JPS6051695B2 - O-naphthoquinone diazide photoresist development method - Google Patents
O-naphthoquinone diazide photoresist development methodInfo
- Publication number
- JPS6051695B2 JPS6051695B2 JP53116370A JP11637078A JPS6051695B2 JP S6051695 B2 JPS6051695 B2 JP S6051695B2 JP 53116370 A JP53116370 A JP 53116370A JP 11637078 A JP11637078 A JP 11637078A JP S6051695 B2 JPS6051695 B2 JP S6051695B2
- Authority
- JP
- Japan
- Prior art keywords
- photoresist
- naphthoquinone diazide
- developer
- formamide
- developed
- 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
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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Description
【発明の詳細な説明】
本発明は０−ナフトキノンジアジド系フォトレジスト、
つまり０−ナフトキノンジアジド成分を光学解基として
含有するフォトレジスト用現像法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides an 0-naphthoquinone diazide photoresist,
That is, the present invention relates to a developing method for a photoresist containing an 0-naphthoquinone diazide component as an optically radical.
集積回路、とりわけシリコン半導体集積回路の作製にお
いて、その微細な回路パターンの作製にフォトエッチン
グ工程が不可欠であり、フォトレジストに対しては解像
力がすぐれていること、現像時の膜残りがないこと、お
よびピンホールの発生が少ないこと等の性能が要求され
る。In the production of integrated circuits, especially silicon semiconductor integrated circuits, the photoetching process is indispensable for the production of fine circuit patterns, and for photoresists, it must have excellent resolution and no film residue during development. Performance such as low occurrence of pinholes is also required.
０−ナフトキノンジアジド成分は光分解基として含有す
るフォトレジストはこのような要求なほぼ満足するもの
としてフォトエッチング工程によく用いられており、例
えば０−ナフトキノンジアジドスルホニルクロライド（
１）とフエノールノボラノツク樹脂（２）とを縮合させ
て製造され（３）で示す構造を有する。Photoresists containing an 0-naphthoquinone diazide component as a photodegradable group are often used in the photo-etching process as they almost satisfy these requirements; for example, 0-naphthoquinone diazide sulfonyl chloride (
It is produced by condensing 1) with phenol novolanok resin (2) and has the structure shown in (3).
このようなフォトレジストとしては、例えばＭｌ３５Ｏ
Ｊ（ＳＨＩＰＬＥＹ社製、商品名）があり、半導体回路
用として高純度なものである。As such a photoresist, for example, Ml35O
J (manufactured by SHIPLEY, trade name), which is of high purity for use in semiconductor circuits.
ところで、このようなＯ−ナフトキノンジアジド成分を
含有するフォトレジストに対する現像液として従来力性
ソーダ、ケイ酸ソーダ等の水溶液が用いられていた。By the way, an aqueous solution of sodium hydroxide, sodium silicate, or the like has conventionally been used as a developer for a photoresist containing such an O-naphthoquinone diazide component.
しかし、このような現像液はアルカリ金属を含むためシ
リコン等の半導体集積回路製作のフォトエッチング工程
に用いた場合、シリコン中にこれら金属元素が拡散し、
半導体集積回路に経時変化を与え、また雑音の原因にな
ることは知られている。また、アルカリ金属を含有しな
い現像液として水溶液アミンと水溶液アルコールを含有
する水溶液が知られており、水溶液アミンとしてはメチ
ルアミン、エチルアミン、モノエタノールアミン等が用
いられ、また水溶液アルコールとしてメタノール、エタ
ノール等が用いられている。However, since such a developer contains alkali metals, when used in the photo-etching process for manufacturing semiconductor integrated circuits made of silicon or other materials, these metal elements diffuse into the silicon.
It is known that it causes changes in semiconductor integrated circuits over time and causes noise. In addition, an aqueous solution containing an aqueous amine and an aqueous alcohol is known as a developing solution that does not contain an alkali metal, and the aqueous amine includes methylamine, ethylamine, monoethanolamine, etc., and the aqueous alcohol includes methanol, ethanol, etc. is used.
しかしながら、このアミンを主体とする現像液には毒性
があり安全衛生上の問題があつた。本発明はかかる点に
鑑みなされたものでアルカリ金属等の金属元素による影
響がなく、また毒性のない作業上安全な現像法を提供す
るものであつＩて現像液にホルムアミドを用いたことを
特徴とする。However, this amine-based developer is toxic and poses health and safety problems. The present invention has been devised in view of the above points, and provides a developing method that is not affected by metal elements such as alkali metals, and is non-toxic and safe for operation.The present invention is characterized in that formamide is used as the developer. shall be.
本発明の現像液は分子式が（４）で表されるホルムアミ
ドを主成分とするものである。０−ナフトキノンジアジ
ド成分を含有するフォトレジストに対して、前記ホルム
アミド１００％の現像液で現像を行うと除去すべき現像
膜が溶解せずに残り、いわゆる膜残りを生じる。The developer of the present invention contains formamide having the molecular formula (4) as a main component. When a photoresist containing a 0-naphthoquinonediazide component is developed with the above-mentioned 100% formamide developer, the developed film to be removed remains undissolved, resulting in so-called film residue.
そこて本発明においてはフォトレジストの溶解度を高め
るた５めに水で希釈したエタノール等のアルコールを適
宜容量添加する。しかし、現像液中のアルコール濃度が
高くなると露光を行わないフォトレジスト部分も溶解さ
せ現像液はその現像作用を失う。本発明においては現像
液はその組成比を異ならせることによつて、０−ナフト
キノンジアジド成分を光分解基として含有するフォトレ
ジストをポジ型フォトレジストとしても、またこれをネ
ガ型フォトレジストとしても用いることができる。添付
図面に示した本発明に係る現像液の組成図を参・照しな
がら詳しく述べると添付図面の太枠で囲こまれた組成比
領域Ｐはホルムアミドが８０％〜１００％、水がＯ％〜
２０％、エタノールが０％〜２０％の組成比の現像液に
対応し、組成比領域内の組成比を有する現像液を用いて
現像すると前記フォトレジスト型となる。つまり、該現
像液中ではフォトレジストの露光部分のみが溶解する。
例えば０−ナフトキノンジアジド成分を光分解基として
含有するフォトレジストとしてＡＺ−１３５０Ｊ（ＳＨ
ＩＰＬＥＹ社製、商品名）を用い、該レジストをアルミ
金属盤上に厚さ９０００Ａに塗布し、８５０Ｗ超高圧水
銀ランプを露光光源として所定の露光マスクを介して１
０８間照射した後、ホルムアミド９０％、エタノール５
℃、水５％を組成とする現像液で室温にて３Ｃ＠間現像
を行うとフォトレジスト厄−１３５０Ｊはポジ型の特性
を示し、露光部分のフォトレジストのみが溶解し、この
部分のフォトレジスト膜厚は６０００Ａとなる。なお、
組成の比率はＶＯｌ％で示したが以下同様とする。また
、添付図面の太枠で囲こまれた組成比領域Ｎはホルムア
ミドが８０％〜７０％、エタノールが１０％〜４０％、
水が２０％〜３０％組成比の現像液に対応し、この組成
比領域内の組成比を有する現像液を用いて現像すると前
記フォトレジストはネガ型となり、該現像液を用いて現
像すると前記フォトレジストの未露光の部分のみが溶解
し、露光部分は溶解しない。例えば、ホルムアミド５０
％、エタノール２５％、水２５％の現像液を用いて前述
の実施例と同一条件でフォトレジストＶ−１３５０Ｊを
現像すると、該フォトレジストはネガ型の特性を示し未
露光部分のフォトレジストのみが溶解し、この部分のフ
ォトレジストの膜厚は６０００Ａとなる。本発明におい
て用いられるホルムアミドは（４）で表される分子式を
有し、これより明らかなように金属元素を含有せず、半
導体集積回路製作のエッチング工程に適用しても上述し
たようなアルカリ金属による回路装置の電気的特性の劣
化を招来することがない。Therefore, in the present invention, in order to increase the solubility of the photoresist, an appropriate amount of alcohol such as ethanol diluted with water is added. However, when the alcohol concentration in the developer becomes high, the portions of the photoresist that are not exposed to light are also dissolved, and the developer loses its developing action. In the present invention, by varying the composition ratio of the developer, a photoresist containing an 0-naphthoquinone diazide component as a photodegradable group can be used as a positive photoresist, and this can also be used as a negative photoresist. be able to. To explain in detail with reference to the composition diagram of the developer according to the present invention shown in the attached drawings, the composition ratio region P surrounded by a thick frame in the attached drawings contains 80% to 100% formamide and 0% water. ~
When developed using a developer having a composition ratio within the composition ratio range, the photoresist type is obtained. That is, only the exposed portions of the photoresist are dissolved in the developer.
For example, AZ-1350J (SH
The resist was coated to a thickness of 9000A on an aluminum metal plate using a 9000A (manufactured by IPLEY Co., Ltd., trade name).
After irradiation for 08 hours, formamide 90%, ethanol 5
When developed at room temperature for 3C with a developing solution containing 5% water at The film thickness is 6000A. In addition,
Although the composition ratio is expressed in VOl%, the same applies hereinafter. In addition, the composition ratio region N surrounded by a thick frame in the attached drawing is 80% to 70% formamide, 10% to 40% ethanol,
The photoresist corresponds to a developer having a composition ratio of 20% to 30% water, and when developed using a developer having a composition ratio within this composition ratio range, the photoresist becomes negative type; Only the unexposed parts of the photoresist dissolve; the exposed parts do not. For example, formamide 50
When photoresist V-1350J was developed under the same conditions as in the previous example using a developer containing 25% ethanol and 25% water, the photoresist exhibited negative type characteristics and only the unexposed portions of the photoresist were exposed. It melts, and the photoresist film thickness at this portion becomes 6000 Å. The formamide used in the present invention has the molecular formula represented by (4), and as is clear from this, it does not contain any metal elements, and even when applied to the etching process of semiconductor integrated circuit production, it does not contain the above-mentioned alkali metals. This does not cause deterioration of the electrical characteristics of the circuit device.
また、ホルムアミドは毒性が少ない上、引火点が１５０
℃と高いため本発明は作業の安全衛生上も好ましい。In addition, formamide is less toxic and has a flash point of 150
℃, the present invention is also preferable in terms of work safety and health.
さらに本発明は現像液の組成比を異ならせるだけで０−
ナフトキノンジアジド系フォトレジスト系をポジ型とし
てもまたネガ型としても現像処理できる利点がある。轟
図面の簡単な説明
添付図面は本発明に係る現像液の組成比を示し、組成比
領域ＰおよびＮに対応する組成比を有する現像液中では
Ｏ−ナフトキノンジアジド成分を光分解基とするフォト
レジストはそれぞれポジ７型およびネガ型の特性を示す
。Furthermore, the present invention provides 0-
There is an advantage that the naphthoquinone diazide photoresist system can be developed as either a positive type or a negative type. Brief explanation of Todoroki drawings The attached drawings show the composition ratio of the developer according to the present invention. The resists exhibit positive-7 and negative-tone properties, respectively.
Claims (1)
ナフトキノンジアジド系フォトレジストを塗布し、所定
の露光マスクを用いてこれを露出した後、現像処理する
Ｏ−ナフトキノンジアジド系フォトレジスト現像法にお
いてホルムアミドおよびエタノールを含む現像液を用い
てＯ−ナフトキノンジアジド系フォトレジストを現像処
理することを特徴とするＯ−ナフトキノンジアジド系フ
ォトレジスト現像法。 ２ 前記現像液がホルムアミドを８０体積％〜１００体
積％、エタノールを０〜２０体積％および水を０〜２０
体積％含有し、該現像液を用いてＯ−ナフトキノンジア
ジド系フォトレジストをポジ型フォトレジストとして現
像処理することを特徴とする特許請求の範囲第１項に記
載のＯ−ナフトキノンジアジド系フォトレジスト現像法
。 ３ 前記現像液がホルムアミドを３０体積％〜７０体積
％、エタノールを１０体積％〜４０体積％および水を２
０体積％〜８０体積％を含有し、該現像液を用いてＯ−
ナフトキノンジアジド系フォトレジストをネガ型フォト
レジストとして現像処理することを特徴とする特許請求
の範囲第１項に記載のＯ−ナフトキノンジアジド系フォ
トレジスト現像法。[Claims] 1. O-
In the O-naphthoquinone diazide photoresist development method, in which a naphthoquinone diazide photoresist is applied, exposed using a predetermined exposure mask, and then developed, an O-naphthoquinone diazide photoresist is applied using a developer containing formamide and ethanol. An O-naphthoquinone diazide photoresist development method characterized by developing a photoresist. 2 The developing solution contains 80% to 100% by volume of formamide, 0 to 20% by volume of ethanol, and 0 to 20% of water.
% by volume, and the O-naphthoquinonediazide photoresist is developed as a positive photoresist using the developing solution. Law. 3 The developer solution contains 30% to 70% of formamide, 10% to 40% of ethanol, and 2% of water.
O-
The O-naphthoquinonediazide photoresist developing method according to claim 1, wherein the naphthoquinonediazide photoresist is developed as a negative photoresist.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53116370A JPS6051695B2 (en) | 1978-09-21 | 1978-09-21 | O-naphthoquinone diazide photoresist development method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53116370A JPS6051695B2 (en) | 1978-09-21 | 1978-09-21 | O-naphthoquinone diazide photoresist development method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5543537A JPS5543537A (en) | 1980-03-27 |
| JPS6051695B2 true JPS6051695B2 (en) | 1985-11-15 |
Family
ID=14685286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP53116370A Expired JPS6051695B2 (en) | 1978-09-21 | 1978-09-21 | O-naphthoquinone diazide photoresist development method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6051695B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6055630A (en) * | 1983-09-06 | 1985-03-30 | Oki Electric Ind Co Ltd | Method for forming resist pattern |
-
1978
- 1978-09-21 JP JP53116370A patent/JPS6051695B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5543537A (en) | 1980-03-27 |
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