WO2011027922A1 - Production method for a polysilane-based compound and polysilane-based compounds produced thereby, a dehydrogenation catalyst used therein, and a method for producing an amorphous silicon thin film by using a polysilane-based compound - Google Patents

Abstract

Provided are a method for producing a linear or cyclic polysilane-based compound by subjecting monosilane, disilane or trisilane to dehydrogenation polymerisation and polysilane-based compounds produced thereby, a dehydrogenation catalyst used in the production method, and a method for producing an amorphous silicon thin film by using the polysilane-based compound. The polysilane-based compound can be used in a variety of electronic devices, notably solar cells, and, more particularly, can be employed to advantage when the amorphous silicon thin films used in the production of silicon solar cells are produced by means of the liquid-phase process.

Description

Method for producing polysilane-based compound and polysilane-based compound prepared according to this, dehydrogenation catalyst used therein, method for producing amorphous silicon thin film with polysilane-based compound

The present specification relates to a method for producing a polysilane-based compound, in particular a liquid polysilane-based compound, and a polysilane-based compound prepared according to the present invention, a dehydrogenation catalyst used in the method, and a method for producing amorphous thin film silicon using a polysilane-based compound. Describe it.

Organosilane polymers are known as polysilane (Si-Si), polysiloxane (Si-O), polycarbosilane (Si-C) and the like.

Polysilane is composed of Si-Si single bond and has various physical properties such as heat resistance, high refractive index, light reactivity, hole transport property, luminescence, etching resistance, low dielectric constant by sigma conjugation. By using the above properties, polysilane can be widely used in the electronics industry, the semiconductor industry, and the photovoltaic industry.

For example, due to the above physical properties, polysilane is a ceramic precursor, an interlayer insulating film, various optoelectronic materials such as photoresist, photosensitive materials such as organic photoconductors, optical transmission materials such as optical waveguides, optical recording materials such as optical memories, and electroluminescent devices. It can be used for a material such as, and can be used as a material such as semiconductor industry and the photovoltaic industry.

As a general method for synthesizing polysilane, Wurtz co-polymerization method has been used in which an organic dichlorosilane is dispersed with an alkali metal at a toluene reflux temperature and dechlorinated.

In addition to the above methods, ring-opening polymerization of cyclic silane oligomers, electroreduction polymerization of organic dichlorosilanes, polymerization methods using ultrasonic waves of organic dichlorosilanes, and the like are known.

The polysilane-based compound may be prepared by dehydrogenation-polymerizing primary, secondary and tertiary silanes in the presence of a catalyst by a dehydrogenation polymerization reaction. However, during the dehydrogenation polymerization reaction, when dehydrogenation of primary, secondary, and tertiary silanes using a general transition metal complex as a catalyst, the dehydrogenation polymerization reactivity is suddenly going to primary silane, secondary silane, and tertiary silane due to steric effect. Will decrease.

Surprisingly, not only the primary silanes, but also the secondary silanes, especially the tertiary silanes, can be prepared when the dehydrogenation polymerization reaction is carried out using the catalysts disclosed herein, thus reducing the primary silane, secondary silane or It was confirmed that the polysilane-based compound that is the dehydrogenated polymer of the tertiary silane was obtained. In addition, the polysilane-based compound thus obtained may be particularly useful in the production of amorphous silicon thin films.

In embodiments of the present invention, there is provided a method for preparing a polysilane-based compound by dehydrogenation-polymerizing primary silane, secondary silane or tertiary silane in the presence of a dehydrogenation catalyst and a polysilane-based compound prepared accordingly.

 In other embodiments of the present invention, there is provided a dehydrogenation catalyst for dehydrogenation polymerization to produce a polysilane-based compound by dehydrogenation polymerization of primary silane, secondary silane or tertiary silane.

In still another embodiment of the present invention, a method of preparing an amorphous silicon thin film using a liquid polysilane-based compound which is a dehydrogenated polymer of the primary silane, the secondary silane or the tertiary silane is provided.

Linear or cyclic polysilane-based compounds, especially liquid polysilanes, using novel catalysts that enable the reduction of dehydrogenation polymerization of secondary silanes, particularly those of which primary dehydrogenation reactivity is limited, as well as primary silanes. System compounds can be prepared. In addition, the gas phase silane can be transformed into a stable polysilane compound through the dehydrogenation polymerization of the catalyst. In addition, the polysilane-based compound to be produced can selectively control the number n value of the repeating units, whereby a liquid polysilane-based compound having a desired molecular weight can be obtained.

The obtained polysilane-based compound can be used in various devices such as semiconductors, and in particular, the obtained liquid polysilane-based compound has no solubility in organic solvents and has excellent solubility in performing a liquid phase process. It can be usefully used to manufacture the amorphous silicon thin film used. The liquid phase manufacturing method is simpler than the conventional CVD method, thereby lowering the unit cost. In addition, since the sophisticated high-resolution printing method can be used, it is easy for mass production. Therefore, this liquid phase method can satisfy the efficiency and economic efficiency of the amorphous silicon thin film solar cell manufacturing at the same time.

1 is a graph showing the results of GC / MSD analysis for Example 1 of the present invention, which shows the abundance value on the Y-axis and the minutes on the X-axis.

Figure 2 is a graph showing the results of GC / MSD analysis for Example 1 of the present invention is to display the abundance value on the Y axis and m / z value on the X axis.

3 is a graph showing the results of GPC analysis for Example 1 of the present invention, the X axis represents minutes (retention time), and the Y axis represents MV values.

4 is a graph showing the results of GC / MSD analysis for Example 2 of the present invention showing the abundance value on the Y-axis and the minutes (minutes) on the X-axis.

FIG. 5 is a graph showing the results of GC / MSD analysis for Example 2 of the present invention showing abundance values on the Y axis and m / z values on the X axis.

6 is a graph showing the results of GPC analysis for Example 2 of the present invention, the X axis represents minutes (retention time), and the Y axis represents MV values.

7 is a graph showing the results of GC / MSD analysis for Example 3 of the present invention showing abundance values on the Y-axis and minutes on the X-axis.

FIG. 8 is a graph showing the results of GC / MSD analysis for Example 3 of the present invention showing abundance values on the Y axis and m / z values on the X axis.

9 is a graph showing the results of GPC analysis for Example 3 of the present invention, the X axis represents minutes (retention time), the Y axis represents the MV value.

10 is a graph showing the results of GC / MSD analysis for Example 4 of the present invention showing the abundance value on the Y-axis and the minutes (minutes) on the X-axis.

FIG. 11 is a graph showing the results of GC / MSD analysis for Example 4 of the present invention showing abundance values on the Y axis and m / z values on the X axis.

12 is a graph showing the results of GPC analysis for Example 4 of the present invention, the X axis represents minutes (retention time), and the Y axis represents MV values.

FIG. 13 is a graph showing the results of GC / MSD analysis for Example 5 of the present invention showing abundance values on the Y-axis and minutes on the X-axis.

14 is a graph showing the results of GC / MSD analysis for Example 5 of the present invention showing abundance values on the Y-axis and m / z values on the X-axis.

