CN110698497A - A-D-A type conjugated micromolecule semiconductor material based on condensed ring and indole-2-ketone - Google Patents

A-D-A type conjugated micromolecule semiconductor material based on condensed ring and indole-2-ketone Download PDF

Info

Publication number
CN110698497A
CN110698497A CN201910862239.2A CN201910862239A CN110698497A CN 110698497 A CN110698497 A CN 110698497A CN 201910862239 A CN201910862239 A CN 201910862239A CN 110698497 A CN110698497 A CN 110698497A
Authority
CN
China
Prior art keywords
semiconductor material
indole
ketone
condensed ring
micromolecule
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.)
Pending
Application number
CN201910862239.2A
Other languages
Chinese (zh)
Inventor
张国兵
陈瑞锟
孙明祥
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.)
Hefei University of Technology
Hefei Polytechnic University
Original Assignee
Hefei Polytechnic 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 Hefei Polytechnic University filed Critical Hefei Polytechnic University
Priority to CN201910862239.2A priority Critical patent/CN110698497A/en
Publication of CN110698497A publication Critical patent/CN110698497A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • 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

The invention discloses an A-D-A type conjugated micromolecule semiconductor material based on condensed rings and indole-2-ketone, which has the advantages of traditional micromolecules and conjugated polymers, has a definite molecular structure, no batch difference and good film forming property. The small molecular semiconductor material has a fused ring rigid donor structure, a thiophene bridge is used as a connecting unit, indole-2-ketone and derivatives thereof are used as an acceptor unit, an A-D-A type novel small molecular semiconductor material is combined, meanwhile, alkyl chains are introduced into the donor and the acceptor unit, and the solubility of the material is ensured.

