Coatings for enhancing the properties and performance of substrate articles and devices

Abstract

It provides coatings that can be applied to a variety of substrate articles, structures, materials and devices. In various applications, substrates include metal surfaces susceptible to the formation of metal oxides, nitrides, fluorides, or chlorides, configured for contact with gases, solids, or liquids that react with the metal surfaces to form reaction products harmful to the substrate article, structure, material, or device. The metal surfaces are coated with a protective coating that prevents reaction of the coated surface with the reactive gas and / or otherwise improves the electrical, chemical, thermal, or structural properties of the substrate article or device. Specifically, a method for forming a patterned ALD coating on a substrate portion includes uniformly coating the portion with the ALD coating, masking areas of the coated substrate portion with a mask that includes a sealed sheet or fixture, and etching back unwanted coating material through the mask.

Description

[Technical Field]

[0001] This application is a joint venture under 35 U.S.C. § 119 of the following U.S. provisional patent applications: U.S. Provisional Patent Application No. 62 / 116,181, filed February 13, 2015, in the name of Carlo Waldfried et al., for "THIN FILM ATOMIC LAYER DEPOSITION COATINGS"; U.S. Provisional Patent Application No. 62 / 167,890, filed May 28, 2015, in the name of Bryan C. Hendrix et al., for "COATINGS TO PREVENT TRANSPORT OF TRACE METALS BY AL2CL6 VAPOR"; and U.S. Provisional Patent Application No. 62 / 167,890, filed July 2, 2015, in the name of Bryan C. Hendrix et al., for "COATINGS FOR ENHANCEMENT OF PROPERTIES AND PERFORMANCE OF SUBSTRATE ARTICLES AND The present invention claims the benefit of U.S. Provisional Patent Application No. 62 / 188,333, entitled "COATINGS FOR ENHANCEMENT OF PROPERTIES AND PERFORMANCE OF SUBSTRATE ARTICLES AND APPARATUS"; and U.S. Provisional Patent Application No. 62 / 221,594, entitled "COATINGS FOR ENHANCEMENT OF PROPERTIES AND PERFORMANCE OF SUBSTRATE ARTICLES AND APPARATUS," filed September 21, 2015, in the name of Bryan C. Hendrix et al. The disclosures of such U.S. Provisional Patent Applications Nos. 62 / 116,181, 62 / 167,890, 62 / 188,333, and 62 / 221,594 are incorporated herein by reference in their entirety for all purposes.

[0002] The present disclosure relates generally to coatings that can be applied to various substrate articles and equipment, for example, with respect to structures and devices having surfaces susceptible to the formation of undesirable oxide, nitride, fluoride, chloride or other halide contaminant species. In certain aspects, the present disclosure relates to semiconductor manufacturing equipment and methods for enhancing the performance thereof, and more particularly to semiconductor manufacturing equipment susceptible to contaminant contamination and particle deposition associated with the presence of aluminum hexachloride vapor in such equipment, and compositions and methods for addressing such harmful contaminant contamination and particle deposition. [Background technology]

[0003] In many technical fields, structures, materials and devices are found that include surfaces that are susceptible to the formation of contaminant species, such as surfaces of aluminum, anodized aluminum oxide, quartz, stainless steel, and the like, that are susceptible to the formation of undesirable oxide, nitride and halide (e.g., fluoride and / or chloride) contaminant species, which can interfere with the use, utilization or function of the associated product, equipment or material.

[0004] Aluminum and aluminum-containing materials are widely used in the field of semiconductor manufacturing. Although aluminum as a metallization material has been largely replaced by copper in nanoscale integrated circuit applications, aluminum still continues to be widely utilized as a wire bonding and connecting material, and as a thin film material (e.g., AlN thin films) as a barrier layer, a component of piezoelectric devices, a cold cathode material, etc., and for use in semiconductor compound compositions for applications such as LEDs and other optoelectronic devices, or Al2O3 layers as a dielectric, dielectric dopant, barrier, optical coating, etc.

[0005] In many such applications, halogen gases are used in semiconductor manufacturing equipment to process films in device manufacturing operations or as co-flowing cleaning agents to remove contaminant deposits that have accumulated on the surfaces and components of the equipment. These halogen gases may contain chloro species that, when in contact with aluminum present on the equipment, e.g., wafer surfaces, or on the surfaces or components of the equipment, may react to form aluminum hexachloride (AlCl) vapor. Such aluminum hexachloride vapor may, in turn, corrode stainless steel surfaces and components in semiconductor manufacturing equipment and may serve to carry measurable levels of metals such as chromium, iron, and nickel to ongoing wafer processing.

[0006] Another class of applications uses Al2Cl6 vapor to deposit aluminum-containing films. Al2O3 is widely deposited by ALD using trimethylaluminum as a reagent source; nevertheless, trimethylaluminum is a pyrophoric solution that incurs significant safety and regulatory costs. Al2Cl6 vapor can be readily generated as solid AlCl3 in a solid-state vaporizer, such as the type of solid-state vaporization unit sold under the trade name ProE-Vap by Entegris, Inc., Billerica, Massachusetts, USA.

[0007] Stainless steel components of semiconductor and manufacturing equipment may be formed from 316 stainless steel or other stainless steel alloys, which are typically electropolished. Such electropolishing typically leaves surfaces coated with a layer of passive oxide containing chromium, iron, nickel, and other alloying elements. Furthermore, such metal components may form traces of the corresponding oxide surface through natural oxidation processes. As a result, when dialuminum hexachloride encounters such metal oxides, the metal oxide reacts with dialuminum hexachloride to form the corresponding vapor-phase metalloaluminum chloride compounds, which may be transported to wafers and semiconductor devices or device precursor structures, depositing trace metals or otherwise causing damage to products being manufactured in the equipment. Alternatively, the metal oxide may react with Al2Cl6 vapor to form Al2O3 and metal chloride particulates that may be transported to device structures and cause damage. Furthermore, solid AlCl3 may contact metal oxide surfaces to form metalloaluminum chloride vapor or solid chloride particles. Summary of the Invention [Problem to be solved by the invention]

[0008] As a result, suppressing the deleterious interactions of aluminum hexachloride with metal surfaces and components in such semiconductor manufacturing equipment and other thin film deposition or etching equipment would be a significant improvement.

[0009] There is also a continuing need for dense, pinhole and defect free coatings for various industrial applications that provide other coating qualities and benefits such as electrical insulation of parts, the ability to conformally coat parts, chemical and etch resistance, corrosion resistance, diffusion barrier properties and adhesion layer properties. [Means for solving the problem]

[0010] (Summary of the Invention) The present disclosure relates generally to coatings applicable to various substrate articles, structures, materials and devices, and in particular aspects to semiconductor manufacturing equipment and methods for enhancing the performance thereof, and more particularly to semiconductor manufacturing equipment susceptible to contaminant contamination and particle deposition associated with the presence of dialuminum hexachloride in such equipment, and compositions and methods for combating such harmful contaminant contamination and particle deposition.

[0011] In one aspect, the present disclosure relates to a structure, material, or device comprising a surface of a metal susceptible to the formation of an oxide, nitride, or halide of said metal, wherein the surface of said metal is configured to come into contact with a gas, solid, or liquid that reacts with such metal oxide, nitride, or halide during use or operation of said structure, material, or device to form reaction products that are deleterious to said structure, material, or device and its use or operation, and wherein the surface of the metal is coated with a protective coating that prevents reaction of the coated surface with the reactive gas.

[0012] In one aspect, the present disclosure relates to a semiconductor manufacturing apparatus including a metal surface susceptible to the formation of an oxide, nitride, or halide of the metal, the metal surface being configured, during operation of the apparatus, to come into contact with a gas, solid, or liquid that reacts with the metal oxide, nitride, or halide to form reaction product particles and / or reaction product vapors that are deleterious to the apparatus and its operation, the metal surface being coated with a protective coating that prevents reaction of the coated surface with the reactive gas.

[0013] A further aspect of the present disclosure relates to a method of improving the performance of a structure, material, or device comprising a surface of a metal susceptible to the formation of an oxide, nitride, or halide of said metal, wherein the surface of said metal is configured to come into contact with a gas, solid, or liquid that will react with said metal oxide, nitride, or halide during use or operation of said structure, material, or device to form reaction products deleterious to said structure, material, or device and its use or operation, comprising coating the surface of the metal with a protective coating that prevents reaction of the coated surface with the reactive gas.

[0014] In another aspect, the present disclosure relates to a method for improving the performance of semiconductor manufacturing equipment including a metal surface susceptible to the formation of metal oxides, nitrides, or halides, wherein the metal surface is configured, during operation of the equipment, to come into contact with a gas, solid, or liquid that reacts with the metal oxide, nitride, or halide to form reaction products deleterious to the equipment and its operation, the method comprising coating the metal surface with a protective coating that prevents reaction of the coated surface with the reactive gas.

[0015] In another aspect, the present disclosure relates to improving the performance of semiconductor manufacturing equipment that contacts reactive solids.

[0016] According to a further aspect of the present disclosure, there is provided a thin film atomic layer deposition coating for industrial applications. The thin film coating according to the present disclosure is described herein.

[0017] Another aspect of the present disclosure relates to composite ALD coatings that include layers of different ALD product materials.

[0018] A further aspect of the present disclosure relates to a composite coating that includes at least one ALD layer and at least one deposited layer that is not an ALD layer.

[0019] In another aspect, the present disclosure relates to a method of forming a patterned ALD coating on a substrate, the method including forming a pattern of a layer of a surface termination material on the substrate that is effective to prevent ALD film growth.

[0020] In another aspect, the present disclosure relates to a method of filling and / or sealing a surface infirmity of a material, the method comprising applying an ALD coating to the surface infirmity of the material at a thickness that results in filling and / or sealing of the infirmity.

[0021] A further aspect of the present disclosure relates to a filter including a matrix of fibers and / or particles formed from a metal and / or polymeric material, the matrix of fibers and / or particles having an ALD coating thereon, where the ALD coating does not alter the pore volume of the matrix of fibers and / or particles by more than 5% compared to a corresponding matrix of fibers and / or particles without the ALD coating thereon, and the fibers and / or particles are formed from a metal, the ALD coating comprises a metal, and the metal of the ALD coating is different from the metal of the fibers and / or particles.

[0022] Yet another aspect of the present disclosure relates to a method of delivering a gas or vapor flow to a semiconductor processing tool, the method comprising: providing a flow path for the gas or vapor flow from a gas or vapor source to the semiconductor processing tool; and flowing the gas or vapor flow through a filter in the flow path to remove extraneous solid material from the flow, the filter comprising a filter of the present disclosure as variously described herein.

[0023] In a further aspect, the present disclosure relates to a filter comprising a calcined matrix of stainless steel fibers and / or particles coated with an ALD coating of alumina, wherein the calcined matrix comprises pores with diameters ranging from 1 to 40 μm, e.g., 10 to 20 μm, and the ALD coating has a thickness ranging from 2 to 500 nm.

[0024] Another aspect of the present disclosure relates to a solid vaporization apparatus comprising a vessel defining an interior volume including a support surface therein for vaporizing a solid material, at least a portion of the support surface having an ALD coating thereon.

[0025] In a further aspect, the present disclosure relates to a thin film coating comprising one or more layers, wherein at least one layer is deposited by atomic layer deposition.

[0026] Another aspect of the present disclosure relates to ALD coatings having thicknesses greater than 1000 Å.

[0027] A further aspect of the present disclosure relates to ALD coatings, including highly dense, pinhole-free, and defect-free layers.

[0028] Yet another aspect of the present disclosure relates to thin film coatings deposited on component surfaces other than integrated circuit devices on silicon wafers.

[0029] In a further aspect, the present disclosure relates to ALD films comprising insulating metal oxides and metals.

[0030] In another aspect, the present disclosure relates to ALD coatings that can be deposited at temperatures ranging from 20°C to 400°C.

[0031] A further aspect of the present disclosure relates to ALD coatings, including single films with defined stoichiometries.

[0032] Another aspect of the present disclosure relates to thin film coatings that include an ALD layer in combination with at least one other layer deposited by a variety of deposition techniques.

[0033] In another aspect, the present disclosure relates to multilayer ALD coatings having a coating thickness not exceeding 2 μm.

[0034] Another aspect of the present disclosure relates to ALD coatings comprised of materials selected from the group consisting of oxides, alumina, aluminum oxynitride, yttria, yttria-alumina mixtures, silicon oxides, silicon oxynitrides, transition metal oxides, transition metal oxynitrides, rare earth metal oxides, and rare earth metal oxynitrides.

[0035] A further aspect of the present disclosure relates to a method of forming a patterned ALD coating on a substrate portion, the method including uniformly covering the portion with an ALD coating and etching back unwanted coating material using a mask.

[0036] Another method aspect of the present disclosure relates to a method of forming a patterned ALD coating on a substrate portion, the method including masking an area of ​​the portion, covering the portion with an ALD coating, and removing the ALD coating from the masked areas of the portion.