15 is a graph showing the results of GPC analysis for Example 5 of the present invention, the X axis represents minutes (retention time), and the Y axis represents MV values.

FIG. 16 is a graph showing the results of GC / MSD analysis for Example 6 of the present invention showing abundance values on the Y-axis and minutes on the X-axis.

17 is a graph showing the results of GC / MSD analysis for Example 6 of the present invention, the abundance value is displayed on the Y-axis, and the m / z value is displayed on the X-axis.

18 is a graph showing the results of GC / MSD analysis for Example 7 of the present invention showing abundance values on the Y-axis and minutes on the X-axis.

19 is a graph showing the results of GC / MSD analysis for Example 7 of the present invention, the abundance value is displayed on the Y-axis, and the m / z value is displayed on the X-axis.

20 is a graph showing the results of GC / MSD analysis for Example 8 of the present invention showing the abundance value on the Y-axis and the minutes (minutes) on the X-axis.

FIG. 21 is a graph showing the results of GC / MSD analysis for Example 8 of the present invention showing abundance values on the Y axis and m / z values on the X axis.

Hereinafter, exemplary embodiments of the present invention will be described.

In the present specification, the polysilane-based compound is used as a meaning including both disilane and oligosilane, unless otherwise specified.

In the present specification, the polysilane-based compound is used as a meaning including polysilane and its derivatives unless otherwise specified.

In exemplary embodiments of the present invention, polysilane-based compounds which are dehydrogenated polymers obtained by dehydrogenation polymerization of primary, secondary and tertiary silanes in the presence of a catalyst can be prepared. The polysilane-based compound prepared may be linear or cyclic.

According to exemplary embodiments of the present invention, dehydrogenation polymerization reactions are possible without the presence of compounds for hydrosilylation (compounds such as cycloolefins having carbon-carbon unsaturated bonds, for example), and also due to steric effects, secondary It can overcome that the dehydrogenation polymerization reactivity falls as it goes to a silane and a tertiary silane.

In addition, it is possible to selectively adjust the number n value of the repeating units, and thus it is possible to adjust the molecular weight of the obtained polysilane-based compound. By controlling the molecular weight, it is possible to prepare a polysilane-based compound having a desired molecular weight, in particular a polysilane-based compound having various polymerization degrees.

For reference, until now, dehydrogenation polymerization has been mainly limited to primary silanes due to differences in reactivity. Secondary silanes have some degree of reactivity, but tertiary silanes have very limited reactivity. However, using the present catalyst capable of dehydrogenation of the tertiary silane, the following method is possible in the dehydrogenation polymerization reaction. In other words, the tertiary silane can be regarded as a kind of terminal group having one hydrogen that can react. If the desired compound is a compound having a polymerization degree of 3, for example, 1 equivalent of primary silane or secondary silane and 2 equivalents of tertiary silane When the reaction is carried out, a compound having a polymerization degree 3 can be obtained as a main product. In the same manner, by reacting 1 equivalent of primary or secondary silane with 1 equivalent of tertiary silane or by reacting 1 equivalent of secondary silane with 1 equivalent of tertiary silane, a compound having a degree of polymerization of 4 can be obtained as the main product. In this way, a liquid silane compound having a degree of polymerization of 5, 6, 7, or the like can be synthesized as a main product.

Hereinafter, the dehydrogenation polymerization reaction in one exemplary embodiment of the present invention will be described in detail.

In one exemplary embodiment of the present invention, a linear or cyclic liquid polysilane-based compound may be obtained through the preparation of the dehydrogenation polymerization reaction of Scheme 1 below.

Scheme 1

In the polysilane-based compound prepared through the dehydrogenation polymerization of [Scheme 1], the n value is not limited to an integer of 1 or more, but may be 1 to 119. Here, n may be 1, 2 to 6, or 7 to 119. Since n is preferably a liquid polysilane of 5 to 6 in view of the fact that a high boiling point does not volatilize when manufacturing the amorphous thin film silicon.

In addition, m is not limited to an integer of 1 or more, but it may be difficult to obtain m more than 7, that is, more than 10 hexagons, so in terms of yield, 1 to 7 (preferably 1 to 6, more preferably 1 to 1). 5). M may be 1, and may be 2 to 7 (or 2 to 6, or 2 to 5). In the case of the cyclic polysilane, m is preferably 2 to 7 (or 2 to 6, or 2 to 5) from the standpoint of ease of production such as ease of addition polymerization during the amorphous thin film silicon manufacturing process.

Specifically, in the linear polysilane-based compound (formula 1) prepared through the dehydrogenation polymerization reaction of [Scheme 1], n may be gaseous or liquid or solid polysilane of 1 (depending on R group). Gaseous, liquid or solid). In addition, n may be a liquid or solid phase (which may be a liquid or solid phase depending on the R group) of 2 to 6 polysilane. In addition, n may be 7 to 119 solid polysilanes.

[Formula 1]

In the cyclic polysilane-based compound (formula 2) prepared through the dehydrogenation polymerization reaction of [Scheme 1], m may be a liquid polysilane of 1, and 2 to 7 or 2 to 6 or 2 to It may be a liquid or solid polysilane of 5 (it may be a liquid or solid phase depending on the R group). For reference, when m is 7 or more, it may be 10 or more, and when m is 6, it may be a pentagon, and when m is 5, it may be an octagon.

[Formula 2]

In the dehydrogenation polymerization reaction of [Scheme 1], the starting material is a primary silane, a secondary silane or a tertiary silane (Formula 3), and the silane may be converted into a stable polysilane compound through the catalysis. For reference, the silane of the following [Formula 3] may be a gas phase, a liquid phase, or a solid phase depending on the R group, and in the case of all having a hydrogen substituent, the silane is a gaseous phase.

[Formula 3]

In the above [Scheme 1], [Formula 1] to [Formula 3], R_One, R₂, R₃ Are each independently hydrogen atom, halogen atom, oxygen atom, nitro group, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkaryl group, alkoxy group, alkoxycarbonyl group, carbonyloxy group, amino Carbonyl groups, dialkyl amino groups, derivatives thereof or they may be substituted by optional substituents. They may be linear or nonlinear and may optionally combine to form a ring. Where R_One, R₂, R₃May be the same or different, respectively.

In one exemplary embodiment, R in [Scheme 1], [Formula 1] to [Formula 3]_One, R₂, R₃Suitable examples of C 1 -C 14 alkyl group, C 1 -C 14 cycloalkyl group, C 1 -C 14 ， aryl group, C 1 -C 14 aralkyl group, C 1 -C 14 alkaryl group, C 1 -C 14 alkoxy group And these substituents may be linear or nonlinear, and may optionally combine to form a ring. Non-limiting examples of such alkyl groups here include methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl, myrisil and the like. In addition, non-limiting examples of such cycloalkyl groups include cyclobutyl, cyclohexyl, and the like. Further non-limiting examples of such aryl groups include phenyl, xenyl, naphthyl and the like. In addition, non-limiting examples of the aralkyl group include benzyl, 2-phenylethyl and the like. In addition, non-limiting examples of the alkaryl groups include tolyl, xylyl, mesityl and the like. In addition, non-limiting examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy and the like.

Or, in an exemplary embodiment, in the [Reaction Scheme 1], [Formula 1] to [Formula 3], preferably, R_One, R₂, R₃ May comprise a group consisting of aryl substituted by halogen, nitro group, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, dialkylamino, derivatives thereof or optional substituents. As a non-limiting example, R_One, R₂, R₃ Are methyl, ethyl, propyl, propenyl, propynyl, butyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, phenyl, benzyl, naphthyl, anthracenyl, mesityl , Xylyl, tolyl, xylyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-t-butylphenyl, 4-methoxyphenyl, 4-isopropoxyphenyl, cumyl, methoxy, on Methoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, trimethylsilyl, dimethylhydrazyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, o-methylphenyl, o-ethylphenyl, It may be selected from the group containing o-isopropylphenyl, ot-butylphenyl, o-methoxyphenyl, o-isopropoxyphenyl, biphenyl, naphthyl, anthracenyl.

Non-limiting examples of monohalosilanes that may be used in the dehydrogenation polymerization in one illustrative embodiment of the present invention include benzylmethylchlorosilane, n-butylmethylchlorosilane, di-n-butylchlorosilane, ethylmethyl Chlorosilane, diethylchlorosilane, dimethylchlorosilane, n-octadecylmethylchlorosilane, phenylmethylchlorosilane, diphenylchlorosilane, cyclohexylmethylchlorosilane, cyclopentylmethylchlorosilane, n-propylmethylchlorosilane, tolyl Methylchlorosilane, allylmethylchlorosilane, 5-hexenylmethylchlorosilane, vinylmethylchlorosilane, and the like.

Non-limiting examples of dihalosilanes that may be used in the dehydrogenation polymerization reaction in one illustrative embodiment of the present invention include t-butyldichlorosilane, phenyldichlorosilane, dichlorocyclohexsilane, dichloroethylsilane, dichloromethylsilane, Dichlorophenylsilane, dichlorohexylsilane, dichloro (3-phenylpropyl) silane, dichloroisopropylsilane, dichloro (4-phenylbutyl) silane, n-propyldichlorosilane, dichloroallylsilane, dichlorovinylsilane, trichlorosilane and the like. Include.

Non-limiting examples of monoalkoxysilanes that may be used in the dehydrogenation polymerization reaction in one illustrative embodiment of the present invention include t-butylphenylmethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethyl-n-pro Foxysilane, n-octadecylmethylmethoxysilane, octylmethylmethoxysilane, cyclopentylethylmethoxysilane, dicyclopentylmethoxysilane, dicyclopentylmethoxysilane, phenylmethylethoxysilane, diphenylethoxysilane And vinyl methyl ethoxysilane.

Non-limiting examples of dialkoxysilanes that may be used in the dehydrogenation polymerization reaction in one illustrative embodiment of the present invention include butyldimethoxysilane, dodecyldiethoxysilane, ethyldiethoxysilane, methyldimethoxysilane, methyldie Methoxysilane, n-octyl diethoxysilane, octadecyldimethoxysilane, phenyl diethoxysilane, phenyldimethoxysilane, vinyldimethoxysilane and the like.

Non-limiting examples of trialkoxysilanes that may be used in the dehydrogenation polymerization reaction in one illustrative embodiment of the present invention include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, and the like.

The following describes a dehydrogenation catalyst (catalyst in [Scheme 1]) that can be used in the embodiments of the present invention.

The dehydrogenation catalyst that can be used in the embodiments of the present invention is a high performance dehydrogenation catalyst for performing the dehydrogenation polymerization reaction, and may use the following homogeneous or non-uniform catalysts.

Homogeneous catalysts are complex compounds in which the core metal and one or more ligands which stabilize these core metals are bonded.

The central metal includes all known metals. Non-limiting examples thereof include alkali metals of Li, Na, K, Rb, Cs, and Fr; Alkaline earth metals of Be, Mg, Ca, Sr, Ba, Ra; The P-block metals of the periodic table of Al, Ga, In, Sn, Tl, Pb, Bi; Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, The B block metal transition metal of the periodic table of Pt, Au, Hg; Of lanthanides, Ac, Th, Pa, U, Np, Pu, Am of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb Actinide-based metals (the actinides) and the like can be used, it is preferable to use a transition metal, more preferably Co, Ni, Pd or Pt.

Specifically, the homogeneous catalyst may be represented by the following [Formula 4].

[Formula 4]

(Wherein, M is a central metal of the complex compound, and may be any metal known as described ^{above. R 1, R 2, R} 3 and R ⁴ are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroaryl, hydrocarbyl, or Substituted heterohydrocarbyl, R ⁵ and R ⁶ excluding hydrogen and are independently hydrocarbyl or substituted hydrocarbyl X is a halogen atom, an alkyl group of C1-C20, an arylalkyl group of C7-C30, C1-C20 Is selected from the group consisting of an alkoxy group having an alkyl group, a C3-C20 alkyl-substituted siloxy group, and an amido group having a hydrocarbon group of C1-C20, and X on both sides of M may be the same or different).

Ligands capable of forming complexes on the central metal may be represented by the following [Formula 5], and their skeleton structures may be represented by the following [Formula 6] to [Formula 8], for example.

[Formula 5]

[Formula 6] represents (S, S) -enantiomer [(S, S) -R ¹ R ² PCH (R ⁵ ) CH (R ⁶ ) PR ³ R ⁴ ], wherein , R)-(enantiomer) [(R, R) -R ¹ R ² PCH (R ⁵ ) CH (R ⁶ ) PR ³ R ⁴ ], where [Formula 8] is a meso-daastomer [meso R ¹ R ² PCH (R ⁵ ) CH (R ⁶ ) PR ³ R ⁴ ].

[Formula 6]

[Formula 7]

[Formula 8]

Wherein R ¹ , R ² , R ³ and R ⁴ are independently hydrocarbyl, substituted hydrocarbyl, heterohydro carbyl, or substituted heterohydro carbyl, and R ⁵ and R ⁶ are hydrocarbyl or substituted except hydrogen Hydrocarbyl.

R ¹ , R ² , R ³ and R ⁴ are preferably independently phenyl, benzyl, naphthyl, anthracenyl, mesityl, xylyl, methyl, ethyl, ethylenyl, propyl, propenyl, propynyl, butyl, Cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl,, tolyl, xylyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-t-butylphenyl, 4-methoxyphenyl, 4-isopropoxyphenyl, cumyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, trimethylsilyl, dimethylhydrazyl, 2-methylcyclohexyl, 2-ethyl Cyclohexyl, 2-isopropylcyclohexyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, ot-butylphenyl, o-methoxyphenyl, o-isopropoxyphenyl, biphenyl, naphthyl, anthra It can be selected from the group including senyl.

More preferably R ¹ , R ² , R ³ and R ⁴ are independently phenyl, tolyl, biphenyl, naphthyl, cyclohexyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-t- Butylphenyl, 4-methoxyphenyl, 4-isopropoxyphenyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, and ot-butylphenyl, o-methoxyphenyl, o-isopropoxyphenyl.

