CN102719792A - Method applying magnetron sputtering method to preparation of transparent conductive film - Google Patents

Method applying magnetron sputtering method to preparation of transparent conductive film Download PDF

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Publication number
CN102719792A
CN102719792A CN2012101998016A CN201210199801A CN102719792A CN 102719792 A CN102719792 A CN 102719792A CN 2012101998016 A CN2012101998016 A CN 2012101998016A CN 201210199801 A CN201210199801 A CN 201210199801A CN 102719792 A CN102719792 A CN 102719792A
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film
sputtering
target
transparent conductive
magnetron sputtering
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李文英
尹桂林
张柯
姜新来
钟建
余震
何丹农
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Shanghai Jiaotong University
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai Jiaotong University
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Abstract

The invention discloses a method applying a magnetron sputtering method to preparation of a transparent conductive film. The method includes: sequentially depositing a Zn1-xCuxO film, a Cu film and a Zn1-xCuxO film on a cleaned substrate at the room temperature by the aid of the magnetron sputtering method so that the Zn1-xCuxO/Cu/Zn1-xCuxO transparent conductive film is obtained; and changing the thickness of the Zn1-xCuxO film and the Cu film by changing sputtering power and sputtering time so that the transparent conductive film with the resistivity smaller than 10<-3>ohm cm and with light transmittance larger than 80% is obtained and can be used for the fields of solar cells, flat-panel displays and the like. The preparation method can be widely applied to industrial production as the magnetron sputtering method has the advantages of simple equipment, cheapness, uniformity in film formation, capability of being used for large-area film preparation and the like.

