JP2001054768A - Cleaning method and cleaning device - Google Patents
Cleaning method and cleaning deviceInfo
- Publication number
- JP2001054768A JP2001054768A JP11232760A JP23276099A JP2001054768A JP 2001054768 A JP2001054768 A JP 2001054768A JP 11232760 A JP11232760 A JP 11232760A JP 23276099 A JP23276099 A JP 23276099A JP 2001054768 A JP2001054768 A JP 2001054768A
- Authority
- JP
- Japan
- Prior art keywords
- cleaning
- hydrofluoric acid
- aqueous solution
- hydrogen
- wafer
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体装置、液晶
表示装置または電子部品の製造工程で用いられる洗浄方
法及び洗浄装置に関し、特に、半導体ウエハや液晶ガラ
ス基板などの基板に付着する鉄、銅、ニッケルなどの金
属不純物、パーティクル（微粒子）、自然酸化膜などを
洗浄除去する場合に適用して好適なものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning method and a cleaning apparatus used in a manufacturing process of a semiconductor device, a liquid crystal display device or an electronic component, and more particularly, to iron and copper adhered to a substrate such as a semiconductor wafer or a liquid crystal glass substrate. It is suitable for cleaning and removing metal impurities such as nickel, particles (fine particles), and natural oxide films.
【０００２】[0002]
【従来の技術】近年の半導体デバイスの高集積化に伴
い、半導体基板上に形成される素子や配線のサイズがサ
ブミクロンのレベルに微細化してきている。2. Description of the Related Art With the recent increase in the degree of integration of semiconductor devices, the size of elements and wirings formed on a semiconductor substrate has been reduced to the submicron level.
【０００３】このような半導体デバイスを安定して製造
するためには、半導体デバイスの製造工程での基板の表
面を高清浄な状態に保つ必要がある。すなわち、有機
物、金属不純物、パーティクル、自然酸化膜等を例えば
超純水を用いて基板表面から完全に除去してから、半導
体基板を各製造プロセスに投入する必要がある。In order to stably manufacture such a semiconductor device, it is necessary to keep the surface of the substrate in a highly clean state in the process of manufacturing the semiconductor device. That is, it is necessary to completely remove organic substances, metal impurities, particles, natural oxide films, and the like from the substrate surface using, for example, ultrapure water, and then put the semiconductor substrate into each manufacturing process.
【０００４】基板表面をウエット洗浄する代表的な方法
として、ＲＣＡ洗浄がある。ＲＣＡ洗浄では、薬液とし
て、硫酸、水酸化アンモニウム、塩酸、硝酸、フッ化水
素酸（以下、ＨＦと称す。）、過酸化水素などの水溶液
が用いられる。例えば、基板表面に付着しているパーテ
ィクルを除去する場合、水酸化アンモニウムと過酸化水
素と超純水とを１：１：５の割合で混合した水溶液が８
０℃前後の温度で用いられる（以下、ＡＰＭ、またはＳ
Ｃ−１と称す。）。また、シリコン基板上の自然酸化膜
や金属不純物を除去する場合、０．５〜５％の濃度のＨ
Ｆ水溶液（希フッ酸水溶液）が用いられる。A typical method for wet cleaning the substrate surface is RCA cleaning. In the RCA cleaning, an aqueous solution of sulfuric acid, ammonium hydroxide, hydrochloric acid, nitric acid, hydrofluoric acid (hereinafter referred to as HF), hydrogen peroxide, or the like is used as a chemical solution. For example, when removing particles adhering to the substrate surface, an aqueous solution obtained by mixing ammonium hydroxide, hydrogen peroxide, and ultrapure water at a ratio of 1: 1: 5 is used.
Used at a temperature around 0 ° C. (hereinafter APM or S
C-1. ). Further, when removing a natural oxide film or metal impurities on a silicon substrate, a H concentration of 0.5 to 5% is used.
An F aqueous solution (dilute hydrofluoric acid aqueous solution) is used.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、従来の
ＳＣ−１による洗浄方法では、洗浄が高温で行われるこ
とから、洗浄溶液から蒸気が発生する。このため、クリ
ーンルームの環境汚染を引き起こしたり、洗浄溶液から
発生する蒸気を排気するために、クリーンルームの空調
設備の負荷が大きくなるという問題があった。However, in the conventional SC-1 cleaning method, since the cleaning is performed at a high temperature, steam is generated from the cleaning solution. For this reason, there is a problem that the load on the air conditioning equipment of the clean room is increased because it causes environmental pollution of the clean room and exhausts steam generated from the cleaning solution.
