CN115583803B - 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 abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 60
- 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
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 36
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 32
- 238000005496 tempering Methods 0.000 claims abstract description 23
- 230000000903 blocking effect Effects 0.000 claims abstract description 18
- 238000004544 sputter deposition Methods 0.000 claims description 141
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 60
- 230000004888 barrier function Effects 0.000 claims description 51
- 239000011701 zinc Substances 0.000 claims description 35
- 229910052786 argon Inorganic materials 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052814 silicon oxide Inorganic materials 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
- 238000010438 heat treatment Methods 0.000 claims description 9
- 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
- 238000004519 manufacturing process Methods 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 5
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 5
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003574 free electron Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 11
- 239000010410 layer Substances 0.000 description 135
- 239000010408 film Substances 0.000 description 55
- 239000000463 material Substances 0.000 description 21
- 239000011521 glass Substances 0.000 description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 238000000151 deposition Methods 0.000 description 10
- 238000000137 annealing Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 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
- 230000000052 comparative effect Effects 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
- 238000010276 construction 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
- 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
- 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
- 239000012466 permeate Substances 0.000 description 1
- 238000007747 plating 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
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Physical Vapour Deposition (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention discloses an AZO transparent conductive film and a preparation method thereof, wherein the AZO transparent conductive film comprises a substrate, and a Na ion blocking layer, a Zn layer, an AZO layer, an oxygen blocking layer and an antireflection layer which are sequentially obtained on the substrate through magnetron sputtering, and then the AZO transparent conductive film with the sheet resistance lower than 20Ω and the transmittance higher than 70% is finally obtained through high-temperature tempering treatment at 600-700 ℃.
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 been widely studied in the fields of flat panel display, film photovoltaics, energy saving for buildings, household appliance glass and the like because of the high light transmittance and conductivity. The Sn doped In 2O3 (ITO) film has the optimal conductive performance and light transmittance, and is a main current application material of the TCO film. However, since In is a rare metal element, it has little reserves on earth, has a certain toxicity, is expensive, and is difficult to be applied to thick film deposition and application. Fluorine doped SnO 2 conductive glass (FTO) produced on line has been partially applied in the fields of construction and photovoltaics, and is also called on-line Low-e glass, the conductivity of which is slightly poorer than that of ITO, although the manufacturing cost is relatively lower and the optical performance is excellent, the on-line 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 index can not be flexibly adjusted according to the requirements of customers. At present, trivalent metal element doped zinc oxide materials, particularly Al doped ZnO (AZO) 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 main flow of AZO film is prepared by magnetron sputtering, and the method is applied to the field of large-area industrial production, is the 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 film coating uniformity, strong controllability, lower cost and the like.
In order to meet the application of the AZO film in the Low-E glass field, the sheet resistance of the AZO film needs to be reduced to below 20 ohms, the conventional method is to increase the thickness of the AZO film to above 800nm, and the problems of increase of the number of targets, increase of preparation cost and the like are easily caused. The Chinese 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 firstly deposited on a glass substrate by adopting magnetron sputtering, the deposited film is subjected to rapid annealing treatment under argon atmosphere, and Zn atoms in the Zn layer permeate into the AZO layer and form Zn gap filling defects after annealing at the temperature of not more than 500 ℃, so that the carrier concentration is improved, the resistivity of the AZO film is further reduced to 3.8x -4 Ω & cm, and the sheet resistance is 32 ohms. 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 of small-area samples, and cannot meet the annealing treatment of large-area glass samples; the rapid annealing treatment can only produce in a single batch, can not realize continuous rapid production, has low production efficiency, and is not suitable for industrialized continuous production of large-area products;
(3) The production cost is higher: because AZO film is easy to oxidize in high-temperature air, the electrical property is reduced sharply, argon is used as protective atmosphere in the subsequent annealing process, and the manufacturing cost is further increased; and the large-area rapid annealing furnace is too expensive;
(4) The sheet resistance is still high and is 32 ohms, and the application requirement of lower than 20 ohms in the Low-E glass field cannot be met;
(5) As the thickness of the AZO film increases, the light reflection increases, which reduces the transmittance of the film
(6) Diffusion of Na ions into the film in glass at high temperature conditions can lead to performance degradation.