Description

A kind of method of using magnetron sputtering method to prepare transparent conductive film
Technical field
The present invention relates to the preparation method of the transparent conductive film of field of semiconductor materials, specifically is to prepare Zn with magnetron sputtering method 1-xCu xO/Cu/Zn 1-xCu xThe O transparent conductive film.
Background technology
As one of main optical material of photoelectron sciemtifec and technical sphere, transparent conductive film (TCO) has been widely used in fields such as solar cell transparency electrode, liquid-crystal display, gas sensor, antistatic coating, aircraft and automotive windshield anti-frost mist glass, energy-saving glass window for building and electrochromic device.Require transparent conductive film to have good visible light transmissivity (> in the practical application; 80%) and low resistivity (<10 -3Ω cm), at present most widely used is the In that mixes Sn 2O 3(ITO) transparent conductive film, but the rare ito thin film that causes of indium is comparatively expensive, has therefore limited its application.Doping ZnO has good transmittance and specific conductivity, especially with the research of Al doping ZnO (AZO) with use the most extensively, but in practical application, still has problem such as the higher or chemically unstable of resistivity.
Zn 1-xCu xO/Cu/Zn 1-xCu xThe O film has following advantage: (1) raw material sources are extensive, low price; (2) to the environment toxicological harmless; (3) capability of resistance to radiation is strong; (4) film preparation of three-decker is simple, and design is convenient in film system; (5) thickness of Cu can accurately be controlled, thus the photoelectric properties of conveniently regulating and controlling film; (6) film is simple.So Zn 1-xCu xO/Cu/Zn 1-xCu xThe O film has good application prospects as transparent conductive film.
Retrieval according to prior art finds that Chinese patent 201110239699.3 (application number) has prepared Zn with the method for ald and magnetron sputtering 1-xCu xO/Cu/Zn 1-xCu xThe O transparent conductive film, but atomic layer deposition apparatus is relatively more expensive, is unfavorable for industrialized production.And magnetron sputtering method has that equipment is simple, low price, film forming evenly, can be used for advantage such as big area system film, obtained application widely at present aborning.
Summary of the invention
The technical problem that the present invention will solve provides a kind of magnetron sputtering and prepares Zn 1-xCu xO/Cu/Zn 1-xCu xThe method of O transparent conductive film overcomes the deficiency that prior art exists, and obtains to have the transparent conductive film of high permeability and low-resistivity.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
The substrate that cleans up is placed in the magnetron sputtering chamber, utilize magnetically controlled sputter method sputter Zn successively under pure argon atmosphere 1-xCu xO film, Cu film, Zn 1-xCu xThe O film obtains resistivity less than 10 -3Ω cm, transmittance is greater than 80% Zn 1-xCu xO/Cu/Zn 1-xCu xThe O transparent conductive film.
Further, above-mentioned preparation method carries out according to the following steps:
(1) substrate is used acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning successively, dries up with 99.99% nitrogen afterwards;
(2) use that to contain the Cu amount be that the ZnCuO ceramic target of 0.5% ~ 2.5% (quality percentage composition) is as Zn 1-xCu xThe sputtering target of O thin film deposition;
(3) with high-purity Cu target of 99.99% sputtering target as the Cu thin film deposition;
(4) the magnetron sputtering chamber is vacuumized;
(5) keeping substrate temperature is room temperature, regulates the distance of substrate and target;
(6) the ZnCuO target adopts radio-frequency sputtering;
(7) Zn 1-xCu xO film and Cu film all make in pure argon atmosphere.
Said Zn 1-xCu xThe thickness of O film is 40～70nm, and said Cu film thickness is 8～30nm.
Said substrate is selected sheet glass for use.
In said (1), the ultrasonic cleaning time is 10min.
In said (4), the magnetron sputtering chamber is vacuumized, make its vacuum tightness less than 1.0 * 10 -4Pa is in order to guarantee the content in oxygen room in the Zn1-xCuxO film.
In said (5), the distance of regulating substrate and target is 10～20cm, prevent since substrate and target distance too closely cause from sputter, the while again can not be too far away, thus the assurance quality of forming film.
In said (6), the ZnCuO target adopts radio-frequency sputtering, and wherein sputtering power is 30W, and sputtering time is 30～60min; The Cu target adopts d.c. sputtering, and sputtering power is 80W, and sputtering time is 10～90s.
In said (7), the purity of pure argon is more than 99.99%, and gas pressure intensity is 0.8～1.6Pa.
Principle of work of the present invention is: ZnO is a wide bandgap semiconductor; Has excellent photoelectric performance; Transparent in the visible region; Metal Cu has low-resistivity, through ZnO being mixed and utilizing the Cu middle layer can effectively improve the specific conductivity of film as conductive layer, keeps visible light transmissivity more than 80% simultaneously.
Compared with prior art, the present invention adopts magnetron sputtering to prepare Zn 1-xCu xO/Cu/Zn 1-xCu xThe O transparent conductive film deposits Zn successively on the sheet glass that cleans up under the room temperature 1-xCu xO film, Cu film, Zn 1-xCu xThe O film changes Zn through changing sputtering power and sputtering time 1-xCu xThe thickness of O film and Cu film finally can obtain resistivity less than 10 -3Ω cm, transmittance can be used for fields such as solar cell, flat-panel monitor greater than 80% transparent conductive film.Equipment is simple because magnetron sputtering method has, low price, film forming evenly, can be used for advantage such as big area system film, this preparation method can be used widely in suitability for industrialized production.
Description of drawings
Fig. 1 is Zn among the present invention 1-xCu xO/Cu/Zn 1-xCu xO film synoptic diagram.
Fig. 2 is Zn among the embodiment 1 1-xCu xO/Cu/Zn 1-xCu xThe transmittance curve of O film.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment is that prerequisite is implemented with technical scheme of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
