JP3535820B2 - Substrate processing method and substrate processing apparatus - Google Patents
Substrate processing method and substrate processing apparatusInfo
- Publication number
- JP3535820B2 JP3535820B2 JP2000307029A JP2000307029A JP3535820B2 JP 3535820 B2 JP3535820 B2 JP 3535820B2 JP 2000307029 A JP2000307029 A JP 2000307029A JP 2000307029 A JP2000307029 A JP 2000307029A JP 3535820 B2 JP3535820 B2 JP 3535820B2
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- water
- hydrogen
- ozone
- processing method
- 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
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- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体素子形成用
のウェハ、ガラス基板、セラミック基板などの各種基板
の上に回路などの構造（パターン）を形成した後、基板
上に残留する有機物などの異物や構造形成中または後に
付着した他の異物を洗浄除去する基板処理方法と基板処
理装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structure for forming a circuit (pattern) on various substrates such as a semiconductor element forming wafer, a glass substrate, a ceramic substrate, and the like. The present invention relates to a substrate processing method and a substrate processing apparatus for cleaning and removing foreign matter and other foreign matter adhered during or after formation of a structure.
【０００２】[0002]
【従来の技術】基板上に微細な電気的素子や回路などの
構造を形成する場合、基板上にフォトレジスト（以下レ
ジストという）などの有機物を塗布、露光、現像して、
任意のレジストパターンを形成し、基板表面をエッチン
グなどの処理をすることによって、前記構造を形成して
いる。この処理を行った後に基板上の不要なレジストを
除去する。2. Description of the Related Art When a structure such as a fine electric element or circuit is formed on a substrate, an organic substance such as a photoresist (hereinafter referred to as resist) is applied, exposed and developed on the substrate,
The structure is formed by forming an arbitrary resist pattern and subjecting the surface of the substrate to etching or the like. After performing this process, unnecessary resist on the substrate is removed.
【０００３】上記のレジストの除去後には、基板上に残
ったレジストの微細片や、構造形成中または後に付着し
た他の異物を基板から洗浄除去する必要がある。従来こ
の洗浄方法は、レジストの種類や条件、あるいは素子形
成工程によって湿式方法と乾式方法とに分けられてい
る。After the removal of the resist, it is necessary to wash and remove fine particles of the resist remaining on the substrate and other foreign substances attached during or after the formation of the structure. Conventionally, this cleaning method is divided into a wet method and a dry method depending on the type and conditions of the resist or the element forming process.
【０００４】上記湿式方法では、多くの場合、硫酸、過
酸化水素水などを主たる成分とする酸化力を有する薬液
を用いている（ＳＰＭ処理）。一方、前記乾式方法で
は、酸素を主たるプロセスガスとして、基板上の有機物
などを酸化分解（アッシング）して除去している。ま
た、基板の汚染状況によっては、酸素プラズマを用いた
アッシング処理、ＳＰＭ処理およびアンモニアと過酸化
水素などを主たる成分とする薬液処理（ＡＰＭ処理）を
適当に組み合わせた洗浄処理が行なわれている。In the above-mentioned wet method, in many cases, a chemical solution containing sulfuric acid, hydrogen peroxide solution or the like as a main component and having an oxidizing power is used (SPM treatment). On the other hand, in the dry method, oxygen is the main process gas, and organic substances and the like on the substrate are removed by oxidative decomposition (ashing). Further, depending on the contamination state of the substrate, a cleaning process is performed by appropriately combining an ashing process using oxygen plasma, an SPM process, and a chemical liquid process (APM process) containing ammonia and hydrogen peroxide as main components.
【０００５】[0005]
【発明が解決しようとする課題】上記従来方法におい
て、湿式方法で処理する場合には、硫酸、過酸化水素、
アンモニアなどの薬剤を使用することから、基板に腐蝕
などの悪影響を与える硫酸蒸気の発生や、アンモニアに
よる鉄分の混入によって、形成された構造に欠陥が生じ
ることがあり、これらを回避するためには、これらの処
理後に、大量の洗浄水を必要とし、かつ排水による環境
負荷が大きいという課題がある。また、乾式方法におい
て酸素プラズマを用いると、該プラズマは高エネルギー
状態であり、化学的に敏感な基板および該基板に形成さ
れた構造に大きなダメージを与えることがあるという課
題がある。In the above conventional method, when a wet method is used, sulfuric acid, hydrogen peroxide,
Since a chemical such as ammonia is used, a defect may occur in the formed structure due to the generation of sulfuric acid vapor, which adversely affects the substrate such as corrosion, or the mixing of iron with ammonia. However, there is a problem that a large amount of washing water is required after these treatments and the environmental load caused by drainage is large. Further, when oxygen plasma is used in the dry method, there is a problem that the plasma is in a high-energy state and may cause large damage to a chemically sensitive substrate and a structure formed on the substrate.
【０００６】従って本発明の目的は、硫酸、過酸化水
素、アンモニア、酸素プラズマなどの使用を必須とせず
に、有害蒸気の発生、鉄分の混入、基板の損傷、環境負
荷などを生じることなく、従来技術と同様な洗浄効果が
得られる基板の処理方法および処理装置を提供すること
である。Therefore, an object of the present invention is to make use of sulfuric acid, hydrogen peroxide, ammonia, oxygen plasma, etc. indispensable, without generating harmful vapor, mixing iron, damaging substrates, environmental load, etc. It is an object of the present invention to provide a substrate processing method and a processing apparatus that can obtain the same cleaning effect as that of the conventional technique.
【０００７】[0007]
【課題を解決するための手段】上記目的は以下の本発明
によって達成される。すなわち、本発明は、基板上に存
在する有機物の除去方法であって、オゾンを含有したガ
スを超純水に溶解した水（以下オゾン水という）で基板
を処理する工程と、水素を含有したガスを超純水に溶解
した水（以下水素水という）で基板を処理する工程とを
含み、オゾン水、または水素水で基板を処理する工程の
いずれかの工程の前に、有機溶剤で基板の洗浄を行な
い、これらの工程を連続的に行うことを特徴とする基板
処理方法；又、レジストを剥離した後に基板上に存在す
る残レジストを含む有機物の除去方法であって、オゾン
水をノズルより吐出して基板を処理する工程と、水素水
をノズルにより吐出して基板を処理する工程とを含み、
上記オゾン水のオゾン濃度が１０ｐｐｍ以上で、上記水
素水の水素濃度が１．０〜１．６ｐｐｍの範囲であり、
且つ、これらの工程を連続的に行うことを特徴とする基
板処理方法；更に、レジストを剥離した後に基板上に存
在する残レジストを含む有機物の除去方法であって、オ
ゾンを含有したガスと水素を含有したガスとを超純水に
溶解した水、もしくはオゾン水と水素水とを混合した水
（以下両者を纏めて混合水という）で基板を処理する
か、あるいはオゾン水と水素水とで基板を同時に処理す
る工程を含み、上記オゾン水または混合水のオゾン濃度
が１０ｐｐｍ以上で、且つ上記水素水または混合水の水
素濃度が１．０〜１．６ｐｐｍであることを特徴とする
基板処理方法；およびこれらの方法を実施する処理装置
を提供する。The above object can be achieved by the present invention described below. That is, the present invention is a method for removing organic substances existing on a substrate, which comprises a step of treating the substrate with water (hereinafter referred to as ozone water) in which a gas containing ozone is dissolved in ultrapure water, and a method of containing hydrogen. A step of treating the substrate with water in which gas is dissolved in ultrapure water (hereinafter referred to as hydrogen water), and the substrate is treated with an organic solvent before any of the steps of treating the substrate with ozone water or hydrogen water. performs cleaning, the substrate processing method and performing these steps continuously; also be present on the substrate after removing the resist
Method for removing organic matter including residual resist
The process of discharging water from the nozzle to process the substrate, and the hydrogen water
And the step of processing the substrate by discharging the
If the ozone concentration of the ozone water is 10 ppm or more,
The hydrogen concentration of the plain water is in the range of 1.0 to 1.6 ppm,
In addition, a group characterized by performing these steps continuously
Plate treatment method; a method of removing organic substances including residual resist existing on the substrate after peeling the resist, wherein water containing ozone and gas containing hydrogen are dissolved in ultrapure water, or The method includes the step of treating the substrate with water in which ozone water and hydrogen water are mixed (hereinafter, both are collectively referred to as mixed water), or simultaneously treating the substrate with ozone water and hydrogen water. Ozone concentration
There at 10ppm or more and the hydrogen concentration of the hydrogen water or mixed water is the substrate processing method characterized in that it is a 1.0 to 1.6 pp m; providing and processing apparatus for carrying out these methods.
【０００８】[0008]
【発明の実施の形態】次に好ましい実施の形態を挙げて
本発明をさらに詳細に説明する。本発明の方法によって
処理される基板とは、例えば、ガラス基板、シリコンも
しくは金属化合物の結晶からなる基板などの各種基板が
挙げられ、特に限定されないが、レジストなどの有機物
を用いて基板上に各種パターンを形成し、レジスト除去
工程を経た基板が本発明の主たる対象となる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. Examples of the substrate to be treated by the method of the present invention include various substrates such as a glass substrate and a substrate made of a crystal of silicon or a metal compound, and are not particularly limited, but various substrates are formed on the substrate using an organic substance such as a resist. A substrate on which a pattern has been formed and which has undergone a resist removal process is the main subject of the present invention.
【０００９】すなわち、レジストを用いて、パターン露
光、現像、ベーキング、エッチング、レジスト剥離など
によって基板上に各種パターンが形成されるが、レジス
ト剥離において、レジストが完全に基板から除去される
ことはなく、微細なレジスト片が基板上に残り、あるい
は一旦剥離した微細レジスト片が基板に再付着したり、
また、上記工程において各種の微細な異物が基板に付着
している場合が多い。本発明はこのような基板の洗浄に
特に有用である。That is, a resist is used to form various patterns on a substrate by pattern exposure, development, baking, etching, resist stripping, etc., but the resist is not completely removed from the substrate during the resist stripping. , A fine resist piece remains on the substrate, or a fine resist piece once peeled off is reattached to the substrate,
Further, in the above process, various fine foreign matters are often attached to the substrate. The present invention is particularly useful for cleaning such substrates.
【００１０】また、レジストに多量のイオンを注入した
場合、例えば、１ｃｍ2当たり１０1 5個以上イオンを注
入した場合には、残レジスト（レジスト剥離後に残った
レジスト片）の除去には前記乾式方法の酸素プラズマな
どを用いるが、イオンの注入量が１０13個程度の場合に
は、本発明の方法でも十分に残レジストの除去が可能で
あり、従って本発明の方法は、ＬＳＩなどの半導体素子
製造工程において、イオンの注入量が１０13個以下の残
レジストの除去に特に有用である。Further, when injected a large amount of ions in the resist, e.g., 1 cm to when injected 2 per 10 1 5 or more ions, the dry to remove the remaining resist (resist stripping after remaining resist strip) Although oxygen plasma or the like is used as the method, when the amount of implanted ions is about 10 13 , the method of the present invention can sufficiently remove the residual resist. Therefore, the method of the present invention is applicable to semiconductors such as LSI. In the device manufacturing process, it is particularly useful for removing the residual resist having an ion implantation amount of 10 13 or less.
【００１１】本発明において使用するオゾン水は、オゾ
ンを含む気体を超純水に溶解させたものであり、オゾン
水のオゾン濃度は１０ｐｐｍ以上であることが必要で、
好ましくは５０〜１００ｐｐｍの濃度である。オゾン濃
度が１０ｐｐｍ未満では、基板に付着しているレジスト
片などの有機物の酸化分解が不充分である。また、オゾ
ン濃度は高い程好ましく、１００ｐｐｍを越えてもよ
い。このようなオゾン水は、公知のオゾン発生装置から
発生したオゾンを含む気体を超純水に接触されることに
より容易に得られる。上記オゾン水は、オゾンの他に、
オゾンの濃度を維持するために、二酸化炭素、炭酸アン
モニウム、酢酸または蟻酸などを含有していてもよい。The ozone water used in the present invention is a gas containing ozone dissolved in ultrapure water, and the ozone concentration of the ozone water must be 10 ppm or more.
The concentration is preferably 50 to 100 ppm. If the ozone concentration is less than 10 ppm, the oxidative decomposition of organic substances such as resist pieces adhering to the substrate is insufficient. Further, the higher the ozone concentration, the more preferable, and it may exceed 100 ppm. Such ozone water can be easily obtained by contacting a gas containing ozone generated from a known ozone generator with ultrapure water. The ozone water is, in addition to ozone,
It may contain carbon dioxide, ammonium carbonate, acetic acid, formic acid or the like in order to maintain the concentration of ozone.
【００１２】上記オゾン水の被処理基板に対する付与速
度は、基板面積１ｃｍ2当たり１ｍｌ／ｍｉｎ以上、好
ましくは１〜１０ｍｌ／ｍｉｎである。付与速度が１ｍ
ｌ／ｍｉｎ未満では、オゾン水が基板の表面全体に行き
渡らないおそれがあり、基板に付着しているレジスト片
などの有機物の酸化分解が不充分である。１ｍｌ／ｍｉ
ｎ以上であれば被処理基板全面に液膜が形成され、有機
物が十分に分解される。また、付与速度が１０ｍｌ／ｍ
ｉｎを越えても、コストが上昇するのみで特別の利益は
ない。The rate of application of the ozone water to the substrate to be treated is 1 ml / min or more, preferably 1 to 10 ml / min, per 1 cm 2 of the substrate area. Application speed is 1m
If it is less than 1 / min, the ozone water may not spread over the entire surface of the substrate, and the oxidative decomposition of organic substances such as resist pieces attached to the substrate is insufficient. 1 ml / mi
When it is n or more, a liquid film is formed on the entire surface of the substrate to be processed, and organic substances are sufficiently decomposed. Also, the application speed is 10 ml / m
Even if it exceeds in, there is no special benefit, only the cost increases.
【００１３】以上のように被処理基板にオゾン水を付与
することにより、基板に付着している微細レジスト片な
どの有機物は酸化分解され、引き続いて行なわれる水素
水による処理で酸化された有機物などが速やかに洗浄除
去されるようになる。また、レジスト片などの有機物が
多い場合やレジストに対するイオン注入量が多い場合に
は、上記のオゾン水による処理は２回以上連続して行な
ってもよい。By applying ozone water to the substrate to be treated as described above, organic substances such as fine resist pieces adhering to the substrate are oxidatively decomposed, and organic substances oxidized by subsequent treatment with hydrogen water, etc. Will be quickly removed by washing. Further, when there are many organic substances such as resist pieces or when the amount of ion implantation into the resist is large, the above-mentioned treatment with ozone water may be continuously performed twice or more.
【００１４】また、オゾン水による処理に際しては、基
板あるいは処理雰囲気を加温してオゾン水による酸化処
理を促進させることができる。加温温度は３０℃以上、
好ましくは６０℃以上であり、このような加温は何れの
方法で行なってもよいが、例えば、加熱超純水や加熱窒
素ガスを処理系に導入することによって行なうことがで
きる。Further, during the treatment with ozone water, the substrate or the treatment atmosphere can be heated to accelerate the oxidation treatment with ozone water. Heating temperature is over 30 ℃,
The temperature is preferably 60 ° C. or higher, and such heating may be performed by any method, but for example, it can be performed by introducing heated ultrapure water or heated nitrogen gas into the processing system.
【００１５】本発明で使用する水素水は、公知の水素発
生装置で発生した水素を含む気体を、公知の方法で超純
水に接触させて得られる。水素水の水素濃度は、０．５
ｐｐｍ以上、好ましくは１．０〜１．６ｐｐｍである。
水素濃度が０．５ｐｐｍ未満では、十分な異物除去が望
めないため不充分である。一方、水素濃度が１．６ｐｐ
ｍを越えると、大気圧下で水素ガスが脱離して危険であ
り、また、気泡の発生があり、洗浄効率の著しい低下を
招くので好ましくない。The hydrogen water used in the present invention is obtained by bringing a gas containing hydrogen generated by a known hydrogen generator into contact with ultrapure water by a known method. Hydrogen concentration of hydrogen water is 0.5
It is not less than ppm, preferably 1.0 to 1.6 ppm.
When the hydrogen concentration is less than 0.5 ppm, sufficient foreign matter removal cannot be expected, which is insufficient. On the other hand, hydrogen concentration is 1.6pp
If it exceeds m, hydrogen gas is desorbed under atmospheric pressure, which is dangerous, and bubbles are generated, resulting in a significant decrease in cleaning efficiency, which is not preferable.
【００１６】上記水素水の被処理基板に対する付与速度
は、基板面積１ｃｍ2当たり１ｍｌ／ｍｉｎ以上、好ま
しくは１〜１０ｍｌ／ｍｉｎである。付与速度が１ｍｌ
／ｍｉｎ未満では、水素水が基板の表面全体に行き渡ら
ないおそれがあり、基板に付着している有機物のオゾン
酸化物および他の異物の洗浄効果が不充分である。１ｍ
ｌ／ｍｉｎ以上であれば、被処理基板全面に水素水の液
膜が形成され、上記オゾン酸化物および他の異物が十分
に洗浄される。また、付与速度が１０ｍｌ／ｍｉｎを越
えても、コストが上昇するのみで特別の利益はない。The rate of application of the hydrogen water to the substrate to be treated is 1 ml / min or more, preferably 1 to 10 ml / min, per 1 cm 2 of the substrate area. Application speed is 1 ml
If it is less than / min, the hydrogen water may not spread all over the surface of the substrate, and the effect of cleaning the organic substance ozone oxides and other foreign substances adhering to the substrate is insufficient. 1m
If it is 1 / min or more, a liquid film of hydrogen water is formed on the entire surface of the substrate to be processed, and the ozone oxide and other foreign matter are sufficiently cleaned. Further, even if the application speed exceeds 10 ml / min, there is no special benefit, only the cost increases.
