STREAM

[001 ] This application claims priority to U.S. Provisional Application No. 61/809,256, filed on April 5, 2013, and to U.S. Provisional Application No.

61/824,127, filed on May 16, 2013.

TECHNICAL FIELD

[002] Methods, systems, and devices for the vapor phase delivery of a high concentration high purity hydrogen peroxide gas stream for use in micro-electronics and other critical process applications.

BACKGROUND

[003] Various process gases may be used in the manufacturing and processing of micro-electronics. 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, 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 corners 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 not been possible using existing technology.

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. 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://hdl.handle.net/2027/mdp.39015003708784. Moreover, studies show that delivery into vacuum leads to even lower concentrations of hydrogen peroxide (see, e.g., Hydrogen Peroxide, Schumb, pp. 228-229). The vapor composition of a 30 % H2O2 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.

[007] 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:

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 _b is the vapor pressure of a pure solution of component B, and Xb is the mole fraction of component B in the two- component solution. Therefore, 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.

[008] 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.

[009] The differential delivery rate that results when a multi-component liquid solution is used as the source of process gases make repeatable process control challenging. 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 % H ₂ O ₂ /H ₂ O) 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 microelectronics applications and other critical processes.

[010] Therefore, a technique is needed to overcome these limitations and, specifically, to allow vapor phase delivery of a sufficiently high concentration of high purity hydrogen peroxide to be used in a critical process application, such as microelectronics manufacturing.

BRIEF DESCRIPTION OF CERTAIN EMBODIMENTS

[01 1 ] Methods, systems, and device for delivering a high concentration hydrogen peroxide gas stream are provided. The methods, systems and devices are particularly useful in micro-electronics applications and other critical processes. One aspect of the present disclosure is directed to a method comprising providing a concentrated aqueous hydrogen peroxide solution in a boiler having a head space, boiling the concentrated aqueous hydrogen peroxide solution to produce a dilute vapor comprising hydrogen peroxide within the head space of the boiler, adding a dilute aqueous hydrogen peroxide solution to the concentrated aqueous hydrogen peroxide solution within the boiler to maintain the concentration of the aqueous hydrogen peroxide solution in the boiler, and delivering a consistent concentration of dilute vapor comprising hydrogen peroxide to a critical process or application.

[012] In another embodiment, the concentrated aqueous hydrogen peroxide solution in the boiler is made in situ from the dilute aqueous hydrogen peroxide solution. In another embodiment, the method can further comprise removing contaminants from the dilute vapor by passing the dilute vapor through a purification assembly before delivering. In another embodiment, the purification assembly produces a condensate stream from the steam passing through. In another embodiment, the purification assembly comprises a plurality of membranes formed from a perfluorinated ion-exchange membrane. In another embodiment, the plurality of membranes are formed from NAFION® membrane. In another embodiment, boiling the aqueous hydrogen peroxide solution is accomplished by controlling the temperature of the concentrated aqueous hydrogen peroxide solution. In another embodiment, boiling the aqueous hydrogen peroxide solution is accomplished by controlling the pressure of the concentrated aqueous hydrogen peroxide solution. In another embodiment, boiling the aqueous hydrogen peroxide solution is

accomplished by controlling the temperature and pressure of the concentrated aqueous hydrogen peroxide solution. In another embodiment, addition of the dilute aqueous hydrogen peroxide solution initiates when boiling begins. In another embodiment, the method further comprises adding a stabilizer that is non-volatile or rejected by the purification assembly, i.e., the stabilizer does not pass through the membrane.

[013] Another aspect of the present disclosure is directed to a chemical delivery system comprising a concentrated aqueous hydrogen peroxide solution, a boiler having a head space configured for boiling the concentrated aqueous hydrogen peroxide solution and producing a dilute vapor comprising hydrogen peroxide within the head space, and a manifold configured for adding a dilute aqueous hydrogen peroxide solution to the concentrated aqueous hydrogen peroxide solution within the boiler to maintain the concentration of the dilute vapor comprising hydrogen peroxide. In addition, the chemical delivery system wherein the manifold is further configured to deliver the dilute vapor comprising hydrogen peroxide to a critical process or application. [014] In another embodiment, the concentrated aqueous hydrogen peroxide solution in the boiler is made in situ from the dilute aqueous hydrogen peroxide solution. In another embodiment, the manifold further comprises a purification assembly configured to remove contaminants from the dilute vapor. In another embodiment, the purification assembly comprises a plurality of membranes formed from a perfluorinated ion-exchange membrane. In another embodiment, the plurality of membranes are formed from NAFION® membrane. In another embodiment, the boiling of the concentrated aqueous hydrogen peroxide solution is controlled by a heat source and a thermocouple coupled to the boiler. In another embodiment, the boiling of the concentrated aqueous hydrogen peroxide solution is controlled by a pressure transducer and a control valve coupled to the boiler. In another

embodiment, the boiling of the concentrated aqueous hydrogen peroxide solution is controlled by controlling the temperature of the aqueous hydrogen peroxide solution in the boiler and pressure of the head space in the boiler. In certain embodiments, the flow rate of the dilute vapor comprising hydrogen peroxide can be monitored by determining the energy used to heat the boiler solution, the change in pressure across an orifice, a combination of those monitoring methods, or any other suitable methods for monitoring gas flow in such systems. In another embodiment, the chemical delivery system can further comprise a stabilizer, which is added to the concentrated aqueous hydrogen peroxide solution, wherein the stabilizer is nonvolatile or rejected by the purification assembly, i.e., the stabilizer does not pass through the membrane.

[015] In certain embodiments, the hydrogen peroxide concentration in the dilute vapor is between 0.1 % to 15% w/w. In certain embodiments, the hydrogen peroxide concentration in the dilute vapor is between 1 % to 15% in mole fraction. In certain embodiments, the temperature of the concentrated aqueous hydrogen peroxide solution can be between 30°C and 130°C. In another embodiment, the pressure of the dilute vapor comprising hydrogen peroxide delivered to the critical process or application is controlled by a downstream valve (e.g., a Teflon ^® valve) and delivered at a pressure of up to about 2000 Torr, between about 0.1 Torr to

2000 Torr, between about 1 Torr to 2000 Torr, between about 1 Torr and 1000 Torr.

A valve downstream of the boiler or SPA can be configured according to the requirements of the applicable operating conditions to control the pressure, flow, and concentration of the hydrogen peroxide containing gas stream. In certain embodiments, a downstream valve prevents the mixing of the hydrogen peroxide containing gas stream with other process gases. An example of a valve that is useful for controlling the pressure, flow, and concentration of the hydrogen peroxide containing gas stream is a stepper controlled needle valve.

[016] In certain embodiments, the methods, systems, and devices of the present invention deliver a vapor comprising hydrogen peroxide and steam without the use of a carrier gas. In certain other embodiments, the vapor comprising hydrogen peroxide and steam includes a carrier gas, e.g., an inert gas may be used to dilute the hydrogen peroxide containing gas stream. In certain other

embodiments, the methods, systems, and devices of the present invention deliver hydrogen peroxide to processes at atmospheric or vacuum pressures by controlling the pressure through a valve (e.g., a Teflon ^® valve) downstream of the boiler or the SPA, where applicable. In certain other embodiments, any residual steam can be removed for the vapor comprising hydrogen peroxide prior delivering the hydrogen peroxide vapor to a critical process or application.

[017] Additional objects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the embodiments and claims.

[018] 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.

[019] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several embodiments of the invention and, together with the description, serve to explain the principles of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

[020] Figure 1 is a P&ID of a manifold that can be used to test methods, systems, and devices for H2O2 delivery according to certain embodiments of the present invention.

[021 ] Figure 2 is a P&ID of a manifold that can be used to test methods, systems, and devices for H ₂ O ₂ delivery according to certain embodiments of the present invention. [022] Figure 3 is a P&ID of a manifold that can be used to test methods, systems, and devices for H2O2 delivery according to certain embodiments of the present invention.

[023] Figure 4A is a chart showing the relationship between H ₂ O ₂

concentration and density for 0-5 wt.% aqueous H2O2 solutions.

[024] Figure 4B is a chart showing the relationship between H2O2

concentration and density for 5-100 wt. % aqueous H2O2 solutions.

DESCRIPTION OF CERTAIN EMBODIMENTS

[025] Embodiments of the methods, systems, and devices provided herein, in which steam can be used to deliver hydrogen peroxide, are shown by reference to Figures 1-3.

[026] Figure 1 depicts a test manifold 100. Manifold 100 can comprise a boiler 1 10 configured to contain a solution 1 1 1 and having a head space in a portion of the boiler 1 10. Boiler 1 10 can be a quartz boiler or formed of a like material that is compatible with the operating conditions. Manifold 100 can further comprise a band heater 120 (e.g., 1 100 W heater band) and a lamp 130 (e.g., 800 W IR lamp) configured to heat solution 1 1 1 and cause a portion of solution 1 1 1 to vaporize. Manifold 100 can be formed of material that is compatible with operating conditions and peroxide solutions.

[027] As shown in Figure 1 , connected to boiler 1 10 can be a pressure relief line 140 which can be in fluid communication with a valve 141 . Valve 141 can be in fluid communication with a scrubber 151 (e.g., Carulite 200 4x8 catalyst scrubber). Valve 141 can be configured to be a pressure relief valve, which can open and release pressure from boiler 1 10 at a predetermined pressure set point to prevent over pressurization of boiler 1 10. Valve 141 can be made of PTFE. In addition, connected to boiler 1 10 can be a drain line 160, which can connect to an open drain 162. In fluid communication with drain line 160 and boiler 1 10 can be a thermocouple 161 . Thermocouple 161 can detect the temperature of solution 1 1 1 in boiler 1 10. In addition, a controller (not shown) (e.g., Watlow EZ-Zone controller) can control band heater 120 and lamp 130 based on feedback from thermocouple 161 . As shown in Figure 1 , also connected to drain 162 can be a level leg 170. Level leg 170 can be a ½" PFA conduit configured to allow for visual determination of the level in boiler 1 10. A valve 163 can be positioned between drain 162 and level leg 170, and valve 163 can be configured to isolate drain 162.

[028] In the upper portion of boiler 1 10 can be a discharge line 180 that allows vapor to exit from the head space of boiler 1 10 and exit manifold 100.

Discharge line 180 can be in fluid communication with level leg 170, as shown in Figure 1.

[029] Discharge line 180 and scrubber 151 can be wrapped in a heat trace 190, which can generate heat and control the temperature of the vapor transported through the wrapped components. By controlling the temperature of the vapor, condensation of the vapor can be reduced or prevented.

EXAMPLE 1

[030] Manifold 100, as shown in Figure 1 was used to test delivery of H ₂ O ₂ with steam. As part of the test, an initial volume of 950 ml of 30% H2O2 and 70% Dl water (w/w) was boiled in boiler 1 10 for a period of 24 minutes. The temperature was maintained during the test between about 108-1 14 °C. After 24 minutes, the final volume of solution in boiler 1 10 was 567 ml. Using a sample of the remaining solution the density was measured using an Antor Paar DMA 4100M Density Meter. Based on the density measurement the H2O2 concentration was calculated. For 0- 5% solutions the equation used to calculate the concentration is shown below as equation 1 .

H ₂ 0 ₂ Cone. [w%] = 276.49 x Density [^] - 275.57 (1 )

[031 ] Figure 4A is a chart showing the linear relationship between the concentration of H ₂ O ₂ in a 0-5 wt. % aqueous H ₂ O ₂ solution and the density of the solution, as described by equation 1 . For 5-100 wt. % aqueous H2O2 solutions, the equation used to calculate the concentration is shown below as equation 2.

H ₂ 0 ₂ Cone. [w%] = 224.66 x Density [^] - 220 (2)

[032] Figure 4B is a chart illustrating the linear relationship between the concentration of H2O2 in a 0-5 wt. % aqueous H2O2 solution and the density of the solution, as described by equation 2.

[033] The final concentration of H2O2 was 41 .4 wt. %. Based on these measurements the consumption rate and delivery rate for both the H2O2 and H ₂ O was calculated. The H2O2 consumption rate was about 1 .29 ml/min and the H ₂ O consumption rate was about 14.6 ml/min. The H ₂ O ₂ gas delivery rate was about 1 .3 slm and the H ₂ O gas delivery rate was about 18.3 slm. These gas delivery rates are averaged based on the initial and final concentration of the solutions. Table 1 below shows some of the parameters and results of the test.

Table 1

No SPA, No Refill

Run Time: 24 Minutes Boiler Temperature: 108-114°C

Solution used 30% H202

[034] The data in Table 1 illustrates that the concentration of the solution can change in minutes without a refill solution, increasing 1 1 .2 wt. % in 24 minutes. This rate of change can bring the concentration into a dangerous range within minutes.

[035] Another embodiment according to an aspect of the methods, systems, and devices provided herein is described below by reference to a manifold 200, as shown in Figure 2. Manifold 200 can comprise all the components of manifold 100 as described above with reference to Figure 1 along with additional components.

Manifold 200 can comprise a purification assembly 210.

[036] According to various embodiments, the purification assembly can be a membrane contactor that is compatible with the operating conditions. For example, the purification assembly can be a steam purification assembly (SPA) constructed similarly to the devices described in commonly assigned U.S. Patent No. 8,287,708, which is herein incorporated by reference.

[037] Purification assembly 210 can be located between discharge line 180 and process outlet 21 1 of manifold 200. Purification assembly 210 can comprise a plurality of membranes formed of, for example, a perfluorinated ion-exchange membrane, such as a NAFION ^® membrane. In certain embodiments, the membrane is an ion exchange membrane, such as a polymer containing exchangeable ions. Preferably, 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 tetrafluoride-propylene rubber, and fluorinated thermoplastic elastomers.

[038] Manifold 200 can further comprise a refill supply 220, a refill line 230, a control valve 240, and a sensor 250. Refill supply 220 can be in fluid communication with control valve 240 and control valve 240 can be in fluid communication with refill line 230 and level leg 170. Sensor 250 can be located in level leg 170 and can be configured to detect the level of solution in level leg 170 or can simply detect the presence of solution at a specific level in level leg 170. Sensor 250 can be in communication with control valve 240 and based on a signal from sensor 250, control valve 240 can be positioned open, closed, or partially open (e.g., 1 -99% open). Based on the position of control valve 240 additional refill supply 220 can be fed to level leg 170. Refill supply 220 can be pressurized. For example, nitrogen gas at 15-20 psig can be coupled to the refill supply 220 to pressurize the supply.

[039] Manifold 200 can further comprise a condensate line 260, which can be in fluid communication with purification assembly 210. Condensate line 260 can be configured to discharge condensate from purification assembly 210 and pass the condensate through an orifice 261 and discharge the condensate into a container 262 configured to collect the condensate. Orifice 261 can be, for example, a 0.008" sapphire orifice. In an alternate embodiment (not shown), condensate line 260 can be in fluid communication with a heated scrubber, which can be configured to eliminate the need for collection of the condensate.

[040] Discharge line 180, scrubber 151 , and purification assembly 210 can be wrapped in a heat trace 190, which can generate heat and can control the temperature of the vapor transported through the wrapped components. By controlling the temperature of the vapor, condensation of the vapor can be reduced or prevented.

EXAMPLE 2

[041 ] Manifold 200, as shown in Figure 2, was used to test delivery of H2O2 with steam including passing the hydrogen-peroxide containing gas stream through purification assembly 210, which was an SPA, as described above. In Example 2, there was no refilling of the solution by way of refill supply 220 to level leg 170, therefore valve 240 remained closed the duration of the test. As part of the test, an initial volume of 950 ml of 30% H2O2 and 70% Dl water (w/w) was boiled in quartz boiler 1 10 for a period of 35 minutes. The temperature was maintained during the test between about 1 12-125 °C. The temperature was maintained by controlling heat band 120 and lamp 130 based on readings from thermocouple 161 .

[042] After the 35 minutes, the final volume of solution in quartz boiler 1 10 was 785 ml. The final concentration of H ₂ O ₂ was 33.08 wt. %. Based on these measurements the consumption rate and delivery rate for both the H2O2 and H ₂ O was calculated. The H2O2 consumption rate was about 0.49 ml/min and the H ₂ O consumption rate was about 4.2 ml/min. The H2O2 gas delivery rate was about 0.47 slm and the H ₂ O gas delivery rate was about 5.2 slm. These gas delivery rates are averaged based on the initial and final concentration of the solutions. As illustrated by the result of example 3 compared to example 2, the boiling point increased with the use of purification assembly 210 because of the pressure increase as a result of the back pressure created by purification assembly 210. In addition, delivery rate decreased with the use of purification assembly 210 in place. Furthermore, purification assembly 210 was compatible with the H2O2 steam, there were no ruptured membranes and no evidence of chemical degradation within purification assembly 210 as a result of the test.

[043] Manifold 200 as described above can be used to deliver a process gas containing a hydrogen peroxide concentration as exhibited by Example 2 and Example 3. However, the duration of the tests were kept fairly short due to the loss in solution and the increase in H ₂ O ₂ concentration within the boiler as a result of the tests, which can result in dangerous H2O2 concentrations in the liquid and/or gas phase. Accordingly, an advantage of the present disclosure is the ability to extend the duration of the test or operating time of the manifolds, up to a nearly continuous operation mode, by adding a dilute H2O2 solution to the concentrated H2O2 solution within the boiler during the test. Example 3 describes a test, according to certain embodiments of the methods and systems disclosed herein, in which a dilute H2O2 solution was added to manifold 200 during the test in an effort to maintain the concentration of the concentrated solution within boiler 1 10 resulting in a maintained drawing of dilute vapor from the head space within the boiler. Thus, the molar concentration of gaseous hydrogen peroxide delivered to a critical process is kept in balance by an equivalent feed of liquid hydrogen peroxide.

[044] Optionally, manifold 200 can further comprise a pressure transducer 310 in fluid communication with pressure control line 140. Pressure transducer 310 can be a Teflon pressure transducer, a stainless steel pressure transducer, or the like. Pressure transducer 310 can be configured to read pressure in boiler 1 10. In addition, pressure transducer 310 can be in communication with valve 141 and together they can control the pressure within boiler 1 10 to a set point. Valve 141 can also be located before scrubber 151 to adjust for variable pressure downstream of the invention. Therefore, manifold 200 can be configured to control boiler 1 10 (i.e., boiling) by temperature same as manifold 100 or by pressure. In yet another embodiment, manifold 200 can be configured to control boiler 1 10 by both

temperature and pressure. It is contemplated that the delivery pressure of the dilute solution can range from 20 torr to 2 barg.

[045] Another embodiment according to an aspect of the methods, systems, and devices provided herein is described below by reference to a manifold 400, as shown in Figure 3. Manifold 400 can comprise all the components of manifold 100 as described above with reference to Figure 1 along with some components described in regards to manifold 200. For example, in addition to all the components from manifold 100, manifold 400 can further comprise refill supply 220, refill line 230, control valve 240, and sensor 250. Manifold 400 can be configured to test that solution and vapor concentration within the boiler can be maintained by refilling boiler 1 10 with refill supply 220 having a proper concentration.

