KR100541939B1 - Precursor for preparing a chalcogenide thin-film in the chemical vapor deposition method, and the preparing the same - Google Patents

Abstract

The present invention relates to a precursor which is an organometallic compound represented by the following formula (1) which can be usefully used in the preparation of a chalcogenide thin film by chemical vapor deposition (hereinafter referred to as CVD), and more particularly, The precursor of Formula 1 is used to provide a chalcogenide thin film having a 1: 1 composition of a metal and a chalcogen element at low temperature.

(Wherein, M is In and Ga, E is a chalcogen element (S, Se); R, R ₁ each independently represent an alkyl group of C1 ~ C6.)

Chalcogenide * Thin film * Chemical vapor deposition * Precursor

Description

Precursor for preparing a chalcogenide thin-film in the chemical vapor deposition method, and the preparing the same

The present invention relates to a precursor which is an organometallic compound represented by the following formula (1) which can be usefully used in the preparation of a chalcogenide thin film by chemical vapor deposition (hereinafter referred to as CVD), and more particularly, The precursor of Formula 1 is used to provide a chalcogenide thin film having a 1: 1 composition of a metal and a chalcogen element at low temperature.

[Formula 1]

(Wherein, M is In and Ga, E is a chalcogen element (S, Se); R, R ₁ each independently represent an alkyl group of C1 ~ C6.)

Chalcogenide refers to a compound composed of sulfur (S), selenium (Se) and tellurium (Te) among elements belonging to group 6B of the periodic table, and typically zinc sulfide (ZnS) and indium selenide. (InSe, In ₂ Se ₃ ), cadmium telluride (CdTe), CuInSe ₂ (hereinafter referred to as CIS), and the like. The chalcogenide is a core material used for magneto-optical memory devices, n-type or p-type semiconductors, solar cells, and the like, and various thin film processes are being developed to manufacture high quality thin films with few defects.

In particular, cadmium telluride (CdTe) and CIS (CuInSe ₂ ), which have been attracting attention since the early 1990s, are new material chalcogenides used in the light absorption layer, which is a key element of solar cells, called green energy. ), Solar cell efficiency using CIS (CuInSe ₂ ) is more than 15%, showing superior performance compared to conventional amorphous silicon materials, and many researches are underway. Above all, thin film manufacturing technology of chalcogenide It is becoming the core technology of the process.

In manufacturing a conventional thin film of chalcogenide can be vaporized at a high temperature unlike other elements due to the characteristics of the chalcogenide it could be thinned using an evaporation method (evaporation) at a high temperature. However, the above evaporation method can easily produce a thin film, but the vapor pressure of the metal and chalcogen element is different, the volatilization temperature of the chalcogen element (sulfur (S) = 444.67 ℃, selenium (Se) = 684.9 ℃, tellurium) (Te) = 989.9 ° C.) It is also almost impossible to obtain a high quality thin film having a high composition.

Therefore, using a physical vapor deposition method (PVD) used in the Republic of Korea Patent Publication No. 2002-0059162 as a recent improved thin film manufacturing method to prepare _a thin film of chalcogenide of various compositions such as (Ge _a Bi _b Sb _c ) Te _X The manufacturing method is described, and in addition, the solution growth method using a conventional chemical method (CBD; Chemical Bath Deposition, Korean Patent No. 10-0220371, CdS thin film production) and the electrodeposition method, which is a kind of plating method using electrochemistry, U. S. Patent No. 6,036, 822, U. S. Patent No. 5, 772, 431) and the like have been reported as thin film manufacturing techniques of various chalcogenides. In addition, in the preparation of a new material CIS (CuInSe ₂ ) thin film used as a solar cell light absorption layer in the chalcogenide, by improving the evaporation method using the volatility at a high temperature in the prior art at the same time under the vacuum method to produce a thin film in an easier process Many studies have been performed, such as Vapor Evaporation Deposition, which evaporates and thins (US Pat. No. 4,523,051, US Pat. No. 5,045,409). In addition, recently, a vacuum evaporation method using a binary material that can be easily controlled by directly evaporating the synthesized binary compound has been reported (Korean Patent Laid-Open Publication No. 2002-0007777, CuInSe ₂ thin film production).

