WO2018090926A1 - Pellicule conductrice transparente et son procédé de préparation, cible de pulvérisation, substrat conducteur transparent et cellule solaire - Google Patents

Pellicule conductrice transparente et son procédé de préparation, cible de pulvérisation, substrat conducteur transparent et cellule solaire Download PDF

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WO2018090926A1
WO2018090926A1 PCT/CN2017/111073 CN2017111073W WO2018090926A1 WO 2018090926 A1 WO2018090926 A1 WO 2018090926A1 CN 2017111073 W CN2017111073 W CN 2017111073W WO 2018090926 A1 WO2018090926 A1 WO 2018090926A1
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transparent conductive
conductive film
solar cell
zinc oxide
target
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Chinese (zh)
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林俊荣
杨本润
高明
魏怡心
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汉能联创移动能源投资有限公司
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    • 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
    • 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
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. 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
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • 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
    • 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]

Definitions

  • the invention relates to the technical field of transparent conductive films, and in particular to a transparent conductive film and a preparation method thereof, a sputtering target, a transparent conductive substrate and a solar battery.
  • Zinc oxide is a wide bandgap semiconductor with a high binding energy of 60 millielectron volts, a band gap width of about 3.3 electron volts, high transmittance for visible light, and easy n-type doping.
  • Zinc oxide has many applications for optoelectronic products such as solar products, light-emitting diodes, blue laser diodes, and flat panel displays. Due to the development of modern technology, the demand and application of new energy sources are more and more extensive.
  • Oxide transparent conductive film is widely used in solar cell, flat panel display, heat radiation mirror and other fields as an important optoelectronic functional material.
  • Zinc oxide-based transparent conductive films doped with zinc oxide have become the focus of current research. Common zinc oxide-based transparent conductive films often use elements such as aluminum, gallium, and indium to enhance the conductivity of the n-type conductive film. Doping of such trivalent cations can achieve good electron conductivity and high visible light transmittance.
  • the zinc oxide film has an optical transmittance of 77.7% in the near-infrared band of 700-2000 nm, which is increased by 1.7%.
  • the doping process greatly improves the light trapping effect of the film layer and improves the optical transmittance of the near-infrared light region.
  • CN102719797A prepares a zinc oxide-based transparent conductive film with up-conversion function, and ZnO is used as a matrix material, and one of Al 3+ , Yb 3+ , Er 3+ and Tm 3+ elements is doped in the ZnO matrix material. Two or more, the atomic molar ratio of Zn to the doped element is controlled to be 10:1 to 100:1.
  • the transparent conductive film is prepared by preparing one or two or more of ZnO, Al 2 O 3 , Yb 2 O 3 , Er 2 O 3 , and Tm 2 O 3 to prepare a ceramic for sputtering.
  • the target material controls the atomic molar ratio of Zn to the doped metal ions to be 10:1 to 100:1, and is sputter-sputtered to obtain a ZnO-based transparent conductive film.
  • the average transmittance of the ZnO-based transparent conductive film in the visible light region (400 to 900 nm) is in the range of 75% to 98%, and the resistivity is in the range of 8.0 ⁇ 10 -3 to 1.0 ⁇ 10 -4 ⁇ cm, which is absorbable.
  • Near-infrared light having a wavelength of 800 nm to 1700 nm and emitting visible light.
  • CN101834009B relates to a zinc oxide transparent conductive film material doped with indium and a preparation method thereof.
  • the method adopts multi-target co-sputtering magnetron sputtering technology to prepare a ZnO:In transparent conductive film with polycrystalline structure on common alkali glass and quartz glass substrate by using zinc oxide ceramic target and indium metal target co-sputtering method.
  • the process conditions are: argon gas and oxygen mixed working gas pressure is 0.2-2.0Pa, oxygen to argon volume ratio is 0-0.2, zinc oxide target and indium target sputtering power are 50-200W and 5-40W, respectively, substrate
  • the temperature is from room temperature to 500 ° C, and the bias voltage is from 0 to -200V.
  • the obtained transparent conductive film has a content of indium atoms as low as 2%, and has excellent electrical conductivity, and a transmittance of more than 90% at 400 to 1100 nm.
