JP3040007B2 - Method of removing resist and curing type pressure-sensitive adhesive and adhesive sheet used therefor - Google Patents
Method of removing resist and curing type pressure-sensitive adhesive and adhesive sheet used thereforInfo
- Publication number
- JP3040007B2 JP3040007B2 JP14694591A JP14694591A JP3040007B2 JP 3040007 B2 JP3040007 B2 JP 3040007B2 JP 14694591 A JP14694591 A JP 14694591A JP 14694591 A JP14694591 A JP 14694591A JP 3040007 B2 JP3040007 B2 JP 3040007B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- resist
- sensitive adhesive
- pressure
- resist material
- 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 - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】この発明は、半導体の製造や回路
の作製などにおいて、不用となつた物品上のレジストを
除去する方法と、これに用いる硬化型感圧性接着剤およ
びそのシ―ト状物、テ―プ状物などの接着シ―ト類に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing a resist on an article which has become unnecessary in the manufacture of semiconductors and circuits, a curable pressure-sensitive adhesive used for the method, and a sheet-like adhesive. It relates to adhesive sheets such as objects and tapes.
【０００２】[0002]
【従来の技術】半導体のデバイス製造において、シリコ
ンウエハ上にレジスト材を塗布し、所定のパタ―ンに露
光・現像後、回路が形成される。回路形成後、レジスト
材は除去され、つぎの回路を形成するため、再度レジス
ト材を塗布するというサイクルが行われる。また、各種
基板に回路を形成するためにも、レジストのパタ―ン形
成が通常行われる。この際不用になつたレジスト材の除
去は、アツシヤ―（灰化手段）や溶剤で行われるのが一
般的である。2. Description of the Related Art In the manufacture of semiconductor devices, a circuit is formed after a resist material is applied on a silicon wafer, exposed and developed in a predetermined pattern. After the circuit is formed, the resist material is removed, and a cycle of applying the resist material again to form the next circuit is performed. Also, in order to form circuits on various substrates, a resist pattern is usually formed. At this time, the unnecessary resist material is generally removed by using an ashes (ashing means) or a solvent.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、レジス
ト材の除去にアツシヤ―を用いると、その作業に長時間
を要したり、レジスト材中の不純物イオンがウエハに注
入されるおそれがある。また、溶剤を用いると、作業環
境に問題を生じる。However, if an ash is used to remove the resist material, the work may take a long time or impurity ions in the resist material may be implanted into the wafer. Also, the use of a solvent causes a problem in the working environment.
【０００４】したがつて、この発明は、不用となつた物
品上のレジストを、上記従来とは全く異なる方法で、簡
単かつ確実に除去することを目的としている。Accordingly, an object of the present invention is to easily and surely remove a resist on an unnecessary article by a method completely different from the conventional technique.
【０００５】[0005]
【課題を解決するための手段】この発明者らは、レジス
ト材の除去に際し、特定の硬化型感圧性接着剤を用いた
接着シ―ト類を応用することにより、レジスト材中の不
純物イオンがウエハに注入されたり、作業環境を害する
といつた問題を生じることなく、レジスト材を簡単にか
つ確実に除去できることを知り、この発明を完成するに
至つた。SUMMARY OF THE INVENTION The present inventors apply an adhesive sheet using a specific curable pressure-sensitive adhesive when removing a resist material so that impurity ions in the resist material can be reduced. The present inventor has found that the resist material can be easily and reliably removed without causing problems such as being injected into a wafer or damaging the working environment, thereby completing the present invention.
【０００６】すなわち、この発明は、レジストパタ―ン
が存在する物品上に、レジスト材との親和性が良好な硬
化型感圧性接着剤を用いた接着シ―ト類を貼り付け、上
記接着剤の硬化後にこの接着シ―ト類とレジスト材とを
一体にはく離することを特徴とするレジストの除去方法
に係るものである。That is, according to the present invention, an adhesive sheet using a curable pressure-sensitive adhesive having a good affinity for a resist material is attached to an article having a resist pattern, and The present invention relates to a method for removing a resist, which comprises releasing the adhesive sheet and the resist material integrally after curing.
【０００７】また、この発明は、上記方法に用いる接着
剤として、感圧接着性ポリマ―に、分子内に不飽和二重
結合を１個以上有し、かつレジスト材との親和性が良好
な不揮発性化合物と、熱重合開始剤または光重合開始剤
とを含ませてなり、初期弾性率が硬化後に５倍以上とな
ることを特徴とする硬化型感圧性接着剤に係るものであ
り、さらに、この接着剤をフイルム基材上に設けてシ―
ト状、テ―プ状としたことを特徴とする接着シ―ト類に
係るものである。Further, the present invention provides, as an adhesive used in the above method, a pressure-sensitive adhesive polymer having at least one unsaturated double bond in a molecule and having good affinity with a resist material. Non-volatile compound , thermal polymerization initiator or photopolymerization initiator
And the initial elastic modulus is 5 times or more after curing.
That it is intended according to the curable pressure sensitive adhesive, wherein, further, provided with the adhesive on the film substrate sheet -
The present invention relates to adhesive sheets characterized in that the adhesive sheets have a shape of tape or tape.
【０００８】[0008]
【発明の構成・作用】この発明のレジストの除去方法に
おいては、まず、レジストパタ―ンが存在する物品上
に、レジスト材との親和性が良好な硬化型感圧性接着剤
を用いた接着シ―ト類を貼り付ける。このとき、レジス
ト材と上記接着剤とは一体化されるが、この一体化を促
進するために、上記貼り付け時に加熱・加圧するのが好
ましい。一体化は、レジストパタ―ンが消えて接着剤中
にレジスト材が完全に取り込まれる場合と、レジストパ
タ―ンが残りレジスト材中に接着剤の一部成分が入り込
む場合とがあるが、そのいずれであつてもよい。In the method for removing a resist according to the present invention, first, an adhesive sheet using a curable pressure-sensitive adhesive having a good affinity for a resist material is formed on an article having a resist pattern. Paste. At this time, the resist material and the adhesive are integrated, and in order to promote the integration, it is preferable to apply heat and pressure during the attachment. There are two types of integration: a case where the resist pattern disappears and the resist material is completely taken into the adhesive, and a case where the resist pattern remains and some components of the adhesive enter the resist material. It may be hot.
【０００９】ここで用いる感圧性接着剤は、物品上のレ
ジスト材との親和性が良好で、かつ加熱や光照射より硬
化する接着剤であり、この目的に特にかなつた接着剤と
して、感圧接着性ポリマ―に、分子内に不飽和二重結合
を１個以上有し、かつレジスト材との親和性が良好な不
揮発性化合物と、熱重合開始剤または光重合開始剤とを
含ませてなり、初期弾性率が硬化後に５倍以上となるこ
とを特徴とする硬化型感圧性接着剤が好ましく用いられ
る。The pressure-sensitive adhesive used here is an adhesive which has a good affinity for the resist material on the article and is cured by heating or light irradiation. A non-volatile compound having at least one unsaturated double bond in the molecule and having a good affinity for a resist material, and a thermal polymerization initiator or a photopolymerization initiator are used in the adhesive polymer.
A curable pressure-sensitive adhesive characterized by being included and having an initial elastic modulus of 5 times or more after curing is preferably used.
【００１０】この硬化型感圧性接着剤においては、感圧
接着性ポリマ―に基づく良好な感圧接着機能を有し、ま
たレジスト材との親和性の良好な上記の不揮発性化合物
がレジスト材と接着剤との前記一体化に寄与し、かつそ
の分子内に含まれる不飽和二重結合の作用で加熱や光照
射より重合硬化する機能を有している。This curable pressure-sensitive adhesive has a good pressure-sensitive adhesive function based on a pressure-sensitive adhesive polymer, and the above-mentioned non-volatile compound having a good affinity for a resist material is used as a resist material. It has a function of contributing to the above-mentioned integration with the adhesive and of being polymerized and cured by heating or light irradiation by the action of an unsaturated double bond contained in the molecule.
【００１１】上記の感圧接着性ポリマ―としては、一般
の感圧性接着剤に適用される公知の各種ポリマ―がいず
れも使用可能であるが、特に好ましいポリマ―として、
アクリル酸アルキルエステルおよび／またはメタクリル
酸アルキルエステルを主モノマ―としたアクリル系ポリ
マ―を推奨できる。As the pressure-sensitive adhesive polymer, any of various known polymers applicable to general pressure-sensitive adhesives can be used. Particularly preferred polymers are as follows.
An acrylic polymer having a main monomer of an alkyl acrylate and / or an alkyl methacrylate can be recommended.
【００１２】このアクリル系ポリマ―は、上記の主モノ
マ―、つまりアクリル酸またはメタクリル酸と炭素数が
通常１２以下のアルコ―ルとのエステルのほか、必要に
よりカルボキシル基ないし水酸基を有するモノマ―や、
その他の改質用モノマ―を用いて、これらを常法により
溶液重合、乳化重合、懸濁重合、塊状重合などの方法で
重合させることにより、得ることができる。The acrylic polymer includes the above-mentioned main monomer, that is, an ester of acrylic acid or methacrylic acid and an alcohol having usually 12 or less carbon atoms, and, if necessary, a monomer having a carboxyl group or a hydroxyl group. ,
It can be obtained by polymerizing these by other methods such as solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization using other modifying monomers.
【００１３】上記のカルボキシル基含有モノマ―として
は、アクリル酸、メタクリル酸、マレイン酸、イタコン
酸などが、水酸基含有モノマ―としては、ヒドロキシエ
チルアクリレ―ト、ヒドロキシプロピルアクリレ―トな
どが、それぞれ用いられる。これらのカルボキシル基な
いし水酸基含有のモノマ―の使用量は、全モノマ―中通
常２０重量％以下の割合とされているのがよい。The carboxyl group-containing monomers include acrylic acid, methacrylic acid, maleic acid and itaconic acid, and the hydroxyl group-containing monomers include hydroxyethyl acrylate and hydroxypropyl acrylate. Used respectively. The amount of the monomer containing a carboxyl group or a hydroxyl group is preferably 20% by weight or less in all monomers.
