WO2014092414A1

WO2014092414A1 - Indium-zinc-oxide semiconductor ink composition in which a spontaneous combustion reaction occurs, and inorganic semiconductor thin film produced thereby

Info

Publication number: WO2014092414A1
Application number: PCT/KR2013/011357
Authority: WO
Inventors: 조성윤; 이창진; 강영훈
Original assignee: 한국화학연구원
Priority date: 2012-12-14
Filing date: 2013-12-09
Publication date: 2014-06-19

Abstract

The aim of the present invention is to provide an indium-zinc-oxide semiconductor ink composition in which a spontaneous combustion reaction occurs, and provide an inorganic semiconductor thin film produced thereby. To this end, the present invention provides a semiconductor ink composition which comprises a complex, represented by formula 1, incorporating a nitrate of a metal A which is an oxidising material and incorporating a metal B which is a fuel material; wherein the metal A and the metal B is each respectively a metal selected from the group consisting of indium, gallium, zinc, titanium, aluminium, lithium and zirconium, and metal A and metal B are different from each other. According to the present invention, the indium-zinc-oxide semiconductor ink composition in which a spontaneous combustion reaction occurs, and the inorganic semiconductor thin film produced thereby, can be used as the channel material of a transistor element, and consequently can produce inorganic thin film transistors having improved electrical performance. Also, the present invention is suitable for solution processing and so is easy to produce as a thin film and capable of low temperature processing, and can produce thin films which are dense and uniform due to a spontaneous combustion reaction that occurs on mixing two metal precursors coordinated with a fuel material and an oxidising material.

Description

【Specification】

[Name of invention]

Sintered zinc oxide based semiconductor ink composition and spontaneous combustion reaction and inorganic semiconductor thin film produced therefrom

Technical Field

The present invention relates to an indium zinc oxide-based semiconductor ink composition in which spontaneous combustion reaction occurs and an inorganic semiconductor thin film prepared through the same.

<2>

Background Art

Recently, a lot of research has been conducted with increasing interest in various characteristics of oxide semiconductors. In particular, the oxide semiconductor is being applied to the active layer of the thin-film transistor (TFT), The use inorganic oxide semiconductor include zinc oxide (ZnO), of rhodium, indium oxide zinc oxide (IZ0), oxidation indeum gallium zinc ^■ (IGZ0) , Indium tin zinc oxide (IZT0) and so on. These oxide semiconductors have a relatively large bend gap of 3 eV or more due to the characteristics of oxide chemical bonds, so they are transparent in the visible region, grow at low temperatures, and can be used at a relatively low cost, and have high mobility. There is an advantage to get.

<4>

The thin film transistor element is a key component required in display information devices, and is essential for displaying a pixel gray level of the display information device by switching one pixel (pi _xe i). It forms a big market in the electronic information industry. Currently, oxide semiconductors are widely used in vacuum-based equipment such as sputtering, atomic layer deposition (ALD), spread laser deposition (PLD), and organometallic chemical vapor deposition (M0CVD).

<6>

However, in recent years, as electronic products such as display devices form a low price point, the electronic information industry in recent years is required to have ultra-low cost and large area processes and mass production. Therefore, there is a need to develop a solution-based process to replace the exposure or vacuum deposition process that involves a high process cost. In the manufacture of thin film transistor devices using such a solution-based process, many studies have been conducted based on organic semiconductors. Many problems remain to be solved in terms of durability and electrical reliability. <8>

On the other hand, a new trend toward the fabrication of inorganic oxide semiconductors by using the solution process has begun, which has been applied to various materials such as indium oxide, tin oxide (IT0), zinc oxide film with aluminum and gallium. Research has been actively conducted to develop low temperature processes. Solution processes include sol-gel, organometallic decomposition (MOD), chemical bath (CBD), and the like.

The sol-gel method, which is mainly used in the production of inorganic oxide semiconductors, is applied to a substrate by spin coating or inkjet printing with a metal precursor solution having a suitable _P H and then thermally treated. During the heat treatment, the inorganic precursor undergoes hydrolysis and condensation reactions, and forms metal oxides due to the combination of metal and oxygen generated from these reactions. In general, inorganic precursors include metal alkoxides, metal acetates, metal nitrides, metal halides, and the like.

