JPH05152270A - Substrate treatment method - Google Patents
Substrate treatment methodInfo
- Publication number
- JPH05152270A JPH05152270A JP31506891A JP31506891A JPH05152270A JP H05152270 A JPH05152270 A JP H05152270A JP 31506891 A JP31506891 A JP 31506891A JP 31506891 A JP31506891 A JP 31506891A JP H05152270 A JPH05152270 A JP H05152270A
- Authority
- JP
- Japan
- Prior art keywords
- ozone
- substrate
- containing gas
- liquid
- ultrapure water
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有機物被膜や付着物の
除去方法に関し、特に半導体装置等をフォトリソグラフ
ィーによって製造する際に使用されている有機高分子化
合物であるフォトレジスト膜あるいは付着した好ましく
ない有機化合物あるいは無機化合物をなどの被処理物を
シリコンウエハ等の基板から除去する基板処理方法に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing organic coatings and deposits, and more particularly to a photoresist film which is an organic polymer compound used when manufacturing semiconductor devices and the like by photolithography, or a deposited photoresist. The present invention relates to a substrate processing method for removing an object to be processed such as a non-organic compound or an inorganic compound from a substrate such as a silicon wafer.
【０００２】[0002]
【従来の技術】ＩＣ、ＬＳＩ等に代表される半導体装置
の製造工程をはじめとした微細加工工程においては、シ
リコン等の半導体基板やガラス基板等に、感光性の有機
高分子化合物を塗布し、所定の回路等のパターンを形成
したフォトマスクを介して紫外線等で露光した後にフォ
トレジストを現像して、基板上にフォトレジストのパタ
ーンを形成し、フォトレジストの形成されていない基板
上にＣＶＤ、スパッタリング等で成膜を行ったり、薬剤
によるエッチング、ＲＩＥ（反応性イオンエッチン
グ）、不純物の元素の加熱による拡散やイオン注入を行
っている。そして、一連の処理が終了した基板上のフォ
トレジストの膜は化学的な処理によって除去されるが、
ＬＳＩ等の製造工程では、一般にこのようなフォトレジ
ストを塗布して各種の処理をした後にフォトレジスト膜
を除去する操作は１回にとどまらず数回行われる。2. Description of the Related Art In a microfabrication process including a manufacturing process of a semiconductor device typified by IC, LSI, etc., a photosensitive organic polymer compound is applied to a semiconductor substrate such as silicon or a glass substrate, After exposure with ultraviolet rays or the like through a photomask on which a pattern such as a predetermined circuit is formed, the photoresist is developed, a photoresist pattern is formed on the substrate, and CVD is performed on the substrate on which the photoresist is not formed. A film is formed by sputtering, etching with a chemical agent, RIE (reactive ion etching), diffusion of an impurity element by heating, or ion implantation is performed. Then, the photoresist film on the substrate after the series of processes is removed by a chemical process,
In the process of manufacturing an LSI or the like, generally, the operation of applying the photoresist and performing various treatments and then removing the photoresist film is performed not only once but several times.
【０００３】フォトレジスト膜の除去は各種の方法が採
用されているが、フォトレジスト膜の除去が不完全であ
るとその後の工程に悪影響を与えるためにフォトレジス
ト膜を完全に除去することが必要である。特に、最近の
ように半導体装置の集積度が高まり、形成される半導体
装置の回路の線幅が細くなると、フォトレジスト膜の残
渣の影響は集積度の低い場合に比べて大きな問題となる
ので完全に除去することが求められており、通常は薬液
による湿式による方法あるいは酸素プラズマ等を使用す
る乾式方法によって行われている。Various methods have been adopted to remove the photoresist film. However, if the removal of the photoresist film is incomplete, the subsequent steps will be adversely affected. Therefore, it is necessary to completely remove the photoresist film. Is. In particular, when the degree of integration of semiconductor devices has increased and the line width of the circuits of the semiconductor devices to be formed has become thinner, as in recent years, the effect of the residue of the photoresist film becomes a greater problem than in the case of low integration. It is required to be removed by a wet method using a chemical solution or a dry method using oxygen plasma or the like.
【０００４】フォトレジスト膜の湿式による除去方法で
は、通常は硫酸が使用されており、硫酸の酸化能力を高
めるために過酸化水素を混合することが行われている。
硫酸と過酸化水素を混合した液を使用してフォトレジス
ト膜の除去を行う場合には、フォトレジスト膜の除去を
行った後に付着している硫酸などの薬液を除去し、更に
残渣あるいはその他の付着物を除去するために超純水等
で洗浄することが広く行われている。In the method of removing the photoresist film by a wet method, sulfuric acid is usually used, and hydrogen peroxide is mixed to enhance the oxidizing ability of sulfuric acid.
When the photoresist film is removed using a liquid mixture of sulfuric acid and hydrogen peroxide, the chemical liquid such as sulfuric acid adhering after the removal of the photoresist film is removed, and the residue or other Washing with ultrapure water or the like is widely performed to remove adhered substances.
【０００５】通常の湿式による半導体用のウエハ上の有
機物被膜あるいはその他の付着物の除去は、被処理ウエ
ハを複数枚収容したウエハカセットを硫酸と過酸化水素
水等との混合液のような処理液を満たした処理槽に所定
の時間浸漬した後に、リンス槽において超純水あるいは
他のリンス液中に浸漬して基板に付着した薬液やフォト
レジスト膜の残渣あるいはその他の付着物の除去を行っ
ていた。In order to remove the organic film or other deposits on the semiconductor wafer by the usual wet method, a wafer cassette containing a plurality of wafers to be processed is treated with a mixed solution of sulfuric acid and hydrogen peroxide solution. After dipping in a treatment tank filled with liquid for a predetermined time, it is immersed in ultrapure water or another rinse liquid in the rinse tank to remove the chemical liquid adhering to the substrate, the residue of the photoresist film or other adhered substances. Was there.
【０００６】硫酸と過酸化水素水の混合液によるフォト
レジスト膜の除去は、過酸化水素が分解して発生する発
生期の酸素による酸化分解作用が大きな役割を果たして
いる。したがって、この混合液の酸化能力を維持するた
めには、被処理物の酸化分解によって消費されて濃度が
薄くなった硫酸および過酸化水素水を取り出して新しい
液を補充することが必要となる。The removal of the photoresist film with a mixed solution of sulfuric acid and hydrogen peroxide plays a major role in the oxidative decomposition action of oxygen during the nascent period when hydrogen peroxide is decomposed. Therefore, in order to maintain the oxidizing ability of this mixed solution, it is necessary to take out the sulfuric acid and the hydrogen peroxide solution, which have been consumed by the oxidative decomposition of the object to be treated and have a reduced concentration, and to replenish them with a new solution.
【０００７】そこで、被処理物の除去能力が低下した廃
液の処理や液の補充の操作という作業を行わなくても同
等の効果を得るために、硫酸にオゾンを供給してフォト
レジスト膜の除去を行う方法が特公昭５２−１２０６３
号公報において提案されている。Therefore, in order to obtain the same effect without performing operations such as the treatment of the waste liquid having a reduced ability to remove the object to be treated and the replenishment of the liquid, ozone is supplied to sulfuric acid to remove the photoresist film. The method of performing is Japanese Patent Publication Sho 52-12063
It is proposed in the publication.
【０００８】しかしながら、一般のフォトレジスト膜の
場合にはこのような硫酸中へオゾンを導入する方法によ
ってもフォトレジスト膜を除去することが可能である
が、反応性イオンエッチングを行ったり、砒素などを高
濃度にイオン注入して不純物のドーピングを行った場合
にはフォトレジスト膜が完全には除去されずに残渣が残
る場合が発生している。これはイオン注入工程等のエネ
ルギーの高いイオンで処理した場合にはフォトレジスト
膜はイオン注入に使用された砒素等がフォトレジストと
化学反応をしてフォトレジスト膜が酸化を受けにくい物
質に変質しているものとみられ、その結果処理液によっ
て酸化分解を受けにくくなったものと考えられる。However, in the case of a general photoresist film, the photoresist film can be removed by such a method of introducing ozone into sulfuric acid, but reactive ion etching or arsenic is used. When impurities are doped by ion implantation at a high concentration, the photoresist film may not be completely removed and a residue may remain. This is because when the photoresist film is treated with high energy ions in the ion implantation process, the arsenic used in the ion implantation chemically reacts with the photoresist, and the photoresist film is transformed into a substance that is not easily oxidized. It is thought that the treatment liquid made it less susceptible to oxidative decomposition.
【０００９】また、フォトレジスト膜の処理に使用する
硫酸は濃度が高いので、処理液中の水の比率は少ない
が、硫酸への溶解度が極めて小さいオゾンを水の比率の
少ない硫酸中へ導入しても処理液中への溶解量は少ない
ので、処理液中へオゾンを導入しても十分にオゾンが利
用されないことになる。したがって、硫酸中にオゾンを
導入してもオゾンによる酸化能力が有効に利用されない
ことがおこる。Further, since the sulfuric acid used for the treatment of the photoresist film has a high concentration, the proportion of water in the treatment liquid is small, but ozone having a very low solubility in sulfuric acid is introduced into sulfuric acid having a small proportion of water. However, since the amount of dissolution in the treatment liquid is small, even if ozone is introduced into the treatment liquid, ozone will not be fully utilized. Therefore, even if ozone is introduced into sulfuric acid, the oxidizing ability of ozone may not be effectively utilized.
【００１０】一方、乾式による処理方法は、酸素プラズ
マに代表されるように高エネルギーの粒子等によってウ
エハに損傷を与える場合があり、またオゾンによる乾式
の処理方法では、高ドーズインプラントレジスト等の場
合に比較的高温度で処理が行われると、熱によりポンピ
ング等が起こり、レジスト残りが生じやすいという問題
があった。On the other hand, the dry processing method may damage the wafer by high-energy particles or the like as represented by oxygen plasma, and the dry processing method by ozone is a high dose implant resist. However, when the treatment is performed at a relatively high temperature, there is a problem that pumping or the like occurs due to heat, and a resist residue easily occurs.
【００１１】そこで、本発明者らは、超純水中にオゾン
を導入してオゾンが溶解あるいは気泡状態で存在する液
で洗浄することにより、オゾンの強力な酸化作用によっ
て、有機物被膜を除去する方法を提案し、更にオゾンに
よる乾式処理方法あるいは他の薬剤による処理方法と組
み合わせることによって、薬剤あるいはオゾンによる乾
式処理方法では除去することができないで残渣として付
着しているイオン注入工程等を経たフォトレジスト膜を
完全に除去することを提案している。Therefore, the inventors of the present invention introduce ozone into ultrapure water and wash it with a liquid in which ozone is dissolved or in the form of bubbles to remove the organic film by the strong oxidizing action of ozone. By proposing a method and combining it with a dry treatment method using ozone or a treatment method using other chemicals, a photo that has been subjected to an ion implantation process etc. that cannot be removed by the dry treatment method using chemicals or ozone and is attached as a residue It is proposed to completely remove the resist film.
【００１２】[0012]
【発明が解決しようとする課題】オゾンを超純水中へ供
給して得られるオゾンが溶解するとともに気泡として存
在している液によって、オゾンを硫酸中に供給した場合
よりも有機物被膜の除去能力が大きいことをみいだした
が、更に有機物被膜の除去速度を増大して、短時間に大
量のウエハ等を処理することが求められている。DISCLOSURE OF INVENTION Problems to be Solved by the Invention The ability of removing an organic film than that in the case of supplying ozone into sulfuric acid by a liquid in which ozone obtained by supplying ozone into ultrapure water is dissolved and is present as bubbles However, it is required to further increase the removal rate of the organic film and process a large number of wafers in a short time.
【００１３】本発明は、従来の有機物被膜あるいは付着
物をオゾンを使用して湿式によって除去する速度を大き
くし、短時間に完全に有機物被膜を除去することを目的
とするものである。It is an object of the present invention to increase the rate at which a conventional organic film or deposit is removed by wet using ozone, and to completely remove the organic film in a short time.
【００１４】[0014]
【課題を解決するための手段】本発明はウエハ等の基板
を処理液中に入れずに、気相中において基板の有機物被
膜等の被処理物の面に、オゾン含有気体を水中を通過さ
せて得られる湿潤オゾン、オゾン含有気体の気泡と水と
が混合した水を作用させることによって、有機物被膜等
の被処理物を除去する基板処理方法である。According to the present invention, an ozone-containing gas is allowed to pass through water to the surface of an object to be processed such as an organic film of the substrate in the vapor phase without putting the substrate such as a wafer in the processing liquid. This is a substrate processing method of removing an object to be processed such as an organic film by causing the wet ozone obtained as described above, water mixed with bubbles of ozone-containing gas and water to act.
【００１５】すなわち、本発明の方法は、湿潤なオゾ
ン、オゾン含有気体の気泡を混合した水を有機物被膜が
形成された基板面、あるいは好ましくない物質が付着し
た基板面に作用させるものであり、 （１）被処理面を上にして基板を水平に置いた密閉した
処理室中へ、水中を通過して湿潤なオゾン含有気体を供
給することによって有機物表面が湿潤なオゾンによって
被覆されて有機物の除去を行う方法。 （２）超純水中へオゾン含有気体を供給して微細な気泡
を発生させ、液面の近傍において上昇した気泡を基板面
の有機物被膜と接触させる方法。からなる基板処理方法
である。That is, in the method of the present invention, wet ozone and water mixed with bubbles of ozone-containing gas are caused to act on the surface of the substrate on which the organic film is formed or the surface of the substrate on which the undesirable substance is adhered, (1) By supplying a wet ozone-containing gas through water into a closed processing chamber in which a substrate is placed horizontally with the surface to be processed facing upward, the surface of the organic material is covered with the wet ozone and the organic material is covered. How to do the removal. (2) A method of supplying an ozone-containing gas into ultrapure water to generate fine bubbles, and bringing the bubbles rising near the liquid surface into contact with the organic film on the substrate surface. And a substrate processing method.
【００１６】被処理面を上にして基板を水平に置き、湿
潤オゾンを供給する場合には、高濃度のオゾン含有気体
を水中を通過させオゾン含有気体を水蒸気で飽和させて
供給すると、基板の表面は湿潤なオゾン供給気体によっ
て表面が徐々に濡れ、基板表面に水の薄い膜が形成され
て有機物被膜の除去に大きな効果を発揮する。When the substrate is placed horizontally with the surface to be treated facing upward and wet ozone is supplied, when a high concentration ozone-containing gas is passed through water and the ozone-containing gas is saturated with water vapor and supplied, The surface is gradually wetted by the moist ozone supply gas, and a thin film of water is formed on the surface of the substrate, which is very effective in removing the organic film.
【００１７】ところが、水を直接に基板面に散布した場
合のように形成される水の膜の厚みが大きいと充分な処
理速度を得ることができない。また、基板を加熱すると
湿潤なオゾン含有気体を供給しても高温な基板表面にお
いて薄い水の被膜が形成されないので、湿潤なオゾンに
よって充分な効果が得られない。However, if the thickness of the water film formed is large as in the case where water is directly sprayed on the substrate surface, a sufficient processing speed cannot be obtained. Further, when the substrate is heated, even if a moist ozone-containing gas is supplied, a thin film of water is not formed on the surface of the substrate at high temperature, so that sufficient effect cannot be obtained by the moist ozone.
【００１８】湿潤なオゾン含有気体は、オゾン含有気体
を超純水とを接触することによって得ることができる
が、オゾン含有気体と超純水との接触は、超純水中へオ
ゾン含有気体を吹き込む方法、超純水から生成した水蒸
気あるいは超純水を霧状として混合する方法、気泡塔で
気液接触するなどの方法によって得ることができる。ま
た、この場合に使用する超純水の温度は５０℃以下とす
ることが好ましい。The moist ozone-containing gas can be obtained by contacting the ozone-containing gas with ultrapure water. The contact between the ozone-containing gas and the ultrapure water is performed by adding the ozone-containing gas into the ultrapure water. It can be obtained by a method of blowing in, a method of mixing water vapor generated from ultrapure water or ultrapure water in the form of a mist, a method of gas-liquid contact in a bubble column, and the like. The temperature of the ultrapure water used in this case is preferably 50 ° C. or lower.
【００１９】本発明の方法では、基板を回転して処理を
行っても良いが、基板面に均一にオゾン含有気体を供給
することができれば基板を静置した状態で処理を行って
も良く、またオゾン含有気体の吹き出し口は基板面に均
一に供給できるように設けることが好ましい。In the method of the present invention, the treatment may be carried out by rotating the substrate, but if the ozone-containing gas can be uniformly supplied to the surface of the substrate, the treatment may be carried out with the substrate standing still, Further, it is preferable that the outlet of the ozone-containing gas is provided so that the ozone-containing gas can be uniformly supplied to the substrate surface.
【００２０】また、超純水中へオゾン含有気体を供給し
て微細な気泡を発生させ、上昇した気泡を液面の近傍に
おいて基板面の有機物被膜と接触させる方法は、超純水
中へ微細な孔からオゾン含有気体を吹き出し、水中を上
昇した気泡が液面の近傍において、基板の有機物被膜を
形成した面に接触し、オゾン含有気体の気泡が有機物被
膜の面で破壊され有機物被膜に作用して除去するもので
ある。オゾンの超純水中への導入部には、微細な穴を多
数有する石英、フッ素樹脂、ガラスあるいはセラミック
スの焼結体から噴出させて、微細な気泡を形成して超純
水との接触を高めることによって、超純水中への溶解と
有機物被膜との接触を高めることが好ましい。Further, a method of supplying an ozone-containing gas into ultrapure water to generate fine bubbles and bringing the raised bubbles into contact with the organic film on the substrate surface in the vicinity of the liquid surface is a method of forming fine bubbles into ultrapure water. Ozone-containing gas is blown from a hole, and bubbles rising in water come into contact with the surface of the substrate on which the organic film is formed near the surface of the liquid, and ozone-containing gas bubbles are destroyed on the surface of the organic film and act on the organic film. And then remove it. At the introduction part of ozone into ultrapure water, it is ejected from a sintered body of quartz, fluororesin, glass or ceramics that has many fine holes to form fine bubbles and make contact with ultrapure water. It is preferable to enhance the dissolution in ultrapure water and the contact with the organic film by increasing the concentration.
【００２１】また、基板を設ける位置は、液面上１〜１
５ｍｍの位置とすることが好ましく、またオゾン含有気
体の流量およびオゾン濃度が大きいほど大きな効果を得
ることができる。基板の保持は、裏面を真空吸着して保
持する方法、あるいは基板の周囲を挟持する等の方法に
よって保持することができる。いずれの方法でも、オゾ
ンによって処理をした後には、基板表面を超純水でシャ
ワーあるいはリンスをして基板表面の残渣等を除去した
後に乾燥する。The position where the substrate is provided is 1 to 1 above the liquid surface.
The position is preferably 5 mm, and the greater the flow rate and the ozone concentration of the ozone-containing gas, the greater the effect can be obtained. The substrate can be held by a method of holding the back surface by vacuum suction, or a method of sandwiching the periphery of the substrate. In any of the methods, after the treatment with ozone, the substrate surface is showered or rinsed with ultrapure water to remove residues and the like on the substrate surface, and then dried.
【００２２】処理室内にオゾン含有気体を供給して処理
を行った後に、処理室内のオゾン含有気体を窒素と置換
して処理室内のオゾン含有気体を除去した後に基板を取
り出し、オゾン含有気体が処理室から漏れることを防止
するとともに、オゾンは極めて大きな酸化力を有し、人
体等にも悪影響を及ぼすので、処理室から排出されるオ
ゾンはオゾン分解装置を設けてオゾンを酸素に分解する
必要がある。After the ozone-containing gas is supplied into the processing chamber for processing, the ozone-containing gas in the processing chamber is replaced with nitrogen to remove the ozone-containing gas in the processing chamber, and then the substrate is taken out to process the ozone-containing gas. In addition to preventing leakage from the chamber, ozone has an extremely large oxidizing power and adversely affects the human body and the like.Therefore, ozone discharged from the processing chamber needs to be equipped with an ozone decomposing device to decompose the ozone into oxygen. is there.
【００２３】[0023]
【作用】本発明は、半導体装置の製造用のウエハ等の基
板上の有機物被膜あるいは基板面に付着した好ましくな
い有機物あるいは無機物を除去する方法において、基板
に湿潤なオゾンを接触させて被処理物を分解する方法で
あり、従来のオゾンを注入した超純水による湿式の有機
物被膜の除去方法あるいはオゾンを加熱した基板に作用
させる乾式による除去方法に比べて処理速度が大きく短
時間に有機物被膜等を除去することができる。The present invention is a method for removing an undesirable organic substance or inorganic substance adhering to an organic film or a substrate surface of a substrate such as a wafer for manufacturing a semiconductor device by bringing wet ozone into contact with the substrate. Is a method of decomposing organic matter, which has a faster processing speed than a conventional method of removing an organic film of wet type using ultrapure water into which ozone is injected or a dry method of applying ozone to a heated substrate. Can be removed.
【００２４】[0024]
【実施例】以下に図面を参照して本発明をさらに詳細に
説明する。図１は、湿潤なオゾンによるウエハ等の基板
上の有機物被膜あるいは基板面上の付着物を除去する方
法の１実施例を示したものである。処理室１内には基板
載置台２に基板３が設けられており、また、処理室には
処理室内の気体を排出する排気装置へ結合した排気管４
が設けられており、オゾン含有気体による処理に先立っ
て、処理室内を密閉して排気管から吸引除去する。処理
室の基板載置台は回転軸に取り付けられており、オゾン
含有気体による処理の際には基板を回転し、処理が均一
に行われる構造を有している。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail below with reference to the drawings. FIG. 1 shows an embodiment of a method for removing an organic coating film on a substrate such as a wafer or deposits on the surface of a substrate by using wet ozone. A substrate 3 is provided on a substrate mounting table 2 in the processing chamber 1, and an exhaust pipe 4 connected to an exhaust device for exhausting gas in the processing chamber is provided in the processing chamber.
Is provided, the inside of the processing chamber is sealed and suctioned and removed from the exhaust pipe prior to the processing with the ozone-containing gas. The substrate mounting table in the processing chamber is attached to the rotating shaft, and has a structure in which the substrate is rotated during the processing with the ozone-containing gas so that the processing is uniformly performed.
【００２５】オゾン発生装置５には酸素貯槽６から酸素
が供給され、オゾン発生装置で発生したオゾン含有気体
は気液接触装置７において、超純水と接触して湿潤とな
り、オゾン含有気体供給管８から処理室内へ供給されて
気体分散板９に設けた孔１０から基板の被処理面に作用
する。気体分散板は、石英、フッ素樹脂等から形成され
ており、基板表面に均一にオゾン含有気体を供給可能な
ように、多孔板あるいは気体が通過できる多孔性の焼結
体から形成されている。Oxygen is supplied to the ozone generator 5 from the oxygen storage tank 6, and the ozone-containing gas generated in the ozone generator comes into contact with the ultrapure water in the gas-liquid contact device 7 to become moist, thereby supplying the ozone-containing gas supply pipe. 8 is supplied into the processing chamber from 8 and acts on the surface to be processed of the substrate through the holes 10 provided in the gas dispersion plate 9. The gas dispersion plate is formed of quartz, fluororesin, or the like, and is formed of a porous plate or a porous sintered body through which the gas can pass so that the ozone-containing gas can be uniformly supplied to the substrate surface.
【００２６】処理室内から排出される気体中のオゾン
は、オゾン分解装置１１によって分解されて排出され
る。処理室には基板を洗浄するための超純水供給ノズル
１２が設けられており、処理の終了した基板面を超純水
によって洗浄する。処理の終了後に処理室の内部を窒素
等の気体によって置換し処理室から基板を取り出して乾
燥する。処理室の内部には極めて反応性が大きな湿潤な
オゾンが供給されるので、処理室の内面および処理室内
部の装置類の表面は石英、あるいはフッ素樹脂等で構成
されている。Ozone in the gas discharged from the processing chamber is decomposed and discharged by the ozone decomposing device 11. An ultrapure water supply nozzle 12 for cleaning the substrate is provided in the processing chamber, and the surface of the processed substrate is cleaned with ultrapure water. After the processing is completed, the inside of the processing chamber is replaced with a gas such as nitrogen, and the substrate is taken out from the processing chamber and dried. Since moist ozone having extremely high reactivity is supplied to the inside of the processing chamber, the inner surface of the processing chamber and the surfaces of devices inside the processing chamber are made of quartz, fluororesin or the like.
【００２７】図２は、本発明の他の実施例を示したもの
であるが、処理槽２１には処理液２２が半分程度満たさ
れており、処理槽中には処理液中に微細なオゾン含有気
体の気泡を発生する気泡発生装置２３が設けられてい
る。処理槽の液面２４の近傍には、基板支持具２５にウ
エハなどの基板２６の被処理面を下向きにして取り付け
ており、発生した気泡が基板の被処理面に衝突し、一部
の気泡は被処理面で割れる。その結果溶存したオゾンお
よびオゾン含有気体の気泡の作用によって被処理物の処
理が行われる。処理槽から発生する気体にはオゾンが含
まれているのでオゾン分解装置によって分解して排出す
る。また、処理の終了した被処理基板は被処理液から取
り出した後に、超純水によってリンスして乾燥をする。FIG. 2 shows another embodiment of the present invention, in which the processing tank 21 is filled with about half of the processing liquid 22, and fine ozone is contained in the processing liquid in the processing tank. A bubble generator 23 for generating bubbles of the contained gas is provided. In the vicinity of the liquid surface 24 of the processing tank, a substrate 26 such as a wafer is attached to the substrate support 25 with the surface to be processed facing downward, and the generated bubbles collide with the surface to be processed of the substrate, and some bubbles are attached. Breaks on the surface to be treated. As a result, the object to be treated is treated by the action of the dissolved ozone and the bubbles of the ozone-containing gas. Since the gas generated from the processing tank contains ozone, it is decomposed by an ozone decomposing device and discharged. Further, the processed substrate to be processed is taken out from the liquid to be processed, rinsed with ultrapure water and dried.
【００２８】実施例１ 表面を清浄化した直径６インチのシリコンウエハに、ポ
ジ型フォトレジスト（東京応化工業（株）製 ＯＦＰＲ
−８００）の厚みがプリベーク後に１，４００ｎｍとな
るようにスピンコータによって塗布した。フォトレジス
ト面を上向きにして処理室内に置き、超純水中を通過し
た濃度８０，０００〜１００，０００ｐｐｍのオゾン含
有気体をオゾン濃度、供給量、処理時間を変化させて、
フォトレジストの膜厚をナノメトリックス社製、ナノス
ペックによって測定した。ただし、この場合にはウエハ
の温度および超純水の温度を常温として処理を行った。
その結果を表１に示す。Example 1 A surface-cleaned silicon wafer having a diameter of 6 inches was coated with a positive photoresist (OFPR manufactured by Tokyo Ohka Kogyo Co., Ltd.).
It was applied by a spin coater so that the thickness of −800) would be 1,400 nm after prebaking. The photoresist surface is placed upward in the processing chamber, and the ozone-containing gas having a concentration of 80,000 to 100,000 ppm that has passed through ultrapure water is changed in ozone concentration, supply amount, and processing time.
The film thickness of the photoresist was measured by Nanospec manufactured by Nanometrics. However, in this case, the processing was performed with the temperature of the wafer and the temperature of the ultrapure water being room temperature.
The results are shown in Table 1.
【００２９】[0029]
【表１】 [Table 1]
【００３０】実施例２ 表面を清浄化した直径６インチのシリコンウエハに、ポ
ジ型フォトレジスト（東京応化工業（株）製 ＯＦＰＲ
−８００）の厚みがプリベーク後に１，４００ｎｍとな
るようにスピンコータによって塗布した。Example 2 A positive type photoresist (OFPR manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to a silicon wafer having a diameter of 6 inches whose surface was cleaned.
It was applied by a spin coater so that the thickness of −800) would be 1,400 nm after prebaking.
【００３１】超純水の液面上１ｃｍのところにフォトレ
ジスト面を下向きにして、シリコンウエハを置き、液面
下１００ｍｍのところに設けた開孔径５０μｍの焼結体
からなる気泡発生装置に、オゾン濃度、オゾン含有気体
の供給量を変化させて処理を行った。A silicon wafer is placed with the photoresist surface facing downward at a position 1 cm above the liquid surface of ultrapure water, and a bubble generator made of a sintered body having an opening diameter of 50 μm is provided 100 mm below the liquid surface. The treatment was performed while changing the ozone concentration and the supply amount of the ozone-containing gas.
【００３２】フォトレジスト面は発生するオゾン含有気
体の気泡に絶えず暴露された状態であった。処理の終わ
ったウエハは超純水でリンスして乾燥後実施例１と同様
にしてフォトレジストの膜厚を測定した。The photoresist surface was constantly exposed to the bubbles of the ozone-containing gas that was generated. The treated wafer was rinsed with ultrapure water and dried, and then the thickness of the photoresist was measured in the same manner as in Example 1.
【００３３】[0033]
【表２】 [Table 2]
【００３４】比較例１ 実施例１と同様のフォトレジストを形成したウエハを水
分を含有しない濃度８，０００ｐｐｍのオゾン含有気体
によって２０℃で５分間処理を行ったが、フォトレジス
トの膜厚は初期の膜厚と変わらずフォトレジストを除去
することはできなかった。Comparative Example 1 A wafer having the same photoresist as in Example 1 was treated with an ozone-containing gas having a water-free concentration of 8,000 ppm at 20 ° C. for 5 minutes. The photoresist could not be removed without changing the film thickness.
【００３５】比較例２ ウエハを液面下５０ｍｍに置いた点を除いては実施例２
と同様の方法によって、気体流量４リットル／分で５分
間処理を行った後にリンスして膜厚を測定したところ、
膜厚は７００ｎｍであり、除去速度は１４０ｎｍ／分で
あった。Comparative Example 2 Example 2 except that the wafer was placed 50 mm below the liquid surface.
In the same manner as above, after treating for 5 minutes at a gas flow rate of 4 liters / minute and then rinsing and measuring the film thickness,
The film thickness was 700 nm and the removal rate was 140 nm / min.
【００３６】比較例３ ウエハの温度を１５０℃および２００℃に加熱して実施
例１と同様にして濃度１１０，０００ｐｐｍのオゾンを
用いて処理を行ったが、除去速度はそれぞれ５０ｎｍ／
分、１５０ｎｍ／分であり、水分を含まないオゾン含有
気体を用いた場合の速度と大差なかった。Comparative Example 3 Wafers were heated to 150 ° C. and 200 ° C. and treated with ozone having a concentration of 110,000 ppm in the same manner as in Example 1, but the removal rate was 50 nm / nm.
Min, 150 nm / min, which was not much different from the speed when an ozone-containing gas containing no water was used.
【００３７】[0037]
【発明の効果】本発明は、半導体装置の製造用のウエハ
等の基板上に形成した有機物被膜、基板面に付着した好
ましくない有機化合物、無機化合物等の被処理物を処理
液中を通過させるなどをして湿潤となったオゾンを供給
して被処理物を分解する方法であり、従来のオゾンを注
入した超純水による湿式の有機物被膜の除去方法あるい
は加熱した基板にオゾンを作用させる乾式による除去方
法に比べて処理速度が大きく短時間に被処理物を除去す
ることができる。According to the present invention, an organic film formed on a substrate such as a wafer for manufacturing a semiconductor device, an object to be treated such as an unfavorable organic compound or an inorganic compound adhering to the substrate surface is passed through a treatment liquid. It is a method of decomposing the object to be treated by supplying ozone that has become wet due to, for example, a conventional method of removing the organic film of wet type with ultrapure water into which ozone is injected or a dry method of applying ozone to a heated substrate. The processing speed is higher than that of the removal method described above and the object to be processed can be removed in a short time.
【図１】本発明の湿潤オゾンによる処理方法を説明する
図である。FIG. 1 is a diagram illustrating a treatment method using wet ozone of the present invention.
【図２】本発明のオゾン含有気体の気泡によって、液面
の近傍での処理方法を説明する図である。FIG. 2 is a diagram illustrating a treatment method in the vicinity of a liquid surface by bubbles of ozone-containing gas according to the present invention.
１…処理室、２…基板載置台、３…基板、４…排気管、
５…オゾン発生装置、６…酸素貯槽、７…気液接触装
置、８…オゾン含有気体供給管、９…気体分散板、１０
…孔、１１…オゾン分解装置、１２…超純水供給ノズ
ル、２１…処理槽、２２…処理液、２３…気泡発生装
置、２４…液面、２５…基板支持具、２６…基板1 ... Processing chamber, 2 ... Substrate mounting table, 3 ... Substrate, 4 ... Exhaust pipe,
5 ... Ozone generator, 6 ... Oxygen storage tank, 7 ... Gas-liquid contact device, 8 ... Ozone-containing gas supply pipe, 9 ... Gas dispersion plate, 10
... hole, 11 ... ozone decomposing device, 12 ... ultrapure water supply nozzle, 21 ... processing tank, 22 ... processing liquid, 23 ... bubble generating device, 24 ... liquid level, 25 ... substrate support, 26 ... substrate
Claims (3)
おいて、処理液中を通過させたオゾン含有気体を基板表
面の被処理物に作用させて、被処理物面にオゾンを含有
する処理液の薄膜を形成して、基板を加熱することなく
被処理物を除去することを特徴とする基板処理方法。1. A method for treating a substrate such as a semiconductor wafer, wherein an ozone-containing gas passed through the treatment liquid is caused to act on an object to be treated on the surface of the substrate to form a treatment liquid containing ozone on the surface of the object to be treated. A substrate processing method comprising forming a thin film and removing an object to be processed without heating the substrate.
ゾン含有気体を吹き込んで形成した微細な気泡であり、
液面の近傍に有機物被膜の形成面を下向きに配置して基
板面に作用させることを特徴とする請求項１記載の基板
処理方法。2. The moist ozone-containing gas is fine bubbles formed by blowing the ozone-containing gas into the treatment liquid,
2. The substrate processing method according to claim 1, wherein a surface on which the organic coating film is formed is arranged downward in the vicinity of the liquid surface to act on the substrate surface.
請求項１または２のいずれかに記載の基板処理方法。3. The substrate processing method according to claim 1, wherein the processing liquid is ultrapure water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31506891A JP2891578B2 (en) | 1991-11-29 | 1991-11-29 | Substrate processing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31506891A JP2891578B2 (en) | 1991-11-29 | 1991-11-29 | Substrate processing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05152270A true JPH05152270A (en) | 1993-06-18 |
| JP2891578B2 JP2891578B2 (en) | 1999-05-17 |
Family
ID=18061043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31506891A Expired - Lifetime JP2891578B2 (en) | 1991-11-29 | 1991-11-29 | Substrate processing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2891578B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1063685A1 (en) * | 1998-11-12 | 2000-12-27 | Mitsubishi Denki Kabushiki Kaisha | Photoresist film removing method and device therefor |
| KR20010034087A (en) * | 1998-11-13 | 2001-04-25 | 다니구찌 이찌로오 | Method and device for removing photoresist film |
| JP2001330969A (en) * | 2000-05-23 | 2001-11-30 | Sekisui Chem Co Ltd | Apparatus for removing photoresist |
| JP2002318545A (en) * | 2001-04-20 | 2002-10-31 | Sony Corp | Manufacturing method and manufacturing apparatus for display panel |
| JP2003133290A (en) * | 2001-10-26 | 2003-05-09 | Seiko Epson Corp | Apparatus for stripping resist, method for stripping resist, and method for manufacturing semiconductor device |
| US6616773B1 (en) | 1999-03-12 | 2003-09-09 | Mitsubishi Denki Kabushiki Kaisha | Substrate treatment method |
| US6715944B2 (en) | 1998-11-12 | 2004-04-06 | Mitsubishi Denki Kabushiki Kaisha | Apparatus for removing photoresist film |
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1991
- 1991-11-29 JP JP31506891A patent/JP2891578B2/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1063685A1 (en) * | 1998-11-12 | 2000-12-27 | Mitsubishi Denki Kabushiki Kaisha | Photoresist film removing method and device therefor |
| US6517999B1 (en) | 1998-11-12 | 2003-02-11 | Shimada Rika Kougyo Kabushiki Kaisha | Method of removing photoresist film |
| US6715944B2 (en) | 1998-11-12 | 2004-04-06 | Mitsubishi Denki Kabushiki Kaisha | Apparatus for removing photoresist film |
| EP1063685A4 (en) * | 1998-11-12 | 2004-04-28 | Mitsubishi Electric Corp | Photoresist film removing method and device therefor |
| KR20010034087A (en) * | 1998-11-13 | 2001-04-25 | 다니구찌 이찌로오 | Method and device for removing photoresist film |
| US6517998B1 (en) | 1998-11-13 | 2003-02-11 | Mitsubishi Denki Kabushiki Kaisha | Method for removing photoresist film and apparatus used therefor |
| US7965372B2 (en) | 1998-11-13 | 2011-06-21 | Mitsubishi Denki Kabushiki Kaisha | Apparatus for removing photoresist film |
| US6616773B1 (en) | 1999-03-12 | 2003-09-09 | Mitsubishi Denki Kabushiki Kaisha | Substrate treatment method |
| US6955178B1 (en) | 1999-12-03 | 2005-10-18 | Mitsubishi Denki Kabushiki Kaisha | Substrate treatment apparatus |
| JP2001330969A (en) * | 2000-05-23 | 2001-11-30 | Sekisui Chem Co Ltd | Apparatus for removing photoresist |
| JP2002318545A (en) * | 2001-04-20 | 2002-10-31 | Sony Corp | Manufacturing method and manufacturing apparatus for display panel |
| JP2003133290A (en) * | 2001-10-26 | 2003-05-09 | Seiko Epson Corp | Apparatus for stripping resist, method for stripping resist, and method for manufacturing semiconductor device |
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|---|---|
| JP2891578B2 (en) | 1999-05-17 |
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