CN101101931A - Near-infrared high-transmission rate non-crystal transparent conductive oxide film and its making method - Google Patents
Near-infrared high-transmission rate non-crystal transparent conductive oxide film and its making method Download PDFInfo
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- CN101101931A CN101101931A CNA2007100442401A CN200710044240A CN101101931A CN 101101931 A CN101101931 A CN 101101931A CN A2007100442401 A CNA2007100442401 A CN A2007100442401A CN 200710044240 A CN200710044240 A CN 200710044240A CN 101101931 A CN101101931 A CN 101101931A
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- sputtering
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- transparent conductive
- oxide film
- conductive oxide
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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
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Abstract
The invention is concerned with the near infrared high transmissivity non-crystal transparent electrode guiding oxide thing film and the making method. It belongs to the transparent electricity guiding film technique. The electricity guiding film mixes with the oxidant indium In2O3:M(M=Mo, W). The invention uses the normal glass as the basal board , the studded target made of the indium metal mixing into molybdenum or tungstenic, and applies the responsive direct current magnetron sputtering technique under the condition of the basal board temperature equals room temperature, and also, under the appropriate state for the sputtering pressure, the oxygen partial pressure, the sputtering current, and the sputtering voltage to achieve the non-crystal structure In2O3:M film. The film is with low resistivity, higher carrier mobility, higher transmissivity in visible light, and especially higher transmissivity in near infrared and so on characteristic of photo-electricity. It can be use widely in the flexibility solar battery field and the near infrared sensor field and so on.
Description
Technical field
The invention belongs to the transparent conductive film technical field, be specifically related to a kind of non-crystal transparent conductive oxide film and preparation method thereof.
Background technology
In the past few decades, transparent conductive oxide (TCO) film has obtained extensive use and more and more has been subjected to people's attention at optoelectronic areas such as flat-panel display device and solar cells because of the transparency that has visible-range simultaneously and the peculiar property of good electrical conductivity.At present, people are by the performance that the whole bag of tricks comprises technology, mix different elements, multi-layer film structure and multicomponent etc. are devoted to improve and optimize the TCO film, to adapt to and to develop new application.The most representative TCO material is In
2O
3: Sn (ITO), it generally has high carrier concentration (10
21Cm
-3Magnitude), low resistivity (10
-4Ω cm); And wide energy gap (＞3eV), make film have high transmissivity (＞80%) at visible-range.
Ito thin film is when wavelength during greater than 1 μ m, and its transmissivity sharply descends.This has just seriously hindered passing through of near infrared region light.And we know, sunlight only accounts for 43% of its full-luminous wave-length coverage (300-2500nm) at the energy of visible-range (400-700nm).Sunlight is 5% of a gross energy at the energy of ultraviolet region (300-400nm), and is 52% of gross energy at the energy of near infrared 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.Improving the transmissivity of transparent conductive film near infrared region, is one of effective way that improves by solar cell.In addition, for the transducer that uses near infrared region, improve the transmissivity of near infrared region, the sensitivity that will help to improve instrument.
One of effective ways that improve the transparent conductive film transparency are the carrier concentrations that reduces film, but can cause the decline of conductivity usually.Another kind method is to improve the carrier mobility of film, and this is a developing direction of improving the photoelectricity performance of TCO.The applicant adopts the reaction direct current magnetron sputtering process to prepare high valence state, and poor (molybdenum and tungsten are present among the film with the hexavalent state ion easily, i.e. Mo
+ 6And W
+ 6In with three valence states
+ 3Between the valence state difference that forms be 3) In
2O
3: the M transparent conductive oxide film, obtained high carrier mobility, and free carrier concentration has only 2-5 * 10
20Cm
-3The low-resistivity film, the average transmittance of its visible region (containing the substrate of 1.2mm heavy sheet glass) is higher than 80%.And experiment finds that this class film improves greatly in the transmissivity of near infrared region, is better than the transmissivity of ito thin film near infrared region.
It is good that direct current magnetron sputtering process has controllability, and the characteristics that deposition rate is high are one of the most practical method for manufacturing thin film.And that the damascene target has a cost is low, and rate of film build is high and can obtain the characteristics of the uniform film of large tracts of land.Therefore the present invention studies and adopts direct current magnetron sputtering process and In:Mo (or W) damascene target to prepare amorphous high-performance In at ambient temperature
2O
3: the M transparent conductive oxide film.Can predict that adopt the oxide ceramics target of indium oxide and molybdenum oxide (or tungsten) preparation, it is good also can to prepare photoelectric properties by radio-frequency magnetron sputter method, has the In of high-transmission rate near infrared region
2O
3: M (M=Mo, W) non-crystal transparent conductive oxide film.
Amorphous In with near infrared region high-transmission rate
2O
3: the M transparent conductive oxide film has actual application prospect in the flexible base, board solar cell and the near infrared sensor field of non-refractory.
Summary of the invention
The objective of the invention is to near-infrared high-transmission rate non-crystal transparent conductive oxide film that proposes the good and easy suitability for industrialized production of a kind of technology stability and preparation method thereof.
The non-crystal transparent conductive oxide film that the present invention proposes is a kind of doped indium oxide film In
2O
3: M, M are Mo or W, are prepared by the reaction dc magnetron sputtering method, and wherein, molybdenum and tungsten are present in the hexavalent state ion among the film, and film thickness is 80-150nm.This film has high carrier mobility, reaches 20cm
2About/Vs, free carrier concentration is lower, generally is lower than 8 * 10
20Cm
-3, resistivity is lower, and remaining on is 6 * 10
-4The magnitude of Ω cm, the average transmittance of visible region is higher than 80%, and the average transmittance of near infrared region is greater than 80%.
The preparation method's of the non-crystal transparent conductive oxide film that the present invention proposes concrete steps are as follows: adopt the magnetically controlled DC sputtering coating technique, indium metal mosaic target with doping molybdenum or tungsten is a target, with glass is substrate, at substrate temperature is under the condition of room temperature, with Ar ion beam irradiation target, with target as sputter, sputtering current is 80-150mA, sputtering voltage is 300-500V, and the operating pressure in the reative cell is 2.5 * 10
-1Pa, O
2The dividing potential drop of reacting gas is 3.3 * 10
-2Pa-4.3 * 10
-2Pa, sputtering time 5-20 minute, i.e. formation has the doping molybdenum of non crystalline structure or the indium oxide transparent conductive oxide film In of tungsten
2O
3: M, M are Mo or W.
The preferable preparation condition of the present invention is as follows:
Substrate temperature is room temperature (for example 20-25 a ℃).
O
2The dividing potential drop of reacting gas is 3.8 * 10
-2Pa-4.3 * 10
-2Pa.
During reaction magnetically controlled DC sputtering plated film, sputtering condition is: sputtering current 100-150mA, sputtering voltage 300-400V, sputtering time 10-15 minute.
Among the present invention, by variable conductance valve with O
2Feed reative cell with Ar gas, feed the prior art of gas when variable conductance valve is the magnetically controlled DC sputtering plated film.
The non-crystal transparent conductive oxide film thickness that the inventive method makes is 100-150nm, can control thickness by the control sputtering time as required.
Experimental result shows, the In of the present invention's preparation
2O
3: (M=Mo, W) film has high valence state poor (molybdenum and tungsten is present in the hexavalent state ion among the film, i.e. Mo M
+ 6And W
+ 6Hexavalent state ion and In
+ 3The valence state difference that three valence state ions form is 3), the photoelectric characteristic of high carrier mobility, low-resistivity, visible-range and near infrared range (700-2500nm) high optical transparency, its carrier mobility reaches 20cm
2/ Vs, free carrier concentration is lower than 5.2 * 10
20Cm
-3, resistivity is 5.9 * 10
-4Ω cm, the average transmittance of visible region (containing substrate) is higher than 80%, and the average transmittance of near infrared region (containing substrate) is greater than 80%.Has the advantage that surmounts the ITO properties of product.And the technology stability of the inventive method is good, the film deposition rate height, and the film of preparation is even.The film of the present invention's preparation has a good application prospect at flexible solar battery and near infrared sensor field.
Description of drawings
Fig. 1 different partial and the different X-ray diffractograms of mixing molybdenum doped indium oxide (IMO) film of preparation under the molybdenum content.
Fig. 2 difference is mixed the relation curve of the carrier mobility of molybdenum doped indium oxide (IMO) film for preparing under the molybdenum content condition with the partial pressure of oxygen variation.
The transmittance graph of molybdenum doped indium oxide (IMO) transparent conductive oxide film in the 300-3000nm wave-length coverage for preparing under the various partials pressure of oxygen of Fig. 3.
Embodiment
Further describe the present invention below by specific embodiment:
Embodiment 1, preparation molybdenum doped indium oxide target: with purity is that 99.99% In metal melting becomes target, embeds same purity symmetrically and is 99.99% molybdenum filament 2wt% and be prepared from, and target diameter is 51mm, and thickness is 3.0mm.Substrate is common slide, successively cleans in each 15 minutes through pure water, alcohol and acetone ultrasonic wave.
Substrate temperature: room temperature.The spacing of target and substrate is fixed as 50mm.Earlier reative cell is evacuated down to before the thin film deposition and is lower than 2 * 10
-3Pa, then by variable conductance valve with O
2Feed reative cell with Ar gas.Operating pressure in the reative cell is 2.5 * 10
-1Pa, sputtering current are 100mA, and sputtering voltage is 350V, control O
2The dividing potential drop of reacting gas is 3.8 * 10
-2Pa.Film preparation is on the simple glass sheet.Sputtering time 10 minutes, film thickness are 130nm.The carrier mobility of film is 20cm
2/ Vs, carrier concentration is 5.2 * 10
20Cm
-3, resistivity is 5.9 * 10
-4Ω cm, the average transmittance of visible region (containing substrate) is higher than 80%, and the average transmittance of near infrared region (containing substrate) is greater than 80%.
Embodiment 2, and tungsten indium oxide target is mixed in preparation: with purity is that 99.99% In metal melting becomes target, embeds same purity symmetrically and is 99.99% tungsten filament 2wt% and be prepared from, and target diameter is 51mm, and thickness is 3.0mm.Substrate is common slide, successively cleans in each 15 minutes through pure water, alcohol and acetone ultrasonic wave.
