JPH02118649A - Positive pattern forming material - Google Patents
Positive pattern forming materialInfo
- Publication number
- JPH02118649A JPH02118649A JP27342888A JP27342888A JPH02118649A JP H02118649 A JPH02118649 A JP H02118649A JP 27342888 A JP27342888 A JP 27342888A JP 27342888 A JP27342888 A JP 27342888A JP H02118649 A JPH02118649 A JP H02118649A
- Authority
- JP
- Japan
- Prior art keywords
- pattern forming
- forming material
- positive
- resin
- group
- 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
- 239000000463 material Substances 0.000 title claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 20
- 150000003839 salts Chemical group 0.000 claims 3
- 239000000126 substance Substances 0.000 claims 3
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 150000007530 organic bases Chemical class 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 229910005948 SO2Cl Inorganic materials 0.000 abstract 1
- 229910006069 SO3H Inorganic materials 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 42
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 20
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 20
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 20
- 239000011976 maleic acid Substances 0.000 description 20
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 20
- 239000003153 chemical reaction reagent Substances 0.000 description 19
- 150000002148 esters Chemical class 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000726103 Atta Species 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- VZPPHXVFMVZRTE-UHFFFAOYSA-N [Kr]F Chemical compound [Kr]F VZPPHXVFMVZRTE-UHFFFAOYSA-N 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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際のパターン形成材料
にかかり、光源として遠紫外線、特にＫｒＦエキシマレ
ーザを用いてポジ型のパターンを形成するパターン形成
材料にかかる。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to pattern forming materials used in manufacturing semiconductor devices, etc., and is used to form positive patterns using deep ultraviolet rays, particularly KrF excimer laser, as a light source. It depends on the material.
従来の技術
近年、半導体デバイスの高密度集積化に伴い、微細加工
、中でもフォトリングラフィに用いられる露光装置の使
用波長は益々短波長化し、今ではＫｒＦ （フッ化クリ
プトン）エキシマレーザ（２４８−４ｎｍ ） が検討
されるまでになっている。しかしながら従来のナフトキ
ノンジアジド−ノボラック樹脂よシなる遠紫外線レジス
トは第２図に示す様、エキシマレーザに対して大きな表
面吸収を示し露光後もほとんど向上しないため、光がレ
ジスト底部まで到達せず良好なパターンは得られない。Conventional technology In recent years, with the high density integration of semiconductor devices, the wavelength used by exposure equipment used for microfabrication, particularly photolithography, has become increasingly shorter, and now KrF (krypton fluoride) excimer lasers (248-4 nm) are used. ) are now being considered. However, as shown in Figure 2, conventional far-UV resists made of naphthoquinonediazide-novolac resins show large surface absorption to excimer lasers and hardly improve after exposure, so the light does not reach the bottom of the resist, resulting in good results. I don't get a pattern.
第３図は従来のレジストを用いたパターン形成方法を示
すもので半導体等の基板１上に従来のし３７、−７
ジスト（例えばＭＰ２４００（シブレイ）５を回転塗付
し１．０μｍのレジスト膜を得る（第３図（ａ））。FIG. 3 shows a pattern forming method using a conventional resist, in which a conventional resist (for example, MP2400 (Sibley) 5) is applied by rotation on a substrate 1 such as a semiconductor to form a 1.0 μm resist film. (Figure 3(a)).
次にＫｒＦエキシマレーザ３をマスク４を介して選択的
にレジスト５を露光する（第３図（ｂ））。そして最後
にアルカリ現像液（２４０１（シブレイ社）：純水＝１
：４）で現像し、露光部を除去し未露光部のパターン６
ａを残す（第３図（Ｃ））。パターン６ａはレジストが
満足すべきものではないため、本来破線６の様にパター
ンが形成されるべきものが、膜べ９が生じ形状も三角形
状の望ましくないものとなる。こうした事は要求される
パターン線幅が１μｍ以下の際、特に顕著で問題となる
。Next, the resist 5 is selectively exposed to light using a KrF excimer laser 3 through a mask 4 (FIG. 3(b)). And finally, alkaline developer (2401 (Sibley): pure water = 1
:Developed in step 4), removed the exposed area, and created pattern 6 of the unexposed area.
a (Fig. 3 (C)). Since the resist of the pattern 6a is not satisfactory, the pattern that should originally be formed as shown by the broken line 6 becomes an undesirable triangular shape due to the formation of a film plate 9. This is particularly noticeable and becomes a problem when the required pattern line width is 1 μm or less.
