Chemical amplification type positive photoresist

Abstract

The invention provides a chemically amplified positive photoresist, and relates to the field of photoresists. The chemically amplified positive photoresist comprises the following raw materials in parts by weight: 10-30 parts of first resin, 20-60 parts of second resin, 10-70 parts of third resin, 0.1-2 parts of photoacid, 5-10 parts of an additive and a solvent, the solid content of the chemically amplified positive photoresist is 20%-60%; the first resin comprises acrylic acid and / or acrylic acid derivatives; the second resin comprises phenolic resin; the third resin comprises polyhydroxystyrene resin. The mixed resin with different acid dissociation groups shows a dissolution rate superior to that of single resin in an alkaline developing solution, so that the film thickness loss of a non-exposure area is inhibited, and the problem of swelling of a developed pattern is reduced.

Description

Technical Field

[0001] The present application relates to the field of photoresists, and particularly to a chemically amplified positive photoresist. Background Art

[0002] In recent years, in the manufacturing of semiconductor devices, liquid crystal display devices, and electronic components, pattern miniaturization has been continuously improved, and the semiconductor industry has experienced rapid development. With the further development of semiconductor device processing, the diversification and high integration of semiconductor packaging, deeper etching of semiconductor devices are required to form fine wirings, and the density of protruding electrodes, metal pillars, etc. is further increased. The improvement of integration density largely depends on the continuous reduction of the minimum feature size, which enables more small components to be integrated into a given area.

[0003] Among the methods for increasing the number of integrated chips per unit area of a silicon wafer in semiconductor chip manufacturing, the most effective method is to minimize the circuit line width (CD critical dimension); in order to minimize the CD as much as possible, it is necessary to adopt high-resolution lithography technology, which requires the resist material to have characteristics such as higher sensitivity to the exposure light source and the resolution to reproduce fine mask patterns.

[0004] Generally used phenolic resin systems have low photosensitivity, a wide molecular weight distribution, and are easily affected by the environment, resulting in unstable product performance, thus affecting the performance of photoresists such as resolution.

[0005] Therefore, there is an urgent need to provide a new resist photoresist material to solve the above problems. Summary of the Invention

[0006] The purpose of the present application is to provide a chemically amplified positive photoresist to solve the above problems.

[0007] To achieve the above purpose, the present application provides a chemically amplified positive photoresist, and its raw materials are calculated by weight and include:

[0008] 10 parts - 30 parts of the first resin, 20 parts - 60 parts of the second resin, 10 parts - 70 parts of the third resin, 0.1 part - 2 parts of photoacid, 5 parts - 10 parts of additive, and solvent;

[0009] The solid content of the chemically amplified positive photoresist is 20% - 60%;

[0010] The first resin includes acrylic acid and / or acrylic acid derivatives;

[0011] The second resin includes phenolic resin;

[0012] The third resin includes polyhydroxystyrene resin.

[0013] Optionally, the structural general formula of the first resin includes:

[0014]

[0015] One or more of the following;

[0016] Among them, R 1 -R 10 Are each independently a hydrogen atom, an alkyl group with 1-5 carbon atoms or a haloalkyl group with 1-5 carbon atoms;

[0017] X is a cycloalkyl group with 5-10 carbon atoms.

[0018] Optionally, the structural unit of the first resin includes:

[0019]

[0020] One or more of the following;

[0021] Among them, R α Includes a hydrogen atom, a linear or branched alkyl group composed of 1-5 carbon atoms or a haloalkyl group composed of 1-5 carbon atoms;

[0022] The hydrogen atom bonded to the carbon atom at the α-position in the structural unit is completely or partially substituted by a halogen atom or not substituted.

[0023] Optionally, the structural general formula of the polyhydroxystyrene resin is:

[0024]

[0025] Among them, R is a hydrogen atom, a linear or branched alkyl group with 1-5 carbon atoms or a haloalkyl group with 1-5 carbon atoms;

[0026] A is a single bond, a divalent hydrocarbon group or a divalent linking group containing a heteroatom;

[0027] B is a substituted or unsubstituted aromatic group;

[0028] x is an integer greater than or equal to 1.

[0029] Optionally, the polyhydroxystyrene resin includes:

[0030]

[0031] One or more of the following;

[0032] Among them, R α Is a hydrogen atom, an alkyl group with 1-5 carbon atoms or a haloalkyl group with 1-5 carbon atoms.

[0033] Optionally, the photoacid includes an ionic photoacid and / or a non-ionic photoacid.

[0034] Optionally, the chemically amplified positive photoresist satisfies at least one of the following conditions:

[0035] A. The general structural formula of the ionic photoacid is:

[0036]

[0037] Wherein, R 11 is a hydrogen atom or a halogen atom;

[0038] R 12 is one of a cycloalkyl group, a straight-chain or branched-chain having 1 to 6 carbon atoms;

[0039] R 13 is one of a cycloalkyloxy group, a phenylthio group, a straight-chain or branched-chain having 1 to 6 carbon atoms;

[0040] R 14 is CF3SO3 - 、[(C2F5)3PF3] - 、[B(C6F5)4] - one of them;

[0041] B. The general structural formula of the non-ionic photoacid is:

[0042]

[0043] Wherein, R 15 is one of an aliphatic hydrocarbon group having 1 to 10 carbon atoms and a perfluoroalkyl group, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms;

[0044] The aliphatic hydrocarbon group having 1 to 10 carbon atoms and the perfluoroalkyl group are substituted or unsubstituted by at least one of a halogen atom, an alkylthio group, and an alicyclic hydrocarbon group;

[0045] The aryl group having 6 to 20 carbon atoms is substituted or unsubstituted by at least one of a halogen atom, an alkylthio group, an alkyl group, and an acyl group;

[0046] The aralkyl group having 7 to 20 carbon atoms is substituted or unsubstituted by a halogen atom and an alkylthio group;

[0047] R 16 is one of O, N, S, P, a straight-chain, branched-chain or cyclic hydrocarbon group;

[0048] C. The mass ratio of the ionic photoacid to the non-ionic photoacid is 0.5 - 1:0.1 - 1.

[0049] Optionally, the ionic photoacid includes one or more of:

[0050]

[0051] Optionally, the non-ionic photoacid includes one or more of:

[0052]

[0053] One or more of the above.

[0054] Optionally, the chemically amplified positive photoresist satisfies at least one of the following conditions:

[0055] A. The weight average molecular weight of the first resin is 10,000 Mw - 200,000 Mw, and the polydispersity is 1 - 10;

[0056] B. The weight average molecular weights of the phenolic resin and the polyhydroxystyrene resin are independently 1,000 Mw - 45,000 Mw;

[0057] C. The additive includes one or more of an acid diffusion inhibitor, a mercapto compound, and a leveling agent;

[0058] D. The solvent includes propylene glycol monomethyl ether acetate.

[0059] Compared with the prior art, the beneficial effects of the present application include:

[0060] The chemically amplified positive photoresist provided by the present application has a mixed resin with different acid dissociation groups. The first resin and the third resin components are acrylic resin and polyhydroxystyrene resin respectively, which can effectively regulate the ADR of the photoresist, increase the contrast of the photoresist, and improve the morphology; the second resin component is phenolic resin, which can adjust the film-forming stress and improve the cracking problem, especially in the field of thick photoresist. The chemically amplified positive photoresist proposed by the present application shows a dissolution rate superior to that of a single resin in an alkaline developer, thereby suppressing the film thickness loss in the non-exposed area and reducing the swelling problem of the pattern after development. Description of the Drawings

[0061] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present application and should not be regarded as limiting the scope of the present application.

[0062] Figure 1 It is a standard evaluation diagram for graphic morphology testing;

[0063] Figure 2 It is a cross-sectional SEM diagram of the exposed film prepared in Example 1. Detailed implementation manners

[0064] As used herein, the terms:

[0065] "Prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing" or any other variation thereof as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article or apparatus comprising the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article or apparatus.

[0066] The conjunctive "consisting of" excludes any unrecited element, step or component. If used in a claim, this phrase will render the claim closed, excluding materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause of the claim body rather than immediately following the subject, it only limits the elements described in that clause; other elements are not excluded from the claim as a whole.

[0067] When an equivalent, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values and lower preferred values, this should be understood to specifically disclose all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, whether or not the ranges are separately disclosed. For example, when the range "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described herein, unless otherwise stated, the range is intended to include its end values and all integers and fractions within the range.

[0068] In these examples, unless otherwise specified, the parts and percentages are by mass.

[0069] "Parts by mass" refers to the basic measurement unit representing the mass ratio relationship of multiple components. 1 part can represent any unit mass, such as 1 g or 2.689 g, etc. If we say that the mass part of component A is a parts and the mass part of component B is b parts, it means the mass ratio of component A to component B is a:b. Or, it means the mass of component A is aK and the mass of component B is bK (K is any number representing a multiple factor). It should not be misunderstood that, different from the number of parts by mass, the sum of the mass parts of all components is not limited to 100 parts.

[0070] "And / or" is used to indicate that one or both of the stated situations may occur. For example, A and / or B includes (A and B) and (A or B).

[0071] This application provides a chemically amplified positive photoresist. Its raw materials, by weight, include:

[0072] 10 parts - 30 parts of a first resin, 20 parts - 60 parts of a second resin, 10 parts - 70 parts of a third resin, 0.1 part - 2 parts of a photoacid, 5 parts - 10 parts of an additive, and a solvent;

[0073] The solid content of the chemically amplified positive photoresist is 20% - 60%;

[0074] The first resin includes acrylic acid and / or acrylic acid derivatives;

[0075] The second resin includes phenolic resin;

[0076] The third resin includes polyhydroxystyrene resin.

[0077] In some embodiments, the general structural formula of the first resin includes:

[0078]

[0079] One or more of;

[0080] Among them, R 1 -R 10 Are each independently a hydrogen atom, an alkyl group with 1 - 5 carbon atoms, or a halogenated alkyl group with 1 - 5 carbon atoms;

[0081] X is a cycloalkyl group with 5 - 10 carbon atoms.

[0082] In some embodiments, the structural units of the first resin include:

[0083]

[0084] One or more of;

[0085] Among them, R α Includes a hydrogen atom, a linear or branched alkyl group composed of 1 - 5 carbon atoms, or a halogenated alkyl group composed of 1 - 5 carbon atoms;

[0086] Exemplarily, the linear or branched alkyl group composed of 1 - 5 carbon atoms includes methyl, ethyl, propyl, isopropyl, n - butyl, isobutyl, tert - butyl, pentyl, isopentyl, or neopentyl, and all or part of the hydrogen atoms in the halogenated alkyl group composed of 1 - 5 carbon atoms are replaced by halogen atoms;

[0087] All or part of the hydrogen atoms bonded to the carbon atom at the α - position in the structural unit are replaced or not replaced by halogen atoms.

[0088] It should be noted that the structural unit of the first resin selected above has good film-forming properties, which helps to improve the coating quality of the photoresist and the accuracy of pattern transfer; the acrylic resin has a high transmittance at wavelengths of 248 nm and 365 nm, which can meet the requirements of high-resolution lithography; in addition, by introducing groups such as adamantane and polycyclic lactones, the etching resistance of the photoresist can be improved; the acrylic resin itself is insoluble in alkaline developer. In some embodiments, the general structural formula of the polyhydroxystyrene resin is as follows:

[0089]

[0090] Wherein, R is a hydrogen atom, a linear or branched alkyl group with 1-5 carbon atoms or a haloalkyl group with 1-5 carbon atoms;

[0091] A is a single bond, a divalent hydrocarbon group or a divalent linking group containing heteroatoms;

[0092] B is a substituted or unsubstituted aryl group;

[0093] x is an integer greater than or equal to 1.

[0094] In some embodiments, the polyhydroxystyrene resin includes:

[0095]

[0096] One or more of;

[0097] Wherein, R α Is a hydrogen atom, an alkyl group with 1-5 carbon atoms or a haloalkyl group with 1-5 carbon atoms.

[0098] It should be noted that the above polyhydroxystyrene resin itself is soluble in alkaline developer. By introducing hydrophobic protecting groups such as acetal or t-Boc, it can be insoluble in the developer before exposure, but after light exposure, the photoacid decomposition will catalyze the deprotection reaction of the resin, thus becoming alkali-soluble and realizing high-contrast pattern transfer; at the same time, it has good thermal stability and chemical stability, and the benzene ring structure endows PHS with good resistance to plasma etching, providing good adhesion, flexibility and corrosion resistance in the photoresist formulation.

[0099] In some embodiments, the photoacid includes ionic photoacid and / or non-ionic photoacid.

[0100] It should be noted that when the ionic photoacid and the non-ionic photoacid are used in combination, the sensitivity, resolution can be improved, the residual gum can be reduced, and the corrosion of the metal substrate can be prevented.

[0101] In some embodiments, the chemically amplified positive photoresist satisfies at least one of the following conditions:

[0102] A. The general structural formula of the ionic photoacid is as follows:

[0103]

[0104] Among them, R 11 is a hydrogen atom or a halogen atom;

[0105] R 12 is one of cycloalkyl, a straight-chain or branched chain with 1 to 6 carbon atoms;

[0106] R 13 is one of cycloalkyloxy, phenylthio, a straight-chain or branched chain with 1 to 6 carbon atoms;

[0107] R 14 is CF3SO3 - 、[(C2F5)3PF3] - 、[B(C6F5)4] - one of them;

[0108] B. The general structural formula of the non-ionic photoacid is as follows:

[0109]

[0110] Among them, R 15 is one of an aliphatic hydrocarbon group and a perfluoroalkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 20 carbon atoms, and an aralkyl group with 7 to 20 carbon atoms;

[0111] The aliphatic hydrocarbon group and perfluoroalkyl group with 1 to 10 carbon atoms are substituted or unsubstituted by at least one of a halogen atom, an alkylthio group, and an alicyclic hydrocarbon group;

[0112] The aryl group with 6 to 20 carbon atoms is substituted or unsubstituted by at least one of a halogen atom, an alkylthio group, an alkyl group, and an acyl group;

[0113] The aralkyl group with 7 to 20 carbon atoms is substituted or unsubstituted by a halogen atom and an alkylthio group;

[0114] R 16 is one of O, N, S, P, a straight-chain, branched-chain or cyclic hydrocarbon group;

[0115] C. The mass ratio of the ionic photoacid to the non-ionic photoacid is 0.5 - 1:0.1 - 1.

[0116] Exemplarily, the mass ratio of the ionic photoacid to the non-ionic photoacid can be 0.5:0.1, 0.5:0.5, 0.5:1, 0.6:0.1, 0.8:0.1, 1:0.1, 1:0.5, 0.5:0.9, or any value between 0.5 - 1:0.1 - 1.

[0117] In some embodiments, the ionic photoacid includes:

[0118]

[0119]

[0120] one or more of the following.

[0121] It should be noted that the above-mentioned ionic photoacids are selected for their high acid strength and reactivity. In particular, the ionic photoacids containing sulfonate anions have a low acid pKa, can efficiently catalyze the deprotection reaction, regulate the dissolution rate of the photoresist in the developer, and improve the contrast; sulfonium salts and iodonium salts are stable at room temperature and are not easily decomposed, which is beneficial to the storage of the photoresist and process control.

[0122] In some embodiments, the non-ionic photoacid includes:

[0123]

[0124] one or more of the following.

[0125] It should be noted that the above-mentioned non-ionic photoacids have a low metal ion or halogen content, a relatively large molecular weight, and a low diffusion rate, which helps to reduce pattern blur caused by acid diffusion and improve edge roughness.

[0126] In some embodiments, the chemically amplified positive photoresist satisfies at least one of the following conditions:

[0127] A. The weight-average molecular weight of the first resin is 10,000 Mw - 200,000 Mw, and the polydispersity is 1 - 10;

[0128] Exemplarily, the weight-average molecular weight of the first resin can be 10,000 Mw, 50,000 Mw, 100,000 Mw, 150,000 Mw, 200,000 Mw, or any value between 10,000 Mw and 200,000 Mw, and the polydispersity can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or any value between 1 and 10;

[0129] B. The weight-average molecular weights of the phenolic resin and the polyhydroxystyrene resin are each independently 1,000 Mw - 45,000 Mw;

[0130] Exemplarily, the weight-average molecular weight of the phenolic resin and the polyhydroxystyrene resin can each independently be 1000 Mw, 10000 Mw, 20000 Mw, 30000 Mw, 40000 Mw, 45000 Mw, or any value between 1000 Mw and 45000 Mw;

[0131] C. The additive includes one or more of an acid diffusion inhibitor, a mercapto compound, and a leveling agent;

[0132] Exemplarily, the acid diffusion inhibitor includes, but is not limited to, one or more of triethylamine, 2,4,5-triphenylimidazole, and N-Boc-4-hydroxypiperidine;

[0133] The mercapto compound includes, but is not limited to, one or more of 4,4'-thiobisbenzenethiol, thiosalicylic acid, 1,3,4-thiadiazole-2-thiol, and bismuth reagent;

[0134] The leveling agent includes, but is not limited to, one or more of BYK-310, DFX-18, NEOS212M, and NEOS215M;

[0135] D. The solvent includes propylene glycol monomethyl ether acetate.

[0136] The embodiments of the present application will be described in detail below in conjunction with specific examples. However, those skilled in the art will understand that the following examples are only used to illustrate the present application and should not be regarded as limiting the scope of the present application. For those not specified in the examples, the operations are carried out under conventional conditions or conditions recommended by the manufacturer. For the reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0137] Example 1

[0138] This example provides a chemically amplified positive photoresist, the raw materials of which include: a first resin, a second resin, a third resin, photoacid P1, an additive, and solvent propylene glycol monomethyl ether acetate;

[0139] Among them, the first resin is abbreviated as R1, which is an acrylate derivative, with a weight-average molecular weight of 10000 Mw - 80000 Mw and a polydispersity of 2. The specific structure is as follows:

[0140]

[0141] The second resin is abbreviated as RF, which is a phenolic resin, with a weight-average molecular weight of 1000 Mw - 45000 Mw, and is a reaction product obtained by the addition and condensation of a mixture of m-cresol and p-cresol with formaldehyde under the condition of an acidic catalyst, where m-cresol / p-cresol = 65 / 35 (molar ratio);

[0142] The third resin, abbreviated as RP, is a polyhydroxystyrene resin with a weight-average molecular weight of 1000 Mw - 45000 Mw, and its specific structure is as follows:

[0143]

[0144] The specific structure of photoacid P1 is as follows:

[0145]

[0146] The additives include a quencher, a ligand, and a leveling agent. The quencher is N-Boc-4-hydroxypiperidine, the ligand is 4,4'-thiobisbenzenethiol, and the leveling agent is DFX-18.

[0147] The chemically amplified positive photoresist composition prepared from the above raw materials has a solid content of 33 wt%, and the physical object is as Figure 1 shown. The amounts of the raw materials are in parts by weight, as specifically shown in Table 1.

[0148] Example 2

[0149] The difference from Example 1 is that photoacid P2 is also added. Among them, the specific structure of photoacid P2 is as follows:

[0150]

[0151] The specific amounts can be seen in Table 1.

[0152] Example 3

[0153] The difference from Example 2 is the amounts used.

[0154] Comparative Example 1

[0155] The difference from Example 1 is that no phenolic resin is set.

[0156] Comparative Example 2

[0157] The difference from Example 1 is that no polyhydroxystyrene resin is set.

[0158] Comparative Example 3

[0159] The difference from Example 1 is that no phenolic resin and polyhydroxystyrene resin are set.

[0160] Comparative Example 4

[0161] The difference from Example 1 is that no first resin is set.

[0162] Comparative Example 5

[0163] The difference from Example 1 is that no first resin and phenolic resin are set.

[0164] Table 1 Photoresist Raw Materials and Their Amounts

[0165]

[0166] Mix the raw materials provided in the above-mentioned examples and comparative examples together and dissolve them fully to separately prepare photoresists.

[0167] Prepare a photoresist film from the above-mentioned photoresist. The specific method is as follows:

[0168] Perform hexamethyldisilazane (HMDS) treatment on an 8-inch silicon wafer to obtain a coated substrate. Coating each photoresist composition of the examples and comparative examples on the substrate by spin coating (pre-rotation speed + main rotation speed), and then performing heat treatment to remove the solvent (PAB: 130 °C, 90 s) to form a photoresist film with a film thickness of 4 μm; then selectively expose the photoresist through a mask using a Nikon I-line stepper exposure machine, with an exposure energy of 150 mJ / cm 2 , and then place it on a hot plate at 110 °C for post-exposure baking (PEB: 110 °C, 60 s); immediately use a development device track 8 to perform spray development with 2.38 wt% tetramethylammonium hydroxide (TMAH) base at 23 °C for 60 s, and finally rinse with deionized water for 30 s to obtain the L / S pattern corresponding to the mask.

[0169] Perform photoresist performance testing on the photoresist film prepared above. The test results are shown in Table 2. The specific test method is as follows:

[0170] Observe the morphology, resolution, adhesion, and process window of the exposed film prepared by the above operations on equipment such as CD-SEM and SEM; immerse the complete developed pattern in an acid copper plating solution at room temperature, and then take it out and observe whether the morphology changes through OM to verify the anti-plating solution characteristics of the photoresist composition.

[0171] Among them, for the resolution test: Observe the photoresist pattern obtained by the above operations on OM and SEM. The film thickness is 4 μm, and measure the minimum opening size.

[0172] For the adhesion test: Observe the exposed film prepared by the above operations. If the pattern completely remains on the substrate, it shows ok; if there is glue peeling, glue pouring, or the pattern is washed off, it shows no.

[0173] For the graphic morphology test: Observe the cross-section of the exposed film prepared by the above operations through SEM. The graphic morphology passes the standard evaluation as Figure 1 shown. The left figure is qualified and is represented by a, the intermediate and the right figure are unqualified and are represented by b and c respectively; among them, the cross-section of the exposed film slice prepared in Example 1 is as Figure 2 shown.

[0174] Sensitivity test: The 8-inch silicon wafer was treated with hexamethyldisilazane (HMDS) to obtain a coated substrate. Each photoresist composition of the examples and comparative examples was spin-coated (pre-rotation speed + main rotation speed) on the substrate, and then heat-treated to remove the solvent (PAB: 130 °C, 90 s) to form a photoresist film with a thickness of 4 μm. Then, a Nikon I-line stepper exposure machine was used to selectively expose the photoresist through a mask, and then it was placed on a hot plate at 110 °C for post-exposure baking (PEB: 110 °C, 60 s). Immediately afterwards, a developing device track 8 was used to perform spray development with 2.38 wt% tetramethylammonium hydroxide (TMAH) base at 23 °C for 60 s, and finally rinsed with deionized water for 30 s to obtain the corresponding L / S pattern of the mask. Then, the exposure amount at which the photoresist pattern was completely opened, that is, the minimum exposure amount for forming the photoresist pattern, was defined as the sensitivity.

[0175] Electroplating resistance: The prepared photoresist silicon wafer was cut into a size of 5 cm × 5 cm, and then immersed in an acid copper electroplating solution at room temperature for 1 h. The morphology of the photoresist was observed by OM to verify the electroplating resistance of the photoresist. If the morphology did not change, it was shown as ok; if the lines fell off or deformed, it was shown as no.

[0176] Film thickness loss: The film thickness dimension T1 was measured after coating and baking, and the film thickness dimension T2 was measured after exposure and development. If T1 - T2 < 0.2 μm, it was shown as ok; if T1 - T2 ≥ 0.2 μm, it was shown as no.

[0177] Table 2 Performance test

[0178]

[0179]

[0180] Analysis:

[0181] It can be seen from the test results that the photoresist composition obtained by mixing acrylic resin, phenolic resin and polyhydroxystyrene resin has good adhesion to the substrate and electroplating resistance, reduces film thickness loss and improves the line morphology at the same time. After adding both ionic photoacid and non-ionic photoacid to the formulation, the resolution and sensitivity of the photoresist are effectively improved.

[0182] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

[0183] In addition, those skilled in the art will appreciate that although some embodiments herein include certain features included in other embodiments rather than other features, the combination of features of different embodiments is meant to be within the scope of this application and forms different embodiments. For example, in the claims above, any one of the claimed embodiments can be used in any combination. The information disclosed in this background section is only for enhancing the understanding of the overall background of this application and should not be taken as an admission or any form of implication that this information constitutes prior art already known to those skilled in the art.

Claims

1. A chemically amplified positive photoresist, characterized in that, Its raw materials, by weight parts, include: 10 parts - 30 parts of a first resin, 20 parts - 60 parts of a second resin, 10 parts - 70 parts of a third resin, 0.1 part - 2 parts of a photoacid, 5 parts - 10 parts of an additive, and a solvent; The solid content of the chemically amplified positive photoresist is 20% - 60%; The first resin includes acrylic acid and / or acrylic acid derivatives; The second resin includes a phenolic resin; The third resin includes a polyhydroxystyrene resin.

2. The chemically amplified positive photoresist according to claim 1, characterized in that, The general structural formula of the first resin includes: one or more of; wherein, R 1 -R 10 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms; X is a cycloalkyl group with 5 - 10 carbon atoms.

3. The chemically amplified positive photoresist according to claim 2, wherein The structural units of the first resin include: one or more of; wherein, R α includes a hydrogen atom, a linear or branched alkyl group composed of 1 to 5 carbon atoms, or a halogenated alkyl group composed of 1 to 5 carbon atoms; All or part of the hydrogen atoms bonded to the carbon atoms at the α-position in the structural units are substituted or unsubstituted by halogen atoms.

4. The chemically amplified positive photoresist according to claim 1, wherein The general structural formula of the polyhydroxystyrene resin is: Wherein, R is a hydrogen atom, a linear or branched alkyl group with 1 - 5 carbon atoms, or a haloalkyl group with 1 - 5 carbon atoms; A is a single bond, a divalent hydrocarbon group, or a divalent linking group containing a heteroatom; B is a substituted or unsubstituted aryl group; x is an integer greater than or equal to 1.

5. The chemically amplified positive photoresist according to claim 4, wherein The polyhydroxystyrene resin includes: one or more of; wherein, R α is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms.

6. The chemically amplified positive photoresist according to claim 5, wherein The photoacid includes an ionic photoacid and / or a non-ionic photoacid.

7. The chemically amplified positive photoresist according to claim 6, characterized in that, Meet at least one of the following conditions: A. The general structural formula of the ionic photoacid is: wherein, R 11 is a hydrogen atom or a halogen atom; R 12 is one of cycloalkyl, a straight or branched chain having 1 to 6 carbon atoms; R 13 is one of cycloalkyloxy, phenylthio, or a straight or branched chain having 1 to 6 carbon atoms; R 14 is CF3SO3 - , [(C2F5)3PF3] - , [B(C6F5)4] - ; or one of the following B. The general structural formula of the non-ionic photoacid is: Among them, R 15 is one of an aliphatic hydrocarbon group having 1 to 10 carbon atoms and a perfluoroalkyl group, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; The aliphatic hydrocarbon group and perfluoroalkyl group with 1 - 10 carbon atoms are substituted or unsubstituted by at least one of a halogen atom, an alkylthio group, and an alicyclic hydrocarbon group; The aryl group with 6 - 20 carbon atoms is substituted or unsubstituted by at least one of a halogen atom, an alkylthio group, an alkyl group, and an acyl group; The aralkyl group with 7 - 20 carbon atoms is substituted or unsubstituted by a halogen atom and an alkylthio group; R 16 is one of O, N, S, P, a linear, branched or cyclic hydrocarbon group; C. The mass ratio of the ionic photoacid to the non-ionic photoacid is 0.5 - 1:0.1 - 1.

8. The chemically amplified positive photoresist according to claim 7, characterized in that, The ionic photoacid includes: one or more of 9. The chemically amplified positive photoresist according to claim 7, characterized in that, The non-ionic photoacid includes: one or more of 10. The chemically amplified positive photoresist according to any one of claims 1-9, characterized in that, Meet at least one of the following conditions: A. The weight-average molecular weight of the first resin is 10000 Mw - 200000 Mw, and the polydispersity is 1 - 10; B. The weight-average molecular weights of the phenolic resin and the polyhydroxystyrene resin are each independently 1000 Mw - 45000 Mw; C. The additive includes one or more of an acid diffusion inhibitor, a mercapto compound, and a leveling agent; D. The solvent includes propylene glycol monomethyl ether acetate.

Images