CN101159178A - Transparency conductive film and preparation method thereof - Google Patents
Transparency conductive film and preparation method thereof Download PDFInfo
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- CN101159178A CN101159178A CNA2007100563035A CN200710056303A CN101159178A CN 101159178 A CN101159178 A CN 101159178A CN A2007100563035 A CNA2007100563035 A CN A2007100563035A CN 200710056303 A CN200710056303 A CN 200710056303A CN 101159178 A CN101159178 A CN 101159178A
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Abstract
The invention relates to a transparent conductive thin film widely applied in the technical fields such as a LCD screen, an electroluminescent display, a solar cell, a TFT, an organic and inorganic semiconductor laser, and thermal-insulating energy-saving glass, as well as a preparation method thereof. The thin film (IVO) is an indium vanadium oxide (In2O3:V) formed by doping V element in a main material In2O3, and the content of V in the IVO material accounts for 0.1 percent-30 percent of the content of In. The thin film can be prepared by a plurality of film plating techniques such as high vacuum thermal evaporation, electron beam deposition and sputtering. The thin film is firm, and has good conductivity, visible light transparency and chemical stability.
Description
Technical field
The present invention relates to a kind of transparent conductive film that is widely used in LCDs, electroluminescent display, solar cell, thin-film transistor, organic and technical fields such as inorganic semiconductor laser, heat-insulating and energy-saving glass and preparation method thereof.
Background technology
Transparent conductive film is meant form a kind of to the visible transparent and the film that can conduct electricity on substrate.As good photoelectricity information material, transparent conductive film has very high light transmission and very low resistivity in visible-range.These excellent characteristic make it have a wide range of applications in LCDs, electroluminescent display, solar cell, thin-film transistor, organic and technical fields such as inorganic semiconductor laser, heat-insulating and energy-saving glass.For transparent conductive film, that extensively adopt in the world at present is the indium oxide (In that mixes tin (Sn)
2O
3) film (be called for short ITO), and manufacture craft and making apparatus have obtained significant progress.
In recent years, transparent conductive film has still all been made significant headway from the employing of raw material from type.By retrieval, find with In to document
2O
3, SnO
2, ZnO etc. is for the binary of material of main part, ternary or polynary various transparent conductive films emerge in an endless stream, and greatly promoted the development of transparent conductive film.Reference is as follows:
J.M.Mochel，U.S.Patent?No.2,564,706(1947).
H.A.McMaster，U.S.Patent?No.2,429,420(1947).
J.M.Mochel，U.S.Patent?No.2,564,707(1951).
H.F.Dates?and?J.K.Davis，U.S.Patent，No.3,331,702(1967).
A.J.Nozik，U.S.Patent?No.3,811,953(1974).
S.Major，A.Banerjee，and?K.L.Chopra，Thin?Solid?Films?122(1984)p.31.
T.Minami，H.Nanto，and?S.Takata，Jpn.J.Appl.Phys.，Part?2：Lett.23(1984)p.L280.
T.Minami，H.Sato，H.Nanto，and?S.Takata，Jpn.J.Appl.Phys.，Part?2：?Lett.24(1985)p.L781.
H.Enoki，T.Nakayama，and?J.Echigoya，Phys.Status?Solidi?A?129(1992)p.181.
Transparent conductive film such as ITO are mainly used to do transparency electrode in thin-film device.In recent years, the development of various photoelectric devices has proposed new requirement to existing transparent conductive film.For example organic electroluminescence device (OLED) belongs to charge carrier injection type device, owing to there is bigger charge carrier injection barrier between ito anode commonly used and the organic layer, causes the low of device charge carrier injection efficiency and has influenced the whole luminescent properties of device.The metal ion of ITO electrode surface can be to the organic layer internal migration at the OLED duration of work in addition, causes the inefficacy of device part and aging.In the solar cell of organic solar batteries and other types, exist similar phenomenon.So although transparent conductive film has been obtained significant progress, people still seek new material, technology in unremitting effort and prepare new transparent conductive film to satisfy the needs of various industrial production and development in science and technology.
Summary of the invention
The purpose of this invention is to provide that a kind of chemical stability is good, electric conductivity is good and visible light transmissivity is high, be specially adapted to the novel transparent conductive film of various organic optoelectronic devices, to overcome the above-mentioned defective that present ITO transparent conductive film exists, the photoelectric properties of device and stability etc. are significantly improved.
Transparent conductive film of the present invention is at material of main part indium oxide (In
2O
3) in be doped with vanadium metal (V) indium barium oxide (In that element constituted
2O
3: V), abbreviate IVO as, the mass ratio of V and In is 0.1%～30% in this IVO material.
