JPH03223858A - Formation of pattern - Google Patents
Formation of patternInfo
- Publication number
- JPH03223858A JPH03223858A JP2019530A JP1953090A JPH03223858A JP H03223858 A JPH03223858 A JP H03223858A JP 2019530 A JP2019530 A JP 2019530A JP 1953090 A JP1953090 A JP 1953090A JP H03223858 A JPH03223858 A JP H03223858A
- Authority
- JP
- Japan
- Prior art keywords
- pattern
- resin
- acid
- group
- exposure
- 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
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 20
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 abstract description 12
- 239000012298 atmosphere Substances 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 abstract description 6
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 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
- 238000002834 transmittance Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000007261 regionalization Effects 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- -1 naphthoquinone diazide compound Chemical class 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- NAMDIHYPBYVYAP-UHFFFAOYSA-N 1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound COCCOCCOC.COCCOCCOC NAMDIHYPBYVYAP-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-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
- 241000538562 Banjos Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000003118 aryl group 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 125000006502 nitrobenzyl group Chemical group 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 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
- RXJCXEVLANFAPS-UHFFFAOYSA-N tert-butyl 2-ethenylbenzoate Chemical compound CC(C)(C)OC(=O)C1=CC=CC=C1C=C RXJCXEVLANFAPS-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Materials For Photolithography (AREA)
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以下の紫外線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 for forming a positive pattern using an ultraviolet excimer laser with a wavelength of 400 nm or less.
従来の技術
近年 半導体デバイスの高密度集積化に伴（＼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ｉ線（３６５ｎｍ）が
実用段階に入り、ＫｒＦ、ｒ−キシマレーザ（２４８，
４ｎｍ）が検討されるまでになっていも しかしなが収
レジストパターン形成材料、特にＫｒＦエキシマレー
ザミ 遠紫外線波長域に適したものは未だ開発されてい
なｌ、ＸＱ 例えばＫｒＦエキシマレーザ光 遠紫外
線に対し感光性が高く、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
八 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 In recent years, with the high density integration of semiconductor devices (\microfabrication), the light source wavelength of exposure equipment used in photolithography has become increasingly shorter.At present, i-line (365 nm) has entered the practical stage, and KrF, r- Ximer laser (248,
However, resist pattern forming materials, especially KrF excimer laser, have not yet been developed that are suitable for the far ultraviolet wavelength range. On the other hand, MP2 is said to have high photosensitivity and high transmittance.
400 (Sibley), the large surface absorption of the novolak resin itself, which is the L base polymer, and the photoreaction of the naphthoquinone diazide compound, which is the photosensitive agent, were not good. Not likely.
また 遠紫外線用パターン形成材料として２４８゜４ｎ
ｍ付近の波長の遠紫外光に高い透過率を有するポリマー
とじて、 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。しかるに このレジスト（
よ ベースポリマーか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％にすぎ唄
十分な光退色性が得られていなｔ、Ｘｏ 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ていなｔ、％
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
となっ島 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エキシマレーザ光を
用いる場合、実用化は困難な状況にある。Also, 248°4n is used as a pattern forming material for far ultraviolet rays.
A resist made of a 2-diazo-1,3-dione compound has been reported as a polymer having high transmittance to deep ultraviolet light having a wavelength around m. However, this resist (
While the base polymer has a transmittance of 70%, the transmittance of the pattern forming material after exposure is only 45%.
In addition, as a result of the pattern formation experiment, the pattern had an angle of about 70 degrees, and a pattern shape that would be a satisfactory etching mask with a vertical shape was not obtained. % Also, the sensitivity of this patterning material is 140 to 150
In other words, highly transparent pattern forming materials using 2-diazo-1,3-dione compounds have low sensitivity, especially KrF, which is not energy efficient. When using excimer laser light, it is difficult to put it into practical use.
近年 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た こ
れ（上 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Ｐ
ｏｌｙｍ Ｅｎｇ。In recent years, materials composed of poly(tertiary butoxycarbonate) styrene and onium salts have been proposed as a means of reducing the amount of exposure energy. For example, (H, Ito et al.
olym Eng.
Ｓ ｃ ｉ、 、２３表１０１２頁（１９８３） ）
等で近年種々の報告がある。第５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秒ドラ
フトベークＬ １．０ミクロン厚のパターン形成材料
を得る（第５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が多しも 次に２
４８．４ｎｍのＫｒＦエキシマレーザ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５図（ｂ））。そして、 ホッ
トプレート３上で前記材料膜を１３０℃で９０秒間加熱
処理（ＦＥＢ）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５図（
ｃ））。Sci., 23 Table 1012 pages (1983))
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
A pattern forming material having a thickness of 1.0 micron was obtained by rotating and applying the material on a hot plate at 90° C. for 90 seconds (Fig. 5(a)). There is an insulating wind on board 1.
Conductive wind An oxide film is often formed.Next 2
Exposure to a 48.4 nm KrF excimer laser 4 through a mask 5 causes the following chemical changes in the acid generator to generate acid (FIG. 5(b)). Then, by subjecting the material film to a heat treatment (FEB) at 130° C. for 90 seconds on the hot plate 3, the following chemical changes occur in the resin and the resin becomes alkali-soluble. (Figure 5 (
c)).
そしてアルカリ現像液（ＭＦ−３１９（シブレイ社））
を用いてパターン形成材料２の露光部を溶解除去しポジ
型パターン１２ａを得る（第５図（ｄ））。and alkaline developer (MF-319 (Sibley))
The exposed portion of the pattern forming material 2 is dissolved and removed using a wafer to obtain a positive pattern 12a (FIG. 5(d)).
この時、ポジ型パターン１２ａは超微細パターンであり
、感度も１５ｍ Ｊ ／ ｃ ｒｎ２程度と良好な結果
が得られｔ：、。At this time, the positive pattern 12a was an ultra-fine pattern, and a good result was obtained with a sensitivity of about 15 mJ/crn2.
発明が解決しようとする課題
しかし本発明者らの検討によれば 第６図に示す微 露
光後、発生した酸を拡散させるための基板加熱（前記Ｐ
Ｅ Ｂ （Ｐｏｓｔ Ｅｘｐｏｓｕｒｅ Ｂａｋｅ）
） ニよってパターン寸法が変化することが判明し九
寸法変動は例えば露光から１時間経過したＦＥＢを行っ
た場合２０％以上もあり、これを超微細ルールの半導体
デバイスの製造へ応用した場合、ウェハ又はチップ間の
パターン寸法ばらつきとなり、半導体素子の分留り、信
頼法 特性に大きな影響をあたえ、設計通りのデバイス
を作成することを不可能である。この様にパターン寸法
が変動する理由（瓜 本発明者ら（よ 樹脂中の官能基
が露光中にアルカリ可溶性反応するためであることを見
い出しな 従来のポリｔ−ＢＯＣスチレン樹脂は遠紫外
線露光により、酸雲囲気下と同じ下記反応か発生する。Problems to be Solved by the Invention However, according to the studies of the present inventors, the heating of the substrate to diffuse the generated acid after the slight exposure shown in FIG.
E B (Post Exposure Bake)
) It has been found that the pattern dimensions change as a result, and the variation in dimension is, for example, more than 20% when FEB is performed one hour after exposure. Otherwise, pattern dimensions may vary between chips, which greatly affects the separation and reliability characteristics of semiconductor elements, making it impossible to create devices as designed. The reason why the pattern dimensions fluctuate in this way is that the functional groups in the resin undergo an alkali-soluble reaction during exposure. , the following reaction occurs, which is the same as under an atmosphere surrounded by an acid cloud.
このよう！ミ 露光により発生する酸をＦＥＢプロセス
で拡散する以前く 樹脂はこの露光工程でアルカリ可溶
性に反応してしまう。その為 露光からＦＥＢまでの時
間に依存しパターン寸法が変化する。ポリｔ−ＢＯＣス
チレンζよ 官能基部分に２ケ所、結合の弱い部分（１
部分）を有する。like this! Before the acid generated by exposure is diffused in the FEB process, the resin reacts to become alkali-soluble during this exposure process. Therefore, the pattern dimensions change depending on the time from exposure to FEB. Poly t-BOC styrene ζ has two weak bonding parts (1
part).
○
これらの結合は酸雰囲気のみならずミ 露先によっても
容易に切断される。すなわちｔ−ＢＯＣは結合の弱い部
分を多く有するた人 露先による分解が発生しやすくな
る。すなわぢ これがパターン寸法変動となると考えら
れる。すなわちこれを防止する事は 寸法余裕の小さい
超微細パターンの半導体集積回路の製造において極めて
重要となる。○ These bonds are easily broken not only by an acid atmosphere but also by a dew point. In other words, t-BOC has many parts with weak bonds and is more likely to be decomposed due to exposure to humans. In other words, this is considered to be a pattern dimension variation. In other words, preventing this is extremely important in manufacturing semiconductor integrated circuits with ultra-fine patterns that have small dimensional margins.
したがって本発明（よ こうした検討に基づき、化学増
幅型のパターン形成材料を用いるととも番ミ光安定性の
高い官能基を導入することにより、寸法精度の高い微細
パターンを形成する寸法を提供する事を目的とする。Therefore, the present invention (based on these studies) provides dimensions for forming fine patterns with high dimensional accuracy by using a chemically amplified pattern forming material and introducing a highly photostable functional group. With the goal.
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 基板上圏 分子内にｔ
ｅｒｔ−ブトキシ基を有する樹脂 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
媒よりなる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
膜を現像してパターン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を提供するものである。また
本発明は 前記樹脂が下記（Ｉ）式で示される基を含む
ことを提供するものである。Means for Solving the Problems The pattern forming method of the present invention (with t in the molecule on the substrate)
a resin having an ert-butoxy group; a photosensitive compound that generates acid upon exposure to light; a step of forming a pattern-forming material film made of a solvent capable of dissolving the resin and the compound; and a step of selectively exposing the material film to deep ultraviolet rays. and a step of developing the material film to form a pattern. The present invention also provides that the resin contains a group represented by the following formula (I).
