CA2625306A1 - Electron acceptors-cored regioregular oligothiophenes as building blocks for soluble low band-gap conjugated polymers - Google Patents
Electron acceptors-cored regioregular oligothiophenes as building blocks for soluble low band-gap conjugated polymers Download PDFInfo
- Publication number
- CA2625306A1 CA2625306A1 CA002625306A CA2625306A CA2625306A1 CA 2625306 A1 CA2625306 A1 CA 2625306A1 CA 002625306 A CA002625306 A CA 002625306A CA 2625306 A CA2625306 A CA 2625306A CA 2625306 A1 CA2625306 A1 CA 2625306A1
- Authority
- CA
- Canada
- Prior art keywords
- alkyl group
- electron
- regioregular
- cored
- formula
- 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.)
- Abandoned
Links
- 229920000547 conjugated polymer Polymers 0.000 title claims description 7
- 230000005669 field effect Effects 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 238000013459 approach Methods 0.000 claims description 12
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 12
- -1 2-ethylhexyl Chemical group 0.000 claims description 11
- 239000000370 acceptor Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 6
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical group C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 claims description 5
- 239000005964 Acibenzolar-S-methyl Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 5
- VVVPGLRKXQSQSZ-UHFFFAOYSA-N indolo[3,2-c]carbazole Chemical compound C1=CC=CC2=NC3=C4C5=CC=CC=C5N=C4C=CC3=C21 VVVPGLRKXQSQSZ-UHFFFAOYSA-N 0.000 claims description 5
- 229960005544 indolocarbazole Drugs 0.000 claims description 5
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 4
- 238000006619 Stille reaction Methods 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 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 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 5
- 239000000463 material Substances 0.000 abstract description 19
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 10
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 7
- 238000000113 differential scanning calorimetry Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [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 description 5
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 5
- 230000037230 mobility Effects 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002800 charge carrier Substances 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- OZNXIGFAKCITRZ-UHFFFAOYSA-N (4-hexylthiophen-2-yl)-trimethylstannane Chemical compound CCCCCCC1=CSC([Sn](C)(C)C)=C1 OZNXIGFAKCITRZ-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- MBDZHPMISHRUFG-UHFFFAOYSA-N 4,7-bis[4-octyl-5-(4-octylthiophen-2-yl)thiophen-2-yl]-2,1,3-benzothiadiazole Chemical compound C(CCCCCCC)C1=C(SC(=C1)C1=CC=C(C2=NSN=C21)C2=CC(=C(S2)C=2SC=C(C2)CCCCCCCC)CCCCCCCC)C=2SC=C(C2)CCCCCCCC MBDZHPMISHRUFG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229920002457 flexible plastic Polymers 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- DOHOHOKWNWTQLM-UHFFFAOYSA-N 4,7-bis(4-octylthiophen-2-yl)-2,1,3-benzothiadiazole Chemical compound CCCCCCCCC1=CSC(C=2C3=NSN=C3C(C=3SC=C(CCCCCCCC)C=3)=CC=2)=C1 DOHOHOKWNWTQLM-UHFFFAOYSA-N 0.000 description 1
- AMYLTENEOQNKGO-UHFFFAOYSA-N 4,7-bis(5-bromo-4-octylthiophen-2-yl)-2,1,3-benzothiadiazole Chemical compound S1C(Br)=C(CCCCCCCC)C=C1C(C1=NSN=C11)=CC=C1C1=CC(CCCCCCCC)=C(Br)S1 AMYLTENEOQNKGO-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 101100059612 Caenorhabditis elegans ceh-17 gene Proteins 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012995 silicone-based technology Methods 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- 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
-
- 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
- C08G61/125—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 oxygen atom in the ring
-
- 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
- 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
-
- 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
- H10K85/151—Copolymers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
-
- 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
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
-
- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/10—Photovoltaic [PV]
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
A series of electron acceptors-cored regioregular oligothiophenes are described. These novel building blocks can be used to construct soluble and crystalline polymeric materials for applications in organic electronic devices such as organic solar cells and field-effect transistors by copolymerization with other conjugated compounds.
Description
ELECTRON ACCEPTORS-CORED REGIOREGULAR OLIGOTHIOPHENES
AS BUILDING BLOCKS FOR SOLUBLE LOW BAND-GAP CONJUGATED
POLYMERS
Field of the Invention The present invention relates to organic electronic devices. More specifically, the invention relates to the use of electron acceptors-cored regioregular oligothiophenes as building blocks for the preparation of polymers for organic semiconductors.
Background of the Invention Organic semiconductors present a new low-cost alternative to conventional silicon-based technology. An organic semiconductor is any organic material that has semiconductor properties. Organic semiconductors have demonstrated promising applications in various applications, such as light-emitting diodes (OLED), field-effect transistors (FET), solar cells, and biosensors. Organic semiconductors have many advantages, such as easy fabrication, mechanical flexibility, and low cost. For successful commercialization of the above devices, the organic semiconductors should possess good chemical and thermal stabilities and acceptable solubility in organic solvent for wet processing.
Organic semiconductors based photovoltaic (OPV) technology is one of the most promising candidates for producing low-cost solar cells due to the low material cost and compatibility with the high throughput wet processes, such as spin-coating and roll-to-roll printing for fabrication on flexible plastic substrates. Although significant progress has been made in organic solar cells in the past 10 years, and the cell power conversion efficiency has been improved from a fraction of a percent to 5-6% on laboratory scale, it is still too low for commercialization.
To further improve power conversion efficiencies, materials or material combinations with better matched electronic levels, and device architectures are needed for the efficient extraction of separated charge carriers. Especially, it is of paramount importance to achieve photo-stable semiconducting polymers with narrow optical bandgaps (-1.5 eV) and high charge mobilities to cover the solar spectrum and efficiently extract the separated charge carriers.
The concept of internal electron donor-acceptor (D-A) interaction has been extensively exploited to prepare low band-gap organic semiconductors. Using this strategy, new low band-gap polymers, such as polythiophene derivatives and polyfluorene derivatives, have been developed to better cover the solar spectrum, especially in the 1.4-1.9 eV region.
(see references: Mu"hlbacher, D.; Scharber, M.; Morana, M.; Zhu, Z.; Waller, D.;
Gaudiana,R.; Brabec, C. Adv. Mater. 2006, 18, 2884-2889; Schulze, K.; Uhrich, C.;
Schuppel, R.; Leo, K.; Pfeiffer, M.; Brier, E.; Reinold, E.; Bauerle, P. Adv.
Mater. 2006, 18, 2872; Roquet, S.; Cravino, A.; Leriche, P.; Aleveque, O.;.Frere, P.;
Roncali, J. J. Am.
Chem. Soc. 2006, 128, 3459.) It is generally accepted that the formation of strong intennolecular 71-TE
stacking is necessary to achieve high charge carrier mobilities in organic semiconductors.
Rigid coplanar fused aromatic rings can efficiently enhance the intermolecualr interaction and hence improve the charge carrier mobilities. (see references: Bromley, S. T.;
Mas-Torrent, M.; Hadley, P.; Rovira, C. J. Am. Chem. Soc. 2004, 126, 6544;
Mcculloch, I.;
Heeney, M.; Bailey, C.; et al Nat. Mater. 2006, 5, 328.) One may be able to achieve semiconducting polymers with narrow band-gap and high charge mobilities if fused heterocyclic structures and the internal charge transfer concept are combined into the polymer backbones. However, the resulting materials will have extremely low solubility and may precipitate out of the polymerization solution, leading to the formation of only low molecular weight materials. In addition, the low solubility of the resulting materials will cause serious problem in the subsequent device fabrication using wet processes.
AS BUILDING BLOCKS FOR SOLUBLE LOW BAND-GAP CONJUGATED
POLYMERS
Field of the Invention The present invention relates to organic electronic devices. More specifically, the invention relates to the use of electron acceptors-cored regioregular oligothiophenes as building blocks for the preparation of polymers for organic semiconductors.
Background of the Invention Organic semiconductors present a new low-cost alternative to conventional silicon-based technology. An organic semiconductor is any organic material that has semiconductor properties. Organic semiconductors have demonstrated promising applications in various applications, such as light-emitting diodes (OLED), field-effect transistors (FET), solar cells, and biosensors. Organic semiconductors have many advantages, such as easy fabrication, mechanical flexibility, and low cost. For successful commercialization of the above devices, the organic semiconductors should possess good chemical and thermal stabilities and acceptable solubility in organic solvent for wet processing.
