CN105624820B - Polystyrene/derivatives of porphyrin composite nano fiber and its preparation method and application - Google Patents

Polystyrene/derivatives of porphyrin composite nano fiber and its preparation method and application Download PDF

Info

Publication number
CN105624820B
CN105624820B CN201610066234.5A CN201610066234A CN105624820B CN 105624820 B CN105624820 B CN 105624820B CN 201610066234 A CN201610066234 A CN 201610066234A CN 105624820 B CN105624820 B CN 105624820B
Authority
CN
China
Prior art keywords
derivatives
porphyrin
polystyrene
composite nano
nano fiber
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
CN201610066234.5A
Other languages
Chinese (zh)
Other versions
CN105624820A (en
Inventor
石乃恩
刘栋
仪明东
薛伟
解令海
黄维
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.)
Nanjing Post and Telecommunication University
Original Assignee
Nanjing Post and Telecommunication 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 Nanjing Post and Telecommunication University filed Critical Nanjing Post and Telecommunication University
Priority to CN201610066234.5A priority Critical patent/CN105624820B/en
Publication of CN105624820A publication Critical patent/CN105624820A/en
Application granted granted Critical
Publication of CN105624820B publication Critical patent/CN105624820B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40Organic transistors
    • H10K10/46Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462Insulated gate field-effect transistors [IGFETs]
    • H10K10/466Lateral bottom-gate IGFETs comprising only a single gate
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10Organic polymers or oligomers
    • H10K85/111Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Semiconductor Memories (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention provides a kind of polystyrene/derivatives of porphyrin composite nano fiber and its preparation method and application, raw material includes polystyrene and derivatives of porphyrin, and the structural formula of the derivatives of porphyrin is:Wherein, R1For one kind of pyridine radicals or phenyl, R2For one kind in unsaturated bond or aromatic functional group, R1、R2It is identical or different.The composite nano fiber is made by method of electrostatic spinning, is applied to transistorized memory as charge storage layer.The electric charge capture layer that the composite nano fiber makees transistorized memory has higher specific surface area, can improve the memory window of memory, and is conducive to carrier and is transmitted in the effective of each function interlayer of device.

