CN100477133C - Near-infrared high transmittance polycrystalline transparent conductive oxide film and preparation method thereof - Google Patents
Near-infrared high transmittance polycrystalline transparent conductive oxide film and preparation method thereof Download PDFInfo
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- CN100477133C CN100477133C CNB2007100411598A CN200710041159A CN100477133C CN 100477133 C CN100477133 C CN 100477133C CN B2007100411598 A CNB2007100411598 A CN B2007100411598A CN 200710041159 A CN200710041159 A CN 200710041159A CN 100477133 C CN100477133 C CN 100477133C
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Abstract
The invention discloses a making method of near infrared high-transmissivity polycrystalline transparent conductive oxide film, which is characterized by the following: adopting conductive oxide film as doped indium oxide and M (M is W and Mo); using common glass as base; reacting indium metal to dop W or Mo insert target under 300-500 deg.c through DC magnetic sputtering technique; obtaining the In2O3:M film with polycrystalline structure under fitful sputtering pressure, partial oxygen pressure, sputtering current and sputtering voltage; fitting for applying in the solar energy battery domain.
Description
Technical field
The invention belongs to the transparent conductive film technical field, be specifically related to a kind of near-infrared high-transmission rate and multi-crystal transparent conductive oxide film and preparation method thereof.
Background technology
Transparent conductive oxide (TCO) film is because of the transparency that has visible-range simultaneously and the peculiar property of good electrical conductivity, thereby is widely used in flat-panel display device and solar cell as transparent " metal " electrode.Wherein the most representative material is In
2O
3: Sn (ITO), SnO
2: F and ZnO:Al (AZO) film.The TCO thin-film material generally has high carrier concentration, low resistivity (10
-4Ω cm); And wide energy gap (＞3eV), make film have high transmissivity (＞80%) at visible-range.
But, traditional commercial TCO film such as ITO, when wavelength during greater than 1 μ m, 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.
Generally speaking, have two kinds of methods can improve the conductivity of TCO film, a kind of is by improving the carrier concentration of film, and another kind is the carrier mobility that improves film.Because carrier concentration is too high, the transparency of film descends, so be restricted by improving the conductivity that carrier concentration improves film.The electric property that improves TCO by the raising carrier mobility becomes the development in future direction.
Summary of the invention
The objective of the invention is to propose a kind of have industrial production, near-infrared high-transmission rate and multi-crystal transparent conductive oxide film that technology stability is good and preparation method thereof.
The multi-crystal transparent conductive oxide film that the present invention proposes is a kind of doped indium oxide film In
2O
3: M, M are W or Mo, survey shooting method by direct magnetic control and prepare, and wherein, tungsten and molybdenum exist among the film with six rank attitude ions, and film thickness is 80-150nm, has high carrier mobility, and free carrier concentration is lower than 2 * 10
20Cm
-3, the average transmittance of visible region is higher than 80%, and the average transmittance of near infrared region is greater than 90%.
The method of the multi-crystal transparent conductive oxide film that the present invention proposes, adopt the magnetically controlled DC sputtering coating technique, indium metal mosaic target with Doped Tungsten or molybdenum is a target, with glass is substrate, under substrate temperature 300-350 ℃ condition, with Ar ion beam irradiation target, with target as sputter, sputtering current is 80-200mA, and sputtering voltage is 300-500V, and the operating pressure in the reative cell is 3.0 * 10
-1Pa, O
2The dividing potential drop of reacting gas is (1.0-3.0) * 10
-2Pa, sputtering time 1-15 minute, i.e. formation has the Doped Tungsten of polycrystalline structure or the indium oxide transparent conductive oxide film In of molybdenum
2O
3: M, M are W or Mo.
The preferable preparation condition of the present invention is as follows:
Substrate temperature is 320-330 ℃.
O
2The dividing potential drop of reacting gas is (1.0-2.0) * 10
-2Pa.
During reaction magnetically controlled DC sputtering plated film, sputtering condition is: sputtering current 100-150mA, sputtering voltage 400-450V, sputtering time 8-10 minute.
Among the present invention, by variable conductance valve with O
2Feed reative cell with Ar gas, variable conductance valve is the common method that the magnetically controlled DC sputtering plated film feeds gas.
The multi-crystal transparent conductive oxide film thickness that the inventive method makes is 80-150nm, can control thickness by the control sputtering time as required.
Experimental result shows, the In of the present invention's preparation
2O
3: the M film has high valence state, and poor (tungsten or molybdenum are present in six rank attitude ions among the film, i.e. W
+ 6And M
+ 6With three rank attitude In
+ 3The valence state difference that forms is 3), the photoelectric characteristic of high carrier mobility, low-resistivity, visible-range and near infrared range high optical transparency, its carrier mobility is (40-70) cm
2/ Vs, resistivity is (3-6) * 10
-4Ω cm, the average transmittance of visible-range is greater than 80%, and the average transmittance of near infrared region (700-2500nm) is greater than 90%.Has the advantage that surmounts the ITO properties of product.And the technology stability of the inventive method is very good, the deposition rate height, and the film of preparation is even, and area is big.The film of the present invention's preparation has a good application prospect in area of solar cell.
Description of drawings
The X-ray diffractogram of mixing tungsten indium oxide (IWO) film for preparing under Fig. 1 different partial.
Fig. 2 is 2 * 10 in partial pressure of oxygen
-2The AFM shape appearance figure of mixing tungsten indium oxide (IWO) film surface for preparing during Pa.
What prepare under the various partials pressure of oxygen of Fig. 3 mixes the transmittance graph of tungsten indium oxide (IWO) transparent conductive oxide film in the 300-3200nm wave-length coverage.ITO curve wherein is corresponding to the transmission spectrum of the ito thin film for preparing under identical preparation condition.
Embodiment
Further describe the present invention below by specific embodiment:
Substrate temperature: 322 ℃.The spacing of target and substrate is fixed as 100mm.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 100mA, and sputtering voltage is 400V, control O
2The dividing potential drop of reacting gas is 2 * 10
-2Pa.Film preparation is on the simple glass sheet, and sputtering time 10 minutes, film thickness are 113nm.The resistivity of film is 3.0 * 10
-4Ω cm, carrier mobility is 71cm
2/ Vs, the average transmittance of visible-range is 83%, the average transmittance of near infrared region (700-2500nm) is greater than 90%.
Substrate temperature: 350 ℃.The spacing of target and substrate is fixed as 95mm.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 1.7Pa, and sputtering current is 200mA, and sputtering voltage is 400V, control O
2The dividing potential drop of reacting gas is 1.5 * 10
-2Pa.Film preparation is on the simple glass sheet, and sputtering time 10 minutes, film thickness are 105nm.The resistivity of film is 3.7 * 10
-4Ω cm, carrier mobility is 50cm
2/ Vs, the average transmittance of visible-range is greater than 80%, and the average transmittance of near infrared region (700-2500nm) is greater than 90%.
Embodiment 4, under 350 ℃ of substrate temperatures, method similarly to Example 3, make polycrystalline IMO film under the following conditions: sputtering current is 150mA, sputtering voltage is 450V, by variable conductance valve with O
2Feed O with Ar gas
2Reative cell is also controlled O
2The dividing potential drop of reacting gas is 1.5 * 10
-2Pa.Sputtering time 10 minutes, film thickness are 110nm.The resistivity of film is 6.0 * 10
-4Ω cm, carrier mobility is 42cm
2/ Vs, the average transmittance of visible-range is greater than 80%, and the average transmittance of near infrared region is greater than 90%.
Claims (5)
1. a near-infrared high-transmission rate and multi-crystal transparent conductive oxide film is characterized in that it being a kind of Doped Tungsten or molybdenum indium oxide film In
2O
3: M, M are W or Mo, survey shooting method by direct magnetic control and prepare, and wherein, tungsten or molybdenum exist among the film with six rank attitude ions, and film thickness is 80-150nm, and carrier mobility is (40-70) cm
2/ Vs, free carrier concentration is lower than 2 * 10
20Cm
-3, the average transmittance of visible region is higher than 80%, and the average transmittance of near infrared region is greater than 90%.
2. the preparation method of a near-infrared high-transmission rate and multi-crystal transparent conductive oxide film, it is characterized in that adopting reaction magnetically controlled DC sputtering coating technique, concrete steps are as follows: the indium metal mosaic target with Doped Tungsten or molybdenum is a target, with glass is substrate, under substrate temperature 300-350 ℃ condition, with Ar ion beam irradiation target, with target as sputter, sputtering current is 80-200mA, and sputtering voltage is 300-500V, and the operating pressure in the reative cell is 3.0 * 10
-1Pa, O
2The dividing potential drop of reacting gas is (1.0-3.0) * 10
-2Pa, sputtering time 1-15 minute, i.e. formation has the Doped Tungsten of polycrystalline structure or the indium oxide transparent conductive oxide film In of molybdenum
2O
3: M, M are W or Mo.
3. the preparation method of multi-crystal transparent conductive oxide film according to claim 2 is characterized in that substrate temperature is 320-330 ℃.
4. the preparation method of multi-crystal transparent conductive oxide film according to claim 2 is characterized in that the dividing potential drop of oxygen reacting gas is (1.0-2.0) * 10
-2Pa.
5. the preparation method of multi-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 400-450V, sputtering time 8-10 minute.
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| CN100477133C true CN100477133C (en) | 2009-04-08 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560642B (en) * | 2009-05-22 | 2011-05-11 | 南开大学 | A method for preparing high-mobility Mo-doped In2O3 transparent conductive film |
| CN101989635B (en) * | 2009-08-07 | 2011-12-14 | 北儒精密股份有限公司 | Electrode Manufacturing Equipment for Solar Cells |
| FR2968414B1 (en) * | 2010-12-06 | 2013-07-05 | Saint Gobain | ELECTROCHEMICAL DIPOSITIVE WITH ELECTRONICALLY CONTROLLED OPTICAL AND / OR ENERGY TRANSMISSION PROPERTIES |
| 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 absorption rate and its manufacturing method |
| CN105112869B (en) * | 2015-08-31 | 2017-11-17 | 哈尔滨工业大学 | A kind of preparation method of doped yttrium cupric oxide infrared transparent conductive film |
| CN109678361A (en) * | 2019-01-16 | 2019-04-26 | 南京航空航天大学 | A kind of preparation method of the alkali silicate glass of containing transition metal |
| CN114057470A (en) * | 2020-07-31 | 2022-02-18 | 广州市尤特新材料有限公司 | Preparation method of molybdenum-doped indium oxide target material and molybdenum-doped indium oxide target material |
| CN114436641B (en) * | 2022-03-02 | 2022-12-20 | 桂林电子科技大学 | Magnetron sputtering ceramic target material and preparation method thereof |
| CN116589201B (en) * | 2023-07-17 | 2023-09-08 | 山东蓝玻玻璃科技有限公司 | Near-infrared high-transmittance coated glass and preparation method thereof |
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2007
- 2007-05-24 CN CNB2007100411598A patent/CN100477133C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| Transparent conductive In2O3:Mo thin filmspreparedbyreactive direct current magnetron sputteringat room temperature. Weina Miao,Xifeng Li,Qun Zhang,et al.Thin Solid Films,Vol.500 . 2005 * |
| 高迁移率透明导电In2O3:Mo薄膜. 李喜峰，缪维娜，张群，黄丽，章壮健，华中一.真空科学与技术学报，第25卷第2期. 2005 * |
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