METHODS AND SYSTEMS FOR PURIFYING HYDROGEN PEROXIDE SOLUTIONS

CROSS-REFERENCE TO RELATED APPLICATIONS

[001] This application claims the benefit of U.S. Provisional Application Ser. No. 62/143,356, filed on April 6, 2015, and U.S. Provisional Application Ser. No. 62/213,526, filed on September 2, 2015, the disclosures of which are hereby expressly incorporated by reference in their entirety and are hereby expressly made a portion of this application.

FIELD OF THE DISCLOSURE

[002] This disclosure relates to methods and systems for purifying source liquids, particularly reactive source liquids, such as hydrogen peroxide or hydrazine, that may be used as a source for high purity process gases.

BACKGROUND

[003] Various process gases may be used in the manufacturing and processing of microelectronics. In addition, a variety of chemicals may be used in other environments demanding high purity gases, e.g., critical processes, including without limitation

microelectronics applications, wafer cleaning, wafer bonding, photoresist stripping, silicon oxidation, surface passivation, photolithography mask cleaning, atomic layer deposition, atomic layer etch, chemical vapor deposition, flat panel displays, disinfection of surfaces contaminated with bacteria, viruses and other biological agents, industrial parts cleaning, pharmaceutical manufacturing, production of nano-materials, power generation and control devices, fuel cells, power transmission devices, and other applications in which process control and purity are critical considerations. In those processes, it is necessary to deliver specific amounts of certain process gases under controlled operating conditions, e.g., temperature, pressure, and flow rate.

[004] For a variety of reasons, gas phase delivery of process chemicals is preferred to liquid phase delivery. For applications requiring low mass flow for process chemicals, liquid delivery of process chemicals is not accurate or clean enough. Gaseous delivery would be desired from a standpoint of ease of delivery, accuracy and purity. Gas flow devices are better attuned to precise control than liquid delivery devices. Additionally, micro-electronics applications and other critical processes typically have extensive gas handling systems that make gaseous delivery considerably easier than liquid delivery. One approach is to vaporize the process chemical component directly at or near the point of use. Vaporizing liquids provides a process that leaves heavy contaminants behind, thus purifying the process chemical. However, for safety, handling, stability, and/or purity reasons, many process gases are not amenable to direct vaporization.

[005] There are numerous process gases used in micro-electronics applications and other critical processes. Ozone is a gas that is typically used to clean the surface of

semiconductors (e.g., photoresist stripping) and as an oxidizing agent (e.g., forming oxide or hydroxide layers). One advantage of using ozone gas in micro-electronics applications and other critical processes, as opposed to prior liquid-based approaches, is that gases are able to access high aspect ratio features on a surface. For example, according to the International Technology Roadmap for Semiconductors (ITRS), current semiconductor processes should be compatible with a half-pitch as small as 20-22 nm. The next technology node for semiconductors is expected to have a half-pitch of 14-16 nm, and the ITRS calls for <10 nm half-pitch in the near future. At these dimensions, liquid-based chemical processing is not feasible because the surface tension of the process liquid prevents it from accessing the bottom of deep holes or channels and the comers of high aspect ratio features. Therefore, ozone gas has been used in some instances to overcome certain limitations of liquid-based processes because gases do not suffer from the same surface tension limitations, Plasma-based processes have also been employed to overcome certain limitations of liquid-based processes. However, ozone- and plasma-based processes present their own set of limitations, including, inter alia, cost of operation, insufficient process controls, undesired side reactions, and inefficient cleaning.

[006] More recently, hydrogen peroxide has been explored as a replacement for ozone in certain applications. However, hydrogen peroxide has been of limited utility, because highly concentrated hydrogen peroxide solutions present serious safety and handling concerns and obtaining high concentrations of hydrogen peroxide in the gas phase has been difficult.

Hydrogen peroxide is typically available as an aqueous solution. In addition, because hydrogen peroxide has a relatively low vapor pressure (boiling point is approximately 150 °C), available methods and devices for delivering hydrogen peroxide generally do not provide hydrogen peroxide containing gas streams with a sufficient concentration of hydrogen peroxide.

[007] For vapor pressure and vapor composition studies of various hydrogen peroxide solutions, see, e.g., Hydrogen Peroxide, Walter C. Schumb, Charles N. Satterfield and Ralph L. Wentworth, Reinhold Publishing Corporation, 1955, New York, available at

http:/lhdl.handle.neU2027/mdp.39015003708784. Moreover, studies show that delivery into vacuum leads to even lower concentrations of hydro gen peroxide (see, e.g., Hydrogen Peroxide, Schumb, pp. 228-229). The vapor composition of a 30 % H ₂ 0 ₂ aqueous solution delivered using a vacuum at 30 mm Hg is predicted to yield approximately half as much hydrogen peroxide as would be expected for the same solution delivered at atmospheric pressure. [008] Gas phase delivery of low volatility compounds presents a particularly unique set of problems. One approach is to provide a multi-component liquid source wherein the process chemical is mixed with a more volatile solvent, such as water or an organic solvent (e.g., isopropanol). However, when a multi-component solution is the liquid source to be delivered (e.g., hydrogen peroxide and water), Raoult's Law for multi-component solutions, becomes relevant. According to Raoult's Law, for an idealized two-component solution, the vapor pressure of the solution is equal to the weighted sum of the vapor pressures for a pure solution of each component, where the weights are the mole fractions of each component:

[009] In the above equation, P _to t is the total vapor pressure of the two-component solution, P _a is the vapor pressure of a pure solution of component A, X _a is the mole fraction of component A in the two-component solution, P is the vapor pressure of a pure solution of component B, and b is the mole fraction of component B in the two-component solution.

Therefore, when A and B have different vapor pressures, the relative mole fraction of each component is different in the liquid phase than it is in the vapor phase above the liquid.

Specifically, the more volatile component (i.e., the component with the higher vapor pressure) has a higher relative mole fraction in the gas phase than it has in the liquid phase. In addition, because the gas phase of a typical gas delivery device, such as a bubbler, is continuously being swept away by a earner gas, the composition of the two-component liquid solution, and hence the gaseous head space above the liquid, is dynamic.

[010] Thus, according to Raoult's Law, if a vacuum is pulled on the head space of a multi-component liquid solution or if a traditional bubbler or vaporizer is used to deliver the solution in the gas phase, the more volatile component of the liquid solution will be preferentially removed from the solution as compared to the less volatile component. This limits the concentration of the less volatile component that can be delivered in the gas phase. For instance, if a carrier gas is bubbled through a 30% hydrogen peroxide/water solution, only about 295 ppm of hydrogen peroxide will be delivered, the remainder being all water vapor (about 20,000 ppm) and the carrier gas.

[011] The differential delivery rate that results when a multi-component liquid solution is used as the source of process gases makes challenging repeatable process control. It is difficult to write process recipes around continuously changing mixtures. In addition, controls for measuring a continuously changing ratio of the components of the liquid source are not readily available, and if available, they are costly and difficult to integrate into the process. In addition, certain solutions become hazardous if the relative ratio of the components of the liquid source changes. For example, hydrogen peroxide in water becomes explosive at concentrations over about 75 %; and thus, delivering hydrogen peroxide by bubbling a dry gas through an aqueous hydrogen peroxide solution, or evacuating the head space above such solution, can take a safe solution (e.g., 30 % H2O2/H2O) and convert it to a hazardous material that is over 75 % hydrogen peroxide. Therefore, currently available delivery devices and methods are insufficient for consistently, precisely, and safely delivering controlled quantities of process gases in many micro-electronics applications and other critical processes.

[012] There has been recent interest in the use of hydrogen peroxide concentrations above 14 weight %, such as 25 weight % or more, such as 50 weight % or more. Such solutions may include certain stabilizers not otherwise used at lower concentrations. The presence of stabilizers may ultimately degrade or otherwise impair the performance of equipment or materials that come into contact with the stabilizers in applications where the concentrated hydrogen peroxide is used. Additionally, the stabilizers may become undesirably deposited on materials or surfaces intended to be cleaned by the hydrogen peroxide gas in any number of applications or critical processes. Thus, there is a need for methods for puiifying such stabilized hydrogen peroxide solutions prior to their use.

BRIEF DESCRIPTION OF THE DRAWINGS

[013] The following figures form part of the present specification and are included to further demonstrate certain aspects and embodiments of the present disclosure. The disclosure may be better understood by reference to one or more of these figures in combination with the description of specific embodiments presented herein.

[014] Figure 1 schematically illustrates purification of replenishment source liquid for a vaporizer. The arrangement of various components of an apparatus that holds and transports different source liquids in accordance with the invention is shown in the diagram.

SUMMARY OF CERTAIN EMBODIMENTS

[015] In one aspect of the invention, a method comprising:

a) providing a solution comprising hydrogen peroxide and one or more cations; and b) contacting the solution with an ion exchange polymer to produce a purified solution having a reduced content of the one or more cations is provided,

[016] The solution may contain the cations as stabilizers, such as when the solution comprises more than 14 weight % hydrogen peroxide. The method reduces the content of the one or more cations in the solution, thereby reducing or eliminating their possible adverse effects during subsequent processing or use of the solution. [017] After contacting with the ion exchange polymer, the purified solution may undergo additional processing steps. The additional processing steps may include, for example, forming a vapor from a purified liquid solution through contact with another ion exchange membrane. The additional processing steps may also include, for example, contacting a purified vapor solution with another ion exchange membrane and/or delivering the resulting vapor to a critical process or application.

[018] Also provided in the present disclosure are systems, devices, and apparatuses for delivering a purified hydrogen peroxide solution. The systems, devices, and apparatuses comprise:

a) a solution comprising hydrogen peroxide and one or more cations;

b) an ion exchange polymer in contact with the solution; and

c) a housing configured to contain the solution and the polymer.

[019] In certain embodiments, the solution in the systems and devices is a liquid; in other embodiments, the solution is a vapor. In certain embodiments, the systems and devices further comprise a second ion exchange polymer in contact with the purified liquid solution. In certain embodiments, the systems and devices further comprise one or more flow control devices for delivering hydrogen peroxide vapor to a critical process or application.

[020] Additional embodiments and features are included in the detailed description that follows, and will be readily apparent to those skilled in the art from the description or recognized by practicing the embodiments as described in the specification and claims.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS [021] Various embodiments of the invention will now be explained in greater detail. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only, and are not restrictive of the invention as claimed. Any discussion of certain embodiments or features serves to illustrate certain exemplary aspects of the invention. The invention is not limited to the embodiments specifically discussed herein.

[022] Unless otherwise indicated, all numbers such as those expressing temperatures, weight percents, concentrations, time periods, dimensions, and values for certain parameters or physical properties used in the specification and claims are to be understood as being modified in all instances by the term "about." It should also be understood that the precise numerical values and ranges used in the specification and claims form additional embodiments of the invention. All measurements are subject to uncertainty and experimental variability.

[023] As used herein, "substantially gas-impermeable membrane" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a membrane that is relatively permeable to some components that may be present in a gaseous or liquid phase, e.g., hydrogen peroxide, but relatively impermeable to other gases such as, but not limited to, hydrogen, nitrogen, oxygen, carbon monoxide, carbon dioxide, hydrogen sulfide, hydrocarbons (e.g., ethylene), volatile acids and bases, refractory compounds, and volatile organic compounds. A substantially gas-impermeable membrane in accordance with the present disclosure can be relatively permeable to other components that may be present in a gaseous or liquid phase, e.g., water, hydrogen peroxide, hydrazine, and the like. Examples of substantially gas-impermeable membranes include NAFION® (E.I. du Pont de Nemours & Co., Wilmington, DE) and salt derivatives, as well as AQUIVION® (Solvay S.A., Brussels, Belgium) or 3M IONOMER® (3M Co., Minneapolis, MN). Gas impermeability can be determined by the "leak rate" of the membrane.

[024] As used herein, "critical process or application" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a process or application in which process control and purity are critical considerations. Examples of critical processes and applications include without limitation microelectronics applications, wafer cleaning, wafer bonding, photoresist stripping, silicon oxidation, surface passivation, photolithography mask cleaning, atomic layer deposition, atomic layer etch,chemical vapor deposition, flat panel displays, disinfection of surfaces contaminated with bacteria, viruses and other biological agents, industrial parts cleaning, pharmaceutical manufacturing, production of nano-materials, power generation and control devices, fuel cells, and power transmission devices.

[025] As used herein, "leak rate" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to the mass or moles of a particular gas that penetrates the membrane surface area per unit of time.

[026] As used herein, "ion exchange membrane" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a membrane comprising chemical groups capable of combining with ions or exchanging with ions between the membrane and an external substance. Such chemical groups include, but are not limited to, sulfonic acid, carboxylic acid, sulfonamide, sulfonyl imide, phosphoric acid, phosphinic acid, arsenic groups, selenic groups, phenol groups, and salts thereof. When making modifications to ion-exchange membranes resulting in salts, such salts are referred to herein as "ion-exchange membrane salts." When the ion exchange membrane is a component of a membrane-based vaporizer that operates by transport of a chemical component of a source liquid across the ion exchange membrane to enter a gas phase, the ion exchange membrane can be referred to as an ion exchange "separation" membrane.

[027] As used herein, "relatively constant" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a value that, although it may change with time, does not change so substantially so as to render the value inoperative or substantially less operative. In the context of increasing the concentration of a low volatile component, such as H ₂ 0 ₂ , it means maintaining a concentration at sufficiently high levels so as to provide a stable gas delivery of the low volatility component gas for sufficient time to be applied to a critical process or application. For example, maintaining a standard deviation of to within 3% or up to 5% of the mean for an hour would be considered relatively constant.

[028] As used herein, "equilibrium concentration" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to the maximum amount of the less volatile component that may be delivered into the gas phase to be used, for example, to decontaminate a material and will be dependent upon temperature and head space pressure. Under such equilibrium conditions, the molar ratio of the less volatile component to the higher volatile component in the gas phase will be equivalent to the molar ratio of the less volatile component to the higher volatile component in the solution phase of the liquid used to replenish the multi-component source liquid. In solutions with multiple components, under such equilibrium conditions in accordance with the present invention, the molar ratio of the less volatile component to the higher volatile components in the gas phase will be equivalent to the molar ratio of the less volatile component to the higher volatile components in the solution phase of the liquid used to replenish the multi-component source liquid.

[029] As used herein, "stable" in the context of the output gas comprising the less volatile component from the multi-component source liquid, such as hydrogen peroxide in the gas-phase at a stable steady state concentration, means an output concentration that does not vary beyond certain parameters such as, for example, by more than 10% in some embodiments and not by more than 5%, 3% or 2% in other embodiments. The term applies once an equilibrium concentration of the less volatile component in the gas phase has been achieved and is being delivered to a critical process or application. The percentages herein are the standard deviation from the mean with respect to the mean of measured gas output.

[030] As used herein, "stable steady state concentration" in the context of the output gas comprising the less volatile component from the multi-component source liquid, means an output that has increased to a concentration that is stable and in equilibrium as those terms are used herein.

[031] As used herein, "gas" means gaseous species that is not a liquid, solid or a plasma as those terms are well understood in the art. Further, a gas is not a mist or a fog as would be generated, for example, by a nebulizer or atomizer. The term further means that there are fewer than 100 particles of liquid from the gas generation source liquid greater than 100 nm in size at standard temperature and pressure conditions in a volume of one liter as measured with a standard condensation nucleation counter. In certain critical application where droplet particles are detrimental, the term gas may preferably means that there are less than 10 particles greater than 100 nm, 50 nm, 25 nm, or lOnm at standard temperature and pressure conditions in a volume of one liter as measured with a standard condensation nucleation counter available from MSP in Minnesota, Particle Measuring Systems or other readily available commercial instruments. In a multicomponent liquid, such as water and hydrogen peroxide, when volatilized and delivered to a critical process application such as a material to be decontaminated, the hydrogen peroxide is in the gas phase. By comparison, it is possible that water, when volatilized and introduced into a carrier gas, may be either a gas or a vapor.

[032] As used herein, "process gas" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a gas that is used in a critical application process, such as the decontamination of a material or cleaning the surfaces of semiconductors or the chemical modification of semiconductor surfaces to form an oxide, hydroxyl ligand.

Similarly, such surfaces may be passivated by the removal of carbon atoms, or reacted with photoresist or photoresist byproducts, or annealing spin-on dielectrics or spin-on silicon based precursors. Exemplary process gases are water, inorganic acids, organic acids, inorganic bases, organic bases, and inorganic and organic solvents. A particular process gas is hydrogen peroxide gas. Another particular process gas includes hydrazine. A process gas "stream" refers to a flow of process gas that may be carried through a pipe, a tube, or other conduit, to a place where the process gas may be used. A process gas stream may include a carrier gas.

[033] As used herein, "earner gas" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a gas that is used to carry another gas through a process train, which is typically a train of piping. Exemplary earner gases are nitrogen, argon, hydrogen, oxygen, C0 ₂ , clean dry air, room air, helium, or other gases or combinations thereof that are stable at room temperature and atmospheric pressure. A carrier gas may be an inert gas. In one embodiment, the carrier gas is nitrogen. The carrier gas may be solely an inert gas or it may have one or more additional components. A carrier gas may further comprise water, for example. By "dry nitrogen" what is meant is a nitrogen gas substantially free of water. In other embodiments, the earner gas may be hydrogen, clean dry air, oxygen, ozone, or combinations thereof. In some embodiments, the carrier gas may be substantially free of water. In certain embodiments, the carrier gas is not passed through a humidifier. In one embodiment, the carrier gas contains an inert gas and water. As used herein, when water is identified as a component of the gas, unless otherwise provided, it is understood to be water in the gas phase.