Substrate temperature: room temperature.The spacing of target and substrate is fixed as 50mm.Earlier reative cell is evacuated down to before the thin film deposition and is lower than 2 * 10
-3Pa, then by variable conductance valve with O
2Feed reative cell with Ar gas.Operating pressure in the reative cell is 3.0 * 10
-1Pa, sputtering current are 150mA, and sputtering voltage is 385V, control O
2The dividing potential drop of reacting gas is 3.5 * 10
-2Pa.Film preparation is on the simple glass sheet.Sputtering time 8 minutes, film thickness are 120nm.The carrier mobility of film is 18cm
2/ Vs, carrier concentration is 6.2 * 10
20Cm
-3, resistivity is 6.3 * 10
-4Ω cm, the average transmittance of visible region (containing substrate) is higher than 80%, and the average transmittance of near infrared region (containing substrate) is greater than 80%.
Claims (4)
1. a near-infrared high-transmission rate non-crystal transparent conductive oxide film is characterized in that it being a kind of doped indium oxide film In
2O
3: M, M are Mo or W, are prepared by the reaction dc magnetron sputtering method, wherein, molybdenum and tungsten are present in the hexavalent state ion among the film, and film thickness is 80-150nm, the average transmittance of visible region is higher than 80%, and the average transmittance of near infrared region is also greater than 80%.
2. the preparation method of a near-infrared high-transmission rate non-crystal transparent conductive oxide film as claimed in claim 1, it is characterized in that adopting reaction magnetically controlled DC sputtering coating technique, concrete steps are as follows: the indium metal mosaic target with doping molybdenum or tungsten is a target, with glass is substrate, is under the condition of room temperature at substrate temperature, with Ar ion beam irradiation target, with target as sputter, sputtering current is 80-150 mA, and sputtering voltage is 300-500 V, and the operating pressure in the reative cell is 2.5 * 10
-1Pa, O
2The dividing potential drop of reacting gas is 3.3-4.3 * 10
-2Pa, sputtering time are 5-20 minute, promptly form to have the doping molybdenum of non crystalline structure or the indium oxide transparent conductive oxide film In of tungsten
2O
3: M, M are Mo or W.
3. the preparation method of non-crystal transparent conductive oxide film according to claim 2 is characterized in that O
2The dividing potential drop of reacting gas is 3.3 * 10
-2Pa-4.3 * 10
-2Pa.
4. the preparation method of non-crystal transparent conductive oxide film according to claim 2, when it is characterized in that reacting the magnetically controlled DC sputtering plated film, sputtering condition is: sputtering current 100-150mA, sputtering voltage 300-400V, sputtering time 10-15 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100442401A CN101101931A (en) | 2007-07-26 | 2007-07-26 | Near-infrared high-transmission rate non-crystal transparent conductive oxide film and its making method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100442401A CN101101931A (en) | 2007-07-26 | 2007-07-26 | Near-infrared high-transmission rate non-crystal transparent conductive oxide film and its making method |
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|---|---|
| CN101101931A true CN101101931A (en) | 2008-01-09 |
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ID=39036110
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102610670A (en) * | 2012-03-30 | 2012-07-25 | 鲁东大学 | Near-infrared transparent conducting film and method for producing same |
| CN103173732A (en) * | 2013-03-08 | 2013-06-26 | 北京航空航天大学 | Preparation method of (doped amorphous) p-type transparent conductive oxide films |
| CN103187472A (en) * | 2011-12-30 | 2013-07-03 | 亚树科技股份有限公司 | Thin film solar cell with high infrared light absorptivity and processing method thereof |
| CN105845314A (en) * | 2016-04-27 | 2016-08-10 | 天津大学 | High-magnetoresistance-effect CoFeB/SiO<2>/n-Si heterojunction structure and preparation method therefor |
-
2007
- 2007-07-26 CN CNA2007100442401A patent/CN101101931A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103187472A (en) * | 2011-12-30 | 2013-07-03 | 亚树科技股份有限公司 | Thin film solar cell with high infrared light absorptivity and processing method thereof |
| CN102610670A (en) * | 2012-03-30 | 2012-07-25 | 鲁东大学 | Near-infrared transparent conducting film and method for producing same |
| CN103173732A (en) * | 2013-03-08 | 2013-06-26 | 北京航空航天大学 | Preparation method of (doped amorphous) p-type transparent conductive oxide films |
| CN103173732B (en) * | 2013-03-08 | 2014-12-03 | 北京航空航天大学 | Preparation method of (doped amorphous) p-type transparent conductive oxide films |
| CN105845314A (en) * | 2016-04-27 | 2016-08-10 | 天津大学 | High-magnetoresistance-effect CoFeB/SiO<2>/n-Si heterojunction structure and preparation method therefor |
| CN105845314B (en) * | 2016-04-27 | 2017-09-05 | 天津大学 | CoFeB/SiO with large magnetic resistance effect2/ n Si heterojunction structures and preparation method |
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Open date: 20080109 |