JPH0193736A - Photosensitive composition - Google Patents
Photosensitive compositionInfo
- Publication number
- JPH0193736A JPH0193736A JP25139587A JP25139587A JPH0193736A JP H0193736 A JPH0193736 A JP H0193736A JP 25139587 A JP25139587 A JP 25139587A JP 25139587 A JP25139587 A JP 25139587A JP H0193736 A JPH0193736 A JP H0193736A
- Authority
- JP
- Japan
- Prior art keywords
- group
- photosensitive composition
- formulas
- present
- silicone polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims description 21
- -1 each of R3-R8 is H Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000003504 photosensitizing agent Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- 238000001312 dry etching Methods 0.000 abstract description 12
- 229920005573 silicon-containing polymer Polymers 0.000 abstract description 10
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 abstract 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 abstract 1
- 150000005691 triesters Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000005530 etching Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 230000003746 surface roughness Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は感光性組成物に関し、更に詳しくは、酸素を用
いたプラズマエツチングに対して高い工ッチング耐性を
有し、従ってレジスト材料として用いるのに好適な感光
性組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photosensitive composition, and more particularly, it has a high etching resistance to plasma etching using oxygen and is therefore suitable for use as a resist material. The present invention relates to a photosensitive composition suitable for.
本発明の感光性組成物は、特定のシリコン系重合体と特
定の感光剤とを組み合わせることにより、良好な解像性
及び良好な耐ドライエツチング性をバランス良く具備す
ることができるようにしたものである。The photosensitive composition of the present invention is capable of providing good resolution and good dry etching resistance in a well-balanced manner by combining a specific silicone polymer and a specific photosensitizer. It is.
近年、集積回路、バブルメモリ素子等の製造において、
パターンの微細化に伴いレジストパターンを精度よく基
板に転写するため、従来のウェットエツチングに変わっ
てガスプラズマ、イオンシャワー等を用いたドライエツ
チングが主流となりつつある。In recent years, in the production of integrated circuits, bubble memory devices, etc.
As patterns become finer, dry etching using gas plasma, ion shower, etc. is becoming mainstream in place of conventional wet etching in order to accurately transfer resist patterns onto substrates.
従来、耐ドライエツチング性を有するレジスト材料とし
てシリコン含有組成物がいくつか提案されている。Conventionally, several silicon-containing compositions have been proposed as resist materials having dry etching resistance.
特開昭６０−１９６７５０号公報には、無機元素を含ま
ない有機高分子化合物と比較して、酸素プラズマエツチ
ング等に対して高いエツチング耐性を有するケイ素含有
スチレン系重合体が記載されている。JP-A-60-196750 describes a silicon-containing styrenic polymer that has higher etching resistance to oxygen plasma etching, etc., than organic polymer compounds that do not contain inorganic elements.
また、特開昭６０−１１９５５０号公報には、半導体素
子等の製造に利用して有用なポリシラン系のパターン形
成材料が記載されている。Furthermore, Japanese Patent Application Laid-open No. 119550/1983 describes a polysilane-based pattern forming material useful for manufacturing semiconductor devices and the like.
さらに、特開昭５９−２０８５４２号公報には、半導体
集積回路等の製造に適用されて微細なパターンを形成す
るケイ素原子含有重合体が記載されている。Further, JP-A-59-208542 describes a silicon atom-containing polymer that is applied to the manufacture of semiconductor integrated circuits and the like to form fine patterns.
しかし、これらのレジスト材料はいずれも電子線対応レ
ジストであり、現在汎用されつつある露光装置のｇ線ス
テッパー（波長：４３６ｎｍ）には使用不能という問題
点があった。However, all of these resist materials are resists compatible with electron beams, and there is a problem in that they cannot be used in the G-line stepper (wavelength: 436 nm) of exposure equipment that is currently being used widely.
一方、このｇ線に吸収波長を有するシリコン系レジスト
として三洋化成社によりポリアセチレン系のポジ型レジ
ストが発表されている。しがし、このレジストは現像が
有機溶媒によるものであり、解像度及び感度が未だ十分
とは言えず、実用性に乏しいという問題点があった。On the other hand, a polyacetylene-based positive resist has been announced by Sanyo Kasei Co., Ltd. as a silicon-based resist having an absorption wavelength in the g-line. However, this resist is developed using an organic solvent, and its resolution and sensitivity are still insufficient, resulting in a problem in that it is impractical.
