WO2019023025A1 - High performance wide-bandgap polymers for organic photovoltaics - Google Patents
High performance wide-bandgap polymers for organic photovoltaics Download PDFInfo
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- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
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- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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- 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
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
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- 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
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- 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
Definitions
- This invention relates to high performance wide-bandgap polymers for organic photovoltaics.
- Organic photovoltaic cells have many potential advantages when compared to traditional silicon-based devices.
- Organic photovoltaic cells are light weight, economical in the materials used, and can be deposited on low cost substrates, such as flexible plastic foils.
- organic photovoltaic devices typically have relatively low power conversion efficiency (the ratio of incident photons to energy generated). This is, in part, thought to be due to the morphology of the active layer.
- the charge carriers generated must migrate to their respective electrodes before recombination or quenching occurs.
- the diffusion length of an exciton is typically much less than the optical absorption length, requiring a tradeoff between using a thick, and therefore resistive, cell with multiple or highly folded interfaces, or a thin cell with a low optical absorption efficiency.
- a copolymer comprising a repeat unit A, wherein repeat unit A comprises
- repeat unit B comprises
- repeat unit D comprises an aryl group.
- X 1 , X 2 , X 3 , and X 4 are independently selected from the group consisting of: H, CI, F, CN, alkyl, alkoxy, ester, ketone, amide and aryl groups and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from the group consisting of: H, Cl, F, CN, alkyl, alkoxy, alkylthio, ester, ketone and aryl groups.
- a copolymer comprising a repeat unit E, wherein repeat unit E comprises
- repeat unit H comprises , an optional repeat unit J, wherein a repeat unit J
- a repeat unit K comprises
- X 1 , X 2 ,X 3 , and X 4 are independently selected from the group consisting of: H, CI, F, CN, alkyl, alkoxy, ester, ketone, amide and aryl groups; R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of: H, CI, F, CN, alkyl, alkoxy, alkylthio, ester, ketone and aryl groups; and D comprises an aryl group.
- a copolymer comprising a repeat unit F, wherein repeat unit F comprises
- repeat unit G comprises
- an optional repeat unit J wherein a repeat unit J comprises ; and a repeat unit K, wherein a repeat unit K comprises
- X 1 , X 2 , X 3 , and X 4 are independently selected from the group consisting of: H, CI, F, CN, alkyl, alkoxy, ester, ketone, amide and aryl groups; R 5 , and Re are independently selected from the group consisting of: H, CI, F, CN, alkyl, alkoxy, alkylthio, ester, ketone and aryl groups; and D comprises an aryl group.
- Figure 1 depicts a conventional device architecture and an inverted device architecture.
- Figure 2 depicts the formation of a functionalized QDT monomer.
- Figure 3 depicts the 1 H NMR spectrum of compound 1
- Figure 4 depicts the 1 H NMR spectrum of compound 2
- Figure 5 depicts the 1 H NMR spectrum of compound 3
- Figure 6 depicts the 'H NMR spectrum of compound 4.
- Figure 7 depicts the 1 H NMR spectrum of QDT-Br.
- Figure 8 depicts the 1 H NMR spectrum of QDT-SnMe3.
- Figure 9 depicts the NMR spectrum of the first step of forming an asymmetrical bithiophene monomer.
- Figure 10 depicts the NMR spectrum of the second step of forming an asymmetrical bithiophene monomer.
- Figure 11 depicts the NMR spectrum of the third step of forming an asymmetrical bithiophene monomer.
- Figure 12 depicts the NMR spectrum of an asymmetrical bithiophene monomer.
- Figure 13 depicts different methods of forming benzodithiophene.
- Figure 14 depicts the UV- Visible absorption of different polymers.
- Alkyl refers to an aliphatic hydrocarbon chains.
- the aliphatic hydrocarbon chains are of 1 to about 100 carbon atoms, preferably 1 to 30 carbon atoms, more preferably, 1 to 20 carbon atoms, and includes straight and branched chains such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neo- pentyl, n-hexyl, and isohexyl.
- alkyl groups can include the possibility of substituted and unsubstituted alkyl groups.
- alkoxy refers to the group R— O— where R is an alkyl group of 1 to 100 carbon atoms.
- alkoxy groups can include the possibility of substituted and unsubstituted alkoxy groups.
- Aryl refers to an optionally substituted, mono-, di-, tri-, or other multicyclic aromatic ring system having from about S to about 50 carbon atoms (and all combinations and subcombinations of ranges and specific numbers of carbon atoms therein), with from about 6 to about 10 carbons being preferred.
- Non-limiting examples include, for example, phenyl, naphthyl, anthracenyl, and phenanthrenyl.
