Tin-containing organometallic compounds

Abstract

Disclosed are tin-containing organometallic compounds of formula I: (R) xSn (A) 4-x, where R is selected from unsaturated hydrocarbons having 2 to 10 carbon atoms and optionally substituted Cp, A is selected from amine groups, alkoxy groups and halides, and X is an integer from 1 to 3, as well as high purity forms of organometallic compounds useful for depositing high purity tin oxides and compositions that improve reactivity and stability.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63,334,430, filed on April 25, 2022, the entire contents of which are incorporated herein. Technical Field

[0003] The present invention relates to organometallic compounds and high purity forms of organometallic compounds useful for depositing high purity tin oxide. More specifically, the present disclosure describes specific compounds and compositions useful for depositing high purity tin oxide having improved reactivity and stability. Background Art

[0004] Extreme ultraviolet (EUV) lithography enables extremely high resolution of the patterns transferred to wafer substrates to form microchips. Unfortunately, conventional chemically amplified resists are highly transparent at EUV wavelengths of 13.5nm (92eV). Therefore, the industry needs to develop a new generation of photosensitive materials to produce smaller microchips for a range of technological applications.

[0005] One strategy to improve the sensitivity of photosensitive materials is to incorporate atoms with enhanced absorption in the EUV region, such as Sn, into resist compositions. Therefore, Sn organometallics with high reactivity and stability are required for use as photosensitive materials in EUV processes and deposition processes. Summary of the invention

[0006] The inventors have determined that lowering the bond energy of the Sn-C bond can improve the performance of Sn photosensitive materials in certain applications (photolytic cleavage of the Sn-C bond during EUV exposure promotes crosslinking, making these materials excellent negative photoresists). Ligands containing unsaturated hydrocarbons, such as allyl groups, may reduce the bond energy of the Sn-C bond.

[0007] Although the above advantages reduce the bond energy of Sn-C bonds in photosensitive materials, it is also conceivable that strengthening the Sn-C bonds in photosensitive materials may also be beneficial in photosensitive materials for other uses. Ligands containing unsaturated hydrocarbons, such as vinyl groups, can provide an increase in the bond energy of Sn-C bonds. By strengthening the Sn-C bond, some of the ligands bonded to Sn can be retained in the deposited film for further EUV processing, which may be beneficial in specific applications.

[0008] In addition, the amino, alkoxy or halide ligands are able to react with the OH groups of the wafer / substrate to achieve efficient ALD deposition. Therefore, the inventors have found that tin organometallics having a combination of ligands containing unsaturated hydrocarbons and ligands containing amino, alkoxy or halide have improved deposition performance, especially atomic layer deposition performance, and can be used as photosensitive materials in patterning applications.

[0009] In one aspect, an organometallic compound of the following formula I is disclosed:

[0010] (R) x Sn(A) 4-x Formula I

[0011] in:

[0012] R is 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;

[0013] A is NR 1 R 2 , OR 3 , pyrrolidinyl, pyrrolyl or halide;

[0014] R 1 and R 2 Each is an alkyl group having 1 to 10 carbon atoms;

[0015] R 1 and R 2 Can be the same or different;

[0016] R 3 is an alkyl group having 2 to 8 carbon atoms;

[0017] x is an integer from 1 to 3; and

[0018] When A is NR 1 R 2 , pyrrolidinyl, pyrrolyl or halide, R is substituted Cp or a non-cyclic unsaturated hydrocarbon having 2 to 10 carbon atoms, or 2 to 8 carbon atoms or 2 to 4 carbon atoms.

[0019] In embodiments, R is an allyl group or a vinyl group. In some embodiments, the allyl group or the vinyl group may be a straight chain. Alternatively, the allyl group may be a group having the general formula: CR 4 R 5 CR 6 =CR 7 R 8 A substituted allyl group, wherein R 4 , R 5 , R 6 , R 7 and R 8 Each is independently selected from the group consisting of H and an alkyl group having 1 to 4 carbon atoms. Similarly, the vinyl group may be a group having the general formula: CR 9 =CR 10 R 11 A substituted vinyl group, wherein R 9 , R 10 and R11 Each is independently selected from the group consisting of H and an alkyl group having 1 to 4 carbon atoms.

[0020] In other embodiments, R is Cp, which is a 12 , R 13 , R 14 , R 15 and R 16 Depending on A, Cp may be substituted or unsubstituted. 12 , R 13 , R 14 , R 15 and R 16 R is 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 can be the same or different. However, when 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.

[0021] In any of the above embodiments, A is NR 1 R 2 In these embodiments, R 1 and R 2 is independently selected from an alkyl group having 1 to 4 carbon atoms. 1 and R 2 is methyl or ethyl. In an embodiment, R 1 and R 2 are different.

[0022] Alternatively, A can be OR 3 In these embodiments, R 3 is an alkyl group having 1 to 4 carbon atoms. 3 is methyl, ethyl or tert-butyl. In other embodiments, A is one of pyrrolyl, pyrrolidinyl or halide.

