CN115583803A - AZO transparent conductive film and preparation method thereof - Google Patents
AZO transparent conductive film and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000004888 barrier function Effects 0.000 claims abstract description 62
- 239000000758 substrate Substances 0.000 claims abstract description 61
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000001301 oxygen Substances 0.000 claims abstract description 50
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 50
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 36
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 35
- 238000004544 sputter deposition Methods 0.000 claims description 134
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 60
- 229910052786 argon Inorganic materials 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000000903 blocking effect Effects 0.000 claims description 5
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 claims description 5
- 238000005496 tempering Methods 0.000 claims description 5
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 129
- 239000010408 film Substances 0.000 description 50
- 239000000463 material Substances 0.000 description 22
- 239000011521 glass Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 238000000151 deposition Methods 0.000 description 11
- 238000000137 annealing Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000003667 anti-reflective effect Effects 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3636—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing silicon, hydrogenated silicon or a silicide
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
- C03B27/012—Tempering or quenching glass products by heat treatment, e.g. for crystallisation; Heat treatment of glass products before tempering by cooling
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3642—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating containing a metal layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
Abstract
The invention discloses an AZO transparent conductive film and a preparation method thereof, the AZO transparent conductive film comprises a substrate, and a Na ion barrier layer, a Zn layer, an AZO layer, an oxygen barrier layer and an anti-reflection layer which are sequentially obtained on the substrate through magnetron sputtering, and then the substrate is subjected to high-temperature toughening treatment at 600-700 ℃, so that the AZO transparent conductive film with the sheet resistance lower than 20 omega and the transmittance higher than 70 percent is finally obtained.
Description
Technical Field
The invention relates to a zinc oxide transparent conductive oxide film, in particular to an AZO transparent conductive film and a preparation method thereof.
Background
Transparent Conductive Oxide (TCO) films have high light transmittance and conductivity, and thus are widely studied in the fields of flat panel display, film photovoltaics, building energy conservation, household appliance glass and the like. Wherein Sn is doped with In 2 O 3 The (ITO) film has the best conductive performance and light transmission performance, and is a main application material of the TCO film. However, since In is a rare metal element, it is not abundant on earth, has a certain toxicity, and is expensive, so it is difficult to be applied to the deposition and application of thick films. On-line produced fluorine doped SnO 2 Conductive glass (FTO) has also found partial application in the architectural, photovoltaic fields, also known as on-lineThe Low-e glass has slightly poorer conductivity than ITO, relatively lower manufacturing cost and excellent optical performance, but the online coating technology for manufacturing the FTO glass has larger limitation, because the film layer can only be synchronously prepared in the glass manufacturing process, and the main technical indexes cannot be flexibly adjusted according to the requirements of customers. At present, trivalent metal element doped zinc oxide materials, particularly Al doped ZnO (AZO for short) materials have the advantages of excellent optical characteristics, wide raw material sources, low price, no toxicity and the like, and are becoming the best choice for replacing ITO and FTO materials.
The preparation method of the AZO film mainstream is a magnetron sputtering method, is applied to the field of large-area industrial production, is a film deposition means with the most mature process and the most wide application, and has the advantages of high deposition rate, strong film adhesion, high coating uniformity, strong controllability, lower cost and the like.
In order to meet the application of the AZO film in the field of Low-E glass, the sheet resistance of the AZO film needs to be reduced to be less than 20 ohms, and the conventional method is to increase the thickness of the AZO film to be more than 800nm, which easily causes the series problems of increase of the number of targets, increase of the preparation cost and the like. The invention patent ZL201410011278.9 discloses an ultrathin (120 nm) AZO transparent conductive film with high carrier concentration and a preparation method thereof, wherein a Zn layer and an AZO layer are deposited on a glass substrate by adopting magnetron sputtering, the deposited film is subjected to rapid annealing treatment in an argon atmosphere, and Zn atoms in the Zn layer penetrate into the AZO layer and form a Zn gap filling defect by annealing at the temperature of not more than 500 ℃, so that the carrier concentration is improved, and the resistivity of the AZO film is further reduced to 3.8 multiplied by 10 -4 Omega cm, sheet resistance 32 ohm. However, the following problems still remain:
(1) Hydrogen is introduced in the sputtering process, so that the safety of the sputtering process is poor;
(2) The conventional rapid annealing furnace can only carry out annealing treatment on a small-area sample, and cannot meet the annealing treatment on a large-area glass sample; the rapid annealing treatment can be only carried out in a single batch, continuous rapid production cannot be realized, the production efficiency is low, and the method is not suitable for industrial continuous production of large-area products;
(3) The production cost is high: since the AZO film is easily oxidized in high-temperature air, the electrical performance is rapidly reduced, so that argon is adopted as a protective atmosphere in the subsequent annealing process, and the manufacturing cost is further increased; and large area rapid annealing furnaces are too expensive;
(4) The sheet resistance is still high and is 32 ohms, and the application requirement of being lower than 20 ohms in the field of Low-E glass cannot be met;
(5) As the thickness of the AZO film increases, the light reflection increases, and the transmittance of the film is reduced
(6) The diffusion of Na ions into the film in glass at high temperatures leads to degradation of the properties.
Disclosure of Invention
In order to realize the problems, the invention firstly provides an AZO transparent conductive film, which comprises a substrate, and a Na ion barrier layer, a Zn layer, an AZO layer, an oxygen barrier layer and an antireflection layer which are sequentially formed on the substrate through magnetron sputtering; wherein the Na ion barrier layer is obtained by sputtering one of silicon, titanium oxide and zirconium oxide on the substrate, the oxygen barrier layer is obtained by sputtering one of silicon oxide, silicon nitride, zirconium oxide, titanium oxide and zinc tin oxide on the AZO layer, and the antireflection layer is obtained by sputtering one of silicon oxide and magnesium fluoride on the oxygen barrier layer.
Further, the thickness of the film layer of the Na ion barrier layer is 10-20 nm; the thickness of the film layer of the Zn layer is 5-30 nm; the thickness of the film layer of the AZO layer is 300-500 nm; the thickness of the film layer of the oxygen barrier layer is 30-50 nm; the thickness of the anti-reflection layer is 40-150 nm.
The invention also provides a preparation method of the AZO transparent conductive film, which comprises the following steps:
(1) Cleaning the substrate to ensure that the surface is free from any dirt;
(2) Performing magnetron sputtering on one of silicon, titanium oxide and zirconium oxide on a substrate to obtain a Na ion barrier layer;
(3) Magnetron sputtering a Zn layer on the Na ion barrier layer;
(4) Performing magnetron sputtering of an AZO layer on the Zn layer;
(5) Performing magnetron sputtering on one of silicon oxide, silicon nitride, zirconium oxide, titanium oxide and zinc tin oxide on the AZO layer to obtain an oxygen barrier layer;
(6) And performing magnetron sputtering on the oxygen barrier layer to obtain the antireflection layer.
Further, the method also comprises the following steps:
(7) And carrying out high-temperature tempering treatment on the substrate on which the Na ion barrier layer, the Zn layer, the AZO layer, the oxygen barrier layer and the antireflection layer are sequentially deposited.
Further, in the step (2), the sputtering mode is one of direct current, intermediate frequency and radio frequency, and the sputtering conditions are as follows: background vacuum degree of 2.0-6.0X 10 -3 Pa, the substrate temperature is 40-80 ℃, and the sputtering power density is 6-10W/cm 2 The sputtering gas is oxygen and argon with the mixing ratio of 1:2-1:3; the thickness of the Na ion barrier layer is 10-20 nm.
Further, in the step (3), the sputtering mode is one of direct current, intermediate frequency and radio frequency, and the sputtering conditions are as follows: background vacuum degree of 2.0-6.0X 10 -3 Pa, the substrate temperature is 40-80 ℃, and the sputtering power density is 10-30W/cm 2 The sputtering gas is argon; the thickness of the Zn layer is 5-30 nm.
Further, in the step (4), the sputtering mode is one of direct current, intermediate frequency and radio frequency, and the sputtering conditions are as follows: background vacuum degree of 2.0-6.0X 10 -3 Pa, the substrate temperature is 50-100 ℃, and the sputtering power density is 10-30W/cm 2 The sputtering gas is oxygen and argon with the mixing ratio of 1:8-1; the thickness of the film layer of the AZO layer is 300-500 nm.
Further, in the step (5), the sputtering mode is one of direct current, intermediate frequency and radio frequency, and the sputtering conditions are as follows: background vacuum degree of 2.0-6.0X 10 -3 Pa, the substrate temperature is 40-80 ℃, and the sputtering power density is 10-22W/cm 2 The sputtering gas is nitrogen and argon with the mixing ratio of 3:1-3:2; the thickness of the film layer of the oxygen barrier layer is 30-50 nm.
Further, in the step (6), the sputtering mode is one of direct current, intermediate frequency and radio frequency, and the sputtering conditions are as follows: background vacuum degree of 2.0-6.0X 10 -3 Pa, the substrate temperature is 40-80 ℃, and the sputtering power density is 8-15W/cm 2 The sputtering gas is oxygen and argon with the mixing ratio of 1:2-1:3; the thickness of the anti-reflection layer is 40-150 nm.
Further, in the step (7), the toughening temperature is 600-700 ℃, the toughening time is 180-220 s, the heating rate is 60-80 ℃/10s, and the cooling rate is 40-50 ℃/s.
The invention has the technical effects that:
(1) The preparation of the AZO transparent conductive film with the functional layer thickness less than 500nm and the sheet resistance less than 20 ohms can be realized.
(2) No hydrogen is introduced in the film plating process, so that the operation risk is reduced.
(3) The industrial continuous production of large-area products is realized: the continuous film coating is adopted, and then the continuous tempering line is utilized to carry out subsequent heat treatment on the plated sample, so that the area of the prepared product can maximally reach 1500mm multiplied by 2000mm, and the production efficiency is improved.
(4) And a barrier layer is adopted on the top of the AZO, so that the oxidation of the film layer in the high-temperature air tempering heat treatment process is avoided.
(5) The introduction of the antireflection layer increases the visible light transmittance of an AZO thin film structural system, and the average transmittance is increased from 79% to 84%.
(6) And a barrier layer is deposited on the surface of the glass, so that the high-temperature diffusion of Na ions in the glass is reduced, and the stable performance of the conductive film is kept.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
FIG. 1 is a structural diagram of an AZO transparent conductive film in a preferred embodiment of the present invention;
FIG. 2 is a graph comparing the transmittance of films with and without an antireflective layer in a preferred embodiment of the invention;
FIG. 3 is a comparison graph of the appearance of a film with and without a Na ion blocking layer in a preferred embodiment of the present invention.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
The invention provides an AZO transparent conductive film with a structure shown in figure 1, which comprises a substrate, and a Na ion barrier layer, a Zn layer, an AZO layer, an oxygen barrier layer and an antireflection layer which are sequentially obtained on the substrate through magnetron sputtering, wherein the preparation method comprises the following steps:
(1) The glass substrate 1 is cleaned to ensure that the surface is free of any contamination.
(2) And depositing the Na ion barrier layer 2 by adopting a magnetron sputtering method. Depositing and forming a barrier layer on the substrate processed in the step (1), wherein the sputtering conditions are as follows: background vacuum degree of 2.0-6.0X 10 -3 Pa, the substrate temperature is 40-80 ℃, and the sputtering power density is 6-10W/cm 2 The sputtering gas is oxygen and argon (the mixing ratio is 1:2-1:3). The sputtering material of the Na ion barrier layer is one of silicon, titanium oxide and zirconium oxide. The sputtering mode is one of direct current, intermediate frequency and radio frequency.
(3) And sputtering and depositing a Zn layer 3 by adopting a magnetron sputtering method. The sputtering conditions were: background vacuum degree of 2.0-6.0X 10 - 3 Pa, the substrate temperature is 40-80 ℃, and the sputtering power density is 10-30W/cm 2 The sputtering gas is argon. The sputtering mode is one of direct current, intermediate frequency and radio frequency.
(4) And (3) sputtering an AZO target (aluminum oxide in the target material: zinc oxide =2 98) by a magnetron sputtering method to deposit and form an AZO layer 4 on the zinc layer. The sputtering conditions were: background vacuum degree of 2.0-6.0X 10 -3 Pa, the substrate temperature is 50-100 ℃, and the sputtering power density is 10-30W/cm 2 The sputtering gas is oxygen and argon (mixing ratio is 1:8-1. The sputtering mode is one of direct current, intermediate frequency and radio frequency.
(5) And depositing an oxygen barrier layer 5 on the AZO layer by adopting a magnetron sputtering method. The sputtering conditions were: background vacuum degree of 2.0-6.0X 10 -3 Pa, the substrate temperature is 40-80 ℃, and the sputtering power density is 10-22W/cm 2 The sputtering gas is nitrogen and argon (mixed)The ratio is 3:1-3:2). The compact barrier layer can effectively isolate the AZO conductive film from reacting with oxygen in the air, so that the durability of the film layer is increased, and the corrosion resistance and the scratch resistance of the film layer can be effectively improved. The material used by the oxygen barrier layer is one of silicon oxide, silicon nitride, zirconium oxide, titanium oxide and zinc tin oxide. The sputtering mode is one of direct current, intermediate frequency and radio frequency.
(6) And depositing an anti-reflection layer 6 on the oxygen barrier layer by adopting a magnetron sputtering method. The sputtering conditions were: background vacuum degree of 2.0-6.0X 10 -3 Pa, the substrate temperature is 40-80 ℃, and the sputtering power density is 8-15W/cm 2 The sputtering gas is oxygen and argon (the mixing ratio is 1:2-1:3); the sputtering mode is one of direct current, intermediate frequency and radio frequency. The anti-reflection layer is generally used for increasing the light transmittance, and the thickness can be increased according to the requirement to change the light transmittance of the film layer. The material used for the anti-reflection layer is one of silicon oxide and magnesium fluoride.
(7) And carrying out high-temperature tempering treatment on the glass substrate on which the Na ion barrier layer, the Zn layer, the AZO layer, the oxygen barrier layer and the antireflection layer are sequentially deposited. The treatment conditions were as follows: the toughening temperature is 600-700 ℃, the toughening time is 180-220 s, the heating rate is 60-80 ℃/10s, and the cooling rate is 40-50 ℃/s. In the toughening heat treatment process, zn atoms can enter AZO to form gap position zinc atoms, unpaired electrons are arranged on outer electron orbits of the gap position zinc atoms to form free electrons, and the carrier concentration and the conductivity of the film layer are improved.
Wherein the thickness of the Na ion barrier layer is 10-20 nm; the thickness of the Zn layer is 5-30 nm; the thickness of the AZO layer is 300-500 nm; the thickness of the oxygen barrier layer is 30-50 nm; the thickness of the anti-reflection layer is 40-150 nm.
Example 1：
(1) The cleaned ultra-white glass is used as a substrate.
(2) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is maintained at 3 multiplied by 10 -3 Pa; using silicon as sputtering material, adopting intermediate frequency sputtering, keeping the substrate temperature at 50 deg.C, and the sputtering power density is 8W/cm 2 The sputtering gas is oxygen with the mixing ratio of 1:2And argon, a Na ion barrier layer with a thickness of 12nm was sputter deposited on the substrate.
(3) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is maintained at 3 multiplied by 10 -3 Pa; zn is used as a sputtering material, direct current sputtering is adopted, the temperature of the substrate is kept at 50 ℃, and the sputtering density is 15W/cm 2 And sputtering and depositing a Zn layer with the thickness of 10nm on the Na ion barrier layer by using argon as sputtering gas.
