Synthesis of fluoroalkyltin precursors

Abstract

The present invention provides certain fluorinated alkyltin compounds believed to be useful for the vapor phase deposition of tin-containing films on the surface of a microelectronic device substrate. Also provided are methods for preparing precursor compounds and methods for using such compounds in depositing tin-containing films on a microelectronic device substrate.

Description

[Technical Field]

[0001] Technical field Claim of priority

[0001] This disclosure claims priority to U.S. Provisional Patent No. 63 / 243,885, filed September 14, 2021, which is incorporated herein by reference.

[0002]

[0002] The present invention belongs to the field of organotin chemistry. In particular, the present invention relates to a method for producing certain fluorine-containing tin compounds that are useful for gas-phase deposition of tin-containing films. [Background technology]

[0003] background

[0003] Certain organotin compounds have been shown to be useful for depositing high-purity tin(II) oxide in the manufacture of microelectronic devices. Of particular interest are organotin compounds having a combination of alkylamino groups and alkyl groups, which are useful as liquid precursors in the deposition of tin-containing films on microelectronic device substrates.

[0004]

[0004] Furthermore, certain organometallic compounds have been shown to be useful as precursors in the deposition of high-purity metal oxide films in applications such as extreme ultraviolet (EUV) lithography techniques used in the manufacture of microelectronic devices. In this method, a specific organometallic precursor is used in combination with a reverse reactant to form a polymerized organometallic film. The EUV patternable film is then exposed, which includes forming a pattern on the surface and exposing the film using a patterned EUV light beam, and subsequently exposing the surface of the resulting microelectronic device to post-exposure baking in ambient air. This treatment with patterned EUV light leaves some exposed and some unexposed areas of the surface, so that the different physical and chemical differences between the two regions allow for further manipulation and patterning. See, for example, U.S. Patent Publication 2021 / 0013034.

[0005]

[0005] Therefore, there is a need for further development of precursor compositions and reverse reagent combinations that can be used in this dry (photo)resist process, as well as a need for improvement of the method used for depositing high-purity tin oxide films. [Overview of the project]

[0006]

[0006] In summary, the present invention provides specific fluorinated alkyltin compounds that are considered useful for vapor deposition of tin-containing films on the surface of microelectronic device substrates. In one embodiment, the present invention relates to formula (I), TIFF0007882942000001.tif15170[In the formula, Y is the basis of the following formula, TIFF0007882942000002.tif15170, where R is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl, and R 1 The compound is selected from H, C1-C8 alkoxy, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkoxy, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl, where m is 0-4 and n is 0-3.

[0007] Detailed explanation

[0007] As used herein and in the appended claims, the singular forms “a,” “an,” and “the” refer to multiple subjects unless the context explicitly indicates otherwise. As used herein and in the appended claims, the term “or” is used generally to mean “and / or” unless the context explicitly indicates otherwise.

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

[0009]

[0009] A numerical range expressed using endpoints includes all numerical values within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5).

[0010]

[0010] In one aspect, the present invention provides a compound of formula (I), TIFF0007882942000003.tif15170[where Y is a group of the following formula, TIFF0007882942000004.tif15170and R is selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, C1-C8 partially fluorinated alkyl, R 1 is selected from H, C1-C8 alkoxy, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkoxy, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl, m is 0 to 4, and n is 0 to 3] compound.

[0011]

[0011] In certain embodiments, R is selected from methyl, ethyl, and isopropyl. In certain embodiments, R 1 is selected from hydrogen, methyl, and ethyl.

[0012]

[0012] In certain embodiments, n is 0 to 2. In some embodiments, R 1 is C1-C8 perfluorinated alkyl.

[0013]

- 0013

[0014]

[0014] Similarly, the compounds of formula (B) can be prepared by fluorinating the corresponding bromo, iodine, or chloro compounds using known fluorinating agents. 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, FLM 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), See 9587-9589 and Mathiessen, Bente et al., Chemistry - A European Journal (2011), 17(28), 7796-7805.

[0015]

[0015] Next, the compound of formula (B), for example, when R is phenyl, is treated with about 1 to 3 molar equivalents of SnCl4 to obtain formula (C), A trichlorotin intermediate can be obtained from TIFF0007882942000007.tif16170.

[0016]

[0016] Next, the compound of formula (C) is reacted with about 2 to about 5 molar equivalents of the compound of formula HN(R)2 in the presence of the compound of formula LiN(CH3)2 to obtain the compound of formula (I). Here, Y is the group of the following formula. TIFF0007882942000008.tif14170

[0017]

[0017] Y is the basis of the following equation, The compound of formula (I), TIFF0007882942000009.tif13170, can be prepared by treating the compound of formula (C) with ROH in the presence of a secondary or tertiary amine, or by treating the compound of formula (C) with MOR [wherein M is selected from alkali metals].

