Preparation of diorganotin dihalides

Abstract

The disclosed and claimed invention relates to a safe and efficient synthesis of diorganotin dihalide compounds of the formula R2SnX2 that are free of tetraalkyltin (R4Sn), trialkyltin halide (R3SnX) and monoalkyltin trihalide (RSnX3) species in the as-synthesized state, and methods for their synthesis and use.

Description

[Technical field]

[0001] The disclosed and claimed invention relates to the corresponding tetraalkyltin (R 4 Sn), trialkyltin halide (R 3 SnX) and monoalkyltin trihalides (RSnX) 3 ) species is not included in the synthesis state of the formula R 2 SnX 2 This invention relates to a safe and efficient synthesis of diorganotin dihalide compounds, as well as methods for their synthesis and use. [Background technology]

[0002] The semiconductor industry is currently investigating the use of metal-containing materials as EUV (extreme ultraviolet) photoresist materials for patterning. Many organometallic complexes, especially tin-containing compounds, have been evaluated as potential precursors for the formation of photoresist materials via spin-coating or chemical vapor deposition. The preparation of organotin precursors for EUV patterning applications involves a series of steps using common halogen and organotin sources and converting them into the final product. One of the main starter materials is tetramethyltin (Me 4 However, tetramethyltin is highly toxic, and there is a strong desire to replace this compound with other materials as a source material for use in EUV processes.

[0003] For example, US 10,787,466 (Patent Document 1) discloses a compound of the formula RSn(OR') 3 or a monoalkyltin trialkoxide compound of the formula RSn(NR' 2 ) 3 The present invention discloses a composition of monoalkyltin triamide compounds of the formula RSn-(NR'COR"), wherein (i) R is a hydrocarbyl group having 1 to 31 carbon atoms and R' is a hydrocarbyl group having 1 to 10 carbon atoms, and (ii) the composition has a dialkyltin compound content of at most 4 mole percent based on the total amount of tin. 3Also disclosed are compositions containing monoalkyltriamidotin compounds of the formula: where R is a hydrocarbyl group having 1 to 31 carbon atoms, and R' and R'' are independently hydrocarbyl groups having 1 to 10 carbon atoms. The presence of dialkyltin compounds (as impurities) in the formulation is believed to affect performance.

[0004] WO2019246254 (Patent Document 2) discloses a precursor solution for radiation patternable coatings formed using an organic solvent and monoalkyltin trialkoxide, the water content of the solvent being adjusted to within 10% of a selected value. Typically, the water content of the solvent is adjusted by adding water, although omission of water can also be used. For example, in some embodiments, the adjusted water content of the solvent can be from about 250 ppm to about 10,000 ppm by weight. Due to the selection of appropriate ligands, the adjusted precursor solution is claimed to be stable for at least about 42 days, and in some cases for at least 8 months.

[0005] US10,732,505 (Patent Document 3) discloses organometallic precursors for the formation of high-resolution lithographic patterning coatings based on metal oxide hydroxide chemistry. The precursor compositions generally contain ligands that can be easily hydrolyzed by water vapor or other -OH sources under moderate conditions. In particular, the organometallic precursors contain radiation-sensitive organic ligands to tin, so that even relatively low radiation doses can be effective for high-resolution patterning, and can result in coatings that are particularly useful for EUV patterning.

[0006] WO2018179704 (Patent Document 4) discloses a method for forming a pattern, comprising: (1) applying a compound for forming an underlayer film onto a substrate; (2) applying a radiation-sensitive compound for forming a resist film directly or indirectly to the underlayer; (3) exposing the resist film; and (4) developing the exposed resist film. The compound may contain a group selected from the group consisting of sulfo, carboxy, phosphono, phosphoric acid, sulfuric acid, sulfonamide, sulfonylimide, -CRF, -CFC, -CFC- ... 1 RF 2 The radiation-sensitive compound comprises (i) a first component which generates under the action of heat a component having an acid group selected from an -OH group or a combination of these groups, and (ii) a second component which is different from the first component but has one of the acid groups. The radiation-sensitive compound comprises a metal-containing compound in a proportion of 50% by weight or more as a solid content.

[0007] Typically, organotin chlorides have been used as raw materials to produce the tin-containing compounds described in the above patents and publications. There are very limited synthetic routes to produce alkyltin chlorides, none of which are suitable for the safe, large-scale production of these materials without the production of highly toxic by-products.

[0008] For example, polymeric diorganotin oxides (R 2 SnO n (R=Me, Et, Bu, C 8 H 17 , Cy, iPr, Ph) in saturated aqueous NH 4 When reacted with X (X = F, Cl, Br, I, OAc), dimeric tetraorganodistannoxanes [R 2 (X)SnOSn(X)R 2 ] 2 , and in some cases diorganotin dihalides or diacetates R 2 SnX 2It has been disclosed that the formation of dimeric tetraorganodistannoxanes is possible by the addition of fluorinated tetraorganodistannoxanes. See J. Beckmann et al., "A novel route for the preparation of dimeric tetraorganodistannoxanes", J. Organomet. Chem., 659(1-2):73-83(2002). The reported method appears to be suitable for the synthesis of fluorinated tetraorganodistannoxanes. The [Bu] in the reaction mixture (established on the basis of tin-119 NMR spectrum) 2 (OH)SnOSn(X)Bu 2 ] 2 (X=Cl, Br) and [Bu 2 (OH)SnOSn(X)Bu 2 ][Bu 2 (X)SnOSn(X)Bu 2 ] coexistence is [R 2 (OH)SnOSn(OH)R 2 ] 2 This suggests a sequential substitution mechanism starting from [Cy 2 (F)SnOSn(F)Cy 2 ] 2 and [Cy 2 (Cl)SnOSn(Cl)Cy 2 ] 2 The redistribution between the mixed halides [Cy 2 (F)SnOSn(Cl)Cy 2 ] 2 [Me 2 (AcO)SnOSn(OAc)Me 2 ] 2 , iPr 2 (Br)SnOSn(Br)iPr 2 ] 2 , [Cy 2 (F)SnOSn(F)Cy 2 ] 2 X-ray crystal structure data has been reported for these compounds. These compounds are linked to R via oxygen atoms. 2 The central (R 2 Sn) 2 O 2This indicates the presence of a core. Acetate and halide complete the coordination around the tin center.

[0009] US 2,675,399 (Patent Document 5) discloses organotin halides prepared in a single step from Sn halides using Mg and an organic halide. Hydrocarbons are used as solvents and the reaction is carried out at 65-185°C. In a typical example, 1.5 mL of EtBr, 12 mL of Et 2 2.0, 4.5 g BuCl, and 30 mL MePh were treated with 24.5 g Mg, stirred until the reaction started, and then 88 g BuCl, 250 mL MePh, and 98.5 g BuSnCl 3 This is treated with a mixture of H 2 After treatment with 2.0, 8.8 g of Bu 2 SnCl 2 , 91.7g Bu 3 SnCl and 7.2 g Bu 4 Similarly, a small amount of iodine is dissolved in 5 mL of BuCl, 5 mL of Et 2 2.0 and 24.4 g of Mg, and when the reaction started, 50 mL of MePh was added, followed by 151.9 g of Bu in 160 mL of MePh. 2 SnCl 2 The mixture is then slowly heated to 95° C. and slowly treated with BuCl (total of 92.5 g) along with 1 mL of EtBr, and refluxed for several hours to give 0.3 g of Bu 2 SnCl 2 , 77.2g Bu 3 SnCl and 72 g Bu 4 Sn is produced.

[0010] Despite the above mentioned synthetic methods, many of the organotin compounds produced are still highly toxic or require the use of toxic raw materials for their production, which in turn results in materials with toxic impurities. This is of particular concern when considering the widespread use of tin compounds. In fact, tin has been reported to have more organometallic derivatives of it in commercial use than any other element. See M. Hoch, “Organotin compounds in the environment - an overview,” Appl. Geochem., 16(7-8):719-743 (2001). As a result of the increased global production of organotin compounds during the last 50 years, significant amounts of organotins have entered various ecosystems. While inorganic forms of Sn are considered non-toxic, the toxicological patterns of organotin compounds are complex. Depending on the nature and number of organic groups attached to the Sn cation, some organotins show specific toxic effects on various organisms even at very low concentrations. Therefore, specific quantification of individual organotin compounds is necessary. In recent years, new highly sensitive analytical techniques have been developed for the detection of organotin compounds in various environmental samples. Large amounts of toxic tributyltin and several other organotin derivatives can be found not only in water and sediments, but also in various aquatic organisms, and mammalian and avian tissues are also contaminated by these compounds. In fact, other studies on human blood and liver have shown increased concentrations of some organotin derivatives.

