JP2007087978A - Manufacturing method of semiconductor device - Google Patents

Manufacturing method of semiconductor device Download PDF

Info

Publication number
JP2007087978A
JP2007087978A JP2005271208A JP2005271208A JP2007087978A JP 2007087978 A JP2007087978 A JP 2007087978A JP 2005271208 A JP2005271208 A JP 2005271208A JP 2005271208 A JP2005271208 A JP 2005271208A JP 2007087978 A JP2007087978 A JP 2007087978A
Authority
JP
Japan
Prior art keywords
film
heat treatment
silicon nitride
nitride film
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2005271208A
Other languages
Japanese (ja)
Other versions
JP4809653B2 (en
Inventor
Sekikin Sho
石琴 肖
Kazuto Ikeda
和人 池田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujitsu Ltd
Original Assignee
Fujitsu Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fujitsu Ltd filed Critical Fujitsu Ltd
Priority to JP2005271208A priority Critical patent/JP4809653B2/en
Publication of JP2007087978A publication Critical patent/JP2007087978A/en
Application granted granted Critical
Publication of JP4809653B2 publication Critical patent/JP4809653B2/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Formation Of Insulating Films (AREA)
  • Insulated Gate Type Field-Effect Transistor (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To form a silicon nitride film having high uniformity in a coating thickness and a high impurity diffusion prevention function. <P>SOLUTION: A method for manufacturing a semiconductor device comprises a process for heat-treating a silicon substrate at first temperature in atmospheric gas containing nitrogen, and performing heat treatment at second temperature that is higher than the first one, thus forming a silicon nitride film on the silicon substrate. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は半導体装置の製造方法に係り、特にＭＯＳトランジスタのゲート絶縁膜に用いられるシリコン窒化膜の形成方法に関するものである。   The present invention relates to a method for manufacturing a semiconductor device, and more particularly to a method for forming a silicon nitride film used for a gate insulating film of a MOS transistor.

シリコンＭＯＳトランジスタのゲート絶縁膜として従来からシリコン酸化膜が用いられてきた。シリコン酸化膜はシリコン基板の熱酸化によって形成されるものであり、化学的に安定且つシリコン基板との界面における欠陥も少ないためこれを用いたＭＯＳトランジスタの高性能・高信頼化に大きく寄与している。   Conventionally, a silicon oxide film has been used as a gate insulating film of a silicon MOS transistor. The silicon oxide film is formed by thermal oxidation of the silicon substrate, and is chemically stable and has few defects at the interface with the silicon substrate. Therefore, it greatly contributes to high performance and high reliability of MOS transistors using the silicon oxide film. Yes.

しかしながら、近年における半導体ＩＣの高速・高集積化に伴ってゲート絶縁膜の薄膜化が進行し、それに伴ってシリコン酸化膜に対しても１〜２nm程度の膜厚が要求されている。シリコン酸化膜の膜厚がこれだけ薄くなると、熱酸化工程中にピンホールその他の膜欠陥の影響を受けてゲート絶縁膜として用いたときの絶縁耐圧を保証することが難しく、また、薄いゲート絶縁膜に印加される高電界によりリーク電流が増加するという問題が生じてくる。さらに、ＣＭＯＳトランジスタのゲート絶縁膜に用いた場合、Ｐ型ゲート電極材のポリシリコンにドープされるボロンが薄いシリコン酸化膜を通してシリコン基板側へ拡散しチャネル層の不純物濃度を変化させてしきい値電圧のシフト等のトランジスタ特性の変動を引き起こすという問題が生じてくる。   However, with the recent increase in the speed and integration of semiconductor ICs, the gate insulating film has been made thinner, and accordingly, the silicon oxide film is required to have a thickness of about 1 to 2 nm. If the silicon oxide film becomes so thin, it is difficult to guarantee the withstand voltage when used as a gate insulation film due to the influence of pinholes and other film defects during the thermal oxidation process, and the thin gate insulation film A problem arises in that the leakage current increases due to the high electric field applied to the. Further, when used as a gate insulating film of a CMOS transistor, boron doped in polysilicon of a P-type gate electrode material diffuses to the silicon substrate side through a thin silicon oxide film, and changes the impurity concentration of the channel layer to change the threshold value. There arises a problem of causing variation in transistor characteristics such as voltage shift.

