KR101530043B1 - Indium precursors with aminothiolate, preparation method thereof and process for the formation of thin films using the same - Google Patents

Abstract

(상기 식에서, R₁, R₂는 각각 독립적으로 C1-C10의 선형 또는 분지형 알킬기이고, R₃, R₄는 각각 독립적으로 C1-C10의 선형 또는 분지형의 알킬기 또는 C1-C10의 선형 또는 분지형의 플루오르화 알킬기이며, n은 1 내지 3 범위의 정수에서 선택된다.)The present invention relates to an indium precursor represented by the following general formula (1), wherein the indium precursor is a precursor containing sulfur and has an advantage that no additional sulfur is added during the manufacture of the thin film, and thermal stability and volatility are improved, An indium thin film can be formed.
[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently a C 1 -C 10 linear or branched alkyl group and R ₃ and R ₄ are each independently a C 1 -C 10 linear or branched alkyl group or a C 1 -C 10 linear or branched Branched fluorinated alkyl group, and n is selected from integers ranging from 1 to 3.)

Description

FIELD OF THE INVENTION [0001] The present invention relates to an indium precursor using aminothiourea, a method for producing the indium precursor, and a method for forming a thin film using the indium precursor using the aminothioureate,

The present invention relates to a novel indium precursor, and more particularly, to an indium precursor capable of easily producing a high quality indium sulfide thin film at a low temperature with improved thermal stability and volatility, a method for producing the indium thin film, .

Thin film solar cells using CuInSe ₂ (CIS) and CuIn _x Ga _{1 - x} Se ₂ (CIGS) thin films can be made thinner than solar cells using conventional silicon crystals and have stable characteristics even when used for a long time And it is known that a high efficiency thin film type solar cell which can replace a silicon crystalline solar cell is highly commercialized due to its high energy conversion efficiency.

CdS (CdS) thin films are mainly used as buffer layers in CIGS and CZTS thin film solar cells, but new buffer layer materials are needed due to toxicity and environmental pollution of cadmium. As the material for the buffer layer with no cadmium _{ZnS, In 2 S 3, ZnSe} , Zn (S x Se 1 -x), In x Se y, ZnIn x Se y, ZnO, Zn x Mg 1 - x O, SnO 2 , SnS ₂ , and SnS have been studied.

Chemical vapor deposition (CVD) or atomic layer deposition (ALD) is used to form the CIS, CIGS, and In ₂ S ₃ thin films.

However, when the CIS and CIGS and In ₂ S ₃ thin films are prepared by the CVD or ALD process as described above, the degree of deposition and the deposition control characteristics are determined according to the properties of the metal precursor. Therefore, indium precursors having excellent properties, The development of an indium precursor is required. For this purpose, US-A-10-2008-0102313 discloses an indium sulfide precursor using a sulfonic acid or the like, but studies on the synthesis of a specific indium sulfide precursor have been lacking. Accordingly, there is a desperate need to develop indium sulfide precursors having improved thermal stability, chemical reactivity, volatility, and deposition rate of indium metal.

U.S. Publication No. 2008-0102313 A

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel indium precursor which can improve the thermal stability and volatility and can easily produce a high quality indium sulfide thin film at a low temperature.

In order to achieve the above object, the present invention provides an indium precursor represented by the following general formula (1).

 [Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently a C 1 -C 10 linear or branched alkyl group and R ₃ and R ₄ are each independently a C 1 -C 10 linear or branched alkyl group or a C 1 -C 10 linear or branched Branched fluorinated alkyl group, and n is selected from integers ranging from 1 to 3.)

The present invention also provides a process for preparing an indium precursor represented by the above formula (1), which comprises reacting a compound represented by the following formula (2) and a compound represented by the following formula (3).

(2)

(Wherein, M is Li, Na, and K, or NH _4, R _1, R ₂ are each independently a C1-C10 linear or branched alkyl group, R _3, R ₄ is a linear C1-C10, each independently Or branched C1-C10 linear or branched fluorinated alkyl group, and n is selected from integers ranging from 1 to 3.)

(3)

InX ₃

(Wherein X is Cl, Br or I).

The present invention also provides a method for growing an indium sulfide thin film using the indium precursor of the above formula (1).

INDUSTRIAL APPLICABILITY The indium precursor represented by Formula 1 of the present invention is a precursor containing sulfur and has improved thermal stability and volatility and has an advantage that no additional sulfur is added during the manufacture of the thin film. Can be manufactured.

Figure 1 is a ¹ H NMR spectrum for In (dmampS) ₃ .
Figure 2 is TG data for In (dmampS) ₃ .

The present invention relates to an indium precursor represented by the following general formula

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently a C 1 -C 10 linear or branched alkyl group and R ₃ and R ₄ are each independently a C 1 -C 10 linear or branched alkyl group or a C 1 -C 10 linear or branched Branched fluorinated alkyl group, and n is selected from integers ranging from 1 to 3.)

Wherein R ₁ and R ₂ are independently selected from CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ , and R ₃ and R ₄ independently of one another are CH ₃ , CF ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ .

The indium precursor represented by Formula 1 according to the present invention may be represented by the following general formula In (daat) ₃ (daat = dialkylaminoalkylthiolate), and the indium precursor represented by Formula 1 may be represented by Formula 2 Can be prepared by reacting a displayed compound (M (daat)) with a compound (InX ₃ ) represented by the following formula ( ₃ ) in an organic solvent to induce a substitution reaction.

(2)

(Wherein, M is Li, Na, and K, or NH _4, R _1, R ₂ are each independently a C1-C10 linear or branched alkyl group, R _3, R ₄ is a linear C1-C10, each independently Or branched C1-C10 linear or branched fluorinated alkyl group, and n is selected from integers ranging from 1 to 3.)

(3)

InX ₃

(Wherein X is Cl, Br or I).

Wherein R ₁ and R ₂ are independently selected from CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ , and R ₃ and R ₄ are independently a _{CH 3, CF 3, C 2} H 5, CH (CH 3) is preferably used selected from ₂ and C (CH _{3) 3.}

As the reaction solvent, hexane, toluene, tetrahydrofuran and the like can be used, and toluene can be preferably used.

A specific reaction process for preparing the indium precursor of the present invention can be represented by the following reaction formula (1).

[Reaction Scheme 1]

Wherein R ₁ and R ₂ are each independently a C 1 -C 10 linear or branched alkyl group and R ₃ and R ₄ are each independently a C 1 -C 10 linear or branched alkyl group or a C 1 -C 10 linear or branched minutes, with a fluorinated alkyl group of branched, n is selected from an integer ranging from 1 to 3, X is Cl, Br or I, M is Li, Na, K or NH _4.)

According to Reaction Scheme 1, a substitution reaction is performed at room temperature for 15 hours to 24 hours using a solvent such as hexane, toluene, or tetrahydrofuran. After filtration, the filtrate is removed under reduced pressure to obtain a white solid compound. In addition, by-products may be formed in the reaction of Scheme 1, and they may be removed by sublimation or recrystallization to obtain a high-purity indium precursor.

The reactants in this reaction are used in stoichiometric equivalents.

The novel indium precursor represented by Formula 1 is a white solid which is stable at room temperature and is thermally stable and has good volatility.

When the indium sulfide thin film is grown using the indium precursor, there is an advantage that no additional sulfur is added during the thin film manufacturing process.

The novel indium precursor of the present invention is preferably used as a precursor for preparing an indium sulfide thin film, particularly a process using a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method widely used in a manufacturing process of a solar cell.

The present invention may be better understood by the following examples, which are for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Synthesis of indium precursor material

Example 1: Preparation of In (dmampS) ₃

To a 125 mL Schlenk flask was added InCl ₃ (0.7 g, 0.0032 mol, 1 eq) and Li (dmampS) (1.32 g, 0.0094 mol, 3 eq) were added. Toluene (50 mL) was added and the mixture was stirred at room temperature for 24 hours. The resulting solution was filtered, and the filtrate solvent was removed under reduced pressure to obtain a white solid compound (1.29 g, yield 80%). Subsequently, sublimation was carried out at 80 ° C (10 ^-2 Torr) in order to purify it.

¹ H-NMR (C ₆ D ₆ ) of the obtained compound is shown in FIG.

¹ H NMR (C ₆ D ₆ , 300 MHz):? 2.34 (s, 8H), 1.56 (s, 6H)

. EA: Calcd (Found) for C 18 H 42 N 3 S 3 In: C, 42.26 (41.23); H, 8.28 (8.31);

                                  N, 8.21 (7.82); S, 18.80 (19.58).

^{FT-IR (KBr, cm -1} ): 2960 (s), 1450 (s), 1360 (m), 1310 (m), 1020 (s), 1030 (s), 831 (s), 646 (w) , 604 (w), 550 (w), 457 (w).

EI-MS, m / e (%): 511

Analysis of indium precursor materials

Thermogravimetric analysis (TGA) was used to measure the thermal stability, volatility and decomposition temperature of the indium precursor compound synthesized in Example 1 above. In the TGA method, argon gas was introduced at a pressure of 1.5 bar / min while warming the product to 900 ° C at a rate of 10 ° C / minute. A TGA graph of the indium precursor compound synthesized in Example 1 is shown in Fig. The indium precursor compound obtained in Example 1 showed a mass reduction at around 200 ° C and a mass reduction of more than 60% at 300 ° C. Through this, it was confirmed that the TG graph T _1/2 is 280 ℃.

Claims (5)

An indium precursor represented by the following general formula (1)
[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently a C 1 -C 10 linear or branched alkyl group and R ₃ and R ₄ are each independently a C 1 -C 10 linear or branched alkyl group or a C 1 -C 10 linear or branched Branched fluorinated alkyl group, and n is selected from integers ranging from 1 to 3.) The method according to claim 1,
Wherein R ₁ and R ₂ are independently selected from CH ₃ , C ₂ H ₅ , CH (CH ₃ ) ₂ and C (CH ₃ ) ₃ , and R ₃ and R ₄ independently of one another are CH ₃ , CF ₃ , C ₂ H ₅ , CH (CH ₃ ) _2, and C (CH ₃ ) ₃ . A process for producing an indium precursor represented by the general formula (1), comprising reacting a compound represented by the following general formula (2) and a compound represented by the following general formula (3)
(2)

(Wherein, M is Li, Na, and K, or NH _4, R _1, R ₂ are each independently a C1-C10 linear or branched alkyl group, R _3, R ₄ is a linear C1-C10, each independently Or branched C1-C10 linear or branched fluorinated alkyl group, and n is selected from integers ranging from 1 to 3.)
(3)
InX ₃
(Wherein X is Cl, Br or I). A method of growing an indium sulfide thin film using the indium precursor of claim 1. The method of claim 4,
Wherein the thin film growth process is performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

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