CN111593324A - Porous matrix filter and method of making the same - Google Patents

Abstract

A porous substrate filter and method of making the same are described. In various applications, a substrate includes a metal surface susceptible to forming an oxide, nitride, fluoride or chloride of such a metal thereon, wherein the metal surface is configured to be contacted, in use, with a gas, solid or liquid that reacts with the metal surface to form a reaction product that is detrimental to the substrate article, structure, material or equipment. The metal surface is coated with a protective coating that prevents the coated surface from reacting with the reactive gas and/or otherwise improving the electrical, chemical, thermal, or structural properties of the substrate article or apparatus. Various methods of coating the metal surface and for selecting the coating material utilized are described.

Description

Porous matrix filter and method of making the same

Information about divisional applications

This application is a divisional application of an invention patent application with an application date of February 13, 2016, an application number of "201680018518.5", and an invention title of "coating for enhancing the properties and performance of substrate products and devices".

Cross-references to related applications

This application claims the benefit of the following U.S. Provisional Patent Application under the terms of 35 U.S.C. § 119: February 13, 2015 in the name of Carlo Waldfried et al and in "Thin Film Atomic Layer Deposition" U.S. Provisional Patent Application No. 62/116,181 filed by THIN FILM ATOMIC LAYER DEPOSITION COATINGS; filed May 28, 2015 in the name of Bryan C. Hendrix et al. and U.S. Provisional Patent Application No. 62/167,890, filed "COATINGS TO PREVENT TRANSPORT OFTRACE METALS BY AL2CL6 VAPOR"; published July 2, 2015 U.S. Provisional Patent Application in the Name of Lane C. Hendricks et al. for "COATINGS FOR ENHANCEMENT OF PROPERTIES AND PERFORMANCE OF SUBSTRATEARTICLES AND APPARATUS" Case No. 62/188,333; and September 21, 2015 in the name of Brian C. Hendricks et al and in "COATINGS FOR ENHANCEMENT OF PROPERTIES AND PERFORMANCE OF SUBSTRATEARTICLES AND APPARATUS)", U.S. Provisional Patent Application No. 62/221,594. The disclosures of such US Provisional Patent Application Nos. 62/116,181, 62/167,890, 62/188,333 and 62/221,594 are hereby incorporated by reference in their respective entireties for all purposes .

technical field

The present invention generally relates to structures suitable for use in a variety of substrate articles and devices (eg, with respect to structures having surfaces susceptible to the formation of undesired oxide, nitride, fluoride, chloride or other halide contaminant species thereon and device) coating. In certain aspects, the present invention relates to semiconductor fabrication equipment and methods of enhancing its performance, and more particularly to semiconductor fabrication equipment susceptible to contamination and particle deposition associated with the presence of aluminum hexachloride vapor in such equipment , and to compositions and methods for combating this adverse contamination and particle deposition.

Background technique

In many areas of research, it is encountered that surfaces containing prone to forming contaminant species such as undesired oxides, nitrides and halides ( For example, fluoride and/or chloride) contaminant species of aluminum, anodized aluminum, quartz, stainless steel, etc. surface) structure, material and device.

In the field of semiconductor manufacturing, aluminum and aluminum-containing materials are widely used. Although aluminum as a metallization material has been significantly replaced by copper in nanoscale integrated circuit applications, aluminum continues to be widely used as a wire bonding and connection material, and as a barrier layer in thin film materials (eg, AlN films) , piezoelectric device components, cold cathode materials, etc., and in compound semiconductor compositions (which are used in applications such as LEDs and other optoelectronic devices ₎ or in _Al2O3 layers as dielectrics, dielectric dopants, barriers, optical coating etc.

In many of these applications, halogen gases are used in semiconductor fabrication equipment for treating films in device fabrication operations, or as co-flow cleaners for removing surfaces deposited on semiconductor fabrication equipment and Accumulated contamination on components. These halogen gases can contain chlorinated species that can reactively form aluminum hexachloride (Al ₂ Cl ) upon contact with aluminum present in the device (eg, on a wafer or on a surface or component of the device) ₆ ) Steam. This aluminum hexachloride vapor can in turn attack stainless steel surfaces and components in semiconductor fabrication equipment and serve to deliver measurable levels of metals such as chromium, iron, and nickel to wafers undergoing processing.

Another type of application uses Al ₂ Cl ₆ vapor to deposit aluminum-containing films. Although _Al2O3 is widely deposited by _ALD using trimethylaluminum as a source reagent, trimethylaluminum is a pyrophoric liquid with significant safety and management costs. In a solids vaporizer (eg, a solids vaporizer unit of the type marketed under the trademark ProE-Vap by Entegris, Inc., Billerica, Massachusetts, USA), the solids Al ₂ Cl ₆ vapor is easily generated above AlCl ₃ .

Stainless steel components of semiconductor manufacturing equipment may be formed from 316 stainless steel or other stainless steel alloys that are typically electropolished. This electropolishing typically coats the surface with a passive oxide layer containing chromium, iron, nickel and other alloying components. In addition, such metal components may form surface traces of corresponding oxides through natural oxidation processes. Thus, when aluminum hexachloride encounters such a metal oxide, the metal oxide reacts with aluminum hexachloride to form the corresponding fumed metal aluminum chloride compound, which can be delivered to the wafer and semiconductor device or device precursor structures and can deposit trace metals or otherwise damage the products being fabricated in the device. Alternatively, metal oxides can react with Al ₂ Cl ₆ vapors to form Al ₂ O ₃ and particulate metal chlorides that can be transported to the device structure and cause damage. Additionally, the AlCl3 solid can contact the metal _oxide surface to form vapor metal aluminum chloride or solid chloride particles.

Therefore, inhibiting the detrimental interaction of aluminum hexachloride with metal surfaces and components in this semiconductor fabrication equipment and other thin film deposition or etching equipment would be a significant improvement.

There is also a continuing need for coatings for a variety of industrial applications that are dense, pinhole-free, and defect-free, and that provide other coating qualities and benefits, such as electrical insulation of parts, conformal coating of parts capacity, chemical and etch resistance, corrosion resistance, diffusion barrier properties, and adhesion layer properties.

SUMMARY OF THE INVENTION

The present invention relates generally to coatings suitable for use in a variety of substrate articles, structures, materials, and equipment, and in particular to semiconductor fabrication equipment and methods of enhancing the performance thereof, and more particularly to susceptibility to exposure to hexachloride The presence of aluminum sulfide in such equipment is associated with contamination and particle deposition in semiconductor fabrication equipment, and relates to compositions and methods for combating such adverse contamination and particle deposition.

In one aspect, the present invention relates to a structure, material or device comprising a metal surface on which oxides, nitrides or halides of the metal are prone to form, the metal surface being configured to The use or operation of the structure, material or device is in contact with a gas, solid or liquid which reacts with the metal oxide, nitride or halide to form a reaction to the structure, material or halide. Apparatus and reaction products detrimental to its use or operation, wherein the metal surface is coated with a protective coating that prevents the coated surface from reacting with the reactive gas.

In one aspect, the present invention relates to a semiconductor fabrication device comprising a metal surface on which oxides, nitrides or halides of the metal are prone to form, the metal surface being configured to The operation of the device is in contact with a gas, solid or liquid that reacts with the metal oxide, nitride or halide to form reaction products (e.g., particles) that are detrimental to the device and its operation reaction product and/or steam reaction product), wherein the metal surface is coated with a protective coating that prevents the coated surface from reacting with the reactive gas.

Another aspect of the invention relates to a method of improving the performance of a structure, material or device comprising a metal surface that is prone to forming thereon oxides, nitrides or halides of the metal, wherein the metal The surface is configured to come into contact with a gas, solid or liquid that reacts with the metal oxide, nitride or halide to form a said structure, material or device and reaction products detrimental to its use or operation, said method comprising coating said metal surface with a protective coating, said protective coating preventing said coated surface from interacting with said reactive gas to react.

In another aspect, the present invention relates to a method of improving the performance of a semiconductor fabrication device comprising a metal surface that readily forms thereon oxides, nitrides or halides of the metal, wherein the metal The surface is configured to come into contact with the gas, solid or liquid during operation of the device that reacts with the metal oxide, nitride or halide to form forms that are detrimental to the device and its operation The reaction product of , the method includes coating the metal surface with a protective coating that prevents the coated surface from reacting with the reactive gas.

In another aspect, the present invention relates to improving the performance of semiconductor fabrication equipment in contact with reactive solids.

According to another aspect of the present invention, thin film atomic layer deposition coatings for industrial applications are provided. Thin film coatings according to the present invention are described in the specification herein.

Another aspect of the invention relates to a composite ALD coating comprising layers of different ALD product materials.

Another aspect of the invention relates to a composite coating comprising at least one ALD layer and at least one deposited layer that is not an ALD layer.

In another aspect, the present invention relates to a method of forming a patterned ALD coating on a substrate, comprising patterning on the substrate with a layer of surface stop material effective to prevent ALD film growth.

In another aspect, the present invention relates to a method of filling and/or sealing a surface infirmity of a material, the method comprising applying an ALD coating to the material in a thickness that affects the filling and/or sealing of the defect on the surface defects.

Another aspect of the present invention relates to a filter comprising a matrix of fibers and/or particles formed from metallic and/or polymeric materials, wherein the matrix of fibers and/or particles is in its having an ALD coating thereon, wherein the ALD coating does not alter the pore volume of the matrix of fibers and/or particles more than the corresponding matrix of fibers and/or particles lacking the ALD coating thereon at 5%, and wherein when the fibers and/or particles are formed of a metal and the ALD coating includes a metal, the metal of the ALD coating is different from the metal of the fibers and/or particles.

Yet another aspect of the present invention relates to a method of delivering a gaseous or vapor stream to a semiconductor processing tool, the method comprising providing the gaseous or vapor stream with a flow from a source of the gaseous or vapor stream to the semiconductor processing tool A flow path and flowing the gaseous or vapor stream in the flow path through a filter to remove foreign solid material from the flow, wherein the filter includes a filter of the present invention, as different herein described.

In another aspect, the present invention relates to a filter comprising a sintered matrix of stainless steel fibers and/or particles coated with an ALD alumina coating, wherein the sintered matrix comprises a For example, pores of diameter in the range from 10 μm to 20 μm) and the ALD coating has a thickness in the range from 2 nm to 500 nm.

Another aspect of the invention relates to a solids vaporizer device comprising a vessel defining an interior volume containing therein a support surface for solid material to be vaporized, wherein at least a portion of the support surface is in its Has ALD coating on it.

In another aspect, the invention relates to a thin film coating consisting of one or more layers, wherein at least one of the layers is deposited by atomic layer deposition.

的膜厚度的ALD涂层。Another aspect of the present invention relates to a device having more than

The film thickness of the ALD coating.

Another aspect of the present invention relates to an ALD coating comprising an extremely dense, pinhole-free, defect-free layer.

Yet another aspect of the present invention relates to a thin film coating deposited on a portion of the surface of an integrated circuit device other than a silicon wafer.

In another aspect, the present invention relates to an ALD coating composed of an insulating metal oxide and a metal.

Another aspect of the present invention relates to an ALD coating that can be deposited at temperatures ranging from 20°C to 400°C.

Another aspect of the invention relates to an ALD coating comprising a single film having a defined stoichiometry.

Another aspect of the invention relates to a thin film coating comprising an ALD layer in combination with at least one other layer deposited by different deposition techniques.

In another aspect, the present invention relates to a multilayer ALD coating having a coating thickness of no more than 2 μm.

Another aspect of the invention relates to a coating of an ALD material selected from the group consisting of oxides, aluminum oxides, aluminum oxynitrides, yttria, yttria-alumina mixtures, silicon oxides, Silicon oxynitride, transition metal oxide, transition metal oxynitride, rare earth metal oxide and rare earth metal oxynitride.

Another aspect of the invention relates to a method of forming a patterned ALD coating on a portion of a substrate, the method comprising: uniformly coating the portion with the ALD coating; desired coating material.

Another method aspect of the invention relates to a method of forming a patterned ALD coating on a portion of a substrate, the method comprising: masking regions of the portion; coating the portion with the ALD coating; and removing the ALD coating from the portion of the mask area.

Yet another method aspect of the present invention relates to a method of forming a patterned ALD coating on a substrate portion, the method comprising: subjecting the substrate portion to a material including a surface termination feature that inhibits ALD film growth patterning; and coating the patterned substrate portion with an ALD coating.

Another aspect of the invention relates to a method of electrically insulating a substrate portion comprising applying a defect-free, pin-hole-free, dense, electrically insulating ALD coating to the substrate portion.

In another aspect, the present invention relates to a coating on a surface of a substrate comprising an ALD coating having chemical and etch resistance properties.

Another aspect of the present invention relates to a coating on a substrate surface that includes an ALD anti-corrosion coating.

Another aspect of the invention relates to a coating on a substrate surface that includes an ALD diffusion barrier layer.

Yet another aspect of the present invention relates to a coating on a surface of a substrate that includes an ALD adhesion layer.

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

In another aspect, the present invention relates to a porous filter comprising a fiber metal membrane coated with a chemically resistant ALD coating.

Another aspect of the present invention relates to a filter comprising a porous material substrate coated with an ALD coating, wherein the porous metal substrate is The average pore size has been reduced by the ALD coating.

