Cyclic aza-stannane and cyclic oxa-stannane compound and preparation method thereof

Abstract

Cyclic azastannanes and cyclic oxastannanes having formulae (I) and (II) are a novel class of cyclic compounds, wherein X is an alkoxy group or a dialkylamino group. These compounds are desirable to have high vapor pressure and high purity (containing low levels of polyalkyl contaminants after purification), and are of particular interest in EUV photoresist applications. Methods of making these compounds are described. # imgabs0 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63 / 412,959, filed on October 4, 2022, the disclosure of which is incorporated herein by reference in its entirety. Background Art

[0003] As semiconductor manufacturing continues to advance, feature sizes continue to shrink, driving the need for new processing methods. Certain organotin compounds have been shown to be useful for depositing 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.

[0004] Materials used in microelectronics manufacturing need to be extremely pure, with strict limits on organic contaminants (e.g., reaction byproducts), metallic contamination, and particulate contamination. Purity requirements are often stringent, especially for photolithography 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 a variety of factors, including performance specifications, but a typical minimum purity target is 3N + Residual metals present in the chemicals can deposit onto semiconductor substrates and degrade the electrical performance of the device being fabricated. Typical specifications are less than 10 ppb for metals and no more than ~100 ppb for total metals.

[0005] Cyclic azasilanes are known to be useful in the functionalization of microelectronic and optoelectronic devices and in ASD applications. Cyclic azastannanes and cyclic oxatannanes, especially those with high purity, have the potential to be used in these microelectronic applications. However, the ability to prepare and isolate cyclic tin compounds with the required high purity levels has not been previously reported. Summary of the invention

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

[0007]

[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, R" is hydrogen, a substituted or unsubstituted primary, secondary or tertiary, saturated or unsaturated linear, branched or cyclic 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 primary, secondary or tertiary, saturated or unsaturated linear, branched or cyclic 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.

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

[0010]

[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 primary, secondary or tertiary, saturated or unsaturated linear, branched or cyclic 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 another embodiment, aspects of the present disclosure relate to a method for preparing a cyclic azastannane having formula (I):

[0013]

[0014] 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 primary, secondary or tertiary, saturated or unsaturated straight chain, branched or cyclic alkyl group having 1 to about 20 carbon atoms, a substituted or unsubstituted, branched or straight chain arylalkyl group having about 7 to about 10 carbon atoms, or a substituted or unsubstituted, branched or straight chain arylalkyl group having about 6 to about 10 carbon atoms. The method comprises reacting an aminoalkyltrialkoxystannane or an aminoalkyltriaryloxystannane with a compound selected from the group consisting of HMDZ, an ammonium salt, sulfuric acid, a phosphonium salt and an organolithium compound.

[0015] In another embodiment, aspects of the present disclosure relate to a method for preparing a cyclic azastannane having formula (I):

[0016]

[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 primary, secondary or tertiary, saturated or unsaturated, linear, branched or cyclic 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 primary, secondary or tertiary, saturated or unsaturated, linear, branched or cyclic alkyl group having about 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, the method comprising heating the aminoalkyltrialkylaminostannane to effect cyclization.

[0018] In another embodiment, aspects of the present disclosure relate to a method for preparing a cyclic oxatannane having formula (II):

[0019]

[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 primary, secondary or tertiary, saturated or unsaturated linear, branched or cyclic 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, the method comprising reacting trichlorotin alcohol with a metal alkoxide to produce a trialkoxytin alcohol, and heating to effect cyclization.

[0021] In another embodiment, aspects of the present disclosure relate to a method for preparing a cyclic oxatannane having formula (II):

[0022]

[0023] 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, and R'' is hydrogen, a substituted or unsubstituted primary, secondary or tertiary, saturated or unsaturated linear, branched or cyclic 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, the method comprising reacting (dialkylamino)trimethylsilane with a cyclic oxatannane having formula (II), wherein X is OR and R is a primary, secondary or tertiary alkyl group having 1 to about 5 carbon atoms.

[0024] Advantageous developments of the invention which can be implemented individually or in combination are specified in the dependent claims.

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

[0026] Embodiment 1. Cyclic azastannane having formula (I):

[0027]

[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, R" is hydrogen, a substituted or unsubstituted primary, secondary or tertiary, saturated or unsaturated linear, branched or cyclic 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 primary, secondary or tertiary, saturated or unsaturated linear, branched or cyclic 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.

[0029] Embodiment 2. A cyclic azatin alkane according to embodiment 1, wherein the cyclic azatin alkane is N,N,N',N',1-pentamethyl-1,2-azatin heterocyclopentane-2,2-diamine, 1-ethyl-N,N,N',N'-tetramethyl-1,2-azatin heterocyclopentane-2,2-diamine, N,N,N',N'-tetramethyl-1-vinyl-1,2-azatin heterocyclopentane-2,2-diamine, 2,2-di-tert-butoxy-1-methyl-1,2-azatin heterocyclopentane, 2,2-di-tert-butoxy-1-ethyl-1,2-azatin heterocyclopentane or 2,2-di-tert-butoxy-1-vinyl-1,2-azatin heterocyclopentane.

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

[0031] Embodiment 4. Cyclic oxatannanes having formula (II):

[0032]

[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 primary, secondary or tertiary, saturated or unsaturated linear, branched or cyclic 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 oxatannane according to embodiment 4, wherein the cyclic oxatannane is 2-dimethoxy-1,2-oxatannane, 2,2-di-tert-butoxy-1,2-oxatannane and 2,2-di-tert-butoxy-3-methyl-1,2-oxatannane.

[0035] Embodiment 6. The cyclic oxatannane of embodiment 4 or 5, having a purity of at least about 90 mol%.

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

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

[0038] Embodiment 9. A method for preparing a cyclic oxatannane according to any one of embodiments 4-6, wherein X is OR, the method comprising reacting trichlorotin alcohol with a metal alkoxide to produce a trialkoxytin alcohol, and heating the trialkoxytin alcohol to effectively cyclize.

[0039] Embodiment 10. A method for preparing a cyclic oxatannane according to any one of embodiments 4-6, wherein X is NR'2, the method comprising reacting (dialkylamino)trimethylsilane with a cyclic oxatannane 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

[0040] Aspects of the present disclosure relate to a class of novel cyclic compounds, which may be referred to as hydridostanarole and hydridostannuans, azastanyclopane and oxostancyclopentanes, or cyclic azastanes and cyclic oxostananes. These compounds ideally have high vapor pressure, high water reactivity, and high purity (containing low levels of polyalkyl contaminants after purification). Such compounds contain amides or alkoxy substituents on the tin atom. Cyclic azastanyclopanes and cyclic oxostananes described herein avoid being contaminated by polyalkyl tin compounds, tetraalkoxides, and tetraamides after purification.

[0041] In some embodiments, cyclic azastannanes and cyclic oxatannanes are volatile and are of particular interest for 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 an inherent ability to diffuse to a substrate in a reaction chamber.

[0042] The cyclic azastannanes and cyclic oxatannanes according to aspects of the present disclosure have the general structures shown in formulas (I) and (II):

[0043]

[0044] In these five-membered to seven-membered ring structures, the tin atom is bonded to a carbon atom and nitrogen or oxygen in the ring, and to two alkoxy or dialkylamino groups, and the hydrocarbon portion of the ring may be unsubstituted or substituted.

[0045] In formula (I) and (II), 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 (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 primary, secondary or tertiary, saturated or unsaturated straight chain, branched or cyclic alkyl group having 1 to about 20 carbon atoms, more preferably about 1 to about 5 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 6 to about 10 carbon atoms. R" can be hydrogen, a substituted or unsubstituted primary, secondary or tertiary, saturated or unsaturated straight chain, branched or cyclic alkyl group having about 7 to about 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to about 10 carbon atoms. The invention can be a primary, secondary or tertiary, saturated or unsaturated straight chain, branched or cyclic alkyl group, 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, for example, R can be methyl, ethyl, isopropyl or tert-butyl, preferably isopropyl or tert-butyl, R' can be methyl or ethyl, and R" can be hydrogen, a straight chain or branched chain alkyl group, such as methyl, ethyl, propyl, isopropyl, n-propyl or tert-butyl, alkenyl, alkynyl or allyl or phenyl; currently preferred are methyl, ethyl and vinyl. Examples of R"' include hydrogen, a straight chain or branched chain alkyl group such as methyl, ethyl, propyl, isopropyl, n-propyl or tert-butyl, alkenyl, alkynyl or allyl or phenyl; currently preferred are hydrogen, methyl, ethyl and vinyl.

[0046] Some specific examples of cyclic azastannane and cyclic oxatannane compounds according to the present disclosure include N,N,N',N',1-pentamethyl-1,2-azatin heterocyclopentane-2,2-diamine, 1-ethyl-N,N,N',N'-tetramethyl-1,2-azatin heterocyclopentane-2,2-diamine, N,N,N',N'-tetramethyl-1-vinyl-1,2-azatin heterocyclopentane-2,2-diamine, 2,2-di-tert-butyl- 1-methyl-1,2-azatin heterocyclopentane, 2,2-di-tert-butoxy-1-ethyl-1,2-azatin heterocyclopentane, 2,2-di-tert-butoxy-1-vinyl-1,2-azatin heterocyclopentane, 2,2-dimethoxy-1,2-oxatin heterocyclopentane, 2,2-di-tert-butoxy-1,2-oxatin heterocyclopentane and 2,2-di-tert-butoxy-3-methyl-1,2-oxatin heterocyclopentane, which have the structures shown below.

[0047]

[0048]

[0049] After purification, the compounds of formula (I) and (II) have high purity, for example, 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 tetratin compounds. In a preferred embodiment, the compound of formula (I) further contains less than about 1 mol% of diazastannane compounds, less than about 1 mol% of tetraalkoxy compounds and / or less than about 1 mol% of tetraamide compounds, for example, 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% of one or more of these impurity compounds. For example, N,N,N',N',1-pentamethyl-1,2-azastannopentane-2,2-diamine contains less than 1% of 1,6-dimethyl-1,6-diaza-5-stanno[4.4]nonane.

[0050]

[0051] 1,6-Dimethyl-1,6-diaza-5-tinspiro[4.4]nonane

[0052] The purity of the compounds described herein can be determined by 119 Sn NMR measurements can have detection limits as low as 0.05 mol % when the sample is tested without dilution in a deuterated solvent.

[0053] 119 Sn NMR spectroscopy is ideally suited for the quantitative analysis of alkyltin compounds due to its high sensitivity to small structural changes and its large spectral range of 6500 ppm (see Davies et al., Eds.; TinChemistry: Fundamentals,Frontiers,andApplications ; Wiley (2008)). This allows for easy identification and quantification of alkyltin compounds and their impurities because 119 The Sn resonances are highly resolved. 119 NMR is similar to GC, HPLC or 1 Other analytical methods such as H NMR have reduced sensitivity compared to alkyltin compounds. To increase sensitivity, alkyltin compounds were analyzed without dilution and a large number of spectral acquisitions (2000+) were acquired to measure the low levels of impurities described in this work.

[0054] The relative purity described herein was obtained using a method similar to the relative purity method described in J. Med. Chem. (57, 22, 9220–9231 (2014)). 119 Sn NMR data. Using reverse gating 1 H decoupling acquisition 119 Sn NMR spectrum with a pulse angle of 40°, a relaxation delay time of 1 s, and a sufficient number of scans to achieve the desired sensitivity. The sample was prepared without dilution in a deuterated solvent. Quantification was performed by integrating all peaks in the spectrum and setting the total peak area to 100. Each peak in the spectrum represents a different tin compound, and the area of ​​each peak represents the concentration or purity of that compound in mol%.

[0055] Method for preparing cyclic azastannane

[0056] As shown in the following examples, the method for preparing a cyclic azastannane having formula (I) and containing an alkoxy or aryloxy group on the ring tin atom (X is OR) preferably comprises reacting an aminoalkyltrialkoxystannane or an aminoalkyltriaryloxystannane with HMDZ (hexamethyldisilazane), an ammonium salt, sulfuric acid, a phosphonium salt, an organolithium compound, or any similar material known in the art or to be developed, which reacts advantageously with an aminoalkyltrialkoxystannane or an aminoalkyltrialkoxystannane to form the desired cyclic azastannane. Therefore, the only limitation to the cyclic azastannane prepared according to the method of the present invention is the ability to synthesize an aminoalkyltrialkoxystannane or an aminoalkyltriaryloxystannane precursor.

[0057]

[0058] Preferred alkali metal alkyl compounds include organometallic lithium compounds, such as the currently preferred butyl lithium. Exemplary phosphonium salts include PyBroP (bromotris(pyrrolidinyl)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 according to the methods described herein include salts of ammonium with any known anion, such as, but not limited to, halides, sulfates, phosphates, and trifluoromethylsulfonates. Particularly preferred ammonium salts include ammonium sulfate and ammonium chloride. Although ammonium salts are neutral, charged species are also within the scope of the present invention.

[0059] The reaction is preferably carried out in the absence of a solvent (pure), but can also be carried out in a solution. Preferred solvents include hydrocarbons (such as but not limited to hexane, hexanes, heptanes and cyclohexane), aromatic compounds (such as but not limited to toluene and xylene) and ethers (such as but not limited to THF and Et2O) and mixtures thereof. Particularly preferred solvents include THF, hydrocarbons and other aprotic solvents. If a solvent is used, the preferred concentration of the reactant in the solvent is from about 5% by weight to about 15% by weight, preferably from about 7% by weight to about 12% by weight, more preferably from about 10% by weight, but can be determined by routine experiments. It is preferred that the reaction is initially carried out at atmospheric pressure and at a temperature of about room temperature to about 150°C, preferably from about 120°C to about 140°C. After the reaction has been carried out for a period of time, preferably from about 30 minutes to 60 minutes, vacuum is drawn, for example, from about 5 to 15 mmHg, and any alcohol by-products formed can be removed from the reaction mixture, for example, by condensing in a cold trap during distillation or other separation techniques known in the art or to be developed.

[0060] Suitable starting materials that can be used in the method according to the present disclosure include aminoalkyltrialkoxystannane (for the preparation of cyclic azastannane, wherein R is an alkyl), which also includes three alkoxy substituents on tin except the amino substituent.The alkoxy substituent can be an alkoxy group preferably including 1 to about 5 carbon atoms, and can be primary, secondary or tertiary alkoxy, such as methoxyl group, ethoxyl group, propoxyl group, isopropoxy, tert-butoxy etc., depending on the alkoxy group present in the cyclic azastannane.If the desired cyclic azastannane includes aryl or aralkyl as R, the starting material is aminoalkyltriaryloxystannane or aminoalkyltriaralkyloxystannane.

[0061] The amino substituent in the aminoalkyltrialkoxystannane or aminoalkyltriaryloxystannane preferably contains at least one NH group, which is preferably located at about 3 to about 6 carbon atoms of the tin atom, such as aminopropyl to form a five-membered ring; the length of the carbon chain determines the size of the ring in the product. If the final compound has an R"' substituent, the carbon chain is optionally substituted with a group R"' in the alpha position relative to the tin. The amino substituent may also contain a substituted or unsubstituted saturated or unsaturated aliphatic hydrocarbon group or a substituted or unsubstituted alkoxy group, as well as additional substituted or unsubstituted amino groups. For example, the amino substituent may be substituted with an alkyl, allyl or substituted amino group, such as aminoethyl.

[0062] Exemplary aminoalkyltrialkoxytins 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)propane-1-amine, N-ethyl-3-(tri-tert-butoxystannyl)propane-1-amine, and 3-(tri-tert-butoxystannyl)-N-vinylpropane-1-amine.

[0063] The aminoalkyltrialkoxystannane starting material can be obtained commercially or prepared, for example, by employing the following reaction sequence.

[0064]

[0065] In the above reaction with aminoalkyltrichlorotinane, X is an alkoxide group, such as methoxide, isopropoxide or tert-butoxide, and is the OR group in the final compound.

[0066] Alternatively, the aminoalkyltributyltin compound used in the third step can be prepared as follows:

[0067]

[0068] In a similar manner, according to another method of the present disclosure, a cyclic azastannane having formula (1) containing NR2 on the ring tin atom can be prepared by heating an aminoalkyltin triamide compound to effect cyclization, as shown below.

[0069]

[0070] Transamination is a universal process that can occur under mild conditions. Although the reactions are reversible, they are usually driven by removing / distilling off more volatile amines. Depending on the boiling point of the amine byproduct and its solubility in solution, the reaction temperature range is preferably from about 25°C to about 80°C. A more preferred operating temperature is from about 45°C to about 65°C, which is usually achieved by gently refluxing the reaction solvent. However, in other embodiments, the reaction is preferably carried out at room temperature. If the temperature is too low, the reaction rate is too slow, and if the temperature is too high, by-products will be produced.

[0071] Preferably, the method is carried out in a suitable solvent. Preferred solvents include hydrocarbons (such as but not limited to hexane, hexanes, heptane and cyclohexane), aromatic compounds (such as but not limited to toluene and dimethylbenzene) and ethers (such as but not limited to THF and Et2O) and mixtures thereof. It is currently preferred that hydrocarbons and aromatic compounds are the main components of solvents, for removing residual metal salts by filtering. Toluene and hexane are currently the most preferred solvents, for easily removing product in vacuum at low temperatures after the reaction.

[0072] The concentration of aminoalkyltin triamide in solution is preferably at most about 3M, more preferably at most about 2M, even more preferably at most about 1M, or at most about 30wt%, more preferably at most about 20wt%, even more preferably at most about 15wt%, and preferably greater than about 1wt%, greater than about 2wt%, greater than about 3wt%, even more preferably greater than about 5wt%. It has been found that these dilute concentrations provide effective selective intramolecular reactions. On the other hand, the productivity under dilute concentrations under industrial conditions is low.

[0073] The aminoalkyltrialkylaminotin starting material can be prepared in the same manner as described above, using a lithium dialkylamide instead of a lithium alkoxide in the reaction with aminoalkyltin trichloride (aminoalkyltrichlorotinane). Exemplary aminoalkyltrichlorotinanes that can be used to form the aminoalkyltrialkylaminotin starting material include N-methyl-3-(trichlorotin alkyl) propane-1-amine, N-ethyl-3-(trichlorotin alkyl) propane-1-amine, and 3-(trichlorotin alkyl)-N-vinylpropane-1-amine, which have the structure shown below.

[0074]

[0075]

[0076] Method for preparing cyclic oxatannane

[0077] Cyclic oxazolidinone containing alkoxy substituents on the ring tin atom can be prepared by trichlorotin alkyl alcohol (alkyl alcohol trichlorotin alkane) by reacting with metal alkoxide (such as sodium methoxide), to produce corresponding trialkoxy tin alcohol, such as 3-(trimethoxytin alkyl) propan-1-ol, 3-(tri-tert-butoxytin alkyl) propan-1-ol or 3-(tri-tert-butoxytin alkyl) butan-1-ol, and then heated to realize cyclization. Exemplary alkyl alcohol trichlorotin alkane includes 3-(trichlorotin alkyl) propan-1-ol and 3-(trichlorotin alkyl) butan-1-ol as shown below.

[0078]

[0079] Cyclic oxatannanes containing amino substituents on the cyclic tin atoms can be prepared by reacting (dialkylamino)trimethylsilane (e.g., (dimethylamino)trimethylsilane)) with an appropriate cyclic oxatannane of formula (II), wherein X is OR. That is, the reaction with (dialkylamino)trimethylsilane converts the alkoxy or aryloxy groups on the cyclic tin atoms into amino groups. Suitable solvents and concentrations for these reactions are as described above. Suitable temperatures for these reasons can be determined by routine experimentation.

[0080] Although silicon and tin are in the same group in the periodic table, the difference between their reactivity means that reactions that are effective for producing silane compounds do not work similarly for tin compounds. For example, aminosilanes can be formed by the direct reaction of chlorosilanes with amines, while aminotin compounds must be formed from lithium amides together with tin chloride. In another example, a multi-step synthesis is required to prepare aminoalkyl trichlorotin compounds, while silicon analogs can be prepared simply by hydrosilylation. In addition, tin methoxide cannot be prepared by reacting chlorosilanes with trimethyl orthoformate and trimethyl orthoacetate, instead, the reaction requires the reaction of tin chloride with MOMe (M = Li, Na or K). The difference in reactivity between tin and silicon is partly derived from the larger size of the tin atom, which provides more room for attack from nitrogen and oxygen atoms. In addition, the tin atom has an empty 5d orbital, which can more easily accept lone pairs of electrons from oxygen or nitrogen atoms.

[0081] All method steps for synthesizing the compounds described herein are preferably carried out substantially in the absence of light exposure, which has an adverse effect on cyclic azastannane and cyclic oxastannane compounds. Shielding can be achieved by any method known in the art, for example, using a light-shielding container, such as amber glass, metal (SUS) container, packaging 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.

[0082] Distillation can be carried out using a stainless - steel column filled with stainless - steel packing. Alternatively, distillation can be performed in a light - shielding apparatus comprising glass (such as glass equipment, glass - lined equipment, glass - coated equipment, etc.). The shielding can be achieved by any method known in the art, for example, using a light - shielding container such as amber glass, a metal (SUS) container, wrapping the container with a light - shielding lid such as cloth, foil or film, using a light - shielding coating or carrying out the distillation in a dark room.

[0083] Another aspect of the present disclosure relates to a solution comprising an organic solvent as described herein and a composition comprising an organotin compound having formula (I) and / or formula (II). In some embodiments, the organotin compound can be obtained by hydrolysis of a mono - organotin compound, such as a mono - organotin compound having formula (I) and / or (II) as described herein. Another aspect of the present disclosure relates to a film prepared from or comprising the composition, the composition containing an organotin compound having formula (I) and / or (II).

[0084] The compounds described herein can be used as resist materials after hydrolysis or other reactions (such as those known in the art). The compounds described herein can comprise groups capable of forming an alkyltin - oxo - hydroxy - patterned composition, which can be hydrolyzed with water or other suitable reagents under suitable conditions to form an alkyltin - oxo - hydroxy - patterned composition, which can be represented by the formula R a SnO (3 / 2-x / 2) (OH) x (0 < x ≤ 3). R a is an organic substituent attached to the Sn atom generated by hydrolysis of formula (I) or formula (II). The hydrolysis and condensation reactions involving compounds having a hydrolyzable group (X) are shown in the following reactions (R represents a general alkyl group):

[0085] RSnX3 + 3H2O → RSn(OH)3+3HX

[0086] RSn(OH)3 → RSnO( 1.5-(x / 2 ))OHx+(x / 2)H2O

[0087] The alkyl - oxo - hydroxy - tin compounds obtained by hydrolysis of a composition containing an RSnX3 compound as a raw material as described above and the oxo - hydroxy - tin compounds represented by the formula R a SnO (3 / 2-x / 2) (OH) x (0 < x ≤ 3) can be used as EUV resist materials.

[0088] The oxo - hydroxy - tin compounds (R aThe method of depositing a tin compound R'SnO) may involve, for example, volatilizing a composition containing a RSnX3 compound under heating or reduced pressure, and reacting the vapor generated by the volatilized composition with water vapor or the like on a substrate on which a tin composition is deposited (dry method). In this method, a thin film containing a tin compound R'SnO can be formed on a substrate.

[0089] Another method may include reacting a composition containing a R'SnX3 compound with water or the like in a solution or in a solid state and hydrolyzing it to obtain an oxohydroxytin compound (R a SnO). Then, for example, the oxohydroxytin compound (R a SnO) is dissolved in an organic solvent to be used as a coating solution. The organic solvent is not limited, however, in particular, suitable solvents include, for example, aromatic compounds (for example, dimethylbenzene, toluene), ethers (anisole, tetrahydrofuran), esters (propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), alcohols (for example, 4-methyl-2-propanol, 1-butanol, methanol, isopropanol, 1-propanol), ketones (for example, methyl ethyl ketone), halogen solvents (for example, CH2Cl2, CHCl3) and mixtures thereof. Typically, organic solvent selection may be subject to solubility parameters, volatility, flammability, toxicity, viscosity and the impact of potential chemical interactions with other processing materials.

[0090] The solution can be applied to the substrate by any coating or printing technique, and a substrate containing the oxohydroxytin compound (R a After the components of the solution have dissolved and combined, the properties of the substance may change due to partial hydration and condensation, especially during the coating process.

[0091] The film obtained by any of the above methods can be stabilized or partially condensed before light exposure by drying, heating or other processes. Typically, the film or coating has an average thickness of less than about 10 microns, and very thin submicron films, such as less than about 100 nanometers (nm), even less than about 50 nm or less than about 30 nm, may be desirable for patterning very small features. The resulting film or coating can be referred to as a resist because the exposure process makes a portion of the composition resistant to development / etching.

[0092] The film or coating can be exposed to appropriate radiation (e.g., extreme ultraviolet, electron beam, deep ultraviolet or ultraviolet) using a selected pattern or negative portion of the pattern to form a latent image having developer-resistant and developer-soluble areas. After exposure to appropriate radiation and before development, the film or coating can be heated or otherwise reacted to further distinguish the latent image from the non-irradiated area. The latent image is contacted with a developer to form a physical image, i.e., a patterned film or coating. The patterned 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 required, the remaining patterned coating can be removed at an appropriate point in the process, but the patterned coating can also be incorporated into the final structure.

[0093] The invention will now be described with reference to the following non-limiting prophetic examples.

[0094] Example 1 (prophetic): Synthesis of N-allyl-N-methyl-1,1,1-tris(methyl-12-azanyl)silaneamine (C) become

[0095] Compound A was prepared according to the method described in Advanced Synthesis & Catalysis, 363, 1646 (2021), and compound B was prepared according to the method described in Russian Journal of Organic Chemistry, 56, 353 (2020).

[0096]

[0097] N-allyl-N-methyl-1,1,1-tri(methyl-12-azyl)silaneamine (C) was then prepared from compound B as follows, as shown in the following scheme. 355.6 g (5 moles) of allylmethylamine (B), 505.95 g (5 moles) of TEA (triethylamine) and 1500 mL of DCM (dichloromethane) were placed in a 5L flask under N2. The mixture was cooled to 0°C and silicon tetrachloride was added dropwise. After addition, the mixture was warmed to room temperature and stirred overnight. Compound C was then separated and purified by distillation.

[0098] A similar reaction can be carried out using compound A instead of compound B.

[0099]

[0100] Example 2 (prophetic): Synthesis of N-methyl-3-(tributylstannyl)propane-1-amine (D)

[0101]

[0102] According to the method of J.Org.Chem., 67(25), 8906(2002), N-methyl-3-(tributyltin alkyl)propane-1-amine (D) was prepared as follows according to the above scheme. Under N2, 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% Bu3SnH) of AIBN were charged into a 5 L flask. The mixture was refluxed for 50 hours. Pure compound D was then obtained by distillation.

[0103] Example 3 (prophetic): Synthesis of N-methyl-3-(trichlorostanninyl)propane-1-amine (E)

[0104]

[0105] N-methyl-3-(trichlorotinyl)propane-1-amine (E) was prepared as follows according to the above scheme. 363.19 (1 mol) of D was charged into a 1 L flask under N2. Tin tetrachloride was added dropwise while controlling the temperature of the reaction mixture to be below 40°C. After addition, the mixture was heated at 70°C for another 4 hours. Pure compound E was then obtained by distillation.

[0106] Example 4 (Prophetic): Synthesis of N,N,N',N',1-pentamethyl-1,2-azatin heterocyclopentane-2,2-diamine (G) become

[0107]

[0108] N,N,N',N',1-pentamethyl-1,2-azatin heterocyclopentane-2,2-diamine (G) was synthesized as follows according to the above scheme. Under N2, 1500 mL of anhydrous hexane and 839.9 g of 2.5M n-BuLi (3.03 mol) were charged into a 5 L flask. 136.6 g of dimethylamine (3.03 mol) was added subsurface at 0 to 10 ° C. The reaction mixture was stirred for another 4 hours while warming to room temperature, and then 396.89 g of compound E (1 mol) premixed in 100 mL of toluene was added dropwise at 0 to 10 ° C. The resulting mixture was warmed to room temperature within 4 hours and stirred at room temperature for another 4 hours. The reaction mixture was filtered through a candle filter (sparkler) to remove the LiCl byproduct. The salt was rinsed with anhydrous hexane (2 x 100 mL). The solvent was removed under reduced pressure and pure compound G was obtained by distillation.

[0109] Example 5 (Prophetic): Synthesis of N-methyl-3-(tri-tert-butoxystannyl)propane-1-amine (H)

[0110]

[0111] N-methyl-3-(tri-tert-butoxytinyl)propane-1-amine (H) was synthesized as follows according to the above scheme. Under N2, 839.9 g of 2.5 M n-BuLi (3.03 mol) was charged into a 5 L flask and cooled to 0°C. 226.98 g of tert-butyl alcohol (50%, 253 g in toluene) was added subsurface at 0 to 10°C. The reaction mixture was stirred for another 4 hours while warming to room temperature, and then 396.89 g of compound E (1 mol) premixed in 100 mL of toluene was added dropwise at 0 to 10°C. The resulting mixture was warmed to room temperature within 4 hours and stirred at room temperature for another 4 hours. The reaction mixture was filtered through a candle filter to remove the LiCl byproduct. The salt was rinsed with anhydrous hexane (2 x 100 mL). The solvent was removed under reduced pressure and pure compound H was obtained by distillation.

[0112] Example 6 (Prophetic): Synthesis of 2,2-di-tert-butoxy-1-methyl-1,2-azatin heterocyclopentane (I)

[0113]

[0114] 2,2-di-tert-butoxy-1-methyl-1,2-azatin heterocyclopentane (I) was prepared as follows according to the above scheme. Under N2, 410.19 g of compound H (1 mol) and 800 mL of anhydrous hexane were charged into a 5 L flask and cooled to 0°C. 277.2 g of BuLi (1 mol) was added dropwise while maintaining the temperature at 0-10°C. After addition, the mixture was warmed to room temperature and stirred overnight. After filtration, the salt was washed twice with an additional 100 mL of anhydrous hexane. Pure compound I was obtained by distillation.

[0115] Example 7 (Prophetic): Synthesis of 2,2-dimethoxy-1,2-oxatin heterocyclopentane (K)

[0116]

[0117] 3-(Trichlorotinyl)propane-1-ol (J) was prepared according to the method described in Organometallics 14, 685 (1995). 2,2-Dimethoxy-1,2-oxatin heterocyclopentane (K) was then prepared as follows according to the above scheme. 284.15 g of compound J (1 mole) and 500 mL of THF were charged into a 5 L flask under N2. 648.2 g of NaOMe (25 wt % in MeOH) was added dropwise while keeping the temperature below 50°C. The mixture was then heated at 50°C for an additional 4 hours. After filtration, the salt was washed twice with an additional 100 mL of anhydrous hexane. The solvent was removed by distillation until no MeOH was observed in the distillate. Pure compound K was then obtained by distillation.

[0118] Example 8 (Prophetic): Synthesis of N,N,N',N'-tetramethyl-1,2-oxatin heterocyclopentane-2,2-diamine (L)

[0119]

[0120] Under N2, 238.8 g (1 mol) of 2,2-dimethoxy-1,2-oxatin heterocyclopentane (K) and 500 mL of THF were charged into a 5 L flask. 947.46 g (dimethylamino) trimethylsilane (2.02 mol) was added dropwise, and the temperature was kept below 50°C. The mixture was then heated at about 60°C-70°C while methoxytrimethylsilane was removed by distillation. After no further observation of methoxytrimethylsilane, the solvent was removed under vacuum. The pure target compound was obtained by distillation.

[0121] Example 9 (Prophetic): Purification of Compounds of the Invention

[0122] The compounds prepared in Examples 1-8 were purified using fractional distillation to obtain target compounds with a purity of at least 95 mol% and up to 99 mol%.

[0123] Those skilled in the art will appreciate that changes may be made to the above embodiments without departing from the broad inventive concept thereof. Therefore, it should be understood that the present invention is not limited to the specific embodiments disclosed, but is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.

Claims

1. Cyclic azastannane having formula (I): in, 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, R" is hydrogen, a substituted or unsubstituted primary, secondary or tertiary, saturated or unsaturated linear, branched or cyclic 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 primary, secondary or tertiary, saturated or unsaturated linear, branched or cyclic 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.

2. The cyclic azastannane according to claim 1, wherein The cyclic azatin alkane is N,N,N',N',1-pentamethyl-1,2-azatin heterocyclopentane-2,2-diamine, 1-ethyl-N,N,N',N'-tetramethyl-1,2-azatin heterocyclopentane-2,2-diamine, N,N,N',N'-tetramethyl-1-vinyl-1,2-azatin heterocyclopentane-2,2-diamine, 2,2-di-tert-butoxy-1-methyl-1,2-azatin heterocyclopentane, 2,2-di-tert-butoxy-1-ethyl-1,2-azatin heterocyclopentane or 2,2-di-tert-butoxy-1-vinyl-1,2-azatin heterocyclopentane.

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

4. Cyclic oxatannanes having formula (II): in, 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 primary, secondary or tertiary, saturated or unsaturated linear, branched or cyclic 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.

5. The cyclic oxatannane according to claim 4, wherein The cyclic oxatannane is 2-dimethoxy-1,2-oxatannane, 2,2-di-tert-butoxy-1,2-oxatannane and 2,2-di-tert-butoxy-3-methyl-1,2-oxatannane.

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

7. The method for preparing the cyclic azastannane according to any one of claims 1 to 3, wherein X is OR, and the method comprises reacting an aminoalkyltrialkoxystannane or an aminoalkyltriaryloxystannane with a compound selected from the group consisting of HMDZ, an ammonium salt, sulfuric acid, a phosphonium salt, and an organolithium compound.

8. The method for preparing a cyclic azastannane according to any one of claims 1 to 3, wherein X is NR'2 and the method comprises heating the aminoalkyltrialkylaminostannane to effect cyclization.

9. The method for preparing a cyclic oxatannane according to any one of claims 4 to 6, wherein X is OR, and the method comprises reacting trichlorotin alcohol with a metal alkoxide to produce a trialkoxytin alcohol, and heating the trialkoxytin alcohol to effect cyclization.

10. The method for preparing a cyclic oxatannane according to any one of claims 4 to 6, wherein X is NR'2, the method comprising reacting a (dialkylamino)trimethylsilane with a cyclic oxatannane 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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