[0018]

[0018] In an alternative synthesis route, the compound of formula (I) with n = 1 can be prepared by direct fluorination of a specific intermediate.

[0019]

[0019] Therefore, in another embodiment, the present invention relates to formula (II), TIFF0007882942000010.tif20170[In the formula, R is C1-C8 alkyl, C2- C8 Selected from alkenyls, C2-C8 alkynyls, and aryls, each R 1 [The element is independently selected from H, C1-C8 alkoxy, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, and aryl.] A method for preparing the compound of the following formula (D), The present invention provides a method comprising treating the compound TIFF0007882942000011.tif16170 with a fluorinating agent.

[0020]

[0020] In the above method, exemplary R group and R 1 The groups include methyl, ethyl, propyl, n-butyl, n-pentyl, vinyl, allyl, 2-alkynylpropane, and phenyl. Suitable fluorinating agents include known nucleophilic deoxyfluorinating agents such as the following: Diethylaminosulfur trifluoride (also known as "DAST"); 2-Pyridinesulfonyl fluoride, CAS No. 878376-35-3, sold under the trademark PyFluor®; [Methyl(oxo){1-[6-trifluoromethyl)-3-pyridyl]ethyl}-λ6-sulfanylidene]cyanamide; CAS number 946578-003, also known as "SulfoxaFluor™"; 1,3-Bis(2,6-diisopropylphenyl)-2,2-difluoro-2,3-dihydro-1H-imidazole, CAS No. 1314657-40-3, sold under the trademark PhenoFluor®; (Diethylamino)difluorosulfonium tetrafluoroborate, CAS number 63517-29-3, also known as XtalFluor-E®, is sold by OmegaChem, Inc. Bis(2-methoxyethyl)aminosulfur trifluoride, CAS number 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;

[0021] 4-Morpholinyl sulfur 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®, is marketed by Sigma Aldrich; 4-tert-Butyl-2,6-dimethylphenylsulfur trifluoride, also known as CAS No. 947725-04-4 and sold as FLUOLEAD (trademark) by TCI Chemicals; N,N-Diethyl-1,1,2,3,3,3-hexafluoropropylamine, also known as CAS No. 309-88-6 and known as Ishikawa Reagent; N,N-Diethyl-α,α-difluoro-3-methylbenzylamine, also known as CAS No. 500131-50-0 and known as DFMBA; Tetramethylfluoroformamidinium hexafluorophosphate, also known as CAS No. 164298-23-1 and known as TFFH, sold by Sigma Aldrich; Fluoro-N,N,N’,N’-bis(tetramethylene)formamidinium hexafluorophosphate, also known as CAS No. 164298-25-3 and known as BTFFH, sold by Sigma Aldrich; and 1,3-Bis(2,6-diisopropylphenyl)-2,2-difluoro-2,3-dihydro-1H-imidazole, also known as CAS No. 1314657-40-3 and known as PhenoFluor (trademark).

[0022]

[0021] In a further alternative means of synthesis, the compound of formula (I) where n is 1 (one), i.e., the compound of the following formula (II), can be produced by direct fluorination of the corresponding mesylate or tosylate. The compound of formula (II) is useful as an intermediate for synthesizing the compound of formula (I).

[0023]

[0022] In a further aspect, the present invention relates to formula (II), TIFF0007882942000012.tif20170 [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, R 1[where m is selected from H, C1-C8 alkoxy, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkoxy, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl, where m is 0-4 and n is 0-3] This provides a method for preparing the compound of formula (E), TIFF0007882942000013.tif16170 [In the formula, R 3 The method involves treating a compound of formula MF [wherein M is selected from lithium, potassium, sodium, or a tetra-C1-C8 alkylammonium group] with a compound of formula MF [wherein M is selected from lithium, potassium, sodium, or a tetra-C1-C8 alkylammonium group]. In certain embodiments, this reaction is carried out in the presence of an ionic liquid, a compound such as polyethylene glycol, or a phase transfer catalyst.

[0024]

[0023] The compound of formula (E) can be prepared from the compound of formula (D) by reacting the compound of formula (D) with a halide methanesulfonyl or toluenesulfonyl, such as methanesulfonyl chloride or toluenesulfonyl chloride, in the presence of a base.

[0025]

[0024] The compound of formula (D) above can be prepared using known chemistry according to the following scheme: TIFF0007882942000014.tif85170

[0026]

[0025] Another method for synthesizing the compound of formula (II) is to synthesize the compound of the following formula, TIFF0007882942000015.tif34170 [In the formula, each X is independently selected from the halogen groups] When reacted with the compound, the following formula is obtained. The compound TIFF0007882942000016.tif19170 is provided, which can then be subjected to a halogen exchange reaction in the presence of the compound of formula MF.

