JP3415207B2 - Metal thin film formation method by chemical vapor deposition - Google Patents
Metal thin film formation method by chemical vapor depositionInfo
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- JP3415207B2 JP3415207B2 JP18251893A JP18251893A JP3415207B2 JP 3415207 B2 JP3415207 B2 JP 3415207B2 JP 18251893 A JP18251893 A JP 18251893A JP 18251893 A JP18251893 A JP 18251893A JP 3415207 B2 JP3415207 B2 JP 3415207B2
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- Prior art keywords
- vapor deposition
- chemical vapor
- thin film
- substrate
- metal thin
- Prior art date
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- Chemical Vapour Deposition (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は半導体デバイスの製造の
際に、基体上に金属薄膜を形成するための化学気相成長
による金属薄膜形成方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a metal thin film by chemical vapor deposition for forming a metal thin film on a substrate in manufacturing a semiconductor device.
【０００２】[0002]
【従来の技術】半導体デバイスの高集積化が進むに伴な
って、絶縁膜に形成されるコンタクトホールやスルホー
ルの径は極度に微細化されてきている。このような微細
パターンの段差部の穴埋め、例えば基板上の絶縁膜中の
コンタクトホールやスルホールへの高融点金属などの穴
埋めの技術としては、化学気相成長法（以下、ＣＶＤと
称する）が有効であることが知られている。2. Description of the Related Art As semiconductor devices have been highly integrated, the diameters of contact holes and through holes formed in an insulating film have been extremely miniaturized. Chemical vapor deposition (hereinafter referred to as CVD) is effective as a technique for filling the stepped portion of such a fine pattern, for example, filling a contact hole or a through hole in an insulating film on a substrate with a refractory metal or the like. Is known to be.
【０００３】金属の薄膜を基板上に堆積して段差部の穴
埋めをする従来のＣＶＤでは、原料ガスとして、例えば
タングステンやモリブデン等のフッ化物を用い、この金
属フッ化物を、還元剤となる還元性ガスである水素やシ
ラン系ガスとの混合ガスとしてＣＶＤ装置に導入し、プ
ラズマや紫外線等によりこの還元性ガスを励起させなが
ら、この原料ガスと還元性ガスの還元反応を基板上で行
い金属の薄膜を堆積している（特開昭６３−６５０７５
号公報、特開昭６４−２３３号公報）。In the conventional CVD in which a metal thin film is deposited on a substrate to fill up the stepped portion, a fluoride such as tungsten or molybdenum is used as a source gas, and this metal fluoride is reduced as a reducing agent. It is introduced into a CVD device as a mixed gas with hydrogen, which is a reducing gas, or a silane-based gas, and while the reducing gas is excited by plasma, ultraviolet rays, etc., a reduction reaction between this source gas and the reducing gas is performed on the substrate. Is deposited (Japanese Patent Laid-Open No. 63-65075).
JP-A-64-233).
【０００４】しかし、化学気相成長法による基体上での
薄膜の形成は、原料ガスと還元性ガスの選択によりほぼ
決まっており、選択された原料ガスと還元性ガスの反応
過程に依存して、ウェーハ基板や堆積した薄膜のエッチ
ング反応がおこる。例えば基板上へのタングステン薄膜
の形成に当たっては、フッ化タングステンを金属タング
ステンに還元するための還元反応は、最終生成物として
還元により基体上に堆積させる金属タングステンの外
に、三フッ化シラン（ＳｉＨＦ3 ）を生成する反応が最
も進行しやすい反応として伴なわれる。そのため、水素
を還元性ガスとして用いた場合には、反応温度として４
００〜５００℃程度の温度が必要であり、この反応温度
ではシリコン基板のエッチング反応が促進されたり、生
成金属薄膜表面が荒れたりする。また、シラン系ガスを
還元性ガスとして用いた場合には、低温で還元反応が進
むが、膜中にシリコンが残り易く膜質の低下を招く。However, the formation of a thin film on a substrate by the chemical vapor deposition method is almost determined by the selection of the source gas and the reducing gas, and depends on the reaction process of the selected source gas and the reducing gas. , The etching reaction of the wafer substrate and the deposited thin film occurs. For example, in forming a tungsten thin film on a substrate, a reduction reaction for reducing tungsten fluoride to metallic tungsten includes the addition of metallic trifluoride (SiHF) in addition to metallic tungsten to be deposited on a substrate by reduction as a final product. The reaction that produces 3 ) is the reaction most likely to proceed. Therefore, when hydrogen is used as the reducing gas, the reaction temperature is 4
A temperature of about 00 to 500 ° C. is required. At this reaction temperature, the etching reaction of the silicon substrate is promoted and the surface of the formed metal thin film is roughened. Further, when a silane-based gas is used as the reducing gas, the reduction reaction proceeds at a low temperature, but silicon tends to remain in the film, resulting in deterioration of the film quality.
【０００５】[0005]
【発明が解決しようとする課題】この様に、還元性ガス
として水素を用いた場合には反応に高温度を必要とする
ために、表面の荒れや基板の侵食等を起こし、これが漏
洩電流や薄膜剥離の原因となっている。一方、シラン系
のガスを用いた場合には膜中にシリコンが混入し、金属
薄膜の高抵抗化や残留応力の原因になるという問題があ
った。As described above, when hydrogen is used as the reducing gas, a high temperature is required for the reaction, so that the surface is roughened or the substrate is eroded, which causes leakage current or It is a cause of thin film peeling. On the other hand, when a silane-based gas is used, there is a problem that silicon is mixed in the film, which causes a high resistance of the metal thin film and a residual stress.
