Process for deposition of tin-containing film or euv-patternable film onto surface of microelectronic device

Abstract

This invention provides certain fluorinated alkyltin compounds, which are believed to be used for vapor deposition of tin-containing films onto the surface of microelectronic device substrates. This invention also provides methods for preparing these precursor compounds and methods for depositing tin-containing films onto microelectronic device substrates using these compounds.

Description

Method for depositing a tin-containing film or an EUV-patternable film onto the surface of a microelectronic device This invention pertains to the field of organotin chemistry. Specifically, it relates to methods for preparing certain fluorinated tin compounds that can be used for the vapor deposition of tin-containing films. It has been shown that certain organotin compounds can be used to deposit highly pure tin(II) oxide in the manufacture of microelectronic devices. Particular attention has been paid to organotin compounds having a combination of an alkylamine group and an alkyl group, which can be used as liquid precursors for depositing tin-containing films onto microelectronic device substrates. In addition, it has been shown that certain organometallic compounds can be used as precursors for depositing high-purity metal oxide films in applications such as extreme ultraviolet (EUV) lithography techniques used in the manufacture of microelectronic devices. In this process, certain organometallic precursors are combined with relative reactants to form a polymeric organometallic film. Then a pattern is formed on the surface, the EUV-patternable film involving the film is exposed using a patterned beam of EUV light, and then the resulting microelectronic device surface is exposed to post-exposure baking in ambient air. This treatment using patterned EUV light leaves some exposed and some unexposed portions of the surface, and thus enables further processing and patterning due to the different physical and chemical differences between the two regions. See, for example, U.S. Patent Publication 2021 / 0013034. Therefore, there is a need to develop precursor compositions and relative reactant pairs that can be used in this dry (photo)resist process and an improved method for the deposition of highly pure tin oxide films. In summary, the present invention provides certain fluorinated alkyltin compounds that are believed to be useful for the vapor deposition of tin-containing films onto the surface of a microelectronic device substrate. In one aspect, the present invention provides a compound of formula (I): (I), wherein Y is a group of the formula or ; wherein R is independently selected from H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluorinated alkyl, C 1 -C 8 Partially fluorinated alkyl, and R 1 is selected from H, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkoxy, C 1 -C 8 perfluoroalkyl and C 1 -C 8 Partially fluorinated alkyl, and m is from 0 to 4, and n is from 0 to 3. Priority Claim This disclosure claims the priority of U.S. Provisional Patent No. 63 / 243,885, filed on September 14, 2021, which is incorporated herein by reference. As used in this specification and the appended claims, unless the context clearly dictates otherwise, the singular forms "a / an" and "the" include plural referents. As used in this specification and the appended claims, unless the context clearly dictates otherwise, the term "or" is generally employed in its sense including "and / or". The term "about" generally refers to a numerical range that is considered equivalent to the recited value (e.g., having the same function or result). In many instances, the term "about" may include numbers rounded to the nearest significant digit. Numeric ranges are inclusive of the recited numbers defining the range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5). In one aspect, the present invention provides a compound of formula (I): (I), wherein Y is a group of the following formula or ; wherein R is independently selected from H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkyl, C 1 -C 8 partially fluorinated alkyl, and R 1 is selected from H, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkoxy, C 1 -C 8 perfluoroalkyl and C 1 -C 8 partially fluorinated alkyl, and m is from 0 to 4, and n is from 0 to 3. In certain embodiments, R is selected from methyl, ethyl, and isopropyl. In certain embodiments, R 1 is selected from hydrogen, methyl, and ethyl. In certain embodiments, n is from 0 to 2. In some embodiments, R 1 is C 1 -C 8 Perfluoroalkyl group. The compound of formula (I) can be prepared according to the following reaction scheme: , where M is selected from lithium, potassium, sodium or a group of the formula MgX, where X is selected from chlorine, iodine and bromine, and R and R 1 are as described above. Next, in the presence of Ph 3 SnF (i.e., triphenyltin fluoride - CAS No. 379-52-2), the intermediate of formula (A) above is reacted with a compound of formula M-F to obtain a compound of formula (B): . Similarly, the compound of formula (B) can be prepared by fluorination of the corresponding bromine, iodine or chlorine compound using a known fluorinating agent. See, for example, Yanpin Liu et al., Organometallics, 2013, 32, 21, 6587-6592; Yoneda, Norihiko et al., Chemistry Letters (1987), (8), 1675-8; Makosza, Mieczyslaw et al., eEROS Encyclopedia of Reagents for Organic Synthesis (2001); Escoula, B. et al., Tetrahedron Letters (1986), 27(13), 1499-1500; Pattison, F.L.M. et al., Journal of the American Chemical Society (1957), 79, 2308-11; Iwasaki, Takanori et al., Chemical Science (2018), 9(8), 2195-2211; Albanese, Domenico et al., Journal of Organic Chemistry (1998), 63(25), 9587-9589; and Mathiessen, Bente et al., Chemistry – A European Journal (2011), 17(28), 7796-7805. Next, the compound of formula (B) (for example, when R is phenyl) can be treated with about 1 to 3 molar equivalents of SnCl 4 to obtain a trichlorotin intermediate of formula (C): . Then, in the presence of an existential LiN(CH 3 ) 2 compound, reacting a compound of formula (C) with about 2 to about 5 molar equivalents of a compound of formula HN(R) 2 to obtain a compound of formula (I), wherein Y is a group of the following formula . A compound of formula (I), wherein Y is a group of the following formula , can be prepared by treating a compound of formula (C) with ROH in the presence of a secondary or tertiary amine or by treating a compound of formula (C) with MOR (wherein M is selected from alkali metals). In an alternative synthetic route, a compound of formula (I) (wherein n is one (1)) can be prepared by direct fluorination of certain intermediates. Thus, in another aspect, the present invention provides a method for preparing a compound of formula (II): wherein R is selected from C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl and aryl, and each R 1 is independently selected from H, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl and aryl, the method comprising treating a compound of formula (D): , with a fluorinating agent. In the above methods, exemplary R and R 1Groups include methyl, ethyl, propyl, n-butyl, n-pentyl, vinyl, allyl, 2-propynyl, phenyl and the like. Suitable fluorinating agents include known nucleophilic deoxygenating fluorinating agents such as: diethylaminosulfur trifluoride (also known as "DAST"); 2-pyridylsulfonyl fluoride, CAS No. 878376-35-3, sold under the trademark PyFluor™; [methyl(oxo){1-[6-(trifluoromethyl)-3-pyridyl]ethyl}-λ 6 -sulfinyl]cyanamide; CAS No. 946578-003, also known as "SulfoxaFluor™"; 1,3-bis(2,6-diisopropylphenyl)-2,2-difluoro-2,3-dihydro-1 H-imidazole, CAS No. 1314657-40-3, sold under the trademark PhenoFluor™; diethylaminodifluorosulfonium tetrafluoroborate, CAS No. 63517-29-3, also known as XtalFluor-E ® sold by OmegaChem, Inc.; bis(2-methoxyethyl)aminosulfur trifluoride, CAS No. 202289-38-1, sold under the trademark Deoxo-Fluor®, Air Products and Chemicals, Inc.; perfluorobutanesulfonyl fluoride, CAS No. 375-72-4, also known as 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride. 4-morpholinylsulfur trifluoride, CAS No. 51010-74-3, also known as Morph-DAST; difluoro-4-morpholinylsulfonium tetrafluoroborate, CAS No. 63517-33-9, also known as XtalFluor-M ®, sold by Sigma Aldrich; 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride, CAS No. 947725-04-4, also known as FLUOLEAD™, sold by TCI chemicals; N,N-diethyl-1,1,2,3,3,3-hexafluoropropylamine, CAS No. 309-88-6, also known as Ishikawa’s reagent; N,N-diethyl-α,α-difluoro-3-methylbenzylamine, CAS No. 500131-50-0, also known as DFMBA; tetramethylfluoroformamidinium hexafluorophosphate, CAS No. 164298-23-1, also known as TFFH, sold by Sigma Aldrich; fluoro-N,N,N′,N′-bis(tetramethylene)formamidinium hexafluorophosphate, CAS No. 164298-25-3, also known as BTFFH, sold by Sigma Aldrich; and 1,3-bis(2,6-diisopropylphenyl)-2,2-difluoro-2,3-dihydro-1H-imidazole, CAS No. 1314657-40-3, also known as PhenoFluor™. In another synthetic alternative, the compound of formula (I) where n is one (1), i.e., the following compound of formula (II), can be prepared by direct fluorination of the corresponding methanesulfonate or tosylate. The compound of formula (II) can be used as an intermediate in the synthesis of the compound of formula (I). In another aspect, the present invention provides a method for preparing a compound of formula (II): , where R is independently selected from H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkyl, C 1 -C 8 partially fluorinated alkyl, and R 1 is selected from H, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkoxy, C 1 -C 8 perfluoroalkyl and C 1 -C 8 partially fluorinated alkyl, and m is from 0 to 4, and n is from 0 to 3, the method comprising treating a compound of formula (E): 1 -C 8 with a compound of formula M-F (where M is selected from lithium, potassium, sodium or tetra-C , where R 2 is tosyl or mesyl. In certain embodiments, this reaction is carried out in the presence of an ionic liquid or a compound such as polyethylene glycol or a phase transfer catalyst. The compound of formula (E) can be prepared from the above compound of formula (D) by reacting the compound of formula (D) with a mesyl halide or a tosyl halide (such as mesyl chloride or tosyl chloride) in the presence of a base. The above compound of formula (D) can be prepared using known chemistry according to the following reaction scheme: In an alternative method for synthesizing the compound of formula (II), a compound of the following formula can be reacted with a compound of the following formula , where each X is independently selected from a halogen group, to obtain a compound of the following formula , which can then undergo a halogen exchange reaction in the presence of a compound of formula M-F. The resulting compound can then be treated with SnCl 4 to obtain the corresponding tin trichloride compound of the following formula , which upon reaction with a compound of formula LiN(R) 2 and at least 2 molar equivalents of a compound of formula (R) 2 After the reaction of the NH compound, the resulting tris(amido)tin compound of formula (III) is obtained: , where R is independently selected from H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkyl, C 1 -C 8 partially fluorinated alkyl, and R 1 is selected from H, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkoxy, C 1 -C 8 perfluoroalkyl and C 1 -C 8 partially fluorinated alkyl, and m is from 0 to 4, and n is from 0 to 3. In yet another alternative, the compound of formula (D) can be prepared according to the following reaction scheme: In the above reaction scheme, R 4 can be selected from the formula -Si(CH 3 ) 3 、 -Si(CH 2 CH 3 ) 3 、 -Si(isopropyl) 3 、 -Si(tert - butyl) 2 (phenyl) and -Si(CH 3 ) 2 (tert - butyl) groups. Thus, in another aspect, the present invention provides a method for preparing a compound of the following formula: , where each R 1 is independently selected from H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl and aryl; the method includes, in the presence of a base, treating a compound of the following formula , with an R 2 -Cl compound to obtain a compound of the following formula , where R 4 is selected from the group consisting of -Si(CH 3 ) 3 、 -Si(CH 2 CH 3 ) 3 、 -Si(isopropyl) 3 、 -Si(tert - butyl) 2 (phenyl) and -Si(CH 3 ) 2 (tert-Butyl) group; then treated with a (phenyl) 3 SnNa compound to obtain a compound of the following formula ; then the hydroxyl group is deprotected. Like the compound of formula (I), it is believed that the compound of formula (III) can be used as a precursor for vapor deposition of a tin-containing film onto the surface of a microelectronic device substrate, and as indicated above, the compound of formula (II) can be used as an intermediate. Thus, in a fourth aspect, the present invention provides compounds of formula (II) and (III): , and , where R is independently selected from H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkyl, C 1 -C 8 partially fluorinated alkyl, and R 1 is selected from H, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkoxy, C 1 -C 8 perfluoroalkyl and C 1 -C 8 a partially fluorinated alkyl group, where m is from 0 to 4, and n is from 0 to 3. In certain embodiments, R is selected from C 1 -C 3 alkyl groups. In certain embodiments, R is selected from methyl, ethyl, and isopropyl. In certain embodiments, R 1 is selected from hydrogen, methyl, or ethyl. As indicated above, it is believed that these organotin precursor compounds can be used in various vapor deposition processes when it is desired to deposit a tin-containing film onto the surface of a microelectronic device. Thus, in a fifth aspect, the present invention provides a method for depositing a tin-containing film onto the surface of a microelectronic device in a reaction zone, which includes introducing a precursor composition containing at least one compound selected from formulas (I) and (III) into the reaction zone under vapor deposition conditions. Additionally, it is believed that the precursors of the present invention are particularly useful for patterning microelectronic device substrates using extreme ultraviolet light (EUV) technology. In this regard, see U.S. Patent Publication 2021 / 0013034, which is incorporated herein by reference. It is contemplated that the precursor composition of the present invention in the form of a vapor stream is mixed with a relative reactant in such a way that an organometallic material in oligomeric or polymeric form is formed on the surface of the microelectronic device. In this way, the film thus formed becomes an EUV-patternable film, considering its reactivity with EUV light. Accordingly, in a sixth aspect, the present invention provides a method for depositing an EUV-patternable film onto the surface of a microelectronic device in a reaction zone, which includes introducing a precursor composition into the reaction zone under vapor deposition conditions, the precursor composition containing reactants selected from: a. a precursor composition selected from at least one compound of formulas (I) and (III); and b. at least one relative reactant selected from compounds that can react with -O-R 2 and -N(R 2 ) 2 partially, where R 2 is selected from C 1 -C 4 alkyl groups. Suitable relative reactants are those that can displace -O-R on the compounds of formulas (I) and (III) as described above 2and / or -N(R 2 ) 2 those compounds of the group, and include substances such as: water, peroxides such as hydrogen peroxide, dihydroxy alcohols or polyhydroxy alcohols, hydrogen sulfide, hydrogen disulfide, trifluoroacetaldehyde monohydrate, fluorinated dihydroxy or polyhydroxy alcohols, and fluorinated diols. The film thus formed is an oligomeric or polymeric organometallic material containing SnO x , where x is from about 1.5 to about 2. Additionally, the thickness of these EUV-patternable films generally varies from about 0.5 to about 100 nm. In certain embodiments, the vapor deposition conditions include reaction conditions known as chemical vapor deposition, pulsed chemical vapor deposition, and atomic layer deposition. In the case of pulsed chemical vapor deposition, a series of precursor compositions and alternating pulses of the relative reactants can be utilized, with or without an intermediate (inert gas) purge step, to build up the film thickness to the desired endpoint. In certain embodiments, the pulse time of the above precursor compounds (i.e., the duration of exposure of the precursor to the substrate) ranges