CN102191466A - Gallium doped zinc oxide target and preparation method of transparent conductive film thereof - Google Patents
Gallium doped zinc oxide target and preparation method of transparent conductive film thereof Download PDFInfo
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- CN102191466A CN102191466A CN2010101276097A CN201010127609A CN102191466A CN 102191466 A CN102191466 A CN 102191466A CN 2010101276097 A CN2010101276097 A CN 2010101276097A CN 201010127609 A CN201010127609 A CN 201010127609A CN 102191466 A CN102191466 A CN 102191466A
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Abstract
The invention relates to gallium doped zinc oxide target and a preparation method of a transparent conductive film thereof. The target is formed by sintering zinc and gallium oxide powder, wherein the weight content of gallium oxide is 0.5-10%; the purity of the target is no less than 99.9%; and the relative density of the target is no less than 95%, and the maximum is up to 99.5%. The transparent conductive film prepared from the target through the sputtering method has good photoelectric properties; the resistivity can be as low as 1.05*10<-4>Omega cm, the maximum transmissivity is up to 92% in the visible light range (400-800 nm), the average transmissivity is no less than 84%; and the transparent conductive film can be widely used in the fields such as solar cells, light emitting diodes, flat-panel display and liquid crystal display.
Description
Technical field
The present invention relates to the preparation method of a kind of Ga-doped zinc oxide sputtering target material and nesa coating thereof, belong to technical field of optoelectronic functional materials.
Background technology
Transparent conductive oxide (transparent conductive oxide, be called for short TCO) visible light is had very high transmitance, and infrared light is had very high reflectivity, have good conductivity simultaneously, therefore be widely used in the fields such as antifog defrosting window glass of solar cell, photodiode, flat board and liquid-crystal display, various hot mirror and the various vehicles.Tin-doped indium oxide (Indium Tin Oxide, be called for short ITO) be the transparent film of leading that is most widely used at present, still the indium metal (content is up to 90% in ITO) as chief component is a scarce resource, costs an arm and a leg, and poisonous, harmful in preparation and use; In addition, when ITO was applied to solar cell, indium wherein was easy to be diffused in the device and goes, and directly influenced the performance and the stability of device, and ITO is unstable in hydrogen plasma simultaneously.Therefore necessary development of new nesa coating substitutes ITO.The adulterated zno-based nesa coating of n type has good conductivity, and visible light is had high permeability, and has good stability in hydrogen plasma; In addition, the zno-based nesa coating can prepare high-quality nesa coating than the easier crystallization of ITO on flexible substrate; In addition, ZnO aboundresources, low price and nontoxic are a kind of environment amenable materials.Therefore, the zno-based nesa coating has become present research focus, and the development trend that progressively replaces ITO is arranged.
Sputtering method is the main method of preparation TCO, and the quality of sputtering target material will directly have influence on the quality of TCO film.The preparation technology of ITO target is very ripe at present, and the research of zno-based nesa coating target has also obtained certain progress.Chinese patent prospectus CN 1289128A discloses and has a kind ofly gone out aluminium-doped zinc oxide (AZO) target that aluminum oxide total mass content is 1-6% (or pure aluminium powder 0.5-3%) by oxide powder and zinc and aluminum oxide (or pure aluminium powder) intermingling sintering, and the target relative density can reach more than 94%.The preparation method of the AZO ceramic target that it is 1at-10at% that Chinese patent prospectus CN 101285164A discloses a kind of aluminium element content.It is the Indium sesquioxide of 90-99% and gallium oxide and the zinc oxide agglomerating InGaZn of 1-10% by mass content that Chinese patent prospectus CN 1558962A discloses a kind of
7O
10Target, the indium content of this target is the same with ITO, all greater than 90%.Chinese patent prospectus CN 1413947A disclose a kind of under normal pressure, normal atmosphere agglomerating Ga-doped zinc oxide (GZO) target, the mass content of its gallium oxide is 2-7%.Mainly be that the utilization ceramic sputtering target material prepares the TCO nesa coating at present, and the main method of preparation ceramic sputtering target material have atmosphere sintering, HIP sintering and hot pressed sintering etc.
Summary of the invention
The objective of the invention is to prepare highly purified Ga-doped zinc oxide target, and use this target to prepare nesa coating through sputtering method.The photoelectric properties of the nesa coating of this method preparation are can ITO comparable, but cost is more much lower than ITO, is expected to substitute ITO.
The present invention proposes the method for preparing the Ga-doped zinc oxide target, and proposed to adopt this target to prepare the method for nesa coating.This method can be prepared high-density, highly purified Ga-doped zinc oxide target easily and have excellent conductive performance and the nesa coating of high permeability.
1. Ga-doped zinc oxide target, it is characterized in that: this target is formed through sintering by zinc, gallium oxide powder; Wherein the mass content of gallium oxide is 0.5-10%; The purity of target is not less than 99.9%; The relative density of target is not less than 95%, reaches as high as 99.5%.
2. the preparation method of 1 described Ga-doped zinc oxide target, it is characterized in that: the preparation process of this target may further comprise the steps:
(1). the zinc for preparing, gallium oxide powder are at first pressed pre-molding at stainless steel mould through 1～50Mpa single shaft, again through 100～300MPa cold isostatic compaction, the block after the moulding is dried down at 70-150 ℃ remove forming agent then.
(2). the block after the oven dry is at normal pressure, air atmosphere or vacuum 0.1-10
-5Sintering under the Pa state, sintering temperature are 900-1500 ℃.
(3). the target germule behind the sintering placed carry out anneal under the purity oxygen atmosphere, annealing temperature is 800-1200 ℃.
(4). the target germule after the anneal, cutting, polishing and installation backboard.
3. the preparation method of 2 described Ga-doped zinc oxide targets, it is characterized in that: the employed zinc of this target of sintering, gallium oxide powder are by coprecipitation method, sol-gel method, hydrolysis method, hydrothermal method, microemulsion method or solid phase Prepared by Ball Milling; Having added mass content in the process of preparation zinc, gallium oxide powder is the dispersion agent of 0-5%, and dispersion agent comprises polyvinyl alcohol, polyoxyethylene glycol, polyvinyl butyral acetal, dioctyl sodium sulfosuccinate, Sodium dodecylbenzene sulfonate, Sodium glycocholate and tween etc.; Under air atmosphere or oxygen atmosphere, through 400-800 ℃ of presintering, carry out granulation then, sieving has promptly obtained zinc, gallium oxide powder after zinc, the gallium oxide presoma drying.
4. gallium adulterated zinc oxide transparent conductive film is characterized in that: this nesa coating is to adopt 1 a described Ga-doped zinc oxide target to prepare through sputtering method.
5. 4 described gallium adulterated zinc oxide transparent conductive films, it is characterized in that: this nesa coating is the hexagonal wurtzite phase structure, and resistivity reaches 10
-4Ω cm, lowest resistivity is 1.05 * 10
-4Ω cm reaches 92% at the high permeability of visible-range 400～800nm, and average transmittances is not less than 84%.
6. the preparation method of 4 described gallium adulterated zinc oxide transparent conductive films is characterized in that: in the sputter coating process, and working gas pure argon mixings 0-20% oxygen composition, pressure is 0.1～2.0Pa, underlayer temperature is room temperature～700 ℃.
The present invention uses above-mentioned target to adopt sputtering method to prepare gallium adulterated zinc oxide transparent conductive film.In the sputter coating process, working gas pure argon mixing 0-20% oxygen is formed, and pressure is 0.1～2.0Pa, and underlayer temperature is room temperature～700 ℃.Prepared gallium adulterated zinc oxide transparent conductive film is the hexagonal wurtzite phase structure, and resistivity can reach 10
-4Ω cm, resistivity is minimum to reach 1.05 * 10
-4Ω cm, (400～800nm) high permeabilities can reach 92%, and average transmittances is not less than 84% at visible-range.
The Ga-doped zinc oxide target of the present invention preparation and nesa coating is with low cost, performance can be comparable with ITO, can substitute a large amount of at present ITO target and nesa coatings thereof that use, save a large amount of noble metal indiums, significantly reduce the cost of nesa coating simultaneously.
Description of drawings
Fig. 1 is the transmitance of the gallium adulterated zinc oxide transparent conductive film for preparing on the silica glass substrate.
Fig. 2 is the X-ray diffraction spectrum of the gallium adulterated zinc oxide transparent conductive film for preparing on the silica glass substrate.
Embodiment
Further specify embodiments of the present invention below by example, purpose is to help further to understand the present invention rather than restriction the present invention, that is the present invention never is limited to following example.
Embodiment 1: the preparation of Ga-doped zinc oxide target
At first adopt solid phase Prepared by Ball Milling zinc, gallium oxide powder.According to Ga
2O
3/ (ZnO+Ga
2O
3) mass ratio is 5% to take by weighing zinc oxide (purity is 99.99%) powder and gallium oxide (purity is 99.99%) powder, takes by weighing the polyoxyethylene glycol that accounts for powder total mass 1%, takes by weighing the abrading-ball that is three times in powder quality; Load weighted powder, polyoxyethylene glycol and abrading-ball are put in the ball grinder, added a certain amount of dehydrated alcohol then, ball grinder is sealingly fastened on the ball mill, then with 270 rev/mins speed ball milling 5 hours.After ball milling is finished slurry is poured out, 80 ℃ of down oven dry 5 hours,, after presintering is finished powder is sieved, granulation promptly obtained can be used for target agglomerating zinc, gallium oxide powder then with powder presintering 5 hours under 700 ℃ and high purity oxygen gas.
