CN1544685A - Preparation of low-resistance / high-resistance composite film through plasma technology - Google Patents
Preparation of low-resistance / high-resistance composite film through plasma technology Download PDFInfo
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- CN1544685A CN1544685A CNA2003101110231A CN200310111023A CN1544685A CN 1544685 A CN1544685 A CN 1544685A CN A2003101110231 A CNA2003101110231 A CN A2003101110231A CN 200310111023 A CN200310111023 A CN 200310111023A CN 1544685 A CN1544685 A CN 1544685A
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Abstract
The invention prepares transparent low-/high- resistance composite film by plasma technique, a novel photoelectron material. It uses low-temperature plasma technique to prepare the composite film. Mainly in view of preparing transparent electrodes of solar energy batteries, it need deposit transparent conductive and high-resistance film repeatedly. It bombards the transparent conductive film with oxygen plasma to primarily process the transparent conductively into the composite film, without redepositing a layer of transparent high-resistance film. It simplifies producing process, and reduces cost of finished products by a large margin. It can also be used in transparent electrodes of LCDs and plastic displays.
Description
Technical field under in the of one
The field is the sub-material of novel photoelectric under this invention.
Two background technologies
(Transparent Conducting Oxide TCO) is the important materials of devices such as preparation solar cell, liquid-crystal display to transparent conductive film.The resistivity of TCO film is lower than 10
-3Ω cm, visible light transmissivity is greater than 85%.Some metal such as Au, Ag, Pt, Cu, Rh, Pd, Al and Cr etc. when thickness during less than 15nm, to visible transparent, are through being used to transparent conductive film.But at the bottom of the metallic film hardness, poor stability has very strong metalluster again, is not the ideal transparent conductive film.At present, as transparent conductive film material, studying and making with the most use is metal oxide, and SnO is more typically arranged
2: F, ZnO:Al, CdO, In
2O
3, CdIn
2O
4, Cd
2SnO
4, Zn
2SnO
4And In
2O
3: Sn (ITO) etc.
In II-VI family polycrystalline compounds semiconductor film film battery, the CdS film is widely used in window layer of solar battery, and forms p-n junction as n type layer and p section bar material CdTe, constitutes solar cell.In the CdS/CdTe battery, expect higher short-circuit current density, CdS thickness must be done very thinly.But behind the CdS layer thickness attenuate, the homogeneity of film is affected, and micropore can appear in film, causes rare short, destroys the pn P-N junction characteristicPN.In order to solve this contradiction, need between transparent conductive film and CdS, introduce layer of transparent resistive formation film.Through practice, relatively more conventional way is to select the intrinsic material of nesa coating, as the transparency high mould material.As electrically conducting transparent SnO
2: the F film, the common anthology of its high resistance film is levied SnO
2As the transparency high mould material.Transparent conductive film ZnO:Al, its resistive formation material anthology is levied ZnO.In addition, Al
2O
3, SiO
2And TiO
2Deng also can be used as the transparency high film.
The method for preparing transparent low-resistance film, transparency high film is a lot, and radio frequency, magnetically controlled DC sputtering are arranged, and normal pressure, low-pressure chemical vapor deposition and physics strengthen chemical vapour deposition etc.
Three summary of the invention
Purpose of the present invention is to seek a kind of new method and new technology, production big area, transparent low resistance/high resistance laminated film cheaply.
The technology used in the present invention means are non-thermal plasma traps.
Metal conductive oxide is two kinds of results that mechanism works, first oxygen room, and it two is effects of dopant ion.At the metal oxide of hot conditions deposit, the oxonium ion of its crystallographic site often has omission, make the Sn ionic not sharing electron be easy to be subjected to external influence, break away from the constraint of Sn ionic, become current carrier.On the other hand, because the F ionic mixes, the oxonium ion of replacement lattice position also can be contributed n type current carrier.If can compensate to intravital oxygen vacancy, simultaneously the F ion is extruded, low-resistance region will be become high resistance area in the part.The present invention utilizes the characteristics that the low-temperature plasma ion density is big, energy is low, with oxygen plasma transparent conductive film is carried out shallow top layer and injects, and forms high resistance area in the 20nm scope, reaches at electrically conducting transparent SnO
2: on the F film system basis, the purpose of disposable formation low-resistance, high resistant composite membrane.
The concrete practice: conductive film is placed in the low-temperature plasma of glow discharge formation, drawing oxygen plasma with bias voltage bombards conductive film, the oxonium ion of certain energy carries out shallow top layer to transparent conductive film and injects, and the oxonium ion that enters will compensate the top layer oxygen vacancy of transparent conductive film.Simultaneously, because a large amount of, speed is the oxonium ion bombardment of per second hundreds of rice, and surface temperature raises rapidly.F ion in the top layer is heated and can makes the top layer form the transparency high district to external diffusion.Like this, just can be disposable with non-thermal plasma trap on the transparent conductive film surface, form the transparent low resistance/high resistance matrix material.Simultaneously, oxygen plasma can make surface temperature raise to the bombardment on conducting film surface, promotes the atomic surface diffusion, improves the planeness of film surface, makes film-forming properties better, and the visible light transmissivity of film and the thickness of film are constant.
Preparing the remarkable advantage of transparent low resistance/high resistance composite membrane with plasma technology, is to need not on transparent low resistance film, deposits new compound, thereby has reduced production link, shortens the production cycle, and technology is simple to operation, can reduce production costs significantly.
Four description of drawings
Fig. 1 is the radio frequency glow discharge structure iron
Wherein, T1 is the radio-frequency sputtering vacuum system, and A, B are upper/lower electrode, and S is a sample, and N is a vacuum pump system, and C is a stopping condenser, and f1 is 13.6MHz, and f2 is the bias voltage operating frequency.
Fig. 2 is the radio frequency glow discharge structure iron
Wherein, T2 is the DC glow sputtering system, and A is a positive electrode, and B is a negative potential, and S is a sample, and N is a vacuum pump system, and E1 is a direct supply.
Five embodiments
Be described with reference to the accompanying drawings embodiments of the present invention.
Embodiment 1: prepare transparent low resistance/high resistance composite membrane with direct current glow discharge
As Fig. 2.Use SnO
2: the F transparent conductive film is made sample, and square resistance 14 Ω cm are put on the negative potential base vacuum 10
-3Pa, working vacuum are 1-100Pa, and working gas is Ar, O
2, volts DS 800-1500 volt, biasing 0-200 volt, bombardment time 10-60 minute.Bombardment back composite membrane resistance is increased to 17-30 Ω cm.Under 1500 volts of voltages quickened, the energy of oxonium ion was still very low, and oxonium ion can only enter the shallow top layer of conducting film, and the degree of depth is no more than 10nm, to the not influence of conductive layer of inside.Simultaneously, speed is the high-density oxonium ion bombarded surface of per second hundreds of rice, and surface temperature is raise rapidly, impels atom along surface diffusion, makes film-forming properties better, has improved the surface topography of film.
In like manner, can be with this method with ZnO:Al, CdO, In
2O
3, CdIn
2O
4, Cd
2SnO
4, Zn
2SnO
4And In
2O
3: Sn transparent conductive films such as (ITO) is prepared into transparent low resistance/high resistance composite membrane.
As Fig. 1.Use SnO
2: the F transparent conductive film is made sample (S), and square resistance 14 Ω cm are put on the negative potential (B) base vacuum 10
-3Pa, working vacuum are 1-100Pa, and working gas is Ar, O
2, radio frequency operation frequency (f1) is 13.6MHz, radio frequency power 20-200W, bias frequency (f2) 0.5-2.0MHz, bias voltage 0-200 volt, bombardment time 10-60 minute.Bombardment back composite membrane resistance is increased to 15-25 Ω cm.Under 200 volts of bias voltages quickened, the energy of oxonium ion was still very low, and oxonium ion can only enter the shallow top layer of conducting film, and the degree of depth is no more than 10nm, to the not influence of conductive layer of inside.Simultaneously, speed is the high-density oxonium ion bombarded surface of per second hundreds of rice, and surface temperature is raise rapidly, impels atom along surface diffusion, makes film-forming properties better, has improved the surface topography of film.
In like manner, can be with this method with ZnO:Al, CdO, In
2O
3, CdIn
2O
4, Cd
2SnO
4, Zn
2SnO
4And In
2O
3: Sn transparent conductive films such as (ITO) is prepared into transparent low resistance/high resistance composite membrane.
Claims (3)
1. method of using non-thermal plasma trap to prepare transparent low resistance/high resistance composite membrane.It is characterized in that, on the basis of transparent low resistance film, bombard, the oxygen vacancy in the transparent low resistance film is compensated, thereby form low resistance/high resistance composite membrane with oxygen plasma.
2. oxygen plasma as claimed in claim 1 can be produced by direct current glow discharge, also can be produced by radio frequency glow discharge.Transparent low resistance film is carried out the bombardment process, the bombardment of can heating, the bombardment of also can not heating, heating is no more than 200 degree.
3. transparent low resistance film as claimed in claim 2 can be ZnO:Al, CdO, In
2O
3, CdIn
2O
4, Cd
2SnO
4, Zn
2SnO
4And In
2O
3: Sn (ITO) etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2003101110231A CN1544685A (en) | 2003-11-27 | 2003-11-27 | Preparation of low-resistance / high-resistance composite film through plasma technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2003101110231A CN1544685A (en) | 2003-11-27 | 2003-11-27 | Preparation of low-resistance / high-resistance composite film through plasma technology |
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| Publication Number | Publication Date |
|---|---|
| CN1544685A true CN1544685A (en) | 2004-11-10 |
Family
ID=34335872
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|---|---|---|---|
| CNA2003101110231A Pending CN1544685A (en) | 2003-11-27 | 2003-11-27 | Preparation of low-resistance / high-resistance composite film through plasma technology |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101609858B (en) * | 2008-06-20 | 2011-06-22 | 福建钧石能源有限公司 | Film deposition method |
| CN102254997A (en) * | 2011-07-14 | 2011-11-23 | 复旦大学 | Method for preparing p-type ZnO film by using plasma immersion ion implantation technology |
| CN103824918A (en) * | 2011-12-31 | 2014-05-28 | 聚灿光电科技(苏州)有限公司 | Uniform current distribution LED |
| CN105063557A (en) * | 2015-08-06 | 2015-11-18 | 国营第二二八厂 | Method for directional resistance value increase of ITO conducting film |
| CN107749318A (en) * | 2016-08-31 | 2018-03-02 | 陈初群 | A kind of preparation method of transparent conductive electrode |
| CN111564536B (en) * | 2020-05-12 | 2021-11-05 | 创维液晶器件(深圳)有限公司 | Preparation method and structure of Micro-LED chip and display terminal |
-
2003
- 2003-11-27 CN CNA2003101110231A patent/CN1544685A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101609858B (en) * | 2008-06-20 | 2011-06-22 | 福建钧石能源有限公司 | Film deposition method |
| CN102254997A (en) * | 2011-07-14 | 2011-11-23 | 复旦大学 | Method for preparing p-type ZnO film by using plasma immersion ion implantation technology |
| CN103824918A (en) * | 2011-12-31 | 2014-05-28 | 聚灿光电科技(苏州)有限公司 | Uniform current distribution LED |
| CN105063557A (en) * | 2015-08-06 | 2015-11-18 | 国营第二二八厂 | Method for directional resistance value increase of ITO conducting film |
| CN105063557B (en) * | 2015-08-06 | 2018-02-09 | 国营第二二八厂 | A kind of method for orienting increase ITO conducting film resistances |
| CN107749318A (en) * | 2016-08-31 | 2018-03-02 | 陈初群 | A kind of preparation method of transparent conductive electrode |
| CN107749318B (en) * | 2016-08-31 | 2020-09-25 | 苏州绘格光电科技有限公司 | Preparation method of transparent conductive electrode |
| CN111564536B (en) * | 2020-05-12 | 2021-11-05 | 创维液晶器件(深圳)有限公司 | Preparation method and structure of Micro-LED chip and display terminal |
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