CN107814918B - 一类氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物及其制备方法与应用 - Google Patents
一类氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物及其制备方法与应用 Download PDFInfo
- Publication number
- CN107814918B CN107814918B CN201711136229.8A CN201711136229A CN107814918B CN 107814918 B CN107814918 B CN 107814918B CN 201711136229 A CN201711136229 A CN 201711136229A CN 107814918 B CN107814918 B CN 107814918B
- Authority
- CN
- China
- Prior art keywords
- polymer
- formula
- thiophene
- benzofuranone
- field effect
- 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
Links
- 229920000547 conjugated polymer Polymers 0.000 title abstract description 20
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 title abstract description 19
- HYZQBRPUMATHOM-UHFFFAOYSA-N S1C=CC=C1.O1C(CC2=C1C=CC=C2)=O.N=2C(C=C1C=CC=CC21)=O Chemical compound S1C=CC=C1.O1C(CC2=C1C=CC=C2)=O.N=2C(C=C1C=CC=CC21)=O HYZQBRPUMATHOM-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000002360 preparation method Methods 0.000 title description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 73
- 230000005669 field effect Effects 0.000 claims abstract description 24
- 239000004065 semiconductor Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 5
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical class CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000004224 protection Effects 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 239000011737 fluorine Chemical group 0.000 claims description 2
- 229910052731 fluorine Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 17
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 abstract description 15
- 150000002576 ketones Chemical class 0.000 abstract description 15
- BGQWUXMSWSSEHK-UHFFFAOYSA-N S1C=CC=C1.O1C(CC2=C1C=CC=C2)=O Chemical compound S1C=CC=C1.O1C(CC2=C1C=CC=C2)=O BGQWUXMSWSSEHK-UHFFFAOYSA-N 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical compound C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- -1 4- octadecyl docosyl Chemical group 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 239000002861 polymer material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 125000005605 benzo group Chemical group 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 3