Another aspect of the invention relates to a filter comprising a matrix of porous material coated with an ALD coating, wherein the thickness of the coating is directionally varied to provide a corresponding pore size gradient in the filter.

In another aspect, the present invention 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.

In another aspect, the invention relates to a solids vaporizer apparatus comprising a vessel defining an interior volume therein, an outlet configured to discharge precursor vapor from the vessel, and a support in the interior volume of the vessel a structure, the support structure is adapted to support a solid precursor material thereon to volatilize the solid precursor material to form the precursor vapor, wherein the solid precursor material comprises an aluminum precursor, and wherein the At least a portion of the surface region in the interior volume is coated with an alumina coating.

Another aspect of the invention relates to a method of enhancing the corrosion resistance of a stainless steel structure, material or device that is exposed to aluminum halide in use or operation, the method comprising coating with aluminum oxide to coat the stainless steel structure, material or device.

Another aspect of the invention relates to a semiconductor processing etch structure, component or device that is exposed to an etch medium in use or operation, the structure, component or device being coated with a coating including an oxide A coating of an yttrium layer, wherein the yttrium oxide layer is optionally overlaid on an aluminum oxide layer in the coating.

Yet another aspect of the present invention relates to a method of enhancing the corrosion and etch resistance of a semiconductor processing etched structure, component or device that is exposed to an etching medium during use or operation, such that The method includes coating the structure, component or device with a coating comprising a layer of yttrium oxide, wherein the layer of yttrium oxide optionally overlies a layer of aluminum oxide in the coating.

In another aspect, the present invention relates to an etch chamber diffuser plate comprising a nickel film encapsulated with an alumina coating.

Another aspect of the present invention relates to a method of enhancing the corrosion and etch resistance of an etch chamber diffuser plate comprising a nickel thin film, comprising coating the nickel thin film with an alumina encapsulation coating.

In another aspect, the present invention relates to a vapor deposition processing structure, assembly or apparatus exposed to a halide medium in use or operation, the structure, assembly or apparatus being coated with a yttrium oxide coating, the oxide Yttrium coatings include ALD yttrium oxide base coatings and PVD yttrium oxide top coatings.

In yet another aspect, the present invention relates to a method of enhancing the corrosion and etch resistance of a vapor deposition process structure, component or device that is exposed to halogenation in use or operation The method includes coating the structure, component, or device with a yttrium oxide coating, the yttrium oxide coating including an ALD yttrium oxide base coating and a PVD yttrium oxide top coating.

Yet another aspect of the present invention relates to a quartz housing structure having an alumina diffusion barrier layer coated on its interior surface.

Another aspect of the present invention relates to a method of reducing the diffusion of mercury into a quartz housing structure susceptible to such diffusion in its operation, the method comprising coating with an alumina diffusion barrier layer cover the inner surface of the quartz housing structure.

Yet another aspect of the invention relates to a plasma source structure, assembly or device exposed to plasma and voltages in excess of 1000V in use or operation, wherein the plasma wetted surface of the structure, assembly or device is coated It is coated with ALD alumina coating, and the alumina coating is overcoated with PVD alumina oxynitride coating.

In one aspect, the present invention relates to a method of enhancing the service life of a plasma source structure, assembly or device that is exposed to plasma and voltages in excess of 1000V in use or operation, The method includes coating a plasma wetted surface of the structure, component or device with an ALD alumina coating and overcoating the alumina coating with a PVD alumina oxynitride coating.

In another aspect, the invention relates to a dielectric stack comprising a sequence of layers comprising an alumina base layer, a nickel electrode layer on the alumina base layer, a nickel electrode layer on the nickel electrode layer ALD aluminum oxide electrical isolation layer, a PVD aluminum oxynitride thermal expansion buffer layer on the ALD aluminum oxide electrical isolation layer, and a CVD silicon oxynitride wafer contact surface and electrical spacer layer on the PVD aluminum oxynitride thermal expansion buffer layer .

In another aspect, the present invention relates to a plasma activated structure, assembly or device comprising an aluminum surface coated with one of the multilayer coatings of (i) and (ii): (i) located in the a CVD silicon base coat on the aluminum surface, and an ALD zirconia layer on the CVD silicon base coat; and (ii) a CVD silicon oxynitride base coat on the aluminum surface, and on the CVD silicon base coat ALD aluminum oxide layer on CVD silicon oxynitride base coat.

Another aspect of the invention relates to a method of reducing particle formation and metal contamination of an aluminum surface of a plasma-activated structure, component or device, the method comprising applying one of the multilayer coatings of (i) and (ii) to coat the aluminum surface: (i) a CVD silicon basecoat on the aluminum surface, and an ALD zirconia layer on the CVD silicon basecoat; and (ii) on the aluminum surface a CVD silicon oxynitride base coating on top, and an ALD aluminum oxide layer on the CVD silicon oxynitride base coating.

Contemplated in another aspect of the present invention is a porous matrix filter comprising a membrane formed of stainless steel, nickel or titanium, wherein the membrane is encapsulated with alumina to a thickness of from 20 μm to 2000 μm range of coating penetration depths.

In a corresponding method aspect, the present invention relates to a method of making a porous matrix filter comprising encapsulating a film formed of stainless steel, nickel or titanium with alumina for coating penetration in the range from 20 μm to 2000 μm depth.

Other aspects, features and embodiments of the present invention will become apparent from the ensuing description and appended claims.

Description of drawings

1 is a schematic representation of a deposition furnace of a semiconductor wafer processing tool in accordance with one aspect of the present invention.

2 is a schematic representation of a deposition furnace process system for delivering a vaporizer with a solid source in the form _of an ampoule for vaporizing AlCl to form Al ₂ Cl ₆ vapor), using Al ₂ Cl ₆ vapor to coat the wafer, where the tray and interior surfaces of the ampoule are coated with Al ₂ O ₃ and all valves, tubes and filters downstream of the ampoule are coated with Al ₂ O ₃ .

3 is a perspective partial cutaway view of a vaporizer vessel with a retainer to help facilitate contact of gas with vapor from material supported by the retainer.

4 is a photomicrograph at 15K magnification of the surface of a porous metal frit of a type useful in filter elements according to another aspect of the present invention.

Figure 5 is a photomicrograph at 20,000X magnification of the surface _of electropolished 316L stainless steel not exposed to AlCl3.

Figure 6 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 is a photomicrograph at 50,000X magnification of a cross _- section of electropolished 316L stainless steel not exposed at all to AlCl3.

Figure 8 is a photomicrograph at 20,000X magnification of uncoated 316L stainless steel after exposure to AlCl3 at 120°C for ₁₀ days in an anhydrous environment.

9 is a photomicrograph at 35,000X magnification of electropolished 316L stainless steel after exposure to AlCl3 at 120°C for ₁₀ days in an anhydrous environment, showing multiple pits along the surface.

Figure 10 is a 35,000X magnification of electropolished 316L stainless steel coated by 100 ALD cycles _{of Al2O3} with trimethylaluminum and water prior to exposure to anhydrous AlCl3 at ₁₂₀ °C for 10 days rate photomicrographs.

Figure 11 is a 35,000X magnification of electropolished 316L stainless steel coated by 1000 ALD cycles _{of Al2O3} with trimethylaluminum and water prior to exposure to anhydrous AlCl3 at ₁₂₀ °C for 10 days rate photomicrographs.

厚的氧化铝涂层，且样本取样片12及13未经涂覆。Figure 12 is a composite photograph of sample stainless steel coupons of which sample coupons 2 and ₃ were taken after exposure to AlCl at 155°C for nine days

Thick alumina coating, and sample coupons 12 and 13 were uncoated.

Figure 13 is an overhead scanning electron microscope (SEM) micrograph of an alumina coated stainless steel sample after exposure to WCl ₅ at 220°C for 10 days.

14 is a focused ion beam (FIB) cross-section of the edge of the coating in the sample of FIG. 13 after exposure to WCl ₅ for 10 days at 220°C.

15 is a perspective view of a stainless steel holder useful for use in vaporizer ampoules for aluminum trichloride (AlCl ₃ ) solid precursor delivery for aluminum processes, wherein the aluminum trichloride precursor is supported by the holder and volatilized to Aluminum trichloride precursor vapor is formed to be discharged from the vaporizer ampoule and delivered to the aluminum process through an associated flow line.

Figure 16 is a perspective view of a stainless steel holder of the type shown in Figure 15 having an alumina coating thereon, such as by atomic layer deposition, such that the stainless steel surface is made of alumina in a corrosive environment Coating encapsulates the corrosive environment involving aluminum trichloride (AlCl ₃ ) exposure to which the holder is subjected during use and operation of the vaporizer ampoule.

17 is a schematic elevation view of an aluminum oxide coating applied to a stainless steel substrate by atomic layer deposition to provide corrosion resistance, prevent chemical reactions with the substrate, and reduce metal in use Pollution.

Figure 18 shows the channels of a plasma etch device coated with yttrium _oxide ( _Y2O3 ).

Figure 19 is a schematic elevation view of a yttrium oxide coating applied by atomic layer deposition on alumina.

Figure 20 is a photograph of a diffuser plate assembly comprising a stainless steel frame and a nickel filter membrane as coated with an alumina coating.

Figure 21 is a schematic elevation view of a diffuser plate assembly with a stainless steel frame and nickel membrane encapsulated with ALD alumina.

22 is a schematic elevation view of a coating structure comprising an aluminum substrate, an ALD alumina coating, and a PVD AlON coating.

Figure 23 is a schematic elevation view of the layer structure of a dielectric stack for a thermal chuck assembly with an alumina substrate having electrode metal thereon on which an ALD alumina electrical isolation layer is located, PVD oxynitride An aluminum coating is on the ALD aluminum oxide electrical isolation layer, and a chemical vapor deposition (CVD) deposited silicon oxynitride (SiON) layer is on the PVD aluminum oxynitride coating.

24 is a schematic elevation view of a multilayer stack comprising a chemical vapor deposition applied silicon layer on an aluminum substrate, with an ALD zirconia layer on a CVD Si layer.

25 is a schematic elevation view of a multi-layer stack including a CVD silicon oxynitride layer on an aluminum substrate and an ALD aluminum oxide layer on a CVD SiON coating.

26 is a photomicrograph of a porous material having a wall thickness of 1.5 mm and a pore size of 2 μm to 4 μm, coated with alumina by atomic layer deposition.

Figure 27 is a schematic representation of an encapsulated film comprising a film formed of stainless steel, nickel, titanium or other suitable material that has been fully encapsulated with alumina deposited by ALD.

Figure 28 is a photomicrograph of a coated filter wherein the coating is alumina with a coating penetration depth of 35 μm.

Figure 29 is a photomicrograph of a coated filter wherein the coating is alumina with a coating penetration depth of 175 μm.

Detailed ways

The present invention generally relates to coatings suitable for use in a variety of substrate articles, materials, structures and devices. In various aspects, the present invention relates to semiconductor fabrication equipment and methods of enhancing its performance, and more particularly to semiconductor fabrication susceptible to contamination and particle deposition associated with the presence of aluminum hexachloride vapor in such equipment apparatus, and to compositions and methods for combating this adverse contamination and particle deposition.

As used herein, identification of a carbon number range (eg, in _C1 to C12 alkyl) is intended to encompass each _of the component carbon number moieties within that range, such that the stated range is encompassed For each intervening carbon number within and any other stated or intervening carbon number, it is further understood that sub-ranges of carbon numbers within the stated range of carbon numbers may independently be included within the scope of the invention within smaller ranges of carbon numbers, and Specifically, such carbon number ranges excluding one or more carbon numbers are included in the invention, and subranges excluding either or both of the carbon number limits of the stated ranges are also included in the invention. Thus, _C1 to _C12 alkyl is intended to include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl, These types of straight-chain as well as branched-chain groups are included. It will thus be appreciated that, in certain embodiments of the present invention, the identification _of carbon number ranges (eg, _C1 to C12) as broadly applicable to substituted moieties enables further limitation of carbon number ranges, as those with substituted moieties A subgroup of a portion of a carbon number range within a broader specification. By way of example, in certain embodiments _of the invention, carbon number ranges (eg, _C1 to C12 alkyl) may be specified more restrictively to encompass subranges, such as _C1 to _C4 alkyl, _C2 to _C8 alkyl, _C2 to _C4 alkyl, C3 to _C5 alkyl, or any other sub _- range within a broad range of carbon numbers. In other words, a carbon number range is considered to affirmatively state each of the carbon number species in the range as a selected group of substituents, moieties or compounds to which the range applies, from which A group selects a particular one of the members of the selection group as an ordinal carbon number sub-range or as a particular carbon number species within this selection group.

Within the broad scope of the present invention, the same construction and selection flexibility applies to stoichiometric coefficients specifying the number of atoms, functional groups, ions or moieties (with respect to specified ranges, numerical constraints (eg, inequalities, greater than constraints, less than constraints)) and values, as well as oxidation state and other variables that determine the particular form, charge state, and composition applicable to dopant sources, implant species, and chemical entities.