- Aryl groups can be optionally substituted with one or with one or more Rx.
- aryl groups can include the possibility of substituted aryl groups, bridged aryl groups and fused aryl groups.
- Ester represents a group of formula— COOR wherein R represents an “alkyl”, “aryl”, a “heterocycloalkyl” or “heteroaryl” moiety, or the same substituted as defined above
- Ketone represents an organic compound having a carbonyl group linked to a carbon atom such as— C(O)Rx wherein Rx can be alkyl, aryl, cycloalkyl, cycloalkenyl or heterocycle.
- Amide as used herein, represents a group of formula wherein R x and R y can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl or heterocycle.
- the architecture When used as a photovoltaic device the architecture may be a conventional architecture device, while in others it may be an inverted architecture device.
- a conventional architecture device typically comprised of multilayered structure with a transparent anode as a substrate to collect positive charge (holes) and a cathode to collect negative charge (electrons), and a photoactive layer sandwiched in between two electrodes.
- An additional charge transport interlayer is inserted in between active layer and electrode for facile hole and electron transport.
- Each charge transport layer can be consisted of one or more layers.
- An inverted device has the same multilayered structure as the conventional architecture device whereas it uses a transparent cathode as a substrate to collect electrons and a cathode to collect holes.
- the inverted device also has the photo-active layer and additional charge transport layers sandwiched in between two electrodes.
- Figure 1 depicts a conventional device architecture and an inverted device architecture.
- repeat unit A are quinoxalinedithiophene (QDT) monomers
- X 1 , X 2 , X 3 , and X 4 are independently selected from the group consisting of: H, CI, F, CN, alkyl, alkoxy, ester, ketone, amide and aryl groups.
- the QDT monomer can be functionalized with a variety of halides and stannanes in order to prepare it for the eventual polymerization reaction.
- the formation of a functionalized QDT monomer is shown in Figure 2.
- the formation of compound 1 begins by forming a 2- ethylhexylmagnesium bromide solution prepared by adding 2-ethylhexyl bromide (17.3 mL, 0.097 mol) dropwise to a mixture of freshly ground magnesium (2.61 g, 0.107 mol) in dry tetrahydrofuran (250 mL).
- the 2-ethylhexylmagnesium bromide solution was stirred at room temperature for around 2 hours. Meanwhile, a solution of LiBr (17 g, 0.196 mol) in dry tetrahydrofuran (100 mL) was added to a solution of CuBr in dry tetrahydrofuran (150 mL). Then, the CuBr/LiBr/tetrahydrofuran solution was cooled to -78 °C and the 2- ethylhexylmagnesium bromide solution was added dropwise. Once that transfer was finished, oxalyl chloride (3.33 mL, 0.039 mol) was added.
- compound 2 can be formed by charging a hot, oven-dried Schlenk flask with FeCl 3 (10.9 g, 67.481 mmol) then evacuated and refilled with argon (3x). Dry dichloromethane (140 mL) was added to the flask via cannula, and then 3,3 -thenil (5 g, 22.494 mmol) was added in one portion. The reaction stirred at room temperature under argon. After around 2 hours, the reaction was quenched with water (-100 mL) and stirred. The solvent was removed via rotovap, and the solid was suspended in water and left at room temperature overnight.
- compound 3 is formed by adding compound 2 (2 g, 0.009 mol), 200- proof ethanol (100 mL), and hydroxylamine hydrochloride (1.577 g, 0.023 mol) to a 250 mL round bottom flask under the flow of argon. The flask can then be topped with a water condenser and argon inlet, and the reaction was heated to refluxed for 22 hours. The reaction can then be cooled to room temperature and 10% palladium on carbon (200 mg) is added. An addition funnel was added to the top of the condenser and the funnel was filled with a solution of hydrazine monohydrate (15 mL) in ethanol (25 mL).
- compound 4 is formed by combining compound 3 (1.6 g, 7.262 mmol) and compound 1 (2.154 g, 7.625 mmol) in a 50 mL Schlenk flask. The flask was evacuated and refilled with argon, then acetic acid was added, and the reaction was heated to 100 °C for 16 h. The reaction mixture was cooled to room temperature, then diluted with water and transferred to a separatory funnel. The aqueous layer was extracted with dichlorom ethane. The aqueous layer was neutralized with Na2C03 and extracted with dichloromethane. The combined organic extracts were dried (MgSO-i), filtered, and concentrated.
- repeat unit B are asymmetrical bithiophene monomers
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from the group consisting of, CI, F, CN, alkyl, alkoxy, alkylthio, ester, ketone and aryl groups.
- the formation of the asymmetrical bithiophene monomer are is described below.
- the formation of the asymmetrical bithiophene monomer can begin with the synthesis of 3-(2-hexyldecyl)thiophene.
- magnesium turnings (3.184 g, 0.131 mol) were added.
- 7-(Bromomethyl)pentadecane (20 g, 0.066 mol) was added into an addition funnel. The system was vacuumed and backfilled with argon three times.
- the reaction mixture was further refluxed 70 °C for 3 hours before stirred at room temperature overnight.
- the reaction was quenched by pouring onto crushed ice.
- a cold HC1 aq. solution was added to dissolve the solid.
- the product was extracted with hexane and dried over anhydrous MgSO 4 .
- the crude product was purified by column chromatography using hexane as the eluent, and then by vacuum distillation, to give a clear colorless liquid as product (6.80 g, 33.6%).
- the NMR spectrum is shown in Figure 9.
- the second step of the formation of the asymmetrical bithiophene monomer can begin with the synthesis of 2-bromo-3-(2-hexyldecyl)thiophene.
- 3-(2-Hexyldecyl)thiophene (5 g, 0.016 mol) was added to a 200 mL Schlenk flask. The system was vacuumed and backfilled with argon three times before 200 mL of anhydrous THF was added. The solution was cooled down to -78 °C before N-bromosuccinimide (2.884 g, 0.016 mol) was added in portions in the absence of light. The reaction mixture was stirred overnight.
- the reaction was quenched by adding an aqueous solution of Na2CO 3 .
- the product was extracted with hexane and then dried over anhydrous MgSO 4 before the removal of solvent.
- the product was further purified with silica gel column with hexane as eluent and colorless liquid (5.48 g, yield of 87.3%) was obtained after dried in vacuum.
- the NMR spectrum is shown in Figure 10.
- the third step of the formation of the asymmetrical bithiophene monomer can begin with the synthesis of 3-(2-hexyldecyl)-2,2'-bithiophene.
- 2-Bromo-3-(2-hexyldecyl)thiophene (5.68 g, 0.015 mol), tributyl(thiophen-2-yl)stannane (5.471 g, 0.015 mol) and Pd2(dba)3 (0.268 g, 0.293 mmol), P(o-tol)3 (0.357 g, 1.173 mmol) were combined in 200 mL Schlenk flask.
- the last step of the formation of the asymmetrical bithiophene monomer can begin with the synthesis of (3-(2-hexyldecy1)-[2,2'-bithiophene]-5,5'-diyl)bis(trimethylstannane)(HDTT) 3- (2-Hexyldecyl)-2-(thiophen-2-yl)thiophene (4.15 g, 10.6 mmol) was added to a 200 mL Schlenk flask. The system was vacuumed and backfilled with argon three times before 100 mL of anhydrous THF was added.
- Figure 13 depicts different methods of forming benzodithiophene. While conventional methods are shown in Figure 13, the invention is not limited to any one specific method of forming benzodithiophene.
- At least one optional repeat unit D refers to an optionally substituted, mono-, di-, tri-, or other multicyclic aromatic ring system having from about 5 to about 50 carbon atoms (and all combinations and subcombinations of ranges and specific numbers of carbon atoms therein), with from about 6 to about 20 carbons being preferred.
- Non-limiting examples include, for example, phenyl, naphthyl, anthracenyl, and phenanthrenyl.
- Aryl groups can be optionally substituted with one or with one or more Rx.
- aryl groups can include the possibility of substituted aryl groups, bridged aryl groups and fused aryl groups. While it is feasible that there is only one repeat unit D in the copolymer, it is also envisioned that multiple repeat unit D's can exist within the copolymer.
- the aryl group can consist of
- R', R", R'" and R" are independently selected from the group consisting of: H, CI, F, CN, alkyl, alkoxy, alkylthio, ester, ketone and aryl groups.
- the aryl group is a 3,3'difluror-2,2'-bithiophene.
- repeat unit A, repeat unit B and optional repeat unit D produce a copolymer.
- the copolymer can be regio-random or regio-regular. It is envisioned that the copolymer can be used as a photovoltaic material. It is also envisioned that the copolymer can be used in the active layer in an electronic device. In one embodiment the number of repeat units A, B and C can range from about 3 to about 10,000 in the copolymer. In an alternate embodiment, the copolymer can form a polymer bandgap greater than 1.8 eV. [00SS] In some embodiments, the copolymer can contain a combination of repeat units A and
- the copolymer can contain a combination of repeat units
- the copolymer can contain a combination of repeat units A and
- the copolymer can contain a combination of repeat units
- the amount of repeat unit A in the copolymer can range from 1 wt% to 99 wt%.