[0023] In an embodiment, the organometallic compound is selected from the group consisting of: (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(pyrrolidine)3, (Cp)Sn(NMe2)3, (Cp)Sn(NEt2)3, (Cp)Sn(NEtMe)3, (Cp)Sn(pyrrolidine)3, (CH2=CHCH2)2Sn(NMe2)2, (CH2=CHCH2)2Sn(NEt2)2, (CH2=CHCH2)2Sn(NEtMe)2, (CH2=CHCH2)2Sn(pyrrolidine)2, (CH2=CH)2Sn(N Me2)2, (CH2=CH)2Sn(NEt2)2, (CH2=CH)2Sn(NEtMe)2, (CH2=CH)2Sn(pyrrolidine)2, (Cp)2Sn(NMe2)2, (Cp)2Sn(NEt2)2, (Cp)2Sn(NEtMe)2, (Cp)2Sn(pyrrolidine)2, (CH2=CHCH2)3Sn(NMe2), (CH2=CHCH2)3Sn(NEt2), (Cp)2Sn(NEtMe)2 H2=CHCH2)3Sn(NEtMe), (CH2=CHCH2)3Sn(pyrrolidine), (CH2=CH)3Sn(NMe2), (CH2=CH)3Sn(NEt2), (CH2=CH)3Sn(NEtMe), (CH2=CH)3Sn(pyrrolidine), (Cp)3Sn(NMe2), (Cp)3Sn(NEt2), (Cp)3Sn(NEtMe), (Cp)3Sn(pyrrolidine).

[0024] BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Embodiments of the present invention will now be described by way of example with reference to the accompanying drawings, in which:

[0026] FIG. 1 shows the reaction mixture containing (CH2=CHCH2)Sn(Cl)3 in toluene. 1 H NMR spectrum (300 MHz, C6D6).

[0027] FIG. 2 shows the reaction mixture containing (CH2=CHCH2)Sn(Cl)3 in toluene. 119 Sn NMR spectrum (186.55 MHz, C6D6).

[0028] FIG. 3 shows the reaction mixture containing (CH2=CHCH2)2Sn(Cl)2 in toluene. 1 H NMR spectrum (300 MHz, C6D6).

[0029] Figure 4 shows the separation of the product mixture containing (CH2=CHCH2)Sn(NMe2)3, (CH2=CHCH2)2Sn(NMe2)2 and (CH2=CHCH2)3Sn(NMe2) after 12 hours at 22°C. 1 H NMR spectrum (300 MHz, C6D6).

[0030] Figure 5 shows the separation of the product mixture containing (CH2=CHCH2)Sn(NMe2)3, (CH2=CHCH2)2Sn(NMe2)2 and (CH2=CHCH2)3Sn(NMe2) after 12 hours at 22°C. 119 Sn NMR spectrum (187 MHz, C6D6).

[0031] Figure 6 shows the product mixture containing (CH2=CHCH2)2Sn(NiPr2)2 and HNiPr2 1 H NMR spectrum (300 MHz, C6D6).

[0032] Figure 7 shows the (CH2=CH)3Sn(NEt2) 1 H NMR spectroscopy (500 MHz C6D6).

[0033] Figure 8 shows the (CH2=CH)3Sn(NEt2) 1 H NMR spectrum (186 MHz C6D6).

[0034] FIG9 shows the vapor pressure curve of (CH2=CH)3Sn(NEt2).

[0035] Figure 10 shows the Cp iPr Sn(NMe2)3 119 Sn NMR spectrum (186 MHz, C6D6).

[0036] Fig.11A A cross section of the deposited intermediate product is shown.

[0037] Fig. 11B A cross section of the developed intermediate product is shown.

[0038] Fig. 11C A cross section of the etched intermediate product is shown.

[0039] Fig.11DA cross section of the final product is shown.

[0040] FIG12 shows a schematic diagram of a multi-stage vacuum distillation apparatus.

[0041] Detailed description

[0042] Before describing several exemplary embodiments, it should be understood that the invention is not limited to the details of construction or process steps set forth in the following description. The invention is capable of other embodiments and of being practiced or carried out in various ways.

[0043] References throughout this specification to "one embodiment," "certain embodiments," "one or more embodiments," or "an embodiment" mean that a particular feature, structure, material, or characteristic associated with the embodiment is included in at least one embodiment. Therefore, phrases such as "in one or more embodiments," "in certain embodiments," or "in an embodiment" appearing in various places in this specification do not necessarily refer to the same embodiment. Furthermore, in one or more embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner.

[0044] Although specific embodiments are referred to herein, it should be understood that these embodiments are only used to illustrate the principles and applications of the present invention. It will be appreciated by those skilled in the art that various modifications and variations may be made to the methods and apparatus of the present invention without departing from the spirit and scope of the present invention. Therefore, the present invention is intended to include modifications and variations within the scope of the appended claims and their equivalents.

[0045] Unless otherwise specified, the terms “a” or “an” mentioned in this specification refer to one or more and are not limited to the singular.

[0046] The following detailed description may be read in conjunction with the accompanying drawings, wherein like reference numerals refer to like elements.

[0047] The present invention discloses an organometallic compound of the following formula I:

[0048] (R) x Sn(A) 4-x Formula I

[0049] in:

[0050] R is 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;

[0051] A is NR 1 R 2 , OR 3 , pyrrolidinyl, pyrrolyl or halide;

[0052] R 1 and R 2 Each is an alkyl group having 1 to 10 carbon atoms;

[0053] R 1 and R 2 Can be the same or different;

[0054] R 3 is an alkyl group having 2 to 8 carbon atoms;

[0055] x is an integer from 1 to 3; and

[0056] When A is NR 1 R 2 , pyrrolidinyl, pyrrolyl or halide, R is substituted Cp or a non-cyclic unsaturated hydrocarbon having 2 to 10 carbon atoms, or 2 to 8 carbon atoms or 2 to 4 carbon atoms.

[0057] Also disclosed are high purity organometallic compounds and methods for purifying the organometallic compounds.

[0058] The inventors have found that dissociation occurs during the synthesis of the compound of formula I. For example, the product (CH2=CHCH2)2Sn(NMe2)2 molecules undergo significant ligand exchange, resulting in the formation of by-products such as (CH2=CHCH2)Sn(NMe2)3 and (CH2=CHCH2)3Sn(NMe2). It is expected that larger ligands, such as substituted allyl, substituted vinyl, substituted or unsubstituted Cp (cyclopentadienyl), heavier amines or heavier alkoxides in the compound of formula I may be able to prevent the generation of by-products and improve stability by reducing ligand exchange.

[0059] In an embodiment, R is of the general formula: CR 4 R 5 CR 6 =CR 7 R 8 Allyl, where R 4 , R 5 , R 6 , R 7 and R 8 R is independently selected from 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 Can be the same or different. In an embodiment, R 4 and R 5 At least one of them is not H, such as 1,1-dimethylallyl, where R4 and R 5 In the embodiment, R 6 is not H, such as 2-methylallyl. In an embodiment, R 7 and R 8 At least one of is not H, for example 3,3-dimethylallyl. In some embodiments, x is 2, and the compound of formula I is represented by the following formula: (CR 4 R 5 CR 6 =CR 7 R 8 )2Sn(A)2, where A is NR 1 R 2 , OR 3 , pyrrolidinyl, pyrrolyl or halide.

[0060] In other embodiments, R is of the general formula: CR 9 =CR 10 R 11 Vinyl, where R 9 , R 10 and R 11 R is independently selected from 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 Can be the same or different. In an embodiment, R 9 is not H, such as 1-ethylvinyl. In an embodiment, R 10 and R 11 At least one of is not H, for example 2,2-dimethylvinyl. In some embodiments, x is 2, and the compound of formula I is represented by the following formula: (CR 9 =CR 10 R 11 )2Sn(A)2, where A is NR 1 R 2 , OR 3 , pyrrolidinyl, pyrrolyl or halide.

[0061] Any of the above compounds of Formula I include those where x is 1. In these embodiments, the compounds of Formula I are represented by the formula: (R) Sn(A)3, where R is an acyclic unsaturated hydrocarbon having 2 to 10 carbon atoms. The compounds of Formula I also include those where x is 3. In these alternative embodiments, the compounds of Formula I are represented by the formula: (R)3Sn(A), where R is an acyclic unsaturated hydrocarbon having 2 to 10 carbon atoms.

[0062] By the following formula: (R) x Sn(A)4-x Any of the above compounds of Formula I represented by include those wherein R is an acyclic unsaturated hydrocarbon having 2 to 8 carbon atoms. In addition, compounds of Formula I include those wherein R is an acyclic unsaturated hydrocarbon having 2 to 4 carbon atoms.

[0063] Any of the above compounds of formula I includes wherein A is NR 1 R 2 Those of R 1 and R 2 R 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 Can be the same or different. In a specific embodiment, R 1 and R 2 Each is an alkyl group having 1 to 10 carbon atoms. In a more specific embodiment, R 1 and R 2 Each is an alkyl group having 2 to 4 carbon atoms. More specifically, R 1 and R 2 Each may be selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl and n-butyl.

[0064] For any of the above compounds, it is contemplated that R may be a straight chain unsaturated hydrocarbon or a branched chain unsaturated hydrocarbon.

[0065] Any of the above compounds of formula I also includes wherein A is OR 3 In these embodiments, the compound of formula I is represented by the formula: (R) x Sn(OR 3 ) 4-x , where R 3 is an alkyl group having 2 to 8 carbon atoms. In other embodiments, R 3 is selected from alkyl groups having 1 to 4 carbon atoms. More specifically, R 3 It may be selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, isobutyl and n-butyl.

[0066] When A is an alkoxy group, such as OR 3 In these embodiments, the compound of formula I is represented by the formula: (Cp) x Sn(OR 3 ) 4-x , where Cp is the 12 , R 13 , R 14 , R 15 and R 16 Cp may be unsubstituted, wherein R 12 , R13 , R 14 , R 15 and R 16 is H, or is 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 Can be the same or different.

[0067] When A is an amine group, such as NR 1 R 2 , or pyrrolidinyl, pyrrolyl or halide, R may be substituted Cp, wherein 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 Can be the same or different.

[0068] Compounds of formula I include those wherein A is pyrrolidinyl or pyrrolyl. These embodiments are respectively represented by the general formula: (R) x Sn(Pyrrolidino) 4-x or (R) x Sn(Pyrrolyl) 4-x It is contemplated that A may also be a halide, such as chlorine, bromine or iodine.

[0069] When R is Cp, the compound of formula I (Cp) x Sn(A) 4-x It can be synthesized as follows. In a glove box, SnCl4 and anhydrous hexane are placed in a 1L round-bottom flask. One equivalent of NaCp*(NaC5Me5) is added dropwise during cooling. The reaction mixture is stirred 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 vacuum distillation. The product is separated by sublimation.

[0070] 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)S n(pyrrolidinyl)3, (Cp)Sn(NMe2)3, (Cp)Sn(NEt2)3, (Cp)Sn(NEtMe)3, (Cp)Sn(pyrrolidine)3, (CH2=CHCH2)2Sn(NMe2)2, (CH2=CHCH2)2Sn(NEt2)2, (CH2=CHCH2)2Sn(NEtMe)2, (CH2=CHCH2)2Sn(pyrrolidine)2, (CH2=CH)2Sn(NM e2)2, (CH2=CH)2Sn(NEt2)2, (CH2=CH)2Sn(NEtMe)2, (CH2=CH)2Sn(pyrrolidine)2, (Cp)2Sn(NMe2)2, (Cp)2Sn(NEt2)2, (Cp)2Sn(NEtMe)2, (Cp)2Sn(pyrrolidine)2, (CH2=CHCH2)3Sn(NMe2), (CH2=CHCH2)3Sn(NEt2), (CH 2=CHCH2)3Sn(NEtMe), (CH2=CHCH2)3Sn(pyrrolidine), (CH2=CH)3Sn(NMe2), (CH2=CH)3Sn(NEt2), (CH2=CH)3Sn(NEtMe), (CH2=CH)3Sn(pyrrolidine), (Cp)3Sn(NMe2), (Cp)3Sn(NEt2), (Cp)3Sn(NEtMe), (Cp)3Sn(pyrrolidine).

[0071] Reducing the bond strength of Sn-C bonds can improve the performance of Sn photosensitive materials during the photolytic breakage of Sn-C bonds when exposed to EUV. This will promote crosslinking, making these materials excellent negative photoresists. Unsaturated hydrocarbons such as allyl ligands are ideal compounds for this application. In addition, the presence of Sn-allyl bonds will increase the reactivity of this molecule during the formation of SnO2 films.

[0072] In photosensitive materials, it may also be advantageous to increase the binding strength of the Sn-C bond. Ligands containing unsaturated hydrocarbons, such as vinyl groups, can provide an increase in the bond energy of the Sn-C bond. By strengthening the Sn-C bond, some of the ligands bonded to Sn can be retained in the deposited film for further EUV processing, which may be advantageous.

[0073] The compounds of formula I can be prepared by methods known in the art. The following examples are illustrative of these procedures but are not meant to be limiting.

[0074] Example 1: Synthesis of (CH2=CHCH2)Sn(Cl)3

[0075] On a double manifold, 6.0 mL SnCl4 (51 mmol), about 60 mL anhydrous toluene and a magnetic stirring bar were charged into a small Schlenk flask. While stirring at room temperature, 4.1 mL Sn(allyl)4 (17 mmol) was added dropwise. The reaction mixture was stirred at 22°C for 90 minutes. A small sample was collected for 1 H NMR and 119 Sn NMR analysis 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 (300 MHz, C6D6) (Figure 1): 1.72 ppm (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 =9.7 Hz, 1H, allyl CH2), 5.15 ppm (m, 1H, allyl CH). 119 Sn NMR (186.55 MHz, C6D6) (Figure 2): -26.8 ppm.

[0076] Example 2: Synthesis of (CH2=CHCH2)2Sn(Cl)2

[0077] On a double manifold, a small Schlenk flask was charged with 2.0 mL SnCl4 (17 mmol), about 30 mL anhydrous toluene, and a magnetic stirring bar. While stirring at room temperature, 4.1 mL Sn(allyl)4 (17 mmol) was added dropwise. The reaction mixture was stirred at 22°C for 90 minutes. A small sample was collected for 1 H NMR and 119 Sn NMR analysis confirmed the formation of (CH2=CHCH2)2Sn(Cl)2, as shown in Figure 3. Removal of solvent may affect stability. Characterization:1 H NMR (300 MHz, C6D6) (Figure 3): 1.96 ppm (m, 1H, allyl CH2), 1.99 ppm (m, 1H, allyl CH2), 4.80-4.88 ppm (m, 2H, allyl CH2), 5.57 ppm (m, 1H, allyl CH). 119 Sn NMR (186.55MHz, C6D6): 48.3ppm.

