Intramolecular stabilized MONO alkyl metal alkoxides and their use thereof

Abstract

The disclosed and claimed subject matter relates to mono alkyl metal compounds of the formula (XR)M(OR1)3, the use thereof in formulations and methods for depositing metal-containing films and the use thereof for EUV lithography.

Description

PROVISIONAL PATENT APPLICATIONATTORNEY DOCKET No. P24-161-US-PSPINTRAMOLECULAR STABILIZED MONO ALKYL METAL ALKOXIDES AND THEIR USE THEREOFBACKGROUND

[0001] Field

[0002] The disclosed and claimed subject matter relates to mono alkyl metal alkoxide compounds, the use thereof in formulations and methods for depositing metal-containing films and the use thereof for EUV lithography.

[0003] Related Art

[0004] Thin films, and in particular thin metal-containing fdms, have a variety of important applications, such as in nanotechnology and the fabrication of semiconductor devices. Examples of such applications include high-refractive index optical coatings, corrosion-protection 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, adhesive diffusion barriers, EUV photoresist patterning materials, hard mask, transparent conducting electrodes, and integrated circuits.

[0005] Various precursors may be used to form metal-containing thin films and a variety of deposition techniques can be employed. Such techniques include reactive sputtering, ion- assisted deposition, sol-gel deposition, spin coating, chemical vapor deposition (CVD) (also known as metalorganic CVD or MOCVD), and atomic layer deposition (ALD) (also known as atomic layer epitaxy). CVD and ALD processes are increasingly used as they have the advantages of enhanced compositional control, high film uniformity, and effective control of doping.

[0006] The semiconductor industry is currently considering the use of metal-containing thin films as EUV photoresist material for patterning. Many organometallic complexes especially tin- containing compounds have been evaluated as potential precursors for the formation of photoresist material via either spin coating, chemical vapor deposition (CVD), and atomic layer deposition (ALD). Some of these inorganic photoresists show higher sensitivity, can form thin layers, have higher etching resistance, and potentially yield both lower line-edge roughness and higher resolution.

[0007] Spin coating is a deposition method whereby precursors of formulations thereof are dissolved in common organic solvents and these solutions are used to deposit thin films of the material on the surface of a rotating substrate (e.g., a wafer). The films can either consist of the precursor / formulation itself or can be a reaction product of the precursor with a co-reagent e.g., oxygen). In both cases it can be difficult to control the film thickness because it depends on coordination of many parameters such as temperature, concentration of the precursor solution, spinning velocity, chemisorption and physisorption effects, chemical depletion effects, and time. The precursor / formulation itself also plays a crucial role in obtaining high quality thin films suitablePROVISIONAL PATENT APPLICATIONATTORNEY DOCKET No. P24-161-US-PSP for different applications e.g., EUV photolithography). Suitable metal precursors / formulations include those which are thermally stable to preclude any thermal decomposition during film deposition. Additionally, it is important that the metal precursors / formulations are soluble in common organic solvents and provide atmospherically stable moieties.

[0008] CVD is a chemical process whereby precursors are used to form a thin film on a substrate surface. In a typical CVD process, the precursors are passed over the surface of a substrate (e.g., a wafer) in a low pressure or ambient pressure reaction reactor. The precursors react and / or decompose on the substrate surface creating a thin film of deposited material. Volatile by-products are removed by gas flow through the reaction chamber. The deposited film thickness can be difficult to control because it depends on coordination of many parameters such as temperature, pressure, gas flow volumes and uniformity, chemical depletion effects, and time.

[0009] ALD is also a method for the deposition of thin films. It is a self-limiting, sequential, unique film growth technique based on surface reactions that can provide precise thickness control and deposit conformal thin films of materials provided by precursors onto surfaces substrates of varying compositions. In ALD, the precursors are admitted separately during the reaction, resulting in a reaction sequence. The first precursor is passed over the substrate surface producing a monolayer on the substrate surface. Any excess unreacted precursor is pumped out of the reaction reactor. A second precursor is then passed over the substrate surface and reacts with the first precursor, forming a second monolayer of film over the first-formed monolayer of film on the substrate surface. This cycle is repeated to create a film of desired thickness.

[0010] However, the continual decrease in the size of microelectronic components, such as semi-conductor devices, presents several technical challenges and has increased the need for improved thin film technologies. In particular, microelectronic components may include features on or in a substrate, which require filling, e.g. , to form a conductive pathway or to form interconnections. Filling such features, especially in smaller and smaller microelectronic components, can be challenging because the features can become increasingly thin or narrow. Consequently, a complete filling of the feature, e.g., via ALD, would require infinitely long cycle times as the thickness of the feature approaches zero. Moreover, once the thickness of the feature becomes narrower than the size of a molecule of a precursor, the feature cannot be completely filled. As a result, a hollow seam can remain in a middle portion of the feature when ALD is performed. The presence of such hollow seams within a feature is undesirable because they can lead to failure of the device. Accordingly, there exists significant interest in the development of thin film deposition methods, particularly ALD methods that can selectively grow a film on one or more substrates and achieve improved filling of a feature on or in a substrate, including depositing a metal-containing film in a manner which substantially fills a feature without any voids.PROVISIONAL PATENT APPLICATIONATTORNEY DOCKET No. P24-161-US-PSP

[0011] In CVD and ALD, the precursor molecule plays a critical role in achieving high quality films with high conformality and low impurities. Suitable metal precursors include those which are thermally stable to preclude any thermal decomposition but activation for initial chemisorption and yet are chemically reactive towards added reagent. Additionally, it is important that the metal precursors are monomeric for maximum volatility, thermally stable and of high purity to ensure clean evaporation leaving only traces of involatile residue. It is also desirable that the precursors are liquid at room temperature. The temperature of the substrate in CVD and ALD processes is an important consideration in selecting a precursor molecule. Higher substrate temperatures usually promote a higher film growth rate. The preferred precursor molecules must be stable in this temperature range. The preferred precursor is capable of being delivered as gas to the reaction vessel from a liquid phase. This way a constant evaporation surface is ensured, which generally provides a more uniform delivery of the precursor to the reaction vessel than solid phase precursors. The preferred precursor needs to be thermally stable during the use on deposition tool and have sufficient vapor pressure to be delivered to deposition tool without significant decomposition. The precursor is typically delivered from a container stored on a deposition tool for extended period of time, often greater than 3 months. The impurities formed by thermal decomposition of precursor may have negative effect on the deposition process. In some application it is also preferred that the precursor has low sensitivity to light for a longer shelf-life.

[0012] There is a need in the art to provide a thermally stable composition and method for using organometallic (Sn and Ge) compounds as precursors for the deposition of organotin- and organogermanium-containing films for certain applications in semiconductor industry such as EUV photoresist materials, hardmasks for patterning process and transparent conducting electrodes. The resulting organotin or organogermanium oxide films using organometallic compounds featuring the thermally stable composition may result in organotin and organogermanium oxide films having different physical and electrical properties needed in semiconductor fabrication compared with that disclosed in the prior art, i.e., organotin oxide films derived from organotin precursors having iPr-Sn or tBu-Sn groups.

[0013] There have been only a few prior art describing organogermanium trisalkoxides incorporating Me, Et, nBu and tBu as the organo groups without illustration of their use as precursors for spin coating formulation or vapor deposition of organogermanium oxide films. These include: (i) Mehrotra, R.C., Journal of Organometallic Chemistry, Vol. 7, 2, 233-235 (1967) and (ii) West, R., Journal of the American Chemical Society, Vol. 76, 1, 310 (1954).

[0014] The synthesis of simple organotin trisalkoxides having Me, Et, iPr, nBu, and tBu as the organo groups have been described in literature. For example: Kennedy, J. D., Journal of Molecular Structure, Vol. 31, 1, 207-209 (1976).PROVISIONAL PATENT APPLICATIONATTORNEY DOCKET No. P24-161-US-PSP

[0015] Further organotin trisalkoxides having hydrocarbyl as organo groups have been described as precursors for solution phase deposition of organotin oxide films. For example: (i) U.S. Patent Application Publication No. 10228618; (ii) U.S. Patent Application Publication No. 2022 / 0064192; (iii) WO2022 / 016128; and (iv) U.S. Patent No. 10,732,505.

[0016] The above references, however, use either complex synthesis routes or starting material which are expensive or complicated to synthesize. Another issue is the selectivity of different syntheses for these monoalkylated tin species. These references also demonstrate the difficulty of synthesizing monoalkyl tin complexes without impurities, namely organotin compounds with more than one alkyl ligand as a side product (which is why multistep syntheses with low yields are often applied to achieve high purities). In contrast, disclosed and claimed herein is a two-step synthesis using a Grignard reagent of the form MgRX / MgR? and Sn(NMe2)4 and the respective alcohol as the starting material. The Grignard reagent is synthesized following by literature known synthetic procedures and Sn(NMe2)4 can either be commercially purchased or synthesized by using SnC14, HNMe2 and nBuLi. This one-step synthesis gives selectively the mono alkylated product and shows only 4-5% overalkylation. In the second step the amides are exchanged by the alkoxides by simply stirring in the respective alcohol maintaining low overalkylation products.

[0017] Other references disclose the introduction of alkyl chains with heteroatoms or hetero cycles with oxygen and nitrogen atoms but did not show any synthetic work or the influence of the hetero atoms on the thermal stability or light stability of the precursor. See, e.g., 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.

[0018] Similarly, different types of alkyl chains with heteroatoms attached to a Sn center used for the deposition (MOCVD and related methods) of tin metal films or films of mixtures of tin and arsine, antimony, or phosphor but not oxygen has been shown. However, only structures where R is specifically a linear chain are shown, and the unexpected stabilizing effects of branched systems with quaternary carbon in a- or - or y-position relative to tin is not considered or suggested. See, e.g., DE4213292. Another patent claims similar compounds for usage as coordination catalysts. In this case similar alkyl chains with heteroatoms attached to a Sn center are claimed, however, the three other ligands at the Sn center are not claimed to be amides. See, e.g., EP0690748.

[0019] Other references disclose the usage of simple monoalkyltin trisalkoxides as photoresist precursor: U.S. Patent No. 10,787,466; WO2019246254, U.S. Patent No. 11,092,889.

[0020] The use of monoalkyltin trisalkoxides for formulations containing Snl2 clusters has also been shown. Snl2 clusters (i.e., (RSn)i2Oi4(OH)6]X2) have been described as photosensitive in EUV and eBeam exposures. See Sharps etal., Chem. Mater., 31, 4840-4850 (2019); U.S. Patent No. 9,310,684; Castellanos et al., Appl. Mat. Int., 12, 9881-9889 (2020); and Herman et al., Appl.PROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSPMat. Int., 11, 4514-4522 (2019). The changes in the material, coated on a wafer as a photosensitive layer, have been investigated and several hypotheses on how a solubility contrast is induced by exposure to ionizing radiation were discussed. See Castellanos et al., Appl. Mat. Int., 12, 9881- 9889 (2020) and Herman et al., Appl. Mat. Int., 11, 4514-4522 (2019).

[0021] Although organotin trisalkoxides are often highly volatile and liquid, they typically show a high sensitivity towards light and relatively low thermal stabilities, making them less suitable for vapor phase deposition applications. The disclosed and claimed subject matter includes compounds having an additional donating function (oxygen or nitrogen) at the organo group, which has a chelating effect and can stabilize the complex. In addition, by utilizing branched alkyl chains with at least one quaternary carbon in one or more of the a- or P- or y-position, hydrogens are excluded and potential a- or - or y-hydrogen elimination is suppressed. Both features increase the thermal and light stability of the claimed compounds making them beneficial for the usage in CVD and ALD processes for deposition of Sn-containing thin films of high purity. Moreover, the functionalization in the alkyl chain gives additional crosslinking opportunities during EUV exposure. Although some alkyl groups with heteroatoms as R have been disclosed in the above-mentioned references, the branched variants are not included but unexpectedly gives improved stability also in solution.SUMMARY

[0022] In one embodiment, the disclosed and claimed subject matter relates to compounds of Formula (I):(hereinafter “(XR)M(0R1)3”) where:(i) M = Sn or Ge;(ii) R is a branched Cs to Cio alkylene linker group where (i) three to eight main chain carbon moieties connect M and X and (ii) at least one of the first three main chain carbon moieties (i.e. , the a- or P- or y-carbon moieties) that connect M and X is a quaternary carbon moiety that is free of hydrogen;(iii) R1is selected from a linear Ci to C6 alkyl group, a branched C4 to C6 alkyl group or a cyclic C3 to C6 alkyl group; and(iv) X is selected is one of -OR2or -NR3R4where R2, R3and R4are each independently selected from a linear Ci to C6 alkyl group, a branched C4 to C6 alkyl group or a cyclic C3 to C6 alkyl group. In one aspect of this embodiment, the compound of Formula (I) includes, consists essentially of or consists of (NMe2CH2CMe2CH2)Sn(O‘Bu)3. In one aspect of thisPROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP embodiment, the compound of Formula (I) includes, consists essentially of or consists of (OMeCH2CH2CMe2)Sn(OtBu)3.

[0023] The disclosed and claimed compounds of Formula (I) include three alkoxides (- OR1) and one alkylene group (-R) with one additional coordination site (X) which can be an amine or ether group. This amine or ether group (X) is coordinated to the metal via a dative bond (shown as dotted line above) to stabilize the disclosed and claimed compounds and is not a covalent bond like the amides (-OR1) have (shown as a full line). As such, the disclosed and claimed compounds do not include compounds with the formula M(0R1)4 and related organotin compounds having the formula RM(OR1)s as disclosed in U.S. Patent Application Publication No 2017 / 0102612.

[0024] In one embodiment, the disclosed and claimed subject matter relates to compositions that include, consist essentially of or consist of one or more compounds of Formula (I).

[0025] In another embodiment, the above-described compounds and / or compositions are used in method(s) for depositing tin-containing films and / or germanium-containing films. In a further aspect of this embodiment, the deposited films include, consist essentially of or consist of one or more of organotin oxide, tin oxide, organogermanium oxide and germanium oxide.

[0026] This summary section does not specify every embodiment and / or incrementally novel aspect of the disclosed and claimed subject matter. Instead, this summary only provides a preliminary discussion of different embodiments and corresponding points of novelty over conventional techniques and the known art. For additional details and / or possible perspectives of the disclosed and claimed subject matter and embodiments, the reader is directed to the Detailed Description section and corresponding figures of the disclosure as further discussed below.

[0027] The order of discussion of the different steps described herein has been presented for clarity’s sake. In general, the steps disclosed herein can be performed in any suitable order. Additionally, although each of the different features, techniques, configurations, etc. disclosed herein may be discussed in different places of this disclosure, it is intended that each of the concepts can be executed independently of each other or in combination with each other as appropriate. Accordingly, the disclosed and claimed subject matter can be embodied and viewed in many different ways.BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and together with the description serve to explain the principles of the disclosed subject matter. In the drawings:

[0029] FIG. 1 illustrates the119Sn NMR of Snl2 compound 9, [((DMDMP)Sn)i2Oi4(OH)s]);

[0030] FIG. 2 illustrates the119Sn NMR of Snl2 compound 10,[((MODMP)Sn)i2Oi4(OH)8]); andPROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP

[0031] FIG. 3 illustrates the e-beam dose curves of thin films made from compounds 9 and 10.DEFINITIONS

[0032] Unless otherwise stated, the following terms used in the specification and claims shall have the following meanings for this application.

[0033] For purposes of this invention and the claims hereto, the numbering scheme for the Periodic Table Groups is according to the IUPAC Periodic Table of Elements.

[0034] The term “and / or” as used in a phrase such as “A and / or B” herein is intended to include “A and B,” “A or B,” “A” and “B.”

[0035] As used herein, “Cx y” designates the number of carbon atoms in a chain. For example, Ci-6 alkyl refers to an alkyl chain having a chain of between 1 and 6 carbons (e.g. , methyl, ethyl, propyl, butyl, pentyl and hexyl). Unless specifically stated otherwise, the chain can be linear or branched.

[0036] Unless otherwise indicated, “alkyl” refers to hydrocarbon groups which can be linear, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl and the like), cyclic e.g., cyclohexyl, cyclopropyl, cyclopentyl and the like) or multicyclic (e.g., norbornyl, adamantly and the like). Suitable acyclic groups can be methyl, ethyl, n-or iso-propyl, n-, iso, or tert-butyl, linear or branched pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl and hexadecyl. Unless otherwise stated, alkyl refers to 1-10 carbon atom moieties. The cyclic alkyl groups may be mono cyclic or polycyclic. Suitable examples of mono-cyclic alkyl groups include substituted cyclopentyl, cyclohexyl, and cycloheptyl groups. As mentioned herein the cyclic alkyl groups may have any of the acyclic alkyl groups as substituent. These alkyl moieties may be substituted or unsubstituted.

[0037] “Hydroxy” (a.k.a. “hydroxyl”) refers to an -OH group.

[0038] “Organo” in organotin trialkoxides refers to an organo group that is bonded to the tin atom via Sn-C bond.

[0039] Unless otherwise indicated, the term “substituted” when referring to an alkyl, alkoxy, fluorinated alkyl and the like refers to one of these moieties which also contains one or more substituents including, but not limited, to the following substituents: alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxy, amino and amino alkyl. Similarly, the term “unsubstituted” refers to these same moieties where no substituents apart from hydrogen are present.

[0040] Alkylene groups are bivalent saturated aliphatic radical (such as ethylene) regarded as derived from an alkane (such as those described above) by removal of two hydrogen atoms from different carbon atoms. When referring to alkylene groups, these include an alkylene chain substituted with (Ci-Cis) alkyl groups in the main carbon chain of the alkylene group. Alkylene groups can also include one or more alkyne groups in the alkylene moiety, where alkyne refers to a triple bond. Essentially an alkylene is a divalent hydrocarbon group as the backbone.PROVISIONAL PATENT APPLICATIONATTORNEY DOCKET No. P24-161-US-PSPAccordingly, a divalent acyclic group may be methylene, 1,1- or 1,2-ethylene, 1,1-, 1,2-, or 1,3 propylene, 2,5-dimethyl-hexene, 2,5-dimethyl-hex-3-yne, and so on. Similarly, a divalent cyclic alkyl group may be 1,2- or 1,3-cyclopentylene, 1,2-, 1,3-, or 1 ,4-cyclohexylene, and the like.

[0041] The terms “substituent,” “radical,” “group” and “moiety” may be used interchangeably.

[0042] As used herein, the terms “metal-containing complex” (or more simply, “complex”) and “precursor” are used interchangeably and refer to metal-containing molecule or compound which can be used to prepare a metal-containing film by a vapor deposition process such as, for example, ALD or CVD. The metal-containing complex may be deposited on, adsorbed to, decomposed on, delivered to, and / or passed over a substrate or surface thereof, as to form a metalcontaining film. In one or more embodiments, the metal-containing complexes disclosed herein are metal halide complexes, particularly molybdenum chloride complexes.

[0043] As used herein, the term “metal-containing film” includes not only an elemental metal film as more fully defined below, but also a film which includes a metal along with one or more elements, for example in form of a metal oxide film, metal nitride film, metal silicide film, a metal carbide film and the like. As used herein, the terms “elemental metal film” and “pure metal film” are used interchangeably and refer to a film which consists of, or consists essentially of, pure metal. For example, the elemental metal film may include 100% pure metal, or the elemental metal film may include 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 along with one or more impurities. Unless context dictates otherwise, the term “metal film” shall be interpreted to mean an elemental metal film.

[0044] As used herein, the term “vapor deposition process” is used to refer to any type of vapor deposition technique, including but not limited to, CVD and ALD. In various embodiments, CVD may take the form of conventional (i.e., continuous flow) CVD, liquid injection CVD, or photo-assisted CVD. CVD may also take the form of a pulsed technique, i.e., pulsed CVD. ALD is used to form a metal-containing film by vaporizing and / or passing at least one metal complex disclosed herein over a substrate surface. For conventional ALD processes see, for example, George S. M., et al. J. Phys. Chem., 1996, 100, 13121-13131. In other embodiments, ALD may take the form of conventional (i.e., pulsed injection) ALD, liquid injection ALD, photo-assisted ALD, plasma-assisted ALD, or plasma-enhanced ALD. The term “vapor deposition process” further includes various vapor deposition techniques described in Chemical Vapour Deposition: Precursors, Processes, and Applications', Jones, A. C.; Hitchman, M. L., Eds. The Royal Society of Chemistry: Cambridge, 2009; Chapter 1, pp. 1-36.

[0045] Throughout the description, the term “ALD or ALD-like” refers to a process including,PROVISIONAL PATENT APPLICATIONATTORNEY DOCKET No. P24-161-US-PSP but not limited to, the following processes: a) each reactant including organotin compound precursor and reactive gas is introduced sequentially into a reactor such as a single wafer ALD reactor, semibatch ALD reactor, or batch furnace ALD reactor; b) each reactant including organotin compound precursor and reactive gas is exposed to a substrate by moving or rotating the substrate to different sections of the reactor and each section is separated by inert gas curtain, i.e. , spatial ALD reactor or roll to roll ALD reactor. The ALD-like is defined herein as a cyclic CVD process that provides a high conformal metal-containing film on a substrate as shown by having at least one of the following: percentage of non-uniformity of about 5% or less as measured by ellipsometry, a deposition rate of 1 A or greater per cycle or a combination thereof.

[0046] As used herein, the term “feature” refers to an opening in a substrate which may be defined by one or more sidewalls, a bottom surface, and upper corners. In various aspects, the feature may be a via, a trench, contact, dual damascene, etc.

[0047] As used herein, the terms “selective growth,” “selectively grown” and “selectively grows” may be used synonymously and refer to film growth on at least a portion of a first substrate and no substantial film growth on a remaining portion of the first substrate as well as more film growth on at least a portion of the first substrate compared to film growth on a remaining portion of the first substrate. For example, selective growth may include growth of a film on a lower portion of a feature while less film growth or no film growth may occur in an upper portion of that feature or outside that feature. With respect to more than one substrate, the terms “selective growth” “selectively grown” and “selectively grows” also encompass film growth on a first substrate and substantially no film growth on a second substrate (or a third substrate, or fourth substrate or a fifth substrate, etc.) as well as more film growth on the first substrate than on the second substrate (or a third substrate, or fourth substrate or a fifth substrate, etc.).

[0048] The term “about” or “approximately,” when used in connection with a measurable numerical variable, refers to the indicated value of the variable and to all values of the variable within ± 5% of the indicated value.

[0049] “Halo” or “halide” refers to a halogen (e.g., F, Cl, Br and I).

[0050] “Snl2 compound” refers to a tin cluster compound having 12 tin atoms.

[0051] “Tin-containing film” refers to organotin oxide or tin oxide which can be employed as material in semi-conductor or display device fabrication process.

[0052] The section headings used herein are for organizational purposes and are not to be construed as limiting the subject matter described. All documents, or portions of documents, cited in this application, including, but not limited to, patents, patent applications, articles, books, and treatises, are hereby expressly incorporated herein by reference in their entirety for any purpose. In the event that any of the incorporated literature and similar materials defines a term in a mannerPROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP that contradicts the definition of that term in this application, this application controls.DETAILED DESCRIPTION

[0053] It is to be understood that both the foregoing general description and the following detailed description are illustrative and explanatory, and are not restrictive of the subject matter, as claimed. The objects, features, advantages and ideas of the disclosed subject matter will be apparent to those skilled in the art from the description provided in the specification, and the disclosed subject matter will be readily practicable by those skilled in the art on the basis of the description appearing herein. The description of any “preferred embodiments” and / or the examples which show preferred modes for practicing the disclosed subject matter are included for the purpose of explanation and are not intended to limit the scope of the claims.

[0054] It will also be apparent to those skilled in the art that various modifications may be made in how the disclosed subject matter is practiced based on described aspects in the specification without departing from the spirit and scope of the disclosed subject matter disclosed herein.

[0055] In the below-described embodiments directed to methods or processes, it is understood that in some embodiments the steps of the methods may be performed in a variety of orders, may be performed sequentially or concurrently (e.g., during at least a portion of another step), and any combination thereof. The respective step of supplying the precursors and the nitrogen-containing source gases may be performed by varying the duration of the time for supplying them to change the stoichiometric composition of the resulting dielectric film.

[0056] As noted above, the disclosed and claimed subject matter relates to mono alkyl metal compounds and their use in methods for depositing metal-containing films. During the typical preparation of such materials, overalkylation typically takes place either due to the strong alkylation agent or through rearrangements of the corresponding products where 2 RSnLs are slowly reacting to R2SnL2 and SnL4. This particular redistribution behavior has not been observed for germanium in literature. One approach to thermally stabilize these types of compounds is to insert another coordination site to the alkyl ligand. This can enhance the overall stability, but also lead to a decreased volatility and even to solidification at room temperature.

[0057] The disclosed and claimed subject matter overcomes the above issues. Namely it provides an easy method for synthesizing compounds of Formula (I): (XRjIWOR' k where:(i) M = Sn or Ge;(ii) R is a branched Cs to Cio alkylene linker group where (i) three to eight main chain carbon moieties connect M and X and (ii) at least one of the first three main chain carbon moieties (i.e. , the a- or [3- or y-carbon moieties) that connect M and X is a quaternary carbon moiety that is free of hydrogen;(iii) R1is selected from a linear Ci to C6 alkyl group, a branched C4 to C6 alkylPROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP group or a cyclic C3 to C6 alkyl group; and(iv) X is selected is one of -OR2or -NR3R4where R2, R3and R4are each independently selected from a linear Ci to C6 alkyl group, a branched C4 to C6 alkyl group or a cyclic C3 to C6 alkyl group. These compounds remain liquids at room temperature and provide high thermal and light stabilities making them ideal for the utilization in vapor phase deposition processes. The introduction of alkyl groups with additional heteroatoms (i.e., -OR2and -NR3R4) results in a dative bond to the metal center, which increase thermal and light stability. Furthermore, blocking the a- or P- or y-C position of the alkylene related to the metal atom with alkyl groups such as one or two methyl groups would block potential a- or - or y-hydrogen elimination decomposition pathway as well as introduces a higher asymmetry to the resulting metal complex. Thus, the thermal stability, volatility and viscosity is improved.

[0058] Organotin and Organogermanium Compounds

[0059] In one embodiment, the disclosed and claimed subject matter relates to compounds of Formula (I): (XRjM OR1^ where(i) M = Sn or Ge;(ii) R is a branched C5 to C10 alkylene linker group where (i) three to eight main chain carbon moieties connect M and X and (ii) at least one of the first three main chain carbon moieties (i.e. , the a- or P- or y-carbon moieties) that connect M and X is a quaternary carbon moiety that is free of hydrogen;(iii) R1is selected from a linear Ci to C6 alkyl group, a branched C4 to C6 alkyl group or a cyclic C3 to C6 alkyl group; and(iv) X is selected is one of -OR2or -NR3R4where R2, R3and R4are each independently selected from a linear Ci to C6 alkyl group, a branched C4 to C6 alkyl group or a cyclic C3 to C6 alkyl group.

[0060] Metals

[0061] In one embodiment, M = Sn.

[0062] In one embodiment, M = Ge.

[0063] R Group

[0064] As noted above, R is a branched C5 to C10 alkylene linker group wherein (i) three to eight main chain carbon moieties connecting M and X and (ii) at least one of the first three main chain carbon moieties (i. e. , the a- or P- or y-positions or a- or P- or y-carbons) connecting M and X is a quaternary carbon moiety that is free of hydrogen. As those skilled in the art will understand, although the R group includes a total of five to ten carbon moieties, at least three to eight of those carbon moieties must form the main chain (i.e., the “backbone”) connecting M and X, and at least one of the first three carbon moieties (i.e., the a-carbon moiety, P-carbon moiety and y-carbonPROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP moiety) in the main chain starting from M must be a hydrogen-free quaternary carbon moiety. Thus, for example, an embodiment where R has three carbon moieties in main chain connecting M and X has the formula / structure (OR1)3M-C“-C*3-C7-X (note that the sidechains / hydrogens on the three backbone carbon moieties are not shown).

[0065] It is further to be understood that the requirement that at least one of the first three carbon moieties (i.e., the a-carbon moiety, P-carbon moiety and y-carbon moiety) in the main chain starting from M must be a hydrogen-free quaternary carbon moiety refers only to the carbon atoms of carbon moieties in the main chain (i.e., the “backbone”) connecting M and X; it does not exclude the presence of hydrogens on other atoms attached or otherwise appended to such main chain carbon moieties (i.e., side chains appended to the main chain carbons such as a -CH3 group).

[0066] In one embodiment, in R the Cs to C10 alkylene linker group consist of three main chain carbons moieties connecting M and X.

[0067] In one embodiment, in R the C5 to C10 alkylene linker group consist of four main chain carbon moieties connecting M and X.

[0068] In one embodiment, in R the Cs to C10 alkylene linker group consist of five main chain carbon moieties connecting M and X.

[0069] In one embodiment, in R the Cs to C10 alkylene linker group consist of six main chain carbon moieties connecting M and X.

[0070] In one embodiment, in R the Cs to C10 alkylene linker group consist of seven main chain carbon moieties connecting M and X.

[0071] In one embodiment, in R the Cs to C10 alkylene linker group consist of eight main chain carbon moieties connecting M and X.

[0072] In one embodiment, in R the a-carbon moiety is a hydrogen- free quaternary carbon moiety.

[0073] In one embodiment, in R the P-carbon moiety is a hydrogen- free quaternary carbon moiety.

[0074] In one embodiment, in R the y-carbon moiety is a hydrogen- free quaternary carbon moiety.

[0075] In one embodiment, in R two or more of the a-carbon moiety, P-carbon moiety and y-carbon moiety are hydrogen-free quaternary carbon moieties.

[0076] In one embodiment, R is a -C(Me2)CH2CH2- group starting from M and connecting to X (i.e., (NR1R2)3M-C(Me2)CH2CH2-X).

[0077] In one embodiment, R is a -CH2C(Me2)CH2- group starting from M and connecting to X (i.e., (NR1R2)3M-CH2C(Me2)CH2-X).

[0078] In one embodiment, R is a -CH2CH2C(Me2)- group starting from M and connectingPROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP to X (i.e., (NR1R2)3M-CH2CH2C(Me2)-X).

[0079] R1Group

[0080] In one embodiment, R1is a linear Ci to C6 alkyl group. In one aspect of this embodiment, R1is a linear Ci alkyl group. In one aspect of this embodiment, R1is a linear C2alkyl group. In one aspect of this embodiment, R1is a linear C3 alkyl group. In one aspect of this embodiment, R1is a linear C4 alkyl group. In one aspect of this embodiment, R1is a linear C5 alkyl group. In one aspect of this embodiment, R1is a linear C6 alkyl group.

[0081] In one embodiment, R1is a branched C4 to C6 alkyl group. In one aspect of this embodiment, R1is a branched C4 alkyl group. In one aspect of this embodiment, R1is a branched Cs alkyl group. In one aspect of this embodiment, R1is a branched C6 alkyl group.

[0082] In one embodiment, R1is a cyclic C3 to C6 alkyl group. In one aspect of this embodiment, R1is a cyclic C3 alkyl group. In one aspect of this embodiment, o R1is a cyclic C4 alkyl group. In one aspect of this embodiment, R1is a cyclic C5 alkyl group. In one aspect of this embodiment, R1is a cyclic C6 alkyl group.

[0083] X Group

[0084] In one embodiment, X is a -OR2group. In one aspect of this embodiment, R2is a linear Ci to C6 alkyl group. In one aspect of this embodiment, R3is a linear Ci alkyl group. In one aspect of this embodiment, R2is a linear C2alkyl group. In one aspect of this embodiment, R2is a linear C3 alkyl group. In one aspect of this embodiment, R2is a linear C4 alkyl group. In one aspect of this embodiment, R2is a linear C5 alkyl group. In one aspect of this embodiment, R3is a linear C6 alkyl group. In another aspect of this embodiment, R2is a branched C4 to C6 alkyl group. In one aspect of this embodiment, R2is a branched C4 alkyl group. In one aspect of this embodiment, R3is a branched C5 alkyl group. In one aspect of this embodiment, R2is a branched C6 alkyl group. In a further aspect of this embodiment, R2is a cyclic C3 to C6 alkyl group. In one aspect of this embodiment, R2is a cyclic C3 alkyl group. In one aspect of this embodiment, R2is a cyclic C4 alkyl group. In one aspect of this embodiment, R2is a cyclic Cs alkyl group. In one aspect of this embodiment, R2is a cyclic C6 alkyl group.

[0085] In one embodiment, X is a -NR3R4group. In one aspect of this embodiment, one or both of R3and R4is a linear Ci to C6 alkyl group. In one aspect of this embodiment, one or both of R3and R4is a linear Ci alkyl group. In one aspect of this embodiment, one or both of R3and R4is a linear C2alkyl group. In one aspect of this embodiment, one or both of R3and R4is a linear C3 alkyl group. In one aspect of this embodiment, one or both of R3and R4is a linear C4 alkyl group. In one aspect of this embodiment, one or both of R3and R4is a linear Cs alkyl group. In one aspect of this embodiment, one or both of R3and R4is a linear C6 alkyl group. In another aspect of this embodiment, one or both of R3and R4is a branched C4 to C6 alkyl group. In one aspect of this embodiment, onePROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP or both of R3and R4is a branched C4 alkyl group. In one aspect of this embodiment, one or both of R3and R4is a branched C5 alkyl group. In one aspect of this embodiment, one or both of R3and R4is a branched C6 alkyl group. In a further aspect of this embodiment, one or both of R3and R4is a cyclic C3 to C6 alkyl group. In one aspect of this embodiment, one or both of R3and R4is a cyclic C3 alkyl group. In one aspect of this embodiment, one or both of R3and R4is a cyclic C4 alkyl group. In one aspect of this embodiment, one or both of R3and R4is a cyclic C5 alkyl group. In one aspect of this embodiment, one or both of R3and R4is a cyclic C6 alkyl group.

[0086] In one embodiment, the compound of Formula (I) includes, consists essentially of or consists of (NMe2CH2CMe2CH2)Sn(O‘Bu)3.

[0087] In one embodiment, the compound of Formula (I) includes, consists essentially of or consists of (OMeCH2CMe2CH2)Sn(O‘Bu)3.

[0088] In one embodiment, the compound of Formula (I) includes, consists essentially of or consists of (NMe2CH2CH2CMe2)Sn(O‘Bu)3.

[0089] In one embodiment, the compound of Formula (I) includes, consists essentially of or consists of (OMeCH2CH2CMe2)Sn(O‘Bu)3.

[0090] Exemplary Embodiments

[0091] In one embodiment, in Formula (I) M is Sn, R is one of -C(Me2)CH2CH2-, - CH2C(Me2)CH2- and -CH2CH2C(Me2)-, R1is one of ‘Bu and ‘amyl and X is -NR4R5where R4and R5each are independently one of Me and Et.

[0092] In one embodiment, in Formula (I) M is Sn, R is one of, -C(Me2)CH2CH2-, - CH2C(Me2)CH2- and -CH2CH2C(Me2)-, R1is one of ‘Bu and ‘amyl and X is -OR3where R3is one of Me and Et.

[0093] In one embodiment, in Formula (I) M is Sn, R is -CH2C(Me2)CH2-, R1is ‘Bu and X is-NMe2 as follows:-dimethylamino)-2,2-dimethyl-propyl-tris-tertbutoxytin).

[0094] In one embodiment, in Formula (I) M is Sn, R is -CH2C(Me2)CH2-, R1is ‘Bu and X is-NEt2 as follows:-diethylamino)-2,2-dimethyl-propyl-tris-tertbutoxytin).

[0095] In one embodiment, in Formula (I) M is Sn, R is -CH2C(Me2)CH2-, R1is ‘amyl andPROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSPX is -NMe2 as follows:-dimethylamino)-2,2-dimethyl-propyl-tris- tertamyloxy tin).

[0096] In one embodiment, in Formula (I) M is Sn, R is -CH2C(Me2)CH2-, R1is ‘amyl and X is-NEt2 as follows:-diethylamino)-2,2-dimethyl-propyl-tris-tertamyloxytin).

[0097] In one embodiment, in Formula (I) M is Sn, R is -CH2CH2C(Me2)-, R1is ‘Bu and X is -NMe2 as follows:-dimethylamino)-l,l-dimethyl-propyl-tris-tertbutyloxytin).

[0098] In one embodiment, in Formula (I) M is Sn, R is -CH2C(Me2)CH2-, R1is ‘Bu and X is -OMe as follows:-methoxy-2,2-dimethyl-propyl-tris-tertbutoxytin).

[0099] In one embodiment, in Formula (I) M is Sn, R is -CH2C(Me2)CH2-, R1is ‘Bu and X is -OEt as follows:-ethoxy-2,2-dimethyl-propyl-tris-tertbutoxytin).

[0100] In one embodiment, in Formula (I) M is Sn, R is -CH2C(Me2)CH2-, R1is ‘amyl andX is -OMe as follows:-methoxy-2,2-dimethyl-propyl-tris-tertamyloxytin).

[0101] In one embodiment, in Formula (I) M is Sn, R is -CH2C(Me2)CH2-, R1is ‘amyl andX is -OEt as follows:-ethoxy-2,2-dimethyl-propyl-tris-tertamyloxytin).

[0102] In one embodiment, in Formula (I) M is Sn, R is -CH2CH2C(Me)2-, R1is ‘Bu and XPROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP is -OMe as follows:-methoxy-l,l-dimethyl-propyl-tris-tertbutoxytin).

[0103] In one embodiment, in Formula (I) M is Sn, R is -CH2CH2C(Me)2-, R1is ‘Bu and X is -OEt as follows:-ethoxy-l,l-dimethyl-propyl-tris-tertbutoxytin).

[0104] In one embodiment, in Formula (I) M is Sn, R is -CtECtEC Me -, R1is ‘amyl andX is -OMe as follows:-methoxy-l,l-dimethyl-propyl-tris-tertamyloxytin).

[0105] In one embodiment, in Formula (I) M is Sn, R is -CtECtEC Me -, R1is ‘amyl andX is -OEt as follows:-ethoxy- 1 , 1 -dimethyl-propyl-tris-tertamyloxytin) .

[0106] Compositions of Organotin Compounds

[0107] In one embodiment, the disclosed and claimed subject matter relates to compositions that include, consist essentially of or consist of (a) one or more of the compounds of Formula (I) described above and (b) one or more solvents.

[0108] In one embodiment, the one or more the compounds of Formula (I) of the compositions includes, consists essentially of or consists of one or more of 3-(N,N-dimethylamino)-2,2-dimethyl- propyl-tris-tertbutoxytin, 3-(N,N-diethylamino)-2,2-dimethyl-propyl-tris-tertbutoxytin, 3-(N,N- dimethylamino)-2,2-dimethyl-propyl-tris-tertamyloxytin, 3-(N,N-diethylamino)-2,2-dimethyl-propyl- tris-tertamyloxytin, 3-(N,N-dimethylamino)- 1 , 1-dimethyl-propyl-tris-tertbutoxytin, 3-methoxy-2,2- dimethyl-propyl-tris-tertbutoxytin, 3-ethoxy-2,2-dimethyl-propyl-tris-tertbutoxytin, 3-methoxy-2,2- dimethyl-propyl-tris-tertamyloxytin, 3-ethoxy-2,2-dimethyl-propyl-tris-tertamyloxytin, 3-methoxy-1.1-dimethyl-propyl-tris-tertbutoxytin, 3-ethoxy-l,l-dimethyl-propyl-tris-tertbutoxytin, 3-methoxy-1.1-dimethyl-propyl-tris-tertamyloxytin and 3-ethoxy- 1 , 1 -dimethyl-propyl-tris-tertamyloxytin.

[0109] In one embodiment, the one or more the compounds of Formula (I) of the compositions includes, consists essentially of or consists of 3-(N,N-dimethylamino)-2,2-dimethyl- propyl-tris-tertbutoxytin.

[0110] In one embodiment, the one or more the compounds of Formula (I) of the compositions includes, consists essentially of or consists of 3-(N,N-dimethylamino)-2,2-dimethyl- propyl-tris-tert amyloxytin.PROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP

[0111] In one embodiment, the one or more the compounds of Formula (I) of the compositions includes, consists essentially of or consists of 3-(N,N-diethylamino)-2,2-dimethyl- propyl-tris-tert amyloxytin.

[0112] In one embodiment, the one or more the compounds of Formula (I) of the compositions includes, consists essentially of or consists of 3-(N,N-diethylamino)-2,2-dimethyl- propyl-tris-tertbutoxytin.

[0113] In one embodiment, the one or more the compounds of Formula (I) of the compositions includes, consists essentially of or consists of 3-(N,N-dimethylamino)-l,l-dimethyl- propyl-tris-tertbutoxytin.

[0114] In one embodiment, the one or more the compounds of Formula (I) of the compositions includes, consists essentially of or consists of 3-methoxy-2,2-dimethyl-propyl-tris-tertbutoxytin.

[0115] In one embodiment, the one or more the compounds of Formula (I) of the compositions includes, consists essentially of or consists of 3-ethoxy-2,2-dimethyl-propyl-tris-tertbutoxytin.

[0116] In one embodiment, the one or more the compounds of Formula (I) of the compositions includes, consists essentially of or consists of 3-methoxy-2,2-dimethyl-propyl-tris-tertamyloxytin.

[0117] In one embodiment, the one or more the compounds of Formula (I) of the compositions includes, consists essentially of or consists of 3-ethoxy-2,2-dimethyl-propyl-tris-tertamyloxytin.

[0118] In one embodiment, the one or more the compounds of Formula (I) of the compositions includes, consists essentially of or consists of 3-methoxy-l,l-dimethyl-propyl-tris-tertbutoxytin.

[0119] In one embodiment, the one or more the compounds of Formula (I) of the compositions includes, consists essentially of or consists of 3-ethoxy-l,l-dimethyl-propyl-tris-tertbutoxytin.

[0120] In one embodiment, the one or more the compounds of Formula (I) of the compositions includes, consists essentially of or consists of 3-methoxy-l,l-dimethyl-propyl-tris-tertamyloxytin.

[0121] In one embodiment, the one or more the compounds of Formula (I) of the compositions includes, consists essentially of or consists of 3-ethoxy-l,l-dimethyl-propyl-tris-tertamyloxytin.

[0122] The compositions of the disclosed and claimed subject matter further include (b) one or more solvent(s). Suitable solvents include hydrocarbon solvents which are particularly desirable due to their ability to be dried to sub-ppm levels of water. Exemplary hydrocarbon solvents that can be used in the compositions include, but are not limited to, toluene, mesitylene, cumene (iso-propylbenzene), p-cymene (4-iso-propyl toluene), 1,3-di-iso-propylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, decahydronaphthalene (decalin) and combinations thereof. In certain embodiments, the hydrocarbon solvent is a high boiling point solvent or has a boiling point of about 100 °C or greater.

[0123] Methods of Depositions

[0124] In another embodiment, the above-described tin compounds and / or compositions arePROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP used in method(s) for depositing tin-containing films.

[0125] In one embodiment, the method for deposition of organotin oxide or tin oxide films of the disclosed and claimed subject matter includes, consists essentially of or consists of the steps of: a. providing one or more substrates in a reactor, where the reactor is heated to temperature of from about 25 °C to about 600 °C and optionally maintained at a pressure of about 100 torr or less; b. introducing into the reactor a vapor including, consisting essentially of or consisting of one or more compounds of Formula (I) or a composition of such compounds that forms a metal-containing (i.e., a tin-containing or a germanium-containing) layer on a surface of the substrate; c. purging the reactor with an inert gas; d. introducing one or more oxygen source to convert the tin-containing layer to an organotin oxide or tin oxide layer; and e. purging the reactor with an inert gas.

[0126] In one embodiment, the oxygen source can be one or more of water vapor, hydrogen peroxide, organic peroxides and mixtures thereof for a thermal ALD or ALD-like process to deposit organotin oxide. In other one embodiment, the oxygen source can be one or more of water plasma, ozone, oxygen, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxides plasma, carbon dioxide plasma, and mixtures thereof for formation of tin oxide materials. In a particular embodiment, the oxygen source includes, consists essentially of or consists of water vapor.

[0127] In a preferred embodiment of the above method, the step (d) one or more oxygen source includes, consists essentially of or consists of water vapor and the process further includes, consists essentially of or consists of the additional steps of introducing a carboxylic acid vapor and purging the same. In particular, the method for deposition of organotin oxide films of the disclosed and claimed subject matter includes, consists essentially of or consists of the steps of: a. providing one or more substrates in a reactor, where the reactor is heated to temperature of from about 25 °C to about 600 °C and optionally maintained at a pressure of about 100 torr or less; b. introducing into the reactor a vapor including, consisting essentially of or consisting of one or more compounds of Formula (I) or a composition of such compounds that forms a metal-containing (i.e., a tin-containing or a germanium-containing) layer on a surface of the substrate; c. purging any unreacted precursor from the reactor using an inert gas; d. introducing one or more oxygen source including, consisting essentially of or consisting of water vapor to convert the tin-containing layer to anPROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP organotin oxide or tin oxide layer; e. purging the reactor with an inert gas; f. introducing one or more carboxylic acid vapor having the formula R5COOH where R5is selected from hydrogen, a linear Ci to C6 alkyl group, a branched C3 to C6 alkyl group, a C3 to C6 cyclic alkyl group, a C2 to C6 alkenyl group, a C3 to C6 alkynyl group, and a C4 to C10 aryl group to react with the organotin oxide layer; and g. purging the reactor with an inert gas.

[0128] Step (b) Delivery of Organotin and / or Organogermanium Precursor

[0129] As noted above, step (b) of the disclosed and claimed methods includes introducing into the reactor a vapor including, consisting essentially of or consisting of one or more compounds of Formula (I) or a composition of such compounds that forms a metal-containing (i.e., a tin- containing or a germanium-containing) layer on a surface of the substrate.

[0130] In one embodiment, the vapor includes, consists essentially of or consists of one or more organotin compound of Formula (I). In one embodiment, the vapor includes, consists essentially of or consists of one or more organogermanium compound of Formula (I).

[0131] 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 second. In another embodiment, the precursor vapor pulse time is about 0.25 second. In another embodiment, the precursor vapor pulse time is about 0.5 second. In 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 is longer than 2 seconds depending on the volume / design of the reactor chamber.

[0132] In one embodiment, the precursor vapor is separated from other precursor materials prior to and / or during the introduction to the reactor. This process avoids any premature reaction of the metal precursor with any other materials.

[0133] In another embodiment, the precursor vapor is alternatively exposed to the substrate with other reactants (e.g., other precursors or reagents). This process enables film growth to proceed by self-limiting control of the surface reactions, the pulse length of each precursor or reagent and the deposition temperature. It should be noted, however, that film growth ceases once the surface of the substrate is saturated with organotin precursor vapor.

[0134] In another embodiment, a flow of argon and / or other gas is employed as a carrier gas to help deliver the organotin precursor vapor to the reaction reactor during the precursor pulsing.PROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP

[0135] Step (d) Oxygen Source

[0136] As noted above, step (d) of the disclosed and claimed method includes introducing one or more oxygen source to convert the metal-containing layer to an organometal oxide or metal oxide layer. In one embodiment, the metal-containing layer includes, consists essentially of or consists of tin. In one embodiment, the metal-containing layer includes, consists essentially of or consists of germanium.

[0137] In one embodiment, the one or more oxygen source includes one or more of oxygen (O2), ozone (O3), nitric oxide (NO), water (H2O) vapor, hydrogen peroxide (H2O2), oxygen plasma (O*), NxOy (where x = 1 or 2 and y = 1, 2, 3 or 4) and combinations thereof. In one aspect of this embodiment, the one or more oxygen source includes oxygen. In one aspect of this embodiment, the one or more oxygen source includes ozone. In one aspect of this embodiment, the one or more oxygen source includes nitric oxide. In one aspect of this embodiment, the one or more oxygen source includes water vapor. In one aspect of this embodiment, the one or more oxygen source includes hydrogen peroxide. In one aspect of this embodiment, the one or more oxygen source includes oxygen and ozone. In one aspect of this embodiment, the one or more oxygen source includes oxygen plasma. In one aspect of this embodiment, the one or more oxygen source includes NxOy where x = 1 or 2 and y = 1, 2, 3 or 4. In one embodiment, the one or more oxidant is a vapor.

[0138] As noted above, in one preferred embodiment, for example, the one or more oxygen source includes, consists essentially of or consists of water vapor. In one aspect of this embodiment, the one or more oxygen source includes water vapor. In one aspect of this embodiment, the one or more oxygen source consists essentially of water vapor. In one aspect of this embodiment, the one or more oxygen source consists of water vapor.

[0139] In one embodiment, the one or more oxygen source pulse time varies from about 0.5 seconds to about 5 seconds. In one embodiment, for example, the one or more oxygen source pulse time is about 2.5 seconds. In one embodiment, for example, the one or more oxygen source pulse time is about 5 seconds. Yet, in another embodiment, the one or more oxygen source pulse time is longer than 5 seconds depending on the volume / design of the reactor chamber.

[0140] Step (f) Carboxylic Acid-Containing Vapor

[0141] As noted above, a preferred embodiment of the disclosed and claimed method includes step (f) introducing one or more carboxylic acid vapor having the formula R5COOH where R5is selected from hydrogen, a linear Ci to C6 alkyl group, a branched C3 to C6 alkyl group, a C3 to C6 cyclic alkyl group, a C2 to C6 alkenyl group, a C3 to C6 alkynyl group, and a C4 to C10 aryl group to react with the organotin oxide layer.

[0142] In another embodiment, the carboxylic acid includes one or more of formic acid, acetic acid, propionic acid, butyric acid, iso-butyric acid, valeric acid, 2-methylbutyric acid, 3-PROVISIONAL PATENT APPLICATIONATTORNEY DOCKET No. P24-161-US-PSP methylbutyric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, fluoroacetic acid, chloroacetic acid, iodoacetic acid, dichloroacetic acid, 4,4,4-trifluorobutanoic acid, 3,3,3-trifluoropropanoic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 4,4-difluorocyclohexanecarboxylic acid, tetrahydro-3-furancarboxylic 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 iso-butyric 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 caproic acid. In one aspect of this embodiment, the carboxylic acid includes enanthic acid. In one aspect of this embodiment, the carboxylic acid includes caprylic acid. In one aspect of this embodiment, the carboxylic acid includes pelargonic acid. In one aspect of this embodiment, the carboxylic acid includes capric 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-trifluorobutanoic acid. In one aspect of this embodiment, the carboxylic acid includes 3,3,3-trifluoropropanoic 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.

[0143] In another embodiment, the carboxylic acid includes, consists essentially of or consists of one more carboxylic acid having a boiling point of than about 250 °C or lower. In a further aspect of this embodiment, the carboxylic acid includes, consists essentially of or consists of one more carboxylic acid having a boiling point of than about 200 °C or lower.

[0144] In another embodiment, the carboxylic acid vapor is substantially free of any carboxylic acids having boiling points of greater than about 250 °C. In a further aspect of this embodiment, the carboxylic acid vapor is substantially free of any carboxylic acids having boiling points of greater than about 200 °C.

[0145] In another embodiment, the carboxylic acid vapor is free of any carboxylic acids having boiling points of greater than about 250 °C. In a further aspect of this embodiment, the carboxylic acidPROVISIONAL PATENT APPLICATIONATTORNEY DOCKET No. P24-161-US-PSP vapor is substantially free of any carboxylic acids having boiling points of greater than about 200 °C.

[0146] Steps (c), (e) and (g) Purging

[0147] As noted above, steps (c), (e) and (g) of the disclosed and claimed methods include purging the reactor vessel with inert gas. Purging with an inert gas removes unabsorbed excess materials and by products from the process reactor. In one embodiment, the purge gas includes argon. In another embodiment, the purge gas includes nitrogen.

[0148] In one embodiment, for example, the purge time varies from about 1 seconds to about90 seconds. In one embodiment, for example, the purge time varies from about 15 seconds to about 90 seconds. In one embodiment, for example, the purge time varies from about 15 seconds to about 60 seconds. In another embodiment, the purge time is about 30 seconds. In another embodiment, the purge time is about 60 seconds. In another embodiment, the purge time is about 90 seconds.

[0149] In one embodiment, the purge gas includes argon. In another embodiment, the purge gas includes nitrogen.

[0150] Operating Conditions

[0151] As noted above, the disclosed and claimed tin-containing film deposition process can be effectively conducted under very favorable ALD or ALD-like conditions.

[0152] In one embodiment the substrate (e.g., aluminum oxide (AI2O3), titanium nitride (TiN), silicon oxide (SiO2), zirconium oxide (ZrO2), amorphous carbon, silicon-containing underlayer) is heated on a heater stage in a reaction reactor that is exposed to the organotin precursor initially to allow the complex to chemically adsorb onto the surface of the substrate. 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 water only process is from about 25 °C to about 200 °C.

[0153] In another embodiment, the reactor pressure for depositions according to the disclosed and claimed process is < to about 100 torr. In another embodiment, the reactor pressure for depositions according to the disclosed and claimed process is < to about 75 torr. In another embodiment, the reactor pressure for depositions according to the disclosed and claimed process is < to about 50 torr. In another embodiment, the reactor pressure for depositions according to the disclosed and claimed process is < to about 40 torr. In another embodiment, the reactor pressure for depositions according to the disclosed and claimed process is < to about 30 torr. In a further aspect of this embodiment, the reactor pressure is < to about 20 torr. In a further aspect of this embodiment, the reactor pressure is < to about 10 torr. In a further aspect of this embodiment, the reactor pressure is < to about 5 torr.

[0154] In another embodiment, the above-described tin compounds and / or compositions are used in method(s) for depositing tin-containing films.PROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP

[0155] In one embodiment, the method for deposition of organotin oxide or tin oxide films of the disclosed and claimed subject matter includes, consists essentially of or consists of the steps of: a. providing one or more substrates in a reactor, where the reactor is heated to temperature of from about 25 °C to about 600 °C and optionally maintained at a pressure of about 100 torr or less; b. introducing into the reactor a vapor including, consisting essentially of or consisting of one or more compounds of Formula (I) or a composition of such compounds that forms a metal-containing (i.e., a tin-containing or a germanium-containing) layer on a surface of the substrate; c. purging the reactor with an inert gas; d. introducing one or more oxygen source to convert the tin-containing layer to an organotin oxide or tin oxide layer; and e. purging the reactor with an inert gas.

[0156] Cycles and Order of Steps

[0157] In the above-described embodiments, as well as the other embodiments described herein, the described steps (e.g., (a) through (e)) define one cycle of the method. It is to be understood that a cycle can be repeated until the desired thickness of a film is obtained.

[0158] In the embodiments described herein, it is understood that the steps of the methods may be performed in a variety of orders, may be performed sequentially or concurrently (e.g., during at least a portion of another step), and any combination thereof. In addition, the respective steps of supplying the reactants (i.e., the organotin precursor, the water-containing vapor and the carboxylic acid-containing vapor) and or the subsequent purges thereof may be performed by varying the duration of the time for supplying them to change film composition.

[0159] Films

[0160] The disclosed and claimed subject matter further includes films prepared by the methods described herein. In one embodiment, the films include, consist essentially of or consist of tin. In one embodiment, the films include, consist essentially of or consist of germanium.

[0161] In one embodiment, the films formed by the methods described herein have trenches, vias or other topographical 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 greaterPROVISIONAL PATENT APPLICATIONATTORNEY DOCKET No. P24-161-US-PSP 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 embodiment, the aspect ratio is greater than about 50.

[0162] The steps of the described and claimed processes may be repeated to provide a desired thickness of the films. The thickness of the films can range from about 10 A to about 5000 A, or about 10 A to about 1000 A, or about 10 A to about 500 A, or about 10 A to about 300 A or about 10 A to about 200 A, or about 50 A to about 1000 A, or about 50 A to about 500 A, or about 50 A to about 300 A or about 50 A to about 200 A. In one embodiment, the films formed by the methods described herein have a thickness of about 10 A to about 5000 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about 10 A to 1000 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about 10 A to 500 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about, 10 A to 300 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about, 10 A to 200 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about, 50 A to 1000 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about, 50 A to 500 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about, 50 A to 300 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about, 50 A to 200 A.

[0163] In some embodiments, a super-cycle ALD or ALD-like process may be performed, one super-cycle includes the following: steps (b) to (e) may be repeated to provide a desired thickness of the films which can range from about 50 A to about 1000 A, about 50 A to about 500 A, about 50 A to about 300 A or about 50 A to about 200 A, followed by steps (f) to (g) to modify the resulting films. The super-cycle can be repeated to provide a desired thickness of film. It is believed that reaction between the carboxylic acid and the resulting film from steps (b) to (e) may improve / stabilize the film, thus allowing the films to be more resistant to environment changes such as moisture or carbon dioxide during semi-conductor fabrication processes. Additionally, in some embodiments, steps (f) to (g) are performed before steps (d) to (e) to provide a desired thickness of the film.

[0164] Process for Preparing Sn-cluster Formulations

[0165] In another embodiment, the above-described tin compounds and / or compositions are used in method(s) for preparing Sn-cluster formulations based on the methods described in e.g. Sharps et al., Chem. Mater., 31, 4840-4850 (2019); U.S. Patent No. 9,310,684; Castellanos et al., Appl. Mat.PROVISIONAL PATENT APPLICATIONATTORNEY DOCKET No. P24-161-US-PSPInt., 12, 9881-9889 (2020); and Herman et al., Appl. Mat. Int., 11, 4514-4522 (2019). The changes in the material, coated on a wafer as a photosensitive layer, have been investigated and several hypotheses on how a solubility contrast is induced by exposure to ionizing radiation were discussed. See Castellanos et al., Appl. Mat. Int., 12, 9881-9889 (2020) and Herman et al., Appl. Mat. Int., 11, 4514-4522 (2019).

[0166] In general, cluster formation can be monitored directly in solution via119Sn-NMR, given a high enough concentration of the material. Via partial removal of the solvent(s), a higher concentration can be achieved. For these experiments, a capillary insert containing a deuterated solvent is typically used. This way, the reaction solution is not altered by addition of a further solvent. Another approach is the isolation of the compounds by complete removal of the solvent and subsequent redissolution in a deuterated solvent.

[0167] Sn-Cluster Formulations and Uses Thereof

[0168] In another aspect, the disclosed and claimed subject matter includes formulations that include (i) one or more of the disclosed and claimed Sn precursor and (ii) one or more solvents suitable for use in a spin-coating process. In one embodiment, the formulation includes (i) two or more of the disclosed and claimed Sn precursors and (ii) one or more solvents suitable for use in a spin-coating process.

[0169] In another aspect, the disclosed and claimed subject matter includes preparing the target compounds in a spin-coating solvent (mixture) at the desired concentration, circumventing the isolation of the material and direct formation of the spin-coatable formulation. In one aspect, such formulations are free of toluene.

[0170] In one embodiment, the one or more solvents suitable for use in a spin-coating process includes one or more of an alcohol, an ester, a ketone, a lactone, a diketone, a solvent with aromatic moieties, a solvent with a carboxylic acid, an amide and mixtures thereof.

[0171] In another embodiment, the one or more solvents suitable for use in a spin-coating process includes one or more of l-methoxy-2-propanyl acetate (PGMEA), l-methoxy-2-propanol (PGME), butyl acetate, amyl acetate, cyclohexyl acetate, 3 -methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone, ethyl-3-ethoxy propanoate, methyl-3- ethoxy propanoate, methyl-3-methoxy propanoate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl pivalate, ethyl pivalate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propanoate, propylene glycol monoethyl ether propanoate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N- methylpyrrolidone, dimethyl sulfoxide, gamma-butyrolactone, gamma valerolactone, cyclopentyl methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, tetramethylene sulfone,PROVISIONAL PATENT APPLICATIONATTORNEY DOCKET No. P24-161-US-PSP propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, toluene, 2-heptanone, 1 -hexanol, 4-methyl-2-pentanol and anisole. In a further aspect of this embodiment, the one or more solvents for use in a spin-coating process includes one or more of toluene, THF, cyclohexanone, PGME, PGMEA, anisole, 2-heptanone and 4- methyl-2-pentanol. In a further aspect of this embodiment, the one or more solvents for use in a spincoating process includes one or more of THF, cyclohexanone, PGME, PGMEA, anisole, 2-heptanone and 4-methyl-2-pentanol. In one aspect, such formulations are free of toluene.

[0172] In another embodiment, the Sn cluster formulations have a concentration of Sn clusters of about 1 mg / mL to about 1000 mg / mL. In another embodiment, the Sn clusters can be formulated into solutions having a concentration of Sn clusters of about 1 mg / mL to about 100 mg / mL. In another embodiment, the Sn clusters can be formulated into solutions having a concentration of Sn clusters of about 1 mg / mL to about 50 mg / mL. In another embodiment, the Sn clusters can be formulated into solutions having a concentration of Sn clusters of about 10 mg / mL to about 50 mg / mL. In another embodiment, the Sn cluster formulations have a concentration of Sn clusters of about 25 mg / mL to about 50 mg / mL. In another embodiment, the Sn cluster formulations have a concentration of Sn clusters of about 50 mg / mL to about 100 mg / mL.

[0173] The disclosed and claimed subject matter further includes using the disclosed and claimed Sn cluster formulations in EUV and ebeam processes. Such formulations are or can be used for patterning a radiation sensitive coating in a process that includes the steps of (i) forming a coating on a substrate surface with one or more of the disclosed and claimed Sn formulations, (ii) drying the coating to produce a dried layer; and (iii) irradiating at least a portion of the dried layer to form a latent image.

[0174] In one embodiment, the substrate of step (i) includes silicon. In one embodiment, the substrate of step (i) includes silicon and at least one additional material layer (i.e. , a stack of materials) on top of which the material is deposited.

[0175] In one embodiment, the dried layer of step (ii) has a thickness of about 1 nm to about 500 nm. In one embodiment, the dried layer of step (ii) has a thickness of about 10 nm to about 100 nm. In one embodiment, the dried layer of step (ii) has a thickness of about 15 nm to about 50 nm.

[0176] In one embodiment, the irradiating of step (iii) includes exposing at least a portion of the dried layer to ionizing radiation. In one aspect of this embodiment, the ionizing radiation has a wavelength range of about 10 nm to about 365 nm. In one aspect of this embodiment, the ionizing radiation is generated via electron beams.

[0177] Method of photopatteming the materials: spincoating on a substrate at 500rpm / 5s then 800-5000 rpm for 15-120 s, exposing with e-beam at 2-100 keV for 1-10000 pC or EUV (13.5 nm) through a mask, baking the exposed wafer for 0.5-20 minutes at 100-200 °C, developing forPROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP15-300 sec in organic solvent (mixtures). Solvents and mixtures thereof include, but are not limited to, 2-hetptanone, cyclohexanone, PGMEA, PGME, a mixture of anisole and PGMEA, a mixture of anisole and cyclohexanone and a mixture of anisole and 2-heptanone.

[0178] It will also be apparent to those skilled in the art that various modifications may be made in how the disclosed subject matter is practiced based on described aspects in the specification without departing from the spirit and scope of the disclosed subject matter disclosed herein.

[0179] Examples

[0180] Reference will now be made to more specific embodiments of the present disclosure and experimental results that provide support for such embodiments. The examples given below more fully illustrate the disclosed and claimed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0181] It will be apparent to those skilled in the art that various modifications and variations can be made in the disclosed subject matter and specific examples provided herein without departing from the spirit or scope of the disclosed subject matter. Thus, it is intended that the disclosed subject matter, including the descriptions provided by the following examples, covers the modifications and variations of the disclosed subject matter that come within the scope of any claims and their equivalents.

[0182] Working Example 1: Synthesis of (DMDMP)Sn(O‘Bu)3(DMDMP = 3-(N,N- dimethylamino)-2,2-dimethyl-propyl) (3-(N,N-dimethylamino)-2,2-dimethyl- propyl-tris-tertbutoxytin) in which the P-carbon is quaternary

[0183] All reactions were carried out with the strict exclusion of moisture and oxygen by using standard inert-atmosphere and Schlenk techniques. Solvents such as tetrahydrofuran (THF), 1,4-dioxane and n-penlane were dried by standard methods before use. Commercially available Sn(NMe2)4 (Strem) was used without further purification. 3-(N,N-dimethylamino)-2,2- dimethylpropyl magnesiumchloride (1) was synthesized following a general synthetic procedure for Grignard reagents using 3-(N,N-dimethylamino)-2,2-dimethyl-propylchlorid and magnesium powder. iPrSn(NMe2)3was synthesized by using iPrSnCl3and LiNMe2.

[0184] Synthesis 1A:

[0185] A solution of compound 1 in THF (c = 0.731 m / L, 10 mL) was dissolved in dry dioxane (10 mL) and the mixture was stirred for 20 min to form the bis alkyl magnesium species 2. While stirring, white solids precipitated. The suspension was filtered and the solution of bis alkyl magnesium species 2 was used without further characterization.PROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP

[0186] Synthesis IB:

[0187] Compound 2 (c = 0.366 m / L; dissolved in 20 mL of 1,4-dioxane / THF) was slowly added to a solution of Sn(NMe2)4 (2.16 g, 7.32 mmol) in THF (20 mL) at -78 °C. The reaction mixture was allowed to warm to room temperature overnight. All volatiles were removed in vacuum, and the residue was extracted with n-pentane (3 x 5 mL). The n-penlane was removed in vacuum, and the residue was purified by distillation (70 °C at 2.8 x 10’2mbar). The product ((DMDMP)Sn(NMe2)3; compound “3”) was obtained as a colorless liquid. Yield: 1.9 g (71 %).

[0188] By using 2 as the starting material in 1,4-dioxane, the ratio of mono 3 and bis alkyl species 4 is 95:5, respectively. A simple distillation is sufficient to separate both products to produce compound 3 with a purity of >99%.

[0189] Analysis

[0190] 8 2.85 (t, Sn-N(CH3)2, 18H), 2.19 (s, N(CH3)2,6H), 1.97 (s, CH2-N(CH3)2, 2H), 1.32 (t, Sn-CTL, 2H), 0.99 (s, C7 / 3, 6H) ppm.119Sn NMR (186.6 MHz, CLDr.) of 3: 8 - 40.4 (s) ppm.

[0191] Synthesis 1C:

[0192] Compound 3 (630 mg, 1.87 mmol) was dissolved in tert-butanol (4.4 ml, 46.72 mmol) and stirred for 16 h at RT. Immediate bubble formation was observed. The excess tertbutanol was removed and the solid was dried to yield 790 mg (99%) of compound 4.

[0193] Analysis

[0194] JH NMR (500 MHz, C6D6) of 4: 8 2.19 (s, N(CH3)2, 6H), 1.79 (s, CH2-O(CH3)2, 2H), 1.55 (s, OC(CH3)3, 27 H), 1.23 (s, Sn-CTL, 2H), 0.87 (s, C7 / 3, 6H) ppm.119Sn NMR (186.6 MHz, C6D6) of 4: 8 - 296.7 (s) ppm.

[0195] Working Example 2: Synthesis of (MODMP)Sn(O‘Bu)3(MODMP = 3- methoxy-l,l-dimethyl-propyl) (3-methoxy-l,l-dimethyl-propyl-tris- tertbutoxytin) in which the a-carbon is quaternary

[0196] All reactions were carried out with the strict exclusion of moisture and oxygen by using standard inert-atmosphere and Schlenk techniques. Solvents such as tetrahydrofuran (THF) and n-pentane were dried by standard methods before use. Commercially available Sn(NMe3)4PROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP(Strem) was used without further purification. 3 -methoxy- 1,1-dimethyl-propylchlorid (5) was synthesized in a two-step process according to literature procedures. See Chem. Eur. J., 8, 3773 (2002); J. Am. Soc., 123, 10127(2001).

[0197] Synthesis 2A:

[0198] 3 -methoxy- 1,1 -dimethylpropyl magnesiumchloride (6) was synthesized following a general synthetic procedure for Grignard reagents using 3 -methoxy- 1,1-dimethyl-propylchlorid (5) and magnesium turnings.

[0199] Synthesis 2B:

[0200] Compound 6 (c = 0.207 m / L; dissolved in 21.3 mL of THF) was slowly added to a solution of Sn(NMe2)4 (1.30 g, 4.41 mmol) in THF (5 mL) at -78 °C. The reaction mixture was allowed to warm to room temperature overnight. All volatiles were removed in vacuum, and the residue was extracted with n-pentane (2 x 20 mL). The n-penlane was removed in vacuum, and the residual liquid was purified by distillation (40 °C at 1.4 x 10’2mbar). The product ((MODMP)Sn(NMe2)3; compound “7”) was obtained as a colorless waxy solid. Yield: 1.4 g (88 %).

[0201] Analysis

[0202] JH NMR (500 MHz, C6D6) of 7: 8 3.17 (t, CH2-OCH3, 2H), 3.06 (s, OCH3, 3H), 2.91 (t, Sn-(N(CH3)2)3, 18H), 1.64 (t, CH2-CH2-OCH3, 2H), 1.26 (t, Sn-C-CH3, 6H) ppm.119Sn NMR (186.6 MHz, C6D6) of 7: 8 - 109 (s) ppm.

[0203] Synthesis 2C:

[0204] Compound 7 (400 mg, 1.14 mmol) was dissolved in tert-butanol (4.4 ml, 46.72 mmol) and stirred for 16 h at RT. Immediate bubble formation was observed. The excess tert- butanol was removed and the solid was dried to yield 490 mg (99%) of compound 8.

[0205] Analysis

[0206] JH NMR (500 MHz, C6D6) of 7: 8 3.21 (t, CH2-OCH3, 2H), 3.15 (s, OCH3, 3H), 1.67 (t, Sn-(OC(CH3)3)3, 27 H), 1.67 (t, CH2-CH2-OCH3, 2H), 1.51 (s, Sn-(OC(CH3)3)3, 27 H),PROVISIONAL PATENT APPLICATIONATTORNEY DOCKET No. P24-161-US-PSP1.30 (s, Sn-C-CH3, 6H) ppm.119Sn NMR (186.6 MHz, C6D6) of 7: 8 - 299 (s) ppm.

[0207] Working Example 3: Snl2 Cluster Fabrication [(XRSn)i2Oi4(OH)s] Formulations

[0208] Synthesis 3A: XR = DMDMP

[0209] According to literature (Sharps et al., Chem. Mater., 31, 4840-4850 (2019); U.S. Patent No. 9,310,684; Castellanos et al., Appl. Mat. Int., 12, 9881-9889 (2020); and Herman et al., Appl. Mat. Int., 11, 4514-4522 (2019)) compound 4 (344 mg, 0.76 mmol) was transformed to the respective Sn-12 cluster (compound 9, [((DMDMP)Sn)i2Oi4(OH)s]) by dissolving it in PGME (10 ml) and adding water (51.4 pl, 2.85 mmol, 3.75 eq.). The solution was stirred for 14 h at RT and a small amount was concentrated for NMR analysis. The rest was used as a spin coating formulation (see Working Example 4).

[0210] Analysis

[0211] FIG. 1 shows the119Sn NMR of compound 9. Only the two expected signals are observed indicating the clean formation of the Snl2 cluster without impurities.119Sn NMR (186.6 MHz, CTIV) of 7: 8 - 285 (m) and -455 (m) ppm.

[0212] Synthesis 3B : XR = MODMP

[0213] According to literature (Sharps et al., Chem. Mater., 31, 4840-4850 (2019); U.S. Patent No. 9,310,684; Castellanos et al., Appl. Mat. Int., 12, 9881-9889 (2020); and Herman et al., Appl. Mat. Int., 11, 4514-4522 (2019)) compound 8 (353 mg, 0.80 mmol) was transformed to the respective Sn-12 cluster (compound 10, [((MODMP)Sn)i2Oi4(OH)s]) by dissolving it in PGME (10 ml) and adding water (54.3 pl, 3.01 mmol, 3.75 eq.). The solution was stirred for 14 h at RT and a small amount was concentrated for NMR analysis. The rest was used as a spin coating formulation (see Working Example 4).

[0214] Analysis

[0215] FIG. 2 shows the119Sn NMR of compound 9. The two expected signals are observed indicating the formation of the Snl2 cluster without minor impurities.119Sn NMR (186.6 MHz, CTIV) of 7: 8 - 340 (m) and -484 (m) ppm.

[0216] Working Example 4: Use of Snl2 Cluster [(XRSn)i2Oi4(OH)s] Formulations in Spin Coating and E-beam Exposure Experiments

[0217] Formulations of compounds 9 and 10 were spin coated on Si wafers (800-4000 rpm), that were treated with oxygen plasma (400 W, 10 min). After a soft bake of 100 °C for 120 s, wafers were exposed with an E-beam radiation (30 keV) with dose levels from 10 to 5000 pC / cm2. After exposure, a post exposure bake was done at 170 °C for 120 s, then wafers were developed with 2-heptanone for 120 s at RT. Afterwards, the wafers were rinsed with water and dried under nitrogen. The unexposed films had a thickness of ~30 nm which was determined by profilometry. The structures were also determined via profilometry and peak height to dose werePROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP translated into fitted dose level curves where these examples showed D50 values of 950 pC / cm2(compound 9) and 220 pC / cm2(compound 10).

[0218] Although the invention has been described and illustrated with a certain degree of particularity, it is understood that the disclosure has been made only by way of example, and that numerous changes in the conditions and order of steps can be resorted to by those skilled in the art without departing from the spirit and scope of the invention.

Claims

PROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSPClaimsWhat is claimed is1. A compound of Formula (I): (XR)M(0R1)3, wherein(i) M = Sn or Ge;(ii) R is a branched Cs to Cio alkylene linker group wherein (i) three to eight main chain carbon moieties connect M and X and (ii) at least one of the first three main chain carbon moieties that connect M and X is a quaternary carbon moiety that is free of hydrogen;(iii) R1is selected from a linear Ci to C6 alkyl group, a branched C4 to C6 alkyl group or a cyclic C3 to C6 alkyl group; and(iv) X is selected is one of -OR2or -NR3R4where R2, R3and R4are each independently selected from a linear Ci to C6 alkyl group, a branched C4 to C6 alkyl group or a cyclic C3 to Co alkyl group.

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

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

4. The organotin compound of claim 1, wherein R is a branched Cs alkylene.

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

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

7. The organotin compound of claim 1, wherein R is a branched Cs alkylene.

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

9. The organotin compound of claim 1, wherein R is a branched Cio alkylene.

10. The organotin compound of claim 1, wherein R the Cs to Cio alkylene linker group consist of three main chain carbon moieties connecting M and X.

11. The organotin compound of claim 1, wherein R the Cs to Cio alkylene linker group consist of four main chain carbons moieties connecting M and X.

12. The organotin compound of claim 1, wherein R the Cs to Cio alkylene linker group consist of five main chain carbons moieties connecting M and X.

13. The organotin compound of claim 1, wherein R the Cs to Cio alkylene linker group consist of six main chain carbons moieties connecting M and X.

14. The organotin compound of claim 1, wherein R the Cs to Cio alkylene linker group consist of seven main chain carbons moieties connecting M and X.

15. The organotin compound of claim 1, wherein R the Cs to Cio alkylene linker group consist of eight main chain carbons moieties connecting M and X.

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

17. The organotin compound of claim 1, wherein R the -carbon moiety is a hydrogen-freePROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP quaternary carbon moiety.

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

19. The organotin compound of claim 1, wherein R two or more of the a-carbon moiety, P- carbon moiety and y-carbon moiety are hydrogen-free quaternary carbon moieties.

23. The organotin compound of claim 1, wherein R1is a linear Ci to C6 alkyl group.

24. The organotin compound of claim 1, wherein R1is a linear Ci alkyl group.

25. The organotin compound of claim 1, wherein R1is a linear C2 alkyl group.

26. The organotin compound of claim 1, wherein R1is a linear C3 alkyl group.

27. The organotin compound of claim 1, wherein R1is a linear C4 alkyl group.

28. The organotin compound of claim 1, wherein R1is a linear Cs alkyl group.

29. The organotin compound of claim 1, wherein R1is a linear C6 alkyl group.

30. The organotin compound of claim 1, wherein R1is a branched C4 to C6 alkyl group.

31. The organotin compound of claim 1, wherein R1is a branched C4 alkyl group.

32. The organotin compound of claim 1, wherein R1is a branched C5 alkyl group.

33. The organotin compound of claim 1, wherein R1is a branched C6 alkyl group.

34. The organotin compound of claim 1, wherein R1is a cyclic C3 to C6 alkyl group.

35. The organotin compound of claim 1, wherein R1is a cyclic C3 alkyl group.

36. The organotin compound of claim 1, wherein R1is a cyclic C4 alkyl group.

37. The organotin compound of claim 1, wherein R1is a cyclic C5 alkyl group.

38. The organotin compound of claim 1, wherein R1is a cyclic C6 alkyl group.

39. The organotin compound of claim 1, wherein X is a -OR2group.

40. The organotin compound of claim 1, wherein X is a -OR2group and R2is a linear Ci to C6 alkyl group.

41. The organotin compound of claim 1 , wherein X is a -OR2group and R2is a linear Ci alkyl group.

42. The organotin compound of claim 1 , wherein X is a -OR2group and R2is a linear C2 alkyl group.

43. The organotin compound of claim 1 , wherein X is a -OR2group and R2is a linear C3 alkyl group.

44. The organotin compound of claim 1 , wherein X is a -OR2group and R2is a linear C4 alkyl group.

45. The organotin compound of claim 1 , wherein X is a -OR2group and R2is a linear C5 alkyl group.

46. The organotin compound of claim 1 , wherein X is a -OR2group and R2is a linear C6 alkyl group.

47. The organotin compound of claim 1, wherein X is a -OR2group and R2is a branched C4 to C6 alkyl group.PROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP48. The organotin compound of claim 1, wherein X is a -OR2group and R2is a branched C4 alkyl group.

49. The organotin compound of claim 1, wherein X is a -OR2group and R2is a branched C5 alkyl group.

50. The organotin compound of claim 1, wherein X is a -OR2group and R2is a branched C6 alkyl group.

51. The organotin compound of claim 1, wherein X is a -OR2group and R2is a cyclic C3 to C6 alkyl group.

52. The organotin compound of claim 1, wherein X is a -OR2group and R2is a cyclic C3 alkyl group.

53. The organotin compound of claim 1, wherein X is a -OR2group and R2is a cyclic C4 alkyl group.

54. The organotin compound of claim 1, wherein X is a -OR2group and R2is a cyclic C5 alkyl group.

55. The organotin compound of claim 1, wherein X is a -OR2group and R2is a cyclic C6 alkyl group.

56. The organotin compound of claim 1, wherein X is a -NR3R4group.

57. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a linear Ci to C6 alkyl group.

58. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a linear Ci alkyl group.

59. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a linear C2 alkyl group.

60. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a linear C3 alkyl group.

61. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a linear C4 alkyl group.

62. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a linear Cs alkyl group.

63. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a linear C6 alkyl group.

64. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a branched C4 to C6 alkyl group.

65. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a branched C4 alkyl group.PROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP66. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a branched C5 alkyl group.

67. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a branched C6 alkyl group.

68. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a cyclic C3 to Ce alkyl group.

69. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a cyclic C3 alkyl group.

70. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a cyclic C4 alkyl group.

71. The organotin compound of claim 1, wherein X is a -NR3R4group and one or both of R3and R4is a cyclic C5 alkyl group.

72. The organotin compound of claim 1 , wherein X is a -NR3R4group and one or both of R3and R4is a cyclic C6 alkyl group.

73. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of (NMe2CH2CMe2CH2)Sn(O‘Bu)3.

74. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of (OMeCH2CMe2CH2)Sn(O‘Bu)3.

75. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of (OMeCH2CH2CMe2)Sn(O‘Bu)3.

76. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of (NMe2CH2CH2CMe2)Sn(O‘Bu)3.

77. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of one or more of 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris- tertbutoxytin, 3-(N,N-diethylamino)-2,2-dimethyl-propyl-tris-tertbutoxytin, 3-(N,N- dimethylamino)-2,2-dimethyl-propyl-tris-tertamyloxytin, 3-(N,N-diethylamino)-2,2-dimethyl- propyl-tris-tertamyloxytin, 3-(N,N-dimethylamino)-l,l-dimethyl-propyl-tris-tertbutoxytin, 3- methoxy-2,2-dimethyl-propyl-tris-tertbutoxytin, 3-ethoxy-2,2-dimethyl-propyl-tris-tertbutoxytin, 3-methoxy-2,2-dimethyl-propyl-tris-tertamyloxytin, 3-ethoxy-2,2-dimethyl-propyl-tris- tertamyloxytin, 3-methoxy- 1 , 1 -dimethyl-propyl-tris-tertbutoxytin, 3-ethoxy- 1 , 1 -dimethyl-propyl- tris-tertbutoxytin, 3 -methoxy- 1,1-dimethyl-propyl-tris-tertamyloxytin and 3 -ethoxy- 1,1 -dimethyl- propyl-tris-tert amyloxytin.

78. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-tertbutoxytin.

79. The compound of claim 1, wherein the compound of Formula (I) comprises, consistsPROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP essentially of or consists of 3-(N,N-diethylamino)-2,2-dimethyl-propyl-tris-tertbutoxytin.

80. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of 3-(N,N-dimethylamino)-2,2-dimethyl-propyl-tris-tertamyloxytin.

81. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of 3-(N,N-diethylamino)-2,2-dimethyl-propyl-tris-tertamyloxytin.

82. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of 3-(N,N-dimethylamino)-l,l-dimethyl-propyl-tris-tertbutoxytin.

83. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of 3-methoxy-2,2-dimethyl-propyl-tris-tertbutoxytin.

84. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of 3-ethoxy-2,2-dimethyl-propyl-tris-tertbutoxytin.

85. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of 3-methoxy-2,2-dimethyl-propyl-tris-tertamyloxytin.

86. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of 3-ethoxy-2,2-dimethyl-propyl-tris-tertamyloxytin.

87. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of 3-methoxy-l,l-dimethyl-propyl-tris-tertbutoxytin.

88. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of 3-ethoxy-l,l-dimethyl-propyl-tris-tertbutoxytin.

89. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of 3-methoxy-l,l-dimethyl-propyl-tris-tertamyloxytin.

90. The compound of claim 1, wherein the compound of Formula (I) comprises, consists essentially of or consists of 3-ethoxy-l,l-dimethyl-propyl-tris-tertamyloxytin.

91. The compound of claim 1, wherein the compound of Formula (I) comprises, consistsPROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP93. A composition comprising (i) one or more compounds of any of claims 1-91 and (ii) one or more solvents selected from the group of toluene, mesitylene, cumene (isopropylbenzene), p-cymene (4-isopropyl toluene), 1,3 -diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n- butylcyclohexane, decahydronaphthalene (decalin) and combinations thereof.

94. A method for depositing organotin oxide or tin oxide films comprising the steps of: a. providing one or more substrates in a reactor, where the reactor is heated to temperature of from about 25 °C to about 600 °C and optionally maintained at a pressure of about 100 torr or less; b. introducing into the reactor a vapor comprising one or more compounds or compositions of any of claims 1-93; c. purging the reactor with an inert gas; d. introducing one or more oxygen source to convert the metal-containing layer to an organometal oxide or metal oxide layer; and e. purging the reactor with an inert gas.

95. The method of claim 94, further comprising the steps of: f. introducing one or more carboxylic acid vapor having the formula R5COOH where R5is selected from hydrogen, a linear Ci to C6 alkyl group, a branched C3 to C6 alkyl group, a C3 to C6 cyclic alkyl group, a C2 to C6 alkenyl group, a C3 to C6 alkynyl group, and a C4 to C10 aryl group to react with the organometal oxide or metal oxide layer; and g. purging the reactor with an inert gas.

96. The method of claim 94, wherein the one or more compounds or compositions comprises tin.

97. The method of claim 94, wherein the one or more compounds or compositions comprises germanium.

98. The method of claim 94, wherein step (b) comprises pulsing the vapor for about 0.1 seconds to about 3 seconds.

99. The method of claim 94, wherein the step (d) one or more oxygen source comprises one or more of oxygen (O2), ozone (O3), nitric oxide (NO), water (H2O) vapor, hydrogen peroxide (H2O2), oxygen plasma (O*), NxOy(wherein x = 1 or 2 and y = 1, 2, 3 or 4) and combinations thereof.PROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP100. The method of claim 94, wherein the step (d) one or more oxygen source comprises water vapor.

101. The method of claim 94, wherein the step (d) one or more oxygen source comprises water vapor.

102. The method of claim 94, wherein step (d) comprises pulsing the one or more oxygen source for about 0.5 seconds to about 5 seconds.

103. The method of claim 94, wherein step (f) one or more carboxylic acid vapor comprises one or more of formic acid, acetic acid, propionic acid, butyric acid, iso-butyric acid, valeric acid, 2- methylbutyric acid, 3 -methylbutyric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, fluoroacetic acid, chloroacetic acid, iodoacetic acid, dichloroacetic acid, 4,4,4- trifluorobutanoic acid, 3,3,3-trifluoropropanoic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 4,4-difluorocyclohexanecarboxylic acid and tetrahydro-3-furancarboxylic acid.

104. The method of claim 94, wherein step (f) one or more carboxylic acid vapor consists of a carboxylic acid has a boiling point of about 250 °C or lower.

105. The method of claim 94, wherein step (f) one or more carboxylic acid vapor consists of a carboxylic acid has a boiling point of about 200 °C or lower.

106. The method of claim 94, wherein step (f) one or more carboxylic acid vapor comprises acetic acid.

107. The method of claim 94, wherein step (f) one or more carboxylic acid vapor consists of acetic acid.

108. A tin-containing film deposited using one or more organotin compounds or compositions of any of claims 1-93.

109. A tin-containing film deposited by the method of any of claims 94-107.

110. An organotin oxide or tin oxide film deposited by the method of any of claims 94-107, wherein the film has an aspect ratio of about 1 to about 60.

111. An organotin oxide or tin oxide film deposited by the method of any of claims 94-107, wherein the film has a thickness of about 10 A to about 5000 A.

112. A germanium-containing film deposited using one or more organogermanium compounds or compositions of any of claims 1-93.

113. A germanium-containing film deposited by the method of any of claims 94- 107.

114. An organogermanium oxide or germanium oxide film deposited by the method of any of claims 94-107, wherein the film has an aspect ratio of about 1 to about 60.

115. An organogermanium oxide or germanium oxide film deposited by the method of any of claims 94-107, wherein the film has a thickness of about 10 A to about 5000 A.

116. A Snl2 cluster composition comprising (i) one or more compounds of any of claims 1-91, (ii) water, and (iii) one or more solvents.PROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSP117. A spin-coatable formulation comprising:(i) one or more of the composition of claim 116; and(ii) one or more solvents suitable for use in a spin-coating process.

118. The spin-coatable formulation of claim 117, wherein the one or more solvents suitable use in a spin-coating process comprises one or more of an alcohol, an ester, a ketone, a lactone, a diketone, a solvent with aromatic moieties, a solvent with a carboxylic acid, an amide and mixtures thereof.

119. The spin-coatable formulation of claim 117, wherein the one or more solvents suitable use in a spin-coating process comprises one or more of l-methoxy-2-propanyl acetate (PGMEA), 1- methoxy-2-propanol (PGME), butyl acetate, amyl acetate, cyclohexyl acetate, 3 -methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone, ethyl-3-ethoxy propanoate, methyl-3-ethoxy propanoate, methyl-3-methoxy propanoate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl pivalate, ethyl pivalate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propanoate, propylene glycol monoethyl ether propanoate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3 -methyl-3 -methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, gamma-butyrolactone, gamma valerolactone, cyclopentyl methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, tetramethylene sulfone, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, toluene, 2-heptanone, 1 -hexanol, 4-methyl-2-pentanol and anisole.

120. The spin-coatable formulation of claim 117, wherein the one or more solvents suitable use in a spin-coating process comprises one or more of toluene, THF, cyclohexanone, PGME, PGMEA, anisole, 2-heptanone and 4-methyl-2-pentanol.

121. The spin-coatable formulation of claim 117, wherein the one or more solvents suitable use in a spin-coating process comprises one or more of THF, cyclohexanone, PGME, PGMEA, anisole, 2- heptanone and 4-methyl-2-pentanol.

122. The spin-coatable formulation of claim 117, wherein the formulation is free of toluene.

123. The spin-coatable formulation of claim 117, wherein the formulation comprises one of 2- hetptanone, cyclohexanone, PGMEA, PGME, a mixture of anisole and PGMEA, a mixture of anisole and cyclohexanone and a mixture of anisole and 2-heptanone.

124. The spin-coatable formulation of claim 117, wherein the formulation has a concentration of Sn cluster of about 1 mg / mL to about 1000 mg / mL.

125. The spin-coatable formulation of claim 117, wherein the formulation has a concentration of Sn cluster of about 1 mg / mL to about 100 mg / mL.

126. The spin-coatable formulation of claim 117, wherein the formulation has a concentration ofPROVISIONAL PATENT APPLICATION ATTORNEY DOCKET No. P24-161-US-PSPSn cluster of about 1 mg / mL to about 50 mg / mL.

127. The spin-coatable formulation of claim 117, wherein the formulation has a concentration of Sn cluster of about 10 mg / mL to about 50 mg / mL.

128. The spin-coatable formulation of claim 117, wherein the formulation has a concentration of Sn cluster of about 25 mg / mL to about 50 mg / mL.

129. The spin-coatable formulation of claim 117, wherein the formulation has a concentration of Sn cluster of about 50 mg / mL to about 100 mg / mL.

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