JPH10172941A - Substrate cleaning method and equipment therefor - Google Patents
Substrate cleaning method and equipment thereforInfo
- Publication number
- JPH10172941A JPH10172941A JP8335705A JP33570596A JPH10172941A JP H10172941 A JPH10172941 A JP H10172941A JP 8335705 A JP8335705 A JP 8335705A JP 33570596 A JP33570596 A JP 33570596A JP H10172941 A JPH10172941 A JP H10172941A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- cleaning
- pure water
- reducing gas
- hydrogen
- 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]
【発明の属する技術分野】本発明は、半導体ウエハ、フ
ォトマスク用のガラス基板、液晶表示装置用のガラス基
板、光ディスク用の基板など（以下、単に基板と称す
る）に対して、純水などの洗浄液を供給して洗浄する基
板洗浄方法及びその装置に係り、特に水溶液により洗浄
処理を行うウエット洗浄に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor wafer, a glass substrate for a photomask, a glass substrate for a liquid crystal display, and a substrate for an optical disk (hereinafter simply referred to as a substrate). BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate cleaning method and an apparatus for cleaning by supplying a cleaning liquid, and particularly to wet cleaning in which a cleaning process is performed using an aqueous solution.
【０００２】[0002]
【従来の技術】Ｓｉウエハなどの半導体基板を洗浄する
基板洗浄処理においては、ＲＣＡ社が提唱した化学的手
法をベースにしたウエット洗浄方法が当然のように使用
されている。つまり、アンモニア：過酸化水素：純水か
らなるアルカリベースの洗浄液（ＳＣ−１液あるいはＡ
ＰＭ液とも呼ばれている）による洗浄処理と、フッ酸
（ＨＦ）水溶液の希釈液からなる洗浄液（ＤＨＦ液とも
呼ばれている）による洗浄処理と、塩酸：過酸化水素：
純水からなる酸ベースの洗浄液（ＳＣ−２液あるいはＨ
ＰＭ液とも呼ばれている）による洗浄処理とを行う。こ
れらの洗浄処理では、ＳＣ−１液で有機性汚れと表面付
着粒子の除去を行い、ＤＨＦ液でシリコン酸化膜の除去
を行い、ＳＣ−２液で表面金属不純物の除去を行うよう
になっている。2. Description of the Related Art In a substrate cleaning process for cleaning a semiconductor substrate such as a Si wafer, a wet cleaning method based on a chemical method proposed by RCA is naturally used. That is, an alkali-based cleaning solution (SC-1 solution or A-solution) consisting of ammonia: hydrogen peroxide: pure water.
Cleaning treatment with a hydrofluoric acid (HF) aqueous solution (also referred to as DHF solution); and hydrochloric acid: hydrogen peroxide:
Acid-based cleaning solution consisting of pure water (SC-2 solution or H
(Also called PM solution). In these cleaning treatments, organic dirt and particles attached to the surface are removed with the SC-1 solution, the silicon oxide film is removed with the DHF solution, and surface metal impurities are removed with the SC-2 solution. I have.
【０００３】その後、上記のように水溶液に種々の薬液
を混合して洗浄液として用いるウエット洗浄方法に代え
て、化学薬品蒸気やガスを不活性ガスで希釈して基板表
面の汚染物を気化しやすい反応生成物に変えて除去する
気相洗浄方法が検討されたが、一部の洗浄工程を除いて
水溶液を利用したウエット洗浄方法が主流となってい
る。これは水分子が非常に分極しやすく、水溶液中では
物質に付着した粒子に働くワンデルワールス力や静電気
力などが気体中よもはるかに小さくなることが洗浄処理
に圧倒的に有利になるからである。そして、基板洗浄処
理工程の一部において気相洗浄方法が採用されているも
のの、再び水溶液を用いたウエット洗浄方法の洗浄メカ
ニズムを解明しようと精力的に研究が進められた。その
結果、洗浄メカニズムがほぼ解明され、新しいウエット
洗浄方法が提案されている（ウルトラクリーンテクノロ
ジーVol.8,No.3,(1996)P.156）。Thereafter, instead of the wet cleaning method in which various chemicals are mixed with the aqueous solution as a cleaning liquid as described above, chemical vapors and gases are diluted with an inert gas to easily vaporize contaminants on the substrate surface. A gas-phase cleaning method of removing instead of a reaction product has been studied, but a wet cleaning method using an aqueous solution except for a part of the cleaning step is mainly used. This is because water molecules are very easy to polarize, and in aqueous solution, the Wanderers force and electrostatic force acting on particles attached to substances are much smaller than in gas, which is overwhelmingly advantageous for cleaning processing. is there. Although a vapor phase cleaning method is employed in a part of the substrate cleaning process, intensive research has been conducted to clarify the cleaning mechanism of the wet cleaning method using an aqueous solution again. As a result, the cleaning mechanism has been almost elucidated, and a new wet cleaning method has been proposed (Ultra Clean Technology Vol. 8, No. 3, (1996) P. 156).
【０００４】その中で基板に付着した表面付着粒子を除
去するには、基板表面とその粒子が同程度で同極性に帯
電して電気的に反発すること、基板表面あるいはその粒
子表面が僅かにエッチングされて、粒子がリフトオフさ
れることが必要と結論付けられている。なお、上記の表
面付着粒子除去条件のうち前者は、電気化学の分野、特
に一般的な洗浄分野では最も基本的な事項として認識さ
れている。In order to remove the particles adhered to the surface of the substrate, the particles are charged to the same degree with the same polarity and repelled, and the surface of the substrate or the surface of the particles is slightly removed. It has been concluded that the particles need to be lifted off after being etched. The former of the above-mentioned conditions for removing particles attached to the surface is recognized as the most basic matter in the field of electrochemistry, particularly in the field of general cleaning.
