CN101985735A - Alumina target material and transparent conductive film prepared thereby - Google Patents
Alumina target material and transparent conductive film prepared thereby Download PDFInfo
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- CN101985735A CN101985735A CN200910112272XA CN200910112272A CN101985735A CN 101985735 A CN101985735 A CN 101985735A CN 200910112272X A CN200910112272X A CN 200910112272XA CN 200910112272 A CN200910112272 A CN 200910112272A CN 101985735 A CN101985735 A CN 101985735A
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Abstract
The invention relates to an alumina target material and a transparent conductive film prepared thereby. A high-quality alumina ceramic target is prepared by cold isostatic pressing molding and vacuum high-temperature sintering, wherein the purity of the target is higher than 99.9 percent, and the relative density is greater than 99 percent. The azoic (AZO) transparent conductive film is prepared on various substrates by multi-target co-sputtering technology through the alumina ceramic target and zinc oxide target or zinc target. The AZO transparent conductive film prepared by the process has high transmittance and continuously adjustable aluminum content and resistivity; and the average transmittance is greater than 80 percent and the resistivity can be lowered to 3.38*10<-4>omega.cm in a range between 400 and 1,000nm. The AZO transparent conductive film can substitute for indium-tin oxide (ITO) to be widely applied to the fields of solar cells, panel displays and the like.
Description
Technical field
The present invention relates to a kind of preparation method of aluminum oxide target and prepare the method for aluminium-doped zinc oxide transparent conductive film, belong to technical field of optoelectronic functional materials with this target.
Technical background
Transparent conductive oxide (transparent conductive oxide is called for short TCO) is a class that is most widely used in the transparent conductive material.The film of this class material preparation not only has very high transmitance at visible region, infrared very high with the near-infrared region reflectivity, UV-light there is strong absorption, and has very low resistivity, therefore can make transparency conductive electrode, radioprotective can be heated form and energy-saving glass etc., is widely used in fields such as flat pannel display, touch-screen, solar cell, photodiode (LED), microwave oven form, vehicle glass and building glass.Tin-doped indium oxide (Indium Tin Oxide is called for short ITO) is the transparent film of leading that is most widely used at present, and still the indium metal as chief component is a rare metal, be scarce resource, cost an arm and a leg, and poisonous, harmful in preparation and use; In addition, unstable in hydrogen plasma.Therefore necessary development of new nesa coating is in order to substitute ITO.Novel transparent conducting film, aluminium are mixed zinc oxide (Aluminum doped zinc oxide, be called for short AZO), and cost of material is cheap, and the source is abundant, and nontoxic, stability is better than ITO in hydrogen plasma, and have can be comparable with ITO photoelectric properties.Has the trend that progressively replaces ITO in a lot of fields.
The preparation method of AZO transparent conductive film can be divided into the method for directly spattering and spatter method two big classes altogether.The general direct use AZO target as sputter growth AZO transparent conductive film of the method for directly spattering, the AZO target is obtained through batch mixing, moulding and sintering by the oxide powder and zinc and the aluminum oxide powder of certain proportioning, prepares used target and conductive film and electrode manufacturing method as the disclosed transparent conductive film of publication number CN101285164A.In addition, use aluminium zinc target and oxygen reaction sputter growth AZO film in addition, directly the target zinc-aluminium that uses of the method for spattering then will prepare the replacing of polylith target than being fixed value if prepare the AZO film of different aluminum content, and this has brought great inconvenience to production.The method of spattering can be used zinc-oxide ceramic target and aluminium target, alumina-ceramic target and zinc target cosputtering growth AZO film under the mixed atmosphere of argon gas and oxygen altogether, or alumina-ceramic target and zinc-oxide ceramic target cosputtering growth AZO film under pure argon atmosphere.The present invention relates to the preparation of a kind of high purity, high density aluminum oxide target, and use this alumina-ceramic target and zinc-oxide ceramic target, zinc metallic target cosputtering growth AZO film, can under the prerequisite of not destroying vacuum system replacing target, realize that aluminium content is adjustable continuously within the specific limits in the film, thereby realize that resistivity, carrier concentration, energy gap and work function are adjustable continuously within the specific limits.
