Composition of conducting polymer and organic opto-electronic device employing the same
A composition including a conducting polymer and an ionomer, and an opto-electronic and an electronic device including the composition are provided. The composition is prepared by doping a conducting polymer with an ionomer which has a low water uptake, has a low content of by-products decomposed by a reaction with electrons, and can crosslink with the conducting polymer. Thus, the opto-electronic device including the composition has improved device performance such as device efficiency and lifetime.
1. A composition, comprising:
a conducting polymer;
a first ionomer represented by one of Formulae (3), (6), (8), (9), (10), (11) and (13)
where m is a number of 1 to 10,000,000;
where 0<m≦10,000,000, 0≦n<10,000,000, z is a number of 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0<n<10,000,000, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, and 0<n<10,000,000;
where 0<m≦10,000,000, 0≦n≦10,000,000, x is a number of 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0<n<10,000,000, each of x and y is independently a number of 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0<n<10,000,000, each of x and y is independently a number of 0 to 20, Y is —SO 3 − M + , —COO − M + , —SO 3 − NHSO 2 CF3 + , or —PO 3 2− (M + ) 2 , and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ; and
at least one of a physical crosslinking agent and a chemical crosslinking agent.
2. The composition of claim 1 , wherein the amount of the first ionomer is 100 to 5,000 parts by weight based on 100 parts by weight of the conducting polymer.
3. The composition of claim 1 , wherein the composition further comprises a second ionomer represented by Formula (1), and the first ionomer and the second ionomer are different from each other:
where 0<m≦10,000,000;
0≦n≦10,000,000;
0≦a≦20;
0≦b≦20;
each of A, B, A′, and B′ is independently selected from the group consisting of C, Si, Ge, Sn, and Pb;
each of R 1 , R 2 , R 3 , R 4 , R 1 ′, R 2 ′, R 3 ′, and R 4 ′ is independently selected from the group consisting of a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted amino group, a cyano group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 heteroalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 heteroalkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 arylalkyl group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted C2-C30 heteroarylalkyl group, a substituted or unsubstituted C2-C30 heteroaryloxy group, a substituted or unsubstituted C5-C20 cycloalkyl group, a substituted or unsubstituted C2-C30 heterocycloalkyl group, a substituted or unsubstituted C1-C30 alkylester group, a substituted or unsubstituted C1-C30 heteroalkylester group, a substituted or unsubstituted C6-C30 arylester group, and a substituted or unsubstituted C2-C30 heteroarylester group, and at least one of R 1 , R 2 , R 3 , and R 4 is an ionic group or includes an ionic group;
each of X and X′ is independently selected from the group consisting of a single bond, O, S, a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C1-C30 heteroalkylene group, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C6-C30 arylalkylene group, a substituted or unsubstituted C2-C30 heteroarylene group, a substituted or unsubstituted C2-C30 heteroarylalkylene group, a substituted or unsubstituted C5-C20 cycloalkylene group, a substituted or unsubstituted C5-C30 heterocycloalkylene group, a substituted or unsubstituted C6-C30 arylester group, and a substituted or unsubstituted C2-C30 heteroarylester group; and
at least one of R 1 , R 2 , R 3 , and R 4 is a hydrophobic functional group having a halogen element when n is 0.
4. The composition of claim 3 , wherein the second ionomer is a hydrocarbon, fluorocarbon or silicone polymer represented by Formula (1) in which n=0 and 0<m<10,000,000.
5. The composition of claim 4 , wherein the second ionomer is a perfluorocarbon.
6. The composition of claim 4 , wherein the second ionomer comprises ionomers represented by Formulae (2) to (7) and (10) to (13):
where m is a number of 1 to 10,000,000, each of x and y is dependently a number of 0 to 10, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where m is a number of 1 to 10,000,000;
where 0<m≦10,000,000, 0≦n<10,000,000, each of x and y is independently a number of 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0≦n<10,000,000, each of x and y is independently a number of 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0≦n<10,000,000, z is a number of 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0≦n<10,000,000, each of x and y is independently a number of 0 to 20, Y is —COO − M + , —SO 3 − NHSO 2 CF 3 + , or —PO 3 2− (M + ) 2 , and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0≦n<10,000,000, x is a number of 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0<n<10,000,000, each of x and y is independently a number of 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0≦n<10,000,000, R f is —(CF 2 ) c — in which c is an integer of 1 to 50, but is not 2, —(CF 2 CF 2 O) d CF 2 CF 2 — in which d is an integer of 1 to 50, or —(CF 2 CF 2 CF 2 O) e CF 2 CF 2 — in which e is an integer of 1 to 50, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0<n<10,000,000, each of x and y is independently a number of 0 to 20, Y is —SO 3 − M + , —COO − M + , —SO 3 − NHSO 2 CF 3 + , or —PO 3 2− (M + ) 2 , and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + .
7. The composition of claim 4 , wherein the second ionomer comprises ionomers represented by Formulae (8) and (9):
where 0<m≦10,000,000, 0<n<10,000,000, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ; and
where 0<m≦10,000,000, and 0<n<10,000,000.
8. The composition of claim 1 , wherein the conducting polymer is at least one polymer selected from the group consisting of polyethylenedioxythiopene (PEDOT), polyaniline, polypyrrole, polyacetylene, polyphenylene, polyphenylenevinylene, polythiopene, and a copolymer thereof.
9. The composition of claim 3 , wherein the ionic group includes an anionic group selected from the group consisting of PO 3 2− , SO 3 − , COO − , I − , and CH 3 COO − , and a cation group capable of forming a couple with the anionic group, the cation group selected from the group consisting of a metal ion and an organic ion, the metal ion is selected from the group consisting of Na + , K + , Mg +2 , Zn +2 , and Al +3 , the organic ion is selected from the group consisting of H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + .
10. The composition of claim 3 , wherein the hydrophobic functional group is a halogen element.
11. The composition of claim 3 , wherein the hydrophobic functional group is fluorine.
12. The composition of claim 1 , wherein the physical crosslinking agent has a hydroxy group (—OH).
13. The composition of claim 1 , wherein the physical crosslinking agent is a compound selected from the group consisting of glycerol, butanol, polyvinylalcohol, polyethyleneglycol, polyethyleneimine, and polyvinylpyrrolidone.
14. The composition of claim 1 , wherein the chemical crosslinking agent is a compound selected from the group consisting of tetraethyloxysilane (TEOS), polyaziridine, melamine-based materials, and epoxy-based materials.
15. The composition of claim 1 , wherein the content of non-ionic monomer units in the first ionomer is 1 to 99 mol %, based on the total content of monomer units of the first ionomer.
16. A conducting film formed from the composition of claim 1 .
17. An opto-electronic device comprising the conducting film of claim 16 .
18. An electronic device comprising the conducting film of claim 16 .
19. A device having a conducting film, the conducting film formed of a conducting polymer doped with a first ionomer represented by Formulae (3), (6), (8), (9), (10), (11) and (13)
where m is a number of 1 to 10,000,000;
where 0<m≦10,000,000, 0≦n<10,000,000, z is a number of 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0<n<10,000,000, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, and 0<n<10,000,000;
where 0<m≦10,000,000, 0≦n<10,000,000, x is a number of 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0<n<10,000,000, each of x and y is independently a number of 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0<n<10,000,000, each of x and y is independently a number of 0 to 20, Y is —SO 3 − M + , —COO − M + , —SO 3 − NHSO 2 CF3 + , or —PO 3 2− (M + ) 2 , and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + .
20. The device of claim 19 , wherein the device is an organic electroluminescent device, and the conducting film is used as a charge injection layer to inject holes or electrons into a light emitting layer.
21. The device of claim 19 , wherein the device is an organic solar cell, and the conducting film is used as an electrode or an electrode buffer layer.
22. The device of claim 19 , wherein the device is an organic transistor, and the conducting film is used an electrode material.
23. An organic electroluminescent device, comprising:
a first electrode;
a second electrode;
an emissive layer between the first electrode and the second electrode; and
a hole injection layer between the first electrode and the emissive layer, the hole injection layer formed of a conducting polymer doped with a first ionomer represented by Formulae (3), (6), (8), (9), (10), (11) and (13)
where m is a number of 1 to 10,000,000;
where 0<m≦10,000,000, 0≦n<10,000,000, z is a number of 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0<n<10,000,000, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, and 0<n<10,000,000;
where 0<m≦10,000,000, 0≦n<10,000,000, x is a number of 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0<n<10,000,000, each of x and y is independently a number of 0 to 20, and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + ;
where 0<m≦10,000,000, 0<n<10,000,000, each of x and y is independently a number of 0 to 20, Y is —SO 3 − M + , —COO − M + , —SO 3 − NHSO 2 CF 3 + , or —PO 3 2− (M + ) 2 , and M + is Na + , K + , Li + , H + , CH 3 (CH 2 ) a NH 3 + in which a is an integer of 0 to 50, or NH 4 + .
24. The composition of claim 1 , wherein the first ionomoer is represented by Formula (3).
25. The composition of claim 1 , wherein the first ionomoer is represented by Formula (6).
26. The composition of claim 1 , wherein the first ionomoer is represented by Formula (8).
27. The composition of claim 1 , wherein the first ionomoer is represented by Formula (9).
28. The composition of claim 1 , wherein the first ionomoer is represented by Formula (10).
29. The composition of claim 1 , wherein the first ionomoer is represented by Formula (11).
30. The composition of claim 1 , wherein the first ionomoer is represented by Formula (13).