そこで、ゲート絶縁膜の薄膜化に対してはシリコン酸化膜に代わってシリコン窒化膜系の絶縁膜材料で対応することが提案されている。シリコン窒化膜は誘電率がシリコン酸化膜より大きいためゲート絶縁膜として用いたときにはより厚い膜厚で同一の電気的特性を実現することができピンホールその他の膜欠陥のデバイス特性へ与える影響を抑え易くなる。また、シリコン窒化膜はシリコン酸化膜に比べて膜密度が大きいため不純物拡散を抑制する機能が大きく、先に述べたＣＭＯＳトランジスタのゲート絶縁膜に適用した場合トランジスタ特性の安定化を図る上で有利である。   Therefore, it has been proposed to cope with the thinning of the gate insulating film by using a silicon nitride insulating film material instead of the silicon oxide film. Since silicon nitride has a dielectric constant greater than that of silicon oxide, when it is used as a gate insulating film, the same electrical characteristics can be achieved with a thicker film, and the effects of pinholes and other film defects on device characteristics can be suppressed. It becomes easy. In addition, since the silicon nitride film has a higher film density than the silicon oxide film, it has a large function of suppressing impurity diffusion, and is advantageous for stabilizing transistor characteristics when applied to the gate insulating film of the CMOS transistor described above. It is.

ゲート絶縁膜として用いるシリコン窒化膜はシリコン基板を直接窒化する方法、たとえばシリコン基板をＮ2ガスやＮＨ３ガス等の窒素を含む雰囲気中で熱処理することにより形成される。熱処理温度は、通常、７００〜１１００℃の範囲に設定される。膜厚をより厚くするためにはさらにこの上にＣＶＤ法等を用いてシリコン窒化膜を堆積することも提案されている(特許文献１)。 The silicon nitride film used as the gate insulating film is formed by directly nitriding a silicon substrate, for example, by heat-treating the silicon substrate in an atmosphere containing nitrogen such as N 2 gas or NH 3 gas. The heat treatment temperature is usually set in the range of 700 to 1100 ° C. In order to increase the film thickness, it has also been proposed to deposit a silicon nitride film thereon using a CVD method or the like (Patent Document 1).

しかしながら、直接窒化により形成したシリコン窒化膜には以下のような問題がある。一般にシリコン窒化膜の性質は膜中の窒素含有量に依存しており、窒素含有量がシリコン窒化膜の化学量論的組成に近づくほど誘電率は大きく且つ不純物拡散を抑制する機能が効果的に働くようになる。前述の直接窒化により形成されたシリコン窒化膜中の窒素含有量は熱処理温度が高いほど大きくなることが知られており、そのため、ゲート絶縁膜として形成する場合には熱処理温度をできるだけ高くすることが必要となるが、一方、熱処理温度を高くした場合、形成されたシリコン窒化膜の表面粗さが顕著になりゲート絶縁膜の膜厚が不均一になる。   However, the silicon nitride film formed by direct nitriding has the following problems. In general, the properties of silicon nitride films depend on the nitrogen content in the film. The closer the nitrogen content is to the stoichiometric composition of the silicon nitride film, the higher the dielectric constant and the more effective the function of suppressing impurity diffusion. Come to work. It is known that the nitrogen content in the silicon nitride film formed by the above direct nitridation increases as the heat treatment temperature increases. Therefore, when forming as a gate insulating film, the heat treatment temperature should be as high as possible. On the other hand, when the heat treatment temperature is raised, the surface roughness of the formed silicon nitride film becomes remarkable, and the film thickness of the gate insulating film becomes non-uniform.

また、シリコン基板上に形成したシリコン窒化膜はシリコン基板との界面に欠陥が発生し易くしきい値電圧のシフト等を引き起こし易いという問題があり、これを回避するためシリコン窒化膜とシリコン基板との界面に界面欠陥の少ないシリコン酸化膜を配した膜構造、たとえば、シリコン基板上にシリコン酸化膜・シリコン窒化膜・シリコン酸化膜を積層したＯＮＯ膜を形成し単層のシリコン窒化膜に代えてゲート絶縁膜として用いる方法が知られている(特許文献２)。   In addition, the silicon nitride film formed on the silicon substrate has a problem that a defect is likely to occur at the interface with the silicon substrate, and a threshold voltage shift or the like is likely to occur. A film structure in which a silicon oxide film with few interface defects is arranged on the interface, for example, an ONO film in which a silicon oxide film, a silicon nitride film, and a silicon oxide film are stacked on a silicon substrate is formed and replaced with a single silicon nitride film A method used as a gate insulating film is known (Patent Document 2).