[0027]

[0026] The obtained compound can then be treated with SnCl4, and the following formula, The corresponding trichlorotin compound for TIFF0007882942000017.tif19170 is obtained, which is then reacted with a compound of formula LiN(R)2 and at least 2 molar equivalents of a compound of formula (R)2NH, and then the following formula (III) is obtained. TIFF0007882942000018.tif24170[wherein R is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl, R 1 [where m is selected from H, C1-C8 alkoxy, C2-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkoxy, C1-C8 perfluoroalkyl, and C1-C8 partially fluorinated alkyl, where m is 0-4 and n is 0-3] We provide tris(amide)tin compounds.

[0028]

[0027] By yet another alternative means, the compound of formula (D) can be produced according to the following scheme. TIFF0007882942000019.tif84170

[0029]

[0028] In the above reaction scheme, R 4 The compound can be selected from the formulas -Si(CH3)3, -Si(CH2CH3)3, -Si(isopropyl)3, -Si(t-butyl)2(phenyl), and -Si(CH3)2(t-butyl).

[0030]

[0029] Therefore, in a further embodiment, the present invention relates to the following formula, TIFF0007882942000020.tif19170 [In the formula, each R 1 [The element is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, and aryl.] This provides a method for preparing the compound of the following formula, TIFF0007882942000021.tif14170 The compound of formula, in the presence of a base, R 4 Treatment with a -Cl compound yields the following equation: TIFF0007882942000022.tif14170 [In the formula, R 4 The formula is -Si(CH3)3. Selected from the group consisting of -Si(CH2CH3)3, -Si(isopropyl)3, -Si(t-butyl)2(phenyl), and -Si(CH3)2(t-butyl)] This provides a compound of the following formula, which is then treated with a compound of the formula (phenyl)3SnNa to produce the next formula. TIFF0007882942000023.tif19170 The compound is provided, followed by deprotection of the hydroxyl group.

[0031]

[0030] Similar to the compound of formula (I), the compound of (III) is considered useful as a precursor in the vapor deposition of tin-containing films on the surface of a microelectronic device substrate, and as described above, the compound of formula (II) is useful as an intermediate. Therefore, in the fourth aspect, the present invention relates to formulas (II) and (III), TIFF0007882942000024.tif20170 and TIFF0007882942000025.tif24170[wherein R is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl, R 1[where m is selected from H, C1-C8 alkoxy, C2-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkoxy, C1-C8 perfluoroalkyl, and C1-C8 partially fluorinated alkyl, where m is 0-4 and n is 0-3] The compound is provided.

[0032]

[0031] In certain embodiments, R is selected from C1-C3 alkyl groups. In certain embodiments, R is selected from methyl, ethyl, and isopropyl groups. In certain embodiments, R 1 This is selected from hydrogen, methyl, or ethyl.

[0033]

[0032] As described above, these organotin precursor compounds are considered useful in various vapor deposition processes where it is desirable to deposit a tin-containing film on the surface of a microelectronic device. Accordingly, in a fifth aspect, the present invention provides a method for depositing a tin-containing film on the surface of a microelectronic device in a reaction zone, the method comprising introducing a precursor composition comprising at least one compound selected from formulas (I) and (III) into the reaction zone under vapor deposition conditions.

[0034]

[0033] Furthermore, the precursors of the present invention are considered particularly useful for patterning microelectronic device substrates using extreme ultraviolet (EUV) technology. In this regard, see U.S. Patent Publication 2021 / 0013034, incorporated herein by reference. The precursor composition of the present invention is intended to be mixed with a counter-reactant in the form of a vapor stream in a manner that forms an organometallic material in the form of an oligomer or polymer on the surface of a microelectronic device. The film thus formed, considering its reactivity with EUV light, becomes an EUV patternable film.

[0035] Therefore, in the sixth aspect, a method for depositing an EUV patternable film on the surface of a microelectronic device within a reaction zone, a. A precursor composition comprising a reactant selected from at least one compound of formulas (I) and (III), b.-O- R and bi-N( R) 2 parts ( R is A method comprising introducing at least one counter-reactant selected from compounds that can react with (selected from C1-C4 alkyl groups) into a reaction zone under gas-phase deposition conditions.

[0036]

[0035] Suitable counter reactants are the -O- compounds of formulas (I) and (III) above. R and bi / or -N( R) The compound can have two groups substituted and includes substances such as water, peroxides such as hydrogen peroxide, dihydroxy or polyhydroxy alcohols, hydrogen sulfide, hydrogen disulfide, trifluoroacetaldehyde monohydrate, fluorinated dihydroxy or polyhydroxy alcohols, and fluorinated glycols.

[0037]

[0036] The thin film formed in this way is SnO x These are oligomer or polymer organometallic materials containing x, where x is approximately 1.5 to 2. Furthermore, the thickness of these EUV patternable thin films generally varies from approximately 0.5 to 100 nm.

[0038]

[0037] In certain embodiments, the gas phase deposition conditions include reaction conditions known as chemical gas deposition, pulsed chemical gas deposition, and atomic layer homing deposition. In the case of pulsed chemical homing deposition, a series of alternating pulses of the precursor composition and counter reactants can be used to accumulate the film thickness to a desired endpoint, with or without an intermediate (inert gas) purge step.

[0039]

[0038] In certain embodiments, the pulse time of the precursor compound shown above (i.e., the duration of the precursor exposure to the substrate) is in the range of about 1 to 30 seconds. When a purge step is used, the duration is about 1 to 20 seconds or 1 to 30 seconds. In other embodiments, the pulse time of the co-reactant is in the range of 5 to 60 seconds.

[0040]

[0039] In one embodiment, the gas phase deposition conditions include a reaction zone temperature of about 0°C to about 250°C, or about 22°C to about 150°C, and a reduced pressure of about 10 mTorr to about 10 Torr.

[0041]

[0040] When used in combination with the reactants described above, a precursor composition comprising a compound selected from at least one of formulas (I) to (VI) above 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 vapor deposition (ALD), or fluid chemical vapor deposition (FCVD) can be utilized.

[0042]

[0041] In a tenth aspect of the present invention, the above compound can be reacted with counter reactants in a reaction zone and the surface of a desired microelectronic device substrate by any suitable method, for example, single-wafer CVD or ALD, or in a furnace including multiple wafers.

[0043]

[0042] Alternatively, the method of the present invention may also be carried out as an ALD or ALD-like method. As used herein, the term "ALD or ALD-like" means, for example, (i) sequentially introducing each reactant and counter reactant, comprising a precursor composition containing a compound selected from formulas (I) and (III), into a reactor such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; or (ii) each reactant being exposed to the surface of a substrate or microelectronic device by moving or rotating the substrate to different sections of the reactor, with each section separated by an inert gas curtain, i.e., a space ALD reactor or a roll-to-roll ALD reactor. In certain embodiments, the thickness of the ALD film is about 0.5 nm to about 40 nm, and the deposition temperature is in the range of about 30°C to about 500°C.

[0044]

[0043] The deposition methods disclosed herein may require one or more purge gases. The purge gas used to purge any unconsumed reactants and / or reaction by-products is an inert gas that does not react with either the precursor composition or the counter-reactants. 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 supplied into the reactor at a flow rate in the range of about 10 to about 2000 sccm for about 0.1 to 1000 seconds, thereby purging any unreacted material and by-products that may remain in the reactor. Such a purge gas may also be used as an inert carrier gas for either or both of the precursor composition and the counter-reactants.

[0045]

[0044] Each step of supplying the precursor composition and the counter-reactants can be carried out by changing the order in which they are supplied and / or by changing the stoichiometric composition of the resulting EUV patternable film.

[0046]

[0045] Energy is added to the precursor composition and co-reactants in the reaction zone to induce a reaction and form an EUV patternable film on the surface of the microelectronic device. 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-rays, electron beams, 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 in which deposition involves plasma, the plasma generation process is a direct plasma generation process in which the plasma is generated directly in the reactor, or alternatively, a remote plasma generation process in which the plasma is generated "remotely" between the reaction zone and the substrate and supplied to the reactor.

[0047]

[0046] As used herein, the term “microelectronic device” refers to semiconductor substrates, including 3D NAND structures, flat panel displays, and microelectromechanical systems (MEMS), manufactured for use in microelectronics, integrated circuits, or computer chip applications. It should be understood that the term “microelectronic device” is not limited to any substrate, including negative channel metal-oxide-semiconductor (nMOS) and / or positive channel metal-oxide-semiconductor (pMOS) transistors, which ultimately become microelectronic devices or microelectronic assemblies. Such microelectronic devices include, for example, tin, SiO2, Si3N4, OSG, FSG, tin carbide, tin hydride carbide, tin nitride, tin hydride nitride, tin carbonitride, hydrogenated tin carbonitride, boron nitride, anti-reflective coatings, photoresists, germanium, germanium-containing materials, boron-containing materials, Ga / As, flexible substrates, porous inorganic materials, metals such as copper or aluminum, and, but are not limited to, at least one substrate that can be selected from a diffusion barrier layer of TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. [Examples]

[0048]

[0047] Example 1

[0048] Ph3SnCH2CH2(CH3)OH can be synthesized according to the procedure described in Davis, DD; Gray, CE Deoxymetalation Reactions. Mechanism of Deoxystannylation. J. Org. Chem. 1970, 35 (5), 1303-1307. (Ph = phenyl).

[0049]

[0049] Example 2

[0050] Cl(CH2)2O-TMS can be synthesized according to the procedure described in Mander, LN; Turner, JV, 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).

