Tin-containing organometallic compounds

Abstract

Formula I:(R) x Sn(A) 4-x wherein R is selected from unsaturated hydrocarbons and A is selected from amino groups, alkoxy groups, and halides, and highly purified forms of said organometallic compounds.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63,334,430, filed April 25, 2022, which is incorporated herein in its entirety.

[0002] FIELD OF THEINVENTION The present disclosure relates to organometallic compounds useful for the deposition of high purity tin oxide, and high purity forms of the organometallic compounds. More specifically, the present disclosure describes certain compounds useful for the deposition of high purity tin oxide, and compositions that provide improved reactivity and greater stability. [Background technology]

[0003] background Extreme ultraviolet (EUV) lithography allows for excellent resolution of patterns transferred onto wafer substrates to form microchips. Unfortunately, conventional chemically amplified resists are highly transparent at EUV wavelengths of 13.5 nm (92 eV). This has created a need in the industry to develop a new generation of photosensitive materials that will enable the production of smaller microchips for a variety of technology applications. Summary of the Invention [Problem to be solved by the invention]

[0004] One strategy to improve the sensitivity of photosensitive materials is to incorporate atoms that have improved absorption in the EUV region, such as Sn, into the resist composition. Therefore, highly reactive and stable Sn organometallics are desired for use as photosensitive materials in EUV and deposition processes. [Means for solving the problem]

[0005] overview Applicants have determined that the performance of Sn-sensitive materials in certain applications can be improved by lowering the bond energy of the Sn-C bonds (photolytic cleavage of Sn-C bonds during exposure to EUV promotes crosslinking, making these materials excellent negative tone photoresists). Ligands that contain unsaturated hydrocarbons, such as allyls, can lower the bond energy of the Sn-C bonds.

[0006] Despite the aforementioned advantage of lowering the bond energy of Sn-C bonds in photosensitive materials, it is contemplated that strengthening Sn-C bonds in photosensitive materials may also be advantageous in photosensitive materials in other applications. Ligands containing unsaturated hydrocarbons such as vinyl can increase the bond energy of Sn-C bonds. By strengthening Sn-C bonds, some of the ligands bonded to Sn may be retained in the deposited film for further EUV processing, which may be advantageous in certain applications.

[0007] Additionally, the amino, alkoxy, or halide ligands allow for reactivity with OH groups of the wafer / substrate layer for effective ALD deposition. Thus, applicants have discovered that tin organometallics having a combination of unsaturated hydrocarbon-containing ligands and amino, alkoxy, or halide-containing ligands have improved properties for use as photosensitive materials in deposition, particularly atomic layer deposition, and patterning applications.

[0008] In one embodiment, organometallic compounds of formula I are disclosed: (R) x Sn(A) 4-x Formula I (In the formula, R is a substituted Cp, unsubstituted Cp, or an acyclic unsaturated hydrocarbon having 2 to 10 carbon atoms, or 2 to 8 carbon atoms, or 2 to 4 carbon atoms; A is NR 1 R 2 , OR 3 , pyrrolidinyl, pyrrolyl, or a halide; R1 and R 2 are each an alkyl group having 1 to 10 carbon atoms, R 1 and R 2 may be the same or different, R 3 is an alkyl group having 2 to 8 carbon atoms, x is an integer from 1 to 3; A is NR 1 R 2 , pyrrolidinyl, pyrrolyl, or halide, where R is a substituted Cp, or an acyclic unsaturated hydrocarbon having 2 to 10 carbon atoms, or 2 to 8 carbon atoms, or 2 to 4 carbon atoms.

[0009] In embodiments, R is an allyl or vinyl group. In some embodiments, the allyl or vinyl group may be linear. Alternatively, the allyl group may be represented by the general formula: CR 4 R 5 CR 6 =CR 7 R 8 (In the formula, R 4 , R 5 , R 6 , R 7 and R 8 may be a substituted aryl group having the general formula: CR 9 =CR 10 R 11 (In the formula, R 9 , R 10 and R 11 may be a substituted vinyl group having (each independently selected from the group consisting of H, and alkyl groups having 1 to 4 carbon atoms).

[0010] In other embodiments, R is R 12 , R 13 , R 14 , R 15 and R 16Cp is a cyclopentadienyl group having the moiety. Depending on A, Cp may be substituted or unsubstituted. R 12 , R 13 , R 14 , R 15 , and R 16 are each independently selected from H and an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl. 12 , R 13 , R 14 , R 15 and R 16 may be the same or different, provided that A is NR 1 R 2 , pyrrolidinyl, pyrrolyl, or halide, R 12 , R 13 , R 14 , R 15 and R 16 At least one of the groups is an alkyl group having 1 to 10 carbon atoms.

[0011] In any of the above embodiments, A is NR 1 R 2 In such an embodiment, R 1 and R 2 is independently selected from alkyl groups having 1 to 4 carbon atoms. 1 and R 2 is methyl or ethyl. In embodiments, R 1 and R 2 is different.

[0012] Alternatively, A is OR 3 In such an embodiment, R 3 is an alkyl group having 1 to 4 carbon atoms. In an embodiment, R 3 is methyl, ethyl, or tert-butyl. In other embodiments, A is one of pyrrolyl, pyrrolidinyl, or a halide.