"Alkyl" as used herein includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, isopentyl, and the like. "Aryl" as used herein includes hydrocarbons or benzene derivatives derived from benzene, said hydrocarbons and said benzene derivatives being unsaturated aromatic carbocyclic groups of from 6 to 10 carbon atoms . Aryl groups can have single or multiple rings. The term "aryl" as used herein also includes substituted aryl groups. Examples include, but are not limited to, phenyl, naphthyl, xylene, phenylethane, substituted phenyl, substituted naphthyl, substituted xylene, substituted phenylethane, and the like. "Cycloalkyl" as used herein includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. In all formulae herein, a carbon number range will be deemed to specify a series of consecutive alternative carbon-containing moieties (including all moieties containing the number of carbon atoms intermediate the endpoints of the carbon number within the specified range and containing equal to the specified range of carbon atoms) part of the number of carbon atoms of the endpoints), for example, _C1 to _C6 include _C1 , _C2 , C3, _C4 , _C5 , and _C6 and each _of such broader ranges may be referred to as such The number of carbons within the range is further limited to its sub-ranges. Thus, for example, a range C ₁ to C ₆ would include provisions for subranges within a broader range (eg, C ₁ to C ₃ , C ₁ to C ₄ , C ₂ to C ₆ , C ₄ to C ₆ , etc.) and may be further limited by the specification of the sub-ranges.

In one aspect, the present invention relates to a structure, material or device comprising a metal surface that readily forms thereon an oxide, nitride or halide (fluoride, chloride, iodide) of the metal and/or bromide), the metal surface is configured to come into contact with a gas, solid or liquid in use or operation of the structure, material or device, the gas, solid or liquid and the metal oxide, nitrogen compound or halide to form a reaction product that is detrimental to the structure, material or device and its use or operation, wherein the metal surface is coated with a coating that prevents the coated surface from reacting with the reactive gas protective coating.

In one aspect, the present invention relates to a semiconductor fabrication device comprising a metal surface on which oxides, nitrides or halides of the metal are prone to form, the metal surface being configured to Use or operation of the device in contact with a gas, solid or liquid that reacts with the metal to form a reaction product that is detrimental to the device and its use or operation, wherein the metal surface is coated There is a protective coating that prevents the coated surface from reacting with the reactive gas.

In this semiconductor fabrication apparatus, the metal oxide may include, in various embodiments, at least one oxide of one or more of Cr, Fe, Co, and Ni, or in other embodiments, the metal The oxide may include at least one oxide of one or more of Cr, Fe, and Ni. For example, metal nitrides can be formed from iron or cobalt in the presence of ammonia during processing in the presence of ammonia, wherein the resulting iron or cobalt _nitride is subsequently reacted with AlCl3 or _TiCl4 . Metal halides may form on metal surfaces during etching operations or cleaning cycle operations. In various embodiments, the metal surface may include a stainless steel surface. In certain embodiments, the gas that reacts with the metal oxide, nitride or halide to form reaction products that are detrimental to the device and its use or operation includes Al ₂ Cl ₆ .

In certain applications, the protective coating may include one or more of coating materials selected from the group consisting of: Al ₂ O ₃ ; oxides of the formula MO, where M is Ca, Mg, or Be; Oxides of _formula M'O2, wherein M' is a stoichiometrically acceptable metal; and oxides of _{formula Ln2O3} , wherein Ln is a lanthanide such as La, Sc, or Y. More generally, the protective coating may include metal oxides that have a free energy of reaction greater than or equal to zero with materials that come into contact with the metal surface during operation of the device.

Another aspect of the invention relates to a method of improving the performance of a structure, material or device comprising a metal surface that is prone to forming thereon oxides, nitrides or halides of the metal, wherein the metal The surface is configured to come into contact with a gas, solid or liquid that reacts with the metal oxide, nitride or halide to form a said structure, material or device and reaction products detrimental to its use or operation, said method comprising coating said metal surface with a protective coating, said protective coating preventing said coated surface from interacting with said reactive gas to react.

In another aspect, the present invention relates to a method of improving the performance of a semiconductor fabrication device comprising a metal surface that readily forms thereon oxides, nitrides or halides of the metal, wherein the metal the surface is configured to come into contact with a gas during use or operation of the device that reacts with the metal oxide, nitride or halide to form reaction products that are detrimental to the device and its use or operation, The method includes coating the metal surface with a protective coating that prevents the coated surface from reacting with the reactive gas.

In various embodiments, the metal oxide, nitride, or halide may 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 may be included, or any other suitable metal oxide, nitride or halide species. For example, the metal surface may include stainless steel. Gases that react with metal oxides, nitrides, or halides to form reaction products that are detrimental to structures, materials, or devices and their use or operation may include Al ₂ Cl ₆ .

The protective coating applied to the metal surface in the foregoing method may comprise one or more of coating materials selected from the group consisting of: Al ₂ O ₃ ; oxides of formula MO, wherein M is Ca, Mg or Be; oxides of the _formula M'O2, where M' is a stoichiometrically acceptable metal; and oxides of the _{formula Ln2O3} , where Ln is a lanthanide such as La, Sc, or Y. More generally, the protective coating may include metal oxides that have a free energy of reaction greater than or equal to zero with gases that come into contact with the metal surface during use or operation of the structure, material, or device.

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

ALD is the preferred technique for applying protective coatings to metal surfaces. In certain applications, plasma-enhanced ALD may be utilized as an ALD process for forming protective coatings on metal surfaces. In various ALD embodiments, the protective coating may include Al ₂ O ₃ . For example, such a protective coating can be applied by atomic layer deposition including a process sequence in which the protective coating is formed in a cyclic ALD process utilizing trimethylaluminum and ozone, or alternatively, by including a cycle in which the protective coating is formed The ALD process is applied by atomic layer deposition in a process sequence utilizing trimethylaluminum and water to form the protective coating.

In other ALD embodiments of the method, the protective coating may comprise a metal oxide of formula MO, where M is Ca, Mg, or Be. For its application, atomic layer deposition may include: a process sequence wherein the protective coating is formed using a cyclopentadienyl M compound and ozone in a cyclic ALD process, or wherein a cyclopentadienyl group is utilized in a cyclic ALD process A process sequence in which the protective coating is formed with an M compound and water, or a process sequence in which the protective coating is formed using an Mβ-diketone compound and ozone in a cyclic ALD process, or other suitable process sequence and metal oxide precursor compound. A wide variety of precursor ligands are available for the deposition of protective coatings, including but not limited to: H, _C1 - _C10 alkyl, linear, branched or cyclic, saturated or unsaturated; aromatic, hetero Ring, alkoxy, cycloalkyl, silyl, silylalkyl, silylamide, trimethylsilylsilyl-substituted alkyl, trioxane Alkylsilyl-substituted alkynes and trialkylsilylamide-substituted alkynes, dialkylamides, ethylene, acetylene, alkynes, substituted alkenes, substituted alkynes, dienes, cyclopentadienylpropanedi alkenes, amines, alkylamines or bidentate amines, ammonia, _RNH2 (wherein R is an organic (e.g.) hydrocarbyl, substituent), amidino, guanidino, diazadiene cyclopentadienyl, Oximes, hydroxylamines, acetates, beta-diketones, beta-ketimine salts, nitriles, nitrates, sulfates, phosphates, halo; hydroxy, substituted hydroxy, and combinations and derivatives thereof.

In still other ALD embodiments of the method of applying a protective coating to a metal surface, the protective coating may comprise a metal oxide of _{formula Ln2O3} , wherein Ln is a lanthanide. For example, Ln can be La, Sc or Y. In applying the lanthanide oxide protective coating, atomic layer deposition may include: a process sequence wherein the protective coating is formed using a cyclopentadienyl Ln compound and ozone in a cyclic ALD process, or wherein the protective coating is formed in a cyclic ALD process A process sequence in which the protective coating is formed using a cyclopentadienyl Ln compound and water, or a process sequence in which the protective coating is formed using a Lnβ-diketone compound and ozone in a cyclic ALD process, or other Suitable for process sequences and lanthanide precursor compounds.

The protective coating can be applied to the metal surface in any suitable thickness, for example a coating thickness in the range from 5 nm to 5 μm.

In various embodiments, the metal surface may be at a temperature in the range from 25°C to 400°C during coating of the metal surface with the protective coating. In other embodiments, this metal surface may be at a temperature in the range 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.

The problems of chemical attack and transport of contaminant species in semiconductor manufacturing operations addressed by the present invention are particularly acute in stainless steel furnaces where wafers are processed for the manufacture of microelectronic devices and other semiconductor manufacturing products. In such furnaces, it has been found that the flow of Al ₂ Cl ₆ vapor transports measurable levels of Cr, Fe and Ni to the wafer as the aluminum hexachloride vapor moves through the system. The current levels measured are consistent with the removal of corresponding oxides of such metals left on the surface of stainless steel (eg, 316L stainless steel) either by natural oxidation or by electropolishing.

The present invention solves this problem by coating the surfaces and components of the furnace with a coating of a material that will not _react with _Al2Cl6 . This enables a solution that is far superior to that used to remove surface oxides, nitrides and halides from stainless steel surfaces and components such that the surface oxides, nitrides and halides do not interact with Al ₂ Cl ₆ A method of conducting the reaction because there will always be a leakage or maintenance event that would expose such surfaces and components to moisture and low levels of ambient moisture of oxygen, nitrogen and halogens. Furthermore, if Al ₂ Cl ₆ were to flow through the furnace in bulk to reactively remove metal oxides, nitrides and halides, this approach would severely degrade tool throughput and not be a viable solution.

In contrast, the present invention employs coating of surfaces and components in furnaces or other semiconductor fabrication equipment such that surfaces and components are _passivated without reacting with _Al2Cl6 . As discussed, the coating advantageously includes one or more of coating materials selected from the group consisting of: Al ₂ O ₃ ; oxides of formula MO, where M is Ca, Mg or Be; formula Oxides of _M'O2 , wherein M' is a stoichiometrically acceptable metal; and oxides of the _{formula Ln2O3} , wherein Ln is a lanthanide such as La, Sc, or Y.

The coating can be applied in any suitable manner to produce a continuous conformal coating on the surfaces and components of semiconductor fabrication equipment, including physical vapor deposition (PVD), chemical vapor deposition (CVD), solution deposition, atomic layer deposition (ALD), etc. technology.

ALD deposition is particularly beneficial for coating filter elements and tube interiors. Trimethylaluminum/ozone (TMA/ _O3 ) or trimethylaluminum/water (TMA/ _{H2O )} are useful compositions for depositing _Al2O3 . Cyclopentadienyl compounds of metal M or Ln can be used to deposit MO or Ln ₂ O ₃ in a cyclic ALD process using ozone (O ₃ ) or water vapor (H ₂ O). β-diketones of M or Ln can be used to deposit MO or Ln ₂ O ₃ in a cyclic ALD process in which reactive pulses of the β-diketone metal precursor alternate with pulses of O ₃ .

To deposit an alumina protective coating, a precursor of a metal (eg, trimethylaluminum) is selected along with an oxygen-containing component (eg, ozone or water), and coating conditions are identified, which may illustratively include TMA /Rinse/ _H2O /Rinse ALD sequence or TMA/Rinse/ _O3 /Rinse sequence at substrate temperatures that can range, for example, from 150°C to 350°C and at from 5 nm to 5 μm range of coating thicknesses. The pulse and flush times of the process sequence can then be determined for the particular reactor and geometry of the surface or component being coated.

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

The temperatures at which aluminum hexachloride exposure will occur in semiconductor equipment are first specified, and then the chemical reactions of the metals of the surfaces and components of the semiconductor fabrication equipment with chemical agents that will contact such surfaces and components are identified. For these chemical reactions at specified temperatures, enthalpy and entropy changes, as well as free energies and reaction constants, can be identified, for example, as shown in Table 1 below.

Table 1

where A is moles, X is a halide and N is any metal. For example, _Nxy can be _HfCl4 or _WCl6 .

The reactions in the first row of Table 1 will not cause corrosion of metals in semiconductor fabrication equipment because the free energy of the reaction is positive. However, the reactions in the second row of Table 1 can lead to corrosion. By changing the surface oxide of the stainless steel semiconductor fabrication equipment from Cr ₂ O ₃ to Al ₂ O ₃ , the driving force for the reaction becomes zero. Alternatively, as shown in the third row of Table 1, the protective oxide can be selected from any metal oxide MO _x for which the free energy of reaction is greater than or equal to zero (and where x has any stoichiometry appropriate value). Furthermore, as shown in the fourth row of Table 1, if a general metal halide vapor _NXy (eg, NF3 _{) is} being delivered, the protective oxide can be selected from the metal oxide MOx for which The free energy of the reaction is greater than or equal to zero.

_The protective coatings of the present invention can be used to protect against corrosive agents such as NF3, _Al2Cl6 , _HfCl4 , _TiCl4 , _ZrCl4 , _WCl6 , _WCl5 , _VCl4 , _NbCl5 , _TaCl5 and other metal _chlorides matter. For example, Al ₂ O ₃ can be utilized as a protective coating material for these etchants. Semiconductor materials (e.g., fluorine, chlorine, bromine, hydrogen fluoride, hydrogen chloride, hydrogen bromide, xenon difluoride, boron trifluoride, silicon tetrafluoride, germanium tetrafluoride, phosphorus trifluoride) that can be delivered as a gas or vapor , arsenic trifluoride, boron trichloride, silicon tetrachloride, ozone) can mediate corrosive behavior, and _Al2O3 coatings can be _usefully used to provide a protective film against such corrosives. Titanium tetrachloride is more corrosive and will have a positive _ΔG for _Y2O3 .

In certain embodiments, Al ₂ O ₃ is utilized as a protective coating material with a positive ΔG for hydrogen bromide exposure on stainless steel surfaces. In other embodiments, Al ₂ O ₃ is utilized as a protective coating material with a positive ΔG for hydrogen chloride exposure of stainless steel surfaces. In still other embodiments, a protective coating material with a positive ΔG is exposed using nickel as the silicon tetrachloride for the stainless steel surface.

In additional embodiments, protective coatings with positive ΔG for stainless steel surfaces exposed to germanium tetrafluoride may include nickel, Al ₂ O ₃ , Cr ₂ O ₃ , gold, nitrides (eg, titanium nitride (TiN)) , any of glass and copper. Passivation with germanium tetrafluoride is effective for stainless steel and nickel because a surface _{Ni -} F, _Cr- F and Fe-F species.

In other embodiments, gold is utilized as a protective coating material with positive ΔG for hydrogen fluoride exposure of stainless steel surfaces.

及

市售的材料的保护涂层)。保护涂层还可用于避免由暴露于氢化物气体所导致的不锈钢脆化，且此类保护涂层可由例如铝、铜或金等材料形成或者以其它方式包括所述材料。In various embodiments, protective coatings for stainless steel and carbon steel include metals (eg, nickel) and metal alloys. In other embodiments, protective coatings for such services may comprise polymeric materials (eg, polytetrafluoroethylene (PTFE)) or PTFE-like materials (including

and

protective coatings of commercially available materials). Protective coatings can also be used to avoid embrittlement of stainless steel caused by exposure to hydride gases, and such protective coatings can be formed from or otherwise include materials such as aluminum, copper, or gold.

The reactants for which the protective coating is provided on the surface may be in solid, liquid and/or gaseous form, and may be in a mixture or a solution comprising one or more solvents.

More generally with regard to ΔG, the stability in the range 10 ⁻⁴ <K<10 ⁺⁴ can be switched by pressure or temperature changes, and when K>10 ⁺⁴ there will be minimal corrosion under any conditions .

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

In the case of an alumina coating on stainless steel as formed in accordance with the present invention, cleaning or other _pretreatment steps may be employed prior to deposition of the _Al2O3 coating. For example, electropolishing or reduction treatments, or a combination of such treatments, may be employed, as may be desirable or advantageous in certain embodiments of the present invention. Any other suitable cleaning or pretreatment steps may additionally or alternatively be utilized.

With respect to aluminum trichloride, it should be noted that _AlCl does not dissolve in solvents or in oils or greases, however, it can be, for example, in a solid delivery vaporizer (where _AlCl or other chemicals are provided for use in the vaporizer) volatilizes when heated to provide a stream of steam dispensed from the vessel) presenting the oil or grease as a heat transfer agent. For example, _AlCl3 or other chemicals to be delivered can be mixed with a high boiling point inert oil or grease to form a paste which is then loaded onto a tray or other support surface in a solid delivery vessel. The oil or grease is then used as a heat transfer agent and as a medium to trap small particles and prevent them from being entrained in the steam stream. These small captured particles then remain in the oil or grease until the small captured particles are vaporized and thereby transferred from the heat transfer agent and ultimately the vaporization vessel. In this way, the oil or grease can improve thermal conductivity and enable lower delivery temperatures of the vaporizer.

Referring now to the drawings, FIG. 1 is a schematic representation of a deposition furnace 102 of a semiconductor wafer processing tool 100 in accordance with one aspect of the present invention.

The furnace 102 defines a heated interior volume 104 in which is positioned a liner 110 that separates the interior volume into an interior volume 108 within the liner and an exterior volume 106 outside the liner, as shown. The wafer carrier 112 with the wafers 114 mounted therein is positioned in the inner volume 108 within the liner 110 so that the wafers can come into contact with the process gas in the furnace.

As shown in the diagram of FIG. 1 , a first process gas may be supplied from a first process gas source 116 to the inner volume 108 of the furnace via a first process gas feed line 118 . In a similar manner, a second process gas may be supplied to the inner volume 108 of the furnace from a second process gas source 120 via a second process gas feed line 122 . The first process gas and the second process gas may be introduced to the furnace simultaneously or sequentially during operation of the tool. For example, the first process gas may include an organometallic precursor for vapor deposition of metal components on the wafer substrate in wafer carrier 112 . For example, the second process gas may include a halide cleaning gas. The gas introduced into the inner volume 108 of the furnace flows upwardly within the liner and, upon exiting the upper open end of the liner 110 , flows downwardly into the annular outer volume 106 . This gas then flows from the furnace in an exhaust line 124 to an abatement unit 126 where the exhaust gas from the furnace is treated to remove harmful components from the exhaust gas, where in the exhaust line The treated gas is vented in 128 for further processing or other disposal. The abatement unit 126 may include wet and/or dry scrubbers, catalytic oxidation devices, or other suitable abatement equipment.

According to the present invention, the surface of the furnace and lining assembly is coated with a layer _{of Al2O3} , making the surface resistant to chemical attack from aluminum hexachloride, which in turn renders the wafers 114 in the furnace defective or even becomes ineffective for its intended purpose.

2 is a schematic representation of a deposition furnace process system for delivering a vaporizer (for vaporizing AlCl ₃ to form Al ₂ Cl ) with a solid source in the form of an ampoule in accordance with another aspect of the present invention ₆ steam), the wafers were coated with Al ₂ Cl ₆ steam, where the tray and interior surfaces of the ampoule were coated with Al ₂ O ₃ and all valves, tubes and filters downstream of the ampoule were coated with Al ₂ O ₃ .

As illustrated, an argon carrier gas supply is provided to the ampoule from a supply vessel ("Ar"), and the carrier gas flows to the ampoule through a carrier gas feed line containing a mass flow controller ("MFC"). _In the ampoule, the carrier gas is contacted with _Al2Cl6 vapor generated by heating the ampoule to volatilize the solid AlCl3 _on the tray supported therein, and the _{volatilized Al2Cl6} then flows to the furnace containing the wafer, aluminum Vapor deposition from Al ₂ Cl ₆ on the wafer. The co-reactants for deposition can be introduced to the furnace through a co-reactant feed line to the furnace as shown. Fluid flow through the furnace is controlled by a pump and pressure control valve assembly to maintain conditions in the furnace suitable for the deposition operation therein.

As mentioned, the tray and interior surfaces of the ampoule, as well as the surface of the flow line downstream from the ampoule and components therein, _were coated with _Al2O3 to prevent corrosion by aluminum hexachloride vapors. The filter in the flow line may be of the type with metal filter elements commercially available under the tradenames Wafergard ^™ and Gasketgard ^™ from Intergel Corporation of Billerica, MA, USA.

3 is a perspective partial cutaway view of a vaporizer ampoule of the type suitable for use in the deposition furnace process system of FIG. 2 . The vaporizer ampoule contains a container 300 having a holder to help facilitate contact of the gas with the vapor from the material supported by the holder. The container 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 container has a bottom wall with a surface 301 and side walls 302 to help define a generally cylindrical interior region in the container 300 having a generally circular shape at or near the top of the container 300 Open your mouth. In certain embodiments, the inner diameter of the generally cylindrical inner region may be in the range of about 3 inches to about 6 inches, for example.

Although the container 300 is illustrated in FIG. 3 as having a unitary body, the container may be formed from separate pieces. The container thus provides an ampoule for vaporizing the material for delivery to the processing facility.

As illustrated in FIG. 3, holder 310 may be positioned above bottom surface 301 to define support surface 311 above bottom surface 301, holder 320 may be positioned above holder 310 to define support surface 321 above support surface 311; holding Holder 330 may be positioned over holder 320 to define support surface 331 over support surface 321; holder 340 may be positioned over holder 330 to define support surface 341 over support surface 331; holder 350 may be positioned over holder 340 above to define support surface 351 above support surface 341 ; and holder 360 may be positioned above holder 350 to define support surface 361 above support surface 351 . Although illustrated in FIG. 3 as using six retainers 310, 320, 330, 340, 350, and 360, any suitable number of retainers may be employed in various embodiments of the vaporizer.

As illustrated in FIG. 3 , a generally annular support 304 may be placed on the bottom surface 301 in the interior region of the container 300 to support the holder 310 above the bottom surface 301 . Tube 305 may then extend through openings in holders 360 , 350 , 340 , 330 , 320 and 310 to a position between holder 310 and bottom surface 301 in a substantially central portion of the interior region of container 300 .

As one example, the vaporizer of FIG. 3 may be modified by coupling baffles or diffusers at the ends of the tubes 305 to help direct the gas flow over the material supported on the bottom surface 301 . In embodiments in which the gas is introduced at or near the lowermost holder supporting the material to be vaporized, the introduced gas may be directed to flow over the material supported by the lowermost holder using any suitable structure and/or or flow through the material.

任何适合弹性体或任何适合金属，例如不锈钢)形成。盖306可界定穿过盖306的大体上中心区域的开口，至少部分地由管305界定的通路或入口可通过所述开口延伸到容器300的内部区域中。盖306固定到容器300的套环，盖306可按压在上O形环308上以帮助将盖306密封于套环上方且可按压在围绕管305的套环上以帮助将盖306按压在固持器360、350、340、330、320及310上。固持器360、350、340、330、320及310的O形环可接着经压缩以帮助将固持器360、350、340、330、320及310密封于彼此上及/或密封于管305上。具有入口耦合件391的阀381可耦合到管305以帮助调节气体到容器300中的引入。盖306还可界定开口，至少部分地由管界定的通路或出口可通过所述开口延伸到容器300中。具有出口耦合件392的阀382可耦合到管以帮助调节气体从容器的递送。As illustrated in Figure 3, the container 300 can have a collar surrounding the opening at the top of the container 300, and a lid 306 that can be positioned over the collar and secured to the collar using screws (eg, screws 307). A groove can optionally be defined around the opening at the top of the collar to help position the O-ring 308 between the container 300 and the lid 306 . O-ring 308 can be made of any suitable material (eg,

Any suitable elastomer or any suitable metal, such as stainless steel). The lid 306 can define an opening through a generally central area of the lid 306 through which a passage or inlet, at least partially defined by the tube 305 , can extend into the interior area of the container 300 . The cap 306 is secured to the collar of the container 300, the cap 306 can be pressed on the upper O-ring 308 to help seal the cap 306 over the collar and can be pressed on the collar around the tube 305 to help press the cap 306 in retention devices 360 , 350 , 340 , 330 , 320 and 310 . The O-rings of the retainers 360 , 350 , 340 , 330 , 320 and 310 may then be compressed to help seal the retainers 360 , 350 , 340 , 330 , 320 and 310 to each other and/or to the tube 305 . A valve 381 with an inlet coupling 391 may be coupled to the tube 305 to help regulate the introduction of gas into the vessel 300 . The lid 306 may also define an opening through which a passage or outlet, at least partially defined by the tube, may extend into the container 300 . A valve 382 with an outlet coupling 392 can be coupled to the tube to help regulate the delivery of gas from the container.

As illustrated in FIG. 3 , a generally circular frit 370 may be positioned over top holder 360 to aid in the delivery of gas flow directed over material supported by holder 360 through the outlet defined by cover 306 Solid material is filtered from the gas stream. The frit 370 can define a generally circular opening through a generally central region of the frit 370 through which the tube 305 can extend. The frit 370 may be pressed over the retainer 360 in any suitable manner when the lid 306 is secured to the container 300 using any suitable structure to help seal the frit 370 over the retainer 360 . In addition to or in place of frit 370, the vaporizer may also include frit positioned in the passageway or outlet for gas delivery from vessel 300 and/or through retainers 310, 320, 330, 340, 350 One or more of and 360 are positioned on one or more frits in one or more vias. The frit in the vaporizer may additionally be coated with Al ₂ O ₃ . _In a similar manner, any other internal components in the vaporizer can be coated with _Al2O3 , such that all surfaces and components in the internal volume _of the vaporizer are coated with _Al2O3 .

In the vaporizer of FIG. 3 , a bypass passage defined by a tube 395 coupled between valves 381 and 382 may be used to assist flushing valves 381 and 382 , inlet coupling 391 and/or outlet coupling 392 . Valve 383 may optionally be coupled to tube 395 to help regulate fluid flow through the bypass passage. Inlet/outlet coupling 397 may optionally be used to help define additional inlets/outlets of the interior area of container 300 to aid in flushing the interior area.

4 is a photomicrograph at 15K magnification of the surface of a porous metal frit of a type useful in filter elements according to another aspect of the present invention.

The high surface area of the frit can be advantageously coated by ALD, where the metal precursor and the oxidative co-reactant reach the surface in separate self-limiting pulses. To coat the frit with _Al2O3 , alternating pulses of trimethylaluminum and water or an _O3 / _{O2 mixture} can be used. Specific conditions can be determined empirically by increasing the pulse length at each step until all surfaces are coated. In certain embodiments, deposition temperatures from 100°C to 400°C may be employed to deposit useful films.

It will be appreciated that other sources of aluminum may be employed in the broad practice of the present invention, such as, for example, AlCl3, other _AlR3 (alkyl) compounds (wherein _R3 is an organic moiety ₎ , or other volatile Al compounds. In this practice of the invention, other oxygen sources such as _N2O , _O2 , alcohols, peroxides, etc. may also be used with the aluminum source reagent to deposit _Al2O3 or related _{AlOx materials} .

