CN112731764A - Negative photoresist composition and method for forming photoresist pattern - Google Patents
Negative photoresist composition and method for forming photoresist pattern Download PDFInfo
- Publication number
- CN112731764A CN112731764A CN202011598952.XA CN202011598952A CN112731764A CN 112731764 A CN112731764 A CN 112731764A CN 202011598952 A CN202011598952 A CN 202011598952A CN 112731764 A CN112731764 A CN 112731764A
- Authority
- CN
- China
- Prior art keywords
- formula
- negative photoresist
- photoresist composition
- percent
- resin
- 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
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
-
- 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
- G03F7/075—Silicon-containing 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
- G03F7/30—Imagewise removal using liquid means
-
- 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
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
Abstract
The invention discloses a negative photoresist composition and a method for forming photoresist pattern, the negative photoresist composition comprises: a component (1): a resin comprising a plurality of repeating units, the repeating units of the resin comprising hydroxyl groups; a component (2): a free radical generator; a component (3): the cross-linking agent adopts a cross-linking agent containing siloxane groups. The negative photoresist composition adopts the crosslinking agent containing the siloxane group, the imaging performance of the negative photoresist is basically unchanged, but the crosslinking agent containing the siloxane shows good heat resistance in the aspect of imaging patterns, and the pattern shape is almost unchanged and keeps good after being baked at 130 ℃ for 150 seconds.
Description
Technical Field
The present invention relates to the field of lithography, and more particularly, to a negative photoresist composition and a method of forming a photoresist pattern.
Background
Photoresist compositions are used in microlithographic processes (microlithographic processes) for applications such as in the fields of illumination LED fabrication, liquid crystal LCD panel fabrication, OLED panel fabrication, micro LED panel fabrication, MEMS chip semiconductor fabrication, integrated circuit chip fabrication, and chip packaging processes. A thin film of the photoresist composition is typically first coated onto a substrate material, such as a silicon wafer used in the manufacture of integrated circuits; then, baking the coated substrate to evaporate the solvent in the photoresist composition and fix the coating layer onto the substrate; the dried coated surface of the substrate is then imagewise exposed to imaging radiation.
The radiation exposure causes a chemical transformation in the exposed areas of the coated surface. Currently, visible light, Ultraviolet (UV), electron beam and X-ray radiant energy are the types of imaging radiation commonly used in microlithography. After imagewise exposure, the coated substrate is treated with a developer solution to dissolve and remove either the radiation-exposed or the unexposed areas of the coated surface of the substrate.
Negative-working photoresist compositions are imagewise exposed to radiation, the areas of the negative-working photoresist composition exposed to the radiation (e.g., undergoing a crosslinking reaction) become insoluble to a developer solution, while the unexposed areas of the negative-working photoresist coating remain relatively soluble to the developer solution. Thus, treatment of an exposed negative-working photoresist composition with a developer causes removal of the unexposed areas of the coating of negative-working photoresist composition and the formation of a reverse image in the coating. For positive-working photoresist compositions, the principle is reversed, and the developer solution is removed from the exposed portions of the coating of positive-working photoresist composition.
Negative-working photoresist compositions are known in the art which generally comprise a polymeric resin, a free radical generator, and a crosslinking agent, and are irradiated with imaging radiation to cause the polymeric resin and the crosslinking agent in the exposed portions of the negative-working photoresist composition to undergo free radical polymerization to cure, become insoluble in a developer solution, and are completely removed by dissolution in an alkaline developer solution, thereby leaving exposed regions in a pattern.
At present, hydrocarbon main chains such as ether-containing polymer chains, aromatic ring main chains, aliphatic alkyl main chains and the like are often used as common crosslinking agents, wherein the ether-containing polymer chains generally have good hydrophilicity but poor heat resistance, and therefore, poor imaging patterns in an exposure area, such as a dome or pattern melting phenomenon of an imaging pattern, are easily caused by the pattern under the action of a developing solution or during high-temperature baking; the main chain structure formed by aromatic ring and/or fatty alkyl has insufficient flexibility, the negative photoresist composition coating film is not good, and the coating is easy to crack during baking or the image pattern is easy to crack under the action of stress.
In view of the above, there is a need to provide a novel negative photoresist composition which is less likely to cause pattern abnormalities during exposure, development and patterning.
Disclosure of Invention
The present invention provides a negative photoresist composition and a method for forming a photoresist pattern, which solve the above problems, and the negative photoresist composition has advantages of good heat resistance and stable pattern after imaging when forming a film.
The present invention provides a negative photoresist composition comprising:
a negative photoresist composition comprising:
a component (1): a resin comprising a plurality of repeating units, the repeating units of the resin comprising hydroxyl groups;
a component (2): a free radical generator;
a component (3): the cross-linking agent is selected from one or two of the cross-linking agents shown in the formulas (1) and (2);
formula (1):
formula (2):
wherein R is0Selected from hydrogen or methyl, R1、R2、R3、R4Each independently selected from hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, or aromatic group of 6 to 12 carbon atoms; m1 is 1-20; m2 is 1-20; m3 is 2-30.
Preferably, R1、R2、R3、R4Each independently selected from methyl, ethyl, propyl, isopropyl,Methoxy, ethoxy, propoxy, isopropoxy or phenyl.
Preferably, the resin is selected from one or more of polyethylene copolymer, polypropylene copolymer, phenolic resin copolymer, polyester copolymer and polyether copolymer.
Preferably, the resin is selected from one or more of the resins represented by formula (3), formula (4), formula (5) and formula (6);
formula (3):
formula (4):
formula (5):
formula (6):
wherein, in the formulae (3) to (6), R5Represents a hydrogen atom, a halogen, an alkyl group of 1 to 4 carbon atoms, or an alkoxy group of 1 to 4 carbon atoms;
wherein in the formula (3), n is 5-1000; in the formula (4), a is less than or equal to 20 percent, b is more than 60 percent, c is more than 5 percent and less than 10 percent; in the formula (5), a is less than or equal to 20 percent, b is less than or equal to 40 percent, and c is more than 40 percent; in the formula (6), a is more than 50 percent, and b is less than or equal to 50 percent.
Preferably, the weight average molecular weight of the substance represented by the formula (3) is 300-.
Preferably, the free radical generator is selected from one or more of free radical generators represented by formula (7), formula (8), formula (9) and formula (10), or free radical generators suitable for 248nm or 193nm exposure light source;
formula (7):
formula (8):
formula (9):
formula (10):
preferably, the negative photoresist composition further comprises a surfactant, an additive, and a solvent; the surfactant is selected from fluorocarbon surfactant and/or silicon-containing surfactant, and the additive comprises a leveling agent and a defoaming agent.
Preferably, the negative photoresist composition comprises, in parts by weight:
5 to 30 parts of component (1);
0.1 to 10 parts of component (2);
1 to 10 parts of component (3);
0.05-5 parts of a surfactant;
0.05-5 parts of additive;
40-190 parts of solvent.
A method of forming a photoresist pattern using a negative photoresist composition, which is the above negative photoresist composition.
Preferably, the method of forming the photoresist pattern includes:
s1, providing a substrate, and coating the negative photoresist composition on the surface of one side of the substrate to form a negative photoresist composition coating;
s2, baking the negative photoresist composition coating to form a negative photoresist film layer;
s3, exposing the negative photoresist film layer by actinic radiation through a photoetching machine device;
s4, baking the exposed negative photoresist film layer;
and S5, applying a developer to the exposed negative photoresist film layer, and removing the unexposed part of the negative photoresist film layer to form the photoresist pattern.
Compared with the prior art, the negative photoresist composition has the beneficial effects that:
(1) the imaging performance of the negative photoresist is basically unchanged under the action of the crosslinking agent containing the siloxane group, but the crosslinking agent containing the siloxane shows good heat resistance in the aspect of imaging patterns, and the pattern shape is almost unchanged and well maintained after being baked at 130 ℃ for 150 seconds. Compared with the prior negative photoresist which does not contain siloxane group, the pattern formed by imaging of the negative photoresist is almost completely melted after being baked for 150 seconds at 130 ℃, and the heat resistance is insufficient.
(2) Under the condition of the i-line free radical generator, the i-line exposure machine and the like can obtain good imaging effect.
(3) This type of photoresist can be used for exposure molding in KrF and ArF exposure machines, with the replacement of free radical generators sensitive to 248nm and 193nm light sources.
(4) In the comparative example, the film reduction rate of the crosslinking agent without siloxane groups under the action of TMAH alkaline developer is higher, while the film reduction rate of the negative photoresist after the new crosslinking agent containing siloxane groups is greatly improved, and a good film retaining effect is shown.
(5) The novel negative photoresist composition containing the siloxane-based crosslinking agent can be applied to the advantage of wide application range.
Detailed Description
Example embodiments will now be described more fully. Example embodiments may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example embodiments to those skilled in the art.
Embodiments of the invention provide a negative photoresist composition comprising component (1), component (2), and component (3). Further, the negative photoresist composition may further include auxiliary components such as a surfactant, an additive, and a solvent.
In a preferred embodiment, component (1): the resin contains a plurality of repeating units, wherein the repeating units of the resin contain hydroxyl groups, and the hydroxyl groups are preferably phenolic hydroxyl groups. Wherein, the phenolic hydroxyl group can be formed by phenol substances, the phenol substances can be monophenol substances or polyphenol substances, and the resin can be monophenol substances, polyphenol substances or copolymers thereof, or copolymers of the monophenol substances, the polyphenol substances and other functional groups.
The resin containing a plurality of repeating units may be one or more of a polyethylene copolymer, a polypropylene copolymer, a phenol resin copolymer, a polyester copolymer, and a polyether copolymer, depending on the polymerization method of the copolymer. The resin of the component (1) of the present invention is less expensive than other resins.
In the present invention, the resin of the component (1) is preferably a phenol resin copolymer.
In some embodiments of the present invention, the resin of component (1) is selected from one or more of the resins represented by formula (3), formula (4), formula (5), and formula (6).
Formula (3):
formula (4):
formula (5):
formula (6):
wherein, in the formulae (3) to (6), R5Represents a hydrogen atom, a halogen, an alkyl group of 1 to 4 carbon atoms, or an alkyl group of 1 to 4 carbon atomsAn oxy group; the above-mentioned halogen is, for example, fluorine, chlorine, bromine, iodine; examples of the alkyl group include saturated aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; examples of the alkoxy group include saturated aliphatic alkoxy groups such as methoxy, ethoxy, propoxy and isopropoxy;
wherein, in the formula (3), n is 5-1000, preferably 5-300; in the formula (4), a is less than or equal to 20 percent, b is more than 60 percent, c is more than 5 percent and less than 10 percent; in the formula (5), a is less than or equal to 20 percent, b is less than or equal to 40 percent, and c is more than 40 percent; in the formula (6), a is more than 50 percent, and b is less than or equal to 50 percent.
In some embodiments of the invention, the weight average molecular weight of the material represented by formula (3) is 300-10000; the weight average molecular weight of the substance represented by the formula (4) is 200-; the weight average molecular weight of the substance represented by the formula (5) is 200-; the weight average molecular weight of the substance represented by the formula (6) is 200-.
A component (2): a radical generator, for example, a radical photo-generator, selected from one or more radical generators represented by formula (7), formula (8), formula (9), formula (10);
formula (7):
formula (8):
formula (9):
formula (10):
among them, the radical generators represented by the formulae (7) to (10) are, for example, radical generators applicable to i (wavelength of 365nm) line; alternatively, the radical generator can be applied to KrF (KrF excimer laser, light source of KrF, wavelength of 248 nm).
A component (3): and the crosslinking agent is selected from one or two of the crosslinking agents represented by the formula (1) and the formula (2).
Formula (1):
formula (2):
wherein R is0Selected from hydrogen or methyl, R1、R2、R3、R4Each independently selected from hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, or aromatic group of 6 to 12 carbon atoms; m1 is 1-20; m2 is 1-20; m3 is 2-30.
In some embodiments of the invention, R1、R2、R3、R4Each independently selected from methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, isopropoxy or phenyl.
In some embodiments of the invention, the crosslinking agent is selected from one or more of crosslinking agents 2-4.
Crosslinking agent 2:
crosslinking agent 3:
crosslinking agent 4:
the research shows that compared with the existing crosslinking agent, the crosslinking agent containing siloxane groups shown in the formula (1) and the formula (2) has remarkably excellent film forming and curing performance, and in the baking process of a coating and a pattern, the pattern is stable in shape and does not melt, and the high-temperature resistance and flexibility are good, so that the cracking phenomenon of the pattern under the action of film cracking or stress can not occur.
In some embodiments of the invention, the negative photoresist composition further comprises a surfactant, for example comprising a fluorocarbon surfactant and/or a silicon-containing surfactant.
The fluorocarbon surfactant is preferably a non-ionic fluorocarbon surfactant, and is one or more of the models Surflon S-386, Surflon S-393, Surflon S-651, Surflon S-611 and Novec FC-4432. The fluorocarbon chain hydrophobic group and the hydrophilic group which are simultaneously arranged in the structure of the adopted fluorocarbon surfactant can ensure that the fluorocarbon surfactant has good solubility in water or various common organic solvents; in addition, the surface tension provided by the non-ionic fluorocarbon surfactant is small, and the surface energy can be well reduced, so that the adhesive force between the photoresist and a film layer to be patterned on the substrate is enhanced, and the photoresist composition can be coated on the film layer to be patterned.
The silicon-containing surfactant is preferably a silicone surfactant.
In some embodiments of the invention, the negative photoresist composition further comprises an additive and a solvent. The additives are preferably leveling agents and defoamers.
The leveling agent is preferably one or more selected from MEGAFACE F-563 (available from DIC), polymethylphenylsiloxane, polydimethylsiloxane, and ETA-706. The dosage of the auxiliary agent is 0.01-1% of the total mass of the formula.
Additionally, specific commercial examples of optional leveling agents are: a modesty 431, a modesty 432, a modesty 495, a modesty 810, a G1ide100, a Glide440, a Flow300, a Flow425, a Flow460, a Byk333, a Byk371, a Byk373, an Efk a3883, an Efka3600, an RF322, an RF325, an RF 328.
The defoaming agent is preferably selected from the group consisting of two highly spreading and penetrating aids of organic polymers and silicone resins. Specific commercially available products are exemplified by: the modesty boards 3100, 5300, Foamex810, Foamex N, Airex920, Byk055, Byk088, Byk067, Efk a2720, Efk a 2721.
The organic solvent used in the negative photoresist is usually selected from medium polarity organic solvents, such as dichloromethane or chloroform, and ketones, esters, ethers, aliphatic and naphthenic compounds or some aromatic solvents, such as: one or more of ethylene glycol isopropyl ether, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether, dimethylacetamide, N-methylpyrrolidone, gamma-butyrolactone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol ester and diethylene glycol butyl ether; the organic solvent of the carbohydrate combined by the ether and the ester has hydrophilicity and good compatibility with dye, and can also be used as a solvent, such as one or more of 3-methoxy butyl acetate, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate and 3-ethoxy ethyl acrylate.
In some embodiments of the invention, the negative photoresist composition comprises, in parts by weight:
5 to 30 parts of component (1);
0.1 to 10 parts of component (2);
1 to 10 parts of component (3);
0.05-5 parts of a surfactant;
0.05-5 parts of additive;
40-190 parts of solvent.
Embodiments also provide a method of forming a photoresist pattern using the above negative photoresist composition.
Specifically, the method of forming a photoresist pattern includes the steps of:
s1, providing a substrate, for example, a substrate selected from a monocrystalline silicon wafer, a polycrystalline silicon wafer, a glass substrate, a copper or aluminum metal substrate, wherein the surface of one side of the substrate comprises a film layer to be patterned, and coating the film layer to be patterned with the negative photoresist composition to form a coating of the negative photoresist composition;
s2, baking the negative photoresist composition coating, wherein the baking temperature can be 60-180 ℃, and preferably 80-130 ℃; the baking time may be 30-180 seconds, preferably 150 seconds; the baking in this step, also known as "pre-baking", is to remove the solvent from the negative photoresist composition to form a negative photoresist film;
s3, exposing the negative photoresist film layer by actinic radiation through a photoetching machine device; the light source wavelength can be full-wave band g-h-i line (356nm-435nm), g line (435nm), i line (365nm), KrF (248nm), ArF (193nm), EUV (13.5nm), etc.; preferably, i-line (365nm), KrF (248 nm);
s4, baking the exposed negative photoresist film layer; as the light amplification condition, the baking temperature after exposure may be 60 to 150 ℃, preferably 90 to 120 ℃; the baking time may be 30 to 150 seconds, preferably 60 seconds;
s5, cooling the substrate to room temperature, preferably 25 ℃ ± 3 ℃; and applying a developer to the exposed negative photoresist film layer, removing the unexposed area of the negative photoresist film layer by the developer, and developing to form the photoresist pattern. The developer may be TMAH and the concentration may be 1-5%, preferably 2.38%.
Preparation of resin A:
firstly, 50g of p-methylphenol, 40g of m-methylphenol and 10g of 3, 5-dimethylphenol are respectively added into a 200ml two-neck flask; secondly, adding 3.5g of 10 wt% succinic acid aqueous solution into a 200ml two-neck flask, and heating to 100 ℃ to obtain reaction liquid; then slowly dripping 37 wt% of formaldehyde solution into the reaction solution for 30 minutes, continuing to react for 30 minutes, heating, and distilling and removing water in the two-neck flask; and connecting the two flasks with a vacuum pump, and distilling and removing unreacted residual monomers under the reduced pressure of 10mmHg to obtain the target product, namely the phenolic resin A. The resin A is phenolic resin.
The finally obtained resin A had a weight average molecular weight of about 3400 as measured by GPC (gel permeation chromatography).
Preparation of resin B:
first, a radical initiator AMBN (azobisisovaleronitrile) was added to 100g of a 2-butanone solvent and stirred until completely dissolved.
Secondly, 300g of 2-butanone is added into a 1000ml three-port reaction kettle, 31.25g of monomer B-1(0.3mol), 70.09g of monomer B-2(0.6mol) and 12.81g of monomer B-3(0.1mol) are sequentially added into the three-port reaction kettle, and the mixture is heated and stirred under the condition of nitrogen until the mixture is completely dissolved; then, the temperature is raised to 80 ℃, then the 2-butanone solution of the standby AMBN is slowly dripped into the three-opening reaction kettle, and the temperature is reduced to the room temperature after the reaction is carried out for 4 hours.
Pouring the reaction solution in the three-opening reaction kettle into a beaker filled with 1000ml of hexane to precipitate white resin powder, filtering by using filter paper to collect the white resin powder, and washing the white resin powder by using hexane for a plurality of times; after drying under vacuum at 50 ℃ for 17 hours, the desired product, resin B powder, was obtained and weighed 98.75g (yield 85%).
The weight average molecular weight of the finally obtained resin B was measured by GPC (gel permeation chromatography), and the measured weight average molecular weight was about 8270.
Preparation of Cross-linker 3
500ml of methanol was charged into a 1000ml three-necked flask, and 43.6g (0.25mol) of 1- (dimethoxy (methyl) silyl) but-3-en-2-one (available from shin-Etsu chemical Co., Ltd.) and 81g (0.77mol) of dimethoxy (dimethyl) silane (available from shin-Etsu chemical Co., Ltd.) were added to the three-necked flask, respectively, in this order under stirring, and after 5 hours of reaction at room temperature, the methanol was removed by a rotary evaporator, and the resulting siloxane polymer was purified by refining with hexane several times to obtain the intended product, namely a crosslinking agent 3, with a yield of 90.12%.
Crosslinking agent 3 was measured for weight average molecular weight by GPC (gel permeation chromatography), and the weight average molecular weight was determined to be about 1127.
Example 1: preparation of negative photoresist composition
Adding 10g of synthetic resin A (phenolic resin) into 50g of PGMEA (propylene glycol monomethyl ether acetate), and stirring for 2 hours until the resin A is completely dissolved to form a reaction solution; then, 0.2g of radical generator-1 (available from Sigma Aldrich), 3g of synthesized crosslinking agent 2, 0.1g of leveling agent MEGAFACE F-563 (available from DIC) were added in this order to the PGMEA in which the resin A was dissolved; finally, 36.5g of PGME (propylene glycol methyl ether) as a solvent was added to the reaction solution, and stirred for 2 hours until the solid was completely dissolved, to obtain a sample. Finally, the sample was filtered through a 0.2 μ M filter (available from 3M company) to obtain a negative photoresist composition, sample No. A1.
Example 2: preparation of negative photoresist composition
The experimental procedure of this example is the same as that of example 1 except that in example 2, the crosslinking agent 3 is used as the crosslinking agent.
A negative photoresist composition made in example 2, sample No. a 2.
Example 3: preparation of negative photoresist composition
The experimental procedure of this example is the same as that of example 1, except that in example 3, the crosslinking agent 4 is used as the crosslinking agent.
A negative photoresist composition made in example 3, sample No. a 3.
Example 4: preparation of negative photoresist composition
10g of synthetic resin B (hydroxystyrene resin) was added to 50g of PGMEA, and stirred for 2 hours to be completely dissolved; then, 0.2g of a radical generator-4 (available from Sigma Aldrich), 3g of a synthesized crosslinking agent 2, and 0.1g of a leveling agent MEGAFACE F-563 (available from DIC) were added in this order to the PGMEA in which the resin B was dissolved; then, 36.5g of PGME (propylene glycol methyl ether) as a solvent was added thereto, and the mixture was stirred for 2 hours until the solid was completely dissolved, thereby obtaining a sample. Finally, the sample was filtered through a 0.2um filter (available from 3M company), negative photoresist composition, sample No. B1.
Example 5: preparation of negative photoresist composition
The experimental procedure of this example is the same as that of example 4, except that in example 5, the crosslinking agent 3 was used as the crosslinking agent.
A negative photoresist composition made in example 5, sample No. B2.
Example 6: preparation of negative photoresist composition
The experimental procedure of this example is the same as that of example 4 except that in example 6, the crosslinking agent 4 is used as the crosslinking agent.
A negative photoresist composition made in example 6, sample No. B3.
Comparative example 1: preparation of negative photoresist composition
Crosslinking agent 1:
adding 10g of synthetic resin A (phenolic resin) into 50g of PGMEA, and stirring for 2 hours until the resin A is completely dissolved; then, 0.2g of free radical generator-1, 3g of cross-linking agent 1 are added in sequence; 0.1g of a leveling agent MEGAFACE F-563 (available from DIC corporation) to PGMEA in which the resin A was dissolved; finally, 28.5g of PGME (propylene glycol methyl ether) as a solvent was added thereto, and the mixture was stirred for 2 hours until the solid was completely dissolved, to obtain a control sample. Finally, the control sample was filtered through a 0.2 μ M filter (available from 3M company) to obtain a negative photoresist composition, reference No. 1.
Comparative example 2: preparation of negative photoresist composition
10g of synthetic resin B (hydroxystyrene resin) was added to 50g of PGMEA, and stirred for 2 hours to be completely dissolved; then, 0.2g of free radical generator-4 and 3g of cross-linking agent 1 are added in sequence; 0.1g of a leveling agent MEGAFACE F-563 (available from DIC corporation) to PGMEA in which resin B was dissolved; finally, 28.5g of PGME (propylene glycol methyl ether) as a solvent was added thereto, and the mixture was stirred for 2 hours until the solid was completely dissolved, to obtain a control sample. Finally, the control sample was filtered through a 0.2 μ M filter (available from 3M company) to obtain a negative photoresist composition, reference No. 1.
Application example 1: observation effect of exposure and development
For the negative photoresist compositions prepared in examples 1-6 and comparative examples 1-2, a2 μm film was formed on a silicon wafer by spin coating using a spin coater Labspin6 manufactured by Sus, the substrate was baked on a hot plate at 120 ℃ for 1 minute and then cooled to 23 ℃ room temperature, and then exposed using an exposure machine MA6 manufactured by Sus, the exposed substrate was developed with TMAH 2.38% developer for 1 minute and then washed with pure water, and after post-baking at 110 ℃, the cross section was observed using a scanning electron microscope SU-8100 manufactured by Hitachi and the line width was measured to determine the resolution change.
Application example 2: film reduction rate test
For the negative photoresist compositions prepared in examples 1-6 and comparative examples 1-2, photoresist films were formed on silicon wafers by spin coating using a spin coater Labspin6 manufactured by Sus corporation, and the substrates were baked on a hot plate at 120 ℃ for 1 minute and then cooled to 23 ℃ for room temperature. The film thickness was measured with a j.a.woollam ellipsometer, the data-SE, to give a film thickness T1. The silicon wafer substrate coated with the photoresist was developed with TMAH 2.38% developer for 1 minute, then cleaned with pure water, baked at 120 ℃, and then measured for film thickness T2 with an ellipsometer. The film reduction rate is (T1-T2)/T1.
TABLE 1 Components and proportions of examples 1-6 and comparative examples 1-2
Results and investigation:
1. and (3) observing imaging effect: as shown in table 2
TABLE 2
2. And (3) film reduction rate test: as shown in table 3
TABLE 3
And (4) conclusion: as can be seen from the inspection data,
(1) under the action of the crosslinking agent containing the siloxane group, the imaging performance of the negative photoresist is basically unchanged, but the crosslinking agent containing the siloxane shows good heat resistance in the aspect of imaging patterns, and the pattern shape is almost unchanged and keeps good after being baked at 130 ℃ for 150 seconds. Compared with the prior negative photoresist which does not contain siloxane group, the pattern formed by imaging of the negative photoresist is almost completely melted after being baked for 150 seconds at 130 ℃, and the heat resistance is insufficient.
(2) Under the condition of the i-line free radical generator, the i-line exposure machine and the like can obtain good imaging effect.
(3) This type of photoresist can be used for exposure molding in KrF and ArF exposure machines, with PAG's being used instead, which are sensitive to 248nm and 193nm light sources.
(4) In the comparative example, the film reduction rate of the crosslinking agent without siloxane groups under the action of TMAH alkaline developer is higher, while the film reduction rate of the negative photoresist after the new crosslinking agent containing siloxane groups is greatly improved, and a good film retaining effect is shown.
(5) The novel negative photoresist composition containing the siloxane-based crosslinking agent can be applied to the advantage of wide application range.
Although embodiments of the present invention have been shown and described, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that those skilled in the art may make changes, modifications, substitutions and alterations to the above embodiments without departing from the spirit and scope of the present invention, all such changes being within the scope of the appended claims.
Claims (10)
1. A negative photoresist composition, comprising:
a component (1): a resin comprising a plurality of repeating units, the repeating units of the resin comprising hydroxyl groups;
a component (2): a free radical generator;
a component (3): the cross-linking agent is selected from one or two of the cross-linking agents shown in the formulas (1) and (2);
formula (1):
formula (2):
wherein R is0Selected from hydrogen or methyl, R1、R2、R3、R4Each independently selected from hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, or aromatic group of 6 to 12 carbon atoms; m1 is 1-20; m2 is 1-20; m3 is 2-30.
2. The negative photoresist composition of claim 1, wherein R is1、R2、R3、R4Each independently selected from methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, isopropoxy or phenyl.
3. The negative photoresist composition of claim 1, wherein the resin is selected from one or more of polyethylene copolymer, polypropylene copolymer, phenolic copolymer, polyester copolymer, and polyether copolymer.
4. The negative photoresist composition of claim 1, wherein the resin is selected from one or more resins represented by formula (3), formula (4), formula (5), formula (6);
formula (3):
formula (4):
formula (5):
formula (6):
wherein, in the formulae (3) to (6), R5Represents a hydrogen atom, a halogen, an alkyl group of 1 to 4 carbon atoms, or an alkoxy group of 1 to 4 carbon atoms;
wherein in the formula (3), n is 5-1000; in the formula (4), a is less than or equal to 20 percent, b is more than 60 percent, c is more than 5 percent and less than 10 percent; in the formula (5), a is less than or equal to 20 percent, b is less than or equal to 40 percent, and c is more than 40 percent; in the formula (6), a is more than 50 percent, and b is less than or equal to 50 percent.
5. The negative photoresist composition of claim 4, wherein the weight average molecular weight of the substance represented by the formula (3) is 300-10000, and the weight average molecular weight of the substance represented by the formula (4) is 200-20000; the weight average molecular weight of the substance represented by the formula (5) is 200-; the weight average molecular weight of the substance represented by the formula (6) is 200-.
6. The negative photoresist composition of claim 1, wherein the radical generator is selected from one or more radical generators represented by formula (7), formula (8), formula (9), formula (10), or radical generators suitable for 248nm or 193nm exposure light;
formula (7):
formula (8):
formula (9):
formula (10):
7. the negative photoresist composition of claim 1, further comprising a surfactant, an additive, and a solvent; the surfactant is selected from fluorocarbon surfactant and/or silicon-containing surfactant, and the additive comprises a leveling agent and a defoaming agent.
8. The negative photoresist composition of claim 7, wherein the negative photoresist composition comprises, in parts by weight:
5 to 30 parts of component (1);
0.1 to 10 parts of component (2);
1 to 10 parts of component (3);
0.05-5 parts of a surfactant;
0.05-5 parts of additive;
40-190 parts of solvent.
9. A method of forming a photoresist pattern using a negative photoresist composition, wherein the negative photoresist composition is the negative photoresist composition of any one of claims 1 to 8.
10. The method of forming a photoresist pattern according to claim 9, wherein the method of forming a photoresist pattern comprises:
s1, providing a substrate, and coating the negative photoresist composition of any one of claims 1 to 8 on a surface of one side of the substrate to form a coating layer of the negative photoresist composition;
s2, baking the negative photoresist composition coating to form a negative photoresist film layer;
s3, exposing the negative photoresist film layer by actinic radiation through a photoetching machine device;
s4, baking the exposed negative photoresist film layer;
and S5, applying a developer to the exposed negative photoresist film layer, and removing the unexposed part of the negative photoresist film layer to form the photoresist pattern.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011598952.XA CN112731764A (en) | 2020-12-29 | 2020-12-29 | Negative photoresist composition and method for forming photoresist pattern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011598952.XA CN112731764A (en) | 2020-12-29 | 2020-12-29 | Negative photoresist composition and method for forming photoresist pattern |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112731764A true CN112731764A (en) | 2021-04-30 |
Family
ID=75611490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011598952.XA Pending CN112731764A (en) | 2020-12-29 | 2020-12-29 | Negative photoresist composition and method for forming photoresist pattern |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112731764A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101639628A (en) * | 2008-07-31 | 2010-02-03 | Jsr株式会社 | Radioactive linear composition for forming of coloring layer, color filter and color liquid crystal display element |
| CN101770172A (en) * | 2008-12-31 | 2010-07-07 | 第一毛织株式会社 | Organic layer photosensitive resin composition and organic layer fabricated using same |
| CN101872115A (en) * | 2008-12-19 | 2010-10-27 | 奥贝达克特公司 | Methods and processes for modifying polymer material surface interactions |
| CN103229103A (en) * | 2010-12-24 | 2013-07-31 | 株式会社艾迪科 | Photosensitive resin composition |
| US20130337381A1 (en) * | 2012-06-15 | 2013-12-19 | Az Electronic Materials (Luxembourg) S.A.R.L. | Negative-working thick film photoresist |
| CN105122137A (en) * | 2013-03-28 | 2015-12-02 | 东丽株式会社 | Photosensitive resin composition, protection film or insulation film, touch panel and method for manufacturing same |
| CN111538210A (en) * | 2020-05-26 | 2020-08-14 | 苏州理硕科技有限公司 | Positive photoresist composition and method for forming photoresist pattern |
-
2020
- 2020-12-29 CN CN202011598952.XA patent/CN112731764A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101639628A (en) * | 2008-07-31 | 2010-02-03 | Jsr株式会社 | Radioactive linear composition for forming of coloring layer, color filter and color liquid crystal display element |
| CN101872115A (en) * | 2008-12-19 | 2010-10-27 | 奥贝达克特公司 | Methods and processes for modifying polymer material surface interactions |
| CN101770172A (en) * | 2008-12-31 | 2010-07-07 | 第一毛织株式会社 | Organic layer photosensitive resin composition and organic layer fabricated using same |
| CN103229103A (en) * | 2010-12-24 | 2013-07-31 | 株式会社艾迪科 | Photosensitive resin composition |
| US20130337381A1 (en) * | 2012-06-15 | 2013-12-19 | Az Electronic Materials (Luxembourg) S.A.R.L. | Negative-working thick film photoresist |
| CN105122137A (en) * | 2013-03-28 | 2015-12-02 | 东丽株式会社 | Photosensitive resin composition, protection film or insulation film, touch panel and method for manufacturing same |
| CN111538210A (en) * | 2020-05-26 | 2020-08-14 | 苏州理硕科技有限公司 | Positive photoresist composition and method for forming photoresist pattern |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI294990B (en) | Hydroxy-amino thermally cured undercoat for 193 nm lithography | |
| JP4516963B2 (en) | Negative resist composition having fluorosulfonamide-containing polymer and pattern forming method | |
| TWI518462B (en) | Coating compositions for use with an overcoated photoresist | |
| KR19990067915A (en) | Polymers and photoresist compositions for short wavelength imaging | |
| TW201011078A (en) | An antireflective coating composition | |
| TW200916539A (en) | An antireflective coating composition comprising fused aromatic rings | |
| KR19990044985A (en) | Novel polymer and photosensitive resist composition | |
| WO2007069640A1 (en) | Novel compound, polymer, and resin composition | |
| TW200304582A (en) | Negative deep ultraviolet photoresist | |
| JP5418906B2 (en) | Anti-reflective coating composition | |
| WO2018016648A1 (en) | Compound, resin, composition, and pattern formation method | |
| WO2018016634A1 (en) | Compound, resin, and composition, as well as resist pattern formation method and circuit pattern formation method | |
| CN111538210B (en) | Positive photoresist composition and method for forming photoresist pattern | |
| JP4466855B2 (en) | Positive resist composition | |
| JP6754742B2 (en) | Photocuring resin composition and photocurable pattern produced from it | |
| TW201100968A (en) | Resist underlayer film forming composition containing polymer having acetal structure on side group and method for forming resist pattern | |
| TWI610979B (en) | Pattern forming method | |
| TW202215154A (en) | Curable resin composition, cured film, laminate, method for manufacturing cured film, and semiconductor device | |
| TW202204476A (en) | Photosensitive resin composition, cured film, laminate, method for producing cured film, and semiconductor device | |
| JP7386860B2 (en) | Acrylic polymerized polysiloxane, composition comprising the same, and cured film using the same | |
| JPWO2018135498A1 (en) | Compound, resin, composition and pattern forming method | |
| CN110892326B (en) | Photosensitive resin composition and cured film | |
| JP7056662B2 (en) | Polymers, resin compositions, resin films, methods for manufacturing patterned resin films, and electronic components | |
| CN112731764A (en) | Negative photoresist composition and method for forming photoresist pattern | |
| TW201934618A (en) | Photosensitive siloxane composition and pattern forming method using the same |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210430 |