JP2000047388A - Chemically sensitizing resist - Google Patents
Chemically sensitizing resistInfo
- Publication number
- JP2000047388A JP2000047388A JP10215366A JP21536698A JP2000047388A JP 2000047388 A JP2000047388 A JP 2000047388A JP 10215366 A JP10215366 A JP 10215366A JP 21536698 A JP21536698 A JP 21536698A JP 2000047388 A JP2000047388 A JP 2000047388A
- Authority
- JP
- Japan
- Prior art keywords
- resist
- water
- chemically amplified
- added bisphenol
- excimer laser
- 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.)
- Granted
Links
- 230000001235 sensitizing effect Effects 0.000 title abstract 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 12
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 9
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 7
- 125000006239 protecting group Chemical group 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 4
- 230000003321 amplification Effects 0.000 claims 2
- 238000003199 nucleic acid amplification method Methods 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- 238000001312 dry etching Methods 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 229930185605 Bisphenol Natural products 0.000 abstract 2
- 238000004090 dissolution Methods 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 6
- 239000002585 base Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- RUPAXCPQAAOIPB-UHFFFAOYSA-N tert-butyl formate Chemical group CC(C)(C)OC=O RUPAXCPQAAOIPB-UHFFFAOYSA-N 0.000 description 3
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、脂環式アクリル系
樹脂と光酸発生剤とを含むＡｒＦエキシマレーザー用化
学増幅系レジストに関する。The present invention relates to a chemically amplified resist for ArF excimer laser containing an alicyclic acrylic resin and a photoacid generator.
【０００２】[0002]
【従来の技術】従来の光リソグラフィでは、露光光にｇ
線（４３６ｎｍ）、ｉ線（３６５ｎｍ）を用いており、
そのレジストとしては、ベース樹脂にノボラック樹脂を
用い、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、そのレジストとしては従来のｇ線、ｉ線用レジスト
では光吸収が大きすぎ、良好なレジストパターンが得ら
れず、また感度も大幅に増大するという状況であった。
これに対し、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系レジストが提案され、短波長リソ
グラフィ用レジスト、さらには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。2. Description of the Related Art In conventional optical lithography, g
Line (436 nm) and i-line (365 nm)
As the resist, a dissolution-suppressing positive resist using a novolak resin as a base resin and naphthoquinonediazide as a photosensitive agent was mainly used. However, excimer laser light (248 n
lithography using m, 193 nm, etc.), and the conventional g-line and i-line resists are too light-absorbing, fail to provide a good resist pattern, and greatly increase sensitivity. It was a situation.
On the other hand, a chemically amplified resist utilizing the sensitization reaction of an acid catalyst generated from a photoacid generator has been proposed, and has become the mainstream as a resist for short-wavelength lithography and also as a resist for electron beam lithography requiring high sensitivity. It is getting.
【０００３】[0003]
【発明が解決しようとする課題】露光波長１９３ｎｍの
ＡｒＦエキシマレーザーリソグラフィ用レジストは、特
に光吸収の問題が大きく、レジスト構成成分に制約が大
きい。これまでに下記式（ａ）に示すような脂環式メタ
クリレート樹脂（ベース樹脂）と、下記式（ｂ）に示す
ような光酸発生剤とからなる２成分系ポジ型レジスト
（例えば、Proc. SPIE, vol.2438, p.433, 1995）が一
般に提案されている。A resist for an ArF excimer laser lithography having an exposure wavelength of 193 nm has a particularly large problem of light absorption, and the components of the resist are greatly restricted. Heretofore, a two-component positive resist comprising an alicyclic methacrylate resin (base resin) represented by the following formula (a) and a photoacid generator represented by the following formula (b) (for example, Proc. SPIE, vol.2438, p.433, 1995) has been generally proposed.
【化１】 Embedded image
【化２】 Embedded image
【０００４】しかし、脂環式メタクリレートを用いた前
記レジストでは、構成成分に芳香環が含まれていないた
め、レジストパターン形成後下地膜にパターンを転写す
る際に用いられるドライエッチングにおいて耐性および
耐熱性が著しく弱く、実用性に劣るという欠点があっ
た。また、溶解コントラストが小さいため、図２に示す
ようにレジストパターン４０２がテーパー形状になり、
解像性が劣るという欠点があった。However, in the above-mentioned resist using alicyclic methacrylate, since a constituent component does not contain an aromatic ring, resistance and heat resistance in dry etching used when transferring a pattern to a base film after forming a resist pattern are obtained. Has a drawback of being extremely weak and inferior in practical use. Further, since the dissolution contrast is small, the resist pattern 402 has a tapered shape as shown in FIG.
