Organic semiconductor formulations
The present teachings relate to organic semiconductor formulations including an organic semiconducting compound in a liquid medium, where the liquid medium includes (1) a compound in liquid state that has electronic properties complementary to the electronic structure of the organic semiconducting compound and optionally (2) a solvent or solvent mixture for solubilizing the organic semiconducting compound. The present formulations can be used as inks in the fabrication of organic semiconductor devices.
1. An organic semiconductor formulation comprising a p-type organic semiconducting compound in a liquid medium, wherein the p-type organic semiconducting compound is selected from the group consisting of an oligothiophene, a thienocoronene, and a thienoacene; and the liquid medium consists essentially of a first liquid and optionally a second liquid,
the first liquid being an electron-poor liquid
(a) is selected from the group consisting of 1-trifluoromethyl-naphthalene, 2-(trifluoromethyl)naphthalene, 2-cyanonaphthalene, 1-cyanonaphthalene, 2-naphthaldehyde, 1-naphthaldehyde, 1-(1-naphthalenyl)ethanone, methyl 2-naphthyl ketone, methyl 2-naphthalenecarboxylate, methyl 1-naphthalenecarboxylate, 1-nitronaphthalene, 2-nitronaphthalene, 5-(trifluoromethyl)-1,2,3,4-tetrahydronaphthalene, 5,6,7,8-tetrahydronaphthalene-2-carbonitrile, 5,6,7,8-tetrahydronaphthalene-1-carbonitrile, 6-nitro-1,2,3,4-tetrahydronaphthalene, 5-nitro-1,2,3,4-tetrahydronaphthalene, methyl 5,6,7,8-tetrahydronaphthalene-1-carboxylate, methyl 5,6,7,8-tetrahydronaphthalene-2-carboxylate; or
(b) is an aromatic compound having a core consisting of a phenyl group fused to a cycloheteroalkyl group comprising at least one of —C(O)—, —SO 2 —, and —CF 2 — in the ring, wherein the cycloheteroalkyl group is selected from the group consisting of:
wherein R is H or a C 1-6 alkyl group; and p′ is 1 or 2; and
the second liquid being selected from the group consisting of petroleum ethers, acetonitrile, benzene, toluene, o-xylene, m-xylene, p-xylene, cyclohexylbenzene, 1-methyl naphthalene, 2-methylnaphthalene, 1-ethyl naphthalene, 2-ethylnapthalene, 1,2,4-trimethylbenzene, mesitylene, tetraline, indane, indene, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, bis(2-methoxyethyl) ether, diethyl ether, di-isopropyl ether, t-butyl methyl ether, methyl acetate, ethyl acetate, methyl formate, ethyl formate, isopropyl acetate, butyl acetate, cyclopentanone, cyclohexanone, and 2-methypyrrolidone.
2. The formulation of claim 1 , wherein the electron-poor liquid is selected from the group consisting of 1-trifluoromethyl-naphthalene, 2-(trifluoromethyl)naphthalene, 2-cyanonaphthalene, 1-cyanonaphthalene, 2-naphthaldehyde, 1-naphthaldehyde, 1-(1-naphthalenyl)ethanone, methyl 2-naphthyl ketone, methyl 2-naphthalenecarboxylate, methyl 1-naphthalenecarboxylate, 1-nitronaphthalene, 2-nitronaphthalene, 5-(trifluoromethyl)-1,2,3,4-tetrahydronaphthalene, 5,6,7,8-tetrahydronaphthalene-2-carbonitrile, 5,6,7,8-tetrahydronaphthalene-1-carbonitrile, 6-nitro-1,2,3,4-tetrahydronaphthalene, 5-nitro-1,2,3,4-tetrahydronaphthalene, methyl 5,6,7,8-tetrahydronaphthalene-1-carboxylate, and methyl 5,6,7,8-tetrahydronaphthalene-2-carboxylate.
3. The formulation of claim 1 , wherein the electron-poor liquid is an aromatic compound having a core consisting of a phenyl group fused to a cycloheteroalkyl group comprising at least one of —C(O)—, —SO 2 —, and —CF 2 — in the ring, wherein the cycloheteroalkyl group is selected from the group consisting of:
wherein R is H or a C 1-6 alkyl group; and p′ is 1 or 2.
4. The formulation of claim 1 , wherein the p-type organic semiconducting compound is a thienoacene.
5. The formulation of claim 4 , wherein the p-type organic semiconducting compound is a thienoacene selected from the group consisting of alkylated [1]benzothieno[3,2-b]benzothiophenes, alkylated dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophenes, and alkylated dibenzo[d,d′]thieno[3,2-b;4,5-b′]dithiophenes.
6. The formulation of claim 1 , wherein the p-type organic semiconducting compound is an oligothiophene, wherein the oligothiophene is dihexyl quarterthiophene.
7. The formulation of claim 1 , wherein the first liquid is present in an amount of about 10 vol % to about 50 vol % of the total volume of the formulation, and the second liquid is present in an amount of about 50 vol % to about 90 vol % of the total volume of the formulation.
8. The formulation of claim 3 , wherein the electron-poor liquid selected from the group consisting of 3,4-dihydronaphthalen-1(2H)-one, 8-methyl-3,4-dihydronaphthalen-1(2H)-one, 7-methyl-3,4-dihydronaphth al en-1(2H)-one, 6-methyl-3,4-dihydronaphthalen-1(2H)-one, 5-methyl-3,4-dihydronaphthalen-1(2H)-one, 2,3-dihydro-1H-inden-1-one, 7-methyl-2,3-dihydro-1H-inden-1-one, 6-methyl-2,3-dihydro-1H-inden-1-one, 5-methyl-2,3-dihydro-1H-inden-1-one, and 4-methyl-2,3-dihydro-1H-inden-1-one.
9. An organic semiconductor formulation comprising a p-type organic semiconducting compound in a liquid medium, wherein the p-type organic semiconducting compound is selected from the group consisting of an oligothiophene, a thienocoronene, and a thienoacene; and the liquid medium consists essentially of a first liquid and optionally a second liquid,
the first liquid being an electron-poor liquid comprising an aromatic compound having either (i) at least one electron-withdrawing functional group (FG ewd ) as a substituent, (ii) an electron-poor aromatic core, or both (i) and (ii), the electron-poor liquid being represented by the formula:
in which p is 0, 1 or 2 and Ar is a phenyl group or a naphthyl group optionally substituted with 1-4 groups independently selected from Cl and a C 1-6 alkyl group, or
in which Ar is a naphthyl group optionally substituted with 1-4 groups independently selected from Cl and a C 1-6 alkyl group, or
in which p is 0, 1 or 2 and Ar″ is an electron-poor 5-14 membered heteroaryl group or a phenyl group fused to an electron-poor 5-, 6- or 7-membered cycloheteroalkyl group optionally substituted with 1-4 groups independently selected from Cl and a C 1-6 alkyl group, or
in which Ar″ is a phenyl group fused to an electron-poor 5-, 6- or 7-membered cycloheteroalkyl group optionally substituted with 1-4 groups independently selected from Cl and a C 1-6 alkyl group;
wherein
FG ewd , at each occurrence, independently is selected from —NO 2 , —CN, —NC, —S(R b ) 2 + , —N(R b ) 3 + , —SC 3 H, —SO 2 R b , —SO 3 R b , —SO 2 NHR b , —SO 2 N(R b ) 2 , —COOH, —COR b , —COOR b , —CONHR b , —CON(R b ) 2 , and CF 3 ; wherein R b , at each occurrence, independently is a C 1-20 alkyl group, a C 1-20 haloalkyl group, a —Y′—C 6-14 aryl group, or a —Y′—C 3-14 cycloalkyl group; Y′ is a divalent C 1-20 alkyl group, a divalent C 1-20 haloalkyl group or a covalent bond; and each of the C 6-14 aryl group and the C 3-14 cycloalkyl group optionally is substituted with 1-4 groups independently selected from F, Cl, Br, I, a methyl group, an ethyl group, and a propyl group,
n, at each occurrence, is 1, 2, 3 or 4, and
n′, at each occurrence is 0, 1, 2, 3 or 4;
the first liquid being in liquid state at about 1 atm at a temperature of 50° C. or less; and
the second liquid being selected from the group consisting of petroleum ethers, acetonitrile, benzene, toluene, o-xylene, m-xylene, p-xylene, cyclohexylbenzene, 1-methyl naphthalene, 2-methylnaphthalene, 1-ethyl naphthalene, 2-ethylnapthalene, 1,2,4-trimethylbenzene, mesitylene, tetraline, indane, indene, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, bis(2-methoxyethyl) ether, diethyl ether, di-isopropyl ether, t-butyl methyl ether, methyl acetate, ethyl acetate, methyl formate, ethyl formate, isopropyl acetate, butyl acetate, cyclopentanone, cyclohexanone, and 2-methypyrrolidone.
10. The formulation of claim 9 , wherein the electron-poor liquid is represented by the formula:
in which p is 0, 1 or 2 and Ar is a phenyl or naphthyl group optionally substituted with 1-4 groups independently selected from Cl and a C 1-6 alkyl group.
11. The formulation of claim 10 , wherein p is 2.
12. The formulation of claim 11 , wherein the electron-poor liquid is selected from the group consisting of 5-(trifluoromethyl)-1,2,3,4-tetrahydronaphthalene, 5,6,7,8-tetrahydronaphthalene-2-carbonitrile, 5,6,7,8-tetrahydronaphthalene-1-carbonitrile, 6-nitro-1,2,3,4-tetrahydronaphthalene, 5-nitro-1,2,3,4-tetrahydronaphthalene, methyl 5,6,7,8-tetrahydronaphthalene-1-carboxylate, and methyl 5,6,7,8-tetrahydronaphthalene-2-carboxylate.
13. The formulation of claim 9 , wherein the electron-poor liquid is represented by the formula:
in which Ar is a naphthyl group optionally substituted with 1-4 groups independently selected from Cl and a C 1-6 alkyl group.
14. The formulation of claim 13 , wherein the electron-poor liquid is selected from the group consisting of 1-trifluoromethyl-naphthalene, 2-(trifluoromethyl)naphthalene, 2-cyanonaphthalene, 1-cyanonaphthalene, 2-naphthaldehyde, 1-naphthaldehyde, 1-(1-naphthalenyl)ethanone, methyl 2-naphthyl ketone, methyl 2-naphthalenecarboxylate, methyl 1-naphthalenecarboxylate, 1-nitronaphthalene, and 2-nitronaphthalene.
15. The formulation of claim 9 , wherein the electron-poor liquid is represented by the formula:
in which p is 0, 1 or 2 and Ar″ is an electron-poor 5-14 membered heteroaryl group or a phenyl group fused to an electron-poor 5-, 6- or 7-membered cycloheteroalkyl group optionally substituted with 1-4 groups independently selected from Cl and a C 1-6 alkyl group.
16. The formulation of claim 9 , wherein the electron-poor liquid is represented by the formula:
in which Ar″ is a phenyl group fused to an electron-poor 5-, 6- or 7-membered cycloheteroalkyl group optionally substituted with 1-4 groups independently selected from Cl and a C 1-6 alkyl group.
17. The formulation of claim 9 , wherein the p-type organic semiconducting compound is a thienoacene.
18. The formulation of claim 17 , wherein the p-type organic semiconducting compound is a thienoacene selected from the group consisting of alkylated [1]benzothieno[3,2-b]benzothiophenes, alkylated dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophenes, and alkylated dibenzo[d,d′]thieno[3,2-b;4,5-b]dithiophenes.
19. The formulation of claim 8 , wherein the first liquid is present in an amount of about 10 vol % to about 50 vol % of the total volume of the formulation, and the second liquid is present in an amount of about 50 vol % to about 90 vol % of the total volume of the formulation.