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical class C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 150000002240 furans Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 241000248771 Amphiops mater Species 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 206010010356 Congenital anomaly Diseases 0.000 description 1
- 206010020675 Hypermetropia Diseases 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- TTXHZPBKQYQXCD-UHFFFAOYSA-N S1C=CC2=C1C=CC=C2.S2C=CC=C2.O2C(CC1=C2C=CC=C1)=O Chemical compound S1C=CC2=C1C=CC=C2.S2C=CC=C2.O2C(CC1=C2C=CC=C1)=O TTXHZPBKQYQXCD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- 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 potential barriers
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/512—Hole transport
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/514—Electron transport
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/92—TFT applications
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Thin Film Transistor (AREA)
Abstract
本发明公开了一类氮杂吲哚酮苯并呋喃酮‑噻吩苯并噻二唑共轭聚合物,其结构式如式Ⅰ所示,该类聚合物具有较宽的紫外‑可见‑近红外吸收光谱、良好的热学稳定性,具有合适的前沿轨道能级,有利于空穴和电子注入,可以制备空气稳定的双极性场效应晶体管。本发明的氮杂吲哚酮苯并呋喃酮‑噻吩苯并噻二唑共轭聚合物的合成步骤少、收率高、聚合物度高、纯化工艺简单易行,适合大规模工业合成。以本发明氮杂吲哚酮苯并呋喃酮‑噻吩苯并噻二唑共轭聚合物半导体材料为半导体层制备的有机场效应晶体管具有很高的空穴和电子迁移率。
Description
技术领域
本发明属于有机半导体材料技术领域,具体涉及一类氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物及其制备方法与应用。
背景技术
聚合物场效应晶体管是以聚合物半导体材料为载流子传输层,通过电场来调节材料导电能力的有源器件,在射频识别标签、柔性和大面积显示屏、可穿戴传感器以及电子皮肤等方面有着广阔的应用前景。按照载流子类别,聚合物半导体材料可以分为p-型、n-型以及双极性三种,其中p-型聚合物材料可以进行空穴传输,n-型聚合物材料可以进行电子传输,而双极性聚合物材料则既可以进行空穴传输,也可以进行电子传输。由于以双极性聚合物材料载流子传输层制备柔性有机集成电路时,比p-型和n-型聚合物材料有着构筑工艺简单等先天性优势,使得双极性聚合物半导体材料近年来越来越受到材料科学和有机微电子研究工作者们的青睐,相关研究已经成为有机电子学领域的热点和焦点之一。
近十年来,p-型和n-型聚合物半导体材料研究取得巨大进展,其空穴迁移率或电子迁移率已经可以和有机小分子真空蒸镀薄膜以及单晶场效应晶体管器件的迁移率参数数值相媲美。相比之下,尽管双极性聚合物半导体材料的研究也取得了较大进步,但无论是在材料的种类、数量、迁移率还是在器件稳定性等方面都存在较大差距。比如,目前具有较高空穴迁移率和电子迁移率(大于1cm2V-1s-1)的双极性聚合物半导体材料仍然局限于少数含吡咯并吡咯二酮结构单元聚合物,并且它们中的大部分也只能在氮气中才能表现出较高的双极性性能(Chen,Z.;Lee,M.J.;Ashraf,R.S.;Gu,Y.;Albert-Seifried,S.;Nielsen,M.M.;Schroeder,B.;Anthopoulos,T.D.;Heeney,M.;McCulloch,I.;Sirringhaus,H.Adv.Mater.2012,24,647;Yuen,J.D.;Fan,J.;Seifter,J.;Lim,B.;Hufschmid,R.;Heeger,A.J.;Wudl,F.J.Am.Chem.Soc.2011,133,20799;Lee,J.;Han,A.-R.;Kim,J.;Kim,Y.;Oh,J.H.;Yang,C.J.Am.Chem.Soc.2012,134,20713;Lee,J.;Han,A.-R.;Yu,H.;Shin,T.J.;Yang,C.;Oh,J.H.J.Am.Chem.Soc.2013,135,9540)。