  • CN102534498A discloses a preparation method of a gallium-doped zinc oxide transparent conductive film, comprising the steps of: preparing a Ga 2 O 3 :ZnO ceramic target; vacuum processing the cavity of the coating device; adjusting the magnetron sputtering coating process Parameters for coating treatment.
  • the gallium-doped zinc oxide transparent conductive film is prepared, and the target used is a single Ga component target.
  • the film with different Ga content is prepared by adjusting the parameters of the magnetron sputtering coating process; the gallium-doped zinc oxide transparent conductive film resistor of the present invention
  • the rate decreases first and then increases with the increase of Ga content, and reaches a minimum of 6.6 ⁇ 10 -4 ⁇ cm when the Ga content is 4.6 wt%, and its visible light transmittance is greater than 85%.
  • the above prior art has the following disadvantages: due to the high resistivity of the intrinsic ZnO material, in order to meet the requirements of being a transparent conductive material, it is necessary to improve the conductivity of the transparent conductive film by doping elements such as Al and Ga, but
  • the zinc oxide-based transparent conductive film has a light absorption phenomenon of near-infrared light (especially 800-1300 nm in this paper), and this phenomenon causes the near-infrared light energy to penetrate the conductive film, thereby causing the solar material to be unable to be absorbed into electric energy. Therefore, in order to improve the conversion efficiency of a solar cell, it is necessary to provide a transparent conductive film which can satisfy both low resistivity requirements and high near-infrared light region average light transmittance.
  • One of the technical problems to be solved by the present invention is to provide a transparent film having excellent photoelectric properties.
  • the conductive film and the preparation method thereof satisfy the requirement of low resistivity and can improve the average light transmittance of the near-infrared light region.
  • the present invention proposes a technique of doping into a zinc oxide-based thin film by doping with a tetravalent cation. Since the tetravalent cation has one more valence electron than the trivalent cation, the tetravalent cation can provide two electrons to contribute to the conductivity of the transparent conductive film when the divalent zinc ion Zn 2+ in the zinc oxide is substituted.
  • a transparent conductive film is formed on the substrate by a sputtering process using a titania-doped zinc oxide-based ceramic target.
  • Ti 4+ is a tetravalent cation and has an ionic radius of 68 pm, which is quite close to the 74 pm ionic radius of zinc ions, tetravalent titanium ions can easily displace zinc ions and have less influence on the host lattice. It is very suitable for doping into zinc oxide-based films.
  • the probability of scattering electrons is proportional to the square of the number of ion charges, and the radius and ion of the internal periodic potential field of the zinc oxide crystal The number of charges is proportional. That is, the titanium oxide doped zinc oxide (also referred to herein as titanium doped zinc oxide) film is compared to the aluminum oxide doped zinc oxide (also referred to herein as aluminum doped zinc oxide) film, a single Ti 4+ ion pair.
  • an impurity ion such as Ti 4+
  • the scattering probability of electrons is 16/9 times that of single Al 3+ ions; when the doping effect contributes the same electron concentration, the Ti 4+ concentration is only 1/2 of Al 3+ ; therefore, the total of Ti 4+ ions to electrons
  • the present invention provides a transparent conductive film comprising a zinc element, an oxygen element, and a titanium element, wherein the proportion of zinc atoms in the transparent conductive film is 98 at% to 99 at %, the proportion of the titanium atom is from 1 at% to 2 at%.
  • the transparent conductive film has a resistivity of (0.4 to 1) ⁇ 10 -3 ⁇ cm, and when the transparent conductive film has a thickness of 1000 nm, an average transmittance of the (800 to 1300) nm near-infrared region. ⁇ 80%.
  • the crystal structure of the transparent conductive film is a hexagonal wurtzite phase structure along a (002) orientation, and the sheet resistance is (4 to 10) ⁇ / ⁇ , and the carrier concentration is (4 to 9.3) ⁇ 10 20 . /cm 3 , mobility is (43 to 57.6) cm 2 V -1 S -1 .
  • the present invention also provides a preparation method of the above transparent conductive film.
  • the transparent conductive film is prepared by depositing a titania-doped zinc oxide-based ceramic target on a substrate by a magnetron sputtering process; wherein the titania-doped zinc oxide-based ceramic target is doped
  • the range of titanium dioxide is from 1 at% to 2 at%.
  • the titania-doped zinc oxide-based ceramic target has a purity of not less than 99.9% and a relative density of not less than 94%.
  • the titania-doped zinc oxide-based ceramic target is doped with titanium dioxide in a range of 1.7 at%, and the obtained transparent conductive film has a resistivity of 4 ⁇ 10 -4 ⁇ cm.
  • the process parameters when the transparent conductive film is prepared by a magnetron sputtering process are as follows: a substrate temperature of 150 to 250 ° C, a working pressure of 1.5 to 3 mtorr, and a cavity bottom pressure of 0.005 mtorr.
  • the titania-doped zinc oxide-based ceramic target is Gel-Casting, Cold Isostatic Pressing (CIP), Hot Isostatic Pressing (Hot Isostatic Pressing). Referred to as HIP), or hot pressing (HP) process.
  • the transparent conductive film prepared by using the sputtering target has excellent photoelectric performance, meets the requirements of low resistivity, and can improve near-infrared light. Area average light transmittance.
  • the present invention provides a sputtering target which is a titania-doped zinc oxide-based ceramic target, and a titanium atom and a sum of (titanium atom + zinc atom) in the sputtering target
  • the atomic ratio is 1% to 2%.
  • the zinc oxide-based ceramic target is doped with titanium dioxide in a range of 1 at% to 2 at%; the sputtering target has a purity of not less than 99.9% and a relative density of not less than 94%.
  • the sputtering target is prepared by gel injection molding, cold isostatic pressing, hot isostatic pressing, or hot pressing sintering; the sputtering target is a planar target or a rotating target.
  • another technical problem to be solved by the present invention is to provide a transparent conductive substrate which has good electrical conductivity, high visible light transmittance, and high average light transmittance of near-infrared light.
  • the transparent conductive substrate provided by the present invention is coated with a transparent conductive film as described above on a transparent substrate; the transparent substrate is a flexible or rigid transparent glass substrate or a transparent polymer substrate, and the polymer substrate comprises a polyamide.
  • PI polyimide film
  • PET high temperature polyester film
  • PTFE Polytetrafluoroethylene film
  • PVDF polyvinylidene fluoride film
  • PP polypropylene film
  • another technical problem to be solved by the present invention is to provide a solar cell having a transparent upper electrode layer using the above transparent conductive film, which improves the near-infrared light absorption phenomenon of the zinc oxide-based transparent conductive film, thereby improving the solar cell. Conversion efficiency.
  • the solar cell provided by the present invention comprises a transparent upper electrode layer, wherein the transparent upper electrode layer is a transparent conductive film as described above.
  • the solar cell is a silicon germanium solar cell, an amorphous silicon solar cell, a crystalline silicon solar cell, a copper indium gallium selenide solar cell, an organic solar cell, a dye-sensitized solar cell, or a perovskite solar cell.
  • Fig. 1 is a graph showing the comparison of light transmittances of aluminum-doped zinc oxide films and titanium-doped zinc oxide films of different thicknesses according to the present invention.
  • FIG. 2 is a graph comparing the band gap wavelengths of the aluminum-doped zinc oxide films of different thicknesses and the titanium-doped zinc oxide films of the present invention.
  • Figure 3 is a graph showing changes in resistivity of different titanium-doped zinc oxide films of the present invention.
  • the transparent conductive film provided by the present invention comprises zinc, oxygen, and a titanium element, wherein the atomic proportion of zinc is 98 at% to 99 at%, and the atomic percentage of titanium is 1 at% to 2 at%.
  • the specific resistance of the transparent conductive film is (0.4 to 1) ⁇ 10 ⁇ 3 ⁇ cm, and when the thickness of the transparent conductive film is 1000 nm, the average transmittance of the near-infrared region (800 to 1300 nm) is ⁇ 80%. .
  • a 1000 nm thick titanium oxide film is taken as an example.
  • the average transmittance of the ⁇ 900 nm) wavelength visible region is comparable to or higher than the 900 nm thick and 1000 nm thick aluminum-doped zinc oxide film.
  • 1000 nm titanium-doped zinc oxide aluminum film The average transmittance is significantly better than that of the aluminum-doped zinc oxide film. It should be noted that when the thickness is above 1000 nm, the average transmittance of near-infrared light is decreased. Therefore, the thickness of 1000 nm or more is generally not selected, so other thicknesses of 1000 nm or more are generally used. The optical properties of the film are less relevant.
