Sequential synthesis technique for deposition of aligned organic electro-optic materials

Patent metadata

Field	Value
Publication number	US-12404449-B2
Application number	US-202318334294-A
Country	US
Kind code	B2
Filing date	Jun 13, 2023
Priority date	Jun 13, 2022
Publication date	Sep 2, 2025
Grant date	Sep 2, 2025

Abstract

Disclosed are organic electrooptic materials. The electrooptic materials are functionalized by novel methods and structures. The electrooptic materials are structured with a head and a tail where the head and tail sequentially assemble into a non-centrosymmetric ordered array. The electrooptic materials are further structured in covalently bonded dimer pairs where one of the pairs is zwitterionic. The non-centrosymmetric ordered array bonds directly to electrodes which allows for efficient application of the electric field. The organic electrooptic materials disclosed offer greater hyperpolarizability, greater bandwidth, reduced operating voltage with less optical loss.

First claim

The invention claimed is:

1. A film comprising a plurality of electrooptic chromophores, a first layer of the electrooptic chromophores bonded to a substrate in a first layer, such that the substrate imparts non-centrosymmetric order onto the electrooptic chromophores, the plurality of electrooptic chromophores including a plurality of least one neutral ground state (NGS) chromophore and a plurality of at least one zwitterionic ground state (ZGS) chromophore;
wherein the least one NGS chromophore comprises:
a head;
a donor;
a bridge;
an acceptor;
a tail;

wherein the head is a reactive group that is covalently bonded to the donor and is configured to react with the underlying surface or a capping agent that supplies a functional group;
wherein the donor is a group that has excess electron density and allows for connection to the head;
wherein the bridge electronically communicates between the donor and acceptor;
wherein the acceptor is deficient in electron density and allows for connection to the tail;
wherein the tail is a reactive group that is covalently bonded to the acceptor and is configured to react with the underlying surface or a capping agent that supplies a functional group; and
wherein the head and tail are configured to allow for sequential polymerization of the least one NGS electrooptic chromophore in non-centrosymmetric alignment; and
wherein the least one ZGS chromophore comprises:
a head;
a donor;
a bridge;
an acceptor;
a tail;

wherein the head is a reactive group that is covalently bonded to the donor and is configured to react with the underlying surface or a capping agent that supplies a functional group;
wherein the donor is a group that has excess electron density and allows for connection to the head;
wherein the bridge electronically communicates between the donor and acceptor;
wherein the acceptor is deficient in electron density and allows for connection to the tail;
wherein the tail is a reactive group that is covalently bonded to the acceptor and is configured to react with the underlying surface or a capping agent that supplies a functional group;
wherein the head and tail allow for sequential polymerization of the electrooptic chromophore; and
wherein one side of the chromophore perpetually carries a positive charge, one side of the chromophore perpetually carries a negative charge and the positive charge and negative charge are separated by the bridge.

2. The film according to claim 1 , wherein the least one NGS electrooptic chromophore head has an alkene, alkyne, hydroxyl, trifluorovinylether, diene, propadiene, or azide group.

3. The film according to claim 1 , wherein the least one NGS electrooptic chromophore the bridge has a structure:

wherein Q is selected from the group consisting of vinyl, aryl, fused aryl, heteroaryl, and fused heteroaryl; X is selected from the group consisting of H, O, S, Se, Te, NH, PH, and AsH; and Y is selected from the group consisting of absent, H, C1-10 alkyl, phenyl, benzyl, C1-10 alkyl substituted phenyl, C1-10 substituted benzyl, and O-tert-butyldiphenylsilyl (OTBDPS).

4. The film according to claim 1 , wherein the acceptor has a structure:

wherein R1 and R2 are independently selected from the group consisting of methyl, trifluoromethyl, ethyl, pentafluoroethyl, phenyl, pentafluorophenyl, and perfluoroalkyl; and Z or Z′ is a structural unit which allows for forming a covalent bond with the tail.

5. The film according to claim 1 , wherein the least one NGS electrooptic chromophore tail has an alkene, alkyne, hydroxyl, trifluorovinylether, diene, propadiene, or azide group.

6. The film according to claim 1 , wherein the film is sol-gel capped and the least one NGS electrooptic chromophore has a structure:

wherein the sulfur can be bonded to a substrate.

7. The film according to claim 1 , wherein the least one ZGS chromophore cation is carbocation, ammonium, pyridinium, phosphonium, phosphininium or borinine.

8. The film according to claim 1 , wherein the least one ZGS chromophore is sol-gel capped and has the structure:

where in the sulfur can be bonded to a substrate.

9. The film according to claim 1 , wherein at least some of the least one NGS chromophores and at least some of the least one ZGS chromophores are present in the form of chromophore dimers that include both an the least one NGS chromophore portion and a the least one ZGS chromophore portion bound together through at least one common structural unit.

10. The film according to claim 9 , wherein the chromophore dimer common structural unit is aryl, bisaryl, trisaryl, teraryl, pentaryl, hexaryl, fused aryl, heteroaryl, bisheteroaryl, trisheteroaryl, terheteroaryl, pentheteroaryl, hexheteroaryl, or fused heteroaryl with at least 4 substituents.

11. The film according to claim 10 , wherein the chromophore dimer is sol-gel capped and has a structure:

12. The film of according to claim 1 , further comprising a second layer, that includes a plurality of least one NGS chromophore and a plurality of at least one ZGS chromophore, covalently bonded to the first layer, such that the non-centrosymmetric order is maintained in the second layer of chromophores.

13. The film according to claim 12 , formed by a cycloaddition reaction between (a) in the layer a first polarizable chromophore comprising at least two first reactive groups crosslinkable by sol-gel followed by cycloaddition and (b) in the second layer a second polarizable chromophore comprising one or more compounds comprising at least two counterpart reactive groups.

14. The film according to claim 1 , wherein the first layer is capped with a sol-gel glass that the second layer is bonded to.

15. The film according to claim 14 , wherein the sol-gel glass comprises of 3-azopropyltrimethoxysilane and catena-octachlorotrisiloxane.

16. The film according to claim 1 , wherein the film has a crosslinked structure between the least one NGS chromophores and the least one ZGS chromophores.

17. The film of according to claim 1 , wherein the film comprises of 1-2000 layers of chromophores.

18. The film according to claim 1 , wherein the substrate comprises a metal, silicon, or a silicon oxide that the first layer of chromophore is bonded to.

19. The film according to claim 1 , wherein the film has an electrooptic coefficient r33 value of about 100 pm/V or greater.

20. A device comprising a film according to claim 1 , wherein the substrate includes a first electrode that the first layer of electrooptic chromophores is bonded to, wherein the device is selected from an electro-optic modulator, antenna, Mach-Zehnder modulator, phase modulator, silicon-organic hybrid modulator, plasmonic-organic hybrid modulator, electrical-to-optical convertor, terahertz detector, frequency shifter, spatial light modulator, and

Assignees

• Univ Washington
• NLM Photonics

Inventors

• Elder Delwin L
• Dalton Iii Larry R
• Johnson Lewis E
• Hammond Scott R
• Robinson Bruce H
• O'Malley Kevin M

Classifications

• C09K2211/104

  with other heteroatoms · CPC title

• C09K2211/1059

  containing three nitrogen atoms as heteroatoms · CPC title

• C09K2211/1033

  with oxygen · CPC title

• C09K2211/1088

  containing oxygen as the only heteroatom · CPC title

• C09K2211/1096

  containing other heteroatoms · CPC title