SYSTEMS, AND METHODS OF USING SAME

Cross-reference to related applications

[0001] The present application claims the benefits of United States Provisional Application No. 62/536,566, filed July 25, 2017, the disclosure of which is hereby incorporated by reference in its entirety.

BACKGROUND INFORMATION

[0002] Technical Field

[0003] The present disclosure relates generally to the field of apparatus, systems, and methods for sourcing normally solid chemical compositions for deposition onto a substrate, and more specifically to sublimer apparatus, systems, and methods of their use, particularly for producing substrates having one or more layers or films comprising the composition deposited onto the substrate, or onto a layer or film previously deposited on the substrate.

[0004] Background Art

[0005] It is a common practice to deposit films or layers of inorganic, organic, organometallic, mixtures of these, and other chemical compositions (commonly referred to as "precursors") onto semiconductor substrates. There are several semiconductor manufacturing companies in the business of applying these films or layers onto the substrates, including semiconductor substrates as well as insulating substrates. In certain instances, the chemical compositions must be sublimed, as they are solids at the temperatures and pressures used in processes such as chemical vapor deposition ("CVD") and atomic layer deposition ("ALD"). "Subiimers" and "sub!irnators" are equivalent terms of art understood to mean apparatus defining a zone or zones for drawing a carrier gas across a solid, subliming composition in order to deliver a treatment composition comprising the sublimed composition plus carrier gas to a substrate. The sublimation and carrying may be accompanied by heating elements or other temperature control subcomponents. In certain sublimers, vacuum pumping may be used rather than a carrier gas.

[0006] Various types of sublimers and methods are used for the above. All generally comprising a container defining a uniform heating zone, and heating apparatus such as electric heating elements for direct or indirect heating of carrier gas. In one sublimer type, designed to increase saturation of carrier gas with the solid precursor being sublimed, and reduce channeling issues seen in more traditional source designs, one or more trays or shelves are provided for holding the solid precursor. For example, U.S. Patent No. 9,034,105 discloses a sublimer configured to flow the gas over the top surface of the shelf, in contact with the solid material supported thereon. Other patent documents disclosing this type of sublimer for increasing saturation of precursor in a carrier gas include Published U.S. Patent Apps. US20050006799 and US2017003751 1 , U.S. Patent No. 8,821,640, and WO/2016069467A1. Published U.S. Patent App. US20160305019, and U.S Patent Nos. 9,109,287, 7,775,508 and 9,593,416, exemplify another type of sublimer where the focus is on improved single solid source "body filled" containers. Gas flow distribution and/or thermal conduction to the solid precursor is improved, with reduced channeling. Various other sublimer designs are disclosed in Published Unexamined Korean Patent Applications KR1020160132326 and KR1020170000379, Published U.S. Patent Apps. US20060264061 and US20160230275, as well as U.S. Patent Nos. 7,488,512; 7,651, 570, and 7,428,373.

[0007] The predominant technique is the first-mentioned above, where one or more trays or shelves are employed to hold or support the solid precursor, and carrier gas is caused to flow tangentially across the top of the precursor. While fairly efficient, these sublimers suffer from a number of deficiencies, one or more of which are addressed in the present disclosure. Since the carrier gas flows tangentially across the top surface of the subliming mass of solid precursor, as the precursor is consumed, this top surface will change location and shape, leading to varied tangential flow velocity across this changing top surface. Stated differently, the interface between the flowing carrier gas and the top surface of the solid precursor will move, but perhaps not all regions of the top surface will experience the same carrier gas flow velocity, leading to varied precursor pickup across a cross-section of the solid precursor. The use of trays or shelves in the disclosed units requires the sealing of trays using O-rings or other gaskets, and loading and cleaning of the trays may be more difficult or cumbersome. Where the trays or shelves are "open" designs (with no defined top and/or no internal walls to segregate portions of the solid from one another), the loaded precursor may move about in the trays or shelves during shipment. During use there is a difficulty in accurately determining the level (height) of precursor left in each tray or shelve, or in different regions of individual trays or shelves. This may limit the applicability of the technique to operations where more frequent shutdown may be tolerated to change out the trays or shelves, which would also be counterproductive.

[0008] It would be an advanced in the field of apparatus, systems, and methods for sourcing normally solid chemical compositions for deposition onto a substrate, and more specifically to sublimer apparatus, systems, and methods of their use, particularly for producing substrates having one or more layers or films comprising the composition deposited onto the substrate, or onto a layer or film previously deposited on the substrate, to provide a sublimer addressing one or more of these identified deficiencies,

[0009] SUMMARY

[0010] In accordance with the present disclosure, apparatus, systems (sublimers) and methods of use of same to sublime solid precursor chemical compositions and deposit same on substrates are described that may reduce or eliminate problems with known apparatus, systems, and methods. An important feature of the apparatus and methods of the present disclosure is use of a carrier gas that does not directly contact the solid precursor chemical composition until after the precursor sublimes and traverses through a porous, thermally conductive material - in that sense, the carrier gas flow is decoupled from the sublimed precursor flux through the porous and thermally conductive material. The precursor vapor flux is generally 'vertical' through the porous and thermally conductive material, and mixes with the carrier gas flowing tangentially across a lower surface of the porous and thermally conductive solid material.

[0011] One aspect of the disclosure is a method comprising (or consisting of, or consisting essentially of):

(a) placing one or more cartridges, each having two or more compartments supporting a solid precursor chemical composition, into a sublimer, the sublimer comprising a first structure and a second structure external of the first structure, the first structure defining a uniform heating zone, the one or more cartridges each having a porous bottom panel (defined to include bottom panels that have areas or regions of porosity, and regions that are not porous), at least one side panel connecting a top panel with a porous bottom panel, and one or more internal walls forming the two or more compartments, the porous bottom panel comprising a porous and thermally conductive solid material (metallic, ceramic, or polymeric) through which vapor phase precursor chemical composition may pass through after subliming, while the side panels and top panel are non-porous to the vapor phase precursor chemical composition (in this configuration the sublimer may be referred to herein as an "oven", and cartridges may be either be rectilinear or curvilinear);

(b) flowing a carrier gas through a pre-heat zone, forming a thermally adjusted carrier gas;

(c) flowing the thermally adjusted carrier gas through the uniform heating zone tangentially past (and without flowing through) the porous bottom panel of the one or more cartridges for a time and temperature sufficient to produce a deposition composition comprising vapor phase precursor chemical composition (or derivative thereof, for example: W2CI10 solid --> WCI5 vapor) dispersed in the thermally adjusted carrier gas.

[0012] Another aspect of the disclosure is a method comprising (or consisting of, or consisting essentially of): (a) loading a volume of a free-flowing solid precursor chemical composition into an enclosed space defined by a first structure of a sublimer, the sublimer comprising the first structure, a second structure attached to the first structure, and a common wall between the first and second structures, a major portion of the common wall comprising a porous and thermally conductive solid material (metallic, ceramic, or polymeric), the first and second structures each being essentially hollow three- dimensional rectilinear (for example rectangular or cubical) or curvilinear (for example cylindrical or spherical) bodies, the second structure having a floor, four side walls, and at least one internal partition wall defining a carrier gas thermal adjustment flow channel and a thermally adjusted carrier gas flow channel, the porous and thermally conductive solid material of the common wall allowing the solid precursor chemical composition to pass through after subliming (in this configuration the sublimer may be referred to herein as an "canister");

(b) flowing a carrier gas through the carrier gas thermal adjustment flow channel, forming a thermally adjusted carrier gas;

(c) flowing the thermally adjusted carrier gas through the thermally adjusted carrier gas flow channel tangentially past (and without flowing through) the porous and thermally conductive solid material of the common wall for a time and temperature sufficient to produce a deposition composition comprising vapor phase precursor chemical composition dispersed in the thermally adjusted carrier gas.

[0013] Another aspect of this disclosure is an apparatus (in this configuration the sublimer may be referred to herein as an "oven") comprising (or consisting essential of, or consisting of):

(a) a first (in certain embodiments, a generally cubical) structure (in certain embodiments having a floor, a ceiling, and three sidewalls connecting the floor and ceiling) defining a uniform heating zone;

(b) one or more solid precursor chemical composition cartridges slidably engageable with internal surfaces of (in certain embodiments two opposing) sidewalls of the first structure, the cartridges each having a porous bottom panel, at least one side panel connecting the porous bottom panel and a top panel, and one or more internal walls forming the two or more compartments, the porous bottom panel comprising a porous and thermally conductive solid material througli which a solid precursor chemical composition may pass after subliming, while the side panels and top panel are non-porous to the vapor phase precursor chemical composition, the cartridges extending generally horizontally and positioned in stacked relationship with sufficient space between the cartridges, and between a lowermost cartridge and the floor of the first generally cubical structure, and between an uppermost cartridge and the ceiling of the first generally cubical structure, such that a fluid may flow across the porous bottom panel of each cartridge;

(c) a carrier gas pre-heat zone (in certain embodiments separated from the uniform heating zone by the floor, the ceiling, and the three sidewalls of the first generally cubical structure, and further separated from the uniform heating zone by a door, the door hinged!y attached to a second generally cubical structure external of the first generally cubical structure, the second generally cubical structure having a floor, a ceiling, and three sidewalls connecting the floor and ceiling, the door extending from opposing sidewalls of the second generally cubical structure and from the floor to the ceiling of the second generally cubical structure);

(d) a carrier gas inlet iluidly connecting a source of carrier gas with the carrier gas pre-heat zone, the carrier gas inlet positioned near a top of the carrier gas pre-heat zone;

(e) a pre~heated carrier gas passage iluidly connecting the carrier gas pre-heat zone and the uniform heating zone, the pre-heated carrier gas passage positioned near a bottom of the uniform heating zone;

(f) a deposition composition passage iluidly connecting the uniform heating zone and a downstream unit; and

(g) one or more carrier gas pre-heat zone heating elements attached to or integral with external surfaces of the first structure, attached to or integral with internal surfaces of the second structure. [0014] Another aspect of this disclosure is an apparatus (in this configuration the sublimer may be referred to herein as a "canister") comprising (consisting essential of, or consisting of):

(a) a first structure comprising a first generally hollow three-dimensional rectilinear or curvilinear body, the first structure configured to be at least partially loaded with a volume of a free-flowing solid precursor chemical composition into an enclosed space defined by the first structure;

(b) a second structure comprising a second generally hollow three-dimensional rectilinear or curvilinear body attached to the first structure, the second structure having a floor, at least one side wall, and at least one internal partition wall defining a earner gas thermal adjustment flow channel and a thermally adjusted carrier gas flow channel: and

(c) a common wall between the first and second structures, a major portion of the common wall comprising a porous and thermally conductive solid material, the porous and thermally conductive solid material of the common wall allowing vapor phase precursor chemical composition to pass through after subliming to form a deposition composition, while the common wall retains a balance of the solid precursor chemical composition in the first structure.

[0015] Substrates including a film or layer comprising the precursor chemical composition or derivative thereof produced according to a method of this disclosure are considered another aspect of this disclosure.

[0016] Systems, apparatus, and methods of the disclosure will become more apparent upon review of the brief description of the drawings, the detailed description of the disclosure, and the claims that follow.

[0017] BRIEF DESCRIPTION OF THE DRAWINGS [0018] The manner in which the objectives of the disclosure and other desirable characteristics can be obtained is explained in the following description and attached drawings in which:

[0019] FIG. 1 is a schematic process flow diagram of one method, system, and apparatus embodiment in accordance with the present disclosure;

[0020] FIGS. 2, 3, and 4 are schematic front elevation views, partially in cross-section, of three sublimer oven embodiments in accordance with the present disclosure;

[0021] FIG. 5 is a perspective view, partially in phantom, of one cartridge embodiment that may be used in the ovens illustrated schematically in FIGS. 2, 3, and 4;

[0022] FIG. 6 is a schematic cross-sectional view of the cartridge illustrated schematically in FIG. 5;

[0023] FIG. 7 is a schematic cross-sectional view of a portion of another sublimer embodiment illustrating how the cartridge illustrated in FIG. 6 may be inserted into the sublimer;

[0024] FIGS. 8, 9, and 10 are schematic cross-sectional views of three other cartridge embodiments;

[0025] FIG. 1 1 is a plan view of a coated-wire mesh used in the cartridge illustrated schematically in FIG. 10:

[0026] FIG. 12 is a schematic perspective view, and FIG. 13 is a schematic cross-sectional view, of another sublimer embodiment in accordance with present disclosure; [0027] FIG. 14 is a schematic perspective view of another sublimer in accordance with the present disclosure, with FIG. 15 being a second perspective view with valves removed, and FIG. 16 being a third perspective view, partially in phantom.

[0028] FIG. 17 is a schematic plan view, with the first structure and common wall removed, of a second structure of the sublimers illustrated schematically in FIGS. 14 and 15;

[0029] FIGS. 18 and 19 are logic diagrams of two method embodiments in accordance with the present disclosure; and

[0030] FIGS. 20 and 21 are schematic prospective views of two other sublimer embodiments in accordance with the present disclosure (cylindrical sublimer, and oven sublimer with carrier gas tube snaking through heated space between first and second structures).

[0031] It is to be noted, however, that FIGS. 1-21 of the appended drawings are schematic in nature, may not be to scale, and illustrate only typical embodiments of this disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments.

[0032] DETAILED DESCRIPTION

[0033] In the following description, numerous details are set forth to provide an understanding of the disclosed systems, apparatus, and methods. However, it will be understood by those skilled in the art that the systems, apparatus, and methods covered by the claims may be practiced without these details and that numerous variations or modifications from the specifically described embodiments may be possible and are deemed within the claims. For example, wherever the term "comprising" is used, embodiments and/or components and or steps where "consisting essentially of and "consisting of are explicitly disclosed herein and are part of this disclosure. An example of "consisting essentially of may be a deposition composition consisting essentially of WCls and the carrier gas argon may have trace amounts of nitrogen, oxygen, and other gases, as well as trace amounts of other W- compounds, Ni-compounds, Ni and other metals, oxides, and other chemical species, and the like. An example of "consisting of may be a porous panel made up of sintered Ni and no other metals or ceramic materials, or sheet metal walls made up of only nickel metal. Another example of "consisting essentially of may be with respect to solid chemical precursor composition that consists essentially of an inorganic compound, such as WCI5, meaning that a minor portion, perhaps up to 10, or up to 5, or up to 4, or up to 3, or up to 2, or up to 1 wt, percent may be a minor portions or trace amounts of other W-compounds, metals, oxides, and other chemical species, and the like. An example of apparatus, systems, and methods using the transition phrase "consisting of includes those where only two or three cartridges are used, or where the only control aspect is feedback control based on precursor concentration in the deposition composition. The term "comprising" and derivatives thereof is not intended to exclude the presence of any additional component, step or procedure, whether or not the same is disclosed herein. In order to avoid any doubt, all compositions, apparatus, systems, and methods claimed herein through use of the term "comprising" may include any additional component, step, or procedure unless stated to the contrary. In contrast, the term, "consisting essentially of excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term "consisting of excludes any component, step or procedure not specifically delineated or listed. The term "or", unless stated otherwise, refers to the listed members individually as well as in any combination. The use of "may", where an embodiment "may include" or "may comprise" a certain feature or step, explicitly discloses embodiments that include that feature or step, as well as embodiments that do not include that feature or step. Moreover, the use of negative limitations is specifically contemplated; for example, certain apparatus, systems, and methods may comprise a number of physical components and features, but may be devoid of certain optional hardware and/or other features. For example, certain sublimer embodiments may be devoid of components that are not compatible with the solid precursor chemical composition being sublimed. Certain other apparatus embodiments may be devoid of any gaskets or O- rings. In certain embodiments the solid porous material may be devoid of anything but sintered nickel. Certain method embodiments may be devoid of a loading step (the solid precursor may already be loaded into the sublimer or into the cartridge). Certain methods may be devoid of any step where the carrier gas contacts the solid precursor chemical composition. All published patent applications and patents referenced herein are hereby explicitly incorporated herein by reference. In the event definitions of terms in the referenced patents and applications conflict with how those terms are defined in the present application, the definitions for those terms that are provided in the present application shall be deemed controlling.

[0034] As explained briefly in the Background, in existing embodiments carrier gas is caused to flow tangentially across the top of the solid precursor chemical composition and/or through the solid precursor chemical composition. While fairly efficient, these sub!imers suffer from a number of deficiencies, one or more of which are addressed in the present disclosure. Since the carrier gas flows tangentially across the top surface of the subliming mass of solid precursor, as the precursor is consumed, this top surface will change location and shape, leading to varied tangential flow velocity across this changing top surface. Stated differently, the interface between the flowing carrier gas and the top surface of the solid precursor will move, but perhaps not all regions of the top surface will experience the same carrier gas flow velocity, leading to varied precursor pickup across a cross-section of the solid precursor. The use of trays or shelves in the disclosed units requires the sealing of trays using O-rings or other gaskets, and loading and cleaning of the trays may be more difficult or cumbersome. Where the trays or shelves are "open" designs (with no defined top and/or no internal walls to segregate portions of the solid from one another), the loaded precursor may move about in the trays or shelves during shipment. During use there is a difficulty in accurately determining the level (height) of precursor left in each tray or shelve, or in different regions of individual trays or shelves. This may limit the applicability of the technique to operations where more frequent shutdown may be tolerated to change out the trays or shelves, which would also be counterproductive.

[0035] It would be an advanced in the field of apparatus, systems, and methods for sourcing normally solid precursor chemical compositions for deposition onto a substrate, and more specifically to sublimer apparatus, systems, and methods of their use, particularly for producing substrates having one or more layers or films comprising the composition deposited onto the substrate, or onto a layer or film previously deposited on the substrate, to provide a sublimer addressing one or more of these identified deficiencies.

[0036] One aspect of the disclosure is a method comprising (or consisting of, or consisting essentially of):

(a) placing one or more cartridges, each having two or more compartments supporting a solid precursor chemical composition, into a sublimer, the sublimer comprising a first structure and a second structure external of the first structure, the first structure defining a uniform heating zone, the one or more cartridges each having a porous bottom panel, at least one side panel connecting the porous bottom panel with a top panel, and one or more internal walls forming the two or more compartments, the porous bottom panel comprising a porous and thermally conductive solid material through which vapor phase precursor chemical composition may pass after subliming;

(b) flowing a carrier gas through a pre~heat zone, forming a thermally adjusted carrier gas;

(c) flowing the thermally adjusted carrier gas through the uniform heating zone tangentially past (but not through) the porous bottom panel of the one or more cartridges for a time and temperature sufficient to produce a deposition composition comprising vapor phase precursor chemical composition, or deri vative thereof dispersed in the thermally adjusted carrier gas.

[0037] Certain methods of this disclosure include those wherein the thermally adjusted carrier gas flows into a pre-heated carrier gas supply plenum between the first structure and the second structure, the pre-heated carrier gas supply plenum positioned below a lowermost one of the one or more cartridges, and the deposition composition flows into a deposition composition plenum inside the first structure, the deposition composition plenum positioned above an uppermost one of the one or more cartridges. [0038] Certain methods of this disclosure include those wherein the flowing of the thermally adjusted carrier gas through the uniform heating zone comprises:

(d) flowing the thermally adjusted carrier gas tangentially across (but not through) a first porous bottom panel of a first cartridge in a first uniform heating zone in a first direction, forming an intermediate composition comprising sublimed precursor composition at a first concentration in the carrier gas; and

(e) flowing the intermediate composition tangentially across (but not through) a second porous bottom panel of a second cartridge in a second uniform heating zone in a second direction, forming the deposition composition having a second concentration of precursor chemical composition greater than the first concentration in the carrier gas, wherein the second direction differs from the first direction by an angle a of at least 90 degrees (or at least 100, or 1 10 or 120 or, 130, or, 140, or 150, or 160, or 170, or 180 degrees).