[0037] A further method aspect of the present disclosure relates to a method of forming a patterned ALD coating on a substrate portion, the method including patterning the substrate portion with a material that includes a surface termination component that inhibits ALD film growth, and coating the patterned substrate portion with the ALD coating.

[0038] A further aspect of the present disclosure relates to a method of electrically insulating a substrate portion, the method comprising applying a defect-free, pinhole-free, dense, electrically insulating ALD coating to the substrate portion.

[0039] The present disclosure relates to coatings, including ALD coatings, on substrate surfaces that have chemical and etch resistant properties.

[0040] Another aspect of the present disclosure relates to coatings on substrate surfaces, including ALD corrosion-resistant coatings.

[0041] A further aspect of the present disclosure relates to a coating on a substrate surface that includes an ALD diffusion barrier layer.

[0042] A further aspect of the present disclosure relates to a coating on a substrate surface that includes an ALD adhesion layer.

[0043] Yet another aspect of the present disclosure relates to a coating on a substrate surface that includes an ALD surface sealant layer.

[0044] In another aspect, the present disclosure relates to a porous filter comprising a fibrous metal membrane coated with a chemically resistant ALD coating.

[0045] A further aspect of the present disclosure relates to a filter including a porous material matrix coated with an ALD coating, wherein the average pore size of the porous metal matrix is ​​reduced by the ALD coating relative to a corresponding porous material matrix not coated with the ALD coating.

[0046] Another aspect of the present disclosure relates to a filter that includes a porous material matrix coated with an ALD coating, where the coating thickness varies in one direction, resulting in a corresponding pore size gradient in the filter.

[0047] In a further aspect, the present disclosure relates to a method of making a porous filter, the method comprising coating a porous material matrix with an ALD coating to reduce the average pore size of the porous material matrix.

[0048] In another aspect, the present disclosure relates to a solid-state vaporizer comprising a vessel defining an interior volume therein, an outlet configured to exhaust precursor vapor from the vessel, and a support structure within the interior volume of the vessel adapted to support a solid precursor material thereon for vaporizing the solid precursor material to form a precursor vapor, wherein the solid precursor material comprises an aluminum precursor, and at least a portion of the surface area in the interior volume is coated with an alumina coating.

[0049] In a further aspect, the present disclosure relates to a method of enhancing the corrosion resistance of a stainless steel structure, material, or device that is exposed to aluminum halide during use or operation, the method comprising coating the stainless steel structure, material, or device with an alumina coating.

[0050] Another aspect of the present disclosure relates to a semiconductor processing etching structure, component or apparatus that is exposed to an etching medium during use or operation, and that is coated with a coating comprising a layer of yttria, optionally overlying a layer of alumina in said coating.

[0051] Yet another aspect of the present disclosure relates to a method of enhancing the corrosion and etch resistance of a semiconductor processing etching structure, component or device that is exposed to an etching medium during use or operation, the method comprising coating the structure, component or device with a coating comprising a layer of yttria, the layer of yttria optionally overlying a layer of alumina in said coating.

[0052] In another aspect, the present disclosure relates to an etch chamber air diffuser plate including a nickel membrane encapsulated by an alumina coating.

[0053] A further aspect of the present disclosure relates to a method of enhancing corrosion and etch resistance for an etch chamber diffuser plate including a nickel film, the method including coating the nickel film with an encapsulating coating of alumina.

[0054] In another aspect, the present disclosure relates to a vapor deposition processing structure, component, or apparatus that is exposed to a halide medium during use or operation, and that is coated with a coating of yttria, including an ALD base coating of yttria and a PVD overcoating of yttria.

[0055] In yet another aspect, the present disclosure relates to a method for enhancing the corrosion and etch resistance of a vapor deposition processing structure, component, or device that is exposed to a halide medium during use or operation, the method comprising coating the structure, component, or device with a coating of yttria, including an ALD base coating of yttria and a PVD overcoating of yttria.

[0056] Yet another aspect of the present disclosure relates to a quartz encapsulation structure, the interior surface of which is coated with an alumina diffusion barrier layer.

[0057] A further aspect of the present disclosure relates to a method for reducing mercury diffusion into a quartz containment structure susceptible to such diffusion during operation of the quartz containment structure, the method comprising coating an interior surface of the quartz containment structure with an alumina diffusion barrier layer.

[0058] A further aspect of the present disclosure relates to a plasma source structure, component, or apparatus that is exposed to plasma and voltages in excess of 1000 V during use or operation, wherein the plasma-wetted surface of the structure, component, or apparatus is coated with an ALD coating of alumina, and the alumina coating is overcoated with a PVD coating of aluminum oxynitride.

[0059] In one aspect, the present disclosure relates to a method for improving the useful life of a plasma source structure, component, or apparatus that is exposed to plasmas and voltages greater than 1000 V during use or operation, the method comprising coating a plasma-wetted surface of the structure, component, or apparatus with an ALD coating of alumina, and overcoating the alumina coating with a PVD coating of aluminum oxynitride.

[0060] In another aspect, the disclosure relates to a dielectric stack comprising sequential layers including an alumina base layer, a nickel electrode layer thereon, an ALD alumina electrical isolation layer on the nickel electrode layer, a PVD aluminum oxynitride thermal expansion buffer layer on the ALD alumina electrical isolation layer, and a CVD silicon oxynitride wafer contact surface and electrical spacer layer on the PVD aluminum oxynitride thermal expansion buffer layer.

[0061] In another aspect, the present disclosure relates to a plasma-activated structure, component, or device comprising an aluminum surface coated with one of (i) and (ii) multilayer coatings: (i) a CVD silicon basecoat on the aluminum surface, and a layer of ALD zirconia on the CVD silicon basecoat; and (ii) a CVD silicon oxynitride basecoat on the aluminum surface, and an ALD alumina layer on the CVD silicon oxynitride basecoat.

[0062] Another aspect of the present disclosure relates to a method for reducing particle formation and metal contamination on an aluminum surface of a plasma-activated structure, component, or apparatus, comprising coating the aluminum surface with one of the following multilayer coatings: (i) a CVD silicon base coat on the aluminum surface, and a layer of ALD zirconia on the CVD silicon base coat; and (ii) a CVD silicon oxynitride base coat on the aluminum surface, and an ALD alumina layer on the CVD silicon oxynitride base coat.

[0063] Another aspect of the present disclosure contemplates a porous matrix filter including a membrane formed from stainless steel, nickel, or titanium, wherein the membrane is encapsulated by alumina to a penetration depth of the coating ranging from 20 to 2000 μm.

[0064] In a corresponding method aspect, the present disclosure relates to a method of making a porous matrix filter, comprising encapsulating a membrane formed from stainless steel, nickel, or titanium with alumina to a penetration depth of the coating ranging from 20 to 2000 μm.

[0065] Other aspects, features, and embodiments of the present disclosure will become more fully apparent from the ensuing description and appended claims. [Brief explanation of the drawings]

[0066] [Figure 1] 1 is a schematic diagram of a vapor deposition furnace of a semiconductor wafer processing tool according to one aspect of the present disclosure. [Figure 2] 1 is a schematic diagram of a deposition furnace process system for coating wafers using Al2Cl6 vapor according to another embodiment of the present disclosure, which utilizes a solid source delivery vaporizer in the form of an ampoule for vaporizing AlCl3 to form Al2Cl6 vapor, in which the interior surfaces of the tray and ampoule are coated with Al2O3, as are all valves, tubes, and filters downstream of the ampoule. [Figure 3] 1 is a partial cutaway perspective view of a vaporizer container having a holder that helps promote gas contact with vapor from a material supported by the holder. [Figure 4] 1 is a photomicrograph, at 15K magnification, of the surface of a porous metal frit of a type useful for use in a filter element according to another embodiment of the present disclosure. [Figure 5] 20,000x magnification photomicrograph of an electropolished 316L stainless steel surface without exposure to AlCl3. [Figure 6] 1 is a photomicrograph at 1000x magnification of the surface of electropolished 316L stainless steel after exposure to AlCl3 at 120°C for 10 days in an anhydrous environment. [Figure 7]1 is a photomicrograph at 50,000x magnification of a cross section of electropolished 316L stainless steel that had not had any exposure to AlCl3. [Figure 8] 20,000x magnification photomicrograph of uncoated 316L stainless steel after 10 days of exposure to AlCl3 at 120°C in an anhydrous environment. [Figure 9] A photomicrograph at 35,000x magnification of electropolished 316L stainless steel after 10 days of exposure to AlCl3 at 120°C in an anhydrous environment shows numerous pits along the surface. [Figure 10] FIG. 3 is a photomicrograph at 35,000x magnification of electropolished 316L stainless steel coated with AlO by 100 cycles of ALD using trimethylaluminum and water before exposure to anhydrous AlCl at 120° C. for 10 days. [Figure 11] FIG. 3 is a photomicrograph at 35,000x magnification of electropolished 316L stainless steel coated with AlO by 1000 cycles of ALD using trimethylaluminum and water before exposure to anhydrous AlCl at 120° C. for 10 days. [Figure 12] 1 is a composite photograph of stainless steel sample coupons taken after 9 days of exposure to AlCl at 155° C. Sample coupons 2 and 3 are coated with a thick 470 Å coating of alumina, while sample coupons 12 and 13 are uncoated. [Figure 13] 1 is a top view scanning electron microscope (SEM) photograph of an alumina coated stainless steel sample after exposure to WCl5 at 220°C for 10 days. [Figure 14] 14 is a focused ion beam (FIB) cross-section of the coating edge of the sample of FIG. 13 after exposure to WCl5 at 220° C. for 10 days. [Figure 15]FIG. 1 is a perspective view of a stainless steel holder useful in a vaporizer ampoule for delivering aluminum trichloride (AlCl) solid precursor to an aluminum process, where the aluminum trichloride precursor is supported by the holder and vaporized to exit the vaporizer ampoule, forming aluminum trichloride precursor vapor, which is then passed through an associated flow circuit to the aluminum process. [Figure 16] FIG. 16 is a perspective view of a stainless steel holder of the type shown in FIG. 15 coated by atomic layer deposition with a coating of alumina on the stainless steel holder, such that the alumina coating encapsulates the stainless steel surface in corrosive environments, including exposure to aluminum trichloride (AlCl), to which the holder is exposed during use and operation of the vaporizer ampoule. [Figure 17] FIG. 1 is a close-up schematic of an alumina coating being applied to a stainless steel substrate by atomic layer deposition to provide corrosion resistance, prevent chemical reaction with the substrate, and reduce metal contamination during use. [Figure 18] FIG. 1 shows a plasma etcher channel coated with yttria (Y2O3). [Figure 19] FIG. 1 is a close-up schematic view of a yttria coating applied on alumina by atomic layer deposition. [Figure 20] 1 is a photograph of a diffuser plate assembly including a stainless steel frame and a nickel filter membrane coated with an alumina coating. [Figure 21] FIG. 1 is an enlarged schematic of a diffuser plate assembly with a stainless steel frame and nickel membrane encapsulated by ALD alumina. [Figure 22] FIG. 1 is an enlarged schematic diagram of the coating structure, including an aluminum substrate, an ALD coating of alumina, and a PVD coating of AION. [Figure 23]FIG. 1 is an enlarged schematic diagram of the layer structure of a dielectric stack useful in a hot chuck component, in this case an alumina substrate having an electrode metal thereon, an electrical isolation layer of ALD alumina thereon, a PVD coating of aluminum oxynitride thereon, and a layer of silicon oxynitride (SiON) deposited by chemical vapor deposition (CVD) thereon. [Figure 24] FIG. 1 is an enlarged schematic diagram of a multilayer stack comprising a silicon layer applied by chemical vapor deposition onto an aluminum substrate with an ALD layer of zirconia on top of the CVD Si layer. [Figure 25] FIG. 1 is an enlarged schematic diagram of a multilayer stack including a CVD layer of silicon oxynitride on an aluminum substrate and an ALD layer of alumina on a CVD SiON coating layer. [Figure 26] 1 is a micrograph of a porous material with a wall thickness of 1.5 mm and a pore size of 2-4 μm that has been coated with alumina by atomic layer deposition. [Figure 27] FIG. 1 is a schematic diagram of an encapsulating membrane, including a membrane formed from stainless steel, nickel, titanium, or other suitable material completely encapsulated by ALD-deposited alumina. [Figure 28] 1 is a photomicrograph of a coated filter where the coating is alumina with a coating penetration depth of 35 μm. [Figure 29] 1 is a photomicrograph of a coated filter where the coating is alumina with a coating penetration depth of 175 μm. DETAILED DESCRIPTION OF THE INVENTION

[0067] The present disclosure relates generally to coatings that can be applied to a variety of substrate articles, materials, structures, and devices. In various aspects, the present disclosure relates to semiconductor manufacturing equipment and methods for enhancing the performance thereof, and more particularly to semiconductor manufacturing equipment that is susceptible to contaminant contamination and particle deposition associated with the presence of dialuminum hexachloride in such equipment, and compositions and methods for combating such harmful contaminant contamination and particle deposition.

[0068] As used herein, for example, C1-C 12 The specification of a carbon number range in alkyl is intended to include each of the constituent carbon number subranges within that range, thereby encompassing each of the intervening carbon numbers in the stated range, and any other stated or intervening carbon number; it is further understood that subranges of carbon numbers within a specified carbon number range may be independently included in smaller carbon number ranges within the scope of the invention, and that ranges of carbon numbers specifically excluding one or more carbon numbers are included in the invention, and that subranges excluding one or both of the carbon number boundaries of a stated range are also included in the invention. Thus, C1-C 12 Alkyl is intended to include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, including straight chain and branched groups of such types. Thus, in specific embodiments of the present invention, the specification of carbon number ranges, e.g., C1-C2, is broadly applicable to substituent moieties. 12 It is understood that the carbon number range can be further restricted as a subgroup of moieties having a carbon number range that falls within the broader specifications of the substituent moiety. By way of example, in certain embodiments of the invention, a carbon number range, e.g., C-C 12 Alkyl can be more precisely specified to include subranges such as C1-C4 alkyl, C2-C8 alkyl, C2-C4 alkyl, C3-C5 alkyl, or any other subrange within the broader carbon number range. In other words, a carbon number range is considered to categorically describe each carbon number species within that range as either a successive carbon number subrange or a specified carbon number species within such a selection group, as a selection group from which the specified number of selection groups may be selected, with respect to the substituent, moiety, or compound to which such range applies.

[0069] The same flexibility of application of structure and selection is applicable to stoichiometric coefficients and values ​​specifying the number of atoms, functional groups, ions, or moieties with respect to specified ranges, numerical limits (e.g., inequalities, above limits, below limits), and other determining variables of oxidation state and specific form, charge state, and compositions applicable to dopant sources, implant species, and chemicals within the broad scope of the present disclosure.

[0070] As used herein, "alkyl" includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, pentyl, and isopentyl. As used herein, "aryl" includes a hydrocarbon derived from benzene or a benzene derivative that is an unsaturated aromatic carbocyclic group of 6 to 10 carbon atoms. An aryl may have a single ring or multiple rings. As used herein, the term "aryl" also includes substituted aryl. Examples include, but are not limited to, phenyl, naphthyl, xylene, phenylethane, substituted phenyl, substituted naphthyl, substituted xylene, substituted phenylethane, and the like. As used herein, "cycloalkyl" includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. In all chemical formulas herein, ranges of carbon numbers are considered to specify a series of alternative carbon-containing moieties, including all moieties containing carbon atoms intermediate to and equal to the end points of the specified range; for example, C1-C6 includes C1, C2, C3, C4, C5, and C6, and each such broader range may be further narrowed as a subrange by reference to the carbon numbers within such range. Thus, for example, the range C1-C6 is inclusive and may be further narrowed by specifying subranges such as C1-C3, C1-C4, C2-C6, C4-C6, etc., that fall within the broader range.

[0071] In one aspect, the present disclosure relates to a structure, material, or device comprising a surface of such a metal that is susceptible to the formation of metal oxides, nitrides, or halides (fluorides, chlorides, iodides, and / or bromides), wherein the surface of the metal is configured to be in contact with a gas, solid, or liquid that will react with the metal oxide, nitride, or halide during use or operation of the structure, material, or device to form reaction products that are deleterious to the structure, material, or device and its use or operation, and the structure, material, or device is coated with a protective coating that prevents reaction of the coated surface with the reactive gas.

[0072] In one aspect, the present disclosure relates to semiconductor manufacturing equipment including a metal surface susceptible to the formation of an oxide, nitride, or halide of the metal, the metal surface configured to come into contact with a gas, solid, or liquid that reacts with the metal during use or operation of the equipment to form reaction products harmful to the equipment and its use or operation, and the semiconductor manufacturing equipment is coated with a protective coating that prevents reaction of the coated surface with the reactive gas.

[0073] In such semiconductor manufacturing equipment, the metal oxide may, in various embodiments, comprise at least one oxide of one or more of Cr, Fe, Co, and Ni, or in other embodiments, the metal oxide may comprise at least one oxide of one or more of Cr, Fe, and Ni. Metal nitrides may form, for example, from iron or cobalt in the presence of ammonia during processing when ammonia is present, and the resulting iron or cobalt nitrides subsequently react with AlCl or TiCl. Metal halides may form on the metal surface during operation and etching or cleaning cycle operations. In various embodiments, the metal surface may include a stainless steel surface. In a specific embodiment, the gas reactive with the metal oxide, nitride, or halide to form reaction products harmful to the equipment and its use or operation comprises AlCl.

[0074] The protective coating in a specific application can comprise one or more coating materials selected from the group consisting of Al2O3, oxides of the formula MO (where M is Ca, Mg, or Be), oxides of the formula M'O2 (where M' is a stoichiometrically allowed metal), and oxides of the formula Ln2O3 (where Ln is a lanthanide element, e.g., La, Sc, or Y). More generally, the protective coating can comprise a metal oxide that has a free energy greater than or equal to zero for reaction with materials in contact with the metal surface during operation of the device.

[0075] A further aspect of the present disclosure relates to a method of improving the performance of a structure, material, or device comprising a surface of such a metal that is susceptible to the formation of metal oxides, nitrides, or halides, wherein the surface of the metal is configured to come into contact with a gas, solid, or liquid that will react with the metal oxide, nitride, or halide during use or operation of the structure, material, or device to form reaction products that are deleterious to the structure, material, or device and its use or operation, comprising coating the surface of the metal with a protective coating that prevents reaction of the coated surface with the reactive gas.

[0076] In another aspect, the present disclosure relates to a method for improving the performance of semiconductor manufacturing equipment including metal surfaces susceptible to the formation of metal oxides, nitrides, or halides, wherein the metal surfaces are configured, during use or operation of the equipment, to come into contact with gases that react with such metal oxides, nitrides, or halides to form reaction products deleterious to the equipment and its use or operation, the method comprising coating the metal surfaces with a protective coating that prevents reaction of the coated surfaces with the reactive gases.

[0077] In various embodiments, the metal oxide, nitride, or halide can include at least one oxide, nitride, or halide of one or more of Cr, Fe, Co, and Ni, and in other embodiments, at least one oxide, nitride, or halide of one or more of Cr, Fe, and Ni, or any other suitable metal oxide, nitride, or halide species. The metal surface may include, for example, stainless steel. Gases reactive with metal oxides, nitrides, or halides to form reaction products deleterious to structures, materials, or devices and their use or operation can include Al2Cl6.

[0078] The protective coating applied to the surface of the metal in the above-described method can comprise one or more coating materials selected from the group consisting of Al2O3, oxides of the formula MO (where M is Ca, Mg, or Be), oxides of the formula M'O2 (where M' is a stoichiometrically allowed metal), and oxides of the formula Ln2O3 (where Ln is a lanthanide element, e.g., La, Sc, or Y). More generally, the protective coating can comprise a metal oxide that has a free energy of reaction greater than or equal to zero with gases that contact the surface of the metal during use or operation of the structure, material, or device.

[0079] The protective coating can be applied to the surface of the metal in the methods of the present disclosure by any suitable technique, and in certain applications, the coating operation can include physical vapor deposition (PVD), chemical vapor deposition (CVD), solution deposition, or atomic layer deposition (ALD) of the protective coating.

[0080] ALD is a preferred technique for applying protective coatings to metal surfaces. In certain applications, plasma-enhanced ALD can be utilized as the ALD process to form protective coatings on metal surfaces. In various ALD embodiments, the protective coating can include Al2O3. Such protective coatings can be applied by atomic layer deposition, including a process sequence in which trimethylaluminum and ozone are utilized in an ALD cyclic process to form the protective coating, or alternatively, by atomic layer deposition, including a process sequence in which trimethylaluminum and water are utilized in an ALD cyclic process to form the protective coating.

[0081] In other ALD implementations of the present method, the protective coating may comprise a metal oxide of the formula MO, where M is Ca, Mg, or Be. Atomic layer deposition, for this application, can include process sequences in which a cyclopentadienyl M compound and ozone are utilized in an ALD cyclic process to form the protective coating, or a cyclopentadienyl M compound and water are utilized in an ALD cyclic process to form the protective coating, or a M beta-diketonate compound and ozone are utilized in an ALD cyclic process to form the protective coating, or other suitable process sequences and metal oxide precursor compounds. A wide variety of precursor ligands are available, including, but not limited to, H, C-C 10The following may be used to deposit protective coatings, including alkyl, linear, branched, or cyclic, saturated or unsaturated; aromatic, heterocyclic, alkoxy, cycloalkyl, silyl, silylalkyl, silylamide, trimethylsilylsilyl-substituted alkyl, trialkylsilyl-substituted alkyne and trialkylsilylamide-substituted alkyne, dialkylamide, ethylene, acetylene, alkyne, substituted alkene, substituted alkyne, diene, cyclopentadienyl arene, amine, alkylamine or bidentate amine, ammonia, RNH (R is an organic substituent, such as a hydrocarbyl substituent), amidinate, guanidinate, diazadiene cyclopentadienyl, oxime, hydroxyamine, acetate, beta-diketonate, beta-ketoiminate, nitrile, nitrate, sulfate, phosphate, halo; hydroxyl, substituted hydroxyl, and combinations and derivatives thereof.

[0082] In yet other ALD implementations of methods for applying protective coatings to metal surfaces, the protective coating may include a metal oxide having the formula Ln2O3, where Ln is a lanthanide element. Ln can be, for example, La, Sc, or Y. In applying a lanthanide oxide protective coating, atomic layer deposition can include a process sequence in which a cyclopentadienyl Ln compound and ozone are utilized in an ALD cyclic process to form the protective coating, or a process sequence in which a cyclopentadienyl Ln and water are utilized in an ALD cyclic process to form the protective coating, or a process sequence in which a Ln beta-diketonate compound and ozone are utilized in an ALD cyclic process to form the protective coating, or any other suitable process sequence and a lanthanide precursor compound.

[0083] The protective coating may be coated onto the surface of the metal in any suitable thickness, for example, a coating thickness in the range of 5 nm to 5 μm.

[0084] In various embodiments, the metal surface may be at a temperature ranging from 25° C. to 400° C. during coating of the metal surface with the protective coating. In other embodiments, such metal surfaces may be at a temperature ranging from 150° C. to 350° C. during the coating operation. In still other embodiments, the temperature of the metal surface may be in other ranges for applying the protective coating to the metal surface.

[0085] The problem of chemical corrosion and transport of contaminant species in semiconductor manufacturing operations, addressed by the present disclosure, is particularly acute in stainless steel furnaces where wafers are processed to produce microelectronic devices and other semiconductor manufacturing products. In such furnaces, the aluminum hexachloride vapor stream has been found to carry measurable levels of Cr, Fe, and Ni to the wafers when AlCl vapor is transferred into the system. The measured flux levels are consistent with the removal of the corresponding oxides of these metals that remain on the surface of stainless steel, e.g., 316L stainless steel, either by natural oxidation or electropolishing.

[0086] The present disclosure addresses the above problem by coating furnace surfaces and components with a coating of a material that does not react with Al2Cl6. This provides a much preferable solution to approaches that remove surface oxides, nitrides, and halides from stainless steel surfaces and components, so that ambient moisture leaks or maintenance events that expose such surfaces and components to moisture, as well as oxygen, nitrogen, and halogens, are consistently low enough that the stainless steel surfaces and components do not react with Al2Cl6. Furthermore, if Al2Cl6 is allowed to flow into the furnace in large quantities to react and remove metal oxides, nitrides, and halogens, such approaches would severely degrade the tool outlet and would not be a viable solution.

[0087] In contrast, the present disclosure uses a coating of surfaces and components in furnaces or other semiconductor manufacturing equipment so that the surfaces and components are passivated and do not react with Al2Cl6. As discussed, the coating advantageously comprises one or more coating materials selected from the group consisting of Al2O3, oxides of the formula MO (where M is Ca, Mg, or Be), oxides of the formula M'O2 (where M' is a stoichiometrically allowed metal), and oxides of the formula Ln2O3 (where Ln is a lanthanide element, e.g., La, Sc, or Y).

[0088] The coatings may be applied in any suitable manner that produces continuous, conformal coatings on surfaces and components of semiconductor manufacturing equipment, including physical vapor deposition (PVD), chemical vapor deposition (CVD), solution deposition, and atomic layer deposition (ALD) techniques.

[0089] In particular, ALD deposition is particularly advantageous for coating the inside of filter elements and tubes. Trimethylaluminum / ozone (TMA / O3) or trimethylaluminum / water (TMA / H2O) are useful compositions for depositing Al2O3. Cyclopentadienyl compounds of metals M or Ln can be used to deposit MO or Ln2O3 in an ALD cyclic process utilizing ozone (O3) or water vapor (H2O). Beta-diketonates of M or Ln can be used to deposit MO or Ln2O3 in an ALD cyclic process utilizing alternating reactive pulses of beta-diketonate metal precursors and pulses of O3.

[0090] For the deposition of an aluminum oxide protective coating, a metal precursor, e.g., trimethylaluminum, is selected along with an aerobic component such as ozone or water, and coating conditions are specified, which may illustratively include an ALD sequence of TMA / purge / HO / purge, or a TMA / purge / O / purge sequence, with a substrate temperature that may range, for example, from 150° C. to 350° C. and a coating thickness in the range of 5 nm to 5 μm. The pulse and purge times for this process sequence can then be determined for the particular reactor and geometry of the surface or component to be coated.

[0091] As a general approach, metal oxides suitable for protecting surfaces from aluminum hexachloride and metal oxides suitable for protecting surfaces from metal halide vapors can be selected based on the following method.

[0092] The temperature at which the aluminum hexachloride exposure occurs on the semiconductor equipment is first specified, and then the chemical reactions that occur with the chemical reagents contacting the surfaces and components of the semiconductor manufacturing equipment with respect to the metals on such surfaces and components are identified. For these chemical reactions at the specified temperatures, the enthalpy and entropy changes, as well as the free energy and reaction constants, can be identified, for example, as shown in Table 1 below.

[0093] [Table 1] JPEG0007737929000002.jpg49150

[0094] In the table, A is the number of moles, X is a halide ion, and N is any metal. For example, NX y can be HfCl4 or WCl6.

[0095] The reaction in the first row of Table 1 does not cause corrosion of metals in semiconductor manufacturing equipment because the free energy of the reaction is positive. However, the reaction in the second row of Table 1 may cause corrosion. Changing the surface oxide of stainless steel semiconductor manufacturing equipment from Cr2O3 to Al2O3 moves the driving force for this reaction toward zero. Alternatively, as shown in the third row of Table 1, any metal oxide MO with a free energy of reaction greater than or equal to zero (and x having any stoichiometrically appropriate value) can be used. x In addition, as shown in the fourth row of Table 1, the vapor of a common metal halide, such as NF3, NX y When the free energy of reaction is zero or more, the metal oxide MO x The protective oxide can be selected from

[0096] The protective coatings of the present disclosure can be utilized to protect against corrosive agents such as NF3, Al2Cl6, HfCl4, TiCl4, ZrCl4, WCl6, WCl5, VCl4, NbCl5, TaCl5, and other metal chlorides. For example, Al2O3 can be utilized as a protective coating material against these corrosive agents. Semiconductor materials, which may be delivered as gases or vapors, such as fluorine, chlorine, bromine, hydrogen fluoride, hydrogen chloride, hydrogen bromide, xenon difluoride, boron trifluoride, silicon tetrafluoride, germanium tetrafluoride, phosphorus trifluoride, arsenic trifluoride, boron trichloride, silicon tetrachloride, and ozone, mediate corrosion behavior, and Al2O3 coatings can be usefully employed to provide protection against such corrosive agents. Titanium tetrachloride is highly corrosive and has a positive ΔG relative to YO3.

[0097] In a specific embodiment, Al2O3 is utilized as a protective coating material with a positive ΔG upon exposure of a stainless steel surface to hydrogen bromide. In another embodiment, Al2O3 is utilized as a protective coating material with a positive ΔG upon exposure of a stainless steel surface to hydrogen chloride. In yet another embodiment, nickel is utilized as a protective coating material with a positive ΔG upon exposure of a stainless steel surface to silicon tetrachloride.

[0098] In a further embodiment, a protective coating having a positive ΔG on a stainless steel surface upon exposure to germanium tetrafluoride can include any of nickel, Al2O3, Cr2O3, gold, nitrides such as titanium nitride (TiN), glass, and copper. Passivation by germanium tetrafluoride is effective on stainless steel and nickel due to the formation of Ni-F, Cr-F, and Fe-F species, which can be thought of as NiF2, CrF3, or FeF3 layers on the nickel or stainless steel.

[0099] In another embodiment, gold is utilized as a protective coating material that has a positive ΔG upon exposure of a stainless steel surface to hydrogen fluoride.

[0100] In various embodiments, protective coatings for stainless steel and carbon steel include metals such as nickel and metal alloys. In other embodiments, protective coatings for such services can include polymeric materials such as polytetrafluoroethylene (PTFE) or PTFE-like materials, including protective coatings of materials commercially available under the trademarks Teflon® and Kalrez®. Protective coatings can also be used to avoid the embrittlement of stainless steel caused by exposure to hydride gas; such protective coatings can be formed from or otherwise include materials such as aluminum, copper, or gold.

[0101] The reactants on whose surfaces a protective coating is provided may be in solid, liquid and / or gas form, and may be in a mixture or solution with one or more solvents.

[0102] More generally, when considering ΔG, 10 -4 <K<10 +4 The stability of the range can change with changes in pressure or temperature, and K>10 +4 In this case, there is little corrosion under any conditions.

[0103] The dense, pinhole-free coatings of the present disclosure formed by ALD or other vapor phase deposition techniques are distinguished from native oxide surfaces. Native oxide films typically form at or near room temperature and are crystalline, and the oxidation associated with such native oxide films may be incomplete. Such native oxide films are more reactive than vapor phase deposited coatings, such as the ALD coatings of the present disclosure. The thick, dense, pinhole-free vapor phase deposited coatings of the present disclosure are amorphous and conformal.

[0104] In the case of alumina coatings on stainless steel formed according to the present disclosure, a cleaning or other pretreatment step is used prior to depositing the Al2O3 coating. For example, an electropolishing or reduction process, or a combination of such processes, may be used, as may be desirable or advantageous in a particular implementation of the present disclosure. Any other suitable cleaning or pretreatment step may also or alternatively be utilized.

[0105] With regard to aluminum trichloride, AlCl3 is not soluble in solvents or oil or grease, but oil or grease may be present as a heat transfer agent, for example, in a solid-delivery vaporizer, in which AlCl3 or other chemicals are provided for vaporization when the vapor is heated, resulting in a vapor stream dispensed from the container. For example, the AlCl3 or other chemical to be delivered is mixed with a high-boiling inert oil or grease to form a paste, which is then loaded onto a tray or other support surface in the solid-delivery container. The oil or grease then acts as a heat transfer agent and a medium for trapping small particles and preventing them from becoming suspended in the vapor stream. These trapped small particles are then held in the oil or grease until they are vaporized, thereby expelling them from the heat transfer agent and ultimately from the vaporizer container. In this manner, the oil or grease can improve thermal conductivity, allowing for a lower vaporizer delivery temperature.

[0106] Referring now to the drawings, FIG. 1 is a schematic diagram of a deposition furnace 102 of a semiconductor wafer processing tool 100 according to one embodiment of the present disclosure.

[0107] As shown, furnace 102 defines a heated interior volume 104 within which is disposed a liner 110 that separates the interior volume into an inner volume 108 within the liner 110 and an outer volume 106 outside the liner. A wafer carrier 112 having a wafer 114 mounted therein is disposed within the interior volume 108 within the liner 110 so that the wafer can be exposed to processing gases within the furnace.

[0108] As shown in the diagram of FIG. 1 , a first process gas may be supplied to the furnace interior volume 108 from a first process gas source 116 via a first process gas feed line 118. Similarly, a second process gas may be supplied to the furnace interior volume 108 from a second process gas source 120 via a second process gas feed line 122. The first and second process gases may be introduced into the furnace simultaneously or sequentially during operation of the tool. The first process gas may include, for example, an organometallic precursor for depositing metal components on the wafer substrate in the wafer carrier 112. The second process gas may include, for example, a halide cleaning gas. Gases introduced into the furnace interior volume 108 flow upward within the liner and, upon exiting the upper open end of the liner 110, flow downward into the annular exterior volume 106. Such gases then flow from the furnace in exhaust line 124 to abatement unit 126, where the furnace exhaust gases are treated to remove hazardous constituents therefrom and the treated gases are discharged in vent line 128 for further processing or other treatment. The abatement unit 126 may include wet and / or dry scrubbers, catalytic oxidation devices or other suitable abatement equipment.

[0109] According to the present disclosure, the surfaces of the furnace and liner components are coated with a layer of Al2O3 so that they are resistant to chemical corrosion from aluminum hexachloride, which in turn can cause the wafers 114 within the furnace to become defective or even render them useless for their intended purpose.

[0110] FIG. 2 is a schematic diagram of a deposition furnace process system for coating wafers using Al2Cl6 vapor according to another embodiment of the present disclosure, which utilizes a solid source delivery vaporizer in the form of an ampoule for vaporizing AlCl3 to form the Al2Cl6 vapor, with the interior surfaces of the tray and ampoule coated with Al2O3, as well as all valves, tubes, and filters downstream of the ampoule coated with Al2O3.

[0111] As illustrated, the ampoule is supplied with argon carrier gas from a supply vessel ("Ar"), which flows into the ampoule through a carrier gas feed line containing a mass flow controller ("MFC"). In the ampoule, the carrier gas contacts Al2Cl6 vapor produced by heating the ampoule to vaporize solid AlCl3 supported on a tray within the ampoule; the vaporized Al2Cl6 is then flowed into a furnace containing wafers onto which aluminum is deposited from the Al2Cl6 vapor. Co-reactants for deposition can be introduced into the furnace as shown through a co-reactant feed line to the furnace. Fluids flowing through the furnace are controlled by a pump and pressure control valve assembly to maintain furnace conditions suitable for conducting the deposition operation therein.

[0112] As mentioned, the inner surfaces of the trays and ampoules are coated with Al2O3, as are all of the flow circuit surfaces and components downstream of the ampoules, to prevent corrosion by aluminum hexachloride vapor. The filters in the flow circuit can be of the type with a metallic filter element, commercially available under the trademarks Wafergard™ and Gasketgard™ from Entegris, Inc. (Billerica, MA, USA).

[0113] FIG. 3 is a partial cutaway perspective view of a vaporizer ampoule of a type suitable for use in the vapor deposition furnace process system of FIG. 2. The vaporizer ampoule includes a vessel 300 having a holder that helps facilitate contact of gas with vapor from a material supported by the holder. The vessel has a plurality of holders 310, 320, 330, 340, 350, and 360 that define respective support surfaces 311, 321, 331, 341, 351, and 361. The vessel generally has a bottom wall having a surface 301 and a sidewall 302 that help define a generally cylindrical interior region within vessel 300 with an annular opening at or near the top of vessel 300. In a specific embodiment, the inner diameter of the generally cylindrical interior region can range, for example, from about 3 inches to about 6 inches.

[0114] Although the container 300 is illustrated in Figure 3 as having a unitary body, the container may be formed from separate components. The container includes an ampoule for vaporizing material for delivery to processing equipment.

[0115] As illustrated in FIG. 3 , holder 310 may be positioned on bottom surface 301 to define support surface 311 thereon, and holder 320 may be positioned on holder 310 to define support surface 321 thereon. Holder 330 may be positioned on holder 320 to define support surface 331 thereon. Holder 340 may be positioned on holder 330 to define support surface 341 thereon. Holder 350 may be positioned on holder 340 to define support surface 351 thereon. Holder 360 may be positioned on holder 350 to define support surface 361 thereon. While illustrated in FIG. 3 as using six holders, 310, 320, 330, 340, 350, and 360, any suitable number of holders may be used in various embodiments of the vaporizer.

[0116] 3, a generally tubular support 304 may be positioned within the interior region of vessel 300 above bottom surface 301 to support holder 310 above bottom surface 301. Tube 305 may then extend from openings in holders 360, 350, 340, 330, 320, and 310, generally in the center of the interior region of vessel 300, to a location between holder 310 and bottom surface 301.

[0117] 3 may be modified by connecting a baffle or diffuser to the end of tube 305 to assist in directing the flow of gas directly over the material supported on bottom surface 301. In embodiments in which the gas is introduced at or near the bottom holder supporting the material to be vaporized, the introduced gas may be directed to flow over and / or at the material supported by the bottom holder using any suitable structure.

[0118] As illustrated in FIG. 3 , container 300 may have a collar around the opening at the top of container 300, and lid 306 may be placed over and secured to the collar using, for example, screws such as screw 307. A groove may optionally be defined in the collar around the opening at the top to aid in placing O-ring 308 between container 300 and lid 306. O-ring 308 may be formed from any suitable material, such as, for example, Teflon®, any suitable elastomer, or any suitable metal, such as, for example, stainless steel. Lid 306 may define an opening, generally through a central region of lid 306, through which a passageway or portal, defined at least in part by tube 305, may extend to an interior region of container 300. As lid 306 is secured to the collar of vessel 300, lid 306 may press O-ring 308 to help seal lid 306 onto the collar and may press the collar around tube 305 to help hold lid 306 against holders 360, 350, 340, 330, 320, and 310. The O-rings of holders 360, 350, 340, 330, 320, and 310 may then be pressed to help seal holders 360, 350, 340, 330, 320, and 310 against each other and / or tube 305. Valve 381, having an inlet connecting to 391, may be connected to tube 305 to help regulate the introduction of gas into vessel 300. The lid 306 may also define an opening through which a passageway or outlet defined at least in part by a tube may extend into the container 300. A valve 382 having an outlet connecting to 392 may be connected to the tube to help regulate the delivery of gas from the container.