开发高性能、空气稳定的双极性聚合物半导体材料的最大难点在于前沿轨道能级的精确调控,因为只有具有合适的最高占有轨道(HOMO)能级(-5.1±0.3eV)和最低未占有轨道(LUMO)能级(-4.0eV左右),才有利于空穴和电子的有效注入,从而获得较高的载流子迁移率,另外也有利于获得高空气稳定的聚合物场效应晶体管器件(Salleo,A.Mater.Today 2007,10,38;Wang,C.L.;Dong,H.L.;Hu,W.P.;Liu,Y.Q.;Zhu,D.B.Chem.Rev.2012,112,2208)。对供-受型(D-A)聚合物半导体材料来说,人们已经发现其HOMO能级主要取决于供电单元的HOMO能级,而其LUMO能级主要取决于受电单元的LUMO能级,但是,双极性聚合物材料的研发工作依然受困于不可预知的供、受体间的电子推拉作用力大小以及薄膜中材料分子的聚集态结构等等。
发明内容
本发明要解决的技术问题在于克服现有双极性聚合物半导体材料性能上的不足,提供一类氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物,该类聚合物具有较宽的紫外-可见-近红外吸收光谱、良好的热学稳定性,具有合适的前沿轨道能级,有利于空穴和电子注入,可以制备空气稳定的双极性场效应晶体管。
本发明的第一目的提供一类氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物。
本发明所提供的氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物,其结构式如式Ⅰ所示:
式Ⅰ中,R1、R2为C1-C100的直链或支链烷基,R1与R2相同或不同,X为氢或者氟,n为聚合度,n=10-200,具体可为10-50,10-20,14或15。
具体地,R1为C20-C50的直链或支链烷基,具体可为4-十八烷基二十二烷基,R2为C2-C20的直链或支链烷基,具体可为C2-C10的直链或支链烷基,更具体可为正己烷基。
本发明的第二目的在于提供一种制备上述氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物的方法。
本发明所提供的制备上述氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物的方法,包括下述步骤:
在惰性气体保护下,使式(Ⅱ)所示化合物、式(Ⅲ)所示化合物在钯催化剂以及配体作用下进行反应,得到氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物,其反应化学方程式如图1所示。
式Ⅱ中,R1的定义同式I中的R1的定义,式Ⅲ中,R2和X的定义同式Ⅰ中的R2和X的定义,式Ⅲ中,R3为C1-C4直链烷基,具体可为甲基。
上述方法中,所述钯催化剂具体可为三(二亚苄基丙酮)二钯或四(三苯基膦)钯。
所述配体具体可为三(邻甲苯基)膦或三苯基膦。
上述方法中,式Ⅱ所示化合物、式Ⅲ所示化合物、钯催化剂和配体的摩尔比依次可为1:0.95~1.05:0.01~0.10:0.02~0.60,具体可为:1.0:1.0:0.04:0.4。
所述反应的反应温度可为60~150℃,具体可为115℃,反应时间可为12~96小时,具体可为48小时。
进一步的,所述反应在有机溶剂中进行,所述有机溶剂具体可为N,N-二甲基甲酰胺、甲苯或氯苯。
本发明的第三目的在于提供上述氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物在制备有机场效应晶体管中的应用。
本发明的再一个目的是提供一种有机场效应晶体管。
本发明所提供的有机场效应晶体管,其半导体层由式Ⅰ所示的氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物制成。
以本发明的氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物半导体材料为半导体层制备的有机场效应晶体管具有优秀的空穴/电子迁移率(μh/μe)和开关比(最优为μh/μe为2.11/2.25cm2V-1s-1,开关比为104-105),具有广阔的应用前景。
采用上述技术方案,本发明的有益效果如下:
(1)本发明所述的氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物具有较宽的紫外-可见-近红外吸收光谱、良好的热学稳定性,具有合适的前沿轨道能级,有利于空穴和电子注入,可以制备空气稳定的双极性场效应晶体管。
(2)本发明的氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物的合成步骤少、收率高、聚合物度高、纯化工艺简单易行,适合大规模工业合成。
(3)以本发明氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物半导体材料为半导体层制备的有机场效应晶体管具有优秀的空穴/电子迁移率(μh/μe)和开关比(最优为μh/μe为2.11/2.25cm2V-1s-1,开关比为104-105),具有广阔的应用前景。
附图说明
图1为本发明中制备氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物的化学反应方程式;
图2为本发明中聚合物PNBDOPV-DTBT和聚合物PNBDOPV-DTF2BT合成路线图;
图3为本发明聚合物PNBDOPV-DTBT和聚合物PNBDOPV-DTF2BT在氯苯溶液的紫外-可见-近红外吸收光谱图;
图4为本发明聚合物PNBDOPV-DTBT和聚合物PNBDOPV-DTF2BT薄膜的紫外-可见-近红外吸收光谱图;
图5为本发明聚合物PNBDOPV-DTBT和聚合物PNBDOPV-DTF2BT的热重分析曲线图;
图6为本发明聚合物PNBDOPV-DTBT和聚合物PNBDOPV-DTF2BT循环伏安法曲线图;
图7为本发明聚合物PNBDOPV-DTBT的原子力显微镜形貌图;
图8为本发明聚合物PNBDOPV-DTF2BT的原子力显微镜形貌图;
图9为本发明聚合物PNBDOPV-DTBT和聚合物PNBDOPV-DTF2BT的晶体管器件结构示意图;
图10为本发明聚合物PNBDOPV-DTBT场效应晶体管的转移曲线图;
图11为本发明聚合物PNBDOPV-DTBT场效应晶体管的输出曲线图;
图12为本发明聚合物PNBDOPV-DTF2BT场效应晶体管的转移曲线图;
图13为本发明聚合物PNBDOPV-DTF2BT场效应晶体管的输出曲线图。
具体实施方式
下面通过具体实施例对本发明进行说明,但本发明并不局限于此。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法;下述实施例中所用的试剂、材料等,如无特殊说明,均可从商业途径得到。
下述实施例中所采用的聚合单体(3反,7反)-3,7-双(6-溴-1-(4-十八烷基二十二烷基)-2-氧-1氢-吡咯并[2,3-b]吡啶-3(2氢)-亚基)苯并[1,2-b:4,5-b']二呋喃-2,6(3氢,7氢)-二酮,制备参照文献:Chem.Sci.2016,7,5753;下述实施例中所采用聚合单体4,7-双(4-己基-5-(三甲基锡基)噻吩-2-基)苯并[c][1,2,5]噻二唑和5,6-二氟-4,7-双(4-己基-5-(三甲基锡基)噻吩-2-基)苯并[c][1,2,5]噻二唑购自深圳睿迅光电材料科技有限公司。
实施例1
PNBDOPV-DTBT,即式Ⅰ中R1=4-十八烷基二十二烷基;R2=正己基;X=H,其合成路线如图2所示,制备方法如下:
将(3反,7反)-3,7-双(6-溴-1-(4-十八烷基二十二烷基)-2-氧-1氢-吡咯并[2,3-b]吡啶-3(2氢)-亚基)苯并[1,2-b:4,5-b']二呋喃-2,6(3氢,7氢)-二酮(173.0mg,0.10mmol)和4,7-双(4-己基-5-(三甲基锡基)噻吩-2-基)苯并[c][1,2,5]噻二唑(79.4,0.10mmol),三(二亚苄基丙酮)二钯(3.6mg)、三(邻甲苯基)膦(12mg)和氯苯(3.0mL)加入到反应瓶中,在氩气中进行三次冷冻-抽气-解冻循环除氧,后将反应混合物加热到115℃氩气保护反应48h。冷却后,加入200mL甲醇/6M盐酸混合物(v/v 20:1),室温下搅拌2h,过滤。所得固体用索氏提取器抽提。抽提溶剂为依次甲醇、丙酮、正己烷、各抽提24h,最后用氯苯提取得到目标聚合物188毫克,收率92%。
结构表征数据如下:
分子量:GPC:Mn=31.1kDa,Mw=84.1kDa,PDI=2.71。
元素分析:C130H200N6O6S3,计算值:C,76.57;H,9.89;N,4.12;探测值:C 76.61,H9.65,N 4.09。
通过上面的分析可知该化合物结构正确,为聚合物PNBDOPV-DTBT,聚合度为15。
实施例2
PNBDOPV-DTF2BT,即式Ⅰ中R1=4-十八烷基二十二烷基;R2=正己基;X=F,其合成路线如图2所示,制备方法如下:
将(3反,7反)-3,7-双(6-溴-1-(4-十八烷基二十二烷基)-2-氧-1氢-吡咯并[2,3-b]吡啶-3(2氢)-亚基)苯并[1,2-b:4,5-b']二呋喃-2,6(3氢,7氢)-二酮(173.0mg,0.10mmol)和5,6-二氟-4,7-双(4-己基-5-(三甲基锡基)噻吩-2-基)苯并[c][1,2,5]噻二唑(83.0mg,0.10mmol),三(二亚苄基丙酮)二钯(3.6mg)、三(邻甲苯基)膦(12mg)和氯苯(3.0mL)加入到反应瓶中,在氩气中进行三次冷冻-抽气-解冻循环除氧,后将反应混合物加热到115℃氩气保护反应48h。冷却后,加入200mL甲醇/6M盐酸混合物(v/v 20:1),室温下搅拌2h,过滤。所得固体用索氏提取器抽提。抽提溶剂为依次甲醇、丙酮、正己烷、各抽提24h,最后用氯苯提取得到目标聚合物186毫克,收率90%。
结构表征数据如下:
分子量:GPC:Mn=29.9kDa,Mw=82.3kDa,PDI=2.68。
元素分析:C130H198F2N6O6S3,计算值:C,75.24;H,9.62;N,4.05;探测值:C 75.06,H9.40,N 4.00。
通过上面的分析可知该化合物结构正确,为聚合物PNBDOPV-DTF2BT,聚合度为14。
实施例3
聚合物PNBDOPV-DTBT和聚合物PNBDOPV-DTF2BT的光谱性能实验
图3和图4分别为实施例1和实施例2制备的聚合物PNBDOPV-DTBT和聚合物PNBDOPV-DTF2BT氯苯溶液和薄膜的紫外-可见-近红外吸收光谱图,从图3可以看出,该类聚合物在紫外-可见-近红外具有较宽的吸收,其主要吸收区域为600至900或者1000纳米,可推测出聚合物分子链内具有较强的分子内电荷转移。由图4可知,薄膜吸收较溶液中有着一定程度的红移,说明在聚合物薄膜中存在较强的分子间相互作用或者增强的π-π相互作用。
