CN100595318C - Method for preparing transparent conductive film and electrode - Google Patents
Method for preparing transparent conductive film and electrode Download PDFInfo
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- CN100595318C CN100595318C CN200710065344A CN200710065344A CN100595318C CN 100595318 C CN100595318 C CN 100595318C CN 200710065344 A CN200710065344 A CN 200710065344A CN 200710065344 A CN200710065344 A CN 200710065344A CN 100595318 C CN100595318 C CN 100595318C
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Abstract
The invention discloses a target for manufacturing a transparent conductive film. The target is AZO ceramics, wherein the content of Al element ranges between 1 at percent and 10 at percent, and the balance is ZnO. The invention also discloses a method for manufacturing the transparent conductive film and a method for manufacturing a transparent conductive electrode. The invention manufactures a binary ceramic target through replacing In and Sn which are scarce and expensive by Al and Zn which are abundant, and deposits a film on a substrate by a method of magnetron sputtering or electron beamevaporating AZO target. The product is used as an FPD transparent conductive electrode after photolithography and etching. The method can reduce cost and obtain the transparent conductive film and the transparent conductive electrode which are low in resistivity, and good in visible light transmittance and in resistance of reduction of plasma.
Description
Technical field
The present invention relates to utilize transparent conductive film to prepare the method that used target is made transparent conductive film and transparency electrode, particularly relate to and utilize the transparent conductive film that contains Thin Film Transistor-LCD (TFT LCD) to prepare the method that used target is made transparent conductive film and electrode.
Background technology
Nesa coating (transparent conductive oxide is called for short TCO) is a class that is most widely used in all transparent conductive materials.Because the film of this material preparation not only has very high transmitance at visible region, infrared very high with the reflectivity near-infrared region, and the resistivity of film is also very low.Therefore both can show the plane electrode material that (FPD) and sun power are used, also be used as energy-conservation aspect,, can also be used for vehicle glass and microwave oven as the building glass surface etc. as the plane.What be most widely used at present in this class material is tin indium oxide (Indium Tin Oxide is called for short ITO).But the indium metal as one of its major ingredient is a rare metal, and the content in the earth's crust has only, and can only be to be present in Pb and the Zn ore deposit in symbiotic mode, and its smelting can cause the pollution of environment.In recent years because the development of flat-panel screens and solar cell, particularly the speedup of global TFT LCD panel production makes the rapid increase of consumption of indium since 2000, its price rapidly rises violently, and increases to the 1050-1070$/kg in this year from the 40-50$/kg of calendar year 2001.Because the indium ore deposit belongs to scarce resource, a large amount of consumption must cause exhaustion.Therefore be necessary to develop the substitute of ITO from the angle of the protection environment that economizes on resources.
Summary of the invention
Purpose of the present invention just provides cheap AZO ceramic target and replaces the ITO ceramic target, and utilizes this ceramic target to prepare transparent conductive film.Another object of the present invention just provides that preparation is a kind of to prepare the transparent and method conductive film electrode.
To achieve these goals, the invention provides a kind of transparent conductive film and prepare used target, wherein said target is the AZO pottery.
In the such scheme, the content of Al element is at 1at%-10at% in the described target, and other components are ZnO.
To achieve these goals, the present invention provides a kind of manufacture method of transparent conductive film simultaneously, comprising:
Magnetron sputtering AZO target, deposition obtains transparent conductive film on matrixes such as glass substrate or other media, and magnetron sputtering time control sputtering chamber O
2Volume content be 1-4%; The pressure 0.35-0.45Pa of Ar; And sputtering power is 40-120W; Vacuum tightness is 0.35-0.45Pa.
To achieve these goals, the present invention provides the manufacture method of another kind of transparent conductive film simultaneously, comprising: electron beam evaporation AZO target, deposition obtains the transparent film of leading on matrixes such as glass substrate or other media.
To achieve these goals, the present invention also provides a kind of manufacture method of transparency conductive electrode simultaneously, comprising: at first adopt magnetron sputtering AZO target, deposition obtains transparent conductive film on glass substrate or the first-class matrix of other media, wherein, control sputtering chamber O during described magnetron sputtering
2Volume content be 1-4%; Pass through the mask plate mask with that and be photo-etched into figure, form electrode shape through over etching again.
The present invention is with respect to prior art, its innovative point just is to replace with resourceful Al and Zn the In and the Sn of scarcity of resources high price, preparation binary ceramic target, method deposit film on glass substrate or other matrixes with magnetron sputtering, pass through photoetching and etching as the FPD transparency conductive electrode, as be used for substituting the ITO electrode.The alternate result not only has low resistivity and good visible light transmissivity, and the reductive action of plasma resistant.
The AZO film that requires as semiconducter device among the present invention is sedimentary by the method for magnetron sputtering, and this is that the good uniformity of deposit film also is the big characteristics of one on big area in addition because this method has guaranteed the low temperature and the high speed characteristics of deposition process.
The present invention takes to utilize the AZO target to substitute the ITO target, carries out thin film deposition with the method for magnetron sputtering on large-area glass substrate.This film has following characteristics: at visible region transmitance height; Resistivity is low; Anti-plasma reduction; Corrosion speed is fast, and it is clean to be easy to etching, does not stay residue; Use the slightly acidic etching liquid, little for equipment corrosion, prolong its life-span.
Below in conjunction with Figure of description and specific embodiment, technical scheme of the present invention is described in further detail.
Description of drawings
Fig. 1 is the X diffractogram that substrate temperature of the present invention prepares the AZO film when being 150 ℃;
Fig. 2 is the optical transmission spectra figure of the present invention's AZO film when mixing different oxygen;
Fig. 3 is the influence synoptic diagram of oxygen partial pressure of the present invention to AZO film average transmittances;
The transmitance synoptic diagram of film when Fig. 4 is different operating gaseous tension of the present invention (0.3-0.45Pa);
Fig. 5 is the influence synoptic diagram of the pressure of working gas of the present invention for the film transmitance;
The optical transmission spectra synoptic diagram of AZO film when Fig. 6 is the different sputtering power of the present invention;
Fig. 7 is the influence synoptic diagram of sputtering power of the present invention for AZO film transmitance;
Fig. 8 is the influence synoptic diagram of oxygen level of the present invention to film resiativity;
Fig. 9 is the influence synoptic diagram of operating pressure of the present invention to film resiativity.
Embodiment
The invention provides a kind of new target of making transparent conductive film, be specially and use the AZO target, the content of AL is 1at%-10at% in this target.
The pure zinc oxide film is a proper semiconductor, and the AZO film mixes shallow level impurity the 3rd main group element Al exactly in ZnO film, and the energy level of Al3+ is positioned at the semi-conductor forbidden band, and near at the bottom of the conduction band.Because the atomic radius of Al is close with the Zn atomic radius of lattice point, it will occupy the lattice lattice point, with the covalent linkage of element formation on every side.Because the valence electron of Al is Duoed one than Zn, the electronics that weak beam is tied up has appearred, this unnecessary electronics only needs energy (being the ionization energy of Al atom) seldom just can free one's minds becomes the unbound electron of doing the communization motion in ZnO film, just becomes the electronics in the conduction band.Because mixing the nonequilibrium carrier of aluminium ZnO film conduction mainly is electronics, so the zinc oxide aluminum film is a kind of N-type semiconductor, can explain its relevant nature with semi-conductive correlation theory.
Why transparent the AZO film is, be because its energy gap reaches 3.4eV, just intrinsic absorbs and is limited to 360nm, be in the ultraviolet region, for the visible light part, because the decline of uptake factor, make the energy of most of visible light can transmissive, have only the small portion energy to be absorbed and reflect, so film has the transparency.Conduction electrons in the AZO film is by Al3+ replacement and the oxygen vacancy of Zn2+ to be provided jointly, and this makes film have conductivity.ZnO low price in transparent conducting ZnO: Al (AZO) film, the source is abundant, and is nontoxic, and stability is better than ITO (tin indium oxide) in hydrogen plasma, and having simultaneously can be with the comparable photoelectric characteristic of ITO.
If material will possess electroconductibility, material internal must have current carrier that carries electric charge and the path that can supply the current carrier high-speed mobile.For the zinc oxide aluminum film, zinc atom and Sauerstoffatom in conjunction with the time, zinc atom tends to lose electronics becomes Zn2+, in a part of Zn2+, its s orbital can be done iso expansion, when Zn2+ is near each other, their s orbital is overlapping, just can form conducting path; Another factor that influences electroconductibility is the generation and the concentration thereof of current carrier, the thermal energy of room temperature is about 30meV, and the energy gap of zinc oxide aluminum is 3.4eV, therefore current carrier can thermal excitation in room temperature, current carrier in the zinc oxide aluminum film is mainly derived from replacement and the oxygen room of Al to Zn, as shown in the formula (representing the room) with V:
Zn2++Al→Zn+Al3++e
O2-→V+1/2O2↑+2e
Therefore, the doping of Al makes the zinc oxide aluminum film have electroconductibility.
In sum, the present invention takes to utilize the AZO target to substitute the ITO target, makes to such an extent that the AZO film has characteristics such as good transmitance and low-resistivity, satisfies the requirement of Thin Film Transistor-LCD.In addition, the AZO film also has anti-plasma reduction; Corrosion speed is fast, and it is clean to be easy to etching, does not stay residue; Use the slightly acidic etching liquid, little for equipment corrosion, prolong good characteristics such as its life-span.
Transparent conductive film making method provided by the invention is to adopt method deposit transparent conductive film on glass substrate or other media of magnetron sputtering AZO target.Be specially and using O
2Content 1-4% and the condition of the sputtering power 120W of the pressure 0.3-0.45Pa of working gas Ar and sputtering chamber under magnetron sputtering AZO target, deposition obtains transparent conductive film on glass substrate or other media.
Further be elaborated below in conjunction with specific embodiment.
Embodiment one
Thick on glass of 0.63mm, with the thick Al alloy firm of method deposition 600nm of magnetically controlled DC sputtering AZO ceramic target.The content that the Al element is closed in control in the ceramic target preparation process is at 1at%-10at%, and the pressure of the content of control O2 and working gas Ar and power etc.The film of preparation is measured its resistivity in room temperature with 4 methods.Then use its transmittance of spectrophotometer measurement again.Test-results such as Fig. 1-Fig. 9.
Fig. 1 is the X diffractogram that substrate temperature prepares the AZO film when being 150 ℃.As can be seen from Figure 1 its structure and ZnO's is consistent, though there is Al to mix, basic structure does not change.
Fig. 2 is the optical transmission spectra figure of AZO film when mixing different oxygen.For the content of O2 in the working gas scope, reach 80% substantially as can see from Figure 2 in the visible region transmitance from 0-4%.
Fig. 3 is the influence synoptic diagram of oxygen partial pressure to AZO film average transmittances.After can finding that from Fig. 3 O2 content surpasses 3% in the working gas, the film transmitance remains unchanged substantially.
The transmitance synoptic diagram of film when Fig. 4 is different operating gaseous tension of the present invention (0.3-0.45Pa); Fig. 5 is the influence synoptic diagram of the pressure of working gas of the present invention for the film transmitance.The pressure of working gas is little for the influence of film transmitance as can be seen from Figure 4 and Figure 5.
The optical transmission spectra synoptic diagram of AZO film when Fig. 6 is the different sputtering power of the present invention; Fig. 7 is the influence synoptic diagram of sputtering power for AZO film transmitance.Increase transmitance with sputtering power is successively decreased as can be seen from Fig. 6 and Fig. 7.
Fig. 8 is the influence synoptic diagram of oxygen level to film resiativity.As can be seen from Figure 8 the resistivity with the increase film of O2 content increases.
Fig. 9 is the influence synoptic diagram of operating pressure to film resiativity.As can be seen from Figure 9 the increase resistance with pressure takes the lead in reducing, and then increases, and resistivity reaches Schwellenwert in 0.35Pa.
From above-mentioned figure as can be seen, resistivity increases with the increase of power, increase resistivity with O2 content increases, reduce in the increase of the transmitance of visible region with power, pressure increase earlier with working gas Ar reduces again, increase with O2 content increases, and just reaches capacity but O2 content surpasses certain value.
Embodiment two
Employing electron beam evaporation AZO target, deposition obtains transparent conductive film on glass substrate or other media.
Embodiment three
If preparation FPD transparent conductive electrode at first adopts the heavy AZO film of method of magnetron sputtering on glass substrate,, become electrode through etching more with that through the mask plate mask and be photo-etched into figure.
It should be noted that at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can use differing materials and equipment to realize it as required, as, utilize above-mentioned target to make various transparent conductive films, obtain various electrically conducting transparent wires by mask and photoetching again.Promptly can make amendment or be equal to replacement, and not break away from the spirit and scope of technical solution of the present invention technical scheme of the present invention.
Claims (5)
1, a kind of manufacture method of transparent conductive film is characterized in that, comprising: magnetron sputtering AZO target, and deposition obtains transparent conductive film on matrix; Control sputtering chamber O during described magnetron sputtering
2Volume content be 1-4%.
2. manufacture method according to claim 1 is characterized in that, the pressure of control sputtering chamber working gas Ar is 0.35-0.45Pa during described magnetron sputtering.
3, manufacture method according to claim 1 is characterized in that, the sputtering power of control sputtering chamber is 40-120W during described magnetron sputtering.
4, manufacture method according to claim 1 is characterized in that, the vacuum tightness of control sputtering chamber is 0.35-0.45Pa during described magnetron sputtering.
5, a kind of manufacture method of transparency conductive electrode is characterized in that, comprising: at first adopt magnetron sputtering AZO target, deposition obtains transparent conductive film on matrix, wherein, and control sputtering chamber O during described magnetron sputtering
2Volume content be 1-4%; Pass through the mask plate mask with that and be photo-etched into figure, form electrode shape through over etching again.
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| CN200710065344A CN100595318C (en) | 2007-04-11 | 2007-04-11 | Method for preparing transparent conductive film and electrode |
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| CN200710065344A CN100595318C (en) | 2007-04-11 | 2007-04-11 | Method for preparing transparent conductive film and electrode |
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| CN100595318C true CN100595318C (en) | 2010-03-24 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101603171B (en) * | 2009-07-29 | 2011-09-14 | 新奥光伏能源有限公司 | Chamber system of equipment for preparing transparent conductive film and process thereof |
| CN102134702B (en) * | 2010-10-22 | 2013-07-10 | 迟伟光 | Method for preparing AZO powder and flat and rotary targets by spray drying process |
| TWI490353B (en) * | 2010-10-29 | 2015-07-01 | Hon Hai Prec Ind Co Ltd | Coated article and method for making the same |
| TWI491751B (en) * | 2010-10-29 | 2015-07-11 | 鴻海精密工業股份有限公司 | Coated article and method for making the same |
| CN102153352B (en) * | 2010-12-17 | 2015-05-20 | 西北稀有金属材料研究院 | Composite adhesive and application thereof in preparation of sintering target |
| CN102517554A (en) * | 2011-12-29 | 2012-06-27 | 广州有色金属研究院 | Method for deposition of AZO film at room temperature |
| CN102709156B (en) * | 2012-05-25 | 2016-09-07 | 中山大学 | A kind of ZnO-based transparent conductive film wet etching method |
| US10727374B2 (en) * | 2015-09-04 | 2020-07-28 | Seoul Semiconductor Co., Ltd. | Transparent conductive structure and formation thereof |
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Non-Patent Citations (2)
| Title |
|---|
| ZnO：Al透明导电薄膜的制备及其特性分析. 徐艺滨等.人工晶体学报，第35卷第3期. 2006 |
| ZnO：Al透明导电薄膜的制备及其特性分析. 徐艺滨等.人工晶体学报，第35卷第3期. 2006 * |
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Owner name: JINGDONGFANG SCIENCE AND TECHNOLOGY GROUP CO., LTD Free format text: FORMER OWNER: BEIJING BOE PHOTOELECTRICITY SCIENCE + TECHNOLOGY CO., LTD. Effective date: 20141128 Owner name: BEIJING BOE PHOTOELECTRICITY SCIENCE + TECHNOLOGY Effective date: 20141128 |
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Effective date of registration: 20141128 Address after: 100015 Jiuxianqiao Road, Beijing, No. 10, No. Patentee after: BOE Technology Group Co., Ltd. Patentee after: Beijing BOE Photoelectricity Science & Technology Co., Ltd. Address before: 100176 Beijing economic and Technological Development Zone, West Central Road, No. 8 Patentee before: Beijing BOE Photoelectricity Science & Technology Co., Ltd. |
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