CN116719208A - Laser direct-writing high-speed high-precision copper-based photoresist and semiconductor patterning method thereof - Google Patents
Laser direct-writing high-speed high-precision copper-based photoresist and semiconductor patterning method thereof Download PDFInfo
- Publication number
- CN116719208A CN116719208A CN202310701857.5A CN202310701857A CN116719208A CN 116719208 A CN116719208 A CN 116719208A CN 202310701857 A CN202310701857 A CN 202310701857A CN 116719208 A CN116719208 A CN 116719208A
- Authority
- CN
- China
- Prior art keywords
- copper
- based photoresist
- writing
- laser direct
- propylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 138
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 122
- 239000010949 copper Substances 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000004065 semiconductor Substances 0.000 title claims abstract description 21
- 238000000059 patterning Methods 0.000 title claims abstract description 14
- 238000000197 pyrolysis Methods 0.000 claims abstract description 48
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000005751 Copper oxide Substances 0.000 claims abstract description 38
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 14
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 28
- 238000004528 spin coating Methods 0.000 claims description 22
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical group COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- XPLSDXJBKRIVFZ-UHFFFAOYSA-L copper;prop-2-enoate Chemical compound [Cu+2].[O-]C(=O)C=C.[O-]C(=O)C=C XPLSDXJBKRIVFZ-UHFFFAOYSA-L 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- VZWHXRLOECMQDD-UHFFFAOYSA-L copper;2-methylprop-2-enoate Chemical compound [Cu+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O VZWHXRLOECMQDD-UHFFFAOYSA-L 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 229960000956 coumarin Drugs 0.000 claims description 2
- 235000001671 coumarin Nutrition 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000009210 therapy by ultrasound Methods 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000000233 ultraviolet lithography Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
Abstract
The invention discloses a laser direct-writing high-speed high-precision copper-based photoresist and a semiconductor patterning method thereof. The laser direct-writing copper-based photoresist comprises a copper-based photoresist monomer, a two-photon initiator, an inhibitor and a solvent; the inhibitor is at least one of TEMPO, BTPOS and DMPO; in the laser direct writing copper-based photoresist, the mass of the copper-based photoresist monomer is 2-8% of the mass of the solvent, the mass of the two-photon initiator is 0.25-2.5% of the mass of the copper-based photoresist monomer, and the mass of the inhibitor is 0.25-2.5% of the mass of the copper-based photoresist monomer. The copper-based photoresist provided by the invention is polymerized under the femtosecond laser with the wavelength of 780nm, the highest precision can reach sub50 nm, the highest writing speed can reach 200mm/s, and the micro-nano pattern of the copper oxide semiconductor can be obtained after pyrolysis.
Description
Technical Field
The invention belongs to the field of micro-nano structure manufacturing, and particularly relates to a laser direct-writing high-speed high-precision copper-based photoresist and a semiconductor patterning method thereof.
Background
The laser direct writing is a maskless photoetching technology, after focusing laser into a small light spot, the position of the light spot is changed by a mode of moving a vibrating mirror, a rotating mirror or a displacement table, exposure is carried out on photoresist, and a required micro-nano pattern is left after development. The traditional ultraviolet lithography needs to use a mask plate, the mask plate is loaded with a design pattern, and ultraviolet light is projected onto a photoresist film after passing through a light-transmitting part of the mask plate, so that the photoresist is exposed. The advantage of laser direct writing is that any pattern can be written without a mask plate, and the moving path of a laser spot is controlled only by a programming method, so that photoresist at a specific position is exposed.
Laser direct writing has a significant disadvantage compared to ultraviolet lithography in terms of writing speed. Taking a 6-inch substrate as an example, the typical time of ultraviolet lithography exposure is within 1 minute, and the time of laser direct writing to a 6-inch substrate is tens of hours or even hundreds of hours, which is one of the reasons that the current laser direct writing is difficult to be used for batch manufacturing, but is also very suitable for manufacturing template products such as mask plates and nano-imprint templates due to the maskless manufacturing mode.
The highest precision of the laser direct-writing photoresist used at present is about 100nm, and the precision of the laser direct-writing photoresist sold in the market is generally above 150 nm.
In order to meet the manufacturing requirements of high-precision devices and templates, high-precision laser direct writing photoresists of sub-100 nm and even sub-50 nm are necessary, and in order to shorten the manufacturing time and reduce the manufacturing cost, the photoresists also have the characteristics of high speed and high sensitivity, and the high precision and the high speed are generally difficult to simultaneously have in the laser direct writing photoresists. In addition, most of laser direct-writing photoresists sold in the market at present are all organic systems, and functional laser direct-writing photoresists which lack organic-inorganic composite function and can be used for patterning functional materials are also urgently needed.