[034] As used herein, "substantially dry carrier gas" means gas, or a particular kind of gas if in relation to clean dry air or nitrogen for example, that is dehumidified by methods known in the art reduce moisture in a gas so as to deliver a gas that is as dry as practicable. Such methods include, but are not limited to using gas purifiers such as those available from commercial manufacturers.

[035] As used herein, "pre-loaded earner gas" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a carrier gas containing an amount of one or more component(s) of a source liquid. In one embodiment, the pre-loaded carrier gas contains an inert gas and water. In another embodiment, the pre-loaded carrier gas comprises one or more of nitrogen, argon, hydrogen, oxygen, CC% clean dry air, helium, or other gases that are stable at room temperature and atmospheric pressure and water. A pre-loaded earner gas is also considered a carrier gas.

[036] As used herein, "undersaturated" means, in the context of a gas, such as a carrier gas or carrier gas, that the partial pressure of the gas is less than the maximum partial pressure for that gas in the head space or the carrier gas or carrier gas for the given temperature and pressure. The term undersaturated applies at a point specific point in time. The carrier gas may be saturated for a specific temperature and pressure and later be modified by reducing the pressure or increasing the temperature such that the head space or carrier gas is now

undersaturated. As used herein, "oversaturated" means, in the context of a gas, such as a carrier gas or carrier gas, that the that the partial pressure of the gas is greater than the maximum partial pressure for that gas in the head space or the carrier gas or carrier gas for the given temperature and pressure. In some embodiments of the invention, the gas stream delivered to the critical process application is at a higher partial pressure of the component less volatile than water than the partial pressure of that component from the multi-component source liquid used to replenish prior to delivery of that liquid.

[037] As used herein, "inert gas" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and includes without limitation a gas that is relatively impermeable to the membrane as described herein. In one embodiment, the inert gas comprises one or more of nitrogen, argon, helium, or other noble gases. In another embodiment, the inert gas is nitrogen. In another embodiment, the inert gas is dry nitrogen. [038] As used herein, "source liquid" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and generally refers without limitation to a liquid solution that provides the source of a gas through change of phase used in an application or process, specifically a process gas. In certain embodiments, the source liquid directly contacts the ion exchange separation membrane of a membrane-based vaporizer.

[039] As used herein, "replenishment source liquid" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a source liquid used to replenish a system that consumes source liquid. A replenishment source liquid may contain additives or chemical stabilizers, and may be used for refilling a liquid reservoir of a vaporizer apparatus. A commercially obtained 50 weight % stabilized hydrogen peroxide solution that includes sodium stannate, potassium stannate, and zinc stannate is an example of a replenishment source liquid. Notably, the ratio of components in a multicomponent liquid serving as the replenishment source liquid may be the same, or may be different from the ratio of components in the source liquid.

[040] As used herein, "purified replenishment source liquid" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a liquid solution prepared by selectively reducing or removing at least one chemical component from a replenishment source liquid. For example, a purified replenishment source liquid may include a reduced amount of a chemical agent found in a replenishment source liquid, where that chemical agent binds to the material of an ion exchange separation membrane by ionic or absorptive interaction.

[041] As used herein, "head space" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a volume of gas in fluid contact with a source liquid that provides at least a portion of the gas contained in the head space.

[042] As used herein, "vaporizer" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a device that generates a gas, a vapor, or a mist from a starting source liquid. Nebulizers and bubblers are embraced by the term, since these devices produce a vapor from a source liquid. In a specific embodiment represented by a membrane-based vaporizer, which generates a gas starting from a source liquid, there is a headspace, a carrier gas inlet, a carrier gas outlet, and a permeable or selectively permeable barrier (e.g., an ion exchange membrane) separating the head space from the source liquid where the source liquid changes phase and may be used as a process gas. The vaporizer may optionally include a heater to control the temperature of the source liquid and/or vapor. The gas generated from the source liquid by energy supplied by a heat source is swept away by the carrier gas. In certain embodiments the earner gas is saturated. In other embodiments the earner gas is not saturated.

[043] As used herein, the term "vaporizes" refers to a procedure that employs a vaporizer (i.e., a device), and that generates a gas, a vapor, or a mist starting from a source liquid.

[044] One embodiment of the invention includes a method, which comprises: a) providing a solution comprising hydrogen peroxide and one or more cations;

and

b) contacting the solution with an ion exchange polymer to produce a purified solution having a reduced content of the one or more cations.

[045] In certain embodiments, the ion exchange polymer, whether or not in the form of a membrane, is a polysulfonic acid polymer. In still other embodiments, the ion exchange membrane is a fluorine-containing polymer, e.g., polyvinylidenefluoride, polytetrafluoroethylene (PTFE), ethylene tetrafluoride-propylene hexafluoride copolymers (FEP), ethylene tetrafluoride- perfluoroalkoxyethylene copolymers (PFE), polychlorotrifluoroethylene (PCTFE), ethylene tetrafluorideethylene copolymers (ETFE), polyvinylidene fluoride, polyvinyl fluoride, vinylidene fluoride- trifluorinated ethylene chloride copolymers, vinylidene fluoride-propylene hexafluoride copolymers, vinylidene fluoridepropylene hexafluoride-ethylene tetrafluoride terpolymers, ethylene tetrafluoridepropylene rubber, and fluorinated thermoplastic elastomers. In another embodiment, the ion exchange polymer is a perfluorinated polysulfonic acid polymer. Other exemplary perfluorinated ionomers include, but are not limited to, perfluoro sulfonic

acid/tetrafluoroethylene copolymers ("PFSA-TFE copolymer") and perfluorocarboxylic acid/tetrafluoroethylene copolymer ("PFCA-TFE copolymer"). In other embodiments the ion exchange polymer is a perfluorinated polysulfonic acid polymer in the form of a membrane such as NAFION® or a hydrolyzed version of a sulfonyl fluoride perfluorinated membrane.

[046] Preferably, the ion exchange separation membrane of a membrane-based vaporizer is a resin. In one embodiment, the ion exchange membrane is a fluorine-containing polymer. The ion exchange membrane is preferably a perfluorinated ionomer comprising a copolymer of ethylene and a vinyl monomer containing an acid group or salts thereof. These membranes are commercially available under the trade names NAFION® (E.I. du Pont de Nemours & Co., Wilmington, DE), FLEMION® (Asahi Glass Company, Ltd., Tokyo, Japan), and ACIPLEX® (Asahi Kasei Chemicals Company, Tokyo, Japan). 3i IONOMER (3M Company, Minneapolis, MN) or AQUIVION® (Solvay S.A., Bmssels, Belgium) could also be used.

[047] In certain embodiments, a single peak molecular weight is preferred. In certain embodiments, bimodal or multimodal molecular weights are preferred. Preferably, the copolymer is between approximately 500EW and approximately 2000EW. In certain embodiments, the ion exchange membrane may contain either a single copolymer or

combinations of copolymers. In certain embodiments, the polymer can be in any configuration, including, but not limited to, block, tapered, random, linear, and others. PFCA-TFE copolymers contain a tetrafluoroethylene ("TFE") "backbone," to which the perfluorocarboxylic acid (perfluoro(4-methyl-3,6-dioxa-7-octene-l-carboxylic acid)) groups are attached. The acid groups can be converted to salt form by a pretreatment with a suitable base. A PFSA-TFE copolymer contains a TFE "backbone," to which perfluorosulfonic acid (perfluoro(4-methyl-3,6- dioxa-7-octene-l -sulfonic acid)) groups are attached. There are between one and six

perfluorosulfonic acid groups per six TFE backbone units. Copolymers are normally classified by equivalent weight ("EW"), or by grams of polymer per mole of functional group.

[048] The pretreatment methods are well known in the art, and can be performed according to the manufacturer's recommendation. Depending on the nature of the liquid to be vaporized, pretreatment conditions can be adjusted to optimize the membrane. Examples of pretreatment conditions that can be adjusted and include, but are not limited to, selection of base, solvents, temperature, soaking in a hydrogen peroxide solution, and other parameters that would be known to a person of skill in the art.

[049] Hydrophilicity can be adjusted by cross-linking with a hydrophilic agent or by co- casting. In such embodiments where hydrophilicity is adjusted by cross-linking with a hydrophilic agent or by co-casting, the polymer already includes cross-linkable groups, or is functionalized to include cross-linkable groups. Other pretreatments without modifying surface chemistiy can be employed. In another embodiment, the polymer can be impregnated with inorganic oxides. This impregnation can improve thermal stability by 5°C - 120°C. This can also increase water transport rate properties by 2% - 40%.

[050] Preferably, the membrane suppresses the diffusion of gases and other

contaminants, such as particles, aerosols, viruses, bacteria, and prions. Preferably, the thickness of the membrane is between 0.5 microns and 2,000 microns. The leak rate is measured by monitoring the pressure in an isolated static system. An example of a leak rate is 10 ^" cm /cm /s for nitrogen at standard temperature and pressure. Leak rates can be as high as 10 ^"3 cm ³ /cm ² /s at standard temperature and pressure or as low as 10 ^" cm /cm /s for a specific gas.

[051] In one method of generating a gas from a source liquid, the source liquid is contacted to a first side of a substantially gas impermeable membrane and the gas generated is received on the second side of the substantially gas impermeable membrane. In certain embodiments, the first and second sides of the substantially gas impermeable membrane have a flat form, wherein the membrane is a sheet. In other embodiments, the membrane can also be in a tubular or cylindrical form, wherein one surface forms the inner potion of a tube, and the opposing surface forms the outer portion of the tube. In all embodiments, the membrane can take any form, provided that a first surface and an opposing second surface sandwich a bulk of membrane material.

[052] Certain properties of the membrane can be adjusted, depending on the process conditions, the nature of the gas being generated, and other factors. Such adjustable properties can include: the physical form of the membrane, the configuration of the membrane, the fabrication method of the membrane, the presence or absence of a support layer of the membrane, the presence or absence of an active layer of the membrane, as well as other properties not listed here.

[053] When the membrane is thin, it is preferred to give the membrane some means of mechanical support. Thicker membranes can be used without such support.

[054] In certain embodiments, the surface area of the membrane can be adjusted based on the volume of gas to be generated. Either a higher or lower surface area can be desirable, depending on the chemistry of membrane. In an alternative embodiment, the resin comprises a composite or mixture of polymers. This composite or mixture of polymers can comprise two or more layers. The layers can have the same or different properties as one another. A layer can provide support to filtration.

[055] In certain embodiments, it is generally preferable for the membranes to be in fiber form, rather than in sheet form, due to the ability to provide greater exposed membrane surface area in a fixed volume when fibers are employed.

[056] The solution may be in liquid or vapor form. When the solution is a liquid, a further embodiment comprises:

a) providing a solution comprising hydrogen peroxide and one or more cations; b) contacting the solution with an ion exchange polymer to produce a purified solution having a reduced content of the one or more cations; and

c) forming a vapor from the purified liquid solution.

[057] The vapor may be formed in c) through any suitable technique, such as through applying heat.

[058] In another embodiment, the vapor is formed in c) by contacting the purified liquid solution with a substantially gas-impermeable ion exchange membrane such as a perfluorinated polysulfonic acid polymer membrane. Such a technique is disclosed in WO 2014/014511, titled "Method, System, and Device for Delivery of High Purity Hydrogen Peroxide," the entire contents of which are incorporated by reference herein. The purified liquid solution may, for example, contact a first side of such a membrane to ultimately obtain a vapor emerging from a second side of the membrane. In this instance, the vapor phase and liquid source are separated by a substantially gas-impermeable ion exchange membrane, such as a perfluorinated

polysulfonic acid polymer membrane. By using such a membrane, the concentration of hydrogen peroxide in the resultant vapor may be increased relative to the hydrogen peroxide concentration that would be obtained directly from the solution without the use of a membrane.

[059] The ion exchange polymer membrane may be composed of any suitable materials, such as those described above for the ion exchange polymer. The membrane may also have any suitable structure. For example, the first and second sides can have the form of substantially flat, opposing planar areas, where the membrane is a sheet. Membranes can also be provided in tubular or cylindrical form where one surface forms the inner position of the tube and an opposing surface lies on the outer surface. The membrane can take any form, so long as the first surface and an opposing second surface sandwich a bulk of the membrane material. Multiple membranes may also be arranged in the form of an assembly, for example, with several membranes configured as lumens inserted at each end into holes of a collector plate.

[060] Depending on the processing conditions, nature of the solution, volume of the solution's vapor to be generated, and other factors, the properties of the membrane can be adjusted, Properties include, but are not limited to physical form (e.g., thickness, surface area, shape, length and width for sheet form, diameter if in fiber form), configuration (flat sheet(s), spiral or rolled sheet(s), folded or crimped sheet(s), fiber array(s)), fabrication method (e.g., extrusion, casting from solution), presence or absence of a support layer, presence or absence of an active layer (e.g., a porous prefilter to adsorb particles of a particular size, a reactive prefilter to remove impurities via chemical reaction or bonding), and the like. It is generally preferred that the membrane be from about 0.5 microns in thiclaiess or less to 2000 microns in thickness or more, preferably from about 1, 5, 10, 25, 50, 100, 200, 300, 400, or 500 microns to about 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, or 1900 microns. When thinner membranes are employed, it can be desirable to provide mechanical support to the membrane (e.g., by employing a supporting membrane, a screen or mesh, or other supporting structure), whereas thicker membranes may be suitable for use without a support. The surface area can be selected based on the mass of vapor to be produced.

[061] In embodiments where a vapor has been formed in c), such as through application of heat to the liquid solution, a further embodiment comprises:

[062] One embodiment of the invention includes a method, which comprises:

a) providing a solution comprising hydrogen peroxide and one or more cations;

b) contacting the solution with an ion exchange polymer to produce a purified solution having a reduced content of the one or more cations; c) forming a vapor from the purified liquid solution; and

d) passing the vapor through an ion exchange polymer membrane, such as a

perfluorinated polysulfonic acid polymer membrane, an example of such a membrane being NAFION® or hydrolyzed versions of sulfonyl fluoride perfluorinated membranes.

[063] Step d) may utilize the membrane to remove contaminants from the vapor stream, and the membrane may have any of the structural characteristics described above.

[064] Methods, systems, and devices for delivering hydrogen peroxide vapor with a perfluorinated ion exchange membrane are disclosed in PCT Publication WO 2014/165637, titled "Delivery of a High Concentration Hydrogen Peroxide Gas Stream," filed on April 3, 2014, the entire contents of which is hereby incoiporated by reference herein, particularly paragraphs [0030] to [0043], In addition, analogous methods, systems, and devices are disclosed in U.S. Provisional Application No. 61/824,127, titled "Delivery of a High Concentration Hydrogen Peroxide Gas Stream," filed on May 16, 2013; and U.S. Provisional Application No. 61/809,256, titled "Delivery of a High Concentration Hydrogen Peroxide Gas Stream," filed on April 5, 2013. The entire contents of those applications are also hereby incorporated by reference herein.

[065] In some embodiments, the solution in a) is in the form of a vapor. Similarly to the vapor that can be formed in c), this purified vapor may also be passed through an ion exchange polymer membrane, such as a perfluorinated polysulfonic acid polymer membrane, for example, for the purpose of removing contaminants.

[066] The purified vapor resulting from any of the embodiments discussed above may be delivered to any suitable critical process or application. Such critical processes and applications include, without limitation, microelectronics applications, wafer cleaning, wafer bonding, photoresist stripping, silicon oxidation, surface passivation, photolithography mask cleaning, atomic layer deposition, chemical vapor deposition, flat panel displays, disinfection of surfaces contaminated with bacteria, viruses and other biological agents, industrial parts cleaning, pharmaceutical manufacturing, production of nano-materials, power generation and control devices, fuel cells, and power transmission devices.

[067] Another embodiment of the invention includes a method, which comprises:

a) providing a solution comprising hydrogen peroxide and one or more cations;

b) contacting the solution with an ion exchange polymer to produce a purified solution having a reduced content of the one or more cations;

c) forming a vapor from the purified liquid solution;

d) passing the vapor through an ion exchange polymer membrane, such as a

perfiuorinated polysulfonic acid polymer membrane, an example of such a membrane being NAFION® or hydrolyzed versions of sulfonyl fluoride perfiuorinated membranes; and

e) delivering the vapor resulting from step c) or step d) to a critical process or application.

[068] The solution in step a), whether liquid or vapor, may comprise water in any suitable amount or may be substantially free of water. In some embodiments the solution is substantially free of water, meaning that water is not puiposefully added to the solution such as through a dedicated source of water. The phrase "substantially free of water" does not exclude the incidental water content that may be present in the sources of other solution components, such as may be present in the source of hydrogen peroxide. The phrase "substantially free of water" similarly does not exclude incidental water content that may arise from decomposition of hydrogen peroxide on system components, or that may enter an enclosure of the solution from the outside environment. In some embodiments, the solution comprises 2% or less by weight of water, or 1.5 weight % or less, or 1.0 weight% or less, or 0.5 weight% or less of water.

[069] In addition to hydrogen peroxide, the solution may further comprise a nonaqueous excipient. Example non-aqueous excipients include, but are not limited to, alcohols, including polyalcohols, phenols, lactones, amides, esters, including polyesters, ethers, carboxylic acids, including polycarboxylic acids, sulfonic acids, sulfmic acids, phosphonic acids, phosphinic acids, organic solvents, inorganic solvents, aromatic compounds, polyaromatic compounds, heterocyclic compounds, including polyheterocyclic compounds, fluorinated ethers, ffuorinated alcohols, fluorinated sulfonic acids, fluorinated carboxylic acids, including polycarboxylic acids, fluorinated phosphonic acids, deep eutectic solvents, and combinations thereof.