As mentioned above, the thin film manufacturing method can be classified into two types, and physical methods using phase deformation, such as physical vapor deposition (PVD) and vacuum evaporation, are accompanied by chemical reactions such as solution growth and electrodeposition. It can be distinguished by chemical methods. However, both methods require various condition factors during the process to provide a chalcogenide thin film having a specific composition ratio. For example, complex factors such as matching the vapor pressure and maintaining the concentration ratio of the solution are required. In addition, the above-mentioned thinning method has advantages in that the manufacturing cost is relatively low and the manufacturing equipment is simple, but it is difficult to control the composition due to the characteristics of the chalcogenide, and it is difficult to see the reproducibility of the thickness and uniformity of the thin film. In particular, in the vacuum evaporation method, most chalcogen elements have a high volatilization point and must be deposited at high temperature and high pressure. Since the volatilization points of the respective elements are also different, the difficulty of depositing a desired composition greatly increases. In addition, there are many disadvantages such as the need for a post-process of heat treatment at a high temperature for replenishment of loss elements and phase formation after deposition (US Pat. No. 6,323,417).

Therefore, many studies have been conducted to solve the above problems, and a representative method is chemical vapor deposition (CVD). Chemical vapor deposition (CVD) has the advantage of uniform and selective deposition of the manufactured thin films, and if a precursor having a constant composition is used, a single composition thin film can be provided reproducibly through an easy process. It is widely used in manufacturing processes. The chemical vapor deposition method requires a precursor having sublimation characteristics while achieving a specific composition ratio of a metal and a chalcogen element. In this study, TiS ₂ thin films were prepared in US Pat. No. 5,112,650. In the US Pat. Nos. 5,837,320, thiocarboxylate groups were formed on divalent metals (Ca, Sr, Ba, Zn, Cd, Pb, Ga, In, Sb, Bi). Introduced a sphere for the production of metal sulfide (Metal-S) thin film. However, existing organometallic precursors are limited to the manufacture of thin films of metal sulfides and limited to specific applications.

To solve this problem, a single organometallic precursor for chemical vapor deposition of chalcogenides, in which all components have a specific composition ratio, forms a chemical complex using a specific metal and a chalcogen element (S, Se, Te) in a constant composition ratio. It should be able to form a phase of chalcogenide after decomposition because it needs to have proper volatilization at low temperature, relatively low decomposition temperature, and relatively stable to heat during vaporization. Recently, such a study has reported a single organometallic precursor (US Pat. No. 5,300,320) in which a chalcogen element is introduced using a tertiary butyl group in gallium (Ga), aluminum (Al), and indium (In) metal. In the preparation of chalcogenide thin films requiring various components and compositions, there are still many limitations in the selection of metals, and in the preparation of chalcogenides composed of multiple metals, they still have a composition lacking S or Se, which is a highly volatile element such as evaporation. There is a problem that becomes.

Accordingly, the inventors of the present invention have studied a variety of metal chalcogenide precursor compounds composed of a constant composition ratio of metal and chalcogen elements and capable of chemical vapor deposition at a low temperature in order to solve the above problems, the precursor having the structure of Formula 1 The synthesis was found to be able to prepare a chalcogenide thin film having a composition of a metal of the ME (M: metal, E: chalcogen element) structure and a chalcogen element of 1: 1, thereby completing the present invention.

Accordingly, an object of the present invention is to provide a precursor of Chemical Formula 1, which is useful for producing a chalcogenide thin film having a composition of 1: 1 of a metal and a chalcogenide by chemical vapor deposition.

Another object of the present invention is to provide a method for producing the precursor.

In order to achieve the above object, the precursor for preparing a chalcogenide thin film by the chemical vapor deposition method of the present invention is characterized in that the organometallic compound represented by the following formula (1).

[Formula 1]

(Wherein, M is In and Ga, E is a chalcogen element (S, Se); R, R ₁ each independently represent an alkyl group of C1 ~ C6.)

Hereinafter, the present invention will be described in more detail.

The precursor represented by Formula 1 of the present invention can be synthesized largely by two methods.

(1) a synthesis method using as a starting material a chalcogenol (R ₁ -EH, E is a chalcogen element, R ₁ is an alkyl group) in the alcohol form of an alkylated metal and a chalcogen element; And (2) a dialkyldicalcogen (R ₁ -EER _1, E is a chalcogen element, R ₁ is an alkyl group) as a starting method.

Hereinafter, the method for synthesizing the precursor of the present invention will be described in detail step by step.

First, the synthesis method 1 is demonstrated.

Synthesis Method 1

Synthesis method (1) of the compound of formula (I) using as a starting material a chalcogenol (R ₁ -EH, E is a chalcogen element, R ₁ is an alkyl group) which is an alcoholic form of an alkylated metal and a chalcogen element represented by the following Scheme 1 ,

First, dissolving 1 equivalent of chalcogenol in a purified solvent; Mixing the solution with 1 equivalent of an alkylated metal (MR) using a shrink line; Reacting the mixed solution with stirring at 4 ° C. in an argon atmosphere for 3-4 hours; And removing the solvent and separating and purifying the insoluble polymer to prepare the compound of Chemical Formula 1.

(Wherein, M, E, R, and R ₁ are the same as defined in the formula (1).)

The chalcogenol is thiol or selenol, and the solvent is specifically tetrahydrofuran (THF), ester, pentane, or methylene chloride.

Next, the synthesis method 2 is demonstrated.

Synthesis Method 2

Synthesis method (2) of the compound of Formula 1 as a starting material using a dialkyldichalcogen represented by the following Scheme 2 (R ₁ -EER _1, E is a chalcogen element, R ₁ is an alkyl group),

First, the metallized alkylation (MR) quantified in the glove box is placed in a flask and pentane, which is a solvent, is added at a temperature of 0 ° C. using a shrink line, and then dialkyldisulfide ((R ₁ ) is used with a cannula. E) injecting ₂ ; CH ₃ S-SCH ₃ ) or dialkyldiselenide ((R ₁ E) ₂ ; CH ₃ SeSeCH ₃ ); Reacting the mixed solution while stirring at room temperature for 12 hours; And separating and purifying the unreacted material and the solvent to prepare a compound of Chemical Formula 1.

(Wherein, M, E, R, and R ₁ are the same as defined in the formula (1).)

Compounds synthesized by Scheme 1 or 2 are analyzed by nuclear magnetic resonance analysis (NMR, ¹ H, ¹³ C), infrared spectroscopy (IR) and mass spectrometer.

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited only to these examples.

Example 1 Synthesis of [Me ₂ In (μ-SC (CH ₃ ) ₃ )] ₂

2-methyl-2-propanethiol (6.25 mmol, 0.564 g) was dissolved in 70 ml of secondary purified tetrahydrafuran (THF), a common solvent, and then trimethylindium (6.25 mmol) was used using a Schrinline. , 1.020 g). Next, the mixed solution was reacted under stirring at 0 ° C. in an argon atmosphere for 3 to 4 hours, and then the solvent was removed and the insoluble polymer was separated and purified to obtain a white solid [Me ₂ In (μ-SC (CH ₃ ) ₃ ). ] ₂ compound was synthesized. The compound was identified by nuclear magnetic resonance analysis (NMR, ¹ H, ¹³ C), infrared spectroscopy (IR) and mass spectrometry.

Example 2 Synthesis of [Me ₂ In (μ-SCH (CH ₃ ) CH ₂ CH ₃ )] ₂

Butane 2-thiol (6.25 mmol, 0.564 g) was dissolved in 70 ml of secondary purified methylene chloride, a common solvent, and then mixed with trimethylindium (6.25 mmol) using a Schhrlein. Next, the mixed solution was reacted under stirring at 0 ° C. in an argon atmosphere for 3-4 hours, and then the solvent was removed and the insoluble polymer was separated and purified to obtain a viscous colorless liquid [Me ₂ In (μ-SCH (CH _3). ) CH ₂ CH ₃ )] ₂ compound was synthesized. Synthesized compounds were identified by nuclear magnetic resonance analysis (NMR, ¹ H, ¹³ C), infrared spectroscopy (IR) and mass spectrometry.

Example 3 Synthesis of [Me ₂ In (μ-SC (CH ₃ ) ₂ CH ₂ CH ₃ )] ₂

2-methylbutane 2-thiol (6.25 mmol, 0.651 g) was dissolved in 70 ml of secondary purified tetrahydrafuran (THF), a common solvent, and then trimethylindium (6.25 mmol) was obtained using a shrink line. Mixed in. Next, the mixed solution was reacted under stirring at 0 ° C. in an argon atmosphere for 3 to 4 hours, and then the solvent was removed and the insoluble polymer was separated and purified to give a viscous colorless liquid [Me ₂ In (μ-SC (CH ₃ ) ₂ CH ₂ CH ₃ )] ₂ compound was synthesized. Synthesized compounds were identified by nuclear magnetic resonance analysis (NMR, ¹ H, ¹³ C), infrared spectroscopy (IR) and mass spectrometry.

Example 4 Synthesis of [Me ₂ In (μ-SC ₆ H ₅ )] ₂

Synthesis was carried out in the same manner as in Example 1, except that benzenethiol (6.25 mmol, 0.689 g) was used instead of methyl thiol.

[Example _{5] [Me 2 In (μ} -SCH (CH 3) 2] 2 : Synthesis of

Synthesis was carried out in the same manner as in Example 1, except that propane 2-thiol (6.25 mmol, 0.476 g) was used instead of methyl thiol.

[Example _{6] [Me 2 In (μ} -SCH 2 CH (CH 3) 2] 2 : Synthesis of

Synthesis was carried out in the same manner as in Example 1, except that 2-methyl-1-propanethiol (6.25 mmol, 0.546 g) was used instead of 2-methyl-2-propanethiol.

Example 7 Synthesis of [Me ₂ In (μ-SeC ₆ H ₅ )] ₂

Benzene selenol (6.25 mmol, 0.982 g) was dissolved in 70 ml of secondary purified tetrahydrafuran (THF), which was a common solvent, and then mixed with trimethylindium (6.25 mmol) using a Schhrinkline. Next, the mixed solution was stirred for 3 to 4 hours in an argon atmosphere at 0 ° C., and then the solvent was removed and the insoluble polymer was separated and purified to obtain a white solid [Me ₂ In (μ-SeC ₆ H ₅ )] ₂ Compounds were synthesized. Synthesized compounds were identified by nuclear magnetic resonance analysis (NMR, ¹ H, ¹³ C), infrared spectroscopy (IR) and mass spectrometry.

Example 8 Synthesis of Me ₂ Ga (μ-SC (CH ₃ ) ₃ )] ₂

2-methyl-2-propanethiol (6.25 mmol, 0.564 g) was dissolved in 70 ml of secondary purified tetrahydrafuran (THF), a common solvent, and then trimethylgallium (6.25 mmol) was used using a shrink line. , 0.723 g). Next, the mixed solution was reacted under stirring at 0 ° C. in an argon atmosphere for 3 to 4 hours, and then the solvent was removed and the insoluble polymer was separated and purified to obtain a white solid Me ₂ Ga (μ-SC (CH ₃ ) ₃ )]. ₂ compounds were synthesized. Synthesized compounds were identified by nuclear magnetic resonance analysis (NMR, ¹ H, ¹³ C), infrared spectroscopy (IR) and mass spectrometry.

Example 9 Synthesis of [Me ₂ Ga (μ-SCH (CH ₃ ) CH ₂ CH ₃ )] ₂

Butane 2-thiol (6.25 mmol, 0.564 g) was dissolved in 70 ml of secondary purified methylene chloride, a common solvent, and then mixed with trimethylgallium (6.25 mmol) using a Schhrlein. Next, the mixed solution was reacted under stirring at 0 ° C. in an argon atmosphere for 3-4 hours, and then the solvent was removed and the insoluble polymer was separated and purified to obtain a viscous colorless liquid [Me ₂ Ga (μ-SCH (CH _3). ) CH ₂ CH ₃ )] ₂ compound was synthesized. Synthesized compounds were identified by nuclear magnetic resonance analysis (NMR, ¹ H, ¹³ C), infrared spectroscopy (IR) and mass spectrometry.

Example 10 Synthesis of [Me ₂ Ga (μ-SC (CH ₃ ) ₂ CH ₂ CH ₃ )] ₂

Synthesis was carried out in the same manner as in Example 8, except that 2-methyl-2-butanethiol (6.25 mmol, 0.651 g) was used instead of 2-methyl-2-propanethiol.

Example 11 Synthesis of [Me ₂ Ga (μ-SC ₆ H ₅ )] ₂

Synthesis was carried out in the same manner as in Example 8, except that benzenethiol (6.25 mmol, 0.689 g) was used instead of 2-methyl-2-propanethiol.

Example 12 Synthesis of [Me ₂ Ga (μ-SCH (CH ₃ )] ₂

Synthesis was carried out in the same manner as in Example 8, except that propane 2-thiol (6.25 mmol, 0.476 g) was used instead of 2-methyl-2-propanethiol.

[Example _{13] [Me 2 Ga (μ} -SCH 2 CH (CH 3) 2] 2 : Synthesis of

Synthesis was carried out in the same manner as in Example 8, except that 2-methyl-1-propanethiol (6.25 mmol, 0.564 g) was used instead of 2-methyl-2-propanethiol.

Example 14 Synthesis of [Me ₂ Ga (μ-SeC ₆ H ₅ )] ₂

Benzene selenol (6.25 mmol, 0.982 g) was dissolved in 70 ml of secondary purified tetrahydrofuran (THF), which was a common solvent, and then mixed with trimethylgallium (6.25 mmol) using a Schrinline. Next, the mixed solution was reacted under stirring at 3 ° C. in an argon atmosphere at 0 ° C. for 3 hours, and then the solvent was removed and the insoluble polymer was separated and purified to obtain a white solid [Me ₂ Ga (μ-SeC ₆ H ₅ )] ₂ Compounds were synthesized. The synthesized compound was confirmed by nuclear magnetic resonance analysis (NMR, ¹ H, ¹³ C), infrared spectroscopy (IR) and mass spectrometry.

Examples 1 to 14 prepared by the method of Synthesis Method 1 are shown in Table 1 below.

Example 15 Synthesis of [Me ₂ In (μ-SeCH ₃ )] ₂

In a glove box, trimethylindium (6.25 mmol, 1.020 g) was added to the flask, and 70 ml of pentane, a solvent, was added at a temperature of 0 ° C. using a shrink line, followed by dimethyl diselen using cannula. A solution in which Nide (6.25 mmol, 1.175 g) was dissolved in 70 ml of pentane was injected. Next, the mixed solution was reacted with stirring at room temperature for 12 hours. Thereafter, the unreacted substance and the solvent were separated and purified to synthesize a white solid [Me ₂ In (μ-SeCH ₃ )] ₂ compound. The synthesized compounds were analyzed by nuclear magnetic resonance analysis (NMR, ¹ H, ¹³ C), infrared spectroscopy (IR) and mass spectrometry.

Example 16 Synthesis of [Me ₂ Ga (μ-SeCH ₃ )] ₂

In a glove box, trimethylgallium (6.25 mmol, 0.723 g) was added to a flask, and pentane, a solvent, was added at a temperature of 0 ° C. using a shrink line, followed by dimethyl diselenide (6.25) using cannula. mmol, 1.175 g) was poured into a solution of 70 ml of pentane. Next, the mixed solution was reacted with stirring at room temperature for 12 hours. Thereafter, the unreacted material and the solvent were separated and purified to synthesize a white solid [Me ₂ Ga (μ-SeCH ₃ )] ₂ compound. The synthesized compounds were analyzed by nuclear magnetic resonance analysis (NMR, ¹ H, ¹³ C), infrared spectroscopy (IR) and mass spectrometry.

Examples 15 to 16 prepared by the method of Synthesis Method 2 are shown in Table 2 below.

Example               A physical compound shape ¹ H-NMR (ppm) ¹³ C-NMR (ppm) IR (cm ^-1 ) Mass (m / z) 15 [Me ₂ In (μ-SeCH ₃ )] ₂ White solid 0.117 [In- CH ₃ (s)] 2.052 [Se- CH ₃ (s)] -1.700 [In- CH ₃ ] 0.053 [Se- CH ₃ ] 2920 ~ 2980 [ν (sp3C-H)] 1428, 1280, 900 [Se-CH ₃ ] 1158 [In-CH ₃ ] 680 ~ 720 [In-CH ₃ rock] 481, 521 [ν (In-C)] 463 16 0.083 [Ga- CH ₃ (s)] 1.984 [Se- CH ₃ (s)] -0.148 [Ga- CH ₃ ] 10.482 [Se- CH ₃ ] 2825 ~ 2960 [ν (sp3C-H)] 1430, 1278, 920 [Se-CH ₃ ] 1205 [Ga-CH ₃ ] 720 ~ 760 [Ga-CH ₃ rock] 540, 580 [ν (Ga-C)] 388 [Me ₂ Ga (μ-SeCH ₃ )] ₂ White solid

[Manufacture example 1-16]

Using the above Examples 1 to 16 as a precursor to prepare a thin film by a CVD vacuum deposition apparatus. The CVD deposition apparatus was deposited while keeping the bubbler temperature of the precursor at 80 ° C. under an argon atmosphere, and changing the deposition substrate temperature to 250˜370 ° C. At this time, the CVD chamber was decompressed 20mtorr, to prepare a thin film of 100 ~ 500nm thickness over 3 hours. In each case, the prepared thin film was confirmed to form a high purity chalcogenide single phase thin film without impurities through X-Ray Diffraction (XRD), and the chalcogen having a grain size of 300-500 nm was obtained through an electron microscope. It was confirmed that a cargo thin film was prepared. In addition, the melting point and decomposition temperature of the precursor at atmospheric pressure were measured by a thermal analyzer. The results are shown in Table 3 below, and the phase change seen as a sublimation between the melting point and the decomposition temperature was confirmed. Based on this, the temperature of the precursor was deposited at about 80 to 100 ° C.

Production Example   Precursor type                     A physical compound Melting point (℃) Decomposition Temperature (℃) M / E composition analysis result after CVD deposition (M / E composition ratio) One Example 1 [Me ₂ In (μ-SC (CH ₃ ) ₃ )] ₂ 87 182  In / S = 1.02 2 Example 2 [Me ₂ In (μ-SCH (CH ₃ ) CH ₂ CH ₃ )] ₂ - 236  In / S = 1.05 3 Example 3 [Me ₂ In (μ-SC (CH ₃ ) ₂ CH ₂ CH ₃ )] ₂ - 207  In / S = 1.13 4 Example 4 [Me ₂ In (μ-SC ₆ H ₅ )] ₂ 115 237  In / S = 1.04 5 Example 5 [Me ₂ In (μ-SCH (CH ₃ ) ₂ ] ₂ 41 182  In / S = 1.10 6 Example 6 [Me ₂ In (μ-SCH ₂ CH (CH ₃ ) ₂ ] ₂ 68 204  In / S = 1.01 7 Example 7 [Me ₂ In (μ-SeC ₆ H ₅ )] ₂ 131 186  In / Se = 1.10 8 Example 8 [Me ₂ Ga (μ-SC (CH ₃ ) ₃ )] ₂ 52 211  Ga / S = 1.02 9 Example 9 [Me ₂ Ga (μ-SCH (CH ₃ ) CH ₂ CH ₃ )] ₂ - 277  Ga / S = 1.11 10 Example 10 [Me ₂ Ga (μ-SC (CH ₃ ) ₂ CH ₂ CH ₃ )] ₂ - 201  Ga / S = 1.08 11 Example 11 [Me ₂ Ga (μ-SC ₆ H ₅ )] ₂ 132 272  Ga / S = 1.02 12 Example 12 [Me ₂ Ga (μ-SCH (CH ₃ ) ₂ ] ₂ - na  Ga / S = 1.05 13 Example 13 [Me ₂ Ga (μ-SCH ₂ CH (CH ₃ ) ₂ ] ₂ na na  Ga / S = 1.10 14 Example 14 [Me ₂ Ga (μ-SeC ₆ H ₅ )] ₂ 122 248  Ga / Se = 1.03 15 Example 15 [Me ₂ In (μ-SeCH ₃ )] ₂ 154 185  In / Se = 1.01 16 Example 16 [Me ₂ Ga (μ-SeCH ₃ )] ₂ 112 135  Ga / Se = 1.01

As can be seen in Table 3, the chalcogenide organometallic precursors synthesized with the new skeletons of Examples 1 to 16 have volatilization characteristics at low temperatures and well meet typical properties of precursors requiring relatively low decomposition temperatures. It was confirmed that. In particular, as the composition ratio of the most important metal and the chalcogenide element can be seen through XPS (Xray Photoelectron Spectroscopy), the composition ratio of the metal / chalcogen element was found to be very constant, 1.01 to 1.11, indicating that the thin film was prepared. Therefore, it was confirmed that the precursor of the new skeleton prepared in the present invention is an excellent precursor for the preparation of chalcogenide (chalcogenide, ME M: metal, E: chalcogen element) thin film having a composition ratio of metal to chalcogen element 1: 1. .

As described above, the present invention provides a method for synthesizing a binary compound precursor as a previous step for the production of a light-absorbing thin film layer of a solar cell using a chemical vapor deposition method, the chalcogenide precursor prepared in this manner is a variety of A single-phase high purity chalcogenide (chalcogenide, ME M: metal, E: chalcogen element) thin film having a metal and chalcogen element composition of 1: 1 can be provided.

Claims (5)

delete Dissolving 1 equivalent of chalcogenol in a purified solvent; Mixing the solution with 1 equivalent of an alkylated metal (MR) using a shrink line; Reacting the mixed solution with stirring at 4 ° C. in an argon atmosphere for 3-4 hours; And Removing solvent and separating and purifying insoluble polymer; Method of preparing a precursor for chemical vapor deposition for the preparation of chalcogenide (chalcogenide) thin film represented by the following formula (1) by the step of Scheme 1 comprising a. [Formula 1]

(Wherein, M is In and Ga, E is a chalcogen element (S, Se); R, R ₁ each independently represent an alkyl group of C1 ~ C6.) Scheme 1

(Wherein, M is In and Ga, E is a chalcogen element (S, Se); R, R ₁ each independently represent an alkyl group of C1 ~ C6.) Put the metal alkylated (MR) quantified in the glove box into the flask and put pentane as a solvent while maintaining the 0 ℃ using a shrink line, and then dialkyl disulfide ((R ₁ E) using a cannula (cannula) Injecting ₂ ; CH ₃ S-SCH ₃ ) or dialkyldiselenide ((R ₁ E) ₂ ; CH ₃ SeSeCH ₃ ); Reacting the mixed solution while stirring at room temperature for 12 hours; And Separating and purifying the unreacted material and the solvent; Method of producing a precursor for chemical vapor deposition for the preparation of chalcogenide (chalcogenide) thin film represented by the following formula (1) by the step of Scheme 2 comprising a. [Formula 1]

(Wherein, M is In and Ga, E is a chalcogen element (S, Se); R, R ₁ each independently represent an alkyl group of C1 ~ C6.) Scheme 2

(Wherein, M, E, R, and R ₁ are the same as defined in the formula (1).) According to claim 2, wherein the chalcogenol is a thiol or selenol (selenol) method of producing a precursor for chemical vapor deposition for the chalcogenide (chalcogenide) thin film. The method of claim 2, wherein the solvent is tetrahydrofuran (THF), ester, pentane, or methylene chloride, characterized in that the method for producing a chemical vapor deposition precursor for a chalcogenide (chalcogenide) thin film.