Disclosure of Invention
The invention aims at providing a laser direct-writing high-speed high-precision copper-based photoresist and a semiconductor patterning method thereof aiming at the limitation of the prior art.
The invention aims at realizing the following technical scheme:
in a first aspect, the present invention provides a laser direct write copper-based photoresist comprising a copper-based photoresist monomer, a two-photon initiator, an inhibitor, and a solvent; the inhibitor is at least one of 2, 6-tetramethyl piperidine-nitrogen-oxide (TEMPO), sebacic acid bis (2, 6-tetramethyl-4-piperidinyl-1-oxy) ester (BTPOS) and 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO), and the increase of line width is inhibited by capturing free radicals diffused in the polymerization process; in the laser direct writing copper-based photoresist, the mass of the copper-based photoresist monomer is 2-8% of the mass of the solvent, the mass of the two-photon initiator is 0.25-2.5% of the mass of the copper-based photoresist monomer, and the mass of the inhibitor is 0.25-2.5% of the mass of the copper-based photoresist monomer.
Preferably, the solvent is Propylene Glycol Methyl Ether Acetate (PGMEA), propylene Glycol Methyl Ether (PGME), or a mixture of the two.
Preferably, the two-photon initiator is 7-diethylamino-3-thiophenecarboxyl coumarin (DETC).
Preferably, the copper-based photoresist monomer is hydrated copper methacrylate, copper acrylate or a mixture of the two.
Preferably, the laser direct writing copper-based photoresist consists of a copper-based photoresist monomer, a two-photon initiator, an inhibitor and a solvent.
The laser direct writing copper-based photoresist is obtained through conventional steps, namely, a copper-based photoresist monomer, a two-photon initiator and an inhibitor are dissolved in a solvent according to a certain proportion, the solvent is filtered by a filter membrane with the thickness of 0.22 mu m after being fully dissolved, and the mixture is fully and uniformly mixed on a uniformly mixer and then is refrigerated (for example, stored in an environment with the temperature of 4 ℃).
In a second aspect, the present invention provides a semiconductor patterning method based on the laser direct writing copper-based photoresist, comprising the steps of:
s1: obtaining laser direct-writing copper-based photoresist;
s2: spin-coating a laser direct-writing copper-based photoresist on a substrate by a spin-coating instrument to form a transparent copper-based photoresist film;
s3: a femtosecond laser direct writing device is adopted, femtosecond laser is used as a light source, and a method of galvanometer writing is adopted to induce the polymerization of the copper-based photoresist film at a designed position, and the designed pattern is obtained by developing with primary and secondary developing solutions in sequence;
s4: and pyrolyzing the obtained pattern written by the copper-based photoresist in an air atmosphere by using a heating device, wherein in the pyrolysis process, organic components in the pattern are oxidized to leave the system, and copper elements are oxidized to copper oxide, so that the micro-nano pattern of the P-type semiconductor copper oxide is obtained.
Preferably, in step S2, the spin coating speed used in the spin coating is 1500-5000rpm, and the spin coating time is 60S.
Preferably, in step S3, the wavelength of the femtosecond laser is between 525 and 780 nm.
Preferably, in the step S3, the energy used in the etching process of the copper-based photoresist is 3-50mW, and the speed is 1000-200000 μm/S (200 mm/S).
Preferably, in step S3, the primary developing solution used for developing is at least one of propylene glycol methyl ether acetate, propylene glycol monomethyl ether, and propylene glycol monoethyl ether, and the secondary developing solution is isopropyl alcohol.
Preferably, in the step S4, the atmosphere during pyrolysis is air atmosphere, the pyrolysis temperature is 500-1000 ℃, the heating rate is 1-10 ℃/min, and the cooling rate is natural cooling.
As a further preferred aspect, the pyrolysis temperature in step S4 is 500-600 ℃, and the substrate used is glass; and S4, the pyrolysis temperature is higher than 600 ℃ and less than or equal to 1000 ℃, and the substrate is quartz.
Compared with the prior art, the invention has the following benefits: the copper-based photoresist is polymerized under the femtosecond laser with the wavelength of 780nm, the precision is below 91nm, the highest precision can reach sub-50 nm, the wavelength is 1/15, and the copper-based photoresist has good line morphology; the highest writing speed can reach 200mm/s while high precision is maintained, the requirement of high-speed high-precision laser direct writing can be met, and the solid glue is suitable for large-area writing and is suitable for manufacturing large-area two-dimensional patterns. After the pattern inscribed by the copper-based photoresist is pyrolyzed in air atmosphere, a corresponding copper oxide micro-nano pattern can be obtained, and copper oxide is a P-type semiconductor and can be used for manufacturing semiconductor micro-nano devices. The copper-based high-speed high-precision laser direct-writing photoresist and the semiconductor patterning method thereof can realize the laser direct-writing direct-manufacturing of the high-speed high-precision copper oxide semiconductor micro-nano device.