Summary of the invention
The present invention is directed to indium content height in the current I TO film, the problem that cost is high, prepare high-quality alumina-ceramic target, and adopted the method for this alumina-ceramic target and zinc-oxide ceramic target, zinc target co-sputtering on transparent substrate such as alkali glass, silica glass, sapphire, gan, zinc oxide, to prepare the novel transparent conducting film that does not contain indium.The nesa coating that adopts this method to prepare can change the aluminium content in the film by the sputtering power of regulating target, can optimize filming technology more easily.
The alumina-ceramic target purity of the present invention's preparation is higher than 99.9%, and relative density is greater than 90%, and glow discharge is stablized in the use, target smooth surface exquisiteness after the long-time etching, and no tubercle produces.
The aluminum oxide target of the present invention's preparation uses high-purity (99.99%) commercial oxidation aluminium powder to be raw material, uses stainless steel mould 1～50Mpa single shaft to press pre-molding, and again through 100～300MPa cold isostatic compaction, 1500 ℃～1900 ℃ sintering of vacuum oven form.The alumina-ceramic of gained obtains high-quality alumina-ceramic target through oxygen atmosphere high temperature annealing, cutting, polishing again.
In the aluminium-doped zinc oxide transparent conductive film of the present invention's preparation, the mass ratio [W of aluminium content and aluminium content and zinc content sum
Al/ (W
Al+ W
Zn)]＜40%, be preferably [W
Al/ (W
Al+ W
Zn)]＜10%, along the hexagonal wurtzite phase structure of (002) orientation, regulating al composition content can be 10
-1～10
-4The resistivity of regulation and control film in the Ω cm scope remains on the interior average transmittances of 400～1000nm wavelength region simultaneously greater than 80%, thereby makes this nesa coating can satisfy the demand of different field.
In the aluminium-doped zinc oxide transparent conductive film of the present invention's preparation, the photoelectric properties of optimization are: resistivity is 3.38 * 10
-4Ω cm, side's resistance is 9.66 Ω/, mobility is 21.4cm
2V
-1S
-1, carrier concentration is 8.63 * 10
20/ cm
3, average transmittances is greater than 80% in 400～1000nm wavelength region;
The present invention adopts zinc target, zinc-oxide ceramic target and the preparation of many target co-sputterings of alumina-ceramic target method, and employed zinc target, zinc-oxide ceramic target and alumina-ceramic target purity are not less than 99.9%, and relative density is not less than 90%.In zinc-oxide ceramic target and many target co-sputterings of alumina-ceramic target method preparation process, working gas is that pure argon, argon hydrogen mix gas, argon oxygen mixes gas, and pressure is 0.1～5.0Pa; Zinc target, zinc oxide target and aluminum oxide target sputtering power are respectively 1～20W/cm
2, 2.5～15W/cm
2With 1.5～10W/cm
2, underlayer temperature is room temperature～500 ℃, bias voltage is 0～-200V.
The present invention proposes to use alumina-ceramic target co-sputtering growth AZO film with respect to prior art, and parameters optimization is prepared and is applicable to transparent conductive film different field, that have the good light electrical property quickly and easily.
Below in conjunction with Figure of description and specific embodiment, technical scheme of the present invention is described further.
Description of drawings
Fig. 1 is the aluminum oxide target behind the etching 100h
Fig. 2 is many target co-sputterings system schematic, and wherein: 1 is substrate, and 2 is baffle plate, and 3 is the magnetic controlling target rifle.
Fig. 3 is for mixing the XRD figure spectrum of zinc oxide transparent conductive film with the aluminium of alumina-ceramic target co-sputtering preparation.
Fig. 4 makes the spectrogram that sees through of sample for experiment.
Fig. 5 shows shape appearance figure for the AFM of the AZO nesa coating for preparing on the silica glass substrate.Surfaceness is 2.34.
Embodiment
Embodiment 1: preparation alumina-ceramic target.