【０００６】また、従来の希フッ酸水溶液を用いた洗浄
では、シリコン基板上のシリコン（以下、Ｓｉと称
す。）が露出した時点でパーティクルが再付着するた
め、洗浄効果には限界があった。さらに、希フッ酸水溶
液を用いただけでは、基板表面に露出したＳｉのダング
リングボンドが完全に水素終端化しないため、シリコン
基板を大気中に放置すると、洗浄後のシリコン基板上に
自然酸化膜が成長するという問題があった。Further, in the conventional cleaning using a dilute hydrofluoric acid aqueous solution, particles are reattached when silicon (hereinafter referred to as Si) on a silicon substrate is exposed, so that the cleaning effect is limited. . Furthermore, if only a dilute hydrofluoric acid aqueous solution is used, the dangling bonds of Si exposed on the surface of the substrate will not be completely terminated with hydrogen. Therefore, when the silicon substrate is left in the air, a natural oxide film is formed on the cleaned silicon substrate. There was a problem of growing.
【０００７】そこで、本発明の目的は、室温での洗浄を
効果的に行うことが可能となるとともに、洗浄後の基板
表面のＳｉを水素終端させることが可能な洗浄方法及び
洗浄装置を提供することである。Accordingly, an object of the present invention is to provide a cleaning method and a cleaning apparatus capable of effectively performing cleaning at room temperature and terminating Si on the substrate surface after cleaning with hydrogen. That is.
【０００８】[0008]
【課題を解決するための手段】上述した課題を解決する
ために、本発明によれば、水素ガスを溶解させたフッ化
水素酸の水溶液を、超音波振動を与えながら、被洗浄物
と接触させることにより、洗浄を行うことを特徴とす
る。According to the present invention, an aqueous solution of hydrofluoric acid in which hydrogen gas is dissolved is brought into contact with an object to be cleaned while applying ultrasonic vibration. The cleaning is performed by performing the cleaning.
【０００９】これによって、シリコン基板上の酸化膜を
エッチングして、シリコン基板上に付着しているパーテ
ィクルをリフトオフさせることが可能となるとともに、
超音波振動時の溶存水素ガスによるキャビテーション効
果とパーティクルの表面組成物の還元反応により、基板
表面に露出したＳｉへの再付着を防止することが可能と
なり、室温での洗浄を効果的に行うことが可能となる。Thus, it becomes possible to lift off particles adhering to the silicon substrate by etching the oxide film on the silicon substrate,
Due to the cavitation effect of dissolved hydrogen gas during ultrasonic vibration and the reduction reaction of the particle surface composition, it is possible to prevent redeposition on Si exposed on the substrate surface, and to perform cleaning at room temperature effectively. Becomes possible.
【００１０】また、希フッ酸水溶液中に水素ガスが添加
されているので、洗浄中に基板表面に露出したＳｉのダ
ングリングボンドをほぼ完全に水素終端化することが可
能となる。この結果、水素終端化されたＳｉ表面は大気
中でも安定を保つため、洗浄後にシリコン基板を大気中
に放置した場合においても、Ｓｉが露出した基板表面に
新たな自然酸化膜が形成されることを防止することが可
能となるとともに、シリコン単結晶の禁制帯内の界面準
位を減少させることが可能となり、デバイス特性を改善
することが可能となる。In addition, since hydrogen gas is added to the diluted hydrofluoric acid aqueous solution, it is possible to almost completely terminate the dangling bonds of Si exposed on the substrate surface during cleaning. As a result, since the hydrogen-terminated Si surface remains stable even in the air, a new natural oxide film is formed on the surface of the exposed Si substrate even when the silicon substrate is left in the air after cleaning. In addition to the above, it is possible to reduce the interface state in the forbidden band of the silicon single crystal, and to improve the device characteristics.
【００１１】本発明で使用されるフッ化水素酸水溶液の
濃度は０．００１〜５重量％、好ましくは０．５重量
％、前記溶液中の水素濃度は０．１〜２．０ｐｐｍ、好
ましくは１ｐｐｍ以上、前記超音波振動の周波数は２０
ｋＨＺ〜１０ＭＨｚ、好ましくは５００ｋＨＺ〜２ＭＨ
ｚであることが好ましい。The concentration of the aqueous solution of hydrofluoric acid used in the present invention is 0.001 to 5% by weight, preferably 0.5% by weight, and the hydrogen concentration in the solution is 0.1 to 2.0 ppm, preferably 1 ppm or more, the frequency of the ultrasonic vibration is 20
kHz to 10 MHz, preferably 500 kHz to 2 MHz
It is preferably z.