Drawings
FIG. 1 is a copper oxide line inscribed by a copper-based photoresist A;
FIG. 2 is an XRD pattern of copper-based photoresist A after UV curing and annealing;
FIG. 3 is a copper oxide line inscribed with a copper-based photoresist B;
FIG. 4 is a copper oxide line inscribed by a copper-based photoresist C;
FIG. 5 is a copper oxide line inscribed by a copper-based photoresist D;
FIG. 6 is a copper oxide line inscribed by a copper-based photoresist E;
FIG. 7 is a copper oxide line inscribed by a copper-based photoresist F;
FIG. 8 is a copper oxide line inscribed with a copper-based photoresist G;
FIG. 9 is a copper oxide line inscribed with a copper-based photoresist H;
FIG. 10 is a copper oxide line inscribed by a copper-based photoresist I;
FIG. 11 is a copper oxide line inscribed by a copper-based photoresist J;
FIG. 12 is a copper oxide line written in a comparative copper-based photoresist A;
FIG. 13 is a zinc oxide line inscribed in a comparative zinc-based photoresist A;
fig. 14 is a schematic diagram of a femtosecond laser direct writing device used in an embodiment of the invention.
Detailed Description
The invention will be further described with reference to the preferred embodiments and the accompanying drawings. The details described in the following examples are intended to be illustrative and not limiting and will assist those skilled in the art in further understanding the invention, but should not be construed to limit the invention in any way. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the basic concept and method of the invention. These are all within the scope of the present invention.
The femtosecond laser direct writing device used in the embodiment of the invention is shown in fig. 1. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
0.5g of copper acrylate is dissolved into 10g of propylene glycol methyl ether acetate, 1.25mg of two-photon initiator DETC and 1.25mg of TEMPO are added, then ultrasonic treatment is carried out for 20 minutes to promote dissolution, a filter membrane with the thickness of 0.22 mu m is used for filtering twice, copper-based photoresist A is obtained, and the copper-based photoresist A is refrigerated and stored in an environment of 4 ℃ after being uniformly mixed for 24 hours on a uniformly mixing instrument.
And (3) dropwise adding the copper-based photoresist A onto a glass substrate, and spin-coating at 3000rpm for 60 seconds to obtain a film of the copper-based photoresist A.
Writing is carried out by using 780nm femtosecond laser, the laser focus position is changed by a galvanometer system to induce the monomer at a selected position of the copper-based photoresist film to polymerize, the energy used for writing is 50mW, and the speed is 200000 mu m/s.
After the writing is completed, developing for 30s in propylene glycol methyl ether acetate, and developing for 2min in isopropanol to obtain the written pattern.
And (3) pyrolyzing the obtained pattern in an air atmosphere for 60min by using a box furnace, wherein the pyrolysis temperature is 500 ℃, the heating rate during pyrolysis is 5 ℃/min, and the cooling rate is natural cooling.
After pyrolysis, a micro-nano pattern of copper oxide was obtained, and the pattern was characterized by SEM, as shown in fig. 1, and the line width of the inscribed line was about 47nm.
Because of the small size of the micro-nano structure, XRD (X-ray diffraction) test is difficult to directly perform, in order to characterize the pyrolyzed sample components, 0.5g of copper-based photoresist A is taken, and subjected to ultraviolet curing at 365nm, pyrolysis is performed under the same conditions, and XRD characterization is performed on the pyrolyzed sample. As shown in fig. 2, each diffraction peak of the XRD spectrum of the pyrolyzed sample was identical to that of the standard card of copper oxide, indicating that the pyrolyzed sample component was copper oxide.
Example 2
0.2g of copper acrylate is dissolved into 10g of propylene glycol monomethyl ether, 4mg of two-photon initiator DETC and 4mg of BTPOS are added, then ultrasonic treatment is carried out for 20 minutes to promote dissolution, a filter membrane with the thickness of 0.22 mu m is used for filtering twice, copper-based photoresist B is obtained, and the copper-based photoresist B is refrigerated and stored in an environment of 4 ℃ after being uniformly mixed for 24 hours on a uniformly mixing instrument.
And (3) dropwise adding the copper-based photoresist B onto a glass substrate, and spin-coating at 1500rpm for 60 seconds to obtain a film of the copper-based photoresist B.
Writing is carried out by using 780nm femtosecond laser, the laser focus position is changed by a galvanometer system to induce the monomer at the selected position of the copper-based photoresist film to polymerize, the energy used in the writing is 10mW, and the speed is 5000 mu m/s.
After the writing is completed, developing for 30s in propylene glycol monomethyl ether, and developing for 2min in isopropanol to obtain a written pattern.
And (3) pyrolyzing the obtained pattern in an air atmosphere for 60min by using a box furnace, wherein the pyrolysis temperature is 500 ℃, the heating rate during pyrolysis is 5 ℃/min, and the cooling rate is natural cooling.
After pyrolysis, a micro-nano pattern of copper oxide was obtained, characterized by SEM, with a line width of 65nm, as shown in fig. 3.
Example 3
0.5g of copper acrylate is dissolved into 10g of propylene glycol monomethyl ether, 2.5mg of a two-photon initiator DETC,1.25mg of BTPOS and 1.25mg of TEMPO are added, then the dissolution is promoted by ultrasonic treatment for 20 minutes, the solution is filtered twice by a filter membrane with the thickness of 0.22 mu m, and the copper-based photoresist C is obtained, and is refrigerated and stored in an environment of 4 ℃ after being uniformly mixed for 24 hours on a uniformly mixing instrument.
And (3) dropwise adding the copper-based photoresist C onto a glass substrate, and spin-coating at 2000rpm for 60 seconds to obtain a film of the copper-based photoresist C.
Writing is carried out by using 780nm femtosecond laser, the laser focus position is changed by a galvanometer system to induce the monomer at the selected position of the copper-based photoresist film to polymerize, the energy used in the writing is 15mW, and the speed is 8000 mu m/s.
After the writing is completed, developing for 30s in propylene glycol monomethyl ether, and developing for 2min in isopropanol to obtain a written pattern.
And (3) pyrolyzing the obtained pattern in an air atmosphere for 60min by using a box furnace, wherein the pyrolysis temperature is 500 ℃, the heating rate during pyrolysis is 5 ℃/min, and the cooling rate is natural cooling.
After pyrolysis, a micro-nano pattern of copper oxide was obtained, characterized by SEM, with a line width of 57nm, as shown in fig. 4.
Example 4
0.8g of copper acrylate is dissolved into 10g of propylene glycol monomethyl ether, 8mg of two-photon initiator DETC and 8mg of DMPO are added, then ultrasonic treatment is carried out for 20 minutes to promote dissolution, a filter membrane with the thickness of 0.22 mu m is used for filtering twice, copper-based photoresist D is obtained, and the copper-based photoresist D is refrigerated and stored in an environment of 4 ℃ after being uniformly mixed for 24 hours on a uniformly mixing instrument.
And (3) dripping the copper-based photoresist D on a quartz substrate, and spin-coating at 4000rpm for 60 seconds to obtain a film of the copper-based photoresist D.
Writing is carried out by using 780nm femtosecond laser, the laser focus position is changed by a galvanometer system to induce the monomer at a selected position of the copper-based photoresist film to polymerize, the energy used in the writing is 3mW, and the speed is 1000 mu m/s.
After the writing is completed, developing for 30s in propylene glycol monomethyl ether, and developing for 2min in isopropanol to obtain a written pattern.
And (3) pyrolyzing the obtained pattern in an air atmosphere for 60min by using a box furnace, wherein the pyrolysis temperature is 700 ℃, the heating rate during pyrolysis is 5 ℃/min, and the cooling rate is natural cooling.
After pyrolysis, a micro-nano pattern of copper oxide was obtained, characterized by SEM, with a line width of 67nm, as shown in fig. 5.
Example 5
0.5g of copper acrylate is dissolved into 10g of propylene glycol monoethyl ether, 5mg of two-photon initiator DETC and 5mg of DMPO are added, then ultrasonic treatment is carried out for 20 minutes to promote dissolution, a filter membrane with the thickness of 0.22 mu m is used for filtering twice, and copper-based photoresist E is obtained, and after being uniformly mixed on a uniformly mixing instrument for 24 hours, the copper-based photoresist E is stored in a refrigerating mode at the temperature of 4 ℃.
And (3) dropwise adding the copper-based photoresist E onto a glass substrate, and spin-coating at 2000rpm for 60 seconds to obtain a film of the copper-based photoresist E.
Writing is carried out by using 780nm femtosecond laser, the laser focus position is changed by a galvanometer system to induce the monomer at a selected position of the copper-based photoresist film to polymerize, the energy used for writing is 25mW, and the speed is 50000 mu m/s.
After the writing was completed, the pattern was developed in propylene glycol monoethyl ether for 30s and then in isopropanol for 2min to obtain the written pattern.
And (3) pyrolyzing the obtained pattern in an air atmosphere for 60min by using a box furnace, wherein the pyrolysis temperature is 600 ℃, the heating rate during pyrolysis is 5 ℃/min, and the cooling rate is natural cooling.
After pyrolysis, a micro-nano pattern of copper oxide was obtained, characterized by SEM, with a line width of 53nm, as shown in fig. 6.
Example 6
0.5g of hydrated copper methacrylate is dissolved into 10g of a mixture of propylene glycol monomethyl ether and propylene glycol monoethyl ether (the mass ratio of the two solvents to be mixed is 1:1), 5mg of a two-photon initiator DETC,2.5mg of DMPO and 2.5mg of BTPOS are added, then the solution is promoted by ultrasonic treatment for 20 minutes, the solution is filtered twice by a filter membrane with the thickness of 0.22 mu m, and the copper-based photoresist F is obtained, and is refrigerated and stored in an environment of 4 ℃ after being uniformly mixed on a uniformly mixer for 24 hours.
And (3) dripping the copper-based photoresist F on a quartz substrate, and spin-coating at 2000rpm for 60 seconds to obtain a film of the copper-based photoresist F.
Writing is carried out by using 780nm femtosecond laser, the position of a laser focus is changed by a galvanometer system to induce the polymerization of monomers at selected positions of the copper-based photoresist film, the energy used in the writing is 20mW, and the speed is 10000 mu m/s.
After the writing is completed, developing for 30s in propylene glycol monomethyl ether, and developing for 2min in isopropanol to obtain a written pattern.
And (3) pyrolyzing the obtained pattern in an air atmosphere for 60min by using a box furnace, wherein the pyrolysis temperature is 800 ℃, the heating rate during pyrolysis is 5 ℃/min, and the cooling rate is natural cooling.
After pyrolysis, a micro-nano pattern of copper oxide was obtained, characterized by SEM, with a line width of 82nm, as shown in fig. 7.
Example 7
0.25G of copper acrylate and 0.25G of hydrated copper methacrylate are dissolved in a mixture of 10G of propylene glycol methyl ether acetate and propylene glycol monoethyl ether (the mass ratio of the two solvents is 1:1), 5mg of two-photon initiator DETC,2.5mg of TEMPO and 2.5mg of DMPO are added, then the dissolution is promoted by ultrasonic treatment for 20 minutes, the solution is filtered twice by a filter membrane of 0.22 mu m, the copper-based photoresist G is obtained, and the copper-based photoresist G is refrigerated and stored in an environment of 4 ℃ after being uniformly mixed for 24 hours on a uniformly mixing instrument.
And (3) dropwise adding the copper-based photoresist G onto a quartz substrate, and spin-coating at 2000rpm for 60 seconds to obtain a film of the copper-based photoresist G.
Writing is carried out by using 780nm femtosecond laser, the laser focus position is changed by a galvanometer system to induce the monomer at a selected position of the copper-based photoresist film to polymerize, the energy used for writing is 35mW, and the speed is 100000 mu m/s.
After the writing is completed, developing for 30s in propylene glycol monomethyl ether, and developing for 2min in isopropanol to obtain a written pattern.
And (3) pyrolyzing the obtained pattern in an air atmosphere for 60min by using a box furnace, wherein the pyrolysis temperature is 800 ℃, the heating rate during pyrolysis is 5 ℃/min, and the cooling rate is natural cooling.
After pyrolysis, a micro-nano pattern of copper oxide was obtained, characterized by SEM, with a line width of 77nm, as shown in fig. 8.
Example 8
0.6g of hydrated copper methacrylate is dissolved into 10g of propylene glycol methyl ether acetate, 3mg of two-photon initiator DETC and 3mg of TEMPO are added, then ultrasonic treatment is carried out for 20 minutes to promote dissolution, a filter membrane with the thickness of 0.22 mu m is used for filtering twice, copper-based photoresist H is obtained, and the copper-based photoresist H is refrigerated and stored in an environment of 4 ℃ after being uniformly mixed for 24 hours on a uniformly mixer.
And (3) dropwise adding the copper-based photoresist H onto a glass substrate, and spin-coating at 5000rpm for 60 seconds to obtain a film of the copper-based photoresist H.
Writing is carried out by using 780nm femtosecond laser, the laser focus position is changed by a galvanometer system to induce the monomer at a selected position of the copper-based photoresist film to polymerize, the energy used in the writing is 15mW, and the speed is 30000 mu m/s.
After the writing is completed, developing for 30s in propylene glycol methyl ether acetate, and developing for 2min in isopropanol to obtain the written pattern.
And (3) pyrolyzing the obtained pattern in an air atmosphere for 60min by using a box furnace, wherein the pyrolysis temperature is 600 ℃, the heating rate during pyrolysis is 5 ℃/min, and the cooling rate is natural cooling.
After pyrolysis, a micro-nano pattern of copper oxide was obtained, characterized by SEM, with a line width of 86nm, as shown in fig. 9.
Example 9
0.5g of hydrated copper methacrylate is dissolved into 10g of a mixture of propylene glycol methyl ether acetate and propylene glycol monomethyl ether (the mass ratio of the two solvents is 1:1), 10mg of two-photon initiator DETC and 10mg of TEMPO are added, then the dissolution is promoted by ultrasonic treatment for 20 minutes, the solution is filtered twice by a filter membrane with the thickness of 0.22 mu m, and the copper-based photoresist I is obtained, and is refrigerated and stored in an environment of 4 ℃ after being uniformly mixed for 24 hours on a uniformly mixing instrument.
And (3) dripping the copper-based photoresist I on a quartz substrate, and spin-coating at 5000rpm for 60 seconds to obtain a film of the copper-based photoresist I.
Writing is carried out by using 780nm femtosecond laser, the laser focus position is changed by a galvanometer system to induce the monomer at a selected position of the copper-based photoresist film to polymerize, the energy used for writing is 35mW, and the speed is 100000 mu m/s.
After the writing is completed, developing for 30s in propylene glycol methyl ether acetate, and developing for 2min in isopropanol to obtain the written pattern.
And (3) pyrolyzing the obtained pattern in an air atmosphere for 60min by using a box furnace, wherein the pyrolysis temperature is 1000 ℃, the heating rate during pyrolysis is 5 ℃/min, and the cooling rate is natural cooling.
After pyrolysis, micro-nano patterns of copper oxide were obtained, which were characterized by SEM with a line width of 91nm, as shown in fig. 10.
Example 10
0.5g of hydrated copper methacrylate is dissolved into 10g of propylene glycol methyl ether acetate, 10mg of two-photon initiator DETC and 10mg of TEMPO are added, then ultrasonic treatment is carried out for 20 minutes to promote dissolution, a filter membrane with the thickness of 0.22 mu m is used for filtering twice, thus obtaining copper-based photoresist J, and the copper-based photoresist J is refrigerated and stored in an environment of 4 ℃ after being uniformly mixed for 24 hours on a uniformly mixer.
And (3) dropwise adding the copper-based photoresist J onto a quartz substrate, and spin-coating at 5000rpm for 60 seconds to obtain a film of the copper-based photoresist J.
Writing is carried out by using 780nm femtosecond laser, the laser focus position is changed by a galvanometer system to induce the monomer at a selected position of the copper-based photoresist film to polymerize, the energy used for writing is 40mW, and the speed used for writing is 120000 mu m/s.
After the writing is completed, developing for 30s in propylene glycol methyl ether acetate, and developing for 2min in isopropanol to obtain the written pattern.
And (3) pyrolyzing the obtained pattern in an air atmosphere for 60min by using a box furnace, wherein the pyrolysis temperature is 1000 ℃, the heating rate during pyrolysis is 5 ℃/min, and the cooling rate is natural cooling.
After pyrolysis, a micro-nano pattern of copper oxide was obtained, characterized by SEM, with a line width of 76nm, as shown in fig. 11.
As can be seen from the images of the copper oxide patterns carved in the examples 1 to 10, the method has clear carved lines, good line shape, good uniformity and minimum resolution of sub-50 nm. The method can obtain the micro-nano pattern of any copper oxide in a laser direct writing mode, and provides a new method for manufacturing copper oxide semiconductor devices.
Comparative example 1
0.5g of copper acrylate is dissolved into 10g of propylene glycol methyl ether acetate, 1.25mg of a two-photon initiator DETC is added, then ultrasonic treatment is carried out for 20 minutes to promote dissolution, a filter membrane with the thickness of 0.22 mu m is used for filtering twice, and the comparative copper-based photoresist A is obtained, and is refrigerated and stored in an environment of 4 ℃ after being uniformly mixed for 24 hours on a uniformly mixing instrument.
And (3) dropwise adding the comparative copper-based photoresist A onto a glass substrate, and spin-coating at 3000rpm for 60 seconds to obtain a film of the comparative copper-based photoresist A.
Writing is carried out by using 780nm femtosecond laser, the laser focus position is changed by a galvanometer system to induce the monomer at a selected position of the copper-based photoresist film to polymerize, the energy used for writing is 50mW, and the speed is 200000 mu m/s.
After the writing is completed, developing for 30s in propylene glycol methyl ether acetate, and developing for 2min in isopropanol to obtain the written pattern.
And (3) pyrolyzing the obtained pattern in an air atmosphere for 60min by using a box furnace, wherein the pyrolysis temperature is 500 ℃, the heating rate during pyrolysis is 5 ℃/min, and the cooling rate is natural cooling.
After pyrolysis, a micro-nano pattern of copper oxide was obtained, and the pattern was characterized by SEM, as shown in fig. 12, and the line width of the inscribed line was about 120nm. The comparative example was free of inhibitor, and the rest of the conditions were the same as in example 1, but the line width was significantly larger than the line in example 1, demonstrating the effect of the inhibitor in effectively inhibiting the increase in line width.