[0039] Certain methods of this disclosure include those wherein the flowing of the carrier gas through the pre~heat zone, forming a thermally adjusted carrier gas comprises flowing the carrier gas into a space between an external surface of the first structure and an internal surface of the second structure, the external surface of the first structure or the internal surface of the second structure, or both, having one or more heating elements positioned thereon, forming a pre~heated carrier gas, the pre-heated carrier gas forced through a nozzle in a bottom panel of the first structure. In certain embodiments the carrier gas may be fed through one or more rubes that snake around in the space between the first and second structures, and heated by a heated air or other fluid transferring heat through the tube or tubes to the carrier gas.,

[0040] Certain methods of this disclosure include those wherein steps (b) and (c) occur continuously. [0041] Certain methods of this disclosure include those wherein the sublimed precursor chemical composition passes through a plurality of tortuous paths in the porous panel, the tortuous paths having an average pore size ranging from about 0.01 to about 10 microns (or from about 0.01 to about 8 microns, or from about 0.02 to about 7 microns, or from about 0.03 to about 5 microns.

[0042] Certain methods of this disclosure comprise sensing a level of the solid precursor chemical composition in one or more of the one or more cartridges using a method selected from the group consisting of gravity sensing, magnetic sensing, optical sensing, RF sensing, capacitance (contact or proximity) sensing.

[0043] Certain methods of this disclosure may compri se sensing a parameter selected from the group consisting of temperature of the pre-heated carrier gas, temperature of the deposition composition inside the first structure, pressure inside the first structure, displacement of the first structure in response to an oscillation input, solid precursor surface shape, and combinations thereof. Certain methods may comprise controlling one or more of the parameters using a control scheme selected from feet forward, feedback, cascade, or combination thereof. Certain methods may comprise using a laser-based device to sense the level and surface characterization.

[0044] Certain methods of this disclosure include those wherein the one or more internal walls may assist in maintaining the solid precursor chemical composition thermally homogeneous by conducting heat into the solid precursor chemical composition.

[0045] Certain methods of this disclosure include those wherein after step (d) but prior to step (e) the first intermediate composition flows vertically upward from the first uniform heating zone to the second uniform heating zone.

[0046] Certain methods of this disclosure include those wherein steps (b)-(e) are continuous and are carried out simultaneously. [0047] Certain methods of this disclosure may comprise adjusting concentration of the precursor chemical composition or derivative thereof in the deposition composition by sensing a parameter downstream of the sublimer and feeding back the sensed parameter to a first structure pressure controller, a carrier gas flow controller, or combination thereof,

[0048] Certain methods of this disclosure include those wherein the thermally adjusted carrier gas and the intermediate composition may flow horizontally in opposite directions.

[0049] Certain methods of this disclosure include those wherein the time and temperature sufficient to produce a deposition composition comprising sublimed precursor chemical composition (or derivative thereof) dispersed in the thermally adjusted carrier gas ranges from about 1 to about 10 minutes at a temperature up to about 400 °F (about 204 ^a C), or up to about 600 °F (about 316 °C).

[0050] Another aspect of the disclosure is a method comprising (or consisting of, or consisting essentially of):

(a) loading a volume of a free-flowing solid precursor chemical composition into an enclosed space defined by a first structure of a sublimer, the sublimer comprising the first structure, a second structure attached to the first structure, and a common wall between the first and second structures, a major portion of the common wall comprising a porous and thermally conductive solid material, the first and second structures each being essentially hollow three-dimensional rectilinear or curvilinear bodies, the second structure having a floor, at least one side wall, and at least one internal partition wall defining a carrier gas thermal adjustment flow channel and a thermally adjusted carrier gas flow channel, the porous and thermally conductive solid material of the common wall allowing vapor phase precursor chemical composition to pass after subliming:

(b) flowing a carrier gas through the carrier gas thermal adjustment flow channel, forming a thermally adjusted carrier gas; (c) flowing the thermally adjusted carrier gas through the thermally adjusted carrier gas flow channel tangentially past (but not through) the porous and thermally conductive solid material of the common wall for a time and temperature sufficient to produce a deposition composition comprising the vapor phase precursor chemical composition dispersed in the thermally adjusted carrier gas.

[0051] Certain methods of this disclosure include those wherein the flowing of the carrier gas through the carrier gas thermal adjustment flow channel may comprise:

(1) flowing the carrier gas to a carrier gas plenum at a first end of the second structure;

(2) routing the carrier gas from the carrier gas plenum to a first outer longitudinal channel and flowing the carrier gas longitudinally therethrough to form a first pre-heated carrier gas;

(3) directing the first pre-heated carrier gas from the first outer longitudinal channel to a first cross flow channel at a second end of the second structure and flowing the first pre-heated carrier gas therethrough to form a second pre-heated carrier gas; and

(4) routing the second pre-heated carrier gas from the cross flow channel into a second outer longitudinal channel and flowing the second pre-heated carrier gas longitudinally therethrough in a flow direction opposite a flow direction of the carrier gas in the first longitudinal channel, forming a third pre-heated carrier gas.

[0052] Certain methods of this disclosure include those wherein the flowing of the thermally adjusted carrier gas through the thermally adjusted carrier gas flow channel tangentially past (but not through) the porous thermally conductive solid material of the common wall comprises:

(5) routing the third pre-heated carrier gas into a first intermediate longitudinal channel and flowing the third pre-heated carrier gas longitudinally therethrough to form a first intermediate deposition composition; (6) directing the first intermediate deposition composition from the first intemiediate longitudinal channel to a second cross flow channel near the second end of the second structure and flowing the first intermediate deposition composition therethrough to form a second intermediate deposition composition;

(8) routing the second intermediate deposition composition from the second cross flow channel into a second intermediate longitudinal channel and flowing the second intermediate deposition composition longitudinally therethrough in a flow direction opposite a flow direction of the first intermediate deposition composition in the first intermediate longitudinal channel, forming a third intermediate deposition composition;

(9) routing the third intermediate deposition composition from the second intermediate longitudinal flow channel into a third cross-flow channel, forming a fourth intermediate deposition composition;

(10) routing the fourth intermediate deposition composition from the third cross-flow channel into a third intermediate longitudinal channel and flowing the fourth intermediate deposition composition longitudinally therethrough in a flow direction the opposite a flow direction of the second intermediate deposition composition in the second intermediate longitudinal channel, forming a fifth intermediate deposition composition;

(11) routing the fifth intermediate deposition composition from the third intermediate longitudinal flow channel into a fourth cross-flow channel, forming a sixth intermediate deposition composition; and

(12) routing the sixth intermediate deposition composition from the fourth cross-flow channel into a fourth intermediate longitudinal channel and flowing the sixth intermediate deposition composition longitudinally therethrough in a flow direction the opposite a flow direction of the fourth intermediate deposition composition in the third intermediate longitudinal channel, forming a final deposition composition;

wherein the concentration of the precursor chemical composition in the carrier gas increases with each step (5)-(12), inclusive. [0053] Another aspect of this disclosure is an apparatus comprising (or consisting essential of, or consisting of):

(a) a first (in certain embodiments, generally cubical) structure (in certain embodiments having a floor, a ceiling, and three sidewalls connecting the floor and ceiling) defining a uniform heating zone;

(b) a plurality of solid precursor chemical composition cartridges slidably engageable with internal surfaces of the first structure, the cartridges each having a porous bottom panel, at least one side panel connecting the bottom panel with a top panel, and one or more internal walls forming the two or more compartments, the porous bottom panel comprising a porous thermally conductive solid material through which vapor phase precursor chemical composition may pass after subliming, the cartridges extending generally horizontally and positioned in stacked relationship with sufficient space between the cartridges, and between a lowermost cartridge and the floor of the first generally cubical structure, and between an uppermost cartridge and the ceiling of the first generally cubical structure, such that a fluid may flow across (but not through) the porous thermally conductive solid material of each cartridge;

(c) a carrier gas pre-heat zone separated from the uniform heating zone by the first structure, and further separated from the uniform heating zone by a second structure external of the first structure;

(d) a carrier gas inlet fluidly connecting a source of carrier gas with the carrier gas pre-heat zone, the carrier gas inlet positioned near a top of the carrier gas pre-heat zone;

(e) a pre-heated carrier gas passage fluidly connecting the carrier gas pre-heat zone and the uniform heating zone, the pre-heated carrier gas passage positioned near a bottom of the uniform heating zone;

(f) a deposition composition passage fluidly connecting the uniform heating zone and a downstream unit; and (g) one or more carrier gas pre-heat zone heating elements attached to or integral with external surfaces of the first structure, attached to or integral with internal surfaces of the second structure. (In certain embodiments, additional heat zones may be present. The porous thermally conductive solid material may need to be slightly hotter than the sublimed, vapor phase precursor chemical composition to reduce or eliminate the vapor re-depositing in the tortuous paths of the porous thermally conductive solid material. This may be accomplished by providing one or more heating elements (for example Ni or Cu wire) in or near the porous thermally conductive solid material itself, or heat management by highly thermally conductive zones and other insulated zones, for example providing heating elements in the walls forming passages between cartridges. Other embodiments may include Joule-heated wires inside a support holding the porous thermally conductive solid material.)

[0054] Certain apparatus of this disclosure include those wherein the first structure may include a plurality of feet resting on a floor of the second structure.

[0055] Certain apparatus of this disclosure may include one or more sensors selected from the group consisting of temperature sensors, pressure sensors, level sensors, and weight sensors, wherein the level sensors are selected from the group consisting of gravity sensors, magnetic sensors, optical sensors, RF sensors, and capacitance (contact or proximity) sensors.

[0056] Certain apparatus of this disclosure include wherein the cartridge floors may comprise a layer of the porous thermally conductive solid material and a layer of an inert mesh material (Teflon-coated wire mesh or the like).

[0057] Certain apparatus of this disclosure may include apparatus wherein the interna! walls comprise 10 gauge nickel 200. [0058] Certain apparatus of this disclosure may include apparatus wherein the cartridges have length and width dimensions sufficient to form tight, sealing fits between the cartridges and the sidewalls of the first structure. Furthermore, in must be understood that cartridges and ovens may vary in shape and size. For example, the following embodiments are contemplated as being within this disclosure: one or more curved cartridges stacked into a cubical oven; one or more rectangular or cubical cartridges stacked into a cylindrical or spherical oven; one or more rectangular or cubical cartridges stacked into a rectangular or cubical oven; and one or more curved cartridges stacked into a cylindrical or spherical oven.

[0059] Certain apparatus of this disclosure may include wherein each cartridge includes at least one vertical flow channel near one end of each cartridge for passing carrier gas (or deposition composition) therethrough from beneath the porous bottom panel to above the top panel of each cartridge. In these embodiments, the carrier gas or deposition composition does not contact the solid precursor chemical composition while traversing through the vertical flow channels.

[0060] Certain apparatus of this disclosure may include those wherein each cartridge comprises tabs fitting in slots in the internal wall of the first structure.

[0061] Certain apparatus of this disclosure may further comprise a laser scanner for level detection and/or solid precursor chemical composition surface characterization.

[0062] Another aspect of this disclosure is an apparatus comprising (or consisting essential of, or consisting of):

(a) a first structure comprising a first generally hollow three-dimensional rectilinear or curvilinear body, the first structure configured to be at least partially loaded with a volume of a free-flowing solid precursor chemical composition into an enclosed space defined by the first structure; (b) a second structure comprising a second generally hollow three-dimensional rectilinear or curvilinear body attached to the first structure, the second structure having a floor, at least one side wall, and at least one internal partition wall defining a carrier gas thermal adjustment flow channel and a thermally adjusted carrier gas flow channel; and

(c) a common wall between the first and second structures, a major portion of the common wall comprising a porous and thermally conductive solid material, the porous and thermally conductive solid material of the common wall allowing vapor phase precursor chemical composition to pass through after subliming to form a deposition composition, while the common wall retains a balance of the solid precursor chemical composition in the first structure.

Certain non-limiting apparatus of this disclosure may further comprise:

(1) the first structure comprises a generally hollow three-dimensional rectilinear body comprising a first sheet of 10 gauge nickel 200 bent to form three longitudinal sidewalls, a distal end wall, and at least one face of a pyramidal feed end, with a triangular section of 10 gauge nickel 200 sheet completing a pyramidal feed end, the pyramidal feed end welded to a boss adapted to connect to a fitting through which the solid precursor chemical composition may be loaded, the three longitudinal sidewalls, the end wall, and the pyramidal feed end welded together at seems therebetween;

(2) the second structure comprises a generally hollow three-dimensional rectilinear body comprising a second sheet of 10 gauge nickel 200 bent to form two longitudinal sidewalls, a distal end wall, a carrier gas feed end wall, and a first half of a flange connection, the feed end wall including a first through passage for feeding the carrier gas into the second structure, and a second through passage for exiting the deposition composition;

(3) the common wall defined by a metal plate comprising a bay having a periphery slightly smaller than a periphery of the metal plate, and a slot into which a plate of the porous thermally conductive solid material is positioned, the metal plate having a length and width forming a second half of the flange connection; (4) the first and second halves of the flange connection secured using a plurality of pairs of nuts and bolts, with a gasket seal between the first and second halves of the flange connection.

[0064] Certain methods of this disclosure may combine the methods of the first and second aspects. For example, certain systems of this disclosure may combine the "oven" and "canister" apparatus into a system where the oven and canister are arranged in parallel or sequential flow relationship. For example, certain methods may comprise:

(d) stopping the flows in steps (h) and (c) of the method of the first aspect;

(e) initiating flow of carrier gas through a previously loaded volume of a free-flowing solid precursor chemical composition loaded into an enclosed space defined by a first structure of a sublimer, the sublimer comprising the first structure, a second structure attached to the first structure, and a common wall between the first and second structures, a major portion of the common wall comprising a porous thermally conductive solid material, the first and second structures each being essentially hollow three-dimensional rectilinear or curvilinear bodies, the second structure having a floor, at least one side wall, and at least one internal partition wall defining a carrier gas thermal adjustment flow channel and a thermally adjusted carrier gas flow channel, the porous thermally conductive solid material of the common wall allowing vapor phase precursor chemical composition to pass after a portion of the solid precursor chemical composition sublimes;

(f) flowing a carrier gas through the carrier gas thermal adjustment flow channel, forming a thermally adjusted carrier gas; and

(g) flowing the thermally adjusted carrier gas through the thermally adjusted carrier gas flow channel tangentially past the porous thermally conductive solid material of the common wall for a time and temperature sufficient to produce a deposition composition comprising the vapor phase precursor chemical composition dispersed in the thermally adjusted carrier gas. [0065] Alternatively, flow may be initiated through the canister of the second method, while flow is still maintained through the oven, followed by stopping flow through the oven. When used sequentially, the first apparatus may produce an initial concentration of vapor phase precursor in the carrier gas, and the second apparatus used to increase the concentration of vapor phase precursor in the carrier gas; or the second sublimer may be used to introduce a second precursor (which may or may not be sublimed solid) into an intermediate composition produced by the first apparatus.

[0066] Various terms are used throughout this disclosure. A "plenum" is a space in which a gas, usually carrier gas, is contained at a pressure greater than or less than atmospheric pressure. "Cartridge" means a structure that contains (or may be configured to contain) solid precursor chemical composition, having a floor, a ceiling, one or more sidewalls connecting the floor and ceiling, and one or more internal walls segregating the internal space. The internal walls may or may not extend the entire length between floor and ceiling. A "canister" means a structure that contains (or may be configured to contain) a free-flowing solid precursor chemical composition. As used herein the phrase "solid precursor chemical composition" means substantially solid compounds or mixtures comprised primarily of chemicals that are solid at standard temperature and pressure (0 °C and 1 atmosphere, 101 kPa), as well as at normal room temperature (about 25 °C), and which sublime upon heating to form gaseous precursors, or derivatives thereof. By "derivatives thereof we mean, for example, that one molecule of W2CI10 (solid) may sublime to form 2WCls (gas). A "free- flowing solid precursor chemical composition" is a solid precursor chemical composition that can be poured or otherwise flowed as a granular composition into a canister. "Sublimer" is simply an apparatus or system (for example, if carrier gas sources are included) that is used to sublime a solid precursor chemical composition to form a gaseous or vapor phase precursor. As used herein the phrase "a first structure and a second structure external of the first structure", when describing the physical relationship of first and second structures, means the second structure surrounds and encloses the first structure. A structure that is simply next to, or adjacent a first structure, is not considered external of the first structure as used herein. A "porous bottom panel" is a porous solid material, and includes both panels whose entire structure is suitably porous and thermally conductive, and panels having regions of porosity and thermal conductivity able to pass a sublimed solid precursor chemical composition, wherein the sublimed precursor chemical composition passes through a plurality of tortuous paths in the panel, the tortuous paths having an average pore size ranging from about 0.01 to about 10 microns (or from about 0,01 to about 8 microns, or from about 0.02 to about 7 microns, or from about 0.03 to about 5 microns. An important consideration is that the porous thermally conductive solid material needs to have a thermal conductivity sufficient to minimize temperature variation (hot/cold spots), for example less than +/- 2 °C, or less than +/- 1 °C, or less than 0.5 °C, and promote uniformity of sublimation - in other words, that the solid precursor sublimes uniformly at all locations where it contacts the porous thermally conductive solid material. "Porous and thermally conductive solid material" includes natural and synthetic materials, and includes metallic, ceramic, and polymeric materials. Examples include sintered metal particles or sintered metal fibers, and combinations of metal mesh and sintered metal porous solid with improved thermal conductivity. The porous and thermally conductive solid material may have thickness ranging from about 0.01 mm to 10 mm, or from about 0.1 mm to 4 mm. "Thermally conductive" means having an intrinsic or bulk material thermal conductivity of at least 1 W/m-K (@ 20 °C), or at least 5 W/m-K (@ 20 °C), or at least 10 W/m-K (@ 20 °C), or at least about 20 W/m-K(@ 20 °C). The thermal conductivity of porous materials are typically from about 10 to about 60 percent of their intrinsic or bulk material values. The intrinsic or bulk material thermal conductivity of 316L stainless steel (SS) is reported to be 16.3 W/m-K @ 20C. Typical sintered SS 316L particle porous materials we tested (grades D, E, F, H, P09, and P05) have thermal conductivities ranging from about 2 to about 8 W/m-K, and have reported pressure drop in gaseous service (air) ranging from about 0.2 to about 20 mbar-m ² /m ³ /min. Suitable porous SS materials are available under the trade designation PSS® MEDIUM from Pall Corporation, Port Washington, New York (USA), including Pall PSS 316L stainless steel medium, which is produced by a Pall proprietary sintering process using no binders or other extraneous substances. Another suitable material may be the SS T316 material known under the trade designation 2 MICRON 3 Layer SINTERED STAINLESS STEEL MESH, available from TWP Inc., Berkeley, California (USA). [0067] A "substrate" is a 2- or 3 -dimensional body (including particles), or one or more surfaces of a 2- or 3 -dimensional body, and includes, but is not limited to insulators, semiconductors, electronic devices, circuits circuit boards, wafers (for example a silicon wafer), or a previously formed film or layer, such as, for example, a metallization or interconnect layer.

[0068] "Film" and "layer" may be used interchangeably, although a film is generally considered to be thinner than a layer. Both films and layers may be deposited on substrates using apparatus, systems, and methods of the present disclosure. The films and layers may be low~k dielectric (such as disclosed in numerous U.S. Patents, such as U.S. Patent No. 8,993,444), high~k dielectric (such as disclosed in numerous U.S. Patents, such as U.S. Patent No. 9,029,959, including, but not limited to, ZrCh, ΗΪΟ2, other dielectric metal oxides, alloys thereof, and their silicate alloys), insulating (for example, but not limited to Si0 ₂ , SiN, and the like), piezoelectric, conducting, non-conducting, semiconducting, porous, mesoporous (such as described in U.S. Patent No, 9,562,005), or non-porous, where "porous" includes mesoporous porosities and porosities above mesoporous, "non-porous" means porosity less than mesoporous, and "mesoporous" refers to porous materials having an average pore size in the range from about 2 to about 50 nanometers (nm), "K." or "k" refers to dielectric constant.

[0069] All numbers, including degree angles, disclosed herein are approximate values, regardless whether the word "about" or "approximate" is used in connection therewith. They may vary by 1%, 2%, 5%, and sometimes, 10 to 20%. Whenever a numerical range with a lower limit, RL and an upper limit, RU, is disclosed, any number falling within the range is specifically disclosed. In particular, the following numbers within the range are specifically disclosed: R = RL + y*(RU— RL), wherein y is a variable ranging from 1% to 100% with a 1% increment, i.e., y is 1%, 2%, 3%, 4%, 5%, . . . , 50%, 51%, 52%, . . . , 95%, 96%, 97%, 98%, 99%, or 100%. Moreover, any numerical range defined by two R numbers as defined in the above is also specifically disclosed. [0070] The sources of carrier gas may be one or more conduits, pipelines, storage facilities, or cylinders. Carrier gases may be supplied from a pipeline, cylinder, storage facility, cryogenic separation unit, membrane permeation separator, or adsorption unit such as a vacuum swing adsorption unit. Suitable carrier gases depend on the ultimate use of the "deposition composition" for film or layer growth, photolithography, epitaxial growth, etching, and metallization, to name a few. Examples of suitable carrier gases include, but are not limited to, nitrogen, argon, xenon, krypton, clean dry air, silane, hydrogen, ammonia, nitrogen trifluoride, hydrogen bromide, and mixtures thereof

[0071] Referring now to the drawings, where the same numerals and letters are used throughout unless otherwise noted, FIG. 1 is a schematic process flow diagram of one method, system, and apparatus embodiment (100) in accordance with the present disclosure. It will be realized that the diagram is highly schematic and is intended to be used in further understanding the more detailed drawings to follow. Carrier gas is caused to flow from one or more cylinders 10, 12 or from a pipeline, conduit or other source through a main carrier gas supply conduit 22, through an optional filter 14, and then into an oven-type sublimer defined by a first structure 16 external of a second structure 18, as illustrated schematically by the arrows. A second or alternate sublimer canister including a first structure 20 having solid precursor chemical composition 42 therein and second structure 46 may be fed carrier gas through an alternate carrier gas supply conduit 22A, as will presently be explained. After passing through either the oven sublimer, carrier gas enriched in sublimed precursor chemical composition is routed through a conduit 23 to a process unit or other end use, or to storage. Similarly, carrier gas enriched in precursor chemical composition may be routed through conduit 23 A a the process unit, other end use, or storage. Valves VI -VI 3 are provided for controlling various flows and/or isolating portions of the system. Additional valves, not illustrated, may be provided, such as pressure relief valves.

[0072] In the oven-type sublimer, carrier gas enters through a carrier gas inlet 48 into an upper space or region 32 between first structure 16 and second structure 18, where the carrier gas flows about and around second structure 18 and is subject to thermal adjustment, typically, although not necessarily, heating, eventually reaching a through passage 34 for the thermally adjusted carrier gas. Second structure 18 may have feet 28, 30 or other supports to assist creating the space for carrier gas to flow. Where the carrier gas is heated, the region or space between first structure 16 and second structure 18 may be refer to as a pre-heat zone. Second structure 18 supports a first or lower cartridge 24 and a second or upper cartridge 26, the cartridges containing solid precursor chemical composition. As the thermally adjusted carrier gas passes through passage 34 it enters a first portion 36 of a uniform heating zone, flowing tangentially and to the left across a porous solid material 44 making up a bottom of lower cartridge 24. As the carrier gas moves leftwards it becomes more concentrated in precursor material that has sublimed through porous solid material 44, eventually reaching a vertical passageway in cartridge 24 (between porous solid material 44 and lower cartridge top panel 45) allowing a first intermediate deposition composition to flow vertically upward and enter into a second portion 38 of the uniform heating zone, flowing now rightwards tangentially across porous solid material 44 of upper cartridge 26. Near the right side end of upper cartridge 26, the enriched carrier gas (or second intermediate composition) flow again vertically upward trough a passageway in upper cartridge 26 (between porous solid material 44 and upper cartridge top panel 45), allowing the second intermediate deposition composition to reach a deposition composition outlet tube or fitting 40, fluidly connected to conduit 23 leading to the process unit, other end use, or storage.

[0073] In the canister-type sublimer, carrier gas is routed through conduit 22A to second structure 46, where the carrier gas is pre-heated and flows across a porous solid material common wall 44, while the solid precursor chemical composition sublimes therethrough, forming a deposition composition that is routed through conduit 23 A to the process unit, other end use, or storage.

[0074] FIGS. 2, 3, and 4 are schematic front elevation views, partially in cross-section, of three sublimer oven embodiments 200, 300, and 400 in accordance with the present disclosure. Embodiments 200 and 300 both illustrate carrier gas passageways 52 and 54, essentially tubes or conduits, allowing carrier gas enriched in precursor chemical to traverse through cartridges 24, 26, respectively, as well as heat conductive vertical walls 50 secured (welded or other wise) to porous solid material 44 in each cartridge 24, 26. Although illustrated as vertical, walls 50 need not be vertical, and in fact may be at some other angle than 90 degrees in relation to solid porous material 44, or may include horizontal fins. Solid precursor chemical composition is illustrated 60 in embodiments 200, 300, while cartridges are not illustrated in embodiment 400 in order to illustrate other features. One difference between embodiments 200 and 300 is the placement of heating elements. In embodiment 200, one or more heating elements 62 are positioned secured on internal surfaces of first structure 16, and a second set of one or more heating elements 64 are secured on external surfaces of second structure 18. In embodiment 300 (FIG. 3), one or more heating elements 66 are positioned in the vertical portions of carrier gas passageway 67 between first and second structures 16, 18. Another difference is the placement of through passage conduit 34 for preheated carrier gas. In embodiment 200, conduit 34 is essentially vertical, while in embodiment 300 conduit 34 is positioned more to the right, allowing more contact between the carrier gas and porous solid material 44 of cartridge 24. Yet another difference is the presence of one or more temperature, pressure, and/or level sensors 68 in embodiment 300 passing through structures 16, 18. In embodiment 200, one or more such sensors (not illustrated for clarity) may be positioned through carrier gas inlet 48. Embodiment 300 also may optionally include an oscillator 160 and a displacement sensor 162, allowing weight determination of the sublimer, as an indication of consumption or presence of solid precursor chemical composition in cartridges 24, 26.