实施例4
聚合物PNBDOPV-DTBT和PNBDOPV-DTF2BT的热学性能实验
图5为聚合物的热重分析曲线,由图5可以看出,聚合物PNBDOPV-DTBT和PNBDOPV-DTF2BT的热分解温度分别为372℃和364℃,说明聚合物PNBDOPV-DTBT和PNBDOPV-DTF2BT具有良好的热稳定性。
实施例5
聚合物PNBDOPV-DTBT和PNBDOPV-DTF2BT的电化学性能实验
如图6所示为聚合物PNBDOPV-DTBT和PNBDOPV-DTF2BT的循环伏安曲线。
循环伏安测试采用常规的三电极体系,其中铂、铂丝、银/氯化银分别做为工作电极、对电极和参比电极,四正丁基六氟磷酸铵为支持电解质。扫描范围为-1.0~2.0伏特(vs.Ag/AgCl),扫描速率为50毫伏每秒。所得循环伏安曲线表明聚合物PNBDOPV-DTBT和PNBDOPV-DTF2BT的起始氧化电位约为1.47和1.65伏特,由此估算它们的HOMO能级约为-5.87和-6.05电子伏特,起始还原电位都为-0.48伏特,由此估算它们的LUMO能级约为-3.92电子伏特。
实施例6
如图7和图8所示为PNBDOPV-DTBT和PNBDOPV-DTF2BT的原子力显微镜形貌图,从图中可以看出,PNBDOPV-DTBT和PNBDOPV-DTF2BT能够形成相互交联的纤维状薄膜结构,表明聚合物分子间存在较强的相互作用力。
实施例7
聚合物PNBDOPV-DTBT和聚合物PNBDOPV-DTF2BT的场效应晶体管制备与性能。
图9为聚合物PNBDOPV-DTBT和聚合物PNBDOPV-DTF2BT的有机场效应晶体管结构示意图。
如图9所示,顶栅-底接触(TGBC)器件制备:采用光刻技术制备金源-漏电极,OFET器件的沟道宽度(W)为4500μm,沟道长度(L)为50μm。绝缘基底为聚对苯二甲酸乙二醇酯(PET)。半导体活性层(约30纳米)通过旋涂3.0mg/mL的聚合物氯仿溶液制备。然后薄膜样品置于手套箱中120℃退火5分钟。随后,一层约900纳米的PMMA介电层通过旋涂60毫克/毫升的PMMA醋酸丁酯溶液制备,所选用的PMMA的重均分子量为1000KDa。然后,将整个器件置于80℃的真空干燥箱中烘烤3小时以除去醋酸丁酯溶剂。最后,在PMMA介电层上蒸镀一层厚度约80纳米的铝层作为栅电极,将整个器件置于140℃的真空干燥箱中烘烤20分钟。在空气中,所制备的TGBC器件在Keithley 4200SCS半导体测试仪上测试场效应性能。
图10-13为聚合物PNBDOPV-DTBT和聚合物PNBDOPV-DTF2BT所制备的场效应晶体管的转移曲线和输出曲线,载流子迁移率可由方程计算得出:
IDS=(W/2L)Ciμ(VG–VT)2(饱和区,VDS=VG–VT)
其中,IDS为漏极电流,μ为载流子迁移率,VG为栅极电压,VT为阈值电压,W为沟道宽度,L为沟道长度,Ci为绝缘体电容(Ci=7.5×10-9法每平方厘米)。利用(IDS,sat)1/2对VG作图,并作线性回归,可由此回归线的斜率推算出载流子迁移率(μ),由回归线与X轴的连接点求得VT。迁移率可以根据公式从转移曲线的斜率计算得出,开关比可由图10和12源漏电流的最大值与最小值之比得出。制备的聚合物场效应晶体管的器件性能如表1所示。
表1:基于聚合物PNBDOPV-DTBT和PNBDOPV-DTF2BT的场效应晶体管器件的性能参数
以聚合物PNBDOPV-DTBT和聚合物PNBDOPV-DTF2BT为半导体层构筑了多个场效应晶体管器件,其中聚合物PNBDOPV-DTBT的空穴/电子迁移率(μh/μe)和开关比(最优为μh/μe为2.11/2.25cm2V-1s-1,开关比为104-105)
通过以上性能的实验结果分析可知,所述的氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物是一类优良的聚合物半导体材料。本发明并不限于本实施例中列举的两个氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物,可以是改变不同的取代基R1和R2得到一系列的新型聚合物,由于篇幅有限,不在此一一列出。
本发明给出的合成步骤少,收率高,聚合物度高,纯化工艺简单易行,适合大规模工业合成。研究结果对于研究聚合物半导体材料的结构与性能的关系以及设计、合成高性能聚合物半导体材料具有指导意义。
Claims (7)
1.一种聚合物,其结构式如式Ⅰ所示:
式Ⅰ中,R1、R2为C1-C100的直链或支链烷基,R1与R2相同或不同,X为氢或者氟,n为聚合度,n=10-200。
2.根据权利要求1所述的聚合物,其特征在于:式Ⅰ中,R1为C20-C50的直链或支链烷基;
R2为C2-C20的直链或支链烷基;
n=10-50。
3.制备权利要求1或2中式Ⅰ所示的聚合物的方法,包括如下步骤:
在惰性气体保护下,使式Ⅱ所示化合物、式Ⅲ所示化合物在钯催化剂以及配体作用下进行反应,得到权利要求1或2中式Ⅰ所示的聚合物:
式Ⅱ中,R1的定义同权利要求1或2式I中的R1的定义,式Ⅲ中,R2和X的定义同权利要求1或2式Ⅰ中的R2和X的定义,R3为C1-C4直链烷基。
