WO2010046025A1 - 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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- WO2010046025A1 WO2010046025A1 PCT/EP2009/007112 EP2009007112W WO2010046025A1 WO 2010046025 A1 WO2010046025 A1 WO 2010046025A1 EP 2009007112 W EP2009007112 W EP 2009007112W WO 2010046025 A1 WO2010046025 A1 WO 2010046025A1
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 58
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 58
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000002834 transmittance Methods 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
- 238000000151 deposition Methods 0.000 claims abstract description 17
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 16
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004411 aluminium Substances 0.000 claims abstract description 9
- 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
- 239000000460 chlorine Substances 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 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
- 238000004544 sputter deposition Methods 0.000 claims description 30
- 239000002019 doping agent Substances 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 66
- 239000011521 glass Substances 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 hydrogen compound Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
Classifications
-
- 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
Definitions
- the present invention concerns a method for the generation of a transparent conductive oxide display coating in accordance with the generic term of claim 1 , a transparent conductive oxide display coating in accordance with the generic term of claim 9 and a use of a transparent conductive oxide display coating in accordance with the generic term of claim 1 1.
- Transparent conductive contacts are especially needed for photovoltaic applications, such as solar cells and solar modules.
- TCO layers transparent conductive oxide coatings
- ITO indium tin oxide
- ITO indium tin oxide
- ZnO zinc oxide
- ZnO has a higher resistance compared to ITO and great efforts have been made to reduce its resistance.
- US 5,078,804 is known a structure with a first ZnO layer of high electrical resistance (low conductivity) and a second ZnO layer of low electrical resistance (high conductivity), with the first ZnO layer arranged on a buffer layer covering the absorber range of a copper indium gallium diselenide (CIGS).
- Both ZnO layers are deposited by RF magnetron sputtering in an oxygen-argon atmosphere or a pure argon atmosphere.
- US 2005/0109392 Al discloses a CIGS solar cell structure, in which the buffer layer is likewise covered with a so-called intrinsic, i.e. pure ZnO layer (i- ZnO), which exhibits a high electrical resistance, and upon which is subsequently applied a ZnO layer, which is doped with aluminum and exhibits low electrical resistance.
- the i-ZnO- layer is deposited by RF magnetron sputtering and the ZnO layer of high conductivity is deposited by magnetron sputtering of an aluminum-doped ZnO target.
- This aluminum- doped ZnO target can also be DC sputtered, which substantially increases the coating rate relative to RF sputtered targets.
- DC sputtering is in industrial use for deposition of these conductive ZnO: Al layers. Disadvantageous in such a TCO layer is the fact that it must be structured. Resistances of 500 ⁇ cm to 1000 ⁇ cm are reachable for high depositing temperatures of 350 0 C and more. Furthermore, conductivity of doped ZnO is limited for lower temperatures and transmittance of ZnO may be influenced unfavorable by dopants.
- the object of the present invention is therefore to make a procedure available, with which TCO display layers of ZnO are producible that have high conductivity as well as high transparency without the need of special structuring and, in particular, which are reachable for temperatures below 350°C.
- resistance and transparency of the coating should be comparable to and preferably transmittance should be better than those of ITO.
- the inventive method is characterized by the fact that a transparent conductive oxide display coating 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 including hydrogen.
- Gallium is the most preferred dopant.
- ZnO layers doped with aluminium, indium, gallium, boron, nitrogen, phosphorous, chlorine, fluorine or antimony or a combination thereof ZnO:X layer
- ZnO :X layers of low resistance and high transmittance can be manufactured and these properties are comparably good as these for ITO and for transmittance it may be - -
- TCO display layers may be deposited directly onto a substrate, like glass, resin and the like, or onto other layers, like functional layers of solar cells or displays.
- the hydrogen content in the process atmosphere is in the range from 1 vol. % to 50 vol. %, in particular in the range from 4 vol. % to 16 vol. % and preferably in the range from 6 vol. % to 12 vol. %. It is possible to work with elementary hydrogen or with an argon-hydrogen mixture. This allows for working very clean, since with atmospheres containing for example methan, carbon will be deposited, which is not desired.
- the substrate temperature during deposition is at most 350°C, in particular, is in the range from 100°C to 250°C and preferably is 230°C.
- these temperature ranges for instance displays are producible comprising resin colour filters having a critical temperature of 250 °C and being damaged above that temperature.
- hydrogen content in the process atmosphere leads for low temperatures to a resistance as low as for gallium doped ZnO at temperatures of at least 350°C.
- temperature regimes useable: cold depositing with successive tempering or warm depositing, with warm depositing possibly preceded by preheating.
- warm deposition is preferred and in particular a temperature ramp is used during deposition.
- Usable deposition methods are chemical vapor deposition, physical vapor deposition, such as sputtering and the like, with DC sputtering mostly preferred, because of its high production throughput, good layer quality and low equipment costs. If the TCO display layer is generated by means of pulsed DC sputtering, process stability can be improved and thus the deposition rate can be advantageously further increased, since higher power densities are possible. An increase in process stability can also be obtained by the use of medium frequency sputtering (MF-sputtering) of at least two targets.
- MF-sputtering medium frequency sputtering
- DC sputtering in the context of the present invention is therefore meant DC sputtering, pulsed DC sputtering and MF- sputtering.
- the power density for DC sputtering is in the range from 2 W/cm 2 to 20 W/cm 2 , in particular in the range from 4 W/cm 2 to 15 W/cm 2 and preferably in the range from 6 W/cm 2 to 1 1 W/cm 2 .
- the resistance is improved as well as the deposition rate.
- the process atmosphere could further contain oxygen.
- a hydrogen source which contains a gas mixture containing hydrogen or a hydrogen compound
- the amount of hydrogen can be controlled more precisely by using a larger mass flow controller (MFC). If a hydrogen source is used containing a chemical compound containing hydrogen, processing of hydrogen, in particular in connection with oxygen, is safer.
- This dopant (Ga) is provided in the range from 3 to 10 wt. %, in particular in the range from 4 to 7 wt. % Ga and preferably with 5.7 wt % Ga.
- doping is carried out with a higher percentage of gallium, since in this case the percentage of aluminium as dopant can be reduced.
- Aluminium is suitable to provide high conductivity.
- the dopant aluminium is preferably provided in the range from 0.1 to 5 wt. %, preferably with 2 wt. %.
- a transparent conductive oxide display coating with low resistance and high transmittance (maximizing of transmittance is possible).
- Independent protection is sought for a transparent conductive oxide display coating comprising ZnO doped with aluminium, indium, gallium, boron, nitrogen, phosphorous, chlorine, fluorine or antimony or a combination thereof, the resistance of the coating is at most 1000 ⁇ cm, in particular at most 600 ⁇ cm and preferably at most 450 ⁇ cm and the coating is depositable at temperatures below 350°C, in particular produced with the method of the present invention.
- the transparent conductive oxide display coating has a transmit- tance of at least 96,5 %, in particular at least 97,5 % and preferably at least 98,7 % at a wavelength of 550 nm.
- the transparent conductive oxide display coating of the present invention Independent protection is sought for a use of the transparent conductive oxide display coating of the present invention for a transparent contact for, displays and the like.
- the transparent contact is only consisting of the transparent conductive oxide display coating.
- Fig. 1 illustrates the dependence of the resistivity on the hydrogen content of the process gas atmosphere for ZnO:Ga layers generated by DC sputtering
- Fig. 2 illustrates the dependence of the resistivity on the power density for ZnO:Ga layers generated by DC sputtering
- Fig. 3 illustrates the dependence of the dynamic sputter rate on the power density for ITO and ZnO: Ga layers generated by DC sputtering
- Fig. 4 illustrates the dependence of the transmittance on the wavelength compared for a ZnO:Ga layer generated by DC sputtering according to the inventive method and for ZnO:Ga and ITO layers deposited without hydrogen, and
- Fig. 5 illustrates the dependence of the transmittance on the wavelength compared for a ZnO: Ga layer generated by DC sputtering according to the inventive method and for a ZnO:Ga layer deposited without hydrogen for 150nm layer thickness.
- Fig. 1 shows the dependence of the resistance on the hydrogen content of the process gas atmosphere for ZnO: Ga layers, which were manufactured in the inventive method by means of DC sputtering.
- the ZnO:Ga layers were deposited with a thickness of about 150 nm onto a glass substrate from a planar target with a power density of about 2 W/cm 2 .
- rotatable targets are useable, too.
- a ceramic target containing both zinc oxide and gallium is used advantageously as the target for DC sputtering.
- a target is mixed ceramic, which is typically producible by compression or sintering.
- metallic targets are also usable which consist of a Zn-Ga alloy with several wt. % gallium. Through addition of oxygen, ZnO:Ga can be sputtered herefrom in the reactive process.
- Fig. 1 illustrates the huge influence of hydrogen content during DC sputtering.
- hydrogen significantly decreases resistance from about 1270 ⁇ cm for ZnO:Ga sputtered without hydrogen to about 500 ⁇ cm to 600 ⁇ cm.
- hydrogen has no negative influence to transmittance of the TCO layer. To the contrary, increasing the hydrogen content in process atmosphere will lead to a slightly improvement in transmittance.
- Fig. 2 shows the dependence of the resistance on the power density of DC sputtering for ZnO:Ga layers.
- the ZnO:Ga layers in this embodiment were deposited with a thickness of about 300 nm onto a glass substrate from a planar target with a hydrogen content in the process atmosphere of 10 vol. %. It becomes clear that increasing power density further reduces resistance of the TCO display layer.
- For ZnO:Ga with 10 % hydrogen a resistance of less than 450 ⁇ cm is reachable and for a power density of about 10 W/cm 2 the resis- tance is about 400 ⁇ cm. This fact is important, since a higher power density is followed by a higher sputter rate (see Fig. 3) and better layer quality.
- the number of cathodes used in the deposition process may be reduced or, alternatively, the process speed may be enhanced, because for in line-processing the processing speed must be equal for each process stage, i.e. locking-in stage, preprocessing stage, DC sputtering, locking-out stage and so on and deposition always has the slowest processing speed and thus defines the over all throughput.
- Fig. 3 shows the dependence of the dynamic sputter rate on the power density for ITO (light squares) and ZnO (dark dots) layers generated by DC sputtering without hydrogen within the process atmosphere.
- Vertical and horizontal lines indicate the arcing limit, i.e. the limit within no arcing occurs and arcing reduces layer quality and reproducibility.
- the arcing limit is more than three times higher (about 1 1 W/cm 2 ) than for ITO (about 3 W/cm 2 ) and for ZnO dynamic sputter rates of about 50 nm m/min are reachable instead of about 20 nm m/min for ITO.
- Dynamic sputter rates of ZnO: Ga without hydrogen are about 10% higher than for ZnO: Ga with hydrogen for equal power densities.
- Fig. 4 shows dependence of transmittance on wavelength compared for ZnO: Ga with and without hydrogen and for ITO. All layers are deposited with layer thicknesses of about 150 nm onto a glass substrate.
- a ZnO:Ga (dark straight line) layer was deposited by DC sputtering with 10 vol. % hydrogen within the process atmosphere.
- a further ZnO:Ga layer was deposited without hydrogen within the process atmosphere. Both layers were deposited at 230°C. It is clearly to see that hydrogen greatly improves transmittance in the region of short wave- lengths, and only reduces the maximum transmittance slightly in the region about 550 nm from about 99,50 % for ZnOiGa without hydrogen at 550 nm to about 98,78 % for ZnO:Ga with hydrogen at 540 nm.
- ZnO:Ga Comparing the ZnO:Ga layer deposited by DC sputtering with 10 vol. % hydrogen within the process atmosphere with ITO (dark dashed line), also deposited at 230°C, it can be seen that ZnO:Ga has an excellent transmittance peak of about 98,8% at 540 nm, which is about 1,6% higher than for ITO (97,2 % at 540 nm).
- the transmittance of ZnO:Ga with hydrogen is higher than the transmittance of ITO over the complete visible range of wavelength (350nm to 750nm), so that the transmittance colour of this coating is more neutral than that of ITO.
- the ZnO:Ga layer deposited by DC sputtering without hydrogen has a transmittance for short wavelength even worse than for ITO. Transmittance peaks for all layers are shown in Table 1.
- the transmittance data in all tables below are valid for 150nm layer thickness.
- transmittance for ZnO:Ga with hydrogen in process atmosphere is only slightly depending from deposition temperature, with slightly better transmittance for higher temperatures.
- Fig. 5 shows the impact or effect of hydrogen on transmittance, that is the dependence of the transmittance on wavelength compared for a ZnO: Ga layer generated by DC sputtering with a process gas containing hydrogen according to the inventive method and for a ZnO: Ga layer deposited without hydrogen at 150nm layer thickness.
- fig. 5 shows the comparison between two ZnO:Ga layers with and without hydrogen at the same layer thickness of 150nm and optimized process parameters which lead to maximized transmission.
- the detailed comparison in figure 5 shows, that the transmission increases over almost the whole visible range of wavelength by addition of hydrogen.
- a ZnO:Ga layer (straight line) was deposited by DC sputtering with 6.0 vol. % hydrogen, 93.7 vol. % argon (Ar) and 0.3 vol. % oxygen (O 2 ).
- a further ZnO:Ga layer (dashed line) was deposited with 99.7 vol. % Ar and 0.3 vol. % O 2 .
- Transmittance values are shown in Table 3 (also an ITO layer which is deposited without hydrogen). It can be clearly seen that hydrogen improves transmittance.