[0119] 3, a generally tubular frit 370 may be disposed on top of upper holder 360 to help filter solid material from the gas stream directed over the material supported by holder 360 before delivery through the outlet defined by lid 306. Frit 370 may define a generally annular opening, generally through a central region of frit 370, through which tube 305 may extend. Frit 370 is secured to vessel 300 such that lid 306 helps seal frit 370 onto holder 360, and frit 370 may be held down on holder 360 in any suitable manner using any suitable structure. In addition to or instead of frit 370, the vaporizer may include frits disposed in a pathway or outlet for delivering gas from vessel 300 and / or one or more frits positioned in one or more flow passages via one or more of holders 310, 320, 330, 340, 350, and 360. The frits in the vaporizer may be further coated with Al2O3. Similarly, any other internal components within the vaporizer may be coated with Al2O3, such that all surfaces and components in the vaporizer's internal volume are coated with Al2O3.

[0120] 3, a bypass path defined by tube 395 connected between valves 381 and 382 may be used to help purge valves 381 and 382, ​​the inlet connected to 391, and / or the outlet connected to 392. Valve 383 may optionally be connected to tube 395 to help regulate fluid flow through the bypass path. An inlet / outlet connected to 397 may optionally be used to help define an additional inlet / outlet for an interior region of vessel 300 to help purge the interior region.

[0121] FIG. 4 is a photomicrograph, at 15K magnification, of the surface of a porous metal frit of a type useful for use in a filter element according to another embodiment of the present disclosure.

[0122] The large surface area of ​​the frit can be advantageously coated by ALD, with the metal precursor and oxidizing co-reactant reaching the surface in separate, self-limiting pulses. Alternating pulses of trimethylaluminum and water or an O / O mixture may be used to coat the frit with AlO. Specific conditions can be empirically determined by increasing the pulse length of each step until all of the surface is coated. In certain embodiments, deposition temperatures of 100 to 400°C can be used to deposit useful films.

[0123] It is understood that other aluminum sources may be used in the broad practice of the present disclosure, such as AlCl, other AlR(alkyl) compounds, where R is an organic moiety or other volatile Al compound. In such practice of the present disclosure, other oxygen sources, such as N2O, O2, alcohols, peroxides, etc., may also be used along with the aluminum source reagent to produce Al2O3 or related AlO x The material can be deposited.

[0124] The features and advantages of the present disclosure will be more fully shown by the following examples, which are intended as illustrative features to facilitate an understanding of the disclosure. [Example]

[0125] [Example 1] The electropolished 316L stainless steel specimens were rinsed with isopropanol to clean the surface. Two specimens were coated with Al2O3 by atomic layer deposition (ALD). One specimen underwent 100 ALD cycles of trimethylaluminum / purge / water / purge, while the other specimen underwent 1000 cycles of the same ALD process. The deposition temperature was 150°C. Two specimens were uncoated. Both the coated and uncoated specimens were loaded into glass ampoules containing solid AlCl3 powder in a nitrogen-purged glove box to prevent moisture or oxygen from interacting with the specimens or AlCl3. The glass ampoules were then sealed with PTFE caps. The ampoules containing the AlCl3 and stainless steel specimens were heated to 120°C for 10 days. At the end of the 10 days, the ampoules were cooled and returned to the glove box. The specimens were removed from the AlCl3 under this inert atmosphere. The mass gain of the samples was 0.4 to 0.7 mg (<0.15%). All surfaces appeared intact to the naked eye. These three samples, as well as an additional sample that did not appear to have been exposed to any AlCl, were then examined in a scanning electron microscope (SEM) on the top surfaces of the samples, and then cross-sectioned with a focused ion beam (FIB) to determine if any corrosion was present on the surfaces.

[0126] Figure 5 shows a surface image of the sample where no AlCl was observed. The surface of this sample is clean and shows the main elements of stainless steel: Fe, Cr and Ni.

[0127] Figure 6 shows an uncoated sample exposed to AlCl. It can be seen that there is a significant surface residue on this sample due to the addition of Al and Cl to the stainless steel main components.

[0128] Figure 7 shows a cross section of a sample that was not exposed to AlCl3, and the absence of surface corrosion is evident.

[0129] Figure 8 shows an uncoated sample exposed to AlCl. There are lines of comparison with the surface, and it is clear that there was 0.1 to 0.2 microns of surface corrosion beneath the areas with Al and Cl-containing residues.

[0130] Figure 9 shows different areas of the AlCl-exposed sample without a surface coating. Native oxide is present on the untreated stainless steel surface. In this area, multiple pits are clearly visible.

[0131] In contrast, Figure 10 shows a cross section of a surface that had a coating of 100 cycles of TMA / HO prior to exposure to AlCl at 120°C. In this case, there is still Al- and Cl-containing residue attached to the surface, but there is no evidence of any corrosion on the stainless steel surface.

[0132] Similarly, Figure 11 shows a cross section of a surface with a 1000 cycle TMA / HO coating prior to exposure to AlCl at 120°C. In this case, there is still Al- and Cl-containing residue attached to the surface, but no evidence of corrosion on the stainless steel surface.

[0133] [Example 2] In one empirical evaluation, the effectiveness of the alumina coating was assessed by exposure to aluminum trichloride (AlCl3) in the first test and tungsten pentachloride (WCl5) in the second test.

[0134] In the first test, electropolished 316L stainless steel specimens were either coated with 470 Å of Al2O3 or uncoated. One specimen of each type was placed in one of two containers containing solid AlCl3. Both containers were filled, sealed, and pressurized with helium to 3 psi gauge inside a glove box purged with N2 and containing O2 and HO levels below 0.1 ppm. External He leak testing revealed that one of the containers had a leak rate of less than 1E-6 standard cubic centimeters per second (scc / s), which is the resolution limit of the measurement, and the other had a leak rate of 2.5E-6 scc / s. The containers were heated to 155°C in the same oven for 9 days, cooled, and the specimens were removed from the glove box. Table 2 shows the mass changes for the various specimens.

[0135] [Table 2]

[0136] FIG. 12 is a composite photograph of the sample specimens of Table 2 after exposure to AlCl at 155° C. for 9 days, each specimen identified by the same ID number set forth in Table 2.

[0137] It is clear from Table 2 that mass change could only be quantified when there was a measurable leak in the container. In this corrosive exposure, the sample mass loss tabulated in Table 2 and the composite photograph of the individual sample specimens in Figure 12 show that coated sample specimen 2 was in substantially better condition than uncoated sample specimen 12 after 9 days of exposure to AlCl at 155°C. There was no change in the Al2O3 coating thickness as measured by XRF.

[0138] In the second test, electropolished 316L stainless steel sample coupons were either coated with a 470 Å thick Al2O3 coating or uncoated. The sample coupons were placed in containers with solid WCl5, with temperatures of 165°C, 180°C, and 220°C maintained in individual containers. All of these containers were filled and sealed inside a N2-purged glove box with O2 and HO levels below 0.1 ppm. The containers were then heated in an oven for 10 days, cooled, and the sample coupons were removed from their individual containers in the glove box.

[0139] Thickness measurements were performed by X-ray fluorescence (XRF) spectroscopy to assess the change in coating thickness from the initial measured thickness of the alumina coating. Table 3 contains XRF measurements of Al2O3 thickness before and after exposure to WCl5, with two sample specimens maintained at 165°C for 10 days, two sample specimens maintained at 180°C for 10 days, and one sample specimen maintained at 220°C for 10 days. Approximately 15-30 Å of the coating was typically etched away in the cleaning process.

[0140] [Table 3]

[0141] FIG. 13 is a scanning electron microscope (SEM) photograph of a top view of a sample exposed to WCl5 at 220°C for 10 days, and FIG. 14 is a focused ion beam (FIB) cross section of the coating edge on such a sample.

[0142] The coated and uncoated samples in this second test were found to be free of corrosion by visual inspection, SEM examination, or weight change. However, at higher temperatures, significant amounts of the Al2O3 coating were removed. Both samples at 165°C were etched by amounts consistent with a cleaning process. One of the samples at 180°C lost 27 Å in thickness, consistent with cleaning, while the other sample lost approximately 66 Å in thickness, significantly more than the cleaning loss. At 220°C, approximately 60% of the coating was removed, as shown in Figure 13, where the alumina coating was removed in some areas (lighter areas) and intact in others (darker areas). In Figure 14, the photomicrograph shows the intact coating on the right, with the edges of the coated areas indicated by arrows.

[0143] While the present disclosure is illustratively directed to semiconductor manufacturing equipment, it is recognized that the protective coating techniques of the present disclosure are likewise applicable to other gas processing equipment for the manufacture of other products such as flat panel displays, photovoltaic cells, solar panels, etc., where the surfaces of the processing equipment are susceptible to corrosion by vapor phase constituents that react with oxides during such use to form reaction products that are deleterious to the products made using such equipment and the processes performed using such equipment.

[0144] Further aspects of the present disclosure related to thin film atomic layer deposition coatings are set out below.

[0145] While various compositions and methods are described, it is to be understood that the invention is not limited to particular molecules, compositions, designs, methods, or protocols, as these may vary. It is also to be understood that the terminology used in this description is for the purpose of describing particular variations or embodiments only, and is not intended to limit the scope of the invention.

[0146] It should also be noted that, as used herein, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, a reference to a "layer" refers to one of a plurality of layers and equivalents thereof known to those skilled in the art, and the like. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art.

[0147] Methods and materials similar or equivalent to those described herein may be used in the practice or testing of embodiments of the present disclosure. All publications mentioned herein are incorporated by reference in their entirety. The inventions claimed herein should not be construed as an admission that such publications are antedated by prior invention. "Optionally" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where the event does not occur. All numerical values ​​herein, whether explicitly stated or not, can be modified by the term "about." The term "about" generally refers to a range of numbers that one of ordinary skill in the art would consider equivalent to the recited value (i.e., having a similar function or result). In some embodiments, the term "about" refers to ±10% of the specified value, and in other embodiments, the term "about" refers to ±2% of the specified value. Although compositions and methods are described in terms of "compromising" various components and steps, such terms of art should be construed as defining a group of members that are essentially adjacent or adjacent to one another.

[0148] As used herein, the term "film" refers to a layer of deposited material having a thickness of less than 1000 micrometers, for example, from such a value to the thickness of an atomic monolayer. In various embodiments, the thickness of the layer of material deposited in the practice of the present invention can be, for example, less than 100, 50, 20, 10, or 1 micrometer, or in various regimes of various thin films, less than 200, 100, 50, 20, or 10 nanometers, depending on the particular application involved. As used herein, the term "thin film" refers to a layer of material having a thickness of less than 1 micrometer.

[0149] While the present disclosure has been described herein with respect to one or more implementations, equivalent changes and modifications will occur to those skilled in the art upon reading and understanding this specification. The present disclosure includes all such modifications and variations. Furthermore, while a particular feature or aspect of the present disclosure may be disclosed with respect to only one of several implementations, such feature or aspect may be combined with one or more other features or aspects of other implementations, which may be desirable and advantageous for any given or particular application. Furthermore, the terms "includes," "having," "has," "with," or variations thereof, to the extent present in this specification, are intended to be inclusive of such terms analogously to the term "comprising." Similarly, the term "exemplary" is merely intended to mean an example, rather than the best. It should also be understood that the features, layers and / or elements shown herein are illustrated and / or taught with specific dimensions and / or orientations relative to one another for purposes of simplicity and ease of understanding, and that the actual dimensions and / or orientations may differ substantially from those illustrated and / or taught herein.

[0150] Thus, the disclosure, particularly implementations, variously described herein with respect to features, aspects, and embodiments of the disclosure may be configured as including, consisting of, or consisting essentially of some or all of such features, aspects, and embodiments, as well as elements and components of the disclosure that are combined to form various further implementations of the disclosure. Accordingly, the disclosure contemplates such features, aspects, and embodiments, or selected one or more thereof, in various permutations and combinations, as being within its scope. Furthermore, the disclosure contemplates embodiments that may be defined by not including any one or more of any of the specific features, aspects, or elements disclosed herein relative to other embodiments of the disclosure.

[0151] According to one aspect of the present disclosure, a thin film coating is provided that is comprised of one of a plurality of layers, at least one of which is deposited by atomic layer deposition.

[0152] According to aspects of the present disclosure, there is provided: ALD coatings with thicknesses greater than 1 Å, and in some applications, greater than 10,000 Å.

[0153] ALD coatings that deliver highly dense, pinhole-free and defect-free layers.

[0154] Thin film coatings intended for deposition on a number of components, but not directly targeting the actual IC devices (transistors) fabricated on the silicon wafer.

[0155] ·ALD coatings can consist of insulating metal oxides such as alumina (Al2O3), yttria (Y2O3), zirconia (ZrO2), titania (TiO2), etc., and metals such as platinum, niobium, or nickel.

[0156] ALD coatings can be deposited between RT (room temperature) and 400°C.

[0157] ALD coatings can be single films with well-defined stoichiometry, e.g., a 1 micron thick alumina layer, or several layers, e.g., {0.25 micron titania + 0.5 micron alumina + 0.25 micron zirconia}, or true multilayer structures, e.g., {1 atomic layer titania + 2 atomic layers alumina} x n (n ranges from 1 to 10,000), or combinations of these.

[0158] Thin film coatings in which an ALD layer is combined with another layer deposited by a different deposition technique such as PE-CVD, PVD, spin-on or sol-gel deposition, atmospheric pressure plasma deposition, etc.

[0159] · Total thickness between 1 micron and 100 microns.

[0160] The portion of the ALD coating thickness of the entire stack that is 2 microns or less on one or more different layers.

[0161] Other coating materials selected from the group of oxides such as alumina, aluminum oxynitride, yttria, yttria-alumina mixtures, silicon oxide, silicon oxynitride, transition metal oxides, transition metal oxynitrides, rare earth metal oxides, rare earth metal oxynitrides.

[0162] ALD coatings can be patterned.

[0163] Method 1: Uniformly coat a portion, then etch back the unwanted material through a mask (this etch back can be mechanical, e.g., bead blasting, physical, e.g., plasma ion, or chemical, e.g., plasma or wet etching).

[0164] Method 2: Mask the unwanted areas, ALD coat, then remove the masked areas. The mask can be a sealing sheet, or a fixture or photoresist (lift-off technique).

[0165] Method 3: Create a pattern on a substrate with a surface termination that blocks ALD film growth. For example, a surface termination layer with a "zero" sticking coefficient for HO and TMA (trimethylaluminum) can be used. As used herein, a surface termination layer is a self-limiting layer, e.g., a self-limiting ALD layer. As used herein, the sticking coefficient is the ratio of the number of adsorbate atoms (or molecules) adsorbed or "attached" to a surface to the total number of those affecting this surface over the same time period.

[0166] According to aspects of the present disclosure, the following uses are provided: Usage: · Dense electrical insulator with no component defects and no pinholes.

[0167] Capable of coating parts with high aspect ratio features. Examples include: (1) parts with deep holes, channels, and three-dimensional features; (2) hardware such as screws and nuts; (3) porous membranes, filters, and three-dimensional network structures; and (4) structures with a matrix of interconnected pores.

[0168] Electrical insulation layer: High dielectric burst strength and high electrical resistance (low leakage). This is achieved by ALD Al2O3. The use of a multilayer consisting of titania-alumina-zirconia (TAZ) further improves the electrical insulation performance. Various multilayer configurations exist: Xnm TiO2+Ynm Al2O3+Znm ZrO2 [Unm TiO2+Vnm Al2O3+Wnm ZrO2T]×n Xnm TiO2+[Vnm Al2O3+Wnm ZrO2T]×m etc.; X, Y, Z, U, V and W can each range from 0.02 nm to 500 nm, and n and m can each range from 2 to 2000.

[0169] Chemically and etch-resistant coatings: ALD layers can be alumina, yttria, cerium oxide, or the like. The total etch-resistant coating can consist of (1) ALD layers alone, or (2) a combination of PVD, CVD, and ALD. (3) ALD can be overcoated to act as a sealant layer, as discussed more fully hereinafter. (4) ALD can be an underlayer that provides a robust foundation. (5) ALD can be interspersed between CVD and / or PVD coating layers.

[0170] ALD coatings can provide chemical resistance for applications such as advanced batteries, gas filters, liquid filters, electroplating tool components, and plasma-wetted components (to protect against corrosion from fluorine and other halogens).

[0171] ALD coatings can act as corrosion-resistant coatings.

[0172] Diffusion barrier layers: Dense, conformal, pinhole-free ALD layers provide excellent diffusion barrier properties for trace metals.

[0173] ALD layers are formed by bonding an underlying substrate (glass, quartz, aluminum, anodized aluminum oxide, alumina, stainless steel, silicon, SiOx, AlON, etc.) with an overcoat layer (PVD yttria, PVD AlON, PVD Al2O3, CVD SiOx, CVD SiO x N y , CVD Al2O3, CVD AlO x N y , DLC, Si, SiC, etc.).

[0174] According to another aspect of the present disclosure, ALD-deposited surface sealant layers are used in coatings. ALD (atomic layer deposition) is an established technology that uses the chemical adsorption of two or more alternating precursors to form highly dense, almost perfectly ordered (physically and stoichiometrically) thin films. This technique allows for precisely controlled film growth, is nearly 100% conformal, and grows films at any surface location accessible to precursor gases, including within very high aspect ratio features. In this regard, ALD-deposited sealant coatings can be used in the following applications:

[0175] (1) Overcoating and sealing an existing surface, thus achieving enhanced and superior properties of this surface / part.

[0176] (2) Applying an ALD sealing coating on top of a CVD, PVD, spray or other coating to provide a sealant against defects in the coating, such as: (i) Filling any imperfections near the coating surface, thus providing a surface impervious to corrosive and etching environments.

[0177] (ii) Filling and sealing any macropores, defects, penetrations, etc. in the coating, resulting in a coating surface layer that is impervious to gases and liquids and terminated by a controlled, smooth, conformal sealant layer.

[0178] (iii) reducing the surface roughness and overall surface area of ​​the coating, thus achieving a smooth and dense surface layer that allows for minimal corrosion in corrosive environments;

[0179] (iv) The overcoating provides a dense, smooth sealing surface, minimizing particle generation and improving hardness, toughness, and scratch resistance.

[0180] In various embodiments of the present disclosure, the ALD sealant can be applied to parts and surfaces requiring: (a) improved etch and corrosion resistance, and / or (b) Reduced friction, wear, and improved mechanical wear resistance The ALD sealant layer can simultaneously act as a diffusion barrier and has the ability to control the electrical properties of the surface as well as surface termination such as hydrophilicity and hydrophobicity.

[0181] A further aspect of the present disclosure involves the use of ALD techniques using metal fiber membranes with chemically resistant coatings such as alumina, yttria, or other coatings of this type that allow gases to pass through the porous filter and coat onto the porous membrane to provide resistance to corrosive gases.

[0182] This aspect of the present disclosure provides a deposition gas-based technique that can penetrate small micron-sized openings to provide uniform coating across the fiber.

[0183] This aspect of the disclosure is demonstrated by depositing an alumina coating on a 4 micron Ni-based gas filter manufactured by Entegris, Inc. (Billerica, MA, USA).

[0184] The ALD techniques of this disclosure offer many advantages, including: 1) Coat penetration into small features such as the micron-sized pores of the filter to ensure complete coverage.

[0185] 2) It seals the fibers and thus protects the filter membrane.

[0186] 3) A variety of different coatings can be deposited using this technique.

[0187] The present disclosure also contemplates the use of ALD coatings to improve the processing characteristics of the substrate article or device being coated. For example, ALD films can be used to address blistering or other undesirable phenomena that can occur during annealing of a substrate article due to mismatched thermal expansion coefficients between layers in a multilayer film article. Thus, ALD films can be used in multilayer film structures to improve such material property differences or otherwise improve the electrical, chemical, thermal, and other performance characteristics of the final product article.

[0188] The present disclosure further contemplates the use of ALD coatings to protect liquid-contacting surfaces of equipment handling fluids that may pose a risk of chemical corrosion during use of such equipment. Such equipment may include, for example, fluid reservoirs and dispensing packages used to supply gases to semiconductor manufacturing tools, where the fluids may adversely affect flow path components and downstream process equipment. Fluids that may pose particular problems in certain applications may contain halogenated gases, such as boron or germanium fluorides. Accordingly, the coatings of the present disclosure may be used to enhance the performance of processing equipment, flow circuits, and system components in these and other applications.

[0189] In a further aspect, the present disclosure relates to a composite ALD coating comprising layers of different ALD product materials. The different ALD product materials can be of any suitable type, for example, at least two metal oxides selected from the group consisting of different metal oxides, such as titania, alumina, zirconia, oxides of the formula MO (where M is Ca, Mg, or Be), oxides of the formula M'O (where M' is a stoichiometrically acceptable metal), and oxides of the formula LnO (where Ln is a lanthanide element such as La, Sc, or Y). In other embodiments, the composite ALD coating can comprise at least one alumina layer. In yet other embodiments, the composite ALD coating can comprise at least one titania or zirconia layer, or other suitable material.

[0190] Such composite ALD coatings can include different metals as the different ALD product materials, e.g., at least two metals selected from the group consisting of platinum, niobium, and nickel. Any suitable different metals can be used.

[0191] In other embodiments, the different ALD product materials can include a metal oxide material as a first ALD product material in a first layer of the composite coating and a metal as a second ALD product material in a second layer of the composite coating. The metal oxide material can be selected from the group consisting of alumina, titania, and zirconia, for example, and the metal is selected from the group consisting of platinum, niobium, and nickel.

[0192] The composite ALD coatings described above can have any suitable number of layers in the coating, for example, from 2 to 10,000 layers.

[0193] In another aspect, the present disclosure relates to a composite coating including at least one ALD layer and at least one deposited layer that is not an ALD layer. The composite coating can be configured, for example, such that the at least one deposited layer that is not an ALD layer is selected from the group consisting of a CVD layer, a PE-CVD layer, a PVD layer, a spin-on layer, a thermal spray layer, a sol-gel layer, and an atmospheric plasma deposited layer. In various embodiments, the layer in the composite coating can include at least one layer of a material selected from the group consisting of alumina, aluminum oxynitride, yttria, yttria-alumina, silicon oxide, silicon oxynitride, transition metal oxide, transition metal oxynitride, rare earth metal oxide, and rare earth metal oxynitride.

[0194] The present disclosure further contemplates a method of forming a patterned ALD coating on a substrate, the method including forming a pattern of a layer of a surface termination material on the substrate that is effective to prevent ALD film growth. Such a surface termination material in certain implementations may exhibit a sticking coefficient of essentially zero for water and trimethylaluminum. In various embodiments, the ALD coating may include alumina.

[0195] The present disclosure further contemplates a method of filling and / or sealing a surface weakness of a material, the method comprising applying an ALD coating to the surface weakness of the material at a thickness that results in filling and / or sealing of the weakness. The weakness may be of any type, such as selected from the group consisting of a scratch, a morphological defect, a pore, a pinhole, a discontinuity, a craze, a rough surface, or a surface asperity.

[0196] Another aspect of the present disclosure relates to a filter that includes a matrix of fibers and / or particles formed from a metal and / or polymeric material, the matrix of fibers and / or particles having an ALD coating thereon, where the ALD coating does not alter the pore volume of the matrix of fibers and / or particles by more than 5% compared to a corresponding matrix of fibers and / or particles without the ALD coating thereon, and the fibers and / or particles are formed from a metal, the ALD coating comprises a metal, and the metal of the ALD coating is different from the metal of the fibers and / or particles.

[0197] A filter can be configured with a matrix of fibers and / or particles within a housing configured to allow fluid to flow through the matrix for filtering the fluid. In various embodiments, the ALD coating can include a suitable type of transition metal, metal oxide, or transition metal oxide. For example, the ALD coating can include a metal oxide selected from the group consisting of titania, alumina, zirconia, oxides of the formula MO (where M is Ca, Mg, or Be), and oxides of the formula Ln2O3 (where Ln is a lanthanide element, La, Sc, or Y). In various implementations, the ALD coating includes alumina. The filter matrix can include nickel fibers and / or particles, stainless steel fibers and / or particles, or fibers and / or particles of other materials, such as polymeric materials, e.g., polytetrafluoroethylene. In various embodiments, the filter can include pores of any suitable diameter. For example, the pores may range from 1 μm to 40 μm in some embodiments, less than 20 μm, less than 10 μm, less than 5 μm, or other suitable values ​​in other embodiments, and in suitable ranges of 1 to 10 μm, 1 to 20 μm, 20 to 40 μm, or other values ​​in other embodiments. The ALD coating itself may be of any suitable thickness, and in various embodiments, may have a thickness ranging from 2 to 500 nm. In general, any suitable pore size and thickness characteristics may be used as appropriate for a particular end use or application.

[0198] A filter can be suitably characterized with respect to its retention rating. For example, in a specific embodiment, the retention rating of a filter can be characterized by a log reduction value of 9 (referred to as 9LRV) for particles larger than 3 nm at a gas flow rate of 30 standard liters per minute or less. Filters coated by the ALD method of the present disclosure can be used in a variety of applications where it is desirable for the filter to achieve a high degree of removal, e.g., 99.9999999%, or 9LRV, as determined by the majority permeating particle size at a particular rated flow rate. Test methods for assessing the 9LRV rating are described in Rubow, KL and Davis, C.B., "Particle Penetration Characteristics of Porous Metal Filter Media For High Purity Gas Filtration," Proceedings of the 37th Annual Technical Meeting of the Institute of Environmental Sciences, pp. 834-840 (1991); Rubow, KL, D.S. Sprause and M.R. Eisenmann, "A Low Pressure Drop Sintered Metal Filter for Ultra-High Purity Gas Systems," Proceedings of the 43rd Annual Technical Meeting of the Institute of Environmental Sciences (1997); and Semiconductor Equipment and Materials International (SEMI) test method SEMI F38-0699 "Test Method for Efficiency Qualification of Point-of-Use Gas Filters," all of which are incorporated herein by reference.

