JP2687578B2 - Highly sensitive resist and method for forming resist pattern - Google Patents
Highly sensitive resist and method for forming resist patternInfo
- Publication number
- JP2687578B2 JP2687578B2 JP1117868A JP11786889A JP2687578B2 JP 2687578 B2 JP2687578 B2 JP 2687578B2 JP 1117868 A JP1117868 A JP 1117868A JP 11786889 A JP11786889 A JP 11786889A JP 2687578 B2 JP2687578 B2 JP 2687578B2
- Authority
- JP
- Japan
- Prior art keywords
- resist
- weight
- parts
- pattern
- general formula
- 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 6
- 239000002253 acid Substances 0.000 claims description 27
- 229920005601 base polymer Polymers 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical group 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 229910021115 PF 6 Inorganic materials 0.000 description 2
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- UIQGEWJEWJMQSL-UHFFFAOYSA-N 2,2,4,4-tetramethylpentan-3-one Chemical compound CC(C)(C)C(=O)C(C)(C)C UIQGEWJEWJMQSL-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- XKGLSKVNOSHTAD-UHFFFAOYSA-N valerophenone Chemical compound CCCCC(=O)C1=CC=CC=C1 XKGLSKVNOSHTAD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Materials For Photolithography (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、各種半導体装置の製造工程をはじめとし
て、各種微細加工のマスク等として用いられる高感度レ
ジスト及びレジストパターンの形成方法に関する。The present invention relates to a method for forming a highly sensitive resist and a resist pattern used as a mask for various microfabrications, including manufacturing steps of various semiconductor devices.
［発明の概要］ 本発明は、レジストにおいて、 ベースポリマー100重量部に対し、酸発生剤0.1〜10重
量部と、一般式 （但し、R,R′Ｒ″は各々炭化水素基を表わす）で示さ
れる化合物0.1〜３重量部とを含有させたことにより、 微細なパターンで良好なレジスト形状を得られるよう
にしたものである。[Summary of the Invention] The present invention provides a resist, in which 0.1 to 10 parts by weight of an acid generator and 100 parts by weight of a general formula (Provided that R and R'R "each represent a hydrocarbon group) and 0.1 to 3 parts by weight of a compound represented by the formula (3) are used to obtain a good resist shape with a fine pattern. is there.
［従来の技術］ 従来、この種の高感度レジストとしては、化学増幅型
レジストが知られている。この化学増幅型レジストは、
オニウム塩系等の酸発生剤に光照射した際に発生する酸
によって誘起される硬化反応又は分解反応を利用したも
のである。[Prior Art] A chemically amplified resist has been known as a highly sensitive resist of this type. This chemically amplified resist is
It utilizes a curing reaction or a decomposition reaction induced by an acid generated when an onium salt-based acid generator is irradiated with light.
かかる化学増幅型レジストの詳細として、クレゾール
系，ポリヒドロキシレン系樹脂のベースポリマーに、メ
ラミン系誘導体（メチロール体）やポリハロゲン化物等
の架橋剤や酸発生剤を加えたものであって、露光で発生
した酸を露光後のベーク（PEB）で拡散するため、従来
のレジストに較べてエキシマ光源（248nm）での露光に
おいて良好なレジスト形状を有するものである。As the details of such a chemically amplified resist, a base polymer of a cresol-based or polyhydroxylene-based resin to which a crosslinking agent such as a melamine derivative (methylol body) or a polyhalide or an acid generator is added, Since the acid generated in 2) is diffused by baking (PEB) after exposure, it has a better resist shape when exposed with an excimer light source (248 nm) than a conventional resist.
［発明が解決しようとする課題］ しかしながら、このような従来の化学増幅型レジスト
にあっては、例えば、光強度のコントラストが低下する
0.35μｍ程度のパターンルールの場合において十分なパ
ターン形状が得られないという問題点があった。[Problems to be Solved by the Invention] However, in such a conventional chemically amplified resist, for example, the contrast of the light intensity is lowered.
In the case of a pattern rule of about 0.35 μm, there is a problem that a sufficient pattern shape cannot be obtained.
第３図は、従来の化学増幅型レジスト塗布膜を露光し
た場合の深さ方向の酸濃度の変化を見たものであるが、
露光後のベークを行なって酸を拡散させても、第４図に
示すように、パターン形状は良好でない。FIG. 3 shows changes in acid concentration in the depth direction when a conventional chemically amplified resist coating film is exposed.
Even if the acid is diffused by baking after the exposure, the pattern shape is not good as shown in FIG.
本発明は、このような従来の問題点に着目して創案さ
れたものであって、より微細なパターンで良好なレジス
ト形状が実現出来る高感度レジスト及びレジストパター
ンの形成方法を得んとするものである。The present invention was devised by focusing on such conventional problems, and an object thereof is to obtain a high-sensitivity resist and a method for forming a resist pattern capable of realizing a good resist shape with a finer pattern. Is.
［課題を解決するための手段］ そこで、本発明は、ベースポリマー100重量部に対
し、酸発生剤0.1〜10重量部と、一般式 （但し、R,R′Ｒ″は各々炭化水素基を表わす）で示さ
れる化合物0.1〜３重量部とを含有させたことを、その
解決手段としている。[Means for Solving the Problems] Therefore, the present invention is based on 100 parts by weight of the base polymer, 0.1 to 10 parts by weight of the acid generator, the general formula The solution is to contain 0.1 to 3 parts by weight of a compound represented by (wherein R and R'R "each represent a hydrocarbon group).
［作用］ 一般式 （但し、R,R′Ｒ″は各々炭化水素基を表わす）で示さ
れる化合物をレジスト中に混入させたことにより、光照
射時にアミンが発生し、このアミンが同時に発生した酸
を中和する。かかる化合物を化学増幅型レジストのベー
スポリマー100重量部に対し、0.1〜３重量部の割合で含
有させることにより、酸の深さ方向の分布を第１図に示
すグラフのように均一化して、レジストパターン形状を
良好にする。[Operation] General formula (However, R and R'R "each represent a hydrocarbon group) By mixing in the resist, an amine is generated at the time of light irradiation, and this amine neutralizes the acid generated at the same time. By including such a compound in a proportion of 0.1 to 3 parts by weight relative to 100 parts by weight of the base polymer of the chemically amplified resist, the distribution of the acid in the depth direction is made uniform as shown in the graph in FIG. Improve the resist pattern shape.
なお、化学増幅型レジストとしては、ノボラック系樹
脂に架橋剤及び酸発生剤を含有したものを用いる。As the chemically amplified resist, a novolac resin containing a crosslinking agent and an acid generator is used.
［実施例］ 以下、本発明に係る高感度レジスト及びレジストパタ
ーンの形成方法の詳細を実施例に基づいて説明する。[Examples] Hereinafter, details of a method for forming a high-sensitivity resist and a resist pattern according to the present invention will be described based on Examples.
本発明はベースポリマー100重量部に対し、酸発生剤
0.1〜10重量部と、一般式 （但し、R,R′Ｒ″は各々炭化水素基を表わす）で示さ
れる化合物0.1〜３重量部とを含有させたものである。The present invention is an acid generator based on 100 parts by weight of the base polymer.
0.1-10 parts by weight and general formula (Wherein R and R'R "each represent a hydrocarbon group) in an amount of 0.1 to 3 parts by weight.
本実施例において、ベースポリマーとして、一般式 で示されるブチルフェニルケトンの重合体を用いた。な
お、tBOCは、ｔ−ブチルケトンを示している。In this example, as the base polymer, the general formula The polymer of butyl phenyl ketone represented by Note that tBOC represents t-butyl ketone.
このベースポリマー100重量部に対して、酸発生剤と
してAr2I+BF4 -（Ar:アリル基）を１重量部と、アシルオ
キシイミノ基を含む、一般式 で示す化合物を0.1重量部を含有させて、ポジ型の高感
度レジストを作成した。For this 100 parts by weight of the base polymer, Ar 2 I + BF 4 as an acid generator -: and 1 part by weight of (Ar allyl group), including acyloxyiminoketones group, the general formula A positive type high-sensitivity resist was prepared by containing 0.1 part by weight of the compound shown in (1).
次に、このレジストをシリコン基板に塗布して膜を形
成し、エキシマ光源（248nm）にて露光を行なった結
果、第１図のグラフに示すように、レジスト膜上部から
下部に亘って、露光により発生した酸濃度は均一化され
たものであった。即ち、一般式（２）で示す化合物が光
照射されることにより、アミンを発生し、このアミンが
酸発生剤から発生した酸を中和するものであり、上記し
た割合で含有させたことにより深さ方向の酸濃度の均一
化が達成されている。Next, this resist was applied to a silicon substrate to form a film, and the film was exposed with an excimer light source (248 nm). As a result, as shown in the graph of FIG. The acid concentration generated by was uniform. That is, the compound represented by the general formula (2) is irradiated with light to generate an amine, and the amine neutralizes the acid generated from the acid generator. A uniform acid concentration in the depth direction is achieved.
このため、例えば0.35μｍのパターンルールにおい
て、PEB後第２図に示すような良好なパターン形状を形
成することが可能となった。Therefore, for example, with a pattern rule of 0.35 μm, it becomes possible to form a good pattern shape as shown in FIG. 2 after PEB.
なお、上記実施例においては、ベースポリマーとして
一般式（１）で示すポリマーを用いたが、例えば、一般
式 で示される重合体の他、各種のポリマーを用いることが
可能である。In the above examples, the polymer represented by the general formula (1) was used as the base polymer. In addition to the polymer represented by, various polymers can be used.
また、酸発生剤の露光に伴なう光化学反応は、以下の
式の如くなり、 酸HBF4が発生する。Further, the photochemical reaction associated with the exposure of the acid generator is as shown in the following formula, Acid HBF 4 is generated.
なお、酸発生剤としては、この他のAr2I+MXn -（MXn：
PF6,AsF6,SbF6,CF3SO3）、Ar3S+MXn -（MXn：BF4,PF6,As
F6,SbF6,CF3SO3）等を用いてもよい。As the acid generator, the other Ar 2 I + MX n - ( MX n:
PF 6, AsF 6, SbF 6 , CF 3 SO 3), Ar 3 S + MX n - (MX n: BF 4, PF 6, As
F 6 , SbF 6 , CF 3 SO 3 ) or the like may be used.
さらに、アシルオキシイミノ基を含む一般式 で示される化合物の他には、 一般式 （但し、R,R′,R″は各々炭化水素基を表わす）で示さ
れる範囲の化合物を用いてもよい。Furthermore, a general formula containing an acyloxyimino group In addition to the compound represented by (However, R, R ′ and R ″ each represent a hydrocarbon group) may be used.
また、上記実施例においては、ベースポリマー100重
量部に対して酸発生剤を１重量部としたが、0.1〜10重
量部の範囲に含有量を設定することが可能である。一
方、 一般式 で示される化合物も、ベースポリマー100重量部に対し
て0.1〜３重量部の範囲に含有量を設定することができ
る。Further, in the above examples, the acid generator was 1 part by weight with respect to 100 parts by weight of the base polymer, but the content can be set within the range of 0.1 to 10 parts by weight. On the other hand, the general formula The content of the compound represented by can also be set within the range of 0.1 to 3 parts by weight with respect to 100 parts by weight of the base polymer.
以上の実施例は、本発明をポジ型のレジストに適用し
て説明したが、ネガ型のレジストに適用する場合は、上
記組成の他に、架橋剤として例えば、以下の構造式 で示される化合物、その他を用いればよい。The above examples have been described by applying the present invention to a positive type resist, but when applied to a negative type resist, in addition to the above composition, as a crosslinking agent, for example, the following structural formula The compound shown by or the like may be used.
本発明は、この他、構成の要旨に付随する各種の材料
変更が可能である。In addition to the above, the present invention is capable of various material changes accompanying the gist of the configuration.
［発明の効果］ 以上の説明から明らかなように、本発明に係る高感度
レジスト及びレジストパターンの形成方法にあっては、
固相中で発生したアミンと酸が中和するため、レジスト
膜上下方向に均一化した酸濃度に依存して、微細なパタ
ーンにおいても良好なレジスト形状を得ることが出来る
効果がある。[Effects of the Invention] As is apparent from the above description, in the high-sensitivity resist and the method for forming a resist pattern according to the present invention,
Since the amine and acid generated in the solid phase are neutralized, there is an effect that a good resist shape can be obtained even in a fine pattern depending on the acid concentration that is uniformized in the vertical direction of the resist film.
特に、パターンルール0.35μｍ付近の光強度のコント
ラストが低下する領域においても良好なパターン形状が
得られる。In particular, a good pattern shape can be obtained even in a region where the contrast of the light intensity is reduced near the pattern rule of 0.35 μm.
第１図は本発明に係る高感度レジストの実施例を用いて
レジスト膜を形成した場合での露光後の酸濃度を深さ方
向に見た結果を示すグラフ、第２図は本実施例のレジス
トパターン形状を示す説明図、第３図は従来のレジスト
の深さ方向の発生酸濃度を示すグラフ、第４図は従来の
レジストパターン形状を示す説明図である。FIG. 1 is a graph showing the results of looking at the acid concentration after exposure in the depth direction when a resist film was formed using the example of the high-sensitivity resist according to the present invention, and FIG. 2 is the graph of this example. FIG. 3 is an explanatory view showing a resist pattern shape, FIG. 3 is a graph showing a generated acid concentration in a depth direction of a conventional resist, and FIG. 4 is an explanatory view showing a conventional resist pattern shape.
Claims (2)
剤0.1〜10重量部と、一般式 （但し、R,R′Ｒ″は各々炭化水素基を表わす）で示さ
れる化合物0.1〜３重量部とを含有させたことを特徴と
する高感度レジスト。1. An acid generator of 0.1 to 10 parts by weight based on 100 parts by weight of a base polymer, and a general formula A high-sensitivity resist containing 0.1 to 3 parts by weight of a compound represented by the formula (wherein R and R'R "each represent a hydrocarbon group).
剤0.1〜10重量部と、一般式 （但し、R,R′Ｒ″は各々炭化水素基を表わす）で示さ
れる化合物0.1〜３重量部とを含有させて成るレジスト
を、基体上に塗布し、次に、該レジストをパターン露光
した後現像を行なうことを特徴とするレジストパターン
の形成方法。2. An acid generator of 0.1 to 10 parts by weight based on 100 parts by weight of a base polymer, and a general formula A resist containing 0.1 to 3 parts by weight of a compound represented by the formula (wherein R and R'R "each represents a hydrocarbon group) is coated on a substrate, and then the resist is pattern-exposed. A method for forming a resist pattern, which comprises performing post-development.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1117868A JP2687578B2 (en) | 1989-05-11 | 1989-05-11 | Highly sensitive resist and method for forming resist pattern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1117868A JP2687578B2 (en) | 1989-05-11 | 1989-05-11 | Highly sensitive resist and method for forming resist pattern |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02296250A JPH02296250A (en) | 1990-12-06 |
| JP2687578B2 true JP2687578B2 (en) | 1997-12-08 |
Family
ID=14722275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1117868A Expired - Fee Related JP2687578B2 (en) | 1989-05-11 | 1989-05-11 | Highly sensitive resist and method for forming resist pattern |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2687578B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0537524A1 (en) * | 1991-10-17 | 1993-04-21 | Shipley Company Inc. | Radiation sensitive compositions and methods |
| JPH05127369A (en) * | 1991-10-31 | 1993-05-25 | Nec Corp | Resist material |
| KR100481601B1 (en) * | 1999-09-21 | 2005-04-08 | 주식회사 하이닉스반도체 | Photoresist composition containing photo base generator with photo acid generator |
| JP5186303B2 (en) * | 2008-07-31 | 2013-04-17 | 東京応化工業株式会社 | Resist composition and resist pattern forming method |
| JP5276958B2 (en) * | 2008-11-19 | 2013-08-28 | 東京応化工業株式会社 | Resist composition and resist pattern forming method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2687567B2 (en) * | 1989-04-11 | 1997-12-08 | ソニー株式会社 | Positive resist and resist pattern forming method |
-
1989
- 1989-05-11 JP JP1117868A patent/JP2687578B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02296250A (en) | 1990-12-06 |
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| LAPS | Cancellation because of no payment of annual fees |