CN103305792A - Zinc-oxide-doped transparent film and preparation method thereof - Google Patents

Zinc-oxide-doped transparent film and preparation method thereof Download PDF

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Publication number
CN103305792A
CN103305792A CN2012100673549A CN201210067354A CN103305792A CN 103305792 A CN103305792 A CN 103305792A CN 2012100673549 A CN2012100673549 A CN 2012100673549A CN 201210067354 A CN201210067354 A CN 201210067354A CN 103305792 A CN103305792 A CN 103305792A
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oxide
doped element
zinc
gas
ranges
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CN2012100673549A
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Inventor
谈一波
吴雪飞
黄琦凯
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Jiangsu Xinyuan Power Co Ltd
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Jiangsu Xinyuan Power Co Ltd
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Abstract

The invention relates to a zinc-oxide-based doping element transparent conductive film which comprises a glass substrate layer and an oxide-zinc-based doping element film layer with a micropore structure. The preparation method comprises the following steps: mixing doping elements with zinc oxide, drying and grinding so as to obtain precursor doping powder, and mixing and sintering so as to obtain an oxide-zinc-based doping element target material; by taking glass as a substrate layer and utilizing a magnetron sputtering method, performing the gas pumping in vacuum to reach 0.6-3.0*10<-4>Pa under the conditions that the sputtering gas is selected from argon, oxygen, hydrogen, an inert gas or a mixed gas thereof, the temperature ranges from a room temperature to 500 DEG C, the working pressure ranges from 0.06 to 3.0Pa, the direct-current sputtering power ranges from 10 to 120W, the deposition time ranges from 3 to 60 minutes. In addition, the base substrate ranges from 5 to 40 nm in distance and the film ranges from 100 to 2000 nm in thickness.

Description

Adulterated zinc oxide transparent film and preparation method thereof
Technical field
The present invention relates to zno-based doped element type transparent conductive film and preparation method thereof, belong to transparent conductive material thin film technique field.
Background technology
Since the self-induced transparency electro-conductive material was found, because of the great demand of industrial trade, transparent conductor material was widely used, and transparent conductive material has high-clarity and high conductivity.Large-scale application is in flat pannel display and photovoltaic new energy resources system.
The zno-based TCO material of doped element is applied in flat-panel monitor and solar cell.The utilization of more solar energies of solar absorption is larger for solar cell, is the photoelectric transformation efficiency that further improves solar cell, is devoted at present to reduce the luminous reflectance of battery surface, strengthens effective absorption of light.A kind of effective measures are that the transparency conductive electrode surface is improved, make the surface form well-regulated structure, in the preparation of monocrystaline silicon solar cell, utilize alkali lye to carry out surface tissue, strengthen Optical Absorption, reduce the reflectivity on surface, thereby improve the efficiency of conversion of sun power.
To the zno-based transparent conductive electrode, mainly process by diluted acid (hydrochloric acid, nitric acid) effects on surface, utilize corrosion principle to form suede structure on the film surface, improve the transfer power of solar cell.Progressively developed in recent years in plasma gas the dry etching processing was carried out on zno-based transparency conductive electrode surface.Above-mentioned alkali liquid corrosion, acid liquid corrosion and dry plasma etch, complex treatment process, homogeneity, repeatability are relatively poor, affect the performance of solar cell.
Development high-performance ZnO base transparent conducting film, exploitation multi-element doping ZnO material technology amasss structure to its surface, has broad application prospects in solar energy electrical equipment field.
Summary of the invention
The object of the invention is to it and overcome the deficiencies in the prior art, transparent conductive material of a kind of Zinc oxide doped element and preparation method thereof is provided.The following technical scheme of concrete employing:
A kind of Zinc oxide-base doped element transparent conductive film comprises that glass lined bottom and surface have the Zinc oxide-base doped element rete of microvoid structure; Described doped element is the simple substance element, the compounds such as oxide compound, oxyhydroxide.
In the preferred scheme, the ratio of described doped element is 0.2~10.0% (mol).
The preparation method of above-mentioned transparent conductive film comprises the steps:
(1) doped element and zinc oxide are mixed, dry, ground, get forerunner's adulterated powder; Forerunner's adulterated powder again with the adulterated powder compression molding after the pre-burning, at 1100-1450 ℃ of sintering 1-16 hour, made doped element Zinc oxide-base target in 500-1000 ℃ of pre-burning 2-24 hour;
The ratio of described doped element is 0.20-10% (mol), and doped element is the simple substance element, oxide compound, oxyhydroxide, vitriol, nitrate, muriate, alkoxide or fluorochemical;
(2) take glass as substrate layer, adopt magnetron sputtering method, vacuum suction is to 0.6-3.0 * 10 -4Pa, sputter gas are argon gas, oxygen, hydrogen, rare gas element or their mixed gas; Temperature is 25 ℃ to 500 ℃ of chambers, and operating pressure is 0.06-3.0Pa, and d.c. sputtering power is 10-120W, and depositing time is 3-60min; The base material substrate distance is 5-40nm, and thickness is 100-2000nm.
Compared with prior art, doping zinc-oxide base transparent conducting film provided by the invention surface has microvoid structure, when guaranteeing good electric property, can improve the solar ray transmitance, thereby improve the photoelectric transformation efficiency of solar cell, and preparation technology is simple, and is with low cost, is suitable for suitability for industrialized production.
Embodiment
The following examples can make the present invention of those of ordinary skill in the art's comprehend, but do not limit the present invention in any way.
The step of zno-based of the present invention (Zinc oxide-base) doping techniques: the transparent conductive material of doping zinc-oxide base is made through mixing, sintering process by the raw material that contains doped element and the raw material that contains zinc element.The ratio of doped element is 0.20-10.0mol%.Doped element is element simple substance, oxide compound, oxyhydroxide, alkoxide, vitriol, nitrate, muriate or fluorochemical.
The zno-based doped element that obtains take aforesaid method is as target, adopt magnetron sputtering method, take glass as substrate, background vacuumizes gas to 1.0-3.0 * 10-4Pa, take high purity argon, oxygen, hydrogen, rare gas element or their mixed gas as working gas, operating air pressure is 0.6-3.0Pa, underlayer temperature is that d.c. sputtering power is controlled between the 10-160W between the room temperature to 500 ℃, and depositing time is 10-60min, target and substrate distance are 5-9cm, obtain the adulterated zinc oxide transparent film.
Embodiment 1
(1) with purity be 99.99% ZnO and simple substance Al, the doping of pressing Al than 2.0mol% mix, oven dry, then in ball mill, ground 2 hours, with forerunner's powder of obtaining 800 ℃ of pre-burnings 6 hours.With the adulterated flour compression moulding after burning, and then in 1250 ℃ of sintering 4 hours, make the ZnO:Al target.
(2) adopt simple glass to make substrate, the substrate ultrasonic cleaning is used alcohol wash again; With the target of step (1) and the substrate after cleaning send into direct current and penetrate magnetic control sputtering device, sputtering instrument background base vacuum is 3 * 10 -4Pa.Sputter gas is the argon gas of purity 99.99%, and operating air pressure is 0.5Pa, and sputtering power is 16w, and sputtering time is to obtain doped zinc oxide transparent conductive film in 100 minutes.
The transparent conductive film well-crystallized of the present embodiment preparation, thickness is 300nm, the resistivity of film is 8.2 * 10 -4Ω .cm.
Embodiment 2
(1) with purity is 99.99% ZnO and MoO 3Powder is pressed MoO 3Doping mix than 3% (mol), with ball mill ball milling 3 hours, make forerunner's powder 1000 ℃ of pre-burnings 4 hours, the adulterated flour compression moulding after firing makes the ZnO:Mo target in 1300 ℃ of sintering 2h again.
(2) make substrate with glass, substrate ultrasonic wave and alcohol wash; The target of step (1) and the glass substrate after the cleaning are sent into the rf magnetron sputtering instrument, and the sputter vacuum is 2.0 * 10 -4Pa, sputter gas are argon gas and oxygen (O 2Gas account for total gas couette 5%); Target and substrate distance are set as 7cm, and sputtering pressure is 0.6Pa, and sputtering power 10W, sputtering time are 60 minutes.
The transparent conductive film well-crystallized of the present embodiment preparation keeps good resistance energy, and resistivity reaches 1.00 * 10 -4Ω .cm.
Embodiment 3
(1) make target with zno-based doped compound (ZnO:Sc), the doping ratio 2.0mol% of Sc prepares target by the method for embodiment 1.
(2) take simple glass as substrate, background is evacuated to 2.0 * 10 -4Pa, take 99.99% argon gas as working gas, operating air pressure remains on 1.0Pa, and target and substrate distance are 5cm, adopt magnetically controlled DC sputtering, and sputtering power 100w, depositing time are 60min.
The transparent conductive film of the present embodiment preparation, film properties is identical with embodiment 1, and electrical property is good.
Embodiment 4
(1) with zinc oxide, aluminium hydroxide, titanium dioxide, doping ratio by Al and Ti is respectively 3.0mol%, 0.25mol% mixing, with the even ball milling of ball mill 8 hours, get the precursor adulterated flour, then in 800 ℃ of sintering after 10 hours, compression molding is again in 1250 ℃, sintering 14 hours makes target.
(2) take simple glass as substrate, background is evacuated to 2.0 * 10 -4Pa, take 99.99% argon gas as working gas, operating air pressure remains on 0.5Pa, and target and substrate distance are 5cm, adopt magnetically controlled DC sputtering, and sputtering power 80w, depositing time are 60min.
The transparent conductive film well-crystallized of the present embodiment preparation keeps good resistance energy, and resistivity reaches 3.00 * 10 -4Ω .cm, the light transmittance remains on more than 95%.

Claims (3)

1. a Zinc oxide-base doped element transparent conductive film is characterized in that comprising that glass lined bottom and surface have the Zinc oxide-base doped element rete of microvoid structure; Described doped element is simple substance element, oxide compound, oxyhydroxide.
2. described transparent conductive film according to claim 1, the ratio that it is characterized in that described doped element is 0.2~10.0mol%.
3. the preparation method of described transparent conductive film according to claim 1 is characterized in that comprising the steps:
(1) doped element and zinc oxide are mixed, dry, ground, get forerunner's adulterated powder; Forerunner's adulterated powder again with the adulterated powder compression molding after the pre-burning, at 1100-1450 ℃ of sintering 1-16 hour, made doped element Zinc oxide-base target in 500-1000 ℃ of pre-burning 2-24 hour;
The ratio of described doped element is 0.20-10mol%, and doped element is the simple substance element, oxide compound, oxyhydroxide, vitriol, nitrate, muriate, alkoxide or fluorochemical;
(2) take glass as substrate layer, adopt magnetron sputtering method, vacuum suction is to 0.6-3.0 * 10 -4Pa, sputter gas are argon gas, oxygen, hydrogen, rare gas element or their mixed gas; Temperature is 25 ℃ to 500 ℃ of chambers, and operating pressure is 0.06-3.0Pa, and d.c. sputtering power is 10-120W, and depositing time is 3-60min; The base material substrate distance is 5-40nm, and thickness is 100-2000nm.
CN2012100673549A 2012-03-14 2012-03-14 Zinc-oxide-doped transparent film and preparation method thereof Pending CN103305792A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103956199A (en) * 2014-04-28 2014-07-30 深圳先进技术研究院 Transparent conducting thin film, manufacturing method thereof and magnetron sputtering device
CN104894520A (en) * 2015-05-06 2015-09-09 大连理工大学 Metal Mg-based UVC wave band transparent conducting structure and preparation method thereof
CN114438464A (en) * 2022-01-26 2022-05-06 中国科学院上海硅酸盐研究所 Bi, Pr and V-free zinc oxide-based pressure-sensitive thin film material and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1588623A (en) * 2004-09-30 2005-03-02 浙江大学 Method or growing N-Al co-blended p type ZnO transistor film by two step method
CN101567395A (en) * 2009-05-26 2009-10-28 中国科学院上海硅酸盐研究所 Surface-texturing n-type ZnO-based transparent conductive film and preparation method thereof
CN101661808A (en) * 2009-09-15 2010-03-03 中国科学院上海硅酸盐研究所 Multi-doping zinc-oxide-base wide-bandgap conducting material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1588623A (en) * 2004-09-30 2005-03-02 浙江大学 Method or growing N-Al co-blended p type ZnO transistor film by two step method
CN101567395A (en) * 2009-05-26 2009-10-28 中国科学院上海硅酸盐研究所 Surface-texturing n-type ZnO-based transparent conductive film and preparation method thereof
CN101661808A (en) * 2009-09-15 2010-03-03 中国科学院上海硅酸盐研究所 Multi-doping zinc-oxide-base wide-bandgap conducting material and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103956199A (en) * 2014-04-28 2014-07-30 深圳先进技术研究院 Transparent conducting thin film, manufacturing method thereof and magnetron sputtering device
CN103956199B (en) * 2014-04-28 2016-09-07 深圳先进技术研究院 Transparent conductive film and preparation method thereof, magnetic control sputtering device
CN104894520A (en) * 2015-05-06 2015-09-09 大连理工大学 Metal Mg-based UVC wave band transparent conducting structure and preparation method thereof
CN114438464A (en) * 2022-01-26 2022-05-06 中国科学院上海硅酸盐研究所 Bi, Pr and V-free zinc oxide-based pressure-sensitive thin film material and preparation method thereof
CN114438464B (en) * 2022-01-26 2023-01-31 中国科学院上海硅酸盐研究所 Bi, pr and V-free zinc oxide-based pressure-sensitive thin film material and preparation method thereof

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