R ⁵ and R ⁶ are preferably independently hydrocarbyl, substituted hydrocarbyl groups excluding hydrogen. Specifically, it may be selected from the group consisting of alkyl, aryloxy, halogen, nitro, alkoxycarbonyl, carbonyloxy, alkoxy, aminocarbonyl, dialkylamino, derivatives thereof, or aryl substituted by an optional substituent. .

PCCP skeletal structural ligands for the stable maintenance of the reaction activity are (S, S)-, or (R, R) -isomers or multiple (S, S)-, or (R, R)-in a mixture of the two isomers. (R ¹ ) (R ² ) P- (R ⁵ ) CHCH (R ⁶ ) -P (R ³ ) (R ⁴ ) may be combined to form a unit.

Examples of stereoisomeric structural ligands forming the P-C-C-P backbone for stable activity include (S, S)-or (R, R)-(phenyl)₂P-CH (methyl) CH (methyl) -P (phenyl)₂, (S, S)-or (R, R)-(4-methoxyphenyl)₂P-CH (methyl) CH (methyl) -P (4-methoxyphenyl)₂, (S, S)-or (R, R)-(4-methylphenyl)₂P-CH (methyl) CH (methyl) -P (4-methylphenyl)₂, (S, S)-or (R, R)-(4-ethylphenyl)₂P-CH (methyl) CH (methyl) -P (phenyl)₂, (S, S)-or (R, R)-(4-ethylphenyl)₂P-CH (ethyl) CH (methyl) -P (4-ethylphenyl)₂, (S, S)-or (R, R)-(4-methoxyphenyl)₂P-CH (ethyl) CH (methyl) -P (phenyl)₂, (S, S)-or (R, R)-(4-ethylphenyl)₂P-CH (ethyl) CH (ethyl) -P (4-ethylphenyl)₂, (S, S)-or (R, R)-(phenyl)₂P-CH (ethyl) CH (ethyl) -P (phenyl)₂, (S, S)-or (R, R)-(phenyl)₂P-CH (isopropyl) CH (methyl) -P (phenyl)₂, (S, S)-or (R, R)-(4-methoxyphenyl)₂P-CH (isopropyl) CH (methyl) -P (4-methoxyphenyl)₂, (S, S)-or (R, R)-(4-ethylphenyl)₂P-CH (isopropyl) CH (methyl) -P (4-ethylphenyl)₂, (S, S)-or (R, R)-(phenyl)₂P-CH (n-propyl) CH (methyl) -P (phenyl)₂, (S, S)-or (R, R)-(4-methoxyphenyl)₂P-CH (n-propyl) CH (methyl) -P (4-methoxyphenyl)₂, (S, S)-or (R, R)-(4-ethylphenyl)₂P-CH (n-propyl) CH (methyl) -P (4-ethylphenyl)₂, (S, S)-or (R, R)-(phenyl)₂P-CH (isopropyl) CH (ethyl) -P (phenyl)₂, (S, S)-or (R, R)-(4-methoxyphenyl)₂P-CH (isopropyl) CH (ethyl) -P (4-methoxyphenyl)₂, (S, S)-or (R, R)-(4-ethylphenyl)₂P-CH (isopropyl) CH (ethyl) -P (4-ethylphenyl)₂, (S, S)-or (R, R) -1,2-di- (P (phenyl)₂Cyclohexane, (S, S)-or (R, R) -1,2-di- (P (4-methoxyphenyl)₂Cyclohexane, (S, S)-or (R, R) -1,2-di- (P (4-ethylphenyl)₂Cyclohexane, (S, S)-or (R, R) -1,2-di- (P (phenyl)₂Cyclopentane, (S, S)-or (R, R) -1,2-di- (P (4-methoxyphenyl)₂Cyclopentane, (S, S)-or (R, R) -1,2-di- (P (4-ethylphenyl)₂Cyclopentane, (S, S)-or (R, R) -3,4-di- (P (phenyl)₂Pyrrole, (S, S)-or (R, R) -3,4-di- (P (4-methoxyphenyl)₂Pyrrole, (S, S)-or (R, R) -3,4-di- (P (4-ethylphenyl)₂Pyrrole, (S, S)-or (R, R) -3,4-di- (P (4-ethylphenyl)₂Imidazole, (S, S)-or (R, R)-(4-ethylphenyl)₂P-CH (dimethylamine) CH (dimethylamine) -P (4-ethylphenyl)₂, (S, S)-or (R, R)-(3-methoxyphenyl)₂P-CH (methyl) CH (methyl) -P (3-methoxyphenyl)₂, (S, S)-or (R, R)-(4-ethoxyphenyl)₂P-CH (methyl) CH (methyl) -P (o-ethoxyphenyl)₂, ((S, S)-or (R, R) -4-dimethylaminephenyl)₂P-CH (methyl) CH (methyl) P (4-dimethylaminephenyl)₂, (S, S)-or (R, R)-(4-ethylcyclohexyl)₂PCH (methyl) CH (methyl) P (4-ethylcyclohexyl)₂(S, S)-or (R, R)-(2-ethylphenyl)₂PCH (methyl) CH (methyl) P (2-ethylphenyl)₂, (S, S)-or (R, R)-(2-isopropylphenyl)₂PCH (methyl) CH (methyl) P (2-isopropylphenyl)₂, (S, S)-or (R, R)-(2-methylphenyl)₂PCH (methyl) CH (methyl) P (2-methylphenyl)₂, (S, S)-or (R, R)-(2-ethylphenyl)₂PCH (methyl) CH (methyl) P (phenyl)₂, (S, S)-or (R, R)-(2-ethylphenyl)₂PCH (ethyl) CH (methyl) P (2-ethylphenyl)₂, (S, S)-or (R, R)-(2-ethylphenyl)₂PCH (ethyl) CH (ethyl) P (2-ethylphenyl)₂, (S, S)-or (R, R)-(2-ethylphenyl)₂PCH (Isopropyl) CH (methyl) P (2-ethylphenyl)₂, (S, S)-or (R, R)-(2-ethylphenyl)₂PCH (n-propyl) CH (methyl) P (2-ethylphenyl)₂, (S, S)-or (R, R)-(2-ethylphenyl)₂PCH (isopropyl) CH (ethyl) P (2-ethylphenyl)₂, 1,2-di- (P (2-ethylphenyl)₂Cyclohexane, (S, S)-or (R, R) -1,2-di- (P (2-ethylphenyl)₂Cyclopentane, (S, S)-or (R, R) -3,4-di- (P (2-ethylphenyl)₂Pyrrole, (S, S)-or (R, R) -3,4-di- (P (2-ethylphenyl)₂Imidazole, (S, S)-or (R, R)-(2-ethylphenyl)₂PCH (dimethylamine) CH (dimethylamine) P (2-ethylphenyl)₂, (S, S)-or (R, R)-(2-methoxyphenyl)₂PCH (methyl) CH (methyl) P (2-methoxyphenyl)₂, (S, S)-or (R, R)-(2-ethoxyphenyl)₂PCH (methyl) CH (methyl) P (2-ethoxyphenyl)₂, (S, S)-or (R, R)-(2-dimethylaminephenyl)₂PCH (methyl) CH (methyl) P (2-dimethylaminephenyl)₂, (S, S)-or (R, R)-(2-ethylcyclohexyl)₂PCH (methyl) CH (methyl) P (2-ethylcyclohexyl)₂There is, but is not limited to this.

In exemplary embodiments of the present invention, the PCCP type stereoisomeric framework of the ligand has a structure independent of known (eg) conventional (R) _n PN (R ′) P (R) _m heteroligands. Is a ligand, and only the hetero atoms in the backbone structure of the ligand are phosphorus (P) atoms.

That is, the ligand used in the first catalyst is composed of two carbon-carbon skeleton structures without nitrogen atoms between two phosphorus atoms, and exhibits excellent catalytic activity by appropriately adjusting the spatial structure in the arrangement direction of the substituents attached to the carbon atoms. In addition, the stability of the reaction activity can be maintained.

In an exemplary embodiment of the invention, X is for example Cl and M may more preferably be Co, Ni, Pd, Pt, which are referred to herein as KH14, KH15, KH16, KH17, respectively. The following shows each chemical structural formula.

[Formula 9]

Bis (2,3-diphenylphosphinobutane)] dichlorocobalt (II)

[Formula 10]

Bis (2,3-diphenylphosphinobutane)] dichloronickel

[Formula 11]

Bis (2,3-diphenylphosphinobutane)] dichloropalladium

[Formula 12]

Bis (2,3-diphenylphosphinobutane)] dichloroplatinum

The catalyst can be prepared, for example, as follows. (S, S)-(phenyl) ₂ PCH (methyl) CH (methyl) P (phenyl) ₂ was added to anhydrous ethanol to a solution of M (central metal such as cobalt (II)) chloride in anhydrous ethanol solution. Slowly dropwise under conditions. When the color of the solution changes, the solution is refluxed at a certain time and temperature. After cooling to room temperature and filtering, the ethanol solution may be dried to obtain the catalyst.

In addition to the homogeneous catalyst described above, a non-uniform catalyst can be used. Non-uniform catalysts can be prepared using homogeneous catalysts.

As a non-limiting example, it is possible to form a metal cluster formed by reducing the homogeneous catalyst, for example. The metal cluster may be a nanocluster, for example, a nanocluster having a size of 2 nm or less.

The dehydrogenation polymerization solvent is not particularly limited as long as the components contained in the respective compositions are precipitated, phase separated, or not reacted with them.

By way of non-limiting example, n-pentane, n-hexane, n-heptane, n-octane, decane, dodecane, cyclohexane, cyclooctane, styrene, dicyclopentane, benzene, toluene, xylene, cumene, durene, indene Hydrocarbon solvents such as tetrahydronaphthalene, decahydronaphthalene and squalane; Diethyl ether, dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, tetra Ether solvents such as hydropyran, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, p-dioxane and tetrahydrofuran; And polar solvents such as propylene carbonate, N-methyl-2-pyrrolidone, dimethylformamide, acetonitrile, dimethyl sulfoxide, methylene chloride and chloroform. Of these, hydrocarbon solvents are preferred in view of the stability of the solution. Of these, the solvent may be used alone or as a mixture of two or more thereof.

According to the polysilane production according to the embodiments of the present invention as described above, it is possible to significantly shorten the time required for the production of polysilane as well as to be suitable for mass production.

The liquid polysilane derivatives obtained above include ceramic precursors, interlayer insulating films, photoelectric materials such as photoresists and organic photoconductors, light transmission materials such as optical waveguides, optical recording materials such as optical memories, and materials for electroluminescent devices. It can be used for the purpose, etc., it can be used in a variety of materials such as semiconductor industry and the photovoltaic industry. In addition, it is particularly useful for forming amorphous silicon thin films, particularly amorphous silicon thin films for silicon solar cells, through a liquid phase process.

For reference, amorphous silicon thin film solar cells have been known to have lower efficiency than crystalline silicon solar cells. However, in terms of materials, only a small amount (eg, 1%) of silicon is required to be very economical. to be.

Generally, as a method of forming an amorphous silicon film or a polysilicon film used for manufacturing a solar cell, thermal CVD (chemical vapor deposition, chemical vapor deposition), plasma CVD, optical CVD, etc. of monosilane gas or disilane gas is used. For example, a thermal CVD method is widely used to form a polysilicon film, and a plasma CVD method is widely used to form an amorphous silicon film. However, such a CVD method uses a gas phase reaction, thereby lowering the efficiency of the device due to contamination of the device by the by-products of silicon particles in the gas phase. In addition, since the raw material is gaseous, it is difficult to obtain uniform step coverage on the substrate having irregularities on the surface. In addition, since the film formation speed is low, the throughput per unit time is low, resulting in low productivity. In addition, in the case of plasma CVD, a complicated high frequency generator and a vacuum device are required, which makes the process expensive.

The liquid polysilane-based compound according to the exemplary embodiments of the present invention can produce amorphous thin film silicon extremely economically by a liquid phase process rather than a vapor phase process.

Specifically, when the polysilane-based compound according to the embodiments of the present invention is applied to the production of the thin film silicon by the liquid phase process, for example, a coating method may be used. For reference, the obtained polysilane-based compound may be further subjected to an additional polymerization process as needed.

As a non-limiting example, the prepared liquid silane may be coated with a thin film on a substrate, and then decomposed and reacted in the coating film through a heat treatment process including an elevated temperature process to form a silicon film.

In a non-limiting example, a silicon film may be formed by using the obtained liquid silane as a solvent and dissolving and applying the obtained solid phase silane thereto. For reference, in order to use a solid silane in the preparation of amorphous thin film silicon, a solvent for dissolving it is required. In embodiments of the present invention, a solid silane which is difficult to dissolve may be easily dissolved and used as a solvent. Has a very big advantage.

For example, a liquid silane having n of 6 or less in [Formula 1] can be used as a solvent and a solid silane of n of 7 or more can be dissolved therein.

In a non-limiting example, when n ≦ 4 in [Formula 1], since the boiling point is relatively low and the decomposition temperature is high, a liquid silane (ie, n is 5 or 6), preferably n> 4, is used to form the silicon film. desirable. However, of course, you may contain monosilane, disilane, trisilane, tetrasilane, and isotetrasilane which are silanes of n <= 4. In addition, as mentioned above, even when a liquid silane such as oligosilane having n ≦ 4 is used, a solid polysilane (n ≧ 7) can be dissolved using the oligosilane as a solvent and a silicon film can be formed by an application method. have.

The coating method may be a general method such as spin coating, dip coating, spray and the like. Application | coating is generally performed at the temperature above normal temperature. At temperatures below room temperature, the liquid silane may solidify.

The heat treatment temperature during the temperature increase of the silicon film depends on the liquid silane used, but the heat treatment temperature is generally 200 to 500 ° C. When the temperature is 200 ° C. or less, the decomposition reaction may not proceed sufficiently and a silicon film having a sufficient thickness may not be formed.

Specifically, the liquid silane is applied to a thickness of 100 nm through spin coating under a nitrogen gas atmosphere. After the coating, the reaction was decomposed by heat treatment at 200 ° C. for 10 minutes at 300 ° C., 10 minutes at 300 ° C., and again at 400 to 500 ° C. for 2 hours. After the heat treatment is completed, the formation of the silicon film after cooling to room temperature can be confirmed by confirming the peak of 480 cm ^-1 , which is a specific wavelength of a-Si, by measuring Raman scattering spectra. .

As described above, when the amorphous thin film silicon is manufactured by the liquid phase method and used for manufacturing the solar cell, the manufacturing efficiency of the amorphous thin film silicon solar cell can be simultaneously maximized and economical.

Hereinafter, one or more exemplary embodiments of the present invention will be described in more detail through non-limiting and exemplary embodiments.

[Catalyst Preparation Example: KH14 Catalyst Preparation]

The above-mentioned KH14 catalyst of [Formula 9] was prepared as follows.

(S, S)-(phenyl) ₂ PCH (methyl) CH (methyl) P (phenyl) ₂ (5.00 g, 12.5 mmol) was added to 50 ml of anhydrous ethanol. Cobalt (II) chloride (1.62 g, 12.5 mmol) ) Was slowly added dropwise under nitrogen conditions to 25 ml of anhydrous ethanol solution. The color of the solution changed from dark blue to green. This solution was refluxed at 80 ° C. for 3 hours. After cooling to room temperature, the ethanol solution was dried after filtration, and the yield was 91%. IR (KBr) data are as follows: 3049 (m), 2926 (w), 1484 (m), 1435 (s), 1312 (w), 1190 (w), 1098 (s), 1027 (w), 999 (m), 878 (w ), 816 (w), 742 (s), 696 (s), 529 (s), and 514 cm ^-1 (m)

[Example of Dehydrogenation Polymerization Reaction: Using KH14 Catalyst]

Example 1 Phenylsilane (PhSiH) ₃ ) And KH14 Dehydrogenation Polymerization

Into a three-neck round bottomed flask (50 mL), the stirring rod was put in a reactor (flask) by drying under reduced pressure, and then dried nitrogen gas was introduced into the reactor, and phenylsilane (1.5 mmol, 0.16 g) was added. After the addition, pre-dried tetrahydrofuran (THF) solvent (2 mL) was injected and stirred to dissolve diphenylsilane. KH14 (3 mol%, 0.045 mmol, 0.019 g), a dehydrogenation catalyst, is dissolved in a pre-dried nitromethane solvent (0.5 mL) and then added dropwise to the reactor to release hydrogen and depolymerization. The amount of hydrogen generated through the hydrogen generation measuring device was quantified. The reaction proceeded for about 3 minutes after catalyst injection. After the reaction was completed, the stirring was stopped to separate the solvent layer and the solid catalyst layer and the catalyst was removed through a filter.

1 is a graph showing the results of GC / MSD analysis for Example 1 of the present invention, which shows the abundance value on the Y-axis and the minutes on the X-axis. Figure 2 is a graph showing the results of GC / MSD analysis for Example 1 of the present invention is to display the abundance value on the Y axis and m / z value on the X axis. 3 is a graph showing the results of GPC analysis for Example 1 of the present invention. For reference, in the GPC data, the X axis represents minutes (retention time) and the Y axis represents MV values.

The solvent was dried and then dissolved in hexane (20-25 ml). The part dissolved in hexane was analyzed by GC / MSD. As a result of GC / MSD analysis, diphenylsilane by redistribution was the main compound, and the formation of polysilane having n value of 2 to 4 was confirmed as the main compound (see FIGS. 1 and 2). In addition, the parts dissolved in tetrahydrofuran, that is, high molecular weight, were analyzed by GPC. GPC analysis confirmed the formation of polysilane (weight average molecular weight 12721) having an average value of 119 (see FIG. 3).

Example 2: Diphenylsilane (Ph ₂ SiH ₂ ) And KH14 Dehydrogenation Polymerization

The same procedure as in Example 1 was carried out except that diphenylsilane was used instead of the starting reaction material, phenylsilane. The reaction proceeded for about 40 minutes after catalyst injection.

4 is a graph showing the results of GC / MSD analysis for Example 2 of the present invention showing the abundance value on the Y-axis and the minutes (minutes) on the X-axis. FIG. 5 is a graph showing the results of GC / MSD analysis for Example 2 of the present invention showing abundance values on the Y axis and m / z values on the X axis. 6 is a graph showing the results of GPC analysis for Example 2 of the present invention. For reference, in the GPC data, the X axis represents minutes (retention time) and the Y axis represents MV values.

GC / MSD analysis of the part dissolved in hexane confirmed that biphenyl and triphenylsilane were the main products by redistribution of the starting material diphenylsilane (see FIGS. 4 and 5). Therefore, it was confirmed that the silane having a small molecular weight of n = 2 to 4 was not formed.

In addition, the part dissolved in tetrahydrofuran was analyzed by GPC. GPC analysis confirmed the formation of polysilane (weight average molecular weight 1360) having an n value of 7 (see FIG. 6).

Example 3: Diethylsilane (Et ₂ SiH ₂ ) And KH14 Dehydrogenation Polymerization

The same procedure as in Example 1 was carried out except that diethylsilane was used instead of phenylsilane as the starting reaction material. The reaction proceeded for about 2 minutes after catalyst injection.

7 is a graph showing the results of GC / MSD analysis for Example 3 of the present invention showing abundance values on the Y-axis and minutes on the X-axis. FIG. 8 is a graph showing the results of GC / MSD analysis for Example 3 of the present invention showing abundance values on the Y axis and m / z values on the X axis. 9 is a graph showing the results of GPC analysis for Example 3 of the present invention. For reference, in the GPC data, the X axis represents minutes (retention time) and the Y axis represents MV values.

As a result of GC / MSD analysis, it was confirmed that polysilane having n value of 2 to 5 was formed (see FIGS. 7 and 8). In addition, the part dissolved in tetrahydrofuran was analyzed by GPC. GPC analysis confirmed the formation of polysilane (weight average molecular weight 1424) having an average value of 16 (see FIG. 9).

Example 4: Methylphenylsilane (MePhSiH) ₂ ) And KH14 Dehydrogenation Polymerization

The same procedure as in Example 1 was carried out except that methylphenylsilane was used instead of the starting reaction material, phenylsilane. The reaction proceeded for about 11 minutes after catalyst injection.

FIG. 10 is a graph showing the results of GC / MSD analysis for Example 4 of the present invention showing abundance values on the Y axis and minutes on the X axis. FIG. 11 is a graph showing the results of GC / MSD analysis for Example 4 of the present invention showing abundance values on the Y axis and m / z values on the X axis. 12 is a graph showing the results of GPC analysis for Example 4 of the present invention. For reference, in the GPC data, the X axis represents minutes (retention time) and the Y axis represents MV values.

GC / MSD analysis of the part dissolved in hexane confirmed the formation of polysilane having n value of 2 to 4 (see FIGS. 10 and 11). The part dissolved in tetrahydrofuran was analyzed by GPC. GPC analysis confirmed polysilane formation with an n value of 7 to 8 on average (see FIG. 12).