Present ito thin film belongs to the oxide conducting material that the N type mixes, and the In in the material of main part is a triad, In
3+Ionic radius be 0.81 , and dopant material Sn is a quadrivalent element, Sn
4+Ionic radius be 0.71 .The Sn atom of each doping can provide a conduction electrons after replacing the In atom.And the dopant material V that the present invention adopts is a pentad.V
4+Ionic radius be 0.63 , V
5+Ionic radius be 0.59 , so the ratio of ionic radii In ion of V is little a lot, belongs to easy doping elements, and after the V atom of each doping replaces the In atom, can provide one to two conduction electrons according to the difference of price.Therefore the IVO film among the present invention belongs to the oxide electroconductive film that the N type mixes.Compare with ITO, under identical doping content, have higher carrier concentration and lower pellicular front resistance.
Electrically conducting transparent IVO film of the present invention can be deposited on various rigidity and flexible and the transparent and nontransparent substrate, for example glass, sapphire, quartz, aluminium foil, silicon chip, plastics and polymethyl methacrylate etc.Preparation technology has technology such as high vacuum thermal evaporation, electron beam deposition, magnetron sputtering, ion sputtering, pulsed laser deposition.The basic fundamental of IVO film in preparation process requires: preparation initial vacuum degree is higher than 5 * 10
-3Pa.Working gas during preparation is an oxygen, and the working vacuum degree is 8 * 10
-3～2 * 10
-1Pa; The heating-up temperature of substrate is 70～350 ℃ during preparation.
The present invention has the following advantages:
1) compare with other traditional transparent conductive films, the prepared IVO film of the present invention has higher visible light transmissivity, excellent conducting performance and excellent chemical stability and film forming fastness.It is many that the content of doped chemical Sn in the earth's crust that the doped chemical V that is adopted is adopted than common commercial ITO enriches, and saved nonrenewable resources effectively;
2) compare with traditional commercial ITO, have good interface between the prepared IVO transparent conductive film of the present invention and the organic layer and contact, make the charge carrier injection efficiency of common organic electro-optic device such as OLED be able to effective raising, luminescent properties significantly improves.
Description of drawings
Fig. 1 is the transmitted spectrum of the IVO film of preparation in the embodiment of the invention 1.
Fig. 2 is the ESEM surface topography of the IVO film of preparation in the embodiment of the invention 2.
Fig. 3 is for being the brightness-current density relation curve of the OLED device of anode development with IVO film of the present invention, and the OLED device that provides common ito anode among the figure simultaneously as a comparison.
Embodiment
The present invention will be further described below in conjunction with example.
Embodiment 1
Adopt DM 450 vacuum coating equipments of Beijing instrument plant, utilize thermal evaporation method to prepare the IVO transparent conductive film, concrete steps are as follows:
A. put into vacuum chamber after will drying up with dry nitrogen with the glass substrate of deionized water and acetone ultrasonic cleaning, and vacuum chamber is evacuated to indoor pressure is lower than 5.0 * 10
-3Pa heats to glass substrate then, and temperature is 70～350 ℃;
B. charge into oxygen to vacuum chamber, the oxygen purity that charges in the vacuum chamber is 99.999%, charges into after the oxygen, and pressure is 8 * 10 in the control vacuum chamber
-3～2 * 10
-1Within the Pa scope, adopt vacuum gauge and mass flowmenter the oxygen that charges into vacuum chamber to be carried out the real-time monitoring of vacuum degree;
C. for avoiding the influence of substrate surface composition to the IVO film forming characteristics, one deck SiO grows on substrate earlier
2, thickness is 1～15nm;
D. at SiO
2The mode that last employing double source steams altogether is thermal evaporation metal In and V simultaneously
2O
5Material, wherein the evaporation rate of metal In is 0.2～3nm/s, V
2O
5Evaporation rate is 0.01～1nm/s, and making the film thickness scope is 30nm～500nm, and the thickness of film growth and speed adopt the quartz crystal oscillator film thickness gauge to monitor in real time, and after film preparation was finished, annealing conditions was 60～250 ℃, and the time is 10～300 minutes.
After film preparation is finished, can adopt annealing process elimination membrane stress and improve its transparency.Annealing temperature is 60～250 ℃, and the time is 10～300 minutes.
The transmitted spectrum of IVO film adopts the UNICO spectrophotometer measurement; The elemental composition of film adopts GENE SIS2000 XMS60S (EDAXINC) x-ray photoelectron spectroscopy to measure.
Fig. 1 is the transmitted spectrum of the IVO film (sample B) of preparation among the embodiment 1.Show that this IVO film reaches 90% at the high permeability of visible range, average infrared transmittivity surpasses 80%.The essential element composition of IVO film is O, In, V, and wherein the mass ratio of V and In is 0.1～30%.Following table 1 has provided the performance parameter of IVO film.
The performance parameter of table 1 IVO film
| Sample number into spectrum | The mass ratio of V and In in the IVO film | The visible light maximum transmission | Resistivity (Ω cm) | Carrier concentration (cm -3) | Carrier mobility (cm 2V -1S -1) |
| ?A | ?0.1％ | 87％ | 1.61×10 -3 | 8.16×10 19 | 29.3 |
| ?B | ?1.8％ | 90％ | 7.95×10 -4 | 2.27×10 20 | 34.5 |
| ?C | ?12％ | 88％ | 5.04×10 -4 | 2.95×10 20 | 40.4 |
| ?D | ?30％ | 84％ | 1.10×10 -3 | 1.20×10 20 | 31.1 |
Embodiment 2
Adopt the box high vacuum coating unit of ZZS700 of Chengdu vacuum machine factory, utilize the electron beam deposition technology to prepare the IVO transparent conductive film, the basic fundamental of vacuum and substrate is required with embodiment 1.One deck Al grows on glass substrate earlier
2O
3, thick 1～15nm.On glass substrate, adopt the method for electron beam evaporation to prepare IVO then.The evaporation raw material are InV alloy (wherein the mass ratio of metal V and In is 1: 3～1: 20), adopt the MDC-360 of MAXTEK company that growth for Thin Film speed and thickness are monitored in real time, and evaporation rate is 0.05～2nm/s.Can realize that by regulating electron beam line and working vacuum degree the mass ratio of V and In is 0.1～30% after the film forming.The film thickness scope is 20nm～500nm.After film preparation was finished, annealing conditions was 60～250 ℃, and the time is 10～300 minutes.Fig. 2 is the ESEM surface topography of the IVO film (thick 100nm) of preparation among the embodiment 2, is measured by HITACHI S-4800 scanning transmission electron microscope.The result shows that this film is made up of the polycrystalline of even compact.The square face resistance of film is～15 Ω/, and the high permeability of visible light reaches 91.5%.
Embodiment 3
Employing purity is 99.99% In
2O
3Powder and purity are 99.99% V
2O
5Powder evenly mixes (In mutually
2O
3With V
2O
5Mass ratio is 98: 2～80: 20), sinter target into.Adopt the deposition techniques IVO film of this target with magnetron sputtering.Wherein underlayer temperature is 200 ℃.Sputtering power is 0～500 watt of a radio frequency target.Sputter rate is 0.04～1nm/s.Can realize that by regulating sputtering power and working vacuum degree the mass ratio of V and In is 0.1～30% after the film forming.The face resistance of this IVO film reaches～15 Ω/, and average visible light transmissivity is higher than 85%.
Embodiment 4
Respectively with the IVO film of vacuum thermal evaporation preparation (25 Ω/) and commercial ito thin film (25 Ω/) be anode, and the method for employing vacuum thermal evaporation has been made the following organic electroluminescence device (OLEDs) of structure:
Glass/IVO/NPB(70nm)/Alq
3(60nm)/LiF(0.5nm)/Al(150nm)；
Glass/ITO/NPB(70nm)/Alq
3(60nm)/LiF(0.5nm)/Al(150nm。
Fig. 3 has provided the brightness-current density relation curve of two kinds of OLED devices.By finding that relatively the IVO anode has higher charge carrier injectability than common ito anode, thereby has improved the luminescent properties of OLED significantly.The OLED device maximum brightness that with IVO is anode has reached 75040cd/m
2, maximum luminous efficiency reaches 6.68cd/A, is respectively to be 3.2 times and 2.1 times of OLED device of anode with ITO.And compare with ITO, be that the OLED device working life of anode significantly improves with IVO, show that IVO has higher chemical stability.
Claims (3)
1. a transparent conductive film is characterized in that, is at material of main part In
2O
3In be doped with the indium barium oxide (In that V element constitutes
2O
3: V), abbreviate IVO as, the mass ratio of V and In is 0.1%～30% in this IVO material.
2. a method for preparing the described transparent conductive film of claim 1 is characterized in that it being to adopt the vacuum thermal evaporation method to obtain described transparent conductive film in vacuum coating equipment, and concrete steps are as follows:
A. put into vacuum chamber after will drying up with dry nitrogen with the glass substrate of deionized water and acetone ultrasonic cleaning, and vacuum chamber is evacuated to indoor pressure is lower than 5.0 * 10
-3Pa heats to glass substrate then, and temperature is 70～350 ℃;
B. charge into oxygen to vacuum chamber, the oxygen purity that charges in the vacuum chamber is 99.999%, charges into after the oxygen, and pressure is 8 * 10 in the control vacuum chamber
-3～2 * 10
-1Within the Pa scope;
C. for avoiding the influence of substrate surface composition to the IVO film forming characteristics, one deck SiO grows on substrate earlier
2, thickness is 1～15nm;
D. at SiO
2The mode that last employing double source steams altogether is thermal evaporation metal In and V simultaneously
2O
5Material, wherein the evaporation rate of metal In is 0.2～3nm/s, V
2O
5Evaporation rate is 0.01～1nm/s, and making the film thickness scope is 30nm～500nm.
3. a method for preparing the described transparent conductive film of claim 1 is characterized in that it being to adopt means of electron beam deposition to obtain described transparent conductive film in vacuum coating equipment, and concrete steps are as follows:
A. put into vacuum chamber after will drying up with dry nitrogen with the glass substrate of deionized water and acetone ultrasonic cleaning, and vacuum chamber is evacuated to indoor pressure is lower than 5.0 * 10
-3Pa heats to glass substrate then, and temperature is 70～350 ℃;
B. charge into oxygen to vacuum chamber, the oxygen purity that charges in the vacuum chamber is 99.999%, charges into after the oxygen, and pressure is 8 * 10 in the control vacuum chamber
-3～2 * 10
-1Within the Pa scope;
C. for avoiding the influence of substrate surface composition to the IVO film forming characteristics, one deck Al grows on substrate earlier
2O
3, thickness is 1～15nm;
D. at Al
2O
3Last employing electron beam evaporation method evaporation InV alloy material, evaporation rate is 0.05～2nm/s, making the film thickness scope is 20nm～500nm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102290443A (en) * | 2011-07-28 | 2011-12-21 | 北京大学深圳研究生院 | Amorphous thin film transistor and preparation method thereof |
| CN107117507A (en) * | 2017-05-16 | 2017-09-01 | 南通中尧特雷卡电梯产品有限公司 | A kind of touch-screen and the elevator console using the touch-screen |
| CN107128761A (en) * | 2017-05-16 | 2017-09-05 | 南通中尧特雷卡电梯产品有限公司 | A kind of touch type elevator operation panel and elevator operation system |
| CN107128760A (en) * | 2017-05-16 | 2017-09-05 | 南通中尧特雷卡电梯产品有限公司 | A kind of elevator console and the apparatus for controlling elevator including the operation panel |
| CN114242338A (en) * | 2021-12-16 | 2022-03-25 | 长春博信光电子有限公司 | Method for improving resistance value of ITO film |
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| CN1195097C (en) * | 2002-07-13 | 2005-03-30 | 华中科技大学 | Process for prapring vanadium oxide film |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102290443A (en) * | 2011-07-28 | 2011-12-21 | 北京大学深圳研究生院 | Amorphous thin film transistor and preparation method thereof |
| CN102290443B (en) * | 2011-07-28 | 2016-03-30 | 京东方科技集团股份有限公司 | A kind of amorphous thin film transistor and preparation method thereof |
| CN107117507A (en) * | 2017-05-16 | 2017-09-01 | 南通中尧特雷卡电梯产品有限公司 | A kind of touch-screen and the elevator console using the touch-screen |
| CN107128761A (en) * | 2017-05-16 | 2017-09-05 | 南通中尧特雷卡电梯产品有限公司 | A kind of touch type elevator operation panel and elevator operation system |
| CN107128760A (en) * | 2017-05-16 | 2017-09-05 | 南通中尧特雷卡电梯产品有限公司 | A kind of elevator console and the apparatus for controlling elevator including the operation panel |
| CN114242338A (en) * | 2021-12-16 | 2022-03-25 | 长春博信光电子有限公司 | Method for improving resistance value of ITO film |
| CN114242338B (en) * | 2021-12-16 | 2024-02-06 | 长春博信光电子有限公司 | Method for improving resistance value of ITO film |
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Assignee: Shenzhen Xilu Photoelectricity Technology Co. Ltd. Assignor: Changchun Inst. of Optics and Fine Mechanics and Physics, Chinese Academy of Sci Contract record no.: 2010440020155 Denomination of invention: Novel organic-inorganic hybrid transparent conductive film and preparation method thereof Granted publication date: 20091202 License type: Exclusive License Open date: 20080409 Record date: 20100902 |
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