[0013] In embodiments, the organometallic compound is (CH2=CHCH2)Sn(NMe2)3, (CH2=CHCH2)Sn(NEt2)3, (CH2=CHCH2)Sn(NEtMe)3, (CH2=CHCH2)Sn(pyrrolidinyl)3, (CH2=CH)Sn(NMe2)3, (CH2=CH)Sn(NEt2)3, (CH2=CH)Sn(NEtMe)3, (CH2=CH)Sn(pyrrolidinyl)3 )3, (Cp)Sn(NMe2)3, (Cp)Sn(NEt2)3, (Cp)Sn(NEtMe)3, (Cp)Sn(pyrrolidinyl)3, (CH2=CHCH2)2Sn(NMe2)2, (CH2 =CHCH2)2Sn(NEt2)2, (CH2=CHCH2)2Sn(NEtMe)2, (CH2=CHCH2)2Sn(pyrrolidinyl)2, (CH2=CH)2Sn(NMe2)2, (CH2 =CH)2Sn(NEt2)2, (CH2=CH)2Sn(NEtMe)2, (CH2=CH)2Sn(pyrrolidinyl)2, (Cp)2Sn(NMe2)2, (Cp)2Sn(NEt2)2, (C p)2Sn(NEtMe)2, (Cp)2Sn(pyrrolidinyl)2, (CH2=CHCH2)3Sn(NMe2), (CH2=CHCH2)3Sn(NEt2), (CH2=CHCH2)3Sn( NEtMe), (CH2=CHCH2)3Sn(pyrrolidinyl), (CH2=CH)3Sn(NMe2), (CH2=CH)3Sn(NEt2), (CH2=CH)3Sn(NEtMe), (CH2=CH)3Sn(pyrrolidinyl), (Cp)3Sn(NMe2), (Cp)3Sn(NEt2), (Cp)3Sn(NEtMe), (Cp)3Sn(pyrrolidinyl).

[0014] Embodiments of the present invention will now be described, by way of example only, with reference to the accompanying drawings, in which: [Brief description of the drawings]

[0015] [Figure 1] FIG. 1H NMR spectrum (300 MHz, C6D6) of a reaction mixture containing (CH2=CHCH2)Sn(Cl)3 in toluene. [Diagram 2]FIG. 1 shows the 119Sn NMR spectrum (186.55 MHz, C6D6) of a reaction mixture containing (CH2=CHCH2)Sn(Cl)3 in toluene. [Diagram 3] FIG. 1 shows the H NMR spectrum (300 MHz, C6D6) of a reaction mixture containing (CH2=CHCH2)2Sn(Cl)2 in toluene. [Figure 4] FIG. 1H NMR spectrum (300 MHz, C6D6) of the isolated product mixture containing (CH2=CHCH2)Sn(NMe2)3, (CH2=CHCH2)2Sn(NMe2)2, and (CH2=CHCH2)3Sn(NMe2) after 12 hours at 22 °C. [Diagram 5] FIG. 119Sn NMR spectrum (187 MHz, C6D6) of the isolated product mixture containing (CH2=CHCH2)Sn(NMe2)3, (CH2=CHCH2)2Sn(NMe2)2, and (CH2=CHCH2)3Sn(NMe2) after 12 hours at 22 °C. [Figure 6] FIG. 1 shows the H NMR spectrum (300 MHz, C6D6) of the product mixture containing (CH2=CHCH2)2Sn(NiPr2)2 and HNiPr2. [Figure 7] FIG. 1 shows the H NMR spectrum (500 MHz, C6D6) of (CH2=CH)3Sn(NEt2). [Figure 8] FIG. 1 shows the H NMR spectrum (186 MHz, C6D6) of (CH2=CH)3Sn(NEt2). [Figure 9] FIG. 1 shows the vapor pressure curve of (CH2=CH)3Sn(NEt2). [Figure 10] FIG. 1 shows the 119Sn NMR spectrum (186 MHz, C6D6) of CpiPrSn(NMe2)3. [Figure 11A] FIG. 2 shows a cross section of a deposited intermediate product. [Figure 11B] FIG. 2 shows a cross section of the developed intermediate product. [Figure 11C] FIG. 2 shows a cross section of an etched intermediate product. [Figure 11D] FIG. 2 shows a cross section of the final product. [Figure 12] FIG. 1 is a schematic diagram of a multi-stage vacuum distillation apparatus. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Detailed Description Before describing some exemplary embodiments, it is to be understood that the invention is not limited to the details of structure or process steps set forth in the following description as the invention is capable of other embodiments and of being practiced or carried out in various ways.

[0017] Reference throughout this specification to "one embodiment," "a particular embodiment," "one or more embodiments," or "an embodiment" means that a particular feature, structure, material, or characteristic described in connection with that embodiment is included in at least one embodiment. Thus, the appearances of phrases such as "in one or more embodiments," "in a particular embodiment," "in one embodiment," or "in an embodiment" in various places throughout this specification do not necessarily refer to the same embodiment. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0018] Although reference is made herein to specific embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the method and apparatus of the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention cover modifications and variations that come within the scope of the appended claims and their equivalents.

[0019] Throughout this specification, the terms "a" or "an" refer to one or more and are not limited to the singular, unless expressly stated otherwise.

[0020] The following detailed description may be read in conjunction with the accompanying drawings, in which like numerals indicate like elements and in which:

[0021] Formula I below: (R) x Sn(A) 4-x Formula I (In the formula, R is a substituted Cp, unsubstituted Cp, or an acyclic unsaturated hydrocarbon having 2 to 10 carbon atoms, or 2 to 8 carbon atoms, or 2 to 4 carbon atoms; A is NR 1 R 2 , OR 3 , pyrrolidinyl, pyrrolyl, or a halide; R 1 and R 2 are each an alkyl group having 1 to 10 carbon atoms, R 1 and R 2 may be the same or different, R 3 is an alkyl group having 2 to 8 carbon atoms, x is an integer from 1 to 3; A is NR 1 R 2 , pyrrolidinyl, pyrrolyl, or halide, R is a substituted Cp, or an acyclic unsaturated hydrocarbon having 2 to 10 carbon atoms, or 2 to 8 carbon atoms, or 2 to 4 carbon atoms. Organometallic compounds of the formula are disclosed.

[0022] Additionally, high purity organometallic compounds and methods for purifying organometallic compounds are disclosed.

[0023] The applicant has found that dissociation occurs during the synthesis of the compound of formula I. For example, the product (CH2=CHCH2)2Sn(NMe2)2 molecule undergoes significant ligand exchange, resulting in the formation of by-products such as (CH2=CHCH2)Sn(NMe2)3 and (CH2=CHCH2)3Sn(NMe2). It is believed that bulkier ligands, such as substituted allyl, substituted vinyl, substituted or unsubstituted Cp that is cyclopentadienyl, heavier amine, or heavier alkoxy, in the compound of formula I may be able to prevent the formation of by-products and improve stability by reducing ligand exchange.

[0024] In an embodiment, R has the general formula: CR 4 R 5 CR 6 =CR 7 R 8 (In the formula, R 4 , R 5 , R 6 , R 7 , and R 8 is an aryl group having H and an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, or n-butyl. 4 , R 5 , R 6 , R 7 and R 8 may be the same or different. In embodiments, R 4 and R 5 at least one of R is not H, e.g., 1,1-dimethylallyl, 4 and R 5 are both methyl. In embodiments, R 6 is not H, for example, 2-methylallyl. 7 and R 8 In some embodiments, x is 2 and the compound of formula I has the formula: (CR 4 R 5 CR 6=CR 7 R 8 )Sn(A)2 (wherein A is NR 1 R 2 , OR 3 , pyrrolidinyl, pyrrolyl, or a halide).

[0025] In other embodiments, R has the general formula: CR 9 =CR 10 R 11 (In the formula, R 9 , R 10 and R 11 R is a vinyl group having H and an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl, or n-butyl. 9 , R 10 and R 11 may be the same or different. In embodiments, R 9 is not H, for example, 1-ethylvinyl. 10 and R 11 In some embodiments, x is 2 and the compound of formula I has the formula: (CR 9 =CR 10 R 11 )Sn(A)2 (wherein A is NR 1 R 2 , OR 3 , pyrrolidinyl, pyrrolyl, or a halide).

[0026] Any of the above compounds of formula I include those where x is 1. In such embodiments, the compounds of formula I are represented by the following formula: (R)Sn(A)3, where R is an acyclic unsaturated hydrocarbon having 2 to 10 carbon atoms. Compounds of formula I also include those where x is 3. In such alternative embodiments, the compounds of formula I are represented by the following formula: (R)3Sn(A), where R is an acyclic unsaturated hydrocarbon having 2 to 10 carbon atoms.

[0027] Formula:(R) x Sn(A) 4-x Any of the above compounds of formula I represented by the formula (I) include those where R is an acyclic unsaturated hydrocarbon having 2 to 8 carbon atoms. Additionally, compounds of formula I include those where R is an acyclic unsaturated hydrocarbon having 2 to 4 carbon atoms.

[0028] In any of the compounds of formula I above, A is NR 1 R 2 R 1 and R 2 is independently selected from H, an alkyl group having 1 to 10 carbon atoms, an aryl group, or an acyl group. 1 and R 2 may be the same or different. In certain embodiments, R 1 and R 2 are each an alkyl group having 1 to 10 carbon atoms. 1 and R 2 are each an alkyl group having 2 to 4 carbon atoms. More specifically, R 1 and R 2 may each be selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl and n-butyl.

[0029] For any of the above compounds, it is contemplated that R can be either a straight chain unsaturated hydrocarbon or a branched unsaturated hydrocarbon.

[0030] In any of the compounds of formula I above, A is OR 3 In such embodiments, the compound of formula I has the formula: (R x Sn(OR 3 ) 4-x (In the formula, R 3 is an alkyl group having 2 to 8 carbon atoms. 3 is selected from the group consisting of alkyl groups having 1 to 4 carbon atoms. More particularly, R 3may be selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl and n-butyl.

[0031] A is OR 3 In such an embodiment, the compound of formula I has the formula: (Cp) x Sn(OR 3 ) 4-x (Wherein, Cp is R 12 , R 13 , R 14 , R 15 and R 16 Cp may be unsubstituted, where R 12 , R 13 , R 14 , R 15 , and R 16 is H or optionally substituted, where R 12 , R 13 , R 14 , R 15 , and R 16 At least one of R is independently selected from an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl. 12 , R 13 , R 14 , R 15 and R 16 may be the same or different.

[0032] A is an amino group, e.g., NR 1 R 2 or pyrrolidinyl, pyrrolyl, or halide, R may be a substituted Cp, where R 12 , R 13 , R 14 , R 15 , and R 16At least one of R is independently selected from an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl. 12 , R 13 , R 14 , R 15 and R 16 may be the same or different.

[0033] Compounds of formula I include those where A is pyrrolidinyl or pyrrolyl. Such embodiments can be represented by the general formula: (R x Sn(pyrrolidinyl) 4-x or (R) x Sn(pyrrolyl) 4-x It is contemplated that A may also be a halide, such as chloro, bromo, or iodo.

[0034] When R is Cp, the compound of formula I, (Cp) x Sn(A) 4-x can be synthesized as follows. In a glove box, place SnCl4 and anhydrous hexane in a 1 L round bottom flask. With cooling, add 1 equivalent of NaCl * (NaC5Me5) is added dropwise. The reaction mixture is allowed to stir at room temperature for 1 hour. The reaction flask is returned to the cooling bath and 3 equivalents of NaOMe in anhydrous THF are added to the flask. The solvent is removed by distillation under reduced pressure. The product is isolated by sublimation.

[0035] Specific organometallic compounds of formula I include the following: (CH2=CHCH2)Sn(NMe2)3, (CH2=CHCH2)Sn(NEt2)3, (CH2=CHCH2)Sn(NEtMe)3, (CH2=CHCH2)Sn(pyrrolidinyl)3, (CH2=CH)Sn(NMe2)3, (CH2=CH)Sn(NEt2)3, (CH2=CH)Sn(NEtMe)3, (CH2=CH)Sn(pyrolidinyl)3, (CH2=CH)Sn(NMe2)3, (CH2=CH)Sn(NEt2)3, (CH2=CH)Sn(NEtMe)3, (CH2=CH)Sn(pyro Lysinyl)3, (Cp)Sn(NMe2)3, (Cp)Sn(NEt2)3, (Cp)Sn(NEtMe)3, (Cp)Sn(pyrrolidinyl)3, (CH2=CHCH2)2Sn(NMe2)2, (CH2=CHCH2)2Sn(NEt2)2, (CH2=CHCH2)2Sn(NEtMe)2, (CH2=CHCH2)2Sn(pyrrolidinyl)2, (CH2=CH)2Sn(NMe2)2, ( CH2=CH)2Sn(NEt2)2, (CH2=CH)2Sn(NEtMe)2, (CH2=CH)2Sn(pyrrolidinyl)2, (Cp)2Sn(NMe2)2, (Cp)2Sn(NEt2)2 , (Cp)2Sn(NEtMe)2, (Cp)2Sn(pyrrolidinyl)2, (CH2=CHCH2)3Sn(NMe2), (CH2=CHCH2)3Sn(NEt2), (CH2=CHCH2)3S Examples of such compounds include n(NEtMe), (CH2=CHCH2)3Sn(pyrrolidinyl), (CH2=CH)3Sn(NMe2), (CH2=CH)3Sn(NEt2), (CH2=CH)3Sn(NEtMe), (CH2=CH)3Sn(pyrrolidinyl), (Cp)3Sn(NMe2), (Cp)3Sn(NEt2), (Cp)3Sn(NEtMe), and (Cp)3Sn(pyrrolidinyl).

[0036] Reducing the bond strength of the Sn-C bonds can improve the performance of Sn-sensitive materials when the Sn-C bonds are photolytically cleaved upon EUV exposure. This promotes cross-linking, making these materials excellent negative-tone photoresists. Unsaturated hydrocarbons, such as allyl ligands, are important compounds for this application. Furthermore, the presence of Sn-allyl bonds improves the reactivity of this molecule during SnO2 film formation.

[0037] In photosensitive materials, it may also be advantageous to increase the bond strength of the Sn-C bond. Ligands containing unsaturated hydrocarbons such as vinyl can increase the bond energy of the Sn-C bond. By strengthening the Sn-C bond, some of the ligands bonded to Sn may be retained in the deposited film for further EUV processing, which may be advantageous.

[0038] Compounds of formula I can be prepared by processes known in the art. The following examples are illustrative of such processes but are not intended to be limiting.

[0039] Example 1: (CH 2 =CHCH 2 )Sn(Cl) 3 Synthesis of A small Schlenk flask on a double manifold was charged with 6.0 mL of SnCl4 (51 mmol), approximately 60 mL of anhydrous toluene, and a magnetic stir bar. With stirring at room temperature, 4.1 mL of Sn(allyl)4 (17 mmol) was added dropwise. The reaction mixture was stirred at 22 °C for 90 min. Small aliquots were then added to the flask. 1 H NMR and 119 A sample was taken for Sn NMR analysis, which confirmed the formation of (CH2=CHCH2)Sn(Cl)3 as shown in Figures 1 and 2. Removal of solvent may affect stability. Characterization: 1 H NMR (300MHz, C6D6) (Figure 1): 1.72ppm (m, 2 J H119Sn = 120Hz, 2 J H117Sn = 124Hz, 1H, allylCH2), 1.75ppm (m, 2 J H119Sn = 118Hz, 2 J H117Sn = 124Hz, 1H, allylCH2), 4.69ppm (m, 3 J HH = 16.6Hz, 1H, allylCH2), 4.74ppm (m, 3 J HH= 9.7Hz, 1H, allylCH2), 5.15ppm (m, 1H, allylCH). 119 Sn NMR (186.55MHz, C6D6) (Figure 2): -26.8ppm. Example 2: (CH 2 =CHCH 2 ) 2 Sn(Cl) 2 Synthesis of A small Schlenk flask on a double manifold was charged with 2.0 mL of SnCl4 (17 mmol), approximately 30 mL of anhydrous toluene, and a magnetic stir bar. With stirring at room temperature, 4.1 mL of Sn(allyl)4 (17 mmol) was added dropwise. The reaction mixture was stirred at 22 °C for 90 min. Small aliquots were then added to the flask. 1 H NMR and 119 A sample was taken for Sn NMR analysis, which confirmed the formation of (CH2=CHCH2)2Sn(Cl)2 as shown in Figure 3. Removal of solvent may affect stability. Characterization: 1 H NMR (300MHz, C6D6) (Figure 3): 1.96ppm (m, 1H, allylCH2), 1.99ppm (m, 1H, allylCH2), 4.80-4.88ppm (m, 2H, allylCH2), 5.57ppm (m, 1H, allylCH). 119 Sn NMR (186.55MHz, C6D6): 48.3ppm. Example 3: (CH 2 =CHCH 2 ) 2 Sn(NMe 2 ) 2 Synthesis of A 1 L round bottom flask on a double manifold was charged with 82 mL of BuLi (2.5 M in hexanes, 0.205 mol), approximately 500 mL of anhydrous toluene, and a magnetic stir bar. The flask was placed in an ice-water bath and HNMe2 was bubbled through the reaction mixture at a rate of 284 mL (0.251 mol) per minute for 20 minutes. The reaction flask was removed from the cooling bath and left stirring at 22° C. for 90 minutes.

[0040] Meanwhile, (CH2=CHCH2)2Sn(Cl)2 was prepared by reacting 6.0 mL of SnCl4 (0.051 mol) with 12.3 mL of Sn(allyl)4 (0.051 mol) dissolved in approximately 100 mL of anhydrous toluene. The reaction was stirred at 22°C for 60 minutes. The flask containing (CH2=CHCH2)2Sn(Cl)2 was placed back into the ice-water bath and the LiNMe2 mixture was slowly added dropwise to the flask via cannula. The final reaction mixture was removed from the cooling bath and stirred at 22°C for 50 minutes.

[0041] The stirring was stopped and the LiCl salt was allowed to stand overnight. The next day, the liquid layer was transferred to a new round-bottom flask. The solvent was removed by vacuum distillation. The final product was obtained by vacuum distillation (2.0–4.5 × 10 -2 The reaction was isolated at 40 °C under Torr. Significant ligand exchange of (CH2=CHCH2)2Sn(NMe2)2 was detected, resulting in the formation of (CH2=CHCH2)SN(NMe2)3 and (CH2=CHCH2)3Sn(NMe2), with a final product distribution of 50:25:25 mol%.

[0042] Characterization: (CH2=CHCH2)3Sn(NMe2): 1 H NMR (300MHz, C6D6) (Figure 4): 1.87ppm (dd, 2 J HH = 1.2Hz; 3 J HH = 0.7Hz, 3H, allylCH2), 1.90 ppm (dd, 2 J HH = 1.2Hz; 3 J HH = 0.7Hz, 3H, AllylCH2), 2.73ppm (s, 3 J H119Sn = 42.6Hz, 3 J H117Sn = 41.1Hz, 6H, NMe2), 4.82ppm (m, 3H, allylCH2), 4.93ppm (ddd, 3 J HH = 16.8Hz, 4 J HH = 3.2Hz,2 J HH = 1.2Hz; 3H, allylCH2), 5.9ppm (m, 3H, allylCH). 119 Sn NMR (186.55MHz, C6D6) (Figure 5): -6.9ppm. (CH2=CHCH2)2Sn(NMe2)2: 1 H NMR (300MHz, C6D6) (Figure 4): 1.92ppm (dd, 2 J HH = 1.2Hz; 3 J HH = 0.7Hz, 2H, allylCH2), 1.94 ppm (dd, 2 J HH = 1.2Hz; 3 J HH = 0.7Hz, 2H, AllylCH2), 2.78ppm (s, 3 J H119Sn = 43.6Hz, 3 J H117Sn = 41.6Hz, 12H, NMe2), 4.83ppm (m, 2H, allylCH2), 4.97ppm (ddd, 3 J HH = 16.8Hz, 4 J HH = 3.0Hz, 2 J HH = 1.2Hz; 2H, allylCH2), 5.9ppm (m, 2H, allylCH). 119 Sn NMR (186.55MHz, C6D6) (Figure 5): -21.6ppm. (CH2=CHCH2)Sn(NMe2)3: 1 H NMR (300MHz, C6D6) (Figure 4): 1.93ppm (dd, 2 J HH = 1.5Hz; 3 J HH = 1.0Hz, 1H, allylCH2), 1.95 ppm (dd, 2 J HH = 1.5Hz; 3 J HH = 1.0Hz, 1H, AllylCH2), 2.81ppm (s,3 J H119Sn = 46.1Hz, 3 J H117Sn = 44.1Hz, 18H, NMe2), 4.83ppm (m, 3 J HH = 9.9Hz, 1H, allylCH2), 4.97ppm (ddd, 3 J HH = 16.8Hz, 4 J HH = 3.0Hz, 2 J HH = 1.2Hz; 1H, allylCH2), 5.9ppm (m, 1H, allylCH). 119 Sn NMR (186.55MHz, C6D6) (Figure 5): -64.9ppm. Example 4: (CH 2 =CHCH 2 ) 2 Sn(NEt 2 ) 2 Synthesis of A Schlenk flask on a double manifold was charged with 27.5 mL of nBuLi (2.5 M in hexanes, 0.069 mol), approximately 125 mL of anhydrous toluene, and a magnetic stir bar. The flask was placed in an ice-water bath and HNEt2 (7.4 mL, 0.072 mol) dissolved in approximately 20 mL of anhydrous toluene was added dropwise to the reaction flask. The reaction flask was removed from the cooling bath and left stirring at 22° C. for 40 min.

[0043] Separately, (CH2=CHCH2)2Sn(Cl)2 was prepared by reacting 2.0 mL of SnCl4 (0.017 mol) with 4.1 mL of Sn(allyl)4 (0.017 mol) dissolved in approximately 80 mL of anhydrous toluene. The reaction was stirred for 60 min at 22 °C. The flask containing (CH2=CHCH2)2Sn(Cl)2 was placed back in the ice-water bath and the LiNMe2 mixture was slowly added dropwise to the flask via cannula. The final reaction mixture was removed from the cooling bath and stirred for 30 min at 22 °C before being distilled under reduced pressure to remove the solvent and recover the product (80 °C at 0.05 Torr).

[0044] Characterization:1 H NMR (300MHz, C6D6): 1.08ppm (t, 3 J HH =6.9Hz, 12H, N(CH2CH3)), 1.95ppm (dd, 2 J HH = 1.5Hz; 3 J HH = 1.0Hz, 2H, AllylCH2), 1.98 ppm (dd, 2 J HH = 1.5Hz; 3 J HH = 1.0Hz, 2H, allylCH2), 3.04ppm (q, 3 J HH =6.9Hz, 8H, N(CH2CH3)), 4.86ppm (m, 2H, allylCH2), 4.98ppm (m, 2H, allylCH2), 5.9ppm (m, 2H, allylCH). 119 Sn NMR (134.35MHz, C6D6): -24.8ppm. Example 5: (CH 2 =CHCH 2 ) 2 Sn(NiPr 2 ) 2 Synthesis of A 1 L round bottom flask on a double manifold was charged with 29.9 mL of nBuLi (2.5 M in hexanes, 0.075 mol), approximately 500 mL of anhydrous toluene, and a magnetic stir bar. The flask was placed in an ice-water bath and HNiPr2 (11 mL, 0.079 mol) dissolved in approximately 20 mL of anhydrous toluene was added dropwise to the reaction flask. The reaction flask was removed from the cooling bath and left stirring overnight at 22°C. The reaction flask was then transferred to an ice-water bath.

[0045] Meanwhile, (CH2=CHCH2)2Sn(Cl)2 was prepared by reacting 2.19 mL of SnCl4 (0.019 mol) with 4.49 mL of Sn(allyl)4 (0.019 mol) dissolved in approximately 100 mL of anhydrous toluene. The reaction was stirred at 22 °C for 3 h. The (CH2=CHCH2)2Sn(Cl)2 mixture was slowly added dropwise through a cannula to the round bottom flask. The final reaction mixture was removed from the cooling bath and stirred overnight at 22 °C. After removal of the solvent from the final product mixture, the product and some of the free amines in the residue were characterized. The product was solid and showed no signs of ligand exchange.

[0046] Characterization: 1 H NMR (300MHz, C6D6) (Figure 6): 0.89ppm (d, 3 J HH =6.7Hz, 24H, iPr-CH3), 1.89ppm (dd, 2 J HH = 1.0Hz; 3 J HH = 1.2Hz, 2H, allylCH2), 1.92 ppm (dd, 2 J HH = 1.0Hz; 3 J HH = 1.2Hz, 2H, allyl CH2), 3.17ppm (septet, 3 J HH =6.7Hz, 4H, iPr-CH), 4.68ppm (m, 2H, allylCH2), 4.78ppm (m, 2H, allylCH2), 5.80ppm (m, 2H, allylCH). Example 6: (CH 2 =CH) 3 Synthesis of SnCl The synthesis of this complex was based on Sanders D. Rosenberg & Ambrose J. Gibbons Jr., The Disproportionation of Tetravinyltin with Tin Tetrachloride and the Cleavage of Some Vinyltin Compounds with Bromine, Vol. 79 J. AM. CHEM. SOC'Y. 2138 pages (1957), https: / / doi.org / 10.1021 / ja01566a029 [hereinafter Rosenberg & Gibbons]. This complex was not isolated but was used in the following salt metathesis reaction step. Characterization: 1 H (300MHz, C6D6): dd 5.77ppm ( 3 J HH = 2.7Hz, 3 J HH = 19.9Hz, 3H, vinyl-CH), dd 5.98ppm ( 3 J HH = 2.7Hz, 3 J HH = 13.4Hz, 3H, vinyl-CH), dd 6.14ppm ( 3 J HH = 13.4Hz, 3 J HH = 19.9Hz, 3H, vinyl-CH). 119 Sn (186MHz, C6D6): s -53.8ppm. Example 7: (CH 2 =CH) 3 Sn(NEt 2 Synthesis of A 500 mL round bottom flask on a double manifold was charged with 10.5 mL of nBuLi (2.5 M in hexane, 0.0263 mol), approximately 250 mL of anhydrous hexane, and a magnetic stir bar. HNEt2 (2.8 mL, 0.027 mol) was added dropwise to the reaction flask. The reaction mixture was left stirring at 22° C. for 60 min.

[0047] Separately, (CH2=CH)3SnCl was prepared by reacting 3.5 mL of Sn(vinyl)4 (0.019 mol) with 0.8 mL of SnCl4 (0.0068 mol). The reaction was stirred at 40°C for 90 min. See Rosenberg & Gibbons.

[0048] The (CH2=CH)3SnCl mixture is slowly added to the LiNEt2 mixture via cannula. The final reaction mixture was stirred overnight at 22° C. The next day, the solvent was removed by distillation under reduced pressure, after which the product was collected in a separate receiving flask (0.08 Torr at 35° C.) to give 5.2 g of product (75% yield).

[0049] Characterization: 1 H (500MHz, C6D6) (Figure 7): t 1.10ppm ( 3 J HH = 6.9Hz, 6H, NEt-CH3), q 3.08ppm ( 3 J HH = 6.9Hz, 4H, NEt-CH2), dd 5.82ppm ( 3 J HH = 3.2Hz, 3 J HH = 20.5Hz, 3H, vinyl-CH), dd 6.16ppm ( 3 J HH = 3.2Hz, 3 J HH = 13.7Hz, 3H, vinyl-CH), dd 6.40ppm ( 3 J HH = 13.7Hz, 3 J HH = 20.5Hz, 3H, vinyl-CH). 119 Sn (186MHz, C6D6) (Figure 8): s -104.1ppm. FIG. 9 shows the vapor pressure curve of (CH2=CH)3Sn(NEt2). Vapor pressure measurement: log 10P=-2691.6 / T+8.6502. Vapor pressure measurements are obtained as follows: A small amount of liquid is evaporated in a closed system where temperature and pressure can be controlled. At a set temperature, the pressure is slowly lowered until the liquid sample evaporates at a rate, which is determined by measuring the drip rate of the liquid from a condenser directly above the liquid. This is repeated for 8 to 10 temperatures, run in duplicate. The results are compared to parallel runs of calibration standards to help calibrate the measured drip rate and pressure at temperature to the known vapor pressure at that temperature.

[0050] Example 8: Cp iPr Sn(NMe 2 ) 3 Synthesis of In a glove box, a small Schlenk flask was charged with 1.2 mL of Sn(NMe2)4 (4.7 mmol) and approximately 13 mL of anhydrous THF. iPr (5.2 mmol) is added. The Schlenk flask is placed on a double manifold and refluxed at 76° C. for 4 h. NMR analysis of the reaction mixture reveals that Cp iPr The formation of Sn(NMe2)3 was confirmed. Upon isolation, the product is a solid.

[0051] Characterization: 1 H (500MHz, C6D6): d 1.36ppm ( 3 J HH = 6.7Hz, 6H, iPr-CH3), s 3.06ppm ( 3 J H119Sn = 42.1Hz, 3 J H117Sn = 40.4Hz, 18H, NMe2), septet 3.18 ( 3 J HH =6.7Hz, 1H, iPr-CH), m 6.21 (2H, Cp-H), m 6.32 (2H, Cp-H). 119 Sn (186MHz, C6D6) (Figure 10): s 63.9ppm. The compounds of formula I may have improved thermal stability and surface reactivity compared to compounds known in the art, which may result in improved ALD films. Poor thermal stability may inhibit the reactivity of the precursor with the substrate surface during ALD deposition, i.e., the precursor is preferably not decomposed prior to ALD deposition. In contrast to ALD, CVD processes use high energy and temperature to react the precursor at the process temperature. The already reacted precursor then reacts on the substrate. Precursor reactivity is less important in CVD processes than in ALD processes, since CVD processes use substantially more energy and decompose the precursor prior to reaction.

[0052] Negative resist deposition 11A-11D show an exemplary process of negative resist deposition using a compound of formula I. A multilayer substrate 10 is provided. In the illustrated example, layer 10A is the only layer of the substrate to be patterned. Subsequently, a layer of photosensitive material 30 containing a compound of formula I is deposited on layer 10A. Next, a mask 40 is selectively applied on portions of the layer of photosensitive material 30 such that the unexposed portions 30A of the layer of photosensitive material 30 are covered by the mask 40 and the exposed portions 30B of the layer of photosensitive material 30 are not covered by the mask 40. Finally, in the illustrated example, a mask glass layer 50 is applied on the mask 40 and the layer of photosensitive material 30. In this way, a deposition intermediate portion 1a is formed as shown in FIG. 11A.

[0053] Next, the deposited intermediate portion 1a is irradiated with extreme ultraviolet (EUV) light through a mask 40 to cause photolytic cleavage of Sn-C bonds that promote cross-linking. After irradiation, the deposited intermediate portion 1a is fired to densify the SnO2 layer. Then, the glass mask 50 is removed.

[0054] The developing step is shown in FIG. 11B. During the developing step, the unexposed portion 30A of the layer of the photosensitive material 30 that was not exposed to EUV light during irradiation is removed so that only the exposed portion 30B of the layer of the photosensitive material 30 remains. The unexposed portion 30B is disposed on the layer 10A of the multilayer substrate 10 as shown in FIG. 11B. In this way, a developed intermediate product 1b is formed as shown in FIG. 11B.

[0055] During the etching step shown in Fig. 11C, layer 10A of multilayer substrate 10 is etched to produce the desired pattern. The etching results in layer 10B being covered by exposed portions 30B of layer of photosensitive material 30. In this way, an etched intermediate product 1c is formed as shown in Fig. 11C.

[0056] Finally, the exposed portions 30B of the layer of photosensitive material 30 are removed, leaving behind the desired pattern. Figure 11D shows the resulting pattern. In this way, product 1 is formed, as shown in Figure 11D.

[0057] The compounds of formula I are particularly advantageous for negative resist deposition processes because the performance of Sn-sensitive materials is improved by tuning the Sn-C bond energy using allyl or vinyl ligands. It is contemplated that these materials are superior to materials known in the art because the photolytic cleavage of the Sn-C bond during exposure to EUV light promotes crosslinking.

[0058] Multi-Stage Distillation From theoretical modeling of the activation energy required to remove the ligand from the molecule by hydrolysis reaction, it has been observed that there is a large range of activation energies between molecules. Thus, differences in reactivity are observed. This indicates that if the activation energy is low, the molecule may be very reactive in forming SnO2, but this value also indicates that it may be more susceptible to decomposition and reaction during the synthesis and purification process. Therefore, it is difficult to obtain purity for compounds within the range of formula I, especially assay purity of >95% or >99%.

[0059] However, using multiple stage vacuum distillation, assay purities of greater than 95% or even greater than 99% can be obtained for compounds within the scope of Formula I. Various forms of multiple stage distillation are known in the chemical manufacturing industry, but have not been employed for the purification of organometallic materials, including compounds of Formula I.

[0060] As shown in the schematic diagram shown in Figure 12, multiple effect distillation (MED) or multi-stage distillation is a distillation process often used for desalination of seawater. Multi-effect distillation or multi-stage distillation consists of several stages or "effects". (In schematic in Figure 14, the first stage is at the top. The top of each stage is steam and the bottom of each stage is liquid feed. The material that runs through the tubes along the left side of the diagram and is at the bottom of the VC is the condensate. How the feed enters the stages other than the first stage is not shown, but it should be easy to understand. F - Feed raw material in, S - Heating steam in, C - Heating steam out, W - Refined material (condensate) out, R - Waste out, O - Coolant in, P - Coolant out. VC is the final stage cooler.) At each stage, the feed is heated by steam in the tubes. Part of the feed evaporates and this steam flows into the tubes of the next stage to heat and evaporate more distillate. Each stage essentially reuses the energy of the previous stage.

[0061] The device can be viewed as a series of closed spaces separated by tube walls, with a heat source at one end and a heat sink at the other. Each space is at subatmospheric pressure due to reduced pressure. Each space consists of two communicating subspaces, the outside of the tubes in stage n and the inside of the tubes in stage n+1. Each space has a lower temperature and pressure than the previous space, and the tube walls have a temperature intermediate between the temperatures of the fluids on either side. The pressure in one space cannot equilibrate with the temperatures of the walls of both subspaces, and so has an intermediate pressure. As a result, in the first subspace, the pressure is too low or the temperature is too high, and the feed material evaporates. In the second subspace, the pressure is too high or the temperature is too low, and the vapor condenses. This transfers the energy of evaporation from the warmer first subspace to the cooler second subspace. In the second subspace, the energy flows by conduction through the tube walls to the next cooler space.

Claims

1. Formula I: (R) ｘ Sn(A) ４－ｘ Formula I (In the formula, R is a substituted Cp, or an acyclic unsaturated hydrocarbon having 2 to 10 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. A is NR １ R ２ , OR ３ , pyrrolidinil, or pyrrolyl, R １ and R ２ These are independently selected from the group consisting of alkyl groups, aryl groups, and acyl groups having 1 to 10 carbon atoms. R ３ This is an alkyl group or aryl group having 1 to 10 carbon atoms. x is an integer between 1 and 3. A is OR ３ When it is, R is a vinyl group, R is a vinyl group, x is 3, and A is NR １ R ２ If R １ and R ２ At least one of them is not Et, Substitution Cp is given by equation C ５ R １２ R １３ R １４ R １５ R １６ (In the formula, R １２ , R １３ , R １４ , R １５ , R １６ At least one of them is H, and R １２ , R １３ , R １４ , R １５ , R １６ (At least one of them is an alkyl group having 1 to 10 carbon atoms.) Organometallic compounds.

2. The organometallic compound according to claim 1, wherein x is 1 or 2.

3. The organometallic compound according to any one of claims 1 to 2, wherein R is an allyl group or a vinyl group.

4. The organometallic compound according to any one of claims 1 to 2, wherein R is a straight-chain unsaturated hydrocarbon.

5. R is the general formula: CR ４ R ５ CR ６ =CR ７ R ８ (In the formula, R ４ , R ５ , R ６ , R ７ and R ８ The organometallic compound according to any one of claims 1 to 2, wherein the allyl group is independently selected from the group consisting of H and an alkyl group having 1 to 4 carbon atoms.

6. R is the general formula: CR ９ =CR １０ R １１ (In the formula, R ９ , R １０ and R １１ The organometallic compound according to any one of claims 1 to 2, wherein the group is a vinyl group having H and an alkyl group having 1 to 4 carbon atoms, each independently selected from the group consisting of H and an alkyl group having 1 to 4 carbon atoms.

7. The organometallic compound according to any one of claims 1 to 2, wherein R is a substituted Cp.

8. The organometallic compound according to any one of claims 1 to 2, wherein x is 2.

9. A is NR １ R ２ The organometallic compound according to any one of claims 1 to 2.

10. R １ and R ２ The organometallic compound according to claim 9, which is independently selected from alkyl groups having 1 to 4 carbon atoms.

11. R １ The organometallic compound according to claim 10, wherein is Me or Et.

12. R ２ The organometallic compound according to claim 10, wherein is Me or Et.

13. R １ and R ２ The organometallic compound according to any one of claims 1 to 2, wherein the characteristics differ.

14. A is OR ３ The organometallic compound according to any one of claims 1 to 2.

15. R ３ The organometallic compound according to claim 14, wherein is an alkyl group having 1 to 4 carbon atoms.

16. R ３ is Me, Et, or ｔ The organometallic compound according to claim 15, wherein the compound is Bu.

17. The organometallic compound according to any one of claims 1 to 2, wherein A is pyrrolyl.

18. The organometallic compound according to any one of claims 1 to 2, wherein A is pyrrolidinyl.

19. R is a vinyl group, and A is NR １ R ２ The organometallic compound according to claim 1, wherein x is 1 or 2.

20. The organometallic compound is (CH ２ =CHCH ２ )Sn(NMe ２ ) ３ , (CH ２ =CH)Sn(pyrrolidinyl) ３ , (CH ２ =CHCH ２ ) ２ Sn(NMe ２ ) ２ , (CH ２ =CHCH ２ ) ２ Sn(NEt ２ ) ２ , (CH ２ =CHCH ２ ) ２ Sn(NEtMe) ２ , (CH ２ =CHCH ２ ) ２ Sn(pyrrolidinyl) ２ , (CH ２ =CH) ２ Sn(NMe ２ ) ２ , (CH ２ =CH) ２ Sn(NEt ２ ) ２ , (CH ２ =CH) ２ Sn(NEtMe)<0管理000094>, (CH ２ =CH) ２ Sn(pyrrolidinyl) ２ , (CH ２ =CH) ２ Sn(OMe) ２ , (CH ２ =CH) ２ Sn(OEt) ２ , (CH ２ =CH) ２ Sn(O ｔ Bu) ２ , (CH ２ =CHCH<管理 ２ ) ３ Sn(NMe ２ ), and (CH ２ =CH) ３ Sn(pyrrolidinyl), which is selected from the group consisting of, the organometallic compound according to claim 1.

Images