JPH03223857A - Pattern forming method - Google Patents
Pattern forming methodInfo
- Publication number
- JPH03223857A JPH03223857A JP2019529A JP1952990A JPH03223857A JP H03223857 A JPH03223857 A JP H03223857A JP 2019529 A JP2019529 A JP 2019529A JP 1952990 A JP1952990 A JP 1952990A JP H03223857 A JPH03223857 A JP H03223857A
- Authority
- JP
- Japan
- Prior art keywords
- group
- acid
- pattern
- resin
- pattern forming
- 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
- 238000000034 method Methods 0.000 title claims description 26
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000002253 acid Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 125000000524 functional group Chemical group 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- -1 2-hydroxyethoxycarbonyl group Chemical group 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 claims description 4
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 claims description 3
- 230000007261 regionalization Effects 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001412 tetrahydropyranyl group Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- SYWSWGZFNZHQHC-UHFFFAOYSA-N 1-hydroxy-2,3,4-trimethylsiline Chemical compound CC1=C(C)C(C)=[Si](O)C=C1 SYWSWGZFNZHQHC-UHFFFAOYSA-N 0.000 description 1
- UTQNKKSJPHTPBS-UHFFFAOYSA-N 2,2,2-trichloroethanone Chemical group ClC(Cl)(Cl)[C]=O UTQNKKSJPHTPBS-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 125000006502 nitrobenzyl group Chemical group 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は半導体素子等を製造する時に用いられるレジス
トパターン形成方法に係り、露光エネルギー源として、
たとえば４００ｎｍ以下の紫外撒エキシマレーザ等を用
いてポジ型のパターンを形成する際のパターン形成方法
に係る。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a resist pattern forming method used in manufacturing semiconductor devices, etc.
For example, the present invention relates to a pattern forming method when forming a positive pattern using an ultraviolet excimer laser of 400 nm or less.
従来の技術
近鍛 半導体デバイスの高密度集積化に伴し＼微細加工
中でもフォトリソグラフィに用いる露光装置の光源波
長は益々短波長化し 現段階では１線（３６５ｎｍ）が
実用段階に入り、ＫｒＦｙ−キシマレーサ（２４８，４
ｎｍ）が検討されるまでになっている。しかしながら、
レジストパターン形成材料、特にＫｒＦエキシマレー
サミ 遠紫外線波長域に適したものは未だ開発されてい
なｌ、Ｘｏ 例えばＫｒＦエキシマレーサ光 遠紫外
線に対し感光性か高く、透過率も高いと言われるＭＰ２
４００（シブレイ社）を用いた場合でＬ ベースポリマ
ーであるノボラック樹脂自身の大きな表面吸収や感光剤
のナフトキノンジアジド系化合物の光反応が良くないた
人 パターン形成後のパターン形状は非常に悪く使用で
きそうにない。Conventional technology As semiconductor devices become more densely integrated, the light source wavelength of exposure equipment used in photolithography becomes increasingly shorter. (248,4
nm) is now being considered. however,
Resist pattern forming materials, especially KrF excimer lasers Materials suitable for deep ultraviolet wavelengths have not yet been developed. For example, KrF excimer laser light MP2 is said to be highly sensitive to far ultraviolet rays and has high transmittance.
400 (Sibley), the large surface absorption of the novolac resin itself, which is the base polymer, and the photoreaction of the naphthoquinone diazide compound, which is the photosensitive agent, were not good.The pattern shape after pattern formation was very poor, making it unusable. Not likely.
まｔ：、、遠紫外線用パターン形成材料として２４８゜
４ｎｍ付近の波長の遠紫外光に高い透過率を有するポリ
マーとして、 ２−ジアゾ−１，３−ジオン化合物より
なるレジストが報告されている。 しかる（へ このレ
ジスト１よ ベースポリマーが７０％の透過率を有する
のに対しパターン形成材料の露光後の透過率は４５％に
すぎず、十分な光退色性が得られていな（■ また パ
ターン形成実験の結果パターンは約７０度のアングルを
有するもので垂直な形状を有する満足したエツチングマ
スクとなるパターン形状は得られでいない。A resist made of a 2-diazo-1,3-dione compound has been reported as a pattern-forming material for deep ultraviolet rays as a polymer having high transmittance for far ultraviolet light having a wavelength of around 248.degree. 4 nm. However, in this resist 1, the base polymer has a transmittance of 70%, but the transmittance of the pattern forming material after exposure is only 45%, indicating that sufficient photobleaching properties have not been obtained (■ Also, the pattern As a result of the formation experiment, the pattern had an angle of about 70 degrees, and a vertical pattern shape that would serve as a satisfactory etching mask could not be obtained.
また このパターン形成材料の感度は１４０から１５０
ｍ Ｊ ／ ｃ ｍ”程度と低感度であることが明らか
となっ九 すなわち２−ジアゾ−１，３−ジオン化合物
を使用する高透明性パターン形成材料は感度が低く、特
にエネルギー効率の良くないＫｒＦエキシマレーサ光を
用いる場合、実用化は困難な状況にある。Also, the sensitivity of this pattern forming material is 140 to 150.
It has become clear that the sensitivity is as low as 2-diazo-1,3-dione compounds, which is as low as 2-diazo-1,3-dione compounds. When using excimer laser light, it is difficult to put it into practical use.
近承 露光エネルギー量を低減させる手段として、たと
えばポリ 〔ターシャルブトキシカルボネート）スチレ
ンと、オニウム塩より構成される材料が提案され九 こ
れは 露光により発生した酸を媒体とする化学増幅型の
パターン形成材料であり、たとえば［Ｈ，ＩｔｏらＰｏ
ｌｙｍ Ｅｎｇ。Recently, as a means to reduce the amount of exposure energy, a material composed of poly[tert-butoxycarbonate] styrene and an onium salt has been proposed.9 This is a chemically amplified pattern using the acid generated by exposure as a medium. For example, [H, Ito et al. Po
lym Eng.
Ｓ ｃ ｉ、 、２３表１０１２頁（１９８３） ３
等で近年種々の報告がある。第４図を用いて従来の化学
増感型のパターン形成材料を用いたパターン形成方法を
説明する。半導体等の基板１上にパターン形成材料１２
を回転塗付し ホットプレート上で９０℃、９０秒間ソ
フトベーク１．、 １．０ミクロン厚のパターン形成材
料を得る（第４図（ａ））。な耘 基板１上には絶縁風
導電風 酸化膜が形成されている場合か多し−次に２
４８．４ｎｍのＫｒＦエキシマレサ４でマスク５を介し
て露光することにより酸発生剤に以下の化学変化を発生
させ酸を発生する（第４図（ｂ））。 そして、 ホッ
トプレート３◎
ｈ）、）
◎−３” ５ｂＦｅＯＨ％５ｂＦｅ。Sci, 23 Table 1012 pages (1983) 3
There have been various reports in recent years. A pattern forming method using a conventional chemically sensitized pattern forming material will be described with reference to FIG. Pattern forming material 12 on substrate 1 such as a semiconductor
1. Rotate the coating and soft bake on a hot plate at 90℃ for 90 seconds. , a pattern forming material with a thickness of 1.0 microns is obtained (FIG. 4(a)). There are many cases where an insulating wind, conductive wind, or oxide film is formed on the substrate 1.Next, 2
By exposing the acid generator to light through a mask 5 using a 48.4 nm KrF excimer laser 4, the following chemical changes occur in the acid generator to generate acid (FIG. 4(b)). And hot plate 3◎ h),) ◎-3” 5bFeOH%5bFe.
〔［相］
上で前記材料膜を１３０℃で９０秒間加熱処理する事に
より、樹脂に下記の化学変化を発生させ、樹脂をアルカ
リ可溶性とする。 （第４図（Ｃ））。[[Phase] By heat-treating the material film above at 130° C. for 90 seconds, the following chemical changes occur in the resin and the resin becomes alkali-soluble. (Figure 4(C)).
そして最後にアルカリ現像液（ＭＰ−３１９（シブレイ
社））を用いてパターン形成材料１２の露光部１２ｂを
溶解除去しポジ型パターン１２ａ、 １２ｃを得る（
第４図（ｄ））。Finally, the exposed portions 12b of the pattern forming material 12 are dissolved and removed using an alkaline developer (MP-319 (Sibley)) to obtain positive patterns 12a and 12c.
Figure 4(d)).
発明が解決しようとする課題
しかるにその方法はパターン寸法が１．０μｍ以下とく
に０．５μｍ以下となると微細パターン１２ｃは第４図
（ｄ）のごとく基板上に形成することが不可能であるこ
とが判明した 破線は本来残るべきパターンが残ってい
ないことを示す。これは本発明者らの検討によればパタ
ーン形成材料と基板との間の密着性がよくない為である
ことがわかつ九 この現像は数μｍレベルのデノくイス
作製では前記例のごとく問題とはならない力＼ １μｍ
以下の微細パタース 特に０．５μｍ以下の超微細ノく
ターンを高密度に形成する工程において（友 重大Ｊｉ
致命的問題となり、結果としてサブミクロンル−ルのデ
バイスを作製する事かできなｌ、％ この様に超微細
パターンが形成できない理由（よ 本発明者らの検討に
よると、パターン形成材料と基板との間の密着性が低い
ことにあることが判明し九 従来のパターン形成材料に
用いられるポリｔ−ＢＯＣスチレン樹脂は その分子内
に親水基を有さない為これを薄膜とした場合その膜は疎
水性となる。Problems to be Solved by the Invention However, in this method, when the pattern size is 1.0 μm or less, particularly 0.5 μm or less, it is impossible to form the fine pattern 12c on the substrate as shown in FIG. 4(d). The broken line indicates that the original pattern that should remain does not remain. According to the studies conducted by the present inventors, it was found that this is due to poor adhesion between the pattern forming material and the substrate. Force that does not equal ＼ 1μm
In the process of forming the following fine patterns with high density, especially ultra-fine patterns of 0.5 μm or less (Tomo Seiki Ji
This becomes a fatal problem, and as a result, it becomes impossible to fabricate submicron-rule devices.The reason why ultra-fine patterns cannot be formed in this way (According to the inventors' study, the pattern forming material and substrate It was discovered that this is due to the low adhesion between becomes hydrophobic.
また基板において３表 パターン形成材料膜を形成する
前に基板表面の状態を均一化するた取 ヘキサメチルジ
シラザン（ＨＭＤＳ）による疎水化処理を行っている。In addition, before forming the pattern-forming material film on the substrate, a hydrophobic treatment is performed using hexamethyldisilazane (HMDS) to homogenize the condition of the substrate surface.
このように基板表面は疎水性となっている。疎水性基板
と疎水性のパターン形成材料は 本発明者らの検討によ
り、密着性が悪く、現像時、露光部が溶解除去されると
同時に本来溶解しない未露光部が低い密着性の為 基板
上に形成できないことが明らかとなっ九 この現象（よ
パターン寸法は１μｍ以下の微細パターンにおいて特に
顕著となも すなわちこれを防止すること（友 特に
寸法が１μｍ以下さらに０．５μｍ以下の超微細なパタ
ーンを形成し 高分留りで超微細な半導体集積回路の製
造において極めて重要となる。従って本発明（よ 化学
増幅型のパターン形成材料を用いると共に 密着性を向
上させることにより、形状が良く膜はがれのない微細パ
ターンを確実に形成する方法を提供することを目的とす
る。In this way, the surface of the substrate is hydrophobic. The inventors have found that hydrophobic substrates and hydrophobic pattern-forming materials have poor adhesion, and during development, the exposed areas are dissolved and removed, while the unexposed areas, which do not normally dissolve, have poor adhesion to the substrate. It has become clear that this phenomenon (particularly in fine patterns with pattern dimensions of 1 μm or less) cannot be prevented.
It forms ultra-fine patterns with dimensions of 1 μm or less, and even 0.5 μm or less, and is extremely important in the production of high-resolution, ultra-fine semiconductor integrated circuits. Therefore, an object of the present invention is to provide a method for reliably forming a fine pattern with a good shape and no peeling by using a chemically amplified pattern forming material and improving adhesion.
課題を解決するための手段
本発明のパターン形成方法（よ 基板上へ 酸雲囲気下
でアルカリ可溶性となる官能基と親水性を有する成分を
有する樹脂 露光による酸を発生する感光性化合塩 前
記樹脂および化合物を溶解可能な溶媒をふくむパターン
形成材料膜を形成する工程と、遠紫外線で前記材料膜を
選択的に露光する工程と、前記材料膜を加熱処理する工
程と、前記材料膜を現像してパターン形成する工程とを
備えた方法を提供するものである。見 本発明は前記成
分が水酸基 カルボキシル基 ２−ヒドロキ（但ＬＲ＋
は水酸基 カルボキシル基 ２−ヒドロキシエトキシカ
ルボニル基 スルフォン酸基を表わＬ Ｒ２，Ｒ−は
おのおの独立で水素原子、ハロゲン原子、低級アルキル
基を表わす）のいずれかを含む方法を提供する。また
本発明は前記官能基がメチル、イソプロピＪし、 ｔｅ
ｒｔ （ターシャルブトキシ）ブチＡｙ、 メトキシ
メチル、イソプロポキシメチル、テトラヒドロピラニ／
１４ テトラヒドロフラニル、 トリメチルシリノＬ
’、ｔｅｒｔブトキシカルボニル、イソプロポキシカル
ボニルのいずれかを含むことを特徴とする方法を提供す
る。Means for Solving the Problems A pattern forming method of the present invention (onto a substrate) A resin having a functional group that becomes alkali-soluble in an atmosphere surrounded by an acid cloud and a hydrophilic component A photosensitive compound salt that generates an acid upon exposure The resin and a step of forming a pattern-forming material film containing a solvent capable of dissolving the compound, a step of selectively exposing the material film to deep ultraviolet rays, a step of heat-treating the material film, and a step of developing the material film. The present invention provides a method comprising a step of forming a pattern using
represents a hydroxyl group, a carboxyl group, a 2-hydroxyethoxycarbonyl group, or a sulfonic acid group; Also
In the present invention, the functional group is methyl, isopropylene,
rt (tertiary butoxy)butyAy, methoxymethyl, isopropoxymethyl, tetrahydropirani/
14 Tetrahydrofuranyl, trimethylsilino L
', tert-butoxycarbonyl, or isopropoxycarbonyl.
作用
本発明の方法について具体的に説明すると、ＫｒＦエキ
シマレーザ光 遠紫外光で露光された感光性化合物Ｃｔ
光反応に従って酸が発生すも 露光工程に続いて加
熱処理すると樹脂の官能基が酸により化学変化を受１す
、アルカリ可溶性となり、現像の賑 現像液に溶出して
くる。他人 未露光部は酸が発生しない為 加熱処理し
ても化学変化は生ぜ衣 アルカリ可溶性基の発現はな（
−その結果本発明の方法によれば 良好なコントラスト
を有したポジ型のパターンが形成される。又 露光で発
生した酸は触媒的に作用する八 露先は必要な酸を発生
させるだけでよく、露光エネルギー量の低減が可能とな
った 現像時に発生する微細パターンのはがれは サブ
ミクロンルールのデバイス作成において重大な問題であ
る。すなわ板パターン形成材料を親水化するために樹脂
に親水性を付加し パターンはがれのない良好な形状を
形成可能なパターン形成方法は 超微細ルールのデバイ
ス作成に必要不可欠なものである。本発明（よ さらに
樹脂に親水性を有する成分を付加することにより、この
樹脂を用いたパターン形成材料は親水性となり、疎水性
基板との密着性が向上すａ すなわ’＆ １．０μｍ
さらに０．５μｍ以下の超微細パターンは現像時、はが
れることなく形成することが可能である。Function: To specifically explain the method of the present invention, a photosensitive compound Ct exposed to KrF excimer laser light and far ultraviolet light.
Although acid is generated as a result of the photoreaction, when heat treatment follows the exposure process, the functional groups of the resin undergo a chemical change due to the acid, becoming alkali-soluble and eluting into the developer during development. Others: Because no acid is generated in the unexposed area, no chemical changes occur even after heat treatment, and no alkali-soluble groups are expressed (
- As a result, according to the method of the present invention, a positive pattern with good contrast is formed. In addition, the acid generated during exposure acts catalytically.8 The exposure tip only needs to generate the necessary acid, making it possible to reduce the amount of exposure energy.Peeling off of the fine pattern that occurs during development is a submicron rule device. This is a serious problem in its creation. In other words, a pattern forming method that adds hydrophilicity to the resin in order to make the plate pattern forming material hydrophilic, and that can form a good shape without pattern peeling, is essential for creating devices with ultra-fine rules. The present invention (moreover, by adding a hydrophilic component to the resin, a pattern forming material using this resin becomes hydrophilic and improves adhesion to a hydrophobic substrate.