Comparative example 2
0.5g of zinc acrylate is dissolved into 10g of propylene glycol methyl ether acetate, 1.25mg of a two-photon initiator DETC and 1.25mg of TEMPO are added, then ultrasonic treatment is carried out for 20 minutes to promote dissolution, a filter membrane with the thickness of 0.22 mu m is used for filtering twice, and the comparative zinc-based photoresist A is obtained, and is refrigerated and stored in an environment of 4 ℃ after being uniformly mixed for 24 hours on a uniformly mixing instrument.
And (3) dropwise adding the comparative zinc-based photoresist A onto a glass substrate, and spin-coating at 3000rpm for 60 seconds to obtain a film of the comparative zinc-based photoresist A.
Writing is carried out by using 780nm femtosecond laser, the laser focus position is changed by a galvanometer system to induce the polymerization of monomers at selected positions of the zinc-based photoresist film, the energy used in the writing is 50mW, and the speed is 20000 mu m/s.
After the writing is completed, developing for 30s in propylene glycol methyl ether acetate, and developing for 2min in isopropanol to obtain the written pattern.
And (3) pyrolyzing the obtained pattern in an air atmosphere for 60min by using a box furnace, wherein the pyrolysis temperature is 500 ℃, the heating rate during pyrolysis is 5 ℃/min, and the cooling rate is natural cooling.
After pyrolysis, a micro-nano pattern of zinc oxide was obtained, and the pattern was characterized by SEM, as shown in fig. 13, and the line width of the inscribed line was about 80nm. In the comparative example, the monomer is replaced by a zinc-based photoresist monomer, and the maximum writing speed can only reach about 20000 mu m/s when the energy is 50mW due to the lower sensitivity of the zinc-based photoresist, and the higher writing speed can not write lines, in this case, the rest conditions are the same as those in the example 1, and the line width is far greater than that in the example 1, so that the high sensitivity and high precision characteristics of the copper-based photoresist monomer are proved.
As can be seen from the images of the copper oxide patterns carved in the examples 1 to 10, the method has clear carved lines, good line shape, good uniformity and minimum resolution of sub-50 nm. The method can obtain the micro-nano pattern of any copper oxide in a laser direct writing mode, and provides a new method for manufacturing copper oxide semiconductor devices.
The foregoing examples illustrate the invention in detail, but are not intended to limit the invention to the specific embodiments thereof. The invention is not limited to the specific embodiments described above, and a person skilled in the art may make various modifications on the basis of the above, and all obvious modifications which are introduced by the technical solution of the invention remain within the scope of the invention.
Claims (10)
1. A laser direct writing copper-based photoresist is characterized in that: the laser direct-writing copper-based photoresist comprises a copper-based photoresist monomer, a two-photon initiator, an inhibitor and a solvent; the inhibitor is at least one of 2, 6-tetramethyl piperidine-nitrogen-oxide, sebacic acid bis (2, 6-tetramethyl-4-piperidinyl-1-oxy) ester and 5, 5-dimethyl-1-pyrroline-N-oxide, and the increase of line width is inhibited by capturing free radicals diffused in the polymerization process; in the laser direct writing copper-based photoresist, the mass of the copper-based photoresist monomer is 2-8% of the mass of the solvent, the mass of the two-photon initiator is 0.25-2.5% of the mass of the copper-based photoresist monomer, and the mass of the inhibitor is 0.25-2.5% of the mass of the copper-based photoresist monomer.
2. The laser direct write copper-based photoresist of claim 1, wherein: the solvent is propylene glycol methyl ether acetate, propylene glycol methyl ether or a mixture of the propylene glycol methyl ether acetate and the propylene glycol methyl ether.
3. The laser direct write copper-based photoresist of claim 1, wherein: the two-photon initiator is 7-diethylamino-3-thiophenecarboxyl coumarin.
4. The laser direct write copper-based photoresist of claim 1, wherein: the copper-based photoresist monomer is hydrated copper methacrylate, copper acrylate or a mixture of the hydrated copper methacrylate and the copper acrylate.
5. The laser direct write copper-based photoresist of claim 1, wherein: the laser direct writing copper-based photoresist consists of a copper-based photoresist monomer, a two-photon initiator, an inhibitor and a solvent.
6. A method for patterning a semiconductor based on the laser direct write copper-based photoresist of claim 1, characterized by: the semiconductor patterning method includes the steps of:
s1: obtaining laser direct-writing copper-based photoresist;
s2: spin-coating a laser direct-writing copper-based photoresist on a substrate by a spin-coating instrument to form a transparent copper-based photoresist film;
s3: a femtosecond laser direct writing device is adopted, femtosecond laser is used as a light source, and a method of galvanometer writing is adopted to induce the polymerization of the copper-based photoresist film at a designed position, and the designed pattern is obtained by developing with primary and secondary developing solutions in sequence;
s4: and pyrolyzing the obtained pattern written by the copper-based photoresist in an air atmosphere by using a heating device, wherein in the pyrolysis process, organic components in the pattern are oxidized to leave the system, and copper elements are oxidized to copper oxide, so that the micro-nano pattern of the P-type semiconductor copper oxide is obtained.
7. The semiconductor patterning method of claim 6, wherein: in step S2, the spin coating speed used in the spin coating is 1500-5000rpm, and the spin coating time is 60S.
8. The semiconductor patterning method of claim 6, wherein: in the step S3, the wavelength of the femtosecond laser is between 525 and 780nm, the energy range used in the etching of the copper-based photoresist is 3-50mW, and the speed range used is 1000 mu m/S-200000 mu m/S (200 mm/S); the primary developing solution used for developing is at least one of propylene glycol methyl ether acetate, propylene glycol monomethyl ether and propylene glycol monoethyl ether, and the secondary developing solution is isopropanol.
9. The semiconductor patterning method of claim 6, wherein: in the step S4, the atmosphere during pyrolysis is air atmosphere, the pyrolysis temperature is 500-1000 ℃, the heating rate is 1-10 ℃/min, and the cooling rate is natural cooling.
10. The semiconductor patterning method of claim 9, wherein: the pyrolysis temperature of the step S4 is 500-600 ℃, and the substrate used is glass; and S4, the pyrolysis temperature is higher than 600 ℃ and less than or equal to 1000 ℃, and the substrate is quartz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310701857.5A CN116719208A (en) | 2023-06-14 | 2023-06-14 | Laser direct-writing high-speed high-precision copper-based photoresist and semiconductor patterning method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310701857.5A CN116719208A (en) | 2023-06-14 | 2023-06-14 | Laser direct-writing high-speed high-precision copper-based photoresist and semiconductor patterning method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116719208A true CN116719208A (en) | 2023-09-08 |
Family
ID=87872957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310701857.5A Pending CN116719208A (en) | 2023-06-14 | 2023-06-14 | Laser direct-writing high-speed high-precision copper-based photoresist and semiconductor patterning method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116719208A (en) |
-
2023
- 2023-06-14 CN CN202310701857.5A patent/CN116719208A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4788485B2 (en) | Colored photosensitive resin composition | |
| KR101047703B1 (en) | Colored photosensitive resin composition and color filter | |
| US5952149A (en) | Resist solution for photolithography including a base resin and an oxygen-free or low-oxygen solvent | |
| TW201940972A (en) | Colored photosensitive resin composition, color filter and image display device using the same no process issue occurs, and holes are prevented from being created in the patterns formed | |
| KR20150045370A (en) | Colorant dispersion | |
| CN116719208A (en) | Laser direct-writing high-speed high-precision copper-based photoresist and semiconductor patterning method thereof | |
| US10613433B2 (en) | Method for producing substrate with fine projection-and-recess pattern, and substrate with fine projection-and-recess pattern obtained thereby | |
| JP2011039317A (en) | Colored photosensitive resin composition | |
| KR20220013561A (en) | Curable resin composition, manufacturing method of curable resin composition, cured film, laminated body, manufacturing method of a cured film, and semiconductor device | |
| CN114326295B (en) | Femtosecond laser direct writing method for zinc oxide micro-nano pattern | |
| KR20190058976A (en) | Photosensitive polyamic acid derivative resins and thermal resistance negative type photoresist composition | |
| KR20150106665A (en) | A colored photosensitive resin composition | |
| JP2007058192A (en) | Colored photosensitive resin composition | |
| KR20140145333A (en) | A colored photosensitive resin composition and color filter comprising the same | |
| TWI234009B (en) | Method of producing colored photosensitive resin composition | |
| JP2012153874A (en) | Hydrophilic monomer, hydrophilic photoresist composition containing the same, and method for forming resist pattern | |
| Lippert et al. | Development and structuring of combined positive‐negative/negative‐positive resists using laser ablation as positive dry etching technique | |
| KR102108232B1 (en) | Colored Photosensitive Resin Composition for Red Pixel, Color Filter and Display Device | |
| CN100468210C (en) | Method for manufacturing semiconductor device using immersion lithography process | |
| KR20040030266A (en) | Colored photosensitive resin compositions | |
| TWI674479B (en) | Colored photosensitive resin composition, color filter manufactured using thereof and image display device having the same | |
| CN109503752A (en) | A kind of low diffusion ArF photoresist polymer photosensitizer PAG and its application | |
| KR101401488B1 (en) | Colored photosensitive resin composition, and color filter and liquid crystal display device prepared by using the same | |
| KR20100094811A (en) | Colored photosensitive resin composition, color filter and liquid crystal display device prepared by using the same | |
| JPH0391752A (en) | Photosensitive resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |