Positive resist composition comprising an alkali-soluble resin a

Radiation imagery chemistry: process – composition – or product th – Diazo reproduction – process – composition – or product – Composition or product which contains radiation sensitive...

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430165, 430191, 430193, 430326, 534557, G03F 7023, G03F 732

Patent

active

052831558

DESCRIPTION:

BRIEF SUMMARY
FIELD OF THE INVENTION

The present invention relates to a resist composition which has a high .gamma.-value.


BACKGROUND ART

A composition containing a compound having a quinone diazide group and an alkali-soluble resin finds use as a positive resist, because upon exposure to light having a wavelength of 300 to 500 nm, the quinone diazide group decomposes to form a carboxyl group whereby the originally alkali-insoluble composition becomes alkali-soluble. The positive resist composition has much better resolution than a negative resist composition and is used in the production of integrated circuits such as IC or LSI.
Recently, particularly with integrated circuits, miniaturization has proceeded with a rise in the integration level, which results in demands for formation of patterns of submicron order and more excellent resolution (high .gamma.-value). However, a resist composition comprising a conventional quinone diazide compound and a conventional alkali-soluble resin has a limit in increase of the .gamma.-value.
For example, if the amount of quinone diazide compound is increased to improve the .gamma.-value, serious problems such as deterioration of sensitivity and increase of residues after developing arise. Therefore, the improvement of the .gamma.-value is limited.


DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a positive resist composition which has a higher .gamma.-value.
The present invention is based on the finding that, when a quinone diazide sulfonic acid ester of a polyvalent phenol having a specific chemical structure is used as a sensitizer, the positive resist composition has a much increased .gamma.-value.
Accordingly, the present invention provides a positive resist composition which comprises an alkali-soluble resin and, as a sensitizer, a quinone diazide sulfonic acid ester of a phenol compound of the formula: ##STR2## wherein Y.sub.1, Y.sub.2, Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4, Z.sub.5, Z.sub.6 and Z.sub.7 are independently a hydrogen atom, a hydroxyl group or a C.sub.1 -C.sub.4 alkyl group which may be substituted with a halogen atom provided that at least one of Y.sub.1 and Y.sub.2 is a hydroxyl group, and at least two of Z.sub.1 to Z.sub.7 are hydroxyl groups.
In particular, the phenol compound (I) in which two of Z.sub.1 to Z.sub.7 are hydroxyl groups is preferred since the resist composition containing the quinone diazide sulfonic ester of such phenol has a particularly high .gamma.-value.
In addition, the phenol compound (I) in which at least one of Z.sub.1, Z.sub.2, Z.sub.3 and Z.sub.4 is a hydroxyl group and at least one of Z.sub.5, Z.sub.6 and Z.sub.7 is a hydroxyl group is preferred since the resist composition has a high film thickness retention.
In the general formula (I), R.sub.1 to R.sub.6 are independently a C.sub.1 -C.sub.10 alkyl group (e.g. a methyl group, an ethyl group, etc.), a C.sub.1 -C.sub.4 alkenyl group, a cycloalkyl group or an aryl group or a hydrogen atom.
Specific examples of the phenol compound (I) are ##STR3##
The quinone diazide sulfonic acid ester of the phenol compound may be prepared by a per se conventional method. For example, the ester is prepared by a condensation reaction of the phenol compound with naphthoquinone diazide sulfonyl halogenide or benzoquinone diazide sulfonyl halogenide in the presence of a weak alkali such as sodium carbonate.
The quinone diazide sulfonic acid esters may be used alone or in combination.
To the resist composition of the present invention, a quinone diazide sulfonic acid ester of other polyvalent phenol compounds may be added. Examples of the other polyvalent phenol compounds are hydroquinone; resorcinol; phloroglucin; 2,4-dihydroxybenzophenone; trihydroxybenzophenones such as 2,3,4-trihydroxybenzophenone, 2,2',3-trihydroxybenzophenone, 2,2',4-trihydroxybenzophenone, 2,2',5-trihydroxybenzophenone, 2,3,3'-trihydroxybenzophenone, 2,3,4'-trihydroxybenzophenone, 2,3',4-trihydroxybenzophenone, 2,3',5-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4',5-trihydroxybenzophenone

REFERENCES:
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patent: 3046118 (1962-07-01), Schmidt
patent: 3046119 (1962-07-01), Sus
patent: 3188210 (1965-06-01), Fritz et al.
patent: 4883739 (1989-11-01), Sakaguchi et al.
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patent: 5077173 (1991-12-01), Schultz et al.
Baker, McOmie, and Wild: Condensation, pp. 3060-3064, 596. Condensation Products of Phenols and Ketones. Part XII . . .

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