- TCO display layers that have a high transmittance and low resistance can be realized in a particularly simple and cost-effective way compared to ITO.
- displays in which these TCO layers can be used as transparent electrically conductive contacts, can be generated much more cost effectively.
- These TCO display layers can also be used in other devices like solar cells and so on. It is to be understood that the present invention is not limited to the embodiment(s) described above and illustrated herein, but encompasses any and all variations falling within the scope of the appended claims.
- gallium doped zinc oxide gallium doped zinc oxide
- other common dopants like aluminium, indium, boron, nitrogen, phosphorous, chlorine, fluorine or antimony and so on, or combinations thereof.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011532516A JP5647130B2 (en) | 2008-10-21 | 2009-10-05 | Transparent conductive zinc oxide display film and method for producing the same |
EP09778822A EP2338178A1 (en) | 2008-10-21 | 2009-10-05 | Transparent conductive zinc oxide display film and production method therefor |
CN200980142398XA CN102187476B (en) | 2008-10-21 | 2009-10-05 | Transparent conductive zinc oxide display film and production method therefor |
US13/123,874 US20120049128A1 (en) | 2008-10-21 | 2009-10-05 | Transparent conductive zinc oxide display film and production method therefor |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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US12/255,019 | 2008-10-21 | ||
EP08018397.3 | 2008-10-21 | ||
EP08018397A EP2180529A1 (en) | 2008-10-21 | 2008-10-21 | Transparent conductive zinc oxide film and production method thereof |
US12/255,019 US20100095866A1 (en) | 2008-10-21 | 2008-10-21 | Transparent conductive zinc oxide film and production method therefor |
Publications (1)
Publication Number | Publication Date |
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WO2010046025A1 true WO2010046025A1 (en) | 2010-04-29 |
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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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---|---|
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) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2961955A1 (en) * | 2010-06-29 | 2011-12-30 | Saint Gobain | Coloring photoactive layer/conductive substrate assembly for coloring photovoltaic cell, has conductive substrate defining contact surface with coloring carrier material and comprising root mean square roughness between specific nanometers |
JP5008211B2 (en) * | 2010-10-01 | 2012-08-22 | 株式会社エス・エフ・シー | Deposition 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 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 (4)
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 |
US20020028571A1 (en) * | 1999-03-30 | 2002-03-07 | Rockwell Science Center Llc | Transparent and conductive zinc oxide film with low growth temperature |
Family Cites Families (9)
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 |
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 KR KR1020117011531A patent/KR20110089143A/en not_active Application Discontinuation
- 2009-10-05 JP JP2011532516A patent/JP5647130B2/en not_active Expired - Fee Related
- 2009-10-05 SG SG2013077318A patent/SG195564A1/en unknown
- 2009-10-05 WO PCT/EP2009/007112 patent/WO2010046025A1/en active Application Filing
- 2009-10-05 CN CN200980142398XA patent/CN102187476B/en not_active Expired - Fee Related
- 2009-10-05 EP EP09778822A patent/EP2338178A1/en not_active Withdrawn
- 2009-10-12 TW TW098134513A patent/TW201022457A/en unknown
Patent Citations (4)
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 |
US20020028571A1 (en) * | 1999-03-30 | 2002-03-07 | Rockwell Science Center Llc | Transparent and conductive zinc oxide film with low growth temperature |
Non-Patent Citations (2)
Title |
---|
CHOPRA K L ET AL: "TRANSPARENT CONDUCTORS. ÖA STATUS REVIEW", THIN SOLID FILMS, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 102, 1 January 1983 (1983-01-01), pages 1 - 46, XP000573894, ISSN: 0040-6090 * |
See also references of EP2338178A1 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2961955A1 (en) * | 2010-06-29 | 2011-12-30 | Saint Gobain | Coloring photoactive layer/conductive substrate assembly for coloring photovoltaic cell, has conductive substrate defining contact surface with coloring carrier material and comprising root mean square roughness between specific nanometers |
JP5008211B2 (en) * | 2010-10-01 | 2012-08-22 | 株式会社エス・エフ・シー | Deposition 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 |
Also Published As
Publication number | Publication date |
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CN102187476A (en) | 2011-09-14 |
EP2338178A1 (en) | 2011-06-29 |
JP2012506486A (en) | 2012-03-15 |
TW201022457A (en) | 2010-06-16 |
KR20110089143A (en) | 2011-08-04 |
SG195564A1 (en) | 2013-12-30 |
CN102187476B (en) | 2013-09-11 |
JP5647130B2 (en) | 2014-12-24 |
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