<ιι> However, the sol-gel oxide semiconductor process temperature is still relatively high to achieve good electrical properties. It is reported that the temperature of the heat treatment process is required to be higher than 300 ^° C for ZnO and higher than 400 ^° C for IZ0 and 450 ^° C for IGZ0. (Adv. Mater. 2012, 24, 2945)

<12>

Many studies have been reported to solve the disadvantages of the heat treatment process of the inorganic semiconductor material. According to the research of Shrringhaus et al., The mobility was heat treated ^at 275 ^° C using indium gallium and zinc alkoxide precursors in a glove box, which is a nitrogen atmosphere, to obtain a mobility of ~ 10 cm ^ s ¹ . According to the present invention, the mobility of ~ 10 cmVV ¹ can be obtained on the aluminum oxide insulator substrate through deep-UV exposure and heat treatment ^at 200 ^° C using ingots, gallium, zinc acetate and nitrate precursors in a nitrogen atmosphere box. 2011, 10, 45., Nature Lett. 2012, 489, 128).

However, such methods are not necessarily experimentally reproduced without a nitrogen atmosphere, special equipment, or high-k gate insulators, and thus there is a problem in that industrial applications may be impaired in practical terms.

<15>

<i6> Marks et al. recently found that indium and zinc nitrate precursors Fee (fuel) material is a urea (Urea) and oxide (oxidizer) material is ammonium nitrate (NH ₄ N0 ₃₎ was added to the final compound of a metal precursor composition that can take advantage of a combustion banung (combustion reaction), by using this, 300 ^° A mobility of 3 cmV ¹ was obtained with the heat treatment of C. Although high mobility was obtained in the low temperature process by using the combustion reaction, fuel material, oxidizing material and base solution column should be added in addition to the metal oxide precursor, and it is difficult to reproduce without quantitative addition (J. Am. Chem Soc. 2012, 134, 9593, Nature Mater. 2011, 10, 382, J. Am. Chem. Soc. 2012, 134, 11583).

<17>

Therefore, the present inventors found a metal precursor coordination of fuel material and oxidizing material while studying a method of manufacturing a zinc oxide semiconductor thin film showing excellent properties, and by mixing the two metal precursors without any additional additives, An inorganic semiconductor ink composition capable of manufacturing an indium zinc oxide semiconductor thin film having improved charge mobility and flicker ratio characteristics was developed, and the present invention was completed.

<19>

[Detailed Description of the Invention]

[Technical problem]

An object of the present invention is to provide a sulphate zinc oxide-based semiconductor ink composition in which a spontaneous combustion reaction occurs and an inorganic semiconductor thin film manufactured through the same.

<21>

Technical Solution

To this end, the present invention

Nitrides of metal A as an oxidizing material;

<24> contains a complex represented by Formula 1 of metal B as a fuel material,

The metal A and the metal B are each one metal selected from the group consisting of indium, gallium, zinc, titanium, aluminum, lithium, and zirconium, and the metal A and the metal B are different from each other. To provide a composition.

<26> [Formula 1]

<28>

(Wherein R ₂ and ¾ are each independently hydrogen or d to C ₂ alkyl, wherein ^ to C ₂ alkyl may be substituted with one or more F).

<30>

In addition, the present invention

(32) preparing a film by printing or coating the inorganic semiconductor ink composition on the substrate; And

It provides a method for producing a semiconductor thin film using a semiconductor ink composition comprising the step (step 2) of heat-treating the film prepared in step 1.

<34>

In addition, the present invention

The above manufacturing method provides a semiconductor thin film formed on the substrate.

<37>

Furthermore, the present invention

A substrate (gate electrode) and a semiconductor thin film manufactured by the manufacturing method are sequentially stacked, and a source and a drain electrode are stacked on or below the zinc oxide semiconductor thin film. The and drain electrodes provide inorganic thin film transistors, which are spaced at regular intervals.

<40>

[Favorable effect]

Indium zinc oxide-based semiconductor ink composition in which the spontaneous combustion reaction occurs according to the present invention and the inorganic semiconductor thin film prepared through the same may be used as a channel material of the transistor device, thereby improving the electrical performance Thin film transistors can be manufactured. In addition, it is suitable for the solution process, making it easy to manufacture a thin film and low temperature process, and is generated by mixing two metal precursors coordinated with the fuel material and the oxidizing material By spontaneous combustion reaction, a compact and uniform thin film can be manufactured, and thus an inorganic thin film transistor with excellent reliability can be manufactured.

<42>

[Brief Description of Drawings]

1 is a schematic view showing an inorganic thin film transistor manufactured according to the present invention; 2 is a graph showing current transfer characteristics of an inorganic thin film transistor prepared from the inorganic semiconductor ink compositions of Example 3 and Comparative Examples 1 to 3 of the present invention;

3 is a graph showing heat generation characteristics at low silver of the inorganic semiconductor ink compositions of Example 3 and Comparative Examples 1 to 3 of the present invention.

<46>

<47> <Code Description>

<4S> 1: substrate (gate electrode)

2: inorganic inorganic film according to the present invention.

3: source electrode A1

4: drain electrode

<52>

- the best form of conduct - for balmyeongwa ^'

<53> The present invention

Nitrides of metal A as an oxidizing material;

It includes a complex represented by the following formula (1) of the metal B as a fuel material,

The metal A and the metal B are each one kind of metal selected from the group consisting of indium, gallium, zinc, titanium, aluminum, lithium and zirconium, and the semiconductor inks are characterized in that the metal A and the metal B are different from each other. To provide a composition.

<57>

<58> [Formula 1]

<59> (Wherein Ri, R ₂ and ¾ are each independently hydrogen or d to C ₂ alkyl, wherein d to C ₂ alkyl may be substituted with one or more F).

<61>

Hereinafter, the present invention will be described in detail.

<63>

According to the present invention, a spontaneous combustion reaction may occur by mixing two metal precursors in which the oxidizing material and the combustion material are coordinated, thereby producing a compact and uniform thin film. The metal A and the metal B of the oxidizing material and the combustion material are preferably at least one metal selected from the group consisting of rhythm, gallium, zinc, titanium, aluminum, lithium and zirconium, wherein the prize metals A and B are mutually Different is desirable.

<65>

According to the prior art, one kind selected from the group consisting of carbohydrazide, urea, citric acid, and glycine is used in addition to the oxide precursor composition as a combustion material. However, since the above materials must be added to the composition solution quantitatively, and thus reproducibility problems may occur in the performance of the transistor device, there is a problem that the industrial utilization may drop in practical terms.

However, in the case of using the metal precursor including the complex of Formula 1 according to the present invention, there is an advantage in that a precursor having excellent electrical properties can be manufactured without additional additives and equipment.

In this case, as an example, the fuel material may be zinc acetylacetonate hydrate.

(Zinc acetylacetonate hydrate, (Zn (C ₅ H ₇ 0 ₂ ) ₂ ᅳ x¾0)), Indium acetylacetonate hydrate, (In (C ₅ H ₇ 0 ₂ ) ₃ · x¾0)) ， Gallium Gallium acetylacetonate, (Ga (C ₅ H ₇ 0 ₂ ) ₃ ), Zinc citrate dihydrate, (Zn ₃ (C ₆ H ₅ 0 ₇ ) ₂ '2¾0)) , a zinc hEX-fluoro-acetyl-acetonide carbonate di-high drain-art (zinc hexaf luoroacetylacetonate dihydrate, (Zn (C 5 HF 6 0 2) 2 - 2H 2 0)) and glycine zinc salt monohydrate (glycine zinc salt monohydrate, (ZnC ₄ H ₁₀ N ₂ 0 ₅ )) etc. can be used.

<69> The semiconductor ink composition according to the present invention

Nitride of metal C as an oxidizing material;

Further comprising at least one selected from the complexes represented by the formula (1) of the metal C as a fuel material,

The metal C is one kind of metal selected from the group consisting of indium, gallium, zinc, titanium, aluminum, litop and zirconium, and the metal C is preferably different from the metal A and the metal B.

<74>

The semiconductor ink composition according to the present invention may be a mixture of two materials in which one kind of oxidizing material and one kind of fuel material are mixed, but is not limited thereto. Two kinds of oxidizing materials, one kind of combustion material, one kind of oxidizing material and two kinds of burning material can be used in combination, and also two kinds of oxidizing materials and two kinds of burning material can be used in combination. At this time, the acid fire fuel and the fuel material preferably contain different metals (see Examples 1 to 33).

<76>

The semiconductor ink composition according to the present invention may further include monoethyleneamine (MEA) as a stabilizer. The semiconductor ink composition may be formed by coating a solution having a homogeneously dispersed precursor material on a substrate and then performing heat treatment. It is possible to produce a homogeneous semiconductor oxide thin film, thereby producing an inorganic thin film transistor having excellent reliability. Accordingly, by further including monoethyleneamine (MEA, monoethyleneamine) as a stabilizer, it is possible to obtain a solution in which the precursor material is more stably dispersed in the solvent, thereby producing a homogeneous semiconductor oxide thin film.

<78>

In this case, when the metal A and the metal B are zinc or indium, it is preferable that the zinc: rhythm is mixed in a molar ratio of 1: 0.7 to 1:10. Specifically, in the case of a mixture of zinc nitride and ginyl acetylacetonate or a mixture of zinc acetylacetonate and indium nitride, it is more preferable that zinc: indium is mixed in a molar ratio of 1: 0.7 to 1: 5.

In addition, when the metal A and the metal B are indium or gallium, specifically, a mixture of indium acetylacetonate and gallium nitride or a mixture of gallium acetylacetonate and indium nitride, This is preferably mixed in a molar ratio of 1: 0.1 to 1: 0.7. More preferably indium: gallium is 1: 0.2 to 1: 0.5 It is good to mix in molar ratio.

Furthermore, when the metal C is gallium, specifically, when the mixture of zinc acetylacetonate and indium nitride or the mixture of gallium acetylacetonate and phosphate nitride further includes gallium acetylacetonate and gallium nitride, Zinc: Inflorescence: Gallium It is preferable to mix these in the molar ratio of 1: 1-3: 0.1-2.

By using the inorganic semiconductor ink composition prepared at the above-described mixing ratio, an inorganic thin film transistor having excellent charge mobility and on / off ratio can be manufactured (see Table 1 and Table 3).

<83>

In the semiconductor ink composition according to the present invention, the semiconductor ink composition further comprises a solvent, and the concentration of the mixture of the oxidizing material, the fuel material and the solvent is 0.05 to

It is preferable that it is 0.25M.

The concentration of the semiconductor ink composition represents the molarity of the precursor material relative to the solvent. Compared with the conventional semiconductor ink composition having a concentration of about 30 M to 0.50 M, the semiconductor ink composition according to the present invention has a dilute concentration of about 3 to 5 times as a concentration of about 0.1 M, thereby reducing raw material cost. There is an effect that can be.

<86>

The solvent is preferably one selected from the group consisting of isopropyl alcohol, chlorobenzene, N-methyl pyridone, ethane, amine, ethanol, methanol, 2-methoxyethanol, and mixtures thereof. It doesn't happen.

<88>

In addition, the present invention

(90) preparing a film by printing or coating the inorganic semiconductor ink composition solution on the substrate; And

<92>

In the method of manufacturing a semiconductor thin film using the semiconductor ink composition according to the present invention, step 1 is a step of preparing a film by printing or coating the inorganic semiconductor ink composition on the substrate.

In this case, the printing or coating of the step 1 is inkjet printing, roll printing, gravure printing, aerosol printing, screen printing, roll coating, spin coating, bar nose It is preferably a method selected from the group consisting of casting, spray coating and dip coating. The zinc oxide semiconductor thin film according to the present invention may be prepared by selecting an easy method among the printing and coating methods, and preferably using spin coating, but not limited thereto.

<95>

In the method of manufacturing a semiconductor thin film using the semiconductor ink composition according to the present invention, step 2 is a step of thermally treating the film prepared in step 1.

<97>

In step 2, the semiconductor thin film is manufactured by thermally treating the thin film coated on the substrate in step 1, and the zinc oxide nanostructure is homogeneously formed inside the manufactured semiconductor thin film, thereby providing excellent charge mobility. Its electrical properties are shown. In addition, due to spontaneous combustion reactions generated by mixing two metal precursor solutions, a compact and uniform thin film can be manufactured, and thus, reliability can be improved.