Organic semiconductors based photovoltaic (OPV) technology is one of the most promising candidates for producing low-cost solar cells due to the low material cost and compatibility with the high throughput wet processes, such as spin-coating and roll-to-roll printing for fabrication on flexible plastic substrates. Although significant progress has been made in organic solar cells in the past 10 years, and the cell power conversion efficiency has been improved from a fraction of a percent to 5-6% on laboratory scale, it is still too low for commercialization.
To further improve power conversion efficiencies, materials or material combinations with better matched electronic levels, and device architectures are needed for the efficient extraction of separated charge carriers. Especially, it is of paramount importance to achieve photo-stable semiconducting polymers with narrow optical bandgaps (-1.5 eV) and high charge mobilities to cover the solar spectrum and efficiently extract the separated charge carriers.
The concept of internal electron donor-acceptor (D-A) interaction has been extensively exploited to prepare low band-gap organic semiconductors. Using this strategy, new low band-gap polymers, such as polythiophene derivatives and polyfluorene derivatives, have been developed to better cover the solar spectrum, especially in the 1.4-1.9 eV region.
(see references: Mu"hlbacher, D.; Scharber, M.; Morana, M.; Zhu, Z.; Waller, D.;
Gaudiana,R.; Brabec, C. Adv. Mater. 2006, 18, 2884-2889; Schulze, K.; Uhrich, C.;
Schuppel, R.; Leo, K.; Pfeiffer, M.; Brier, E.; Reinold, E.; Bauerle, P. Adv.
Mater. 2006, 18, 2872; Roquet, S.; Cravino, A.; Leriche, P.; Aleveque, O.;.Frere, P.;
Roncali, J. J. Am.
Chem. Soc. 2006, 128, 3459.) It is generally accepted that the formation of strong intennolecular 71-TE
stacking is necessary to achieve high charge carrier mobilities in organic semiconductors.
Rigid coplanar fused aromatic rings can efficiently enhance the intermolecualr interaction and hence improve the charge carrier mobilities. (see references: Bromley, S. T.;
Mas-Torrent, M.; Hadley, P.; Rovira, C. J. Am. Chem. Soc. 2004, 126, 6544;
Mcculloch, I.;
Heeney, M.; Bailey, C.; et al Nat. Mater. 2006, 5, 328.) One may be able to achieve semiconducting polymers with narrow band-gap and high charge mobilities if fused heterocyclic structures and the internal charge transfer concept are combined into the polymer backbones. However, the resulting materials will have extremely low solubility and may precipitate out of the polymerization solution, leading to the formation of only low molecular weight materials. In addition, the low solubility of the resulting materials will cause serious problem in the subsequent device fabrication using wet processes.
Poly(3-hexylthiophene) (P3HT)/soluble [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) bulk heterojunction (BHJ) system is one of the most promising systems and has been intensively studied. The state-of-art power conversion efficiency of this system is 5-6%. However further improvement in the power conversion efficiency is limited by the relatively large band-gap of P3HT (2.0 eV), resulting in inefficient coverage of the solar spectrum. (see references: Ma, W.; Yang, C.; Gong, X.; Lee, K.; Heeger, A. J.
Adv.
Funct. Mater. 2005, 15, 1617; Li, G.; Shrotriya, V.; Huang, J.; Yao, Y.;
Moriarty, T.;
Emery, K.; Yang, Y. Nat. Mater. 2005, 4, 826; Kim, K.; Liu, J.; Namboothiry, M. A. G.;
Carroll, D. App. Phys. Lett. 2007, 90, 163511.) Recently, a low band-gap benzothiadiazole and cyclopentadithiophene copolymer was prepared to show promising PCE values (3.2-5.5%) and high carrier mobility (10-cm2=V-l =s 1). However, no information on the crystallinity of this material has been reported, and the solubility of this polymer in common organic solvents is low. (see references: Peet, J.; Kim, J. Y.; Coates, N. E.; Ma, W. L.; Moses, D.; Heeger, A. J.;
Bazan, G. C. Nat. Mater. 2007, 6, 497-500; Zhang, M.; Tsao, H. N.; Pisula, W.;
Yang, C.;
Mishra, A. K.; Mullen, K. J. Am. Chem. Soc. 2007, 129, 3472.) Although numerous materials have been designed and synthesized for applications in organic solar cells as electron donors and light absorbers, none of them meet the requirements for the commercialization. (Blouin, N.; Michaud, A.; Gendron, D.;
Wakim, S.; Blair, E.; Neagu-Plesu, R.; Belletete, M.; Durocher, G.; Tao, Y.; Leclerc, M.; J. Am.
Chem. Soc. 2008 130 732; ) The demands on the materials are severe as a wide range of optical and electronic properties are required simultaneously, together with excellent stability and processibility. To make rigid conjugated semiconducting polymers soluble in certain solvents for solution processing, a sufficient amount of substituent has to be introduced to the polymers as side chains. As a result, these side-chains may dilute the content of electro-active components and lower the polymer crystallinity, which in turn result in lower conductivity.
Summary of the Invention Disclosed is a way to balance the dilemma between the solubility and crystallinity. The present inventors have discovered that with rational design of the substituent structure and substitution pattern, semiconducting polymers with high crystallinity and excellent solubility can be obtained.
According to embodiments of this invention, there is provided electron acceptors-cored regioregular oligothiophenes. The inventors have discovered that incorporation of the regioregular oligothiophenes substituted electron acceptors into the polymer backbones not only reduces the band-gaps but also improves the solubility of the resulting polymers.
Moreover, the synthesized polymers were also highly crystalline and demonstrated excellent photovoltaic performance when blended with PCBM as the photoactive layer.
A series of electron acceptors-cored regioregular oligothiophenes are designed and synthesized as shown in Formula I.
R, R, Br qs\ EA Br s m RZ RZ l ( ~
Br EA / \ Br s m s m wherein m is 2 to 6 Rl is an alkyl group, CnH2r+l, n=4-12 R2 is an alkyl group, CnH2n+1, n=4-12 EA is an electron-withdrawing group, and can be any one of the following structures:
Adv.
Funct. Mater. 2005, 15, 1617; Li, G.; Shrotriya, V.; Huang, J.; Yao, Y.;
Moriarty, T.;
Emery, K.; Yang, Y. Nat. Mater. 2005, 4, 826; Kim, K.; Liu, J.; Namboothiry, M. A. G.;
Carroll, D. App. Phys. Lett. 2007, 90, 163511.) Recently, a low band-gap benzothiadiazole and cyclopentadithiophene copolymer was prepared to show promising PCE values (3.2-5.5%) and high carrier mobility (10-cm2=V-l =s 1). However, no information on the crystallinity of this material has been reported, and the solubility of this polymer in common organic solvents is low. (see references: Peet, J.; Kim, J. Y.; Coates, N. E.; Ma, W. L.; Moses, D.; Heeger, A. J.;
Bazan, G. C. Nat. Mater. 2007, 6, 497-500; Zhang, M.; Tsao, H. N.; Pisula, W.;
Yang, C.;
Mishra, A. K.; Mullen, K. J. Am. Chem. Soc. 2007, 129, 3472.) Although numerous materials have been designed and synthesized for applications in organic solar cells as electron donors and light absorbers, none of them meet the requirements for the commercialization. (Blouin, N.; Michaud, A.; Gendron, D.;
Wakim, S.; Blair, E.; Neagu-Plesu, R.; Belletete, M.; Durocher, G.; Tao, Y.; Leclerc, M.; J. Am.
Chem. Soc. 2008 130 732; ) The demands on the materials are severe as a wide range of optical and electronic properties are required simultaneously, together with excellent stability and processibility. To make rigid conjugated semiconducting polymers soluble in certain solvents for solution processing, a sufficient amount of substituent has to be introduced to the polymers as side chains. As a result, these side-chains may dilute the content of electro-active components and lower the polymer crystallinity, which in turn result in lower conductivity.
Summary of the Invention Disclosed is a way to balance the dilemma between the solubility and crystallinity. The present inventors have discovered that with rational design of the substituent structure and substitution pattern, semiconducting polymers with high crystallinity and excellent solubility can be obtained.
According to embodiments of this invention, there is provided electron acceptors-cored regioregular oligothiophenes. The inventors have discovered that incorporation of the regioregular oligothiophenes substituted electron acceptors into the polymer backbones not only reduces the band-gaps but also improves the solubility of the resulting polymers.
Moreover, the synthesized polymers were also highly crystalline and demonstrated excellent photovoltaic performance when blended with PCBM as the photoactive layer.
A series of electron acceptors-cored regioregular oligothiophenes are designed and synthesized as shown in Formula I.
