Organotin Precursor Compounds

Abstract

The present invention provides certain organotin compounds believed to be useful for the deposition of tin-containing films on the surface of microelectronic device substrates, as well as for the deposition of EUV patternable films. Certain novel precursor compositions are also provided. Methods of forming films using the novel precursors are also disclosed.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This invention claims priority to U.S. Provisional Patent Application No. 63 / 282,893, filed November 24, 2021, which is incorporated herein by reference.

[0002] This invention is in the field of organotin chemistry, and in particular relates to certain organotin precursor compounds. [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 in the fabrication of microelectronic devices. This method utilizes specific organometallic precursors along with a counter reactant to form a polymerized organometallic film. A pattern is then formed on the surface, exposing the EUV-patternable film to light, 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, thus allowing for further manipulation and patterning due to the distinct physical and chemical differences between the two regions. See, for example, U.S. Patent Publication No. 2021 / 0013034.

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

[0005] In summary, the present invention provides certain organotin compounds believed to be useful for depositing tin-containing films on the surface of microelectronic device substrates. Certain novel precursor compounds are also provided. Generally, the precursor compounds of the present invention are organotin compounds having two or three tin centers, e.g., alkoxide and / or amide functional groups. The precursors are believed to be particularly useful in EUV patterning operations. DETAILED DESCRIPTION OF THE INVENTION

[0006] 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.

[0007] The term "about" generally refers to a range of numbers that are considered equivalent to the recited value (e.g., have the same function or result). In many instances, the term "about" may include numbers that are rounded to the nearest significant figure.

[0008] 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).

[0009] In one aspect, the present invention provides a method for depositing a tin-containing film on a surface of a microelectronic device in a reaction zone, the method comprising: TIFF0007825049000001.tif27170 (in the formula, R 1 is a group selected from -C(R)2-, -CR(X)-, -O-, and -N(R)-; R is selected from H and C1-C5 alkyl; X is selected from F, Cl, Br, I, —OCH3, —OCH2CH3, —OCH2CH2CH3, and —OCH(CH3)2; and R 2 are H, -N(R)2, -OR, and -R 1 (selected from and introducing into a reaction zone under deposition conditions a precursor composition comprising at least one compound selected from:

[0010] The compounds of formula (I) are believed to be useful as precursors in the deposition of tin-containing films on microelectronic device substrates. As used herein, the term "tin-containing" film includes elemental tin, tin oxide, tin carbide, and tin nitride, as well as different proportions of each in a given film. If an elemental tin film is desired, a reducing agent such as hydrogen may be used as a co-reactant. If a tin nitride film is desired, a co-reactant such as ammonia or nitrogen may be used.

[0011] In another aspect, the present invention provides a method for depositing a tin-containing film on a surface of a microelectronic device in a reaction zone, the method comprising: TIFF0007825049000002.tif27170 (in the formula, R 1 is a divalent group selected from —C(R)—, —CR(X)—, —O—, and —N(R)—; R is selected from H and C1-C5 alkyl; X is selected from F, Cl, Br, I, —OCH3, —OCH2CH3, —OCH2CH2CH3, and —OCH(CH3)2; and R 2 are H, -N(R)2, and -OR, and -R 1 (selected from a precursor composition comprising at least one compound selected from at least one counter reactant selected from compounds capable of reacting with -OR and -N(R); into a reaction zone under deposition conditions.

[0012] In this regard, compounds of formula (I) are believed to be useful in EUV patterning operations when utilizing counter reactants such as those described above.

[0013] In another aspect, the present invention provides a method for depositing a tin-containing film on a surface of a microelectronic device in a reaction zone, the method comprising: TIFF0007825049000003.tif11170 (in the formula, R 1 is a divalent radical selected from —CH—, —C═C—, —C≡C—, —O—, —N(R)—, —ORRO-, and —CH(X)—; R is selected from H and C1-C5 alkyl; X is selected from F, Cl, Br, I, —OCH3, —OCH2CH3, —OCH2CH2CH3, and —OCH(CH3)2; n is an integer from 0 to 5, R 2 are H, -N(R)2, and -OR, and -R 1 and m is an integer from 0 to 2. and introducing into a reaction zone under deposition conditions a precursor composition comprising at least one compound selected from:

[0014] Similar to the compound of formula (I), the compound of formula (II) is believed to be useful as a precursor in the deposition of tin-containing films on microelectronic device substrates. Thus, the compound of formula (II) can be used with a variety of co-reactants to deposit the desired tin-containing films as elemental tin, tin oxide, and tin nitride. Furthermore, when used with a counter-reactant, such as those described below, the precursor and method can be used to prepare EUV-patternable films.