Furthermore, ultrafine patterns of 0.5 μm or less can be formed without peeling off during development.
実施例
本発明者ら（よ 親水性を有する成分を種々検討した結
果 水酸基 カルボキシル基 ２−ヒドロ（但ＬＲ＋は
水酸基 カルボキシル基 ２−ヒドロキシエトキシカル
ボニル基 スルフォン酸基を表わＬ Ｒ２，Ｒ−はおの
おの独立で水素原子、ハロゲン原子、低級アルキル基を
表わす）等力（樹脂の親水性を向上させ、酸雰囲気下で
アルカリ可溶性となる官能基を有する成分と共重合した
樹脂を用いたパターン形成材料ζよ 高い親水性を有し
現像中レジストパターンはがれが生じないことを見出し
た なお親水性を有する成分は 前記のものに限定され
るものではな賎 また 官能基としては メチル イソ
プロピル、 ｔｅｒｔ−ブチル、メトキシメチル、イソ
プロポキシメチノｋ テトラヒドロピラニル、テトラヒ
ドロフラニル、 トリメチルシリル、 ｔｅｒｔ−ブト
キシカルボニノｋ イソプロポキシカルボニル等があげ
られる力交 酸雰囲気下でアルカリ可溶性を示すもので
あれば何でもよく、これらに限定されるものではなし兎
また酸発生剤についても同様で、露光により酸を発生
ずるものであれば何でもよく、例え（戯 ニトロベンジ
ル化合物 オニウム塩 スルフォン酸化合物カルボン酸
化合物等があげられる力（もちろんこれらに限定される
ものではなし−溶媒についても同様で、前記樹脂及び酸
発生剤を溶解可能なものであれば何でもよｌ、Ｘｏ
以下に実施例を用いて本発明をさらに詳細に説明する力
丈 本発明はこれら実施例に何ら制限されるものではな
ｔ、％実施例１
下記の組成で試薬を調整し パターン形成材料とした
（２）ｐ−トルエンスルフォン酸−２，６−シニトロベ
ンジル Ｉｇ（３）ジエ
チレングリコールジメチルエーテル０ｇ
ここで（１）の樹脂（よ 酸雰囲気でアルカリ可溶性を
示す官能基としてｔｅｒｔ−（ターシャル）ブトキシ基
を用１．Ｘ、親水性を有する成分として水酸基（ヒドロ
キシスチレン）を用いた一例である。Examples The present inventors (as a result of various studies on hydrophilic components) Hydroxyl group Carboxyl group 2-hydro (LR+ represents a hydroxyl group, a carboxyl group, a 2-hydroxyethoxycarbonyl group, a sulfonic acid group, and L R2 and R- each represent a A pattern-forming material ζ that uses a resin copolymerized with a component that has a functional group that improves the hydrophilicity of the resin and makes it soluble in alkali in an acid atmosphere. It has been found that the resist pattern does not peel off during development due to its high hydrophilicity.The hydrophilic components are not limited to those mentioned above, and the functional groups include methyl, isopropyl, tert-butyl, and methoxy. Methyl, isopropoxymethinok, tetrahydropyranyl, tetrahydrofuranyl, trimethylsilyl, tert-butoxycarboninok, isopropoxycarbonyl, etc. Anything that shows alkali solubility in an acid atmosphere may be used, but is not limited to these. The same is true for acid generators, as long as they generate acid upon exposure to light, any agent may be used.For example, nitrobenzyl compounds, onium salts, sulfonic acid compounds, carboxylic acid compounds, etc. The same applies to the solvent; any solvent may be used as long as it can dissolve the resin and acid generator.
The present invention will be explained in more detail using Examples below.The present invention is not limited to these Examples in any way.Example 1 A reagent was prepared with the following composition and used as a pattern forming material. (2) 2,6-cinitrobenzyl p-toluenesulfonate Ig (3) Diethylene glycol dimethyl ether 0 g Here, the resin of (1) (a tert-butoxy group is added as a functional group exhibiting alkali solubility in an acidic atmosphere) 1.X is an example in which a hydroxyl group (hydroxystyrene) is used as a hydrophilic component.
ｔｅｒｔ−ブトキシ基は下記に示すごとく酸雰囲気下で
Ｃ−Ｏの結合が切断され 結果として水酸基を形成する
。As shown below, the C--O bond of the tert-butoxy group is cleaved in an acid atmosphere, resulting in the formation of a hydroxyl group.
また（２）は酸発生剤として用いたもので、露光により
以下の反応が発生する。Further, (2) was used as an acid generator, and the following reaction occurs upon exposure.
ＣＨ３＋５Ｏ３Ｈ
また（３） ｉｌ 前記両者を溶解可能な溶媒の例で
あり、遠紫外領域に高い透過率を有する＆ＫｒＦエキシ
マレーサ用パターン形成材料の溶媒として良好な結果が
期待される。第１図を用いて本発明のパターン形成方法
を説明する。シリコン等の半導体載板１上に上記の組成
で調製されたパターン形成材料２を用いて回転塗付して
レジスト薄膜とし、９０ｔ−、９０秒間ホットプレート
３でソフトベー・′・Ｌ 薄膜中の溶媒を蒸発除去し
厚さ １．０μｍのパターン形成材料薄膜を得る（第
１図（ａ））。CH3+5O3H and (3) il This is an example of a solvent that can dissolve both of the above, and is expected to give good results as a solvent for pattern forming materials for &KrF excimer lasers that have high transmittance in the deep ultraviolet region. The pattern forming method of the present invention will be explained using FIG. The pattern forming material 2 prepared with the above composition is spin-coated onto a semiconductor mounting plate 1 made of silicon or the like to form a resist thin film, and the solvent in the thin film is heated using a hot plate 3 at 90T for 90 seconds. is removed by evaporation to obtain a thin film of pattern forming material with a thickness of 1.0 μm (FIG. 1(a)).
な抵 基板１表面は絶縁Ａ 導電風 半導体膜等が形成
されている場合も多い。次に２４８．４ ｎ ｍのＫｒ
Ｆエキシマレーザ４をマスク５を介して露光することに
より、前記のごとく酸発生剤（２）を光分解する。 （
第１図（ｂ））。そして１３０ｔ、 ９Ｑ秒間ホット
プレート３でベーク（ＰＥＢ）Ｉ−前記のごとくターシ
ャルブトキシ基をアルカリ可溶性反応させる（第１図（
Ｃ））。そしてアルカリ現像液（２゜３８％テトラメチ
ルアンモニウムハイドロオキサイト（ＴＭＡＨ）水溶液
）で６０秒間現像することによりパターン形成材料２の
露光部２ｂを溶解除去し ポジ型パターン２ａ、２ｃを
得た（第１図（ｄ））。In many cases, the surface of the resistor substrate 1 is formed with an insulating conductive semiconductor film or the like. Then 248.4 nm of Kr
By exposing the F excimer laser 4 to light through the mask 5, the acid generator (2) is photodecomposed as described above. (
Figure 1(b)). Then, bake (PEB) I on a hot plate 3 for 130t and 9Q seconds to cause an alkali-soluble reaction of the tertiary butoxy group (Fig. 1 (
C)). The exposed areas 2b of the pattern forming material 2 were then dissolved and removed by developing with an alkaline developer (2°38% tetramethylammonium hydroxide (TMAH) aqueous solution) for 60 seconds to obtain positive patterns 2a and 2c. Figure 1 (d)).
このように 以上の方法により、パターン２ａおよび１
．０μｍ以下の微細パターン２Ｃを、基板１上からはが
れることなく形成することが可能となった したがって
、 このレジストパターン２ ａ。In this way, by the above method, patterns 2a and 1
．． It became possible to form a fine pattern 2C of 0 μm or less without peeling off the substrate 1. Therefore, this resist pattern 2a.
２ｃをマスクとして基板１の表面部を正確に選択エツチ
ングする加工が可能となる。Using 2c as a mask, the surface of the substrate 1 can be selectively etched accurately.
本発明に用いるパターン形成材料（膜厚１μｍ）の露光
前後の紫外線分光曲線図を第２図に示す。FIG. 2 shows ultraviolet ray spectral curves before and after exposure of the pattern forming material (film thickness: 1 μm) used in the present invention.
露光前後で透過率はほぼ変化せず、約６５％と高い値を
示し島 パターン形成実験の結果 レジストパターン２
ａとして好形状な０．３μｍラインアンドスペースパタ
ーンを形成することが可能であった 更にこのパターン
形成材料（１μｍ）の照射特性を第３図に示す。Ｔ値５
９反感度１０ｍＪ／Ｃｍ２と高コントラスト、高感度で
あっ九 ここで、本発明の一実施例のパターン形成材料
と従来の材料を用いた方法の各基板上での限界パターン
解像度及びパターンアングルを下表に示す。The transmittance remains almost unchanged before and after exposure, showing a high value of approximately 65%.Results of pattern formation experiments Resist pattern 2
It was possible to form a well-shaped 0.3 μm line-and-space pattern as a.Furthermore, the irradiation characteristics of this pattern forming material (1 μm) are shown in FIG. T value 5
9 Anti-sensitivity: 10 mJ/Cm2, high contrast and high sensitivity. Shown in the table.
（以下余白）
本発明のパターン形成方法は 樹脂に親水性基を導入す
ることにより、従来の化学増幅型レジストを用いたパタ
ーン形成方法で、形成不可能な超微細パターンを良好な
パターンアングルおよび感度で形成することができた
また本発明のパターン形成方法は 従来密着性に乏しい
とされる（Ｓ１０２）やスピン・オン・グラス（ＳＯＧ
＞膜上でもシリコン基板と同様にはがれのない良好な形
状のパターンが形成でき九 すなわ板 本発明のパター
ン形成方法ｌｅｔ、、 １．０μｍさらに０．５μｍ
以下の超微細レジストパターンを良好な形状で感度よく
確実に形成することが可能で、結果として設計通りにデ
バイスを作製することが可能となり、サブハーフミクロ
ンルールの超微細な半導体集積回路デバイス等の作製に
おいて意義大なものであも実施例２
酸発生剤（２）を下記の組成に変更する以外ζよ実施例
１と同様の実験を行っ九
その結果
実施例１
と同様の良好な結果が５ｍＪ
７ｃｍ２の感度で得られ九
実施例３
酸発生剤（２）
を下記の組成に変更する以外は
実施例１
と同様の実験を行っ九
その結果
実施例１
と同様の良好な結果が１５ｍ Ｊ
７ｃｍ２の感度で得られ總
実施例４
樹脂（１）
を下記の組成に変更する以外（よ
実施
例１と同様の実験を行った
Ｕに（にＨａ ） ３
ＵＩ′ｉ
Ｗ
ｕｕｕｕ
この樹脂は 親水性を有する基（水酸基）力（実施例１
のものより少ない比率で導入されたものである。実験を
行った結果 本樹脂を用いても良好な密着性が得られ実
施例１と同様の結果が得られ７”：０
実施例５
樹脂（１）を下記の組成に変更する以外は 実施例１と
同様の実験を行っ九
この樹脂１よ 親水性を有する成分として、スルフォン
酸を導入したものである。実験の結果、実施例１と同様
の良好な結果が得られに
実施例６
樹脂（］）を下記のものに変更する以外は実施例１と同
様の実験を行っｔも
Ｈ３
その結果 実施例Ｉと同様の良好な結果が得られ九
実施例７
樹脂を下記の組成に変更する以外Ｃよ
と同様の実験を行っ九
実施例１
Ｈ３
この樹脂（よ 分子内にポリパラビニルフェノールと、
Ｃ三Ｎを導入する事により耐熱性を向上させ、かつ、水
酸基を導入する事により、密着性向上を同時に得る事を
目的としたものである。その結果高い耐熱性を有する０
、３μｍパターン力（良好な密着性で形成する事ができ
へ
実施例８
現像液を２．３８％ＴＭＡＨ（テトラメチルアンモニウ
ムハイドロオキサイト）と１０％イソプロパツール水溶
液に変更する以外（よ 実施例７と同様の実験を行っ九
現像液にイソプロパツール等のアルコールを混入する
事により、現像液中に極性が土シ パターン形成材料
膜とのぬれ性が向上することか判明し九 現像液とパタ
ーン形成材料膜のぬれ性を向上させる事は露光部のパタ
ーン形成材料の溶解速度を増加させるへ より一層の高
感度化が可能となる。その結果 実施例９と同様の結果
力＜、 ３．５ｍＪ／ｃｍ２という非常に高い感度で
得られ島 な耘 本実施例において、酸雰囲気でアルカ
リ可溶性を示す基として安定性の高いターシャルブトキ
シ基を用いて説明した万丈 他にターシャルブトキシカ
ルボネート基 インプロポキシ力ルホネート展 イソプ
ロポキシ展 テトラヒドロフラニル基 テトラヒドロフ
ラニル基 トリメチルシリル基等が挙げられ またこれ
らに限定されるものではな賎
また酸発生剤についても同様で、下記一般式で示される
化合物力（溶液安定性 酸発生効率等が良好で、これを
パターン形成材料として用いた場合、良好な結果が期待
される力（露光により酸を発生するものであれば何でも
よく、これらに限定されるものではない。(Left below) The pattern forming method of the present invention introduces hydrophilic groups into the resin to create ultra-fine patterns with good pattern angle and sensitivity that cannot be formed using conventional pattern forming methods using chemically amplified resists. could be formed with
In addition, the pattern forming method of the present invention can be applied to materials such as spin-on-glass (SOG) and spin-on glass (S102), which are conventionally considered to have poor adhesion.
>A well-shaped pattern without peeling can be formed on a film as well as on a silicon substrate.
It is possible to reliably form the following ultra-fine resist patterns with good shape and sensitivity, and as a result, it is possible to fabricate devices as designed, such as ultra-fine semiconductor integrated circuit devices of sub-half micron rule. Example 2 The same experiment as in Example 1 was carried out except that the acid generator (2) was changed to the following composition.As a result, the same good results as in Example 1 were obtained. Example 3 The same experiment as in Example 1 was carried out except that the acid generator (2) was changed to the following composition. As a result, the same good results as in Example 1 were obtained at 15 mJ. Example 4 The same experiment as in Example 1 was conducted except that resin (1) was changed to the following composition. Group (hydroxyl group) having properties (Example 1)
It was introduced at a lower rate than that of As a result of the experiment, good adhesion was obtained using this resin, and the same results as in Example 1 were obtained.Example 5 Example 5 Except for changing the composition of resin (1) to the following. An experiment similar to that of Example 1 was conducted to obtain a resin (1) in which sulfonic acid was introduced as a hydrophilic component.As a result of the experiment, good results similar to those of Example 1 were obtained. The same experiment as in Example 1 was carried out except that the resin was changed to the one shown below.Results The same good results as in Example I were obtained.Example 7 Except for changing the resin to the following composition Example 1 H3 This resin (with polyparavinylphenol in the molecule,
The purpose is to simultaneously improve heat resistance by introducing C3N and improve adhesion by introducing hydroxyl groups. As a result, it has high heat resistance.
Example 8 Except for changing the developer to 2.38% TMAH (tetramethylammonium hydroxide) and 10% isopropanol aqueous solution (Example 8) An experiment similar to 7 was conducted and it was found that by mixing alcohol such as isopropanol into the developer, the polarity was increased in the developer and the wettability with the pattern forming material film was improved. Improving the wettability of the pattern-forming material film increases the dissolution rate of the pattern-forming material in the exposed area, making it possible to achieve even higher sensitivity.As a result, the same result as in Example 9 was achieved.3. In this example, a highly stable tert-butoxy group was used as a group exhibiting alkali solubility in an acid atmosphere. Examples include impropoxy sulfonate, isopropoxy, tetrahydrofuranyl group, tetrahydrofuranyl group, trimethylsilyl group, etc., but are not limited to these.The same also applies to acid generators, and compounds represented by the following general formula (solution stability If the material has good acid generation efficiency and is used as a pattern forming material, good results can be expected (any material that generates acid upon exposure may be used, but is not limited to these).
一般式
（式中、Ｒ′′はトリクロルアセチルＬｐ−トルエンス
ルホニル基 ｐ−１リフルオロメチルベンゼンスルホニ
ル基 メタンスルホニル基又はトリフルオロメタンスル
ホニル基を表わＬＲ”及びＲＰＩは夫々、独立して水素
原子、／’１０ゲン原子又はニトロ基を表わす。）
一般式
（成虫 Ｒｏ及びＲ２２は夫々、独立して直鎖状、分岐
状又は環状のアルキル基 ハロアルキル基又表わＬ
Ｒ”及びＲ２′′は夫々、独立して水素原子、ハロゲン
原子、直鎖状、分岐状又は環状アルキル基 ハロアルキ
ル基 アルコキシ基 ニトロ基又はシアノ基を表わす。General formula (wherein R'' represents a trichloroacetyl Lp-toluenesulfonyl group, p-1 a trifluoromethylbenzenesulfonyl group, a methanesulfonyl group, or a trifluoromethanesulfonyl group; LR'' and RPI each independently represent a hydrogen atom, /'10 represents a gen atom or a nitro group.) General formula (Imago Ro and R22 each independently represent a linear, branched, or cyclic alkyl group, a haloalkyl group, or L
R'' and R2'' each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a haloalkyl group, an alkoxy group, a nitro group or a cyano group.
）を表わす。）
一般式
（式ｃｆｌｌｌ、Ｒ２６及びＲ２？は夫々、独立して水
素原子、ハロゲン原子、直鎖法 分岐状又は環状のアル
キル基 又はアルコキシ基を表わＬ Ｚｅはバークロ
レート、 ｐ−トルエンスルホネート又はトリフルオロ
メタンスルホネートを表わす。）
一般式
（式＋Ｙはカルボニル基 スルホニル基 スルフィニル
基を表わＬ Ｒ”は低級アルキル基 トリフルオロ、
メチル基 フェニル基又はアルキル置換フェニル基を表
わＬ Ｒ”及びＲ３５は夫々、独立して低級アルキル
基 ハロゲン原子又は水素原子を表わＬ Ｒ”は水素
原子、ハロゲン原子、低級アルキル基 アルコキシ基又
はアルキルチオ基を表わす。）
一般式
（成虫 Ｒ２１Ｒ１２Ｒ２２及びＲ２４は夫々、独立し
て水素原子、ハロゲン原子、直鎖状、分岐状又は環状の
アルキル基 ハロアルキル基 アルコキシ基 アラルキ
ル展 置換フェニル基 フェニル基 ニトロ基又はシア
ノ基を表わＬ Ｒ”−Ｒ”Ｒ２２〜Ｒ２２及びＲ２３
〜Ｒ２４はＡ、＆ 及びＣを介在して夫々、独立して
炭素数５〜８の脂環 ヘテロ脂環 芳香環又はヘテロ芳
香環を表わす。）溶媒に関しても本実施例では遠紫外線
領域で吸収の少ないジエチレングリコールジメチルエー
テルを用いた力（樹脂及び酸発生剤が溶解可能なもので
あれば何でもよく、例えば エチルセロソルブアセテー
ト、メチルセロツルアセテート、エチルラクテート メ
チルラクテート、ジエチレングリコールジメチルエーテ
ルｋ ジエチレングリコールモノブチルエーテル等が挙
げられるがこの限りではなｌ、％ また露光光源につ
いても同様の事が言うことができ、露光により酸発生す
るものであれば何でもよく、例えばｇ線（４３６ｎｍ）
やｉ線（３６５ｎｍ）、電子線 Ｘ線等が挙げられる力
（もちろんこの限りではなし−
発明の効果
本発明は 紫外線特にＫｒＦエキシマレーザに対し高感
度 高コントラストおよび超微細なりソグラフィプロ
セスにおいて密着性の高い新規なパターン形成材料な用
いたパターン形成方法を提供するものであり、本発明に
よれば０．３μｍルール等の超微細デバイス等への適用
が可能となり、結果として半導体素子等の微細（１，歩
留りの向上に続がり、大なる工業的価値を発揮するもの
であも). ) General formula (Formula cfllll, R26 and R2? each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, or an alkoxy group; L Ze is verchlorate, p-toluenesulfonate or Represents trifluoromethanesulfonate. General formula (Formula + Y represents a carbonyl group, sulfonyl group, sulfinyl group, L R" is a lower alkyl group, trifluoro,
Methyl group represents a phenyl group or an alkyl-substituted phenyl group LR'' and R35 each independently represent a lower alkyl group, a halogen atom or a hydrogen atom LR'' represents a hydrogen atom, a halogen atom, a lower alkyl group an alkoxy group or Represents an alkylthio group. ) General formula (Imago) R21R12R22 and R24 each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a haloalkyl group, an alkoxy group, an aralkyl group, a substituted phenyl group, a phenyl group, a nitro group or a cyano group. L R''-R''R22~R22 and R23
~R24 each independently represents an alicyclic ring, heteroalicyclic ring, aromatic ring or heteroaromatic ring having 5 to 8 carbon atoms with A, & and C interposed therebetween. ) Regarding the solvent, in this example, diethylene glycol dimethyl ether, which has low absorption in the deep ultraviolet region, was used. Examples include, but are not limited to, methyl lactate, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, etc.l,% The same can be said about the exposure light source; any source that generates acid upon exposure may be used, such as G-line. (436nm)
, I-ray (365 nm), electron beam, The present invention provides a pattern forming method using a novel pattern forming material with a high level of performance.According to the present invention, it is possible to apply it to ultra-fine devices such as the 0.3 μm rule, and as a result, it is possible to apply it to ultra-fine devices such as the 0.3 μm rule. 1.It can exhibit great industrial value following the improvement of yield.
第１図（友 本発明のパターン形成方法の工程断面＠
第２図（友 本発明の一実施例のパターン形成材料の紫
外線分光曲線図（ただし 実線は露光能 破線は露光後
）、第３図は本発明の一実施例のパターン形成材料の照
射特性＠ 第４図（よ 従来のパターン形成方法の工程
断面図である。
１ 、、、、シリコン基板、 ２ 、、、、本発明のパ
ターン形成材料Ｕ ２ａ、 ２Ｃ，、、、レジスト
パターン、３ 、、、、ホットプレート、 ４ 、、、
、Ｋ ｒ Ｆエキシマレーザ、 ５．、、、マスク。Figure 1 (Friend) Process cross section of the pattern forming method of the present invention @
Figure 2 (friend) is an ultraviolet spectral curve diagram of a pattern forming material according to an embodiment of the present invention (where the solid line indicates exposure capacity and the broken line indicates after exposure), and Figure 3 shows the irradiation characteristics of a pattern forming material according to an embodiment of the present invention @ FIG. 4 is a process sectional view of a conventional pattern forming method. 1. Silicon substrate 2. Pattern forming material U of the present invention 2a, 2C, . . . Resist pattern 3. ,,hot plate, 4,,,
, K r F excimer laser, 5. ,,,mask.
Claims (3)
能基と親水性を有する成分を有する樹脂露光により酸を
発生する感光性化合物、前記樹脂及び化合物を溶解可能
な溶媒をふくむパターン形成材料膜を形成する工程と、
遠紫外線で前記材料膜を選択的に露光する工程と、前記
材料膜を加熱処理する工程と、前記材料膜を現像して前
記材料膜のパターンを形成する工程とを備えたことを特
徴とするパターン形成方法。(1) On the substrate, a pattern-forming material film containing a resin having a functional group that is alkali-soluble in an acid atmosphere and a hydrophilic component, a photosensitive compound that generates acid upon exposure, and a solvent that can dissolve the resin and compound. a step of forming;
The method is characterized by comprising a step of selectively exposing the material film to deep ultraviolet rays, a step of heat-treating the material film, and a step of developing the material film to form a pattern of the material film. Pattern formation method.
カルボニル基、スルフォン酸基又は▲数式、化学式、表
等があります▼（但し、Ｒ＿１は水酸基、カルボキシル
基、２−ヒドロキシエトキシカルボニル基、スルフォン
酸基を表わし、Ｒ＿２、Ｒ＿３は夫々独立で水素原子ハ
ロゲン原子、低級アルキル基を表わす）のいずれかを含
むことを特徴とする特許請求の範囲第１項に記載のパタ
ーン形成方法(2) Components include hydroxyl group, carboxyl group, 2-hydroxycarbonyl group, sulfonic acid group, or ▲mathematical formula, chemical formula, table, etc.▼(However, R_1 is hydroxyl group, carboxyl group, 2-hydroxyethoxycarbonyl group, sulfonic acid group) and R_2 and R_3 each independently represent a hydrogen atom, a halogen atom, or a lower alkyl group).
ル、メトキシメチル、イソプロポキシメチル、テトラヒ
ドロピラニル、テトラヒドロフラニル、トリメチルシリ
ル、ｔｅｒｔ−ブトキシカルボニル、イソプロポキシカ
ルボニルのいずれかを含むことを特徴とする特許請求の
範囲第１項に記載のパターン形成方法。(3) A patent claim characterized in that the functional group includes any one of methyl isopropyl, tert-butyl, methoxymethyl, isopropoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, trimethylsilyl, tert-butoxycarbonyl, and isopropoxycarbonyl. The pattern forming method according to item 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019529A JP2621533B2 (en) | 1990-01-30 | 1990-01-30 | Pattern formation method |
| US07/646,920 US5252435A (en) | 1990-01-30 | 1991-01-28 | Method for forming pattern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019529A JP2621533B2 (en) | 1990-01-30 | 1990-01-30 | Pattern formation method |
Related Child Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7259754A Division JP2647065B2 (en) | 1995-10-06 | 1995-10-06 | Pattern formation method |
| JP7259755A Division JP2615530B2 (en) | 1995-10-06 | 1995-10-06 | Pattern formation method |
| JP8306123A Division JP2713299B2 (en) | 1996-11-18 | 1996-11-18 | Pattern formation method |
| JP8306124A Division JP2699971B2 (en) | 1996-11-18 | 1996-11-18 | Pattern formation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03223857A true JPH03223857A (en) | 1991-10-02 |
| JP2621533B2 JP2621533B2 (en) | 1997-06-18 |
Family
ID=12001866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019529A Expired - Lifetime JP2621533B2 (en) | 1990-01-30 | 1990-01-30 | Pattern formation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2621533B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05232706A (en) * | 1992-02-25 | 1993-09-10 | Japan Synthetic Rubber Co Ltd | Radiation sensitive resin compound |
| JPH07199467A (en) * | 1993-12-28 | 1995-08-04 | Nec Corp | Photosensitive resin composition and method for forming pattern |
| JPH0882933A (en) * | 1995-10-06 | 1996-03-26 | Matsushita Electric Ind Co Ltd | Pattern forming method |
| JPH0882934A (en) * | 1995-10-06 | 1996-03-26 | Matsushita Electric Ind Co Ltd | Pattern forming method |
| JPH11223951A (en) * | 1998-11-27 | 1999-08-17 | Jsr Corp | Positive type radiation sensitive resin composition |
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|---|---|---|---|---|
| JPH05232706A (en) * | 1992-02-25 | 1993-09-10 | Japan Synthetic Rubber Co Ltd | Radiation sensitive resin compound |
| JPH07199467A (en) * | 1993-12-28 | 1995-08-04 | Nec Corp | Photosensitive resin composition and method for forming pattern |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2621533B2 (en) | 1997-06-18 |
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