CN110690311B - Si substrate GaSe visible light detector and preparation method thereof - Google Patents

Si substrate GaSe visible light detector and preparation method thereof Download PDF

Info

Publication number
CN110690311B
CN110690311B CN201911022490.4A CN201911022490A CN110690311B CN 110690311 B CN110690311 B CN 110690311B CN 201911022490 A CN201911022490 A CN 201911022490A CN 110690311 B CN110690311 B CN 110690311B
Authority
CN
China
Prior art keywords
gase
functional layer
substrate
temperature
visible light
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
CN201911022490.4A
Other languages
Chinese (zh)
Other versions
CN110690311A (en
Inventor
王文樑
李国强
杨昱辉
孔德麒
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.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
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 South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201911022490.4A priority Critical patent/CN110690311B/en
Publication of CN110690311A publication Critical patent/CN110690311A/en
Application granted granted Critical
Publication of CN110690311B publication Critical patent/CN110690311B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/08Semiconductor 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 in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/09Devices sensitive to infrared, visible or ultraviolet radiation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/02Details
    • H01L31/0224Electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/0248Semiconductor 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 characterised by their semiconductor bodies
    • H01L31/0256Semiconductor 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 characterised by their semiconductor bodies characterised by the material
    • H01L31/0264Inorganic materials
    • H01L31/032Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

The invention discloses a Si substrate GaSe visible light detector and a preparation method thereof, comprising a Si substrate, wherein a first GaSe functional layer grown at low temperature PLD and a second GaSe functional layer grown at high temperature PLD are sequentially arranged on the upper surface of the Si substrate, the thicknesses of the first GaSe functional layer and the second GaSe functional layer are the same, and two ends of the upper surface of the second GaSe functional layer are connected with Ti/Ni/Au metal layer electrodes. The invention effectively reduces the reflection loss of the surface to visible light, enhances the resonance absorption of the visible light, and realizes high-sensitivity and high-bandwidth detection.

Description

Si substrate GaSe visible light detector and preparation method thereof
Technical Field
The invention relates to the field of visible light detectors, in particular to a Si substrate GaSe visible light detector and a preparation method thereof.
Background
A photodetector is a device that converts an optical signal into an electrical signal using the principle of the photoelectric effect. Light is an electromagnetic wave and can be classified into various types according to the wavelength thereof. Light having a wavelength in the range of 380nm to 780nm is called visible light. Visible light detectors have important applications in the military and civilian fields due to their specific spectral response ranges.
In recent years, photodetectors based on multilayer direct bandgap two-dimensional materials (such as In 2Se3) have received widespread attention as potential alternatives to high performance photovoltaic devices. Multilayer two-dimensional materials are easier to deposit than single-layer two-dimensional materials, and therefore direct bandgap multilayer two-dimensional materials are more practical.
GaSe is a typical III-vi semiconductor material that has many excellent photovoltaic properties. GaSe is a p-type semiconductor, and has high carrier mobility (0.1 cm 2V-1s-1), low dark current and high resistivity. Meanwhile, the photoelectric property of GaSe has strong layer thickness dependence. The forbidden bandwidth becomes larger gradually with the decrease of the layer number. Furthermore, gaSe has an indirect bandgap of about 2.11eV and its direct bandgap is only 25meV greater than the indirect bandgap. Thus, at room temperature, electrons can easily be transferred between conduction band minima. Meanwhile, gaSe also has proper optical band gap, nonlinear optical property and light response characteristic. Therefore, the GaSe is suitable for being applied to the preparation research of the visible light detector.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention provides a Si substrate GaSe visible light detector and a preparation method thereof. The invention has the advantages of good quality of the grown GaSe film, high external quantum efficiency of the device, high response speed, high bandwidth and the like.
The invention adopts the following technical scheme:
The Si substrate GaSe visible light detector comprises a Si substrate, wherein a first GaSe functional layer grown at low temperature PLD and a second GaSe functional layer grown at high temperature PLD are sequentially arranged on the upper surface of the Si substrate, the thicknesses of the first GaSe functional layer and the second GaSe functional layer are the same, and two ends of the upper surface of the second GaSe functional layer are connected with Ti/Ni/Au metal layer electrodes.
Preferably, the thickness of the first GaSe functional layer and the second GaSe functional layer is 5-6nm.
Preferably, the Ti/Ni/Au metal layer electrode is an interdigital electrode.
Preferably, in the Ti/Ni/Au metal layer electrode, the thickness of the Ti metal layer is 25-35nm, the thickness of the Ni metal layer is 90-110 nm, and the thickness of the Au metal layer is 90-110 nm.
Preferably, the upper surface of the second GaSe functional layer is plated with a layer of nano-scale Ag particles.
A preparation method of a Si substrate GaSe visible light detector comprises the following steps:
S1, growing a first GaSe functional layer on a Si substrate by adopting a low-temperature PLD method, growing a second GaSe functional layer by adopting a high-temperature PLD method, and analyzing the surface morphology of a sample by adopting an AFM;
S2, uniformly coating, drying, exposing, developing and oxygen ion treatment on the upper surface of the second GaSe functional layer to determine the shape of the electrode, and evaporating Ti/Ni/Au metal layer electrodes on two ends of the upper surface of the second GaSe functional layer through an evaporation process.
Preferably, the temperature of the first GaSe functional layer grown by adopting a low-temperature PLD method is 440-460 ℃, the pulse energy is 0.46-0.50J/cm 2, and the growth time is 25-45 min.
Preferably, the temperature of growing the second GaSe functional layer by adopting a high-temperature PLD method is 840-860 ℃, the pulse energy is 0.42-0.54J/cm 2, and the growth time is 25-45 min.
Preferably, the drying time is 38-45 s, the exposure time is 5-8 s, the development time is 40-45 s, and the oxygen ion treatment time is 1.5-2.5 min.
Preferably, the growth time of the first GaSe functional layer is 30min.
The invention has the beneficial effects that:
(1) According to the invention, two GaSe functional layers are adopted to promote the transverse migration rate of carriers;
(2) The first GaSe functional layer grows on the Si substrate PLD at low temperature, so that the problem that the material can react with the substrate at an interface due to direct high-temperature growth is solved;
(3) The detector prepared by the method has high material quality, good performance, time saving, high efficiency and low energy consumption, and is beneficial to large-scale production;
(4) According to the invention, the visible light sensitization micro-nano structure design is carried out on the surface of the detection chip, so that the reflection loss of the surface to visible light is effectively reduced, the resonance absorption of the visible light is enhanced, and the high-sensitivity and high-bandwidth detection is realized.
Drawings
FIG. 1 is a schematic cross-sectional view of the structure of the present invention;
FIG. 2 is a schematic top plan view of FIG. 1;
FIG. 3 is an AFM test pattern of a first GaSe functional layer sample grown at low temperature by PLD in the examples;
FIG. 4 is a graph showing the light response characteristics of the probe prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
A Si substrate GaSe visible light detector is shown in fig. 1, and comprises a Si substrate 1, wherein a first GaSe functional layer 2 grown at low temperature PLD and a second GaSe functional layer 3 grown at high temperature PLD are sequentially arranged on the upper surface of the Si substrate, the thicknesses of the first GaSe functional layer and the second GaSe functional layer are the same, and two ends of the upper surface of the second GaSe functional layer are connected with Ti/Ni/Au metal layer electrodes 4.
In this embodiment, the first and second GaSe functional layers have the same structural dimensions, and preferably have a thickness of 5nm.
In this example, the Ti metal layer in the Ti/Ni/Au metal layer electrode 4 had a thickness of 30nm, the Ni metal layer had a thickness of 100nm, and the Au metal layer had a thickness of 100nm.
In the prior art, the visible light detector is prepared mainly by adopting an MOCVD method, and the film grown by the method has poor quality and high roughness.
A method for preparing a Si substrate GaSe visible light detector comprises the following steps:
S1, growing a first GaSe functional layer on a Si substrate by adopting a low-temperature PLD method, growing a second GaSe functional layer by adopting a high-temperature PLD method, and analyzing the surface morphology of a sample by adopting an AFM;
S2, uniformly coating, drying, exposing, developing and oxygen ion treatment on the upper surface of the second GaSe functional layer to determine the shape of the electrode, and evaporating Ti/Ni/Au metal layer electrodes on two ends of the upper surface of the second GaSe functional layer through an evaporation process.
As shown in fig. 2, the electrodes are interdigital electrodes, and the Ti/Ni/Au metal layer electrodes 4 are vapor-deposited on both ends of the upper surface of the second GaSe functional layer 3 by vapor deposition process.
The temperature is 450 ℃ when the first GaSe functional layer is grown by adopting a low-temperature PLD method, the pulse energy is 0.48J/cm 2, the growth time is 30min, and the evaporation rate of the electrode is 0.25nm/min.
The temperature is 850 ℃, the pulse energy is 0.48J/cm 2, the growth time is 30min, and the evaporation rate of the electrode is 0.25nm/min when the GaSe functional layer is grown by adopting a high-temperature PLD method.
The prepared visible light detector was tested, and fig. 3 is an AFM test pattern of a first GaSe functional layer sample grown epitaxially by PLD in example. It can be seen that the sample has grown GaSe material with a surface roughness of 6.5nm. Tests show that the PLD has a smoother surface and smaller roughness when the growth time is 30 min.
FIG. 4 is a graph showing the light response characteristics of the Si substrate GaSe visible light detector obtained in this example. As can be seen from the curve, the Si substrate GaSe visible light detector obtained in the embodiment has obvious wave peaks in the 620nm wave band, and the responsivity is 2.5 mu A/W. Tests show that the photoelectric detector has high responsivity in the visible light wave band range, which indicates that the photoelectric detector has high sensitivity.
Example 2
The preparation process of this example is the same as that of example 1, except that:
The temperature of the first GaSe functional layer grown by adopting a low-temperature PLD method is 440, the pulse energy is 0.46J/cm 2, and the growth time is 25min.
The temperature is 840 ℃ when the GaSe functional layer is grown by adopting a high-temperature PLD method, the pulse energy is 0.42J/cm 2, the growth time is 45min, and the evaporation rate of the electrode is 0.25nm/min.
Example 3
The preparation process of this example is the same as that of example 1, except that:
The temperature of the first GaSe functional layer grown by adopting a low-temperature PLD method is 460 ℃, the pulse energy is 0.46J/cm 2, and the growth time is 25min.
The temperature is 860 ℃ when the GaSe functional layer is grown by adopting a high-temperature PLD method, the pulse energy is 0.42J/cm 2, the growth time is 25min, and the evaporation rate of the electrode is 0.25nm/min.
The embodiments described above are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described above, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention should be made in the equivalent manner, and are included in the scope of the present invention.

Claims (7)

1. The Si substrate GaSe visible light detector is characterized by comprising a Si substrate, wherein a first GaSe functional layer grown at low temperature PLD and a second GaSe functional layer grown at high temperature PLD are sequentially arranged on the upper surface of the Si substrate, the thicknesses of the first GaSe functional layer and the second GaSe functional layer are the same, and two ends of the upper surface of the second GaSe functional layer are connected with Ti/Ni/Au metal layer electrodes;
The thickness of the first GaSe functional layer and the second GaSe functional layer is 5-6nm;
The temperature of the first GaSe functional layer grown by adopting a low-temperature PLD method is 440-460 ℃, the pulse energy is 0.46-0.50J/cm 2, and the growth time is 25-45 min;
The second GaSe functional layer is grown by adopting a high-temperature PLD method, the temperature is 840-860 ℃, the pulse energy is 0.42-0.54J/cm 2, and the growth time is 25-45 min.
2. The Si-substrate GaSe visible light detector of claim 1, wherein the Ti/Ni/Au metal layer electrode is an interdigital electrode.
3. The GaSe visible light detector of claim 2, wherein in the Ti/Ni/Au metal layer electrode, the Ti metal layer has a thickness of 25-35nm, the Ni metal layer has a thickness of 90-110 nm, and the Au metal layer has a thickness of 90-110 nm.
4. The Si-substrate GaSe visible light detector of claim 1, wherein the upper surface of the second GaSe functional layer is coated with a layer of nano-sized Ag particles.
5. A method of producing a Si-substrate GaSe visible light detector as defined in any one of claims 1 to 4, comprising the steps of:
S1, growing a first GaSe functional layer on a Si substrate by adopting a low-temperature PLD method, growing a second GaSe functional layer by adopting a high-temperature PLD method, and analyzing the surface morphology of a sample by adopting an AFM;
S2, uniformly coating, drying, exposing, developing and oxygen ion treatment on the upper surface of the second GaSe functional layer to determine the shape of the electrode, and evaporating Ti/Ni/Au metal layer electrodes on two ends of the upper surface of the second GaSe functional layer through an evaporation process.
6. The method according to claim 5, wherein the baking time is 38 to 45 seconds, the exposure time is 5 to 8 seconds, the development time is 40 to 45 seconds, and the oxygen ion treatment time is 1.5 to 2.5 minutes.
7. The method of claim 5, wherein the first GaSe functional layer is grown for 30 minutes.
CN201911022490.4A 2019-10-25 2019-10-25 Si substrate GaSe visible light detector and preparation method thereof Active CN110690311B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911022490.4A CN110690311B (en) 2019-10-25 2019-10-25 Si substrate GaSe visible light detector and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911022490.4A CN110690311B (en) 2019-10-25 2019-10-25 Si substrate GaSe visible light detector and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110690311A CN110690311A (en) 2020-01-14
CN110690311B true CN110690311B (en) 2024-07-05

Family

ID=69114060

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911022490.4A Active CN110690311B (en) 2019-10-25 2019-10-25 Si substrate GaSe visible light detector and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110690311B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103236469A (en) * 2013-04-22 2013-08-07 哈尔滨工业大学 Method for preparing gallium telluride two-dimensional structural material and method for producing flexible transparent two-dimensional structural gallium telluride optical detector
CN108400183A (en) * 2018-02-28 2018-08-14 华南理工大学 AlGaN Base Metals-semiconductor-metal type ultraviolet detector and preparation method thereof on a kind of Si substrates