[0015] Thus, in another aspect, the present invention provides a method for depositing a tin-containing film on a surface of a microelectronic device in a reaction zone, the method comprising: TIFF0007825049000004.tif11170 (in the formula, R 1 is a divalent radical selected from —CH—, —C═C—, —C≡C—, —O—, —N(R)—, —ORRO-, and —CH(X)—; R is selected from H and C1-C5 alkyl; X is selected from F, Cl, Br, I, —OCH3, —OCH2CH3, —OCH2CH2CH3, and —OCH(CH3)2; n is an integer from 0 to 5, R 2 are H, -N(R)2, and -OR, and -R 1 and m is an integer from 0 to 2. a precursor composition comprising at least one compound selected from at least one counter reactant selected from compounds capable of reacting with -OR and -N(R); into a reaction zone under deposition conditions.

[0016] R 2 Compounds of formula (II) in which the group is an amide group can be prepared according to the following Scheme I: TIFF0007825049000005.tif17170 Scheme I. (In the formula, R 1 and R 2 is as above, and M is an alkali metal or alkaline earth metal. Exemplary metals (M) include alkaline earth and alkali metal salts, including but not limited to lithium, sodium, potassium, magnesium, calcium, and zinc.

[0017] Furthermore, compounds of formula (II) can be prepared according to the following scheme II: TIFF0007825049000006.tif39170 Scheme II. (where "TMS" is trimethylsilyl) It can be prepared according to

[0018] See, for example, "Stille Cross-Coupling of Activated Alkyltin Reagents under 'Ligandless' Conditions," A. Herve, et al., J. Org. Chem. 2005, 70, 5, 1953-1956. In Scheme II, R 1 and R 2 is as defined above, and M is a transition metal. Exemplary metals (M) include alkaline earth metal salts and alkali metal salts, including but not limited to lithium, sodium, potassium, magnesium, calcium, and zinc, and X is a halogen atom.

[0019] Compounds of formula (I) can be prepared according to the following Scheme III: TIFF0007825049000007.tif27170 Scheme III (In the formula, R, R 1 , and R 2 is as above, and M is a transition metal. Exemplary metals (M) include alkaline earth and alkali metal salts, including but not limited to lithium, sodium, potassium, magnesium, calcium, and zinc.

[0020] For example, (i) “Some Applications of the Methylene Di-Grignard Reagent for the Synthesis of Main Group IV Organometallic Compounds”, JW, Bruin, et al., Journal of Organometallic Chemistry, Volume 288, Issue 1,11 June 1985, pages 13-25; (ii) “A General Route to Alkylene-, Arylene-, or Benzylene-Bridged Ditin Hexachlorides and Hexaalkynides”, B. Jousseaume, et al., Organometallics 2002, 21, 22, 4590-4594; and (iii) “Macrocycles Containing Tin.Syntheses of Symmetrical Macrocycles Containing Two or Four Diphenylstanna Units”, Y. Azuma et al. al., Organometallics 1984, 3, 1, 9-14.

[0021] In a further aspect, the present invention provides certain compounds of formula (I) and (II) that are believed to be useful as precursors herein. In one aspect, the present invention provides compounds of formula: TIFF0007825049000008.tif27170 (in the formula, R 1 is a group selected from -C(R)2-, -CR(X)-, -O-, and -N(R)-; R is selected from H and C1-C5 alkyl; X is selected from F, Cl, Br, I, —OCH3, —OCH2CH3, —OCH2CH2CH3, and —OCH(CH3)2; and R 2 is selected from groups of formula -N(R)2 and -OR A precursor composition is provided comprising the compound of formula (I).

[0022] In this embodiment, similar to compounds of formula (I) and (II) herein, each R is independently selected from hydrogen and C1-C5 alkyl; thus, groups of formula -N(R)2 include secondary amines of formula -NHR.

[0023] In a further aspect, the present invention provides a compound of formula: TIFF0007825049000009.tif9170 (in the formula, R 1 is a group selected from -CH2-, -C=C-, -C≡C-, -O-, -N(R)-, -ORRO-, and -CH(X)-, R is selected from H and C1-C5 alkyl; R 2 is a group of formula -N(R)2, and X is selected from F, Cl, Br, I, —OCH3, —OCH2CH3, —OCH2CH2CH3, and —OCH(CH3)2. A precursor composition is provided comprising the compound of formula (I).

[0024] In this embodiment, each R is independently selected from hydrogen and C1-C5 alkyl; thus, a group of formula -N(R)2 includes a secondary amine of formula -NHR.

[0025] As noted above, these organotin precursor compounds are believed to be useful in a variety of vapor deposition methods where deposition of tin-containing films on the surfaces of microelectronic devices is desired.

[0026] Also, as noted above, the precursors of the present invention are believed to be particularly useful in patterning microelectronic device substrates using extreme ultraviolet (EUV) technology. See U.S. Patent Publication No. 2021 / 0013034, incorporated herein by reference. It is contemplated that the precursor compositions of the present invention, in the form of a vapor stream, are mixed with a counter-reactant in a manner that forms an organometallic material in oligomeric or polymeric form on the microelectronic device surface. The films thus formed, when rendered reactive with EUV light, become EUV-patternable films.

[0027] Suitable counter reactant(s) are compounds capable of displacing the alkoxide or amide groups of the compounds of formulas (I) and (II) above, and include materials such as water, peroxides, e.g., 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 x where x is from about 1.5 to about 2. Furthermore, these EUV-patternable thin films generally vary in thickness from about 0.5 to about 100 nm.

[0029] In certain embodiments, the pulse time of the precursor compounds (i.e., the duration of precursor exposure to the substrate) ranges from about 1 to 30 seconds. If 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 ranges from 5 to 60 seconds.

[0030] In one embodiment, the 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 reduced pressure of about 10 mTorr to about 10 Torr.

[0031] Precursor compositions containing the precursor compounds described herein, when used with the counter-reactant materials mentioned above, can be used to form (a) tin-containing films and (b) high-purity EUV-patternable films. Any suitable deposition technique can be utilized, such as chemical vapor deposition (CVD), digital (pulsed) CVD, atomic layer deposition (ALD), or flowable chemical vapor deposition (FCVD). In the case of pulsed deposition, a series of alternating pulses of the precursor composition and counter-reactant(s), with or without intermediate (e.g., inert gas) purge steps, can be utilized to build up the film thickness to a desired endpoint.

[0032] The compounds described herein may be reacted with the reaction counter reactant(s) in a reaction zone and the surface of the desired microelectronic device substrate in any suitable manner, for example, in a single wafer CVD or ALD, or in a furnace containing multiple wafers.

[0033] Alternatively, the methods of the present invention can be carried out as ALD or ALD-like methods. As used herein, the term "ALD or ALD-like" refers to methods in which (i) each reactant, including a precursor composition comprising a compound selected from Formulas (I) and (II), and counter-reactant(s) 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) each reactant is exposed to the substrate or microelectronic device surface by moving or rotating the substrate through 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 can be from about 0.5 nm to about 40 nm, and the deposition temperature ranges from about 30°C to about 500°C.

[0034] The deposition methods disclosed herein may include 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 either the precursor composition or the counter-reactant(s). 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 to 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 may also be utilized as inert carrier gases for either or both of the precursor composition and counter-reactant(s).

[0035] Each step of supplying the precursor composition and counter reactant(s) can be performed by varying the order in which they are supplied and / or by varying the stoichiometry of the resulting EUV patternable film.

[0036] Energy is applied to the precursor composition and co-reactant(s) 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 in which deposition involves plasma, the plasma generation method can include a direct plasma generation method in which the plasma is generated directly in the reactor, or a remote plasma generation method in which the plasma is generated "remote" from the reaction zone and substrate and fed into the reactor.

[0037] As used herein, the term "microelectronic device" corresponds to a semiconductor substrate, including 3D NAND structures, flat panel displays, and microelectromechanical systems (MEMS), fabricated for use in microelectronic integrated circuits or computer chip applications. It should be understood that the term "microelectronic device" is not meant to be limiting in any way and includes any substrate that contains N-type metal oxide semiconductor (nMOS) and / or P-type metal oxide semiconductor (pMOS) transistors and that ultimately becomes a microelectronic device or microelectronic assembly. Such microelectronic devices include at least one substrate that can 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, photoresist, 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.

