CN102187476B - Transparent conductive zinc oxide display film and production method therefor - Google Patents
Transparent conductive zinc oxide display film and production method therefor Download PDFInfo
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- CN102187476B CN102187476B CN200980142398XA CN200980142398A CN102187476B CN 102187476 B CN102187476 B CN 102187476B CN 200980142398X A CN200980142398X A CN 200980142398XA CN 200980142398 A CN200980142398 A CN 200980142398A CN 102187476 B CN102187476 B CN 102187476B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 239000011248 coating agent Substances 0.000 claims abstract description 36
- 239000012298 atmosphere Substances 0.000 claims abstract description 21
- 238000000151 deposition Methods 0.000 claims abstract description 15
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004411 aluminium Substances 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 239000000460 chlorine Substances 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 229910052738 indium Inorganic materials 0.000 claims abstract description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000005516 engineering process Methods 0.000 claims description 21
- 230000008021 deposition Effects 0.000 claims description 11
- 239000002019 doping agent Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 73
- 150000002431 hydrogen Chemical class 0.000 description 7
- 235000014692 zinc oxide Nutrition 0.000 description 7
- 238000010891 electric arc Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000001552 radio frequency sputter deposition Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 241001076960 Argon Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000013876 argon Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 hydrogen compound Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3485—Sputtering using pulsed power to the target
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The present invention concerns a method for the generation of a transparent conductive oxide display coating (TCO display layer), in particular a transparent conductive oxide display coating as a transparent contact for flat panel displays and the like. The TCO display layer is generated by depositing zinc oxide and additionally aluminium, indium, gallium, boron, nitrogen, phosphorous, chlorine, fluorine or antimony or a combination thereof, with the process atmosphere containing hydrogen. These TCO layers can be realized in a particularly simple and cost-effective way compared to ITO. The properties of the inventive TCO layers are nearly as good as those for ITO, regarding high transmittance and low resistance.
Description
Technical field
The present invention is about the purposes of the transparent conductive oxide display coating of the transparent conductive oxide display coating of a kind of method of the transparent conductive oxide display coating for generation of generic term as claimed in claim 1, a kind of generic term as claimed in claim 9 and a kind of generic term as claimed in claim 11.
Background technology
Transparent conductive contact especially is that photovoltaic applications (such as solar cell and solar energy module) is required.For this reason, mainly use transparent conductive oxide coating (tco layer), mainly use tin indium oxide (ITO) up to now.In addition, especially for flat-panel monitor, ITO is based on the monitor market and reaches many years.Yet meanwhile, zinc oxide (ZnO) is just being enjoyed the degree huge in fashion of industrial use, and especially because the price of target is lower for ZnO, deposition rate ITO is more economical for this.
Unfortunately, compare with ITO, ZnO has high electrical resistance and has paid the resistance that very big effort reduces ZnO.In this regard, the zinc oxide tco layer of known especially two-part structure presents optics and the electrical characteristics that can compare with the ITO layer.By US 5,078, the structure of the 2nd ZnO layer of 804 known ZnO layers with high resistance (low conductivity) and low resistance (high conductivity), wherein a ZnO layer is disposed on the resilient coating of the absorbent scope that covers Copper Indium Gallium Selenide (CIGS).Two ZnO layers all get via the RF magnetron sputtering deposition under oxygen-argon atmosphere or straight argon atmosphere.In addition, US 2005/0109392A1 discloses the CIGS solar battery structure, wherein resilient coating is similarly and presents high-resistance so-called intrinsic, that is pure ZnO layer (i-ZnO) covers, and applies with aluminium at this pure ZnO layer subsequently and mix and present low-resistance ZnO layer.Deposit the i-ZnO layer and deposit the ZnO layer of high conductivity via the magnetron sputtering of the ZnO target of adulterated al via the RF magnetron sputtering.The ZnO target of this adulterated al also can be through direct current (DC) sputter, and this measure increases the spreading rate with respect to the RF sputtering target material in fact.DC sputters at and is used for these conducting ZnOs of deposition in the industrial use: the Al layer.Inferior position in this tco layer is that described tco layer must give the structurized fact.The resistance of 500 μ Ω cm to 1000 μ Ω cm can reach 350 ℃ and more temperature high deposition.In addition, the conductivity of the ZnO through mixing is limited can be subjected to the dopant adverse influence for the transmissivity of lower temperature and ZnO.
