# US 2014/0151657 A1 · Furan and Selenophene Derivatized Benzo [1,2-b:4,5-b'] Dithiophene-Thienothiophene Based Conjugated Polymers For High-Efficiency Organic Solar Cells

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- Number: US 2014/0151657 A1
- Document ID: US20140151657A1
- Status: Published application
- Kind: A1
- Application number: 14/084,358
- Filed: 2013-11-19
- Published: 2014-06-05
- Earliest claimed: 2012-12-03
- Assignees: Solarmer Energy, Inc.; Phillips 66 Company
- Applicants: Solarmer Energy, Inc.; Phillips 66 Company
- Inventors: Wei Wang; Chenjun Shi; Ruby Chen; Jun Yang; Yue Wu; Hui Huang; Kathy Woody; Joe Bullock; Amit Palkar; Ting He
- Web page: https://patentgrep.com/patent/US20140151657A1

## CPC

- H10K 85/151: {Copolymers}
- H10K 85/113: {Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene}
- H10K 30/30: comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
- H10K 30/50: Photovoltaic [PV] devices
- H10K 85/215: {comprising substituents, e.g. PCBM}
- Y02E 10/549: Organic PV cells
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Compositions, synthesis and applications for furan, thiophene and selenophene derivatized benzo[1,2-b:3,4-b′]dithiophene(BDT)-thienothiophene (BDT-TT) based polymers, namely, poly[(4,8-bis(5-(2-ethyhexyl)selenophen-2-yl)-benzo[1,2-b;4,5-b′]dithiophene)-2,6-diyl-alt-(4-(2-ethylhexanoyl)-3-fluorothieno[3,4-b]thiophene)-2-6-diyl (CS-15), poly[(4,8-bis(5-(2-ethyhexyl)selenophen-2-yl)-benzo[1,2-b;4,5-b′]dithiophene)-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene)-2-carboxylate-2-6-diyl (CS-16), poly[(4,8-bis(5-(2-ethyhexyl)furan-2-yl)-benzo[1,2-b;4,5-b′]dithiophene)-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene)-2-carboxylate-2-6-diyl (CS-18) and poly[(4,8-bis(5-hexylfuran-2-yl)-benzo[1,2-b;4,5-b′]dithiophene)-2,6-diyl-alt-(4-(2-ethylhexanoyl)-3-fluorothieno[3,4-b]thiophene)-2-6-diyl (CS-24) are disclosed. Further, an organic solar cell constructed of a derivatized benzo[1,2-b:3,4-b′]dithiophene(BDT)-thienothiophene (BDT-TT) based polymer is discussed.

## Claims

### Claim 1

1) A derivatized benzo[1,2-b:3,4-b′]dithiophene-thienothiophene based polymer having the formula
wherein R is selected from the group consisting of alkyls and alkoxys, wherein R1 is selected from the group consisting of furan, thiophene, selenophene and derivatives thereto, wherein X is selected from the group consisting of hydrogen, fluorine, chlorine, bromine and iodine.

### Claim 2 (depends on 1)

2) The derivatized benzo[1,2-b:3,4-b′]dithiophene-thienothiophene based polymer of claim 1, wherein R is selected from the group consisting of C1 to C15 alkyls and C1 to C15 alkoxys.

### Claim 3 (depends on 1)

3) The derivatized benzo[1,2-b:3,4-b′]dithiophene-thienothiophene based polymer of claim 1, wherein R is selected from the group consisting of C4 to C10 alkyls and C4 to C10 alkoxys.

### Claim 4 (depends on 1)

4) The derivatized benzo[1,2-b:3,4-b′]dithiophene-thienothiophene based polymer of claim 1, wherein R1 is selected from the group consisting of furan and derivatives thereto.

### Claim 5 (depends on 1)

5) The derivatized benzo[1,2-b:3,4-b′]dithiophene-thienothiophene based polymer of claim 1, wherein R1 is selected from the group consisting of selenophene and derivatives thereto.

### Claim 6 (depends on 1)

6) The derivatized benzo[1,2-b:3,4-b′]dithiophene-thienothiophene based polymer of claim 1, wherein n is equal to 1 to 100.

### Claim 7 (depends on 1)

7) The derivatized benzo[1,2-b:3,4-b′]dithiophene-thienothiophene based polymer of claim 1, wherein n is equal to 1 to 50.

### Claim 8

8) A monomer solution, comprising:
a) At least one furan, thiophene or selenophene derivatized benzo[1,2-b:3,4-b′]dithiophene monomer dissolved in anhydrous tetrahydrofuran, from about 3 to about 5 mmol;
b) N-butyllithium, from about 8.5 to about 9.5 mmol; and
c) Trimethylstannane, from about 10 to about 12 mmol.

### Claim 9

9) A polymer solution, comprising:
a) At least one first reactant selected from the group consisting of 1-(4,6-dibromo-3-fluorothieno[3,4-b]thiophen-2-yl)-2-ethylhexan-1-one and 2-ethylhexyl 4,6-dibromo-3-fluorothieno[3,4-b]thiophene-2-carboxylate dissolved in from about 4:1 to about 6:1 toluene and dimethylformamide, from about 0.25 to about 0.35 mmol;
b) At least one second reactant selected from the group consisting of bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl)bis(trimethylstannane) and (4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl)bis(trimethylstannane) dissolved in the toluene and dimethyformamide solvent, from about 0.25 to about 0.35 mmol; and
c) palladium-tetrakis(triphenylphosphine) catalyst, from about 1.5 to about 2.5 mg/mL.

### Claim 10 (depends on 1)

10) A bulk heterojunction material, comprising:
a) At least one furan, thiophene or selenophene derivatized derivatized benzo[1,2-b:3,4-b′]dithiophene-thienothiophene based polymer as in claim 1 as a donor; and
b) An acceptor.

### Claim 11 (depends on 10)

11) The bulk heterojunction material of claim 10, wherein the bulk heterojunction material is comprised of at least one furan derivatized benzo[1,2-b:3,4-b′]dithiophene-thienothiophene based polymer selected from the group consisting of poly[(4,8-bis(5-(2-ethyhexyl)furan-2-yl)-benzo[1,2-b;4,5-b′]dithiophene)-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene)-2-carboxylate-2-6-diyl and poly[(4,8-bis(5-hexylfuran-2-yl)-benzo[1,2-b;4,5-b′]dithiophene)-2,6-diyl-alt-(4-(2-ethylhexanoyl)-3-fluorothieno[3,4-b]thiophene)-2-6-diyl.

### Claim 12 (depends on 10)

12) The bulk heterojunction material of claim 10, wherein the bulk heterojunction material is comprised of at least one selenophene derivatized benzo[1,2-b:3,4-b′]dithiophene-thienothiophene based polymer selected from the group consisting of poly[(4,8-bis(5-(2-ethyhexyl)selenophen-2-yl)-benzo[1,2-b;4,5-b′]dithiophene)-2,6-diyl-alt-(4-(2-ethylhexanoyl)-3-fluorothieno[3,4-b]thiophene)-2-6-diyl, poly[(4,8-bis(5-(2-ethyhexyl)selenophen-2-yl)-benzo[1,2-b;4,5-b′]dithiophene)-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene)-2-carboxylate-2-6-diyl.

### Claim 13 (depends on 10)

13) The bulk heterojunction material of claim 10, wherein the acceptor is selected from the group consisting of PC70BM, BisIndene-C70, BisPC70BM, BisBenzene-C70, TrisPC70BM and PC76BM.

### Claim 14 (depends on 11)

14) The bulk heterojunction material of claim 11, wherein the acceptor is selected from the group consisting of PC70BM, BisIndene-C70, BisPC70BM, BisBenzene-C70, TrisPC70BM and PC76BM.

### Claim 15 (depends on 12)

15) The bulk heterojunction material of claim 12, wherein the acceptor is selected from the group consisting of PC70BM, BisIndene-C70, BisPC70BM, BisBenzene-C70, TrisPC70BM and PC76BM.

### Claim 16 (depends on 1)

16) An organic solar cell device comprising:
a) An aluminum or silver layer;
b) A bulk heterojunction layer, wherein the bulk heterojunction layer comprises:
i. At least one furan, thiophene or selenophene derivatized benzo[1,2-b:3,4-b′]dithiophene-thienothiophene based polymer as in claim 1 as a donor; and
ii. An acceptor; and
c) An indium tin oxide glass layer.

### Claim 17 (depends on 16)

17) The organic solar cell device of claim 16, wherein the furan derivatized benzo[1,2-b:3,4-b′]dithiophene-thienothiophene is selected from the group consisting of poly[(4,8-bis(5-(2-ethyhexyl)furan-2-yl)-benzo[1,2-b;4,5-b′]dithiophene)-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene)-2-carboxylate-2-6-diyl and poly[(4,8-bis(5-hexylfuran-2-yl)-benzo[1,2-b;4,5-b′]dithiophene)-2,6-diyl-alt-(4-(2-ethylhexanoyl)-3-fluorothieno[3,4-b]thiophene)-2-6-diyl.

### Claim 18 (depends on 16)

18) The organic solar cell device of claim 16, wherein the bulk heterojunction layer comprises at least one selenophene derivatized benzo[1,2-b:3,4-b′]dithiophene-thienothiophene selected from the group consisting of poly[(4,8-bis(5-(2-ethyhexyl)selenophen-2-yl)-benzo[1,2-b;4,5-b′]dithiophene)-2,6-diyl-alt-(4-(2-ethylhexanoyl)-3-fluorothieno[3,4-b]thiophene)-2-6-diyl, poly[(4,8-bis(5-(2-ethyhexyl)selenophen-2-yl)-benzo[1,2-b;4,5-b′]dithiophene)-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene)-2-carboxylate-2-6-diyl.

### Claim 19 (depends on 15)

19) The organic solar cell device of claim 15, wherein the acceptor is selected from the group consisting of PC70BM, BisIndene-C70, BisPC70BM, BisBenzene-C70, TrisPC70BM and PC76BM.

### Claim 20 (depends on 17)

20) The organic solar cell device of claim 17, wherein the acceptor is selected from the group consisting of PC70BM, BisIndene-C70, BisPC70BM, BisBenzene-C70, TrisPC70BM and PC76BM.

### Claim 21 (depends on 18)

21) The organic solar cell device of claim 18, wherein the acceptor is selected 105 from the group consisting of PC70BM, BisIndene-C70, BisPC70BM, BisBenzene-C70, TrisPC70BM and PC76BM.