JPH08279497A - Semiconductor manufacturing equipment and semiconductor equipment - Google Patents
Semiconductor manufacturing equipment and semiconductor equipmentInfo
- Publication number
- JPH08279497A JPH08279497A JP7082266A JP8226695A JPH08279497A JP H08279497 A JPH08279497 A JP H08279497A JP 7082266 A JP7082266 A JP 7082266A JP 8226695 A JP8226695 A JP 8226695A JP H08279497 A JPH08279497 A JP H08279497A
- Authority
- JP
- Japan
- Prior art keywords
- raw material
- metal compound
- container
- material container
- plate
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4481—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Formation Of Insulating Films (AREA)
- Semiconductor Memories (AREA)
- Chemical Vapour Deposition (AREA)
- Semiconductor Integrated Circuits (AREA)
Abstract
(57)【要約】
【目的】常温，常圧で液体または固体の金属化合物原料
を用いるＣＶＤ法において、原料容器を低温化しても充
分な原料供給量が得られる原料供給機構を提供する。
【構成】原料容器１内に多数の孔の開いたプレート４を
数枚設置し、その上にＢａ（ＤＰＭ)2，Ｓｒ（ＤＰＭ)2
等の金属化合物原料３をのせ、キャリアガスを原料容器
１の下部より供給する。原料の有効表面積を増大させる
ことができるため、定常状態で飽和蒸気圧に近づく。そ
れにより、低温でも充分な原料供給量が得られる。
(57) [Summary] [Object] To provide a raw material supply mechanism capable of obtaining a sufficient raw material supply amount even when the temperature of a raw material container is lowered in a CVD method using a liquid or solid metal compound raw material at room temperature and atmospheric pressure. [Structure] Several plates 4 having many holes are installed in a raw material container 1, and Ba (DPM) 2 and Sr (DPM) 2 are placed thereon.
A metal compound raw material 3 such as the above is placed, and a carrier gas is supplied from the lower portion of the raw material container 1. Since the effective surface area of the raw material can be increased, the saturated vapor pressure is approached in the steady state. As a result, a sufficient amount of raw material can be supplied even at low temperatures.
Description
【０００１】[0001]
【産業上の利用分野】本発明は半導体製造装置として用
いられるＣＶＤ装置の原料供給機構に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a raw material supply mechanism for a CVD apparatus used as a semiconductor manufacturing apparatus.
【０００２】[0002]
【従来の技術】高誘電性絶縁膜材料である（Ｂａ，Ｓ
ｒ）ＴｉＯ3(ＢＳＴ）は、比誘電率が２００〜６００と
ＳｉＯ2 に比べて百倍程度大きく、２５６Mbit以降のＤ
ＲＡＭ用キャパシタ絶縁膜材料として注目されている。
ＢＳＴの形成方法としては、主にスパッタ法が用いられ
ている。例えば、文献「ジャパニーズ ジャーナル オ
ブ アプライド フィジックス，１９９３年，４１２６
ページから４１３０ページ（Japanese Journal of Appl
ied Phisics, pp.4126−4130 (1993))」に記載されてい
る。しかし、ＣＶＤ法によって立体構造の下部電極上に
も均一に堆積できれば、ＤＲＡＭの高集積化に優位であ
る。2. Description of the Related Art A high dielectric insulating film material (Ba, S
r) TiO 3 (BST) has a relative dielectric constant of 200 to 600, which is about 100 times larger than that of SiO 2 , and D after 256 Mbit.
It has attracted attention as a material for a capacitor insulating film for RAM.
A sputtering method is mainly used as a method for forming BST. For example, the document “Japanese Journal of Applied Physics, 1993, 4126.
From page 4130 (Japanese Journal of Appl
ied Phisics, pp. 4126-4130 (1993)) ". However, if it can be uniformly deposited on the lower electrode having a three-dimensional structure by the CVD method, it is advantageous for high integration of DRAM.
【０００３】現在の所、Ｂａ，ＳｒのＣＶＤ原料は、ジ
ピバロイルメタンバリウム、すなわち、Ｂａ（Ｃ11Ｈ19
Ｏ2)2（略称としてＢａ(ＤＰＭ)2），ジピバロイルメタ
ンストロンチウム、すなわち、Ｓｒ（Ｃ11Ｈ19Ｏ2)
2（略称としてＳｒ（ＤＰＭ)2)、などの固体の有機化合
物が検討されている。例えば、文献「ジャパニーズ ジ
ャーナル オブ アプライド フィジックス，１９９１
年，２２００ページから２２０３ページ(Japanese Jour
nal of Applied Phisics, pp.2200−2203(1991))」や、
文献「ジャパニーズ ジャーナル オブ アプライド
フィジックス，１９９３年，４０６９ページから４０７
３ページ(Japanese Journal of AppliedPhisics, pp.40
69−4073(1993)）」に記載されている。At present, the CVD raw material for Ba and Sr is dipivaloylmethane barium, that is, Ba (C 11 H 19
O 2 ) 2 (abbreviated as Ba (DPM) 2 ), dipivaloylmethane strontium, that is, Sr (C 11 H 19 O 2 ).
