JPH07319163A - Positive type resist material - Google Patents

Abstract

PURPOSE:To obtain a resist material for exposure with high energy beams having high sensitivity, high resolution and superior applicability to a process. CONSTITUTION:This resist material sensitive to high energy beams and developable with an aq. alkali soln. contains a resin obtd. by substituting t- butoxycarbonylmethyloxy groups for part of the hydroxyl groups of polyhydroxystyrene, a dissolution inhibitor having two or more t-butyl groups in one molecule, an onium salt represented by the formula (R)nAM [where R is an arom. group or a substd. arom. group, plural R's may be different from each other, A is sulfonium or iodonium, M is p-toluenesulfonate or trifluoromethanesulfonate and (n) is 2 or 3] and a nitrogen-contg. compd. The ratio of the velocity of dissolution of an exposed part to that of an unexposed part can be increased and a high resolution pattern can be formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to deep ultraviolet rays, electron beams and X-rays.
The present invention relates to a positive resist material having high sensitivity to high energy rays such as rays and capable of forming a pattern by developing with an alkaline aqueous solution and suitable for a fine processing technique.

[0002]

2. Description of the Related Art As LSIs become more highly integrated and operate at higher speeds, finer pattern rules are required. In photoexposure, which is currently used as a general-purpose technology, an essential factor is the wavelength of the light source. The limit of resolution is approaching. g line (43
6 nm) or i-line (365 nm) as a light source, the pattern rule of about 0.5 μm is the limit, and the integration degree of the LSI manufactured using this is 16M.
Up to bit DRAM. However, the trial manufacture of LSI has already reached this stage, and the development of further miniaturization technology is urgently needed. Against this background, far-ultraviolet lithography is promising as a next-generation microfabrication technology. Deep UV lithography is 0.3-0.4
Processing of μm is also possible, and when a resist having a small light absorption is used, it is possible to form a pattern having a side wall that is nearly vertical to the substrate. Further, since the patterns can be transferred at one time, it is advantageous in terms of throughput over electron beam lithography. In recent years, a high-intensity KrF excimer laser is used as a light source for far-ultraviolet rays, and a resist material having low light absorption and high sensitivity is required for use as a mass production technique. Recently developed chemical amplification using acid as a catalyst
n) The resist material (eg, Liu et al., Journal of Vacuum Science and Technology (J. Vac. Sci. Technol.), Volume B6, page 379 (1988)) is a conventional high-sensitivity resist. It has the same or higher sensitivity, high resolution, and high dry etching resistance. Therefore, it is a particularly promising resist material for deep ultraviolet lithography. Shipley is a negative resist.
Consisting of novolac resin, melamine compound and acid generator 3
We have already commercialized the component chemical amplification resist (product name SAL601ER7). However, no chemically amplified positive resist has been commercialized yet. Negative resist can be used for wiring and gate formation in the LSI manufacturing process.
In the formation of contact holes, fine processing is difficult because a fog is likely to occur when a negative resist is used, and a positive resist is far more suitable.

Therefore, there is a strong demand for high-performance positive resists. Conventionally, ItO et al. Have calculated that the OH group of polyhydroxystyrene is t-butoxycarbonyl group (t
We are developing positive type chemically amplified resist by adding onium salt to PBOCST resin protected with Boc group). However, the onium salt used contains antimony as a metal component [Reference: Polymers in Electronics, ACS Symposium Series (Polyme
rs in Electronics, ACS symposium Series), No. 242
(American Chemical Society, Washington DC. 1984),
Page 11]. To avoid contamination of the substrate, metal components in the resist material are generally disliked. Therefore, PBOCST resist is not preferable in terms of process. Ueno et al. Have announced a deep UV positive resist containing poly (p-styreneoxytetrahydropyranyl) as the main component and an acid generator added (Reference: 36th Joint Lecture Meeting of the Japan Society of Applied Physics, 1989). 1p-k-7). However, according to the study by the present inventors, this material system was easy to undergo positive-negative inversion with respect to far ultraviolet rays, electron beams and X-rays. In the above-described two-component positive resist comprising a resin in which an OH group is protected by a protecting group and an acid generator, many protecting groups must be decomposed in order to be dissolved in a developing solution. . At that time, there is a high possibility of causing a change in film thickness, stress in the film, generation of bubbles, and the like. As a chemically sensitized positive resist, a three-component system having a more differentiated function, that is, a material system including an alkali-soluble resin, a dissolution inhibitor, and an acid generator is more preferable than the amount of the dissolution inhibitor that the acid should decompose. Since a small amount is required, it is possible to further reduce the change in film thickness and the generation of bubbles as described above, and it is presumed to be more useful for precise fine processing.