【００１４】また、上記その他の改質用モノマ―として
は、酢酸ビニル、プロピオン酸ビニル、スチレン、アク
リロニトリル、アクリルアミド、グリシジルメタクリレ
―トなどが用いられる。これらの改質用モノマ―の使用
量は、前記の主モノマ―との合計量中通常５０重量％以
下の割合とされているのがよい。Further, as the above-mentioned other monomers for modification, vinyl acetate, vinyl propionate, styrene, acrylonitrile, acrylamide, glycidyl methacrylate and the like are used. It is preferable that the amount of the reforming monomer used is usually 50% by weight or less of the total amount of the main monomer.
【００１５】このようなモノマ―から構成されるアクリ
ル系ポリマ―の分子量は、重量平均分子量で、通常３０
万〜２００万であるのが好ましい。分子量が低すぎると
これに前記の不揮発性化合物を配合したときに低粘度と
なつて、保存中に流れるなどの不都合を生じやすく、ま
た高くなりすぎると取り扱い上の問題を生じやすい。ま
た、このアクリル系ポリマ―は、レジストはく離時の作
業性を勘案して、そのガラス転移点が２５０度Ｋ以下で
あるのが好ましい。これより高くなると、硬化後に硬く
なりすぎてはく離が重くなる傾向がみられる。ただし、
このような高いガラス転移点を有するアクリル系ポリマ
―の使用をすべて排除しようというものではなく、場合
により使用可能である。The acrylic polymer composed of such a monomer has a weight average molecular weight of usually 30.
It is preferably from 10,000 to 2,000,000. If the molecular weight is too low, when the above-mentioned non-volatile compound is blended with the compound, the viscosity becomes low, so that inconvenience such as flowing during storage tends to occur, and if it is too high, handling problems tend to occur. It is preferable that the acrylic polymer has a glass transition point of 250 ° K or less in consideration of workability at the time of resist stripping. If it is higher than this, the resin tends to be too hard after curing and the peeling tends to be heavy. However,
The use of acrylic polymers having such a high glass transition point is not exhaustive, but may be used in some cases.
【００１６】また、上記のアクリル系ポリマ―にて代表
される感圧接着性ポリマ―に配合するべき不揮発性化合
物は、既述のように、レジストパタ―ンが存在する物品
上に貼り付けられたのち、この化合物の作用でレジスト
材と接着剤が一体化し、その後硬化するという機能を有
する。したがつて、この不揮発性化合物としては、分子
内に熱や光などで硬化できる不飽和二重結合を１個以上
有するとともに、レジスト材との親和性が良好であるこ
とが要求され、さらに感圧接着性ポリマ―との相溶性が
よく保存時に流れ出ないことも望まれる。Further, the non-volatile compound to be incorporated in the pressure-sensitive adhesive polymer represented by the above-mentioned acrylic polymer is attached to an article having a resist pattern as described above. Thereafter, the resist material and the adhesive are integrated by the action of this compound, and then have a function of being cured. Therefore, the non-volatile compound is required to have at least one unsaturated double bond which can be cured by heat, light, or the like in a molecule and to have good affinity with a resist material. It is also desirable that they have good compatibility with the pressure-sensitive adhesive polymer and do not flow out during storage.
【００１７】ここで、レジスト材との親和性が良好とい
うのは、レジスト材を溶解もしくは膨潤する現象が顕著
であることを指し、レジスト材中に移行・拡散する現象
も含まれる。この目安として、溶剤を十分乾燥したレジ
スト材を不揮発性化合物中に浸漬し、１３０℃に２４時
間保存したときに、レジスト材が溶解するか、または取
り出されたレジスト材の重量が２倍以上になる、つまり
レジスト材の不揮発性化合物に対する膨潤度が２以上と
なる程度でよい。また、この化合物が不揮発性であると
は、接着剤の塗布乾燥工程などにおいてこの化合物が簡
単に揮散してしまうことがないことを意味している。Here, the fact that the affinity with the resist material is good means that the phenomenon of dissolving or swelling the resist material is remarkable, and includes the phenomenon of migration and diffusion into the resist material. As a guideline, when a resist material obtained by sufficiently drying a solvent is immersed in a nonvolatile compound and stored at 130 ° C. for 24 hours, the resist material dissolves or the weight of the removed resist material is more than doubled. That is, the degree of swelling of the resist material with respect to the nonvolatile compound may be 2 or more. Further, that the compound is non-volatile means that the compound does not easily evaporate in the step of applying and drying the adhesive.
【００１８】このような不揮発性化合物としては、たと
えば、フエノキシポリエチレングリコ―ル（メタ）アク
リレ―ト、ε−カプロラクトン（メタ）アクリレ―ト、
ポリエチレングリコ―ルジ（メタ）アクリレ―ト、ポリ
プロピレングリコ―ルジ（メタ）アクリレ―ト、トリメ
チロ―ルプロパントリ（メタ）アクリレ―ト、ジペンタ
エリスリト―ルヘキサ（メタ）アクリレ―ト、ウレタン
（メタ）アクリレ―ト、エポキシ（メタ）アクリレ―
ト、オリゴエステル（メタ）アクリレ―トなどが挙げら
れ、これらの中から、用いる感圧接着性ポリマ―の種
類、対象とされるレジスト材に応じて、その一種または
二種以上を選択使用する。Examples of such nonvolatile compounds include phenoxypolyethylene glycol (meth) acrylate, ε-caprolactone (meth) acrylate,
Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane (meth) acrylate ―Epoxy (meth) acryle―
And oligoester (meth) acrylates. One or more of these are selected and used depending on the type of pressure-sensitive adhesive polymer to be used and the target resist material. .
【００１９】この不揮発性化合物の使用量としては、感
圧接着性ポリマ―１００重量部に対して、通常２０〜２
００重量部とするのがよい。この使用量が過少となる
と、レジストのはく離効果が十分でなく、また過多とな
ると、保存時に接着剤が流れだすため、好ましくない。The amount of the non-volatile compound used is usually 20 to 2 parts per 100 parts by weight of the pressure-sensitive adhesive polymer.
It is good to be 00 parts by weight. If the amount is too small, the peeling effect of the resist is not sufficient, and if it is too large, the adhesive flows out during storage, which is not preferable.
【００２０】このような感圧接着性ポリマ―と不揮発性
化合物とを含む硬化型感圧性接着剤は、ウエハなどの物
品に貼り付ける際の作業性の点から、上記ポリマ―を架
橋して凝集力を高めておくのが好ましい。たとえば、感
圧接着性ポリマ―としてカルボキシル基ないし水酸基含
有モノマ―を共重合させたアクリル系ポリマ―を用い、
このポリマ―の上記官能基と反応する多官能性化合物、
たとえばポリイソシアネ―ト、ポリエポキシ、各種金属
塩、キレ―ト化合物などを接着剤中に含ませておき、シ
―ト状などの成形段階で上記の反応を促進させて、上記
ポリマ―の架橋を行わせるようにすればよい。A curable pressure-sensitive adhesive containing such a pressure-sensitive adhesive polymer and a non-volatile compound is crosslinked and agglomerated from the viewpoint of workability when affixed to an article such as a wafer. preferably, keep increasing the power. For example, using an acrylic polymer obtained by copolymerizing a carboxyl group or a hydroxyl group-containing monomer as a pressure-sensitive adhesive polymer,
A polyfunctional compound that reacts with the functional groups of the polymer,
For example, a polyisocyanate, a polyepoxy, various metal salts, a chelate compound, and the like are included in an adhesive, and the above reaction is promoted in a molding step such as a sheet-like process to crosslink the polymer. What is necessary is just to make it perform.
【００２１】上記の多官能性化合物の使用量としては、
感圧接着性ポリマ―１００重量部に対して通常２０重量
部以下とし、この範囲内で上記ポリマ―の分子量が低け
れば多く、高ければ少なくなるように、適宜選択すれば
よい。多官能性化合物の使用量が多すぎると、接着力が
低下するため、好ましくない。The amount of the polyfunctional compound used is as follows:
The amount is usually 20 parts by weight or less based on 100 parts by weight of the pressure-sensitive adhesive polymer, and within this range, the molecular weight of the polymer may be appropriately selected such that the lower the molecular weight, the higher the molecular weight, and the lower the molecular weight. If the amount of the polyfunctional compound is too large, the adhesive strength is undesirably reduced.
【００２２】また、硬化型感圧性接着剤には、上記の多
官能性化合物の使用と同じ目的で微粉シリカなどの充て
ん剤を含ませるようにしてもよい。さらに、この接着剤
中には、粘着付与樹脂、着色剤、老化防止剤などの公知
の各種添加剤を必要に応じて含ませることができる。こ
れらの使用量は、通常の使用量でよい。The curable pressure-sensitive adhesive may contain a filler such as finely divided silica for the same purpose as the use of the above-mentioned polyfunctional compound. Further, in the adhesive, various known additives such as a tackifier resin, a colorant, an antioxidant and the like can be contained as required. These usage amounts may be normal usage amounts.
【００２３】このような各種成分を含ませうる硬化型感
圧性接着剤には、さらにその硬化手段に応じた重合開始
剤が添加される。たとえば、熱硬化の場合は、ベンゾイ
ルパ―オキサイド、アゾビスイソブチロニトリルなどの
加熱によりラジカルを発生する熱重合開始剤が用いら
れ、紫外線などの光硬化の場合は、ベンゾイン、ベンゾ
インエチルエ―テル、ジベンジルなどの光照射によりラ
ジカルを発生する光重合開始剤が用いられる。これらの
重合開始剤は、感圧接着性ポリマ―１００重量部に対し
て、通常０．１〜１０重量部の範囲で使用される。To the curable pressure-sensitive adhesive which can contain such various components, a polymerization initiator according to the curing means is further added. For example, in the case of thermal curing, a thermal polymerization initiator such as benzoyl peroxide and azobisisobutyronitrile that generates radicals by heating is used. In the case of photocuring such as ultraviolet light, benzoin and benzoin ethyl ether are used. , Dibenzyl or the like, a photopolymerization initiator which generates radicals by light irradiation is used. These polymerization initiators are generally used in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the pressure-sensitive adhesive polymer.
【００２４】このように構成される硬化型感圧性接着剤
は、その初期弾性率、つまり硬化前の弾性率が通常０．
５〜５０ｇ／mm2 程度であつて、かつこれが硬化後に５
倍以上となる、特にこの硬化後の弾性率が３〜４００ｇ
／mm2 程度となるように調整されているのが望ましい。The curable pressure-sensitive adhesive thus constituted has an initial elastic modulus, that is, an elastic modulus before curing, which is usually 0.1.
5 to 50 g / mm 2 , which is 5 g after curing.
More than twice, especially the elastic modulus after curing is 3 to 400 g
/ Mm 2 is desirable.
【００２５】このような弾性率に調整されていると、硬
化前の感圧接着特性と硬化後のレジストはく離性とに共
に好結果が得られるためである。弾性率の調整は、感圧
接着性ポリマ―の種類、これに添加する前記の不揮発性
化合物やその他の配合成分の使用量、多官能性化合物に
よる架橋の度合、硬化条件などを適宜選択することによ
り、容易に行うことが可能である。When the elastic modulus is adjusted to such a value, good results can be obtained in both the pressure-sensitive adhesive property before curing and the peelability of the resist after curing. Adjustment of the elastic modulus is performed by appropriately selecting the kind of the pressure-sensitive adhesive polymer, the amount of the non-volatile compound or other compounding components to be added thereto, the degree of crosslinking by the polyfunctional compound, the curing conditions, and the like. Can be easily performed.
【００２６】なお、上記の弾性率は、断面積５mm2 の接
着剤を、標線距離１０mmとして、２３℃±２℃の温度下
で、５０mm／分の引張速度で引張試験を行い、応力−歪
み曲線を得、初期の傾きから求める方法で、測定される
値を意味する。The above modulus of elasticity is determined by conducting a tensile test at a tensile speed of 50 mm / min at a temperature of 23 ° C. ± 2 ° C. using an adhesive having a cross-sectional area of 5 mm 2 and a mark length of 10 mm. A value measured by a method in which a distortion curve is obtained and obtained from an initial slope.
【００２７】このような硬化型感圧性接着剤は、前記の
使用に際し、場合によりこれ単独でシ―ト状やテ―プ状
などに成形されることもあるが、通常はフイルム基材を
用いてこの上に乾燥後の厚さが約１０〜１８０μｍとな
るように塗着され、レジスト除去用の接着シ―ト類とさ
れる。フイルム基材としては、ポリエチレン、ポリプロ
ピレン、ポリエチレンテレフタレ―トなどからなる厚さ
が通常約１２〜１００μｍの樹脂フイルムが用いられ、
特に接着剤の硬化を光照射にて行う場合は、紫外線など
の光を透過するものが選択使用される。In the above-mentioned use, such a curable pressure-sensitive adhesive may be formed into a sheet, a tape or the like depending on the case, but usually, a film base material is used. It is coated on the lever so that the thickness after drying is about 10 to 180 μm, and is used as adhesive sheets for removing the resist. As the film substrate, a resin film having a thickness of usually about 12 to 100 μm made of polyethylene, polypropylene, polyethylene terephthalate, or the like is used,
In particular, when the curing of the adhesive is performed by light irradiation, a material that transmits light such as ultraviolet rays is selectively used.
【００２８】この発明のレジストの除去方法において、
レジストパタ―ンが存在する物品上に、既述のように、
上記構成の硬化型感圧性接着剤を用いた接着シ―ト類を
貼り付け、レジスト材と上記接着剤とを一体化させたの
ちは、加熱または光照射などによる所定の硬化処理に供
される。ウエハなどの物品に与える熱的影響を考慮に入
れる場合は、光照射による硬化処理が特に好適で、その
照射量は、紫外線では３００〜３０００mj／cm2 の範囲
とするのがよい。In the method for removing a resist according to the present invention,
On the article where the resist pattern exists, as described above,
After bonding an adhesive sheet using the curable pressure-sensitive adhesive having the above structure and integrating the resist material and the adhesive, the resist sheet is subjected to a predetermined curing treatment by heating or light irradiation. . When taking into consideration the thermal effect on an article such as a wafer, curing treatment by light irradiation is particularly suitable, and the irradiation amount is preferably in the range of 300 to 3000 mj / cm 2 for ultraviolet light.
【００２９】この硬化処理により、上記接着剤はレジス
ト材と一体化した状態で硬化して、その弾性率が前記の
如く著しく増大し、これに伴つてレジスト材とウエハな
どの物品との接着力が大きく低下する。その結果、この
硬化後に接着シ―ト類をはく離することにより、物品上
のレジスト材は、上記接着シ―ト類と一体となつて、簡
単にかつ完全にはく離除去される。By this curing treatment, the above-mentioned adhesive is cured in a state of being integrated with the resist material, and its elastic modulus is remarkably increased as described above, whereby the adhesive strength between the resist material and an article such as a wafer is increased. Greatly decreases. As a result, by peeling the adhesive sheets after the curing, the resist material on the article is easily and completely peeled off together with the adhesive sheets.
【００３０】このようにレジスト材をはく離除去する方
法によると、アツシヤ―を用いる従来方法のような作業
の長時間化や、レジスト材中の不純物イオンがウエハに
注入されるといつた心配がなく、また溶剤を用いる従来
方法におけるような作業環境の悪化といつた心配も特に
ない。According to the method of stripping and removing the resist material as described above, there is no need to worry that the operation is prolonged as in the conventional method using an asher or that the impurity ions in the resist material are implanted into the wafer. Also, there is no particular concern that the working environment is deteriorated as in the conventional method using a solvent.
【００３１】[0031]
【発明の効果】以上のように、この発明においては、ウ
エハなどの物品上のレジストに、特定の硬化型感圧性接
着剤を用いた接着シ―ト類を貼り付け、上記接着剤の硬
化後にこの接着シ―ト類とレジストとを一体にはく離処
理するものであるため、レジスト材中の不純物イオンが
ウエハに注入されたり、作業環境を害するといつた問題
を一切生じることなく、簡単かつ確実にレジストの除去
目的を達成できる。As described above, in the present invention, an adhesive sheet using a specific curable pressure-sensitive adhesive is attached to a resist on an article such as a wafer, and after the adhesive is cured, Since the adhesive sheet and the resist are peeled off integrally, it is easy and reliable without any problems such as impurity ions in the resist material being implanted into the wafer or damaging the working environment. Thus, the purpose of removing the resist can be achieved.
【００３２】[0032]
【実施例】つぎに、この発明の実施例を記載してより具
体的に説明する。なお以下、部とあるのは重量部を意味
する。Next, an embodiment of the present invention will be described in more detail. Hereinafter, "parts" means parts by weight.
【００３３】実施例１ アクリル酸ｎ−ブチル８０部、アクリル酸エチル１５
部、アクリル酸５部からなるモノマ―混合物を、酢酸エ
チル１５０部、アゾビスイソブチロニトリル０．１部を
用いて、窒素気流下６０℃にて１２時間溶液重合を行
い、重量平均分子量が５６万、ガラス転移点が２３１度
Ｋのアクリル系ポリマ―の溶液を得た。Example 1 80 parts of n-butyl acrylate, 15 parts of ethyl acrylate
Part, a monomer mixture consisting of 5 parts of acrylic acid was subjected to solution polymerization under a nitrogen stream at 60 ° C. for 12 hours using 150 parts of ethyl acetate and 0.1 part of azobisisobutyronitrile. A solution of an acrylic polymer having a glass transition point of 560,000 K was obtained.
【００３４】このアクリル系ポリマ―の溶液２５０部
に、ウレタンアクリレ―ト（共栄社油脂化学工業株式会
社製の商品名ＵＡ−１０１Ｈ）１００部、ベンジルジメ
チルケタ―ル３部、ジフエニルメタンジイソシアネ―ト
３部を均一に混合し、硬化型感圧性接着剤溶液とした。To 250 parts of this acrylic polymer solution, 100 parts of urethane acrylate (trade name: UA-101H, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), 3 parts of benzyldimethylketal, and diphenylmethane diisocyanate Three parts of the net were uniformly mixed to obtain a curable pressure-sensitive adhesive solution.
【００３５】つぎに、この硬化型感圧性接着剤溶液を、
厚さが５０μｍのポリエステルフイルム上に、乾燥後の
厚さが５０μｍとなるように塗布し、１５０℃で１０分
乾燥して、レジスト除去用の接着テ―プを作製した。Next, this curable pressure-sensitive adhesive solution is
It was applied on a 50 μm-thick polyester film so that the thickness after drying became 50 μm, and dried at 150 ° C. for 10 minutes to prepare an adhesive tape for removing the resist.
【００３６】比較例１ 実施例１のアクリル系ポリマ―の溶液２５０部に、ジフ
エニルメタンジイソシアネ―ト３部を均一に混合して、
感圧性接着剤溶液を調製したのち、この溶液を実施例１
と同様にポリエステルフイルム上に塗布して、レジスト
除去用の接着テ―プを作製した。Comparative Example 1 Diphenylmethane diisocyanate (3 parts) was uniformly mixed with 250 parts of the acrylic polymer solution of Example 1,
After preparing a pressure-sensitive adhesive solution, this solution was used in Example 1.
It was applied on a polyester film in the same manner as described above to prepare an adhesive tape for removing the resist.
【００３７】実施例２ アクリル酸２−エチルヘキシル６０部、アクリル酸ブチ
ル３０部、酢酸ビニル５部、アクリル酸５部よりなるモ
ノマ―混合物を、実施例１と同様の方法で重合して、重
量平均分子量が６２万、ガラス転移点が２０７度Ｋのア
クリル系ポリマ―の溶液を得た。Example 2 A monomer mixture comprising 60 parts of 2-ethylhexyl acrylate, 30 parts of butyl acrylate, 5 parts of vinyl acetate and 5 parts of acrylic acid was polymerized in the same manner as in Example 1 to obtain a weight average. A solution of an acrylic polymer having a molecular weight of 620,000 and a glass transition point of 207 K was obtained.
【００３８】このアクリル系ポリマ―の溶液２５０部
に、オリゴエステルアクリレ―ト（東亜合成化学工業株
式会社製の商品名アロニツクスＭ−５４００）１００
部、ベンジルジメチルケタ―ル５部、トリレンジイソシ
アネ―ト３部を均一に混合して、硬化型感圧性接着剤溶
液を得、この溶液を実施例１と同様にポリエステルフイ
ルム上に塗布して、レジスト除去用の接着テ―プを作製
した。To 250 parts of this acrylic polymer solution, 100 parts of oligoester acrylate (trade name: Alonix M-5400 manufactured by Toa Gosei Chemical Industry Co., Ltd.)
Parts, 5 parts of benzyldimethylketal and 3 parts of tolylene diisocyanate were uniformly mixed to obtain a curable pressure-sensitive adhesive solution. This solution was applied on a polyester film in the same manner as in Example 1. Thus, an adhesive tape for removing the resist was prepared.
【００３９】上記の実施例１，２および比較例１の各接
着テ―プにつき、その感圧性接着剤の初期弾性率を調べ
た結果、また特に実施例１，２の両接着テ―プにつき高
圧水銀ランプを用いて紫外線を１０００mj／cm2 の照射
量で照射し硬化させたのちの上記弾性率を調べた結果
は、つぎのとおりであつた。The initial elastic modulus of the pressure-sensitive adhesive of each of the adhesive tapes of Examples 1 and 2 and Comparative Example 1 was examined. The results of examining the above elastic modulus after curing by irradiating ultraviolet rays at a dose of 1000 mj / cm 2 using a high-pressure mercury lamp were as follows.
【００４０】 初期弾性率（ｇ／mm2 ） 硬化後の弾性率（ｇ／mm2 ） 実施例１ ９．５ １１０．５ 実施例２ ５．３ ８０．２ 比較例１ １３．４ ― Initial elastic modulus (g / mm 2 ) Modulus of elasticity after curing (g / mm 2 ) Example 1 9.5 110.5 Example 2 5.3 80.2 Comparative example 1 13.4 —
【００４１】実施例３ 実施例１の接着テ―プを、シリコンウエハの表面にノボ
ラツクとキノンジアジドからなるレジストを塗布し露光
・現像したパタ―ン上に、１００℃の加熱ロ―ルで加熱
圧着して、貼り付けたのち、高圧水銀ランプを用いて、
紫外線を１０００mj／cm2 の照射量で照射して、感圧性
接着剤を硬化させた。Example 3 The adhesive tape of Example 1 was heated and pressed with a heating roll of 100 ° C. on a pattern obtained by applying a resist consisting of novolak and quinonediazide to the surface of a silicon wafer, exposing and developing the resist. Then, after pasting, using a high-pressure mercury lamp,
Ultraviolet rays were irradiated at an irradiation amount of 1000 mj / cm 2 to cure the pressure-sensitive adhesive.
【００４２】この硬化後、接着テ―プをはく離したとこ
ろ、上記のレジストは接着テ―プと一体にはく離除去さ
れた。シリコンウエハの表面を蛍光顕微鏡で観察した
が、レジスト材の存在は全く認められなかつた。After the curing, the adhesive tape was peeled off, and the resist was peeled off together with the adhesive tape. When the surface of the silicon wafer was observed with a fluorescence microscope, the presence of the resist material was not recognized at all.
【００４３】実施例４ 実施例２の接着テ―プを用い、実施例３と同様にしてレ
ジストのはく離除去処理を行つたところ、実施例１と同
様の良好な結果が得られた。Example 4 Using the adhesive tape of Example 2 and removing the resist in the same manner as in Example 3, the same good results as in Example 1 were obtained.
