Intramolecularly stabilized monoalkyl metal compounds with improved thermal and photostability and uses thereof

Abstract

The disclosed and claimed subject matter relates to monoalkyl metal compounds of formula (XR) M (NR1R2) 3 and their use in methods of depositing metal-containing films.

Description

background Technical Field

[0001] The disclosed and claimed subjects relate to monoalkyl metal compounds and their use in methods for depositing metal-containing films. Background Technology

[0002] Thin films, especially those containing metals, have a variety of important applications, such as in the fabrication of nanotechnology and semiconductor devices. Examples of such applications include 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, EUV photoresist patterning materials, hard masks, transparent conductive electrodes, and integrated circuits.

[0003] 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). The use of CVD and ALD processes is increasing due to their advantages of enhanced compositional control, high film uniformity, and effective doping control.

[0004] CVD is a chemical process in which precursors are used to form thin films on a substrate surface. In a typical CVD process, precursors pass through the substrate (e.g., a wafer) surface in a low- or atmospheric-pressure reactor. The precursors react and / or decompose on the substrate surface, resulting in a thin film of deposited material. Volatile byproducts are removed by gas flow through the reaction chamber. 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 effects, and time.

[0005] ALD (Alternating Discharge) is also a method for depositing thin films. It is a self-limiting, sequential, and unique film growth technique based on surface reactions that provides precise thickness control and allows conformal film deposition of materials supplied by precursors onto substrate surfaces with different compositions. In ALD, precursors are introduced individually during the reaction process, forming a reaction sequence. The first precursor passes through the substrate surface, creating a monolayer on the substrate surface. Any excess unreacted precursor is pumped out of the reaction chamber. A second precursor is then passed through 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.

[0006] However, the continuous shrinking of microelectronic components (such as semiconductor devices) presents several technical challenges and increases the demand 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 pathways or interconnects. Filling such features, especially in increasingly smaller microelectronic components, can be challenging because these features may become increasingly thin or narrow. Therefore, as the thickness of a feature approaches zero, complete filling of the feature (e.g., 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. Thus, when performing ALD, hollow seams may remain in the middle portion of the feature. The presence of such hollow seams within a feature is undesirable as they can lead to device failure. Therefore, there is significant interest in the development of thin-film deposition methods, particularly ALD methods, which 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 the feature without any voids.

[0007] In CVD and ALD, precursor molecules play a crucial role in achieving high-quality films with high conformability and low impurities. Suitable metal precursors include those that are thermally stable to prevent any thermal decomposition but thermally activated for initial chemical adsorption, and remain chemically reactive to added reagents. Furthermore, it is important that the metal precursor is monomeric to obtain maximum volatility, thermally stable, and of high purity to ensure clean evaporation, leaving only trace amounts of non-volatile residues. It is also desirable that the precursor is liquid at room temperature. The substrate temperature in CVD and ALD processes is an important consideration in the selection of precursor molecules. Higher substrate temperatures generally promote higher film growth rates. Preferred precursor molecules must be stable within this temperature range. Preferred precursors are capable of being transported as a gas from the liquid phase to the reaction vessel. This ensures a constant evaporation surface, which typically transports the precursor to the reaction vessel more uniformly than a solid-phase precursor. Preferred precursors need to be thermally stable during use on the deposition equipment and have sufficient vapor pressure to be transported to the deposition equipment without significant decomposition. Precursors are typically transported from containers stored on the deposition equipment for extended periods (typically more than 3 months). Impurities formed through the thermal decomposition of the precursor can negatively impact the deposition process. In some applications, it is also preferable to have a precursor with low photosensitivity to achieve a longer shelf life.

[0008] There is a need in the art to provide a thermally stable composition and a method for depositing organotin and organogermanium films using organometallic (Sn and Ge) compounds as precursors for certain applications in the semiconductor industry, such as EUV photoresist materials, hard masks for patterning, and transparent conductive electrodes. Compared to films disclosed in the prior art (i.e., organotin oxide films derived from organotin precursors having iPr-Sn or tBu-Sn groups), organotin or organogermanium oxide films obtained using organometallic compounds that form thermally stable compositions can produce organotin and organogermanium oxide films with different physical and electrical properties required in semiconductor manufacturing.

[0009] Only a few existing technologies describe organogermanium triamides containing Me, Et, nBu, and tBu groups and their use as precursors for the vapor deposition of organogermanium oxide films. These include: (i) WO2007140012; (ii) EP1464724; (iii) Thornten, P., “Germylamines,” Science of Synthesis , Vol. 5, 97-100 (2003); (iv) Shutov, PL et al. (2001), "Syntheses and Characterization of 1-Haloazagermatranes," Zeitschrift fuer Naturforschung, B: Chemical Sciences , Vol. 56, 2, 137-140 (2001); and (v) U.S. Patent No. 5,344,948. Organogermanium triamide complexes with alkyl chains having additional coordination sites (which enhance thermal stability) do not appear to have been described in the literature.

[0010] Organotin triamides having Me, Et, iPr, nBu, and tBu groups, as well as dialkylamide groups (such as dimethylamide, ethylmethylamide, and diethylamide), and their use as precursors in the vapor deposition of organotin oxide films have been described. For example: (i) Lorberth, J., and MR Kula, “Methyltin Amides,” Chem. Ber ., 98(2): 520-525 (1965); (ii) Jones, K. and MF Lappert, “Amino Derivatives of Metals and Metalloids: Preparation of Aminostannanes, Stannylamines, andStannazanes,” J. Chem. Soc. , 1944-1951 (1965); (iii) Haenssgen, D. et al., "Synthesis of the First Mono-tert-butyltin Compounds," J. Organomet. Chem. ,293(2): 191-195 (1985); (iv) U.S. Patent Application Publication No. 2022306657; (v) Kula, M.-R. et al., “Proton Magnetic Resonance Spectra of Organotindiethylamides,” Chem. Ber. , 97(5): 1294-1297 (1964); (vi) U.S. Patent Application Publication No. 2022242888; (vii) U.S. Patent Application Publication No. 2019 / 337969; (viii) WO2022 / 016128; and (ix) U.S. Patent No. 10,732,505.

[0011] Other organotin triamides with hydrocarbon groups have been described as precursors for solution-phase deposition of organotin oxide films. For example: U.S. Patent Application Publication No. 10228618; U.S. Patent Application Publication No. 2022 / 0064192.

[0012] However, the aforementioned references use complex synthetic routes or expensive or synthetically complex starting materials. Another issue is the selectivity of different syntheses for these monoalkyltin compounds. These references also demonstrate the difficulty of synthesizing monoalkyltin complexes without impurities (i.e., organotin compounds with more than one alkyl ligand as byproducts) (which is why multi-step synthesis with low yields is often employed to achieve high purity). In contrast, what is disclosed and claimed herein is a one-step synthesis using a Grignard reagent in the form of MgRX / MgR2 and Sn(NMe2)4 as a starting material. The Grignard reagent was synthesized according to a known synthetic procedure, and Sn(NMe2)4 is commercially available or can be obtained using SnCl4, HNMe2, and... n BuLi synthesis. This one-step synthesis selectively yields monoalkylated products and shows only 4-5% peralkylation.

[0013] Other references disclose the introduction of alkyl chains with heteroatoms or heterocycles with oxygen and nitrogen atoms, but do not show any synthetic work or the effect of heteroatoms on the thermal or photostability of the precursors. See, for example, Pieper, N. et al., “Aminoalkyl Tin Compounds,” Organometallics, 16:1043-1052 (1997), U.S. Patent Application Publication No. 20230072538 and U.S. Patent Application Publication No. 2023 / 0374338.

[0014] Similarly, different types of alkyl chains with heteroatoms attached to the Sn center have been shown for deposition (MOCVD and related methods) of tin metal films or films of tin mixed with arsenic, antimony, or phosphorus (but not oxygen). However, only structures in which R is specifically a straight chain have been shown, and the unexpected stabilizing effect of branched systems with quaternary carbons at the α-, β-, or γ-positions relative to tin has not been considered or proposed. See, for example, DE4213292. Another patent claims protection for similar compounds as coordination catalysts. In this case, similar alkyl chains with heteroatoms attached to the Sn center are claimed; however, the other three ligands at the Sn center are not claimed to be amides. See, for example, EP0690748.

[0015] Another reference discloses the use of monoalkyltinamides with nitrogen in the alkyl chain as precursors for photoresist. This includes branched alkyl chains; however, all compounds contain alkyl chains with the most secondary and tertiary carbons, such that at least one hydrogen atom is present at each carbon position of the alkyl chain. Similarly, unexpected stabilizing effects of branched systems having at least one quaternary carbon at the α-, β-, or γ-position relative to tin have not been considered or proposed. See, for example, U.S. Patent Application Publication No. 2024 / 0201586.

[0016] Although organotin triamides are generally highly volatile and liquid, they typically exhibit high photosensitivity and relatively low thermal stability, making them unsuitable for vapor deposition applications. The disclosed and claimed subjects include compounds with additional electron-donating functionality (oxygen or nitrogen) at the alkyl chain, which have a chelating effect and can stabilize the complex. Furthermore, by utilizing branched alkyl chains having at least one quaternary carbon at one or more of the α-, β-, or γ-positions, hydrogen atoms are excluded, and potential α-, β-, or γ-hydrogen elimination is suppressed. These two features improve the thermal and photostability of the claimed compounds compared to known monoalkyltin triamide complexes (such as MeSn(NMe2)3 or iPrSn(NMe2)3), making the claimed complexes advantageous for use in CVD and ALD processes for depositing high-purity Sn-containing thin films. Summary of the Invention

[0017] In one embodiment, the disclosed and claimed subject matter relates to compounds of formula (I): (The following is "(XR)M(NR)") 1 R 2 )3”) in (i) M = Sn or Ge; (ii) R is a branch C5 to C 10 An alkylene linking group, wherein (i) three to eight main chain carbon moieties link M and X, and (ii) the first three main chain carbon moieties linking M and X (i.e., α-, β-, or γ-). - At least one of the carbon moieties is a hydrogen-free quaternary carbon moieties; (iii)R 1 and R 2 Each is independently selected from straight-chain C1 to C6 alkyl, branched C4 to C6 alkyl, or cyclic C3 to C6 alkyl; and (iv)X is selected from -OR 3 or -NR 4 R 5 One of them, where R 3 R 4 and R 5 Each compound is independently selected from straight-chain C1 to C6 alkyl groups, branched C4 to C6 alkyl groups, or cyclic C3 to C6 alkyl groups. In one aspect of this embodiment, the compound of formula (I) comprises (NMe2CH2CMe2CH2)Sn(NMe2)3, is substantially composed of, or is composed of, it. In one aspect of this embodiment, the compound of formula (I) comprises (OMeCH2CH2CMe2)Sn(NMe2)3, is substantially composed of, or is composed of, it.

[0018] The disclosed and claimed compounds of formula (I) contain three amides (-NR). 1 R 2 The compound is composed of an alkylene group (-R) and an additional coordination site (X), which may be an amine or an ether group. This amine or ether group (X) coordinates with the metal via a coordinate bond (as shown by the dashed lines above) to stabilize the disclosed and claimed compound, rather than a covalent bond, such as an amide (-NR). 1 R 2 The disclosed and claimed compounds do not include those having the formula M(NR) disclosed in U.S. Patent No. 11,500,284. 1 R 2 Compounds of formula RM(NR) and those discussed therein 1 R 2 )3 Related organotin compounds.

[0019] In one embodiment, the disclosed and claimed subject matter relates to compounds comprising one or more of formula (I), compositions substantially composed of, or composed of the same formula (I).

[0020] In another embodiment, the above-described compounds and / or compositions are used in a method for depositing tin-containing films and / or germanium-containing films. In a further aspect of this embodiment, the deposited film comprises, is substantially composed of, or is composed of, one or more of organotin oxides, tin oxides, organogermanium oxides, and germanium oxides.

[0021] The summary of this invention does not detail every embodiment and / or incremental novelty of the disclosed and claimed subject matter. Rather, the summary provides only a preliminary discussion of different embodiments and corresponding novel points relative to conventional and known technologies. For additional details and / or possible perspectives on the disclosed and claimed subject matter and embodiments, please refer to the detailed description and corresponding drawings below, which will be discussed further.

[0022] The order in which the different steps described herein are presented is for clarity. In general, 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 places within this disclosure, it is contemplated that each concept can be performed independently of each other or, where appropriate, in combination with each other. Therefore, the disclosed and claimed subject matter can be embodied and considered in a variety of different ways. Attached Figure Description

[0023] The accompanying drawings, included to provide a further understanding of the disclosed subject matter and incorporated into and forming part of this specification, 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 (DMDMP)Sn(NMe2)3 (compound "3") was shown. 1 H NMR; Figure 2 Compound 3 was shown 13 C NMR; Figure 3 Compound 3 was shown 119 Sn NMR; Figure 4 The results show the preparation of compound 3 by conventional synthetic methods. 1 H NMR; Figure 5 The results show the preparation of compound 3 by conventional synthetic methods. 13 C NMR; Figure 6 Thermogravimetric analysis (TGA) of compounds 3 and 7 is shown; Figure 7 Differential scanning calorimetry (DSC) analysis of compound 3 is shown; Figure 8The images show compound 3 recorded at room temperature at various time intervals. 119 Sn NMR spectrum; Figure 9 The results showed that iPrSn(NMe2)3 after 24 days of light exposure 119 Sn NMR spectrum; Figure 10 The (MODMP)Sn(NMe2)3 (compound "7") was shown. 1 H NMR; Figure 11 Compound 7 was shown. 119 Sn NMR; Figure 12 The DSC of compound 7 is shown; Figure 13 The growth rate of (DMDMP)Sn(NMe2)3 versus the number of cycles is shown for an ALD-like cycle containing (DMDMP)Sn(NMe2)3 (5 sec) - purge (60 sec) - H2O (0.1 sec) - purge (90 sec) at 90 °C, demonstrating linear growth of the ALD-like sample; and Figure 14 The growth rate of (DMDMP)Sn(NMe2)3 versus the number of cycles is shown for an ALD-like cycle containing (DMDMP)Sn(NMe2)3 (5 sec) - purge (60 sec) - H2O (0.1 sec) - purge (90 sec) at 110 °C, demonstrating linear growth of the ALD-like cycle.

[0024] definition Unless otherwise stated, the following terms used in this specification and claims shall have the following meanings in this application.

[0025] For the purposes of this invention and its claims, the numbering scheme for the periodic table family is based on the IUPAC periodic table.

[0026] The term “and / or” is used in phrases such as “A and / or B” in this article to include “A and B”, “A or B”, and “A” and “B”.

[0027] As used in this article, "C" x-y "" indicates the number of carbon atoms in the chain. For example, C 1-6 Alkyl refers to an alkyl chain having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl). Unless otherwise specified, the chain can be straight or branched.

[0028] Unless otherwise stated, "alkyl" refers to a hydrocarbon group that can be straight-chain, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.), or polycyclic (e.g., norbornyl, adamantyl, etc.). Suitable acyclic groups can be methyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl or tert-butyl, straight-chain or branched pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, and hexadecyl. Unless otherwise stated, alkyl refers to a moiety of 1 to 10 carbon atoms. Cycloalkyl can be monocyclic or polycyclic. Suitable examples of monocyclic alkyl include substituted cyclopentyl, cyclohexyl, and cycloheptyl. As described herein, cycloalkyl can have any acyclic alkyl group as a substituent. These alkyl moieties can be substituted or unsubstituted.

[0029] "Hydroxyl" (also known as "hydroxyl group") refers to the -OH group.

[0030] Unless otherwise stated, the term "substituted" in the context of alkyl, alkoxy, fluorinated alkyl, etc., refers to one of these moieties that also contains one or more substituents, including but not limited to: alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, alkoxy, alkylaryl, haloalkyl, halogen, hydroxyl, amino, and aminoalkyl. Similarly, the term "unsubstituted" refers to these same moieties that are free of substituents other than hydrogen.

[0031] Alkylenes are divalent saturated aliphatic groups (such as ethylenes) derived from alkanes (such as those described above) by removing two hydrogen atoms from different carbon atoms. When referring to alkylenes, these include those whose carbon chains are separated by (C1-C2) hydrogen atoms. 18 Alkyl-substituted alkylene chains. Alkylenes may also contain one or more alkynyl groups in the alkylene moiety, where alkynyl refers to a triple bond. Essentially, an alkylene group is a divalent hydrocarbon group serving as its backbone. Therefore, the divalent acyclic group can be methylene, 1,1- or 1,2-ethylene, 1,1-, 1,2- or 1,3-propylene, 2,5-dimethyl-hexylene, 2,5-dimethyl-hex-3-ynyl, etc. Similarly, the divalent cyclic alkyl group can be 1,2- or 1,3-cyclopentylene, 1,2-, 1,3- or 1,4-cyclohexylene, etc.

[0032] The terms “substituent,” “base,” “group,” and “part” are used interchangeably.

[0033] As used herein, the terms "metal-containing complex" (or 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 a vapor deposition process (e.g., ALD or CVD). Metal-containing complexes can be deposited on a substrate or its surface, adsorbed onto a substrate or its surface, decomposed on a substrate or its surface, transported to a substrate or its surface, and / or pass 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.

[0034] As used herein, the term "metal-containing film" includes not only elemental metal films as more fully defined below, but also films containing 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 contain 100% pure metal, or an elemental metal film may contain 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.

[0035] As used herein, the term "vapor deposition process" refers 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 Applications Jones, AC; Hitchman, ML (eds.), The Royal Society of Chemistry: Cambridge, 2009; Chapter 1, pp. 1-36, describes various vapor deposition techniques.

[0036] Throughout this specification, the term “ALD or ALD-like” refers to processes including, but not limited to, those that: a) sequentially introduce each reactant, comprising an organotin compound precursor and a reactive gas, 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 an organotin compound precursor and a reactive gas, 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). “ALD-like” is defined herein as a cyclic CVD process that delivers a highly conformal metallized film on a substrate, such as by having at least one of the following: a non-uniformity percentage of approximately 5% or less as measured by an ellipsometry, a deposition rate of 1 Å or higher per cycle, or a combination thereof.

[0037] 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.

[0038] 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.).

[0039] When used for measurable numerical variables, the term “about” or “approximately” refers to the indicated value of the variable and all values ​​within ±5% of that indicated value.

[0040] "Halogenated" or "halogenated" refers to halogens (e.g., F, Cl, Br, and I).

[0041] "Tin-containing film" refers to organotin oxide or tin oxide, which can be used as a material in the manufacturing process of semiconductors or display devices.

[0042] 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. Detailed Implementation

[0043] 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. The purpose, features, advantages, and concepts of the disclosed subject matter are clear to those skilled in the art based on the description provided herein, 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.

[0044] 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.

[0045] In the embodiments of the methods or processes described below, it should be understood that in some embodiments, the steps of the method may be performed in a variety of sequences, may be performed sequentially or simultaneously (e.g., during at least a portion of another step), and may be performed in any combination thereof. The corresponding steps of supplying the precursor and the nitrogen-containing source gas can be performed by varying the duration of their supply to alter the stoichiometric composition of the resulting dielectric membrane.

[0046] As described above, the disclosed and claimed subject matter relates to monoalkyl metal compounds and their use in methods for depositing metal-containing films. In the typical preparation of such materials, over-alkylation typically occurs, either due to strong alkylating agents or due to rearrangement of the corresponding products, where two RSnL3 ligands slowly react to form R2SnL2 and SnL4. This particular redistribution behavior has not been observed for germanium in the literature. One method for thermally stabilizing these types of compounds is to insert another coordination site into the alkyl ligand. This can improve overall stability but also leads to reduced volatility or even curing at room temperature.

[0047] The disclosed and claimed subject matter overcomes the aforementioned problems. Specifically, it provides a simple method for synthesizing compounds of formula (I): (XR)M(NR) 1 R 2 )3, of which (i) M = Sn or Ge; (ii) R is a branch C5 to C 10 Alkylene linking group, wherein (i) three to eight main chain carbon moieties link M and X, and (ii) at least one of the first three main chain carbon moieties linking M and X (i.e., α-, β- or γ-carbon moieties) is a hydrogen-free quaternary carbon moieties; (iii)R 1 and R 2 Each is independently selected from straight-chain C1 to C6 alkyl, branched C4 to C6 alkyl, or cyclic C3 to C6 alkyl; and (iv) X is selected as -OR 3 or -NR 4 R 5 One of them, of which R 3 R 4 and R 5 Each compound is independently selected from straight-chain C1 to C6 alkyl groups, branched C4 to C6 alkyl groups, or cyclic C3 to C6 alkyl groups. These compounds remain liquid at room temperature and offer high thermal and light stability, making them ideal for vapor deposition processes. The introduction of alkyl groups with additional heteroatoms (i.e., -OR) 3 and -NR 4 R 5 This forms coordination bonds with the metal center, which improves thermal and light stability. Furthermore, blocking the α-, β-, or γ-C-positions of the alkylene groups associated with the metal atom with alkyl groups (such as one or two methyl groups) blocks potential α-, β-, or γ-hydrogen elimination decomposition pathways and introduces greater asymmetry into the resulting metal complex. Therefore, thermal stability, volatility, and viscosity are improved.

[0048] Organotin and organogermanium compounds In one embodiment, the disclosed and claimed subject matter relates to compounds of formula (I): (XR)M(NR) 1 R 2 )3, of which (i) M = Sn or Ge; (ii) R is a branch C5 to C 10 Alkylene linking group, wherein (i) three to eight main chain carbon moieties link M and X, and (ii) at least one of the first three main chain carbon moieties linking M and X (i.e., α-, β- or γ-carbon moieties) is a hydrogen-free quaternary carbon moieties; (iii)R 1 and R 2 Each is independently selected from straight-chain C1 to C6 alkyl, branched C4 to C6 alkyl, or cyclic C3 to C6 alkyl; and (iv) X is selected as -OR 3 or -NR4 R 5 One of them, of which R 3 R 4 and R 5 Each is independently selected from straight-chain C1 to C6 alkyl, branched C4 to C6 alkyl, or cyclic C3 to C6 alkyl.

[0049] Metal In one implementation, M = Sn.

[0050] In one implementation, M = Ge.

[0051] R group As mentioned above, R is the branch C5 to C6. 10 An alkylene linking group, wherein (i) three to eight main chain carbon moieties link M and X, and (ii) at least one of the first three main chain carbon moieties linking M and X (i.e., α- or β- or γ-position or α- or β- or γ-carbon) is a hydrogen-free quaternary carbon moieties. As those skilled in the art will understand, although the R group comprises a total of five to ten carbon moieties, at least three to eight of these carbon moieties must form the main chain linking M and X (i.e., the “backbone”), and at least one of the first three carbon moieties in the main chain starting from M (i.e., the α-carbon moieties, β-carbon moieties, and γ-carbon moieties) must be a hydrogen-free quaternary carbon moieties. Thus, for example, an embodiment wherein R has three carbon moieties in the main chain linking M and X has the formula / structure (NR). 1 R 2 3M-C α -C β -C γ -X (Note that the side chains / hydrogens on the three skeletal carbon moieties are not shown).

[0052] It should also be understood that the requirement that at least one of the first three carbon motifs (i.e., the α-carbon motif, β-carbon motif, and γ-carbon motif) in the main chain starting from M must be a hydrogen-free quaternary carbon motif only applies to the carbon atoms in the carbon motifs of the main chain (i.e., the "backbone") connecting M and X; it does not exclude other atoms (i.e., atoms attached to or additionally attached to such main chain carbon motifs) ， The presence of hydrogen atoms on side chains attached to the main carbon chain (e.g., -CH3 groups).

[0053] In one implementation, in R, C5 to C 10 The alkylene linking group consists of three main chain carbon moieties that connect M and X.

[0054] In one implementation, in R, C5 to C 10 The alkylene linking group consists of four main chain carbon moieties that connect M and X.

[0055] In one implementation, in R, C5 to C 10 The alkylene linking group consists of five main chain carbon moieties that link M and X.

[0056] In one implementation, in R, C5 to C 10 The alkylene linking group consists of six main chain carbon moieties that link M and X.

[0057] In one implementation, in R, C5 to C 10 The alkylene linking group consists of seven main chain carbon moieties that link M and X.

[0058] In one implementation, in R, C5 to C 10 The alkylene linking group consists of eight main chain carbon moieties that link M and X.

[0059] In one implementation, in R, the α-carbon moiety is a hydrogen-free quaternary carbon moiety.

[0060] In one implementation, in R, the β-carbon moiety is a hydrogen-free quaternary carbon moiety.

[0061] In one implementation, in R, the γ-carbon moiety is a hydrogen-free quaternary carbon moiety.

[0062] In one embodiment, in R, two or more of the α-carbon moiety, β-carbon moiety, and γ-carbon moiety are hydrogen-free quaternary carbon moieties.

[0063] In one embodiment, R is a -C(Me2)CH2CH2- group that starts from M and is attached to X (i.e., (NR)). 1 R 2 )3M-C(Me2)CH2CH2-X).

[0064] In one embodiment, R is a -CH2C(Me2)CH2- group that starts from M and is attached to X (i.e., (NR)). 1 R 2 )3M-CH2C(Me2)CH2-X).

[0065] In one embodiment, R is a -CH2CH2C(Me2) group that starts from M and is attached to X (i.e., (NR)). 1 R 2 )3M-CH2CH2C(Me2)-X).

[0066] R 1 and R 2 Group In one implementation, R 1 and R 2One or both of them are straight-chain C1 to C6 alkyl groups. In one aspect of this embodiment, R 1 and R 2 One or both of them are straight-chain C1 alkyl groups. In one aspect of this embodiment, R 1 and R 2 One or both of them are straight-chain C2 alkyl groups. In one aspect of this embodiment, R 1 and R 2 One or both of them are straight-chain C3 alkyl groups. In one aspect of this embodiment, R 1 and R 2 One or both of them are straight-chain C4 alkyl groups. In one aspect of this embodiment, R 1 and R 2 One or both of them are straight-chain C5 alkyl groups. In one aspect of this embodiment, R 1 and R 2 One or both of them are straight-chain C6 alkyl groups.

[0067] In one implementation, R 1 and R 2 One or both of them are branched C4 to C6 alkyl groups. In one aspect of this embodiment, R 1 and R 2 One or both of them are branched C4 alkyl groups. In one aspect of this embodiment, R 1 and R 2 One or both of them are branched C5 alkyl groups. In one aspect of this embodiment, R 1 and R 2 One or two of them are branched C6 alkyl groups.

[0068] In one implementation, R 1 and R 2 One or both are cyclic C3 to C6 alkyl groups. In one aspect of this embodiment, R 1 and R 2 One or both of them are cyclic C3 alkyl groups. In one aspect of this embodiment, R 1 and R 2 One or both of them are cyclic C4 alkyl groups. In one aspect of this embodiment, R 1 and R 2 One or both of them are cyclic C5 alkyl groups. In one aspect of this embodiment, R 1 and R 2 One or both of them are cyclic C6 alkyl groups.

[0069] X group In one implementation, X is -OR 3 Group. In one aspect of this embodiment, R3 It is a straight-chain C1 to C6 alkyl group. In one aspect of this embodiment, R... 3 It is a straight-chain C1 alkyl group. In one aspect of this embodiment, R... 3 It is a straight-chain C2 alkyl group. In one aspect of this embodiment, R... 3 It is a straight-chain C3 alkyl group. In one aspect of this embodiment, R... 3 It is a straight-chain C4 alkyl group. In one aspect of this embodiment, R... 3 It is a straight-chain C5 alkyl group. In one aspect of this embodiment, R... 3 It is a straight-chain C6 alkyl group. In another aspect of this embodiment, R... 3 It is a branched C4 to C6 alkyl group. In one aspect of this embodiment, R... 3 It is a branched C4 alkyl group. In one aspect of this embodiment, R... 3 It is a branched C5 alkyl group. In one aspect of this embodiment, R 3 It is a branched C6 alkyl group. In a further aspect of this embodiment, R... 3 It is a cyclic C3 to C6 alkyl group. In one aspect of this embodiment, R... 3 It is a cyclic C3 alkyl group. In one aspect of this embodiment, R 3 It is a cyclic C4 alkyl group. In one aspect of this embodiment, R... 3 It is a cyclic C5 alkyl group. In one aspect of this embodiment, R... 3 It is a cyclic C6 alkyl group.

[0070] In one implementation, X is -NR 4 R 5 Group. In one aspect of this embodiment, R 4 and R 5 One or both of them are straight-chain C1 to C6 alkyl groups. In one aspect of this embodiment, R 4 and R 5 One or both of them are straight-chain C1 alkyl groups. In one aspect of this embodiment, R 4 and R 5 One or both of them are straight-chain C2 alkyl groups. In one aspect of this embodiment, R 4 and R 5 One or both of them are straight-chain C3 alkyl groups. In one aspect of this embodiment, R 4 and R 5 One or both of them are straight-chain C4 alkyl groups. In one aspect of this embodiment, R 4 and R 5 One or both of them are straight-chain C5 alkyl groups. In one aspect of this embodiment, R 4 and R 5One or both are straight-chain C6 alkyl groups. In another aspect of this embodiment, R 4 and R 5 One or both of them are branched C4 to C6 alkyl groups. In one aspect of this embodiment, R 4 and R 5 One or both of them are branched C4 alkyl groups. In one aspect of this embodiment, R 4 and R 5 One or both of them are branched C5 alkyl groups. In one aspect of this embodiment, R 4 and R 5 One or both of them are branched C6 alkyl groups. In a further aspect of this embodiment, R 4 and R 5 One or both are cyclic C3 to C6 alkyl groups. In one aspect of this embodiment, R 4 and R 5 One or both of them are cyclic C3 alkyl groups. In one aspect of this embodiment, R 4 and R 5 One or both of them are cyclic C4 alkyl groups. In one aspect of this embodiment, R 4 and R 5 One or both of them are cyclic C5 alkyl groups. In one aspect of this embodiment, R 4 and R 5 One or both of them are cyclic C6 alkyl groups.

[0071] In one embodiment, the compound of formula (I) includes (NMe2CH2CMe2CH2)Sn(NMe2)3, is substantially composed of, or is composed of.

[0072] In one embodiment, the compound of formula (I) includes (OMeCH2CMe2CH2)Sn(NMe2)3, is substantially composed of, or is composed of.

[0073] In one embodiment, the compound of formula (I) includes (NMe2CH2CH2CMe2)Sn(NMe2)3, is substantially composed of, or is composed of.

[0074] In one embodiment, the compound of formula (I) includes (OMeCH2CH2CMe2)Sn(NMe2)3, is substantially composed of, or is composed of.

[0075] Exemplary Implementation In one implementation, in formula (I), M is Sn, R is one of -C(Me2)CH2CH2-, -CH2C(Me2)CH2-, and -CH2CH2C(Me2)-, and R 1 and R2 Each is independently one of Me and Et, and X is -NR. 4 R 5 , where R 4 and R 5 Each is independently one of Me and Et.

[0076] In one implementation, in formula (I), M is Sn, R is one of -C(Me2)CH2CH2-, -CH2C(Me2)CH2-, and -CH2CH2C(Me2)-, and R 1 and R 2 Each is independently one of Me and Et, and X is -OR 3 , where R 3 It is one of Me and Et.

[0077] In one implementation, in formula (I), M is Sn, R is -CH2C(Me2)CH2-, and R 1 and R 2 Let X be Me, and X be -NMe2, as shown below: (i.e., 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(dimethylamino)tin).

[0078] In one implementation, in formula (I), M is Sn, R is -CH2C(Me2)CH2-, and R 1 and R 2 Let X be Me and X be -NEt2, as shown below: (i.e., 3-(N,N-diethylamino)-2,2-dimethyl-propyl-tris-(dimethylamino)tin).

[0079] In one implementation, in formula (I), M is Sn, R is -CH2C(Me2)CH2-, and R 1 It is Me and R 2 It is Et, and X is -NMe2, as shown below: (i.e., 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin).

[0080] In one implementation, in formula (I), M is Sn, R is -CH2C(Me2)CH2-, and R 1 and R 2 Let X be Et, and X be -NEt2, as shown below: (i.e., 3-(N,N-diethylamino)-2,2-dimethyl-propyl-tris-(diethylamino)tin).

[0081] In one implementation, in formula (I), M is Sn, R is -CH2C(Me2)CH2-, and R 1 It is Me and R 2 It is iPr, and X = -NMe2, as shown below: (i.e., 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(methyl-isopropylamino)tin).

[0082] In one implementation, in formula (I), M is Sn, R is -CH2CH2C(Me2)-, R 1 and R 2 Let X be Me, and X be -NMe2, as shown below: (i.e., 3-(N,N-dimethylamino)-1,1-dimethyl-propyl-tris-(dimethylamino)tin).

[0083] In one implementation, in formula (I), M is Sn, R is -CH2C(Me2)CH2-, and R 1 and R 2 It is Me, and X is -OMe, as shown below: (i.e., 3-methoxy-2,2-dimethyl-propyl-tris-(dimethylamino)tin).

[0084] In one implementation, in formula (I), M is Sn, R is -CH2C(Me2)CH2-, and R 1 and R 2 It is Me, and X is -OEt, as shown below: (i.e., 3-ethoxy-2,2-dimethyl-propyl-tris-(dimethylamino)tin).

[0085] In one implementation, in formula (I), M is Sn, R is -CH2C(Me2)CH2-, and R 1 It is Me and R 2 It is Et, and X is -OMe, as shown below: (i.e., 3-methoxy-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin).

[0086] In one implementation, in formula (I), M is Sn, R is -CH2C(Me2)CH2-, and R 1 It is Me and R 2 It is Et, and X is -OEt, as shown below: (i.e., 3-ethoxy-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin).

[0087] In one implementation, in formula (I), M is Sn, R is -CH2C(Me2)CH2-, and R 1 and R 2 It is Et, and X is -OMe, as shown below: (i.e., 3-methoxy-2,2-dimethyl-propyl-tris-(diethylamino)tin).

[0088] In one implementation, in formula (I), M is Sn, R is -CH2C(Me2)CH2-, and R 1 It is Me and R 2 It is iPr, and X is -OMe, as shown below: (i.e., 3-ethoxy-2,2-dimethyl-propyl-tris-(methylisopropylamino)tin).

[0089] In one implementation, in formula (I), M is Sn, R is -CH2CH2C(Me)2-, R 1 and R 2 It is Me, and X is -OMe, as shown below: (i.e., 3-methoxy-1,1-dimethyl-propyl-tris-(dimethylamino)tin).

[0090] In one implementation, in formula (I), M is Sn, R is -CH2CH2C(Me)2-, R 1 and R 2 It is Me, and X is -OEt, as shown below: (i.e., 3-ethoxy-1,1-dimethyl-propyl-tris-(dimethylamino)tin).

[0091] In one implementation, in formula (I), M is Sn, R is -CH2CH2C(Me)2-, R 1 It is Me and R 2 It is Et, and X is -OMe, as shown below: (Right now ， 3-Methoxy-1,1-dimethyl-propyl-tris-(ethylmethylamino)tin).

[0092] In one implementation, in formula (I), M is Sn, R is -CH2CH2C(Me)2-, R 1 It is Me and R 2 It is Et, and X is -OEt, as shown below: (Right now ， 3-Ethoxy-1,1-dimethyl-propyl-tris-(ethylmethylamino)tin).

[0093] Compositions of organotin compounds In one embodiment, the disclosed and claimed subject matter relates to compositions comprising (a) one or more compounds of formula (I) as described above and (b) one or more solvents, substantially consisting of or composed of the same.

[0094] In one embodiment, one or more compounds of formula (I) in the composition include 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(dimethylamino)tin, 3-(N,N-diethylamino)-2,2-dimethyl-propyl-tris-(dimethylamino)tin, 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin, 3-(N,N-diethylamino)-2,2-dimethyl-propyl-tris-(diethylamino)tin, 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(methyl-isopropylamino)tin, 3-(N,N-dimethylamino)-1,1-dimethyl-propyl-tris-(dimethylamino)tin, 3-methoxy-2,2-dimethyl-propyl-tris-(dimethylamino)tin, One or more of 3-ethoxy-2,2-dimethyl-propyl-tris-(dimethylamino)tin, 3-methoxy-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin, 3-ethoxy-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin, 3-methoxy-2,2-dimethyl-propyl-tris-(diethylamino)tin, 3-ethoxy-2,2-dimethyl-propyl-tris-(methylisopropylamino)tin, 3-methoxy-1,1-dimethyl-propyl-tris-(dimethylamino)tin, 3-ethoxy-1,1-dimethyl-propyl-tris-(dimethylamino)tin, 3-methoxy-1,1-dimethyl-propyl-tris-(ethylmethylamino)tin and 3-ethoxy-1,1-dimethyl-propyl-tris-(ethylmethylamino)tin, substantially composed of or composed of the same.

[0095] In one embodiment, one or more compounds of formula (I) of the composition comprise 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(dimethylamino)tin, substantially constitute therewith, or consist of therewith.

[0096] In one embodiment, one or more compounds of formula (I) of the composition comprise 3-(N,N-diethylamino)-2,2-dimethyl-propyl-tris-(dimethylamino)tin, substantially constitute therewith, or consist of therewith.

[0097] In one embodiment, one or more compounds of formula (I) of the composition comprise 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin, substantially constitute therewith, or consist of therewith.

[0098] In one embodiment, one or more compounds of formula (I) of the composition comprise 3-(N,N-diethylamino)-2,2-dimethyl-propyl-tris-(diethylamino)tin, substantially constitute therewith, or consist of therewith.

[0099] In one embodiment, one or more compounds of formula (I) of the composition comprise 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(methyl-isopropylamino)tin, substantially composed of, or composed of.

[0100] In one embodiment, one or more compounds of formula (I) of the composition comprise 3-(N,N-dimethylamino)-1,1-dimethyl-propyl-tris-(dimethylamino)tin, substantially constitute therewith, or consist of therewith.

[0101] In one embodiment, one or more compounds of formula (I) of the composition comprise, substantially comprise, or comprise of 3-methoxy-2,2-dimethyl-propyl-tris-(dimethylamino)tin.

[0102] In one embodiment, one or more compounds of formula (I) of the composition comprise, substantially comprise, or comprise of 3-ethoxy-2,2-dimethyl-propyl-tris-(dimethylamino)tin.

[0103] In one embodiment, one or more compounds of formula (I) of the composition comprise, substantially comprise, or comprise of 3-methoxy-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin.

[0104] In one embodiment, one or more compounds of formula (I) of the composition comprise, substantially comprise, or comprise of 3-ethoxy-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin.

[0105] In one embodiment, one or more compounds of formula (I) of the composition comprise, substantially comprise, or comprise of 3-methoxy-2,2-dimethyl-propyl-tris-(diethylamino)tin.

[0106] In one embodiment, one or more compounds of formula (I) of the composition comprise, substantially comprise, or comprise of 3-ethoxy-2,2-dimethyl-propyl-tris-(methylisopropylamino)tin.

[0107] In one embodiment, one or more compounds of formula (I) of the composition comprise, substantially comprise, or comprise of 3-methoxy-1,1-dimethyl-propyl-tris-(dimethylamino)tin.

[0108] In one embodiment, one or more compounds of formula (I) of the composition comprise, substantially comprise, or comprise of 3-ethoxy-1,1-dimethyl-propyl-tris-(dimethylamino)tin.

[0109] In one embodiment, one or more compounds of formula (I) of the composition comprise, substantially comprise, or comprise of 3-methoxy-1,1-dimethyl-propyl-tris-(ethylmethylamino)tin.

[0110] In one embodiment, one or more compounds of formula (I) of the composition comprise, substantially comprise, or comprise of 3-ethoxy-1,1-dimethyl-propyl-tris-(ethylmethylamino)tin.

[0111] The compositions of the disclosed and claimed subject matter also comprise (b) one or more solvents. Suitable solvents include hydrocarbon solvents, which are particularly desirable because they can be dried to sub-ppm water content. Exemplary hydrocarbon solvents that can be used in the compositions include, but are not limited to: toluene, mesitylene, cumene (isopropylbenzene), p-cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, decahydronaphthalene (naphthalene), and combinations thereof. In some embodiments, the hydrocarbon solvent is a high-boiling solvent or has a boiling point of 100°C or higher.

[0112] Deposition methods In another embodiment, the tin compounds and / or compositions described above are used in a method for depositing tin-containing films.

[0113] In one embodiment, the method for depositing organotin oxide or tin oxide films of the disclosed and claimed subject matter comprises the following steps, substantially consists of the following steps, or consists of the following steps: a. Providing one or more substrates in a reactor, wherein the reactor is heated to a temperature of about 25 °C to about 600 °C and optionally maintained at a pressure of about 100 Torr or less; b. Introduce into the reactor a vapor comprising one or more compounds of formula (I) or a combination thereof, substantially composed of such compounds or composed of such compounds, which forms a metal-containing (i.e., tin- or germanium-containing) layer on the substrate surface. c. Purge the reactor with inert gas; d. Introducing one or more oxygen sources to convert the tin-containing layer into an organotin oxide or tin oxide layer; and e. Purge the reactor with inert gas.

[0114] In one embodiment, for a thermal ALD or ALD-like process for depositing organotin oxides, the oxygen source can be one or more of water vapor, hydrogen peroxide, organic peroxides, and mixtures thereof. In another embodiment, for forming tin oxide materials, the oxygen source can be one or more of water plasma, ozone, oxygen, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxide plasma, carbon dioxide plasma, and mixtures thereof. In a specific embodiment, the oxygen source includes, is substantially composed of, or is composed of water vapor.

[0115] In a preferred embodiment of the above method, one or more oxygen sources in step (d) comprise water vapor, are substantially composed of, or are composed of water vapor, and the method further comprises an additional step of introducing carboxylic acid vapor and purging the vapor, which is substantially composed of, or is composed of, it. In particular, the method for depositing organotin oxide films of the disclosed and claimed subject matter comprises the following steps, which are substantially composed of, or are composed of, the following steps: a. Providing one or more substrates in a reactor, wherein the reactor is heated to a temperature of about 25 °C to about 600 °C and optionally maintained at a pressure of about 100 Torr or less; b. Introduce into the reactor a vapor comprising one or more compounds of formula (I) or a combination thereof, substantially composed of such compounds or composed of such compounds, which forms a metal-containing (i.e., tin- or germanium-containing) layer on the substrate surface. c. Purge any unreacted precursors from the reactor using an inert gas; d. Introduce one or more oxygen sources, including water vapor, substantially composed of or composed of water vapor, to convert the tin-containing layer into an organotin oxide or tin oxide layer; e. Purge the reactor with inert gas; f. Introduce one or more formulas R 3 The carboxylic acid vapor 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, C3 to C6 ynyl and C4 to C6 alkyl groups. 10 Aryl groups, to react with organotin oxide layers; and g. Purge the reactor with inert gas.

[0116] Step (b) Delivery of organotin and / or organogermanium precursors As described above, step (b) of the disclosed and claimed method includes introducing a vapor comprising one or more compounds of formula (I) or a composition thereof, substantially of such compounds, or of such compounds into a reactor, which forms a metal-containing (i.e., tin-containing or germanium-containing) layer on a substrate surface.

[0117] In one embodiment, the vapor comprises, is substantially composed of, or is composed of an organotin compound of formula (I). In one embodiment, the vapor comprises, is substantially composed of, or is composed of an organogermanium compound of formula (I).

[0118] In one embodiment, the precursor vapor pulse time is from about 0.1 seconds to about 3 seconds. In another embodiment, the precursor vapor pulse time is from about 0.3 seconds to about 3 seconds. In another embodiment, the precursor vapor pulse time is about 0.1 seconds. In another embodiment, the precursor vapor pulse time is about 0.25 seconds. In another embodiment, the precursor vapor pulse time is about 0.5 seconds. In yet another embodiment, the precursor vapor pulse time is about 1 second. In another embodiment, the precursor vapor pulse time is about 1.5 seconds. In another embodiment, the precursor vapor pulse time is about 2 seconds. In yet another embodiment, the precursor vapor pulse time exceeds 2 seconds depending on the volume / design of the reaction chamber.

[0119] In one embodiment, the precursor vapor is separated from other precursor materials before and / or during its introduction into the reactor. This process avoids premature reaction between the metallic precursor and any other materials.

[0120] In another embodiment, the precursor vapor may optionally be exposed to the substrate along with other reactants (e.g., other precursors or reagents). This process allows film growth to be performed under self-limiting control of the surface reaction, the pulse length of each precursor or reagent, and the deposition temperature. However, it should be noted that film growth ceases once the surface of the substrate is saturated with organotin precursor vapor.

[0121] In another embodiment, a stream of argon and / or other gases is used as a carrier gas to help deliver organotin precursor vapor into the reactor during precursor pulses.

[0122] Step (d) Oxygen source As described above, step (d) of the disclosed and claimed method includes introducing one or more oxygen sources to convert the metal-containing layer into an organometallic oxide or metal oxide layer. In one embodiment, the metal-containing layer comprises tin, is substantially composed of tin, or is composed of tin. In one embodiment, the metal-containing layer comprises germanium, is substantially composed of germanium, or is composed of germanium.

[0123] In one embodiment, one or more oxygen sources include oxygen (O2), ozone (O3), nitric oxide (NO), water vapor (H2O), hydrogen peroxide (H2O2), and oxygen plasma (O2O2). ), N x O y(where x = 1 or 2, and y = 1, 2, 3, or 4) and one or more combinations thereof. In one aspect of this embodiment, one or more oxygen sources include oxygen. In one aspect of this embodiment, one or more oxygen sources include ozone. In one aspect of this embodiment, one or more oxygen sources include nitric oxide. In one aspect of this embodiment, one or more oxygen sources include water vapor. In one aspect of this embodiment, one or more oxygen sources include hydrogen peroxide. In one aspect of this embodiment, one or more oxygen sources include oxygen and ozone. In one aspect of this embodiment, one or more oxygen sources include oxygen plasma. In one aspect of this embodiment, one or more oxygen sources include N... x O y Where x = 1 or 2, and y = 1, 2, 3, or 4. In one embodiment, one or more oxidants are vapors.

[0124] As described above, in a preferred embodiment, for example, one or more oxygen sources comprise, are substantially composed of, or are composed of water vapor. In one aspect of this embodiment, one or more oxygen sources comprise water vapor. In one aspect of this embodiment, one or more oxygen sources are substantially composed of water vapor. In one aspect of this embodiment, one or more oxygen sources are composed of water vapor.

[0125] In one embodiment, the pulse duration of one or more oxygen sources varies from about 0.5 seconds to about 5 seconds. In one embodiment, for example, the pulse duration of one or more oxygen sources is about 2.5 seconds. In another embodiment, for example, the pulse duration of one or more oxygen sources is about 5 seconds. However, in another embodiment, depending on the volume / design of the reaction chamber, the pulse duration of one or more oxygen sources is longer than 5 seconds.

[0126] Step (f) contains carboxylic acid vapor As described above, a preferred embodiment of the disclosed and claimed method includes step (f): introducing one or more methods having formula R 3 The carboxylic acid vapor 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, C3 to C6 ynyl and C4 to C6 alkyl groups. 10 Aryl groups react with organotin oxide layers.

[0127] In another embodiment, the carboxylic acid includes one or more of the following: formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, 2-methylbutyric acid, 3-methylbutyric 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, 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 propionic acid. In one aspect of this embodiment, the carboxylic acid includes butyric 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 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 cyclobutanecarboxylic acid. In one aspect of this embodiment, the carboxylic acid includes cyclopentanecarboxylic acid. In one aspect of this embodiment, the carboxylic acid includes cyclohexanecarboxylic acid. In one aspect of this embodiment, the carboxylic acid includes 4,4-difluorocyclohexanecarboxylic acid. In one aspect of this embodiment, the carboxylic acid includes tetrahydro-3-furancarboxylic acid.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] Steps (c), (e), and (g) purging As described above, steps (c), (e), and (g) of the disclosed and claimed method include purging the reaction vessel with an inert gas. The inert gas purging removes unadsorbed excess material and byproducts from the process reactor. In one embodiment, the purging gas comprises argon. In another embodiment, the purging gas comprises nitrogen.

[0132] In one embodiment, for example, the purging time varies from about 1 second to about 90 seconds. In another embodiment, for example, the purging time varies from about 15 seconds to about 90 seconds. In another embodiment, for example, the purging time varies from about 15 seconds to 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.

[0133] In one embodiment, the purge gas comprises argon. In another embodiment, the purge gas comprises nitrogen.

[0134] Operating conditions As described above, the disclosed and claimed tin-containing film deposition method can be carried out effectively under very favorable ALD or ALD-like conditions.

[0135] In one embodiment, a substrate (e.g., alumina (Al₂O₃), titanium nitride (TiN), silicon oxide (SiO₂), zirconium oxide (ZrO₂), amorphous carbon, or a silicon-containing underlayer) is heated on a heater stage in a reaction 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 600°C. In a further aspect of this embodiment, the substrate temperature is from about 25°C to about 500°C. In a further aspect of this embodiment, the substrate temperature is from about 25°C to about 400°C. A preferred substrate temperature for processes using only water is from 25°C to about 200°C.

[0136] 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.

[0137] Loops and Step Sequence In the embodiments described above and in other embodiments described herein, the steps described (e.g., (a) to (e)) define a cycle of the method. It should be understood that the cycle may be repeated until the desired film thickness is obtained.

[0138] 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, aqueous vapors, and carboxylic acid vapors) and / or their subsequent purging can be performed by varying the duration of their supply to alter the membrane composition.

[0139] membrane The disclosed and claimed subjects also include membranes prepared by the methods described herein. In one embodiment, the membrane comprises tin, is substantially composed of tin, or is composed of tin. In one embodiment, the membrane comprises germanium, is substantially composed of germanium, or is composed of germanium.

[0140] In one embodiment, the membrane formed by the method described herein has grooves, vias, or other morphological features with an aspect ratio of about 1 to about 60. In a further aspect of this embodiment, the aspect ratio is about 1 to about 50. In a further aspect of this embodiment, the aspect ratio is about 1 to about 40. In a further aspect of this embodiment, the aspect ratio is about 1 to about 30. In a further aspect of this embodiment, the aspect ratio is about 1 to about 20. In a further aspect of this embodiment, the aspect ratio is about 1 to about 10. In a further aspect of this embodiment, the aspect ratio is greater than about 1. In a further aspect of this embodiment, the aspect ratio is greater than about 2. In a further aspect of this embodiment, the aspect ratio is greater than about 5. In a further aspect of this embodiment, the aspect ratio is greater than about 10. In a further aspect of this embodiment, the aspect ratio is greater than about 15. In a further aspect of this embodiment, the aspect ratio is greater than about 20. In a further aspect of this embodiment, the aspect ratio is greater than about 30. In a further aspect of this embodiment, the aspect ratio is greater than about 40. In a further aspect of this implementation scheme, the aspect ratio is greater than approximately 50.

[0141] The steps of the described and claimed methods can be repeated to provide the desired membrane thickness. The membrane thickness can range from about 10 Å to about 5000 Å, or about 10 Å to about 1000 Å, or about 10 Å to about 500 Å, or about 10 Å to about 300 Å, or about 10 Å to about 200 Å, or about 50 Å to about 1000 Å, or about 50 Å to about 500 Å, or about 50 Å to about 300 Å, or about 50 Å to about 200 Å. In one embodiment, the membrane formed by the method described herein has a thickness of about 10 Å to about 5000 Å. In another aspect of this embodiment, the membrane formed by the method described herein has a thickness of about 10 Å to 1000 Å. In another aspect of this embodiment, the membrane formed by the method described herein has a thickness of about 10 Å to 500 Å. In another aspect of this embodiment, the thickness of the membrane formed by the method described herein is about 10 Å to 300 Å. In another aspect of this embodiment, the thickness of the membrane formed by the method described herein is about 10 Å to 200 Å. In another aspect of this embodiment, the thickness of the membrane formed by the method described herein is about 50 Å to 1000 Å. In another aspect of this embodiment, the thickness of the membrane formed by the method described herein is about 50 Å to 500 Å. In another aspect of this embodiment, the thickness of the membrane formed by the method described herein is about 50 Å to 300 Å. In yet another aspect of this embodiment, the thickness of the membrane formed by the method described herein is about 50 Å to 200 Å.

[0142] In some embodiments, a supercycle ALD or ALD-like process can be performed, a supercycle comprising the following steps: steps (b) to (e) can be repeated to provide a desired film 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 (f) to (g) to modify the resulting film. The supercycle can be repeated to provide the desired film thickness. It is believed that the reaction between the carboxylic acid and the film obtained in steps (b) to (e) can improve / stabilize the film, thereby allowing the film to have greater resistance to environmental changes (such as moisture or carbon dioxide) during semiconductor manufacturing. Furthermore, in some embodiments, steps (f) to (g) are performed prior to steps (d) to (e) to provide the desired film thickness.

[0143] 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.

[0144] 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 examples 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, covers modifications and variations of the disclosed subject matter that fall within the scope of any claims and their equivalents.

[0145] Working Example 1: Synthesis of (DMDMP)Sn(NMe)3 (DMDMP = 3-(N,N-dimethylamino)-2,2-dimethylpropyl)(3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(dimethylamino)tin), wherein the β-carbon is a quaternary carbon. All reactions were carried out under strict conditions of moisture and oxygen exclusion using a standard inert atmosphere and the Schlenk technique. Solvents such as tetrahydrofuran (THF), 1,4-dioxane, and n-pentane were dried by standard methods before use. Commercially available Sn(NMe2)4 (Strem) was used without further purification. 3-(N,N-dimethylamino)-2,2-dimethylpropylmagnesium chloride (1) was synthesized using 3-(N,N-dimethylamino)-2,2-dimethylpropyl chloride and magnesium powder according to the general synthetic procedure for Grignard reagents. iPrSn(NMe2)3 was synthesized using iPrSnCl3 and LiNMe2.

[0146] Synthetic 1A: A solution of compound 1 in THF (c = 0.731 m / L, 10 mL) was dissolved in anhydrous dioxane (10 mL), and the mixture was stirred for 20 minutes to form dialkylmagnesium substance 2. A white solid precipitated during stirring. The suspension was filtered, and the solution of dialkylmagnesium substance 2 was used without further characterization.

[0147] Synthesis 1B: Compound 2 (c = 0.366 m / L; dissolved in 20 mL of 1,4-dioxane / THF) was slowly added at -78 °C to a solution of Sn(NMe2)4 (2.16 g, 7.32 mmol) in 20 mL of THF. The reaction mixture was heated to room temperature overnight. All volatiles were removed under vacuum, and the residue was extracted with n-pentane (3 x 5 mL). The n-pentane was removed under vacuum, and the residue was extracted by distillation (70 °C, 2.8 x 10⁻⁶ mL). -2 Purified at mbar. The resulting product ((DMDMP)Sn(NMe2)3; compound "3") was a colorless liquid. Yield: 1.9 g (71%).

[0148] Using compound 2 as the starting material in 1,4-dioxane, the ratio of monoalkyl compound 3 to dialkyl compound 4 was 95:5. Simple distillation was sufficient to separate the two products to yield compound 3 with a purity >99%. See also Figure 1-3 .

[0149] analyze Figure 1 : 1 H NMR (500 MHz, C6D6): δ 2.85 (t, 3 J SnH = 20.6 Hz, Sn-N(C H 3)2, 18H),2.19 (s, N(C H 3)2, 6H), 1.97 (s, C H 2-N(CH3)2, 2H), 1.32 (t, 2 J SnH = 35.6 Hz, Sn-C H 2, 2H), 0.99 (s, C H 3, 6H) ppm. Figure 2 :3 13 C NMR (125.8 MHz, C6D6): δ 72.9 (t, 1 J SnC = 30.8 Hz, Sn- C H2), 49.0 (N( C H3)2), 43.1 (t, 2 J SnC = 4.2 Hz, Sn-N( C H3)2), 35.7(t, 2 J SnC = 10.8 Hz, C quat. ), 29.4 (t, 3 J SnC = 22.4 Hz, C( C H3)2), 27.5 (N C H2) ppm. Figure 3 :3 119 Sn NMR (186.6 MHz, C6D6): δ - 40.4 (s) ppm. Figure 1-3The NMR spectrum of compound 3 with a purity >99% is shown.

[0150] This purity level is based on the integral of the Sn NMR signal of the compound prepared via the above synthetic route. Conversely, the same compound prepared via other conventional routes exhibits a much higher tendency for over-alkylation. In the conventional / alternative synthesis, compound 3 is prepared directly from compound 1: The conventional synthesis of compound 3 using compound 1 in THF results in the formation of monoalkyl compound 3 and dialkyl compound 4 in a 90:10 ratio, which makes product purification more difficult. Two distillations are required to separate the two compounds. Figure 4 and Figure 5 As shown, when compounds 3 and 4 are prepared and separated via the conventional route, there are significantly more impurities (based on peak integrals).

[0151] Figure 6 Thermogravimetric analysis (TGA) of compound 3 prepared by the disclosed and claimed methods is shown. Figure 6 In the study, it was demonstrated that compound 3 has a volatility of >99%, which further confirms that 3 is suitable for vapor deposition of organotin oxide films.

[0152] Figure 7 Differential scanning calorimetry (DSC) of compound 3 is shown; the experiment was conducted in a gold-plated crucible. The DSC shows an onset temperature of 196.6 °C, which can be considered the decomposition temperature.

[0153] Figure 8 Compound 3 recorded at room temperature is shown. 119 Sn NMR spectrum. Based on... 119 The integrated values ​​obtained from the Sn NMR spectrum showed no change after 10 days. This comparison of fresh samples (>99% NMR) with samples exposed to laboratory light for 10 days (>99% NMR) and 24 days (99% NMR) indicates a slow decomposition process under light exposure. After 24 days of light exposure, compound 3 showed new decomposition products at -49 ppm (1% NMR). In contrast, iPrSn(NMe2)3 showed 45% decomposition after 24 days under the same light exposure conditions. Figure 9 This data indicates that the compound exhibits significantly higher light stability compared to commonly used and known monoalkyltin compounds, such as iPrSn(NMe2)3 disclosed in U.S. Patent No. 11,500,284 and the prior art cited therein.

[0154] Working Example 2: Synthesis of (MODMP)Sn(NMe)3 (MODMP = 3-methoxy-1,1-dimethylpropyl)(3-methoxy-1,1-dimethylpropyl-tris-(dimethylamino)tin), wherein the α-carbon is a quaternary carbon. All reactions were carried out under a standard inert atmosphere and with strict exclusion of moisture and oxygen using the Schlenk technique. Solvents such as tetrahydrofuran (THF) and n-pentane were dried by standard methods before use. Commercially available Sn(NMe2)4(Strem) was used without further purification. 3-Methoxy-1,1-dimethyl-propyl chloride (5) was synthesized in two steps according to a literature procedure. See [link to relevant documentation]. Chem. Eur. J. ,8, 3773 (2002); J. Am. Soc. , 123, 10127(2001).

[0155] Synthesize 2A: 3-Methoxy-1,1-dimethylpropylmagnesium chloride (6) was synthesized using 3-methoxy-1,1-dimethyl-propyl chloride (5) and magnesium shavings according to the general synthetic procedure for Grignard reagents.

[0156] Synthesize 2B: Compound 6 (c = 0.207 m / L; dissolved in 21.3 mL THF) was slowly added at -78 °C to a solution of Sn(NMe2)4 (1.30 g, 4.41 mmol) in THF (5 mL). The reaction mixture was heated to room temperature overnight. All volatiles were removed under vacuum, and the residue was extracted with n-pentane (2 x 20 mL). The n-pentane was removed under vacuum, and the residual liquid was purified by distillation (40 °C, 1.4 x 10 mL). -2 The product ((MODMP)Sn(NMe2)3; compound "7") was obtained as a colorless waxy solid. Yield: 1.4 g (88%).

[0157] analyze Figure 10 :7 1 H NMR (500 MHz, C6D6): δ 3.17 (t, 3 J HH = 6.1 Hz, C H 2-OCH3, 2H), 3.06 (s, OC) H 3, 3H), 2.91 (t, 3 J SnH= 19.8 Hz, Sn-(N(CH3)2)3, 18H ), 1.64 (t, 3 J HH =6.1 Hz, C H 2-CH2-OCH3, 2H), 1.26 (t, 3 J SnH = 47.6 Hz, Sn-CC H 3, 6H) ppm. Figure 11 :7 119 Sn NMR (186.6 MHz, C6D6): δ - 109 (s) ppm. Figure 10-11 The NMR spectrum of compound 7 with 97% purity is shown. 1 H and 119 The small impurity peaks in the Sn NMR spectrum can be attributed to dialkylated substances.

[0158] Figure 6 The TGA of compound 7 prepared by the disclosed and claimed methods is shown. Figure 6 In the study, it was demonstrated that compound 7 has a volatility of >99%, and it was further confirmed that 7 is suitable for vapor deposition of organotin oxide films.

[0159] Figure 12 The DSC of compound 7 is shown; the experiment was conducted in a gold-plated crucible. The DSC shows an onset temperature of 188 °C, which can be considered the decomposition temperature.

[0160] Working Example 3: Deposition of Tin-Containing Film Compound 3-(DMDMP)Sn(NMe)3 Conditions: Deposition temperatures were 90 °C and 110 °C, respectively; reactor pressure was approximately 2 Torr; (DMDMP)Sn(NMe)3 (5 s) was used as the organotin precursor with a pulse time range of 0.1 to 5 s, and water was used as the oxygen source with a pulse time of 0.1 s.

[0161] like Figure 13 and Figure 14 As shown, linear growth behavior was observed using the ALD-sample process, demonstrating that (DMDMP)Sn(NMe)3 can be used for vapor deposition of tin-containing films.

[0162] Although the invention has been described and illustrated with a degree of specificity, 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 compound of formula (I): (XR)M(NR) 1 R 2 )3, of which (i) M = Sn or Ge; (ii) R is a branch C5 to C 10 An alkylene linking group, wherein (i) three to eight main chain carbon moieties link M and X, and (ii) at least one of the first three main chain carbon moieties linking M and X is a hydrogen-free quaternary carbon moieties; (iii) R 1 and R 2 Each is independently selected from straight-chain C1 to C6 alkyl, branched C4 to C6 alkyl, or cyclic C3 to C6 alkyl; and (iv) X is selected as -OR 3 or -NR 4 R 5 One of them, of which R 3 R 4 and R 5 Each is independently selected from straight-chain C1 to C6 alkyl, branched C4 to C6 alkyl, or cyclic C3 to C6 alkyl.

2. The compound of claim 1, wherein M = Sn.

3. The compound of claim 1, wherein M = Ge.

4. The compound of claim 1, wherein R is a branched C5 alkylene group.

5. The compound of claim 1, wherein R is a branched C6 alkylene group.

6. The compound of claim 1, wherein R is a branched C7 alkylene group.

7. The compound of claim 1, wherein R is a branched C8 alkylene group.

8. The compound of claim 1, wherein R is a branched C9 alkylene group.

9. The compound of claim 1, wherein R is a branched C. 10 Alkylene.

10. The compound of claim 1, wherein R comprises the C5 to C6 groups. 10 The alkylene linking group consists of three main chain carbon moieties that connect M and X.

11. The compound of claim 1, wherein the C5 to C6 groups of R are... 10 The alkylene linking group consists of four main chain carbon moieties that connect M and X.

12. The compound of claim 1, wherein R comprises the C5 to C6 groups. 10 The alkylene linking group consists of five main chain carbon moieties that link M and X.

13. The compound of claim 1, wherein the C5 to C6 groups of R are... 10 The alkylene linking group consists of six main chain carbon moieties that link M and X.

14. The compound of claim 1, wherein R comprises the C5 to C6 groups. 10 The alkylene linking group consists of seven main chain carbon moieties that link M and X.

15. The compound of claim 1, wherein the C5 to C6 groups of R are... 10 The alkylene linking group consists of eight main chain carbon moieties that link M and X.

16. The compound of claim 1, wherein the α-carbon moiety of R is a hydrogen-free quaternary carbon moiety.

17. The compound of claim 1, wherein the β-carbon moiety of R is a hydrogen-free quaternary carbon moiety.

18. The compound of claim 1, wherein the γ-carbon moiety of R is a hydrogen-free quaternary carbon moiety.

19. The compound of claim 1, wherein two or more of the α-carbon moiety, β-carbon moiety, and γ-carbon moiety of R are hydrogen-free quaternary carbon moieties.

20. The compound of claim 1, having the formula (NR) 1 R 2 )3M-C(Me2)CH2CH2-X.

21. The compound of claim 1, having the formula (NR) 1 R 2 )3M-CH2C(Me2)CH2-X).

22. The compound of claim 1, having the formula (NR) 1 R 2 )3M-CH2CH2C(Me2)-X).

23. The compound of claim 1, wherein R 1 and R 2 One or both of them are straight-chain C1 to C6 alkyl groups.

24. The compound of claim 1, wherein R 1 and R 2 One or both of them are straight-chain C1 alkyl groups.

25. The compound of claim 1, wherein R 1 and R 2 One or both of them are straight-chain C2 alkyl groups.

26. The compound of claim 1, wherein R 1 and R 2 One or both of them are straight-chain C3 alkyl groups.

27. The compound of claim 1, wherein R 1 and R 2 One or both of them are straight-chain C4 alkyl groups.

28. The compound of claim 1, wherein R 1 and R 2 One or both of them are straight-chain C5 alkyl groups.

29. The compound of claim 1, wherein R 1 and R 2 One or both of them are straight-chain C6 alkyl groups.

30. The compound of claim 1, wherein R 1 and R 2 One or two of them are branched C4 to C6 alkyl groups.

31. The compound of claim 1, wherein R 1 and R 2 One or both of them are branched C4 alkyl groups.

32. The compound of claim 1, wherein R 1 and R 2 One or both of them are branched C5 alkyl groups.

33. The compound of claim 1, wherein R 1 and R 2 One or both of them are branched C6 alkyl groups.

34. The compound of claim 1, wherein R 1 and R 2 One or both of them are cyclic C3 to C6 alkyl groups.

35. The compound of claim 1, wherein R 1 and R 2 One or both of them are cyclic C3 alkyl groups.

36. The compound of claim 1, wherein R 1 and R 2 One or both of them are cyclic C4 alkyl groups.

37. The compound of claim 1, wherein R 1 and R 2 One or both of them are cyclic C5 alkyl groups.

38. The compound of claim 1, wherein R 1 and R 2 One or both of them are cyclic C6 alkyl groups.

39. The compound of claim 1, wherein X is -OR 3 Group.

40. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a straight-chain C1 to C6 alkyl group.

41. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a straight-chain C1 alkyl group.

42. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a straight-chain C2 alkyl group.

43. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a straight-chain C3 alkyl group.

44. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a straight-chain C4 alkyl group.

45. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a straight-chain C5 alkyl group.

46. ​​The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a straight-chain C6 alkyl group.

47. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a branched C4 to C6 alkyl group.

48. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a branched C4 alkyl group.

49. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a branched C5 alkyl group.

50. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a branched C6 alkyl group.

51. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a cyclic C3 to C6 alkyl group.

52. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a cyclic C3 alkyl group.

53. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a cyclic C4 alkyl group.

54. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a cyclic C5 alkyl group.

55. The compound of claim 1, wherein X is -OR 3 Group, and R 3 It is a cyclic C6 alkyl group.

56. The compound of claim 1, wherein X is -NR 4 R 5 Group.

57. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or both of them are straight-chain C1 to C6 alkyl groups.

58. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or both of them are straight-chain C1 alkyl groups.

59. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or both of them are straight-chain C2 alkyl groups.

60. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or both of them are straight-chain C3 alkyl groups.

61. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or both of them are straight-chain C4 alkyl groups.

62. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or both of them are straight-chain C5 alkyl groups.

63. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or both of them are straight-chain C6 alkyl groups.

64. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or two of them are branched C4 to C6 alkyl groups.

65. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or two of them are branched C4 alkyl groups.

66. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or both of them are branched C5 alkyl groups.

67. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or two of them are branched C6 alkyl groups.

68. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or two of them are cyclic C3 to C6 alkyl groups.

69. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or two of them are cyclic C3 alkyl groups.

70. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or both of them are cyclic C4 alkyl groups.

71. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or both of them are cyclic C5 alkyl groups.

72. The compound of claim 1, wherein X is -NR 4 R 5 Group, and R 4 and R 5 One or both of them are cyclic C6 alkyl groups.

73. The compound of claim 1, wherein the compound of formula (I) comprises (NMe2CH2CMe2CH2)Sn(NMe2)3, is substantially composed of, or is composed of.

74. The compound of claim 1, wherein the compound of formula (I) comprises (OMeCH2CMe2CH2)Sn(NMe2)3, is substantially composed of, or is composed of.

75. The compound of claim 1, wherein the compound of formula (I) comprises (OMeCH2CH2CMe2)Sn(NMe2)3, is substantially composed of, or is composed of.

76. The compound of claim 1, wherein the compound of formula (I) comprises (NMe2CH2CH2CMe2)Sn(NMe2)3, is substantially composed of, or is composed of.

77. The compound of claim 1, wherein the compound of formula (I) comprises one or more of the following, is substantially composed of one or more of the following, or is composed of one or more of the following: 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(dimethylamino)tin, 3-(N,N-diethylamino)-2,2-dimethyl-propyl-tris-(dimethylamino)tin, 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin, 3-(N,N-diethylamino)-2,2-dimethyl-propyl-tris-(diethylamino)tin, 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(methylisopropylamino)tin, 3-(N,N-dimethylamino)-1,1-dimethyl-propyl-tris-(dimethylamino)tin, 3-methoxy-2,2-dimethyl-propyl-tris-(dimethylamino)tin, 3-ethoxy -2,2-dimethyl-propyl-tris-(dimethylamino)tin, 3-methoxy-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin, 3-ethoxy-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin, 3-methoxy-2,2-dimethyl-propyl-tris-(diethylamino)tin, 3-ethoxy-2,2-dimethyl-propyl-tris-(methylisopropylamino)tin, 3-methoxy-1,1-dimethyl-propyl-tris-(dimethylamino)tin, 3-ethoxy-1,1-dimethyl-propyl-tris-(dimethylamino)tin, 3-methoxy-1,1-dimethyl-propyl-tris-(ethylmethylamino)tin and 3-ethoxy-1,1-dimethyl-propyl-tris-(ethylmethylamino)tin.

78. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(dimethylamino)tin.

79. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-(N,N-diethylamino)-2,2-dimethyl-propyl-tris-(dimethylamino)tin.

80. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin.

81. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-(N,N-diethylamino)-2,2-dimethyl-propyl-tris-(diethylamino)tin.

82. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-(methylisopropylamino)tin.

83. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-(N,N-dimethylamino)-1,1-dimethyl-propyl-tris-(dimethylamino)tin.

84. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-methoxy-2,2-dimethyl-propyl-tris-(dimethylamino)tin.

85. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-ethoxy-2,2-dimethyl-propyl-tris-(dimethylamino)tin.

86. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-methoxy-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin.

87. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-ethoxy-2,2-dimethyl-propyl-tris-(ethylmethylamino)tin.

88. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-methoxy-2,2-dimethyl-propyl-tris-(diethylamino)tin.

89. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-ethoxy-2,2-dimethyl-propyl-tris-(methylisopropylamino)tin.

90. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-methoxy-1,1-dimethyl-propyl-tris-(dimethylamino)tin.

91. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-ethoxy-1,1-dimethyl-propyl-tris-(dimethylamino)tin.

92. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-methoxy-1,1-dimethyl-propyl-tris-(ethylmethylamino)tin.

93. The compound of claim 1, wherein the compound of formula (I) comprises, is substantially composed of, or is composed of 3-ethoxy-1,1-dimethyl-propyl-tris-(ethylmethylamino)tin.

94. The compound of claim 1, wherein the compound of formula (I) comprises one or more of the following, is substantially composed of one or more of the following, or is composed of one or more of the following: 。 95. A composition comprising (i) one or more compounds as claimed in any one of claims 1 to 95, and (ii) one or more solvents.

96. A composition comprising (i) one or more compounds as claimed in any one of claims 1 to 95, and (ii) one or more solvents selected from toluene, mesitylene, cumene (isopropylbenzene), p-cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, decahydronaphthalene (naphthalene), and combinations thereof.

97. A method for depositing an organotin oxide or tin oxide film, comprising the following steps: a. Placing one or more substrates in a reactor, wherein the reactor is heated to a temperature of about 25°C to about 600°C and optionally maintained at a pressure of about 100 Torr or less; b. Introducing vapors comprising one or more compounds or compositions as described in any one of claims 1 to 96 into the reactor; c. Purge the reactor with inert gas; d. Introducing one or more oxygen sources to convert the metal-containing layer into an organometallic oxide or metal oxide layer; and e. Purge the reactor with an inert gas.

98. The method of claim 97, further comprising the step of: f. Introduce one or more formulas with R 3 The carboxylic acid vapor 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, C3 to C6 ynyl and C4 to C6 alkyl groups. 10 Aryl groups, to react with the organometal oxide or metal oxide layer; and g. Purge the reactor with an inert gas.

99. The method of claim 97, wherein the one or more compounds or compositions comprise tin.

100. The method of claim 97, wherein the one or more compounds or compositions comprise germanium.

101. The method of claim 97, wherein step (b) comprises pulsed the vapor for about 0.1 seconds to about 3 seconds.

102. The method of claim 97, wherein the one or more oxygen sources in step (d) comprise one or more of the following: oxygen (O2), ozone (O3), nitric oxide (NO), water (H2O) vapor, hydrogen peroxide (H2O2), oxygen plasma (O2O2). ), N x O y (where x = 1 or 2, and y = 1, 2, 3 or 4) and their combinations.

103. The method of claim 97, wherein one or more oxygen sources in step (d) comprise water vapor.

104. The method of claim 97, wherein one or more oxygen sources in step (d) comprise water vapor.

105. The method of claim 97, wherein step (d) comprises pulsed the one or more oxygen sources for about 0.5 seconds to about 5 seconds.

106. The method of claim 98, wherein the one or more carboxylic acid vapors in step (f) comprise one or more of the following: formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, 2-methylbutyric acid, 3-methylbutyric 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, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 4,4-difluorocyclohexanecarboxylic acid, and tetrahydro-3-furancarboxylic acid.

107. The method of claim 98, wherein the one or more carboxylic acid vapors in step (f) consist of carboxylic acids having a boiling point of about 250°C or lower.

108. The method of claim 98, wherein the one or more carboxylic acid vapors in step (f) consist of carboxylic acids having a boiling point of about 200°C or lower.

109. The method of claim 98, wherein the one or more carboxylic acid vapors in step (f) comprise acetic acid.

110. The method of claim 98, wherein the one or more carboxylic acid vapors in step (f) consist of acetic acid.

111. A tin-containing film deposited using one or more organotin compounds or compositions as described in any one of claims 1-96.

112. A tin-containing film deposited by any one of claims 97-110.

113. An organotin oxide or tin oxide film deposited by the method of any one of claims 97-110, wherein the film has an aspect ratio of about 1 to about 60.

114. An organotin oxide or tin oxide film deposited by the method of any one of claims 97-110, wherein the thickness of the film is from about 10 Å to about 5000 Å.

115. A germanium-containing film deposited using one or more organic germanium compounds or compositions as described in any one of claims 1-96.

116. A germanium-containing film deposited by the method described in any one of claims 97-110.

117. An organic germanium oxide or germanium oxide film deposited by the method of any one of claims 97-110, wherein the film has an aspect ratio of about 1 to about 60.

118. An organic germanium oxide or germanium oxide film deposited by the method of any one of claims 97-110, wherein the thickness of the film is from about 10 Å to about 5000 Å.

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