Cross-linked co-polymers for making optoelectronic devices

Patent metadata

Field	Value
Publication number	US-2016200845-A1
Application number	US-201314912725-A
Country	US
Kind code	A1
Filing date	Aug 23, 2013
Priority date	Aug 23, 2013
Publication date	Jul 14, 2016
Grant date	—

Abstract

Compositions, devices, and methods are provided regarding cross-linked co-polymers that include chromophores, where the chromophores are aligned so as to provide electro-optic activity to the cross-linked co-polymer.

First claim

1 . A cross-linked co-polymer comprising a first repeating unit and a second repeating unit, wherein the first repeating unit is represented as

wherein:
X 1 is O, NR 3 , or S;
Y is O or S;
R 1 is H, alkyl, cyano, or halo;
R 2 is H, alkyl, or aryl;
R 3 is H or alkyl;
L is —alkylene-, —O-alkylene-, —NR 4 -alkylene-, -heterocyclylene-, —O-heterocyclylene-, —NR 4 -heterocyclylene-, -arylene-, —O-arylene-, —NR 4 -arylene-, -heteroarylene-, —O-heteroarylene-, or —NR 4 -heteroarylene-; where R 4 is H, alkyl, or aryl; and
D is a chromophore represented by one of the following formulas:

where
R 5 , R 7 , R 8 and R 9 are each independently alkyl or aryl;
R 6 is alkyl, perhaloalkyl, aryl, or aralkyl;
Z is alkenylene, arylene, or heteroarylene;
V is H or an alkylene group bonded to Z;
Q is alkylene, arylene, or aralkylene;
K 1 and K 2 are each independently CH or N;
T is alkylene or arylene, and T is in an ortho or a meta position on the ring with respect to the bond to K;
A is cyano, nitro, CF 3 or

where R 11 is alkyl, perhaloalkyl, aryl, or aralkyl, and A is in a para or an ortho position on the ring with respect to the bond to K 1 ;
W 1 W 2 , W 3 , and W 4 are each independently cyano, perhaloalkyl, CO 2 R 10 SO 2 R 10 , S(O)(OR 10 ) 2 , P(O)(OR 10 ) 2 ;
W 3 is independently perhaloalkyl, CO 2 R 10 , SO 2 R 10 , S(O)(OR 10 ) 2 , P(O)(OR 10 ) 2 ;
R 10 is alkyl or perhaloalkyl,
n is 1, 2, 3, 4, 5, 6, 7, 8, 10, or 11, and
m is 1, 2, 3, or 4.

2 .- 3 . (canceled)

4 . The cross-linked co-polymer of claim 1 , wherein L is —O-ethylene-, —O-propylene-, or —O-butylene-.

5 . The cross-linked co-polymer of claim 1 , wherein the second repeating unit is derived from a styrenic monomer, a acrylate monomer, a cyanoacrylate monomer, an acrylamide monomer, or an olefinic monomer.

6 .- 8 . (canceled)

9 . The cross-linked co-polymer of claim 1 , wherein X 1 is O.

10 .- 11 . (canceled)

12 . The cross-linked co-polymer of claim 1 , wherein T is in a meta position with respect to the bond to K 1 .

13 . The cross-linked co-polymer of claim 1 , wherein K 2 is CH.

14 . The cross-linked co-polymer of claim 1 , wherein K 1 and K 2 are both N.

15 . The cross-linked co-polymer of claim 1 , wherein n is 1, 2, 3, or 4.

16 . The cross-linked co-polymer of claim 1 , wherein R 5 , R 7 , R 8 and R 9 are each independently alkyl.

17 . The cross-linked co-polymer of claim 1 , wherein R 6 is methyl, CF 3 , or p-methoxyphenyl.

18 . The cross-linked co-polymer of claim 1 , wherein Q is —CH 2 -Ph-.

19 . The cross-linked co-polymer of claim 1 , wherein R 11 is methyl, CF 3 , or p-methoxyphenyl.

20 . The cross-linked co-polymer of claim 1 , wherein W 1 , W 2 , W 3 , and W 4 are each independently cyano, CF 3 , CF 2 CF 3 , CO 2 Me, CO 2 Et, SO 2 CF 3 , SO 2 Ph, S(O)(OPhCH 3 ) 2 , P(O)(OCH 3 ) 2 , P(O)(OCF 3 ) 2 , P(O)(OPh) 2 , or P(O)(OPhCH 3 ) 2 .

21 . The cross-linked co-polymer of claim 1 , wherein
R 9 is C l -C 6 alkyl; K 1 and K 2 are both N; A is p-cyano, p-nitro, or p-CF 3 ; T is methylene, ethylene, propylene, or butylene; and n is 1, 2, 3, or 4.

22 . The cross-linked co-polymer of claim 1 , wherein the chromophore is

23 . An optoelectronic device comprising
a cross-linked co-polymer of claim 1 , comprising a first and a second end; and a light source proximal to the first end of the co-polymer configured to illuminate light onto the first end such that the light propagates from the first end to the second end; wherein
the optoelectronic device has a bandwidth of about 1 GHz to about 10 THz.

24 . The optoelectronic device of claim 23 , wherein
a portion of the cross-linked co-polymer is split into a first branch and a second branch and subsequently rejoined; a portion of the first branch is attached to two electrodes that span the diameter of the first branch.

25 .- 45 . (canceled)

46 . A method of producing a cross-linked co-polymer, comprising
heating a film comprising a co-polymer and a cross-linker in the presence of an electric field; wherein
the co-polymer comprises a first repeating unit and a second repeating unit, where the first repeating unit is represented as
where

Y is Y or S;
R 1 is H, alkyl, cyano, or halo;
R 2 is H, alkyl, or aryl;
L is a linking moiety; and
G is an O- or N-bound blocking group;

the cross-linker is represented as
X 2 -D-X 2
where
X 2 is OH, NHR 3 , or SH;
R 3 is H or alkyl;
D is a chromophore, each X 2 is separated from the other by at least 10 atoms in the chromophore and at least two of the 10 atoms are part of a conjugated 7c-electron system; and

heating the co-polymer with the cross-linker in the presence of the electric field generates G-H, wherein G-H is an alkyl alcohol, an aryl alcohol, an imidazole, a pyrazole, a triazole, a tetrazole, an imide, a 62 dicarbonyl compound, a β-cyano carbonyl compound, a pyrrolidine, a morpholine, a thiomorpholine, a pyridine, a piperidine, or a combination of any two or more thereof.

47 .- 64 . (canceled)

65 . The method of claim 46 , wherein the electric field is applied by a contact poling or a corona discharge.

66 .- 83 . (canceled)

84 . The method of claim 46 , wherein G-H is removed during the heating step by evaporation, sublimation, or a combination thereof.

85 .- 87 . (canceled)

Assignees

• Empire Technology Dev Llc

Inventors

• Carlson William Brenden
• Phelan Gregory David

Classifications

• G02F1/0018

  Electro-optical materials · CPC title

• C09K2211/145

  containing oxygen as the only heteroatom · CPC title

• G02F1/3558

  Poled materials, e.g. with periodic poling; Fabrication of domain inverted structures, e.g. for quasi-phase-matching [QPM] · CPC title

• C08J3/247

  Heating methods · CPC title

• C09K2211/1433

  bridged by heteroatoms, e.g. N, P, Si or B · CPC title