  • the transparent conductive film is prepared by depositing a titania-doped zinc oxide-based ceramic target on a substrate by a magnetron sputtering process; wherein the titania-doped zinc oxide-based ceramic target is doped with titanium dioxide
  • the range is from 1 at% to 2 at%.
  • the crystal structure of the formed transparent conductive film is a hexagonal wurtzite phase structure along a (002) orientation, the sheet resistance is (4 to 10) ⁇ / ⁇ , and the carrier concentration is (4 to 9.3) ⁇ 10 20 /cm. 3 , the mobility is (43 ⁇ 57.6) cm 2 V -1 S -1 .
  • the band gap wavelength of the transparent conductive film of the present invention is about 345 nm, compared with the control group 1 and the control group 2, in comparison with the band gap wavelengths of the aluminum-doped zinc oxide film and the titanium-doped zinc oxide film shown in FIG.
  • the aluminum-doped zinc oxide film has a band gap wavelength of 352.5 nm, and the invention has a small band gap wavelength and a high band gap energy.
  • the sputtering target for forming a transparent conductive film is a high-density titanium-doped zinc oxide-based target having a purity of not less than 99.9% and a relative density of not less than 94%.
  • the transparent titanium oxide-based zinc oxide-based ceramic target is doped with titanium dioxide in a range of 1.7 at%.
  • the resistivity of the conductive film is only 4 ⁇ 10 -4 ⁇ cm.
  • the preparation method of the sputtering target is preferably, but not limited to, a gel casting method, a cold isostatic pressing, a hot isostatic pressing, or a hot pressing sintering process, etc.; the sputtering target may be a planar target It can also be a rotating target, and so on.
  • the present invention also provides a transparent conductive substrate on which a transparent conductive film as described above is plated;
  • the transparent substrate is a flexible or rigid transparent glass substrate, or a transparent polymer substrate, the polymer
  • the substrate includes polyamide, polyimide film (PI), high temperature polyester film (PET), polytetrafluoroethylene film (PTFE), polyvinylidene fluoride film (PVDF), or polypropylene film (PP).
  • the present invention also provides a solar cell, which is a silicon germanium solar cell, an amorphous silicon solar cell, a copper indium gallium selenide solar cell, an organic solar cell, a dye-sensitized solar cell, or a perovskite solar cell.
  • a battery comprising: an upper substrate, a transparent upper electrode layer, a solar absorption layer, a lower electrode layer, and a lower substrate.
  • the transparent upper electrode layer is made of the above transparent conductive film.
  • the silicon germanium solar cell comprises: an upper substrate, a transparent upper electrode layer, and a silicon germanium solar absorber.
  • the layer is stacked, the lower electrode layer, and the lower substrate.
  • the amorphous silicon solar cell includes an upper substrate, a transparent upper electrode layer, an amorphous silicon solar absorption layer, a lower electrode layer, and a lower substrate.
  • the copper indium gallium selenide solar cell comprises: an upper substrate, a transparent upper electrode layer, a copper indium gallium selenide solar absorption layer, a lower electrode layer, and a lower substrate.
  • the organic solar cell includes an upper substrate, a transparent upper electrode layer, an organic solar absorption layer, a lower electrode layer, and a lower substrate.
  • the dye-sensitized solar cell comprises: an upper substrate, a transparent upper electrode layer, a dye-sensitized solar absorption layer, a lower electrode layer, and a lower substrate.
  • the perovskite solar cell comprises: an upper substrate, a transparent upper electrode layer, a perovskite solar absorption layer, a lower electrode layer, and a lower substrate.
  • the solar cell may further be a crystalline silicon solar cell comprising: a transparent upper electrode layer, a crystalline silicon solar absorber, and a lower electrode layer; and the transparent upper electrode layer adopts the above transparent conductive film.
  • Example 1 Sputtering a high-infrared transmittance-doped titanium-doped zinc oxide-based transparent conductive film.
  • the titanium-doped zinc oxide ceramic target for sputtering has a purity of 99.95% and a target relative density of 94%.
  • the planar target is installed in the vacuum chamber, and the direction of the target cathode and the film-forming substrate is adjusted to be vertical and vertical, and the titanium-doped zinc oxide target is not moved, and the film-forming substrate can be rotated to make the deposited film uniform.
  • Vacuum is applied to the bottom of the vacuum chamber to a vacuum of more than 1.0 ⁇ 10 -5 torr (Torr, pressure unit), and the vacuum pumping process is maintained for 30 minutes to ensure that the water vapor and air in the chamber are removed.
  • the substrate temperature was kept at 200 ° C, and 40 sccm of argon and 0.1-1 sccm (Standard Cubic Centimeter per Minute) oxygen were introduced into the vacuum chamber to adjust the vacuum chamber pressure to 3 mtorr.
  • the titanium oxide target corresponding to the titanium oxide target has a power of 200 W, an adjustment bias of -100 V, and a rotation speed of the film-forming substrate sample of 8 rpm, under which the film growth rate is ⁇ 25 nm/min.
  • the target is pre-sputtered for 30 min prior to the formal deposition of the film.
  • a titanium-doped zinc oxide transparent conductive film having a thickness of -1000 nm was prepared according to the above process conditions. Elemental analysis showed that the atomic ratio of titanium atoms to the sum of titanium atoms and zinc atoms in the titanium-doped zinc oxide transparent conductive film was 1.5% [Ti/(Ti+Zn)] ,, the titanium content was very low, and the crystal structure was The hexagonal wurtzite phase structure along the (002) orientation has a resistivity of 4.2 ⁇ 10 -4 ⁇ cm, a sheet resistance of 4.2 ⁇ / ⁇ , a carrier concentration of 4 ⁇ 10 20 /cm 3 , and a mobility of 43 cm. 2 V -1 S -1 , (800 to 1300 nm) has an average light transmittance of about 82% and a surface roughness of 3.2 nm.
  • Control group 1 Sputtering an aluminum-doped zinc oxide-based transparent conductive film.
  • the aluminum-doped zinc oxide ceramic target for sputtering has a purity of 99.95% and a target relative density of 99.3%.
  • the planar target is installed in the vacuum chamber, and the direction of the target cathode and the film-forming substrate is adjusted to be vertical and vertical, and the aluminum-doped zinc oxide target is not moved, and the film-forming substrate can be rotated to make the deposited film uniform.
  • Vacuum is applied to the vacuum chamber bottom to a vacuum of more than 1.0 ⁇ 10 -5 torr, and the vacuum pumping process is maintained for 30 minutes.
  • the substrate temperature was kept at 200 ° C, and 40 sccm of argon gas and 0.1-1 sccm of oxygen were introduced into the vacuum chamber to adjust the vacuum chamber pressure to 3 mtorr.
  • the RF power supply corresponding to the titanium-doped zinc oxide target was 200 W.
  • the adjustment bias was -100 V, and the film formation substrate rotation speed was 8 rpm. Under this condition, the film growth rate was ⁇ 23 nm/min. Before the film was officially deposited, the target was pre-sputtered for 30 min.
  • An aluminum-doped zinc oxide transparent conductive film having a thickness of -900 nm was prepared according to the above process conditions. Elemental analysis showed that the atomic ratio of aluminum atoms to the sum of aluminum atoms and zinc atoms in the aluminum-doped zinc oxide transparent conductive film was [Al/Al+Zn]] ⁇ 1.5%, and its crystal structure was hexagonal along the (002) orientation.
  • the wurtzite phase structure has a resistivity of 8.08 ⁇ 10 -4 ⁇ cm, a sheet resistance of 8.97 ⁇ / ⁇ , a carrier concentration of 2 ⁇ 10 20 /cm 3 , and a mobility of 12 cm 2 V -1 S -1 .
  • the average transmittance of (800 to 1300 nm) was ⁇ 74%, and the transmittance was as shown in Fig. 1, and the surface roughness was 6.7 nm.
  • Control 2 Sputtering an aluminum-doped zinc oxide-based transparent conductive film.
  • the aluminum-doped zinc oxide ceramic target for sputtering has a purity of 99.95% and a target relative density of 99.3%.
  • the planar target is installed in the vacuum chamber, and the direction of the target cathode and the film-forming substrate is adjusted to be vertical and vertical, and the aluminum-doped zinc oxide target is not moved, and the film-forming substrate can be rotated to make the deposited film uniform.
  • Vacuum is applied to the vacuum chamber bottom to a vacuum of more than 1.0 ⁇ 10 -5 torr, and the vacuum pumping process is maintained for 30 minutes.
  • the substrate temperature was kept at 200 ° C, and 40 sccm of argon gas and 0.1-1 sccm of oxygen were introduced into the vacuum chamber to adjust the vacuum chamber pressure to 3 mtorr.
  • the RF power supply corresponding to the titanium-doped zinc oxide target was 200 W.
  • the adjustment bias voltage is -100V, and the rotation speed of the film-forming substrate sample is 8 rpm. Under this condition, the film growth rate was ⁇ 23 nm/min, and the target was pre-sputtered for 30 min before the film was officially deposited.
  • An aluminum-doped zinc oxide transparent conductive film having a thickness of -1000 nm was prepared according to the above process conditions. Elemental analysis showed that the atomic ratio of aluminum atoms to the sum of aluminum atoms and zinc atoms in the aluminum-doped zinc oxide transparent conductive film was [Al/Al+Zn]] ⁇ 1.5%, and its crystal structure was hexagonal along the (002) orientation.
  • the wurtzite phase structure has a resistivity of 6.85 ⁇ 10 -4 ⁇ cm, a sheet resistance of 6.85 ⁇ / ⁇ , a carrier concentration of 2 ⁇ 10 20 /cm 3 , and a mobility of 13 cm 2 V -1 S -1
  • the transmittance is as shown in Fig. 1. The average transmittance (800 to 1300 nm) is ⁇ 66.8%, and the surface roughness is 7.3 nm.
  • Example 2 Sputtering a high-infrared transmittance-doped titanium-doped zinc oxide-based transparent conductive film.
  • the titanium-doped zinc oxide ceramic target for sputtering has a purity of 99.95% and a target relative density of 94%.
  • the planar target is installed in the vacuum chamber, and the direction of the target cathode and the film-forming substrate is adjusted to be vertical and vertical, and the titanium-doped zinc oxide target is not moved, and the film-forming substrate can be rotated to make the deposited film uniform.
  • Vacuum is applied to the bottom of the vacuum chamber to a vacuum of more than 1.0 ⁇ 10 -5 torr, and the vacuum pumping process is maintained for 30 minutes to ensure that the water vapor and air in the chamber are removed.
  • the substrate temperature was kept at 200 ° C, and 40 sccm of argon gas and 0.1-1 sccm of oxygen were introduced into the vacuum chamber to adjust the vacuum chamber pressure to 3 mtorr.
  • the RF power supply corresponding to the titanium-doped zinc oxide target was 200 W.
  • the adjustment bias was -100 V, and the film formation substrate rotation speed was 8 rpm. Under this condition, the film growth rate was ⁇ 25 nm/min, and the target was pre-sputtered for 30 min before the film was officially deposited.
  • a titanium-doped zinc oxide transparent conductive film having a thickness of -1000 nm was prepared according to the above process conditions.
  • the elemental analysis showed that the atomic ratio of titanium atom to the sum of titanium atom and zinc atom in the titanium-doped zinc oxide transparent conductive film was [Ti/(Ti+Zn)] ⁇ 1.7%, the titanium content was very low, and the crystal structure was along
  • the (002) oriented hexagonal wurtzite phase structure has a resistivity of 4.0 ⁇ 10 -4 ⁇ cm, a sheet resistance of 4.0 ⁇ / ⁇ , a carrier concentration of 4.3 ⁇ 10 20 /cm 3 , and a mobility of 57.6 cm. 2 V -1 S -1 , the average transmittance was -83.7% (800 to 1300 nm), and the surface roughness was 2.9 nm.
  • the transparent conductive film of the present invention can also be gel or chemical vapor deposition. (CVD), evaporation, atomic layer deposition (ALD), molecular beam epitaxy (MBE) and other processes are prepared.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • MBE molecular beam epitaxy
  • the present invention has at least one or more of the following features compared to the prior art:
  • High near-infrared wavelength (800-1300 nm) transmittance For the prior art of CN103646972B, CN105565798A, CN102719797A, CN101834009B, CN102534498A, etc., the present invention has a high near-infrared light (800-1300 nm) transmittance at 1000 nm. Under the condition of thickness, the average transmittance can reach 80% or more.
  • the light wavelength transmittance in the visible light region is significantly lower than the present invention, for example, the transmittance at the light wavelength of 550 nm exceeds 90%.
  • the invention is advantageous for improving solar cell conversion efficiency.
  • Small band gap wavelength For the prior art such as CN101834009B, CN102534498A, etc., the present invention has a smaller band gap wavelength. In CN101834009B, the band gap wavelength is about 375 nm, and in CN102534498A, the band gap wavelength is about 360 nm.
  • Lower resistivity The present invention has a lower resistivity in the prior art for CN103646972B, CN105565798A, CN102719797A, CN101834009B, CN102534498A and the like.
  • the specific resistance is 4 ⁇ 10 -4 ⁇ cm.
  • the resistivity is less than 1 ⁇ 10 -3 cm, the range of doped titanium dioxide is 1-2 at%. After the doping amount exceeds 2 at%, the resistivity increases with the increase of the doping amount.
  • the low resistivity characteristic of the present invention is advantageous for enhancing solar cell conversion efficiency.
  • Lower doping material cost CN103646972B, doped with B, doped with Al, doped with Ga. CN105565798A, doped with Ba 2 O 3 . CN102719797A, doped with Yb 3+ , Er 3+ , Tm 3+ . CN101834009B, doped with In. CN102534498A, doping elements such as Ga.
  • the present invention is doped with titanium dioxide, and the titanium dioxide is a non-rare earth metal oxide, which is inexpensive, and therefore, is advantageous for reducing the power generation cost of the solar cell.
  • the present invention is doped with titanium dioxide, has simple preparation process and better controllability, is beneficial to improving the performance of the transparent conductive film, and reducing the power generation cost of the solar cell.
  • Single target sputtering CN101834009B uses a multi-target co-sputtering technique of indium metal target and zinc oxide target, and CN102534498A uses a multi-target co-sputtering technique of gallium metal target and zinc oxide target.
  • This invention The use of a single titanium-doped zinc oxide target, using a single target sputtering technology, is conducive to simplifying sputtering technology, reducing equipment investment, and reducing the power generation cost of solar cells.

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Abstract

L'invention concerne une pellicule conductrice transparente et son procédé de préparation, une cible de pulvérisation, un substrat conducteur transparent et une cellule solaire. La pellicule mince conductrice transparente est fabriquée au moyen d'un matériau cible d'oxyde de zinc dopé au titane à haute densité et d'une technique de processus de pulvérisation par magnétron, et dans la pellicule conductrice transparente, les atomes de zinc occupent entre 98 % at et 99 % at, et les atomes de titane occupent entre 1 % at et 2 % at. La pellicule conductrice transparente a d'excellentes propriétés photoélectriques et une résistivité électrique inférieure à 1 × 10−3 Ω·cm, et lorsque l'épaisseur de la pellicule conductrice transparente est de 1000 nm, la transmittance moyenne n'est pas inférieure à 80 % dans la plage des infrarouges proches (800-1300 nm). La pellicule conductrice transparente peut être largement utilisée dans les champs techniques des cellules solaires, des dispositifs d'affichage, des panneaux tactiles, des diodes électroluminescentes, etc.
PCT/CN2017/111073 2016-11-15 2017-11-15 Pellicule conductrice transparente et son procédé de préparation, cible de pulvérisation, substrat conducteur transparent et cellule solaire WO2018090926A1 (fr)

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CN110436915A (zh) * 2019-08-05 2019-11-12 北京航大微纳科技有限公司 一种fbar压电层用氧化锌掺杂靶材材料及其制备方法
CN112941464A (zh) * 2021-01-28 2021-06-11 山东省科学院能源研究所 一种多层透明导电薄膜及其制备方法与应用
CN112941464B (zh) * 2021-01-28 2022-09-16 山东省科学院能源研究所 一种多层透明导电薄膜及其制备方法与应用
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CN114163141B (zh) * 2021-11-18 2024-01-26 成都赛林斯科技实业有限公司 一种抗辐射光学玻璃及其制备方法
CN114551717A (zh) * 2022-02-10 2022-05-27 中国矿业大学 钙钛矿型碱土矾酸盐薄膜铁电异质结构及其制备方法
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CN116395977A (zh) * 2023-02-20 2023-07-07 电子科技大学 一种应用于智能窗的氧化钒薄膜制备方法

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