KR101531606B1 - Indium zinc oxide semiconductor ink composition generating self-combustion reaction and the inorganic semiconductor film thereof - Google Patents

Abstract

An object of the present invention is to provide an indium zinc oxide-based semiconductor ink composition in which a spontaneous combustion reaction occurs, and an inorganic semiconductor thin film produced thereby. For this purpose, the present invention comprises a nitrate of a metal A which is an oxidizing material and a complex represented by the formula 1 of a metal B which is a fuel material, wherein the metals A and B are indium, gallium, zinc, titanium, Aluminum, lithium and zirconium, and the metal A and the metal B are different from each other. INDUSTRIAL APPLICABILITY The indium zinc oxide-based semiconductor ink composition in which the spontaneous combustion reaction according to the present invention is generated and the inorganic semiconductor thin film produced therefrom can be used as a channel material of a transistor device and thus an inorganic thin film transistor having improved electrical performance can be manufactured have. In addition, it is suitable for solution process and can produce thin and uniform thin film by spontaneous combustion reaction which is generated by mixing of two metal precursors in which a fuel material and an oxidizing material are coordinated, Thus, an inorganic thin film transistor having excellent reliability can be manufactured.

Description

[0001] The present invention relates to an indium zinc oxide-based semiconductor ink composition which generates a spontaneous combustion reaction, and an inorganic semiconductor thin film produced thereby.

The present invention relates to an indium zinc oxide-based semiconductor ink composition in which a spontaneous combustion reaction occurs, and an inorganic semiconductor thin film produced thereby.

Recently, much attention has been paid to various characteristics of oxide semiconductors, and a lot of researches have been made. Particularly, oxide semiconductors have been applied as active layers of thin film transistors (TFTs), and inorganic oxide semiconductors used therefor include zinc oxide (ZnO), indium oxide, indium zinc oxide (IZO), indium gallium gallium oxide (IGZO) Indium tin zinc (IZTO) and so on. These oxide semiconductors have a relatively large bandgap of more than 3 eV due to the nature of chemical bonds of oxides, and show transparent characteristics in the visible light region. They can grow at lower temperatures than silicon, There are advantages to be gained.

The thin film transistor device is a core part required in a display information device and is essential for pixel gradation representation of a display information device by switching one pixel. It is forming a big market in the electronic information industry. At present, oxide semiconductor is widely used as vacuum-based equipment such as sputtering, atomic layer deposition (ALD), pulse laser deposition (PLD), and metalorganic chemical vapor deposition (MOCVD).

However, as electronic products such as display devices have recently formed a low price range, the electronic information industry in recent years has become increasingly important for ultra low price, large area process and mass production. Therefore, in order to replace an exposure or vacuum deposition process involving high process costs, it is necessary to develop a solution-based process. Though many researches based on organic semiconductors have been made on the fabrication of thin film transistor devices using such a solution-based process, organic thin film transistors have not only the basic characteristics of thin film transistors such as mobility, flicker rate and current density but also durability And many problems to be solved in terms of electrical reliability remain.

On the other hand, a new tendency to produce inorganic oxide semiconductors using solution processes has begun to appear. This is due to the fact that various materials such as indium oxide, indium tin oxide (ITO), aluminum and gallium- Researches have been actively carried out to develop. Sol-gel method, organic metal decomposition method (MOD), chemical bath method (CBD), and the like are available for the solution process.

In the sol-gel method, which is mainly used in the production of inorganic oxide semiconductors, a metal precursor solution having an appropriate pH is coated on a substrate through spin coating or inkjet printing, and then heat-treated. During the heat treatment, inorganic precursors undergo hydrolysis and condensation reactions, and metal oxides are formed due to the combination of metal and oxygen generated from these reactions. Typical inorganic precursors include metal alkoxides, metal acetates, metal nitrates, and metal halides.

However, the sol-gel oxide semiconductor process temperature is still relatively high to obtain excellent electrical properties. It is reported that the temperature of the heat treatment process is more than 300 ° C for ZnO, 400 ° C or more for IZO, and 450 ° C or more for IGZO. (Adv. Mater. 2012, 24, 2945)

Many studies have been reported to solve the disadvantages of the heat treatment process of such an inorganic semiconductor material. According to a study by Shrringhaus et al., A mobility of ~ 10 cm ² V ^-1 s ^-1 was obtained by heat treatment at 275 ° C using a precursor of indium, gallium, and zinc in a nitrogen atmosphere, glove box. , A deep-UV exposure and a heat treatment at 200 ° C using indium, gallium, zinc acetate, and nitrate precursors in a nitrogen atmosphere, results in a mobility of ~ 10 cm ² V ^-1 s ^-1 (Nature 2011, 10, 45, Nature Lett. 2012, 489, 128).

However, these methods are not reproducible experimentally without a nitrogen atmosphere, special equipment, or a high-k gate insulator, so that there is a problem in that the practical use of the method may deteriorate industrially.

According to the results of Marks et al., Recently, Urea, which is a fuel material and ammonium nitrate (NH ₄ NO ₃ ), which is an oxidizer material, are added to indium and zinc nitrate precursors, Was prepared and its mobility ~ 3 cm ² V ^-1 s ^-1 was obtained with the heat treatment at 300 ℃. Although high mobility is obtained by the combustion reaction at low temperatures, addition of a fuel material, an oxidizing material and a base solution in addition to the metal oxide precursor is required, and it is difficult to reproduce without quantitative addition (J. Am. Chem. Soc., 2012, 134, 9593, Nature Mater. 2011, 10, 382, J. Am.

The inventors of the present invention have discovered a metal precursor in which a fuel material and an oxidizing material are coordinated while studying a method of manufacturing an indium zinc semiconductor thin film exhibiting excellent characteristics. By mixing two metal precursors without additional additives, charge mobility and flicker An inorganic semiconductor ink composition capable of producing a thin film of indium zinc oxide semiconductor having improved specific characteristics has been developed and the present invention has been completed.

An object of the present invention is to provide an indium zinc oxide-based semiconductor ink composition in which a spontaneous combustion reaction occurs, and an inorganic semiconductor thin film produced thereby.

To this end,

Nitrate of metal A which is an oxidizing material;

And a complex of a metal B, which is a fuel material, represented by the following general formula (1)

Wherein the metal A and the metal B are one kind of 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. do.

[Chemical Formula 1]

(Wherein R ₁ , R ₂ and R ₃ are each independently hydrogen or C ₁ to C ₂ alkyl, wherein C ₁ to C ₂ alkyl may be substituted with one or more F)

In addition,

Printing or coating the inorganic semiconductor ink composition above the substrate to form a film (step 1); And

And a step of heat-treating the film produced in the step 1 (step 2).

In addition,

A semiconductor thin film formed on the substrate is provided through the above-described manufacturing method.

Further,

A source and a drain electrode are stacked on a substrate (gate electrode) and a semiconductor thin film formed by the above-described manufacturing method sequentially on the top or bottom of the zinc oxide semiconductor thin film, And the spacing is spaced apart from each other by a predetermined distance.

INDUSTRIAL APPLICABILITY The indium zinc oxide-based semiconductor ink composition in which the spontaneous combustion reaction according to the present invention is generated and the inorganic semiconductor thin film produced therefrom can be used as a channel material of a transistor device and thus an inorganic thin film transistor having improved electrical performance can be manufactured have. In addition, it is suitable for solution process and can produce thin and uniform thin film by spontaneous combustion reaction which is generated by mixing of two metal precursors in which a fuel material and an oxidizing material are coordinated, Thus, an inorganic thin film transistor having excellent reliability can be manufactured.

1 is a schematic view showing an inorganic thin film transistor manufactured according to the present invention;
FIG. 2 is a graph showing the current transfer characteristics of the inorganic thin film transistor made of the inorganic semiconductor ink composition of Example 3 of the present invention and Comparative Examples 1 to 3; FIG.
3 is a graph showing heat generation characteristics at low temperatures of the inorganic semiconductor ink composition of Example 3 of the present invention and Comparative Examples 1 to 3. Fig.

The present invention

Nitrate of metal A which is an oxidizing material;

And a complex of a metal B, which is a fuel material, represented by the following general formula (1)

Wherein the metal A and the metal B are one kind of 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. do.

[Chemical Formula 1]

(Wherein R ₁ , R ₂ and R ₃ are each independently hydrogen or C ₁ to C ₂ alkyl, wherein C ₁ to C ₂ alkyl may be substituted with one or more F)

Hereinafter, the present invention will be described in detail.

According to the present invention, a spontaneous combustion reaction can be generated by mixing the oxidizing material and the two metal precursors coordinated with the combustion material, thereby making it possible to produce a dense and uniform thin film. The metal A and the metal B of the oxidizing material and the combustion material are preferably one metal selected from the group consisting of indium, gallium, zinc, titanium, aluminum, lithium and zirconium, It is preferable that they are different.

According to the prior art, one species selected from the group consisting of carbohydrazide, urea, citric acid and glycine can be added to the oxide precursor composition as a combustion material, There is a problem in that it is necessary to quantitatively add the above materials to the solution of the composition additionally, and reproducibility problems may occur in the performance of the transistor device.

However, when a metal precursor containing the complex of Formula 1 according to the present invention is used, it is possible to produce a precursor exhibiting excellent electrical properties without additional additives and equipment.

At this time, for example, the fuel material may include zinc acetylacetonate hydrate (Zn (C ₅ H ₇ O ₂ ) ₂ .xH ₂ O), indium acetylacetonate hydrate (In ( C ₅ H ₇ O ₂ ) ₃ .xH ₂ O), gallium acetylacetonate (Ga (C ₅ H ₇ O ₂ ) ₃ ), zinc citrate dihydrate (Zn ₃ (C ₆ H ₅ O ₇ ) ₂ .2H ₂ O), zinc hexafluoroacetylacetonate dihydrate (Zn (C ₅ HF ₆ O ₂ ) ₂ .2H ₂ O) and glycine zinc Glycine zinc salt monohydrate (ZnC ₄ H ₁₀ N ₂ O ₅ ), and the like can be used.

The semiconductor ink composition according to the present invention comprises

Nitrate of metal C as an oxidizing material;

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

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

The semiconductor ink composition according to the present invention may be a mixture of two kinds of materials obtained by mixing one kind of oxidizing material and one kind of fuel material, but the present invention is not limited thereto. Two kinds of oxidizing materials and one kind of combustion material, one kind of oxidizing material and two kinds of combustion materials may be mixed and used, and two kinds of oxidizing materials and two kinds of combustion materials may be mixed and used. At this time, it is preferable that the oxidizing material and the fuel material each contain different metals (see Examples 1 to 33).

The semiconductor ink composition according to the present invention may further comprise monoethyleneamine (MEA) as a stabilizer. The semiconductor ink composition can form a uniform thin semiconductor oxide film by coating a solution on which a precursor material is homogeneously dispersed on a substrate and then performing heat treatment, thereby manufacturing an inorganic thin film transistor having excellent reliability. Thus, a solution in which the precursor material is more stably dispersed in the solvent can be obtained by further containing monoethyleneamine (MEA, monoethyleneamine) as a stabilizer, and thus a homogeneous thin film of semiconductor oxide can be produced.

At this time, when the metal A and the metal B are zinc or indium, zinc and indium are preferably mixed in a molar ratio of 1: 0.7 to 1:10. Specifically, in the case of a mixture of zinc nitrate and indium acetylacetonate or a mixture of zinc acetylacetonate and indium nitrate, 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 nitrate, or a mixture of gallium acetylacetonate and indium nitrate, 1: 0.7 in terms of molar ratio. More preferably, indium: gallium is mixed in a molar ratio of 1: 0.2 to 1: 0.5.

Further, when the metal C is gallium, specifically, when a mixture of zinc acetylacetonate and indium nitrate or a mixture of gallium acetylacetonate and indium nitrate further contains gallium acetylacetonate or gallium nitrate, zinc: indium: gallium Is preferably mixed at a molar ratio of 1: 1 - 3: 0.1 - 2.

An inorganic thin film transistor having excellent charge mobility and on / off ratio can be produced by using the inorganic semiconductor ink composition prepared at the above-described mixing ratio (see Tables 1 and 3).

In the semiconductor ink composition according to the present invention, the semiconductor ink composition preferably further comprises a solvent, and the concentration of the mixture of the oxidizing material, the fuel material and the solvent is preferably 0.05 to 0.25 M.

The concentration of the semiconductor ink composition represents the molar concentration of the precursor material relative to the solvent. Since the conventional semiconductor ink composition has a concentration of about 0.30 M to 0.50 M, the semiconductor ink composition according to the present invention has a concentration of about 0.1 M and a dilution of about 3 to 5 times, so that the raw material cost can be reduced There is an effect.

The solvent is preferably one selected from the group consisting of isopropyl alcohol, chlorobenzene, N-methylpyrrolidone, ethanolamine, ethanol, methanol, 2-methoxyethanol and mixtures thereof, but is not limited thereto.

In addition,

Printing or coating the above inorganic semiconductor ink composition solution onto the substrate to produce a film (step 1); And

And a step of heat-treating the film produced in the step 1 (step 2).

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

At this time, the printing or coating of the step 1 may be carried out by an inkjet printing method, a roll printing method, a gravure printing method, an aerosol printing method, a screen printing method, a roll coating method, a spin coating method, a bar coating method, Is a method selected from the group consisting of The zinc oxide semiconductor thin film according to the present invention can be manufactured by selecting one of the above printing and coating methods, and is preferably, but not limited to, spin coating.

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

In the step 2, the thin film coated on the substrate is heat-treated in the step 1 to produce a semiconductor thin film, and the indium zinc oxide nanostructure is uniformly formed in the produced semiconductor thin film, thereby exhibiting excellent electrical properties such as charge mobility. In addition, a dense and uniform thin film can be produced by the spontaneous combustion reaction generated by mixing the two metal precursor solutions, thereby improving the reliability.

A typical chemical reaction formula of the combustion reaction proposed in the present invention is as follows.

5 Zn (C ₅ H ₇ O ₂ ) ₂ .xH ₂ O + 16 In (NO ₃ ) ₃ .xH ₂ O

→ 5 ZnO 8 In ₂ O ₃ (s) + 24 N ₂ (g) + 5 CO ₂ (g) + x H ₂ O (g)

The combustion reaction in which carbon dioxide and water are formed by the chemical reaction between the oxidizing material and the fuel material proceeds as shown in the above chemical reaction formula 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. It is an object of the present invention to provide a method for producing a semiconductor thin film by a combustion reaction between a metal precursor (oxidation material) having oxidation characteristics and a metal precursor The generated internal heat can be used as energy required for conversion from the precursor to the oxide. Thereby significantly reducing the external energy required for oxide formation, that is, the temperature required for the heat treatment. Therefore, a high process temperature, which is considered to be a great disadvantage in the solution process of the oxide semiconductor, can be reduced.

In the method for producing a semiconductor thin film using the semiconductor ink composition according to the present invention, the heat treatment in the step 2 is preferably performed at 200 ° C to 350 ° C, but is not limited thereto.

According to the present invention, as the oxidizing material and the fuel material are mixed, a spontaneous combustion reaction occurs, and as a result, the oxide forming temperature is lowered by the exothermic reaction. Accordingly, since the oxide is easily formed, the electrical characteristics of the transistor including the semiconductor thin film can be greatly improved, which is advantageous.

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

Further,

A source electrode and a drain electrode are stacked on a substrate (gate electrode) and the semiconductor thin film sequentially on the upper or lower surface of the zinc oxide semiconductor thin film, and the source and drain electrodes are spaced apart from each other The present invention also provides an inorganic thin film transistor. A schematic view of an inorganic thin film transistor according to the present invention is shown in Fig.

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

At this time, a silicon (Si) wafer, a glass substrate, a plastic substrate, or the like can be used as the substrate, and a 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 can be applied to a memory device, a glass substrate can be applied to a display device, and a plastic substrate has a flexible characteristic It can be applied to required electronic devices.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Example 1-33 Preparation of inorganic semiconductor ink composition 1

Indium nitrate hydrate (In (NO ₃ ) ₃ .xH ₂ O), zinc nitrate hexahydrate (Zn (NO ₃ ) ₂ .6H ₂ O)) as a starting material, Gallium nitrate hydrate (Ga (NO ₃ ) ₃ .xH ₂ O), zinc acetylacetonate hydrate (Zn (C ₅ H ₇ O ₂ ) ₂ .xH ₂ O) , Indium acetylacetonate hydrate (In (C ₅ H ₇ O ₂ ) ₃ .xH ₂ O), gallium acetylacetonate (Ga (C ₅ H ₇ O ₂ ) ₃ )), And 2-methoxyethanol was used as the solvent. At this time, the components were mixed at the concentrations shown in Table 1 below, and stirred for one day at room temperature to obtain a homogeneous and transparent solution to prepare an inorganic semiconductor ink composition.

division Component (ratio) Zn
(ACAC) Zn
(Nitrate) In
(ACAC) In
(Nitrate) Ga
(ACAC) Ga
(Nitrate) Example 1 0.017 M 0.085 M Example 2 0.034 M 0.068 M Example 3 0.051 M 0.051 M Example 4 0.068 M 0.034 M Example 5 0.085 M 0.017 M Example 6 0.017 M 0.085 M Example 7 0.034 M 0.068 M Example 8 0.051 M 0.051 M Example 9 0.068 M 0.034 M Example 10 0.085 M 0.017 M Example 11 0.017 M 0.085 M Example 12 0.034 M 0.068 M Example 13 0.051 M 0.051 M Example 14 0.068 M 0.034 M Example 15 0.085 M 0.017 M Example 16 0.017 M 0.085 M Example 17 0.034 M 0.068 M Example 18 0.051 M 0.051 M Example 19 0.068 M 0.034 M Example 20 0.085 M 0.017 M Example 21 0.008 M 0.05 M 0.042 M Example 22 0.017 M 0.05 M 0.034 M Example 23 0.025 M 0.05 M 0.025 M Example 24 0.034 M 0.05 M 0.017 M Example 25 0.042 M 0.05 M 0.008 M Example 26 0.05 M 0.05 M 0.025 M Example 27 0.05 M 0.05 M 0.025 M Example 28 0.05 M 0.025 M 0.05 M Example 29 0.06 M 0.005 M 0.06 M Example 30 0.05 M 0.05 M 0.025 M Example 31 0.05 M 0.05 M 0.012 M 0.012 M Example 32 0.05 M 0.05 M 0.025 M Example 33 0.05 M 0.05 M 0.012 M 0.012 M

≪ Comparative Example 1-7 > Production of inorganic semiconductor ink composition 2

Indium nitrate hydrate (In (NO ₃ ) ₃ .xH ₂ O), zinc nitrate hexahydrate (Zn (NO ₃ ) ₂ .6H ₂ O)) as a starting material, Gallium nitrate hydrate (Ga (NO ₃ ) ₃ .xH ₂ O), zinc acetylacetonate hydrate (Zn (C ₅ H ₇ O ₂ ) ₂ .xH ₂ O)), Indium acetylacetonate hydrate (In (C ₅ H ₇ O ₂ ) ₃ .xH ₂ O), gallium acetylacetonate (Ga (C ₅ H ₅ O ₂ ) ₃ ), chloride Indium (InCl ₃ ) and zinc chloride (ZnCl ₂ ) were used, and 2-methoxyethanol was used as the solvent. At that time, the components were mixed at the concentrations shown in Table 2 below, and stirred for one day at room temperature to obtain a homogeneous and transparent solution, thereby preparing an inorganic semiconductor ink composition

division Component (ratio) Zn
(ACAC) Zn
(Nitrate) Zn
(Chloride) In
(ACAC) In
(Nitrate) In
(Chloride) Ga
(ACAC) Ga
(Nitrate) Comparative Example 1 0.05 M 0.05 M Comparative Example 2 0.05 M 0.05 M Comparative Example 3 0.05 M 0.05 M Comparative Example 4 0.068 M 0.034 M Comparative Example 5 0.068 M 0.034 M Comparative Example 6 0.05 M 0.05 M 0.025 M Comparative Example 7 0.05 M 0.05 M 0.025 M

<Experimental Example 1> Current Transfer Characteristics of Thin Film Transistor

The inorganic semiconductor ink compositions of the above Preparation Examples and Examples were coated on top of a silicon substrate having 300 nm of silicon dioxide deposited thereon by spin coating and then heat-treated at 350 ° C for 1 hour on a hot plate to produce a semiconductor thin film Respectively. An inorganic thin film transistor was fabricated on the semiconductor thin film by depositing source and drain electrodes having a width / length of 3000 μm / 50 μm in a thickness of 150 nm using an evaporator, The charge mobility and on / off ratio of the inorganic thin film transistor were measured, and the results are shown in Table 3 and FIG. 3 is a graph showing the current transfer characteristics of the thin film transistor using the inorganic thin film semiconductor ink according to the third embodiment of the present invention.

Charge mobility
(cm ² / V · s) Flashing Ratio
(on / off ratio) Example 1





IZO 7.79 ~ 10 ⁷ Example 2 8.49 ~ 10 ⁸ Example 3 13.8 ~ 10 ⁸ Example 4 1.78 ~ 10 ⁸ Example 5 0.31 ~ 10 ⁴ Example 6 3.25 ~ 10 ⁶ Example 7 6.78 ~ 10 ⁶ Example 8 7.23 ~ 10 ⁸ Example 9 3.41 ~ 10 ⁶ Example 10 0.37 ~ 10 ⁴ Example 11





IGO N / A N / A Example 12 N / A N / A Example 13 N / A N / A Example 14 1.47 ~ 10 ⁶ Example 15 1.07 ~ 10 ⁶ Example 16 N / A N / A Example 17 N / A N / A Example 18 N / A N / A Example 19 2.17 ~ 10 ⁶ Example 20 3.07 ~ 10 ⁶ Example 21







IGZO 1.55 x 10 ^-4 ~ 10 ³ Example 22 0.09 ~ 10 ⁵ Example 23 1.45 ~ 10 ⁶ Example 24 2.25 ~ 10 ⁷ Example 25 6.07 ~ 10 ⁷ Example 26 0.24 ~ 10 ⁶ Example 27 0.46 ~ 10 ⁶ Example 28 0.11 ~ 10 ⁶ Example 29 0.13 ~ 10 ⁶ Example 30 0.22 ~ 10 ⁶ Example 31 0.16 ~ 10 ⁶ Example 32 0.18 ~ 10 ⁶ Example 33 0.12 ~ 10 ⁶ Comparative Example 1

IZO 0.72 ~ 10 ⁶ Comparative Example 2 1.63 ~ 10 ⁷ Comparative Example 3 2.20 ~ 10 ⁷ Comparative Example 4
IGO N / A N / A Comparative Example 5 1.24 × 10 ^-4 ~ 10 ³ Comparative Example 6
IGZO 1.55 x 10 ^-4 ~ 10 ³ Comparative Example 7 2.22 × 10 ^-4 ~ 10 ³

As shown in Table 3, in the case of Examples 1 to 3 according to the present invention, the charge mobility of Comparative Examples 1 to 3 using the same kind of IZO precursor (2.20 cm ² / V · s), whereby the zinc: indium contained in the precursor material is preferably mixed at a molar ratio of 1: 0.7 to 1:10, more preferably at a molar ratio of 1: 0.7 to 1: 5 It is more preferable to mix them.

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

In particular, it can be confirmed that, when zinc and indium are mixed at a molar ratio of 1: 1 as in Examples 3 and 8 according to the present invention, they exhibit better charge mobility. Particularly, in the case of Example 3 according to the present invention, it was confirmed that the charge mobility value was remarkably excellent at a maximum of 13.8 cm ² / V · s.

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 in a molar ratio of 1: 1 - 3: 0.1 - 2 have. Compared to the inorganic semiconductor ink compositions of Comparative Examples 1 to 7 prepared from nitrates or acetylacetonate only precursors without mixing nitrate and acetylacetonate, the charge transport mobility and flickering ratio It can be confirmed that it is relatively high.

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

Experimental Example 2: Thermal characteristics of inorganic semiconductor ink precursor

In order to examine the thermal characteristics of the inorganic semiconductor ink produced according to the present invention, the inorganic semiconductor ink prepared in Comparative Examples 1 to 3 and Example 3 was dried to remove the solvent, and then, the thermal mass and a differential thermal analyzer (SDT 2060, TA instruments, USA), and the exothermic and endothermic behaviors of the compositions were observed. The results are shown in FIG.

As shown in FIG. 3, it can be seen that the temperature at which organic components are completely decomposed is about 300 ° C or more in the case of Comparative Examples 1 to 3, and about 400 to 500 ° C in the case of Comparative Example 2. As a result, it can be seen that a strong exothermic phenomenon does not occur and the combustion reaction does not occur in the comparative example. In Example 3, it was confirmed that the weight decrease and strong heat generation were observed at about 200 ° C, and the combustion reaction was progressed.

Table 3 shows that the electrical properties of Example 3 are superior to those of Comparative Examples 1 to 3 in that the nitrate salt as the oxidizing material and the acetylacetonate as the fuel material are mixed and heat- Since the reaction is performed, the temperature required for the reaction of the oxides such as hydrolysis, condensation reaction, and decomposition of the organic matters of the precursor is lowered, and thus the 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 as a result, the oxide formation temperature is lowered and the oxide is easily formed, so that the electrical characteristics can be greatly improved.

1: substrate (gate electrode)
2: The inorganic semiconductor film according to the present invention
3: source electrode (Al)
4: drain electrode

Claims (9)

Nitrate of metal A which is an oxidizing material;
And a complex of a metal B, which is a fuel material, represented by the following general formula (1)
Wherein the metal A and the metal B are indium and zinc, respectively; Or zinc and indium, zinc: indium is in a molar ratio of 1: 0.7 to 1:10,
Wherein the metal A and the metal B are indium and gallium, respectively; Or gallium and indium; wherein the indium: gallium molar ratio is 1: 0.1 to 1: 0.7.

[Chemical Formula 1]

(Wherein R _1, R ₂ and R ₃ are each independently a C ₁ to C ₂ alkyl substituted by hydrogen or C ₁ to C ₂ alkyl, or one or more F.)
The method according to claim 1,
The semiconductor ink composition
Nitrate of metal C as an oxidizing material; or,
Further comprising at least one selected from the complexes represented by the above formula (1) of the metal C as the fuel material,
Wherein the metal C is gallium or zinc, the metal C is different from the metal A and the metal B, and the molar ratio of zinc: indium: gallium is 1: 1 to 3: 0.1 to 2.
The method according to claim 1,
Wherein the semiconductor ink composition further comprises monoethanolamine as a stabilizer.
The method according to claim 1,
Wherein the semiconductor ink composition further comprises a solvent and the concentration of the oxidizing material and the fuel material in the mixture of the oxidizing material, the fuel material and the solvent is 0.05 to 0.25 M.
Printing or coating the semiconductor ink composition of claim 1 onto a substrate to produce a film (step 1); And
And a step (2) of heat-treating the film produced in the step (1).
6. The method of claim 5,
The printing or coating of step 1 above may be effected from the group consisting of ink jet printing, roll printing, gravure printing, aerosol printing, screen printing, roll coating, spin coating, bar coating, spray coating and dip coating Wherein said method comprises the steps of:
6. The method of claim 5,
Wherein the heat treatment in step 2 is performed at a temperature of 200 ° C to 350 ° C.
A semiconductor thin film formed on a substrate through the manufacturing method of claim 5.
A source electrode and a drain electrode are stacked in this order on the semiconductor thin film, and the source electrode and the drain electrode are spaced apart from each other by a predetermined distance .

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