# US 2003/0201429 A1 · Low loss electro-optic polymers and devices made therefrom > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2003/0201429 A1 - Document ID: US20030201429A1 - Status: Published application - Kind: A1 - Application number: 10/136,869 - Filed: 2002-04-30 - Published: 2003-10-30 - Earliest claimed: 2002-04-30 - Inventors: Mingqian He; Paul J. Shustack; Jianguo Wang - Web page: https://patentgrep.com/patent/US20030201429A1 ## CPC - G02F 1/3617: {having the non-linear optical group in a side chain} - G02F 1/3614: {Heterocycles having S as heteroatom} - G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS ## Abstract The synthesis of novel, high μβ electro-optical chromophores is described. These chromophores are polymerizable with a host polymer or copolymer. The chromophore polymerizable groups comprise epoxy, thioepoxy, oxetane and thiooxetane material which undergo a ring opening polymerization reaction in the presence of a cationic photoinitiator and actinic radiation. The high μβ chromophores, mixed with a selected host polymer, copolymer, oligomer, or one or a plurality of polymerizable monomers, can be used to prepare optical waveguides and other optical elements and/or devices. The electro-optical chromophores of the invention can be used as a replacement for LiNbO3 in the formation of electro-optical devices, particularly electro-optical modulators. ## Claims ### Claim 1 An electro-optic chromophore comprising a compound whose formula is represented by the structure 13 wherein (a) D is an electron donor having one or a plurality of terminally pendent, polymerizable cyclic ether or cyclic thioether groups; (b) B is or contains at least one bivalent aromatic ring; and (c) R2 and R3 are each, independently, either H or a substituted or unsubstituted C1-C10 alkyl, a substituted or unsubstituted C2-C10 alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted alkylaryl, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocycle, or a substituted or unsubstituted cyclohexyl; or R2 and R3 together form a ring structure or substituted ring structure ### Claim 2 (depends on 1) The chromophore according to claim 1, wherein D terminally contains one or a plurality of polymerizable groups selected from the group consisting of epoxy, episulfide, oxetane and thietane. ### Claim 3 (depends on 1) The chromophore according to claim 1, wherein D is selected from the group consisting of -p-C6H4-AR4 or -p-C6H4-p-C6H4-AR4, and -naphthalene-C6H4-AR4, wherein: (a) A is S or NR5, (b) R4 is selected from the group consisting of epoxy, episulfide, oxetane and thietane, and (c) R5 is selected from the group consisting of C1-C6 alkyls, epoxy, episulfide, oxetane and thietane. ### Claim 4 (depends on 2) The compound according to claim 2, wherein said compound is cationically polymerizable or thermally polymerizable with second compound selected from the group consisting of polymers and oligomers having pendent groups reactable with the groups pendent from D. ### Claim 5 (depends on 3) The compound according to claim 3, wherein said compound is cationically polymerizable or thermally polymerizable with second compound selected from the group consisting of polymers and oligomers having pendent groups reactable with the groups pendent from D. ### Claim 6 An electro-optic chromophore comprising a compound whose formula is represented by the structure 14 wherein (a) Z is O or S; (b) R1 and R1a each are, independently, H or a C1-C10 alkyl group; (c) R2 and R3 each are, independently, H, a substituted or unsubstituted C1-C10 alkyl, a substituted or unsubstituted C2-C10 alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted alkylaryl, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocycle, or a substituted or unsubstituted cyclohexyl; or R2 and R3 together form a ring structure or substituted ring structure; (d) q is in the range of 1 to 3; and (e) D is an electron donor having one or a plurality of terminally pendent, polymerizable cyclic ether or cyclic thioether groups. ### Claim 7 (depends on 6) The chromophore according to claim 6, wherein D contains one or a plurality of terminal polymerizable moieties from the group consisting of epoxy, episulfide, oxetane and thietane. ### Claim 8 (depends on 6) The compound according to claim 6, wherein said compound is cationically polymerizable or thermally polymerizable, and will form copolymers with additional cationically polymerizable or thermally polymerizable monomers and/or oligomers. ### Claim 9 (depends on 7) The compound according to claim 7, wherein said compound is cationically polymerizable or thermally polymerizable, and will form copolymers in the presence of additional cationically polymerizable or thermally polymerizable monomers and/or oligomers. ### Claim 10 A non-linear optical chromophore comprising a compound whose formula is represented by the structure 15 wherein (a) A is S or NR5, (b) R4 is selected from the group consisting of epoxy, episulfide, oxetane and thietane, and (c) R5 is selected from the group consisting of C1-C6 alkyls, epoxy, episulfide, oxetane and thietane. ### Claim 11 (depends on 10) The compound according to claim 10, wherein said compound is cationically polymerizable or thermally polymerizable with second compound selected from the group consisting of polymers and oligomers having pendent groups reactable with the groups pendent from R4A. ### Claim 12 (depends on 10) The compound according to claim 10, wherein said compound is cationically of thermally polymerizable with polymers and oligomers having pendent groups reactable with the groups pendent from R4A, said polymers and oligomers being selected from the group consisting of polyacrylates, polymethacrylates, polyethers and polythioethers, polysulfones, polyesters, maleimide-acrylate or methacrylate copolymers or oligomers, vinyl carboxylates, vinyl acetate or chloride, ethylene, propylene, stryrene, and similar polymers or oligomers known in the art. ### Claim 13 A photocurable composition suitable for the fabrication of electro-optical elements and devices, said composition comprising: (a) a non-linear optical chromophore comprising a compound whose formula is represented by the following Structure II 16 wherein (i) D is an electron donating group having one or a plurality of terminally pendent, polymerizable cyclic ether or cyclic thioether groups; (ii) Z is O or S, (iii) R1 and R1a are H or a C1-C10 alkyl group; and (iv) R2 and R3 each are, independently, H, a substituted or unsubstituted C1-C10 alkyl, a substituted or unsubstituted C2-C10 alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted alkylaryl, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocycle, or a substituted or unsubstituted cyclohexyl; or R2 and R3 together form a ring structure or substituted ring structure (v) q is in the range of 1-3; and (b) a host polymer or oligomers containing the groups reactive with the chromophore's reactive groups; and (c) a cationic photoinitiator. ### Claim 14 (depends on 13) The chromophore according to claims 13, wherein the host polymer or oligomer reactive with the chromophore's reactive groups are selected from the group consisting of acrylates, methacrylates, polyethers and polythioethers, polyesters, maleimide acrylates and methacrylates copolymers, vinyl carboxylates, vinyl acetate and vinyl chloride, ethylene, propylene, and styrene. ### Claim 15 (depends on 13) The composition according to claim 13, wherein the host polymer is a copolymer of a maleimide first monomer, and one or a plurality of second monomers. ### Claim 16 (depends on 13) The composition according to claim 13, wherein the host polymer is a copolymer of a maleimide first monomer, and a second monomer selected from the group consisting of acrylates and methacrylates. ### Claim 17 (depends on 13) The composition according to claim 13, wherein D is selected from the group consisting of -p-C6H4-AR4 or -p-C6H4-p-C6H4-AR4, wherein (a) A is S or NR5, (b) R4 is selected from the group consisting of epoxy, episulfide, oxetane and thietane, and (c) R5 is selected from the group consisting of C1-C6 alkyls, epoxy, episulfide, oxetane and thietane. ### Claim 18 (depends on 15) The composition according to claim 15, wherein said plurality of second monomers comprise a glycidyl methacrylate monomer and a highly fluorinated acrylate monomer. ### Claim 19 (depends on 13) The composition according to claim 13 wherein, when photocured and on a photoinitiator-excluded basis, the cured composition comprises 1-40 volume percent chromophore and 99-60 volume percent copolymer. ### Claim 20 (depends on 13) The composition according to claim 13, wherein when photocured the cured composition exhibits a r33 value greater than 12 pm/V at a wavelength of 1550 nm. ### Claim 21 (depends on 16) The composition according to claim 16, wherein when photocured the cured composition exhibits a r33 value greater than 15 pm/V at 1550 nm. ### Claim 22 (depends on 13) The composition according to claim 13, wherein R2 is -4-cyclohexylphenyl and R3 is methyl. ### Claim 23 (depends on 17) The composition according to claim 17, wherein R2 is -4-cyclohexylphenyl and R3 is methyl. ### Claim 24 An optical device or element made from a photocured composition comprising: (a) a compound whose formula is represented by the structure 17 wherein (i) D is an electron donor having one or a plurality of terminally pendent, polymerizable cyclic ether or cyclic thioether groups; (ii) B is or contains at least one bivalent aromatic ring; and (iii) R2 and R3 are each, independently, either H or a substituted or unsubstituted C1-C10 alkyl, a substituted or unsubstituted C2-C10 alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted alkylaryl, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocycle, or a substituted or unsubstituted cyclohexyl; or R2 and R3 together form a ring structure or substituted ring structure (b) a copolymer of (i) a maleimide first monomer and (ii) one or a plurality of second monomers. ### Claim 25 (depends on 20) The composition according to claim 20, wherein said plurality of second monomers comprise a glycidyl methacrylate monomer and a highly fluorinated acrylate monomer. ### Claim 26 (depends on 20) The device or element according to claim 20, wherein said element is an optical waveguide. ### Claim 27 (depends on 21) The device or element according to claim 21, wherein said element is an optical waveguide. ### Claim 28 (depends on 20) The device or element according to claim 20, wherein the value of r33 is greater than 15 pm/V at a wavelength of 1550 nm. ### Claim 29 (depends on 21) The device or element according to claim 21, wherein the value of r33 is greater than 15 at a wavelength of 1550 nm. ### Claim 30 A method for fabricating an optical or electro-optic structure containing a photodefinable high μβ chromophore layer, said method comprising the steps of: (a) applying to a substrate a composition containing a chromophore having at least one terminal cationically polymerizable group to form a photopolymerizable composition layer, said composition including at least one cationic photoinitiator; (b) imagewise exposing the photopolymerizable composition layer to sufficient actinic radiation to effect the at least partial polymerization of an imaged portion and to form at least one non-imaged portion of said composition layer; (c) removing said at least one non-imaged portion without removing said imaged portion, thereby forming a light transmissive pattern from said imaged portion; (d) applying an cladding polymerizable composition onto the patterned layer; and (e) at least partially curing said cladding composition, wherein said cladding and the core-interfacing surface of said support have a lower refractive index than said core. ### Claim 31 (depends on 26) The method according to claim 26, wherein the high μβ chromophore layer composition comprises a chromophore whose formula is represented by the structure: 18 wherein (a) D is an electron donor having one or a plurality of terminally pendent, polymerizable cyclic ether or cyclic thioether groups; (b) B is or contains at least one bivalent aromatic ring; and (c) R2 and R3 are each, independently, either H or a substituted or unsubstituted C1-C10 alkyl, a substituted or unsubstituted C2-C10 alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted alkylaryl, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocycle, or a substituted or unsubstituted cyclohexyl; or R2 and R3 together form a ring structure or substituted ring structure. ### Claim 32 (depends on 27) The method according to claim 27, wherein said cyclic ethers and cyclic thioethers are selected from the group consisting of epoxy, episulfide, oxetane and thietane. ### Claim 33 (depends on 26) The composition according to claim 26, wherein when photocured the cured composition exhibits a r33 value greater than 15 pm/V at 1550 nm. ### Claim 34 A method for fabricating an optical or electro-optic structure containing a photodefinable high μβ chromophore, said method comprising the steps of: (a) spin coating a substrate with a first polymeric cladding layer material having an refractive index less than the refractive index of the chromophore containing material that will be subsequently applied; (b) exposing the material of Step (a) to actinic radiation for a selected time, followed by baking at a selected temperature for a selected time to form a substrate having a first bottom cladding layer adhered thereto; (c) spin coating on the first cladding material a second cladding layer material having an refractive index less than that of the chromophore containing waveguide material that will be subsequently applied, followed by prebaking at a selected temperature for a selected time; (d) placing a positive photomask over the second cladding material and applying actinic radiation followed by a baking at a selected temperature for a selected time to produce a form of an optical or electro-optical element or device; (e) developing the form of Step (d) by washing away uncured polymer with a solvent in which the second cladding material is soluble; (f) spin coating a high μβ chromophore/polymer composition containing a cationic photoinitiator to the form of Step (e) and curing same in an inert atmosphere by application of actinic radiation, followed by baking in an inert atmosphere, at a selected temperature for a selected time to thereby form an optical or electro-optical structure containing a high μβ chromophore; (g) spin coating a top overcladding material on the structure of Step (e), and curing same as described in Step (b) to produce said optical or electro-optical element or device wherein said chromophore contains terminal reactive moieties selected from the group consisting of cyclic ethers and cyclic thioethers. ### Claim 35 (depends on 30) The method according to claim 30, wherein said high μβ chromophore composition spin coated to form said structure comprises: (a) a chromophore whose formula is represented by the structure 19 wherein (i) D is an electron donating group having one or a plurality of terminally pendent, polymerizable cyclic ether or cyclic thioether moieties; (ii) Z is or S, (iii) R1 and R1a are H or a C1-C10 alkyl group; and (iv) R2 and R3 each are, independently, H, a substituted or unsubstituted C1-C10 alkyl, a substituted or unsubstituted C2-C10 alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted alkylaryl, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocycle, or a substituted or unsubstituted cyclohexyl; or R2 and R3 together form a ring structure or substituted ring structure (v) q is in the range of 1-3; and (b) a host polymer or oligomer being selected from the group consisting of polyacrylates, polymethacrylates, polyethers and polythioethers, polysulfones, polyesters, maleimide-acrylate or methacrylate copolymers or oligomers, vinyl carboxylates, vinyl acetate or chloride, ethylene, propylene, stryrene, and similar polymers or oligomers known in the art. ### Claim 36 (depends on 31) The method according to claim 31, wherein said host polymer is a copolymer of a maleimide first monomer and one or a plurality of second monomers, said host polymer having terminal groups reactive with the terminal groups of said chromophore. ### Claim 37 (depends on 30) The method according to claim 30, wherein said cyclic ethers and cyclic thioethers are selected from the group consisting of epoxy, episulfide, oxetane and thietane. ### Claim 38 (depends on 31) The method according to claim 31, wherein said cyclic ethers and cyclic thioethers are selected from the group consisting of epoxy, episulfide, oxetane and thietane. ### Claim 39 (depends on 30) The chromophore/polymer composition according to claim 30, wherein when photocured the cured composition exhibits a r33 value greater than 15 pm/V at 1550 nm.