Tokyo Ohka Kogyo Co., Ltd.

Katsumi Oomori

Kazufumi Sato

Hiroto Yukawa

Mitsuru Sato

Kiyoshi Ishikawa

Fumitake Kaneko

Etsuko Iguchi

Ryusuke Uchida

Toshimasa Nakayama

Tomotaka Yamada

Yohei Kinoshita

Kazuo Tani

Hideo Hada

Kazuyuki Nitta

Akiyoshi Yamazaki

Satoshi Maemori

Yoshiki Sugeta

Toshikazu Takayama

Yasuhiko Katsumata

Mitsuro Sato

Yukihiro Sawayanagi

Disclosed is a positive-working chemical-amplification photoresist composition used in the patterning works in the manufacture of semiconductor devices, with which quite satisfactory patterning of a photoresist layer can be accomplished even on a substrate surface provided with an undercoating film of silicon nitride, phosphosilicate glass, borosilicate glass and the like in contrast to the prior art using a conventional photoresist composition with which satisfactory patterning can hardly be accomplished on such an undercoating film. The photoresist composition comprises, besides a film-forming resin capable of being imparted with increased solubility in an alkaline solution by interacting with an acid and a radiation-sensitive acid-generating compound, a phosphorus-containing oxo acid such as phosphoric acid and phosphonic acid or an ester thereof.

Positive-working chemical-amplification photoresist composition

Disclosed is a novel positive-working chemical-amplification photoresist composition capable of giving an extremely finely patterned resist layer in the manufacturing process of semiconductor devices. The photoresist composition comprises: (A) 100 parts by weight of a copolymeric resin consisting of from 50 to 85% by moles of (a) hydroxyl group-containing styrene units, from 15 to 35% by moles of (b) styrene units and from 2 to 20% by moles of (c) acrylate or methacrylate ester units each having a solubility-reducing group capable of being eliminated in the presence of an acid; and (B) from 1 to 20 parts by weight of a radiation-sensitive acid-generating agent which is an onium salt containing a fluoroalkyl sulfonate ion having 3 to 10 carbon atoms as the anion such as bis(4-tert-butylphenyl) iodonium nonafluorobutane sulfonate.

The invention discloses an improvement in the photolithographic patterning process of a photoresist layer in the manufacture of semiconductor devices in which occurrence of defects in the patterned resist layer can be greatly suppressed resulting in increased reliability of the semiconductor devices and productivity thereof. The improvement can be accomplished by using a chemical-amplification positive-working photoresist composition which exhibits a rate of film thickness reduction in the range from 0.09 to 1.0 nm/second when the photoresist layer before light-exposure is kept in a 2.38% aqueous solution of tetramethylammonium hydroxide at 23&deg; C. to dissolve away the resist layer.

Method for the preparation of a semiconductor device

Disclosed is a novel positive-working chemical-amplification photoresist composition capable of giving an extremely finely patterned resist layer in the manufacturing process of semiconductor devices. The photoresist composition comprises: (A) 100 parts by weight of a copolymeric resin consisting of from 50 to 85% by moles of (a) hydroxyl group-containing styrene units, from 15 to 35% by moles of (b) styrene units and from 2 to 20% by moles of (c) acrylate or methacrylate ester units each having a solubility-reducing group capable of being eliminated in the presence of an acid; and (B) from 1 to 20 parts by weight of a radiation-sensitive acid-generating agent which is an iodonium salt containing a fluoroalkyl sulfonate ion having 3 to 10 carbon atoms as the anion such as bis(4-tert-butylphenyl) iodonium nonafluorobutane sulfonate.

The invention discloses an improvement in the photo-lithographic patterning process of a photoresist layer in the manufacture of semiconductor devices in which occurrence of defects in the patterned resist layer can be greatly suppressed resulting in increased reliability of the semiconductor devices and productivity thereof. The improvement can be accomplished by using a chemical-amplification positive-working photoresist composition which exhibits a rate of film thickness reduction in the range from 0.09 to 1.0 nm/second when the photoresist layer before light-exposure is kept in a 2.38% aqueous solution of tetramethylammonium hydroxide at 23&deg; C. to dissolve away the resist layer.