R, R, Br qs\ EA Br s m RZ RZ l ( ~
Br EA / \ Br s m s m wherein m is 2 to 6 Rl is an alkyl group, CnH2r+l, n=4-12 R2 is an alkyl group, CnH2n+1, n=4-12 EA is an electron-withdrawing group, and can be any one of the following structures:
EA
N N
N
N/ S \N N/ N N H N N/ S IN N/ N
O ~--J
R R
NC CN F F
NC CN NC CN NC CN
~ \ - ~ ~ \ / N~ N I I F F
/--` NC CN N,p,N p R R
Electron acceptors-cored regioregular oligothiophenes in formula I are synthesized either by a divergent or convergent approach, or by the combination of both approaches. In the divergent approach, the 3-alkylthiophene unit was attached one by one to the electron acceptor cores. On the contrary, in the convergent approach, regioregular oligothiophenes were first synthesized and then attached to the electron acceptors.
Also disclosed is the use of electron acceptors-cored regioregular oligothiophenes as building blocks for the preparation of soluble and crystalline polymeric materials, as shown in Formula II. The dibromides of the compounds in Formula I can be copolymerized with diboronates or distannanes of pi-conjugated compounds (electron donors) to form electron D-A conjugated polymers via Suzuki or Stille reaction, respectively.
R, R, / EA ED
S m s m n (II) and EA 4s \ ED
s m m n wherein m is 2 to 6 R, is an alkyl group, CnHZn+], n=4-12 R2 is an alkyl group, CnH2õ+l, n=4-12 EA is an electron-withdrawing group, selected Formula I
ED is a pi-conjugated electron donating group, and can be any one of the following structures:
ED =
R R R
Si N S R s R
j ~ u - - - C \ / ~
S S S S~Z ~
S S
N
R R
R R
S
wherein each R is independently selected from the group consisting of substituted and unsubstituted alkyl and aryl groups;
Also disclosed is the application of polymeric materials of Formula II in organic electronic devices, such as solar cells and field-effect transistors.
Brief Description of the Drawings Embodiments of the invention will now be described in conjunction with the accompanying drawings, wherein:
Figures lA, 1B, and 1C illustrate examples of organic electronic materials derived from electron acceptors-cored regioregular oligothiophenes in accordance with an aspect of the invention;
Figure 2 illustrates a schematic representation of a bulk heterojunction organic solar cell (BHJ-OSC);
Figure 3 illustrates a typical photo current-voltage curve of a bulk heterojunction solar cell based on a material of formula II;
Figure 4 illustrates differential scanning calorimetry (DSC) Curves of P(InCzTh2BTDTh2) showing its tendency to form crystalline structure; and Figure 5 illustrates DSC Curves of P(InCzTh3BTDTh3) showing its tendency to form crystalline structure.
This invention will now be described in detail with respect to showing how certain specific representative embodiments thereof can be made, the materials, apparatus and process steps being understood as examples that are intended to be illustrative only. In particular, the invention is not intended to be limited to the methods, materials, conditions, process parameters, apparatus and the like specifically recited herein.
Detailed Description of the Preferred Embodiments In accordance with the teachings of this invention, soluble crystalline conjugated materials are made from electron acceptors-cored regioregular oligothiophenes for applications in organic electronic devices. Such electron acceptors-cored regioregular oligothiophenes can be used as building blocks for the preparation of soluble low band-gap conjugated polymers for organic electronic devices, such as organic solar cells (OSC).
A series of electron acceptors-cored regioregular oligothiophenes are designed and synthesized as shown in Formula I.
R, Rl Br / 4\M EA Br s s Cp Br EA \ Br s m s wherein mis2to6 R, is an alkyl group, CnH2õ+1, n=4-12 R2 is an alkyl group, CnH2õ+l, n=4-12 EA is an electron-withdrawing group, and can be any one of the following structures:
EA
N N
Q/\ N N N N N/ N
N,S,N N,O,N \ / ,S, RJ~R
NC CN F F
NC CN NC CN NC CN _ N/ ~N ~ / I 1 I ~/
H NC CN NN C F F
R R ~~
Electron acceptors-cored regioregular oligothiophenes in formula I are synthesized either by a divergent or convergent approach, or by the combination of both approaches. In the divergent approach, the 3-alkylthiophene unit was attached one by one to the electron acceptor cores. On the contrary, in the convergent approach, regioregular oligothiophenes were first synthesized and then attached to the electron acceptors.
Also disclosed is the use of electron acceptors-cored regioregular oligothiophenes as building blocks for the preparation of soluble and crystalline polymeric materials. The dibromides of the compounds in Formula I can be copolymerized with diboronates or distannanes of pi-conjugated compounds (electron donors) to form electron D-A
conjugated polymers via Suzuki or Stille reaction, respectively.
Referring to Figures 1 A, l B and 1 C, D-A examples of low band gap materials for use in accordance with one aspect of the invention are illustrated, and are generally represented by the following general Formula (II).
R, R~
4(q EA 4sim ED
n (II) and ~ ~ EA 4 \ ED
S m S m n EA=
N N
N
N/ g' N N/ p' N N~ N N/ S \N N~ N
R R
NC CN F F
NC CN NC CN NC CN
/~ I
N~ N \ / I I F F
\ / ~ \
J~ NC CN N,O,N 0 R R
ED =
R R R
Si N S R S R
S\ ts S S
N
R R
R R
S S
wherein mis2to6 R, is an alkyl group, CõH2ri+I, n=4-12 R2 is an alkyl group, CõH2n+1, n=4-12 Each R is independently selected from the group consisting of substituted and unsubstituted alkyl and aryl groups;
D-A low band gap polymers of Formula (II) may be selected such that:
mis2to4;
R1 is an alkyl group, CõH2õ+], n=6-12 R2 is an alkyl group, CõHzn+l, n=4-12 R is an alkyl group, such as butyl, hexyl, octyl, 2-ethylhexyl, 2-butyloctyl, and 2-hexyldecyl.
The Pi conjugated bridge ED is indolocarbazole, thieothiophene, 3,3'-dialkyllsilylene-2,2'-bithiophene, or 9,9-dialkylfluorene;
The electron withdrawing moiety is benzothiadiazole, banzooxadiazole, or benzopyrazine.
Specifically mentioned as an example is indolocanbazole/4,7-Bis(3,4'-dioctyl-2,2'-bithiophen-5-yl)-2,1,3-benzothiadiazole alternating copolymer (P(InCzTh2BTDTh2)), as illustrated in Figure lA. P(InCzTh2BTDTh2) is a highly crystalline but still soluble material and showed good photovoltaic performance with a power conversion efficiency of 3.6% when blended with PCBM as the photoactive layer.
Further examples are given in Figure 1.
Synthesis of dibromonated bis(oligothiophene)benzothiadiazole monomers.
Scheme 1, The synthetic route towards dibromonated bis(oligothiophene)benzothiadiazole monomers (ThnBTD-2Br).
CgH 17 Me3Sn / CaH17 CBH CaHii CsH,?
Br~Br S\ 2 ts S\ NBS Br Br N, ,N --- / \ S S
S Pd(PPha)a N. .N N N
1 S S~
ThBTD ThBTD-2Br CBHn C8H17 CaH t7 CaH 17 2, Pd(PPh3)4 S S NBS Br S S S~ S Br S S
CeH17 NS N C8H17 a i~ S.
Th2BTD Th2BTD-2Br C8H17 CaHi7 CaHi7 CaH" NBS
2, Pd(PPhs)a S S
S S S S
C8H17 N.S,N C8H17 Th3BTD
C8H17 CaHn C8H17 8H17 Br S S S S Br C8H17 N,S,N C8H17 Th3BTD-2Br 4,7-bis(5-bromo-4-octyl-2-thienyl)-2,1,3-benzothiadiazole (ThBTD-2Br): A
mixture of 4,7-di(4-octyl-2-thienyl)-2,1,3-benzothiadiazole (4.2 g, 8.0 mmol), N-bromosuccinimide (NBS) (1.84 g, 17.6 mmol), silica gel (0.2 g) were dissolved in dichloromethane (25 mL) and stirred at room temperature for 4.0 h. The reaction mixture was filtered through a short silica gel column and desired product was obtained as a red solid (5.08 g, 93%). 1H
NMR (acetone-d6): S= 8.04 (s, 2H), 7.94 (s, 2H), 2.68 (t, 4H), 1.71 (m, 4H), 1.50-1.22 (m, 20H), 0.84 (t, 6H).
4,7-bis(3,4'-dioctyl-2,2'-bithiophen-5-yl)-2,1,3-benzothiadiazole (Th2BTD):
Pd(PPh3)4 (116 mg, 0.1 mmol) was added to a solution of ThBTD-2Br (3.41 g, 5.0 mmol) and trimethyl-(4-hexyl-2-thienyl)stannane (5.39 g, 15.0 mmol) in anhydrous DMF (10 mL).
The mixture was stirred under argon for 24 h at 100 C and then allowed to cool to room temperature. Saturated NaHCO3 aqueous solution was added. The aqueous layer was removed, and the organic layer was washed three times with distilled water.
The organic layer was dried over magnesium sulfate, and the solvent was removed under a reduced pressure. The residue was purified by column chromatography on silica gel (eluent:
hexane) to give the desired compound (4.02 g, 88%). 'H NMR (acetone-d6): S=
8.13 (s, 2H), 8.07 (s, 2H), 7.20 (s, 2H), 7.18 (s, 2H), 2.88 (t, 4H), 2.68 (t, 4H), 1.82-1.66 (m, 8H), 1.48-1.24 (m, 40H), 0.88 (t, 12H).
4, 7-bi s( 5' -bromo-3,4' -dioctyl-2,2' -bithiophen-5 -yl)-2,1, 3-benzothiadi azol e(Th2BTD-2Br): A mixture of Th2BTD (2.19 g, 2.40 mmol), N-bromosuccinimide (NBS) (0.854 g, 4.8 mmol), silica gel (0.2 g) were dissolved in dichloromethane (10 mL) and stirred at -C for 4 h. The reaction mixture was filtered through a short silica gel column using hexane as the eluent. The desired product was obtained as a dark purple solid (2.08 g, 81%). 1 H NMR (benzene-d6): S= 8.10 (s, 211), 8.05 (s, 2H), 7.12 (s, 2H), 2.84 (t, 4H), 2.63 (t, 4H), 1.70 (m, 8H), 1.48-1.20 (m, 40H), 0.86 (t, 12H). 13C NMR
(benzene-d6):
153.2, 143.4, 141.5, 138.2, 136.7, 132.6, 131.5, 127.6, 126.1, 125.6, 109.9, 32.7, 31.4, 30.44, 30.37, 30.33, 30.27, 30.23, 30.16, 30.10, 30.04, 30.01, 23.48, 23.47, 14.8.
4,7-bis(3,4'-dioctyl-2,2'-bithiophen-5-yl)-2,1,3-benzothiadiazole (Th3BTD):
Pd(PPh3)4 (46 mg, 0.04 mmol) was added to a solution of Th2BTD-2Br (2.14 g, 2.0 mmol) and trimethyl-(4-hexyl-2-thienyl)stannane (2.15 g, 6.0 mmol) in anhydrous DMF (10 mL).
The mixture was stirred under argon for 24 h at 100 C and then allowed to cool to room temperature. Saturated NaHCO3 aqueous solution was added. The aqueous layer was removed, and the organic layer was washed three times with distilled water.
The organic layer was dried over magnesium sulfate, and the solvent was removed under a reduced pressure. The residue was purified by column chromatography on silica gel (eluent:
hexane) to give the desired compound 2.16 g (83%). 'H NMR (benzene-d6): 8=
8.22 (s, 2H), 7.58 (s, 2H), 7.32 (s, 2H), 6.64 (s, 2H), 3.00 (t, 4H), 2.85 (t, 4H), 2.45 (t, 4H), 1.84 (m, 4H), 1.70 (m, 4H), 1.53-1.26 (m, 64H), 0.95-0.89 (m, 18H).
4, 7-bis(5' -bromo-3,4' -dioctyl-2,2' -bithiophen-5-yl)-2,1, 3 -benzothiadiazole(Th3B TD-2Br): A mixture of Th3BTD (1.81 g, 1.39 mmol), N-bromosuccinimide (NBS) (0.50 g, 2.78 mmol), silica gel (0.15 g) were dissolved in dichloromethane (30 mL) and stirred at -10 C for 5.5 h. The reaction was quenched with water (100 mL) and then extracted with dichloromethane for 2 times. Washed with water and dried with magnesium sulfate. Pure product was obtained by a silica gel column using hexane as eluent as a dark to purple solid (1.54g, 76%). 1H NMR (benzene-d6): 6= 8.20 (s, 2H), 7.58 (s, 2H), 7.26 (s, 2H), 6.92 (s, 2H), 2.98 (t, 4H), 2.73(t, 4H), 2.48 (t, 4H), 1.84 (m, 4H), 1.64 (m, 4H), 1.53-1.45 (m, 8H), 1.40-1.25 (m, 56H), 0.95-0.89 (m, 18H). 13C NMR (benzene-d6): 153.3, 143.4, 141.5, 141.3, 138.2, 136.3, 135.4, 133.0, 131.8, 131.3, 129.6, 127.7, 126.2, 125.7, 109.8, 32.6, 31.5, 31.4, 30.5, 30.42, 30.40, 30.3, 30.22, 30.17, 30.13, 30.10, 30.04, 30.02, 29.97, 23.46, 14.8, 14.7.
Synthesis of the copolymers based on benzothiadiazole-cored oligothiophene and indolocarbazole.
Scheme 2, the reaction scheme for the polymerization:
CgH17_~
CaH17 C8H17 N
Pd(PPh3)4, KZC03 Br 0 / \ Br + Q - - - 0~
$ x /\ S B"O aliqua 336, toluene N,S,N N
~CgH17 C6H17~
x = 2 P(InCzTh2BTDTh2) S x S X~ x= 3 P(InCZTh3BTDTh3) N~ ~N N
S' ~CA7 Synthesis of P(InCzThZBTDTh2): To a solution of Th2BTD-2Br (0.31 mmol) and indolocarbazole monomer (0.3 mmol) in a mixture of 1/1 (v/v) toluene/NaZCO3 (2M, aqueous) was added tetra(triphenylphosphine)palladium(0) (0.006 mmol) in glove box.
The reaction mixture was stirred with reflux under the protection with argon for 48 hrs.
Then, a degassed solution of phenylboronic acid (0.045 mmol) in toluene (1 mL) was added. The end-capping reaction was run at reflux for one more day. After the solution was cooled down to room temperature, the aqueous layer was removed and the organic layer was dropped into methanol to precipitate the polymer. Dark purple fiber-like solid was obtained by filtration, redissolved in chlorobenzne, f ltered to remove any salts, and reprecipitated in methanol. The resultant polymer was further purified by Soxlet extraction with hexanes. Yield: 89.9 %. GPC: Mõ = 19,5000, PDI = 2.08. DSC: Tg = 158 C, T,,, = 260 C.
Synthesis of P(InCzTh3BTDTh3): A similar procedure as the preparation of P(InCzThZBTDTh2) was used except Th3BTD-2Br (0.31 mmol) and indolocarbazole monomer (0.3 mmol) were added. The resulting dark purple fiber-like solid was purified by Soxlet extraction with hexanes. Yield: 85.8 %. GPC result: Mõ = 30,100, PDI
= 1.91.
DSC result: Tg = 78.5 C, T,,, = 191 C.
Referring to Figure 2, there is illustrated the structure of a bulk heterojunction organic solar cell in accordance with one aspect of the invention. A transparent substrate is partially coated with a transparent electrode, such as conductive oxide, conducting polymer, and conducting nanocomposite, in this case indium-tin-oxide (ITO) to form the anode. A thin layer of PEDOT-PSS was spin-coated on top of ITO as a hole injection layer. Then a blend film of P(InCzTh2BTDTh2) and PCBM (a fullerene derivative [6,6]-phenyl C61-butyric acid methyl ester) was spin-coated on PEDOT-PSS as a photoactive layer. Finally, LiF( I nm) and Al (100 nm) were vacuum-deposited as a cathode.
In other embodiments and uses, the substrate can be any suitable substrate.
For example, it may be rigid or flexible. The substrate may be plastic or glass. It can be as thin as 10 microns, if presents as a flexible plastic or substantially thicker if present as a rigid glass.
It is also contemplated to use a PET sheet substrate.
Figure 3 illustrates a typical photo current-voltage curve of a bulk heterojunction solar cell based on a blend film of P(InCzTh2BTDTh2) and PCBM (1:2 wt/wt). Under AM
1.5 simulated solar illumination (100 mW/cm2), this device gave a Voc of 0.69 V, a Jsc of 9.17 mA/cm2, and an overall efficiency of 3.6 %.
Figure 4 illustrates differential scanning calorimetry (DSC) Curves of P(InCzTh2BTDTh2) showing its tendency to form crystalline structure. Figure 5 illustrates DSC Curves of P(InCzTh3BTDTh3) showing its tendency to form crystalline structure. The DSC analysis was performed under a nitrogen atmosphere (60 mL/
min) on a TA Instruments DSC 2920 at a heating/cooling rate of 10 C/min. If the polymer is an amorphous material, it only shows a glass transition temperature in the DSC scan.
