CN100595847C - Electrically conducting transparent film and its preparing process - Google Patents

Electrically conducting transparent film and its preparing process Download PDF

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Publication number
CN100595847C
CN100595847C CN200710160242A CN200710160242A CN100595847C CN 100595847 C CN100595847 C CN 100595847C CN 200710160242 A CN200710160242 A CN 200710160242A CN 200710160242 A CN200710160242 A CN 200710160242A CN 100595847 C CN100595847 C CN 100595847C
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magnesium
zinc
gallium
aluminium
transparent conductive
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CN200710160242A
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Chinese (zh)
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CN101221830A (en
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叶志镇
马全宝
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention discloses a transparent conductive film which is a gallium doped or aluminium doped zinc-magnesium-oxygen film. The mol percentage of each component is as follows: the aluminium or gallium occupies 1.0 to 5.0 percent, the magnesium occupies 1 to 20.0 percent, the remaining is the zinc, and the mol number ratio of zinc-magnesium-aluminium or zinc-magnesium-gallium to O is 1:1. The DCreactive magnetic control sputtering method is adopted and the film is prepared by taking a zinc-magnesium-aluminium alloy or a zinc-magnesium-gallium alloy as a target. The method of the invention issimple, the doped quantity is easy to control, and a deposition system is simple, easy to operate and can realize the extensive metallic-membrane plating. Compared with other preparative techniques,the method is more beneficial to the realization of the industrial production. The gallium doped zinc-magnesium-oxygen or aluminium doped zinc-magnesium-oxygen transparent conductive film prepared bythe invention has high transmittance, good electrooptics performance, repetitiveness and stability.

Description

A kind of transparent conductive film and preparation method thereof
Technical field
The present invention relates to the preparation method of zinc oxide transparent conductive film, especially aluminium is mixed the preparation method that zinc-magnesium oxygen and gallium are mixed zinc-magnesium oxygen transparent conductive film.
Background technology
Transparent conductive oxide has obtained using widely in fields such as making luminescent device, non-crystal silicon solar cell, fiber waveguide, transducer and plate of flat liquid crystal display as a kind of important optoelectronic information material.In this class material, zinc oxide (ZnO) film is the n N-type semiconductor N material of a kind of broad stopband (3.3eV), easily produces defective and carries out doping impurity, with respect to indium tin oxide (ITO) and SnO 2, have low price, abundant raw material, nontoxic, depositing temperature relatively low and in the hydrogen plasma environment advantage such as good stability, be a kind of material that is hopeful to substitute ITO most.By mixing B, Al, Ga, In, F etc. can make its conductivity improve one to two order of magnitude.In all metal-doped elements, Al and Ga are considered to the most promising doped chemical.In addition, the doping of Mg can improve the energy gap of ZnO.In the ZnO ultraviolet light-emitting diode, the n-ZnMgO transparent conductive film can be used as the combined efficiency again that electronics-hole in the ZnMgO homojunction is improved on the barrier layer.But, mix aluminium zinc-magnesium oxygen at present and mix the thin research that is used on the LED of gallium zinc-magnesium oxygen electrically conducting transparent and also do not attract much attention, nowadays also there is not the research report of this respect.
Summary of the invention
The purpose of this invention is to provide that a kind of aluminium is mixed zinc-magnesium oxygen or gallium is mixed zinc-magnesium oxygen transparent conductive film and preparation method thereof.
Transparent conductive film of the present invention is the zinc-magnesium oxygen film that gallium mixes or aluminium mixes, and each mole percent level of forming is:
Aluminium or gallium 1.0~5.0%
Magnesium 1~20.0%
Surplus is a zinc, and said components content sum is 100%, and (Zn+Mg+Al) or (Zn+Mg+Ga) ratio with the molal quantity of O is 1: 1.
The preparation method of transparent conductive film of the present invention, step is as follows:
To directly put into the reative cell of direct current reaction magnetron sputtering device after the substrate cleaning, reative cell vacuum degree is evacuated to 3 * 10 -3Pa is a target with zinc-magnesium aluminium or zinc-magnesium gallium alloy, and aluminium or gallium molar content are 1.0~5.0%, and the magnesium molar content is 1~20.0%, with pure Ar and pure O 2As sputter gas input reative cell, Ar: O 2=2: 1~8: 1, under 0.5~2.0Pa pressure, under 200~350 ℃, carry out the sputter growth.
Above-mentioned substrate can be glass or quartz or plastics or organic flexible substrate or silicon chip or sapphire.The purity of described Ar is more than 99.99%, and oxygen purity is more than 99.99%.
The present invention is with O 2As oxygen source, Ar is as auxiliary sputter gas.In the sputter procedure, sputtered atom (Zn, Ga or Al) under the protection of Ar with O 2React, deposition forms the high transparent high conductive ZnMgO film that Ga mixes or Al mixes on substrate.
The present invention is by changing Ar and O 2Voltage ratio can change and mix aluminium or mix the gallium amount.Film thickness is determined by growth time.
Beneficial effect of the present invention is: the inventive method is simple, use be alloy target material, doping is easy to control, depositing system is simple, easy to operate, can realize large-area coating film, compares with other technology of preparing, more helps realizing suitability for industrialized production.The gallium that the present invention makes is mixed zinc-magnesium oxygen and aluminium and is mixed zinc-magnesium oxygen transparent conductive film and have high permeability, and good electrooptics performance is repeated and stable.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates that gallium is mixed zinc-magnesium oxygen transparent conductive film;
Fig. 2 is the optical transmission spectrum that gallium is mixed zinc-magnesium oxygen transparent conductive film.
Embodiment
Embodiment 1
Be put on the specimen holder of direct current reaction magnetron sputtering device reaction chamber after will glass substrate cleaning, place down on the substrate deposition surface, can effectively prevent granular impurity to the staining of substrate surface, and reative cell vacuum degree is evacuated to 3 * 10 -3Pa is a target with the zinc-magnesium gallium alloy, and the molar content of gallium is 5.0%, and the molar content of magnesium is 10%, is that 99.99% Ar and purity are 99.99% O with purity 2As sputter gas, two kinds of gases are imported reative cell, Ar: O by flowmeter control respectively 2=4: 1, the pressure of reative cell is 1.5Pa.Power at 100W begins sputter, and underlayer temperature is 300 ℃, and growth time 10min obtains the transparent conductive film of thick about 500nm.
The gallium of preparation is mixed zinc-magnesium oxygen transparent conductive film and is at room temperature had excellent electro-optical properties, and among this embodiment, film resiativity is 4.6 * 10 -4Ω .cm, Hall mobility is 7.5cm 2/ V.s, electronic carrier concentration is 1.82 * 10 21Cm -3, the visible light average transmittance be 90% and more than, and place 1 year its electro-optical characteristic and do not have significant change, stable performance is a kind of zinc-oxide film of good high transparent high conductive.
The X-ray diffraction of above-mentioned film (XRD) collection of illustrative plates is seen Fig. 1, has only (002) and (004) diffraction maximum of ZnO to occur, and the gallium that shows the inventive method preparation is mixed zinc-magnesium oxygen transparent conductive film and had good crystal property.
Figure 2 shows that the optical transmission spectrum of above-mentioned film.As seen from the figure, reach 90% and above (not containing substrate), show that gallium that the inventive method prepares mixes zinc-magnesium oxygen transparent conductive film and have the good optical performance in the average transmittance of visible region.
Embodiment 2
Be put on the specimen holder of direct current reaction magnetron sputtering device reaction chamber after will silicon chip substrate cleaning, place down on the substrate deposition surface, can effectively prevent granular impurity to the staining of substrate surface, and reative cell vacuum degree is evacuated to 3 * 10 -3Pa is a target with the zinc-magnesium aluminium alloy, and the molar content of aluminium is 1.0%, and the molar content of magnesium is 1%, is that 99.99% Ar and purity are 99.99% O with purity 2As sputter gas, two kinds of gases are imported reative cell, Ar: O by flowmeter control respectively 2=8: 1, the pressure of reative cell is 2.0Pa.Power at 100W begins sputter, and underlayer temperature is 200 ℃, and growth time 10min obtains the transparent conductive film of thick about 500nm.
The aluminium of preparation is mixed zinc-magnesium oxygen transparent conductive film and is at room temperature had excellent electro-optical properties, and among this embodiment, film resiativity is 5.0 * 10 -4Ω .cm, Hall mobility is 7.8cm 2/ V.s, electronic carrier concentration is 1.6 * 10 21Cm -3, the visible light average transmittance be 90% and more than.

Claims (4)

1. a transparent conductive film is characterized in that it is the zinc-magnesium oxygen film that gallium mixes or aluminium mixes, and each mole percent level of forming is:
Aluminium or gallium 1.0~5.0%
Magnesium 1~20.0%
Surplus is a zinc, and said components content sum is 100%, and (Zn+Mg+Al) or (Zn+Mg+Ga) ratio with the molal quantity of O is 1: 1.
2. the preparation method of the described transparent conductive film of claim 1 is characterized in that step is as follows:
To directly put into the reative cell of direct current reaction magnetron sputtering device after the substrate cleaning, reative cell vacuum degree is evacuated to 3 * 10 -3Pa is a target with zinc-magnesium aluminium or zinc-magnesium gallium alloy, and aluminium or gallium molar content are 1.0~5.0%, and the magnesium molar content is 1~20.0%, with pure Ar and pure O 2As sputter gas input reative cell, Ar: O 2=2: 1~8: 1, under 0.5~2.0Pa pressure, under 200~350 ℃, carry out the sputter growth.
3. the preparation method of transparent conductive film according to claim 2 is characterized in that said substrate is the quartzy or organic flexible substrate of glass or silicon chip or sapphire.
4. the preparation method of transparent conductive film according to claim 2, the purity that it is characterized in that Ar is more than 99.99%, oxygen purity is more than 99.99%.
CN200710160242A 2007-12-14 2007-12-14 Electrically conducting transparent film and its preparing process Expired - Fee Related CN100595847C (en)

Priority Applications (1)

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Application Number Priority Date Filing Date Title
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CN100595847C true CN100595847C (en) 2010-03-24

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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101300560B1 (en) * 2009-07-01 2013-09-03 삼성코닝정밀소재 주식회사 ZnO-based conductor
KR20120094035A (en) * 2009-12-16 2012-08-23 미쓰비시 마테리알 가부시키가이샤 Transparent conductive film, solar cell using same, sputtering target for forming said transparent conductive film, and manufacturing method therefor
CN103199189B (en) * 2012-01-09 2015-04-22 清华大学 Codope ZnO thin film with high visible light transmittance and high piezoelectric constants
CN103132018B (en) * 2013-03-12 2015-03-18 电子科技大学 Method for improving electric conductivity of amorphous silicon membrane
CN109628899A (en) * 2019-01-24 2019-04-16 苏州罗纳尔材料科技有限公司 Rotate zinc-magnesium target and preparation method thereof
JPWO2021090790A1 (en) * 2019-11-08 2021-05-14
CN113088907A (en) * 2021-03-26 2021-07-09 哈尔滨工业大学 Preparation method of MgGaZnO film with deep ultraviolet detection function
CN114807856A (en) * 2022-04-28 2022-07-29 浙江大学 Fluorine-doped indium tin oxide transparent conductive film and preparation method thereof

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Application publication date: 20080716

Assignee: Nanjing Huijin Jinyuan Optoelectronic Materials Co., Ltd.

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Denomination of invention: Transparent conducting thin film and preparation method thereof

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