[0078] Example 3: Synthesis of (CH2=CHCH2)2Sn(NMe2)2

[0079] On a dual manifold, 82 mL BuLi (2.5 M in hexane, 0.205 mol), about 500 mL anhydrous toluene and a magnetic stirring bar were added to a 1 L round-bottom flask. 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 taken out from a cooling bath and stirred at 22 ° C for 90 minutes.

[0080] Meanwhile, (CH = CHCH ) Sn (Cl) was prepared by reacting 6.0 mL SnCl (0.051 mol) with 12.3 mL Sn (allyl) (0.051 ml) in about 100 mL anhydrous toluene. The reaction was stirred at 22° C. for 60 minutes. The flask containing (CH = CHCH ) Sn (Cl) was placed back in an ice-water bath and the LiNMe mixture was slowly added dropwise to the flask via a dropper. The final reaction mixture was taken out from the cooling bath and stirred at 22° C. for 50 minutes.

[0081] Stop stirring and allow the LiCl salt to precipitate overnight. The next day, transfer the liquid layer to a new round-bottom flask. Remove the solvent by vacuum distillation. -2 Torr) to separate the final product. Significant ligand exchange of (CH2=CHCH2)2Sn(NMe2)2 was detected, leading to the formation of (CH2=CHCH2)SN(NMe2)3 and (CH2=CHCH2)3Sn(NMe2). Ultimately, the product distribution reached 50:25:25 mol%.

[0082] Characterization:

[0083] (CH2=CHCH2)3Sn(NMe2): 1 H NMR (300 MHz, C6D6) (Figure 4): 1.87 ppm (dd, 2 J HH =1.2Hz; 3 J HH=0.7Hz,3H,allylCH2),1.90ppm(dd, 2 J HH =1.2Hz; 3 J HH =0.7Hz,3H,allylCH2),2.73ppm(s, 3 J H119Sn =42.6Hz, 3 J H117Sn =41.1 Hz, 6H, NMe2), 4.82 ppm (m, 3H, allyl CH2), 4.93 ppm (ddd, 3 J HH =16.8Hz, 4 J HH =3.2Hz, 2 J HH =1.2 Hz; 3H, allyl CH2), 5.9 ppm (m, 3H, allyl CH). 119 Sn NMR (186.55 MHz, C6D6) (Figure 5): -6.9 ppm.

[0084] (CH2=CHCH2)2Sn(NMe2)2: 1 H NMR (300 MHz, C6D6) (Figure 4): 1.92 ppm (dd, 2 J HH =1.2Hz; 3 J HH =0.7Hz,2H,allylCH2),1.94ppm(dd, 2 J HH =1.2Hz; 3 J HH =0.7Hz,2H,allylCH2),2.78ppm(s, 3 J H119Sn =43.6Hz, 3 J H117Sn =41.6 Hz, 12H, NMe2), 4.83 ppm (m, 2H, allyl CH2), 4.97 ppm (ddd, 3 J HH =16.8Hz, 4 J HH =3.0Hz, 2 J HH =1.2 Hz; 2H, allyl CH2), 5.9 ppm (m, 2H, allyl CH). 119 Sn NMR (186.55 MHz, C6D6) (Figure 5): -21.6 ppm.

[0085] (CH2=CHCH2)Sn(NMe2)3: 1 H NMR (300 MHz, C6D6) (Figure 4): 1.93 ppm (dd, 2 J HH =1.5Hz; 3 J HH =1.0Hz,1H,allylCH2),1.95ppm(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 =1.2 Hz; 1H, allyl CH2), 5.9 ppm (m, 1H, allyl CH). 119 Sn NMR (186.55 MHz, C6D6) (Figure 5): -64.9 ppm.

[0086] Example 4: Synthesis of (CH2=CHCH2)2Sn(NEt2)2

[0087] On a dual manifold, 27.5 mL of nBuLi (2.5 M in hexane, 0.069 mol), about 125 mL of anhydrous toluene, and a magnetic stirring bar were added to a Schlenk flask. The flask was placed in an ice-water bath, and a solution of HNEt2 (7.4 mL, 0.072 mol) in about 20 mL of anhydrous toluene was added dropwise to the reaction flask. The reaction flask was removed from the cooling bath and stirred at 22° C. for 40 minutes.

[0088] Meanwhile, (CH = CHCH) Sn(Cl) was prepared by reacting 2.0 mL SnCl (0.017 mol) with 4.1 mL Sn(allyl) (0.017 mol) in about 80 mL anhydrous toluene. The reaction was stirred at 22 ° C for 60 minutes. The flask containing (CH = CHCH) Sn(Cl) was placed back in an ice-water bath and the LiNMe mixture was slowly added dropwise to the flask via a dropper. The final reaction mixture was taken out from the cooling bath, stirred at 22 ° C for 30 minutes, and then distilled under reduced pressure to remove the solvent and collect the product (80 ° C, 0.05 Torr).

[0089] 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),1.98ppm(dd, 2 J HH =1.5Hz; 3 J HH =1.0Hz,2H,allylCH2),3.04ppm(q, 3 J HH =6.9 Hz, 8H, N(CH2CH3)), 4.86 ppm (m, 2H, allyl CH2), 4.98 ppm (m, 2H, allyl CH2), 5.9 ppm (m, 2H, allyl CH). 119 Sn NMR (134.35MHz, C6D6): -24.8ppm.

[0090] Example 5: Synthesis of (CH2=CHCH2)2Sn(NiPr2)2

[0091] On a dual manifold, 29.9 mL of nBuLi (2.5 M in hexane, 0.075 mol), about 500 mL of anhydrous toluene, and a magnetic stirring bar were loaded into a 1 L round bottom flask. The flask was placed in an ice-water bath, and a solution of HNiPr2 (11 mL, 0.079 mol) in about 20 mL of anhydrous toluene was added dropwise to the reaction flask. The reaction flask was removed from the cooling bath and stirred overnight at 22 ° C. The reaction flask was then transferred to an ice-water bath.

[0092] Meanwhile, (CH2=CHCH2)2Sn(Cl)2 was prepared by reacting 2.19 mL SnCl4 (0.019 mol) with 4.49 mL Sn(allyl)4 (0.019 mol) in about 100 mL anhydrous toluene. The reaction was stirred at 22°C for 3 hours. The (CH2=CHCH2)2Sn(Cl)2 mixture was slowly added dropwise to a round bottom flask via a dropper. The final reaction mixture was removed from the cooling bath and stirred overnight at 22°C. After removing the solvent from the final product mixture, the product and some free amines in the residue were characterized. The product was a solid with no signs of ligand exchange.

[0093] Characterization: 1 H NMR (300 MHz, C6D6) (Figure 6): 0.89 ppm (d, 3 J HH =6.7Hz,24H,iPr-CH3),1.89ppm(dd, 2 J HH =1.0Hz; 3 J HH =1.2Hz,2H,allylCH2),1.92ppm(dd, 2 J HH =1.0Hz; 3 J HH =1.2Hz,2H,allylCH2),3.17ppm(sept, 3 J HH =6.7 Hz, 4H, iPr-CH), 4.68 ppm (m, 2H, allyl CH2), 4.78 ppm (m, 2H, allyl CH2), 5.80 ppm (m, 2H, allyl CH).

[0094] Example 6: Synthesis of (CH2=CH)3SnCl

[0095] The synthesis of the complex is 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", 79 J. AM. CHEM. SOC'Y. 2138 (1957), https: / / doi.org / 10.1021 / ja01566a029 [hereinafter referred to as Rosenberg & Gibbons]. The complex was not isolated and 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 =19.9 Hz, 3H, vinyl-CH). 119 Sn (186MHz, C6D6): s-53.8ppm.

[0096] Example 7: Synthesis of (CH2=CH)3Sn(NEt2)

[0097] On a dual manifold, a 500 mL round bottom flask was charged with 10.5 mL nBuLi (2.5 M in hexane, 0.0263 mol), about 250 mL anhydrous hexane and a magnetic stirring bar. HNEt2 (2.8 mL, 0.027 mol) was added dropwise to the reaction flask. The reaction mixture was stirred at 22 °C for 60 minutes.

[0098] Meanwhile, (CH2=CH)3SnCl was prepared by reacting 3.5 mL Sn(vinyl)4 (0.019 mol) and 0.8 mL SnCl4 (0.0068 mol). The reaction was stirred at 40°C for 90 minutes. See Rosenberg & Gibbons.

[0099] The (CH2=CH)3SnCl mixture was slowly added to the LiNEt2 mixture via a dropper. The final reaction mixture was stirred overnight at 22°C. The next day, the solvent was removed by distillation under reduced pressure, and the product was collected in a separate receiving bottle (0.08 Torr, 35°C), collecting 5.2 g of product (75% yield).

[0100] 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),dd6.16ppm( 3 J HH =3.2Hz, 3 J HH =13.7Hz,3H,vinyl-CH),dd 6.40ppm( 3 J HH =13.7Hz, 3 J HH =20.5 Hz, 3H, vinyl-CH). 119 Sn (186 MHz, C6D6) (Figure 8): s -104.1 ppm.

[0101] Figure 9 shows the vapor pressure curve of (CH2=CH)3Sn(NEt2). Vapor pressure measurement: log 10 P = -2691.6 / T + 8.6502. Vapor pressure measurements are made as follows: A small amount of liquid is evaporated in a closed system where the temperature and pressure are controlled. At a set temperature, the pressure is slowly reduced until the liquid sample evaporates at a rate determined by measuring the rate of decline of the liquid in a condenser just above the liquid. This is repeated at 8-10 temperatures and in duplicate. The results are compared to a side-by-side run of a calibration standard which helps to adjust the measured rate of decline and pressure at temperature to the known vapor pressure at that temperature.

[0102] Example 8: Cp iPr Synthesis of Sn(NMe2)3

[0103] In a glove box, a small Schlenk flask was charged with 1.2 mL Sn(NMe2)4 (4.7 mmol) and about 13 mL anhydrous THF. 0.679 g sodium chloride (5.2 mmol) was added. The Schlenk flask was transferred to a double manifold and refluxed at 76°C for 4 hours. NMR analysis of the reaction mixture confirmed the presence of Cp iPr Sn(NMe2)3 is formed. After isolation, the product is a solid.

[0104] 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),sept 3.18( 3 J HH =6.7Hz,1H,iPr-CH),m6.21(2H,Cp-H),m 6.32(2H,Cp-H). 119 Sn (186 MHz, C6D6) (Figure 10): s 63.9 ppm.

[0105] Compared with compounds known in the art, the compounds of formula I can have improved thermal stability and surface reactivity, thereby improving ALD films. Poor thermal stability can hinder the reactivity of the precursor with the substrate surface during ALD deposition, that is, the precursor should not decompose before ALD deposition. In contrast to ALD, in the CVD process, high energy and high temperature are used to react the precursor at the process temperature. The reacted precursor is then reacted on the substrate. Since the CVD process uses much more energy and decomposes the precursor before reaction, the reactivity of the precursor is not as important in the CVD process as in the ALD process.

[0106] Negative resist deposition

[0107] Figures 11A-11DA typical process for negative resist deposition using a compound of Formula I is shown. A multilayer substrate 10 is provided. In the embodiment shown, layer 10A is the only layer in the substrate to be patterned. Subsequently, a photosensitive material layer 30 including a compound of Formula I is deposited on layer 10A. Then, a mask 40 is selectively applied to portions of the photosensitive material layer 30 such that unexposed portions 30A of the photosensitive material layer 30 are covered by the mask 40 and exposed portions 30B of the photosensitive material layer 30 are not covered by the mask 40. Finally, in the embodiment shown, a mask glass layer 50 is applied over the mask 40 and the photosensitive material layer 30. Thus, a photosensitive layer 30 is formed as shown in FIG. Fig.11A The deposition middle portion 1a is shown.

[0108] Then, the deposited middle portion 1a is irradiated with extreme ultraviolet (EUV) light through mask 40, resulting in photolytic cleavage of Sn-C bonds, thereby promoting crosslinking. After irradiation, the deposited middle portion 1a is baked to densify the SnO2 layer. Then, the glass mask 50 is removed.

[0109] The development steps are as follows Fig. 11B During the development step, the unexposed portion 30A of the photosensitive material layer 30 that was not exposed to EUV light during the irradiation is removed so that only the exposed portion 30B of the photosensitive material layer 30 remains. Fig. 11B As shown, the unexposed portion 30B is located on the layer 10A of the multilayer substrate 10. Thus, the Fig. 11B The developed intermediate product 1b is shown.

[0110] In the etching step, as Fig. 11C As shown, layer 10A of multilayer substrate 10 is etched into a desired pattern. Etching produces layer 10B, which is covered by exposed portion 30B of photosensitive material layer 30. Thus, a layer 10A is formed as shown in FIG. Fig. 11C The etched intermediate product 1c is shown.

[0111] Finally, the exposed portion 30B of the photosensitive material layer 30 is removed, leaving the desired pattern. Fig.11D The resulting pattern is shown in Figure 1. Fig.11D The product 1 is shown.

[0112] The compounds of formula I are particularly advantageous for negative resist deposition processes because the performance of Sn photosensitive materials can be improved by adjusting the bond energy of Sn-C using allyl or vinyl ligands. It is expected that the photolytic cleavage of Sn-C bonds during exposure to EUV light will promote crosslinking, making these materials superior to materials known in the art.

[0113] Multi-stage distillation

[0114] From theoretical models of the activation energy required to strip a ligand from a molecule by a hydrolysis reaction, there is a wide range of activation energies between molecules. Therefore, differences in reactivity are observed. This suggests that when the activation energy is low, the molecule may be a highly reactive molecule to form SnO2, but this value also suggests that the molecule may be more susceptible to decomposition and reaction during synthesis and purification. Therefore, it is difficult to obtain purity of compounds within the range of Formula I, especially assay purities greater than 95% or even greater than 99%.

[0115] However, for compounds within the scope of Formula I, assay purities of greater than 95% and even greater than 99% can be achieved using multistage vacuum distillation. Various forms of multistage distillation are known in chemical manufacturing, but have not been used to purify organometallic materials including Formula I compounds.

[0116] As shown in Figure 12, multiple effect or multistage distillation (MED) is a distillation process commonly used in desalination of seawater. It consists of multiple stages or "effects". (In the schematic diagram of Figure 14, the first stage is at the top. The top area of ​​each stage is steam, and the bottom area of ​​each stage is liquid feed. The material flowing along the pipes on the left side of the figure and at the bottom of VC is condensate. It is not shown how the feed enters other stages beyond the first stage, but the parts should be easy to understand. F-feed inlet. S-heating steam feed inlet. C-heating steam outlet. W-purified material (condensate) outlet. R-waste outlet. O-cooling liquid inlet. P-cooling liquid outlet. VC is the last stage cooler.) In each stage, the feed is heated by steam in the tubes. Some of the feed evaporates, and this steam flows into the pipes of the next stage, heating and evaporating more distillate. Each stage essentially reuses the energy of the previous part.

[0117] 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 a pressure below atmospheric pressure through a vacuum. Each space consists of two connected subspaces, the outside of the n-stage pipe and the inside of the n+1-stage pipe. The temperature and pressure of each space are lower than the previous space, and the temperature of the tube walls is between the temperatures of the fluids on both sides. The pressure in the space cannot be balanced with the temperature of the walls of the two subspaces; it has an intermediate pressure. As a result, the pressure in the first subspace is too low or the temperature is too high, and the feed evaporates. In the second subspace, the pressure is too high or the temperature is too low, and the steam condenses. This carries the evaporation energy from the warmer first subspace to the cooler second subspace. In the second subspace, the energy flows through the tube walls to the cooler next space by conduction.

Claims

1. An organometallic compound of formula I: (R) x Sn(A) 4-x Formula I in: R is 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 halide; R 1 and R 2 Each is independently selected from the group consisting of an alkyl group, an aryl group, and an acyl group having 1 to 10 carbon atoms; R 3 is selected from an alkyl group, an aryl group or an acyl group having 1 to 10 carbon atoms; x is an integer from 1 to 3; and When A is NR 1 R 2 When R is substituted with Cp or a non-cyclic unsaturated hydrocarbon having 2 to 10 carbon atoms, or 2 to 8 carbon atoms, or 2 to 4 carbon atoms, pyrrolidinyl, pyrrolyl or halide.

2. The organometallic compound according to claim 1, characterized in that: The x is 1 or 2.

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

4. The organometallic compound according to any one of claims 1 to 3, characterized in that The R is a straight chain unsaturated hydrocarbon.

5. The organometallic compound according to any one of claims 1 to 3, characterized in that The R is of the general formula: CR 4 R 5 CR 6 =CR 7 R 8 Allyl, where R 4 , R 5 , R 6 , R 7 and R 8 Each is independently selected from H and an alkyl group having 1 to 4 carbon atoms.

6. The organometallic compound according to any one of claims 1 to 3, characterized in that The R is of the general formula: CR 9 =CR 10 R 11 Vinyl, where R 9 , R 10 , and R 11 Each is independently selected from H and an alkyl group having 1 to 4 carbon atoms.

7. The organometallic compound according to any one of claims 1 to 2, characterized in that The R is Cp.

8. The organometallic compound according to any one of claims 1 to 7, characterized in that The x is 2.

9. The organometallic compound according to any one of claims 1 to 8, characterized in that The A is NR 1 R 2 .

10. The organometallic compound according to claim 9, characterized in that The R 1 and R 2 Independently selected from alkyl groups having 1 to 4 carbon atoms.

11. The organometallic compound according to claim 10, characterized in that The R 1 For Me or Et.

12. The organometallic compound according to claim 10, characterized in that The R 2 It's Me or Et.

13. The organometallic compound according to any one of claims 1 to 12, characterized in that The R 1 and R 2 different.

14. The organometallic compound according to any one of claims 1 to 8, characterized in that The A is OR 3 .

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

16. The organometallic compound according to claim 15, characterized in that The R 3 is Me, Et or t Bu.

17. The organometallic compound according to any one of claims 1 to 8, characterized in that The A is a pyrrolyl group.

18. The organometallic compound according to any one of claims 1 to 8, characterized in that The A is a pyrrolidinyl group.

19. The organometallic compound according to any one of claims 1 to 8, characterized in that The A is a halide.

20. The organometallic compound according to claim 1, wherein the organometallic compound is selected from the group consisting of (CH2=CHCH2)Sn(NMe2)3, (CH2=CH)Sn(pyrrolidinyl)3, (CH2=CHCH2)Sn(OEt)3, (Cp)Sn(O i Pr)3, (CH2=CHCH2)2Sn(NMe2)2, (CH2=CHCH2)2Sn(NEt2)2, (CH2=CHCH2)2Sn(NEtMe)2, (CH2=CHCH2)2Sn(pyrrolidinyl)2, (CH2=CHCH2)2Sn(OMe)2, (CH2=CHCH2)2Sn(OEt ... t Bu)2, (CH2=CH)2Sn(NMe2)2, (CH2=CH)2Sn(NEt2)2, (CH2=CH)2Sn(NEtMe)2, (CH2=CH)2Sn(pyrrolidinyl)2, (CH2=CH)2Sn(OMe)2, (CH2=CH)2Sn(OEt ... t Bu)2, (Cp)2Sn(OMe)2, (Cp)2Sn(OEt)2, (Cp)2Sn(O i Pr)2, (CH2=CHCH2)3Sn(NMe2), (CH2=CH)3Sn(pyrrolidinyl), (CH2=CHCH2)3Sn(OEt) and (Cp)3Sn(O i Pr).

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