Description

Polystyrene/derivatives of porphyrin composite nano fiber and its preparation method and application
Technical field
The invention belongs to fiber device arts, and in particular to a kind of polystyrene/derivatives of porphyrin composite Nano is fine Dimension and its preparation method and application.
Background technology
Nanofiber refers to a diameter of Nano grade and the one-dimensional material with certain draw ratio, it, which not only has, usually receives Skin effect, small-size effect etc. possessed by rice material, also with excellent mechanical property, electronics and photon transmission characteristic and Photoconductive property etc., makes it show important application value in photoelectric device and sensor etc..The preparation being currently known The method of nanofiber has pulling method, template synthesis method, phase separation method, self-assembly method etc., if but consider process controllability, The requirement such as equipment complexity, the scope of application, cost, yield and fibre dimensions controllability, above method have respective limitation.It is quiet Electrospinning with its it is easy to operate, applied widely, production efficiency is high the advantages that and more researcher favor.
Meanwhile existing transistorized memory usually selects zero dimension material, as metal nanoparticle, polyfluorene nano particle, Fullerene etc., or two-dimensional material, such as graphene and its redox products, molybdenum disulfide, as carrier storage material, but These materials are integrated into transistorized memory there are many defects, as preparation process it is complicated, it is of high cost, equipment and environment are wanted Seek harshness etc..
The content of the invention
The technical problem of solution:A kind of polystyrene/porphin is provided the purpose of the present invention is overcome the deficiencies in the prior art Quinoline derivant composite nano fiber and its preparation method and application, the composite fibre make the electric charge capture layer energy of transistorized memory Enough improve the memory window of memory.
Technical solution:
Polystyrene/derivatives of porphyrin composite nano fiber, raw material include polystyrene and derivatives of porphyrin, the porphyrin The structural formula of derivative is:
Wherein, R1For one kind of pyridine radicals or phenyl, R2For one kind in unsaturated bond or aromatic functional group, R1、R2It is identical It is or different.
Further, a diameter of 50~800nm of the polystyrene/derivatives of porphyrin composite nano fiber.
Further, the weight ratio of polystyrene and derivatives of porphyrin is 100:0.5~5.
The preparation method of the polystyrene/derivatives of porphyrin composite nano fiber, is that derivatives of porphyrin first is dissolved in N, Dinethylformamide, adds polystyrene, and heating stirring to polystyrene is completely dissolved, finally by resulting solution Static Spinning The obtained composite nano fiber of silk.
Further, the reception device of electrostatic spinning is two parallel metal bars, and metal distance between tie rods is 0.1~5cm.
The polystyrene/application of the derivatives of porphyrin composite nano fiber in transistorized memory, being will be described multiple Close the electronics trapping layer that transistorized memory is made in nanofiber.
The present invention uses reception device of two parallel metal bars with same negative high voltage as electrostatic spinning, is determined To polystyrene/derivatives of porphyrin composite nano fiber, i.e., arrangement with certain orientation composite nano fiber.Relative to Conventional receiver mode obtains nanofiber, and nanofiber of the invention is transferred to SiO2Method on/Si substrates is simpler fast Victory, integrates easy to ensuing memory.In addition, the nanofiber of orientation with the nanofiber being distributed in a jumble compared with lower Roughness, and arrangement and the channel vertical of nanofiber is not in the parallel situation for isolating raceway groove, in orientated nano fibers The pentacene of surface growth is more smooth, and then transistor field-effect also can be better.On this basis, nanofiber does charge-trapping Layer, has the specific surface area of higher, more highdensity storage site can be formed in identical raceway groove, so as to be stored beneficial to improving Window, meanwhile, nanofiber surface can form the built in field of higher and be transmitted beneficial to the effective of carrier.
Beneficial effect:
1. polystyrene/derivatives of porphyrin composite nano fiber is thinner than spin coating as the electronics trapping layer of transistorized memory Film has the specific surface area of higher, and the storage density of higher can be reached in same raceway groove, and then improves the memory window of memory Mouthful;
2. under same grid voltage, polystyrene/derivatives of porphyrin composite nano fiber surface energy forms the built-in electricity of higher , transmitted beneficial to carrier in the effective of each function interlayer of device;
3. the doping concentration of derivatives of porphyrin is the 1% of PS weight, gained transistorized memory can reach the storage of 33V Window, and device has higher reliability.
Brief description of the drawings
Fig. 1 is the electrostatic spinning technique that embodiment 1 uses and the schematic diagram of nanofiber transfer;
Fig. 2 is the scanning electron microscope diagram of polystyrene/derivatives of porphyrin composite nano fiber prepared by embodiment 1;
Fig. 3 is the device architecture schematic diagram of transistorized memory prepared by embodiment 1;
Fig. 4 is the transfer curve of transistorized memory prepared by embodiment 1;
Fig. 5 is the curve of output of transistorized memory prepared by embodiment 1;
Fig. 6 is the drift of the transfer curve of transistorized memory prepared by embodiment 1;
Fig. 7 is the curve of holding time of transistorized memory prepared by embodiment 1;
Fig. 8 is the drift of the transfer curve of transistorized memory prepared by embodiment 2;
Embodiment
Following embodiments further illustrate present disclosure, but should not be construed as limiting the invention.Without departing substantially from In the case of spirit and essence of the invention, the modification and replacement made to the method for the present invention, step or condition, belong to the present invention Scope.Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.
The synthesis of mesoporphyrin derivative of the present invention is with reference to Light-Harvesting and Ultrafast Energy Migration in Porphyrin-Based Metal-Organic Frameworks, Journal of the American Chemical Society, 2013,135 (2), pp 862-869.
Embodiment 1
Weigh a certain amount of derivatives of porphyrin to be dissolved in n,N-Dimethylformamide, ultrasound, adds polystyrene, make polyphenyl Ethylene concentration is 100mg/mL, derivatives of porphyrin:Polystyrene is 1wt%, heats and is stirred until poly- on 50 DEG C of warm tables Compound is completely dissolved, untill solution is in homogeneous, transparence.By the above-mentioned solution configured injection 2mL standard syringe in into Row electrospinning, as shown in Figure 1, front end of the syringe needle connecting external diameter be the stainless steel syringe needle of 0.6mm as nozzle, and connect 15KV just High pressure, parallel metal bar of the spacing for 2cm is placed as reception device in nozzle underface, and connects the negative high voltage of -500V, nozzle With reception device at a distance of 15cm, syringe pump fltting speed is set to carry out electrospinning for 0.001mm/s, the polystyrene oriented/ Derivatives of porphyrin composite nano fiber.
Fig. 2 is the scanning electron microscope diagram piece of polystyrene/derivatives of porphyrin composite nano fiber, can from figure It is smooth to composite nano fiber pattern, average, a diameter of 390nm.
By SiO2/ Si pieces cut into the substrate of 1.5 × 1.5cm, 10 minutes ultrasonic respectively with acetone, ethanol, ultra-pure water, then Dried up with high pressure nitrogen, then prevent from being completely dried it in 20 minutes in 120 DEG C of baking ovens.The substrate of wash clean is lain against multiple Close under nanofiber, and ensure that composite nano fiber is vertical with substrate side, slowly lift substrate and successfully shift nanofiber. The substrate for carrying nanofiber is transferred in glove box, flow perturbation cannot be subject to halfway, otherwise the arrangement of nanofiber It can be destroyed.Substrate is lain against on the warm table in glove box, 200 DEG C annealing 1 it is small when nanofiber soften and strengthen and The contact of substrate.Next it is less than 0.03nm/s in the pentacene of nanofiber surface evaporation 50nm thickness, evaporation rate.Finally, Mask plate is installed on pentacene surface, and ensures that the raceway groove on mask plate is vertical with nanofiber, copper steam-plating source-drain electrode, obtains It is crystal using the polystyrene of orientation/derivatives of porphyrin composite nano fiber as the transistorized memory of charge storage layer, Fig. 3 The device architecture schematic diagram of pipe memory.
The performance of test gained transistorized memory, by SiO2One jiao of/Si pieces is scratched, and only retains grid Si, will be partly Three probes of conductor Parameters Instrument connect source-drain electrode and grid respectively, test its transfer and curve of output, transfer curve respectively Drift and reliability.
Fig. 4 is the transfer curve of transistorized memory,
Fig. 5 is the curve of output of transistorized memory, and as can be seen from the figure gained transistorized memory has reliable Field-effect.
Fig. 6 is the drift of transistorized memory transfer curve, and as can be seen from the figure the memory window of transistor is reachable 33V, has stronger storage capacity.
Fig. 7 is the curve of holding time of transistorized memory, as can be seen from the figure transistorized memory ON state and OFF state Electric current do not occur substantially to decay after the test of 10000s, on-off ratio still has 5.2 × 104, which has preferable Stability.
Embodiment 2
Weigh a certain amount of derivatives of porphyrin to be dissolved in n,N-Dimethylformamide, ultrasound, adds polystyrene, make polyphenyl Ethylene concentration is 100mg/mL, derivatives of porphyrin:Polystyrene is 0.5wt%, heated on 50 DEG C of warm tables and stir until Polymer is completely dissolved, untill solution is in homogeneous, transparence.By in the standard syringe of the above-mentioned solution configured injection 2mL Carry out electrospinning, as shown in Figure 1, front end of the syringe needle connecting external diameter be the stainless steel syringe needle of 0.6mm as nozzle, and connect 15KV's Positive high voltage, parallel metal bar of the spacing for 2cm is placed as reception device in nozzle underface, and connects the negative high voltage of -500V, sprays Head, at a distance of 15cm, sets syringe pump fltting speed to carry out electrospinning, the polyphenyl second oriented for 0.001mm/s with reception device Alkene/derivatives of porphyrin composite nano fiber, gained composite nano fiber pattern is smooth, average, a diameter of 380nm.
By SiO2/ Si pieces are cut into the substrate of 1.5 × 1.5cm, 10 minutes ultrasonic respectively with acetone, ethanol, ultra-pure water, then Dried up with high pressure nitrogen, then being placed 20 minutes in 120 DEG C of baking ovens is completely dried it.Nanofiber is transferred to wash clean Substrate on, then with glove box 200 DEG C of warm tables annealing 1 it is small when, then its show be deposited pentacene and copper source and drain electricity Pole, and ensure that the raceway groove on mask plate is vertical with nanofiber, obtain with the polystyrene of orientation/derivatives of porphyrin composite Nano Transistorized memory of the fiber as charge storage layer.Three probes of semiconductor parameter instrument are connected into source-drain electrode and grid respectively Pole, the storage performance of test transistor memory.
Fig. 8 is the drift of transistorized memory transfer curve, and as can be seen from the figure the memory window of transistor is 16V, Less than the window that embodiment 1 prepares transistorized memory, this explanation does not reach as the derivatives of porphyrin in storage site in doping To before critical value, its content is proportional to the storage capacity of device.

Claims (3)

  1. A kind of 1. transistorized memory, it is characterised in that:The electronics trapping layer of the transistorized memory is by polystyrene/porphyrin Derivative composite nano fiber is made;
    The polystyrene/derivatives of porphyrin composite nano fiber is to use polystyrene and derivatives of porphyrin as raw material Static Spinning Silk is made, and the structural formula of the derivatives of porphyrin is:
    ,
    Wherein, R1For one kind of pyridine radicals or phenyl, R2For one kind in unsaturated bond or aromatic functional group, R1、R2It is identical or not Together.
  2. 2. transistorized memory according to claim 1, it is characterised in that:Polystyrene/the derivatives of porphyrin is compound A diameter of 50~800nm of nanofiber.
  3. 3. transistorized memory according to claim 1, it is characterised in that:Polystyrene/the derivatives of porphyrin is compound The raw material polystyrene of nanofiber and the weight ratio of derivatives of porphyrin are 100:0.5~5.
CN201610066234.5A 2016-01-30 2016-01-30 Polystyrene/derivatives of porphyrin composite nano fiber and its preparation method and application Active CN105624820B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610066234.5A CN105624820B (en) 2016-01-30 2016-01-30 Polystyrene/derivatives of porphyrin composite nano fiber and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610066234.5A CN105624820B (en) 2016-01-30 2016-01-30 Polystyrene/derivatives of porphyrin composite nano fiber and its preparation method and application

Publications (2)

Publication Number Publication Date
CN105624820A CN105624820A (en) 2016-06-01
CN105624820B true CN105624820B (en) 2018-05-11

Family

ID=56040149

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610066234.5A Active CN105624820B (en) 2016-01-30 2016-01-30 Polystyrene/derivatives of porphyrin composite nano fiber and its preparation method and application

Country Status (1)

Country Link
CN (1) CN105624820B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106433618A (en) * 2016-09-21 2017-02-22 天津工业大学 Preparation method for fluorescent colorimetric chemical sensor and application of fluorescent colorimetric chemical sensor in gas detection
CN106442497A (en) * 2016-09-21 2017-02-22 天津工业大学 Preparation method of porphyrin/nano porous fiber membrane hydrogen chloride gas sensor
CN106684244B (en) * 2016-11-03 2019-07-09 南京邮电大学 A kind of floating gate type flexibility low-voltage organic field effect tube memory
CN108796825B (en) * 2018-06-22 2019-08-27 南京邮电大学 Detect the porous nano-fibre film and the preparation method and application thereof of wet environment explosive vapors
CN111548683B (en) * 2020-05-13 2021-09-28 南京邮电大学 Polystyrene-porphyrin derivative nano vertical array film and preparation method and application thereof
CN113802208B (en) * 2021-10-09 2022-09-13 吉林大学 Multifunctional transparent nanofiber screen window and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1876901A (en) * 2006-07-10 2006-12-13 南开大学 Receiver for collecting electrospun polymer fiber tube
CN101285791A (en) * 2008-05-23 2008-10-15 浙江大学 Ampere type biosensor electrode and method for making same
CN101338189A (en) * 2008-08-27 2009-01-07 吉林大学 High voltage electrospinning method for preparing multi-fluorescence-encoded micro-beads
CN101937777A (en) * 2010-07-20 2011-01-05 东华大学 Method for manufacturing dye sensitized solar cell
CN105133188A (en) * 2015-07-31 2015-12-09 南京邮电大学 Polymer nanometer fiber film doped with carbazole derivative and preparation method and application
CN105261700A (en) * 2015-09-07 2016-01-20 武汉理工大学 Fiber-based non-volatile memory device and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9198462B2 (en) * 2011-09-04 2015-12-01 Jalaledin Ghanavi Nanostructural filter for removing toxic compounds