Description

A-D-A type conjugated micromolecule semiconductor material based on condensed ring and indole-2-ketone
Technical Field
The invention belongs to the technical field of organic micromolecule semiconductor materials, and particularly relates to an A-D-A type conjugated micromolecule semiconductor material based on condensed rings and indole-2-ketone.
Background
In recent years, the research on the application of conjugated polymer materials in organic photovoltaics and organic thin film transistors has attracted extensive attention, and the photovoltaic energy conversion efficiency and the field effect mobility of the conjugated polymer materials respectively exceed 10 percent and 10cm2V-1s-1. However, the conjugated polymer has polydispersity, the molecular weight thereof is in a dispersed distribution, and the polymer has batch variation and poor repeatability, which brings challenges to future commercial application. The organic micromolecules have definite molecular structures, single molecular weight, good repeatability and high purity, but the solution processability is poor, so that the development of the micromolecule semiconductor material capable of being processed by solution has important significance. The D-A interaction similar to that of a polymer is carried out in/among conjugated small molecules of a donor/acceptor (D/A) structure, and the D/A small molecules have the advantages of the conjugated polymer and the traditional small molecules, including a definite molecular structure, high purity, good solution processability and the like. Therefore, the conjugated small molecules of the D/A structure are effective structures for developing structure-defined, solution-processable organic semiconductor materials.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides an A-D-A type conjugated micromolecule semiconductor material based on condensed rings and indole-2-ketone, the micromolecule semiconductor material has a donor structure with condensed ring rigidity, a thiophene bridge is used as a connecting unit, indole-2-ketone and derivatives thereof are used as receptor units to combine into a novel micromolecule semiconductor material of a donor-receptor-donor type (A-D-A type), and meanwhile, alkyl chains are introduced into the donor and the receptor units to ensure the solubility of the material.
In order to achieve the above object, the present invention provides the following technical solutions:
A-D-A type conjugated micromolecule semiconductor material based on condensed ring and indole-2-ketone, wherein the structural formula of the micromolecule semiconductor material is as follows:
wherein X is CH, CF, or N;
R1is CnH2n+1An alkyl chain, n is more than or equal to 1; or R1Is an alkyl benzene chain
Figure BDA0002200149650000022
Further, the main chain structure of the small molecular material is an indole-2-ketone acceptor and a fused ring donor.
Further, the branched chain structure of the small molecule material is as follows:
R1is CnH2n+1An alkyl chain, n is more than or equal to 1; or R1Is an alkyl benzene chain
Figure BDA0002200149650000023
R2Is CnH2n+1Alkyl chain, n is more than or equal to 1.
Further, the micromolecule material is prepared by Stille or C-H activation reaction.
The invention also provides a preparation method of the micromolecule semiconductor material, which is prepared by Stille or C-H activation reaction by taking the condensed ring as a donor unit and the indole-2-ketone as an acceptor unit, wherein the monomer structure is as follows:
Figure BDA0002200149650000031
the A-D-A type conjugated micromolecule semiconductor material based on the condensed ring and the indole-2-ketone is applied to the preparation of organic thin film transistors, organic photovoltaic cells and thermoelectric conversion devices.
The invention has the advantages that:
the novel conjugated micromolecule semiconductor material is an A-D-A type conjugated micromolecule semiconductor material prepared by utilizing the coplanar property of a condensed ring donor and the strong electron deficiency characteristic of indole-2-ketone, and has strong intramolecular/intermolecular interaction, so that high carrier mobility is expected to be obtained; meanwhile, a flexible alkyl chain is introduced, excellent solubility is achieved, the novel A-D-A type conjugated micromolecule semiconductor material has the characteristic of solution processing, and the novel A-D-A type conjugated micromolecule semiconductor material can be applied to the fields of organic thin film transistors, organic photovoltaics and other organic electronics.
Drawings
FIG. 1 is a schematic diagram showing the synthesis route of the novel A-D-A type conjugated small molecule semiconductor material.
FIG. 2 is a schematic diagram showing the synthetic route of the small molecule M1 in example 1.
FIG. 3 is a schematic diagram showing the synthetic route of the small molecule M2 in example 2.
Fig. 4 shows the ultraviolet spectrum of the conjugated small molecule M1.
Fig. 5 shows the field effect behavior of the conjugated small molecule M1.
Detailed Description
The technical scheme of the invention is further explained by combining the specific examples as follows:
as shown in figure 1, the target conjugated A-D-A type micromolecular semiconductor material is obtained by using bromide of indole diketone and derivatives thereof as an acceptor unit, using condensed rings as a donor unit, synthesizing through Stille and C-H activation reaction, and purifying a monomer by adopting column chromatography.
Example 1
Synthesis of A-D-A type conjugated Small molecule semiconductor Material M1 (see FIG. 2)
(1) Synthesis of intermediate 1: the raw materials 6-bromoisatin (3g,13.3mmol), 1-iodohexane (3.52g,16.6mmol), K were added to two bottles, respectively2CO3(3.67g,36.54mmol) and N, N-dimethylformamide (40mL) as a solvent, reacting at 50 ℃ overnight, directly rotary evaporating the solvent, adding water, extracting with dichloromethane, collecting the organic layer, drying, rotary evaporating the solvent, and then passing through the column to obtain 2.7 g;
(2) synthesis of intermediate 2: adding the intermediate 1(2.0g) and hydrazine hydrate (40mL) into a two-neck flask, refluxing for 24 hours, cooling to room temperature, adding water, extracting with dichloromethane, collecting the organic layer, drying, rotary evaporating the solvent, and then passing through a column to obtain 1.2 g;
(3) synthesis of intermediate 3: adding the intermediate 2(1.1g, 5.02mmol), 5-bromo-2-formylthiophene (1.4g,7.53mmol) and chloroform solvent (25mL) into a two-necked flask, adding 2 drops of piperidine, refluxing for 24 hours, cooling to room temperature, directly evaporating the solvent in a rotary manner, and passing through a column to obtain 1.3 g;
(4) synthesis of M1: intermediate 3(0.10g,0.26mmol) and bis-tin monomer (0.15g, 0.11mmol) were added to a Schlenk flask, respectively, air was removed, and Pd was added2(dba)3Catalyst (4mg), P (o-tol)3(5mg) and toluene (15mL) were reacted at 110 ℃ for 24h, water was added, extraction was performed with chloroform, and the organic layer was collected, dried, rotary evaporated, and passed through a column to obtain 50 mg.
Example 2
Synthesis of A-D-A type conjugated Small molecule semiconductor Material M2 (see FIG. 3)
(1) Synthesis of intermediate 4: respectively adding raw materials 6-bromo-7-azaindole (3.0g,15.24mmol), 1-iodohexane (3.60g,16.77mmol), sodium hydride (0.74g,18.3mmol) and a solvent N, N-dimethylformamide (10mL) into two bottles, reacting at room temperature overnight, directly carrying out rotary evaporation on the solvent, adding water, extracting with dichloromethane, collecting an organic layer, drying, carrying out rotary evaporation on the solvent, and then carrying out column chromatography to obtain 3.9 g;
(2) synthesis of intermediate 5: adding the intermediate 4(3.9g,13.87mmol), PCC (9.0g,41.61mmol), aluminum trichloride (10mg), acetonitrile (25mL) and 1, 2-dichloroethane (25mL) into two bottles respectively, refluxing for 3 hours, cooling to room temperature, adding water, extracting with dichloromethane, collecting an organic layer, drying, rotary evaporating the solvent, and passing through a column to obtain 2.1 g;
(3) synthesis of intermediate 6: adding intermediate 5(1.32g,5.68mmol), hydrazine hydrate (20mL) and ethanol (5mL) into a two-necked flask, refluxing overnight, cooling to room temperature, extracting with dichloromethane, collecting the organic solvent, drying, rotary evaporating the solvent, and passing through a column to obtain 0.85 g;
(4) synthesis of intermediate 7: respectively adding the intermediate 6(0.85g, 3.89mmol), 5-bromo-2-aldehyde thiophene (1.6g,5.84mmol), 2 drops of piperidine and chloroform (10mL) into two bottles, refluxing for overnight reaction, cooling to room temperature, extracting with dichloromethane, collecting an organic layer, drying, carrying out rotary evaporation on the solvent, and carrying out column chromatography to obtain 1 g;
(5) synthesis of M2: in a Schlenk flask, intermediate 7(0.044g, 0.12mmol), condensed ring tin monomer (0.06g, 0.045mmol) were added, respectively, air was removed, and Pd was added2(dba)3(3mg),P(o-tol)3(4mg), chlorobenzene (10mL), was reacted at 130 ℃ for 12 hours, cooled to room temperature, added with water, extracted with chloroform, and the organic layer was collected, dried, rotary evaporated, and subjected to column chromatography to obtain 40 mg.
Example 3
Other monomers are adopted to synthesize a series of A-D-A type micromolecular materials, and the specific steps are the same as those of the embodiment 1 and the embodiment 2. In a Schlenk flask, 0.11mol of fused ring donor unit, 2.3 times of acceptor unit, anhydrous solvent (Stille reaction is toluene, C-H activation reaction is N, N-dimethylacetamide), air is removed, catalyst and ligand are added, wherein Stille reaction is (Pd)2dba3)Pd2(dba3) And P (o-tol)3(P(o-toly)3) The C-H activation reaction is palladium acetate and PCy3.HBF4Reacting at 110 ℃ for 24 hours, cooling to room temperature, adding water and chloroform, collecting an organic layer, drying, performing rotary evaporation, and passing through a column to obtain a target product, wherein the structural formula of the target product is shown as the following.
Figure BDA0002200149650000061
FIG. 4 shows the absorption spectrum of M1 in solution, with a maximum absorption peak of 550 nm. FIG. 5 shows the transfer and output curves of an organic thin film transistor device with M1 as the semiconductor layer, the device achieving excellent field effect performance and the maximum hole mobility exceeding 0.7cm2V-1s-1. Therefore, the novel conjugated micromolecules related to the invention are semiconductor materials which can be processed by solution and have excellent performance, and can be applied to the fields of organic thin film transistors, organic photovoltaic devices and organic thermoelectric materials.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (5)

1. A-D-A type conjugated micromolecule semiconductor material based on condensed ring and indole-2-ketone is characterized in that the micromolecule semiconductor material has a structural formula as follows:
Figure FDA0002200149640000011
wherein X is CH, CF, or N;
R1is CnH2n+1An alkyl chain, n is more than or equal to 1; or R1Is an alkyl benzene chain
Figure FDA0002200149640000012
2. The A-D-A type conjugated micromolecule semiconductor material based on condensed ring and indole-2-ketone according to claim 1, characterized in that the main chain structure of the micromolecule semiconductor material is an acceptor of the indole-2-ketone and a donor of the condensed ring.
3. The A-D-A type conjugated micromolecule semiconductor material based on condensed ring and indole-2-ketone according to claim 1, wherein the branched chain structure of the micromolecule semiconductor material is as follows:
R1is CnH2n+1An alkyl chain, n is more than or equal to 1; or R1Is an alkyl benzene chain
Figure FDA0002200149640000013
R2Is CnH2n+1Alkyl chain, n is more than or equal to 1.
4. The A-D-A type conjugated micromolecule semiconductor material based on condensed ring and indole-2-ketone according to claim 1, characterized in that the synthetic method is prepared by Stille or C-H activation reaction.
5. Use of a conjugated small molecule semiconductor material of the a-D-a type based on fused rings and indol-2-ones according to any of claims 1-4 for the preparation of organic thin film transistors, organic photovoltaic cells and thermoelectric conversion devices.
CN201910862239.2A 2019-09-12 2019-09-12 A-D-A type conjugated micromolecule semiconductor material based on condensed ring and indole-2-ketone Pending CN110698497A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910862239.2A CN110698497A (en) 2019-09-12 2019-09-12 A-D-A type conjugated micromolecule semiconductor material based on condensed ring and indole-2-ketone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910862239.2A CN110698497A (en) 2019-09-12 2019-09-12 A-D-A type conjugated micromolecule semiconductor material based on condensed ring and indole-2-ketone

Publications (1)

Publication Number Publication Date
CN110698497A true CN110698497A (en) 2020-01-17

Family

ID=69194953

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910862239.2A Pending CN110698497A (en) 2019-09-12 2019-09-12 A-D-A type conjugated micromolecule semiconductor material based on condensed ring and indole-2-ketone

Country Status (1)

Country Link
CN (1) CN110698497A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106543201A (en) * 2016-11-01 2017-03-29 西安近代化学研究所 A kind of A D A type conjugated molecules based on replacement indeno thiophene condensed ring unit and preparation method thereof
CN106905344A (en) * 2015-12-23 2017-06-30 北京大学 Based on seven simultaneously LARGE CONJUGATE MOLECULES of condensed ring unit and preparation method thereof and applications in solar cells
WO2017191466A1 (en) * 2016-05-06 2017-11-09 Imperial Innovations Limited Organic ternary blends
CN109081849A (en) * 2018-07-20 2018-12-25 合肥工业大学 A kind of conjugation small molecule material and preparation method thereof based on pyridazole diketone and two indeno Dithiophene condensed ring
CN109180637A (en) * 2018-09-11 2019-01-11 杭州师范大学 A-D-A type photovoltaic small molecule receptor and its preparation method and application based on indeno [1,2-b] fluorenes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106905344A (en) * 2015-12-23 2017-06-30 北京大学 Based on seven simultaneously LARGE CONJUGATE MOLECULES of condensed ring unit and preparation method thereof and applications in solar cells
WO2017191466A1 (en) * 2016-05-06 2017-11-09 Imperial Innovations Limited Organic ternary blends
CN106543201A (en) * 2016-11-01 2017-03-29 西安近代化学研究所 A kind of A D A type conjugated molecules based on replacement indeno thiophene condensed ring unit and preparation method thereof
CN109081849A (en) * 2018-07-20 2018-12-25 合肥工业大学 A kind of conjugation small molecule material and preparation method thereof based on pyridazole diketone and two indeno Dithiophene condensed ring
CN109180637A (en) * 2018-09-11 2019-01-11 杭州师范大学 A-D-A type photovoltaic small molecule receptor and its preparation method and application based on indeno [1,2-b] fluorenes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BENOIT LIEGAULT ET AL.: "Establishment of broadly applicable reaction conditions for the palladium-catalyzed direct arylation of heteroatom-containing aromatic compounds", 《J.ORG.CHEM.》 *
FEIFEI WANG ET AL.: "Bis(7-aza-2-oxoindolin-3-ylidene)dihydropyrroloindole-dione based D-A conjugated polymers for electron and ambipolar organic thin film transistors", 《DYES AND PIGMENTS》 *