発明が解決しようとする課題
今までＫｒＦエキシマレーザ露光に対し大きな透された
。この結合を有する感光性化合物はＫｒＦエキシマレー
ザ露光により、ジアゾ基が脱離し、それに伴い分子内転
位反応、もしくは主鎖のＣ−Ｃ結合の切断反応が起とジ
ケトンを生成する。ケトン基はパターン形成材料中又は
アルカリ現像液中結合を有する感光性化合物は、露光部
が現像液に溶解するポジ型となる。ポジ型の感光性化合
物は、露光部の溶解速度を向上させる働きとともに未露
光部を現像液に溶解させない働きが必要である。Problems to be Solved by the Invention Until now, there has been a great deal of inconvenience regarding KrF excimer laser exposure. When a photosensitive compound having this bond is exposed to a KrF excimer laser, the diazo group is eliminated, and an intramolecular rearrangement reaction or a cleavage reaction of the C--C bond in the main chain occurs to generate a diketone. A photosensitive compound having a ketone group bonded in a pattern forming material or in an alkaline developer becomes a positive type in which the exposed area dissolves in the developer. The positive-type photosensitive compound must have the function of improving the dissolution rate of the exposed area and the function of preventing the unexposed area from dissolving in the developer.
未露光部の溶解速度を低下させる官能基として分子内に
少くとも１つ以上−５ｏ２ｃ４基、−８ｏ３Ｈ基、−８
Ｏ３ＣＨｓ基を有する感光性化合物が提案された。At least one -5o2c4 group, -8o3H group, -8 in the molecule as a functional group that reduces the dissolution rate of the unexposed area.
Photosensitive compounds with O3CHs groups have been proposed.
上記の官能基は、樹脂の一〇Ｈ基とエステル結合し溶解
性を低下させる働きがあるが、不安定な基であるため、
ジアゾ基とともに分子内に存在させる事が難しい。そこ
で、−８０２０１、−８Ｏ３Ｈ１ｓｏ ３０）（５基は
ベンゼン環に付加する型で感光性化合物内に導入される
。しかしベンゼン環はとりｎｍ に吸収ピークを有する
為、感光性化合物は光退色性が低下する。すなわち、光
退色性、未露光５・・−７
部の溶解速度低下、感光性、合成の容易性のすべてを満
足するポジ型感光性化合物が望まれている現状にある。The above functional group has the function of ester bonding with the 10H group of the resin and lowering the solubility, but since it is an unstable group,
It is difficult to make it exist in the molecule together with the diazo group. Therefore, -80201, -8O3H1so 30) (5 groups are introduced into the photosensitive compound in the form of addition to the benzene ring. However, since the benzene ring has an absorption peak at nm, the photosensitive compound is not photobleachable. In other words, there is currently a need for a positive-working photosensitive compound that satisfies all of the following: photobleaching, dissolution rate reduction of 5 to -7 parts unexposed, photosensitivity, and ease of synthesis.
課題を解決するための手段
本発明は、上記問題点を解決する為に、分子内に少くと
も１つ以上＋ＣＨ２−）ｎ（ｎは６〜２ｏの整数）を有
するポジ型感光性化合物（好ましくはその末端に一５ｏ
２ｒ４ 、−８Ｏ５Ｈ、−５ｏ５ｃＨｓ基を有する）と
樹脂および前記両者を溶解可能な溶媒よりなるポジ型パ
ターン形成材料を提供するものである。Means for Solving the Problems In order to solve the above problems, the present invention provides a positive photosensitive compound (preferably is 15o at its end
2r4, -8O5H, -5o5cHs groups), a resin, and a solvent capable of dissolving both.
作用
分子内のアルキル鎖を長くする事によって、感光性化合
物自体がアルカリ現像液に対する溶解性が低くなる。そ
のためこれを用いたポジ型パターン形成材料の未露光部
はアルカリ現像液に対する溶解速度が低下し、露光部と
の溶解速度に大きな差が生じるため良好なレジストパタ
ーンを得る事ができる。By lengthening the alkyl chain within the working molecule, the photosensitive compound itself becomes less soluble in alkaline developers. Therefore, the dissolution rate of the unexposed areas of the positive pattern forming material using this material in the alkaline developer is reduced, and a large difference occurs in the dissolution rate with the exposed areas, so that a good resist pattern can be obtained.