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1876901A (en) * 2006-07-10 2006-12-13 南开大学 Receiver for collecting electrospun polymer fiber tube
CN101285791A (en) * 2008-05-23 2008-10-15 浙江大学 Ampere type biosensor electrode and method for making same
CN101338189A (en) * 2008-08-27 2009-01-07 吉林大学 High voltage electrospinning method for preparing multi-fluorescence-encoded micro-beads
CN101937777A (en) * 2010-07-20 2011-01-05 东华大学 Method for manufacturing dye sensitized solar cell
CN105133188A (en) * 2015-07-31 2015-12-09 南京邮电大学 Polymer nanometer fiber film doped with carbazole derivative and preparation method and application
CN105261700A (en) * 2015-09-07 2016-01-20 武汉理工大学 Fiber-based non-volatile memory device and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"A facile and sensitive fluorescent sensor using electrospun nanofibrous film for nitroaromatic explosive detection";Yufei Yang;《J. Mater. Chem.》;20110731;第21卷;11895-11900 *
Light-Harvesting and Ultrafast Energy Migration in Porphyrin-Based Metal−Organic Frameworks;Ho-Jin Son;《Journal of the American Chemical Society》;20121218;第135卷;862-869 *

Also Published As

Publication number Publication date
CN105624820A (en) 2016-06-01

Similar Documents

Publication Publication Date Title
CN105624820B (en) Polystyrene/derivatives of porphyrin composite nano fiber and its preparation method and application
CN102412369B (en) Organic/inorganic hybrid solar cell and preparation method thereof
Kuwabara et al. Mechanistic insights into UV-induced electron transfer from PCBM to titanium oxide in inverted-type organic thin film solar cells using AC impedance spectroscopy
Wu et al. Hybrid photovoltaic devices based on poly (3-hexylthiophene) and ordered electrospun ZnO nanofibers
Mali et al. Novel synthesis and characterization of mesoporous ZnO nanofibers by electrospinning technique
Rice et al. Controlling vertical morphology within the active layer of organic photovoltaics using poly (3-hexylthiophene) nanowires and phenyl-C61-butyric acid methyl ester
CN107195781B (en) PMMA-doped small molecule-based high-mobility transistor and preparation method thereof
CN105469996A (en) Perovskite solar cell based on metal nanoparticle interface modification and preparation method of perovskite solar cell
KR20130117144A (en) Inverted organic solar cell and method for producing the same
CN102544378A (en) Organic/inorganic hybridization solar cell based on zinc oxide (ZnO) homogeneous core-shell structure nanorod array and production method thereof
CN109980090A (en) A kind of efficient ternary organic photovoltaic cell and preparation method thereof
CN106601803A (en) Method for preparing indium oxide/aluminium oxide nanofiber filed effect transistor through UV light pretreatment
WO2018161707A1 (en) Organic photoactive layer composite ink, organic solar cell and preparation method thereof
CN101894913B (en) Method for preparing macromolecular field effect transistor with ultrahigh charge mobility
Tan et al. Electrodepostied polyaniline films decorated with nano-islands: Characterization and application as anode buffer layers in solar cells
CN105990527A (en) Inverted polymer solar cell with silver nanowire/ZnO laminated layer as electronic collection layer and manufacturing method thereof
CN108232016A (en) Perovskite solar cell based on cellulose modifying hole transmission layer
CN107103944B (en) A kind of oriented alignment method of metal nanometer line
CN105185911B (en) A kind of polymer solar battery based on solvent doping and preparation method thereof
Vohra et al. Efficient ultrathin organic solar cells with sustainable β-carotene as electron donor
CN108832007B (en) Preparation method of perovskite and semiconductor type silicon hybrid solar cell
CN103151462B (en) A kind of based on TiO2hybrid solar cell of homogeneity core-shell nano array and preparation method thereof
Ben Dkhil et al. Reduction of Charge-Carrier Recombination at ZnO–Polymer Blend Interfaces in PTB7-Based Bulk Heterojunction Solar Cells Using Regular Device Structure: Impact of ZnO Nanoparticle Size and Surfactant
CN102983275A (en) Polymer solar cell with water-soluble vanadium pentoxide hole-transport layer and fabrication method of polymer solar cell
WO2023035446A1 (en) Perovskite thin film and preparation method therefor

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant