JP3320190B2 - Method for manufacturing semiconductor device - Google Patents
Method for manufacturing semiconductor deviceInfo
- Publication number
- JP3320190B2 JP3320190B2 JP04812094A JP4812094A JP3320190B2 JP 3320190 B2 JP3320190 B2 JP 3320190B2 JP 04812094 A JP04812094 A JP 04812094A JP 4812094 A JP4812094 A JP 4812094A JP 3320190 B2 JP3320190 B2 JP 3320190B2
- Authority
- JP
- Japan
- Prior art keywords
- pure water
- hydrochloric acid
- cleaned
- cleaning
- semiconductor device
- 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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- Cleaning Or Drying Semiconductors (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、半導体装置の製造方法
に係り、詳しくは、ウェハ表面の表面状態の保障技術に
適用することができ、特に、既存の装置を用いつつ、純
水洗浄過程でウェハ表面に成長する酸化物を安価にかつ
簡便に抑制することができる半導体装置の製造方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a semiconductor device, and more particularly, to a technique for guaranteeing a surface condition of a wafer surface. The present invention relates to a method for manufacturing a semiconductor device capable of easily and inexpensively suppressing oxides growing on a wafer surface.
【０００２】近年、半導体装置の高集積化が進むに連
れ、製造工程におけるウェハ表面の洗浄の役割は益々重
要となっている。そして、そのウェハ洗浄の役割は、ウ
ェハ表面の異物及び汚染物質の除去の他に、近年、その
ウェハ表面状態を保障することに拡張されてきている。
これらの洗浄の役割の中でも、本発明は、特にウェハ表
面状態の保障に関する。In recent years, as semiconductor devices have become highly integrated, the role of cleaning the wafer surface in the manufacturing process has become increasingly important. In addition, the role of the wafer cleaning has recently been extended to guarantee the condition of the wafer surface, in addition to the removal of foreign substances and contaminants on the wafer surface.
Among these cleaning roles, the present invention particularly relates to ensuring the surface condition of the wafer.
【０００３】[0003]
【従来の技術】従来、半導体装置の製造工程における洗
浄工程は、主としてＳｉウェハ等の被洗浄物表面の異物
あるいは汚染物の除去を主眼においている。しかしなが
ら、近年、半導体装置の高集積化に伴い、それを構成す
る各種の膜の膜厚が益々薄くなってきている。このこと
は、各種の膜に占める界面構造の割合が相対的に大きく
なることを示し、その化学的な構造が膜自体の質を左右
する可能性がある。即ち、被洗浄物の表面状態によって
は、その後のその上に形成する膜の膜質を左右する可能
性があり、これらは当然デバイスの電気的な特性あるい
は信頼性に影響を及ぼす。2. Description of the Related Art Conventionally, a cleaning process in a manufacturing process of a semiconductor device mainly focuses on removing foreign substances or contaminants on the surface of an object to be cleaned such as a Si wafer. However, in recent years, with the increase in the degree of integration of semiconductor devices, the thicknesses of various films constituting the semiconductor devices have become increasingly smaller. This indicates that the proportion of the interface structure in the various films becomes relatively large, and the chemical structure may affect the quality of the film itself. That is, depending on the surface condition of the object to be cleaned, there is a possibility that the film quality of the film formed thereon may be influenced, and these naturally affect the electrical characteristics or reliability of the device.
【０００４】従来の半導体装置の製造方法においては、
弗酸等の化学処理によって半導体あるいはその上に成膜
した膜の表面を露出した後、その表面上に存在する微粒
子等の異物あるいは金属等の不純物を除去するために、
純水を用いて洗浄を行っている。しかしながら、この純
水洗浄方法では、純水洗浄の過程で酸化物が被洗浄物表
面に新たに形成されるという問題があった。このよう
に、半導体やその上に成膜した膜表面に酸化物が形成さ
れた状態でデバイスを作成すると、デバイスの電気的特
性等が低下してしまう。In a conventional method of manufacturing a semiconductor device,
After exposing the surface of the semiconductor or the film formed thereon by chemical treatment such as hydrofluoric acid, in order to remove foreign substances such as fine particles or impurities such as metal present on the surface,
Cleaning is performed using pure water. However, this pure water cleaning method has a problem that an oxide is newly formed on the surface of the object to be cleaned in the process of pure water cleaning. As described above, when a device is manufactured in a state where an oxide is formed on the surface of a semiconductor or a film formed thereon, the electrical characteristics and the like of the device deteriorate.
【０００５】上記した純水洗浄での酸化物の成長につい
ては、例えばＭ．Ｍｏｒｉｔａ ｅｔ ａｌ．：Ａｐｐ
ｌ．Ｐｈｙｓ．Ｌｅｔｔ．５５（１９８９）５６２．で
報告されたものがあり、これは純水の溶存酸素量に依存
することが判っている。このため、この溶存酸素量を低
減させれば、この純水洗浄時に生じる酸化物の成長を抑
制することができる。このような背景から、近年、この
溶存酸素量を制御できる純水作製装置が注目されてきて
いる。この純水作製装置によれば、純水中の溶存酸素量
を低減することができるため、純水洗浄時の被加工物表
面に成長する酸化物を抑制することができるという利点
を有する。The growth of oxides in the above-described pure water cleaning is described in, for example, M. See Morita et al. : App
l. Phys. Lett. 55 (1989) 562. It has been found that this depends on the dissolved oxygen content of pure water. Therefore, if the amount of dissolved oxygen is reduced, it is possible to suppress the growth of oxides generated during the pure water cleaning. From such a background, in recent years, attention has been paid to a pure water producing apparatus capable of controlling the amount of dissolved oxygen. According to this pure water producing apparatus, since the amount of dissolved oxygen in pure water can be reduced, there is an advantage that oxides that grow on the surface of the workpiece during pure water cleaning can be suppressed.
【０００６】[0006]
【発明が解決しようとする課題】上記した純水作製装置
を用いた従来の半導体装置の製造方法では、純水中の溶
存酸素量を低減することができるため、純水洗浄時の被
加工物表面に成長する酸化物を抑制することができると
いう利点を有しているが、この装置は、純水中の溶存酸
素量を制御する複雑で高価な制御機構等を有する等、コ
ストが増加するうえ、既存の半導体工場にこれを導入し
ようとすると、非常に大掛かりで面倒であるという問題
があった。In the conventional method of manufacturing a semiconductor device using the above-described pure water producing apparatus, the amount of dissolved oxygen in pure water can be reduced, and therefore, the work piece during pure water cleaning can be reduced. Although it has the advantage of being able to suppress oxides growing on the surface, this device has a complicated and expensive control mechanism for controlling the amount of dissolved oxygen in pure water, which increases costs. Furthermore, there is a problem that it is very large and troublesome to introduce this into an existing semiconductor factory.
【０００７】そこで、既存の装置を用いつつ純水洗浄過
程で被加工物表面に成長する酸化物を安価にかつ簡便に
抑制することができる半導体装置の製造方法を提供する
ことを目的としている。Accordingly, it is an object of the present invention to provide a method of manufacturing a semiconductor device capable of easily and inexpensively suppressing oxides growing on the surface of a workpiece in a pure water cleaning process while using existing equipment.
【０００８】[0008]
【課題を解決するための手段】請求項１記載の発明は、
被洗浄物表面から酸化物を除去処理した後、被洗浄物表
面を純水に塩酸を添加した塩酸水溶液で洗浄する工程を
含むことを特徴とするものである。請求項２記載の発明
は、上記請求項１の発明において、前記被洗浄物表面の
酸化物除去処理は、弗酸及び緩衝弗酸処理のうち、少な
くともどちらか一方の処理で行うことを特徴とするもの
である。According to the first aspect of the present invention,
After removing the oxide from the surface of the object to be cleaned, the method includes a step of cleaning the surface of the object to be cleaned with an aqueous hydrochloric acid solution obtained by adding hydrochloric acid to pure water. According to a second aspect of the present invention, in the first aspect of the present invention, the oxide removal treatment on the surface of the object to be cleaned is performed by at least one of hydrofluoric acid and buffered hydrofluoric acid. Is what you do.
【０００９】請求項３記載の発明は、上記請求項１，２
記載の発明において、前記塩酸水溶液の塩酸濃度は、少
なくとも１０ｐｐｍ以上であることを特徴とするもので
ある。請求項４記載の発明は、上記請求項１乃至３記載
の発明において、前記被洗浄物は、シリコンあるいはそ
の上に形成した各種の膜であることを特徴とするもので
ある。The third aspect of the present invention is directed to the first and second aspects.
In the invention described above, the hydrochloric acid aqueous solution has a hydrochloric acid concentration of at least 10 ppm or more. According to a fourth aspect of the present invention, in the first to third aspects, the object to be cleaned is silicon or various films formed thereon.
【００１０】請求項５記載の発明は、被洗浄物を洗浄槽
内に作製した塩酸水溶液中に投入して洗浄を行った後、
更に同一槽内に純水を供給して洗浄を行うことを特徴と
するものである。請求項６記載の発明は、上記請求項５
記載の発明において、前記被洗浄物の投入は、前記洗浄
槽内に作製した前記塩酸水溶液に純水を供給し始めてか
ら行うことを特徴とするものである。[0010] According to a fifth aspect of the present invention, after the object to be cleaned is poured into an aqueous hydrochloric acid solution prepared in a cleaning tank to perform cleaning,
Further, the cleaning is performed by supplying pure water into the same tank. The invention according to claim 6 is the invention according to claim 5.