The features and advantages of the present invention are more fully shown by the following examples having an illustrative character to facilitate the understanding of the invention.

Example 1

Electropolished 316L stainless steel samples were rinsed with isopropanol to clean the surface. Both samples were coated with Al ₂ O ₃ by atomic layer deposition (ALD). One sample was subjected to 100 ALD cycles of trimethylaluminum/rinse/water/rinse and the other sample was subjected to 1000 cycles of the same ALD process. The deposition temperature was 150°C. Two samples were uncoated. Two coated samples and one of the uncoated samples were loaded into glass ampoules with solid AlCl ₃ powder in a nitrogen flushed glove box to prevent moisture or oxygen from interacting with the sample or AlCl ₃ . The glass ampoule is then sealed with a PTFE cap. _The ampoules with AlCl3 and stainless steel samples were heated to 120°C for 10 days. At the end of the 10 days, the ampoules were cooled and brought back to the glove box. _The sample is removed from the AlCl3 under this inert environment. The mass gain of the sample was 0.4 mg to 0.7 mg (<0.15%). All surfaces look pristine. Next, the samples were examined in a Scanning Electron Microscope (SEM) on the top surfaces of these _three samples and an additional sample not exposed to AlCl at all and then cross-sectioned by a Focused Ion Beam (FIB) to Determine if there is any surface erosion.

Figure 5 shows a surface image _of a sample without any AlCl3 seen. The surface of this sample is clean and exhibits the main elements of stainless steel: Fe, Cr and Ni.

Figure ₆ shows uncoated samples exposed to AlCl3. It can be seen that there is significant surface residue on this sample with the addition of Al and Cl to the main components of the stainless steel.

Figure 7 shows a cross-section _of a sample not exposed to AlCl3. Clearly, there is no surface erosion.

Figure ₈ shows an uncoated sample exposed to AlCl3. There is a line for comparison with the surface, making it apparent that there is no 0.1 to 0.2 micron surface erosion below the region with Al and Cl containing residues.

Figure 9 shows different regions _of a sample exposed to AlCl3 without a surface coating. Natural oxides are present on untreated stainless steel surfaces. In this area, multiple pits are clearly visible.

In contrast, Figure 10 shows a cross-section of the surface of the coating with 100 cycles _of TMA/ _H2O prior to exposure to AlCl3 at 120°C. In this case, there was still Al and Cl containing residues adhering to the surface, but there was no evidence of any erosion of the surface of the stainless steel.

Likewise, Figure 11 shows a cross-section of the surface of the coating with 1000 cycles _of TMA/ _H2O prior to exposure to AlCl3 at 120°C. In this case, there was still Al and Cl containing residues adhering to the surface, but there was no evidence of any erosion of the surface of the stainless steel.

Example 2

In certain empirical evaluations, the efficacy of the alumina coating was estimated when exposed to aluminum trichloride (AlCl ₃ ) in the first test and to tungsten pentachloride (WCl ₅ ) in the second test.

的Al₂O₃或未经涂覆。将每一类型的一个样本放置于具有固体AlCl₃的两个容器中的一者中。将两个容器装载、密封于N₂冲洗的手套箱内部且用所述手套箱内部的氦气加压到3psig，其中O₂及H₂O水平低于0.1ppm。外侧He泄漏测试确定，容器中的一者具有低于1E-6标准立方厘米/秒(scc/s)(其为测量的分辨极限)的泄漏速率，且另一容器具有2.5E-6scc/s的泄漏速率。在手套箱中，在相同炉子中将容器加热到155℃达九天、冷却且将取样片移除。表2展示各种取样片的质量改变。In the first test, sample coupons of electropolished 316L stainless steel were coated with

Al ₂ O ₃ or uncoated. One sample of each type was placed in one of the two containers with solid AlCl ₃ . Both vessels were loaded, sealed inside a _N2 flushed glove box and pressurized to 3 psig with helium inside the glove box with _O2 and _H2O levels below 0.1 ppm. The outside He leak test determined that one of the containers had a leak rate below 1E-6 standard cubic centimeters per second (scc/s), which is the resolution limit of the measurement, and the other had 2.5E-6 scc/s leak rate. In the glove box, the vessel was heated to 155°C in the same oven for nine days, cooled and the coupons removed. Table 2 shows the mass change for various coupons.

Table 2. Mass change of various coupons immersed in AlCl3 at 155°C for ₉ days.

sample type ID leak rate initial mass post quality Change %Change scc He/s g g g Coated coupons 2 2.50E-06 3.3986 3.3967 -0.0019 -0.06% Coated coupons 3 <1E-6 3.3896 3.3896 0.0000 0.00% Uncoated coupons 12 2.50E-06 3.3913 3.3824 -0.0089 -0.26% Uncoated coupons 13 <1E-6 3.4554 3.4554 0.0000 0.00%

12 is a composite photograph of the sample coupons of Table 2 after exposure to AlCl ₃ at 155° C. for nine days, wherein the corresponding coupons are identified by the same ID number as set forth in Table 2. FIG.

It is clear from Table 2 that the mass change is only quantifiable when there is a measurable leak of the container. In this corrosive exposure, the mass loss of the samples as listed in Table 2 and the composite photo of the corresponding sample coupons in Figure 12 show that the coated sample coupons were after exposure to _ACl at 155°C for nine days 2 is in substantially better condition than the uncoated sample coupon 12. There was no change in _{Al2O3 coating} thickness, as measured by XRF.

厚的Al₂O₃涂层或未经涂覆。将样本取样片放置于具有固体WCl₅的容器中，其中在相应容器中维持165℃、180℃及220℃温度条件。将所有容器装载且密封于N₂冲洗的手套箱内部，其中O₂及H₂O水平低于0.1ppm。接着在手套箱中，在炉子中将容器加热达十天、冷却且将样本取样片从相应容器移除。In the second test, sample coupons of electropolished 316L stainless steel were coated with

_{Thick Al2O3} coating or uncoated. The sample coupons were placed in containers with solid _WCl5 , with temperature conditions of 165°C, 180°C and 220°C maintained in the respective containers. All containers were loaded and sealed inside a _N2 flushed glove box with _O2 and _H2O levels below 0.1 ppm. Then in the glove box, the containers were heated in an oven for ten days, cooled and the sample coupons were removed from the respective containers.

到

的涂层。Thickness measurements were made by x-ray fluorescence (XRF) spectroscopy to evaluate the change in coating thickness of the alumina coating from the initially measured thickness. Table 3 contains XRF measurements of Al ₂ O ₃ thickness before and after exposure to WCl ₅ for two sample coupons maintained at 165°C for 10 days in this exposure, Two sample coupons at 180°C for 10 days and one sample coupon maintained at 220°C for 10 days in this exposure. The cleaning process typically etch away approximately

arrive

coating.

Table 3. XRF measurements of Al ₂ O ₃ film thickness before and after exposure to WCl ₅ at various temperatures for 10 days.

Figure 13 is an overhead scanning electron microscope (SEM) micrograph of a sample exposed to WCl ₅ at 220°C for 10 days, and Figure 14 is a focused ion beam (FIB) cross-section of the edge of the coating in this sample.

的厚度，此与清洁一致，但另一样本损失大约

的厚度，此显著高于清洁的厚度。在220℃下，如图13中所展示移除涂层的约60％，其中在一些区(较浅区部分)中移除氧化铝涂层且在其它区(较深区部分)中氧化铝涂层完整无损。在图14中，显微照片展示在右侧的涂层完整无损，且经涂覆区的边缘由箭头指示。The coated and uncoated samples in this second test showed no evidence of corrosion visually or by SEM inspection or by weight change. However, at higher temperatures, a significant amount of the Al ₂ O ₃ coating was removed. The two samples at 165°C were etched in amounts consistent with the cleaning process. Loss of one of the samples at 180°C

thickness, which is consistent with cleaning, but the other sample loses approx.

thickness, which is significantly higher than that of cleaning. At 220°C, about 60% of the coating was removed as shown in Figure 13, with the alumina coating removed in some regions (the shallower portion) and alumina in other regions (the deeper portion) The coating is intact. In Figure 14, the photomicrograph shows that the coating on the right is intact and the edges of the coated areas are indicated by arrows.

It will be appreciated that while the present invention is illustratively directed to semiconductor manufacturing equipment, the protective coating methods of the present invention are equally applicable to other gas processing devices used to manufacture other products, such as flat panel displays, photovoltaic cells, solar panels, etc., wherein Surfaces in processing equipment are susceptible to erosion by gas-phase components that react with oxides on such facilities to form reaction products that are detrimental to the products made with the equipment and the processes performed with the equipment.

Another aspect of the invention involving thin film atomic layer deposition coatings is set forth below.

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

It must be noted that, as used herein, the singular forms "a (a, an)" and "the (the)" include plural references unless the context clearly dictates otherwise. Thus, for example, reference to a "layer" is a reference to one or more layers and equivalents thereof, etc. known to those skilled in the art. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.

Methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention. All publications mentioned herein are incorporated by reference in their entirety. Nothing herein should be construed as an admission that the invention claimed herein is not entitled to antedate such publications based on prior invention. "Optional" or "optionally" means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event occurs and instances where it does not. All numerical values herein may be modified by the term "about" whether or not explicitly indicated. The term "about" generally refers to a range of numbers that one of ordinary skill in the art would consider equivalent to the stated value (ie, having a similar function or result). In some embodiments, the term "about" refers to ±10% of the stated value, and in other embodiments, the term "about" refers to ±2% of the stated value. While the compositions and methods are described in terms of "comprising" various components and steps, such terms should be construed as defining a substantially closed or closed group of members.

As used herein, the term "film" refers to a layer of deposited material having a thickness below 1000 microns (eg, from a value as low as a value for atomic monolayer thickness). In various embodiments, for example, the film thickness of the deposited material layer in the practice of the present invention may be less than 100 microns, 50 microns, 20 microns, 10 microns, or 1 micron, or various thin film regimes ) below 200 nanometers, 100 nanometers, 50 nanometers, 20 nanometers or 10 nanometers, depending on the specific application involved. As used herein, the term "thin film" means a layer of material having a thickness of less than 1 micron.

While the invention has been described herein with respect to one or more embodiments, equivalent changes and modifications will come to mind to those skilled in the art upon reading and understanding this specification. The present invention includes all such modifications and alterations. Additionally, although a particular feature or aspect of the invention may have been disclosed with respect to only one of several embodiments, this feature or aspect may be combined with one or more other features or aspects of other embodiments, such as for any given Certain or specific applications may be desirable and advantageous. Furthermore, with respect to the terms "includes", "having", "has", "with" or variations thereof herein, such terms are intended to be used in conjunction with the term "including" (comprising)" is inclusive. Also, the term "exemplary" means only an example, not a best example. It will also be appreciated that for simplicity and ease of understanding, features, layers and/or elements depicted herein are illustrated and/or taught in specific dimensions and/or orientations relative to each other, and actual dimensions and/or or orientation may vary substantially from the dimensions and/or orientations illustrated and/or taught herein.

Thus, the present invention as variously stated herein with respect to its features, aspects, and examples may, in particular embodiments, be structured to include, consist of, or consist essentially of: such Some or all of the features, aspects, and embodiments, as well as elements and components of the invention, which are aggregated to form various other embodiments of the invention. The present invention accordingly contemplates that such features, aspects and embodiments, or selected ones or several thereof, in various permutations and combinations are within the scope of the present invention. Furthermore, the invention contemplates embodiments that may be defined by excluding any one or more of the specific features, aspects or elements disclosed herein in conjunction with other embodiments of the invention.

According to one aspect of the present invention, there is provided a thin film coating consisting of one or more layers, wherein at least one layer is deposited by atomic layer deposition.

According to aspects of the present invention, the following are provided:

且在一些应用中多于

的膜厚度的ALD涂层。-has more than

and in some applications more than

The film thickness of the ALD coating.

- Provides an ALD coating with extremely dense, pin-hole-free, defect-free layers.

- Thin film coatings intended for deposition application on numerous parts but not directly for actual IC device (transistor) fabrication on Si wafers.

- ALD coatings can be made of insulating metal oxides (eg, aluminum oxide (Al ₂ O ₃ ), yttria (Y ₂ O ₃ ), zirconium oxide (ZrO ₂ ), titanium dioxide (TiO ₂ ), etc.) and metals (eg, platinum, niobium) or nickel).

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

- The ALD coating can be a single film with a defined stoichiometry, such as a 1 micron thick aluminum oxide layer or several layers (eg {0.25 micron titania + 0.5 micron aluminum oxide + 0.25 micron zirconia}) or true multilayer structure (eg, {1 atomic layer of titanium dioxide + 2 atomic layer of aluminum oxide} x n, where n is in the range 1 to 10,000), or a combination thereof.

- Thin film coatings in which the ALD layer is combined with another layer deposited by different deposition techniques (eg PE-CVD, PVD, spin-on or sol-gel deposition, atmospheric pressure plasma deposition, etc.).

- The total film thickness is between 1 micron and 100 microns.

- The fraction of the ALD coating thickness of the entire stack is less than or equal to 2 microns, where 2 microns is in one or more different layers.

- other coating materials selected from the group of oxides such as aluminium oxide, aluminium oxynitride, yttrium oxide, yttria-alumina mixture, silicon oxide, silicon oxynitride, transition metal oxides, transition metals Nitrogen oxides, rare earth metal oxides, rare earth metal oxynitrides.

- Ability to pattern ALD coatings:

- Method 1: Coat the part uniformly and then etch back the unwanted material through a mask (the etch back can be mechanical (eg bead blasting), physical (eg plasma ion) or chemical ( For example, plasma or wet etching)).

- Method 2: Masking unwanted areas, ALD coating and then removing masked areas. The mask can be a sealing sheet or fixture or a photoresist (lift-off technique).

- Method 3: Patterning on the substrate from a surface stop layer that prevents the growth of the ALD film. For example, surface stop layers with "zero" adhesion coefficients for _H2O and TMA (trimethylaluminum) can be employed. As used herein, a surface termination layer is a self-limiting layer, such as a self-limiting ALD layer. As used herein, the adhesion coefficient is the ratio of adsorbate atoms (or molecules) adsorbed or "adhered" to a surface to the total number of items impinging on the surface during the same time period.

According to aspects of the present invention, the following applications are provided:

application:

- Partially defect-free, pin-hole-free, dense, electrically insulating.

- Ability to coat parts with high aspect ratio features. Examples: (1) Parts with deep holes, channels, and 3D features, (2) Hardware such as screws and nuts, (3) Porous membranes, filters, 3D network structures, (4) Structures with a matrix of connected pores.

- Electrical insulating layer: high dielectric breakdown strength and high resistance (low leakage). This is achieved by ALD Al ₂ O ₃ . The electrical insulator performance was further improved using multilayer titania-alumina-zirconia (TAZ). Various multi-tier configurations exist:

X nm TiO ₂ +Y nm Al ₂ O ₃ +Z nm ZrO ₂

[U nm TiO ₂ +V nm Al ₂ O ₃ +W nm ZrO ₂ T]×n

X nm TiO ₂ +[V nm Al ₂ O ₃ +W nm ZrO ₂ T]×m

etc.; wherein X, Y, Z, U, V, and W can each range from 0.02 nm to 500 nm, and wherein each of n and m can range from 2 to 2000.

- Chemical and etch resistant coating: The ALD layer may be aluminum oxide, yttrium oxide, ceria or the like. The entire etch resistant coating may consist of: (1) ALD layer only, (2) a combination of PVD, CVD and ALD, (3) ALD may be an overcoat and used as an encapsulant layer, as hereinafter Discussed more fully, (4) ALD can be a base layer to provide a robust foundation, and (5) ALD can be interspersed between CVD coatings and/or PVD coatings.

-ALD coatings provide chemical resistance for applications such as advanced batteries, gas filters, liquid filters, electroplating tool components, plasma wet components (to protect against fluorine and other halogens).

-ALD coating can be used as anti-corrosion coating.

-Diffusion barrier layer; dense, conformal and pin-free ALD layer provides excellent trace metal diffusion barrier properties.

-ALD layer can be used as underlying substrate (glass, quartz, aluminum, anodized aluminum, aluminum oxide, stainless steel, silicon, SiOx, AlON, etc.) and overlying coatings (PVD yttrium oxide, PVD AlON, PVD _{Al2O 3.} Adhesion layer between CVD _SiOx , CVD _SiOxNy , _{CVD Al2O3} , _CVDAlOxNy , DLC, Si, SiC, etc. ₎ .

According to another aspect of the present invention, the ALD deposited surface sealant layer is used for the coating. ALD (Atomic Layer Deposition) is an established technique that uses the chemisorption of two or more alternating precursors to form extremely dense, (physically and stoichiometrically) nearly perfectly arranged films. The techniques allow for precisely controlled film growth, are nearly 100% conformal, and will grow 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:

(1) Overcoats and seals existing surfaces and thus provides enhanced and superior properties of said surfaces/portions

(2) Applying an ALD seal coat on top of a CVD, PVD, spray, or other coating to provide a sealant against imperfections in the coating, such as:

(i) fills any cracks close to the coating surface and thus provides a surface that is impermeable to corrosive and etching environments

(ii) Fill and seal any macrovoids, coating defects, intrusions, etc. to provide a coating surface layer that is impermeable to gases and liquids and terminates with a controlled smooth conformal sealant layer

(iii) Reduce surface roughness and overall surface area of the coating, thus providing a smooth and dense surface layer that allows minimal erosion in corrosive environments

(iv) Minimize particle generation, improve hardness, toughness and scratch resistance by providing a dense and smooth sealing surface with an overcoat

In various aspects of the present invention, ALD sealants can be applied to parts and surfaces that require:

(a) improved etch and corrosion resistance, and/or

(b) Reduced friction, wear and improved mechanical wear resistance

The ALD encapsulant layer also acts as a diffusion barrier, and it has the ability to control surface electrical properties as well as surface termination such as hydrophilicity and hydrophobicity.

Another aspect of the present invention relates to the use of ALD techniques on fiber metal films with chemically resistant coatings such as alumina, yttria, or other coatings of this type. ALD technology allows gases to penetrate the porous filter and coat over the fibrous membrane, providing resistance to corrosive gases.

This aspect of the invention provides a deposition gas based technique that is permeable to small micron sized openings and uniformly coats the fibers.

This aspect of the invention has been demonstrated by depositing an alumina coating on a 4 micron Ni-based gas filter made by Intergel Corporation of Billerica, MA, USA.

The ALD technology of the present invention provides many benefits, such as:

1) The coating penetrates into small features such as the micron-sized porosity of the filter, ensuring complete coverage

2) Airtight sealing of the fibers, thus protecting the filter membrane

3) Various coatings can be deposited using this technique

The present invention also contemplates the use of ALD coatings to improve the handling characteristics of coated substrate articles or devices. For example, ALD films can be used to combat blistering or other undesired phenomena that can occur during annealing of substrate articles due to mismatched thermal expansion coefficients between layers of a multilayer film article. Thus, ALD films can be used in multilayer film structures to mitigate such material property differences, or to otherwise improve the electrical, chemical, thermal, and other performance properties of the final product article.

The present invention further contemplates the use of ALD coatings to protect fluid contacting surfaces of devices that handle fluids that may be at risk of chemical attack during use of such devices. For example, such a device may include a fluid storage and dispensing package for supplying gases to semiconductor fabrication tools, where the fluid may adversely affect flow path components and downstream processing equipment. Fluids that may present particular problems in certain applications may contain halide gases, such as fluorides of boron or germanium. Accordingly, in these and other applications, the coatings of the present invention can be employed to enhance the performance of processing equipment, flow lines, and system components.

In another aspect, the present invention relates to a composite ALD coating comprising layers of different ALD product materials. The different ALD product materials can be of any suitable type, and can include, for example, different metal oxides, such as at least two metal oxides selected from the group consisting of: titania; alumina; zirconia; oxides, wherein M is Ca, Mg, or Be; oxides of _formula M'O2, wherein M' is a stoichiometrically acceptable metal; and oxides of _{formula Ln2O3} , wherein Ln is a lanthanide, For example La, Sc or Y. In other embodiments, the composite ALD coating can include at least one layer of aluminum oxide. In still other embodiments, the composite ALD coating may comprise at least one layer of titania or zirconia or other suitable material.

This composite ALD coating may include a different metal than the different ALD product materials (eg, at least two metals selected from the group consisting of platinum, niobium, and nickel). Any suitable metal can be used.

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

The composite ALD coatings described above can have any suitable number of layers in the coating, such as from 2 to 10,000 layers.

In another aspect, the present invention relates to a composite coating comprising at least one ALD layer and at least one deposited layer that is not an ALD layer. For example, the composite coating can be structured such that 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 coating, a spray coating, Sol-gel layer and atmospheric pressure plasma deposition layer. In various embodiments, the layers in the composite coating can include at least one layer of a material selected from the group consisting of aluminum oxide, aluminum oxynitride, yttrium oxide, yttria-alumina, silicon oxide, Silicon oxynitride, transition metal oxide, transition metal oxynitride, rare earth metal oxide and rare earth metal oxynitride.

The present invention further contemplates a method of forming a patterned ALD coating on a substrate comprising patterning the substrate with a layer of surface stop material effective to prevent the growth of the ALD film. In certain embodiments, this surface termination material can exhibit substantially zero adhesion coefficients to water and trimethylaluminum. In various embodiments, the ALD coating may include aluminum oxide.

The present invention further contemplates a method of filling and/or sealing a surface defect of a material, the method comprising applying an ALD coating to the surface defect of a material in a thickness that affects the filling and/or sealing of the defect. The defects may be of any type, and may be selected, for example, from the group consisting of cracks, morphological defects, pores, pin holes, notches, intrusions, surface roughness, and surface asperities.

Another aspect of the present invention relates to a filter comprising a matrix of fibers and/or particles formed from metallic and/or polymeric materials on which the matrix of fibers and/or particles is having an ALD coating, wherein the ALD coating does not alter the pore volume of the matrix of fibers and/or particles by more than 5% compared to the corresponding matrix of fibers and/or particles lacking the ALD coating thereon, and Wherein when the fibers and/or particles are formed of metal and the ALD coating includes metal, the metal of the ALD coating is different from the metal of the fibers and/or particles.

The filter can be configured as a matrix having fibers and/or particles in a housing configured for fluid flow through the matrix to filter the fluid. In various embodiments, the ALD coating may include suitable types of transition metals, metal oxides, or transition metal oxides. For example, the ALD coating can include a metal oxide selected from the group consisting of: titania; alumina; zirconia; oxides of formula MO, where M is Ca, Mg, or Be; and formula Ln ₂ Oxides of _O3 , where Ln is a lanthanide, La, Sc or Y. In various embodiments, the ALD coating includes aluminum oxide. The matrix of the filter may comprise nickel fibers and/or particles, stainless steel fibers and/or particles, or fibers and/or particles of other materials such as polymeric materials such as polytetrafluoroethylene. In various embodiments, the filter may include pores of any suitable diameter. For example, in some embodiments, the pores may range from 1 μm to 40 μm, and in other embodiments, the pores may be less than 20 μm, less than 10 μm, less than 5 μm, or other suitable values, and in other embodiments , the pores may be in the range from 1 μm to 10 μm, from 1 μm to 20 μm, from 20 μm to 40 μm, or other suitable value ranges. The ALD coating itself may have any suitable thickness, and in various embodiments may have a thickness ranging from 2 nm to 500 nm. In general, any suitable pore size and thickness characteristics may be employed as appropriate for a particular end use or application.

A filter may have suitable properties with regard to its retention rating. For example, in certain embodiments, the filter's retention rating may be a log reduction value of 9 (denoted as 9LRV) for particles larger than 3 nm at a gas flow rate of 30 standard liters/minute or less. characterization. The ALD-coated filters of the present invention can be used where it is desirable for the filter to achieve a high efficiency removal rate (eg, a removal rate of 99.9999999% as determined by the maximum permeate particle size (ie, 9LRV) at a particular rated flow rate) ) in various applications. The test method used to estimate the 9LRV rating is described in: "Particle Penetration of Porous Metal Filter Media for High Purity Gas Filtration by Huber K.L. (Rubow, K.L.) and Davis C.B. (Davis, C.B.) Particle Penetration Characteristics of PorousMetal Filter Media For High Purity Gas Filtration" (Proceedings of the 37th Annual Technical Meeting of the Institute of Environmental Sciences, pp. 834-840); Huber K.L., D.S. Prause, and M.R. Ai "A Low PressureDrop Sintered Metal Filter for Ultra-High Purity Gas Systems" by M.R. Eisenmann (43rd Annual Technical Meeting of the Institute of Environmental Sciences) Conference Proceedings (1997)); and "Test Method for EfficiencyQualification of Point-of-Use Gas Filters" of Semiconductor Equipment and Materials International (SEMI) Test Method SEMI F38-0699 )", all of which are incorporated herein by reference.

Sintered metal filters/diffusers that can be coated with a protective coating by ALD in accordance with the present invention include those described in US Pat. Nos. 5,114,447, 5,487,771, and 8,932,381 and in diffuser.

到

(例如，

/循环)。The gas filter coated with the protective coating according to the present invention can be configured differently. In certain illustrative embodiments, the filter may have a pore size in the range from 1 μm to 40 μm, or from 1 μm to 20 μm, or from 20 μm to 40 μm, or other suitable values. Such gas filters are available in stainless steel and nickel configurations. Both the stainless steel and nickel configurations are susceptible to metal contamination when exposed to aggressive gaseous environments. According to the present invention, the filter matrix of such a gas filter can be coated with a chemically inert and robust aluminum oxide film using ALD coating techniques. The ALD process can include any number of deposition cycles, eg, ranging from 100 cycles to 5000 cycles. In certain embodiments, the trimethylaluminum/ _H2O process with extended wait and rinse times may be used at temperatures that may, for example, be in the range of 200°C to 300°C (eg, 250°C) ALD aluminum oxide films were deposited from 50 cycles to 1500 cycles, with deposition per cycle

arrive

(E.g,

/cycle).

In various embodiments, an ALD alumina coating process may be performed to provide an alumina coating thickness on the gas filter, which may range, for example, from 15 nm to 200 nm . In other embodiments, the ALD alumina coating thickness may range from 20 nm to 50 nm.

The gas filter coatings described above, as formed by ALD coating techniques, can be performed to provide varying aluminum content in the aluminum oxide film. For example, in various embodiments, the aluminum content of such films may 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 ranges from 30 atomic percent to 32 atomic percent of the aluminum oxide film Inside.

In other illustrative embodiments, the gas filter may comprise an in-line metal gas filter having a pore size ranging from 2 μm to 5 μm, wherein the filter comprises a titanium filter matrix, wherein the ALD alumina coating has a Thickness in the range from 10 nm to 40 nm (eg, 20 nm thickness). In still other embodiments, the gas filter may comprise a nickel-based gas filter matrix having a pore size ranging from 2 μm to 5 μm, wherein the ALD alumina coating may have a pore size ranging from 10 nm to 40 nm thickness (eg, 20 nm thickness).

The protective coatings of the present invention can also be used to coat surfaces in chemical supply packages (eg, fluid storage and dispensing vessels, solid agent vaporization vessels, and the like). In addition to the materials to be stored in and dispensed from such fluid storage and dispensing vessels, such vessels may variously contain storage media for the stored materials, The stored material can be dispensed from the storage medium for dispensing the stored material from a material supply packaged vessel. Such storage media may comprise physical adsorbents (on which the fluid is reversibly adsorbed), ionic storage media for reversible fluid storage, and the like. For example, a solid delivery package of the type disclosed in International Publication WO2008/028170 published March 6, 2008, the disclosure of which is hereby incorporated by reference in its entirety, may have on its interior surface is coated with the protective coating of the present invention.

Other types of chemical supply packages in which the interior surface of the supply vessel is coated with the protective coating of the present invention may be employed, such as for delivery of gases (eg, such as boron trifluoride, germanium tetrafluoride, silicon tetrafluoride, etc. Gas and other gases used in the manufacture of semiconductor products) internal pressure regulated fluid supply vessels, flat panel displays and solar panels.

Another aspect of the invention relates to a method of delivering a gaseous or vapor stream to a semiconductor processing tool, the method comprising providing a flow path for the gaseous or vapor stream from a source of the gaseous or vapor stream to the semiconductor processing tool, and A gaseous or vapor stream is flowed in a flow path through a filter to remove foreign solid material from the stream, wherein the filter includes a filter of the type as variously described herein.

In this method, the gaseous or vapor stream can include any suitable fluid species, and in certain embodiments, this stream includes aluminum hexachloride. Particular filters used in such fluid applications include ALD coatings including alumina, where the matrix includes stainless steel fibers and/or particles.

The semiconductor processing tools in the aforementioned methods may be of any suitable type, and may include, for example, vapor deposition furnaces.

As mentioned above, filters can vary in ALD coatings and substrates. In certain embodiments, the filter includes a sintered matrix of stainless steel fibers and/or particles coated with an ALD alumina coating, wherein the sintered matrix includes a Pores with diameters ranging from 1 μm to 10 μm, from 10 μm to 20 μm), or other suitable pore diameter values, and wherein in any of such embodiments the ALD coating has a diameter in the range from 2 μm to 500 nm thickness within the range.

In another aspect, the present invention relates to the use of ALD for pore size control in fine filtration applications to achieve specially tailored filters beyond the capabilities provided only by sintered metal matrix filters. In this regard, it becomes increasingly difficult to control pore size in sintered metal matrix filters as the target pore size shrinks to less than 5 μm. According to the present invention, ALD coatings can be used to effectively reduce pore size with a high degree of control over pore size and pore size distribution. Although coatings deposited by ALD can be substantially thicker than those employed in other applications, ALD provides extraordinary control over pore size and pore size distribution while still achieving chemical resistance benefits (eg, with ALD alumina coatings) possibility.

Accordingly, ALD coatings of sintered metal matrix material can be applied to the sintered metal matrix structure at larger thicknesses, wherein the coating thickness is such that the pore size in the coated metal matrix structure is reduced to very low levels (eg, , down to the submicron pore size level).

This method can also be used to achieve a filter that produces a porosity gradient (eg, from the gas inlet face to the gas outlet face), where relatively larger sized pores are present at the gas inlet face of the filter and relatively smaller Pores of large and small size exist at the gas discharge face, with a porosity gradient between corresponding faces of the filter. With this porosity gradient, the filter can be used, for example, to capture large particles at the inlet side of the filter and smaller particles on the outlet side of the filter, such that overall efficient filtration is achieved effect.

Accordingly, the present invention contemplates filters comprising an ALD-coated porous material substrate, wherein the pore size of the porous metal substrate has been increased by the ALD coating relative to a corresponding porous material substrate not coated with an ALD coating. Reduced (eg, from 5% to 95% of the average pore size by ALD coating).

The present invention also contemplates filters comprising porous material substrates coated with ALD coatings, wherein the coating thickness is directionally varied to provide a corresponding pore size gradient in the filter (eg, from the inlet face to the outlet face of the filter) , as described above.

Another aspect of the invention relates to a method of making a porous filter comprising coating a porous material substrate with an ALD coating to reduce the average pore size of the porous material substrate. The method can be used to achieve a predetermined reduction in the average pore size of the porous material matrix and/or a directional varying pore size gradient in the porous material matrix.

In any of the above aspects and embodiments, the porous material matrix may comprise a sintered metal matrix such as titanium, stainless steel, or other metal matrix materials.

In another aspect, the invention relates to a solids vaporizer device comprising a vessel defining an interior volume containing therein a support surface for solid material to be vaporized, wherein the support surface is At least a portion has an ALD coating thereon. The support surface may comprise the interior surface of the vessel (eg, the vessel wall surface and/or the floor of the vessel or an extended surface that is integrally formed with the wall surface and/or floor surface such that the support surface includes the interior surface of the vessel) , and/or the support surface may include the surface of a support member in the interior volume, such as a tray that provides a support surface for the solid material to be vaporized. The tray may be partially or fully coated with an ALD coating. In other embodiments, the vessel may contain an array of vertically spaced trays each providing a support surface for the solid material. Each of such trays in the array can be coated with an ALD coating.

Vessels can be fabricated in which the interior wall surfaces of the vessel that bound their interior volume are coated with an ALD coating. For example, the ALD coating may include aluminum oxide (eg, having a thickness ranging from 2 nm to 500 nm). The support surface coated by the ALD coating in any of the preceding embodiments may be a stainless steel surface. The vaporizer vessel itself may be formed of stainless steel. The vaporizer device may be provided in a solid loading state containing vaporizable solid material on a support surface of the vessel (eg, on the support surface of a stacked tray in the interior volume of the vessel). The vaporizable solid material may be of any suitable type, and may include, for example, precursor materials for vapor deposition or ion implantation operations. The vaporizable solid material may include organometallic compounds or metal halide compounds (eg, aluminum trichloride). It will be appreciated that the ALD coating applied to the support surface of the vessel may be particularly suitable for certain vaporizable solid materials. It will also be appreciated that the ALD coating can be applied to all interior surfaces in the interior volume of the vessel, including the wall and floor surfaces of the vessel and by any trays or other supports for vaporizable solids disposed in the interior volume of the vessel The surface on which the structure appears.

The following disclosure is directed to various illustrative examples of coated substrate articles, devices, and apparatus of the present disclosure that illustrate certain features, aspects, and characteristics of the coating techniques described herein.

Alumina coatings according to the present invention can be applied to the surface of a holder used in vaporizer ampoules, such as the type shown in Figure 3 of the present invention, as previously described herein. 15 is a perspective view of a stainless steel holder useful for use in vaporizer ampoules for aluminum trichloride (AlCl ₃ ) solid precursor delivery for aluminum processes, wherein the aluminum trichloride precursor is supported by the holder and volatilized to Aluminum trichloride precursor vapor is formed to be discharged from the vaporizer ampoule and delivered to the aluminum process through an associated flow line. For example, aluminum processes can be used for metallization of semiconductor device structures suitable for on and/or in wafer substrates.

Figure 16 is a perspective view of a stainless steel holder of the type shown in Figure 15 having an alumina coating thereon, such as by atomic layer deposition, such that the stainless steel surface is made of alumina in a corrosive environment Coating encapsulates the corrosive environment involving aluminum trichloride (AlCl ₃ ) exposure to which the holder is subjected during use and operation of the vaporizer ampoule. By this alumina coating, the holder is protected from corrosion and metal contamination of the precursor vapors is substantially reduced. In addition to this alumina coating of the holder, the entire interior surface of the vaporizer ampoule, as well as the exterior surface of the ampoule, can likewise be coated to provide extended protection from exposure to aluminum trichloride (AlCl ₃ ) solid precursors Corrosive environment derived from the treatment performed ₍ to volatilize the AlCl3 solid precursor to generate precursor vapors for aluminum processing, or for other uses).

The aluminum oxide coating on the surface of the holder and/or other vaporizer ampoule facility may be of any suitable thickness, and may range in thickness from 20 nm to 250 nm or more, for example. In various embodiments, the thickness of the coating on the holder surface may range from 50 nm to 125 nm. It will be appreciated that any suitable thickness of the aluminum oxide coating may be applied by performing a corresponding vapor deposition operation for a corresponding number of deposition cycles and deposition times, where appropriate thicknesses may be determined empirically as appropriate to provide a desired level of resistance to the metal surface. Corrosion protection.

17 is a schematic elevational view of an alumina coating applied by atomic layer deposition to a stainless steel substrate as described above to a solid precursor holder for use in a vaporizer ampule. The alumina coating provides corrosion resistance, prevents chemical reactions with the substrate, and reduces metal contamination in the use of vaporizers for aluminum trichloride precursor vapor generation.

In another application, a yttrium oxide coating can be applied to the surface of an etching device or device component, such as the surface of an injector nozzle used in a plasma etching apparatus. Figure 18 shows the channels of a plasma etch device coated with yttrium _oxide ( _Y2O3 ). Yttrium oxide provides an etch-resistant coating suitable for surfaces and portions with complex shapes, such as high aspect ratio features. When deposited by atomic layer deposition, yttrium oxide forms a dense, conformal pinhole-free coating that is resistant to etching and provides substantially reduced particle shedding and erosion relative to surfaces lacking this yttrium oxide coating.

A yttrium oxide coating can be applied over the aluminum oxide by atomic layer deposition, as shown in the schematic elevation view of FIG. 19 . When applied to plasma etch equipment and equipment components, the ALD yttrium oxide layer provides enhanced corrosion and etch resistance, thereby protecting the underlying surface from harmful plasma exposures such as exposure to chloro- and fluoro-based and other halogen based plasmas). The ALD yttrium oxide layer thereby reduces the generation of unwanted particles and increases the lifetime of the portion of the plasma etching equipment surface coated with the yttrium oxide coating.

In another application, a load lock assembly for an etch chamber apparatus is exposed in use to residual etching chemicals from the etch chamber, resulting in severe corrosion of metal components. An example is a diffuser plate, which may be constructed of stainless steel or other metal or metal alloy, with a filter membrane formed of, for example, nickel or other metal or metal alloy. This diffuser plate assembly can be coated with an alumina coating to encapsulate and protect the diffuser plate and filter membrane. Corrosion of the membrane is prevented by complete encapsulation of the filter membrane.

Figure 20 is a photograph of a diffuser plate assembly comprising a stainless steel frame and a nickel filter membrane as coated with an alumina coating. Figure 21 is a schematic elevation view of a diffuser plate assembly with a stainless steel frame and nickel membrane encapsulated with ALD alumina. ALD coatings provide corrosion and etch resistance layers that protect from harmful chemicals (eg, hydrogen bromide-based chemicals), thereby reducing particles and increasing the life of the assembly.

Another application involves semiconductor processing equipment exposed to chlorine-based precursors from ALD processing and to fluorine-based plasmas from chamber cleaning operations. In such applications, yttrium oxide coatings can be used to provide good etch resistance and to coat parts with complex shapes. One approach in such applications is the use of a combination of physical vapor deposition (PVD) of yttrium oxide and atomic layer deposition (ALD), where ALD is used for thinner coatings of high aspect ratio features and critical components, and PVD is used for thinner coatings. A thick coat is used for the remainder of the section. In this application, the yttrium oxide ALD layer provides corrosion and etch resistance, protection from fluorine-based chemicals and fluorine-based plasmas, thereby reducing particle generation and increasing the performance of the portion coated with the protective yttrium oxide coating life.

Another application involves coating quartz housing structures, such as bulbs for ultraviolet (UV) curing lamps in back-end (BEOL) and front-end (FEOL) UV curing operations. In the operation of UV lamps, such as those in which the bulb is made of quartz, mercury will diffuse into the quartz at the high temperatures involved (eg, about 1000° C.) during operation, and this mercury diffusion will cause the UV lamp to degrade Degradation and a substantial reduction in the operational lifetime of the UV lamps. To combat this mercury migration into the quartz housing (bulb) material, alumina and/or yttrium oxide is coated on the interior surface of the bulb to provide a diffusion barrier layer against mercury intrusion into the quartz housing material.

More generally, aluminum oxide coatings can be used to overcoat and encapsulate various types of metal components to impart corrosion resistance, prevent chemical reactions with substrates, and reduce metal contamination, allowing components such as gas lines, The operating life of valves, pipes, housings, etc.) is correspondingly extended. By using atomic layer deposition, the interior surfaces of parts, including parts with complex interior surface geometries, can be coated, and an aluminum oxide layer or other protective coating can be employed to provide dense pin-free holes above the substrate surface and Conformal protection layer.

