KR101627331B1 - Compound for transparent electroconductive thin film, method for forming thin film using the same and transparent electroconductive thin film manufacutred thereby - Google Patents

Compound for transparent electroconductive thin film, method for forming thin film using the same and transparent electroconductive thin film manufacutred thereby Download PDF

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KR101627331B1
KR101627331B1 KR1020120103571A KR20120103571A KR101627331B1 KR 101627331 B1 KR101627331 B1 KR 101627331B1 KR 1020120103571 A KR1020120103571 A KR 1020120103571A KR 20120103571 A KR20120103571 A KR 20120103571A KR 101627331 B1 KR101627331 B1 KR 101627331B1
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thin film
boron
transparent conductive
conductive thin
indium
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KR1020120103571A
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Korean (ko)
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KR20140037458A (en
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이영주
박종일
김주영
오윤석
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재단법인 포항산업과학연구원
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Abstract

In the embodiments of the present invention, a transparent conductive thin film composition, a transparent conductive thin film formation method using the same, and a transparent conductive thin film formed by the method are disclosed. The transparent conductive thin film composition is indium (In), gallium (Ga), boron (B), zinc (Zn) and oxygen, the ratio (In + Ga) of indium, gallium, boron and zinc, including, but the (O 2) / (In + Ga + B + Zn) is 25 to 65 atomic%, and the content of boron is 4 to 8 atomic%.

Description

TECHNICAL FIELD The present invention relates to a transparent conductive thin film composition, a transparent conductive thin film forming method using the same, and a transparent conductive thin film using the transparent conductive thin film composition and a transparent conductive thin film using the transparent conductive thin film composition,

The present invention relates to a transparent conductive thin film composition, a method of forming a transparent conductive thin film using the same, and a transparent conductive thin film. More specifically, the present invention relates to a transparent conductive thin film composition by sputtering a composite of indium, gallium, zinc, A method of forming a thin film excellent in transparency and conductivity, and a transparent conductive thin film produced thereby.

Generally, a transparent conductive thin film has high electric conductivity and high visible light transmittance and is widely used for a liquid crystal display (LCD), a plasma display (PDP), an organic light emitting display (OLED), a touch panel, , And anti-static.

Materials being used most often to produce a transparent conductive thin film is being used most often is tin oxide (SnO 2) is 3 ~ 10wt% doped indium tin oxide (ITO), indium oxide (In 2 O 3). Sputtering is the most widely used method for manufacturing the ITO film, and there are spraying, vacuum evaporation, sputtering and ion plating.

The ITO films prepared by the above methods are excellent in transparency and conductivity as well as excellent in etching property and adhesiveness to a substrate and are most widely used at present. However, indium is not only a scarce resource, it is harmful to the living body, and it causes nodule generation when sputtering ITO target. Due to the scarcity of resources, human hazards, and the generation of nodules during sputtering, it is necessary to study alternative materials that can reduce indium in ITO or replace ITO.

A new study on the transparent electrode material corresponding to this necessity has been carried out by using fluorine (F) or antimony (Sb) doped tin oxide (FTO, ATO) and zinc oxide (AZO, GZO, IZO), but more specific studies on the content are needed.

In order to solve the above problems, the present invention provides a transparent conductive thin film composition comprising indium, gallium, boron and zinc oxide, a method of forming a thin film having improved transparency and conductivity by coating the composition on the surface thereof, Thin film.

In one of the invention or a number of embodiments of indium (In), gallium (Ga), boron (B), zinc (Zn), and comprising an oxygen (O 2), the ratio of indium, gallium, boron, and zinc ( Wherein the content of boron is 4 to 8 atomic percent (atomic%), and the content of In + Ga / In + Ga + B + Zn is 25 to 65 atomic% .

In one or more embodiments of the present invention, a mixture of indium oxide (In 2 O 3 ), gallium oxide (Ga 2 O 3 ), boron oxide (B 2 O 3 ), and zinc oxide (ZnO) Producing; Preparing a sintered body by sintering the mixture by molding the mixture into a mold, and then heat-treating the sintered body; And forming a thin film on the substrate prepared by sputtering using the sintered body.

Wherein the mixture contains 25 to 65 atomic percent of indium, gallium, boron and zinc (In + Ga) / (In + Ga + B + Zn) and the boron content is 4 to 8 atomic percent %).

In addition, in one or more embodiments of the present invention, a transparent conductive thin film formed by the above method can be provided.

According to an embodiment of the present invention, a thin film having excellent transparency and conductivity can be formed by adding boron to a complex of indium, gallium, and zinc oxide.

1 is a scanning electron microscope (SEM) image of a transparent conductive material produced according to Example 1 of the present invention.
2 is EDX data of the transparent conductive material produced in Example 1 according to the present invention.
3 is a flow chart illustrating a process of forming a transparent conductive thin film according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. However, it is to be understood that the present invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. It is intended that the disclosure of the present invention be limited only by the terms of the appended claims.

An embodiment according to the present invention relates to a composition for preparing a transparent conductive thin film and a composition of a low-resistance transparent conductive thin film prepared using the same.

There is also provided a method for forming a thin film having excellent transparency and conductivity by coating a composite material of indium, gallium, boron and zinc oxide on the surface of glass, ceramic, or plastic, and a transparent conductive thin film produced thereby.

In the examples according to the present invention, boron oxide was added to a mixture of indium, gallium and zinc oxide to improve the sintering characteristics of the indium, gallium and zinc oxide complexes at a general temperature and to improve the overall properties of the conductive thin films.

In order to achieve the above object, in the embodiment of the present invention, the atomic ratio of (In + Ga) / (In + Ga + B + Zn) composed of indium, gallium, boron, zinc and oxygen is 25 to 65 atomic percent (atomic%) of a metal oxide.

Further, the content of boron in the examples according to the present invention is 4 to 8 atomic percent (atomic%).

If the atomic ratio of (In + Ga) / (In + Ga + B + Zn) is lower than 25 atomic percent or the boron exceeds 8 atomic percent, the conductivity is lowered. If the ratio of boron is 4 atomic percent , The influence of boron on sintering is insufficient. Further, when the atomic ratio of (In + Ga) / (In + Ga + B + Zn) exceeds 65 atomic percent, there is a problem that the price is excessively increased and the difference from the conventional ITO is small. In the examples, the content of boron and the ratio of (In + Ga) / (In + Ga + B + Zn) are limited to the above range.

At this time, since the indium and gallium are in the same group (longitudinal group) in the periodic table, their electrical properties are almost similar, and since indium and gallium are expensive rare metals, it is preferable to reduce the amount thereof.

FIG. 3 is a flow chart for forming a transparent conductive thin film according to an embodiment of the present invention. Referring to FIG.

Referring to FIG. 3, the method for forming a transparent conductive thin film includes the steps of forming a metal oxide powder of indium oxide (In 2 O 3 ), gallium oxide (Ga 2 O 3 ), boron oxide (B 2 O 3 ), and zinc oxide (ZnO) (S110). The sintered body (sintered body) is subjected to sputtering (sputtering) using a sintered body as a target Thereby forming a thin film on the substrate (S120).

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

In an embodiment of the present invention, 90 to 120 g of indium oxide (In 2 O 3 ) powder, 50 to 80 g of gallium oxide (Ga 2 O 3 ) powder, a zinc oxide (ZnO) powder 45 to 70 g of boron oxide (B 2 O 3 ) and 20 to 25 g of oxide powder in a total amount of 250 to 300 g were put into a polyethylene port and sufficiently filled with ethanol and then ball milled for 24 hours using a zirconia ball (ZrO 2 ball) (ball milling) method, followed by thorough stirring and drying on a plate at 120 ° C.

In order to mold and sinter the dried mixed powder, the dried mixed powder was put into a metal mold, pressed at a pressure of 300 kg / cm 2 , molded, and then sintered in air. The heating rate for sintering was 10 ° C / min and sintering was carried out at 1350 ° C for 6 hours. The composition of this molded article was analyzed using EPMA, and the results are shown in Table 1.

In the embodiment of the present invention, in order to deposit the formed body on the surface of the workpiece, an RF power of 30 W, a gas pressure of 5 X 10 -3 Torr, an argon (Ar) gas flow rate of 15 SCCM, an oxygen (O 2 ) gas flow rate : 5 SCCM, substrate temperature: room temperature, and thickness of 3000 Å.

The electrical conductivity and transparency of the sputtered material were measured. The electrical conductivity was measured using a 4-point probe surface resistance meter for a 3000 Å thick film. The transparency was measured for a 3000 Å thick film with a transmittance at 550 nm Were measured. In addition, the composition analysis was performed using EPMA for a film having a thickness of 3000 Å.

Composition analysis of the sintered body (atomic%) division Element composition ratio (atomic%) In Ga Zn B O (In + Ga) /
(In + Ga + B + Zn) Example 1 12.36 10.34 14.61 5.62 57.08 52.88 Example 2 15.43 9.00 12.22 5.79 57.56 57.58 Example 3 9.71 8.74 18.45 6.80 56.31 42.22 Example 4 8.01 6.56 22.22 7.65 55.56 32.79 Example 5 6.05 6.81 24.95 7.18 55.01 28.57 Example 6 7.74 6.96 22.44 7.35 55.51 33.04 Comparative Example 1 14.75 14.10 13.94 0.00 57.21 67.42 Comparative Example 2 11.47 10.27 22.83 0.00 55.43 48.78 Comparative Example 3 8.93 8.44 28.29 0.00 54.34 38.04

Composition analysis of thin films (atomic%) division Element composition ratio (atomic%) In Ga Zn B O (In + Ga) /
(In + Ga + B + Zn) Example 1 12.55 10.14 13.50 5.77 58.04 54.08 Example 2 15.88 9.11 11.87 5.92 57.22 58.42 Example 3 9.45 7.32 19.22 7.42 56.59 38.63 Example 4 8.12 8.75 20.88 5.22 57.03 39.26 Example 5 8.11 6.23 21.57 7.25 56.84 33.23 Example 6 5.98 6.45 25.23 7.08 55.26 27.78 Comparative Example 1 15.22 13.97 14.04 0.00 56.77 67.52 Comparative Example 2 11.42 10.42 24.05 0.00 54.12 47.58 Comparative Example 3 9.21 7.87 28.99 0.00 53.93 37.07

Table 2 shows the composition analysis of the thin films for the examples and comparative examples in Table 1. The reason why the compositions of the sintered bodies and the thin films are slightly different in Table 1 and Table 2 is that the sintered body The sintered body is subjected to a process of depositing a thin film in a vacuum, since the degree of each substance in a vacuum state is different from that of a gas in the deposition process.

The transparent conductive thin film produced according to the embodiment of the present invention has a transmittance of 80% or more and a thickness of 5,000 Å or less. If the transmittance is less than 80% or the thickness is larger than 5000 Å, have. That is, transparency and conductivity are important in a transparent conductive thin film. Since all the materials have a resistance inversely proportional to the thickness of the material, the electrical conductivity increases when the material is thickly deposited. However, when the material is thickly deposited, the transparency becomes poor and becomes opaque. Therefore, in order to compensate for this, a small amount of boron oxide (B 2 O 3 ) and zinc oxide (ZnO) are further added in the embodiment of the present invention.

The addition of the boron oxide and zinc oxide results in an additional electron orbit generated by the boron and zinc atoms, which improves the conductivity, and the transmittance can be improved while obtaining the required conductivity at a thin thickness.

Characterization of thin films division Transmittance (%)
(550 nm) resistance
(Ohms / □) XRD Features Remarks Example 1 93 77 Amorphous Confirm sintering Example 2 91 79 Amorphous Confirm sintering Example 3 92 81 Amorphous Confirm sintering Example 4 90 84 Crystalline Confirm sintering Example 5 84 93 Crystalline Example 6 82 95 Crystalline Comparative Example 1 94 86 Amorphous Confirm sintering Comparative Example 2 89 92 Crystalline Comparative Example 3 82 99 Crystalline

Table 3 shows the results of evaluating the characteristics of the transparent conductive thin film prepared according to the embodiment of the present invention. The dielectric glass prepared according to the present invention was analyzed using an X-ray diffractometer and an electron microscope .

Generally, it is preferable to induce the crystalline thin film to emerge as crystalline because of its better conductivity characteristic than the amorphous thin film. However, if the ratio of indium is high, a little conductivity may be expressed even in amorphous state. However, the most important property of the transparent conductive material is conductivity, and crystallinity is one of the indices indicating this.

Examples 1 to 3 are amorphous and Examples 4 to 6 are crystalline. Further, in the results of the comparative example in which boron oxide is not contained, Comparative Example 1 is amorphous and Comparative Examples 2 and 3 are crystalline. In order to examine the effect of boron on the sintering, the sintering degree was analyzed through an electron microscope. As a result, it was confirmed that Examples 1 to 3 and Comparative Example 1 were sintered. Since the In: Ga: Zn ratios of Examples 1 to 2 and Comparative Example 1, Examples 3 to 4 and Comparative Example 2, and Examples 5 to 6 and Comparative Example 3 are similar, the comparison between Examples 3 and 4 and Comparative Example 2 It was confirmed that boron contributes to sintering irrespective of the result, and it showed low resistance at the side where sintering occurred and electric conductivity was improved. FIG. 1 shows a scanning electron microscope photograph of Example 1 according to the present invention, and FIG. 2 shows an elemental analysis result of the thin film of Example 1.

In embodiments of the present invention, a transparent conductive thin film is prepared using a composition of indium, gallium, boron, and zinc oxide, and the thin film has a visible light transmittance of 80% or more and electric conductivity is superior to an oxide composition without boron Respectively. These thin films have good bondability with substrates and can be used as electrodes in LCDs, PDPs, OLEDs and touch panels, as well as in electromagnetic shielding materials, heating elements and solar cells.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, You will understand.

It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

Claims (4)

(Ga), boron (B), zinc (Zn), and oxygen (O 2 )
(In + Ga) / (In + Ga + B + Zn) of indium, gallium, boron and zinc is 25 to 65 atomic% and the content of boron is 4 to 8 atomic% Wherein the transparent conductive thin film composition is a transparent conductive thin film composition. Preparing a mixture by mixing powders of indium oxide (In 2 O 3 ), gallium oxide (Ga 2 O 3 ), boron oxide (B 2 O 3 ) and zinc oxide (ZnO);
Preparing a sintered body by sintering the mixture by molding the mixture into a mold, and then heat-treating the sintered body; And
And forming a thin film on the substrate prepared by sputtering using the sintered body,
Wherein the mixture contains 25 to 65 atomic percent of indium, gallium, boron and zinc (In + Ga) / (In + Ga + B + Zn) and the boron content is 4 to 8 atomic percent %). ≪ / RTI > delete A transparent conductive thin film formed by the method of claim 2.
KR1020120103571A 2012-09-18 2012-09-18 Compound for transparent electroconductive thin film, method for forming thin film using the same and transparent electroconductive thin film manufacutred thereby KR101627331B1 (en)

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JP2009035790A (en) 2007-08-03 2009-02-19 Nikko Kinzoku Kk Sintered compact, method for producing transparent electroconductive film, and transparent electroconductive film
JP2012056309A (en) 2010-08-12 2012-03-22 Lintec Corp Transparent conductive film, manufacturing method thereof, and solar cell/electroluminescence element using transparent conductive film

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JPH08264022A (en) * 1995-03-27 1996-10-11 Gunze Ltd Transparent conductive film
JPH08330692A (en) * 1995-05-29 1996-12-13 Asahi Glass Co Ltd Electrode pattern formation method and base body with electrode

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JP2009035790A (en) 2007-08-03 2009-02-19 Nikko Kinzoku Kk Sintered compact, method for producing transparent electroconductive film, and transparent electroconductive film
JP2012056309A (en) 2010-08-12 2012-03-22 Lintec Corp Transparent conductive film, manufacturing method thereof, and solar cell/electroluminescence element using transparent conductive film

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