JPS63229715A - Resist hardening method - Google Patents
Resist hardening methodInfo
- Publication number
- JPS63229715A JPS63229715A JP6242187A JP6242187A JPS63229715A JP S63229715 A JPS63229715 A JP S63229715A JP 6242187 A JP6242187 A JP 6242187A JP 6242187 A JP6242187 A JP 6242187A JP S63229715 A JPS63229715 A JP S63229715A
- Authority
- JP
- Japan
- Prior art keywords
- resist
- coating film
- pattern
- resin
- high molecular
- 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
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229920000620 organic polymer Polymers 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 4
- 230000007261 regionalization Effects 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 20
- 229920005989 resin Polymers 0.000 abstract description 20
- 239000004593 Epoxy Substances 0.000 abstract description 9
- 238000001312 dry etching Methods 0.000 abstract description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract description 8
- 239000004926 polymethyl methacrylate Substances 0.000 abstract description 8
- 229930185605 Bisphenol Natural products 0.000 abstract description 7
- 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 abstract description 7
- 229920003986 novolac Polymers 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 238000000059 patterning Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 4
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 238000004132 cross linking Methods 0.000 description 8
- 238000003848 UV Light-Curing Methods 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013036 cure process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Description
【発明の詳細な説明】
〔概 要〕
レジストの有機高分子材料を架橋させる物質を、パター
ン形成後のレジストに塗付して、レジストの有機高分子
材料を硬化させることにより、レジストのハードニング
を効果的にかつ確実に行なう。[Detailed Description of the Invention] [Summary] A substance that crosslinks the organic polymer material of the resist is applied to the resist after pattern formation to harden the organic polymer material of the resist, thereby hardening the resist. effectively and reliably.
本発明はレジストプロセスに関するものであり、さらに
詳しく述べるならば、ホトレジストのパターンをハード
ニング（硬化）する方法に関する。TECHNICAL FIELD This invention relates to resist processing, and more particularly, to a method of hardening a pattern in photoresist.
半導体装置の製造プロセスにおいて、酸化物、ポリシリ
コン、アルミニウムなどをエツチングするためにホトレ
ジストパターンをマスクとしてドライエツチングするこ
とが行なわれる。ドライエツチングの際の反応熱により
ホトレジストが熱せられ、レジストパターンの精度が低
下するという問題がある。この問題の対策としてホトレ
ジストの耐熱性、耐ドライエツチング性を向上させるた
めの硬化手段として、レジストパターン形成後に、ＵＶ
−キュア処理が行なわれる。この処理は、レジストパタ
ーンに、波長が２００から４００ｎｍの紫外線を照射し
て、ノボラック樹脂の架橋反応を生せしめる事を基本と
するものである。かかる処理によって、レジスト樹脂が
硬化されそして耐熱性および耐ドライエツチ性が向上す
る。さらにキュア処理中もしくはその前に１００℃以上
の温度にレジスト樹脂を加熱することにより、レジスト
樹脂から、上記架橋反応を妨害する水を蒸発させ反応を
効果的に行なうことも知られている。In the manufacturing process of semiconductor devices, dry etching is performed using a photoresist pattern as a mask in order to etch oxides, polysilicon, aluminum, etc. There is a problem in that the photoresist is heated by reaction heat during dry etching, resulting in a decrease in the accuracy of the resist pattern. As a countermeasure to this problem, as a curing means to improve the heat resistance and dry etching resistance of the photoresist, after forming the resist pattern, UV
- A cure process is performed. This treatment is based on irradiating the resist pattern with ultraviolet rays having a wavelength of 200 to 400 nm to cause a crosslinking reaction of the novolac resin. Such treatment hardens the resist resin and improves its heat resistance and dry etch resistance. Furthermore, it is also known that by heating the resist resin to a temperature of 100° C. or higher during or before the curing treatment, water that interferes with the crosslinking reaction can be evaporated from the resist resin to effectively carry out the reaction.
しかしながら、レジストの耐ドライエツチ性の要求がま
すます高められ、２００℃以上の温度での耐熱性が要求
されるようになるにつれて、従来のＵＶ−キュア処理で
は十分な性能をもったレジストパターンが得られなくな
っている。特に、近年解像度を向上させるために分子量
が低いレジスト樹脂が用いられる場合にはレジスト樹脂
の耐熱性が低くなるため、１００℃以上の温度でレジス
トパターンが変形するという問題がある。また、通常の
分子量のレジスト樹脂でも膜厚が厚い場合にはレジスト
パターンの体積が大きくなりパターンがくずれ易くなる
ため、レジストパターンの破壊が起こった。However, as the demand for dry etch resistance of resists increases and heat resistance at temperatures of 200°C or higher is required, conventional UV-curing processes cannot produce resist patterns with sufficient performance. It's no longer possible. In particular, in recent years, when a resist resin with a low molecular weight is used to improve resolution, the heat resistance of the resist resin becomes low, resulting in a problem that the resist pattern is deformed at a temperature of 100° C. or higher. Further, even if the resist resin has a normal molecular weight, when the film thickness is large, the volume of the resist pattern becomes large and the pattern is easily destroyed, resulting in destruction of the resist pattern.
〔問題点を解決するための手段〕
本発明者は、上記問題点はレジストの架橋反応の促進に
より解決されることを見出し、架橋反応促進方法につき
鋭意検討の結果、ホトレジストによるパターン形成後、
該レジストの有機高分子材料の架橋剤を含有する塗膜を
該レジストパターン上に形成し、レジストと塗膜を反応
させ、その後、塗膜を除去する方法を完成した。[Means for Solving the Problems] The present inventors have found that the above problems can be solved by promoting the crosslinking reaction of the resist, and as a result of intensive studies on methods for promoting the crosslinking reaction, after pattern formation with photoresist,
A method was completed in which a coating film containing a crosslinking agent of the organic polymer material of the resist is formed on the resist pattern, the resist and the coating film are reacted, and then the coating film is removed.
すなわち、本発明は、通常の露光、現像によりレジスト
パターンを形成した後のレジストキュアーを、ＵＶキュ
アで行なわず、該パターン上に塗布された塗膜中の架橋
剤とレジスト樹脂との反応により行なうことを特徴とす
るものであり、かかる反応により単にＵＶキュアに依る
場合よりも耐ドライエツチ性が高められる。なお、本発
明においては、塗膜中の架橋剤とＵＶキュアの併用が可
能であり、この場合は、塗膜上からＵＶ照射を行なうこ
とにより耐ドライエツチ性は著しく高められる。That is, in the present invention, resist curing after forming a resist pattern by normal exposure and development is not performed by UV curing, but is performed by a reaction between a crosslinking agent in a coating film applied on the pattern and a resist resin. This reaction improves the dry etch resistance compared to the case where UV curing alone is used. In the present invention, it is possible to use a crosslinking agent in the coating film together with UV curing, and in this case, the dry etch resistance can be significantly improved by UV irradiation from above the coating film.
以下、本発明を実施するための条件を説明する。Hereinafter, conditions for carrying out the present invention will be explained.
レジストの樹脂と架橋剤の種類は上記架橋反応が生じる
ものであれば、特にその種類に制限はない。レジストと
しては、ノボランク系ポジ型ホトレジストに限らずネガ
レジスト、ＥＢレジスト、ＤＵＶレジスト、ｘ−ルジス
トおよび樹脂においても本発明の方法を適用可能である
。樹脂の分子量については、低分子量の樹脂で１００℃
以上の温度に加熱すると耐熱性が不足する樹脂よりなる
レジストに、本発明の方法を適用することができるし、
また高分子量の樹脂よりなる耐熱性の高いレジストに本
発明の方法を適用しても、耐熱性、耐ドライエツチング
性向上の利点が得られる。There are no particular restrictions on the types of resin and crosslinking agent used in the resist, as long as the above crosslinking reaction occurs. As for resists, the method of the present invention is applicable not only to novolanque positive type photoresists but also to negative resists, EB resists, DUV resists, x-regist, and resins. Regarding the molecular weight of the resin, the temperature is 100℃ for low molecular weight resin.
The method of the present invention can be applied to resists made of resins that lack heat resistance when heated to temperatures above
Furthermore, even when the method of the present invention is applied to a highly heat resistant resist made of a high molecular weight resin, the advantages of improved heat resistance and dry etching resistance can be obtained.
本発明が最も特徴とするところの、架橋剤については、
ビスフェノールエポキシ、ノボラックエポキシ等を使用
することができる。これらの架橋剤は、単独で、好まし
くは溶液もしくは樹脂中に混合させて、レジスト中に塗
布する。この樹脂はＰＭＭＡ、 ＰＶＡ等の樹脂であ
ってもよいが、架橋剤を含有するレジストと該架橋剤は
架橋しないようにレジストと架橋剤の組み合わせを行う
必要がある。Regarding the crosslinking agent, which is the most characteristic feature of the present invention,
Bisphenol epoxy, novolak epoxy, etc. can be used. These crosslinking agents are applied alone, preferably in solution or mixed in a resin, into the resist. This resin may be a resin such as PMMA or PVA, but it is necessary to combine the resist and the crosslinking agent so that the resist containing the crosslinking agent and the crosslinking agent do not crosslink.
架橋剤とレジストの反応は４０〜１００℃で行うことが
好ましい。温度が４０℃未満では架橋反応の進行が緩慢
であり、一方１００℃を越えるとレジストパターンの変
形が激しくなるので好ましくない。The reaction between the crosslinking agent and the resist is preferably carried out at 40 to 100°C. If the temperature is less than 40°C, the crosslinking reaction will progress slowly, while if it exceeds 100°C, the resist pattern will be severely deformed, which is not preferable.
ＵＶ照射を併用する場合は、紫外線の波長は従来法の場
合と同じであってよい。ＵＶ−キュア時には従来法と同
様に１００℃以上の温度で加熱を行なってもよいが、か
かる加熱を行なわなくとも、１００℃以下で、十分にレ
ジストの架橋を行うことができる。ＵＶ照射を併用する
場合、架橋剤の媒体は架橋剤が架橋に必要とする紫外線
の吸収端を有しないことが必要である。かかる媒体とし
てはＰＭＭＡがある。If UV irradiation is also used, the wavelength of the ultraviolet light may be the same as in the conventional method. During UV-curing, heating may be performed at a temperature of 100° C. or higher as in the conventional method, but the resist can be sufficiently crosslinked at a temperature of 100° C. or lower without such heating. When UV irradiation is used in combination, it is necessary that the crosslinking agent medium does not have the ultraviolet absorption edge required for crosslinking. Such a medium is PMMA.
以上のように、架橋剤とレジストを反応させるとレジス
トの表面から反応が進行し、表面から樹脂の硬化が起こ
る。その後、架橋剤を含有する塗膜を適当な溶剤で熔解
すると、耐ドライエツチ性にすぐれたレジストパターン
が得られる。As described above, when the crosslinking agent and the resist are reacted, the reaction proceeds from the surface of the resist, and the resin hardens from the surface. Thereafter, by dissolving the coating film containing the crosslinking agent in a suitable solvent, a resist pattern with excellent dry etch resistance can be obtained.
以下、実施例によりさらに本発明を説明する。The present invention will be further explained below with reference to Examples.
第１図に概略を示すＵＶ−キュア装置を用いて実験を行
なった。図中、３はＵＶ−ランプ、４はホットプレート
、５はウェハー、６はヒーター、７は電源、８はフィル
ター、９はレジストパターンである。Experiments were conducted using a UV-cure apparatus schematically shown in FIG. In the figure, 3 is a UV lamp, 4 is a hot plate, 5 is a wafer, 6 is a heater, 7 is a power source, 8 is a filter, and 9 is a resist pattern.
２．０μｍ厚、パターンサイズ１０μｍノボラック系ポ
ジ型ホトレジストのパターン９を以下の条件でキュアし
た。Pattern 9 of a novolak positive type photoresist having a thickness of 2.0 μm and a pattern size of 10 μm was cured under the following conditions.
第２図の拡大図に示すように、ビスフェノールエポキシ
をＰＭＭＡに５〜１０％溶解した薬品１０を、パターン
ユング後のレジストに、塗布し、レジストパターン９を
ヒーター６で８０℃に保ちながら、ＵＶ−ランプ３とし
てＸｅ−Ｈｇランプ（照度２５．０ｍ Ｗ／ ｃｄ （
３５０ｎ ｍにおいて））を用い、１００秒間照射を行
なった。その後、硫酸によりビスフェノールエポキシ含
有ＰＭＭＡの塗膜を除去した。As shown in the enlarged view of FIG. 2, a chemical 10 in which 5 to 10% bisphenol epoxy is dissolved in PMMA is applied to the resist after patterning, and while the resist pattern 9 is kept at 80°C with a heater 6, UV - Xe-Hg lamp as lamp 3 (illuminance 25.0m W/cd (
Irradiation was carried out for 100 seconds at 350 nm)). Thereafter, the coating film of PMMA containing bisphenol epoxy was removed using sulfuric acid.
ＵＶ−キュアされたレジストの耐熱性を調べるため、レ
ジストパターン９を被着ウェハー５を２５０℃で熱処理
したところ、レジストパターン９の形状変化は認められ
なかった。In order to examine the heat resistance of the UV-cured resist, the wafer 5 to which the resist pattern 9 was attached was heat-treated at 250° C., but no change in the shape of the resist pattern 9 was observed.
比較のために、ビスフェノールエポキシ含有ＰＭＭＡを
塗布しないで同一条件でＵＶキュアを行ない、レジスト
パターン９の形状変化を調べたところ著しい形状変化に
よってパターンサイズが１０±３μｍの範囲で局部的に
増減した。For comparison, UV curing was performed under the same conditions without applying PMMA containing bisphenol epoxy, and changes in the shape of the resist pattern 9 were examined. The pattern size locally increased or decreased within a range of 10±3 μm due to a significant change in shape.
さらに、上記条件の減圧ＵＶ−キュアされたレジストパ
ターン９および比較実験のレジストパターンを用いて、
三塩化ホウ素及び塩素を含むガスを用いたＲＴＥ （リ
アクティブ・イオン・エツチング）によるドライエツチ
ングにより、アルミニウムのパターンサイズを行なった
ところ、ビスフェノールエポキシ含有ＰＭＭＡ塗膜を用
い、ＵＶ−キュアされたレジストパターンのみ設計どお
りの寸法が得られた。Furthermore, using the low pressure UV-cured resist pattern 9 under the above conditions and the resist pattern of the comparative experiment,
The aluminum pattern was sized by dry etching using RTE (reactive ion etching) using a gas containing boron trichloride and chlorine, and the resist pattern was UV-cured using a bisphenol epoxy-containing PMMA coating. Only the dimensions as designed were obtained.
上記実験より明らかであるとうり、本発明によると耐熱
性および耐ドライエツチング性が優れたレジストパター
ンを、正確な所望形状で形成することができる。As is clear from the above experiments, according to the present invention, a resist pattern with excellent heat resistance and dry etching resistance can be formed in an accurate desired shape.
本発明はキュアの効果を高め、架橋反応を促進する。そ
のために、耐熱性および耐ドライエツチング性が高めら
れたレジストパターンを形成することが可能になる。The present invention enhances the curing effect and promotes the crosslinking reaction. Therefore, it becomes possible to form a resist pattern with improved heat resistance and dry etching resistance.
第１図はＵＶ−キュア装置の概念図、
第２図はキュア中のレジストパターンの概念図、３・・
・ＵＶ−ランプ、 ４・・・ホットプレート、５・・
・ウェハー、 ６・・・ヒーター、７・・・電源
、 ８・・・フィルター、９・・・レジスト
パターン、
１０・・・ビスフェノールエポキシ含有ＰＭＭＡ。
め１図
り、２０Figure 1 is a conceptual diagram of the UV-cure device, Figure 2 is a conceptual diagram of the resist pattern during curing, 3...
・UV-lamp, 4...hot plate, 5...
- Wafer, 6... Heater, 7... Power supply, 8... Filter, 9... Resist pattern, 10... PMMA containing bisphenol epoxy. 1 plan, 20
Claims (1)
有機高分子材料の架橋剤を含有する塗膜を該レジストパ
ターン上に形成し、レジストと塗膜を反応させ、その後
、塗膜を除去することを特徴とするレジストハードニン
グ方法。 ２、前記レジストと塗膜の反応は紫外線を照射しながら
行うことを特徴とする特許請求の範囲第１項記載のレジ
ストハードニング方法。[Claims] 1. After pattern formation with photoresist, a coating film containing a crosslinking agent of the organic polymer material of the resist is formed on the resist pattern, the resist and the coating film are reacted, and then the coating film is A resist hardening method characterized by removing. 2. The resist hardening method according to claim 1, wherein the reaction between the resist and the coating film is carried out while irradiating ultraviolet rays.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6242187A JPS63229715A (en) | 1987-03-19 | 1987-03-19 | Resist hardening method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6242187A JPS63229715A (en) | 1987-03-19 | 1987-03-19 | Resist hardening method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63229715A true JPS63229715A (en) | 1988-09-26 |
Family
ID=13199673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6242187A Pending JPS63229715A (en) | 1987-03-19 | 1987-03-19 | Resist hardening method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63229715A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005055294A1 (en) * | 2003-12-02 | 2005-06-16 | Tokyo Electron Limited | Developing method and developing apparatus |
| WO2006018960A1 (en) * | 2004-08-18 | 2006-02-23 | Tokyo Electron Limited | Developing method |
-
1987
- 1987-03-19 JP JP6242187A patent/JPS63229715A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005055294A1 (en) * | 2003-12-02 | 2005-06-16 | Tokyo Electron Limited | Developing method and developing apparatus |
| JP2005189842A (en) * | 2003-12-02 | 2005-07-14 | Tokyo Electron Ltd | Developing method and developing apparatus |
| US7486377B2 (en) | 2003-12-02 | 2009-02-03 | Tokyo Electron Limited | Developing method and developing apparatus |
| JP4652031B2 (en) * | 2003-12-02 | 2011-03-16 | 東京エレクトロン株式会社 | Development processing equipment |
| US8054443B2 (en) | 2003-12-02 | 2011-11-08 | Tokyo Electron Limited | Developing method and developing apparatus |
| WO2006018960A1 (en) * | 2004-08-18 | 2006-02-23 | Tokyo Electron Limited | Developing method |
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