Summary of the invention
Therefore, target of the present invention is for producing a spendable program, via this program, can make and has high conductivity and the high grade of transparency and need not special constructionization and especially can reach the TCO display layer of the ZnO of the temperature that is lower than 350 ℃.Specifically, the resistance of coating and transparency should be compared with resistance and the transparency of ITO, and transmissivity should preferably surpass the transmissivity of ITO.
This target is reached by the method for claim 1, TCO display layer as claimed in claim 9 and TCO display layer use as claimed in claim 11.The advantageous embodiment of these targets is the target of dependent claims.
The inventive method is characterised in that: having under the technology atmosphere situation that comprises hydrogen, produce transparent conductive oxide display coating via the combination of depositing zinc oxide and extra aluminium, indium, gallium, boron, nitrogen, phosphorus, chlorine, fluorine or antimony or above-mentioned substance.Gallium is the optimum doping agent.In this way, the ZnO layer (ZnO:X layer) that mixes with the combination of aluminium, indium, gallium, boron, nitrogen, phosphorus, chlorine, fluorine or antimony or above-mentioned substance will be made.
This case inventor shockingly finds because the hydrogen content in the technology atmosphere can make the ZnO:X layer of low resistance and high-transmission rate, and these character of these character and ITO is good on an equal basis, and the character of described ZnO:X layer can be better for transmissivity.Because the price of ZnO target is more much lower than the price of ITO target, thus the processing cost of tco layer reduce in a large number, but tco layer character and the layer quality almost remain unchanged.
The TCO display layer of these inventions directly can be deposited on the substrate (such as glass, resin etc.), or be deposited on other layer (such as the functional layer of solar cell or display).
One especially in the preferred embodiment, the hydrogen content in the technology atmosphere is in the scope of 1 volume % to 50 volume %, especially in the scope of 4 volume % to 16 volume %, and preferable in the scope of 6 volume % to 12 volume %.May work with element hydrogen or with argon-hydrogen mixture one.This measure allows to use very cleaning, because under the situation of the atmosphere that contains (for example) methane, will deposit unwanted carbon.
Advantageously, substrate temperature is 350 ℃ at the most between depositional stage, especially, and in 100 ℃ to 250 ℃ scope and be preferably 230 ℃.In these temperature ranges, for example, can make the display that comprises the resin colored filter, described resin colored filter has 250 ℃ critical temperature and exceeds this temperature with impaired.Advantageously, the hydrogen content in the technology atmosphere produce at low temperatures with under at least 350 ℃ temperature for the same low resistance of ZnO of doped gallium.Can use different state of temperatures: via cold deposition or the warm deposition of continuous tempering, wherein preheating may be prior to warm deposition.For the inventive method, warm be deposited as preferable and especially between depositional stage, use temperature ramp.
Available deposition process is chemical vapour deposition (CVD), physical vapour deposition (PVD) (such as sputter etc.), because high output, good layer quality and the low equipment cost made, the DC sputter is best.If via produce TCO display layer through the means of pulse DC sputter because may obtain higher power density, then technology stability can obtain improvement and therefore deposition rate can advantageously further increase.Also can obtain the increase of technology stability via RF sputtering (MF sputter) among at least two kinds of targets of use.Therefore, in content of the present invention, via the DC sputter mean the DC sputter, through the DC of pulse sputter and MF sputter.
The power density of DC sputter is preferable at 2W/cm
2To 20W/cm
2Scope in, especially at 4W/cm
2To 15W/cm
2Scope in, and preferable at 6W/cm
2To 11W/cm
2Scope in.For these power densities, resistance and deposition rate obtain improvement.
In order further to improve and to adjust resistance and transmissivity, this technology atmosphere can further contain aerobic.
