CN1280676C - Positive photoresist composition and method for forming photoresist pattern - Google Patents

Abstract

The invention provides a positive photoresist composition with uniform reactivity, which is coated and then subjected to thermal crosslinking reaction and photolysis reaction in different processing steps to form a pattern circuit. The novel photoresist composition is composed of a multicomponent resin composition, a photoacid generator and a reactive monomer. When the photoresist composition is soft-baked (soft-baking), the reactive monomer and the multi-component resin composition first form a polymer having a network structure. Then the photoresist composition is irradiated by an exposure light source, and the generated acid can make the multicomponent resin in the photoresist respectively undergo the chemical amplification type resin deprotection reaction and the photodecomposition reaction of the network structure resin. Therefore, the positive photoresist of the invention can obtain better depth-width ratio and resolution ratio of the photoresist in the lithography process due to better alkaline contrast capability and uniform reactivity.

Description

Positive photoresist composition and method for forming photoresist pattern

technical field

The invention relates to a multi-component positive-type photoresist composition, in particular to a positive-type photoresist composition with uniform reactivity used in thick film yellow light lithography technology.

Background technique

With the development trend of semiconductor devices shrinking in size, there is an urgent need to form more precise patterns in the lithography process, so that the design of semiconductor devices can achieve a higher degree of integration. Under this technology trend and market demand, the substrate technology will develop in the direction of high-density wiring, thinner, thinner lines, and high aspect ratio, so as to meet the diverse needs of electronic and optoelectronic carrier technology in the future.

In the current lithography process of high-density wiring carrier substrates, the negative photoresist is generally used for the thick film yellow light lithography process of the carrier substrate, but due to the requirements of photoresist thickness and resolution, positive The positive-type photoresist helps to increase the thickness of the photoresist film and the resolution, and when the positive-type photoresist is used to make the perforation pattern, it has a lower defect rate than the negative-type photoresist.

Positive photoresist is currently mainly used in the IC industry as thin film photoresist, and can be divided into I-Line DNQ/Novolac system and deep ultraviolet chemical amplification system according to the exposure light source. The coating thickness of the DNQ/Novolac system photoresist is generally about 0.5-5 μm, and the resolution is about 0.35-5 μm. The coating thickness of the chemically amplified specific ratio protective group resin for deep ultraviolet light is about 0.2-0.5 μm, and the resolution is about 0.3-0.09 μm. At present, in the lithography process of high-density wiring carrier substrates, the generally required coating thickness is about 10-50 μm, and the best resolution is required to be between 10-50 μm. Under the trend of multi-layering, the use of positive photoresist for thin-film manufacturing will be limited in application. For example, the thickness of the photoresist film required to be coated will become larger (usually greater than 5 μm, compared with the original 0.2 μm to The applicable range of 1μm exceeds a lot), resulting in a decrease in optical penetration, which in turn causes the required exposure energy to be too high, resulting in a difference in the degree of light received by the surface and the bottom area of the photoresist, and often due to the uneven reaction between the exposure light source and the photoresist material relationship, resulting in uneven photoresist surface and sidewalls, making it impossible to obtain high-resolution thick film photoresist.

The resin composition with chemical amplification characteristics, because it has an acid-labile functional group, can undergo a deprotection reaction under the acid-catalyzed reaction after exposure to remove the acid-labile functional group, thus changing the composition of the photoresist. Hydrophilic and hydrophobic properties, and because the acid-labile functional group will further release the acid after the deprotection reaction, which can reduce the exposure energy required by the photoresist, so it is often used as a component of the positive photoresist one. However, the chemically amplified photoresist composition has insufficient dissolution resistance and polymerization uniformity, resulting in poor contrast between unexposed and exposed photoresist film layers, easily distorting the outline of the circuit and causing rough edges.

In the next few years, affected by the requirements of precision circuits, high-density interconnected multi-layer substrates will become the mainstream, and the resolution of photoresist must be increased to 10-25 μm, and the process technology with higher photoresist film thickness will be adopted. Therefore, The development of a positive photoresist with high uniform reactivity and high efficiency is the focus of urgent research in the current lithographic etching process technology.

Contents of the invention

In view of this, the object of the present invention is to provide a positive photoresist composition with uniform reactivity. After coating, thermal crosslinking reaction and photolysis reaction are respectively performed in different process steps to form pattern circuits. The positive-type photoresist composition is not easily soluble in aqueous alkali solution. Under the irradiation of the exposure light source, the acid produced by the photoacid in the composition will cause the photoresist composition to undergo multiple reactions, including the reaction of the network structure resin. The de-acetalization reaction and the deprotection reaction of the chemically amplified resin are used to simultaneously change the hydrophilic and hydrophobic properties of the photoresist constituent molecules and the molecular weight of the photoresist constituent molecules to achieve the purpose of uniformly reacting the positive photoresist composition. Now, when the positive-type photoresist composition with uniform reactivity of the present invention is used in the thick film photoresist patterning process, the photoresist can be completely reacted without increasing the exposure energy, so it will not occur due to exposure light source Photoresist defects caused by scattering and uneven reaction of photoresist materials, and because the positive photoresist composition of the present invention has high uniform reactivity and better resistance to dissolution, it can be used in lithographic etching technology for better resolution.

In order to achieve the above object, the photoresist composition of the present invention is a positive photoresist composition composed of various resins, and the photoresist composition includes dissolved in an organic solvent to form a uniform solution form:

(a) phenolic resin compound, 100 parts by weight;

(b) a resin compound having an acid-labile functional group, 1 to 100 parts by weight;

(c) reactive monomers, which have a vinyl ether or epoxy group (alicyclic epoxide) as the main structure, 1 to 100 parts by weight; and

(d) A photoacid generator, 1 to 35 parts by weight.

The positive photoresist composition with uniform reactivity of the present invention mainly combines the advantages of the molecular weight modification system and the chemical amplification system traditionally used in positive photoresists. In the positive photoresist of the present invention, the phenolic resin compound and the resin compound with the acid-labile functional group constitute a multi-component resin, which can not only reduce the photoresist by utilizing the resin compound with the acid-labile functional group The exposure energy required by the agent, and the multi-component resin can also reduce the sensitivity of the acid-catalyzed reaction after exposure, and the resin compound with an acid-labile functional group can undergo a deprotection reaction under acid catalysis to remove Stable functional groups, thereby changing the hydrophilic and hydrophobic properties of photoresist constituent molecules, and obtaining the characteristics of positive photoresist; the multi-component resin can further reduce the alkali solution solubility of the photoresist composition as a whole; and in photoresist Adding reactive monomers with vinyl ether as the main structure can effectively bind phenolic resin compounds and resin compounds with acid-labile functional groups in a highly cross-linked network structure during the soft-baking process before exposure In this way, the photoresist film layer before exposure can have better polymerization uniformity, increase the photoresist contrast ability, and further make the photoresist profile meet the requirements of the process; and the reactive monomer is combined with the resin Under the acid catalysis after exposure, the highly cross-linked network structure formed by the object can also be decomposed, resulting in a change in the molecular weight of the photoresist composition, which increases the solubility of the exposed photoresist and further increases the photoresist. High aspect ratio and resolution.

In order to further illustrate the content of the present invention, each component in the positive photoresist composition under the multiple reaction mode will be described one by one below.

The positive-type photoresist composition with uniform reactivity of the present invention comprises at least one phenolic resin as component (a), which can be a polymer having an ortho, meta, p-phenolic resin or a cresol resin structure derivative matter, also can be the compound with the structure described in formula (I)

Formula (I),

Wherein R ₁ can be the same or different, and is selected from one of the following groups: -CH ₂ -, Alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl or aryl, wherein the alkyl, alkoxy, alkenyl or alkynyl contains 2-12 carbon atoms and is linear or branched , The cycloalkyl group contains 3-12 carbon atoms, and the value of n is between 1-100.

According to the positive photoresist composition with uniform reactivity according to the present invention, wherein in the phenolic resin compound having the structure described in formula (I), the hydrogen on each carbon atom can be replaced by halogen, cyano, Methyl, -R", -CO ₂ H, -CO ₂ R", -COR", -R"CN, -CONH ₂ , -CONHR", -CONR" ₂ , -OCOR" or OR", wherein R" is selected from one or more of the following groups: substituted or unsubstituted alkyl, alkynyloxy, alkoxy, alkenyl, alkynyl, alkenyloxy, heterocycle containing 1-12 carbon atoms group, aryl group, aralkyl group, heteroaryl group, or aliphatic polycyclic group, and in the phenolic resin compound having the structure described in formula (I), the value of n is preferably between 2 and 30.

The resin compound suitable for component (b) of the present invention having an acid-unstable functional group is selected from acrylic resins (also known as acrylic resins) having an acid-unstable functional group, and acrylic resins having an acid-unstable functional group. Polyhydroxystyrene (PHS) resin or mixtures thereof. Wherein, the acid-labile functional group refers to a group that is unstable under the positively charged state produced by acid-catalyzed deprotection, and is easy to release H ⁺ ions by itself so as to become a stable molecule by itself, and the pair The acid-labile functional group can be selected from one or more of the following groups: tert-butyl, tetrahydropyran-2-yl, 2-methyltetrahydropyran-2-yltetrahydrofuran-2-yl , 2-methyltetrahydrofuran-2-yl, 1-methoxypropyl, 1-methoxy-1-methylethyl, 1-ethoxypropyl, 1-ethoxy-1-methyl Ethyl, 1-methoxyethyl, 1-ethoxyethyl, 1-butoxyethyl, 1-tert-butoxyethyl, 1-isobutoxyethyl, tert-butoxycarbonyl , tert-butoxycarbonylmethyl, trimethylsilyl, 3-tert-butyldimethylsilyl and 2-acetyl Base-1-yl (2-acetylmenth-1-yl).

Preferably, the acrylic resin (also known as acrylic resin) having an acid-labile functional group is selected from one or more of the following resins: tetraethylene glycol diacrylate, tetraethylene glycol dimethyl Acrylates, Neopentyl Glycol Diacrylate, Neopentyl Glycol Dimethacrylate, Polyethylene Glycol Diacrylate, Polyethylene Glycol Dimethacrylate, Ethoxylated Bisphenol A Di Acrylates, Ethoxylated Bisphenol A Dimethacrylate, Trimethylolpropane Trimethacrylate, Trimethylolpropane Triacrylate, Pentaerythritol Triacrylate, Ethoxylated Trimethylolpropane Copolymers of propane triacrylate, glyceryl propoxy triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, glycidyl acrylate, glycidyl methacrylate and mixtures thereof.

The reactive monomer suitable for component (c) of the present invention is preferably a reactive monomer with vinyl ether or epoxy group as the main structure, and the vinyl ether reactive monomer can be selected from one of the following monomers or more: 1,4-cyclohexanedimethanol diglycidyl ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, ethylene glycol divinyl ether, di Glycol divinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether or lactone; and cycloaliphatic epoxide (cycloaliphatic epoxide) can be N,N-dishrink Glyceryl-4-dehydrated glyceryl aniline (N, N-diglycidyl-4-glycidyloxyaniline), 3,4-epoxycyclohexanemethyl carboxylate, 3,4-epoxycyclohexane carboxylate, 1,2-cyclohexane diglycidyldicarboxylate (1,2-cyclohexane diglycidyldicarboxylate).

The photoacid generator suitable for component (d) of the present invention is any suitable photoacid generator, and the preferred photoacid generator is selected from one or more of the following salts: onium salt, triaryl permeate Salt, alkaryl permedium salt, diaryliodonium salt, diaryl chloride onium salt, diaryl bromide salt, sulfonate, diazonium salt and diazonaphthoquinone sulfonate.

Specific examples of the aforementioned triaryl cobaltium salts include triaryl cobaltium hexafluorophosphate, triphenyl trifluoromethanesulfonate (triphenyl triflate), triphenyl antimonate, methoxytriphenyltrifluoromethanesulfonate (methoxytriphenyl triflate), methoxytriphenyl antimonate, trimethyl triphenyltrifluoromethanesulfonate (trimethyl triphenyltriflate), or a mixture of the above compounds.

According to the positive-type photoresist composition with uniform reactivity of the present invention, for (a) phenolic resin and (b) resin having an acid-labile functional group, the applicable molecular weight is between 2000 and 150000, For phenolic resins and resins with acid-labile functional groups, the preferred molecular weight is between 3,000 and 100,000.

The positive-type photoresist composition with uniform reactivity of the present invention undergoes a multiple reaction mode after being irradiated by an exposure light source, and the multiple reaction mode includes synchronous reactions of changes in the hydrophilic and hydrophobic properties of the photoresist component molecules and changes in the molecular weight of the photoresist component molecules .

According to the positive photoresist composition with uniform reactivity of the present invention, multiple resins with different molecular weight distributions can be included at the same time, so as to further increase the uniformity of the photoresist and increase the resistance to dissolution before exposure.

According to the positive photoresist composition with uniform reactivity according to the present invention, it may further include:

The photoresist additive of (e), 0.1 to 100 parts by weight.

The photoresist additive can be selected from one or more of the following additives: dissolution inhibitors, antioxidants, heat stabilizers, light stabilizers, lubricants, colorants, defoamers, leveling agents, fillers and thickeners.

In the positive photoresist composition with multiple reaction modes of the present invention, the weight ratio of the resin compound having an acid labile functional group to the phenolic resin compound is preferably 1:6 to 1:1.

The present invention also relates to a method for forming a photoresist pattern from the positive-type photoresist composition with uniform reactivity, the method comprising the following steps: coating the positive-type photoresist composition with uniform reactivity on the processed substrate A photoresist composition; selectively exposing the formed thick film photoresist to an exposure light source; and developing the exposed thick film photoresist with alkaline aqueous solution. The positive photoresist composition having uniform reactivity is as defined above.

Description of drawings

Figures 1a to 1b are SEM images of the photoresist composition of Comparative Example 1 coated on the copper foil substrate after exposure and development. The width/gap is 1/1.8 and 1/1.6 respectively;

Figures 2a to 2b are SEM images of the photoresist composition of Comparative Example 2 coated on the copper foil substrate after exposure and development. The photoresist resolutions are respectively 9.8 μm and 13.3 μm, and the The line width/space is 1/2.1 and 1/2 respectively.

Figures 3a to 3c are SEM images of the photoresist composition of Example 1 coated on the copper foil substrate after exposure and development. The line width/space are 1/1.1, 1/1 and 1/1, respectively.

Figures 4a to 4b are SEM images of the photoresist composition of Example 2 coated on the copper foil substrate after exposure and development. The width/gap are 1/1.1 and 1/1.35 respectively.

Detailed ways

The methods, features and advantages of the present invention will be further described below through several examples and comparative examples with reference to the accompanying drawings, but they are not intended to limit the scope of the present invention.

Comparative Example 1

A cresol-formaldehyde resin with a molecular weight (Mw) of 3300 (purchased from Bordeone Company, No. DPD-193A) was dissolved in γ-butyrolactone, and the resin concentration was 66.6 wt%. Take 25 grams of the above resin solution, add 2.72 grams of polyhydroxystyrene (PHS) copolymer resin in which the hydrogen on the hydroxyl group is substituted by tert-butyl, and then use ultrasonic vibration to completely dissolve it. Finally, add photoacid triarylhexa Triaryl Sulfonium Hexafluorophosphate 50% inPropylene Carbonate (Triaryl Sulfonium Hexafluorophosphate 50% inPropylene Carbonate) (purchased from SARTOMER Chemical, No. SarCat ^(R) K185) 0.27 g, stirred until uniformly mixed, thus completing the composition preparation. The composition and weight percentage of this photoresist composition are as table 1:

Table 1 Photoresist composition Weight percent (wt%) D_PD-193APHSSarCat ^(R) K185γ-butyrolactone 35.739.720.9753.58

The photoresist composition is coated on a 1/2oz copper foil substrate with a thickness of 10 μm; the above-mentioned photoresist film layer is soft baked (soft baking), and the soft baking condition is 10 minutes at 80 ° C; the exposure light source is Parallel light UV (wavelength 365nm±10%), exposure energy 200mJ/cm ² , to expose the photoresist; then perform post-exposure bake (PEB), the post-exposure bake condition is at 120°C Do this for 10 minutes.

After post-exposure baking of the photoresist film, the photoresist film was developed in an ultrasonic vibration tank by using 2.38% tetramethylammonium hydroxide aqueous solution (SD-1, electronic grade), and the development time was controlled to be 300 seconds. Please refer to Figures 1a to 1b, which are scanning electron microscope (SEM) images showing photoresist patterns obtained after exposure and development. From the SEM images, it can be seen that the photoresist widths are 10.5 μm and 15 μm respectively, and the obtained lines The width/space is 1/1.8 and 1/1.6 respectively, and the resist line width/space ratio of the original pattern is set to 1/1.

Comparative Example 2

Get 8 gram molecular weight (Mw) and be 330 cresol resins (purchased from Bordeone Company, serial number D_PD-193A), and 2 gram molecular weights (Mw) are 6000～8500 cresol resins (purchased from Bordeone Company, serial number D_PD-140A ), they were dissolved in 15 grams of γ-butyrolactone, and the resin concentration was 66.6wt%. Next, add 2.72 grams of polyhydroxystyrene (PHS) random copolymer resin in which the hydrogen on part of the hydroxyl group is replaced by tert-butyl group, and then use ultrasonic vibration to completely dissolve it. Finally, add photoacid triaryl hexafluorophosphoric acid Salt 50% propylene glycol carbonate solution (TriarylSulfonium Hexafluorophosphate 50% in PropyleneCarbonate) (purchased from SARTOMER Chemical Company (SARTOMER Chemical), No. SarCat ^(R) K185) 0.27 g, stirred until uniformly mixed, thus completing the preparation of the composition. The composition and weight percentage of this photoresist composition are as table 2:

Table 2 Photoresist composition Weight percent (wt%) D_PD-193AD_PD-193APHSSarCat ^(R) K185 gamma-butyrolactone 28.587.159.720.9753.58

The photoresist composition is coated on a 1/2oz copper foil substrate with a thickness of 10 μm; the above-mentioned photoresist film layer is soft-baked, and the soft-baking condition is 10 minutes at 80 ° C; the exposure light source is parallel light UV ( The wavelength is 365nm±10%), the exposure energy is 300mJ/cm ² , and the photoresist is exposed; then post-exposure baking (PEB) is performed, and the post-exposure baking condition is 120° C. for 10 minutes.

After post-exposure baking, the photoresist film was developed in an ultrasonic vibration tank by using 2.38% tetramethylammonium hydroxide aqueous solution (SD-1, electronic grade), and the developing time was controlled to be 160 seconds. Please refer to Figures 2a to 2b, which are scanning electron microscope (SEM) images showing photoresist patterns obtained after exposure and development. It can be seen from the SEM images that the photoresist widths are 9.8 μm and 13.3 μm respectively, and the obtained The line width/space is 1/2.1 and 1/2 respectively, and the photoresist line width/space ratio of the original pattern is set to 1/1.

The positive photoresist described in the above comparative examples is a photoresist composition with similar properties and chemically amplified characteristics, which can reduce the exposure energy required by the photoresist during the lithography process. However, the anti-dissolution ability and polymerization uniformity of this chemically amplified photoresist composition are insufficient, resulting in poor contrast between the unexposed and exposed photoresist film layers. At the same time, the photoresist also dissolves the thickness of the two sides of the unexposed photoresist film layer, so that the photoresist line width after exposure and development is significantly reduced compared with the previously preset photoresist line width, which will cause the process The distortion of the pattern definition in the middle, and it is easy to cause the distortion of the line outline and the rough edge.

Example 1

A cresol-formaldehyde resin with a molecular weight (Mw) of 3300 (purchased from Bordeone Company, No. D_PD-193A) was dissolved in γ-butyrolactone, and the concentration of the resin solution was 66.6 wt%. Take 25 grams of the above-mentioned resin solution, add it to 2.72 grams of polyhydroxystyrene (PHS) random copolymer resin in which hydrogen on part of the hydroxyl group is substituted by tert-butyl, and then use ultrasonic vibration to completely dissolve it. Then, add 0.3 grams of triethylene glycol tetravinyl ether, and finally, add a 50% propylene glycol carbonate solution (Triaryl Sulfonium Hexafluorophosphate 50% inPropylene Carbonate) of photoacid triaryl hexafluorophosphate columbium salt (purchased from Sartomer, USA) Chemical Company (SARTOMER Chemical, No. SarCat ^(R ) K185) 0.27 g, stirred until uniformly mixed, thus completing the preparation of the composition. The composition and weight percentage of this photoresist composition are as table 3:

table 3 Photoresist composition Weight percent (wt%) D_PD-193APHSSarCat ^® K185 Triethylene glycol tetravinyl ether γ-butyrolactone 35.359.610.951.0653.03

The photoresist composition is coated on a 1/2oz copper foil substrate with a thickness of 10 μm; the above-mentioned photoresist film layer is soft-baked, and the soft-baking condition is 130 ° C for 15 minutes; the exposure light source is parallel light UV ( The wavelength is 365nm±10%), the exposure energy is 200mJ/cm ² , and the photoresist layer is exposed; then post-exposure baking is performed at 130° C. for 15 minutes.

After post-exposure baking, the photoresist film was developed in an ultrasonic vibration tank by using 2.38% tetramethylammonium hydroxide aqueous solution (SD-1, electronic grade), and the developing time was controlled to be 180 seconds. Please refer to Figures 3a to 3c, which are scanning electron microscope (SEM) images showing photoresist patterns obtained after exposure and development. From the SEM images, it can be seen that the photoresist widths are 9.5 μm, 15 μm and 20 μm, and the obtained The line width/space ratio of the original pattern is set to 1/1.

Example 2

A cresol-formaldehyde resin with a molecular weight (Mw) of 3300 (purchased from Bordeone Company, No. D_PD-193A) was dissolved in cyclopentanone (cyclopentanone), and the resin concentration was 66.6 wt%. Take 25 grams of the above resin solution, add 2.72 grams of polyhydroxystyrene (PHS) random copolymer resin in which the hydrogen on part of the hydroxyl group is substituted by tert-butyl, and then use ultrasonic vibration to completely dissolve it. Then, add 0.4 g of triethylene glycol tetravinyl ether, and then add a 50% propylene glycol carbonate solution (Triaryl Sulfonium Hexafluorophosphate 50% inPropylene Carbonate) of photoacid triaryl hexafluorophosphate (purchased from Sartomer Chemical Co. (SARTOMERChemical), No. SarCat ^(R) K185) 0.27 g, stirred until uniformly mixed, thus completing the preparation of the composition. The composition and weight percent of its photoresist composition are as table 4:

Table 4 Photoresist composition Weight percent (wt%) D_PD-193APHSSarCat ^® K185 Triethylene glycol tetraethylene ether cyclopentanone 35.239.580.951.4152.83

The photoresist composition is coated on a 1/2oz copper foil substrate with a thickness of 10 μm; the above-mentioned photoresist film layer is soft-baked, and the soft-baking condition is 130 ° C for 15 minutes; the exposure light source is parallel light UV ( The wavelength is 365nm±10%), the exposure energy is 200mJ/cm ² , and the photoresist layer is exposed; then post-exposure baking is performed at 130° C. for 15 minutes.

After post-exposure baking, the photoresist film was developed in an ultrasonic vibration tank by using 2.38% tetramethylammonium hydroxide aqueous solution (SD-1, electronic grade), and the developing time was controlled to be 260 seconds. Please refer to Figures 4a to 4b, which are scanning electron microscope (SEM) images showing photoresist patterns obtained after exposure and development. From the SEM images, it can be seen that the photoresist widths are 14.3 μm and 17 μm respectively, and the obtained lines The width/space is 1/1.1 and 1/1.35 respectively, and the resist line width/space ratio of the original pattern is set to 1/1.

In summary, the present invention relates to a positive-type photoresist composition having a highly cross-linked network structure of multi-component resins, which has excellent resistance to dissolution in alkaline aqueous solution. When the photoresist is irradiated by the exposure light source, the acid produced will cause the chemically amplified resin in the multi-component resin to undergo a deprotection reaction and the polymeric resin to undergo a deacetalization reaction, thus changing the composition of the photoresist at the same time. The hydrophilic and hydrophobic properties and the molecular weight of the photoresist components make the unexposed and exposed photoresist film layers have better contrast, and higher resolution can be obtained during the photoresist manufacturing process. When the present invention is compared with the known technology, there is no similar method in the known technology. The reason is that the photoresist needs to have an appropriate proportion of multi-component resins at the same time to carry out the deprotection reaction of the chemically amplified resin and the removal of the polymerized resin. Acetal reaction; in addition, in order to form a highly cross-linked network structure to improve the polymerization uniformity of the photoresist before exposure, it is also necessary to add an appropriate proportion of network structure reactive monomers to the photoresist composition. Therefore, the ratio of each component is allocated under a specific ratio range so that it can achieve the purpose of controlling the photoreaction efficiency of the photoresist and increasing the uniformity of the reaction, which is the key to the positive photoresist composition of the present invention. feature.

Claims (22)

1. A positive photoresist composition with uniform reactivity, comprising: dissolved in an organic solvent to form a uniform solution: (a) phenolic resin compound, 100 parts by weight; (b) a resin compound having an acid-labile functional group, 1 to 100 parts by weight; (c) reactive monomers, which have vinyl ether reactive monomers or alicyclic epoxides as the main structure, 1 to 100 parts by weight; and (d) A photoacid generator, 1 to 35 parts by weight. 2. the positive photoresist composition with uniform reactivity as claimed in claim 1, is characterized in that, described phenolic resin compound is the compound with the described structure of formula (I)

Formula (I), Wherein _R can be the same or different, and is selected from one of the following groups: -CH ₂ -,

Alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl and aryl, wherein the alkyl, alkoxy, alkenyl and alkynyl contain 2-12 carbon atoms and are linear or branched, The cycloalkyl group contains 3-12 carbon atoms, and the value of n is 1-100. 3. The positive-type photoresist composition with uniform reactivity as claimed in claim 2, is characterized in that, the hydrogen on each carbon atom in the phenolic resin compound with formula (I) structure is optionally replaced by halogen , cyano, -R", -CO ₂ H, -CO ₂ R", -COR", -R"CN, -CONH ₂ , -CONHR", -CONR" ₂ , -OCOR" or OR", wherein R" is selected from substituted or unsubstituted alkyl, alkynyloxy, alkoxy, alkenyl, alkynyl, alkenyloxy, heterocyclyl, aryl, aralkyl, Heteroaryl, aliphatic polycyclic, or combinations thereof. 4. The positive photoresist composition with uniform reactivity as claimed in claim 2, characterized in that, in the phenolic resin compound having the structure of formula (I), the value of n is 2-30. 5. The positive photoresist composition with uniform reactivity as claimed in claim 1, wherein the acid-labile functional group is selected from one or more of the following groups: tert-butyl , Tetrahydropyran-2-yl, 2-methyltetrahydropyran-2-yl, tetrahydrofuran-2-yl, 2-methyltetrahydrofuran-2-yl, 1-methoxypropyl, 1-methyl Oxy-1-methylethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, 1-methoxyethyl, 1-ethoxyethyl, 1-butane Oxyethyl, 1-tert-butoxyethyl, 1-isobutoxyethyl, tert-butoxycarbonyl, tert-butoxycarbonylmethyl, trimethylsilyl, 3-tert-butyldimethyl ylsilyl and 2-acetyloxinyl-1-yl. 6 . The positive photoresist composition with uniform reactivity according to claim 1 , wherein the resin compound having acid-labile functional groups is an acrylic resin having acid-labile functional groups. 7. The positive photoresist composition with uniform reactivity as claimed in claim 1, wherein the resin compound having an acid-labile functional group is polyhydroxystyrene having an acid-labile functional group resin. 8. The positive photoresist composition with uniform reactivity as claimed in claim 6, wherein the acrylic resin having an acid labile functional group is selected from one or more of the following resins: Tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethyl acrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, Pentaerythritol Triacrylate, Ethoxylated Trimethylolpropane Triacrylate, Glyceryl Propoxy Triacrylate, Pentaerythritol Tetraacrylate, Dipentaerythritol Pentaacrylate, Glycidyl Acrylate, Epoxy Methacrylate Copolymers of propyl esters and mixtures thereof. 9. The positive photoresist composition with uniform reactivity as claimed in claim 1, wherein said photoacid generator is selected from onium salt, sulfonate, diazonium salt, naphthoquinone diazide Sulfonates or mixtures thereof. 10. The positive-type photoresist composition with uniform reactivity as claimed in claim 9, wherein said onium salt is selected from triaryl percited salts, alkaryl percited salts, diaryl iodonium salts, Diaryl chloride salts, diaryl bromide salts or mixtures thereof. 11. The positive-type photoresist composition with uniform reactivity according to claim 10, wherein the triaryl cobaltium salt is a triaryl cobaltium hexafluorophosphate. 12. The positive photoresist composition with uniform reactivity as claimed in claim 9, wherein the salt is selected from the group consisting of triphenyl trifluoromethanesulfonate, triphenyl antimonate, methoxy In the group consisting of triphenyltrifluoromethanesulfonate, methoxytriphenyltrifluoromethanesulfonate, trimethyltriphenyltrifluoromethanesulfonate and mixtures thereof. 13. The positive photoresist composition with uniform reactivity as claimed in claim 1, wherein said vinyl ether reactive monomer is selected from 1,4-cyclohexanedimethanol diglycidyl Ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene Glycol divinyl ether, neopentyl glycol divinyl ether, hexylene glycol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1, 4-Cyclohexanedimethanol divinyl ether or mixtures thereof. 14. The positive photoresist composition with uniform reactivity as claimed in claim 1, wherein the cycloaliphatic epoxide is selected from the group consisting of N, N-diglycidyl-4-dehydrated glyceryl Aniline, 3,4-epoxycyclohexanemethyl carboxylate, 3,4-epoxycyclohexane carboxylate, 1,2-cyclohexane diglycidyl dicarboxylate or mixtures thereof. 15. The positive photoresist composition with uniform reactivity as claimed in claim 1, wherein the component (a) phenolic resin and component (b) have a resin with an acid-labile functional group, the molecular weight of which is Between 2,000 and 150,000. 16. The positive-type photoresist composition with uniform reactivity as claimed in claim 1, wherein the component (a) phenolic resin and component (b) have a resin with an acid-labile functional group, the molecular weight of which is Between 3000 and 100000. 17. The positive-type photoresist composition with uniform reactivity as claimed in claim 1, wherein the positive-type photoresist composition with uniform reactivity undergoes a multiple reaction mode after being irradiated by the exposure light source , and the multiple reaction mode includes the synchronous reaction of changing the hydrophilic and hydrophobic properties of the photoresist constituent molecules and changing the molecular weight of the photoresist constituent molecules. 18. The positive photoresist composition with uniform reactivity as claimed in claim 1, wherein said photoresist composition further comprises: (e) Photoresist additive, 0.1 to 100 parts by weight. 19. The positive-type photoresist composition with uniform reactivity as claimed in claim 18, wherein the photoresist additive is selected from dissolution inhibitors, antioxidants, heat stabilizers, light stabilizers , one or more of lubricants, colorants, defoamers, leveling agents, fillers and thickeners. 20. The positive-type photoresist composition with uniform reactivity as claimed in claim 1, wherein the weight ratio of the resin compound having an acid-labile functional group to the phenolic resin compound is in the range of 1 : Between 6 and 1:1. 21. A method for forming a photoresist pattern, comprising the following steps in sequence: coating a positive photoresist composition with uniform reactivity on the treated substrate; selectively irradiating the formed photoresist with an exposure light source; and Treat the exposed photoresist with an alkaline aqueous solution, Wherein, the positive photoresist composition with uniform reactivity comprises: (a) phenolic resin compound, 100 parts by weight; (b) a resin compound having an acid-labile functional group, 1 to 100 parts by weight; (c) reactive monomers, which have vinyl ether as the main structure, 1 to 100 parts by weight; and (d) A photoacid generator, 1 to 35 parts by weight. 22. The method for forming a photoresist pattern according to claim 21, wherein the positive photoresist composition with uniform reactivity undergoes a multiple reaction mode after being irradiated by the exposure light source, and the multiple The reaction mode includes the synchronous reaction of the change of the hydrophilic and hydrophobic properties of the photoresist constituent molecules and the change of the molecular weight of the photoresist constituent molecules.

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