[0011] For example, Sn alkyl poisoning is caused by Pb(C 2 H 5 ) 4It has been found through clinical observations that symptoms are similar to those of tin peralkyls. See W. Zeman et al., "The genesis of disturbances of circulatory regulation. Toxic effect of tin peralkyls" Dtsch. Arch. Klin. Med., 198:713-721 (1951). Other studies have shown that Sn alkyls are easily absorbed through the skin or lungs. Toxicity studies in mice by intraperitoneal injection have shown that Sn(CH 3 ) 4 The 2-hr LD50 of Sn(C 2 H 5 The 24-hr values ​​are 18 mg / kg and 130 mg / kg, respectively. These results suggest a chronic toxic effect of metal alkyls. 2 H 5 ) 4 With Cl, the LD50 was "only" 60 mg / kg, but all animals that survived 25 minutes recovered.

[0012] Mono-, di-, and trimethyltins have been found to be toxic to microorganisms from aquatic sediments, and the di- and trimethyl compounds were more toxic than the monomethyl compounds, as measured by either viable cell counts or [3H]thymidine incorporation. See GW Tettibone, and JJ Cooney, "Toxicity of methyltins to microbial populations in estuarine sediments," J. Ind. Microbiol., 2(6):373-378 (1988), which examines and discloses the toxicity of three organotin compounds to natural populations of microorganisms in sediments from Boston Harbor. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] US10,787,466 [Patent Document 2] WO2019246254 [Patent Document 3] US10,732,505 [Patent Document 4] WO2018179704 [Patent Document 5] US2,675,399 [Patent Document 6] US10,73287,466 [Patent Document 7] US2019 / 0391486 [Patent Document 8] US2020 / 117085A [Non-Patent Document]

[0014] [Non-Patent Document 1] J.Beckmann et al., “A novel route for the preparation of dimeric tetraorganodistannoxanes”, J.Organomet.Chem., 659(1-2):73-83(2002) [Non-Patent Document 2] M.Hoch, “Organotin compounds in the environment - an overview,” Appl.Geochem., 16(7-8):719-743(2001) [Non-Patent Document 3] W.Zeman et al., “The genesis of disturbances of circulatory regulation.Toxic effect of tin peralkyls” Dtsch.Arch.Klin.Med., 198:713-721(1951) [Non-Patent Document 4] GWPettibone, and JJCooney, “Toxicity of methyltins to microbial populations in estuarine sediments” J.Ind.Microbiol., 2(6):373-378(1988) [Non-Patent Document 5] Kennedy, JD, “Auto-association in organometallic compounds: a nuclear magnetic double resonance study of methyl- and n-butyl-tin alkoxides.” J.Chem.Soc., Perkin Trans., 2(2):242-248(1977) [Non-Patent Document 6] Reuter, H. and D. Schroeder, “Preparation, crystal structure and reactions of isopropyltin triisopropoxide” J. Organomet.Chem., 455(1-2):83-87(1993) [Non-Patent Document 7] Jones, K. and MFLappert “Aminostannanes, stannylamines, and stannazanes” Proc. Chem. Soc., London, 358-359, (1962) Summary of the Invention [Problem to be solved by the invention]

[0015] Thus, although the literature describes numerous routes for producing diorganotin dihalide materials (e.g., dimethyltin dichloride), these are cumbersome, uneconomical (e.g., redistribution methods use tetramethyltin and tin tetrachloride, many are direct methods using catalysts and relatively high temperatures, others use molten tin and methyl chloride, and others are the addition of conventional Grignard reagents to tin tetrachloride) and / or rely on toxic materials. Thus, there is a need to develop diorganotin dihalides that contain little or no toxic impurities in the as-synthesized state and are produced in an economically viable and environmentally safe manner. In addition, there is a need for new synthetic routes that do not utilize toxic raw materials (e.g., tetramethyltin) as in the case of conventional synthetic methods via the reaction of tetraorganotins with tin tetrahalides to produce diorganotin dihalides. There is also a desire to provide an environmentally friendly method for synthesizing diorganotin dihalides that does not contain toxic materials as synthesized, and therefore the waste streams from production and / or purification do not contain hazardous and / or toxic unreacted raw materials (e.g., tetramethyltin and partially reacted trimethylchlorotin), thereby reducing downstream contact (e.g., in the filtrate) with these hazardous materials. [Means for solving the problem]

[0016] In one embodiment, the disclosed and claimed invention provides a method for preparing, as synthesized (i.e., without further purification), the corresponding tetraalkyltin (R 4 Sn), trialkyltin halide (R 3 SnX) and monoalkyltin trihalides (RSnX) 3 ) Species-free formula R 2 SnX 2 wherein (i) R is an unsubstituted linear C 1 -C 10 Alkyl, halogen-substituted linear C 1 -C 6 Linear C substituted with alkyl and amino groups1 -C 6 Alkyl groups, unsubstituted branched C 3 -C 10 Branched C substituted with alkyl and halogen 3 -C 10 Branched C substituted with alkyl and amino groups 3 -C 10 Alkyl groups, unsubstituted amines, substituted amines, -Si(CH 3 ) 3 , unsubstituted C 3 -C 8 Cyclic alkyl groups, halogen-substituted C 3 -C 8 Cyclic alkyl, amino substituted C 3 -C 8 Cyclic alkyl groups, unsubstituted C 3 -C 8 Aromatic groups, halogen-substituted C 3 -C 8 C substituted with aromatic or amino groups 3 -C 8 Aromatic group, C 3 -C 10 Heterocyclic groups, C 3 -C 10 Alkenyl groups, and C 3 -C 10 and (ii) X is Cl, Br, F, or I. In one aspect of this embodiment, R is a methyl group. In another aspect of this embodiment, R is an ethyl group. In one aspect of this embodiment, X is Cl. In another aspect of this embodiment, R is a methyl group and X is Cl. In another aspect of this embodiment, R is an ethyl group and X is Cl.

[0017] In another aspect, the disclosed and claimed invention provides the corresponding tetraalkyltin (R 4 Sn), trialkyltin halide (R 3 SnX) and monoalkyltin trihalides (RSnX) 3 ) Formula R that does not contain species as an essence 2 SnX2 Synthesis of diorganotin dihalides (R 2 Regarding the synthesis from SnO:

[0018] [ka] where: (i) R is an unsubstituted linear C 1 -C 10 Alkyl, halogen-substituted linear C 1 -C 6 Linear C substituted with alkyl and amino groups 1 -C 6 Alkyl groups, unsubstituted branched C 3 -C 10 Branched C substituted with alkyl and halogen 3 -C 10 Branched C substituted with alkyl and amino groups 3 -C 10 Alkyl groups, unsubstituted amines, substituted amines, -Si(CH 3 ) 3 , unsubstituted C 3 -C 8 Cyclic alkyl groups, halogen-substituted C 3 -C 8 Cyclic alkyl, amino substituted C 3 -C 8 Cyclic alkyl groups, unsubstituted C 3 -C 8 Aromatic groups, halogen-substituted C 3 -C 8 C substituted with aromatic or amino groups 3 -C 8 Aromatic group, C 3 -C 10 Heterocyclic groups, C 3 -C 10 Alkenyl groups and C 3 -C 10and (ii) X is Cl, Br, F, or I. In one aspect of this embodiment, R is a methyl group. In another aspect of this embodiment, R is an ethyl group. In one aspect of this embodiment, X is Cl. In another aspect of this embodiment, R is a methyl group and X is Cl. In another aspect of this embodiment, R is an ethyl group and X is Cl.

[0019] In another aspect, the formula R 2 SnX 2 The diorganotin dihalides of formula (II) are represented by the formula R 2 SnL 2 It can also be converted to the compound:

[0020] [ka] wherein L is a hydrolyzable monoanionic ligand capable of replacing X through chemical exchange or other chemical reactions, and L is an alkoxy (-OR 1 ), organic amino (-NR 2 R 3 ), carboxylate (-OOCR 4 ), amidinate (-R 5 N(CR 6 )NR 7 , Imide (-N(COR 8 )(COR 9 ), alkynides (-CCR 10 ), where R 1-10 are each independently hydrogen, linear C 1 -C 10 Alkyl group, branched C 3 -C 10 Alkyl group, C 3 -C 10 Cyclic alkyl groups, C 3 -C 10 Heterocyclic groups, C 3 -C 10 Alkenyl group, C 3 -C 10 Alkynyl groups, and C 4 -C 10aryl groups, where R 1 cannot be hydrogen, R 2-3 cannot both be hydrogen.

[0021] In another aspect, the disclosed and claimed invention provides a method for producing the diorganotin dihalide compounds and / or the diorganotin dihalide compounds, comprising preparing RSnX dihalide compounds suitable as a source or precursor for further forming an EUV photoresist composition as a spin-coat material or as a precursor for deposition. 3 or RSnL 3 For example, the organotin compounds of the formula RSnX may be used as raw materials / steps for the production of other organotin compounds such as 3 Compounds of formula (III) can be prepared from precursors via formula (III):

[0022] [ka] Formula RSnX 3 The compound of formula RSnL is then reacted with the compound of formula (IV) 3 can be converted to a compound of the formula:

[0023] [ka] wherein L is a hydrolyzable monoanionic ligand capable of replacing X through chemical exchange or other chemical reactions, and L is an alkoxy (-OR 1 ), organic amino (-NR 2 R 3 ), carboxylate (-OOCR 4 ), amidinate (-R 5 N(CR 6 )NR 7 , Imide (-N(COR 8 )(COR 9 ), alkynides (-CCR 10 ), where R 1-10 are each independently hydrogen, linear C 1 -C 10Alkyl group, branched C 3 -C 10 Alkyl group, C 3 -C 10 Cyclic alkyl groups, C 3 -C 10 Heterocyclic groups, C 3 -C 10 Alkenyl group, C 3 -C 10 Alkynyl groups, and C 4 -C 10 aryl groups.

[0024] In another aspect, the disclosed and claimed invention provides a method for producing the diorganotin dihalide compounds and / or the method for producing the diorganotin dihalide compounds, comprising reacting diorganotin dihalide compounds of formula R n SnX 4-n in which R is an organic ligand having 1-31 carbon atoms bonded to Sn by a metal-carbon bond, and X is a ligand having a hydrolyzable bond with Sn.

[0025] In another aspect, the disclosed and claimed invention encompasses the use of the diorganotin dihalide compounds and / or the process for making the diorganotin dihalide compounds in a process for making monoalkyltin triamide compounds, such as those described in U.S. Pat. No. 10,73287,466, the contents of which are incorporated herein by reference, comprising the steps of: 2 Zn, RZnNR' 2 or a combination thereof in a solution containing an organic solvent, 2 ) 4 wherein R is a hydrocarbyl group having 1 to 31 carbon atoms, X is a halogen, and R' is a hydrocarbyl group having 1 to 10 carbon atoms.

[0026] In another aspect, the disclosed and claimed invention provides a method for producing the diorganotin dihalide compounds and / or the method for producing the diorganotin dihalide compounds, comprising reacting an organic solvent with a first monoalkyltin trialkoxide (RSn(OR')), as described, for example, in US 2019 / 0391486, the contents of which are incorporated herein by reference. 3 in a method for synthesizing a conditioned precursor solution for a radiation-patternable coating comprising a mixture of an organic solvent and a first monoalkyltin trialkoxide having a tin concentration of from about 0.004M to about 1.0M, the method comprising mixing the organic solvent and a first monoalkyltin trialkoxide to form the conditioned precursor solution, the solvent being conditioned to have a water content within ±15% of a selected value, and the conditioned water content being no more than 10,000 ppm by weight, and the first monoalkyltin trialkoxide being produced from the diorganotin dihalide compound and / or from a method for producing the diorganotin dihalide compound.

[0027] In another aspect, the disclosed and claimed invention includes the use of the diorganotin dihalide compounds of the disclosed and claimed invention in or for the preparation of formulations useful for EUV processing, such formulations being used or usable to pattern radiation sensitive coatings in processes including: (i) forming a coating on a substrate surface using a precursor solution, wherein the precursor solution (a) is prepared from and / or utilizes a method for producing the diorganotin dihalide compound described above, (b) has a uniform composition resulting from adjusting the water content of the solvent used to produce the adjusted precursor solution to about ±15% of a target value, and (c) has a selected water content of from about 300 ppm to about 10,000 ppm by weight; (ii) drying the coating; and (iii) irradiating the dried coating to form a latent image.

[0028] This summary section is not intended to identify every aspect and / or radically novel aspect of the disclosed and claimed invention. Instead, this summary provides only a preliminary description of various aspects and corresponding points of novelty over conventional and known techniques. For additional details and / or possible perspectives of the disclosed and claimed invention and aspects, reference is made to the detailed description of the invention and corresponding drawings, which are further described below.

[0029] The order in which the different steps described herein are presented is provided for purposes of clarity. In general, the steps disclosed herein may be performed in any suitable order. Additionally, although different features, techniques, configurations, etc. described herein may each be described in different parts of this specification, it is intended that each of these concepts can be implemented independently of one another or in combination with one another, where appropriate. Thus, the invention as disclosed and claimed can be embodied and viewed in many different ways.

[0030] definition Unless otherwise stated, the following terms used in the specification and claims have the following meanings in this application.

[0031] In this application, the use of the singular includes the plural, and the singular means "at least one" unless specifically stated otherwise. Furthermore, the use of the term "comprises" as well as other verb forms such as "comprises" is not limiting. Additionally, the use of terms such as "element" or "component" includes both elements or components that contain one unit and elements or components that contain more than one unit, unless specifically stated otherwise. Unless otherwise indicated, the conjunction "and" as used herein is intended to be inclusive, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or instead of" is intended to be exclusive. As used herein, the conjunction "and / or" refers to any combination of the previously described elements, including the use of a single element.

[0032] The terms "about" or "approximately" when used in connection with a measurable, numerical variable refer to the indicated value of the variable and all values ​​of the variable that are within experimental error of the indicated value (e.g., within a 95% confidence limit of the mean) or within a percentage of the indicated value (e.g., ±10%, ±5%), whichever is greater.

[0033] As used herein, "C x-y " (x and y are each integers) specifies the number of carbon atoms in the chain. For example, C 1-6 Alkyl refers to alkyl chains having between 1 and 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl). Unless otherwise specifically stated, the chain can be linear or branched.

[0034] Unless otherwise indicated, "alkyl" refers to a hydrocarbon group, which may be a linear or branched hydrocarbon group (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.), a cyclic hydrocarbon group (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.), or a polycyclic hydrocarbon group (e.g., norbornyl, adamantyl, etc.). Suitable acyclic groups may be methyl, ethyl, n- or iso-propyl, n-, iso- or tert-butyl, linear or branched pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, and hexadecyl. Unless otherwise indicated, alkyl refers to a moiety having 1 to 10 carbon atoms. Cyclic alkyl groups may be monocyclic or polycyclic. Suitable examples of monocyclic alkyl groups include substituted cyclopentyl, cyclohexyl, and cycloheptyl groups. As described herein, cyclic alkyl groups may have any of the acyclic alkyl groups as a substituent. These alkyl moieties may be substituted or unsubstituted.

[0035] "Halogenated alkyl" refers to a linear, cyclic, or branched saturated alkyl group as defined above in which one or more of the hydrogens have been replaced with a halogen (e.g., F, Cl, Br, and I). Thus, for example, fluorinated alkyl (also known as "fluoroalkyl") refers to a linear, cyclic, or branched saturated alkyl group as defined above in which one or more of the hydrogens have been replaced with a fluorine (e.g., trifluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, etc.). Such haloalkyl moieties (e.g., fluoroalkyl moieties), when not perhalogenated / multihalogenated, may be unsubstituted or further substituted.

[0036] "Alkoxy" (also known as "alkyloxy") refers to an alkyl group, as defined above, attached through an oxy (-O-) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, etc.). These alkoxy moieties may be substituted or unsubstituted.

[0037] "Alkylcarbonyl" refers to an alkyl group as defined above attached through a carbonyl group (-C(=O-)) moiety (e.g., methylcarbonyl, ethylcarbonyl, propylcarbonyl, butylcarbonyl, cyclopentylcarbonyl, etc.), which may be substituted or unsubstituted.

[0038] "Halo" or "halide" refers to halogens (e.g., F, Cl, Br, and I).

[0039] "Hydroxy" (also known as "hydroxyl") refers to the --OH group.

[0040] The term "aryl" refers to an aromatic cyclic functional group having 4 to 10 carbon atoms, 5 to 10 carbon atoms, or 6 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, 1-phenylethyl (Ph(Me)CH-), 1-phenyl-1-methyl-ethyl (Ph(Me) 2 C-), benzyl, chlorobenzyl, tolyl, o-xylyl, 1,2,3-triazolyl, pyrrolyl, and furanyl.

[0041] Unless otherwise indicated, the term "substituted" refers to one of these moieties that also includes one or more substituents, including, but not limited to, alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxy, amino, and aminoalkyl, when referring to alkyl, alkoxy, fluorinated alkyl, and the like. Similarly, the term "unsubstituted" refers to these same moieties in which there are no substituents other than hydrogen.

[0042] The section headings used herein are for organizational purposes only and should not be construed as limiting the subject matter described. All references or portions of references cited herein, including but not limited to patents, patent applications, papers, books, and treatises, are incorporated herein in their entirety for all purposes. In the event that the definitions of terms in any of the references and similar materials incorporated herein conflict with those herein, the definitions herein shall control. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0043] It should be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to be limiting with respect to the invention as set forth in the claims. The objectives, features, advantages and concepts of the disclosed invention will be apparent to those skilled in the art from the description set forth herein, and further, the disclosed invention can be easily implemented by those skilled in the art based on the description set forth herein. Any description of a "preferred embodiment" and / or examples showing a preferred mode for carrying out the disclosed invention is included for illustrative purposes and is not intended to limit the scope of the claims.

[0044] Diorganotin dihalide compounds As previously described, the disclosed invention provides, as synthesized (i.e., without further purification), the corresponding tetraalkyltin (R 4 Sn), trialkyltin halide (R 3 SnX) and monoalkyltin trihalides (RSnX) 3 ) species, formula R 2 SnX 2 (wherein R is an unsubstituted linear C 1 -C 10 Alkyl, halogen-substituted linear C 1 -C 6 Linear C substituted with alkyl and amino groups 1 -C 6 Alkyl groups, unsubstituted branched C 3 -C 10 Branched C substituted with alkyl and halogen 3 -C 10 Branched C substituted with alkyl and amino groups 3 -C 10 Alkyl groups, unsubstituted amines, substituted amines, -Si(CH 3 ) 3 , unsubstituted C 3 -C 8 Cyclic alkyl groups, halogen-substituted C 3 -C 8 Cyclic alkyl, amino substituted C 3 -C 8Cyclic alkyl groups, unsubstituted C 3 -C 8 Aromatic groups, halogen-substituted C 3 -C 8 C substituted with aromatic or amino groups 3 -C 8 Aromatic group, C 3 -C 10 Heterocyclic groups, C 3 -C 10 Alkenyl groups, and C 3 -C 10 and (ii) X is Cl, Br, F or I.

[0045] In one aspect of this embodiment, R is of the formula R 2 SnX 2 In another aspect of this embodiment, R is a methyl group in the diorganotin dihalide compound of the formula R 2 SnX 2 In one aspect of this embodiment, X is an ethyl group in the diorganotin dihalide compound of formula R 2 SnX 2 In another aspect of this embodiment, the diorganotin dihalide compound of formula R 2 SnX 2 In the diorganotin dihalide compound, R is a methyl group and X is Cl (i.e., dimethyltin dichloride; Me 2 SnCl 2 In another aspect of this embodiment, the formula R 2 SnX 2 In the diorganotin dihalide compound, R is an ethyl group and X is Cl (i.e., diethyltin dichloride; Et 2 SnCl 2 ).

[0046] In one aspect of this embodiment, the formula R 2 SnX 2 The compound has a purity of about 98% by weight or greater based on analytical methods such as NMR, GC or other standard analytical methods.

[0047] In one aspect of this embodiment, the formula R 2 SnX 2 The compound has a purity of about 98.5% by weight or greater based on analytical methods such as NMR, GC or other standard analytical methods.

[0048] In one aspect of this embodiment, the formula R 2 SnX 2 The compounds have a purity of about 99% by weight or greater based on analytical methods such as NMR, GC or other standard analytical methods.

[0049] In one aspect of this embodiment, the formula R 2 SnX 2 The compounds have a purity of about 99.5% by weight or greater based on analytical methods such as NMR, GC or other standard analytical methods.

[0050] As described in more detail below, in particular Me 2 SnCl 2 and Et 2 SnCl 2 The diorganotin dihalide compounds of the disclosed and claimed invention, including but not limited to, (i) as synthesized (i.e., without further purification), are the corresponding tetraalkyltin (R 4 Sn; for example (Me) 4 Sn), trialkyltin halide (R 3 SnX; For example (Me) 3 SnX) and monoalkyltin trihalides (RSnX) 3 ;For example, MeSnX 3 ) species, and (ii) can be used in or to prepare other precursors and / or formulations useful in deposition and EUV processes.

[0051] Method for producing diorganotin dihalide compounds As described above, the disclosed invention provides a method for preparing a diorganotin oxide (R 2 SnO) from the formula R 2 SnX 2Regarding the synthesis of diorganotin dihalide compounds:

[0052] [ka] where: (i) R is an unsubstituted linear C 1 -C 10 Alkyl, halogen-substituted linear C 1 -C 6 Linear C substituted with alkyl and amino groups 1 -C 6 Alkyl groups, unsubstituted branched C 3 -C 10 Branched C substituted with alkyl and halogen 3 -C 10 Branched C substituted with alkyl and amino groups 3 -C 10 Alkyl groups, unsubstituted amines, substituted amines, -Si(CH 3 ) 3 , unsubstituted C 3 -C 8 Cyclic alkyl groups, halogen-substituted C 3 -C 8 Cyclic alkyl, amino substituted C 3 -C 8 Cyclic alkyl groups, unsubstituted C 3 -C 8 Aromatic groups, halogen-substituted C 3 -C 8 C substituted with aromatic or amino groups 3 -C 8 Aromatic group, C 3 -C 10 Heterocyclic groups, C 3 -C 10 Alkenyl groups, and C 3 -C 10 and (ii) X is Cl, Br, F or I. 2 SnX 2 The resulting compounds, as synthesized (i.e., without further purification), are the corresponding tetraalkyltin (R 4 Sn), trialkyltin halide (R 3SnX) and monoalkyltin trihalides (RSnX) 3 ) seeds not included.

[0053] In one aspect of this embodiment, R is a diorganotin oxide (R 2 In the compound SnO, the methyl group is (i.e., dimethyltin oxide; (Me) 2 In another aspect of this embodiment, R is a diorganotin oxide (R 2 In the compound SnO, the ethyl group is (i.e., diethyltin oxide; (Et) 2 SnO). Commercially available diorganotin oxides (R 2 SnO) compounds include, but are not limited to, dibutyltin(IV) oxide, dioctyltin oxide, and bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)tin oxide; other desirable diorganotin oxides (R 2 SnO) compounds can be produced.

[0054] Produced according to the above synthesis, and when synthesized, tetraalkyltin (R 4 Sn), trialkyltin halide (R 3 SnX) and monoalkyltin trihalides (RSnX) 3 ), formula R 2 SnX 2 Examples of diorganotin dihalide compounds include, but are not limited to, those shown in Table 1:

[0055] [Table 1] In one aspect of this embodiment, R is of the formula R 2 SnX 2 In another aspect of this embodiment, R is a diorganotin dihalide compound of the formula R 2 SnX 2In one aspect of this embodiment, X is a diorganotin dihalide compound of the formula R 2 SnX 2 In one aspect of this embodiment, the diorganotin dihalide compound of formula R 2 SnX 2 In the diorganotin dihalide compounds of the formula (I), it is preferred that R is a methyl group and X is Cl (i.e., dimethyltin dichloride; Me 2 SnCl 2 In one aspect of this embodiment, a compound of the formula R 2 SnX 2 In the diorganotin dihalide compound of the formula (I), it is preferred that R is an ethyl group and X is Cl (i.e., diethyltin dichloride; Et 2 SnCl 2 ).

[0056] The disclosed and claimed formula R 2 SnX 2 The method for synthesizing the diorganotin dihalide compound of the formula (i) Diorganotin oxide (R 2 SnO), where (i) R is an unsubstituted linear C 1 -C 10 Alkyl, halogen-substituted linear C 1 -C 6 Linear C substituted with alkyl and amino groups 1 -C 6 Alkyl groups, unsubstituted branched C 3 -C 10 Branched C substituted with alkyl and halogen 3 -C 10 Branched C substituted with alkyl and amino groups 3 -C 10 Alkyl groups, unsubstituted amines, substituted amines, -Si(CH 3 ) 3 , unsubstituted C 3 -C 8 Cyclic alkyl groups, halogen-substituted C 3 -C 8Cyclic alkyl, amino substituted C 3 -C 8 Cyclic alkyl groups, unsubstituted C 3 -C 8 Aromatic groups, halogen-substituted C 3 -C 8 C substituted with aromatic or amino groups 3 -C 8 Aromatic group, C 3 -C 10 Heterocyclic groups, C 3 -C 10 Alkenyl groups, and C 3 -C 10 forming a mixture of an alkynyl group and a suitable organic solvent; (ii) adding an aqueous solution of an acid of formula HX, where X is one of Cl, Br, F or I, to the mixture of step (i) to produce a biphasic mixture (i.e., an organic phase and an aqueous phase); (iii) stirring the biphasic mixture of step (ii) for a period of time; (iv) separating the organic and aqueous phases of the biphasic mixture; (v) optionally further extracting the aqueous phase; (vi) Formula R 2 SnX 2 isolating the compound of formula (I); and (vii) optionally, a compound of formula R 2 SnX 2 purifying the compound of formula (I); Includes.

[0057] In step (i), diorganotin oxide (i.e., R 2 SnO) is combined with a suitable organic solvent to form a mixture. As indicated above, R is an unsubstituted linear C 1 -C 10 Alkyl, halogen-substituted linear C 1 -C 6 Linear C substituted with alkyl and amino groups 1 -C 6 Alkyl groups, unsubstituted branched C 3 -C 10Branched C substituted with alkyl and halogen 3 -C 10 Branched C substituted with alkyl and amino groups 3 -C 10 Alkyl groups, unsubstituted amines, substituted amines, -Si(CH 3 ) 3 , unsubstituted C 3 -C 8 Cyclic alkyl groups, halogen-substituted C 3 -C 8 Cyclic alkyl, amino substituted C 3 -C 8 Cyclic alkyl groups, unsubstituted C 3 -C 8 Aromatic groups, halogen-substituted C 3 -C 8 C substituted with aromatic or amino groups 3 -C 8 Aromatic group, C 3 -C 10 Heterocyclic groups, C 3 -C 10 Alkenyl groups, and C 3 -C 10 In one aspect of this embodiment, R is a methyl group (i.e., dimethyltin oxide; (Me) 2 In another aspect of this embodiment, R is an ethyl group (i.e., diethyltin oxide; (Et) 2 SnO).

[0058] In step (i), a suitable solvent may be used. Examples of such solvents include, but are not limited to, linear, branched, cyclic or poly-ethers (e.g., tetrahydrofuran (THF), diethyl ether, diglyme, and / or tetraglyme); linear, branched or cyclic alkanes, alkenes, aromatics and halocarbons (e.g., pentane, hexanes, toluene and dichloromethane), and combinations thereof. Preferred solvents include toluene and dichloromethane (also known as methylene chloride). One particularly preferred solvent is methylene chloride. The mixture, when prepared, may be in the form of a slurry.

[0059] In step (ii), an aqueous solution of an acid of formula HX, where X is one of Cl, Br, F, or I, is added to the diorganotin oxide mixture (e.g., dimethyltin oxide and an organic solvent) from step (i). In one aspect of this embodiment, the acid is HCl. In one aspect of this embodiment, the acid is HBr. In one aspect of this embodiment, the acid is HF. In one aspect of this embodiment, the acid is HI. The addition of the aqueous solution of the acid produces a biphasic mixture (comprising an organic phase and an aqueous phase) due to the presence of water in the acid solution. It is noted that the amount of water in the acid solution can be varied and / or adjusted as desired or needed. In one aspect, the diorganotin oxide is dimethyltin oxide ((Me) 2 In another embodiment, the diorganotin oxide is diethyltin oxide (Et), the solvent comprises methylene chloride, and the aqueous acid comprises HCl. 2 SnO), the solvent comprises methylene chloride, and the aqueous acid comprises HCl.

[0060] In step (iii), the biphasic mixture from step (ii) is stirred for a period of time. The length of time can be relatively short (e.g., 10 to 60 minutes), but can be longer if desired. In one aspect, the process reaction time is from about 10 minutes to about 12 hours. In another aspect, the reaction time is from about 10 minutes to about 10 hours. In another aspect, the reaction time is from about 10 minutes to about 6 hours. In another aspect, the reaction time is from about 10 minutes to about 3 hours. In another aspect, the reaction time is from about 10 minutes to about 1 hour. In another aspect, the reaction time is from about 10 minutes to about 30 minutes.

[0061] In step (iv) and after said stirring, the aqueous and organic phases of said biphasic mixture are separated, which may be accomplished by any acceptable method.

[0062] In step (v), the compound of formula R 2 SnX 2 The aqueous phase can optionally be further extracted to recover additional diorganotin dihalide compounds. This extraction can be carried out with any suitable solvent, such as those previously described. In one embodiment, this is carried out with the same solvent used in step (i). For example, in one aspect of this embodiment, the aqueous phase is extracted with additional methylene chloride.

[0063] In step (vi), a compound of formula R 2 SnX 2 The compound of formula (I) is isolated. In this step, the organic solvent used is removed. Removal of the solvent can be accomplished using any suitable procedure(s). The isolated material can then be reconstituted in any suitable solvent. In one aspect of this embodiment, the isolated material can be reconstituted in toluene.

[0064] As mentioned above, when synthesized, the formula R 2 SnX 2 Compounds of (e.g., Me 2 SnCl2 ) is the corresponding tetraalkyltin (R 4 Sn), trialkyltin halide (R 3 SnX) and monoalkyltin trihalides (RSnX) 3 ) species in nature. However, in step (vii), 2 SnX 2 The compound of formula R is optionally further purified to remove other impurities. This purification can be carried out using any suitable procedure or procedures. In one aspect, 2 SnX 2 The compound of formula R can be purified by distillation. 2 SnX 2 The compound of formula R can be purified by crystallization. 2 SnX 2 The compound of formula R is purified to a purity of about 98% by weight or greater based on analytical methods such as NMR, GC or other standard analytical methods. 2 SnX 2 The compound of formula R is purified to a purity of about 99% by weight or greater based on analytical methods such as NMR, GC or other standard analytical methods. 2 SnX 2 The compound is purified and 1 The purity is about 99.5% by weight or greater based on analytical methods such as 1 H NMR, GC or other standard analytical methods.

[0065] In one aspect, some or all of the steps of the method are performed at a temperature between about -40°C and a temperature below the boiling point of the solvent(s) used. In another aspect, some or all of the steps of the method are performed at a temperature between about -40°C and about 100°C. In another aspect, some or all of the steps of the method are performed at a temperature between about -40°C and about 30°C. In another aspect, some or all of the steps of the method are performed at a temperature between about -40°C and about room temperature. In another aspect, all steps are performed at a temperature between about -40°C and a temperature below the boiling point of the solvent(s) used. In another aspect, all of the steps of the method are performed at room temperature.

[0066] In one aspect, the compound of formula R 2 SnX 2 In another aspect, the yield of the compound of formula R from the method is about 80% or greater. 2 SnX 2 In another aspect, the yield of the compound of formula R from the method is about 85% or greater. 2 SnX 2 In another aspect, the yield of the compound of formula R from the method is about 90% or greater. 2 SnX 2 The yield of this compound is about 95% or greater than 95%.

[0067] Uses of diorganotin dihalide compounds and methods for making same - Patents.com As noted above, in another aspect, the formula R 2 SnX 2 The diorganotin dihalide compounds of formula (II) are represented by the formula R 2 SnL 2 It is also possible to convert the compound into

[0068] [ka] wherein L is a hydrolyzable monoanionic ligand capable of replacing X through chemical exchange or other chemical reactions, and L is an alkoxy (-OR 1 ), organic amino (-NR 2 R 3 ), carboxylate (-OOCR 4 ), amidinate (-R 5 N(CR 6 )NR 7 , Imide (-N(COR 8 )(COR 9 ), alkynides (-CCR 10 ), where R 1-10 are each independently hydrogen, linear C 1 -C 10 Alkyl group, branched C 3 -C 10 Alkyl group, C 3 -C 10 Cyclic alkyl groups, C 3 -C 10 Heterocyclic groups, C 3 -C 10 Alkenyl group, C 3 -C 10 Alkynyl groups, and C 4 -C 10 aryl groups, where R 1 cannot be hydrogen, and R 2-3 cannot both be hydrogen.

[0069] In another aspect, the disclosed and claimed invention provides a method for producing the diorganotin dihalide compounds and / or the diorganotin dihalide compounds, comprising preparing RSnX dihalide compounds suitable as a source or precursor for further forming an EUV photoresist composition as a spin-coat material or as a precursor for deposition. 3 or RSnL 3 For example, the organotin compounds of the formula RSnX may be used as raw materials / steps for the production of other organotin compounds such as 3 Compounds of formula (III) can be prepared from precursors via formula (III):

[0070] [ka] Formula RSnX 3 The compound of formula RSnL is then reacted with the compound of formula (IV) 3 can be converted to a compound of the formula:

[0071] [ka] wherein L is a hydrolyzable monoanionic ligand capable of replacing X through chemical exchange or other chemical reactions, and L is an alkoxy (-OR 1 ), organic amino (-NR 2 R 3 ), carboxylate (-OOCR 4 ), amidinate (-R 5 N(CR 6 )NR 7 , Imide (-N(COR 8 )(COR 9 ), alkynides (-CCR 10 ), where R 1-10 are each independently hydrogen, linear C 1 -C 10 Alkyl group, branched C 3 -C 10 Alkyl group, C 3 -C 10 Cyclic alkyl groups, C 3 -C 10 Heterocyclic groups, C 3 -C 10 Alkenyl group, C 3 -C 10 Alkynyl groups, and C 4 -C 10 aryl groups, where R 1 cannot be hydrogen, and R 2-3 cannot both be hydrogen.

[0072] For example, the formula R 2 SnX 2 The diorganotin dihalide compound and / or the process for producing the diorganotin dihalide compound of formula R2 SnL 2 or RSnL 3 For example, the reactions exemplified by formulas (V) and (VI) can be used as starting materials / steps in chemical exchange reactions to prepare compounds of the formula:

[0073] [ka] These reactions are described, for example, in Kennedy, JD, "Auto-association in organometallic compounds: a nuclear magnetic double resonance study of methyl- and n-butyl-tin alkoxides," J. Chem. Soc., Perkin Trans., 2(2): 242-248 (1977) (Non-Patent Document 5); Reuter, H. and D. Schroeder, "Preparation, crystal structure and reactions of isopropyltin triisopropoxide," J. Organomet. Chem., 455(1-2): 83-87 (1993) (Non-Patent Document 6); and Jones, K. and M. F. Lappert, "Aminostannanes, stannylamines, and stannazanes," Proc. Chem. Soc., London, 358-359, (1962) (Non-Patent Document 7), the contents of which are incorporated herein in their entirety.

[0074] Similarly, R 2 SnL 2 or RSnL 3 (wherein L is alkoxy or carboxylate) is R 2 SnX 2 or RSnX 3can also be prepared by reacting the corresponding alcohol or carboxylic acid in the presence of an organic amine, for example as shown in formula (VII) (see, for example, US 2020 / 117085 A, the contents of which are incorporated herein by reference in their entirety).

[0075] [ka] In another aspect, the disclosed and claimed invention provides a method for producing the diorganotin dihalide compounds and / or the method for producing the diorganotin dihalide compounds, comprising preparing diorganotin dihalide compounds of formula R n SnX 4-n where R is an organic ligand having 1-31 carbon atoms bonded to Sn by a metal-carbon bond, and X is a ligand having a hydrolyzable bond to Sn. Such methods include using a compound of formula R 2 SnX 2 The compound of formula R n SnX 4-n where n is 1-3 and X is a ligand having a hydrolyzable bond to Sn.

[0076] The diorganotin dihalide compounds and / or compounds of formula R which can be produced by the method for producing the diorganotin dihalide compounds 2 SnL 2 or RSnL 3 Other compounds of the formula include: t Bu 2 Sn(NEt 2 ) 2 , t Bu 2 Sn(NMe 2 ) 2 , n Bu 2 Sn(NMe 2 ) 2 , iPr 2 Sn(NMe 2 ) 2 , t Am 2 Sn(NMe 2 ) 2 , (cyclopentyl) 2 Sn(NMe 2 ) 2 , Me 2 Sn(NMe 2 ) 2 , (cyclobutyl) 2 Sn(NMe 2 ) 2 , (cyclopentyl) 2 Sn(NMe 2 ) 2 , (cyclohexyl) 2 Sn(NMe 2 ) 2 , ((C 6 H 5 )CH 2 ) 2 Sn(NMe 2 ) 2 , ((C 6 H 5 )(CH 3 )CH) 2 Sn(NMe 2 ) 2 , ((C 6 H 5 )(CH 3 ) 2 C) 2 Sn(NMe 2 ) 2 , ((CH 3 ) 2 (CN)C) 2 Sn(NMe 2 ) 2 , ((CH 3 )(CN)CH) 2 Sn(NMe 2 ) 2 , t Bu 2 Sn(O t Bu) 2 , Me 2 Sn(O t Bu) 2 , n Bu 2 Sn(O t Bu)2 , i Pr 2 Sn(O t Bu) 2 , t Am 2 Sn(O t Bu) 2 , (cyclobutyl) 2 Sn(O t Bu) 2 , (cyclopentyl) 2 Sn(O t Bu) 2 , (cyclohexyl) 2 Sn(O t Bu) 2 , ((C 6 H 5 )CH 2 ) 2 Sn(O t Bu) 2 , ((C 6 H 5 )(CH 3 )CH) 2 Sn(O t Bu) 2 , ((C 6 H 5 )(CH 3 ) 2 C) 2 Sn(O t Bu) 2 , ((CH 3 ) 2 (CN)C) 2 Sn(O t Bu) 2 , ((CH 3 )(CN)CH) 2 Sn(O t Bu) 2 , t Bu 2 Sn(O t Am) 2 , Me 2 Sn(O t Am) 2 , n Bu 2 Sn(O t Am) 2、 i Pr 2 Sn(O t Am) 2 ,t I am 2 Sn(O t Am) 2 (シクロブッル) 2 Sn(O t Am) 2 、(シクロペンチル) 2 Sn(O t Am) 2 、(シクロロシリル) 2 Sn(O t Am) 2 、((C 6 H 5 )CH 2 ) 2 Sn(O t Am) 2 、((C 6 H 5 )(CH 3 )CH) 2 Sn(O t Am) 2 、((C 6 H 5 )(CH 3 ) 2 C) 2 Sn(O t Am) 2 、((CH 3 ) 2 (CN)C) 2 Sn(O t Am) 2 、((CH 3 )(CN)CH) 2 Sn(O t Am) 2 、 t BuSn(NET 2 ) 3 、 t BuSn(NMe 2 ) 3、 t BuSn(O t Bu)3、 i PrSn(NMe 2 ) 3 、MeSn(O t (It is) 3 、 n BuSn(O t (Bu) 3 、 n BuSn(NMe 2 ) 3, (CH 3 ) 3 CSn(NMe 2 ) 3 , (CH 3 ) 2 CHSn(NMe 2 ) 3 , (CH 3 ) 2 (CH 3 CH 2 )CSn(NMe 2 ) 3 , CyclopentylSn(NMe 2 ) 3 , C.H. 3 Sn(NMe 2 ) 3 , CyclobutylSn(NMe 2 ) 3 , CyclopentylSn(NMe 2 ) 3 , CyclohexylSn(NMe 2 ) 3 (C 6 H 5 )CH 2 Sn(NMe 2 ) 3 , (C 6 H 5 )(CH 3 )CHSn(NMe 2 ) 3 , (C 6 H 5 )(CH 3 ) 2 CSn(NMe 2 ) 3 , (CH 3 ) 2 (CN)CSn(NMe 2 ) 3 , (CH 3 )(CN)CHSn(NMe 2 ) 3 , (CH 3 ) 3 CSn(O t Bu) 3 , (CH 3 ) 2 CHSn(O t Bu) 3 , (CH 3 ) 2 (CH 3CH 2 )CSn(O t This) 3 、(CH 2 ) 2 CHSn(O t This) 3 、CH 3 Sn(O t This) 3 、(CH 2 ) 3 CHSn(O t This) 3 、(CH 2 ) 4 CHSn(O t This) 3 、(C 6 H 5 )CH 2 Sn(O t This) 3 、(C 6 H 5 )(CH 3 )CHSn(O t This) 3 、(C 6 H 5 )(CH 3 ) 2 CSn(O t This) 3 、(CH 3 ) 2 (CN)CSn(O t This) 3 、(CH 3 )(CN)CHSn(O t This) 3 、(CH 3 ) 3 CSn(O t (Am) 3 、(CH 3 ) 2 CHSn(O t (Am) 3 、(CH 3 ) 2 (CH 3 CH 2 )CSn(O t (Am) 3 ,shikuropropiropiruSn(O t (Am) 3 、CH 3 Sn(O t (Am) 3, cyclobutylSn(O t Am) 3 , CyclopentylSn(O t Am) 3 , CyclohexylSn(O t Am) 3 , (C 6 H 5 )CH 2 Sn(O t Am) 3 , (C 6 H 5 )(CH 3 )CHSn(O t Am) 3 , (C 6 H 5 )(CH 3 ) 2 CSn(O t Am) 3 , (CH 3 ) 2 (CN)CSn(O t Am) 3 , (CH 3 )(CN)CHSn(O t Am).

[0077] In another aspect, the disclosed and claimed invention provides a method for preparing the diorganotin dihalide compounds and / or methods for preparing the diorganotin dihalide compounds, for example, by reacting a diorganotin dihalide compound with an organic solvent and a first monoalkyltin trialkoxide (RSn(OR') 3in a method for synthesizing a conditioned precursor solution for a radiation-patternable coating comprising a mixture of an organic solvent having a tin concentration of from about 0.004M to about 1.0M with a first monoalkyltin trialkoxide; the method comprises mixing the organic solvent and the first monoalkyltin trialkoxide to produce the conditioned precursor solution, the solvent being conditioned to have a water content within ±15% of a selected value and the conditioned water content being no more than 10,000 ppm by weight, and the first monoalkyltin trialkoxide being prepared from the diorganotin dihalide compound and / or from a method for preparing the diorganotin dihalide compound. In some embodiments, the compound of formula RSn(OR') 3 In the alkyltin trialkoxide compounds of formula (I), R and R' are independently hydrocarbyl groups, e.g., alkyl or cycloalkyl having 1 to 31 carbon atoms, which alkyl or cycloalkyl have one or more carbon atoms substituted, optionally with one or more heteroatom functional groups including O, N, Si, Ge, Sn, Te, and / or halogen atoms, or with alkyl or cycloalkyl further functionalized with phenyl or cyano groups. In some embodiments, R' contains ≦10 carbon atoms and can be, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, or t-amyl. Such methods can be carried out, for example, by reacting a compound of formula (I) R 2 SnX 2 The compound of formula RSn(OR') 3and (ii) mixing an organic solvent and the first monoalkyltin trialkoxide to produce a conditioned precursor solution, where (a) the solvent is conditioned to have a water content of ±15% of a selected value, (b) the conditioned water content is at most 10,000 ppm by weight, and (c) R' is one or more of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, or t-amyl. In one aspect of this embodiment, the selected value is from about 250 ppm to about 10,000 ppm by weight. In another aspect of this embodiment, the selected value is from about 300 ppm to about 5,000 ppm by weight.

[0078] In another aspect, the disclosed and claimed invention encompasses the use of the diorganotin dihalide compounds of the disclosed and claimed invention in or for the preparation of formulations useful for EUV processing, which can be used to pattern a radiation-sensitive coating in a process that includes (i) forming a coating on a substrate surface using a precursor solution, the precursor solution (a) being prepared from and / or utilizing the diorganotin dihalide compounds, (b) having a uniform composition as a result of adjusting the water content of the solvent used to produce the adjusted precursor solution to within about ±15% of a desired value, and (c) having a selected water content of from about 300 ppm to about 10,000 ppm by weight; (ii) drying the coating; and (iii) irradiating the dried coating to form a latent image.

[0079] Another aspect of the disclosed and claimed invention is to provide a composition comprising 98% by weight or more of the formula R 2 SnX 2 Diorganotin dihalide compounds of R 4 Sn, R 3 SnX and RSnX 3 and up to 2% by weight of other impurities.

[0080] Another aspect of the disclosed and claimed invention is to provide a compound comprising R 4 Sn, R 3 SnX and RSnX 3 The formula R 2 SnX 2 The diorganotin oxide (R 2 The use of SnO.

[0081] It will also be apparent to those skilled in the art that various modifications may be made in the practice of the disclosed invention based on the aspects described herein without departing from the spirit and scope of the invention disclosed herein. EXAMPLES

[0082] More specific embodiments of the present disclosure and experimental results supporting such embodiments are described below. These examples are provided below to more fully explain the disclosed invention, and should not be construed as limiting the disclosed invention in any way.

[0083] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed invention and the specific examples provided herein without departing from the spirit or scope of the disclosed invention. Thus, the disclosed invention, including the description provided by way of the following examples, is intended to cover modifications and variations of the disclosed invention that come within the scope of any claims and their equivalents.

[0084] Materials and Methods: The disclosed and claimed methods utilize commercially available materials (eg, dimethyltin oxide, methylene chloride, etc.).

[0085] Example 1: Synthesis of dimethyltin dichloride A 22 L flask was equipped with a glass stirring shaft and Teflon stirring paddle, an industrial condenser, a 2.5 L addition funnel, a glass thermowell, and a sidearm adapter, and the flask was flushed with nitrogen gas and charged with 1983 g of dimethyltin oxide. 10 L of dichloromethane (CH 2 Cl 2 ) was charged to the flask and stirring of the resulting slurry was commenced. 5.0 L of 12.2 M HCl in water was added (in two portions) to the addition funnel. This solution was added to the stirring slurry over a period of one hour, during which the temperature rose from about 24° C. to about 35° C. The slurry eventually became a clear yellow solution. The reaction was stirred for several hours and layers developed immediately upon stopping the stirring. The organic layer was separated from the aqueous layer and the aqueous layer was then poured into CH4. 2 Cl 2 The solid was extracted three times with toluene and the organic layers were combined and the solvent removed under vacuum. The solid was taken up in 2 L of toluene, heated to 70° C. and the flask was placed in a cooler to crystallize the material. The toluene was filtered off from the material and the colorless solid was washed with cold pentane and dried under vacuum. Dimethyltin dichloride (2385 g; 90% yield) was isolated as a free-flowing powder. The corresponding tetraalkyltin, trialkyltin halide or monoalkyltin trihalide species can be prepared by: 1 H NMR / 119 Not detected by Sn NMR.

[0086] Comparative Example Me 2 SnCl 2 was prepared from tetramethyltin and tin tetrachloride in a neat reaction by stirring at 90-135°C for 15-16 hours. Solvent was then added to the mixture and cooled to induce crystallization. The crystals were then isolated and washed to remove residual toxic impurities. The supernatant, containing up to 4% methyltin chloride, was bottled and transferred to hazardous waste for proper disposal. No tetraalkyltins were detected. The final material was Me 2 SnCl 2Tested to be >99% pure.

[0087] The Me of this comparison method 2 SnCl 2 Although R can be purified after extensive workup of the reaction, it could not be synthesized directly (i.e., in situ) without detectable impurities. In contrast, the method affords "crude" R 2 Since the SnO raw material does not contain tri- or tetra-alkyltin impurities, it directly produces diorganotin dihalide compounds that are completely free of tetra- or tri-alkyltin species as synthesized. 2 The addition of HX to SnO species was 1 H NMR / 119 The corresponding R was isolated in greater than 99.5% purity by Sn NMR, and in some cases greater than 99.9% purity. 2 SnX 2 Only

[0088] Although the invention has been described and illustrated with a certain degree of detail, it is understood that this disclosure is made by way of example only, and that numerous variations in the conditions and order of the steps can be adopted by those skilled in the art without departing from the spirit and scope of the invention.

Claims

1. Formula R 2 SnX 2 [wherein (i) R is an unsubstituted linear C 1 -C 10 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C 3 -C 10 alkyl group, a branched C 3 -C 10 alkyl group substituted with a halogen, a branched C 3 -C 10 alkyl group substituted with an amino group, an unsubstituted amine, a substituted amine, —Si(CH 3 ) 3 , an unsubstituted C 3 -C 8 cyclic alkyl group, a C 3 -C 8 cyclic alkyl group substituted with a halogen, a C 3 -C 8 cyclic alkyl group substituted with an amino group, an unsubstituted C 3 -C 8 aromatic group, a C 3 -C 8 aromatic group substituted with a halogen, a C 3 -C 8 aromatic group substituted with an amino group, a C 3 -C 10 heterocyclic group, a C 3 -C 10 alkenyl groups, and C 3 -C 10 alkynyl groups; and (ii) X is Cl, Br, F or I.

2. A process for producing a diorganotin dihalide compound of formula (I) which, as synthesized, does not contain R 4 Sn, R 3 SnX, or RSnX 3 , comprising the steps of: (i) Diorganotin oxide (R ２ SnO), where (i) R is an unsubstituted linear C １ -C １０ Alkyl groups, halogen-substituted linear C １ -C ６ Linear C substituted with alkyl or amino groups １ -C ６ Alkyl group, unsubstituted branched C ３ -C １０ Branched C substituted with alkyl groups and halogens ３ -C １０ Branched C substituted with alkyl and amino groups ３ -C １０ Alkyl groups, unsubstituted amines, substituted amines, -Si(CH ３ ) ３ , unsubstituted C ３ -C ８ Cyclic alkyl group, halogen-substituted C ３ -C ８ Cyclic alkyl group, C substituted with amino group ３ -C ８ Cyclic alkyl group, unsubstituted C ３ -C ８ Aromatic groups, halogen-substituted C ３ -C ８ Aromatic group, C substituted with amino group ３ -C ８ aromatic group, C ３ -C １０ Heterocyclic group, C ３ -C １０ Alkenyl groups, and C ３ -C １０ forming a mixture of an alkynyl group and an organic solvent; (ii) adding an aqueous solution of an acid of formula HX, where X is one of Cl, Br, F, or I, to the mixture of step (i) to produce a biphasic mixture comprising an organic phase and an aqueous phase; (iii) stirring the biphasic mixture of step (ii) for a period of time; (iv) separating the organic and aqueous phases of the biphasic mixture; (v) optionally further extracting the aqueous phase; (vi) Formula R ２ SnX ２ isolating the compound of formula (I); and (vii) optionally, a compound of formula R ２ SnX ２ purifying the compound of formula (I); The method comprising:

2. The method of claim 1 , wherein R is a methyl group.

3. 2. The method of claim 1 , wherein R is an ethyl group.

4. 2. The method of claim 1 , wherein X is Cl.

5. 2. The method of claim 1, wherein R is a methyl group and X is Cl.

6. 2. The method of claim 1, wherein R is an ethyl group and X is Cl.

7. Diorganotin oxide is dimethyltin oxide (Me ２ 2. The method of claim 1 , wherein the SiO 2 is SiO.

8. Diorganotin oxide is diethyltin oxide ((Et) ２ 2. The method of claim 1 , wherein the SiO 2 is SiO.

9. 10. The method of claim 1, wherein the solvent comprises one or more of linear, branched, cyclic or poly-ethers, linear, branched or cyclic alkanes, alkenes, aromatics and halocarbons, and combinations thereof.

10. The method of claim 1 , wherein the solvent comprises methylene chloride.

11. The method of claim 1 , wherein the aqueous acid comprises HCl.

12. 10. The method of claim 1, wherein the aqueous acid comprises one or more of HBr, HF, and HI.

13. Diorganotin oxide is dimethyltin oxide (Me ２ 2. The method of claim 1, wherein the aqueous solution is 0.1% by weight of the compound (SnO), the solvent comprises methylene chloride, and the aqueous acid comprises HCl.

14. Diorganotin oxide is diethyltin oxide ((Et) ２ 2. The method of claim 1, wherein the aqueous solution is 0.1% by weight of the compound (SnO), the solvent comprises methylene chloride, and the aqueous acid comprises HCl.

15. The method of any one of claims 1 to 14, wherein the duration of step (iii) is from about 10 minutes to about 12 hours.

16. Formula R ２ SnX ２ The method according to any one of claims 1 to 14, wherein the compound of formula (I) is isolated using a solvent comprising toluene.

17. Formula R ２ SnX ２ The method according to any one of claims 1 to 14, wherein the compound of formula (I) is purified by one or more of distillation and crystallization.

18. 15. The method according to any one of claims 1 to 14, wherein some or all of the method steps are carried out at a temperature between about -40°C and a temperature up to the boiling point of the solvent(s) used.

19. The method of any one of claims 1 to 14, wherein some or all of the method steps are carried out at a temperature between about -40°C and about 100°C.

20. Formula R ２ SnX ２ The method according to any one of claims 1 to 14, wherein the yield of compound of is about 80% or more than 80%.

21. The method according to any one of claims 1 to 14, comprising the step of: ２ SnX ２ The compound of formula R ２ SnL ２ wherein L is alkoxy (-OR １ ), organic amino (-NR ２ R ３ ), carboxylate (-OOCR ４ ), amidinate (-R ５ N (CR ６ ) N.R. ７ ), imide (-N(COR ８ ) (COR ９ )), alkynides (-CCR １０ ), where R １－１０ are each independently hydrogen, linear C １ -C １０ Alkyl group, branched C ３ -C １０ Alkyl group, C ３ -C １０ Cyclic alkyl group, C ３ -C １０ Heterocyclic group, C ３ -C １０ Alkenyl group, C ３ -C １０ Alkynyl groups, and C ４ -C １０ aryl groups, where R １ cannot be hydrogen and R ２－３ and cannot both be hydrogen.

22. The method according to any one of claims 1 to 14, comprising the step of: ２ SnX ２ The compound of formula RSnL ３ wherein L is alkoxy (-OR １ ), organic amino (-NR ２ R ３ ), carboxylate (-OOCR ４ ), amidinate (-R ５ N (CR ６ ) N.R. ７ ), imide (-N(COR ８ ) (COR ９ )), alkynides (-CCR １０ ), where R １－１０ are each independently hydrogen, linear C １ -C １０ Alkyl group, branched C ３ -C １０ Alkyl group, C ３ -C １０ Cyclic alkyl group, C ３ -C １０ Heterocyclic group, C ３ -C １０ Alkenyl group, C ３ -C １０ Alkynyl groups, and C ４ -C １０ aryl groups, where R １ cannot be hydrogen and R ２－３ and cannot both be hydrogen.

23. The method according to any one of claims 1 to 14, comprising the step of: ２ SnX ２ The compound of formula R ｎ SnX ４－ｎ where n is 1 to 3 and X is a ligand having a hydrolyzable bond to Sn.

24. The method according to any one of claims 1 to 14, comprising the step of: ２ SnX ２ The compound ｔ B ２ Sn(NEt ２ ) ２ , ｔ B ２ Sn(NMe ２ ) ２ , ｎ B ２ Sn(NMe ２ ) ２ , ｉ P ２ Sn(NMe ２ ) ２ , ｔ A.M. ２ Sn(NMe ２ ) ２ , (cyclopentyl) ２ Sn(NMe ２ ) ２ , Me ２ Sn(NMe ２ ) ２ , (cyclobutyl) ２ Sn(NMe ２ ) ２ , (cyclopentyl) ２ Sn(NMe ２ ) ２ , (cyclohexyl) ２ Sn(NMe ２ ) ２ , ((C ６ H ５ ) CH ２ ) ２ Sn(NMe ２ ) ２ , ((C ６ H ５ ) (CH ３ ) C.H. ２ Sn(NMe ２ ) ２ , ((C ６ H ５ ) (CH ３ ) ２ C) ２ Sn(NMe ２ ) ２ , ((CH ３ ) ２ (CN)C) ２ Sn(NMe ２ ) ２ , ((CH ３ ) (CN) CH) ２ Sn(NMe ２ ) ２ , ｔ B ２ Sn(O ｔ B) ２ , Me ２ Sn(O ｔ B) ２ , ｎ B ２ Sn(O ｔ B) ２ , ｉ P ２ Sn(O ｔ B) ２ , ｔ A.M. ２ Sn(O ｔ B) ２ , (cyclobutyl) ２ Sn(O ｔ B) ２ , (cyclopentyl) ２ Sn(O ｔ B) ２ , (cyclohexyl) ２ Sn(O ｔ B) ２ , ((C ６ H ５ ) CH ２ ) ２ Sn(O ｔ B) ２ , ((C ６ H ５ ) (CH ３ ) C.H. ２ Sn(O ｔ B) ２ , ((C ６ H ５ ) (CH ３ ) ２ C) ２ Sn(O ｔ B) ２ , ((CH ３ ) ２ (CN)C) ２ Sn(O ｔ B) ２ , ((CH ３ ) (CN) CH) ２ Sn (O) ｔ (Bu) ２ 、 ｔ Is it ２ Sn (O) ｔ (Am) ２ 、Me ２ Sn (O) ｔ (Am) ２ 、 ｎ Is it ２ Sn (O) ｔ (Am) ２ 、 ｉ P ２ Sn (O) ｔ (Am) ２ 、 ｔ Am ２ Sn (O) ｔ (Am) ２ (シロロュチル) ２ Sn (O) ｔ (Am) ２ 、 (シクロペンチル) ２ Sn (O) ｔ (Am) ２ 、 ２ Sn (O) ｔ (Am) ２ ,((C ６ H ５ )CH ２ ) ２ Sn (O) ｔ (Am) ２ ,((C ６ H ５ )(CH ３ )CHH) ２ Sn (O) ｔ (Am) ２ ,((C ６ H ５ )(CH ３ ) ２ C) ２ Sn (O) ｔ (Am) ２ ,((CH ３ ) ２ (C)C) ２ Sn (O) ｔ (Am) ２ ,((CH ３ (CN)CHA) ２ Sn (O) ｔ (Am) ２ 、 ｔ Bus (Net) ２ ) ３ , ｔ BuSn(NMe ２ ) ３ , ｔ BuSn(O ｔ Bu) 3, ｉ PrSn(NMe ２ ) ３ , MeSn(O ｔ B) ３ , ｎ BuSn(O ｔ B) ３ , ｎ BuSn(NMe ２ ) ３ , (CH ３ ) ３ CSn(NMe ２ ) ３ , (CH ３ ) ２ CHSn(NMe ２ ) ３ , (CH ３ ) ２ (CH ３ CH ２ )CSn(NMe ２ ) ３ , CyclopentylSn(NMe ２ ) ３ , C.H. ３ Sn(NMe ２ ) ３ , CyclobutylSn(NMe ２ ) ３ , CyclopentylSn(NMe ２ ) ３ , CyclohexylSn(NMe ２ ) ３ (C ６ H ５ ) CH ２ Sn(NMe ２ ) ３ , (C ６ H ５ ) (CH ３ )CHSn(NMe ２ ) ３ , (C ６ H ５ ) (CH ３ ) ２ CSn(NMe ２ ) ３ , (CH ３ ) ２ (CN)CSn(NMe ２ ) ３ 、 (CH ３ )(CN)CHSn(NMe ２ ) ３ 、 (CH ３ ) ３ CSn(O ｔ Bu) ３ 、 (CH ３ ) ２ CHSn(O ｔ Bu) ３ 、 (CH ３ ) ２ (CH ３ CH ２ )CSn(O ｔ Bu) ３ 、 (CH ２ ) ２ CHSn(O ｔ Bu) ３ 、CH ３ Sn(O ｔ Bu) ３ 、 (CH ２ ) ３ CHSn(O ｔ Bu) ３ 、 (CH ２ ) ４ CHSn(O ｔ Bu) ３ 、 (C ６ H ５ )CH ２ Sn(O ｔ Bu) ３ 、 (C ６ H ５ )(CH ３ )CHSn(O ｔ Bu) ３ 、 (C ６ H ５ )(CH ３ ) ２ CSn(O ｔ Bu) ３ 、 (CH ３ ) ２ (CN)CSn(O ｔ Bu) ３ 、 (CH ３ )(CN)CHSn(O ｔ Bu) ３ 、 (CH ３ ) ３ CSn(O ｔ A m) ３ , (CH ３ ) ２ CHSn(O ｔ A m) ３ , (CH ３ ) ２ (CH ３ CH ２ )CSn(O ｔ A m) ３ , cyclopropylSn(O ｔ A m) ３ , C.H. ３ Sn(O ｔ A m) ３ , cyclobutylSn(O ｔ A m) ３ , cyclopentylSn(O ｔ A m) ３ , cyclohexylSn(O ｔ A m) ３ , (C ６ H ５ ) CH ２ Sn(O ｔ A m) ３ , (C ６ H ５ ) (CH ３ )CHSn(O ｔ A m) ３ , (C ６ H ５ ) (CH ３ ) ２ CSn(O ｔ A m) ３ , (CH ３ ) ２ (CN)CSn(O ｔ A m) ３ , (CH ３ )(CN)CHSn(O ｔ The process further comprises converting the fluorinated isomers to one or more of the following: