Conjugated polymers and their use in optoelectronic devices
View Patent ↗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.
1. A polymer comprising a repeating unit (M 1a ) having a formula selected from:
or a repeating unit (M 1b ) having a formula selected from:
wherein:
Ar 1 and Ar 2 independently are an optionally substituted C 6-14 aryl group or an optionally substituted 5-14 membered heteroaryl group;
Ar 3 and Ar 4 independently are an optionally substituted 5- or 6-membered heteroaryl group;
L, at each occurrence, independently is selected from —O—, —S—, —Se—, —OC(O)—, —C(O)O—, a divalent C 1-20 alkyl group, a divalent C 1-20 haloalkyl group, and a covalent bond;
L 1 , at each occurrence, independently is selected from —O—, —S—, —Se—, —OC(O)—, —C(O)O—, a divalent C 1-20 alkyl group, and a divalent C 1-20 haloalkyl group;
U and U′ independently are selected from O, S, and Se;
V and V′ independently are CR or N;
W, at each occurrence, independently is selected from O, S, and Se;
W′, at each occurrence, independently is CR or N;
R, at each occurrence, independently is selected from H, F, Cl, —CN, and L′R′, wherein
L′, at each occurrence, is selected from —O—, —S—, —Se—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and R′, at each occurrence, independently is selected from a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, and a C 1-40 haloalkyl group; and
the polymer has a degree of polymerization in the range of 3 to 10,000.
2. The polymer of claim 1 comprising the repeating unit (M 1a ) having a formula selected from:
wherein L is selected from —O—, —S—, —OC(O)—, a divalent C 1-20 alkyl group, and a covalent bond; and Ar 1 and Ar 2 are as defined in claim 1 .
3. The polymer of claim 2 , wherein the moieties
independently are selected from:
wherein any of the carbon atoms optionally is substituted with F, Cl, —CN, or L′R′, wherein L′, at each occurrence, is selected from —O—, —S—, —Se—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and R′, at each occurrence, independently is selected from a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, and a C 1-40 haloalkyl group.
4. The polymer of claim 1 comprising the repeating unit (M 1b ) having a formula selected from:
wherein L 1 is selected from —O—, —S—, —OC(O)—, and a divalent C 1-20 alkyl group; and Ar 3 and Ar 4 are as defined in claim 1 .
5. The polymer of claim 4 , wherein the repeating unit (M 1b ) has a formula selected from:
wherein R c , at each occurrence, independently is selected from F, Cl, —CN, and L″R″, wherein L″, at each occurrence, is selected from —O—, —S—, —Se—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and R″, at each occurrence, independently is selected from a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, and a C 1-40 haloalkyl group; and d, at each occurrence, independently is 1, 2 or 3.
6. The polymer of claim 1 further comprising a repeating unit (M 2 ) that is different from the repeating unit (M 1a ) and the repeating unit (M 1b ).
7. The polymer of claim 6 , wherein the repeating unit (M 2 ) comprises an electron-poor polycyclic heteroaryl group.
8. The polymer of claim 7 , wherein the repeating unit (M 2 ) has a formula selected from:
wherein:
Ar, at each occurrence, independently is an optionally substituted 5-8 membered heteroaryl group;
R 1 and R 2 independently are selected from H, a halogen, —CN, and L′R′, wherein L′, at each occurrence, is selected from —O—, —S—, —Se—, —C(O)—, —OC(O)—, —C(O)O—, a divalent C 1-20 alkyl group, a divalent C 1-20 haloalkyl group, and a covalent bond; and R′, at each occurrence, independently is selected from H, a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, a C 1-40 haloalkyl group, an optionally substituted C 6-14 aryl group and an optionally substituted 5-14 membered heteroaryl group; and
m; and m′ are 0, 1, or 2.
9. The polymer of claim 1 having a formula selected from:
wherein:
each R independently can be H or Cl;
R c , at each occurrence, independently is selected from F, Cl, —CN, and L″R″, wherein L″, at each occurrence, is selected from —O—, —S—, —Se—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and R″, at each occurrence, independently is selected from a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, and a C 1-40 haloalkyl group;
R 1 , R 3 and R 4 independently can be selected from H, F, Cl, and CN;
R 13 and R 14 independently can be selected from H, F, Cl, R 15 , OR 15 , and SR 15 ; wherein
R 15 , at each occurrence, independently can be selected from a C 1-20 alkyl group, a C 1-20 alkenyl group, and a C 1-20 haloalkyl group;
c can be 0, 1 or 2;
d can be 1, 2 or 3; and
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;
wherein the polymer has a molecular weight in the range of about 3,000 to about 300,000.
10. The polymer of claim 9 , wherein R 1 is selected from F, Cl, and CN.
11. The polymer 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.
12. An electronic, optical or optoelectronic device comprising a polymeric semiconductor component, the polymeric semiconductor component comprising the polymer of claim 1 .
13. The device of claim 12 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.
14. The device of claim 13 , wherein the organic photovoltaic device is a bulk heterojunction photovoltaic device.
15. The device of claim 13 , wherein the polymeric semiconductor component is photoactive and the polymer of claim 1 is present in a blend material, wherein the polymer of claim 1 functions as an electron-donor compound and the blend material further comprises an electron-acceptor compound.
16. The device of claim 15 , wherein the electron-acceptor compound is a fullerene compound.
17. The device of claim 13 , wherein the electron-acceptor compound is an electron-transporting polymer.
18. The device of claim 17 , wherein the electron-transporting polymer comprises a bis(imide)arene unit.
19. The device of claim 18 , wherein the arene group in the bis(imide)arene unit is naphthalene.
20. The polymer of claim 1 comprising the repeating unit (M 1a ) having a formula selected from:
wherein the moieties
wherein any of the carbon atoms optionally is substituted with F, Cl, —CN, or L′R′, wherein L′, at each occurrence, is selected from —O—, —S—, —Se—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and R′, at each occurrence, independently is selected from a C 1-40 alkyl group, a C 2-40 alkenyl group, a C 2-40 alkynyl group, and a C 1-40 haloalkyl group; and
L is selected from O, S, OC(O), a divalent C 1-20 alkyl group, and a covalent bond.