Another application of the protective coating of the present invention is, for example, the protective coating of the surface of plasma sources in semiconductor manufacturing, flat panel display manufacturing, and solar panel manufacturing. Such plasma sources can be of any suitable type and, for example, can generate ammonia plasma, hydrogen plasma, nitrogen trifluoride plasma, and other kinds of plasma. A protective coating can be used to replace the plasma _- wetted portion of the anodized surface to provide enhanced plasma etch resistance (eg, exposure to NF plasma for >1000 hours), while accommodating hydrogen (H*) and fluorine (F*) Surface recombination and high electrical isolation voltage (eg, greater than 1000V).

Figure 22 shows an aluminum substrate, an ALD alumina coating, and a PVD AlON coating. The thickness of the respective aluminum oxide and aluminum oxynitride coatings can be any suitable thickness. By way of example, the thickness of the alumina coating may range from 0.05 μm to 5 μm, and the thickness of the PVD coating may range from 2 μm to 25 μm. In certain embodiments, the alumina coating has a thickness of 1 μm and the PVD AlON coating has a thickness of 10 μm. In this structure, the PVDAlON coating provides etch resistance and plasma surface recombination capabilities to the device, and the alumina coating provides an electrically insulating coating in addition to etch resistance.

Another application involves dielectric stacks for thermal chuck assemblies, which may have a layer structure as shown in FIG. 23 . As shown, an alumina substrate has an electrode metal (eg, nickel) thereon on which an ALD alumina electrical isolation layer is located. A PVD aluminum oxynitride coating is deposited on the aluminum oxide layer, and a chemical vapor deposition (CVD) deposited silicon oxynitride (SiON) layer is deposited on the AlON layer. In this layer structure, the CVD SiON layer provides a cleaning path for the contact surfaces and electrical spacers, the PVD AlON layer provides a coefficient of thermal expansion (CTE) buffer layer, the ALD aluminum oxide layer provides the electrical isolation layer, and the nickel on the aluminum oxide substrate provides electrode metal layer.

Yet another application involves a plasma activation chuck assembly of a plasma activation chamber, wherein the aluminum portion is coated with a multi-layer stack including the multi-layer stack shown in FIGS. 24 and 25 . The multi-layer stack of Figure 24 includes a chemical vapor deposition applied silicon layer on an aluminum substrate, with an ALD zirconia layer on a CVD Si layer. In this multi-layer stack, the ALD zirconia layer is used to provide a clean and dense access to the contact surface, thereby serving as a diffusion barrier and an electrical isolation layer. The CVD silicon layer provides a clean buffer layer on the aluminum substrate. The multi-layer stack of Figure 25 includes a CVD silicon oxynitride layer on an aluminum substrate, and an ALD aluminum oxide layer on a CVD SiON coating, wherein the ALD aluminum oxide layer serves as an electrical isolation layer, a diffusion barrier layer, and a contact The surface provides a layer of clean dense pathways. The CVD SiON layer provides a clean buffer layer in the multilayer coating structure.

Another application of the coating techniques of the present invention relates to the coating of porous substrates and filter articles, wherein coatings such as alumina can be deposited by atomic layer deposition, which achieves penetration depth and coating into the porous substrate or filter material. Independent control of layer thickness. Depending on the article and its specific end use, partial or full alumina coating penetration may be employed.

26 is a photomicrograph of a porous material having a wall thickness of 1.5 mm and a pore size of 2 μm to 4 μm, coated with alumina by atomic layer deposition. Figure 27 is a schematic representation of an encapsulated film comprising a film formed of stainless steel, nickel, titanium, or other suitable material that has been fully encapsulated with alumina deposited by ALD to provide exposure to the The encapsulating film provides corrosion and etch resistance, protection from chemical attack, reduction in particle generation, and reduction in metal contamination.

The use of atomic layer deposition as indicated provides the ability to independently control coating penetration depth and coating thickness. This capability is useful for controlling the pore size and flow constraints of ultrafine thin films (eg, ultrafine thin films having nominal pore sizes ranging from 20 nm to 250 nm (eg, nominal pore sizes of approximately 100 nm).

Figure 28 is a photomicrograph of a coated filter wherein the coating is alumina with a coating penetration depth of 35 μm. Figure 29 is a photomicrograph of a coated filter wherein the coating is alumina with a coating penetration depth of 175 μm.

Consistent with the foregoing disclosures herein, in one aspect, the present invention relates to a solids vaporizer apparatus comprising a vessel defining an interior volume therein, an outlet configured to discharge precursor vapors from the vessel, and the vessel a support structure in said interior volume of said support structure adapted to support solid precursor material thereon for volatilization of said solid precursor material to form said precursor vapor, wherein said solid precursor material comprises an aluminum precursor, and wherein at least a portion of the surface region in the interior volume is coated with an aluminum oxide coating. In various embodiments of this solid vapor device, the surface area may include at least one of a surface area of the support structure and a surface area in the interior volume of the vessel. In other embodiments, the surface area may include a surface area of the support structure and a surface area in the interior volume of the container. In still other embodiments, the alumina-coated surface region in the interior volume comprises stainless steel. In various embodiments of the solid vaporizer device, the alumina coating may have a thickness ranging from 20 nm to 125 nm. For example, the alumina coating may include the ALD alumina coating of any of the preceding aspects and embodiments.

In another aspect, the present invention relates to a method of enhancing the corrosion resistance of a stainless steel structure, material or device exposed to aluminum halide in use or operation, the method comprising using aluminum oxide coating to coat the stainless steel structure, material or device. In this method, for example, the aluminum oxide coating may have a thickness ranging from 20 nm to 125 nm. For example, the aluminum oxide coating can be applied by atomic layer deposition.

In another aspect, the present invention relates to a semiconductor processing etch structure, component or device that is exposed to an etching medium in use or operation, the structure, component or device being coated with A coating comprising a layer of yttrium oxide, wherein the layer of yttrium oxide optionally overlies an aluminum oxide layer in the coating. For example, the etched structure, component or device may include an etch device injector nozzle.

Another aspect of the invention relates to a method of enhancing the corrosion and etch resistance of a semiconductor processing etched structure, component or device that is exposed to an etching medium during use or operation, whereby The method includes coating the structure, component or device with a coating comprising a layer of yttrium oxide, wherein the layer of yttrium oxide optionally overlies a layer of aluminum oxide in the coating.

Yet another aspect of the present invention relates to an etch chamber diffuser plate comprising a nickel film encapsulated with an alumina coating. In this etch chamber diffuser plate, the alumina coating may include an ALD alumina coating.

Another aspect of the invention relates to a method of enhancing the corrosion and etch resistance of an etch chamber diffuser plate comprising a nickel film, the method comprising coating the nickel film with an aluminum oxide encapsulation coating. For example, the alumina coating may include an ALD coating.

In another aspect, the present invention relates to a vapor deposition processing structure, assembly or apparatus exposed to a halide medium in use or operation, the structure, assembly or apparatus being coated with a yttrium oxide coating, the oxide Yttrium coatings include ALD yttrium oxide base coatings and PVD yttrium oxide top coatings. In this structure, assembly, or device, the surface coated with the ALD yttrium oxide base coating and the PVD yttrium oxide top coating may include aluminum.

Another aspect of the invention relates to a method of enhancing the corrosion and etch resistance of a vapor deposition process structure, assembly or device that is exposed to a halide medium in use or operation, The method includes coating the structure, component or device with a yttrium oxide coating including an ALD yttrium oxide base coating and a PVD yttrium oxide top coating. As described above, the structure, assembly or device may comprise an aluminum surface coated with the yttria coating.

Another aspect of the present invention relates to a quartz housing structure having an alumina diffusion barrier layer coated on its interior surface.

A corresponding aspect of the invention relates to a method of reducing the diffusion of mercury into a quartz housing structure susceptible to such diffusion in its operation, the method comprising coating with an alumina diffusion barrier layer the inner surface of the quartz housing structure.

In another aspect, the present invention relates to a plasma source structure, assembly or device which, in use or operation, is exposed to plasma and voltages in excess of 1000V, wherein the plasma wets the surface of the structure, assembly or device An ALD alumina coating was applied, and the alumina coating was overcoated with a PVD alumina oxynitride coating. For example, the plasma wetted surface may comprise aluminum or aluminum oxynitride.

Another aspect of the invention relates to a method of enhancing the service life of a plasma source structure, assembly or device that is exposed to plasma and voltages in excess of 1000V during use or operation, so that The method includes coating a plasma wetted surface of the structure, component or device with an ALD alumina coating and overcoating the alumina coating with a PVD alumina oxynitride coating. As indicated above, the plasma wetted surface may comprise aluminum or aluminum oxynitride.

Additional aspects of the invention relate to a dielectric stack comprising a sequence layer comprising an alumina base layer, a nickel electrode layer on the alumina base layer, ALD alumina on the nickel electrode layer An electrical isolation layer, a PVD aluminum oxynitride thermal expansion buffer layer on the ALD aluminum oxide electrical isolation layer, and a CVD silicon oxynitride wafer contact surface and an electrical spacer layer on the PVD aluminum oxynitride thermal expansion buffer layer.

Contemplated in another aspect of the present invention is a plasma activated structure, component or device comprising an aluminum surface coated with one of the multi-layer coatings of (i) and (ii): (i) located in the a CVD silicon base coating on the aluminum surface, and an ALD zirconia layer on the CVD silicon base coating; and (ii) a CVD silicon oxynitride base coating on the aluminum surface, and an ALD zirconia layer on the aluminum surface ALD aluminum oxide layer on CVD silicon oxynitride base coat.

A corresponding method for reducing particle formation and metal contamination of aluminum surfaces of plasma-activated structures, components or devices is contemplated, the method comprising coating with one of the multi-layer coatings of (i) and (ii) Overlying the aluminum surface: (i) a CVD silicon basecoat on the aluminum surface, and an ALD zirconia layer on the CVD silicon basecoat; and (ii) a CVD on the aluminum surface A silicon oxynitride base coating, and an ALD aluminum oxide layer on the CVD silicon oxynitride base coating.

In another aspect, the present invention contemplates a porous matrix filter comprising a membrane formed of stainless steel, nickel or titanium, wherein the membrane is encapsulated with alumina to achieve a coating in the range from 20 μm to 2000 μm Layer penetration depth. More specifically, in various embodiments, the porosity may have a nominal pore size in the range from 10 nm to 1000 nm.

Another aspect of the invention relates to a method of making a porous matrix filter comprising encapsulating a film formed of stainless steel, nickel or titanium with alumina to a coating penetration depth ranging from 20 μm to 2000 μm. In a particular embodiment of this method, encapsulation includes ALDing the alumina, and the method is performed to provide in the porous matrix filter having a nominal pore size in the range from 10 nm to 1000 nm porosity.

Although the invention has been described herein with reference to specific aspects, features and illustrative embodiments, it will be appreciated that the utility of the invention is not limited thereby, but extends to and encompasses numerous other changes, modifications and alternative embodiments, such as Such other changes, modifications, and alternative embodiments will suggest themselves to those skilled in the art based on the descriptions herein. Accordingly, the present invention as hereinafter claimed is intended to be broadly construed and understood to include all such changes, modifications and alternative embodiments within its spirit and scope.

Claims (10)

1. A porous substrate filter comprising a metal film, wherein the metal film is encapsulated with a metal oxide coating having a penetration depth in the range from 20 μ ι η to 2000 μ ι η.

2. The porous matrix filter of claim 1, wherein the metal membrane is formed of stainless steel, nickel, or titanium.

3. The porous matrix filter of claim 1, wherein the metal thin film is a sintered matrix of stainless steel fibers, particles, or a combination of both.

4. The porous matrix filter of claim 1, wherein the metal oxide coating comprises a metal oxide selected from the group consisting of: titanium dioxide; alumina; zirconium oxide; an oxide of formula MO, wherein M is Ca, Mg or Be; an oxide of the formula M 'O2, wherein M' is a stoichiometrically acceptable metal; and formula Ln₂O₃Wherein Ln is a lanthanide La, Sc or Y.

5. The porous matrix filter of claim 1, wherein the metal oxide coating is an alumina coating.

6. The porous matrix filter of claim 1 wherein the metal oxide coating is an ALD coating having a thickness ranging from 2nm to 500 nm.

7. The porous matrix filter of claim 1 wherein the metal oxide coating is an ALD coating having a thickness that is directionally varied to provide a corresponding pore size gradient within the porous matrix filter.

8. A filter comprising a substrate of metal fibers, metal particles, or a combination of metal fibers and metal particles, the substrate having an ALD coating thereon,

wherein the ALD coating does not alter the pore volume of the substrate of the metal fiber, metal particle, or combination of metal fiber and metal particle by more than 5% as compared to a corresponding substrate of the metal fiber, metal particle, or combination of metal fiber and metal particle lacking the ALD coating thereon, and

wherein the matrix is characterized by pores having a diameter in the range of from 1 μm to 40 μm.

9. A method of making a porous matrix filter comprising encapsulating a thin metal film by ALD using a metal oxide coating to a penetration depth in the range from 20 to 2000 μ ι η.

10. The method of claim 9, wherein the coating thickness is directionally varied to provide a corresponding pore size gradient in the filter.

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