Forming films with improved hierarchical coverage

Abstract

An apparatus is provided. The device includes a substrate having at least one structure having an aspect ratio of at least 10: 1. The device includes a film positioned overlying the at least one structure in a step of at least 90%. The film comprises: a metal oxide or metalloid oxide; and a concentration of less than 1 * 1020 hydrogen atoms per cubic centimeter as measured by SIMS. Also provided herein are methods for forming a film on a substrate, and related systems and methods.

Description

Technical Field

[0001] This disclosure relates to the formation of membranes with improved class coverage, related apparatus, related systems, and related methods.

[0002] Cross-reference of related applications

[0003] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 535,287, filed August 29, 2023, and U.S. Provisional Patent Application No. 63 / 656,991, filed June 6, 2024, pursuant to 35 USC 119, the entire disclosure of each of which is hereby incorporated herein by reference. Background Technology

[0004] Films deposited via vapor deposition processes can result in inhomogeneous films. Problems related to the self-decomposition and insufficient diffusion of the metal precursor source, or the dosage of the metal precursor source, can lead to inhomogeneous film deposition. Similarly, co-reactants can have problems associated with decomposition, insufficient diffusion, insufficient dosage, or any combination thereof on the film surface.

[0005] Public content

[0006] Some embodiments of this disclosure relate to a method. In some embodiments, the method is a method for forming a film. In some embodiments, the method includes exposing a substrate having at least one structure with an aspect ratio of at least 10:1 to a first precursor gas. In some embodiments, the method includes flowing a feed gas to an ozone generator to generate a second precursor gas, the feed gas comprising at least 1 volume% N2 based on the total volume of the feed gas. In some embodiments, the method includes exposing the substrate to the second precursor gas to form a film having at least 90% step coverage on the at least one structure of the substrate.

[0007] Some embodiments of this disclosure relate to an apparatus. In some embodiments, the apparatus includes a substrate. In some embodiments, the substrate has at least one structure having an aspect ratio of at least 10:1. In some embodiments, the apparatus includes a film. In some embodiments, the film is positioned on the at least one structure with at least 90% grade coverage. In some embodiments, the film includes a metal oxide. In some embodiments, the film includes a particle size of less than 1 × 10⁻⁶ as measured by SIMS. 20 The concentration of hydrogen atoms per cubic centimeter. Attached Figure Description

[0008] Some embodiments of this disclosure are described herein by way of example only, with reference to the accompanying drawings. Detailed reference is now made to the drawings, and it should be emphasized that the illustrated embodiments are merely examples and for illustrative discussion of embodiments of this disclosure. In this regard, the description in conjunction with the drawings will enable those skilled in the art to understand how embodiments of this disclosure can be practiced.

[0009] Figure 1 This is a flowchart of a method for forming a membrane according to some embodiments.

[0010] Figure 2 This is a block diagram of a system for vapor deposition according to some embodiments. Detailed Implementation

[0011] Other objects and advantages of this disclosure will become apparent from the following description taken in conjunction with the accompanying drawings, among the disclosed benefits and improvements. Detailed embodiments of this disclosure are disclosed herein; however, it should be understood that the disclosed embodiments are merely illustrative of the disclosure as it may be embodied in various forms. Furthermore, each example given with respect to the various embodiments of this disclosure is intended to be illustrative and not limiting.

[0012] Any existing patents and publications referenced in this document are incorporated herein by reference in their entirety.

[0013] Throughout this specification and claims, unless otherwise expressly stated herein, the following terms shall have the meanings explicitly and consequentially used herein. The phrases “in one embodiment,” “in an embodiment,” and “in some embodiments” as used herein do not necessarily refer to the same embodiment, but may refer to the same embodiment. Furthermore, the phrases “in another embodiment” and “in some other embodiments” as used herein do not necessarily refer to different embodiments, but may refer to different embodiments. All embodiments of this disclosure are intended to be combined without departing from the scope or spirit of this disclosure.

[0014] As used herein, unless otherwise expressly stated in the text, the term "based on" is non-exclusive and allows for consideration of additional factors not described. Furthermore, throughout this specification, the terms "a" and "described" have multiple meanings. "In" has both the meanings of "in" and "on".

[0015] Some embodiments relate to methods, systems, and apparatuses for forming films with improved class coverage on a substrate. Some film deposition processes exhibit unpredictable poor class coverage. As disclosed herein, it has been found that when a precursor gas including N2 is the feed gas supplied to an ozone generator and the resulting gas from the ozone generator (e.g., corona plasma) is used in the vapor phase deposition process, abruptly increasing the concentration of nitrogen (N2) in the precursor gas to above the conventional levels of 10 to 15 ppm leads to an improvement in class coverage. Therefore, in some embodiments, methods, systems, apparatuses, and methods are provided for forming films (e.g., metal oxide films) with at least 90% class coverage on at least one high aspect ratio structure of a substrate.

[0016] Examples of vapor deposition processes include (but are not limited to) at least one of the following: chemical vapor deposition (CVD) processes, digital or pulsed chemical vapor deposition processes, plasma-enhanced cyclic chemical vapor deposition (PECCVD) processes, flowable chemical vapor deposition (FCVD) processes, atomic layer deposition (ALD) processes, thermal atomic layer deposition, plasma-enhanced atomic layer deposition (PEALD) processes, metal-organic chemical vapor deposition (MOCVD) processes, plasma-enhanced chemical vapor deposition (PECVD) processes, or any combination thereof.

[0017] As used herein, the term "tiered coverage" refers to the ratio of the thickness of a film on a first surface of the substrate to the thickness of a film on a second surface of the substrate. In some embodiments, the first surface and the second surface of the substrate are different. For example, in some embodiments, the first surface of the substrate is the surface at the bottom of a high aspect ratio structure (e.g., a trench) and the second surface of the substrate is the surface at the top of a high aspect ratio structure (e.g., a trench). Non-limiting examples of high aspect ratio structures, as disclosed herein, include (e.g., but not limited to) at least one of trenches, chambers, cavities, holes, channels, or any combination thereof. It should be understood that other structures will have a high aspect ratio and therefore these should not be considered limiting.

[0018] Figure 1 This is a flowchart of a method 100 for forming a film according to some embodiments. For example... Figure 1 As shown, a method 100 for forming a film may include one or more of the following steps: exposing a substrate 102 to a first precursor gas; flowing a feed gas 104 to an ozone generator to generate a second precursor gas; and exposing the substrate 106 to the second precursor gas to form a film on the substrate. In some embodiments, performing one or more of steps 102, 104, and 106 includes a deposition cycle. In some embodiments, the method 100 for forming a film includes any range or subrange between one deposition cycle and 100,000 deposition cycles.

[0019] In some embodiments, the method 100 for forming a film includes exposing a substrate 102 to a first precursor gas. In some embodiments, exposure 102 includes introducing the first precursor gas into a chamber containing the substrate. In some embodiments, exposure 102 includes allowing the first precursor gas to flow into the chamber containing the substrate. In some embodiments, exposure 102 includes supplying the first precursor gas to the chamber containing the substrate. In some embodiments, exposure 102 includes pumping the first precursor gas into the chamber containing the substrate. In some embodiments, exposure 102 includes pulsating the first precursor gas into the chamber containing the substrate. In some embodiments, exposure 102 includes pulsating the first precursor gas into the chamber containing the substrate for a duration. In some embodiments, exposure 102 is sufficient to allow the first precursor gas and the substrate to be in direct or close proximity or direct physical contact.

[0020] In some embodiments, exposure 102 includes pulsating a first precursor gas into a substrate-containing chamber for a duration. In some embodiments, the duration is a duration of any range or subrange between 0.01 seconds and 60 minutes or longer. For example, in some embodiments, the duration is a duration of 0.01 seconds to 50 minutes, 0.01 seconds to 40 minutes, 0.01 seconds to 30 minutes, 0.01 seconds to 20 minutes, 0.01 seconds to 10 minutes, 0.01 seconds to 1 minute, 0.01 seconds to 45 seconds, 0.01 seconds to 30 seconds, 0.01 seconds to 15 seconds, 0.01 seconds to 10 seconds, 0.01 seconds to 5 seconds, 0.01 seconds to 3 seconds, 0.01 seconds to 1 second, 0.01 seconds to 0.5 seconds, 0.01 seconds to 0.1 seconds, or 0.01 seconds to 0.05 seconds. In some embodiments, the duration is a duration of 0.05 seconds to 60 minutes, 0.10 seconds to 60 minutes, 0.2 seconds to 60 minutes, 0.3 seconds to 60 minutes, 0.4 seconds to 60 minutes, 0.5 seconds to 60 minutes, 0.6 seconds to 60 minutes, 0.7 seconds to 60 minutes, 0.8 seconds to 60 minutes, 0.9 seconds to 60 minutes, 1 second to 60 minutes, 3 seconds to 60 minutes, 5 seconds to 60 minutes, 15 seconds to 60 minutes, 30 seconds to 60 minutes, 1 minute to 60 minutes, 10 minutes to 60 minutes, 20 minutes to 60 minutes, 30 minutes to 60 minutes, 40 minutes to 60 minutes, or 50 minutes to 60 minutes.

[0021] In some embodiments, the duration is a duration of 0.01 seconds to 5 minutes or longer, or any range or subrange between 0.01 seconds and 5 minutes. For example, in some embodiments, the duration is a duration of 0.01 seconds to 4 minutes, 0.01 seconds to 3 minutes, 0.01 seconds to 2 minutes, 0.01 seconds to 1 minute, 0.01 seconds to 50 seconds, 0.01 seconds to 40 seconds, 0.01 seconds to 30 seconds, 0.01 seconds to 20 seconds, 0.01 seconds to 10 seconds, 0.01 seconds to 5 seconds, or 0.01 seconds to 3 seconds, 0.01 seconds to 1 second, 0.01 seconds to 0.5 seconds, 0.01 seconds to 0.1 seconds, or 0.01 seconds to 0.05 seconds. In some embodiments, the duration is a duration of 0.05 seconds to 5 minutes, 0.10 seconds to 5 minutes, 0.2 seconds to 5 minutes, 0.3 seconds to 5 minutes, 0.4 seconds to 5 minutes, 0.5 seconds to 5 minutes, 0.6 seconds to 5 minutes, 0.7 seconds to 5 minutes, 0.8 seconds to 5 minutes, 0.9 seconds to 5 minutes, 1 second to 5 minutes, 3 seconds to 5 minutes, 5 seconds to 5 minutes, 15 seconds to 5 minutes, 30 seconds to 5 minutes, 1 minute to 5 minutes, 2 minutes to 5 minutes, 3 minutes to 5 minutes, or 4 minutes to 5 minutes.

[0022] In some embodiments, exposure 102 is performed at a temperature range or subrange between 100°C and 500°C. For example, in some embodiments, exposure 102 is performed at temperatures ranging from 100°C to 475°C, 100°C to 450°C, 100°C to 425°C, 100°C to 400°C, 100°C to 375°C, 100°C to 350°C, 100°C to 325°C, 100°C to 300°C, 100°C to 275°C, 100°C to 250°C, 100°C to 225°C, 100°C to 200°C, 100°C to 175°C, 100°C to 150°C, or 100°C. The temperature range is 125℃, 125℃ to 500℃, 150℃ to 500℃, 175℃ to 500℃, 200℃ to 500℃, 225℃ to 500℃, 250℃ to 500℃, 275℃ to 500℃, 300℃ to 500℃, 325℃ to 500℃, 350℃ to 500℃, 375℃ to 500℃, 400℃ to 500℃, 425℃ to 500℃, 450℃ to 500℃, or 475℃ to 500℃.

[0023] In some embodiments, the substrate is a high aspect ratio substrate. For example, in some embodiments, the high aspect ratio substrate includes a substrate having at least one structure with a high aspect ratio. In some embodiments, the substrate may have multiple structures, each of which has a high aspect ratio. The number of structures with high aspect ratios is not particularly limited but may range from one structure to thousands of structures. At least one structure is not particularly limited but may include any structure with a high aspect ratio disclosed herein. In some embodiments, at least one structure includes at least one of a trench, chamber, cavity, aperture, channel, or any combination thereof. Although high aspect ratio structures are disclosed herein, it should be understood that the embodiments disclosed herein also include substrates that do not have a high aspect ratio structure.

[0024] The aspect ratio of a structure can refer to the ratio of width, depth, height, length, or diameter to any combination of two. In some embodiments, for example, the aspect ratio refers to the ratio of the depth of a circular hole (e.g., a fine hole) to its diameter. In some embodiments, the aspect ratio refers to the ratio of the depth of a non-circular hole (e.g., a trench) to its width. Non-limiting examples of substrates comprising high aspect ratio substrates include (but are not limited to) at least one of diaphragms, showerheads, liners, tubes, gas lines, valves, syringes, trays, or any combination thereof.

[0025] At least one structure on the substrate may be a structure having an aspect ratio of at least 10:1. For example, in some embodiments, the substrate has at least one structure having an aspect ratio of at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, at least 60:1, at least 70:1, at least 80:1 or at least 90:1. In some embodiments, the substrate has at least one structure having an aspect ratio of 10:1 to 100:1, 10:1 to 90:1, 10:1 to 80:1, 10:1 to 70:1, 10:1 to 60:1, 10:1 to 50:1, 10:1 to 40:1, 10:1 to 30:1, 10:1 to 20:1, 20:1 to 100:1, 30:1 to 100:1, 40:1 to 100:1, 50:1 to 100:1, 60:1 to 100:1, 70:1 to 100:1, 80:1 to 100:1, or 90:1 to 100:1. In some embodiments, at least one structure and the substrate are a single integral piece. In some embodiments, at least one structure and the substrate are manufactured separately and assembled together.

