JPH01296246A - Method for developing photosensitive material - Google Patents
Method for developing photosensitive materialInfo
- Publication number
- JPH01296246A JPH01296246A JP12755888A JP12755888A JPH01296246A JP H01296246 A JPH01296246 A JP H01296246A JP 12755888 A JP12755888 A JP 12755888A JP 12755888 A JP12755888 A JP 12755888A JP H01296246 A JPH01296246 A JP H01296246A
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive material
- water
- rinsing
- developing
- propanol
- 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
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000149 argon plasma sintering Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 abstract description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 108010010803 Gelatin Proteins 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract description 3
- 229920000159 gelatin Polymers 0.000 abstract description 3
- 239000008273 gelatin Substances 0.000 abstract description 3
- 235000019322 gelatine Nutrition 0.000 abstract description 3
- 235000011852 gelatine desserts Nutrition 0.000 abstract description 3
- 108090000623 proteins and genes Proteins 0.000 abstract description 3
- 102000004169 proteins and genes Human genes 0.000 abstract description 3
- 229920001059 synthetic polymer Polymers 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 abstract 1
- -1 e.g. Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 6
- 206010034972 Photosensitivity reaction Diseases 0.000 description 5
- 239000007921 spray Substances 0.000 description 4
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000008049 diazo compounds Chemical class 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PLYDMIIYRWUYBP-UHFFFAOYSA-N ethyl 4-[[2-chloro-4-[3-chloro-4-[(3-ethoxycarbonyl-5-oxo-1-phenyl-4h-pyrazol-4-yl)diazenyl]phenyl]phenyl]diazenyl]-5-oxo-1-phenyl-4h-pyrazole-3-carboxylate Chemical compound CCOC(=O)C1=NN(C=2C=CC=CC=2)C(=O)C1N=NC(C(=C1)Cl)=CC=C1C(C=C1Cl)=CC=C1N=NC(C(=N1)C(=O)OCC)C(=O)N1C1=CC=CC=C1 PLYDMIIYRWUYBP-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000007 visual 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〕
本発明は感材の現像方法に係わり、特にフォトリソ“グ
ラフィー法の現像方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for developing a sensitive material, and particularly to a method for developing a photolithographic method.
従来、水溶性感光材料としては、ゼラチン、カゼイン、
グリユー等の天然蛋白質、或いはポリビニルアルコール
等の合成高分子に対し重クロム酸アンモニウム、ジアゾ
化合物などで感光性を付与したものが広く使用されてい
る。これらの水溶性感光材料は、いずれもネガ型の感光
性を有しており、光とくに紫外線を適当なマスクを介し
て照射した後に、水または温水を用いたデイツプ現像、
フロー現像およびスプレー現像等の現像方法を用いれば
、水に対する溶解性の違いから容易に現像を行うことが
できる。Conventionally, water-soluble photosensitive materials include gelatin, casein,
Natural proteins such as GRIEU, or synthetic polymers such as polyvinyl alcohol, which are made photosensitized with ammonium dichromate, diazo compounds, etc., are widely used. All of these water-soluble photosensitive materials have negative photosensitivity, and after being irradiated with light, especially ultraviolet rays, through an appropriate mask, deep development using water or warm water,
If a developing method such as flow development or spray development is used, development can be easily performed due to the difference in solubility in water.
ところで、最近、上述の水溶性感光材料に対して機能性
の材料を添加することにより、新たな機能を付加しよう
とする試みが行われている。これらの機能性の材料とし
て、電気的性質、磁気的性質、光学的性質等の目的に応
じ種々の物質が検討されているが、その多くは透明性が
十分でなく光を散乱させる性質を有している。このため
、露光に用いた紫外線の一部は、添加した機能性の材料
によって反射、散乱或いは吸収されてしまうので、感材
感度の低下或いはエツジのシャープネスが低下するとい
う問題を生じている。Incidentally, recently, attempts have been made to add new functions to the above-mentioned water-soluble photosensitive materials by adding functional materials. Various materials are being considered as materials for these functionalities depending on their purpose, such as electrical properties, magnetic properties, optical properties, etc., but most of them are not sufficiently transparent and have the property of scattering light. are doing. For this reason, a part of the ultraviolet rays used for exposure is reflected, scattered or absorbed by the added functional material, resulting in problems such as a decrease in the sensitivity of the sensitive material or a decrease in edge sharpness.
本発明は上記問題を解決するものであって、水溶性感光
材料へのａ化性材料の添加を可能とし、かつ、より微細
なパターンを形成可能にする感材の現像方法を提供する
ことを目的とする。The present invention solves the above-mentioned problems, and aims to provide a method for developing a light-sensitive material that enables the addition of an a-forming material to a water-soluble light-sensitive material and also enables the formation of finer patterns. purpose.
上記課題を解決するために本発明は、水溶性感光材ｒ）
に対して、水若しくは温水により現像を行った後に、メ
タノール、エタノール、２−プロパノール等のアルコー
ル類或いはアセトン等の相溶性有機溶剤によりリンスを
行うことを特徴とし、さらに、現像工程とリンス工程と
の間にリンスに用いる相溶性有機溶剤の水溶液によるリ
ンス工程を設けることを特徴とする。In order to solve the above problems, the present invention provides a water-soluble photosensitive material r)
However, after developing with water or hot water, rinsing is performed with an alcohol such as methanol, ethanol, 2-propanol, or a compatible organic solvent such as acetone, and furthermore, a developing step and a rinsing step are performed. A rinsing step using an aqueous solution of a compatible organic solvent used for rinsing is provided in between.
本発明において効果が得られる水溶性感光材料は、ゼラ
チン、カゼイン、グリユー等の天然蛋白質、°或いはポ
リビニルアルコール等の合成高分子に対し重クロム酸ア
ンモニウム、ジアゾ化合物などで感光性を付与したもの
であれば特に限定されない。本発明の効果は、これら水
溶性感光材料単体であってもｒ１１１認できるが、その
効果が顕著であるのは感光材料中に種々の光散乱性物質
が含まれている場合である。この光散乱性物質としては
、金属、無機化合物、有機化合物のいずれであってもか
まわないが、その粒径は大き過ぎると光散乱の程度が強
すぎて感光性が失われるため、通常数μｍ以下、望まし
くは１μｍ以下のものが一般に使用されている。Water-soluble photosensitive materials that can be used effectively in the present invention include natural proteins such as gelatin, casein, and green, or synthetic polymers such as polyvinyl alcohol, which have been made photosensitized with ammonium dichromate, diazo compounds, etc. If so, there are no particular limitations. Although the effects of the present invention can be seen even with these water-soluble photosensitive materials alone, the effects are most noticeable when the photosensitive materials contain various light-scattering substances. This light-scattering substance may be a metal, an inorganic compound, or an organic compound, but if the particle size is too large, the degree of light scattering will be too strong and photosensitivity will be lost, so it is usually several μm. Hereinafter, those having a diameter of preferably 1 μm or less are generally used.
上記水溶性感光材料は、通常のフォトリソグラフィーの
工程、すなわち■塗布、■プレベータ、■露光、■現像
、■ポストヘークの各工程によっても製版が可能である
が、光散乱性の影響により、第り図に示すようにエツジ
形状は極端に悪化する場合がある０図は（ａ）に示すフ
ォトマスクのパターンを介して露光した感材の画像パタ
ーンが（ｂ）に示すように、エツジ形状が悪化している
ことを示している。The above-mentioned water-soluble photosensitive materials can be made into plates by the usual photolithography processes, namely, ■coating, ■prebeta, ■exposure, ■development, and ■posthake, but due to the influence of light scattering, As shown in the figure, the edge shape may be extremely deteriorated. In the figure, the image pattern of the photosensitive material exposed through the photomask pattern shown in (a) has a deteriorated edge shape, as shown in (b). It shows that you are doing it.
本発明においては前記■現像工程の後に、メタノール、
エタノール、２−プロパノール等のアルコール類或いは
アセトン等の相溶性有機溶剤によるリンス工程を行うこ
とを特徴とする。すなわち、従来と同様の現像工程、す
なわち水または温水を用いたデイツプ現像、フロー現像
およびスプレー現像に引き続き、メタノール、エタノー
ル、２−プロパノール等のアルコール類或いはアセトン
等の相溶性有１１１１ ’ｔ８剤によるリンス工程を行
う。リンスの方法としては、現像同様にデイツプ、フロ
ー、スプレーのいずれであってもよい。さらに、現像工
程とリンス工程の間に感材が乾燥してしまうと、本発明
の効果が得られないため、現像後は乾燥工程を経ずに直
ちにリンス工程へ移行することが必要である。望ましく
は、現像工程とリンス工程との間に、リンス工程で使用
する溶剤と同一の溶剤の水溶液からなる中間リンスを設
ける。さらに望ましくは、前記中間リンス工程の段数を
増して、現像液である水からリンス工程で使用する溶剤
まで連続的に濃度が変化する中間リンスを設けることで
ある。上記の方法によりエツジ形状が極端に悪かった感
光材料であっても、エツジ形状を改善することができる
ようになった。In the present invention, methanol,
It is characterized by performing a rinsing step using alcohols such as ethanol and 2-propanol, or compatible organic solvents such as acetone. That is, following the conventional development process, that is, dip development, flow development, and spray development using water or hot water, a compatible 1111't8 agent such as alcohols such as methanol, ethanol, and 2-propanol, or acetone is used. Perform the rinsing process. The rinsing method may be dip, flow, or spray, similar to development. Furthermore, if the photosensitive material dries between the development step and the rinsing step, the effects of the present invention cannot be obtained, so it is necessary to immediately proceed to the rinsing step after development without passing through the drying step. Desirably, an intermediate rinse consisting of an aqueous solution of the same solvent as that used in the rinsing step is provided between the developing step and the rinsing step. More desirably, the number of stages of the intermediate rinsing step is increased to provide an intermediate rinsing in which the concentration of the solvent used in the rinsing step changes continuously from water as a developer. By the above method, it has become possible to improve the edge shape of a photosensitive material even if the edge shape is extremely poor.
以下、本発明の感材の現像方法を実施例に基づき具体的
に説明する。Hereinafter, the method for developing a photosensitive material of the present invention will be specifically explained based on Examples.
（実施例１〕
水溶性感光材料として、ポリビニルアルコールに重クロ
ム酸アンモニウムで感光性を付与したものを用い、この
感光材料に粒径１μｍ以下の顔料を５重量％添加し、着
色感光材を調製した。［１ｎ料の種類は特に限定される
ものではないが、ここではピラゾロンレッドを使用した
。(Example 1) A colored photosensitive material was prepared by adding 5% by weight of a pigment with a particle size of 1 μm or less to the water-soluble photosensitive material using polyvinyl alcohol made photosensitized with ammonium dichromate. [The type of 1n material is not particularly limited, but pyrazolone red was used here.
次に、上記顔料式りの感光材料をスピンコ−１・法によ
り１．０μｍの１１２厚になるようにパイレンクスガラ
ス上に塗布後、７０＠Ｃの循環式オーブン中で３０分間
加熱することによりプレベータを行った。Next, the above pigment-based photosensitive material was coated on Pyrex glass to a thickness of 1.0 μm using the spinco-1 method, and then heated in a circulating oven at 70 C for 30 minutes. I did a pre-beta.
露光には、プロキシギャップを３０μｍに設定したプロ
キシ露光装置を使用し、１００μｍのライン・スペース
のパターンを有するフォトマスクを介して適正な露光量
の紫外線を照射した。For exposure, a proxy exposure device with a proxy gap set to 30 μm was used, and an appropriate amount of ultraviolet rays was irradiated through a photomask having a line-space pattern of 100 μm.
現像は、先ず、水によるスプレー現像を６０秒間行った
後に、２−プロパノールを３０秒間スプレーにより吹き
付はリンスを行った。その後、スピンドライにより乾燥
したところ顔料を添加していない感光材料の場合と同程
度の良好な画素が得られた。これに対して、比較のため
に２−プロパノールのリンス処理を行わなかったもので
は、画像パターンのエツジが極端に変形しており、２−
プロパノールによるリンスが画質を改善することがｉｎ
認された。In the development, first, spray development with water was performed for 60 seconds, and then 2-propanol was sprayed for 30 seconds, followed by rinsing. Thereafter, when it was dried by spin drying, good pixels were obtained which were comparable to those of the photosensitive material to which no pigment was added. On the other hand, when rinsing with 2-propanol was not performed for comparison, the edges of the image pattern were extremely deformed, and 2-propanol was not rinsed.
Rinsing with propanol has been shown to improve image quality.
It has been certified.
〔実施例２〕
上記実施例と同様に、顔料を添加した水溶性感光材料を
用いて、塗布、プレベータ、露光、現像を行った後に、
５０％２−プロパノール水混合液を１５秒間スプレーを
用いた中間リンスを行い、この後、１００％２−プロパ
ノールによる本リンスを行った。この中間リンスを行う
ことにより、スピンドライ時発生する乾燥しみは大幅に
減少し、目視外観における品位が向上した。なお、中間
リンスを行うことによりエツジの改善効果の変化は認め
られなかった。[Example 2] In the same manner as in the above example, a water-soluble photosensitive material to which pigments were added was used, and after coating, prebeta, exposure, and development,
An intermediate rinse was performed by spraying a 50% 2-propanol/water mixture for 15 seconds, followed by a main rinse using 100% 2-propanol. By performing this intermediate rinsing, the dry stains that occur during spin drying were significantly reduced, and the visual appearance was improved. Note that no change in the edge improvement effect was observed by performing an intermediate rinse.
以上のように本発明によれば、従来、充分な解像性が得
られなかったために実用化が困難であった水溶性感光材
料への機能性材料の添加が可能となり、或いは、従来法
で形成したパターンをより微細なパターンに形成するこ
とができる。As described above, according to the present invention, it is now possible to add functional materials to water-soluble photosensitive materials, which have conventionally been difficult to put into practical use because sufficient resolution could not be obtained, or The formed pattern can be formed into a finer pattern.
第１図は従来の感材の現像方法によるパターンにおける
エツジの変形を説明するための図である。
出 願 人 大日本印刷株式会社
代理人弁理士 白 井 博 樹（外４名）■
１−Ｌ
（ａ）フォトン入り
（ｂ）慰抛白像FIG. 1 is a diagram for explaining the deformation of edges in a pattern produced by a conventional photosensitive material developing method. Applicant Dai Nippon Printing Co., Ltd. Representative Patent Attorney Hiroki Shirai (4 others) ■ 1-L (a) Contains photon (b) Statue of white oppressor
Claims (3)
現像を行った後に、メタノール、エタノール、２−プロ
パノール等のアルコール類或いはアセトン等の相溶性有
機溶剤によりリンスを行うことを特徴とする感材の現像
方法。(1) After developing a water-soluble photosensitive material with water or warm water, rinsing is performed with an alcohol such as methanol, ethanol, 2-propanol, or a compatible organic solvent such as acetone. How to develop the material.
溶性有機溶剤の水溶液によるリンス工程を設けることを
特徴とする請求項１記載の感材の現像方法。(2) The method for developing a photosensitive material according to claim 1, further comprising a rinsing step using an aqueous solution of a compatible organic solvent used for rinsing between the developing step and the rinsing step.
含むことを特徴とする請求項１または請求項２記載の感
材の現像方法。(3) The method for developing a photosensitive material according to claim 1 or 2, wherein the water-soluble photosensitive material contains a light-scattering substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12755888A JPH01296246A (en) | 1988-05-24 | 1988-05-24 | Method for developing photosensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12755888A JPH01296246A (en) | 1988-05-24 | 1988-05-24 | Method for developing photosensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01296246A true JPH01296246A (en) | 1989-11-29 |
Family
ID=14962992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12755888A Pending JPH01296246A (en) | 1988-05-24 | 1988-05-24 | Method for developing photosensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01296246A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0851305A1 (en) * | 1996-12-26 | 1998-07-01 | Clariant International Ltd. | Rinsing and stripping process for lithography |
| CN110673440A (en) * | 2019-10-12 | 2020-01-10 | 中国科学院理化技术研究所 | Photolithographically patternable graphene/native protein compositions, methods of making, and patterning the same |
-
1988
- 1988-05-24 JP JP12755888A patent/JPH01296246A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0851305A1 (en) * | 1996-12-26 | 1998-07-01 | Clariant International Ltd. | Rinsing and stripping process for lithography |
| CN110673440A (en) * | 2019-10-12 | 2020-01-10 | 中国科学院理化技术研究所 | Photolithographically patternable graphene/native protein compositions, methods of making, and patterning the same |
| CN110673440B (en) * | 2019-10-12 | 2023-11-28 | 中国科学院理化技术研究所 | Lithographically patternable graphene/native protein compositions, methods of making and patterning thereof |
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