公开(公告)号：US5736296A

公开(公告)日：1998-04-07

申请号：US625931

申请日：1996-04-01

Applicant: Mitsuru Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Etsuko Iguchi ,  Yoshika Sakai ,  Kazufumi Sato ,  Toshimasa Nakayama

Inventor： Mitsuru Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Etsuko Iguchi ,  Yoshika Sakai ,  Kazufumi Sato ,  Toshimasa Nakayama

IPC: G03F7/004 ,  G03F7/039

CPC classification number: G03F7/039 ,  G03F7/0045 ,  Y10S430/106

Abstract: Disclosed is an improved, chemically-amplifying positive resist composition for radiations, especially UV rays, deep-UV rays, excimer laser beams, X-rays, electron beams. The composition comprises (A) a resin component whose solubility in an alkaline aqueous solution is increased by the action of acids, (B) a compound which generates an acid when exposed to radiations, and (A) a resin component, (B) an acid-generating agent and (C) an organic carboxylic acid compound, in which said resin component (A) is a mixture comprising (a) a polyhydroxystyrene where from 10 to 60 mol % of the hydroxyl groups have been substituted by residues of a general formula (I): ##STR1## wherein R.sup.1 represents a hydrogen atom or a methyl group, R.sup.2 represents a methyl group or an ethyl group, and R.sup.3 represents a lower alkyl group having 1 to 4 carbon atoms; and (b) a polyhydroxystyrene where from 10 to 60 mol % of the hydroxyl groups have been substituted by tert-butoxycarbonyloxy groups. The composition has a high sensitivity, a high resolution, high heat resistance, good width characteristic in focus depth and good post-exposure storage stability, has good storage stability as a resist solution, and gives resist patterns with good profiles, without depending on the substrate to which it is applied. The composition is useful for forming fine patterns in producing ultra-LSIs.

Abstract translation: 公开了用于辐射，特别是紫外线，深紫外线，准分子激光束，X射线，电子束的改进的化学增幅正性抗蚀剂组合物。 该组合物包含（A）通过酸的作用在碱性水溶液中的溶解度增加的树脂成分，（B）暴露于辐射时产生酸的化合物，（A）树脂成分，（B） 酸性发生剂和（C）有机羧酸化合物，其中所述树脂组分（A）是包含（a）多羟基苯乙烯的混合物，其中10至60mol％的羟基已被一般的残基取代 式（I）：其中R 1表示氢原子或甲基，R 2表示甲基或乙基，R 3表示碳原子数1〜4的低级烷基。 和（b）聚羟基苯乙烯，其中10至60摩尔％的羟基已被叔丁氧羰基氧基取代。 该组合物具有高灵敏度，高分辨率，高耐热性，聚焦深度的良好宽度特性和良好的曝光后储存稳定性，作为抗蚀剂溶液具有良好的储存稳定性，并且具有良好外形的抗蚀剂图案，而不依赖于 底物。 该组合物可用于在制造超LSI时形成精细图案。

公开(公告)号：US6159652A

公开(公告)日：2000-12-12

申请号：US20408

申请日：1998-02-09

Applicant: Mitsuru Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Etsuko Iguchi ,  Yoshika Sakai ,  Kazufumi Sato ,  Toshimasa Nakayama

Inventor： Mitsuru Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Etsuko Iguchi ,  Yoshika Sakai ,  Kazufumi Sato ,  Toshimasa Nakayama

IPC: G03F7/004 ,  G03F7/039

CPC classification number: G03F7/039 ,  G03F7/0045 ,  Y10S430/106

Abstract: Disclosed is an improved, chemically-amplifying positive resist composition for radiations, especially UV rays, deep-UV rays, excimer laser beams, X-rays, electron beams. The composition comprises (A) a resin component whose solubility in an alkaline aqueous solution is increased by the action of acids, (B) a compound which generates an acid when exposed to radiations, and (A) a resin component, (B) an acid-generating agent and (C) an organic carboxylic acid compound, in which said resin component (A) is a mixture comprising (a) a polyhydroxystyrene where from 10 to 60 mol % of the hydroxyl groups have been substituted by residues of a general formula (I): ##STR1## wherein R.sup.1 represents a hydrogen atom or a methyl group, R.sup.2 represents a methyl group or an ethyl group, and R.sup.3 represents a lower alkyl group having 1 to 4 carbon atoms;and (b) a polyhydroxystyrene where from 10 to 60 mol % of the hydroxyl groups have been substituted by tert-butoxy-carbonyloxy groups. The composition has a high sensitivity, a high resolution, high heat resistance, good width characteristic in focus depth and good post-exposure storage stability, has good storage stability as a resist solution, and gives resist patterns with good profiles, without depending on the substrate to which it is applied. The composition is useful for forming fine patterns in producing ultra-LSIs.