【００４４】比較例２ 比較例１の接着テ―プを用い、実施例３と同様にしてレ
ジストのはく離処理を行つてみたところ、接着テ―プだ
けがはく離され、レジストはシリコンウエハの表面にほ
とんど残つていた。COMPARATIVE EXAMPLE 2 Using the adhesive tape of Comparative Example 1, the resist was peeled off in the same manner as in Example 3. As a result, only the adhesive tape was peeled off, and the resist was left on the surface of the silicon wafer. Almost remained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ // Ｈ０５Ｋ 3/06 Ｈ０５Ｋ 3/06 Ｃ (72)発明者 川西 道朗 大阪府茨木市下穂積１丁目１番２号 日 東電工株式会社内 (72)発明者 水野 文夫 東京都青梅市今井2326番地 株式会社 日立製作所デバイス開発センタ内 (72)発明者 森内 昇 東京都青梅市今井2326番地 株式会社 日立製作所デバイス開発センタ内 (56)参考文献 特開 昭60−70795（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 21/027 G03F 7/00 - 7/42 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI // H05K 3/06 H05K 3/06 C (72) Inventor Michio Kawanishi 1-2-1, Shimohozumi, Ibaraki-shi, Osaka Nitto Inside Electric Works Co., Ltd. (72) Inventor Fumio Mizuno 2326 Imai, Ome-shi, Tokyo Inside the Device Development Center, Hitachi, Ltd. ) References JP-A-60-70795 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01L 21/027 G03F 7/ 00-7/42
Claims (5)
レジスト材との親和性が良好な硬化型感圧性接着剤を用
いた接着シ―ト類を貼り付け、上記接着剤の硬化後にこ
の接着シ―ト類とレジスト材とを一体にはく離すること
を特徴とするレジストの除去方法。1. An article having a resist pattern,
Affixing an adhesive sheet using a curable pressure-sensitive adhesive having a good affinity for the resist material, and peeling off the adhesive sheet and the resist material after the adhesive is cured. Characteristic method of removing resist.
二重結合を１個以上有し、かつレジスト材との親和性が
良好な不揮発性化合物と、熱重合開始剤または光重合開
始剤とを含ませてなり、初期弾性率が硬化後に５倍以上
となることを特徴とするレジスト除去用の硬化型感圧性
接着剤。2. A non-volatile compound having at least one unsaturated double bond in a molecule of a pressure-sensitive adhesive polymer and having a good affinity for a resist material , a thermal polymerization initiator or photopolymerization. Open
Initiator is included and the initial elastic modulus is 5 times or more after curing
Curable pressure sensitive adhesives for resist removal, characterized in that a.
キルエステルおよび／またはメタクリル酸アルキルエス
テルを主モノマ―としたアクリル系ポリマ―からなる請
求項２に記載のレジスト除去用の硬化型感圧性接着剤。3. The curable pressure-sensitive resin for resist removal according to claim 2, wherein the pressure-sensitive adhesive polymer comprises an acrylic polymer having an alkyl acrylate and / or an alkyl methacrylate as a main monomer. adhesive.
多官能性化合物を含む請求項２または請求項３に記載の
レジスト除去用の硬化型感圧性接着剤。4. The curable pressure-sensitive adhesive for removing a resist according to claim 2, further comprising a polyfunctional compound for crosslinking the pressure-sensitive adhesive polymer.
いずれかに記載の硬化型感圧性接着剤を設けたことを特
徴とするレジスト除去用の接着シ―ト類。DOO acids - 5. The adhesive sheet for resist removal, characterized in that a curable pressure sensitive adhesive according to any one of claims 2 to 4 on the film substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14694591A JP3040007B2 (en) | 1991-05-22 | 1991-05-22 | Method of removing resist and curing type pressure-sensitive adhesive and adhesive sheet used therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14694591A JP3040007B2 (en) | 1991-05-22 | 1991-05-22 | Method of removing resist and curing type pressure-sensitive adhesive and adhesive sheet used therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04345015A JPH04345015A (en) | 1992-12-01 |
| JP3040007B2 true JP3040007B2 (en) | 2000-05-08 |
Family
ID=15419131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14694591A Expired - Lifetime JP3040007B2 (en) | 1991-05-22 | 1991-05-22 | Method of removing resist and curing type pressure-sensitive adhesive and adhesive sheet used therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3040007B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009514602A (en) * | 2005-11-02 | 2009-04-09 | セカンド サイト メディカル プロダクツ インコーポレイテッド | Implantable microelectronic device and manufacturing method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997000534A1 (en) * | 1995-06-15 | 1997-01-03 | Nitto Denko Corporation | Method of removing resist, and adhesive or adhesive sheet used for the method |
| JP2000042921A (en) * | 1998-07-23 | 2000-02-15 | Fuji Seisakusho:Kk | Separation of masking and cleaning method |
| JP2001076871A (en) | 1999-06-29 | 2001-03-23 | Nitto Denko Corp | Organic electroluminescent element and its manufacture |
| JP4999801B2 (en) * | 2008-08-07 | 2012-08-15 | 株式会社フジクラ | Etching method |
-
1991
- 1991-05-22 JP JP14694591A patent/JP3040007B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009514602A (en) * | 2005-11-02 | 2009-04-09 | セカンド サイト メディカル プロダクツ インコーポレイテッド | Implantable microelectronic device and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04345015A (en) | 1992-12-01 |
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