JP5584428B2 - 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, a polymer having a carbonyl group bonded to a hetero atom in the main chain and a photoacid generator The present invention relates to a photoresist technique in which a film is formed, irradiated with light, and a negative 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.
As the photoresist, a positive resist and a negative resist are known. The exposed areas of the positive photoresist are removed by the development process, leaving the unexposed areas as a layer on the substrate. On the other hand, the irradiation area of the negative working photoresist remains as a relief structure.

The inventors have already used a resin having a carbonyl group (C═O) bonded to a heteroatom in the main chain without having any special reactive group in the side chain of the resin skeleton. "Reactive development image forming method" for forming a resist was developed (Patent Document 1, Non-Patent Document 1), and further, "Reactive development image forming method" was improved to efficiently produce a negative photoresist. The method which can do was developed (patent document 2).
In this negative photoresist forming method, a polymer having a carbonyl group (C═O) in the main chain is mixed with a photoacid generator such as a diazonaphthoquinone compound and an anion regenerating agent such as an N-substituted maleimide compound. And developing with a developer comprising a solvent containing tetra-substituted ammonium hydroxide, a low molecular alcohol and water, and the solubility of the exposed and unexposed areas after UV irradiation in the developer. This is a technique for forming a negative photoresist using the difference.

JP2003-76013 JP2007-328333

J. Microlith. Microfab. Microsyst., 3, 159-167 (2004).

  The negative photoresist forming method developed by the present inventors (Patent Document 2) has significantly improved sensitivity compared to the positive photoresist forming method (Patent Document 1), and a photosensitive agent (photoacid generator). However, when an anion regenerator such as an N-substituted maleimide compound is contained in the polymer, there is a concern that the physical properties of the formed photoresist may be deteriorated.

  As a result of examining the structure of the polymer in the negative photoresist forming method (Patent Document 2), the present inventors have not included an anion regenerating agent such as an N-substituted maleimide compound in a polymer that has been considered essential until now. In addition, a polymer having a carbonyl group (C = O) in the main chain is mixed with only a photoacid generator such as a diazonaphthoquinone compound, and developed by irradiating with ultraviolet rays. The present inventors have found that a negative photoresist similar to the conventional one can be formed in an amount, and have completed the present invention.

That is, the present invention provides a photoresist layer containing a condensed polymer containing a carbonyl group (C═O) bonded to a hetero atom (C═O) in the main chain and a photoacid generator on the substrate and not containing an anion regenerant, The method comprises a step of masking with a desired pattern, a step of irradiating the pattern surface with ultraviolet rays at an exposure amount of less than 100 mJ / cm ² , and a development step of treating the photoresist layer with a developer. A reaction development image forming method comprising a solvent containing a solvent, a low molecular alcohol and water . It is possible to form a relief structure of the desired pattern as the photoresist layer of this.

2 is a SEM photograph of the photoresist formed in Reference Example 1 . 4 is a SEM photograph of the photoresist formed in Reference Example 2 . 10 is a SEM photograph of the photoresist formed in Reference Example 3 . 2 is an SEM photograph of the photoresist formed in Example 1 . 3 is a SEM photograph of the photoresist formed in Example 2 . 6 is a SEM photograph of the photoresist formed in Reference Example 4 . 10 is a SEM photograph of the photoresist formed in Reference Example 5 . 10 is a SEM photograph of the photoresist formed in Reference Example 6 . 10 is a SEM photograph of the photoresist formed in Reference Example 7 .

The condensed polymer containing a carbonyl group (C═O) bonded to a hetero atom used in the present invention in the main chain is an imide bond, a carbonate bond, an ester bond, a urethane bond, an amide bond, or an amide bond, or A polymer containing a plurality of these bonds.
Examples of the polymer that is the subject of the present invention include polyetherimide, polyamide, polyamideimide, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalate, polyarylate, polyurethane, and copolymers related thereto. Can be mentioned.
The polymer to which the reaction development image forming method of the present invention can be preferably applied is a carboxyl group which reacts with a functional group capable of reacting with a base (for example, a carboxyl group or a phenolic hydroxyl group), an acid or a base, and the like. Or a reactive group capable of generating a phenolic hydroxyl group (such as an ester or phenolic ether bonded to a protecting group) or a group that undergoes a crosslinking reaction upon irradiation with light (such as an acryloyl group or a methacryloyl group).

The polymer used in the present invention contains a photoacid generator.
The photoacid generator used in the present invention may be any one that generates acid upon 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. Examples include benzophenone, 2,3,4,4′-tetrahydroxybenzophenone and trihydroxybenzene, such as 1,3,5-trihydroxybenzene, or an ester-forming compound 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 15 to 30% by weight based on the total solid content.

On the other hand, the polymer used in the present invention is characterized by not containing an anion regenerant.
Examples of the anion regenerating agent include the following compounds.
(1) Compound having a structure represented by the following formula:

In the above formula, X represents a substituent represented by the following formula.
In the formula, Y represents —NR ¹ ₂ , —OR ¹ (excluding —OH), —CR ¹ ₃ or —SR ¹ (excluding —SH), preferably —NR ¹ ₂ or — Represents CR ¹ ₃ .
In these formulas, each R ¹ independently represents a hydrogen atom, an aliphatic group or an aromatic group, preferably an aromatic group, more preferably a phenyl group. Examples of the aliphatic group include alkyl groups such as a methyl group, a propyl group, a hexyl group, and a cyclohexyl group.

(2) Compound having a structure represented by the following formula:
R ² -CONHR ¹
Or R ² —COCH (R ¹ ) ₂
In the formula, each R ² independently represents an aliphatic group or an aromatic group. Examples of the aliphatic group include alkyl groups such as a butyl group, an isobutyl group, and a hexyl group, and examples of the aromatic group include a phenyl group and a phenylene group.
R ¹ is defined as above.

(3) Compound having a structure represented by the following formula:
In the formula, at least one of R ³ represents an aliphatic group or an aromatic group, and the other represents a hydrogen atom. Examples of the aliphatic group include alkyl groups such as an oxymethylene group and an octyl group, and examples of the aromatic group include a phenyl group and a phenylene group.
Z represents an oxygen atom (—O—) or a sulfur atom (—S—).

(4) Compound having a structure represented by the following formula:
^{_{CH (R 4) 2 C (}} R 1) 2 OCO-N (R 1) 2
In the formula, at least one of R ⁴ represents an electron withdrawing group, and the other represents a hydrogen atom, an aliphatic group, or an aromatic group. Examples of the aliphatic group include an alkyl group, and examples of the aromatic group include a phenyl group and a phenylene group. Examples of the electron withdrawing group include a fluorenyl group, an organic sulfoxide group, a cyano group, a nitro group, an ester group, a carbonyl group, an amide group, and a pyridyl group, preferably a fluorenyl group. Examples of the aromatic group include a phenyl group and a phenylene group.
R ¹ is defined as above.

Examples of such an anion regenerating agent include N-methylmaleimide, N-ethylmaleimide, N- (n-propyl) maleimide, N- (n-hexyl) maleimide, N- (n-octyl) maleimide, N- Laurylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide (N-substituted maleimide compounds), N-phenylcitraconimide, N-phenylsuccinimide, N, N'-m-phenylenebismaleimide, N -Phenylcrotonamide, bis (N-phenyl) fumaramide, divinylsulfone, ethyl acetoacetate, 4-phenyl-3-buten-2-one, N-phenylisovaleroamide, N-methylbenzamide, polyamideimide, bisphenol A di Glycidyl ether, N- (9-fluorenylmethylcarbonyl) -2-methoxyethylamine, 1,4-diph Examples include phenyl-1,4-butanedione.
The anion regenerator may be one in which the above structure is chemically bonded to a polymer as appropriate. Examples of such a polymer include a polyimide having a maleimide structure as a side chain, a maleimide polyimide at both ends (an example of a chemical formula is shown in the following formula), and the like.

The photoresist of the present invention may contain additives such as coupling agents, leveling agents, plasticizers, other film-forming resins, surfactants and stabilizers. The total amount of these additives does not exceed 25% by weight based on the total solid content of the photoresist.
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.

  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-dimethyl. Acetamide, dimethylformamide, dimethyl sulfoxide, acetonitrile, diglyme, phenol, cresol, toluene, methylene chloride, chloroform, tetrahydrofuran, dioxane, acetone and the like.

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 used. 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.
The exposure amount of the irradiated ultraviolet rays is 20 to 300 mJ / cm ² . Since the photoresist composition of the present invention has higher sensitivity than the case where an anion regenerant is included, a photoresist layer can be formed with a small exposure amount. That is, it can be said that the photoresist composition of the present invention can form a photoresist layer with an exposure amount of 100 mJ / cm ² or less.

After the exposure, the photoresist layer is developed with a developer.
The developer used in the present invention comprises a solvent containing tetra-substituted ammonium hydroxide, a low molecular alcohol and water.
This tetra-substituted ammonium hydroxide turns the alcohol component in the developer into an alkoxide.
This tetra-substituted ammonium hydroxide is represented by the following formula.
NR ' ₄ OH
In the formula, R ′ may be the same or different and each represents a hydrocarbon group, preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms.
Preferred tetra-substituted ammonium hydroxides include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide.

  Part of this low molecular alcohol becomes an alkoxide in the developer. Therefore, an alcohol having a molecular weight of 150 or less, particularly an alkyl alcohol having 1 to 8 carbon atoms, preferably 1 to 3 carbon atoms per hydroxyl group, is preferably used. Examples of such low molecular alcohols include methanol, ethanol, 1-propanol, 2-propanol, butanol, octanol, ethylene glycol, 2-methoxyethanol, 2-ethoxyethanol and the like.

  The “solvent containing water” in the developer is a solvent that is compatible with water or a low molecular alcohol and has the ability to dissolve the polymer, the photoacid generator, and the anion regenerant. Examples of such a solvent include NMP, dimethylformamide, dimethyl sulfoxide, tetramethylurea, butyrolactone, diacetoxyethylene glycol, cyclohexanone, polyethylene glycol (number average molecular weight of about 500 or less).

  The composition of a preferred developer is tetra-substituted ammonium hydroxide (such as TMAH) / organic solvent (such as NMP) / water / alcohol (such as methanol), and the weight ratio thereof is preferably 0.2 to 0.6 / It is 0-1.0 / 0.5-2.0 / 2.0-5.0.

Development is performed in consideration of the type of polymer and other components, the type of developer, 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 negative photoresist of the present invention can have a polymer coating 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 composition was applied by spin coating on the surface of a copper foil having a diameter of 10 cm that had not been surface-treated. Subsequently, it dried in the infrared hot air dryer. A test pattern (10-200 μm line and space pattern) for a negative photomask 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. Irradiation was performed with an exposure amount that would produce an image.
The coating film after irradiation was immersed or sonicated in the developer, washed with pure water, dried with an infrared lamp, and then observed for resolution. In some examples, the formed photoresist was observed by SEM (JEOL, scanning electron microscope: JSM-6390LV, acceleration voltage: 1.2 kV). The heat resistance of the obtained photoresist film was evaluated by TGA (Shimadzu Corporation, TGA-50).

Reference example 1
After adding 1.0 g of polyetherimide (PEI) (number average molecular weight 19,000) to 4.7 g of N-methylpyrrolidone (NMP) and dissolving it, diazonaphthoquinone photosensitizer PC-5 (R) as a photoacid generator 0.2 g (Toyo Gosei Co., Ltd., 1,2-naphthoquinone-2-diazide-5-sulfonic acid-p-cresol ester) was added and stirred for about 1 hour at room temperature with a stirrer to prepare a photoresist formulation. This solution was applied onto a 35 μm electrolytic copper foil (shine surface) by spin coating (800 rpm / 10 sec + 1300 rpm / 30 sec), prebaked with a far-infrared hot air circulating dryer (90 ° C./10 min), and then the membrane A photosensitive PEI coating with a thickness of about 10 μm was obtained.
This was irradiated with light in the i-line to g-line band through a PET photomask by an ultraviolet exposure machine (Oak). The exposure measured with an illuminometer for the i-line band was 100 mJ / cm ² .
After exposure, develop at 50 ° C under ultrasonic treatment using 6g of developer consisting of tetramethylammonium hydroxide (TMAH) / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio). And washed with 100 g of ion exchanged water for 1 minute. As a result, a negative image was obtained. The development time at this time was 3 minutes 58 seconds. The resolution was 20 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

Reference example 2
After dissolving 1.0 g of PEI in 4.7 g of NMP, 0.3 g of photosensitizer PC-5 (R) was added, and the mixture was stirred with a stirrer at room temperature for about 1 hour to prepare a photoresist composition. Pre-baking and exposure were performed in the same manner as in Reference Example 1 .
The exposed PEI coating is developed at 50 ° C under ultrasonic treatment using 6g of developer solution consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio). Then, it was washed with 100 g of ion exchange water for 1 minute. As a result, a negative image was obtained. The development time at this time was 2 minutes. The resolution was 20 μm with a line and space pattern. The SEM photograph of this photoresist is shown in Fig. 2.

Reference example 3
After adding PEI 1.0 g to NMP 4.7 g and dissolving, 0.15 g of the photosensitizer PC-5 (R) was added and stirred with a stirrer at room temperature for about 1 hour to prepare a photoresist formulation. Pre-baking and exposure were performed in the same manner as in Reference Example 1 .
The exposed PEI coating is developed at 50 ° C under ultrasonic treatment using 6g of developer solution consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio). Then, it was washed with 100 g of ion exchange water for 1 minute. As a result, a negative image was obtained. The development time at this time was 3 minutes 58 seconds. The resolution was 20 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

Example 1
The photosensitive PEI coating film obtained by the same operation as in Reference Example 1 was irradiated with light in the i-line to g-line band through a PET photomask using an ultraviolet exposure machine. The exposure measured with an illuminometer for the i-line band was 25 mJ / cm ² .
After exposure, use 6g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 4 minutes and 38 seconds. The resolution was 20 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

Example 2
The photosensitive PEI coating film obtained by the same operation as in Reference Example 1 was irradiated with light in the i-line to g-line band through a PET photomask using an ultraviolet exposure machine. The exposure measured with an illuminometer for the i-line band was 50 mJ / cm ² .
After exposure, use 6g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 4 minutes and 28 seconds. The resolution was 20 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

Reference example 4
The photosensitive PEI coating film obtained by the same operation as in Reference Example 1 was irradiated with light in the i-line to g-line band through a PET photomask using an ultraviolet exposure machine. The exposure measured with an illuminometer for the i-line band was 150 mJ / cm ² .
After exposure, use 6g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 4 minutes 02 seconds. The resolution was 20 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

Reference Example 5
The photosensitive PEI coating film obtained by the same operation as in Reference Example 1 was irradiated with light in the i-line to g-line band through a PET photomask using an ultraviolet exposure machine. The exposure measured with an illuminometer for the i-line band was 200 mJ / cm ² .
After exposure, use 6g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 4 minutes 07 seconds. The resolution was 20 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

Reference Example 6
(Polym. Chem., 39, 3451 (2001)), a block polyimide of the following formula (number average molecular weight 40,000) was synthesized.
Using this block polyimide instead of PEI, the same operation as in Reference Example 1 was performed to prepare a photoresist composition. Using this photoresist composition, the same operation as in Reference Example 1 was performed to obtain a photosensitive coating film. After exposure, use 6g of developer consisting of TMAH / NMP / ion-exchanged water / methanol = 0.4 / 1.0 / 1.0 / 3.6 (weight ratio), develop at 50 ° C under ultrasonic treatment, and use 100g of ion-exchanged water. Washed for 1 minute. As a result, a negative image was obtained. The development time at this time was 2 minutes and 27 seconds. The resolution was 20 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

Reference Example 7
The same exposure as in Reference Example 1 was performed on a photosensitive PEI coating film obtained by the same operation as in Reference Example 1 through a PET photomask. After exposure, use 5.6 g of developer consisting of TMAH / ion-exchanged water / ethanol = 0.5 / 1.5 / 3.6 (weight ratio), develop at 50 ° C. under ultrasonic treatment, and wash with 100 g of ion-exchanged water for 1 minute. did. As a result, a negative image was obtained. The development time at this time was 2 minutes and 13 seconds. The resolution was 20 μm with a line and space pattern. An SEM photograph of this photoresist is shown in FIG.

Reference Example 8
After adding and dissolving 1.0 g of polyetherimide (PEI) (number average molecular weight 21,000) to 4.7 g of N-methylpyrrolidone (NMP), diazonaphthoquinone photosensitizer PC-5 (R) as a photoacid generator (Toyo Gosei Co., Ltd., 1,2-naphthoquinone-2-diazide-5-sulfonic acid-p-cresol ester) 0.2g and PMI (N-phenylmaleimide) 0.2g were added and stirred with a stirrer at room temperature for about 1 hour. A photoresist formulation was prepared. It is coated on a glass plate by spin coating (800rpm / 10sec + 1400rpm / 30sec), pre-baked with a far-infrared hot air circulation dryer (90 ° C / 10min), and a photosensitive PEI coating with a film thickness of about 10μm Got.
This was irradiated with light in the i-line to g-line band by an ultraviolet exposure machine (Oak). The exposure measured with an illuminometer for the i-line band was 100 mJ / cm ² . This film was peeled off from the glass plate and then packed into a platinum cell, and evaluated by TGA. First, it was heated in air at 200 ° C. for 2 hours, once cooled, and then heated in air to 800 ° C. at a temperature rising rate of 10 ° C./min. The obtained results are shown in FIG. The 5% weight reduction temperature of the film with PMI and PC-5 (R) added to PEI at 20wt% is 362 ° C, whereas the film with 20% PC-5 (R) added at 5% weight reduction. The temperature was 378 ° C., and improvement in heat resistance was confirmed.

Claims (4)

A photoresist layer containing a condensed polymer containing a carbonyl group (C═O) bonded to a hetero atom in the main chain and a photoacid generator on the substrate and not containing an anion regenerant is provided and masked with a desired pattern. A step of irradiating the pattern surface with ultraviolet light at an exposure amount of less than 100 mJ / cm ² , and a developing step of treating the photoresist layer with a developer, wherein the developer comprises tetra-substituted ammonium hydroxide, a low molecular alcohol, and Ri consists solvent containing water, the anion regenerant following formula
(In the formula, X represents a substituent represented by the following formula,
In the formula, Y represents —NR ¹ ₂ , —OR ¹ (excluding —OH), —CR ¹ ₃ or —SR ¹ (excluding —SH), and R ¹ is independently selected. And represents a hydrogen atom, an aliphatic group or an aromatic group. ), A compound represented by the following formula
R ² -CONHR ¹
Or
R ² —COCH (R ¹ ) ₂
(Wherein R ² independently represents an aliphatic group or an aromatic group, and R ¹ is defined in the same manner as described above),
(In the formula, at least one of R ³ represents an aliphatic group or an aromatic group, the other represents a hydrogen atom, and Z represents an oxygen atom (—O—) or a sulfur atom (—S—).) Or a compound represented by the following formula
_{^{CH (R 4) 2 C (}} R 1) 2 OCO-N (R 1) 2
(Wherein at least one of R ⁴ represents an electron withdrawing group, and the other represents a hydrogen atom, an aliphatic group or an aromatic group. R ¹ is defined in the same manner as described above). A reactive development image forming method. The method according to claim 1, wherein an exposure amount of the irradiated ultraviolet rays is 20 to 50 mJ / cm ² . The method according to claim 1 or 2, wherein the photoacid generator is 1,2-naphthoquinone-2-diazide-5-sulfonic acid-p-cresol ester. The composition of the developer has a tetra-substituted ammonium hydroxide / organic solvent / water / low molecular alcohol (weight ratio) of 0.2 to 0.6 / 0 to 1.0 / 0.5 to 2.0 / 2. It is 0-5.0, The method as described in any one of Claims 1-3 .