JPH10273781A - Cvd apparatus - Google Patents
Cvd apparatusInfo
- Publication number
- JPH10273781A JPH10273781A JP7848297A JP7848297A JPH10273781A JP H10273781 A JPH10273781 A JP H10273781A JP 7848297 A JP7848297 A JP 7848297A JP 7848297 A JP7848297 A JP 7848297A JP H10273781 A JPH10273781 A JP H10273781A
- Authority
- JP
- Japan
- Prior art keywords
- raw material
- solvent
- solid
- solid raw
- supplying
- 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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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ＣＶＤ（ケミカル
ベーパーデポジション）装置に関し、詳しくは、固体原
料を溶媒に溶解した溶液を原料として用いるＣＶＤ装置
に関する。The present invention relates to a CVD (chemical vapor deposition) apparatus, and more particularly, to a CVD apparatus using a solution obtained by dissolving a solid material in a solvent as a material.
【０００２】[0002]
【従来の技術】ＣＶＤ装置における薄膜生成原料として
固体原料を用いる際には、固体原料を直接加熱するとと
もに該固体原料にキャリヤガスを接触させ、気化した原
料蒸気をキャリヤガスで搬送して反応室に供給する方法
と、固体原料を溶媒に溶解させて溶液（溶液原料）と
し、この溶液原料を気化器内で加熱して気化させ、これ
をキャリヤガスで搬送して反応室に供給する方法とが知
られている。2. Description of the Related Art When a solid raw material is used as a raw material for forming a thin film in a CVD apparatus, the solid raw material is directly heated, a carrier gas is brought into contact with the solid raw material, and the vaporized raw material vapor is transported by the carrier gas. And a method of dissolving a solid raw material in a solvent to form a solution (solution raw material), heating the solution raw material in a vaporizer to vaporize the raw material, transporting the raw material with a carrier gas and supplying it to a reaction chamber. It has been known.
【０００３】固体原料を直接加熱する方法では、原料供
給量を増やすために固体原料を２００℃前後の高温に加
熱しているため、熱によって重合や分解が進んでしまう
ことがあった。また、固体原料の蒸気をキャリヤガスに
同伴させて反応室に供給するので、キャリヤガスと固体
原料とを効率よく接触させる必要があるが、接触状態が
経時的に変化してしまうので、再現性よく薄膜を作製す
ることが困難であった。In the method of directly heating a solid raw material, since the solid raw material is heated to a high temperature of about 200 ° C. in order to increase the raw material supply amount, the heat may cause polymerization or decomposition. Also, since the vapor of the solid raw material is supplied to the reaction chamber along with the carrier gas, it is necessary to efficiently contact the carrier gas and the solid raw material. It was difficult to form a thin film well.
【０００４】一方、溶液状態とした原料を用いる方法
は、固体原料を直接加熱する方法に比べて、原料を高温
に保持する必要がないため、熱による原料の変質が抑え
られ、成膜速度も向上することが知られており、比較的
大径の基板上にも均一な薄膜を作製することができるの
で、８インチ以上の基板に薄膜を形成する際に好適に用
いられている。On the other hand, in the method using a raw material in a solution state, since the raw material does not need to be maintained at a high temperature as compared with a method in which a solid raw material is directly heated, deterioration of the raw material due to heat is suppressed and the film forming speed is reduced. It is known to improve the properties, and a uniform thin film can be formed even on a substrate having a relatively large diameter. Therefore, it is suitably used when forming a thin film on a substrate of 8 inches or more.
【０００５】[0005]
【発明が解決しようとする課題】しかし、上述のような
溶液原料を用いたＣＶＤ法では、成膜操作を繰り返すう
ちに原料が変質し、成膜速度が低下するという現象を生
じることがあった。これは、固体原料を溶媒に溶解した
液体の状態では分子が動き易くなり、固体のときに比べ
ると容易に反応が進行するため、溶液中の不純物や溶存
ガスとの反応が進んだり、配位子の交換や分子の重合が
進み、加熱したときの蒸気圧が非常に低い物質に変化す
ることが原因と考えられる。However, in the above-described CVD method using a solution raw material, a phenomenon may occur in which the raw material is deteriorated and the film forming speed is reduced while the film forming operation is repeated. . This is because molecules move easily in a liquid state in which a solid raw material is dissolved in a solvent, and the reaction progresses more easily than in a solid state. It is considered that the cause is that the exchange of molecules and the polymerization of molecules progress, and the vapor pressure upon heating changes to a very low substance.