Contain the admixture of gas hydrogen source of (containing hydrogen or hydrogen compound) if use, then can be via using the amount of controlling hydrogen than large mass controller (MFC) more accurately.Contain the chemical compound hydrogen source of (containing hydrogen) if use, the then processing of hydrogen, it is safer especially to link to each other with oxygen.
The layer of making ZnO doping is favourable, and wherein gallium is as the optimum doping agent.This dopant (Ga) of 3 weight % to 10 weight % scopes is provided, the Ga of 4 weight % to 7 weight % scopes especially, and be preferably the Ga of 5.7 weight %.
Preferable, mix with the gallium of higher percent, because under this situation, can reduce as the percentage of the aluminium of dopant.Aluminium is suitable for providing high conductivity.Be preferably the dopant aluminium that 0.1 weight % to 5 weight % scope is provided, be preferably 2 weight %.
Using just now, described suitable boundary condition allows manufacturing to have the transparent conductive oxide display coating of low resistance and high-transmission rate (may have the maximization transmissivity).
Seek independent protective for the transparent conductive oxide display coating that comprises the ZnO that mixes with the combination of aluminium, indium, gallium, boron, nitrogen, phosphorus, chlorine, fluorine or antimony or above-mentioned substance; the resistance of this coating is 1000 μ Ω cm at the most; especially at the most 600 μ Ω cm; and preferable 450 μ Ω cm at the most; and this coating can especially be made with method of the present invention in the temperature deposit that is lower than 350 ℃.
In preferred embodiment, this transparent conductive oxide display coating has at least 96.5% at the wavelength place of 550nm, especially at least 97.5% and preferable at least 98.7% transmissivity.
For the purposes of the transparent conductive oxide display coating of the transparent contacts for display etc. of the present invention is sought independent protective.This transparent contacts is preferable only to be made up of transparent conductive oxide display coating.
Description of drawings
Feature of the present invention and other advantage are from hereinafter to the description of illustrated embodiment in graphic and apparent.With simple schematic form,
Fig. 1 diagram is for the ZnO:Ga layer that produces via the DC sputter, and the resistivity of described ZnO:Ga layer is to the dependence of the hydrogen content of process gas atmosphere;
Fig. 2 diagram is for the ZnO:Ga layer that produces via the DC sputter, and the resistivity of described ZnO:Ga layer is to the dependence of power density;
Fig. 3 diagram is for the ITO and the ZnO:Ga layer that produce via the DC sputter, and the dynamic sputter rate of described ITO and ZnO:Ga layer is to the dependence of power density;
Fig. 4 diagram for the ZnO:Ga layer that produces via the DC sputter according to the inventive method with compare for ZnO:Ga and ITO layer in no hydrogen situation deposit, three's transmissivity is to the dependence of wavelength; And
Fig. 5 is shown under the 150nm layer thickness, for the ZnO:Ga layer that produces via the DC sputter according to the inventive method with compare for the ZnO:Ga layer in no hydrogen situation deposit, both transmissivities are to the dependence of wavelength.
Embodiment
Fig. 1 shows the ZnO:Ga layer of making via the DC sputter in the methods of the invention, and the resistance of described ZnO:Ga layer is to the dependence of the hydrogen content of process gas atmosphere.From having about 2W/cm
2The planar targets of power density, the ZnO:Ga layer of the about 150nm of deposit thickness on glass substrate.Certainly, also can use rotatable target (rotatable target).The ceramic target that will contain zinc oxide and gallium is advantageously used for the target of DC sputter.This target is the hybrid ceramic of making via compression or sintering usually.Perhaps, also can use metal targets by the Zn-Ga alloy composition with some weight % galliums.Via adding oxygen, sputter ZnO:Ga in the reaction process thus.
Fig. 1 is shown in the tremendous influence of hydrogen content during the DC sputter.In this embodiment, hydrogen is decreased to about 500 μ Ω cm to 600 μ Ω cm with resistance significantly from the about 1270 μ Ω cm for the ZnO:Ga of sputter under no hydrogen situation.For the hydrogen content between 4 volume % and 16 volume %, there is the resistance minimum value of wide scope.Advantageously, hydrogen does not have negative effect to the transmissivity of tco layer.On the contrary, the hydrogen content in the increase technology atmosphere will cause the slight improvement of transmissivity.
In order to set forth the positive influences of hydrogen, suppose that the dopant gallium will improve the conductivity of ZnO, but produce the lattice defect that increases resistance, and hydrogen can make these defective passivation so that resistance reduces significantly.In addition, proved conclusively in the literature hydrogen in ZnO as donor (donor), hydrogen provides the additional charge carrier to conduction band.
Fig. 2 shows that for the ZnO:Ga layer resistance is to the dependence of the power density of DC sputter.In this embodiment, in the technology atmosphere, have under the situation of 10 volume % hydrogen contents, from the ZnO:Ga layer of the about 300nm of plane target deposit thickness on glass substrate.Obviously increase the resistance that power density further reduces TCO display layer.For the ZnO:Ga with 10% hydrogen, can reach the resistance less than 450 μ Ω 2cm, and for about 10W/cm
2Power density, resistance is about 400 μ Ω cm.This fact is important, because higher power density is accompanied by higher sputter rate (referring to Fig. 3) and better layer quality.In addition, via higher sputter rate, the number that is used for the negative electrode of depositing operation can reduce, or alternatively, processing speed can improve, because in production-line technique, processing speed must each the processing stage (that is, locked stage, pretreatment stage, DC sputter, latch stage etc.) equate, and deposition has the slowest processing speed all the time, and therefore define total output.
Fig. 3 shows that both dynamic sputter rate is to the dependence of power density for the ITO (shallow square) that produces via the DC sputter under the no hydrogen situation in the technology atmosphere and ZnO (dark round dot) layer.Vertical line and horizontal line indication arc discharge limit, that is, in that not taking place, arc discharge and arc discharge reduce the scope of layer quality and reproducibility with interior limit.For ZnO, arc discharge limit (about 11W/cm of ZnO
2) than arc discharge limit (about 3W/cm of ITO
2) be higher than three times, and for ZnO, can reach the dynamic sputter rate of about 50nm m/min, rather than the dynamic sputter rate of about 20nm m/min of ITO.Even this means under the given power density, the sputter rate of ITO is higher than the sputter rate of ZnO, also is higher than the absolute possibility sputter rate of ITO with the absolute possibility sputter rate of interior ZnO in the arc discharge limit.Therefore, because the number of negative electrode can reduce or processing speed can increase, and the ZnO target is more cheap than ITO target, so handle the TCO display layer of ZnO than the TCO display layer considerably cheaper of processing ITO.
For equal power density, the dynamic sputter rate of ZnO:Ga is than the dynamic sputter rate high about 10% that ZnO:Ga under the hydrogen situation is being arranged under no hydrogen situation.
Fig. 4 shows that both transmissivities are to the dependence of wavelength for having ZnO:Ga and ITO under hydrogen and the no hydrogen situation to compare.All layers deposit the layer thickness of about 150nm on glass substrate.
In the technology atmosphere, have under the situation of 10 volume % hydrogen, deposit ZnO:Ga (dark straight line) layer via the DC sputter.Another ZnO:Ga layer of the situation deposit of no hydrogen (shallow straight line) in the technology atmosphere.Two layers are all 230 ℃ of deposit.Obviously as seen, in short wavelength's zone, hydrogen is greatly improved transmissivity, and only in the zone of about 550nm maximum transmission rate is reduced to about 98.78% (being in the ZnO:Ga that has under the hydrogen situation at 540nm) a little from about 99.50% (being in ZnO:Ga under the no hydrogen situation at 550nm).
Relatively in the technology atmosphere, have under the situation of 10 volume % hydrogen, via the ZnO:Ga layer of DC sputtering sedimentation and also at the ITO of 230 ℃ of deposit (dark dotted line), as seen ZnO:Ga has at the 540nm place about 98.8% fabulous transmissivity peak value, the transmissivity peak value (at 540nm place 97.2%) of the transmissivity peakedness ratio ITO of described ZnO:Ga high about 1.6%.Be higher than the transmissivity of ITO in the transmissivity that ZnO:Ga under the hydrogen situation is arranged in the complete visible range (350nm to 750nm) of wavelength, so that the transmission color of this coating is than the transmission color of ITO dimer (neutral).On the contrary, the ZnO:Ga layer via the DC sputtering sedimentation has the transmissivity more very different than the transmissivity of ITO (for the short wavelength) under no hydrogen situation.The transmissivity peak value of in table 1, showing all layers.
Below transmisivity data in all tables the 150nm layer thickness is suitable for.
Table 1:
| Material | Wavelength [nm] | Maximum transmission rate [%] |
| At no H 2ZnO:Ga under the situation | 550 | 99.50 |
| H is being arranged 2ZnO:Ga under the situation | 540 | 98.78 |
| ITO | 540 | 97.20 |
Advantageously, in the technology atmosphere, there is the transmissivity of ZnO:Ga under the hydrogen situation only to rely on depositing temperature a little, under higher temperature, can has transmissivity a little preferably.
For ZnO:Al (that is, the zinc oxide of adulterated al), in table 2, show the result who relatively measures.In two examples, hydrogen content is all 14% in the technology atmosphere, but the substrate temperature difference.
Table 2:
Fig. 5 is illustrated under the 150nm layer thickness, for containing under the processing gas situation of hydrogen according to the inventive method, the ZnO:Ga layer that produces via the DC sputter with carry out hydrogen to the influence of transmissivity or the comparison of effect for the ZnO:Ga layer in no hydrogen situation deposit, that is transmissivity is to the dependence of wavelength.
Compare with Fig. 4, Fig. 5 is illustrated in the same layer thickness of 150nm and produces under the optimal processing parameter of max transmissive, in the comparison that has under hydrogen and the no hydrogen situation between two ZnO:Ga layers.In detail relatively showing among Fig. 5, on the visible-range of whole wavelength almost, can increase transmission via adding hydrogen.
Have 6.0 volume % hydrogen, 93.7 volume % argons (Ar) and 0.3 volume % oxygen (O
2) situation under, deposit ZnO:Ga layer (straight line) via the DC sputter.Have 99.7 volume %Ar and 0.3 volume %O
2Another ZnO:Ga layer (dotted line) of situation deposit.In table 3, show the transmittance values ITO layer of no hydrogen situation deposit (also).Can be clear that hydrogen improvement transmissivity.
Indicated value measures with respect to cleaning, transparent glass.Therefore, these indicated values are quite high.
Table 3:
In above-mentioned research, obviously by means of the present invention, compare with ITO and can especially simply reach the cost effective and efficient manner and realize having high-transmission rate and low-resistance TCO display layer.Therefore, cost produces the display that these tco layers can be used as transparent conductive contact effectively more.These TCO display layers also can be used in other device (such as solar cell etc.).
Should be appreciated that, the invention is not restricted to above describe and illustrated embodiment herein, but contain any and all changes of the category that belongs to appended claims.For example, although all results that describe are relevant with the zinc oxide of doped gallium, but those who familiarize themselves with the technology be it is evident that other general dopant is available, such as aluminium, indium, boron, nitrogen, phosphorus, chlorine, fluorine or antimony etc., or the combination of above-mentioned substance.
Claims (20)
- One kind via deposition through mixing zinc oxide and produce the method for transparent conductive oxide display coating, transparent conductive oxide display layer in particular for the transparent contacts of display, described method is characterised in that this transparent conductive oxide display coating is produced under the situation with the technology atmosphere that comprises pure hydrogen.
- 2. the method for claim 1, described method is characterised in that the hydrogen content in this technology atmosphere is in the scope of 1 volume % to 50 volume %.
- 3. the method for claim 1, described method is characterised in that the hydrogen content in this technology atmosphere is in the scope of 4 volume % to 16 volume %.
- 4. each described method in the claim as described above, described method is characterised in that substrate temperature is 350 ℃ at the most between depositional stage.
- 5. method as claimed in claim 4, described method be characterised in that, at substrate temperature between depositional stage in 100 ℃ to 250 ℃ scope.
- 6. method as claimed in claim 4, described method is characterised in that substrate temperature is 230 ℃ between depositional stage.
- 7. the method for claim 1, described method is characterised in that this transparent conductive oxide display coating produces via sputter.
- 8. method as claimed in claim 7, described method be characterised in that, this transparent conductive oxide display coating is via direct current (DC) sputter, produce through direct current sputtering or intermediate frequency (MF) sputter of pulse.
- 9. method as claimed in claim 7, described method is characterised in that power density is at 2W/cm 2To 20W/cm 2Scope in.
- 10. method as claimed in claim 7, described method is characterised in that power density is at 4W/cm 2To 15W/cm 2Scope in.
- 11. the method for claim 1, described method be characterised in that, this technology atmosphere further contains aerobic, contain the admixture of gas of aerobic or contain any compound of aerobic.
- 12. the method for claim 1, described method are characterised in that dopant is the combination of aluminium, indium, gallium, boron, nitrogen, phosphorus, chlorine, fluorine or antimony or above-mentioned substance.
- 13. method as claimed in claim 12, described method are characterised in that, the gallium of 3 weight % to 10 weight % scopes is provided.
- 14. method as claimed in claim 12, described method are characterised in that, the gallium of 4 weight % to 7 weight % scopes is provided.
- 15. method as claimed in claim 12, described method are characterised in that, the aluminium of 0.1 weight % to 5 weight % scope is provided.
- 16. transparent conductive oxide display coating that comprises zinc oxide and dopant, described coating is characterised in that, the resistivity of this coating is 1000 μ Ω cm at the most, and this coating is in the temperature deposit that is lower than 350 ℃, and makes with each described method in the claim as described above.
- 17. transparent conductive oxide display coating as claimed in claim 16, described coating are characterised in that, are the coating of 150nm for thickness, the transmissivity of this coating is at least 96.5% at the wavelength place of 540nm.
- 18. transparent conductive oxide display coating as claimed in claim 17, described coating are characterised in that, are the coating of 150nm for thickness, the transmissivity of this coating is at least 97.5% at the wavelength place of 540nm.
- 19. the purposes as claim 16 or 17 described transparent conductive oxide display coatings, described purposes are characterised in that this transparent conductive oxide display coating is used for the transparent contacts of display.
- 20. purposes as claimed in claim 19, described purposes are characterised in that this transparent contacts only is made up of this transparent conductive oxide display coating.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08018397A EP2180529A1 (en) | 2008-10-21 | 2008-10-21 | Transparent conductive zinc oxide film and production method thereof |
| EP08018397.3 | 2008-10-21 | ||
| US12/255,019 | 2008-10-21 | ||
| US12/255,019 US20100095866A1 (en) | 2008-10-21 | 2008-10-21 | Transparent conductive zinc oxide film and production method therefor |
| PCT/EP2009/007112 WO2010046025A1 (en) | 2008-10-21 | 2009-10-05 | Transparent conductive zinc oxide display film and production method therefor |
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| CN102187476A CN102187476A (en) | 2011-09-14 |
| CN102187476B true CN102187476B (en) | 2013-09-11 |
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| CN200980142398XA Expired - Fee Related CN102187476B (en) | 2008-10-21 | 2009-10-05 | Transparent conductive zinc oxide display film and production method therefor |
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| EP (1) | EP2338178A1 (en) |
| JP (1) | JP5647130B2 (en) |
| KR (1) | KR20110089143A (en) |
| CN (1) | CN102187476B (en) |
| SG (1) | SG195564A1 (en) |
| TW (1) | TW201022457A (en) |
| WO (1) | WO2010046025A1 (en) |
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| FR2961955B1 (en) * | 2010-06-29 | 2012-07-20 | Saint Gobain | PHOTOVOLTAIC CELL WITH COLORING |
| WO2012043732A1 (en) * | 2010-10-01 | 2012-04-05 | 株式会社エス・エフ・シー | Film forming method |
| DE102011116191A1 (en) * | 2011-10-13 | 2013-04-18 | Southwall Europe Gmbh | Multi-layer systems for selective reflection of electromagnetic radiation from the wavelength spectrum of sunlight and method for its production |
| EP2738815B1 (en) | 2012-11-30 | 2016-02-10 | Samsung Electronics Co., Ltd | Semiconductor materials, transistors including the same, and electronic devices including transistors |
| CN105695947A (en) * | 2016-04-09 | 2016-06-22 | 浙江大学 | Nonmetal co-doped ZnO transparent conducting thin film with high migration rate and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4623601A (en) * | 1985-06-04 | 1986-11-18 | Atlantic Richfield Company | Photoconductive device containing zinc oxide transparent conductive layer |
| US4638111A (en) * | 1985-06-04 | 1987-01-20 | Atlantic Richfield Company | Thin film solar cell module |
| US5078803A (en) * | 1989-09-22 | 1992-01-07 | Siemens Solar Industries L.P. | Solar cells incorporating transparent electrodes comprising hazy zinc oxide |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62190613A (en) * | 1986-02-17 | 1987-08-20 | 株式会社半導体エネルギー研究所 | Manufacture of zinc oxide conductive film |
| WO1992018990A1 (en) * | 1991-04-10 | 1992-10-29 | Tokio Nakada | Method for manufacturing transparent conductive film |
| JP2928016B2 (en) * | 1992-03-25 | 1999-07-28 | 株式会社富士電機総合研究所 | Method for forming transparent conductive film |
| US20020084455A1 (en) * | 1999-03-30 | 2002-07-04 | Jeffery T. Cheung | Transparent and conductive zinc oxide film with low growth temperature |
| JP2002363732A (en) * | 2001-03-15 | 2002-12-18 | Asahi Glass Co Ltd | Transparent conductive film manufacturing method, and transparent substrate having transparent conductive film |
| JP2003105533A (en) * | 2001-10-01 | 2003-04-09 | Mitsubishi Heavy Ind Ltd | Method of producing transparent electroconductive film and transparent electroconductive film |
| JP2004207383A (en) * | 2002-12-24 | 2004-07-22 | Central Glass Co Ltd | Electromagnetic shielding film |
| JP2004296597A (en) * | 2003-03-26 | 2004-10-21 | Canon Inc | Process for fabricating multilayer photovoltaic element |
| JP4599595B2 (en) * | 2005-12-05 | 2010-12-15 | 学校法人金沢工業大学 | Method and apparatus for producing transparent conductive film |
| JP2007327079A (en) * | 2006-06-06 | 2007-12-20 | Sony Corp | Transparent conductive laminate film, and its manufacturing method |
-
2009
- 2009-10-05 CN CN200980142398XA patent/CN102187476B/en not_active Expired - Fee Related
- 2009-10-05 JP JP2011532516A patent/JP5647130B2/en not_active Expired - Fee Related
- 2009-10-05 KR KR1020117011531A patent/KR20110089143A/en not_active Application Discontinuation
- 2009-10-05 EP EP09778822A patent/EP2338178A1/en not_active Withdrawn
- 2009-10-05 WO PCT/EP2009/007112 patent/WO2010046025A1/en active Application Filing
- 2009-10-05 SG SG2013077318A patent/SG195564A1/en unknown
- 2009-10-12 TW TW098134513A patent/TW201022457A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4623601A (en) * | 1985-06-04 | 1986-11-18 | Atlantic Richfield Company | Photoconductive device containing zinc oxide transparent conductive layer |
| US4638111A (en) * | 1985-06-04 | 1987-01-20 | Atlantic Richfield Company | Thin film solar cell module |
| US5078803A (en) * | 1989-09-22 | 1992-01-07 | Siemens Solar Industries L.P. | Solar cells incorporating transparent electrodes comprising hazy zinc oxide |
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| SG195564A1 (en) | 2013-12-30 |
| CN102187476A (en) | 2011-09-14 |
| JP2012506486A (en) | 2012-03-15 |
| JP5647130B2 (en) | 2014-12-24 |
| WO2010046025A1 (en) | 2010-04-29 |
| EP2338178A1 (en) | 2011-06-29 |
| KR20110089143A (en) | 2011-08-04 |
| TW201022457A (en) | 2010-06-16 |
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