しかし、通常パターン形成材料には水溶性樹脂６ノ＼／
例えばノボラック樹脂、水系溶媒例えばエチルセルンル
ブアセテートを用いる事が多い。感光性化合物のアルカ
リ可溶性を低下させると、溶媒への溶解度も低下し、十
分な感光性、溶解制御性を有するほど溶媒に溶解できな
くなる。本発明者らの検討の結果特に、ｎが５から２０
までの化合物は、溶媒への溶解性、アルカリ現像液への
溶解制御性。However, water-soluble resins such as novolac resins and water-based solvents such as ethylcerene rubber acetate are usually used as pattern forming materials. When the alkali solubility of a photosensitive compound is reduced, its solubility in a solvent is also reduced, and the compound cannot be dissolved in a solvent enough to have sufficient photosensitivity and dissolution controllability. As a result of the inventors' studies, in particular, n is 5 to 20.
The compounds listed above have solubility in solvents and controllable dissolution in alkaline developing solutions.
感光性ともに良好である事が判明した。It was found that both photosensitivity was good.
本発明のレジストにおいて感光性化合物の末端に一８０
２Ｇｌｌ、または−３Ｏ３Ｈ、−８Ｏ５ＣＨ５等の官能
基を有するものは、樹脂のアルカリ可溶部である一ＯＨ
基とエステル結合等をおこし、樹脂のアルカリ可溶性を
よシー層抑える事ができる。特に分子内に上記官能基を
２個以上有するものは、上記エステル反応が１分子中２
カ所以上で発生し、架橋反応が進行し分子量増大をもた
らすため、樹脂の溶解性をさらに一層抑制させることが
できる。In the resist of the present invention, at the end of the photosensitive compound,
Those having functional groups such as 2Gll, -3O3H, -8O5CH5, etc. are 1OH, which is the alkali-soluble part of the resin.
By forming ester bonds with groups, it is possible to suppress the alkali solubility of the resin. In particular, when the molecule has two or more of the above-mentioned functional groups, the above-mentioned ester reaction is
The solubility of the resin can be further suppressed because the crosslinking reaction proceeds and increases the molecular weight.
なお本発明に用いられる感光性化合物において５ｏ２ｃ
β、または−３Ｏ３Ｈ、−８ｏ３ＣＩ（３等の官能基は
ベンゼン環、ナフタレン環のいずれの位置にあってもよ
く、いずれの場合も感光剤としての効果に相違はない。In addition, in the photosensitive compound used in the present invention, 5o2c
The functional groups such as β, -3O3H, -8o3CI (3, etc.) may be located at either the benzene ring or the naphthalene ring, and there is no difference in the effect as a photosensitizer in either case.
また良好なパターンを得るには２４８．４ ｎｍにおけ
る吸収強度がｄθｅｐ ＵＶ露光により大きな差を生じ
ることが必要不可欠である。Furthermore, in order to obtain a good pattern, it is essential that the absorption intensity at 248.4 nm has a large difference due to dθep UV exposure.
本発明のレジストに用いる感光性化合物において、−Ｃ
Ｈ３、−ｃＨ，、ａＨ，、５Ｏ２Ｇ１等の水素原子以外
の置換基をベンゼン環に付加したものや、これに替えて
ナフタレン環を使用したものや、上記置換基をナフタレ
ン環に付加したものは、通常２５Ｏｎｍ 付近にピーク
をもつベンゼン環の吸収全２０〜フＱｎ
２４８、４ｎｍにおける透過率を露光前後ともに１０〜
３０％向上させた。In the photosensitive compound used in the resist of the present invention, -C
Those in which substituents other than hydrogen atoms such as H3, -cH,, aH,, 5O2G1, etc. are added to the benzene ring, those in which a naphthalene ring is used in place of this, and those in which the above substituents are added to the naphthalene ring are , the total absorption of the benzene ring, which usually has a peak around 25 Onm, is 248. The transmittance at 4 nm is 10 -
Improved by 30%.
なお−０Ｈ３ 、 −ＣＨ２ＣＨ， 、 ５Ｏ２Ｇ１等
の置換基はベンゼン環中のいずれの位置でもよく、いず
れの場合も透過率が向上する事を発明者らは確認してい
る。Note that the substituents such as -0H3, -CH2CH, and 5O2G1 may be placed at any position in the benzene ring, and the inventors have confirmed that the transmittance improves in any case.
実施例
以下に実施例を用いて本発明を更に詳細に説明するが一
本発明はとれらにより同等制限を受けるものではない。EXAMPLES The present invention will be explained in more detail using examples below, but the present invention is not equally limited by these examples.
（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。(Example 1) A reagent was prepared with the following composition and used as a pattern forming material.
Ｎ２ ０
ＣＨ３そＣＨ２→５ｃｍｃ−ｃ ＋ＧＨ２→−５ＣＨ３
・・・・・・２ｇスチレンとマレイン酸のハーフエ
ステル樹脂 ・・・・・・８，！９ジエチレングリコ
ールジメチルエーテル ・・・・・・・・・３０ｇ第１
図を用いて本発明に係る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。半導体基板等の基板１上に上
記組成で溶解されたパターン形成材料２を回転塗布し、
１．Ｑ／１ｍのレジスト膜を得る（第１図（ａ））。な
お基板１上には酸化膜。N2 0 CH3 so CH2→5cmc-c +GH2→-5CH3
...2g styrene and maleic acid half ester resin ...8,! 9 Diethylene glycol dimethyl ether 30g 1st
A pattern forming method using the pattern forming material according to the present invention will be explained with reference to the drawings. Spinning a pattern forming material 2 dissolved in the above composition onto a substrate 1 such as a semiconductor substrate,
1. A resist film of Q/1m is obtained (FIG. 1(a)). Note that there is an oxide film on the substrate 1.
絶縁膜，導電膜等が形成されている場合が多い。Insulating films, conductive films, etc. are often formed.
次に２４８４ｎｍのエキシマレーザ光３でマスク４を介
して選択的にパルス露光を行なう（第１図（ｂ））。Next, selective pulse exposure is performed using a 2484 nm excimer laser beam 3 through a mask 4 (FIG. 1(b)).
そして最後に通常のアルカリ現像液を用いて現像を行な
うことにより、パターン形成材料２の光露光部のみを溶
解除去してレジストパターン２ａを得た（第１図（Ｃ）
）。なおこのときレジストパターン２ａはアスペクト比
が９０度の好形状で、膜べ９も１ｏ％以下のサブミクロ
ンパターンでアッタ。Finally, by performing development using an ordinary alkaline developer, only the light-exposed areas of the pattern forming material 2 were dissolved and removed, resulting in a resist pattern 2a (Fig. 1(C)).
). At this time, the resist pattern 2a has a good shape with an aspect ratio of 90 degrees, and the film plate 9 also has an atta of a submicron pattern of 10% or less.
（実施例２）
下記の組成で試薬を調製しパターン形成材料を作成し、
実施例１と同様の実験を行った。(Example 2) A reagent was prepared with the following composition to create a pattern forming material,
An experiment similar to Example 1 was conducted.
Ｎ２０
ａＨ６（−ｃＨ→…Ｃ−Ｃ−Ｃ（−ＯＨ→πＣＨ３・・
２ｇ前記のスチレンとマレイン酸のハーフエステル樹脂
・・・８ｇジエチレングリコールジメチルエーテル ・
・・・・・３０ｇその結果、実施例１と同様の良好な結
果が得られた。N20 aH6(-cH→...C-C-C(-OH→πCH3...
2g of the above half ester resin of styrene and maleic acid...8g of diethylene glycol dimethyl ether
...30g As a result, the same good results as in Example 1 were obtained.
（実施例３）
下記の組成で試薬を調製しパターン形成材料を作成し、
実施例１と同様の実験を行った。(Example 3) A reagent was prepared with the following composition to create a pattern forming material,
An experiment similar to Example 1 was conducted.
Ｎ２０
ＣＨ３（−ＯＨ分πｃ−ｃ−ａモＣＨ，、す汀ｃＨ３・
・・２ｇ前記のスチレンとマレイン酸の）・−フエステ
ル樹脂 ・・・８ｇジエチレングリコールジメチルエー
テル ・・・・・・３０ｇ１０７、７
その結果、実施例１と同様の良好な結果が得られた。N20 CH3 (-OH part πc-c-amo CH,, sutiercH3・
2g of the above-mentioned styrene and maleic acid)-phester resin 8g diethylene glycol dimethyl ether 30g 107,7 As a result, the same good results as in Example 1 were obtained.
（実施例４）
下記の組成で試薬を調製しパターン形成材料を作成し、
実施例１と同様の実験を行った。(Example 4) A reagent was prepared with the following composition to create a pattern forming material,
An experiment similar to Example 1 was conducted.
Ｎ２ ０
３０２（Ｊ（−ＧＨ２片ｃ−ｃ−ａ （−０）１２汁５
０２ＣＣ・・・・・・・・２ｇ
前記のスチレンとマレイン酸のノ・−フエステル樹脂・
・・８９ジエチレングリコールジメチルエーテル ・・
・・・・３０ｇその結果、実施例１と同様の良好な結果
が得られた。N2 0 302 (J (-GH2 piece c-c-a (-0) 12 juice 5
02CC・・・・・・2g The above-mentioned styrene and maleic acid nophester resin.
・・89 diethylene glycol dimethyl ether ・・
...30g As a result, the same good results as in Example 1 were obtained.
（実施例５）
下記の組成で試薬を調製しノ（ターン形成材料を・・・
・・・・・２ｇ
前記のスチレンとマレイン酸の）・−フエステル樹脂・
・・８ｇジエチレングリコールジメチルエーテル ・・
・・・・・・・３０ｇその結果、実施例１と同様の良好
な結果が得られ１１１．７
た。(Example 5) A reagent was prepared with the following composition (turn forming material...
...2g of the above styrene and maleic acid) - Phester resin
・・8g diethylene glycol dimethyl ether ・・
...30g As a result, good results similar to those in Example 1 were obtained.
（実施例６） 下記の組成で試薬を調製しパターン形成材料をた。(Example 6) A reagent with the following composition was prepared and a pattern forming material was used.
（実施例８）
下記の組成で試薬を調製しパターン形成材料を・・・・
・・・・・２Ｉ
前記のスチレンとマレイン酸のハーフエステル樹脂・・
・８ｇジエチレングリコールジメチルエーテル ・・・
・・・３０ｇその結果、実施例１と同様の良好な結果が
得られた。(Example 8) Prepare a reagent with the following composition and use it as a pattern forming material...
...2I The above styrene and maleic acid half ester resin...
・8g diethylene glycol dimethyl ether...
...30g As a result, the same good results as in Example 1 were obtained.
（実施例７）
下記の組成で試薬を調製しパターン形成材料を作成し、
実施例１と同様の実験を行った。(Example 7) A reagent was prepared with the following composition to create a pattern forming material,
An experiment similar to Example 1 was conducted.
前記のスチレンとマレイン酸のハーフエステ／４４脂・
・・８１！ｉ！ジエチレングリコールジメチルエーテル
・・・・・・３０ｇその結果、実施例１と同様の良好
な結果が得られた。The above styrene and maleic acid half-esthetic/44 fat.
...81! i! Diethylene glycol dimethyl ether 30g As a result, the same good results as in Example 1 were obtained.
（実施例９）
下記の組成で試薬を調製しパターン形成材料を・・・・
・・・・・２ｇ
前記のスチレンとマレイン酸のハーフエステル樹脂・・
・８ｇジエチレングリコールジメチルエーテル ・・・
・・・３０ｇその結果、実施例１と同様の良好な結果が
得られ・・・・・・・・２ｇ
前記のスチレンとマレイン酸のハーフエステｚ＋４［Ｗ
・・・８ｇジエチレングリコールジメチルエーテル ・
・・・・・３０ｇその結果、実施例１と同様の良好な結
果が得られ１３７、
た。(Example 9) Prepare a reagent with the following composition and use it as a pattern forming material...
...2g The above half ester resin of styrene and maleic acid...
・8g diethylene glycol dimethyl ether...
...30g As a result, the same good results as in Example 1 were obtained...2g The above styrene and maleic acid half ester Z+4[W
...8g diethylene glycol dimethyl ether ・
...30g As a result, good results similar to those in Example 1 were obtained137.
（実施例１０）
下記の組成で試薬を調製しパターン形成材料を作成し、
実施例１と同様の実験を行った。(Example 10) A reagent was prepared with the following composition to create a pattern forming material,
An experiment similar to Example 1 was conducted.
・・・・・・・・・２ｇ
前記のスチレンとマレイン酸のハーフエステ／４４脂・
・・８ｇジエチレングリコールジメチルエーテル ・・
・・−・３０９その結果、実施例１と同様の良好な結果
が得られた。・・・・・・・・・2g The above styrene and maleic acid half-esthetic/44 fat・
・・8g diethylene glycol dimethyl ether ・・
...309 As a result, good results similar to those of Example 1 were obtained.
（実施例１１）
下記の組成で試薬を調製しパターン形成材料を作成し、
実施例１と同様の実験を行った。(Example 11) A reagent was prepared with the following composition to create a pattern forming material,
An experiment similar to Example 1 was conducted.
１４、、−７
ジエチレングリコールジメチルエーテル ・・・・・・
３０ｇその結果、実施例１と同様の良好な結果が得られ
た。14,,-7 Diethylene glycol dimethyl ether...
30g As a result, the same good results as in Example 1 were obtained.
（実施例１２）
下記の組成で試薬を調製しパターン形成材料を作成し、
実施例１と同様の実験を行った。(Example 12) A reagent was prepared with the following composition to create a pattern forming material,
An experiment similar to Example 1 was conducted.
前記のスチレンとマレイン酸のハーフエステｔｖ 樹脂
・・・８ｇジエチレングリコールジメチルエーテル
・・・・・・３０ｇその結果、実施例１と同様の良好
な結果が得られた。The above-mentioned half-ester tv resin of styrene and maleic acid: 8 g Diethylene glycol dimethyl ether: 30 g As a result, the same good results as in Example 1 were obtained.
（実施例１３）
下記の組成で試薬を調製しパターン形成材料を・・・・
・・・・２Ｉ
前記のスチレンとマレイン酸のハーフエステル樹脂・・
８ｇ
前記のスチレンとマレイン酸のノ・−フエステｚ４ｍ・
・・８ｇジエチレングリコールジメチルエーテル ・・
・・・・３０ｇその結果、実施例１と同様の良好な結果
が得られた。(Example 13) Prepare a reagent with the following composition and use it as a pattern forming material...
...2I The above half ester resin of styrene and maleic acid...
8g The above-mentioned styrene and maleic acid No-Feste Z4m
・・8g diethylene glycol dimethyl ether ・・
...30g As a result, the same good results as in Example 1 were obtained.
（実施例１４）
下記の組成で試薬を調製しパターン形成材料を作成し、
実施例１と同様の実験を行った。(Example 14) A reagent was prepared with the following composition to create a pattern forming material,
An experiment similar to Example 1 was conducted.
・・・・・・・・２ｇ
前記のスチレンとマレイン酸のハーフエステ／ｌ／ 樹
脂 ・・・８ｇジエチレングリコールジメチルエーテ
ル ・・・・・・３０ｇその結果、実施例１と同様の良
好な結果が得られた。......2g Half ester of styrene and maleic acid/l/Resin...8g Diethylene glycol dimethyl ether...30g As a result, the same good results as in Example 1 were obtained. Ta.
（実施例１５）
下記の組成で試薬を調製しパターン形成材料を作成し、
実施例１と同様の実験を行った。(Example 15) A reagent was prepared with the following composition to create a pattern forming material,
An experiment similar to Example 1 was conducted.
前記のスチレンとマレイン酸のノ−−エステル樹脂・・
・８ｇジエチレングリコールジメチルエーテル ・・・
・・・３０．９その結果、実施例１と同様の良好な結果
が得られた。The above-mentioned styrene and maleic acid non-ester resin...
・8g diethylene glycol dimethyl ether...
...30.9 As a result, good results similar to those of Example 1 were obtained.
（実施例１６）
下記の組成で試薬を調製しパターン形成材料を作成し、
実施例１と同様の実験を行った。(Example 16) A reagent was prepared with the following composition to create a pattern forming material,
An experiment similar to Example 1 was conducted.
前記のスチレンとマレイン酸のノ・−７エステル樹脂
・・８ｇジエチレングリコールジメチルエーテル ・
・・・・・３０ｇその結果、実施例１と同様の良好な結
果が得られた。The above-mentioned styrene and maleic acid 7-ester resin
・・8g diethylene glycol dimethyl ether ・
...30g As a result, the same good results as in Example 1 were obtained.
（実施例１７）
下記の組成で試薬を調製しパターン形成材料を前記のス
チレンとマレイン酸のノー−７エステル樹脂 ・・・８
ｇジエチレングリコールジメチルエーテル ・・・・・
・３０ｇその結果、実施例１と同様の良好な結果が得ら
れた。(Example 17) A reagent was prepared with the following composition, and the pattern forming material was the above-mentioned No-7 ester resin of styrene and maleic acid...8
g Diethylene glycol dimethyl ether...
・30g As a result, the same good results as in Example 1 were obtained.
（実施例１８）
下記の組成で試薬を調製しパターン形成材料を・・・・
・・・・２ｇ
前記のスチレンとマレイン酸のハーフエステ／Ｖ 樹Ｑ
Ｗ ・・・８ｇジエチレングリコールジメチルエーテ
ル ・・・・・・３０ｇその結果、実施例１と同様の良
好な結果が得られた。(Example 18) Prepare a reagent with the following composition and use it as a pattern forming material...
...2g The above styrene and maleic acid half-esthetic/V Tree Q
W: 8g Diethylene glycol dimethyl ether: 30g As a result, the same good results as in Example 1 were obtained.
（実施例１９）
下記の組成で試薬を調製しパターン形成材料を作成し、
実施例１と同様の実験を行った。(Example 19) A reagent was prepared with the following composition to create a pattern forming material,
An experiment similar to Example 1 was conducted.
Ｎ２０
ｓｏｘＨ＋ＧＨｚ前ｃ−ｃ−ｃ （−ｃＨ２珊５Ｏ３Ｈ
・・・２ｇ前記のスチレンとマレイン酸の７・−７エス
テｔｖ４ｔｄ脂 ・・・８ｇジエチレングリコールジ
メチルエーテル ・・・・・・３ｏｇ１８、、
その結果、実施例１と同様の良好な結果が得られた。N20 soxH+GHz c-c-c (-cH2san5O3H
...2g of the above-mentioned 7-7 ester tv4td fat of styrene and maleic acid ...8g diethylene glycol dimethyl ether ...3og18 As a result, the same good results as in Example 1 were obtained.
紫外線で光反応し、アルカリ現像液に対する溶解速度を
早めるものであればこの限りではない。また樹脂につい
ても、スチレンとマレイン酸のハーフエステル樹脂を用
いたが、アルカリ可溶性であればノボラック樹脂、ポリ
ビニルフェノール樹脂。This is not the case as long as it photoreacts with ultraviolet rays and accelerates its dissolution rate in an alkaline developer. Regarding the resin, we used a half ester resin of styrene and maleic acid, but if it is alkali-soluble, we can use novolac resin or polyvinylphenol resin.
セルロース樹脂、スチレン系の樹脂等でもよく、またこ
れらに限定されるものではない。溶媒についても同様で
、本実施例においては、遠紫外領域で高い透過率を有す
るジエチレングリコールジメチルエーテルを用いたが、
エチルセロンルブアセテート、メチルセロンルブアセテ
ート等を使用しても同等問題はなかった。Cellulose resin, styrene resin, etc. may be used, and the material is not limited to these. The same goes for the solvent; in this example, diethylene glycol dimethyl ether, which has high transmittance in the deep ultraviolet region, was used.
There was no similar problem even when using ethylseron rub acetate, methyl seron rub acetate, etc.
発明の効果
本発明は例えば２４８ 、４ ｎｍのＫｒＦエキシマレ
ーザ光などに対して優れた反応性を有する新規なし１９
、＼−／
シストを提供するものであり、例えばＫｒＦエキシマレ
ーザ光（２４８４ｎｍ ）などの遠紫外線（ｄｅｅｐＵ
Ｖ ）露光用レジストやＯＥＭ等に応用した場合にはサ
ブミクロンオーダの形状の良い微細パターンが容易に得
られるので、半導体産業に於ける超微細パターン形成に
とって価値大なものである。Effects of the Invention The present invention is novel and has excellent reactivity to, for example, 248 and 4 nm KrF excimer laser light.
, \-/ For example, deep ultraviolet (deep U) such as KrF excimer laser light (2484 nm)
V) When applied to exposure resists, OEM, etc., it is easy to obtain fine patterns with good shapes on the order of submicrons, so it is of great value for forming ultra-fine patterns in the semiconductor industry.
第１図は本発明の一実施例のパターン形成材料を用いた
パターン形成方法の工程断面図、第２図は従来のパター
ン形成材料の紫外線分光曲線図、第３図は従来のパター
ン形成材料を用いたパターン形成方法の工程断面図であ
る。
１・・・・・・基板、２・・・・・・本発明のパターン
形成材料、３・・・・・・ＫｒＦエキシマレーザ、４・
・・・・・マスク、６・・・・・従来のパターン形成材
料、２ａ・・・・・・本発明のパターン形成材料パター
ン。Fig. 1 is a process cross-sectional view of a pattern forming method using a pattern forming material according to an embodiment of the present invention, Fig. 2 is an ultraviolet spectral curve diagram of a conventional pattern forming material, and Fig. 3 is a process cross-sectional view of a pattern forming method using a pattern forming material according to an embodiment of the present invention. It is a process sectional view of the pattern formation method used. DESCRIPTION OF SYMBOLS 1...Substrate, 2...Pattern forming material of the present invention, 3...KrF excimer laser, 4...
... Mask, 6 ... Conventional pattern forming material, 2a ... Pattern forming material pattern of the present invention.
Claims (3)
があります▼（ｎは５〜２０の整数）で示される基を有
し遠紫外線に反応するポジ型感光性化合物とベース樹脂
、および前記化合物と樹脂を溶解可能な溶媒よりなるポ
ジ型パターン形成材料。(1) Positive photosensitive compound and base resin that have at least one group in the molecule ▲ Contains a mathematical formula, chemical formula, table, etc. ▼ (n is an integer from 5 to 20) and reacts to deep ultraviolet rays. , and a positive pattern forming material comprising a solvent capable of dissolving the compound and the resin.
とする特許請求の範囲第１項に記載のポジ型パターン形
成材料。 ▲数式、化学式、表等があります▼〔式中、Ｘは−ＳＯ
＿２Ｃｌ、−ＳＯ＿３Ｈ、−ＳＯ＿３ＣＨ＿３基を含む
（但し−ＳＯ＿２Ｃｌはその第４級塩を含み、−ＳＯ＿
３Ｈはそのアンモニウム塩の基、有機塩基の塩及び第４
級塩を含む）〕。(2) The positive pattern forming material according to claim 1, wherein the positive photosensitive compound has the following group. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X is -SO
Contains _2Cl, -SO_3H, -SO_3CH_3 groups (however, -SO_2Cl includes its quaternary salt, and -SO_
3H is the group of its ammonium salt, the salt of organic base and the quaternary
(including grade salt)].
▲数式、化学式、表等があります▼結合を有する事を特
徴とす る特許請求の範囲第１項又は第２項に記載のポジ型パタ
ーン形成材料。(3) The positive photosensitive compound according to claim 1 or 2, wherein the positive photosensitive compound has at least one ▲ mathematical formula, chemical formula, table, etc. ▼ bond in the molecule. Mold pattern forming material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27342888A JPH02118649A (en) | 1988-10-28 | 1988-10-28 | Positive pattern forming material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27342888A JPH02118649A (en) | 1988-10-28 | 1988-10-28 | Positive pattern forming material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02118649A true JPH02118649A (en) | 1990-05-02 |
Family
ID=17527765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27342888A Pending JPH02118649A (en) | 1988-10-28 | 1988-10-28 | Positive pattern forming material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02118649A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001144054A (en) * | 1999-09-29 | 2001-05-25 | Applied Materials Inc | Pad cleaning brush for chemical mechanical polishing apparatus and method of manufacturing same |
| JP2007216262A (en) * | 2006-02-16 | 2007-08-30 | Nippon Steel Corp | Device and method for attaching/detaching in-mold electromagnetic stirring device |
-
1988
- 1988-10-28 JP JP27342888A patent/JPH02118649A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001144054A (en) * | 1999-09-29 | 2001-05-25 | Applied Materials Inc | Pad cleaning brush for chemical mechanical polishing apparatus and method of manufacturing same |
| JP2007216262A (en) * | 2006-02-16 | 2007-08-30 | Nippon Steel Corp | Device and method for attaching/detaching in-mold electromagnetic stirring device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100583095B1 (en) | Photoresist composition containing photo radical generator with photo acid generator | |
| JP2770740B2 (en) | Sulfonium salt compound having bridged cyclic alkyl group and photoacid generator | |
| US5364734A (en) | Postive-working radiation-sensitive mixture and radiation-sensitive recording material produced therewith | |
| JPH0210350A (en) | Positive type photoresist | |
| KR100354284B1 (en) | Sulfonium Salt Compound, Photoresist Composition and Method for Patterning by Employing Same | |
| US6849384B2 (en) | Photoacid generators, photoresist compositions containing the same and pattering method with the use of the compositions | |
| JP2001294570A (en) | Sulfonium slat, photoresist composition, method for forming pattern using the same | |
| US6060212A (en) | 193 nm positive-working photoresist composition | |
| JPH04199152A (en) | Photosensitive composition | |
| JP2615742B2 (en) | Resist using photosensitive compound | |
| JP2964990B2 (en) | Photosensitive resin composition containing photoacid generator having cross-linked cyclic alkyl group, and pattern forming method using the same | |
| JPH02118649A (en) | Positive pattern forming material | |
| JPH07117752B2 (en) | Photosensitive resin composition | |
| JPH01154048A (en) | Photosensitive composition | |
| JPH0792675A (en) | Photosensitive compound and photosensitive composition | |
| JPH02118651A (en) | Pattern forming material | |
| Hayashi et al. | Negative resist for i-line lithography utilizing acid catalyzed silanol-condensation reaction | |
| JPH0210355A (en) | Pattern forming material | |
| JPH0261640A (en) | Photosensitive composition | |
| JP2849666B2 (en) | New resist material | |
| JPH02118648A (en) | Positive pattern forming material | |
| JPH02118655A (en) | Contrast enhancing material to be used for forming pattern | |
| JPH01140143A (en) | Pattern forming material | |
| JPH01106037A (en) | Pattern forming material | |
| JPH02106751A (en) | Pattern forming material |