Improving photosensitivity of metal-organic resists using carboxylic acids

Abstract

The disclosed and claimed subject matter relates to a method for depositing a tin-containing film. The method includes: (i) contacting a substrate with a vapor of an organotin precursor in a deposition reactor, (ii) purging the reaction vessel with an inert gas, (iii) contacting the substrate with a vapor containing water vapor to form a layer of an organotin oxygen network, (iv) purging the reaction vessel with an inert gas, (v) contacting the substrate with a vapor containing a carboxylic acid, and (vi) purging the reaction vessel with an inert gas.

Description

Related applications

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 515,921, filed July 27, 2023, which is hereby incorporated herein by reference. Technical Field

[0002] The disclosed and claimed subject matter relates to a method for depositing a tin-containing film. The method generally includes (i) contacting a substrate with organotin precursor vapor in a deposition reactor, (ii) purging the reaction vessel with an inert gas, (iii) contacting the substrate with water vapor to form an organotin oxo network layer, (iv) purging the reaction vessel with an inert gas, (v) contacting the substrate with carboxylic acid vapor, and (vi) purging the reaction vessel with an inert gas. Repeatable processing steps can be repeated to provide an organotin oxo film of the desired thickness. Background Technology

[0003] Thin films, and especially metal-containing thin films, have a variety of important applications, such as in the fabrication of nanotechnology and semiconductor devices. Examples of such applications include conductive metal oxides, EUV patterning, high-refractive-index optical coatings, anti-corrosion coatings, photocatalytic self-cleaning glass coatings, biocompatible coatings, dielectric capacitor layers and gate dielectric insulating films in field-effect transistors (FETs), capacitor electrodes, gate electrodes, binder diffusion barrier layers, and integrated circuits. Metal thin films and dielectric thin films are also used in microelectronic applications, such as high-k dielectric oxides for dynamic random access memory (DRAM) applications and ferroelectric perovskites for infrared detectors and non-volatile ferroelectric random access memory (NV-FeRAM).

[0004] Various precursors can be used to form metal-containing thin films, and a variety of deposition techniques can be employed. These techniques include reactive sputtering, ion-assisted deposition, sol-gel deposition, chemical vapor deposition (CVD) (also known as metal-organic CVD or MOCVD), and atomic layer deposition (ALD) (also known as atomic layer epitaxy). CVD and ALD processes are increasingly used because they offer advantages such as enhanced compositional control, high film uniformity, and efficient doping control.

[0005] CVD is a chemical process that forms a thin film on a substrate surface using a precursor. In a typical CVD process, the precursor passes over the substrate (e.g., a wafer) surface in a low- or atmospheric-pressure reactor. The precursor reacts and / or decomposes on the substrate surface, resulting in a thin film of deposited material. Volatile byproducts are removed by the gas flow through the reactor. The thickness of the deposited film can be difficult to control because it depends on the synergy of many parameters, such as temperature, pressure, gas flow rate and uniformity, chemical depletion effect, and time.

[0006] ALD (Alternating Layer Deposition) is also a method used for thin film deposition. It is a self-limiting, sequential, and unique film growth technique based on surface reactions that provides precise thickness control and deposits conformal films from precursor-provided materials onto substrate surfaces of varying compositions. In ALD, the precursor is introduced individually during the deposition process. A first precursor passes over the substrate surface, creating a monolayer on the substrate surface. Any excess unreacted precursor is pumped out of the reactor. A second precursor then passes over the substrate surface and reacts with the first precursor, forming a second monolayer on top of the first monolayer formed on the substrate surface. This cycle is repeated to produce a film of the desired thickness.

[0007] However, the continuous shrinking of microelectronic components (such as semiconductor devices) presents several technical challenges and increases the need for improved thin-film technologies. In particular, microelectronic components may include features on or within a substrate that require filling, for example, to form conductive paths or interconnects. Filling such features, especially in increasingly smaller microelectronic components, can be challenging because features may become increasingly thin or narrow. Therefore, as the thickness of a feature approaches zero, complete filling, for example via ALD, requires extremely long cycle times. Furthermore, once the thickness of a feature becomes narrower than the size of a precursor molecule, the feature cannot be completely filled. As a result, hollow seams may remain in the middle portion of the feature when ALD is performed. The presence of such hollow seams within a feature is undesirable because they can lead to device failure. Therefore, there is great interest in developing thin-film deposition methods, particularly ALD methods, that can selectively grow films on one or more substrates and achieve improved filling of features on or within the substrate (including depositing metal-containing films in a manner that substantially fills features without any voids).

[0008] CVD and ALD are particularly attractive for fabricating conformal metal-containing films on substrates such as silicon, silicon oxide, metal nitrides, metal oxides, and other metal-containing layers using these metal-containing precursors. As described above, in these techniques, the vapor of a volatile metal compound is introduced into a process reactor, where it comes into contact with the surface of a silicon wafer (on which a chemical reaction occurs), depositing a thin film of pure metal or metal compound. CVD occurs if the precursor reacts thermally at the wafer surface or with a reagent simultaneously added to the process reactor, and film growth occurs in a steady-state deposition. CVD can be applied in continuous or pulsed modes to achieve the desired film thickness. In ALD, the precursor is chemisorbed onto the wafer as a self-saturating monolayer. Excess unreacted precursor is purged with an inert gas (such as argon), and then excess reagent is added, which reacts with the chemisorbed precursor monolayer to form a metal or metal compound. The excess reagent is then purged with an inert gas. Because the chemisorption of the precursor and reagent is self-limiting, this cycle can then be repeated multiple times to accumulate the metal or metal compound to the desired thickness with atomic precision. ALD (Alternating Layer Deposition) provides ultrathin yet continuous deposition of metal-containing films with precise control over film thickness, excellent film thickness uniformity, and highly conformal film growth to uniformly cover deeply etched and highly complex structures such as interconnect vias and trenches. Therefore, ALD is generally preferred for thin film deposition on features with high aspect ratios.

[0009] Suitable metal precursors for ALD include those that are thermally stable to prevent any thermal decomposition during the chemisorption phase, but are chemically reactive to the added reagents. Furthermore, it is important that the metal precursor is monomeric to achieve maximum volatility and clean evaporation, leaving only trace amounts of non-volatile residues. It is also desirable that the precursor is liquid at room temperature.

[0010] The CVD / ALD process for depositing MOR (metal-organic resist) materials using organotin compounds as precursors and oxygen sources (such as water vapor or organic co-reactants) is known.

[0011] WO22016123A1 discloses a membrane formed from a precursor and an organic co-reactant, as well as a method for forming and using such a membrane. The membrane can be used as a photo-patternable membrane or a radiation-sensitive membrane. In some embodiments, the carbon content within the membrane can be tuned by decoupling the sources of the radiation-sensitive metallic element and the radiation-sensitive organic portion during the deposition process. In non-limiting embodiments, the radiation may include extreme UV (EUV) or deep UV (DUV) radiation.

[0012] WO2022016128 discloses a method for forming a photosensitive metal-polymer hybrid photoresist film for photolithography to improve extreme UV sensitivity and patterning quality, as discussed. The method includes depositing a metal-containing layer on a substrate surface by providing a metal precursor to the surface, wherein the substrate is disposed within a cavity; purging the metal precursor from the cavity; and depositing an organic layer on the surface of the metal-containing layer by providing an organic precursor to the surface, wherein the organic layer contains photosensitive organic portions, thereby forming a patterned radiation-sensitive film.

[0013] US2022155689A discloses a method for depositing photoresist onto a substrate in a processing chamber. In one embodiment, the method includes allowing an oxidant to flow into the processing chamber through a first path in the nozzle, and allowing an organometallic substance to flow into the processing chamber through a second path in the nozzle. In another embodiment, the first path and the second path are isolated such that the oxidant and the organometallic substance do not mix within the nozzle. In yet another embodiment, the method further includes reacting the oxidant and the organometallic substance in the processing chamber to deposit photoresist on the substrate.

[0014] US patent 2022262625 discloses a method for depositing metal oxo photoresist on a substrate using a chemical vapor deposition process in a vacuum chamber. The method includes providing a metal precursor vapor from an ampoule maintained at a first temperature into the vacuum chamber. The method also includes providing an oxidant vapor into the vacuum chamber, wherein a reaction between the metal precursor vapor and the oxidant vapor results in the formation of a photoresist layer on the substrate surface. The photoresist layer is a metal oxygen-containing material. During the formation of the photoresist layer on the substrate surface, the substrate is maintained at a second temperature below the first temperature.

[0015] US2022002869 discloses a method for depositing metal oxide photoresist to form a photoresist layer on a substrate in a vacuum chamber using a dry deposition process, including providing a metal precursor vapor into the vacuum chamber. In one embodiment, the method further includes providing an oxidant vapor into the vacuum chamber, wherein a reaction between the metal precursor vapor and the oxidant vapor forms a photoresist layer on the substrate surface.

[0016] US2022199406 discloses a method for forming a metal-oxygen photoresist on a substrate. In one embodiment, the method includes repeated deposition cycles, wherein each iteration of the deposition cycle includes: a) flowing a metal precursor into a chamber containing the substrate; and b) flowing an oxidant into the chamber, wherein the oxidant and the metal precursor react to form the metal-oxygen photoresist.

[0017] US10732505 discloses an organometallic precursor for forming high-resolution photolithographically patterned coatings based on metal oxide hydroxides. The precursor composition typically contains ligands that are readily hydrolyzed by water vapor or other OH source compositions under moderate conditions. The organometallic precursor typically contains a radiation-sensitive organic ligand with tin, which allows for coatings that are effective for high-resolution patterning at relatively low radiation doses and are particularly suitable for EUV patterning.

[0018] Mullings, MN et al., "Tin Oxide Atomic Layer Deposition from Tetrakis(dimethylamino)tin and Water." J. Vac. Sci. Technol. , 31(6) (2013) describes the amorphous deposition (ALD) of tin oxide on Si(100) and glass substrates via low-temperature growth in the range of 30–200 °C using tetra(dimethylamino)tin precursor and water as counter reactants. According to this article, high-quality, amorphous SnO2 films with moderately tunable optical properties can thus be obtained by ALD using tin precursor and water at temperatures as low as 30 °C.

[0019] US2021397085 discloses forming an imaging layer on a substrate surface that can be patterned using next-generation photolithography techniques, and the resulting patterned film can be used as a photolithographic mask, for example, for the production of semiconductor devices.

[0020] US2021013034 discloses a method for fabricating thin films on a semiconductor substrate, which can be patterned using EUV, including mixing a vapor stream of an organometallic precursor with a vapor stream of a reverse reactant to form a polymerized organometallic material; and depositing the organometallic polymer-like material onto the surface of the semiconductor substrate. The mixing and deposition operations can be performed by chemical vapor deposition (CVD), atomic layer deposition (ALD), and ALD with CVD components (such as discontinuous, ALD-like processes where the metal precursor and reverse reactant are separated in time or space).

[0021] Given the above, there is a need for improved deposition methods using organotin compounds as precursors for depositing photosensitive materials with better photosensitivity (for certain applications in the semiconductor industry, such as patterning processes specifically involving EUV for future technology nodes). As mentioned above, CVD and ALD are used as the primary deposition techniques for producing thin films for semiconductor devices. These methods enable the deposition of conformal films (e.g., metals, metal oxides, metal nitrides, metal silicides, etc.) through the chemical reaction of a metal compound (precursor) with a reactive gas in the gas phase (CVD) or surface (ALD). This disclosed and claimed subject matter provides an improved deposition method (i.e., an ALD-like process) using a combination of ALD and CVD, where three precursors (i.e., organotin compounds, water, and carboxylic acids) are used, unlike typical ALD processes which typically involve only two precursors. It is also worth noting that CVD processes can have particle problems when water vapor is used as a co-reactant.

[0022] This paper describes a method for depositing organotin oxide films via a thermal ALD-like process, such as, but not limited to, a cyclic chemical vapor deposition (CCVD) process employing three precursors, in contrast to related prior art processes that typically involve only two precursors. It is believed that by sequentially introducing an organotin compound and water, followed by the introduction of a carboxylic acid, the reaction between the organotin compound and water vapor can provide superior photosensitive organotin oxide materials with improved photosensitivity, smoother films, and fewer particles. Furthermore, the ALD-like process described herein offers the following advantages: (a) growth rates ranging from approximately 2 Å / cycle to 50 Å / cycle, from approximately 2 Å / cycle to approximately 30 Å / cycle, and from approximately 2 Å / cycle to approximately 50 Å / cycle (compared to the growth rates of typical ALD processes in the range of approximately 0.1 Å / cycle to approximately 2 Å / cycle); and (b) improved photosensitivity, i.e., approximately 1 to 20 mJ / cm², compared to related prior art processes. 2 Approximately 5 to 20 mJ / cm 2 Approximately 10 to 20 mJ / cm 2 EUV D50 velocity range (mJ / cm) 2 Improvement of ). Summary of the Invention

[0023] In one embodiment, the disclosed and claimed subject matter relates to a method for depositing a tin-containing film, comprising (i) contacting a substrate with an organotin precursor vapor in a deposition reaction vessel, (ii) purging the reaction vessel with an inert gas, (iii) contacting the substrate with a water-containing vapor to form an organotin oxide network layer, (iv) purging the reaction vessel with an inert gas, (v) contacting the substrate with a carboxylic acid-containing vapor, and (vi) purging the reaction vessel with an inert gas. These processing steps can be repeated to provide an organotin oxide film of desired thickness. In a further aspect, the method consists essentially of steps (i), (ii), (iii), (iv), (v), and (vi).

[0024] The summary does not describe in detail every embodiment and / or incremental novelty of the disclosed and claimed subject matter. Rather, it provides only a preliminary discussion of different embodiments and corresponding novel points relative to conventional and known technologies. For additional details and / or possible insights regarding the disclosed and claimed subject matter and embodiments, please refer to the detailed description section of this disclosure and the accompanying drawings, which will be discussed further below.

[0025] For clarity, the order in which the different steps described herein are discussed is presented. Generally, the steps disclosed herein can be performed in any suitable order. Furthermore, although each of the different features, techniques, configurations, etc., disclosed herein may be discussed in different parts of this disclosure, it is intended that each concept can be performed independently of each other or appropriately combined with each other. Therefore, the disclosed and claimed subject matter can be embodied and considered in a variety of different ways. Attached Figure Description

[0026] The accompanying drawings are included to provide a further understanding of the disclosed subject matter and are incorporated in and form part of this specification. They illustrate embodiments of the disclosed subject matter and, together with the specification, serve to explain the principles of the disclosed subject matter. In the drawings: Figure 1 The dosage curves for the organotin-H2O-carboxylic acid quantitative feeding sequence of Example 1 are shown.

[0027] definition Unless otherwise stated, the following terms used in the specification and claims shall have the following meanings in relation to this application.

[0028] For the purposes of this invention and its claims, the numbering scheme for the periodic table family is based on the IUPAC periodic table of elements.

[0029] The term “and / or” used in phrases such as “A and / or B” in this article is intended to include “A and B”, “A or B”, and “A” and “B”.

[0030] The terms “substituent,” “base,” “group,” and “part” are used interchangeably.

[0031] As used herein, the terms "metal-containing complex" (or more simply, "complex") and "precursor" are used interchangeably and refer to metal-containing molecules or compounds that can be used to prepare metal-containing films by vapor deposition processes such as ALD or CVD. Metal-containing complexes can be deposited, adsorbed, decomposed, delivered, and / or passed through a substrate or its surface to form a metal-containing film. In one or more embodiments, the metal-containing complexes disclosed herein are metal halide complexes, particularly molybdenum chloride complexes.

[0032] As used herein, the term "metal-containing film" includes not only elemental metal films as more fully defined below, but also films comprising metals and one or more elements, such as metal oxide films, metal nitride films, metal silicide films, metal carbide films, etc. As used herein, the terms "elemental metal film" and "pure metal film" are used interchangeably and refer to films composed of or substantially composed of pure metals. For example, an elemental metal film may comprise 100% pure metal, or an elemental metal film may comprise at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, at least about 99.9%, or at least about 99.99% pure metal and one or more impurities. Unless the context otherwise requires, the term "metal film" should be construed as referring to an elemental metal film.

[0033] As used herein, the term "vapor deposition process" is used to refer to any type of vapor deposition technique, including but not limited to CVD and ALD. In various embodiments, CVD can take the form of conventional (i.e., continuous flow) CVD, liquid injection CVD, or light-assisted CVD. CVD can also take the form of pulsed techniques, i.e., pulsed CVD. ALD is used to form metal-containing films by evaporating and / or passing at least one metal composite disclosed herein through a substrate surface. For conventional ALD processes, see, for example, George SM et al. J. Phys. Chem., 1996, 100 , 13121-13131. In other embodiments, the ALD may take the form of conventional (i.e., pulse-injection) ALD, liquid-injection ALD, light-assisted ALD, plasma-assisted ALD, or plasma-enhanced ALD. The term "vapor deposition process" also includes Chemical Vapor Deposition: Precursors, Processes, and ApplicationsJones, AC; Hitchman, ML (eds.), The Royal Society of Chemistry: Cambridge, 2009; Chapter 1, pp. 1-36, describes various vapor deposition techniques.

[0034] Throughout this specification, the term "ALD or ALD sample" refers to processes including, but not limited to, those that: a) sequentially introduce each reactant, comprising silicon precursors and reactive gases, into a reactor such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; b) expose each reactant, comprising silicon precursors and reactive gases, to a substrate by moving or rotating the substrate to different sections of the reactor, with the sections separated by an inert gas curtain (i.e., a space ALD reactor or a roll-to-roll ALD reactor).

[0035] As used herein, the term "feature" refers to an opening in a substrate that may be defined by one or more sidewalls, a bottom surface, and an upper corner. In various respects, a feature may be a via, a trench, a contact, a dual damascene, etc.

[0036] As used herein, the terms “selective growth,” “selectively grown,” and “selectively grown” are used synonymously and refer to film growth on at least a portion of a first substrate and substantially no film growth on the remaining portion of the first substrate, and to more film growth on at least a portion of the first substrate compared to film growth on the remaining portion of the first substrate. For example, selective growth may include film growth on a lower portion of a feature, while less or no film growth may occur on a higher portion of the feature or outside the feature. For more than one substrate, the terms “selective growth,” “selectively grown,” and “selectively grown” also encompass film growth on a first substrate and substantially no film growth on a second substrate (or a third substrate, or a fourth substrate, or a fifth substrate, etc.), and more film growth on the first substrate than on the second substrate (or a third substrate, a fourth substrate, or a fifth substrate, etc.).

[0037] When the terms “about” or “approximately” are used in conjunction with a measurable numerical variable, they refer to the indicated value of the variable and all values ​​of the variable within the experimental error of the indicated value (e.g., within the 95% confidence limit of the mean) or within a percentage of the indicated value (e.g., ±10%, ±5%), whichever is greater.

[0038] "Halogen" or "halogenated" refers to halogens (e.g., F, Cl, Br, and I).

[0039] The chapter headings used herein are for organizational purposes and should not be construed as limiting the subject matter. All documents or portions thereof cited in this application, including but not limited to patents, patent applications, articles, books, and papers, are hereby expressly incorporated herein by reference in their entirety for any purpose. If any terminology in any incorporated literature and similar material is defined in a manner that contradicts the definition of that term in this application, the definition in this application shall prevail.

[0040] Detailed description It should be understood that the foregoing general description and the following detailed description are illustrative and explanatory, and do not limit the claimed subject matter. Based on the description provided in the specification, the purpose, features, advantages, and concepts of the disclosed subject matter are clear to those skilled in the art, and the disclosed subject matter is readily practiced by those skilled in the art based on the description provided herein. Descriptions of any “preferred embodiments” and / or examples showing preferred modes of practice for the disclosed subject matter are included for explanatory purposes and are not intended to limit the scope of the claims.

[0041] It will also be apparent to those skilled in the art that various modifications can be made to how the disclosed subject matter is implemented based on the aspects described in the specification without departing from the spirit and scope of the subject matter disclosed herein.

[0042] In one embodiment, the disclosed and claimed subject matter relates to a method for depositing a tin-containing film, comprising (i) contacting a substrate with an organotin precursor vapor in a deposition reactor, (ii) purging the reaction vessel with an inert gas, (iii) contacting the substrate with a water-containing vapor to form an organotin oxide network layer, (iv) purging the reaction vessel with an inert gas, (v) contacting the substrate with a carboxylic acid-containing vapor, and (vi) purging the reaction vessel with an inert gas. These processing steps can be repeated to obtain an organotin oxide film of desired thickness. In a further aspect, the method consists essentially of steps (i), (ii), (iii), (iv), (v), and (vi).

[0043] Delivery of organotin precursors As described above, step (i) of the disclosed and claimed method includes contacting the substrate with an organotin precursor vapor.

[0044] In one embodiment, the organotin precursor has the following formula: RSn(NR) 1 R 2 )3, where R, R 1 and R 2Each is independently selected from straight-chain C1 to C6 alkyl, branched C3 to C6 alkyl, C3 to C6 cycloalkyl, C2 to C6 alkenyl, C2 to C6 ynyl and C4 to C6 alkyl groups. 10 Aryl. In other embodiments, R, R 1 and R 2 It may contain at least one element selected from oxygen, sulfur, nitrogen and halogens (F, Cl, Br or I).

[0045] In another embodiment, the organotin precursor includes MeSn(NMe2)3, MeSn(NEt2)3, EtSn(NMe2)3, EtSn(NEt2)3, n-PrSn(NMe2)3, i-PrSn(NMe2)3, n-BuSn(NMe2)3, i-BuSn(NMe2)3, s-BuSn(NMe2)3, t-BuSn(NMe2)3, cyclopentyl The organotin precursor comprises one or more of the following: β-Sn(NMe2)3, MeSn(NEtMe)3, EtSn(NEtMe)3, n-PrSn(NEtMe)3, i-PrSn(NEtMe)3, n-BuSn(NEtMe)3, i-BuSn(NEtMe)3, s-BuSn(NEtMe)3, t-BuSn(NEtMe)3, cyclopentylSn(NEtMe)3, and combinations thereof. In one aspect of this embodiment, the organotin precursor comprises MeSn(NMe2)3. In one aspect of this embodiment, the organotin precursor comprises MeSn(NEt2)3. In one aspect of this embodiment, the organotin precursor comprises EtSn(NMe2)3. In one aspect of this embodiment, the organotin precursor comprises EtSn(NEt2)3. In one aspect of this embodiment, the organotin precursor comprises n-PrSn(NMe2)3. In one aspect of this embodiment, the organotin precursor comprises i-PrSn(NMe2)3. In one aspect of this embodiment, the organotin precursor comprises n-BuSn(NMe2)3. In one aspect of this embodiment, the organotin precursor comprises i-BuSn(NMe2)3. In one aspect of this embodiment, the organotin precursor comprises s-BuSn(NMe2)3. In one aspect of this embodiment, the organotin precursor comprises t-BuSn(NMe2)3. In one aspect of this embodiment, the organotin precursor comprises cyclopentylSn(NMe2)3. In one aspect of this embodiment, the organotin precursor comprises MeSn(NEtMe)3. In one aspect of this embodiment, the organotin precursor comprises EtSn(NEtMe)3. In one aspect of this embodiment, the organotin precursor comprises n-PrSn(NEtMe)3. In one aspect of this embodiment, the organotin precursor comprises i-PrSn(NEtMe)3. In one aspect of this embodiment, the organotin precursor comprises n-BuSn(NEtMe)3. In one aspect of this embodiment, the organotin precursor comprises i-BuSn(NEtMe)3. In one aspect of this embodiment, the organotin precursor comprises s-BuSn(NEtMe)3. In one aspect of this embodiment, the organotin precursor comprises t-BuSn(NEtMe)3. In one aspect of this embodiment, the organotin precursor comprises cyclopentylSn(NEtMe)3.

[0046] In another embodiment, the organotin precursor vapor pulse time is from about 0.1 seconds to about 3 seconds. In another embodiment, the organotin precursor vapor pulse time is from about 0.3 seconds to about 3 seconds. In another embodiment, the organotin precursor vapor pulse time is about 0.1 seconds. In another embodiment, the organotin precursor vapor pulse time is about 0.25 seconds. In another embodiment, the organotin precursor vapor pulse time is about 0.5 seconds. In another embodiment, the organotin precursor vapor pulse time is about 1 second. In another embodiment, the organotin precursor vapor pulse time is about 1.5 seconds. In another embodiment, the organotin precursor vapor pulse time is about 2 seconds. However, in another embodiment, the organotin precursor vapor pulse time exceeds 2 seconds, depending on the volume / design of the reaction chamber.

[0047] In one embodiment, the organotin precursor vapor is isolated from other precursor materials before and / or during its introduction into the reactor. This process avoids pre-reaction of the metallic precursor with any other materials.

[0048] In another embodiment, organotin precursor vapor is alternately exposed to the substrate along with other reactants (e.g., water vapor and / or other precursors or reagents). This process allows film growth to be carried out through self-limiting control of surface reactions, pulse lengths for each precursor or reagent, and deposition temperatures. However, it should be noted that film growth ceases once the chemical reaction on the substrate surface is completed with the organotin precursor vapor.

[0049] In another embodiment, argon and / or other inert gas streams are used as carrier gases to help deliver organotin precursor vapors into the reactor during precursor pulses.

[0050] Organotin precursor vapor purging As described above, step (ii) of the disclosed and claimed method includes purging the reaction vessel with an inert gas. The inert gas purging removes unadsorbed excess organotin precursor vapor from the process reactor. In one embodiment, the purging gas comprises argon. In one embodiment, the purging gas comprises helium. In another embodiment, the purging gas comprises nitrogen.

[0051] In one embodiment, for example, the purging time varies between about 1 second and about 90 seconds. In another embodiment, for example, the purging time varies between about 15 seconds and about 90 seconds. In another embodiment, for example, the purging time varies between about 15 seconds and about 60 seconds. In yet another embodiment, the purging time is about 30 seconds. In yet another embodiment, the purging time is about 60 seconds. In yet another embodiment, the purging time is about 90 seconds.

[0052] Reactants containing water vapor As described above, step (iii) of the disclosed and claimed method includes contacting the substrate with a water-containing vapor to form an organotin oxide network layer.

[0053] In one embodiment, for example, the water vapor pulse time varies between about 0.5 seconds and about 5 seconds. In another embodiment, for example, the water vapor pulse time is about 2.5 seconds. In yet another embodiment, for example, the water vapor pulse time is about 5 seconds. However, in another embodiment, the organotin precursor vapor pulse time exceeds 5 seconds, depending on the volume / design of the reaction chamber.

[0054] Water vapor purging steps As described above, step (iv) of the disclosed and claimed method includes purging the reaction vessel with an inert gas after water vapor treatment. The inert gas purging removes any residual material from the process reactor used for water vapor treatment. In one embodiment, the purging gas comprises argon. In one embodiment, the purging gas comprises helium. In another embodiment, the purging gas comprises nitrogen.

[0055] In one embodiment, for example, the optional inert gas purging time varies between about 15 seconds and about 90 seconds. In another embodiment, for example, the optional inert gas purging time varies between about 15 seconds and about 60 seconds. In another embodiment, the optional inert gas purging time is about 30 seconds. In another embodiment, the optional inert gas purging time is about 60 seconds. In yet another embodiment, the optional inert gas purging time is about 90 seconds.

[0056] Carboxylic acid vapor As described above, step (v) of the disclosed and claimed method includes contacting the substrate with a carboxylic acid vapor. In one embodiment, the carboxylic acid has the following formula: R 3 COOH, where R 3 Selected from hydrogen, straight-chain C1 to C6 alkyl, branched C3 to C6 alkyl, C3 to C6 cycloalkyl, C2 to C6 alkenyl, C2 to C6 ynyl and C4 to C6 alkyl. 10 Aryl. In another embodiment, R 3 It contains at least one element selected from oxygen, sulfur, nitrogen, and halogens (F, Cl, Br, or I).

[0057] In another embodiment, the carboxylic acid includes one or more of formic acid, acetic acid, dihydroxyacetic acid, propionic acid, lactic acid, butyric acid, isobutyric acid, valeric acid, 2-methylbutyric acid, 3-methylbutyric acid, neopentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, fluoroacetic acid, chloroacetic acid, iodoacetic acid, dichloroacetic acid, 4,4,4-trifluorobutyric acid, 3,3,3-trifluoropropionic acid, heptafluorobutyric acid (also known as perfluorobutyric acid), perfluorovaleric acid, 3,3,3-trifluoro-2,2-dimethylpropionic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 4,4-difluorocyclohexanecarboxylic acid, tetrahydro-3-furanic acid, and combinations thereof. In one aspect of this embodiment, the carboxylic acid includes formic acid. In one aspect of this embodiment, the carboxylic acid includes acetic acid. In one aspect of this embodiment, the carboxylic acid includes dihydroxyacetic acid. In one aspect of this embodiment, the carboxylic acid includes propionic acid. In one aspect of this embodiment, the carboxylic acid includes lactic acid. In one aspect of this embodiment, the carboxylic acid includes butyric acid. In one aspect of this embodiment, the carboxylic acid includes heptafluorobutyric acid. In one aspect of this embodiment, the carboxylic acid includes isobutyric acid. In one aspect of this embodiment, the carboxylic acid includes valeric acid. In one aspect of this embodiment, the carboxylic acid includes 2-methylbutyric acid. In one aspect of this embodiment, the carboxylic acid includes 3-methylbutyric acid. In one aspect of this embodiment, the carboxylic acid includes neopentanoic acid. In one aspect of this embodiment, the carboxylic acid includes hexanoic acid. In one aspect of this embodiment, the carboxylic acid includes heptanoic acid. In one aspect of this embodiment, the carboxylic acid includes octanoic acid. In one aspect of this embodiment, the carboxylic acid includes nonanoic acid. In one aspect of this embodiment, the carboxylic acid includes decanoic acid. In one aspect of this embodiment, the carboxylic acid includes fluoroacetic acid. In one aspect of this embodiment, the carboxylic acid includes chloroacetic acid. In one aspect of this embodiment, the carboxylic acid includes iodoacetic acid. In one aspect of this embodiment, the carboxylic acid includes dichloroacetic acid. In one aspect of this embodiment, the carboxylic acid includes 4,4,4-trifluorobutyric acid. In one aspect of this embodiment, the carboxylic acid includes 3,3,3-trifluoropropionic acid. In one aspect of this embodiment, the carboxylic acid includes heptafluorobutyric acid. In one aspect of this embodiment, the carboxylic acid includes perfluorovaleric acid. In one aspect of this embodiment, the carboxylic acid comprises 3,3,3-trifluoro-2,2-dimethylpropionic acid. In one aspect of this embodiment, the carboxylic acid comprises cyclobutanecarboxylic acid. In one aspect of this embodiment, the carboxylic acid comprises cyclopentanecarboxylic acid. In one aspect of this embodiment, the carboxylic acid comprises cyclohexanecarboxylic acid. In one aspect of this embodiment, the carboxylic acid comprises 4,4-difluorocyclohexanecarboxylic acid. In one aspect of this embodiment, the carboxylic acid comprises tetrahydro-3-furancarboxylic acid.

[0058] In another embodiment, the carboxylic acid includes one or more carboxylic acids with a boiling point of 250°C or lower, or is substantially composed of or constitutes thereof. In a further aspect of this embodiment, the carboxylic acid includes one or more carboxylic acids with a boiling point of 200°C or lower, or is substantially composed of or constitutes thereof.

[0059] In another embodiment, the carboxylic acid vapor is substantially free of any carboxylic acids with a boiling point greater than 250°C. In a further aspect of this embodiment, the carboxylic acid vapor is substantially free of any carboxylic acids with a boiling point greater than 200°C.

[0060] In another embodiment, the carboxylic acid vapor does not contain any carboxylic acids with a boiling point greater than 250°C. In a further aspect of this embodiment, the carboxylic acid vapor is substantially free of any carboxylic acids with a boiling point greater than 200°C.

[0061] Carboxylic acid vapor purging steps As described above, step (vi) of the disclosed and claimed method includes purging the reaction vessel with an inert gas after treatment with carboxylic acid vapors. The inert gas purging removes any residual material from the process reactor used for the carboxylic acid vapor treatment. In one embodiment, the purging gas comprises argon. In another embodiment, the purging gas comprises helium. In yet another embodiment, the purging gas comprises nitrogen.

[0062] For example, in one embodiment, the optional inert gas purging time varies between about 15 seconds and about 90 seconds. In another embodiment, for example, the optional inert gas purging time varies between about 15 seconds and about 60 seconds. In another embodiment, the optional inert gas purging time is about 30 seconds. In another embodiment, the optional inert gas purging time is about 60 seconds. In yet another embodiment, the optional inert gas purging time is about 90 seconds.

[0063] photosensitivity Radiation-sensitive resists are films designed to alter their solubility upon exposure to radiation. In a further aspect, the disclosed and claimed methods also include exposing a tin-containing film to a radiation source selected from KrF (248 nm), ArF (193 nm), VUV (157 nm), EUV (13 nm), electron beams, X-rays, and ion beams. Patterning is formed by selectively exposing only desired areas of the film. The film is exposed to radiation (photons in the case of EUV, electrons in the case of EBL), and the sample is then washed in a solvent (called a developer) that dissolves either the exposed areas (positive resist) or the unexposed areas (negative resist). In either case, the radiation-exposed pattern now becomes a pattern on the substrate with or without the resist. The resist can then be used as a mask for further semiconductor processing steps, such as etching or deposition.

[0064] Figure 1 A graph of the dose matrix test is shown. This graph was generated by exposing an array of identical patterns on a sample with a resist film. The dose or radiation provided at each point in the array is different. Figure 1 A graph showing the height of resist retention after development for each dose is provided, but we can also use other measures of the resulting pattern quality. As can be seen, the resist sensitivity can be obtained by observing the lowest dose that still provides the desired pattern. Higher sensitivity (response at lower doses) is generally preferred. Also of interest is contrast, which is a measure of how rapidly the film's response increases as the dose exceeds the desired minimum.

[0065] Operating conditions As stated above, the disclosed and claimed tin deposition process can be carried out efficiently under very favorable ALD conditions.

[0066] In one embodiment, the substrate is one or more of amorphous carbon, silicon oxide (SiO2), aluminum oxide (Al2O3), titanium nitride (TiN), hafnium oxide (HfO2), zirconium oxide (ZrO2), a lower layer composed of two or more elements (such as Si, O, C, N, Ge, Sn, Sb, and Te), and combinations thereof, heated on a heater stage in a reactor initially exposed to an organotin precursor to allow the composite to chemisorb onto the substrate surface. In one embodiment, the substrate temperature is from about 25°C to about 300°C. In a further aspect of this embodiment, the substrate temperature is from about 25°C to about 250°C. In a further aspect of this embodiment, the substrate temperature is from about 25°C to about 200°C, or from about 50°C to about 150°C, or from about 50°C to about 130°C, or from about 60°C to about 130°C, or from about 70°C to about 120°C, or from about 80°C to about 110°C. Without theoretical limitations, it is expected that substrate temperatures below 120°C can promote the reaction of organotin precursors and water on the substrate surface, thereby promoting the formation of organotin oxide films.

[0067] In another embodiment, the reactor pressure for deposition according to the disclosed and claimed method is ≤ about 100 Torr. In another embodiment, the reactor pressure for deposition according to the disclosed and claimed method is ≤ about 75 Torr. In another embodiment, the reactor pressure for deposition according to the disclosed and claimed method is ≤ about 50 Torr. In another embodiment, the reactor pressure for deposition according to the disclosed and claimed method is ≤ about 40 Torr. In another embodiment, the reactor pressure for deposition according to the disclosed and claimed method is ≤ about 30 Torr. In a further aspect of this embodiment, the reactor pressure is ≤ about 20 Torr. In a further aspect of this embodiment, the reactor pressure is ≤ about 10 Torr. In a further aspect of this embodiment, the reactor pressure is ≤ about 5 Torr.

[0068] Cycle and sequence of steps In the above embodiments and other embodiments described herein, the described steps (e.g., (i) to (vi)) define a cycle of the method. It should be understood that the cycle can be repeated until a film of the desired thickness is obtained.

[0069] In the embodiments described herein, it should be understood that the steps of the method can be performed in a variety of sequences, can be performed sequentially or simultaneously (e.g., during at least a portion of another step), and in any combination thereof. Furthermore, the corresponding steps of supplying reactants (i.e., organotin precursors, water-containing vapors, and carboxylic acid-containing vapors) and / or subsequently purging them can be performed by varying the duration of their supply to alter the membrane composition.

[0070] Exemplary methods In one exemplary embodiment of the disclosed and claimed subject matter, an organotin oxide film is formed on a substrate using an ALD / ALD-like deposition method. The substrate and reactor are heated to a temperature of about 25°C to about 200°C, and the reactor pressure is (optionally) maintained at about 100 Torr or lower. The deposition steps include: (i) Introduce at least one substance with RSn(NR) into the reactor 1 R 2 )3 organotin precursor vapor, wherein R, R 1 and R 2 Each is independently selected from straight-chain C1 to C6 alkyl, branched C3 to C6 alkyl, C3 to C6 cycloalkyl, C2 to C6 alkenyl, C2 to C6 ynyl and C4 to C6 alkyl groups. 10 Aryl; (ii) Purge with inert gas; (iii) Introduce water vapor; (iv) Purge with inert gas; (v) Introducing equation R 3 COOH containing carboxylic acid vapor, of which R 3 Independently selected from hydrogen, straight-chain C1 to C6 alkyl, branched C3 to C6 alkyl, C3 to C6 cycloalkyl, C2 to C6 alkenyl, C2 to C6 ynyl and C4 to C6 alkyl. 10 Aryl; and (vi) Purge with an inert gas.

[0071] Steps (i) to (vi) can be repeated to provide an organotin oxide film of the desired thickness, ranging from about 50 Å to about 1000 Å, about 50 Å to about 500 Å, about 50 Å to about 300 Å, or about 50 Å to about 200 Å. In one embodiment, the film thickness formed by the method described herein is about 50 Å to about 1000 Å. In another aspect of this embodiment, the film thickness formed by the method described herein is about 50 Å to 500 Å. In another aspect of this embodiment, the film thickness formed by the method described herein is about 50 Å to 300 Å. In another aspect of this embodiment, the film thickness formed by the method described herein is about 50 Å to 200 Å.

[0072] In another exemplary embodiment of the disclosed and claimed subject matter, an organotin oxide film is formed on a substrate using an ALD / ALD-like deposition method. The substrate and reactor are heated to a temperature of about 25°C to about 200°C, and the reactor pressure is (optionally) maintained at about 100 Torr or lower. The deposition steps include: (i) Introduce at least one substance with RSn(NR) into the reactor 1 R 2 )3 organotin precursor vapor, wherein R, R 1 and R 2 Each is independently selected from straight-chain C1 to C6 alkyl, branched C3 to C6 alkyl, C3 to C6 cycloalkyl, C2 to C6 alkenyl, C2 to C6 ynyl and C4 to C6 alkyl groups. 10 Aryl; (ii) Purge with inert gas; (iii) Introduce water vapor; (iv) Purge with inert gas; (v) Introducing equation R 3 COOH containing carboxylic acid vapor, of which R 3 Independently selected from hydrogen, straight-chain C1 to C6 alkyl, branched C3 to C6 alkyl, C3 to C6 cycloalkyl, C2 to C6 alkenyl, C2 to C6 ynyl and C4 to C6 alkyl. 10 Aryl; and (vi) Purge with an inert gas.

[0073] In some embodiments, steps (i) to (iv) can be repeated to provide an organotin oxide film of the desired thickness, ranging from about 50 Å to about 1000 Å, about 50 Å to about 500 Å, about 50 Å to about 300 Å, or about 50 Å to about 200 Å, followed by steps (v) to (vi) to modify the resulting organotin oxide film. In some embodiments, an ultracycle ALD or ALD-like process can be performed, wherein an ultracycle includes repeating steps (i) to (iv) to provide an organotin oxide film of the desired thickness, ranging from about 50 Å to about 1000 Å, about 50 Å to about 500 Å, about 50 Å to about 300 Å, or about 50 Å to about 200 Å, followed by steps (v) to (vi) to modify the resulting organotin oxide film. The ultracycle can be repeated to provide an organotin oxide film of the desired thickness. It is believed that the reaction between carboxylic acid and the resulting organotin oxide film from steps (i) to (iv) can improve / stabilize the organotin oxide film, thereby making the organotin oxide film more resistant to environmental changes (such as moisture or carbon dioxide) during semiconductor manufacturing.

[0074] Example Reference will now be made to more specific embodiments of this disclosure and experimental results supporting such embodiments. The embodiments given below illustrate the disclosed and claimed subject matter more fully and should not be construed as limiting the disclosed subject matter in any way.

[0075] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed subject matter and the specific embodiments provided herein without departing from the spirit or scope of the disclosed subject matter. Therefore, it is intended that the disclosed subject matter, including the description provided in the following embodiments, cover modifications and variations of the disclosed subject matter within the scope of the appended claims and their equivalents.

[0076] Example 1 Conditions: Deposition temperature was 90°C; reactor pressure was approximately 2 Torr; i-PrSn(NMe2)3 was used as the organotin precursor. Table 1 summarizes the results.

[0077] Table 1 As shown in Table 1, the direct reaction between i-PrSn and acetic acid (Ex. 2) is considerably slower than the growth rate between i-PrSn(NMe2)3 (hereinafter referred to as "i-PrSn") and water (Ex. 1). For example, in Ex. 2, the GPC of the direct reaction between i-PrSn and acetic acid at 90 °C is only 0.2 Å / cycle, which results in an extremely long film deposition time due to the low precursor conversion efficiency. In contrast, the GPC of Ex. 1 is approximately 12 Å / cycle. By comparison, a GPC of up to 13 Å / cycle can be achieved using the i-PrSn-acetic acid-H2O sequence (Ex. 4). Photosensitivity was measured using an electron beam; a lower photosensitivity value means that the resulting organotin oxide film is more sensitive (i.e., higher photosensitivity) as a photosensitive material for future patterned applications. In Table 1, "NA" reflects the significantly higher precursor consumption required to produce a 250 Å film at 0.2 Å / cycle.

[0078] Table 1 also compares the photosensitivity of the two sequences containing the carboxylic acid with the baseline sequence in which the carboxylic acid is not used. Although adding the carboxylic acid before H2O vapor in the sequence resulted in a higher GPC (Ex. 4), the photosensitivity (dose) measured by EBL was approximately the same as the isopropyltris(dimethylamino)tin-H2O baseline (Ex. 1). Conversely, when the carboxylic acid was added after water (Ex. 3), a faster photosensitivity was achieved (as indicated by the smaller D50 in the EBL dose curve). Figure 1 As shown, the significant increase in photosensitivity (approximately 25%) for the organotin-H2O-carboxylic acid sequence was unexpected and not disclosed in any previous studies. Figure 1 It is generated by exposing an array of identical patterns on a sample with a resist film. The dose or radiation provided at each point in the array is different. Figure 1 The graphs in the diagram show the degree of resist retention at each dose after development. Resist sensitivity is evaluated by observing the lowest dose that still provides the desired pattern. Higher sensitivity (response at lower doses) is generally preferred. Also of interest is contrast, a measure of how rapidly the film response increases as the dose exceeds the minimum desired dose.

[0079] Based on the above, it has been demonstrated that adding a carboxylic acid (e.g., acetic acid) after the organotin precursor and water significantly and unexpectedly improves photosensitivity compared to the baseline of reacting organotin with water alone. Although the growth per cycle is lower (approximately 40% of the baseline process), the new sequence provides the advantage of improved photosensitivity, which directly translates into higher productivity and lower cost of ownership.

[0080] Example 2 Conditions: Deposition temperatures were 90 °C and 130 °C; reactor pressure was approximately 2 Torr; t-BuSn(NMe2)3(t-BuSn) and n-BuSn(NMe2)3(n-BuSn) were used as organotin precursors, respectively. Table 1 summarizes the results. Acetic acid end-capping was performed immediately in the same chamber after organotin oxide film deposition.

[0081] Table 2 As shown in Table 2, for t-BuSn at different deposition temperatures - Both the H2O and n-BuSn-H2O-H2O processes demonstrated an approximately 4x improvement in EUV light velocity with in-situ acetic acid capping. Compared to t-BuSn-H2O, t-BuSn-H2O with acetic acid capping showed a significantly improved EUV D50 velocity (mJ / cm²). 2 Improvement of approximately 9 mJ / cm 2 The acetic acid-capped n-BuSn-H2O showed an improvement of approximately 17 mJ / cm compared to n-BuSn-H2O. 2 The in-situ acetic acid capping step is performed at the same temperature as the deposition process. In this setting, the film thickness (and growth per cycle) remains the same, or even enhanced, as in the opposite of adding acetic acid to the deposition sequence, as in Example 1. Therefore, improvements in EUV speed can be achieved without sacrificing growth per cycle and productivity.

[0082] Example 3 Conditions: Deposition temperature was 130 °C; reactor pressure was approximately 2 Torr; t-BuSn(NMe2)3(t-BuSn) was used as the organotin precursor. Table 3 summarizes the results. Neopentanoic acid was used immediately in the same chamber after the organotin oxygen film deposition was completed.

[0083] Table 3 Although the invention has been described and illustrated in a certain degree of detail, it should be understood that this disclosure is by way of example only, and those skilled in the art can make numerous changes to the conditions and order of the steps without departing from the spirit and scope of the invention.

Claims

1. A method for depositing a tin-containing film, comprising: (i) Contacting the substrate with organotin precursor vapor in a deposition reaction vessel; (ii) Purge the reaction vessel with an inert gas; (iii) Contact the substrate with water vapor to form an organotin oxide network layer; (iv) Purge the reaction vessel with an inert gas; (v) Contacting the substrate with a carboxylic acid vapor; and (vi) Purge the reaction vessel with an inert gas.

2. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises the formula: RSn(NR) 1 R 2 )3 organotin precursors, wherein R, R 1 and R 2 Each is independently selected from straight-chain C1 to C6 alkyl, branched C3 to C6 alkyl, C3 to C6 cycloalkyl, C2 to C6 alkenyl, C2 to C6 ynyl and C4 to C6 alkyl groups. 10 Aryl.

3. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises MeSn(NMe2)3, MeSn(NEt2)3, EtSn(NMe2)3, EtSn(NEt2)3, n-PrSn(NMe2)3, i-PrSn(NMe2)3, n-BuSn(NMe2)3, i-BuSn(NMe2)3, s-BuSn(NMe2)3 One or more of the following: t-BuSn(NMe2)3, cyclopentylSn(NMe2)3, MeSn(NEtMe)3, EtSn(NEtMe)3, n-PrSn(NEtMe)3, i-PrSn(NEtMe)3, n-BuSn(NEtMe)3, i-BuSn(NEtMe)3, s-BuSn(NEtMe)3, t-BuSn(NEtMe)3, cyclopentylSn(NEtMe)3, and combinations thereof.

4. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises an organotin precursor.

5. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises MeSn(NMe2)3.

6. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises MeSn(NEt2)3.

7. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises EtSn(NMe2)3.

8. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises EtSn(NEt2)3.

9. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises n-PrSn(NMe2)3.

10. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises i-PrSn(NMe2)3.

11. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises n-BuSn(NMe2)3.

12. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises i-BuSn(NMe2)3.

13. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises s-BuSn(NMe2)3.

14. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises t-BuSn(NMe2)3.

15. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises cyclopentylSn(NMe2)3.

16. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises MeSn(NEtMe)3.

17. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises EtSn(NEtMe)3.

18. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises n-PrSn(NEtMe)3.

19. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises i-PrSn(NEtMe)3.

20. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises n-BuSn(NEtMe)3.

21. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises i-BuSn(NEtMe)3.

22. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises s-BuSn(NEtMe)3.

23. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises t-BuSn(NEtMe)3.

24. The method of claim 1, wherein the organotin precursor in step (i) of contacting the substrate with the organotin precursor vapor in the deposition reaction vessel comprises cyclopentylSn(NEtMe)3.

25. The method of claim 1, wherein step (i) of contacting the substrate with organotin precursor vapor in the deposition reaction vessel comprises pulsating the organotin precursor vapor for about 0.1 seconds to about 3 seconds.

26. The method of claim 1, wherein step (ii) purging the reaction vessel with an inert gas comprises a purging time of about 1 second to about 90 seconds.

27. The method of claim 1, wherein step (ii) purging the reaction vessel with an inert gas comprises a purging time of about 15 seconds to about 90 seconds.

28. The method of claim 1, wherein step (ii) purging the reaction vessel with an inert gas comprises a purging time of about 15 seconds to about 60 seconds.

29. The method of claim 1, wherein step (ii) purging the reaction vessel with an inert gas comprises a purging time of about 30 seconds.

30. The method of claim 1, wherein step (ii) purging the reaction vessel with an inert gas comprises a purging time of approximately 60 seconds.

31. The method of claim 1, wherein step (ii) purging the reaction vessel with an inert gas comprises a purging time of approximately 90 seconds.

32. The method of claim 1, wherein step (ii) purging the reaction vessel with an inert gas comprises purging with an inert gas containing argon.

33. The method of claim 1, wherein step (ii) purging the reaction vessel with an inert gas includes purging with an inert gas containing nitrogen.

34. The method of claim 1, wherein step (ii) purging the reaction vessel with an inert gas comprises purging with an inert gas containing helium.

35. The method of claim 1, wherein step (iii) of contacting the substrate with water vapor to form an organotin oxide network layer comprises pulsed the water vapor for about 0.5 seconds to about 5 seconds.

36. The method of claim 1, wherein step (iii) of contacting the substrate with water vapor to form an organotin oxide network layer comprises pulsed the water vapor for about 2.5 seconds.

37. The method of claim 1, wherein step (iii) of contacting the substrate with water vapor to form an organotin oxide network layer comprises pulsed the water vapor for about 5 seconds.

38. The method of claim 1, wherein step (iii) of contacting the substrate with water vapor to form an organotin oxide network layer comprises pulsed the water vapor for more than 5 seconds.

39. The method of claim 1, wherein step (iv) purging the reaction vessel with an inert gas comprises a purging time of about 15 seconds to about 90 seconds.

40. The method of claim 1, wherein step (iv) purging the reaction vessel with an inert gas comprises a purging time of about 15 seconds to about 60 seconds.

41. The method of claim 1, wherein step (iv) purging the reaction vessel with an inert gas comprises a purging time of approximately 30 seconds.

42. The method of claim 1, wherein step (iv) purging the reaction vessel with an inert gas comprises a purging time of approximately 60 seconds.

43. The method of claim 1, wherein step (iv) purging the reaction vessel with an inert gas comprises a purging time of approximately 90 seconds.

44. The method of claim 1, wherein step (iv) purging the reaction vessel with an inert gas comprises purging with an inert gas containing argon.

45. The method of claim 1, wherein step (iv) purging the reaction vessel with an inert gas comprises purging with an inert gas containing nitrogen.

46. ​​The method of claim 1, wherein step (iv) purging the reaction vessel with an inert gas comprises purging with an inert gas containing helium.

47. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing a carboxylic acid comprising the formula: R 3 Carboxylic acids of COOH, wherein R 3 Selected from hydrogen, straight-chain C1 to C6 alkyl, branched C3 to C6 alkyl, C3 to C6 cycloalkyl, C2 to C6 alkenyl, C2 to C6 ynyl and C4 to C6 alkyl. 10 Aryl.

48. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing a carboxylic acid vapor, and the carboxylic acid comprises one or more of formic acid, acetic acid, dihydroxyacetic acid, propionic acid, lactic acid, butyric acid, isobutyric acid, valeric acid, 2-methylbutyric acid, 3-methylbutyric acid, neopentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, fluoroacetic acid, chloroacetic acid, iodoacetic acid, dichloroacetic acid, 4,4,4-trifluorobutyric acid, 3,3,3-trifluoropropionic acid, heptafluorobutyric acid (also known as perfluorobutyric acid), perfluorovaleric acid, 3,3,3-trifluoro-2,2-dimethylpropionic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 4,4-difluorocyclohexanecarboxylic acid, tetrahydro-3-furanic acid, and combinations thereof.

49. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing formic acid, wherein the carboxylic acid comprises formic acid.

50. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor, wherein the carboxylic acid comprises acetic acid.

51. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing dihydroxyacetic acid.

52. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing propionic acid, wherein the carboxylic acid comprises propionic acid.

53. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing lactic acid.

54. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing butyric acid, wherein the carboxylic acid comprises butyric acid.

55. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing isobutyric acid.

56. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing valeric acid, wherein the carboxylic acid comprises valeric acid.

57. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing heptafluorobutyric acid.

58. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing perfluoropentanoic acid.

59. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing 3,3,3-trifluoro-2,2-dimethylpropionic acid.

60. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing carboxylic acid, wherein the carboxylic acid comprises neopentanoic acid.

61. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing 2-methylbutyric acid.

62. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing 3-methylbutyric acid.

63. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing hexanoic acid.

64. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing heptanoic acid.

65. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing octanoic acid.

66. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing nonanoic acid.

67. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing decanoic acid, wherein the carboxylic acid comprises decanoic acid.

68. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing fluoroacetic acid.

69. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing chloroacetic acid.

70. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing iodoacetic acid.

71. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing dichloroacetic acid.

72. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing 4,4,4-trifluorobutyric acid.

73. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing 3,3,3-trifluoropropionic acid.

74. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing cyclobutane carboxylic acid.

75. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing cyclopentanecarboxylic acid, wherein the carboxylic acid comprises cyclopentanecarboxylic acid.

76. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing cyclohexanecarboxylic acid.

77. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing 4,4-difluorocyclohexanecarboxylic acid.

78. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing a carboxylic acid vapor, wherein the carboxylic acid comprises tetrahydro-3-furanoic acid.

79. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing one or more carboxylic acids having a boiling point of 250°C or lower.

80. The method of claim 1, wherein step (v) contacts the substrate with a carboxylic acid vapor containing one or more carboxylic acids having a boiling point of 200°C or lower.

81. The method of claim 1, wherein step (v) contacts the substrate with the carboxylic acid containing carboxylic acid vapor, and the carboxylic acid is substantially free of any carboxylic acid with a boiling point greater than 250°C.

82. The method of claim 1, wherein step (v) contacts the substrate with the carboxylic acid containing carboxylic acid vapor, and the carboxylic acid is substantially free of any carboxylic acid with a boiling point greater than 200°C.

83. The method of claim 1, wherein step (v) involves contacting the substrate with the carboxylic acid vapor containing carboxylic acid, wherein the carboxylic acid does not contain any carboxylic acid with a boiling point greater than 250°C.

84. The method of claim 1, wherein step (v) involves contacting the substrate with the carboxylic acid vapor containing carboxylic acid, wherein the carboxylic acid does not contain any carboxylic acid with a boiling point greater than 200°C.

85. The method of claim 1, wherein step (vi) purging the reaction vessel with an inert gas comprises a purging time of about 15 seconds to about 90 seconds.

86. The method of claim 1, wherein step (vi) purging the reaction vessel with an inert gas comprises a purging time of about 15 seconds to about 60 seconds.

87. The method of claim 1, wherein step (vi) purging the reaction vessel with an inert gas comprises a purging time of approximately 30 seconds.

88. The method of claim 1, wherein step (vi) purging the reaction vessel with an inert gas comprises a purging time of approximately 60 seconds.

89. The method of claim 1, wherein step (vi) purging the reaction vessel with an inert gas comprises a purging time of approximately 90 seconds.

90. The method of claim 1, wherein step (vi) purging the reaction vessel with an inert gas comprises purging with an inert gas containing argon.

91. The method of claim 1, wherein step (vi) purging the reaction vessel with an inert gas comprises purging with an inert gas containing nitrogen.

92. The method of claim 1, wherein step (vi) purging the reaction vessel with an inert gas comprises purging with an inert gas containing helium.

93. The method of any one of claims 1 to 92 further comprises exposing the tin-containing film to a radiation source selected from KrF (248 nm), ArF (193 nm), VUV (157 nm), EUV (13 nm), electron beam, X-ray and ion beam.

94. An organotin oxide material deposited by any one of claims 1 to 93.

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