4.根据权利要求3所述的方法,其特征在于:所述方法中,所述钯催化剂为三(二亚苄基丙酮)二钯或四(三苯基膦)钯;
所述配体为三(邻甲苯基)膦或三苯基膦;
式Ⅱ所示化合物、式Ⅲ所示化合物、钯催化剂和配体的摩尔比依次为1:0.95~1.05:0.01~0.10:0.02~0.60;
所述反应的反应温度为60~150℃,反应时间为12~96小时。
5.根据权利要求3或4所述的方法,其特征在于:所述方法中,所述反应在有机溶剂中进行,
所述有机溶剂为N,N-二甲基甲酰胺、甲苯或氯苯。
6.权利要求1或2中式Ⅰ所示的聚合物在制备有机场效应晶体管中的应用。
7.一种有机场效应晶体管,其半导体层由权利要求1或2中式Ⅰ所示的聚合物制成。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711136229.8A CN107814918B (zh) | 2017-11-16 | 2017-11-16 | 一类氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物及其制备方法与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711136229.8A CN107814918B (zh) | 2017-11-16 | 2017-11-16 | 一类氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物及其制备方法与应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107814918A CN107814918A (zh) | 2018-03-20 |
CN107814918B true CN107814918B (zh) | 2019-09-13 |
Family
ID=61609866
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711136229.8A Active CN107814918B (zh) | 2017-11-16 | 2017-11-16 | 一类氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物及其制备方法与应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107814918B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113136024B (zh) * | 2020-01-19 | 2022-05-06 | 中国科学院化学研究所 | 一种聚合物及其制备方法和应用以及有机场效应晶体管 |
CN116546824A (zh) * | 2022-05-07 | 2023-08-04 | 浙江大学 | 一种有机场效应晶体管及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104927031A (zh) * | 2015-06-09 | 2015-09-23 | 中国科学院化学研究所 | 异靛青-含硫稠环聚合物及其制备方法与应用 |
CN105384918A (zh) * | 2015-12-15 | 2016-03-09 | 中国科学院化学研究所 | 氮杂异靛青聚合物及其制备方法与应用 |
-
2017
- 2017-11-16 CN CN201711136229.8A patent/CN107814918B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104927031A (zh) * | 2015-06-09 | 2015-09-23 | 中国科学院化学研究所 | 异靛青-含硫稠环聚合物及其制备方法与应用 |
CN105384918A (zh) * | 2015-12-15 | 2016-03-09 | 中国科学院化学研究所 | 氮杂异靛青聚合物及其制备方法与应用 |
Non-Patent Citations (1)
Title |
---|
"Embedding electron-deficient nitrogen atoms in polymer backbone towards high performance n-type polymer field-effect transistors";YaZhong Dai et al;《Chemical Science》;20160613;第7卷(第9期);第5753-5757页 * |
Also Published As
Publication number | Publication date |
---|---|
CN107814918A (zh) | 2018-03-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Xing et al. | New fullerene design enables efficient passivation of surface traps in high performance pin heterojunction perovskite solar cells | |
Zhang et al. | Synthesis and photovoltaic properties of new low bandgap isoindigo-based conjugated polymers | |
CN106589326B (zh) | 二氟连二噻吩类聚合物及其制备方法与其在场效应晶体管中的应用 | |
Elsawy et al. | Isoindigo-based small molecules for high-performance solution-processed organic photovoltaic devices: the electron donating effect of the donor group on photo-physical properties and device performance | |
WO2018157427A1 (zh) | 一种异原子取代的苯并噻二唑基聚合物给体材料及其制备方法和应用 | |
CN106866943B (zh) | 一种萘酰亚胺-氟化二噻吩乙烯共轭聚合物及其制备方法与应用 | |
CN104725613B (zh) | 含萘并二酰亚胺环的n‑型水醇溶共轭聚合物材料及制备方法和应用 | |
Mikroyannidis et al. | Low band gap vinylene compounds with triphenylamine and benzothiadiazole segments for use in photovoltaic cells | |
CN104761563A (zh) | 含有吸电子基团的对苯撑乙烯类化合物及其制备和应用 | |
CN103804271A (zh) | 含有吸电子基团的异靛青类化合物及其制备和应用 | |
CN107814918B (zh) | 一类氮杂吲哚酮苯并呋喃酮-噻吩苯并噻二唑共轭聚合物及其制备方法与应用 | |
Cho et al. | Diketopyrrolopyrrole-based copolymers bearing highly π-extended donating units and their thin-film transistors and photovoltaic cells | |
Chao et al. | Enhanced thermal stability of organic photovoltaics via incorporating triphenylamine derivatives as additives | |
Han et al. | Solution processable low bandgap thienoisoindigo-based small molecules for organic electronic devices | |
Zhang et al. | Synthesis and optimization solid-state order using side-chain position of thieno-isoindigo derivative-based D–A polymers for high-performance ambipolar organic thin films transistors | |
CN107286157A (zh) | 一种苝二酰亚胺类化合物及其制备方法、应用 | |
Li et al. | A diketopyrrolopyrrole-based macrocyclic conjugated molecule for organic electronics | |
Wei et al. | Heteroheptacene-cored semiconducting molecules for non-fullerene organic solar cells | |
Park et al. | Isoindigo-based polymer solar cells with high open circuit voltages up to 1.01 áV | |
CN106832230A (zh) | 一种氟化二噻吩乙烯聚合物及其制备方法与应用 | |
Hong et al. | A novel small molecule based on dithienophosphole oxide for bulk heterojunction solar cells without pre-or post-treatments | |
EP2835407A1 (en) | Conjugated polymer compounds | |
CN110818729B (zh) | 基于多元芳香环的酰亚胺类共轭小分子及其制备方法与在有机光电器件中的应用 | |
He et al. | Polythiophenes with alkylthiophene side chains for efficient polymer solar cells | |
Park et al. | Semiconducting π-extended porphyrin dimer and its characteristics in OFET and OPVC |
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 |