Stabilized electro-optic materials and electro-optic devices made therefrom
View Patent ↗According to an embodiment, an electro-optic polymer comprises a host polymer and a guest nonlinear optical chromophore having the structure D-π-A, wherein: D is a donor, π is a π-bridge, and A is an acceptor; a bulky substituent group is covalently attached to at least one of D, π, or A; and the bulky substituent group has at least one non-covalent interaction with part of the host polymer that impedes chromophore depoling.
1. An electro-optic polymer comprising a host polymer and a poled guest nonlinear optical chromophore having the structure D-π-A, wherein: D is a donor; π is a π-bridge; A is an acceptor; at least one aryl substituent group is covalently attached to π; and the aryl substituent group has at least one non-covalent interaction with part of the host polymer that impedes chromophore depoling.
2. The electro-optic polymer of claim 1 , wherein the non-covalent interaction is a pi-interaction, a size interaction, or a preorganized binding interaction.
3. The electro-optic polymer of claim 2 , wherein the pi-interaction comprises at least one pi-system on the aryl group and at least one pi-system on the host polymer.
4. The electro-optic polymer of claim 3 , wherein the pi-system on the aryl group comprises an aryl, polycyclic aryl, heterocyclic aryl, polyheterocyclic aryl group.
5. The electro-optic polymer of claim 4 , wherein the pi-system on the host polymer comprises an aryl, polycyclic aryl, heterocyclic aryl, polyheterocyclic aryl group.
6. The electro-optic polymer of claim 5 , wherein the pi-system on the aryl group is a pi-interacting donor or pi-interacting acceptor that is complementary to a pi-interacting donor or pi-interacting acceptor of the pi-system on the host polymer.
7. The electro-optic polymer of claim 1 , wherein the electro-optic polymer has a glass transition temperature, and the bulky substituent impedes chromophore depoling below the glass transition temperature.
8. The electro-optic polymer of claim 1 , wherein the chromophore comprises at least two aryl groups.
9. The electro-optic polymer of claim 8 , wherein one aryl group is attached to π and one aryl group is attached to D or A.
10. The electro-optic polymer of claim 1 , wherein: the chromophore has a melting point greater than 120° C.; the polymer has a glass transition temperature above 120° C.; and the electro-optic composite has a glass transition temperature above 120° C.
11. The electro-optic polymer of claim 10 , wherein the loading density of the chromophore is greater than 20% by weight.
12. The electro-optic polymer of claim 10 , wherein the loading density of the chromophore is greater than about 35% by weight.
13. The electro-optic polymer of claim 1 , wherein D comprises
wherein R 1 independently comprises and alkyl, heteroalkyl, aryl, or heteroaryl group; R 2 independently at each occurrence comprises an H, alkyl group, heteroalkyl group, aryl group, or heteroaryl group; R 3 independently at each occurrence comprises a halogen, an alkyl group, and heteroalkyl group, an aryl group, or a heteroaryl group; n is 0-3, and R 1 comprises the bulky group.
14. The electro-optic polymer of claim 13 , wherein the electro-optic chromophore further comprises an aryl group attached to D or A.
15. An electro-optic composite comprising the nonlinear optical chromophore of claim 1 , wherein the composite has greater than 80% temporal stability at 85° C. after 100 hours.
16. An electro-optic device comprising the electro-optic polymer of claim 1 .
17. The electro-optic device of claim 16 , wherein the electro-optic device includes a Mach-Zehnder interferometer, a Michelson interferometer, a micro-ring resonator, or a directional coupler.
18. An electro-optic polymer comprising a poled nonlinear optical chromophore and a host polymer, wherein the nonlinear optical chromophore is substituted with two or more aryl groups including one or more aryl groups substituted onto a π-bridge of the chromophore; and
wherein the host polymer is configured to cooperate with the aryl groups to impede chromophore depoling.
19. The electro-optic polymer of claim 18 , wherein the nonlinear optical chromophore has the structure D-π-A, and wherein: D is a donor; π is a π-bridge; A is an acceptor; D is substituted with an aryl group; and π is substituted with an aryl group.
20. The electro-optic polymer of claim 19 , wherein the aryl groups and the polymer cooperate via pi-interactions.
21. An electro-optic polymer comprising:
a poled nonlinear optical chromophore and a host polymer;
wherein the nonlinear optical chromophore has he structure D-π-A, wherein D is a donor, π is a π-bridge, and A is an acceptor;
wherein D substituted with an aryl group;
wherein π is substituted with an aryl group; and
wherein the aryl groups and the polymer cooperate via pi-interactions to impede chromophore depoling.
22. The electro-optic polymer of claim 21 , wherein the aryl groups independently are an aryl hydrocarbon, an aryl polycyclic hydrocarbon, a heteroaryl, or a polycyclic heteroaryl.
23. The electro-optic polymer of claim 21 , wherein the host polymer is a polycarbonate, a poly(arylene ether), a polysulfone, a polyimide, a polyester, a polyacrylate, or any copolymer thereof.
24. The electro-optic polymer of claim 21 , wherein the host polymer has a Tg greater than 150° C. and is a polysulfone; a polyester; a polycarbonate; a polyimide; a polyimideester; a polyarylether; a poly(methacrylic acid ester); a poly(ether ketone); a polybenzothiazole; a polybenzoxazole; a polybenzobisthiazole; a polybenzobisoxazole; a poly(aryl oxide); a polyetherimide; a polyfluorene; a polyarylenevinylene; a polyquinoline, a polyvinylcarbazole; or any copolymer thereof.
25. An electro-optic device comprised of the electro-optic polymer of claim 18 , wherein the electro-optic device has a V pi that does not increase more than 5% after 2000 hours at 85° C.
26. An electro-optic device comprised of the electro-optic polymer of claim 18 , wherein the electro-optic device has a V pi that does not increase more than 10% after 2000 hours at 85° C.
27. An electro-optic device comprised of the electro-optic polymer of claim 18 , wherein the electro-optic device has a V pi that does not increase more than 15% after 2000 hours at 85° C.
28. An electro-optic device comprised of the electro-optic polymer of claim 18 , wherein the electro-optic device has a V pi that does not increase more than 20% after 2000 hours at 85° C.
29. An electro-optic polymer comprising a poled nonlinear optical chromophore and a host polymer, wherein:
the nonlinear optical chromophore has a bulky substituent comprising at least one aryl group substituted onto a pi-bridge of the chromophore; and
the host polymer has an aryl group selected to interact with the aryl group of the substituent.
30. The electro-optic polymer of claim 29 , wherein the substituent comprises 2 or 3 aryl groups.
31. The electro-optic polymer of claim 30 , wherein the chromophore has the structure D-π-A and the triaryl group has the structure
wherein: D is a donor; π is a p-bridge; A is an acceptor; X is a substituent center; Ar 1 , Ar 2 , and Ar 3 are the aryl groups; and L is a covalent linker attached to D, π, or A.
32. An electro-optic polymer including a nonlinear optical chromophore having the structure D-π-A, wherein D is a donor, π is a π-bridge, A is an acceptor, and at least one of D or A is covalently attached to a bulky group comprising at least one aryl group, wherein π is covalently attached to a bulky group comprising at least one aryl group, and wherein the electro-optic polymer has greater temporal stability than when an alkyl group is substituted for the aryl groups.
33. The electro-optic polymer of claim 32 , wherein the bulky group comprises at least two aryl groups, and wherein the electro-optic polymer has greater temporal stability than when alkyl groups are substituted for the aryl groups.
34. The electro-optic polymer of claim 33 , wherein the bulky group comprises at least three aryl groups, and wherein the electro-optic polymer has greater temporal stability than when alkyl groups are substituted for the aryl groups.
35. An electro-optic polymer comprising a nonlinear optical chromophore and a host polymer, wherein: the nonlinear optical chromophore has a substituent group comprising at least two aryl groups with at least one of the aryl groups being substituted onto a pi-bridge of the electro-optic polymer; the host polymer comprises a subunit comprising at least two aryl groups; and the aryl groups of the nonlinear optical chromophore align preferentially with the aryl groups of the subunit.
36. The electro-optic polymer of claim 35 , wherein the host polymer is a polysulfone; a polyester; a polycarbonate; a polyimide; a polyimideester; a polyarylether; a poly(methacrylic acid ester); a poly(ether ketone); a polybenzothiazole; a polybenzoxazole; a polybenzobisthiazole; a polybenzobisoxazole; a poly(aryl oxide); a polyetherimide; a polyfluorene; a polyarylenevinylene; a polyquinoline, a polyvinylcarbazole; or any copolymer thereof.