Take by weighing the 60g aluminum oxide powder, splash into right amount alcohol as forming agent, use the mould pressurization 15MPa premolding of diameter as 75mm, the muffin that obtains uses cold isostatic press compression moulding under 200MPa, and the powder agglomates after the compression moulding is put into the forming agent that 80 ℃ of baking oven 20h remove powder agglomates.The powder agglomates of handling well is put into vacuum oven, treats that vacuum tightness is higher than 2 * 10
-3The Pa heating, sintering temperature is 1800 ℃.The ceramic block that sinters is put into tube furnace, feeds pure oxygen, and the control tube internal gas pressure is a pressure-fired, 1200 ℃ of 20h that anneal down.It is 50.8mm that the ceramic block that obtains is polished to diameter, and thickness is the target of 4.5mm.The density that records this aluminum oxide target with Archimedes's method reaches 3.96g/cm
3
Embodiment 2: use zinc-oxide ceramic target and alumina-ceramic target co-sputtering growth AZO transparent conductive film.
Quartz substrate is put into magnetron sputtering coater and is carried out the reverse sputtering cleaning after deionized water, acetone, alcohol ultrasonic cleaning.Sputter is 99.9% with zinc-oxide ceramic target purity, and aluminum oxide target purity is 99.9%, and relative density is all greater than 90%.Target is installed on respectively in two target rifles in opposition to each other (as shown in Figure 2), and adjusting target rifle and vertical direction angle is～30 °, is evacuated to vacuum chamber base vacuum degree and is higher than 2.0 * 10
-4Pa.Underlayer temperature remains on 400 ℃, feeds 20sccm argon gas (sccm represents standard milliliter per minute) in vacuum chamber, and the adjusting pressure in vacuum tank is 0.15Pa, and the radio-frequency power supply power regulation of zinc oxide target correspondence is 5W/cm
2, the radio-frequency power supply power regulation of aluminum oxide target correspondence is 3.5W/cm
2, the sample slewing rate is 6 rev/mins, film growth rate is about 10nm/min under this condition, the earlier pre-sputter 20min of target before formal deposit film.Prepare the AZO nesa coating that thickness is about 300nm according to above-mentioned processing condition.Mass ratio [the W that shows aluminium content and aluminium content and zinc content sum in this AZO nesa coating after tested
Al/ (W
Al+ W
Zn)] ≈ 2.0%, its crystalline structure is that resistivity is 7.04 * 10 along the hexagonal wurtzite phase structure of (002) orientation
-4Ω cm, square resistance are 20.1 Ω, and carrier concentration is 4.80 * 10
20/ cm
3, mobility is 18.48cm
2V
-1S
-1, average transmittances is greater than 80% in 400～1000nm wavelength region, and surfaceness is 2.8nm.
Embodiment 3: use zinc-oxide ceramic target and alumina-ceramic target low temperature cosputtering growth AZO transparent conductive film.
The alkali glass substrate is put into magnetron sputtering coater and is carried out the reverse sputtering cleaning after deionized water, acetone, alcohol ultrasonic cleaning.Sputter is 99.9% with zinc-oxide ceramic target purity, and aluminum oxide target purity is 99.9%, and relative density is all greater than 90%.Target is installed on respectively in two target rifles in opposition to each other (as shown in Figure 2), and adjusting target rifle and vertical direction angle is 30 °, is evacuated to vacuum chamber base vacuum degree and is higher than 2.0 * 10
-4Pa.Underlayer temperature remains on 200 ℃, feeds the 20sccm argon gas in vacuum chamber, and the adjusting pressure in vacuum tank is 0.25Pa, and the radio-frequency power supply power regulation of zinc oxide target correspondence is 5W/cm
2, the radio-frequency power supply power regulation of aluminum oxide target correspondence is 4W/cm
2, regulating bias voltage is-50V that the sample slewing rate is 6 rev/mins, the earlier pre-sputter 20min of target before formal deposit film.Prepare the AZO nesa coating that thickness is 300nm according to above-mentioned processing condition.Mass ratio [the W that shows aluminium content and aluminium content and zinc content sum in this AZO nesa coating after tested
Al/ (W
Al+ W
Zn)] ≈ 2.2%, its crystalline structure is that resistivity is 4.75 * 10 along the hexagonal wurtzite phase structure of (002) orientation
-3Ω cm, square resistance are 135.8 Ω, and average transmittances is greater than 80% in 400～1000nm wavelength region, and surfaceness is 2.1nm.