<99>

Representative chemical reaction of the combustion reaction proposed in the present invention is as follows.

<101>

_{<102> 5 Zn (C 5} H 7 0 2) 2 · x¾0 + 16 In (N0 3) 3 - x¾0

<i03> → 5 ZnO 8 ln ₂ 0 ₃ (s) + 24 N ₂ (g) + 5 C0 ₂ (g) + x H ₂ 0 (g)

<104>

As in the chemical reaction method, a combustion reaction is performed in which carbon dioxide and water are formed by a chemical reaction between an oxidizing material and a fuel material, and heat is generated accordingly.

The spontaneous combustion reaction is an important feature of forming a semiconductor thin film from the inorganic semiconductor ink composition according to the present invention, a metal precursor (oxidizing material) having an oxidizing property and a metal precursor (combusting material) having a burning property. Internal heat generated from the combustion reaction can be used as energy for the conversion from precursor to oxide. Accordingly, the external energy applied to the oxide formation, that is, the temperature required for heat treatment can be considerably lowered. Therefore, it is possible to reduce the high process temperature, which is considered a major disadvantage in the solution process of oxide semiconductors.

<107>

In the method of manufacturing a semiconductor thin film using the semiconductor ink composition according to the present invention, the heat treatment of Step 2 is preferably performed ^at 200 ^° C to 350 ^° C, but is not limited thereto. According to the present invention, when the oxidizing material and the fuel material are mixed, spontaneous combustion reaction occurs and the oxide formation silver is lowered by the exothermic reaction. Therefore, since the oxide is easily formed, the electrical properties of the transistor including the semiconductor thin film can be greatly improved, which is advantageous.

<110>

The present invention provides a semiconductor thin film formed on the substrate through the above manufacturing method. The semiconductor thin film manufactured by the manufacturing method according to the present invention may be used as an N-type semiconductor thin film of an inorganic thin film transistor, and accordingly, electrical characteristics such as charge mobility and on / off ratio of the inorganic thin film transistor may be used. Can improve.

<112>

Furthermore, the present invention

A substrate (gate electrode) and the semiconductor thin film are sequentially stacked, and source and drain electrodes are stacked on or under the zinc oxide semiconductor thin film, and the source and drain electrodes are fixed. An inorganic thin film transistor is provided that is spaced apart from each other. A schematic diagram of an inorganic thin film transistor in the present invention is shown in FIG.

<115>

The inorganic thin film transistor according to the present invention includes the semiconductor thin film inside the film, and thus has excellent electrical characteristics such as charge mobility and flashing ratio. In addition, it can be applied to various electronic devices such as memory and display, and especially to the display device due to the high transmittance of zinc oxide thin film.

In this case, a silicon (Si) wafer, a glass substrate, a plastic substrate, or the like may be used, and the substrate is selected according to a product to which the inorganic thin film transistor is to be applied. For example, when the substrate is a silicon (Si) wafer substrate, an inorganic thin film transistor may be applied to a memory device, and in the case of a glass substrate, it may be applied to a display device, and in the case of a plastic substrate, the substrate may be flexible. It can be applied to electronic devices that require characteristics.

<118>

[Form for implementation of invention]

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for the description of the present invention and the scope of the present invention is not limited by the following examples. <120>

<i2i> <Example 1-33> Preparation of Inorganic Semiconductor Ink Composition 1

<122> Indium nitrate hydrate as a starting material

(In (N0 ₃ ) ₃ -x¾0)), zinc nitrate hexahydrate, (Zn (N¾) ₂ · 6¾0)), gallium nitrate hydrate, (Ga (N0 ₃ ) ₃ x¾0)), zinc acetylacetonate hydrate (Zn (C ₅ H ₇ ¾) ₂ · x¾0)), indium acetylacetonate hydrate, (In (C ₅ H ₇ 0 ₂ ) ₃ · x¾0)), gallium acetylacetonate (Ga (C ₅ H ₇ 0 ₂ ) ₃ )), and 2-mechanism was used as a solvent. At this time, the components were mixed at the concentration as shown in Table 1 below to prepare an inorganic semiconductor ink composition by stirring for one day at a temperature of room temperature to obtain a homogeneous and transparent solution.

<123>

<124> [S. One]

Comparative Example l-7 Preparation of Inorganic Semiconductor Ink Composition 2

Indium nitrate hydrate as a starting material

_{_{(In (N0 3) 3 ·}} x¾0)), zinc nitrate hex hydrate (Zinc nitrate hexahydrate, (Zn ( N¾) 2 · 6¾0)), gallium nitrate high. Rate (Gallium nitrate hydrate, (Ga ( N0 3) ₃ -xH ₂ 0)), zinc acetylacetonate hydrate (Zn (C ₅ H ₇ 0 ₂ ) ₂ -x¾0)), rhythmic acetylacetonate hydride R2013 / 011357

13

Sites (Indium acetylacetonate hydrate, (In ( C 5 H 7 0 2) 3 · x¾0)) eu gallium acetylacetonate four bytes (Gal Hum acetylacetonate (Ga (C 5 ¾0 2) 3)), chloride indeum (InCl _3), Zinc chloride

(C1 ₂ ) was used, and 2-methoxyethane was used as the solvent. At this time, the constitutive minutes at room temperature to obtain a ^{concentration,} homogeneous and clear solution is as heunhap such as the following Table 2 was stirred for one day to prepare the inorganic semiconductor ink composition

<127>

<128> [Table 2]

<I29>

<I30> <Experimental Example 1> Current Transfer Characteristics of Thin Film Transistors

<I3I> The inorganic semiconductor ink compositions of the above production examples and examples were coated on a silicon substrate on which 300 nm of silicon dioxide was deposited by spin coating, followed by heat treatment at a temperature of 350 ° C. on a hotplate for 1 hour. A semiconductor thin film was prepared. An inorganic thin film transistor was fabricated by depositing a source / drain electrode having a width of 3000 μηι / 50 μ (η size) to a thickness of 150 nm by using an evaporator on the semiconductor thin film. ， The charge mobility and on / off ratio of the prepared inorganic thin film transistors were measured, and the results are shown in Table 3 and Fig. 3. In this case, Fig. 3 was prepared in Example 3 of the present invention. A graph showing current transfer characteristics of a thin film transistor using the inorganic thin film semiconductor ink.

<132>

<133> [Table 3] 2013/011357

14

As shown in Table 3, in Examples 1 to 3 according to the present invention, the charge mobility of Comparative Examples 1 to 3 using the same kind of IZ0 precursor (2.20 cm v − for Comparative Example 2). It can be seen that it is relatively superior to s), through which the zinc: indium contained in the precursor material is mixed in a molar ratio of 1: 7 to 1:10.

It is preferable that it is preferable to mix with a molar ratio of 1: 0.7 to 1: 5. Also, in the case of Examples 6 to 9 according to the present invention, it is relatively superior to the charge mobility of Comparative Examples 1 to 3 (2.20 cm ² / V · s in Comparative Example 2) It can be seen that through this, it is understood that the zinc: indium contained in the precursor material is preferably mixed in a molar ratio of 1: 0.7 to 1: 5.

In particular, when the zinc: indium is mixed in a molar ratio of 1: 1, as shown in Example 3 and Example 8 according to the present invention it can be seen that it shows an excellent charge mobility. In particular, in the case of Example 3 according to the present invention, it was confirmed that the remarkably excellent charge exhibited the same value at a maximum of 13.8 cm ² / V · s.

<137>

On the other hand, when three or more kinds of precursor materials are mixed as in Examples 21 to 33 according to the present invention, it is preferable that zinc: indium: gallium is mixed so as to have a molar ratio of 1: 1 — 3: 0.1-2. It can be seen. In this case, when the inorganic thin film transistors are prepared in comparison with the inorganic semiconductor ink compositions of Comparative Examples 1 to 7 prepared from precursors composed of only nitrides or acerylacetonates without mixing nitrides and acetylacetonates, It can be seen that the flashing ratio is relatively high.

<139>

Therefore, it can be seen that by using the inorganic semiconductor ink composition according to the present invention, an inorganic thin film transistor having improved electrical characteristics can be manufactured.

<141>

Experimental Example 2 Thermal Properties of Inorganic Semiconductor Ink Precursor

In order to examine the thermal characteristics of the inorganic semiconductor ink prepared according to the present invention, after drying the inorganic semiconductor ink prepared in Comparative Examples 1 to 3 and 3 to remove the solvent, the thermal mass and the time difference The thermal analysis (SDT 2060, TA instruments, USA) was used to observe the mass change and the exothermic and endothermic behavior of the composition by heat irradiation (101 min), and the results are shown in FIG. 3.

<144>

As shown in FIG. 3, in Comparative Examples 1 to 3, the temperature at which the organic component is completely decomposed is about 300 ^° C. or higher, and in Comparative Example 2, about 400 to 500 ° C. You can see that. In this case, it can be seen that in the case of the comparative example, a strong exothermic phenomenon does not occur and thus no combustion reaction occurs. In the case of Example 3 it can be seen that the rapid weight loss and strong heat generation near about 200 ^° C, through this combustion It can be seen that the reaction proceeds.

In addition, in the case of Example 3, it can be confirmed through Table 3 that the electrical properties are superior to Comparative Example 1 to Comparative Example 3, which is heat-treated after mixing the oxidizing material nitride and acetylacetonate as fuel material Accordingly, since spontaneous combustion reaction occurs, the temperature required for the oxide reaction such as hydrolysis, condensation reaction, and decomposition of organic matter of the precursor is lowered, and thus an oxide thin film can be easily formed.

Therefore, according to the present invention, as the oxidizing material and the fuel material are mixed, a spontaneous combustion reaction occurs and accordingly, the formation of the oxide is lowered and the oxide is easily formed. have .

Claims

[Claim of claim] [Claim 1] A nitride of metal A which is an oxidizing material; A complex of a metal B, which is a fuel material, is represented by the following Chemical Formula 1, and the metal A and the metal B are one metal selected from the group consisting of indium, gallium, zinc, titanium, aluminum, lithium, and zirconium, respectively. , Wherein the metal A and the metal B are different from each other:

[Formula 1]

(In the above, R ₂ and R ₃ are each independently hydrogen or to C ₂ alkyl, wherein d to C ₂ alkyl may be substituted with one or more F.)

[Claim 2]

The method of claim 1,

The semiconductor ink composition is

Nitrides of metal C as oxidizing materials;

The metal C is one kind of metal selected from the group consisting of indium, gallium, zinc, titanium, aluminum, litop and zirconium, and the metal C is different from the metal A and the metal B.

[Claim 3]

The method of claim 1,

The semiconductor ink composition further comprises a monoethane amine as a stabilizer A semiconductor ink composition characterized by the above-mentioned.

[Claim 4]

The method of claim 1,

When the metal A and the metal B is zinc or indium, the zinc: rhythm has a molar ratio of 1: 0.7 to 1:10.

[Claim 5]

The method of claim 1,

The semiconductor ink composition further comprises a solvent, the concentration of the mixture of the oxidizing material, fuel material and solvent is a semiconductor ink composition, characterized in that 0.05 to 0.25 M

[Claim 6]

Preparing a film by printing or coating the inorganic semiconductor ink composition solution of claim 1 on a substrate (step 1); And ^'

A method of manufacturing a semiconductor thin film using a semiconductor ink composition comprising a step (step 2) of heat-treating the film prepared in step 1.

[Claim 7]

The method of claim 6,

The printing or coating of step 1 includes inkjet printing, printing, gravure printing, aerosol printing, screen printing, roll coating, spin coating, bar coating, spray coating and dip coating. Method for producing a semiconductor thin film using a semiconductor ink composition, characterized in that the method selected from.

[Claim 8]

The method of claim 6,

The heat treatment of step 2 is a method of manufacturing a semiconductor thin film using a semiconductor ink composition, characterized in that carried out ^at 200 ^° C to 350 ^° C.

[Claim 9] A semiconductor thin film formed on the substrate through the manufacturing method of claim 6.

[Claim 10]

A substrate (gate electrode) and the semiconductor thin film of claim 9 are sequentially stacked, and a source and a drain electrode are stacked on the zinc oxide semiconductor thin film, and the source and drain electrodes are spaced at a predetermined interval. Inorganic thin-film transistors