【０００６】これに対応するためには、溶液原料を少量
ずつ調製し、短時間で使い切るようにすることが考えら
れるが、多大な手間を必要とすることになる。In order to cope with this, it is conceivable to prepare the solution raw material little by little and use it up in a short time, but it requires a lot of labor.
【０００７】そこで本発明は、溶液原料を自動的に調製
することができ、固体原料及び溶液原料の変質を防止す
ることができる溶液原料供給手段を備えたＣＶＤ装置を
提供することを目的としている。Accordingly, an object of the present invention is to provide a CVD apparatus provided with a solution material supply means capable of automatically preparing a solution material and preventing deterioration of a solid material and a solution material. .
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するた
め、本発明のＣＶＤ装置は、固体原料を溶媒に溶解した
溶液を加熱して気化させる気化器の前段に、固体原料と
溶媒とを混合して固体原料を溶媒に溶解させる混合容器
と、該混合容器に所定量の溶媒を供給するための溶媒容
器及び送液手段と、前記固体原料を貯留するとともに所
定量の固体原料を前記混合容器に供給するための固体原
料容器及び粉体供給手段とを設けたことを特徴としてい
る。In order to achieve the above object, a CVD apparatus according to the present invention comprises a step of mixing a solid raw material and a solvent before a vaporizer for heating and vaporizing a solution obtained by dissolving the solid raw material in the solvent. A mixing container for dissolving the solid raw material in the solvent, a solvent container for supplying a predetermined amount of the solvent to the mixing container, and a liquid sending means, and a storage container for storing the solid raw material and the predetermined amount of the solid raw material for the mixing container. Characterized in that a solid raw material container and powder supply means for supplying the raw material to the container are provided.
【０００９】[0009]
【発明の実施の形態】図１は、本発明のＣＶＤ装置の一
形態例を示す系統図である。このＣＶＤ装置は、基板１
を加熱するヒーター２を備えた反応室３と、この反応室
３に薄膜生成原料を供給する原料供給系４とにより形成
されており、原料供給系４には、固体原料と溶媒とを混
合して溶液原料を製造するための混合容器５と、該混合
容器５内の溶液原料を供給するためのポンプ６と、溶液
原料を加熱して気化させる気化器７と、気化器７で気化
した原料蒸気を搬送するためのキャリヤガスを流量制御
器８を介して供給するキャリヤガス供給経路９とが設け
られている。通常、この原料供給系４は、薄膜の生成に
必要な原料の種類に応じて複数系統設けられている。FIG. 1 is a system diagram showing one embodiment of a CVD apparatus according to the present invention. This CVD apparatus has a substrate 1
And a raw material supply system 4 for supplying a thin film forming raw material to the reaction chamber 3. The raw material supply system 4 is a mixture of a solid raw material and a solvent. Container 5 for producing a solution raw material by heating, a pump 6 for supplying the solution raw material in the mixing container 5, a vaporizer 7 for heating and vaporizing the solution raw material, and a raw material vaporized by the vaporizer 7 A carrier gas supply path 9 for supplying a carrier gas for transporting steam via a flow controller 8 is provided. Usually, a plurality of raw material supply systems 4 are provided according to the types of raw materials necessary for forming a thin film.
【００１０】また、反応室３の直前には、原料の一つで
ある酸素を流量制御器１０を介して供給するための酸素
供給経路１１と、キャリヤガスに同伴された原料蒸気と
酸素とを混合するための混合器１２とが設けられてお
り、各原料供給系４から供給される原料蒸気は、混合器
１２で酸素と混合した状態で反応室３内に供給される。Immediately before the reaction chamber 3, an oxygen supply path 11 for supplying oxygen, which is one of the raw materials, via a flow rate controller 10, and a raw material vapor and oxygen entrained in a carrier gas are supplied. A mixer 12 for mixing is provided, and the raw material vapor supplied from each raw material supply system 4 is supplied into the reaction chamber 3 while being mixed with oxygen in the mixer 12.
【００１１】前記混合容器５には、溶媒容器２１及び送
液手段であるポンプ２２を有する溶媒供給経路２３と、
固体原料容器２４及び粉体供給手段である粉体フィーダ
ー２５を有する固体原料供給経路２６とが設けられてい
る。また、この混合容器５には、適宜な撹拌手段、例え
ばマグネチックスターラー等が設けられている。The mixing container 5 has a solvent supply path 23 having a solvent container 21 and a pump 22 as a liquid sending means.
