JP3379302B2 - Plasma processing method - Google Patents
Plasma processing methodInfo
- Publication number
- JP3379302B2 JP3379302B2 JP26557095A JP26557095A JP3379302B2 JP 3379302 B2 JP3379302 B2 JP 3379302B2 JP 26557095 A JP26557095 A JP 26557095A JP 26557095 A JP26557095 A JP 26557095A JP 3379302 B2 JP3379302 B2 JP 3379302B2
- Authority
- JP
- Japan
- Prior art keywords
- plasma
- water vapor
- processed
- downflow
- treatment
- 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
Links
- 238000003672 processing method Methods 0.000 title claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 60
- 229910052739 hydrogen Inorganic materials 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 51
- 239000007789 gas Substances 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 15
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 238000009832 plasma treatment Methods 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 description 58
- 229910052710 silicon Inorganic materials 0.000 description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 19
- 239000010703 silicon Substances 0.000 description 19
- 238000007254 oxidation reaction Methods 0.000 description 18
- 230000001590 oxidative effect Effects 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 17
- 230000001603 reducing effect Effects 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000010453 quartz Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 230000007423 decrease Effects 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000000804 electron spin resonance spectroscopy Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910018557 Si O Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002250 progressing effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- -1 NF 3 Chemical compound 0.000 description 1
- 241000287462 Phalacrocorax carbo Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010571 fourier transform-infrared absorption spectrum Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004441 surface measurement Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Landscapes
- Plasma Technology (AREA)
- Chemical Vapour Deposition (AREA)
- Drying Of Semiconductors (AREA)
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【発明の属する技術分野】本発明は、プラズマ処理方法
に係わり、もっと具体的には、水素プラズマダウンフロ
ーによって、半導体基板表面に損傷を与えずに自然酸化
膜を除去したり、水素終端処理を行ったり、酸化を行っ
たりすることに適用できるプラズマ処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma processing method, and more specifically, hydrogen plasma downflow is used to remove a natural oxide film without damaging the surface of a semiconductor substrate or to perform hydrogen termination processing. The present invention relates to a plasma processing method applicable to performing or oxidizing.
【０００２】[0002]
【従来の技術】近年、半導体装置の製造工程において
は、例えば、シリコン基板の表面に生成した自然酸化膜
に起因するいろいろな障害が知られており、この自然酸
化膜を除去し、さらに水素終端を行ういろいろな方法が
提案されている。その方法としては、希釈ふっ酸を用い
たウエット処理方法（G.S.Higashi et al.,J. Appl. Ph
ys.,56,656,1990)や水素プラズマを用いたドライ処理方
法 (A.Kishimoto et al.,J.Appl. Phys.,29,2273,199
0)、水素原子（水素ラジカル）を用いたドライ処理方法
（T.Takahagi et al.,J. Appl. Phys.,68,2187,1990)な
どがある。しかし、これらの方法では、自然酸化膜を除
去した後のシリコン基板の表面に損傷を与えることが知
られている。それに対して、水素＋水素プラズマダウン
フローにＮＦ3を添加した処理方法 (J.Kikuchi et al.,
J.Appl. Phys.,33,2207,1994)は、処理した後の表面に
与える損傷が少ない方法として提案されており、発明者
らも特願平05-074076 「半導体装置の製造装置及び半導
体装置の製造方法」として既に提案している。2. Description of the Related Art In recent years, various obstacles due to, for example, a natural oxide film formed on the surface of a silicon substrate have been known in the process of manufacturing a semiconductor device. Various methods of doing are proposed. As the method, a wet treatment method using diluted hydrofluoric acid (GSHigashi et al., J. Appl. Ph.
ys., 56,656,1990) or a dry treatment method using hydrogen plasma (A. Kishimoto et al., J. Appl. Phys., 29, 2273, 199).
0), a dry treatment method using hydrogen atoms (hydrogen radicals) (T. Takahagi et al., J. Appl. Phys., 68, 2187, 1990). However, it is known that these methods damage the surface of the silicon substrate after removing the natural oxide film. On the other hand, a treatment method in which NF 3 is added to hydrogen + hydrogen plasma downflow (J. Kikuchi et al.,
J. Appl. Phys., 33, 2207, 1994) has been proposed as a method that causes less damage to the surface after treatment, and the inventors of the present invention have also proposed Japanese Patent Application No. 05-074076 "Semiconductor Device Manufacturing Equipment and Semiconductor It has already been proposed as a “device manufacturing method”.
【０００３】一方、シリコン表面にゲート酸化膜として
用いられるような極薄酸化膜を形成する際に、水素ラジ
カルを一緒に用いると酸化膜の特性が向上することが報
告されており K.Ohmi et al.,Ext.Abs.of 1995 Interna
tional Conference on SolidState Devices and Materi
als,Osaka (1995)258 、半導体表面の酸化処理を還元性
を有する水素ラジカルと合わせて行うことの有効性が示
されている。On the other hand, it has been reported that when forming an ultrathin oxide film used as a gate oxide film on a silicon surface, the use of hydrogen radicals together improves the characteristics of the oxide film. K. Ohmi et al. al., Ext.Abs.of 1995 Interna
tional Conference on SolidState Devices and Materi
als, Osaka (1995) 258, the effectiveness of performing the oxidation treatment of the semiconductor surface together with a reducing hydrogen radical is shown.
【０００４】[0004]
【発明が解決しようとする課題】水素＋水蒸気プラズマ
ダウンフローにＮＦ3 を添加した水素プラズマダウンフ
ロー処理では、自然酸化膜を除去する特徴があるが、同
時に基板の表面を酸化させる特徴も兼ね備えている。酸
化膜を生成し、その後酸化膜を除去したシリコン表面
は、原子レベルで観察すると平坦な表面が得られること
が知られている。しかし、従来の処理方法では、酸化膜
の生成と同時に、アンモニア系薄膜も生成され、このア
ンモニア系薄膜によって酸化作用が阻害されて、平坦な
表面を得ることができなかった。 Problem to be Solved by the Invention Hydrogen + steam plasma
Hydrogen plasma downflow with NF3 added to downflow
The raw process has the characteristic of removing the natural oxide film.
Sometimes it also has the characteristic of oxidizing the surface of the substrate. acid
Silicon surface with oxide film removed and oxide film removed
Is that a flat surface can be obtained when observed at the atomic level
It has been known. However, in the conventional processing method, the oxide film
At the same time as the generation of
The MONMONIA-based thin film hinders the oxidization action, resulting in a flat surface.
Could not get the surface.
【０００５】[0005]
【０００６】さらに、水素プラズマダウンフロー処理に
よる酸化方法における水素ラジカルの発生は、５００〜
９００°Ｃの高温の処理容器壁あるいは被処理物の表面
における水素分子の分解によるとされている。還元力つ
まり水素ラジカル量は、水素ガス流量と容器壁あるいは
被処理物の温度による。一方、酸化膜の成膜速度は、処
理温度に依存する。このため、還元力を一定に保ちなが
ら、酸化力を増減させることは困難であった。Further, the generation of hydrogen radicals in the oxidation method by hydrogen plasma down-flow treatment is 500 to
It is said that hydrogen molecules are decomposed on the wall of the processing container at a high temperature of 900 ° C or the surface of the object to be processed. The reducing power, that is, the amount of hydrogen radicals depends on the flow rate of hydrogen gas and the temperature of the container wall or the object to be treated. On the other hand, the deposition rate of the oxide film depends on the processing temperature. Therefore, it is difficult to increase or decrease the oxidizing power while keeping the reducing power constant.
【０００７】そこで本発明は、（１）基板温度を制御す
ることによって、処理中に生成した被処理物の表面に堆
積する薄膜の一部を除去し、それによって被処理物の表
面の酸化と酸化膜除去を同時に進行させたり、（２）水
素に添加する水蒸気量を制御することによって、被処理
物の表面の酸化と酸化膜除去を同時に進行させたり、
（３）水素に添加する水蒸気量を制御することによっ
て、被処理物の表面に対して酸素ラジカル量を増大させ
て酸化作用を促進させたり、酸素ラジカル量を増減させ
て、酸化力を制御させることができるプラズマ処理方法
を提供することを目的としている。Therefore, the present invention (1) controls a substrate temperature to remove a part of a thin film deposited on the surface of an object to be processed generated during the processing, thereby oxidizing the surface of the object to be processed. Oxide film removal proceeds at the same time, or (2) oxidation of the surface of the object to be processed and oxide film removal proceed at the same time by controlling the amount of water vapor added to hydrogen,
(3) By controlling the amount of water vapor added to hydrogen, the amount of oxygen radicals on the surface of the object to be treated is increased to accelerate the oxidizing action, or the amount of oxygen radicals is increased or decreased to control the oxidizing power. It is an object of the present invention to provide a plasma processing method capable of performing the plasma processing.
【０００８】[0008]
【課題を解決するための手段】上で述べた課題は、水素
と、酸素原子を含む分子とを含む混合ガスからなるプラ
ズマダウンフローに、ふっ素を含むガスを添加し、該プ
ラズマダウンフローの下流で被処理物を処理するプラズ
マ処理方法において、ダウンフロー処理を行う前に被処
理物の温度を上げて処理を開始することにより、被処理
物表面の酸化膜除去と、酸化膜の生成を同時に行なう第
１の工程と、次いで、該被処理物の温度を下げて、被処
理物表面の酸化膜の除去と被処理物表面の水素終端を行
なう第２の工程とを含むか、あるいは、ダウンフロー処
理工程の途中で被処理物の温度を上げることにより、被
処理物表面の酸化膜除去と、酸化膜の生成を同時に行な
う第３の工程と、次いで、該被処理物の温度を下げて、
被処理物表面の酸化膜の除去と被処理物表面の水素終端
を行なう第２の工程とを含むプラズマ処理方法によって
解決される。[Means for Solving the Problems] The above-mentioned problem is that a gas containing fluorine is added to a plasma downflow consisting of a mixed gas containing hydrogen and molecules containing oxygen atoms, and a downstream gas of the plasma downflow is added. In the plasma processing method of treating an object to be treated with the above method, the temperature of the object to be treated is raised before the downflow treatment to start the treatment.
And oxide removal of goods surface, a first step for generating the oxide film at the same time, then, lowering the temperature of該被treated, the treatment
The oxide film on the surface of the physical object is removed and hydrogen is terminated on the surface of the object to be processed.
Or and a Nau second step, or by raising the temperature of the middle object to be processed in the down-flow process step, the
The oxide film on the surface of the processed material is removed and the oxide film is generated at the same time.
Cormorant a third step, then, lowering the temperature of該被treated,
Removal of oxide film on the surface of the object to be processed and hydrogen termination on the surface of the object to be processed
And a second step of performing a plasma treatment method.
【０００９】こゝで、前記少なくとも一つの酸素原子を
含む分子が、水蒸気または酸素であり、前記第１と前記
第３の工程の温度が３０°Ｃないし４０°Ｃ、前記第２
の工程の温度が２７°Ｃ以下であり、前記少なくともふ
っ素を含むガスが、ＮＦ3 、ＣＦ4 、ＳＦ6 、Ｃ4 Ｆ8
であり、前記被処理物が、半導体基板であり、さらに、
前記被処理物が、表面に酸化物を有する半導体基板であ
る。Here, the molecule containing at least one oxygen atom is water vapor or oxygen, and the temperature of the first and third steps is 30 ° C. to 40 ° C.
The temperature of the step is 27 ° C. or lower, and the gas containing at least fluorine is NF 3 , CF 4 , SF 6 , C 4 F 8
And the object to be processed is a semiconductor substrate,
The object to be treated is a semiconductor substrate having an oxide on its surface.
【００１０】[0010]
【００１１】水素＋水蒸気プラズマにふっ素を含むガス
を添加したプラズマダウンフローに曝されて基板表面に
膜が生成したり、生成した膜が除去されたりする現象
は、図３〜図５に例示したフーリエ変換赤外吸収スペク
トル分光法（以下、ＦＴ−ＩＲ法と略称）で測定した結
果から分かるように、基板温度に依存している。つま
り、基板に堆積される膜に含まれるＮ−Ｈ吸収は、低い
温度では時間と共に堆積していくが、温度が高くなると
増加しなくなる。一方、基板表面に生成され、あるいは
除去される酸化膜によるＳｉ−Ｏ吸収は、低い温度では
時間と共に減少していくが、温度が高くなると吸収が促
進される。The phenomenon in which a film is formed on the substrate surface or is removed by being exposed to a plasma downflow in which a gas containing fluorine is added to hydrogen + steam plasma is illustrated in FIGS. 3 to 5. As can be seen from the result of measurement by Fourier transform infrared absorption spectrum spectroscopy (hereinafter abbreviated as FT-IR method), it depends on the substrate temperature. That is, the N—H absorption contained in the film deposited on the substrate is deposited with time at a low temperature, but does not increase at a higher temperature. On the other hand, the Si—O absorption by the oxide film generated or removed on the substrate surface decreases with time at low temperature, but the absorption is promoted at higher temperature.
