JPS622251A - Photosensitive resin composition and pattern formation - Google Patents

Photosensitive resin composition and pattern formation

Info

Publication number
JPS622251A
JPS622251A JP60141400A JP14140085A JPS622251A JP S622251 A JPS622251 A JP S622251A JP 60141400 A JP60141400 A JP 60141400A JP 14140085 A JP14140085 A JP 14140085A JP S622251 A JPS622251 A JP S622251A
Authority
JP
Japan
Prior art keywords
resin composition
photosensitive resin
aromatic group
group
different
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP60141400A
Other languages
Japanese (ja)
Inventor
Haruyori Tanaka
啓順 田中
Katsuhide Onose
小野瀬 勝秀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Telegraph and Telephone Corp
Original Assignee
Nippon Telegraph and Telephone Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Telegraph and Telephone Corp filed Critical Nippon Telegraph and Telephone Corp
Priority to JP60141400A priority Critical patent/JPS622251A/en
Publication of JPS622251A publication Critical patent/JPS622251A/en
Pending legal-status Critical Current

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Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/72Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

PURPOSE:To obtain a negative type photoresist high in sensitivity to UV rays and to enhance dry etching resistance by incorporating an onium salt producing an acid on photodecomposition and a sensitizing dye in polymethyl (meth) acrylate having an epoxy group. CONSTITUTION:The polymethacrylate having, in the molecule, silicone and epoxy groups each represented by formula (I) contains at least one of the onium salts represented by formula (II), (III), and (VI), and a spectral sensitizer. In the formulae, R is H or alkyl; each of R<1>-R<3> is alkyl, silyl, or optionally substituted aryl, and each may be same or different; each of l, m, n is a positive integer; each of R<4>-R<6> optionally substituted aryl and may be same or different; and MXa is BF4, PF6, AsF6, or SbF6.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は感光性樹脂組成物とパターン形成方法に関し、
更に詳しくは紫外線用ネガ形ホトレジスト材料とそれを
2層レジストの上層レジストとして用いるパターン形成
方法に関する。
Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a photosensitive resin composition and a pattern forming method,
More specifically, the present invention relates to a negative photoresist material for ultraviolet rays and a pattern forming method using the same as an upper layer resist of a two-layer resist.

(従来の技術) 従来、  LSI加工プロセスにおけるパターン形成に
はスループットKfiれたホトリソグラフィが広く用い
られている。感光性樹脂組成物すなわちホトレジストに
は高感度・高解像性を満足し、しかもLSI加工におけ
るプラズマ加工耐性の高いノボラック樹脂系ポジ形ホト
レジストが使用されている。
(Prior Art) Conventionally, photolithography with a throughput of Kfi has been widely used for pattern formation in LSI fabrication processes. As the photosensitive resin composition, that is, the photoresist, a novolac resin-based positive photoresist is used, which satisfies high sensitivity and high resolution, and has high resistance to plasma processing in LSI processing.

しかし、近年配線の多層化、三次元アレイ構造の素子な
どを実現するために段差のある基板上にレジストハター
ンを形成することが望まれている。
However, in recent years, it has been desired to form a resist pattern on a substrate with steps in order to realize multilayer wiring, elements with a three-dimensional array structure, and the like.

したがって段差をカバーするために、レジスト膜を厚く
する必些かある。
Therefore, it is necessary to thicken the resist film in order to cover the level difference.

更に、高速のイオンを基板に到達させることなく捕獲す
るには、レジスト膜厚も厚くしなくてはならない。しか
し従来のレジストでは、膜厚が厚くなるに従い解像性が
低下し、@細なパターン乞形成することができなかった
、 この問題を解決するために、レジストを7層ではなく多
層化することにより、膜厚が厚く、しかも微細な高形状
比パターンを形成する方法が提案されている。すなわち
、m1tei目に有機ポリマーの厚膜を形成し、その上
の第2層VC薄膜のレジスト材料を形成したのち第2J
C,4のレジスト材料に紫外線を照射し、i像後得られ
るパターンをマスクとして第1 、+−の有機ポリマー
を酸素プラズマエツチング(0,1目E)で異方性エツ
チングすることにより、高形状比のパターンを得ようと
するものである( n、 J、 Lln 5olid 
S+a+e Technol、 j4’ 73(/FJ
’/))。
Furthermore, in order to capture high-speed ions without them reaching the substrate, the resist film must also be thick. However, with conventional resists, the resolution decreases as the film thickness increases, making it impossible to form fine patterns. Accordingly, a method of forming a thick and fine pattern with a high shape ratio has been proposed. That is, after forming a thick film of an organic polymer on the m1tei and forming a resist material for the second layer VC thin film thereon, the second J
The resist material C, 4 is irradiated with ultraviolet rays, and the pattern obtained after the i-image is used as a mask to anisotropically etch the first and + organic polymers by oxygen plasma etching (0, 1 E). The purpose is to obtain a shape ratio pattern (n, J, Lln 5olid
S+a+e Technol, j4' 73(/FJ
'/)).

この場合第λ層のレジスト材料はO!月E耐性が高くな
ければならないので、S1含有ポリマを用いることが提
案されている。
In this case, the resist material of the λ-th layer is O! It has been proposed to use S1-containing polymers since the E resistance must be high.

例えば、ハザキスらはポリメチルビニルシロキサンを用
いてパターン形成した( M、 Hatzabis e
ta11’roc、 Intl (Enn(9Micr
o、+  / 71八PjJ’&)。
For example, Hatzabis et al. used polymethylvinylsiloxane to form patterns (M, Hatzabis et al.
ta11'roc, Intl (Enn(9Micr
o, +/718PjJ'&).

しかしながら、ンロキサンボリマはガラス転移温度(T
g)が室温より低く、はこりが付着しやすい、膜厚制御
が困維、現像時のパターン変形による解像性低下などの
問題がある。′rg  を向上させるため1則鎖ンCフ
ェニル4鼻を)4本人(7たクロロメチル化ポリフェニ
ルンロキサンは磁子巌、xgvこ対しては感度は高いが
紫外線に対しては低感度であり。
However, the glass transition temperature (T
g) is lower than room temperature, causing problems such as flakes are likely to adhere, film thickness control is difficult, and resolution is reduced due to pattern deformation during development. In order to improve the rg, the chloromethylated polyphenylated polyphenylene loxane is highly sensitive to xgv, but has low sensitivity to ultraviolet rays. can be.

ホトレジストとして使用できない欠点があった(  M
、   Morila  elal  ;   J、 
  Electrochrm   Soc    /J
/   (10)/りg4t 1”、2110.2>。
There was a drawback that it could not be used as a photoresist (M
, Morila elal; J.
Electrochrm Soc/J
/ (10)/g4t 1”, 2110.2>.

(発明が解決しようとする問題点) 本発明の目的は上記の問題点を解決した高゛r。(Problem to be solved by the invention) The object of the present invention is to solve the above-mentioned problems.

で紫外線に対し高感度なそして0.ILIE耐性に優れ
之感光性樹脂組成物およびそれを使用し之パターン形成
方法を提供することにある。
Highly sensitive to ultraviolet light and 0. An object of the present invention is to provide a photosensitive resin composition having excellent ILIE resistance and a pattern forming method using the same.

(問題点を解決するための手段) 本発明を概説すれば1本発明のg/の発明は感光性樹脂
組成物に関する発明であって、下記一般式(11 (但し、Rは水素またはアルキル基、 R’l R21
凡3はアルキル基、シリル基、芳香族基、ま之は置換芳
香族基の中から選ばれた7種を示し、互に同じでも異な
っていてもよく、又、tm+ nは正の整数を示す)で
表わされるシリコン含有メタクリレートポリマーに下記
一般式(■l、@1.(財)でN、 MXa(II) 1”L’fL’I  MXa@) 几’R’R’S  MXa             
                  (g(几’+R
’+几6は芳香族基ま比は置換芳香族基を示し、同じで
あっても異なっていても良い。MX、は11F、 l 
PF、l、八5k”6 + Sbk’@の中から選ばれ
fc/種を示す。)で表わされるオニウム塩を/種類以
上および分光増感剤を添加したことを特徴とする。
(Means for Solving the Problems) To summarize the present invention, the g/invention of the present invention relates to a photosensitive resin composition, which has the following general formula (11 (where R is hydrogen or an alkyl group). , R'l R21
3 represents an alkyl group, a silyl group, an aromatic group, and a symbol represents 7 types selected from substituted aromatic groups, which may be the same or different, and tm+n represents a positive integer. MXa (II) 1"L'fL'I MXa@) 几'R'R'S MXa
(g(几'+R
'+几6 represents an aromatic group, and the ratio represents a substituted aromatic group, which may be the same or different. MX, is 11F, l
It is characterized by the addition of at least one onium salt selected from PF, 1, 85k''6 + Sbk'@ and represented by fc/species) and a spectral sensitizer.

