JPH08176051A - Spirobiindane derivative and resist material containing the same - Google Patents

Abstract

PURPOSE: To obtain new compound useful as a dissolution inhibitor of a photoresist, providing a positive type resist material for high energy rays, having excellent sensitivity and resolving power. CONSTITUTION: This compound is shown by formula I (R<1> is a protective group readily eliminable under acidic conditions; R<2> is H or an alkyl; (m) is 1 or 2; (n) is 1-3) such as 6,6'-bis(tert-butoxycarbonyloxy)-2,2',3,3'-tetrahydro-3,3,3',3'- tetramethyl-1,1'-spiro[1H-indane]. The compound is obtained by reacting a spirobiindanol derivative of formula II with a compound such as di-tert-butyl dicarbonate or dihydro-2H-pyrane to introduce an R1 -protecting group. Preferably 2-5mol of a compound to introduce the R1 -protecting group is used based on 1mol of the compound of formula II.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel spirobiindane derivative and a resist material containing the derivative, and further, a spirobiindane derivative useful as a dissolution inhibitor for photoresist and a positive processing suitable for fine processing using the derivative. Type resist material.

[0002]

2. Description of the Related Art Conventionally, with the high integration and high density of LSIs (high-density integrated circuits), miniaturization of pattern rules has been demanded, but light emitted from a light source used in a normal optical exposure technique. Has a long wavelength and is not a single wavelength, so there is a limit to the miniaturization of the pattern rule. Therefore, g-line (wavelength 436 nm) or i emitted from the ultra-high pressure mercury lamp
The use of a line (wavelength 365 nm) as a light source has also been considered. However, even in these cases, the resolution of the pattern rule is limited to about 0.5 μm, and the LSI that can be manufactured by this is only the integration degree of about 16 Mbit DRAM. Therefore, in recent years, far-ultraviolet lithography, which has a shorter wavelength than g-line and i-line, is regarded as promising. It is also possible to form a pattern rule of 0.1 to 0.3 μm by using deep-UV lithography. When a resist material having low light absorption is used, the side wall close to vertical to the substrate is formed. It is possible to form patterns that have. Furthermore, it is also possible to transfer patterns at one time, which is superior to lithography using electron beams in that the pattern formation processing efficiency (throughput) is higher. Further, since it becomes possible to use a KrF excimer laser having a high luminous intensity as a light source for far-ultraviolet rays, a resist material having a particularly small absorbance and a high sensitivity is used from the viewpoint of mass-producing an LSI using various light sources. Is required.

In response to such requirements, a chemically amplified resist material having sensitivity equal to or higher than that of a conventional high-sensitivity resist material, high resolution and high dry etching resistance, and manufactured by using an acid as a catalyst has been developed. (Eg L
iu, et. al., Journal of Vacuum Science and Technology (J. Vac. Sci. Techno.) B
6, 379 (1988)], a chemically amplified negative resist material (trade name SAL601E) consisting of three components, a novolak resin, a melamine compound and an acid generator by Shipley.
R7) has already been commercialized. However, when a negative resist material is used in the LSI manufacturing process, it is easy to form wirings and gate portions, but it is difficult to form contact holes that require fine processing. It was In addition, the chemically-amplified positive resist material that has been conventionally proposed is used as it is for deep ultraviolet rays,
When it is used for pattern formation by electron beam or X-ray, the solubility of the resist surface is lowered, and the pattern after development tends to be overhanged, which makes it difficult to control the pattern size and dry etching is performed. Not only impairs the dimensional controllability during substrate processing due to, but also tends to cause pattern collapse [eg KG Chiong, e
t. al. J. Vac. Sci. Techno. B 7, 1771 (1989
)].

At present, there is a strong demand for the development of a chemically amplified positive resist material which solves the above problems. In response to such a demand, a chemically amplified positive resist material has been proposed in which an onium salt is added to a poly (butoxycarbonyloxystyrene) resin in which a hydroxyl group of a poly (hydroxystyrene) derivative is protected with a tert-butoxycarbonyl group. (For example, Ito, et. Al., Polymers in Electo
ronics, ACS Symposium Series, 242, 11 (1984)].
However, when the above-mentioned onium salt contains antimony as a metal component and a resist material containing the onium salt is used, not only the substrate is contaminated, but also the resist material is aged after irradiation with deep ultraviolet rays or the like. The problem is that the change is extremely large.

Further, a positive type resist material for deep ultraviolet rays, which comprises a poly (p-styreneoxytetrahydropyranyl) resin as a main component and an acid generator added thereto, has been proposed (Ueno et al., 36th session). Japan Society of Applied Physics
1989, 1p-k-7). However, the above-mentioned positive resist material has a drawback that it is easy to reverse from a positive type to a negative type with respect to deep ultraviolet rays, electron beams or X-rays. The above-mentioned two-component positive resist composition comprising a resin having a hydroxyl group protected by a protecting group and an acid generator needs to decompose many protecting groups in order to be dissolved in a developing solution. In the above, there are problems that the film thickness of the resist is changed, and that stress and bubbles are easily generated in the film.

As a chemically amplified positive resist material that overcomes the problems of the above-described two-component positive resist material, a three-component positive resist material comprising an alkali-soluble resin, a dissolution inhibitor and an acid generator is used. Is being developed. As a three-component positive resist material, a resist material containing a novolak resin, an acetal compound as a dissolution inhibitor, and an acid generator (RAY / Hoechst)
Have been developed for X-ray lithography. However, since the resist material undergoes chemical amplification at room temperature, its resist sensitivity greatly depends on the time from X-ray exposure to development. Therefore, since it is necessary to control the time very strictly, it is difficult to stabilize the dimension of the pattern, and the absorption of the KrF excimer laser (wavelength 248 nm) is large, and the laser is used. It is unsuitable for lithographic use.

In general, when chemical amplification is performed, heat treatment is often required after exposure. In this case, although the number of steps is increased as compared with a resist material that is chemically amplified at room temperature, it is not necessary to strictly control the time from exposure to development, so that the resist characteristics are stable.
Further, in the case of a system in which hydrolysis is performed in the process of performing chemical amplification, water for hydrolysis is required, so it is necessary to add water to the resist material. However, as the solvent used when applying the resist material to the substrate, generally, an unnecessary organic solvent such as ethoxyethyl acetate is often used in water, and the resin itself used as the resist material is also compatible with water. Since many of them do not, it is difficult to add water to the resist material, and even if it is added, the control of the water becomes complicated. On the other hand, in the decomposition reaction of the tert-butoxycarbonyloxy group, the reaction proceeds with the two components of the tert-butoxycarbonyloxy group and the acid which is the catalyst, and water is not required. Is preferred.

Further, many of the compounds having a tert-butoxycarbonyloxy group have an effect of inhibiting the solubility of the novolak resin, that is, the tert-butoxycarbonyloxy group has a dissolution inhibiting effect on the novolak resin. It has been known. From such a viewpoint, a three-component positive resist material composed of a novolac resin, a dissolution inhibitor in which a tert-butoxycarbonyl group is introduced into bisphenol A, and pyrogallol methanesulfonate is proposed [Schlegel et al., 1990. Spring, 3rd
The 7th Joint Lecture Meeting of The Japan Society of Applied Physics, 28-p-ZE-4]. However, it is difficult to put this system into practical use because the novolak resin absorbs a large amount of light. Further, a positive type resist material for deep ultraviolet rays has been proposed in which bis (p-tert-butoxycarbonyloxyphenyl) iodonium hexafluoroantimonate, which is a material that also serves as a dissolution inhibitor and an acid generator, is mixed with a novolak resin. [Schwalm
Et al., Polymer for Microelectronics, Tokyo, 1989, Session A 38]. However, since the above positive resist material contains antimony in addition to the large light absorption of the novolac resin, it is difficult to put it into practical use.

By the way, in a three-component chemical amplification type positive resist material comprising a resin, a dissolution inhibitor and an acid generator, the dissolution rate of the resist film in an alkali developing solution is controlled by the dissolution inhibitor. That is, (dissolution rate of the portion irradiated with high energy rays) /
It is known that increasing the (dissolution rate of the non-irradiated portion) [hereinafter referred to as the dissolution rate ratio] has a great influence on the performance as a resist material. That is, when a portion of the resist film when irradiated with high energy rays such as ultraviolet rays is added to the resist material, a substance capable of quickly dissolving in an alkali developing solution (dissolution inhibitor),
The formation efficiency of the resist pattern becomes extremely good. Such a dissolution inhibitor has a great influence on the performance of the photoresist, and as a conventionally known one,
For example, di-tert-butoxycarbonylbisphenol A represented by the following formula (2) (formula 2) and the following formula (3) (formula 2)
Di-tert-butoxycarbonylbisphenol F represented by the following formula, 4-tert-butoxycarbonylbiphenyl represented by the following formula (4) (chemical formula 2), tert-butyl represented by the following formula (5) (chemical formula 2) Examples thereof include cholate and tert-butyl deoxycholate represented by the following formula (6) (formula 2).

[0010]

Embedded image

However, any of the dissolution inhibitors cannot obtain a sufficient dissolution contrast between the exposed portion and the unexposed portion of the resist, so that sufficient resolution and sensitivity cannot be obtained, and the resist changes with time. There was a problem that the shape of the pattern changed. For example, in the case of di-tert-butoxycarbonylbisphenol A and di-tert-butoxycarbonylbisphenol F, they have a large dissolution inhibiting effect on the resin and have a small ultraviolet absorption rate.
Although it has the characteristic of being inexpensive, the dissolution rate ratio is small and the solubility in the resin is low, so the addition amount is limited. In the case of 4-tert-butoxycarbonylbiphenyl, although the dissolution rate ratio is relatively large, the light transmittance to the resist film cannot be controlled because of the large ultraviolet absorption rate. Further, in the case of tert-butyl cholate and tert-butyl deoxycholate, the ultraviolet absorptivity is small, the compatibility is good when used for novolak resins, although it is excellent as a dissolution inhibitor,
When it is used for a poly (hydroxystyrene) derivative, the dissolution inhibiting effect is insufficient, so that the resist film in the non-irradiated part is dissolved in the alkali developing solution, and the raw material is used. Supply is unstable because it is a natural product. Under the circumstances described above, a positive resist material for high energy rays, which is excellent in sensitivity, resolution and stability over time, is currently desired.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive resist material having high sensitivity and high resolution for high energy rays.

[0013]

The present inventors have arrived at the present invention as a result of extensive studies on the above problems. That is, the present invention relates to a spirobiindane derivative represented by the following general formula (1) (chemical formula 3), an alkali-soluble resin,
A high energy sensitive positive resist composition containing a dissolution inhibitor and an acid generator, which is developable in an alkaline aqueous solution, and contains a spirobiindane derivative represented by the general formula (1) as the dissolution inhibitor. Positive resist material.

[0014]

Embedded image (In the formula, R ₁ represents a protecting group that can be easily removed under acidic conditions, R ₂ represents a hydrogen atom, an alkyl group, an alkoxy group, a nitro group or a halogen atom, and m represents 1 or 2, n represents an integer of 1 to 3)

In the spirobiindane derivative represented by the general formula (1), R ₁ represents a protecting group which can be easily removed under acidic conditions. R ₁ is preferably a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tetrahydropyranyl group, a methoxymethyl group, a diphenylmethyl group, a triphenylmethyl group, a trimethylsilyl group,
tert-butyldimethylsilyl group, methyl group, methylthiomethyl group, phenacyl group, cyclopropylmethyl group, allyl group, benzyl group, o-nitrobenzyl group, p-methoxybenzyl group, p-picolyl group, acetyl group, pivaloyl group , A methoxycarbonyl group, a 2,2,2-trichloroethyloxycarbonyl group, an allyloxycarbonyl group or a benzyloxycarbonyl group, and more preferably a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tetrahydropyranyl group. , A methoxymethyl group, a diphenylmethyl group, a triphenylmethyl group, a trimethylsilyl group or a tert-butyldimethylsilyl group.