[0038] In situations where compounds of formula (I) and / or (II) are used with a co-reactant or counter-reactant, particularly in EUV patterning, they may be provided in the form of a kit. The container of the kit should be suitable for storing and transporting the compositions and advantageously include a means for conveying the components in one or more containers into a reaction zone where the tin-containing film or EUV-patternable film is deposited on the microelectronic device substrate. Additionally, the container(s) and system may include a dispense port for dispensing the composition(s) to a process tool. For example, gas pressure may be applied to the headspace of a conventional pressurized container, or a pump may be used to enable fluid communication for the introduction of such components into the reaction zone of a vapor deposition apparatus. Additionally, the system may include a dispense port for dispensing the components to a process tool.

[0039] Thus, in a further aspect, the present invention provides a kit comprising, in one or more containers, one or more compounds of formula (I) and / or (II) as described herein and one or more compounds (i.e., counter reactants) selected from water, peroxide, di- or polyhydroxy alcohols, hydrogen sulfide, hydrogen disulfide, trifluoroacetaldehyde monohydrate, fluorinated di- or polyhydroxy alcohols, and fluorinated glycols. [Example]

[0040] Synthesis of 1,3-bis(bis(trimethylsilylamido)iodotin(IV)]propane Bis(bis(trimethylsilylamido))tin(II) (5 g, 11.3 mmol) was placed in a 40 mL scintillation vial equipped with a magnetic stir bar and dissolved in hexane (15 mL) to form a dark orange / red solution. In a separate vial, 1,3-diiodopropane was dissolved in hexane (10 mL) and added dropwise to the Sn(II)-containing solution with stirring over a period of 1 minute. The reaction exhibited a slight exotherm during the addition and presented as a pale orange solution, which was stirred at room temperature for 1 hour. At this point, the reaction was concentrated by removing 15 mL of solvent under reduced pressure, and the resulting orange solution was stored at -35 °C overnight. The next morning, the reaction presented as a frozen yellow solid. After warming to room temperature, yellow crystals suitable for solid-state X-ray crystallography were collected for analysis. The remaining reaction contents were dried under reduced pressure to yield the target molecule as a free-flowing yellow powder (4.67 g, 70.4%). 1 H-NMR(C6D6,400 MHz);s,36H,0.41 ppm; 119 Sn-NMR(C6D6,150 MHz);-153.35 ppm.

[0041] Aspects In a first aspect, the present invention provides a method for depositing a tin-containing film on a surface of a microelectronic device in a reaction zone, the method comprising: TIFF0007825049000010.tif27170 (in the formula, R 1is a group selected from -C(R)2-, -CR(X)-, -O-, and -N(R)-; R is selected from H and C1-C5 alkyl; X is selected from F, Cl, Br, I, —OCH3, —OCH2CH3, —OCH2CH2CH3, and —OCH(CH3)2; and R 2 are H, -N(R)2, -OR, and -R 1 (selected from and introducing into a reaction zone under deposition conditions a precursor composition comprising at least one compound selected from:

[0042] In a second aspect, the present invention provides a compound comprising R 1 is a group of formula -N(R).

[0043] In a third aspect, the present invention provides a compound comprising R 2 is a group of formula -N(R)2.

[0044] In a fourth aspect, the present invention provides the method of any one of the first to fourth aspects, wherein the vapor deposition conditions are atomic layer deposition conditions.

[0045] In a fifth aspect, the present invention provides a method for depositing a tin-containing film on a surface of a microelectronic device in a reaction zone, the method comprising: TIFF0007825049000011.tif27170 (in the formula, R 1 is a divalent group selected from —C(R)—, —CR(X)—, —O—, and —N(R)—; R is selected from H and C1-C5 alkyl; X is selected from F, Cl, Br, I, —OCH3, —OCH2CH3, —OCH2CH2CH3, and —OCH(CH3)2; and R 2 are H, -N(R)2, and -OR, and -R 1 (selected from a precursor composition comprising at least one compound selected from at least one counter reactant selected from compounds capable of reacting with -OR and -N(R); into a reaction zone under deposition conditions.

[0046] In a sixth aspect, the present invention provides a method for producing an EUV patternable film on a surface of a microelectronic device substrate, comprising: Formula (I): TIFF0007825049000012.tif27170 (in the formula, R 1 is a divalent group selected from —C(R)—, —CR(X)—, —O—, and —N(R)—; R is selected from H and C1-C5 alkyl; X is selected from F, Cl, Br, I, —OCH3, —OCH2CH3, —OCH2CH2CH3, and —OCH(CH3)2; and R 2 are H, -N(R)2, and -OR, and -R 1 (selected from mixing a vapor stream of a precursor composition comprising at least one compound selected from the group consisting of: depositing a metalorganic material onto the surface of a substrate to form an EUV patternable film; The present invention provides a method comprising:

[0047] In a seventh aspect, the present invention provides a compound comprising R 1 is a group of formula -N(R)-.