Both polymers P(InCzTh2BTDTh2) and P(InCzTh3BTDTh3) show a nice melting peak in the heating scan and crystallizing peak in the cooling scan. Each of these polymers have a solubility more than 10 mg/mL in chloroform, chlorobenzene, and o-dichlorobenzene.
Numerous modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
N N
N
N/ S \N N/ N N H N N/ S IN N/ N
O ~--J
R R
NC CN F F
NC CN NC CN NC CN
~ \ - ~ ~ \ / N~ N I I F F
/--` NC CN N,p,N p R R
Electron acceptors-cored regioregular oligothiophenes in formula I are synthesized either by a divergent or convergent approach, or by the combination of both approaches. In the divergent approach, the 3-alkylthiophene unit was attached one by one to the electron acceptor cores. On the contrary, in the convergent approach, regioregular oligothiophenes were first synthesized and then attached to the electron acceptors.
Also disclosed is the use of electron acceptors-cored regioregular oligothiophenes as building blocks for the preparation of soluble and crystalline polymeric materials, as shown in Formula II. The dibromides of the compounds in Formula I can be copolymerized with diboronates or distannanes of pi-conjugated compounds (electron donors) to form electron D-A conjugated polymers via Suzuki or Stille reaction, respectively.
R, R, / EA ED
S m s m n (II) and EA 4s \ ED
s m m n wherein m is 2 to 6 R, is an alkyl group, CnHZn+], n=4-12 R2 is an alkyl group, CnH2õ+l, n=4-12 EA is an electron-withdrawing group, selected Formula I
ED is a pi-conjugated electron donating group, and can be any one of the following structures:
ED =
R R R
Si N S R s R
j ~ u - - - C \ / ~
S S S S~Z ~
S S
N
R R
R R
S
wherein each R is independently selected from the group consisting of substituted and unsubstituted alkyl and aryl groups;
Also disclosed is the application of polymeric materials of Formula II in organic electronic devices, such as solar cells and field-effect transistors.
Brief Description of the Drawings Embodiments of the invention will now be described in conjunction with the accompanying drawings, wherein:
Figures lA, 1B, and 1C illustrate examples of organic electronic materials derived from electron acceptors-cored regioregular oligothiophenes in accordance with an aspect of the invention;
Figure 2 illustrates a schematic representation of a bulk heterojunction organic solar cell (BHJ-OSC);
Figure 3 illustrates a typical photo current-voltage curve of a bulk heterojunction solar cell based on a material of formula II;
Figure 4 illustrates differential scanning calorimetry (DSC) Curves of P(InCzTh2BTDTh2) showing its tendency to form crystalline structure; and Figure 5 illustrates DSC Curves of P(InCzTh3BTDTh3) showing its tendency to form crystalline structure.
This invention will now be described in detail with respect to showing how certain specific representative embodiments thereof can be made, the materials, apparatus and process steps being understood as examples that are intended to be illustrative only. In particular, the invention is not intended to be limited to the methods, materials, conditions, process parameters, apparatus and the like specifically recited herein.
Detailed Description of the Preferred Embodiments In accordance with the teachings of this invention, soluble crystalline conjugated materials are made from electron acceptors-cored regioregular oligothiophenes for applications in organic electronic devices. Such electron acceptors-cored regioregular oligothiophenes can be used as building blocks for the preparation of soluble low band-gap conjugated polymers for organic electronic devices, such as organic solar cells (OSC).
A series of electron acceptors-cored regioregular oligothiophenes are designed and synthesized as shown in Formula I.
R, Rl Br / 4\M EA Br s s Cp Br EA \ Br s m s wherein mis2to6 R, is an alkyl group, CnH2õ+1, n=4-12 R2 is an alkyl group, CnH2õ+l, n=4-12 EA is an electron-withdrawing group, and can be any one of the following structures:
EA
N N
Q/\ N N N N N/ N
N,S,N N,O,N \ / ,S, RJ~R
NC CN F F
NC CN NC CN NC CN _ N/ ~N ~ / I 1 I ~/
H NC CN NN C F F
R R ~~
Electron acceptors-cored regioregular oligothiophenes in formula I are synthesized either by a divergent or convergent approach, or by the combination of both approaches. In the divergent approach, the 3-alkylthiophene unit was attached one by one to the electron acceptor cores. On the contrary, in the convergent approach, regioregular oligothiophenes were first synthesized and then attached to the electron acceptors.
Also disclosed is the use of electron acceptors-cored regioregular oligothiophenes as building blocks for the preparation of soluble and crystalline polymeric materials. The dibromides of the compounds in Formula I can be copolymerized with diboronates or distannanes of pi-conjugated compounds (electron donors) to form electron D-A
conjugated polymers via Suzuki or Stille reaction, respectively.
Referring to Figures 1 A, l B and 1 C, D-A examples of low band gap materials for use in accordance with one aspect of the invention are illustrated, and are generally represented by the following general Formula (II).
R, R~
4(q EA 4sim ED
n (II) and ~ ~ EA 4 \ ED
S m S m n EA=
N N
N
N/ g' N N/ p' N N~ N N/ S \N N~ N
R R
NC CN F F
NC CN NC CN NC CN
/~ I
N~ N \ / I I F F
\ / ~ \
J~ NC CN N,O,N 0 R R
ED =
R R R
Si N S R S R
S\ ts S S
N
R R
R R
S S
wherein mis2to6 R, is an alkyl group, CõH2ri+I, n=4-12 R2 is an alkyl group, CõH2n+1, n=4-12 Each R is independently selected from the group consisting of substituted and unsubstituted alkyl and aryl groups;
D-A low band gap polymers of Formula (II) may be selected such that:
mis2to4;
R1 is an alkyl group, CõH2õ+], n=6-12 R2 is an alkyl group, CõHzn+l, n=4-12 R is an alkyl group, such as butyl, hexyl, octyl, 2-ethylhexyl, 2-butyloctyl, and 2-hexyldecyl.
The Pi conjugated bridge ED is indolocarbazole, thieothiophene, 3,3'-dialkyllsilylene-2,2'-bithiophene, or 9,9-dialkylfluorene;
The electron withdrawing moiety is benzothiadiazole, banzooxadiazole, or benzopyrazine.
Specifically mentioned as an example is indolocanbazole/4,7-Bis(3,4'-dioctyl-2,2'-bithiophen-5-yl)-2,1,3-benzothiadiazole alternating copolymer (P(InCzTh2BTDTh2)), as illustrated in Figure lA. P(InCzTh2BTDTh2) is a highly crystalline but still soluble material and showed good photovoltaic performance with a power conversion efficiency of 3.6% when blended with PCBM as the photoactive layer.
Further examples are given in Figure 1.
Synthesis of dibromonated bis(oligothiophene)benzothiadiazole monomers.
Scheme 1, The synthetic route towards dibromonated bis(oligothiophene)benzothiadiazole monomers (ThnBTD-2Br).
CgH 17 Me3Sn / CaH17 CBH CaHii CsH,?
Br~Br S\ 2 ts S\ NBS Br Br N, ,N --- / \ S S
S Pd(PPha)a N. .N N N
1 S S~
ThBTD ThBTD-2Br CBHn C8H17 CaH t7 CaH 17 2, Pd(PPh3)4 S S NBS Br S S S~ S Br S S
CeH17 NS N C8H17 a i~ S.
Th2BTD Th2BTD-2Br C8H17 CaHi7 CaHi7 CaH" NBS
2, Pd(PPhs)a S S
S S S S
C8H17 N.S,N C8H17 Th3BTD
C8H17 CaHn C8H17 8H17 Br S S S S Br C8H17 N,S,N C8H17 Th3BTD-2Br 4,7-bis(5-bromo-4-octyl-2-thienyl)-2,1,3-benzothiadiazole (ThBTD-2Br): A
mixture of 4,7-di(4-octyl-2-thienyl)-2,1,3-benzothiadiazole (4.2 g, 8.0 mmol), N-bromosuccinimide (NBS) (1.84 g, 17.6 mmol), silica gel (0.2 g) were dissolved in dichloromethane (25 mL) and stirred at room temperature for 4.0 h. The reaction mixture was filtered through a short silica gel column and desired product was obtained as a red solid (5.08 g, 93%). 1H
NMR (acetone-d6): S= 8.04 (s, 2H), 7.94 (s, 2H), 2.68 (t, 4H), 1.71 (m, 4H), 1.50-1.22 (m, 20H), 0.84 (t, 6H).
4,7-bis(3,4'-dioctyl-2,2'-bithiophen-5-yl)-2,1,3-benzothiadiazole (Th2BTD):
Pd(PPh3)4 (116 mg, 0.1 mmol) was added to a solution of ThBTD-2Br (3.41 g, 5.0 mmol) and trimethyl-(4-hexyl-2-thienyl)stannane (5.39 g, 15.0 mmol) in anhydrous DMF (10 mL).
