JPH07196755A - Resist material, its production and image forming method - Google Patents
Resist material, its production and image forming methodInfo
- Publication number
- JPH07196755A JPH07196755A JP5350920A JP35092093A JPH07196755A JP H07196755 A JPH07196755 A JP H07196755A JP 5350920 A JP5350920 A JP 5350920A JP 35092093 A JP35092093 A JP 35092093A JP H07196755 A JPH07196755 A JP H07196755A
- Authority
- JP
- Japan
- Prior art keywords
- resist
- resin
- novolac resin
- formylated
- added
- 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
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】 本発明は、半導体、マイクロマ
シンなどの微細な加工・製造に利用する新規なレジスト
材料に関するものである。TECHNICAL FIELD The present invention relates to a novel resist material used for fine processing / manufacturing of semiconductors, micromachines and the like.
【０００２】[0002]
【従来の技術】レジスト材料は、半導体製造やマイクロ
マシンなどのマイクロリソグラフィー（微細加工技術）
に利用され、シリコンウエハー基板表面の上に画像形成
がおこなわれた後、エッチング工程において基板表面を
被覆保護する目的で使用される。このレジスト画像の形
成方法にはポジ型とネガ型がある。ポジ型レジストは、
シリコンウエハー等の基板の表面をレジスト膜で覆って
被覆基板を製造して、その上をフォトマスクで覆って紫
外線等の光を照射すれば、現像液によって光の当たった
部分が溶解除去される。一方、光の当たらなかった部分
は溶解せずに残存して所望のレジスト画像が基板上に形
成される。それとは逆にネガ型レジストは、未照射部分
のレジストが溶解して、照射された部分の樹脂が残存す
るレジストを指す。2. Description of the Related Art Resist materials are microlithography (microfabrication technology) for semiconductor manufacturing and micromachines.
It is used for the purpose of coating and protecting the surface of a substrate in an etching process after an image is formed on the surface of a silicon wafer substrate. This resist image forming method includes a positive type and a negative type. Positive resist
When a coated substrate is manufactured by covering the surface of a substrate such as a silicon wafer with a resist film, and covering it with a photomask and irradiating it with light such as ultraviolet rays, the exposed portion is dissolved and removed by the developing solution. . On the other hand, the portion not exposed to light remains without being dissolved and a desired resist image is formed on the substrate. On the contrary, the negative resist refers to a resist in which the resist in the unirradiated portion is dissolved and the resin in the irradiated portion remains.
【０００３】半導体の製造工程においては、ポジ型レジ
ストを必要とする工程とネガ型レジストを必要とする工
程とがあり、両工程を必ず必要としている。実際には、
必要に応じて別々の材料を使用しており、ネガ、ポジ両
方を兼ね備えた材料は市販されていないのが現状であ
る。In a semiconductor manufacturing process, there are a process requiring a positive resist and a process requiring a negative resist, and both processes are necessarily required. actually,
Separate materials are used as needed, and the material having both negative and positive properties is not commercially available at present.
【０００４】また、レジスト画像は、腐食工程を終了し
た後に次の工程へ廻すため、一旦、はぎ取らねばならな
い。現在、ネガ型のレジストにおいては、この剥膜工程
において有機溶剤が使用されているが、これは作業環境
に毒性の強い溶剤蒸気が放出され、問題がある。Also, the resist image must be once stripped off because it is passed to the next step after the corrosion step is completed. Currently, in a negative type resist, an organic solvent is used in this film peeling process, but this has a problem that solvent vapor which is highly toxic to the working environment is released.
【０００５】最近、要求される画像の線幅がサブミクロ
ンになるにしたがって照射に用いる光は、波長が３６０
ｎｍの紫外線（以下ＵＶと称する）からより短い波長の
デイープＵＶ（３００ｎｍ以下）へ変わってきている。Recently, as the required line width of an image becomes submicron, the light used for irradiation has a wavelength of 360.
nm of ultraviolet rays has been changed to a shorter wavelength (hereinafter referred to as UV) de Lee-loop UV (300nm or less).
【０００６】膨潤しやすい材料は画像の崩れをおこすた
め、画像形成材料には適しない。しかしながら、フェノ
ールノボラック樹脂は、現像液に対して膨潤し難い材料
であると言われているし、フェノールノボラック樹脂の
ような芳香族ポリマーはドライエッチング性も高いこと
が知られている。A material that easily swells causes a collapse of an image and is not suitable as an image forming material. However, it is said that the phenol novolac resin is a material that does not easily swell in a developing solution, and an aromatic polymer such as the phenol novolac resin is known to have a high dry etching property.