EXAMPLE 3

[046] Manifold 400, as shown in Figure 3, was used to test delivery of H2O2 with steam without passing the steam through purification assembly 210. As part of the test, an initial volume of 882 ml of 39.2% H ₂ O ₂ and 60.8% Dl water (w/w) was boiled in boiler 1 10 for a period of 35 minutes. The temperature was maintained during the test between about 1 13-1 15 °C. The temperature was maintained by controlling heat band 120 and lamp 130 based on readings from thermocouple 161 . During the test, refill supply 220 comprised a 9.9% H ₂ O ₂ and 90.1 % H ₂ O (w/w) solution at a pressure between 10-18 psig. The initial refill supply 220 volume was 531 ml. [047] After 35 minutes, the final concentration of H2O2 solution in boiler 1 10 was 40.8 wt. %. The final volume of the refill supply 220 was 67 ml. The H2O2 vapor delivery rate was calculated to be about 1 .35 slm, based on Raoult's Law. Table 2 below shows some of the parameters and results of the test.

Table 2

[048] Example 3 illustrates that a concentration of 39.2% H ₂ O ₂ after 35 minutes increased only 1 .6% to 40.8%. Accordingly, Example 3 illustrates that the H2O2 concentration can be substantially maintained and controlled utilizing the systems and methods of the present disclosure.

EXAMPLE 4

[049] Manifold 200, as shown in Figure 2, was used to test the delivery of H2O2 with steam including passing the hydrogen peroxide containing gas stream through purification assembly 210, which was an SPA, as described above. Two tests were performed for 35 minutes each. The first test was performed with a 20.4% aqueous H ₂ O ₂ solution in the boiler and the second test was performed with a 44.5% aqueous H2O2 solution in the boiler.

[050] The test parameters and results of the first test are shown below in Table 3. Table 3

[051 ] The H ₂ O ₂ vapor delivery rate for the first test was calculated to be about 0.34 slm, based on Raoult's Law.

[052] The tests parameters and results of the second test are shown below in Table 4.

Table 4

[053] The H ₂ O ₂ vapor delivery rate was calculated to be about 0.77 slm, based on Raoult's Law.

[054] Examples 1 -4 demonstrate that the total H ₂ O ₂ output of a system according to an aspect of the present invention can be matched with the appropriate refill solution concentration to maintain the solution concentration in the boiler and the H ₂ O ₂ vapor delivery rate. Table 6 shows the range of refill solutions required for the aqueous H ₂ O ₂ boiler solutions of different wt. % H ₂ O ₂ at 50°C and 130°C.

Table 6

[055] The refill concentration was calculated using the equations found in "Hydrogen Peroxide" by Schumb, Satterfield, and Wentworth (1995), which is incorporated herein by reference. [056] According to various embodiments, the boiler can be a quartz boiler and the various components of the manifold can be made of materials that are compatible with the operating conditions, for example, stainless steel, PFA, or PTFE. Such materials can aid in production of higher purity process gas.

[057] According to various embodiments, a stabilizer can be added to the solution within the boiler that is non-volatile or rejected by the membrane, i.e., the stabilizer does not pass through the membrane. Adding the stabilizer can increase the safety of the method and process.

[058] According to another embodiment, a dilute H2O2 H2O solution can be introduced into the boiler and the dilute solution can be boiled down to form the concentrated solution. Once reaching the concentrated solution any additional loss can be replenished by adding additional dilute H ₂ O ₂ solution to make up for the vapor lost to the boiler head space. Accordingly, this can deliver dilute vapor of H2O2 and steam. This method allows for the concentrated hydrogen peroxide solution in the boiler to be made in situ from the dilute aqueous hydrogen peroxide solution. This can allow for consistent delivery of steam with H ₂ O ₂ vapor by using the dilute solution feed to balance the vapor phase head space within the boiler.

[059] Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as

exemplary only, with a true scope and spirit of the invention being indicated by the following claims.