【００１２】こうした現象を利用して、本発明では、水
素＋水蒸気プラズマダウンフロー処理工程の中で、処理
前あるいは処理の途中で処理温度を３０〜４０°Ｃ（第
１と第３の工程）に昇温し、その後引き続いて処理の途
中で処理温度を２７°Ｃ（第２の工程）に降温するよう
にしている。その結果、第１あるいは第３の工程におい
て、基板の表面に不具合な損傷を与えずに、酸化膜の生
成と酸化膜の除去を同時に進行させることができる。ま
た、第２の工程において、酸化膜が除去され、水素終端
した表面が得られる。Utilizing such a phenomenon, in the present invention, the treatment temperature is 30 to 40 ° C. (first and third steps) in the hydrogen + steam plasma downflow treatment step before or during the treatment. After that, the processing temperature is lowered to 27 ° C. (second step) in the middle of the processing. As a result, in the first or third step, the generation of the oxide film and the removal of the oxide film can be simultaneously progressed without giving a bad damage to the surface of the substrate. Further, in the second step, the oxide film is removed and a hydrogen-terminated surface is obtained.
【００１３】また、水素と水蒸気とを少なくとも含む混
合ガスからなるプラズマダウンフローに、少なくともふ
っ素を含むガスを添加し、該プラズマダウンフローの下
流で被処理物を処理するプラズマ処理方法において、ダ
ウンフロー処理工程の初めに前記水蒸気を２％ないし７
％添加する工程と、次いで、前記水蒸気を２％未満添加
する工程とを含むか、ダウンフロー処理工程の初めに前
記水蒸気を２％ないし７％添加する工程と、次いで、前
記水蒸気を７％を越えて添加する工程とを含むプラズマ
処理方法によって解決される。Further, in the plasma processing method of adding a gas containing at least fluorine to a plasma downflow consisting of a mixed gas containing at least hydrogen and water vapor, and processing an object to be processed downstream of the plasma downflow, the downflow is performed. At the beginning of the treatment process, the water vapor is 2% to 7%.
And adding%, then either a step of adding less than 2% of the steam, the steps of the water vapor is added 2% to 7% at the beginning of the down-flow process step, then 7% of the water vapor It is solved by the plasma processing method comprising the step of adding across.
【００１４】つまり、本発明においては、水素＋水蒸気
プラズマダウンフローにＮＦ3 を添加した処理における
基板表面の酸化を促進させるために酸素ラジカル量を増
大させるようにしている。この酸素ラジカル量は、図６
〜図７に示した電子スピン共鳴分光法（以下、ＥＳＲ法
と略称）によって測定した結果から分かるように、水蒸
気プラズマに添加する水蒸気量によって極大値を示す。
具体的には、水蒸気の添加量が２％ないし７％の範囲で
酸素ラジカル量が著しく増大する。That is, in the present invention, the amount of oxygen radicals is increased in order to promote the oxidation of the substrate surface in the process of adding NF 3 to the hydrogen + steam plasma downflow. This oxygen radical amount is shown in FIG.
As can be seen from the results of measurement by electron spin resonance spectroscopy (hereinafter abbreviated as ESR method) shown in FIG. 7, the maximum value is shown by the amount of water vapor added to the water vapor plasma.
Specifically, the amount of oxygen radicals significantly increases when the amount of water vapor added is in the range of 2% to 7%.
【００１５】さらに、水素と水蒸気とを少なくとも含む
混合ガスからなるプラズマダウンフローの下流で被処理
物を処理する水素プラズマダウンフロー処理方法におい
て、処理工程の初めに前記水蒸気を２％ないし７％添加
する工程と、次いで、前記処理工程の途中で前記水蒸気
を７％を越えて添加する工程とを含むか、または、
処理
工程の初めに前記水蒸気を２％ないし７％添加する工程
と、次いで、前記処理工程の途中で前記水蒸気を２％未
満添加する工程とを含むか、または、処理工程の初めに
前記水蒸気を７％を越えて添加する工程と、次いで、前
記処理工程の途中で前記水蒸気を２％ないし７％添加す
る工程とを含むか、または、処理工程の初めに前記水蒸
気を２％未満添加する工程と、次いで、前記処理工程の
途中で前記水蒸気を２％ないし７％添加する工程とを含
むプラズマ処理方法によって解決される。Further, in the hydrogen plasma downflow processing method for processing an object to be processed downstream of a plasma downflow consisting of a mixed gas containing at least hydrogen and steam, 2% to 7% of the steam is added at the beginning of the processing step. a step of, then either a step of adding over 7% of the water vapor in the course of the treatment process, or,
A step of the water vapor is added 2% to 7% at the beginning of the treatment process, then either a step of adding less than 2% of the water vapor in the course of the treatment process, or the steam at the beginning of the process and adding over 7%, then either a step of adding 2% to 7% of the water vapor in the course of the treatment process, or, adding less than 2% of the steam at the beginning of the process If, then, a step of adding 2% to 7% of the water vapor in the course of the processing steps including
It is solved by non-plasma processing method.
【００１６】つまり、水素プラズマダウンフロー中の水
素ラジカル量は、図８から分かるように、水蒸気添加量
が１％前後で一定値となる。つまり、ダウンフロー中の
水素ラジカル量を一定に保ちながら、酸素ラジカル量を
増減して、酸化力を抑制して、還元力を促進させたり、
あるいは還元作用よりも酸化作用を強く生じさせたりす
ることができる。That is, as can be seen from FIG. 8, the amount of hydrogen radicals in the hydrogen plasma downflow has a constant value when the amount of added steam is around 1%. That is, while keeping the amount of hydrogen radicals in the downflow constant, increase or decrease the amount of oxygen radicals, suppress the oxidizing power, promote the reducing power,
Alternatively, the oxidizing action can be stronger than the reducing action.
【００１７】そこで、本発明では、このような水素プラ
ズマダウンフローの特性を用いて、処理工程の中で水素
プラズマ中に添加する水蒸気の量を制御して、被処理物
の表面の酸化を促進したり、酸化を抑制したりして、被
処理物の表面に不具合な損傷を与えずに酸化膜の生成と
酸化膜の除去を同時に進行させることができる。Therefore, in the present invention, the characteristics of the hydrogen plasma downflow are used to control the amount of water vapor added to the hydrogen plasma during the treatment process to promote the oxidation of the surface of the object to be treated. It is possible to simultaneously perform the generation of the oxide film and the removal of the oxide film without damaging the surface of the object to be processed by suppressing the oxidation or suppressing the oxidation.