[0048] In an eighth aspect, the present invention provides a compound comprising R 2 is a group of formula —N(R) 2 .

[0049] In a ninth aspect, the present invention provides the method of any one of the fifth to eighth aspects, wherein the vapor deposition conditions are atomic layer deposition conditions.

[0050] In a tenth aspect, the present invention provides a method for depositing a tin-containing film on a surface of a microelectronic device in a reaction zone, the method comprising: TIFF0007825049000013.tif11170 (in the formula, R 1 is a divalent radical selected from —CH—, —C═C—, —C≡C—, —O—, —N(R)—, —ORRO-, and —CH(X)—; R is selected from H and C1-C5 alkyl; X is selected from F, Cl, Br, I, —OCH3, —OCH2CH3, —OCH2CH2CH3, and —OCH(CH3)2; n is an integer from 0 to 5, R 2 are H, -N(R)2, -OR, and -R 1 and m is an integer from 0 to 2. and introducing into a reaction zone under deposition conditions a precursor composition comprising at least one compound selected from:

[0051] In an eleventh aspect, the present invention provides a compound comprising: R 1 is a group of formula -N(R)-.

[0052] In a twelfth aspect, the present invention provides a compound comprising: R 2 is a group of formula —N(R) 2 .

[0053] In a thirteenth aspect, the present invention provides the method of any one of the tenth to twelfth aspects, wherein the vapor deposition conditions are atomic layer deposition conditions.

[0054] In a fourteenth aspect, the present invention provides a method for depositing a tin-containing film on a surface of a microelectronic device in a reaction zone, the method comprising: TIFF0007825049000014.tif11170 (in the formula, R 1is a divalent radical selected from —CH—, —C═C—, —C≡C—, —O—, —N(R)—, —ORRO-, and —CH(X)—; R is selected from H and C1-C5 alkyl; X is selected from F, Cl, Br, I, —OCH3, —OCH2CH3, —OCH2CH2CH3, and —OCH(CH3)2; n is an integer from 0 to 5, R 2 are H, -N(R)2, and -OR, and -R 1 and m is an integer from 0 to 2. a precursor composition comprising at least one compound selected from at least one counter reactant selected from compounds capable of reacting with -OR and -N(R); into a reaction zone under deposition conditions.

[0055] In a fifteenth aspect, the present invention provides a method for producing an EUV patternable film on a surface of a microelectronic device substrate, comprising: Formula (II): TIFF0007825049000015.tif11170 (in the formula, R 1 is a divalent radical selected from —CH—, —C═C—, —C≡C—, —O—, —N(R)—, —ORRO-, and —CH(X)—; R is selected from H and C1-C5 alkyl; X is selected from F, Cl, Br, I, —OCH3, —OCH2CH3, —OCH2CH2CH3, and —OCH(CH3)2; n is an integer from 0 to 5, R 2 are H, -N(R)2, and -OR, and -R 1 and m is an integer from 0 to 2. mixing a vapor stream of a precursor composition comprising at least one compound selected from the group consisting of: depositing a metalorganic material onto the surface of a substrate to form an EUV patternable film; The present invention provides a method comprising:

[0056] In a sixteenth aspect, the present invention provides a compound comprising: R 1 is a group of formula -N(R)-.

[0057] In a seventeenth aspect, the present invention provides a compound comprising R 2 is a group of formula -N(R)2.

[0058] In an eighteenth aspect, the present invention provides the method of any one of the fourteenth to seventeenth aspects, wherein the vapor deposition conditions are atomic layer deposition conditions.

[0059] In a nineteenth aspect, the present invention provides a compound of formula (I): TIFF0007825049000016.tif27170 (in the formula, R 1 is a group selected from -C(R)2-, -CR(X)-, -O-, and -N(R)-; R is selected from H and C1-C5 alkyl; X is selected from F, Cl, Br, I, —OCH3, —OCH2CH3, —OCH2CH2CH3, and —OCH(CH3)2; and R 2 is selected from groups of formula -N(R)2 and -OR A precursor composition is provided comprising the compound of formula (I).