【００１２】[0012]
【発明の実施の形態】以下、本発明の実施の一形態につ
いて、図面を参照しながら説明する。図１（ａ）は、本
発明の一実施例に係る洗浄装置の構成を示す側面図、図
１（ｂ）は、本発明の一実施例に係る洗浄装置の構成を
示す上面図である。図１において、洗浄装置には、２槽
構造の洗浄バス１、２が設けられ、洗浄バス１、２間の
隙間には、脱気された冷却水３が入れられている。ま
た、洗浄バス２の底には、超音波振動発生手段４が設け
られている。この実施形態における超音波振動発生手段
４は、超音波振動子である。なお、超音波振動子の発振
周波数は２０ｋＨＺ〜１０ＭＨｚ程度に設定することが
好ましい。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1A is a side view illustrating a configuration of a cleaning apparatus according to one embodiment of the present invention, and FIG. 1B is a top view illustrating a configuration of the cleaning apparatus according to one embodiment of the present invention. In FIG. 1, the cleaning apparatus is provided with cleaning baths 1 and 2 having a two-tank structure, and a deaerated cooling water 3 is put in a gap between the cleaning baths 1 and 2. Further, an ultrasonic vibration generating means 4 is provided at the bottom of the cleaning bath 2. The ultrasonic vibration generating means 4 in this embodiment is an ultrasonic vibrator. The oscillation frequency of the ultrasonic vibrator is preferably set to about 20 kHz to 10 MHz.
【００１３】洗浄バス１には、フッ化水素酸を水に溶解
させた希フッ酸水溶液８が満たされている。ここで、フ
ッ化水素酸を希釈する水は、純水または超純水であるこ
とが好ましい。なお、上記の「純水」とは、２５℃換算
の電気抵抗率が１５．０ＭΩ・ｃｍ以上、ＴＯＣ（水中
に存在する有機物中の炭素）濃度５０ｐｐｂ以下、０．
２μｍ以上の微粒子数１０個／ｍｌ以下の清浄度の高い
水をいい、「超純水」とは、２５℃換算の電気抵抗率が
１８．０ＭΩ・ｃｍ以上、ＴＯＣ濃度５ｐｐｂ以下、
０．０５μｍ以上の微粒子数１０個／ｍｌ以下の清浄度
の極めて高い水をいう。また、希フッ酸水溶液８のフッ
化水素酸の濃度は、０．００１〜５重量％程度であるこ
とが好ましい。フッ化水素酸の濃度が０．００１重量％
未満になると、被洗浄物表面からの金属不純物の除去効
果が十分に得られないからである。また、フッ化水素酸
の濃度が５重量％以上となっても、添加分に見合った金
属不純物の除去効果が得られないからである。The cleaning bath 1 is filled with a dilute hydrofluoric acid aqueous solution 8 in which hydrofluoric acid is dissolved in water. Here, the water for diluting the hydrofluoric acid is preferably pure water or ultrapure water. The above-mentioned “pure water” is defined as having a 25 ° C.-converted electrical resistivity of 15.0 MΩ · cm or more, a TOC (carbon in an organic substance present in water) concentration of 50 ppb or less, and a COP of 50 ppm or less.
Water with high cleanliness of 10 μm / ml or less of fine particles having a particle size of 2 μm or more. “Ultra pure water” means that the electrical resistivity at 25 ° C. conversion is 18.0 MΩ · cm or more,
It refers to water with extremely high cleanliness of 10 μm / ml or less of particles having a particle size of 0.05 μm or more. The concentration of hydrofluoric acid in the diluted hydrofluoric acid aqueous solution 8 is preferably about 0.001 to 5% by weight. 0.001% by weight of hydrofluoric acid
If it is less than this, the effect of removing metal impurities from the surface of the object to be cleaned cannot be sufficiently obtained. Further, even if the concentration of hydrofluoric acid is 5% by weight or more, the effect of removing metal impurities corresponding to the added amount cannot be obtained.
【００１４】水素供給源５は水素ガス７を発生させ、こ
の水素ガス７は配管６を介して希フッ酸水溶液８内に送
られ、希フッ酸水溶液８内でバブリングしながら希フッ
酸水溶液８内に溶解する。ここで、溶液中の水素濃度
は、０．１〜２．０ｐｐｍ程度であることが好ましい。
溶液中の水素濃度が０．１ｐｐｍ以下では、希フッ酸水
溶液８内に水素ガス７を溶解させた場合の効果が充分で
ないからである。一方、溶液中の水素濃度が２．０ｐｐ
ｍ以上では、これ以上は溶解しないからである。なお、
水素の溶解度は溶媒である超純水を冷却することにより
溶解度を高くすることができる。The hydrogen supply source 5 generates a hydrogen gas 7, which is sent into a dilute hydrofluoric acid aqueous solution 8 through a pipe 6, while bubbling in the dilute hydrofluoric acid aqueous solution 8. Dissolve in. Here, the hydrogen concentration in the solution is preferably about 0.1 to 2.0 ppm.
If the hydrogen concentration in the solution is 0.1 ppm or less, the effect of dissolving the hydrogen gas 7 in the diluted hydrofluoric acid aqueous solution 8 is not sufficient. On the other hand, when the hydrogen concentration in the solution is 2.0 pp
If it is more than m, it will not be dissolved any more. In addition,
The solubility of hydrogen can be increased by cooling ultrapure water as a solvent.
【００１５】水素ガス７は、水素ボンベからの水素ガス
７を用いることができるが、水の電気分解によって生成
した水素ガス７を用いるようにしてもよい。水素ガス７
を水の電気分解によって生成することにより、水素ボン
ベからの水素ガス７を用いた場合に比べ、水素ボンベの
交換の手間を軽減できるとともに、水素ボンベを保管す
るための設置場所を確保する必要がなくなる。As the hydrogen gas 7, hydrogen gas 7 from a hydrogen cylinder can be used, but hydrogen gas 7 generated by electrolysis of water may be used. Hydrogen gas 7
By hydrogen electrolysis of water, it is possible to reduce the trouble of replacing the hydrogen cylinder as compared with the case where hydrogen gas 7 from the hydrogen cylinder is used, and it is necessary to secure an installation place for storing the hydrogen cylinder. Disappears.
【００１６】なお、希フッ酸水溶液８内に水素ガス７を
溶解させるには、水素ガス７を希フッ酸水溶液８内でバ
ブリングさせる方法のほか、水素ガス透過性を有する材
料からなる中空糸の表面に水素ガスを供給するととも
に、中空糸の内側に純水又は超純水を供給し、気液接触
により純水又は超純水に水素ガスを溶解する方法があ
る。また、純水又は超純水供給ポンプの上流側に水素ガ
スを供給し、ポンプ内の撹拌によって溶解させるように
してもよい。さらに、純水又は超純水にエジェクタを介
して水素ガスを溶解させるようにしてもよい。In order to dissolve the hydrogen gas 7 in the dilute hydrofluoric acid aqueous solution 8, a method of bubbling the hydrogen gas 7 in the dilute hydrofluoric acid aqueous solution 8 and a method of dissolving a hollow fiber made of a material having hydrogen gas permeability are used. There is a method in which hydrogen gas is supplied to the surface, pure water or ultrapure water is supplied inside the hollow fiber, and hydrogen gas is dissolved in pure water or ultrapure water by gas-liquid contact. Alternatively, hydrogen gas may be supplied to the upstream side of the pure water or ultrapure water supply pump and dissolved by stirring in the pump. Further, hydrogen gas may be dissolved in pure water or ultrapure water via an ejector.
【００１７】なお、洗浄装置には、希フッ酸水溶液８内
に溶解している水素ガス７の濃度を検出する水素濃度検
出手段を設けるようにしてもよい。水素濃度検出手段
は、希フッ酸水溶液８内に溶解している水素ガス７の濃
度を検出すると、その検出結果を水素供給源５に伝え
る。水素供給源５は、水素濃度検出手段から送られた検
出結果に基づいて、配管６に送る水素ガス７の量を調節
し、希フッ酸水溶液８内に溶解している水素ガス７の濃
度を所定値に保持することができる。The cleaning apparatus may be provided with a hydrogen concentration detecting means for detecting the concentration of the hydrogen gas 7 dissolved in the diluted hydrofluoric acid aqueous solution 8. When detecting the concentration of the hydrogen gas 7 dissolved in the diluted hydrofluoric acid aqueous solution 8, the hydrogen concentration detecting means transmits the detection result to the hydrogen supply source 5. The hydrogen supply source 5 adjusts the amount of the hydrogen gas 7 sent to the pipe 6 based on the detection result sent from the hydrogen concentration detecting means, and adjusts the concentration of the hydrogen gas 7 dissolved in the diluted hydrofluoric acid aqueous solution 8. It can be kept at a predetermined value.
【００１８】洗浄対象となるＳｉウエハ９はホルダ１０
に保持され、洗浄バス１内の希フッ酸水溶液８中に浸漬
される。すると、希フッ酸水溶液８の作用により、Ｓｉ
ウエハ９上の自然酸化膜がエッチングされ、Ｓｉウエハ
９上に付着しているパーティクルがリフトオフされる。
また、超音波振動時の溶存水素ガス７によるキャビテー
ション効果とパーティクルの表面組成物の還元反応によ
り、パーティクルのＳｉウエハ９上への再付着を防止し
て、Ｓｉウエハ９を効果的に洗浄することが可能とな
る。The Si wafer 9 to be cleaned is a holder 10
And immersed in a diluted hydrofluoric acid aqueous solution 8 in the cleaning bath 1. Then, by the action of the diluted hydrofluoric acid aqueous solution 8, Si
The natural oxide film on the wafer 9 is etched, and particles attached on the Si wafer 9 are lifted off.