[0075] Embodiment 400, illustrated schematically in FIG. 4, includes a door 70 hingedly attached to first structure 16 using a pair of hinges 72. Door 70 includes a window 74. Second (internal) structure 18 includes a ceiling 76, opposing sidewalls 78, 80, a back sidewall 79, and a floor 82. First (external) structure 16 includes a floor 84, ceiling 86, opposing sidewalls 88, 90, and a back sidewall (not viewable in FIG. 4). Also illustrated are mounting brackets 92 for cartridges 24, 26 (not illustrated in FIG. 4), and which may also serve to secure sidewalls 88, 90 to back sidewall 79. Similar brackets are illustrated securing ceiling 76 and floor 82 to opposing sidewalls 78, 80 and back sidewall 79. [0076] FIG. 5 is a perspective view, partially in phantom, of one cartridge embodiment 500 that may be used in the oven-type sublimers illustrated schematically in FIGS. 2, 3, and 4. FIG. 6 is a schematic cross-sectional view along cross-section "A-A" of the cartridge illustrated schematically in FIG. 5, and FIG. 7 is a schematic cross-sectional view of a portion of another sublimer embodiment 600 illustrating how several of the cartridges illustrated in FIGS. 5 and 6 may be inserted into the sublimer illustrated in FIG. 7. Referring first to FIG. 7, embodiment 600 as illustrated includes only second (internal) structure 18 for clarity in order to illustrate certain features, including a lowermost cartridge 102, a next higher cartridge 104, a second next highest cartridge 106, and an uppermost cartridge 108. One cartridge embodiment 500 is illustrated in more detailed cross-sectional view of FIG. 6. Arrows 1 10 in each cartridge 102, 104, 106, and 108 reflect the settling movement of solid precursor chemical composition 60 in each cartridge as the precursor sublimes through porous solid material 44. As illustrated schematically in FIG. 7, lowermost cartridge 102 includes sidewalls 1 11 , 1 12, and top panel 45; next higher cartridge 104 includes sidewa!ls 1 13, 114, and top panel 45; second next highest cartridge 106 includes sidewalls 1 15, 1 16, and top panel 45; and uppermost cartridge 108 includes sidewalls 1 17, 1 18, and top panel 45. An important feature of embodiment 600 is provision of inserts or rails 120, 122, which fit into respective female receptors or slots 138, 140 in second structure 18, as illustrated schematically in FIG. 7, providing a tight fit of sidewalls of each cartridge 102, 104, 106, 108 into second structure 18. As illustrated schematically in FIG. 5, cartridge embodiment 500 includes an internal wall 124 near the left-hand side of cartridge 102, internal wall 124 in turn forming, with top panel 45, a gap 132 between internal wall 124 and sidewall 1 12. Sidewall may be attached to internal wall 124 at one or more locations by screws, nuts, and spacers, not illustrated. This configuration eliminates the need for carrier gas tubes or passageways 52, 54 as provided in embodiments 200, 300 (FIGS. 2 and 3). Angle "a" is indicated in FIG, 5 as illustrating that the carrier gas flow exiting gap 132 may not travel in exact opposite direction as that flowing beneath the cartridge. Angle a may be at least 90 degrees (or at least 100, or 110 or 120 or, 130, or, 140, or 150, or 160, or 170, or 180 degrees). [0077] FIGS. 8, 9, and 10 are schematic cross-sectional views of three other cartridge embodiments 700, 800, and 900 in accordance with the present disclosure. Embodiment 700 (FIG. 8) includes a level sensor (transmitter 140, receiver 142) arranged vertically and positioned to sense level of solid precursor chemical composition in the cartridge. Embodiment 800 (FIG. 9) includes a level sensor 150 positioned in a sidewall of second structure 18, and designed to sense level horizontally, with dashed arrows 152, 154, and 156 indicating "full", "half-full", and "0" for level of solid precursor chemical composition. Cartridge embodiment 900 illustrated schematically in FIG. 10 illustrates solid porous material 44, such as sintered nickel or other sintered metal or ceramic or porous polymeric material supported by a mesh 47 of coated wires 49 (see FIG. 11 plan view of coated-wire mesh). Coated wires may be polytetrafluoro ethylene-coated steel or other metal wire. The metal wire may be heated by running an electric current therethrough. Embodiments 700, 800, and 900, as illustrated schematically, omit carrier gas passageways for clarity, but each embodiment would include either a carrier gas passageway 52 (or 54), or the construction illustrated schematically in FIG. 5. Solid precursor chemical composition 60 sublimes through sintered nickel or other solid porous material 44 and then through mesh 47 into carrier gas, as explained herein.

[0078] FIG. 12 is a schematic perspective view, and FIG. 13 is a schematic cross-sectional view, of another sublimer embodiment 1000 in accordance with present disclosure. In this configuration the sublimer may be referred to as a canister-type sublimer. Embodiment 1000 includes first and second generally hollow three-dimensional rectilinear bodies 202, 204 and a common wall 206 therebetween. Extending around a lower periphery of common wall 206 is a first half-flange 208, mating substantially with a second half-flange 210 extending from and around an upper periphery of body 204. The structure is held together by a plurality of bolts 212 secured with nuts 214. In embodiment 1000, first generally hollow three-dimensional rectilinear body 202 is welded, brazed, or otherwise secured to common wall 206, and comprises a single sheet of 10 gauge nickel 200 bent to form the three-dimensional rectilinear shape, in this case a rectangular parallelepiped (cuboid, a parallelepiped in which all faces are rectangles). The sheet is bent to form a top 216, opposing sidewalls 218, 220, a distal end wall 224, and three sides of a four-sided feed end pyramid 226. The fourth side of pyramid is a separate piece 228. Where edges of the rectangles of the single sheet of nickel meet the edges are welded or brazed together, as is triangular side 228 of pyramid 226. A solid precursor feed valve or port. 230, illustrated with a quick-connect/quick-disconnect fitting (QC/QD) is provided, and this is secured with a short conduit 231 to a boss 232, which is in turn welded or brazed to pyramid 226 and separate triangular piece 228 as illustrated schematically in FIG. 12. Carrier gas is introduced into second structure 204 via a valve 234 provided with a QC/QD coupling, short conduit 235, boss 237, while deposition composition exits the structure through similar arrangement of valve 236 with QC/QD fitting, short conduit 239, and boss 241. FIG. 13 illustrates schematically a sheet of porous solid material 238 installed in a slot 242 in common wall 206, and a bay 240 in common wall 206 for allowing solid precursor chemical composition to come into direct contact with one side of the porous solid material 238. The opposing side of the solid porous material 238 is exposed to carrier gas flowing through second generally hollow three-dimensional rectilinear structure 204, as will presently be explained in reference to FIGS. 16 and 17. Sintered metal (nickel) or other metal or porous ceramic material plates 244 are provided, arranged as illustrated schematically in FIG. 17. Nickel sheet metal 246 provides sidewalls and bottom of second structure 204. A gasket 248 provides an extra seal between half-flanges 208, 210.

[0079] FIG. 14 is a schematic perspective view of another sublirner embodiment 1100 in accordance with the present disclosure, with FIG. 15 being a second perspective view with valves removed, and FIG, 16 being a third perspective view, partially in phantom. FIG. 17 is a schematic plan view, with the first structure and common wall removed, of the second structure of the sublirner embodiment 1100 illustrated schematically in FIGS, 14 and 15. Embodiment 1100 is similar to embodiment 1000 but differs in being welded (or brazed) construction rather than bolted. Furthermore, no gasket is required in embodiment 1100. First generally hollow three-dimensional rectilinear structure 204 is the same in both embodiments, however, second generally hollow three-dimensional rectilinear structure 250 has no half- flange feature, nor does common wall 252. FIG. 15 illustrates a threaded inlet for solid precursor filling and emptying, if necessary, a carrier gas threaded inlet hole 256, and a threaded deposition composition exit hole 258, each of these accommodating a male threaded piece on respective bosses 232, 237, 241 (FIG. 12). FIGS. 16 and 17 illustrate schematically sintered metal (sintered nickel preferably) walls 244, as well as end walls 243, 245, 247, all arranged to allow carrier gas to flow as illustrated schematically by the solid arrows in FIG. 17. A short conduit 260 is provided, through which deposition composition exits the sublimer. Carrier gas is first preheated in outermost chambers, then allowed to traverse next innermost chambers and then the innermost chambers to contact common wall of solid porous material 252 (FIG. 15). Solid precursor material sublimes through solid porous material of common wall 252, producing the deposition composition, which exits conduit 260 and valve 236.

[0080] FIGS. 18 and 19 are logic diagrams of two method embodiments 1200 and 1300 in accordance with the present disclosure. Method embodiment 1200 comprises, consists essentially of, or consists of (Box 302) placing one or more cartridges, each having two or more compartments supporting a solid precursor chemical composition, into a sublimer, the sublimer comprising a first structure and a second structure external of the first structure, the first structure defining a uniform heating zone, the one or more cartridges each having a porous bottom panel, four side panels, a top panel, and one or more internal walls forming the two or more compartments, the porous bottom panel comprising a porous solid material through which the solid precursor chemical composition may pass after subliming (Box 304). Method embodiment 1200 further includes flowing a carrier gas through a pre-heat zone, forming a thermally adjusted carrier gas (Box 306), and flowing the thermally adjusted carrier gas through the uniform heating zone tangentially under the porous bottom panel of the one or more cartridges for a time and temperature sufficient to produce a deposition composition comprising sublimed precursor chemical composition, or derivative thereof, dispersed in the thermally adjusted carrier gas (Box 308).

[0081] Method embodiment 1300 comprises, consists essentially of, or consists of (Box 402) loading a volume of a free-flowing solid precursor chemical composition into an enclosed space defined by a first structure of a sublimer, the sublimer comprising the first structure, a second structure attached to the first structure, and a common wall between the first and second structures, a major portion of the common wall comprising a porous solid material, the first and second structures each being essentially hollow three-dimensional rectilinear bodies, the second structure having a floor, four side walls, and at least one internal partition wall defining a carrier gas thermal adjustment flow channel and a thermally adjusted carrier gas flow channel, the porous solid material of the common wall allowing the solid precursor chemical composition to pass after subliming (Box 404). Method embodiment 1300 further comprises flowing a carrier gas through the carrier gas thermal adjustment flow channel, forming a thermally adjusted carrier gas (Box 406) and flowing the thermally adjusted carrier gas through the thermally adjusted carrier gas flow channel tangentially past the porous solid material of the common wall for a time and temperature sufficient to produce a deposition composition comprising sublimed precursor chemical composition dispersed in the thermally adjusted carrier gas (Box 408).

[0082] FIGS. 20 and 21 are schematic prospective views illustrating two other sublimer embodiments 1400 and 1500 in accordance with the present disclosure. Embodiment 1400 illustrated schematically in FIG. 20 is a curvilinear variation of embodiments 1000 and 1100 illustrated schematically in FIGS. 12-17, and features first and second generally cylindrical bodies 502 and 504. A porous, thermally conductive common wall (not illustrated for clarity) would separate bodies 502, 504. A carrier gas feed tube 508 is held by upper and lower bosses 510, 520 into a Ni sheet metal top end or lid 516, and a Ni sheet metal plate 518, respectively. A deposition composition tube 512 is similarly secured using bosses 514, 522. A solid precursor chemical composition inlet QC/QD fitting 530 is provided, secured to lid 516 via a short conduit 528 and boss 532. A carrier gas QC/QD fitting 534 is provided, as is a deposition composition QC/QD fitting 536. Upper generally cylindrical body 502 comprises, in this embodiment, lid 516 friction- fitted or compression-fitted at seal 542 to a transparent cylinder 540, formed of polycarbonate plastic or glass. This is in turn friction-fitted or compression-fitted at 548 to second generally cylindrical body 504, which comprises in this embodiment a Ni sheet metal shell 546 and sintered Ni cylindrical walls 544 through which carrier gas passes, Ni sheet metal shell may include heating elements (or common wall may be heated as explained herein with respect to FIGS. 10-11, for example), or the carrier gas may be preheated prior to entering the device, or both. As the solid precursor chemical composition sublimes through the solid, thermally conductive common wall (not illustrated), it mixes with the carrier gas flowing through cylindrical channels formed by sintered metal cylindrical walls 544.

[0083] Embodiment 1500 illustrated schematically in FIG. 21 is a variation of embodiments 200 and 300, illustrated schematically in FIGS. 2 and 3, respectively. Embodiment 1500 features a coiled tube 168 for feeding carrier gas into the sublimer, having a vertical portion 169 and a horizontal portion 170. Coiled tube 168 is positioned with a plenum 167 between first and second structures 16, 18. Plenum 167 may be at a pressure less than, greater than, or at atmospheric pressure. Heating elements 166 are positioned inside plenum 167, and may be secured to inside surfaces of first structure 16. Other heating elements 66 may be positioned in plenum 167, as desired. Coiled tube 168 may allow for greater heat transfer area and longer residence time for the carrier gas to be heated in certain embodiments.

[0084] More exotic metals or sintered metals may be used for all or portions of the internal walls 244, and end walls 243, 245, 247, if desired, such as precious metals and/or noble metals (or alloys). Noble metals and/or other exotic corrosion and/or fatigue-resistant materials include metals such as platinum (Pt), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), osmium (Os), iridium (Ir), and gold (Au); alloys of two or more noble metals; and alloys of one or more noble metals with a base metal may be employed. In certain embodiments a protective layer or layers or components may comprise an alloy attached to a base metal using brazing, welding or soldering of certain regions.

[0085] During operation of apparatus and systems of the present disclosure, carrier gas flow passageways and plenums may include one or more carrier gas flow diverters (baffles and the like) for effecting direct heat exchange from heating elements to carrier gas, or from overheated carrier gas to a cooling element. Carrier gas flow diverters may for example comprise one or more baffles, distributor plates, grids, and the like for causing a tortuous flow path. Carrier gas flow diverters may take any shape, for example flat plates, corrugated plates, plates having a variety of projections or protuberances therefrom such as spikes, knobs, lumps, bumps, and the like, of a variety of sizes, or all the same size. Flow of carrier gas streams is preferably continuous, or at least semi-continuous, while solid precursor chemical composition is being sublimed. Carrier gas flows may be continued while there is no solid precursor chemical composition being sublimed, but may also be reduced or stopped. One or more mass flow controllers may be employed in each carrier gas supply conduit to a sublimer. Mass flow controllers may be, and preferably are attached directly to the sublimer, or may be remote from the sublimer.

[0086] Apparatus, systems, and methods of the present disclosure may include one or more thermocouples for temperature monitoring and control, pressure sensors, and/or level sensors for monitoring and/or control of temperature of the subliming operation, for example using a controller. In certain apparatus, systems, and methods control of carrier gas flow and heating or cooling may be adjustable with respect to flow of the carrier gas, electric current, or both. Adjustment may be via automatic, semi-automatic, or manual control. A signal may be transmitted by wire or wirelessly from a thermocouple, pressure sensor, level sensor, or other sensor to a controller, which may control the apparatus, systems, and methods by adjusting any number of parameters, for example carrier gas flow rate may be adjusted through use of a signal to one or more carrier gas mass flow controllers, it being understood that suitable transmitters and actuators, such as mass flow controllers, control valves and the like, are not illustrated for clarity.

[0087] A pressure control, precursor concentration in carrier gas, and/or Joule heating process control scheme may be employed. A master controller may be employed, but the disclosure is not so limited, as any combination of controllers could be used. The controller may be selected from PI controllers, PID controllers (including any known or reasonably foreseeable variations of these), and may compute a residual equal to a difference between a measured value and a set point to produce an output to one or more control elements. The controller may compute the residual continuously or non-continuously. Other possible implementations of the disclosure are those wherein the controller comprises more specialized control strategies, such as strategies selected from feed forward, cascade control, internal feedback loops, model predictive control, neural networks, and Kalman filtering techniques.

[0088] The term "control", used as a transitive verb, means to verify or regulate by comparing with a standard or desired value. Control may be closed loop, feedback, feed-forward, cascade, model predictive, adaptive, heuristic and combinations thereof. The term "controller" means a device at least capable of accepting input from sensors and meters in real time or near-real time, and sending commands directly to control elements, and/or to local devices associated with control elements able to accept commands. A controller may also be capable of accepting input from human operators; accessing databases, such as relational databases; sending data to and accessing data in databases, data warehouses or data marts; and sending information to and accepting input from a display device readable by a human. A controller may also interface with or have integrated therewith one or more software application modules, and may supervise interaction between databases and one or more software application modules.

[0089] The phrase "PID controller" means a controller using proportional, integral, and derivative features. In some cases the derivative mode may not be used or its influence reduced significantly so that the controller may be deemed a PI controller. It will also be recognized by those of skill in the control art that there are existing variations of PI and PID controllers, depending on how the discretization is performed. These known and foreseeable variations of PI, PID and other controllers are considered within the discl osure.

[0090] The controller may utilize Model Predictive Control (MFC). MFC is an advanced multivariable control method for use in multiple input/multiple output (MIMO) systems. MPC computes a sequence of manipulated variable adjustments in order to optimise the future behavior of the process in question. It may be difficult to explicitly state stability of an MPC control scheme, and in certain embodiments of the present disclosure it may be necessary to use nonlinear MPC. In so-called advanced control of various systems, PID control may be used on strong mono-variable loops with few or nonproblematic interactions, while one or more networks of MFC might be used, or other multivariable control structures, for strong interconnected loops. Furthermore, computing time considerations may be a limiting factor. Some embodiments may employ nonlinear MPC.

[0091 ] A feed forward algorithm, if used, will in the most general sense be task specific, meaning that it will be specially designed to the task it is designed to solve. This specific design might be difficult to design, but a lot is gained by using a more general algorithm, such as a first or second order filter with a given gain and time constants.

[0092] The choice of a particular material for any component is dictated among other parameters by the chemistry, pressure, and temperature of carrier gas and solid precursor chemical composition used, and type of product to be produced downstream of the sublimer. The skilled artisan, having knowledge of the particular application, pressures, temperatures, and available materials, will be able design the most cost effective, safe, and operable structures, plenums, chambers, conduits, cartridges and sublimers for each particular application without undue experimentation.

[0093] Embodiments disclosed herein include:

[0094] A: A method comprising (consisting essential of, or consisting of):

(a) placing one or more cartridges, each having two or more compartments supporting a solid precursor chemical composition, into a sublimer, the sublimer comprising a first structure and a second structure external of the first structure, the first structure defining a uniform heating zone, the one or more cartridges each having a porous bottom panel, at least one, side panel, a top panel, and one or more internal walls forming the two or more compartments, the porous bottom panel comprising a porous thermally conductive solid material through which vapor phase precursor chemical composition may pass after subliming, while the side panels and top panel are non-porous to the vapor phase precursor chemical composition; (b) flowing a carrier gas through a pre-heat zone, forming a thermally adjusted carrier gas;

(c) flowing the thermally adjusted carrier gas through the uniform heating zone tangentially past (but not through) the porous bottom panel of the one or more cartridges for a time and temperature sufficient to produce a deposition composition comprising vapor phase precursor chemical composition (or derivative thereof) dispersed in the thermally adjusted carrier gas.

[0095] B: A method comprising (or consisting essential of, or consisting of):

(a) loading a volume of a free-flowing solid precursor chemical composition into an enclosed space defined by a first structure of a sublimer, the sublimer comprising the first structure, a second structure attached to the first structure, and a common wall between the first and second structures, a major portion of the common wall comprising a porous thermally conductive solid material, the first and second structures each being essentially hollow three-dimensional rectilinear or curvilinear bodies, the second structure having a floor, at least one side wall, and at least one internal partition wall defining a carrier gas thermal adjustment flow channel and a thermally adjusted carrier gas flow channel, the porous and thermally conductive solid material of the common wall allowing vapor phase precursor chemical composition to pass after subliming;

(b) flowing a carrier gas through the carrier gas thermal adjustment flow channel, forming a thermally adjusted carrier gas;

(c) flowing the thermally adjusted carrier gas through the thermally adjusted carrier gas flow channel tangentially past (but not through) the porous solid material of the common wall for a time and temperature sufficient to produce a deposition composition comprising vapor phase precursor chemical composition dispersed in the thermally adjusted carrier gas,

[0096] C: An apparatus comprising (or consisting essential of, or consisting of):

(a) a first structure defining a uniform heating zone; (b) one or more solid precursor chemical composition cartridges slidably engageable with internal surfaces of the first structure, the cartridges each having a porous bottom panel, at least one side panel, a top panel, and one or more internal walls forming two or more compartments, the porous bottom panel comprising a porous and thermally conductive solid material through which a vapor phase precursor chemical composition may pass after subliming, the cartridges extending generally horizontally and positioned in stacked relationship with sufficient space between the cartridges, and between a lowermost cartridge and the floor of the first generally cubical structure, and between an uppermost cartridge and the ceiling of the first generally cubical structure, such that a fluid may flow across the porous bottom panel of each cartridge, while the side panels and top panel are non-porous to the vapor phase precursor chemical composition;

(c) a carrier gas pre-heat zone (in certain embodiments separated from the uniform heating zone by the floor, the ceiling, and the three sidewalls of a first generally cubical structure, and further separated from the uniform heating zone by a door, the door hingedly attached to a second generally cubical structure external of the first generally cubical structure, the second generally cubical structure having a floor, a ceiling, and three sidewalls connecting the floor and ceiling, the door extending from opposing sidewalls of the second generally cubical structure and from the floor to the ceiling of the second generally cubical structure);

(d) a carrier gas inlet fluidly connecting a source of carrier gas with the carrier gas pre-heat zone, the carrier gas inlet positioned near a top of the carrier gas pre-heat zone;

(e) a pre-heated carrier gas passage fluidly connecting the carrier gas pre-heat zone and the uniform heating zone, the pre-heated carrier gas passage positioned near a bottom of the uniform heating zone;

(f) a deposition composition passage fluidly connecting the uniform heating zone and a downstream unit; and (g) one or more carrier gas pre-heat zone heating elements attached to or integral with external surfaces of the first structure, and/or attached to or integral with internal surfaces of the second structure.

[0097] D: An apparatus comprising (or consisting essential of, or consisting of):

(a) a first structure comprising a first generally hollow three-dimensional rectilinear or curvilinear body, the first structure configured to be at least partially loaded with a volume of a free-flowing solid precursor chemical composition into an enclosed space defined by the first structure;

(b) a second structure comprising a second generally hollow three-dimensional rectilinear or curvilinear body attached to the first structure, the second structure having a floor, at least one side wall, and at least one internal partition wall defining a carrier gas thermal adjustment flow channel and a thermally adjusted carrier gas flow channel: and

(c) a common wall between the first and second structures, a major portion of the common wall comprising a porous and thermally conductive solid material, the porous solid material of the common wall allowing vapor phase precursor chemical composition to pass through after subliming to form a deposition composition, while the common wall retains a balance of the solid precursor chemical composition in the first structure.

[0098] Each of the embodiments A and C may have one or more of the following additional elements in any combination:

Element 1. Apparatus, systems and methods wherein the thermally adjusted carrier gas flows into a pre-heated carrier gas supply plenum between the first structure and the second structure, the pre-heated carrier gas supply plenum positioned below a lowermost one of the one or more cartridges, and the deposition composition flows into a deposition composition plenum inside the first structure, the deposition composition plenum positioned above an uppermost one of the one or more cartridges. El ement 2. Apparatus, systems and methods wherein flowing of the thermally adjusted carrier gas through the uniform heating zone comprises:

(d) flowing the thermally adjusted carrier gas tangentially across a first porous bottom panel of a first cartridge in a first uniform heating zone in a first direction, forming an intermediate composition comprising sublimed precursor composition at a first concentration in the carrier gas; and

(e) flowing the intermediate composition tangentially across a second porous bottom panel of a second cartridge in a second uniform heating zone in a second direction, forming the deposition composition having a second concentration of precursor chemical composition greater than the first concentration in the carrier gas, wherein the second direction differs from the first direction by an angle a of at least 90 degrees (or at least 100, or 110 or 120 or, 130, or, 140, or 150, or 160, or 170, or 180 degrees).

Elem ent 3: Apparatus, systems and methods wherein the flowing of the carrier gas through the pre-heat zone, forming a thermally adjusted carrier gas comprises flowing the carrier gas into a space between an external surface of the first structure and an internal surface of the second structure, the external surface of the first structure or the internal surface of the second structure, or both, having one or more heating elements positioned thereon, forming a pre-heated carrier gas, the pre-heated carrier gas forced through a nozzle in a bottom panel of the first structure- Element 4: Apparatus, systems and methods wherein steps (b) and (c) occur continuously.

Element 5: Apparatus, systems and methods wherein the sublimed precursor chemical composition passes through a plurality of tortuous paths in the porous panel, the tortuous paths having an average pore size ranging from about 0.01 to about 10 microns (or from about 0.01 to about 8 microns, or from about 0.02 to about 7 microns, or from about 0.03 to about 5 microns.

Element 6: Apparatus, systems and methods comprising sensing a level of the solid precursor chemical composition in one or more of the one or more cartridges using a method selected from the group consisting of gravity sensing, magnetic sensing, optical sensing, RF sensing, capacitance (contact or proximity) sensing.

Element 7: Apparatus, systems and methods comprising sensing a parameter selected from the group consisting of temperature of the pre-heated carrier gas, temperature of the deposition composition inside the first structure, pressure inside the first structure, displacement of the first structure in response to an oscillation input, solid precursor surface shape, and combinations thereof.

Element 8: Apparatus, systems and methods comprising controlling one or more of the parameters using a control scheme selected from feed forward, feedback, cascade, or combination thereof.

Element 9: Apparatus, systems and methods comprising using a laser-based device to sense the level and surface characterization.

Element! 0: Apparatus, systems and methods wherein the one or more internal walls assist in maintaining the solid precursor chemical composition thermally homogeneous by conducting heat into the solid precursor chemical composition.

Element 11 : Apparatus, systems and methods wherein after step (d) but prior to step (e) the first intermediate composition flow vertically upward from the first uniform heating zone to the second uniform heating zone.

Element 12: Apparatus, systems and methods wherein steps (b)-(e) are continuous and are carried out simultaneously.

Element 13: Apparatus, systems and methods comprising adjusting concentration of the precursor chemical composition or derivative thereof in the deposition composition by sensing a parameter downstream of the sublimer and feeding back the sensed parameter to a first structure pressure controller, a carrier gas flow controller, or combination thereof.

Element 14: Apparatus, systems and methods wherein the thermally adjusted carrier gas and the intermediate composition flow horizontally in opposite directions.

Element 15: Apparatus, systems and methods wherein the time and temperature sufficient to produce a deposition composition comprising sublimed precursor chemical composition (or derivative thereof) dispersed in the thermally adjusted carrier gas ranges from about 1 to about 10 minutes at temperature up to about 400 °F (about 204 °C) up to about 600 °F (up to about 316 °C).

Element 16: Apparatus, systems and methods wherein the cartridge floors comprise a layer of the porous solid material and a layer of an inert mesh material (Teflon-coated wire mesh or the like).

Element 17: Apparatus, systems and methods wherein the internal walls comprise 10 gauge nickel 200.

Element 18: Apparatus, systems and methods wherein the cartridges have length and width dimensions sufficient to form tight, sealing fits between the cartridges and the sidewalis of the first structure.

Element 19: Apparatus, systems and methods wherein each cartridge includes at least one vertical flow channel near one end of each cartridge for passing carrier gas (or deposition composition) therethrough from beneath the porous bottom panel to above the top panel of each cartridge without contacting the solid precursor chemical composition.

Element 20: Apparatus, systems and methods wherein each cartridge comprises tabs or rails fitting in slots in the internal wall of the first general cubical structure.

[0099] Each of the embodiments B and D may have one or more of the following additional elements in any combination:

Element 21 : Apparatus, systems and methods wherein the flowing of the carrier gas through the carrier gas thermal adjustment flow channel comprises:

(1) flowing the carrier gas to a carrier gas plenum at a first end of the second structure;

(2) routing the carrier gas from the carrier gas plenum to a first outer longitudinal channel and flowing the carrier gas longitudinally therethrough to form a first pre-heated carrier gas;

(3) directing the first pre-heated carrier gas from the first outer longitudinal channel to a first cross flow channel at a second end of the second structure and flowing the first pre-heated carrier gas therethrough to form a second pre-heated carrier gas; and (4) routing the second pre-heated carrier gas from the cross flow channel into a second outer longitudinal channel and flowing the second pre-heated carrier gas longitudinally therethrough in a flow direction opposite a flow direction of the carrier gas in the first longitudinal channel, forming a third pre-heated carrier gas.

Element 22: Apparatus, systems and methods wherein the flowing the thermally adjusted carrier gas through the thermally adjusted carrier gas flow channel tangentially past the porous and thermally conductive solid material of the common wall comprises:

(5) routing the third pre-heated carrier gas into a first intermediate longitudinal channel and flowing the third pre-heated carrier gas longitudinally therethrough to form a first intermediate deposition composition;

(6) directing the first intermediate deposition composition from the first intermediate longitudinal channel to a second cross flow channel near the second end of the second structure and flowing the first intermediate deposition composition therethrough to form a second intermediate deposition composition;

(8) routing the second intermediate deposition composition from the second cross flow channel into a second intermediate longitudinal channel and flowing the second intermediate deposition composition longitudinally therethrough in a flow direction opposite a flow direction of the first intermediate deposition composition in the first intermediate longitudinal channel, forming a third intermediate deposition composition;

(9) routing the third intermediate deposition composition from the second intermediate longitudinal flow channel into a third cross-flow channel, forming a fourth intermediate deposition composition;

(10) routing the fourth intermediate deposition composition from the third cross-flow channel into a third intermediate longitudinal channel and flowing the fourth intermediate deposition composition longitudinally therethrough in a flow direction the opposite a flow direction of the second intermediate deposition composition in the second intermediate longitudinal channel, forming a fifth intermediate deposition composition; (11) routing the fifth intermediate deposition composition from the third intermediate longitudinal flow channel into a fourth cross-flow channel, forming a sixth intermediate deposition composition; and

(12) routing the sixth intermediate deposition composition from the fourth cross-flow channel into a fourth intermediate longitudinal channel and flowing the sixth intermediate deposition composition longitudinally therethrough in a flow direction the opposite a flow direction of the fourth intermediate deposition composition in the third intermediate longitudinal channel, forming a final deposition composition;

wherein the concentration of the precursor chemical composition in the carrier gas increases with each step (5)-(12), inclusive.

Element 23: Substrates including a film or layer comprising the precursor chemical composition or derivative thereof produced according to the methods of Embodiment A combined with one or more of Elements 1-20.

[0100] Although only a few exemplary embodiments of this disclosure have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of this disclosure. Accordingly, all such modifications are intended to be included within the scope of this disclosure as defined in the following claims. In the claims, no clauses are intended to be in the means-plus-function format allowed by 35 U.S.C. § 112, Section F, unless "means for" is explicitly recited together with an associated function. "Means for" clauses are intended to cover the structures, materials, and/or acts described herein as performing the recited function and not only structural equivalents, but also equivalent structures.