Cyclic azastannane and cyclic oxostannane compounds and methods for their preparation

Abstract

Cyclic azastannanes and oxostannanes having formulas (I) and (II), where X is an alkoxy or dialkylamino group, are a novel class of cyclic compounds. These compounds desirably have high vapor pressures and high purity (containing low levels of polyalkyl impurities after purification), making them particularly interesting for EUV photoresist applications. Methods for preparing these compounds are described. JPEG2025533836000030.jpg33170

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 412,959, filed October 4, 2022, the entire disclosure of which is incorporated herein by reference. [Background technology]

[0002] As semiconductor manufacturing continues to advance, feature sizes continue to shrink, increasing the need for new processing methods. Certain organotin compounds have been shown to be useful for the deposition of tin oxide hydroxide coatings in applications such as extreme ultraviolet (EUV) lithography. For example, alkyltin compounds provide radiation-sensitive Sn-C bonds that can be used to pattern structures by lithography.

[0003] Materials used in microelectronics manufacturing must be extremely pure, with stringent limits on organic impurities (e.g., reaction by-products), metallic impurities, and particulate impurities. Purity requirements are generally stringent, especially for lithography applications, because the chemicals come into contact with semiconductor substrates, and organometallic impurities in compounds such as (iPr)Sn(NMe2)3 can affect the properties of the resulting film. The exact purity target is determined by various factors, including performance criteria, but a typical minimum purity target is 3N+. Residual metals present in chemicals can deposit on semiconductor substrates and degrade the electrical performance of the fabricated devices. Typical specifications for metals are less than 10 ppb for individual metals and approximately 100 ppb for total metals.

[0004] Cyclic azasilanes are known to be useful for functionalizing microelectronic and optoelectronic devices and in ASD applications. Cyclic azastannanes and oxostannanes, especially those of high purity, may also be useful in these microelectronic applications. However, the ability to prepare and isolate cyclic tin compounds with the desired high purity levels has not previously been reported. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Davies et al., Eds.; Tin Chemistry: Fundamentals, Frontiers, and Applications; Wiley (2008) [Non-patent document 2] J. Med. Chem. (57, 22, pp. 9220-9231 (2014)) [Non-patent document 3] Advanced Synthesis & Catalysis, 363, 1646(2021) [Non-patent document 4] Russian Journal of Organic Chemistry, 56, 353(2020) [Non-Patent Document 5] J. Org. Chem., 67(25), 8906(2002) [Non-patent document 6] Organometallics 14, 685 (1995) Summary of the Invention [Means for solving the problem]

[0006] Cyclic azastannanes according to embodiments of the present disclosure have the following formula (I):

[0007] [ka]

[0008] wherein X is OR or NR'2, n is an integer from 1 to 3, R is a primary, secondary, or tertiary alkyl group having 1 to about 5 carbon atoms or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms, R' is a primary alkyl group having 1 to about 2 carbon atoms, and R'' is hydrogen, a substituted or unsubstituted, saturated or unsaturated, linear, branched, or cyclic primary, secondary, or tertiary alkyl group having 1 to about 20 carbon atoms, or a substituted or unsubstituted aryl group having about 7 to about 10 carbon atoms. and R''' is hydrogen, a substituted or unsubstituted, saturated or unsaturated, linear, branched, or cyclic primary, secondary, or tertiary alkyl group having from 1 to about 20 carbon atoms, a substituted or unsubstituted, branched or linear aralkyl group having from about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having from about 6 to about 10 carbon atoms.

[0009] Cyclic oxostannanes according to embodiments of the present disclosure have the following formula (II):

[0010] [ka]

[0011] wherein X is OR or NR'2, n is an integer from 1 to 3, R is a primary, secondary, or tertiary alkyl group having 1 to about 5 carbon atoms or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms, R' is a primary alkyl group having 1 to about 2 carbon atoms, and R''' is hydrogen, a substituted or unsubstituted, saturated or unsaturated, linear, branched, or cyclic primary, secondary, or tertiary alkyl group having 1 to about 20 carbon atoms, a substituted or unsubstituted, branched or linear aralkyl group having about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms.

[0012] In further embodiments, aspects of the present disclosure include compounds of formula (I):

[0013] [ka]

[0014] wherein X is OR; n is an integer from 1 to 3; R is a primary, secondary, or tertiary alkyl group having 1 to about 5 carbon atoms or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms; R″ is hydrogen, a substituted or unsubstituted, saturated or unsaturated, linear, branched, or cyclic primary, secondary, or tertiary alkyl group having 1 to about 20 carbon atoms, a substituted or unsubstituted, branched or linear aralkyl group having about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms; and R′″ is hydrogen, a substituted or unsubstituted, saturated or unsaturated, linear, branched, or cyclic primary, secondary, or tertiary alkyl group having 1 to about 20 carbon atoms, a substituted or unsubstituted, branched or linear aralkyl group having about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms. and a substituted or unsubstituted, saturated or unsaturated, linear, branched, or cyclic primary, secondary, or tertiary alkyl group having from about 7 to about 10 carbon atoms, a substituted or unsubstituted, branched or linear aralkyl group having from about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having from about 6 to about 10 carbon atoms, comprising reacting an aminoalkyltrialkoxystannane or an aminoalkyltriaryloxystannane with a compound selected from the group consisting of HMDZ, ammonium salts, sulfuric acid, phosphonium salts, and organolithium compounds.

[0015] In further embodiments, aspects of the present disclosure include compounds of formula (I):

[0016] [ka]

[0017] wherein X is NR'2, n is an integer from 1 to 3, R' is a primary alkyl group having 1 to about 2 carbon atoms, R'' is a substituted or unsubstituted, saturated or unsaturated, straight-chain, branched, or cyclic primary, secondary, or tertiary alkyl group having 1 to about 20 carbon atoms, a substituted or unsubstituted, branched or straight-chain aralkyl group having about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms, and R''' is hydrogen, and a substituted or unsubstituted, saturated or unsaturated, linear, branched, or cyclic primary, secondary, or tertiary alkyl group having from 1 to about 20 carbon atoms, a substituted or unsubstituted, branched or linear aralkyl group having from about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having from about 6 to about 10 carbon atoms, which comprises heating an aminoalkyltrialkylaminostannane to cause cyclization.

[0018] In further embodiments, aspects of the present disclosure include compounds of formula (II):

[0019] [ka]

[0020] wherein X is OR; n is an integer from 1 to 3; R is a primary, secondary, or tertiary alkyl group having 1 to about 5 carbon atoms or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms; and R''' is hydrogen, a substituted or unsubstituted, saturated or unsaturated, straight-chain, branched, or cyclic primary, secondary, or tertiary alkyl group having 1 to about 20 carbon atoms, a substituted or unsubstituted branched or straight-chain aralkyl group having about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms, comprising reacting trichlorostannyl alcohol with a metal alkoxide to form a trialkoxystannyl alcohol, and heating to cause cyclization.

[0021] In further embodiments, aspects of the present disclosure include compounds of formula (II):

[0022] [ka]

[0023] wherein X is NR'2, n is an integer from 1 to 3, R' is a primary alkyl group having from 1 to about 2 carbon atoms, and R''' is hydrogen, a substituted or unsubstituted, saturated or unsaturated, linear, branched, or cyclic primary, secondary, or tertiary alkyl group having from 1 to about 20 carbon atoms, a substituted or unsubstituted, branched or linear aralkyl group having from about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having from about 6 to about 10 carbon atoms, the method comprising reacting (dialkylamino)trimethylsilane with a cyclic oxostannane having formula (II):

[0024] Advantageous refinements of the invention, which can be implemented alone or in combination, are set out in the dependent claims.

[0025] In summary, the following embodiments are proposed as being particularly preferred within the scope of the present invention:

[0026] Embodiment 1: A cyclic azastannane having the following formula (I):

[0027] [ka]

[0028] wherein X is OR or NR'2, n is an integer from 1 to 3, R is a primary, secondary, or tertiary alkyl group having 1 to about 5 carbon atoms or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms, R' is a primary alkyl group having 1 to about 2 carbon atoms, and R'' is hydrogen, a substituted or unsubstituted, saturated or unsaturated, linear, branched, or cyclic primary, secondary, or tertiary alkyl group having 1 to about 20 carbon atoms, or a substituted or unsubstituted aryl group having about 7 to about 10 carbon atoms. and R''' is hydrogen, a substituted or unsubstituted, saturated or unsaturated, linear, branched, or cyclic primary, secondary, or tertiary alkyl group having from 1 to about 20 carbon atoms, a substituted or unsubstituted, branched or linear aralkyl group having from about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having from about 6 to about 10 carbon atoms.

[0029] Embodiment 2: The cyclic azastannane according to embodiment 1, wherein the cyclic azastannane is N,N,N',N',1-pentamethyl-1,2-azastannolidine-2,2-diamine, 1-ethyl-N,N,N',N'-tetramethyl-1,2-azastannolidine-2,2-diamine, N,N,N',N'-tetramethyl-1-vinyl-1,2-azastannolidine-2,2-diamine, 2,2-di-tert-butoxy-1-methyl-1,2-azastannolidine, 2,2-di-tert-butoxy-1-ethyl-1,2-azastannolidine, or 2,2-di-tert-butoxy-1-vinyl-1,2-azastannolidine.

[0030] Embodiment 3: A cyclic azastannane according to embodiment 1 or 2, having a purity of at least about 90 mol %.

[0031] Embodiment 4: A cyclic oxostannane having the formula (II):

[0032] [ka]

[0033] wherein X is OR or NR'2, n is an integer from 1 to 3, R is a primary, secondary, or tertiary alkyl group having 1 to about 5 carbon atoms or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms, R' is a primary alkyl group having 1 to about 2 carbon atoms, and R''' is hydrogen, a substituted or unsubstituted, saturated or unsaturated, linear, branched, or cyclic primary, secondary, or tertiary alkyl group having 1 to about 20 carbon atoms, a substituted or unsubstituted, branched or linear aralkyl group having about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms.

[0034] Embodiment 5: The cyclic oxostannane according to embodiment 4, wherein the cyclic oxostannane is 2,2-dimethoxy-1,2-oxastannolane, 2,2-di-tert-butoxy-1,2-oxastannolane, and 2,2-di-tert-butoxy-3-methyl-1,2-oxastannolane.

[0035] Embodiment 6: A cyclic oxostannane according to embodiment 4 or 5, having a purity of at least about 90 mol %.

[0036] Embodiment 7: A method of producing a cyclic azastannane according to any of Embodiments 1-3, wherein X is OR, comprising reacting an aminoalkyltrialkoxystannane or aminoalkyltriaryloxystannane with a compound selected from the group consisting of HMDZ, ammonium salts, sulfuric acid, phosphonium salts, and organolithium compounds.

[0037] Embodiment 8: A method of producing a cyclic azastannane according to any of embodiments 1-3, wherein X is NR'2, comprising heating an aminoalkyltrialkylaminostannane to effect cyclization.

[0038] Embodiment 9: A method of producing a cyclic oxostannane according to any of embodiments 4-6, wherein X is OR, comprising reacting trichlorostannyl alcohol with a metal alkoxide to produce a trialkoxystannyl alcohol, and heating the trialkoxystannyl alcohol to cause cyclization.

[0039] Embodiment 10: A method of producing a cyclic oxostannane according to any of embodiments 4-6, wherein X is NR', comprising reacting a (dialkylamino)trimethylsilane with a cyclic oxostannane having formula (II), wherein X is OR and R is a primary, secondary, or tertiary alkyl group having 1 to about 5 carbon atoms or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms. DETAILED DESCRIPTION OF THE INVENTION

[0040] Aspects of the present disclosure relate to a novel class of cyclic compounds, which may be referred to as hydridostannapyrroles and hydridostannafurans, azastannacyclopentanes and oxostannacyclopentanes, or cyclic azastannanes and cyclic oxostannanes. These compounds desirably have high vapor pressure, high reactivity with water, and high purity (including low levels of polyalkyl impurities after purification). Such compounds contain amide or alkoxy substituents on the tin atom. The cyclic azastannanes and cyclic oxostannanes described herein avoid impurities containing polyalkyltin compounds, tetraalkoxides, and tetraamides after purification.

[0041] In some embodiments, cyclic azastannanes and cyclic oxostannanes are volatile and are of particular interest in EUV photoresist applications. For purposes of this disclosure, a volatile compound is one that has sufficient vapor pressure to be transported by a carrier gas, such as argon, and / or has the inherent ability to diffuse to a substrate within a reaction chamber.

[0042] Cyclic azastannanes and cyclic oxostannanes according to embodiments of the present disclosure have the following formulae (I) and (II):

[0043] [ka]

[0044] It has the general structure shown below.

[0045] In these 5- to 7-membered ring structures, the tin atom is bonded to a carbon atom and a nitrogen or oxygen within the ring, and to two alkoxy or dialkylamino groups, and the hydrocarbon portion of the ring can be unsubstituted or substituted.

[0046] In formulas (I) and (II), X is OR or NR'2, n is an integer of 1 to 3, R is a primary, secondary, or tertiary alkyl group having 1 to about 5 carbon atoms (preferably 1 to about 4 carbon atoms) or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms, R' is a primary alkyl group having 1 to about 2 carbon atoms, and R'' is hydrogen, a substituted or unsubstituted, saturated or unsaturated, linear, branched, or cyclic primary, secondary, or tertiary alkyl group having 1 to about 20 carbon atoms, more preferably about 1 to about 5 carbon atoms, a substituted or unsubstituted, branched or linear aralkyl group having about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms. R''' is hydrogen, a substituted or unsubstituted, saturated or unsaturated, linear, branched, or cyclic, primary, secondary, or tertiary alkyl group having from 1 to about 20 carbon atoms (preferably from about 1 to about 6 carbon atoms), a substituted or unsubstituted, branched or linear aralkyl group having from about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having from about 6 to about 10 carbon atoms. For example, R can be a methyl, ethyl, isopropyl, or t-butyl group, preferably an isopropyl or t-butyl group; R' can be a methyl or ethyl group; and R'' can be hydrogen, a linear or branched alkyl group (such as methyl, ethyl, propyl, isopropyl, n-propyl, or t-butyl), an alkenyl, alkynyl, or aryl group, or a phenyl group, with methyl, ethyl, and vinyl groups being currently preferred. Examples of R''' include hydrogen, a straight-chain or branched alkyl group (such as methyl, ethyl, propyl, isopropyl, n-propyl, or t-butyl), an alkenyl, alkynyl, or allyl group, or a phenyl group, with hydrogen, methyl, ethyl, and vinyl groups currently being preferred.

[0047] Some specific examples of cyclic azastannane compounds and cyclic oxostannane compounds according to the present disclosure include N,N,N',N',1-pentamethyl-1,2-azastannolidine-2,2-diamine, 1-ethyl-N,N,N',N'-tetramethyl-1,2-azastannolidine-2,2-diamine, N,N,N',N'-tetramethyl-1-vinyl-1,2-azastannolidine-2,2-diamine, 2,2-di-tert-butoxy-1-methyl 2,2-di-tert-butoxy-1-ethyl-1,2-azastannolidine, 2,2-di-tert-butoxy-1-vinyl-1,2-azastannolidine, 2,2-dimethoxy-1,2-oxastannolane, 2,2-di-tert-butoxy-1,2-oxastannolane, and 2,2-di-tert-butoxy-3-methyl-1,2-oxastannolane, which have the structures shown below.

[0048] [ka]

[0049] After purification, the compounds having formulas (I) and (II) have a high purity, such as greater than about 90 mol%, greater than about 95 mol%, greater than about 97 mol%, greater than about 99 mol%, greater than about 99.2 mol%, greater than about 99.5 mol%, greater than about 99.6 mol%, greater than about 99.7 mol%, greater than about 99.8 mol%, or greater than about 99.9 mol%, and contain less than about 1% of tetrakistin compounds. In a preferred embodiment, the compounds having formula (I) further contain less than about 1 mol% of one or more of these impurity compounds: less than about 1 mol% of diazastannane compounds, less than about 1 mol% of tetraalkoxide compounds, and / or less than about 1 mol% of tetraamide compounds, e.g., less than about 0.8 mol%, less than about 0.5 mol%, less than about 0.3 mol%, less than about 0.2 mol%, or less than about 0.1 mol%. For example, N,N,N',N',1-pentamethyl-1,2-azastannolidine-2,2-diamine contains less than 1% 1,6-dimethyl-1,6-diaza-5-stannaspiro[4.4]nonane.

[0050] [ka]

[0051] The purity of the compounds described herein is 119 It can be determined by Sn NMR, which can have a detection limit as low as 0.05 mol% when the sample is run neat in a deuterated solvent.

[0052] 119 Sn NMR spectroscopy is ideally suited for the quantitative analysis of alkyltin compounds due to its high sensitivity to slight structural changes and its broad spectral range of 6500 ppm (see Davies et al., Eds.; Tin Chemistry: Fundamentals, Frontiers, and Applications; Wiley (2008)). This facilitates the identification and quantification of alkyltin compounds and their impurities because: 119 This is because the Sn resonance is highly resolved. 119 Sn NMR can be performed by GC, HPLC, or 1 It suffers from low sensitivity compared to other analytical methods such as H NMR. To improve sensitivity, alkyltin compounds are analyzed neat and a large number of spectral acquisitions (2000+) are performed to measure the low levels of impurities described in this work.

[0053] As described herein 119 Sn NMR data were obtained using a method similar to the relative purity method described in J. Med. Chem. (57, 22, 9220-9231 (2014)). 119 Sn NMR spectra are inverse gated 1Spectra were acquired using 1H decoupling, a 40° pulse, a 1-second relaxation delay, and sufficient scans to achieve the required sensitivity. Samples were prepared neat in deuterated solvents. Quantitation was performed by integrating all peaks in the spectrum and setting the total peak area to 100. Each peak in the spectrum represents a distinct tin compound, and the area of ​​each peak represents the concentration or purity of that compound in mol%.

[0054] Method for preparing cyclic azastannanes A method for preparing cyclic azastannanes having formula (I) and containing an alkoxy or aryloxy group on the tin ring atom (X is OR) preferably comprises reacting an aminoalkyltrialkoxystannane or aminoalkyltriaryloxystannane with HMDZ (hexamethyldisilazane), ammonium salts, sulfuric acid, phosphonium salts, organolithium compounds, or any similar material known or to be developed in the art that will react favorably with aminoalkyltrialkoxystannanes or aminoalkyltriaryloxystannanes to form the desired cyclic azastannane, as shown in the examples below. Thus, the only limitation on the cyclic azastannanes that can be produced according to the methods of this invention is the ability to synthesize the aminoalkyltrialkoxystannane or aminoalkyltriaryloxystannane precursor.

[0055] [ka]

[0056] Preferred alkali metal alkyl compounds include organometallic lithium compounds, such as the currently preferred butyllithium. Exemplary phosphonium salts include PyBroP (bromotri(pyrrolidino)phosphonium hexafluorophosphate), BroP (bromotris(dimethylamino)phosphonium hexafluorophosphate), PyBOP ((benzotriazol-1-yloxy)tripyrrolidinophosphonium hexafluorophosphate), and BOP ((benzotriazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate). Preferred ammonium salts that can be used in accordance with the methods described herein include salts of ammonium with any known anion, such as, but not limited to, halides, sulfate, phosphate, and trifluoromethanesulfonate. Particularly preferred ammonium salts include ammonium sulfate and ammonium chloride. While preferred, when the ammonium salt is neutral, charged species are also within the scope of the present invention.

[0057] The reaction is preferably carried out in the absence of a solvent (neat), but may also be carried out in solution. Preferred solvents include hydrocarbons (such as, but not limited to, hexane, heptane, and cyclohexane), aromatics (such as, but not limited to, toluene and xylene), and ethers (such as, but not limited to, THF and EtO), as well as mixtures thereof. Particularly preferred solvents include THF, hydrocarbons, and other aprotic solvents. The preferred concentration of reactants in the solvent (if a solvent is used) is about 5% to about 15% by weight, preferably about 7% to about 12% by weight, and more preferably about 10% by weight, but may be determined by routine experimentation. Initially, the reaction is preferably carried out under atmospheric pressure and at a temperature from about room temperature to about 150°C, preferably from about 120°C to about 140°C. After the reaction has proceeded for a predetermined period of time, preferably about 30 to 60 minutes, a vacuum, such as about 5 to 15 mm Hg, can be applied and any alcohol by-product formed can be removed from the reaction mixture, such as by condensation in a cold trap during distillation or by other separation methods known or to be developed in the art.

[0058] Suitable starting materials that can be used in the methods of the present disclosure include aminoalkyltrialkoxystannanes (for preparing cyclic azastannanes, where R is an alkyl group) that contain three alkoxy substituents on the tin in addition to the amino substituent. The alkoxy substituents may be alkoxy groups preferably containing from 1 to about 5 carbon atoms and may be primary, secondary, or tertiary alkoxy groups, such as methoxy, ethoxy, propoxy, isopropoxy, t-butoxy, etc., depending on the alkoxy groups that will be present in the cyclic azastannane. When the desired cyclic azastannane contains an aryl or aralkyl group as R, the starting material is an aminoalkyltriaryloxystannane or aminoalkyltriaralkoxystannane.

[0059] The amino substituent in the aminoalkyltrialkoxystannane or aminoalkyltriaryloxystannane preferably contains at least one NH group located about 3 to about 6 carbon atoms from the tin atom, e.g., aminopropyl, forming a five-membered ring, the length of the carbon chain determining the ring size in the product. The carbon chain is optionally substituted with an R'" group alpha to the tin, if the final compound has an R'" substituent. The amino substituent may also contain a substituted or unsubstituted, saturated or unsaturated aliphatic hydrocarbon group or a substituted or unsubstituted alkoxy group, and an additional substituted or unsubstituted amino group. For example, the amino substituent may be substituted with an alkyl group, an aryl group, or a substituted amino group such as aminoethyl.

[0060] Exemplary aminoalkyltrialkoxystannanes include N,N,N',N',N'',N''-hexamethyl-1-(3-(methylamino)propyl)stannanetriamine, 1-(3-(ethylamino)propyl)-N,N,N',N',N'',N''-hexamethylstannanetriamine, N,N,N',N',N'',N''-hexamethyl-1-(3-(vinylamino)propyl)stannanetriamine, N-methyl-3-(tri-tert-butoxystannyl)propan-1-amine, N-ethyl-3-(tri-tert-butoxystannyl)propan-1-amine, and 3-(tri-tert-butoxystannyl)-N-vinylpropan-1-amine.

[0061] The aminoalkyltrialkoxystannane starting materials may be purchased commercially or may be prepared, for example, using the following reaction sequence.

[0062] [ka]

[0063] In the above reaction with aminoalkyltrichlorostannane, X is an alkoxide group such as methoxide, isopropoxide, or t-butoxide, which is the OR group in the final compound.

[0064] Alternatively, the aminoalkyltributyltin compound used in the third step above can be prepared as follows:

[0065] [ka]

[0066] In a similar manner, according to another method of the present disclosure, cyclic azastannanes of formula (I) containing an NR2 substituent on the tin ring atom can be prepared by heating an aminoalkyltin triamide compound to cause cyclization by self-molecular transamination as shown below.

[0067] [ka]

[0068] The transamination reaction is a versatile process that can occur under mild conditions. The reaction is reversible but is usually driven by the removal / distillation of the more volatile amine. The reaction temperature range is preferably from about 25°C to about 80°C, depending on the boiling point of the amine by-product and its solubility in the solution. A more preferred operating temperature is from about 45°C to about 65°C, typically achieved by gently refluxing the reaction solvent. However, in other embodiments, it is preferred to carry out the reaction at room temperature. If the temperature is too low, the reaction rate will be too slow, while if the temperature is too high, by-products will be produced.

[0069] Preferably, this process is carried out in a suitable solvent. Preferred solvents include hydrocarbons (such as, but not limited to, hexane, heptane, and cyclohexane), aromatics (such as, but not limited to, toluene and xylene), and ethers (such as, but not limited to, THF and EtO), and mixtures thereof. In particular, hydrocarbons and aromatics are currently preferred as the main components of the solvent for removing residual metal salts by filtration. Toluene and hexane are currently the most preferred solvents because they allow for easy removal of the product under vacuum at low temperatures after the reaction.

[0070] The concentration of the aminoalkyltin triamide in the solution is preferably at most about 3M, more preferably at most about 2M, even more preferably at most about 1M, or at most about 30 wt%, more preferably at most about 20 wt%, even more preferably at most about 15 wt%, preferably greater than about 1 wt%, greater than about 2 wt%, greater than about 3 wt%, even more preferably greater than about 5 wt%. These dilute concentrations have been found to result in an effective, selective intramolecular reaction. However, productivity is lower at dilute concentrations under industrial conditions.

[0071] The aminoalkyltrialkylaminotin starting materials can be prepared in the same manner as above, using lithium dialkylamides instead of lithium alkoxides in the reaction with aminoalkyltin trichlorides (aminoalkyltrichlorostannanes). Exemplary aminoalkyltrichlorostannanes that can be used to form the aminoalkyltrialkylaminotin starting materials include N-methyl-3-(trichlorostannyl)propan-1-amine, N-ethyl-3-(trichlorostannyl)propan-1-amine, and 3-(trichlorostannyl)-N-vinylpropan-1-amine, which have the structures shown below.

[0072] [ka]

[0073] Method for preparing cyclic oxostannanes Cyclic oxostannanes containing alkoxy substituents on the tin ring atom can be prepared from trichlorostannyl alcohols (alkyloltrichlorostannanes) by reaction with a metal alkoxide, such as sodium methoxide, to produce the corresponding trialkoxystannyl alcohol, e.g., 3-(trimethoxystannyl)propan-1-ol, 3-(tri-tert-butoxystannyl)propan-1-ol, or 3-(tri-tert-butoxystannyl)butan-1-ol, followed by heating to effect cyclization. Exemplary alkyloltrichlorostannanes include 3-(trichlorostannyl)propan-1-ol and 3-(trichlorostannyl)butan-1-ol, as shown below.

[0074] [ka]

[0075] Cyclic oxostannanes containing amino substituents on the tin ring atom can be prepared by reacting a (dialkylamino)trimethylsilane (such as (dimethylamino)trimethylsilane) with the appropriate cyclic oxostannane having formula (II) where X is OR. That is, reaction with a (dialkylamino)trimethylsilane converts the alkoxy or aryloxy group on the tin ring atom to an amino group. Suitable solvents and concentrations for these reactions are described above. Suitable temperatures for these reactions can be determined by routine experimentation.

[0076] Although silicon and tin belong to the same group on the periodic table, differences in their reactivity mean that reactions effective in producing silane compounds do not work as well for stannane compounds. For example, aminosilanes can be formed by the direct reaction of chlorosilanes with amines, whereas aminotin compounds must be formed from lithium amides and tin chloride. In another example, a multi-step synthesis is required to prepare aminoalkyltrichlorotin compounds, whereas silicon analogs can be easily prepared via hydrosilylation. Furthermore, tin methoxide cannot be prepared by reacting chlorosilanes with trimethyl orthoformate and trimethyl orthoacetate; rather, the reaction requires the reaction of tin chloride with MOMe (M = Li, Na, or K). The difference in reactivity between tin and silicon is due in part to the larger size of the tin atom, providing more space for nitrogen and oxygen atoms to attack. Furthermore, tin atoms have an empty 5d orbital that can more easily accept lone pairs from oxygen or nitrogen atoms.

[0077] All steps in the synthesis of the compounds described herein are preferably carried out substantially free from light exposure, which can have a deleterious effect on the cyclic azastannane compounds and cyclic oxostannane compounds. Shielding can be achieved by any method known in the art, such as using a light-shielding container such as an amber glass or metal (SUS) container, covering the container with a light-shielding cover such as cloth, foil, or film, using a light-shielding coating, or conducting the reaction in a dark room.

[0078] Distillation may be carried out using a stainless steel column packed with stainless steel packing material. Alternatively, distillation may be carried out in a light-shielding device comprising glass, such as glass equipment, glass-lined equipment, glass-coated equipment, etc. Shielding can be achieved by any method known in the art, such as using a light-shielding container such as an amber glass or metal (SUS) container, covering the container with a light-shielding cover such as cloth, foil, or film, using a light-shielding coating, or performing the distillation in a darkroom.

[0079] A further aspect of the present disclosure is a solution containing an organic solvent described herein and a composition containing an organotin compound having the formula (I) and / or formula (II), which in some embodiments can be obtained by hydrolyzing a monoorganotin compound such as those having the formula (I) and / or (II) described herein. An additional aspect of the present disclosure relates to a film prepared from or containing a composition containing an organotin compound having the formula (I) and / or (II).

[0080] The compounds described herein can be used as resist materials after hydrolysis or after other reactions such as those known in the art. The compounds described herein may contain a group capable of forming an alkyltin oxo-hydroxy-patterning composition, which, under suitable conditions, is hydrolyzed with water or other suitable reagents to give a formula R a SnO (3 / 2- x / 2) (OH) x (0 < x ≦ 3), which can form an alkyltin oxo-hydroxy-patterning composition. R a is an organic substituent bonded to the Sn atom, generated by hydrolysis of the formula (I) or formula (II). The hydrolysis and condensation reactions associated with compounds having a hydrolyzable group (X) are shown in the following reactions (R means a general alkyl group): RSnX3 + 3H2O → RSn(OH)3 + 3HX RSn(OH)3 → RSnO( 1.5-(x / 2 ))OHx + (x / 2) H2O

[0081] The alkyloxohydroxytin compound obtained by hydrolyzing using a composition containing the above RSnX3 compound as a raw material and the oxohydroxytin compound represented by the formula R a SnO (3 / 2- x / 2) (OH) x (0 < x ≦ 3) can be used as an EUV resist material.

[0082] The composition containing the RSnX3 compound is hydrolyzed to obtain an oxohydroxytin compound (R a A method for obtaining the tin compound R'SnO may involve, for example, volatilizing a composition containing an RSnX compound under heating or reduced pressure, and reacting the vapor generated by volatilizing the composition on a substrate onto which the tin composition has been deposited with water vapor or the like (dry method). In this method, a thin film containing the tin compound R'SnO can be formed on the substrate.

[0083] Another method is to react a composition containing the R'SnX3 compound in solution or in solid state with water or the like and hydrolyze it to produce an oxohydroxytin compound (R a SnO), and then, for example, by dissolving it in an organic solvent, an oxohydroxytin compound (R a SnO) may also be used as the coating solution. While the organic solvent is not limited, particularly suitable solvents include, for example, aromatic compounds (e.g., xylene, toluene), ethers (anisole, tetrahydrofuran), esters (propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), alcohols (e.g., 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol), ketones (e.g., methyl ethyl ketone), halogenated solvents (e.g., CHCl, CHCl), and mixtures thereof. Generally, the choice of organic solvent can be influenced by solubility parameters, volatility, flammability, toxicity, viscosity, and potential chemical interactions with other processing materials.

[0084] The solution may be applied to the substrate by any coating or printing technique, and the oxohydroxytin compound (R a Thin films or coatings containing SnO can be formed on substrates. After the components of the solution dissolve and combine, the properties of the species can change as a result of partial hydration and condensation, especially during the application process.

[0085] Thin films obtained by any of the above methods may be stabilized or partially condensed through drying, heating, or other processes prior to exposure to light. Typically, the thin films or coatings have an average thickness of less than about 10 microns, with very thin submicron films, e.g., less than about 100 nanometers (nm), or even less than about 50 nm or less than about 30 nm, being desirable for patterning very small features. The resulting thin film or coating can be referred to as a resist, because the exposure to light renders portions of the composition resistant to development / etching.

[0086] The thin film or coating can be exposed to appropriate radiation (e.g., extreme ultraviolet, electron beam, deep ultraviolet, or ultraviolet) using a selected pattern or the negative portion of the pattern to form a latent image with areas that are resistant to the developer and areas that are soluble in the developer. After exposure to the appropriate radiation and before development, the thin film or coating can be heated or otherwise reacted to further differentiate the latent image from unexposed areas. The latent image is contacted with a developer to form a physical image, i.e., a patterned thin film or coating. The patterned thin film or coating can be further heated to stabilize the remaining patterned coating on the surface. The patterned coating can be used as a physical mask to perform further processing according to the pattern, such as etching the substrate and / or attaching additional materials. After using the patterned resist as desired, the remaining patterned coating can be removed at the appropriate processing point, although the patterned coating can also be incorporated into the final structure.

[0087] The invention will now be described with reference to the following non-limiting examples. [Example]

[0088] Example 1 N-allyl-N-methyl-1,1,1-tris(methyl-λ 2 Synthesis of (Azanail)silanamine (C) Compound A is prepared according to the method described in Advanced Synthesis & Catalysis, 363, 1646 (2021), and compound B is prepared according to the method described in Russian Journal of Organic Chemistry, 56, 353 (2020).

[0089] [ka]

[0090] Then, N-allyl-N-methyl-1,1,1-tris(methyl-λ 2 -azaneil)silanamine (C) is prepared from compound B as shown in the following scheme. Under N2, a 5 L flask is charged with 355.6 g (5 mol) of allylmethylamine (B), 505.95 g (5 mol) of TEA (triethylamine), and 1500 mL of DCM (dichloromethane). The mixture is cooled to 0 °C and silicon tetrachloride is added dropwise. After the addition, the mixture is allowed to warm to room temperature and stirred overnight. Compound C is then isolated and purified by distillation. A similar reaction can be carried out using compound A instead of compound B.

[0091] [ka]

[0092] Example 2 Synthesis of N-methyl-3-(tributylstannyl)propan-1-amine (D)

[0093] [ka]

[0094] According to the method of J. Org. Chem., 67(25), 8906 (2002), N-methyl-3-(tributylstannyl)propan-1-amine (D) is prepared by the above scheme as follows: Under N2, a 5 L flask is charged with 36.42 g (0.2 mmol) of C, 1979 g (6.8 mmol) of Bu3SnH, 2000 mL of toluene, and 98.95 mg (5 wt% of Bu3SnH) of AIBN. The mixture is refluxed for 50 hours. Then, pure compound D is obtained by distillation.

[0095] Example 3 Synthesis of N-methyl-3-(trichlorostannyl)propan-1-amine (E)

[0096] [ka]

[0097] N-methyl-3-(trichlorostannyl)propan-1-amine (E) is prepared according to the above scheme as follows: A 1 L flask is charged with 363.19 g (1 mol) of D under N2. Tin tetrachloride is added dropwise while controlling the temperature of the reaction mixture below 40°C. After the addition, the mixture is heated at 70°C for an additional 4 hours. Pure compound E is then obtained by distillation.

[0098] Example 4 Synthesis of N,N,N',N',1-pentamethyl-1,2-azastannolidine-2,2-diamine (G)

[0099] [ka]

[0100] Synthesize N,N,N',N',1-pentamethyl-1,2-azastannolidine-2,2-diamine (G) according to the above scheme as follows: Under N2, charge a 5 L flask with 1500 mL of anhydrous hexane and 839.9 g of 2.5 M n-BuLi (3.03 mol). Add 136.6 g of dimethylamine (3.03 mol) subsurface at 0-10 °C. Stir the reaction mixture for an additional 4 h while warming to room temperature, then add 396.89 g of compound E (1 mol) premixed in 100 mL of toluene dropwise at 0-10 °C. Allow the resulting mixture to warm to room temperature over 4 h and stir for an additional 4 h at room temperature. Filter the reaction mixture through a sparkler to remove the LiCl by-product. Rinse the salt with anhydrous hexane (2 x 100 mL). Remove the solvent under reduced pressure, and obtain pure compound G by distillation.

[0101] Example 5 Synthesis of N-methyl-3-(tri-tert-butoxystannyl)propan-1-amine (H)

[0102] [ka]

[0103] N-methyl-3-(tri-tert-butoxystannyl)propan-1-amine (H) was synthesized according to the above scheme as follows: Under N2, a 5 L flask was charged with 839.9 g of 2.5 M n-BuLi (3.03 mol) and cooled to 0 °C. 226.98 g of tert-butyl alcohol (50% in toluene, 253 g) was added subsurface at 0-10 °C. The reaction mixture was allowed to warm to room temperature and stirred for an additional 4 h. Then, 396.89 g of compound E (1 mol) premixed in 100 mL of toluene was added dropwise at 0-10 °C. The resulting mixture was allowed to warm to room temperature over 4 h and stirred for an additional 4 h at room temperature. The reaction mixture was filtered through a sparkler to remove the LiCl by-product. The salt was rinsed with anhydrous hexane (2 × 100 mL). The solvent was removed under reduced pressure, and pure compound H was obtained by distillation.

[0104] Example 6 Synthesis of 2,2-di-tert-butoxy-1-methyl-1,2-azastannolidine(I)

[0105] [ka]

[0106] Prepare 2,2-di-tert-butoxy-1-methyl-1,2-azastannolidine (I) according to the above scheme as follows: Under N2, charge a 5 L flask with 410.19 g of compound H (1 mol) and 800 mL of anhydrous hexane and cool to 0 °C. Add 277.2 g of BuLi (1 mol) dropwise while maintaining the temperature between 0 and 10 °C. After addition, allow the mixture to warm to room temperature and stir overnight. After filtration, wash the salt twice with an additional 100 mL of anhydrous hexane. Obtain pure compound I by distillation.

[0107] Example 7 Synthesis of 2,2-dimethoxy-1,2-oxastannolane (K)

[0108] [ka]

[0109] 3-(Trichlorostannyl)propan-1-ol (J) is prepared according to the method described in Organometallics 14, 685 (1995). 2,2-Dimethoxy-1,2-oxastannolane (K) is then prepared according to the above scheme as follows: A 5 L flask is charged under N with 284.15 g of compound J (1 mol) and 500 mL of THF. 648.2 g of NaOMe (25 wt % in MeOH) is added dropwise while maintaining the temperature below 50°C. The mixture is then heated at 50°C for an additional 4 hours. After filtration, the salt is washed twice with an additional 100 mL of anhydrous hexane. The solvent is removed by distillation until no MeOH is observed in the distillate. Pure compound K is then obtained by distillation.

[0110] Example 8 Synthesis of N,N,N',N'-tetramethyl-1,2-oxastannolane-2,2-diamine (L)

[0111] [ka]

[0112] Under N2, a 5 L flask is charged with 238.8 g (1 mol) of 2,2-dimethoxy-1,2-oxastannolane (K) and 500 mL of THF. 947.46 g of (dimethylamino)trimethylsilane (2.02 mol) is added dropwise, maintaining the temperature below 50 °C. The mixture is then heated to approximately 60-70 °C while the methoxytrimethylsilane is distilled off. After no further methoxytrimethylsilane is observed, the solvent is removed under vacuum. The pure target compound is obtained by distillation.

[0113] Example 9 Purification of the Compounds of the Invention The compounds prepared in Examples 1-8 are purified using fractional distillation, resulting in target compounds with purities of at least 95 mol % and as high as greater than 99 mol %.

[0114] Those skilled in the art will appreciate that changes could be made to the above-described embodiments without departing from the broad inventive concept thereof. It is therefore understood that the invention is not limited to the particular embodiments disclosed, but that it is intended to cover modifications within the spirit and scope of the invention as defined by the appended claims.

Claims

1. A cyclic azastannane having the formula (I): 【Chemical 1】 (In the formula, X is OR or NR' 2 and n is an integer from 1 to 3, R is a primary, secondary, or tertiary alkyl group having 1 to about 5 carbon atoms or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms; R' is a primary alkyl group having 1 to about 2 carbon atoms; R″ is hydrogen, a substituted or unsubstituted, saturated or unsaturated, straight-chain, branched, or cyclic primary, secondary, or tertiary alkyl group having from 1 to about 20 carbon atoms, a substituted or unsubstituted, branched or straight-chain aralkyl group having from about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having from about 6 to about 10 carbon atoms; R''' is hydrogen, a substituted or unsubstituted, saturated or unsaturated, straight-chain, branched, or cyclic primary, secondary, or tertiary alkyl group having from 1 to about 20 carbon atoms, a substituted or unsubstituted, branched or straight-chain aralkyl group having from about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having from about 6 to about 10 carbon atoms).

2. 2. The cyclic azastannane of claim 1, wherein the cyclic azastannane is N,N,N',N',1-pentamethyl-1,2-azastannolidine-2,2-diamine, 1-ethyl-N,N,N',N'-tetramethyl-1,2-azastannolidine-2,2-diamine, N,N,N',N'-tetramethyl-1-vinyl-1,2-azastannolidine-2,2-diamine, 2,2-di-tert-butoxy-1-methyl-1,2-azastannolidine, 2,2-di-tert-butoxy-1-ethyl-1,2-azastannolidine, or 2,2-di-tert-butoxy-1-vinyl-1,2-azastannolidine.

3. 3. The cyclic azastannane of claim 1 or 2, having a purity of at least about 90 mol %.

4. A cyclic oxostannane having the formula (II): 【Chemistry 2】 (In the formula, X is OR or NR' 2 and n is an integer from 1 to 3, R is a primary, secondary, or tertiary alkyl group having 1 to about 5 carbon atoms or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms; R' is a primary alkyl group having 1 to about 2 carbon atoms; R''' is hydrogen, a substituted or unsubstituted, saturated or unsaturated, straight-chain, branched, or cyclic primary, secondary, or tertiary alkyl group having from 1 to about 20 carbon atoms, a substituted or unsubstituted, branched or straight-chain aralkyl group having from about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having from about 6 to about 10 carbon atoms).

5. 5. The cyclic oxostannane of claim 4, wherein the cyclic oxostannane is 2,2-dimethoxy-1,2-oxastannolane, 2,2-di-tert-butoxy-1,2-oxastannolane, and 2,2-di-tert-butoxy-3-methyl-1,2-oxastannolane.

6. 6. The cyclic oxostannane of claim 4 or 5, having a purity of at least about 90 mol %.

7. 4. A method for producing a cyclic azastannane according to any one of claims 1 to 3, wherein X is OR, comprising the steps of: A process comprising reacting an aminoalkyltrialkoxystannane or an aminoalkyltriaryloxystannane with a compound selected from the group consisting of HMDZ, ammonium salts, sulfuric acid, phosphonium salts, and organolithium compounds.

8. The cyclic azastannane according to any one of claims 1 to 3, wherein X is NR' 2 1. A method for producing a compound comprising the steps of: A process comprising heating an aminoalkyltrialkylaminostannane to effect cyclization.

9. 7. A method for producing a cyclic oxostannane according to any one of claims 4 to 6, wherein X is OR, comprising the steps of: A method comprising reacting trichlorostannyl alcohol with a metal alkoxide to form a trialkoxystannyl alcohol and heating the trialkoxystannyl alcohol to cause cyclization.

10. The cyclic oxostannane according to any one of claims 4 to 6, wherein X is NR' 2 1. A method for producing a compound comprising the steps of:

1. A process comprising reacting a (dialkylamino)trimethylsilane with a cyclic oxostannane having formula (II), wherein X is OR and R is a primary, secondary, or tertiary alkyl group having 1 to about 5 carbon atoms or a substituted or unsubstituted aryl group having about 6 to about 10 carbon atoms.

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