Tin(II) amide / alkoxide precursors for EUV-patternable films

Abstract

The present invention provides certain mixed Sn(II) amide / alkoxide precursor compounds. These compounds are useful in precursor compositions for vapor deposition of tin-containing films, such as tin oxide films, on microelectronic device surfaces. These precursor compounds are useful, for example, in vapor deposition methods, when paired with certain counter reactants, for extreme ultraviolet light (EUV) lithography techniques used in microelectronic device manufacturing. In this method, the resulting organotin polymer surface is thus EUV patternable, insofar as it is exposed to a patterned beam of EUV light and the exposed portions are subjected to further reaction, thereby creating chemically and physically distinct regions, which allow further processing and lithography of exposed and / or non-exposed regions, and lithography to pursue the final assembled microelectronic device.

Description

[Technical Field]

[0001] Priority claims This disclosure claims priority to U.S. Provisional Patent Application No. 63 / 239,648, filed September 1, 2021, which is incorporated herein by reference.

[0002] The present invention is in the field of organotin chemistry and, in particular, relates to certain Sn(II) vapor deposition precursor compounds and methods for their synthesis. [Background technology]

[0003] Certain organometallic compounds have been shown to be useful as precursors for the deposition of high-purity metal oxide films in applications such as extreme ultraviolet (EUV) lithography techniques used to fabricate microelectronic devices. In this method, certain organometallic precursors are utilized in conjunction with a counter-reactant to form a polymerized organometallic film. A pattern is then formed on the surface by exposing the EUV-patternable film, which involves exposing the film to a patterned beam of EUV light, followed by a post-exposure bake of the resulting microelectronic device surface in ambient air. This treatment with patterned EUV light leaves some exposed and some unexposed portions of the surface, which allows for further processing and patterning due to the distinct physical and chemical differences between the two regions. See, e.g., U.S. Patent Publication No. 2021 / 0013034.

[0004] Thus, there is a need for further development regarding precursor composition and counter-reactant pairings that can be used in the present dry (photo)resist processes. Summary of the Invention

[0005] In summary, the present invention provides certain Sn(II) amide, Sn(II) alkoxide, and mixed Sn(II) amide / alkoxide precursor compounds. These compounds are useful in precursor compositions for the vapor deposition of tin-containing films, such as tin oxide films, on the surface of microelectronic device substrates. Furthermore, the precursor compounds of the present invention, when combined with certain co-reactants in vapor deposition processes, are useful in extreme ultraviolet (EUV) lithography techniques used in microelectronic device fabrication. In this method, the resulting organotin polymer surface is EUV-patternable when exposed to a patterned beam of EUV light and the exposed portions are subjected to further reaction, thereby creating chemically and physically distinct regions that allow further processing and lithography of exposed and / or unexposed regions, as well as lithography to produce a final assembled microelectronic device. [Brief explanation of the drawings]

[0006] [Figure 1] FIG. 1 is a graph of STA-DSC (Simultaneous Thermal Analysis-Differential Scanning Calorimetry) plots of the compounds Sn(Ot-butyl)(N(CH3)2), Sn(O-isopropyl)(N(CH3)2), Sn(O-neopentyl)(N(CH3)2), and [Sn(N(CH3)2)2]2. DETAILED DESCRIPTION OF THE INVENTION

[0007] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. As used in this specification and the appended claims, the term "or" is generally used in its sense including "and / or" unless the content clearly dictates otherwise.

[0008] The term "about" generally refers to a range of numbers that are considered equivalent to the recited value (e.g., having the same function or result). In many cases, the term "about" may include numbers that are rounded to the nearest significant figure.

[0009] Numerical ranges expressed using endpoints include all numbers subsumed within that range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0010] In one aspect, the present invention provides compounds of formula (I), (II) and (III): TIFF0007781261000001.tif37170 [wherein R is a C1-C4 alkyl, and R 1 is C1-C5 alkyl] In one embodiment, the composition contains 100 ppm or less of a material other than a compound of formula (I), (II), and (III).

[0011] In the above formula, R 1 is selected from groups such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, and neopentyl. In one embodiment, each R is methyl and each R 1 is isopropyl. In one embodiment, each R is methyl and each R 1 is tert-butyl. In one embodiment, each R is methyl and each R 1 In another embodiment, each R is methyl and each R 1 is neopentyl. In certain embodiments, the precursor composition is highly pure, such that it contains no more than 50, 10, or 1 ppm of materials other than the specified compounds of formulas (I), (II), and (III). In certain embodiments, the materials other than the specified compounds are silicon-containing materials.

[0012] In another embodiment, the compounds of formula (I), (II) and (III) are compounds of the formula: TIFF0007781261000002.tif24170, wherein each R is a C1-C4 alkyl, to give a compound of formula HOR 1 an alcohol of the formula 1 is C1-C5 alkyl] in one step. A non-polar aprotic solvent such as hexane can be used in this reaction. Scheme 1: Please refer to TIFF0007781261000003.tif47170.

[0013] This synthetic approach produces products comprised of compounds of formula (I) and / or (II), and / or (III), either alone, in mixtures, or with each compound in dynamic equilibrium with the others. These organotin precursor compounds are in either liquid or solid form and possess sufficient volatility to be useful in a variety of vapor phase deposition methods when deposition of tin-containing films onto microelectronic device surfaces is desired.

[0014] As noted above, the starting material of Formula (A) can be prepared in highly pure form using the following procedure. It has been found that the compound of Formula (A) is photosensitive to gaseous decomposition by-products. Generally, SnCl is dissolved in a polar aprotic solvent such as tetrahydrofuran, cooled to a temperature of about 15°C, and then treated with a stoichiometric portion of solid LiN(R) (e.g., LiN(CH) where R is methyl). The slightly exothermic reaction is then cooled back to about 15°C, and then an additional portion is added, and the cycle is repeated until completion. The resulting reaction mixture is then evaporated in vacuo, and the resulting solid is washed with a nonpolar solvent such as hexane. Recrystallization from hexane typically results in a purity of at least about 99.0%, or at least about 99.7%. (In other words, less than about 1 weight percent impurities.) The order of addition and solvent selection has been found to be critical. However, when SnCl is added to LiN(CH) in a non-polar solvent such as hexane, then the compound LiSn(N(CH)) is isolated as the major product, instead of the desired [Sn(N(CH)] compound.

[0015] Using this approach, compounds of Formula (A) can be prepared, with or without subsequent purification, to provide materials having less than about 1 weight percent, less than about 0.5 weight percent, or less than about 0.1 weight percent impurities other than the compound of Formula (A). This level of purity is believed to be one factor that allows compounds of Formula (A) to be used directly as liquid precursors in the vapor deposition of tin-containing films onto microelectronic device substrates. Thus, in a third aspect, the present invention provides a method for depositing a tin-containing film onto a microelectronic device surface in a reaction zone under vapor deposition conditions, comprising introducing into the reaction zone a precursor composition comprising at least one compound of Formula (A).

[0016] In the above embodiment, as noted in Scheme 1 above, a compound of formula HOR 1is utilized in an amount of approximately 2 molar equivalents (eg, about 1.8 to about 2.2 molar equivalents) relative to the number of moles of starting material of formula (A).

[0017] In another aspect, the present invention provides a compound of formula HOR 1 is utilized in an amount of approximately 4 molar equivalents (e.g., about 3.6 to about 4.4, or about 3.8 to about 4.2, or about 3.9 to about 4.1 molar equivalents) relative to the number of moles of starting material of formula (A), to provide compounds of formulas (IV), (V), and (VI). This reaction can be carried out as shown in Scheme II below: Proceed as shown in TIFF0007781261000004.tif42170.

[0018] In another aspect, the present invention provides a precursor composition comprising at least one compound selected from Formulas (IV), (V), and (VI), wherein the composition contains 100 ppm or less of materials other than compounds of Formulas (IV), (V), and (VI). In certain embodiments, the precursor composition is highly pure, and thus contains 50, 10, or 1 ppm or less of materials other than the specified compounds of Formulas (IV), (V), and (VI). In certain embodiments, the materials other than the specified compounds are silicon-containing compounds.

[0019] Compounds of formula (IV), (V), and (VI), like compounds (I), (II), and (III) mentioned above, are useful as precursors. As with compounds (I), (II), and (III), the present synthetic approach produces products comprised of compounds of formula (IV) and / or (V), and / or (VI), either alone, in mixtures, or in mixtures with each compound in dynamic equilibrium with the others.

[0020] In another embodiment, a compound of formula SnX2, where X is selected from chloro, bromo, or iodo, is reacted with approximately 1 molar equivalent of a compound of formula MOR 1(e.g., about 0.8 to about 1.2, or about 0.9 to about 2.1 molar equivalents) of a compound of formula M-N(R), where M is selected from Groups I and II of the Periodic Table, to form a compound of formula M-N(R), according to Scheme III: Compounds of formula (I), (II) and (III) according to TIFF0007781261000005.tif42170 are obtained.

[0021] In one embodiment, M is selected from lithium, sodium, potassium, and magnesium.

[0022] In another embodiment, a compound of formula SnX2, where X is selected from chloro, bromo, or iodo, is reacted with approximately 2 molar equivalents (e.g., about 1.8 to about 2.2, or about 1.9 to about 2.1 molar equivalents) of a compound of formula MOR 1 wherein M is selected from Groups I and II of the Periodic Table, according to Scheme IV: As shown in TIFF0007781261000006.tif46170, compounds of formula (IV), (V) and (VI) are provided.

[0023] In one embodiment, M is selected from lithium, sodium, potassium, and magnesium.

[0024] In another aspect, the present invention provides compounds of formula (IV), (V) and (VI), which are believed to be useful as precursors as described for compounds (I), (II) and (III).

[0025] As mentioned above, the compounds of the present invention are believed to be particularly useful in patterning substrates of microelectronic devices using extreme ultraviolet light (EUV) technology. In this regard, see U.S. Patent Publication No. 2021 / 0013034, which is incorporated herein by reference. It is contemplated that the precursor composition of the present invention is mixed in the form of a vapor stream with a counter-reactant in such a manner as to form an organometallic material in oligomeric or polymeric form on the surface of a microelectronic device, such as a silicon wafer. In this way, the film thus formed becomes an EUV-patternable film, given its reactivity with EUV light.

[0026] Thus, in another aspect, the present invention provides a method for depositing an EUV patternable film on a microelectronic device surface in a reaction region under vapor deposition conditions, a. a precursor composition selected from at least one compound of formulas (I) to (VI) and (A); b.-OR 1 and -N(R)2 moieties, where R 1 is selected from C1-C5 alkyl, and R is C1-C4 alkyl; A precursor composition is provided comprising a reactant selected from:

[0027] As specified, suitable counter reactants are the -OR groups of the compounds of formulae (I) to (VI) and (A) described above. 1 and / or compounds that can replace the -N(R)2 group, including materials such as water, peroxides such as hydrogen peroxide, di- or polyhydroxy alcohols, hydrogen sulfide, hydrogen disulfide, trifluoroacetaldehyde monohydrate, fluorinated di- or polyhydroxy alcohols, and fluorinated glycols.

[0028] The thin film thus formed is SnO xwherein x is from about 0.1 to about 2. Moreover, these EUV-patternable thin films typically vary in thickness from about 0.5 to about 100 nm.

[0029] In certain embodiments, vapor deposition conditions include reaction conditions known as chemical vapor deposition, pulsed chemical vapor deposition, and atomic layer deposition. Pulsed chemical vapor deposition utilizes a series of alternating pulses of precursor compositions and counter-reactants, with or without intermediate (inert gas) purge steps, to build film thickness to a desired endpoint.

[0030] In certain embodiments, the pulse time (i.e., the duration of exposure of the precursor to the substrate) for the precursor compounds indicated above ranges from about 1 to 30 seconds. If a purge step is utilized, the duration is about 1 to 20 seconds or 1 to 30 seconds. In other embodiments, the pulse time for the co-reactant ranges from 5 to 60 seconds.

[0031] In one embodiment, the vapor deposition conditions include a temperature in the reaction zone of about 0° C. to about 250° C., or about 22° C. to about 150° C., and a vacuum of about 10 mTorr to about 10 Torr.

[0032] A precursor composition comprising a compound selected from at least one of formulas (I) to (VI) and (A) above, when used in conjunction with the above-mentioned counter reactant material, can be used to form (a) a tin-containing film and (b) a high-purity EUV-patternable film. In the eighth and ninth embodiments, any suitable vapor deposition technique, such as chemical vapor deposition (CVD), digital (pulsed) CVD, atomic layer deposition (ALD), or flowable chemical vapor deposition (FCVD), can be utilized.

[0033] In a tenth aspect of the present invention, the above compounds can be reacted with a counter reactant and the surface of a substrate of a desired microelectronic device in a reaction region in any suitable manner, for example, in a single wafer CVD or ALD, or in a furnace containing multiple wafers.

[0034] Alternatively, the method of the present invention can be carried out as an ALD or ALD-like method. As used herein, the term "ALD or ALD-like" refers to a method such as (i) in which each reactant, including a precursor composition comprising a compound selected from Formulas (I) to (VI), and (in the case of the ninth embodiment) a counter reactant, are sequentially introduced into a reactor, such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor, or (ii) in which each reactant is exposed to the substrate or microelectronic device surface by moving or rotating the substrate through different sections of the reactor, each section being separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0035] The deposition methods disclosed herein can involve one or more purge gases. A purge gas is an inert gas used to purge away unconsumed reactants and / or reaction by-products and that does not react with either the precursor composition or the counter-reactant. Exemplary purge gases include, but are not limited to, argon, nitrogen, helium, neon, and mixtures thereof. In certain embodiments, a purge gas, such as Ar, is fed into the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 1000 seconds to purge unreacted materials and any by-products that may remain in the reactor. Such purge gases can also be utilized as inert carrier gases for either or both of the precursor composition and the counter-reactant.

[0036] Each step of supplying the precursor composition and counter reactant can be performed by varying the order in which they are supplied and / or by varying the stoichiometric composition of the resulting EUV patternable film.

[0037] Energy is applied to the precursor composition and co-reactant in the reaction zone to induce a reaction and form an EUV-patternable film on the microelectronic device surface. Such energy can be provided by, but is not limited to, heat, pulsed heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma methods, and combinations thereof. In certain embodiments, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. In embodiments where deposition involves plasma, methods for generating the plasma can include direct plasma generation methods, in which the plasma is generated directly in the reactor, or alternatively, remote plasma generation methods, in which the plasma is generated "remote" from the reaction zone and substrate and fed into the reactor.

[0038] As used herein, the term "microelectronic device" corresponds to a semiconductor substrate, including 3D NAND structures, flat panel displays, and microelectromechanical systems (MEMS), that is fabricated for use in microelectronic, integrated circuit, or computer chip applications. The term "microelectronic device" is not meant to be limiting in any way and should be understood to include any substrate, such as a silicon wafer, that ultimately becomes a microelectronic device or microelectronic assembly. Such microelectronic devices contain at least one substrate that may be selected from, for example, tin, SiO2, Si3N4, OSG, FSG, tin carbide, hydrogenated tin carbide, tin nitride, hydrogenated tin nitride, tin carbonitride, hydrogenated tin carbonitride, boron nitride, antireflective coatings, photoresists, germanium, germanium-containing, boron-containing, Ga / As, flexible substrates, porous inorganic materials, metals such as copper and aluminum, and diffusion barrier layers such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. Thus, in an eleventh aspect, the present invention provides a microelectronic device substrate having an EUV-patternable film deposited thereon by the techniques described herein.

[0039] Another embodiment relates to a kit comprising one or more containers of one or more components suitable for use in depositing the EUV-patternable films of the present invention. The containers of the kit should be suitable for storage and shipping of the compositions and advantageously include means for delivering the components in the one or more containers into the reaction zone where the EUV-patternable film deposits on the substrate of the microelectronic device. In addition, the containers and systems can include dispense ports for dispensing the compositions to a process tool.

[0040] Thus, in a further aspect, the present invention provides a method for producing a pharmaceutical composition comprising: a. a precursor composition comprising at least one compound of formula (I) through (VI) or (A), as described herein; and b.-OR 1 and -N(R)2 moieties, where R 1 is selected from C1-C5 alkyl, and R is C1-C4 alkyl; The kit includes a kit comprising, in one or more containers, one or more components selected from:

[0041] In certain embodiments, the counter reactant is selected from water, peroxide, di- or polyhydroxy alcohol, hydrogen sulfide, hydrogen disulfide, trifluoroacetaldehyde monohydrate, fluorinated di- or polyhydroxy alcohol, and fluorinated glycol. [Example]

[0042] Example 1 Synthesis of [Sn(NMe2)2]2 (Caution: [Sn(N(CH3)2)2]2 is light sensitive and must be handled with care. Photochemical decomposition results in the production of tin metal and gaseous by-products that can create pressure and produce an energy mixture.)

[0043] In a nitrogen-filled glovebox operated in the absence of ambient light, SnCl (60 g, 313 mmol) was placed in a 1 L, three-necked jacketed flask equipped with an addition funnel, stirring paddle, and thermocouple. The SnCl was then dissolved in tetrahydrofuran (500 mL), whereupon a slight exotherm was observed (31 °C). The jacketed flask was covered with aluminum foil and cooled to 15 °C, and solid LiN(CH) (5 g) was added over 10 min. During this time, the pot temperature rose from 15.1 °C to 24.4 °C. The reaction was then cooled back to 15 °C before subsequent 5 g aliquots of LiNMe were added. This repeated addition of 5 g increments of LiNMe every 10 min and cooling cycle was continued until all of the LiNMe (32.7 g, 641 mmol) had been added. After the final addition of LiNMe2, when the exotherm subsided, the cooling of the jacketed flask was removed and the reaction was stirred at room temperature for 30 minutes. At this stage, the reaction appeared as a dark gray mixture and was filtered through a disposable polyethylene filter frit. The resulting dark brown solution was dried under reduced pressure with heating (35°C) and washed with hexane (100 mL) to produce a gray solid, which was redried using similar conditions. The resulting free-flowing gray powder was extracted with hexane (250 mL) at 65°C, filtered on a disposable polyethylene frit, and the filter cake and combined organic layers, washed with hexane (50 mL), were dried under reduced pressure to give the product as a free-flowing, pale yellow powder. Yield: 60.77 g, 93.8%. The product was recrystallized by dissolving in hexane (125 mL) at 65 °C and cooling in a freezer at -35 °C, and the decanted mother liquor and product were dried under reduced pressure to give 56.3 g (86.9% yield) of crystalline [Sn(NMe)] with a purity of 99.79%. 1 H-NMR (C6D6, 400 MHz); d, 24H, 2.80 ppm; 13 C-NMR (C6D6, 100 MHz); 44.38 ppm; 119 Sn-NMR (C6D6, 150 MHz); 123.80 ppm. ("Me" = methyl)

[0044] Example 2 Synthesis of LiSn(NMe2)3 In a nitrogen-filled glovebox, a 2 L three-neck half-jacketed flask was equipped with an overhead paddle stirrer, a gas inlet adapter, and a wide-mouth funnel. The flask was cooled to 2°C using an external refrigerator filled with silicone oil. n-Butyllithium (1.6 M in hexane, 1 L, 1.6 mol) was measured using a volumetric flask and added to the cooled three-neck flask with stirring. The solution was cooled for 15 minutes, and the wide-mouth funnel was replaced with a condenser. A gas cylinder containing dimethylamine was equipped with 1 / 4" PTFE tubing, connected to the three-neck flask via the gas inlet adapter, and tared on a balance. The gas inlet tube was positioned 1" below the nBuLi solution, and dimethylamine gas was added to the stirred solution at a rate of 0.55 g / min. As the dimethylamine was added, the reaction mixture became slightly turbid and the amount of white precipitate was observed to increase. After 78 g (1.70 mol) of dimethylamine had been consumed, gas addition was temporarily discontinued, the reaction was diluted with hexane (400 mL), and the gas inlet adapter was replaced with a thermocouple. The flask's condenser was replaced with an addition funnel, and SnCl was added in 50 g portions at 1 hour intervals, with the temperature gradually increasing from 24.7 °C to 25.9 °C over the course of 3 hours. When SnCl (153 g, 0.81 mol) was completely added, the reaction was stirred at 50 °C overnight.

[0045] The next morning, the reaction, which appeared as a brown / gray mixture, was hot filtered through a disposable 2 L polyethylene filter frit into a 2 L four-neck flask equipped with a magnetic stir bar. The flask and filter cake were washed with additional hexane (100 mL). The combined flaxen solution was dried with heat under reduced pressure to give a C6D6 solution, consistent with previous reports of this molecule. 1 H- and 119This produced [Sn(NMe2)2]2 (60.19 g, 0.14 mol) as a free-flowing, pale yellow, crystalline powder, as evidenced by Sn-NMR. The filter cake was extracted with tetrahydrofuran (2 x 150 mL) until the filtrate was colorless. The resulting deep reddish / brown solution was dried under reduced pressure to give LiSn(NMe2)3 (127.9 g, 0.62 mol) as the major isolated product as an off-white solid. 1 H-NMR (d8-THF, 400 MHz); s, 18H, 2.57 ppm; 7 Li-NMR (d8-THF, 155 MHz); 2.99 ppm; 13 C-NMR (d8-THF, 100 MHz); 44.68 ppm; 119 Sn-NMR (d8-THF, 150 MHz); 57.10 ppm.

[0046] Example 3 Synthesis of dimethylamidoisopropoxide tin(II) In a nitrogen-filled glovebox, [Sn(N(CH))] (3.0 g, 7.21 mmol) was placed in a 40 mL vial equipped with a magnetic stir bar and diluted with hexane (9 mL) to form a slightly cloudy yellow mixture. Separately, isopropanol (HO) i [Sn(N(CH3)2)]2 (0.865 g, 14.4 mmol) was diluted with hexane (6 mL) and the resulting solution was added dropwise to the [Sn(N(CH3)2)]2 solution over the course of 2 minutes. Gradually, the reaction appeared as a pale yellow solution, and after stirring for 10 minutes, the volatiles were removed under reduced pressure to give a pale yellow liquid. The product was placed in a 50 mL flask equipped with a magnetic stir bar, whereby a short-path distillation head was attached along with a 10 mL collection flask and the equipment placed in a heating mantle and placed under dynamic vacuum. The product distilled out as a pale yellow liquid at a head temperature of 67 °C and a system pressure of 1.62 Torr. The product was isolated as a slightly yellow liquid (weight: 1.90 g, yield: 59%). 1H-NMR (C6D6, 400 MHz); d, 6H, 1.31 ppm; s, 6H, 2.44 ppm; septet, 1H, 4.42 ppm; 119 Sn-NMR (C6D6, 150 MHz); 31.83 ppm.

[0047] Example 4 Synthesis of dimethylamido-tert-butoxide tin(II) In a nitrogen-filled glovebox, [Sn(N(CH))] (5 g, 12.0 mmol) was placed in a 40 mL vial equipped with a magnetic stir bar and diluted with hexane (10 mL) to form a slightly cloudy yellow mixture. In a separate vial, tert-butanol (HO) was added. t [Bu] (1.77 g, 23.9 mmol) was dissolved in hexane (5 mL) and added dropwise to the stirred [Sn(N(CH3)2)2]2 mixture; effervescence was observed upon addition of the alcohol. Upon complete addition, the reaction appeared as a colorless solution and was stirred at room temperature for 1 h, at which point volatiles were removed under reduced pressure to yield a pale yellow liquid. The product was distilled in a nitrogen-filled glovebox using a heating temperature range of 73–77 °C and a system pressure of 1.82–1.75 Torr, similar to the procedure reported for dimethylamido-isopropoxidetin(II). The product was isolated as a pale yellow liquid (weight: 3.2 g, yield: 57%). 1 H-NMR (C6D6, 400 MHz); d, 9H, 1.38 ppm; s, 6H, 2.44 ppm; 119 Sn-NMR (C6D6, 150 MHz); 31.77 ppm. TIFF0007781261000007.tif32170 Simultaneous thermal analysis: TIFF0007781261000008.tif47170* Note (compound number): 1. Sn(Ot-butyl)(N(CH3)2) 2. Sn(O-isopropyl)(N(CH3)2) 3. Sn(O-neopentyl)(N(CH3)2) 4. [Sn(N(CH3)2)2]2

[0048] Aspects In a first aspect, the present invention provides compounds of formula (I), (II) and (III): TIFF0007781261000009.tif31170 [wherein R is a C1-C4 alkyl, and R 1 is C1-C5 alkyl] A precursor composition is provided, comprising at least one compound selected from:

[0049] In a second aspect, the present invention provides a composition of the first aspect, wherein the composition contains 100 ppm or less of a material other than a compound of formula (I), (II) and (III).

[0050] In a third aspect, the present invention provides a compound wherein R is methyl and R 1 is selected from methyl, ethyl, isopropyl, t-butyl and neopentyl.

[0051] In a fourth aspect, the present invention provides a compound of formula (III) TIFF0007781261000010.tif19170 [wherein R is methyl and R 1 is selected from methyl, ethyl, isopropyl, t-butyl and neopentyl. The present invention provides a composition of the first, second or third aspect comprising at least one compound of

[0052] In a fifth aspect, the present invention provides a compound according to the present invention, wherein R is methyl and R 1 is methyl.

[0053] In a sixth aspect, the present invention provides a compound according to the present invention, wherein R is methyl and R 1 is ethyl.

[0054] In a seventh aspect, the present invention provides a compound wherein R is methyl and R 1 is isopropyl.

[0055] In an eighth aspect, the present invention provides a compound wherein R is methyl and R 1 is neopentyl.

[0056] In a ninth aspect, the present invention provides a compound wherein R is methyl and R 1 is tert-butyl.

[0057] In a tenth aspect, the present invention provides a precursor composition of the first aspect, wherein the composition comprises a compound of formula (I).

[0058] In an eleventh aspect, the present invention provides a precursor composition according to claim 1, wherein the composition comprises a compound of formula (II).

[0059] In a twelfth aspect, the present invention provides compounds of formula (I), (II) and (III): TIFF0007781261000011.tif31170 [wherein R is a C1-C4 alkyl, and R 1 is C1-C5 alkyl] 1. A method for preparing Compounds of formula (A): TIFF0007781261000012.tif25170, formula HOR 1 with a compound of formula HOR 1 is present in an amount of about 0.8 to about 1.2 molar equivalents based on the total number of moles of the compound of formula (A).

[0060] In a thirteenth aspect, the present invention provides a compound of formula (A): TIFF0007781261000013.tif25170 [wherein each R is independently selected from C1-C4 alkyl] A precursor composition comprising:

[0061] In a fourteenth aspect, the present invention provides the precursor composition of the thirteenth aspect, wherein the composition has less than about 1 weight percent impurities.

[0062] In a fifteenth aspect, the present invention provides compounds of formula (I), (II) and (III): TIFF0007781261000014.tif32170 [wherein R is a C1-C4 alkyl, and R 1 is C1-C5 alkyl] 1. A method for preparing Compounds of formula (A): TIFF0007781261000015.tif25170, formula HOR 1 with a compound of formula HOR 1 is present in an amount of about 3.8 to about 4.2 molar equivalents based on the total number of moles of the compound of formula (A).

[0063] In a sixteenth aspect, the present invention provides compounds of formula (IV), (V) and (VI): TIFF0007781261000016.tif31170 [wherein R is a C1-C4 alkyl, and R 1 is C1-C5 alkyl] wherein the composition contains 100 ppm or less of materials other than compounds of formulas (IV), (V), and (VI).

[0064] In a seventeenth aspect, the present invention provides a compound of formula (I), (II) and (III): TIFF0007781261000017.tif31170, comprising reacting a compound of formula SnX2, wherein X is selected from chloro, bromo, or iodo, with approximately one molar equivalent of a compound of formula MN(R)2, and approximately one molar equivalent of a compound of formula MOR 1 wherein M is selected from Groups 1 and 2 of the Periodic Table, and R 1is C1-C4 alkyl.

[0065] In an eighteenth aspect, the present invention provides (IV), (V) and (VI) TIFF0007781261000018.tif31170, comprising reacting a compound of formula SnX2, wherein X is selected from chloro, bromo, or iodo, with approximately 2 molar equivalents of a compound of formula MN(R)2 and approximately 1.8 to about 2.2 molar equivalents of a compound of formula MOR 1 wherein M is selected from Groups 1 and 2 of the Periodic Table, and R 1 is C1-C5 alkyl.

[0066] In a nineteenth aspect, the present invention provides a method for depositing a tin-containing film onto a microelectronic device surface in a reaction zone, the method comprising: and introducing into a reaction region a precursor composition comprising at least one compound of formula (I) TIFF0007781261000019.tif24170 to a surface in the reaction region under vapor deposition conditions.

[0067] In a twentieth aspect, the present invention provides a method for producing a composition comprising: a. a precursor composition selected from at least one compound of formulas (I) to (VI) and (A) according to any one of the first to eleventh, thirteenth and sixteenth aspects; and b.-OR 1 and -N(R)2 moieties, where R 1 is selected from C1-C5 alkyl, and R is C1-C4 alkyl; and introducing into the reaction region a reactant selected from:

[0068] In a twenty-first aspect, the present invention provides the method of the twentieth aspect, wherein the vapor deposition conditions comprise chemical vapor deposition.

[0069] In a twenty-second aspect, the present invention provides the method of the twentieth aspect, wherein the vapor deposition conditions comprise atomic layer deposition.

[0070] In a twenty-third aspect, the present invention provides a compound wherein R is methyl and R 1 is selected from methyl, ethyl, isopropyl, t-butyl, and neopentyl.

[0071] In a twenty-fourth aspect, the present invention provides the method of any one of the twentieth to twenty-third aspects, wherein the counter reactant is selected from water, peroxide, di- or polyhydroxy alcohol, hydrogen sulfide, hydrogen disulfide, trifluoroacetaldehyde monohydrate, fluorinated di- or polyhydroxy alcohol, and fluorinated glycol.

[0072] In a twenty-fifth aspect, the present invention provides a substrate of a microelectronic device having an EUV patternable film formed by the method of any one of the twentieth to twenty-fourth aspects deposited on the substrate of the microelectronic device.

[0073] In a twenty-sixth aspect, the present invention provides a substrate of the twenty-fifth aspect, wherein the precursor composition comprises at least one compound selected from formulae (I), (II) and (III) according to any one of the first to eleventh aspects.

[0074] In a twenty-seventh aspect, the present invention provides a method for producing a composition comprising: a. a precursor composition comprising at least one compound of formula (I) to (VI) and (A) according to any one of the first to eleventh, thirteenth or sixteenth aspects; b.-OR 1 and -N(R)2 moieties, where R 1is selected from C1-C5 alkyl, and R is C1-C4 alkyl; The kit includes one or more components selected from the group consisting of:

[0075] In a twenty-eighth aspect, the present invention provides the kit of the twenty-sixth aspect, wherein the counter reactant is selected from water, peroxide, a di- or polyhydroxy alcohol, hydrogen sulfide, hydrogen disulfide, trifluoroacetaldehyde monohydrate, a fluorinated di- or polyhydroxy alcohol, and a fluorinated glycol.

[0076] In a 29th aspect, the present invention provides a kit of the 27th or 28th aspect, wherein the precursor composition comprises at least one compound selected from formulae (I), (II) and (III) and (A) according to any one of the 1st to 11th, or 13th or 14th aspects.

[0077] While several illustrative embodiments of the present disclosure have thus been described, those skilled in the art will readily appreciate that still other embodiments may be made and used within the scope of the claims appended hereto. Numerous advantages of the present disclosure encompassed by this document have been set forth in the foregoing description. It will be understood, however, that this disclosure is in many respects merely illustrative. The scope of the present disclosure will, of course, be defined in the language in which the appended claims are expressed.

Claims

[Claim 1] Compounds of formula (I), (II) and (III): wherein R is C １ ~C ４ alkyl, and R １ is C １ ~C ５ alkyl] 1. A method for preparing Compound of formula (A): wherein R is C 1 -C 4 alkyl. to the formula HOR １ Compounds of wherein R 1 is C 1 -C 5 alkyl. with a compound of formula HOR １ is present in an amount of 1.8 to 2.2 molar equivalents based on the total number of moles of the compound of formula (A).

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