JPS6352372B2 - - Google Patents
Info
- Publication number
- JPS6352372B2 JPS6352372B2 JP10029679A JP10029679A JPS6352372B2 JP S6352372 B2 JPS6352372 B2 JP S6352372B2 JP 10029679 A JP10029679 A JP 10029679A JP 10029679 A JP10029679 A JP 10029679A JP S6352372 B2 JPS6352372 B2 JP S6352372B2
- Authority
- JP
- Japan
- Prior art keywords
- salicylaldehyde
- bis
- polycondensate
- phenylenediamine
- present
- 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.)
- Expired
Links
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 12
- 229920002120 photoresistant polymer Polymers 0.000 claims description 8
- MPGOFFXRGUQRMW-UHFFFAOYSA-N [N-]=[N+]=[N-].[N-]=[N+]=[N-].O=C1C=CC=CC1=O Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].O=C1C=CC=CC1=O MPGOFFXRGUQRMW-UHFFFAOYSA-N 0.000 claims description 5
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 4
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- OWPBOKWFRAIKTD-UHFFFAOYSA-N 5-[(3-formyl-4-hydroxyphenyl)methyl]-2-hydroxybenzaldehyde Chemical compound C1=C(C=O)C(O)=CC=C1CC1=CC=C(O)C(C=O)=C1 OWPBOKWFRAIKTD-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012262 resinous product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- ZRUOTKQBVMWMDK-UHFFFAOYSA-N 2-hydroxy-6-methylbenzaldehyde Chemical compound CC1=CC=CC(O)=C1C=O ZRUOTKQBVMWMDK-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
【発明の詳細な説明】
本発明は新規なポジ型フオトレジスト組成物に
関する。さらに詳しく言えば、本発明は新規な感
光性樹脂を用いることを特徴とするポジ型フオト
レジスト組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel positive photoresist compositions. More specifically, the present invention relates to a positive photoresist composition characterized by using a novel photosensitive resin.
近年、ICの高密度化に伴い、ポジ型フオトレ
ジストの解像力、感度、耐熱性の向上が望まれて
いる。特に耐熱性に関してはドライエツチングに
関連して、その向上が強く要求されている。 In recent years, with the increasing density of ICs, it has been desired to improve the resolution, sensitivity, and heat resistance of positive photoresists. In particular, there is a strong demand for improvement in heat resistance in connection with dry etching.
本発明者等は従来のポジ型フオトレジストの耐
熱性を改善し、前記要求にこたえうる新規なフオ
トレジストを開発すべく研究を重ねた結果、後述
する如き新規な感光性樹脂を使用することによつ
てその目的を達成しうることを見出した。 As a result of repeated research to improve the heat resistance of conventional positive photoresists and develop a new photoresist that can meet the above requirements, the present inventors decided to use a new photosensitive resin as described below. I discovered that I could achieve that goal.
すなわち、本発明は、(a)ビス−サリチルアルデ
ヒドとｏ−フエニレンジアミンとの重縮合物と(b)
スルホニルクロライド基を有するｏ−ベンゾキノ
ンジアジドまたはｏ−ナフトキノンジアジドとを
化学的に縮合させて得られる新規な感光性樹脂を
用いることを特徴とするポジ型フオトレジスト組
成物を提供するものである。 That is, the present invention provides (a) a polycondensate of bis-salicylaldehyde and o-phenylenediamine; and (b)
The present invention provides a positive photoresist composition characterized by using a novel photosensitive resin obtained by chemically condensing o-benzoquinone diazide or o-naphthoquinone diazide having a sulfonyl chloride group.
本発明者等の創製に係る前記の新規な感光性樹
脂は、(a)ビス−サリチルアルデヒドとｏ−フエニ
レンジアミンとの重縮合物と(b)スルホニルクロラ
イド基を有するｏ−ベンゾキノンジアジドまたは
ｏ−ナフトキノンジアジドとを有機溶剤中、アル
カリの存在下で縮合反応を起させることによつて
製造することができる。 The novel photosensitive resin created by the present inventors is composed of (a) a polycondensate of bis-salicylaldehyde and o-phenylenediamine, and (b) o-benzoquinonediazide having a sulfonyl chloride group or o-benzoquinonediazide having a sulfonyl chloride group. -naphthoquinone diazide in an organic solvent in the presence of an alkali to cause a condensation reaction.
上記(a)のビス−サリチルアルデヒドとｏ−フエ
ニレンジアミンの重縮合物は、例えば以下のよう
にして製造される。ビス−サリチルアルデヒドと
ｏ−フエニレンジアミンとを氷酢酸と有機溶剤例
えばテトラヒドロフランを用いて、溶液とし、撹
拌すると重縮合物が析出してくる。 The polycondensate of bis-salicylaldehyde and o-phenylenediamine (a) above is produced, for example, as follows. When bis-salicylaldehyde and o-phenylenediamine are made into a solution using glacial acetic acid and an organic solvent such as tetrahydrofuran and stirred, a polycondensate precipitates out.
これを取し有機溶媒を用いて精製し、減圧乾
燥する。 This is taken, purified using an organic solvent, and dried under reduced pressure.
上記のビス−サリチルアルデヒドは、メチレン
基又はスルホン基などを介してサリチルアルデヒ
ド２分子を結合せしめたビス体構造の化合物をい
い、例えば５，5′−メチレン−ビス−サリチルア
ルデヒド、ビス−サリチルアルデヒド５，5′−ス
ルホンなどが例示される。上記のビス−サリチル
アルデヒドおよびｏ−フエニレンジアミンは、本
発明の目的を害わない範囲で種々の置換基を有す
ることができる。 The above-mentioned bis-salicylaldehyde refers to a compound having a bis structure in which two molecules of salicylaldehyde are bonded via a methylene group or a sulfone group, such as 5,5'-methylene-bis-salicylaldehyde, bis-salicylaldehyde, etc. Examples include 5,5'-sulfone. The above-mentioned bis-salicylaldehyde and o-phenylenediamine can have various substituents within the range that does not impede the purpose of the present invention.
本発明において用いられる前記の感光性樹脂
へ、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジ
メチルアセトアミドなどの有機溶剤に易溶であ
り、フエノールホルムアルデヒドノボラツク樹
脂、ｍ−クレゾールホルムアルデヒドノボラツク
樹脂あるいは前記の重縮合物(a)との相溶性も良
い。 The photosensitive resin used in the present invention is easily soluble in organic solvents such as N,N-dimethylformamide and N,N-dimethylacetamide, and is phenol formaldehyde novolac resin, m-cresol formaldehyde novolac resin, or It also has good compatibility with polycondensate (a).
本発明においては通常、前記の感光性樹脂とベ
ースレジンとを混合して使用するが、前記の感光
性樹脂のみを使用することもできる。さらに、本
発明の組成物には必要に応じて染料、安定剤など
の添加剤を含ませることができる。また本発明の
組成物は、通常、有機溶剤に溶解して使用される
がこのような溶剤としてはＮ，Ｎ−ジメチルホル
ムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジオ
キサン、エチルセロソルブアセテート、メチルセ
ロソルブ、テトラヒドロフラン等が例示される。
これらは２種以上の混合物として使用するのが好
ましい。 In the present invention, the above-mentioned photosensitive resin and base resin are usually used as a mixture, but it is also possible to use only the above-mentioned photosensitive resin. Furthermore, the composition of the present invention may contain additives such as dyes and stabilizers, if necessary. The composition of the present invention is usually used after being dissolved in an organic solvent, and examples of such solvents include N,N-dimethylformamide, N,N-dimethylacetamide, dioxane, ethyl cellosolve acetate, methyl cellosolve, and tetrahydrofuran. etc. are exemplified.
It is preferable to use a mixture of two or more of these.