[0026] The substrate may include a substrate for microelectronic applications and / or semiconductor applications. In some embodiments, the substrate includes at least one of the following: silicon, silicon oxide, silicon-on-insulator (SOI), carbon-doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, metal, metal nitride, metal alloy, or any combination thereof. In some embodiments, the substrate includes a semiconductor. In some embodiments, the substrate includes at least one of titanium, titanium nitride, tungsten, tungsten nitride, tantalum, tantalum nitride, or any combination thereof.

[0027] The first precursor gas includes at least one of an elemental metal, a metal halide, a metal halide oxide, an organometallic compound, an organometallic complex, or any combination thereof. In some embodiments, the first precursor gas includes at least one of the following: HfCl4, ZrCl4, AlCl3, TiCl4, TaCl5, NbCl5, VCl4, GaCl3, InCl3, or any combination thereof. In some embodiments, the first precursor gas includes at least one of the following: dimethylhydrazine, trimethylaluminum (TMA), hafnium chloride (HfCl4), zirconium chloride (ZrCl4), indium trichloride, indium monochloride, aluminum trichloride, titanium iodide, carbonyl tungsten, Ba(DPM)2, bis(di-neopentylmethyl)strontium (Sr(DPM)2), TiO(DPM)2, tetra(di-neopentylmethyl)zirconium (Zr(DPM)4), decaborane, octadecborane, boron, magnesium, gallium, indium, antimony, copper, phosphorus, arsenic, lithium, sodium tetrafluoroborate, a precursor incorporating an alkylmidyl ligand, an organometallic precursor, and zirconium tributoxide. (Zr(t-OBu)4), tetra(diethylamino)zirconium (Zr(Net2)4), tetra(diethylamino)hafnium (Hf(Net2)4), tetra(dimethylamino)titanium (TDMAT), tributylaminotri(diethylamino)tantalum (TBTDET), penta(dimethylamino)tantalum (PDMAT), penta(ethylmethylamino)tantalum (PEMAT), tetra(dimethylamino)zirconium (Zr(NMe2)4), tributanol hafnium (Hf(tOBu)4), xenon difluoride (XeF2), xenon tetrafluoride (XeF4), xenon hexafluoride (XeF6), or any combination thereof.

[0028] In some embodiments, the first precursor gas includes at least one of the following: rare earth β-diketone compounds (e.g., (La(THD)3) and / or (Y(THD)3)), rare earth cyclopentadienyl (Cp) compounds (e.g., La(iPrCp)3), rare earth amidine compounds (e.g., tris(methylamidanyl)lanthanum La(FAMD)3), cyclooctadienyl compounds containing rare earth metals, and alkylamide compounds (e.g., tris(dimethylamidanyl)cyclopentadienylhafnium (Hf(C5H5)(N(CH3))). )2)3), tris(dimethylamido)cyclopentadienylzirconium (Zr(C5H5)(N(CH3)2)3), tetra(ethylmethylamino)hafnium (TEMAHf)), tetra(ethylmethylamino)zirconium (TEMAZr), tetra(diethylamino)hafnium ((Et2N)4Hf or TDEAH) and / or tetra(dimethylamino)hafnium ((Me2N)4Hf or TDMAH), alkoxides, silicon halogen compounds, silicon tetrachloride, Si2Cl6, silicon tetrafluoride, silicon tetraiodide or any combination thereof.

[0029] In some embodiments, the first precursor gas includes at least one of the following: decaborane, hafnium tetrachloride, zirconium tetrachloride, indium trichloride, organometallic β-diketone complex, tungsten hexafluoride, cyclopentadienylcycloheptadienyl-titanium (CpTiCht), aluminum trichloride, titanium iodide, cyclooctatetraenylcyclopentadienyltitanium, dicyclopentadienyltitanium bis(azide), trimethylgallium, trimethylindium, alkylaluminum (such as trimethylaluminum, triethylaluminum, trimethylaminealuminane), dimethylzinc, tetramethyltin, trimethylantimony, diethylcadmium, carbonyltungsten, or any combination thereof.

[0030] In some embodiments, the first precursor gas comprises at least one of the following: elemental boron, copper, phosphorus, decaborane, gallium halide, indium halide, antimony halide, arsenic halide, gallium halide, aluminum iodide, titanium iodide, MoO2Cl2, MoOCl4, MoCl5, WCl5, WOCl4, WCl6, cyclopentadienylcycloheptanetrienyl titanium (CpTiCht), cyclooctatetraenylcyclopentadienyl titanium, dicyclopentadienyl titanium bis(azide), In(CH3)2(hfac), dibromomethylantimonide, carbonyl tungsten, organometallic β-diketone complexes, organometallic alkoxide complexes, organometallic carboxylate complexes, organometallic aryl complexes, organometallic amide complexes, or any combination thereof. In some embodiments, the vaporizable precursor comprises at least one of the following, consists of at least one of the following, or is substantially composed of at least one of the following: MoO2Cl2, MoOCl4, WO2Cl2, WOCl4, or any combination thereof.

[0031] In some embodiments, the first precursor gas includes at least one of the following: decborane, (B 10 H 14 ), pentoborane (B5H9), octadecoborane (B18 H 22 Boric acid (H3BO3), SbCl3, SbCl5, or any combination thereof. In some embodiments, the first precursor gas includes at least one of the following: AsCl3, AsBr3, AsF3, AsF5, AsH3, As4O6, As2Se3m, As2S2, As2S3, As2S5, As2Te3, B4H 11 B4H 10 , B3H6N3, BBr3, BCl3, BF3, BF3.O(C2H5)2, BF3.HOCH3, B2H6, F2, HF, GeBr4, GeCl4, GeF4 , GeH4, H2, HCl, H2Se, H2Te, H2S, WF6, SiH4, SiH2Cl2, SiHCl3, SiCl4, SiH3Cl, Si2Cl6, NH 3. NH3, Ar, Br2, HBr, BrF5, CO2, CO, COCl2, COF2, Cl2, ClF3, CF4, C2F6, C3F8, C4F8, C5F8 , CHF3, CH2F2, CH3F, CH4, SiH6, He, HCN, Kr, Ne, Ni(CO)4, HNO3, NO, N2, NO2, NF3, N2O, C8H 24 O4Si4, PH3, POCl3, PCl5, PF3, PFS, SbH3, SO2, SF6, SF4, Si(OC2H5)4, C4H 16 Si4O4, Si(CH3)4, SiH(CH3)3, TiCl4, Xe, SiF4, WOF4, TaBr5, TaCl5, TaF5, Sb(C2H5)3, Sb(CH3)3, In(CH3)3, PBr5, PBr3, RuF5, or any combination thereof. It should be understood that other precursors may be used herein without departing from this disclosure. In some embodiments, the first precursor gas is a metal precursor.

[0032] In some embodiments, the method 100 for forming a membrane includes flowing a feed gas 104 to an ozone generator to generate a second precursor gas. In some embodiments, flowing 104 includes supplying the feed gas to the ozone generator. In some embodiments, flowing 104 includes pumping the feed gas to the ozone generator. In some embodiments, flowing 104 includes introducing the feed gas into the ozone generator. In some embodiments, flowing 104 includes conveying the feed gas to the ozone generator. In some embodiments, flowing 104 includes, for example, drawing the feed gas into the ozone generator under vacuum. In some embodiments, flowing 104 includes flowing the feed gas directly to the ozone generator to generate the second precursor gas. In some embodiments, flowing 104 includes flowing a first feed gas to the ozone generator and flowing a second feed gas to the ozone generator. In some embodiments, the first feed gas is different from the second feed gas. In some embodiments, the first feed gas includes, for example, nitrogen and / or N2. In some embodiments, the second feed gas includes an oxidizing gas. In some embodiments, flowing 104 includes flowing a single gas stream comprising the feed gas.

[0033] In some embodiments, the feed gas comprises at least 1 volume% of N2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 2 volume% of N2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 5 volume% of N2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 10 volume% of N2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 15 volume% of N2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 20 volume% of N2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 25 volume% of N2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 30 volume% of N2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 35 volume% of N2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises any range or subrange between 1 volume% and 40 volume% of N2, or between 1% and 40%, based on the total volume of the feed gas. For example, in some embodiments, the feed gas includes 1% to 40% by weight, 1% to 35% by weight, 1% to 30% by weight, 1% to 25% by weight, 1% to 20% by weight, 1% to 15% by weight, 1% to 10% by weight, 1% to 5% by weight, 5% to 40% by weight, 10% to 40% by weight, 15% to 40% by weight, 20% to 40% by weight, 25% to 40% by weight, 30% to 40% by weight, or 35% to 40% by weight of N2 based on the total volume of the feed gas.

[0034] In some embodiments, the feed gas comprises at least 50 vol% O2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 60 vol% O2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 65 vol% O2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 70 vol% O2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 75 vol% O2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 80 vol% O2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 85 vol% O2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises at least 90 vol% O2 based on the total volume of the feed gas. In some embodiments, the feed gas comprises any range or subrange between 50 vol% and 99 vol% O2 based on the total volume of the feed gas. For example, in some embodiments, the feed gas includes 50% to 99% of the total volume of the feed gas, 50% to 90% of the total volume of the feed gas, 50% to 85% of the total volume of the feed gas, 50% to 75% of the total volume of the feed gas, 50% to 70% of the total volume of the feed gas, 50% to 65% of the total volume of the feed gas, 50% to 60% of the total volume of the feed gas, 50% to 55% of the total volume of the feed gas, 55% to 99% of the total volume of the feed gas, 60% to 99% of the total volume of the feed gas, 65% to 99% of the total volume of the feed gas, 70% to 99% of the total volume of the feed gas, 75% to 99% of the total volume of the feed gas, 80% to 99% of the total volume of the feed gas, 85% to 99% of the total volume of the feed gas, or 90% to 99% of the total volume of the feed gas.

[0035] In some embodiments, the feed gas comprises 0.1% to 20% by volume of H2, or any range or subrange between 0.1% and 20% based on the total volume of the feed gas. For example, in some embodiments, the feed gas comprises 0.1% to 19%, 0.1% to 18%, 0.1% to 17%, 0.1% to 16%, 0.1% to 15%, 0.1% to 14%, 0.1% to 13%, 0.1% to 12%, 0.1% to 11%, 0.1% to 10%, 0.1% to 9%, 0.1% to 8%, 0.1% to 7%, 0.1% to 6%, 0.1% to 5%, 0.1% to 4%, 0.1% to 3%, 0.1% to 2%, 0.1% to 1%, 0.1% to 0.9%, 0.1% to 0.8%, 0. 1% to 0.7%, 0.1% to 0.6%, 0.1% to 0.5%, 0.1% to 0.4%, 0.1% to 0.3%, 0.1% to 0.2%, 1% to 20%, 2% to 20%, 3% to 20%, 4% to 20%, 5% to 20%, 6% to 20%, 7% to 20%, 8% to 20%, 9% to 20%, 10% to 20%, 11% to 20%, 12% to 20%, 13% to 20%, 14% to 20%, 15% to 20%, 16% to 20%, 17% to 20%, 18% to 20%, or 19% to 20%.

[0036] In some embodiments, the second precursor gas includes ozone (O3). In some embodiments, the second precursor gas further includes at least one of elemental oxygen (O), oxygen gas (O2), water (H2O), hydrogen peroxide (H2O2), nitrous oxide (N2O), nitric oxide (NO), nitrous oxide pentoxide (N2O5), nitrogen dioxide (NO2), NO3, or any combination thereof. In some embodiments, the second precursor gas includes one or more of the first precursor gases.

[0037] In some embodiments, the method 100 for forming a film includes exposing a substrate 106 to a second precursor gas to form a film on the substrate. In some embodiments, exposure 106 includes exposing the substrate to the second precursor gas to form a film on at least one structure of the substrate. In some embodiments, exposure 106 includes introducing the second precursor gas into a chamber containing the substrate. In some embodiments, exposure 106 includes flowing the second precursor gas into the chamber containing the substrate. In some embodiments, exposure 106 includes supplying the second precursor gas into the chamber containing the substrate. In some embodiments, exposure 106 includes pumping the second precursor gas into the chamber containing the substrate. In some embodiments, exposure 106 includes pulsating the second precursor gas into the chamber containing the substrate. In some embodiments, exposure 106 includes pulsating the second precursor gas into the chamber containing the substrate for a duration. In some embodiments, exposure 106 is sufficient to bring the second precursor gas and the substrate into direct or close proximity or direct physical contact.

[0038] In some embodiments, exposure 106 includes pulsating a second precursor gas into a substrate-containing chamber for a duration. In some embodiments, the duration is a duration of 0.01 seconds to 60 minutes or longer, or any range or subrange between 0.01 seconds and 60 minutes. For example, in some embodiments, the duration is a duration of 0.01 seconds to 50 minutes, 0.01 seconds to 40 minutes, 0.01 seconds to 30 minutes, 0.01 seconds to 20 minutes, 0.01 seconds to 10 minutes, 0.01 seconds to 1 minute, 0.01 seconds to 45 seconds, 0.01 seconds to 30 seconds, 0.01 seconds to 15 seconds, 0.01 seconds to 10 seconds, 0.01 seconds to 5 seconds, 0.01 seconds to 3 seconds, 0.01 seconds to 1 second, 0.01 seconds to 0.5 seconds, 0.01 seconds to 0.1 seconds, or 0.01 seconds to 0.05 seconds. In some embodiments, the duration is a duration of 0.05 seconds to 60 minutes, 0.10 seconds to 60 minutes, 0.2 seconds to 60 minutes, 0.3 seconds to 60 minutes, 0.4 seconds to 60 minutes, 0.5 seconds to 60 minutes, 0.6 seconds to 60 minutes, 0.7 seconds to 60 minutes, 0.8 seconds to 60 minutes, 0.9 seconds to 60 minutes, 1 second to 60 minutes, 3 seconds to 60 minutes, 5 seconds to 60 minutes, 15 seconds to 60 minutes, 30 seconds to 60 minutes, 1 minute to 60 minutes, 10 minutes to 60 minutes, 20 minutes to 60 minutes, 30 minutes to 60 minutes, 40 minutes to 60 minutes, or 50 minutes to 60 minutes.

[0039] In some embodiments, the duration is a duration of 0.01 seconds to 5 minutes or longer, or any range or subrange between 0.01 seconds and 5 minutes. For example, in some embodiments, the duration is a duration of 0.01 seconds to 4 minutes, 0.01 seconds to 3 minutes, 0.01 seconds to 2 minutes, 0.01 seconds to 1 minute, 0.01 seconds to 50 seconds, 0.01 seconds to 40 seconds, 0.01 seconds to 30 seconds, 0.01 seconds to 20 seconds, 0.01 seconds to 10 seconds, 0.01 seconds to 5 seconds, or 0.01 seconds to 3 seconds, 0.01 seconds to 1 second, 0.01 seconds to 0.5 seconds, 0.01 seconds to 0.1 seconds, or 0.01 seconds to 0.05 seconds. In some embodiments, the duration is a duration of 0.05 seconds to 5 minutes, 0.10 seconds to 5 minutes, 0.2 seconds to 5 minutes, 0.3 seconds to 5 minutes, 0.4 seconds to 5 minutes, 0.5 seconds to 5 minutes, 0.6 seconds to 5 minutes, 0.7 seconds to 5 minutes, 0.8 seconds to 5 minutes, 0.9 seconds to 5 minutes, 1 second to 5 minutes, 3 seconds to 5 minutes, 5 seconds to 5 minutes, 15 seconds to 5 minutes, 30 seconds to 5 minutes, 1 minute to 5 minutes, 2 minutes to 5 minutes, 3 minutes to 5 minutes, or 4 minutes to 5 minutes.

[0040] In some embodiments, exposure 106 is performed at a temperature range or subrange between 100°C and 500°C. For example, in some embodiments, exposure 102 is performed at temperatures ranging from 100°C to 475°C, 100°C to 450°C, 100°C to 425°C, 100°C to 400°C, 100°C to 375°C, 100°C to 350°C, 100°C to 325°C, 100°C to 300°C, 100°C to 275°C, 100°C to 250°C, 100°C to 225°C, 100°C to 200°C, 100°C to 175°C, 100°C to 150°C, or 100°C. The temperature range is 125℃, 125℃ to 500℃, 150℃ to 500℃, 175℃ to 500℃, 200℃ to 500℃, 225℃ to 500℃, 250℃ to 500℃, 275℃ to 500℃, 300℃ to 500℃, 325℃ to 500℃, 350℃ to 500℃, 375℃ to 500℃, 400℃ to 500℃, 425℃ to 500℃, 450℃ to 500℃, or 475℃ to 500℃.

[0041] In some embodiments, the resulting membrane has a class coverage of at least 90%. For example, in some embodiments, the membrane has a class coverage of at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or greater. In some embodiments, the membrane has a class coverage of any range or subrange between 90% and 100%. For example, in some embodiments, the membrane has a class coverage of 90% to 99%, 90% to 98%, 90% to 97%, 90% to 96%, 90% to 95%, 90% to 94%, 90% to 93%, 90% to 92%, 90% to 91%, 91% to 100%, 92% to 100%, 93% to 100%, 94% to 100%, 95% to 100%, 96% to 100%, 97% to 100%, 98% to 100%, 99% to 100%, 91% to 99%, 92% to 99%, 93% to 99%, 94% to 99%, 95% to 99%, 96% to 99%, 97% to 99%, or 98% to 99%.

[0042] In some embodiments, the membrane comprises a metal oxide. In some embodiments, for example, the membrane comprises hafnium oxide. In some embodiments, the membrane comprises zirconium oxide. In some embodiments, the membrane comprises aluminum oxide. In some embodiments, the membrane comprises titanium oxide. In some embodiments, the membrane comprises tantalum oxide. In some embodiments, the membrane comprises niobium oxide. In some embodiments, the membrane comprises vanadium oxide. In some embodiments, the membrane comprises gallium oxide. In some embodiments, the membrane comprises indium oxide. In some embodiments, the membrane comprises silicon oxide.

[0043] The membrane can have a thickness of any range or subrange between 1 nm and 5 μm or between 1 nm and 5 μm. In some embodiments, for example, the film has a thickness of 1 nm to 4 μm, 1 nm to 3 μm, 1 nm to 2 μm, 1 nm to 1 μm, 1 nm to 900 nm, 1 nm to 800 nm, 1 nm to 700 nm, 1 nm to 600 nm, 1 nm to 500 nm, 1 nm to 400 nm, 1 nm to 300 nm, 1 nm to 200 nm, 1 nm to 100 nm, 100 nm to 5 μm, 200 nm to 5 μm, 300 nm to 5 μm, 400 nm to 5 μm, 500 nm to 5 μm, 600 nm to 5 μm, 700 nm to 5 μm, 800 nm to 5 μm, 900 nm to 5 μm, 1 μm to 5 μm, 2 μm to 5 μm, 3 μm to 5 μm, or 4 μm to 5 μm. In some embodiments, the film has a thickness of 0.1 nm to 10 nm, 0.1 nm to 9 nm, 0.1 nm to 8 nm, 0.1 nm to 7 nm, 0.1 nm to 6 nm, or 0.1 nm to 5 nm.

[0044] The membrane can have a resolution of less than 1 × 10⁻⁶ as measured by secondary ion mass spectrometry (SIMS). 20 A concentration of hydrogen atoms per cubic centimeter. For example, in some embodiments, the membrane may have a concentration of less than 1 × 10⁻⁶. 20 One hydrogen atom per cubic centimeter, less than 0.9 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter, less than 0.8 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter, less than 0.7 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter, less than 0.6 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter, less than 0.5 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter, less than 0.4 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter, less than 0.3 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter, less than 0.2 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter or less than 0.1 × 10⁻⁶ 20 A concentration of hydrogen atoms per cubic centimeter. In some embodiments, the membrane may have a concentration of less than 9 × 10⁻⁶ hydrogen atoms per cubic centimeter as measured by SIMS. 19 One hydrogen atom per cubic centimeter, less than 8 × 10⁻⁶ 19 One hydrogen atom per cubic centimeter, less than 7 × 10⁻⁶ 19 One hydrogen atom per cubic centimeter, less than 6 × 10⁻⁶ 19 One hydrogen atom per cubic centimeter, less than 5 × 10⁻⁶ 19One hydrogen atom per cubic centimeter, less than 4 × 10⁻⁶ 19 One hydrogen atom per cubic centimeter, less than 3 × 10⁻⁶ 19 One hydrogen atom per cubic centimeter, less than 2 × 10⁻⁶ 19 One hydrogen atom per cubic centimeter or less than 1 × 10⁻⁶ 19 The concentration of hydrogen atoms per cubic centimeter.

