CN112885503B - Preparation method and application of ultrathin silver-based OMO (organic molybdenum oxide) composite transparent conductive film - Google Patents

Preparation method and application of ultrathin silver-based OMO (organic molybdenum oxide) composite transparent conductive film Download PDF

Info

Publication number
CN112885503B
CN112885503B CN202110036640.8A CN202110036640A CN112885503B CN 112885503 B CN112885503 B CN 112885503B CN 202110036640 A CN202110036640 A CN 202110036640A CN 112885503 B CN112885503 B CN 112885503B
Authority
CN
China
Prior art keywords
oxide
film
ultrathin
composite
omo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110036640.8A
Other languages
Chinese (zh)
Other versions
CN112885503A (en
Inventor
陈新亮
刘璋
侯国付
张晓丹
赵颖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nankai University
Original Assignee
Nankai University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nankai University filed Critical Nankai University
Priority to CN202110036640.8A priority Critical patent/CN112885503B/en
Publication of CN112885503A publication Critical patent/CN112885503A/en
Application granted granted Critical
Publication of CN112885503B publication Critical patent/CN112885503B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • 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
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive 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
    • C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
    • 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
    • C23C14/14—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
    • 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
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • 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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H01L31/022491—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of a thin transparent metal layer, e.g. gold
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/36—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
    • H01L33/40—Materials therefor
    • H01L33/42—Transparent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

A preparation method and application of an ultrathin silver-based OMO composite transparent conductive film belong to the field of optoelectronic devices. The invention adopts magnetron sputtering technology and the like to grow the ultrathin Ag-Zn film, wherein Ag metal target (doping agent is Zn) is taken as a raw material, Ar gas is taken as sputtering gas, and trace O is selectively introduced in the film coating process2(ii) a Oxide thin films are grown by utilizing a reactive plasma deposition technology and the like, so that Oxide/Ag-Zn/Oxide or Oxide/Ag-Zn (O)/Oxide composite thin films are formed and obtained. The threshold thickness (5 nm) of the ultrathin Ag-Zn film is obviously lower than that of an Ag film prepared by a conventional method, the near infrared NIR transmittance and the transmittance in a wide spectral range can be greatly improved on the premise of keeping good conductivity, the manufacturing temperature and the coating cost are low, the environment is friendly, and the OMO composite film can be applied to photoelectric devices.

Description

Preparation method and application of ultrathin silver-based OMO (organic molybdenum oxide) composite transparent conductive film
Technical Field
The invention relates to a preparation method of a transparent conductive electrode, in particular to a preparation method and application of an OMO composite film transparent conductive electrode based on an ultrathin silver film.
Background
Transparent conductive electrode-TCE (transparent conductive electrode-TCE) has shown a wide application prospect in the field of optoelectronic devices (such as solar cells), and references: k Ellmer. Nature Photonics 6(2012) 809-817. In is doped with Sn In Transparent Conductive Oxide (TCO)2O3(ITO) and F-doped SnO2The (FTO) film has good photoelectric characteristics and chemical stability, and becomes the bottom electrode material which is most widely applied in the field of photoelectric devices. However, when TCE is to be fabricated on top of a device (e.g., a translucent solar cell), the impact of the fabrication process on the substrate needs to be considered. High-performance ITO is limited to vacuum deposition and needs high-temperature annealing (more than 200 ℃), the photoelectric performance of ITO prepared by magnetron sputtering at room temperature is relatively poor, sputtering particles with large kinetic energy can damage a bottom layer, and although one buffer layer can avoid the damage, additional parasitic absorption can be introduced. And the toxicity and rarity of the In element have limited the development of ITO, researchers have been working on developing indium-free TCEs. An ideal TCE should have the following characteristics: (1) the conductive material has good conductive property and optical transmittance; (2) chemical stability and compatibility with adjacent layers; (3) the preparation process is simple and is suitable for large-scale production; (4) low cost, safety and no pollution. In the novel TCE, a PEDOT (Poly ethylene glycol ether ketone) electrode and a PSS (Poly ethylene glycol ether ketone) electrode show acidity and water absorbability and are not beneficial to long-term stability of ST-PSCs; silver nanowires and multilayer graphene have good photoelectric properties, but the preparation method is complex and time-consuming, so that the repeatability is poor; the carbon nano tube has low cost and good stability, but the application of the carbon nano tube is limited by the excessively high square resistance (2-25 k omega/sq). And they all lack high-throughput manufacturing processes, are difficult to manufacture on a large scale, and are difficult to produce commercially in a short period of time.
The ultra-thin metal film based medium/metal/medium (DMD) composite film can greatly improve the overall transmittance according to the optical interference effect and the mature large-scale manufacturing process of each part on the premise of maintaining the good conductivity of the metal film, and becomes a very competitive new generation TCE, reference: YG Bi, YF Liu et al. adv. optical Mater 7(2019) 1-23. The composite layer based on oxides as the medium is called OMO. Common candidates for dielectric layers are oxides: the bottom layer oxide functions as a seed layer (promoting two-dimensional growth of the metal layer), a protective layer (preventing metal from directly contacting the bottom layer), and an optical coupling layer; the top oxide layer mainly functions as an optical coupling layer and a protective layer (to insulate the metal layer from moisture, oxygen). In addition, oxide materials with proper work functions can be selected according to the requirements of the photoelectric device. The metal layer is the core of the DMD structure, the overall conductivity is improved through the metal interlayer, but the transmittance of the DMD composite film in a Near Infrared (NIR) region is rapidly reduced due to the strong reflection of the thicker metal layer. Therefore, it is desirable to reduce the thickness of the metal layer and reduce the NIR reflection while ensuring good conductivity of the metal layer. There is now a minimum thickness at which the metal layers can just connect to form a conductive path, referred to as the percolation threshold thickness. The growth mode of common metal materials (e.g., Au, Ag, Cu) is island growth (Volmer-Weber growth mode, i.e., Ag atoms tend to bond to each other more during the initial deposition of Ag thin film than during the bonding to the substrate, forming island structures), which makes the metal thin film have a higher threshold thickness (10-20 nm). If the thickness is less than the threshold value, the metal thin film is not only poor in conductivity but also has parasitic absorption of light due to the local surface plasmon effect, and the transmittance of the entire film is limited.
In recent years, researchers have conducted a great deal of research to obtain ultra-thin metal films with lower threshold thickness and better photoelectric properties. In 2014, Zhang et al of Michigan university in SiO2On the substrate, a smooth and thermally stable ultrathin Ag film is deposited, the thickness of the Ag film can be reduced to 6nm by doping 10 at% of Al into Ag for the first time, the transmittance of the composite film Ag-Al/ZnO (7nm/45nm) can be more than 80% within 400-800nm, the square resistance is 23.4 omega, and the reference: c Zhang, D Zhao et al advanced Materials 26(2014) 5696-. Same year, Korean materialIn the process of sputtering Ag, Wang et al introduce a trace amount of oxygen to disturb the lattice structure of Ag atoms, so that the cohesive force of the Ag atoms is weakened, and in the early nucleation stage, Ag increases nucleation sites under the induction of oxygen, thereby being beneficial to subsequent two-dimensional growth. An ultrathin Ag film with the threshold thickness of 6nm is also realized, the ZnO/AgOx (8nm)/ZnO composite film realizes the average transmittance of 91% (relative transmittance) of 400-1000nm, the maximum transmittance is 95%, the square resistance is 20 omega, and the reference: w Wang, M Song et al. advanced Function Materials 24(2014) 1551-1561. In 2019, Wang et al, China academy of sciences, Wang et al, connected with the institute of physical and chemical research, Wang et al, proposed MoO3/Au/MoO3(30nm/7nm/80nm) structure due to MoO3The larger surface tension is beneficial to the conversion of the growth mode of Au atoms into a Frank-VanderMerwe growth mode, Au presents a nano-grid structure when the thickness is 7nm, and under the condition of keeping good conductivity (19.6 omega/sq), the average transmittance of 800-: z Wang, X Zhu et al. advanced Function Materials 30(2019) 1-8. In the same year, Xu and the like of Ningbo materials of Chinese academy of sciences further reduce the thickness of the ultrathin Ag film to 5nm by doping CdO into Ag, and the Ag-CdO film of the ultrathin Ag film realizes 89% transmittance and 32.9 omega/sq square resistance at 550nm, has a smooth surface and roughness of only 0.2nm, and is disclosed in reference documents: j Xu, J Li et al advanced Materials Interfaces 1900608(2019) 1-8.
The research method mainly adopts the mode of doping Al metal and CdO in the Ag film or ultrathin metal Au, and the like, promotes the transverse growth of the Ag film, and reduces the threshold thickness. However, the Au material is expensive, the Ag film and the film manufactured by the corresponding doping technology are thick and complex in process, and the optical and electrical properties still have a larger promotion space. According to the current research situation and the key scientific and technical problems at home and abroad and based on that Ag is a face-centered cubic lattice structure and Zn is a close-packed hexagonal lattice structure, the applicant proposes that Zn is doped in Ag lattices, so that a substitutional defect or a gap defect is easily formed by doping heterogeneous metal elements, and based on the difference of crystal structures and atomic radii of the two, lattice distortion is easily promoted, so that more film nucleation points are induced; in addition, an O element is doped and introduced, so that the threshold thickness of the pure metal Ag film is further reduced, and the optical transmittance of the OMO integral structure in the visible light and near infrared region NIR is further improved. The research on the aspect has not been reported internationally.
The invention adopts magnetron Sputtering (Sputtering) technology and the like to grow the ultrathin Ag-Zn film, wherein Ag metal target (doping agent is Zn) is taken as a raw material, Ar gas is taken as Sputtering gas, and trace O is selectively introduced in the film coating process2(ii) a Growing Oxide thin film (such as MGZO, NiOx, SnOx or Ga) by using Reactive Plasma Deposition (RPD) technique2O3Thin film) to form and obtain an Oxide/Ag-Zn/Oxide or Oxide/Ag-Zn (O)/Oxide composite thin film, and applying the thin film to optoelectronic devices such as perovskite solar cells, perovskite/crystalline silicon tandem solar cells, organic solar cells, flexible light emitting diodes, flexible display devices and the like. The method for preparing the high-quality ultrathin Ag-Zn film and the application are different from other methods reported internationally at present.
Disclosure of Invention
The invention aims to provide a method for growing an ultrathin Ag-Zn film by a magnetron sputtering technology aiming at the technical analysis, wherein an Ag metal target (a doping agent is Zn) is used as a raw material, Ar gas is used as a sputtering gas, and trace O is selectively introduced in the film coating process2Thereby forming ultra-thin Ag-Zn or Ag-Zn (O); growing Oxide thin film (such as MGZO, NiOx, SnOx or Ga) by using Reactive Plasma Deposition (RPD) technique2O3Film), the composite film can be constructed to realize Oxide/Ag-Zn/Oxide or Oxide/Ag-Zn (O)/Oxide composite film, and can be applied to photoelectrons and flexible electronic devices, such as perovskite solar cells, perovskite/crystalline silicon laminated solar cells, organic solar cells, flexible light-emitting diodes, flexible display devices and the like. The method overcomes the defect of overlarge NIR reflection in a near infrared region caused by overlarge permeation threshold thickness in the conventional growth of the Ag film, improves the overall visible light and optical transmittance in the near infrared region, and simultaneously keeps good conductivity. The OMO structure TCE realized based on the ultrathin Ag-Zn can be applied to photoelectronic and flexible electronic devices, and the device performance is effectively improved.
The technical scheme of the invention is as follows:
a preparation method of an OMO structure transparent conductive film based on an ultrathin Ag-Zn film adopts magnetron sputtering equipment, takes Zn-doped Ag target material with the component purity of 99.99 percent as a raw material, adopts Ar gas as sputtering gas, and introduces a small amount of O in the film coating process2(ii) a In MGZO, NiOx, SnOx or Ga2O3Growing Ag-Zn film on the film substrate at low temperature (such as room temperature) to obtain Oxide/Ag-Zn or Oxide/Ag-Zn (O) film. Further growing MGZO, NiOx, SnOx or Ga on the top layer at low temperature (e.g. room temperature)2O3Obtaining the Oxide/Ag-Zn/Oxide or Oxide/Ag-Zn (O)/Oxide composite film.
The composite film structure is Oxide/Ag-Zn/Oxide or Oxide/Ag-Zn (O)/Oxide, and the substrate is a glass substrate or a flexible substrate material, such as PET, PI, but not limited to PET or PI.
The atomic percentage of Zn dopant in the target material component in the Ag target is 2-20%;
the preparation method of the Ag-Zn film comprises but is not limited to magnetron sputtering technology, thermal evaporation technology and the like;
the thickness of the Oxide film is 20-100 nm; Ag-Zn or Ag-Zn (O) film thickness is 3-12 nm;
the pressure of the deposition gas Ar is 0.1-3.0 Torr; the flow of the introduced oxygen is 0sccm to 20sccm in the coating process; the substrate temperature is from liquid nitrogen temperature to 150 ℃.
The grown Oxide is selected from the group consisting of, but not limited to, MGZO, NiOx, SnOx, or Ga2O3Films and the like;
the growing method of the Oxide film comprises but is not limited to magnetron sputtering technology or reactive plasma deposition technology and the like;
the Oxide (e.g. MGZO, NiOx, SnOx or Ga)2O3Etc.) film thickness of 20-100 nm.
The composite film structure is Oxide/Ag-Zn/Oxide or Oxide/Ag-Zn (O)/Oxide applied to photoelectron and flexible electronic devices, such as organic solar cells, perovskite/crystalline silicon laminated solar cells, light emitting diodes, flexible display devices and the like.
The film is based on ultrathin Ag-Zn or Ag-Zn (O)The composite structure Oxide/Ag-Zn/Oxide or Oxide/Ag-Zn (O)/Oxide composite film is applied, wherein the structural characteristics of the perovskite solar cell are as follows: glass/ITO/HTL (PEDOT: PSS or NiOx, etc.)/PVK/ETL (PCBM or SnO)2etc./Oxide/Ag-Zn or Ag-Zn (O)/Oxide/Ag; the structural characteristics of the perovskite/crystalline silicon laminated solar cell are Ag/ITO/a-Si H (p)+)/a-Si:H(i)/c-Si(n)/a-Si:H(i)/a-Si:H(n+) ITO/HTL (NiOx, etc.)/PVK/ETL (PCBM or SnO)xetc./Oxide/Ag-Zn or Ag-Zn (O)/Oxide/Ag/MgF2。
The invention has the advantages and effects that: compared with the Ag film obtained by the conventional sputtering and evaporation technology, the ultrathin Ag-Zn film grown by the magnetron sputtering and doping technology has lower permeation threshold thickness, and can greatly improve the NIR optical transmittance under the condition of maintaining excellent electrical properties. In addition, by growing the dielectric layer at room temperature, the OMO structure Oxide/Ag-Zn/Oxide or Oxide/Ag-Zn (O)/Oxide film is manufactured to be applied to photoelectrons (solar cells, light emitting diodes and the like) and flexible electronic devices.
Drawings
FIG. 1 is a schematic view of the structure of glass/MGZO/Ag-Zn (O)/MGZO thin film.
FIG. 2 is an SEM photograph of an MGZO/Ag-Zn (O) thin film and an optical transmittance chart of a glass/MGZO/Ag-Zn (O)/MGZO thin film.
FIG. 3 is a schematic structural diagram of the SnOx/Ag-Zn/SnOx thin film applied to a pin type semi-transparent perovskite solar cell.
FIG. 4 is a schematic structural diagram of a PET/MGZO/Ag-Zn (O)/MGZO thin film and a schematic structural diagram of a flexible perovskite solar cell.
FIG. 5 is a schematic structural diagram of a SnOx/Ag-Zn (O)/SnOx film applied to a perovskite/crystalline silicon tandem solar cell at two ends.
Detailed Description
Example 1:
1. by utilizing a magnetron sputtering technology, an Ag target with the purity of 99.99 percent is used as a target material, and the doping agent component Zn in the target material is doped with 8 percent of atoms; the flow rate of the sputtering gas Ar gas is 20sccm, and the doping gas O2The flow rate of the sputtering target is 1sccm, the sputtering power is 140W, and the film specification of the chamber is 0.3 Pa; on glass/MGZO (-50 nm) substratesGrowing Ag-Zn (O) film, with the substrate temperature at room temperature and the film thickness of-4.5 nm. And then growing a layer of MGZO on the top layer at room temperature by adopting an RPD technology, wherein the thickness of the film is 50 nm. The composite film structure is glass/MGZO/Ag-Zn (O)/MGZO, as shown in FIG. 1.
FIG. 2(a) is an SEM image of a glass/(-50 nm) MGZO/(-4.5 nm) Ag-Zn (O) thin film, which exhibits a dense continuous layered structure; FIG. 2(b) is the optical transmittance of glass/MGZO/Ag-Zn (O)/MGZO film, the film has higher transmittance in the full spectrum range, the average transmittance in the 400-1200nm range is 85.9%, and the average transmittance in the NIR range is 83.7%, which is significantly higher than that of the DMD structure of the conventional Ag film, and the sheet resistance is about 30 Ω/sq.
Example 2:
1. by utilizing a magnetron sputtering technology, an Ag target with the purity of 99.99 percent is used as a target material, and the doping agent component Zn in the target material is doped with 8 percent of atoms; the flow rate of the sputtering gas Ar gas is 20sccm, the sputtering power is 140W, and the film specification of the chamber is 0.3 Pa; an Ag-Zn film is grown on a glass/SnOx (about 50nm) substrate, the substrate temperature is 50 ℃, and the film thickness is about 5 nm. And then growing a layer of SnOx on the top layer at room temperature by adopting an RPD technology, wherein the thickness of the film is 50 nm. The composite film structure is glass/SnOx/Ag-Zn/SnOx.
2. The OMO composite film is applied to a perovskite solar cell, and FIG. 3 is a schematic structural diagram of a pin type semitransparent perovskite solar cell. Firstly, preparing a precursor solution, and preparing a cavity PEDOT (PSS or NiOx), a perovskite absorption layer (MAPbI3 or FAMAPbIxBr) and an electron transport layer SnOx or PCBM on an ITO substrate by combining spin coating and an annealing process; and then, manufacturing a composite transparent electrode SnOx/Ag-Zn/SnOx on the top of the cell by using a Reactive Plasma Deposition (RPD) technology and a sputtering technology, and finally, evaporating a metal Ag or Au electrode on the top layer, wherein the characteristics are used for forming the solar cell device.
Example 3:
1. by utilizing a magnetron sputtering technology, an Ag target with the purity of 99.99 percent is used as a target material, and the doping agent component Zn in the target material is doped with 8 percent of atoms; the flow rate of the sputtering gas Ar gas is 20sccm, and the doping gas O2At a flow rate of 1.0sccm, sputteringThe emitting power is 140W, and the film gauge of the chamber is 0.3 Pa; growing Ag-Zn (O) film on a PET/MGZO (about 50nm) substrate, wherein the temperature of the substrate is room temperature, and the thickness of the film is about 4.5 nm. And then a layer of MGZO is grown on the top layer at room temperature by adopting a Reactive Plasma Deposition (RPD) technology, and the thickness of the film is 50 nm. The composite film structure is PET/MGZO/Ag-Zn (O)/MGZO, as shown in FIG. 4 (a).
2. The OMO composite film is applied to a flexible perovskite solar cell, and FIG. 4(b) is a schematic structural diagram of the flexible perovskite solar cell. Preparing an MGZO/Ag-Zn (O)/MGZO film on flexible PET, preparing a precursor solution, combining spin coating and an annealing process, and preparing an electron transport layer SnO on a flexible OMO composite film substrate2Perovskite absorber layer (MAPbI3 or fampbixbr), and hole transport layer Spiro-OMeTAD; and finally, evaporating a metal Au electrode on the top layer, wherein the characteristics form the battery device.
Example 4:
1. by utilizing a magnetron sputtering technology, an Ag target with the purity of 99.99 percent is used as a target material, and the doping agent component Zn in the target material is doped with 8 percent of atoms; the flow rate of the sputtering gas Ar is 20sccm, the sputtering power is 140W, and the film gauge of the chamber is 0.3 Pa; growing Ag-Zn (O) film on a glass/SnOx (about 50nm) substrate, wherein the substrate temperature is room temperature, and the film thickness is about 5 nm. And then growing a layer of SnOx on the top layer at room temperature by adopting an RPD technology, wherein the thickness of the film is 50 nm. The composite film structure is glass/SnOx/Ag-Zn (O)/SnOx.
2. The OMO composite film is applied to a perovskite/crystalline silicon tandem solar cell at two ends, and FIG. 5 is a schematic structural diagram of the perovskite/crystalline silicon tandem solar cell at two ends. A crystalline Silicon Heterojunction (SHJ) bottom cell was first prepared: on a polished monocrystalline silicon c-Si wafer with the thickness of 260mm, the front surface is kept polished so as to facilitate deposition of a perovskite top cell, and the rear surface is subjected to chemical treatment to obtain a textured structure. After cleaning, respectively depositing intrinsic and p-type a-Si: H films on a suede surface by adopting a PECVD technology, depositing intrinsic and n-type a-Si: H films on a polished surface, then sequentially depositing ITO and Ag on the suede surface by adopting a magnetron sputtering technology, and depositing an ITO composite layer on the polished surface by adopting a thermal evaporation technology; preparing a perovskite roof battery: preparing precursor solution by spinningCombining coating, thermal evaporation and annealing processes, and sequentially preparing a hole transport layer PTAA, a perovskite absorption layer and an electron transport layer C on the ITO composite layer60And SnO2. Then, a composite transparent electrode SnOx/Ag-Zn (O)/SnOx is manufactured on the top of the cell by utilizing an RPD technology and a sputtering technology, and finally, a metal Ag electrode and MgF are evaporated on the top layer2And an anti-reflection layer, wherein the characteristics form a solar cell device.

Claims (8)

1. A preparation method of an ultrathin silver-based OMO composite transparent conductive film is characterized by comprising the following steps: adopting magnetron sputtering technology, taking Zn-doped Ag target with the component purity of 99.99 percent as a raw material, taking sputtering gas as Ar gas, and selectively introducing trace O in the film coating process2Realizing the ultrathin Ag-Zn or Ag-Zn (O) film; the Oxide film is grown at low temperature by utilizing magnetron sputtering or reactive plasma deposition technology, so that an Oxide/Ag-Zn/Oxide or Oxide/Ag-Zn (O)/Oxide film with a composite structure based on the ultrathin Ag-Zn or Ag-Zn (O) film is obtained;
growing an ultrathin Ag-Zn or Ag-Zn (O) film by utilizing a magnetron sputtering technology, wherein the atomic percent of Zn in a target material component in an Ag target is 2-9.5%; the Oxide film is MGZO, NiOx, SnOx or Ga2O3A film.
2. The method for preparing the ultra-thin silver-based OMO composite transparent conductive film according to claim 1, wherein the method comprises the following steps: the composite film Oxide/Ag-Zn/Oxide or Oxide/Ag-Zn (O)/Oxide substrate is a glass substrate or a flexible substrate material, and the flexible substrate material comprises but is not limited to PET or PI.
3. The method for preparing the ultra-thin silver-based OMO composite transparent conductive film according to claim 1, wherein the method comprises the following steps: the coating techniques used for ultra-thin Ag-Zn or Ag-Zn (O) include, but are not limited to, magnetron sputtering or thermal evaporation techniques.
4. The method for preparing the ultra-thin silver-based OMO composite transparent conductive film according to claim 1, wherein the method comprises the following steps: oxide film fabrication techniques include, and are not limited to, magnetron sputtering or reactive plasma deposition techniques.
5. The method for preparing the ultrathin silver-based OMO composite transparent conductive film according to claim 1, which is characterized by comprising the following steps of: in Oxide/Ag-Zn/Oxide or Oxide/Ag-Zn (O)/Oxide, the Oxide film has a thickness of 20-100 nm; the thickness of the Ag-Zn or Ag-Zn (O) film is 3-12 nm.
6. The method for preparing the ultra-thin silver-based OMO composite transparent conductive film according to claim 1, wherein the method comprises the following steps: in the method for growing the ultrathin Ag-Zn or Ag-Zn (O) film by utilizing the magnetron sputtering technology, the pressure of Ar gas is 0.1 to 3.0 Torr; the flow rate of the introduced oxygen is 0to 20sccm in the process; the substrate temperature is from liquid nitrogen temperature to 150 ℃.
7. The use of the ultrathin Ag-Zn or Ag-Zn (O) film-based Oxide/Ag-Zn/Oxide or Oxide/Ag-Zn (O)/Oxide composite film prepared by the preparation method according to any one of claims 1 to 6, which is characterized in that: the method is applied to optoelectronic and flexible electronic devices, including but not limited to organic solar cells, perovskite/crystalline silicon tandem solar cells, light emitting diodes and flexible display devices.
8. The use of the ultra-thin Ag-Zn or Ag-Zn (o) thin film based composite structure Oxide/Ag-Zn/Oxide or Oxide/Ag-Zn (o)/Oxide composite thin film according to claim 7, wherein the structural characteristics of the perovskite solar cell are: glass/ITO/HTL/PVK/ETL/Oxide/Ag-Zn or Ag-Zn (O)/Oxide/Ag, wherein HTL is PEDOT, PSS or NiOx, ETL is PCBM or SnO2(ii) a The structural characteristics of the perovskite/crystalline silicon laminated solar cell are Ag/ITO/a-Si H (p)+)/a-Si:H(i)/c-Si(n)/a-Si:H(i)/a-Si:H(n+) ITO/HTL/PVK/ETL/Oxide/Ag-Zn or Ag-Zn (O)/Oxide/Ag/MgF2Wherein HTL is NiOx, ETL is PCBM or SnOx。
CN202110036640.8A 2021-01-12 2021-01-12 Preparation method and application of ultrathin silver-based OMO (organic molybdenum oxide) composite transparent conductive film Active CN112885503B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110036640.8A CN112885503B (en) 2021-01-12 2021-01-12 Preparation method and application of ultrathin silver-based OMO (organic molybdenum oxide) composite transparent conductive film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110036640.8A CN112885503B (en) 2021-01-12 2021-01-12 Preparation method and application of ultrathin silver-based OMO (organic molybdenum oxide) composite transparent conductive film

Publications (2)

Publication Number Publication Date
CN112885503A CN112885503A (en) 2021-06-01
CN112885503B true CN112885503B (en) 2022-06-21

Family

ID=76044289

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110036640.8A Active CN112885503B (en) 2021-01-12 2021-01-12 Preparation method and application of ultrathin silver-based OMO (organic molybdenum oxide) composite transparent conductive film

Country Status (1)

Country Link
CN (1) CN112885503B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113345644B (en) * 2021-06-07 2022-10-11 北方民族大学 Flexible Ag/Zn conductive film and preparation method and application thereof
CN113862497A (en) * 2021-09-23 2021-12-31 先导薄膜材料有限公司 AgZn target material and preparation method thereof
CN114005603A (en) * 2021-11-02 2022-02-01 合肥工业大学智能制造技术研究院 Method for improving conductivity of nano-silver film

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0668713A (en) * 1992-08-20 1994-03-11 Tonen Corp Transparent conductive film
JP2005314131A (en) * 2004-04-27 2005-11-10 Sumitomo Metal Mining Co Ltd Oxide sintered compact, sputtering target, transparent conductive thin film, and their production method
CN101752454A (en) * 2008-12-04 2010-06-23 上海空间电源研究所 Preparation method of ultrathin Cu-In-Ga-Se thin film solar cell with light trap structure
CN102134699A (en) * 2011-02-24 2011-07-27 海洋王照明科技股份有限公司 Preparation method of multilayer transparent conductive thin film as well as prepared thin film and application thereof
CN105624625A (en) * 2016-03-09 2016-06-01 南京邮电大学 Method for improving photoelectric properties of ZnO/Ag/ZnO transparent conductive film
CN108914077A (en) * 2018-08-02 2018-11-30 南京邮电大学 One kind being based on Nb2O5Transparent conductive oxide film and preparation method thereof
CN111593310A (en) * 2020-05-09 2020-08-28 哈尔滨工业大学 Method for preparing transparent conductive film with high photoelectric stability by magnetron sputtering

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102543271B (en) * 2012-02-17 2014-12-24 华东师范大学 Transparent conductive film with enhanced thermal stability and application thereof
CN102779944B (en) * 2012-08-06 2015-04-15 上海电力学院 Transparent conductive thin film
CN104616726B (en) * 2014-12-17 2017-10-24 青岛墨烯产业科技有限公司 One kind is without indium transparency electrode and preparation method thereof
CN106637204A (en) * 2016-12-01 2017-05-10 梁结平 Depositing method for Ag/ZnO/Mg photoelectric transparent conducting thin film
CN107254664B (en) * 2017-06-27 2019-05-17 河北大学 A kind of ultra-thin silver-based film, MULTILAYER COMPOSITE transparent conductive film and the preparation method and application thereof
CN108385072B (en) * 2018-01-18 2020-04-21 中国科学院宁波材料技术与工程研究所 Transparent conductive film with single-layer structure and preparation method and application thereof
CN109136869B (en) * 2018-07-17 2020-07-31 中山市华南理工大学现代产业技术研究院 Metal gallium oxide-doped transparent conductive film for ultraviolet band and preparation method thereof
CN111593320A (en) * 2020-05-22 2020-08-28 青岛峰峦新材料科技有限责任公司 Graphene-based transparent flexible conductive film layer and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0668713A (en) * 1992-08-20 1994-03-11 Tonen Corp Transparent conductive film
JP2005314131A (en) * 2004-04-27 2005-11-10 Sumitomo Metal Mining Co Ltd Oxide sintered compact, sputtering target, transparent conductive thin film, and their production method
CN101752454A (en) * 2008-12-04 2010-06-23 上海空间电源研究所 Preparation method of ultrathin Cu-In-Ga-Se thin film solar cell with light trap structure
CN102134699A (en) * 2011-02-24 2011-07-27 海洋王照明科技股份有限公司 Preparation method of multilayer transparent conductive thin film as well as prepared thin film and application thereof
CN105624625A (en) * 2016-03-09 2016-06-01 南京邮电大学 Method for improving photoelectric properties of ZnO/Ag/ZnO transparent conductive film
CN108914077A (en) * 2018-08-02 2018-11-30 南京邮电大学 One kind being based on Nb2O5Transparent conductive oxide film and preparation method thereof
CN111593310A (en) * 2020-05-09 2020-08-28 哈尔滨工业大学 Method for preparing transparent conductive film with high photoelectric stability by magnetron sputtering

Also Published As

Publication number Publication date
CN112885503A (en) 2021-06-01

Similar Documents

Publication Publication Date Title
CN112885503B (en) Preparation method and application of ultrathin silver-based OMO (organic molybdenum oxide) composite transparent conductive film
JP5252066B2 (en) Transparent conductive film laminate and manufacturing method thereof, thin film solar cell and manufacturing method thereof
TWI568008B (en) Production method of transparent conductive film and method for manufacturing thin film solar cell
CN102270705B (en) Method for preparing transparent conductive electrode with dual-structure texture surface
US20150303327A1 (en) Transparent-conductive-film laminate, manufacturing method therefor, thin-film solar cell, and manufacturing method therefor
KR20090084539A (en) Surface-textured zinc oxide based transparent conductive thin film having double layer structure and method for preparting the same
CN110970562A (en) Perovskite/crystalline silicon laminated solar cell and preparation method thereof
CN102779891A (en) CIGS thin film type solar cell device and preparation method thereof
CN104617165A (en) Molybdenum disulfide/buffering later/silicon n-i-p solar cell device and preparation method thereof
Acosta et al. AZO/Ag/AZO multilayers electrodes evaluated using a photonic flux density figure of merit for solar cells applications
JP2013521642A (en) Photovoltaic cell
KR101819775B1 (en) Multilayer transparent electroconductive film and method for manufacturing same, as well as thin-film solar cell and method for manufacturing same
CN102199758B (en) Method for growing ZnO-TCO thin film with suede structure and application
Marins et al. Flexible nip thin film silicon solar cells on polyimide foils with textured ZnO: Ga back reflector
US20150311362A1 (en) Transparent-conductive-film laminate, manufacturing method therefor, thin-film solar cell, and manufacturing method therefor
CN112909187A (en) Perovskite crystalline silicon two-end laminated solar cell structure and preparation method thereof
CN102220562B (en) Preparation method of zinc oxide transparent conductive film with sueded structure
US10332691B2 (en) Method for manufacturing HEMT/HHMT device based on CH3NH3PbI3 material
KR102467983B1 (en) Semi-transparent perovskite solar cell having amorphous oxide top electrode with high transparency and Method for manufacturing the same
US10103282B2 (en) Direct texture transparent conductive oxide served as electrode or intermediate layer for photovoltaic and display applications
TW201327862A (en) Conductive substrate and fabricating method thereof, and solar cell
JP5405923B2 (en) Photoelectric conversion element and manufacturing method thereof
KR20210099964A (en) Manufacturing method of the transparent bifacial solar cells and the transparent bifacial solar cells manufactured thereof
Schmidt et al. Highly transparent and conductive ZTO/Ag/ZTO multilayer top electrodes for large area organic solar cells
Jin et al. Sputtering under Mild Heating Enables High-Quality ITO for Efficient Semi-Transparent Perovskite Solar Cells

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant