CN113960881B - KrF negative photoresist and preparation method and application thereof - Google Patents
KrF negative photoresist and preparation method and application thereof Download PDFInfo
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- CN113960881B CN113960881B CN202111417731.2A CN202111417731A CN113960881B CN 113960881 B CN113960881 B CN 113960881B CN 202111417731 A CN202111417731 A CN 202111417731A CN 113960881 B CN113960881 B CN 113960881B
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 125000006239 protecting group Chemical group 0.000 claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 37
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000002378 acidificating effect Effects 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 125000000129 anionic group Chemical group 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- AXVPVXHGWJWEPI-UHFFFAOYSA-N (2-methylphenyl)carbamic acid Chemical compound CC1=CC=CC=C1NC(O)=O AXVPVXHGWJWEPI-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- IRNSYGIUGHROTJ-UHFFFAOYSA-N benzyl 2-methylbenzoate Chemical group CC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRNSYGIUGHROTJ-UHFFFAOYSA-N 0.000 claims description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 3
- 229940116333 ethyl lactate Drugs 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 abstract description 7
- 238000002791 soaking Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 17
- 230000008569 process Effects 0.000 description 8
- 229920006026 co-polymeric resin Polymers 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- -1 but not limited to Chemical class 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XHJLADWDZOROLZ-UHFFFAOYSA-N benzyl n-(2-methylphenyl)carbamate Chemical compound CC1=CC=CC=C1NC(=O)OCC1=CC=CC=C1 XHJLADWDZOROLZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
- H01L21/0275—Photolithographic processes using lasers
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention provides a KrF negative photoresist and a preparation method and application thereof, relating to the technical field of photoresist preparation, and comprising the following components: a poly-p-hydroxystyrene copolymer, an acidic catalyst, a photoactivator, and optionally a solvent, wherein the poly-p-hydroxystyrene copolymer comprises a poly-p-hydroxystyrene copolymer comprising a protecting group, and the photoactivator comprises an anionic initiator. The KrF negative photoresist of the invention has the advantages that the acidic catalyst catalyzes the protecting group of the poly-p-hydroxystyrene copolymer to fall off in the non-exposure area, and the compound generated by the anionic initiator can deactivate the acidic catalyst after the exposure area is exposed by ultraviolet light with the wavelength of 248nm, so that the protecting group is not catalyzed any more. The invention solves the technical problem that the poly-p-hydroxystyrene resin is difficult to remove photoresist by a wet method after crosslinking, and achieves the technical effect that photoresist can be removed cleanly by soaking at normal temperature.
Description
Technical Field
The invention relates to the technical field of photoresist preparation, in particular to a KrF negative photoresist and a preparation method and application thereof.
Background
Deep ultraviolet negative photoresist for KrF excimer laser (248 nm) exposure is not as important as positive photoresist but is used in applications of this type of photoresist for the fabrication of 0.25-0.15 micron critical dimension chips.
The prior KrF negative photoresist is mainly poly-p-hydroxystyrene, and is also added with a cross-linking agent and a photosensitive catalyst, which are used for producing acid by the catalyst after exposure, and the catalyst is used for carrying out cross-linking reaction with the cross-linking agent during middle baking, so that a macromolecular polymer is finally generated and is insoluble in alkaline developer, thereby forming a negative image after development. However, the characteristics of the poly-p-hydroxystyrene make it difficult to remove photoresist by a wet method after crosslinking, but only remove photoresist by a dry method of plasma bombardment after pattern transfer is completed, which greatly reduces the process efficiency and improves the production cost.
In view of this, the present invention has been made.
Disclosure of Invention
One of the purposes of the invention is to provide a KrF negative photoresist, which can be removed by adopting a wet photoresist removing method and can be completely removed by soaking at normal temperature.
The second purpose of the invention is to provide a preparation method of the KrF negative photoresist, which has simple process and high excellent rate.
The invention also provides an application of the KrF negative photoresist.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
in a first aspect, the present invention provides a KrF negative photoresist comprising the following components:
A poly-p-hydroxystyrene copolymer, an acidic catalyst, a photoactivator, and optionally a solvent;
the poly-p-hydroxystyrene copolymer comprises a poly-p-hydroxystyrene copolymer containing a protecting group;
the protecting group-containing poly (p-hydroxystyrene) copolymer comprises at least one of a compound represented by the following general formula (1) and a compound represented by the general formula (2):
wherein a: b= (5 to 7): (5-3);
Wherein, m: n= (5-7): (5-3);
the photoactivator comprises an anionic initiator.
