JPH02297555A - Positive type photoresist developing solution - Google Patents
Positive type photoresist developing solutionInfo
- Publication number
- JPH02297555A JPH02297555A JP63262687A JP26268788A JPH02297555A JP H02297555 A JPH02297555 A JP H02297555A JP 63262687 A JP63262687 A JP 63262687A JP 26268788 A JP26268788 A JP 26268788A JP H02297555 A JPH02297555 A JP H02297555A
- Authority
- JP
- Japan
- Prior art keywords
- soln
- resist
- quaternary ammonium
- positive type
- hydrazine
- 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.)
- Granted
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 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 abstract description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- -1 naphthoquinone diazide compound Chemical class 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- IJRVQAXSAHHCNH-UHFFFAOYSA-M butyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(C)C IJRVQAXSAHHCNH-UHFFFAOYSA-M 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はポジ型フォトレジスト現像液に関し、さらに詳
しくは水酸化第四級アンモニウム水溶液にヒドラジンを
含有したフォトレジスト現像液に係り、特に高解像度で
微細パターンの形成が可能で、パターン寸法のバラツキ
も少なく優れたプロファイルを与えることができるポジ
型レジスト現像液であり、半導体集積回路などの製造に
有用なものである。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a positive photoresist developer, and more particularly to a photoresist developer containing hydrazine in an aqueous solution of quaternary ammonium hydroxide. It is a positive resist developer that can form fine patterns with less variation in pattern dimensions and can provide an excellent profile, making it useful for manufacturing semiconductor integrated circuits and the like.
［従来技術およびその問題点］
近年の電子工業の発展は著しく、最近の半導体集積回路
は超ＬＳＩに代表されるように高集積化及びそれに伴う
回路を描画する際の最少線幅も次第に微細化しレジスト
パターンを精度良く形成することが強く要望されている
。 上記要求に応えることが出来るのはポジ型レジスト
であり、これは従来使用されてきたネガ型レジストより
解像度が優れているものである。 ポジ型レジストの代
表的なものとしてはベースであるアルカリ可溶性ノボラ
ック樹脂と光分解剤であるナフトキノンジアジド化合物
とをともに含むものである。[Prior art and its problems] The electronic industry has developed significantly in recent years, and recent semiconductor integrated circuits, as typified by VLSI, have become highly integrated, and the minimum line width for drawing circuits has also become progressively finer. There is a strong demand for forming resist patterns with high precision. A positive type resist can meet the above requirements, and has a higher resolution than the conventionally used negative type resist. A typical positive type resist contains both an alkali-soluble novolak resin as a base and a naphthoquinone diazide compound as a photodegrading agent.
このナフトキノンジアジド系のポジ型レジストの現像液
としてアルカリ水溶液が使用されるが半導体集積回路素
子を製造する場合には現像液に金属イオンを含有するア
ルカリ水溶液を用いることが好ましくないのは言うまで
もない。 そこで金属イオンを含まない有機アルカリの
現像液、例えば水酸化テトラメチルアンモニウム（ＩＢ
Ｍ ｒＴｅｃｈｎｉｃａｌ Ｄｉｓｃｌｏｓｕｒｅ
Ｂｕｌｅｔｔｉｎ Ｊ第１３巻、第７号、第２００９ペ
ージ、１９７０年）やコリン（米国特許４゜２３９、６
６１号）等の水溶液が一般的に使用される。Although an alkaline aqueous solution is used as a developer for this naphthoquinonediazide-based positive resist, it goes without saying that it is not preferable to use an alkaline aqueous solution containing metal ions as a developer when manufacturing semiconductor integrated circuit elements. Therefore, an organic alkaline developer containing no metal ions, such as tetramethylammonium hydroxide (IB
M rTechnical Disclosure
Bulletin J Vol. 13, No. 7, Page 2009, 1970) and Colin (U.S. Pat. No. 4,239,6
Aqueous solutions such as No. 61) are generally used.
しかし水酸化テトラメチルアンモニウムあるいはコリン
等の現像液を用い線幅が微細なパターンを描画する場合
にはレジストプロファイル及び寸法制御精度が極端に低
下する。このためレジスト感度を上げるために現像液の
アルカリＳ度を上げたり、現像液温度を上げたり、ある
いは現像時間を長くしたりするが所謂スループットに対
する十分な効果を上げることは出来ない。 またこの他
に解像度を向上させるための改良技術として水酸化第四
級アンモニウム水溶液に種々の界面活性剤、有機化合物
を添加したものが提案されている。However, when drawing a pattern with a fine line width using a developer such as tetramethylammonium hydroxide or choline, the accuracy of resist profile and dimension control is extremely reduced. For this reason, in order to increase the resist sensitivity, the alkaline S degree of the developer is increased, the developer temperature is increased, or the development time is lengthened, but it is not possible to achieve a sufficient effect on so-called throughput. In addition, as an improved technique for improving the resolution, a technique in which various surfactants and organic compounds are added to an aqueous solution of quaternary ammonium hydroxide has been proposed.
界面活性剤を添加したものとしては、たとえば、特開昭
５８−９１４３号、特開昭６１−７０５５１号、特開昭
６１−１５１５３７号、特開昭６１−１６７４８号、特
開昭６１−２３２４５３号、特開昭６１−２３２４５４
号、特開昭６２−３２４５２号、特開昭６２−３２４５
４号、特開昭６２−４７１２５号などがあり、界面活性
剤とさらにアルコール、炭化水素などの他の有機化合物
を添加したものとしてはたとえば、特開昭６２−２３２
４５３号、特開昭５８−５７１２８号、などがあり、そ
の他に種々の有機化合物姿添加したものもあり、たとえ
ば、特開昭６０−２４１０５号、特開昭６２−３８７５
５号、特開昭６２−５７１６２号、特開昭６２−６７５
３５号など種々のものが数多く提案されている。しかし
ながらこれらのものでもそれぞれ一長一短があり、微細
線幅のリソグラフィーにおいては解像度や寸法精度等に
ついて必ずしも満足すべきものとは言い難い。Examples of those containing a surfactant include JP-A-58-9143, JP-A-61-70551, JP-A-61-151537, JP-A-61-16748, and JP-A-61-232453. No., Japanese Patent Publication No. 61-232454
No., JP-A-62-32452, JP-A-62-3245
4, JP-A No. 62-47125, etc., and examples of products containing surfactants and other organic compounds such as alcohols and hydrocarbons include JP-A No. 62-232.
453, JP-A No. 58-57128, etc., and there are also those in which various organic compounds are added, for example, JP-A-60-24105, JP-A-62-3875.
No. 5, JP-A-62-57162, JP-A-62-675
Many different types have been proposed, such as No. 35. However, each of these has advantages and disadvantages, and it is difficult to say that they are necessarily satisfactory in terms of resolution, dimensional accuracy, etc. in lithography of fine line widths.
本発明は、高解像度であって、優れたレジストプロファ
イルが得られるとともに、パターン寸法のバラツキが小
さい微細パターンの形成が行い得るポジ型フォトレジス
ト現像液を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a positive photoresist developer capable of forming fine patterns with high resolution and excellent resist profiles, and with small variations in pattern dimensions.
［問題点を解決するための手段］
本発明者らは、上記の点に鑑み鋭意研究の結果有機アル
カリ水溶液である水酸化第四級アンモニウム水溶液にヒ
ドラジンを添加することによって微細パターンを精度良
く形成することの出来ることを見い出し本発明に到った
。[Means for Solving the Problems] In view of the above points, the present inventors have conducted extensive research and have succeeded in forming fine patterns with high accuracy by adding hydrazine to a quaternary ammonium hydroxide aqueous solution, which is an organic alkaline aqueous solution. We have discovered what can be done and have arrived at the present invention.
すなわち本発明は一般式（Ｉ）
［Ｒ，Ｒ２Ｒ，Ｒ，Ｎ］＋・ＯＨ−（Ｉ）（ただしＲ，
−Ｒ，は同一でも異なっていてもよく、炭素数１〜１０
のアルキル基または炭素数２〜１０のアーリル基を表わ
す）で示される水酸化第四級アンモニウムの水溶液にヒ
ドラジンを含有させてなるポジ型レジスト現像液に関す
る。That is, the present invention provides general formula (I) [R,R2R,R,N]+.OH-(I) (wherein R,
-R, may be the same or different, and have 1 to 10 carbon atoms
The present invention relates to a positive resist developer comprising hydrazine contained in an aqueous solution of quaternary ammonium hydroxide (representing an alkyl group or an aryl group having 2 to 10 carbon atoms).
上記一般式（Ｉ）で示される水酸化第四級アンモニウム
としては、水酸化テトラメチルアンモニウム、水酸化テ
トラエチルアンモニウム、水酸化トリメチルブチルアン
モニウム、水酸化トリメチルベンジルアンモニウム、水
酸化トリメチルフェニルアンモニウム等である。特に好
ましい水酸化第四級アンモニウムとしては水酸化テトラ
メチルアンモニウムである。Examples of the quaternary ammonium hydroxide represented by the above general formula (I) include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylbenzylammonium hydroxide, and trimethylphenylammonium hydroxide. A particularly preferred quaternary ammonium hydroxide is tetramethylammonium hydroxide.
本発明に使用される水酸化第四級アンモニウムの水溶液
濃度は０．５〜ｌＱｗｔ％であり好ましくは１〜６ ｗ
ｔ％である。The aqueous solution concentration of quaternary ammonium hydroxide used in the present invention is 0.5 to 1Qwt%, preferably 1 to 6w.
t%.
本発明において、ヒドラジンは一般的には５０から５０
００ ｐｐｍの範囲で、通常は１０（１〜１５００ ｐ
ｐｍの範囲で使用されるが、好適には２５０〜１ｏｏｏ
ｐｐｍである。５０ｐｐｍ以下では充分な効果が発揮
されず、１だ５０００ ｐｐｍを超える多量では露光部
と非露光部との選択溶解性が著しく悪くなり現像後のレ
ジスト形状が悪化して所望のレジストパターンが得られ
難い。In the present invention, hydrazine is generally 50 to 50
00 ppm, usually 10 (1-1500 ppm)
It is used in the range of pm, preferably 250 to 1ooo.
It is ppm. If the amount is less than 50 ppm, a sufficient effect will not be exhibited, and if the amount exceeds 1 or 5,000 ppm, the selective solubility between exposed and non-exposed areas will be extremely poor, and the resist shape after development will deteriorate, making it impossible to obtain the desired resist pattern. hard.
本発明の現像液の対象となるポジ型レジストとしては特
に限定されるものではないが、たとえばｍ−タレゾール
ノボラック樹脂のようなアルカリ可溶性ノボラック樹脂
とナフトキノンジアジド化合物とを構成成分として含む
ものであればよい。The positive resist to which the developer of the present invention is applied is not particularly limited, but may include, for example, a resist containing an alkali-soluble novolac resin such as m-talesol novolac resin and a naphthoquinonediazide compound as a constituent component. Bye.
次に本発明の実施例につき説明する。Next, examples of the present invention will be described.
［実施例］
現像液として水酸化テトラメチルアンモニウム（ＴＭＡ
Ｈ）の２．３８重量％水溶液に、表に示すようにヒドラ
ジンを加えた現像液を調製した。[Example] Tetramethylammonium hydroxide (TMA
A developing solution was prepared by adding hydrazine to a 2.38% by weight aqueous solution of H) as shown in the table.
なお、比較としてヒドラジンを加えないものおよび添加
量の少ないものを調整し試験に供した。For comparison, samples without and with a small amount of hydrazine added were prepared and tested.
３インチシリコンウェハーにアルカリ可溶性ノボラック
樹脂とナフトキノンジ了シト化合物を構成成分として含
む０ＦＰＲ−８００（東京応化工業社製）をスピナーに
より膜厚１．２μｍになるように塗布し、クリーンオー
ブン中８０℃で２０分ブレベークし密着露光装置を用い
テストチャートレチクルを介して露光処理を行なった。0FPR-800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) containing an alkali-soluble novolac resin and a naphthoquinone diphosphate compound as constituent components was applied to a 3-inch silicon wafer using a spinner to a thickness of 1.2 μm, and the film was heated at 80°C in a clean oven. After baking for 20 minutes, exposure processing was performed through a test chart reticle using a contact exposure device.
次いで表に示した現像液を用いて浸せき法で２３℃、６
０秒の現像処理を行なった後、超純水によるリンス処理
を行ない乾燥した。その後非露光部の膜厚減少速度、現
像後のレジストパターンの断面形状のテーパー角度、及
びスカムの状態を測定または観察した。なおレジストテ
ーパ角度は現像したレジスト膜の断面形状を走査型電子
顕微鏡で観察、測定し、スカムの状態は現像後の基板の
状態を走査型電子顕微鏡で観察した。Then, using the developer shown in the table, it was immersed at 23°C for 60 minutes.
After developing for 0 seconds, rinsing with ultrapure water and drying was performed. Thereafter, the rate of film thickness reduction in the non-exposed area, the taper angle of the cross-sectional shape of the resist pattern after development, and the state of scum were measured or observed. The resist taper angle was determined by observing and measuring the cross-sectional shape of the developed resist film using a scanning electron microscope, and the state of the scum was determined by observing the state of the substrate after development using a scanning electron microscope.
［発明の効果］
本発明の現像液は、高解像度で微細パターンの形成が可
能であり、パターン寸法のバラツキが小さい優れたプロ
ファイルを与えることができる他、スカムも認められな
いものである。[Effects of the Invention] The developer of the present invention is capable of forming fine patterns with high resolution, can provide an excellent profile with small variations in pattern dimensions, and is free from scum.
特許出願人 三菱瓦斯化学株式会社 代理人 弁理士 小 堀 貞 文 手続補正書（自発） 平成１年り月／８日Patent applicant: Mitsubishi Gas Chemical Co., Ltd. Agent: Patent Attorney Sadafumi Kohori Procedural amendment (voluntary) 1999 month/8th
Claims (1)
しＲ＿１〜Ｒ＿４は同一でも異なっていてもよく、炭素
数１〜１０のアルキル基または炭素数２〜１０のアーリ
ル基を表わす）で示される水酸化第四級アンモニウム水
溶液に、ヒドラジンを含有させてなるポジ型フォトレジ
スト現像液。[Claims] General formula [R_1R_2R_3R_4N]^+・OH^- (However, R_1 to R_4 may be the same or different and represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 2 to 10 carbon atoms. ) A positive photoresist developer comprising a quaternary ammonium hydroxide aqueous solution containing hydrazine.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63262687A JP2712397B2 (en) | 1988-10-20 | 1988-10-20 | Positive photoresist developer |
| DE68923844T DE68923844T2 (en) | 1988-10-20 | 1989-10-13 | Developer for positive photoresists. |
| EP89119048A EP0364895B1 (en) | 1988-10-20 | 1989-10-13 | Positive type photoresist developer |
| KR1019890015187A KR960003909B1 (en) | 1988-10-20 | 1989-10-20 | Positive type photoresist developer and the preparation thereof |
| US07/857,076 US5175078A (en) | 1988-10-20 | 1992-03-18 | Positive type photoresist developer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63262687A JP2712397B2 (en) | 1988-10-20 | 1988-10-20 | Positive photoresist developer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02297555A true JPH02297555A (en) | 1990-12-10 |
| JP2712397B2 JP2712397B2 (en) | 1998-02-10 |
Family
ID=17379199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63262687A Expired - Lifetime JP2712397B2 (en) | 1988-10-20 | 1988-10-20 | Positive photoresist developer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2712397B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6385542A (en) * | 1986-09-29 | 1988-04-16 | Konica Corp | Developing solution composition for photosensitive material and developing method |
| JPS63200154A (en) * | 1987-02-16 | 1988-08-18 | Konica Corp | Developing solution for photosensitive planographic printing plate which can commonly process negative type and positive type |
-
1988
- 1988-10-20 JP JP63262687A patent/JP2712397B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6385542A (en) * | 1986-09-29 | 1988-04-16 | Konica Corp | Developing solution composition for photosensitive material and developing method |
| JPS63200154A (en) * | 1987-02-16 | 1988-08-18 | Konica Corp | Developing solution for photosensitive planographic printing plate which can commonly process negative type and positive type |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2712397B2 (en) | 1998-02-10 |
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