CN101299423B - Amorphous tungsten-doped tin dioxide transparent conductive oxide thin film and preparation method thereof - Google Patents
Amorphous tungsten-doped tin dioxide transparent conductive oxide thin film and preparation method thereof Download PDFInfo
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- CN101299423B CN101299423B CN2008100392089A CN200810039208A CN101299423B CN 101299423 B CN101299423 B CN 101299423B CN 2008100392089 A CN2008100392089 A CN 2008100392089A CN 200810039208 A CN200810039208 A CN 200810039208A CN 101299423 B CN101299423 B CN 101299423B
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Abstract
The invention belongs to the technical field of the transparent conductive film, particularly to the amorphous W-doped cassiterite transparent conductive film and the preparation method. The invention uses the cassiterite and the metal tungsten powder through the grinding, mixing, tabletting and sintering to obtain the block material as the target materials.Through the pulse plasma deposit (PPD) technology on the common glass substrate, SnO2:W film with the amorphous structure is prepared, wherein the film has the excellent optical and electrical performance of low resistivity, high carrier mobility, high visible light range transmissivity and high near infrared range transmissivity. The film obtained by the method can be applied with good application foreground in the flat panel display,the photoelectric sensor and the solar cell.
Description
Technical field
The invention belongs to the transparent conductive film technical field, be specifically related to a kind of tungsten-doped tin dioxide non-crystal transparent conductive oxide film and preparation method thereof.
Background technology
Conductivity and the visible region transparency of transparent conductive oxide film (TCO) because of having metal becomes material indispensable in flat-panel monitor, solar cell and the transparent electronics.Tin-doped indium oxide (ITO) is the maximum transparent conductive material of commercial always, but the reserves of indium metal are limited, can not satisfy the market demand that enlarges day by day, and in the past several years, its price has been turned over ten times! Therefore the substitution material of exploring ito thin film becomes one of trend of transparent conductive film research from now on.At present, people comprise technology, select different host materials (as In by the whole bag of tricks
2O
3, ZnO, SnO
2Deng), the different elements that mix (as high valence state metallic element), multi-layer film structure and multicomponent etc. be devoted to improve and optimize the performance of TCO film, to adapt to and to develop new application.
The tin ash based film material is to obtain the commercial transparent conductive material of using the earliest, has good chemical stability, not only can avoid indium diffusion couple photoelectric device Effect on Performance in the ito thin film, and can overcome the oxygen absorption problem that Al-Doped ZnO film exists, be that preparation is efficient, the important materials of high stability thin-film solar cells window electrode and photoelectric device.In recent years, the research of tin ash base transparent conducting film mainly concentrated on to mix by cation or anion displacement improve its photoelectric properties, studying more is to form Sb by mixing
5+Displacement Sn
4+And F
-Displacement O
2-ATO transparent conductive film and FTO transparent conductive film.The ATO film Sb can occur under different temperature and partial pressure of oxygen
5+And Sb
3+If two kinds of valence states are Sb
5+Replace Sn
4+, then introduce one apart from SnO
2The donor level that conduction band is very near; Sb
3+Replace Sn
4+, then produce one apart from SnO
2The acceptor level that valence band is very near.Generally, both of these case all can take place, and compound, compensating effect occurs, makes doping efficiency reduce.The present invention considers the high valence state stability and the ionic radius (W more approaching with tin of tungsten
6+: 67pm; Sn
4+: 69pm; Sb
4+: 62pm; Sb
3-: 245pm), first the tin ash matrix is carried out tungsten and mix, obtained having the non crystalline structure SnO of low-resistivity, high carrier mobility, high visible light transmissivity and nearinfrared transmittance by the pulse plasma body technique
2: the W transparent conductive film.In addition, the amorphous SnO that undopes of this experimental technique preparation
2Film also has the conductivity and the transparency preferably.
The same pulsed laser deposition of pulsed plasma deposition technique (PPD) (PLD) method is similar, all be based on the ablation process of plating, promptly transferred to the very little position of target material surface very high energy moment, cause its temperature to be higher than distillation restriction, target comes out and utilizes remaining kinetic energy to move to substrate surface and deposit the formation film with regard to ablated like this.PLD has validity and the universality same with PLD, but more simple in the operation, equipment cost is more cheap.
The amorphous SnO of this method preparation
2: the W transparent conductive film has large-scale production, has a good application prospect in flat panel display, transparent photoelectric device and fields such as solar cell and near infrared sensor.
Summary of the invention
The objective of the invention is to propose a kind of novel transparent conductive oxide film that does not contain the expensive metal indium and preparation method thereof.
