JPH11153869A - Chemically amplified resist - Google Patents
Chemically amplified resistInfo
- Publication number
- JPH11153869A JPH11153869A JP9319967A JP31996797A JPH11153869A JP H11153869 A JPH11153869 A JP H11153869A JP 9319967 A JP9319967 A JP 9319967A JP 31996797 A JP31996797 A JP 31996797A JP H11153869 A JPH11153869 A JP H11153869A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- chemically amplified
- resist
- molecular weight
- polyhydroxystyrene
- 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
Links
Landscapes
- Materials For Photolithography (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、半導体集積回路用
フォトレジストに関し、特に現像性解像性の改善された
ポジ型の化学増幅型レジストに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoresist for a semiconductor integrated circuit, and more particularly to a positive chemically amplified resist having improved developability and resolution.
【0002】[0002]
【従来の技術】従来の半導体集積回路の光リソグラフィ
では、露光光にg線(436nm)、i線(365nm)が
使用され、レジストとしては、ベース樹脂にノボラック
樹脂、感光剤にナフトキノンジアジドを用いた溶解抑止
型ポジ型レジストが主流であった。しかしより微細化に
有利な遠紫外光であるエキシマレーザー光(248n
m、193nm等)を用いたリソグラフィが必要とな
り、そのレジストとしは従来のg線、i線用レジストで
は感度が大幅に増大し光吸収が大きすぎるために、良好
なレジストパターンが得られい問題があった。2. Description of the Related Art In conventional photolithography of semiconductor integrated circuits, g-ray (436 nm) and i-ray (365 nm) are used as exposure light, and novolak resin is used as a base resin and naphthoquinone diazide is used as a photosensitive agent. Dissolution-suppressing positive resist was the mainstream. However, excimer laser light (248 n
, 193 nm, etc.), and a conventional g-line or i-line resist has a problem that a good resist pattern cannot be obtained because the sensitivity is greatly increased and light absorption is too large. was there.
【0003】上記従来のレジストの問題点を解決するた
めに、光酸発生剤から発生する酸触媒の増感反応を利用
した化学増幅型レジストが考案され、短波長リソグラフ
ィ用レジスト、また高感度が要求される電子線リソグラ
フィ用レジストとして主流となりつつある。In order to solve the above-mentioned problems of the conventional resist, a chemically amplified resist utilizing a sensitization reaction of an acid catalyst generated from a photoacid generator has been devised. It is becoming mainstream as a required resist for electron beam lithography.
【0004】しかし、化学増幅型レジスト、特に保護型
ポリビニルフェノール樹脂と光酸発生剤から成る2成分
系ポジ型レジスト、もしくはこれに保護型ビスフェノー
ルA等を溶解抑止剤として添加した3成分系ポジ型レジ
ストでは、露光によって発生した酸がレジスト膜表面領
域で消失あるいは空気中の塩基で中和されて失活し、後
の露光後ベーキング(以下、PEBという)処理で可溶
化反応が進行しないため、表面難溶化層が発生し、その
ため図2に示すように、現像後得られるウェハー201
上に形成したレジストパターン202がT型形状にな
り、解像性、焦点深度や寸法精度が損なわれるという問
題点がある。However, a chemically amplified resist, particularly a two-component positive resist comprising a protective polyvinylphenol resin and a photoacid generator, or a three-component positive resist obtained by adding a protective bisphenol A or the like as a dissolution inhibitor thereto. In the resist, the acid generated by the exposure disappears in the surface region of the resist film or is neutralized and deactivated by a base in the air, and the solubilization reaction does not proceed in a subsequent post-exposure baking (hereinafter, referred to as PEB) treatment. A surface insolubilized layer is generated, and therefore, as shown in FIG.
There is a problem that the resist pattern 202 formed thereon has a T-shape and the resolution, the depth of focus and the dimensional accuracy are impaired.
【0005】この問題点を解決する方法として、従来よ
り、いくつかの方法が提案されいる。例えば、特開平4
−369211号公報には、PEB処理の雰囲気を不活
性ガスに置換し酸失活を防止する方法が開示されてい
る。また特開平4−221951号公報には、形成され
た表面難溶化層を薄く取り除く方法や、特開平4−20
4848号公報には、レジスト表面に保護膜を塗布し酸
失活を防止する方法が開示されている。As a method for solving this problem, several methods have been conventionally proposed. For example, JP
JP-B-369211 discloses a method in which the atmosphere of PEB treatment is replaced with an inert gas to prevent acid deactivation. Also, JP-A-4-221951 discloses a method of thinly removing a formed surface insoluble layer,
Japanese Patent No. 4848 discloses a method of applying a protective film on a resist surface to prevent acid deactivation.
【0006】[0006]
【発明が解決しようとする課題】しかし、上記のPEB
処理雰囲気を不活性ガスで置換し、酸失活を防止する方
法では、処理装置が複雑になり、また加工費の増加が避
けられない。また表面難溶化層を薄く取り除く方法で
は、その層の残渣やその層下のレジストの特性への影響
によりレジストの解像性が損なわれる問題が起こりやす
い。However, the above-mentioned PEB
The method of replacing the processing atmosphere with an inert gas to prevent acid deactivation complicates the processing apparatus and inevitably increases the processing cost. Further, in the method of removing the surface insoluble layer thinly, a problem that the resolution of the resist is deteriorated due to the influence on the residue of the layer and the properties of the resist under the layer is likely to occur.
【0007】また、上記のレジスト表面に保護膜を塗布
し酸失活を防止する方法では、レジスト表面での酸失活
の防止に対しては、その効果は不十分で、また露光後P
EB処理までの間にレジスト表面から酸が消失した場
合、この方法では表面難溶化層の形成は防止することが
できず、現像後のレジストパターン形状はT型形状にな
りやすいという問題がある。特に微細パターン形成に対
しては、このような表面難溶化層に起因するフォトレジ
ストパターンの形状劣化、解像性、焦点深度、寸法精度
の劣化は致命的である。Further, the above-mentioned method of applying a protective film to the resist surface to prevent acid deactivation does not have sufficient effect on preventing acid deactivation on the resist surface.
If the acid disappears from the resist surface before the EB treatment, this method cannot prevent the formation of the hardly-solubilized layer on the surface, and the resist pattern after development tends to have a T-shape. In particular, for the formation of a fine pattern, the deterioration of the shape of the photoresist pattern, the resolution, the depth of focus, and the deterioration of the dimensional accuracy caused by such a surface insoluble layer are fatal.
【0008】[0008]
【課題を解決するための手段】本発明の化学増幅型レジ
ストは、少なくともアルカリ難溶の保護基を有する樹脂
と光酸発生剤とから成る化学増幅ポジ型レジスト材料に
ポリヒドロキシスチレン樹脂を溶解促進剤として添加し
た構成からなる。The chemically amplified resist of the present invention promotes dissolution of a polyhydroxystyrene resin in a chemically amplified positive resist material comprising at least a resin having a protective group which is hardly soluble in alkali and a photoacid generator. It has a configuration added as an agent.
【0009】上記、溶解促進剤のポリヒドロキシスチレ
ン樹脂としては、分子量1000〜30000、分子量
分散1.5〜3.5のポリヒドロキシスチレン樹脂が使
用される。このポリヒドロキシスチレン樹脂をアルカリ
難溶の保護基を有する樹脂と光酸発生剤とから成る化学
増幅ポジ型レジスト材料に添加することによりレジスト
表面の現像液に対する溶解速度を促進させ、表面難溶化
層の形成を抑え、化学増幅型ポジ型レジストのT型形状
形成を抑制する効果がある。As the above-mentioned polyhydroxystyrene resin as a dissolution accelerator, a polyhydroxystyrene resin having a molecular weight of 1,000 to 30,000 and a molecular weight dispersion of 1.5 to 3.5 is used. By adding this polyhydroxystyrene resin to a chemically amplified positive resist material comprising a resin having a protective group which is hardly soluble in alkali and a photoacid generator, the dissolution rate of the resist surface in a developing solution is promoted, and the surface hardly soluble layer is formed. Has the effect of suppressing the formation of a T-shaped profile of the chemically amplified positive resist.
【0010】[0010]
【発明の実施の形態】次に、本発明の実施の形態につい
て説明する。本発明の実施の形態の化学増幅型レジスト
に添加される溶解促進剤は、次の一般式(1)で表され
るポリヒドロキシスチレン樹脂である。Next, an embodiment of the present invention will be described. The dissolution promoter added to the chemically amplified resist according to the embodiment of the present invention is a polyhydroxystyrene resin represented by the following general formula (1).
【0011】 [0011]
【0012】但し、nは整数で、ポリヒドロキシスチレ
ン樹脂の分子量によって決まる。Here, n is an integer and is determined by the molecular weight of the polyhydroxystyrene resin.
【0013】上記一般式(1)で表されるポリヒドロキ
シスチレン樹脂は分子量1000〜30000、分子量
分散1.5〜3.5が適当であり、この分子量が100
0未満や分子量分散が3.5を越える場合には、未露光
部の溶解速度が大きくなりすぎ、レジストパターンの矩
形性が損なわれる。また、該樹脂の分子量が30000
を越える場合や分子量分散が1.5未満では、レジスト
パターンがTトップ形状になり、解像性が損なわれる。The polyhydroxystyrene resin represented by the general formula (1) suitably has a molecular weight of 1,000 to 30,000 and a molecular weight dispersion of 1.5 to 3.5.
If it is less than 0 or the molecular weight dispersion exceeds 3.5, the dissolution rate of the unexposed portion becomes too high, and the rectangularity of the resist pattern is impaired. In addition, the molecular weight of the resin is 30,000
When the molecular weight dispersion exceeds 1.5, or when the molecular weight dispersion is less than 1.5, the resist pattern has a T-top shape, and the resolution is impaired.
【0014】上記ポリヒドロキシスチレン樹脂をターシ
ャリブトキシカルボニル(t−BOC)保護ポリヒドロ
キシスチレン樹脂のベース樹脂と光酸発生剤のトリフェ
ニルスルホニウムヘキサフロロアンチモネンとプロピレ
ングリコールモノメチルエーテルアセテート(PGME
A)の溶剤を含む2成分化学増幅ポジ型レジストに対ベ
ース樹脂比で1〜10重量%添加して化学増幅型レジス
トを調整した。The above polyhydroxystyrene resin is prepared by using a base resin of tertiary butoxycarbonyl (t-BOC) -protected polyhydroxystyrene resin, triphenylsulfonium hexafluoroantimonene as a photoacid generator, and propylene glycol monomethyl ether acetate (PGME).
A chemically amplified resist was prepared by adding 1 to 10% by weight of a two-component chemically amplified positive resist containing the solvent in a) with respect to a base resin ratio.
【0015】上記本発明の実施の形態の化学増幅型レジ
ストを使用したパターン形成方法について図1を参照し
て説明する。図1は本発明の実施の形態の化学増幅型レ
ジストの露光現像後のウェハー上のパターンの断面図で
ある。A pattern forming method using the chemically amplified resist according to the embodiment of the present invention will be described with reference to FIG. FIG. 1 is a sectional view of a pattern on a wafer after exposure and development of a chemically amplified resist according to an embodiment of the present invention.
【0016】まず、ウェハー101上に上記の化学増幅
型レジストを回転塗布法で塗布し、レジスト膜を形成し
乾燥する。次いで、所望の半導体集積回路パターンを描
いたマスクまたはレチクルを通してKrFエキシマレー
ザーステッパーで露光量30mJ/cm2 程度で露光
し、100℃で1〜2分のPEB処理をホットプレート
上で行った。First, the above-described chemically amplified resist is applied onto the wafer 101 by a spin coating method, a resist film is formed, and the resist film is dried. Next, exposure was performed with a KrF excimer laser stepper at an exposure amount of about 30 mJ / cm 2 through a mask or reticle on which a desired semiconductor integrated circuit pattern was drawn, and PEB treatment was performed on a hot plate at 100 ° C. for 1 to 2 minutes.
【0017】次いで、液温20〜25℃の約3重量%の
テトラメチルアンモニウムハイドロオキサイド(TMA
H)水溶液で約1分間浸漬して現像を行った。その結
果、図1に示すような表面難溶化層の無い断面形状が矩
形の化学増幅型レジストパターン102を得ることがで
きた。Then, about 3% by weight of tetramethylammonium hydroxide (TMA) at a liquid temperature of 20 to 25 ° C.
H) Development was performed by immersion in an aqueous solution for about 1 minute. As a result, a chemically amplified resist pattern 102 having a rectangular cross-section without the surface insolubilized layer as shown in FIG. 1 could be obtained.
【0018】上記の実施の形態では、レジストのベース
樹脂としてターシャリブトキシカルボニル保護ポリヒド
ロキシスチレン樹脂を使用したが、ターシャリブチルア
クリレート樹脂が使用しても同様の効果を得ることがで
きることが判明した。In the above embodiment, a tertiary butoxycarbonyl-protected polyhydroxystyrene resin was used as the base resin for the resist. However, it has been found that the same effect can be obtained by using a tertiary butyl acrylate resin. .
【0019】[0019]
【発明の効果】以上説明したように本発明の化学増幅型
レジストは、化学増幅型ポジ型レジストパターンのT型
形状をほぼ完全に解消することができ、矩形なレジスト
パターンを得ることができる。また本発明の溶解促進剤
であるポリヒドロキシスチレンの分子量、分子量分散、
またレジスト材料への添加量を調節することにより、レ
ジスト膜の現像液に対する溶解速度を制御することがで
き、レジストの高性能化が可能となる。その結果、解像
性、焦点深度、寸法精度とも10%以上の向上を図るこ
とができる。特に微細パターン形成に対してはその効果
は大きく、矩形のフォトレジストパターンを再現性よく
形成することができる。As described above, the chemically amplified resist of the present invention can almost completely eliminate the T-shaped shape of the chemically amplified positive resist pattern, and can obtain a rectangular resist pattern. Further, the molecular weight of the polyhydroxystyrene as a dissolution promoter of the present invention, molecular weight dispersion,
Further, by adjusting the amount of addition to the resist material, the dissolution rate of the resist film in the developing solution can be controlled, and the performance of the resist can be improved. As a result, it is possible to improve resolution, depth of focus, and dimensional accuracy by 10% or more. In particular, the effect is great for forming a fine pattern, and a rectangular photoresist pattern can be formed with good reproducibility.
【図1】本発明の実施の形態の化学増幅型レジストのパ
ターン断面図である。FIG. 1 is a pattern sectional view of a chemically amplified resist according to an embodiment of the present invention.
【図2】従来の化学増幅型レジストパターン断面図であ
る。FIG. 2 is a sectional view of a conventional chemically amplified resist pattern.
101、201 ウェハー 102、202 化学増幅型レジストパターン 101, 201 Wafer 102, 202 Chemically amplified resist pattern
Claims (4)
るベース樹脂と光酸発生剤とから成る化学増幅ポジ型レ
ジスト材料にポリヒドロキシスチレン樹脂を溶解促進剤
として添加することを特徴とする化学増幅型レジスト。1. A chemically amplified positive resist composition comprising a base resin having at least a protective group hardly soluble in alkali and a photoacid generator, wherein a polyhydroxystyrene resin is added as a dissolution accelerator. Resist.
30000、分子量分散1.5〜3.5のポリヒドロキ
シスチレン樹脂を用いた請求項1記載の化学増幅型レジ
スト。2. The molecular weight of the dissolution promoter of 1,000 to 1,000.
2. The chemically amplified resist according to claim 1, wherein a polyhydroxystyrene resin having a molecular weight distribution of from 30,000 to 1.5 to 3.5 is used.
ン樹脂の添加量が対ベース樹脂比1〜30重量%である
請求項1または2記載の化学増幅型レジスト。3. The chemically amplified resist according to claim 1, wherein the amount of the polyhydroxystyrene resin used as the dissolution promoter is 1 to 30% by weight relative to the base resin.
ス樹脂としてターシャリブトキシカルボニル保護ポリヒ
ドロキシスチレン樹脂またはターシャリブチルアクリレ
ート樹脂を使用した請求項1,2または3記載の化学増
幅型レジスト。4. The chemically amplified resist according to claim 1, wherein tertiary butoxycarbonyl protected polyhydroxystyrene resin or tertiary butyl acrylate resin is used as the base resin having a protective group that is hardly soluble in alkali.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9319967A JPH11153869A (en) | 1997-11-20 | 1997-11-20 | Chemically amplified resist |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9319967A JPH11153869A (en) | 1997-11-20 | 1997-11-20 | Chemically amplified resist |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH11153869A true JPH11153869A (en) | 1999-06-08 |
Family
ID=18116260
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9319967A Pending JPH11153869A (en) | 1997-11-20 | 1997-11-20 | Chemically amplified resist |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH11153869A (en) |
-
1997
- 1997-11-20 JP JP9319967A patent/JPH11153869A/en active Pending
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