A solid material container 24 and a solid material supply path 26 having a powder feeder 25 as a powder supply means are provided. The mixing vessel 5 is provided with a suitable stirring means, for example, a magnetic stirrer or the like.
【００１２】前記粉体フィーダー２５は、ホッパー２５
ａの底部にスクリュー２５ｂを有するものであって、こ
の粉体フィーダー２５には、混合容器５への固体原料供
給量をあらかじめ定められた量とするため、例えば、固
体原料供給中の粉体フィーダー２５の重量変化を測定
し、減算法によって所定重量減少したときにスクリュー
２５ｂを停止させる機能等を備えた制御手段が設けられ
ている。The powder feeder 25 includes a hopper 25
In order to supply a predetermined amount of the solid raw material to the mixing vessel 5, for example, a powder feeder during the supply of the solid raw material is provided in the powder feeder 25. Control means having a function of measuring a change in weight of the screw 25 and stopping the screw 25b when a predetermined weight is reduced by a subtraction method is provided.
【００１３】また、前記溶媒供給経路２３にも、溶媒容
器２１内の溶媒を所定量混合容器５に供給するための制
御手段が設けられている。この制御手段としては、例え
ば、ポンプ２２に容積型の流量制御が可能なものを用い
てポンプ２２の作動時間を制御したり、配管途中に積算
流量計を設けて流量を測定することによってポンプ２２
を制御したり、溶媒容器２１の重量を測定して減算法に
よってポンプ２２を制御したりするなどの方法を採用す
ることができる。The solvent supply path 23 is also provided with control means for supplying a predetermined amount of the solvent in the solvent container 21 to the mixing container 5. As the control means, for example, the pump 22 is capable of controlling the operation time of the pump 22 by using a pump capable of positive displacement control, or is provided with an integrating flow meter in the piping to measure the flow rate.
Or a method of measuring the weight of the solvent container 21 and controlling the pump 22 by a subtraction method.
【００１４】前記混合容器５への固体原料及び溶媒の供
給は、連続的に行うこともできるが、通常は、混合容器
５内の溶液原料が所定量以下になったときに、所定量の
固体原料及び溶媒を混合容器５内に供給し、必要量の溶
液原料を調製することが好ましい。The supply of the solid raw material and the solvent to the mixing container 5 can be performed continuously, but usually, when the amount of the solution raw material in the mixing container 5 becomes equal to or less than a predetermined amount, a predetermined amount of the solid material is supplied. It is preferable that the raw material and the solvent are supplied into the mixing vessel 5 to prepare a required amount of the solution raw material.
【００１５】また、上記溶液原料の調製は、手動で開始
させることもできるが、混合容器５内の溶液原料の量を
測定する手段、例えば重量や液面高さで測定したり、溶
液原料の消費量を積算したりする手段を設け、これに前
記固体原料供給用の制御手段や溶媒供給用の制御手段を
連動させて自動的に開始させることも可能である。ま
た、薄膜形成を行う処理回数に応じて所要量の溶液原料
をあらかじめ調製するようにしてもよい。なお、混合容
器５の容量や、調製する溶液原料の量は、溶液原料の消
費速度、溶液原料中の固体原料の変質速度、固体原料や
溶媒の供給精度に応じて設定すればよい。さらに、各容
器には、固体原料や溶媒を補充するための経路を設けた
り、容器内，粉体フィーダー内等にシールガスを導入す
る経路を設けたりすることができ、各配管には、適当な
位置に弁を設けることにより、内部の清掃点検や原料等
の種類の変更を容易に行うことが可能となる。Although the preparation of the solution raw material can be started manually, a means for measuring the amount of the solution raw material in the mixing vessel 5, for example, by measuring the weight or the liquid level, or measuring the amount of the solution raw material, It is also possible to provide a means for accumulating the consumption amount, and to automatically start the control by interlocking the control means for supplying the solid raw material and the control means for supplying the solvent. Further, a required amount of a solution raw material may be prepared in advance according to the number of times of performing the thin film formation. The capacity of the mixing container 5 and the amount of the solution raw material to be prepared may be set according to the consumption rate of the solution raw material, the rate of change of the solid raw material in the solution raw material, and the supply accuracy of the solid raw material and the solvent. Further, each container may be provided with a route for replenishing the solid raw material and the solvent, or a route for introducing a sealing gas into the container, the powder feeder, or the like. Providing a valve at an appropriate position makes it possible to easily perform internal cleaning inspection and change the type of raw material and the like.
