CN115537741A - Film structure, preparation method thereof and electronic device - Google Patents
Film structure, preparation method thereof and electronic device Download PDFInfo
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- CN115537741A CN115537741A CN202110728289.9A CN202110728289A CN115537741A CN 115537741 A CN115537741 A CN 115537741A CN 202110728289 A CN202110728289 A CN 202110728289A CN 115537741 A CN115537741 A CN 115537741A
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- 238000002360 preparation method Methods 0.000 title abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 80
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052709 silver Inorganic materials 0.000 claims abstract description 78
- 239000004332 silver Substances 0.000 claims abstract description 78
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 65
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 60
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 37
- 229910052786 argon Inorganic materials 0.000 claims abstract description 34
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 26
- 238000000151 deposition Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000004544 sputter deposition Methods 0.000 claims description 10
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 238000002834 transmittance Methods 0.000 abstract description 18
- 230000007547 defect Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 21
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 9
- 230000005012 migration Effects 0.000 description 7
- 238000013508 migration Methods 0.000 description 7
- 150000003378 silver Chemical class 0.000 description 7
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 238000005381 potential energy Methods 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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Classifications
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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
- C23C14/22—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
-
- 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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- Engineering & Computer Science (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a film structure, a preparation method thereof and an electronic device, wherein the method comprises the following steps: providing a first metal oxide film; depositing a silver film on one side of the first metal oxide film by using a magnetron sputtering method; and depositing a second metal oxide film on the side of the silver film away from the first oxide film; the working gas of the magnetron sputtering method is argon and nitrogen, and the argon and the nitrogen are used as the working gas to form the continuous silver film, so that the defect that the film thickness, the light transmittance and the electric property are difficult to be considered in the prior art is overcome, and the photoelectric property of the film structure is improved.
Description
Technical Field
The invention relates to the field of electronic devices, in particular to a film structure, a preparation method thereof and an electronic device.
Background
Indium Tin Oxide (ITO) is a transparent conductive oxide that is widely used in the field of optoelectronic devices. However, high-performance ITO must be annealed at high temperature, and thus cannot be compatible with an organic substrate, ITO prepared at room temperature has high resistivity, the only way to improve conductivity is to increase the thickness, and the light transmittance is reduced while the film brittleness is increased along with the increase of the thickness, and the film is volatile after being bent for many times, and cannot meet the requirements of a flexible device; on the other hand, the lack of indium (In) resources and the large market demand of transparent conductive films have also limited the large-scale use of ITO transparent conductive films.
The film structure benefits from a specific Oxide-Metal-Oxide (OMO) sandwich structure, the preparation process is simple, mass production is easy to realize, meanwhile, the flexibility and the stability are good, and the film structure is suitable for developing cheap and flexible transparent conductive electrodes. At present, the most studied and most excellent photoelectric property is the film structure of metal oxide-silver-metal oxide (MO/Ag/MO), but silver has poor wettability on a metal oxide film, so that a silver layer is easy to form a three-dimensional island-shaped growth mode on the metal oxide film, and an ultrathin continuous silver film is difficult to obtain. Therefore, how to obtain an ultrathin continuous interlayer metal by suppressing the three-dimensional island-like growth of silver on the surface of a metal oxide has been an obstacle to further improvement of the performance of a film structure electrode.
Disclosure of Invention
The invention provides a film structure, a preparation method thereof and an electronic device, which can obtain a continuous silver film on the surface of a metal oxide film, thereby improving the photoelectric property of the film structure and being suitable for preparing the electronic device with stable performance.
In a first aspect, an embodiment of the present invention provides a method for preparing a film structure, where the method includes:
providing a first metal oxide film;
depositing a silver film on one side of the first metal oxide film by using a magnetron sputtering method; and
depositing a second metal oxide film on the side of the silver film away from the first oxide film;
wherein, the working gas of the magnetron sputtering method is argon and nitrogen.
