Intrinsically low resistivity hybrid sol-gel polymer clads and electro-optic devices made therefrom
View Patent ↗A low resistivity hybrid organic-inorganic material may include a proportion of charge traps including a trap element indirectly covalently bonded to a donor or acceptor element. The trap element may include tin. The donor or acceptor element may include indium and/or antimony. Bonding includes cross-linking via oxygen bonds and via organic cross-linkers. The material may be formed as a hybrid sol-gel. The material may have optical transmission and refractive index characteristics. The material may be formed as optical cladding proximal to a non-linear optical layer, and may form a portion of a second order nonlinear optical device. The second order nonlinear optical device may include and electro-optic device including an organic chromophore-loaded modulation layer.
1. An electro-optic device, comprising:
an electro-optic core; and
abutting or proximate the electro-optic core, at least one optical cladding formed as an intrinsically low resistivity hybrid organic-inorganic polymer network,
wherein the at least one intrinsically low resistivity hybrid organic-inorganic polymer network optical cladding includes:
a network of at least one positive oxidation state element covalently bound by oxo-metal bonds and organic cross-links; and
a trap element covalently bound to the network and configured to conduct electricity by jumping conduction.
2. The electro-optic device of claim 1 , wherein the at least one positive oxidation state element includes silicon, and wherein the oxo-metal bonds include silicate bonds.
3. The electro-optic device of claim 1 , wherein the organic cross-links include at least one of an epoxy or an acrylate cross-linked group.
4. The electro-optic device of claim 1 , wherein the trap element includes tin.
5. The electro-optic device of claim 1 , wherein the tin is covalently bound to the network by at least one selected from the group consisting of oxo-metal bonds and organic cross-links.
6. The electro-optic device of claim 1 , wherein the optical cladding includes antimony covalently bound to at least the tin by at least oxo-metal bonds.
7. An electro-optic device, comprising:
an electro-optic core; and
abutting or proximate the electro-optic core, at least one optical cladding formed as an intrinsically low resistivity hybrid organic-inorganic polymer network, wherein the at least one intrinsically low resistivity hybrid organic-inorganic polymer network optical cladding is prepared according to a sol-gel process; and includes:
wherein:
M is Si, Ti, Al, or Zr,
T is a trap element,
Da is a donor or acceptor element selected to undergo reversible oxidation/reduction with the trap element,
OR is independently at each occurrence, a hydrolysable group,
R 1 is an organic cross-linker,
R 2 is independently at each occurrence, a hydrolysable group, an alkyl group, or an aryl group,
x is 0 or more,
y is 0 or more, and at least one of x and y is 1 or more,
z is the oxidation state of T, minus y,
w is the oxidation state of Da, minus x,
n1 and n2 are within about a factor of 5 of one another,
the sum of n1 and n2 is between about 2 times and 10 times n3, and
the ratio of n3/n4 is about equal to x.
8. The electro-optic device of claim 7 , wherein R 1 is:
wherein:
R is a linear or branched alkyl group; and
R 3 is an alkyl or aryl group.
9. An electro-optic device, comprising:
an electro-optic core; and
abutting or proximate the electro-optic core, at least one optical cladding formed as an intrinsically low resistivity hybrid organic-inorganic polymer network, wherein the at least one intrinsically low resistivity hybrid organic-inorganic polymer optical cladding includes:
wherein:
M is Si, Ti, Al, or Zr,
Sn is tin in its 4+ oxidation state or in its 2+ oxidation state,
Sb is antimony in its 3+ oxidation state if tin is in its 4+ oxidation state or antimony in its 5+ oxidation state if tin is in its 2+ oxidation state,
OR is, independently at each occurrence, a hydrolysable group,
R 1 is an organic cross-linker,
R 2 is independently at each occurrence, a hydrolysable group, an alkyl group, or an aryl group,
x is 0 or more,
y is 0 or more, and at least one of x and y is 1 or more,
z is the oxidation state of Sn, minus y minus 2,
w is the oxidation state of Sb, minus x minus 2,
n1 and n2 are within about a factor of 5 of one another,
the sum of n1 and n2 is between about 2 times and 10 times n3, and
the ratio of n3/n4 is about equal to (x+2).
10. The electro-optic device of claim 9 , wherein Sb is Sb 3+ , x is 1 and w is zero.
11. The electro-optic device of claim 9 , wherein Sb is Sb 5+ , x is 1 to 3 and w is (3-x).
12. The electro-optic device of claim 9 , wherein R 1 is:
wherein:
R is a linear or branched alkyl group; and
R 3 is an alkyl or aryl group.
13. The electro-optic device of claim 9 , wherein the intrinsically low resistivity hybrid organic-inorganic polymer network is made using a sol-gel process.
14. An electro-optic device, comprising:
an electro-optic core; and
abutting or proximate the electro-optic core, at least one optical cladding formed as an intrinsically low resistivity hybrid organic-inorganic polymer network, wherein the at least one intrinsically low resistivity hybrid organic-inorganic polymer network optical cladding includes:
wherein:
wavy lines are organic cross-link bonds or oxo-metal bonds to other parts of the hybrid organic-inorganic polymer network,
R 1 is an organic cross-linker,
—, and —O— are bonds to other parts of the hybrid organic-inorganic polymer network;
the two dots above the Sb 3+ atom indicate an electron pair in the outer orbital,
n1 and n2 are within about a factor of 5 of one another,
the sum of n1 and n2 is between about 2 times and 10 times n3, and
n4 is smaller than n3.
15. The electro-optic device of claim 14 , wherein R 1 is:
wherein:
R is a linear or branched alkyl group; and
R 3 is an alkyl or aryl group.
16. The electro-optic device of claim 14 , wherein:
n1 is about 1.8,
n2 is about 1.8,
n3 is about 1, and
n4 is about 0.33.
17. The electro-optic device of claim 14 , wherein the tin and antimony groups are configured to undergo the reaction:
whereby the tin becomes conductive via jumping conduction; and
wherein:
—, —O—, and —OR are bonds to other parts of the hybrid organic-inorganic polymer network;
R 2 is an organic spacer group or a bond to other parts of the hybrid organic-inorganic polymer network
the two dots above the Sb 3+ atom indicate an electron pair in the outer orbital, and
the dotted arrow indicates a transfer of the electron pair from the outer orbital of the antimony atom to the tin atom.
18. An electro-optic device, comprising:
an electro-optic core; and
abutting or proximate the electro-optic core, at least one optical cladding formed as an intrinsically low resistivity hybrid organic-inorganic polymer network, wherein the at least one intrinsically low resistivity hybrid organic-inorganic optical cladding includes:
wherein:
wavy lines are organic cross-link bonds or oxo-metal bonds to other parts of the hybrid organic-inorganic polymer network,
R 1 is an organic cross-linker,
the two dots above the Sn 2+ atom indicate an electron pair in the outer orbital,
n1 and n2 are within about a factor of 5 of one another,
the sum of n1 and n2 is between about 2 times and 10 times n3, and
n4 is smaller than n3.
19. The electro-optic device of claim 18 , wherein R 1 is:
wherein:
R is a linear or branched alkyl group; and
R 3 is an alkyl or aryl group.
20. The electro-optic device of claim 18 , wherein:
n1 is about 1.8,
n2 is about 1.8,
n3 is about 1, and
n4 is about 0.20.
21. The electro-optic device of claim 18 , wherein the tin and antimony groups are configured to undergo the reaction:
whereby the tin becomes conductive via jumping conduction; and
wherein:
the two dots above the Sn atom indicate an electron pair in the outer orbital,
R 2 is an organic spacer group,
x is 1 or more,
w is (3-x); and
the dotted arrow indicates a transfer of the electron pair from the tin atom to the antimony atom.
22. The electro-optic device of claim 1 , wherein the electro-optic core includes at least one hyperpolarizable organic chromophore and a cross-linked polymer.
23. The electro-optic device of claim 22 , wherein the at least one hyperpolarizable organic chromophore and the polymer form a guest-host material.
24. The electro-optic device of claim 1 , wherein the at least one optical cladding includes a bottom clad and a top clad, the bottom and top clads formed as an intrinsically low resistivity hybrid organic-inorganic polymer network prepared according to a sol-gel process, and wherein the electro-optic core is disposed between the bottom and top clads.
25. The electro-optic device of claim 24 , further comprising at least one organic polymer clad disposed over or under at least one of the bottom or top hybrid clads.
26. The electro-optic device of claim 24 , further comprising:
a substrate;
a bottom electrode disposed on the substrate;
wherein the bottom clad, electro-optic core, and top clad are disposed over the bottom electrode; and
a top electrode disposed over the top clad.
27. The electro-optic device of claim 26 , further comprising a waveguide structure disposed parallel to the top electrode.
28. The electro-optic device of claim 26 , wherein at least one of the top and bottom electrodes is configured as a high speed strip electrode.
29. The electro-optic device of claim 26 , wherein the top and bottom electrodes are configured to provide an electrical drive pulse of about 0.9 to 1.1 volts through the bottom clad, electro-optic core, and top clad.
30. The electro-optic device of claim 26 , wherein the top electrode is configured as a poling electrode.
31. The electro-optic device of claim 24 , wherein:
the bottom clad is about 1-2.0 microns thick;
the electro-optic core is about 3 microns thick at a trench waveguide; and
the top clad is about 0.5 to 2.0 microns thick.
32. The electro-optic device of claim 24 wherein:
the bottom clad is about 2-2.4 microns thick;
the electro-optic core is about 3 microns thick; and
the top clad is about 0.5 to 2.0 microns thick.
33. The electro-optic device of claim 1 , wherein the intrinsically low resistivity hybrid organic-inorganic polymer network includes a covalently bound trap element and a covalently bound electron donor or electron receiver element.
34. A method for making an electro-optic device, comprising:
making an intrinsically low resistivity hybrid organic-inorganic material by:
combining with a first sol-gel precursor including at least three hydrolysable groups;
a second sol-gel precursor including at least two hydrolysable groups and an organic cross-linking group;
a third sol-gel precursor including a trap element bound to at least two hydrolysable groups; and
a fourth sol-gel precursor including an electron donor or acceptor element bound to at least two hydrolysable groups;
to form:
a network of at least one positive oxidation state element covalently bound by oxo-metal bonds and organic cross-links; and
a trap element covalently bound to the network and configured to conduct electricity by jumping conduction;
wherein at least one of the third and fourth sol-gel precursors includes at least three hydrolysable groups;
depositing the intrinsically low resistivity hybrid organic-inorganic material as at least one optical cladding; and
forming an electro-optic core abutting or proximate to the at least one optical cladding.
35. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 34 , wherein:
the first sol-gel precursor and the second sol-gel precursor are mixed and hydrolysed in a part A;
the third sol-gel precursor and the fourth sol-gel precursor are mixed and hydrolysed in a part B; and
the parts A and B are then be combined.
36. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 34 , wherein the first sol-gel precursor and the second sol-gel precursor include silicon.
37. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 34 , wherein the organic cross-linking group of the second sol-gel precursor includes an epoxy or an acrylate.
38. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 37 , wherein the organic cross-linking group includes a glycidoxypropyl group.
39. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 34 , wherein the trap element is tin.
40. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 34 , wherein:
the fourth sol-gel precursor includes an electron donor.
41. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 40 , wherein:
the fourth sol-gel precursor includes antimony or indium.
42. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 34 , wherein:
the fourth sol-gel precursor includes an electron acceptor including antimony in a 5+ oxidation state.
43. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 34 , further comprising:
gelling and organically cross-linking the mixture; and
drying and curing the gel to form a film.
44. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 43 , wherein:
the film forms a hybrid organic-inorganic polymer material having relatively low electrical resistivity arising from jumping conduction between instances of the covalently-bound trap element.
45. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 44 , wherein:
the covalently bound trap element includes tin.
46. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 45 , wherein:
at least a portion of the tin is configured to receive excess electrons from the electron donor element upon at least one of being thermally energized or being exposed to an electric field.
47. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 45 , wherein:
at least a portion of the tin is configured to donate electrons to the electron acceptor element upon at least one of being thermally energized or being exposed to an electric field.
48. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 34 , wherein:
the first sol-gel precursor and the second sol-gel precursor are combined and hydrolysed in a part A according to the reaction:
wherein:
M is, independently at each occurrence, Si, Ti, Al, or Zr;
OR is a hydrolysable group;
R 1 is an organic cross-linker;
R 2 is a hydrolysable group, an alkyl spacer group, or an aryl spacer group; and
n1 and n2 are within a factor of 5 of one another;
wherein the third and fourth sol-gel precursors are combined in a Part B; and
wherein Part A is then combined with Part B to form the intrinsically low resistivity hybrid organic-inorganic material.
49. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 48 , wherein n1 and n2 are within about a factor of 2 of one another.
50. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 34 , wherein:
the first and second sol-gel precursors are combined in a Part A;
wherein the third sol-gel precursor and the fourth sol-gel precursor are mixed and hydrolysed in a part B according to the reaction:
wherein:
the two dots above the Sb 3+ indicate an electron pair,
OR is a hydrolysable group,
R 2 is a hydrolysable group, an alkyl spacer group, or an aryl spacer group, and
n3 is greater than n4; and
wherein Part A is then combined with Part B to form the intrinsically low resistivity hybrid organic-inorganic material.
51. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 48 , wherein the ratio n3/n4 is about equal to 3.
52. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 34 , wherein:
the first and second sol-gel precursors are combined in a Part A;
wherein the third sol-gel precursor and the fourth sol-gel precursor are mixed and hydrolysed in a part B according to the reaction:
wherein:
OR is a hydrolysable group,
R 2 is a hydrolysable group, an alkyl spacer group, or an aryl spacer group, x is between 1 and 3,
n3 is greater than n4; and
wherein Part A is then combined with Part B to form the intrinsically low resistivity hybrid organic-inorganic material.
53. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 48 , wherein the ratio n3/n4 is equal to about x+2.
54. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 34 , further comprising:
gelling and organically cross-linking the mixture; and
drying and curing the gel to form an optical cladding.
55. The method for making an intrinsically low resistivity hybrid organic-inorganic material of claim 34 , further comprising:
combining with the first, second, third and fourth sol-gel precursors, an inorganic salt dopant configured to temporarily further reduce the resistivity of the material.