Solid organic compounds such as 2 (abbreviated as Sr (DPM) 2 ) are being studied. For example, the document “Japanese Journal of Applied Physics, 1991.
Year 2200 to 2203 pages (Japanese Jour
nal of Applied Phisics, pp.2200-2203 (1991)) '',
Reference "Japanese Journal of Applied
Physics, 1993, pp. 4069-407
3 pages (Japanese Journal of Applied Physics, pp.40
69-4073 (1993)) ".
【０００４】図３に、従来の原料容器の断面図を示す。
常温，常圧で液体または固体の金属化合物原料３を入れ
た容器１内にバルブ２を介して窒素，アルゴン等の不活
性ガス（キャリアガス）を流し、原料を一部昇華または
気化させた後、成膜室に輸送する。通常のＣＶＤ法で
は、キャリアガス流量は数十cc／min 〜数百cc／min 程
度であり、容器内圧力は数十Torr〜数百Torr程度とな
る。FIG. 3 shows a sectional view of a conventional raw material container.
After injecting an inert gas (carrier gas) such as nitrogen or argon through a valve 2 into a container 1 containing a liquid or solid metal compound raw material 3 at room temperature and atmospheric pressure to partially sublimate or vaporize the raw material , To the film forming chamber. In the ordinary CVD method, the carrier gas flow rate is about several tens cc / min to several hundreds cc / min, and the pressure in the container is about several tens Torr to several hundred Torr.
【０００５】[0005]
【発明が解決しようとする課題】上述した金属化合物原
料は一般に蒸気圧が低い。さらに通常、原料容器内での
原料の蒸気圧は、物理的に決定される飽和蒸気圧には及
ばないまま平衡状態に落ち着いてしまう。そのため、原
料供給量を増やすには、キャリア流量を多くする手段が
とられる。しかし、キャリア流量やそれにともなって変
化する成膜室内の圧力は、ＣＶＤ法で膜質を決定する重
要なパラメータであり、原料供給量の増大のために律速
されるのは好ましくない。The metal compound raw materials described above generally have a low vapor pressure. Further, usually, the vapor pressure of the raw material in the raw material container settles in an equilibrium state without reaching the physically determined saturated vapor pressure. Therefore, in order to increase the raw material supply amount, a means for increasing the carrier flow rate is taken. However, the carrier flow rate and the pressure in the film forming chamber that changes with it are important parameters that determine the film quality by the CVD method, and it is not preferable that the rate is limited due to an increase in the amount of raw material supply.
【０００６】そのため、ＢＳＴ膜の実用的な成長速度を
得るには、原料容器を２００℃以上に昇温して、原料の
蒸気圧を増大させる方法がとられる。その場合、昇華ま
たは気化した原料の再固化を防ぐために原料容器から成
膜室までの原料輸送部も200℃以上に昇温する必要があ
り、バルブの劣化等の問題が生じる。さらに、成膜室へ
のガス導入部も２００℃以上にする必要があり、酸素と
の混合部で原料と酸素が反応し、反応生成物が成膜室内
壁に付着する問題も生じる。そのため、Ｂａ，Ｓｒの高
蒸気圧原料の開発が進められているが、現状では安定な
化合物原料は得られていない。Therefore, in order to obtain a practical growth rate of the BST film, a method of increasing the vapor pressure of the raw material by raising the temperature of the raw material container to 200 ° C. or higher is adopted. In that case, in order to prevent re-solidification of the sublimated or vaporized raw material, it is necessary to raise the temperature of the raw material transport section from the raw material container to the film forming chamber to 200 ° C. or higher, which causes a problem such as deterioration of the valve. Further, the gas introduction part to the film forming chamber also needs to be set to 200 ° C. or higher, and the raw material and oxygen react with each other in the mixing part with oxygen, which causes a problem that reaction products adhere to the inner wall of the film forming chamber. Therefore, the development of high vapor pressure raw materials of Ba and Sr has been advanced, but at present, stable compound raw materials have not been obtained.