【００１６】このように、ＣＶＤ装置の原料供給系４
に、混合容器５と、所定量の溶媒を供給する溶媒供給経
路２３と、所定量の固体原料を供給する固体原料供給経
路２６とを設け、溶液原料の使用状況に合わせて自動的
に溶媒と固体原料とを混合して所定量の溶液原料を調整
するようにしたことにより、溶液の状態で長期間原料を
保存する必要がなくなるので、重合や分解等による溶液
原料の変質を防止することができるとともに、固体原料
を常温で保持できるので、安定した状態で再現性よく薄
膜作製を行うことが可能となる。As described above, the raw material supply system 4 of the CVD apparatus
Provided with a mixing vessel 5, a solvent supply path 23 for supplying a predetermined amount of solvent, and a solid source supply path 26 for supplying a predetermined amount of solid raw material. By mixing the solid raw material and adjusting the predetermined amount of the solution raw material, it is not necessary to store the raw material in a solution state for a long period of time, so that the deterioration of the solution raw material due to polymerization or decomposition can be prevented. In addition, since the solid raw material can be maintained at room temperature, a thin film can be produced in a stable state with good reproducibility.
【００１７】本発明で使用できる上記固体原料として
は、Ｂａ（ＤＰＭ）2 ，Ｓｒ（ＤＰＭ）2 ，Ｔｉ（Ｏｉ
Ｐｒ）2 （ＤＰＭ）2 ，Ｔｉ（ＯＭｅ）2 （ＤＰ
Ｍ）2 ，Ｃｕ（ＤＰＭ）2 ，Ｃａ（ＤＰＭ）2 ，Ｂｉ
（Ｃ6 Ｈ5 ）3 ，Ｂｉ｛（Ｃ6 Ｈ5 ）ＣＨ3 ｝3 ，Ｙ
（ＤＰＭ）3 ，Ｂａ（ＨＦＡ）2 ，Ｓｒ（ＨＦＡ）2 ，
Ｃｕ（ＨＦＡ）2 ，Ｃａ（ＨＦＡ）2 等のβ−ジケトネ
ート金属錯体や、この他、シクロペンタジエニル，フェ
ニル化合物及びその誘導体等を挙げることができ、溶媒
としては、ジエチルアミン，トリエチルアミン，エチレ
ンジアミン，ピリジン，ビピリジル，ジエチルエーテ
ル，テトラヒドロフラン等を挙げることができる。な
お、前記ＤＰＭはジピバロイルメタン、ＨＦＡはヘキサ
フロオロアセチルアセトネート、ＯｉＰｒはイソプロポ
キシをそれぞれ示す。The solid materials usable in the present invention include Ba (DPM) 2 , Sr (DPM) 2 , and Ti (Oi
Pr) 2 (DPM) 2 , Ti (OMe) 2 (DP
M) 2 , Cu (DPM) 2 , Ca (DPM) 2 , Bi
(C 6 H 5 ) 3 , Bi ｛(C 6 H 5 ) CH 3 ｝ 3 , Y
(DPM) 3 , Ba (HFA) 2 , Sr (HFA) 2 ,
Examples thereof include β-diketonate metal complexes such as Cu (HFA) 2 and Ca (HFA) 2 , and cyclopentadienyl, phenyl compounds and derivatives thereof. Examples of the solvent include diethylamine, triethylamine, ethylenediamine, and the like. Pyridine, bipyridyl, diethyl ether, tetrahydrofuran and the like can be mentioned. The DPM is dipivaloylmethane, HFA is hexafluoroacetylacetonate, and OiPr is isopropoxy.
【００１８】また、このような固体原料を用いて得られ
る薄膜としては、ＢＳＴ（Ｂａ，Ｓｒ）ＴｉＯ3 、Ｙ１
（ＳｒＢｉ2 Ｔｉ2 Ｏ9 ）、ＰＺＴ（Ｐｂ（Ｚｒ，Ｔ
ｉ）Ｏ3 ）、Ｂｉ4 Ｔｉ3 Ｏ12等の各種高誘電体や強誘
電体、Ｂｉ−Ｓｒ−Ｃａ−Ｃｕ−Ｏ系、Ｙ−Ｂａ−Ｃｕ
−Ｏ系等の超電導体酸化物薄膜がある。Further, as a thin film obtained by using such a solid material, BST (Ba, Sr) TiO 3 , Y1
(SrBi 2 Ti 2 O 9 ), PZT (Pb (Zr, T
i) Various high dielectrics and ferroelectrics such as O 3 ) and Bi 4 Ti 3 O 12 , Bi—Sr—Ca—Cu—O, Y—Ba—Cu
There is a superconductor oxide thin film such as -O type.