Abstract translation: 公开了用于辐射，特别是紫外线，深紫外线，准分子激光束，X射线，电子束的改进的化学增幅正性抗蚀剂组合物。 该组合物包含（A）通过酸的作用在碱性水溶液中的溶解度增加的树脂成分，（B）暴露于辐射时产生酸的化合物，（A）树脂成分，（B） 酸性发生剂和（C）有机羧酸化合物，其中所述树脂组分（A）是包含（a）多羟基苯乙烯的混合物，其中10至60mol％的羟基已被一般的残基取代 式（I）：其中R1表示氢原子或甲基，R2表示甲基或乙基，R3表示碳原子数1〜4的低级烷基。 和（b）聚羟基苯乙烯，其中10至60摩尔％的羟基已被叔丁氧基 - 羰基氧基取代。 该组合物具有高灵敏度，高分辨率，高耐热性，聚焦深度的良好宽度特性和良好的曝光后储存稳定性，作为抗蚀剂溶液具有良好的储存稳定性，并且具有良好外形的抗蚀剂图案，而不依赖于 底物。 该组合物可用于在制造超LSI时形成精细图案。

公开(公告)号：US5908730A

公开(公告)日：1999-06-01

申请号：US898320

申请日：1997-07-22

Applicant: Kazuyuki Nitta ,  Kazufumi Sato ,  Akiyoshi Yamazaki ,  Yoshika Sakai ,  Toshimasa Nakayama

Inventor： Kazuyuki Nitta ,  Kazufumi Sato ,  Akiyoshi Yamazaki ,  Yoshika Sakai ,  Toshimasa Nakayama

IPC: G03F7/004 ,  G03F7/038 ,  G03F7/039

CPC classification number: G03F7/038 ,  G03F7/0045 ,  G03F7/039

Abstract: Proposed is a positive- or negative-working chemical-sensitization photoresist composition having advantages in respect of the contrast and resolution of patterning, photosensitivity and cross sectional profile of the patterned resist layer as well as in respect of stability of the latent image formed by pattern-wise exposure to light before post-exposure baking treatment. The composition comprises: (A) 100 parts by weight of a film-forming resinous ingredient which causes a change, i.e. increase or decrease, of solubility in an aqueous alkaline solution by the interaction with an acid; and (B) from 0.5 to 20 parts by weight of a radiation-sensitive acid-generating agent which is a diazomethane compound represented by the general formulaR.sup.1 --SO.sub.2 --C(.dbd.N.sub.2)--SO.sub.2 --R.sup.2,in which R.sup.1 and R.sup.2 are each, independently from the other, a monovalent cyclic group substituted on the cyclic nucleus by an acid-dissociable group such as a tert-butoxycarbonyl and acetal groups.

Abstract translation: 提出了一种正性或负性的化学增感光致抗蚀剂组合物，其在图案化抗蚀剂层的图案的对比度和分辨率，光敏性和横截面轮廓方面以及关于通过图案形成的潜像的稳定性方面具有优势 在曝光前烘烤处理下曝光。 该组合物包含：（A）100重量份成膜树脂成分，其通过与酸的相互作用而引起在碱性水溶液中的溶解度的改变，即增加或减少; 和（B）0.5〜20重量份的辐射敏感性酸产生剂，其为通式R 1 -SO 2 -C（= N 2）-SO 2 -R 2表示的重氮甲烷化合物，其中R 1和R 2为 各自独立地是通过酸解离基团如叔丁氧基羰基和缩醛基在环状核上取代的一价环状基团。

公开(公告)号：US5948589A

公开(公告)日：1999-09-07

申请号：US658234

申请日：1996-06-04

Applicant: Kazufumi Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Yoshika Sakai ,  Toshimasa Nakayama

Inventor： Kazufumi Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Yoshika Sakai ,  Toshimasa Nakayama

IPC: G03F7/004 ,  G03F7/039 ,  H01L21/027

CPC classification number: G03F7/039 ,  G03F7/0045 ,  Y10S430/106

Abstract: Proposed is an improved chemical sensitization-type positive-working photoresist composition of high sensitivity and high pattern resolution for the photolithographic patterning works in the manufacture of semiconductor devices, which exhibits excellent post-exposure stability of the latent image formed by the pattern-wise exposure of the resist layer to actinic rays not to be affected relative to the fidelity of pattern reproduction and sensitivity even by standing for a length of time after the exposure to actinic rays before the subsequent processing treatment. The composition is characterized by the formulation of, in addition to an acid generating compound to release an acid by the irradiation with actinic rays and a resinous ingredient capable of being imparted with increased solubility in an aqueous alkaline developer solution by the presence of an acid, an amine compound such as triethylamine and a carboxylic acid such as salicylic acid in combination.

Abstract translation: 提出了一种用于半导体器件制造中的光刻图案化工艺的高灵敏度和高图案分辨率的改进的化学增感型正性光致抗蚀剂组合物，其显示出通过图案曝光形成的潜像的优异的后曝光稳定性 的抗蚀剂层相对于图案再现和灵敏度的保真度而不受影响的光化射线，即使在随后的处理处理之后暴露于光化射线之后静置一段时间。 该组合物的特征在于除了通过光化射线照射释放酸的酸产生化合物和能够通过存在酸在碱性显影剂水溶液中赋予增加的溶解性的树脂成分之外， 胺化合物如三乙胺和羧酸如水杨酸组合。

公开(公告)号：US5945248A

公开(公告)日：1999-08-31

申请号：US898124

申请日：1997-07-22

Applicant: Kazuyuki Nitta ,  Kazufumi Sato ,  Akiyoshi Yamazaki ,  Yoshika Sakai ,  Toshimasa Nakayama

Inventor： Kazuyuki Nitta ,  Kazufumi Sato ,  Akiyoshi Yamazaki ,  Yoshika Sakai ,  Toshimasa Nakayama

IPC: G03F7/004 ,  G03F7/039 ,  G03C1/52

CPC classification number: G03F7/0045 ,  Y10S430/106 ,  Y10S430/121

Abstract: Proposed is a positive-working chemical-sensitization photoresist composition having advantages in respect of high resolution of patterning, high photosensitivity and orthogonal cross sectional profile of the patterned resist layer as well as in respect of little dependency of the performance on the nature of the substrate surface. The composition comprises:(A) 100 parts by weight of a film-forming hydroxyl-containing resin of a specified narrow molecular weight distribution substituted by acid-dissociable groups for a part of the hydroxyl groups which causes an increase of solubility in an aqueous alkaline solution by the interaction with an acid; and(B) from 0.5 to 20 parts by weight of a radiation-sensitive acid-generating agent which is a disulfone compound represented by the general formulaR.sup.1 --SO.sub.2 --(C.dbd.N.sub.2 ).sub.n --SO.sub.2 --R.sup.2,in which the subscript n is 0 or 1 and R.sup.1 and R.sup.2 are each, independently from the other, a monovalent cyclic group selected from the group consisting of pyridyl group, benzoxazolyl group and aryl groups substituted by at least one amino group or dialkylamino group, such as bis(4-pyridylsulfonyl) diazomethane, bis(benzoxazolyl-2-sulfonyl) diazomethane, bis(4-dimethylaminophenylsulfonyl) diazomethane and bis(5-dimethylamino-1-naphthyl) disulfone.

Abstract translation: 提出了一种正性化学增感光致抗蚀剂组合物，其在图案化抗蚀剂层的图案化高分辨率，高光敏性和正交截面轮廓方面具有优点，以及在性能对基材性质的几乎不依赖性方面具有优势 表面。 该组合物包含：（A）100重量份具有特定窄分子量分布的成膜羟基树脂，其部分羟基被酸解离基团取代，导致在碱性水溶液中的溶解度增加 溶液与酸的相互作用; 和（B）0.5〜20重量份作为通式R 1 -SO 2（C = N 2）n -SO 2 -R 2表示的二砜化合物的辐射敏感性发酸剂，其中下标n 是0或1，R 1和R 2各自独立地选自吡啶基，苯并恶唑基和被至少一个氨基或二烷基氨基取代的芳基的一价环状基团，例如双（4 （4-二甲基氨基苯磺酰基）重氮甲烷和双（5-二甲基氨基-1-萘基）二砜。

公开(公告)号：US5770343A

公开(公告)日：1998-06-23

申请号：US654522

申请日：1996-05-29

Applicant: Kazufumi Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Yoshika Sakai ,  Toshimasa Nakayama

Inventor： Kazufumi Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Yoshika Sakai ,  Toshimasa Nakayama

IPC: G03F7/004 ,  G03F7/039 ,  H01L21/027 ,  G03F7/30

CPC classification number: G03F7/039 ,  G03F7/0045 ,  Y10S430/106

Abstract: Proposed is a novel positive-working photoresist composition of the chemical sensitization type capable of giving a finely patterned resist layer having an excellent cross sectional profile even for a discretely isolated pattern with high sensitivity and high resolution. The composition comprises, besides (a) a compound generating an acid by the irradiation with actinic rays, (b) a resinous ingredient capable of being imparted with increased solubility in an alkaline developer solution in the presence of an acid and (c) an organic solvent which is a ketone, ether or ester as the basic ingredients of the chemical sensitization type photoresist compositions, (d) an N,N-dialkyl carboxylic acid amide such as N,N-dimethyl formamide and N,N-dimethyl acetamide in a specified proportion relative to the component (b).

公开(公告)号：US5955240A

公开(公告)日：1999-09-21

申请号：US738784

申请日：1996-10-29

Applicant: Kazufumi Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Yoshika Sakai ,  Toshimasa Nakayama

Inventor： Kazufumi Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Yoshika Sakai ,  Toshimasa Nakayama

IPC: G03F7/004 ,  G03F7/039 ,  H01L21/027

CPC classification number: G03F7/0392 ,  G03F7/0045 ,  Y10S430/106

Abstract: Disclosed is an improved, chemically-amplifying positive resist composition for radiations, especially UV rays, deep-UV rays, excimer laser beams, X-rays, electron beams. The composition comprises (A) a resin component whose solubility in an alkaline aqueous solution is increased by the action of acids, (B) a chemical compound which generates an acid when exposed to radiations, and (C) an organic carboxylic acid compound and (D) an amine, in which said resin component (A) is a mixture comprising (a) a polyhydroxystyrene having a weight-average molecular weight of from 8,000 to 25,000 and a molecular weight distribution (Mw/Mn) of 1.5 or less where from 10 to 60 mol % of the hydroxyl groups have been substituted by residues of a general formula (I): ##STR1## wherein R.sup.1 represents a hydrogen atom or a methyl group, R.sup.2 represents a methyl group or an ethyl group, and R.sup.3 represents a lower alkyl group having 1 to 4 carbon atoms;and (b) a polyhydroxystyrene having a weight-average molecular weight of from 8,000 to 25,000 and a molecular weight distribution (M.sub.w /M.sub.n) of 1.5 or less where from 10 to 60 mol % of the hydroxyl groups have been substituted by tert-butoxycarbonyloxy groups. The composition has a high sensitivity, a high resolution, high heat resistance, good width characteristic in focus depth and good post-exposure storage stability, has good storage stability as a resist solution, and gives resist patterns with good profiles, without depending on the substrate to which it is applied. The composition is useful for forming fine patterns in producing ultra-LSIs.

Abstract translation: 公开了用于辐射，特别是紫外线，深紫外线，准分子激光束，X射线，电子束的改进的化学增幅正性抗蚀剂组合物。 该组合物包含（A）通过酸的作用在碱性水溶液中的溶解度增加的树脂成分，（B）暴露于辐射时产生酸的化合物，（C）有机羧酸化合物和（ D）胺，其中所述树脂组分（A）是包含（a）重均分子量为8,000至25,000的聚羟基苯乙烯和分子量分布（Mw / Mn）为1.5以下的混合物，其中， 10〜60mol％的羟基已被通式（I）的残基取代：其中R1表示氢原子或甲基，R2表示甲基或乙基，R3表示低级烷基 具有1至4个碳原子; 和（b）重均分子量为8,000〜25,000，分子量分布（Mw / Mn）为1.5以下的聚羟基苯乙烯，其中10〜60摩尔％的羟基已被叔丁氧羰基氧基 团体 该组合物具有高灵敏度，高分辨率，高耐热性，聚焦深度的良好宽度特性和良好的曝光后储存稳定性，作为抗蚀剂溶液具有良好的储存稳定性，并且具有良好外形的抗蚀剂图案，而不依赖于 底物。 该组合物可用于在制造超LSI时形成精细图案。

公开(公告)号：US5874195A

公开(公告)日：1999-02-23

申请号：US966791

申请日：1997-11-10

Applicant: Kazufumi Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Yoshika Sakai ,  Toshimasa Nakayama

Inventor： Kazufumi Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Yoshika Sakai ,  Toshimasa Nakayama

IPC: G03F7/004 ,  G03F7/039 ,  H01L21/027 ,  G03F7/30

CPC classification number: G03F7/039 ,  G03F7/0045 ,  Y10S430/106

Abstract: Proposed is a novel positive-working photoresist composition of the chemical sensitization type capable of giving a finely patterned resist layer having an excellent cross sectional profile even for a discretely isolated pattern with high sensitivity and high resolution. The composition comprises, besides (a) a compound generating an acid by the irradiation with actinic rays, (b) a resinous ingredient capable of being imparted with increased solubility in an alkaline developer solution in the presence of an acid and (c) an organic solvent which is a ketone, ether or ester as the basic ingredients of the chemical sensitization type photoresist compositions, (d) an N,N-dialkyl carboxylic acid amide such as N,N-dimethyl formamide and N,N-dimethyl acetamide in a specified proportion relative to the component (b).

Abstract translation: 提出了一种新型的化学增感型正性光致抗蚀剂组合物，即使对于具有高灵敏度和高分辨率的离散隔离图案，也能够给出具有优异横截面轮廓的精细图案化的抗蚀剂层。 除了（a）通过光化射线照射产生酸的化合物外，组合物还包含（b）能够在酸存在下赋予碱性显影剂溶液中增加的溶解性的树脂成分，和（c）有机 作为化学增感型光致抗蚀剂组合物的基本成分的酮，醚或酯的溶剂，（d）N，N-二甲基甲酰胺如N，N-二甲基甲酰胺和N，N-二甲基乙酰胺 相对于组分（b）的指定比例。

公开(公告)号：US5856058A

公开(公告)日：1999-01-05

申请号：US660378

申请日：1996-06-07

Applicant: Kazufumi Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Yoshika Sakai ,  Toshimasa Nakayama

Inventor： Kazufumi Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Yoshika Sakai ,  Toshimasa Nakayama

IPC: G03F7/004 ,  G03F7/022 ,  G03F7/039 ,  G03F7/09 ,  H01L21/027 ,  G03F7/023

CPC classification number: G03F7/0226 ,  G03F7/022 ,  G03F7/091

Abstract: Proposed is a novel chemical sensitization-type positive-working photoresist composition used for the photolithographic patterning works in the manufacture of semiconductor devices exhibiting an excellent halation-preventing effect in the patternwise exposure to light. The composition comprises, in addition to conventional ingredients including an acid-generating agent capable of releasing an acid by the irradiation with actinic rays and a resinous ingredient capable of being imparted with increased solubility in an aqueous alkaline developer solution in the presence of an acid, a unique halation inhibitor which is an esterification product between a specified phenolic compound and a naphthoquinone-1,2-diazide sulfonic acid.

Abstract translation: 提出了一种新型化学增感型正性光致抗蚀剂组合物，用于制造在图案曝光中具有优异的防晕效果的半导体器件中的光刻图案化工作。 该组合物除了包括能够通过光化射线照射释放酸的酸产生剂和能够在酸存在下在碱性显影剂水溶液中赋予增加的溶解性的树脂成分之外， 一种独特的卤化抑制剂，它是指定的酚类化合物与萘醌-1,2-二叠氮磺酸之间的酯化产物。

公开(公告)号：US5854357A

公开(公告)日：1998-12-29

申请号：US20411

申请日：1998-02-09

Applicant: Mitsuru Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Etsuko Iguchi ,  Yoshika Sakai ,  Kazufumi Sato ,  Toshimasa Nakayama

Inventor： Mitsuru Sato ,  Kazuyuki Nitta ,  Akiyoshi Yamazaki ,  Etsuko Iguchi ,  Yoshika Sakai ,  Kazufumi Sato ,  Toshimasa Nakayama

IPC: G03F7/004 ,  G03F7/039 ,  C08F8/00

CPC classification number: G03F7/039 ,  G03F7/0045 ,  Y10S430/106

Abstract: A polyhydroxystyrene where from 10 to 60 mol % of the hydroxyl groups have been substituted by tert-butoxycarbonyloxy groups.

Abstract translation: 聚羟基苯乙烯，其中10至60摩尔％的羟基已被叔丁氧羰基氧基取代。