（但Ｌ Ｒ１，Ｒ２，Ｒｓはおのおの独立て 水素原
子、ハロゲン原子、低級アルキル基を表わす）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（よ
光反応に従って酸が発生する。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、現像の胤 現像液に溶出してく
る。他人 未露光部は酸が発生しないム 加熱処理して
も化学変化は生ぜず、アルカリ可溶性基の発現はな（−
本発明の方法によれ（瓜 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為 露光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 露
光からＦＥＢまでの時間に依存し 前述のごとくレジス
トパターン寸法が変動することは 実際のパターンと設
計寸法との間に誤差をもたらす。これらは従来の半導体
プロセス（１μｍ以上のルール）では重要なファクター
とはならない力＜、 １μｍ以下、特に０．５μｍ以下
の超微細デバイス形成プロセスにおいてデバイス特性、
分留り、信頼性を大きく左右するファクターとなる。本
発明は さらにパターン形成材料に光安定性の高い官能
基すなわちｔｅｒｔ−ブトキシ基を導入してパターン形
成を行うことにより、設計寸法通りにレジストパターン
を形成することが可能となり、超微細ルールの半導体デ
バイス等の作製に必要不可欠である。(However, L R1, R2, and Rs each independently represent a hydrogen atom, a halogen atom, or a lower alkyl group.) Effect To specifically explain the method of the present invention, a photosensitive compound exposed to KrF excimer laser light and deep ultraviolet light. (According to the photoreaction, acid is generated. When heat treatment follows the exposure process, the functional groups of the resin undergo chemical changes due to the acid.
It becomes alkali soluble and is eluted into the developing solution. Others No acid is generated in the unexposed area.No chemical change occurs even after heat treatment, and no alkali-soluble groups are expressed (-
By the method of the present invention, a positive pattern with good contrast is formed.Also, since the acid generated during exposure acts catalytically, exposure only needs to generate the necessary acid, and the exposure energy As mentioned above, variations in the resist pattern dimensions, which depend on the time from exposure to FEB, lead to errors between the actual pattern and the design dimensions. The above rules) force is not an important factor in device characteristics in the process of forming ultra-fine devices of 1 μm or less, especially 0.5 μm or less.
Fractionation is a factor that greatly influences reliability. Furthermore, by introducing a highly photostable functional group, that is, a tert-butoxy group, into the pattern forming material and performing pattern formation, it is possible to form a resist pattern according to the designed dimensions, and it is possible to form a resist pattern according to the designed dimensions. It is essential for manufacturing devices, etc.
実施例
本発明者ら（よ パターン寸法が変動する理由は前述の
ごとく樹脂の官能基が光安定性に乏しいことにあると考
え 光安定性が高くかつ酸雰囲気下でアルカリ可溶性を
示す官能基を導入した樹脂をパターン形成材料として用
いる方法を見い出した樹脂中に光安定性が高くかつ酸雰
囲気下でアルカリ可溶性を示す官能基を導入することに
より、露光プロセスでは酸発生反応のみが発生Ｌ 後の
ＦＥＢプロセスでのみアルカリ可溶性反応を発生させる
ことが可能となる。そのためパターン寸法を決定するパ
ラメータは前記三者のみとなり、露光からＦＥＢまでの
時間に依存しなくなる。すなわち寸法精度に秀れたパタ
ーン形成方法となる。そして本発明者らは前記官能基を
種々検討した結果ｔｅｒｔ−（ターシャル）ブトキシ基
が光安定性に秀れかつ酸雰囲気下で感度良くアルカリ可
溶性反応が発生することを見出し九 な扛 酸発生剤に
ついて１友 露先により酸を発生するものであれば何で
もよく、例え（Ｌ 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い。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（Ｘｏ 以下に実施例を用いて
本発明を更に詳細に説明する力士 本発明はこれら実施
例に何ら制限されるものではなｌ、Ｘ。Example The present inventors believe that the reason why the pattern dimensions fluctuate is that the functional groups of the resin have poor photostability as described above. We found a method to use the introduced resin as a pattern-forming material.By introducing into the resin a functional group that has high photostability and is alkali-soluble in an acid atmosphere, only the acid generation reaction occurs during the exposure process. It is possible to generate an alkali-soluble reaction only in the FEB process.Therefore, the parameters that determine pattern dimensions are only the above three, and are no longer dependent on the time from exposure to FEB.In other words, pattern formation with excellent dimensional accuracy As a result of examining various functional groups, the present inventors found that tert-(tert)butoxy group has excellent photostability and causes an alkali-soluble reaction with good sensitivity in an acid atmosphere. About acid generators: Any type of acid generator may be used as long as it generates acid depending on its tip, such as nitrobenzyl compounds, onium salts, sulfonic acid compounds, carboxylic acid compounds, etc. (Of course, it is not limited to these) The same goes for the solvent, and any solvent may be used as long as it can dissolve the resin and acid generator. There are no restrictions, X.
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 １ｇ（３）ジエ
チレングリコールジメチルエーテル（ＤＩＧＬＹＭＥ）
７０ｇここで（１）の樹
脂は 酸雰囲気でアルカリ可溶性を示す官能基としてタ
ーシャルブトキシ基を用いた一例である。ターシャルブ
トキシ基（上 下記に示すごとく酸雰囲気下で加熱する
事により（１）のロニ一一一二〕 の部分のＣ−０結合
が切断され結果として水酸基を形成する。Example 1 A reagent was prepared with the following composition and used as a pattern forming material (2) 1 g of 2,6-cinitrobenzyl p-toluenesulfonate (3) Diethylene glycol dimethyl ether (DIGLYME)
70g Here, the resin (1) is an example in which a tertiary butoxy group is used as a functional group showing alkali solubility in an acid atmosphere. The C-0 bond of the tertiary butoxy group (Ron-1-1-2 of (1) by heating in an acid atmosphere as shown below) is cleaved, resulting in the formation of a hydroxyl group.
また（２）は酸発生剤として挙げたもので、露光により
以下の反応が発生すも
ＣＨ３＋ＳＯｓ Ｈ
また（３） ＋ｉ 前記両者を溶解可能な溶媒であり
、遠赤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発揮
される。 ｔａｒ ｔ−ブトキシ基（戴その官能基中に
結合の弱い部分が１ケ所しか存在しなシ℃シかｋ この
結合１よ 従来のｔ−ＢＯＣＯＣ（ＣＨ３）３
〒
より強い結合力を有し 露光では容易に切断される事は
なｌ、Ｘｏ すなわ叛 ＰＥＢプロセス中のへアルカ
リ可溶性反応が発生ずるた人 パターン寸法を生じない
。第１図を用いて本発明のパターン形成方法を説明すも
シリコン等の半導体基板Ｉ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
膜とり、 ９０℃、９０秒間ホットプレート３でソフ
トベークし 薄膜中の溶媒を蒸発除去し 厚さ １．０
μｍのパターン形成材料薄膜を得る（第１図（ａ））。In addition, (2) is listed as an acid generator, and when exposed to light, the following reaction occurs: CH3 + SOs H and (3) +i is a solvent that can dissolve both of the above, and has high transmittance in the far infrared region. &KrF Good results are exhibited as a solvent for pattern forming materials for excimer lasers. tar t-butoxy group (there is only one weak bond in the functional group) This bond 1 has a stronger bonding force than conventional t-BOCOC(CH3)3 Therefore, it is not easy to cut the Xo, that is, the alkali-soluble reaction during the PEB process does not result in pattern dimensions.The pattern forming method of the present invention will be explained with reference to FIG. Pattern forming material 2 prepared with the above composition is coated on a semiconductor substrate I such as silicon by rotation to form a thin resist film, and soft baked on a hot plate 3 at 90°C for 90 seconds to remove the solvent in the thin film by evaporation. Thickness 1.0
A .mu.m thin film of pattern forming material is obtained (FIG. 1(a)).
な耘 基板１表面は絶縁風 導電風 半導体膜等が形成
されている場合も多し−次に２４８．４ｎｍのＫｒＦ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
、前述のごとく酸発生剤（２）を光分解する。Insulating wind, conductive wind, semiconductor films, etc. are often formed on the surface of the substrate 1.Next, by exposing the 248.4 nm KrF excimer laser 4 through the mask 5, the acid generator is removed as described above. (2) is photolyzed.
（第１図（ｂ））。そして１３０ｔ、 ９０秒間ホッ
トプレート３でベークし 前述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））。(Figure 1(b)). Then, it is baked on the hot plate 3 for 90 seconds at 130 tons to cause the tertiary butoxy group to undergo an alkali-soluble reaction as described above (FIG. 1 (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２
ｂを溶解除去し ポジ型レジストパターン２ａを得た（
第１図（ｄ））。Then, with an alkaline developer (2.38% tetramethylammonium hydroxide (TMAH) aqueous solution)
The exposed area 2 of the pattern forming material 2 is developed by second development.
b was dissolved and removed to obtain a positive resist pattern 2a (
Figure 1(d)).
このレジストパターン２ａをエツチングマスクとして下
の基板１の表面をエツチング加工する。Using this resist pattern 2a as an etching mask, the surface of the underlying substrate 1 is etched.
本発明に用いたパターン形成材料（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
示した 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
．５．感度１０ｍＪ／Ｃｍ２ と高コントラスト、高感
度であった 第４図に本発明のパターン形成方法による
露光からＦＥＢまでの時間に対するパターン寸法依存性
を示す。The transmittance did not change almost before and after exposure and showed a high value of about 65% Resist pattern 2 as a result of a pattern formation experiment
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
．． 5. High contrast and high sensitivity were achieved with a sensitivity of 10 mJ/Cm2. Figure 4 shows the dependence of pattern size on the time from exposure to FEB by the pattern forming method of the present invention.
１０時間経過後もパターン寸法の変動゛は観察されなか
っ九 すなわ板 本発明のパターン形成方法は０．５μ
ｍ以下の超微細パターンを、設計寸法通りに良好な形状
で形成する事が可能で、結果として半導体デバイスの設
計通りの特性、信頼性を高分留りで形成することが可能
であり、サブハーフミクロンデバイス作製において、意
義大なものである。No variation in pattern dimensions was observed even after 10 hours.
It is possible to form ultra-fine patterns of less than m in size in good shape according to the designed dimensions, and as a result, it is possible to form semiconductor devices with the characteristics and reliability as designed in a high fraction. This is of great significance in the production of half-micron devices.
実施例２
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５ｍＪ／ｃｍ
２の感度で得られた
実施例３
酸発生剤（２）を下記の組成に変更する以外ζ表実施例
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／
ｃｍ２の感度で得られた
実施例４
樹脂（１）を下記の組成に変更する以外Ｇｅｌ 実施
例１と同様の実験を行っ九
ＣＨａ−ＣＣＨｓ ｍ： ｎ
＝３： ｌＣＨ３Ｍ ｗ ＝ １００００
この樹脂（よ 耐熱性を向上させる基（Ｃ三Ｎ）万丈実
施例１のものより少ない比率で導入されたものである。Example 2 Example 1 except that the acid generator (2) was changed to the following composition.
The same experiment as in Example 1 was carried out and the results were as good as in Example 1.
Example 3 Obtained with a sensitivity of 2.Example 3 The same experiment as in ζ table Example 1 was carried out except that the acid generator (2) was changed to the following composition.ResultsThe same good results as in Example 1 were obtained at 15mJ. /
Example 4 Obtained with sensitivity of cm2 Gel The same experiment as in Example 1 was conducted except that the resin (1) was changed to the following composition, and 9 CHa-CCHs m: n
= 3: lCH3M w = 10000 In this resin, a group (C3N) which improves heat resistance was introduced in a smaller proportion than that in Banjo Example 1.
実験を行った結果 実施例１と同様の結果が得られた
実施例５
樹脂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ｋ
この樹脂は 分子内にイミド結合を導入する事によって
耐熱性を向上させんとしたものである。実験の結果 実
施例１と同様の良好な結果が得られ実施例６
樹脂（１）
を下記のものに変更する以外は実施例
と同様の実験を行った
ＣＨａ
その結果
実施例
と同様の良好な結果が得られ
た。Results of the experiment Example 5 The same results as in Example 1 were obtained.Experiments were conducted in the same manner as in Example 1 except that the composition of the resin was changed to the following.This resin introduced an imide bond into the molecule. The aim was to improve heat resistance by doing so. Results of the experiment Good results similar to those in Example 1 were obtained. The results were obtained.
実施例７
樹脂（１）
を下記のものに変更する以外は実施例
と同様の実験を行っ九
この樹脂（よ
分子内にアルカリ可溶解基
（−０Ｈ）を
導入する事により、
疎水性基板との密着性を向上
させる事を目的とした その結果 良好な形状の０．３
μｍ Ｌ ／ Ｓパターンが形成する事ができへ実施例
８
樹脂を下記の組成に変更する以外（よ 実施例１と同様
の実験を行っ九
Ｃｌ：ｍ： ｎ＝１： １： １響
ＣＨｓ Ｍ ｗ ＝ １００００こ
の樹脂？１ 分子内にＣミＮを導入する事により耐熱
性を向上させ、かス 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九実施例９
パターン形成材料をＳＯＧが形成された基板上に成膜す
る以外（表 実施例８と同様の実験を行っｋ その結果
実施例８と同様に良好な形状を有する ０．３μｍの
ラインアンドスペースパターンカ丈パターンはがれする
ことなく良好な密着性を有することがわかっ九
実施例１０
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）＆１０％イソプロパツール水溶
液に変更する以外は 実施例９と同様の実験を行っｋ
このよう（ミ 現像液にインプロパツール等のアルコー
ルを混入する事により、現像液中に極性が生改 パター
ン形成材料膜とのぬれ性が向上することが判明した 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電
光部のパターン形成材料の溶解速度を増加させるム 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／ｃｍ”という非常に
高い感度で得られた な耘 酸発生剤についてＸ上下記
一般式で示される化合物万丈 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Ｌ℃
一般式
（成虫 Ｒ”はトリクロルアセチル基 ｐ−トルエンス
ルホニルＪＬｐ−ト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Ｌ Ｒ”及びＲ２１は夫々、独立して
水素原子、ハロゲン原子又はニトロ基を表わす。）
一般式
（式Ｃ１ｔ Ｒ２２及びＲ１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
し
Ｒ２４及びＲｉａ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。）を表わす。）
一般式
（式＋ Ｒ”及びＲ２？は夫々、独立して水素原子、
ハロゲン原子、直鎖状、分岐状又は環状のアルキル基
又はアルコキシ基を表わり、、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
基を表わり、、 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Ｒ”″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 ＲＩＩＲ２２Ｒ２！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
ル基 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”〜Ｒ２２Ｒ２１！ 、、、 Ｒ２
２及びＲ２″〜Ｒ２４はＡ、 Ｂ、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万丈 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ζ戴 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
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１．％ 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Ｌ＋％
発明の効果
本発明（よ 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リソグラフィプロセスに対
する安定性を有するとともく 寸法変動の少ない新規な
パターン形成材料を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ルールの半導体
デバイス等への適用が可能となり、結果として半導体素
子等の微細イＫ 歩留りの向上に続がり、超微細かつ高
密度な半導体集積回路等の安定な製造に大きく寄与する
ものである。Example 7 The same experiment as in Example 7 was carried out except that the resin (1) was changed to the one shown below. By introducing an alkali-soluble group (-0H) into the molecule of this resin, a hydrophobic substrate was formed. The aim was to improve the adhesion of the
A μm L/S pattern could be formed. Example 8 The same experiment as in Example 1 was conducted except that the resin was changed to the following composition. w = 10000 This resin?1 The purpose was to improve heat resistance by introducing C-N into the molecule, and to improve adhesion by introducing a hydroxyl group at the same time.9 Example 9 Pattern forming material Except for forming a film on the substrate on which SOG was formed (Table) The same experiment as in Example 8 was conducted. As a result, the line and space pattern of 0.3 μm had a good shape as in Example 8. The height pattern peeled off. Example 10 Same experiment as Example 9 except that the developer was changed to 2.38% TMAH (tetramethylammonium hydroxide) & 10% isopropanol aqueous solution. go
In this way, it was found that by mixing alcohol such as Improper Tool into the developer, the polarity of the developer was regenerated and the wettability with the pattern-forming material film was improved. Improving the wettability increases the dissolution rate of the pattern-forming material in the electrophotographic part, making it possible to achieve even higher sensitivity.As a result, the same result as in Example 9 was achieved, with a power of <3.5 mJ/cm. Regarding the acid generator obtained with extremely high sensitivity, the compound represented by the following general formula has good solution stability, acid generation efficiency, etc., and when used as a pattern forming material, good results can be obtained. Expected power (any substance that generates acid upon exposure may be used, but is not limited to these) General formula (Imago R" is trichloroacetyl group p-toluenesulfonyl JLp-trifluoromethylbenzenesulfonyl group LR" and R21 each independently represent a hydrogen atom, a halogen atom, or a nitro group.) General formula (Formula C1t R22 and R1 each independently represent a straight chain (R24 and Ria 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). ) General formula (Formula + R" and R2? each independently represent a hydrogen atom,
Halogen atom, linear, branched or cyclic alkyl group
or represents an alkoxy group, ze is verchlorate,
Represents p-toluenesulfonate or trifluoromethanesulfonate. ) General formula (Formula + Y represents a carbonyl group, sulfonyl group, sulfinyl group, R" represents a lower alkyl group, trifluoromethyl group, phenyl group or alkyl-substituted phenyl group, L R" and R"" are each independently R'' represents a hydrogen atom, a halogen atom, a lower alkyl group, an alkoxy group, or an alkylthio group. General formula (Imago RIIR22R2! and R24 are each independently a hydrogen atom) , halogen atom, linear, branched or cyclic alkyl group Haloalkyl group Alkoxy group Aralkyl group Substituted phenyl group Phenyl group Represents a nitro group or a cyano group L R”~R22R21! ,,, R2
2 and R2'' to R24 each independently represent an alicyclic ring, heteroalicyclic ring, aromatic ring, or heteroaromatic ring having 5 to 8 carbon atoms with A, B, and C interposed in between. Anything can be used as long as the resin and acid generator can be dissolved, such as ethyl cellosolve acetate, methyl cellotulacetate, ethyl lactate, methyl lactate, diethylene glycol dimethyl ether, which has low absorption in the far ultraviolet region. Examples include, but are not limited to, 1.% monobutyl ether, etc. The same can be said about the exposure light source, and any light source that generates acid upon exposure may be used, such as g-line (436 nm) or i-line. (365nm),
Electron beams, X-rays, etc. (of course, this is not the case) The present invention provides a pattern forming method using a small amount of new pattern forming material, and the present invention enables application to 0.3 μm rule semiconductor devices, etc., and as a result, improves the fineness of semiconductor devices, etc., and improves yield. This will greatly contribute to the stable manufacture of ultra-fine and high-density semiconductor integrated circuits.
第１図（よ 本発明のパターン形成方法の工程断面医
第２図は 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 実線は露光詠 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
特性は 第４図１よ 本発明の一実施例のパターン形成
方法の寸法変動医第５図（表 従来のパターン形成方法
の工程断面医第６図１よ 従来のパターン形成方法の寸
法変動図であム
１ 、、、、シリコン基板、 ２ 、、、、本発明の゛
パターン形成材料ＷＬ ２ａ、、、、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。FIG. 1 (See Figure 1.)
Figure 2 is an ultraviolet ray spectral curve diagram of a pattern-forming material according to an embodiment of the present invention (the solid line shows the result after exposure, and the broken line shows the result after exposure).
, FIG. 3 shows the irradiation characteristics of the pattern forming material according to an embodiment of the present invention. Cross-sectional diagram of Fig. 6 1 is a diagram of dimensional variations in a conventional pattern forming method. ,, Hot plate, 4, K r F excimer laser, 5, Mask.
Claims (2)
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よりなるパターン形成材
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、前記材料膜を現像して前記材料パタ
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) Forming a pattern-forming material film on the substrate consisting of a resin having a tert-butoxy group in its molecule, a photosensitive compound that generates an acid upon exposure, and a solvent that can dissolve the resin and the compound; A pattern forming method comprising the steps of selectively exposing the material film to ultraviolet light and developing the material film to form the material pattern.
特徴とする特許請求の範囲第１項記載のパターン形成方
法。 ▲数式、化学式、表等があります▼（ I ） （但Ｌ、Ｒ＿１、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）(2) The pattern forming method according to claim 1, wherein the resin contains a group represented by the following formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, L, R_1, R_2, and R_3 are each independent and represent a hydrogen atom, a halogen atom, or a lower alkyl group)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019530A JPH03223858A (en) | 1990-01-30 | 1990-01-30 | Formation of pattern |
| DE1991618936 DE69118936T2 (en) | 1990-01-30 | 1991-01-24 | Process for producing an image structure |
| EP19910300564 EP0440376B1 (en) | 1990-01-30 | 1991-01-24 | Process for forming pattern |
| US07/646,920 US5252435A (en) | 1990-01-30 | 1991-01-28 | Method for forming pattern |
| KR1019910001465A KR940007794B1 (en) | 1990-01-30 | 1991-01-29 | Process for formaiton of pattern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019530A JPH03223858A (en) | 1990-01-30 | 1990-01-30 | Formation of pattern |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03223858A true JPH03223858A (en) | 1991-10-02 |
Family
ID=12001895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019530A Pending JPH03223858A (en) | 1990-01-30 | 1990-01-30 | Formation of pattern |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03223858A (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03223857A (en) * | 1990-01-30 | 1991-10-02 | Matsushita Electric Ind Co Ltd | Pattern forming method |
| US6027854A (en) * | 1997-02-28 | 2000-02-22 | Shin-Etsu Chemical Co., Ltd. | Polymers chemically amplified positive resist compositions, and patterning method |
| US6033828A (en) * | 1997-01-27 | 2000-03-07 | Shin-Etsu Chemical Co., Ltd. | Partially hydrogenated polymers and chemically amplified positive resist compositions |
| US6136502A (en) * | 1997-10-08 | 2000-10-24 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US6156481A (en) * | 1998-10-29 | 2000-12-05 | Shin-Etsu Chemical Co., Ltd. | Positive resist composition |
| US6156477A (en) * | 1997-01-24 | 2000-12-05 | Shin-Etsu Chemical Co., Ltd. | Polymers and chemically amplified positive resist compositions |
| US6384169B1 (en) | 1997-10-08 | 2002-05-07 | Shin-Etsu Chemical Co., Ltd. | Styrene polymer, chemically amplified positive resist composition and patterning process |
| US6414101B1 (en) | 1999-03-26 | 2002-07-02 | Shin-Etsu Chemical Co., Ltd. | Dendritic polymers and making method |
| US6511785B1 (en) | 1999-11-12 | 2003-01-28 | Shin Etsu Chemical Co., Ltd. | Chemically amplified positive resist composition and patterning method |
| US6641975B2 (en) | 2000-08-14 | 2003-11-04 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| EP1378795A1 (en) | 2002-07-04 | 2004-01-07 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US6737214B2 (en) | 2000-03-09 | 2004-05-18 | Shin-Etsu Chemical Co., Ltd. | Chemical amplification resist compositions |
| US6746817B2 (en) | 2000-11-01 | 2004-06-08 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US6949323B2 (en) | 2001-10-30 | 2005-09-27 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US7267923B2 (en) | 2003-05-26 | 2007-09-11 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US7344827B2 (en) | 2003-05-07 | 2008-03-18 | Shin-Etsu Chemical Co., Inc. | Fine contact hole forming method employing thermal flow process |
| KR100854888B1 (en) * | 2007-08-20 | 2008-08-28 | 주식회사 하이닉스반도체 | Method of forming micro pattern for semiconductor device |
| US7501223B2 (en) | 2006-10-13 | 2009-03-10 | Shin-Etsu Chemical Co., Ltd. | Polymer, resist composition and patterning process using the same |
| US7618763B2 (en) | 2005-11-08 | 2009-11-17 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58122533A (en) * | 1982-01-14 | 1983-07-21 | Somar Corp | Photosensitive material |
| JPS5945439A (en) * | 1982-08-23 | 1984-03-14 | インタ−ナシヨナル ビジネス マシ−ンズ コ−ポレ−シヨン | Resist composition |
| JPS6435433A (en) * | 1987-07-01 | 1989-02-06 | Basf Ag | Radiation sensitive mixture for photosensitive layer forming material |
| JPH0218564A (en) * | 1988-05-19 | 1990-01-22 | Basf Ag | Making of radiation sensitive mixture and relief pattern |
| JPH03198059A (en) * | 1989-12-27 | 1991-08-29 | Sony Corp | Photosensitive resin composition |
| JPH03241355A (en) * | 1989-10-13 | 1991-10-28 | E I Du Pont De Nemours & Co | Photosensitive element |
-
1990
- 1990-01-30 JP JP2019530A patent/JPH03223858A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58122533A (en) * | 1982-01-14 | 1983-07-21 | Somar Corp | Photosensitive material |
| JPS5945439A (en) * | 1982-08-23 | 1984-03-14 | インタ−ナシヨナル ビジネス マシ−ンズ コ−ポレ−シヨン | Resist composition |
| JPS6435433A (en) * | 1987-07-01 | 1989-02-06 | Basf Ag | Radiation sensitive mixture for photosensitive layer forming material |
| JPH0218564A (en) * | 1988-05-19 | 1990-01-22 | Basf Ag | Making of radiation sensitive mixture and relief pattern |
| JPH03241355A (en) * | 1989-10-13 | 1991-10-28 | E I Du Pont De Nemours & Co | Photosensitive element |
| JPH03198059A (en) * | 1989-12-27 | 1991-08-29 | Sony Corp | Photosensitive resin composition |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03223857A (en) * | 1990-01-30 | 1991-10-02 | Matsushita Electric Ind Co Ltd | Pattern forming method |
| US6156477A (en) * | 1997-01-24 | 2000-12-05 | Shin-Etsu Chemical Co., Ltd. | Polymers and chemically amplified positive resist compositions |
| US6033828A (en) * | 1997-01-27 | 2000-03-07 | Shin-Etsu Chemical Co., Ltd. | Partially hydrogenated polymers and chemically amplified positive resist compositions |
| US6027854A (en) * | 1997-02-28 | 2000-02-22 | Shin-Etsu Chemical Co., Ltd. | Polymers chemically amplified positive resist compositions, and patterning method |
| US6136502A (en) * | 1997-10-08 | 2000-10-24 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US6384169B1 (en) | 1997-10-08 | 2002-05-07 | Shin-Etsu Chemical Co., Ltd. | Styrene polymer, chemically amplified positive resist composition and patterning process |
| US6613844B2 (en) | 1997-10-08 | 2003-09-02 | Shin-Etsu Chemical Co., Ltd. | Styrene polymer, chemically amplified positive resist composition and patterning process |
| US6156481A (en) * | 1998-10-29 | 2000-12-05 | Shin-Etsu Chemical Co., Ltd. | Positive resist composition |
| US6414101B1 (en) | 1999-03-26 | 2002-07-02 | Shin-Etsu Chemical Co., Ltd. | Dendritic polymers and making method |
| US6511785B1 (en) | 1999-11-12 | 2003-01-28 | Shin Etsu Chemical Co., Ltd. | Chemically amplified positive resist composition and patterning method |
| US6737214B2 (en) | 2000-03-09 | 2004-05-18 | Shin-Etsu Chemical Co., Ltd. | Chemical amplification resist compositions |
| US6641975B2 (en) | 2000-08-14 | 2003-11-04 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US6746817B2 (en) | 2000-11-01 | 2004-06-08 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US6949323B2 (en) | 2001-10-30 | 2005-09-27 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| EP1378795A1 (en) | 2002-07-04 | 2004-01-07 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US6869748B2 (en) | 2002-07-04 | 2005-03-22 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US7344827B2 (en) | 2003-05-07 | 2008-03-18 | Shin-Etsu Chemical Co., Inc. | Fine contact hole forming method employing thermal flow process |
| US7267923B2 (en) | 2003-05-26 | 2007-09-11 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US7618763B2 (en) | 2005-11-08 | 2009-11-17 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
| US7501223B2 (en) | 2006-10-13 | 2009-03-10 | Shin-Etsu Chemical Co., Ltd. | Polymer, resist composition and patterning process using the same |
| KR100854888B1 (en) * | 2007-08-20 | 2008-08-28 | 주식회사 하이닉스반도체 | Method of forming micro pattern for semiconductor device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH03223858A (en) | Formation of pattern | |
| US5252435A (en) | Method for forming pattern | |
| JPS5817112A (en) | Positive novolak photoresist composition and blend | |
| JP2004086203A (en) | Fine pattern forming material and method for manufacturing electronic device | |
| JPH01300250A (en) | Photoresist composition | |
| JPH0262544A (en) | Photoresist composition | |
| JP2002156764A (en) | Method for forming fine resist hole pattern | |
| JP2712700B2 (en) | Pattern formation method | |
| KR940007794B1 (en) | Process for formaiton of pattern | |
| JP2615742B2 (en) | Resist using photosensitive compound | |
| JP2621533B2 (en) | Pattern formation method | |
| JP2661317B2 (en) | Pattern formation method | |
| JP2699971B2 (en) | Pattern formation method | |
| JP2615530B2 (en) | Pattern formation method | |
| JP2713299B2 (en) | Pattern formation method | |
| JPH0261640A (en) | Photosensitive composition | |
| JP2647065B2 (en) | Pattern formation method | |
| JPH04221814A (en) | Pattern forming method | |
| JP3925882B2 (en) | Positive photosensitive resin composition | |
| JPH0450947A (en) | Pattern forming method | |
| JPH03208056A (en) | Photosensitive composition | |
| JPH03223859A (en) | Formation of pattern | |
| JP2861992B2 (en) | New resist material | |
| JPH01106044A (en) | Pattern forming material | |
| JPH01154047A (en) | Photosensitive composition |