The non-crystal transparent conductive oxide film that the present invention proposes is a kind of tungsten-doped tin dioxide SnO
2: W film is prepared by the pulsed plasma deposition process.Specifically be on glass substrate, with oxygen and argon gas, to be working gas, when substrate temperature is 380-420 ℃, prepare the SnO of non crystalline structure
2: W film, thickness are 50-120nm, and the doping of tungsten is SnO
2The 0.5%-5% of quality, the carrier mobility of this film is at (21.4-45.7) cm
2Between/the Vs, free carrier concentration is in (4.3-9.6) * 10
19Cm
-3Between, resistivity is minimum to reach 2.1 * 10
-3Ω cm, the average transmittance of visible region is higher than 89%, and the average transmittance of near infrared region reaches 95%.
The preparation of the novel transparent conductive oxide film that the present invention proposes, adopt the pulsed plasma deposition process, concrete steps are: with the tungsten-doped tin dioxide powder is raw material, forms ceramic target through grinding, compressing tablet, sintering, wherein, the doping of tungsten is tin ash (SnO
2) 0.5%-5% of quality, with the simple glass is substrate, be under 380-420 ℃ the condition at substrate temperature, with oxygen and argon gas is working gas, and operating pressure is 2.8-3.2Pa, and oxygen partial pressure is 1.2-2.0Pa, pulse current is 3.2-4.0mA, pulse voltage is-14kV--18kV that sedimentation time is 10-100 minute, promptly forms the tungsten-doped tin dioxide transparent conductive oxide thin film with non crystalline structure.
The preferable preparation condition of the present invention is as follows:
Substrate temperature is 400 ℃-410 ℃, and partial pressure of oxygen is 1.2-2.0Pa.
During the pulsed plasma deposition, sedimentary condition is: pulse current 3.6mA, pulse voltage-15kV--16kV, sedimentation time 20-30 minute.
The doping of tungsten is SnO
2The 1%-3% of quality.
The non-crystal transparent conductive oxide film thickness that the inventive method makes is 50-120nm, and can regulate thickness by controlling the ablation time as required.
Experimental result shows, the amorphous SnO of the present invention's preparation
2: W film has that resistivity is low, carrier mobility is high, visible-range and the good characteristic of near infrared range optical transparence, and its carrier mobility is 21.4-45.7cm
2/ Vs, carrier concentration is 4.3-9.6 * 10
19Cm
-3, lowest resistivity is respectively 2.1 * 10
-3Ω cm, the average transmittance of visible region (400-200nm) (not containing substrate) is higher than 89%, and the average transmittance of near infrared region (700-2500nm) (not containing substrate) is about 95%.In transparent electronics, has potential using value.And the technology cost of the inventive method is low, stable performance, film deposition rate height.The film of the present invention preparation has a good application prospect aspect effectively the utilizing of solar cell window electrode pair visible light wave range and near infrared band expanding.
Description of drawings
Fig. 1. difference is mixed the X-ray diffractogram of the tungsten-doped tin dioxide film of W content and different partial preparation.
Fig. 2 difference is mixed the influence of W content to amorphous tungsten-doped tin dioxide film electrical properties.
Fig. 3 amorphous tungsten-doped tin dioxide film is at the transmittance curve of 320-3200nm scope.
Embodiment
Further describe the present invention below by specific embodiment:
The tungsten doping content is 1wt%.Earlier the settling chamber is evacuated down to before the thin film deposition and is lower than 6.5 * 10
-3Pa, then by variable conductance valve with O
2Feed vacuum chamber with Ar gas.Operating pressure in the settling chamber is 3.0Pa, and the simple glass underlayer temperature is 400 ℃, and partial pressure of oxygen is 1.8Pa, operating current 3.6mA, operating voltage-16kV, sedimentation time 20 minutes.Film thickness is 72nm, and carrier mobility is at 44cm
2/ Vs, carrier concentration is 4.9 * 10
19Cm
-3, resistivity is 2.9 * 10
-3Ω cm, the average transmittance of visible region was higher than for 89% (not containing substrate), and the average transmittance of near infrared region reached for 95% (not containing substrate).
The tungsten doping content is 3wt%.Earlier the settling chamber is evacuated down to before the thin film deposition and is lower than 6.5 * 10
-3Pa, then by variable conductance valve with O
2Feed vacuum chamber with Ar gas.Operating pressure in the settling chamber is 3.0Pa, and the simple glass underlayer temperature is 400 ℃, and partial pressure of oxygen is 1.2Pa, operating current 3.6mA, operating voltage-16kV, sedimentation time 20 minutes.Film thickness is 60nm, carrier mobility 21.4cm
2/ Vs, carrier concentration 5.8 * 10
19Cm
-3, resistivity 3.6 * 10
-3Ω cm, the average transmittance of visible region was higher than for 89% (not containing substrate), and the average transmittance of near infrared region reached for 95% (not containing substrate).
Adopt Kosaka ET3000 type surface profiler MEASUREMENTS OF THIN thickness, use BD-90 type four point probe instrument MEASUREMENTS OF THIN square resistance and target resistivity, adopt Tianjin, island UV2450 type ultraviolet/visible spectrophotometer MEASUREMENTS OF THIN transmission spectrum.Adopt the Hall effect of ear tester (Bio-Rad Microscience HL5500 Hall system) MEASUREMENTS OF THIN suddenly under the room temperature, thereby obtain the carrier mobility and the carrier concentration of film.Utilize the electric conductivity of Seebeck effect tester observational measurement target and film.Go up employing Cu K at Rigaku D/max-rB type X-ray diffractometer (XRD)
α 1For light source obtains film XRD spectrum 20 °～80 ° interscans.
Claims (5)
1. a non-crystal transparent conductive oxide film is characterized in that it being a kind of tungsten-doped tin dioxide SnO
2: W film, prepare by the pulsed plasma deposition process, film thickness is 50-120nm, wherein, the content of W is SnO
2The 0.5%-5% of quality.
2. the preparation method of a non-crystal transparent conductive oxide film as claimed in claim 1, it is characterized in that adopting the pulsed plasma deposition technique, concrete steps are as follows: is target with the tungsten-doped tin dioxide powder through the block materials that ground and mixed, compressing tablet, sintering form, and the doping of tungsten is SnO
2The 0.5%-5% of quality, with the simple glass is substrate, be under 380-420 ℃ the condition at substrate temperature, with oxygen and argon gas is that working gas deposits, operating pressure in the reative cell is 2.8-3.2Pa, and oxygen partial pressure is 1.2-2.0Pa, and pulse current is 3.2-4.0mA, deposition voltage is-14kV--18kV that sedimentation time is 10-100 minute.
3. the preparation method of non-crystal transparent conductive oxide film according to claim 2 is characterized in that substrate temperature is 400 ℃-410 ℃.
4. the preparation method of non-crystal transparent conductive oxide film according to claim 2, the doping content that it is characterized in that tungsten is 1%～3% of a tin ash quality.
5. the preparation method of non-crystal transparent conductive oxide film according to claim 2, when it is characterized in that the pulsed plasma deposition, pulse current 3.4-3.6mA, pulse voltage-15kV--16kV, sedimentation time 20-30 minute.
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| CN101299423B true CN101299423B (en) | 2010-12-15 |
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| US9818888B2 (en) * | 2015-03-12 | 2017-11-14 | Vitro, S.A.B. De C.V. | Article with buffer layer and method of making the same |
| JP2018160657A (en) * | 2017-03-23 | 2018-10-11 | 株式会社東芝 | Solar cell, multi-junction solar cell, solar cell module, and solar power generation system |
| CN108262052A (en) * | 2018-01-11 | 2018-07-10 | 上海大学 | Carbonitride-witch culture conductor oxidate hetero-junction thin-film and preparation method thereof |
| CN108465465A (en) * | 2018-04-04 | 2018-08-31 | 广东工业大学 | A kind of semiconductive thin film and preparation method thereof |
| CN112086532B (en) * | 2020-10-15 | 2021-10-22 | 湖北大学 | SnO2Basic homojunction self-driven ultraviolet photoelectric detector and preparation method thereof |
| CN113699491B (en) * | 2021-08-31 | 2023-09-12 | 江西省科学院应用物理研究所 | Method for preparing tungsten-doped composite coating |
Citations (2)
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|---|---|---|---|---|
| CN1234591A (en) * | 1999-05-10 | 1999-11-10 | 昆明理工大学 | Synthesis method for preparing silver-tin dioxide electric contact materials |
| US5984997A (en) * | 1997-08-29 | 1999-11-16 | Nanomaterials Research Corporation | Combustion of emulsions: A method and process for producing fine powders |
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2008
- 2008-06-19 CN CN2008100392089A patent/CN101299423B/en not_active Expired - Fee Related
Patent Citations (2)
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|---|---|---|---|---|
| US5984997A (en) * | 1997-08-29 | 1999-11-16 | Nanomaterials Research Corporation | Combustion of emulsions: A method and process for producing fine powders |
| CN1234591A (en) * | 1999-05-10 | 1999-11-10 | 昆明理工大学 | Synthesis method for preparing silver-tin dioxide electric contact materials |
Non-Patent Citations (6)
| Title |
|---|
| Bando, Yoshichika.Reactive Deposition of W-, Mo- and V-deped SnO₂ |
| Films.Bulletin of the Institute for Chemical Research, Kyoto.1992,70(4),430-434. |
| Muranaka, Shigetoshi |
| Muranaka, Shigetoshi;Bando, Yoshichika.Reactive Deposition of W-, Mo-and V-deped SnO₂Films.Bulletin of the Institute for Chemical Research, Kyoto.1992,70(4),430-434. * |
| R.K. Gupta, K. Ghosh, S.R. Mishra, P.K. Kahol.High mobility W-doped In2O3 thin films: Effect of growth temperature and oxygen pressure on structural, electrical and optical properties.Applied Surface Science.2007,(254),1661-1665. * |
| 王雅静,姜月顺,戴国瑞,李枚枚.二氧化锡非晶超微粒薄膜制备与薄膜性能的研究.化学研究与应用.1999,11(1),37-40. * |
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