[0045] The membrane can have a strength less than 10 × 10⁻⁶ as measured by SIMS. 18 A concentration of carbon atoms per cubic centimeter. For example, in some embodiments, the membrane has a concentration of less than 10 × 10⁻⁶. 18 carbon atoms per cubic centimeter, less than 9 × 10⁻⁶ 18 carbon atoms per cubic centimeter, less than 8 × 10 18 carbon atoms per cubic centimeter, less than 7 × 10 18 carbon atoms per cubic centimeter, less than 6 × 10 18 carbon atoms per cubic centimeter, less than 5 × 10 18 carbon atoms per cubic centimeter, less than 4 × 10 18 carbon atoms per cubic centimeter, less than 3 × 10⁻⁶ 18 carbon atoms per cubic centimeter, less than 2 × 10 18 One carbon atom per cubic centimeter or less than 1 × 10⁻⁶ 18 A concentration of one carbon atom per cubic centimeter.

[0046] In some embodiments, method 100 does not include flowing feed gas to an ozone generator to generate ozone components and / or causing NO to... x The gas flows to combine with ozone components to produce a second precursor gas.

[0047] Figure 2 This is a block diagram of a system 200 for vapor deposition according to some embodiments. (e.g.) Figure 2As shown, in some embodiments, system 200 includes a feed gas comprising O2 and N2. In some embodiments, O2 is supplied from oxygen source 202 and N2 is supplied from nitrogen source 204. Although O2 and N2 are shown to be supplied in separate gas streams, it should be understood that other configurations are possible, such as (e.g., but not limited to) O2 and N2 being supplied in a single stream or two or more streams. O2 from oxygen source 202 and N2 from nitrogen source 204 flow to ozone generator 208 to generate a second precursor gas 214. In some embodiments, the second precursor 214 comprises ozone (O3). In some embodiments, system 200 includes a metal precursor source 210 for supplying a metal precursor to a vapor deposition apparatus 212 (e.g., a chamber). In some embodiments, system 200 includes an inert source 206 for supplying an inert gas (e.g., (e.g., but not limited to) N2) to vapor deposition apparatus 212. At vapor deposition apparatus 212, a vapor deposition process is performed to form a film on at least one structure of a substrate, wherein the film has at least 90% layer coverage.

[0048] Some embodiments relate to an apparatus, such as (e.g., but not limited to) for use in semiconductor applications and other microelectronic applications. In some embodiments, the apparatus includes any film disclosed herein. In some embodiments, for example, the apparatus includes a substrate having at least one structure with a high aspect ratio. In some embodiments, the apparatus includes a film positioned at least on at least one structure having a high aspect ratio. In some embodiments, the film is positioned on the apparatus to improve grade coverage. In some embodiments, the film is in direct contact with the substrate and / or at least one structure.

[0049] In some embodiments, the device includes a substrate. In some embodiments, the substrate is a high aspect ratio substrate. For example, in some embodiments, a high aspect ratio substrate includes a substrate having at least one structure with a high aspect ratio. In some embodiments, the substrate may have multiple structures, each of which has a high aspect ratio. The at least one structure is not particularly limited, but may include any structure with a high aspect ratio disclosed herein. In some embodiments, the at least one structure includes at least one of a trench, a chamber, a cavity, a hole, a channel, or any combination thereof.

[0050] At least one structure on the substrate may be a structure having an aspect ratio of at least 10:1. For example, in some embodiments, the substrate has at least one structure having an aspect ratio of at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, at least 60:1, at least 70:1, at least 80:1 or at least 90:1. In some embodiments, the substrate has at least one structure having an aspect ratio of 10:1 to 100:1, 10:1 to 90:1, 10:1 to 80:1, 10:1 to 70:1, 10:1 to 60:1, 10:1 to 50:1, 10:1 to 40:1, 10:1 to 30:1, 10:1 to 20:1, 20:1 to 100:1, 30:1 to 100:1, 40:1 to 100:1, 50:1 to 100:1, 60:1 to 100:1, 70:1 to 100:1, 80:1 to 100:1, or 90:1 to 100:1. In some embodiments, at least one structure and the substrate are a single integral piece. In some embodiments, at least one structure and the substrate are manufactured separately and assembled together.

[0051] The substrate may include a surface on which the film is formed, as disclosed herein. In some embodiments, the substrate includes at least one of silicon, silicon oxide, silicon-on-insulator (SOI), carbon-doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, metal, metal nitride, metal alloy, or any combination thereof.

[0052] In some embodiments, the apparatus includes a membrane positioned on a substrate. In some embodiments, the membrane is in direct contact with the substrate. In some embodiments, the membrane is positioned on at least one structure. In some embodiments, the membrane is in direct contact with one or more surfaces of at least one structure. In some embodiments, the membrane is positioned on at least one structure with at least 90% grade coverage. In some embodiments, for example, the membrane is positioned on at least one structure with at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% grade coverage. In some embodiments, the membrane is positioned on at least one structure with a stepped coverage of any range or subrange between 90% and 100%, 90% and 99%, 90% and 98%, 90% and 97%, 90% and 96%, 90% and 95%, 90% and 94%, 90% and 93%, 90% and 92%, 90% and 91%, 91% and 100%, 92% and 100%, 93% and 100%, 94% and 100%, 95% and 100%, 96% and 100%, 97% and 100%, 98% and 100%, 99% and 100%, or 90% and 100%.

[0053] In some embodiments, the membrane comprises a metal oxide. In some embodiments, for example, the membrane comprises hafnium oxide. In some embodiments, the membrane comprises zirconium oxide. In some embodiments, the membrane comprises aluminum oxide. In some embodiments, the membrane comprises titanium oxide. In some embodiments, the membrane comprises tantalum oxide. In some embodiments, the membrane comprises niobium oxide. In some embodiments, the membrane comprises vanadium oxide. In some embodiments, the membrane comprises gallium oxide. In some embodiments, the membrane comprises indium oxide. In some embodiments, the membrane comprises silicon oxide.

[0054] The membrane can have a thickness of any range or subrange between 5 nm and 5 μm. In some embodiments, for example, the film has a thickness of 5 nm to 4 μm, 5 nm to 3 μm, 5 nm to 2 μm, 5 nm to 1 μm, 5 nm to 900 nm, 5 nm to 800 nm, 5 nm to 700 nm, 5 nm to 600 nm, 5 nm to 500 nm, 5 nm to 400 nm, 5 nm to 300 nm, 5 nm to 200 nm, 5 nm to 100 nm, 100 nm to 5 μm, 200 nm to 5 μm, 300 nm to 5 μm, 400 nm to 5 μm, 500 nm to 5 μm, 600 nm to 5 μm, 700 nm to 5 μm, 800 nm to 5 μm, 900 nm to 5 μm, 1 μm to 5 μm, 2 μm to 5 μm, 3 μm to 5 μm, or 4 μm to 5 μm.

[0055] The membrane can have a resolution of less than 1 × 10⁻⁶ as measured by secondary ion mass spectrometry (SIMS). 20 A concentration of hydrogen atoms per cubic centimeter. For example, in some embodiments, the membrane may have a concentration of less than 1 × 10⁻⁶. 20 One hydrogen atom per cubic centimeter, less than 0.9 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter, less than 0.8 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter, less than 0.7 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter, less than 0.6 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter, less than 0.5 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter, less than 0.4 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter, less than 0.3 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter, less than 0.2 × 10⁻⁶ 20 One hydrogen atom per cubic centimeter or less than 0.1 × 10⁻⁶ 20 A concentration of hydrogen atoms per cubic centimeter. In some embodiments, the membrane may have a concentration of less than 9 × 10⁻⁶ hydrogen atoms per cubic centimeter as measured by SIMS. 19One hydrogen atom per cubic centimeter, less than 8 × 10⁻⁶ 19 One hydrogen atom per cubic centimeter, less than 7 × 10⁻⁶ 19 One hydrogen atom per cubic centimeter, less than 6 × 10⁻⁶ 19 One hydrogen atom per cubic centimeter, less than 5 × 10⁻⁶ 19 One hydrogen atom per cubic centimeter, less than 4 × 10⁻⁶ 19 One hydrogen atom per cubic centimeter, less than 3 × 10⁻⁶ 19 One hydrogen atom per cubic centimeter, less than 2 × 10⁻⁶ 19 One hydrogen atom per cubic centimeter or less than 1 × 10⁻⁶ 19 The concentration of hydrogen atoms per cubic centimeter.

[0056] The membrane can have a strength less than 10 × 10⁻⁶ as measured by SIMS. 18 A concentration of carbon atoms per cubic centimeter. For example, in some embodiments, the membrane has a concentration of less than 10 × 10⁻⁶. 18 carbon atoms per cubic centimeter, less than 9 × 10⁻⁶ 18 carbon atoms per cubic centimeter, less than 8 × 10 18 carbon atoms per cubic centimeter, less than 7 × 10 18 carbon atoms per cubic centimeter, less than 6 × 10 18 carbon atoms per cubic centimeter, less than 5 × 10 18 carbon atoms per cubic centimeter, less than 4 × 10 18 carbon atoms per cubic centimeter, less than 3 × 10⁻⁶ 18 carbon atoms per cubic centimeter, less than 2 × 10 18 One carbon atom per cubic centimeter or less than 1 × 10⁻⁶ 18 A concentration of one carbon atom per cubic centimeter.

[0057] Example 1

[0058] Various alumina films were deposited on substrates with high aspect ratio structures via atomic layer deposition (ALD). The deposition process involved 100 to 200 cycles of exposure of the substrate to AlCl3 and oxidizing gases. Each sample involved a substrate with a trench structure having an aspect ratio of 11:1. Each sample was exposed to AlCl3 and co-reactant gases at 250°C. Each sample had a different co-reactant gas. Sample 1 used water as a co-reactant. Sample 2 used ozone as a co-reactant. In Sample 2, 100 ppm N2 in O2 was fed into a corona discharge ozone generator (MKS O3MegaAX8561) at 50% power at a 2 slm flow rate. Sample 3 used ozone generated at 39% power from a mixture of 20% N2 and 80% O2. The ozone generator had a maximum power of 1750 watts. Growth / cycle (GPC, in angstroms / cycle), class coverage on the trench structure, and impurity content were measured. The results are summarized in Tables 1 and 2 below.

[0059] Table 1

[0060]

[0061] Table 2

[0062]

[0063] As demonstrated above, when a mixture of 20% N2 and 80% O2 was supplied to the ozone generator and the substrate was exposed to ozone-containing gas from the generator, the graded coverage of the alumina film in Sample 3 was dramatically improved. Using this process, lower C and H2 contents were measured in the resulting film in Sample 3 compared to other samples. Furthermore, Sample 3 exhibited improved growth / cycling compared to other samples.

[0064] aspect

[0065] The following describes various aspects. It should be understood that any one or more features described in the following aspects may be combined with any one or more other aspects.

[0066] Aspect 1. An apparatus comprising:

[0067] A substrate having at least one structure having an aspect ratio of at least 10:1; and

[0068] A membrane, which is positioned on the at least one structure with at least 90% of its layer coverage;

[0069] The membrane comprises:

[0070] Metal oxides or metal-like oxides; and

[0071] Less than 1×10 as measured by SIMS 20The concentration of hydrogen atoms per cubic centimeter.

[0072] Aspect 2. The apparatus according to aspect 1, wherein the substrate comprises at least one of silicon, silicon oxide, silicon-on-insulator (SOI), carbon-doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, metal, metal nitride, metal alloy, or any combination thereof.

[0073] Aspect 3. The apparatus according to any one of aspects 1 to 2, wherein the at least one structure is defined by the substrate and includes at least one of a trench, a gas chamber, a cavity, a hole, a channel, or any combination thereof.

[0074] Aspect 4. The apparatus according to any one of aspects 1 to 3, wherein the aspect ratio of the at least one structure is 10:1 to 100:1.

[0075] Aspect 5. The apparatus according to any one of aspects 1 to 4, wherein the membrane is in direct contact with a surface of the at least one structure.

[0076] Aspect 6. The apparatus according to any one of aspects 1 to 5, wherein the membrane comprises at least one of hafnium oxide, zirconium oxide, aluminum oxide, titanium oxide, tantalum oxide, niobium oxide, vanadium oxide, gallium oxide, indium oxide, silicon oxide, or any combination thereof.

[0077] Aspect 7. The apparatus according to any one of aspects 1 to 6, wherein the membrane has a thickness of 1 nm to 5 μm.

[0078] Aspect 8. The apparatus according to any one of aspects 1 to 7, wherein the membrane has a thickness of 1 nm to 500 nm.

[0079] Aspect 9. The apparatus according to any one of aspects 1 to 8, wherein the membrane comprises a diameter less than 10 × 10⁻⁶ as measured by SIMS. 18 One carbon atom per cubic centimeter.

[0080] Aspect 10. A method comprising:

[0081] A substrate having at least one structure having an aspect ratio of at least 10:1 is exposed to a first precursor gas.

[0082] The feed gas is flowed to an ozone generator to produce a second precursor gas, the feed gas comprising at least 1 volume% N2 based on the total volume of the feed gas.

[0083] The substrate is exposed to the second precursor gas to form a film having at least 90% gradation coverage on at least one structure of the substrate.

[0084] Aspect 11. The method according to aspect 10, wherein the substrate comprises at least one of silicon, silicon oxide, silicon-on-insulator (SOI), carbon-doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, metal, metal nitride, metal alloy, or any combination thereof.

[0085] Aspect 12. The method according to any one of aspects 10 to 11, wherein the at least one structure is defined by the substrate and includes at least one of a trench, a gas chamber, a cavity, a hole, a channel, or any combination thereof.

[0086] Aspect 13. The method according to any one of aspects 10 to 12, wherein the aspect ratio of the at least one structure is 10:1 to 100:1.

[0087] Aspect 14. The method according to any one of Aspects 10 to 13, wherein the first precursor gas comprises at least one of SiCl4, hexachlorosilane, HfCl4, ZrCl4, AlCl3, trimethylaluminum, TiCl4, TaCl5, NbCl5, VCl4, GaCl3, InCl3, tris(dimethylamido)cyclopentadienylhafnium, tris(dimethylamido)cyclopentadienylzirconium, tetra(ethylmethylamino)hafnium, tetra(ethylmethylamino)zirconium, tetra(diethylamino)hafnium, tetra(dimethylamino)hafnium, or any combination thereof.

[0088] Aspect 15. The method according to any one of aspects 10 to 14, wherein the feed gas comprises:

[0089] Based on 2% to 40% of the total volume of the feed gas, N2; and

[0090] Based on 60% to 98% of the total volume of the feed gas, O2.

[0091] Aspect 16. The method according to any one of aspects 10 to 15, wherein the feed gas comprises:

[0092] Based on 10% to 30% by volume of N2 of the total volume of the feed gas; and

[0093] O2 is 70% to 90% of the total volume of the feed gas.

[0094] Aspect 17. The method according to any one of aspects 10 to 16, wherein the second precursor gas comprises ozone (O3).

[0095] Aspect 18. The method according to any one of aspects 10 to 17, wherein the second precursor gas further comprises at least one of oxygen (O2), water (H2O), hydrogen peroxide (H2O2), nitrous oxide (N2O), nitric oxide (NO), nitrous pentoxide (N2O5), nitrogen dioxide (NO2), or any combination thereof.

[0096] Aspect 19. The method according to any one of aspects 10 to 18, wherein the membrane comprises:

[0097] Metal oxides or metal-like oxides; and

[0098] Less than 1×10 as measured by SIMS 20 The concentration of hydrogen atoms per cubic centimeter.

[0099] Aspect 20. The method according to any one of aspects 10 to 19, wherein the membrane comprises at least one of hafnium oxide, zirconium oxide, aluminum oxide, titanium oxide, tantalum oxide, niobium oxide, vanadium oxide, gallium oxide, indium oxide, silicon oxide, or any combination thereof.

[0100] It should be understood that changes may be made to details, particularly the shape, size, and arrangement of the building materials and components used, without departing from the scope of this disclosure. This specification and the described embodiments are merely examples, and the true scope and spirit of this disclosure are indicated by the appended claims.

Claims

1. An apparatus comprising: A substrate having at least one structure having an aspect ratio of at least 10:1; and A membrane, which is positioned on the at least one structure with at least 90% of its layer coverage; The membrane comprises: Metal oxides or metal-like oxides; and Less than 1×10 as measured by SIMS 20 The concentration of hydrogen atoms per cubic centimeter.

2. The apparatus of claim 1, wherein the substrate comprises at least one of silicon, silicon oxide, silicon-on-insulator (SOI), carbon-doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, metal, metal nitride, metal alloy, or any combination thereof.

3. The apparatus of claim 1, wherein the at least one structure is defined by the substrate and includes at least one of a trench, a gas chamber, a cavity, a hole, a channel, or any combination thereof.

4. The apparatus according to claim 1, wherein the aspect ratio of the at least one structure is from 10:1 to 100:

1.

5. The apparatus of claim 1, wherein the membrane is in direct contact with a surface of the at least one structure.

6. The apparatus of claim 1, wherein the membrane comprises at least one of hafnium oxide, zirconium oxide, aluminum oxide, titanium oxide, tantalum oxide, niobium oxide, vanadium oxide, gallium oxide, indium oxide, silicon oxide, or any combination thereof.

7. The apparatus of claim 1, wherein the membrane has a thickness of 1 nm to 5 μm.

8. The apparatus of claim 1, wherein the membrane has a thickness of 1 nm to 500 nm.

9. The apparatus of claim 1, wherein the membrane comprises a thickness less than 10 × 10⁻⁶ as measured by SIMS. 18 One carbon atom per cubic centimeter.

10. A method comprising: A substrate having at least one structure having an aspect ratio of at least 10:1 is exposed to a first precursor gas. The feed gas is flowed to an ozone generator to produce a second precursor gas, the feed gas comprising at least 1 volume% N2 based on the total volume of the feed gas. The substrate is exposed to the second precursor gas to form a film having at least 90% gradation coverage on at least one structure of the substrate.

11. The method of claim 10, wherein the substrate comprises at least one of silicon, silicon oxide, silicon-on-insulator (SOI), carbon-doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, sapphire, metal, metal nitride, metal alloy, or any combination thereof.

12. The method of claim 10, wherein the at least one structure is defined by the substrate and includes at least one of a trench, a gas chamber, a cavity, a hole, a channel, or any combination thereof.

13. The method of claim 10, wherein the aspect ratio of the at least one structure is from 10:1 to 100:

1.

14. The method of claim 10, wherein the first precursor gas comprises at least one of SiCl4, hexachlorosilane, HfCl4, ZrCl4, AlCl3, trimethylaluminum, TiCl4, TaCl5, NbCl5, VCl4, GaCl3, InCl3, tris(dimethylamido)cyclopentadienyl hafnium, tris(dimethylamido)cyclopentadienyl zirconium, tetra(ethylmethylamino) hafnium, tetra(ethylmethylamino) zirconium, tetra(diethylamino) hafnium, tetra(dimethylamino) hafnium, or any combination thereof.

15. The method of claim 10, wherein the feed gas comprises: N2 is 2% to 40% of the total volume of the feed gas. and Based on 60% to 98% of the total volume of the feed gas, O2.

16. The method of claim 10, wherein the feed gas comprises: N2 is 10% to 30% of the total volume of the feed gas; and O2 is 70% to 90% of the total volume of the feed gas.

17. The method of claim 10, wherein the second precursor gas comprises ozone (O3).

18. The method of claim 10, wherein the second precursor gas further comprises at least one of oxygen (O2), water (H2O), hydrogen peroxide (H2O2), nitrous oxide (N2O), nitric oxide (NO), dinitrogen pentoxide (N2O5), nitrogen dioxide (NO2), or any combination thereof.

19. The method of claim 10, wherein the membrane comprises: Metal oxides or metal-like oxides; and Less than 1×10 as measured by SIMS 20 The concentration of hydrogen atoms per cubic centimeter.

20. The method of claim 10, wherein the membrane comprises at least one of hafnium oxide, zirconium oxide, aluminum oxide, titanium oxide, tantalum oxide, niobium oxide, vanadium oxide, gallium oxide, indium oxide, silicon oxide, or any combination thereof.

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