阅读说明：本技术 基于氢化硅杂吡咯、氢化硅杂氮杂吡咯和硫代硅杂环戊烷的化学组合物 (Chemical compositions based on hydrosilazoles, hydrosilazolazapyrroles and thiosilacyclopentanes ) 是由 童建颖 吴慧珍 孙娜波 于 2021-10-09 设计创作，主要内容包括：本发明公开了基于氢化硅杂吡咯、氢化硅杂氮杂吡咯和硫代硅杂环戊烷的化学组合物,涉及化学组合物技术领域,该化学组合物包括氢化硅杂吡咯、氢化硅杂氮杂吡咯和硫代硅杂环戊烷,所述氢化硅杂吡咯或氢化硅杂氮杂吡咯的化学式为：其中R是一个取代或未取代的有机基团,有一个碳或硅与环氮结合,R’是一个烷基。本发明在均匀的溶液中也能与分离的硅烷醇发生反应,并且还能与其他质子发生反应,甲硅烷基氢化物官能团可以保持完整,或者根据所需的最终产物,可以脱氢以形成碳氮化硅,可以用作区域特异性还原剂,或者可以进行氢化硅烷化,因此,本发明的材料在许多应用中具有吸引力,包括氮化硅和碳氮化硅膜的形成。(The invention discloses a chemical composition based on hydrosilazoles, hydrosilazoles azapyrroles and thiosilacyclopentane, and relates to the technical field of chemical compositions, wherein the chemical composition comprises hydrosilazoles, hydrosilazoles azapyrroles and thiosilacyclopentanes, and the chemical formula of the hydrosilazoles or the hydrosilazoles azapyrroles is as follows: wherein R is a substituted or unsubstituted organic group having a carbon or silicon bonded to the ring nitrogen, and R' is an alkyl group. The invention also enables the separation of silanes in homogeneous solutionThe alcohol reacts and can also react with other protons, the silyl hydride functionality can remain intact, or, depending on the desired end product, can dehydrogenate to form silicon carbonitride, can serve as a regiospecific reducing agent, or can undergo hydrosilylation, and thus the materials of the present invention are attractive in many applications, including the formation of silicon nitride and silicon carbonitride films.)

1. Chemical composition based on hydrosilazoles, hydrosilazoles azapyrroles and thiosilacyclopentanes, comprising hydrosilazoles, hydrosilazoles azapyrroles and thiosilacyclopentanes, characterized in that: the chemical formula of the hydrosilazoles or hydrosilazoles azapyrroles is as follows:

wherein R is a substituted or unsubstituted organic group having a carbon or silicon bonded to the ring nitrogen, and R' is an alkyl group;

the chemical formula of the thiosilacyclopentane is as follows:

wherein R "and R'" are each hydrogen or alkyl.

2. The chemical composition based on hydrosilazoles, hydrosilazoles azapyrroles and thiosilacyclopentanes according to claim 1, characterized in that: r in the hydrosilazoles or hydrosilazoles is alkyl, aryl, ester, chiral phenethylamine, trimethylsilyl or tertiary amine group.

3. The chemical composition based on hydrosilazoles, hydrosilazoles azapyrroles and thiosilacyclopentanes according to claim 1, characterized in that: the hydrogenated pyrrole is in n-butyl-2-silicon pyridine.

4. The chemical composition based on hydrosilazoles, hydrosilazoles azapyrroles and thiosilacyclopentanes according to claim 1, characterized in that: the hydrosilazoles are (N-trimethylsilyl-2-methyl-silapyrroles).

5. The chemical composition based on hydrosilazoles, hydrosilazoles azapyrroles and thiosilacyclopentanes according to claim 1, characterized in that: the hydrogenated silapyrrole or hydrogenated silaazapyrrole is used for preparing a silicon nitride or silicon carbonitride film.

6. The chemical composition based on hydrosilazoles, hydrosilazoles azapyrroles and thiosilacyclopentanes according to claim 1, characterized in that: the hydrogenated polysilypyrroles or hydrogenated silaazapyrroles are used for preparing regiospecific reducing agents.

7. The chemical composition based on hydrosilazoles, hydrosilazoles azapyrroles and thiosilacyclopentanes according to claim 1, characterized in that: the thiosilacyclopentane in the thiosilacyclopentane is 1-thia-2-silacyclopentane.

Technical Field

The invention relates to the technical field of chemical compositions, in particular to a chemical composition based on hydrosilazoles, hydrosilazoles azapyrroles and thiosilacyclopentanes.