ＯＮＯ膜の形成に際しては、シリコン酸化膜、シリコン窒化膜をそれぞれＣＶＤ法等により積層形成する方法を用いることもできるが、この方法では工程数が多くなりコストや生産性の面で問題がある。そこで、シリコン基板上に熱酸化法によりシリコン酸化膜を形成し、その後窒素を含む雰囲気中で熱処理することによりシリコン酸化膜に窒素を導入する方法が知られている。この方法によればシリコン基板との界面にはシリコン酸化膜が配置されるため界面欠陥を小さくすることができるもののシリコン酸化膜中に充分な窒素を導入することが難しく、その上に形成したゲート電極材等からの不純物の拡散を防ぐ効果が十分でないという問題がある。   In forming the ONO film, a method of laminating a silicon oxide film and a silicon nitride film by a CVD method or the like can also be used. However, this method has a problem in terms of cost and productivity because the number of steps increases. Therefore, a method is known in which a silicon oxide film is formed on a silicon substrate by a thermal oxidation method, and then nitrogen is introduced into the silicon oxide film by heat treatment in an atmosphere containing nitrogen. According to this method, since the silicon oxide film is arranged at the interface with the silicon substrate, the interface defect can be reduced, but it is difficult to introduce sufficient nitrogen into the silicon oxide film, and the gate formed thereon There is a problem that the effect of preventing the diffusion of impurities from the electrode material or the like is not sufficient.

そこで、シリコン基板上にシリコン窒化膜を直接窒化等の方法により形成し、その後で酸化処理することによりＯＮＯ膜を形成する方法が提案されている。シリコン基板とシリコン窒化膜の界面には格子間距離の違い等に基づいた大きなストレスが発生しており、このストレスが界面欠陥の原因となっているが、シリコン窒化膜の酸化処理時にはこれらの欠陥を含む界面領域がシリコン窒化膜自体より優先的に酸化される結果、シリコン窒化膜とシリコン基板との間にシリコン酸化膜が形成されることになる。この方法によれば、シリコン酸化膜を形成した後で膜中に窒素を導入する方法に比べて充分な窒素含有量を確保することができ、その結果、不純物の拡散防止機能が効果的に働くようになり、且つ誘電率を大きくする上でも有利である。
特開平５−５５５８７号公報 特開２０００−２３２１７０号公報 Therefore, a method has been proposed in which a silicon nitride film is directly formed on a silicon substrate by a method such as nitridation, and thereafter an ONO film is formed by oxidation treatment. A large amount of stress is generated at the interface between the silicon substrate and the silicon nitride film due to the difference in interstitial distance, and this stress causes interface defects. As a result of the preferential oxidation of the interface region containing silicon over the silicon nitride film itself, a silicon oxide film is formed between the silicon nitride film and the silicon substrate. According to this method, a sufficient nitrogen content can be ensured as compared with a method in which nitrogen is introduced into the film after forming the silicon oxide film, and as a result, the function of preventing the diffusion of impurities works effectively. This is also advantageous in increasing the dielectric constant.
JP-A-5-55587 JP 2000-232170 A

以上のように、シリコン基板上に直接窒化により形成したシリコン窒化膜、あるいは、このシリコン窒化膜を酸化処理することにより形成したＯＮＯ膜はゲート絶縁膜の薄膜化の要求に応じて従来のシリコン酸化膜に代えて用いることができる。しかしながら直接窒化により形成したシリコン窒化膜自体には、依然として先に述べた問題が残っている。即ち、シリコン基板を窒素を含む雰囲気中で熱処理することによりシリコン窒化膜を形成する際、熱処理温度を低くするとシリコン窒化膜はシリコン基板上で均一に成長し膜厚均一性は高いものの窒素の導入量は制限されるため不純物拡散防止機能が低下し、逆に熱処理温度を高くすると窒素の導入量が増加し不純物拡散防止機能は改善されるもののシリコン基板上での膜表面粗さが顕著になり均一なゲート絶縁膜を形成することが難しくなる。   As described above, the silicon nitride film directly formed on the silicon substrate by nitridation or the ONO film formed by oxidizing this silicon nitride film can be used in accordance with the demand for thinning the gate insulating film. It can replace with a film | membrane and can be used. However, the above-mentioned problems still remain in the silicon nitride film itself formed by direct nitridation. That is, when a silicon nitride film is formed by heat-treating the silicon substrate in an atmosphere containing nitrogen, if the heat treatment temperature is lowered, the silicon nitride film grows uniformly on the silicon substrate and the film thickness is high, but nitrogen is introduced. As the amount is limited, the function of preventing impurity diffusion decreases, and conversely, if the heat treatment temperature is increased, the amount of nitrogen introduced increases and the function of preventing impurity diffusion is improved, but the film surface roughness on the silicon substrate becomes significant. It becomes difficult to form a uniform gate insulating film.

そこで、本発明は膜厚均一性に優れるとともに不純物拡散防止機能の高いシリコン窒化膜を形成することを目的とする。   Accordingly, an object of the present invention is to form a silicon nitride film having excellent film thickness uniformity and a high impurity diffusion preventing function.

上記課題の解決は、シリコン基板を窒素を含む雰囲気ガス中において第１の温度で熱処理し、続いて第１の温度より高い第２の温度で熱処理することにより前記シリコン基板上にシリコン窒化膜を形成する工程を有することを特徴とする半導体装置の製造方法、
あるいは、第２の温度での熱処理に続いて第２の温度より高い第３の温度で熱処理することにより前記シリコン基板上にシリコン窒化膜を形成する工程を有することを特徴とする上記半導体装置の製造方法、
あるいは、窒素を含む雰囲気ガスとしてＮＨ３ガスあるいはＮ２Ｈ２ガスを用いることを特徴とする上記半導体装置の製造方法、
あるいは、前記シリコン窒化膜の形成工程に続き、酸素を含む雰囲気ガス中において所定温度で熱処理することにより前記シリコン窒化膜と前記シリコン基板の界面及び前記シリコン窒化膜の表面にそれぞれシリコン酸化膜あるいはシリコン酸窒化膜を形成する工程を有することを特徴とする上記半導体装置の製造方法によって達成される。 The solution to the above problem is to heat-treat a silicon substrate at a first temperature in an atmosphere gas containing nitrogen, and subsequently heat-treat the silicon substrate at a second temperature higher than the first temperature, thereby forming a silicon nitride film on the silicon substrate. A method of manufacturing a semiconductor device, comprising a step of forming,
Alternatively, the method includes forming a silicon nitride film on the silicon substrate by performing a heat treatment at a third temperature higher than the second temperature following the heat treatment at the second temperature. Production method,
Alternatively, NH 3 gas or N 2 H 2 gas is used as an atmosphere gas containing nitrogen,
Alternatively, following the step of forming the silicon nitride film, a silicon oxide film or silicon is formed on the interface between the silicon nitride film and the silicon substrate and on the surface of the silicon nitride film by performing a heat treatment at a predetermined temperature in an atmosphere gas containing oxygen. This is achieved by the above-described method for manufacturing a semiconductor device, comprising the step of forming an oxynitride film.

図１は窒素を含む雰囲気ガス中でシリコン基板を熱処理しシリコン窒化膜を形成する工程における熱処理プロセスを示したものであり、（a）は従来方法、（b）は本発明に係る方法を示している。同図（a）に示したように、従来の熱処理プロセスでは窒素を含む雰囲気中にシリコン基板を配置した状態で雰囲気温度を常温から上昇させ一定時間所定の熱処理温度Ｔ１に保持し、その後常温まで温度を低下させる。熱処理温度Ｔ１を膜厚均一性が損なわれない程度に低く設定した場合には窒素の導入量が制限されて不純物拡散防止機能が低下し、一方、熱処理温度を高く設定した場合、窒素の導入量が増加し化学量論的組成Ｓｉ３Ｎ４に近づくため不純物拡散防止機能は改善されるもののシリコン基板上での膜厚が不均一となる。そこで、本発明では、同図（b）に示したように、最初に熱処理温度を所定の値Ｔ２に保持しその後熱処理温度Ｔ２より高い熱処理温度Ｔ３に上昇させる。熱処理温度Ｔ２を膜厚均一性が損なわれない程度に低く設定するとともに熱処理温度Ｔ３を不純物拡散防止機能が損なわれない程度に高く設定することにより膜厚均一性に優れ且つ膜中の窒素濃度の高いシリコン窒化膜をシリコン基板上に形成することができるので、高速・高集積化に適したゲート絶縁膜を得ることが可能となる。 FIG. 1 shows a heat treatment process in a step of forming a silicon nitride film by heat-treating a silicon substrate in an atmosphere gas containing nitrogen. (A) shows a conventional method, and (b) shows a method according to the present invention. ing. As shown in FIG. 2A, in the conventional heat treatment process, the atmosphere temperature is raised from room temperature in a state where the silicon substrate is disposed in an atmosphere containing nitrogen, and is maintained at a predetermined heat treatment temperature T1 for a certain period of time. Reduce temperature. When the heat treatment temperature T1 is set so low that the film thickness uniformity is not impaired, the amount of nitrogen introduced is limited and the impurity diffusion preventing function is lowered. On the other hand, when the heat treatment temperature is set high, the amount of nitrogen introduced Increases and approaches the stoichiometric composition Si 3 N 4 , the function of preventing impurity diffusion is improved, but the film thickness on the silicon substrate becomes non-uniform. Therefore, in the present invention, as shown in FIG. 2B, the heat treatment temperature is first maintained at a predetermined value T2, and then raised to a heat treatment temperature T3 higher than the heat treatment temperature T2. By setting the heat treatment temperature T2 as low as the film thickness uniformity is not impaired, and setting the heat treatment temperature T3 as high as the impurity diffusion prevention function is not impaired, the film thickness is excellent and the nitrogen concentration in the film is reduced. Since a high silicon nitride film can be formed on a silicon substrate, a gate insulating film suitable for high speed and high integration can be obtained.

シリコン基板上に膜厚均一性に優れ且つ不純物拡散防止機能の高いシリコン窒化膜を簡単な工程で形成した。   A silicon nitride film having excellent film thickness uniformity and a high impurity diffusion preventing function was formed on a silicon substrate by a simple process.

シリコン基板をＮＨ３ガス雰囲気中で本発明に係る熱処理プロセスを通すことによりシリコン窒化膜を形成し、従来の熱処理プロセスを用いて形成したシリコン窒化膜との膜質比較を行った。シリコン窒化膜の膜質は膜表面粗さ、膜中窒素含有量によって評価した。ここで、膜表面粗さはＡＦＭ(原子間力顕微鏡)を用いて測定した１μm×１μmの面積内における膜厚の平均自乗粗さＲｑ(nm)で表すこととする。 A silicon nitride film was formed by passing a silicon substrate through a heat treatment process according to the present invention in an NH 3 gas atmosphere, and the film quality was compared with a silicon nitride film formed using a conventional heat treatment process. The film quality of the silicon nitride film was evaluated by the film surface roughness and the nitrogen content in the film. Here, the film surface roughness is represented by the mean square roughness Rq (nm) of the film thickness within an area of 1 μm × 1 μm measured using an AFM (atomic force microscope).

図２は熱処理温度と膜厚の平均自乗粗さＲｑの関係をプロットしたものである。同図において、曲線aは従来の熱処理プロセスを用いたときの結果を示しており、横軸はこのときの熱処理温度を示している。熱処理温度以外の膜形成条件は形成されたシリコン窒化膜の膜厚が１nmとなるように設定した。即ち、曲線aにおいて、熱処理温度７５０℃のときには、熱処理時間５分、ＮＨ３ガス流量０．１ slm、圧力２.６ torr、熱処理温度が８５０℃のときには、熱処理時間１５秒、ＮＨ３ガス流量０．１ slm、圧力２.６ torr、熱処理温度が９５０℃のときには、熱処理時間１０秒、ＮＨ３ガス流量０．１ slm、圧力２.６ torrに設定した。これは同一膜厚における膜厚の平均自乗粗さＲｑの値によって膜質比較を容易に行えるようにしたものである。 FIG. 2 is a plot of the relationship between the heat treatment temperature and the mean square roughness Rq of the film thickness. In the figure, a curve a shows a result when a conventional heat treatment process is used, and a horizontal axis shows a heat treatment temperature at this time. The film formation conditions other than the heat treatment temperature were set so that the thickness of the formed silicon nitride film was 1 nm. That is, in the curve a, when the heat treatment temperature is 750 ° C., the heat treatment time is 5 minutes, the NH 3 gas flow rate is 0.1 slm, the pressure is 2.6 torr, and when the heat treatment temperature is 850 ° C., the heat treatment time is 15 seconds and the NH 3 gas flow rate. When 0.1 slm, pressure 2.6 torr, and heat treatment temperature were 950 ° C., heat treatment time 10 seconds, NH 3 gas flow rate 0.1 slm, pressure 2.6 torr were set. This makes it easy to compare the film quality by the value of the mean square roughness Rq of the film thickness at the same film thickness.

図２中曲線ｂは本発明に係る熱処理プロセスを用いたときの結果を示している。本実施例では熱処理プロセスを２つのステップに分けて行い、最初の熱処理プロセス（１ｓｔステッププロセス）に続けて行う熱処理プロセス(２ｎｄステッププロセス)の温度を高く設定する。ここでは、１ｓｔステッププロセスの熱処理温度を６００℃で一定とし、２ｎｄステッププロセスの熱処理温度を７５０℃、８５０℃、９５０℃と変化させた。曲線bに対する横軸の温度は２ｎｄステッププロセスの熱処理温度を示している。曲線aと同じく熱処理温度以外の膜形成条件は膜厚が１nmとなるように設定している。即ち、１ｓｔステッププロセスにおいて熱処理温度６００℃のとき、熱処理時間３０秒、ＮＨ３ガス流量１ slm、圧力０．１ torrに設定しており、２ｎｄステッププロセスにおいて熱処理温度７５０℃のとき、熱処理時間５分、ＮＨ３ガス流量０．１ slm、圧力２.６ torr、熱処理温度が８５０℃のとき、熱処理時間１５秒、ＮＨ３ガス流量０．１ slm、圧力２.６ torr、熱処理温度が９５０℃のとき、熱処理時間１０秒、ＮＨ３ガス流量０．１ slm、圧力２.６ torrに設定している。 A curve b in FIG. 2 shows a result when the heat treatment process according to the present invention is used. In this embodiment, the heat treatment process is performed in two steps, and the temperature of the heat treatment process (2nd step process) performed subsequent to the first heat treatment process (1st step process) is set high. Here, the heat treatment temperature of the 1st step process was fixed at 600 ° C., and the heat treatment temperatures of the 2nd step process were changed to 750 ° C., 850 ° C., and 950 ° C. The temperature on the horizontal axis with respect to the curve b indicates the heat treatment temperature of the 2nd step process. As with the curve a, the film formation conditions other than the heat treatment temperature are set so that the film thickness is 1 nm. That is, when the heat treatment temperature is 600 ° C. in the 1st step process, the heat treatment time is 30 seconds, the NH 3 gas flow rate is 1 slm, and the pressure is 0.1 torr. When the heat treatment temperature is 750 ° C. in the 2nd step process, the heat treatment time is 5 Min, NH 3 gas flow rate 0.1 slm, pressure 2.6 torr, heat treatment temperature 850 ° C., heat treatment time 15 seconds, NH 3 gas flow rate 0.1 slm, pressure 2.6 torr, heat treatment temperature 950 ° C. In this case, the heat treatment time is 10 seconds, the NH 3 gas flow rate is 0.1 slm, and the pressure is 2.6 torr.

一般に、ゲート絶縁膜における膜厚の平均自乗粗さＲｑは平均膜厚1 nmの１０％以下、０．１nm以下にすることが望ましい。従来方法では曲線aに見られるように、７５０℃以上になると急激に膜厚の平均自乗粗さＲｑが増加し０．１nmを大きく越えるためゲート絶縁膜として用いることが難しくなる。一方、７５０℃以下に設定した場合には形成されたシリコン窒化膜の窒素含有量はＲＢＳによる測定の結果、４〜１０ atm％と小さく、この窒素含有量では不純物拡散防止機能が大きく低下しゲート絶縁膜として用いることが難しくなる。   In general, the mean square roughness Rq of the film thickness in the gate insulating film is desirably 10% or less and 0.1 nm or less of the average film thickness of 1 nm. As can be seen from the curve a in the conventional method, when the temperature exceeds 750 ° C., the mean square roughness Rq of the film thickness increases rapidly and greatly exceeds 0.1 nm, making it difficult to use as a gate insulating film. On the other hand, when the temperature is set to 750 ° C. or lower, the nitrogen content of the formed silicon nitride film is as small as 4 to 10 atm% as a result of measurement by RBS. It becomes difficult to use as an insulating film.

一方、本発明に係る２ステッププロセスによれば、２ｎｄステッププロセスの熱処理温度を８５０℃以上にした場合にも膜厚の平均自乗粗さＲｑは０．１nmを大きく越えることはなくゲート絶縁膜として十分な表面平滑度を維持することができ、また、膜中窒素含有量はＲＢＳによる測定の結果、３５ atm％以上となり十分な不純物拡散防止機能を有することがわかった。   On the other hand, according to the two-step process according to the present invention, even when the heat treatment temperature in the 2nd step process is set to 850 ° C. or higher, the mean square roughness Rq of the film thickness does not greatly exceed 0.1 nm. Sufficient surface smoothness can be maintained, and the nitrogen content in the film was measured by RBS to be 35 atm% or more, and it was found that the film had a sufficient impurity diffusion preventing function.

さらに、以上のようにして形成されたシリコン窒化膜を熱酸化することによりシリコン基板上にＯＮＯ膜を形成した。得られたＯＮＯ膜はシリコン基板との界面にシリコン酸化膜が形成されているため界面欠陥が少なく、これによりシリコン窒化膜を単層でゲート絶縁膜として用いた場合に比べてしきい値電圧の変動の小さな特性の安定したトランジスタ特性を実現することが可能となる。   Furthermore, the ONO film was formed on the silicon substrate by thermally oxidizing the silicon nitride film formed as described above. Since the obtained ONO film has a silicon oxide film formed at the interface with the silicon substrate, there are few interface defects, so that the threshold voltage of the ONO film is smaller than that in the case where the silicon nitride film is used as a single layer as a gate insulating film. It is possible to realize stable transistor characteristics with small fluctuation characteristics.

上記実施例では熱処理プロセスを２つのステップに分けて行ったが、これに限らず熱処理プロセスを２つ以上のステップに分けて行った場合にも従来方法に比べて優れた結果を得ることができる。例えば、熱処理温度を７５０℃、８５０℃、９５０℃の３ステップに分けて行うことによりシリコン窒化膜を形成したとき、膜厚の平均自乗粗さＲｑは０．１０６nmとなった。２ステッププロセスと同様に熱処理温度以外の膜形成条件は形成されたシリコン窒化膜の膜厚が１nmとなるように設定した。即ち、熱処理温度７５０℃のとき、熱処理時間３０秒、ＮＨ３ガス流量０．１ slm、圧力０．１torr、熱処理温度が８５０℃のとき、熱処理時間１５秒、ＮＨ３ガス流量０．１ slm、圧力２.６ torr、熱処理温度が９５０℃のとき、熱処理時間５秒、ＮＨ３ガス流量０．１ slm、圧力２.６ torrに設定した。 In the above embodiment, the heat treatment process is divided into two steps. However, the present invention is not limited to this, and even when the heat treatment process is divided into two or more steps, superior results can be obtained compared to the conventional method. . For example, when the silicon nitride film is formed by performing the heat treatment at three steps of 750 ° C., 850 ° C., and 950 ° C., the mean square roughness Rq of the film thickness is 0.106 nm. As in the two-step process, the film formation conditions other than the heat treatment temperature were set so that the thickness of the formed silicon nitride film was 1 nm. That is, when the heat treatment temperature is 750 ° C., the heat treatment time is 30 seconds, the NH 3 gas flow rate is 0.1 slm, the pressure is 0.1 torr, and when the heat treatment temperature is 850 ° C., the heat treatment time is 15 seconds, the NH 3 gas flow rate is 0.1 slm, When the pressure was 2.6 torr and the heat treatment temperature was 950 ° C., the heat treatment time was 5 seconds, the NH 3 gas flow rate was 0.1 slm, and the pressure was 2.6 torr.

なお、上記実施例では窒素を含む雰囲気ガスとしてＮＨ３ガスを用いたが、Ｎ２Ｈ２ガス等を用いることもできる。 In the above embodiment, NH 3 gas is used as the atmosphere gas containing nitrogen, but N 2 H 2 gas or the like can also be used.

シリコン基板上に膜厚均一性及び不純物拡散防止機能に優れたシリコン窒化膜を形成することができるので、ＭＯＳトランジスタのゲート絶縁膜に適用することにより半導体ＩＣの高速・高集積化に有効である。   Since a silicon nitride film with excellent film thickness uniformity and impurity diffusion prevention function can be formed on a silicon substrate, it is effective for high speed and high integration of semiconductor ICs when applied to the gate insulating film of MOS transistors. .

従来の熱処理プロセスと本発明に係る熱処理プロセスを示す図。The figure which shows the conventional heat processing and the heat processing which concerns on this invention. 熱処理温度と膜厚の平均自乗粗さＲｑの関係を示す図。The figure which shows the relationship between heat processing temperature and the average square roughness Rq of a film thickness.

Claims (4)

シリコン基板を窒素を含む雰囲気ガス中において第１の温度で熱処理し、続いて第１の温度より高い第２の温度で熱処理することにより前記シリコン基板上にシリコン窒化膜を形成する工程を有することを特徴とする半導体装置の製造方法。   A step of forming a silicon nitride film on the silicon substrate by heat-treating the silicon substrate at a first temperature in an atmosphere gas containing nitrogen and subsequently heat-treating the silicon substrate at a second temperature higher than the first temperature. A method of manufacturing a semiconductor device. 第２の温度での熱処理に続いて第２の温度より高い第３の温度で熱処理することにより前記シリコン基板上にシリコン窒化膜を形成する工程を有する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 semiconductor according to claim 1, further comprising a step of forming a silicon nitride film on the silicon substrate by performing a heat treatment at a third temperature higher than the second temperature following the heat treatment at the second temperature. Device manufacturing method. 窒素を含む雰囲気ガスとしてＮＨ３ガスあるいはＮ２Ｈ２ガスを用いることを特徴とする請求項１乃至請求項２記載の半導体装置の製造方法。 3. The method of manufacturing a semiconductor device according to claim 1, wherein NH 3 gas or N 2 H 2 gas is used as the atmosphere gas containing nitrogen. 前記シリコン窒化膜の形成工程に続き、酸素を含む雰囲気ガス中において所定温度で熱処理することにより前記シリコン窒化膜と前記シリコン基板の界面及び前記シリコン窒化膜の表面にそれぞれシリコン酸化膜あるいはシリコン酸窒化膜を形成する工程を有することを特徴とする請求項１乃至請求項２記載の半導体装置の製造方法。   Following the step of forming the silicon nitride film, a silicon oxide film or silicon oxynitride is formed on the interface between the silicon nitride film and the silicon substrate and the surface of the silicon nitride film by performing a heat treatment at a predetermined temperature in an atmosphere gas containing oxygen. 3. The method of manufacturing a semiconductor device according to claim 1, further comprising a step of forming a film.
JP2005271208A 2005-09-16 2005-09-16 Manufacturing method of semiconductor device Expired - Fee Related JP4809653B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005271208A JP4809653B2 (en) 2005-09-16 2005-09-16 Manufacturing method of semiconductor device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2005271208A JP4809653B2 (en) 2005-09-16 2005-09-16 Manufacturing method of semiconductor device

Publications (2)

Publication Number Publication Date
JP2007087978A true JP2007087978A (en) 2007-04-05
JP4809653B2 JP4809653B2 (en) 2011-11-09

Family

ID=37974703

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2005271208A Expired - Fee Related JP4809653B2 (en) 2005-09-16 2005-09-16 Manufacturing method of semiconductor device

Country Status (1)

Country Link
JP (1) JP4809653B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016167501A (en) * 2015-03-09 2016-09-15 東京エレクトロン株式会社 Deposition method, deposition device and storage medium

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0353530A (en) * 1989-07-21 1991-03-07 Sony Corp Manufacture of semiconductor device
JP2001044194A (en) * 1999-06-24 2001-02-16 Lucent Technol Inc Integrated circuit
JP2004064037A (en) * 2002-06-03 2004-02-26 Sanyo Electric Co Ltd Method of manufacturing semiconductor device
JP2005093865A (en) * 2003-09-19 2005-04-07 Toshiba Corp Method of manufacturing semiconductor device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0353530A (en) * 1989-07-21 1991-03-07 Sony Corp Manufacture of semiconductor device
JP2001044194A (en) * 1999-06-24 2001-02-16 Lucent Technol Inc Integrated circuit
JP2004064037A (en) * 2002-06-03 2004-02-26 Sanyo Electric Co Ltd Method of manufacturing semiconductor device
JP2005093865A (en) * 2003-09-19 2005-04-07 Toshiba Corp Method of manufacturing semiconductor device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016167501A (en) * 2015-03-09 2016-09-15 東京エレクトロン株式会社 Deposition method, deposition device and storage medium

Also Published As

Publication number Publication date
JP4809653B2 (en) 2011-11-09

Similar Documents

Publication Publication Date Title
US7851383B2 (en) Method and system for forming a controllable gate oxide
TWI420601B (en) Method of making a nitrided gate dielectric
JP2006165589A (en) Method of manufacturing semiconductor device
JP2008288227A (en) Manufacturing method of semiconductor device
JP2007123825A (en) Method of manufacturing semiconductor device
KR101521555B1 (en) Method of manufacturing a substrate using a germanium condensation process and method of manufacturing a semicondictor device usnig the same
JP3887364B2 (en) Manufacturing method of semiconductor device
JP2007194239A (en) Process for fabricating semiconductor device
JP5050351B2 (en) Manufacturing method of semiconductor device
US9159779B2 (en) Method of fabricating semiconductor device
US8501634B2 (en) Method for fabricating gate structure
JP4809653B2 (en) Manufacturing method of semiconductor device
JP2002222941A (en) Mis semiconductor device and manufacturing method therefor
JP4477981B2 (en) Manufacturing method of semiconductor device
WO2009119148A1 (en) Film forming method and semiconductor device manufacturing method
JP5039396B2 (en) Manufacturing method of semiconductor device
KR100621542B1 (en) Dielectric multilayer of microelectronic device and fabricating method the same
JP2008258614A (en) Method of growing thin oxynitride film on substrate
JP2006339370A (en) Manufacturing method of semiconductor device
KR100680970B1 (en) Method for forming gate of semiconductor device
JP2005101503A (en) Semiconductor device, and manufacturing method thereof
US20080242114A1 (en) Thermal anneal method for a high-k dielectric
KR100549584B1 (en) Method for manufacturing isolation layer of semiconductor device
JP4220991B2 (en) Manufacturing method of semiconductor device
JP2010028008A (en) Method for manufacturing semiconductor device

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20080704

A711 Notification of change in applicant

Free format text: JAPANESE INTERMEDIATE CODE: A712

Effective date: 20080731

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20110325

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20110531

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20110715

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20110816

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20110819

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20140826

Year of fee payment: 3

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

LAPS Cancellation because of no payment of annual fees