【００１９】[0019]
【発明の効果】以上説明したように、本発明のＣＶＤ装
置によれば、固体原料を溶解した溶液を安定した状態で
使用することができるので、膜質や膜厚の安定化が図
れ、再現性も向上させることができる。As described above, according to the CVD apparatus of the present invention, a solution in which a solid material is dissolved can be used in a stable state, so that the film quality and thickness can be stabilized, and the reproducibility can be improved. Can also be improved.
【図１】 本発明のＣＶＤ装置の一形態例を示す系統図
である。FIG. 1 is a system diagram showing one embodiment of a CVD apparatus of the present invention.
１…基板、３…反応室、４…原料供給系、５…混合容
器、７…気化器、９…キャリヤガス供給経路、１１…酸
素供給経路、１２…混合器、２１…溶媒容器、２２…ポ
ンプ、２３…溶媒供給経路、２４…固体原料容器、２５
…粉体フィーダー、２５ａ…ホッパー、２５ｂ…スクリ
ュー、２６…固体原料供給経路DESCRIPTION OF SYMBOLS 1 ... Substrate, 3 ... Reaction chamber, 4 ... Raw material supply system, 5 ... Mixing container, 7 ... Vaporizer, 9 ... Carrier gas supply path, 11 ... Oxygen supply path, 12 ... Mixer, 21 ... Solvent container, 22 ... Pump, 23: solvent supply path, 24: solid material container, 25
… Powder feeder, 25a hopper, 25b screw, 26… solid material supply path
Claims (1)
で加熱気化させて反応室に供給し、所定温度に加熱され
た基板上に薄膜を作製するＣＶＤ装置において、前記気
化器の前段に、前記固体原料と溶媒とを混合して固体原
料を溶媒に溶解させる混合容器と、該混合容器に所定量
の溶媒を供給するための溶媒容器及び送液手段と、前記
固体原料を貯留するとともに所定量の固体原料を前記混
合容器に供給するための固体原料容器及び粉体供給手段
とを設けたことを特徴とするＣＶＤ装置。In a CVD apparatus, a solution in which a solid raw material is dissolved in a solvent is heated and vaporized by a vaporizer and supplied to a reaction chamber, and a thin film is formed on a substrate heated to a predetermined temperature. A mixing container for mixing the solid raw material and a solvent to dissolve the solid raw material in the solvent, a solvent container and a liquid sending means for supplying a predetermined amount of solvent to the mixing container, and storing the solid raw material A CVD apparatus comprising: a solid material container for supplying a predetermined amount of solid material to the mixing container; and powder supply means.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7848297A JPH10273781A (en) | 1997-03-28 | 1997-03-28 | Cvd apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7848297A JPH10273781A (en) | 1997-03-28 | 1997-03-28 | Cvd apparatus |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10273781A true JPH10273781A (en) | 1998-10-13 |
Family
ID=13663224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7848297A Pending JPH10273781A (en) | 1997-03-28 | 1997-03-28 | Cvd apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10273781A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005256058A (en) * | 2004-03-10 | 2005-09-22 | Tosoh Corp | Iridium-containing membrane forming material and method for manufacturing iridium-containing membrane |
| JP2007162135A (en) * | 2005-12-09 | 2007-06-28 | Tera Semicon Corp | System for manufacturing flat panel display |
-
1997
- 1997-03-28 JP JP7848297A patent/JPH10273781A/en active Pending
Cited By (3)
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| JP2005256058A (en) * | 2004-03-10 | 2005-09-22 | Tosoh Corp | Iridium-containing membrane forming material and method for manufacturing iridium-containing membrane |
| JP2007162135A (en) * | 2005-12-09 | 2007-06-28 | Tera Semicon Corp | System for manufacturing flat panel display |
| KR100779118B1 (en) | 2005-12-09 | 2007-11-27 | 주식회사 테라세미콘 | Display Panel Manufacturing System |
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