[0060] In a twentieth aspect, the present invention provides a compound of formula (II): TIFF0007825049000017.tif11170 (in the formula, R 1 is a divalent radical selected from —CH—, —C═C—, —C≡C—, —O—, —N(R)—, —ORRO-, and —CH(X)—; R is selected from H and C1-C5 alkyl; X is selected from F, Cl, Br, I, —OCH3, —OCH2CH3, —OCH2CH2CH3, and —OCH(CH3)2; n is an integer from 0 to 5, R 2 is a group of formula -N(R)2, and m is an integer from 0 to 2. A precursor composition comprising:

[0061] In a twenty-first aspect, the present invention provides a kit comprising, in one or more containers, one or more compounds of formula (I) and / or (II) as claimed in the nineteenth and twentieth aspects, and one or more compounds selected from water, peroxide, a dihydroxy alcohol or polyhydroxy alcohol, hydrogen sulfide, hydrogen disulfide, trifluoroacetaldehyde monohydrate, a fluorinated dihydroxy alcohol or polyhydroxy alcohol, and a fluorinated glycol.

[0062] Having thus described several exemplary embodiments of the present disclosure, those skilled in the art will readily appreciate that still other embodiments may be made and used within the scope of the appended claims. Many advantages of the present disclosure, which are covered 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 is, of course, defined in the language in which the appended claims are expressed.

Claims

1. 1. A method for depositing a tin-containing film on a surface of a microelectronic device in a reaction zone, comprising: (In the formula, R １ is -C(R) ２ is a group selected from -, -CR(X)-, -O-, and -N(R)-; R is H and C １ -C ５ alkyl, X is F, Cl, Br, I, -OCH ３ , -OCH ２ CH ３ , -OCH ２ CH ２ CH ３ , and —OCH(CH ３ ) ２ and R ２ is H, -N(R) ２ , and -R １ (selected from 1. A method comprising introducing into a reaction zone under deposition conditions a precursor composition comprising at least one compound selected from:

2. 1. A method for depositing a tin-containing film on a surface of a microelectronic device in a reaction zone, comprising: (In the formula, R １ is -C(R) ２ a divalent group selected from —, —CR(X)—, —O—, and —N(R)—; R is H and C １ -C ５ alkyl, X is F, Cl, Br, I, -OCH ３ , -OCH ２ CH ３ , -OCH ２ CH ２ CH ３ , and —OCH(CH ３ ) ２ and R ２ is H, -N(R) ２ -OR) a precursor composition comprising at least one compound selected from -OR and -N(R) ２ and at least one counter-reactant selected from compounds capable of reacting with into a reaction zone under deposition conditions.

3. 1. A method for depositing a tin-containing film on a surface of a microelectronic device in a reaction zone, comprising: (In the formula, R １ is an —N(R)— group, R is H and C １ -C ５ alkyl, n is an integer from 0 to 5, R ２ is H, -N(R) ２ -OR; and m is an integer of 1 to 2.

1. A method comprising introducing into a reaction zone under deposition conditions a precursor composition comprising at least one compound selected from:

4. 1. A method for depositing a tin-containing film on a surface of a microelectronic device in a reaction zone, comprising: (In the formula, R １ is -CH ２ a divalent group selected from -, -C═C-, -C≡C-, -O-, -N(R)-, -O-R-R-O-, and -CH(X)-; R is H and C １ -C ５ alkyl, X is F, Cl, Br, I, -OCH ３ , -OCH ２ CH ３ , -OCH ２ CH ２ CH ３ , and —OCH(CH ３ ) ２ is selected from n is an integer from 0 to 5, R ２ is H, -N(R) ２ -OR; and m is an integer of 1 to 2. a precursor composition comprising at least one compound selected from -OR and -N(R) ２ and at least one counter-reactant selected from compounds capable of reacting with into a reaction zone under deposition conditions.

5. Formula (I): (In the formula, R １ is -C(R) ２ is a group selected from -, -CR(X)-, -O-, and -N(R)-; R is H and C １ -C ５ alkyl, X is F, Cl, Br, I, -OCH ３ , -OCH ２ CH ３ , -OCH ２ CH ２ CH ３ , and —OCH(CH ３ ) ２ and R ２ is represented by the formula -N(R) ２ and —OR groups).

1. A tin precursor composition for forming an EUV patternable thin film comprising the compound of formula:

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