CN102610670A - Near-infrared transparent conducting film and method for producing same - Google Patents
Near-infrared transparent conducting film and method for producing same Download PDFInfo
- Publication number
- CN102610670A CN102610670A CN2012100885400A CN201210088540A CN102610670A CN 102610670 A CN102610670 A CN 102610670A CN 2012100885400 A CN2012100885400 A CN 2012100885400A CN 201210088540 A CN201210088540 A CN 201210088540A CN 102610670 A CN102610670 A CN 102610670A
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- film
- transparent conductive
- conductive film
- infrared transparent
- preparation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a near-infrared transparent conducting film and a method for producing the same, which belong to the technical field of electronic materials. The near-infrared transparent conducting film is an H-doped In2O3 film. The film takes common glass as a substrate, a ceramic target In2O3 as a target raw material, Ar gas as a sputtering gas, O2 gas and H2O steam as reaction gases, a reaction radio frequency magnetic control sputtering technology is adopted to produce an amorphous state H-doped In2O3 film at the room temperature, vacuum annealing is carried out for 60-120 minutes under the temperature of 170-200 DEG C, so the H-doped In2O3 film with a polycrystalline structure is formed. The produced film has low resistivity, high carrier mobility, high transmissivity in visible light near-infrared ranges and other excellent photoelectric properties. The method has a low technological temperature, is simple and convenient to produce, low in cost and easy for large-area filming.
Description
Technical field
The present invention relates to a kind of near-infrared transparent conductive film and preparation method thereof, belong to technical field of electronic materials.
Background technology
People produce very big interest to the development thin-film solar cells in recent years, and transparent conductive film provides material foundation for making the large area film solar cell.Transparent conductive film has high conductivity and visible-range high light transmittance, is used as the preceding electrode of thin-film solar cells, and the permission solar radiation directly is transmitted to the zone of action and collects the electric current of battery effectively.The most representative transparent conductive film has indium oxide (ITO) film of mixing tin, the tin oxide (SnO that mixes antimony at present
2: Sb) film, mix the tin oxide (SnO of fluorine
2: F) film and zinc oxide (ZnO:Al) film of mixing aluminium.Transparent conductive film generally reaches resistivity 10
-4Ω .cm magnitude, visible region transmitance are greater than 80%, and there is cut-off characteristics the ultra-violet (UV) band, and infrared region has high reflectivity.
As everyone knows, incide in the tellurian sunlight spectrum, sunlight visible-range (400 ~ 700nm) energy only account for its full-luminous wave-length coverage (300 ~ 2500nm) 43%.(300 ~ 400nm) energy is 5% of a gross energy to sunlight, and is 52% of gross energy at the energy of near infrared region at ultraviolet region.How to make full use of the solar energy of near infrared region, improve the utilization ratio of solar cell, become the problem that people pay close attention to.The infrared reflectivity of conventional transparent conductive film is high, has limited with them as the effective utilization to the near infrared band solar radiant energy of the solar cell of transparency electrode.Therefore, the development of near-infrared transparent conductive film is significant with exploitation.
In order to improve the transmitance of transparent conductive film, the way that adopts usually is to reduce carrier concentration, but has damaged the electric conductivity of transparent conductive film like this.Theoretical according to Drude, under the situation of the electric conductivity that does not damage transparent conductive film, improving transparent conductive film is to improve the mobility of charge carrier rate in the unique feasible way of the transmitance of near infrared band, reduces carrier concentration simultaneously.Utilize the poor (W of high valence state
6+Or Mo
6+With In
3+The valence state difference be 3) In that mixes
2O
3: W (W doping In
2O
3, i.e. IWO) and In
2O
3: Mo (Mo doping In
2O
3, i.e. IMO) and transparent conductive film adapted to application development in this respect.Retrieval through to existing document finds that the near-infrared transparent conductive film has W doping In
2O
3Film and Mo doping In
2O
3Film; The method for preparing the near-infrared transparent conductive film has direct current magnetron sputtering process, is disclosed Chinese invention patent " near-infrared high-transmission rate non-crystal transparent conductive oxide film and preparation method thereof " among the CN101101931A, Granted publication number " the near infrared region high-transmission rate In for people such as disclosed Chinese invention patent " near-infrared high-transmission rate and multi-crystal transparent conductive oxide film and preparation method thereof " among the CN100477133C and Feng Jiahan referring to publication number
2O
3: the research of W transparent conductive oxide film ", " vacuum " 45 (2008) 27-30; Electron-beam vapor deposition method number is " a kind of preparation high mobility doped with Mo In of disclosed Chinese invention patent among the CN101560642B referring to Granted publication
2O
3The method of transparent conductive film "; The radio frequency magnetron reactive sputtering, referring to people's such as Yuan Guo " depositing temperature is to the influence of IMO transparent conductive film photoelectric properties ", " vacuum science and technological journal " 30 (2010) 676-679.
Direct current magnetron sputtering process utilizes indium metal to mix the mosaic target of molybdenum or tungsten, is the In for preparing under the condition of room temperature at substrate temperature
2O
3: W and In
2O
3: the carrier mobility of Mo film reaches 20 cm
2/ Vs, free carrier concentration is lower than 8 * 10
20Cm
-3, resistivity remains on 6 * 10
-4Ω .cm, the mean transmissivity of visible light and near infrared range is higher than 80%; The In that under 300 ~ 350 ℃ of conditions of substrate temperature, prepares
2O
3: W and In
2O
3: the carrier mobility of Mo film is 40 ~ 70cm
2/ Vs, free carrier concentration is lower than 2 * 10
20Cm
-3, resistivity remains on (3 ~ 6) * 10
-4Ω .cm, the mean transmissivity of visible region is higher than 80%, and the mean transmissivity of near infrared region is greater than 90%.Radio-frequency magnetron sputter method adopts In
2O
3With metal M o powder be that the synthetic ceramic target of raw material is as sputtering target material, at the In of 350 ℃ of preparations of underlayer temperature
2O
3: the carrier mobility of Mo film is 45cm
2/ Vs, free carrier concentration is 2.15 * 10
20Cm
-3, resistivity is 6.9 * 10
-4Ω .cm, at the mean transmissivity of visible light and near infrared region greater than 80%.Electron-beam vapor deposition method is with high-purity ceramic target In
2O
3: MoO
3As source material, at the typical In of 330 ~ 400 ℃ of preparations of underlayer temperature
2O
3: Mo film resiativity 2.5 * 10
-4Ω .cm, free carrier concentration 5.8 * 10
20Cm
-3, carrier mobility 47.1cm
2/ Vs, visible light and near infrared region mean transmissivity 80%.The amorphous state near-infrared transparent conductive film carrier mobility of the room temperature preparation of bibliographical information is little, carrier concentration is high and resistivity is big, and bibliographical information polycrystalline attitude near-infrared transparent conductive film growth temperature is more than 300 ℃.In film growth techniques, should reduce the growth temperature of near-infrared transparent conductive film, the photoelectric properties that can guarantee material again are the important topics of research.The present invention utilizes magnetron sputtering technique, prepares the H doping In of high mobility, low-resistivity and visible light-near infrared region high permeability
2O
3Film.
Summary of the invention
For the photoelectric properties that overcome near-infrared transparent conductive film in the prior art and the contradiction between the film growth temperature, the present invention proposes a kind of near-infrared transparent conductive film H doping In
2O
3And preparation method thereof.Through H doping In
2O
3Material and H passivation In
2O
3The fault of construction of material prepares high mobility near-infrared transparent conductive film at low temperatures.
The near-infrared transparent conductive film that the present invention proposes is a kind of H doping In
2O
3Film, film thickness are 72 ~ 240nm, and carrier mobility is 126 ~ 140 cm
2/ Vs, free carrier concentration is lower than 1.9 * 10
20Cm
-3, resistivity is lower than 3.1 * 10
-4Ω .cm, the mean transmissivity of visible light and near infrared range is higher than 80%.
The present invention also proposes a kind of preparation near-infrared transparent conductive film H doping In
2O
3Method, may further comprise the steps:
Step 1, use purity are 99.99% ceramic target In
2O
3As the target raw material, be substrate with the simple glass.With sonochemistry glass cleaning substrate, then with In
2O
3Target is sent into the rf magnetron sputtering appearance with the glass substrate of cleaning.Adopt reaction radiofrequency magnetron sputtering technology room temperature preparation amorphous state H doping In on glass substrate
2O
3Film.The process conditions of rf magnetron sputtering are: the sputtering chamber target is to the distance 60 ~ 70mm of substrate, and the sputtering chamber base vacuum is less than 1.0 * 10
-3Pa.Ar gas is sputter gas, O
2Gas and H
2The O steam is a reacting gas, O
2With Ar+ O
2Flow rate ratio be 0.003 ~ 0.005, H
2The dividing potential drop of O steam is 1 * 10
-4Pa ~ 5 * 10
-4Operating pressure in the Pa, reative cell is 0.5Pa, sputtering power 50 ~ 100W.
Step 2 is to the amorphous state H doping In of preparation
2O
3Film carries out vacuum annealing to be handled, and annealing temperature is 170 ~ 200 ℃, and annealing time is 60 ~ 120 minutes, obtains the H doping In of polycrystalline structure
2O
3Film.
Advantage of the present invention and good effect:
The present invention is through annealing amorphous state H doping In
2O
3Film changes into polycrystalline H doping In
2O
3Film, the inventive method crystallization temperature is low, be the effective ways of the big crystal grain of preparation and few intragranular defective, but low temperature obtains the high mobility polycrystalline film.H can be used as shallow donor's energy level in transparent conductive oxide, can form O-H (H with O
+) group and charge carrier is provided, the fault of construction that the intervention of H can the passivation transparent conductive material.Experimental result shows, the H doping In of the present invention's preparation
2O
3The film carrier mobility is 126 ~ 140 cm
2/ Vs, free carrier concentration is lower than 1.9 * 10
20Cm
-3, resistivity is lower than 3.1 * 10
-4Ω .cm, the mean transmissivity of visible light and near infrared range were higher than for 80% (containing 2mm thickness glass substrate).The near-infrared transparent conductive film of the inventive method preparation is more superior than the amorphous state near-infrared transparent conductive film photoelectric properties of prior art for preparing; Polycrystalline attitude near-infrared transparent conductive film with prior art for preparing is compared, and the film growth temperature obviously reduces.The inventive method technological temperature is low, the equipment simple cheap, the easily manufactured and recyclable utilization of target, with low cost be easy to the large tracts of land film forming.The film of the present invention's preparation has a good application prospect in area of solar cell.
Embodiment
Embodiment 1:
Step 1, use purity are 99.99% ceramic target In
2O
3As the target raw material, be substrate with the simple glass.With sonochemistry glass cleaning substrate, then with In
2O
3Target is sent into the rf magnetron sputtering appearance with the glass substrate of cleaning.Adopt reaction radiofrequency magnetron sputtering technology room temperature preparation amorphous state H doping In on glass substrate
2O
3Film.The process conditions of rf magnetron sputtering are: the sputtering chamber target to substrate apart from 60mm, the sputtering chamber base vacuum is less than 1.0 * 10
-3Pa.Ar gas is sputter gas, O
2Gas and H
2The O steam is a reacting gas, O
2With Ar+ O
2Flow rate ratio be 0.0038, H
2The dividing potential drop of O steam does
1 * 10
-4Operating pressure in the Pa, reative cell is 0.5Pa, and sputtering power 75W, film thickness are 72nm.
Step 2 is to the amorphous state H doping In of preparation
2O
3Film carries out vacuum annealing to be handled, and annealing temperature is 200 ℃, and annealing time is 120 minutes, obtains the H doping In of polycrystalline structure
2O
3Film.
Detection shows that this film carrier mobility is 140 cm
2/ Vs, free carrier concentration is 1.5 * 10
20Cm
-3, resistivity is 2.9 * 10
-4Ω .cm, the mean transmissivity of visible light and near infrared range is higher than 80%.
Embodiment 2:
Preparation technology is said with embodiment 1 basically, different is sputtering chamber target to substrate apart from 70mm, O
2With Ar+ O
2Flow rate ratio be 0.003, H
2The dividing potential drop of O steam is 5 * 10
-4Pa, sputtering power 50W, film thickness are 240nm.Detection shows that this film carrier mobility is 130 cm
2/ Vs, free carrier concentration is 1.8 * 10
20Cm
-3, resistivity is 2.7 * 10
-4Ω .cm, the mean transmissivity of visible light and near infrared range is higher than 83%.
Embodiment 3:
Preparation technology is said with embodiment 1 basically, different is sputtering chamber target to substrate apart from 65mm, O
2With Ar+ O
2Flow rate ratio be 0.005, H
2The dividing potential drop of O steam is 3 * 10
-4Pa, sputtering power 100W, film thickness are 150nm.Vacuum annealing temperature is 170 ℃, and annealing time is 60 minutes.Detection shows that this film carrier mobility is 126 cm
2/ Vs, free carrier concentration is 1.61 * 10
20Cm
-3, resistivity is 3.07 * 10
-4Ω .cm, the mean transmissivity of visible light and near infrared range is higher than 80%.
Embodiment 4:
Preparation technology is said with embodiment 1 basically, different is sputtering chamber target to substrate apart from 70mm, O
2With Ar+ O
2Flow rate ratio be 0.004, H
2The dividing potential drop of O steam is 2 * 10
-4Pa, sputtering power 80W, film thickness are 100nm.Vacuum annealing temperature is 180 ℃, and annealing time is 100 minutes.Detection shows that this film carrier mobility is 130 cm
2/ Vs, free carrier concentration is 1.6 * 10
20Cm
-3, resistivity is 3.0 * 10
-4Ω .cm, the mean transmissivity of visible light and near infrared range is higher than 80%.
Claims (6)
1. a near-infrared transparent conductive film is characterized in that it being a kind of H doping In
2O
3Film, film thickness are 72 ~ 240nm, and carrier mobility is 126 ~ 140 cm
2/ Vs, free carrier concentration is lower than 1.9 * 10
20Cm
-3, resistivity is lower than 3.1 * 10
-4Ω .cm, the mean transmissivity of visible light and near infrared range is higher than 80%.
2. method for preparing the said near-infrared transparent conductive film of claim 1 is characterized in that: using purity is 99.99% ceramic target In
2O
3As the target raw material, Ar gas is sputter gas, O
2Gas and H
2The O steam is a reacting gas, adopts reaction radiofrequency magnetron sputtering technology room temperature preparation amorphous state H doping In on glass substrate
2O
3Film; Amorphous state H doping In with preparation
2O
3Film vacuum annealing 60 ~ 120 minutes under 170 ~ 200 ℃ of temperature forms the H doping In with polycrystalline structure
2O
3Film.
3. the preparation method of near-infrared transparent conductive film according to claim 2 is characterized in that the operating pressure in the reative cell is 0.5Pa.
4. the preparation method of near-infrared transparent conductive film according to claim 2 is characterized in that O
2With Ar+ O
2Flow rate ratio be 0.003 ~ 0.005.
5. the preparation method of near-infrared transparent conductive film according to claim 2 is characterized in that H
2The dividing potential drop of O steam does
1×10
-4?Pa~5×10
-4?Pa。
6. the preparation method of near-infrared transparent conductive film according to claim 2 is characterized in that sputtering power 50 ~ 100W.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100885400A CN102610670A (en) | 2012-03-30 | 2012-03-30 | Near-infrared transparent conducting film and method for producing same |
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|---|---|---|---|
| CN2012100885400A CN102610670A (en) | 2012-03-30 | 2012-03-30 | Near-infrared transparent conducting film and method for producing same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826763A (en) * | 2012-09-25 | 2012-12-19 | 上海北玻玻璃技术工业有限公司 | Method for producing transparent conducting oxide (TCO) coated glass |
| CN104164654A (en) * | 2014-07-23 | 2014-11-26 | 华灿光电股份有限公司 | Method for preparing transparent conductive film |
| CN106521415A (en) * | 2016-10-27 | 2017-03-22 | 中山大学 | Modified transparent conductive indium oxide film annealing method |
| CN107557745A (en) * | 2017-10-31 | 2018-01-09 | 君泰创新（北京）科技有限公司 | The preparation method of non-crystal transparent conductive oxide film |
| CN112144029A (en) * | 2020-09-11 | 2020-12-29 | 中兴能源有限公司 | Preparation method of high-transmittance high-mobility ITO (indium tin oxide) film |
| CN112397596A (en) * | 2020-12-28 | 2021-02-23 | 东方日升新能源股份有限公司 | Low-cost high-efficiency solar cell and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101931A (en) * | 2007-07-26 | 2008-01-09 | 复旦大学 | Near-infrared high-transmission rate non-crystal transparent conductive oxide film and its making method |
| CN101985741A (en) * | 2009-07-29 | 2011-03-16 | 中国科学院福建物质结构研究所 | Method for improving conductivity of indium-doped zinc oxide transparent conductive film |
-
2012
- 2012-03-30 CN CN2012100885400A patent/CN102610670A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101931A (en) * | 2007-07-26 | 2008-01-09 | 复旦大学 | Near-infrared high-transmission rate non-crystal transparent conductive oxide film and its making method |
| CN101985741A (en) * | 2009-07-29 | 2011-03-16 | 中国科学院福建物质结构研究所 | Method for improving conductivity of indium-doped zinc oxide transparent conductive film |
Non-Patent Citations (2)
| Title |
|---|
| T. KOIDA, ET AL: "High-mobility hydrogen-doped In2O3 transparent conductive oxide for a-Si:H/c-Si heterojunction solar cells", 《SOLAR ENERGY MATERIALS ＆ SOLAR CELLS》 * |
| T. KOIDA, ET AL: "Hydrogen-doped In2O3 as High-mobility Transparent Conductive Oxide", 《JAPANESE JOURNAL OF APPLIED PHYSICS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826763A (en) * | 2012-09-25 | 2012-12-19 | 上海北玻玻璃技术工业有限公司 | Method for producing transparent conducting oxide (TCO) coated glass |
| CN104164654A (en) * | 2014-07-23 | 2014-11-26 | 华灿光电股份有限公司 | Method for preparing transparent conductive film |
| CN106521415A (en) * | 2016-10-27 | 2017-03-22 | 中山大学 | Modified transparent conductive indium oxide film annealing method |
| CN106521415B (en) * | 2016-10-27 | 2020-05-19 | 中山大学 | Improved annealing method for indium oxide transparent conductive film |
| CN107557745A (en) * | 2017-10-31 | 2018-01-09 | 君泰创新（北京）科技有限公司 | The preparation method of non-crystal transparent conductive oxide film |
| CN112144029A (en) * | 2020-09-11 | 2020-12-29 | 中兴能源有限公司 | Preparation method of high-transmittance high-mobility ITO (indium tin oxide) film |
| CN112397596A (en) * | 2020-12-28 | 2021-02-23 | 东方日升新能源股份有限公司 | Low-cost high-efficiency solar cell and preparation method thereof |
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Application publication date: 20120725 |