Further, the molecular weight Mw of the protective group-containing poly (p-hydroxystyrene) copolymer is 1000 to 20000.
Further, the acid catalyst is at least one of organic acid and inorganic acid;
further preferably, the organic acid includes at least one of formic acid, acetic acid, propionic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and p-toluenesulfonic acid;
further preferably, the inorganic acid includes at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrofluoric acid.
Further, the anionic initiator comprises benzyl orthotoluate.
Further, the solvent comprises at least one of propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl acetate and ethyl lactate.
Further, the KrF negative photoresist comprises the following components in parts by weight:
10 to 60 parts of poly (p-hydroxystyrene) copolymer resin containing protective groups, 0.2 to 5 parts of acid catalyst, 0.2 to 5 parts of anionic initiator and 5 to 100 parts of solvent.
Further, the KrF negative photoresist comprises the following components in parts by weight:
20 parts of a poly (p-hydroxystyrene) copolymer resin containing a protecting group, 0.2 part of an acidic catalyst, 0.4 to 0.5 part of o-toluylcarbamate and 100 parts of a solvent.
In a second aspect, the present invention provides a method for preparing the KrF negative photoresist, comprising the steps of:
and dissolving the components by using the solvent to obtain the KrF negative photoresist.
Further, filtration is included after dissolution.
Further preferably, the filtering comprises filtering with a filter membrane;
Further preferably, the pore size of the filter membrane is 0.01-1 micron.
In a third aspect, the invention provides the use of the KrF negative photoresist in integrated circuit fabrication.
Compared with the prior art, the invention has at least the following beneficial effects:
The KrF negative photoresist provided by the invention can be developed without resin crosslinking, so that wet photoresist removal can be adopted, the photoresist can be removed cleanly by soaking at normal temperature, and dry photoresist removal with high cost and low efficiency is avoided, so that the process cost is greatly reduced and the production efficiency is improved; specifically, in the KrF negative photoresist of the present invention, the acidic catalyst catalyzes the protecting group of the poly-p-hydroxystyrene copolymer to be detached in the non-exposure area, so that the poly-p-hydroxystyrene copolymer is soluble in an alkaline developer, and after the exposure area is exposed to ultraviolet light with wavelength of 248nm, the compound generated by the anionic initiator can deactivate the acidic catalyst, so that the protecting group is not catalyzed any more, and after the poly-p-hydroxystyrene copolymer is developed by the alkaline developer, a negative image is formed.
The preparation method of the KrF negative photoresist provided by the invention has the advantages of simple process and high excellent rate.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to a first aspect of the present invention, there is provided a KrF negative photoresist comprising the following components:
A poly-p-hydroxystyrene copolymer, an acidic catalyst, a photoactivator, and optionally a solvent;
In the present invention, the poly-p-hydroxystyrene copolymer includes a poly-p-hydroxystyrene copolymer containing a protecting group; the protecting group-containing poly (p-hydroxystyrene) copolymer comprises at least one of a compound represented by the following general formula (1) and a compound represented by the general formula (2):
wherein a: b= (5 to 7): (5-3), the typical but non-limiting ratio of a to b is 5: 5. 5: 4. 5: 3. 6: 5. 6: 4. 6: 3. 7: 5. 7: 4. 7:3, a step of;
Wherein, m: n= (5-7): (5-3), the typical but non-limiting ratio of m to n is 5: 5. 5: 4. 5: 3. 6: 5. 6: 4. 6: 3. 7: 5. 7: 4. 7:3, a step of;
In the present invention, the photoactivator includes, but is not limited to, an anionic initiator.
The KrF negative photoresist is based on a deactivation mechanism, the photoresist of the invention utilizes the poly (p-hydroxystyrene) copolymer resin with a protecting group to match with the deactivation mechanism (namely, the poly (p-hydroxystyrene) copolymer with the protecting group is matched with an acid catalyst and an anion initiator), and can realize that a negative image can be manufactured under the condition of no crosslinking, so that the photoresist can be simply, conveniently and quickly removed with low cost. Because the negative photoresist can realize that a negative image can be manufactured under the condition of no crosslinking, wet photoresist removal can be adopted, the photoresist can be removed cleanly through normal temperature soaking, for example, a photoresist removing solvent N-methylpyrrolidone or other solvents which are common in the industry can be used, the photoresist can be removed cleanly through normal temperature soaking for less than 2min, the production efficiency is improved, and the production cost is reduced; and the common negative photoresist is prepared into a negative image by adopting a poly-p-hydroxystyrene resin crosslinking mode, so that wet photoresist stripping is difficult, and only a dry photoresist stripping mode with higher cost can be used, thereby reducing the production efficiency and improving the production cost.
In a preferred embodiment, the protective group-containing poly (p-hydroxystyrene) copolymers of the invention have a molecular weight Mw of from 1000 to 20000, typical but non-limiting molecular weights Mw being, for example 1000、2000、3000、4000、5000、6000、7000、8000、9000、10000、11000、12000、13000、14000、15000、16000、17000、18000、19000、20000.
The molecular weight preferred by the invention can further enable the KrF negative photoresist to exert better developing effect.
In a preferred embodiment, the acidic catalyst of the present invention is at least one of an organic acid including, but not limited to, at least one of formic acid, acetic acid, propionic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and p-toluenesulfonic acid, and an inorganic acid including, but not limited to, at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrofluoric acid.
In a preferred embodiment, the anionic initiator of the present invention includes, but is not limited to, benzyl orthotoluate.
The preferred acid catalyst of the invention can better catalyze the protecting group of the poly-p-hydroxystyrene copolymer to fall off in the non-exposure area, and the compound generated by the benzyl o-toluylcarbamate can better deactivate the preferred acid catalyst after the exposure area is exposed by the ultraviolet light with the wavelength of 248nm, so that the protecting group is not catalyzed any more.
In a preferred embodiment, the solvent of the present invention includes, but is not limited to, at least one of propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl acetate, and ethyl lactate.
The solvent preferred in the present invention can better dissolve the above components to produce a KrF negative photoresist.
In a preferred embodiment, the KrF negative photoresist of the present invention comprises the following components in parts by weight:
10 to 60 parts of poly (p-hydroxystyrene) copolymer resin containing protective groups, 0.2 to 5 parts of acid catalyst, 0.2 to 5 parts of anionic initiator and 5 to 100 parts of solvent.
In the present invention, typical but non-limiting parts by weight of the protecting group-containing poly (p-hydroxystyrene) copolymer resin are, for example, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts; typical but non-limiting parts by weight of the acidic catalyst are, for example, 0.2 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts; typical but non-limiting parts by weight of anionic initiators are for example 0.2 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts; typical but non-limiting parts by weight of solvents are for example 5 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts.
In a preferred embodiment, the KrF negative photoresist of the present invention comprises the following components in parts by weight:
20 parts of a poly (p-hydroxystyrene) copolymer resin containing a protecting group, 0.2 part of an acidic catalyst, 0.4 to 0.5 part of o-toluylcarbamate and 100 parts of a solvent.
The proportion of the components in parts by weight, which is preferred by the invention, can lead the KrF negative photoresist to obtain better developing effect, and the wet photoresist stripping effect is better and the removal is faster.
According to a second aspect of the present invention, there is provided a method for preparing the above KrF negative photoresist, comprising the steps of:
The components are dissolved by using a solvent to obtain the KrF negative photoresist.
In a preferred embodiment, the invention further comprises filtration after dissolution.
The invention utilizes the solvent to dissolve each component, and then filters to obtain the KrF negative photoresist; wherein filtration includes, but is not limited to, filtration with a filter membrane having a pore size of 0.01 to 1 micron, with typical but non-limiting pore sizes such as 0.01 micron, 0.02 micron, 0.05 micron, 0.1 micron, 0.2 micron, 0.5 micron, 1 micron.
The preparation method of the KrF negative photoresist provided by the invention has the advantages of simple process and high excellent rate.
According to a third aspect of the present invention, there is provided the use of the above KrF negative photoresist in integrated circuit fabrication.
The application of the invention can better manufacture the integrated circuit, reduce the process cost and improve the production efficiency.
The invention is further illustrated by the following examples. The materials in the examples were prepared according to the existing methods or were directly commercially available unless otherwise specified.
Example 1
The KrF negative photoresist of this example mainly comprises the components in the weight ratio shown in the following table, after the components are mixed, the solvent propylene glycol methyl ether acetate is fully dissolved, and then the solution is filtered by a filter membrane with a pore diameter of 0.05 microns, so as to obtain the KrF negative photoresist, wherein the structure of the poly (p-hydroxystyrene) copolymer containing the protecting group is (a: b=6:4, and mw=10000):
example 2
The KrF negative photoresist of this example mainly comprises the components in the weight ratio shown in the following table, after the components are mixed, the solvent propylene glycol methyl ether acetate is fully dissolved, and then the solution is filtered by a filter membrane with a pore diameter of 0.05 microns, so as to obtain the KrF negative photoresist, wherein the structure of the poly (p-hydroxystyrene) copolymer containing the protecting group is (a: b=6:4, and mw=10000):
Example 3
The KrF negative photoresist of this example mainly comprises the components in the weight ratio shown in the following table, after mixing the components, the solvent propylene glycol methyl ether is fully dissolved, and then the solution is filtered by a filter membrane with a pore size of 0.05 microns, so as to obtain the KrF negative photoresist, wherein the structure of the poly (p-hydroxystyrene) copolymer containing the protecting group is (m: n=6:4, and mw=10000):
Example 4
The KrF negative photoresist of this example mainly comprises the components in the weight ratio shown in the following table, after the components are mixed, the solvent propylene glycol methyl ether acetate is fully dissolved, and then the solution is filtered by a filter membrane with a pore diameter of 0.05 microns, so as to obtain the KrF negative photoresist, wherein the structure of the poly (p-hydroxystyrene) copolymer containing the protecting group is (a: b=5:5, and mw=8000):
Example 5
The KrF negative photoresist of this example is mainly composed of the components in the weight ratio shown in the following table, after mixing the components, the solvent propylene glycol methyl ether acetate is used for fully dissolving, and then a filter membrane with the aperture of 0.05 microns is used for filtering, so as to obtain the KrF negative photoresist, wherein the poly (p-hydroxystyrene) copolymer resin containing the protecting group isThe mass ratio of the two is 1:1, 10g each, where a: b=5:5, m: n=5:5, and mw=10000 for both.
Example 6
This example differs from example 1 in that the protecting group-containing poly (p-hydroxystyrene) copolymer of this example has mw=20000, and the remaining components, parameters, and preparation steps are the same as in example 1, resulting in a KrF negative photoresist.
Example 7
This example differs from example 2 in that the protecting group-containing poly (p-hydroxystyrene) copolymer of this example has a: b=7:3, and the remaining components, parameters, and preparation steps are the same as in example 2, resulting in a KrF negative photoresist.
Example 8
This example differs from example 3 in that the protecting group-containing poly (p-hydroxystyrene) copolymer of this example has mw=20000, and the remaining components, parameters, and preparation steps are the same as in example 3, resulting in a KrF negative photoresist.
Example 9
This example differs from example 3 in that the protecting group-containing poly (p-hydroxystyrene) copolymer of this example has m: n=7: 3, the remaining components, parameters and preparation steps were the same as in example 3, to obtain a KrF negative photoresist.
Comparative example 1
The negative photoresist of the comparative example mainly comprises the components in the weight ratio shown in the following table, after the components are mixed, the components are fully dissolved by using a solvent propylene glycol methyl ether acetate, and then the mixture is filtered by using a filter membrane with a pore diameter of 0.05 microns, so as to obtain the negative photoresist, wherein Mw=10000 of the poly (p-hydroxystyrene) homopolymer.
| Poly (p-hydroxystyrene) homopolymers | 20g |
| Glycoluril (glycoluril) | 2g |
| Triphenylsulfonium hexafluoroantimonate | 0.5g |
| Propylene glycol methyl ether acetate | 100g |
Comparative example 2
This comparative example differs from example 1 in that the a: b=4:6 of the protecting group-containing poly (p-hydroxystyrene) copolymer of this comparative example, and the remaining components, parameters and preparation steps are the same as in example 1, to obtain a KrF negative photoresist.
Comparative example 3
This comparative example differs from example 2 in that the a: b=8:2 of the protecting group-containing poly (p-hydroxystyrene) copolymer of this comparative example, and the remaining components, parameters and preparation steps are the same as in example 2, to obtain a KrF negative photoresist.
Comparative example 4
This comparative example differs from example 3 in that the protecting group-containing poly (p-hydroxystyrene) copolymer of this comparative example has m: n=4:6, and the remaining components, parameters, and preparation steps are the same as in example 3, resulting in a KrF negative photoresist.
Experimental example 1
Spin-coating the negative photoresist provided in examples 1 to 9 and comparative examples 1 to 4 on the treated silicon wafer, respectively, pre-baking (PAB) 100 ℃/60s with a hot plate, adjusting the rotation speed to make the dried film thickness 500nm, exposing with a KrF exposure machine (pattern size 200 nm), then immersing and developing with 2.38wt% TMAH for 40s with 130 ℃/60s with a hot plate, and then cleaning with deionized water to obtain a negative image, adjusting the exposure dose to make the line width 200nm, and obtaining the substrates prepared from the negative photoresist provided in examples 1 to 9 and comparative examples 1 to 4, respectively.
Among them, the negative photoresists provided in comparative examples 2 to 4, because the ratio of the protecting groups is not proper, were not completely deprotected in the photolithography process, were not developed cleanly, and failed to form an effective photolithographic image.
The substrates prepared in examples 1 to 9 and comparative example 1 were immersed in an N-methylpyrrolidone solvent at 23℃and the photoresist dissolution time was observed, and as a result, it was found that the negative photoresist on the substrates corresponding to examples 1 to 9 was dissolved within 60 seconds, while the negative photoresist on the substrate corresponding to comparative example 1 was not changed or changed significantly, and the negative photoresist was not dissolved, as shown in Table 1.
TABLE 1
| Sample of | Dissolution time(s) |
| Example 1 | 35 |
| Example 2 | 33 |
| Example 3 | 38 |
| Example 4 | 29 |
| Example 5 | 36 |
| Example 6 | 52 |
| Example 7 | 34 |
| Example 8 | 56 |
| Example 9 | 38 |
| Comparative example 1 | Undissolved for 10min |
Therefore, compared with the common negative photoresist or the KrF negative photoresist which is not in the protection scope of the invention, the KrF negative photoresist provided by the invention can adopt wet photoresist removal, and the photoresist can be removed cleanly by soaking at normal temperature, thereby avoiding dry photoresist removal with high cost and low efficiency, greatly reducing the process cost and improving the production efficiency.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A KrF negative photoresist, comprising the following components:
a poly-p-hydroxystyrene copolymer, an acidic catalyst, a photoactivator, and a solvent;
the poly-p-hydroxystyrene copolymer comprises a poly-p-hydroxystyrene copolymer containing a protecting group;
the protecting group-containing poly (p-hydroxystyrene) copolymer comprises at least one of a compound represented by the following general formula (1) and a compound represented by the general formula (2):
wherein a: b= (5 to 7): (5-3);
Wherein, m: n= (5-7): (5-3);
The photoactivator is an anionic initiator;
The KrF negative photoresist comprises the following components in parts by weight:
10 to 60 parts of poly (p-hydroxystyrene) copolymer containing a protecting group, 0.2 to 5 parts of acid catalyst, 0.2 to 5 parts of anionic initiator and 5 to 100 parts of solvent;
the anionic initiator is benzyl orthotoluate.
2. The KrF negative photoresist according to claim 1, wherein the molecular weight Mw of the poly (p-hydroxystyrene) copolymer containing a protecting group is 1000 to 20000.
3. The KrF negative photoresist according to claim 1, wherein the acidic catalyst is at least one of an organic acid and an inorganic acid.
4. The KrF negative photoresist according to claim 3, wherein the organic acid comprises at least one of formic acid, acetic acid, propionic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and p-toluenesulfonic acid.
5. The KrF negative photoresist according to claim 3, wherein the inorganic acid comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrofluoric acid.
6. The KrF negative photoresist according to claim 1, wherein the solvent comprises at least one of propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl acetate, and ethyl lactate.
7. The KrF negative photoresist according to claim 1, wherein the KrF negative photoresist comprises the following components in parts by weight:
20 parts of a poly (p-hydroxystyrene) copolymer containing a protecting group, 0.2 part of an acidic catalyst, 0.4-0.5 part of o-toluylcarbamate and 100 parts of a solvent.
8. A method for preparing the KrF negative photoresist according to claim 1, comprising the steps of:
and dissolving the components by using the solvent to obtain the KrF negative photoresist.
9. The method of claim 8, further comprising filtering after dissolving;
the filtering comprises filtering with a filter membrane;
the pore diameter of the filter membrane is 0.01-1 micron.
10. Use of the KrF negative photoresist according to any one of claims 1-7 in integrated circuit fabrication.
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| CN108132584A (en) * | 2017-12-22 | 2018-06-08 | 江苏汉拓光学材料有限公司 | A kind of photoetching compositions comprising poly(4-hydroxystyrene) Type of Collective object and acrylate copolymer |
| CN108864341A (en) * | 2017-05-12 | 2018-11-23 | 湖北固润科技股份有限公司 | Poly(4-hydroxystyrene) based epoxy resin, its synthesis and application |
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| JP3832467B2 (en) * | 2003-11-17 | 2006-10-11 | Ｊｓｒ株式会社 | Negative radiation sensitive resin composition |
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| CN108864341A (en) * | 2017-05-12 | 2018-11-23 | 湖北固润科技股份有限公司 | Poly(4-hydroxystyrene) based epoxy resin, its synthesis and application |
| CN108132584A (en) * | 2017-12-22 | 2018-06-08 | 江苏汉拓光学材料有限公司 | A kind of photoetching compositions comprising poly(4-hydroxystyrene) Type of Collective object and acrylate copolymer |
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