- the amount of repeat unit B in the copolymer can range from 1 wt% to 99 wt%.
- the amount of repeat unit D in the copolymer can range from 0 wt% to 99 wt. %.
- anode When used in an organic photovoltaic device the copolymer can be used in conjunction with an anode.
- the anode for the organic photovoltaic device can be any conventionally known anode capable of operating as an organic photovoltaic device. Examples of anodes that can be used include: indium tin oxide, aluminum, carbon, graphite, graphene, PEDOT:PSS, copper, metal nanowires
- the copolymer when used in an organic photovoltaic device the copolymer can be used in conjunction with a cathode.
- the cathode for the organic photovoltaic device can be any conventionally known cathode capable of operating as an organic photovoltaic device. Examples of cathodes that can be used include: indium tin oxide, carbon, graphite, graphene, PEDOT:PSS, copper, silver, gold, metal nanowires.
- the copolymer When used in an organic photovoltaic device the copolymer can be deposited onto an electron transport layer. Any commercially available electron transport layer can be used that is optimized for organic photovoltaic devices.
- the electron transport layer can comprise In this embodiment, are metal oxides.
- a and B can be any commercially available electron transport layer that is optimized for organic photovoltaic devices.
- the electron transport layer can comprise In this embodiment, are metal oxides.
- a and B can be any commercially available electron transport layer that is optimized for organic photovoltaic devices.
- the electron transport layer can comprise In this embodiment, are metal oxides.
- a and B can be used in an organic photovoltaic device.
- A can be different metals selected to achieve ideal electron transport layers.
- A can be aluminum, indium, zinc, tin, copper, nickel, cobalt, iron, ruthenium, rhodium, osmium, tungsten, magnesium, indium, vanadium, titanium and molybdenum.
- B can be aluminum, indium, zinc, tin, copper, nickel, cobalt, iron, ruthenium, rhodium, osmium, tungsten, vanadium, titanium and molybdenum.
- various fullerene dopants can be combined with to make an electron transport layer for the organic photovoltaic device.
- flillerene dopants that can be combined include and [6,6]-phenyl- C 60 -butyric-N-2-trimethylammonium ethyl ester iodide.
- R' can be selected from either N, O,
- R" can be alkyl chains or substituted alkyl chains. Examples of substitutions for the substituted alkyl chains include halogens, N, Br, O, Si, or S. In one example
- R" can be selected from , or
- fullerene dopants that can be used include: [6,6]-phenyl-C 60 -butyric-N-(2- aminoethyl)acetamide, [6,6]-phenyl-C 60 -butyric-N-triethyleneglycol ester and [6,6]-phenyl-C 60 - butyric-N-2-dimethylaminoethyl ester.
- Sample A In a Schlenk flask, QDT-Br (53.53 mg, 0.086 mmol), (3-(2-hexyldecyl)- [2,2'-bithiophene]-5,5'-diyl)bis(trimethylstannane) (61.40 mg, 0.086 mmol), P(o-tol)3 (4.17 mg, 0.014 mmol), and Pd2dba3 (3.14 mg, 0.003 mmol) were combined, then degassed for 2 h.
- Sample B In a Schlenk flask, QDT-Br (55.42 mg, 0.089 mmol), stannane, l,l'-[3,3"'- (108.00 mg,
- Sample C In a Schlenk flask, QDT-Br (50.00 mg, 0.080 mmol), Stannane, 1,1 - naphmo[l,2-6:5,6-6']dithiophene-2,7-diylbis[l,l,l-trimethyl (45.31 mg, 0.080 mmol), P(o-tol)3 (3.90 mg, 0.013 mmol), and Pd2dba3 (2.93 mg, 0.003 mmol) were combined, then degassed for 2 h.
- Sample D In a Schlenk flask, QDT-SnMe3 (40.00 mg, 0.050 mmol), 2,1,3- Benzothiadiazole, 4,7-bis[5-bromo-4-(2-octyldodecyl)-2-thienyl]-5,6-difluoro (45.31 mg, 0.080 mmol), P(o-tol)3 (2.46 mg, 0.008 mmol), andPd 2 dba3 (1.85 mg, 0.002 mmol) were combined, then degassed for 2 h.
- Sample E In a Schlenk flask, QDT-Br (100.3 mg, 0.161 mmol), (3-(2-hexyldecyl>- [2,2'-bithiophene]-5,5'-diyl)bis(trimethylstannane) (57.5 mg, 0.08 mmol), Stannane, l,l'-[4,8- bi s[5-(2-ethylhexyl)-2-thienyl]benzo[ 1 ,2-b :4,5-6']dithiophene-2,6-diyl]bis[ 1,1,1 -trimethyl (72.6 mg, 0.08 mmol), P(o-tol> (7.8 mg, 0.026 mmol), and Pd2dba3 (5.9 mg, 0.006 mmol) were combined, then degassed for 1 h.
- Sample F In a Schlenk flask, QDT-Br (100.1 mg, 0.160 mmol), (3-(2-hexyldecyl> [2,2'-bithiophene]-5,5'-diyl)bis(trimethylstannane) (80.4 mg, 0.11 mmol), Stannane, l,l'-(3,3'- difluoro[2,2'-bithiophene]-5,5'-diyl)bis[l,l,l-trimethyl (25.4 mg, 0.05 mmol), P(o-tol)3 (7.8 mg, 0.026 mmol), and Pd2dba3 (5.9 mg, 0.006 mmol) were combined, then degassed for 1 h.
- Zinc/tin oxide (ZTO):phenyl-C60-butyric-N-(2-hydroxyethyl)acetamide (PCBNOH) sol-gel solution was prepared by dissolving zinc acetate di hydrate or tin(II) acetate in 2- methoxyethanol and ethanolamine.
- ZTO:PCBNOH sol-gel electron transport layer solution was prepared by mixing 3.98 g of ⁇ ( ⁇ c)2, 398 mg of Sn(OAc)2 and 20.0 mg PCBNOH in 54 mL of 2-methoxyethanol with adding 996 uL of ethanolamine. Solutions were then further diluted to 65% by adding more 2-methoxyethanol and stirred for at least an hour before spin casting onto indium tin oxide substrate to form the electron transport layer.
- Indium tin oxide patterned glass substrates were cleaned by successive ultra- sonications in acetone and isopropanol. Each 15-min step was repeated twice and the freshly cleaned substrates were left to dry overnight at 60 °C. Preceding fabrication, the substrates were further cleaned for 1.5 min in a UV-ozone chamber and the electron transport layer was immediately spin coated on top.
- Sol-gel electron transport layer solution was filtered directly onto the indium tin oxide with a 0.25 um poly(vinylidene fluoride) filter and spin cast at 4000 rpm for 40 s. Films were then annealed at 250 °C for 15 min, and directly transferred into a nitrogen filled glove box. [0084] The photoactive layer was deposited on the electron transport layer via spin coating at 600 rpm for 40 s with the solution and the substrate being preheated at 110 °C and directly transferred into a glass petri dish for overnight solvent annealing.
- the substrates were loaded into the vacuum evaporator where MoCh (hole transport layer) and Ag (anode) were sequentially deposited by thermal evaporation. Deposition occurred at a pressure of ⁇ 4 x 10 -6 torr. MoO 3 and Ag had thicknesses of 5.0 nm and 120 nm, respectively. Samples were then encapsulated with glass using an epoxy binder and treated with UV light for 3 min.
- Jsc Short-circuit current density
- Voc V
- Open-circuit voltage Voc
- FF fill factor
- PCE %) The power conversion efficiency (PCE) of a photovoltaic cell is the percentage of the solar energy shining on a photovoltaic device that is converted into usable electricity.
- R 5 ⁇ cm 2
- series resistance Rs
- Rsh ⁇ cm 2
- parallel resistance though the photovoltaic cell.
Abstract
Description
Claims
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US20120071617A1 (en) * | 2009-05-27 | 2012-03-22 | Basf Se | Diketopyrrolopyrrole polymers for use in organic semiconductor devices |
US20130092912A1 (en) * | 2010-06-08 | 2013-04-18 | Wei You | Polymers with tunable band gaps for photonic and electronic applications |
US20130144065A1 (en) * | 2010-08-05 | 2013-06-06 | Polyera Corporation | Semiconductor materials prepared from bridged bithiazole copolymers |
US20150349261A1 (en) | 2014-05-30 | 2015-12-03 | Solarmer Energy, Inc. | Difluorothienothiophene based conjugated polymers |
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US20120071617A1 (en) * | 2009-05-27 | 2012-03-22 | Basf Se | Diketopyrrolopyrrole polymers for use in organic semiconductor devices |
US8629238B2 (en) | 2009-05-27 | 2014-01-14 | Basf Se | Diketopyrrolopyrrole polymers for use in organic semiconductor devices |
US20130092912A1 (en) * | 2010-06-08 | 2013-04-18 | Wei You | Polymers with tunable band gaps for photonic and electronic applications |
US20130144065A1 (en) * | 2010-08-05 | 2013-06-06 | Polyera Corporation | Semiconductor materials prepared from bridged bithiazole copolymers |
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