【００１７】上記オゾン水による処理および水素水によ
る処理は、基板の汚染の程度に従って、いずれも複数回
繰り返してもよい。また、オゾン水と水素水との処理の
順序は、オゾン水による処理を先に行ない、その後に水
素水による処理を行なうのが好ましいが、その逆でもよ
い。さらにオゾン水による処理と水素水による処理を交
互に行ってもよい。The treatment with ozone water and the treatment with hydrogen water may be repeated a plurality of times depending on the degree of contamination of the substrate. Regarding the order of treatment with ozone water and hydrogen water, it is preferable that the treatment with ozone water be performed first and then the treatment with hydrogen water, but the reverse order is also possible. Further, the treatment with ozone water and the treatment with hydrogen water may be performed alternately.
【００１８】さらに本発明では、オゾン水による処理と
水素水による処理とを同時に行ってもよい。また、前記
オゾン水と水素水とを適当な比率で混合した混合液
（Ａ）で基板を処理してもよく、また、オゾンを含む気
体と水素を含む気体を超純水に溶解させた処理液（Ｂ）
（以下ＡおよびＢを纏めて混合水という）で処理しても
よい。さらに混合水による処理の前後にオゾン水または
水素水による処理を付加してもよい。いずれの場合にも
使用するオゾン水、水素水または混合水のオゾン濃度ま
たは水素濃度、あるいはこれらの液の基板に対する付与
速度並びに基板などの加熱は前記と同様でよい。Further, in the present invention, the treatment with ozone water and the treatment with hydrogen water may be carried out simultaneously. Further, the substrate may be treated with the mixed liquid (A) in which the ozone water and the hydrogen water are mixed in an appropriate ratio, or a treatment in which a gas containing ozone and a gas containing hydrogen are dissolved in ultrapure water. Liquid (B)
(Hereinafter, A and B are collectively referred to as mixed water). Furthermore, a treatment with ozone water or hydrogen water may be added before or after the treatment with mixed water. In any case, the ozone concentration or hydrogen concentration of ozone water, hydrogen water or mixed water used, the rate of application of these liquids to the substrate, and the heating of the substrate may be the same as described above.
【００１９】以上のようにオゾン水と水素水、あるいは
混合水で基板を処理することにより、基板に付着してい
る微細レジスト片などの酸化物や他の異物は速やかに洗
浄除去される。特に水素水による処理、あるいは混合水
による処理に際しては、水素水または混合水に超音波を
照射して水素を活性化させることによって、基板の洗浄
効果が一層促進される。超音波処理は通常の方法でよ
く、特に限定されないが、超音波の周波数は０．５ＭＨ
ｚ以上、好ましくは１ＭＨｚ以上である。なお、前記オ
ゾン水にも超音波を照射しても構わない。By treating the substrate with ozone water and hydrogen water or mixed water as described above, oxides and other foreign matter such as fine resist pieces adhering to the substrate can be promptly washed and removed. Particularly, in the treatment with hydrogen water or the treatment with mixed water, the cleaning effect of the substrate is further promoted by irradiating the hydrogen water or the mixed water with ultrasonic waves to activate hydrogen. The ultrasonic treatment may be a usual method and is not particularly limited, but the ultrasonic frequency is 0.5 MH.
z or higher, preferably 1 MHz or higher. The ozone water may be irradiated with ultrasonic waves.
【００２０】以上のオゾン水、水素水あるいは混合水に
よる基板の処理は、被処理基板を水平回転させながら行
なうことが好ましく、被処理基板の回転数は５００ｒｐ
ｍ以上、好ましくは１０００〜３０００ｒｐｍである。
基板の回転数が５００ｒｐｍ未満では 遠心力による基
板上での処理液の置換、および除去した異物のスピンア
ウトなどの点で不充分であり、一方、回転数が３０００
ｒｐｍを越えると、基板がスピンドライして基板面に必
要な液膜を形成することが困難になるなどの点で好まし
くない。The above-mentioned treatment of the substrate with ozone water, hydrogen water or mixed water is preferably carried out while horizontally rotating the substrate to be treated, and the number of revolutions of the substrate to be treated is 500 rp.
m or more, preferably 1000 to 3000 rpm.
When the rotation speed of the substrate is less than 500 rpm, it is insufficient in terms of the replacement of the processing liquid on the substrate by the centrifugal force and the spin-out of the removed foreign matter, while the rotation speed of the substrate is 3000.
If the rpm is exceeded, the substrate is spin-dried and it becomes difficult to form a necessary liquid film on the substrate surface, which is not preferable.
【００２１】以上のオゾン水、水素水あるいは混合水に
よる基板の処理は、オゾンが毒性のあるガスであること
や外部からの埃などの混入を避けるためにも、全体が密
閉され、外界と遮断された雰囲気内で行なうことが好ま
しい。なお、処理終了後には、処理領域に残っているオ
ゾンは熱分解や紫外線照射によって容易に無害化でき
る。The above treatment of the substrate with ozone water, hydrogen water or mixed water is hermetically sealed and shielded from the outside in order to prevent ozone from being a toxic gas and to prevent dust from entering from the outside. It is preferable to carry out in a controlled atmosphere. After the treatment is completed, ozone remaining in the treated area can be easily rendered harmless by thermal decomposition or ultraviolet irradiation.
【００２２】また、本発明において、必須ではないが、
必要に応じて、オゾン水、水素水または混合水で基板を
処理する工程のいずれかの工程の前に、オゾンガス、酸
素ガスなどの酸化性ガスを用いて基板に付着している有
機物を灰化処理したり、上記工程の前に有機溶剤で基板
の洗浄を行なったり、あるいは上記工程の後にフッ化水
素を含んだ水で基板を処理するすることにより本発明の
効果を一層高めることができる。Further, although not essential in the present invention,
If necessary, before any step of treating the substrate with ozone water, hydrogen water or mixed water, oxidize the organic substances adhering to the substrate using an oxidizing gas such as ozone gas or oxygen gas. The effects of the present invention can be further enhanced by treating the substrate, washing the substrate with an organic solvent before the above process, or treating the substrate with water containing hydrogen fluoride after the above process.
【００２３】次に本発明の処理装置について説明する。
本発明の前記方法を実施するための処理装置は、図１に
示すように、処理槽１と、該処理槽中において水平回転
する基板保持体２と、処理槽の上部に設けられ、下方に
液体を吐出するノズル３と、該ノズルに液体を供給する
導管４と、全体を閉鎖するチャンバー５とを有し、上記
ノズル３が基板９の直径以上の長さと基板の直径より狭
い幅とを有する棒状であることを特徴としている。その
他、前記基板保持体２を回転させるモーター６、その他
の必要な薬剤、例えば、超純水、塩酸、硫酸、弗化水素
などの酸、アンモニアなどのアルカリ溶液、炭酸ガス、
窒素ガス、カルボン酸系化合物などを供給する導管７、
処理層１に溜った液体を排出するドレイン８などを有す
る。Next, the processing apparatus of the present invention will be described.
As shown in FIG. 1, a processing apparatus for carrying out the method of the present invention is provided with a processing tank 1, a substrate holder 2 which horizontally rotates in the processing tank, an upper portion of the processing tank, and a lower portion. It has a nozzle 3 for discharging a liquid, a conduit 4 for supplying the liquid to the nozzle, and a chamber 5 for closing the whole, and the nozzle 3 has a length equal to or larger than the diameter of the substrate 9 and a width narrower than the diameter of the substrate. It is characterized by having a rod shape. In addition, a motor 6 for rotating the substrate holder 2 and other necessary chemicals such as ultrapure water, acids such as hydrochloric acid, sulfuric acid and hydrogen fluoride, alkaline solutions such as ammonia, carbon dioxide gas,
Conduit 7 for supplying nitrogen gas, carboxylic acid compound, etc.
It has a drain 8 for discharging the liquid accumulated in the treatment layer 1.
【００２４】図１に示す装置において、基板保持体２上
に、適当な手段、例えば、バキューム式や側面支持式な
どのチャック方式で、一枚または複数枚の基板９が載置
され、前記説明のように、必要に応じて基板を前処理し
た後、水平回転している基板上にオゾン水、水素水ある
いは混合水が一連の工程で供給されて基板が洗浄され
る。基板が洗浄された後、必要に応じて基板を超純水で
リンスし、基板保持体２の回転数を高め、所謂スピンド
ライ法により基板に付着している液体を乾燥除去して、
洗浄された基板が得られる。In the apparatus shown in FIG. 1, one or more substrates 9 are placed on the substrate holder 2 by an appropriate means, for example, a chuck system such as a vacuum system or a side support system. As described above, after pretreating the substrate as necessary, ozone water, hydrogen water or mixed water is supplied to the horizontally rotating substrate in a series of steps to clean the substrate. After the substrate is washed, the substrate is rinsed with ultrapure water as needed to increase the rotation speed of the substrate holder 2 and dry and remove the liquid adhering to the substrate by a so-called spin dry method.
