# US 8,772,442 B2 · Conjugated polymers and their use in optoelectronic devices

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 8,772,442 B2
- Document ID: US8772442B2
- Status: Granted
- Kind: B2
- Application number: 13/830,038
- Filed: 2013-03-14
- Published: 2013-08-08
- Granted: 2014-07-08
- Earliest claimed: 2010-10-22
- Assignees: Polyera Corporation
- Applicants: Polyera Corporation
- Inventors: Zhengguo Zhu; Hualong Pan; Martin Drees; Hakan Usta; Shaofeng Lu; Antonio Facchetti
- Web page: https://patentgrep.com/patent/US8772442B2

## CPC

- H10K 85/113: {Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene}
- C08G 75/06: from cyclic thioethers
- H10K 85/111: {comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene}
- H10K 85/151: {Copolymers}
- H10K 85/40: Organosilicon compounds, e.g. TIPS pentacene
- C08G 61/123: {derived from five-membered heterocyclic compounds}
- C08G 2261/124: alternating
- C08G 2261/1412: Saturated aliphatic units
- C08G 2261/1424: containing ether groups, including alkoxy
- C08G 2261/146: Side-chains containing halogens
- C08G 2261/3223: containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
- C08G 2261/3243: containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
- C08G 2261/3246: containing nitrogen and sulfur as heteroatoms
- C08G 2261/344: containing heteroatoms
- C08G 2261/364: containing hetero atoms
- C08G 2261/414: Stille reactions
- C08G 2261/512: Hole transport
- C08G 2261/794: with polymeric dopants
- C08G 2261/91: Photovoltaic applications
- C08G 2261/92: TFT applications
- C08G 2261/95: Use in organic luminescent diodes
- H10K 30/30: comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
- H10K 50/11: characterised by the electroluminescent [EL] layers
- H10K 50/14: Carrier transporting layers
- Y02E 10/549: Organic PV cells
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Disclosed are certain polymeric compounds and their use as organic semiconductors in organic and hybrid optical, optoelectronic, and/or electronic devices such as photovoltaic cells, light emitting diodes, light emitting transistors, and field effect transistors. The disclosed compounds can provide improved device performance, for example, as measured by power conversion efficiency, fill factor, open circuit voltage, field-effect mobility, on/off current ratios, and/or air stability when used in photovoltaic cells or transistors. The disclosed compounds can have good solubility in common solvents enabling device fabrication via solution processes.

## Claims

### Claim 1

An electronic, optical or optoelectronic device comprising a polymeric semiconductor component, the polymeric semiconductor component comprising a polymer having the formula:
wherein:
Ar and Ar′ are identical or different optionally substituted 5-8 membered heteroaryl groups;
π and π′ are identical or different optionally substituted 11-24 membered polycyclic aryl or heteroaryl groups;
X1 and X2 independently are selected from the group consisting of N, CH and CR1, provided that at least one of X1 and X2 is CR1;
X3 is N or CR3;
X4 is N or CR4;
R1 is selected from selected from the group consisting of F, Cl, —C(O)R5, —CF2R5, and CN;
R3 and R4 independently are selected from selected from the group consisting of H, F, Cl, —C(O)R5, CN, R5, OR5, and SR5, wherein R5, at each occurrence, independently is selected from selected from the group consisting of a C1-20 alkyl group and a C1-20 haloalkyl group;
X is selected from the group consisting of O, S, and NR6, wherein R6 is H or a C1-20 alkyl group;
a and b independently are 0 or 1;
m and m′ are 0, 1, or 2;
n and n′ are 0, 1, or 2, provided that m and m′ are 1 and/or n and n′ are 1, and/or at least one of a and b is 1;
x and y are real numbers representing mole fractions, wherein 0.05≦x≦0.95, 0.05≦y≦0.95, and the sum of x and y is about 1; and
wherein the polymer has a molecular weight in the range of about 3,000 to about 300,000.

### Claim 2 (depends on 1)

The device of claim 1, wherein the polymer is represented by formula (II) or (III):
wherein c is 1 or 2; and Ar, Ar′, π, π′, R1, R3, R4, m, m′, n, n′, a, b, x and y are as defined in claim 1.

### Claim 3 (depends on 1)

The device of claim 1, wherein the polymer is represented by formula (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (Va), (Vb), (Vc), (Vd), (Ve) or (Vf):
wherein Ar, Ar′, π, π′, m, m′, n, n′, a, b, x and y are as defined in claim 1.

### Claim 4 (depends on 1)

The device of claim 1, wherein Ar and Ar′ if both present are different and/or π and π′ are different, and a, b, m, m′, n, n′, x and y are as defined in claim 1.

### Claim 5 (depends on 1)

The device of claim 1, wherein the polymer is represented by formula (VII):
wherein:
R13 and R14 independently are selected from the group consisting of H, R15, OR15, and SR15, wherein R15, at each occurrence, independently is selected from the group consisting of a C1-20 alkyl group, a C1-20 alkenyl group, and a C1-20 haloalkyl group;
c is 1 or 2; and
π, π′, R1, R3, R4, m, m′, n, n′, x and y are as defined in claim 1.

### Claim 6 (depends on 1)

The device of claim 1, wherein π and π′ are optionally substituted 11-24 membered polycyclic heteroaryl groups having the formula:
wherein:
X1 and X2 independently are selected from the group consisting of S, O, NR7, CH═CH, and CR8, provided that one of X1 and X2 is selected from the group consisting of S, O, CH═CH, and NR7, and the other X1 and X2 is CR8;
Y1 and Y2 independently are selected from the group consisting of S, O, NR7, CH═CH, and CR8, provided that one of Y1 and Y2 is selected from the group consisting of S, O, CH═CH, and NR7, and the other Y1 and Y2 is CR8;
Z1 and Z2 independently are selected from the group consisting of CR9, SiR10R11, NR12, and a covalent bond, provided that at least one of Z1 and Z2 is CR9, SiR10R11, or NR12;
R7, at each occurrence, independently is selected from H or a C1-20 alkyl group;
R8 and R9 independently are H, R12, OR12, SR12, or -Het-R12, wherein -Het- is a divalent 5-8 membered aryl or heteroaryl group;
R10 and R11 independently are selected from the group consisting of a C1-20 alkyl group, a C1-20 alkenyl group, and a C1-20 haloalkyl group; and
R12, at each occurrence, independently is selected from the group consisting of a C1-20 alkyl group, a C1-20 alkenyl group, and a C1-20 haloalkyl group.

### Claim 7 (depends on 6)

The device of claim 6, wherein π and π′ independently are selected from the group consisting of:
wherein R9 is selected from the group consisting of a C6-20 alkyl group, a —O—C6-20 alkyl group, a —O—C6-20 alkenyl group, a —O—C6-20 haloalkyl group, a —S—C6-20 alkyl group, a —S—C6-20 alkenyl group, a —S—C6-20 haloalkyl group, a -thienyl-C6-20 alkyl group, a -thienyl-C6-20 alkenyl group, and a -thienyl-C6-20 haloalkyl group; and each of R10, R11, and R12 independently is selected from the group consisting of a C6-20 alkyl group, a C6-20 alkenyl group, and a C6-20 haloalkyl group.

### Claim 8 (depends on 1)

The device of claim 1, wherein the polymer is represented by formula (IX):
R8 and R9 independently are H, R15, OR15, SR15 or -Het-R15, wherein -Het- is a divalent 5-8 membered aryl or heteroaryl group; provided that at least one of R8 and R9 is not H;
R13 and R14 independently are selected from the group consisting of H, R15, OR15, and SR15;
R15, at each occurrence, independently is selected from the group consisting of a C1-20 alkyl group, a C1-20 alkenyl group, and a C1-20 haloalkyl group;
c is 1 or 2; and
R1, R3, R4, x and y are as defined in claim 1.

### Claim 9 (depends on 1)

The device of claim 1, wherein the repeating unit comprising x mole fraction of the polymer and the repeating unit comprising y mole fraction of the polymer are different, and wherein 0.3≦x≦0.7 and 0.3≦y≦0.7, and wherein the sum of x and y is about 1.

### Claim 10 (depends on 9)

The device of claim 9, wherein the repeating unit comprising x mole fraction of the polymer and the repeating unit comprising y mole fraction of the polymer are repeated in a random manner.

### Claim 11 (depends on 1)

The device of claim 1, wherein the polymer is selected from:

### Claim 12 (depends on 1)

The device of claim 1 configured as an organic photovoltaic device comprising an anode, a cathode, optionally one or more anode interlayers, optionally one or more cathode interlayers, and in between the anode and the cathode the polymeric semiconductor component according to claim 1.

### Claim 13 (depends on 12)

The device of claim 12, wherein the organic photovoltaic device is a bulk heterojunction photovoltaic device.

### Claim 14 (depends on 13)

The device of claim 13, wherein the polymeric semiconductor component is photoactive and the polymer of formula (I) is present in a blend material, wherein the polymer of formula (I) functions as an electron-donor compound and the blend material further comprises an electron-acceptor compound.

### Claim 15 (depends on 14)

The device of claim 14, wherein the electron-acceptor compound is a fullerene compound.

### Claim 16 (depends on 12)

The device of claim 12, wherein the power conversion efficiency is at least about 3%.

### Claim 17 (depends on 1)

The device of claim 1 configured as an organic light emitting diode comprising a substrate, an anode, a cathode, and in between the anode and the cathode the polymeric semiconductor component according to claim 1.

### Claim 18 (depends on 1)

The device of claim 1 configured as an organic transistor, further comprising a source electrode, a drain electrode, a gate electrode, and a dielectric layer, wherein the dielectric layer is in contact with the polymeric semiconductor component on one surface, and the gate electrode on another surface.

### Claim 19 (depends on 18)

The device of claim 18, wherein the organic transistor is an organic field effect transistor.

### Claim 20 (depends on 18)

The device of claim 18, wherein the organic transistor is an organic light emitting transistor.