[0050]

[0051] Example 3 Ph3SnCH2CH2OTMS

[0052] To 32.6 mL of a 0.1 M solution of sodium triphenylstannate (3.27 mmol) in tetrahydrofuran (THF) in a 100 mL round-bottom flask cooled to -65°C, a solution of (2-chloroethoxy)trimethylsilane (0.500 g, 3.27 mmol) was added over 5 minutes in 5 mL of THF. Only minimal exothermic reaction was observed. The reaction mixture was stirred at -65°C for 1 hour and then warmed to ambient temperature. All volatile substances were removed from the reaction mixture under reduced pressure, and the mixture was slurryed in the smallest amount of hexane and filtered through a Celite bed. The filtrate was concentrated to obtain 0.650 g of yellow oil (42%). 1 H-NMR (149 MHz CDCl3, 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 { 1 H} NMR (100 MHz, CDCl3289K): d 139.88, 137.60, 129.00, 128.72, 60.13, 17.44, -0.63 ppm. 119 Sn { 1 H} NMR (149 MHz CDCl3, 298K): d - 99.61 ppm.

[0051]

[0053] Example 4: Ph3SnCH2CH2OH(Prophetic) deprotection with Ph3SnCH2CH2OTMS

[0054] The conversion of Ph3SnCH2CH2OTMS to Ph3SnCH2CH2OH can be performed by modifying the procedure referenced in the protection of hydroxyl groups containing 1,2- and 1,3-diols. (In Protective Groups in Organic Synthesis; John Wiley & Sons, Ltd, 1999; pp 119-121.) TIFF0007882942000026.tif37170 (MeOH = methanol)

[0052]

[0055] Dissolve anhydrous citric acid (2.05 g, 10.7 mmol) in 60 mL of methanol in a 100 mL flask, and transfer trimethyl[2-(triphenylstannyl)ethoxy]silane (5.00 g, 10.7 mmol) to the flask. Stir the reaction mixture for 24 hours, remove volatile components under reduced pressure, and extract with 100 mL of THF. Wash the THF solution with saturated sodium bicarbonate solution, then with water, then separate and dry over magnesium sulfate. Next, remove volatile substances under reduced pressure to obtain the product as a white solid.

[0053]

[0056] Example 5 Ph3SnCH2CH2OTBDMS(Prophetic)

[0057] To a THF solution of sodium triphenylstanate (54.0 mL, 54.0 mmol), 10 mL of anhydrous tetrahydrofuran solution of tert-butyl(2-chloroethoxy)dimethylsilane (10.5 g, 54.0 mmol) was added dropwise at -65°C. The dark green solution was heated to ambient temperature over 18 hours, and then all volatile substances were removed under vacuum. The residue was made into a slurry in the smallest possible amount of hexane, filtered through a Celite bed, and the filtrate was concentrated under vacuum. (TBDS = tert-butyldimethylsilyl).

[0054]

[0058] Example 6 Ph3SnCH2CH2OTBDMS(Prophetic) derived from Ph3SnCH2CH2OH TIFF0007882942000027.tif34170

[0055]

[0059] To a 10 mL solution of tert-butyldimethyl[2-(triphenylstannyl)ethoxy]silane (5.00 g, 9.81 mmol) in THF, add a solution of tetrabutyl(fluoro)amine (19.6 mL, 19.6 mmol) (1.0 M in THF). Stir the mixture for 18 hours and add 30 mL of water. Extract the mixture twice with diethyl ether (20 mL aliquot), and wash the combined organic layers sequentially with saturated NH4Cl solution and saturated brine solution. Dry the product solution over magnesium sulfate, and then remove all volatiles under reduced pressure.

[0056]

[0060] Example 7 Ph3SnCH2CH2OTs derived from Ph3SnCH2CH2OH(Prophetic) TIFF0007882942000028.tif43170

[0057]

[0061] Equipped with a PTFE-coated stirring egg, a 100 mL round-bottom flask, cooled to approximately 5°C in an ice bath, contained a stirring solution of Ph3SnCH2CH2OH (3.95 g, 10.00 mmol) in pyridine (6.00 mL, 74.4 mmol). p-toluenesulfonyl chloride (2.19 g, 11.5 mmol) was added in several batches. The resulting mixture was stirred in an ice bath for 3 hours, diluted with 35.0 mL of dichloromethane, and continuously washed with 10 mL of 2 M HCl, 10 mL of water, and 10 mL of 10% sodium bicarbonate aqueous solution. The organic layer was separated, dried over magnesium sulfate, and all volatile components were removed under reduced pressure.

[0058]

[0062] Example 8 Ph3SnCH2CH2-F derived from Ph3SnCH2CH2OTs(Prophetic) TIFF0007882942000029.tif42170

[0059]

[0063] To a 9.55 mL solution of 1.0 M tetrabutylammonium fluoride in THF (9.55 mmol), add Ph3SnCH2CH2OTs (5.00 g, 9.10 mmol). Reflux the solution for 18 hours, then remove all volatile components.

[0060]

[0064] Example 9 Ph3SnCH2CH2-F derived from Ph3SnCH2CH2OH (Prophetic) TIFF0007882942000030.tif33170

[0061]

[0065] To a chilled (-70°C) solution of diethylaminosulfur trifluoride (2.29 g, 12.8 mmol) in 25 mL of dichloromethane, a solution of Ph3SnCH2CH2OH (5.00 g, 12.6 mmol) is added dropwise. The stirred solution is warmed to ambient temperature over 3 hours. The reaction mixture is added to 50 mL of saturated sodium bicarbonate solution cooled to 0°C, and then extracted twice with 20 mL aliquots of dichloromethane. The combined organic phase is dried over magnesium sulfate and filtered through a silica plug. Then, volatile components are removed from the product solution under reduced pressure.

[0062]

[0066] Example 10 Cl3SnCH2CH2-F derived from Ph3SnCH2CH2-F (Prophetic) TIFF0007882942000031.tif32170

[0063]

[0067] In a 100 mL flask equipped with a stirring bar and a thermowell, (2-fluoroethyl)triphenylstannane (40.00 g, 100 mmol) is added, followed by tetrachlorostannane (52.1 g, 200 mmol) in several additions. Once the additions are complete, the flask is mounted in a distillation apparatus equipped with a 1'-Vigreux column. The product is then fractionally distilled under reduced pressure from phenyltrichlorotin and diphenyldichlorotin.

[0064]

[0068] Example 11: (Me2N)3SnCH2CH2-F derived from Cl3SnCH2CH2-F (Prophetic) TIFF0007882942000032.tif22170

[0065]

[0069] In a 250 mL three-necked round-bottom flask equipped with a stirring egg, charge butyllithium (36.0 mL, 57.6 mmol) and 35 mL of hexane. Cool the solution to 0°C and then treat with dimethylamine (6.58 g, 146 mmol). Next, cool the resulting slurry to -10°C and treat by adding 25 mL of hexane solution of trichloro(2-fluoroethyl) stannane (5.00 g, 18.3 mmol) dropwise over 2 hours. Warm the reaction mixture to ambient temperature over 18 hours and then filter. Concentrate the filtrate under reduced pressure to obtain the desired product.

[0066] manner

[0070] In the first aspect, the present invention relates to formula (I), TIFF0007882942000033.tif15170[In the formula, Y is the basis of the following formula, TIFF0007882942000034.tif15170, where R is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl. 1 [where m is selected from H, C1-C8 alkoxy, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkoxy, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl, where m is 0-4 and n is 0-3] The compound is provided.

[0067]

[0071] In a second aspect, the present invention relates to a system in which Y is the following base, The present invention provides a compound of the first embodiment, which is TIFF0007882942000035.tif14170.

[0068]

[0072] In a third aspect, the present invention relates to a system in which Y is the following base, The present invention provides a compound of the first embodiment, which is TIFF0007882942000036.tif13170.

[0069]

[0073] In a fourth aspect, the present invention provides a compound of the first, second, or third aspect, wherein n is 2.

[0070]

[0074] In a fifth aspect, the present invention provides a compound according to any one of the first to fourth aspects, wherein R is selected from C1 to C3 alkyl groups.

[0071]

[0075] In a sixth aspect, the present invention provides a compound according to any one of the first to fifth aspects, wherein R is selected from methyl, ethyl, and isopropyl.

[0072]

[0076] In the seventh aspect, the present invention relates to R 1 The present invention provides one of the first to sixth embodiments of a compound in which is selected from hydrogen, methyl, or ethyl.

[0073]

[0077] In the eighth aspect, the present invention provides a compound according to any one of the first to seventh aspects, wherein R is selected from methyl, ethyl, and isopropyl, 1 The element is selected from hydrogen, methyl, or ethyl.

[0074]

[0078] In the ninth aspect of the present invention, R is methyl, 1 The present invention provides one compound according to any one of the first to eighth embodiments, wherein the compound is methyl.

[0075]

[0079] In the tenth aspect, the present invention relates to formula (II), TIFF0007882942000037.tif20170[wherein R is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl, R 1A method for preparing a compound in which [ is selected from H, C1-C8 alkoxy, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkoxy, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl, where m is 0-4 and n is 0-3] The following equation (D), The present invention provides a method comprising treating the compound TIFF0007882942000038.tif16170 with a fluorinating agent.

