JPH0664343B2 - Resin composition for resist - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention is a resin suitable for a negative type resist which is crosslinked by irradiation with ultraviolet rays, X-rays, γ-rays or electron beams to become a polymer insoluble in a solvent. It relates to a composition.

[Conventional technology]

Many are known as resin compositions for resists, acrylic acid-based polymers, phenol-based polymers,
A resin composition composed of a styrene-based polymer or the like is used in applications such as manufacturing of semiconductor devices.

[Problems to be solved by the invention]

Due to high integration of semiconductor devices, there is a strong demand for high sensitivity, high resolution and other functions for resin compositions for resists, and development of resin compositions for resists with new excellent properties is desired. There is.

[Means for solving problems]

The present inventor earnestly studied the development of the above new resin composition for a high-performance resist, and completed the present invention.

That is, the present invention provides (1) general formula (I) (Wherein, X is a halogen atom), and a polymer having an α-halogenoisopropenylcumene unit represented by the formula (2) and the general formula (II) And a polymer having a diisopropenylbenzene unit represented by the following.

In the present invention, the α-halogenoisopropenylcumene unit and the diisopropenylbenzene unit do not necessarily have to be present in different polymer chains, and the α-halogenoisopropenylcumene unit and the diisopropenylbenzene unit may be present in the same polymer chain. Units may exist.

In the present invention, α with respect to all monomer units in the polymer
-Halogenoisopropenylcumene unit abundance ratio of 0.02
The above is preferable, and the sum of α-halogenoisopropenylcumene unit and diisopropenylbenzene unit is preferably 0.05 or more in terms of sensitivity when used for a resist, and the gel produced by irradiation is preferable. It is also preferable from the viewpoint of durability.

The ratio of α-halogenoisopropenylcumene units to diisopropenylbenzene units is preferably 10/90 to
90/10. If it is less than 10/90, it is not preferable in terms of sensitivity, and if it is 90/10 or more, it is not preferable because of the durability of the gel produced by crosslinking.

The molecular weight of the polymer constituting the composition of the present invention is not particularly limited, but is 1000 or more, preferably 10,000 to 1,000,000 in consideration of the moldability of the coating film. Further, in order to improve the adhesion to the substrate, the durability of the coating film, the improvement of sensitivity and the like, additives other than these polymers may be added.

In the present invention, the α-halogenoisopropenylcumene unit is m relative to the isopropenyl group forming the polymer chain.
It has a structure in which a halogenopropane group is bonded to the position or p-position, and examples of the halogen atom include fluorine, chlorine, bromine and iodine. The diisopropenylbenzene unit is in the m-position or p-position to the isopropenyl group forming the polymer chain.
It has a structure in which an isopropenyl group is bonded to the position. As the monomer unit other than these unit amount units, those having various structures can be used, but preferably a monomer unit having an aromatic ring, that is, styrene, α-methylstyrene or an alkyl group or alkoxy group on the aromatic ring. A preferable monomer unit is a styrene derivative having a substituent such as a group or a halogen atom.

Although various kinds of polymers can be used to form the composition of the present invention, α-halogenoisopropenylcumene, diisopropenylbenzene and / or another monomer is used as a monomer in an appropriate combination and used alone. Alternatively, a copolymerization reaction is performed,
It is possible to obtain an α-halogenoisopropenylcumene unit-containing polymer, a diisopropenylbenzene unit-containing polymer, or a polymer containing both of them. Further, the above-mentioned diisopropenylbenzene unit-containing polymer is dissolved in a solvent such as a halogenated hydrocarbon, and a hydrogen halide such as hydrogen fluoride, hydrogen chloride, hydrogen bromide or hydrogen iodide is partially converted to an isopropenyl group or By introducing all the isopropenyl groups until they become halogenopropyl groups, an α-halogenoisopropenylcumene unit-containing polymer or a polymer containing both α-halogenoisopropenylcumene units and diisopropenylbenzene units is obtained. You can also As a method for obtaining a polymer having a large number of diisopropenylbenzene units, a specific method is disclosed in, for example, JP-A-59-207905.

In the present invention, if necessary, the solvent-insoluble portion is removed from the polymer obtained by the above-mentioned method, and in some cases, the adhesion to the substrate described above, the durability of the coating film, and a sensitivity improver are added, The resin composition solution for resist may be used as it is, or the solvent may be removed to obtain a solid composition. The composition of the present invention is usually dissolved in a suitable solvent and applied to a substrate,
When the coating film obtained by drying is irradiated with ultraviolet rays, X-rays, γ-rays, or an electronic tip, only the irradiated part undergoes a crosslinking reaction and becomes insoluble in a solvent, and therefore it can be used for a negative type resist.

〔The invention's effect〕

The composition of the present invention has high sensitivity to irradiation with ultraviolet rays, X-rays, γ-rays, electron rays and the like, and is extremely useful as a resist polymer.

〔Example〕

 Hereinafter, the present invention will be further described with reference to examples.

Reference example 1 100 ml benzene, 36 ml styrene in a 200 ml round bottom flask,
14 ml of diisopropenylbenzene (m-form 96%, the rest is isopropenylcumene), 0.3 g of azobisisobutyronitrile
Was added and the mixture was reacted at 70 ° C. for 14 hours, and then the reaction mixture was poured into 1 of methanol to precipitate the copolymer. After weighing, it was weighed and found to be 9.9 g. When the content of isopropenyl group was measured by proton NMR, the diisopropenylbenzene unit was 18.6 mol% and the intrinsic viscosity number of the toluene solution at 30 ° C. was 0.39. This is referred to as polymer A.

Polymer A5g obtained above was dissolved in 200 ml of chloroform,
Introduce 2 g of hydrogen chloride gas over 10 minutes, stir for another 30 minutes, then introduce nitrogen gas to remove unreacted hydrogen chloride gas, filter the reaction solution, and vacuum dry the solution to 5.2 g weight. Combined B was obtained. It was confirmed by elemental analysis and proton NMR that substantially all the isopropenyl groups were changed to chloro proton groups. The intrinsic viscosity measured with a toluene solution at 30 ° C. was 0.34.

The same reaction as described above was performed except that the amount of hydrogen chloride gas introduced was 0.3 g. The polymer C thus obtained was subjected to elemental analysis and protons.
According to NMR, 8.6 mol% was converted to a chloropropane group, and 10 mol% remained an isopropenyl group. or
The intrinsic viscosity measured with a toluene solution at 30 ° C was 0.35.

Reference Example 2 Using a 200 ml round bottom flask, 60 ml of toluene, 34 ml of α-methylstyrene and diisopropenylbenzene (96 wt% is m
-Diisopropenylbenzene, the rest is m-isopropenylcumene) 16ml, diglyme 1ml, -10 ℃
Butyllithium (10 wt% hexane solution) (1.5 ml) was added thereto, and the mixture was reacted for 1 hour. Then, the mixture was poured into a large amount of methanol, filtered and dried to obtain 21.5 g of Polymer D. According to proton NMR, the diisopropenyl unit content was 28 mol%, and the intrinsic viscosity number of the toluene solution at 30 ° C. was 0.42.

Using this polymer D, a polymer E in which the isopropenyl group was completely changed to a chloropropyl group was obtained in the same manner as in Reference Example 1. The intrinsic viscosity of this polymer E was 0.40.

Examples 1 to 5 and Reference Examples 1 to 3 Polymers A to E were individually or mixed in the ratios shown in Table 1 and dissolved in chloroform, coated on a glass plate and dried to form a coating film having a thickness of about 2 μm. Formed. An aluminum grid with a 2 mm interval was placed on this coating film, and light was irradiated from a distance of 10 cm with a 300 W mercury lamp (Toshiba 300H) for 60 minutes. Then, this coating film was treated with chloroform and the solubility of the light-irradiated part was examined.
The results are shown in Table 1.

Claims (1)

[Claims] 1. A general formula I: (Wherein X represents a halogen atom) and a polymer having an α-halogenoisopropenylcumene unit represented by the formula (2) and the general formula II A resin composition for resist containing a polymer having a diisopropenylbenzene unit represented by: