JPH0147774B2 - - Google Patents

Info

Publication number
JPH0147774B2
JPH0147774B2 JP3230082A JP3230082A JPH0147774B2 JP H0147774 B2 JPH0147774 B2 JP H0147774B2 JP 3230082 A JP3230082 A JP 3230082A JP 3230082 A JP3230082 A JP 3230082A JP H0147774 B2 JPH0147774 B2 JP H0147774B2
Authority
JP
Japan
Prior art keywords
photosensitive
group
compounds
present
photoresist film
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
Application number
JP3230082A
Other languages
Japanese (ja)
Other versions
JPS58150948A (en
Inventor
Masanao Oozeki
Shigehiro Tanaka
Takako Fujimoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dainippon Ink and Chemicals Co Ltd filed Critical Dainippon Ink and Chemicals Co Ltd
Priority to JP3230082A priority Critical patent/JPS58150948A/en
Publication of JPS58150948A publication Critical patent/JPS58150948A/en
Publication of JPH0147774B2 publication Critical patent/JPH0147774B2/ja
Granted legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/022Quinonediazides

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)

Description

【発明の詳細な説明】[Detailed description of the invention]

本発明はIC、LSI等の素子の製造に際し使用さ
れる超微細工用レジストとして、また平版印刷版
の製造に際し使用される感光材料として応用可能
な高感度のポジ型感光性組成物に関する。 ポジ型感光性物質の代表的なものとして、1,
2−キノンジアジド化合物があり、かかる1.2−
キノンジアジド化合物に関しては、例えば西独特
許第938233号公報をはじめとし、J.コーサー著
「ライト−センシテイブ・システムズ」(John
Wiley&Sons、Inc)第339〜357頁に紹介された
多くの特許公報、技術文献によつて、非常に数多
くの化合物が知られている。更に、これら公知の
1,2−キノシジアジト化合物の中でも、特に芳
香族ポリヒドロキシ化合物の1,2−ナフトキノ
ン−2−ジアジドスルホン酸エステルが好適であ
ることもまた知られている。 Shipley社から現在「AZ−1350J」の商標の下
に販売されているホトレジストは、超微細加工分
野で実用的に広く使用されている最も代表的なも
のであり、該レジストに使用されている感光性物
質は、既に、IBMレポート(IBM J,Res.
Develop.Vol.23、No.1、JANNARY 1979)によ
つて、その化学的構造が明らかになされている。
即ち、このIBMレポートによつて、上記ホトレ
ジストの感光性物質が式 で表わされる化合物であることがが明らかにされ
ている。 本発明者等は、この感光性物質が、現に実用的
に広く使用されている代表的なものであるという
現実からみて、ポジ型感光性物質の現在の実用的
水準を示しているものと理解している。一方、超
微細加工分野では、現在の加工生産性を更に向上
させるために現在実用的に使用されているホトレ
ジストよりも高感度のホトレジストを切望してい
る情況にある。 本発明は、かかる情況に鑑みて成されたもので
あり、その目的とするところは、高感度のポジ型
感光性組成物を提供することにある。 本発明者等は各種の感光性物質の化学的構造と
感度との関係について検討した結果、ポリヒドロ
キシベンゾフエノンの1,2−ナフトキノン−2
−ジアジト−スルホン酸エステルの化合物群の中
で、少なくともベンゾフエノン核のカルボニル基
に燐接する2位及び2′位が夫々水酸基で置換され
た化合物が特異的に高い感度を有することを見出
して本発明に致達した。 即ち、本発明は、一般式 式中、R及びR′は互に同一又は異なつてよく、
水素原子、1〜2個の炭素原子を有するアルコキ
シル基、水酸基、ニトロ基又は−O−D基を表わ
す。Dは1,2−ナフトキノン−2−ジアジド−
スルホニル基を表わす。mは0〜3の整数、
m′は0〜4の整数を表わす。 で表わされる化合物及びアルカリ可溶性樹脂から
成る感光性組成物に関する。 式(1)の化合物の中で特に好ましい化合物として
次の化合物を挙げることができる。 式(1)の化合物と混合されるアルカリ可溶性樹脂
としては、従来からポジ型感光性組成物の調製に
際し使用されている各種のアルカリ可溶性樹脂を
使用することができる。このような樹脂としては
例えばフエノールホルムアルデヒド樹脂、クレゾ
ールホルムアルデヒド樹脂、スチレン−無水マレ
イン酸樹脂、シエラツク等がある。式(1)の化合物
は感光性組成物の全固形分に対し20〜35重量%配
合することが好ましい。 本発明に係る感光性組成物は、適当な溶媒に溶
解して支持体上に塗布される。適当な溶媒として
は、例えばメチルセロソルブ、エチルセロソル
ブ、メチルセロソルブアセテート、エチルセロソ
ルブアセテート、シクロヘキサノン、ジメチルス
ルオキサイド、ジメチルホルムアミド、ジオキサ
ン、テトラヒドロフラン等があり、これらは単独
又は混合して使用される。 本発明に係る感光性組成を塗布する支持体とし
ては、例えば、シリコンウエハー、アルミニウム
板、銅板、プリント配線用銅張績層板等が用途に
応じて適宜使用される。本発明に係る感光性組成
物をスピンナー、コーター等の適当な塗布手段で
支持体上に塗布し、乾燥することによつて感光層
が形成される。感光層は、パターンマスク、パタ
ーンフイルムの如き透明原画を透過した光線が照
対され、次いでアルカリ現像液で現像される。 アルカリ現像液としては、例えば水酸化ナトリ
ウム、水酸化カリウム、珪酸ナトリウム、珪酸カ
リウム、第三燐酸ナトリウム、第三燐酸カリウ
ム、炭酸ナトリウム、炭酸カリウムの如き無機ア
ルカリ、エタノールアミンの如き有機アルカリの
水溶液から成り、更に必要に応じて界面活性剤、
ベンジルアルコールの如きアルコールが加えられ
た現像剤を使用することができる。 以下、実施例によつて本発明を更に詳細に説明
する。 実施例 フエノールノボラツク樹脂(大日本インキ化学
工業社製「プライオ−フエン」)6gと第1表及
び第2表記載の各感光性物質(注)3gとをセロソル
ブアセテート20mlに溶解させて感光性樹脂溶液を
調製し、スピンナーで、この溶液をシリコンウエ
ハーの上に塗布し、90℃に加熱されたホツトプレ
ート上で30分間加熱乾燥させることにより、感光
膜を形成した。各感光膜の膜厚を1.2μとした。 (注)第1表中の(a)〜(g)の化合物は本発明に係る感光
物質であり、第2表中の(h)〜(K)の化合物は比較
のために使用した公知の感光性物質であつて、
(h)は本発明細書の冒頭に起載した如く現在超微
細加工分野で広く使用されているShipley社の
ホトレジスト「AZ−1350J」に使用されている
感光性物質であり、(i)〜(K)は本発明に係る感光
性物質と化学的構造が類似する化合物であつ西
独特許第938233号公報に記載されたものであ
る。 次いで、次に述べる露光方法に従つて、各感光
膜に露光し、これを現像することにより、各感光
膜の感度を測定した。露光に際し、協栄セミコン
ダクタ−社製の紫外線照射装置「K−200」を使
用し、感光膜表面での光量を33mW/cm2に設定し
た。現像に際し、PH12.5のNaOH水溶液を現像液
として使用した。 露光方法は、第1図及び第2図に示す如く、シ
リコンウエハー1上に形成された感光膜2をl
1,l2,l3,l4,l5及びl6の区分線に
よつて、S0,S1,S2,S3,S4,S5及
びS6の7つの区分に区画し、先づ、ハードマス
ク3の図示左端をl6の区分線に位置させて、S
6の区分を露出させると共に区分をハードマスク
3で遮蔽し、露出した感光膜に1秒間露出した。
次いで、ハードマスク3を図面右方に移動させ、
その左端をl5の区分線に位置させ、再び1秒間
露光した。以下同様に、l4、l3,l2及びl
1の各区分線に順次ハードマスク3の左端を位置
させ、各位置で1秒間露光した。この操作でS
0,S1,S2,S3,S4,S5,S6の各区
分は夫々0、1、2、3、4、5、6秒間露光さ
れた。かくして、紫外線被曝量の異なる区分の形
成された感光層2を現像液中に1分間浸漬した状
態で軽く振盪した後、これを水洗し乾操した。こ
の現像によつて感光膜2が除去された幾つかの区
分の中の紫外線被曝量の最も少ない区分における
露光秒数を感度とし第3表に掲示した。 この現像条件は未露光部の感光膜が現像液で溶
かされてその膜厚が減少する現象(所謂膜減り)
の起らない条件に設定されている。現像条件の設
定に際し、感光膜に膜減りの起らないことの確認
は、日本光学社製サーフイスフイニツシユマイク
ロスコープを使用することによつて行つた。
The present invention relates to a highly sensitive positive-working photosensitive composition that can be applied as a resist for ultra-fine processing used in the production of elements such as ICs and LSIs, and as a photosensitive material used in the production of lithographic printing plates. Typical positive photosensitive materials include: 1.
There are 2-quinonediazide compounds, such as 1.2-
Regarding quinonediazide compounds, for example, West German Patent No. 938233 and J. Coser's ``Light-Sensitive Systems'' (John
Wiley & Sons, Inc.), pages 339-357, a large number of compounds are known from the many patent publications and technical literature. Furthermore, it is also known that among these known 1,2-quinocidiazide compounds, 1,2-naphthoquinone-2-diazide sulfonic acid esters of aromatic polyhydroxy compounds are particularly suitable. The photoresist currently sold by Shipley under the trademark "AZ-1350J" is the most representative one that is practically widely used in the field of ultrafine processing, and the photoresist used in the resist is Sexual substances have already been identified in the IBM report (IBM J, Res.
Develop.Vol.23, No.1, JANNARY 1979), its chemical structure was clarified.
That is, according to this IBM report, the photosensitive material of the photoresist is It has been revealed that the compound is represented by The present inventors understand that this photosensitive material represents the current practical level of positive photosensitive materials in view of the fact that it is a typical photosensitive material that is actually widely used. are doing. On the other hand, in the field of ultrafine processing, there is a strong need for a photoresist with higher sensitivity than the photoresists currently in practical use in order to further improve the current processing productivity. The present invention has been made in view of such circumstances, and its purpose is to provide a highly sensitive positive-working photosensitive composition. As a result of studying the relationship between the chemical structure and sensitivity of various photosensitive substances, the present inventors found that 1,2-naphthoquinone-2 of polyhydroxybenzophenone
- Among the group of compounds of diazito-sulfonic acid esters, it was discovered that a compound in which at least the 2-position and the 2'-position connected to the carbonyl group of the benzophenone nucleus were each substituted with a hydroxyl group had a specifically high sensitivity, and the present invention reached. That is, the present invention provides the general formula In the formula, R and R′ may be the same or different from each other,
It represents a hydrogen atom, an alkoxyl group having 1 to 2 carbon atoms, a hydroxyl group, a nitro group or an -O-D group. D is 1,2-naphthoquinone-2-diazide-
Represents a sulfonyl group. m is an integer from 0 to 3,
m' represents an integer from 0 to 4. The present invention relates to a photosensitive composition comprising a compound represented by the formula and an alkali-soluble resin. Among the compounds of formula (1), the following compounds are particularly preferred. As the alkali-soluble resin to be mixed with the compound of formula (1), various alkali-soluble resins conventionally used in the preparation of positive-working photosensitive compositions can be used. Such resins include, for example, phenol formaldehyde resin, cresol formaldehyde resin, styrene-maleic anhydride resin, and silica resin. The compound of formula (1) is preferably blended in an amount of 20 to 35% by weight based on the total solid content of the photosensitive composition. The photosensitive composition according to the present invention is dissolved in a suitable solvent and applied onto a support. Suitable solvents include, for example, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexanone, dimethyl sulfoxide, dimethyl formamide, dioxane, and tetrahydrofuran, which may be used alone or in combination. As the support to which the photosensitive composition according to the present invention is coated, for example, a silicon wafer, an aluminum plate, a copper plate, a copper-clad laminate for printed wiring, etc. are used as appropriate depending on the purpose. A photosensitive layer is formed by applying the photosensitive composition according to the present invention onto a support using a suitable coating means such as a spinner or coater and drying it. The photosensitive layer is irradiated with a light beam transmitted through a transparent original image such as a patterned mask or patterned film, and then developed with an alkaline developer. Examples of alkaline developers include aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, sodium triphosphate, potassium triphosphate, sodium carbonate, and potassium carbonate, and organic alkalis such as ethanolamine. and, if necessary, a surfactant,
Developers loaded with alcohol such as benzyl alcohol can be used. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 6 g of phenol novolac resin (“Plyophene” manufactured by Dainippon Ink and Chemicals) and 3 g of each photosensitive substance (note) listed in Tables 1 and 2 were dissolved in 20 ml of cellosolve acetate to make it photosensitive. A resin solution was prepared, and this solution was applied onto a silicon wafer using a spinner, and then heated and dried on a hot plate heated to 90° C. for 30 minutes to form a photoresist film. The thickness of each photoresist film was 1.2μ. (Note) Compounds (a) to (g) in Table 1 are photosensitive materials according to the present invention, and compounds (h) to (K) in Table 2 are known compounds used for comparison. A photosensitive substance,
(h) is a photosensitive material used in Shipley's photoresist "AZ-1350J", which is currently widely used in the field of ultrafine processing, as mentioned at the beginning of the specification of the present invention, and (i) ~ (K) is a compound having a similar chemical structure to the photosensitive substance according to the present invention and is described in West German Patent No. 938233. Next, each photoresist film was exposed and developed according to the exposure method described below, and the sensitivity of each photoresist film was measured. During exposure, an ultraviolet irradiation device "K-200" manufactured by Kyoei Semiconductor Co., Ltd. was used, and the amount of light on the surface of the photoresist film was set at 33 mW/cm 2 . During development, an aqueous NaOH solution with a pH of 12.5 was used as a developer. In the exposure method, as shown in FIGS. 1 and 2, a photoresist film 2 formed on a silicon wafer 1 is
The hard mask 3 is divided into seven sections S0, S1, S2, S3, S4, S5 and S6 by dividing lines 1, l2, l3, l4, l5 and l6. Position it on the dividing line and press S.
Section 6 was exposed and the section was covered with hard mask 3, and the exposed photoresist film was exposed for 1 second.
Next, move the hard mask 3 to the right side of the drawing,
Its left end was positioned at the division line 15 and exposed again for 1 second. Similarly, l4, l3, l2 and l
The left end of the hard mask 3 was sequentially positioned at each dividing line of 1, and exposed for 1 second at each position. With this operation, S
Each section of 0, S1, S2, S3, S4, S5, and S6 was exposed for 0, 1, 2, 3, 4, 5, and 6 seconds, respectively. The photosensitive layer 2, in which the sections having different amounts of ultraviolet exposure were formed, was immersed in the developer for 1 minute and gently shaken, then washed with water and dried. The number of seconds of exposure in the category where the amount of ultraviolet rays was least exposed among the several sections in which the photoresist film 2 was removed by this development was defined as the sensitivity and is listed in Table 3. This development condition is a phenomenon in which the unexposed areas of the photoresist film are dissolved by the developer and the film thickness decreases (so-called film thinning).
The conditions are set so that this does not occur. When setting the development conditions, it was confirmed that no film loss occurred in the photoresist film by using a Nippon Kogaku Surf Finish Microscope.

【表】【table】

【表】【table】

【表】【table】

【表】【table】 【図面の簡単な説明】[Brief explanation of drawings]

図面は、感光層の露光方法の説明図で、第1図
は平面図、第2図は断面図である。 1……シリコンウエハー、2……感光層、3…
…ハードマスク。
The drawings are explanatory diagrams of a method of exposing a photosensitive layer, with FIG. 1 being a plan view and FIG. 2 being a sectional view. 1... Silicon wafer, 2... Photosensitive layer, 3...
...hard mask.

Claims (1)

【特許請求の範囲】 1 一般式 式中、R及びR′は互に同一又は異なつてよく、
水素原子、1〜2個の炭素原子を有するアルコキ
シル基、水酸基、ニトロ基又は−O−D基を表わ
す。Dは1,2−ナフトキノン−2−ジアジド−
スルホニル基を表わす。mは0〜3の整数、
m′は0〜4の整数を表わす。 で表わされる化合物及びアルカリ可溶性樹脂から
成る感光性組成物。
[Claims] 1. General formula In the formula, R and R′ may be the same or different from each other,
It represents a hydrogen atom, an alkoxyl group having 1 to 2 carbon atoms, a hydroxyl group, a nitro group or an -O-D group. D is 1,2-naphthoquinone-2-diazide-
Represents a sulfonyl group. m is an integer from 0 to 3,
m' represents an integer from 0 to 4. A photosensitive composition comprising a compound represented by: and an alkali-soluble resin.
JP3230082A 1982-03-03 1982-03-03 Photosensitive composition Granted JPS58150948A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP3230082A JPS58150948A (en) 1982-03-03 1982-03-03 Photosensitive composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3230082A JPS58150948A (en) 1982-03-03 1982-03-03 Photosensitive composition

Publications (2)

Publication Number Publication Date
JPS58150948A JPS58150948A (en) 1983-09-07
JPH0147774B2 true JPH0147774B2 (en) 1989-10-16

Family

ID=12355094

Family Applications (1)

Application Number Title Priority Date Filing Date
JP3230082A Granted JPS58150948A (en) 1982-03-03 1982-03-03 Photosensitive composition

Country Status (1)

Country Link
JP (1) JPS58150948A (en)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60164740A (en) * 1984-02-06 1985-08-27 Japan Synthetic Rubber Co Ltd Positive type photosensitive resin composition
JPS62123444A (en) * 1985-08-07 1987-06-04 Japan Synthetic Rubber Co Ltd Radiation sensitive resinous composition
JPH0654381B2 (en) * 1985-12-24 1994-07-20 日本合成ゴム株式会社 Positive resist for integrated circuit fabrication
JP2787943B2 (en) * 1987-12-29 1998-08-20 三菱化学株式会社 Positive photoresist composition
JP2622267B2 (en) * 1988-03-23 1997-06-18 日立化成工業株式会社 Photosensitive resin composition
JP2629814B2 (en) * 1988-05-09 1997-07-16 日本合成ゴム株式会社 Positive radiation-sensitive resin composition
JP2800186B2 (en) * 1988-07-07 1998-09-21 住友化学工業株式会社 Method for producing positive resist composition for producing integrated circuits
JP2636348B2 (en) * 1988-07-20 1997-07-30 住友化学工業株式会社 Composition for positive resist
JP2715480B2 (en) * 1988-10-13 1998-02-18 住友化学工業株式会社 Composition for positive resist
JP2944296B2 (en) 1992-04-06 1999-08-30 富士写真フイルム株式会社 Manufacturing method of photosensitive lithographic printing plate
JP3278306B2 (en) 1994-10-31 2002-04-30 富士写真フイルム株式会社 Positive photoresist composition
US5541033A (en) * 1995-02-01 1996-07-30 Ocg Microelectronic Materials, Inc. Selected o-quinonediazide sulfonic acid esters of phenolic compounds and their use in radiation-sensitive compositions
JP2790132B2 (en) * 1996-10-18 1998-08-27 住友化学工業株式会社 Method of forming positive resist pattern for integrated circuit production
AU4072799A (en) 1998-05-12 1999-12-13 American Home Products Corporation 2,3,5-substituted biphenyls useful in the treatment of insulin resistance and hyperglycemia
US6221902B1 (en) 1998-05-12 2001-04-24 American Home Products Corporation Biphenyl sulfonyl aryl carboxylic acids useful in the treatment of insulin resistance and hyperglycemia
US6110963A (en) * 1998-05-12 2000-08-29 American Home Products Corporation Aryl-oxo-acetic acids useful in the treatment of insulin resistance and hyperglycemia
US6232322B1 (en) 1998-05-12 2001-05-15 American Home Products Corporation Biphenyl oxo-acetic acids useful in the treatment of insulin resistance and hyperglycemia
US6699896B1 (en) 1998-05-12 2004-03-02 Wyeth Oxazole-aryl-carboxylic acids useful in the treatment of insulin resistance and hyperglycemia
US6451827B2 (en) 1998-05-12 2002-09-17 Wyeth 2,3,5-substituted biphenyls useful in the treatment of insulin resistance and hyperglycemia
US6310081B1 (en) 1999-05-10 2001-10-30 American Home Products Corporation Biphenyl sulfonyl aryl carboxylic acids useful in the treatment of insulin resistance and hyperglycemia

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Publication number Publication date
JPS58150948A (en) 1983-09-07

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