CN102560390B - Preparation method of transparent conductive film - Google Patents
Preparation method of transparent conductive film Download PDFInfo
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- CN102560390B CN102560390B CN 201010602491 CN201010602491A CN102560390B CN 102560390 B CN102560390 B CN 102560390B CN 201010602491 CN201010602491 CN 201010602491 CN 201010602491 A CN201010602491 A CN 201010602491A CN 102560390 B CN102560390 B CN 102560390B
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Abstract
The invention discloses a preparation method of a transparent conductive film, relating to the field of light-emitting materials. The preparation method comprises the steps of: preparing an AZO target and an ATO target; loading the ATO target and a substrate in a vacuum cavity of magnetron sputtering coating equipment, vacuumizing; and regulating a process parameter of magnetron sputtering coating for carrying out coating. According to the invention, by adopting the magnetron sputtering coating equipment, through hydrogen doping, the low-resistance transparent conductive film is prepared on the organic flexible substrate and has a visible light average transmission ratio of more than 85 percent and the minimum specific resistance of 9.2*10<-4>omega.cm, which can reach commercial indexes.
Description
Technical field
The present invention relates to field of photovoltaic materials, relate in particular to a kind of method of utilizing magnetron sputtering method low temperature to prepare transparent conductive film.
Background technology
In recent years, the research of flexible substrate nesa coating has caused the concern of countries in the world, because flexible substrate nesa coating application prospect is considerable, it not only has the characteristics of glass substrate nesa coating, and also have the advantage of many uniquenesses, but as flexing, lightweight, shock-resistant, be easy to big area production, be convenient to transportation etc.Have wide practical use in solar cell of luminescent device, plastic liquid crystal indicating meter and plastic etc.Most transparent conductive film materials is all to use tin-doped indium oxide (Sn-doped In on using at present
2O
3, be called for short ito thin film).Although ito thin film is a kind of transparent conductive film material that present comprehensive photoelectric properties is excellent, be most widely used, but indium is poisonous, expensive, poor stability, exist indium diffusion to cause the problems such as device performance decay, people try hard to seek a kind of ITO replacement material of cheap and excellent performance.Wherein, Al-Doped ZnO (Al-dopedZnO is called for short the AZO film) and antimony doped tin oxide (Sb-doped SnO
2, be called for short the ATO film) and have the material cheapness, nontoxic, can with characteristics such as the comparable electricity of ITO and optical properties, become the most competitive transparent conductive film material.But the problem that the AZO film exists surface and the absorption of grain boundary oxygen to cause electric property to descend, and ATO just in time can make up the shortcoming of AZO in this respect.But it is reported demonstration, there is again too high in resistance in ATO, is difficult to the problems such as etching.These shortcomings have both limited their range of application.The compound system of AZO and ATO film expects that it can possess simultaneously advantage both and as a kind of novel transparent conductive material, become a new focus of nesa coating research.
Summary of the invention
The object of the invention is to provide a kind of method of utilizing the standby type compound transparent conducting film of low temperature magnetic sputtering legal system, and its design comprises the steps:
(1), select Al
2O
3: ZnO=1: 99～3.5: 96.5 (mass percents), preferred Al
2O
3: ZnO=2: 98 powders, after evenly mixing, high temperature sintering becomes the AZO target; Select Sb
2O
3: SnO
2=10: 90～20: 80 (mol ratio), preferred Sb
2O
3: SnO
2=15: 85 powders, after evenly mixing, high temperature sintering becomes the ATO target;
(2), will obtain pack into the vacuum cavity of magnetic-controlled sputtering coating equipment of AZO target and ATO target and substrate in step (1), with mechanical pump and molecular pump, the vacuum tightness of vacuum cavity is evacuated to 1.0 * 10
-3Pa～1.0 * 10
-5Between Pa, preferred 6.0 * 10
-4Pa;
(3), adjust the magnetron sputtering plating processing parameter: target (that target?) be as above 80～120mm with the substrate spacing, preferred 60mm; Operating pressure 0.2～1.5Pa, preferred 1.0Pa; The working gas flow 15～25sccm of hydrogen and argon gas gas mixture (wherein, the volumn concentration of hydrogen is 3%～10%), preferably 20sccm, and substrate preheating temperature is controlled at 25 ℃～100 ℃ and carries out coated film deposition 120min.
The present invention adopts magnetron sputtering equipment, by the doping of hydrogen, has realized the preparation of low-resistance nesa coating on organic flexible substrate, obtains film visible light average transmittances greater than 85%, and lowest resistivity is 9.2 * 10
-4Ω cm can reach commercial index.
Description of drawings
Fig. 1 is the process flow sheet of electrically conducting transparent membrane preparation method of the present invention;
Fig. 2 is that content of the present invention is the transmitted light spectrogram for preparing laminated film under 3% hydrogen;
Fig. 3 is hydrogen content of the present invention when being 3%, and preparation-obtained laminated film uses the change in resistance curve after 48 hours under differing temps.
Embodiment
The present invention as shown in Figure 1, comprises the steps: in a kind of method of utilizing the standby type compound transparent conducting film of low temperature magnetic sputtering legal system that provides
S1 selects Al
2O
3: ZnO=1: 99～3.5; (96.5 mass percent), preferred Al
2O
3: ZnO=2: 98 powders, after evenly mixing, high temperature sintering becomes the AZO target; Select Sb
2O
3: SnO
2=10: 90～20: 80 (mol ratio), preferred Sb
2O
3: SnO
2=15: 85 powders, after evenly mixing, high temperature sintering becomes the ATO target;
S2 will obtain pack into the cavity of magnetic-controlled sputtering coating equipment of AZO target and ATO target and substrate in step S1, with mechanical pump and molecular pump, the vacuum tightness of cavity is evacuated to 1.0 * 10
-3Pa～1.0 * 10
-5Between Pa, preferred 6.0 * 10
-4Pa;
S3, adjust the magnetron sputtering plating processing parameter: the line of centres of AZO target and ATO target is 80～120mm to the distance of substrate, preferred 90mm; Operating pressure 0.2～1.5Pa, preferred 1.0Pa; The working gas flow 15～25sccm of hydrogen and argon gas gas mixture (wherein, the volumn concentration of hydrogen is 3%～10%), preferred 20sccm; , and the substrate preheating temperature is controlled at 25 ℃～100 ℃ and carries out plated film 120min.
Wherein, in step S3, the deposition of beginning plated film, wherein the sputtering power of AZO target is set as 100W, and the power setting of ATO target is that 120W carries out coated film deposition 120min.
Adopt the present invention to adopt magnetron sputtering equipment, by the doping of hydrogen, realized the preparation of low-resistance nesa coating on organic flexible substrate, obtain film visible light average transmittances greater than 85%, lowest resistivity is 9.2 * 10
-4Ω cm can reach commercial index.
The below is the specific embodiment of our noodle producing method
Embodiment 1
Select Al
2O
3: ZnO=1.5: 98.5 (mass percent) powder, and Sb
2O
3: SnO
2=15: 85 (mol ratio) powder respectively through after evenly mixing, in 900 ℃ of AZO target, ATO targets that sinter Φ 50 * 2mm into, and is packed AZO target and ATO target in the vacuum cavity of magnetic-controlled sputtering coating equipment into.Then, successively use acetone, dehydrated alcohol and deionized water ultrasonic cleaning flexible substrate, and dry up with high pure nitrogen, put into the vacuum cavity of magnetic-controlled sputtering coating equipment.The line of centres of AZO target and ATO target is set as 90mm to the distance of substrate.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4Pa, passing into the working gas flow is the hydrogen of 20sccm and the gas mixture of argon gas (wherein, hydrogen content is 8%, volume percent), pressure is adjusted into 1.0Pa; Begin subsequently film, and the sputtering power of AZO target is set as 100W, the power setting of ATO target is 120W, is 120min in 25 ℃ of lower coated film depositions of substrate preheating, obtains the AZTO film, and the specific conductivity of this AZTO film is 7.2 * 10
-3Ω cm, visible light average transmittances 88%.
Embodiment 2
Select Al
2O
3: ZnO=1: 99 (mass percent) powder, and Sb
2O
3: SnO
2=10: 90 (mol ratio) powder respectively through after evenly mixing, in 1300 ℃ of AZO target, ATO targets that sinter Φ 50 * 2mm into, and is packed AZO target and ATO target in the vacuum cavity of magnetic-controlled sputtering coating equipment into.Then, successively use acetone, dehydrated alcohol and deionized water ultrasonic cleaning flexible substrate, and dry up with high pure nitrogen, put into the vacuum cavity of magnetic-controlled sputtering coating equipment.The line of centres of AZO target and ATO target is set as 80mm to the distance of substrate.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 * 10
-5Pa, passing into the working gas flow is the hydrogen of 25sccm and the gas mixture of argon gas (wherein, hydrogen content is 6%, volume percent), pressure is adjusted into 1.0Pa; Begin subsequently the deposition of film, and the sputtering power of AZO target is set as 100W, the power setting of ATO target is 120W, is 120min in 50 ℃ of lower coated film depositions of substrate preheating, obtains the AZTO film, and the specific conductivity of this AZTO film is 6.5 * 10
-3Ω cm, visible light average transmittances 83%.
Select Al
2O
3: ZnO=2: 98 (mass percent) powder, and Sb
2O
3: SnO
2=20: 80 (mol ratio) powder respectively through after evenly mixing, in 1250 ℃ of AZO target, ATO targets that sinter Φ 50 * 2mm into, and is packed AZO target and ATO target in the vacuum cavity of magnetic-controlled sputtering coating equipment into.Then, successively use acetone, dehydrated alcohol and deionized water ultrasonic cleaning flexible substrate, and dry up with high pure nitrogen, put into the vacuum cavity of magnetic-controlled sputtering coating equipment.The line of centres of AZO target and ATO target is set as 120mm to the distance of substrate.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 * 10
-3Pa, passing into the working gas flow is the hydrogen of 25sccm and the gas mixture of argon gas (wherein, hydrogen content is 3%, volume percent), pressure is adjusted into 1.0Pa; Begin subsequently the deposition of film, wherein the sputtering power of AZO target is set as 100W, and the power setting of ATO target is 120W, is 120min in 75 ℃ of lower coated film depositions of substrate preheating, obtains the AZTO film, and the specific conductivity of this AZTO film is 9.2 * 10
-4Ω cm, visible light average transmittances 85%.
Select Al
2O
3: ZnO=3.5: 96.5 (mass percent) powder, and Sb
2O
3: SnO
2=18: 82 (mol ratio) powder respectively through after evenly mixing, in 1200 ℃ of AZO target, ATO targets that sinter Φ 50 * 2mm into, and is packed AZO target and ATO target in the vacuum cavity of magnetic-controlled sputtering coating equipment into.Then, successively use acetone, dehydrated alcohol and deionized water ultrasonic cleaning flexible substrate, and dry up with high pure nitrogen, put into the vacuum cavity of magnetic-controlled sputtering coating equipment.The line of centres of AZO target and ATO target is set as 90mm to the distance of substrate.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 6.0 * 10
-4Pa, passing into the working gas flow is the hydrogen of 15sccm and the gas mixture of argon gas (wherein, hydrogen content is 10%, volume percent), pressure is adjusted into 1.0Pa; Begin subsequently the deposition of film, wherein the sputtering power of AZO target is set as 100W, and the power setting of ATO target is 120W, is 120min in 100 ℃ of lower coated film deposition times of substrate preheating, obtains the AZTO film, and the specific conductivity of this AZTO film is 1.2 * 10
-3Ω cm, visible light average transmittances 80%.
In above-described embodiment 3, preparation-obtained laminated film when hydrogen content is 3%, visible light average transmittances are greater than 85%, and resistivity is 9.2 * 10
-4Ω cm, and be less than 5% at the resistance change rate of continuous use after 48 hours under 80 ℃, reached the technical indicator of multiple commercial nesa coating, as shown in Fig. 2 and 3.
Fig. 2 is that content is the transmitted light spectrogram for preparing laminated film under 3% hydrogen; In figure the gained sample at the average transmittances of visible region all greater than 90%;
Fig. 3 is hydrogen content when being 3%, and preparation-obtained laminated film uses the change in resistance curve after 48 hours under differing temps; In figure, the change in resistance rate of underlayer temperature below 80 ℃ is less than 5%.
Should be understood that, above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (9)
1. the preparation method of a transparent conductive film, is characterized in that, comprises the steps:
Step S1 is with Al
2O
3Sinter the AZO target in 900～1300 ℃ after mixing, grind according to mass percent 2:98 with ZnO, and with Sb
2O
3And SnO
2Sinter the ATO target in 900～1300 ℃ after mixing, grind according to mass percent 10:90～20:80;
Step S2 with the AZO target, ATO target and the substrate that obtain in the step S1 vacuum cavity of magnetic-controlled sputtering coating equipment of packing into, and is arranged on 1.0 * 10 with the vacuum tightness of vacuum cavity
-3Pa～1.0 * 10
-5Between Pa;
Step S3, adjusting the magnetron sputtering plating processing parameter is: the line of centres of AZO target and ATO target is 80～120mm to the distance of substrate, magnetron sputtering operating pressure 0.2～1.5Pa, the working gas flow 15～25sccm of hydrogen and nitrogen mixture, and the substrate preheating temperature is controlled at 25 ℃～100 ℃ and carries out plated film 120min.
2. preparation method according to claim 1, is characterized in that, in described step S1, and Sb
2O
3And SnO
2According to mass percent 15:85.
3. preparation method according to claim 1, is characterized in that, in described step S2, the vacuum tightness of vacuum cavity is arranged on 6.0 * 10
-4Pa.
4. according to claim 1 or 3 described preparation methods, it is characterized in that, in described step S2, substrate is packed into and is comprised the steps: substrate is successively used acetone, dehydrated alcohol and deionized water ultrasonic cleaning before the cavity of magnetic-controlled sputtering coating equipment, then dries up with high pure nitrogen.
5. preparation method according to claim 1, is characterized in that, in described step S3, the line of centres of AZO target and ATO target is 90mm to the distance of substrate.
6. preparation method according to claim 1, is characterized in that, in described step S3, the magnetron sputtering operating pressure is 1.0Pa.
7. preparation method according to claim 1, is characterized in that, in described step S3, the working gas flow is 20sccm.
8. according to claim 1 or 7 described preparation methods, is characterized in that, in described working gas flow, the volumn concentration of hydrogen is 3%～10%.
9. preparation method according to claim 1, is characterized in that, in described step S3, also comprises: the sputtering power of AZO target is set as 100W, and the power setting of ATO target is 120W, and the coated film deposition time is 120min.
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| CN102560390B true CN102560390B (en) | 2013-11-06 |
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| CN106946468A (en) * | 2017-02-15 | 2017-07-14 | 江西沃格光电股份有限公司 | Resistive formation, contactor control device and preparation method thereof |
| CN109407373A (en) * | 2018-09-18 | 2019-03-01 | 江西沃格光电股份有限公司 | High resistant plated film, color membrane substrates and liquid crystal display panel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100859148B1 (en) * | 2007-03-23 | 2008-09-19 | 희성금속 주식회사 | High flatness transparent conductive thin films and its manufacturing method |
| CN101660121A (en) * | 2009-09-15 | 2010-03-03 | 中国科学院上海硅酸盐研究所 | Cation-anion co-doping n-type zinc-oxide-base transparent conducting film and preparation method thereof |
| CN102465272A (en) * | 2010-11-15 | 2012-05-23 | 海洋王照明科技股份有限公司 | Multielement composite transparent conductive film and preparation method and application thereof |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100859148B1 (en) * | 2007-03-23 | 2008-09-19 | 희성금속 주식회사 | High flatness transparent conductive thin films and its manufacturing method |
| CN101660121A (en) * | 2009-09-15 | 2010-03-03 | 中国科学院上海硅酸盐研究所 | Cation-anion co-doping n-type zinc-oxide-base transparent conducting film and preparation method thereof |
| CN102465272A (en) * | 2010-11-15 | 2012-05-23 | 海洋王照明科技股份有限公司 | Multielement composite transparent conductive film and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| 有机衬底SnO_2∶Sb透明导电膜的研究;马瑾等;《半导体学报》;20020608(第06期);全文 * |
| 氩气压强对直流磁控溅射ZnO:Al薄膜结构和性能的影响;许积文等;《材料科学与工程学报》;20071020(第05期);全文 * |
| 许积文等.氩气压强对直流磁控溅射ZnO:Al薄膜结构和性能的影响.《材料科学与工程学报》.2007,(第05期), |
| 马瑾等.有机衬底SnO_2∶Sb透明导电膜的研究.《半导体学报》.2002,(第06期), |
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Granted publication date: 20131106 Termination date: 20181223 |