[0199] Calcined metallic filter / aerators that can be coated with an ALD protective coating according to the present disclosure include those described in U.S. Pat. Nos. 5,114,447; 5,487,771; and 8,932,381 and U.S. Patent Application Publication No. 2013 / 0305673.

[0200] Gas filters coated with protective coatings according to the present disclosure can be configured in a variety of ways. In certain exemplary embodiments, the filters can have pore sizes ranging from 1 to 40 μm, or from 1 to 20 μm, or from 20 to 40 μm, or other suitable values. Such gas filters can be present in stainless steel and nickel configurations. Both stainless steel and nickel are susceptible to metal contamination when exposed to corrosive gas environments. The filter matrix of such gas filters can be overcoated with a chemically inert, robust thin film using ALD coating techniques according to the present disclosure. The ALD process can include any number of deposition cycles, for example, ranging from 100 to 5,000 cycles. In particular implementations, ALD alumina films can be deposited using 50 to 1500 cycles using a trimethylaluminum / HO method with deposition of 0.75 Å to 1.25 Å per cycle, e.g., 1.1 Å / cycle, at temperatures that can range from, for example, 200° C. to 300° C., e.g., 250° C., and extended wait and purge times.

[0201] In various embodiments, an ALD alumina coating process can be performed to provide an alumina coating thickness on the gas filter that can range from, for example, 15 nm to 200 nm, hi other embodiments, the ALD alumina coating thickness can range from 20 nm to 50 nm.

[0202] The gas filter coatings described above formed by ALD coating techniques can be performed to produce various aluminum contents in the aluminum oxide film. For example, in various embodiments, the aluminum content of such films can range from 25 atomic percent to 40 atomic percent. In other embodiments, the aluminum content ranges from 28 atomic percent to 35 atomic percent, and in still other embodiments, the aluminum content of the ALD coating is in the aluminum oxide film range of 30 atomic percent to 32 atomic percent.

[0203] In other exemplary embodiments, the gas filter may include an in-line metallic gas filter having a pore size in the range of 2 to 5 μm, the filter including a titanium filter matrix, and the ALD alumina coating having a thickness that can range from 10 nm to 40 nm, e.g., 20 nm. In yet other embodiments, the gas filter may include a nickel-based gas filter matrix having a pore size in the range of 2 to 5 μm, and the ALD alumina coating having a thickness that can range from 10 nm to 40 nm, e.g., 20 nm.

[0204] The protective coatings of the present disclosure may also be used to coat surfaces in chemical reagent supply packages, such as fluid reservoirs and dispensing containers, vaporizer containers for solid reagents, and the like. In addition to the materials stored in and dispensed from such containers, such fluid reservoirs and dispensing containers may also contain various storage media for the stored materials, from which the stored materials can be released from the containers of the material supply package to dispense the materials. Such storage media may include physical adsorbents to which fluids are reversibly adsorbed, ionic storage media for reversible fluid storage, and the like. For example, solid delivery packages of the type disclosed in International Publication WO 2008 / 028170, published March 6, 2008, the disclosure of which is incorporated herein by reference in its entirety, may be coated on their interior surfaces with the protective coatings of the present disclosure.

[0205] Other types of chemical reagent supply packages may be used, where the protective coating of the present disclosure is coated on the interior surface of a supply vessel, such as a fluid supply vessel with regulated internal pressure, for delivering gases such as boron trifluoride, germanium tetrafluoride, silicon tetrafluoride, and other gases utilized in the manufacture of semiconductor products, flat panel displays, and solar panels.

[0206] A further aspect of the present disclosure relates to a method of delivering a gas or vapor flow to a semiconductor processing tool, comprising providing a flow path for the gas or vapor flow from a gas or vapor source to the semiconductor processing tool, and passing the gas or vapor flow through a filter in the flow path to remove extraneous solid material from the flow, the filter including a filter of the type variously described herein.

[0207] In such methods, the gas or vapor stream may comprise any suitable fluid species, and in certain embodiments, such stream comprises dialuminum hexachloride. Particular filters useful for applying such fluids include ALD coatings comprising alumina, and the matrix comprises stainless steel fibers and / or particles.

[0208] The semiconductor processing tool in the above-described methods may be of any suitable type and may include, for example, a deposition furnace.

[0209] As noted above, filters can vary in ALD coating and matrix. In specific embodiments, the filter comprises a calcined matrix of stainless steel fibers and / or particles coated with an ALD coating of alumina, the calcined matrix comprising pores with diameters ranging from 1 to 40 μm, e.g., 1 to 20 μm, 1 to 10 μm, 10 to 20 μm, or other suitable pore size values, and the ALD coating in any of these embodiments has a thickness ranging from 2 to 500 nm.

[0210] In another aspect, the present disclosure relates to the use of ALD to control pore size in microfiltration applications to achieve custom filters that exceed the performance offered by calcined metal matrix filters alone. In this regard, controlling pore size in calcined metal matrix filters becomes increasingly more challenging as target pore sizes decrease to less than 5 μm. With the present disclosure, ALD coatings can be used to effectively reduce pore sizes with a high degree of pore size control and pore size distribution. While coatings deposited by ALD can be substantially thicker than those used in other applications, ALD allows for remarkable control of pore size and pore size distribution while still achieving the benefits of chemical resistance, for example, with ALD coatings of alumina.

[0211] Thus, ALD coatings of fired metal matrix materials can be applied to substantial thicknesses over fired metal matrix structures, with the coating thickness being such as to reduce the pore size in the coated metal matrix structure to very small levels, e.g., submicron pore size levels.

[0212] Such techniques can also be used to create filters with a porosity gradient, such as a porosity gradient from the gas inlet face to the gas outlet face, with relatively larger pore sizes present at the gas inlet face and relatively smaller pore sizes present at the gas outlet face of the filter, with a porosity gradient present between the respective faces of the filter. With such a porosity gradient, a filter can be used, for example, to capture larger particles on the inlet side of the filter and smaller particles on the outlet side of the filter, resulting in an overall more effective filtration.

[0213] Accordingly, the present disclosure contemplates a filter including a porous material matrix coated with an ALD coating, wherein the pore size of the porous metal matrix is ​​reduced by the ALD coating, e.g., the average pore size is reduced by 5% to 95% by the ALD coating relative to a corresponding porous material matrix not coated with the ALD coating.

[0214] The present disclosure also contemplates a filter comprising a porous material matrix coated with an ALD coating, where the coating thickness varies in one direction, resulting in a corresponding pore size gradient in the filter, as described above, e.g., from the inlet face to the outlet face of the filter.

[0215] A further aspect of the present disclosure relates to a method of making a porous filter, comprising coating a porous material matrix with an ALD coating to reduce the average pore size of the porous material matrix. The method can be utilized to achieve a predetermined reduction in the average pore size of the porous material matrix and / or a gradient of different pore sizes in one direction in the porous material matrix.

[0216] The porous material matrix in any of the above aspects and embodiments may comprise a sintered metal matrix of, for example, titanium, stainless steel or other metal matrix material.

[0217] In another aspect, the present disclosure relates to a solid vaporization apparatus comprising a vessel defining an interior volume including a support surface therein for vaporizing a solid material, at least a portion of which has an ALD coating thereon. The support surface may include an interior surface of the vessel, such as a vessel wall surface, and / or the vessel floor, or an extended surface integrally formed with the wall and / or floor surface, such that the support surface includes the interior surface of the vessel and / or the support surface may include a surface of a support member, such as a trade, that provides a support surface for the solid material to be vaporized within the interior volume. The trays may be partially or completely coated with the ALD coating. In other embodiments, the vessel may include a row of vertically spaced trays, each tray providing a support surface for the solid material. Each such tray in the row may be coated with an ALD coating.

[0218] The vessel can be fabricated with an interior wall surface of the vessel, adjacent to its interior volume, coated with an ALD coating. The ALD coating can include, for example, alumina, having a thickness ranging from 2 to 500 nm. The support surface coated with the ALD coating in any of the foregoing embodiments can be a stainless steel surface. The vaporizer vessel itself can be formed from stainless steel. The vaporizer device can be provided in a solid-loaded state, containing a vaporizable solid material on the support surface of the vessel, for example, on the support surface of a stacked tray in the vessel's interior volume. The vaporizable solid material can be of any suitable type and may include, for example, a precursor material for a vapor deposition or ion implantation operation. The vaporizable solid material can include an organometallic compound or a metal halide compound such as aluminum trichloride. It is understood that the ALD coating applied to the support surface of the vessel can be specifically adapted to a particular vaporizable solid material. It is also understood that the ALD coating may be applied to all interior surfaces within the interior volume of the vessel, including the wall and floor surfaces of the vessel, as well as surfaces provided by any trays or other support structures for evaporable solids disposed in the interior volume of the vessel.

[0219] The following disclosure is directed to various examples of coated substrate articles, devices and apparatus of the present disclosure that illustrate particular features, aspects and properties of the coating technology described herein.

[0220] Alumina coatings according to the present disclosure, as previously described herein, can be applied to the surface of holders utilized in vaporizer ampoules, such as the type of ampoule shown in this Figure 3. Figure 15 is a perspective view of a stainless steel holder useful for use in a vaporizer ampoule for delivering aluminum trichloride (AlCl) solid precursor for an aluminum process, where the aluminum trichloride precursor is supported by the holder and vaporized to form aluminum trichloride precursor vapor for exiting the vaporizer ampoule and delivered to the aluminum process through an associated flow circuit. The aluminum process can be used, for example, for metallization of semiconductor device structures on and / or at a suitable wafer substrate.

[0221] Figure 16 is a perspective view of a stainless steel holder of the type shown in Figure 15, in which a coating of alumina has been applied thereon by atomic layer deposition, thereby encapsulating the stainless steel surface in the corrosive environment, including aluminum trichloride (AlCl) exposure, to which the holder is exposed during use and operation of the vaporizer ampoule. Such an alumina coating protects the holder from corrosion and substantially reduces metal contamination of the precursor vapor. In addition to such an alumina coating on the holder, the entire interior surface of the vaporizer ampoule and the exterior surface of the ampoule can be similarly coated to provide extended protection from the corrosive environment resulting from processing and vaporizing the aluminum trichloride (AlCl) solid precursor to generate precursor vapor for aluminum processing or other uses.

[0222] The alumina coating on the surface of the holder and / or other vaporizer ampoule may be of any suitable thickness, for example, a thickness ranging from 20 nm to 250 nm or more. In various embodiments, the thickness of the coating on the holder surface may be in the range of 50 to 125 nm. By performing a corresponding deposition operation with a corresponding number of deposition cycles and deposition times, it is understood that an alumina coating of any suitable thickness may be applied, and the suitable thickness may be determined empirically to provide the desired level of corrosion protection on the metal surface.

[0223] 17 is a close-up schematic of the alumina coating applied by atomic layer deposition to a stainless steel substrate, as described above, in application to a solid precursor holder utilized in a vaporizer ampoule. The alumina coating provides corrosion resistance, prevents chemical reactions with the substrate, and reduces metal contamination during use of the vaporizer to generate aluminum trichloride precursor vapor.

[0224] In another application, yttria coatings can be applied to surfaces of etching equipment or equipment components, such as the surfaces of injector nozzles used in plasma etching tools. Figure 18 shows a channel of a plasma etching equipment coated with yttria (YO). Yttria provides an etch-resistant coating suitable for surfaces and parts with complex geometries, such as high aspect ratio features. When deposited by atomic layer deposition, yttria forms a dense, conformal, pinhole-free coating that resists etching and substantially reduces the shedding and corrosion associated with surfaces without such yttria coatings.

[0225] Yttria coatings can be applied by atomic layer deposition onto alumina, as shown in the enlarged schematic view of Figure 19. In applications to plasma etching equipment and equipment components, ALD yttria layers provide improved corrosion and etch resistance and protect underlying surfaces from harmful plasma exposure, such as exposure to chloro- and fluoro- and other halogen-based plasmas. As a result, ALD yttria layers reduce unwanted particle generation and extend the life of plasma etching equipment components whose surfaces are coated with the yttria coating.

[0226] In another application, load lock components used in etch chamber apparatus are exposed to residual etching chemicals from the etch chamber during use, resulting in severe corrosion of the metal components. One example is a diffuser plate, which may be made from stainless steel or other metal or metal alloy, with a filter membrane formed from nickel or other metal or metal alloy. Such a diffuser plate assembly can be coated with an alumina coating to encapsulate and protect the diffuser plate and filter membrane. Complete encapsulation of the filter membrane prevents corrosion of the membrane.

[0227] Figure 20 is a photograph of a diffuser plate assembly including a stainless steel frame and nickel filter membrane coated with an alumina coating. Figure 21 is a close-up schematic of a diffuser plate assembly in which the stainless steel frame and nickel membrane are encapsulated with ALD alumina. The ALD coating provides a corrosion- and etch-resistant layer that protects against harmful chemicals, such as hydrogen bromide-based chemicals, reducing particles and extending the life of the assembly.