(4) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is maintained at 3 multiplied by 10 -3 Pa; the method comprises the following steps of mixing alumina: zinc oxide =2:98 AZO is a sputtering material, intermediate frequency sputtering is adopted, the substrate temperature is kept at 50 ℃, and the sputtering density is 15W/cm 2 And sputtering an AZO layer with the thickness of 300nm on the Zn layer by using oxygen and argon in a mixing ratio of 1.
(5) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is maintained at 3 multiplied by 10 -3 Pa; using silicon as sputtering material, adopting DC sputtering, keeping the substrate temperature at 50 deg.C, and the sputtering power density at 15W/cm 2 The sputtering gas is nitrogen and argon with the mixing ratio of 3:1, and a silicon nitride oxygen blocking layer with the thickness of 30nm is sputtered and deposited on the AZO layer.
(6) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is maintained at 3 multiplied by 10 -3 Pa; silicon is used as a sputtering material, direct current sputtering is adopted, the temperature of a substrate is kept at 50 ℃, sputtering gas is the sputtering pressure of 1:2 oxygen and argon in a mixing ratio, and a silicon nitride antireflection layer with the thickness of 80nm is sputtered and deposited on an oxygen barrier layer.
(7) Carrying out high-temperature toughening treatment on the glass substrate on which the Na ion barrier layer, the Zn layer, the AZO layer, the oxygen barrier layer and the antireflection layer are sequentially deposited, wherein the treatment conditions are as follows: the toughening temperature is 600 ℃, the toughening time is 180s, the heating rate is 60 ℃/10s, and the cooling rate is 40 ℃/s.
Example 2：
(1) The cleaned ultra-white glass is used as a substrate.
(2) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is kept at 5 multiplied by 10 -3 Pa; titanium oxide is used as sputtering material, intermediate frequency sputtering is adopted, and the temperature of the substrate is keptThe temperature is kept at 60 ℃, and the sputtering density is 8W/cm 2 The sputtering gas is oxygen and argon with the mixing ratio of 1.
(3) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is kept at 5 multiplied by 10 -3 Pa; zn is used as a sputtering material, intermediate frequency sputtering is adopted, the temperature of a substrate is kept at 60 ℃, and the sputtering density is 20W/cm 2 And sputtering and depositing a Zn layer with the thickness of 15nm on the Na ion barrier layer by using argon as sputtering gas.
(4) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is kept at 5 multiplied by 10 -3 Pa; the method comprises the following steps of mixing alumina: zinc oxide =2:98 AZO is a sputtering material, intermediate frequency sputtering is adopted, the substrate temperature is kept at 60 ℃, and the sputtering density is 20W/cm 2 The sputtering gas is oxygen and argon with the mixing ratio of 1:9, and an AZO layer with the thickness of 400nm is sputtered and deposited on the Zn layer.
(5) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is kept at 5 multiplied by 10 -3 Pa; silicon nitride is used as a sputtering material, intermediate frequency sputtering is adopted, the temperature of a substrate is kept at 60 ℃, and the sputtering power density is 18W/cm 2 The sputtering gas is nitrogen and argon with the mixing ratio of 2:1, and an oxygen barrier layer with the thickness of 40nm is sputtered and deposited on the AZO layer.
(6) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is kept at 5 multiplied by 10 -3 Pa; silicon oxide is used as a sputtering material, intermediate frequency sputtering is adopted, the temperature of a substrate is kept at 60 ℃, the sputtering gas is oxygen and argon with the mixing ratio of 1.
(7) Carrying out high-temperature toughening treatment on the glass substrate on which the Na ion barrier layer, the Zn layer, the AZO layer, the oxygen barrier layer and the antireflection layer are sequentially deposited, wherein the treatment conditions are as follows: the toughening temperature is 650 ℃, the toughening time is 200s, the heating rate is 70 ℃/10s, and the cooling rate is 45 ℃/s.