In addition, the cavitation effect of the dissolved hydrogen gas 7 during ultrasonic vibration and the reduction reaction of the particle surface composition prevent the particles from re-adhering to the Si wafer 9 and effectively clean the Si wafer 9. Becomes possible.
【００１９】また、Ｓｉウエハ９の表面のＳｉのダング
リングボンドが水素終端化され、洗浄後にＳｉウエハ９
を希フッ酸水溶液８から引き上げ、Ｓｉウエハ９を大気
中にさらした場合においても、Ｓｉウエハ９の表面に新
たな自然酸化膜が形成されることを防止することが可能
となり、半導体製造プロセスに悪影響を及ぼすことを防
止することが可能となる。The dangling bonds of Si on the surface of the Si wafer 9 are terminated with hydrogen, and after cleaning, the Si wafer 9
Can be prevented from forming a new natural oxide film on the surface of the Si wafer 9 even when the Si wafer 9 is exposed to the atmosphere even when the Si wafer 9 is exposed to the atmosphere. It is possible to prevent adverse effects.
【００２０】なお、図１の実施例では、浸漬洗浄を行う
方法について説明したが、噴射洗浄を行うこともでき
る。噴射洗浄の場合、水素ガスが溶解された希フッ酸水
溶液に超音波振動を付与しながら、ノズル等から希フッ
酸水溶液を被洗浄物に噴射する。洗浄液に超音波振動を
付与するには、振動子を内蔵する洗浄液噴射ノズルによ
り超音波を照射することができる。また、振動子を内蔵
したバー型の音波トランスミッタ、もしくは振動子を石
英ロッドに取り付けた音波トランスミッタより超音波を
照射するようにしてもよい。また、水素ガスを添加した
超純水と希フッ酸水溶液を別々のノズル等から噴射し、
被洗浄物上で適切な濃度になるように液量をコントロー
ルしてもよい。また、バス内のウエハを左右・上下に揺
らしながら洗浄することも可能である。Although the method of performing immersion cleaning has been described in the embodiment of FIG. 1, spray cleaning can also be performed. In the case of spray cleaning, a dilute hydrofluoric acid aqueous solution is jetted from a nozzle or the like to the object to be cleaned while applying ultrasonic vibration to the dilute hydrofluoric acid aqueous solution in which hydrogen gas is dissolved. In order to apply ultrasonic vibration to the cleaning liquid, ultrasonic waves can be irradiated by a cleaning liquid injection nozzle having a built-in vibrator. Further, ultrasonic waves may be emitted from a bar-type sound wave transmitter having a built-in vibrator or a sound wave transmitter having the vibrator mounted on a quartz rod. In addition, ultrapure water and diluted hydrofluoric acid aqueous solution to which hydrogen gas has been added are jetted from separate nozzles and the like,
The amount of the liquid may be controlled so as to have an appropriate concentration on the object to be cleaned. It is also possible to wash the wafer in the bath while swinging it left and right and up and down.
【００２１】次に、本発明の実施例について、他の洗浄
方法と比較しながら説明する。本発明に係る洗浄方法の
一例として、８インチのＳｉウエハを０．５重量％の希
フッ酸水溶液中に浸漬し、希フッ酸水溶液中の水素ガス
の濃度が１．６ｐｐｍとなるように水素ガスを希フッ酸
水溶液（超純水にフッ化水素酸を溶解させた水溶液）中
にバブリングさせ、出力が６００Ｗで周波数が１ＭＨｚ
の超音波振動（メガソニック）を与えながら、室温（２
５℃）で１分間洗浄を行い、洗浄後のＳｉウエハ上の１
枚当たりの微粒子数（個／枚、サイズが０．１７μｍ以
上のもの）を求めた。以下、この洗浄方法をＤＨＦ／Ｈ
2 ／ＭＳ洗浄（実施例１）と記す。Next, embodiments of the present invention will be described in comparison with other cleaning methods. As an example of the cleaning method according to the present invention, an 8-inch Si wafer is immersed in a 0.5% by weight dilute hydrofluoric acid aqueous solution, and hydrogen is diluted so that the concentration of hydrogen gas in the dilute hydrofluoric acid aqueous solution becomes 1.6 ppm. The gas is bubbled into a diluted hydrofluoric acid aqueous solution (an aqueous solution in which hydrofluoric acid is dissolved in ultrapure water), and the output is 600 W and the frequency is 1 MHz.
While applying ultrasonic vibration (megasonic) at room temperature (2
5 ° C.) for 1 minute, and 1
The number of fine particles per sheet (particles / sheet, having a size of 0.17 μm or more) was determined. Hereinafter, this cleaning method is referred to as DHF / H
2 / MS washing (Example 1).
【００２２】一方、比較例１〜３として、ブランク（未
洗浄のＳｉウエハ）、ＳＣ−１洗浄後のＳｉウエハ、Ｈ
2 ／ＭＳ洗浄（純水中への水素ガスのバブリング＋超音
波照射）後のＳｉウエハを用いた。On the other hand, as Comparative Examples 1 to 3, a blank (uncleaned Si wafer), a Si wafer after SC-1 cleaning, and H
A Si wafer after 2 / MS cleaning (bubbling of hydrogen gas into pure water + ultrasonic irradiation) was used.
【００２３】表１は、各洗浄方法での洗浄後の微粒子数
の算出結果を示す。Table 1 shows the calculation results of the number of fine particles after cleaning in each cleaning method.
【００２４】[0024]
【表１】 表１において、ブランク（比較例１）では微粒子数が１
５０００個であるのに対し、１０分間のＳＣ−１洗浄
（比較例２）では４７個、５分間のＨ2 ／ＭＳ洗浄（比
較例３）では２８個、１分間のＤＨＦ／Ｈ2 ／ＭＳ洗浄
（実施例１）では３個である。従って、ＤＨＦ／Ｈ2 ／
ＭＳ洗浄では、短時間で基板表面の微粒子をほぼ完全に
除去することができ、ＤＨＦ／Ｈ2 ／ＭＳ洗浄による微
粒子の除去に対する有効性が示された。[Table 1] In Table 1, the number of fine particles was 1 in the blank (Comparative Example 1).
To which the in 5000, 47 in 10 minutes SC-1 cleaning (Comparative Example 2), 28 in the H 2 / MS washed for 5 minutes (Comparative Example 3), 1 minute DHF / H 2 / MS In cleaning (Example 1), the number is three. Therefore, DHF / H 2 /
In the MS cleaning, the fine particles on the substrate surface could be almost completely removed in a short time, and the effectiveness in removing the fine particles by the DHF / H 2 / MS cleaning was shown.
【００２５】次に、ＤＨＦ／Ｈ2 ／ＭＳ洗浄後のＳｉウ
エハの表面のＳｉの水素終端化の程度を調べた。一方、
比較例４、５として、ブランク（ＳｉＯ2 表面。ただ
し、ブランクのＳｉＯ2 表面は、硫酸と過酸化水素とを
４：１の割合で混合させた溶液で１０分間洗浄したも
の。）、ＤＨＦ（０．５％の濃度の希フッ酸水溶液）洗
浄後のＳｉウエハを用いた。Next, the degree of hydrogen termination of Si on the surface of the Si wafer after DHF / H 2 / MS cleaning was examined. on the other hand,
As Comparative Examples 4 and 5, a blank (SiO 2 surface; the blank SiO 2 surface was washed for 10 minutes with a solution in which sulfuric acid and hydrogen peroxide were mixed at a ratio of 4: 1), DHF ( A Si wafer after cleaning (a diluted hydrofluoric acid aqueous solution having a concentration of 0.5%) was used.
【００２６】表２は、各洗浄方法での洗浄後のＳｉ−Ｈ
2 の伸縮振動スペクトルの吸光度を示す。なお、Ｓｉ−
Ｈ2 の伸縮振動スペクトルの吸光度は、ＦＴ−ＩＲ（Ｆ
ｏｕｒｉｅｒ Ｔｒａｎｓｆｏｒｍ Ｉｎｆｒａｒｅｄ
Ｓｐｅｃｔｒｏｍｅｔｅｒ）で測定した。Table 2 shows that Si—H after cleaning by each cleaning method.
2 shows the absorbance of the stretching vibration spectrum of 2 . In addition, Si-
The absorbance of the stretching vibration spectrum of H 2 is FT-IR (F
Our Transform Infrared
(Spectrometer).
【００２７】[0027]
【表２】 表２において、ブランク（比較例４）では吸光度が０で
あるのに対し、１分間のＤＨＦ洗浄（比較例５）では
０．０１５、１分間のＤＨＦ／Ｈ2 ／ＭＳ洗浄（実施例
１）では０．０２７である。従って、ＤＨＦ／Ｈ2 ／Ｍ
Ｓ洗浄では、ＤＨＦ洗浄に比べて、Ｓｉ−Ｈ2 の伸縮振
動スペクトルの吸光度が増加し、Ｓｉウエハの表面のＳ
ｉの水素終端化に対する有効性が示された。[Table 2] In Table 2, the absorbance is 0 for the blank (Comparative Example 4), while the DHF washing for 1 minute (Comparative Example 5) is 0.015 and the DHF / H 2 / MS washing for 1 minute (Example 1). Is 0.027. Therefore, DHF / H 2 / M
In the S cleaning, the absorbance of the stretching vibration spectrum of Si—H 2 increases compared to the DHF cleaning, and the S wafer on the surface of the Si wafer
The effectiveness of i for hydrogen termination was demonstrated.
【００２８】次に、ＤＨＦ／Ｈ2 ／ＭＳ洗浄後のＳｉウ
エハの表面粗さを調べた。一方、比較例６、７として、
ブランク（ＳｉＯ2 表面。ただし、ブランクのＳｉＯ2
表面は、硫酸と過酸化水素とを４：１の割合で混合させ
た溶液で１０分間洗浄したもの。）、ＤＨＦ（０．５％
の濃度の希フッ酸水溶液）洗浄後のＳｉウエハを用い
た。Next, the surface roughness of the Si wafer after DHF / H 2 / MS cleaning was examined. On the other hand, as Comparative Examples 6 and 7,
Blank (SiO 2 surface, but blank SiO 2
The surface was washed for 10 minutes with a solution in which sulfuric acid and hydrogen peroxide were mixed at a ratio of 4: 1. ), DHF (0.5%
(A diluted hydrofluoric acid aqueous solution having a concentration of 2%) was used.
【００２９】表３は、各洗浄方法での洗浄後の表面粗さ
Ｒａ（ｎｍ）を示す。なお、表面粗さＲａは、ＡＦＭ
（Ａｔｏｍｉｃ Ｆｏｒｃｅ Ｍｉｃｒｏｓｃｏｐｅ）
で測定した。Table 3 shows the surface roughness Ra (nm) after each cleaning method. The surface roughness Ra was determined by AFM.
(Atomic Force Microscope)
Was measured.
【００３０】[0030]
【表３】 表３において、ブランク（比較例６）では表面粗さＲａ
が０．１５であるのに対し、１分間のＤＨＦ洗浄（比較
例７）では０．１２、１分間のＤＨＦ／Ｈ2 ／ＭＳ洗浄
（実施例１）では０．０９である。従って、ＤＨＦ／Ｈ
2 ／ＭＳ洗浄では、ＤＨＦ洗浄に比べて表面粗さＲａが
低減し、洗浄時にＳｉウエハを平坦化させる効果のある
ことが示された。[Table 3] In Table 3, the blank (Comparative Example 6) had a surface roughness Ra.
Is 0.15, whereas the DHF cleaning for 1 minute (Comparative Example 7) is 0.12, and the DHF / H 2 / MS cleaning for 1 minute (Example 1) is 0.09. Therefore, DHF / H
In the 2 / MS cleaning, the surface roughness Ra was reduced as compared with the DHF cleaning, and it was shown that there was an effect of flattening the Si wafer during the cleaning.
【００３１】[0031]
【発明の効果】以上説明したように、本発明によれば、
水で希釈されたフッ化水素酸に水素ガスを添加した溶液
に超音波振動を与えながら接触させることにより、シリ
コン基板上に付着しているパーティクルをリフトオフさ
せ、パーティクルを基板表面から除去することが可能と
なるとともに、洗浄中に基板表面に露出したＳｉのダン
グリングボンドを完全に水素終端化することが可能とな
り、洗浄後にシリコン基板を大気中に放置した場合にお
いても、Ｓｉが露出した基板表面に新たな自然酸化膜が
形成されることを防止することが可能となる。As described above, according to the present invention,
By contacting a solution obtained by adding hydrogen gas to hydrofluoric acid diluted with water while applying ultrasonic vibration, the particles adhering to the silicon substrate can be lifted off and the particles can be removed from the substrate surface. This makes it possible to completely terminate the dangling bonds of Si exposed on the substrate surface during cleaning with hydrogen, and even when the silicon substrate is left in the air after cleaning, the Si surface is exposed. Thus, it is possible to prevent a new natural oxide film from being formed.
【図１】図１（ａ）は、本発明の一実施例に係る洗浄装
置の構成を示す側面図、図１（ｂ）は、本発明の一実施
例に係る洗浄装置の構成を示す上面図である。FIG. 1A is a side view showing a configuration of a cleaning apparatus according to one embodiment of the present invention, and FIG. 1B is a top view showing the configuration of the cleaning apparatus according to one embodiment of the present invention. FIG.
１、２ 洗浄バス ３ 冷却水 ４ 超音波振動発生手段 ５ 水素供給源 ６ 配管 ７ 水素ガス ８ 希フッ酸水溶液 ９ ウエハ １０ ホルダ 1, 2 Cleaning bath 3 Cooling water 4 Ultrasonic vibration generating means 5 Hydrogen supply source 6 Piping 7 Hydrogen gas 8 Dilute hydrofluoric acid aqueous solution 9 Wafer 10 Holder
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小島 泉里 神奈川県厚木市岡田２丁目９番８号 野村 マイクロ・サイエンス株式会社内 Ｆターム(参考） 3B201 AA03 AB01 AB44 BB02 BB85 BB93 BB96 BB98 CB01 CC21 CD42 CD43 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Izumi Kojima 2-9-8 Okada, Atsugi-shi, Kanagawa F-term in Nomura Micro Science Co., Ltd. (Reference) 3B201 AA03 AB01 AB44 BB02 BB85 BB93 BB96 BB98 CB01 CC21 CD42 CD43
Claims (5)
溶液を、超音波振動を与えながら、被洗浄物と接触させ
ることを特徴とする洗浄方法。1. A cleaning method, comprising contacting an aqueous solution of hydrofluoric acid in which hydrogen gas is dissolved with an object to be cleaned while applying ultrasonic vibration.
０１〜５重量％である請求項１記載の洗浄方法。2. The method according to claim 1, wherein the concentration of the aqueous solution of hydrofluoric acid is 0.0
The cleaning method according to claim 1, wherein the amount is from 01 to 5% by weight.
０ｐｐｍである請求項１又は２記載の洗浄方法。3. The method according to claim 1, wherein the aqueous solution has a hydrogen concentration of 0.1 to 2.
3. The cleaning method according to claim 1, wherein the amount is 0 ppm.
１０ＭＨｚであることを特徴とする請求項１から３のい
ずれか１項記載の洗浄方法。4. The ultrasonic vibration has a frequency of 20 kHz to
The cleaning method according to claim 1, wherein the frequency is 10 MHz.
触させるフッ化水素酸水溶液接触手段と、 水素ガスを所定濃度となるように前記水溶液に溶解させ
る水素ガス添加手段と、 所定の周波数の超音波振動を前記水溶液に与える超音波
振動発生手段とを備えることを特徴とする洗浄装置。5. A hydrofluoric acid aqueous solution contacting means for contacting an aqueous solution of hydrofluoric acid with an object to be cleaned, a hydrogen gas adding means for dissolving hydrogen gas in the aqueous solution so as to have a predetermined concentration, An ultrasonic vibration generating means for applying ultrasonic vibration of a frequency to the aqueous solution.
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|---|---|---|---|
| JP11232760A JP2001054768A (en) | 1999-08-19 | 1999-08-19 | Cleaning method and cleaning device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11232760A JP2001054768A (en) | 1999-08-19 | 1999-08-19 | Cleaning method and cleaning device |
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| Publication Number | Publication Date |
|---|---|
| JP2001054768A true JP2001054768A (en) | 2001-02-27 |
Family
ID=16944331
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| WO2003043751A1 (en) * | 2001-11-21 | 2003-05-30 | Agency For Science, Technology And Research | An apparatus and method for cleaning glass substrates using a cool hydrogen flame |
| KR100475774B1 (en) * | 2002-11-27 | 2005-03-10 | (주)울텍 | The Method and apparatus for Removal of Bubbles on the Substrate by Ultrasonic Waves |
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| JP2007311536A (en) * | 2006-05-18 | 2007-11-29 | Covalent Materials Corp | Method of manufacturing semiconductor device, semiconductor substrate, and method of manufacturing the same |
| CN100396390C (en) * | 2003-10-10 | 2008-06-25 | 财团法人工业技术研究院 | Surface treatment method and instrument of air bubble utilizing backing |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003043751A1 (en) * | 2001-11-21 | 2003-05-30 | Agency For Science, Technology And Research | An apparatus and method for cleaning glass substrates using a cool hydrogen flame |
| KR100475774B1 (en) * | 2002-11-27 | 2005-03-10 | (주)울텍 | The Method and apparatus for Removal of Bubbles on the Substrate by Ultrasonic Waves |
| CN100396390C (en) * | 2003-10-10 | 2008-06-25 | 财团法人工业技术研究院 | Surface treatment method and instrument of air bubble utilizing backing |
| KR100527247B1 (en) * | 2004-03-24 | 2005-11-09 | (주)울텍 | The Apparatus for wet etching |
| WO2007034534A1 (en) * | 2005-09-20 | 2007-03-29 | Tadahiro Ohmi | Semiconductor device manufacturing method and semiconductor manufacturing apparatus |
| US8030182B2 (en) | 2005-09-20 | 2011-10-04 | Tadahiro Ohmi | Semiconductor device manufacturing method and semiconductor manufacturing apparatus |
| JP2007311536A (en) * | 2006-05-18 | 2007-11-29 | Covalent Materials Corp | Method of manufacturing semiconductor device, semiconductor substrate, and method of manufacturing the same |
| CN110404897A (en) * | 2019-07-05 | 2019-11-05 | 北京无线电计量测试研究所 | A kind of Hydrogen Atom Frequency Standard ionization bubble aging method |
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