[0228] Another application relates to semiconductor processing equipment exposed to chlorine-based precursors from ALD processes and fluorine-based plasmas from chamber cleaning operations. In such applications, yttria coatings can be used to provide good etch resistance and coat parts with complex geometries. One approach in such applications is the combined use of yttria physical vapor deposition (PVD) and atomic layer deposition (ALD), where ALD is used for thinner coatings of high aspect ratio features and critical elements, and thicker PVD coatings are used for the remainder of the part. In such applications, the ALD yttria layer provides corrosion and etch resistance, protection from fluorine-based chemicals and plasmas, reduces particle generation, and extends the life of parts coated with the protective yttria coating.

[0229] A further application relates to the coating of quartz encapsulation structures, such as the bulbs of ultraviolet (UV) curing lamps used in back-end-of-line (BEOL) and front-end-of-line (FEOL) UV curing operations. In the operation of UV lamps where the bulbs are made from quartz, mercury diffuses into the quartz during operation at the high temperatures involved, e.g., on the order of 1000°C, and such mercury diffusion significantly reduces the UV lamp's degradation and its operational life. To combat this mercury migration into the quartz encapsulant (bulb) material, alumina and / or yttria are coated on the inner surface of the bulb to provide a diffusion barrier layer against mercury penetration into the quartz encapsulant material.

[0230] The plasma channel coating and water channel coating 48 may include an ALD coating of alumina, onto which a physical vapor deposition (PVD) ALD coating of aluminum oxynitride (AlON) is deposited, as shown in the enlarged schematic diagram of FIG. 22 , which shows the aluminum substrate, the ALD coating of alumina, and the PVD coating of AlON. The thicknesses of the respective alumina and aluminum oxynitride coatings can be any suitable thickness. By way of example, the thickness of the alumina coating can range from 0.05 to 5 μm, and the thickness of the PVD coating can range from 2 to 25 μm. In a specific embodiment, the alumina coating has a thickness of 1 μm, and the PVD AlON coating has a thickness of 10 μm. In this structure, the PVD AlON coating provides a device with etch resistance and plasma surface recombination capabilities, and the alumina coating provides an electrical isolation coating in addition to providing etch resistance.

[0231] A further application relates to a dielectric stack for a hot chuck component, which may have the layer structure shown in Figure 23. As shown, an alumina substrate has an electrode metal, e.g., nickel, thereon, and on top of the nickel is an electrical isolation layer of ALD alumina. A PVD coating of aluminum oxynitride is deposited on the alumina layer, and a layer of silicon oxynitride (SiON) deposited by chemical vapor deposition (CVD) is deposited on the AlON layer. In this layer structure, the CVD SiON layer provides clean passages for the contact surfaces and electrical spacers, the PVD AlON layer provides a coefficient of thermal expansion (CTE) buffer layer, the ALD layer of alumina provides the electrical isolation layer, and the nickel provides the electrode metal layer on the alumina substrate.

[0232] A further application relates to a plasma-activated chunk component of a plasma-activated chamber, in which an aluminum part is coated with a multilayer stack, including the multilayer stacks shown in FIGS. 24 and 25. The multilayer stack of FIG. 24 includes a chemical vapor deposited silicon layer on an aluminum substrate, with an ALD layer of zirconia on top of the CVD Si layer. In this multilayer stack, the ALD zirconia layer functions to provide a clean, dense pathway for the contact surface, acting as a diffusion barrier and electrical insulator. The CVD silicon layer provides a clean buffer layer on the aluminum substrate. The multilayer stack of FIG. 25 includes a CVD layer of silicon oxynitride on an aluminum substrate and an ALD layer of alumina on a CVD SiON coating layer, with the ALD alumina layer functioning as an electrical insulator, diffusion barrier, and layer providing a clean, dense pathway for the contact surface. The CVD SiON layer provides a clean buffer layer in the multilayer coating structure.

[0233] A further application of the coating technology of the present disclosure relates to the coating of porous matrices and filter articles, where coatings such as alumina can be deposited by atomic layer deposition, allowing for independent control of penetration depth and coating thickness in the porous matrix or filter material. Either partial or complete alumina coating penetration can be used depending on the article and its particular end use.

[0234] Figure 26 is a micrograph of a porous material with a wall thickness of 1.5 mm and pore sizes of 2-4 μm that has been coated with alumina by atomic layer deposition. Figure 27 is a schematic illustration of an encapsulation membrane, including a membrane formed from stainless steel, nickel, titanium, or other suitable material fully encapsulated by ALD-deposited alumina, which provides corrosion- and etch-resistant encapsulation, protection from chemical corrosion, reduced particle generation, and reduced metal contamination.

[0235] The use of atomic layer deposition as demonstrated allows for independent control of the penetration depth and thickness of the coating. This capability is useful for controlling the pore size and flow restriction of ultrafine membranes, such as those with nominal pore sizes ranging from 20 nm to 250 nm, e.g., those with nominal pore sizes as low as 100 nm.

[0236] Figure 28 is a photomicrograph of a coated filter where the coating is alumina with a coating penetration depth of 35 μm, and Figure 29 is a photomicrograph of a coated filter where the coating is alumina with a coating penetration depth of 175 μm.

[0237] Consistent with the disclosures hereinabove, in one aspect, the present disclosure relates to a solid-state vaporization apparatus comprising a vessel defining an interior volume therein, an outlet configured to exhaust precursor vapor from the vessel, and a support structure within the vessel's interior volume adapted to support a solid precursor material thereon for vaporizing the solid precursor material to form precursor vapor, wherein the solid precursor material comprises an aluminum precursor, and at least a portion of the surface area within the interior volume is coated with an alumina coating. In various embodiments of such a solid-state vaporization apparatus, the surface area may include at least one of the surface area of ​​the support structure and a surface area of ​​the vessel within the interior volume. In other embodiments, the surface area may include a surface area of ​​the support structure and a surface area of ​​the vessel within the interior volume. In yet other embodiments, the surface area within the interior volume coated with the alumina coating comprises stainless steel. In various implementations of the solid-state vaporization apparatus, the alumina coating can have a thickness ranging from 20 to 125 nm. The alumina coating can, for example, comprise an ALD alumina coating in any of the aspects and embodiments described above.

[0238] In another aspect, the present disclosure relates to a method for enhancing the corrosion resistance of a stainless steel structure, material, or device that is exposed to aluminum halides during use or operation, the method comprising coating the stainless steel structure, material, or device with an alumina coating. The alumina coating in such a method can have a thickness in the range of 20 to 125 nm, for example. The alumina coating can be applied, for example, by atomic layer deposition.

[0239] In a further aspect, the present disclosure relates to a semiconductor processing etching structure, component or apparatus that is exposed to an etching medium during use or operation and is coated with a coating comprising a layer of yttria, optionally overlying a layer of alumina in said coating. The etching structure, component or apparatus can include, for example, an etching apparatus injector nozzle.

[0240] Another aspect of the present disclosure relates to a method of enhancing the corrosion and etch resistance of a semiconductor processing etching structure, component or device that is exposed to an etching medium during use or operation, the method comprising coating the structure, component or device with a coating comprising a layer of yttria, the layer of yttria optionally overlying a layer of alumina in said coating.

[0241] Yet another aspect of the present disclosure relates to an etch chamber diffuser plate that includes a nickel film encapsulated by an alumina coating. In such an etch chamber diffuser plate, the alumina coating may include an ALD alumina coating.

[0242] A further aspect of the present disclosure relates to a method of enhancing the corrosion and etch resistance of an etching chamber diffuser plate comprising a nickel film, the method comprising coating the nickel film with an encapsulating coating of alumina, which may comprise, for example, an ALD coating.

[0243] In another aspect, the present disclosure relates to a vapor deposition processing structure, component, or apparatus that is exposed to a halide medium during use or operation, and that is coated with a coating of yttria, including an ALD base coating of yttria and a PVD overcoating of yttria, wherein the surfaces coated with the ALD base coating of yttria and the PVD overcoating of yttria may comprise aluminum.

[0244] A further aspect of the present disclosure relates to a method for enhancing the corrosion and etch resistance of a vapor deposition processing structure, component, or device that is exposed to a halide medium during use or operation, the method comprising coating the structure, component, or device with a coating of yttria, including an ALD base coating of yttria and a PVD overcoating of yttria. As noted above, the structure, component, or device may include an aluminum surface that is coated with a coating of yttria.

[0245] In another aspect, the present disclosure relates to a quartz encapsulation structure, the interior surface of which is coated with an alumina diffusion barrier layer.

[0246] A corresponding aspect of the present disclosure relates to a method for reducing mercury diffusion into a quartz containment structure susceptible to such diffusion during operation of the quartz containment structure, the method comprising coating an interior surface of the quartz containment structure with an alumina diffusion barrier layer.

[0247] In a further aspect, the present disclosure relates to a plasma source structure, component, or apparatus that, during use or operation, is exposed to plasma and voltages in excess of 1000 V, wherein the plasma-wetted surface of the structure, component, or apparatus is coated with an ALD coating of alumina, and the alumina coating is overcoated with a PVD coating of aluminum oxynitride. The plasma-wetted surface can comprise, for example, aluminum or aluminum oxynitride.

[0248] A further aspect of the present disclosure relates to a method for improving the service life of a plasma source structure, component, or device that is exposed to plasmas and voltages greater than 1000 V during use or operation, the method comprising coating a plasma-wetted surface of the structure, component, or device with an ALD coating of alumina, and overcoating the alumina coating with a PVD coating of aluminum oxynitride. As indicated above, the plasma-wetted surface may comprise aluminum or aluminum oxynitride.

[0249] An additional aspect of the present disclosure relates to a dielectric stack comprising sequential layers including an alumina base layer, a nickel electrode layer thereon, an ALD alumina electrical isolation layer on the nickel electrode layer, a PVD aluminum oxynitride thermal expansion buffer layer on the ALD alumina electrical isolation layer, and a CVD silicon oxynitride wafer contact surface and electrical spacer layer on the PVD aluminum oxynitride thermal expansion buffer layer.

[0250] In another aspect of the present disclosure, a plasma-activated structure, component, or device is contemplated that includes an aluminum surface coated with one of the multilayer coatings (i) and (ii): (i) a CVD silicon basecoat on the aluminum surface, and a layer of ALD zirconia on the CVD silicon basecoat; and (ii) a CVD silicon oxynitride basecoat on the aluminum surface, and an ALD alumina layer on the CVD silicon oxynitride basecoat.

[0251] Corresponding methods for reducing particle formation and metal contamination on aluminum surfaces of plasma-activated structures, components, or devices are contemplated, comprising coating the aluminum surface with one of (i) and (ii) multilayer coatings: (i) a CVD silicon base coat on the aluminum surface, and a layer of ALD zirconia on the CVD silicon base coat; and (ii) a CVD silicon oxynitride base coat on the aluminum surface, and an ALD alumina layer on the CVD silicon oxynitride base coat.

[0252] In another aspect, the present disclosure contemplates a porous matrix filter including a membrane formed from stainless steel, nickel, or titanium, wherein the membrane is encapsulated by alumina to a penetration depth of the membrane ranging from 20 to 2000 μm. More particularly, in various embodiments, the porosity can have a nominal pore size ranging from 10 to 1000 nm.

[0253] Another aspect of the present disclosure relates to a method of making a porous matrix filter, the method comprising encapsulating a membrane formed from stainless steel, nickel, or titanium with alumina to a coating penetration depth ranging from 20 to 2000 μm. In a specific embodiment of such a method, the encapsulating step comprises ALD of alumina, which is carried out to produce porosity in the porous matrix filter having a nominal pore size ranging from 10 to 1000 nm.

[0254] While the present disclosure has been described herein with reference to particular aspects, features, and exemplary embodiments, it is understood that the applicability of the present disclosure is not so limited, but rather extends to and encompasses other variations, modifications, and alternative embodiments, as would suggest themselves to one skilled in the art of the present disclosure based on the description herein. Correspondingly, the present disclosure, as hereinafter claimed, is intended to be broadly construed and understood, as including all such variations, modifications, and alternative embodiments within its spirit and scope.

Claims

1. 1. A method of forming a patterned ALD coating on a substrate portion, comprising: masking an area of ​​the substrate portion with a mask comprising a sealing sheet or jig; coating a substrate portion with an ALD coating; removing the mask along with the ALD coating from the masked area of ​​the substrate portion; wherein the mask excludes photoresist and the substrate portion is a component of a semiconductor manufacturing device.

2. The method of claim 1 , wherein the ALD coating comprises an insulating metal oxide selected from alumina, yttria, zirconia, and titania.

3. The method of claim 1 , wherein the ALD coating is aluminum oxide.

4. The method of claim 1 , wherein the coating has a thickness in the range of 20 nm to 125 nm.

5. The method of claim 1 , wherein the coating has a thickness in the range of 5 nm to 5 μm.

6. 10. The method of claim 1, wherein the substrate portion comprises at least one feature selected from the group consisting of deep holes, channels, three-dimensional features, hardware selected from screws and nuts, porous membranes, filters, three-dimensional network structures, and structures having a bonded pore matrix.

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