As a three-component positive resist, Hoechst Co. added a novolak resin with an acetal compound as a dissolution inhibitor and further added an acid generator-R.
AY / PF- has been developed for X-ray lithography.
In a system in which hydrolysis is performed in this chemical amplification process, water is required for the hydrolysis reaction, and therefore it is necessary that the resist material contains water. In general, an organic solvent that is immiscible with water, such as ethoxyethyl acetate, is often used as the coating solvent for the resist material, and the resist resin itself is often a material that is not easily compatible with water. It is not preferable to mix a predetermined amount of water with such a material system, and even if it is possible to mix it, the components to be controlled increase, so that the system becomes more complicated and is not preferable. .
On the other hand, in the decomposition reaction of the tBoc group, the reaction proceeds with the two components of the tBoc group and the acid which is the catalyst, and water is not required as the third component, so the reaction is simple and convenient for use in chemical amplification. Is. Many of the compounds converted to tBoc have the effect of inhibiting the solubility of novolak resin,
It is known that groups are useful for developing their ability to inhibit lysis. Schlegel et al., A novolak resin, a dissolution inhibitor obtained by converting bisphenol A into tBoc,
A three-component positive resist consisting of pyrogallol methanesulfonate has been announced (Spring 1990, 3rd
The 7th Joint Lecture Meeting of The Japan Society of Applied Physics 28p-ZE-
4). Onishi et al. Have developed a resist using a compound in which a part of the hydroxyl groups of polyhydroxystyrene is replaced with a t-butoxycarbonylmethyloxy group as a dissolution inhibitor [J.Photopolym.Sci.Technol (J.Photopolym.Sci.Technol .), 5th
Vol. 47 (1992)]. This material has an advantage that the dissolution rate ratio between the exposed portion and the unexposed portion can be increased, but the compatibility with the base polymer becomes a problem as the added amount increases. Schwalm et al. Have developed bis (pt-butoxycarbonyloxyphenyl) iodonium hexafluoroantimonate as a material combining a dissolution inhibitor and an acid generator [Polymer for Microelectronics (Polymer for Microelectroni
cs) (Tokyo, 1989), Session A38]. This is mixed with a novolac resin to form a deep UV positive resist. However, this material system is not practically preferable because it contains a metal and the novolac resin has a large light absorption.

Further, the conventional chemically amplified positive type resist has a drawback that the pattern tends to be overhanged when it is formed by deep ultraviolet rays, electron beams or X-rays. It is considered that this is because the solubility of the resist surface is lowered [Reference; K. G. Thion (KG Chiong)
Et al., Journal of Vacuum Science and Technology, Volume B7, (6), p. 1771 (1
989), S. A. Macdonald
Et al, Proceeding of SPII (SP
IE)]. The overhang shape makes pattern size control difficult, and impairs dimensional controllability even during substrate processing using dry etching. Also, since the lower part of the pattern is thin, it is easy to cause the pattern to collapse. In addition, for chemically amplified resists, if the exposure time from exposure to PEB becomes longer,
There is a problem that the resist characteristics change, which is a major bottleneck for practical use. This problem is called time delay.

[0006]

As described above,
Many chemically amplified positive resists based on novolac resin or polyhydroxystyrene, which have sensitivity to deep ultraviolet rays, electron beams and X-rays, have been published, but all of them have problems. At present, it is still difficult to put it to practical use. An object of the present invention is to provide a positive resist material for high energy beam exposure, which is superior to the prior art in high sensitivity, high resolution and process applicability.

[0007]

The present invention will be described in brief. The present invention relates to a positive resist material, in which a part of hydroxyl groups of polyhydroxystyrene is substituted with a t-butoxycarbonylmethyloxy group. 2 in one molecule
A dissolution inhibitor containing at least one t-butyl group, and a general formula (Formula 1): (R) nAM (wherein R may be the same or different and represents an aromatic group or a substituted aromatic group, and A is sulfonium). Or iodonium, M represents a p-toluenesulfonate group or a trifluoromethanesulfonate group, and n represents 2 or 3), and is a high energy ray-sensitive compound capable of developing with an alkaline aqueous solution containing three components of an onium salt represented by The positive resist is characterized by further containing a nitrogen-containing compound.

In the chemically amplified positive type resist, the major problems at present are that patterns tend to overhang and time delay. The pattern becomes overhanging because the poorly soluble layer formed on the surface is easily formed. One of the main causes is that the nitrogen-containing compound in the air diffuses from the resist surface to form nitrogen in the resist film thickness direction. This is because the distribution of the contained compounds is formed. The presence of the nitrogen-containing compound deactivates the acid generated by exposure, so that the dissolution inhibitor is less likely to decompose on the surface. Therefore, the insolubilized layer is formed on the surface. Also,
The cause of the time delay problem is also presumed to be largely related to nitrogen-containing compounds in the air. The acid on the resist surface generated by the exposure reacts with the nitrogen-containing compound in the air and is deactivated. The longer the standing time to PEB is, the more the amount of deactivating acid increases, and the sensitivity further decreases. This becomes a problem of time delay.

In the present invention, it has been discovered that when a nitrogen-containing compound is added to a chemically amplified positive type resist, two problems of pattern overhang and time delay can be solved at once. Since the nitrogen-containing compound already exists in the resist, it is presumed that even if the nitrogen-containing compound in the air diffuses into the resist film, its distribution cannot be formed in the resist film thickness direction. Therefore, the hardly soluble layer is not formed only on the resist surface.

Various amine compounds as nitrogen-containing compounds,
As a result of examining amide compounds, compounds having a boiling point of 150 ° C. or higher were effective. This is 1 after applying the resist
It is presumed that the compound having a boiling point of less than 150 ° C. evaporates during the prebaking at 00 ° C., so that it almost does not exist in the resist film and the effect is not recognized.

The nitrogen-containing compounds that can be used include the following compounds. Aniline, N-methylaniline,
N, N-dimethylaniline, p-toluidine, o-toluidine, m-toluidine, 2,4-lutidine, quinoline, isoquinoline, formamide, N-methylformamide, N, N-dimethylformamide, acetamide,
N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone, imidazole, α-picoline, β-picoline, γ-picoline, o
-Aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-quinolinecarboxylic acid, 2-amino-4-nitrophenol, 2- (p-chlorophenyl) -4,6
-Triazine compounds such as trichloromethyl-s-triazine.

A major drawback of adding a nitrogen-containing compound is that the sensitivity of the resist is lowered, but two or more t-butyl groups in one molecule using a p-toluenesulfonate-based or trifluoromethanesulfonate-based onium salt are used. By using a dissolution inhibitor containing ## STR4 ## and suppressing the addition amount of the nitrogen-containing compound to 4% by weight or less, the decrease in sensitivity can be suppressed. When it is important to increase the sensitivity of the resist, the amount of the nitrogen-containing compound added is preferably 1 wt% or less.

[0013] The following formulas as onium salts (Formula 2), a compound represented by (Formula 3): (Formula _{2) (C 6 H 5)} 2 I + - O 3 SCF 3, ( Formula 3) (C _{6 ^{H 5) 3 S + - O}} 3 SCF 3 are known. However, the formula (Chemical Formula 2) has low solubility in a solvent suitable for coating the resist such as ethyl cellosolve acetate, ethyl lactate, and 1-methoxy-2-propanol, so that an appropriate amount cannot be mixed in the resist. . Although the solubility of the formula (Formula 3) is relatively good, when a three-component resist is prepared using this, the film thickness is reduced by the exposure amount of 1 to ⁴ μC / cm ² regardless of the type of the dissolution inhibitor, but the exposure The part turned negative before it completely melted, and did not become a positive type. Regarding such negative reversal, Schlegel et al. Have also published (reference; the above-mentioned), and the fact that trifluoromethanesulfonate-based onium salts cannot be used for a three-component positive resist containing a tBoc-based dissolution inhibitor, It was common sense until.

Conventionally, the most practical onium salt of an acid generator for a chemically amplified resist is said to be an aromatic sulfonium salt (reference: Okawa, et al., 37th Joint Lecture Meeting on Applied Physics, 1990). 28p-PD-2). However, as described above, the sulfonium salt of trifluoromethanesulfonic acid is not put to practical use as an acid generator for a three-component positive resist having a tBoc compound as a dissolution inhibitor. The present inventors have found that the organic onium salt, which has high solubility in a resist coating solvent, is used in a positive resist material composed of a polyhydroxystyrene resin, a tBoc dissolution inhibitor and an acid generator. An intensive study was conducted on an acid generator exhibiting good positive characteristics.

As a result, the following onium salts can be used. Bis (pt-butylphenyl) iodonium trifluoromethanesulfonate, diphenyl (p
-Methoxyphenyl) sulfonium trifluoromethanesulfonate, phenyl (p-fluorophenyl) iodonium trifluoromethanesulfonate, phenyl (p-methoxyphenyl) iodonium trifluoromethanesulfonate, diphenyl (p-fluorophenyl) sulfonium trifluoromethanesulfonate, diphenyl (p-hydroxy) (Phenyl) sulfonium trifluoromethanesulfonate, phenyl (p-thiophenoxyphenyl) iodonium trifluoromethanesulfonate, and compounds in which the trifluoromethanesulfonate group portion of the above compound is replaced with a p-toluenesulfonate group.

The onium salt content in the resist of the present invention is preferably 0.5 to 15 wt%. If it is less than 0.5%, positive resist characteristics are exhibited, but the sensitivity is low. As the content of the acid generator increased, the resist sensitivity tended to increase and the contrast (γ) improved. Even if it is more than 15%, it shows a positive resist property, but it cannot be expected to further increase the sensitivity due to the increase of the content, onium salt is an expensive reagent, and the increase of low molecular components in the resist increases the resist film. It is preferable that the content of the onium salt is 15% or less by decreasing the mechanical strength of the above.

The resist material according to the present invention, which uses an onium salt, essentially contains two or more t-butyl groups in one molecule as a dissolution inhibitor. The content of the dissolution inhibitor is preferably 7-40 wt%. If it is less than 7%, the dissolution inhibiting effect is small, and if it exceeds 40%, the mechanical strength and heat resistance of the resist are lowered. The tBoc compound as a dissolution inhibitor for a positive resist, which has been conventionally announced, is almost the only material obtained by converting the OH group of bisphenol A to tBoc. However, as a result of diligent studies, the present inventors have found that phloglucin, tetrahydroxybenzophenone, phenolphthalein, cresolphthalein, thymolphthalein, and the like, which are tBoc-ized, are also useful as dissolution inhibitors. It was also found that the t-butyl ester compound of carboxylic acid is also an effective dissolution inhibitor. Since the dissolution inhibitor that produces carboxylic acid after this decomposition can increase the dissolution rate ratio between the exposed area and the unexposed area, it exhibited excellent characteristics in terms of resolution, focus margin and time delay. Alkali-soluble novolac resin or polyhydroxystyrene can be used as the base resin, but when novolac resin is used, there is a problem that absorption by KrF laser light is large.
It is preferable to use polyhydroxystyrene, which has low absorption, for the resist for KrF. However, polyhydroxystyrene may have a small dissolution inhibiting effect when a dissolution inhibitor is added. This is because polyhydroxystyrene has a high solubility, and in order to control the solubility, one in which a part of the hydroxyl groups is substituted with a tBoc group has been used.

However, when a part of the hydroxyl groups was replaced with a t-butoxycarbonylmethyloxy group, a dissolution inhibiting effect of one digit or more was obtained as compared with the case of the tBoc group. Further, it has been found that the carboxylic acid having excellent alkali solubility is generated in the exposed area due to the resist reaction, so that the dissolution rate ratio between the exposed area and the unexposed area can be increased. It is known that the higher the dissolution rate of the exposed area and the unexposed area, the better the resolution. Therefore, some of the hydroxyl groups of polyhydroxystyrene are t-
The base resin substituted with the butoxycarbonylmethyloxy group was superior in resolution to the base resin substituted with the tBoc group. Further, the alkali solubility of the exposed area was improved, resulting in high sensitivity. The substitution rate with the t-butoxycarbonylmethyloxy group is preferably 10 to 50 mol%. If it is higher than 50 mol%, the solubility in an alkaline aqueous solution is lowered, so that the sensitivity is extremely lowered in a commonly used developer, and if it is lower than 10 mol%, the dissolution inhibiting effect is small.

The weight average molecular weight of polyhydroxystyrene is preferably 10,000 or more from the viewpoint of the heat resistance of the formed resist pattern, but the one obtained by radical polymerization has a large dispersity and therefore is dissolved in an alkaline aqueous solution. Includes difficult and high molecular weight, which causes tailing after pattern formation. Therefore, it is advantageous to form a pattern with high accuracy when the molecular weight is large and the dispersity is as small as possible. In the present invention, when polyhydroxystyrene obtained by living polymerization (molecular weight: 14,000, dispersity: 1.1) was used, a 0.2 μm line & space pattern could be formed accurately without trailing. Moreover, regarding heat resistance, pattern deformation was not observed even after baking at 150 ° C. for 10 minutes. Molecular weight obtained by radical polymerization 1.2
In all of them, the dispersity was 3.0, and the tail of the pattern was seen in the 0.2 μm line and space pattern. However, it is still possible to form fine patterns.
When the nitrogen-containing compound was not added, pattern tailing was observed even in the 0.5 μm line & space pattern, so addition of the nitrogen-containing compound was effective for improving resolution. Although the reason is not clear yet, the nitrogen-containing compounds most excellent in the above resist composition from the viewpoint of sensitivity and resolution were pyrrolidone, N-methylpyrrolidone, and various aminobenzoic acids.

Pattern formation using the resist of the present invention can be performed as follows. The resist solution is spin-coated on the substrate and prebaked. Irradiate with high energy rays. At this time, the acid generator decomposes to generate an acid. By performing PEB, tBoc can be catalyzed by acid.
The group decomposes and the dissolution inhibiting effect disappears. A positive type pattern is obtained by developing with an alkaline aqueous solution and rinsing with water. The tBoc conversion of the OH group is a method of protecting a functional group that is often used in peptide synthesis, and can be easily performed by reacting with tert-butyl dicarbonate in a pyridine solution.

The synthetic examples of the raw materials used in the present invention are shown below, but the invention is not limited thereto. Synthesis Example 1 t-Butoxycarbonylmethyloxylation of polyhydroxystyrene 5 g of polyhydroxystyrene is dissolved in 40 ml of pyridine, and 2.5 g of t-butyl bromoacetate is added with stirring at 45 ° C. The reaction is carried out for 5 hours in N ₂ stream. The reaction solution is added dropwise to 1 liter of water containing 20 g of concentrated hydrochloric acid to obtain a white precipitate. After filtration, 50 ml of acetone
The precipitate was dissolved in and was added dropwise to 1 liter of water. After filtering the precipitate, it was vacuum dried at 40 ° C. or lower. As a result of obtaining the introduction rate of the t-butoxycarbonylmethyloxy group by using the peak of the OH group at 8 ppm in 1 H-NMR, 20.
It was 6%.

[0022]

The present invention will be described in the following examples, but the present invention is not limited to these examples.

Example 1 Resin in which some of the hydroxyl groups of polyhydroxystyrene were t-butoxycarbonylmethylated (Synthesis Example 1) 80.6 parts by weight 2,2-bis [p- (t-butoxycarbonyloxy) phenyl] propane 14 parts by weight Bis (pt-butylphenyl) iodonium trifluoromethanesulfonate 5 parts by weight N-methylpyrrolidone 0.4 parts by weight Ziglyme (solvent) 400 parts by weight A resist solution consisting of 400 parts by weight was spin-coated on a silicon substrate at 2000 rpm, and then applied on a hot plate. Prebaked at 85 ° C. for 1 minute. The film thickness was 0.7 μm. Accelerating voltage 3
After drawing with an electron beam of 0 kV, PEB was performed at 85 ° C. for 3 minutes. Develop with a 2.4% aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute, and then develop with water.
Rinse for 0 seconds. It shows positive characteristics and D ₀ sensitivity is 7
It was μC / cm ² . The D ₀ sensitivity was 27 mJ / cm ² when evaluated with KrF excimer laser light (wavelength 248 nm) which was far ultraviolet rays instead of the electron beam. PEB at 85 ° C
Electron beam sensitivity is 5.5 μC / cm ²
Met. 0.3 μm for KrF excimer laser exposure
The line & space pattern and the hole pattern were resolved, and the pattern with vertical side walls was formed. Further, 0.2 μm was resolved by electron beam drawing. No change in sensitivity or resolution was observed even if left in the atmosphere for 3 hours or more before PEB.

Examples 2 to 16 In place of the dissolution inhibitor 2,2-bis [pt-butoxycarbonyloxy) phenyl] propane of Example 1, Table 1
The resist evaluation was carried out in the same manner as in Example 1 using the dissolution inhibitor of. Table 1 shows the sensitivity of KrF excimer laser exposure. With each material, the KrF excimer laser exposure resolved the 0.3 μm line and space pattern and the hole pattern, and formed a pattern having vertical sidewalls. Further, 0.2 μm was resolved by electron beam drawing. Before PEB 3
No change in sensitivity or resolution was observed even if left in the air for more than an hour.

[0025]

[Table 1]

The structural formulas of the dissolution inhibitors in Table 1 are shown below.

[0027]

[Chemical 4]

[0028]

[Chemical 5]

[0029]

[Chemical 6]

[0030]

[Chemical 7]

[0031]

[Chemical 8]

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

[0035]

[Chemical 12]

[0036]

[Chemical 13]

[0037]

[Chemical 14]

[0038]

[Chemical 15]

[0039]

[Chemical 16]

[0040]

[Chemical 17]

[0041]

[Chemical 18]

[0042]

[Chemical 19]

Examples 17 to 28 Onium salt bis (pt-butylphenyl) of Example 1
Iodonium trifle

[0044]

[Table 2]

Ts: p-toluenesulfonate, O ₃ S
CF _3: trifluoromethanesulfonate

Examples 29 to 59 In place of the nitrogen-containing compound N-methylopyrrolidone of Example 1, the nitrogen-containing compounds of Tables 3 and 4 were used to evaluate the resist properties in the same manner as in Example 1. Tables 3 and 4 show the sensitivities of KrF excimer laser exposure. With each material, the KrF excimer laser exposure resolved the 0.3 μm line and space pattern and the hole pattern, and formed a pattern having vertical sidewalls. Further, 0.2 μm was resolved by electron beam drawing. No change in sensitivity or resolution was observed even if left in the atmosphere for 3 hours or more before PEB.

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

The positive resist obtained by the present invention is sensitive to high energy rays and is excellent in sensitivity, resolution and plasma etching resistance. Moreover, the heat resistance of the resist pattern is excellent. In addition, the pattern is unlikely to be overhung, and the dimensional controllability is excellent. Since it contains a nitrogen-containing compound, it is less susceptible to the effects of nitrogen-containing compounds in the atmosphere and has the characteristic that the problem of time delay can be ignored. The base resin uses polyhydroxystyrene in which some of the hydroxyl groups have been replaced with t-butoxycarbonylmethyloxy groups, so the dissolution rate ratio between the exposed and unexposed areas can be increased, and high resolution is achieved. A pattern can be formed. From these, it is particularly useful for fine processing with electron beams, X-rays, and deep ultraviolet rays. In particular, since the absorption at the exposure wavelength of the KrF excimer laser is small, there is a feature that a fine pattern which is perpendicular to the substrate can be easily formed.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Yoshio Kawai, 1-1-6 Uchisaiwai-cho, Chiyoda-ku, Tokyo Nihon Telegraph and Telephone Corporation (72) Ito Matsuda 1-1-6 Uchisai-cho, Chiyoda-ku, Tokyo Nihon Telegraph and Telephone Corp. (72) Inventor Toshinori Ishihara 2-6-1, Otemachi, Chiyoda-ku, Tokyo Shin-Etsu Chemical Co., Ltd.

Claims (2)

[Claims] 1. A resin in which a part of hydroxyl groups of polyhydroxystyrene is substituted with a t-butoxycarbonylmethyloxy group, a dissolution inhibitor containing two or more t-butyl groups in one molecule, and a general formula: 1): (R) nAM (wherein R may be the same or different and represents an aromatic group or a substituted aromatic group, and A represents sulfonium or iodonium).
M represents a p-toluenesulfonate group or a trifluoromethanesulfonate group. n is 2 or 3), a high energy ray-sensitive positive resist developable with an alkaline aqueous solution, which contains three components of an onium salt, further contains a nitrogen-containing compound. material. 2. The nitrogen-containing compound is pyrrolidone, N-
The positive type according to claim 1, which is one or more nitrogen-containing compounds selected from methylpyrrolidone, orthoaminobenzoic acid, metaaminobenzoic acid, paraaminobenzoic acid, orthophenylenediamine, metaphenylenediamine, and paraphenylenediamine. Resist material.