本発明のポジ型フオトレジスト組成物は、これ
を用いると、基板上に形成された感光性樹脂膜が
耐熱性において、従来製品と比較し著しく優れて
いるものでポストベークを、より高温で行うこと
が可能となり、基板と樹脂膜との接着がより強固
に行われることとなる。また、従来製品では、ポ
ストベークを140〜150℃を越えると熱による変化
が著しく、例えば“だれ”、“かぶり”を生じ、画
像形成が不可能であるのに対し、本発明の組成物
では、200℃に至る温度においてすら、“だれ”、
“かぶり”を生ずることなく、ポストベークの目
的を充分に達し得る。 When the positive photoresist composition of the present invention is used, the photosensitive resin film formed on the substrate has significantly superior heat resistance compared to conventional products, and post-baking is performed at a higher temperature. This makes it possible to achieve stronger adhesion between the substrate and the resin film. In addition, with conventional products, when post-baking exceeds 140-150°C, changes due to heat are significant, resulting in "sagging" and "fogging", making it impossible to form images, whereas with the composition of the present invention, image formation is impossible. , even at temperatures up to 200℃,
The purpose of post-bake can be fully achieved without causing "fogging".
なお、本発明の組成物により、基板上に形成さ
れた感光性樹脂膜は、通常の現像液例えば、リン
酸水素ナトリウムとメタケイ酸ナトリウムなどを
主成分とする無機アルカリ現像液または第４級ア
ンモニウム塩を主成分とする有機アルカリ現像液
を用いて現像処理することができる。 Note that the photosensitive resin film formed on the substrate by the composition of the present invention can be formed using a normal developer, for example, an inorganic alkaline developer containing sodium hydrogen phosphate and sodium metasilicate as main components or a quaternary ammonium developer. Development processing can be performed using an organic alkaline developer containing salt as a main component.
次に実施例によつて本発明を詳細に説明する。 Next, the present invention will be explained in detail with reference to Examples.
実施例 １
(a) ５，5′−メチレン−ビス−サリチルアルデヒ
ドとｏ−フエニレンジアミンとの重縮合物10ｇ
とｏ−ナフトキノンジアジド−５−スルホン酸
クロライド40ｇをＮ，Ｎ−ジメチルホルムアミ
ド500mlに溶解し、トリエチルアミン40mlを滴
下後室温で４時間反応させる。反応終了後15％
塩酸100mlと水500mlを加えると黄色に着色した
樹脂状生成物が析出してくるので、これを取
し充分に純水洗浄したのちＮ，Ｎ−ジメチルア
セトアミドとテトラヒドロフランで精製する。
生成物を減圧乾燥すると黄色粉体が得られる。Example 1 (a) 10 g of polycondensate of 5,5'-methylene-bis-salicylaldehyde and o-phenylenediamine
40 g of o-naphthoquinonediazide-5-sulfonic acid chloride were dissolved in 500 ml of N,N-dimethylformamide, and 40 ml of triethylamine was added dropwise thereto, followed by reaction at room temperature for 4 hours. 15% after reaction completion
When 100 ml of hydrochloric acid and 500 ml of water are added, a yellow colored resinous product precipitates out, which is collected, thoroughly washed with pure water, and then purified with N,N-dimethylacetamide and tetrahydrofuran.
Drying the product under reduced pressure yields a yellow powder.
なお、上記の５，5′−メチレン−ビス−サリ
チルアルデヒドとｏ−フエニレンジアミンとの
重縮合物は以下の如くして調製されたものであ
る。 The above polycondensate of 5,5'-methylene-bis-salicylaldehyde and o-phenylenediamine was prepared as follows.
(イ) ５，5′−メチレン−ビス−サリチルアルデ
ヒドの合成
蒸留したサリチルアルデヒド80ｇを氷酢酸
50ml、トリオキサン7.0ｇの溶液中へ入れよ
く撹拌しながら窒素置換する。その後窒素雰
囲気中で、90℃まで加熱して濃硫酸0.5mlと
氷酢酸2.5mlの混酸をゆつくりと滴下する。
滴下後、90〜95℃で22時間反応を行なう。反
応終了後、反応液を３の氷水中へ注ぎ一晩
放置する。放置後結晶を取してエーテルで
よく洗浄し、アセトンで再結晶を行なうと
m.p.142〜143℃の５，5′−メチレン−ビス−
サリチルアルデヒドが収率48％で得られる。 (a) Synthesis of 5,5'-methylene-bis-salicylaldehyde 80g of distilled salicylaldehyde was mixed with glacial acetic acid.
Pour 50 ml of solution into a solution of 7.0 g of trioxane and purify with nitrogen while stirring well. Thereafter, in a nitrogen atmosphere, the mixture is heated to 90°C and a mixed acid of 0.5 ml of concentrated sulfuric acid and 2.5 ml of glacial acetic acid is slowly added dropwise.
After dropping, the reaction is carried out at 90-95°C for 22 hours. After the reaction is completed, the reaction solution is poured into ice water from Step 3 and left overnight. After standing, remove the crystals, wash thoroughly with ether, and recrystallize with acetone.
mp142-143℃5,5'-methylene-bis-
Salicylaldehyde is obtained with a yield of 48%.
(ロ) ５，5′−メチレンビス−サリチルアルデヒ
ドとｏ−フエニレンジアミンとの重縮合物の
合成
上記(a)で得た５，5′−メチレン−ビス−サ
リチルアルデヒド1.507ｇをテトラヒドロフ
ラン５ml、氷酢酸20ml中へ入れ、さらにｏ−
フエニレンジアミン666mgを氷酢酸20mlに溶
かした溶液を加え撹拌する。10〜20秒で、目
的とする重縮合物ポリマーが析出してくるの
で、これを取して、メタノール、エーテル
で洗浄し減圧乾燥すると1.750ｇのポリマー
が得られた。分解点260℃。 (b) Synthesis of polycondensate of 5,5'-methylenebis-salicylaldehyde and o-phenylenediamine 1.507g of 5,5'-methylenebis-salicylaldehyde obtained in (a) above was mixed with 5ml of tetrahydrofuran and iced. Pour into 20ml of acetic acid and add o-
Add a solution of 666 mg of phenylenediamine dissolved in 20 ml of glacial acetic acid and stir. The desired polycondensate polymer precipitated in 10 to 20 seconds, and was collected, washed with methanol and ether, and dried under reduced pressure to obtain 1.750 g of polymer. Decomposition point 260℃.
(b) 上記(a)で得た黄色粉体５ｇとアルカリ可溶性
フエノールホルムアルデヒドノボラツク樹脂15
ｇとをＮ，Ｎ−ジメチルホルムアミド30ｇとテ
トラヒドロフラン６ｇの混合溶剤に溶解し、
過する。得られた感光液を、常法により表面処
理したウエハー基板上に、スピンナーで1.5μの
塗膜になるように塗布し、85℃で10分間プリベ
ーク後、マスクを通して超高圧水銀灯で露光す
る。露光後、現像液、TMK（関東化学製）を
用いて１分間現像した後、充分に水洗し、180
℃で30分間ポストベークして、フツ化水素酸と
フツ化アンモニウムの混合水溶液でエツチング
したところ、解像力、寸法精度のすぐれたエツ
チング画像が得られた。得られた感光性樹脂膜
は、耐エツチング性にもすぐれている。(b) 5 g of yellow powder obtained in (a) above and 15 g of alkali-soluble phenol formaldehyde novolak resin
g in a mixed solvent of 30 g of N,N-dimethylformamide and 6 g of tetrahydrofuran,
pass The resulting photosensitive solution is applied with a spinner to a 1.5 μm film on a wafer substrate whose surface has been treated in a conventional manner, and after prebaking at 85° C. for 10 minutes, it is exposed through a mask to an ultra-high pressure mercury lamp. After exposure, develop for 1 minute using developer TMK (manufactured by Kanto Kagaku), wash thoroughly with water, and
After post-baking at ℃ for 30 minutes and etching with a mixed aqueous solution of hydrofluoric acid and ammonium fluoride, an etched image with excellent resolution and dimensional accuracy was obtained. The obtained photosensitive resin film also has excellent etching resistance.
実施例 ２ (a) 実施例１(a)で製造した黄色粉体を用いる。Example 2 (a) The yellow powder produced in Example 1(a) is used.
(b) 上記の黄色粉体10ｇをＮ，Ｎ−ジメチルホル
ムアミド30ｇ、メチルセロソルブ15ｇに溶解し
過する。得られた感光液を実施例１(b)と同様
にして、ウエハー基板上に塗布し塗膜を形成さ
せ以下実施例１(b)と同様の操作を行うとすぐれ
たエツチング画像が得られた。(b) Dissolve 10 g of the above yellow powder in 30 g of N,N-dimethylformamide and 15 g of methyl cellosolve. The obtained photosensitive solution was applied to a wafer substrate to form a film in the same manner as in Example 1(b), and the following operations were carried out in the same manner as in Example 1(b). An excellent etched image was obtained. .
実施例 ３
実施例１(a)で得た黄色粉体５ｇと５，5′−メチ
レン−ビス−サリチルアルデヒドとｏ−フエニレ
ンジアミンの重縮合物５ｇとをＮ，Ｎ−ジメチル
ホルムアミド30ｇとメチルセロソルブ10ｇの混合
溶剤に溶解し、過する。得られた感光液を用
い、以下実施例１(b)と同様の操作を行なつたとこ
ろ、解像力、寸法精度のすぐれたエツチング画像
が得られた。Example 3 5 g of the yellow powder obtained in Example 1(a) and 5 g of a polycondensate of 5,5'-methylene-bis-salicylaldehyde and o-phenylenediamine were mixed with 30 g of N,N-dimethylformamide and methyl Dissolve 10g of Cellosolve in a mixed solvent and filter. Using the obtained photosensitive liquid, the same operations as in Example 1(b) were carried out, and an etched image with excellent resolution and dimensional accuracy was obtained.
実施例 ４
(a) ビス−サリチルアルデヒド−５，5′−スルホ
ンとｏ−フエニレンジアミンの重縮合物10ｇと
ｏ−ナフトキノンジアジド−５−スルホン酸ク
ロライド40ｇをＮ，Ｎ−ジメチルアセトアミド
500mlに溶解し、トリエチルアミン40mlを滴下
後、40℃で３時間反応させ、反応終了後15％塩
酸100mlと水500mlを加えると黄色に着色した樹
脂状生成物が得られた。これをＮ，Ｎ−ジメチ
ルアセトアミドとテトラヒドロフランで精製す
る。得られた固体状物質を減圧乾燥する。Example 4 (a) 10 g of a polycondensate of bis-salicylaldehyde-5,5'-sulfone and o-phenylenediamine and 40 g of o-naphthoquinonediazide-5-sulfonic acid chloride were mixed with N,N-dimethylacetamide.
After dissolving in 500 ml of the solution, 40 ml of triethylamine was added dropwise, and the mixture was reacted at 40° C. for 3 hours. After the reaction was completed, 100 ml of 15% hydrochloric acid and 500 ml of water were added to obtain a resinous product colored yellow. This is purified with N,N-dimethylacetamide and tetrahydrofuran. The obtained solid substance is dried under reduced pressure.
(b) 上記(a)で得られた固体状物質10ｇとフエノー
ルホルムアルデヒドノボラツク樹脂20ｇとを
Ｎ，Ｎ−ジメチルホルムアミド30ｇ、メチルセ
ロソルブ30ｇの混合溶剤に溶解し、過する。
得られた感光液を、実施例１(b)と同様にして操
作を行なつたところ、解像力、寸法精度のすぐ
れたエツチング画像が得られた。(b) 10 g of the solid material obtained in (a) above and 20 g of phenol formaldehyde novolak resin are dissolved in a mixed solvent of 30 g of N,N-dimethylformamide and 30 g of methyl cellosolve and filtered.
When the obtained photosensitive solution was operated in the same manner as in Example 1(b), an etched image with excellent resolution and dimensional accuracy was obtained.
Claims (1)
ンジアミンとの重縮合物と(b)スルホニルクロライ
ド基を有するｏ−ベンゾキノンジアジドまたはｏ
−ナフトキノンジアジドとを化学的に縮合させて
得られる感光性樹脂を用いることを特徴とするポ
ジ型フオトレジスト組成物。1 (a) a polycondensate of bis-salicylaldehyde and o-phenylenediamine and (b) o-benzoquinonediazide or o-benzoquinonediazide having a sulfonyl chloride group
- A positive photoresist composition characterized by using a photosensitive resin obtained by chemically condensing naphthoquinonediazide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10029679A JPS5625730A (en) | 1979-08-08 | 1979-08-08 | Positive type photoresist composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10029679A JPS5625730A (en) | 1979-08-08 | 1979-08-08 | Positive type photoresist composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5625730A JPS5625730A (en) | 1981-03-12 |
| JPS6352372B2 true JPS6352372B2 (en) | 1988-10-18 |
Family
ID=14270201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10029679A Granted JPS5625730A (en) | 1979-08-08 | 1979-08-08 | Positive type photoresist composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5625730A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX170270B (en) * | 1984-06-01 | 1993-08-11 | Rohm & Haas | IMAGES ON A SURFACE AND A METHOD FOR FORMING THERMALLY STABLE POSITIVE AND NEGATIVE IMAGES ON A SURFACE |
| JP3872829B2 (en) * | 1995-08-30 | 2007-01-24 | 株式会社東芝 | Manufacturing method of colored thin film pattern |
| JP4653903B2 (en) * | 2001-05-09 | 2011-03-16 | 俊夫 増田 | Salicylideneaniline-based polymer, method for producing the same, and multicolor light emitting material using the same |
| JP7133364B2 (en) * | 2018-05-31 | 2022-09-08 | 群栄化学工業株式会社 | Polyimine, varnish, film and method for producing the same, cured film and method for producing the same, and laminate and method for producing the same |
-
1979
- 1979-08-08 JP JP10029679A patent/JPS5625730A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5625730A (en) | 1981-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH052226B2 (en) | ||
| JPS6236663A (en) | Naphthoquinonediazide type compound and positive type photoresist composition containing it | |
| JPH03228057A (en) | Positive type photoresist composition | |
| JPH02285351A (en) | Positive type photoresist composition | |
| JPS60121445A (en) | Positive type photosensitive resin composition | |
| JPH0523429B2 (en) | ||
| JPS6210646A (en) | Positive type photoresist composition | |
| JP2002040636A (en) | Photo-acid generating agent, photoresist composition containing the same and pattern forming method using the composition | |
| JPS6352372B2 (en) | ||
| JPH01309052A (en) | Positive type photoresist composition | |
| JP2697039B2 (en) | Method for producing positive resist composition | |
| JPH10168173A (en) | Production of polybenzoxazole and polybenzothiazole precursors | |
| JPS6352371B2 (en) | ||
| JP3365318B2 (en) | Polymer compound, resist material and pattern forming method | |
| JPS6210645A (en) | Positive type photoresist composition | |
| JP2676902B2 (en) | Triphenylmethane derivative and process for producing the same | |
| JP2558716B2 (en) | Positive photoresist composition | |
| JPS63279246A (en) | Positive photoresist composition | |
| JPS62270951A (en) | Cresol novolak resin for positive type photoresist | |
| JPH0446947B2 (en) | ||
| JPS58203434A (en) | Positive type photoresist composition | |
| JPH032293B2 (en) | ||
| JPH0525257A (en) | Production of radiation-sensitive component, and positive resist composition | |
| JPH0527430A (en) | Positive photoresist composition | |
| JPH0820730B2 (en) | Positive type radiation sensitive resin composition |