【０００７】[0007]
【課題を解決するための手段】金属化合物原料の蒸気圧
が低いとはいえ、原料容器内で飽和蒸気圧まで達するな
らば充分な原料供給量が得られる。すなわち、従来の原
料容器構造では、飽和蒸気圧に遠く及ばないまま定常状
態に落ち着いてしまうことが問題である。[MEANS FOR SOLVING THE PROBLEMS] Although the vapor pressure of the metal compound raw material is low, if the saturated vapor pressure is reached in the raw material container, a sufficient raw material supply amount can be obtained. That is, in the conventional raw material container structure, there is a problem that the saturated vapor pressure is not reached far and the steady state is reached.
【０００８】定常状態で飽和蒸気圧に近づけるには、図
４に示すように容器内でキャリアガスに曝される原料の
表面積を大きくすれば良い。ただし、原料は表面から消
費されるので、形状によっては原料が消費されるに従っ
て表面積が変化してしまう場合がある。すると、ＢＳＴ
成長速度が経時的に変化してしまう。そこで、図５のよ
うに原料容器内に数枚のプレートを設置し、そこに原料
を置くことによって原料の有効表面積を増大させようと
考えた。しかし、原料容器内は粘性流領域となる圧力で
使用するため、キャリアガスを容器上部から流す方式で
は原料容器の上部と下部で圧力差が生じ、効果が充分に
得られないと予想される。In order to approach the saturated vapor pressure in the steady state, the surface area of the raw material exposed to the carrier gas in the container may be increased as shown in FIG. However, since the raw material is consumed from the surface, the surface area may change as the raw material is consumed depending on the shape. Then BST
The growth rate changes with time. Therefore, as shown in FIG. 5, it was considered to install several plates in the raw material container and place the raw material there to increase the effective surface area of the raw material. However, since the inside of the raw material container is used at a pressure that is in a viscous flow region, it is expected that a pressure difference will occur between the upper part and the lower part of the raw material container in the method of flowing the carrier gas from the upper part of the container, and the effect cannot be sufficiently obtained.
【０００９】そこで本発明においては、図２に示すよう
に、キャリアガスを容器下部から流すようにし、原料容
器内の圧力の均一化を図った。また、図１に示すよう
に、原料容器内に多数の孔の開いたキャピラリプレート
を設置し、その上に原料を置くことによって、原料の有
効表面積を増大させるとともに、下部からのキャリアガ
スに均一に曝されるようにした。Therefore, in the present invention, as shown in FIG. 2, the carrier gas is caused to flow from the lower portion of the container to make the pressure in the raw material container uniform. In addition, as shown in FIG. 1, a capillary plate with a large number of holes is installed in the raw material container, and the raw material is placed on the capillary plate to increase the effective surface area of the raw material and to make uniform the carrier gas from the bottom. To be exposed to.
【００１０】[0010]
【作用】上記の手段によって、金属化合物原料の蒸気圧
が飽和蒸気圧に近づくため、低温においても充分な原料
供給量が得られる。By the above means, the vapor pressure of the metal compound raw material approaches the saturated vapor pressure, so that a sufficient raw material supply amount can be obtained even at a low temperature.
【００１１】[0011]
（実施例１）図１（メッシュ方式）の原料容器を作製し
た。２００cc用のステンレス製の原料容器（１５２mmの
ＩＣＦフランジを使用）１中に円形の爪を三段に取り付
け、そこにキャピラリプレート４を乗せた。キャピラリ
プレート４はガラス製で、外径Φ８７mm，厚さ１mmの円
形のものを用いた。プレート内のΦ７７mmの範囲内（有
効面）に直径２５μｍの多数の孔が開いており、開口率
（孔の面積／プレートの有効面積）は５７％とした。こ
のキャピラリプレート４を３枚入れ、それぞれの上に金
属化合物原料３を均一に乗せた。キャリアガスのＮ2 は
原料容器１の下部からバルブ２を介して導入され、３枚
のキャピラリプレートの孔を順に抜けて原料を昇華また
は気化させ、容器上部からバルブ２を介して成膜室に導
入される。(Example 1) The raw material container of FIG. 1 (mesh method) was produced. Circular claws were attached in three stages in a 200 cc stainless steel raw material container (using an ICF flange of 152 mm), and a capillary plate 4 was placed thereon. The capillary plate 4 was made of glass and had a circular shape with an outer diameter of Φ87 mm and a thickness of 1 mm. A large number of holes having a diameter of 25 μm were opened in the range of φ77 mm (effective surface) in the plate, and the aperture ratio (area of holes / effective area of plate) was set to 57%. Three of these capillary plates 4 were put, and the metal compound raw material 3 was uniformly placed on each of them. N 2 as a carrier gas is introduced from the lower part of the raw material container 1 through the valve 2 to sequentially pass through the holes of the three capillary plates to sublimate or vaporize the raw material and enter the film forming chamber from the upper part of the container via the valve 2 to the film forming chamber. be introduced.
【００１２】図２（プレート方式）の原料容器を作製し
た。２００cc用のステンレス製の原料容器（１５２mmの
ＩＣＦフランジを使用）１中に直径５mmのステンレス棒
に５枚のステンレス製のプレート５を固定し、容器内に
取り付けた。それぞれのプレート５上に金属化合物原料
３を均一に乗せた。キャリアガスのＮ2 は図１の例と同
様に原料容器の下部から導入され、５枚のプレート上の
原料を気化させ、容器上部から成膜室に導入される。A raw material container shown in FIG. 2 (plate system) was produced. Five stainless steel plates 5 were fixed to a stainless steel rod having a diameter of 5 mm in a 200 cc stainless steel raw material container (using an ICF flange of 152 mm) 1 and mounted inside the container. The metal compound raw material 3 was uniformly placed on each plate 5. The carrier gas N 2 is introduced from the lower part of the raw material container as in the example of FIG. 1, the raw materials on the five plates are vaporized, and then introduced into the film forming chamber from the upper part of the container.
【００１３】図３に示す従来の原料容器、図１(メッシ
ュ方式）および図２(プレート方式）に示す本発明によ
る原料容器にＳｒ（ＤＰＭ)2を４０ｇずつ入れ、図６に
示すＣＶＤ装置を用いて、Ｓｒ酸化膜の成膜を行った。
Ｓｒ（ＤＰＭ)2は常温，常圧で固体である。本発明によ
る原料容器を用いれば、両方式とも原料の有効面積を従
来方式に比べて３倍程度に増大することができる。ＨＦ
洗浄して自然酸化膜を除去したＳｉ基板上に基板温度４
００℃で成膜し、膜厚をエリプソメトリで測定した。キ
ャリアガス(Ｎ2）の流量は１００ccm、酸素の流量は２
００ccm、成膜室の圧力は２Torrとした。40 g of Sr (DPM) 2 is put in each of the conventional raw material container shown in FIG. 3 and the raw material container according to the present invention shown in FIG. 1 (mesh system) and FIG. 2 (plate system), and the CVD apparatus shown in FIG. A Sr oxide film was formed by using the above.
Sr (DPM) 2 is a solid at room temperature and pressure. By using the raw material container according to the present invention, it is possible to increase the effective area of the raw material by about 3 times as compared with the conventional method in both types. HF
Substrate temperature 4 on the Si substrate from which the native oxide film was removed by cleaning
A film was formed at 00 ° C. and the film thickness was measured by ellipsometry. Carrier gas (N 2 ) flow rate is 100 ccm, oxygen flow rate is 2
The pressure in the film forming chamber was set to 00 ccm and 2 Torr.
【００１４】図７にＳｒ酸化膜成長速度の原料容器温度
依存性を示す。本発明による原料容器を用いれば、従来
の原料容器を用いた場合に比べて、Ｓｒ酸化膜の成長速
度を３倍以上に増大させることができる。特に、原料の
蒸気圧が小さくなる低温側で成長速度増大の効果は大き
い。また、メッシュ方式では、プレート方式に比べて原
料の有効面積は同等であるのにかかわらず成長速度増大
の効果が大きいことが分かる。これは、メッシュ方式で
は固体の原料がキャリアガスによって空中に巻き上げら
れるため、原料の有効面積増大の効果がより大きくなる
ものと考えられる。FIG. 7 shows the dependence of the growth rate of the Sr oxide film on the temperature of the raw material container. By using the raw material container according to the present invention, the growth rate of the Sr oxide film can be increased three times or more as compared with the case of using the conventional raw material container. In particular, the effect of increasing the growth rate is great on the low temperature side where the vapor pressure of the raw material becomes small. Further, it can be seen that the mesh method has a larger effect of increasing the growth rate than the plate method, although the effective area of the raw material is the same. This is considered to be because, in the mesh method, the solid raw material is wound up in the air by the carrier gas, so that the effective area of the raw material is increased.
【００１５】また、Ｂａ（ＤＰＭ)2を用いてＢａ酸化膜
を成膜する場合も同様の結果が得られた。成膜条件はＳ
ｒ酸化膜を形成した場合と同じである。結果を図８に示
す。本発明による原料容器を用いれば、従来の原料容器
を用いた場合に比べて、Ｂａ酸化膜の成長速度を２倍以
上に増大させることができる。また、メッシュ方式で
は、プレート方式に比べて成長速度増大の効果が大き
い。Similar results were obtained when a Ba oxide film was formed using Ba (DPM) 2 . Film forming condition is S
This is the same as when the r oxide film is formed. The results are shown in Fig. 8. By using the raw material container according to the present invention, the growth rate of the Ba oxide film can be more than doubled as compared with the case of using the conventional raw material container. Further, the mesh method has a greater effect of increasing the growth rate than the plate method.
【００１６】ここで、プレートの枚数は、多ければ多い
ほど効果が大きいことは容易に想像できるが、飽和蒸気
圧に近づくにつれて効果の程度は小さくなる。また、容
器内部にこれらの構造物が多く入ると、汚染が入りやす
くなり、均熱性も悪くなるため、メッシュ方式は３〜５
枚、プレート方式も３〜７枚程度が望ましい。Here, it can be easily imagined that the greater the number of plates, the greater the effect, but the effect becomes smaller as the saturated vapor pressure is approached. Further, if many of these structures enter the container, contamination easily occurs and the heat uniformity deteriorates.
The number of sheets and the number of plates are also preferably about 3 to 7.
【００１７】また、キャピラリプレートの孔径は固体原
料の粒径よりも小さい必要があり、数μｍから数十μｍ
程度が望ましい。ただし、液体の金属化合物原料でも粘
性があるものならば、孔を抜けて下方に落ちることがな
いため使用できる。開口率も多ければ多いほど圧損が小
さくなり、原料容器内の圧力を均一にすることができ
る。また、図９に示すように、開口率と酸化膜の成長速
度は相関があるため、充分な成長速度を得るためには、
開口率はプレートの有効面積の５０％以上であることが
好ましい。Further, the pore diameter of the capillary plate must be smaller than the particle diameter of the solid raw material, and is several μm to several tens μm.
The degree is desirable. However, even if the liquid metal compound raw material is viscous, it can be used because it does not fall down through the holes. The larger the opening ratio, the smaller the pressure loss, and the pressure in the raw material container can be made uniform. Further, as shown in FIG. 9, since the aperture ratio and the growth rate of the oxide film are correlated, in order to obtain a sufficient growth rate,
The aperture ratio is preferably 50% or more of the effective area of the plate.
【００１８】Ｂａ，Ｓｒの化合物原料はＳｒ(ＤＰ
Ｍ)2，Ｂａ(ＤＰＭ)2に限らず、ジエトキシバリウム、
すなわち、Ｂａ(ＯＣ2Ｈ5)2 、ジイソプロポキシバリウ
ム、すなわち、Ｂａ(ｉ−ＯＣ3Ｈ7)2、ジエトキシスト
ロンチウム、すなわち、Sr(OC2H5)2、ジイソプロポキシ
ストロンチウム、すなわち、Ｓｒ（ｉ−ＯＣ3Ｈ7)2、バ
リウムビスアセチルアセナート、すなわち、Ｂａ（Ａｃ
Ａｃ)2、バリウムビスヘキサフルオロアセチルアセナー
ト、すなわち、Ｂａ（ＨＦＡ)2、ストロンチウムビスア
セチルアセナート、すなわち、Ｓｒ（ＡｃＡｃ)2、スト
ロンチウムビスヘキサフルオロアセチルアセナート、す
なわち、Ｓｒ（ＨＦＡ)2等の有機化合物原料や、ＢａＦ
2，ＢａＣｌ2，ＢａＢｒ2，ＢａＩ2，ＳｒＦ2，ＳｒＣ
ｌ2，ＳｒＢｒ2,ＳｒＩ2 等のハロゲン化合物を用いて
も、従来の原料容器を用いた場合に比べて、Ｂａ酸化膜
またはＳｒ酸化膜の成長速度を２倍以上に増大させるこ
とができた。The raw materials for the compounds of Ba and Sr are Sr (DP
M) 2 and Ba (DPM) 2 as well as diethoxy barium,
That, Ba (OC 2 H 5) 2, diisopropoxy barium, i.e., Ba (i-OC 3 H 7) 2, diethoxy strontium, i.e., Sr (OC 2 H 5) 2, diisopropoxy strontium, i.e. , Sr (i-OC 3 H 7 ) 2 , barium bisacetylacetate, that is, Ba (Ac
Ac) 2 , barium bishexafluoroacetylacenate, ie, Ba (HFA) 2 , strontium bisacetylacenate, ie, Sr (AcAc) 2 , strontium bishexafluoroacetylacenate, ie, Sr (HFA) 2, etc. Organic compound raw materials and BaF
2 , BaCl 2 , BaBr 2 , BaI 2 , SrF 2 , SrC
Even when a halogen compound such as l 2 , SrBr 2 or SrI 2 was used, the growth rate of the Ba oxide film or the Sr oxide film could be more than doubled as compared with the case of using the conventional raw material container. .
【００１９】本発明による原料供給機構により、Ｔａ，
Ｓｉ，Ｔｉ，Ｚｒ，Ｈｆ，Ｙ，Ｎｂ，Ｐｂ，Ｓｒ，Ｂ
ａ，Ｂｉ，Ｌａ，Ｐｔ，Ｒｕ，Ｗの化合物原料を用いて
も、それぞれの金属膜，酸化膜，窒化膜の成長速度増大
の効果が確認された。By the raw material supply mechanism according to the present invention, Ta,
Si, Ti, Zr, Hf, Y, Nb, Pb, Sr, B
Even when the compound raw materials of a, Bi, La, Pt, Ru, and W were used, the effect of increasing the growth rate of each metal film, oxide film, and nitride film was confirmed.
【００２０】（実施例２）メッシュ方式の原料容器を２
台用意し、それぞれＢa(ＤＰＭ)2とＳr(ＤＰＭ)2を入
れ、ＢＳＴ膜の形成を行った。なお、Ｔｉは室温で液体
であるトリイソプロポキシドチタニウム、すなわち、Ｔ
ｉ（ＯＣ3Ｈ7)4をキャリアガスＮ2(流量５０ccm）でバ
ブリングすることによって供給した。酸素の流量は２０
０ccm、成膜室の圧力は２Torrとした。Ｓｉ基板上に反
応防止膜としてスパッタ法でＴｉＮを１００ｎｍ形成
し、その後、スパッタ法でＰｔを２００ｎｍ形成し、そ
の上にＢＳＴを基板温度４００℃で形成した。Ｂａ，Ｓ
ｒ，Ｔｉの組成比は、Ｂａ：Ｓｒ：Ｔｉ＝０.５：０.
５：１となるように、ＢａとＳｒキャリア流量を調整し
た。原料容器温度１６０℃における、ＢＳＴ膜の成長速
度は１０ｎｍ／min であり、従来技術による成長速度の
０.５ｎｍ／minに比べて２０倍の向上が得られた。(Embodiment 2) Two mesh type raw material containers are used.
A stand was prepared, and Ba (DPM) 2 and Sr (DPM) 2 were respectively put therein to form a BST film. Incidentally, Ti is triisopropoxide titanium which is a liquid at room temperature, that is, T
i (OC 3 H 7 ) 4 was supplied by bubbling with carrier gas N 2 (flow rate 50 ccm). The flow rate of oxygen is 20
The pressure in the film forming chamber was 0 ccm and 2 Torr. A TiN film having a thickness of 100 nm was formed as a reaction preventing film on a Si substrate by a sputtering method, and then Pt was formed to have a thickness of 200 nm by a sputtering method, and BST was formed thereon at a substrate temperature of 400 ° C. Ba, S
The composition ratio of r and Ti is Ba: Sr: Ti = 0.5: 0.
The Ba and Sr carrier flow rates were adjusted so as to be 5: 1. The growth rate of the BST film at a raw material container temperature of 160 ° C. was 10 nm / min, which was 20 times higher than the growth rate of 0.5 nm / min obtained by the conventional technique.
【００２１】さらに、ＢＳＴ膜を１００ｎｍ形成した
後、６５０℃、１分のＲＴＡ（酸素雰囲気）で結晶化さ
せ、Ａｕをマスク蒸着することによって上部電極を形成
しキャパシタを作製した。電気的特性の測定の結果、Ｓ
ｉＯ2換算膜厚１.１ｎｍ（BST膜厚１００ｎｍ）で耐圧
２Ｖ（判定電流密度１０-7Ａ／cm2 ）以上を満足してお
り、従来構造による原料容器を用いたものを比較しても
変わり無い電圧−電流密度特性が得られた。なお、１０
０ＫＨｚで求めた容量から計算すると比誘電率は約３５
０であり、従来方式のものと同等であった。Further, after forming a BST film of 100 nm, it was crystallized by RTA (oxygen atmosphere) at 650 ° C. for 1 minute and Au was mask-deposited to form an upper electrode to form a capacitor. As a result of measurement of electrical characteristics, S
It has a withstand voltage of 2 V (judgment current density of 10 −7 A / cm 2 ) or more at an io 2 equivalent film thickness of 1.1 nm (BST film thickness of 100 nm), and is compared with a conventional structure using a raw material container. Unchanged voltage-current density characteristics were obtained. 10
When calculated from the capacitance obtained at 0 KHz, the relative dielectric constant is about 35.
It was 0, which was equivalent to that of the conventional method.
【００２２】本発明を用いて成膜できる絶縁膜材料はＢ
ＳＴに限らず、実施例１で示した原料を用いて、ＰｂＴ
ｉＯ3，Ｐｂ（ＺｒXＴｉ1-X)Ｏ3，ＳｒＴｉＯ3，Ｂｉ系
層状強誘電体化合物薄膜等の酸化物の混合物においても
成長速度増大の効果が得られた。The insulating film material which can be formed by using the present invention is B
Not limited to ST, using the raw materials shown in Example 1, PbT
The effect of increasing the growth rate was also obtained in a mixture of oxides such as iO 3 , Pb (Zr X Ti 1-X ) O 3 , SrTiO 3 , and Bi-based layered ferroelectric compound thin films.
【００２３】（実施例３）本発明による原料供給機構を
用いてダイナミック・ランダム・アクセス・メモリ（Ｄ
ＲＡＭ）を作製した。メモリセルの要部断面図を図１０
に示す。ここで、容量素子はＳｉＯ2換算膜厚１.１ｎｍ
（ＢＳＴ膜厚１００ｎｍ）で耐圧２Ｖ（判定電流密度１
０-7Ａ／cm2 ）以上を満足しており、さらにＤＲＡＭと
しての動作が確認された。また、本発明による原料供給
機構を用いて形成された容量素子は、通信用ＬＳＩなど
で大容量を必要とするコンデンサー部分にも適用でき
る。(Embodiment 3) A dynamic random access memory (D
RAM) was prepared. FIG. 10 is a sectional view of the main part of the memory cell.
Shown in Here, the capacitance element is a SiO 2 converted film thickness of 1.1 nm.
(BST film thickness 100 nm) withstand voltage 2 V (judgment current density 1
0-7 A / cm 2 ) or more was satisfied, and further the operation as a DRAM was confirmed. Further, the capacitive element formed by using the raw material supply mechanism according to the present invention can be applied to a capacitor portion that requires a large capacity in a communication LSI or the like.
【００２４】また、本発明による原料供給機構を用いて
ＰｂＴｉＯ3，Ｐｂ(ＺrXＴi1-X)Ｏ3，Ｂｉ系層状化合物
薄膜等の強誘電体膜を形成し、フェロエレクトリック・
ランダム・アクセス・メモリ（ＦＲＡＭ）等の不揮発性
メモリに適用しても効果が確認された。Further, a ferroelectric film such as PbTiO 3 , Pb (Zr X Ti 1-X ) O 3 , Bi-based layered compound thin film is formed by using the raw material supply mechanism according to the present invention.
The effect was confirmed even when applied to a nonvolatile memory such as a random access memory (FRAM).
【００２５】[0025]
【発明の効果】本発明によって原料容器を低温化しても
充分な原料供給量が得られるため、装置の熱劣化等の問
題が起こらない温度（２００℃以下）まで低温化して
も、従来技術の２倍以上の膜成長速度が得られる。According to the present invention, a sufficient amount of raw material can be supplied even if the temperature of the raw material container is lowered. Therefore, even if the temperature is lowered to a temperature (200 ° C. or less) at which a problem such as thermal deterioration of the apparatus does not occur, it is possible to obtain A film growth rate twice or more can be obtained.
【図１】本発明によるメッシュ方式原料容器の説明図。FIG. 1 is an explanatory view of a mesh type raw material container according to the present invention.
【図２】本発明によるプレート方式原料容器の説明図。FIG. 2 is an explanatory view of a plate-type raw material container according to the present invention.
【図３】従来技術による原料容器の説明図。FIG. 3 is an explanatory view of a raw material container according to a conventional technique.
【図４】原料蒸気圧の原料有効面積依存性を示す特性
図。FIG. 4 is a characteristic diagram showing the material effective area dependency of the material vapor pressure.
【図５】原料有効面積増大のための容器構造の説明図。FIG. 5 is an explanatory view of a container structure for increasing the effective material area.
【図６】本発明の実施例で用いたＣＶＤ装置の系統図。FIG. 6 is a system diagram of a CVD apparatus used in an example of the present invention.
【図７】Ｓｒ酸化膜成長速度の原料容器温度依存性を示
す特性図。FIG. 7 is a characteristic diagram showing the dependency of the growth rate of the Sr oxide film on the temperature of the raw material container.
【図８】Ｂａ酸化膜成長速度の原料容器温度依存性を示
す特性図。FIG. 8 is a characteristic diagram showing the dependence of the Ba oxide film growth rate on the temperature of the raw material container.
【図９】酸化膜成長速度のメッシュ開口率依存性を示す
特性図。FIG. 9 is a characteristic diagram showing the dependence of the oxide film growth rate on the mesh aperture ratio.
【図１０】本発明による原料供給機構を用いて作製した
ＤＲＡＭの要部の断面図。FIG. 10 is a sectional view of a main part of a DRAM manufactured by using the raw material supply mechanism according to the present invention.
１…原料容器、２…バルブ、３…金属化合物原料、４…
キャピラリプレート。1 ... Raw material container, 2 ... Valve, 3 ... Metal compound raw material, 4 ...
Capillary plate.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｌ 21/822 9276−4Ｍ Ｈ０１Ｌ 27/10 ６５１ 27/108 21/8242 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location H01L 21/822 9276-4M H01L 27/10 651 27/108 21/8242
Claims (6)
原料を用いるＣＶＤ装置において、原料容器内に少なく
とも１枚のプレートが具備されており、前記プレート上
に金属化合物原料をのせ、キャリアガスを流して気化ま
たは昇華させることによって原料を供給することを特徴
とする半導体製造装置。1. A CVD apparatus using a solid or liquid metal compound raw material at room temperature and normal pressure, wherein at least one plate is provided in the raw material container, the metal compound raw material is placed on the plate, and a carrier gas is provided. A semiconductor manufacturing apparatus, characterized in that a raw material is supplied by flowing a gas to vaporize or sublime it.
原料を用いるＣＶＤ装置において、原料容器内に多数の
孔が開いているプレートが具備されており、前記プレー
ト上に金属化合物原料をのせ、下部からキャリアガスを
流して気化または昇華させることによって原料を供給す
ることを特徴とする半導体製造装置。2. A CVD apparatus using a solid or liquid metal compound raw material at room temperature and normal pressure, wherein a raw material container is provided with a plate having a large number of holes, and the metal compound raw material is placed on the plate. A semiconductor manufacturing apparatus characterized in that a raw material is supplied by causing a carrier gas to flow from the lower part to be vaporized or sublimated.
面積は、前記プレートの有効面積の５０％以上である半
導体製造装置。3. The semiconductor manufacturing apparatus according to claim 2, wherein the total area of the holes of the plate is 50% or more of the effective area of the plate.
原料は、ＢａまたはＳｒの化合物原料である半導体製造
装置。4. A semiconductor manufacturing apparatus, wherein the metal compound raw material according to claim 1 or 2 is a Ba or Sr compound raw material.
装置を用いて形成した、（Ｂａ，Ｓｒ）ＴｉＯ3(ストロ
ンチウム・チタン酸バリウム）膜を用いる半導体装置。5. A semiconductor device using a (Ba, Sr) TiO 3 (strontium / barium titanate) film formed by using the semiconductor manufacturing apparatus according to claim 1.
ナミック・ランダム・アクセス・メモリである半導体装
置。6. The semiconductor device according to claim 5, which is a dynamic random access memory.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7082266A JPH08279497A (en) | 1995-04-07 | 1995-04-07 | Semiconductor manufacturing equipment and semiconductor equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7082266A JPH08279497A (en) | 1995-04-07 | 1995-04-07 | Semiconductor manufacturing equipment and semiconductor equipment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08279497A true JPH08279497A (en) | 1996-10-22 |
Family
ID=13769683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7082266A Pending JPH08279497A (en) | 1995-04-07 | 1995-04-07 | Semiconductor manufacturing equipment and semiconductor equipment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08279497A (en) |
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| CN112458434B (en) * | 2021-01-29 | 2021-06-01 | 江苏南大光电材料股份有限公司 | Encapsulation of Solid Precursors and Their Applications in Vapor Deposition Processes |
| CN116103636A (en) * | 2023-04-12 | 2023-05-12 | 上海星原驰半导体有限公司 | Solid-phase precursor output device and vapor deposition system |
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