Background

Molecular layer deposition for nanofeature devices, including semiconductors and microelectromechanical systems, is currently of great interest, with the expectation that monolayers can be rapidly and preferably quantitatively deposited with minimal by-products, and silicon carbonitride films are widely used for a variety of dielectric, passivation, and etch stops.

The current production process for producing silicon nitride or silicon carbonitride films is described in U.S. Pat. No.6,200,100, No.4,200,666 using trisilylamine ((SiH)₃)₃N) and an inert gas with optionally ammonia; diethylsilane and ammonia gas at 800 ℃ for LPCVD process as described in A.Hochberg (Mat.Res.Soc.Symp,24,509(1991)) et al; and b.arkles (j. electrochemical so., vol.133, No.1, pp.233-234(1986)) cyclic silazanes and ammonia, Chemical Vapor Deposition (CVD) process.

More recently, halogen-containing precursors such as tetraiodosilane and hexachlorodisilane have been described in U.S. patent No.6,586,056 m.tanaka et al, but suffer from application drawbacks related to the corrosiveness of the precursors and film contaminants and by-products, and another approach is the use of bis (tert-butylamino) silane in the plasma-assisted pulse deposition process described in U.S. patent application publication No. 2011/0256734(j.gumpher et al, j.electrochem. soc.,151, G353(2004)), which produces good quality SiN films at temperatures as low as 550 ℃. Both of these methods present complex thin film carbon contamination and high thermal and plasma energy requirements, while also incompatible with substrate stability, and other alternative methods are also described in EP 2644609 a2, in which fluorinated precursors are proposed, which although theoretically allow lower deposition temperatures, the fluorine introduced often affects the electrical properties of the silicon-based structures. The following problems exist in the prior art:

in the current major applications, these compounds either contain too much carbon or introduce oxygen into the film due to the substitution of the silicon atoms in the ring, and thus the need for new silicon nitride and silicon carbonitride precursors for depositing silicon nitride at low temperatures has not been met.

Disclosure of Invention

The present invention relates to a novel class of cyclic azasilanes known as hydrosilazoles (or cyclic azasilyl hydrides) and hydroazoles. Unlike known cyclic azasilanes that contain alkyl or alkoxy substituents on the silicon atom, the materials of the present invention are a class of hydridosilanes that can reduce or eliminate the carbon and oxygen contributions from the substituents on the silicon atom. In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

a chemical composition based on hydrosilazoles, hydrosilazoles azapyrroles and thiosilacyclopentanes, the chemical composition comprising hydrosilazoles, hydrosilazoles azapyrroles and thiosilacyclopentanes, the hydrosilazoles or hydrosilazoles azapyrroles having the formula:

wherein R is a substituted or unsubstituted organic group having a carbon or silicon bonded to the ring nitrogen, and R' is an alkyl group;

the invention also relates to a novel thiasilacyclopentane compound, which has the chemical formula:

wherein R "and R'" are each hydrogen or alkyl.

The technical scheme of the invention is further improved as follows: r in the hydrosilazoles or hydrosilazoles is alkyl, aryl, ester, chiral phenethylamine, trimethylsilyl or tertiary amine group.

The technical scheme of the invention is further improved as follows: the hydrogenated pyrrole is in n-butyl-2-silicon pyridine.

The technical scheme of the invention is further improved as follows: the hydrosilazoles are (N-trimethylsilyl-2-methyl-silapyrroles).

The technical scheme of the invention is further improved as follows: the hydrogenated silapyrrole or hydrogenated silaazapyrrole is used for preparing a silicon nitride or silicon carbonitride film.

The technical scheme of the invention is further improved as follows: the hydrogenated polysilypyrroles or hydrogenated silaazapyrroles are used for preparing regiospecific reducing agents.

The technical scheme of the invention is further improved as follows: the thiosilacyclopentane in the thiosilacyclopentane is 1-thia-2-silacyclopentane.

Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:

1. the present invention provides chemical compositions based on hydrosilazoles, hydrosilazoles and thiosilacyclopentanes that are also reactive in homogeneous solution with isolated silanols, such as triethylsilanol, and also with other protons, including amines and thiols, the silyl hydride functionality can remain intact or, depending on the desired end product, can be dehydrogenated to form silicon carbonitride, can be used as a regiospecific reducing agent, or can undergo hydrosilylation, and thus, the materials of the present invention are attractive in many applications, including the formation of silicon nitride and silicon carbonitride films.

2. The present invention provides chemical compositions based on hydrosilazoles, hydrosilazoles and thiosilacyclopentanes that react with hydroxyl surfaces to form films containing thiol groups, the thiol groups formed in the reaction reacting with olefins or other thiol compounds to further modify the surface.

Drawings

FIG. 1 is a schematic representation of the molecular structures of hydrosilazoles and hydroazezoles of the present invention;

FIG. 2 is a schematic diagram of the molecular structure of the thiosilacyclopentane of the present invention.

Detailed Description

The present invention is further illustrated in detail below with reference to examples:

example 1

The invention provides chemical compositions based on hydrosilazoles, hydrosilazoles and thiosilacyclopentanes, including hydrosilazoles, hydrosilazoles and thiosilacyclopentanes, the chemical formula of hydrosilazoles or hydrosilazoles being:

wherein R is a substituted or unsubstituted organic group having a carbon or silicon bonded to the ring nitrogen, and R' is an alkyl group;

the chemical formula of the thiosilacyclopentane is:

wherein R "and R'" are each hydrogen or alkyl;

wherein R in the hydrosilazoles or hydrosilazoles is an alkyl group, an aryl group, an ester group, a chiral phenethylamine, a trimethylsilyl group or a tertiary amine group, the hydrosilazoles, wherein in the N-butyl-2-silapyridine, the hydrosilazoles are (N-trimethylsilyl-2-methyl-silapyrroles), the hydrosilazoles or hydrosilazoles are used for preparing silicon nitride or silicon carbonitride films, the hydrosylpyrroles or hydrosilazoles are used for preparing regiospecific reducing agents, and the thiosilacyclopentane in the thiosilacyclopentane is 1-thia-2-silacyclopentane.

In this example, small hydrocarbon groups having up to six carbon atoms (including phenyl) and nitrogen substituted hydrocarbons such as dimethylaminoethyl, R' may preferably have up to about twenty carbon atoms, more preferably less than about six carbon atoms, most preferably methyl, ethyl, propyl or butyl, which in homogeneous solution are also capable of reacting with isolated silanols such as triethylsilanol and also with other protons including amines and thiols, the silyl hydride functionality may remain intact or, depending on the desired end product, may be dehydrogenated to form silicon carbonitride, may be used as a regiospecific reducing agent, or may be hydrosilylated, and thus the materials of the present invention are attractive in many applications, including the formation of silicon nitride and silicon carbonitride films, the reaction of thiosilacyclopentane with hydroxyl surfaces to form films containing thiol groups, the mercapto group formed in this reaction may further react with an olefin or other mercapto compound.

Example 2

On the basis of example 1, the invention provides the technical scheme that: preferably, simple specific examples of the compounds of the present invention include N-methyl-2-silapyrrole and N-butyl-2-silapyrrole: other examples include those with more complex functional substitutions on the nitrogen, including chiral phenethylamines, trimethylsilyl and tertiary amine groups, and the present invention also relates to a process for producing the above-described hydrosilazoles which comprises reducing the corresponding cyclic azasilanes having alkoxide substitution on the silicon atom, and thus, the only limitation on the hydrosilazoles which can be produced according to the process of the present invention is the ability to synthesize alkoxy-containing precursors, the materials of the present invention reacting quantitatively by ring-opening reaction with inorganic and organic hydroxyl groups, including hydroxyl groups on siliceous, aluminum and titanium substrates, and with organic hydroxyl groups, including alcohols.

Example 3

On the basis of example 1, the invention provides the technical scheme that: preferably, the thiosilacyclopentane compounds of the invention are described by a method analogous to that described above for the preparation of hydrosilazoles: the preparation of 2, 2-alkoxy-1-thia-2-silacyclopentane from a thiosilacyclopentane compound having an alkoxide group on silicon, for example, 1-thia-2-silacyclopentane, is accomplished by reduction.

The following will be described in connection with non-limiting examples:

the first embodiment is as follows: synthesis of N-butyl-2-silapyrrole (N-butyl-azasilacyclopentane): under argon, 400mL of 2-methyltetrahydrofuran was placed in a 2L 4-neck flask equipped with a cooling tank, mechanical stirrer, thermometer in the pan, addition funnel and dry ice distillation head, then 25.3g (0.67mol) of aluminum hydride were added in portions, the mixture was cooled to-10 ℃ and 203.4g (1.0mol) of N-butyl-azadimethoxysilacyclopentane was added via the addition funnel between-5 and 0 ℃ over 2 hours, after the addition was complete, the mixture in the pan was kept at 0 ℃ for about 2 hours, 345g of mineral oil was added, the mixture in the pan was stripped at a temperature of 80 ℃ in the pan, 0.5mmHg, and the crude product was re-distilled under reduced pressure to give 68.Ig (48% yield) of the target compound, boiling point: 60-2/25mmHg, density @20 ℃: 0.783, FTIR: vS-H: 2120.0 (vs).

Example two: synthesis of N- (3-dimethylaminopropyl) -2-methyl-1-2-silapyrrole (N-dimethylaminopropyl-Aza-1-methyl-silacyclopentane): 300mL of 2-methyltetrahydrofuran was placed in a 2L 4-necked flask equipped with a cooling tank, mechanical stirrer, thermometer in the pan, addition funnel and dry ice distillation head under argon, followed by 9.5g (0.25mol) of aluminum hydride in portions, the mixture was cooled to-10 ℃ and 162.3g (0.75mol) of N-N-dimethylaminopropyl-N-methylmethoxysilane-chloropentane was added through the addition funnel between-5 and 0 ℃ over a period of 2 hours, after which time the mixture in the pan was held at 0 ℃ for about 2 hours, 260 g of mineral oil was added to the pan, the mixture in the pan was stripped off at a temperature of 80 ℃ and 0.5mmHg in the pan, and the crude product was re-distilled under reduced pressure to give the target compound having a boiling point: 52-4/0.5mmHg, density @20 ℃: 0.857, FTIR: vS-H: 2111 (vs).

Example three: synthesis of N-trimethylsilyl-2-silapyrrole (N-trimethylsilyl-aza-1-methyl-silacyclopentane): under argon, 400mL of 2-methyltetrahydrofuran was placed in a 2L 4-neck flask equipped with a cooling tank, mechanical stirrer, thermometer in the pan, addition funnel and dry ice distillation head, then 25.3g (0.67mol) of aluminum hydride were added in portions, the mixture was cooled to-10 ℃ and 203.4g (1.0mol) of N-trimethylsilyl-azadimethoxysilacyclopentane was added via the addition funnel between-5 and 0 ℃ over 2 hours, after the addition was complete, the mixture in the pan was kept at 0 ℃ for about 2 hours, 345g of mineral oil was added to the pan, the mixture in the pan was stripped at a temperature of 80 ℃ C., 0.5mmHg, and the crude product was redistilled under reduced pressure to provide the target compound having the boiling point: 48-50/10mmHg, density @20 ℃: 0.846, FTIR: vS-H: 2120 (vs).

Example four: synthesis of l-thio-2-silacyclopentane: 490mL of diethylene glycol was placed in a 2L 4-neck flask equipped with a cooling bath, mechanical stirrer, thermometer in the pan, addition funnel and dry ice distillation head under argon, then 27.8g (0.73mol) of lithium aluminum hydride was added in portions, the mixture was cooled to-10 ℃ and 200.4g (1.22mol) of 2, 2-dimethoxy-1-thia-2-silacyclopentane was added via the addition funnel over a period of 2 hours between-5 and 0 ℃, after the addition was complete, the mixture in the pan was held at 0 ℃ for about 2 hours, the mixture in the pan was stripped at a temperature below 80 ℃ under 0.5mmHg, the crude product was redistilled under reduced pressure to give the title compound containing 50% of diethylene glycol: boiling point: 55/1.2mmHg, density @20 ℃: 0.827, FTIR: vS-H: 2140 (vs).

To sum up: the present invention provides chemical compositions based on hydrosilazoles, hydrosilazoles and thiosilacyclopentanes which are also capable of reacting with isolated silanols, such as triethylsilanol, and also with other protons, including amines and thiols, in homogeneous solution, the silyl hydride functionality can remain intact, or, depending on the desired end product, can be dehydrogenated to form silicon carbonitride, can be used as a regiospecific reducing agent, or can undergo hydrosilylation, and thus, the materials of the present invention are attractive in many applications, including the formation of silicon nitride and silicon carbonitride films, with thiosilacyclopentane reacting with hydroxyl surfaces to form films containing thiol groups, and the thiol groups formed in this reaction can react with alkenes or other thiol compounds to further modify the surface.

The present invention has been described in general terms in the foregoing, but it will be apparent to those skilled in the art that modifications and improvements can be made thereto based on the present invention. Therefore, modifications or improvements are within the scope of the invention without departing from the spirit of the inventive concept.