[070] The solution in step a) comprises one or more cations. The cations may be present, for example, as stabilizers for the hydrogen peroxide solution, such as for a solution comprising more than 14 weight % hydrogen peroxide, such as 25 weight % or more, such as 50 weight % or more.

[071] In some embodiments, the one or more cations comprise one or more metal cations. Example metal cations include sodium, potassium, barium, calcium, copper, magnesium, manganese, nickel and zinc cations. In one embodiment, the one or more metal cations comprise a sodium, potassium, magnesium, copper or calcium cation; in another embodiment the one or more metal cations comprise a magnesium or calcium cation; and in a further embodiment the one or more metal cations comprise a copper cation. In an additional embodiment, the one or more metal cations comprise a sodium or potassium cation, such as can be derived from sodium starmate or potassium stannate, respectively. [072] The metal cations may be present in any suitable amount in the solution, whether used as stabilizers or for other puiposes. For instance, the solution may comprise 15 ppm or less by weight of metal cations, or 10 ppm or more by weight of metal cations.

[073] The solution also comprises hydrogen peroxide in any suitable amount. For example, the solution may comprise hydrogen peroxide in an amount of 10 weight % or more, 15 weight % or more, 20 weight % or more, 25 weight % or more, 30 weight % or more, 35 weight % or more, 40 weight % or more, 45 weight % or more, 50 weight % or more, 55 weight % or more, 60 weight % or more, 65 weight % or more, or 70 weight % or more.

[074] The ion exchange polymer in a) may be in the form of any shape or structure. For example, it may be in the form of a membrane having any of the structural characteristics of the ion exchange membranes discussed previously. The ion exchange polymer in a) could also be in the form of, for example, a bead or pellet.

[075] Perfluorinated polysulfonic polymers are ion exchange polymers such as those made when hydrolyzing sulfonyl fluoride perfluorinated membranes to obtain a perfluorinated polysulfonic acid membrane. Examples of such polymers are disclosed in WO 2014/014511, with those examples being incorporated by reference herein. NAFION® is an example of a perfluorinated sulfonic acid membrane. The ion exchange polymer (such as a perfluorinated polysulfonic polymer) in a), and the ion exchange polymer membranes (such as perfluorinated polysulfonic polymer membranes) described previously, may have identical compositions or may be made of different variants of ion exchange material. The ion exchange polymer (such as perfluorinated polysulfonic polymer) material, whether in the form of a membrane or not, includes such a material that has been chemically treated e.g., with an acid, base, or salt to modify its reactivity. For example, in certain embodiments, the NAFION® material, whether in the form of a membrane or not, may be treated in a way to form, e.g., the ammonium species.

[076] The solution is contacted with the ion exchange polymer in step b) to produce a solution having a reduced content of the one or more cations.

[077] The phrase "reduced content of the one or more cations" refers to a reduced concentration of at least one cation in the solution after contact with the polymer compared to the concentration of that cation before contact with the polymer. The phrase "reduced content of the one or more cations" does not require complete removal of any cation from the solution. The phrase "reduced content of the one or more "cations" also does not require a reduction in the concentration of several, most or all cations in the solution. In some exemplary embodiments, however, contact of the solution with the polymer reduces the content of at least two, at least three, at least four, or at least five cations in the solution.

[078] Some embodiments therefore comprise contacting the solution with the ion exchange polymer under conditions sufficient to remove 70 weight % or more of at least one cation from the solution. Exemplary cations in this embodiment include sodium, potassium, barium, calcium, copper, magnesium, manganese, nickel and zinc cations.

[079] Another embodiment comprises contacting the solution with the ion exchange polymer under conditions sufficient to remove 80 weight % or more of at least one cation from the solution. Exemplary cations in this embodiment include sodium, potassium, barium, calcium, magnesium, manganese, nickel and zinc cations.

[080] Another embodiment comprises contacting the solution with the ion exchange polymer under conditions sufficient to remove 90 weight % or more of at least one cation from the solution. Exemplary cations in this embodiment include potassium, barium, calcium, magnesium and manganese cations.

[081] A further embodiment comprises contacting the solution with the ion exchange polymer under conditions sufficient to remove 50 weight % or more, or 60 weight % or more of the combined total of all cations, or 50 weight % or more, or 60 weight % or more of the combined total of all metal cations, from the solution.

[082] The solution may be contacted with the ion exchange polymer using any suitable technique. For instance, the solution may be directed to flow over a surface of the polymer, such as by passing from an inlet end to an outlet end of an enclosure containing the polymer. The solution may also contact the polymer by positioning the polymer in an enclosure that contains a volume of the solution that is either static or in fluid motion. Thus, in one embodiment contacting step b) may comprise passing the solution through a packed bed comprising the ion exchange polymer. In another embodiment contacting step b) comprises placing the ion exchange polymer in a liquid solution.

[083] The solution may contact the ion exchange polymer under any conditions sufficient to reduce the content of the one or more cations. For instance, the solution may contact the polymer for a cumulative time of at least 5 seconds, at least 10 seconds, at least 30 seconds, at least 1 minute, at least 5 minutes, at least 10 minutes, at least 15 minutes, at least 30 minutes, at least 45 minutes, at least 1 hour, at least 2 hours, or at least 3 hours. The contact may also take place at any appropriate temperature, such as at room temperature (22°C).

[084] The present disclosure also includes a vaporizer device or apparatus, and analogous systems, for delivering purified hydrogen peroxide vapor. The systems, devices, and apparatuses comprise: a) a solution comprising hydrogen peroxide and one or more cations;

b) an ion exchange polymer in contact with the solution; and

c) a housing configured to contain the solution and the polymer.

[085] In certain embodiments, the vaporizer contains the membranes which are preferably fixed in a module or other suitable apparatus. In embodiments in which the membranes are in fiber form, preferably the membranes are arranged in cylindrical arrays or bundles. In other embodiments, other configurations can be employed, such as square, triangular, irregular, or other configurations. The membrane module preferably includes a plurality of hollow membrane fibers each of which extend longitudinally between, and are mounted at each end to, a respective header. In other embodiments, other configurations are contemplated, such as looped fibers wherein both ends are secured in a single header, among other configurations. Preferably, the fibers can be taut or slack, close or loosely packed formation, or spaced apart. The fibers preferably have a packing density of from 5% or less to about 95% or more, or any density in between those two values. The fibers may optionally be partitioned into a certain number of bundles in order to form a space or spaces therein between. Optionally, a single bundle of fibers may be employed,

[086] In some embodiments, it is preferred to maintain some spacing in between the fibers to facilitate circulation of the source liquid (e.g., the purified replenishment source liquid). Optionally, a fiber bundle can be protected by a module support screen. Optionally, casing can provide support to a header or headers. Optionally, clips or rings can be employed to bind the fiber bundle. Preferably, materials employed in the header and any supports or casing are selected such that these materials are able to tolerate elevated temperature and pressure conditions and will resist reacting with or contaminating any gas generated. In some certain embodiments, one or more membrane module may be arranged into a cassette or battery, each cassette or battery being provided with a source liquid, pumps, valves, and instrumentation.

[087] In some embodiments carrier gas enters from the lower header and exits from the upper header. In other embodiments the carrier gas enter from above and exits from the lower header. In each case gas generated from the source liquid permeates the membrane is swept away by earner gas.

[088] The carrier gas may be saturated, oversaturated, or understaturated with the gas generated by the source liquid.

[089] In certain embodiments the vaporizer contains level sensors, commercially available from Gems Sensors & Controls, Inc., Plainville, CT. Any person of ordinary skill in the art recognizes the use of level sensors in the embodiments of the invention,

[090] In certain embodiments the vaporizer contains thermal sensors, commercially available from Omega Engineering, Inc., Stamford, CT. Any person of ordinary skill in the art recognizes the use of thermal sensors in the embodiments of the invention.

[091] In certain embodiments the vaporizer contains over temperature sensors, commercially available from Omega Engineering, Inc., Stamford, CT. Any person of ordinary skill in the art recognizes the use of temperature sensors in the embodiments of the invention.

[092] In certain embodiments the vaporizer contains a drain valve, commercially available from BioChem Fluidics, Inc., Boonton, NJ. Any person of ordinary skill in the art recognizes the use of a drain valve in the embodiments of the invention.

[093] In certain embodiments the vaporizer contains a replenishment vessel, commercially available from BioChem Fluidics, Inc, Boonton, NJ. Any person of ordinary skill in the art recognizes the use of a replenishment vessel in the embodiments of the invention. [094] In certain embodiments, gas generated from a source liquid can be delivered at subatmospheric pressures. Delivery at sub-atmospheric pressures is desirable in many applications, such as atomic layer deposition. Sub-atmospheric pressures can be achieved with downstream vacuum pumps.

[095] In certain embodiments, the device comprises a primary pump on the permeate side, and a second pump connected to the source liquid side. In these embodiments, the vapor pressure differential or downstream pressure can be managed by adjusting the power input to the vaporizer, amount of carrier gas flow rate, carrier gas pressure, pressure drop between the liquid to the permeate side, or downstream venting.

[096] Once choke flow is reached across the membrane or on the permeate side of the vaporizer, further lowering of pressure on the permeate side of the vaporizer no longer increases the permeation rate across the membrane. Only by increasing the vapor pressure of the source liquid by adding power through the heater to the vaporizer will increase permeation of the gas generated by the source liquid increase.

[097] In one embodiment the power supplied to the vaporizer is through heating the outside of the vaporizer with electrical heaters. One skilled in the art could apply energy through other method, such as steam, transfer liquids, ambient heat, heating of the carrier gas, and other techniques.

[098] Figure 1 illustrates the relationship between various source liquids, purification media, and a vaporizer in accordance with the invention. A supply of replenishment source liquid 13 is stored in replenishment source liquid container 1 (e.g., a first container). Fluid connection 4 facilitates transfer of replenishment source liquid 13 to purification replenishment source liquid container 2 (e.g., a second container). Replenishment source liquid 13 can be transferred from replenishment source liquid container 1 to purification replenishment source liquid container 2 by any convenient means, including a pump, pressurized gas, or gravity feed. Inside purification replenishment source liquid container 2 is purification material 3, which contacts replenishment source liquid 13 and converts it to purified replenishment source liquid 14. In a preferred embodiment, purification material 3 is in the form of a membrane. Purification material 3 preferably includes a perfluorinated ionomer (e.g., a PTSA-TFA copolymer) with high surface area, and can be a NAFION® PTSA-TFA copolymer membrane. Purified replemshment source liquid 14 is transported via fluid connection 5 to pump 6, and then through fluid line 7 to vaporizer 11. A preferred type of pump is a diaphragm pump, as may be obtained from Bio- Chem Fluidics (Wildomar, CA). Many other pumps, as well as pressurized transfer or gravity feed systems also may be used for transporting purified replemshment source liquid 14 from purification replenishment source liquid container 2 to vaporizer 11. The vaporizer may be a flash vaporizer, a nebulizer, a bubbler, or more preferably a membrane-based vaporizer. Purified replemshment source liquid 14 is added to source liquid 10, which is contained in vaporizer 11. Carrier gas 12 enters vaporizer 11. In some embodiments, carrier gas 12 may enter vaporizer 11 as bubbles (e.g., through a sparger).

[099] As illustrated in the diagram, and in the preferred case of a membrane-based vaporizer, earner gas 12 enters through hollow fiber ion exchange separation membrane 15. The membrane is preferably made from an ion exchange membrane, and is preferably made from the same material as purification material 3. For example, both purification material 3 and hollow fiber ion exchange separation membrane 15 can be made of an ionic fluoropolymer such as NAFION® ion exchange membrane. Source liquid 10 vaporizes across hollow fiber ion exchange separation membrane 15, and then is swept away by a flow of carrier gas 12. Process gas stream 8 exits the vaporizer as a mixture of a volatile chemical component of vaporized source liquid 10 and earner gas 12.

Examples

[100] Materials used in the examples: 50 weight % (w%) stabilized hydrogen peroxide (Sigma Aldrich), NAFION® Membrane 1100EW, 0.1 N NaOH solution, 1 weight %

bromothymol blue, Sodium Sulfate (ACS grade), DI water, Hot/Stir Plate, Stir bar, 500mL and 100 mL beakers, Timer, 10-100 μΐ, pipette, Analytical Scale (±0.001g), and Ceramic Scissors.

[101] Example 1 : NAFION® Based Purification of Peroxide Stabilizer Test Procedures. The following five tests outlined below were conducted:

Test #1 : Titration of NAFION® Lumen Control 1

• Titrate a l.OOOg sample of NAFION® following Test #6 to determine the relative acid conversion of stock NAFION®

Test #2: Titration of NAFION® Lumen Control 2

• Titrate a 1.000g sample of NAFION® following the Acid Titration Procedure to determine the relative acid conversion of stock NAFION®

Test #3: Purification of 50w% Peroxide Using Excess NAFION®

• Add an excess amount of NAFION®, 3.000g, to 50ml of 50w% peroxide solution in a 100ml beaker

• Let the NAFION® soak in solution at room temperature (22 °C) for one hour

• Remove the lumen from the peroxide solution and rinse with DI water for 2

minutes

• Dry NAFION® under de-ionizer fan for 2 hours

• Weigh two l.OOOg samples and titrate each sample following Test #6 o Results identified as 3 a and 3b respectively

Test #4: NAFION® Purification Efficiency Test

• 45ml of the purified 50w% peroxide solution from Test 3 and +1.OOOg of

NAFION® are placed in a lOOmL beaker

• Let the NAFION® soak in solution at room temperature (22 °C) for one hour

• Remove the lumen from the peroxide solution and rinse with DI water for 2 minutes

• Dry NAFION® under de-ionizer fan for 2 hours

• Titrate the 1.OOOg sample following Test #6

Test #5: Excess 50w% Peroxide Purification Test

• A 1.OOOg sample of NAFION® is added to 350ml of stabilized 50w% hydrogen peroxide

• Let the NAFION® soak in solution at 50 °C for one hour

• Remove the lumen from the peroxide solution and rinse with DI water for 2 minutes

• Dry NAFION® under de-ionizer fan for 2 hours

• Titrate the 1.OOOg sample following Test #6

Test# 6: Acid Titration Procedure

• Prepare 0.1 M KOH solution

• Cut 1.0 gram sample NAFION® into ½ inch sections, and place in 50 ml of DI water in a 500ml beaker

• Add 2.0 g K ₂ S0 ₄ to beaker, and 3 drops of bromothymol blue to beaker

• Place beaker on a hot plate with a stir bar, heating to approximately 40-50 °C • Add drop wise 0.1 M KOH to solution until solution turns blue

• Calculate % converted based upon an EW of 1100

(KOH mols added)

% Converted = (Dry Mass NAFION®) g * 100

(HOO g/mol)

[102] Example 2: Trace Metal Analysis of Stock and Purified Stabilized 50w% Hydrogen Peroxide, A quantitative analysis was run on the 50w% peroxide solution itself. lOOmL of 50w% stabilized peroxide was purified with 6.016g of NAFION® for 2.25 hours at 22 °C. The mass of NAFION® added to the 100 mL solution had six times the amount of sulfonic acid sites required to purify this volume of solution based on the 5.88 x 10 ^" mol/L stabilizer concentration determined by titrations 3a and 3b.

[103] Test Results. Table 1 below provides the test conditions and titration results for the experiments.

Table 1: Test Conditions and Titration Results

[104] Table 2 provides the trace metal ion analysis of stock and purified stabilized 50w% hydrogen peroxide.

Table 2: Trace Metal Ion Analysis of Stock and Purified Stabilized 50w% Hydrogen

Peroxide

[105] Test 1 and test 2 results determined that the NAFION® used in all tests during this experiment has a starting acid conversion of 98.0 ± 1.0%. Reduction from 98% acid conversion in all NAFION® samples after exposure to the test conditions 3-6 will be used to calculate the moles of ionic stabilizers that were removed per volume of stabilized 50w% peroxide solution.

[106] Test 3 used an excess amount of NAFION® to pull ionic stabilizers out of the 50ml of peroxide solution. The 3.049g mass of NAFION® dropped to an average acid conversion of 87.4 ± 0.2% (average of 3a and 3b titrations). The 10.6% drop in acid conversion on the 3.049g NAFION® sample corresponds to removing 2.94 x 10 ⁴ mol of ions per 50ml of peroxide solution. Multiplying this value by 20 standardizes the concentration in mol of ions per liter; the concentration of ionic stabilizers in stabilized 50w% peroxide was found to be 5.88 x 10 ^"3 mol/L.

[107] Test 4 conditions evaluated the efficiency of the stabilizer removal achieved by test 3. The 1.040g sample mass was placed in the purified peroxide solution from test 3. The NAFION® sample lost 1.4% of its acid content. The ionic stabilizer concentration of the purified peroxide after test 3 was calculated from the total moles of sulfonic acid lost from the 1.040g sample mass; 1.32 x 10 ^"5 mol of ions per 45ml of solution which corresponds to a stabilizer concentration of 2.94 x 10 ^"4 mol/L. The single treatment process defined in test 3 was highly effective at removing ionic stabilizers. The ionic stabilizer concentration reduced by 20 fold which corresponds to removing 95.2% of the ionic stabilizers through a single NAFION® treatment process.

[108] Test 5 examined NAFION®'s ability to participate in stabilizer exchange at lower acid conversion levels. This test determined that 5 NAFION® lumens can utilize at least 95% of the membranes ion exchange capacity to remove ionic stabilizers from 50w% hydrogen peroxide solutions. The 1.158g sample of NAFION® was converted from 98,0%o to 3.8%.

Alongside with NAFION®' s excellent resistance to degradation in highly corrosive peroxide solutions, ionic stabilizers were able to fully saturate the membrane deeming NAFION® an efficient resin to use in hydrogen peroxide purification.

[109] The trace metal analysis results of the stock 50w% peroxide solution determined that 97.8% of the ionic stabilizer content was due to the following metal ions in increasing order: Cd (9.35%), Sn (16.55%), Na (19.43%), and K (52.53%). The total concentration of ionic stabilizers in the stock solution was 13.90 ppm by mass. After the purification with the +6.0g of NAFION®, the ionic stabilizer concentration was reduced to 5.382 ppm by mass. 61.3% of the ionic stabilizer content was removed using a single ion exchange purification step,

[110] Table 2 highlights the metal ion species that NAFION® was highly effective at removing (Ba, Ca, Cu, Mg, Mn, Ni, K, Na, and Zn). Of the major ionic contributors, NAFION® treatment was able to remove 90.7% of the potassium ions and 83.6%) of the sodium ions. The NAFION® membrane removed > 93% of the Ca, Mg, and Mn ions, 86.3% of Ni, and > 78% of the Cu and Ni ions. Overall, NAFION® membrane was found effective at removing the ionic stabilizer content in stabilized peroxide solutions.

[Ill] It was further observed that the polymers could be re-acidified in acidic medium such as 10%) by weight nitric acid. Other acids may also be used. The ability to re-acidify the polymers indicates that the loss in acid content was due to ionic contamination.

[112] Example 3 : Purification of 50 w% Hydrogen Peroxide Using Excess NAFION® Ion Exchange Membrane. Example 3 describes procedures used to determine whether the initial contact with the NAFION® ion exchange membrane, described in Example 2, was sufficient to purify the hydrogen peroxide by removal of all ionic stabilizers.

[113] An approximately 3.000g sample of NAFION® ion exchange membrane was placed in 50mL of 50w% stabilized hydrogen peroxide (Sigma Aldrich; St. Louis, MO) contained in a lOOmL beaker. The membrane was allowed to soak in the solution at room temperature (22°C) for one hour. Next, the membrane was removed from the hydrogen peroxide solution and rinsed with deionized water for two minutes. The soaked and rinsed membrane was dried under a deionizer fan for two hours. Two samples of the dried NAFION® ion exchange membrane were titrated according to the procedure given under Example 1. Hydrogen peroxide solution remaining in the beaker following removal of the NAFION® ion exchange membrane (i.e., "purified" hydrogen peroxide) was reserved for use in the procedure of Example 4.

[114] Results of the membrane titration procedure provided insight into the quantity of ionic stabilizers present in the 50 w% stabilized hydrogen peroxide stock solution. Membrane fragments of 1.018 g and 1.16 g required 8.1 mL and 9.2 mL of the strong base to achieve color change of the pH indicator. These results were associated with 87.5% and 87.2% acid conversion, respectively. Thus, using an excess amount of membrane to remove all ionic stabilizers from 50 mL of the solution, the 3.049 g mass of NAFION® ion exchange membrane dropped to an average acid conversion of 87.4 ±0.2%. The 10.6% drop in acid conversion on the 3.049 g membrane sample corresponds to removing 2.94 x 10 ^"4 mol of ions per 50 mL of hydrogen peroxide solution. Multiplying this value by 20 standardizes the concentration in mol of ions per liter. The concentration of ionic stabilizers in the stabilized 50 w% hydrogen peroxide solution was found to be 5.88 x 10 ^" mol/L.

[115] Example 4: Purification Efficiency Testing. Example 4 describes procedures used to determine whether the initial contact with the NAFION® ion exchange membrane, described in Example 3, was sufficient to purify the hydrogen peroxide by removal of all ionic stabilizers.

[116] A 45 mL volume of the purified 50 w% hydrogen peroxide solution from

Example 3 (i.e., the solution remaining in the beaker following removal of the NAFION® ion exchange membrane) was combined with a fresh 1.000 g sample of NAFION® ion exchange membrane in a 100 mL beaker. The membrane was allowed to soak in the solution at room temperature (22°C) for one hour. Next, the membrane was removed from the hydrogen peroxide solution and rinsed with deionized water for two minutes. The soaked and rinsed NAFION® ion exchange membrane was dried under a deionizer fan for two hours. An approximately 1.000 g sample of the dried membrane was titrated according to the procedure given under Example 1.

[117] Results from this testing were useful for evaluating the efficiency of stabilizer purification achieved in the procedure of Example 3. After starting with a 1.040 g sample of NAFION® ion exchange membrane in the procedure, a 0.9 g mass of the membrane was titrated and found to require 7.9 mL of the strong base to achieve color change of the pH indicator. This was associated with 96.6% acid conversion, thereby indicating the ion exchange membrane had lost 1.4 % of its acid content. The ionic stabilizer concentration of the purified hydrogen peroxide from Example 3 was calculated from the total moles of sulfonic acid lost from the 1.040 g sample mass. Here, 1.32 x 10 ^"5 mol of ions per 45 mL of solution corresponded to a stabilizer concentration of 2.94 x 10 ^"4 mol/L. The single treatment process described under Example 3 was highly effective at removing ionic stabilizers. Indeed, the ionic stabilizer concentration was reduced by 20 fold, which corresponds to removing 95.2% of the ionic stabilizers by the single treatment.

[118] Example 5: Assessing Capacity of NAFION® to Bind Stabilizers. Example 5 describes procedures used to assess the capacity of the NAFION® ion exchanger sulfonic acid sites can be used to bind and remove stabilizers from a stabilized hydrogen peroxide solution.

[119] Here a small amount of the ion exchange membrane was added to a large amount of stabilized hydrogen peroxide to determine how much of the NAFION® ion exchange membrane sulfonic acid sites could be used to bind and remove stabilizers from the hydrogen peroxide solution. An approximately 1.000 g sample of NAFION® ion exchange membrane was added to 350 mL of stabilized 50w% hydrogen peroxide solution and allowed to soak at 50°C for one 5 hour. Next, the membrane was removed from the hydrogen peroxide solution and rinsed with deionized water for two minutes. The soaked and rinsed NAFION® ion exchange membrane was dried under a deionizer fan for two hours. Approximately 1.000 g sample of the dried membrane was titrated according to the procedure given under Example 1.

[120] Results addressed the ability of the NAFION® ion exchange membrane to participate in stabilizer binding at lower acid conversion levels. A 1.158 g sample of the NAFION ion exchange membrane required 0.4 mL of the strong base solution to achieve color change of the pH indicator, thereby demonstrating conversion of 3.8% (from 98.0%). Thus, at least 95% of the ion exchange capacity of the membrane could be used to remove ionic stabilizers from 50 w% hydrogen peroxide solutions. In addition to excellent resistance to degradation in the presence of highly corrosive hydrogen peroxide solutions, ionic stabilizers were able to fully saturate the NAFION® ion exchange membrane. These features make the NAFION® ion exchange membrane an excellent resin for purifying hydrogen peroxide from stabilized hydro en peroxide solutions.

[121] Example 6: Use of Purified Replenishment Source Liquid Improves Vaporizer Function. Example 6 illustrates how the use of purified replenishment source liquid can improve performance characteristics of a membrane-based vaporizer system. In this illustration, source liquid is purified by first contacting purification media made of the same material as the ion exchange separation membrane of the membrane-based vaporizer. [122] There initially are obtained two identical membrane-based vaporizers useful for producing gas phase hydrogen peroxide from a source liquid. Each vaporizer is equipped with a reservoir that receives one or another type of a hydrogen peroxide solution. In the an-angement of components of each apparatus, a tube conveys the source liquid from the reservoir to the ion exchange separation membrane, which is made of PFSA-TFE copolymer and sold under the NAFION® trademark (E.I. du Pont de Nemours & Co., Wilmington, DE). The reservoir of the first vaporizer is filled with a 50 w% stabilized aqueous hydrogen peroxide solution (Sigma Aldrich; St. Louis, MO), which serves as the replenishment source liquid. The reservoir of the second vaporizer apparatus is filled with a "purified" source liquid that resulted from batch processing of 50 w% stabilized aqueous hydrogen peroxide solution with an amount of

NAFION® membrane for a period of time sufficient to permit selective binding of any sodium or potassium ions, and selective adsorption of any other ionic or non-ionic agents that may bind to the membrane. In the batch processing approach, the purification media (i.e., the NAFION® membrane) and the liquid being purified are simply combined and incubated or allowed to stand in a single container before the two components are separated (e.g., by simple removal of solid material; or by straining, filtering, etc.).

[123] When operated under standard conditions, the first vaporizer generates steady levels of hydrogen peroxide gas over the course of about a week. The second vaporizer, using the purified replenishment source liquid, generates steady levels of hydrogen peroxide gas for a time longer than a week. This illustrates how use of the purified replenishment source liquid improves vaporizer function, for example by permitting steady gas production over a longer period of time, and by extending the useful life of the ion exchange separation membrane. [124] In an alternative approach for production of the purified replenishment source liquid, a cartridge containing NAFION® ion exchange media is inserted in-line with the tube conveying liquid from the reservoir of a membrane-based vaporizer to the ion exchange separation membrane of the vaporizer. This arrangement facilitates on-board purification of the replenishment source liquid so that purified replenishment source liquid, and not the

replenishment source liquid (i.e., containing metal ions, stabilizers, etc.) reaches the ion exchange separation membrane.

[125] While the invention has been described in detail with respect to certain embodiments, the invention is not limited to those embodiments. It should be understood that modifications and combinations may be made to the illustrated embodiments and other disclosed features to form yet additional embodiments within the scope of the invention.

CLAIMS

We claim:

1. A method, which comprises:

a) providing a solution comprising hydrogen peroxide and one or more cations; and

b) contacting the solution with an ion exchange polymer to produce a purified solution having a reduced content of the one or more cations.

2. The method of claim 1 , wherein the solution is a liquid,

3. The method of claim 2, which further comprises: c) forming a vapor from the purified liquid solution.

4. The method of claim 3, wherein forming the vapor from the purified liquid solution in step c) comprises contacting the purified liquid solution with an ion exchange polymer membrane.

5. The method of claim 3, further comprising: d) passing the vapor from the purified solution through an ion exchange polymer membrane.

6. The method of any one of claims 3-5, further comprising: e) delivering the vapor resulting from step c) or step d) to a critical process or application.

7. The method of claim 1 , wherein the solution is a vapor.

8. The method of claim 7, further comprising: d) passing the purified solution vapor through an ion exchange polymer membrane. 9. The method of any one of claims 7-8, further comprising: e) delivering the vapor resulting from step b) or step d) to a critical process or application.

10. The method of any one of claims 1-9, wherein the solution further comprises water.

11. The method of any one of claims 1-9, wherein the solution is substantially free of water.

12. The method of any one of claims 1-11, wherein the solution further comprises a nonaqueous excipient.

13. The method of claim 12, wherein the non-aqueous excipient is selected from alcohols, phenols, lactones, amides, esters, ethers, carboxylic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids, organic solvents, inorganic solvents, aromatic compounds, polyaromatic compounds, heterocyclic compounds, fluorinated ethers, fluorinated alcohols, fluorinated sulfonic acids, fluorinated carboxylic acids, fluorinated phosphonic acids, deep eutectic solvents, and combinations thereof.

14. The method of any one of claims 1-13, wherein the one or more cations comprise one or more metal cations.

15. The method of claim 14, wherein the one or more metal cations comprise a sodium, potassium, barium, calcium, copper, magnesium, manganese, nickel or zinc cation.

16. The method of claim 15, wherein the one or more metal cations comprise a sodium, potassium, magnesium, copper or calcium cation.

17. The method of claim 15, wherein the one or more metal cations comprise a magnesium or calcium cation. 18. The method of claim 15, wherein the one or more metal cations comprise a copper cation.

19. The method of claim 15, wherein the one or more metal cations comprise a sodium or potassium cation.

20. The method of claim 19, wherein the metal cation is derived from sodium stannate or potassium stannate.

21. The method of any one of claims 1-20, wherein the solution in step a) comprises 15 ppm or less by weight of metal cations.

22. The method of any one of claims 1-20, wherein the solution in step a) comprises 10 ppm or more by weight of metal cations.

23. The method of any one of claims 1-22, wherein the solution in step a) comprises 14 weight % or more of hydrogen peroxide.

24. The method any one of claims 1-23, wherein the solution in step a) comprises 25 weight % or more of hydrogen peroxide.

25. The method any one of claims 1-24, wherein the solution in step a) comprises 50 weight % or more of hydrogen peroxide.

26. The method of any one of claims 1-25, wherein the ion exchange polymer in step a) is in the form of a membrane.

27. The method of any one of claims 1-25, wherein the ion exchange polymer in a) is in the form of a bead or pellet. 28. The method of any one of claims 1-25, wherein contacting step b) comprises passing the solution through a packed bed comprising the ion exchange polymer.

29. The method of any one of claims 1-6 and 8-28, wherein contacting step b) comprises placing the ion exchange polymer in a liquid solution.

30. The method of any one of claims 1-29, which comprises contacting the solution with the ion exchange polymer in step a) under conditions sufficient to remove 70 weight % or more of at least one cation from the solution.

31. The method of claim 30, wherein the at least one cation is a sodium, potassium, barium, calcium, copper, magnesium, manganese, nickel or zinc cation.

32. The method of any one of claims 1-29, which comprises contacting the solution with the ion exchange polymer in step a) under conditions sufficient to remove 80 weight % or more of at least one cation from the solution.

33. The method of claim 32, wherein the at least one cation is a sodium, potassium, barium, calcium, magnesium, manganese, nickel or zinc cation.

34. The method of any one of claims 1 -29, which comprises contacting the solution with the ion exchange polymer in step a) under conditions sufficient to remove 90 weight % or more of at least one cation from the solution.

35. The method of claim 34, wherein the at least one cation is a potassium, barium, calcium, magnesium or manganese cation. 36. The method of any one of claims 1-29, which comprises contacting the solution with the ion exchange polymer in step a) under conditions sufficient to remove 50 weight % or more of the combined total of all cations from the solution.

37. The method of any one of claims 1-36, wherein the ion exchange polymer is a polysulfonic acid polymer

38. The method of any one of claims 1-37, wherein the ion exchange polymer is a perfluorinated polysulfonic acid polymer.

39. The method of any one of claims 4, 5 or 8, wherein the ion exchange polymer membrane is a polysulfonic acid polymer membrane.

40. The method of any one of claims 4, 5, 8 or 39, wherein the ion exchange polymer membrane is a perfluorinated polysulfonic acid polymer membrane.

41. The method of any one of claims 1 -40, further comprising the step of regenerating the ion exchange polymer.

42. The method of claim 41 , wherein the method comprises treating the ion exchange polymer with an acid.

43. The method of claim, 42 wherein the acid is nitric acid.

44. The method of claim 43, wherein the nitric acid is 10% by weight in an aqueous solution.

45. An apparatus, which comprises :

a) a solution comprising hydrogen peroxide and one or more cations; b) an ion exchange polymer in contact with the solution; and c) a housing configured to contain the solution and the polymer.

46. _, The apparatus of claim 45, wherein the solution is a liquid.

47. The apparatus of claim 46, further comprising: d) a second ion exchange polymer in contact with the purified liquid solution.

48. The apparatus of any one of claims 46-47, further comprising: e) one or more flow control devices for delivering hydrogen peroxide vapor to a critical process or application.

49. The method of claim 45, wherein the solution is a vapor.

50. The apparatus of claim 49, further comprising: d) a second ion exchange polymer in contact with the purified liquid solution.

51. The apparatus of any one of claims 49-50, further comprising: e) flow control devices for delivering hydrogen peroxide vapor to a critical process or application.

52. The apparatus of any one of claims 45-52, wherein the solution further comprises water.

53. The apparatus of any one of claims 45-52, wherein the solution is substantially free of water.

54. The apparatus of any one of claims 45-53, wherein the solution further comprises a nonaqueous excipient.

55. The apparatus of claim 54, wherein the non-aqueous excipient is selected from alcohols, phenols, lactones, amides, esters, ethers, carboxylic acids, sulfonic acids, sulfuric acids, phosphonic acids, phosphinic acids, organic solvents, inorganic solvents, aromatic compounds, polyaromatic compounds, heterocyclic compounds, fluorinated ethers, fluorinated alcohols, fluorinated sulfonic acids, fluorinated carboxylic acids, fluorinated phosphonic acids, deep eutectic solvents, and combinations thereof.

56. The apparatus of any one of claims 45-55, wherein the one or more cations comprise one or more metal cations.

57. The apparatus of claim 56, wherein the one or more metal cations comprise a sodium, potassium, barium, calcium, copper, magnesium, manganese, nickel or zinc cation.

58. The apparatus of claim 56, wherein the one or more metal cations comprise a sodium, potassium, magnesium, copper or calcium cation.

59. The apparatus of claim 56, wherein the one or more metal cations comprise a magnesium or calcium cation.

60. The apparatus of claim 56, wherein the one or more metal cations comprise a copper cation.

61. The apparatus of claim 56, wherein the one or more metal cations comprise a sodium or potassium cation.

62. The apparatus of claim 56, wherein the metal cation is derived from sodium stannate or potassium stannate.

63. The apparatus of any one of claims 45-62, wherein the solution comprises 15 ppm or less by weight of metal cations. 64. The apparatus of any one of claims 45-62, wherein the solution comprises 10 ppm or more by weight of metal cations.

65. The apparatus of any one of claims 45-64, wherein the solution comprises 14 weight % or more of hydrogen peroxide,

66. The apparatus any one of claims 45-64, wherein the solution comprises 25 weight % or more of hydrogen peroxide.

67. The apparatus any one of claims 45-64, wherein the solution comprises 50 weight % or more of hydrogen peroxide.

68. The apparatus of any one of claims 45-67, wherein the ion exchange polymer is in the form of a membrane.

69. The apparatus of any one of claims 45-67, wherein the ion exchange polymer is in the form of a bead or pellet.

70. The apparatus of any one of claims 45-69, wherein the ion exchange polymer is a polysulfonic acid polymer.

71. The apparatus of any one of claims 45-69, wherein the ion exchange polymer is a perfluorinated polysulfonic acid polymer.

72. The apparatus of claim 47, wherein the ion exchange polymer membrane is a

polysulfonic acid polymer membrane.

73. The apparatus of claim 72, wherein the ion exchange polymer membrane is a

perfluorinated polysulfonic acid polymer membrane. 74. The apparatus of claim 50, wherein the ion exchange polymer membrane is a polysulfonic acid polymer membrane.

75. The apparatus of claim 74, wherein the ion exchange polymer membrane is a perfluorinated polysulfonic acid polymer membrane,

76. The apparatus of any one of claims 45-75, wherein the apparatus comprises a header configured to direct the flow of a carrier gas.

77. The apparatus of claim 76, wherein the ion exchange polymer of element b) is seemed within the header.

78. The apparatus of any one of claims 45-77, wherein the further comprising at least one sensor element selected from the group consisting of level sensors, thermal sensors, temperature sensors, and pressure sensors.

79. The apparatus of any one of claims 45-78, further comprising a drain valve.

80. The apparatus of any one of claims 45-79, further comprising a replenishment vessel.

81. The apparatus of any one of claims 45-80, further comprising a primary pump on the permeate side of the ion exchange polymer.

82. The apparatus of claim 81, further comprising a second pump connected to the solution side of the ion exchange polymer.

83. The apparatus of any one of claims 45-80, further comprising electrical heaters to heat the solution. Attorney Docket No. RAS-008PCT

ABSTRACT

Compositions, methods, devices, and systems for purifying a source liquid from a replenishment stock solution that includes stabilizing agents, such as metal ions, prior to vaporization. Certain embodiments effect the purification with a solid perfluoronated ionomer, such as a

perfluoronated ionomer membrane. Advantageously, source liquids purified in this manner provide feed stocks for production of ultra-pure gaseous reagents. As well, performance characteristics of membrane-based vaporizers relying on transport processes are improved.

|HMJ This application claims the benefit of C S. Provisional A plication Ser. Mo. 62/143,356, filed on April 6, -2015 _» &» U.S.. Provisional Application Ser..No, 62 213,526, filed on September 2, 20 I 5, the disclosures of which are hereby expressly incor orated by reference in their entiist* and are hereby expressly made a portion of this application. wwm W THE DISCLOSURE

PHKBJ I s disclosur relates to methods md systems for purifying source liquids, paitic !ariy reactive source liquids, s«ch as hydrogen peroxide or hydrazine, that may be used as a source for high purity process gases.

BACKGROUND

[0031 Various process gases may be used in the manufacturing and processing of. microelectronics, in addition, a variety of chemical s ma be used in otter environments demanding high parity gases, e.g,, critical processes, including without limitation

microelectronics applications, wafer ©leaning, wafer bonding, photoresist. stripping, silicon oxidation, snrface passivation, photolithography mask cleaning, atomic layer deposition, atomic layer etch, chemical vapor deposition, flat parse! displays, disinfection of surfaces contaminated with bacteria, viruses and other biological agents, industrial parts cleaning, pharmaceu tical manufacturing, production of nano-niaterials, power generation and control devices, fuel cells, power transmission devices* and other applications In which process control and purity are i critical considerations, In those processes, it is necessary to deliver specific smouats of certain process gases under controlled operating conditions, e,g, _> tempeimture, pressure, and Sow rate.

£0 J For a variety of reasons, gas phase delivery of process chemicals is preferred to liquid phase delivery. For applications *eq« «g low m ss flow for process chemicals, liquid delivery of process chemicals is not accurate or clean enough. Gaseous delivery would be desired from a standpoint of ease of delivery, accuracy and pu ity. Oas flow devices are better attuned to precise control than liquid delivery devices. Additionally, mieaveleciTonies applications and other critical processes■ ^■ typically have extensive gas handling systems that make gaseous delivery considerably easier than liquid delivery. One approach Is io vaporize the process chemical component directly at or near the point of use. Vaporising liquids provides a process that leaves heavy contaminants behind, thus purifying the process chemical However, for safety, handling _s stability _s and/or purity reasons, many process gases ate not amenable to direct vaporization.

|88§j There are numerous process gases used in micro-electronics applications .and other critical processes. i> is a gas that is typically used to clean, the surface of

semiconductors (e g. _» photoresist stripping) and as an oxIdMng agent (e.g.,, forming oxide or hydroxide layers). One advantage of ns.bg o¾o»e gas in micro-electronics applications and other critical processes, as opposed to prior liquid-based approaches, is that gases are able to access high aspect ratio features on a surface. For example, according to the International Technology Eoadmap for ^■' Semiconductors (IT1¾¾ current semiconductor processes should be compatible with- -a half-pitch as small -as 20-22 »m. The next technology node for semiconductors is expected to have a half-pitch of 14-16 nm, and the ITRS calls for <10 nm bait-pitch in the nea ^' .future. At these dimensions, liquid-based chemical processing is not feasible because the surface tension of the process liquid preven s i t From accessing the bottom of deep holes or channels and the comers of high aspect ratio features. Therefore, o¾o«e gas has bees used In some Instances to overcome certain limitations of liquid-based processes because gases do not suffer from the same surface tension limitations,. Plasma-based processes have also been employed to overcome certain limitations of liquid-based processes. Howe r, ozone- and plasma-based processes present their own set of limitations, including, inter alia,, cost of operation, insufficient process controls, undeslred side reactions, and inefficient cleaning.

[Wty More recently, bydrdgen peroxide has been explored a replacement for ozone in certain applications, However, hydrogen peroxide has been of limited utility, because highly concentrated hyd ogen peroxide solutions present .serious safety and h ndling ^' concerns and obtaining high concentrations of hydrogen peroxide in the gas phase has been difficult.

Hydrogen peroxide is typically available as an aqueous sohiiion. In addition, because hydrogen peroxide has a relativel lo vapor pressure (boiling point is apprommately 150 °C), available method and devices for delivering hydrogen peroxide generally do no provide hydrogen peroxide containing gas streams with a sufficient concentration of hydrogen peroxide,

|8i7| For vapor pressure and vapor composition studies of various hydrogen peroxide solutions, see e,g. _f ydrogen Perodde. Walter C. Se umb, Charles R Satterfseld and- Ralph L. Went orth, Reinhold Publishing Corporation, 1 55, Mew York, available at

http: lhdibandie,neU202? mdp,390l50i 3?0Sf 84< Moreover, studies show that delivery into vacuum leads to even lower concentrations of hydrogen peroxide (see, e.g., H rogen P¾rax|de. Sehurub, pp. 228-229). The vapor eompositlon of a 30 % HsQa aqueous solution delivered using vacuum at 30 mm Hg is predicted to yield apptbxirnately half as much hydrogen peroxide as would fee expected For the same- solution delivered at atmospheric pressure.

3 (¾iS| Gas phase delivery of low volatility compounds _, presents a particularly ni u se of problems. Cine approach Is to provide a multi-component liquid source wherein the process chemical is raked with a more volatile solvent, such as water or an -organic solvent (e.g., ssopropanol). However, when a multi-component solution i the liquid source to be deli ered (e.g., hydrogen peroxide and water), Raool s Law for nmiti-eoruponent solutions, becomes relevant According to Raoult's Law* for m idealized two-component solution, the vapor pressure offhe solution is equal to the weighted sum of the vapor pressures for a pure solution of each component where the weights are the mole fractions of each component in the above equation,. PM i s the total vapor pressure of the two-component solution, ¾ is the vapor pressure of a pure solution of component .A, X* s t e mole fraction of component A i the two-component solution, P¾ is fee vapor pressure of a pure solution of component .B, and X _¾ is the mole fraction of component B in the two~eornponent solution.

Therefore, when A and B have different vapor pressures, the relative mole fraction of each component is different in the liquid phase than it is in the vapor phase above the liquid.

Specifically, the more volatile component (i.e., the component with the higher vapor pressure) has a higher relative mole fraction in ^' the gas phase than it has In the liquid phase. In addition, because the gas phase of a typical gas delivery device, such as a bubbler, is continuously being swept away by a carrier gas, the composition of the two-component liquid solution, and hence the gaseous head space above the liquid, is dynamic.

|0101 Thus, according to Raoui s l w, if a vacuum is pulled on the head space of a multi-component liquid solution or if a traditional bubbler or vaporizer Is used to deliver the solution in the gas phase, the more -volatile component of the liquid solution will he

4 preferentiall removed from the solution compared to the less volatile component This- limits the concentration of the less volatile component that can fee-delivered ixt the gas phase. For instance, if a carrier gas Is babbled through a 30% hydrogen peTOxkle/water s lution, only about 295 ppm of hydrogen peroxide will he delivered, the remainder being all water vapor (about ^■ 20,000 ppm) an th carrier gas.

The differential delivery rate that, results when a multi-component liquid solution Is used as the source of process gases makes challenging repeatafole process control, it is difficult to rite process recipes around coatmaously changing mixtures. In addition, controls- f©r.«aeaseiing a continuously changin rati© of the components of the liquid source are not readily available, and if avai lable, they are costly and difficul to integrate into the process, In addition, certain soluti ons become hazardous if the rel ativ e ratio of the components of the liquid source changes. For example, hydroge peroxide -in water becomes explosive at concentrations over about 75 %; and hus, delivering hydrogen peroxide by bubbling, a dry gas through an a ue us hydrogen peroxide solution, or evacuating the head space above such solution, caa take a safe solution (e.g.,, 30 % ¾0 ₂ ¾O) and convert It to a hazardous material that Is over 75 % hydrogen peroxide _* Therefore, currently available delivery devices and methods are insufficient for consistently _t precisely, and safely delivering controlled quantities of process gases in man micro-electronics - ^' applications and other critical processes.

f §i 2 J There has been recent interest m the nse of hydrogen peroxide concentrations above 14 weight %, such as 25 weight % or more, sach as 50 weight % or more. Such solutions may Include certain stabilizers not otherwise used a lower concentrations. The presence of stabilizers may ultimately degrade or otherwise impair the performance of equipment o materials tha come into contact with the stabilizers in applications where the concentrated

S ydro en peroxide Is used, Additionally _^ the stabilizers may become undesirably deposited on materials or surfaces intended to be cleaned by the hydrogen peroxide gas in any number of applications or critical processes. Thus _* there is a need for methods fo purifying such, stabilized hydrogen peroxide solutions prior to their use.

BRIEF DESCRIPTION OF THE DRAWINGS

|013| The following figures form part, of the present specification and are included to further demonstrate certain aspects and embodiments of the present di sclosure. The disclosure may be better understood by reference to one or more of these figures in combination with the description of specific embodiments presented herein.

(014f Figure I schematically illustrates purification of eplenisl meni source Ikfuid for a vaporker. The arrangement of various components of an apparatus that holds and transports different source liquids in accordance with th inversion is shown in the diagram.

SUMMARY OF CERTAIN E BODIM N S

In one aspect of the invention, a method comprising:

a) providing a solution comprising hydrogen peroxide and one or more cations; and h ^" ) contacting the solution with a Ion exchange polymer to produce purified solution. having a reduced content of the one or more cations is provided.

f¾$6J The solution may contain the cations as -sla iHaers-, such as when the solution comprises more than 1 weight % h drogen peroxide. The method reduces the content of the one or more cations In the solution, thereby reducing or e!iminating the!r possible adverse effects during subsequent processin or use of the solution.,

6 f # 1 ?1 After contacting with the hn exchange polymer, the purified solution may undergo additional processing steps. The additional processing steps may Include, lor example, forming a vapor from a purified liquid solution through contact with another ion exchange membrane. The additional processing steps may also include, for exam le, contacting a purified vapor solution with, another ion exchange membrane and/or delivering the resulting vapor to a critical process or application.

f 11 $| Also provided in the present disclosure are systems,, de ices, and apparatuses for delivering a purified hydrogen peroxide solution, The systems, devices, and apparatuses comprise:

a) a solution comprising hydrogen peroxide and one or more cations;

b) an ion exchange polymer in contact with the solution; and

c) a housing configured to contain the solutio and the polymer,

J In certain embodiments, the solution in the systems- and devices is a liquid; in other embo iments, the solutio is a vapor, in certain embodiments, the systems and devices further comprise a second ion exchange polymer in contact with the purified liquid solution, in certain embodiments, the systems and devises further comprise one or more flow control devices for delivering hydrogen peroxide vapor to a critical process or application,

[Did] Additional embodiments aid features are included in the detailed description that follows, and will be readily apparent to those skilled in the. art from the description or recognized by practicing the -embodiment -as described in the specification and claims.

DETAILED BESCRI ilON OF CERTAIN EMBODIMENTS |021] Various embodiments of the invention will now be explained In greater detail It is to be oaderstoc l that both the foregoing general description and the Following detailed description are exemplary and explanatory only, and are not restrictive of the invention a claimed. Any discussion of certain embodiments or features serves to illustrat certain exemplary aspects of the invention. The invention knot limited to the embodiments specifically discussed herein,

[#22 J Unless otherwise indicated, all numbers such as those expressing temperatures, weight pereents, concentrations, time periods, dimensions, and values for certain parameters or physical properties used in the specification and claims are to be Ui¾derstood as being modified in all instances b the term '"about." It should also be understood that the precise numerical values and ranges used In the specification and claims form additional embodiments of the invention. All measurements are subject to uncertainty and experimental variability _*

|023| As used herein, "substantially gas-impermeable membrane" is a broad term, and is to be gi ven its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a membrane that is relatively permeable to some components that may be present in a gaseous or liquid phase, e.g., hydrogen peroxide, but relatively impermeable- to other gases such as, but not limited to, hydrogen, nitrogen, oxygen, carbon monoxide, carbon dioxide, hydrogen sulfide, hydrocarbons (e.g., ethylene), volatile acids and bases, refractory compounds, and volatile organic compounds, A substantially gas-impermeable membrane in accordance with the present disclosure can be relatively permeable to other components that may be present In a gaseous or liquid phase, e. g., water, hydrogen peroxide, hydrazine, and the l ike. Examples of substantially gss mpermeabl membranes include NAFKM® (E.L du Pont de Nemours <& Co., Wilmington,

8 DB) and salt derivatives, as well as AQ0IV10N® (Solvay S.A., Brussels, Belgium) or 3M lON ^' O ER® (3M Co., . ^' Minneapolis,. MM), Gas itrspeoBea lliiy can be detertniaed by the "leak Fate ⁵ ' of the membrane.

|024} As used herein, "critical process or appHeation* is a broad term, and is to be given its ordinary and customary mean n to a person of ordinary skill in the art (and is sot to be limited to a special or customized meaning), and refers without limitation to a process or application in which process control and purit are Critical considerations. Examples of critical processes and applications Include without limitation microelectronics applications, wafer e!eaning, water bonding, photoresist stripping _* silicon oxidation, surface passivation, photolithography mask cleaning, atomic layer deposition, atomic layer etch _s Chemic l vapor deposition* flat pastel displays* disinfection of surfaces contaminated with bacteria, viruses and other biological agents, Industrial parts cleaning, pharmaceutical an facturin , production of nano-materiais, power generation and control devices, foe! cells, and power transmission devices _*

102-51 As used herein, "leak rate" is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill In the art (and is not to be limited to a special or customized meaning), and refers without limitation to the mass or moles of a particular gas that penetrates the membrane surface area per unit of time.

|026J As used herein, "ion exchange membrane* is a broad term, and is to be given its ordinar and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or cus omiz d meaning), and refers without limitation to a membrane comprising chemical groups capable of combining with ions or exchanging with ions between the membrane and an externa! substance. Such chemical groups Include, but are not limited to, sulfonic acid,

9 earhoxylie acid, sulfonamide, -sulfonyl imide, phosphoric acid, plxisphlnic acid, arsenic groups, selenjc groups, phenol groups, and salts t ereof. When making modifications to ion-exchange membranes resulting in salts, such salts are referred to herein as ^s 1on~exehange membrane sails " When the Ion exchange membrane Is a component of a membrane-based vaporizer that operates by transport of a chemical component of a source liquid across the ion exchange membrane to enter a gas phase, the ion exchange membrane can be referred to as an ton exchange "se a tio ^ membrane.

1 _. 271 As nsed herein, "relatively constant" is a broad term, and is to be given its ordinary aid customary meaning to a person of ordinary skill in the art (a d is not to be limited to a special or customised meaning), and-tefers without limitation to a value that* although it may change with time, does not change so substantially so as to render the value inoperative or substantially les operative. In the context of increasing the concentration of a low volatile component, such as ¾<¾, it means mai ntaining a concentration at sufficiently high levels so as to provide a stabl gas delivery of the low volatility component gas for sufficient time to be applied to a critical process or application. For example, maintaining a standard deviation of to within 3% or up t 5% of the mean for an boor would be considered relatively constant,

f 62S) As used herein, "equilibrium concentration'' is a broad term, and is to he given Its ordinary and customary meani ng to a. person of ordinar skill in the art (and is not to be limited to a -special or customized, meaning), and refers without limitation to the maximum amount of the less volatile component that may be delivered into the gas phase to be used, for example, to decontaminate a material -and ^' will be dependent apon temperature and head space pressure. Under such equilibrium conditions, the molar ratio of the less volatile component to the higher volatile component in the gas phase will he equivalent to the molar ratio of the less volatile component to the .higher volatile component in the solution phase of the liquid used to replenish the niidtln raponen source liquid in solutions with multiple continents, under such equilibrium conditions in accordance with the present invention, the molar ratio of the less volatile com onent to the higher volatile components in the gas phase will he equivalent to the molar ratio of the less volati le component to the higher voktlle components in the solution phase of ilre liquid osed to replenish the mulii -component source liquid.

[029] As used herein, "stable" in the context of the output gas comprising the less volatile ^■ component from the multi-eompoaent source liquid, such as hydrogen peroxide in the gas-phase at a stable steady state concentration, means an output concentration that does not vary beyond certain parameters such as, for example, by more than 10% in some embodiments and not by more than 5% _> 3% or 2% in other embodiments. The term applies once an equilibrium concentration of the less volatile component In the gas phase has been achieved and is being delivered to a critical process or application, The percentages herein are th ^' standard deviation from the mean ^' with respect to the me an of measured gas output

|I36| As used herein, "stable steady state concentration" I» the context of the output gas comprising the less volatile component from the multi-component source liquid, means an output that has increased to a concentration that Is stable and In equilibrium as those terms are used herein.

|Θ3Ι| As used herein, gas" means gaseous species that is not. a liquid, solid or a plasma as those terms are well understood in the art.. Further,, a gas Is not a mist or a fog as -would be generated, for example, by a nebulizer or atomizer. The term iurther means that there are fewer than 100 particles of liquid front the gas generation source liquid greater than 100 BSI In size at standard temperature and pressure conditions in a vol ume of one l iter as measured with a

I I -stan ar condensation nucleation counter. In certain critical application where droplet particles are detrimental, the term gas may preferabl means that there are less than 10 particles greater than 100 am, 50 am, 25 nn¾ or lOnm at standard temperature and pressure conditions m a volume of one liter as measured with a standard condensation nucteation counter available from MSP In Minnesota, Particle Measuring Systems or other readily available .commercial instruments. In a multicomponent liquid, such as water and hydrogen peroxide, when volatilized arid delivered to a critical process application such as a material to he decontaminated, the hydrogen peroxide is In th gas phase. By comparison, it is possible that water, when voia&iized and introduced into a carrier gas, may be either a ga or a vapor,

ffB2] As used herein _* "process gas" is abroad term,, and is to be given its ordinary and customary meaning to a perso of ordinary skill in the art (and is not to be limited to a special or cu tom s d meaning), and refers withou limitation to a ga that is used in a critical application process, such as the decontamination of a material or cleaning the surfaces of semiconductors or the chemical modification of semiconductor surfaces to form an oxide, hydrexyl iigaod.

Similarly, such surfaces may he passivated by th removal of carbon atoms, or reacted with photoresist or photoresis byproducts _* or annealing spin-on dielectrics, or spin-on silicon based precursors. Exemplary process gases are water, inorganic acids, organic acids, inorganic bases, organic bases, and inorganic and organic solvents. A particular process gas is hydrogen peroxide gas. Another particular process gas includes hydrazine. A process gas "st eam refers to a flow of process gas that may be carried through a pipe, tube, or other conduit, to a place where the process gas may be used. A process gas stream may Include a carrier gas.

|033| As used herein, "earne gas' is a broad term, and i to he given its ordinar and customary meaning to a person of ordinary skil l in the art (and is not to be limited to a special Or customized meaning), and refers without limitation to a gas that is used to carry another gas through a process train, which is typically a train of piping. Exemplary carrier gases are nitrogen, argon, hydrogen, oxygen, Ct¼, clean dry ak _} room air, helium, or other gases or combinations thereof that are stable at room temperature and atmospheric pressure . A carrier gas may be an inert, gas, in one embodiment, the earner gas is nitrogen. The carrier gas may be solely an inert gas or it ma have one or more additional components. A carrier gas may farther comprise water, for example. By "dry nitrogen* ^* what is meant is a nitrogen gas substantially free of water. I other embodiments, the carrier gas may he hydrogen, clean dry air, oxygen, ozone, or combinations thereof ^* . In some embodiments, the carrier gas may be substantially free of water. In certain embodiments, the carrier gas is not passed through a humidifier, in one embodiment, the carrier gas contains an inert gas and water. As used herein, when water is identified as a. component of the gas, unless otherwise provided, ϋ is understood to be water in the gas phase.

J034J As used herein, ^' "substantially dry carrier gas" means gas, or a particular kind of gas if in relation to clean dr air or nitroge for example, that is dehiatiidified by methods known in the art redue* moisture I s a gas so as to deli ver a gas that is as dry as practicable. S uch methods include, but are not limited to using gas purifiers such as those available ..from commercial manufacturers,

|03S| As used herein, '"pre-loaded carrier gas" is a broad term, and is to be gi ven its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a carrier gas containing an amount of one or more co onents) of a source liquid, in one embodiment, the pre- loaded- carrier gas contains an nert gas and water. In another embodiment, the pre-loaded carrier gas

13 comprises ose or more of nitrogen . argon, hydrogen, oxygen, C€¾, clean dry a!r _» helium, or other gases that are stable at room temperature and atmospheric pressure and wafer. A pre-loaded earner gas- s also considered a carrier gas.

3S| As used ^' herein, ^* ¾ndersataptted ^M means, in the context of a gas, such as a carrie gas or carrier gas, that the partial pressure of the gas Is less than the maximum partial pressure for that gas its the head space or the carrier gas or carrier gas for the given temperature and pressure, The term undersaiorated applies at a point specific point in time. The carrier gas may be saturated for a specific temperature and pressure and later be modified by reducing the pressure or increasin the temperature such that the head space or carrier gas is now

uirdersatufated. As used herein, "oversatumied ^5* means, in tire context of a gas, sssch as a carrier gas or carrier gas, that the that the partial pressure of the gas Is greater than the maximum partial pressure for that gas i the head space or the carrier gas or carrier gas for the -given temperature and pressure. In some embodiments of the invention, the gas stream delivered to the critical process application is at a higher partial pressure of the component less volatile than water tha the partial pressure of that component from the mniti-eomponent source liquid used to replenish prior to delivery of that liquid.

[037f As used erein, "Inert gas" Is a broad teen, and Is to he given Its ordinary and cu t mary meaning to a person of ordinary skill In the art (and is not to fee limited to a special or ^• c«storai¾ed meaning), and includes without limitation- a. gas that Is relatively impermeable to the membrarse as described herein. In one embodiment, the inert gas comprises one or more of nitrogen, argon, helium, or other noble gases. In another embodiment, the Inert gas Is nitrogen. In another embodiment, the inert gas Is dry nitrogen.

14 j¾8Sf As used herein, "source liquid" is a broad term, and is to be given Its ordinary and customary meaning t a person of ordinary skill in the -art (and Is not to b limited to a special or eustomked meainng), and generally refers wi hout limitation to a liquid solution that provides the source of a gas through change of phase used In an application or process, specifically a process gas. In certain embodime ts, the souree. liquid directly contacts the ion exchange separation membrane ^' .of a membrane-based vaporiser.

|§3f J As used herein, "replenishment source liquid" Is a broad terrn, and is t be given its ordinary and customary meaning to a person of ordinary skill in the art ^' {and is not to be limited to a special or customised meaning), and r¾fers without limitation to a souree liquid used to replenish a system that consum s souree liquid. A replenishment source liquid may contain additives or chemical stabilizers, and may be used for refiling a liquid reservoir of a vaporiser apparatus. A commercially obtained SO weight % stabilised hydrogen peroxide solution that includes sod ums siaanate, potassium sta mate, and zmc stannate is an example of a replenishment source liquid. Nota ly the ratio of components in a multlcomponent liquid serving as the replenishment source liquid may be the same, or may be different from the ratio of components In the source liquid.

!§ §| As used herein* "purified replenishment source liquid" Is a broad terra, and is to he given Its ordinary and customary meaning to a person of ordinary skill i n the art (and is not to be limited to a special or customized meaning), and refers without limitation to a liquid solution prepared b selectively reducing or removing at least one chemical component from a replenishment source liquid. For example, a purified replenishment source liquid may include a reduced amount of chemical agent found in a replenishment source liquid, where that chemical

IS agent binds to the materia! of an. ion exchange separation membrane by ionic or absorptive interaction,

!¾ .i.| As used herein, "head space" is broad term, and is to be give its ordinary and customary meaning to a person of ordinary skill in the ait {and is sot to be limited to a special or customized meaning), nd refers without lirnitation to a volume of gas in fluid contact ¾¾th a so rce liquid that provides a least a portion of the gas contained in the head space.

|#42| As used erein, 'Vaporizer is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary ski!! in the art (and is not to be limited to a special or customized me ning) _* ^' nd refers without limitation to a device thai generates a gas, a vapo , or a mist from a starting source liquid. Nebulizers and bubblers are embraced by the term, since these devices produce a vapor frooi a source liquid. In a specific embodiment represented b a membrane-basecl vaporizer, which generates a gas starling from a source liquid, there is a headspace _* a carrier gas inlet, a carrier gas outlet, and a permeable or selectively permeable barrier (e.g,, an ion exchange membrane) separating tile head space from the. source liquid where the source liquid changes phase and may be used as a process gas. The vaporizer may optionally Include a heater to control the temperature of the source liquid and/or vapor. The gas generated from the. source liquid by energy supplied by a heat source is swept away by the carrier gas. In certain embodiments the carrier gas is saturated, in other embodiments the carrier gas is not saturated.

{043) As used herein, the term 'Vaporizes" refers to a procedure that employs a vaporfeer (ie, ₅ a device), and that generates a. gas, a vapor, or a mist starting from a source liquid.

{044} One embodiment of the inventi on Includes a method, which comprises:

16 a) providin a solution comprising hydrogen peroxide and one or more cations;

and

b) contacting the solution with an km exchange polymer to produce a purified solution haying a reduced content of the one or more cations,

!§4SJ In certain embodiments, the ion exchange polymer, whether or not in the form of a membrane, is a polysdfonic- acid polymer. In still other embodiments, the ion exchange membrane is a tluerine-costaining polymer, e.g., polyvinylideaeSnoride, polyteirafl Oroethyiene (FF B), ethylene tetxafluoride-propylene hexalluoride copolymers (PEP), ethylene tetr&ilaoride- periluoroalkoxyetnylene copolymers (PFE), polychlorotrifluoroe hylene (PCTFE), ethylene te Tailuorideethylene copolymers (ETFE), poIyvkylMene fluoride, polyvinyl fluoride, vinyhdene fluorioV triSuorinated ethylene chloride copolymers, vinyl kiene 11 uoride-propy ene hexafluoride copolymers, vinylidene tluoridepropy!ene hexail«oride-ethylene tetrailuoricle terpolyniers, ethylene ten-aSnoridepropylene mbber _f and fluorinated thermoplastic elastomers, in another embodiment _s the ion exchange polymer is a perftyorinated polysnlfonk acid polymer. Other exemplary perfl orinated ionomers include _* but are not limited to, perSnorosulfbnic

aeid feteSnotoethylene copolymers ("PFSA-TFE. copolymer ^" "} and perfltiorocarboxylie acia/teirat uoroetliylene copolymer f PFCA-TFE copolymer"}., in other embodiments the ion exchange polymer is a perflnorinated polysulfome acid polymer in the form of a membrane such as ΝΑΡΙΟΝ or a hydrolys'.ed version of a sulfonyl fluoride perfiuorinated membrane,

[0 61 Preferably, the ion exchange separation membrane of a membrane-based vaporizer is a resin, in one embodiment, the ion exchange membrane is a flnorioe-contaimng polymer. The ion exchange membrane is preferably a perfeorinated iononier comprising a copolymer of ethylene and a vinyl monomer containing an acid group or salts thereof. These

1 ? .me fcranes are coms¾etd Ify available under the trade names NAFION ¹ © (E,L du Pent de Nemours <& Co,, Wilmington, DE), FtEMION® (Asa Okss Company, Ltd., Tokyo, Japan), and ACIPLEX® (AsaM Kase Chemicals Company, Tokyo, Japan) _* 3M lONO E (3M Company, Minneapolis, MN) or AQUlV10N (Solvay S.A. _: . Brussels, Belgium) could also bo used,

|§ 7| Irt certain ^' embodiments, a singl peak molecular weight is preferred. In certain embodiments, bi modal or mu!thftodal molecular weights are preferred. Preferably, the copolym r is between approximately SGOEW and approximately 20O0EW. In. certain

embodiments, the ion exchange membrane may contain either a single . 'Co olymer or

combinations of copolymers* In. certain embodiments, the polymer can fee in any configuration, including, but not limited to, block, tapered, random, linear, and others. PFCA-T E copolymers contain a tetimSuoroethyiene C'TFE") ⁱ %ackbone,' ^? to which the peri uoroearhoxylle acid

groups cm be converted to salt form by a pretreaiment with a suitable base. A PFSA-TP E copolymer contains a TFB ''backbone," to which perfluorosulfbnle acid (perfliRW0{ ~meihyi-3,6- dtoxa-7«octeae«l -sulfonic acid}) groups are attached. There are between one and six

perfiuorosulfonic acid groups per six TFB backbone units. Copolymers are normally classified by equivalent wei ht ¾W"), or by grams of polymer per mole of functional group.

£048J The pretreatmeni methods are well known in the art, and can be performed according io the manufacturer's recommendation. Depending on the nature of the liquid to be vaporized, pretreatment conditions can be adjusted to optimize the membrane. Examples of pretreatment condi tions that ca be adjusted and Include, but ate not limited -to, selection of b se,

18 solvents, temperature, soaking In a hydrogen peroxide solution, and other parameters that would be known to a person of skill in the art.

|04$| Bydrophiiicity can be adjusted by eross-i inking with a hydroplhiiic agent or by co- easting;. In such embodiments where hydrop Iiclt is adjusted by cross-linking with a.

hydropbilic agent or by co-casting, the polymer already includes eross-lisikable groups, or is .ft ctionalized to include cross-linkable gro ps. Other prelreatmeuts without modifying surface chemistry can be employed. I» another embodiment, the polymer can be impregnated with inorganic oxides. This impregnation can improve thermal stability by S°C ~ I20°€. This can also increase water transport rate properties b 2% ~ 40%,

ffSfiJ Preferably, the membrane suppresses the diffusion of gases and other

contaminants, such as particles, aerosols, viruses, bacteria,, and prions. Preferably, the thickness of the membrane is between 0.5 microns and 2,000 microns. The leak rate is measured by monitoring the pressure in an Isolated static system. An exam le of a leak rate is W ⁹ cnr7cni ² /s for nitrogen at standard temperature and pressure, Leali rates can be as high as 1.0 ^* * enrVcm¾ at standard temperatnre and pressure or as lo as 1 ^{'5 ¾} cm^ cm s for a specific gas.

[051 j in one method of generating a gas from a source liquid, the source liquid is contacted to a first side of a substantially gas Impermeable membrane gad the gas generated Is received on the second side of the substanti ll gas impermeable membrane. In certain embodiments, the first arid second sides of the substantially gas impemteable membrane have a Sat form, wherein the membrane is a sheet, in other embodiments, the _. membrane can also be in tubular or .cylindrical form, wherei one surface form the inner potion of a tube, and the opposing surface forms the outer portion of the tube. I all embodiments _* the membrane ca

19 take any form, provided that a first -surface and m opposing second surface sandwich a biilk of membrane .material.

[052] Certain properties of the menibraie cm be adjusted, depending on the process condi ions, the n ure of fhe gas being generated, and other factors. Such adjustable properties can mclude; the physical form of the membrane, the configuration of the membrane, the fabricatio method of the Me feraae, the presence or absence of a support layer of the membrane, the presence or absence of an active layer of the membrane, as well as other properties not listed here.

055] When the membrane is tbim if is preferred to give the membrane some means of mechanical support. Thicker membranes can be used without such Support.

[054 j In certain embodiments, the surface area of the membrane can be adj usted based on the volume of gas to be generated. Either a higher or lower surface area can be desirable, depending on the chemistry of membrane. In an alternative embodiment, the resin comprises a composite or ^■ mixture of polymers. This composite or msxtore of polymers can comprise two o more layers, The layers can have the same or different properties as one another. A layer can provide support to filtration,

fiJSSj In certain embodiments, i is generally preferable for the membranes to be in fiber form, rather than in sheet form, due to the ability to pro vide greater exposed membrane surface area in a fixed volume when fibers are employed,

[056] T¾e solution may be in liquid or vapor form. When the solution is a liquid, fiuther embodiment comprises:

a) providing a solution comprising hydrogen peroxide and on or more- cations;

29 b) cont cting the solution wfth an ion exchan e polymer to produce a purified solution havin a reduced content of the one or more cations; arid

c) fom»ng a vapor from the purified liquid solution.

057j The vapor may be formed in c) through any suitable technique, such as through applying heat

|0S81 in another embodiment,, the vapor is formed in e) by contacting the purified liquid solution with a substantially gas~in perroeable ion exchange membrane such as a perf!uorinated polystdfonic acid polymer membrane _* S eh a technique is disclosed in WO 2014/014511, titled "Method, S stem, and Device for Deli very of High Purity Hydrogen Peroxide," the entire contents of which are incorporated by reference here n* The purified liquid solution raay _s for example, contact a first side of sueh a membrane to ultimately obtain a vapor emerging from a second side of the membrane. In this instance, the vapor phase and liquid source are separated by substantially gas mpermeable ion exchange membrane, such as a pertluofinated

poiyeuifonic acid polymer membrane. By using such a membrane, the concentration of hydrogen peroxide in the resultant vapor may be increased relative to the hydrogen peroxide concentration that would be obtained directly from the solution without the use of a membrane. f §59J The ton exchange polymer membrane may he composed of any suitable materials, such as those described above for the ion exchange polymer. The membrane may also have any suitable structure. For example, the first and second sides cars have the fonn of substantially flat, opposing planar areas, where the membrane is a sheet. Membranes can also be provided In tubular or cylindrical form where one surface forms the Inner position of the tube and an opposing surface lies on the outer surface. The ^' membrane can take any form, so long as the first surface and an opposing second surface sandwich a bulk of the membrane material. Multiple

^■■ ί memb nes may also be arranged in th fotm of an assembly, for ex m le, -with several membr nes configured as lumens insetted at each end into holes of a collector plate,

f§6ft] Depending on the processing conditions, nature of the solution, vol ume of the solution s vapor to e generated, and other factors, the properties of the membrane can he adjusted. Properties include, but are not limited to physical form (e.g., thickness, surface area, shape, length and width for sheet form, diameter if in fiber form), configuration (flat sbeet(s), spiral or roiled sheet(s), folded or crimped sheei(s} _; fiber arrayCs)), _* fabrication method (e.g, _» extrasioa, casting from solution), presence or absence of a support layer, presence or absence of m active layer (e.g., a porous prefdier io adsorb pariicks of a particular size, a reactive preftlier to .remove impurities vi chemical reaction or bonding), and. the like, it is generally preferred that the membrane be from about 0.5 microns in thickness or less to 2000 microns in thickness or more, preferably from about 1, 5, MX 23, 30, 100, 200, 300, 400, or 500■microns to about 600, ?OO _} .8O0, 900, 1000, 11.00* 1200, 1300, 1400, 1500, 1600, 1700, 1S00, or ISW mcrons. When thinner ^■ membranes, are employed, i ca be desirable to provide mechanical support to the membrane {e>g«, by employing a supporting memhtane, a. screen or .mesh, or other supporting xiracture), whereas thicker membranes may be suitable ^' for use without a support. The surface area can be s lected, based on the mass of vapor to be produced.,

[§61] In embodiments where a vapor ha been formed in c), such as through appheation of heat to the liquid solution, a further embodiment comprises:

f I]: One embodiment of the invention includes a method, which comprises:

a) providing a -solution comprising hydrogen peroxide ari one or more cations;

b) contacting the solution with a ion exchange polymer to produce -a purified solution having reduced content of the one or more cations;

22 c) forming a vapor from the purified liquid solution and

d) passing the vapor through an ion exchange polymer membrane, .such as a

perfluorinstcd polysnlfonie acid polymer membrane, an example of such a membrane being HAFIONi) or hydrolyzed versions of suifonyi fluoride peril uor nated membranes.

ff 63J Step d) may utilize the membrane to remove coiitaniinants f om the vapor stream, and the membrane may have any of the■structural characteristics described above,

|#64| Methods, systems, and devices for delivering hydrogen, peroxide vapor with a perfluorinated ion exchange membrane are disclosed in PCX Publication WO 201 /165637, titled "Delivery of a High Concentration Hydrogen Peroxide Gas Stream," filed on April 3, 2014, the entire contents of which is hereb Incorporated by reference herein, particularly paragraphs fOCBO] to [0Θ4.3}. In addition, analogous methods, systems, and devices are disclosed In U.S. Provisional Application Ho. 61/824,127, titled "Delivery^ of ¾ High Concentration Hydrogen Peroxide Gas Stream," filed on May 16, 2013; and U.S. Provisional Application No. 61/809,256, titled "Delivery of a High Concentration Hydroge Peroxide Gas Steam," filed on April 5 _» 2013. The entire contents of those applications are also hereby incorporated by reference herein.

i¾6S| In some embodiments, the solution in a) Is in the form of a vapor. Similarly to the vapor that ca be formed in e), this puri fied vapor may also be passed through an ion exchange polymer membrane, such as a perfluorinaied po!ysolfbnic acid polymer membrane, for example, for the purpose of removing contaminants.

[!M½| The purified vapor resulting from an of the embodiments discussed above may be del ivered to my suitable critical process or application. Such critical processes and applications include, without limitation, microelectronics applications, wafer cleaning, wafer bonding, photoresist stripping, silicon oxidation, surface passivation, photoi ^' iihogmphy mask cleaning, atomic layer deposition, chemical vapor deposition, flat panel displays, disinfection of surfaces cofttaniinated with bacteria, viruses sad other biological agents, industrial parts deanmg, b miaeeafcal manufacturing, produc ion of naoo-materials, power generation and control devices, foci cells, and power transmission devices,

67 Another embodiment of the invention incl udes a method, which comprises:

a) providing a solution comprising hydrogen peroxide and one or more cations;

b) contacting the solution wit an on exchange polymer to produce purified solution having a reduced content of the one or more cations;

c) foraimg a vapor from the purified li u d solution;

d> passing the vapor through an ton exchange olymer membrane, such as a

perfluorinaied polysuli nie acid polymer membrane, an example of such a membrane being KAFiON or hydrolyzed versions of ^■ sulfonyi fluoride peril uorinated membranes; and

e) delivering the vapor res ftingi om step e) or step d) to a critical proces or application. | 81 The solution in step a), whether liquid or vapor, may comprise water in any suitable mmt or may be substantially free of water, la some embodiments the solution Is substantially free of water, meaning that water is not purposefully added to the solution such as through a dedicated source of water. The phrase .."substantially free of water" does not exclude the incidental water content that ma be present in the -sources of other solution components, such as may be present In the source of hydrogen peroxide. The phrase "substantially free of water" similarly does not exclude incidental water content that may arise from decomposition of hydrogen peroxide on system components, or tha ma enter an enclosure of the solution from the outside em ronment in some■embodiments, the solution comprises 2% or less by weight of water, or 1.5 weight % or less, or 1 ,0 welght% or less, or 0.5 weight% or less of water,

fifif In. addition to hydrogen peroxide, the solution may &rther comprise a nonaqueous excipleni Example aon aqueoas excipients include, but are not limited to, alcohols, including poly alcohols, phenols, lact nes _* mides, esters,, including polyesters, ethers, cathoxylie acids, including p iyearhoxylic acids, sulfonic acids, sulS k acids, phosphonie acids, phosphinic acids, organic solvents. Inorganic solvents, aromatic compounds, poiyaroiaailc compounds, heterocyclic compounds, including polyhe erocydic compounds, imorlnated ethers, fluoritt ed alcohols, iiaorinated sulfonic acids, uorinaied earboxylic acids, inctadmg polycarboxylie acids, flnormated phosphonie acids, deep eotectic sol ents, and combinations thereof, ^'

|070] The solution in step a) comprises one or more cations. The cations may he present, for example, as stabilizers tor the hydrogen peroxide solution, such as for a solution comprising more than 14 weight % hydrogen peroxide, such as 25 weight % or more, such as SO weight % or more.

In some embodiments, the one or more cations comprise one or more metal cations. Example metal cations include sodium, potassium, barium, calcium. copper _s magnesinm, mangaiK®e _> . ^' nickel and zinc cadons. In one embodiment, the one or more metal cations comprise a sodium, potassium, magnesium,: copper or calcium cation; in another embodiment tlie one or more metal cations comprise a magnesium or ealcmm cation and in i½ther embodiment the one or more metal cations comprise a copper cation. In an additional embodiment, the one or more metal cations comprise a sodium or potassium cation, .such, a can be derived from sodium stannate or potassium stannate, respectively. (Ιί72| The raetai cations m be present, in any suitable amount In the solution, whether used as stabilisers ox ibr other purposes. For instance, the solution may comprise 15 ppm or less by weight of metal cations, or 1.0 ppm r more by weigM of metal cations.

|0731 fee solution also comprises hydrogen peroxide In any ^' suitable amount. For example, the solution may comprise hydrogen peroxide In an amount of 10 weight % or more, IS weight % or more, 20 weight % or m re* 25 weight % or more, 3 weight % or mo ., 35 weight % or more, 40. weight % or more, 45 weight % or more, 50 weight % or more, 55 ^' weigh! ¾ or more, 60 weight % or more, 65 weight % or more, o 70 weight % or more.

|#74J The io exchange polymer In a) may be in the form of any shape or siru ture. For example, ft may be in the for of a membrane having my of the /structural characteristics of the ioa exchange membranes discussed previously. The ion exchange polymer in a) could also he in the form of, for example _* a head or pellet.

Ϊ0?5| Periluorkated poiys lfonk polymers are ion exchange polymer such as those made when hydrolyzing suifonyl fluoride perfleorinated membranes to obtain a perfiuoririaied polystilfonic acid membrane. Examples of such polymers are d sclosed In WO 2014/01 5 ! 1 , with those examples being incorporated by reference hereto, NAFIO CD is an example of a perfi oriaated sulfonic acid membrane. The ion exchange polymer (such as a peri uor ated pol siil&nic polymer) in a), and the ion exchange polymer membranes (such as peri uorinated polysulfonic-polymer membranes) described previously, may have identical compositions or may be made of different variants of ion exchange material. The ion exchange polymer (such as perfluorinaied polysoifonic polymer) material, whether in the form of a .membrane or sot, includes such a material tha has been chemically treated e«g. _» with an acid, base, or salt to modify its reactivity. For example, in certain embodiments, the NA ION® mater al, whether in he form of a membrane or not, ma be treated In a way to fo m, e,g. _s the atnittoiuum species.

|©7 1 1¾e solution is contacted with the ion exchange polymer in step b) to produce a solution having a reduced content of the one or more cations ,

I §77J ¾ ^» phrase "reduced content of the one or mote cations refers to a reduced concentration of at least one cation n the sol ution after contact with the polymer compared to fee concentration of that cation before contact with the polymer. The .phrase "reduced content of the one or mere cations'* does not require complete removal of any cation from the solution. The phrase "reduced content of the one or more *c¾tto»$ also does not requit a redaction in the concentration of several, most or all cations m the solution. In some exemplary embodiments, however, contact of the solution with the polymer reduces the content of at least two, at least three, at least four, or at least five cations in the solution,

|078] Some embodiments therefore comprise contacting fee solution with the io exchan e polymer tmder conditions sufficient to remove 70 weight % or more of at least one cation from the solution. Exemplary cations in this embodiment Include sodium, potassium, .barium, calcium,, copper, magnesium, manganese, nickel and zinc cations,

?&] Another embodiment comprises contacting the solution with the ion exchange polymer under conditions sufficient to remove 80 weight % or more of at least one cation from the solution. Exemplary ^' cations in this embodiment include sodium, potasslnn , barium, calcium, magnesium, manganese, nickel and- z nc cations,

f ^' 088| Another embodiment comprises contacting, the solution with the Ion exchange polymer under condi tions sufficient to remove 90 weight % or more of at least one cation from:

27 the solution. Exemplary cations is this embodiment include potassium,, barium, calcium, magnesiufii arid manganese cations.

fiSiJ A further embodiment comprises contacting the solution with the km exchange olyme under conditions sufficient to remove 50 weight % ot more, o 0 weight % or more of th combined total of all cations, or 50 weight % or more, or 6 ^* 0 weight % or more of the combined to tal of all metal cations, from the solution.

{083 | The solution may be contacted with the ion exchange polymer using any suitable technique. For instance, the solution may he directed to flow over a surface of the polymer, such as by passing from an inlet end to an outlet end of an enclosure containing the polymer; The solution ma also contact the polymer by positioning the polymer in an enclosure that contains a volume of the solution that ss either static or in fluid motion. Thus,, i one embodiment contacting step h) may comprise passing the solution through a packed bed comprising the ion exchange polymer. In another embodiment contacting step b) comprises placing the Ion

tge polymer in a liquid solution,- |§83| The solution may contact the ion exchange polymer under any conditions sufficient to reduce the content of the one or more cations. For instance, the solution may contact the polyme for a cumulative time of at least 5 seconds, at least 10 seconds, at least 30 seconds, at least I minute, at least 5 minutes, at least 10 minutes, at least 15 minutes, at least 30 minutes, at least 45 minutes, at least I hour, at least 2 hours, or at leas 3 hours. The contact may also take place at any appropriate temperature, such as at room temperature (22°C),

|©S4| The present disclosure also includes a vaporizer device o apparatus, and analogous systems, for delivering purified hydrogen peroxide vapor. The systems, devices, and apparatuses comprise:

2S a) a solution comprising hydrogen peroxide and one or more cations;

b) an ion exchange polymer in contact with the solution; .and

c) a housing configured to contain the solution and the polymer.

|0S5| In certai embodiments, the vaporiser contains the membranes which are preferably fixed in a module or other mutable apparatus. In embodiments in which the membranes are in fiber form, preferably the membranes are arranged in cylindrical arrays or bundles, In other embodiments., other configurations can be employed, such as square, triangular, irregular, or other configurations. The membrane module preferably includes a plurality of hollow membrane fibers each of which, extend longitudinally between, and are mounted at each end to, a respective header. In other embodiments, other configurations are contemplated, such as looped fibers wherein both ends are secured in a single header, among other configurations. Preferably, the fibers can be tain or slack, close or loosely packed formation, or spaced apart The fibers preferably have a packing density of from S% or less to about 95% or more,, or any density in between those two values. The fibers may optionally be partitioned into a certain number of bundles in order to form a space or spaces therein between. Optionally, a single bundle of fibers may he employed.

|0S6| In some embodiments, it is preferred to maintain some spacing in between the fibers to facilitate circulation of the source liquid (e.g., the purified replenishment source liquid), Optionally, a fiber bundle can be protected by a mod le support screen. Optionally, casing can provide support to a header or headers. Optionally, clips or rings can he employed to bind th .fiber bundle. Preferably, materials employed in the header and arty supports or casing are selected such that these materials are able to tolerate elevated temperature and pressure conditions and will resist reacting with or contaminatin any gas generated. n some certain

29 .embodiments, one or more membrane module may be arranged Into a cassette or battery, each cassette or battery being provided with a source liquid, pumps, valves, and Instom eniation.

[887J Iti some embodiments carrier gas enters f¼ni the lower header and exits from the upper header, In other embodiments the carrier gas eater from above and exits fi¾m the lower header, i eaeft ease gas generated from the source liquid permeates mem ane is swept away by carrier gas,

[©88] The carrier gas may he saturated, t ersaturateti, or imderstatnrated with the gas generated by the SOUK* liquid.

I» certain embodiments the vaporizer contains level sensors, commercially available from Gems Sensors & Controls,- Inc., Plakville,€X Any person of ordinary skill in the art recognizes the use of level sensors in the embodiments of the invention,

f 190J I certain embodiments the vaporizer contains thermal sensors, commercially available from Omega Engineering, Inc., Stamford, CT. Any person of ordinary skill i the art recognizes the use of thermal sensors in the embodiments of the invention.

In certain embodiments the vaporizer contains over temperature sensors, commercially available from Omega Engineering, Inc., Stamford, CT. An person of ordinary skill in the art recognizes the use of temperature, sensors in the embodiments of the invention.

in certain embodiments the vaporiser contains a drain valve, commercially available- from BioChem Fluidics, Inc., Boo On, NJ, Any person of ordinary skill in the art recognizes the use of a drain valv in the embodiments of the Invention,

f©¾$| In certai embodiments the vaporizer contains a replenishment vessel, commercially available from BioChem Floidics, inc, Boonton, NJ. Any person of ordinary skill in the art recognizes the use of a replenishment vessel in the embodiments of the invention.

30 | ¾1 1ft certain embodiments, gas generated from a sou ce liquid can be delivered at st»atmospheric pressures. Deliver ' at s fe-aimospherfc pressures is desirable m many applications, such as atomic layer deposition. Sub-atmospheric pressures can be achieved with, downstream vacuum um s

|095| In certain embodiments, the device comprises a primary -pump on the permeate side, and a second pump connected to the source liquid side. In these embodiments,, the vapor pressure differentia! or downstream pressure can be managed b adjusting the power input to the vaporizer, amount of carrier gas flow rate, carrier gas pressure, pressur drop between the liquid to the permeate side, or downstream venting,.

f§§ 6} Once choke flow is reached across the memb ne or on the permeato side of the vaporizer, further lowering of pressure an the permeate side of the vaporizer no longer increases the permeation rate across the membrane. Only by increasing the vapor pressure of the source liquid by adding power through the heater to the vaporizer will increase permeation of the gas generated by the source liquid increase,

|t f in one embodimen the power supplied to the vaporizer is through heating the outside of the vaporizer wi th electrical heaters . One skilled in the art could apply energy through other method, such as steam, transfer liquids, ambient heat, heating of the carrier gas, and other techniques,

0f i| Figure 1 illustrates the relationshi between various source liquids, purification med a _e and a vapo izer in accordance with the Invention, A supply of replenishment source liquid 13 is stored in replenishment source liquid container Ϊ (e.g., a first container). Fluid connection 4 facilitates transfer of replenishment source liquid 13 to purification replenishmen source liquid container 2 (e.g,,. a second container). Replenishment source liquid 13 can he transferred from

31 replenishment source liquid container I to purification replenishment source liquid container 2 by any .convenient -means, including a pump, pressurized gas, o -gravity feed. Inside purification rep enishment source liquid container 2 is purification material 3, which contacts replenishment source liquid 13 and converts ft. to purified replenishment source liquid 14 In a preferred embodiment _* purification material 3 is in the form of a membrane. Purification materia! 3 preferably includes a peril uorinaied lonomer (e.g, ₅ a PTSA~TFA copolymer) with high surface area, and can be a ΝΑΗΟΝΦ PTSA-TFA copolymer membrane. Purified replenishment source liqui 14 Is transported" via fluid connection 5 to pump 6 _» and then through fluid line 7 to vaporizer 11, A preferred type of pump is a diaphragm pump, as may be obtained from Bio* C!iem Ftuidics (Wildomar, CA). Many other pumps* as well as pressurized transfer or gravity feed systems lso may be used for transporting purified replenishment source liquid M from purification .re lenishment source liquid container 2 to vaporizer 1.1. The vaporizer ma be a flash vaporizer, a nebulizer, ^a bubbler _* or more preferably a membrane-based- vaporizer. Purified replenishment source liquid 14 is added to source liquid 1 _» which is contained in vaporizer 11> Carrier gas 12 enters vaporizer II. in some embodiments, carrier gas 12 may enter vaporizer 1 a bubbles (e.g., through a sparger).

10991 As illustrated in the diagram., and In the preferred case of a membrane -based v&porker, carrier gas 12 enters through hollow fiber ion exchange separation membrane 15. The membrane is preferably made from an ion exchange mem ran , and is preferably made from the same material as purification material 3. For example, both purification -material 3 and hollow fiber ion exchange separation membrane Ϊ5 can he made of an ionic fluoropolymer such as NAFION® ion -exchange membrane. Source liquid W vaporizes across hollow fiber ion exchange separation me bran 15, and then i swept away by a flow of carrier gas 12. Process gas stream 8 exits the vaporizer as a mixture of a volatile chemical component of vaporized source liquid W and carrier gas 12.

Ex&Mp! s f l lff} Materials used in the examples: 50 weight % (w%) stabilized hydrogen peroxide (Sigma Aldrkfc), ΝΑΡΤΟΝ Membrane 1 J00BW, 0.1 N NaOI-I solution, I weight %

bromoihymot him, ^' Sodium Sulfate (ACS grade), DI water, Hot/Stir Plate, Stir bar, 500mL and 100-mL beakers. Timer, 10-100 uL pipette. Analytical Scale (·£0.00 lg), and Ceramic Scissors, ί 10-1 J Bxamglg 1;,^ Test Procedures,

¾ following five tests outlined below were conducted:

Test #1: Titration of NAFION® Lamm Control Ϊ

* Titrate a .00% sample of KAF!ON© following Test #6 to determine the relative acid COB version of stock NAFIO ®

Test #2: Titration of NAFIQN® Lumen Control 2

* Titrate a 1 ,00Og sample of NAFION® following the Acid Titration Procedure to determine ¾e relative acid conversion of stock MAPI ON®

Test #3: Purification ^' of 50w%- Peroxide Using Excess H ^' AFIQN®

* Add excess amount of NAFiOND, 3,O0 g _s to S0ml of 50w% peroxide solution In a l OOmi beaker

^» Let the ΉΑΡΙ0Ν® soak, In solution at room temperature (22 °C) for one hour

* Remove the lumen from the peroxide solution and rinse with DI water for 2

minutes

* Dry NAFION® under de-i niser- fan..for 2 hoers

^»' Weigh, two 1.OQOg sam les and titrate each sample following Test M6 o Results identified as 3a and 3b respectively

Test #4: NAFIONC' Purification Efficiency Test

* 4Smi of e pur fied 50w% peroxide solution from Test 3 mid -H ,000g of

NAFIOM® are placed in a lOOmL beaker

» Let the NAFION® soak in solution at room temperature (22 °C) for one hour

* Rem ve the lumen from the peroxide solution and rinse with D water for 2 minutes

« Dry NAFIQH® under dfe-toi zer fen" for 2 hoars

» Titrate the 1 ,000g sample following Test #6

Test #5: Excess 5 % Peroxide Purification Test

« A 1.0O0g. sample of AFION® is added to 350ml of stabilized 5Gw% hydrogen peroxide

^» Let the NAF10N® soak in solution at. SO ^C 'C for one hour

» Remove the lumen from the peroxide solution and rinse with Dl water for 2 minutes

* Dry MAP!ClN® under de-ionizer fan for 2 hours

* Titrate the 1 ,0OOg sample following Test #6

Test# 6: Acid Titration Procedure

* Prepare 0.1 M KOH solution

* Cut 1.0 gram sample NAFIQN® in o ½ inch sections, md place in 50 ml of Dl water in a 500ml beaker

* Add 2.0 g 2SO to beaker, and 3 drops of bromot ymoJ blue to beaker

* Place beaker on a hot plate with a stir bar, heating to approximately 40-50 ⁸ C

34 * Add drop wise 0.1 M KOB to solution until so ution turns blue

* Calculate % converted based upon EW of 1 Ϊ 00

(KOH fflois added)

% Converted∞ (Dry Mass NAFIOM * 100

(llOO gmoi)

flftl]. Example ¾ Traeg,j½fefed Analysis of Stock and Pimfsed S I ¾ d 50w%

Hydrogen Peroxide, A quantitative a mlysls was irua on the S0w% peroxide solution itself 1 Ot&L of S0w% stabilized peroxide was purified with 6,016g of MAFIOM® for 2.25 hours at 22 ^• °C< The nmss NAFiON® added to ih& 100 m solution had six times the am urs of sulfonic acid sites required to purify this volume of solution based on the 5 JS x 10 -mol L stabilizer eoaeeniratiors detemuned by titrations 3 a and 3b.

|103| est Results. Table 1 below provides t e test conditions and titration results for the experiments.

Tabl 1; Test C¾a t¼Bg ¾s¾d Tifrafiosj Results

|M 4| Table 2 provides the trace metal, ion analysis of stock and purified stabilised S0w% hydrogen peroxide.

36

|liS] Test 1 and test 2 resulis determ ned thai the NAFfOM® used in all tests 4««ng this experiment has a starting acid conversion of 98,0 ± 1.0%. Reduction from 98% acid conversion m all NAFION® samples after exposure to the test conditions 3 -6 will b used to

37 calculate the moles of ionic stabilizers that were removed per volume of stabilized S0w% eroxide solution,

[Ϊ06| Test 3 used an excess mount of NAFION® to pull ionic stabilizers out of the Sites! of peroxide solution. The 3.049g mass of NAFION® dropped to an average acid conversion of 87.4 0,2% (average of 3a and 3b titrations). The 10.6% drop in acid conversion on the 3.049g N AFION® sample corresponds io removing 2.94 x !0 ^' mol of ions per 50ml of peroxide solution. Ma p!ying this value by 20 standardises the concentration in mol of ions per liter; the concentration of Ionic stabilizers in stabilized 5Gw% peroxide was found to be 5 J8 x mol L.

I Tes 4 conditions evaluated the efficiency of the stabilizer removal achieved by test 3. The L040g sample mass was placed in the purified peroxide solution from test 3, The N AFION© sample lost 1.4% of Its add conten The ionic stabilizer concentration of the uiifle peroxide after test 3 was calculated from the total moles of sulfonic add lost from the 1.040g sample mass 1.32 x mol of ions per 45m! of solution which corresponds to a sia liEer concentration of 2.94 x !0 ^" mol L. The single tre son! process defined in test 3 was highly effective at removing ioeic stabilizers. The ionic stabiliser concentration reduced by 20 fold which corresponds to removing 95,2% of the ionic stabilizers throngh a single MAFION# treatment process,

1108| Tes 5 examined NA ION# ^J s ability to participate in stabilizer exchange at lower acid conversion, levels. This tes determined that 51 lumens can utilize at least 95% of the membranes ion exchange .capacity to remove Ionic stabilizers from 50 hydrogen peroxide solutions. Th 1 J5Sg sample of NATION® was converted from 98,0% to 3,8%, Alongside with ΝΑΡίΟΝ * excellent resistance t degradation in highly corrosive peroxide solutions,, sonic stabilizers were able to fully .saturate the membrane deeming ΝΆΒΙ0Μ ail efficient resin to use In hydrogen peroxide purification.

|10¾ The trace metal analysis results of the stock S0w% peroxide solution cleten»ined that 97.8% of the ionic stabilizer content was due to tbe following racial ions in increasing order: Cd (935%), $a (16.55%), Ma (19.43%), and K (52,53%), Tbe total concentration of ionic sta i!kers in the stock solution was 13.90 ppm by m ss. After the purification with the -Hj.Og of NAFION¾ the Ionic stabilizer concentratio was reduced to 5.382 ppm by mass. 61.3% of the ionic siabiii2er content was removed using a single ion exchange purification step.

[11 #1 Table 2 Mgblight the metal ion species that NAFION® was highly effective at removing (Ba, Ca, Cu, Mg, Mn, Mi, K, Ha, and 2a). Of the major ionic contributors, NAFICJN® treatment was able to remove 90,7% of the potassium ions and 83 ,6% of the sodium ions. The ΉΑΡΪΟΝ membrane removed > 93% of tbe C Mg, and Mn loos, 86.3% of Ml, d > 78% of the Cu and Ni ions. Overall, NAFION® membrane was found effective at removing the ionic stabilizer content in stabilized peroxide solutions,

fllij it was further observed thai the polymers could he re~aeidiikd in acidic medium such as 10% by weight nitric acid. Other acids may also be used. The ability to re«aeldlfy the polymers indicates that the loss in acid content was due to ionic contamination,

|ί ί 2| Example 3; P unification of 50 w% H ydrogeti Peroxide Using Excess N AFION® Ion Exchange Membrane . Ex&nipie 3 describes procedures used to determine whether the Initial contact with the NAFION® ion exchange membrane, described in Example 2, was sufficient to purify the hydrogen peroxide by removal of all ionic stabilizers ,

[113] An approximately 3,00Og sample of ΝΑΡίΟΝ ion exchange membrane was placed m 50mL of 50w% stabilised hydrogen peroxide (Sigm Aldrich; Si, Louis, MO) contained in a lOOmL- beaker. Tbe membrane was allowed to soak in the solstion at room temperature (22°G) for one hour. Next, the membrane was removed from the hydrogen peroxide solution and rinsed with deionized -water for two minutes. The soaked and rmsed membrane was dried under a deiordzer fan for two hoars. Two samples of th dried NAF!0M# ion exchange membrane were titrated according to the procedure given under Example I , Hydrogen peroxide solution remaining m the beaker following removal of the MAF!ON® ion exchange membrane (i.e., "purified" hydrogen peroxide) was reserved for use in the procedure of Example 4.

|1!4| Results of tbe membrane titration procedure provided insight into tbe quantity of Ionic stabilizers present in the 50 w% stabilized hydrogen peroxide stock solution. Membrane fragments of 1.018 g and 1.16 g -requited fU mL and 9,2 mL of the strong base to achieve color change of the pB indicator. These results were associated with 87,5% and 87.2% acid conversion, respeeiively. Thus, using an excess amount of membrane to remove all ionic stabilizers fern 50 mL of the solution, the 3,049 g mass o NAFIQN® Ion exchange membrane dropped to m average acid conversion of $7.4 ±0,2%, Tbe i 0.6% drop in acid conversion on tbe 3,049 g membrane sample corresponds to removing 2.94 x 10 ^" * mol of ions per 50 mL of hydrogen peroxide solution. Multiplying this valise by 20 standardizes the concentration in moi of ions per liter. The cooeentration of ionic stabilizers- in tbe stabilized 50 w% hydrogen peroxide solution was found to be 5.8S x 10 ^' " ^* niol/L,

1115} Example 4. Purification Efficiency Testing. Example 4 describes procedures used to -determine whether the initial contact with the N AFIOM® ion exchange membrane* described in Example 3, was sufficient to purity the hydrogen peroxide by removal of all ionic stabilizers,

[116] A 45 mL volume of tbe purified 50 w% hydrogen peroxide solution from

Example 3 (i.e., the solution remaining in tbe beaker following removal of tbe NAFiON® ion

40 exchange membrane} was combined with a fresh i ,000 g sample of MARION® ion exc ange, membrane in a 100 niL beaker. The membr ne was allowed to soak in the solution at room temperature (22 ^d C) for one hour . Next, the membrane was removed lorn the hydrogen peroxide solution and r!fesed with delonlged: water for two minutes, The soaked and rinsed N AFION® ion exchange membrane was dried under a dekmizer fan for two hours. An approximately 1.000 g sam e of the dried membrane was titrated according to the procedure given under Example I , f 117] Results from this testing were useful for evaluating the efficiency of stabilizer purification achieved in the procedure of ^' Exam le 3. ASer st lling with a 1.040 g sample of NAFION® Ion exchange membrane in the procedure, a 0.9 g mass of the membrane was titrated and found to require 7.9 mL of the strong base to ach ie ve c olor change of the pH Indicator. This was associated with 96.6% acid conversion, thereby indicating the Ion exchange membrane had lost 1.4 % of its acid content. The ionic stabilizer concentration of the purified hydrogen peroxide from ^' Example 3 was calculated from the total moles of sulfonic acid lost from the 1,040 g sample mass. Here, 1,32 ¾t UF ⁵ mo! of ions per 45 mL of solution corresponded to a st&Mli er concentration of 2,9 x 1 G ^" mei/L, The single treatment process described unde Example 3 was highly effective at removing ionic stabilizers. Indeed, the ionic stabilizer concentration was reduced by 20 fold, whi ch corresponds to removing 95 ,2% of the lonle stabilizers fey the single treatment.

fii&] Exam e 5;. Assessing Capjgityof MAFIOH Example 5 describes procedures used to assess the capacity of the AFIOH® ion exchanger sulfonic acid sites can be used to bind and remove stabilizers from a stabilised hydrogen peroxide solution.

[119] Here a small amount of the Ion exchange membrane was added to a large amount of stabilized hydrogen peroxide to determine bow much of the NAFiON® i on exchange

4! membrane sulfonic acid sites coald be used to bind and remove stabilizers from the hydrogen peroxide solution, An approximately 1.000 g sample of NAFION® ion exchange membrane was added to 350 mh of stabilized 50w% hydiogea peroxide solution and allowed to soak at 50°C for one 5 hour. Next, the membrane was removed from the hydrogen peroxide solution and rinsed with delonized water for two minutes. The soaked and rinsed NAFION® ion exchange membrane was dried under a deionizer fm for two hours. Approximately 1.000 g sample o f the dried membrane was titrated according to the procedure given under Example L

|12§J Results addressed the ability of the NAFION® ion exchange membrane to participate in stabilizer binding at lower acid conversion levels, A L I 5E g sample of the NAFION Ion exchange raenibr fie required 0.4 mh of the strong base solution to achieve color change of the pH indicator, thereby demonstrating conversion of 3 J% (from 98.0%). Thus, at least 95% of the Ion exchange capacity of the membrane could be used to remove ionic stabilizers i¾m 50 w% hydrogen peroxide solutions. I addition to excellent resistance to degradation tn the presence of highly corrosive hydrogen . ^■ peroxide solutions, ionic stabilizers were able to fully saturate the NAFION® ion exchange membrane. These features mates the ΝΑΡΪ0Ν® ion exchange membrane an excellent resin for purifying hydrogen peroxide from stabilized hydrogen peroxide solutions,

¾Ij Example 6: Use of Purified Replenishment Source Uquid improves Vaporiser F¾¾| Qn. Example 611 lustras.es how the use of purified replenishment source liquid can improve performanee characteristics of a merobrane-hased vaporizer system. In this Illustrations source liquid is puntle by first contacting purification media made of the same material as the ion exchange separation membrane of the -membrane* based vaporizer . |ί22| There initially are obtained two identical menihrane-based vaporizers useful for producing gas phase hydrogen peroxide fern a source Mojuid. Each v po iser is equipped with, a reservoir that receives one or another type of a hydrogen peroxide solution. In the arrangement of cotsftpoaents of each a aratus, a tube conveys the source liquid from the .reservoir to the- ion exchan e separation membrane, which is made of PFSA-TFB copolymer and sold under the AFION® trademark (EJ. da Font de Nemours & Co. , Wilmington, DE), The reservoir of the first vaporizer is filled with a 50 w% stabilized aqueous hydrogen peroxide solution (Sigma Aldrieh; St. Louis, MO), which serves as the -replenishment source liquid. The reservoir of the second vaporizer apparatus is filled with a "purified" source liquid mat resulted from batch processing of 50 w% stabilized aqueous hydrogen peroxide solution with an amount of

NAFI0M€> membrane for a period of time sufficient io permit selective binding of any sodium or potassium ions, and selective adsorption .of any ot her Ionic or non-Ionic agents that may bind t the membrane, in the hatch processing approach, the purification media (i.e., the ΑΡΙΟΝ membrane) and the liquid being purified are simply combined and incubated or allowed to stand in a single container before the two components are separated (e.g., by simple removal of solid material; or b straining, filtering, etc,) _*

|I23| When operated under standard conditions, the first vaporizer generates steady levels of hydrogen peroxide gas over the course of about a week. The second vaporizer, using the purified replenishment source liquid* generates steady levels of hydrogen peroxide gas for a time longer than a week. This illustrates how use of the purified replenishment source liquid improves vaporizer function, for example by permitting steady gas production over a longer period of time, and by extending the useful life of the Ion. exchange separation membrane. 1 I24J In a« alternative approach for production of the purified replenishment source liquid, & cartridge containin NAPION® ion exchange edia Is inserted in-line with the tube conveying liquid from the reservoir of a metnbiane-based vap naerio the ion exchange sepafatioft tneffi!¾¾i¾e of the vaporiser. This arrangement facilitates on-board purification of the replenishment sonrce liquid so that purified replenlshrnent source liquid, and ot the

replenishment source liquid (Le _*» containing metal ions, stabilisers, etc) reaches the ion exchange separation membrane,

p2S) While the Invention ha been described in detail with respect to certain embodiments, the Invention Is not limited to those embodiments. It should be understood that modifications and combinations may fee made to the illustrated embodiments and other disclosed features to form yet additional embodiments within the scope of the invention.

44