Disclosure of Invention
In order to achieve the above problems, the present invention 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 sequentially obtained on the substrate by magnetron sputtering; the Na ion blocking layer is formed by sputtering one of silicon, titanium oxide and zirconium oxide on the substrate, the oxygen blocking layer is formed by sputtering one of silicon oxide, silicon nitride, zirconium oxide, titanium oxide and zinc tin oxide on the AZO layer, and the anti-reflection layer is formed by sputtering one of silicon oxide and magnesium fluoride on the oxygen blocking layer.
Further, the thickness of the film layer of the Na ion blocking 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 film layer of the antireflection 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 of any dirt;
(2) Sputtering one of silicon, titanium oxide and zirconium oxide on a substrate by magnetron to obtain a Na ion barrier layer;
(3) Magnetron sputtering a Zn layer on the Na ion barrier layer;
(4) Magnetron sputtering 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 (3) magnetically sputtering one of silicon oxide and magnesium fluoride on the oxygen barrier layer to obtain the anti-reflection layer.
Further, the method further comprises the steps of:
(7) And carrying out high-temperature tempering treatment on the substrate sequentially deposited with the Na ion barrier layer, the Zn layer, the AZO layer, the oxygen barrier layer and the antireflection layer.
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: the background vacuum degree is 2.0-6.0X10 -3 Pa, the substrate temperature is 40-80 ℃, the sputtering power density is 6-10W/cm 2, and the sputtering gas is oxygen and argon with the mixing ratio of 1:2-1:3; the thickness of the film layer of the Na ion blocking 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: the background vacuum degree is 2.0-6.0X10 -3 Pa, the substrate temperature is 40-80 ℃, the sputtering power density is 10-30W/cm 2, and the sputtering gas is argon; the thickness of the film layer 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: the background vacuum degree is 2.0-6.0X10 -3 Pa, the substrate temperature is 50-100 ℃, the sputtering power density is 10-30W/cm 2, and the sputtering gas is oxygen and argon with the mixing ratio of 1:8-1:10; the thickness 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: the background vacuum degree is 2.0-6.0X10 -3 Pa, the substrate temperature is 40-80 ℃, the sputtering power density is 10-22W/cm 2, and 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: the background vacuum degree is 2.0-6.0X10 -3 Pa, the substrate temperature is 40-80 ℃, the sputtering power density is 8-15W/cm 2, and the sputtering gas is oxygen and argon with the mixing ratio of 1:2-1:3; the thickness of the film layer of the antireflection layer is 40-150 nm.
Further, in the step (7), the tempering temperature is 600-700 ℃, the tempering 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 AZO transparent conductive film with the thickness of the functional layer smaller than 500nm and the sheet resistance smaller than 20 ohms can be prepared.
(2) No hydrogen is introduced in the film plating process, so that the operation danger is reduced.
(3) Realizing the industrialized continuous production of large-area products: the continuous coating is adopted, then the continuous tempering line is used for carrying out subsequent heat treatment on the coated sample, the area of the prepared product can reach 1500mm multiplied by 2000mm at maximum, and the production efficiency is improved.
(4) And a barrier layer is adopted at the top of AZO, so that the oxidation of the film layer in the high-temperature air tempering heat treatment process is avoided.
(5) By introducing the antireflection layer, the visible light transmittance of the AZO film structure system is increased, and the average transmittance is increased from 79% to 84%.
(6) And a blocking layer is deposited on the surface of the glass, so that high-temperature diffusion of Na ions in the glass is reduced, and the performance of the conductive film is kept stable.
The conception, specific structure, and technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, features, and effects of the present invention.
Drawings
FIG. 1 is a schematic diagram of an AZO transparent conductive film according to a preferred embodiment of the present invention;
FIG. 2 is a graph showing the comparison of the transmittance of a thin film with or without an anti-reflection layer according to a preferred embodiment of the present invention;
FIG. 3 is a comparative view of the appearance of a film with or without a Na ion blocking layer according to a preferred embodiment of the present invention.
Detailed Description
The following description of the preferred embodiments of the present invention refers to the accompanying drawings, which make the technical contents thereof more clear and easy to understand. The present invention may be embodied in many different forms of embodiments and the scope of the present invention is not limited to only the embodiments described 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 dirt.
(2) The Na ion barrier layer 2 was deposited by magnetron sputtering. Depositing a barrier layer on the substrate treated in the step (1), wherein the sputtering conditions are as follows: the background vacuum degree is 2.0-6.0X10 -3 Pa, the substrate temperature is 40-80 ℃, the sputtering power density is 6-10W/cm 2, and the sputtering gas is oxygen and argon (the mixing ratio is 1:2-1:3). The sputtering material of the Na ion blocking layer is one of silicon, titanium oxide and zirconium oxide. The sputtering mode is one of direct current, intermediate frequency and radio frequency.
(3) The Zn layer 3 is sputter deposited by magnetron sputtering. The sputtering conditions were: the background vacuum degree is 2.0-6.0X10 - 3 Pa, the substrate temperature is 40-80 ℃, the sputtering power density is 10-30W/cm 2, and the sputtering gas is argon. The sputtering mode is one of direct current, intermediate frequency and radio frequency.
(4) And sputtering an AZO target (alumina in the target material: zinc oxide=2:98) by adopting a magnetron sputtering method, and depositing the AZO target on the zinc layer to form the AZO layer 4. The sputtering conditions were: the background vacuum degree is 2.0-6.0X10 -3 Pa, the substrate temperature is 50-100 ℃, the sputtering power density is 10-30W/cm 2, and the sputtering gas is oxygen and argon (the mixing ratio is 1:8-1:10). The sputtering mode is one of direct current, intermediate frequency and radio frequency.
(5) And sputtering on the AZO layer by adopting a magnetron sputtering method to deposit and form an oxygen barrier layer 5. The sputtering conditions were: the background vacuum degree is 2.0-6.0X10 -3 Pa, the substrate temperature is 40-80 ℃, the sputtering power density is 10-22W/cm 2, and the sputtering gas is nitrogen and argon (the mixing 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 improved, and the corrosion resistance and scratch resistance of the film layer can be effectively improved. The oxygen barrier layer is made of 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 sputtering on the oxygen barrier layer by adopting a magnetron sputtering method to deposit and form the anti-reflection layer 6. The sputtering conditions were: the background vacuum degree is 2.0-6.0X10 -3 Pa, the substrate temperature is 40-80 ℃, 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 sequentially deposited with the Na ion barrier layer, the Zn layer, the AZO layer, the oxygen barrier layer and the antireflection layer. The treatment conditions were as follows: the tempering temperature is 600-700 ℃, the tempering time is 180-220 s, the heating rate is 60-80 ℃/10s, and the cooling rate is 40-50 ℃/s. The tempering heat treatment process can enable Zn atoms to enter AZO to form gap zinc atoms, unpaired electrons are arranged on the outer electron orbits of the zinc atoms at the gap, free electrons are formed, and carrier concentration and conductivity of the film layer are improved.
Wherein, the film thickness of the Na ion barrier layer is 10-20 nm; the film thickness of the Zn layer is 5-30 nm; the film thickness of the AZO layer is 300-500 nm; the thickness of the oxygen barrier layer is 30-50 nm; the thickness of the antireflection 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 kept at 3 multiplied by 10 -3 Pa; silicon is used as a sputtering material, intermediate frequency sputtering is adopted, the temperature of a substrate is kept at 50 ℃, the sputtering power density is 8W/cm 2, sputtering gas is oxygen and argon with the mixing ratio of 1:2, and a Na ion barrier layer with the thickness of 12nm is sputtered and deposited on the substrate.
(3) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is kept at 3 multiplied by 10 -3 Pa; zn is used as sputtering material, DC sputtering is adopted, the temperature of the substrate is kept at 50 ℃, the sputtering density is 15W/cm 2, the sputtering gas is argon, and a Zn layer with the thickness of 10nm is sputtered and deposited on the Na ion barrier layer.
(4) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is kept at 3 multiplied by 10 -3 Pa; alumina: zinc oxide = 2:98 are sputtering materials, adopting intermediate frequency sputtering, keeping the temperature of the substrate at 50 ℃, the sputtering density at 15W/cm 2, sputtering gas being oxygen and argon with the mixing ratio of 1:10, and sputtering and depositing an AZO layer with the thickness of 300nm on the Zn layer.
(5) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is kept 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 ℃, the sputtering power density is 15W/cm 2, the sputtering gas is nitrogen and argon with the mixing ratio of 3:1, and a silicon nitride oxide barrier 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 kept at 3 multiplied by 10 -3 Pa; and (3) taking silicon as a sputtering material, adopting direct current sputtering, keeping the temperature of a substrate at 50 ℃, sputtering the silicon nitride anti-reflection layer with the thickness of 80nm on the oxygen barrier layer by sputtering with the sputtering gas of the mixed ratio of 1:2 oxygen and argon sputtering air pressure.
(7) Carrying out high-temperature tempering treatment on the glass substrate sequentially deposited with the Na ion barrier layer, the Zn layer, the AZO layer, the oxygen barrier layer and the anti-reflection layer, wherein the treatment conditions are as follows: the tempering temperature is 600 ℃, the tempering 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 a sputtering material, intermediate frequency sputtering is adopted, the temperature of a substrate is kept at 60 ℃, the sputtering density is 8W/cm 2, sputtering gas is oxygen and argon with the mixing ratio of 1:2.5, and a Na ion barrier layer with the thickness of 15nm is sputtered and deposited on the substrate.
(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 ℃, the sputtering density is 20W/cm 2, the sputtering gas is argon, and a Zn layer with the thickness of 15nm is sputtered and deposited on the Na ion barrier layer.
(4) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is kept at 5 multiplied by 10 -3 Pa; alumina: zinc oxide = 2:98 are sputtering materials, adopting intermediate frequency sputtering, keeping the temperature of the substrate at 60 ℃, the sputtering density at 20W/cm 2, sputtering gas being oxygen and argon with the mixing ratio of 1:9, and sputtering and depositing an AZO layer with the thickness of 400nm 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 ℃, 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 ℃, sputtering gas is oxygen and argon with the mixing ratio of 1:2.5, and an antireflection layer with the thickness of 100nm is sputtered and deposited on the oxygen barrier layer.
(7) Carrying out high-temperature tempering treatment on the glass substrate sequentially deposited with the Na ion barrier layer, the Zn layer, the AZO layer, the oxygen barrier layer and the anti-reflection layer, wherein the treatment conditions are as follows: the tempering temperature is 650 ℃, the tempering 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) The background vacuum degree of the vacuum cavity of the magnetron sputtering equipment is kept at 6 multiplied by 10 -3 Pa; and (3) using silicon as a sputtering material, adopting radio frequency sputtering, keeping the temperature of the substrate at 70 ℃, and sputtering the substrate at 10W/cm < 2 >, wherein sputtering gas is oxygen and argon in a mixing ratio of 1:3, and sputtering and depositing a Na ion barrier layer with the thickness of 20nm on the substrate.
(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 sputtering material, radio frequency sputtering is adopted, the temperature of the substrate is kept at 70 ℃, the sputtering density is 30W/cm 2, and a Zn layer with the thickness of 20nm is sputtered and 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; alumina: zinc oxide = 2:98 are sputtering materials, adopting radio frequency sputtering, keeping the temperature of the substrate at 70 ℃, the sputtering density at 30W/cm 2, sputtering gas being oxygen and argon with the mixing ratio of 1:10, and sputtering and depositing an AZO layer with the thickness of 500nm on the Zn layer.
(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 ℃, the sputtering power density is 22W/cm 2, the sputtering gas is nitrogen and argon with the mixing ratio of 3:2, the sputtering air pressure is 350Pa and 300Pa respectively, and an oxygen barrier layer with the thickness of 50nm is sputtered and deposited on an 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; and (3) using silicon oxide as a sputtering material, adopting radio frequency sputtering, keeping the temperature of a substrate at 70 ℃, and sputtering oxygen and argon with the mixing ratio of 1:3, wherein the sputtering air pressure is respectively 150Pa and 350Pa, and sputtering and depositing an antireflection layer with the thickness of 120nm on the oxygen barrier layer.
(7) Carrying out high-temperature tempering treatment on the glass substrate sequentially deposited with the Na ion barrier layer, the Zn layer, the AZO layer, the oxygen barrier layer and the anti-reflection layer, wherein the treatment conditions are as follows: the tempering temperature is 700 ℃, the tempering time is 220s, the heating rate is 80 ℃/10s, and the cooling rate is 50 ℃/s.
Fig. 2 is a graph comparing the film transmittance with or without the anti-reflection layer in the preferred embodiment, and it can be seen that the average transmittance of the film with the anti-reflection layer is 84% higher than 79% without the anti-reflection layer.
FIG. 3 is a comparative view of the appearance of a film with or without a Na ion blocking layer in a preferred embodiment, showing that the film produces spots due to Na ions precipitated to the film as shown in FIG. 3 (a); comparing fig. 3 (b) with the Na ion blocking layer, it can be seen that the generation of spots on the film is avoided after the Na ion blocking layer is added.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention without requiring creative effort by one of ordinary skill in the art. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (8)
1. The 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 antireflection layer which are sequentially obtained on the substrate through magnetron sputtering; the Na ion blocking layer is formed by sputtering one of silicon, titanium oxide and zirconium oxide on the substrate, the oxygen blocking layer is formed by sputtering one of silicon oxide, silicon nitride, zirconium oxide, titanium oxide and zinc tin oxide on the AZO layer, and the anti-reflection layer is formed by sputtering one of silicon oxide and magnesium fluoride on the oxygen blocking layer; wherein the thickness of the film layer of the Na ion blocking 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 film layer of the antireflection layer is 40-150 nm; the AZO transparent conductive film is subjected to high-temperature tempering treatment, so that Zn atoms in the Zn layer enter the AZO layer to form gap zinc atoms, unpaired electrons are arranged on an outer electron orbit of the zinc atoms at the gap, free electrons are formed, carrier concentration and conductivity of the film layer are improved, and finally the sheet resistance of the AZO transparent conductive film is smaller than 20 ohms.
2. A method for preparing an AZO transparent conductive film according to claim 1, comprising the steps of:
(1) Cleaning the substrate to avoid any dirt on the surface;
(2) Sputtering one of silicon, titanium oxide and zirconium oxide on a substrate by magnetron to obtain a Na ion barrier layer;
(3) Magnetron sputtering a Zn layer on the Na ion barrier layer;
(4) Magnetron sputtering 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) One of silicon oxide and magnesium fluoride is magnetically sputtered on the oxygen barrier layer to obtain an antireflection layer;
(7) And carrying out high-temperature tempering treatment on the substrate sequentially deposited with the Na ion barrier layer, the Zn layer, the AZO layer, the oxygen barrier layer and the antireflection layer, so that Zn atoms in the Zn layer enter the AZO layer to form gap zinc atoms, unpaired electrons exist on an outer electron orbit of the zinc atoms at the gap, free electrons are formed, the carrier concentration and the conductivity of the film are improved, and finally the sheet resistance of the AZO transparent conductive film is smaller than 20 ohms.
3. The method for preparing an AZO transparent conductive film according to claim 2, 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: the background vacuum degree is 2.0-6.0X10 -3 Pa, the substrate temperature is 40-80 ℃, the sputtering power density is 6-10W/cm 2, and the sputtering gas is oxygen and argon with the mixing ratio of 1:2-1:3; the thickness of the film layer of the Na ion blocking layer is 10-20 nm.
4. The method for preparing an AZO transparent conductive film according to claim 2, 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: the background vacuum degree is 2.0-6.0X10 -3 Pa, the substrate temperature is 40-80 ℃, the sputtering power density is 10-30W/cm 2, and the sputtering gas is argon; the thickness of the film layer of the Zn layer is 5-30 nm.
5. The method for preparing an AZO transparent conductive film according to claim 2, 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: the background vacuum degree is 2.0-6.0X10 -3 Pa, the substrate temperature is 50-100 ℃, the sputtering power density is 10-30W/cm 2, and the sputtering gas is oxygen and argon with the mixing ratio of 1:8-1:10; the thickness of the AZO layer is 300-500 nm.
6. The method for preparing an AZO transparent conductive film according to claim 2, 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: the background vacuum degree is 2.0-6.0X10 -3 Pa, the substrate temperature is 40-80 ℃, the sputtering power density is 10-22W/cm 2, and 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.
7. The method for preparing an AZO transparent conductive film according to claim 2, 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: the background vacuum degree is 2.0-6.0X10 -3 Pa, the substrate temperature is 40-80 ℃, the sputtering power density is 8-15W/cm 2, and the sputtering gas is oxygen and argon with the mixing ratio of 1:2-1:3; the thickness of the film layer of the antireflection layer is 40-150 nm.
8. The method for producing an AZO transparent conductive film according to claim 2, wherein in the step (7), the tempering temperature is 600 to 700 ℃, the tempering time is 180 to 220s, the heating rate is 60 to 80 ℃/10s, and the cooling rate is 40 to 50 ℃/s.
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