The mixture was stirred under argon for 24 h at 100 C and then allowed to cool to room temperature. Saturated NaHCO3 aqueous solution was added. The aqueous layer was removed, and the organic layer was washed three times with distilled water.
The organic layer was dried over magnesium sulfate, and the solvent was removed under a reduced pressure. The residue was purified by column chromatography on silica gel (eluent:
hexane) to give the desired compound (4.02 g, 88%). 'H NMR (acetone-d6): S=
8.13 (s, 2H), 8.07 (s, 2H), 7.20 (s, 2H), 7.18 (s, 2H), 2.88 (t, 4H), 2.68 (t, 4H), 1.82-1.66 (m, 8H), 1.48-1.24 (m, 40H), 0.88 (t, 12H).
4, 7-bi s( 5' -bromo-3,4' -dioctyl-2,2' -bithiophen-5 -yl)-2,1, 3-benzothiadi azol e(Th2BTD-2Br): A mixture of Th2BTD (2.19 g, 2.40 mmol), N-bromosuccinimide (NBS) (0.854 g, 4.8 mmol), silica gel (0.2 g) were dissolved in dichloromethane (10 mL) and stirred at -C for 4 h. The reaction mixture was filtered through a short silica gel column using hexane as the eluent. The desired product was obtained as a dark purple solid (2.08 g, 81%). 1 H NMR (benzene-d6): S= 8.10 (s, 211), 8.05 (s, 2H), 7.12 (s, 2H), 2.84 (t, 4H), 2.63 (t, 4H), 1.70 (m, 8H), 1.48-1.20 (m, 40H), 0.86 (t, 12H). 13C NMR
(benzene-d6):
153.2, 143.4, 141.5, 138.2, 136.7, 132.6, 131.5, 127.6, 126.1, 125.6, 109.9, 32.7, 31.4, 30.44, 30.37, 30.33, 30.27, 30.23, 30.16, 30.10, 30.04, 30.01, 23.48, 23.47, 14.8.
4,7-bis(3,4'-dioctyl-2,2'-bithiophen-5-yl)-2,1,3-benzothiadiazole (Th3BTD):
Pd(PPh3)4 (46 mg, 0.04 mmol) was added to a solution of Th2BTD-2Br (2.14 g, 2.0 mmol) and trimethyl-(4-hexyl-2-thienyl)stannane (2.15 g, 6.0 mmol) in anhydrous DMF (10 mL).
The mixture was stirred under argon for 24 h at 100 C and then allowed to cool to room temperature. Saturated NaHCO3 aqueous solution was added. The aqueous layer was removed, and the organic layer was washed three times with distilled water.
The organic layer was dried over magnesium sulfate, and the solvent was removed under a reduced pressure. The residue was purified by column chromatography on silica gel (eluent:
hexane) to give the desired compound 2.16 g (83%). 'H NMR (benzene-d6): 8=
8.22 (s, 2H), 7.58 (s, 2H), 7.32 (s, 2H), 6.64 (s, 2H), 3.00 (t, 4H), 2.85 (t, 4H), 2.45 (t, 4H), 1.84 (m, 4H), 1.70 (m, 4H), 1.53-1.26 (m, 64H), 0.95-0.89 (m, 18H).
4, 7-bis(5' -bromo-3,4' -dioctyl-2,2' -bithiophen-5-yl)-2,1, 3 -benzothiadiazole(Th3B TD-2Br): A mixture of Th3BTD (1.81 g, 1.39 mmol), N-bromosuccinimide (NBS) (0.50 g, 2.78 mmol), silica gel (0.15 g) were dissolved in dichloromethane (30 mL) and stirred at -10 C for 5.5 h. The reaction was quenched with water (100 mL) and then extracted with dichloromethane for 2 times. Washed with water and dried with magnesium sulfate. Pure product was obtained by a silica gel column using hexane as eluent as a dark to purple solid (1.54g, 76%). 1H NMR (benzene-d6): 6= 8.20 (s, 2H), 7.58 (s, 2H), 7.26 (s, 2H), 6.92 (s, 2H), 2.98 (t, 4H), 2.73(t, 4H), 2.48 (t, 4H), 1.84 (m, 4H), 1.64 (m, 4H), 1.53-1.45 (m, 8H), 1.40-1.25 (m, 56H), 0.95-0.89 (m, 18H). 13C NMR (benzene-d6): 153.3, 143.4, 141.5, 141.3, 138.2, 136.3, 135.4, 133.0, 131.8, 131.3, 129.6, 127.7, 126.2, 125.7, 109.8, 32.6, 31.5, 31.4, 30.5, 30.42, 30.40, 30.3, 30.22, 30.17, 30.13, 30.10, 30.04, 30.02, 29.97, 23.46, 14.8, 14.7.
Synthesis of the copolymers based on benzothiadiazole-cored oligothiophene and indolocarbazole.
Scheme 2, the reaction scheme for the polymerization:
CgH17_~
CaH17 C8H17 N
Pd(PPh3)4, KZC03 Br 0 / \ Br + Q - - - 0~
$ x /\ S B"O aliqua 336, toluene N,S,N N
~CgH17 C6H17~
x = 2 P(InCzTh2BTDTh2) S x S X~ x= 3 P(InCZTh3BTDTh3) N~ ~N N
S' ~CA7 Synthesis of P(InCzThZBTDTh2): To a solution of Th2BTD-2Br (0.31 mmol) and indolocarbazole monomer (0.3 mmol) in a mixture of 1/1 (v/v) toluene/NaZCO3 (2M, aqueous) was added tetra(triphenylphosphine)palladium(0) (0.006 mmol) in glove box.
The reaction mixture was stirred with reflux under the protection with argon for 48 hrs.
Then, a degassed solution of phenylboronic acid (0.045 mmol) in toluene (1 mL) was added. The end-capping reaction was run at reflux for one more day. After the solution was cooled down to room temperature, the aqueous layer was removed and the organic layer was dropped into methanol to precipitate the polymer. Dark purple fiber-like solid was obtained by filtration, redissolved in chlorobenzne, f ltered to remove any salts, and reprecipitated in methanol. The resultant polymer was further purified by Soxlet extraction with hexanes. Yield: 89.9 %. GPC: Mõ = 19,5000, PDI = 2.08. DSC: Tg = 158 C, T,,, = 260 C.
Synthesis of P(InCzTh3BTDTh3): A similar procedure as the preparation of P(InCzThZBTDTh2) was used except Th3BTD-2Br (0.31 mmol) and indolocarbazole monomer (0.3 mmol) were added. The resulting dark purple fiber-like solid was purified by Soxlet extraction with hexanes. Yield: 85.8 %. GPC result: Mõ = 30,100, PDI
= 1.91.
DSC result: Tg = 78.5 C, T,,, = 191 C.
Referring to Figure 2, there is illustrated the structure of a bulk heterojunction organic solar cell in accordance with one aspect of the invention. A transparent substrate is partially coated with a transparent electrode, such as conductive oxide, conducting polymer, and conducting nanocomposite, in this case indium-tin-oxide (ITO) to form the anode. A thin layer of PEDOT-PSS was spin-coated on top of ITO as a hole injection layer. Then a blend film of P(InCzTh2BTDTh2) and PCBM (a fullerene derivative [6,6]-phenyl C61-butyric acid methyl ester) was spin-coated on PEDOT-PSS as a photoactive layer. Finally, LiF( I nm) and Al (100 nm) were vacuum-deposited as a cathode.
In other embodiments and uses, the substrate can be any suitable substrate.
For example, it may be rigid or flexible. The substrate may be plastic or glass. It can be as thin as 10 microns, if presents as a flexible plastic or substantially thicker if present as a rigid glass.
It is also contemplated to use a PET sheet substrate.
Figure 3 illustrates a typical photo current-voltage curve of a bulk heterojunction solar cell based on a blend film of P(InCzTh2BTDTh2) and PCBM (1:2 wt/wt). Under AM
1.5 simulated solar illumination (100 mW/cm2), this device gave a Voc of 0.69 V, a Jsc of 9.17 mA/cm2, and an overall efficiency of 3.6 %.
Figure 4 illustrates differential scanning calorimetry (DSC) Curves of P(InCzTh2BTDTh2) showing its tendency to form crystalline structure. Figure 5 illustrates DSC Curves of P(InCzTh3BTDTh3) showing its tendency to form crystalline structure. The DSC analysis was performed under a nitrogen atmosphere (60 mL/
min) on a TA Instruments DSC 2920 at a heating/cooling rate of 10 C/min. If the polymer is an amorphous material, it only shows a glass transition temperature in the DSC scan.
Both polymers P(InCzTh2BTDTh2) and P(InCzTh3BTDTh3) show a nice melting peak in the heating scan and crystallizing peak in the cooling scan. Each of these polymers have a solubility more than 10 mg/mL in chloroform, chlorobenzene, and o-dichlorobenzene.
Numerous modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (13)
1. A series of electron acceptors-cored regioregular oligothiophenes of Formula I
wherein m is 2 to 6 R1 is an alkyl group, C n H2n+1, n=4-12 R2 is an alkyl group, C n H2n+1, n=4-12 EA is an electron-withdrawing group, and can be any one of the following structures
wherein m is 2 to 6 R1 is an alkyl group, C n H2n+1, n=4-12 R2 is an alkyl group, C n H2n+1, n=4-12 EA is an electron-withdrawing group, and can be any one of the following structures
2. A method of forming series of electron acceptors-cored regioregular oligothiophenes of Formula I:
wherein m is 2 to 6 R1 is an alkyl group, C n H2n+1, n=4-12 R2 is an alkyl group, C n H2n+1, n=4-12 EA is an electron-withdrawing group, and can be any one of the following structures the method comprising: synthesizing the regioregular oligothiophene.
wherein m is 2 to 6 R1 is an alkyl group, C n H2n+1, n=4-12 R2 is an alkyl group, C n H2n+1, n=4-12 EA is an electron-withdrawing group, and can be any one of the following structures the method comprising: synthesizing the regioregular oligothiophene.
3. The method of claim 2, wherein the step of synthesizing is done via a divergent approach.
4. The method of claim 3, wherein the 3-alkylthiophene unit was attached one by one to the electron acceptor cores.
5. The method of claim 2, wherein the step of synthesizing is done via a convergent approach.
6. The method of claim 5, wherein regioregular oligothiophenes were first synthesized and then attached to the electron acceptors.
7. The method of claim 2, wherein step of synthesizing is done via a combination of a convergent approach and a divergent approach.
8. A method of forming a soluble and crystalline low band gap polymer using a regioregular oligothiophene substituted electron acceptors, comprising:
synthesizing the regioregular oligothiophene as defined in the methods of any one of claims 2 to 7; and copolymerizing the dibromides of the substituted electron acceptor with diboronates or distannanes of the electron donors to form D-A conjugated polymers, wherein the polymer is defined by Formula II:
wherein m is 2 to 6 R1 is an alkyl group, C n H2n+1, n=4-12 R2 is an alkyl group, C n H2n+1, n=4-12 Each R is independently selected from the group consisting of substituted and unsubstituted alkyl and aryl groups.
synthesizing the regioregular oligothiophene as defined in the methods of any one of claims 2 to 7; and copolymerizing the dibromides of the substituted electron acceptor with diboronates or distannanes of the electron donors to form D-A conjugated polymers, wherein the polymer is defined by Formula II:
wherein m is 2 to 6 R1 is an alkyl group, C n H2n+1, n=4-12 R2 is an alkyl group, C n H2n+1, n=4-12 Each R is independently selected from the group consisting of substituted and unsubstituted alkyl and aryl groups.
9. The method of claim 8, wherein:
m is 2 to 4;
R1 is an alkyl group, C n H2n+1, n=6-12 R2 is an alkyl group, C n H2n+1, n=4-12 R is an alkyl group, such as butyl, hexyl, octyl, 2-ethylhexyl, 2-butyloctyl, and 2-hexyldecyl.
The Pi conjugated bridge ED is indolocarbazole, thieothiophene, 3,3'-dialkyllsilylene-2,2'-bithiophene, or 9,9-dialkylfluorene;
The electron withdrawing moiety is benzothiadiazole, banzooxadiazole, or benzopyrazine.
m is 2 to 4;
R1 is an alkyl group, C n H2n+1, n=6-12 R2 is an alkyl group, C n H2n+1, n=4-12 R is an alkyl group, such as butyl, hexyl, octyl, 2-ethylhexyl, 2-butyloctyl, and 2-hexyldecyl.
The Pi conjugated bridge ED is indolocarbazole, thieothiophene, 3,3'-dialkyllsilylene-2,2'-bithiophene, or 9,9-dialkylfluorene;
The electron withdrawing moiety is benzothiadiazole, banzooxadiazole, or benzopyrazine.
10. The method of claim 8, wherein the step of coplymerizing is done via a Suzuki reaction.
11. The method of claim 8, wherein the step of coplymerizing is done via a Stille reaction.
12. Use of electron acceptors-cored regioregular oligothiophenes in formula I
as building blocks for the preparation of soluble and crystalline low band gap polymers with a general structure in Formular II.
wherein m is 2 to 6 R1 is an alkyl group, C n H2n+1, n=4-12 R2 is an alkyl group, C n H2n+1, n=4-12 Each R is independently selected from the group consisting of substituted and unsubstituted alkyl and aryl groups;
EA is an electron-withdrawing unit, and can be any one listed in formula I.
as building blocks for the preparation of soluble and crystalline low band gap polymers with a general structure in Formular II.
wherein m is 2 to 6 R1 is an alkyl group, C n H2n+1, n=4-12 R2 is an alkyl group, C n H2n+1, n=4-12 Each R is independently selected from the group consisting of substituted and unsubstituted alkyl and aryl groups;
EA is an electron-withdrawing unit, and can be any one listed in formula I.
13. Use of a D-A conjugated polymer represented by Formula (II) for applications in organic electronic devices, such as solar cells and field-effect transistors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002625306A CA2625306A1 (en) | 2008-03-11 | 2008-03-11 | Electron acceptors-cored regioregular oligothiophenes as building blocks for soluble low band-gap conjugated polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002625306A CA2625306A1 (en) | 2008-03-11 | 2008-03-11 | Electron acceptors-cored regioregular oligothiophenes as building blocks for soluble low band-gap conjugated polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2625306A1 true CA2625306A1 (en) | 2009-09-11 |
Family
ID=41060213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002625306A Abandoned CA2625306A1 (en) | 2008-03-11 | 2008-03-11 | Electron acceptors-cored regioregular oligothiophenes as building blocks for soluble low band-gap conjugated polymers |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2625306A1 (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010041687A1 (en) * | 2008-10-09 | 2010-04-15 | コニカミノルタホールディングス株式会社 | Organic photoelectric conversion element, solar cell, and optical sensor array |
| WO2011060526A1 (en) * | 2009-11-18 | 2011-05-26 | National Research Council Of Canada | Fluorinated monomers, oligomers and polymers for use in organic electronic devices |
| EP2333017A1 (en) | 2009-10-26 | 2011-06-15 | Taiwan Textile Research Institute | A novel dye-dopant, a composition comprising the same and a photovoltaic device including such composition |
| CN102153732A (en) * | 2011-01-10 | 2011-08-17 | 常州大学 | Copolymer of stereo-regular thiophene oligomer and benzothiadiazole and preparation method thereof |
| US20120156829A1 (en) * | 2009-08-28 | 2012-06-21 | Zhikuan Chen | Polymeric semiconductors, devices, and related methods |
| CN102786669A (en) * | 2012-07-30 | 2012-11-21 | 常州大学 | Polymer semi-conductor material, preparation method and application thereof |
| CN103280531A (en) * | 2013-05-10 | 2013-09-04 | 中国科学院长春应用化学研究所 | Polymer solar cell |
| US8624232B2 (en) | 2009-08-28 | 2014-01-07 | Prashant Sonar | Ambipolar polymeric semiconductor materials and organic electronic devices |
| WO2014074027A1 (en) * | 2012-11-07 | 2014-05-15 | Lanxess Deutschland Gmbh | Polymers and their use in photovoltaic devices |
| US20140142308A1 (en) * | 2011-03-08 | 2014-05-22 | Nankai University | Photoelectric materials and preparation thereof |
| CN103833980A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | Bidiselenophen-silolezodi(diazosulfide) copolymer, preparation method and application thereof |
| CN103848970A (en) * | 2012-11-29 | 2014-06-11 | 海洋王照明科技股份有限公司 | Polymer containing bithiophene diazosulfide unit, its preparation method and solar cell device |
| CN104098758A (en) * | 2013-04-09 | 2014-10-15 | 河南师范大学 | Synthetic method for serial efficient organic solar cell materials |
| CN104211910A (en) * | 2013-05-29 | 2014-12-17 | 海洋王照明科技股份有限公司 | Conjugated polymer, preparation method and applications thereof |
| CN104211914A (en) * | 2013-05-29 | 2014-12-17 | 海洋王照明科技股份有限公司 | Conjugated polymer, preparation method, and applications thereof |
| CN104211911A (en) * | 2013-05-29 | 2014-12-17 | 海洋王照明科技股份有限公司 | Conjugated polymer, preparation method, and applications thereof |
| CN104211919A (en) * | 2013-05-29 | 2014-12-17 | 海洋王照明科技股份有限公司 | Conjugated polymer, preparation method, and applications thereof |
| WO2018157427A1 (en) * | 2017-03-03 | 2018-09-07 | 南方科技大学 | Heteroatom-substituted benzothiadiazole-based polymer donor material, and preparation method and application thereof |
| GB2591997A (en) * | 2020-02-04 | 2021-08-18 | Sumitomo Chemical Co | Photoactive material |
| CN114853763A (en) * | 2022-03-23 | 2022-08-05 | 大连理工大学 | D-pi-A compound and application thereof in perovskite solar cell passivation |
-
2008
- 2008-03-11 CA CA002625306A patent/CA2625306A1/en not_active Abandoned
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010041687A1 (en) * | 2008-10-09 | 2010-04-15 | コニカミノルタホールディングス株式会社 | Organic photoelectric conversion element, solar cell, and optical sensor array |
| JP5655568B2 (en) * | 2008-10-09 | 2015-01-21 | コニカミノルタ株式会社 | Organic photoelectric conversion element, solar cell, and optical sensor array |
| US8765968B2 (en) * | 2009-08-28 | 2014-07-01 | Agency For Science, Technology And Research | Polymeric semiconductors, devices, and related methods |
| US9166167B2 (en) | 2009-08-28 | 2015-10-20 | Agency For Science, Technology And Research | P-type materials and organic electronic devices |
| US20120156829A1 (en) * | 2009-08-28 | 2012-06-21 | Zhikuan Chen | Polymeric semiconductors, devices, and related methods |
| US9627621B2 (en) | 2009-08-28 | 2017-04-18 | Agency For Science, Technology And Research | Polymeric semiconductors, devices, and related methods |
| US8624232B2 (en) | 2009-08-28 | 2014-01-07 | Prashant Sonar | Ambipolar polymeric semiconductor materials and organic electronic devices |
| EP2333017A1 (en) | 2009-10-26 | 2011-06-15 | Taiwan Textile Research Institute | A novel dye-dopant, a composition comprising the same and a photovoltaic device including such composition |
| US8927684B2 (en) | 2009-11-18 | 2015-01-06 | National Research Council Of Canada | Fluorinated monomers, oligomers and polymers for use in organic electronic devices |
| WO2011060526A1 (en) * | 2009-11-18 | 2011-05-26 | National Research Council Of Canada | Fluorinated monomers, oligomers and polymers for use in organic electronic devices |
| CN102153732B (en) * | 2011-01-10 | 2013-04-17 | 常州大学 | Copolymer of stereo-regular thiophene oligomer and benzothiadiazole and preparation method thereof |
| CN102153732A (en) * | 2011-01-10 | 2011-08-17 | 常州大学 | Copolymer of stereo-regular thiophene oligomer and benzothiadiazole and preparation method thereof |
| US20140142308A1 (en) * | 2011-03-08 | 2014-05-22 | Nankai University | Photoelectric materials and preparation thereof |
| US9184315B2 (en) * | 2011-03-08 | 2015-11-10 | Nankai University | Photoelectric materials and preparation thereof |
| CN102786669B (en) * | 2012-07-30 | 2014-06-18 | 常州大学 | Polymer semi-conductor material, preparation method and application thereof |
| CN102786669A (en) * | 2012-07-30 | 2012-11-21 | 常州大学 | Polymer semi-conductor material, preparation method and application thereof |
| WO2014074027A1 (en) * | 2012-11-07 | 2014-05-15 | Lanxess Deutschland Gmbh | Polymers and their use in photovoltaic devices |
| CN103833980A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | Bidiselenophen-silolezodi(diazosulfide) copolymer, preparation method and application thereof |
| CN103833980B (en) * | 2012-11-27 | 2016-01-13 | 海洋王照明科技股份有限公司 | Di-selenophen-thiophene is coughed up and two (diazosulfide) multipolymer and its preparation method and application |
| CN103848970A (en) * | 2012-11-29 | 2014-06-11 | 海洋王照明科技股份有限公司 | Polymer containing bithiophene diazosulfide unit, its preparation method and solar cell device |
| CN104098758A (en) * | 2013-04-09 | 2014-10-15 | 河南师范大学 | Synthetic method for serial efficient organic solar cell materials |
| CN103280531A (en) * | 2013-05-10 | 2013-09-04 | 中国科学院长春应用化学研究所 | Polymer solar cell |
| CN104211914A (en) * | 2013-05-29 | 2014-12-17 | 海洋王照明科技股份有限公司 | Conjugated polymer, preparation method, and applications thereof |
| CN104211911A (en) * | 2013-05-29 | 2014-12-17 | 海洋王照明科技股份有限公司 | Conjugated polymer, preparation method, and applications thereof |
| CN104211919A (en) * | 2013-05-29 | 2014-12-17 | 海洋王照明科技股份有限公司 | Conjugated polymer, preparation method, and applications thereof |
| CN104211910A (en) * | 2013-05-29 | 2014-12-17 | 海洋王照明科技股份有限公司 | Conjugated polymer, preparation method and applications thereof |
| WO2018157427A1 (en) * | 2017-03-03 | 2018-09-07 | 南方科技大学 | Heteroatom-substituted benzothiadiazole-based polymer donor material, and preparation method and application thereof |
| GB2591997A (en) * | 2020-02-04 | 2021-08-18 | Sumitomo Chemical Co | Photoactive material |
| CN114853763A (en) * | 2022-03-23 | 2022-08-05 | 大连理工大学 | D-pi-A compound and application thereof in perovskite solar cell passivation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2625306A1 (en) | Electron acceptors-cored regioregular oligothiophenes as building blocks for soluble low band-gap conjugated polymers | |
| Jung et al. | Recent progress in high efficiency polymer solar cells by rational design and energy level tuning of low bandgap copolymers with various electron-withdrawing units | |
| EP2075274B1 (en) | Soluble polythiophene derivatives | |
| US7973074B2 (en) | π-conjugated mono-, oligo- and polymeric compounds, and photovoltaic cells comprising them | |
| US8058387B2 (en) | Soluble polythiophene derivatives | |
| Lee et al. | Low band-gap polymers based on quinoxaline derivatives and fused thiophene as donor materials for high efficiency bulk-heterojunction photovoltaic cells | |
| US7754847B2 (en) | Soluble polythiophene derivatives | |
| Zhang et al. | Synthesis of low bandgap polymer based on 3, 6-dithien-2-yl-2, 5-dialkylpyrrolo [3, 4-c] pyrrole-1, 4-dione for photovoltaic applications | |
| Kim et al. | Benzotriazole-based donor–acceptor type semiconducting polymers with different alkyl side chains for photovoltaic devices | |
| CA2781791A1 (en) | Novel photoactive polymers | |
| US8901415B2 (en) | Conducting polymer to which pyrene compounds are introduced, and organic solar cell using same | |
| JP5746226B2 (en) | Cyclopentadienedithiophene-quinoxaline copolymer, production method thereof, and application thereof | |
| CN101939351A (en) | Perylene-imide semiconductor polymers | |
| WO2009103030A1 (en) | Novel compositions and methods including alternating copolymers comprising dithienopyrrole units | |
| Hou et al. | Synthesis and photovoltaic properties of the copolymers of 2-methoxy-5-(2′-ethylhexyloxy)-1, 4-phenylene vinylene and 2, 5-thienylene-vinylene | |
| WO2010088419A2 (en) | Cross-conjugated polymers for organic electronic devices and related methods | |
| Song et al. | A low-bandgap alternating copolymer containing the dimethylbenzimidazole moiety | |
| WO2008143850A2 (en) | Mixed halogen polymerization | |
| Patil et al. | Synthesis and photovoltaic properties of narrow band gap copolymers of dithieno [3, 2-b: 2′, 3′-d] thiophene and diketopyrrolopyrrole | |
| WO2012087243A1 (en) | New p-type low bandgap polymers and their use | |
| CN101492529B (en) | Soluble polythiophene derivative and application thereof in photoelectric component | |
| Kim et al. | Synthesis and characterization of indeno [1, 2-b] fluorene-based low bandgap copolymers for photovoltaic cells | |
| Wu et al. | A copolymer based on benzo [1, 2-b: 4, 5-b′] dithiophene and quinoxaline derivative for photovoltaic application | |
| US20150194608A1 (en) | Building block for low bandgap conjugated polymers | |
| Tu et al. | Side-chain engineering of diindenocarbazole-based large bandgap copolymers toward high performance polymer solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |