Photoresist, patterned film, patterned substrate, semiconductor device and method for manufacturing the same

Abstract

The present application provides a photoresist, a patterned film, a patterned substrate, a semiconductor device and a preparation method thereof. The photoresist includes a film-forming resin, a photoacid generator, an additive and a solvent. The additive includes an anti-aging agent. The anti-aging agent includes a compound with a structural formula as follows, where R<supgt;1< / supgt>, R<supgt;2< / supgt>, R<supgt;3< / supgt> and R<supgt;4< / supgt> are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, -(C=O)-R<supgt;5< / supgt> or -(C=O)O-R<supgt;6< / supgt>. The photoresist provided by the present application contains an anti-aging agent with an epoxy structure, which is beneficial to inhibiting the aging reaction of the photoresist, improving the stability of the photoresist and prolonging the storage period of the photoresist.

Description

Technical Field

[0001] This application relates to the field of semiconductor fabrication, and specifically to photoresists, patterned films, patterned substrates, semiconductor devices, and methods for fabricating the same. Background Art

[0002] With the continuous development of semiconductor technology, the industry has increasingly higher requirements for the performance of photoresists. In related technologies, due to reasons such as raw materials, there is a small amount of residual acid in the photoresist when it leaves the factory, which easily causes the photoresist to age, reduces the stability of the photoresist, shortens the storage period of the photoresist, and is not conducive to the industrial application of the photoresist. Therefore, a photoresist with anti-aging properties, high stability, and a long storage period is needed. Summary of the Invention

[0003] In view of this, this application provides a photoresist, a patterned film, a patterned substrate, a semiconductor device, and a method for fabricating the same. The photoresist contains an anti-aging agent, which can react with the residual acid in the photoresist, slow down the aging process, improve the stability of the photoresist, and extend the storage period of the photoresist.

[0004] In a first aspect, this application provides a photoresist, the photoresist includes a film-forming resin, a photoacid generator, an additive, and a solvent, and the additive includes an anti-aging agent;

[0005] The anti-aging agent includes a compound with the structural formula wherein, R 1 、R 2 、R 3 and R 4 are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, -(C=O)-R 5 or -(C=O)O-R 6 ;

[0006] R 5 is a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group;

[0007] R 6 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group.

[0008] Optionally, at least one of the R 1 and the R 2 and / or the R3 and the R 4 at least one of them is selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, -(C=O)-R 5 or -(C=O)O-R 6 .

[0009] Optionally, the substituted or unsubstituted alkyl, the substituted or unsubstituted alkenyl, the substituted or unsubstituted alkynyl, the substituted or unsubstituted cycloalkyl, the substituted or unsubstituted alkoxy, the -(C=O)-R 5 and the -(C=O)O-R 6 have 1-15 carbon atoms.

[0010] Optionally, the substituents in the substituted alkyl, the substituted alkenyl, the substituted alkynyl, the substituted cycloalkyl, and the substituted alkoxy include one or more of a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl, or a substituted or unsubstituted aryloxy.

[0011] Optionally, the anti-aging agent includes , , , , , , and one or more of them; wherein, a and b are integers from 1 to 18 respectively.

[0012] Optionally, in the photoresist, the mass percentage of the anti-aging agent is 0.001%-2%.

[0013] Optionally, the additive further includes a fluororesin.

[0014] In the photoresist, the mass percentage of the fluororesin is 0.05%-2%. Optionally, in the photoresist, the mass percentage of the film-forming resin is 2%-20%; and / or, the mass percentage of the photoacid generator is 0.1%-10%; and / or, the mass percentage of the additive is 0.1%-10%; and / or, the mass percentage of the solvent is 50%-98%.

[0015] Optionally, the photoresist further includes a photo-decomposable base; in the photoresist, the mass percentage of the photo-decomposable base is 0.1%-10%.

[0016] Optionally, the film-forming resin includes an acrylate polymer.

[0017] Optionally, the solvent includes one or more of propylene glycol monomethyl ether acetate, γ-butyrolactone, glycol monomethyl ether, ethyl lactate, cyclohexanone, and diheptanone.

[0018] Optionally, the acid residue concentration of the photoresist aged at 40 °C for 28 days is less than or equal to 5×10 -3 mol / kg.

[0019] The photoresist provided by this application has an anti-aging agent, which can react with the residual acid in the photoresist, prevent the occurrence of the aging reaction, improve the stability of the photoresist, extend the storage period of the photoresist, and enhance the comprehensive performance of the photoresist.

[0020] In a second aspect, this application provides a patterned film, which is prepared using the photoresist described in the first aspect.

[0021] Due to the good stability of the photoresist provided by this application, the prepared patterned film has strong contrast, clear patterns, and high structural reliability.

[0022] In a third aspect, this application provides a patterned substrate, which is prepared using the photoresist described in the first aspect.

[0023] The patterned substrate provided by this application has clear patterns and good structural stability.

[0024] In a fourth aspect, this application provides a semiconductor device, which is prepared using the photoresist described in the first aspect.

[0025] The semiconductor device provided by this application has high precision and excellent comprehensive performance.

[0026] In a fifth aspect, this application provides a method for manufacturing a semiconductor device, including: coating the photoresist described in the first aspect on a substrate to form a photoresist film layer on the substrate; obtaining a patterned film after masking, exposing, and developing the photoresist film layer.

[0027] The manufacturing method provided by this application is simple, has low manufacturing costs, and is conducive to its industrial production. Description of the Drawings

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. The specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0029] Figure 1 This is a graph showing the change in acid residue concentration after aging at 40°C for Examples 1-2 and Comparative Examples 1-4 of the present application. Detailed implementation manners

[0030] Next, the technical solutions in the embodiments of the present application will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present application.

[0031] In the semiconductor manufacturing process, a photosensitive photoresist can be used as an etching-resistant coating. Through photochemical reactions and processes such as exposure and development, a certain difference in solubility is formed between the exposed area and the unexposed area in the coating, thereby realizing the preparation of a patterned film or a patterned substrate and obtaining a semiconductor device with excellent performance. In the related art, due to reasons such as raw materials, there is a small amount of residual acid in the photoresist when it leaves the factory. The residual acid easily causes a deprotection reaction of the film-forming resin in the photoresist, resulting in the aging of the photoresist; the acid products generated by the deprotection reaction further increase the acid concentration in the photoresist, further deepening the aging degree of the photoresist, reducing the storage stability of the photoresist, shortening the storage period of the photoresist, and being unfavorable for the industrial application of the photoresist; in addition, during the semiconductor manufacturing process, the presence of residual acid will cause a deprotection reaction of the film-forming resin, which will have an adverse impact on the structural stability and etching performance of the etching-resistant coating, reducing the clarity of the obtained patterned film and patterned substrate, and resulting in a decline in the performance of the semiconductor device.

[0032] To solve the above technical problems, the present application provides a photoresist. The photoresist includes a film-forming resin, a photoacid generator, an additive, and a solvent. The additive includes an anti-aging agent, and the anti-aging agent includes a compound with the structural formula wherein, R 1 、R 2 、R 3 and R 4 are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, -(C=O)-R 5 or -(C=O)O-R 6 ; R 5 is a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group; R 6is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group. In the present application, the film-forming resin, as the backbone component of the photoresist, is conducive to the formation of an etch-resistant coating with good mechanical properties and excellent etch resistance by the photoresist, facilitating subsequent processes such as exposure and development; the photoacid generator interacts and reacts with the film-forming resin under light irradiation, resulting in differences between the exposed area and the non-exposed area, and forming a specific pattern after development, which is conducive to the formation of a patterned film and / or a patterned substrate; the additive includes an anti-aging agent with an epoxy structure, which reacts with the residual acid in the photoresist, can reduce the concentration of the residual acid, avoid the deprotection reaction between the residual acid and the film-forming resin, inhibit the aging reaction of the photoresist, reduce the aging rate of the photoresist, improve the stability of the photoresist, extend the storage period of the photoresist, and can also avoid reacting with the film-forming resin during exposure, improve the structural stability of the etch-resistant coating, thereby improving the clarity of the patterned film and / or the patterned substrate, and being conducive to improving the comprehensive performance of semiconductor devices. The photoresist provided by the present application has good stability, a long storage period, and good etch performance, which is conducive to the industrial application of the photoresist.

[0033] In the present application, the anti-aging agent includes a compound with the structural formula The epoxy structure can capture the residual acid in the photoresist system through ring-opening reactions or interactions such as hydrogen bonds, avoid the detachment of the acid-unstable groups hanging on the film-forming resin, inhibit the generation of new acids, and thus effectively inhibit it at the starting stage of aging, thereby inhibiting the decomposition and failure of the film-forming resin due to the deprotection reaction before exposure, inhibiting the occurrence of the aging reaction, improving the stability and storage period of the photoresist, reducing the loss cost of the anti-aging agent, further reducing the preparation cost of micro-patterning in the semiconductor preparation process, and improving the preparation efficiency and shortening the preparation process flow. The anti-aging agent provided by the present application can improve the anti-aging ability and coating performance of the photoresist, be conducive to obtaining an etch-resistant coating with excellent stability, and improve the clarity and precision of the pattern.

[0034] In one embodiment of the present application, R 1 、R 2 、R 3 and R 4 can be the same group or different groups. In one example of the present application, R 1 can be a substituted or unsubstituted cycloalkyl group, R 2 is -(C=O)-R 5 , R 3 and R 4 are substituted or unsubstituted alkyl groups. In another example of the present application, R 1 、R2 and R 3 and R 4 are each independently a substituted or unsubstituted alkyl group.

[0035] In one embodiment of the present application, at least one of R 1 and R 2 , and / or at least one of R 3 and R 4 is selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, -(C=O)-R 5 or -(C=O)O-R 6 . This is beneficial for further improving the anti-aging ability of the photoresist and preventing the occurrence of aging reactions. In one example of the present application, R 1 can be a substituted or unsubstituted alkoxy group, and R 2 , R 3 and R 4 are hydrogen atoms. In another example of the present application, R 1 can be a substituted or unsubstituted alkyl group, R 3 can be -(C=O)-R 5 , and R 2 and R 4 are hydrogen atoms.

[0036] In one embodiment of the present application, R 1 , R 2 , R 3 and R 4 can be selected from -(C=O)-R 5 or -(C=O)O-R 6 . R 5 can be, but is not limited to, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group, etc. R 6 can be, but is not limited to, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group, etc. In one example of the present application, R 5 can be a substituted or unsubstituted alkyl group. In another example of the present application, R 6 can be a substituted or unsubstituted aryl group.

[0037] An alkyl group is a monovalent group obtained by removing one hydrogen atom from an alkane molecule. In one embodiment of the present application, the number of carbon atoms in the alkyl group is 1-25, and it may include a straight-chain alkyl group and a branched-chain alkyl group. Specifically, the number of carbon atoms in the alkyl group may be, but is not limited to, 1, 4, 6, 8, 10, 12, 14, 16, or 25, etc. Exemplarily, the alkyl group may include, but is not limited to, one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 4-methylbutyl, 2,2-dimethylpropyl, n-hexyl, heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylpentyl, 5-methylpentyl, 2-ethylbutyl, 3-ethylbutyl, heptyl, octyl, nonyl, and decyl. In one embodiment of the present application, the alkyl group may be 4-methylbutyl. In another embodiment of the present application, the alkyl group may be pentyl. In some embodiments, the number of carbon atoms in the alkyl group may be 5-15, which can not only inhibit the self-polymerization reaction of the epoxy structure in the anti-aging agent, maintain the appropriate viscosity of the photoresist, improve the coating performance of the photoresist, but also reduce the aging rate of the photoresist and extend the storage time of the photoresist.

[0038] In one embodiment of the present application, the number of carbon atoms in the alkenyl group is 2-25, and it may include a straight-chain alkenyl group and a branched-chain alkenyl group. Specifically, the number of carbon atoms in the alkenyl group may be, but is not limited to, 1, 4, 6, 8, 10, 12, 14, 16, or 25, etc. Exemplarily, the alkenyl group may include, but is not limited to, one or more of vinyl, propenyl, isopropenyl, butenyl, butadienyl, pentenyl, pentadienyl, hexenyl, hexadienyl, heptenyl, octenyl, nonenyl, and decenyl. In one embodiment of the present application, the alkenyl group may be propenyl. In another embodiment of the present application, the alkenyl group may be pentadienyl. In some embodiments, the number of carbon atoms in the alkenyl group may be 5-15, which can not only inhibit the self-polymerization reaction of the anti-aging agent, maintain the appropriate viscosity of the photoresist, improve the coating performance of the photoresist, but also reduce the aging rate of the photoresist and extend the storage time of the photoresist.

[0039] In one embodiment of the present application, the number of carbon atoms in the alkynyl group is 2-25, and it may include a straight-chain alkynyl group and a branched-chain alkynyl group. Specifically, the number of carbon atoms in the alkynyl group may be, but is not limited to, 1, 4, 6, 8, 10, 12, 14, 16, or 25, etc. Exemplarily, the alkynyl group may include, but is not limited to, one or more of ethynyl, propynyl, butynyl, pentynyl, and hexynyl. In one embodiment of the present application, the alkynyl group may be propynyl. In another embodiment of the present application, the alkynyl group may be pentynyl. In some embodiments, the number of carbon atoms in the alkynyl group may be 5-15, which can not only inhibit the self-polymerization reaction of the anti-aging agent, maintain the appropriate viscosity of the photoresist, improve the coating performance of the photoresist, but also reduce the aging rate of the photoresist and extend the storage time of the photoresist.

[0040] In one embodiment of the present application, the cycloalkyl group has 3 to 25 carbon atoms and can be a cyclic alkyl group with a single ring or multiple rings. For example, the multiple rings can be fused, bridged, or spiro rings, etc. Specifically, the number of carbon atoms in the cycloalkyl group can be, but is not limited to, 3, 4, 6, 8, 10, 12, 14, 16, or 25, etc. Exemplarily, the cycloalkyl group can include, but is not limited to, one or more of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and adamantyl. In one embodiment of the present application, the cycloalkyl group can be cyclopropyl. In another embodiment of the present application, the cycloalkyl group can be cyclohexyl. In some embodiments, the number of carbon atoms in the cycloalkyl group can be 5 to 15, which can not only inhibit the self-polymerization reaction of the anti-aging agent, maintain an appropriate viscosity of the photoresist, improve the coating performance of the photoresist, but also reduce the aging rate of the photoresist and extend the storage time of the photoresist.

[0041] In one embodiment of the present application, the alkoxy group has 2 to 25 carbon atoms and can include straight-chain alkoxy groups, branched-chain alkoxy groups, and cycloalkoxy groups. Specifically, the number of carbon atoms in the alkoxy group can be, but is not limited to, 1, 4, 6, 8, 10, 12, 14, 16, or 25, etc. Exemplarily, the alkoxy group can include, but is not limited to, one or more of methoxy, ethoxy, propoxy, butoxy, pentyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy. In one embodiment of the present application, the alkoxy group can be methoxy. In another embodiment of the present application, the alkoxy group can be cyclopropoxy. In some embodiments, the number of carbon atoms in the alkoxy group can be 5 to 15, which can not only inhibit the self-polymerization reaction of the anti-aging agent, maintain an appropriate viscosity of the photoresist, improve the coating performance of the photoresist, but also reduce the aging rate of the photoresist and extend the storage time of the photoresist.

[0042] In one embodiment of the present application, the aryl group has 6 to 18 carbon atoms. Specifically, the number of carbon atoms in the aryl group can be, but is not limited to, 6, 8, 10, 12, 14, or 18, etc. Specifically, the aryl group can include, but is not limited to, one or more of phenyl, naphthyl, and anthryl. In one embodiment of the present application, the aryl group can be phenyl. In another embodiment of the present application, the aryl group can be naphthyl.

[0043] In an embodiment of the present application, the number of carbon atoms in the aryloxy group is 6 - 25. Specifically, the number of carbon atoms in the aryloxy group can be, but is not limited to, 6, 8, 10, 12, 14, or 18, etc. Specifically, the aryloxy group can include, but is not limited to, one or more of phenoxy, naphthoxy, and anthryloxy. In an embodiment of the present application, the aryl group can be phenoxy. In another embodiment of the present application, the aryl group can be naphthoxy. In some embodiments, the number of carbon atoms in the aryloxy group can be 5 - 15, which can not only inhibit the self - polymerization reaction of the anti - aging agent, maintain the appropriate viscosity of the photoresist, improve the coating performance of the photoresist, but also reduce the aging rate of the photoresist and extend the storage time of the photoresist.

[0044] In an embodiment of the present application, the substituents in the substituted alkyl, substituted alkenyl, substituted alkynyl, substituted cycloalkyl, and substituted alkoxy include one or more of halogen atoms, hydroxyl groups (-OH), substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted aryloxy groups. In an embodiment of the present application, the substituent can be a hydroxyl group, and R 1 can be an alkyl group substituted with a hydroxyl group. In another embodiment of the present application, the substituent can be an aryl group, and R 1 can be an alkyl group substituted with a hydroxyl group.

[0045] In an embodiment of the present application, the anti - aging agent includes a compound with the structural formula , specifically, the anti - aging agent can include, but is not limited to, , , , , , , and one or more of them. In an embodiment of the present application, the structural formula of the anti - aging agent can be . In another embodiment of the present application, the structural formula of the anti - aging agent can be .

[0046] In an embodiment of the present application, the anti - aging agent includes one or more compounds with the structural formula shown. In an embodiment of the present application, the anti - aging agent includes a compound with the structural formula shown. In another embodiment of the present application, the anti - aging agent includes multiple different compounds with the structural formula shown. The quantity and type of the anti - aging agent in the photoresist of the present application can be selected according to actual usage requirements.

[0047] In an embodiment of the present application, a and b are independently selected as integers from 1 to 18, which is beneficial to suppressing the self-polymerization reaction of the anti-aging agent, improving the coating ability of the photoresist, and enhancing the storage period and stability of the photoresist. Specifically, a can be, but is not limited to, 1, 2, 4, 6, 8, 10, 12, 14, 16, or 18, etc., and b can be, but is not limited to, 1, 2, 4, 6, 8, 10, 12, 14, 16, or 18, etc. In an embodiment of the present application, a is an integer from 5 to 18, which is beneficial to improving the anti-aging ability of the photoresist. In another embodiment of the present application, b can be an integer from 7 to 18, which is beneficial to improving the solubility of the photoresist. a and b can have the same value or different values. The a in the above different structural formulas has no correlation, and the b in the different structural formulas also has no correlation, only for the convenience of expression.

[0048] In an embodiment of the present application, in the photoresist, the mass percentage of the anti-aging agent is 0.001% - 2%. An appropriate amount of the anti-aging agent can improve the anti-aging performance of the photoresist and extend the storage period of the photoresist. Specifically, in the photoresist, the mass percentage of the anti-aging agent can be, but is not limited to, 0.001%, 0.01%, 0.05%, 0.1%, 0.2%, 0.5%, 1%, 1.2%, 1.5%, or 2%, etc. In an embodiment of the present application, in the photoresist, the mass percentage of the anti-aging agent can be 0.01% - 1%. In another embodiment of the present application, in the photoresist, the mass percentage of the anti-aging agent can be 0.5% - 2%.

[0049] In an embodiment of the present application, the film-forming resin is a basic skeleton component of the photoresist, which is beneficial to forming an etching-resistant coating and improving the structural reliability of the etching-resistant coating. Specifically, the film-forming resin can include, but is not limited to, acrylate polymers, etc. In an embodiment of the present application, the film-forming resin can be an acrylate polymer, and the acrylate polymer is a homopolymer or copolymer of acrylate and its derivatives, methacrylate and its derivatives, etc. In some embodiments, the film-forming resin can be polyacrylate. In other embodiments, the film-forming resin can be polymethacrylate. In the present application, the film-forming resin does not include epoxy resin, because epoxy resin is prone to cross-linking and has poor solubility, resulting in being unable to be cleaned and removed after subsequent exposure and development, which will affect the performance of electronic components.

[0050] In an embodiment of the present application, in the photoresist, the mass percentage of the film-forming resin is 2% - 20%. An appropriate amount of the film-forming resin can improve the film-forming performance of the photoresist, enhance the mechanical strength of the etching-resistant coating, and at the same time maintain an appropriate viscosity, which is beneficial to the coating performance of the photoresist. Specifically, in the photoresist, the mass percentage of the film-forming resin can be, but is not limited to, 2%, 6%, 8%, 10%, 12%, 14%, 16%, 18% or 20%, etc. In an embodiment of the present application, the mass percentage of the film-forming resin can be 2% - 15%. In another embodiment of the present application, the mass percentage of the film-forming resin can be 10% - 20%. In some embodiments, the photoresist can be freeze-dried first, and then the obtained solid can be tested by nuclear magnetic resonance to calculate the mass ratio of the film-forming resin in the photoresist.

[0051] In an embodiment of the present application, the photoacid generator can generate an acid (such as a proton strong acid) under light irradiation conditions, interact with the film-forming resin, so that the solubility difference is generated between the exposed area and the unexposed area, and a specific pattern is formed after development, which is beneficial to the formation of the patterned film and / or the patterned substrate, and improves the clarity of the patterned film and / or the patterned substrate. Specifically, the photoacid generator can include, but is not limited to, ionic photoacid generators. The cation of the ionic photoacid generator is selected from phenylsulfonium salts, for example, triphenylsulfonium salts; its anion includes an anion fragment containing a fluorine element; in some specific embodiments, the cation in the above photoacid generator is ,

[0052] The anion fragment includes but is not limited to , , , , , , , , , . The above photoacid generator has a certain transparency and absorbance to light with a wavelength of 193 nm and has a high acid generation efficiency.

[0053] In an embodiment of the present application, in the photoresist, the mass percentage of the photoacid generator is 0.1% - 10%. An appropriate amount of the photoacid generator can improve the exposure performance of the photoresist, enhance the clarity and contrast of the patterned film, and reduce the aging rate of the photoresist. Specifically, in the photoresist, the mass percentage of the photoacid generator can be 0.1%, 1%, 2%, 4%, 6%, 8% or 10%, etc. In an embodiment of the present application, in the photoresist, the mass percentage of the photoacid generator can be 0.1% - 6%. In another embodiment of the present application, in the photoresist, the mass percentage of the photoacid generator can be 5% - 10%. In some embodiments, the photoresist can be subjected to freeze-drying and other treatments to remove the solvent. The solid substance obtained after freeze-drying is dissolved in a certain amount of deuterated reagent and subjected to nuclear magnetic resonance testing. The nuclear magnetic resonance test results are peak-assigned, and then the content of the photoacid generator in the photoresist is calculated and determined.

[0054] In an embodiment of the present application, the photo-decomposable base (PDB) belongs to a thermodynamically stable compound, shows alkalinity when unirradiated, and can decompose into a neutral compound or a weakly acidic compound in the exposed area when irradiated, can neutralize the acid generated by the photoacid generator, can improve the exposure performance of the photoresist and the post-exposure bake delay time, and can also enhance the contrast of the pattern obtained after exposure and reduce the edge roughness of the obtained pattern. Specifically, the photo-decomposable base can include, but is not limited to, , , , , , , , . The above reagents are highly sensitive to light with a wavelength of 160 nm - 200 nm.

[0055] In an embodiment of the present application, in the photoresist, the mass percentage of the photo-decomposable base is 0.1% - 10%. An appropriate amount of the photo-decomposable base can improve the exposure performance of the photoresist and enhance the pattern clarity and contrast of the patterned film. Specifically, in the photoresist, the mass percentage of the photo-decomposable base can be 0.1%, 1%, 2%, 4%, 6%, 8% or 10%, etc. In an embodiment of the present application, in the photoresist, the mass percentage of the photo-decomposable base can be 0.1% - 6%. In another embodiment of the present application, in the photoresist, the mass percentage of the photo-decomposable base can be 5% - 10%. In some embodiments, the photoresist can be subjected to freeze-drying and other treatments to remove the solvent. The solid substance obtained after freeze-drying is dissolved in a certain amount of deuterated reagent and subjected to nuclear magnetic resonance testing. The nuclear magnetic resonance test results are peak-assigned, and then the content of the photo-decomposable base in the photoresist is calculated and determined.

[0056] In one embodiment of the present application, the solvent can improve the dispersion ability of each component and enhance the coating performance of the photoresist. Specifically, the solvent can include, but is not limited to, one or more of propylene glycol methyl ether acetate (PGMEA), γ-butyrolactone (GBL), ethyl lactate (EL), cyclohexanone (CYC), diheptanone, etc. In one example of the present application, the solvent can be propylene glycol methyl ether acetate.

[0057] In one embodiment of the present application, in the photoresist, the mass percentage of the solvent is 50%-98%. An appropriate amount of solvent can improve the coating ability of the photoresist, enhance the uniformity of the etching-resistant coating, and facilitate the formation of the patterned film. Specifically, in the photoresist, the mass percentage of the solvent can be, but is not limited to, 50%, 60%, 70%, 80%, 90%, or 98%, etc. In one example of the present application, in the photoresist, the mass percentage of the solvent can be 40%-70%. In another example of the present application, in the photoresist, the mass percentage of the solvent can be 60%-98%.

[0058] In one embodiment of the present application, the additive further includes a fluororesin. The fluororesin can improve the hydrophobic property of the photoresist, enhance the curing ability and hydrophobic property of the photoresist. When a water film is formed on the surface of the etching-resistant coating, water will not penetrate into the etching-resistant coating to affect the patterning process and the performance of the obtained patterned film, thereby further broadening the application scenarios of the photoresist. Specifically, the fluororesin can include, but is not limited to, fluorinated methacrylic resins, etc. In one example of the present application, the fluororesin can be a fluorinated methacrylic resin, etc.

[0059] In one embodiment of the present application, in the photoresist, the mass percentage of the fluororesin is 0.05%-2%. An appropriate amount of anti-aging agent can inhibit the occurrence of aging reactions in the photoresist, improve the stability and waterproof property of the photoresist, and extend the storage period of the photoresist. Specifically, in the photoresist, the mass percentage of the fluororesin can be, but is not limited to, 0.05%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, or 2%, etc. In one example of the present application, in the photoresist, the mass percentage of the fluororesin can be 0.05%-1%. In another example of the present application, in the photoresist, the mass percentage of the fluororesin can be 0.8%-2%.

[0060] In an embodiment of the present application, in the photoresist, the mass percentage of the additive is 0.1% - 10%. An appropriate amount of the additive can improve the waterproof performance and storage period of the photoresist, and enhance the coating performance of the photoresist. Specifically, in the photoresist, the mass percentage of the additive can be 0.1%, 1%, 2%, 4%, 6%, 8% or 10%, etc. In an embodiment of the present application, in the photoresist, the mass percentage of the additive can be 0.1% - 6%. In another embodiment of the present application, in the photoresist, the mass percentage of the additive can be 5% - 10%.

[0061] In an embodiment of the present application, the photoresist may further include other additives, such as a leveling agent, etc. Thus, it is beneficial to enhance the coating performance of the patterned photoresist. Those skilled in the art can determine the addition amount of the above additives in the photoresist according to actual production needs.

[0062] In an embodiment of the present application, the acid residue concentration of the photoresist aged at 40°C for 28 days is less than or equal to 5×10 -3 mol / kg. The photoresist provided by the present application includes an anti-aging component, which inhibits the aging of the photoresist, reduces the acid residue concentration of the photoresist, extends the storage period and stability of the photoresist, and is beneficial to the commercial application of the photoresist. Specifically, the acid residue concentration of the photoresist aged at 40°C for 28 days can be but is not limited to less than or equal to 5×10 -3 mol / kg, less than or equal to 4×10 -3 mol / kg, less than or equal to 3.5×10 -3 mol / kg, less than or equal to 3×10 -3 mol / kg, less than or equal to 2.5×10 -3 mol / kg or less than or equal to 2×10 -3 mol / kg, etc. In an embodiment of the present application, the acid residue concentration of the photoresist aged at 40°C for 28 days can be less than or equal to 2.5×10 -3 mol / kg, which is beneficial to further improving the storage period of the photoresist. In another embodiment of the present application, the acid residue concentration of the photoresist aged at 40°C for 28 days can be less than or equal to 4×10 -3 mol / kg. In some embodiments, the acid residue concentration of the photoresist can be characterized by potentiometric titration.

[0063] In one embodiment of the present application, a method for preparing a photoresist includes: mixing a film-forming resin, a photoacid generator, an additive, and a solvent to obtain a photoresist. The method for preparing the photoresist provided by the present application is simple, has a low preparation cost, and the obtained photoresist has excellent anti-aging effects, good stability, and a long storage period, which is conducive to the commercial application of the photoresist.

[0064] The present application also provides a patterned film, which is prepared using the photoresist provided in any of the above embodiments. The patterned film can be used for the preparation of a mask in the semiconductor manufacturing process, which is conducive to subsequently transferring the pattern of the patterned film to a substrate such as a wafer through processes such as exposure, and forming a pattern corresponding to the mask on the substrate. The photoresist provided by the present application has high stability and good exposure effects, and the obtained mask has clear patterns and strong contrast, which is conducive to pattern transfer.

[0065] In one embodiment of the present application, a method for preparing a patterned film includes: coating a photoresist on a substrate to form a photoresist film layer; exposing and developing the photoresist film layer through a photomask to form a patterned film on the surface of the substrate.

[0066] The present application also provides a patterned substrate, which is prepared using the photoresist described in any of the above embodiments. The patterned substrate can be applied in the preparation of semiconductor devices, improving the production progress and quality of semiconductor devices, and being conducive to improving the comprehensive performance of semiconductor devices.

[0067] In one embodiment of the present application, a method for preparing a patterned substrate includes: forming a patterned film on and under a substrate, and transferring the pattern of the patterned film to the substrate to obtain a patterned substrate.

[0068] In one embodiment of the present application, the pattern formed by the photoresist forms a selective protection effect on the underlying substrate material during the etching step. After etching under certain conditions, the unprotected substrate material is etched, but the etching rate at the protected area is slower than that at the unprotected area. Finally, a pattern is formed on the substrate material, that is, the pattern is transferred to the substrate. The etching process can specifically transfer the pattern to the substrate through HF etching, ion etching, or ion implantation processes.

[0069] The present application provides a semiconductor device, which is prepared using the patterned film described in any of the above embodiments, or using the patterned substrate described in any of the above embodiments. The semiconductor device provided by the present application has high precision, which is conducive to improving the comprehensive performance of semiconductor devices.

[0070] In an embodiment of the present application, a semiconductor device includes a structure obtained by etching or electron implantation of a substrate. In an example of the present application, the semiconductor device is a structure obtained by etching or electron implantation of a silicon wafer as the substrate.

[0071] In the present application, there is no limitation on the specific type of the semiconductor device. In an embodiment of the present application, the semiconductor device may be an integrated circuit device including a chip, etc. During the preparation process of the chip, after the foregoing patterning process is completed, the preparation of other functional layers may be carried out.

[0072] The present application also provides a method for preparing a semiconductor device, including:

[0073] S101: Coating the photoresist described in any of the above embodiments on the surface of the substrate to form a photoresist film layer;

[0074] S102: Obtaining a patterned thin film after masking, exposure, and development of the photoresist film layer. The preparation method provided by the present application is simple, and the obtained semiconductor device has excellent comprehensive performance, which is beneficial to its commercial application. In an embodiment of the present application, the substrate is selected according to actual needs. Specifically, the substrate may be, but is not limited to, a silicon wafer, a silicon wafer with a coating, and exemplarily, the coating may be an antireflection coating, an etching-resistant coating, an epitaxial layer, a metal layer, a dielectric layer, a modification layer, or a matching layer, etc. Usually, other coatings can be obtained by preprocessing the substrate, and the preprocessing method may be: performing O2 plasma surface hydrophilic activation on the silicon wafer substrate; or cleaning in a Piranha solution (H2O: 30% ammonia water: 30% H2O2 = 5: 1: 1) for 15 mins - 20 mins, and then completing the hydrophilic treatment through deionized water washing and isopropyl alcohol washing; or performing surface hydrophobic treatment on the substrate by covering hexamethyldisilazane (HMDS) on the substrate by evaporation or spin coating; the hydrophobic treatment may be after the hydrophilic treatment; or adding a bottom antireflection coating (BARC), a bottom carbon-containing coating (spin on carbon, SOC), or a bottom silicon-containing coating (spin on glass, SOG).

[0075] In an embodiment of the present application, the substrate may be cleaned before coating to remove impurities and dust on the surface of the substrate. Specifically, the cleaning method may be, but is not limited to, using a solvent, an acid, ultrasonic waves, or spray cleaning, etc. In an example of the present application, the cleaning method may be ultrasonic cleaning.

[0076] In an embodiment of the present application, the exposure light source can be, but is not limited to, light with a wavelength of 100 nm - 380 nm, X-rays, electron beams, ion beams, etc.

[0077] In an embodiment of the present application, after coating and before exposure, a baking treatment can be performed to remove excess solvent in the film layer and improve the structural reliability of the photoresist; a baking treatment can also be performed after exposure and before development to promote chemical reactions in the etch-resistant coating. The baking temperature is 60°C - 200°C, and the baking time is 20 s - 120 s. Specifically, the baking temperature can be, but is not limited to, 60°C, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, etc., and the baking time can be, but is not limited to, 20 s, 40 s, 60 s, 80 s, 100 s, 120 s, etc. In an embodiment of the present application, the baking temperature can be 60°C - 150°C, and the baking time can be 20 s - 80 s. In an embodiment of the present application, the baking temperature can be 100°C - 200°C, and the baking time can be 70 s - 120 s.

[0078] In an embodiment of the present application, a developing solution is used for development. Since the chemical properties of the exposed area in the photoresist film layer change and the solubility changes, it is necessary to use the developing solution to clean the exposed photoresist film layer to obtain a patterned thin film. The cleaning time is 10 s - 300 s, which can be divided into single-step cleaning and multi-step cleaning. After cleaning the photoresist film layer, if the exposed area is washed away, it is positive development, forming a positive pattern, and at this time the photoresist is a positive photoresist; if the exposed area is not washed away, it is negative development, forming a negative pattern, and at this time the photoresist is a negative photoresist.

[0079] In one embodiment of the present application, the developing solution includes a developer. The developer can be selected according to the properties of the photoresist and used in combination to improve the etching effect. The developing time is 10s-120s. Specifically, the developer can include but is not limited to organic solutions, inorganic solutions, pure solvents, mixed solvents, solvents containing other additives, etc.; illustratively, the organic solvent can be but is not limited to one or more of ketones, alcohols, ethers, esters, lactones and high-boiling alcohols; among them, ketones can be but are not limited to cyclohexanone or methyl-2-n-pentyl ketone, etc.; alcohols can be but are not limited to 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol or diacetone alcohol, etc.; ethers can be but are not limited to propylene glycol mono Methyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether or diethylene glycol dimethyl ether, etc.; esters may be, but are not limited to, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, tert-butyl acetate, tert-butyl propionate or propylene glycol monotert-butyl ether acetate, etc.; lactones may be, but are not limited to, γ-butyrolactone; high boiling point alcohol solvents may be, but are not limited to, diethylene glycol, propylene glycol, glycerol, 1,4-butanediol or 1,3-butanediol, etc. In one embodiment of the present application, the developer may be a tetramethylammonium hydroxide (TMAH) aqueous solution with a concentration of 0.5%-5%. In some embodiments, after development, rinsing and baking are also included to remove impurities on the surface of the patterned film and improve the structural reliability of the patterned film.

[0080] In one embodiment of the present application, after forming a patterned thin film on a substrate, the method further includes: etching the substrate or injecting electrons to form a pattern on the surface of the substrate, thereby forming a structure required for a semiconductor device on the surface of the substrate to obtain a semiconductor device.

[0081] The effect of the technical solution of the present application is further illustrated below through specific examples.

[0082] Example 1

[0083] By mass percentage, the photoresist includes: 3% film-forming resin (polymethacrylate), 0.72% photoacid generator ( , Rs1, Rs2, Rs3 are H), 0.013% photolysis alkali ( ), additives (0.1% of fluorine-containing polymethacrylate and 0.5% of anti-aging agent), 96.15% of solvent (propylene glycol methyl ether acetate) anti-aging agent including the structural formula of compounds.

[0084] Example 2

[0085] The difference from Example 1 is that the anti-aging agent includes .

[0086] Comparative Example 1

[0087] The difference from Example 1 is that the structural formula of the anti-aging agent is .

[0088] Comparative Example 2

[0089] The difference from Example 1 is that the structural formula of the anti-aging agent is .

[0090] Comparative Example 3

[0091] The difference from Example 1 is that the structural formula of the anti-aging agent is .

[0092] Comparative Example 4

[0093] The difference from Example 1 is that no anti-aging agent is added.

[0094] Performance testing

[0095] The photoresists prepared in the above Examples 1-2 and Comparative Examples 1-4 were tested for the anti-aging performance of the photoresist. Test process: The photoresist was placed at 40 °C for high-temperature aging, and the acid residue concentrations at the 0th week, 1st week, 2nd week, 3rd week, 4th week, 5th week, and 6th week were tested. The test results are shown in Table 1. Figure 1 This is a graph showing the change in acid residue concentration after aging at 40 °C for Examples 1-2 and Comparative Examples 1-4 of this application; where the time is in weeks.

[0096] The photoresists prepared in the above Examples 1-2 and Comparative Example 4 were tested for the exposure parameters involved when the photoresist was exposed to form a pattern of S56P90->50. The test results of the optimal exposure energy EE (Energy), optimal focus FO (Focus), rate of change of feature size with energy K, exposure energy margin EL (Exposure), depth of focus DOF (Depth of Focus), line width uniformity (LCDU) (Local Critical Dimension Uniformity), and circular edge roughness CER (Circular Edge Roughness) are shown in Table 2.

[0097] Table 1 Anti-aging performance test

[0098]

[0099] Table 2 Exposure Performance Test

[0100]

[0101] It can be seen from Examples 1-2 and Comparative Examples 1-4 that the photoresist provided by the present application has excellent anti-aging performance, and after long-term high-temperature storage, the acid residue concentration is significantly lower than that of the comparative examples. It can be seen from Examples 1-2 and Comparative Example 4 that the photoresist provided by the present application includes an anti-aging agent having an epoxy structure. While having excellent anti-aging performance, it still has good exposure performance. The photoresist provided by the present application has excellent anti-aging performance, high stability, and a long storage period, which is beneficial to the industrial application of the photoresist.

[0102] The above is the preferred embodiment of the present application, but it should not be construed as limiting the scope of the present application. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present application, several improvements and refinements can be made, and these improvements and refinements are also regarded as the protection scope of the present application.

Claims

1. A photoresist, characterized in that: The photoresist comprises a film-forming resin, a photoacid generator, an additive and a solvent, wherein the additive comprises an anti-aging agent; The anti-aging agent includes a structural formula of A compound wherein R 1 , R 2 , R 3 and R 4 independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, -(C=O)-R 5 OR-(C=O)OR 6 , and the R 1 and the R 2 At least one of, and / or, the R 3 and the R 4 At least one of them is -(C=O)OR 6 ; R 5 is a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group; R 6 is substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, or substituted or unsubstituted aryl.

2. The photoresist according to claim 1, wherein The R 1 and the R 2 At least one of, and / or said R 3 and the R 4 At least one of them is selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, -(C=O)-R 5 .

3. The photoresist according to claim 1, wherein the substituted or unsubstituted alkyl, the substituted or unsubstituted alkenyl, the substituted or unsubstituted alkynyl, the substituted or unsubstituted cycloalkyl, the substituted or unsubstituted alkoxy, the -(C=O)-R 5 and the -(C=O)OR 6 The number of carbon atoms is 1-15.

4. The photoresist according to claim 1, wherein The substituents in the substituted alkyl, substituted alkenyl, substituted alkynyl, substituted cycloalkyl and substituted alkoxy include one or more of a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted alkoxy, a substituted or unsubstituted aryl and a substituted or unsubstituted aryloxy group.

5. The photoresist according to claim 1, wherein The anti-aging agent includes , One or more of; Wherein, a and b are integers of 1-18 respectively.

6. The photoresist according to claim 1, wherein In the photoresist, the mass percentage of the anti-aging agent is 0.001%-2%.

7. The photoresist according to claim 1, wherein The additives also include fluorine-containing resin; In the photoresist, the mass percentage of the fluorine-containing resin is 0.05%-2%.

8. The photoresist according to claim 1, wherein In the photoresist, the mass percentage of the film-forming resin is 2%-20%; and / or the mass percentage of the photoacid generator is 0.1%-10%; and / or the mass percentage of the additive is 0.1%-10%; and / or the mass percentage of the solvent is 50%-98%.

9. The photoresist according to claim 1, wherein The photoresist further comprises a photodegradable base; in the photoresist, the mass percentage of the photodegradable base is 0.1%-10%.

10. The photoresist according to claim 1, wherein The film-forming resin includes an acrylic polymer; The solvent includes one or more of propylene glycol methyl ether acetate, γ-butyrolactone, glycol methyl ether, ethyl lactate, cyclohexanone and diheptanone.

11. The photoresist according to claim 1, wherein The acid residual concentration of the photoresist after aging at 40°C for 28 days is less than or equal to 5×10 -3 mol / kg.

12. A patterned film, characterized in that: The patterned film is made using the photoresist as described in any one of claims 1 to 11.

13. A patterned substrate, characterized in that: The patterned substrate is made using the photoresist as described in any one of claims 1-11.

14. A semiconductor device, characterized in that: The semiconductor device is made using the photoresist as described in any one of claims 1-11.

15. A method for preparing a semiconductor device, characterized in that: include: Applying the photoresist according to any one of claims 1 to 11 on a substrate to form a photoresist film layer on the substrate; The photoresist film layer is subjected to masking, exposure and development to obtain a patterned film.

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