# US 10,503,065 B2 · Photolithographic patterning of devices > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,503,065 B2 - Document ID: US10503065B2 - Status: Granted - Kind: B2 - Application number: 15/501,128 - Filed: 2015-07-31 - Published: 2017-08-03 - Granted: 2019-12-10 - Earliest claimed: 2014-08-01 - Assignees: Orthogonal, Inc. - Applicants: Orthogonal, Inc. - Inventors: Terrence Robert O'Toole; John Andrew DeFranco; Frank Xavier Byrne - Web page: https://patentgrep.com/patent/US10503065B2 ## CPC - G03F 7/0046: {with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence)} - C11D 7/505: {Mixtures of (hydro)fluorocarbons} - G03F 7/0002: {Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping} - G03F 7/0035: {Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface} - G03F 7/038: Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021) - G03F 7/0392: {the macromolecular compound being present in a chemically amplified positive photoresist composition} - G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain} - G03F 7/325: {Non-aqueous compositions} - G03F 7/40: Treatment after imagewise removal, e.g. baking - H10K 71/221: {by lift-off techniques} - H10K 71/233: {by photolithographic etching} - H10K 71/40: Thermal treatment, e.g. annealing in the presence of a solvent vapour - G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G) - C11D: DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL - H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES ## Abstract A method of patterning a device is disclosed using a resist precursor structure having at least two fluoropolymer layers. A first fluoropolymer layer includes a first fluoropolymer material having a fluorine content of at least 50% by weight and is substantially soluble in a first hydrofluoroether solvent or in a first perfluorinated solvent, but substantially less soluble in a second hydrofluoroether solvent relative to both the first hydrofluoroether and the first perfluorinated solvent. The second fluoropolymer layer includes a second fluoropolymer material having a fluorine content less than that of the first fluoropolymer material and is substantially soluble in the first or second hydrofluoroether solvents, but substantially less soluble in the first perfluorinated solvent relative to both the first and second hydrofluoroether solvents. ## Claims ### Claim 1 A method of patterning a device, comprising: a) over a device substrate, forming a resist precursor structure including i) a first fluoropolymer layer including a first fluoropolymer material having a fluorine content of at least 50% by weight and substantially soluble in a first hydrofluoroether solvent or in a first perfluorinated solvent, but substantially less soluble in a second hydrofluoroether solvent relative to both the first hydrofluoroether and the first perfluorinated solvent, and ii) a second fluoropolymer layer including a second fluoropolymer material having a fluorine content less than that of the first fluoropolymer material and substantially soluble in the first or second hydrofluoroether solvents, but substantially less soluble in the first perfluorinated solvent relative to both the first and second hydrofluoroether solvents; and b) photo-lithographically forming a patterned resist structure and a complementary pattern of uncovered substrate, wherein such forming includes contact of at least a portion of the second fluoropolymer layer with a first fluorinated developing agent comprising the first or second hydrofluoroether solvent. ### Claim 2 (depends on 1) The method of claim 1 further including treating the device substrate to form an intermediate patterned device structure, wherein the patterned resist structure acts as mask. ### Claim 3 (depends on 1) The method of claim 1 further including removing a top layer of the patterned resist structure by contact with a lift-off agent comprising a third hydrofluoroether solvent that is optionally the same as the first hydrofluoroether solvent or the second hydrofluoroether solvent, or a second perfluorinated solvent that is optionally the same as first perfluorinated solvent. ### Claim 4 (depends on 1) The method of claim 1 wherein the resist precursor structure further comprises a third photopolymer layer provided over the first and second fluoropolymer layers. ### Claim 5 (depends on 4) The method of claim 4 wherein the third photopolymer layer is provided from a photosensitive polymer material composition comprising at least 50% by weight of one or more non-fluorinated coating solvents. ### Claim 6 (depends on 5) The method of claim 5 wherein the photo-lithographically forming step includes exposing the third photopolymer layer to patterned radiation to form an exposed photopolymer layer and contacting the exposed photopolymer layer with an aqueous or non-fluorinated organic developing agent to form a first pattern of photopolymer and a complementary second pattern of uncovered fluoropolymer. ### Claim 7 (depends on 6) The method of claim 6 wherein the first fluorinated developing agent comprises the first hydrofluoroether thereby removing uncovered portions of the first and second fluoropolymer layers to form the patterned resist structure and the complementary pattern of uncovered substrate corresponding to the second pattern. ### Claim 8 (depends on 6) The method of claim 6 wherein the second fluoropolymer layer is provided over the first fluoropolymer layer, and wherein the first fluorinated developing agent comprises the second hydrofluoroether which removes uncovered portions of the second fluoropolymer layer to form a pattern of uncovered first fluoropolymer layer. ### Claim 9 (depends on 8) The method of claim 8 further comprising contacting the uncovered first fluoropolymer layer with a second fluorinated developing agent comprising the first perfluorinated solvent or the first hydrofluoroether solvent to form the patterned resist structure and the complementary pattern of uncovered substrate corresponding to the second pattern. ### Claim 10 (depends on 6) The method of claim 6 wherein the first fluoropolymer layer is provided over the second fluoropolymer layer, and prior to contacting with the first fluorinated developing agent, further comprising contacting at least a portion of the first fluoropolymer layer with a second fluorinated developing agent comprising the first perfluorinated solvent. ### Claim 11 (depends on 5) The method of claim 5 wherein the third photopolymer layer further comprises a fluorinated surfactant. ### Claim 12 (depends on 4) The method of claim 4 wherein the third photopolymer layer is a negative tone photoresist. ### Claim 13 (depends on 4) The method of claim 4 wherein the first fluoropolymer layer is provided over the second fluoropolymer layer, and the third photopolymer layer is a photosensitive fluoropolymer provided from a composition comprising a hydrofluoroether coating solvent. ### Claim 14 (depends on 13) The method of claim 13 wherein the photo-lithographically-forming step includes exposing the third photopolymer layer to patterned radiation to form an exposed photopolymer layer and contacting the exposed photopolymer layer with the first fluorinated developing agent to form a first pattern of photopolymer. ### Claim 15 (depends on 14) The method of claim 14 wherein the first fluorinated developing agent comprises the first hydrofluoroether that further removes uncovered portions of the first and second fluoropolymer layers to form the patterned resist structure and the complementary pattern of uncovered substrate corresponding to the second pattern. ### Claim 16 (depends on 1) The method of claim 1 wherein the second fluoropolymer layer is a fluorinated photopolymer layer provided over the first fluoropolymer layer from a composition comprising the second fluoropolymer material, which is a photosensitive fluoropolymer material, and a hydrofluoroether coating solvent. ### Claim 17 (depends on 16) The method of claim 16 wherein the photo-lithographically-forming step includes exposing the fluorinated photopolymer layer to patterned radiation to form an exposed photopolymer layer and contacting the exposed photopolymer layer with the first fluorinated developing agent to form a first pattern of photopolymer. ### Claim 18 (depends on 17) The method of claim 17 wherein the first fluorinated developing agent comprises the first hydrofluoroether that further removes uncovered portions of the first and fluoropolymer layer to form the patterned resist structure and the complementary pattern of uncovered substrate corresponding to the second pattern. ### Claim 19 (depends on 1) The method of claim 1 wherein the first hydrofluoroether solvent is saturated having at least four more perfluorinated carbon atoms than hydrogen-containing carbon atoms. ### Claim 20 (depends on 1) The method of claim 1 wherein the first hydrofluoroether solvent is a saturated segregated hydrofluoroether having at least five perfluorinated carbon atoms and less than three hydrogen-containing carbon atoms. ### Claim 21 (depends on 1) The method of claim 1 wherein the second hydrofluoroether solvent is saturated having fewer than four more perfluorinated carbon atoms than hydrogen-containing atoms and has a fluorine content of at least 60% by weight. ### Claim 22 (depends on 1) The method of claim 1 wherein the second hydrofluoroether solvent is a saturated segregated hydrofluoroether having less than five perfluorinated carbon atoms or is a non-segregated hydrofluoroalkylether. ### Claim 23 (depends on 1) The method of claim 1 wherein the first perfluorinated solvent is an unsaturated perfluorocarbon, perfluoroether or perfluoroalkyl amine. ### Claim 24 (depends on 1) The method of claim 1 wherein the first fluoropolymer material comprises a fluorinated cyclic structure. ### Claim 25 (depends on 1) The method of claim 1 wherein the first fluoropolymer material comprises a perfluorinated cyclic ether or dioxol. ### Claim 26 (depends on 1) The method of claim 1 wherein the second fluoropolymer material is not perfluorinated. ### Claim 27 (depends on 1) The method of claim 1 wherein the second fluoropolymer material includes a repeating unit having a fully or partially fluorinated alkyl or alkyl ether group. ### Claim 28 (depends on 1) The method of claim 1 wherein the second fluoropolymer material includes a copolymer comprising a first repeating unit having a fluorinated group and a second repeating unit having a non-fluorinated alkyl or alkyl ether group. ### Claim 29 (depends on 1) The method of claim 1 wherein the second fluoropolymer material is formed from one or more monomers comprising an acrylate or an acrylate derivative. ### Claim 30 (depends on 1) The method of claim 1 wherein the patterned resist structure has an undercut profile.