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7138697B2 (en) * 2004-02-24 2006-11-21 International Business Machines Corporation Structure for and method of fabricating a high-speed CMOS-compatible Ge-on-insulator photodetector
US7381966B2 (en) * 2006-04-13 2008-06-03 Integrated Micro Sensors, Inc. Single-chip monolithic dual-band visible- or solar-blind photodetector
CN101887930A (en) * 2010-05-26 2010-11-17 中国科学院半导体研究所 Method for preparing silicon detector with high photoelectric response at room temperature
US8384179B2 (en) * 2010-07-13 2013-02-26 University Of Electronic Science And Technology Of China Black silicon based metal-semiconductor-metal photodetector
US9861975B2 (en) * 2014-12-03 2018-01-09 National Applied Research Laboratories Visible light response catalyst structure and process for manufacturing the same
CN107634106B (en) * 2017-09-19 2019-10-08 北京工业大学 A kind of two-dimensional material photodetector enhancing visible light and near infrared band light absorption
CN107644921B (en) * 2017-10-18 2023-08-29 五邑大学 Novel avalanche diode photoelectric detector and preparation method thereof
CN107994099B (en) * 2017-11-23 2019-08-09 西北工业大学 Based on two-dimentional gallium selenide material field effect transistor preparation method
CN108231924A (en) * 2018-02-28 2018-06-29 华南理工大学 It is grown in non polarity A lGaN base MSM type ultraviolet detectors in r surface sapphire substrates and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103236469A (en) * 2013-04-22 2013-08-07 哈尔滨工业大学 Method for preparing gallium telluride two-dimensional structural material and method for producing flexible transparent two-dimensional structural gallium telluride optical detector
CN108400183A (en) * 2018-02-28 2018-08-14 华南理工大学 AlGaN Base Metals-semiconductor-metal type ultraviolet detector and preparation method thereof on a kind of Si substrates

Also Published As

Publication number Publication date
CN110690311A (en) 2020-01-14

Similar Documents

Publication Publication Date Title
US11710801B2 (en) Silicon carbide-based full-spectrum-responsive photodetector and method for producing same
CN111554757A (en) Plasmon enhancement-based graphene mid-infrared light detector and preparation method thereof
CN105470320A (en) Molybdenum disulfide/semiconductor heterojunction photoelectric detector and manufacturing method therefor
CN110676339B (en) Gallium oxide nanocrystalline film solar blind ultraviolet detector and preparation method thereof
Li et al. Broadband InSb/Si heterojunction photodetector with graphene transparent electrode
Wu et al. Fabrication and photoresponse of ZnO nanowires/CuO coaxial heterojunction
CN110444626A (en) Si substrate InGaN visible-light detector and preparation method and application
CN109698250B (en) Grid-regulated AlGaN-based metal-semiconductor-metal ultraviolet detector and preparation method thereof
CN109742179A (en) A kind of photodetector and preparation method thereof based on stannic selenide/silicon heterogenous
CN108630782B (en) Preparation method of wide detection waveband dual-plasma working photoelectric detector
CN110459628A (en) A kind of multiple quantum wells blue light detector and preparation method and application
CN110690313A (en) Si substrate MoS2Near-infrared light detector and preparation method thereof
Fei et al. Improved responsivity of MgZnO film ultraviolet photodetectors modified with vertical arrays ZnO nanowires by light trapping effect
CN110416333B (en) Ultraviolet photoelectric detector and preparation method thereof
CN110112233A (en) Based on silver nanowires-graphene/gallium oxide nano-pillar photodetection structure, device and preparation method
CN112054074B (en) Photoelectric detector array and preparation method thereof, photoelectric detector and preparation method thereof
CN110164993A (en) A kind of ultraviolet band multi-wavelength detector and preparation method thereof
CN110690311B (en) Si substrate GaSe visible light detector and preparation method thereof
CN210805799U (en) Si substrate GaSe visible light detector
CN116799092A (en) Solar blind ultraviolet detector based on gallium oxide base and preparation method thereof
CN116895705A (en) Interdigital graphene type InGaN visible light detector and preparation method thereof
CN109950359A (en) It is a kind of to be passivated enhanced low-dimensional nanometer detection device and preparation method using hafnium oxide
TW200950109A (en) UV inspector for zinc oxide nano-pillar
CN210607284U (en) Multi-quantum well blue light detector
CN111081886A (en) PIN diode based on gallium oxide perovskite multilayer stacked structure and preparation method thereof

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