Claims (7)
1. the transparent conductive film of aluminum oxide target and the preparation of this target, it is characterized in that: purity is higher than 99.9%, and relative density is higher than 90%, smooth surface exquisiteness in this target etching process, no tubercle produces, and glow discharge is stable, can be used in to produce high-quality AZO transparent conductive film.
2. the transparent conductive film of described aluminum oxide target of claim 1 and the preparation of this target, it is characterized in that: use high-purity commercial oxidation aluminium powder to be raw material, use stainless steel mould 1～50MPa single shaft to press pre-molding, through 100～300MPa cold isostatic compaction, 1500 ℃～1900 ℃ sintering of vacuum oven form again.The alumina-ceramic of gained obtains high-quality alumina-ceramic target through oxygen atmosphere high temperature annealing, cutting, polishing again.
3. the transparent conductive film of aluminum oxide target and the preparation of this target is characterized in that: in this conducting film, and the mass ratio [W of aluminium content and aluminium content and zinc content sum
Al/ (W
Al+ W
Zn)]＜40%, along the hexagonal wurtzite phase structure of (002) preferred orientation, regulating al composition content can be 10
-1～10
-4The resistivity of regulation and control film in the Ω cm scope remains on the interior average transmittances of 400～1000nm wavelength region simultaneously greater than 80%, and the al composition that changes in the film can realize that the photoelectric properties of this nesa coating are adjustable in a big way.
4. the described AZO transparent conductive film of claim 3, it is characterized in that: prepared AZO nesa coating is to adopt magnetically controlled sputter method to prepare on transparent substrate such as alkali glass, silica glass, sapphire, gan, zinc oxide, and film thickness is 5～2000nm.
5. the preparation method of the described aluminium-doped zinc oxide transparent conductive film of claim 3 is characterized in that: adopt the preparation of zinc-oxide ceramic target and many target co-sputterings of alumina-ceramic target method, also can adopt the preparation of aluminum oxide target and zinc target response sputtering method.
6. the preparation method of the described aluminium-doped zinc oxide transparent conductive film of claim 5, it is characterized in that: employed zinc, zinc-oxide ceramic target and alumina-ceramic target purity are not less than 99.9%, and relative density is not less than 90%.
7. the preparation method of right 4 or 5 described aluminium-doped zinc oxide transparent conductive films, it is characterized in that: in described zinc target or zinc-oxide ceramic target and many target co-sputterings of the alumina-ceramic target procedure, working gas is that pure argon, argon hydrogen mix gas, argon oxygen mixes gas, and pressure is 0.1～5.0Pa; Zinc target, zinc oxide target and aluminum oxide target sputtering power density are respectively 1～20W/cm
2, 2.5～15W/cm
2With 1.5～10W/cm
2, underlayer temperature is room temperature～500 ℃, bias voltage is 0～-200V.
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| CN200910112272XA CN101985735A (en) | 2009-07-29 | 2009-07-29 | Alumina target material and transparent conductive film prepared thereby |
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|---|---|---|---|
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102231387A (en) * | 2011-06-28 | 2011-11-02 | 合肥工业大学 | Electrode for realizing ohmic contact with n type ZnS quasi-one-dimensional nanometer material and preparation method thereof |
| CN103046013A (en) * | 2012-12-30 | 2013-04-17 | 青海天誉汇新能源开发有限公司 | Method for preparing photovoltaic cell transparent oxide film with flexible substrate |
| CN103203912A (en) * | 2012-01-12 | 2013-07-17 | 上海北玻玻璃技术工业有限公司 | Novel AZO coated glass and preparation technology thereof |
| CN103617831A (en) * | 2013-11-15 | 2014-03-05 | 中国科学院宁波材料技术与工程研究所 | High-mobility ratio aluminum-doped zinc oxide transparent conductive thin film and preparation method thereof |
| TWI453294B (en) * | 2011-11-04 | 2014-09-21 | Ferrotec Ceramics Corp | Sputtering target and its manufacturing method |
| CN108642463A (en) * | 2018-06-04 | 2018-10-12 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of preparation method for electrode laminated film before solar cell |
| CN110073029A (en) * | 2017-03-15 | 2019-07-30 | 捷客斯金属株式会社 | Al2O3Sputtering target and its manufacturing method |
| CN112390628A (en) * | 2020-11-23 | 2021-02-23 | 先导薄膜材料（广东）有限公司 | Preparation method of aluminum oxide target material |
| WO2021135681A1 (en) * | 2019-12-31 | 2021-07-08 | 欧钛鑫光电科技（苏州）有限公司 | Method for preparing nitride target material |
| CN115353373A (en) * | 2022-08-31 | 2022-11-18 | 宁波江丰电子材料股份有限公司 | Alumina target material and preparation method and application thereof |
| CN115404444A (en) * | 2022-07-26 | 2022-11-29 | 信利半导体有限公司 | Manufacturing method of AZO transparent conductive film and transparent solar cell device |
-
2009
- 2009-07-29 CN CN200910112272XA patent/CN101985735A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102231387A (en) * | 2011-06-28 | 2011-11-02 | 合肥工业大学 | Electrode for realizing ohmic contact with n type ZnS quasi-one-dimensional nanometer material and preparation method thereof |
| TWI453294B (en) * | 2011-11-04 | 2014-09-21 | Ferrotec Ceramics Corp | Sputtering target and its manufacturing method |
| US10504706B2 (en) | 2011-11-04 | 2019-12-10 | Ferrotec Ceramics Corporation | Sputtering target and method for producing the same |
| CN103203912B (en) * | 2012-01-12 | 2016-08-24 | 上海北玻玻璃技术工业有限公司 | A kind of new A ZO coated glass and preparation technology thereof |
| CN103203912A (en) * | 2012-01-12 | 2013-07-17 | 上海北玻玻璃技术工业有限公司 | Novel AZO coated glass and preparation technology thereof |
| CN103046013A (en) * | 2012-12-30 | 2013-04-17 | 青海天誉汇新能源开发有限公司 | Method for preparing photovoltaic cell transparent oxide film with flexible substrate |
| CN103617831A (en) * | 2013-11-15 | 2014-03-05 | 中国科学院宁波材料技术与工程研究所 | High-mobility ratio aluminum-doped zinc oxide transparent conductive thin film and preparation method thereof |
| CN103617831B (en) * | 2013-11-15 | 2016-02-03 | 中国科学院宁波材料技术与工程研究所 | Preparing aluminum-doped zinc oxide transparent conducting films of a kind of high mobility and preparation method thereof |
| CN110073029A (en) * | 2017-03-15 | 2019-07-30 | 捷客斯金属株式会社 | Al2O3Sputtering target and its manufacturing method |
| CN108642463A (en) * | 2018-06-04 | 2018-10-12 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of preparation method for electrode laminated film before solar cell |
| WO2021135681A1 (en) * | 2019-12-31 | 2021-07-08 | 欧钛鑫光电科技（苏州）有限公司 | Method for preparing nitride target material |
| CN112390628A (en) * | 2020-11-23 | 2021-02-23 | 先导薄膜材料（广东）有限公司 | Preparation method of aluminum oxide target material |
| CN112390628B (en) * | 2020-11-23 | 2022-08-05 | 先导薄膜材料（广东）有限公司 | Preparation method of aluminum oxide target material |
| CN115404444A (en) * | 2022-07-26 | 2022-11-29 | 信利半导体有限公司 | Manufacturing method of AZO transparent conductive film and transparent solar cell device |
| CN115353373A (en) * | 2022-08-31 | 2022-11-18 | 宁波江丰电子材料股份有限公司 | Alumina target material and preparation method and application thereof |
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Application publication date: 20110316 |