JPH1098032A - Formation of thin film and thin film forming device - Google Patents
Formation of thin film and thin film forming deviceInfo
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- JPH1098032A JPH1098032A JP24959096A JP24959096A JPH1098032A JP H1098032 A JPH1098032 A JP H1098032A JP 24959096 A JP24959096 A JP 24959096A JP 24959096 A JP24959096 A JP 24959096A JP H1098032 A JPH1098032 A JP H1098032A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光励起を用いた気
相化学堆積法に基く薄膜の形成方法及び形成装置に係
り、特に、低基板温度で高スループット及び膜厚均一性
に優れた薄膜の形成方法及び形成装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for forming a thin film based on a chemical vapor deposition method using photoexcitation, and more particularly to a method for forming a thin film having a high throughput and a uniform film thickness at a low substrate temperature. The present invention relates to a forming method and a forming apparatus.
【０００２】[0002]
【従来の技術】半導体装置の製造工程に於て、誘電体薄
膜（窒化硅素、二酸化硅素等）の形成工程に関しては、
従来主に気相化学堆積法（ＣＶＤ）が用いられていた。
ＣＶＤ法に於ては、原料として供給される気体分子は熱
或いはプラズマによって分解或いは励起され薄膜堆積に
供されていた。熱分解によって誘電体薄膜を形成する場
合、基板温度は４００℃以上で成膜している。プラズマ
励起による方法では、基板温度は３００℃以上で成膜し
ている。2. Description of the Related Art In the process of manufacturing a semiconductor device, a process of forming a dielectric thin film (silicon nitride, silicon dioxide, etc.)
Conventionally, a chemical vapor deposition (CVD) method has been mainly used.
In the CVD method, gas molecules supplied as a raw material are decomposed or excited by heat or plasma and used for thin film deposition. When a dielectric thin film is formed by thermal decomposition, the film is formed at a substrate temperature of 400 ° C. or higher. In the method using plasma excitation, the film is formed at a substrate temperature of 300 ° C. or higher.
【０００３】最近、上記熱或いはプラズマ励起に替わる
方法として、光励起ＣＶＤ法が用いられている。反応槽
中に導入された原料気体分子（アンモニア、亜酸化窒素
等）は、光（波長３００ｎｍ以下）によって励起され成
膜反応に供される為、基板温度３００℃以上で薄膜を堆
積出来る。Recently, a photo-excited CVD method has been used as an alternative to the above-mentioned heat or plasma excitation. The raw material gas molecules (ammonia, nitrous oxide, etc.) introduced into the reaction tank are excited by light (wavelength of 300 nm or less) and supplied to a film forming reaction, so that a thin film can be deposited at a substrate temperature of 300 ° C. or more.
【０００４】[0004]
【発明が解決しようとする課題】前記従来技術の内、熱
分解によるＣＶＤ法では、４００℃以上の高基板温度を
要する為、半導体装置の電極金属形成工程の後、誘電体
薄膜を形成した場合、電極金属と半導体基板との熱的反
応により、電気的特性が著しく劣化する。低温で成膜可
能なプラズマ励起ＣＶＤ法の場合、電極の劣化を抑止す
ることが可能であるが、プラズマ中のイオンが半導体表
面に照射されることにより、表面層に欠陥を生じやすく
素子の特性が劣化する。Among the above-mentioned prior arts, the CVD method using thermal decomposition requires a high substrate temperature of 400 ° C. or more, so that a dielectric thin film is formed after the electrode metal forming step of a semiconductor device. In addition, electrical characteristics are significantly deteriorated due to a thermal reaction between the electrode metal and the semiconductor substrate. In the case of the plasma-excited CVD method, which can form a film at a low temperature, it is possible to suppress the deterioration of the electrodes. Deteriorates.
【０００５】光励起ＣＶＤ法では、低温且つイオン衝撃
のない成膜が可能であり、素子の電気特性の劣化はな
い。しかしながら、光励起の場合、次に列挙する問題点
があった。[0005] The photo-excited CVD method allows a film to be formed at a low temperature without ion bombardment, and does not deteriorate the electrical characteristics of the device. However, in the case of optical excitation, there are the following problems.
【０００６】１）反応槽内で原料ガス（例えば、シラン
とアンモニア）の反応をさせる為、光を導入する光学窓
に薄膜の堆積が生ずると、基板表面に照射される実効的
光強度が低下し、堆積速度の低下を来す。1) When a thin film is deposited on an optical window through which light is introduced to cause a reaction between source gases (for example, silane and ammonia) in a reaction tank, the effective light intensity applied to the substrate surface decreases. Resulting in a reduced deposition rate.
【０００７】２）薄膜の成長速度の基板面内分布は、基
板に照射される光の面内分布に強く依存するため、大面
積基板への高均一膜厚薄膜の形成が困難である。2) The in-plane distribution of the growth rate of the thin film in the plane of the substrate strongly depends on the in-plane distribution of the light applied to the substrate, and it is difficult to form a thin film having a uniform thickness on a large-area substrate.
【０００８】[0008]
【課題を解決するための手段】光励起を反応槽と分離し
たガスセル内で行う。The photoexcitation is performed in a gas cell separated from the reaction tank.
【０００９】[0009]
【発明の実施の形態】まず、原料気体分子の内、それ自
体の分解によっては薄膜の堆積が生じない気体分子（例
えば、アンモニア、亜酸化窒素）の光励起を反応槽と分
離したガス導入装置内で行う。 しかる後、励起された
気体分子をノズルを通して反応槽内へ導入し、これとは
別に直接反応槽内へ導入した第２の原料ガス（例えば、
シラン）と反応せしめ、基板及び反応槽に直接光を導入
することなく、窒化硅素や二酸化硅素を堆積させる。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, photoexcitation of gas molecules (for example, ammonia and nitrous oxide), which do not form a thin film due to decomposition of the raw material gas molecules, in a gas introduction device separated from a reaction tank. Do with. Thereafter, the excited gas molecules are introduced into the reaction tank through the nozzle, and separately from the second raw material gas (for example,
Silane) and deposit silicon nitride or silicon dioxide without introducing light directly into the substrate and the reaction tank.
【００１０】本方式では、薄膜の成長速度の面内分布
は、ノズルから照射された励起分子線の強度分布によっ
て決定される為、光の強度分布とは係わりがない。In this method, the in-plane distribution of the growth rate of the thin film is determined by the intensity distribution of the excited molecular beam emitted from the nozzle, and is not related to the intensity distribution of light.
【００１１】更に、本発明に於ては、ガス導入装置に導
入する光を、装置の外に設置した光学系を用いて、導入
装置内で集束させる事が出来るため、導入したガスに対
する励起効率が極めて高い。即ち、高密度の励起分子を
供給出来るため、薄膜の堆積速度を増大させる事が出来
る。Further, according to the present invention, the light introduced into the gas introducing device can be focused in the introducing device by using an optical system installed outside the device, so that the excitation efficiency for the introduced gas can be improved. Is extremely high. That is, since high-density excited molecules can be supplied, the deposition rate of the thin film can be increased.
【００１２】実施例１ 図１を用いて実施例１を説明する。本実施例では、モノ
シラン（ＳｉＨ4）とアンモニア（ＮＨ3）を用いてＧａ
Ａｓ（００１）基板上に窒化硅素膜を形成する形成方法
及び形成装置について説明する。まず、反応槽１内に設
置された試料台２にＧａＡｓ基板３を装填する。試料台
２には基板加熱用ヒータが設置されている。基板３は、
回転機構により毎分１０回転させた。反応槽１は、ター
ボ分子ポンプ（ＴＭＰ）により、真空度を３×１０~10
Ｔｏｒｒまで排気されている。次に、基板３をヒータに
より加熱し３００℃に保持する。続いて、バルブ４を開
きＮＨ3ガス（流量５０ｓｃｃｍ）を導入する。この
時、バルブ５を調整してガスセル６内の真空度を１０Ｔ
ｏｒｒに保つ。ガスセル６（一辺５ｃｍの立方体）内の
ＮＨ3ガスは、オリフィス７を通って反応槽１内に入
る。この時、反応槽１の真空度は０．５Ｔｏｒｒであっ
た。続いて、ＡｒＦエキシマレーザ（波長１９３ｎｍ、
強度１００ｍＪ、周波数１００Ｈｚ）を光学窓８を介し
てガスセル６に導入する。この時、エキシマレーザ光
は、レンズ９によってガスセル内に焦点を持つように集
光されている。エキシマレーザを１０分照射する。その
後、エキシマレーザ照射を中断し、バルブ１０を明けて
ＳｉＨ4（流量５ｓｃｃｍ）をノズル１１より導入す
る。反応槽１の真空度が１Ｔｏｒｒに安定するのを待っ
た後、エキシマレーザをガスセル６に照射することによ
りＮＨ3ガスが励起され、窒化硅素膜の堆積が開始され
る。堆積後、エリプソメータにより膜厚を測定した所、
５分間のレーザ照射により１５０ｎｍの窒化硅素膜が堆
積していた。直径４インチの基板上の膜厚分布は、２％
以下であった。同じく屈折率分布は、３％以下であっ
た。Embodiment 1 Embodiment 1 will be described with reference to FIG. In this embodiment, monosilane (SiH 4 ) and ammonia (NH 3 ) are used to form Ga.
A method and an apparatus for forming a silicon nitride film on an As (001) substrate will be described. First, a GaAs substrate 3 is loaded on a sample stage 2 installed in a reaction tank 1. The sample stage 2 is provided with a substrate heating heater. Substrate 3
The rotation was performed 10 times per minute by a rotation mechanism. The reaction tank 1 is evacuated by a turbo molecular pump (TMP) to a degree of vacuum of 3 × 10 to 10
It has been exhausted to Torr. Next, the substrate 3 is heated at 300 ° C. by a heater. Subsequently, the valve 4 is opened, and NH 3 gas (flow rate 50 sccm) is introduced. At this time, the degree of vacuum in the gas cell 6 was adjusted to 10 T by adjusting the valve 5.
Keep at orr. The NH 3 gas in the gas cell 6 (a cube having a side of 5 cm) enters the reaction tank 1 through the orifice 7. At this time, the degree of vacuum in the reaction tank 1 was 0.5 Torr. Subsequently, an ArF excimer laser (wavelength 193 nm,
(Intensity 100 mJ, frequency 100 Hz) is introduced into the gas cell 6 through the optical window 8. At this time, the excimer laser light is focused by the lens 9 so as to have a focal point in the gas cell. The excimer laser is irradiated for 10 minutes. Thereafter, the excimer laser irradiation is interrupted, the valve 10 is opened, and SiH 4 (flow rate 5 sccm) is introduced from the nozzle 11. After waiting for the degree of vacuum in the reactor 1 to stabilize at 1 Torr, the NH 3 gas is excited by irradiating the gas cell 6 with an excimer laser, and the deposition of the silicon nitride film is started. After deposition, the film thickness was measured with an ellipsometer.
A 150 nm silicon nitride film was deposited by the laser irradiation for 5 minutes. 2% film thickness distribution on 4 inch diameter substrate
It was below. Similarly, the refractive index distribution was 3% or less.
【００１３】通常のレーザＣＶＤ或いは光ＣＶＤに於て
は、薄膜の堆積を続けると、次第に光学窓が曇り、堆積
速度が低下するが、本実施例に於ては、累積膜厚１００
ｍｍまでの範囲では、５％以上の堆積速度低下は見られ
なかった。In ordinary laser CVD or optical CVD, if the deposition of a thin film is continued, the optical window gradually becomes cloudy and the deposition rate is reduced.
In the range up to mm, a decrease in deposition rate of 5% or more was not observed.
【００１４】本実施例に於ては、窒化硅素膜について説
明したが、ＮＨ3ガスに替えて亜酸化窒素ガスを導入し
た所、膜厚分布が窒化硅素と同等の二酸化硅素膜を形成
することが出来た。In this embodiment, a silicon nitride film has been described. However, when nitrous oxide gas is introduced instead of NH 3 gas, a silicon dioxide film having a film thickness distribution equivalent to that of silicon nitride is formed. Was completed.
【００１５】また、ＳｉＨ4に替えてホスフィン（Ｐ
Ｈ3）を導入することにより、窒化燐膜の形成も出来
た。[0015] In addition, phosphine instead of SiH 4 (P
By introducing H 3 ), a phosphorus nitride film could be formed.
【００１６】実施例２ 図２を用いて実施例２を説明する。本実施例に於ても、
モノシラン（ＳｉＨ4）とアンモニア（ＮＨ3）を用いて
ＧａＡｓ（００１）基板上に窒化硅素膜を形成する形成
方法及び形成装置について説明する。ガス導入前の基板
装填法及び反応槽の真空排気に関しては、実施例１と同
じ方法を用いた。本実施例では、ＮＨ3ガスの導入法の
みが異なる。Embodiment 2 Embodiment 2 will be described with reference to FIG. In this embodiment,
A method and an apparatus for forming a silicon nitride film on a GaAs (001) substrate using monosilane (SiH 4 ) and ammonia (NH 3 ) will be described. The same method as in Example 1 was used for the substrate loading method before gas introduction and the evacuation of the reaction tank. In this embodiment, only the method of introducing NH 3 gas is different.
【００１７】まず、一辺５ｃｍの正方形断面でガス導入
方向の長さが１５ｃｍのガスセル１３中にバルブ１２を
開く事によってＮＨ3ガス（流量５０ｓｃｃｍ）を導入
する。ＮＨ３ガスは、オリフィス１４を通って反応槽１
に入る。この時の真空度は、ガスセル１３内で１０Ｔｏ
ｒｒ、反応槽１内で０．５Ｔｏｒｒであった。続いて、
バルブ１０を開いてＳｉＨ4（流量５ｓｃｃｍ）をノズ
ル１１より導入する。この時、反応真空度は１Ｔｏｒｒ
となった。First, NH 3 gas (flow rate 50 sccm) is introduced by opening the valve 12 into a gas cell 13 having a square section of 5 cm on a side and a length of 15 cm in the gas introduction direction. The NH 3 gas passes through the orifice 14 and reacts in the reaction tank 1.
to go into. The degree of vacuum at this time is 10 To
rr was 0.5 Torr in the reaction tank 1. continue,
The valve 10 is opened and SiH 4 (flow rate 5 sccm) is introduced from the nozzle 11. At this time, the reaction vacuum was 1 Torr
It became.
【００１８】続いて、エキシマレーザ光（波長１９３ｎ
ｍ、強度１００ｍＪ、周波数１００Ｈｚ）を光学窓１５
（５×１１０ｍｍの長方形）を通してガスセル１３に導
入し、ＮＨ3ガスを励起して窒化硅素膜の堆積を始め
る。エキシマレーザ光は、２×１００ｍｍの矩形平行ビ
ームを集束させずに直接導入した。Subsequently, excimer laser light (wavelength 193n)
m, intensity 100 mJ, frequency 100 Hz)
(5 × 110 mm rectangle) and introduced into the gas cell 13 to excite NH 3 gas to start the deposition of the silicon nitride film. The excimer laser light was directly introduced without focusing a rectangular parallel beam of 2 × 100 mm.
【００１９】堆積後、エリプソメータにより膜厚を測定
した所、１０分間のレーザ照射により３００ｎｍの窒化
硅素膜が堆積していた。直径４インチの基板上の膜厚分
布は、１．５％以下であった。同じく屈折率分布は、２
％以下であった。After the deposition, the film thickness was measured by an ellipsometer. As a result, a 300-nm silicon nitride film was deposited by laser irradiation for 10 minutes. The film thickness distribution on a substrate having a diameter of 4 inches was 1.5% or less. Similarly, the refractive index distribution is 2
% Or less.
【００２０】本実施例に於ても、累積膜厚１００ｍｍま
での範囲では、５％以上の堆積速度低下は見られなかっ
た。In this embodiment, no decrease in the deposition rate of 5% or more was observed in the range up to the cumulative film thickness of 100 mm.
【００２１】実施例３ 図３を用いて実施例３を説明する。本実施例に於ては、
ホスフィン（ＰＨ3）、モノシラン（ＳｉＨ4）及びアン
モニア（ＮＨ3）を用いてＧａＡｓ（００１）基板上に
窒化燐及び窒化硅素膜を形成する形成方法及び形成装置
について説明する。ガス導入前の基板装填法及び反応槽
の真空排気に関しては、実施例１と同じ方法を用いた。Embodiment 3 Embodiment 3 will be described with reference to FIG. In this embodiment,
A method and an apparatus for forming a phosphorus nitride and silicon nitride film on a GaAs (001) substrate using phosphine (PH 3 ), monosilane (SiH 4 ), and ammonia (NH 3 ) will be described. The same method as in Example 1 was used for the substrate loading method before gas introduction and the evacuation of the reaction tank.
【００２２】まず、バルブ４を開きＰＨ3ガス（流量５
０ｓｃｃｍ）を導入する。この時、バルブ５を調整して
ガスセル６内の真空度を５Ｔｏｒｒに保つ。ガスセル６
内のＰＨ3ガスは、オリフィス７を通って反応槽１内に
入る。この時、反応槽１の真空度は０．２５Ｔｏｒｒで
あった。続いて、ＡｒＦエキシマレーザ（波長１９３ｎ
ｍ、強度１００ｍＪ、周波数１００Ｈｚ）を光学窓８を
介してガスセル６に導入する。この時、エキシマレーザ
光は、レンズ９によってガスセル内に焦点を持つように
集光されている。エキシマレーザを１０分照射する。そ
の後、エキシマレーザ照射を中断し、ガスセル１３中に
バルブ１２を開く事によってＮＨ3ガス（流量５０ｓｃ
ｃｍ）を導入する。ＮＨ3ガスは、オリフィス１４を通
って反応槽１に入る。この時の真空度は、ガスセル１３
内で１０Ｔｏｒｒ、反応槽１内で０．７５Ｔｏｒｒであ
った。続いて、エキシマレーザ光を光学窓８及び１５を
通してガスセル６及び１３に導入し、ＰＨ3ガス及びＮ
Ｈ3ガスを励起して窒化燐膜の堆積を始める。こうして
堆積させた窒化燐膜の成長速度は、毎分２０ｎｍであっ
た。ＰＨ3ガスをエキシマレーザ光で励起せずに導入し
た場合、成長速度は毎分１０ｎｍであった。ＳｉＨ4の
場合はエキシマレーザ光によって解離が生じないため、
ＳｉＨ4にレーザを照射しても成長速度が増大すること
はないが、ＰＨ3ガスはレーザ照射により解離するた
め、ＮＨ3ガスとの反応が促進され成長速度が増大した
ものである。First, the valve 4 is opened and the PH 3 gas (flow rate 5
0 sccm). At this time, the degree of vacuum in the gas cell 6 is maintained at 5 Torr by adjusting the valve 5. Gas cell 6
PH 3 gas enters the reaction tank 1 through the orifice 7. At this time, the degree of vacuum in the reaction tank 1 was 0.25 Torr. Subsequently, an ArF excimer laser (wavelength 193n)
m, intensity 100 mJ, frequency 100 Hz) is introduced into the gas cell 6 through the optical window 8. At this time, the excimer laser light is focused by the lens 9 so as to have a focal point in the gas cell. The excimer laser is irradiated for 10 minutes. Thereafter, the excimer laser irradiation is interrupted, and the valve 12 is opened in the gas cell 13 so that the NH 3 gas (flow rate 50 sc
cm). NH 3 gas enters the reactor 1 through the orifice 14. At this time, the degree of vacuum is
10 Torr in the reactor and 0.75 Torr in the reactor 1. Subsequently, excimer laser light is introduced into the gas cells 6 and 13 through the optical windows 8 and 15, and PH 3 gas and N
The H 3 gas is excited to start the deposition of the phosphorus nitride film. The growth rate of the phosphorus nitride film thus deposited was 20 nm per minute. When PH 3 gas was introduced without being excited by excimer laser light, the growth rate was 10 nm / min. In the case of SiH 4 , since dissociation does not occur due to excimer laser light,
Irradiation of SiH 4 with a laser does not increase the growth rate, but PH 3 gas is dissociated by the laser irradiation, so that the reaction with NH 3 gas is accelerated and the growth rate is increased.
【００２３】[0023]
【発明の効果】本発明によれば、光励起ＣＶＤにより窒
化膜或いは酸化膜を形成した場合に於て、光導入用の光
学窓への薄膜の堆積が抑止される為、成長速度が長期に
渡って安定に保たれる。また、基板上に堆積した薄膜の
膜厚の面内分布が入射光の分布の影響を受けない為、膜
厚均一性の高い薄膜が形成出来る。According to the present invention, when a nitride film or an oxide film is formed by photoexcited CVD, deposition of a thin film on an optical window for introducing light is suppressed, so that the growth rate is extended over a long period of time. And is kept stable. Further, since the in-plane distribution of the film thickness of the thin film deposited on the substrate is not affected by the distribution of incident light, a thin film having high film thickness uniformity can be formed.
【図１】本発明の実施例１の薄膜形成装置の断面図であ
る。FIG. 1 is a sectional view of a thin film forming apparatus according to a first embodiment of the present invention.
【図２】本発明の実施例２の薄膜形成装置の断面図であ
る。FIG. 2 is a sectional view of a thin film forming apparatus according to a second embodiment of the present invention.
【図３】本発明の実施例３の薄膜形成装置の断面図であ
る。FIG. 3 is a sectional view of a thin film forming apparatus according to a third embodiment of the present invention.
１…反応槽、２…試料台、３…基板、４…バルブ、５…
バルブ、６…ガスセル、７…オリフィス、８…光学窓、
９…レンズ、１０…バルブ、１１…ノズル、１２…バル
ブ、１３…ガスセル、１４…オリフィス、１５…光学
窓。DESCRIPTION OF SYMBOLS 1 ... Reaction tank, 2 ... Sample stand, 3 ... Substrate, 4 ... Valve, 5 ...
Valve, 6 gas cell, 7 orifice, 8 optical window,
9: lens, 10: valve, 11: nozzle, 12: valve, 13: gas cell, 14: orifice, 15: optical window.
Claims (4)
め、反応槽内に装填した基板表面に上記気体分子を原料
とする薄膜を堆積する薄膜形成方法において、上記反応
槽の外部で上記気体分子を個別に光励起したる後、該光
励起分子を上記反応槽内へ導入することによって上記薄
膜を堆積せしめることを特徴とする薄膜の形成方法。1. A thin film forming method for photo-exciting at least one kind of gas molecules and depositing a thin film using said gas molecules as a raw material on the surface of a substrate loaded in a reaction tank, wherein said gas molecules are formed outside said reaction tank. A method for forming a thin film, comprising: individually exciting light, and then introducing the photoexcited molecules into the reaction tank to deposit the thin film.
連結しかつ光導入用光学窓を有する少なくとも１つのガ
スセルを具備していることを特徴とする薄膜形成装置。2. A thin film forming apparatus comprising: a reaction vessel having a substrate heating section; and at least one gas cell connected to the reaction vessel and having a light introducing optical window.
セルの上記反応槽との上記連結部に備えられたオリフィ
スによりなされていることを特徴とする請求項２記載の
薄膜形成装置。3. The thin film forming apparatus according to claim 2, wherein the connection between the reaction tank and the gas cell is made by an orifice provided in the connection portion of the gas cell with the reaction tank.
学窓に集束せしめる光学レンズを具備していることを特
徴とする請求項２又は３に記載の薄膜形成装置。4. The thin film forming apparatus according to claim 2, wherein said thin film forming apparatus further comprises an optical lens for focusing on said optical window for light introduction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24959096A JPH1098032A (en) | 1996-09-20 | 1996-09-20 | Formation of thin film and thin film forming device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24959096A JPH1098032A (en) | 1996-09-20 | 1996-09-20 | Formation of thin film and thin film forming device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1098032A true JPH1098032A (en) | 1998-04-14 |
Family
ID=17195284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24959096A Pending JPH1098032A (en) | 1996-09-20 | 1996-09-20 | Formation of thin film and thin film forming device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1098032A (en) |
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