JPH04166945A - Resist composition and formation of resist pattern - Google Patents
Resist composition and formation of resist patternInfo
- Publication number
- JPH04166945A JPH04166945A JP2294706A JP29470690A JPH04166945A JP H04166945 A JPH04166945 A JP H04166945A JP 2294706 A JP2294706 A JP 2294706A JP 29470690 A JP29470690 A JP 29470690A JP H04166945 A JPH04166945 A JP H04166945A
- Authority
- JP
- Japan
- Prior art keywords
- alkali
- resist
- substituent
- resin
- halogen
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title 1
- 239000002253 acid Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 125000001424 substituent group Chemical group 0.000 claims abstract description 18
- 125000005843 halogen group Chemical group 0.000 claims abstract description 11
- 230000005865 ionizing radiation Effects 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 229920003986 novolac Polymers 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 claims description 6
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid Chemical group OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 6
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 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 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 6
- 229920001577 copolymer Polymers 0.000 claims 4
- 230000002378 acidificating effect Effects 0.000 claims 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 2
- 239000000178 monomer Substances 0.000 claims 2
- 125000005372 silanol group Chemical group 0.000 claims 2
- LMWMTSCFTPQVCJ-UHFFFAOYSA-N 2-methylphenol;phenol Chemical compound OC1=CC=CC=C1.CC1=CC=CC=C1O LMWMTSCFTPQVCJ-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 26
- 238000004090 dissolution Methods 0.000 abstract description 23
- 230000002401 inhibitory effect Effects 0.000 abstract description 17
- 239000003513 alkali Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000002585 base Substances 0.000 abstract description 4
- 239000012433 hydrogen halide Substances 0.000 abstract description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 229940072293 axid Drugs 0.000 abstract 1
- SGXXNSQHWDMGGP-IZZDOVSWSA-N nizatidine Chemical compound [O-][N+](=O)\C=C(/NC)NCCSCC1=CSC(CN(C)C)=N1 SGXXNSQHWDMGGP-IZZDOVSWSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 238000010894 electron beam technology Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Landscapes
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔概要〕
電離放射線用ポジ型レジストに関し、
アルカリ現像が可能で感度と解像性に優れたレジスト組
成物を提供することを目的とし、アルカリ可溶性樹脂を
基材樹脂とし、該基材樹脂と、構造式中にハロゲン系置
換基を少なくとも一種類以」二含むと共に、−ＯＣＯＣ
Ｒ１Ｒ２Ｒ３または一０Ｃ００ＣＲＩＲ２Ｒ３で表され
る置換基を含む酸発生剤とからなることを特徴としてレ
ジスト組成物を構成する。こ＼で、ハロゲン系置換基は
ハロゲン基、ハロゲン化アルキル基、ポリハロゲン化ア
ルキル基を、また、Ｒ１＋ Ｒ２，Ｒ３は炭素数か１〜
１２のアルキル基、フェニル基、または水素の一部か全
部をメチル基かエチル基で置換したフェニル基を、また
アルカリ可溶性樹脂とは、ノボラック樹脂、骨格中にヒ
ドロキシスチレンまたはカルボキシスチレン構造を含む
樹脂、シリコン含有アルカリ可溶性樹脂の何れかを指す
。[Detailed Description of the Invention] [Summary] Regarding positive resists for ionizing radiation, the present invention aims to provide a resist composition that can be developed with alkali and has excellent sensitivity and resolution, and uses an alkali-soluble resin as a base resin. , the base resin contains at least one type of halogen substituent in the structural formula, and -OCOC
and an acid generator containing a substituent represented by R1R2R3 or 10C00CRIR2R3. Here, the halogen substituent is a halogen group, a halogenated alkyl group, a polyhalogenated alkyl group, and R1+ R2, R3 are carbon atoms or 1 to 1.
12 alkyl groups, phenyl groups, or phenyl groups in which some or all of the hydrogens are substituted with methyl or ethyl groups, and alkali-soluble resins include novolak resins, resins containing hydroxystyrene or carboxystyrene structures in the skeleton , refers to any silicon-containing alkali-soluble resin.
本発明は感度と解像性の優れた電離放射線用ポジ型レジ
ストに関する。The present invention relates to a positive resist for ionizing radiation that has excellent sensitivity and resolution.
大量の情報を高速に処理する必要性から情報処理装置の
主体を構成する半導体装置は集積化か進んてＬＳＪやＶ
ＬＳ Ｉが実用化されているが更に集積化する傾向にあ
る。Due to the need to process large amounts of information at high speed, the semiconductor devices that make up the main body of information processing equipment are becoming more integrated, such as LSJ and V
Although LSI has been put into practical use, there is a trend toward further integration.
すなわち、最新のＶＬＳ Ｉの最小パターン幅は０．４
μｍのものが用いられており、更に縮小する傾向にある
。In other words, the minimum pattern width of the latest VLS I is 0.4
Micrometers are used, and there is a tendency to further reduce the size.
こ＼で、微細パターンの形成にはパターン形成材料を膜
形成しである半導体被処理基板上に、レジストをスピン
コード法により被覆した後、マスクの密着露光あるいは
投影露光などの方法てレジストを選択的に露光した後、
現像してレジストパターンを作り、これをマスクとして
ドライエツチングまたはウェットエツチングを行って被
処理基板上に薄膜パターンを形成する写真蝕刻技術（フ
ォトリソグラフィ或いは電子線リソグラフィ）か用いら
れている。In order to form a fine pattern, a resist is coated on the semiconductor substrate to be processed using a spin code method, and then a resist is selected using a method such as contact exposure using a mask or projection exposure. After exposure to
A photolithography technique (photolithography or electron beam lithography) is used in which a resist pattern is developed and used as a mask to perform dry etching or wet etching to form a thin film pattern on a substrate to be processed.
そこで、被処理基板上に微細パターンを形成するために
は、これに使用するレジストが高解像性なことが必要で
あり、また生産性を向上するためには高感度のものが必
要である。Therefore, in order to form fine patterns on the substrate to be processed, the resist used must have high resolution, and in order to improve productivity, it must be highly sensitive. .
最近、感度と解像度を向上てきるレジストとして化学増
幅型レジストが注目されている。Recently, chemically amplified resists have been attracting attention as resists that can improve sensitivity and resolution.
このレジストは組成中に酸発生剤を含んでおり、光照射
により発生した酸が触媒的に作用し、分子の分解や架橋
などの反応を起こすために感度か高い。This resist contains an acid generator in its composition, and the acid generated by light irradiation acts as a catalyst and causes reactions such as molecular decomposition and crosslinking, so it has high sensitivity.
また、酸の拡散距離が約５ｎｍと極めて小さいために解
像性も優れている。Furthermore, since the acid diffusion distance is extremely small, about 5 nm, the resolution is also excellent.
か−る化学増幅型レジストは組成の面から概ね次の四種
類に分類されている。Such chemically amplified resists are generally classified into the following four types in terms of composition.
（１） アルカリ可溶性樹脂＋架橋剤＋酸発生剤・・
・（ネガ型レジスト）
（２）アルカリ可溶性樹脂士溶解抑制剤十酸発生剤・・
・（ポジ型レジスト）
（３）アルカリ不溶性樹脂土酸発生剤
・・・（ポジ型レジスト）
（４）アルカリ可溶性樹脂土酸発生剤
・・・（ポジ型レジスト）
なお、酸発生剤としてはスルホニウム塩（例えばＰｈ５
Ｓ” ５ｂＰ６− ）やヨードニウム塩（例えば円１２
１′″５ｌ）Ｆ６− ）などのオニウム塩か知られてい
る。(1) Alkali-soluble resin + crosslinking agent + acid generator...
・(Negative resist) (2) Alkali-soluble resin dissolution inhibitor decaic acid generator...
・(Positive resist) (3) Alkali-insoluble resin acid generator...(Positive resist) (4) Alkali-soluble resin acid generator...(Positive resist) Note that sulfonium is used as the acid generator. Salt (e.g. Ph5
S''5bP6-) and iodonium salts (e.g. 12
Onium salts such as 1'''5l)F6-) are known.
こ＼で、（４）に関連したレジストについて述べると、
か＼るオニウム塩をリンスＩ・に加え、アルカリ現像液
に対する溶解抑止剤として使用する方法が発表されてい
る。Now, let's talk about the resist related to (4).
A method has been published in which an onium salt is added to Rinse I and used as a dissolution inhibitor for an alkaline developer.
（Ｉ（、Ｉｔｏ他、 Ｊ、 Ｅｌｅｃｔｒｏｃｈｅｍ、
Ｓｏｃ、 Ｖｏｌ、 １３５． Ｎｏ、 ９．２３２
２、１９８８）
然し、この方法は光照射により発生する酸か触媒的に利
用されている訳ではないので厳密には化学増幅型とは言
えない。(I(, Ito et al., J, Electrochem,
Soc, Vol, 135. No, 9.232
2, 1988) However, this method cannot be strictly called a chemical amplification type because the acid generated by light irradiation is not used as a catalyst.
また、オニウム塩はクレゾールノボラック樹脂に対して
は溶解抑止効果は高いかポリヒドロキシスチレンに対し
ては充分とは言えない。Furthermore, onium salts have a high dissolution inhibiting effect on cresol novolac resins, but cannot be said to have a sufficient effect on polyhydroxystyrene.
その後、ｒｓＬｌｃｃＥｓｓ ｊ と名付けた溶解抑止
剤かＢＡＳＰ社とＳｉｅｍｅｎｓ社の共同研究として発
表された。Subsequently, a dissolution inhibitor named rsLlccEss j was announced as a joint research between BASP and Siemens.
ｒＰｏｌｙｍｅｒ ｆｏｒ Ｍｉｃｒｏｅｌｅｃｔｒｏ
ｎｉｃｓ、８９ ｉｎ Ｔｏｋｙｏ」この溶解抑止剤は
基本的にはオニウム塩であるか、特徴として構造中に酸
によって分解されて極性か変化する置換基をもっている
ために、電離放射線露光部と未露光部との溶解性の差が
一層大きくなっている。rPolymer for Microelectro
nics, 89 in Tokyo" This dissolution inhibitor is basically an onium salt or has a substituent in its structure that changes polarity when decomposed by acid, so it has a tendency to separate areas exposed to ionizing radiation and areas unexposed. The difference in solubility between
この種のレジストは酸か触媒として作用する化学増幅型
レジストであり、タレゾールノボラックのみならずポリ
ヒドロキシスチレンに対しても充分な溶解抑止効果をも
っている。This type of resist is a chemically amplified resist that acts as an acid or catalyst, and has a sufficient dissolution inhibiting effect not only on Talesol novolac but also on polyhydroxystyrene.
以」二記したように、（４）に分類される化学増幅型レ
ジストは溶解を抑制すると共に酸を発生する材料（以下
略して溶解抑止酸発生剤）として何れもオニウム塩を使
用している。As mentioned above, chemically amplified resists classified as (4) all use onium salts as materials that suppress dissolution and generate acid (hereinafter referred to as dissolution-inhibiting acid generators). .
然し、このような酸発生剤はイオン系であるために長波
長（＞３００ｎｍ）の紫外線に対しては感度か低いと云
う問題がある。However, since such acid generators are ionic, they have a problem of low sensitivity to long wavelength (>300 nm) ultraviolet rays.
また、リンスｌ〜の溶剤として一般に使用されているジ
−ｔ−ブチルエーテル、メチルイソブチルケトンなどに
対して溶解度が低く、必要量まで溶すことが難しい。Furthermore, it has low solubility in di-t-butyl ether, methyl isobutyl ketone, etc. that are generally used as solvents for rinses 1 and 2, and it is difficult to dissolve them in the required amount.
また、オニウム塩は有毒なことも問題となっている。Another problem is that onium salts are toxic.
溶解抑止酸発生剤とアルカリ可溶性樹脂とからなるレジ
スト組成物は二成分からなるために濃度比の適性化が容
易に行なわれる利点がある。A resist composition consisting of a dissolution-inhibiting acid generator and an alkali-soluble resin has the advantage that the concentration ratio can be easily adjusted because it consists of two components.
然し、従来の溶解抑止酸発生剤はイオン系のために長波
長の紫外線に対しては感度か低く、また溶媒に対して溶
解度か低い。However, since conventional dissolution-inhibiting acid generators are ionic, they have low sensitivity to long wavelength ultraviolet rays and low solubility in solvents.
そこで、長波長の紫外線に対して感度と解像性が優れ、
アルカリ現像可能なレジストを実用化することか課題で
ある。Therefore, it has excellent sensitivity and resolution to long wavelength ultraviolet rays,
The challenge is to put a resist that can be developed in alkali into practical use.
上記の課題はアルカリ可溶性樹脂を基材樹脂とし、この
基材樹脂と、構造式中にハロゲン系置換基を少なくとも
一種類以上含むと共に、−０ＣＯＣ１’ｉ’、Ｒ２Ｒ３
または−ＣＯＯＣＲ＋ＲｚＲＰで表される置換基を含む
酸発生剤とからなることを特徴としてリンス１へ組成物
を構成することにより解決することがてきる。The above problem is solved by using an alkali-soluble resin as a base resin, and containing at least one type of halogen substituent in the structural formula, -0COC1'i', R2R3
Alternatively, the problem can be solved by forming a composition in the rinse 1 characterized by consisting of an acid generator containing a substituent represented by -COOCR+RzRP.
こゝで、ハロケン系置換基はハロゲン基、ハロゲン化ア
ルキル基、ポリハロゲン化アルギル基を指し、また、Ｒ
１，Ｒ２，Ｒ３は炭素数が１〜１２のアルキル基、フェ
ニル基、または水素の一部か全部をメチル基かエチル基
で置換したフェニル基を指し、またアルカリ可溶性樹脂
とは、ノボラック樹脂。Here, the halokene-based substituent refers to a halogen group, a halogenated alkyl group, a polyhalogenated argyl group, and R
1, R2, and R3 refer to an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a phenyl group in which part or all of the hydrogen atoms are substituted with a methyl group or an ethyl group, and the alkali-soluble resin is a novolac resin.
骨格中にヒドロキシスチレンまたはカルボキシスチレン
構造を含む樹脂、シリコン含有アルカリ可溶性樹脂の何
れかを指す。Refers to either a resin containing a hydroxystyrene or carboxystyrene structure in the skeleton or an alkali-soluble silicon-containing resin.
本発明に係り、構造式中にハロゲン系置換基を少なくと
も一種類以上含むと共に、−ＯＣＯＣＲ１Ｒ７Ｒ。According to the present invention, the structural formula includes at least one type of halogen substituent, and -OCOCR1R7R.
または−０ＣＯＯＣＲ，Ｒ２Ｒ３で表される置換基を含
む酸発生剤はアルカリ現像液に対して充分な溶解抑止効
果をもっている。An acid generator containing a substituent represented by -0COOCR or R2R3 has a sufficient effect of inhibiting dissolution in an alkaline developer.
すなわち、この溶解抑止酸発生剤をアルカリ可溶性樹脂
に加えて調整したレジストは、そのま＼てはアルカリ現
像液には溶解しないか、電離放射線を照射すると、露光
部の溶解抑止酸発生剤は、ハロゲンを含む置換基からハ
ロゲン原子かラジｈルの形で外れ、残存している溶媒か
ら水素原子を抜き取ってハロゲン化水素となる。That is, a resist prepared by adding this dissolution-inhibiting acid generator to an alkali-soluble resin does not dissolve in an alkaline developer, or when irradiated with ionizing radiation, the dissolution-inhibiting acid generator in the exposed area becomes A halogen atom is removed from a halogen-containing substituent in the form of a radical h, and a hydrogen atom is extracted from the remaining solvent to form a hydrogen halide.
次に、これが−０ＣＯＣＲＩＲ２Ｒ２または−ＣＯＯＣ
Ｒ，Ｒ２Ｒ３で示される置換基を攻撃する。Then this is -0COCRIR2R2 or -COOC
Attacks the substituent represented by R, R2R3.
その結果、これらの置換基の中でＣ０ＣＲ，Ｒ２Ｒ，ま
たはＣ００ＣＲ＋Ｒ２Ｒ１の部分が加水分解により外れ
て水酸基となり、極性が大きく変化する。As a result, among these substituents, the C0CR, R2R, or C00CR+R2R1 portion is removed by hydrolysis and becomes a hydroxyl group, resulting in a significant change in polarity.
このため、アルカリ現像液に対する溶解性が増大し、従
ってポジ型のレジストパターンを得ることができる。Therefore, the solubility in an alkaline developer increases, and therefore a positive resist pattern can be obtained.
なお、か〜る溶解抑止酸発生剤は非イオン性であること
から溶媒に対する溶解性が良好で、構造を工夫すること
により長波長域の紫外線に対する感度を向上することが
できる。Since the dissolution-inhibiting acid generator is nonionic, it has good solubility in solvents, and by devising the structure, it is possible to improve the sensitivity to ultraviolet rays in the long wavelength range.
また、毒性も低く、実用的である。In addition, it has low toxicity and is practical.
なお、−ＯＣＯＣＲ１Ｒ２Ｒ，または−ＣＯＯＣＲ，Ｒ
２Ｒ，で示される置換基において、アルキル基の炭素数
を１〜１２に制限している理由はアルキル基の炭素数が
大きくなると、酸による攻撃が妨げられる（立体障害）
からである。In addition, -OCOCR1R2R, or -COOCR,R
In the substituent represented by 2R, the number of carbon atoms in the alkyl group is limited to 1 to 12 because as the number of carbon atoms in the alkyl group increases, attack by acids is hindered (steric hindrance).
It is from.
なお、溶解抑止酸発生剤が充分な酸発生機能を示すため
にはハロゲンを含む置換基の数か、−ＯＣＯＣＲ１Ｒ２
Ｒ３または−ＣＯＯＣＲ，Ｒ２Ｒ３で示される置換基の
数の１０％以上８０％以下であることが必要である。In addition, in order for the dissolution inhibiting acid generator to exhibit sufficient acid generation function, the number of substituents containing halogen, -OCOCR1R2
It is necessary that the number of substituents represented by R3 or -COOCR, R2R3 is 10% or more and 80% or less.
実施例１：
第１図（Ａ）に示し、酸発生剤の一種として知られてい
るテトラブロモビスフェノールＡの水酸基をアルカリ触
媒（ピリジン）を使用し−ＣＯＣ（ＣＩ−１３）３で置
換して同図（Ｂ）に示す溶解抑止酸発生剤を合成した。Example 1: The hydroxyl group of tetrabromobisphenol A, which is shown in FIG. The dissolution-inhibiting acid generator shown in FIG. 2(B) was synthesized.
この溶解抑止酸発生剤０．３ｇと重量平均分子量が５．
４ ＸＩＯ３のクレゾールノボラック１ｇとをメチルイ
ソブチルケトン（略称ＭＩＢＫ）３．７ｇに溶解し、０
．２μｍのメンブランフィルタで濾過することによりレ
ジスト溶液を作成した。The weight average molecular weight of 0.3 g of this dissolution inhibiting acid generator is 5.
4 Dissolve 1 g of XIO3 cresol novolak in 3.7 g of methyl isobutyl ketone (abbreviated as MIBK),
．． A resist solution was prepared by filtering through a 2 μm membrane filter.
このレジスト溶液をＳｉウェハ上に０．７μｍの厚さに
塗布して露光用の試料とし、電子線露光を行った。This resist solution was coated onto a Si wafer to a thickness of 0.7 μm to prepare a sample for exposure, and electron beam exposure was performed.
そして、露光した後、直ちにホットプレートにで１０５
℃で２分間ベークした後、０．２Ｎのテトラメチルアン
モニウムハイドロオキサイド（略称ＴＭＡＨ）よりなる
アルカリ現像液で１０分間浸漬現像を行った。After exposure, immediately put it on a hot plate at 105
After baking at .degree. C. for 2 minutes, immersion development was performed for 10 minutes in an alkaline developer consisting of 0.2N tetramethylammonium hydroxide (abbreviated as TMAH).
そして、電子線感度を測定したところ、残膜率０％の時
の露光量（これを感度と呼ぶことにする）は６μＣ／ｃ
ｍ２であった。When the electron beam sensitivity was measured, the exposure amount (this will be referred to as sensitivity) when the residual film rate was 0% was 6μC/c.
It was m2.
また、０．３μｍのライン・アンド・スペースを解像す
ることができた。Furthermore, it was possible to resolve lines and spaces of 0.3 μm.
実施例２：
実施例１と同様にして形成した露光用の試料に波長が４
．４人の軟Ｘ線を照射し、同様にして感度と解像性を調
べた。Example 2: A sample for exposure formed in the same manner as in Example 1 had a wavelength of 4.
．． Four people were irradiated with soft X-rays and sensitivity and resolution were examined in the same way.
その結果、感度は４０ｍＪ／ｃｍ２であり、解像性はＸ
線マスクの最小線幅である０、４μｍのライン・アンド
・スペースを解像することができた。As a result, the sensitivity was 40mJ/cm2, and the resolution was
It was possible to resolve lines and spaces of 0.4 μm, which is the minimum line width of the line mask.
実施例３：
実施例１と同様にして形成した露光用の試料に波長が２
４８ｎｍのＫｒＦエキシマレーザを照射し、感度と解像
性を調べた。Example 3: A sample for exposure formed in the same manner as in Example 1 had a wavelength of 2.
The sensitivity and resolution were examined by irradiating with a 48 nm KrF excimer laser.
その結果、感度は５３ｍＪ／ｃｍ２であり、解像性はフ
ォトマスクの最小線幅である０、４μｍのライン・アン
ド・スペースを解像することができた。As a result, the sensitivity was 53 mJ/cm2, and the resolution was able to resolve lines and spaces of 0.4 μm, which is the minimum line width of the photomask.
実施例４：
実施例１で作成した溶解防止酸発生剤０．３ｇと重量平
均分子量が１．ＯＸＩＯ’のポリパラヒドロキシスチレ
ン１ｇをＭＩＢＫ ３．７ｇに溶解し、０．２μｍのメ
ンブランフィルタで濾過することによりレジスト溶液を
作成した。Example 4: 0.3 g of the anti-dissolution acid generator prepared in Example 1 and a weight average molecular weight of 1. A resist solution was prepared by dissolving 1 g of polyparahydroxystyrene (OXIO') in 3.7 g of MIBK and filtering the solution through a 0.2 μm membrane filter.
このレジスト溶液をＳｉウェハ上に０．７μｍの厚さに
塗布して露光用の試料とし、電子線露光を行った。This resist solution was coated onto a Si wafer to a thickness of 0.7 μm to prepare a sample for exposure, and electron beam exposure was performed.
そして、露光した後、直ちにホットプレート上で１０５
°Ｃで２分間ベークした後、０．２ＮのＴＭＡＨよりな
るアルカリ現像液で１０分間浸漬現像を行った。After exposure, immediately place it on a hot plate at 105
After baking at °C for 2 minutes, immersion development was performed for 10 minutes in an alkaline developer consisting of 0.2N TMAH.
そして、電子線感度を測定したところ、４μＣ／ｃｍ２
であった。When the electron beam sensitivity was measured, it was found to be 4μC/cm2.
Met.
また、０．３μｍのライン・アンド・スペースを解像す
ることができた。Furthermore, it was possible to resolve lines and spaces of 0.3 μm.
実施例５：
実施例４と同様にして形成した露光用の試料に波長が４
３４人の軟Ｘ線を照射し、同様にして感度と解像性を調
べた。Example 5: A sample for exposure formed in the same manner as in Example 4 had a wavelength of 4.
Thirty-four people were irradiated with soft X-rays, and sensitivity and resolution were examined in the same manner.
その結果、感度は３５ｍＪ／ｃｍ２であり、解像性はＸ
線マスクの最小線幅である０、４μｍのライン・アンド
・スペースを解像することかできた。As a result, the sensitivity was 35 mJ/cm2, and the resolution was
It was possible to resolve line and spaces of 0.4 μm, which is the minimum line width of a line mask.
実施例６゜
実施例４と同様にして形成した露光用の試料に波長が２
４８ｎｍのＫｒＦエキシマレーザを照射し、感度と解像
性を調へた。Example 6゜A sample for exposure formed in the same manner as in Example 4 had a wavelength of 2.
The sensitivity and resolution were adjusted by irradiating with a 48 nm KrF excimer laser.
その結果、感度は５０ｍＪ／ｃｍ２てあり、解像性はフ
ォトマスクの最小線幅である０、４μｍのライン・アン
ド・スペースを解像することかできた。As a result, the sensitivity was 50 mJ/cm2, and the resolution was able to resolve lines and spaces of 0.4 μm, which is the minimum line width of the photomask.
実施例７：
第１図（Ａ）に示し、酸発生剤の一種として知られてい
るテトラブロモビスフェノールへの水酸基をアルカリ触
媒（ピリジン）を使用し−ＣＯＣＰｈ（ＣＨ３）３て置
換して溶解抑止酸発生剤を合成した。Example 7: As shown in Figure 1 (A), the hydroxyl group of tetrabromobisphenol, which is known as a type of acid generator, is replaced with -COCPh(CH3)3 using an alkali catalyst (pyridine) to inhibit dissolution. An acid generator was synthesized.
この溶解抑止酸発生剤０．３ｇと重量平均分子量が２．
１ ＸＩＯ３で第２図に構造式を示すＳｉ含有アルカリ
可溶性樹脂１ｇをＭＩＢＫ ３．７ｇ ＋、：溶解し１
．０゜２μｍのメンブランフィルタで濾過することによ
りレジスト溶液を作成した。The weight average molecular weight of 0.3 g of this dissolution inhibiting acid generator is 2.
1 Dissolve 1 g of Si-containing alkali-soluble resin whose structural formula is shown in Figure 2 in XIO3 with 3.7 g of MIBK +, 1
．． A resist solution was prepared by filtering through a 0°2 μm membrane filter.
このレジスト溶液をＳ１ウエハ上に０．７μｍの厚さに
塗布して露光用の試料とし、電子線露光を行った。This resist solution was coated onto an S1 wafer to a thickness of 0.7 μm to prepare a sample for exposure, and electron beam exposure was performed.
そして、露光した後、直ぢにホットプレートで１０５°
Ｃで２分間ベークした後、０．２ＮのＴＭＡＨよりなる
アルカリ現像液で１０分間浸漬現像を行った。After exposure, directly heat the film at 105° on a hot plate.
After baking at C for 2 minutes, immersion development was performed for 10 minutes in an alkaline developer consisting of 0.2N TMAH.
そして、電子線感度を測定したところ、５μＣ／ｃｍ２
であった。When the electron beam sensitivity was measured, it was found to be 5μC/cm2.
Met.
また、０．３μｍのライン・アンド・スペースを解像す
ることができた。Furthermore, it was possible to resolve lines and spaces of 0.3 μm.
実施例８：
実施例７と同様にして形成した露光用の試料に波長が４
．４人の軟Ｘ線を照射し、同様にして感度と解像性を調
べた。Example 8: A sample for exposure formed in the same manner as in Example 7 had a wavelength of 4.
．． Four people were irradiated with soft X-rays and sensitivity and resolution were examined in the same way.
その結果、感度は５５ｍＪ７ｃｍ２であり、解像性はＸ
線マスクの最小線幅である０．４μｍのライン・アンド
・スペースを解像することかできた。As a result, the sensitivity was 55mJ7cm2, and the resolution was
It was possible to resolve line and spaces of 0.4 μm, which is the minimum line width of the line mask.
実施例９：
実施例７と同様にして形成した露光用の試料に波長が２
４８ｎｍのＫｒＰエキシマレーザを照射し、感度と解像
性を調べた。Example 9: A sample for exposure formed in the same manner as in Example 7 had a wavelength of 2.
The sensitivity and resolution were examined by irradiating with a 48 nm KrP excimer laser.
その結果、感度は３４ｍＪ／ｃｍ２てあり、解像性はフ
ォトマスクの最小線幅である０．４μｍのライン・アン
ド・スペースを解像することができた。As a result, the sensitivity was 34 mJ/cm2, and the resolution was able to resolve lines and spaces of 0.4 μm, which is the minimum line width of the photomask.
実施例１Ｏ：
径５インチのＳｉ基板上にノボラック樹脂（品名ＭＰー
１３００，シブレイ社製）を２μｍの厚さにスピンコー
１へした後、実施例１て形成したレジストを０。Example 1O: After applying a novolac resin (product name MP-1300, manufactured by Sibley Corporation) to a thickness of 2 μm using a spin coat 1 on a Si substrate with a diameter of 5 inches, the resist formed in Example 1 was applied to the substrate.
５μｍの厚さにスピンコードし、電子線走査を行って選
択的に露光させ、アルカリ現像液で現像してパターンニ
ングを行った。It was spin-coded to a thickness of 5 μm, selectively exposed by electron beam scanning, and patterned by development with an alkaline developer.
次に、この試料を平行平板型のドライエツチング装置に
入れ、酸素プラズマ（ ２ Ｐａ． ０． ２２ Ｗ／
ｃｍ２）で１５分間に亙ってドライエツチングを行い、
」二層パターンを下層に転写した。Next, this sample was placed in a parallel plate type dry etching device and exposed to oxygen plasma (2 Pa. 0.22 W/
cm2) for 15 minutes,
” The two-layer pattern was transferred to the lower layer.
その結果、アスペクト比か高く、また０．４μｍのライ
ン・アンド・スペースを解像することかてきた。As a result, the aspect ratio was high and it was possible to resolve lines and spaces of 0.4 μm.
なお、光源として軟Ｘ線およびＫｒＦエキシマレーザを
用いた場合も類似の結果を得ることができた。Note that similar results were obtained when soft X-rays and KrF excimer laser were used as the light source.
本発明によれば、感度と解像性に優れ、アルカリ現像で
きる電離放射線用ポジ型レジストを実用化することがで
きる。According to the present invention, it is possible to put into practical use a positive resist for ionizing radiation that has excellent sensitivity and resolution and can be developed with alkali.
第１図は実施例１に使用した溶解抑止酸発生剤の構造式
、
第２図はＳｉ含存アルカリ可溶性樹脂の構造式、である
。FIG. 1 shows the structural formula of the dissolution-inhibiting acid generator used in Example 1, and FIG. 2 shows the structural formula of the Si-containing alkali-soluble resin.
Claims (5)
と、構造式中にハロゲン系置換基を少なくとも一種類以
上含むと共に、−ＯＣＯＣＲ＿１Ｒ＿２Ｒ＿３または−
ＯＣＯＯＣＲ＿１Ｒ＿２Ｒ＿３で表される置換基を含む
酸発生剤とからなることを特徴とするレジスト組成物。 こゝで、ハロゲン系置換基はハロゲン基、ハロゲン化ア
ルキル基、ポリハロゲン化アルキル基を指す。 また、Ｒ＿１、Ｒ＿２、Ｒ＿３は炭素数が１〜１２のア
ルキル基、フェニル基、または水素の一部か全部をメチ
ル基かエチル基で置換したフェニル基を指す。(1) An alkali-soluble resin is used as a base resin, and the base resin and the structural formula contain at least one type of halogen substituent, and -OCOCR_1R_2R_3 or -
A resist composition comprising an acid generator containing a substituent represented by OCOOCR_1R_2R_3. Here, the halogen-based substituent refers to a halogen group, a halogenated alkyl group, and a polyhalogenated alkyl group. Further, R_1, R_2, and R_3 refer to an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a phenyl group in which part or all of the hydrogen atoms are substituted with a methyl group or an ethyl group.
からなる請求項１記載のレジスト組成物。 こゝで、ノボラック樹脂はフェノールノボラック、クレ
ゾールノボラック、フェノールクレゾールノボラック樹
脂を指す。(2) The resist composition according to claim 1, wherein the alkali-soluble resin is a novolak resin. Here, novolak resin refers to phenol novolak, cresol novolak, and phenol cresol novolak resin.
キシスチレンまたはカルボキシスチレン構造を含む樹脂
からなる請求項１記載のレジスト組成物。 こゝで、骨格中にヒドロキシスチレンまたはカルボキシ
スチレン構造を含む樹脂とは、 ポリヒドロキシスチレン、ポリカルボキシスチレン、ヒ
ドロキシスチレンと炭素−炭素二重結合を含むモノマと
の共重合体、カルボキシスチレンと炭素−炭素二重結合
を含むモノマとの共重合体、ヒドロキシスチレンとカル
ボキシスチレンとの共重合体の何れかを指す。(3) The resist composition according to claim 1, wherein the alkali-soluble resin is a resin containing a hydroxystyrene or carboxystyrene structure in its skeleton. Here, resins containing a hydroxystyrene or carboxystyrene structure in the skeleton include polyhydroxystyrene, polycarboxystyrene, a copolymer of hydroxystyrene and a monomer containing a carbon-carbon double bond, and a copolymer of carboxystyrene and a carbon-carbon double bond. Refers to either a copolymer with a monomer containing a carbon double bond or a copolymer of hydroxystyrene and carboxystyrene.
ルカリ可溶性樹脂からなる請求項１記載のレジスト組成
物。 こゝで、シリコン含有アルカリ可溶性樹脂とはアセチル
化されたシロキサンポリマ、 アセチル化されたシルフェニレンシロキサンポリマ、シ
ラノール基をもつシロキサンポリマ、シラノール基をも
つシルフェニレンシロキサンポリマ、カルボキシル基ま
たは酸性水酸基をもつシロキサンポリマ、カルボキシル
基または酸性水酸基をもつシルフェニレンシロキサンポ
リマの何れかを指す。(4) The resist composition according to claim 1, wherein the alkali-soluble resin comprises a silicon-containing alkali-soluble resin. Here, silicon-containing alkali-soluble resins include acetylated siloxane polymers, acetylated silphenylene siloxane polymers, siloxane polymers with silanol groups, silphenylene siloxane polymers with silanol groups, and polymers with carboxyl groups or acidic hydroxyl groups. Refers to either a siloxane polymer or a silphenylene siloxane polymer having a carboxyl group or an acidic hydroxyl group.
処理基板に被覆した後、電離放射線を照射し、アルカリ
水溶液で現像することを特徴とするレジストパターン形
成方法。(5) A method for forming a resist pattern, which comprises coating a substrate with the resist composition according to any one of claims 1 to 4, irradiating it with ionizing radiation, and developing it with an alkaline aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2294706A JPH04166945A (en) | 1990-10-31 | 1990-10-31 | Resist composition and formation of resist pattern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2294706A JPH04166945A (en) | 1990-10-31 | 1990-10-31 | Resist composition and formation of resist pattern |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04166945A true JPH04166945A (en) | 1992-06-12 |
Family
ID=17811250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2294706A Pending JPH04166945A (en) | 1990-10-31 | 1990-10-31 | Resist composition and formation of resist pattern |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04166945A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2386591A3 (en) * | 2010-05-07 | 2012-03-21 | Shin-Etsu Chemical Co., Ltd. | Novel silphenylene skeleton-containing silicon type polymer and method for manufacturing the same |
-
1990
- 1990-10-31 JP JP2294706A patent/JPH04166945A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2386591A3 (en) * | 2010-05-07 | 2012-03-21 | Shin-Etsu Chemical Co., Ltd. | Novel silphenylene skeleton-containing silicon type polymer and method for manufacturing the same |
| US8476379B2 (en) | 2010-05-07 | 2013-07-02 | Shin-Etsu Chemical Co., Ltd. | Silphenylene skeleton-containing silicone type polymer and method for manufacturing the same |
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