A cleaned substrate is obtained.
【００２５】また、基板を混合水で処理する場合には、
前記オゾン水と水素水とを所定の比率で混合するか、あ
るいはオゾンを含有するガスと水素を含有するガスとを
超純水に所定濃度で溶解した水溶液（混合水）を調製し
ておき、図示のいずれかの経路で該混合水をノズル３に
供給および吐出させればよい。また、オゾン水と水素水
とで基板を同時に処理する場合には、オゾン水と水素水
との供給量を所定の割合にコントロールしてノズル３に
送り、基板９に対して同時に吐出させればよい。When the substrate is treated with mixed water,
The ozone water and hydrogen water are mixed in a predetermined ratio, or an aqueous solution (mixed water) is prepared by dissolving a gas containing ozone and a gas containing hydrogen in ultrapure water at a predetermined concentration, The mixed water may be supplied to and discharged from the nozzle 3 through any of the illustrated paths. Further, when the substrate is treated with ozone water and hydrogen water at the same time, the supply amount of ozone water and hydrogen water is controlled to a predetermined ratio and sent to the nozzle 3 so that they are simultaneously discharged to the substrate 9. Good.
【００２６】上記本発明の装置において、特にノズルの
構成に特徴を有する。その１例を図２に示す。図２は、
ノズルの斜視図、側面図および正面図であり、該ノズル
の長さは、基板の直径とほぼ同一またはより長くし、幅
は基板の直径よりも狭くして棒状になっている。該ノズ
ルは、図示の例ではオゾン水または混合水が供給される
セル２１と水素水または混合水が供給されるセル２２が
仕切り２３によって形成され、各セルにはそれぞれの液
を供給する導管２４がそれぞれ設けられるとともに、下
部には液体を吐出する吐出口２５がそれぞれ設けられて
いる。このようにオゾン水、水素水または混合水の流路
を多数のセルに分割し、かつ各セルにオゾン水、水素水
または混合水を供給し、各吐出口から吐出させることに
より、オゾン水、水素水または混合水の均一な吐出が可
能となる。The above-mentioned device of the present invention is characterized in the structure of the nozzle. One example is shown in FIG. Figure 2
3A and 3B are a perspective view, a side view, and a front view of the nozzle, and the length of the nozzle is substantially the same as or longer than the diameter of the substrate, and the width thereof is narrower than the diameter of the substrate and has a rod shape. In the illustrated example, the nozzle is formed by a partition 23 into a cell 21 to which ozone water or mixed water is supplied and a cell 22 to which hydrogen water or mixed water is supplied, and a conduit 24 for supplying respective liquid to each cell. Are provided, and ejection ports 25 for ejecting the liquid are provided at the lower portions. In this way, ozone water, hydrogen water or a mixed water flow path is divided into a large number of cells, and ozone water, hydrogen water or mixed water is supplied to each cell and discharged from each discharge port, It is possible to uniformly discharge hydrogen water or mixed water.
【００２７】オゾン水または混合水を吐出する各セル２
１、および水素水または混合水を吐出する各セル２２に
は、セルを長さ方向に貫通している超音波発生器である
石英ロッド２６が設けられ、オゾン水、水素水または混
合水にそれぞれ超音波が照射されるようになっている。
水素水または混合水を超音波処理することが望ましく、
オゾン水の超音波照射は必須ではないので、オゾン水の
セルには石英ロッド２６は設けなくてもよい。上記石英
ロッド２６にはアンプが連結され、石英ロッド２６を振
動させて超音波を発生させるようになっている。Each cell 2 for discharging ozone water or mixed water
1, and each cell 22 that discharges hydrogen water or mixed water is provided with a quartz rod 26 that is an ultrasonic wave generator that penetrates the cell in the lengthwise direction. It is designed to be irradiated with ultrasonic waves.
It is desirable to sonicate hydrogen water or mixed water,
Since the ultrasonic irradiation of ozone water is not essential, the quartz rod 26 may not be provided in the ozone water cell. An amplifier is connected to the quartz rod 26, and the quartz rod 26 is vibrated to generate ultrasonic waves.
【００２８】水素水または混合水のみを超音波処理し、
オゾン水は超音波処理しない場合に備えて、オゾン水の
セル２１と水素水または混合水のセル２２との間には超
音波遮蔽板であるショックアブソーバー２７が設けられ
ていることが好ましい。以上の如き構成のノズルを用い
てオゾン水、水素水または混合水を基板表面に供給する
ことにより、基板自体が高速回転していることから、上
記オゾン水、水素水または混合水が基板表面に均一に散
布され、基板は均一に洗浄処理される。Sonicate only hydrogen water or mixed water,
It is preferable that a shock absorber 27, which is an ultrasonic shielding plate, is provided between the ozone water cell 21 and the hydrogen water or mixed water cell 22 in case the ozone water is not subjected to ultrasonic treatment. By supplying ozone water, hydrogen water or mixed water to the substrate surface using the nozzle having the above-mentioned configuration, since the substrate itself is rotating at a high speed, the ozone water, hydrogen water or mixed water can be applied to the substrate surface. The substrate is uniformly sprayed and the substrate is uniformly cleaned.
【００２９】[0029]
【実施例】次に実施例および比較例を挙げて本発明をさ
らに具体的に説明する。以下の実施例および比較例はあ
くまで一つの例であり、本発明を何ら限定するものでは
ない。また、基板に付着する汚染物の量の増減により好
適な処理条件は変化し、かつ残レジストを除去するだけ
が本発明の目的でないことを理解すべきである。本発明
の方法においては、有機物で汚染された基板と有機物に
起因する異物の除去全般に関して効果が望めることを、
下記実施例によって理解すべきである。また、本発明に
よれば、本発明の方法によって処理された後の基板は、
その表面の清浄度が高いことから、そこに形成される構
造（パターン）の特性が向上することも示唆される。な
お、以下においてＳＰＭ（処理）とは、硫酸（濃度９６
重量％）と過酸化水素水（濃度３０重量％）との混合物
による処理を意味し、ＡＰＭ（処理）とは、アンモニア
水（濃度２８重量％）と過酸化水素水（濃度３０重量
％）との混合物による処理を意味し、これらの処理液は
適宜超純水で希釈して使用する。EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. The following examples and comparative examples are merely examples, and do not limit the present invention in any way. It should also be understood that the preferred processing conditions will change with increasing or decreasing amounts of contaminants adhering to the substrate, and that removal of residual resist is not the only purpose of the present invention. In the method of the present invention, it is expected that an effect can be expected with respect to the removal of foreign substances caused by organic substances and substrates contaminated with organic substances.
It should be understood by the following examples. Also according to the invention, the substrate after being treated by the method of the invention is
Since the cleanliness of the surface is high, it is also suggested that the characteristics of the structure (pattern) formed therein are improved. In the following, SPM (treatment) means sulfuric acid (concentration 96
%) And a hydrogen peroxide solution (concentration 30% by weight), and APM (treatment) means ammonia water (concentration 28% by weight) and hydrogen peroxide solution (concentration 30% by weight). Means a treatment with a mixture of these, and these treatment liquids are appropriately diluted with ultrapure water before use.
【００３０】参考例１（サンプルの調製）
８インチＣＺＳｉウェハ（以下基板という）をウェット
浸漬型洗浄装置にてＡＰＭ処理（アンモニア：過酸化水
素水：超純水＝１：１：８）、７０℃、超音波処理）し
た。処理した基板を乾燥後、該基板にＩ線感光レジスト
を枚葉式スピンコーターにて塗布し、Ｉ線で全面露光を
行い、レジストを感光させ、およびベークした。その
後、ＢＦ2あるいはＡｓをイオン注入した。ＢＦ2のドー
プ量が５．０Ｅ１３atoms／ｃｍ2（加速電圧：１５ｋｅ
Ｖ）のものをサンプルＡとし、Ａｓのドープ量が８．０
Ｅ１３atoms／ｃｍ2（加速電圧：３０ｋｅＶ）のものを
サンプルＢとし、何もドープしないものをサンプルＣと
した。サンプルの調製条件を下記表１に示す。各サンプ
ルは何れも光干渉型膜厚測定装置にてレジスト膜厚を測
定した。Reference Example 1 (Preparation of Sample) An 8-inch CZSi wafer (hereinafter referred to as a substrate) was subjected to APM treatment (ammonia: hydrogen peroxide solution: ultra pure water = 1: 1: 8) in a wet immersion type cleaning apparatus, 70 Sonicated). After the treated substrate was dried, an I-ray photosensitive resist was applied to the substrate with a single-wafer spin coater, the entire surface was exposed with I-line, the resist was exposed to light, and baked. Then, BF 2 or As was ion-implanted. The doping amount of BF 2 is 5.0E13 atoms / cm 2 (accelerating voltage: 15 ke
V) is used as sample A, and the As doping amount is 8.0.
The sample having E13 atoms / cm 2 (accelerating voltage: 30 keV) was designated as sample B, and the sample not doped with anything was designated as sample C. The sample preparation conditions are shown in Table 1 below. The resist film thickness of each sample was measured by an optical interference type film thickness measuring device.
【００３１】 [0031]
【００３２】実施例１（サンプルの処理）
それぞれのサンプルについて、オゾン水によるレジスト
の剥離を行い、剥離後の洗浄には、オゾン水、水素水ま
たは混合水を用いる本発明の方法（シーケンス処理１〜
３）を用いた。処理は、図１に示す装置を用いて連続的
にレジストの剥離、洗浄およびその後の乾燥までの処理
を一括して同一装置、同一の処理チャンバー内で行っ
た。各サンプルのシーケンス処理の組み合わせを下記表
２に示す。なお、reference処理１は比較例である。Example 1 (Treatment of Sample) For each sample, the resist was stripped with ozone water, and ozone water, hydrogen water or mixed water was used for cleaning after stripping (the sequence treatment 1). ~
3) was used. The treatment was carried out by using the apparatus shown in FIG. 1 in a continuous manner in which the resist peeling, washing and subsequent drying were collectively performed in the same apparatus and the same processing chamber. Table 2 below shows combinations of sequence processing of each sample. The reference process 1 is a comparative example.
【００３３】 [0033]
【００３４】シーケンス処理１：オゾン水によるレジスト剥離処理
：各サンプルを処理す
るオゾン水は、図２に示すノズルから吐出した。この処
理ステップにおける処理条件を下記表３に示す。また、
処理前後のレジスト膜厚も示す。この時のオゾン水の吐
出量は、基板面積１ｃｍ2当たり１０ｍｌ／ｍｉｎであ
る。オゾン水の吐出口とは別の吐出口から石英ヒーター
によって５０℃に加熱された超純水を基板に吐出し、そ
の上からさらにオゾン水を上記と同一吐出量で吐出し
た。 Sequence treatment 1 : Resist stripping treatment with ozone water : Ozone water for treating each sample was discharged from the nozzle shown in FIG. The processing conditions in this processing step are shown in Table 3 below. Also,
The resist film thickness before and after the treatment is also shown. The discharge rate of ozone water at this time is 10 ml / min per 1 cm 2 of substrate area. Ultrapure water heated to 50 ° C. by a quartz heater was discharged onto the substrate from a discharge port different from the discharge port of ozone water, and ozone water was further discharged from above on the same discharge amount.
【００３５】 [0035]
【００３６】レジスト剥離後のオゾン水による酸化分解
処理：レジスト剥離後の基板についてレーザー光源の顕
微鏡による観察を行った。基板表面にはレジスト膜の残
留は確認されなかったが、若干のレジスト片や比較的大
きな異物が残留していた。これら異物はカーボンやシリ
コンの酸化物を主たる成分とする異物である。レジスト
剥離直後の基板に残留している異物は約３μｍにピーク
を持つ粒度分布をしていた。従って、これら異物は酸化
力のあるオゾン水で容易に酸化分解されるので、オゾン
水による異物の酸化分解処理を行った。酸化分解処理
は、図２に示すノズルよりオゾン水を吐出して行った。
処理前後の異物測定はレーザー光散乱型異物カウンター
にて行った。この時の各サンプルの処理条件とその結果
を下記表４に示す。オゾン水はノズルから、基板面積１
ｃｍ 2当たり１０ｍｌ／ｍｉｎで吐出した。[0036]Oxidative decomposition by ozone water after resist stripping
processing: Substrate after resist stripping
Observation with a microscope was performed. The resist film remains on the substrate surface
No residue was confirmed, but some resist pieces and relatively large
There was residual foreign material. These foreign substances are carbon and
It is a foreign substance whose main component is an oxide of carbon. Resist
Foreign matter remaining on the substrate immediately after peeling peaks at about 3 μm
Had a particle size distribution with. Therefore, these foreign substances are oxidized.
Since ozone is easily oxidized and decomposed with powerful ozone water, ozone
Oxidative decomposition treatment of foreign matter with water was performed. Oxidative decomposition treatment
Was performed by discharging ozone water from the nozzle shown in FIG.
For measuring foreign matter before and after processing, laser light scattering type foreign matter counter
I went there. Processing conditions and results of each sample at this time
Is shown in Table 4 below. Ozone water from the nozzle, substrate area 1
cm 2It was discharged at a rate of 10 ml / min.
【００３７】 [0037]
【００３８】オゾン水による酸化分解処理後の水素水に
よる洗浄処理：水素水は、図２に示す超音波発振子を有
するノズルから吐出して各サンプルを処理した。この時
の超音波の周波数は１．５ＭＨｚである。処理前後の異
物測定はレーザー光散乱型異物カウンターにて行った。
処理前における顕微鏡によるレビューでは、殆どレジス
ト片は確認されず、微小な異物が残留するのみであっ
た。また、異物の粒度分布は３μｍから約１μｍにシフ
トしており、レジスト剥離後に残留していた比較的大き
な異物が酸化分解されたことが示された。水素水のＯＲ
Ｐ値は約−５５０ｍＶであり、粒子と基板上の表面電位
が同じ負にチャージするため、静電的な反発により異物
が除去される。また、超音波によるキャビテーションの
効果によって物理的にも異物が除去され、かつ水素、ヒ
ドロキシなどのラジカルが発生する。この処理ステップ
後に窒素気流中で３０００ｒｐｍのスピンドライを行っ
た。処理後のサンプルはいずれも良好に洗浄されてい
た。For hydrogen water after oxidative decomposition treatment with ozone water
Cleaning treatment by : Hydrogen water was discharged from a nozzle having an ultrasonic oscillator shown in FIG. 2 to treat each sample. The frequency of ultrasonic waves at this time is 1.5 MHz. The measurement of foreign matter before and after the treatment was performed with a laser light scattering type foreign matter counter.
In a review with a microscope before the treatment, almost no resist pieces were confirmed, and only minute foreign matter remained. Further, the particle size distribution of the foreign matter was shifted from 3 μm to about 1 μm, showing that the relatively large foreign matter remaining after the resist was stripped was oxidized and decomposed. OR of hydrogen water
The P value is about −550 mV, and the surface potentials on the particles and the substrate are negatively charged, so that the foreign matter is removed by electrostatic repulsion. In addition, the foreign matter is physically removed by the effect of cavitation by ultrasonic waves, and radicals such as hydrogen and hydroxy are generated. After this treatment step, spin drying was performed at 3000 rpm in a nitrogen stream. All the treated samples were washed well.
【００３９】 [0039]
【００４０】シーケンス処理２ ＳＰＭ処理によるレジスト剥離処理
：サンプルを処理す
るＳＰＭ処理は、一般的な薬液バス洗浄装置によって行
なった。この処理ステップにおける処理条件を下記表６
に示す。また、処理前後のレジスト膜厚も示す。
Sequence Treatment 2 Resist Stripping Treatment by SPM Treatment : The SPM treatment for treating the sample was performed by a general chemical bath cleaning device. Table 6 below shows the processing conditions in this processing step.
Shown in. The resist film thickness before and after the treatment is also shown.
【００４１】レジスト剥離後の基板をレーザー光源の顕
微鏡による観察を行った。基板表面にはレジスト膜の残
留は確認されなかった。レジスト剥離直後の基板に残留
している異物は、約１μｍにピークを持つ粒度分布をし
ていた。次のオゾン水による酸化分解ステップに入っ
た。The substrate after the resist was peeled off was observed with a microscope of a laser light source. No residual resist film was confirmed on the substrate surface. The foreign matter remaining on the substrate immediately after the resist was peeled off had a particle size distribution having a peak at about 1 μm. Next, the oxidative decomposition step with ozone water was started.
【００４２】レジスト剥離後のオゾン水による酸化分解
処理：レジスト剥離後の基板をレーザー光源の顕微鏡に
よる観察を行った。基板表面にはレジスト膜の残留は確
認されなかったが、若干のレジスト片や比較的大きな異
物が残留していた。これら異物はカーボンやシリコンの
酸化物を主たる成分とする異物である。レジスト剥離直
後の基板に残留している異物は約０．５μｍにピークを
持つ粒度分布をしていた。従って、これら異物は酸化力
のあるオゾン水で容易に酸化分解されるので、オゾン水
による酸化分解処理を行った。図２に示すノズルよりオ
ゾン水を吐出して処理を行った。処理前後の異物測定は
レーザー光散乱型異物カウンターにて行った。この時の
各サンプルの処理条件とその結果を表７に示す。オゾン
水は、ノズルから基板面積１ｃｍ2当たり１０ｍｌ／ｍ
ｉｎで吐出した。 Oxidative decomposition by ozone water after resist stripping
Treatment : The substrate after the resist was stripped was observed with a laser light source microscope. No residual resist film was confirmed on the surface of the substrate, but some resist pieces and relatively large foreign matter remained. These foreign substances are those whose main components are oxides of carbon and silicon. The foreign matter remaining on the substrate immediately after the resist was peeled off had a particle size distribution having a peak at about 0.5 μm. Therefore, since these foreign substances are easily oxidatively decomposed with ozone water having an oxidizing power, oxidative decomposition treatment with ozone water was performed. Ozone water was discharged from the nozzle shown in FIG. 2 for processing. The measurement of foreign matter before and after the treatment was performed with a laser light scattering type foreign matter counter. Table 7 shows the processing conditions and the results of each sample at this time. Ozone water is 10 ml / m from the nozzle per 1 cm 2 of substrate area.
It was discharged in.
【００４３】 [0043]
【００４４】オゾン水による酸化分解処理後の水素水に
よる洗浄処理：水素水を、図２に示す超音波発振子を有
するノズルから吐出し、各サンプルを処理した。この時
の超音波の周波数は１．５ＭＨｚである。それぞれのサ
ンプルの処理条件とその結果を下記表８に示す。処理前
後の異物測定はレーザー光散乱型異物カウンターにて行
った。処理前における顕微鏡によるレビューでは微小な
異物が残留するのみであった。この処理ステップ後に窒
素気流中で３０００ｒｐｍのスピンドライを行った。処
理後のサンプルはいずれも良好に洗浄されており、本例
が、従来処理と比して遜色ない結果を与えることが示さ
れ、従来の処理に代替可能であることが示唆された。For hydrogen water after oxidative decomposition treatment with ozone water
Cleaning treatment by : Hydrogen water was discharged from a nozzle having an ultrasonic oscillator shown in FIG. 2 to treat each sample. The frequency of ultrasonic waves at this time is 1.5 MHz. The processing conditions and the results of each sample are shown in Table 8 below. The measurement of foreign matter before and after the treatment was performed with a laser light scattering type foreign matter counter. A microscopic review before processing showed that only minute foreign matter remained. After this treatment step, spin drying was performed at 3000 rpm in a nitrogen stream. All the treated samples were well washed, and this example was shown to give comparable results to the conventional treatment, suggesting that the conventional treatment could be substituted.
【００４５】 [0045]
【００４６】シーケンス処理３ ＳＰＭ処理によるレジスト剥離処理
：サンプルを処理す
るＳＰＭ処理は、一般的な薬液バス洗浄装置によって行
なった。この処理ステップにおける処理条件を下記表９
に示す。また、処理前後のレジスト膜厚も示す。 Sequence Treatment 3 Resist Stripping Treatment by SPM Treatment : The SPM treatment for treating the sample was performed by a general chemical bath cleaning device. The processing conditions in this processing step are shown in Table 9 below.
Shown in. The resist film thickness before and after the treatment is also shown.
【００４７】 [0047]
【００４８】レジスト剥離後の基板についてレーザー光
源の顕微鏡による観察を行った。基板表面には大きな異
物は殆ど確認されなかったが、サンプルによっては異物
の付着が非常に多かった。これはＳＰＭの劣化に起因す
る現象と思われる。この剥離処理の後、処理基板を超純
水中に５分間浸漬してＳＰＭをリンス除去し、スピンド
ライによる乾燥を行なった。The substrate after the resist was peeled off was observed with a laser light source microscope. Almost no large foreign matter was observed on the surface of the substrate, but depending on the sample, a large amount of foreign matter adhered. This is considered to be a phenomenon caused by deterioration of SPM. After this peeling treatment, the treated substrate was immersed in ultrapure water for 5 minutes to remove the SPM, and dried by spin drying.
【００４９】レジスト剥離後のオゾン水を添加した水素
水（混合水）による洗浄処理：上記ＳＰＭ処理後、水素
水（１．５ｐｐｍ）にオゾン水を添加した混合水を用い
て基板を処理した。この時に添加するオゾン水の濃度は
６０ｐｐｍである。この時のオゾン濃度は除去すべき異
物の汚染度によって選択すべきであり、本例で汚染物が
有機物を主としていることと併せて、汚染の度合いも高
いことにより、上記の如き濃度を設定している。基板の
処理には、基板面積１ｃｍ2当たり３ｍｌ／ｍｉｎの混
合水を吐出して、図２に示す超音波発振子を有するノズ
ルから吐出し、各サンプルを洗浄処理した。この時の超
音波の周波数は１．５ＭＨｚである。それぞれのサンプ
ルの処理条件とその結果を下記表１０に示す。処理前後
の異物測定はレーザー光散乱型異物カウンターにて行っ
た。処理前における顕微鏡によるレビューでは殆どレジ
スト片は確認されず、微小な異物が残留するのみであっ
た。また、異物の粒度分布は３μｍから約１μｍにシフ
トしており、レジスト剥離後に残留していた比較的大き
な異物は酸化分解されたことを示している。水素水単独
のＯＲＰ値は約−５５０ｍＶであり、粒子と基板上の表
面電位が同じ負にチャージするため、静電的な反発によ
り酸化物が除去される。また、超音波によるキャビテー
ションの効果によって物理的にも異物が除去され、かつ
水素、ヒドロキシなどのラジカルが発生する。この処理
ステップ後に窒素気流中で３０００ｒｐｍのスピンドラ
イを行った。処理後のサンプルはいずれも良好に洗浄さ
れていた。 Hydrogen added with ozone water after resist stripping
Cleaning treatment with water (mixed water) : After the SPM treatment, the substrate was treated with a mixed water obtained by adding ozone water to hydrogen water (1.5 ppm). The concentration of ozone water added at this time is 60 ppm. At this time, the ozone concentration should be selected according to the degree of contamination of the foreign matter to be removed.In addition to the fact that the contaminants are mainly organic substances in this example, the degree of contamination is also high. ing. For the treatment of the substrate, 3 ml / min of mixed water per 1 cm 2 of the substrate area was ejected and ejected from the nozzle having the ultrasonic oscillator shown in FIG. 2 to wash each sample. The frequency of ultrasonic waves at this time is 1.5 MHz. The processing conditions and the results of each sample are shown in Table 10 below. The measurement of foreign matter before and after the treatment was performed with a laser light scattering type foreign matter counter. In a review with a microscope before the treatment, almost no resist pieces were confirmed, and only minute foreign matter remained. Further, the particle size distribution of the foreign matter is shifted from 3 μm to about 1 μm, which indicates that the relatively large foreign matter remaining after the resist is stripped is oxidized and decomposed. The ORP value of hydrogen water alone is about −550 mV, and the surface potentials on the particles and the substrate are negatively charged, so that the oxide is removed by electrostatic repulsion. In addition, the foreign matter is physically removed by the effect of cavitation by ultrasonic waves, and radicals such as hydrogen and hydroxy are generated. After this treatment step, spin drying was performed at 3000 rpm in a nitrogen stream. All the treated samples were washed well.
【００５０】 [0050]
【００５１】以上の結果からして、特に、レジスト剥離
後の異物の除去にオゾン水と水素水、または混合水によ
る処理が有効であることが示された。なお、本例は枚葉
装置で行なっているが、レジストの如き大量の有機物の
除去を伴わない、これらの異物の除去のみの場合は、水
素水、オゾン水または混合水を用いて浸漬型の処理を行
なっても、ほぼ同様の効果が得られる。従って本発明は
異物の除去という観点において装置の態様にかかわらず
有用である。From the above results, it was shown that the treatment with ozone water and hydrogen water or mixed water is particularly effective for removing foreign matters after the resist is stripped. Although this example is performed by a single-wafer apparatus, it does not involve the removal of a large amount of organic substances such as a resist, and in the case of only removing these foreign substances, hydrogen water, ozone water or mixed water is used for immersion type. Even if the treatment is performed, almost the same effect can be obtained. Therefore, the present invention is useful regardless of the mode of the apparatus in terms of removing foreign matters.
【００５２】比較例１（リファレンス処理１）ＳＰＭによるレジスト剥離処理
：ＳＰＭによるレジスト
剥離処理の条件を下記表１１に示す。また、処理前後の
レジスト膜厚を示す。処理は薬液浸漬型装置にて行っ
た。レジストは全て剥離された。Comparative Example 1 (Reference Treatment 1) Resist Stripping Treatment by SPM: The conditions of the resist stripping treatment by SPM are shown in Table 11 below. In addition, the resist film thickness before and after the treatment is shown. The treatment was performed with a chemical liquid immersion type device. All resist was stripped.
【００５３】 [0053]
【００５４】顕微鏡によるレビューを行ったところ、大
きな異物は殆ど確認されなかったが、サンプルによって
異物の付着が非常に多かった。これはＳＰＭの劣化に起
因する現象と思われる。この洗浄処理の後、処理基板を
超純水中に５分間浸漬してＳＰＭをリンス除去し、スピ
ンドライによる乾燥を行なった後に、ＡＰＭによる洗浄
処理を行った。When a review with a microscope was performed, almost no large foreign matter was confirmed, but foreign matter adhered very much depending on the sample. This is considered to be a phenomenon caused by deterioration of SPM. After this cleaning treatment, the treated substrate was immersed in ultrapure water for 5 minutes to remove SPM, dried by spin drying, and then cleaned by APM.
【００５５】ＳＰＭによるレジスト剥離処理後のＡＰＭ
による洗浄処理：洗浄漕の下部に振動子を有する薬液浸
漬型洗浄装置に、それぞれのサンプルを浸漬して処理を
行った。この時の超音波の周波数は１．５ＭＨｚであ
る。処理前後の異物測定はレーザー光散乱型異物カウン
ターにて行った。処理条件と結果を下記表１２に示す。
残留していた異物は殆ど除去された。 APM after resist stripping treatment by SPM
Cleaning treatment by : Each sample was immersed in a chemical liquid immersion type cleaning device having a vibrator at the bottom of the cleaning tank for processing. The frequency of ultrasonic waves at this time is 1.5 MHz. The measurement of foreign matter before and after the treatment was performed with a laser light scattering type foreign matter counter. The processing conditions and results are shown in Table 12 below.
Most of the remaining foreign matter was removed.
【００５６】 [0056]
【００５７】前記実施例が、上記比較例の従来処理と遜
色ない結果を与えたことは、本発明の処理シーケンス
が、従来処理の代替に耐え得るということの証明であ
り、本発明は、前述の課題を解決し、特に有用であるこ
とが証明された。The fact that the above-mentioned embodiment gave a result comparable to the conventional treatment of the above-mentioned comparative example is proof that the treatment sequence of the present invention can withstand the substitution of the conventional treatment. The problem was solved and proved to be particularly useful.
【００５８】[0058]
【発明の効果】本発明の方法は、半導体素子構造を形成
した後の不要なレジストを除去するプロセスにおいて、
オゾン水、水素水または混合水のみを使用しているの
で、環境負荷の小さい、かつ素子構造にダメージを与え
ない低コストな方法である。本発明の方法は、腐食によ
る素子の電気特性低下を最小限に食い止め、製品歩留ま
りの向上が期待できるため、半導体製造装置のランニン
グコストの低減と安全性の向上を可能にする。このよう
にオゾン水、水素水または混合水を用いたレジスト剥離
後の洗浄工程における一連の処理は、環境負荷の低減お
よび素子形成工程の簡便化により、省エネルギーなどの
今後の製造業における諸問題にも適応できる。According to the method of the present invention, in the process of removing the unnecessary resist after forming the semiconductor device structure,
Since only ozone water, hydrogen water, or mixed water is used, this is a low-cost method that has a small environmental load and does not damage the element structure. According to the method of the present invention, deterioration of electric characteristics of the element due to corrosion can be suppressed to a minimum and improvement of product yield can be expected. Therefore, it is possible to reduce the running cost and the safety of the semiconductor manufacturing apparatus. In this way, a series of treatments in the cleaning process after removing the resist using ozone water, hydrogen water or mixed water may reduce problems in the future such as energy saving by reducing the environmental load and simplifying the element formation process. Can also be adapted.
【００５９】これまでは硫酸、アンモニア、過酸化水
素、または有機溶剤などを用いて、基板上に存在する残
レジストなどの異物を除去していた。本発明の方法は、
これらの薬液を用いないため、半導体素子の構造や配線
材料を著しく腐食することがないため、素子構造のダメ
ージが軽減され、例えば、素子性能の信頼性を向上し、
腐食を防ぐための工程、あるいは処理に用いる材料のコ
スト低減につながり、また、配線材料への腐食の軽減
は、素子の電気抵抗の低下、消費電力の低減および素子
性能の高速化につながる。Up to now, sulfuric acid, ammonia, hydrogen peroxide, or an organic solvent has been used to remove foreign matters such as residual resist existing on the substrate. The method of the present invention is
Since these chemicals are not used, the structure of the semiconductor element and the wiring material are not significantly corroded, damage to the element structure is reduced, and, for example, the reliability of element performance is improved,
This leads to a reduction in the cost of the material used for the step or treatment for preventing corrosion, and the reduction of the corrosion to the wiring material leads to a reduction in the electric resistance of the element, a reduction in power consumption, and an increase in the element performance.
【００６０】また、従来の水素水を活性化して用いる処
理は、微小な異物を除去することが可能であるとされて
いるが、本発明の方法は、前述のオゾン水による処理に
水素水による処理を組み合わせること、または混合水を
用いることにより、硫酸などの高純度の従来の薬液を使
用することなく、例えば、レジストなどのレジストの剥
離から、その後の洗浄までの工程を一括して行うことが
可能であることに意義があり、それを可能にした本発明
の方法および装置を用いることにより、その処理が初め
て可能となる。Further, it is said that the conventional treatment using activated hydrogen water can remove minute foreign matters, but the method of the present invention uses the hydrogen water for the treatment with ozone water. By combining treatments or using mixed water, for example, the steps from stripping of resist such as resist to subsequent cleaning can be performed at once without using a high-purity conventional chemical liquid such as sulfuric acid. It is significant that the processing is possible by using the method and apparatus of the present invention that makes it possible.
【００６１】本発明によれば、このようにレジスト剥離
と洗浄の工程が一括して行われることが可能となり、処
理工程ごとの基板の持ち運びが不要で、かつ危険薬液と
の接触機会の削減および汚染物接触機会の削減などのメ
リットが生じる。また、該メリットはこの一括処理がコ
スト削減などに貢献し得ることの所以である。According to the present invention, the resist stripping and cleaning steps can be performed at once in this way, the carrying of the substrate for each processing step is not required, and the chance of contact with a dangerous chemical solution is reduced. Benefits such as reduced opportunities for contact with pollutants will occur. Further, the merit is that this collective processing can contribute to cost reduction and the like.
【図１】 本発明の処理装置の概略図。FIG. 1 is a schematic diagram of a processing apparatus of the present invention.
【図２】 ノズルの構造を説明する図。FIG. 2 is a diagram illustrating the structure of a nozzle.
１：処理槽 ２：基板保持体 ３：ノズル ４：導管 ５：チャンバー ６：モーター ７：導管 ８：ドレイン ９：基板 ２１，２２：セル ２３：仕切り ２４：導管 ２５：吐出口 ２６：石英ロッド ２７：ショックアブソーバー 1: Processing tank 2: substrate holder 3: Nozzle 4: conduit 5: Chamber 6: Motor 7: conduit 8: Drain 9: Substrate 21,22: cell 23: Partition 24: conduit 25: Discharge port 26: Quartz rod 27: Shock absorber
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｇ０３Ｆ 7/40 Ｈ０１Ｌ 21/30 ５７２Ｂ (56)参考文献 特開2000−117208（ＪＰ，Ａ) 特開2000−138198（ＪＰ，Ａ) 特開2000−70885（ＪＰ，Ａ) 特開 平４−354334（ＪＰ，Ａ) 特開 平４−146616（ＪＰ，Ａ) 特開2000−331977（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 21/304 641 H01L 21/304 643 H05K 3/26 G03F 7/40 B08B 3/12 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 7 identification code FI G03F 7/40 H01L 21/30 572B (56) Reference literature JP 2000-117208 (JP, A) JP 2000-138198 (JP, A) JP 2000-70885 (JP, A) JP 4-354334 (JP, A) JP 4-146616 (JP, A) JP 2000-331977 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) H01L 21/304 641 H01L 21/304 643 H05K 3/26 G03F 7/40 B08B 3/12
Claims (18)
って、オゾンを含有したガスを超純水に溶解した水（以
下オゾン水という）で基板を処理する工程と、水素を含
有したガスを超純水に溶解した水（以下水素水という）
で基板を処理する工程とを含み、オゾン水、または水素
水で基板を処理する工程のいずれかの工程の前に、有機
溶剤で基板の洗浄を行ない、これらの工程を連続的に行
うことを特徴とする基板処理方法。1. A method for removing an organic substance existing on a substrate, comprising a step of treating the substrate with water obtained by dissolving a gas containing ozone in ultrapure water (hereinafter referred to as ozone water), and a gas containing hydrogen. Water dissolved in ultrapure water (hereinafter referred to as hydrogen water)
The step of treating the substrate with an organic solvent is performed before any of the steps of treating the substrate with ozone water or hydrogen water, and performing these steps continuously. A characteristic substrate processing method.
る残レジストを含む有機物の除去方法であって、オゾン
水をノズルより吐出して基板を処理する工程と、水素水
をノズルにより吐出して基板を処理する工程とを含み、
上記オゾン水のオゾン濃度が１０ｐｐｍ以上で、上記水
素水の水素濃度が１．０〜１．６ｐｐｍの範囲であり、
且つ、これらの工程を連続的に行うことを特徴とする基
板処理方法。 2. Exist on the substrate after stripping the resist
Method for removing organic matter including residual resist
The process of discharging water from the nozzle to process the substrate, and the hydrogen water
And the step of processing the substrate by discharging the
If the ozone concentration of the ozone water is 10 ppm or more,
The hydrogen concentration of the plain water is in the range of 1.0 to 1.6 ppm,
In addition, a group characterized by performing these steps continuously
Plate processing method.
る残レジストを含む有機物の除去方法であって、オゾン
を含有したガスと水素を含有したガスとを超純水に溶解
した水、もしくはオゾン水と水素水とを混合した水（以
下混合水という）で基板を処理するか、あるいはオゾン
水と水素水とで基板を同時に処理する工程を含み、上記
オゾン水または混合水のオゾン濃度が１０ｐｐｍ以上
で、且つ上記水素水または混合水の水素濃度が１．０〜
１．６ｐｐｍであることを特徴とする基板処理方法。3. A method for removing an organic matter containing a residual resist existing on a substrate after peeling the resist, which comprises dissolving ozone-containing gas and hydrogen-containing gas in ultrapure water, or ozone. A step of treating the substrate with water in which water and hydrogen water are mixed (hereinafter referred to as mixed water), or simultaneously treating the substrate with ozone water and hydrogen water ;
Ozone water or mixed water has an ozone concentration of 10 ppm or more
And the hydrogen concentration of the hydrogen water or the mixed water is 1.0 to
1.6 pp m is the substrate processing method characterized by the above-mentioned.
しくは金属化合物の結晶からなる基板である請求項１〜
３のいずれか１項に記載の基板処理方法。Wherein the target substrate is a glass substrate, according to claim 1 which is a substrate made of crystalline silicon or a metal compound
4. The substrate processing method according to any one of 3 above.
入された有機物で汚染された基板である請求項１〜３の
いずれか１項に記載の基板処理方法。5. The substrate to be processed is a substrate contaminated with an organic substance or an organic substance into which ions are implanted, according to any one of claims 1 to 3.
The substrate processing method according to any one.
いて付着した有機物で汚染された基板である請求項１〜
３のいずれか１項に記載の基板処理方法。6. target substrate, according to claim 1 which is a substrate which is contaminated with organic material adhering the semiconductor device manufacturing process
4. The substrate processing method according to any one of 3 above.
対する付与速度が、基板面積１ｃｍ2当たり１ｍｌ／ｍ
ｉｎ以上である請求項１〜３のいずれか１項に記載の基
板処理方法。7. The application rate of ozone water or mixed water to a substrate to be treated is 1 ml / m 2 per 1 cm 2 of substrate area.
The substrate processing method according to any one of claims 1 to 3 is in more.
より活性化して被処理基板に付与する請求項１〜３のい
ずれか１項に記載の基板処理方法。8. A hydrogen water, or mixed water, activated by sonication applied to the substrate to be processed according to claim 1-3 Neu
The substrate processing method according to item 1 .
行なう請求項１〜３のいずれか１項に記載の基板処理方
法。9. The substrate processing method according to any one of claims 1 to 3 that performs processing while horizontally rotating the target substrate.
以上である請求項９に記載の基板処理方法。10. The number of rotations of the substrate to be processed is 500 rpm.
The substrate processing method according to claim 9, which is the above.
項１〜３のいずれか１項に記載の基板処理方法。11. The substrate processing method according to any one of claims 1 to 3 for performing processing in the same processing apparatus.
理する請求項１〜３のいずれか１項に記載の基板処理方
法。12. A substrate processing method according to any one of claims 1 to 3 for processing heated substrate to be processed in 30 ° C. or higher.
導入して行なう請求項１２に記載の基板処理方法。13. The substrate processing method according to claim 12, wherein heating is performed by introducing heated ultrapure water or heated nitrogen.
を処理する工程のいずれかの工程の前に、酸化性ガスを
用いて有機物を灰化処理する請求項１〜３のいずれか１
項に記載の基板処理方法。14. ozone water, prior to any step of treating the substrate with hydrogen water or mixed water, one of the claims 1-3 for ashing the organic material with an oxidizing gas 1
Substrate processing method according to item .
を処理する工程のいずれかの工程の後に、フッ化水素を
含んだ水で基板を処理する請求項１〜３のいずれか１項
に記載の基板処理方法。15. ozone water, after any of the steps of treating the substrate with hydrogen water or mixed water, any one of claims 1 to 3 for processing a substrate in containing hydrogen fluoride water < substrate processing method described in <br />.
転する基板保持体と、処理槽の上部に設けられ、下方に
液体を供給するノズルと、該ノズルに液体を供給する導
管と、全体を閉鎖するチャンバーとを有し、上記ノズル
が基板の直径以上の長さと基板の直径より狭い幅とを有
する棒状であることを特徴とする基板の処理装置。16. A processing tank, a substrate holder that horizontally rotates in the processing tank, a nozzle provided at an upper portion of the processing tank for supplying a liquid below, and a conduit for supplying a liquid to the nozzle as a whole. And a chamber for closing the chamber, and the nozzle has a rod shape having a length equal to or larger than the diameter of the substrate and a width narrower than the diameter of the substrate.
求項１６に記載の処理装置。17. The processing apparatus according to claim 16, further comprising an ultrasonic wave generator in the nozzle.
流路または混合水の流路を有し、これらの流路が超音波
に対して遮蔽されている請求項１７に記載の処理装置。18. The process according to claim 17, wherein the nozzle has a flow path of ozone water, a flow path of hydrogen water, or a flow path of mixed water, and these flow paths are shielded from ultrasonic waves. apparatus.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000307029A JP3535820B2 (en) | 2000-10-06 | 2000-10-06 | Substrate processing method and substrate processing apparatus |
| US09/742,423 US6743301B2 (en) | 1999-12-24 | 2000-12-22 | Substrate treatment process and apparatus |
| US10/827,352 US6983756B2 (en) | 1999-12-24 | 2004-04-20 | Substrate treatment process and apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000307029A JP3535820B2 (en) | 2000-10-06 | 2000-10-06 | Substrate processing method and substrate processing apparatus |
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| Publication Number | Publication Date |
|---|---|
| JP2002118085A JP2002118085A (en) | 2002-04-19 |
| JP3535820B2 true JP3535820B2 (en) | 2004-06-07 |
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| JP2000307029A Expired - Lifetime JP3535820B2 (en) | 1999-12-24 | 2000-10-06 | Substrate processing method and substrate processing apparatus |
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| JP4039662B2 (en) * | 2002-08-13 | 2008-01-30 | 株式会社Ｓｕｍｃｏ | Method for cleaning semiconductor substrate or element |
| JP4766836B2 (en) * | 2004-03-01 | 2011-09-07 | 大日本印刷株式会社 | Photomask substrate cleaning method |
| JP4772306B2 (en) | 2004-09-06 | 2011-09-14 | 株式会社東芝 | Immersion optical device and cleaning method |
| JP4824395B2 (en) * | 2004-12-13 | 2011-11-30 | 積水化学工業株式会社 | Resist removing method and resist removing apparatus |
| JP4685478B2 (en) * | 2005-03-11 | 2011-05-18 | 富士通株式会社 | Method for forming metal film pattern |
| JP2007150102A (en) * | 2005-11-29 | 2007-06-14 | Fujitsu Ltd | Exposure device, and cleaning method of optical element |
| JP2007227543A (en) * | 2006-02-22 | 2007-09-06 | Toshiba Corp | Immersion optical device, cleaning method, and immersion exposure method |
| JP2007281089A (en) * | 2006-04-04 | 2007-10-25 | Toyota Motor Corp | Manufacturing method of buildup multilayer wiring board |
| JP2012146690A (en) * | 2009-03-31 | 2012-08-02 | Kurita Water Ind Ltd | Cleaning method for electronic material and cleaning apparatus for electronic material |
| JP2011035300A (en) * | 2009-08-05 | 2011-02-17 | Asahi Sunac Corp | Cleaning apparatus and method |
| JP2012222329A (en) * | 2011-04-14 | 2012-11-12 | Tokyo Electron Ltd | Liquid processing method and liquid processing device |
| JP5752504B2 (en) * | 2011-06-30 | 2015-07-22 | 株式会社トクヤマ | Wiring substrate plating method, plated wiring substrate manufacturing method, and silver etching solution |
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