本発明の目的は、上記した問題点の解消にあり、良好な
解像性及び良好な耐ドライエツチング性をバランス良（
具備する感光性組成物を提供することにある。The purpose of the present invention is to solve the above-mentioned problems, and to achieve a good balance between good resolution and dry etching resistance.
An object of the present invention is to provide a photosensitive composition comprising:
本発明の感光性組成物は、
（Ａ）−膜化：
（両式中、Ｒ，及びＲ２は、それぞれ、同一でも異なっ
てもよく、低級アルキレン基を表し、Ｒ３乃至Ｒ８は、
それぞれ、同一でも異なってもよく、水素原子、水酸基
、メチル基またはメチロール基を表し、Ｒ７乃至ＲＩ２
は、それぞれ、同一でも異なってもよく、低級アルキル
基を表し、Ｒ１３は、ＣＨ，又はＣＨ２０Ｃ）！！を表
わし、Ｅは、フェノール、１〜３の置換基を有するフェ
ノール誘導体又はＨ
（Ｒ１，は、低級アルキレン基を表わし、Ｒ１５％ Ｒ
Ｉ６及びＲ４は、低級アルキル基を表わす）を表わし、
ＸはＯくＸ≦１の範囲の数であり、Ｙは１−Ｘの数であ
る）
で示される単位の少くとも一方を有するシリコン系重合
体
（Ｂ）ｌ、２−ナフトキノンジアジド−５−スルホン酸
のトリ及びテトラエステル化合物からなる群より選択さ
れる少なくとも１種の感光剤からなることを特徴とする
ものである。The photosensitive composition of the present invention has the following characteristics: (A) - Film formation: (In both formulas, R and R2 may be the same or different, and represent a lower alkylene group, and R3 to R8 are
Each may be the same or different and represents a hydrogen atom, a hydroxyl group, a methyl group, or a methylol group, and R7 to RI2
may be the same or different and each represents a lower alkyl group, and R13 is CH, or CH20C)! ! , E represents phenol, a phenol derivative having 1 to 3 substituents, or H (R1, represents a lower alkylene group, R15% R
I6 and R4 represent a lower alkyl group),
(X is a number in the range of O x ≦ 1, Y is a number in the range of 1-X) (B) 1,2-naphthoquinonediazide-5- It is characterized by comprising at least one photosensitizer selected from the group consisting of tri- and tetraester compounds of sulfonic acid.
本発明に使用されるシリコン系重合体は、前記した一般
式で示される重合体である。ここで、ＲいＲ２及びＲ１
４は、炭素数１〜５のアルキレン基であるのが好ましく
、これは、エチレン基、プロピレン基、ブチレン基、ア
ミジノ基等を意味する。またＲ７乃至Ｒ１□とＬｓ乃至
Ｒ１？は、炭素数１〜７のアルキル基であるのが好まし
く、これは、メチル基、エチル基、プロピル基、ブチル
基、イソブチル基、ｔｅｒ ｔ−ブチル基、ペンチル基
等を意味する。The silicone polymer used in the present invention is a polymer represented by the general formula described above. Here, R2 and R1
4 is preferably an alkylene group having 1 to 5 carbon atoms, which means an ethylene group, a propylene group, a butylene group, an amidino group, and the like. Also, R7 to R1□ and Ls to R1? is preferably an alkyl group having 1 to 7 carbon atoms, which means a methyl group, ethyl group, propyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, etc.
またフェノール誘導体とは、ｏ−ｌｍ−及びｐ−クレゾ
ール、キシレノール、レゾルシノール等を意味する。さ
らに、ＸとＹとの比率は任意であるが、有機アルカリ水
溶液への現像性を考慮すると、Ｙは０．７以下が好まし
い。またこの重合体の分子量は、重量平年分子量（ＭＷ
）で、通常、３．０００〜３０．０００であるのが好ま
しい、何故ならば、ｈが３．０００未満ではエツチング
後の表面荒れや現像時の膨潤を招き易＜ 、３０．００
０を超えると感度の低下が比較的大きくなるからであり
、更に好ましくは、３．０００〜１０．０００である。Moreover, the phenol derivative means o-lm- and p-cresol, xylenol, resorcinol, and the like. Furthermore, although the ratio of X and Y is arbitrary, in consideration of developability in an organic alkali aqueous solution, Y is preferably 0.7 or less. In addition, the molecular weight of this polymer is the weight average molecular weight (MW
), and is usually preferably 3.000 to 30.000, because if h is less than 3.000, surface roughness after etching and swelling during development are likely to occur.<, 30.00
This is because if it exceeds 0, the decrease in sensitivity will be relatively large, and more preferably it is 3.000 to 10.000.
このシリコン系重合体の詳細は特願昭６１−１８９８２
１号明細書に記載されているため、参照されたい。なお
、このシリコン系重合体の一製造例を示す。Details of this silicone polymer can be found in Japanese Patent Application No. 61-18982.
Since it is described in the specification of No. 1, please refer to it. An example of the production of this silicone polymer will be shown below.
で示される化合物４０ｇをホルマリン（３７％水溶液）
９．４ｇ、エチルセロソルブアセテート４４ｇ及びシュ
ウ酸二水和物２００■と同時に投入し、１２０℃で５．
５時間加熱、攪拌し重合させる。次に、水−メタノール
（１： １）中に再沈澱させ、未反応の化合物を除去し
、減圧、乾燥することによって、上記（Ａ）項に記載し
た２つの一般式のうちの前者のシリコン系重合体（Ｉ）
が得られる。40g of the compound shown in formalin (37% aqueous solution)
9.4 g of ethyl cellosolve acetate, 44 g of ethyl cellosolve acetate, and 200 g of oxalic acid dihydrate were added at the same time, and heated to 120°C for 5.
Heat and stir for 5 hours to polymerize. Next, by reprecipitating in water-methanol (1:1), removing unreacted compounds, and drying under reduced pressure, the silicon of the former of the two general formulas described in item (A) above is obtained. System polymer (I)
is obtained.
得られた重合体（Ｉ）のｈは５，３００ （ゲルパー−
ミエーションクロマトグラフ法により測定した）であり
、分散度はＭｗ／Ｍｎで２．６５であった。ただし、Ｍ
ｎは数平均分子量を表し、分散度は単分散ポリスチレン
を標準とした。The h of the obtained polymer (I) is 5,300 (Gelper
), and the degree of dispersion was Mw/Mn of 2.65. However, M
n represents the number average molecular weight, and the degree of dispersion is based on monodisperse polystyrene.
さらに、上記−製造例において、重合反応をアリカリ性
媒体中で行なうと、上記（Ａ）項に記載した２つの一般
式のうちの後者のシリコン系重合体（ｎ）が得られた。Furthermore, in the above-mentioned production example, when the polymerization reaction was carried out in an alkaline medium, a silicon-based polymer (n) of the latter of the two general formulas described in section (A) above was obtained.
本発明に使用される感光剤は、１．２−ナフトキノンジ
アジド−５−スルホン酸のトリ及びテトラエステル化合
物からなる群から選択される少なくとも１種のものであ
る。この感光剤の具体例としては、２，３．４−）リヒ
ドロキシベンゾフェノンと１．２−ナフトキノンジアジ
ド−５−スルホン酸のトリエステル化合物、あるいは２
，３゜４．２’、３”、４”−ヘキサヒドロキシジフェ
ニルプロパンと１．２−ナフトキノンジアジド−５−ス
ルホン酸のテトラエステル化合物が挙げられる。The photosensitizer used in the present invention is at least one selected from the group consisting of tri- and tetraester compounds of 1,2-naphthoquinonediazide-5-sulfonic acid. Specific examples of this photosensitizer include a triester compound of 2,3,4-)lyhydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid;
, 3° 4.2', 3'', 4''-hexahydroxydiphenylpropane and a tetraester compound of 1,2-naphthoquinonediazide-5-sulfonic acid.
この感光剤の配合割合はシリコン系重合体１００重量部
に対し、通常、１５〜３５重量部であるのが好ましい。The blending ratio of the photosensitizer is generally preferably 15 to 35 parts by weight per 100 parts by weight of the silicone polymer.
この配合割合が１５重量部未満では十分な感度が得られ
にくく、３５重量部を超えると解像性及び耐ドライエツ
チング性が成る程度低下してしまう。If the blending ratio is less than 15 parts by weight, it is difficult to obtain sufficient sensitivity, and if it exceeds 35 parts by weight, the resolution and dry etching resistance will deteriorate to a certain degree.
本発明の感光性組成物は、さらに必要に応じて、本発明
の効果を損なわない限り、種々の添加剤が配合されても
よい。The photosensitive composition of the present invention may further contain various additives, as necessary, as long as they do not impair the effects of the present invention.
本発明の感光性組成物は、前記（Ａ）項及び（Ｂ）項に
記載した成分に、さらに他の添加剤を適宜に加え、これ
らを所定量、混合攪拌して常法により容易に製造するこ
とができる。The photosensitive composition of the present invention can be easily produced by a conventional method by adding other additives to the components described in (A) and (B) above, and mixing and stirring a predetermined amount of these. can do.
本発明の感光性組成物は、良好な解像性及び良好な耐ド
ライエツチング性をバランス良く具備するものであるた
め、例えば２層構造レジストの上層レジストとして極め
て有用であり、その他にも半導体素子の製造分野に広く
適用可能なものである。The photosensitive composition of the present invention has good resolution and good dry etching resistance in a well-balanced manner, so it is extremely useful, for example, as an upper layer resist of a two-layer structure resist, and is also used for semiconductor devices. It is widely applicable to the manufacturing field.
以下に、実施例を掲げ、本発明を更に詳しく説明する。EXAMPLES Below, the present invention will be explained in more detail with reference to Examples.
実施例１
前述の一製造例により得られたシリコン系重合体（Ｉ）
Ｉｇ及び２．３．４−トリヒドロキシベンゾフェノンと
１．２−ナフトキノンジアジド−５−スルホン酸とのト
リエステル化合物２００ｍｇをエチルセロソルブアセテ
−）４．６ｇに溶解して混合し、本発明の感光性組成物
を得た。Example 1 Silicone polymer (I) obtained by the above-mentioned production example
Ig and 200 mg of a triester compound of 2.3.4-trihydroxybenzophenone and 1.2-naphthoquinonediazide-5-sulfonic acid were dissolved in 4.6 g of ethyl cellosolve acetate and mixed. A composition was obtained.
シリコンウェハー上に０ＦＰＲ８００（商品名、東京応
化社製）を２μｍスピンコードし、２００度で５分間ホ
ントプレート上でハードベーキングした。ついでその上
に本発明の組成物を２．５０Ｏｒｐｍでスピン塗布し、
９０℃で２０分乾燥して２層レジスト（上層膜厚：０．
５μｍ）を作成した。2 μm of 0FPR800 (trade name, manufactured by Tokyo Ohka Co., Ltd.) was spin-coded on a silicon wafer, and hard baked on a real plate at 200 degrees for 5 minutes. Then, the composition of the present invention is spin-coated thereon at 2.50 rpm,
Dry at 90°C for 20 minutes to form a two-layer resist (upper layer thickness: 0.
5 μm) was created.
縮小投影露光装置（日本光学工業（樽製）で露光後、３
．６％水酸化テトラメチルアンモニウム水溶液で９０秒
間現像した。ｇ線ステッパーの解像限界と言われている
０、５μｍライン／スペースが解像できた。After exposure with a reduction projection exposure device (Nippon Kogaku Kogyo (barrel)),
．． It was developed for 90 seconds with a 6% aqueous tetramethylammonium hydroxide solution. We were able to resolve lines/spaces of 0.5 μm, which is said to be the resolution limit of a g-line stepper.
また、この基板を反応性エツチング装置により１４分間
エツチングした。このときのエツチングレート
０□＊Ｉｋ １００ Ｓ ＣＣＭであった。これにより
０．５μｍライン／スペースのパターンが転写された。Further, this substrate was etched for 14 minutes using a reactive etching device. The etching rate at this time was 0□*Ik 100 S CCM. As a result, a 0.5 μm line/space pattern was transferred.
パターン形状は矩形性が優れ、厚い有機層にパターン転
写を行う際のパターン変換差は観測されなかった。The pattern shape had excellent rectangularity, and no difference in pattern conversion was observed when transferring the pattern to a thick organic layer.
さらにまた、下層の０ＦＰＲ−８００とのエツチングレ
ート比（下層エツチングレート／上層エツチングレート
）は２０倍あり、十分な耐ドライエツチング性を有して
いることが確認された。Furthermore, the etching rate ratio (lower layer etching rate/upper layer etching rate) of the lower layer 0FPR-800 was 20 times, and it was confirmed that the film had sufficient dry etching resistance.
実施例２
前述の一製造例により得られたシリコン系重合体（Ｉ）
Ｉｇ及び２．３．４．２′、３゛、４′−へキサヒドロ
キシジフェニルプロパンと１．２−ナフトキノンジアジ
ド−５−スルホン酸とのテトラエステル化合物２００ｍ
ｇをエチルセロソルブ−エチルセロソルブアセテート（
１： １） ４．６ｇに混合溶解して本発明の感光性
組成物を得た。Example 2 Silicone polymer (I) obtained by the above-mentioned production example
Ig and 2.3.4.2', 3', 4'-hexahydroxydiphenylpropane and 1,2-naphthoquinonediazide-5-sulfonic acid tetraester compound 200m
g to ethyl cellosolve - ethyl cellosolve acetate (
1:1) were mixed and dissolved in 4.6 g to obtain a photosensitive composition of the present invention.
実施例１と同じ露光・現像を行った。ただし、現像時間
は９０秒であった。０．５μｍライン／スペースを解像
することができた。The same exposure and development as in Example 1 was performed. However, the development time was 90 seconds. It was possible to resolve 0.5 μm lines/spaces.
図示された残膜率−エネルギーの関係から求めた感度、
ｒ値、ｇ ’Ｉｔ、’Ａステッパーでの解像度の結果を
次に示す。なお図面において、Ｏは実施例１による感光
性組成物の場合、■は実施例２による感光性組成物の場
合、△は０ＦＰＲ−８００（比較用）の場合をそれぞれ
示す。Sensitivity determined from the relationship between residual film rate and energy shown in the diagram,
r value, g'It,'Resolution results with the A stepper are shown below. In the drawings, O indicates the photosensitive composition according to Example 1, ■ indicates the photosensitive composition according to Example 2, and Δ indicates the case of 0FPR-800 (for comparison).
感度（ｍＪ／ｃｍ”） ｒ値 解像度（μｍ）実
施例１ ５２ ２．６ ０．５実施例２
１９ ２．０ ０．５感度はトリエス
テル化合物を含む組成物（実施例１）よりテトラエステ
ル化合物を含む組成物（実施例２）が２．７倍高く、２
つの実施例は共に市−、ｐｙｉ品より高いｒ値でかつ高
解像度であった。更に、耐ドライエツチング性は２０倍
高かった。以上により、本発明の組成物は良好な解像度
及び良好な耐ドライエツチング性をバランス良く具備す
ることが確認された。Sensitivity (mJ/cm”) r value Resolution (μm) Example 1 52 2.6 0.5 Example 2
19 2.0 0.5 sensitivity was 2.7 times higher for the composition containing a tetraester compound (Example 2) than for the composition containing a triester compound (Example 1);
Both examples had higher r values and higher resolution than the Ichi- and PYI products. Furthermore, the dry etching resistance was 20 times higher. From the above, it was confirmed that the composition of the present invention has good resolution and good dry etching resistance in a well-balanced manner.
実施例３
実施例１のシリコン系重合体として前述の一製造例によ
り得られた重合体（ｎ）を用いた以外は、実施例１と同
様にして本発明の感光性組成物を得た。Example 3 A photosensitive composition of the present invention was obtained in the same manner as in Example 1, except that the polymer (n) obtained in the above-mentioned production example was used as the silicone polymer of Example 1.
実施例１と同じ露光・現像を行った。０．５μｍライン
／スペースを解像することができた。また、感度及び耐
ドライエツチング性についても実施例１とほぼ同様の効
果が認められた。The same exposure and development as in Example 1 was performed. It was possible to resolve 0.5 μm lines/spaces. Furthermore, almost the same effects as in Example 1 were observed regarding sensitivity and dry etching resistance.
以上に詳述した通り、本発明の感光性組成物は良好な解
像性及び良好な耐ドライエツチング性をバランス良く具
備するものであるため、例えば半導体素子の製造分野に
おける有用性が期待でき、その工業的価値は極めて大で
ある。As detailed above, the photosensitive composition of the present invention has good resolution and good dry etching resistance in a well-balanced manner, so it can be expected to be useful in the field of manufacturing semiconductor devices, for example. Its industrial value is extremely large.
図は残膜率とエネルギーの関係で表示された感度曲線を
示す。
○ −−一−−・−・・−・・・・実施例１■ −・−
・−・−・・一実施例２The figure shows a sensitivity curve expressed as a relationship between residual film rate and energy. ○ −−1−−・−・・−・・Example 1■ −・−
・−・−・・Example 2
Claims (1)
なってもよく、低級アルキレン基を表し、Ｒ＿３乃至Ｒ
＿８は、それぞれ、同一でも異なってもよく、水素原子
、水酸基、メチル基またはメチロール基を表し、Ｒ＿９
乃至Ｒ＿１＿２は、それぞれ、同一でも異なってもよく
、低級アルキル基を表し、Ｒ＿１＿３は、ＣＨ＿２又は
ＣＨ＿２ＯＣＨ＿２を表わし、Ｅは、フェノール、１〜
３の置換基を有するフェノール誘導体又は▲数式、化学
式、表等があります▼ （Ｒ＿１＿４は、低級アルキレン基を表わし、Ｒ＿１＿
５、Ｒ＿１＿６及びＲ＿１＿７は、低級アルキル基を表
わす）を表わし、Ｘは０＜Ｘ≦１の範囲の数であり、Ｙ
は１−Ｘの数である） で示される単位の少くとも一方を有するシリコン系重合
体 （Ｂ）１、２−ナフトキノンジアジド−５−スルホン酸
のトリ及びテトラエステル化合物からなる群より選択さ
れる少なくとも１種の感光剤 からなることを特徴とする感光性組成物。[Claims] (A) General formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In both formulas, R_1 and R_2 may be the same or different, respectively. Often represents a lower alkylene group, R_3 to R
_8 may be the same or different and each represents a hydrogen atom, a hydroxyl group, a methyl group, or a methylol group, and R_9
to R_1_2 may be the same or different and represent a lower alkyl group, R_1_3 represents CH_2 or CH_2OCH_2, and E is phenol, 1 to
There are phenol derivatives with 3 substituents or ▲mathematical formulas, chemical formulas, tables, etc.▼ (R_1_4 represents a lower alkylene group, R_1_
5, R_1_6 and R_1_7 represent a lower alkyl group), X is a number in the range of 0<X≦1, and Y
is the number of 1-X) (B) selected from the group consisting of tri- and tetraester compounds of 1,2-naphthoquinonediazide-5-sulfonic acid A photosensitive composition comprising at least one photosensitizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25139587A JPH0193736A (en) | 1987-10-05 | 1987-10-05 | Photosensitive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25139587A JPH0193736A (en) | 1987-10-05 | 1987-10-05 | Photosensitive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0193736A true JPH0193736A (en) | 1989-04-12 |
Family
ID=17222206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25139587A Pending JPH0193736A (en) | 1987-10-05 | 1987-10-05 | Photosensitive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0193736A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5161480A (en) * | 1990-08-24 | 1992-11-10 | Yazaki Corporation | Indication display unit for a vehicle |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6344652A (en) * | 1986-08-13 | 1988-02-25 | Sony Corp | Resist material |
| JPS63316849A (en) * | 1987-06-19 | 1988-12-26 | Sony Corp | Method for forming resist pattern |
-
1987
- 1987-10-05 JP JP25139587A patent/JPH0193736A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6344652A (en) * | 1986-08-13 | 1988-02-25 | Sony Corp | Resist material |
| JPS63316849A (en) * | 1987-06-19 | 1988-12-26 | Sony Corp | Method for forming resist pattern |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5161480A (en) * | 1990-08-24 | 1992-11-10 | Yazaki Corporation | Indication display unit for a vehicle |
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