JP4538631B2 - Reaction development image forming method - Google Patents

Description

  The present invention relates to a photoresist technique that can be used in the manufacture of semiconductor integrated circuits, printed wiring boards, liquid crystal panels, and the like, and more specifically, using a polymer having a carbonyl group in the side chain and a photoacid generator. The present invention relates to a photoresist technique in which a film is irradiated with light and a positive image is formed through a development process.

Photoresists are commonly used in photolithographic organic polymers used in the related art in photographic deck processing, for the production of printed circuit boards and printed circuit boards, or for the production of semiconductor laminates in microelectronics. .
In order to create circuit structures in the manufacture of microelectronic semiconductor integrated components, the semiconductor substrate is imaged with a photoresist layer coated with a photoresist and subsequent development creates a photoresist relief structure. This relief structure is used on a semiconductor substrate as a mask for creating an actual circuit pattern by etching-doping or coating using a metal or other semiconductor or insulating substrate. Thereafter, the photoresist mask is usually removed. A microchip relief structure is formed on the substrate using a plurality of such processing cycles.
Two different types of photoresists are known: a positive resist and a negative resist. The difference between the two types is that the exposed area of the positive photoresist is removed by the development process, leaving the unexposed area as a layer on the substrate. On the other hand, the irradiation area of the negative working photoresist remains as a relief structure. Positive photoresists have inherently high image resolution and are used in the manufacture of VLSI (very large scale integrated circuits).

  Previous photoresists have functional groups (such as carboxyl groups and phenolic hydroxyl groups) capable of acid-base reactions with bases in the side chains of polymers, or react with acids or bases to react with carboxyl groups or phenolic hydroxyl groups. It is essential to have a reactive group (such as an ester or a phenol type ether bonded to a protective group) that can generate a chemical group (see, for example, Patent Documents 1 to 3). For example, in order to make a simple polycarbonate into a resist by a conventional method, it is necessary to introduce a carboxyl group, a phenolic hydroxyl group or a group in which an appropriate protective group is bonded to the side chain of this polymer. The introduction of these functional groups was very difficult.

The inventors have already developed a photoresist using a resin having a carbonyl group (C═O) bonded to a hetero atom in the main chain without having any special reactive group in the side chain of the resin skeleton. For this purpose, a new means called “reactive development image forming method” was developed (Patent Document 4).
This “reactive development image forming method” is a kind of positive photoresist technology. First, a resin containing a carbonyl group (C═O) having a photoresist layer bonded to a hetero atom (C═O) in the main chain and a photoacid generator Then, the layer is appropriately masked in a desired pattern and then irradiated with ultraviolet rays. The photoacid generator generates an acid by this ultraviolet irradiation. When this is washed with a developer containing an alkali (particularly a nucleophilic amine), a salt is formed by reacting with the acid produced by the alkali (particularly the nucleophilic amine), and the polarity of the exposed area Will increase. As a result, an alkali (particularly a nucleophilic amine) in the developing solution attacks the carbonyl group bonded to the hetero atom constituting the main chain of the polymer in the exposed region. This attack breaks the main chain at the carbonyl group. Due to the cleavage of the main chain, the polymer is reduced in molecular weight and dissolved in the developer.

JP2001-66781 JP2001-192573 JP2001-249458 JP2003-76013

As an improved method of the “reactive development image forming method” (Patent Document 4), the present inventors have used a polymer having a carbonyl group in the side chain and formed a photoresist by making it soluble in a developer. "Reactive development image forming method" (Japanese Patent Application 2003-375137) was developed.
However, this method is complicated because it requires a two-step development process. The present invention is a further improvement of the “reactive development image forming method” (Japanese Patent Application No. 2003-375137), and is characterized in that the development process is carried out in one step.

In the “reactive development image forming method” of the present invention, a polymer containing a carbonyl group such as a carboxylic acid analog group in the side chain is used, and a developer containing a metal alkoxide and a polar solvent is used in the development stage after light irradiation. Thus, it was found that development can be performed in one step.
That is, the present invention comprises a step of providing a photoresist layer comprising a polymer having a carbonyl group in the side chain and a photoacid generator on a substrate, masking with a desired pattern, irradiating the pattern surface with ultraviolet light, and The development step involves processing the photoresist layer with a developer, and the developer is represented by the following formula MO-R-X
(Wherein M represents an alkali metal or alkaline earth metal, R represents an alkylene group, X represents a primary amino group, a secondary amino group, or a tertiary amino group) and a polar solvent. This is a reactive development image forming method.

  The present invention also provides a photoresist structure having a photoresist layer formed on the substrate by the above method, wherein the thickness of the photoresist layer is 0.1 to 500 μm, and the polymer is a side chain. The photoresist structure does not have a reactive group that can react with an acid or a base to generate a carboxyl group or a phenolic hydroxyl group. A relief structure having a desired pattern can be formed as the photoresist layer.

The reaction mechanism of the “reactive development image forming method” of the present invention is considered as follows.
In the previous “Reactive Development Image Forming Method” (Japanese Patent Application No. 2003-375137), UV light is first applied to a polymer having a carbonyl group such as a carboxylic acid analog group in the side chain and a photoacid generator (photosensitive agent) added. Irradiate. The development stage consists of two stages, as shown below.

First, development in the first stage is performed with a developer containing a metal alkoxide having a specific structure (hydrophilic nucleophile), and development in the second stage is further conducted with a developer containing acid. In these two stages, pattern formation was performed utilizing the difference in solubility between the irradiated portion and the non-irradiated portion.

On the other hand, in the “reactive development image forming method” of the present invention, the same polymer is used, but the development stage is one stage as shown below.
In this method, a developer containing a metal alkoxide and a polar solvent is used. Since the polymers (polymer B and C) produced by the metal alkoxide have improved polarity, they are soluble in the developer when developed using a developer containing a highly polar solvent. However, since the non-irradiated portion does not exhibit solubility in this developer, pattern formation can be performed using the difference in solubility of the non-irradiated portion.

The polymer used in the present invention has a carbonyl group (C═O) in the side chain.
A polymer having a carbonyl group (C═O) in the side chain has the following formula:
It has a substituent represented by. R ² is an alkyl group or an aryl group .
The condensed polymer containing a carbonyl group (C═O) bonded to a hetero atom in the main chain is a subject of a photoresist by the other reactive development image forming method of the present inventors (Patent Document 4). Even if it is a polymer, as long as it has the said substituent in a side chain, the method of this invention may be applied.

Preferred polymers include polyvinyl, polyether, polyethersulfone, polysulfone, polyoxyphenylene, polysulfide, polyketone and the like. As polyvinyl, acrylonitrile, methyl acrylate, phenyl acrylate, methyl methacrylate, phenyl methacrylate, nitrophenyl methacrylate, methyl α-cyanoacrylate, styrene, isobutene, alkyl vinyl ether, aryl vinyl ether, vinyl chloride, vinyl acetate, Examples thereof include those obtained by addition polymerization of ethylene, propylene and butadiene, or copolymers comprising these. It may be a polymer having an imide, carbonate, ester, urethane or amide bond in the main chain.
To introduce a carbonyl group in the polymer, Ma maleic acid in the polymer, maleic anhydride, maleic anilide, maleic anil (N- phenylmaleimide), maleic anil acid, maleic amide, maleamic acid, maleimide, or their esters mode Nomar such derivatives may be obtained with by addition polymers.
As the polymer of the present invention, a copolymer obtained by polymerizing a plurality of monomers constituting these polymers may be used.

The photoacid generator used in the present invention may be any one that facilitates the reaction between the light irradiated portion of the polymer and the metal alkoxide by generating an acid by light irradiation. Examples of the photoacid generator include quinonediazide compounds, onium salts, sulfonic acid esters, and organic halogen compounds. The quinonediazide compound includes 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid and a low-molecular aromatic hydroquinone compound such as 2,3,4-trihydroxy. Mention may be made of benzophenone, 2,3,4,4′-tetrahydroxybenzophenone and trihydroxybenzene, for example 1,3,5-trihydroxybenzene, or ester-forming compounds of cresol. Examples of onium salts include triphenylsulfonium hexafluoroantimonate and triphenylsulfonium hexafluorophosphate. These are used with esters such as t-butyl benzoate. Among these, 1,2-naphthoquinone-2-diazide-5-sulfonic acid-p-cresol ester is particularly preferable.
The photoacid generator is used in the photoresist in an amount of 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 20 to 30% by weight based on the total solid content.

  Solvents suitable for the production of photoresist solutions are in principle all solvents in which the non-volatile components of the photoresist, such as polymers and photoacid generators and other additives, are sufficiently soluble and do not irreversibly react with these components. It is. Suitable solvents include, for example, aprotic polar solvents such as N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”), butyrolactone, cyclohexanone, diacetoxyethylene glycol, sulfolane, tetramethylurea, N, N′— Examples thereof include dimethylacetamide, dimethylformamide, dimethylsulfoxide, acetonitrile, diglyme, phenol, cresol, toluene, methylene chloride, chloroform, tetrahydrofuran, dioxane, acetone and the like.

Other conventional improving additives that may be present in the positive photoresists of the present invention include coupling agents, leveling agents, plasticizers, other film-forming resins, surfactants and stabilizers. These modifiers are well known to those skilled in the art. Even when all of these modifiers are combined, they do not exceed 25% by weight based on the total solid content of the photoresist solvent.
The photoresist of the present invention is formulated by mixing or dissolving the components in a solvent or solvent mixture by a method known per se. Once the components are dissolved in the solution, the resulting photoresist solution may be filtered using a filtration membrane having 0.1-1 μm pores.

A photoresist layer can be formed on the substrate using such a photoresist solution. As the substrate, any organic material such as resin, inorganic material, metal, etc. may be used, but a copper substrate or a silicon substrate is preferable.
Coating onto the substrate is usually done by dipping, spraying, roll coating or spin coating. The resulting layer thickness depends on the viscosity, solids content and spin coating speed of the photoresist solution. The photoresist of the present invention can make a layer and a relief structure having a layer thickness of 0.1 to 500 μm, preferably 1 to 100 μm. The thin layer in the multi-layer circuit can be 1-50 μm as a temporary photoresist or as an insulating layer.
After the photoresist is applied to the substrate, it is usually pre-dried at a temperature range of 50 to 120 ° C. An oven or a heating plate can be used. The drying time in the oven is 5 to 60 minutes.

Thereafter, the photoresist layer is irradiated with ultraviolet rays after being masked with a desired pattern. Ultraviolet rays refer to electromagnetic waves having a central wavelength of 250 to 450 nm, preferably 300 to 400 nm. Usually actinic light is used, but high-energy radiation such as X-rays or electron beam rays can also be tried. Direct irradiation or via an exposure mask can be performed. A radiation beam can also be applied to the surface of the photoresist layer.
Usually, radiation is performed using an ultraviolet lamp. It is preferable to use a commercially available radiation apparatus such as a contact or non-contact exposure machine, a scanning projection type exposure apparatus or a wafer stepper.

Development is performed after exposure. In the development process, the photoresist layer is formed by the following formula MO-R-X
Development processing is performed with a first developer containing a metal alkoxide represented by the formula:
M is an alkali metal or alkaline earth metal, preferably an alkali metal, more preferably sodium or potassium.
R represents an alkylene group. The number of carbon atoms of R 2 to 6, especially 2 to 4 is not preferable.
MO may be bonded to any of the primary, secondary or tertiary carbons of the alkylene group (R), but is preferably bonded to the primary or secondary carbons. Most preferably.
X represents a primary amino group (—NH ₂ ) .

This metal alkoxide is used by dissolving in a solvent.
Since this developer is usually prepared by adding sodium into HO—R—NH ₂ (R is the same as above), the main solvent is HO—R—NH ₂ . The concentration of MO—R—NH ₂ / HO—R—NH ₂ (M and R are the same as above) at this time is preferably about 5 to 20 mol% (10 mol% as a standard). A developer is obtained by further mixing another solvent.
A polar solvent, preferably a highly polar solvent is used as the second solvent. This polar solvent has a role of dissolving a polymer having improved polarity as a result of reaction development in a developer. Such a polar solvent medium is an A alcohol class. As alcohols, methanol, ethanol, propanol and the like are preferably used.

In addition, since this solvent dissolves the polymer (polymer B and C in Chemical Formula 2) produced by the treatment with the metal alkoxide, it is preferable to select an optimal solvent as the solvent depending on the type of polymer.
For example, when the polymer is a vinyl ether-maleimide copolymer type, good development characteristics are exhibited with an alkoxide solution / methanol = 1/2 to 4/1 (particularly 3/1), and a pattern is formed in about 1 to 3 minutes. The

HO-R-NH _2: weight ratio of solvent to be added later is preferably from about 1: 2 to 25: 1 or so, and most preferably 3: 1 (where the alkyl vinyl ether -N- phenylmaleimide alternating copolymer) Degree.
It is also possible to isolate a metal alkoxide once made in HO—R—NH _{2 and} then dissolve it in a solvent and use it as a developer. As a solvent in that case, a mixed solvent of N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylformamide and the like and an alcohol can be used.

Development is performed in consideration of the type of polymer or metal alkoxide, exposure energy, type of development, preliminary drying temperature, development temperature, and development time.
You may wash | clean with a suitable solvent after image development.
The positive photoresist of the present invention can have a polymer film having a layer thickness of 0.1 to 500 μm, preferably 1 to 100 μm, and a sharp contoured relief structure.

The following examples illustrate the invention, but are not intended to limit the invention.
In this example, a photoresist was formed by the following method and observed. The photoresist was produced by filtering the photoresist composition of each example through a filter membrane having a pore size of 3 μm. This photoresist formulation was applied by spin coating on the surface of a 10 cm diameter copper foil that had not been surface-treated. Subsequently, it dried in the infrared hot air dryer. A test pattern for a positive photomask (through hole and line and space pattern of 10 to 200 μm) is placed on this photoresist compound coating film, and a 2 kw ultra-high pressure mercury lamp irradiation device (Oak Seisakusho product: JP-2000G) is used. Then, irradiation was performed with an exposure amount that could provide an image.
The coating film after irradiation was immersed in the developer, washed with alcohol, dried with an infrared lamp, and the resolution was observed. In some examples, the formed photoresist was observed by SEM (manufactured by JEOL Ltd., scanning electron microscope: SM-5500LV, acceleration voltage: 10 kV).

2 g of N-phenylmaleimide-butyl vinyl ether alternating copolymer (hereinafter referred to as PMnBV) synthesized by radical copolymerization of N-phenylmaleimide and butyl vinyl ether was dissolved in 4.7 g of NMP to obtain an NMP varnish of PMnBV ( Solid content: 30% by weight). Next, 0.6 g of diazonaphthoquinone-based photosensitizer PC-5 (Toyo Gosei Co., Ltd., 1,2-naphthoquinone-2-diazide-5-sulfonic acid-p-cresol ester) was added to the varnish, and about 1 hour at room temperature. A photoresist composition (photosensitive PMnBV composition) was prepared by stirring with a stirrer. This solution is applied on a 35μm electrolytic copper foil (Mitsui Kinzoku Co., Ltd. product, 35μm thickness) (mat surface) by spin coating (600rpm / 10sec + 1200rpm / 30sec), using a far-infrared hot air circulation dryer. After pre-baking (90 ° C./15 minutes), a photosensitive PMnBV coating film having a film thickness of 13.3 μm was obtained. Using ultraviolet exposure machine (manufactured by Oak Co.), (measured in a luminometer for i-line band) 2000 mJ / cm ² light of g-line bands from i-line through a photomask made of PET was irradiated. After exposure, development was performed by immersing in a developer solution (weight ratio: 3/1) of 60 g of sodium 2-aminoethoxide / ethanolamine solution (10 mol%) and 20 g of methanol at 50 ° C for 1 minute and 5 seconds. It was. Next, it was rinsed with 20 g of methanol for 1 minute to obtain a positive image. The resolution was 20 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

  Instead of PMnBV, an N-phenylmaleimide-isobutyl vinyl ether alternating copolymer (hereinafter referred to as PMiBV) synthesized by radical copolymerization of N-phenylmaleimide and isobutyl vinyl ether was used, and the same operation as in Example 1 was performed. A photoresist formulation was prepared. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coated film having a thickness of 14.8 μm. After exposure, development was performed by immersing in a developer solution (weight ratio: 3/1) of 60 g of sodium 2-aminoethoxide / ethanolamine solution (10 mol%) and 20 g of methanol at 50 ° C for 1 minute and 15 seconds. It was. Next, it was rinsed with 20 g of methanol for 1 minute to obtain a positive image. The resolution was 20 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

  In place of PMnBV, an N-phenylmaleimide-tert-butyl vinyl ether alternating copolymer (hereinafter referred to as PMtBV) synthesized by radical copolymerization of N-phenyl maleimide and tert-butyl vinyl ether was used in the same manner as in Example 1. Thus, a photoresist composition was prepared. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coated film having a thickness of 15.5 μm. After exposure, development was performed by immersing in a developer solution (weight ratio: 3/1) of 60 g of sodium 2-aminoethoxide / ethanolamine solution (10 mol%) and 20 g of methanol at 50 ° C for 2 minutes and 30 seconds. It was. Next, it was rinsed with 20 g of methanol for 1 minute to obtain a positive image. The resolution was 20 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

  In place of PMnBV, an N-phenylmaleimide-cyclohexyl vinyl ether alternating copolymer (hereinafter referred to as “PMCV”) synthesized by radical copolymerization of N-phenylmaleimide and cyclohexyl vinyl ether was used, and the same operation as in Example 1 was performed. To prepare a photoresist formulation. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coated film having a thickness of 17.8 μm. After exposure, development was performed by immersing in a developer solution (weight ratio: 3/1) containing 60 g of sodium 2-aminoethoxide / ethanolamine solution (10 mol%) and 20 g of methanol at 50 ° C for 2 minutes and 50 seconds. It was. Next, it was rinsed with 20 g of methanol for 1 minute to obtain a positive image. The resolution was 20 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

  In place of PMnBV, an N-phenylmaleimide-styrene alternating copolymer (hereinafter referred to as PMS) synthesized by radical copolymerization of N-phenylmaleimide and styrene was used, and the same operation as in Example 1 was performed. A resist formulation was prepared. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coated film having a thickness of 13.0 μm. After exposure, develop for 22 minutes at 50 ° C under ultrasonic treatment using a developer (weight ratio: 20/1) in which 50 g of sodium 2-aminoethoxide / ethanolamine solution (10 mol%) and 2.5 g of methanol are mixed. Went. Next, it was rinsed with 20 g of methanol for 1 minute to obtain a positive image. The resolution was 20 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

  Instead of PMS, N-phenylmaleimide-styrene alternating copolymer and maleic anhydride-styrene alternating copolymer are ternary copolymers synthesized by radical copolymerization of N-phenylmaleimide, maleic anhydride and styrene. Using a copolymer copolymer (hereinafter referred to as PMS-co-MAS), the same operation as in Example 1 was performed to prepare a photoresist composition. Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coating film having a thickness of 12.5 μm. After exposure, develop for 10 minutes at 50 ° C under ultrasonic treatment using a developer (weight ratio: 20/1) mixed with 50 g of sodium 2-aminoethoxide / ethanolamine solution (10 mol%) and 2.5 g of methanol. Went. Next, it was rinsed with 20 g of methanol for 1 minute to obtain a positive image. The resolution was 20 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

  The same operation as in Example 1 was performed to prepare a photoresist composition (PMnBV). Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coated film with a thickness of 13.3 μm. After exposure, the developer (weight ratio: 3/1) in which 60 g of sodium 3-amino-1-propoxide / 3-amino-1-propanol solution (10 mol%) and 20 g of methanol were mixed was mixed at 50 ° C. for 1 minute 30 Development was performed by dipping for 2 seconds. Next, it was rinsed with 20 g of methanol for 1 minute to obtain a positive image. The resolution was 25 μm with a line and space pattern.

  The same operation as in Example 1 was performed to prepare a photoresist composition (PMnBV). Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coated film with a thickness of 13.3 μm. After exposure, development was performed by immersing in a developer solution (weight ratio: 3/1) of 60 g of potassium 2-aminoethoxide / ethanolamine solution (10 mol%) and 20 g of methanol at 50 ° C for 1 minute and 10 seconds. It was. Next, it was rinsed with 20 g of methanol for 1 minute to obtain a positive image. The resolution was 20 μm with a line and space pattern.

  The same operation as in Example 1 was performed to prepare a photoresist composition (PMnBV). Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coated film having a thickness of 13.3 μm. After exposure, the developer (weight ratio: 3/1) in which 60 g of sodium 1-amino-2-propoxide / 1-amino-2-propanol solution (10 mol%) and 20 g of methanol are mixed is mixed at 50 ° C. for 1 minute 20 Development was performed by dipping for 2 seconds. Next, it was rinsed with 20 g of methanol for 1 minute to obtain a positive image. The resolution was 25 μm with a line and space pattern.

  The same operation as in Example 1 was performed to prepare a photoresist composition (PMnBV). Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coated film with a thickness of 13.3 μm. After exposure, development was performed by immersing in a developer solution (weight ratio: 3/1) containing 60 g of sodium 2-aminoethoxide / ethanolamine solution (10 mol%) and 20 g of ethanol at 50 ° C for 1 minute and 10 seconds. It was. Next, it was rinsed with 20 g of methanol for 1 minute to obtain a positive image. The resolution was 20 μm with a line and space pattern.

  The same operation as in Example 1 was performed to prepare a photoresist composition (PMnBV). Using this photoresist composition, the same operation as in Example 1 was performed to obtain a photosensitive coated film with a thickness of 13.3 μm. After exposure, development was performed by immersing in a developer (weight ratio: 4/1) in which 60 g of sodium 2-aminoethoxide / ethanolamine solution (10 mol%) and 15 g of propanol were mixed at 50 ° C. for 1 minute and 40 seconds. It was. Next, it was rinsed with 20 g of methanol for 1 minute to obtain a positive image. The resolution was 25 μm with a line and space pattern.

  A substrate having a photoresist layer of a pattern formed by the reaction development image forming method of the present invention can be used for microelectronics and optoelectronic circuits and components. For example, semiconductor integrated circuits, printed wiring boards, liquid crystal panels It can be used as a waveguide or the like.

The SEM photograph of the photoresist (Example 1) formed using the resin PMnBV and using sodium 2-aminoethoxide / ethanolamine solution (10 mol%) / methanol (weight ratio: 3/1) as the developer is shown. FIG. The SEM photograph of the photoresist (Example 2) formed using the resin PMiBV and using sodium 2-aminoethoxide / ethanolamine solution (10 mol%) / methanol (weight ratio: 3/1) as the developer is shown. FIG. The SEM photograph of the photoresist (Example 3) formed using the resin PMtBV and using sodium 2-aminoethoxide / ethanolamine solution (10 mol%) / methanol (weight ratio: 3/1) as the developer is shown. FIG. The SEM photograph of the photoresist (Example 4) formed using the resin PMCV and using sodium 2-aminoethoxide / ethanolamine solution (10 mol%) / methanol (weight ratio: 3/1) as the developer is shown. FIG. The SEM photograph of the photoresist (Example 5) formed using resin PMS and using sodium 2-aminoethoxide / ethanolamine solution (10 mol%) / methanol (weight ratio: 20/1) as the developer is shown. FIG. Using a resin PMS-co-MAS, a photoresist (Example 6) formed using sodium 2-aminoethoxide / ethanolamine solution (10 mol%) / methanol (weight ratio: 20/1) as a developer It is a figure which shows a SEM photograph.

Claims (4)

The following formula on the side chain on the substrate
(Wherein R ² represents an alkyl group or an aryl group) A photoresist layer comprising a polymer having a substituent and a photoacid generator is provided and masked with a desired pattern. The step of irradiating, and the step of developing the photoresist layer with a developer, the developer having the formula MO-RX
(Wherein, M is an alkali metal or alkaline earth metal, R represents an alkylene group, X represents. A primary amino group (-NH ₂₎₎ observed containing a metal alkoxide and a polar solvent represented by the polar solvent Reactive development image forming method in which is an alcohol The reaction developed image forming method according to claim 1 before Kia alcohols such is methanol, ethanol or propanol. By the method described in 請 Motomeko 1 or 2, the method of fabricating the photoresist structure with a photoresist layer thickness is 0.1~500μm on the substrate. The method according to claim 3, wherein the photoresist layer has a relief structure having a desired pattern.