The invention discloses a chemical-amplification positive-working photoresist composition of the crosslinked type used for photolithographic patterning works in the manufacture of electronic devices. While the composition comprises a film-forming resinous ingredient capable of being imparted with increased alkali-solubility in the presence of an acid and a radiation-sensitive acid-generating compound, optionally, with further admixture of an aliphatic amine compound and an acid compound, the inventive photoresist composition is characterized by the unique resinous ingredient which consists of four types of monomeric units including hydroxystyrene units, styrene units, monomeric units having acid-dissociable solubility-reducing groups and crosslinking units. The acid-dissociable solubility-reducing group is not conventional tert-butoxycarbonyloxy group but characteristically a 1-alkylcyclohexyl group or a polycyclic saturated aliphatic hydrocarbon group.

Crosslinked positive-working photoresist composition

Disclosed is a novel positive-working chemical-amplification photoresist composition capable of giving an extremely finely patterned resist layer in the manufacturing process of semiconductor devices and a method for forming a finely patterned resist layer therewith. The photoresist composition comprises: (A) 100 parts by weight of a copolymeric resin consisting of from 50 to 85% by moles of (a) hydroxyl group-containing styrene units, from 15 to 35% by moles of (b) styrene units and from 2 to 20% by moles of (c) tert-butyl (meth)acrylate units; and (B) from 1 to 20 parts by weight of a radiation-sensitive acid-generating agent which is an onium salt containing a fluoroalkyl sulfonate ion having 1 to 10 carbon atoms as the anion such as diphenyliodonium trifluoromethane sulfonate. In the pattern-forming method with the photoresist composition, the photoresist coating layer is subjected to heat treatments before and after the pattern-wise exposure to light at a relatively low temperature of 100-110 &deg; C. so that a satisfactory patterning can be accomplished even for an isolated pattern having a line width as small as 0.15 &mgr;m.

Positive-working chemical-amplification photoresist composition and method for forming a resist pattern using the same

Disclosed is a novel positive-working chemical-amplification photoresist composition used in the photolithographic patterning works in the manufacture of semiconductor devices capable of giving an excellently patterned resist layer with remarkably small film thickness reduction by the development treatment with an aqueous alkaline developer solution in the areas unexposed to patternwise exposure to light. Characteristically, the resinous ingredient in the composition, which is formulated in combination with a radiation-sensitive acid-generating agent and imparted with an increase in the solubility in an alkaline developer solution, is a ternary copolymeric resin consisting of the monomeric units of (a) hydroxystyrene units, (b) styrene units and (c) 1-alkylcyclohexyl (meth)acrylate units each in a specified molar fraction.

Positive-working photoresist composition

Disclosed is a novel positive-working chemical-amplification photoresist composition capable of giving an extremely finely patterned resist layer in the manufacturing process of semiconductor devices and a method for forming a finely patterned resist layer therewith. The photoresist composition comprises: (A) 100 parts by weight of a copolymeric resin consisting of from 50 to 85% by moles of (a) hydroxyl group-containing styrene units, from 15 to 35% by moles of (b) styrene units and from 2 to 20% by moles of (c) tert-butyl (meth)acrylate units; and (B) from 1 to 20 parts by weight of a radiation-sensitive acid-generating agent which is an onium salt containing a fluoroalkyl sulfonate ion having 1 to 10 carbon atoms as the anion such as diphenyliodonium trifluoromethane sulfonate.

Disclosed is a method for forming an extremely finely patterned resist layer on a substrate surface by using a positive-working chemical-amplification photoresist composition in the manufacturing process of semiconductor devices. The method for the formation of a patterned resist layer comprises the steps of: (1) forming, on a substrate, a layer of a photoresist composition comprising: (A) a copolymeric resin consisting of (a) from 50 to 85% by moles of hydroxyl group-containing styrene units, (b) from 15 to 35% by moles of styrene units and (c) from 2 to 20% by moles of acrylate or methacrylate ester units each having a solubility-reducing group capable of being eliminated in the presence of an acid; and (B) a radiation-sensitive acid-generating agent which is an onium salt containing a fluoroalkyl sulfonate ion having 1 to 10 carbon atoms as the anion such as bis(4-tert-butylphenyl) iodonium nonafluorobutane sulfonate; (2) subjecting the photoresist layer to a first heat treatment at a temperature in the range from 120&deg; C. to 140&deg; C.; (3) subjecting the photoresist layer to pattern-wise exposure to light; (4) subjecting the photoresist layer to a second heat treatment at a temperature in the range from 110&deg; C. to 130&deg; C. but lower than the temperature of the first heat treatment; and (5) subjecting the photoresist layer to a development treatment.

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Chigasaki, Japan

Katsumi Oomori