Example 3
(1) The cleaned ultra-white glass is used as a substrate.
(2) Maintaining the background vacuum degree of the vacuum cavity of the magnetron sputtering equipmentAt 6X 10 -3 Pa; using silicon as a sputtering material, adopting radio frequency sputtering, keeping the temperature of a substrate at 70 ℃, sputtering the substrate at the density of 10W/cm < 2 >, and sputtering a Na ion barrier layer with the thickness of 20nm on the substrate by sputtering and depositing oxygen and argon in the mixing ratio of 1:3 as sputtering gas.
(3) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is kept at 6 multiplied by 10 -3 Pa; zn is used as a sputtering material, radio frequency sputtering is adopted, the temperature of a substrate is kept at 70 ℃, and the sputtering density is 30W/cm 2 A Zn layer with a thickness of 20nm was sputter deposited on the Na ion barrier layer.
(4) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is kept at 6 multiplied by 10 -3 Pa; the method comprises the following steps of mixing alumina: zinc oxide =2:98 AZO is a sputtering material, radio frequency sputtering is adopted, the temperature of the substrate is kept at 70 ℃, and the sputtering density is 30W/cm 2 And sputtering oxygen and argon in a mixing ratio of 1.
(5) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is kept at 6 multiplied by 10 -3 Pa; zirconium oxide is used as a sputtering material, radio frequency sputtering is adopted, the temperature of a substrate is kept at 70 ℃, and the sputtering power density is 22W/cm 2 The sputtering gas is nitrogen and argon with the mixing ratio of 3:2, the sputtering pressure is 350Pa and 300Pa respectively, and an oxygen barrier layer with the thickness of 50nm is sputtered and deposited on the AZO layer.
(6) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is kept at 6 multiplied by 10 -3 Pa; silicon oxide is used as a sputtering material, radio frequency sputtering is adopted, the temperature of a substrate is kept at 70 ℃, sputtering gases are oxygen and argon with the mixing ratio of 1:3, the sputtering pressure is 150Pa and 350Pa respectively, and an antireflection layer with the thickness of 120nm is sputtered and deposited on an oxygen barrier layer.
(7) Carrying out high-temperature toughening treatment on the glass substrate on which the Na ion barrier layer, the Zn layer, the AZO layer, the oxygen barrier layer and the antireflection layer are sequentially deposited, wherein the treatment conditions are as follows: the toughening temperature is 700 ℃, the toughening time is 220s, the heating rate is 80 ℃/10s, and the cooling rate is 50 ℃/s.
Fig. 2 is a comparison of the transmission of the film with and without the antireflective layer in the preferred embodiment, showing that the average transmission of the film with the antireflective layer is 84% higher than 79% of the film without the antireflective layer.
FIG. 3 is a comparison of the appearance of the film with and without the Na ion blocking layer in the preferred embodiment, and it can be seen that in the absence of the Na ion blocking layer, as shown in FIG. 3 (a), the film layer is spotted due to the precipitation of Na ions into the film layer; comparing with fig. 3 (b), the addition of the Na ion barrier layer can be seen to prevent the generation of spots on the film.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the prior art according to the concepts of the present invention should be within the scope of protection determined by the claims.
Claims (10)
1. An AZO transparent conductive film is characterized by comprising a substrate, and a Na ion barrier layer, a Zn layer, an AZO layer, an oxygen barrier layer and an anti-reflection layer which are sequentially obtained on the substrate through magnetron sputtering; wherein the Na ion barrier layer is obtained by sputtering one of silicon, titanium oxide and zirconium oxide on the substrate, the oxygen barrier layer is obtained by sputtering one of silicon oxide, silicon nitride, zirconium oxide, titanium oxide and zinc tin oxide on the AZO layer, and the antireflection layer is obtained by sputtering one of silicon oxide and magnesium fluoride on the oxygen barrier layer.
2. The AZO transparent conductive film according to claim 1, wherein the Na ion blocking layer has a film thickness of 10 to 20nm; the thickness of the film layer of the Zn layer is 5-30 nm; the thickness of the film layer of the AZO layer is 300-500 nm; the thickness of the film layer of the oxygen barrier layer is 30-50 nm; the thickness of the anti-reflection layer is 40-150 nm.
3. A preparation method of an AZO transparent conductive film is characterized by comprising the following steps:
(1) Cleaning the substrate to make the surface of the substrate free from any dirt;
(2) Performing magnetron sputtering on one of silicon, titanium oxide and zirconium oxide on a substrate to obtain a Na ion barrier layer;
(3) Magnetron sputtering a Zn layer on the Na ion barrier layer;
(4) Performing magnetron sputtering of an AZO layer on the Zn layer;
(5) Performing magnetron sputtering on one of silicon oxide, silicon nitride, zirconium oxide, titanium oxide and zinc tin oxide on the AZO layer to obtain an oxygen barrier layer;
(6) And performing magnetron sputtering on the oxygen barrier layer to obtain the antireflection layer.
4. The AZO transparent conductive film preparation method according to claim 3, further comprising the steps of:
(7) And carrying out high-temperature tempering treatment on the substrate on which the Na ion barrier layer, the Zn layer, the AZO layer, the oxygen barrier layer and the antireflection layer are sequentially deposited.
5. The AZO transparent conductive film preparation method according to claim 3, wherein in the step (2), the sputtering mode is one of direct current, intermediate frequency and radio frequency, and the sputtering conditions are as follows: background vacuum degree of 2.0-6.0X 10 -3 Pa, the substrate temperature is 40-80 ℃, and the sputtering power density is 6-10W/cm 2 The sputtering gas is oxygen and argon with the mixing ratio of 1:2-1:3; the thickness of the Na ion barrier layer is 10-20 nm.
6. The AZO transparent conductive film preparation method according to claim 3, wherein in the step (3), the sputtering mode is one of direct current, intermediate frequency and radio frequency, and the sputtering conditions are as follows: background vacuum degree of 2.0-6.0X 10 -3 Pa, the substrate temperature is 40-80 ℃, and the sputtering power density is 10-30W/cm 2 The sputtering gas is argon; the thickness of the Zn layer is 5-30 nm.
7. The AZO transparent conductive film preparation method according to claim 3, wherein in the step (4), the sputtering mode is one of direct current, intermediate frequency and radio frequency, and the sputtering conditions are as follows: background vacuum degree of 2.0-6.0X 10 -3 Pa, substrate temperature of 50-100 deg.C, sputtering power densityThe degree is 10-30W/cm 2 The sputtering gas is oxygen and argon with the mixing ratio of 1:8-1; the thickness of the film layer of the AZO layer is 300-500 nm.
8. The AZO transparent conductive film preparation method according to claim 3, wherein in the step (5), the sputtering mode is one of direct current, intermediate frequency and radio frequency, and the sputtering conditions are as follows: background vacuum degree of 2.0-6.0X 10 -3 Pa, the substrate temperature is 40-80 ℃, and the sputtering power density is 10-22W/cm 2 The sputtering gas is nitrogen and argon with the mixing ratio of 3:1-3:2; the thickness of the film layer of the oxygen barrier layer is 30-50 nm.
9. The AZO transparent conductive film preparation method according to claim 3, wherein in the step (6), the sputtering mode is one of direct current, intermediate frequency and radio frequency, and the sputtering conditions are as follows: background vacuum degree of 2.0-6.0X 10 -3 Pa, the substrate temperature is 40-80 ℃, and the sputtering power density is 8-15W/cm 2 The sputtering gas is oxygen and argon with the mixing ratio of 1:2-1:3; the thickness of the anti-reflection layer is 40-150 nm.
10. The AZO transparent conductive film preparation method according to claim 4, wherein in the step (7), the toughening temperature is 600-700 ℃, the toughening time is 180-220 s, the temperature rise rate is 60-80 ℃/10s, and the temperature drop rate is 40-50 ℃/s.
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