There was a disadvantage that the resolution was poor.
【０００５】上記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ており、例えばドライエッ
チング耐性、耐熱性を向上させる手法として、フェノー
ル系樹脂と光酸発生剤を含む２成分系ポジ型化学増幅レ
ジストに架橋剤を添加する方法が提案されている（特開
平５−３２３６１０）。Several methods have been proposed to solve the above problems. For example, as a method for improving dry etching resistance and heat resistance, a two-component system containing a phenolic resin and a photoacid generator has been proposed. A method of adding a crosslinking agent to a positive chemically amplified resist has been proposed (JP-A-5-323610).
【０００６】本発明は、上記事情に鑑みてなされたもの
で、ＡｒＦエキシマレーザー用化学増幅系レジストにお
いて、溶解コントラストを大きくすることにより、解像
性を向上させ、かつドライエッチング耐性を向上させた
化学増幅系レジストを提供することを目的とする。The present invention has been made in view of the above circumstances, and in a chemically amplified resist for ArF excimer laser, resolution has been improved and dry etching resistance has been improved by increasing the dissolution contrast. An object of the present invention is to provide a chemically amplified resist.
【０００７】[0007]
【課題を解決するための手段】本発明は、前記目的を達
成するため、少なくとも脂環式アクリル系樹脂と光酸発
生剤とを含むＡｒＦエキシマレーザー用化学増幅系レジ
ストにおいて、水添加ビスフェノール誘導体を混合して
なることを特徴とする化学増幅系レジストを提供する。In order to achieve the above object, the present invention provides a chemically amplified resist for ArF excimer laser containing at least an alicyclic acrylic resin and a photoacid generator, wherein a water-added bisphenol derivative is used. Provided is a chemically amplified resist characterized by being mixed.
【０００８】また、本発明は、前記目的を達成するた
め、少なくとも脂環式アクリル系樹脂と光酸発生剤とを
含むＡｒＦエキシマレーザー用化学増幅系レジストにお
いて、極性が変化する保護基を有する水添加ビスフェノ
ール誘導体を混合してなることを特徴とする化学増幅系
レジストを提供する。In order to achieve the above-mentioned object, the present invention provides a chemically amplified resist for ArF excimer laser containing at least an alicyclic acrylic resin and a photoacid generator. Provided is a chemically amplified resist characterized by being mixed with an added bisphenol derivative.
【０００９】本発明のＡｒＦ用化学増幅系レジストは、
溶解コントラスト、ドライエッチング耐性を解消するた
め、シクロヘキシル環を有する水添加ビスフェノールＡ
誘導体を添加している。これにより、未露光部の溶解速
度が小さくなり、レジスト膜の現像液に対する溶解コン
トラストを大きくすることができ、その結果レジストの
解像性を向上させることができる。また、環構造を有す
るシクロヘキシル環がドライエッチング時のレジストの
膜減りを抑え、また、耐熱性を向上させることができ
る。The chemically amplified resist for ArF of the present invention comprises:
Water-soluble bisphenol A having a cyclohexyl ring to eliminate dissolution contrast and dry etching resistance
Derivatives are added. As a result, the dissolution rate of the unexposed portion is reduced, and the dissolution contrast of the resist film with respect to the developing solution can be increased. As a result, the resolution of the resist can be improved. Further, a cyclohexyl ring having a ring structure can suppress a decrease in the film thickness of the resist during dry etching, and can improve heat resistance.
【００１０】[0010]
【発明の実施の形態】本発明において、脂環式アクリル
系樹脂としては、例えば前記式（ａ）の脂環式メタクリ
レート樹脂が挙げられ、光酸発生剤としては、例えば前
記式（ｂ）の化合物が挙げられ、水添加ビスフェノール
誘導体としては、例えば下記式（ｃ）で示される化合物
が挙げられるが、これらに限定されるものではない。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, examples of the alicyclic acrylic resin include the alicyclic methacrylate resin of the above formula (a), and examples of the photoacid generator include those of the above formula (b) Examples of the water-added bisphenol derivative include, but are not limited to, compounds represented by the following formula (c).
【化３】 Embedded image
【００１１】ここで、式（ｃ）の化合物において、官能
基Ｒとしては、例えば水酸基、酸により脱離するターシ
ャリーブトキシカルボニル（ｔ−ＢＯＣ）基、テトラヒ
ドロピラニル（ＴＨＰ）基等の極性が変化する保護基が
挙げられるが、これらに限定されるものではない。ま
た、官能基Ｒは互いに同じであってもよく、異なってい
てもよい。Here, in the compound of the formula (c), the functional group R has, for example, a hydroxyl group, a tertiary butoxycarbonyl (t-BOC) group which is eliminated by an acid, a tetrahydropyranyl (THP) group or the like. Examples include, but are not limited to, changing protecting groups. Further, the functional groups R may be the same or different.
【００１２】[0012]
【実施例】本発明の実施例について説明する。レジスト
としては、脂環式アクリレート樹脂および光酸発生剤か
ら構成される２成分化学増幅ポジ型ＡｒＦ用レジストを
用いた。このレジストに対し、前記式（ｃ）の水添加ビ
スフェノールＡ誘導体（官能基Ｒはいずれも水酸基）
を、対脂環式アクリレート樹脂比で３重量％添加した。
これによりドライエッチング耐性、耐熱性が約１０％向
上し、図１に示す矩形のレジストパターン３０２を得る
ことができた。An embodiment of the present invention will be described. As the resist, a two-component chemically amplified positive ArF resist composed of an alicyclic acrylate resin and a photoacid generator was used. For this resist, a water-added bisphenol A derivative of the above formula (c) (functional groups R are all hydroxyl groups)
Was added in an amount of 3% by weight relative to the alicyclic acrylate resin.
Thereby, the dry etching resistance and the heat resistance were improved by about 10%, and the rectangular resist pattern 302 shown in FIG. 1 was obtained.
【００１３】このとき、官能基Ｒとしては水酸基の他
に、前記ｔ−ＢＯＣ基、ＴＨＰ基等が挙げられる。これ
らの官能基が異なる水添加ビスフェノールＡ誘導体を添
加することによっても同様の効果が得られるが、アルカ
リ現像液に対する溶解性が異なるため、レジスト形状、
解像度が異り、したがってベースとなるレジストの組成
に合わせて添加量を適当に選ぶ必要がある。At this time, as the functional group R, in addition to the hydroxyl group, the above-mentioned t-BOC group, THP group and the like can be mentioned. The same effect can be obtained by adding a water-added bisphenol A derivative having a different functional group, but since the solubility in an alkali developer is different, the resist shape,
Since the resolution is different, it is necessary to appropriately select the addition amount according to the composition of the base resist.
【００１４】[0014]
【発明の効果】以上説明したように、本発明のＡｒＦ用
化学増幅系レジストは、溶解コントラストを大きくし、
レジストの解像性を向上させることができる。また、ド
ライエッチング時のレジストの膜減りを抑え、かつ耐熱
性を向上させることができる。さらに、官能基の種類、
添加量を適当に選ぶことにより、レジストの解像性に最
も影響を与える溶解コントラストを最適にし、解像性、
ドライエッチング耐性、耐熱性を１０％以上向上するこ
とができる。そのため、現像後の脱水ベーク時、ドライ
エッチング時にレジストパターンの変形が抑えられ、高
解像性を確保することができる。しかも、矩形なレジス
トパターンが得られるため、寸法精度を向上させること
ができる。As described above, the chemically amplified resist for ArF of the present invention increases the dissolution contrast,
The resolution of the resist can be improved. Further, it is possible to suppress a decrease in the film thickness of the resist at the time of dry etching and improve heat resistance. In addition, the type of functional group,
By appropriately selecting the amount of addition, the dissolution contrast that most affects the resolution of the resist is optimized, and the resolution,
Dry etching resistance and heat resistance can be improved by 10% or more. Therefore, deformation of the resist pattern during dehydration baking and dry etching after development is suppressed, and high resolution can be ensured. In addition, since a rectangular resist pattern is obtained, dimensional accuracy can be improved.
【００１５】また、水添加ビスフェノールＡは芳香環は
持たないものの、シクロヘキシル環を有するため、Ａｒ
Ｆエキシマレーザー光の１９３ｎｍに大きな光吸収を持
たず、かつドライエッチング耐性を向上することができ
る。Further, although the water-added bisphenol A does not have an aromatic ring, but has a cyclohexyl ring,
It does not have a large light absorption at 193 nm of the F excimer laser light and can improve dry etching resistance.
【００１６】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。The effect is particularly great for forming a fine pattern, and a rectangular photoresist pattern can be formed with good reproducibility.
【図１】本発明の化学増幅系レジストによるレジストパ
ターンの一例を示す断面図である。FIG. 1 is a cross-sectional view showing an example of a resist pattern using a chemically amplified resist of the present invention.
【図２】従来の化学増幅系レジストによるレジストパタ
ーンの一例を示す断面図である。FIG. 2 is a cross-sectional view showing an example of a resist pattern using a conventional chemically amplified resist.
３０１ ウェハー ３０２ レジストパターン ４０１ ウェハー ４０２ レジストパターン 301 wafer 302 resist pattern 401 wafer 402 resist pattern
Claims (4)
生剤とを含むＡｒＦエキシマレーザー用化学増幅系レジ
ストにおいて、水添加ビスフェノール誘導体を混合して
なることを特徴とする化学増幅系レジスト。1. A chemical amplification resist for ArF excimer laser containing at least an alicyclic acrylic resin and a photoacid generator, wherein a water-added bisphenol derivative is mixed.
ベース樹脂１００重量部に対し３〜１０重量部であるこ
とを特徴とする請求項１に記載の化学増幅系レジスト。2. A mixed amount of a water-added bisphenol derivative,
2. The chemically amplified resist according to claim 1, wherein the amount is 3 to 10 parts by weight based on 100 parts by weight of the base resin.
生剤とを含むＡｒＦエキシマレーザー用化学増幅系レジ
ストにおいて、極性が変化する保護基を有する水添加ビ
スフェノール誘導体を混合してなることを特徴とする化
学増幅系レジスト。3. A chemically amplified resist for ArF excimer laser containing at least an alicyclic acrylic resin and a photoacid generator, wherein a water-added bisphenol derivative having a protecting group whose polarity changes is mixed. Chemical amplification resist.
フェノール誘導体の混合量が、ベース樹脂１００重量部
に対し３〜１０重量部であることを特徴とする請求項３
に記載の化学増幅系レジスト。4. The method according to claim 3, wherein the mixing amount of the water-added bisphenol derivative having a protecting group whose polarity is changed is 3 to 10 parts by weight based on 100 parts by weight of the base resin.
3. The chemically amplified resist according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21536698A JP3206740B2 (en) | 1998-07-30 | 1998-07-30 | Chemically amplified resist |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21536698A JP3206740B2 (en) | 1998-07-30 | 1998-07-30 | Chemically amplified resist |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000047388A true JP2000047388A (en) | 2000-02-18 |
| JP3206740B2 JP3206740B2 (en) | 2001-09-10 |
Family
ID=16671113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21536698A Expired - Fee Related JP3206740B2 (en) | 1998-07-30 | 1998-07-30 | Chemically amplified resist |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3206740B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003051443A (en) * | 2001-06-28 | 2003-02-21 | Hynix Semiconductor Inc | Method of forming fine pattern in semiconductor device |
| WO2011111805A1 (en) * | 2010-03-10 | 2011-09-15 | Fujifilm Corporation | Actinic ray-sensitive or radiation-sensitive resin composition, and resist film and pattern forming method using the same |
| US8802792B2 (en) | 2010-09-17 | 2014-08-12 | Empire Technology Development Llc | Partially hydrogenated bisphenol-A-based polymers as substitutes for bisphenol-A-based polymers |
-
1998
- 1998-07-30 JP JP21536698A patent/JP3206740B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003051443A (en) * | 2001-06-28 | 2003-02-21 | Hynix Semiconductor Inc | Method of forming fine pattern in semiconductor device |
| WO2011111805A1 (en) * | 2010-03-10 | 2011-09-15 | Fujifilm Corporation | Actinic ray-sensitive or radiation-sensitive resin composition, and resist film and pattern forming method using the same |
| JP2011186340A (en) * | 2010-03-10 | 2011-09-22 | Fujifilm Corp | Active ray-sensitive or radiation-sensitive resin composition, and resist film and pattern forming method using the same |
| US8795945B2 (en) | 2010-03-10 | 2014-08-05 | Fujifilm Corporation | Actinic ray-sensitive or radiation-sensitive resin composition, and resist film and pattern forming method using the same |
| US8802792B2 (en) | 2010-09-17 | 2014-08-12 | Empire Technology Development Llc | Partially hydrogenated bisphenol-A-based polymers as substitutes for bisphenol-A-based polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3206740B2 (en) | 2001-09-10 |
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