Example 5: Dichlorosilane (Cl ₂ SiH ₂ ) And KH14 Dehydrogenation Polymerization

Since dichlorosilane is a gas phase at room temperature, after drying the reactor, the weight of the empty reactor was measured in advance, and then the temperature of the reactor was lowered to -78 ° C to trap the dichlorosilane in the reactor and weighed to determine the amount of the dichlorosilane as a reactant. The reaction method was carried out in the same manner as in Example 1, except that tetraethylene glycol dimethyl ether was used instead of THF as the solvent for dissolving dichlorosilane. The reaction proceeded for about 3 minutes after catalyst injection. Trimethylolsoformate (CH (OMe) ₃ ) was used for the methoxy reaction.

FIG. 13 is a graph showing the results of GC / MSD analysis for Example 5 of the present invention showing abundance values on the Y-axis and minutes on the X-axis. 14 is a graph showing the results of GC / MSD analysis for Example 5 of the present invention showing abundance values on the Y-axis and m / z values on the X-axis. 15 is a graph showing the results of GPC analysis for Example 5 of the present invention. For reference, in the GPC data, the X axis represents minutes (retention time) and the Y axis represents MV values.

GC / MSD analysis confirmed the formation of a polysilane having n value of 2 to 5 (see FIGS. 13 and 14). In addition, the part dissolved in tetrahydrofuran was analyzed by GPC. GPC analysis confirmed the formation of polysilane with n value of 9 (see FIG. 15).

Example 6: Dimethylchlorosilane (Me ₂ Dehydrogenation Polymerization Using ClSiH) and KH14

The same procedure as in Example 1 was carried out except that dimethylchlorosilane was used instead of phenylsilane as the starting reaction material. The reaction proceeded for about 2 minutes after catalyst injection.

FIG. 16 is a graph showing the results of GC / MSD analysis for Example 6 of the present invention showing abundance values on the Y-axis and minutes on the X-axis. 17 is a graph showing the results of GC / MSD analysis for Example 6 of the present invention, the abundance value is displayed on the Y-axis, and the m / z value is displayed on the X-axis.

GC / MSD analysis confirmed the formation of tetramethyldiphenyldisilane having n value of 2 (see FIGS. 16 and 17).

Example 7: Triethylsilane (HSiEt ₃ ) And KH14 Dehydrogenation Polymerization

The reaction was carried out in the same manner as in Example 1 except that triethylsilane was used instead of the starting reaction material phenylsilane and the reaction solvent was reacted without using a solvent instead of tetrahydrofuran. The reaction proceeded for about 50 minutes after catalyst injection.

18 is a graph showing the results of GC / MSD analysis for Example 7 of the present invention showing abundance values on the Y-axis and minutes on the X-axis. 19 is a graph showing the results of GC / MSD analysis for Example 7 of the present invention, the abundance value is displayed on the Y-axis, and the m / z value is displayed on the X-axis.

GC / MSD analysis confirmed that hexaethyldisilane having a n value of 2 was formed as a main product (see FIGS. 18 and 19).

Example 8: Trimethoxysilane (HSi (OMe) ₃ ) And KH14 Dehydrogenation Polymerization

In the same manner as in Example 1 except for using trimethoxysilane instead of starting reaction material phenylsilane and tetraethylene glycol dimethyl ether instead of tetrahydrofuran. Was performed. The reaction proceeded for about 45 minutes after catalyst injection.

20 is a graph showing the results of GC / MSD analysis for Example 8 of the present invention showing the abundance value on the Y-axis and the minutes (minutes) on the X-axis. FIG. 21 is a graph showing the results of GC / MSD analysis for Example 8 of the present invention showing abundance values on the Y axis and m / z values on the X axis.

As a result of GC / MSD analysis, it was confirmed that hexamethoxydisilane having an n value of 2 was formed as a main product. In addition to hexamethoxydisilane, small amounts of octamethoxytrisilane and decamethoxytetrasilane were formed by reaction with dimethoxysilane formed by redistribution of trimethoxysilane as a starting material (see FIGS. 20 and 21). .

The present specification relates to a method for producing a polysilane-based compound, in particular a liquid polysilane-based compound, and a polysilane-based compound prepared according to the present invention, a dehydrogenation catalyst used in the method, and a method for producing amorphous thin film silicon using a polysilane-based compound. Describe it. The polysilane-based compound can be usefully used in the production of a variety of electronic devices, including solar cells, in particular by the liquid phase process of the amorphous silicon thin film used in the production of silicon solar cells.

Claims (31)

1. A method for producing a polysilane-based compound by dehydrogenation-polymerizing primary silane, secondary silane or tertiary silane in the presence of a dehydrogenation catalyst,

   The dehydrogenation catalyst is a method for producing a polysilane-based compound having the following [Formula 4].

   [Formula 4]

   

   Wherein M is a metal. R ¹ , R ² , R ³ and R ⁴ are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydro carbyl, or substituted heterohydro carbyl, and R ⁵ and R ⁶ are Excluding hydrogen and independently hydrocarbyl or substituted hydrocarbyl X is a halogen atom, an alkyl group of C1-C20, an arylalkyl group of C7-C30, an alkoxy group having an alkyl group of C1-C20, a C3-C20 alkylsubstituted siloxane Is selected from the group consisting of amido groups having hydrocarbon groups of C1-C20, and X on both sides of M may be the same or different.)
2. The method of claim 1,

   M in Formula 4 is an alkali metal; Alkaline earth metals; P-block metals of the periodic table; B block metals of the periodic table; Lanthanum series metals; Or a method of producing a polysilane-based compound which is an actinide gelatinization metal.
3. The method of claim 1,

   M in Formula 4 is Co, Ni, Pd or Pt manufacturing method of a polysilane-based compound.
4. The method of claim 3, wherein

   X is a method for producing a polysilane-based compound is Cl.
5. The method of claim 1,

   The dehydrogenation catalyst is a method for producing a polysilane-based compound is a catalyst cluster of the formula [4] or a mixed catalyst in which the catalyst of the formula [4] is mixed in the cluster.
6. The method of claim 5,

   The cluster is a method for producing a polysilane-based compound is a nano cluster having a size of 2nm or less.
7. The method of claim 1,

   The dehydrogenation polymerization reaction is a method for producing a polysilane-based compound is carried out by the following [scheme 1].

   Scheme 1

   

   Wherein n and m are each an integer of 1 or more, and R_One, R₂, R₃ Are the same or different, and each hydrogen atom, halogen atom, oxygen atom, nitro group, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkaryl group, alkoxy group, alkoxycarbonyl group, carbonyloxy Groups, aminocarbonyl groups, dialkyl amino groups, derivatives thereof or they may be substituted by optional substituents. R_One, R₂, R₃May each be linear or non-linear and may optionally combine to form a ring.)
8. The method of claim 1,

   The primary silane is benzylmethylchlorosilane, n-butylmethylchlorosilane, di-n-butylchlorosilane, ethylmethylchlorosilane, diethylchlorosilane, dimethylchlorosilane, n-octadecylmethylchlorosilane, phenylmethylchlorosilane , Diphenylchlorosilane, cyclohexylmethylchlorosilane, cyclopentylmethylchlorosilane, n-propylmethylchlorosilane, tolylmethylchlorosilane, allylmethylchlorosilane, 5-hexenylmethylchlorosilane, vinyl methylchlorosilane Monohalosilane selected from; Or t-butylphenylmethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethyl-n-propoxysilane, n-octadecylmethylmethoxysilane, octylmethylmethoxysilane, cyclopentylethylmethoxysilane, di A method for producing a polysilane-based compound, which is a monoalkoxysilane selected from the group consisting of cyclopentylmethoxysilane, dicyclopentylmethoxysilane, phenylmethylethoxysilane, diphenylethoxysilane, and vinylmethylethoxysilane.
9. The method of claim 1,

   The secondary silane is t-butyldichlorosilane, phenyldichlorosilane, dichlorocyclohexsilane, dichloroethylsilane, dichloromethylsilane, dichlorophenylsilane, dichlorohexylsilane, dichloro (3-phenylpropyl) silane, dichloroisopropylsilane, dichloro Dihalosilane selected from the group consisting of (4-phenylbutyl) silane, n-propyldichlorosilane, dichloroallylsilane, dichlorovinylsilane, and trichlorosilane; Or butyldimethoxysilane, dodecyl diethoxysilane, ethyl diethoxysilane, methyldimethoxysilane, methyl diethoxysilane, n-octyl diethoxysilane, octadecyldimethoxysilane, phenyl diethoxysilane, phenyldimethoxysilane, The manufacturing method of the polysilane type compound which is the dialkoxysilane chosen from the group which consists of vinyldimethoxysilane.
10. The method of claim 1,

    And said tertiary silane is a trialkoxysilane selected from the group consisting of trimethoxysilane, triethoxysilane and tri-n-propoxysilane.
11. As dehydrogenation catalyst of dehydration polymerization reaction for dehydrogenation polymerization of primary silane, secondary silane or tertiary silane to produce polysilane-based compound,

    A dehydrogenation catalyst having the following [Formula 4].

    [Formula 4]

    

    Wherein M is a metal. R ¹ , R ² , R ³ and R ⁴ are independently hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydro carbyl, or substituted heterohydro carbyl, and R ⁵ and R ⁶ are Excluding hydrogen and independently hydrocarbyl or substituted hydrocarbyl X is a halogen atom, an alkyl group of C1-C20, an arylalkyl group of C7-C30, an alkoxy group having an alkyl group of C1-C20, a C3-C20 alkylsubstituted siloxane Is selected from the group consisting of amido groups having hydrocarbon groups of C1-C20, and X on both sides of M may be the same or different.)
12. The method of claim 11,

    M in Formula 4 is an alkali metal; Alkaline earth metals; P-block metals of the periodic table;

    B block metals of the periodic table; Lanthanum series metals; Or a dehydrogenation catalyst, which is an actinide gelatinization metal.
13. The method of claim 11,

    M in Formula 4 is Co, Ni, Pd or Pt dehydrogenation catalyst.
14. The method of claim 13,

    [Chemical Formula 4] X is Cl, a dehydrogenation catalyst.
15. The method of claim 11,

    The dehydrogenation catalyst is a dehydrogenation catalyst of the catalyst cluster of the formula [4].
16. The method of claim 15,

    The cluster is a dehydrogenation catalyst is a nano cluster having a size of less than 2nm.
17. A polysilane-based compound prepared according to claim 1 as a dehydrogenated polymer of primary silane, secondary silane or tertiary silane.

    [Formula 1]

    

    Where n is an integer of at least 1, and R is_One, R₂, R₃ Are the same or different, and each hydrogen atom, halogen atom, oxygen atom, nitro group, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkaryl group, alkoxy group, alkoxycarbonyl group, carbonyloxy Groups, aminocarbonyl groups, dialkyl amino groups, derivatives thereof or they may be substituted by optional substituents. R_One, R₂, R₃May each be linear or non-linear and may optionally combine to form a ring.)
18. The method of claim 17,

    N in [Formula 1] is a polysilane-based compound of 1 ~ 119.
19. The method of claim 17,

    The compound of [Formula 1] is a polysilane-based compound in the liquid phase.
20. The method of claim 17,

    Polysilane type compound of the liquid phase of which n is 5-6 of [Formula 1].
21. The method of claim 17,

    R_One, R₂, R₃ Are each independently methyl, ethyl, propyl, propenyl, propynyl, butyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, phenyl, benzyl, naphthyl, anthracenyl, Mesityl, xylyl, tolyl, xylyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-t-butylphenyl, 4-methoxyphenyl, 4-isopropoxyphenyl, cumyl, methoxy , Ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, trimethylsilyl, dimethylhydrazyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, o-methylphenyl, o-ethyl A polysilane-based compound selected from the group consisting of phenyl, o-isopropylphenyl, ot-butylphenyl, o-methoxyphenyl, o-isopropoxyphenyl, biphenyl, naphthyl, anthracenyl.
22. A polysilane-based compound prepared according to claim 1, which is a dehydrogenated polymer of primary silane, secondary silane or tertiary silane.

    [Formula 2]

    

    (Wherein m is an integer of 1 or more, and R ₁ and R ₂ are the same or different, and each hydrogen atom, halogen atom, oxygen atom, nitro group, alkyl group, cycloalkyl group, aryl group, aralkyl group, al alkaryl group, an alkoxy group, an alkoxycarbonyl group, a carbonyl-oxy group, aminocarbonyl group, a dialkylamino group, a derivative thereof, or they may be substituted by an arbitrary substituent. R _1, R ₂ are each a linear or May be non-linear, and may optionally combine to form a ring.)
23. The method of claim 22,

    Polysilane-type compound whose m of [Formula 2] is 1-7.
24. The method of claim 22,

    The compound of [Formula 2] is a polysilane compound in the liquid phase.
25. The method of claim 22,

    Polysilane type compound of the liquid phase whose m of [Formula 2] is 2-5.
26. The method of claim 22,

    R ₁ , R ₂ are each independently methyl, ethyl, propyl, propenyl, propynyl, butyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, phenyl, benzyl, naph Tyl, anthracenyl, mesityl, xylyl, tolyl, xylyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-t-butylphenyl, 4-methoxyphenyl, 4-isopropoxyphenyl , Cumyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, trimethylsilyl, dimethylhydrazyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-isopropylcyclohexyl, o- Polysilane-based compound selected from the group consisting of methylphenyl, o-ethylphenyl, o-isopropylphenyl, ot-butylphenyl, o-methoxyphenyl, o-isopropoxyphenyl, biphenyl, naphthyl, anthracenyl.
27. A method for producing an amorphous silicon thin film using the polysilane-based compound according to any one of claims 17 to 26.
28. The method of claim 27,

    Method for producing an amorphous silicon thin film of the polysilane-based compound is a liquid compound.
29. The method of claim 28,

    A method of manufacturing an amorphous silicon thin film by applying the liquid polysilane-based compound on a substrate and heat treatment.
30. The method of claim 29,

    Method of producing an amorphous silicon thin film by performing a heat treatment while heating at 200 ~ 500 ℃.
31. The method of claim 27,

    A method of preparing an amorphous silicon thin film using a polysilane compound using a liquid and a solid compound as the polysilane compound but using a liquid polysilane compound as a solvent and dissolving a solid polysilane compound.

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