また、本発明の第2の発明はパターン形成方法に関する
発明であって、基材上に有機高分子材層を設け、その上
に感光性樹脂組成物層を設け、その後紫外線を所望のパ
ターン状に照射し、照射部位のみ該感光性樹脂組成物層
を現像溶媒に不溶化させ、現像により未照射部の感光性
樹脂組成物を除去したのち、照射部分の感光性樹脂組成
物をマスクとして酸素を用いるドライエツチングにより
該感光性樹脂組成物で覆われていない部分の該有機高分
子材層をエツチング除去することによりパターンを形成
する方法において、上記シリコン含有メタクリレートポ
リマにオニウム塩を添加してなる感光性樹脂組成物を用
いることを特徴とする。
Further, the second invention of the present invention relates to a pattern forming method, in which an organic polymer material layer is provided on a base material, a photosensitive resin composition layer is provided thereon, and then ultraviolet rays are applied to form a desired pattern. The photosensitive resin composition layer in only the irradiated area is insolubilized in a developing solvent, and the photosensitive resin composition in the unirradiated area is removed by development. Oxygen is then irradiated using the photosensitive resin composition in the irradiated area as a mask. In the method of forming a pattern by etching away the portions of the organic polymer material layer that are not covered with the photosensitive resin composition by dry etching, the photosensitive material is prepared by adding an onium salt to the silicon-containing methacrylate polymer. The method is characterized by using a resin composition with a viscous character.

一般式中のtが大きくなると溶媒溶解性が低下し、使用
しうる現像溶媒の範囲がケトン類にまで拡大てれ、高解
像性のパターン形成に有利となる。
When t in the general formula becomes large, the solvent solubility decreases, and the range of usable developing solvents is expanded to include ketones, which is advantageous for high-resolution pattern formation.

しかし、tの増大はSi含有率の低下をまねき、酸素プ
ラズマ耐性が低下すること、あるいはガラス転移温度(
Tg)が低下し、材料がガム状となって扱1.−.K(
くなるなどの欠点がある。特に、シリコンの重量含有率
がlλ−以下になると酸素プラズマ耐性が著しく減少す
るため、tVi3以下であることが好ましい。
However, an increase in t leads to a decrease in the Si content, resulting in a decrease in oxygen plasma resistance or a glass transition temperature (
Tg) decreases and the material becomes gummy and cannot be handled 1. −. K(
There are drawbacks such as: In particular, if the weight content of silicon is less than lλ-, the oxygen plasma resistance will be significantly reduced, so it is preferably less than tVi3.

架橋を生じ、当該材料の溶媒浴解性を低下させる。Crosslinking occurs, reducing the solvent bath solubility of the material.

したがって感光性樹脂組成物はネガ形ホトレジストとな
る。口が増大すればrRにより、架橋が生じやすくなる
が、S1含有率の低下をまねき、酸素プラズマ耐性が低
下する。このため、口は当該材料の光架橋が生ずる最低
盆でよ< n/(m+n)が0、.20以王好ましくは
0. / 0−0. Ojである。
Therefore, the photosensitive resin composition becomes a negative photoresist. If the opening increases, crosslinking becomes more likely to occur due to rR, but this leads to a decrease in S1 content and oxygen plasma resistance decreases. Therefore, the opening should be the lowest tray where photocrosslinking of the material occurs. 20 or more, preferably 0. / 0-0. It's Oj.

次にオニウム塩としてはスル7オニウム塩、ヨードニウ
ム塩、ジアゾニウム塩があげられる。ジアゾニウム塩以
外は吸収が300 nm以下にある念め、近紫外線(3
jO−4L30 nm) Ig:、対して光分解しにく
い。このため分光増感が必要となる。分光増感剤として
はペリレンなどの多環芳香族、ベニル化合物、ニトロベ
ンゼン、P−ニトロフェノール、P−ニトロアニリン等
の芳香族ニトロ化合物。
Examples of onium salts include sulfonium salts, iodonium salts, and diazonium salts. To be sure that all substances other than diazonium salts have absorption below 300 nm, use near ultraviolet light (300 nm or less).
jO-4L30 nm) Ig:, is difficult to photodecompose. For this reason, spectral sensitization is required. Spectral sensitizers include polycyclic aromatics such as perylene, benyl compounds, aromatic nitro compounds such as nitrobenzene, P-nitrophenol, and P-nitroaniline.

アントラキノ/のキノン系化合物、j−−40アセナフ
テンのア七ナフテン系化合物、アントロン系化合物が有
効である。
Anthraquino/quinone compounds, j--40 acenaphthene a7naphthene compounds, and anthrone compounds are effective.

次に、有機ポリマーとしては、酸素プラズマによりエツ
チングされるものであればいずれのものでもよいが、パ
ターン形成後これをマスクとして基板をドライエツチン
グする際、耐性を高めるため、芳香族含有ポリマーが好
ましい。
Next, as the organic polymer, any organic polymer may be used as long as it can be etched by oxygen plasma, but aromatic-containing polymers are preferred in order to increase resistance when dry etching the substrate using this as a mask after pattern formation. .

例えばポリエステル系、ノボラック系、エポキシ系・ 
ポリアミドイミド系、ポリイミド系樹脂など広範囲な高
分子物質を適用することができる。
For example, polyester, novolak, epoxy, etc.
A wide range of polymeric substances such as polyamide-imide and polyimide resins can be applied.

さらに一般式(1)(II)([11)IIM)中ノR
’、 R” 、 R” 、 R’ 、 R’。
Furthermore, R in general formula (1) (II) ([11) IIM]
', R'', R'', R', R'.

几6 の置換芳香族の置換基としてはメチル基、エチル
基、グリンジル基、ビニル基、プロピル基。
Examples of the substituted aromatic substituents of 几6 include a methyl group, an ethyl group, a grindyl group, a vinyl group, and a propyl group.

フェニル基、ナフチル基、メチルフェニ’L−[、fロ
ロメチルフェニル基、とニルフェニル基ナトカ上げられ
る。
Examples include phenyl group, naphthyl group, methylphenyl group, f-lolomethylphenyl group, and nylphenyl group.

当該材料のシリコン含有メタクリレートポリマの製造方
法としては、メタクリル酸カリウムとR’ + R” 
、几3Viアルキル基、シリル基、芳香族基。
As a method for producing the silicon-containing methacrylate polymer of the material, potassium methacrylate and R' + R''
, 几3Vi alkyl group, silyl group, aromatic group.

又は置換芳香族基を示し、tは正の整数を示す)との反
応によりSi含有メタクリレートモノマーを製造し、こ
れとグリシジルメタクリレートを共重合することにより
得られる。
or a substituted aromatic group, and t is a positive integer) to produce a Si-containing methacrylate monomer, and copolymerizing this with glycidyl methacrylate.

以下、本発明を実施例により更に具体的に説明するが1
本発明はこれら実施例に限定されない。
Hereinafter, the present invention will be explained in more detail with reference to Examples.
The invention is not limited to these examples.

(実施例/〜≠) トリメチルシリルメチルメタクリレートとグリシジルメ
タクリレートの共重合比がPJ−/夕 であるシリコン
含有メタクリレートポリマを合成し、それに各種ジアゾ
、7ニウム塩を上記ポリマに対し10重量%添加したと
きのレジスト特性を表/に示す。
(Example/~≠) When a silicon-containing methacrylate polymer in which the copolymerization ratio of trimethylsilyl methyl methacrylate and glycidyl methacrylate is PJ-/Y was synthesized, and 10% by weight of various diazo and 7nium salts were added to the above polymer. Table 1 shows the resist characteristics of .

感度及び解像性の評価は以下の方法で行つ几。Siウェ
ー・に約0.2μm厚さで材料を塗布し、jOoCで3
0分間Nt気流中グリベークした。グリベーク後、超高
圧水銀灯を用いて紫外線を照射した。
Sensitivity and resolution are evaluated using the following method. The material was applied to the Si wafer to a thickness of approximately 0.2 μm, and
Gribake was carried out in a Nt stream for 0 minutes. After glybake, ultraviolet rays were irradiated using an ultra-high pressure mercury lamp.

照射後、ジアセトンアルコールとエチルシクロヘキサン
(/// )の混合溶媒で現像し、照射部の残膜が初期
膜厚のJ′osとなるところの照射量を感度とした。解
像性は正方形の残しパターンを紫外線露光、現像した時
、剥離せずに・ζターンが形成できろ最小の正方形の一
辺の長さで評価した。感度はいずれも100mJ/Cm
”以下であり、エツチング速度はJ″nm / m l
 n以下であり之。この結果より2層レジストの上層レ
ジストとして使用できる。
After irradiation, development was performed with a mixed solvent of diacetone alcohol and ethylcyclohexane (///), and the irradiation amount at which the residual film in the irradiated area became J'os, the initial film thickness, was defined as the sensitivity. Resolution was evaluated based on the length of the smallest square side that could form a ζ-turn without peeling when the remaining square pattern was exposed to ultraviolet light and developed. Sensitivity is 100mJ/Cm for both
” and the etching rate is J”nm/ml
It is less than or equal to n. From this result, it can be used as an upper layer resist of a two-layer resist.

(実施例!〜ざ) 実施例/のシリコン含有メタクリレートポリマに各種ヨ
ードニウム塩をポリマに対して10重黛チそして分光増
感剤としてチオキサントンを0.5重量%添加したとき
のレジスト特性を表2に示す。
(Example!~) Table 2 shows the resist properties when various iodonium salts were added at 10% by weight to the silicon-containing methacrylate polymer of Example / and 0.5% by weight of thioxanthone was added as a spectral sensitizer. Shown below.

評価は実施例/と同様で行った。現像溶媒とじてはジイ
ソブチルケトンとエチルシクロヘキサン(///)の混
合液を用いた。
Evaluation was performed in the same manner as in Example. A mixed solution of diisobutyl ketone and ethylcyclohexane (///) was used as the developing solvent.

(実施例り〜/l) 実施例/のシリコン含有メタクリレートポリマに各種ス
ル7オニウム塩をポリマに対してlO重i%そして分光
増感剤としてフェノチアジンを0、3−重量%添加した
ときのレジスト特性t−表3に示す。評価は実施例/ど
同様に行った。現像溶媒は実施例j−J’と同じものを
用いた。
(Example ~/l) Resist obtained when various sulfonium salts were added to the silicon-containing methacrylate polymer of Example / in an amount of 10% by weight based on the polymer, and 0.3% by weight of phenothiazine was added as a spectral sensitizer. Characteristics t-shown in Table 3. Evaluation was carried out in the same manner as in Examples. The same developing solvent as in Examples j-J' was used.

(実施例73〜/7) 実施例IOにおけるフェノチアジンの代りに各種分光増
感剤を0.!重jTh%添加し几ときのレジスト特性を
表グに示す。評価は実施例IOと同様に行った。比較例
として無添加のものをあげたが、分光増感により高感度
化されることがわかる。
(Example 73-/7) Various spectral sensitizers were used in place of the phenothiazine in Example IO. ! The resist properties when a heavy jTh% is added are shown in Table 1. Evaluation was performed in the same manner as in Example IO. As a comparative example, a sample without additives was shown, but it can be seen that the sensitivity can be increased by spectral sensitization.

(実施例/r−,2/) 実施例l0VCおいてシリコン含有メタクリレートの共
重合比を変化させたときのレジスト特性を表jに示す。
(Example/r-, 2/) Table j shows the resist characteristics when the copolymerization ratio of silicon-containing methacrylate was changed in Example 10VC.

評価は実施例10と同様に行っ之。Evaluation was carried out in the same manner as in Example 10.

グリシジルメタクリレートの量が増加するに伴い感度は
向上するが、酸素プラズマに対するエツチング速度が大
きくなる欠点があつ之。
As the amount of glycidyl methacrylate increases, the sensitivity improves, but the drawback is that the etching rate with respect to oxygen plasma increases.

(実施例λλ) シリコンウェハ上に人Z−/310  レジスト(シブ
レー社!B)を1μmの厚さに塗布し、200″Cで3
0分間加熱し不溶化させた。このAzレジストの上に実
施例10に示し念感光性樹脂組成物を0.2μmの厚さ
に塗布し、50°Cで30分間N。
(Example λλ) A silicon wafer was coated with Jin Z-/310 resist (Sibley Co., Ltd.!B) to a thickness of 1 μm, and heated at 200″C for 3
It was heated for 0 minutes to insolubilize it. On this Az resist, the photosensitive resin composition shown in Example 10 was applied to a thickness of 0.2 μm, and N was heated at 50° C. for 30 minutes.

気流中プリベークした。プリベーク後、紫外線照射を行
っ之。照射後、実施例ioに示し次現像溶媒で現像し、
O1!μmスペースを/、0μmピッチで形成した。そ
の後平行平板型ドライエツチング装置で酸素ガスをエッ
チャントガスとしてエツチングを行った。
Prebaked in airflow. After prebaking, UV irradiation was performed. After irradiation, it is developed with the following developing solvent as shown in Example io,
O1! μm spaces were formed at a pitch of /, 0 μm. Thereafter, etching was performed using a parallel plate type dry etching apparatus using oxygen gas as an etchant gas.

酸素ガス圧lOミリトル、  RF’パワー〇、/WΔ
が。
Oxygen gas pressure lO millitorr, RF' power〇, /WΔ
but.

電極電圧0.7 KVのエツチング条件では実施例10
の感光性樹脂組成物のエツチング速度は3 nm /m
in以下であり念。ま九、A!レジストのエツチング速
度はIOnm1分であり、1llL分間のエツチングで
感光性樹脂組成物VC覆われない部分のAxレジストは
完全に基板上から消失し之。エソチンyn、o、rμm
のスペースパターンがレジスト厚/1.2μmで形成で
きた。これは従来の単層のホトレジストで解像できない
領域である。
Example 10 under etching conditions of electrode voltage 0.7 KV.
The etching rate of the photosensitive resin composition is 3 nm/m
Just in case it is less than in. Maku, A! The etching rate of the resist was IO nm 1 minute, and the portion of the Ax resist not covered with the photosensitive resin composition VC completely disappeared from the substrate after etching for 111 minutes. Esotin yn, o, rμm
A space pattern of 1.2 μm was formed with a resist thickness of 1.2 μm. This is an area that cannot be resolved with conventional single layer photoresist.

(発明の効果) 以上説明したように5本発明で得られ念感光性樹脂組成
物はエポキシ基を含有するメタクリレートポリマに光分
解により酸を生ずるオニウム塩と増感剤を加えた之め紫
外線に対して高感度のネガ形ホトレジストとなる。
(Effects of the Invention) As explained above, the photosensitive resin composition obtained by the present invention is made by adding an onium salt and a sensitizer that produce an acid upon photolysis to a methacrylate polymer containing an epoxy group, so that it is resistant to ultraviolet rays. On the other hand, it becomes a highly sensitive negative photoresist.

ま之、シリコンを含有するため酸素プラズマ耐性が高く
、シたがって2層レジストの上j−レジストとして使用
できる。1層レジストは下層に芳香族含有ポリマーが使
用できるので基板加工に用いるドライエツチングへの耐
性が高<、te、下層を厚くすることにより、基板上の
段差を平坦化し、上層レジストを薄く均一に塗布でき、
高解像化できる。このため、本発明に°よれば、従来の
ホトレジストでは達成できなかった高感度で高形状比。
However, since it contains silicon, it has high resistance to oxygen plasma, and therefore can be used as an upper J-resist of a two-layer resist. Single-layer resists can use aromatic-containing polymers in the lower layer, so they have high resistance to dry etching used in substrate processing. By making the lower layer thicker, the steps on the substrate can be flattened, making the upper resist layer thinner and more uniform. Can be applied,
High resolution possible. Therefore, according to the present invention, high sensitivity and high shape ratio, which could not be achieved with conventional photoresists, can be achieved.

しかもCF、などを用いるドライエツチング耐性の高い
パターンを形成できるという顕著な効果がある。
Moreover, it has the remarkable effect of forming a pattern with high dry etching resistance using CF or the like.

Claims (2)

【特許請求の範囲】[Claims] (1)下記一般式( I ) ▲数式、化学式、表等があります▼ (但し、Rは水素またはアルキル基、R^1、R^2、
R^3はアルキル基、シリル基、芳香族基、または置換
芳香族基の中から選ばれた1種を示し、互に同じでも異
なっていても良く、またl、m、nはそれぞれ正の整数
を示す。)で表わされるシリコン含有メタクリレートポ
リマに 下記一般式(II)、(III)、(IV) R^4N^+_2MX^−_a R^4R^5I^+MX^−_a R^4R^5R^6S^+MX^−_a (R^4、R^5、R^6は芳香族基または置換芳香族
基を示し、同じであっても異なっていても良い。 MX_aはBF_4、PF_6、AsF_6、SbF_
6の中から選ばれた1種を示す。) で表わされるオニウム塩を1種類以上および分光増感剤
を添加したことを特徴とする感光性樹脂組成物。
(1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R is hydrogen or an alkyl group, R^1, R^2,
R^3 represents one type selected from an alkyl group, a silyl group, an aromatic group, or a substituted aromatic group, and may be the same or different, and l, m, and n each represent a positive Indicates an integer. ) to silicon-containing methacrylate polymers represented by the following general formulas (II), (III), (IV) R^4N^+_2MX^-_a R^4R^5I^+MX^-_a R^4R^5R^6S^+MX ^-_a (R^4, R^5, R^6 represent an aromatic group or a substituted aromatic group, and may be the same or different. MX_a is BF_4, PF_6, AsF_6, SbF_
One type selected from 6 is shown. 1. A photosensitive resin composition comprising one or more onium salts represented by the following formula and a spectral sensitizer.
(2)基材上に有機高分子材層を設け、その上に感光性
樹脂組成物層を設け紫外線を所望のパターン状に照射し
、照射部位のみ該感光性樹脂組成物層を現像溶媒に不溶
化させ、現像により未照射部の該感光性樹脂組成物を除
去したのち、照射部分の感光性樹脂組成物をマスクとし
て酸素を用いるドライエッチングにより該感光性樹脂組
成物で覆われていない部分の該有機高分子材層をエッチ
ング除去することによりパターンを形成する方法におい
て、感光性樹脂組成物として 下記一般式( I ) ▲数式、化学式、表等があります▼ (但し、Rは水素またはアルキル基、R^1、R^2、
R^3はアルキル基、シリル基、芳香族基、または置換
芳香族基の中から選ばれた1種を示し、互に同じでも異
なっていても良く、またl、m、nはそれぞれ正の整数
を示す。)で表わされるシリコン含有メタクリレートポ
リマに 下記一般式(II)、(III)、(IV) R^4N^+_2MX^−_a R^4R^5I^+MX^−_a R^4R^5R^6S^+MX^−_a (R^4、R^5、R^6は芳香族基または置換芳香族
基を示し、同じであっても異なつていても良い。 MX_aはBF_4、PF_6、AsF_6、SbF_
6の中から選ばれた1種を示す。) で表わされるオニウム塩を1種類以上および分光増感剤
を添加したものを用いることを特徴とするパターン形成
方法。
(2) An organic polymer material layer is provided on the base material, a photosensitive resin composition layer is provided on top of the organic polymer material layer, and ultraviolet rays are irradiated in a desired pattern, and only the irradiated areas are coated with the photosensitive resin composition layer in a developing solvent. After insolubilizing and removing the unirradiated areas of the photosensitive resin composition by development, the areas not covered with the photosensitive resin composition are dry-etched using oxygen using the irradiated areas of the photosensitive resin composition as a mask. In the method of forming a pattern by etching away the organic polymer material layer, the photosensitive resin composition has the following general formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R is hydrogen or an alkyl group. , R^1, R^2,
R^3 represents one type selected from an alkyl group, a silyl group, an aromatic group, or a substituted aromatic group, and may be the same or different, and l, m, and n each represent a positive Indicates an integer. ) to silicon-containing methacrylate polymers represented by the following general formulas (II), (III), (IV) R^4N^+_2MX^-_a R^4R^5I^+MX^-_a R^4R^5R^6S^+MX ^-_a (R^4, R^5, R^6 represent an aromatic group or a substituted aromatic group, and may be the same or different. MX_a is BF_4, PF_6, AsF_6, SbF_
One type selected from 6 is shown. A pattern forming method characterized by using one or more onium salts represented by ) and a spectral sensitizer.
JP60141400A 1985-06-27 1985-06-27 Photosensitive resin composition and pattern formation Pending JPS622251A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60141400A JPS622251A (en) 1985-06-27 1985-06-27 Photosensitive resin composition and pattern formation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60141400A JPS622251A (en) 1985-06-27 1985-06-27 Photosensitive resin composition and pattern formation

Publications (1)

Publication Number Publication Date
JPS622251A true JPS622251A (en) 1987-01-08

Family

ID=15291118

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60141400A Pending JPS622251A (en) 1985-06-27 1985-06-27 Photosensitive resin composition and pattern formation

Country Status (1)

Country Link
JP (1) JPS622251A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0247066A (en) * 1988-08-09 1990-02-16 Nec Corp Manufacture of ceramic electronic component

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0247066A (en) * 1988-08-09 1990-02-16 Nec Corp Manufacture of ceramic electronic component

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