In the spirobiindane derivative represented by the general formula (1), R ₂ represents a hydrogen atom, an alkyl group, an alkoxy group, a nitro group or a halogen atom. R ₂ is
Preferably, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
It is an alkoxy group having 1 to 20 carbon atoms, a nitro group or a halogen atom, more preferably a hydrogen atom and 1 to 1 carbon atoms.
An alkyl group having 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a chlorine atom, and more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or n.
-Butyl group, isobutyl group, tert-butyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group or chlorine atom. Particularly preferably, R ₂ is a hydrogen atom. Further, in the spirobiindane derivative represented by the general formula (1), m is 1 or 2,
m is preferably 1. Moreover, in the spirobiindane derivative represented by General formula (1), n represents the integer of 1-3, More preferably, n is 1 or 2.

The spirobiindane derivative represented by the general formula (1) of the present invention is a compound having in the spirobiindane skeleton two or more hydroxyl groups substituted with a protecting group which can be easily removed under acidic conditions, and is preferable. Is a spirobiindane derivative represented by the following general formulas (1-a) to (1-d) (Chemical Formula 4) having two hydroxyl groups. More preferably, it is a spirobiindane derivative represented by the general formula (1-b) or the general formula (1-c),
The spirobiindane derivative represented by c) is particularly preferable.

[0018]

[Chemical 4] (In the formula, R ₁ , R ₂ and n are the same as above)

Specific preferred examples of the spirobiindane derivative represented by the general formula (1) include spirobiindane derivatives shown below, but these do not limit the present invention. Exemplified Compound No. 1. 6,6'-bis (tert-butoxycarbonyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3', 3 '
-Tetramethyl-1,1'-spirobi [1H-indane] 1. 6,6'-bis (tert-butoxycarbonyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3',
3 ', 5,5'-hexamethyl-1,1'-spirobi [1H-
Indan] 3. 6,6'-bis (tert-butoxycarbonyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3', 3 '
-Tetramethyl-5,5'-diethyl-1,1'-spirobi [1H-indane] 4. 6,6'-bis (tert-butoxycarbonyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3', 3 '
4. Tetramethyl-7,7'-diisopropyl-1,1'-spirobi [1H-indane] 5. 6,6'-bis (tert-butoxycarbonyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3', 3 '
-Tetramethyl-5,5'-dimethoxy-1,1'-spirobi [1H-indane] 6. 6,6'-bis (tert-butoxycarbonyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3', 3 '
-Tetramethyl-7,7'-diethoxy-1,1'-spirobi [1H-indane] 7. 6,6'-bis (tert-butoxycarbonyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3', 3 '
-Tetramethyl-5,5'-dichloro-1,1'-spirobi [1H-indane] 8. 6,6'-bis (tert-butoxycarbonylmethyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3
9. 3 ', 3'-Tetramethyl-1,1'-spirobi [1H-indane] 9. 6,6'-bis (tert-butoxycarbonylmethyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3
3 ', 3', 4,4'-hexamethyl-1,1'-spirobi [1
H-Indan] 10. 6,6'-bis (tert-butoxycarbonylmethyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3
3 ', 3'-tetramethyl-7,7'-di-n-propyl-
1,1'-spirobi [1H-indane]

11. 6,6'-bis (tert-butoxycarbonylmethyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-4,4'-di-tert
-Butyl-1,1'-spirobi [1H-indane] 12. 6,6'-bis (tert-butoxycarbonylmethyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3
3 ', 3'-Tetramethyl-4,4'-dimethoxy-1,1'-
Spirobi [1H-Indan] 13. 6,6'-bis (tert-butoxycarbonylmethyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3
3 ', 3'-tetramethyl-5,5'-diethoxy-1,1'-
Spirobi [1H-Indan] 14. 6,6'-bis (tert-butoxycarbonylmethyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3
3 ', 3'-tetramethyl-5,5'-di-n-propoxy-
1,1′-spirobi [1H-indane] 15. 6,6'-bis (tert-butoxycarbonylmethyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3
16. 3 ', 3'-Tetramethyl-4,4'-dichloro-1,1'-spirobi [1H-indane] 16. 6,6'-bis (2 "-tetrahydropyranyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3', 3 '
-Tetramethyl-1,1'-spirobi [1H-indane] 17. 6,6'-bis (2 "-tetrahydropyranyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3',
3 ', 5,5'-hexamethyl-1,1'-spirobi [1H-
Indan] 18. 6,6'-bis (2 "-tetrahydropyranyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3',
3 ', 7,7'-hexamethyl-1,1'-spirobi [1H-
Indan] 19. 6,6'-bis (2 "-tetrahydropyranyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3', 3 '
-Tetramethyl-5,5'-diethyl-1,1'-spirobi [1H-indane] 20. 6,6'-bis (2 "-tetrahydropyranyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3', 3 '
-Tetramethyl-7,7'-diisopropyl-1,1'-spirobi [1H-indane]

21. 6,6'-bis (2 "-tetrahydropyranyloxy) -2,2 ', 3,3'-tetrahydro-
3,3,3 ', 3'-Tetramethyl-5,5'-dimethoxy-
1,1′-spirobi [1H-indane] 22. 6,6'-bis (2 "-tetrahydropyranyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3', 3 '
-Tetramethyl-7,7'-di-n-butoxy-1,1'-
Spirobi [1H-indane] 23. 6,6'-bis (2 "-tetrahydropyranyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3', 3 '
-Tetramethyl-4,4'-dichloro-1,1'-spirobi [1H-indane] 24. 6,6'-bis (methoxymethyloxy) -2,
2 ', 3,3'-Tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobi [1H-indane] 25. 6,6'-bis (methoxymethyloxy) -2,
2 ', 3,3'-Tetrahydro-3,3,3', 3 ', 5,5'-
Hexamethyl-1,1'-spirobi [1H-indane] 26. 6,6'-bis (methoxymethyloxy) -2,
2 ', 3,3'-Tetrahydro-3,3,3', 3 ', 7,7'-
Hexamethyl-1,1'-spirobi [1H-indane] 27. 6,6'-bis (methoxymethyloxy) -2,
28. 2 ', 3,3'-Tetrahydro-3,3,3', 3'-tetramethyl-5,5'-di-n-propyl-1,1'-spirobi [1H-indane] 28. 6,6'-bis (methoxymethyloxy) -2,
2 ', 3,3'-Tetrahydro-3,3,3', 3'-tetramethyl-7,7'-di-n-butyl-1,1'-spirobi [1
H-Indan] 29. 6,6'-bis (methoxymethyloxy) -2,
2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-4,4'-dimethoxy-1,1'-spirobi [1H-
Indan]

30. 6,6'-bis (methoxymethyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3',
3'-tetramethyl-5,5'-diisopropoxy-1,1 '
-Spirobi [1H-indane] 31. 6,6'-bis (methoxymethyloxy) -2,
2 ', 3,3'-Tetrahydro-3,3,3', 3'-tetramethyl-4,4'-dichloro-1,1'-spirobi [1H-indane] 32. 6,6'-bis (diphenylmethyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobi [1H-indane] 33. 6,6'-bis (diphenylmethyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3 ', 5
5'-hexamethyl-1,1'-spirobi [1H-indane] 34. 6,6'-bis (diphenylmethyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3 ', 7,
7'-hexamethyl-1,1'-spirobi [1H-indane] 35. 6,6'-bis (diphenylmethyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-5,5'-di-n-propyl-1,1'-spirobi [1H-indane] 36. 6,6'-bis (diphenylmethyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-7,7'-di-n-butyl-1,1'-spirobi [1H-indane] 37. 6,6'-bis (diphenylmethyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-4,4'-dimethoxy-1,1'-spirobi [1
H-Indan] 38. 6,6'-bis (diphenylmethyloxy)-
2.2 ', 3,3'-Tetrahydro-3,3,3', 3'-tetramethyl-5,5'-diisopropoxy-1,1'-spirobi [1H-indane] 39. 6,6'-bis (diphenylmethyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-4,4'-dichloro-1,1'-spirobi [1H
-Indan] 40. 6,6'-bis (triphenylmethyloxy)-
2,2 ', 3,3'-Tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobi [1H-indane]

41. 6,6'-bis (triphenylmethyloxy) -2,2 ', 3,3'-tetrahydro-3,3
3 ', 3', 4,4'-hexamethyl-1,1'-spirobi [1
H-Indan] 42. 6,6'-bis (triphenylmethyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3 ', 5
5'-hexamethyl-1,1'-spirobi [1H-indane] 43. 6,6'-bis (triphenylmethyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-7,7'-diethyl-1,1'-spirobi [1H
-Indan] 44. 6,6'-bis (triphenylmethyloxy)-
45. 2,2 ', 3,3'-Tetrahydro-3,3,3', 3'-tetramethyl-5,5'-diisobutyl-1,1'-spirobi [1H-indane] 45. 6,6'-bis (triphenylmethyloxy)-
2,2 ′, 3,3′-tetrahydro-3,3,3 ′, 3′-tetramethyl-4,4′-diethoxy-1,1′-spirobi [1
H-Indan] 46. 6,6'-bis (triphenylmethyloxy)-
2,2 ', 3,3'-Tetrahydro-3,3,3', 3'-tetramethyl-7,7'-di-n-butoxy-1,1'-spirobi [1H-indane] 47. 6,6'-bis (triphenylmethyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-5,5'-dichloro-1,1'-spirobi [1H
-Indan] 48. 6,6'-bis (trimethylsilyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobi [1H-indane] 49. 6,6'-bis (trimethylsilyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3 ', 5
5'-hexamethyl-1,1'-spirobi [1H-indane] 50. 6,6'-bis (trimethylsilyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3 ', 7,
7'-hexamethyl-1,1'-spirobi [1H-indane]

51. 6,6'-bis (trimethylsilyloxy) -2,2 ', 3,3'-tetrahydro-3,3
3 ', 3'-Tetramethyl-7,7'-diethyl-1,1'-spirobi [1H-indane] 52. 6,6'-bis (trimethylsilyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-5,5'-di-tert-butyl-1,1'-spirobi [1H-indane] 53. 6,6'-bis (trimethylsilyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-7,7'-dimethoxy-1,1'-spirobi [1
H-Indan] 54. 6,6'-bis (trimethylsilyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-5,5'-di-n-propoxy-1,1'-spirobi [1H-indane] 55. 6,6'-bis (trimethylsilyloxy)-
2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-7,7'-dichloro-1,1'-spirobi [1H
-Indan] 56. 6,6'-bis (tert-butyldimethylsilyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3',
3'-Tetramethyl-1,1'-spirobi [1H-indane] 57. 6,6'-bis (tert-butyldimethylsilyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3',
3 ', 4,4'-hexamethyl-1,1'-spirobi [1H-
Indan] 58. 6,6'-bis (tert-butyldimethylsilyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3',
3 ', 5,5'-hexamethyl-1,1'-spirobi [1H-
Indan] 59. 6,6'-bis (tert-butyldimethylsilyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3',
3'-tetramethyl-5,5'-diisopropyl-1,1'-
Spirobi [1H-Indan] 60. 6,6'-bis (tert-butyldimethylsilyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3',
3'-tetramethyl-7,7'-di-n-butyl-1,1'-
Spirobi [1H-Indan]

61. 6,6'-bis (tert-butyldimethylsilyloxy) -2,2 ', 3,3'-tetrahydro-
3,3,3 ', 3'-Tetramethyl-4,4'-dimethoxy-
1,1'-spirobi [1H-indane] 62. 6,6'-bis (tert-butyldimethylsilyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3',
3'-Tetramethyl-5,5'-diethoxy-1,1'-spirobi [1H-indane] 63. 6,6'-bis (tert-butyldimethylsilyloxy) -2,2 ', 3,3'-tetrahydro-3,3,3',
3'-Tetramethyl-5,5'-dichloro-1,1'-spirobi [1H-indane] 64. 5,5 ', 6,6'-Tetrakis (tert-butoxycarbonyloxy) -2,2', 3,3'-tetrahydro-
3,3,3 ', 3'-Tetramethyl-1,1'-spirobi [1
H-Indan] 65. 4,4 ', 6,6'-Tetrakis (tert-butoxycarbonylmethyloxy) -2,2', 3,3'-tetrahydro-3,3,3 ', 3'-tetramethyl-1,1'- Spirobi [1H-indan] 66. 6,6 ', 7,7'-Tetrakis (2 "-tetrahydropyranyloxy) -2,2', 3,3'-tetrahydro-3,3,3 ', 3'-tetramethyl-1,1' -Spirobi [1H-indane] 67.5,5 ', 6,6'-tetrakis (methoxymethyloxy) -2,2', 3,3'-tetrahydro-3,3,3
3 ', 3'-Tetramethyl-1,1'-spirobi [1H-indane] 68. 6,6 ', 7,7'-Tetrakis (diphenylmethyloxy) -2,2', 3,3'-tetrahydro-3,3,3
3 ', 3'-Tetramethyl-1,1'-spirobi [1H-indane] 69. 4,4 ', 6,6'-tetrakis (triphenylmethyloxy) -2,2', 3,3'-tetrahydro-3,
3,3 ', 3'-Tetramethyl-1,1'-spirobi [1H-
Indan] 70. 5,5 ', 6,6'-Tetrakis (trimethylsilyloxy) -2,2', 3,3'-tetrahydro-3,3,3
3 ', 3'-Tetramethyl-1,1'-spirobi [1H-indane] 71. 5,5 ', 6,6'-Tetrakis (tert-butyldimethylsilyloxy) -2,2', 3,3'-tetrahydro-3,3,3 ', 3'-tetramethyl-1,1'- Spirobi [1H-Indan]

The spirobiindane derivative represented by the general formula (1) can be produced, for example, according to the method disclosed in JP-A-6-287163. That is,
It can be produced by introducing the protecting group for R ₁ into the spirobiindanol derivative represented by the general formula (7) (formula 5). Examples of the compound capable of introducing a protective group into the spirobiindanol derivative include di-tert-butyl dicarbonate, tert-butyl chloroacetate, dihydro-2H-pyran, methoxymethyl chloride, diphenylmethyl chloride and triphenylmethyl. Examples thereof include chloride, trimethylsilyl chloride, and tert-butyldimethylsilyl chloride.

[0027]

Embedded image (In the formula, R ₂ , m and n are the same as above)

In this case, the ratio of the compound capable of introducing the protecting group of R _{1 to} the spirobiindanol derivative represented by the general formula (7) is as follows.
The amount of the compound is preferably 1.8 to 10 mol, and more preferably 2 to 5 mol, based on mol. In the reaction, a catalyst can be used if necessary. Preferred examples of the catalyst include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, alkali metal compounds such as sodium hydrogen carbonate, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine,
Examples thereof include amine compounds such as ethanolamine, isopropanolamine, triethanolamine, 2-dimethylaminoethanol, morpholine and ammonia.

Examples of the reaction solvent include halogen solvents such as dichloromethane, dichloroethane and chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and dimethylsulfoxide. Examples thereof include aprotic polar solvents such as sulfolane, ether solvents such as tetrahydrofuran and dioxane, and basic solvents such as pyridine and triethylamine. Although the use of a large amount of solvent does not hinder the effect of the present invention, it is self-evident that the use of a larger amount than necessary itself requires a large device and a container, resulting in a reduction in production efficiency. Usually, it is desirable to carry out the reaction in a solvent of 0.5 to 100 times (volume / weight) with respect to the spirobiindanol derivative represented by the general formula (7), and more preferably 1 to 50. Double (volume / weight).

The reaction temperature is preferably in the range of -10 ° C to the boiling point of the reaction solvent, more preferably room temperature to the boiling point of the reaction solvent. Although the reaction time depends on the reaction temperature, most of the spirobiindanol derivative represented by the general formula (7) is converted to the desired spirobiindane derivative represented by the general formula (1) by a treatment for 30 minutes or more. can do. Whether or not the spirobiindanol derivative represented by the general formula (7) has been converted into the spirobiindane derivative represented by the general formula (1) is determined by a known analysis means (eg, various chromatography, IR spectrum, NMR spectrum). ), The heat treatment time can be determined by these analytical means. The long-time heat treatment does not have a bad influence, but spending a long time itself only causes a reduction in working efficiency and production efficiency, and is usually 30 minutes to 20 hours, more preferably 1 hour to 15 hours. A heat treatment time of hours is sufficient. The stirring device is not particularly limited, but the spirobiindanol derivative represented by the general formula (7) and R
It is desirable to use a device that has the agitation capability necessary to keep the compound capable of introducing the ₁ protecting group dispersed in the solvent.

The spirobiindane derivative represented by the general formula (1) produced by the method of the present invention is
If necessary, after being subjected to treatments such as neutralization, washing with water, extraction, etc., it can be easily isolated from the reaction system (for example, the solvent is distilled off and filtered) by a known means and device. The spirobiindane derivative produced by this reaction can be isolated with sufficiently high purity. However, purification to a higher degree of purity is preferable for using the spirobiindane derivative as the resist material of the present invention. The spirobiindane derivative can be further purified by a known method (eg, column chromatography, recrystallization, solvent sludge). It was revealed that the thus-obtained spirobiindane derivative represented by the general formula (1) has excellent performance as a dissolution inhibitor for a positive resist material. The positive resist composition of the present invention contains an alkali-soluble resin, a dissolution inhibitor and an acid generator, and can be developed with an aqueous alkali solution. A positive resist material containing a spirobiindane derivative represented by the general formula (1). Further, as described below, various known formulations for producing known resist materials can be further applied.

As the alkali-soluble resin, 298 nm
It is not specified as long as it has low absorption and is soluble in alkali, but a poly (hydroxystyrene) derivative is preferable. Further, as a preferable poly (hydroxystyrene) derivative, poly (hydroxystyrene) is used.
Resins, hydrogenated poly (hydroxystyrene) resins, poly (hydroxystyrene) resins in which some hydrogen atoms of the hydroxyl groups are replaced with tert-butoxycarbonyl groups, some hydrogen atoms of the hydroxyl groups are replaced with tert-butoxycarbonyl groups Examples of the hydrogenated poly (hydroxystyrene) resin and a copolymer of styrene and hydroxystyrene can be given. These resins may be used alone or in combination of two or more. Further, as the alkali-soluble resin for the resist material of the present invention, in addition to the above poly (hydroxystyrene) derivative,
It is also possible to use an alkali-soluble resin such as phenol aralkyl resin, naphthol aralkyl resin, a copolymer of phenol and dicyclopentadiene, a polymethyl (meth) acrylate and a copolymer of styrene and maleic anhydride. The content of the alkali-soluble resin in the resist material of the present invention is 45 to 95% by weight.
Is more preferable, more preferably 60 to 90% by weight, and particularly preferably, the content of the alkali-soluble resin in the resist material is 70 to 85% by weight.

Hereinafter, as preferred examples of the alkali-soluble resin, a poly (hydroxystyrene) derivative and a poly (hydroxystyrene) derivative in which hydrogen atoms of some hydroxyl groups are tert-butoxycarbonylated will be described in detail. Among the alkali-soluble resins according to the present invention, as a poly (hydroxystyrene) derivative in which hydrogen atoms of some hydroxyl groups are tert-butoxycarbonylated, tert
-The butoxycarbonylation rate is preferably in the range of 10 to 80%, more preferably 20 to 70%. In particular, the tert-butoxycarbonylation rate is 30-60
% Range is preferred. If the tert-butoxycarbonylation rate is too high, the solubility in an alkaline aqueous solution will decrease, while if the tert-butoxycarbonylation rate is too low, the dissolution inhibiting effect will tend to be reduced. As a method for tert-butoxycarbonylating a hydrogen atom of a hydroxyl group in a poly (hydroxystyrene) derivative, a method commonly used in peptide synthesis is generally used, that is, for example, a poly (hydroxystyrene) derivative and di-tert. It can be easily produced by reacting -butyl dicarbonate.

In order to produce a resist film having high heat resistance, the weight average molecular weight of the poly (hydroxystyrene) derivative is preferably 10,000 or more. Further, in order to form a highly accurate pattern, the molecular weight distribution of the resin is preferably monodisperse. Therefore, it is preferable to use a monodisperse poly (hydroxystyrene) derivative as obtained by living polymerization. By the way, the monodispersity means that the molecular weight distribution is Mw / Mn = 1.05 to 1.50. Here, Mw represents the weight average molecular weight of the resin, and Mw
n represents a number average molecular weight. When performing living polymerization, the weight average molecular weight can be determined by the weight of the monomer and the number of moles of the initiator, or by the light scattering method. on the other hand,
The number average molecular weight can be measured using a membrane osmometer. As a method for obtaining a monodisperse resin, (a) a method of fractionating a resin having a wide molecular weight distribution produced by a radical polymerization method, and (b) a method of obtaining a monodisperse resin from the beginning by a living polymerization method , And the like.
Of these, it is preferable to use a living polymerization method that does not require a separation treatment.

The living polymerization method, for example, the case of poly (p-hydroxystyrene) resin will be described in detail below. First, in order to prevent the reaction between the hydroxyl group in the p-hydroxystyrene monomer and the polymerization initiator, a protective group for protecting the hydroxyl group is introduced. Examples of the protecting group include tert-
Butyl group, dimethylphenylcarbylmethylsilyl group,
Examples thereof include a tert-butoxycarbonyl group, a tetrahydropyranyl group, a trimethylsilyl group, and a tert-butyldimethylsilyl group. Of these, the tert-butoxycarbonyl group is particularly preferable. Living polymerization is performed using the monomer having the protective group introduced therein, and then deprotection is performed to obtain the target poly (p-hydroxystyrene) resin. The above-mentioned polymerization initiator is preferably an organometallic compound, more preferably n-butyllithium, sec-butyllithium, tert-butyllithium,
Sodium naphthalene, anthracene sodium, α-
It is an organic alkali metal compound such as sodium methyl styrene tetrameride, cumyl potassium, cumyl cesium and the like.

The living polymerization reaction is preferably carried out in an organic solvent. Preferred organic solvents are, for example, aromatic hydrocarbons such as benzene, toluene and chlorobenzene, and ether compounds such as tetrahydrofuran, dioxane, tetrahydropyran and dimethoxyethane. , N-hexane, cyclohexane, and other aliphatic hydrocarbons. These organic solvents may be used alone or in combination. Of these, tetrahydrofuran is preferred.
The concentration of the monomer during the polymerization is preferably 1 to 50%.
And more preferably 1 to 30%. Further, the reaction is preferably carried out under a stream of an inert gas such as nitrogen or argon, or under high vacuum. The reaction temperature is -100
The boiling point of the organic solvent used is preferably from -78 ° C, especially when tetrahydrofuran is used as the organic solvent.
C. to 0.degree. C. is preferable, and when benzene is used, it is preferable to carry out the reaction at room temperature. Although the reaction time depends on the reaction temperature, the p-hydroxystyrene monomer having most of the protecting groups introduced therein can be converted into the desired resin in 5 minutes or more. The heat treatment for a long time does not have a bad influence, but spending a long time itself only causes a reduction in work efficiency and production efficiency, and usually 5 minutes to 1 minute.
A reaction time of 5 hours, more preferably 30 minutes to 10 hours is sufficient.

The degree of polymerization and the molecular weight distribution of the desired resin are
It can be judged by gel permeation chromatography. When the desired degree of polymerization is reached, a living polymer having a desired molecular weight can be obtained by adding a polymerization reaction terminator to the reaction system. Examples of the polymerization reaction terminator include methanol, water and methyl bromide. Furthermore, the target living polymer can be purified and isolated by precipitating the obtained reaction mixture using a suitable solvent (for example, methanol), washing and drying. When the reaction is performed by the above method, the yield is almost 100%, and the molecular weight of the obtained resin can be appropriately adjusted by adjusting the amount of the monomer used and the number of moles of the reaction initiator. The molecular weight distribution of the resin produced by this method is monodisperse. Then, the protecting group protecting the hydroxyl group of the resin is deprotected to obtain a poly (p-hydroxystyrene) resin. The deprotection reaction is easily carried out by dissolving the resin in a solvent such as dioxane, acetone, acetonitrile, benzene or a mixed solvent thereof, and then adding hydrochloric acid, hydrobromic acid, pyridinium p-toluenesulfonate or the like. be able to. Through the above steps, a monodisperse poly (p-hydroxystyrene) resin can be produced.

The dissolution inhibitor of the present invention is a substance which becomes soluble in an alkaline aqueous solution when the resist film is irradiated with high energy rays such as deep ultraviolet rays and, if necessary, heat-treated and then treated with an alkali developing solution. And the spirobiindane derivative represented by the general formula (1) is used. The content of the dissolution inhibitor in the resist material of the present invention is preferably 7 to 40% by weight, more preferably 10 to 30% by weight.
Particularly preferably, the content of the dissolution inhibitor in the resist material is 10 to 20% by weight. If the content of the dissolution inhibitor in the resist material is too large, the mechanical strength and heat resistance of the resist film will decrease, and if the content is too small, the dissolution inhibiting effect will tend to be small.

The acid generator according to the present invention is a compound which decomposes when irradiated with a high energy ray to generate an acid. The acid generator according to the present invention is a compound that decomposes to generate an acid when irradiated with a high energy ray. As the acid generator,
For example, triphenylsulfonium tosylate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium tetrafluoroborate, phenyldi (4-tert-butoxyphenyl) sulfonium triflate, 4 -A sulfonium salt such as methoxyphenyldiphenylsulfonium tosylate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, 4-fluorophenyldiphenylsulfonium tosylate, diphenyliodonium tosylate, di (4-tert-butylphenyl) iodonium triflate or the like. Onium salts such as iodonium salts, orthobenzoquinonediazide, ortho Naphthoquinonediazide ortho anthraquinone diazide, a substituted or unsubstituted di (phenylsulfonyl) diazo compounds such as diazomethane, naphthoquinone-1,2-diazide-4-sulfonic acid esters,
Examples thereof include reaction products of benzyl tosylate such as 2,6-dinitrobenzyl tosylate, benzoin tosylate, triazine derivative or sulfonyl chloride of orthonaphthoquinonediazide and a compound having a hydroxyl group or an amino group. These acid generators may be used alone or in combination. The content of the acid generator contained in the resist composition of the present invention is preferably 1 to 10% by weight, more preferably 3 to 8% by weight. If the content is too small, the sensitivity of the resist material cannot be improved, and if the content is too large, the mechanical strength of the resist film decreases and the cost of the resist material increases. Particularly preferably, the content of the acid generator is
It is 0.3 to 8% by weight.

It is preferable that the resist composition of the present invention contains a sensitizer, if desired, within a range not impairing the effects of the present invention. Examples of the sensitizer include 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl).
Mention may be made of ethyl] benzene, mercaptooxazole, mercaptobenzoxazole, mercaptobenzothiazole, benzoxazolinone, benzothiazolone, mercaptobenzimidazole, urazole, thiouracil, mercaptopyrimidine, imidazolone and their derivatives. At this time, the content of the sensitizer is preferably 40% by weight or less, and more preferably 20% by weight or less with respect to the acid generator. The resist material of the present invention may further contain compatible additives, for example, an additional resin, a plasticizer, a stabilizer or a developed image for improving the performance of the resist film to make the developed image more visible. A commonly used compound such as a coloring agent can be added.

The formation of a positive pattern on a substrate using the resist material of the present invention can be easily carried out by a known method (for example, JP-A-6-287163).
That is, (1) a resist material solution is spin-coated on a substrate and then pre-baked to obtain a coated substrate, (2)
The obtained coated substrate is irradiated with a high energy ray through a photomask to generate an acid by decomposing the acid generator in the coating film. (3) Heat treatment is performed, and the generated acid is used as a catalyst for R1. (4) A substrate having a latent image formed by decomposing a protective group that can be easily removed under acidic conditions to eliminate the dissolution inhibiting effect of a resist is obtained. Is developed and washed with water to form a positive pattern.

[0042]

EXAMPLES The present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited to these production examples and examples. Production Example 1 (Production of Exemplified Compound 8) 6,6′-dihydroxy-2,2 ′, 3,3′-tetrahydro-3,3,3 ′, 3′-tetramethyl-1,1′-spirobi [1H -Indan] 13 g (40 mmol), triethylamine 9.8 g (100 mmol) and 1,2-dichloroethane 100 g were charged into a reaction vessel and dissolved,
25 g of di-tert-butyl dicarbonate (11
(0 mmol) was added dropwise over 30 minutes. After completion of dropping, 5
The mixture was refluxed for a period of time, gradually cooled, washed with water, and the solvent was distilled off to obtain a crude product. The crude product was purified with methanol sludge to obtain the desired 6,6′-bis (tert-butoxycarbonylmethyloxy) -2,2 ′, 3,3′-tetrahydro-3,
3,3 ', 3'-Tetramethyl-1,1'-spirobi [1H-
Indane] was obtained as white crystals. Yield 18.6 g, yield 99.0%, melting point 172-178 ° C. ¹ H-NMR (DMSO-d ₆ , δ) 1.3 (s, 6H), 1.4 (s, 6H), 1.4
(S, 18H), 2.2 (s, 2H), 2.3 (s, 2H), 6.5 (d, 2H, J = 2.1Hz), 7.0 (dd, 2H, J = 8) .2, 2.1 Hz), 7.3 (d, 2H, J = 8.2 Hz)

Production Example 2 [Production of 20% tert-butoxycarbonylated poly (p-hydroxystyrene)] 500 g of poly (p-hydroxystyrene) resin having a weight average molecular weight of 5000 was dissolved in 1500 g of dioxane,
In the solution, di-tert-butyl dicarbonate D
IBO (manufactured by Ibitz) 91.6 g (0.4 mol)
Was added, and after stirring and dissolution, 63.6 g of triethylamine was added.
(0.6 mol) was added dropwise over 30 minutes. After stirring for 3 hours, 8000 g of pure water was added to precipitate the product,
After filtration, washing, and drying, the desired 20% tert-butoxycarbonylated poly (p-hydroxystyrene) 550
g was obtained as a white solid.

Examples 1 to 8 With respect to the positive resist material prepared by using the base resin, the dissolution inhibitor and the acid generator shown in Table 1 (Table 1), a resist coated substrate was produced by the following method, Evaluation was performed by the following method. The results are summarized in Table 2 (Table 2). The base resin shown in Table 1 was produced in Production Example 2
In addition, the dissolution inhibitor was produced according to Production Example 1. [Production Method of Resist Coated Substrate] A positive resist material prepared by the following composition was spin-coated on a silicone substrate at 2000 rpm, and prebaked at 85 ° C. for 1 minute on a hot plate to form a resist film having a thickness of A resist-coated substrate having a thickness of 0.7 μm was manufactured. Base resin 81 parts by weight Dissolution inhibitor (compound represented by general formula (1)) 14 parts by weight Acid generator 5 parts by weight Coating solvent (ethoxyethyl acetate) 400 parts by weight Total 500 parts by weight

[Evaluation Method of Resist Coated Substrate] The characteristics of the resist material were measured by the following method using the resist coated substrate manufactured by the above method. (1) Sensitivity: reduction exposure projection device N on each resist coated substrate
After exposure using SR-1505EX (manufactured by Nikon Corporation) at an excess interval of 10 mJ from 10 mJ, 100
After heating for 90 seconds at 90 ° C., then immersion development with a 2.4% by weight tetramethylammonium hydroxide aqueous solution for 65 seconds, washing for 30 seconds with water, and drying, the sensitivity is determined as appropriate exposure time (minimum exposure time required for patterning. ) Was measured. The results are expressed as values in units of 10 mJ, and the smaller the value, the shorter the exposure time and the better the sensitivity. (2) Cross-sectional shape (a): Immediately after exposure development treatment: Each resist-coated substrate was exposed with a reduction exposure projection device NSR-1505EX (manufactured by Nikon Corp.) for an optimal exposure time to obtain 100 silicon wafers. ℃, 90 seconds heating, then 2.4% by weight
The cross-sectional shape of the resist pattern obtained by immersion development with an aqueous solution of tetramethylammonium hydroxide for 65 seconds, washing with water for 30 seconds, and drying was observed with a microscope. A hang or a strong taper was marked as x. (B) Development treatment after exposure for 1 hour: A silicon wafer obtained by exposing each resist-coated substrate with a reduction exposure projection device NSR-1505EX (manufactured by Nikon Corporation) for an optimum exposure time, 100 ° C., 90 seconds After heating, it was allowed to stand at room temperature for 1 hour, then immersion developed with a 2.4% by weight tetramethylammonium hydroxide aqueous solution for 65 seconds, washed with water for 30 seconds, and dried to obtain a cross-sectional shape of a resist pattern with a microscope. Observe with a vertical side, ○, and if the side is not vertical and has an overhang or strong taper ×
And

[0046]

[Table 1] tBC-HS: tert-butoxycarbonylated poly (p-
Hydroxystyrene) THP-HS: Tetrahydropyranylated poly (p-hydroxystyrene) Copolymer: Copolymer of styrene and hydroxystyrene

Comparative Example 1 Example 1 was repeated except that di-tert-butoxycarbonylbisphenol A represented by the above formula (2) was used in place of the compound of Exemplified Compound No. 1 as the dissolution inhibitor. A resist-coated substrate was obtained by the same method as the method, and the above evaluation was performed. The results are shown in Table 2. Comparative Example 2 Similar to the method shown in Example 4, except that di-tert-butoxycarbonylbiphenyl represented by the above formula (4) was used as the dissolution inhibitor instead of the compound of Exemplified Compound No. 24. A resist coated substrate was obtained by the method and the above evaluation was performed. The results are shown in Table 2.

[0048]

[Table 2] As is clear from Table 2, the resist material using the spirobiindane derivative represented by the general formula (1) of the present invention as the dissolution inhibitor is the same as the resist material prepared using the conventionally used dissolution inhibitor. The sensitivity and resolution are excellent in comparison.

[0049]

According to the present invention, it is possible to provide a positive resist material for high energy rays which is excellent in sensitivity and resolution.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07D 309/12 C07F 7/18 A G03F 7/004 501 7/039 501 H01L 21/027

Claims (6)

[Claims] 1. A spirobiindane derivative represented by the following general formula (1) (formula 1). Embedded image (In the formula, R ₁ represents a protecting group that can be easily removed under acidic conditions, R ₂ represents a hydrogen atom, an alkyl group, an alkoxy group, a nitro group or a halogen atom, and m represents 1 or 2, n represents an integer of 1 to 3) 2. The protecting group represented by R ₁ , is a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group,
The spirobiindane derivative according to claim 1, which is selected from the group consisting of a tetrahydropyranyl group, a methoxymethyl group, a diphenylmethyl group, a triphenylmethyl group, a trimethylsilyl group and a tert-butyldimethylsilyl group. 3. A high-energy sensitive positive resist composition containing an alkali-soluble resin, a dissolution inhibitor and an acid generator, which is developable in an alkaline aqueous solution and is used as the dissolution inhibitor. A positive resist material containing the spirobiindane derivative according to 2. 4. The positive resist material according to claim 3, wherein the alkali-soluble resin is a poly (hydroxystyrene) derivative. 5. An (a) poly (hydroxystyrene) derivative in which a part of hydrogen atoms of hydroxyl groups are substituted with tert-butoxycarbonyl groups as an alkali-soluble resin, (b) a dissolution inhibitor and (c) an acid generator. , 0.45 ≦ (a), 0.07 ≦ (b) ≦ 0.40, 0.005 ≦ (c) ≦ 0.15, and (a) + (b) + The positive resist material according to claim 3 or 4, wherein the positive resist material is contained at a ratio of (c) = 1. 6. A poly (hydroxystyrene) derivative is
The positive resist material according to claim 3, which is a monodisperse poly (hydroxystyrene) derivative obtained by a living polymerization reaction.