between about 1 and 30 seconds. When a purge step is utilized, the duration is about 1 to 20 seconds or 1 to 30 seconds. In other embodiments, the pulse time of the co-reactant ranges from 5 to 60 seconds. In one embodiment, the vapor deposition conditions include a temperature in the reaction zone of from about 0°C to about 250°C, or from about 22°C to about 150°C, and a reduced pressure of from about 10 mTorr to about 10 Torr. When used in combination with the relative reactant materials mentioned above, a precursor composition containing a compound selected from at least one of the above formulas (I) to (VI) can be employed to form (a) a tin-containing film and (b) a high-purity EUV-patternable film. In the eighth and ninth aspects, any suitable vapor deposition technique can be utilized, such as chemical vapor deposition (CVD), digital (pulsed) CVD, atomic layer deposition (ALD), or fluidized chemical vapor deposition (FCVD). In the tenth aspect of the present invention, the above compounds can be reacted in the reaction zone in any suitable manner, for example, by single-wafer CVD or ALD or in a furnace containing multiple wafers with the (said) relative reactants and the surface of the desired microelectronic device substrate. 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 the following: (i) introducing each reactant sequentially into a reactor (such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor), the reactant comprising a precursor composition containing a compound selected from formula (I) and (III), a counter-reactant, or (ii) exposing each reactant to the surface of a substrate or a microelectronic device by moving or rotating the substrate to different sections of the reactor and separating the sections by an inert gas curtain (i.e., a spatial ALD reactor or a roll-to-roll ALD reactor). In certain embodiments, the thickness of the ALD film can be from about 0.5 nm to about 40 nm and the deposition temperature ranges from about 30 °C to about 500 °C. The deposition methods disclosed herein may involve one or more purge gases. The purge gas used to purge unconsumed reactants and / or reaction by-products is an inert gas that does not react with 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, the purge gas (such as Ar) is supplied to the reactor at a flow rate in the range from about 10 to about 2000 sccm for about 0.1 to 1000 seconds to purge unreacted materials and any by-products that may be present in the reactor. These purge gases can also be used as an inert carrier gas for either or both of the precursor composition and the counter-reactant. Each step of supplying the precursor composition and the counter-reactant can be carried out by changing the order of their supply and / or changing the stoichiometric composition of the resulting EUV-patternable film. Energy is applied to the precursor composition and the co-reactant in the reaction zone to induce a reaction and form an EUV-patternable film on the surface of the microelectronic device. This 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-rays, e-beam, photons, remote plasma methods, and combinations thereof. In certain embodiments, a secondary RF frequency source can be used to modify the plasma properties of the substrate surface. In embodiments where the deposition involves plasma, the plasma generation method can include a direct plasma generation method, where the plasma is generated directly in the reaction zone, or alternatively, a remote plasma generation method, where the plasma is generated "away" from the reaction zone and the substrate and is supplied to the reactor. As used herein, the term "microelectronic device" corresponds to a semiconductor substrate that includes a 3D NAND structure, a flat panel display, and a microelectromechanical system (MEMS), which is fabricated for microelectronic integrated circuit or computer chip applications. It should be understood that the term "microelectronic device" is not intended to be limited in any way and includes any substrate that includes negative-channel metal-oxide-semiconductor (nMOS) and / or positive-channel metal-oxide-semiconductor (pMOS) transistors and that will ultimately become a microelectronic device or microelectronic assembly. Such microelectronic devices contain at least one substrate, which can be selected from, for example, tin, SiO 2 , Si 3 N 4 , OSG, FSG, tin carbide, tin carbide hydride, tin nitride, tin nitride hydride, tin carbonitride, tin carbonitride hydride, boron nitride, antireflective coating, photoresist, germanium, germanium-containing, boron-containing, Ga / As, flexible substrate, porous inorganic material, 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. Examples Examples 1 Ph 3 SnCH 2 CH 2 (CH 3 )OH can be synthesized according to the procedure seen in Davis, D. D., Gray, C. E. Deoxymetalation Reactions. Mechanism of Deoxystannylation. J. Org. Chem. 1970, 35(5), 1303 - 1307. (Ph = phenyl). Examples 2 Cl(CH 2 ) 2O-TMS can be synthesized according to the procedure described in Mander, L. N., Turner, J. V. Chloroethoxy(Trimethyl)Silane: A Hard-Base Trap Which Preserves Tms Ether Groups and Improves the Wittig Methylenation of Gibberellins. Tetrahedron Letters 1981, 22(41), 4149-4152. (TMS = trimethylsilyl). Example 3 Ph 3 SnCH 2 CH 2 OTMS A solution of (2-chloroethoxy)trimethylsilane (0.500 g, 3.27 mmol) in 5 mL of THF was added over 5 minutes to a solution of 32.6 mL of 0.1 M sodium triphenylstannate (3.27 mmol) in THF in a 100 mL round-bottom flask cooled to -65 °C. Only a minimal exotherm was observed. The reaction mixture was allowed to stir at -65 °C for 1 hour and then warmed to ambient temperature. The reaction mixture was stripped of all volatiles under reduced pressure, slurried in a minimal amount of hexane, and filtered through a Celite bed. The filtrate was concentrated to give 0.650 g of a yellow oil (42%). 1 H-NMR (149 MHz CDCl 3 , 298K): δ 7.61-7.57 (m, 6H), 7.18-7.11 (m, 9H), 3.78 (t, 2H), 1.68 (t, 2H), -0.13 (s, 9H). 13 C {¹H} NMR (100 MHz, CDCl 3 289K): δ139.88, 137.60, 129.00, 128.72, 60.13, 17.44, -0.63 ppm. 119 Sn {¹H} NMR (149 MHz CDCl 3, 298K): δ - 99.61 ppm. Example 4 Ph 3 SnCH 2 CH 2 OTM S- Deprotection is Ph 3 SnCH 2 CH 2 OH (Prophetic) Ph 3 SnCH 2 CH 2 OTMS to Ph 3 SnCH 2 CH 2 The conversion of OH can be carried out by the procedures mentioned on pages 119 to 121 of Protection for the Hydroxyl Group, Including 1,2- and 1,3-Diols. Protective Groups in Organic Synthesis; John Wiley & Sons, Ltd, 1999; modifications of the procedures mentioned. Anhydrous citric acid (2.05 g, 10.7 mmol) was dissolved in 60 mL of methanol in a 100 mL flask, and trimethyl[2-(triphenylstannyl)ethoxy]silane (5.00 g, 10.7 mmol) was transferred to the flask. The reaction mixture was stirred for 24 hours, the volatiles were stripped off under reduced pressure, and the residue was extracted with 100 mL of THF. The THF solution was washed with saturated sodium bicarbonate solution, then with water, and then separated and dried over magnesium sulfate. Then the volatiles were removed under reduced pressure to give the product as a white solid. Example 5 Ph 3 SnCH 2 CH 2 OTBDMS (Prophetic) A solution of sodium triphenylstannate (54.0 mL, 54.0 mmol) in THF at -65 °C was added dropwise with a solution of tert-butyl(2-chloroethoxy)dimethylsilane (10.5 g, 54.0 mmol) in 10 mL of anhydrous tetrahydrofuran. The dark green solution was allowed to warm to ambient temperature over 18 h and then all volatiles were stripped in vacuo. The residue was slurried in a minimum amount of hexanes, filtered through a bed of celite, and the filtrate was concentrated in vacuo. (TBDS = tert-butyldimethylsilyl). Example 6 From Ph 3 SnCH 2 CH 2 OTBDMS of Ph 3 SnCH 2 CH 2 OH (Prophetic) A solution of tetrabutyl(fluoro)ammonium (19.6 mL, 19.6 mmol) (1.0 M in THF) was added to a solution of tert-butyldimethyl[2-(triphenylstannyl)ethoxy]silane (5.00 g, 9.81 mmol) in 10 mL of THF. The mixture was stirred for 18 h and 30 mL of water was added. The mixture was extracted 2x with diethyl ether (20 mL aliquots), and the combined organic layers were washed successively with saturated NH 4 Cl solution and saturated brine. The product solution was dried over magnesium sulfate and then all volatiles were stripped under reduced pressure. Example 7 From Ph 3 SnCH 2 CH 2 OH of Ph 3 SnCH 2 CH 2 OTs (Prophetic) To a stirred solution of Ph 3 SnCH 2CH 2 p - Toluenesulfonyl chloride (2.19 g, 11.5 mmol) was added in portions to a solution of OH (3.95 g, 10.00 mmol). The resulting mixture was stirred in an ice bath for 3 hours, diluted with 35.0 mL of dichloromethane, and successively washed with 10 mL of 2M HCl, 10 mL of water, and 10 mL of 10% aqueous sodium bicarbonate. The organic layer was separated, dried over magnesium sulfate, and stripped of all volatiles under reduced pressure. Example 8 From Ph 3 SnCH 2 CH 2 OTs of Ph 3 SnCH 2 CH 2 -F (Prophetic) Ph was added to a solution of 9.55 mL of 1.0M tetrabutylammonium fluoride in THF (9.55 mmol). 3 SnCH 2 CH 2 OTs (5.00 g, 9.10 mmol). The solution was refluxed for 18 hours and then stripped of all volatiles. Example 9 From Ph 3 SnCH 2 CH 2 OH of Ph 3 SnCH 2 CH 2 -F (Prophetic) Ph was added dropwise to a solution of diethylaminosulfur trifluoride (2.29 g, 12.8 mmol) in 25 mL of dichloromethane cooled to -70 °C. 3 SnCH 2 CH 2A solution of OH (5.00 g, 12.6 mmol) was allowed. The stirred solution was allowed to warm to ambient temperature over 3 hours. The reaction mixture was added to 50 mL of saturated sodium bicarbonate solution cooled to 0 °C and then extracted 2x with 20 mL aliquots of dichloromethane. The combined organic phases were dried over magnesium sulfate and filtered through a silica plug. The product solution was then stripped of volatiles under reduced pressure. Example 10 From Ph 3 SnCH 2 CH 2 -F of Cl 3 SnCH 2 CH 2 -F (Prophetic) (2-Fluoroethyl)triphenylstannane (40.00 g, 100 mmol) was placed in a 100 mL flask equipped with a stir bar and a heat trap and then treated in several aliquots with tin tetrachloride (52.1 g, 200 mmol). When addition was complete, the flask was fitted to a distillation apparatus with a 1' Vigreux column. The product was then fractionated away from phenyltrichlorostannane and diphenyldichlorostannane under reduced pressure. Example 11 From Cl 3 SnCH 2 CH 2 -F of (Me 2 N) 3 SnCH 2 CH 2 -F (Prophetic) Butyllithium (36.0 mL, 57.6 mmol) and 35 mL of hexane were placed in a 3-necked 250 mL round bottom flask equipped with a stir egg. The solution was cooled to 0 °C and then treated with dimethylamine (6.58 g, 146 mmol). The resulting slurry was then cooled to -10 °C and treated dropwise over 2 hours with a solution of trichloro(2-fluoroethyl)stannane (5.00 g, 18.3 mmol) in 25 mL of hexane. The reaction mixture was allowed to warm to ambient temperature over 18 hours and then filtered. The filtrate was concentrated under reduced pressure to afford the desired product. Aspect In a first aspect, the present invention provides a compound of formula (I): (I), wherein Y is a group of the following formula or ; wherein R is independently selected from H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkyl, C 1 -C 8 partially fluorinated alkyl, and R 1 is selected from H, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkoxy, C 1 -C 8 perfluoroalkyl and C 1 -C 8 partially fluorinated alkyl, and m is from 0 to 4, and n is from 0 to 3. In a second aspect, the present invention provides a compound as in the first aspect, wherein Y is a group of the following formula . In a third aspect, the present invention provides a compound as in the first aspect, wherein Y is a group of the following formula 。 In a fourth aspect, the present invention provides a compound as in the first, second, or third aspect, wherein n is 2. In a fifth aspect, the present invention provides a compound as in any one of the first to fourth aspects, wherein R is selected from C 1 -C 3 alkyl. In a sixth aspect, the present invention provides a compound as in any one of the first to fifth aspects, wherein R is selected from methyl, ethyl, and isopropyl. In a seventh aspect, the present invention provides a compound as in any one of the first to sixth aspects, wherein R 1 is selected from hydrogen, methyl, or ethyl. In an eighth aspect, the present invention provides a compound as in any one of the first to seventh aspects, wherein R is selected from methyl, ethyl, and isopropyl, and wherein R 1 is selected from hydrogen, methyl, or ethyl. In a ninth aspect, the present invention provides a compound as in any one of the first to eighth aspects, wherein R is methyl and R 1 is methyl. In a tenth aspect, the present invention provides a method for preparing a compound of formula (II): , wherein R is independently selected from H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkyl, C 1 -C 8 partially fluorinated alkyl, and R 1 is selected from H, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkoxy, C 1 -C 8 perfluoroalkyl and C 1 -C 8 a partially fluorinated alkyl group, where m is from 0 to 4 and n is from 0 to 3. The method includes treating a compound of formula (D): , with a fluorinating agent. In an eleventh aspect, the present invention provides a method as in the tenth aspect, wherein the fluorinating agent is selected from sulfur trioxide bis(diethylamide); [methyl(oxo){1-[6-(trifluoromethyl)-3-pyridyl]ethyl}-λ 6 -sulfenyl]cyanamide; 1,3-bis(2,6-diisopropylphenyl)-2,2-difluoro-2,3-dihydro-1 H-imidazole ; (diethylamino)difluorosulfonium tetrafluoroborate; bis(2-methoxyethyl)aminosulfur trifluoride; perfluorobutanesulfonyl fluoride; 4-morpholinylsulfur trifluoride; difluoro-4-morpholinylsulfonium tetrafluoroborate; 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride; N,N-diethyl-1,1,2,3,3,3-hexafluoropropylamine; N,N-diethyl-α,α-difluoro-3-methylbenzylamine; tetramethylfluoroformamidinium hexafluorophosphate; fluoro-N,N,N′,N′-bis(tetramethylene)formamidinium hexafluorophosphate; and 1,3-bis(2,6-diisopropylphenyl)-2,2-difluoro-2,3-dihydro-1H-imidazole. In a twelfth aspect, the present invention provides a method as in the tenth or eleventh aspect, wherein R is phenyl. In a thirteenth aspect, the present invention provides a method as in any one of the tenth to twelfth aspects, wherein R 1 is hydrogen or C 1 -C 8Alkyl. In a fourteenth aspect, the present invention provides a method for preparing a compound of formula (II): , where R is independently selected from H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkyl, C 1 -C 8 partially fluorinated alkyl, and R 1 is selected from H, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkoxy, C 1 -C 8 perfluoroalkyl and C 1 -C 8 partially fluorinated alkyl, and m is from 0 to 4, and n is from 0 to 3, the method comprising treating a compound of formula (B) with a compound of formula M-F (where M is selected from lithium, potassium, sodium or tetra C 1 -C 8 alkylammonium): , wherein R 2 is tosyl or mesyl. In a fifteenth aspect, the present invention provides a method as in the fourteenth aspect, wherein R is phenyl. In a sixteenth aspect, the present invention provides a method as in the fourteenth or fifteenth aspect, wherein R 1 is hydrogen or C 1 -C 8 alkyl. In a seventeenth aspect, the present invention provides a method for preparing a compound of the following formula: , wherein each R 1 is independently selected from H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl and aryl; the method includes, in the presence of a base, treating a compound of the following formula , with a compound of the formula R 2 -Cl to obtain a compound of the following formula , wherein R 2 is selected from the group of -Si(CH 3 ) 3 , -Si(CH 2 CH 3 ) 3 , -Si(isopropyl) 3 , -Si(tert-butyl) 2 (phenyl) and -Si(CH 3 ) 2 (tert-butyl); then using (phenyl) 3Treatment of SnNa compound to obtain a compound of the following formula , and then deprotect the hydroxyl group. In the eighteenth aspect, the present invention provides a compound selected from the compounds of formula (II) and (III): , and , where R is independently selected from H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkyl, C 1 -C 8 partially fluorinated alkyl, and R 1 is selected from H, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkoxy, C 1 -C 8 perfluoroalkyl and C 1 -C 8 partially fluorinated alkyl, and m is from 0 to 4, and n is from 0 to 3. In the nineteenth aspect, the present invention provides a compound as in the eighteenth aspect, where R is methyl. In a twentieth aspect, the present invention provides a compound as in the eighteenth or nineteenth aspect, wherein R 1 is hydrogen or C 1 -C 8 alkyl. In a twenty-first aspect, the present invention provides a method for depositing a tin-containing film onto the surface of a microelectronic device in a reaction zone, the method comprising introducing a precursor composition into the reaction zone under vapor deposition conditions, the precursor composition comprising at least one compound selected from formulas (I) and (III): , wherein Y is a group of the following formula or ; wherein R is independently selected from H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkyl, C 1 -C 8 partially fluorinated alkyl, and R 1 is selected from H, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkoxy, C 1 -C 8 Perfluoroalkyl and C 1 -C 8 Partially fluorinated alkyl, where m is from 0 to 4 and n is from 0 to 3; and , where R is independently selected from H, C 1 -C 8 Alkyl, C 2 -C 8 Alkenyl, C 2 -C 8 Alkynyl, aryl, C 1 -C 8 Perfluorinated alkyl, C 1 -C 8 Partially fluorinated alkyl, and R 1 Is selected from H, C 1 -C 8 Alkoxy, C 1 -C 8 Alkyl, C 2 -C 8 Alkenyl, C 2 -C 8 Alkynyl, aryl, C 1 -C 8 Perfluoroalkoxy, C 1 -C 8 Perfluoroalkyl and C 1 -C 8 Partially fluorinated alkyl, where m is from 0 to 4 and n is from 0 to 3; and at least one selected from those capable of reacting with -O-R 2 and -N(R 2 ) 2 a relative reactant of a partially reactive compound, wherein R 2 is selected from C 1 -C 4 alkyl. In a twenty-second aspect, the present invention provides a method as in the twenty-first aspect, wherein the precursor composition comprises at least one compound selected from formula (I), wherein Y is a group of the following formula: , and wherein each R is independently selected from methyl, ethyl, isopropyl and tert-butyl; and R 1 is selected from hydrogen, methyl and ethyl. In a twenty-third aspect, the present invention provides a method as in the twenty-first aspect, wherein the precursor composition comprises at least one compound selected from formula (I), wherein Y is a group of the following formula: , and wherein each R is independently selected from methyl, ethyl, isopropyl and tert-butyl; and R 1 is selected from hydrogen, methyl and ethyl. In a twenty-fourth aspect, the present invention provides a method as in the twenty-first, twenty-second or twenty-third aspect, wherein R is methyl. In a twenty-fifth aspect, the present invention provides a method as in the twenty-first to twenty-fourth aspects, wherein R 1 is hydrogen or C 1 -C 8 alkyl. In a twenty-sixth aspect, the present invention provides a method for depositing an EUV-patternable film onto the surface of a microelectronic device in a reaction zone, the method comprising introducing a precursor composition into the reaction zone under vapor deposition conditions, the precursor composition comprising a reactant selected from: a. a precursor composition selected from at least one compound of formula (I) and (III); (I), wherein Y is a group of the following formula or ; wherein R is independently selected from H, C 1 -C 8 alkyl, C 2-C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkyl, C 1 -C 8 partially fluorinated alkyl, and R 1 is selected from H, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 perfluoroalkoxy, C 1 -C 8 perfluoroalkyl and C 1 -C 8 partially fluorinated alkyl, and m is from 0 to 4, and n is from 0 to 3; and , where R is independently selected from H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl, C 1 -C 8 Perfluoroalkyl, C 1 -C 8 Partially fluorinated alkyl, and R 1 Selected from H, C 1 -C 8 Alkoxy, C 1 -C 8 Alkyl, C 2 -C 8 Alkenyl, C 2 -C 8 Alkynyl, aryl, C 1 -C 8 Perfluoroalkoxy, C 1 -C 8 Perfluoroalkyl and C 1 -C 8 Partially fluorinated alkyl, and m is from 0 to 4, and n is from 0 to 3; and b. at least one selected from compounds capable of reacting with -O-R 2 and -N(R 2 ) 2 Partial reaction of the compound with the relative reactant, wherein R 2 Selected from C 1 -C 4 Alkyl. In a twenty-seventh aspect, the present invention provides a method as in the twenty-sixth aspect, wherein the precursor composition comprises at least one compound selected from the compounds of formula (I), and wherein Y is a group of the following formula: , and wherein each R is independently selected from methyl, ethyl, isopropyl and tert-butyl; and R 1 Selected from hydrogen, methyl and ethyl. In a twenty-eighth aspect, the present invention provides a method as in the twenty-sixth aspect, wherein the precursor composition comprises at least one compound selected from formula (I), and wherein Y is a group of the following formula: , and wherein each R is independently selected from methyl, ethyl, isopropyl and tert-butyl; and R 1 is selected from hydrogen, methyl and ethyl. In a twenty-ninth aspect, the present invention provides a method as in the twenty-sixth, twenty-seventh or twenty-eighth aspect, wherein R is methyl. In a thirtieth aspect, the present invention provides a method as in the twenty-sixth to twenty-ninth aspects, wherein R 1 is hydrogen or C 1 -C 8 alkyl. Accordingly, several illustrative embodiments of the present invention have been described. Those skilled in the art should readily appreciate that additional embodiments can be made and used within the scope of the appended claims. Many advantages of the invention covered by this document have been set forth in the foregoing description. However, it should be understood that the invention is illustrative in many aspects. Of course, the scope of the invention is defined in the language of the appended claims.

Claims

1. A method for depositing a tin-containing film onto the surface of a microelectronic device in a reaction zone, the method comprising introducing a precursor composition into the reaction zone under vapor deposition conditions, the precursor composition comprising at least one compound selected from formula (III): , wherein R is independently selected from H, C1-C8 perfluorinated alkyl, C1-C8 partially fluorinated alkyl, each R1 is selected from H, C1-C8 alkoxy, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluoroalkoxy, C1-C8 perfluoroalkyl and C1-C8 partially fluorinated alkyl, and m is 0 to 4 and n is 3; and at least one relative reactant selected from compounds capable of reacting with -O-R2 and -N(R2)2 portions, wherein R2 is selected from C1-C4 alkyl.

2. A method for depositing a tin-containing film onto the surface of a microelectronic device in a reaction zone, the method comprising introducing a precursor composition into the reaction zone under vapor deposition conditions, the precursor composition comprising at least one compound selected from formula (I): (I), wherein Y is a group of the following formula: , and wherein each R is independently selected from methyl, ethyl, isopropyl and tertiary butyl; and R1 is selected from hydrogen, methyl and ethyl, and m is 0 to 4, and n is 0; and at least one relative reactant selected from compounds capable of reacting with the -O-R2 and -N(R2)2 moieties, wherein R2 is selected from C1-C4 alkyl.

3. A method for depositing a tin-containing film onto the surface of a microelectronic device in a reaction zone, the method comprising introducing a precursor composition into the reaction zone under vapor deposition conditions, the precursor composition comprising at least one compound selected from formula (I): (I), wherein Y is a group of the following formula: , and wherein each R is independently selected from methyl, ethyl, isopropyl and tertiary butyl; and R1 is selected from hydrogen, methyl and ethyl, and m is 0 to 4, and n is 0; and at least one relative reactant selected from compounds capable of reacting with the -O-R2 and -N(R2)2 moieties, wherein R2 is selected from C1-C4 alkyl.

4. A method for depositing a tin-containing film onto the surface of a microelectronic device in a reaction zone, the method comprising introducing a precursor composition into the reaction zone under vapor deposition conditions, the precursor composition comprising at least one compound selected from formulas (I) and (III): (I), wherein Y is a group of the following formula; wherein R is methyl, and R1 is selected from H, C1-C8 alkoxy, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluoroalkoxy, C1-C8 perfluoroalkyl and C1-C8 partially fluorinated alkyl, and m is 0 to 4, and n is 0; and, R is a methyl group, each R1 is selected from C1-C8 alkoxy, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluoroalkoxy, C1-C8 perfluoroalkyl and C1-C8 partially fluorinated alkyl, and m is 0 to 4 and n is 0 to 3; and at least one relative reactant selected from compounds that can react with -O-R2 and -N(R2)2 moieties, wherein R2 is selected from C1-C4 alkyl.

5. A method for depositing a tin-containing film onto the surface of a microelectronic device in a reaction zone, the method comprising introducing a precursor composition into the reaction zone under vapor deposition conditions, the precursor composition comprising at least one compound selected from formulas (I) and (III): (I), wherein Y is a group of the following formula; wherein R is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, C1-C8 partially fluorinated alkyl, and wherein R1 is independently selected from hydrogen and C1-C8 alkyl, and m is 0 to 4, and n is 0; and, R is independently selected from H, C1-C8 perfluorinated alkyl, C1-C8 partially fluorinated alkyl, each R1 is selected from hydrogen and C1-C8 alkyl, and m is 0 to 4 and n is 0 to 3; and at least one relative reactant selected from compounds that can react with -O-R2 and -N(R2)2 moieties, wherein R2 is selected from C1-C4 alkyl.

6. A method for depositing an EUV-patternable film onto the surface of a microelectronic device in a reaction zone, the method comprising, under vapor deposition conditions, introducing a precursor composition into the reaction zone, the precursor composition comprising reactants selected from: a. a precursor composition selected from at least one compound of formula (I) and (III); (I), wherein Y is a group of the following formula; wherein R is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, C1-C8 partially fluorinated alkyl, and R1 is selected from H, C1-C8 alkoxy, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluoroalkoxy, C1-C8 perfluoroalkyl and C1-C8 partially fluorinated alkyl, and m is 0 to 4, and n is 0; and, R is independently selected from H, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, C1-C8 partially fluorinated alkyl, and R1 is selected from H, C1-C8 alkoxy, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluoroalkoxy, C1-C8 perfluoroalkyl and C1-C8 partially fluorinated alkyl, and m is 0 to 4 and n is 0 to 3; and b. at least one relative reactant selected from compounds capable of reacting with the -O-R2 and -N(R2)2 moieties, wherein R2 is selected from C1-C4 alkyl.

7. The method of claim 6, wherein the precursor composition comprises at least one compound selected from formula (I), wherein Y is a group of the following formula: , and wherein each R is independently selected from methyl, ethyl, isopropyl and third butyl; and R1 is selected from hydrogen, methyl and ethyl.

8. The method of claim 6, wherein the precursor composition comprises at least one compound selected from formula (I), wherein Y is a group of the following formula: , and wherein each R is independently selected from methyl, ethyl, isopropyl and third butyl; and R1 is selected from hydrogen, methyl and ethyl.

9. The method of claim 6, wherein R1 is hydrogen or C1-C8 alkyl.