【０００５】半導体基板のプロセスにおいては、その処
理に応じて基板表面にシリコン酸化膜、シリコン窒化
膜、金属被膜、フォトレジスト被膜などの種々の被膜が
形成されるので、その被膜の種類によって表面付着粒子
となり得る材料も様々である。上述したように表面付着
粒子を除去するためにはその材料を同極性に帯電させる
ことが必要であるが、このためにはアルカリ性水溶液を
用いる方が有利であることが半導体製造分野において最
近になって検証された。したがって、シリコン表面のエ
ッチング能力を備えるアルカリ性のＮＨ4 ＯＨ：Ｈ2 Ｏ
2 ：Ｈ2 Ｏ 溶液が表面付着粒子の除去に有効であると
説明されている。しかしながら、シリコン酸化膜やシリ
コン窒化膜などの絶縁膜は、水素イオンや水素ラジカル
により還元されないので、フッ酸は絶縁膜表面の付着粒
子除去に必須であると考えられている。また、表面電位
を制御するためには、負イオン界面活性剤を添加しても
同様な効果が期待できると述べられている。In the process of a semiconductor substrate, various films such as a silicon oxide film, a silicon nitride film, a metal film, and a photoresist film are formed on the substrate surface in accordance with the processing. There are various materials that can become particles. As described above, in order to remove particles attached to the surface, it is necessary to charge the material to the same polarity. For this purpose, it has recently been advantageous in the field of semiconductor manufacturing to use an alkaline aqueous solution. Has been verified. Therefore, alkaline NH 4 OH: H 2 O having an etching capability of the silicon surface.
2 : It is described that the H 2 O solution is effective for removing particles attached to the surface. However, since an insulating film such as a silicon oxide film or a silicon nitride film is not reduced by hydrogen ions or hydrogen radicals, hydrofluoric acid is considered to be essential for removing adhered particles on the surface of the insulating film. In addition, it is stated that a similar effect can be expected even when a negative ion surfactant is added to control the surface potential.
【０００６】[0006]
【発明が解決しようとする課題】基板表面から付着粒子
を除去して基板を清浄にする洗浄処理に必要なことは、
基板表面から付着粒子を引き離すこと、及び引き離した
粒子が再付着することのないように基板から遠ざけるこ
とである。基板の表面から付着粒子を引き離すために
は、超音波振動を加えた純水を供給する超音波方式や、
ブラシにより機械的に洗浄するブラシ方式や、純水を高
圧噴流で供給する高圧ジェット方式などの手法を用いる
ことによりエッチング能力を持つ薬液を使用せずに済む
が、これらの手法により基板表面から引き離した粒子の
再付着防止のためには、アルカリ性の薬剤あるいは負イ
オン界面活性剤などの薬剤を添加しなければならない。
その一方、表面電位制御のために添加された薬剤は、量
の多少にかかわらず最終的には洗い流さなければならな
い。つまり、薬剤添加により再付着防止処理を施して表
面付着粒子を除去した後には、それらを洗浄除去するた
めに必ずリンス工程を追加しなければならない。したが
って、リンス工程の追加により基板洗浄処理に要する時
間が増加し、基板洗浄処理におけるスループットが低下
するという問題点がある。What is required for a cleaning process for removing adhered particles from the substrate surface and cleaning the substrate is as follows.
The purpose is to separate adhered particles from the substrate surface and to keep the separated particles away from the substrate so that they do not reattach. To separate the adhered particles from the surface of the substrate, an ultrasonic method of supplying pure water with ultrasonic vibration,
By using a method such as a brush method that mechanically cleans with a brush or a high-pressure jet method that supplies pure water with a high-pressure jet, it is not necessary to use a chemical solution that has the etching ability.However, these methods separate the substrate from the substrate surface. In order to prevent the particles from re-adhering, an agent such as an alkaline agent or a negative ion surfactant must be added.
On the other hand, the agent added for controlling the surface potential must be finally washed out regardless of the amount. In other words, after the surface adhesion particles are removed by performing the anti-adhesion treatment by adding a chemical, a rinsing step must be added to wash and remove the particles. Therefore, there is a problem that the time required for the substrate cleaning processing increases due to the addition of the rinsing step, and the throughput in the substrate cleaning processing decreases.
【０００７】さらに、当然のことながらその薬剤を洗い
流すためのリンス工程には一切の薬剤混入が許されない
ので純水のみを使った処理となるが、比抵抗が非常に高
い超純水では粒子が付着しやすいのでリンス工程で万一
粒子が混入した場合には、混入した粒子が基板に付着す
る危険性がある。特に、メーカーからユーザーに引き渡
された新規購入の基板洗浄装置は、その製造時やその搬
入時に生じた汚染のため最終のリンス工程と言えども基
板への粒子付着の危険性が付きまとう。このような新規
購入の装置の場合は、その使用を継続することによって
少しずつ清浄な状態へと落ち着いて行くが、突発的に発
生する汚染により基板に粒子が付着することも十分に考
慮して、最終のリンス工程に使用する洗浄液には安全率
を見込んだ付着防止対策を施すことが必要となっている
のが現実である。[0007] Further, naturally, in the rinsing step for washing out the chemical, no chemical contamination is allowed, so that treatment using pure water alone is performed. However, particles are not formed in ultrapure water having a very high specific resistance. If particles are mixed during the rinsing step, there is a risk that the mixed particles will adhere to the substrate. In particular, a newly purchased substrate cleaning device handed over from a manufacturer to a user has a risk of particles adhering to the substrate even in the final rinsing process due to contamination generated during its manufacture and transport. In the case of such a newly purchased device, it is gradually settled to a clean state by continuing to use the device, but it is necessary to carefully consider that particles may adhere to the substrate due to sudden contamination. It is a reality that the cleaning solution used in the final rinsing step needs to take an anti-adhesion measure in consideration of a safety factor.
【０００８】本発明は、このような事情に鑑みてなされ
たものであって、水溶液中に溶かし込んだ還元ガスで表
面電位を制御することにより、基板から除去した粒子が
再付着することを防止できる基板洗浄方法及びその装置
を提供することを目的とする。[0008] The present invention has been made in view of such circumstances, and by controlling the surface potential with a reducing gas dissolved in an aqueous solution, the particles removed from the substrate are prevented from re-adhering. It is an object of the present invention to provide a method and apparatus for cleaning a substrate that can be performed.
【０００９】[0009]
【課題を解決するための手段】本発明は、このような目
的を達成するために、次のような構成をとる。すなわ
ち、請求項１に記載の基板洗浄方法は、基板に洗浄液を
供給して洗浄を行う基板洗浄方法において、純水に還元
ガスを溶解させた水溶液を前記洗浄液としたことを特徴
とするものである。The present invention has the following configuration in order to achieve the above object. That is, a substrate cleaning method according to claim 1 is characterized in that in the substrate cleaning method of performing cleaning by supplying a cleaning liquid to a substrate, an aqueous solution in which a reducing gas is dissolved in pure water is used as the cleaning liquid. is there.
【００１０】また、請求項２に記載の基板洗浄方法は、
請求項１に記載の基板洗浄方法において、前記還元ガス
を水素としたことを特徴とするものである。[0010] The method for cleaning a substrate according to a second aspect is characterized in that:
2. The method for cleaning a substrate according to claim 1, wherein the reducing gas is hydrogen.
【００１１】また、請求項３に記載の基板洗浄方法は、
請求項１または請求項２に記載の基板洗浄方法におい
て、前記純水を冷却したことを特徴とするものである。[0011] The method for cleaning a substrate according to a third aspect of the present invention includes:
The substrate cleaning method according to claim 1 or 2, wherein the pure water is cooled.
【００１２】また、請求項４に記載の基板洗浄装置は、
基板に洗浄液を供給して洗浄を行う基板洗浄装置におい
て、純水に還元ガスを溶解させる溶解手段と、前記溶解
手段により生成された水溶液を前記洗浄液として基板に
供給する洗浄液供給部とを備えていることを特徴とする
ものである。Further, the substrate cleaning apparatus according to claim 4 is
In a substrate cleaning apparatus for performing cleaning by supplying a cleaning liquid to a substrate, the substrate cleaning apparatus includes a dissolving unit that dissolves a reducing gas in pure water, and a cleaning liquid supply unit that supplies an aqueous solution generated by the dissolving unit to the substrate as the cleaning liquid. It is characterized by having.
【００１３】また、請求項５に記載の基板洗浄装置は、
請求項４に記載の基板洗浄装置において、還元ガスの圧
力を調整して前記溶解手段に供給する圧力調整手段を備
えていることを特徴とするものである。Further, the substrate cleaning apparatus according to claim 5 is
The substrate cleaning apparatus according to claim 4, further comprising a pressure adjusting unit that adjusts the pressure of the reducing gas and supplies the reduced gas to the dissolving unit.
【００１４】また、請求項６に記載の基板洗浄装置は、
請求項４または請求項５に記載の基板洗浄装置におい
て、純水を冷却して前記溶解手段に供給する冷却手段を
備えていることを特徴とするものである。Further, the substrate cleaning apparatus according to claim 6 is
The substrate cleaning apparatus according to claim 4 or 5, further comprising cooling means for cooling pure water and supplying the purified water to the dissolving means.
【００１５】また、請求項７に記載の基板洗浄装置は、
請求項４ないし請求項６のいずれかに記載の基板洗浄装
置において、前記溶解手段は、純水が供給される液室
と、前記液室内に設けられ、還元ガスに対して透過性を
有する複数の中空糸とを備え、前記中空糸の中空部から
還元ガスを透過させることにより純水に還元ガスを溶解
させることを特徴とするものである。Further, the substrate cleaning apparatus according to claim 7 is
7. The substrate cleaning apparatus according to claim 4, wherein the dissolving unit is provided in a liquid chamber to which pure water is supplied, and a plurality of liquid chambers provided in the liquid chamber and having permeability to a reducing gas. And dissolving the reducing gas in pure water by transmitting the reducing gas through the hollow portion of the hollow fiber.
【００１６】[0016]
【作用】請求項１に記載の発明方法の作用は次のとおり
である。従来は、例えば、アルカリ性の薬剤を純水に混
合する割合を調整してｐＨを調整することにより基板の
表面電位を制御していた。特に、再付着を防止するため
には基板と粒子の電位極性を同程度同極性にしてそれら
を反発させる必要がある。電気化学の分野では、多くの
物質の等電点（表面電位がゼロとなって、電気泳動現象
などの界面動現象などを全く示さなくなる物質固有の
値）が酸性側にあるので、同極性にするにはアルカリ性
の側で極性を揃えることが有利であると考えられてい
た。このことは基板の洗浄においても例外ではなく、同
様にアルカリ性にすることでほとんどの粒子を負に帯電
させることが可能であることが確認されている。The operation of the method according to the present invention is as follows. Conventionally, for example, the surface potential of a substrate has been controlled by adjusting the pH by adjusting the ratio of mixing an alkaline agent with pure water. In particular, in order to prevent re-adhesion, it is necessary to make the potential polarity of the substrate and the particles the same and to repel them. In the field of electrochemistry, the isoelectric point of many substances (a value peculiar to substances that have no surface potential and exhibit no interfacial phenomena such as electrophoresis) is on the acidic side. It was thought that it was advantageous to make the polarity uniform on the alkaline side. This is not an exception in washing the substrate, and it has been confirmed that almost particles can be negatively charged by making the particles alkaline.
【００１７】発明者等は、アルカリ性の薬剤を混合して
ｐＨを調整する代わりに、純水に直接還元ガスを溶かし
込んで還元ガスの活量を調整しても電位を制御できるこ
とに気が付いた。この場合、還元ガスの活量ではｐＨが
ほとんど変化しないことが実験的に確認されていること
から、イオンの介在により電位が決定されるのではな
く、還元ガスが直接的に物質表面と反応して電子を与え
ることにより電位が決定されているものと考えられる。
このように還元ガスを純水中に溶解させた水溶液を洗浄
液として基板に供給することにより、基板表面と粒子の
電位を同極性に制御することができる。また、この洗浄
液はアルカリ性の薬剤や負イオン界面活性剤などの薬剤
を含まないので、最終のリンス工程でも使用することが
できる。The present inventors have noticed that the potential can be controlled by dissolving the reducing gas directly in pure water and adjusting the activity of the reducing gas, instead of adjusting the pH by mixing an alkaline agent. In this case, since it has been experimentally confirmed that the pH hardly changes with the activity of the reducing gas, the reducing gas reacts directly with the material surface instead of determining the potential by the presence of ions. It is considered that the potential is determined by giving electrons.
By supplying an aqueous solution obtained by dissolving a reducing gas in pure water to the substrate as a cleaning liquid, the potential of the substrate surface and the potential of the particles can be controlled to have the same polarity. Further, since this cleaning liquid does not contain a chemical such as an alkaline chemical or a negative ion surfactant, it can be used in the final rinsing step.
【００１８】また、請求項２に記載の発明方法によれ
ば、還元ガスである水素を純水に溶存させることによ
り、アルカリ性の薬剤や負イオン界面活性剤などの薬剤
を混合することなく基板表面と粒子の電位を同極性に制
御することができる。Further, according to the method of the present invention, hydrogen as a reducing gas is dissolved in pure water, so that the surface of the substrate can be mixed without mixing an alkaline agent or an agent such as a negative ion surfactant. And the potential of the particles can be controlled to the same polarity.
【００１９】また、請求項３に記載の発明方法によれ
ば、還元ガス（例えば水素）を溶かし込む純水を冷却し
ておくことにより、還元ガスの飽和溶解濃度を高くする
ことができ、電位を制御するのに充分な電子を洗浄液に
含ませることができる。Further, according to the method of the present invention, by cooling the pure water into which the reducing gas (eg, hydrogen) is dissolved, the saturated dissolved concentration of the reducing gas can be increased, and the potential of the reducing gas can be increased. Can be included in the cleaning liquid to control the temperature.
【００２０】また、請求項４に記載の発明装置の作用は
次のとおりである。溶解手段により純水に還元ガス（例
えば水素）を溶解させ、このようにして生成された水溶
液を洗浄液として洗浄液供給部より基板に供給する。洗
浄液には、還元ガスが溶解されているので、基板表面と
粒子の電位を同極性に制御することができる。また、こ
の洗浄液は従来例のようにアルカリ性の薬剤や負イオン
界面活性剤などの薬剤を含まないので、最終のリンス工
程においても使用することができる。The operation of the device according to the present invention is as follows. The reducing gas (eg, hydrogen) is dissolved in pure water by a dissolving means, and the aqueous solution thus generated is supplied to the substrate from the cleaning liquid supply unit as a cleaning liquid. Since the reducing gas is dissolved in the cleaning liquid, the potential of the substrate surface and the potential of the particles can be controlled to have the same polarity. Further, since this cleaning liquid does not contain a chemical such as an alkaline chemical or a negative ion surfactant as in the conventional example, it can be used in the final rinsing step.
【００２１】また、請求項５に記載の発明装置によれ
ば、還元ガスの圧力を圧力調整手段により調整して溶解
手段に供給すると、純水に溶解する還元ガスの濃度を制
御することができる。例えば、還元ガスとして水素を溶
解させる場合には、安全性を考慮してその濃度を調整し
ても良い。According to the apparatus of the present invention, when the pressure of the reducing gas is adjusted by the pressure adjusting means and supplied to the dissolving means, the concentration of the reducing gas dissolved in the pure water can be controlled. . For example, when dissolving hydrogen as a reducing gas, its concentration may be adjusted in consideration of safety.
【００２２】また、請求項６に記載の発明装置によれ
ば、冷却手段により純水を冷却しておくと還元ガスの飽
和溶解濃度を高くすることができ、電位を制御するのに
充分な電子を洗浄液に含ませることができる。According to the apparatus of the present invention, if pure water is cooled by the cooling means, the saturated dissolved concentration of the reducing gas can be increased, and sufficient electrons can be controlled to control the potential. Can be included in the cleaning solution.
【００２３】また、請求項７に記載の発明装置によれ
ば、還元ガスに対して透過性を有する複数の中空糸の中
空部から還元ガスを透過させることにより、液室内の純
水に還元ガスを溶解させているので、還元ガスの供給口
と液室内との接触面積が大きくなる。According to the apparatus of the present invention, the reducing gas is permeated from the hollow portions of the plurality of hollow fibers permeable to the reducing gas, so that the pure gas in the liquid chamber is reduced to the pure water in the liquid chamber. Is dissolved, the contact area between the supply port of the reducing gas and the liquid chamber increases.
【００２４】[0024]
【発明の実施の形態】以下、図面を参照して本発明の一
実施例を説明する。図１は本発明に係る基板洗浄装置の
概略縦断面図であり、図２はその平面図である。第１の
電動モータ１の駆動によって鉛直方向の軸芯回りで回転
する回転軸２の上端部には、基板Ｗを真空吸着保持する
スピンチャック３が取り付けられている。これらにより
基板Ｗを鉛直方向の軸芯周りで回転可能に保持する基板
保持手段４が構成されている。その基板保持手段４によ
って保持される基板Ｗの上方の所定箇所には、第２の電
動モータ５によって回転変位可能に支持ブラケット６が
配設されている。その支持ブラケット６には還元ガスを
純水に溶解させた水溶液を洗浄液として基板Ｗに供給す
るためのノズル７が配設されている。なお、ノズル７が
本発明における洗浄液供給部に相当する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic vertical sectional view of a substrate cleaning apparatus according to the present invention, and FIG. 2 is a plan view thereof. A spin chuck 3 for holding a substrate W by vacuum suction is attached to an upper end of a rotating shaft 2 that rotates around a vertical axis by driving of a first electric motor 1. These constitute a substrate holding means 4 for holding the substrate W rotatably about a vertical axis. A support bracket 6 is disposed at a predetermined position above the substrate W held by the substrate holding means 4 so as to be rotationally displaceable by a second electric motor 5. The support bracket 6 is provided with a nozzle 7 for supplying an aqueous solution in which a reducing gas is dissolved in pure water to the substrate W as a cleaning liquid. Note that the nozzle 7 corresponds to the cleaning liquid supply unit in the present invention.
【００２５】上記の基板保持手段４としては、上述した
真空吸着式に限らず、例えば、スピンチャック３上に基
板Ｗの外周縁を支持する複数個の基板支持部材を立設
し、これらの基板支持部材の上端部に基板Ｗの水平方向
の位置を規制する位置決めピンを設けて、基板Ｗをスピ
ンチャック３の上面から離間した状態で回転可能に保持
させるように構成するものであってもよい。The substrate holding means 4 is not limited to the vacuum suction type described above. For example, a plurality of substrate supporting members for supporting the outer peripheral edge of the substrate W are provided on the spin chuck 3 and these substrate holding members are erected. A positioning pin for regulating the horizontal position of the substrate W may be provided at the upper end of the support member so as to rotatably hold the substrate W while being separated from the upper surface of the spin chuck 3. .
【００２６】基板保持手段４およびそれによって保持さ
れた基板Ｗの周囲は、図示しない昇降駆動機構によって
昇降可能なカップ８で囲われ、基板Ｗの洗浄時に、基板
Ｗの上に供給される洗浄液の飛散を防止できるように構
成されている。The periphery of the substrate holding means 4 and the substrate W held by the substrate W are surrounded by a cup 8 which can be raised and lowered by a lifting drive mechanism (not shown). It is configured to prevent scattering.
【００２７】カップ８の側方（図中の右側）には、カッ
プ８を非作用位置に下降した状態で、基板Ｗの表面上の
洗浄位置と、基板Ｗの上方から外れた非洗浄時の待機位
置とにわたって変位可能に基板Ｗの表面を洗浄する洗浄
ブラシ９が配設されている。この洗浄ブラシ９は、洗浄
時に付着した粒子などを除去するため、待機位置にある
ときに待機ポット１０に収容される。また、洗浄ブラシ
９による基板Ｗの洗浄時には、洗浄液供給ノズル１１か
ら純水などの洗浄液を供給する。On the side of the cup 8 (on the right side in the figure), the cup 8 is lowered to the non-operating position, and the cleaning position on the surface of the substrate W and the position at the time of non- A cleaning brush 9 for cleaning the surface of the substrate W so as to be displaceable over the standby position is provided. The cleaning brush 9 is accommodated in the standby pot 10 when it is at the standby position, in order to remove particles and the like attached at the time of cleaning. When the substrate W is cleaned by the cleaning brush 9, a cleaning liquid such as pure water is supplied from the cleaning liquid supply nozzle 11.
【００２８】上記のノズル７には、本発明の溶解手段と
しての溶解装置１２が移送管１３を介して接続されてい
る。溶解装置１２は、還元ガスである水素に対して透過
性を有する浸透膜１４により気室１５ａと液室１５ｂと
に仕切られて構成されている。その気室１５ａには開閉
弁１６及び圧力調整器Ｐを備えた水素ガスを供給する導
入管１７と排気管１８とが接続され、液室１５ｂには純
水供給管１９および冷却装置２０、移送管１３が接続さ
れている。なお、上記の浸透膜１４は、例えば、約０．
０５μｍ程度の無数の孔を有し、水分子を透過せず気体
分子のみを透過する。The nozzle 7 is connected to a melting device 12 as a melting means of the present invention via a transfer pipe 13. The dissolving apparatus 12 is configured to be partitioned into a gas chamber 15a and a liquid chamber 15b by a permeable membrane 14 having permeability to hydrogen as a reducing gas. The gas chamber 15a is connected to an inlet pipe 17 for supplying hydrogen gas provided with an on-off valve 16 and a pressure regulator P and an exhaust pipe 18, and the liquid chamber 15b is connected to a pure water supply pipe 19 and a cooling device 20, Tube 13 is connected. The above permeable membrane 14 is, for example, about 0.1 mm.
It has a myriad of pores of about 05 μm and does not transmit water molecules but only gas molecules.
【００２９】本発明の圧力調整手段に相当する圧力調整
器Ｐは、溶解装置１２に供給される水素の圧力を調整す
るものである。この圧力調整器Ｐによって水素の圧力を
調整することにより、純水中に溶解する水素の濃度を制
御することができる。The pressure adjuster P corresponding to the pressure adjusting means of the present invention adjusts the pressure of hydrogen supplied to the melting device 12. By adjusting the pressure of hydrogen by the pressure regulator P, the concentration of hydrogen dissolved in pure water can be controlled.
【００３０】純水供給管１９に配設されている冷却装置
２０は、純水を冷却して溶解装置１２に供給するもので
ある。その冷却温度としては、例えば、０〜２０℃（ま
たは室温程度）の範囲が好ましい。このように純水の温
度を下げて溶解装置１２に供給することにより水素ガス
の飽和溶解濃度を高くし、高濃度で水素ガスを溶解でき
るように構成されている。純水に高濃度で水素を溶解さ
せることにより、基板Ｗ及び表面付着粒子の電位を制御
するのに充分な電子を含ませることができ、確実に粒子
を基板Ｗから除去することができる。このようにして純
水に水素を溶解させ、この水溶液を洗浄液としてノズル
７から基板Ｗに供給するようになっている。The cooling device 20 provided in the pure water supply pipe 19 cools the pure water and supplies the pure water to the dissolving device 12. As the cooling temperature, for example, a range of 0 to 20 ° C. (or about room temperature) is preferable. Thus, by lowering the temperature of the pure water and supplying it to the dissolving device 12, the saturated dissolution concentration of the hydrogen gas is increased, and the hydrogen gas can be dissolved at a high concentration. By dissolving hydrogen at a high concentration in pure water, sufficient electrons for controlling the potentials of the substrate W and the particles attached to the surface can be contained, and the particles can be reliably removed from the substrate W. In this way, hydrogen is dissolved in pure water, and this aqueous solution is supplied to the substrate W from the nozzle 7 as a cleaning liquid.
【００３１】なお、洗浄液に含まれる水素の濃度は、上
記の圧力調整器Ｐの圧力及び／または冷却装置２０の冷
却温度を調整することにより設定する。その濃度は高濃
度でも良いが水素の溶解濃度は必ずしも飽和濃度である
必要はない。水素には爆発の危険性が伴うので、安全性
を考慮して爆発限界の４％以下の濃度に設定しても良
い。このように設定した場合には、水素の溶解度が０．
０１８（at P= １Kg/cm2）であるから飽和水素濃度は８
×１０-4モル／リットルとなり、混合気体の圧力を１Kg
/cm2にするとヘンリーの法則から水素分圧が４％の場合
の最大溶解濃度は３．２×１０-5モル／リットルとな
る。したがって、ｐＨ値換算で０．７程度制御範囲が狭
まることになるが圧力調整器Ｐで圧力を高めることによ
りそれを補うことができる。The concentration of hydrogen contained in the cleaning liquid is set by adjusting the pressure of the pressure regulator P and / or the cooling temperature of the cooling device 20. The concentration may be high, but the dissolved concentration of hydrogen does not necessarily have to be the saturated concentration. Since hydrogen has a risk of explosion, the concentration may be set to 4% or less of the explosion limit in consideration of safety. When set as described above, the solubility of hydrogen is set to 0.1.
018 (at P = 1 kg / cm 2 ), the saturated hydrogen concentration is 8
× 10 -4 mol / l, and the pressure of the mixed gas is 1 kg
/ cm 2 , the maximum dissolved concentration at a hydrogen partial pressure of 4% is 3.2 × 10 −5 mol / liter according to Henry's law. Therefore, the control range is reduced by about 0.7 in terms of pH value, but this can be compensated for by increasing the pressure with the pressure regulator P.
【００３２】次いで、上記のように構成された基板洗浄
装置を用いた基板洗浄方法について説明する。純水を一
定温度に冷却して溶解装置１２に供給し、その液室１５
ｂに冷却した純水を流通させるとともに、導入管１７か
ら一定圧力に調整した水素を供給し、、その気室１５ａ
に水素を流通させる。気室１５ａからは浸透膜１４を通
して水素が液室１５ｂ側に浸透し、冷却された純水に水
素が一定濃度で溶解する。このようにして純水に一定濃
度で水素を溶解させた水溶液を洗浄液として、基板保持
手段４によって回転状態で保持された基板Ｗにノズル７
から一定時間だけ供給する。Next, a substrate cleaning method using the substrate cleaning apparatus configured as described above will be described. Pure water is cooled to a certain temperature and supplied to the dissolving apparatus 12, where the liquid chamber 15
b, while supplying cooled pure water through the inlet pipe 17 and supplying hydrogen adjusted to a constant pressure to the gas chamber 15a.
Hydrogen is passed through. From the gas chamber 15a, hydrogen penetrates into the liquid chamber 15b through the permeable membrane 14, and hydrogen is dissolved in cooled pure water at a constant concentration. The aqueous solution obtained by dissolving hydrogen at a constant concentration in pure water as described above is used as a cleaning liquid, and the nozzle 7
From a certain time.
【００３３】このように還元ガスである水素を純水に溶
解させた水溶液を洗浄液として基板Ｗに供給することに
より、水素が直接的に基板Ｗおよび付着している粒子に
反応して電子を与え、基板Ｗと付着粒子の表面電位を同
程度の負極性に制御することができる。したがって、基
板Ｗに付着している粒子が基板Ｗと電気的に反発してそ
の表面から除去されるとともに、基板Ｗから除去された
粒子が再付着することを防止できる。この過程において
は電子を放出した水素がイオン化するが、ｐＨを変化さ
せるほどの量ではない。上記の洗浄液は、アルカリ性の
薬剤や負イオン界面活性剤などの薬剤を含まないので、
その後に最終リンス工程を行う必要がなく洗浄処理が短
縮できてスループットを向上させることができる。ま
た、上記の洗浄液を最終のリンス工程でも使用すること
ができる。By supplying an aqueous solution in which hydrogen as a reducing gas is dissolved in pure water to the substrate W as a cleaning liquid, the hydrogen directly reacts with the substrate W and attached particles to give electrons. In addition, the surface potential of the substrate W and the attached particles can be controlled to the same negative polarity. Therefore, the particles adhered to the substrate W are electrically repelled from the substrate W and are removed from the surface thereof, and the particles removed from the substrate W can be prevented from being attached again. In this process, the hydrogen that has released electrons is ionized, but not in such an amount as to change the pH. Since the above-mentioned cleaning liquid does not contain chemicals such as alkaline chemicals and anionic surfactants,
After that, there is no need to perform a final rinsing step, so that the cleaning process can be shortened and the throughput can be improved. Further, the above-mentioned cleaning liquid can be used in the final rinsing step.
【００３４】なお、上述した装置では、浸透膜１４を採
用した溶解装置１２で水素を純水に溶解させるようにし
たが、この溶解装置１２に代えて図３に示すような溶解
装置を採用してもよい。なお、図３は、溶解装置の概略
縦断面図である。この溶解装置３０は、水素に対して透
過性を有する中空糸を複数本束ねた浸透部３１を有し、
浸透部３１の気室である各中空糸の中空部に導入管１７
より水素を供給して排気管１８へ排出する。冷却装置２
０を経て冷却された純水は液室３３に導入され、移送管
１３へ向かう間に浸透部３１の各中空糸から水素を溶か
し込まれるようになっている。このように上記の溶解装
置３０は、その浸透部３１が複数本の中空糸から構成さ
れているので、上記の溶解装置１２のように平面的に気
室１５ａと液室１５ｂとが接しているものに比較して水
素の供給口と液室３３との接触面積を非常に大きくする
ことができる。したがって、溶解装置３０を小型化する
ことができるとともに効率よく水素を純水に溶解させる
ことができる。In the above-described apparatus, hydrogen is dissolved in pure water by the dissolving device 12 employing the permeable membrane 14, but a dissolving device as shown in FIG. You may. FIG. 3 is a schematic longitudinal sectional view of the melting apparatus. The dissolving device 30 has a permeation portion 31 in which a plurality of hollow fibers permeable to hydrogen are bundled,
Introducing pipe 17 into the hollow part of each hollow fiber, which is the air chamber of permeation part 31
More hydrogen is supplied and discharged to the exhaust pipe 18. Cooling device 2
The pure water cooled through 0 is introduced into the liquid chamber 33, and hydrogen is dissolved from each hollow fiber of the permeation section 31 while going to the transfer pipe 13. As described above, in the dissolving device 30, since the permeation portion 31 is formed of a plurality of hollow fibers, the air chamber 15 a and the liquid chamber 15 b are in planar contact with each other as in the dissolving device 12. The contact area between the hydrogen supply port and the liquid chamber 33 can be made very large as compared with the case of the above. Therefore, the dissolving device 30 can be downsized, and hydrogen can be efficiently dissolved in pure water.
【００３５】なお、上記の説明では、基板を一枚ずつ洗
浄する枚葉式の基板洗浄装置を例に採って説明したが、
本発明は複数枚の基板を同時に洗浄するバッチ式の基板
洗浄装置にも適用することができる。In the above description, a single wafer type substrate cleaning apparatus for cleaning substrates one by one has been described as an example.
The present invention can also be applied to a batch type substrate cleaning apparatus for simultaneously cleaning a plurality of substrates.
【００３６】[0036]
【発明の効果】以上の説明から明らかなように、請求項
１に記載の発明方法によれば、アルカリ性の薬剤や負イ
オン界面活性剤などの薬剤を使用することなく、還元ガ
スを純水に溶解させた水溶液を洗浄液として基板に供給
することにより、基板と粒子の表面電位を同極性に制御
することができる。したがって、基板に付着した粒子を
電気的に反発させて基板から除去することができるとと
もに、その再付着を防止することができる。また、薬剤
を使用していないので、最終リンス工程を行う必要がな
く洗浄処理が短縮できてスループットを向上させること
ができる。また、この洗浄液を最終のリンス工程でも使
用することができる。As is apparent from the above description, according to the method of the present invention, the reducing gas can be converted into pure water without using a chemical such as an alkaline chemical or an anionic surfactant. By supplying the dissolved aqueous solution to the substrate as a cleaning liquid, the surface potentials of the substrate and the particles can be controlled to have the same polarity. Therefore, particles adhered to the substrate can be electrically repelled and removed from the substrate, and re-adhesion can be prevented. Further, since no chemical is used, there is no need to perform a final rinsing step, the cleaning process can be shortened, and the throughput can be improved. Further, this cleaning liquid can be used in the final rinsing step.
【００３７】また、請求項２に記載の発明方法によれ
ば、還元ガスである水素を純水に溶存させることによ
り、基板と粒子の表面電位を同極性に制御でき、基板に
付着した粒子を除去するとともに再付着を防止できる。According to the second aspect of the present invention, the surface potential of the substrate and the particles can be controlled to the same polarity by dissolving hydrogen as a reducing gas in pure water. It can be removed and re-adhesion can be prevented.
【００３８】また、請求項３に記載の発明方法によれ
ば、還元ガスの飽和溶解濃度を高めて表面電位を制御す
るのに充分な電子を洗浄液に含ませることができ、確実
に付着粒子を基板から除去することができる。According to the third aspect of the present invention, sufficient electrons can be contained in the cleaning liquid to control the surface potential by increasing the saturated dissolution concentration of the reducing gas, and the adhered particles can be reliably removed. It can be removed from the substrate.
【００３９】また、請求項４に記載の発明装置によれ
ば、請求項１に記載の基板洗浄方法を好適に実施でき
る。According to the apparatus of the fourth aspect, the method of cleaning a substrate according to the first aspect can be suitably performed.
【００４０】また、請求項５に記載の発明装置によれ
ば、還元ガスの圧力を調整することにより洗浄液中の還
元ガス濃度を調整することができる。Further, according to the apparatus of the present invention, the concentration of the reducing gas in the cleaning liquid can be adjusted by adjusting the pressure of the reducing gas.
【００４１】また、請求項６に記載の発明装置によれ
ば、還元ガスの飽和溶解濃度を高めて表面電位を制御す
るのに充分な電子を洗浄液に含ませることができ、確実
に付着粒子を基板から除去することができる装置を提供
できる。According to the apparatus of the sixth aspect of the present invention, sufficient electrons can be contained in the cleaning liquid to increase the saturated dissolution concentration of the reducing gas and control the surface potential, and the adhered particles can be reliably removed. An apparatus that can be removed from a substrate can be provided.
【００４２】また、請求項７に記載の発明装置によれ
ば、還元ガスの供給口と液室内の接触面積を大きくで
き、還元ガスを効率よく純水に溶解させることができ
る。したがって、溶解手段を小型化することができる。According to the apparatus of the present invention, the contact area between the supply port of the reducing gas and the liquid chamber can be increased, and the reducing gas can be efficiently dissolved in pure water. Therefore, the size of the melting means can be reduced.
【図１】本発明に係る基板洗浄装置を示す概略縦断面図
である。FIG. 1 is a schematic longitudinal sectional view showing a substrate cleaning apparatus according to the present invention.
【図２】図１の平面図である。FIG. 2 is a plan view of FIG.
【図３】溶解装置の他の構成を示す概略縦断面図であ
る。FIG. 3 is a schematic longitudinal sectional view showing another configuration of the melting apparatus.
４ … 基板保持手段 ７ … ノズル（洗浄液供給部） １２ … 溶解装置（溶解手段） １４ … 浸透膜 ２０ … 冷却装置（冷却手段） ３０ … 溶解装置（溶解手段） ３１ … 浸透部 ３３ … 液室 Ｐ … 圧力調整器（圧力調整手段） Ｗ … 基板 DESCRIPTION OF SYMBOLS 4 ... Substrate holding | maintenance means 7 ... Nozzle (cleaning liquid supply part) 12 ... Dissolution apparatus (dissolution means) 14 ... Permeation film 20 ... Cooling apparatus (cooling means) 30 ... Dissolution apparatus (dissolution means) 31 ... Permeation part 33 ... Liquid chamber P … Pressure regulator (pressure regulating means) W… Substrate
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｇ１１Ｂ 7/26 Ｇ１１Ｂ 7/26 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI G11B 7/26 G11B 7/26
Claims (7)
洗浄方法において、純水に還元ガスを溶解させた水溶液
を前記洗浄液としたことを特徴とする基板洗浄方法。1. A substrate cleaning method for supplying a cleaning liquid to a substrate to perform cleaning, wherein an aqueous solution in which a reducing gas is dissolved in pure water is used as the cleaning liquid.
て、前記還元ガスを水素としたことを特徴とする基板洗
浄方法。2. The substrate cleaning method according to claim 1, wherein said reducing gas is hydrogen.
浄方法において、前記純水を冷却したことを特徴とする
基板洗浄方法。3. The substrate cleaning method according to claim 1, wherein the pure water is cooled.
洗浄装置において、純水に還元ガスを溶解させる溶解手
段と、前記溶解手段により生成された水溶液を前記洗浄
液として基板に供給する洗浄液供給部とを備えているこ
とを特徴とする基板洗浄装置。4. In a substrate cleaning apparatus for supplying a cleaning liquid to a substrate for cleaning, a dissolving means for dissolving a reducing gas in pure water, and a cleaning liquid supply for supplying an aqueous solution generated by the dissolving means to the substrate as the cleaning liquid. A substrate cleaning apparatus, comprising:
て、還元ガスの圧力を調整して前記溶解手段に供給する
圧力調整手段を備えていることを特徴とする基板洗浄装
置。5. The substrate cleaning apparatus according to claim 4, further comprising a pressure adjusting unit that adjusts the pressure of the reducing gas and supplies the reduced gas to the dissolving unit.
浄装置において、純水を冷却して前記溶解手段に供給す
る冷却手段を備えていることを特徴とする基板洗浄装
置。6. The substrate cleaning apparatus according to claim 4, further comprising cooling means for cooling pure water and supplying the pure water to the dissolving means.
載の基板洗浄装置において、前記溶解手段は、純水が供
給される液室と、前記液室内に設けられ、還元ガスに対
して透過性を有する複数の中空糸とを備え、前記中空糸
の中空部から還元ガスを透過させることにより純水に還
元ガスを溶解させることを特徴とする基板洗浄装置。7. The substrate cleaning apparatus according to claim 4, wherein the dissolving means is provided in a liquid chamber to which pure water is supplied and in the liquid chamber, and is provided for a reducing gas. A substrate cleaning apparatus, comprising: a plurality of permeable hollow fibers; and dissolving the reducing gas in pure water by transmitting the reducing gas through a hollow portion of the hollow fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33570596A JP3394143B2 (en) | 1996-12-16 | 1996-12-16 | Substrate cleaning method and apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33570596A JP3394143B2 (en) | 1996-12-16 | 1996-12-16 | Substrate cleaning method and apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10172941A true JPH10172941A (en) | 1998-06-26 |
| JP3394143B2 JP3394143B2 (en) | 2003-04-07 |
Family
ID=18291565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33570596A Expired - Fee Related JP3394143B2 (en) | 1996-12-16 | 1996-12-16 | Substrate cleaning method and apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3394143B2 (en) |
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| JP2000330262A (en) * | 1999-05-20 | 2000-11-30 | Mitsubishi Electric Corp | Method for washing photomask, apparatus therefor and photomask washing solution |
| JP2002166150A (en) * | 2000-08-17 | 2002-06-11 | Inst Fr Petrole | Distribution apparatus causing multiphase mixing and reaction vessel relevant thereto |
| KR100447369B1 (en) * | 2001-03-29 | 2004-09-08 | 샤프 가부시키가이샤 | Adherent film recovering device and method of recovering adherent film |
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| Publication number | Publication date |
|---|---|
| JP3394143B2 (en) | 2003-04-07 |
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