Similar Documents

Publication Publication Date Title
CN106977491B (en) Spiro [ fluorene-9, 9-xanthene ] hole transport material and application thereof
CN108864137B (en) Receptor compound, preparation method and application thereof, and photovoltaic cell containing receptor compound
JP5665992B2 (en) Benzodithiophene organic semiconductor material and preparation method thereof
Yang et al. A solution-processable D–A–D small molecule based on isoindigo for organic solar cells
WO2012068733A1 (en) Conjugated polymer containing isoindigo units, preparation method and use thereof
JP5425338B2 (en) Copolymer containing anthracene and pearselenol, its production method and its application
Zhang et al. Synthesis of star-shaped small molecules carrying peripheral 1, 8-naphthalimide functional groups and their applications in organic solar cells
Du et al. Conjugated polymers with 2, 7-linked 3, 6-difluorocarbazole as donor unit for high efficiency polymer solar cells
CN112979611B (en) Bowl alkenyl perovskite solar cell hole transport layer material and preparation method and application thereof
CN112608309B (en) Non-condensed ring organic small molecular material containing fluorene ring group and preparation method and application thereof
TWI473804B (en) Perylene tetracarboximide derivatives for photovoltaic devices
KR20200026162A (en) Organic semiconducting material and its synthesis and organic semiconducting component with the material
CN110790776B (en) Electron-transport conjugated small-molecule semiconductor material
WO2021203663A1 (en) Electroluminescent polymer based on phenanthroimidazole units, preparation method therefor, and use thereof
CN109748880A (en) The compound and its application on organic electroluminescence device of a kind of fluorenes of dimethylanthracene containing spiral shell and nitrogenous hexa-member heterocycle
CN110698497A (en) A-D-A type conjugated micromolecule semiconductor material based on condensed ring and indole-2-ketone
CN108218870B (en) Tetraaza nano graphene functional material and preparation method thereof
CN108997116A (en) A kind of fullerene acrylic acid derivative and its preparation method and application
CN107840944B (en) Random copolymer with difluoro benzothiadiazole and bitetrathiophene as main chains and preparation method and application thereof
CN114349771B (en) Hexabenzocoronene-based non-fullerene acceptor material and preparation and application thereof
CN104744666B (en) Segment type polymeric material of conjugated chain containing more piece and its preparation method and application
CN106977705B (en) Dithieno imide derivatives, intermediates thereof, preparation method and use
CN110218296B (en) Structure, synthesis and application of carbazole polymer hole transport material
CN111057008B (en) D-A type excited proton transfer high-efficiency fluorescent material and preparation method and application thereof
CN110818730A (en) Thiophene pyrrolopyrrole diketone and hemiindigo based solution-processable conjugated small molecule semiconductor material

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20200117

RJ01 Rejection of invention patent application after publication