Add an amount of dehydrated alcohol and put into to above-mentioned zinc, gallium oxide powder and install mould in the stainless steel mould, pre-molding under the uniaxial tension of 20MPa, then through 250MPa isostatic cool pressing 5 minutes, subsequently the block after the moulding is placed on 80 ℃ of oven dry 5 hours down; After treating the block oven dry, it is transferred in the vacuum sintering furnace, be evacuated to and be warmed up to 1050 ℃ of sintering 20 hours after pressure is lower than 0.1Pa; After sintering is finished furnace temperature is dropped to 900 ℃, in sintering oven, feed high purity oxygen gas then and keep pressure-fired to carry out anneal 20 hours; Treat after anneal is finished furnace temperature drop to room temperature take out ceramic block and on request size carry out mechanical workout and the Ga-doped zinc oxide target that backboard just can obtain being used for sputter coating be installed.The density of measuring this target through Archimedes's method reaches 5.39g/cm
3
Embodiment 2: the preparation of gallium adulterated zinc oxide transparent conductive film
Adopt example 1 prepared Ga-doped zinc oxide target to prepare nesa coating with magnetron sputtering method.Target is installed on the magnetic controlling target rifle correspondence position, is evacuated to vacuum chamber base vacuum degree and is higher than 2.0 * 10
-4Pa is a substrate with the silica glass, and underlayer temperature remains on 400 ℃, in vacuum chamber, feed 20sccm argon gas (sccm represents standard milliliter per minute), the adjusting pressure in vacuum tank is 0.15Pa, and regulating radio-frequency power supply power is 100W, the earlier pre-sputter 10min of target before formal deposit film.Prepare the gallium adulterated zinc oxide transparent conductive film that thickness is about 320nm according to above-mentioned processing condition.The crystalline structure that shows this nesa coating after tested is the hexagonal wurtzite phase structure along (002) orientation, and resistivity is 3.58 * 10
-4Ω cm, (400～800nm) high permeabilities can reach 92% to visible-range, and average transmittances is 85%.
Claims (6)
1. Ga-doped zinc oxide target, it is characterized in that: this target is formed through sintering by zinc, gallium oxide powder; Wherein the mass content of gallium oxide is 0.5-10%; The purity of target is not less than 99.9%; The relative density of target is not less than 95%, reaches as high as 99.5%.
2. the preparation method of the described Ga-doped zinc oxide target of claim 1, it is characterized in that: the preparation process of this target may further comprise the steps:
(1). the zinc for preparing, gallium oxide powder are at first pressed pre-molding at stainless steel mould through 1～50Mpa single shaft, again through 100～300MPa cold isostatic compaction, the block after the moulding is dried down at 70-150 ℃ remove forming agent then.
(2). the block after the oven dry is at normal pressure, air atmosphere or vacuum 0.1-10
-5Sintering under the Pa state, sintering temperature are 900-1500 ℃.
(3). the target germule behind the sintering placed carry out anneal under the purity oxygen atmosphere, annealing temperature is 800-1200 ℃.
(4). the target germule after the anneal, cutting, polishing and installation backboard.
3. the preparation method of the described Ga-doped zinc oxide target of claim 2, it is characterized in that: the employed zinc of this target of sintering, gallium oxide powder are by coprecipitation method, sol-gel method, hydrolysis method, hydrothermal method, microemulsion method or solid phase Prepared by Ball Milling; Having added mass content in the process of preparation zinc, gallium oxide powder is the dispersion agent of 0-5%, and dispersion agent comprises polyvinyl alcohol, polyoxyethylene glycol, polyvinyl butyral acetal, dioctyl sodium sulfosuccinate, Sodium dodecylbenzene sulfonate, Sodium glycocholate and tween etc.; Under air atmosphere or oxygen atmosphere, through 400-800 ℃ of presintering, carry out granulation then, sieving has promptly obtained zinc, gallium oxide powder after zinc, the gallium oxide presoma drying.
4. gallium adulterated zinc oxide transparent conductive film is characterized in that: this nesa coating is to adopt the described Ga-doped zinc oxide target of claim 1 to prepare through sputtering method.
5. the described gallium adulterated zinc oxide transparent conductive film of claim 4, it is characterized in that: this nesa coating is the hexagonal wurtzite phase structure, and resistivity reaches 10
-4Ω cm, lowest resistivity is 1.05 * 10
-4Ω cm reaches 92% at the high permeability of visible-range 400～800nm, and average transmittances is not less than 84%.
6. the preparation method of the described gallium adulterated zinc oxide transparent conductive film of claim 4 is characterized in that: in the sputter coating process, working gas pure argon mixing 0-20% oxygen is formed, and pressure is 0.1～2.0Pa, and underlayer temperature is room temperature～700 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509648A (en) * | 2011-10-24 | 2012-06-20 | 北京科技大学 | Preparation method for Ga-doped ZnO nanometer material |
| CN106222618A (en) * | 2016-08-29 | 2016-12-14 | 基迈克材料科技（苏州）有限公司 | SnO2the preparation method of doping ZnO sputtering target material |
| CN109437884A (en) * | 2018-10-19 | 2019-03-08 | 先导薄膜材料（广东）有限公司 | The preparation method of cadmium stannate target |
| CN112341168A (en) * | 2020-09-23 | 2021-02-09 | 先导薄膜材料（广东）有限公司 | Rare earth doped zinc-gallium-aluminum oxide powder and preparation method thereof |
| CN116751048A (en) * | 2023-06-05 | 2023-09-15 | 洛阳晶联光电材料有限责任公司 | Gallium-aluminum doped zinc oxide target material and preparation method and application thereof |
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| CN1413947A (en) * | 2002-12-20 | 2003-04-30 | 清华大学 | Zinc gallium oxide ceramic target material and its preparation method and application |
| CN1718840A (en) * | 2005-06-21 | 2006-01-11 | 山东大学 | Preparation method of gallium adulterated zinc oxide transparent conductive film |
| WO2007000867A1 (en) * | 2005-06-28 | 2007-01-04 | Nippon Mining & Metals Co., Ltd. | Gallium oxide-zinc oxide sputtering target, method of forming transparent conductive film and transparent conductive film |
| CN101208452A (en) * | 2005-06-28 | 2008-06-25 | 日矿金属株式会社 | Gallium oxide-zinc oxide sputtering target, method for forming transparent conductive film, and transparent conductive film |
| JP2008144246A (en) * | 2006-12-13 | 2008-06-26 | Idemitsu Kosan Co Ltd | Method for producing sputtering target |
| JP2009007664A (en) * | 2007-06-28 | 2009-01-15 | Samsung Corning Precision Glass Co Ltd | Sputtering target for zinc oxide based amorphous thin film, and manufacturing method thereof |
| US20090250669A1 (en) * | 2005-12-08 | 2009-10-08 | Nippon Mining & Metals Co., Ltd. | Gallium Oxide/Zinc Oxide Sputtering Target, Method of Forming Transparent Conductive Film and Transparent Conductive Film |
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| CN1413947A (en) * | 2002-12-20 | 2003-04-30 | 清华大学 | Zinc gallium oxide ceramic target material and its preparation method and application |
| CN1718840A (en) * | 2005-06-21 | 2006-01-11 | 山东大学 | Preparation method of gallium adulterated zinc oxide transparent conductive film |
| WO2007000867A1 (en) * | 2005-06-28 | 2007-01-04 | Nippon Mining & Metals Co., Ltd. | Gallium oxide-zinc oxide sputtering target, method of forming transparent conductive film and transparent conductive film |
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| JP2009007664A (en) * | 2007-06-28 | 2009-01-15 | Samsung Corning Precision Glass Co Ltd | Sputtering target for zinc oxide based amorphous thin film, and manufacturing method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509648A (en) * | 2011-10-24 | 2012-06-20 | 北京科技大学 | Preparation method for Ga-doped ZnO nanometer material |
| CN102509648B (en) * | 2011-10-24 | 2013-11-27 | 北京科技大学 | Preparation method for Ga-doped ZnO nanometer material |
| CN106222618A (en) * | 2016-08-29 | 2016-12-14 | 基迈克材料科技（苏州）有限公司 | SnO2the preparation method of doping ZnO sputtering target material |
| CN106222618B (en) * | 2016-08-29 | 2018-12-18 | 基迈克材料科技（苏州）有限公司 | The preparation method of SnO2 doping ZnO sputtering target material |
| CN109437884A (en) * | 2018-10-19 | 2019-03-08 | 先导薄膜材料（广东）有限公司 | The preparation method of cadmium stannate target |
| CN112341168A (en) * | 2020-09-23 | 2021-02-09 | 先导薄膜材料（广东）有限公司 | Rare earth doped zinc-gallium-aluminum oxide powder and preparation method thereof |
| CN116751048A (en) * | 2023-06-05 | 2023-09-15 | 洛阳晶联光电材料有限责任公司 | Gallium-aluminum doped zinc oxide target material and preparation method and application thereof |
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Application publication date: 20110921 |