[0076]

[0080] In the eleventh aspect, the present invention provides a method according to the tenth aspect, wherein the fluorinating agent is diethylaminosulfur trifluoride, [methyl(oxo){1-[6-trifluoromethyl)-3-pyridyl]ethyl}-λ6-sulfanylidene]cyanamide; 1,3-bis(2,6-diisopropylphenyl)-2,2-difluoro-2,3-dihydro-1H-imidazole; (diethylamino)difluorosulfonium tetrafluoroborate; bis(2-methoxyethyl)aminosulfur trifluoride; perfluorobutanesulfonyl fluoride; 4-morpholinyl sulfur trifluoride; difluoro-4-morpholinylsulfonium tetrafluoroborate; 4-tert-butyl-2,6-dimethylphenyl sulfur trifluoride; N,N-diethyl-1,1,2,3,3,3-hexafluoropropylamine; Selected from 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.

[0077]

[0081] In a twelfth aspect, the present invention provides a method according to the tenth or eleventh aspect, wherein R is phenyl.

[0078]

[0082] In the 13th aspect, the present invention is R 1The present invention provides one of the tenth to twelfth embodiments, wherein is hydrogen or a C1-C8 alkyl group.

[0079]

[0083] In the fourteenth aspect, the present invention relates to the following formula (II), TIFF0007882942000039.tif20170 [In the formula, R is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl. 1 [where m is selected from H, C1-C8 alkoxy, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkoxy, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl, where m is 0-4 and n is 0-3] A method for preparing a compound of formula ( E ), TIFF0007882942000040.tif16170 [In the formula, R 2 The present invention provides a method comprising treating a compound of the form toluenesulfonyl or methanesulfonyl with a compound of the form MF [wherein M is selected from lithium, potassium, sodium, or a tetra-C1-C8 alkylammonium group].

[0080]

[0084] In a 15th aspect, the present invention provides the method of the 14th aspect, wherein R is phenyl.

[0081]

[0085] In the sixteenth aspect, the present invention relates to R 1 The present invention provides a method according to a 14th or 15th embodiment, wherein is hydrogen or a C1-C8 alkyl group.

[0082]

[0086] In the seventeenth aspect, the present invention relates to the following formula: TIFF0007882942000041.tif19170 [In the formula, each R 1 [The element is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, and aryl.] A method for preparing a compound of the following formula, TIFF0007882942000042.tif14170 The compound, in the presence of a base, formula R 4 Treatment with a -Cl compound yields the following: TIFF0007882942000043.tif14170 [In the formula, R 4 This provides a compound selected from the group -Si(CH3)3, -Si(CH2CH3)3, -Si(isopropyl)3, -Si(t-butyl)2(phenyl), and -Si(CH3)2(t-butyl), which is then treated with a compound of the formula (phenyl)3SnNa to obtain the following formula: TIFF0007882942000044.tif19170 The compound is provided, followed by deprotection of the hydroxyl group.

[0083]

[0087] In the eighteenth aspect, the present invention relates to the following formulas (II) and (III), TIFF0007882942000045.tif20170 and TIFF0007882942000046.tif24170[wherein R is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl, R 1 [where m is selected from H, C1-C8 alkoxy, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkoxy, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl, where m is 0-4 and n is 0-3] We provide compounds selected from the following compounds.

[0084]

[0088] In a 19th aspect, the present invention provides a compound of the 18th aspect, wherein R is methyl.

[0085]

[0089] In the 20th aspect, the present invention is R 1 The present invention provides a compound of the 18th or 19th embodiment, wherein the element is hydrogen or a C1-C8 alkyl group.

[0086] In a 21st aspect, the present invention relates to a method for depositing a tin-containing film on the surface of a microelectronic device in a reaction zone, wherein the following formulas (I) and (III) are used: TIFF0007882942000047.tif15170 [In the formula, Y is the basis of the following formula, TIFF0007882942000048.tif15170 R is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl. 1 [where m 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, m is 0-4 and n is 0-3], and TIFF0007882942000049.tif24170 [In the formula, R is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl. 1 A precursor composition comprising at least one compound 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, where m is 0-4 and n is 0-3, -O- R and bi-N( R) 2 parts ( R is At least one counter-reactant selected from compounds that can react with (selected from C1-C4 alkyl groups), The present invention provides a method that includes introducing a substance into a reaction zone under gas-phase deposition conditions.

[0087]

[0091] In the 22nd aspect of the present invention, the precursor composition is of formula (I) [wherein Y is a base of the following formula, TIFF0007882942000050.tif14170, where each R is independently selected from methyl, ethyl, isopropyl, and t-butyl, R 1 [Selected from hydrogen, methyl, and ethyl] A method according to a 21st embodiment is provided, comprising at least one compound selected from the following.

[0088]

[0092] In the 23rd aspect of the present invention, the precursor composition is of formula (I) [wherein Y is a base of the following formula, TIFF0007882942000051.tif13170, where each R is independently selected from methyl, ethyl, isopropyl, and t-butyl, R 1 [Selected from hydrogen, methyl, and ethyl] A method according to a 21st embodiment is provided, comprising at least one compound selected from the following.

[0089]

[0093] In a 24th aspect, the present invention provides a method according to the 21st, 22nd, or 23rd aspect, wherein R is methyl.

[0090]

[0094] In the 25th aspect, the present invention is R 1 The present invention provides one of the 21st to 24th embodiments, wherein is hydrogen or a C1-C8 alkyl group.

[0091]

[0095] In a 26th aspect, the present invention relates to a method for depositing an EUV patternable film on the surface of a microelectronic device within a reaction zone, a. The following equations (I) and (III), TIFF0007882942000052.tif15170 [In the formula, Y is the basis of the following formula, TIFF0007882942000053.tif15170 R is independently selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl. 1 [where m 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, m is 0-4 and n is 0-3], and TIFF0007882942000054.tif24170 [In the formula, R is selected from H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkyl, C1-C8 partially fluorinated alkyl, and R 1 [where m is selected from H, C1-C8 alkoxy, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, aryl, C1-C8 perfluorinated alkoxy, C1-C8 perfluorinated alkyl, and C1-C8 partially fluorinated alkyl, where m is 0-4 and n is 0-3] A precursor composition comprising a reactant selected from, b.-O- R and bi-N( R) 2 parts [ R is [Selected from C1-C4 alkyl groups] and at least one counter-reactant selected from compounds that can react with [C1-C4 alkyl groups], The present invention provides a method that includes introducing a substance into a reaction zone under gas-phase deposition conditions.

[0092]

[0096] In the 27th aspect of the present invention, the precursor composition is of formula (I) [wherein Y is a base of the following formula, TIFF0007882942000055.tif14170, where each R is independently selected from methyl, ethyl, isopropyl, and t-butyl, R 1 The present invention provides a method according to a 26th embodiment, comprising at least one compound selected from hydrogen, methyl, and ethyl.

[0093]

[0097] In the 28th aspect of the present invention, the precursor composition is of formula (I) [wherein Y is a base of the following formula, TIFF0007882942000056.tif13170, where each R is independently selected from methyl, ethyl, isopropyl, and t-butyl, R 1 The present invention provides a method according to a 26th embodiment, comprising at least one compound selected from hydrogen, methyl, and ethyl.

[0094]

[0098] In a 29th aspect, the present invention provides a method according to the 26th, 27th, or 28th aspect, wherein R is methyl.

[0095]

[0099] In the 30th aspect, the present invention is R 1 The present invention provides one of the 26th to 29th embodiments, wherein is hydrogen or a C1-C8 alkyl group.

[0096]

[0100] While several exemplary embodiments of this disclosure have been described above, those skilled in the art will readily understand that further embodiments can be created and used within the scope of the appended claims. Many of the advantages of the disclosure covered by this document have been described above. However, it will be understood that this disclosure is in many respects merely illustrative. Of course, the scope of this disclosure is defined in the language in which the appended claims are expressed.

Claims

1. Equation (I) [In the formula, Y is the basis of the following formula, and R is C １ to C3 alkyl, and R １ is H, C １ to C ８ alkoxy, C １ to C ８ alkyl, C ２ to C ８ alkenyl, C ２ to C ８ alkynyl, aryl, C １ to C ８ perfluorinated alkoxy, C １ to C ８ perfluorinated alkyl, and C １ to C ８ partially fluorinated alkyl, and m is 0 to 4 and n is 0 to 2] A compound of [unclear].

2. The compound according to claim 1, wherein R1 is selected from H, methyl, and ethyl.

3. A method for depositing a tin-containing film on the surface of a microelectronic device within a reaction zone, wherein the following formula (I) [In the formula, Y is the basis of the following formula, And R is C １ ~Selected independently from C3 alkyl, R １ H, C １ ~C ８ Alkoxy, C １ ~C ８ Alkyl, C ２ ~C ８ Alkenil, C ２ ~C ８ Alkinyl, aryl, C １ ~C ８ Perfluorinated alkoxy, C １ ~C ８ Perfluorinated alkyl, and C １ ~C ８ Selected from partially fluorinated alkyl groups, where m is 0 to 4 and n is 0 to 2. A precursor composition comprising at least one compound of, - At least one counter-reactant selected from compounds that can react with the -O-R moiety and A method comprising introducing into a reaction zone under gas-phase deposition conditions.

4. The method according to claim 3, wherein at least one counter-reactant is selected from water, peroxide, dihydroxy or polyhydroxy alcohol, hydrogen sulfide, hydrogen disulfide, trifluoroacetaldehyde monohydrate, fluorinated dihydroxy or polyhydroxy alcohol, and fluorinated glycol.

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