【０００７】ホルミル化ｐ−ヒドロキシポリスチレンが
デイープＵＶで光分解を利用するレジストとして知られ
ているが、現像液の極性によってネガ型レジストにも、
ポジ型レジストにもなることが報告されている。[0007] While formylated p- hydroxy polystyrene is known as a resist utilizing photolysis in de Lee-loop UV, to a negative resist by the polarity of the developer,
It has been reported that it can also be used as a positive resist.
【０００８】[0008]
【発明が解決しようとしている課題】本発明に係るレジ
ストは、画像線幅のサブミクロン級の細線化に対応出来
ることを意図したデイープＵＶが利用可能な画像成形材
料を製造できることが望ましく、耐膨潤性や耐ドライエ
ッチング性も優れていることが望ましい。According to the invention you are trying to solve problems] The present invention resist, it is desirable to de Lee-loop UV intended to be able to correspond to thinning of the submicron image line width can be produced an image forming material available It is desirable that the swelling resistance and dry etching resistance are also excellent.
【０００９】また、マイクロリソグラフィーの作業工程
において使用レジスト材料の系が単純になったり、工程
上の自由度が高くなって融通性が利くようになるために
１種類のレジスト材料でネガ画像、ポジ画像の両方の役
割を果たせることが望ましい。Further, in the working process of microlithography, the system of the resist material used is simplified, and the flexibility in the process is increased so that the flexibility is improved. It is desirable to be able to play both roles of the image.
【００１０】また、半導体の製造工程ではレジストの剥
膜工程を必要とするけれど、その際、有毒な蒸気を発生
する有機溶媒を使用せずに、安全な水性剥離液を使用で
きることが望ましい。Further, although a resist film stripping step is required in the semiconductor manufacturing process, it is desirable that a safe aqueous stripping solution can be used without using an organic solvent which produces toxic vapor.
【００１１】[0011]
【課題を解決する手段】上記課題を解決する方法として
以下のとおり 一般式[Means for Solving the Problems] As a method for solving the above problems, the following general formula is used.
【化２】 式中の Ｒ1：Ｈ：ｏ−ＣＨ3，ｍ−ＣＨ3，ｐ−Ｃ
Ｈ3：ｐ−Ｃ（ＣＨ3）3 ｎ ：２以上 で表されるホルミル化ノボラック樹脂を主成分とするレ
ジスト材料。[Chemical 2] R 1 : H: o-CH 3 , m-CH 3 , p-C in the formula
H 3: p-C (CH 3) 3 n: resist material mainly composed of formylated novolac resin represented by 2 or more.
【００１２】フェノールノボラック樹脂を有機溶媒に溶
解ないし分散し、触媒として３級アミンを添加し、ギ酸
と脱水剤の無水酢酸とを添加し、室温好ましくは２５℃
以下の攪拌下で反応させることを特徴とする上記ホルミ
ル化ノボラック樹脂を主成分とするレジスト材料を製造
する方法。A phenol novolac resin is dissolved or dispersed in an organic solvent, a tertiary amine is added as a catalyst, formic acid and acetic anhydride as a dehydrating agent are added, and the temperature is preferably 25 ° C.
A method for producing a resist material containing the above-mentioned formylated novolac resin as a main component, which is characterized in that the reaction is carried out under stirring.
【００１３】上記ホルミル化ノボラック樹脂を主成分と
するレジスト膜を基板上に形成させ、マスクを通してＵ
Ｖ照射装置から紫外線を照射し、極性の高いアルカリ性
水溶媒で現像するポジ型レジスト画像の形成方法。A resist film containing the above-mentioned formylated novolac resin as a main component is formed on a substrate, and U is passed through a mask.
A method of forming a positive resist image, which comprises irradiating ultraviolet rays from a V irradiator and developing with a highly polar alkaline water solvent.
【００１４】上記ホルミル化ノボラック樹脂を主成分と
し、上記と同様の操作をおこない、極性の低い有機溶媒
で現像するネガ型レジスト画像形成方法。A method for forming a negative resist image, which comprises the above-mentioned formylated novolak resin as a main component, and performs the same operation as described above, and develops with an organic solvent having a low polarity.
【００１５】[0015]
【具体的な構成・作用】本発明に係るレジストは、詳し
くは実施例でその合成方法を示すが、原料として側鎖に
水酸基を有するフェノールノボラック樹脂、例えばｎ−
フェノールノボラック樹脂、ｏ−クレゾールノボラック
樹脂、ｍ−クレゾールノボラック樹脂，ｐ−クレゾール
ノボラック樹脂、ｐ−ｔｅｒｔブチルフェノールノボラ
ック樹脂を用い、その水酸基のホルミル化反応によって
行われる。それには一つの方法として有機溶媒として特
に限定はしないが例えば、テトラヒドロフラン、アセト
ン、メチルエチルケトンに原料樹脂を溶解ないし分散さ
せる。次ぎに、触媒として３級アミン、特に限定はしな
いがピリジン、トリエチルアミン、トリメチルアミンを
添加し、更にぎ酸と脱水剤の無水酢酸とを添加する。温
度を室温好ましくは２５℃以下で攪拌しながら１日〜数
日間反応させることによって得られる。一般式[Specific Structure / Function] The resist according to the present invention will be described in detail in the examples of its synthesis method. As a raw material, a phenol novolac resin having a hydroxyl group in its side chain, for example, n-
Phenol novolac resin, o-cresol novolac resin, m-cresol novolac resin, p-cresol novolac resin and p-tert butylphenol novolac resin are used by the formylation reaction of their hydroxyl groups. As one method therefor, the organic solvent is not particularly limited, but for example, the raw material resin is dissolved or dispersed in tetrahydrofuran, acetone, or methyl ethyl ketone. Next, a tertiary amine as a catalyst, which is not particularly limited, pyridine, triethylamine, and trimethylamine is added, and formic acid and a dehydrating agent acetic anhydride are further added. It can be obtained by reacting at room temperature, preferably 25 ° C. or lower, with stirring for 1 day to several days. General formula
【化３】式中の Ｒ1：Ｈ：ｏ−ＣＨ3，ｍ−ＣＨ3，
ｐ−ＣＨ3：ｐ−Ｃ（ＣＨ3）3 ｎ ：２以上 で表されるように側鎖にホルミル基が導入される。いろ
いろな原料ノボラック樹脂を使用することによって得ら
れたホルミル化ノボラック樹脂の結果を表１に示す。Embedded image In the formula, R 1 : H: o-CH 3 , m-CH 3 ,
p-CH 3: p-C (CH 3) 3 n: formyl group on the side chain as represented by 2 or more is introduced. The results of the formylated novolak resins obtained by using various starting novolak resins are shown in Table 1.
【００１６】[0016]
【表１】 [Table 1]
【００１７】得られたホルミル化ノボラック樹脂は、い
ずれもエステル化率が１００モル％であり、そのうちホ
ルミル基は８３％以上含まれている。もし、このエステ
ル化率が低く、未反応フェノール水酸基が残っているな
らば、ホルミル化ノボラック樹脂の現像液溶解性に影響
を与え、ポジ型画像は得られないし、ネガ型においては
感度が数千ｍＪ／ｃｍ2以上になり、著しく低感度にな
り、完全エステル化することがレジスト材料を得るため
に不可欠の条件である。Each of the obtained formylated novolac resins has an esterification rate of 100 mol%, of which 83% or more of the formyl group is contained. If this esterification rate is low and unreacted phenolic hydroxyl groups remain, it will affect the solubility of the formylated novolak resin in the developing solution, a positive image cannot be obtained, and the sensitivity of the negative tone is several thousand. It is indispensable for obtaining a resist material that mJ / cm 2 or more, remarkably low sensitivity and complete esterification are obtained.
【００１８】また、そのほかのホルミル化の方法として
実施例でも示すが有機溶媒に溶解ないし分散させた後、
触媒の三級アミンを添加し、脱水剤としてクロロ炭酸エ
チルとぎ酸とを添加し、室温３０℃以下で数時間以上攪
拌する方法、あるいは、ぎ酸と脱水剤として濃硫酸とを
添加し、加熱・攪拌下で反応させることによってもホル
ミル化することが可能になる。As another method of formylation, which will be shown in Examples, after being dissolved or dispersed in an organic solvent,
A method in which a tertiary amine as a catalyst is added, ethyl chlorocarbonate and formic acid are added as a dehydrating agent, and the mixture is stirred at room temperature of 30 ° C. or lower for several hours or more, or formic acid and concentrated sulfuric acid as a dehydrating agent are added and heated. -Formylation can also be achieved by reacting with stirring.
【００１９】本発明に係るレジストの画像形成方法にお
いては、シリコン基板上のレジスト膜にマスクを当てて
紫外線を照射し、次ぎに適当な極性の溶液、例えばテト
ラメチルアンモニウムハイドロオキサイドの水溶液を好
ましくは１〜５％の濃度のものをはじめカ性ソーダー、
カ性カリ等の水溶液、アンモニア水等を現像液に用いれ
ば、照射部分の極性の高い樹脂は、未照射部分の樹脂よ
りも速く溶解する。現像時間を１分間に限定すれば結果
的に未照射部分の樹脂が未溶解のまま残ってポジ型の画
像が得られる。それに対してクロロホルム、塩化メチレ
ン、トリクロロエチレン、四塩化炭素、テトラクロロエ
タン、ｎ−ヘキサンのような比較的極性の低い溶媒１種
類または２種類以上の混合溶媒を現像液とすれば、前記
とは逆に未照射部分の極性の低い樹脂が照射部分よりも
速く溶解することによってネガ型画像が得られた。これ
らのネガ画像、ポジ画像を走査電子顕微鏡で観察すれ
ば、膨潤を起こすこと無く、鮮明に現像されていること
が認められた。In the method of forming a resist image according to the present invention, a resist film on a silicon substrate is exposed to ultraviolet rays by applying a mask, and then a solution of an appropriate polarity, for example, an aqueous solution of tetramethylammonium hydroxide is preferably used. 1 ~ 5% concentration of caustic soda,
When an aqueous solution of caustic potash or the like, ammonia water or the like is used as the developing solution, the resin having high polarity in the irradiated portion dissolves faster than the resin in the unirradiated portion. If the developing time is limited to 1 minute, as a result, the resin in the unirradiated portion remains undissolved and a positive image is obtained. On the other hand, if one or a mixture of two or more solvents having a relatively low polarity such as chloroform, methylene chloride, trichloroethylene, carbon tetrachloride, tetrachloroethane, n-hexane is used as the developing solution, the opposite is true. A negative image was obtained by dissolving the less polar resin in the unirradiated area faster than in the irradiated area. When these negative and positive images were observed with a scanning electron microscope, it was confirmed that they were clearly developed without causing swelling.
【００２０】[0020]
【実施例】次に、実施例によってこの発明をさらに具体
的に説明する。EXAMPLES Next, the present invention will be described more specifically by way of examples.
【００２１】実施例１ フェノールノボラック樹脂１．０ｇをテトラヒドロフラ
ン（ＴＨＦ）１０ｍｌに溶解し、無水酢酸２ｍｌとぎ酸
２．０ｇ、ピリジン０．３ｍｌを添加し、室温で４日間
攪拌下で反応させる。反応修了後、反応混合液を氷水中
に注げば、ポリマーが白色に沈澱してくる。沈澱はアセ
トンに再溶解し、氷水中に再沈澱させて精製し、減圧下
で乾燥させる。収率約９０％であった。Example 1 1.0 g of phenol novolac resin was dissolved in 10 ml of tetrahydrofuran (THF), 2 ml of acetic anhydride, 2.0 g of formic acid and 0.3 ml of pyridine were added, and the mixture was reacted at room temperature for 4 days with stirring. After completion of the reaction, the reaction mixture is poured into ice water, and the polymer precipitates in white. The precipitate is redissolved in acetone, reprecipitated in ice water for purification and dried under reduced pressure. The yield was about 90%.
【００２２】実施例２ ｐ−クレゾールノボラック樹脂１．０ｇをＴＨＦ１０ｍ
ｌに溶解し、無水酢酸２ｍｌとぎ酸１．４ｇ、ピリジン
０．３ｍｌを添加し、氷冷下で４日間攪拌しながら反応
させる。反応修了後、反応液を氷水中に注げば、ポリマ
ーが白色に沈澱してくる。沈澱はアセトンに再溶解し、
氷水中に再沈澱させて精製し、減圧下で乾燥させる。収
率約９０％であった。Example 2 1.0 g of p-cresol novolac resin was added to 10 m of THF.
2 ml of acetic anhydride, 1.4 g of formic acid and 0.3 ml of pyridine are added, and the mixture is reacted with stirring for 4 days under ice cooling. After completion of the reaction, the reaction solution is poured into ice water, and the polymer precipitates in white. The precipitate is redissolved in acetone,
Purify by reprecipitation in ice water and dry under reduced pressure. The yield was about 90%.
【００２３】実施例３ ｏ−クレゾールノボラック樹脂１．０ｇをＴＨＦ１０ｍ
ｌに溶解し、無水酢酸２ｍｌとぎ酸１．４ｇ、ピリジン
０．３ｍｌを添加し、室温で４日間攪拌下で反応させ
る。反応修了後、反応液を氷水中に注げば、ポリマーが
白色に沈澱してくる。沈澱はアセトンに再溶解し、氷水
中に再沈澱させて精製し、減圧下で乾燥させる。収率約
９０％であった。Example 3 1.0 g of o-cresol novolac resin was added to 10 m of THF.
Dissolve in 1 l, add 2 ml of acetic anhydride, 1.4 g of formic acid and 0.3 ml of pyridine, and react under stirring at room temperature for 4 days. After completion of the reaction, the reaction solution is poured into ice water, and the polymer precipitates in white. The precipitate is redissolved in acetone, reprecipitated in ice water for purification and dried under reduced pressure. The yield was about 90%.
【００２４】実施例４ ｍ−クレゾールノボラック樹脂１．０ｇをＴＨＦ１０ｍ
ｌに溶解し、無水酢酸２ｍｌとぎ酸１．４ｇ、ピリジン
０．３ｍｌを添加し、室温で４日間攪拌下で反応させ
る。反応修了後、反応液を氷水中に注げば、ポリマーが
白色に沈澱してくる。沈澱はアセトンに再溶解し、氷水
中に再沈澱させて精製し、減圧下で乾燥させる。収率約
９０％であった。Example 4 1.0 g of m-cresol novolac resin was added to 10 m of THF.
Dissolve in 1 l, add 2 ml of acetic anhydride, 1.4 g of formic acid and 0.3 ml of pyridine, and react under stirring at room temperature for 4 days. After completion of the reaction, the reaction solution is poured into ice water, and the polymer precipitates in white. The precipitate is redissolved in acetone, reprecipitated in ice water for purification and dried under reduced pressure. The yield was about 90%.
【００２５】実施例５ ｐ−ｔｅｒｔフェノールノボラック樹脂１．０ｇをＴＨ
Ｆ１０ｍｌに溶解し、無水酢酸２ｍｌとぎ酸１．０ｇ、
ピリジン０．３ｍｌを添加し、室温で３日間攪拌下で反
応させる。反応修了後、反応液を氷水中に注げば、ポリ
マーが白色に沈澱してくる。沈澱はアセトンに再溶解
し、メタノールに再沈澱させて精製し、減圧下で乾燥さ
せる。収率約９５％であった。Example 5 1.0 g of p-tert phenol novolac resin was added to TH
Dissolve in 10 ml of F, 2 ml of acetic anhydride and 1.0 g of formic acid,
0.3 ml of pyridine is added and the mixture is reacted at room temperature for 3 days with stirring. After completion of the reaction, the reaction solution is poured into ice water, and the polymer precipitates in white. The precipitate is redissolved in acetone, reprecipitated in methanol for purification and dried under reduced pressure. The yield was about 95%.
【００２６】実施例６ フェノールノボラック樹脂２．０ｇをテトラヒドロフラ
ン（ＴＨＦ）１０ｍｌに溶解し、ぎ酸２．６ｇ、ピリジ
ン４．５ｍｌを添加し、クロロ炭酸エチル８．２ｇを室
温でゆっくり滴下し、攪拌しながら反応させる。約５時
間以上反応させた後、反応混合液を氷水中に注げば、ポ
リマーが白色に沈澱してくる。沈澱はアセトンに再溶解
し、氷水中に再沈澱させて精製し、減圧下で乾燥させ
る。収率約８５％であった。Example 6 2.0 g of phenol novolac resin was dissolved in 10 ml of tetrahydrofuran (THF), 2.6 g of formic acid and 4.5 ml of pyridine were added, and 8.2 g of ethyl chlorocarbonate was slowly added dropwise at room temperature and stirred. While reacting. After reacting for about 5 hours or more, the reaction mixture is poured into ice water, and the polymer precipitates in white. The precipitate is redissolved in acetone, reprecipitated in ice water for purification and dried under reduced pressure. The yield was about 85%.
【００２７】実施例７ 感度については、照射エネルギーとレジスト膜の現像液
残膜率との関係を求め、残膜率が５０％の時（Ｅ1/2）
の照射エネルギーをそのレジストの感度とした。ホルミ
ル基、アセチル基の含有率（ｍｏｌ％）はＮＭＲより求
めた。また、代表的な例について赤外吸収スペクトルを
図１、およびＮＭＲスペクトルを図２に示す。得られた
樹脂は、紫外線、好ましくはデイープＵＶ光を照射すれ
ば脱カルボニル反応を容易に起こして水酸基を生じる
（図１：照射試料．波線）。即ち、極性が低いホルミル
エステル基から極性がより高いフェノール水酸基へ変化
する。そのため、本発明の樹脂を主成分とするレジスト
は、現像に用いる溶媒の極性を調節すれば、例えばアル
カリ水溶液を用いればポジ型レジストになるし、有機溶
媒を用いればネガ型レジストになった。Example 7 Regarding the sensitivity, the relation between the irradiation energy and the residual film ratio of the developing solution of the resist film was determined, and when the residual film ratio was 50% (E 1/2 ).
The irradiation energy of was used as the sensitivity of the resist. The content ratio (mol%) of formyl group and acetyl group was determined by NMR. An infrared absorption spectrum and a NMR spectrum of a typical example are shown in FIGS. 1 and 2, respectively. The resulting resin easily undergoes a decarbonylation reaction when exposed to ultraviolet rays, preferably deep UV light to generate hydroxyl groups (FIG. 1: irradiated sample, wavy line). That is, a formyl ester group having a low polarity is changed to a phenol hydroxyl group having a higher polarity. Therefore, the resist containing the resin of the present invention as a main component becomes a positive resist by using an alkaline aqueous solution, or a negative resist by using an organic solvent, if the polarity of the solvent used for development is adjusted.
【００２８】実施例８ 実施例１から６で得られたポリマーをエチルセロソルブ
アセテートに５重量％の濃度で溶解してレジスト溶液を
作り、スピンナーによってシリコンウエハーの上へ回転
塗布し、レジスト膜を形成する。常法により、１００℃
でプレベークをおこなった後、その上にマスクを当てて
デイープＵＶを照射した。現像液としてテトラメチルア
ンモニュームハイドロオキサイド３％溶液へ１分間浸漬
して現像すれば、露光部分が溶解して未露光部分を残し
たポジ型の画像が得られた。Example 8 The polymers obtained in Examples 1 to 6 were dissolved in ethyl cellosolve acetate at a concentration of 5% by weight to prepare a resist solution, which was spin-coated on a silicon wafer by a spinner to form a resist film. To do. According to the usual method, 100 ℃
In After performing the pre-baking, it was irradiated with de Lee-loop UV by applying a mask on it. When the film was immersed in a 3% tetramethylammonium hydroxide solution as a developing solution for 1 minute for development, a positive image was obtained in which an exposed portion was dissolved and an unexposed portion remained.
【００２９】実施例９ 実施例１から５で得られたポリマーを用い、 前記実施
例６と同様の操作をおこなってシリコンウエハー上にレ
ジスト膜を作成し、同じ条件でプレベーク後その上にマ
スクを当ててデイープＵＶを照射した。現像液としてク
ロロホルム：トリクロロエチレン混合液（混合比は種類
によって変わる）へ１分間浸漬して現像すれば、未露光
部分が溶解して露光部分を残したネガ型の画像が得られ
た。Example 9 Using the polymers obtained in Examples 1 to 5, a resist film was formed on a silicon wafer by the same operation as in Example 6, prebaked under the same conditions, and a mask was formed thereon. It was irradiated with de Lee-loop UV against. When a developing solution was immersed in a mixed solution of chloroform: trichloroethylene (mixing ratio varies depending on the type) for 1 minute to develop, a negative image in which unexposed portions were dissolved and exposed portions were obtained was obtained.
【００３０】[0030]
【発明の効果】本発明に係るこのレジストは、芳香族系
のデイープＵＶポリマーであることから耐ドライエッチ
ング性は充分に高く、サブミクロンの細線化に対応可能
であることが特徴であり、また、レジストの画像形成に
は１種類のレジストでネガ型の画像でもポジ型の画像で
も得られることが可能になる。従って、半導体の製造に
は本レジスト１種類を用意すれば良く、ネガ用、ポジ用
とレジスト材料を分けて用意する必要はない。現像液の
種類を変えるだけでレジストのタイプを自由に選ぶこと
が可能になるため作業工程に自由度が増し、融通性が利
くようになる。また、レジスト画像の剥膜は、膜全面を
再露光してアルカリ水溶液で処理すれば安全且つ、容易
に可能となる。The resist according to the effect the present invention is, dry etching resistance because it is de Lee-loop UV polymers of aromatic systems sufficiently high, it is a feature which can cope with thinning of the sub-micron In addition, it is possible to obtain a negative image or a positive image with one type of resist for image formation of the resist. Therefore, one kind of this resist may be prepared for manufacturing a semiconductor, and it is not necessary to separately prepare a resist material for a negative resist and a resist material for a positive resist. Since the resist type can be freely selected only by changing the type of the developing solution, the flexibility in the working process is increased and the flexibility is improved. Further, the peeling of the resist image can be safely and easily performed by re-exposing the entire surface of the film and treating it with an alkaline aqueous solution.
【図１】ホルミル化ノボラック樹脂の赤外吸収スペクト
ルの図である。デイープＵＶを５００ｍＪ／ｃｍ2照射し
た後（破線）、照射する前（実線）。FIG. 1 is a diagram of an infrared absorption spectrum of a formylated novolak resin. After de Lee-loop UV to 500 mJ / cm 2 irradiation (dashed line), before irradiation (solid line).
【図２】ホルミル化ノボラック樹脂のＮＭＲスペクトル
の図である。FIG. 2 is a diagram of an NMR spectrum of a formylated novolak resin.
Claims (4)
Ｈ3：ｐ−Ｃ（ＣＨ3）3 ｎ ：２以上 で表されるホルミル化ノボラック樹脂を主成分とするレ
ジスト材料。1. A general formula: R 1 : H: o-CH 3 , m-CH 3 , p-C in the formula
H 3: p-C (CH 3) 3 n: resist material mainly composed of formylated novolac resin represented by 2 or more.
溶解ないし分散し、触媒として３級アミンを添加し、ギ
酸と脱水剤の無水酢酸とを添加し、室温好ましくは２５
℃以下の攪拌下で反応させることを特徴とする前記請求
項１のレジスト材料の樹脂製造方法。2. A phenol novolac resin is dissolved or dispersed in an organic solvent, a tertiary amine is added as a catalyst, formic acid and acetic anhydride as a dehydrating agent are added, and the temperature is preferably 25
The method for producing a resin for a resist material according to claim 1, wherein the reaction is carried out under stirring at a temperature of not higher than ° C.
スト膜を基板上に形成させ、マスクを通してＵＶ照射装
置から紫外線を照射し、極性の高いアルカリ性水溶媒で
現像するポジ型レジスト画像の形成方法。3. A positive type resist image formed by forming a resist film containing the resin of claim 1 as a main component on a substrate, irradiating ultraviolet rays from a UV irradiating device through a mask, and developing with a highly polar alkaline water solvent. Forming method.
と同様の操作をおこない、極性の低い有機溶媒で現像す
るネガ型レジスト画像形成方法。4. A negative resist image forming method comprising the resin of claim 1 as a main component and performing the same operation as in the preceding paragraph, and developing with an organic solvent having a low polarity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35092093A JP3188577B2 (en) | 1993-12-28 | 1993-12-28 | Resist material, method of manufacturing resist material, and method of forming resist image |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35092093A JP3188577B2 (en) | 1993-12-28 | 1993-12-28 | Resist material, method of manufacturing resist material, and method of forming resist image |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07196755A true JPH07196755A (en) | 1995-08-01 |
| JP3188577B2 JP3188577B2 (en) | 2001-07-16 |
Family
ID=18413809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35092093A Expired - Fee Related JP3188577B2 (en) | 1993-12-28 | 1993-12-28 | Resist material, method of manufacturing resist material, and method of forming resist image |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3188577B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001042519A (en) * | 1999-05-24 | 2001-02-16 | Mitsubishi Chemicals Corp | Positive photosensitive composition and positive photosensitive lithographic printing plate |
-
1993
- 1993-12-28 JP JP35092093A patent/JP3188577B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001042519A (en) * | 1999-05-24 | 2001-02-16 | Mitsubishi Chemicals Corp | Positive photosensitive composition and positive photosensitive lithographic printing plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3188577B2 (en) | 2001-07-16 |
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