KR20140037458A - 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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KR20140037458A
KR20140037458A KR1020120103571A KR20120103571A KR20140037458A KR 20140037458 A KR20140037458 A KR 20140037458A KR 1020120103571 A KR1020120103571 A KR 1020120103571A KR 20120103571 A KR20120103571 A KR 20120103571A KR 20140037458 A KR20140037458 A KR 20140037458A
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thin film
boron
transparent conductive
indium
oxide
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KR1020120103571A
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KR101627331B1 (en
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이영주
박종일
김주영
오윤석
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재단법인 포항산업과학연구원
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Abstract

According to one embodiment of the present invention, disclosed are a transparent electroconductive thin film composition, a method for forming a transparent electroconductive thin film using the same, and a transparent electroconductive thin film manufactured thereby. The transparent electroconductive thin film composition includes indium (In), gallium (Ga), boron (B), zinc (Zn), and oxygen (O2), wherein the ratio of the indium, gallium, boron, and zinc, (In+Ga)/(In+Ga+B+Zn), is 25 to 65 atomic percent and boron content is 4-8 atomic percent.

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 for forming a transparent conductive thin film and a transparent conductive thin film using the same, and more particularly, by sputtering a composite of indium, gallium, zinc, and boric oxide on a material surface of glass, ceramic, or plastic. It relates to a method for forming a thin film excellent in transparency and conductivity, and to 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). Methods of manufacturing the ITO film include spraying, vacuum evaporation, sputtering and ion plating, and sputtering methods are most commonly used commercially.

The ITO film produced by the above methods is not only excellent in transparency and conductivity, but also has excellent etching property and good adhesion to the substrate. 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 such scarcity of resources, human hazards, and nodule generation problems during sputtering, research on alternative materials that can reduce indium in ITO or replace ITO is needed.

In response to this need, new research on transparent electrode materials has been conducted: tin oxide (FTO, ATO) doped with fluorine (F) or antimony (Sb), and zinc oxide (AZO, GZO, doped with aluminum, gallium, and indium). IZO) and the like, but more specific research is required.

The present invention for solving the above problems is a transparent conductive thin film composition comprising indium, gallium, boron and zinc oxide, a method for forming a thin film having improved transparency and conductivity by coating it on the material surface and the transparent conductive material produced thereby To provide a thin film.

In one or more embodiments of the present invention include indium (In), gallium (Ga), boron (B), zinc (Zn) and oxygen (O 2 ), the ratio of the indium, gallium, boron and zinc ( Provided is a transparent conductive thin film composition, wherein In + Ga) / (In + Ga + B + Zn) is 25 to 65 atomic percent (atomic%), and the boron content is 4 to 8 atomic percent (atomic%). Can be.

In addition, in one or more embodiments of the present invention, a mixture is prepared by mixing indium oxide (In 2 O 3 ), gallium oxide (Ga 2 O 3 ), boron oxide (B 2 O 3 ), and zinc oxide (ZnO) powder. Manufacturing step; Preparing a sintered body in which the mixture is put into a mold and molded into a press, followed by heat treatment; And forming a thin film on a substrate prepared by sputtering using the sintered body.

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

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

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

1 is a scanning electron micrograph of a transparent conductive material prepared by Example 1 according to the present invention.
2 is EDX data of the transparent conductive material prepared by Example 1 according to the present invention.
3 is a flowchart illustrating a process of forming a transparent conductive thin film according to an embodiment of the present invention.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail with 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.

Embodiment according to the present invention relates to a composition for manufacturing a transparent conductive thin film, a composition of a low resistance transparent conductive thin film prepared using the same.

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

In the embodiment according to the present invention was added to the mixture of indium, gallium and zinc oxide to improve the sintering characteristics of the indium, gallium, zinc oxide composite at a general temperature and thereby to improve the overall properties of the conductive thin film.

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

In addition, the content of boron in the embodiment 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 boron exceeds 8 atomic percent, there is a problem of low conductivity, and the ratio of boron is 4 atomic percent If less, the effect of boron on sintering is insufficient. In addition, when the atomic ratio of (In + Ga) / (In + Ga + B + Zn) exceeds 65 atomic percent, there is a problem in that the price is excessively increased and the difference from the existing ITO is less. In the examples, the content of boron and the ratio of (In + Ga) / (In + Ga + B + Zn) are limited to the above ranges.

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.

In addition, the embodiment according to the present invention provides a method for forming a transparent conductive thin film, Figure 3 is a flowchart for forming a transparent conductive thin film according to an embodiment of the present invention.

Referring to FIG. 3, the method for forming a transparent conductive thin film includes 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). The mixture is prepared by mixing (S100), the prepared mixture is put into a mold, processed by molding, and then heat-treated to prepare a sintered body (S110), and then sputtering (sputtering) as a target of the sintered material By forming a thin film on the substrate (S120).

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

In the embodiment according to the present invention, 90-120 g of indium oxide (In 2 O 3 ) powder, 50-80 g of gallium oxide (Ga 2 O 3 ) powder, zinc oxide (ZnO) powder as a solid oxide for powder mixing of the metal oxide Add 45 ~ 70g of boron oxide (B 2 O 3 ) and 20 ~ 25g of total 250 ~ 300g of oxide powder into a polyethylene pot, fill with ethanol, and ball mill for 24 hours using ZrO 2 ball. The mixture was mixed by a ball milling method and then dried with sufficient stirring on a plate at 120 ° C.

In order to mold and sinter the dried mixed powder, the dried mixed powder was placed in a mold, pressed and molded at a pressure of 300 Kg / cm 2 , and then sintered in air. The temperature increase rate for sintering was 10 ℃ / min, sintering was carried out at 1350 ℃ for 6 hours. The composition analysis of the molded body was performed using EPMA, and the results are shown in Table 1.

In addition, in the embodiment according to the present invention in order to deposit the molded body on the material surface RF power: 30W, gas pressure: 5X10 -3 Torr, argon (Ar) gas flow rate: 15 SCCM, oxygen (O 2 ) gas flow rate : 5 SCCM, board | substrate temperature: Sputtering was performed at normal temperature, and film thickness 3000 Pa.

Electrical conductivity and transparency were measured for the sputtered material, and the conductivity was measured using a 4-point probe surface resistance meter for a film having a thickness of 3000 mW, and the transparency was measured at 550 nm for a film having a thickness of 3000 mW. Was measured. In addition, the compositional analysis was measured using EPMA for a film of 3000 mm 3 thickness.

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 manufactured by the embodiment according to the present invention has a transmittance of 80% or more and a thickness of 5000 kPa or less. If the transmittance is less than 80% or the thickness is larger than 5000 kPa, the electrical conductivity is increased. have. In other words, transparency and conductivity are important in the transparent conductive thin film. Since all materials have a resistance inversely proportional to the thickness of the material, the electrical conductivity is increased when the thickness is thickly deposited. However, when the material is thickly deposited, the permeability decreases and becomes opaque. Thus, in order to compensate for this, additionally, boron oxide (B 2 O 3 ) and zinc oxide (ZnO) are added in a small amount.

By addition of the boron oxide and zinc oxide, additional electron orbits are generated by the boron and zinc atoms to improve conductivity, and improve transmittance 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 Sintered Check Example 2 91 79 Amorphous Sintered Check Example 3 92 81 Amorphous Sintered Check Example 4 90 84 Crystalline Sintered Check Example 5 84 93 Crystalline Example 6 82 95 Crystalline Comparative Example 1 94 86 Amorphous Sintered Check Comparative Example 2 89 92 Crystalline Comparative Example 3 82 99 Crystalline

In addition, Table 3 shows the evaluation of the characteristics of the transparent conductive thin film prepared according to the embodiment according to the present invention, which was analyzed using an X-diffraction analyzer and an electron microscope for the dielectric glass produced by the present invention. .

Generally, it is preferable to induce the crystalline thin film to emerge as crystalline because of its better conductivity 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 1-3 are amorphous and Examples 4-6 are crystalline. In addition, when looking at the result of the comparative example which does not contain a boron oxide, the comparative example 1 is amorphous, and the comparative examples 2-3 are crystalline. As a result of analyzing the degree of sintering through an electron microscope to see the effect of boron on the sintering, 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, Comparative Examples 1, 3 to 4, Comparative Examples 2, 5 to 6, and Comparative Example 3 are similar, the comparison between Examples 3 to 4 and Comparative Example 2 As a result, it was confirmed that boron contributes to sintering regardless of crystallinity, and it showed that electrical resistance was improved by showing low resistance on the sintering side. A scanning electron micrograph of Example 1 according to the present invention is shown in FIG. 1, and the results of elemental analysis of the thin film of Example 1 are shown in FIG. 2.

In the embodiment according to the present invention to prepare a transparent conductive thin film using a composition consisting of indium, gallium, boron, zinc oxide, the thin film has a visible light transmittance of 80% or more and the electrical conductivity is superior to the oxide composition without boron. Confirmed. These thin films can be used as electrodes in LCDs, PDPs, OLEDs, and touch panels because of their good adhesion to substrates, and can also be used in electromagnetic shielding materials, heating elements, solar cells, and the like.

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)

Indium (In), gallium (Ga), boron (B), zinc (Zn) and oxygen (O 2 ),
The ratio of indium, gallium, boron and zinc (In + Ga) / (In + Ga + B + Zn) is 25 to 65 atomic percent (atomic%), while the content of boron is 4 to 8 atomic percent (atomic%) Transparent conductive thin film composition, characterized in that. Preparing a mixture by mixing indium oxide (In 2 O 3 ), gallium oxide (Ga 2 O 3 ), boron oxide (B 2 O 3 ), and zinc oxide (ZnO) powder;
Preparing a sintered body in which the mixture is put into a mold and molded into a press, followed by heat treatment; And
And forming a thin film on the substrate prepared by sputtering using the sintered body. 3. The method of claim 2,
The mixture has an indium, gallium, boron, and zinc ratio (In + Ga) / (In + Ga + B + Zn) of 25 to 65 atomic percent (atomic%), and the content of boron is 4 to 8 atomic percent (atomic). %) Is a transparent conductive thin film forming method. The transparent conductive thin film formed by the method according to claim 2 or 3.
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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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160057789A (en) * 2014-11-14 2016-05-24 삼성전자주식회사 Electrically conductive thin films

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160057789A (en) * 2014-11-14 2016-05-24 삼성전자주식회사 Electrically conductive thin films

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