In some embodiments, the flow ratio of nitrogen to argon is (0.1 to 1): 100.
in some embodiments, the argon, and/or the nitrogen, has a purity greater than or equal to 99.0%.
In some embodiments, the first metal oxide and the second metal oxide are independently selected from ZnO, mgZnO, alZnO, tiO 2 、MoO 3 At least one of the first oxide andthe second oxides are the same or different.
In some embodiments, the silver film has a thickness of 5 to 10 nanometers.
In some embodiments, a pressure atmosphere of 0.5 to 5Pa is provided during the deposition of the silver film using the magnetron sputtering method.
In some embodiments, the depositing a silver film on one side of the first metal oxide film using a magnetron sputtering method includes: providing a silver target, introducing nitrogen as a working gas into argon by using a magnetron sputtering device, and sputtering a silver film on one side of the first metal oxide film after fully mixing.
In some embodiments, the purity of the silver target is greater than or equal to 99.9%.
In a second aspect, the present invention also provides a membrane structure made by the method of any of the above embodiments.
In a third aspect, the present invention also provides an electronic device comprising the film structure described in the above embodiments.
In some embodiments, the above electronic device includes a first electrode and a second electrode disposed oppositely, and a light emitting layer disposed between the first electrode and the second electrode, the material of the first electrode or the second electrode being the film structure.
In a fourth aspect, the present invention also provides a method for manufacturing an electronic device including a first electrode and a second electrode which are oppositely disposed, and a light-emitting layer disposed between the first electrode and the second electrode, wherein the first electrode or the second electrode is a film structure, and the method for manufacturing the film structure includes:
providing a first metal oxide film;
depositing a silver film on one side of the first metal oxide film by using a magnetron sputtering method; and
depositing a second metal oxide film on a side of the silver film remote from the first oxide film,
wherein, the working gas of the magnetron sputtering method is argon and nitrogen.
Has the beneficial effects that:
the invention provides a film structure and a preparation method of an electronic device, wherein argon and nitrogen are used as working gases, the nitrogen can inhibit migration and fusion of silver clusters (Ag (N)) on the surface of a metal oxide in the growth process, and the migration of the Ag (N) clusters on the surface of the metal oxide is inhibited, so that the growth process of the Ag (N) clusters is mainly bridged by changing the appearance of surface atoms of adjacent clusters under the trend of surface chemical potential energy. The growth mode greatly inhibits the three-dimensional island growth of the silver film, inhibits the formation and growth of grooves or holes, can form a continuous silver film, and breaks through the defect that the prior art is difficult to consider the film thickness, the light transmittance and the electrical property, thereby improving the photoelectric property of the film structure. In addition, the nitrogen has good stability, the target poisoning probability can be reduced, the doping amount is controllable, and the stability of the performance of the electronic device can be improved.
The invention provides a film structure, and for improving the conductivity of the existing film structure, the thickness of a silver film in the film structure needs to be increased, and the increase of the thickness of the silver film influences the transparency, flexibility and stability of the film structure. According to the invention, in the process of sputtering the silver film, nitrogen is doped in argon, so that the silver film is in a continuous state, the conductivity of the film structure can be improved, the thickness of the film structure is controlled, and the transparency, flexibility and stability are prevented from being influenced
The invention provides an electronic device, which has more stable performance compared with the prior art because the film structure has more excellent conductivity by using the film structure as an electrode; on the other hand, since the film structure has better flexibility, it can also be applied to a flexible display panel.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below.
FIG. 1 is a schematic flow diagram of one embodiment of a method of making a membrane structure provided by embodiments of the present invention;
FIG. 2 is a schematic diagram of an embodiment of a membrane structure provided by embodiments of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a film structure, a preparation method of the film structure and an electronic device. The following are detailed below. It should be noted that the following description of the embodiments is not intended to limit the preferred order of the embodiments. In addition, in the description of the present invention, the term "including" means "including but not limited to". The terms first, second, third and the like are used merely as labels, and do not impose numerical requirements or an established order. Various embodiments of the invention may exist in a range of versions; it is to be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within a range of numbers, such as 1, 2, 3, 4, 5, and 6, for example, regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the indicated range. The term "maximum transmittance" as used in the present embodiment refers to a maximum value of light transmittance in a certain visible light wavelength range.
First, as shown in fig. 1, an embodiment of the present invention provides a method for preparing a film structure, where the method includes:
s1, providing a first metal oxide film;
s2, depositing a silver (Ag) film on one side of the first metal oxide film by using a magnetron sputtering method; and
and S3, depositing a second metal oxide film on the side, far away from the first oxide film, of the silver film to form a film structure. In this example, the working gases of the magnetron sputtering method were argon and nitrogen.
The preparation method of the film structure provided by the embodiment of the invention comprises the steps of introducing argon (Ar) and nitrogen (N) above a metal oxide substrate 2 ) As the working gas to form the continuous silver film, the defect that the prior art is difficult to consider the film thickness, the light transmittance and the electrical property is overcome, and the photoelectric property of the film structure is improved.
In the present invention, the expression "continuous" means a morphological state of the silver film, and is in a relatively "discontinuous" state, and the "discontinuous" silver film means that grooves and pores are formed between silver clusters, and the surface of the silver film is not flat as a whole. When the silver film is in a continuous state, the grooves and holes among the silver clusters are small, and the surface of the silver film is in a flat state in the whole view, so that the conductivity can be improved.
The principle of forming the continuous silver film in the embodiment of the invention is as follows: the nitrogen can inhibit the migration and fusion of the silver clusters (Ag (N)) in the growth process, and the migration of Ag (N) on the surface of the metal oxide is inhibited, so that the growth process of the Ag (N) clusters is mainly characterized in that the bridging is formed by changing the appearance of surface atoms of adjacent clusters under the trend of surface chemical potential energy. The growth mode greatly inhibits the three-dimensional island growth of the silver film and inhibits the formation and growth of grooves or holes, thereby forming a continuous silver film.
In some embodiments, the step S1 of providing a first metal oxide film specifically includes:
providing a substrate; and
depositing a first metal oxide film on the substrate.
The substrate material is a material known in the art, and may be glass, or may be other transparent polymers, such as polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyaniline (PEN), polyvinyl alcohol (PVA), and the like, but is not limited thereto.
In some embodiments, before providing the first metal oxide film in step S1, the method further includes:
preparing a first oxide target, a second oxide target and a silver target, and performing a pre-sputtering treatment on the first oxide target, the second oxide target and the silver target to remove oxide layers and impurities on the surfaces of the first oxide target, the second oxide target and the silver target, for example, in one embodiment, the first oxide target is ZnO, the ZnO purity is 99.9%, the silver target is nano silver, and the nano silver purity is 99.9%.
In some embodiments, the first metal oxide film may be deposited by magnetron sputtering, or prepared by other physical vapor deposition methods known in the art, such as vacuum evaporation, arc plasma coating, and the like. In view of simplification of the process, it is preferable in the present invention to deposit the first metal oxide film by magnetron sputtering, and then the S2 step may be directly performed.
In some embodiments, in step S2, the flow ratio of nitrogen to argon is (0.1 to 1): 100, it is understood that the flow ratio of nitrogen to argon may be (0.1 to 1): any value between 100, for example: 0.1: other values not listed between 100. The invention finds that when the flow ratio of nitrogen to argon can be between 0.1 and 100. If the proportion of nitrogen is too small, the function of suppressing migration and fusion of the silver clusters on the surface of the metal oxide during growth is not achieved, and if the proportion of nitrogen is too large, the film forming effect is impaired. In a preferred embodiment, the flow ratio of nitrogen to argon is 0.5. In one embodiment, the flow rate of argon is 50 milliliters per minute (sccm) and the flow rate of nitrogen is 0.25 milliliters per minute.
In some embodiments, the purity of the argon and/or nitrogen is greater than or equal to 99.0%. If the purity of argon and/or nitrogen is too low, the film forming effect is impaired.
In some embodiments, the thickness of the silver film ranges from 5 nanometers (nm) to 10 nanometers, and it is understood that the thickness of the silver film can be any value between 5 nanometers (nm) and 10nm, for example: 5nm, 6nm, 7 nm, 8nm, 9 nm, 10nm, or other values between 5nm and 10nm, which may affect the conductivity of the film structure if the thickness of the silver film is too thin, or affect the light transmittance of the film structure if the thickness of the silver film is too thick. The silver film is disposed as an interlayer between the first metal oxide film and the second metal oxide film, and in one embodiment, the first metal oxide film and the second metal oxide film have a thickness of 28nm to 32nm.
In some embodiments, during the deposition of the silver film by the magnetron sputtering method, the gas pressure ranges from 0.5Pa to 5Pa, and it is understood that the vacuum degree can range from 0.5Pa to 5Pa, for example: 0.5Pa, 1Pa, 2Pa, 3Pa, 4Pa, 5Pa, or other values between 0.5Pa and 5Pa not listed, if the vacuum degree is too high, the production cost will be increased, and if the vacuum degree is too low, the impurity gas and moisture in the air will be unfavorable for the sputtering operation.
In some embodiments, depositing a silver film on one side of the first metal oxide film using a magnetron sputtering method comprises: when a silver target is provided and nitrogen gas is introduced as a working gas into argon gas by a magnetron sputtering apparatus, and the silver film is sputtered on one side of the first metal oxide film after sufficient mixing, for example, after 20 seconds(s), the mixing of argon gas and nitrogen gas is not facilitated and the film forming effect is impaired if the time is too short. In one embodiment, the magnetron sputtering method is a direct current magnetron sputtering method.
In some embodiments, the purity of the silver target is greater than or equal to 99.9%, and if the target purity of the silver film is too low, the conductive effect of the film structure is affected.
In some embodiments, after the step S2 is completed, a step S3 of forming a second oxide film on the surface of the silver film is performed. The second oxide film may be prepared using the same process as the first metal oxide film.
In some embodiments, the material of the first metal oxide film and the material of the second metal oxide film are independently selected from zinc oxide (ZnO), zinc magnesium oxide (MgZnO), zinc aluminum oxide (AlZnO), titanium dioxide (TiO) 2 ) Molybdenum trioxide (MoO) 3 ) That is, the material of the first metal oxide may be selected from zinc oxide (ZnO), zinc magnesium oxide (MgZnO), zinc aluminum oxide (AlZnO), titanium dioxide (TiO) 2 ) Molybdenum trioxide (MoO) 3 ) The material of the second metal oxide may be selected from zinc oxide (ZnO), zinc magnesium oxide (MgZnO), zinc aluminum oxide (AlZnO), titanium dioxide (TiO) 2 ) Molybdenum trioxide (MoO) 3 ) The material of the first metal oxide and the material of the second oxide may be the same or different. Thus, when the sputtering working gas is argon or nitrogen, the silver clusters can have good wettability on the metal oxide films, and a continuous silver film can be formed.
On the basis of the above embodiments, the present invention also provides a membrane structure made by the method described in any of the above embodiments.
As shown in fig. 2, fig. 2 shows a basic structure of the film structure 10, wherein the film structure 10 includes a first metal oxide film 11, a second metal oxide film 13, and a silver film 12 sandwiched between the first metal oxide film 11 and the second metal oxide film 13.
The invention provides a film structure, and for improving the conductivity of the existing film structure, the thickness of a silver film in the film structure needs to be increased, and the increase of the thickness of the silver film influences the transparency, the flexibility and the stability of the film structure. The principle of the invention is as follows: in the process of sputtering the silver film, nitrogen is doped into argon, so that the surface of the silver film is in a continuous state, the conductivity of the film structure is improved, the thickness of the film structure is controlled, and the transparency, flexibility and stability are prevented from being influenced.
On the basis of the above embodiments, the present invention also provides an electronic device including the film structure described in the above embodiments.
In some embodiments, the electronic device includes a first electrode and a second electrode which are oppositely disposed, and a light-emitting layer disposed between the first electrode and the second electrode, and the material of the first electrode or the second electrode is the film structure. In a specific embodiment, the first electrode may be an anode and the second electrode may be a cathode.
For example: one example of such an electronic device is a quantum dot light emitting diode device (QLED) comprising: the QLED comprises a substrate, a cathode arranged on the substrate, an electron transport layer arranged on the cathode, a quantum dot light-emitting layer arranged on the electron transport layer, a hole transport layer arranged on the quantum dot light-emitting layer, a hole injection layer arranged on the hole transport layer and an anode arranged on the hole injection layer, wherein after the film structure is used as the cathode or the anode of the QLED, the QLED can have more stable performance.
Another example of the electronic device is an Organic Light Emitting Diode (OLED) display panel, in which organic light emitting diodes are formed on an array substrate, and a pixel electrode of each sub-pixel unit may serve as an anode or a cathode of the organic light emitting diode or may be electrically connected to the anode or the cathode of the organic light emitting diode for driving the organic light emitting diode to emit light for a display operation, and the organic light emitting diode device may have more stable performance after applying the film structure described in this embodiment as the cathode or the anode of the OLED device.
The electronic device disclosed by the invention can be applied to wearable equipment such as smart bracelets, smart watches, VR (Virtual Reality) and the like; the flexible OLED display and lighting device can also be used for mobile phones, electronic books and electronic newspapers, televisions, personal portable computers, foldable and rollable OLEDs and other flexible OLED display and lighting devices, and the like.
The invention provides an electronic device, wherein the film structure is used as a transparent electrode, and compared with the prior art, the transparent electrode has more excellent conductivity, so that the electronic device can have more stable performance; on the other hand, the transparent electrode layer has better flexibility, so that the transparent electrode layer can also be applied to a flexible display panel.
The present invention also provides a method for manufacturing an electronic device including a first electrode and a second electrode which are oppositely disposed, and a light-emitting layer disposed between the first electrode and the second electrode, the first electrode or the second electrode being a film structure, the method for manufacturing the film structure including:
providing a first metal oxide film;
depositing a silver film on one side of the first metal oxide film by using a magnetron sputtering method; and
depositing a second metal oxide film on a side of the silver film remote from the first oxide film,
wherein, the working gas of the magnetron sputtering method is argon and nitrogen.
According to the preparation method of the electronic device, the electronic device comprises a first electrode and a second electrode, the first electrode and the second electrode are of film structures, in the preparation of the film structures, argon and nitrogen are used as working gases, the nitrogen can inhibit migration and fusion of silver clusters (Ag (N)) on the surface of a metal oxide in the growth process, the migration of the Ag (N) clusters on the surface of the metal oxide is inhibited, and therefore the growth process of the Ag (N) clusters is mainly characterized in that bridging is formed by changing the shapes of surface atoms of adjacent clusters under the trend of surface chemical potential energy. The growth mode greatly inhibits the three-dimensional island growth of the silver film, inhibits the formation and growth of grooves or holes, can form a continuous silver film, and breaks through the defect that the prior art is difficult to consider the film thickness, the light transmittance and the electrical property, thereby improving the photoelectric property of the film structure. And the nitrogen has good stability, the target poisoning probability can be reduced, the doping amount is controllable, and the stability of the performance of the electronic device can be improved.
The following examples are only exemplary embodiments of the present invention and are not intended to limit the present invention.
Example 1
The specific process of example 1 is as follows:
(1) Before the electrode is prepared, the oxide target and the metal Ag target are respectively subjected to pre-sputtering treatment to remove an oxide layer and impurities on the surface of the target, wherein the purity of the ZnO target is 99.9 percent, and the purity of the Ag target is 99.9 percent.
(2) When the background vacuum of the vacuum chamber reaches 5 x 10 -4 And Pa, starting a substrate rotating button, introducing Ar gas at the same time, and starting film plating when the Ar gas flow is 50 sccm.
(4) And (3) switching on an alternating current power supply, depositing a bottom layer ZnO film, and starting under a high-pressure environment because an oxide target is difficult to start, and then reducing the pressure to a working pressure (0.5 Pa to 5 Pa) to form a ZnO layer with the thickness of 30nm.
(5) After the bottom ZnO is prepared, a sample is not required to be led out, and a direct current power supply is directly connected to deposit the Ag film. A small amount of doping gas N is introduced in the preparation process of the Ag film 2 The flow rate was 0.25sccm, and sputtering was started 20 seconds after the introduction of the dopant gas to ensure thorough mixing of the gases, with an Ag layer thickness of 6.5nm.
(6) The preparation process of the upper ZnO film is the same as that of the bottom ZnO film, and the film structure is obtained.
The maximum transmittance and surface resistance of the film structure in the visible light wavelength range, as measured by an ultraviolet-visible spectrophotometer and a resistance tester, were 88% and 18 Ω/sq, respectively.
Example 2
Example 2 is the same process as example 1 except that the Ag layer thickness is different, wherein the Ag layer thickness of example 2 is 10nm. The maximum transmittance and the surface resistance of the film structure in the visible wavelength range were found to be 85% and 12.8 Ω/sq, respectively, by an ultraviolet-visible spectrophotometer and a resistance tester.
Example 3
Except Ar gas and N 2 The other processes of example 3 and example 2 were the same except that the flow rate was different, wherein the flow rate of Ar was 50sccm 2 The flow rate was 0.05sccm and the Ag layer thickness was 10nm.
The maximum transmittance and the surface resistance of the film structure in the visible wavelength range obtained by an ultraviolet-visible spectrophotometer and a resistance tester were 86% and 20 Ω/sq, respectively.
Example 4
In addition to Ar gas and N 2 Except for the difference in gas flow rate, the other processes of example 4 and example 2 were the same, wherein the flow rate of Ar was 50sccm, and N was 2 The flow rate was 0.03sccm and the Ag layer thickness was 10nm.
The maximum transmittance and the surface resistance of the film structure obtained by an ultraviolet visible spectrophotometer and a resistance tester in the visible wavelength range are respectively 86% and 55 omega/sq, and the surface resistance is too large and is more than 20 omega/sq.
Example 5
Except Ar gas and N 2 The other processes of example 5 and example 2 were the same except that the flow rate was different, wherein the flow rate of Ar was 50sccm 2 The gas flow was 0.5sccm and the Ag layer thickness was 10nm.
The maximum transmittance and the surface resistance of the film structure in the visible wavelength range obtained by an ultraviolet-visible spectrophotometer and a resistance tester were 85% and 20 Ω/sq, respectively.
Example 6
Except Ar gas and N 2 The flow rate of Ar was 50sccm, and the flow rates of Ar in example 6 and example 2 were the same as in example 2 2 The gas flow was 0.8sccm and the Ag layer thickness was 10nm. The maximum transmittance and the surface resistance of the film structure in the visible light wavelength range are respectively 86% and 38 omega/sq through an ultraviolet-visible spectrophotometer and a resistance tester, and the surface resistance is too large and is more than 20 omega/sq.
Comparative example
This example was conducted in the same manner as example 2 except that argon gas was not introduced thereinto, wherein the flow rate of Ar was 50sccm, and the thickness of Ag layer was 10nm.
The maximum transmittance and the surface sheet resistance of the film structure in the visible wavelength range are respectively 88% and 327 omega/sq through an ultraviolet-visible spectrophotometer and a resistance tester, and the surface resistance is too large and is more than 20 omega/sq.
From the above results, it can be seen that:
in embodiments 1 to 6 of the present invention, since the film structure has a uniform surface morphology and the surface of the silver film is flat and continuous, the thickness of 6nm to 10nm is achieved, that is, the surface resistance is between 10 Ω/sq and 55 Ω/sq, and the film structure prepared by the method has good conductivity, and the maximum transmittance in the visible light wavelength range is up to 85% or more, and has good transparency.
Comparing example 2 with the comparative example, it was shown that, when the silver film was deposited using the magnetron sputtering technique, the surface resistance of the film structure was greater than 300 Ω/sq above the metal oxide substrate when the working gas was only argon, and the surface resistance of the film structure was 12.8 Ω/sq when the working gases were argon and nitrogen, indicating that the continuity of the prepared silver film was better when nitrogen was fed than when nitrogen was not fed.
In examples 1, 2, 3 and 5 of the present invention, the surface resistance was within 20 Ω/sq, and it can be seen that the prepared film structure was excellent in conductivity, and the maximum transmittance in the visible light wavelength range was 85% or more, and had good transparency, indicating that the flow ratio of nitrogen gas and argon gas was (0.1 to 1): within 100, the continuity of the prepared silver film is better.
In summary, according to the film structure and the method for manufacturing an electronic device provided by the embodiments of the present invention, the continuous silver film is formed above the metal oxide substrate by using argon and nitrogen as the working gases, so that the defect that the film thickness, the light transmittance, and the electrical property are difficult to be considered in the prior art is overcome, and the photoelectric property of the film structure is improved. In addition, the nitrogen has good stability, the target poisoning probability can be reduced, the doping amount is controllable, and the stability of the performance of the electronic device can be improved.
The invention provides a film structure, and for improving the conductivity of the existing film structure, the thickness of a silver film in the film structure needs to be increased, and the increase of the thickness of the silver film influences the transparency, flexibility and stability of the film structure. According to the invention, in the process of sputtering the silver film, nitrogen is doped in argon, so that the silver film is in a continuous state, the conductivity of the film structure can be improved, the thickness of the film structure is controlled, and the transparency, flexibility and stability are prevented from being influenced.
The present invention provides an electronic device which can have more stable performance by using the film structure as a transparent electrode having more excellent conductivity; on the other hand, the transparent electrode layer has better flexibility, so that the transparent electrode layer can also be applied to a flexible display panel.
The above detailed description of the film structure, the preparation method thereof, and the electronic device provided in the embodiments of the present invention apply specific examples to explain the principles and embodiments of the present invention, and the description of the above embodiments is only used to help understanding the method and the core concept of the present invention; meanwhile, for those skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (10)
1. A method of making a film structure, the method comprising:
providing a first metal oxide film;
depositing a silver film on one side of the first metal oxide film by using a magnetron sputtering method; and
depositing a second metal oxide film on a side of the silver film remote from the first oxide film,
wherein, the working gas of the magnetron sputtering method is argon and nitrogen.
2. The method according to claim 1, wherein the flow ratio of the nitrogen gas to the argon gas is (0.1 to 1): 100.
3. the method according to claim 1, characterized in that said argon, and/or said nitrogen, have a purity greater than or equal to 99.0%.
4. The production method according to claim 1, wherein a material of the first metal oxide film and a material of the second metal oxide film are independently selected from ZnO, mgZnO, alZnO, tiO 2 、MoO 3 The material of the first metal oxide and the material of the second metal oxide are the same or different.
5. The method according to claim 1, wherein the silver film has a thickness of 5 to 10nm.
6. The production method according to claim 1, wherein a gas pressure atmosphere of 0.5Pa to 5Pa is provided in depositing the silver film by the magnetron sputtering method.
7. The method of claim 1, wherein depositing a silver film on one side of the first metal oxide film using a magnetron sputtering method comprises: and providing a silver target, introducing nitrogen as a working gas into argon by using a magnetron sputtering device, and sputtering a silver film on one side of the first metal oxide film after fully mixing.
8. The method according to claim 7, wherein the purity of the silver target is greater than or equal to 99.9%.
9. A film structure made by the method of any one of claims 1 to 8.
10. An electronic device comprising the film structure of claim 9 as a cathode or an anode.
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