【００１８】[0018]
【発明の実施の形態】図１は本発明の処理を行う水素プ
ラズマダウンフロー処理装置の構成図、図２はＦＴ−Ｉ
Ｒ法による測定系の模式図、図３は酸化膜生成−酸化膜
除去の温度依存性（２６°Ｃ）、図４は酸化膜生成−酸
化膜除去の温度依存性（３０°Ｃ）、図５は酸化膜生成
−酸化膜除去の温度依存性（４３°Ｃ）、図６は酸素ラ
ジカル量の水蒸気添加量依存性（１Ｔorr ）、図７は酸
素ラジカル量の水蒸気添加量依存性（３Ｔorr ）、図８
は水素ラジカル量の水蒸気添加量依存性である。1 is a block diagram of a hydrogen plasma downflow processing apparatus for carrying out the processing of the present invention, and FIG. 2 is an FT-I.
Schematic diagram of measurement system by R method, FIG. 3 is temperature dependence of oxide film formation-oxide film removal (26 ° C.), FIG. 4 is temperature dependence of oxide film formation-oxide film removal (30 ° C.), diagram 5 is the temperature dependence of oxide film formation-oxide film removal (43 ° C.), FIG. 6 is the dependence of the amount of oxygen radicals on the amount of water vapor added (1 Torr), and FIG. 7 is the dependence of the amount of oxygen radicals on the amount of water vapor added (3 Torr). , Fig. 8
Is the dependence of the amount of hydrogen radicals on the amount of water vapor added.
【００１９】図において、１は石英チャンバ、２は主ガ
ス導入手段、2aは水素ガス導入管、2bは水蒸気導入管、
2c、2dはマスフローコントローラ、2e、2fはバルブ、３
は真空排気手段、４は継ぎ手、５はプラズマ生成部、5a
はマイクロ波電源、６はガス混合部、７は添加ガス導入
手段、7aはマスフローコントローラ、7bはバルブ、８は
ダウンフロー処理部、8aはヒータ、8bは熱電対、8cは電
源、９は被処理物、10は水素プラズマダウンフロー処理
装置、20はＦＴ−ＩＲ測定系、21は赤外線検知器、22は
赤外線光源である。In the figure, 1 is a quartz chamber, 2 is a main gas introducing means, 2a is a hydrogen gas introducing pipe, 2b is a steam introducing pipe,
2c and 2d are mass flow controllers, 2e and 2f are valves, 3
Is a vacuum exhaust means, 4 is a joint, 5 is a plasma generation part, 5a
Is a microwave power source, 6 is a gas mixing section, 7 is an additive gas introducing means, 7a is a mass flow controller, 7b is a valve, 8 is a downflow processing section, 8a is a heater, 8b is a thermocouple, 8c is a power source, and 9 is a target. The object to be processed, 10 is a hydrogen plasma downflow processing apparatus, 20 is an FT-IR measurement system, 21 is an infrared detector, and 22 is an infrared light source.
【００２０】〔実施例１〕図１において、水素プラズマ
ダウンフロー処理装置10の構成は以下のとおりである。
すなわち、内径９mmφの円筒状の石英チャンバ１の、一
端部には水素＋水蒸気の主ガス導入手段２が接続され、
他端部には真空排気手段３が接続されている。主ガス導
入手段２は、水素ガス導入管2aと水蒸気導入管2bからな
り、導入管2a、2bのそれぞれには、マスフローコントロ
ーラ2c、2dと、それらの下流にバルブ2e、2fが設けられ
ており、水素ガスと水蒸気のそれぞれの流量を調整した
あと両者を所定の比率で混合して継ぎ手４から石英チャ
ンバ１の中に導入できるようになっている。[Embodiment 1] In FIG. 1, the structure of a hydrogen plasma downflow processing apparatus 10 is as follows.
That is, a main gas introducing means 2 of hydrogen + steam is connected to one end of a cylindrical quartz chamber 1 having an inner diameter of 9 mmφ,
The vacuum exhaust means 3 is connected to the other end. The main gas introducing means 2 comprises a hydrogen gas introducing pipe 2a and a steam introducing pipe 2b. The introducing pipes 2a and 2b are respectively provided with mass flow controllers 2c and 2d and valves 2e and 2f downstream thereof. After adjusting the respective flow rates of hydrogen gas and water vapor, they can be mixed at a predetermined ratio and introduced into the quartz chamber 1 from the joint 4.
【００２１】また、石英チャンバ１には継ぎ手４に近い
上流側にプラズマ生成部５が設けられており、マイクロ
波電源5aから供給される2.45ＧＨｚによって水素ガス＋
水蒸気のプラズマを生成できる。また、石英チャンバ１
の、プラズマ生成部５から２００mm下流部はガス混合部
６になっており、添加ガス導入手段７が接続されてい
る。この添加ガス導入手段７は、マスフローコントロー
ラ7aとその下流に設けられたバルブ7bを介して、例え
ば、ＮＦ3 、ＣＦ4 、ＳＦ6 、Ｃ4 Ｆ8 などのふっ素を
含むガスを水素＋水蒸気プラズマガスに制御性よく添加
できるようになっている。さらに、８００mm下流側には
ダウンフロー処理部８が設けられており、シリコンウェ
ーハのような被処理物９を配置できるようになってい
る。このダウンフロー処理部８は、石英チャンバ１の回
りにヒータ8aが設けられており、熱電対8bで電源8cを調
整してダウンフロー処理部８の温度、つまり被処理物９
を所定の温度に制御することができる。石英チャンバ１
は真空排気手段３によって真空排気され、所定の真空度
に保てるようになっている。Further, the quartz chamber 1 is provided with a plasma generator 5 on the upstream side near the joint 4, and the hydrogen gas + is supplied by 2.45 GHz supplied from the microwave power source 5a.
A plasma of water vapor can be generated. Also, the quartz chamber 1
The portion 200 mm downstream from the plasma generation portion 5 is a gas mixing portion 6, to which an additive gas introducing means 7 is connected. This additive gas introducing means 7 uses a gas containing fluorine such as NF 3 , CF 4 , SF 6 , C 4 F 8 and the like through a mass flow controller 7a and a valve 7b provided downstream thereof for hydrogen + steam plasma. It can be added to gas with good controllability. Further, a downflow processing part 8 is provided on the downstream side of 800 mm so that an object 9 to be processed such as a silicon wafer can be arranged. The downflow processing unit 8 is provided with a heater 8a around the quartz chamber 1, and the temperature of the downflow processing unit 8, that is, the object to be processed 9 is adjusted by adjusting the power source 8c with the thermocouple 8b.
Can be controlled to a predetermined temperature. Quartz chamber 1
Is evacuated by vacuum evacuation means 3 so that it can be maintained at a predetermined degree of vacuum.
【００２２】図２はＦＴ−ＩＲ測定系20は、図１に示し
た水素プラズマダウンフロー処理装置10のダウンフロー
処理部８に組み込まれている。つまり、ダウンフロー処
理部８の上下には、赤外線に透明な窓が設けてあり、被
処理物９の表面側には例えばＭＣＴ（Hg-Cd-Te) の赤外
線検知器21が設けられ、被処理物９の裏側には干渉計を
介して赤外線光源22が設けられている。In FIG. 2, the FT-IR measurement system 20 is incorporated in the downflow processing unit 8 of the hydrogen plasma downflow processing apparatus 10 shown in FIG. That is, infrared transparent windows are provided above and below the downflow processing unit 8, and an infrared detector 21 such as MCT (Hg-Cd-Te) is provided on the surface side of the object 9 to be processed. An infrared light source 22 is provided on the back side of the processed material 9 via an interferometer.
【００２３】処理方法は、被処理物９にはシリコンウェ
ーハを用いた。ダウンフロー処理部８の温度条件は、図
示してないヒータによって加熱することによって２６°
Ｃ、３０°Ｃ、４３°Ｃの三つの条件とした。また、雰
囲気は、水素：９０sccm、水蒸気：１０sccm、ＮＦ3 ：
９０sccm、圧力：３Torr、マイクロ波のパワー：５０Ｗ
で一定とした。水素プラズマダウンフロー処理を１分間
行い、ＦＴ−ＩＲ法によってシリコンの表面を測定し、
このダウンフロー処理と表面の測定を５回繰り返した。
ダウンフロー処理時間の累計は５分間である。As the processing method, a silicon wafer was used as the object 9 to be processed. The temperature condition of the downflow processing unit 8 is 26 ° by heating with a heater (not shown).
Three conditions of C, 30 ° C and 43 ° C were set. The atmosphere is hydrogen: 90 sccm, water vapor: 10 sccm, NF 3 :
90sccm, pressure: 3Torr, microwave power: 50W
It was fixed at. Hydrogen plasma downflow treatment is performed for 1 minute, and the surface of silicon is measured by the FT-IR method.
This downflow treatment and surface measurement were repeated 5 times.
The total downflow processing time is 5 minutes.
【００２４】こうして、シリコンの表面の酸化膜の増
減、および酸化膜を除去した結果生成し、酸素ラジカル
によるシリコンの表面の酸化を抑制するといわれる堆積
膜の増減を観察した。その結果は、縦軸はＮ−ＨとＳｉ
−Ｏのそれぞれの吸収率（％）、横軸は波数（ｃｍ-1)
の図で示した。Thus, the increase / decrease of the oxide film on the surface of silicon and the increase / decrease of the deposited film which is generated as a result of removing the oxide film and is said to suppress the oxidation of the surface of silicon by oxygen radicals were observed. The result shows that the vertical axis is NH and Si.
-O absorption rate (%) of each, horizontal axis is wave number (cm -1 ).
It is shown in the figure.
【００２５】図３は、シリコンウェーハの表面に酸化膜
を形成したウェーハを２６°Ｃでダウンフロー処理した
ときの結果である。酸化膜を表すＳｉ−Ｏの吸収（１０
４０ｃｍ-1）は処理時間とともに減少していき、酸化膜
がエッチングされていることを示している。堆積膜に含
まれるＮ−Ｈの吸収（３３００ｃｍ-1）は、処理時間が
増していくと増加していき堆積膜が形成されていること
を示している。処理時間５分後には酸化膜は除去され
た。図示してない５分以降は、堆積膜の吸収に増加は見
られなく、シリコン表面における酸化膜の形成とその除
去が生じていないことが分かる。堆積膜は昇華性がある
のでウェーハを加熱すれば除去できる。FIG. 3 shows the results of down-flowing a wafer having an oxide film formed on the surface of a silicon wafer at 26 ° C. Absorption of Si-O (10
40 cm −1 ) decreases with the processing time, indicating that the oxide film is etched. The absorption of N—H contained in the deposited film (3300 cm −1 ) increases as the processing time increases, indicating that the deposited film is formed. After the treatment time of 5 minutes, the oxide film was removed. After 5 minutes (not shown), there is no increase in the absorption of the deposited film, indicating that the formation and removal of the oxide film on the silicon surface have not occurred. Since the deposited film has sublimability, it can be removed by heating the wafer.
【００２６】図４はシリコンウェーハの表面を３０°Ｃ
でダウンフロー処理したときの結果を示す。Ｓｉ−Ｏに
よる吸収は増加しており、酸化が進行していることを示
す。また、Ｎ−Ｈによる吸収も増加しており、酸化膜の
除去が同時に進行していることを示す。これは、ウェー
ハを加熱したことにより、堆積膜の膜厚が減少し、酸素
ラジカルによる酸化が同時に生じているからだと考えら
れる。その後、ウェーハの温度を２６°Ｃに降温したと
ころ、５分間のダウンフロー処理で酸化膜が除去され
た。このような酸化と酸化膜除去の同時進行は、ウェー
ハ温度４０°Ｃまで確認された。因みに、図５はシリコ
ンウェーハの表面を４３°Ｃに加熱してダウンフロー処
理をしたときの結果であるが、堆積膜の付着はなく、シ
リコン表面の酸化が進行している。FIG. 4 shows the surface of a silicon wafer at 30 ° C.
Shows the result when downflow processing is performed. Absorption by Si-O is increasing, indicating that oxidation is in progress. In addition, absorption by N—H is also increasing, showing that removal of the oxide film is progressing at the same time. It is considered that this is because the film thickness of the deposited film is reduced by heating the wafer and the oxidation due to the oxygen radicals is simultaneously generated. Then, when the temperature of the wafer was lowered to 26 ° C., the oxide film was removed by the downflow treatment for 5 minutes. Such simultaneous progress of oxidation and oxide film removal was confirmed up to a wafer temperature of 40 ° C. By the way, FIG. 5 shows the result when the surface of the silicon wafer was heated to 43 ° C. and the downflow treatment was performed, but there is no deposition film deposition and oxidation of the silicon surface is progressing.
【００２７】〔実施例２〕実施例１では、酸素ラジカル
による酸化促進のために、被処理物であるシリコンウェ
ーハを加熱して堆積膜の膜厚を減少させた。しかし、酸
化作用を促進させるには酸素ラジカル量を増大させるこ
とによっても同様の効果が得られる。そこで、図１にお
いて、添加ガス導入手段７は用いず、水蒸気導入管2bの
マスフローコントローラ2dとバルブ2fを制御して水蒸気
の添加量を加減した。発生する酸素ラジカルの測定は、
図示してないが、石英チャンバ１にＥＳＲキャビティと
バラトロンセンサを付設してＥＳＲ法によって行った。[Embodiment 2] In Embodiment 1, in order to accelerate the oxidation by oxygen radicals, the silicon wafer which is the object to be processed is heated to reduce the thickness of the deposited film. However, the same effect can be obtained by increasing the amount of oxygen radicals in order to accelerate the oxidizing action. Therefore, in FIG. 1, the added gas introduction means 7 is not used, and the mass flow controller 2d and the valve 2f of the water vapor introduction pipe 2b are controlled to adjust the amount of added water vapor. The measurement of oxygen radicals generated is
Although not shown, the quartz chamber 1 was provided with an ESR cavity and a Baratron sensor, and the ESR method was used.
【００２８】図６と図７は、水素プラズマダウンフロー
中に添加する水蒸気の添加量によって、ダウンフロー中
の酸素ラジカル量がどのように変化するかをＥＳＲ法に
よって測定した結果である。縦軸は酸素ラジカル量（任
意単位）、横軸は水蒸気の添加量（％、水蒸気／水素＋
水蒸気）である。FIGS. 6 and 7 show the results of measurement by the ESR method as to how the amount of oxygen radicals in the downflow changes depending on the amount of water vapor added during the hydrogen plasma downflow. The vertical axis represents the amount of oxygen radicals (arbitrary unit), the horizontal axis represents the amount of water vapor added (%, water vapor / hydrogen +
Water vapor).
【００２９】圧力：１Torrと３Ｔorr のとき共に、水蒸
気の添加量が２％ないし７％の添加量で酸素ラジカルの
発生量に増加が見られた。その結果、例えば水蒸気添加
量５％とし、シリコンウェーハの温度を２６°Ｃに保っ
てダウンフロー処理を行ったところ、実施例１と同様
に、酸化と酸化膜除去の同時進行が見られた。At both pressures of 1 Torr and 3 Torr, the amount of oxygen radicals produced increased when the amount of water vapor added was 2% to 7%. As a result, for example, when the amount of water vapor added was 5% and the down-flow treatment was carried out while maintaining the temperature of the silicon wafer at 26 ° C., as in Example 1, simultaneous progress of oxidation and oxide film removal was observed.
【００３０】〔実施例３〕図８は、実施例２と同様の測
定手段を用いて酸素ラジカルと同時に水素ラジカルを測
定した結果、つまり、水素ラジカル量の水蒸気添加量依
存性を示したものである。水素ラジカル量は、水蒸気を
１％以上添加すると、水素ラジカルの発生量は、水蒸気
が無添加のとき、すなわち水素のみの場合と比べて、１
Ｔorr で１００倍、３Ｔorr で５００倍となり、それ以
上に水蒸気の添加量を増やしても水素ラジカル量は一定
値を保つ。[Embodiment 3] FIG. 8 shows the results of measuring hydrogen radicals at the same time as oxygen radicals using the same measuring means as in Embodiment 2, that is, the dependency of the amount of hydrogen radicals on the amount of water vapor added. is there. Regarding the amount of hydrogen radicals, when steam is added in an amount of 1% or more, the amount of hydrogen radicals generated is 1
Torr is 100 times, and 3 Torr is 500 times, and the hydrogen radical amount keeps a constant value even if the amount of water vapor added is further increased.
【００３１】従って、処理工程の初めに水蒸気を２％な
いし７％添加した雰囲気で処理を行い、次いで、処理工
程の途中で水蒸気を７％を越えて添加した雰囲気で処理
を行った。そうすると、還元作用は一定なので、酸化作
用は相対的に増加し、その後、酸化作用を相対的に減少
させることができる。 Therefore, the treatment was performed in the atmosphere in which 2% to 7% of steam was added at the beginning of the treatment step, and then in the atmosphere in which the amount of steam exceeded 7% was added in the middle of the treatment step. Then, since the reducing effect is constant, the oxidizing effect is relatively increased, and then the oxidizing effect can be relatively decreased .
【００３２】また、処理工程の初めに水蒸気を２％ない
し７％添加した雰囲気で処理を行い、次いで、処理工程
の途中で水蒸気を２％未満添加した雰囲気で処理を行っ
た。そうすると、還元作用は一定なので、酸化作用は相
対的に増加し、その後、酸化作用を相対的に減少させる
ことができる。 Further, the treatment was conducted in the atmosphere containing 2% to 7% of steam at the beginning of the treatment step, and then the treatment was conducted in the atmosphere containing less than 2% of water vapor during the treatment step. Then, since the reducing effect is constant, the oxidizing effect is relatively increased, and then the oxidizing effect can be relatively decreased .
【００３３】さらに、処理工程の初めに水蒸気を７％を
越えて添加した雰囲気で処理を行い、次いで、処理工程
の途中で水蒸気を２％ないし７％を添加した雰囲気で処
理を行った。そうすると、還元作用は一定なので、酸化
作用は相対的に減少し、その後、酸化作用を相対的に増
加させることができる。 Further, at the beginning of the treatment step, the treatment was carried out in an atmosphere containing more than 7% of steam, and then, in the middle of the treatment step, treatment was carried out in an atmosphere of adding 2% to 7% of steam. Then, since the reducing effect is constant, the oxidizing effect is relatively decreased, and then the oxidizing effect can be relatively increased .
【００３４】さらに、処理工程の初めに水蒸気を２％未
満添加した雰囲気で処理を行い、次いで、処理工程の途
中で水蒸気を２％ないし７％を添加して処理を行った。
そうすると、還元作用は一定なので、酸化作用は相対的
に減少し、その後、酸化作用を相対的に増加させること
ができる。 Further, at the beginning of the treatment step, the treatment was carried out in an atmosphere containing less than 2% of steam, and then 2% to 7% of steam was added during the treatment step.
Then, since the reducing effect is constant, the oxidizing effect is relatively decreased, and then the oxidizing effect can be relatively increased .
【００３５】[0035]
【発明の効果】本発明によれば、水素＋水蒸気プラズマ
ダウンフローに例えばＮＦ3 を添加した処理方法によっ
て、被処理物の温度を３０ないし４０°Ｃに保つか、あ
るいは水素に添加する水蒸気の添加量を２ないし７％に
することによって、シリコンなどの被処理物の表面の酸
化を促進させることができる。その結果、シリコンなど
の被処理物の表面に対して、酸化と酸化膜除去を同時に
進行させることが制御性よく可能となり、シリコンなど
の被処理物の表面を損傷させることなく微小量のエッチ
ングを行うことができる。According to the present invention, the temperature of the object to be treated is kept at 30 to 40 ° C. or the amount of water vapor added to hydrogen is changed by a treatment method in which NF 3 is added to the hydrogen + steam plasma downflow. The addition amount of 2 to 7% can promote the oxidation of the surface of the object to be treated such as silicon. As a result, it is possible to control oxidation and removal of the oxide film simultaneously on the surface of the object to be processed such as silicon with good controllability, and to etch a minute amount without damaging the surface of the object to be processed such as silicon. It can be carried out.
【００３６】また、本発明になる水素＋水蒸気プラズマ
ダウンフロー処理方法による酸素ラジカルの還元作用を
同時に用いる酸化プロセスによれば、還元作用を一定に
保ちながら、酸化力を増減させることができる。Further, according to the oxidation process which simultaneously uses the reducing action of oxygen radicals by the hydrogen + steam plasma downflow treatment method according to the present invention, it is possible to increase or decrease the oxidizing power while keeping the reducing action constant.
【図１】 本発明の処理を行う水素プラズマダウンフロ
ー処理装置の構成図である。FIG. 1 is a configuration diagram of a hydrogen plasma downflow processing apparatus that performs the processing of the present invention.
【図２】 ＦＴ−ＩＲ法による測定系の模式図である。FIG. 2 is a schematic diagram of a measurement system by an FT-IR method.
【図３】 酸化膜生成−酸化膜除去の温度依存性（２６
°Ｃ）である。FIG. 3 shows temperature dependence of oxide film formation-oxide film removal (26
° C).
【図４】 酸化膜生成−酸化膜除去の温度依存性（３０
°Ｃ）である。FIG. 4 shows temperature dependence of oxide film formation-oxide film removal (30
° C).
【図５】 酸化膜生成−酸化膜除去の温度依存性（４３
°Ｃ）である。FIG. 5: Temperature dependence of oxide film formation-oxide film removal (43
° C).
【図６】 酸素ラジカル量の水蒸気添加量依存性（１Ｔ
orr ）である。FIG. 6 Dependence of the amount of oxygen radicals on the amount of added water vapor (1T
orr).
【図７】 酸素ラジカル量の水蒸気添加量依存性（３Ｔ
orr ）である。FIG. 7 Dependence of amount of oxygen radicals on amount of added water vapor (3T
orr).
【図８】 水素ラジカル量の水蒸気添加量依存性であ
る。FIG. 8 shows the dependency of the amount of hydrogen radicals on the amount of water vapor added.
１ 石英チャンバ
２ 主ガス導入手段 2a 水素ガス導入管
2b 水蒸気導入管
2c、2d マスフローコントローラ 2e、2f バル
ブ
３ 真空排気手段
４ 継ぎ手
５ プラズマ生成部 5a マイクロ波電源
６ ガス混合部
７ 添加ガス導入手段
7a マスフローコントローラ 7b バルブ
８ ダウンフロー処理部 8a ヒータ
8b 熱電対
8c 電源
９ 被処理物
10 水素プラズマダウンフロー処理装置
20 ＦＴ−ＩＲ測定系
21 赤外線検知器
22 赤外線光源1 quartz chamber 2 main gas introducing means 2a hydrogen gas introducing pipe
2b Steam inlet pipe 2c, 2d Mass flow controller 2e, 2f Valve 3 Vacuum exhaust means 4 Joint 5 Plasma generation part 5a Microwave power source 6 Gas mixing part 7 Additive gas introduction means 7a Mass flow controller 7b Valve 8 Downflow processing part 8a Heater
8b Thermocouple 8c Power supply 9 Workpiece 10 Hydrogen plasma downflow processing device 20 FT-IR measurement system 21 Infrared detector 22 Infrared light source
フロントページの続き (56)参考文献 特開 平６−338478（ＪＰ，Ａ) 特開 昭62−72131（ＪＰ，Ａ) 特開 平５−102092（ＪＰ，Ａ) 特開 平６−140368（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 21/3065 C23C 16/50 H01L 21/205 H05H 1/46 Continuation of front page (56) Reference JP-A-6-338478 (JP, A) JP-A-62-72131 (JP, A) JP-A-5-102092 (JP, A) JP-A-6-140368 (JP , A) (58) Fields investigated (Int. Cl. 7 , DB name) H01L 21/3065 C23C 16/50 H01L 21/205 H05H 1/46
Claims (10)
合ガスからなるプラズマダウンフローに、ふっ素を含む
ガスを添加し、該プラズマダウンフローの下流で被処理
物を処理するプラズマ処理方法において、 ダウンフロー処理を行う前に被処理物の温度を３０°Ｃ
ないし４０°Ｃに上げて処理を開始することにより、被
処理物表面の酸化膜除去と、酸化膜の生成を同時に行な
う第１の工程と、 次いで、該被処理物の温度を２７°Ｃ以下に下げて、被
処理物表面の酸化膜の除去と被処理物表面の水素終端を
行なう第２の工程とを含むことを特徴とするプラズマ処
理方法。1. A plasma processing method in which a gas containing fluorine is added to a plasma downflow composed of a mixed gas containing hydrogen and molecules containing oxygen atoms, and an object to be processed is processed downstream of the plasma downflow. , The temperature of the object to be processed is 30 ° C before performing the downflow process .
To a temperature of 27 ° C. or lower by starting the treatment by increasing the temperature to 40 ° C. to 40 ° C. to simultaneously remove the oxide film on the surface of the subject and generate an oxide film. And a second step of removing an oxide film on the surface of the object to be processed and terminating hydrogen on the surface of the object to be processed.
合ガスからなるプラズマダウンフローに、ふっ素を含む
ガスを添加し、該プラズマダウンフローの下流で被処理
物を処理するプラズマ処理方法において、 ダウンフロー処理工程の途中で被処理物の温度を３０°
Ｃないし４０°Ｃに上げることにより、被処理物表面の
酸化膜除去と、酸化膜の生成を同時に行なう第３の工程
と、 次いで、該被処理物の温度を２７°Ｃ以下に下げて、被
処理物表面の酸化膜の除去と被処理物表面の水素終端を
行なう第２の工程とを含むことを特徴とするプラズマ処
理方法。2. A plasma processing method in which a gas containing fluorine is added to a plasma downflow composed of a mixed gas containing hydrogen and molecules containing oxygen atoms, and an object to be processed is processed downstream of the plasma downflow. , The temperature of the object to be processed is 30 ° during the downflow process .
The third step of simultaneously removing the oxide film on the surface of the object to be processed and forming the oxide film by raising the temperature to C to 40 ° C., and then lowering the temperature of the object to be processed to 27 ° C. or lower, A plasma processing method comprising: a second step of removing an oxide film on the surface of the object to be processed and terminating hydrogen on the surface of the object to be processed.
は酸素である請求項１または２記載のプラズマ処理方
法。3. The plasma processing method according to claim 1, wherein the molecule containing an oxygen atom is water vapor or oxygen.
プラズマダウンフローに、ふっ素を含むガスを添加し、
該プラズマダウンフローの下流で被処理物を処理するプ
ラズマ処理方法において、 ダウンフロー処理工程の初めに前記水蒸気を２％ないし
７％添加する工程と、次いで、前記水蒸気を２％未満添
加する工程とを含むことを特徴とするプラズマ処理方
法。 4. A mixed gas containing hydrogen and water vapor
Add a gas containing fluorine to the plasma downflow,
A process for processing an object to be processed downstream of the plasma downflow.
In the plasma treatment method, the water vapor content of 2% to
7%, and then add less than 2% of the water vapor.
And a plasma treatment method including the step of adding
Law.
プラズマダウンフローに、ふっ素を含むガスを添加し、
該プラズマダウンフローの下流で被処理物を 処理するプ
ラズマ処理方法において、 ダウンフロー処理工程の初めに前記水蒸気を２％ないし
７％添加する工程と、 次いで、前記水蒸気を７％を越えて添加する工程とを含
むことを特徴とするプラズマ処理方法。 5. A mixed gas containing hydrogen and water vapor
Add a gas containing fluorine to the plasma downflow,
A process for processing an object to be processed downstream of the plasma downflow.
In the plasma treatment method, the water vapor content of 2% to
A step of adding 7%, and then a step of adding the water vapor in excess of 7%.
A plasma processing method comprising:
プラズマダウンフローの下流で被処理物を処理するプラ
ズマ処理方法において、 処理工程の初めに前記水蒸気を２％ないし７％添加する
工程と、 次いで、前記処理工程の途中で前記水蒸気を７％を越え
て添加する工程とを含むことを特徴とするプラズマ処理
方法。 6. A mixed gas containing hydrogen and water vapor
A plug that processes the object to be processed downstream of the plasma downflow.
In the Zuma treatment method, 2% to 7% of the steam is added at the beginning of the treatment step.
Over 7% of the water vapor in the process and then in the middle of the treatment process
Plasma treatment characterized by including a step of
Method.
プラズマダウンフローの下流で被処理物を処理するプラ
ズマ処理方法において、 処理工程の初めに前記水蒸気を２％ないし７％添加する
工程と、 次いで、前記処理工程の途中で前記水蒸気を２％未満添
加する工程とを含むことを特徴とするプラズマ処理方
法。 7. A mixed gas containing hydrogen and water vapor
A plug that processes the object to be processed downstream of the plasma downflow.
In the Zuma treatment method, 2% to 7% of the steam is added at the beginning of the treatment step.
And then add less than 2% of water vapor in the middle of the treatment step.
And a plasma treatment method including the step of adding
Law.
プラズマダウンフローの下流で被処理物を処理するプラ
ズマ処理方法において、 処理工程の初めに前記水蒸気を７％を越えて添加する工
程と、 次いで、前記処理工程の途中で前記水蒸気を２％ないし
７％添加する工程とを含むことを特徴とするプラズマ処
理方法。 8. A mixed gas containing hydrogen and water vapor
A plug that processes the object to be processed downstream of the plasma downflow.
In the Zuma treatment method, a step of adding more than 7% of the steam at the beginning of the treatment step
And extent, then, from 2% to the water vapor in the course of the process steps
Plasma treatment, including the step of adding 7%
Reasoning method.
プラズマダウンフローの下流で被処理物を処理するプラ
ズマ処理方法において、 処理工程の初めに前記水蒸気を２％未満添加する工程
と、 次いで、前記処理工程の途中で前記水蒸気を２％ないし
７％添加する工程とを含むことを特徴とするプラズマ処
理方法。 9. A mixed gas containing hydrogen and water vapor
A plug that processes the object to be processed downstream of the plasma downflow.
In the Zuma treatment method, a step of adding less than 2% of the water vapor at the beginning of the treatment step
If, then, from 2% to the water vapor in the course of the process steps
Plasma treatment, including the step of adding 7%
Reasoning method.
面に酸化物を有する半導体基板である請求項１、２、
４、５、６、７、８または９記載のプラズマ処理方法。 10. The object to be processed is a semiconductor substrate or a surface.
A semiconductor substrate having an oxide on its surface.
4, 5, 6, 7, 8 or 9 plasma treatment method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26557095A JP3379302B2 (en) | 1995-10-13 | 1995-10-13 | Plasma processing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26557095A JP3379302B2 (en) | 1995-10-13 | 1995-10-13 | Plasma processing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09106977A JPH09106977A (en) | 1997-04-22 |
| JP3379302B2 true JP3379302B2 (en) | 2003-02-24 |
Family
ID=17418956
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26557095A Expired - Lifetime JP3379302B2 (en) | 1995-10-13 | 1995-10-13 | Plasma processing method |
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| Country | Link |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100605884B1 (en) * | 1998-11-11 | 2006-08-01 | 동경 엘렉트론 주식회사 | Surface treatment method and surface treatment apparatus |
| JP4612063B2 (en) * | 1998-11-11 | 2011-01-12 | 東京エレクトロン株式会社 | Surface treatment method and apparatus |
| WO2006025136A1 (en) * | 2004-09-01 | 2006-03-09 | Shibaura Mechatronics Corporation | Plasma treatment apparatus and method of plasma treatment |
| JP2009060145A (en) * | 2008-12-05 | 2009-03-19 | Tokyo Electron Ltd | Method for removing oxide film |
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1995
- 1995-10-13 JP JP26557095A patent/JP3379302B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09106977A (en) | 1997-04-22 |
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