【０００６】そこで、本発明の目的は、シリコンの不純
物の混入のない低抵抗、低残留応力の金属薄膜で、基板
の侵食を防止して漏洩電流を押さえ、膜表面の平坦性を
向上した化学気相成長法による金属薄膜形成方法を提供
することにある。Therefore, an object of the present invention is to provide a metal thin film having a low resistance and a low residual stress, which is free from impurities of silicon, to prevent corrosion of the substrate, suppress leakage current, and improve the flatness of the film surface. It is to provide a method for forming a metal thin film by a vapor phase growth method.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
の本発明は、化学気相成長法により金属薄膜を半導体デ
バイス基板上に形成する方法において、原料ガスと還元
性ガスを交互に不連続的に半導体デバイス基板上に導入
して、一定温度で化学気相成長を行い、この化学気相成
長を繰り返し行うことにより所要の膜厚の金属薄膜を半
導体デバイス基板上に形成することを特徴とする化学気
相成長による金属薄膜形成方法である。また、本発明
は、化学気相成長法により金属薄膜を基体上に形成する
方法において、原料ガスと還元性ガスを交互に不連続的
に基体上に導入して、３５０〜５００℃の一定温度で、
減圧下において化学気相成長を行い、この化学気相成長
を繰り返し行うことにより所要の膜厚の金属薄膜を基体
上に形成することを特徴とする化学気相成長による金属
薄膜形成方法である。また、本発明は、化学気相成長法
により金属薄膜を基体上に形成する方法において、原料
ガスと、励起手段により形成した還元性ガスの励起種を
交互に不連続的に基体上に導入して、一定温度で化学気
相成長を行い、この化学気相成長を繰り返し行うことに
より所要の膜厚の金属薄膜を基体上に形成することを特
徴とする化学気相成長による金属薄膜形成方法である。
また、本発明は、化学気相成長法により金属薄膜を半導
体デバイス基板上に形成する方法において、六フッ化タ
ングステンガスと水素ガスを交互に不連続的に基体上に
導入して、一定温度で化学気相成長を行い、この化学気
相成長を繰り返し行うことにより所要の膜厚の金属薄膜
を基体上に形成することを特徴とする化学気相成長によ
る金属薄膜形成方法である。 SUMMARY OF THE INVENTION To achieve the above object, the present invention provides a method for forming a metal thin film on a semiconductor device by chemical vapor deposition.
In the method of forming on a vice substrate , a source gas and a reducing gas are alternately and discontinuously introduced onto the semiconductor device substrate , chemical vapor deposition is performed at a constant temperature, and this chemical vapor deposition is repeated. half a metal thin film of desired film thickness by
A method for forming a metal thin film by chemical vapor deposition, which is characterized in that it is formed on a conductor device substrate . Also, the present invention
Forms a metal thin film on a substrate by chemical vapor deposition
In the method, the source gas and the reducing gas are alternately and discontinuously
At a constant temperature of 350 to 500 ° C.,
Chemical vapor deposition is performed under reduced pressure, and this chemical vapor deposition is performed.
By repeatedly performing
Metal by chemical vapor deposition characterized by being formed on
This is a thin film forming method. The present invention also provides a chemical vapor deposition method.
In the method of forming a metal thin film on a substrate by
The gas and the excited species of the reducing gas formed by the excitation means
Introduced alternately and discontinuously on the substrate, chemical vapor at a constant temperature
Phase growth and repeated chemical vapor deposition
A special feature is to form a metal thin film with a required film thickness on the substrate.
This is a method for forming a metal thin film by chemical vapor deposition as a characteristic.
In addition, the present invention is a method of semiconducting a metal thin film by chemical vapor deposition
In a method of forming on a body device substrate, a hexafluoride
Alternately and discontinuously on the substrate
Introduce and perform chemical vapor deposition at a constant temperature.
Metal thin film of required thickness by repeating phase growth
Is formed on a substrate by chemical vapor deposition.
This is a method for forming a metal thin film.
【０００８】[0008]
【作用】本発明は、化学気相成長法により金属の薄膜を
半導体デバイス基板などの基体上に形成する際に、原料
ガスと還元性ガスとを交互に不連続的に基体上に導入
し、原料ガス導入により基体上に吸着した原料ガスを、
次いで導入された還元性ガスで還元して、金属の薄膜を
形成し、この工程を一定温度で繰り返し行って所要の膜
厚の金属薄膜を基体上に形成するものである。When the metal thin film is formed on the substrate such as a semiconductor device substrate by the chemical vapor deposition method, the source gas and the reducing gas are alternately and discontinuously introduced onto the substrate, The raw material gas adsorbed on the substrate by introducing the raw material gas,
Then, it is reduced with the reducing gas introduced to form a metal thin film, and this step is repeated at a constant temperature to form a metal thin film of a required film thickness on the substrate.
【０００９】また、本発明では、還元性ガス導入時に、
還元性ガスを適切な励起手段により励起させて、水素ラ
ジカル等の励起種として基体上に導入することにより、
還元反応温度を低下でき、金属薄膜をより短時間で形成
できる。Further, according to the present invention, when the reducing gas is introduced,
By exciting the reducing gas by an appropriate excitation means and introducing it as an excited species such as hydrogen radicals on the substrate,
The reduction reaction temperature can be lowered and the metal thin film can be formed in a shorter time.
【００１０】これは、例えば水素ガスを還元性ガスとし
て、例えば電子サイクロトロン共鳴により形成されるプ
ラズマや、紫外線により励起させ、水素ラジカルの励起
種として導入して、基体表面に吸着した例えば六フッ化
タングステンの原料ガスが還元して、薄膜状の金属タン
グステンを形成する。この場合、基体温度は原料ガスの
吸着状態にのみ影響し、還元反応自体には影響すること
がないため、基体温度は反応性ガスを励起させないとき
より低くなる。基体温度が低いため、原料ガスによるシ
リコン基板等の基体の侵食と、膜表面の荒れ防止をさら
によくする。This is because, for example, hydrogen gas is used as a reducing gas and excited by, for example, plasma formed by electron cyclotron resonance or ultraviolet rays, introduced as an excited species of hydrogen radicals, and adsorbed on the surface of the substrate, for example, hexafluoride. The source gas of tungsten is reduced to form thin film metal tungsten. In this case, the substrate temperature affects only the adsorbed state of the raw material gas and does not affect the reduction reaction itself, so that the substrate temperature becomes lower than that when the reactive gas is not excited. Since the substrate temperature is low, the erosion of the substrate such as the silicon substrate by the source gas and the roughening of the film surface are further prevented.
【００１１】本発明で用いる基体とは、半導体集積回路
製造用のシリコンや化合物半導体などのウェーハ基板、
液晶表示装置やプラズマ表示装置などに用いられるガラ
ス基板およびその他の半導体デバイス製造用基板などの
基体であり、特にその表面に絶縁膜を設けた基板、特に
コンタクトホールやスルホールのごとき段差部のあるも
ので、その段差部を金属で埋め込む必要のあるものであ
る。The substrate used in the present invention is a wafer substrate of silicon or compound semiconductor for manufacturing semiconductor integrated circuits,
Substrates such as glass substrates used for liquid crystal display devices and plasma display devices and substrates for manufacturing other semiconductor devices, especially substrates having an insulating film on the surface thereof, particularly those having stepped portions such as contact holes and through holes Therefore, it is necessary to embed the stepped portion with metal.
【００１２】本発明で用いる原料ガスは、金属ハロゲン
化物、例えば六フッ化タングステン、四塩化チタンおよ
び有機金属化合物、例えばトリメチルアルミニウム、ト
リエチルアルミニウムなどの一種である、また、本発明
で用いる還元性ガスは、上記原料ガスを還元することが
できるガスで、例えば水素、ヒドラジン、ホスフィン、
ジボランなどの一種であり、還元性ガスとしてのシラン
系ガスは膜中にシリコンが混入するので、本発明では用
いない。The raw material gas used in the present invention is a kind of metal halide such as tungsten hexafluoride, titanium tetrachloride and an organometallic compound such as trimethylaluminum and triethylaluminum. Further, the reducing gas used in the present invention is also used. Is a gas capable of reducing the above raw material gas, such as hydrogen, hydrazine, phosphine,
Silane gas, which is a kind of diborane or the like, is not used in the present invention because silicon is mixed in the film as a reducing gas.
【００１３】本発明における基体温度（ＣＶＤプロセス
温度）は、還元性ガス励起手段を用いないときには、全
ＣＶＤプロセスを通じて、ＣＶＤプロセスに用いられる
従来の基体温度範囲、すなわち、３５０〜５００℃、好
ましくは４００〜５００℃から選択された一定温度であ
り、還元性ガスの励起手段を用いる場合には、室温から
４００℃未満の一定温度である。The substrate temperature (CVD process temperature) in the present invention is the conventional substrate temperature range used in the CVD process throughout the entire CVD process, that is, 350 to 500 ° C., preferably 350 to 500 ° C., when the reducing gas exciting means is not used. The temperature is a constant temperature selected from 400 to 500 ° C., and when the reducing gas excitation means is used, the temperature is a constant temperature from room temperature to less than 400 ° C.
【００１４】すなわち、本発明では、全ＣＶＤプロセス
を通して、上記の範囲から選択された一定の基体温度を
用いるので、基体温度を変えるための基体の加熱、冷却
のヒートサイクル（複数回）を行う必要がない。このた
め、ＣＶＤプロセス時間が短縮される。また、励起手段
を用いると、これを用いないときに比べＣＶＤプロセス
時間はさらに短縮できる。That is, in the present invention, since a constant substrate temperature selected from the above range is used throughout the entire CVD process, it is necessary to perform a heat cycle (a plurality of times) for heating and cooling the substrate to change the substrate temperature. There is no. Therefore, the CVD process time is shortened. Further, when the exciting means is used, the CVD process time can be further shortened as compared with the case where the exciting means is not used.
【００１５】本発明では、原料ガスと還元性ガスの導入
を交互に行うため、原料ガスによる基体の侵食や膜表面
の荒れが防止され、また還元性ガスにシラン系化合物を
用いないために、シリコン等の不純物の混入しない低ス
トレス、低抵抗の金属薄膜がＣＶＤにより形成できる。In the present invention, since the raw material gas and the reducing gas are introduced alternately, the erosion of the substrate by the raw material gas and the roughening of the film surface are prevented, and the silane compound is not used as the reducing gas. A low stress, low resistance metal thin film in which impurities such as silicon are not mixed can be formed by CVD.
【００１６】[0016]
【実施例】以下、本発明の実施例を添付した図面を参照
して説明する。Embodiments of the present invention will be described below with reference to the accompanying drawings.
【００１７】実施例１
図１に示したＣＶＤ装置を用いて原料ガスである六フッ
化タングステン（ＷＦ6 ）と、還元性ガスである水素ガ
ス（Ｈ2 ）とを半導体デバイス基板上に、図２に示す時
間間隔とガス流量で交互に導入して金属タングステン膜
を形成した。Example 1 Tungsten hexafluoride (WF 6 ) which is a source gas and hydrogen gas (H 2 ) which is a reducing gas are formed on a semiconductor device substrate by using the CVD apparatus shown in FIG. The metal tungsten film was formed by alternately introducing the gas at a time interval and a gas flow rate shown in 2.
【００１８】すなわち、ＣＶＤ室４内を圧力制御装置８
を経て真空ポンプ５で数１０Torrに減圧した後に、ガス
導入口１より原料ガス６として六フッ化タングステン
（ＷＦ6 ）をガス流量制御装置２ａを介してＣＶＤ室４
内へ、図３Ａで示すように導入した。このとき、ＣＶＤ
室４内および半導体デバイス基板９は４００℃で一定に
加熱保持した。That is, the pressure control device 8 is provided inside the CVD chamber 4.
After the pressure is reduced to several tens Torr by a vacuum pump 5, tungsten hexafluoride (WF 6 ) as a raw material gas 6 is introduced from a gas inlet port 1 into a CVD chamber 4 through a gas flow controller 2a.
Introduced therein as shown in FIG. 3A. At this time, CVD
The inside of the chamber 4 and the semiconductor device substrate 9 were heated and held at 400 ° C. constantly.
【００１９】原料ガス（ＷＦ6 ）は、半導体デバイス基
板９上に３〜５分子の層厚で吸着され（ＷＦｘ）、次い
で、図３Ｂで示すように原料ガスの供給を中断し、還元
性ガス７としての水素（Ｈ2 ）をガス流量制御装置２ｂ
を介してＣＶＤ室４内へ導入する。半導体デバイス基板
９上に吸着した原料（ＷＦｘ）は、水素ガス（Ｈ2 ）に
よって還元されて、タングステン（Ｗ）の薄膜を半導体
デバイス基板９に堆積させた（図３Ｃ）。The raw material gas (WF 6 ) is adsorbed on the semiconductor device substrate 9 in a layer thickness of 3 to 5 molecules (WF x ), and then the supply of the raw material gas is interrupted as shown in FIG. Hydrogen (H 2 ) as the gas 7 is supplied to the gas flow rate controller 2b.
It is introduced into the CVD chamber 4 via. The raw material (WF x ) adsorbed on the semiconductor device substrate 9 was reduced by hydrogen gas (H 2 ) to deposit a thin film of tungsten (W) on the semiconductor device substrate 9 (FIG. 3C).
【００２０】以後、薄膜が所望の厚さに半導体デバイス
基板９上に形成できるように原料ガスと還元性ガスを交
互に図２で示す時間間隔とガス流量で供給を繰り返すこ
とによりタングステン（Ｗ）の薄膜を形成した。Thereafter, the source gas and the reducing gas are alternately supplied at the time intervals and the gas flow rates shown in FIG. 2 so that a thin film having a desired thickness can be formed on the semiconductor device substrate 9. Thin film was formed.
【００２１】従来の六フッ化タングステン（ＷＦ6 ）と
水素ガス（Ｈ2 ）の混合ガス、および六フッ化タングス
テン（ＷＦ6 ）と還元性ガスとして四水素化ケイ素（Ｓ
ｉＨ4 ）の混合ガスをそれぞれ用いるＣＶＤでタングス
テン薄膜を同じ基体上に形成した場合と、本発明の方法
で成膜した場合の基体温度と物性を下記表１に比較して
示す。Conventional mixed gas of tungsten hexafluoride (WF 6 ) and hydrogen gas (H 2 ), or tungsten hexafluoride (WF 6 ) and silicon tetrahydride (S) as reducing gas.
Table 1 below shows the substrate temperature and physical properties when a tungsten thin film is formed on the same substrate by CVD using a mixed gas of iH 4 ) and when the film is formed by the method of the present invention.
【００２２】[0022]
【表１】 [Table 1]
【００２３】表１中、段差被覆率とは、平面上の生成膜
の膜厚ａに対するホール底部上の生成膜の膜厚ｂの比、
ｂ／ａ×１００％で表示したもので、１００％に近い程
よい。また、表面荒さは表面反射率から評価したもので
あり、◎印は表面状態が実質的にミラー表面であり、優
れていること、○印は表面状態がミラー表面に近く良好
なこと、△印は表面状態がミラー表面にはほど遠く不良
であることを表す。In Table 1, the step coverage is the ratio of the film thickness a of the film formed on the plane to the film thickness b of the film formed on the bottom of the hole.
It is expressed by b / a × 100%, and the closer to 100% the better. The surface roughness is evaluated from the surface reflectance, and ◎ indicates that the surface state is substantially the mirror surface and is excellent, and ○ indicates that the surface state is close to the mirror surface and good, and the Δ mark Indicates that the surface condition is far from the mirror surface and is defective.
【００２４】上記表１から、原料ガス供給と、還元性ガ
ス供給を交互に不連続的に繰り返すことからなる本発明
は、基体浸蝕のない、表面平坦性に優れた金属薄膜が形
成されていることがわかる。From Table 1 above, according to the present invention, in which the supply of the raw material gas and the supply of the reducing gas are alternately and discontinuously repeated, the metal thin film having no surface erosion and excellent surface flatness is formed. I understand.
【００２５】実施例２
図４に示すように、励起手段としてＲＦ誘導プラズマを
備えたＣＶＤ装置を用いて、原料ガスとして六フッ化タ
ングステン（ＷＦ6 ）と、還元性ガスとして水素ガス
（Ｈ2 ）とを半導体デバイス基板９上に、図２の時間間
隔と類似の時間間隔とガス流量で交互に不連続的に導入
して金属タングステン膜を形成した。Example 2 As shown in FIG. 4, a CVD apparatus equipped with RF induction plasma as an excitation means was used, and tungsten hexafluoride (WF 6 ) was used as a source gas and hydrogen gas (H 2 was used as a reducing gas. 2) and (4) are alternately and discontinuously introduced on the semiconductor device substrate 9 at time intervals and gas flow rates similar to those of FIG. 2 to form a metal tungsten film.
【００２６】すなわち、放電管３内をＣＶＤ室４内と共
に圧力制御装置８を経て真空ポンプ５で数１０Torrに減
圧した後に、ガス導入口より原料ガス６として六フッ化
タングステン（ＷＦ6 ）をガス流量制御装置２ａを介し
て放電管３へ導入する。このとき、反応室４内および半
導体デバイス基板９の温度は３００℃もしくはそれ以下
に加熱した。That is, the inside of the discharge tube 3 is decompressed to several tens Torr by the vacuum pump 5 through the pressure control device 8 together with the inside of the CVD chamber 4, and then tungsten hexafluoride (WF 6 ) is used as a source gas 6 from the gas inlet. It is introduced into the discharge tube 3 via the flow rate control device 2a. At this time, the temperature in the reaction chamber 4 and the semiconductor device substrate 9 was heated to 300 ° C. or lower.
【００２７】半導体デバイス基板９上に原料ガス（ＷＦ
6 ）は３〜５分子の層厚で吸着される（ＷＦｘ）。次い
で、原料ガスの供給を中断し、還元性ガス７としての水
素（Ｈ2 ）をガス流量制御装置２ｂを介して放電管３内
へ導入する。そして、高周波発生器１０により高周波を
導入して放電管３内にプラズマを形成し、Ｈ2 ガスを励
起状態（Ｈ）にして基体上に供給する。半導体デバイス
基板９上に吸着した原料（ＷＦｘ）は、励起Ｈによって
還元されてタングステン（Ｗ）の薄膜を半導体デバイス
基板９に堆積させた。On the semiconductor device substrate 9, the source gas (WF
6 ) is adsorbed with a layer thickness of 3 to 5 molecules (WF x ). Then, the supply of the raw material gas is interrupted, and hydrogen (H 2 ) as the reducing gas 7 is introduced into the discharge tube 3 via the gas flow rate control device 2b. Then, a high frequency is introduced by the high frequency generator 10 to form plasma in the discharge tube 3, and the H 2 gas is excited (H) and supplied onto the substrate. The raw material (WF x ) adsorbed on the semiconductor device substrate 9 was reduced by excitation H to deposit a thin film of tungsten (W) on the semiconductor device substrate 9.
【００２８】以後、薄膜が所望の厚さに形成できるよう
に原料ガスと還元性ガスの供給を交互に繰り返すことに
よりタングステン（Ｗ）の薄膜を形成した。このとき放
電を安定させるためにアルゴンガスなどを添加すること
もできる。Thereafter, a thin film of tungsten (W) was formed by alternately repeating the supply of the source gas and the reducing gas so that the thin film could be formed to a desired thickness. At this time, argon gas or the like can be added to stabilize the discharge.
【００２９】上記プロセスにより実施例１と同等の特性
を有する金属タングステン薄膜を得た。還元性ガスの励
起手段としてＲＦ誘導プラズマを用いることにより、励
起手段を用いないときよりも低い基体温度を用いること
ができ、しかもＣＶＤプロセス時間を短縮できた。A metal tungsten thin film having the same characteristics as in Example 1 was obtained by the above process. By using the RF induction plasma as the exciting means for the reducing gas, it was possible to use a lower substrate temperature than when the exciting means was not used, and the CVD process time could be shortened.
【００３０】実施例３
図５に示すように、励起手段として電子サイクロトロン
共鳴を備えたＣＶＤ装置を用いて、実施例２と同様にし
て、ＣＶＤにより金属タングステン膜を半導体デバイス
基板９上に形成した。Example 3 As shown in FIG. 5, using a CVD apparatus equipped with electron cyclotron resonance as an excitation means, a metal tungsten film was formed on the semiconductor device substrate 9 by CVD in the same manner as in Example 2. .
【００３１】すなわち、実施例２で用いたＲＦ誘導放電
管の代わりに、マイクロ波発振器１３と電磁石１２から
なる電子サイクロトロン共鳴放電管１４を用い、原料ガ
ス６である六フッ化タングステン（ＷＦ6 ）と還元性ガ
ス７である水素ガス（Ｈ2 ）とを図２に示した時間間隔
と同様に交互に導入し、水素（Ｈ2 ）ガスを電子サイク
ロトロン共鳴放電により励起種（Ｈ）生成を行い、実施
例２と同様にして、実施例１と同等の特性を有する金属
タングステン薄膜を得た。このとき放電を安定させるた
めにアルゴンガスなどを添加してもよい。That is, instead of the RF induction discharge tube used in Example 2, an electron cyclotron resonance discharge tube 14 composed of a microwave oscillator 13 and an electromagnet 12 is used, and the source gas 6 is tungsten hexafluoride (WF 6 ). 2 and hydrogen gas (H 2 ) which is the reducing gas 7 are alternately introduced at the same time intervals as shown in FIG. 2, and the hydrogen (H 2 ) gas is excited to generate excited species (H) by electron cyclotron resonance discharge. A metal tungsten thin film having the same characteristics as in Example 1 was obtained in the same manner as in Example 2. At this time, argon gas or the like may be added to stabilize the discharge.
【００３２】還元性ガスの励起手段として電子サイクロ
トロン共鳴を用いることにより、励起手段を用いないと
きよりも低い基体温度を用いることができ、しかもＣＶ
Ｄプロセス時間を短縮できた。By using electron cyclotron resonance as the means for exciting the reducing gas, it is possible to use a lower substrate temperature than when no excitation means is used, and further, CV
D Process time could be shortened.
【００３３】実施例４
図６に示すように、励起手段として紫外線を使用した光
励起を用いたＣＶＤ装置を用いて、実施例２と同様にし
て、ＣＶＤにより金属タングステン膜を半導体デバイス
基板９上に形成した。Example 4 As shown in FIG. 6, a metal tungsten film was deposited on the semiconductor device substrate 9 by CVD in the same manner as in Example 2 using a CVD apparatus using photoexcitation using ultraviolet rays as an excitation means. Formed.
【００３４】すなわち、実施例２で用いたＲＦ誘導放電
管の代わりに、紫外線ランプ１５を半導体デバイス基板
９上に設置してあり、原料ガス６である六フッ化タング
ステン（ＷＦ6 ）と還元性ガス７である水素ガス
（Ｈ2 ）の交互導入と紫外線光による還元性ガス
（Ｈ2 ）の励起種（Ｈ）生成とを上記実施例２と同様に
して行って、実施例１と同等の特性を有する金属タング
ステン薄膜を得た。That is, instead of the RF induction discharge tube used in Example 2, an ultraviolet lamp 15 is installed on the semiconductor device substrate 9, and it is reduced with tungsten hexafluoride (WF 6 ) which is the raw material gas 6. Alternate introduction of hydrogen gas (H 2 ) which is gas 7 and generation of excited species (H) of reducing gas (H 2 ) by ultraviolet light were performed in the same manner as in Example 2 above, and the same as Example 1 was performed. A metallic tungsten thin film having characteristics was obtained.
【００３５】還元性ガスの励起手段として紫外線ランプ
を用いることにより、励起手段を用いないときよりも低
い基体温度を用いることができ、しかもＣＶＤプロセス
時間を短縮できた。By using the ultraviolet lamp as the exciting means for the reducing gas, it was possible to use a lower substrate temperature than when the exciting means was not used, and the CVD process time could be shortened.
【００３６】なお、紫外線光源としてはエキマレーザな
どの紫外線レーザや水素放電による真空紫外線光源など
を用いることもできる。また、実施例４に実施例２およ
び３の方法を組み合わせることも可能である。As the ultraviolet light source, an ultraviolet laser such as an excimer laser or a vacuum ultraviolet light source by hydrogen discharge can be used. It is also possible to combine the method of Embodiments 2 and 3 with Embodiment 4.
【００３７】[0037]
【発明の効果】以上説明したように本発明によれば、原
料ガスを還元性ガス用いて分解する化学気相成長法によ
り金属薄膜を形成する方法において、原料ガスと還元性
ガスを交互に不連続的に基体上に導入することにより、
基体の侵食や金属薄膜表面の荒れのない、漏洩電流を抑
え、金属薄膜表面の平坦性が向上した金属薄膜が得られ
る。As described above, according to the present invention, in the method of forming a metal thin film by the chemical vapor deposition method in which the source gas is decomposed by using the reducing gas, the source gas and the reducing gas are not alternately supplied. By continuously introducing onto the substrate,
It is possible to obtain a metal thin film in which the flatness of the surface of the metal thin film is improved by preventing leakage current without erosion of the substrate and roughening of the surface of the metal thin film.
【００３８】また、還元性ガスの導入時、励起手段を用
いて還元性ガスの励起種を生成し、この励起種を基体上
に吸着した原料ガスの分解に用いることにより、励起種
を用いないときよりもより低い基体温度を用いることが
でき、ＣＶＤ時間を短縮することができる。When introducing the reducing gas, the exciting species are used to generate the excited species of the reducing gas, and the excited species are used for decomposing the raw material gas adsorbed on the substrate, so that the excited species are not used. Substrate temperatures lower than can be used and CVD times can be shortened.
【図面の簡単な説明】[Brief description of drawings]
【図１】 本発明の実施例１に用いたＣＶＤ装置の概略
図である。FIG. 1 is a schematic diagram of a CVD apparatus used in a first embodiment of the present invention.
【図２】 本発明の実施例１において、原料ガスと還元
性ガスとを交互に不連続的に導入する時間間隔をガス流
量と供に示す。FIG. 2 shows, together with the gas flow rate, the time intervals at which the source gas and the reducing gas are alternately and discontinuously introduced in Example 1 of the present invention.
【図３】 本発明の実施例１による薄膜形成のステップ
を示す概略図である。FIG. 3 is a schematic view showing steps of forming a thin film according to Example 1 of the present invention.
【図４】 本発明の実施例２に用いたＣＶＤ装置の概略
図である。FIG. 4 is a schematic diagram of a CVD apparatus used in Example 2 of the present invention.
【図５】 本発明の実施例３に用いたＣＶＤ装置の概略
図である。FIG. 5 is a schematic view of a CVD apparatus used in Example 3 of the present invention.
【図６】 本発明の実施例４に用いたＣＶＤ装置の概略
図である。FIG. 6 is a schematic diagram of a CVD apparatus used in Example 4 of the present invention.
１…ガス導入口、 ２…ガス流量
制御装置、３…放電管、 ４
…反応室、５…真空ポンプ、 ６
…原料ガス、７…還元性ガス、
８…圧力制御装置、９…半導体デバイス基板、
１０…高周波発振器、１１…コイル、
１２…電磁石、１３…マイクロ波発振
器、 １４…電子サクロトロン共鳴放電
管、１５…紫外線ランプ。1 ... Gas inlet, 2 ... Gas flow control device, 3 ... Discharge tube, 4
… Reaction chamber, 5… Vacuum pump, 6
... Raw material gas, 7 ... Reducing gas,
8 ... Pressure control device, 9 ... Semiconductor device substrate,
10 ... High-frequency oscillator, 11 ... Coil,
12 ... Electromagnet, 13 ... Microwave oscillator, 14 ... Electron sacrotron resonance discharge tube, 15 ... UV lamp.
フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 16/00 - 16/56 H01L 21/285 ＩＮＳＰＥＣ（ＤＩＡＬＯＧ) ＪＩＣＳＴファイル（ＪＯＩＳ)Front page continued (58) Fields surveyed (Int.Cl. 7 , DB name) C23C 16/00-16/56 H01L 21/285 INSPEC (DIALOG) JISST file (JOIS)
Claims (10)
デバイス基板上に形成する方法において、原料ガスと還
元性ガスを交互に不連続的に半導体デバイス基板上に導
入して、一定温度で化学気相成長を行い、この化学気相
成長を繰り返し行うことにより所要の膜厚の金属薄膜を
半導体デバイス基板上に形成することを特徴とする化学
気相成長による金属薄膜形成方法。1. A metal thin film is used as a semiconductor by chemical vapor deposition.
In the method of forming on a device substrate , a source gas and a reducing gas are alternately and discontinuously introduced onto the semiconductor device substrate , chemical vapor deposition is performed at a constant temperature, and this chemical vapor deposition is repeated. A metal thin film of the required thickness by
A method for forming a metal thin film by chemical vapor deposition, which is formed on a semiconductor device substrate .
一定温度で、減圧下において行うことを特徴とする請求
項１に記載の化学気相成長による金属薄膜形成方法。 2. The chemical vapor deposition is performed at 350 to 500 ° C.
Claim that is carried out under reduced pressure at a constant temperature
Item 2. A method for forming a metal thin film by chemical vapor deposition according to Item 1.
に形成する方法において、原料ガスと還元性ガスを交互
に不連続的に基体上に導入して、３５０〜５００℃の一
定温度で、減圧下において化学気相成長を行い、この化
学気相成長を繰り返し行うことにより所要の膜厚の金属
薄膜を基体上に形成することを特徴とする化学気相成長
による金属薄膜形成方法。3. A metal thin film on a substrate by chemical vapor deposition
In the method of forming into
Discontinuously introduced onto the substrate at 350-500 ° C
Chemical vapor deposition under reduced pressure at constant temperature
A metal with a required film thickness can be obtained by repeating the chemical vapor deposition.
A method for forming a metal thin film by chemical vapor deposition , which comprises forming a thin film on a substrate .
に形成する方法において、原料ガスと、励起手段により
形成した還元性ガスの励起種を交互に不連続的に基体上
に導入して、一定温度で化学気相成長を行い、この化学
気相成長を繰り返し行うことにより所要の膜厚の金属薄
膜を基体上に形成することを特徴とする化学気相成長に
よる金属薄膜形成方法。 4. A metal thin film on a substrate by chemical vapor deposition
In the method of forming into
The excited species of the reducing gas that have formed are alternately and discontinuously on the substrate.
The chemical vapor deposition at a constant temperature
By repeating vapor phase growth, a thin metal film with the required film thickness can be obtained.
A method for forming a metal thin film by chemical vapor deposition , which comprises forming a film on a substrate .
子サイクロトロン共鳴および紫外線光よりなる群から選
択された少なくとも一つの手段を用いることを特徴とす
る請求項４に記載の化学気相成長による金属薄膜形成方
法。5. The chemical vapor deposition metal according to claim 4 , wherein the exciting means is at least one means selected from the group consisting of RF induction plasma, electron cyclotron resonance, and ultraviolet light. Thin film forming method.
未満の一定温度で行われることを特徴とする請求項４ま
たは５に記載の化学気相成長による金属薄膜形成方法6. The chemical vapor deposition is performed at room temperature to 350 ° C.
5. The method according to claim 4, wherein the temperature is less than a constant temperature.
Or 5 , a method for forming a metal thin film by chemical vapor deposition
び有機金属化合物よりなる群から選択された少なくとも
１種であり、前記還元性ガスは前記原料ガスをその構成
金属に分解することができるガスの１種であることを特
徴とする請求項１〜６のいずれか一つに記載の化学気相
成長による金属薄膜形成方法。7. The source gas is at least one selected from the group consisting of metal halides and organometallic compounds, and the reducing gas is a gas capable of decomposing the source gas into its constituent metals. It is 1 type, The metal thin film forming method by chemical vapor deposition of any one of Claims 1-6 characterized by the above-mentioned.
スであり、前記還元性ガスは水素ガスであることを特徴
とする請求項７に記載の化学気相成長による金属薄膜形
成方法。8. The method for forming a metal thin film by chemical vapor deposition according to claim 7 , wherein the source gas is tungsten hexafluoride gas and the reducing gas is hydrogen gas.
とを特徴とする請求項４〜８のいずれか一つに記載の化
学気相成長による金属薄膜形成方法。 9. The substrate is a semiconductor device substrate.
9. The method according to any one of claims 4 to 8, characterized in that
Method for forming metal thin film by chemical vapor deposition.
上に形成する方法において、六フッ化タングステンガス
と水素ガスを交互に不連続的に基体上に導入して、一定
温度で化学気相成長を行い、この化学気相成長を繰り返
し行うことにより所要の膜厚の金属薄膜を基体上に形成
することを特徴とする化学気相成長による金属薄膜形成
方法。 10. A metal thin film as a substrate by chemical vapor deposition
In the method of forming above, tungsten hexafluoride gas
And hydrogen gas are alternately and discontinuously introduced onto the substrate to maintain a constant
Perform chemical vapor deposition at temperature and repeat this chemical vapor deposition
By doing so, a thin metal film of the required thickness is formed on the substrate
Of metal thin film by chemical vapor deposition
Method.
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|---|---|---|---|
| JP4-198778 | 1992-07-24 | ||
| JP19877892 | 1992-07-24 | ||
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| JP2002313146A Division JP2003160871A (en) | 1992-07-24 | 2002-10-28 | Method for forming thin film by chemical vapor deposition |
| JP2002313145A Division JP3522737B2 (en) | 1992-07-24 | 2002-10-28 | Method for forming tungsten thin film by chemical vapor deposition |
| JP2002313147A Division JP3522738B2 (en) | 1992-07-24 | 2002-10-28 | Metal thin film formation method by chemical vapor deposition |
| JP2002313149A Division JP2003160873A (en) | 1992-07-24 | 2002-10-28 | Method for forming metallic thin film by chemical vapor deposition |
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| US7419904B2 (en) | 2004-04-12 | 2008-09-02 | Ulvac Inc. | Method for forming barrier film and method for forming electrode film |
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| KR100385946B1 (en) * | 1999-12-08 | 2003-06-02 | 삼성전자주식회사 | Method for forming a metal layer by an atomic layer deposition and a semiconductor device with the metal layer as a barrier metal layer, an upper electrode, or a lower electrode of capacitor |
| FR2795745B1 (en) * | 1999-06-30 | 2001-08-03 | Saint Gobain Vitrage | PROCESS FOR DEPOSITING A TUNGSTENE AND / OR MOLYBDENE LAYER ON A GLASS, CERAMIC OR VITROCERAMIC SUBSTRATE, AND SUBSTRATE THUS COATED |
| KR20010059541A (en) * | 1999-12-30 | 2001-07-06 | 박종섭 | Method for forming metal line of semiconductor device |
| JP4505915B2 (en) * | 2000-01-13 | 2010-07-21 | 東京エレクトロン株式会社 | Deposition method |
| US7964505B2 (en) | 2005-01-19 | 2011-06-21 | Applied Materials, Inc. | Atomic layer deposition of tungsten materials |
| US7101795B1 (en) * | 2000-06-28 | 2006-09-05 | Applied Materials, Inc. | Method and apparatus for depositing refractory metal layers employing sequential deposition techniques to form a nucleation layer |
| US6936538B2 (en) * | 2001-07-16 | 2005-08-30 | Applied Materials, Inc. | Method and apparatus for depositing tungsten after surface treatment to improve film characteristics |
| WO2003029515A2 (en) * | 2001-07-16 | 2003-04-10 | Applied Materials, Inc. | Formation of composite tungsten films |
| JP4032872B2 (en) * | 2001-08-14 | 2008-01-16 | 東京エレクトロン株式会社 | Method for forming tungsten film |
| JP4595989B2 (en) * | 2001-08-24 | 2010-12-08 | 東京エレクトロン株式会社 | Deposition method |
| JP4178776B2 (en) | 2001-09-03 | 2008-11-12 | 東京エレクトロン株式会社 | Deposition method |
| TW589684B (en) * | 2001-10-10 | 2004-06-01 | Applied Materials Inc | Method for depositing refractory metal layers employing sequential deposition techniques |
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1993
- 1993-07-23 JP JP18251893A patent/JP3415207B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7419904B2 (en) | 2004-04-12 | 2008-09-02 | Ulvac Inc. | Method for forming barrier film and method for forming electrode film |
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| Publication number | Publication date |
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| JPH0689873A (en) | 1994-03-29 |
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