Molecular and polymeric semiconductors and related devices
The present invention relates to new semiconducting compounds having at least one optionally substituted benzo[d][1,2,3]thiadiazole moiety. The compounds disclosed herein can exhibit high carrier mobility and/or efficient light absorption/emission characteristics, and can possess certain processing advantages such as solution-processability and/or good stability at ambient conditions.
1. An organic thin film transistor comprising a substrate, a thin film semiconductor, a dielectric layer, a gate electrode, and source and drain electrodes, wherein the thin film semiconductor comprises a polymer having a first repeating unit M 1 , said polymer having a degree of polymerization (n) ranging from 3 to 1,000, wherein M 1 comprises one or more divalent benzo[d][1,2,3]thiadiazole units represented by formula (I):
wherein each R 1 independently is selected from the group consisting of H, F, Cl, Br, I, —CN, —NO 2 , CH 3 , OCH 3 , CF 3 , and a phenyl group, provided at least one R 1 is selected from F, Cl, Br, I, —CN, —NO 2 , and CF 3 .
2. The organic thin film transistor of claim 1 , wherein said polymer has a degree of polymerization (n) ranging from 8 to 100.
3. The organic thin film transistor of claim 1 , wherein M 1 is selected from the group consisting of:
wherein:
pi-2 is an optionally substituted conjugated polycyclic moiety;
Ar, at each occurrence, is independently an optionally substituted 5- or 6-membered aryl or heteroaryl group;
Z is a conjugated noncyclic linker;
m and m′ independently are 0, 1, 2, 3, 4, 5 or 6, provided that at least one of m and m′ is not 0;
m″ is 1, 2, 3, 4, 5 or 6; and
p and p′ independently are 0 and 1, provided that at least one of p and p′ is 1.
4. The organic thin film transistor of claim 3 , wherein pi-2 is an optionally substituted C 8-26 aryl group or 8-26 membered heteroaryl group.
5. The organic thin film transistor of claim 4 , wherein pi-2 is selected from the group consisting of:
wherein:
R a is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, and —C(O)OR;
R b is selected from the group consisting of H, R, and -L-R f ;
R c is H or R;
R d is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R,
—C(O)OR, and -L-R f ;
R e is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R,
—C(O)OR, and R f ;
R f is a C 6-20 aryl group or a 5-20-membered heteroaryl group, each optionally substituted with 1-8 groups independently selected from the group consisting of F, Cl, —CN, R, —OR, and —SR;
L is selected from the group consisting of —O—, —S—, —C(O)—, —OC(O)—, —O(O)O—, and a covalent bond; and
R is selected from the group consisting of a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 2-40 alkenyl group, and a C 2-40 alkynyl group.
6. The organic thin film transistor of claim 3 , wherein Ar in (Ar) m , (Ar) m′ , and (Ar) m″ is represented by:
wherein each W independently is selected from the group consisting of N, CH, and CR 4 , wherein R 4 is selected from the group consisting of F, Cl, —CN, R 2 , OR 2 , SR 2 , C(O)R 2 , OC(O)R 2 , and C(O)OR 2 , and wherein R 2 is selected from the group consisting of 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.
7. The organic thin film transistor of claim 6 , wherein (Ar) m , (Ar) m′ , and (Ar) m″ independently are selected from the group consisting of:
8. The organic thin film transistor of claim 3 , wherein Z is selected from the group consisting of:
wherein R 4 is selected from the group consisting of F, Cl, —CN, R 2 , OR 2 , SR 2 , C(O)R 2 , OC(O)R 2 , and C(O)OR 2 , and wherein R 2 is selected from the group consisting of 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.
9. The organic thin film transistor of claim 3 , wherein the polymer further comprises one or more repeating units other than M 1 , the one or more other repeating units (M 2 ) being selected from the group consisting of:
wherein:
pi-2 is an optionally substituted conjugated polycyclic moiety;
Ar, at each occurrence, is independently an optionally substituted 5- or 6-membered aryl or heteroaryl group;
Z is a conjugated noncyclic linker;
m and m′ independently are 0, 1, 2, 3, 4, 5 or 6, provided that at least one of m and m′ is not 0;
m″ is 1, 2, 3, 4, 5 or 6; and
p and p′ independently are 0 and 1, provided that at least one of p and p′ is 1.
10. The organic thin film transistor of claim 9 , wherein:
Z is selected from the group consisting of:
(Ar) m , (Ar) m′ , and (Ar) m″ independently are selected from the group consisting of:
wherein R 4 is selected from F, Cl, —CN, R 2 , OR 2 , SR 2 , C(O)R 2 , OC(O)R 2 , and C(O)OR 2 , and wherein R 2 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
pi-2 is selected from the group consisting of:
wherein:
R a is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, and —C(O)OR;
R b is selected from the group consisting of H, R, and -L-R f ;
R c is H or R;
R d is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R,
—C(O)OR, and -L-R f ; and
R e is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R,
—C(O)OR, and R f ; wherein
R f is a C 6-20 aryl group or a 5-20-membered heteroaryl group, each optionally substituted with 1-8 groups independently selected from the group consisting of F, Cl, —CN, R, —OR, and —SR;
L is selected from the group consisting of —O—, —S—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and R is selected from the group consisting of a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 2-40 alkenyl group, and a C 2-40 alkynyl group; and
R is selected from the group consisting of a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 2-40 alkenyl group, and a C 2-40 alkynyl group.
11. The organic thin film transistor of claim 10 , wherein M 1 is selected from the group consisting of:
wherein
R 4 is selected from R 2 , OR 2 , and SR 2 , where R 2 is a linear or branched C 1-40 alkyl or haloalkyl group; and
M 2 is selected from the group consisting of:
wherein (Ar) m and (Ar) m′ are selected from the group consisting of:
12. The organic thin film transistor of claim 11 , wherein the compound is a copolymer having a formula selected from the group consisting of:
wherein M 1A and M 1B represent different repeating units M 1 , and M 2A and M 2B represent different repeating units M 2 , x and y are real numbers representing molar ratios, and n is the degree of polymerization.
13. The organic thin film transistor of claim 12 , wherein the compound is a random copolymer.
14. The organic thin film transistor of claim 1 , wherein M 1 is selected from the group consisting of:
wherein:
pi-2 is selected from the group consisting of:
wherein:
R a is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, and —C(O)OR;
R b is selected from the group consisting of H, R, and -L-R f ;
R c is H or R;
R d is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R,
—C(O)OR, and -L-R f ;
R e is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R,
—C(O)OR, and R f ;
R f is a C 6-20 aryl group or a 5-20-membered heteroaryl group, each optionally substituted with 1-8 groups independently selected from the group consisting of F, Cl, —CN, R, —OR, and —SR;
L is selected from the group consisting of —O—, —S—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and
R is selected from the group consisting of a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 2-40 alkenyl group, and a C 2-40 alkynyl group;
Ar, at each occurrence, is independently a 5- or 6-membered aryl or heteroaryl group each optionally substituted with 1-4 R 5 groups independently selected from a halogen, CN, a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 1-40 alkoxy group, and a C 1-40 alkylthio group;
Z is a conjugated noncyclic linker;
m and m′ independently are 0, 1, 2, 3, 4, 5 or 6, provided that at least one of m and m′ is not 0;
m″ is 1, 2, 3, 4, 5 or 6; and
p and p′ independently are 0 and 1, provided that at least one of p and p′ is 1.
15. The organic thin film transistor of claim 14 , wherein M 1 is selected from:
wherein R 4 is selected from R 2 , OR 2 , and SR 2 , where R 2 is a linear or branched C 1-40 alkyl or haloalkyl group.
16. The organic thin film transistor of claim 14 , wherein the polymer is a homopolymer of a single repeating unit M 1 or copolymer only of two or more different repeating units M 1 .
17. The organic thin film transistor of claim 14 , wherein the polymer further comprises one or more repeating units other than M 1 , the one or more other repeating units (M 2 ) being selected from the group consisting of:
18. The organic thin film transistor of claim 14 , wherein the one or more other repeating units (M 2 ) have the formula
wherein m″ is selected from 1, 2, 3, or 4, and wherein each Ar of (Ar) m″ is represented by:
wherein each W independently is selected from the group consisting of N, CH, and CR 4 , wherein R 4 is selected from the group consisting of F, Cl, —CN, R 2 , OR 2 , SR 2 , C(O)R 2 , OC(O)R 2 , and C(O)OR 2 , and wherein R 2 is selected from the group consisting of 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.
19. 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 a semiconductor component comprising a blend material, the blend material comprising an electron-acceptor compound and an electron-donor compound, wherein the electron-acceptor compound is a fullerene compound or an electron-transporting polymer, and wherein the electron-donor compound is a polymer having a first repeating unit M 1 , said polymer having a degree of polymerization (n) ranging from 3 to 1,000, wherein M 1 comprises one or more divalent benzo[d][1,2,3]thiadiazole units represented by formula (I):
wherein each R 1 independently is selected from the group consisting of H, F, Cl, Br, I, —CN, —NO 2 , CH 3 , OCH 3 , CF 3 , and a phenyl group, provided at least one R 1 is selected from F, Cl, Br, I, —CN, —NO 2 , and CF 3 .
20. The organic photovoltaic device of claim 19 , wherein M 1 is selected from the group consisting of:
wherein:
pi-2 is selected from the group consisting of:
wherein:
R a is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, and —C(O)OR;
R b is selected from the group consisting of H, R, and -L-R f ;
R c is H or R;
R d is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R,
—C(O)OR, and -L-R f ;
R e is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R,
—C(O)OR, and R f ;
R f is a C 6-20 aryl group or a 5-20-membered heteroaryl group, each optionally substituted with 1-8 groups independently selected from the group consisting of F, Cl, —CN, R, —OR, and —SR;
L is selected from the group consisting of —O—, —S—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and
R is selected from the group consisting of a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 2-40 alkenyl group, and a C 2-40 alkynyl group;
Ar, at each occurrence, is independently a 5- or 6-membered aryl or heteroaryl group each optionally substituted with 1-4 R 5 groups independently selected from a halogen, CN, a C 1-40 alkyl group, a C 1-40 haloalkyl group, a C 1-40 alkoxy group, and a C 1-40 alkylthio group;
Z is a conjugated noncyclic linker;
m and m′ independently are 0, 1, 2, 3, 4, 5 or 6, provided that at least one of m and m′ is not 0;
m″ is 1, 2, 3, 4, 5 or 6; and
p and p′ independently are 0 and 1, provided that at least one of p and p′ is 1.