# US 5,344,522 A · Pattern forming process and process for preparing semiconductor device utilizing said pattern forming process > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,344,522 A - Document ID: US5344522A - Status: Granted - Kind: A - Application number: 08/013,180 - Filed: 1993-01-29 - Granted: 1994-09-06 - Earliest claimed: 1990-05-09 - Assignees: Canon Kabushiki Kaisha - Inventors: Takayuki Yagi; Toshiyuki Komatsu; Yasue Sato; Shinichi Kawate - Web page: https://patentgrep.com/patent/US5344522A ## CPC - H10P 50/71: {using masks for conductive or resistive materials} - G03F 7/16: Coating processes; Apparatus therefor (applying coatings to base materials in general B05; applying photosensitive compositions to base for photographic purposes G03C1/74) - G03F 7/167: {from the gas phase, by plasma deposition (G03F7/2035 takes precedence)} - G03F 7/2043: {with the production of a chemical active agent from a fluid, e.g. an etching agent; with meterial deposition from the fluid phase, e.g. contamination resists} - H10P 50/692: {characterised by their composition, e.g. multilayer masks or materials} - H10P 50/73: {using masks for insulating materials} - Y10S 438/908: Utilizing cluster apparatus - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - 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) - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract A process for forming an etching pattern, which includes selectively irradiating a light to a clean surface of a material to be worked by etching so as to form radicals from a photoradical forming substance in an atmosphere of the substance, forming a modified portion having an etching resistance at a photo-irradiated portion of the surface, and then subjecting an unmodified portion of the surface of the material to be worked to an etching treatment, thereby forming an etching pattern corresponding to a pattern formed by the irradiation. ## Claims ### Claim 1 A process for forming an etching pattern, comprising the steps of: selectively irradiating light to a clean surface of a material to be worked by etching, so as to form radicals from a photoradical forming substance in an atmosphere of the substance, the light having a wavelength not longer than the UV-ray absorption end of the photoradical forming substance; forming a modified portion having etching resistance at a photo-irradiated portion of the surface; and then subjecting an unmodified portion of the surface of the material to be worked to an etching treatment comprising dry etching using halogen atom radicals, thereby forming an etching pattern corresponding to a pattern formed by said light irradiation. ### Claim 2 (depends on 1) A process for forming an etching pattern according to claim 1, wherein the clean surface of said material to be worked by etching is formed by irradiating radicals obtained from at least one of the group consisting of hydrogen gas and inert gases to the surface of the material to be worked by etching. ### Claim 3 (depends on 1) A process for forming an etching pattern according to claim 1, wherein the clean surface of said material to be worked by etching forms the modified portion without exposing a thin film formed by a thin film forming method to air. ### Claim 4 (depends on 1) A process for forming an etching pattern according to claim 1, further comprising forming the clean surface of the material to be worked by etching by modifying the surface of a thin film formed by a thin film forming method by irradiating the thin film with one of hydrogen ions and fluorine ions. ### Claim 5 (depends on 1) A process for forming an etching pattern according to claim 1, wherein said photoradical forming substance is a substance for forming oxygen radicals. ### Claim 6 (depends on 5) A process for forming an etching pattern according to claim 5, wherein said photoradical forming substance is at least one substance selected from the group consisting of oxygen, ozone, nitrous oxide, carbon dioxide and nitrogen dioxide. ### Claim 7 (depends on 1) A process for forming an etching pattern accoridng to claim 1, wherein the surface of said material to be worked comprises at least one material selected from the group consisting of Al, Si, SiN, C, Ge, GaAs, Ti, Ta, Mo, W and Nb. ### Claim 8 (depends on 1) A process for forming an etching pattern according to claim 1, wherein said light irradiation is effected through a photomask. ### Claim 9 (depends on 1) A process for forming an etching pattern according to claim 1, wherein said dry etching is carried out by using at least one substance selected from the group consisting of Cl.sub.2, CF.sub.3 Cl, CCl.sub.4 and NF.sub.3. ### Claim 10 (depends on 1) A process for forming an etching pattern according to claim 1, wherein said halogen atom radicals are selected from the group consisting of chlorine radicals and fluorine radicals. ### Claim 11 (depends on 8) A process for forming an etching pattern according to claim 8, wherein said photomask has a light shielding pattern and a light absorbing member provided corresponding to said light shielding pattern. ### Claim 12 (depends on 1) A process for forming an etching pattern according to claim 1, wherein the formation of said modified portion and said etching treatment are carried out in different treatment spaces. ### Claim 13 (depends on 12) A process for forming an etching pattern according to claim 12, further comprising moving the material to be worked between the different treatment spaces through a conveying chamber adjacent to each of the treatment spaces. ### Claim 14 (depends on 13) A process for forming an etching pattern according to claim 13, further comprising providing a gate valve between the conveying chamber and each of the treatment spaces. ### Claim 15 A process for forming an etching pattern, comprising the steps of: providing a resist pattern of a polymerized film formed by a CVD method on a clean surface of a material to be worked by etching; and then subjecting the surface of the material to be worked having the resist pattern provided thereon to an etching treatment. ### Claim 16 (depends on 15) A process for forming an etching pattern according to claim 15, wherein the clean surface of said material to be worked by etching is formed by irradiating a plasma obtained from at least one selected from the group consisting of hydrogen gas and inert gases to the surface of the material to be worked by etching. ### Claim 17 (depends on 15) A process for forming an etching pattern according to claim 15, wherein the clean surface of said material to be worked by etching forms said resist pattern without exposing a thin film formed by a thin film forming method to air. ### Claim 18 (depends on 15) A process for forming an etching pattern according to claim 15, wherein the clean surface of said material to be worked by etching is formed by modifying the surface of a thin film formed by a thin film forming method by irradiating the thin film with one of hydrogen ion and fluorine ions. ### Claim 19 (depends on 15) A process for forming an etching pattern according to claim 15, wherein said step of providing a resist pattern comprises the steps of forming a polymerized film on the clean surface of the material to be worked by etching by a CVD method and selectively removing a desired portion of said polymerized film. ### Claim 20 (depends on 19) A process for forming an etching pattern according to claim 19, wherein the selective removal of the desired portion from the polymerized film is carried out by irradiating light to the desired portion of said polymerized film in an atmosphere of a photoradical forming substance, thereby causing decomposition to remove the polymerized film at a portion irradiated with the light by the generated radicals. ### Claim 21 (depends on 19) A process for forming an etching pattern according to claim 19, wherein the selective removal of the polymerized film at the desired portion is carried out by irradiating light capable of decomposing and removing said polymerized film by heat generation to the desired portion of said polymerized film. ### Claim 22 (depends on 20) A process for forming an etching pattern according to claim 20, wherein the photoradical forming substance is one forming oxygen radicals. ### Claim 23 (depends on 22) A process for forming an etching pattern according to claim 22, wherein the photoradical forming substance is at least one selected from the group consisting of oxygen, nitrogen dioxide, ozone, nitrous oxide and carbon dioxide. ### Claim 24 (depends on 15) A process for forming an etching pattern according to claim 15, wherein the polymerized film comprises a hydrocarbon compound of which at least a portion of the hydrogen thereof is substituted by at least one selected from the group consisting of fluorine and chlorine. ### Claim 25 (depends on 15) A process for forming an etching pattern according to claim 15, wherein said etching treatment is effected by using halogen element radicals. ### Claim 26 (depends on 15) A process for forming an etching pattern according to claim 15, wherein said etching treatment is a dry etching. ### Claim 27 (depends on 26) A process for forming an etching pattern according to claim 26, wherein said dry etching is carried out by using a compound capable of generating halide radicals. ### Claim 28 (depends on 27) A process for forming an etching pattern according to claim 27, wherein said halide radicals are selected from the group consisting of chlorine radicals and fluorine radicals. ### Claim 29 (depends on 27) A process for forming an etching pattern according to claim 27, wherein said compound is at least one selected from the group consisting of Cl.sub.2, CF.sub.3 Cl, CCl.sub.4 and NF.sub.3. ### Claim 30 (depends on 20) A process for forming an etching pattern according to claim 20, wherein said light irradiation is effected through a photomask. ### Claim 31 (depends on 30) A process for forming an etching pattern according to claim 30, wherein said photomask has a light shielding pattern and a light absorbing member provided corresponding to said light shielding pattern. ### Claim 32 (depends on 15) A process for forming an etching pattern according to claim 15, wherein the formation of said resist pattern of the polymerized film and said etching treatment are carried out in different treatment spaces. ### Claim 33 (depends on 32) A process for forming an etching pattern according to claim 32, further comprising moving the material to be worked between the different treatment spaces through a conveying chamber adjacent to each of the treatment spaces. ### Claim 34 (depends on 33) A process for forming an etching pattern according to claim 33, further comprising providing a gate valve between the conveying chamber and each of the treatment spaces. ### Claim 35 (depends on 15) A process for forming an etching pattern according to claim 15, wherein the surface of said material to be worked comprises at least one material selected from the group consisting of Al, Si, Cr, Au, CdS, GaAs and Ge. ### Claim 36 A process for forming a semiconductor device comprising the steps of: cleaning a surface of a substrate; depositing a film of one of a semiconductor, a metal and an insulator on the substrate cleaned in said cleaning; forming a mask by irradiating the substrate with a selected light to form a desired device structure on the film deposited in said depositing step; and effecting etching by using the mask formed in said forming step as a light shielding member, wherein each of the cleaning, depositing, forming and etching steps are consistently carried out in a state shielded from air and under a reduced pressure. ### Claim 37 (depends on 36) A process for preparing a semiconductor device according to claim 36, wherein said selective light irradiating step is carried out in a reactive gas atmosphere to modify the surface of the film deposited on the substrate in said film depositing step. ### Claim 38 (depends on 36) A process for preparing a semiconductor device according to claim 36, wherein a photoetching by selective photo-irradiation is effected in place of said mask forming step and said photoetching step. ### Claim 39 (depends on 36) A process for forming a semiconductor device according to claim 36, wherein said cleaning step is carried out by irradiating radicals obtained from at least one of the group consisting of hydrogen gas and inert gases to the surface of the substrate. ### Claim 40 (depends on 36) A process for forming a semiconductor device according to claim 36, wherein said mask forming step is carried out in an atmosphere of a substance that forms photoradicals by irradiation with light for forming the photoradicals. ### Claim 41 (depends on 40) A process for forming a semiconductor device according to claim 40, wherein said substance that forms photoradicals is at least one substance selected from the group consisting of oxygen, ozone, nitrous oxide, carbon dioxide and nitrogen dioxide. ### Claim 42 (depends on 36) A process for forming a semiconductor device according to claim 36, wherein said etching step is performed by dry etching. ### Claim 43 (depends on 42) A process for forming a semiconductor device according to claim 42, wherein said etching step is carried out by using halogen atom radicals. ### Claim 44 (depends on 36) A process for forming a semiconductor device according to claim 36, wherein the surface of said substrate comprises at least one material selected from the group consisting of Al, Si, SiN, C, Ge, GaAs, Ti, Ta, Mo, W and Nb. ### Claim 45 (depends on 36) A process for forming a semiconductor device according to claim 36, wherein said mask forming step is carried out in an atmosphere of a substance that forms photoradicals by irradiation with light for forming the photoradicals, the light having a wavelength not longer than the UV-ray absorption end of said substance. ### Claim 46 (depends on 42) A process for forming a semiconductor device according to claim 42, wherein said dry etching is carried out by using at least one substance selected from the group consisting of C1.sub.2, CF.sub.3 C1, CC1.sub.4 and NF.sub.3. ### Claim 47 (depends on 36) A process for forming a semiconductor device according to claim 36, wherein said halogen atom radicals are selected from the group consisting of chlorine radicals and fluorine radicals. ### Claim 48 (depends on 36) A process for forming a semiconductor device according to claim 36, wherein the light irradiation in said mask forming step is effected through a photomask having a light shielding pattern with a desired pattern. ### Claim 49 (depends on 48) A process for forming a semiconductor device according to claim 48, wherein said photomask further has a light absorbing member provided corresponding to said light shielding pattern.