Adopt sheet glass as substrate, sheet glass with acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 10min, is dried up with 99.99% pure nitrogen gas then, it is indoor to put into magnetron sputtering.At film forming gas is under the situation of pure argon, and the maintenance substrate temperature is a room temperature, carries out Zn successively 1-xCu xO, Cu, Zn 1-xCu xThe sputter of O film, promptly the ZnCuO target adopts radio-frequency sputtering, and sputtering power is 30W, and sputtering time is 40min, processes the Zn that thickness is about 45nm 1-xCu xThe O film; The Cu target adopts d.c. sputtering, and sputtering power is 80W, and sputtering time is 25s, processes the Cu middle layer that thickness is about 10nm, and the total thickness of film is about 100nm, and wherein the thickness of film is recorded by ellipsometer.Utilize the vanderburg four electrode method to measure the resistivity of film afterwards, utilize ultraviolet spectrophotometer to measure the transmittance of film.As shown in Figure 2, be Zn among the embodiment 1 1-xCu xO/Cu/Zn 1-xCu xThe transmittance curve of O film.
Embodiment 2:
Sheet glass with acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 10min, is dried up with 99.99% pure nitrogen gas then, and it is indoor to put into magnetron sputtering.At film forming gas is under the situation of pure argon, and the maintenance substrate temperature is a room temperature, carries out Zn successively 1-xCu xO, Cu, Zn 1-xCu xThe sputter of O film, promptly the ZnCuO target adopts radio-frequency sputtering, and sputtering power is 30W, and sputtering time is 40min, processes the Zn that thickness is about 45nm 1-xCu xThe O film; The Cu target adopts d.c. sputtering, and sputtering power is 80W, and sputtering time is 35s, processes the Cu middle layer that thickness is about 14nm, and the total thickness of film is about 102nm, and wherein the thickness of film is recorded by ellipsometer.Utilize the vanderburg four electrode method to measure the resistivity of film afterwards, utilize ultraviolet spectrophotometer to measure the transmittance of film.
Embodiment 3:
Sheet glass with acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 10min, is dried up with 99.99% pure nitrogen gas then, and it is indoor to put into magnetron sputtering.At film forming gas is under the situation of pure argon, and the maintenance substrate temperature is a room temperature, carries out Zn successively 1-xCu xO, Cu, Zn 1-xCu xThe sputter of O film, promptly the ZnCuO target adopts radio-frequency sputtering, and sputtering power is 30W, and sputtering time is 60min, processes the Zn that thickness is about 65nm 1-xCu xThe O film; The Cu target adopts d.c. sputtering, and sputtering power is 80W, and sputtering time is 25s, processes the Cu middle layer that thickness is about 10nm, and the total thickness of film is about 140nm, and wherein the thickness of film is recorded by ellipsometer.Utilize the vanderburg four electrode method to measure the resistivity of film afterwards, utilize ultraviolet spectrophotometer to measure the transmittance of film.
Embodiment 4:
Sheet glass with acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 10min, is dried up with 99.99% pure nitrogen gas then, and it is indoor to put into magnetron sputtering.At film forming gas is under the situation of pure argon, and the maintenance substrate temperature is a room temperature, carries out Zn successively 1-xCu xO, Cu, Zn 1-xCu xThe sputter of O film, promptly the ZnCuO target adopts radio-frequency sputtering, and sputtering power is 30W, and sputtering time is 60min, processes the Zn that thickness is about 65nm 1-xCu xThe O film; The Cu target adopts d.c. sputtering, and sputtering power is 80W, and sputtering time is 40s, processes the Cu middle layer that thickness is about 16nm, and the total thickness of film is about 146nm, and wherein the thickness of film is recorded by ellipsometer.Utilize the vanderburg four electrode method to measure the resistivity of film afterwards, utilize ultraviolet spectrophotometer to measure the transmittance of film.
Embodiment 5:
Sheet glass with acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 10min, is dried up with 99.99% pure nitrogen gas then, and it is indoor to put into magnetron sputtering.At film forming gas Ar/N 2Under the situation for 2:1, the maintenance substrate temperature is a room temperature, carries out Zn successively 1-xCu xO, Cu, Zn 1-xCu xThe sputter of O film, promptly the ZnCuO target adopts radio-frequency sputtering, and sputtering power is 30W, and sputtering time is 40min, processes the Zn that thickness is about 45nm 1-xCu xThe O film; The Cu target adopts d.c. sputtering, and sputtering power is 80W, and sputtering time is 30s, processes the Cu middle layer that thickness is about 12nm, and the total thickness of film is about 102nm.Utilize the vanderburg four electrode method to measure the resistivity of film afterwards, utilize ultraviolet spectrophotometer to measure the transmittance of film.
Embodiment 6:
Sheet glass with acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 10min, is dried up with 99.99% pure nitrogen gas then, and it is indoor to put into magnetron sputtering.At film forming gas is under the situation of pure argon, and the maintenance substrate temperature is a room temperature, carries out Zn successively 1-xCu xO, Cu, Zn 1-xCu xThe sputter of O film, promptly the ZnCuO target adopts radio-frequency sputtering, and sputtering power is 80W, and sputtering time is 50min, processes the Zn that thickness is about 60nm 1-xCu xThe O film; The Cu target adopts d.c. sputtering, and sputtering power is 80W, and sputtering time is 40s, processes the Cu middle layer that thickness is about 16nm, and the total thickness of film is about 136nm, and wherein the thickness of film is recorded by ellipsometer.Utilize the vanderburg four electrode method to measure the resistivity of film afterwards, utilize ultraviolet spectrophotometer to measure the transmittance of film.
More than the membrane structure that obtains of each embodiment as shown in Figure 1, deposit certain thickness Zn on the substrate 1 successively 1-xCu xO film 2, Cu film 3 and Zn 1-xCu xO film 4, the optics and the electric property of gained film are as shown in table 1 below.
The optics and the electric property of film among each embodiment of table 1
The embodiment numbering 1 2 3 4 5 6
Resistivity/* 10 -4Ω·cm 2.3 0.95 4.5 1.9 1.2 2.9
Average transmittances/% 85 80 85 84 83 87
Although content of the present invention has been done detailed introduction through above-mentioned preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple modification of the present invention with to substitute all will be conspicuous.Therefore, protection scope of the present invention should be limited appended claim.

Claims (10)

1. one kind is utilized magnetron sputtering method to prepare Zn 1-xCu xO/Cu/Zn 1-xCu xThe method of O transparent conductive film is characterized in that: the substrate that cleans up is placed in the magnetron sputtering chamber, utilize magnetically controlled sputter method sputter Zn successively under pure argon atmosphere 1-xCu xO film, Cu film, Zn 1-xCu xThe O film obtains resistivity less than 10 -3Ω cm, transmittance is greater than 80% Zn 1-xCu xO/Cu/Zn 1-xCu xThe O transparent conductive film.
2. method according to claim 1 is characterized in that, this method is carried out according to the following steps:
(1) substrate is used acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning successively, dries up with 99.99% nitrogen afterwards;
(2) use that to contain the Cu amount be that 0.5% ~ 2.5% ZnCuO ceramic target is as Zn 1-xCu xThe sputtering target of O thin film deposition;
(3) with high-purity Cu target of 99.99% sputtering target as the Cu thin film deposition;
(4) the magnetron sputtering chamber is vacuumized;
(5) keeping substrate temperature is room temperature, regulates the distance of substrate and target;
(6) the ZnCuO target adopts radio-frequency sputtering; The Cu target adopts d.c. sputtering;
(7) Zn 1-xCu xO film and Cu film all make in pure argon atmosphere.
3. method according to claim 1 and 2 is characterized in that, said Zn 1-xCu xThe thickness of O film is 40～70nm, and said Cu film thickness is 8～30nm.
4. method according to claim 2 is characterized in that, in said (1), the ultrasonic cleaning time is 10min.
5. method according to claim 2 is characterized in that, in said (4), the magnetron sputtering chamber is vacuumized, and makes its vacuum tightness less than 1.0 * 10 -4Pa.
6. method according to claim 2 is characterized in that, in said (5), the distance of regulating substrate and target is 10～20cm.
7. method according to claim 2 is characterized in that, in said (6), the ZnCuO target adopts radio-frequency sputtering, and wherein sputtering power is 30W, and sputtering time is 30～60min.
8. according to claim 2 or 7 described methods, it is characterized in that in said (6), the Cu target adopts d.c. sputtering, sputtering power is 80W, and sputtering time is 10～90s.
9. method according to claim 2 is characterized in that, in said (7), the purity of pure argon is more than 99.99%, and gas pressure intensity is 0.8～1.6Pa.
10. method according to claim 1 and 2 is characterized in that said substrate is selected sheet glass for use.
CN2012101998016A 2012-06-18 2012-06-18 Method applying magnetron sputtering method to preparation of transparent conductive film Pending CN102719792A (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN104593733A (en) * 2015-02-13 2015-05-06 哈尔滨工业大学 Pulsed laser deposition preparation method for copper-doped zinc oxide nanorod
CN104616726A (en) * 2014-12-17 2015-05-13 青岛墨烯产业科技有限公司 Indium-free transparent electrode and preparation method thereof
CN109225247A (en) * 2018-10-18 2019-01-18 上海纳米技术及应用国家工程研究中心有限公司 Tungsten oxide-cuprous oxide heterojunction photovoltaic pole material preparation method and products thereof and application
CN114107917A (en) * 2021-11-11 2022-03-01 中国科学院宁波材料技术与工程研究所 Copper-doped zinc oxide transparent conductive film and preparation method thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104616726A (en) * 2014-12-17 2015-05-13 青岛墨烯产业科技有限公司 Indium-free transparent electrode and preparation method thereof
CN104593733A (en) * 2015-02-13 2015-05-06 哈尔滨工业大学 Pulsed laser deposition preparation method for copper-doped zinc oxide nanorod
CN104593733B (en) * 2015-02-13 2017-01-04 哈尔滨工业大学 The pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods
CN109225247A (en) * 2018-10-18 2019-01-18 上海纳米技术及应用国家工程研究中心有限公司 Tungsten oxide-cuprous oxide heterojunction photovoltaic pole material preparation method and products thereof and application
CN114107917A (en) * 2021-11-11 2022-03-01 中国科学院宁波材料技术与工程研究所 Copper-doped zinc oxide transparent conductive film and preparation method thereof
CN114107917B (en) * 2021-11-11 2022-11-15 中国科学院宁波材料技术与工程研究所 Copper-doped zinc oxide transparent conductive film and preparation method thereof

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Application publication date: 20121010