In the invention described above, the charging of the object to be cleaned is performed after pure water is supplied to the aqueous hydrochloric acid solution prepared in the cleaning tank.
【００１１】請求項７記載の発明は、上記請求項５，６
記載の発明において、前記塩酸水溶液の塩酸濃度は、少
なくとも１００００ｐｐｍ以上であることを特徴とする
ものである。請求項８の発明は、上記請求項５乃至７記
載の発明において、前記被洗浄物は、シリコンあるいは
その上に形成した各種の膜であることを特徴とするもの
である。[0011] The invention according to claim 7 is the invention according to claims 5 and 6.
In the invention described above, the hydrochloric acid concentration of the aqueous hydrochloric acid solution is at least 10,000 ppm or more. According to an eighth aspect of the present invention, in the above-described fifth to seventh aspects, the object to be cleaned is silicon or various films formed thereon.
【００１２】請求項９記載の発明は、上記請求項５乃至
８記載の発明において、前記洗浄は、前記被洗浄物表面
から酸化物を除去する処理の後に行うことを特徴とする
ものである。請求項１０記載の発明は、上記請求項５乃
至９記載の発明において、前記被洗浄物表面の酸化物除
去処理は、弗酸及び緩衝弗酸処理のうち、少なくともど
ちらか一方の処理で行うことを特徴とするものである。According to a ninth aspect of the present invention, in the above-described fifth to eighth aspects, the cleaning is performed after the treatment for removing the oxide from the surface of the object to be cleaned. According to a tenth aspect of the present invention, in the above-described fifth to ninth aspects, the oxide removal treatment on the surface to be cleaned is performed by at least one of hydrofluoric acid and buffered hydrofluoric acid treatments. It is characterized by the following.
【００１３】請求項１１記載の発明は、上記請求項５，
６記載の発明において、前記純水の供給量は、塩酸水溶
液の塩酸濃度が１０ｐｐｍ未満にならない量であること
を特徴とするものである。[0013] The invention according to claim 11 is the fifth invention.
6. The invention according to claim 6, wherein the supply amount of the pure water is an amount such that the hydrochloric acid concentration of the aqueous hydrochloric acid solution does not become less than 10 ppm.
【００１４】[0014]
【作用】本発明者は、鋭意検討した結果、純水中に存在
するＯ2 を反応させて汚染源とはならない別の化合物に
生成することができれば、純水中の溶存酸素量を低減す
ることができることに着目し、純水に塩酸を添加した塩
酸水溶液で被洗浄物表面を洗浄したところ、純水中に存
在するＯ2 をＨＣｌ水溶液を構成するＨ+ によってＨ2
Ｏに還元することができるため、純水中の溶存酸素量を
低減することができ、その結果、洗浄時に被洗浄物表面
に酸化物を生じ難くすることができた。なお、ＨＣｌの
ＨとＣｌは、電気陰性度に差があるため、Ｈの電子がＣ
ｌ側に偏っており、このため、両者のＨとＣｌは、純水
中でイオン性となっている。The present inventors have conducted intensive studies and found that if O 2 present in pure water can be reacted to form another compound that does not become a pollutant, the amount of dissolved oxygen in pure water can be reduced. When the surface of the object to be cleaned was washed with an aqueous hydrochloric acid solution obtained by adding hydrochloric acid to pure water, O 2 present in the pure water was converted into H 2 by H + constituting the aqueous HCl solution.
Since it can be reduced to O, the amount of dissolved oxygen in pure water can be reduced, and as a result, oxides can be hardly generated on the surface of the object to be cleaned during cleaning. Since H and Cl of HCl have a difference in electronegativity, the electrons of H are C
H and Cl of both are ionic in the pure water.
【００１５】このため、前述の如く、純水中に存在する
Ｏ2 をＨＣｌ水溶液を構成するＨ+によってＨ2 Ｏに還
元することができる。この時、塩酸水溶液の塩酸濃度
は、通常の純水の溶存酸素量が室温、大気気圧下で約１
０ｐｐｍであることを考慮すると、少なくとも１０ｐｐ
ｍ以上であるのが好ましく、この場合、純水中の溶存酸
素量を効率良く低減することができる。ここで、塩酸濃
度を１０ｐｐｍより小さくすると、ＨＣｌ水溶液を構成
するＨ+ の量が減って純水中の溶存酸素量を低減する効
果が小さくなる。また、塩酸水溶液の濃度は、少なくと
も１ｖｏｌ％以上であるのが好ましく、この場合、純水
中の溶存酸素量を効率良く低減することができる。ここ
で、塩素濃度を１ｖｏｌ％より小さくすると、ＨＣｌ水
溶液を構成するＨ+ の量が減って純水中の溶存酸素量を
低減する効果が小さくなる。For this reason, as described above, O 2 present in pure water can be reduced to H 2 O by H + constituting an aqueous HCl solution. At this time, the hydrochloric acid concentration of the aqueous hydrochloric acid solution is such that the amount of dissolved oxygen in ordinary pure water is about 1 at room temperature and atmospheric pressure.
Considering 0 ppm, at least 10 pp
m or more, and in this case, the amount of dissolved oxygen in pure water can be efficiently reduced. Here, when the hydrochloric acid concentration is less than 10 ppm, the amount of H + constituting the aqueous HCl solution is reduced, and the effect of reducing the amount of dissolved oxygen in pure water is reduced. Further, the concentration of the aqueous hydrochloric acid solution is preferably at least 1 vol% or more. In this case, the amount of dissolved oxygen in pure water can be efficiently reduced. Here, when the chlorine concentration is less than 1 vol%, the amount of H + constituting the aqueous HCl solution is reduced, and the effect of reducing the amount of dissolved oxygen in pure water is reduced.
【００１６】本発明に係る洗浄は、被洗浄物洗浄槽内に
作製した塩酸水溶液中に投入して行えばよく、また、こ
の投入後に通常の流水純水洗浄を行うように構成しても
よく、この場合、塩酸水溶液処理で除去できなかった表
面の異物等を効率良く除去することができる。この時、
被洗浄物の投入は、洗浄内に作製した塩酸水溶液に純水
を供給し始めてから行うように構成してもよく、この場
合、工場内でロボットを使って自動ライン化を実現する
ことができる。The cleaning according to the present invention may be carried out by charging the aqueous solution of hydrochloric acid prepared in the cleaning tank for the object to be cleaned, or may be configured to perform normal running pure water cleaning after the charging. In this case, foreign substances on the surface that could not be removed by the hydrochloric acid aqueous solution treatment can be efficiently removed. At this time,
The object to be cleaned may be introduced after pure water is supplied to the hydrochloric acid aqueous solution prepared in the cleaning, and in this case, automatic production can be realized using a robot in the factory. .
【００１７】本発明に係る被洗浄物は、シリコンあるい
はその上に形成したゲート酸化膜等の各種の膜に好まし
く適用させることができる。また、本発明に係る洗浄
は、前記被洗浄物表面から酸化物を除去する処理の後に
行う場合に好ましく適用させることができる。この被洗
浄物表面の酸化物除去処理は、弗酸あるいは緩衝弗酸処
理で行うのが好ましく、この場合、被洗浄物表面に生じ
た酸化物を効率良く除去することができる。The object to be cleaned according to the present invention can be preferably applied to various films such as silicon or a gate oxide film formed thereon. Further, the cleaning according to the present invention can be preferably applied when the cleaning is performed after the treatment for removing the oxide from the surface of the object to be cleaned. This treatment for removing oxides on the surface of the object to be cleaned is preferably performed by hydrofluoric acid or buffered hydrofluoric acid treatment. In this case, oxides generated on the surface of the object to be cleaned can be efficiently removed.
【００１８】[0018]
【実施例】以下、本発明の実施例を図面を参照して説明
する。まず、被洗浄物をＨＦ処理した後に、通常の純水
洗浄する比較例の洗浄方法について説明する。図１はＨ
Ｆ処理を施した直後とその後の通常のオーバーフロー純
水洗浄を１０分間行った時のＳｉ（１００）表面のＳｉ
−Ｈ伸縮振動による吸収の現れる波数範囲の赤外吸収ス
ペクトルを示す図である。ＨＦ処理は、Ｓｉ等の被洗浄
物表面に生じているＳｉＯ2 を除去し、その後、被洗浄
物のＳｉ表面をＨで終端することが知られている。この
図１には、被洗浄物の最表面のＳｉ原子にＨが１つ結合
したモノハイドライド（〜２０８０ｃｍ-1）、２つ結合
したダイハイドライド（〜２１１０ｃｍ-1）、３つ結合
したトリハイドライド（〜２１３０ｃｍ-1）で終端され
ており、酸化物等が存在していないことを示している。
また、この後に通常のオーバーフロー純水洗浄を１０分
間行った場合の赤外吸収スペクトルも同図に示してい
る。この場合、ＨＦ処理後直後の場合と異なり、２１５
０〜２３００ｃｍ-1の周辺に吸収が現れている。この吸
収は、Ｓｉ表面のＳｉ−Ｈ結合のバックボンドのＳｉ−
Ｓｉ結合の間にＯが入り込んだＳｉ−Ｈ結合による吸収
であり、これから、純水洗浄時に被洗浄物のＳｉ表面に
再度酸化物が成長しているのが判る。即ち、比較例の洗
浄方法では、ＨＦ処理によって被洗浄物のＳｉ表面の酸
化物（ＳｉＯ2 ）を除去しても、その後に表面の異物、
あるいは不純物を除去する目的で行う純水洗浄過程で新
たに被洗浄物のＳｉ表面に酸化物が成長してしまうとい
う問題が生じる。Embodiments of the present invention will be described below with reference to the drawings. First, a description will be given of a cleaning method of a comparative example in which an object to be cleaned is subjected to HF treatment and then normal pure water cleaning. FIG. 1 shows H
Immediately after the F treatment and after the normal overflow pure water cleaning for 10 minutes, the Si (100) surface Si
It is a figure which shows the infrared absorption spectrum of the wave number range where the absorption by -H stretching vibration appears. It is known that the HF treatment removes SiO 2 generated on the surface of the object to be cleaned, such as Si, and then terminates the Si surface of the object to be cleaned with H. The Figure 1, Monohydride H to Si atoms of the outermost surface bound one of the object to be cleaned (~2080cm -1), 2 single bound dihydride (~2110cm -1), 3 single bound tri hydride (〜2130 cm −1 ), indicating that no oxide or the like is present.
The infrared absorption spectrum when normal overflow pure water washing is performed for 10 minutes thereafter is also shown in FIG. In this case, unlike the case immediately after the HF processing, 215
Absorption appears around 0-2300 cm -1 . This absorption is due to the Si—H bond of the Si—H bond on the Si surface.
This is absorption due to the Si—H bond in which O has entered between the Si bonds, and it can be seen from this that the oxide has grown again on the Si surface of the object to be cleaned during the pure water cleaning. That is, in the cleaning method of the comparative example, even if the oxide (SiO 2 ) on the Si surface of the object to be cleaned is removed by the HF treatment, foreign matter on the surface,
Alternatively, there arises a problem that an oxide newly grows on the Si surface of the object to be cleaned in a pure water cleaning process performed for the purpose of removing impurities.
【００１９】（実施例１）次に、図２はＨＦ処理後にオ
ーバーフロー純水洗浄を１０分間行った比較例の場合と
ＨＦ処理後に洗浄槽内に作製した１０００ｐｐｍのＨＣ
ｌ溶液に１０分間浸漬した場合の本実施例１の場合のＳ
ｉ（１００）表面のＳｉ−Ｈ伸縮振動による吸収の現れ
る波数範囲の赤外吸収スペクトルを示す図である。この
図２から、純水に塩酸を添加したＨＣｌ溶液で被洗浄物
を洗浄する本実施例１では、塩酸を添加しないで純水で
洗浄する比較例の場合よりも、被洗浄物のＳｉ表面に酸
化物の成長が抑制されていることが判る。(Example 1) Next, FIG. 2 shows a comparative example in which overflow pure water cleaning was performed for 10 minutes after HF treatment and a 1000 ppm HC produced in a cleaning tank after HF treatment.
1 in Example 1 when immersed in a solution for 10 minutes.
It is a figure which shows the infrared absorption spectrum of the wave number range in which the absorption by the Si-H stretching vibration of the i (100) surface appears. From FIG. 2, it can be seen that in the first embodiment in which the object to be cleaned is washed with an HCl solution in which hydrochloric acid is added to pure water, the Si surface of the object to be cleaned is greater than in the comparative example in which cleaning is performed with pure water without adding hydrochloric acid. It can be seen that oxide growth was suppressed.
【００２０】このように、本実施例１では、純水に塩酸
を添加した塩酸水溶液で被洗浄物表面を洗浄したため、
純水中に存在するＯ2 をＨＣｌ水溶液を構成するＨ+ に
よってＨ2 Ｏに還元することができるため、純水の溶存
酸素量を低減することができ、その結果、洗浄時に被洗
浄物表面に酸化物を形成し難くすることができる。な
お、塩酸（ＨＣｌ）のＨとＣｌは、電気陰性度に差があ
るため、Ｈの電子がＣｌ側に偏っており、このため、両
者のＨとＣｌは、純水中でイオン性となっている。この
ため、前述の如く、純水中に存在するＯ2 をＨＣｌ水溶
液を構成するＨ+によってＨ2 Ｏに還元することができ
る。As described above, in the first embodiment, since the surface of the object to be cleaned is washed with the hydrochloric acid aqueous solution obtained by adding hydrochloric acid to pure water.
O 2 present in the pure water can be reduced to H 2 O by H + constituting the aqueous HCl solution, so that the amount of dissolved oxygen in the pure water can be reduced. It is possible to make it difficult to form an oxide. Since H and Cl of hydrochloric acid (HCl) have a difference in electronegativity, electrons of H are biased toward the Cl side. Therefore, both H and Cl become ionic in pure water. ing. Therefore, as described above, O 2 present in pure water can be reduced to H 2 O by H + constituting an aqueous HCl solution.
【００２１】（実施例２）次に、図３はＨＦ処理後にオ
ーバーフロー純水洗浄を１０分間行った比較例の場合と
ＨＦ処理後に１００００ｐｐｍ（１ｖｅｌ％）のＨＣｌ
溶液にＳｉ（１００）ウェハを投入し、引き続き同一槽
に純水を供給しながらオーバーフロー洗浄を１０分間行
った本実施例２の場合のＳｉ（１００）表面のＳｉ−Ｈ
伸縮振動による吸収の現れる波数範囲の赤外吸収スペク
トルを示す図である。この図３から、ＨＣｌ溶液に被洗
浄物を投入した後、純水洗浄する本実施例２では、若干
酸化物の成長が認められるが、比較例の純水洗浄の場合
と比較すると、明らかに酸化物の成長が抑制されている
ことが判る。(Example 2) Next, FIG. 3 shows a case of a comparative example in which overflow pure water cleaning was performed for 10 minutes after the HF treatment, and 10,000 ppm (1 vel%) of HCl after the HF treatment.
A Si (100) wafer was put into the solution, and overflow cleaning was performed for 10 minutes while continuously supplying pure water to the same tank.
It is a figure which shows the infrared absorption spectrum of the wave number range in which the absorption by stretching vibration appears. As can be seen from FIG. 3, oxides were slightly grown in Example 2 in which the object to be cleaned was poured into the HCl solution and then washed with pure water. It can be seen that oxide growth is suppressed.
【００２２】このように、本実施例２では、純水に塩酸
を添加した塩酸水溶液で被洗浄物表面を洗浄したため、
純水中に存在するＯ2 をＨＣｌ水溶液を構成するＨ+ に
よってＨ2 Ｏに還元することができるため、純水の溶存
酸素量を低減することができ、その結果、洗浄時に被洗
浄物表面に酸化物を形成し難くすることができる。な
お、塩酸（ＨＣｌ）のＨとＣｌは、電気陰性度に差があ
るため、Ｈの電子がＣｌ側に偏っており、このため、両
者のＨとＣｌは、純水中でイオン性となっている。この
ため、前述の如く、純水中に存在するＯ2 をＨＣｌ水溶
液を構成するＨ+によってＨ2 Ｏに還元することができ
る。As described above, in the second embodiment, the surface of the object to be cleaned is washed with the hydrochloric acid aqueous solution obtained by adding hydrochloric acid to pure water.
O 2 present in the pure water can be reduced to H 2 O by H + constituting the aqueous HCl solution, so that the amount of dissolved oxygen in the pure water can be reduced. It is possible to make it difficult to form an oxide. Since H and Cl of hydrochloric acid (HCl) have a difference in electronegativity, electrons of H are biased toward the Cl side. Therefore, both H and Cl become ionic in pure water. ing. Therefore, as described above, O 2 present in pure water can be reduced to H 2 O by H + constituting an aqueous HCl solution.
【００２３】また、本実施例２では、被洗浄物を塩酸水
溶液で処理した後、純水を供給しながら流水洗浄を行っ
ているため、塩酸水溶液処理で除去できなかった異物等
を効率良く除去することができる。なお、本実施例２に
おいては、被洗浄物の投入を、洗浄槽内に作製した塩酸
水溶液に純水を供給し始めてから行うように構成しても
よく、上記と同様の効果を得ることができる。In the second embodiment, after the object to be cleaned is treated with an aqueous solution of hydrochloric acid and then washed with running water while supplying pure water, foreign substances which cannot be removed by the treatment with the aqueous solution of hydrochloric acid can be efficiently removed. can do. In the second embodiment, the cleaning object may be charged after pure water is supplied to the hydrochloric acid aqueous solution prepared in the cleaning tank, and the same effect as described above may be obtained. it can.
【００２４】また、上記実施例２においては、洗浄初期
の塩酸濃度を１００００ｐｐｍ（１ｖｅｌ％）している
ため、純水を供給しながら流水洗浄を行っても、塩酸濃
度が１０ｐｐｍ以下に下がらないようにしているため、
洗浄液中の溶存酸素量が低減したままの状態を保つこと
ができる。なお、上記実施例１，２においては、洗浄中
の塩酸水溶液の塩酸濃度は、少なくとも１０ｐｐｍ以上
であるのが好ましく、特に実施例２においては、純水供
給前の塩酸濃度が１００００ｐｐｍ以上であることが好
ましい。この場合、純水中の溶存酸素量を効率良く低減
することができる。In Example 2, the hydrochloric acid concentration in the initial stage of the washing is 10,000 ppm (1 vel%), so that the hydrochloric acid concentration does not drop to 10 ppm or less even if the washing is carried out with running pure water. Because
It is possible to maintain a state in which the amount of dissolved oxygen in the cleaning liquid has been reduced. In Examples 1 and 2, the hydrochloric acid concentration of the aqueous hydrochloric acid solution during washing is preferably at least 10 ppm, and particularly in Example 2, the hydrochloric acid concentration before pure water supply was 10,000 ppm or more. Is preferred. In this case, the amount of dissolved oxygen in pure water can be efficiently reduced.
【００２５】上記実施例１，２は、被洗浄物をシリコン
で構成する好ましい態様の場合について説明したが、本
発明においては、例えば、そのＳｉ上に形成したゲート
酸化膜等の各種の膜にも好ましく適用させることができ
る。In the first and second embodiments, the preferred embodiment in which the object to be cleaned is made of silicon has been described. However, in the present invention, for example, various films such as a gate oxide film formed on the Si are used. Can also be preferably applied.
【００２６】[0026]
【発明の効果】本発明によれば、既存の装置を用いつつ
純粋洗浄過程で被加工表面に成長する酸化物を安価にか
つ簡便に抑制することができるという効果がある。According to the present invention, there is an effect that oxides that grow on the surface to be processed during the pure cleaning process can be easily and inexpensively controlled using an existing apparatus.
【図１】比較例のＨＦ処理直後とその後オーバーフロー
純水洗浄を１０分間行った時のＳｉ（１００）表面のＳ
ｉ−Ｈ伸縮振動による吸収の現れる波数範囲の赤外吸収
スペクトルを示す図である。FIG. 1 shows the S (100) surface of Si (100) surface immediately after the HF treatment of a comparative example and after the overflow pure water cleaning was performed for 10 minutes.
It is a figure which shows the infrared absorption spectrum of the wave number range in which the absorption by iH stretching vibration appears.
【図２】ＨＦ処理後にオーバーフロー純水洗浄を１０分
間行った比較例の場合とＨＦ処理後に０．１ｖｏｌ％
（１０００ｐｐｍ）のＨＣｌ溶液に１０分間浸漬した本
実施例１の場合のＳｉ（１００）表面のＳｉ−Ｈ伸縮振
動による吸収の現れる波数範囲の赤外吸収スペクトルを
示す図である。FIG. 2 shows the case of a comparative example in which overflow pure water cleaning was performed for 10 minutes after the HF treatment, and 0.1 vol% after the HF treatment.
It is a figure which shows the infrared-absorption spectrum of the wave number range in which the absorption by Si-H stretching vibration of the Si (100) surface in the case of this Example 1 immersed in (1000 ppm) HCl solution for 10 minutes appears.
【図３】ＨＦ処理後にオーバーフロー純水洗浄を１０分
間行った比較例の場合とＨＦ処理後に１ｖｏｌ％（１０
０００ｐｐｍ）のＨＣｌ溶液にウェハを投入し、引き続
きオーバーフロー純水洗浄を１０分間行った本実施例２
の場合のＳｉ（１００）表面のＳｉ−Ｈ伸縮振動による
吸収の現れる波数範囲の赤外吸収スペクトルを示す図で
ある。FIG. 3 shows a case of a comparative example in which overflow pure water cleaning was performed for 10 minutes after HF treatment, and 1 vol% (10%) after HF treatment.
Example 2 in which the wafer was put into an HCl solution of 2,000 ppm, and then the wafer was washed with overflowed pure water for 10 minutes.
FIG. 9 is a diagram showing an infrared absorption spectrum in a wave number range in which absorption due to Si—H stretching vibration of the Si (100) surface occurs in the case of FIG.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−21595（ＪＰ，Ａ) 特開 平５−175182（ＪＰ，Ａ) 特開 平３−228327（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 21/304 H01L 21/306 H01L 21/308 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-21595 (JP, A) JP-A-5-175182 (JP, A) JP-A-3-228327 (JP, A) (58) Field (Int.Cl. 7 , DB name) H01L 21/304 H01L 21/306 H01L 21/308
Claims (11)
後、被洗浄物表面を純水に塩酸を添加した塩酸水溶液で
洗浄する工程を含むことを特徴とする半導体装置の製造
方法。1. A method for manufacturing a semiconductor device, comprising: after removing an oxide from a surface of an object to be cleaned, cleaning the surface of the object to be cleaned with an aqueous hydrochloric acid solution obtained by adding hydrochloric acid to pure water.
酸及び緩衝弗酸処理のうち、少なくともどちらか一方の
処理で行うことを特徴とする請求項１記載の半導体装置
の製造方法。2. The method for manufacturing a semiconductor device according to claim 1, wherein the oxide removal treatment on the surface of the object to be cleaned is performed by at least one of hydrofluoric acid treatment and buffered hydrofluoric acid treatment. .
１０ｐｐｍ以上であることを特徴とする請求項１又は２
記載の半導体装置の製造方法。 Wherein the hydrochloric acid concentration of the aqueous hydrochloric acid solution, according to claim 1 or 2, characterized in that at least 10ppm or more
The manufacturing method of the semiconductor device described in the above .
に形成した各種の膜であることを特徴とする請求項１乃
至３記載の半導体装置の製造方法。4. The method according to claim 1, wherein the object to be cleaned is silicon or various films formed thereon.
中に投入して洗浄を行った後、更に同一槽内に純水を供
給して洗浄を行うことを特徴とする半導体装置の製造方
法。5. The semiconductor device according to claim 1, wherein the object to be cleaned is poured into an aqueous hydrochloric acid solution prepared in a cleaning tank to perform cleaning, and then pure water is further supplied to the same tank to perform cleaning. Production method.
製した前記塩酸水溶液に純水を供給し始めてから行うこ
とを特徴とする請求項５記載の半導体装置の製造方法。6. The method of manufacturing a semiconductor device according to claim 5, wherein the object to be cleaned is charged after pure water is supplied to the aqueous hydrochloric acid solution prepared in the cleaning tank.
１００００ｐｐｍ以上であることを特徴とする請求項
５，６記載の半導体装置の製造方法。7. The method according to claim 5, wherein a hydrochloric acid concentration of the hydrochloric acid aqueous solution is at least 10,000 ppm or more.
に形成した各種の膜であることを特徴とする請求項５乃
至７記載の半導体装置の製造方法。8. The method according to claim 5, wherein the object to be cleaned is silicon or various films formed thereon.
を除去する処理の後に行うことを特徴とする請求項５乃
至８記載の半導体装置の製造方法。9. The method of manufacturing a semiconductor device according to claim 5, wherein said cleaning is performed after a process of removing an oxide from the surface of the object to be cleaned.
弗酸及び緩衝弗酸処理のうち、少なくともどちらか一方
の処理で行うことを特徴とする請求項５乃至９記載の半
導体装置の製造方法。10. The process for removing oxides on the surface of the object to be cleaned,
10. The method of manufacturing a semiconductor device according to claim 5, wherein at least one of hydrofluoric acid and buffered hydrofluoric acid treatment is performed.
濃度が１０ｐｐｍ未満にならない量であることを特徴と
する請求項５，６記載の半導体装置の製造方法。11. The method according to claim 5, wherein the supply amount of the pure water is such that the hydrochloric acid concentration of the aqueous hydrochloric acid solution does not become less than 10 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04812094A JP3320190B2 (en) | 1994-03-18 | 1994-03-18 | Method for manufacturing semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04812094A JP3320190B2 (en) | 1994-03-18 | 1994-03-18 | Method for manufacturing semiconductor device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07263392A JPH07263392A (en) | 1995-10-13 |
| JP3320190B2 true JP3320190B2 (en) | 2002-09-03 |
Family
ID=12794475
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|---|---|---|---|
| JP04812094A Expired - Lifetime JP3320190B2 (en) | 1994-03-18 | 1994-03-18 | Method for manufacturing semiconductor device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11204478A (en) | 1998-01-19 | 1999-07-30 | Mitsubishi Electric Corp | Method and apparatus for cleaning semiconductor substrate |
| JP6529715B2 (en) * | 2013-11-29 | 2019-06-12 | 株式会社Sumco | Method of manufacturing silicon wafer |
| CN107863288A (en) * | 2016-09-22 | 2018-03-30 | 中芯国际集成电路制造(上海)有限公司 | A kind of method for cleaning Semiconductor substrate |
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1994
- 1994-03-18 JP JP04812094A patent/JP3320190B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH07263392A (en) | 1995-10-13 |
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