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EP0287093A2
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Inorganic-organic composite compositons exhibiting nonlinear optical response
Assignee: CNA Holdings LLC
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Filing: 1988-04-14
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Granted: —
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Expires: 2008-04-14
Abstract
Abstract This invention provides an optical medium which consists of an inorganic glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response. In one embodiment this invention provides a sol-gel process for producing a composite of a transparent homogeneous microporous inorganic oxide glass monolith and an organic compound which exhibits nonlinear optical response.
Inventors
- 👤 Tessie M. Che
- 👤 Dagobert E. Stuetz
- 👤 Alan Buckley
- 👤 Donald R. Ulrich
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-04 08:31
CPC Classifications
C; C03; C03C; C03C1/00; C03C1/006; C03C14/00; C03C14/008; C03C23/00; C03C23/0095; C09; C09K; C09K19/00; C09K19/04; C09K19/38; C09K19/3833; C09K19/3842; C09K19/3852; G; G02; G02F; G02F1/00; G02F1/35; G02F1/355; G02F1/3555; G02F1/361; C03C2214/00; C03C2214/17; C03C2214/32; C09K2323/00; C09K2323/06; C09K2323/061
Claims Analysis
Total Claims: 62
Claim 1
Independent Claim
26 words
An optical medium comprising a composite composition of an inorganic oxide glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response.
Claim 2
Dependent Claim
26 words
An optical medium comprising a composite composition of an inorganic oxide glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response.
Claim 3
Dependent Claim
14 words
An optical medium in accordance with claim 1 wherein the inorganic oxide comprises silica.
Claim 4
Dependent Claim
24 words
An optical medium in accordance with claim 1 wherein the inorganic oxide comprises a mixture of silica and at least one additional inorganic oxide.
Claim 5
Dependent Claim
24 words
An optical medium in accordance with claim 1 wherein the glass monolith microporous structure has pore diameters in the range between about 15-2000 angstroms.
Claim 6
Dependent Claim
31 words
An optical medium in accordance with claim 1 wherein the organic component is concentrated in a zone of the microporous structure which is adjacent to a surface of the glass monolith.
Claim 7
Dependent Claim
27 words
An optical medium in accordance with claim 1 wherein the content of the organic component has a gradient distribution in the microporous structure of the glass monolith.
Claim 8
Dependent Claim
18 words
An optical medium in accordance with claim 1 which has a thickness dimension less than about 5 millimeters.
Claim 9
Dependent Claim
26 words
An optical medium in accordance with claim 1 wherein between about 5-95 percent of the glass monolith microporous structure volume is filled with the organic component.
Claim 10
Dependent Claim
22 words
An optical medium in accordance with claim 1 wherein the organic component is characterized by an external field-induced orientation of aligned molecules.
Claim 11
Dependent Claim
36 words
An optical medium in accordance with claim 1 wherein the optical medium exhibits a second order nonlinear optical susceptibility χ (2) of at least about 1 x 10⁻⁶ esu as measured at 1.91 µm excitation wavelength.
Claim 12
Dependent Claim
35 words
An optical medium in accordance with claim 1 wherein the optical medium exhibits a third order nonlinear optical susceptibility χ (3) of at least 1 x 10⁻⁹ esu as measured at 1.91 µm excitation wavelength.
Claim 13
Dependent Claim
39 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic glass monolith with a microporous structure containing an organic component which comprises a compound having a molecular weight less than about 1000 and exhibiting nonlinear optical response.
Claim 14
Dependent Claim
39 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic glass monolith with a microporous structure containing an organic component which comprises a compound having a molecular weight less than about 1000 and exhibiting nonlinear optical response.
Claim 15
Dependent Claim
22 words
A nonlinear optical medium in accordance with claim 12 wherein the organic component is composed of at least one additional organic constituent.
Claim 16
Dependent Claim
24 words
A nonlinear optical medium in accordance with claim 12 wherein the organic component is composed of an additional organic constituent which is thermoplastic polymer.
Claim 17
Dependent Claim
31 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic glass monolith with a microporous structure containing an organic component which comprises a thermoplastic polymer exhibiting nonlinear optical response.
Claim 18
Dependent Claim
31 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic glass monolith with a microporous structure containing an organic component which comprises a thermoplastic polymer exhibiting nonlinear optical response.
Claim 19
Dependent Claim
27 words
A nonlinear optical medium in accordance with claim 15 wherein the organic component is composed of at least one additional organic constituent which exhibits nonlinear optical response.
Claim 20
Dependent Claim
20 words
A nonlinear optical medium in accordance with claim 15 wherein the organic component comprises a side chain liquid crystalline polymer.
Claim 21
Dependent Claim
15 words
A nonlinear optical medium in accordance with claim 15 wherein the organic component comprises 4-nitroaniline.
Claim 22
Dependent Claim
15 words
A nonlinear optical medium in accordance with claim 15 wherein the organic component comprises 2-methyl-4-nitroaniline.
Claim 23
Dependent Claim
15 words
A nonlinear optical medium in accordance with claim 15 wherein the organic component comprises 4-N,N-dimethylamino-4ʹ-nitrostilbene.
Claim 24
Dependent Claim
82 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic oxide glass monolith with a microporous structure containing a quinodimethane compound corresponding to the formula: where R and R¹ are substituents selected from hydrogen and aliphatic, alicyclic and aromatic groups containing between about 1-20 carbon atoms; n is an integer with a value between about 1-3; and at least one of the R substituents is an electron-donating group, and at least one of the R¹ substituents is an electron-withdrawing group.
Claim 25
Dependent Claim
82 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic oxide glass monolith with a microporous structure containing a quinodimethane compound corresponding to the formula: where R and R¹ are substituents selected from hydrogen and aliphatic, alicyclic and aromatic groups containing between about 1-20 carbon atoms; n is an integer with a value between about 1-3; and at least one of the R substituents is an electron-donating group, and at least one of the R¹ substituents is an electron-withdrawing group.
Claim 26
Dependent Claim
22 words
A nonlinear optical medium in accordance with claim 21 wherein the quinodimethane compound is selected from 13,13-diamino-14,14-dicyanodiphenoquinodimethane; 13,13-di(dimethylamino)-14,14-dicyanodiphenoquinodimethane; 13,13-di(diethylamino)-14,14-dicyanodiphenoquinodimethane; 13,13-di(n-hexadecylamino)-14,14-dicyanodiphenoquinodimethane; and 13,13-ethylenediamino-14,14-dicyanodiphenoquinodimethane.
Claim 27
Dependent Claim
72 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic oxide glass monolith with a microporous structure containing a quinodimethane compound corresponding to the formula: where R and R¹ are substituents selected from hydrogen and aliphatic, alicyclic and aromatic groups containing between about 1-20 carbon atoms; and at least one of the R substituents is an electron-donating group, and at least one of the R¹ substituents is an electron-withdrawing group.
Claim 28
Dependent Claim
72 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic oxide glass monolith with a microporous structure containing a quinodimethane compound corresponding to the formula: where R and R¹ are substituents selected from hydrogen and aliphatic, alicyclic and aromatic groups containing between about 1-20 carbon atoms; and at least one of the R substituents is an electron-donating group, and at least one of the R¹ substituents is an electron-withdrawing group.
Claim 29
Dependent Claim
22 words
A nonlinear optical medium in accordance with claim 23 wherein the quinodimethane compound is selected from 13,13-ethylenediamino-14,14-dicyano-4,5,9,10-tetrahydropyrenoquinodimethane; 13,13-diamino-14,14-dicyano-4,5,9,10-tetrahydropyrenoquinodimethane; 13,13-di(dimethylamino)-14,14-dicyano-4,5,9,10-tetrahydropyrenoquinodimethane; 13,13-di(diethylamino)-14,14-dicyano-4,5,9,10-tetrahydropyrenoquinodimethane; and 13,13-di(n-hexadecylamino)-14,14-dicyano-4,5,9,10-tetrahydropyrenoquinodimethane.
Claim 30
Dependent Claim
72 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic oxide glass monolith with a microporous structure containing a quinodimethane compound corresponding to the formula: where R and R¹ are substituents selected from hydrogen and aliphatic, alicyclic and aromatic groups containing between about 1-20 carbon atoms, and at least one of the R substituents is an electron-donating group, and at least one of the R¹ substituents is an electron-withdrawing group.
Claim 31
Dependent Claim
72 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic oxide glass monolith with a microporous structure containing a quinodimethane compound corresponding to the formula: where R and R¹ are substituents selected from hydrogen and aliphatic, alicyclic and aromatic groups containing between about 1-20 carbon atoms, and at least one of the R substituents is an electron-donating group, and at least one of the R¹ substituents is an electron-withdrawing group.
Claim 32
Dependent Claim
20 words
A nonlinear optical medium in accordance with claim 25 wherein the quinodimethane compound is selected from 11,11-diamino-12,12-dicyano-2,6-naphthoquinodimethane; 11,11-di(dimethylamino)-12,12-dicyano-2,6-naphthoquinodimethane; and 11,11-di(n-hexadecylamino)-12,12-dicyano-2,6-naphthoquinodimethane.
Claim 33
Dependent Claim
113 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic glass monolith with a microporous structure containing a thermoplastic polymer which is characterized by a recurring monomeric unit corresponding to the formula: where P is a polymer main chain unit, S is a flexible spacer group having a linear chain length of between about 0-20 atoms, M is a pendant group which exhibits a second order nonlinear optical susceptibility β of at least about 5 x 10⁻³⁰ esu as measured at 1.91 µm excitation wavelength, and where the pendant groups comprise at least about 10 weight percent of the polymer, and the polymer has a glass transition temperature about above 40°C.
Claim 34
Dependent Claim
113 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic glass monolith with a microporous structure containing a thermoplastic polymer which is characterized by a recurring monomeric unit corresponding to the formula: where P is a polymer main chain unit, S is a flexible spacer group having a linear chain length of between about 0-20 atoms, M is a pendant group which exhibits a second order nonlinear optical susceptibility β of at least about 5 x 10⁻³⁰ esu as measured at 1.91 µm excitation wavelength, and where the pendant groups comprise at least about 10 weight percent of the polymer, and the polymer has a glass transition temperature about above 40°C.
Claim 35
Dependent Claim
24 words
A nonlinear optical medium in accordance with claim 29 wherein the optical medium is characterized by an external field-induced orientation of aligned polymer molecules.
Claim 36
Dependent Claim
113 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic glass monolith with a microporous structure containing a thermoplastic polymer which is characterized by a recurring monomeric unit corresponding to the formula: where P is a polymer main chain unit, S is a flexible spacer group having a linear chain length of between about 0-20 atoms, Mʹ is a pendant group which exhibits a third order nonlinear optical susceptibility γ of at least about 1 x 10⁻³⁶ esu as measured at 1.91 µm excitation wavelength, and where the pendant groups comprise at least about 10 weight percent of the polymer, and the polymer has a glass transition temperature above about 40°C.
Claim 37
Dependent Claim
113 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic glass monolith with a microporous structure containing a thermoplastic polymer which is characterized by a recurring monomeric unit corresponding to the formula: where P is a polymer main chain unit, S is a flexible spacer group having a linear chain length of between about 0-20 atoms, Mʹ is a pendant group which exhibits a third order nonlinear optical susceptibility γ of at least about 1 x 10⁻³⁶ esu as measured at 1.91 µm excitation wavelength, and where the pendant groups comprise at least about 10 weight percent of the polymer, and the polymer has a glass transition temperature above about 40°C.
Claim 38
Dependent Claim
24 words
A nonlinear optical medium in accordance with claim 29 wherein the optical medium is characterized by an external field-induced orientation of aligned polymer molecules.
Claim 39
Dependent Claim
91 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic glass monolith with a microporous structure containing a thermoplastic polymer which is characterized by a recurring monomeric unit corresponding to the formula: where P is a polymer main chain unit; m is an integer of at least 3; Sʹ is a flexible spacer group having a linear chain length of between about 1-25 atoms; X is -NR-, -O- or -S-; R is hydrogen or a C₁-C₄ alkyl group; Y is Z is an electron-donating group or an electron-withdrawing group.
Claim 40
Dependent Claim
91 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic glass monolith with a microporous structure containing a thermoplastic polymer which is characterized by a recurring monomeric unit corresponding to the formula: where P is a polymer main chain unit; m is an integer of at least 3; Sʹ is a flexible spacer group having a linear chain length of between about 1-25 atoms; X is -NR-, -O- or -S-; R is hydrogen or a C₁-C₄ alkyl group; Y is Z is an electron-donating group or an electron-withdrawing group.
Claim 41
Dependent Claim
17 words
A nonlinear optical medium in accordance with claim 31 wherein the main chain is a polyvinyl structure.
Claim 42
Dependent Claim
29 words
A nonlinear optical medium in accordance with claim 31 wherein the main chain is selected from a polysiloxane structure; a polyoxyalkylene structure; a polyamide structure; and a polyester structure.
Claim 43
Dependent Claim
68 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic glass monolith with a microporous structure containing a thermoplastic polymer which is characterized by a recurring monomeric unit corresponding to the formula: where m¹ is an integer of at least 5; n is an integer between about 4-20; X¹ is -NR¹, -O- or -S-; R¹ is hydrogen or methyl; and Z¹ is -NO₂, -CN or -CF₃.
Claim 44
Dependent Claim
68 words
A nonlinear optical medium comprising a composite composition of a homogeneous inorganic glass monolith with a microporous structure containing a thermoplastic polymer which is characterized by a recurring monomeric unit corresponding to the formula: where m¹ is an integer of at least 5; n is an integer between about 4-20; X¹ is -NR¹, -O- or -S-; R¹ is hydrogen or methyl; and Z¹ is -NO₂, -CN or -CF₃.
Claim 45
Dependent Claim
40 words
A transparent optical medium which is coated on a transparent or reflective substrate, wherein the optical medium is a composite composition comprising an inorganic oxide glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response.
Claim 46
Dependent Claim
40 words
A transparent optical medium which is coated on a transparent or reflective substrate, wherein the optical medium is a composite composition comprising an inorganic oxide glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response.
Claim 47
Dependent Claim
61 words
A transparent optical medium which is in the form of a thin sheet having a thickness less than about 2 millimeters and which as each side surface coated with a transparent electrically conductive film, wherein the optical medium is a composite composition comprising an inorganic oxide glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response.
Claim 48
Dependent Claim
61 words
A transparent optical medium which is in the form of a thin sheet having a thickness less than about 2 millimeters and which as each side surface coated with a transparent electrically conductive film, wherein the optical medium is a composite composition comprising an inorganic oxide glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response.
Claim 49
Dependent Claim
37 words
An optical light switch or light modulator device with an optical medium element comprising a composite composition consisting of an inorganic oxide glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response.
Claim 50
Dependent Claim
37 words
An optical light switch or light modulator device with an optical medium element comprising a composite composition consisting of an inorganic oxide glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response.
Claim 51
Dependent Claim
26 words
An optical light switch or light modulator device in accordance with claim 37 wherein the optical medium element is in a transparent or potentially transparent state.
Claim 52
Dependent Claim
27 words
An optical light switch or light modulator device in accordance with claim 37 wherein the organic component is characterized by an external field-induced orientation of aligned molecules.
Claim 53
Dependent Claim
48 words
A process for switching or modulating light transmission which comprises introducing an incident fundamental light frequency into a transparent optical medium which is comprised of a composite composition consisting of an inorganic oxide glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response.
Claim 54
Dependent Claim
48 words
A process for switching or modulating light transmission which comprises introducing an incident fundamental light frequency into a transparent optical medium which is comprised of a composite composition consisting of an inorganic oxide glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response.
Claim 55
Dependent Claim
80 words
A process for producing a composite composition comprising a homogeneous inorganic oxide glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response, which comprises hydrolyzing tetraalkoxysilane under acidic or basic pH conditions in a sol-gel reaction medium comprising water, a water-miscible organic solvent and an organic component which exhibits nonlinear optical response, until gellation of the reaction medium is completed, and removing the solvent medium to provide a porous glass monolith with incorporated organic component.
Claim 56
Dependent Claim
80 words
A process for producing a composite composition comprising a homogeneous inorganic oxide glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response, which comprises hydrolyzing tetraalkoxysilane under acidic or basic pH conditions in a sol-gel reaction medium comprising water, a water-miscible organic solvent and an organic component which exhibits nonlinear optical response, until gellation of the reaction medium is completed, and removing the solvent medium to provide a porous glass monolith with incorporated organic component.
Claim 57
Dependent Claim
27 words
A process in accordance with claim 41 wherein substantially all of the pores in the microporous structure have diameters within about a 100 angstrom diameter variation range.
Claim 58
Dependent Claim
13 words
A composite composition produced in accordance with the sol-gel process of claim 41.
Claim 59
Dependent Claim
85 words
A process for producing a composite composition comprising an inorganic oxide glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response, which comprises (1) hydrolyzing tetraalkoxysilane under acidic or basic pH conditions in a sol-gel reaction medium comprising water and a water-miscible organic solvent component until gellation of the reaction medium is completed; (2) removing the solvent medium to provide a porous glass monolith; and (3) impregnating the porous glass monolith with an organic component which exhibits nonlinear optical response.
Claim 60
Dependent Claim
85 words
A process for producing a composite composition comprising an inorganic oxide glass monolith with a microporous structure containing an organic component which exhibits nonlinear optical response, which comprises (1) hydrolyzing tetraalkoxysilane under acidic or basic pH conditions in a sol-gel reaction medium comprising water and a water-miscible organic solvent component until gellation of the reaction medium is completed; (2) removing the solvent medium to provide a porous glass monolith; and (3) impregnating the porous glass monolith with an organic component which exhibits nonlinear optical response.
Claim 61
Dependent Claim
27 words
A process in accordance with claim 44 wherein substantially all of the pores in the microporous structure have diameters within about a 100 angstrom diameter variation range.
Claim 62
Dependent Claim
12 words
A composite composition produced in accordance with the process of claim 44.
References Cited (Backward Citations)
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