JPH09213643A - Thin film depositing device and method for depositing thin film utilizing it - Google Patents
Thin film depositing device and method for depositing thin film utilizing itInfo
- Publication number
- JPH09213643A JPH09213643A JP8243666A JP24366696A JPH09213643A JP H09213643 A JPH09213643 A JP H09213643A JP 8243666 A JP8243666 A JP 8243666A JP 24366696 A JP24366696 A JP 24366696A JP H09213643 A JPH09213643 A JP H09213643A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- chamber
- substrate
- droplets
- precursor solution
- 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.)
- Withdrawn
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000000151 deposition Methods 0.000 title claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 52
- 239000002243 precursor Substances 0.000 claims abstract description 45
- 239000010408 film Substances 0.000 claims abstract description 11
- 239000007921 spray Substances 0.000 claims abstract 5
- 239000010936 titanium Substances 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 19
- 238000000427 thin-film deposition Methods 0.000 claims description 17
- 238000005507 spraying Methods 0.000 claims description 16
- 125000002524 organometallic group Chemical group 0.000 claims description 15
- 238000007736 thin film deposition technique Methods 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052788 barium Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- -1 titanium alkoxide compound Chemical class 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 230000003287 optical effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 8
- 238000007740 vapor deposition Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
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
- C23C16/4486—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 producing an aerosol and subsequent evaporation of the droplets or particles
-
- 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
- C23C16/22—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 deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
-
- 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
- C23C16/458—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 supporting substrates in the reaction chamber
- C23C16/4582—Rigid and flat substrates, e.g. plates or discs
- C23C16/4583—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally
- C23C16/4584—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally the substrate being rotated
-
- 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
- C23C16/48—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 by irradiation, e.g. photolysis, radiolysis, particle radiation
- C23C16/482—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 by irradiation, e.g. photolysis, radiolysis, particle radiation using incoherent light, UV to IR, e.g. lamps
-
- 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
- C23C16/52—Controlling or regulating the coating process
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Toxicology (AREA)
- Chemical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Semiconductor Memories (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は薄膜蒸着装置（thin
film deposition apparatus）及びこれを利用した薄膜
蒸着方法に係り、特に常温で基板上に均一な薄膜を蒸着
させる薄膜蒸着装置及びこれを利用した薄膜蒸着方法に
関する。TECHNICAL FIELD The present invention relates to a thin film deposition apparatus (thin
The present invention relates to a film deposition apparatus and a thin film deposition method using the same, and more particularly to a thin film deposition apparatus for depositing a uniform thin film on a substrate at room temperature and a thin film deposition method using the same.
【０００２】[0002]
【従来の技術】一般的に、厚さが１ミクロンより薄い薄
膜を製造するために、ゾルーゲル法、化学気相蒸着（ch
emical vapor deposition）法及びスパッタリング法等
の方法が知られている。2. Description of the Related Art Generally, a sol-gel method, chemical vapor deposition (ch
Methods such as an emical vapor deposition) method and a sputtering method are known.
【０００３】ゾルーゲル法は前駆体ゾル溶液をスピンナ
により回転する基板上に塗布した後加熱、乾燥及びアニ
ーリング工程を経てゼリー化することにより所望の薄膜
を得る方法である。この方法では前駆体ゾル溶液の組成
を調節することにより薄膜の組成を容易に制御しうる
が、前駆体ゾル溶液を大気中に露出された状態でのみ塗
布する短所と、加熱及び乾燥過程が急激な温度変化を伴
う短所がある。The sol-gel method is a method for obtaining a desired thin film by applying a precursor sol solution onto a rotating substrate by a spinner, and then heating, drying and annealing to form a jelly. In this method, the composition of the thin film can be easily controlled by adjusting the composition of the precursor sol solution, but there is a disadvantage that the precursor sol solution is applied only in a state of being exposed to the atmosphere, and the heating and drying processes are rapid. It has the disadvantage of being accompanied by various temperature changes.
【０００４】化学気相蒸着法は前駆体物質を蒸発や昇華
の方法で気体化した後、これを蒸着チャンバに導入し基
板上に蒸着させる方法である。この方法では前駆体の揮
発程度を一定に再現することが難しく、基板を加熱する
と共に蒸着工程を行わなければならないという短所があ
る。また、前駆体として使用される物質等の大部分が毒
性を有している。The chemical vapor deposition method is a method in which a precursor substance is vaporized by a method such as evaporation or sublimation and then introduced into a vapor deposition chamber for vapor deposition on a substrate. In this method, it is difficult to reproduce the degree of volatilization of the precursor at a constant level, and there is a disadvantage that the substrate must be heated and the vapor deposition process must be performed. Most of the substances used as precursors are toxic.
【０００５】スパッタリング法は所望の薄膜のような物
質が焼桔されたターゲットに加速された電子を撃って所
望の成分等が飛出るようにし、これを基板に蒸着させる
方法である。従って、スパッタリング法は所望の薄膜の
組成を得るためにターゲットの量を一定に再現すること
に困る。また、基板に多様な膜等が存在する場合これら
膜上に均一な厚さの薄膜を蒸着することに難しい点があ
り、基板を加熱すると共に蒸着工程を行わなければなら
ない短所がある。The sputtering method is a method in which a target such as a desired thin film is fired on a target and accelerated electrons are shot so that desired components and the like are ejected, and this is deposited on a substrate. Therefore, the sputtering method has a problem in that the target amount is constantly reproduced to obtain a desired thin film composition. In addition, when there are various films on the substrate, it is difficult to deposit a thin film having a uniform thickness on these films, and the substrate must be heated and the deposition process must be performed.
【０００６】[0006]
【発明が解決しようとする課題】従って、本発明の目的
は前述した短所を克服しうる薄膜蒸着装置を提供するこ
とにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a thin film deposition apparatus which can overcome the above-mentioned disadvantages.
【０００７】また、本発明の他の目的は前記薄膜蒸着装
置を利用した薄膜蒸着方法を提供することにある。Another object of the present invention is to provide a thin film deposition method using the thin film deposition apparatus.
【０００８】[0008]
【課題を解決するための手段】前記目的を達成するため
に本発明は、基板上に化学化合物の薄膜を蒸着する装置
において、前駆体溶液が盛られている貯蔵槽と、前記前
駆体溶液を移送させる移送手段と、前記移送された前駆
体溶液の温度を調節し、前記移送された前駆体溶液を液
滴に変換させる液滴噴霧装置と、前記液滴噴霧装置に連
結されたノズルを通して前記液滴が注入されるチャンバ
と、前記チャンバ内に前記基板が置かれるステージと、
前記チャンバの圧力を調節するための圧力調節手段より
なり、前記基板上に前記注入された液滴を蒸着させて薄
膜を形成することを特徴とする薄膜蒸着装置を提供す
る。In order to achieve the above object, the present invention provides an apparatus for depositing a thin film of a chemical compound on a substrate, a storage tank in which a precursor solution is placed, and the precursor solution. The transfer means for transferring, the droplet spraying device for controlling the temperature of the transported precursor solution to convert the transferred precursor solution into droplets, and the nozzle through the nozzle connected to the droplet spraying device. A chamber in which the droplets are injected, a stage in which the substrate is placed,
A thin film deposition apparatus comprising a pressure adjusting unit for adjusting the pressure of the chamber, and forming a thin film by depositing the injected droplets on the substrate.
【０００９】前記液滴噴霧装置に運搬気体を制御しうる
質量流速制御器（ＭＦＣ）が連結されていて、前記チャ
ンバの上部に前記基板上で前記注入された液滴が膜とし
ての反応が促進されるように光エネルギーソース、例え
ば紫外線ランプが設けられていて、前記チャンバ内に蒸
着される薄膜の厚さをモニターするモニター部を具備す
る。A mass flow rate controller (MFC) capable of controlling a carrier gas is connected to the droplet spraying device to promote a reaction of the injected droplets as a film on the substrate above the chamber. As described above, a light energy source such as an ultraviolet lamp is provided, and a monitor unit for monitoring the thickness of the thin film deposited in the chamber is provided.
【００１０】前記ステージは回転でき、基板加熱手段を
含み、前記圧力調節手段は前記チャンバに連結された真
空ラインと、前記チャンバ内の圧力を前記真空ラインを
通して調節する２つ以上のポンプと、真空ライン中に設
置されてチャンバ内の圧力を一定に保たせるスロットリ
ングバルブと、前記真空ラインの不純物をフィルタリン
グするトラップと、前記チャンバの圧力を測るイオンゲ
ージよりなる。The stage is rotatable and includes a substrate heating means, the pressure adjusting means includes a vacuum line connected to the chamber, two or more pumps for adjusting the pressure in the chamber through the vacuum line, and a vacuum. It includes a throttling valve installed in the line to keep the pressure in the chamber constant, a trap for filtering impurities in the vacuum line, and an ion gauge for measuring the pressure in the chamber.
【００１１】前記他の目的を達成するために本発明は、
基板上に化学化合物の薄膜を蒸着する方法において、前
駆体溶液を用意する段階と、密閉されたチャンバ内に基
板を用意し、前記チャンバを所定の圧力で保つ段階と、
前記前駆体溶液を液滴噴霧装置に移送する段階と、前記
移送された前駆体溶液を一定の温度で調節する段階と、
前記液滴噴霧装置で前記移送された前駆体溶液を液滴に
変換させる段階と、前記液滴を前記チャンバ内に注入さ
せて前記基板上に液滴を蒸着させる段階と、前記蒸着さ
れた液滴を加熱乾燥させ前記基板上に薄膜を形成する段
階よりなることを特徴とする薄膜蒸着方法を提供する。[0011] In order to achieve the other object, the present invention provides:
In a method of depositing a thin film of a chemical compound on a substrate, a step of preparing a precursor solution, a step of preparing the substrate in a closed chamber and maintaining the chamber at a predetermined pressure,
Transferring the precursor solution to a droplet spraying device, adjusting the transferred precursor solution at a constant temperature,
Converting the transferred precursor solution into droplets by the droplet spraying device, injecting the droplets into the chamber to deposit the droplets on the substrate, and the deposited liquid. A thin film deposition method comprising the steps of heating and drying the droplets to form a thin film on the substrate.
【００１２】前記チャンバの圧力を２００〜７００Ｔｏ
ｒｒに調節し、前記基板上に液滴を注入する段階で前記
基板を回転させる。The chamber pressure is set to 200 to 700 To.
Adjusting to rr, the substrate is rotated at the step of injecting a droplet onto the substrate.
【００１３】前記薄膜を形成する段階後に前記薄膜を熱
処理する段階を含み、前記熱処理は５５０〜８５０℃の
加熱炉で行う。After the step of forming the thin film, the step of heat treating the thin film is included, and the heat treatment is performed in a heating furnace at 550 to 850 ° C.
【００１４】前記薄膜は強誘電体膜または超伝導薄膜で
あり、前記強誘電体膜はＰｂＴｉＯ3 、Ｐｂ（Ｔｉ、Ｚ
ｒ）Ｏ3 、（Ｐｂ、Ｌａ）ＴｉＯ3 、（Ｐｂ、Ｌａ）
（Ｔｉ、Ｚｒ）Ｏ3 、ＢａＴｉＯ3 、ＳｒＴｉＯ3 、
（Ｂａ、Ｓｒ）ＴｉＯ3 、ＢｉＳｒ2 Ｔａ2 Ｏ9 及びＢ
ｉＳｒ2 Ｎｂ2 Ｏ9 の中から選択された何れか１つであ
り、前記超伝導薄膜はＹＢａ2 Ｃｕ3 Ｏ7-x である。The thin film is a ferroelectric film or a superconducting thin film, and the ferroelectric film is made of PbTiO 3 , Pb (Ti, Z).
r) O 3 , (Pb, La) TiO 3 , (Pb, La)
(Ti, Zr) O 3 , BaTiO 3 , SrTiO 3 ,
(Ba, Sr) TiO 3 , BiSr 2 Ta 2 O 9 and B
Any one selected from iSr 2 Nb 2 O 9 and the superconducting thin film is YBa 2 Cu 3 O 7-x .
【００１５】また、本発明は前駆体溶液を液滴化学蒸着
法により基板上にバリウム−ストロンチウム−チタン酸
塩薄膜を形成する方法において、前記前駆体溶液はバリ
ウムとストロンチウムの有機金属溶質等を各々有機溶媒
等に混合して有機金属溶液を形成する段階と、前記有機
金属溶液にチタンアルコキシド化合物を混合する段階よ
りなることを特徴とするバリウム−ストロンチウム−チ
タン酸塩薄膜形成方法を提供する。Further, the present invention provides a method of forming a barium-strontium-titanate thin film on a substrate by a precursor solution using a droplet chemical vapor deposition method, wherein the precursor solution contains barium and strontium organometallic solutes, respectively. There is provided a method for forming a barium-strontium-titanate thin film, which comprises the steps of mixing with an organic solvent or the like to form an organometallic solution and mixing the organometallic solution with a titanium alkoxide compound.
【００１６】前記チタンアルコキシド化合物はＴｉ（Ｏ
Ｃ2 Ｈ5 ）4 、Ｔｉ（ＯＣ3 Ｈ7 ）4 、Ｔｉ（ＯＣ4 Ｈ
9 ）4 、Ｔｉ（ＯＣ5 Ｈ11）4 及びＴｉ（ＯＣＨ3 ＯＣ
2 Ｈ5 ）4 の中から選択された何れか１つであり、前記
有機溶媒等は酢酸及び２−メトキシエタノールや酢酸及
びアセチルアセトンである。The titanium alkoxide compound is Ti (O
C 2 H 5 ) 4 , Ti (OC 3 H 7 ) 4 , Ti (OC 4 H
9 ) 4 , Ti (OC 5 H 11 ) 4 and Ti (OCH 3 OC
It is any one selected from 2 H 5 ) 4 , and the organic solvent and the like are acetic acid and 2-methoxyethanol, acetic acid and acetylacetone.
【００１７】前記有機金属溶液を形成する段階後に前記
有機金属溶液に炭素数の大きな有機溶媒を希釈する段階
をさらに具備し、前記炭素数の大きな有機溶媒は２−メ
トキシエタノール、ベンゼン、１−ブタノール及び１−
プロパノールの中から選択された何れか１つである。The method further comprises the step of diluting an organic solvent having a large carbon number into the organic metal solution after forming the organic metal solution, wherein the organic solvent having a large carbon number is 2-methoxyethanol, benzene, 1-butanol. And 1-
It is any one selected from propanol.
【００１８】前記チタンアルコキシド化合物の混合時ま
たは混合後に有機金属溶質の反応を促進させるために前
記有機金属溶液に付加剤を添加する段階をさらに具備
し、前記付加剤はＤＭＦ（dimetylformamide）やエチレ
ングリコール（ethylene glycol ）を利用する。The method further comprises the step of adding an additive to the organometallic solution in order to accelerate the reaction of the organometallic solute during or after the titanium alkoxide compound is mixed, and the additive is DMF (dimetylformamide) or ethylene glycol. Use (ethylene glycol).
【００１９】本発明によれば、金属薄膜の組成制御が易
く、常温で薄膜を形成しうる。According to the present invention, the composition of the metal thin film can be easily controlled and the thin film can be formed at room temperature.
【００２０】[0020]
【発明の実施の形態】以下、添付した図面を参照して、
本発明の一実施の形態を説明する。BRIEF DESCRIPTION OF THE DRAWINGS FIG.
An embodiment of the present invention will be described.
【００２１】図１は、本発明を適用した薄膜蒸着装置の
概略図である。この薄膜蒸着装置は前駆体溶液が盛られ
ている貯蔵槽１と、前記前駆体溶液を移送させる移送手
段３、例えばポンプと、前記移送された前駆体溶液の温
度を一定にし、前記移送された前駆体溶液を超音波を利
用して液滴に変換させる液滴噴霧装置（atomizer）５
と、質量流速制御器７により流量が制御された運搬気体
により液滴が流入されるチャンバ９と、前記チャンバ内
に基板８が置かれるステージ１１と、前記チャンバ９の
圧力を調節するための圧力調節手段１８と、前記液滴噴
霧装置５の水位を調節する水位調節器２１と、前記基板
８に蒸着される薄膜の厚さをモニタリングする厚さモニ
タ部２３と、前記水位調節器２１と厚さモニタ部２３を
制御するコンピューター部２５で構成されている。図１
で、部材番号６はエアーバルブを示す。FIG. 1 is a schematic view of a thin film deposition apparatus to which the present invention is applied. In this thin film deposition apparatus, a storage tank 1 in which a precursor solution is placed, a transfer means 3 for transferring the precursor solution, for example, a pump, and a temperature of the transferred precursor solution are kept constant and transferred. Droplet atomizer 5 that transforms the precursor solution into droplets using ultrasonic waves
A chamber 9 into which droplets are introduced by a carrier gas whose flow rate is controlled by the mass flow rate controller 7, a stage 11 on which a substrate 8 is placed in the chamber, and a pressure for adjusting the pressure in the chamber 9. Adjusting means 18, a water level adjuster 21 for adjusting the water level of the droplet spraying device 5, a thickness monitor 23 for monitoring the thickness of the thin film deposited on the substrate 8, the water level adjuster 21 and the thickness. The monitor unit 23 includes a computer unit 25 that controls the monitor unit 23. FIG.
The member number 6 indicates an air valve.
【００２２】前記液滴噴霧装置５は複数の振動子が付着
されていて、所望の液滴の大きさを得るために相異なる
振動子を選んで作動させうる。液滴発生時の液滴の大き
さと振動子の振動数間の理論的な関係は次の式で知られ
ている。A plurality of vibrators are attached to the droplet spraying device 5, and different vibrators can be selected and operated in order to obtain a desired droplet size. The theoretical relationship between the size of a droplet when it is generated and the frequency of the oscillator is known by the following equation.
【００２３】 液滴平均直径＝［σ／（ρＬ×ｆ2 ）］1/3 ここで、ｆは振動数であり、σとρＬは各々前駆体溶液
の表面張力と密度を示す。上の式は振動数１２ＫＨｚ〜
３ＭＨｚの領域で有効である。Droplet average diameter = [σ / (ρL × f 2 )] 1/3 where f is the frequency, and σ and ρL are the surface tension and density of the precursor solution, respectively. The above formula is frequency 12kHz ~
It is effective in the 3 MHz region.
【００２４】チャンバ９の上部に液滴が導入される部分
６はシャワーヘッド形態のノズルよりなり、必要に応じ
て他の形態のノズルで交替しうる。また、チャンバ９の
上部に紫外線領域のエネルギーを利用して基板８に蒸着
された液滴等の膜としての転換反応を促進させるように
光エネルギーソース２７、例えば紫外線ランプが設置さ
れている。前記紫外線ランプは環形で構成し、基板全体
に紫外線が照射されるようにしうる。The portion 6 into which liquid drops are introduced is formed of a shower head type nozzle, and may be replaced by another type of nozzle as required. Further, a light energy source 27, for example, an ultraviolet lamp, is installed above the chamber 9 so as to promote the conversion reaction as a film of droplets or the like deposited on the substrate 8 by utilizing the energy in the ultraviolet region. The ultraviolet lamp may have a ring shape so that the entire substrate is irradiated with ultraviolet rays.
【００２５】基板８が置かれる移動ステージ１１は回転
でき、基板加熱手段を具備して蒸着過程から基板８に到
達する液滴の流れが最大限の対称性を保てる。また、ス
テージ１１は基板８を加熱するのでチャンバ９内で加熱
乾燥過程を同時に行える。The moving stage 11 on which the substrate 8 is placed can be rotated, and a substrate heating means is provided so that the flow of liquid droplets reaching the substrate 8 from the deposition process can maintain maximum symmetry. In addition, since the stage 11 heats the substrate 8, the heating and drying process can be simultaneously performed in the chamber 9.
【００２６】前記圧力調節手段１８は真空ライン１２
と、チャンバ内の圧力を一定に保たせるスロットリング
バルブ１３と、不純物をフィルタリングするトラップ１
５と、前記チャンバ内の圧力を調節する拡散ポンプ１７
及びフォアポンプ（fore pump）１９と、圧力を測定す
るイオンゲージ１４で構成される。前記真空ライン１２
は液滴の流れがチャンバ９内部で対称を成すようにステ
ージ１１の中心軸に対して対称を成す２つ以上の真空ポ
ート１６を具備し、真空ライン１２を通して運搬気体と
未蒸着された液滴等が抜出す。The pressure adjusting means 18 is a vacuum line 12
A throttling valve 13 for keeping the pressure in the chamber constant, and a trap 1 for filtering impurities.
5 and a diffusion pump 17 for adjusting the pressure in the chamber
And a fore pump 19 and an ion gauge 14 for measuring pressure. The vacuum line 12
Is equipped with two or more vacuum ports 16 that are symmetrical with respect to the central axis of the stage 11 so that the flow of the droplets is symmetrical within the chamber 9, and the carrier gas and the undeposited droplets are conveyed through the vacuum line 12. And so on.
【００２７】ここで、図１に示した薄膜形成装置を利用
した薄膜形成方法を説明する。Here, a thin film forming method using the thin film forming apparatus shown in FIG. 1 will be described.
【００２８】具体的に、所望の組成の薄膜を蒸着するた
めに前記前駆体溶液を貯蔵槽１に入れる。引続き、蒸着
させるための基板８をチャンバ９に位置させて拡散ポン
プ１７及びフォアポンプ１９を使用して十分に排気して
高真空状態、例えば１０-6Ｔｏｒｒを保った後運搬気体
を以ってチャンバの圧力を２００〜７００Ｔｏｒｒに合
わせる。Specifically, the precursor solution is placed in the storage tank 1 to deposit a thin film having a desired composition. Subsequently, the substrate 8 for vapor deposition is placed in the chamber 9 and sufficiently evacuated using the diffusion pump 17 and the fore pump 19 to maintain a high vacuum state, for example, 10 −6 Torr, and then a carrier gas is used. Adjust the chamber pressure to 200-700 Torr.
【００２９】次いで、ステージ８の回転速度を１０〜６
００ｒｐｍで調節し、液滴噴霧装置５を可動させると貯
蔵槽１の前駆体溶液が一定量ほど液滴噴霧装置に移送さ
れる。次いで、移送された前駆体溶液の温度を３０〜７
０℃で調節しながら前記液滴噴霧装置５を利用して液滴
を発生させた後、移送させて１〜２０分の間基板８に蒸
着する。引続き、液滴の導入を遮断させた状態で徐々に
減圧して前記基板８に蒸着された液滴を乾燥させて１２
０〜５００℃で加熱する。このような液滴の導入及び乾
燥を２〜５回反復後チャンバ９の圧力を常圧に還元させ
て基板８を取出した後５５０〜８５０℃の加熱炉で後続
熱処理過程を行う。こうして、基板８上に得られる厚さ
は３００〜３０００Åである。Next, the rotation speed of the stage 8 is set to 10 to 6
When the droplet spraying device 5 is moved by adjusting at 00 rpm, a certain amount of the precursor solution in the storage tank 1 is transferred to the droplet spraying device. Then, the temperature of the transferred precursor solution is set to 30 to 7
The liquid droplets are generated by using the liquid droplet spraying device 5 while controlling at 0 ° C., and then the liquid droplets are transferred and deposited on the substrate 8 for 1 to 20 minutes. Subsequently, the pressure applied to the substrate 8 is gradually reduced while the introduction of the liquid droplets is blocked, and the liquid droplets deposited on the substrate 8 are dried.
Heat at 0-500 ° C. After repeating such introduction and drying of droplets 2 to 5 times, the pressure in the chamber 9 is reduced to normal pressure, the substrate 8 is taken out, and the subsequent heat treatment process is performed in a heating furnace at 550 to 850 ° C. Thus, the thickness obtained on the substrate 8 is 300-3000Å.
【００３０】本発明の液滴化学蒸着法を利用する薄膜形
成装置によれば、高品質の強誘電体薄膜及び超伝導薄膜
のような複合化合物の薄膜を形成するに使用しうる。例
えばＰｂＴｉＯ3 、Ｐｂ（Ｔｉ、Ｚｒ）Ｏ3 、（Ｐｂ、
Ｌａ）ＴｉＯ3 、（Ｐｂ、Ｌａ）（Ｔｉ、Ｚｒ）Ｏ3 、
ＢａＴｉＯ3 、ＳｒＴｉＯ3 、（Ｂａ、Ｓｒ）Ｔｉ
Ｏ3 、ＢｉＳｒ2 Ｔａ2 Ｏ9 及びＢｉＳｒ2 Ｎｂ2 Ｏ9
のような強誘電体薄膜とＹＢａ2 Ｃｕ3 Ｏ7-x のような
超伝導薄膜を形成しうる。The thin film deposition apparatus using the droplet chemical vapor deposition method of the present invention can be used to form thin films of composite compounds such as ferroelectric thin films and superconducting thin films of high quality. For example, PbTiO 3 , Pb (Ti, Zr) O 3 , (Pb,
La) TiO 3 , (Pb, La) (Ti, Zr) O 3 ,
BaTiO 3 , SrTiO 3 , (Ba, Sr) Ti
O 3 , BiSr 2 Ta 2 O 9 and BiSr 2 Nb 2 O 9
And a superconducting thin film such as YBa 2 Cu 3 O 7-x can be formed.
【００３１】図２及び図３は本発明の一例としてバリウ
ム−ストロンチウム−チタン酸塩（（Ｂａ、Ｓｒ）Ｔｉ
Ｏ3 ）強誘電体薄膜の製造方法を説明するために示した
流れ図である。2 and 3 show an example of the present invention, barium-strontium-titanate ((Ba, Sr) Ti).
3 is a flow chart shown for explaining a method of manufacturing an O 3 ) ferroelectric thin film.
【００３２】まず、バリウム−ストロンチウム−チタン
酸塩（barium strontium titanate）の前駆体溶液を用
意する。バリウム有機金属溶質、例えばバリウムアセテ
ートと酢酸の有機溶媒を混合する（１０１段階）。スト
ロンチウム有機金属溶質、例えばストロンチウムアセテ
ートと２−メトキシエタノールの有機溶媒を混合する
（１０２段階）。１０１段階及び１０２段階の各混合物
を再び混合する（１０３段階）。１０１段階及び１０２
段階で、有機金属溶媒のバリウムとストロンチウムは有
機溶媒の温度１５〜６０℃、望ましくは３０〜４０℃で
１〜１０時間反応させ均一に溶かす。本実施例では有機
溶媒等を酢酸及び２−メトキシエタノールを使用した
が、酢酸及びアセチルアセトンも使用できる。First, a barium strontium titanate precursor solution is prepared. An organic solvent of barium organometallic solute such as barium acetate and acetic acid is mixed (step 101). A strontium organometallic solute, for example, strontium acetate and an organic solvent of 2-methoxyethanol are mixed (step 102). Each of the mixtures of steps 101 and 102 are mixed again (step 103). 101 steps and 102
In the step, barium and strontium as the organic metal solvent are uniformly dissolved by reacting at a temperature of the organic solvent of 15 to 60 ° C., preferably 30 to 40 ° C. for 1 to 10 hours. Although acetic acid and 2-methoxyethanol were used as the organic solvent in this example, acetic acid and acetylacetone can also be used.
【００３３】次いで、前記１０１段階と１０２段階の結
果物溶液を混合して有機金属溶液を用意する（１０４段
階）。ここで、１０４段階の有機金属溶液は０．５０〜
０．７０モル／リットルのバリウムと液は０．３０〜
０．５０モル／リットルのストロンチウムを含む。次い
で、必要であれば（１０５段階）、２−メトキシエタノ
ール、ベンゼン、１−ブタノールまたは１−プロパノー
ルのように炭素の数の大きな有機溶媒１０７を１０４段
階の有機金属溶液と１〜１０時間ほど混合して希釈させ
る（１０９段階）。Next, the resultant solutions of steps 101 and 102 are mixed to prepare an organometallic solution (step 104). Here, the organometallic solution of 104 steps is 0.50 to
0.70 mol / liter of barium and liquid is 0.30
It contains 0.50 mol / l strontium. Then, if necessary (step 105), an organic solvent 107 having a large carbon number such as 2-methoxyethanol, benzene, 1-butanol or 1-propanol is mixed with the organometallic solution of step 104 for about 1 to 10 hours. To dilute (step 109).
【００３４】その後、必要であれば（１１０段階）、基
板の性質によりアルコール、アセチルアセトネート（ac
etylacetonate ）系塩等他の有機溶媒１１１を今まで備
えられた有機金属溶液と沸騰点以下の温度で１〜１０時
間ほど反応させる（１１２段階）。このように形成され
た有機金属溶液に反応性の大きなチタンアルコキシド化
合物を混合した後１〜２０時間ほど反応させる。この
際、使用されるチタンアルコキシド化合物の具体的な例
としてはＴｉ（ＯＣ2 Ｈ5 ）4 、Ｔｉ（ＯＣ
3 Ｈ7 ）4 、Ｔｉ（ＯＣ4 Ｈ9 ）4 、Ｔｉ（ＯＣ
5 Ｈ11）4 、Ｔｉ（ＯＣＨ3 ＯＣ2Ｈ5 ）4 等がある。After that, if necessary (step 110), alcohol, acetylacetonate (ac
Etylacetonate) -based salt or another organic solvent 111 is reacted with the organometallic solution provided so far at a temperature below the boiling point for 1 to 10 hours (step 112). The organometallic solution thus formed is mixed with a highly reactive titanium alkoxide compound and then reacted for 1 to 20 hours. In this case, specific examples of the titanium alkoxide compound used include Ti (OC 2 H 5 ) 4 and Ti (OC
3 H 7 ) 4 , Ti (OC 4 H 9 ) 4 , Ti (OC
5 H 11 ) 4 , Ti (OCH 3 OC 2 H 5 ) 4 and the like.
【００３５】次いで、必要により（１１４段階）特に有
機金属溶質等の間に反応性を高めるために付加剤を前記
チタンアルコキシド化合物の混合時または混合後に０．
１〜５重量％添加しうる（１１５段階）。付加剤として
はＤＭＦ、エチレングリコールがある。このようにバリ
ウム−ストロンチウム−チタン酸塩の前駆体溶液を用意
する（１１７段階）。次いで、前記図１に示したように
薄膜形成装置を利用して前記前駆体溶液の液滴を形成し
た後（１１９段階）これを基板に２００〜７００Ｔｏｒ
ｒで１〜２０分間蒸着する（１２１段階）。引続き、前
記蒸着された液滴を乾燥させて（１２３段階）薄膜を形
成した後（１２５段階）、酸素雰囲気で熱処理を６００
〜８００℃で約１時間実施する（１２７段階）。前記液
滴の蒸着及び乾燥は繰返して行う（１２６段階）。Next, if necessary (step 114), an addition agent is added to the titanium alkoxide compound for the purpose of enhancing the reactivity, especially during the organometallic solute or the like, at or after mixing with the titanium alkoxide compound.
1 to 5% by weight may be added (step 115). Examples of the additive include DMF and ethylene glycol. Thus, a barium-strontium-titanate precursor solution is prepared (step 117). Then, as shown in FIG. 1, a droplet of the precursor solution is formed using the thin film forming apparatus (step 119), and the precursor solution is applied to the substrate at 200 to 700 Tor.
Vapor deposition is performed at r for 1 to 20 minutes (step 121). Subsequently, the deposited droplets are dried (step 123) to form a thin film (step 125), and then heat-treated at 600 in an oxygen atmosphere.
It is carried out at about 800 ° C. for about 1 hour (step 127). The deposition and drying of the droplets are repeated (step 126).
【００３６】[0036]
【発明の効果】以上、前述した本発明の液滴化学蒸着法
を利用する薄膜形成装置及びこれを利用した薄膜形成方
法は従来の薄膜形成方法の問題点を解決することにより
金属物質の組成制御が易く、常温の条件で薄膜を形成し
うる。As described above, the thin film forming apparatus using the droplet chemical vapor deposition method of the present invention and the thin film forming method using the same solve the problems of the conventional thin film forming method to control the composition of the metal substance. Easily, and a thin film can be formed at room temperature.
【００３７】また、本発明のバリウム−ストロンチウム
−チタン酸塩有機金属の前駆体溶液は使用される有機金
属物質の毒性が弱く、有機金属濃度を高めて蒸着速度が
速くでき、液滴化学蒸着法に必須的な超音波噴霧能力が
抜群であり、常温蒸着条件にもってこいの長所を有して
いて、蒸着された薄膜の組成調節及び再現性が素晴らし
く、大面積の基板でも厚さの均一性が保たせる。In addition, the barium-strontium-titanate organometallic precursor solution of the present invention has a low toxicity of the organometallic substance used, and can increase the organometallic concentration to increase the vapor deposition rate. It has an excellent ultrasonic spraying capability, which is essential for room temperature vapor deposition conditions.It has excellent composition control and reproducibility of the vapor deposited thin film, and it has a uniform thickness even on a large substrate. To keep.
【００３８】本発明は前記実施例に限定されなく、多く
の変形が本発明の技術的思想内で当分野で通常の知識を
有する者により可能であることは明白である。The present invention is not limited to the above embodiments, and it is obvious that many modifications can be made by a person having ordinary skill in the art within the technical idea of the present invention.
【図１】 本発明による薄膜蒸着装置を説明するための
概略図である。FIG. 1 is a schematic diagram for explaining a thin film deposition apparatus according to the present invention.
【図２】 本発明による薄膜蒸着方法を説明するために
示した流れ図である。FIG. 2 is a flow chart shown for explaining a thin film deposition method according to the present invention.
【図３】 上記図２に続く薄膜蒸着方法を説明するため
の流れ図である。FIG. 3 is a flowchart for explaining the thin film deposition method following FIG.
【符号の説明】 １…貯蔵槽 ３…移送手段 ５…液滴噴霧装置 ６…エアーバルブ ７…質量流速制御器 ８…基板 ９…チャンバ １１…ステージ １８…圧力調節手段 ２１…水位調節器 ２３…厚さモニタ部 ２５…コンピューター[Explanation of Codes] 1 ... Storage tank 3 ... Transfer means 5 ... Droplet spraying device 6 ... Air valve 7 ... Mass flow rate controller 8 ... Substrate 9 ... Chamber 11 ... Stage 18 ... Pressure adjusting means 21 ... Water level adjuster 23 ... Thickness monitor 25 ... Computer
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 21/8242 (72)発明者 鄭 鉉 振 大韓民国大田廣域市儒城區九城洞373−１ 番地 カイスト化工科内Continuation of the front page (51) Int.Cl. 6 Identification number Internal reference number FI Technical indication location H01L 21/8242 (72) Inventor Zheng Hyun Zhen 373-1 No. 37, Kwong-dong, Yuseong-gu, Daejeon, South Korea Within the department
Claims (26)
置において、 前駆体溶液が盛られる貯蔵槽と、 前記前駆体溶液を移送させる移送手段と、 前記移送された前駆体溶液の温度を調節し、前記移送さ
れた前駆体溶液を液滴に変換させる液滴噴霧装置と、 前記液滴噴霧装置に連結されたノズルを通して前記液滴
が注入されるチャンバと、 前記チャンバ内に前記基板が置かれるステージと、 前記チャンバの圧力を調節するための圧力調節手段より
なり、前記基板上に前記注入された液滴を蒸着させて薄
膜を形成することを特徴とする薄膜蒸着装置。1. An apparatus for depositing a thin film of a chemical compound on a substrate, a storage tank in which a precursor solution is placed, a transfer means for transferring the precursor solution, and a temperature of the transferred precursor solution. A droplet spraying device for converting the transferred precursor solution into droplets, a chamber into which the droplets are injected through a nozzle connected to the droplet spraying device, and the substrate placed in the chamber. A thin film deposition apparatus comprising: a stage to be placed and a pressure adjusting means for adjusting the pressure of the chamber, and forming a thin film by depositing the injected droplets on the substrate.
る質量流速制御器が連結されていることを特徴とする請
求項１に記載の薄膜蒸着装置。2. The thin film deposition apparatus according to claim 1, wherein a mass flow rate controller capable of controlling a carrier gas is connected to the droplet spraying device.
注入された液滴が膜としての反応が促進されるように光
エネルギーソースが設けられていることを特徴とする請
求項１に記載の薄膜蒸着装置。3. The light energy source according to claim 1, wherein an optical energy source is provided above the chamber so as to promote the reaction of the injected droplets as a film on the substrate. Thin film deposition equipment.
であることを特徴とする請求項３に記載の薄膜蒸着装
置。4. The thin film deposition apparatus of claim 3, wherein the light energy source is an ultraviolet lamp.
調節する水位調節器が連結されていることを特徴とする
請求項１に記載の薄膜蒸着装置。5. The thin film deposition apparatus according to claim 1, wherein a water level controller for controlling the water level of the precursor solution is connected to the droplet spraying device.
をモニターするモニター部を具備することを特徴とする
請求項１に記載の薄膜蒸着装置。6. The thin film deposition apparatus according to claim 1, further comprising a monitor unit for monitoring a thickness of a thin film deposited in the chamber.
を含むことを特徴とする請求項１に記載の薄膜蒸着装
置。7. The thin film deposition apparatus of claim 1, wherein the stage is rotatable and includes a substrate heating unit.
された真空ラインと、前記チャンバ内の圧力を前記真空
ラインを通して調節する２つ以上のポンプと、真空ライ
ン中に設置されてチャンバ内の圧力を一定に保たせるス
ロットリングバルブと、前記真空ラインの不純物をフィ
ルタリングするトラップと、前記チャンバの圧力を測る
イオンゲージよりなることを特徴とする請求項１に記載
の薄膜蒸着装置。8. The pressure adjusting means comprises a vacuum line connected to the chamber, two or more pumps for adjusting the pressure inside the chamber through the vacuum line, and a pressure inside the chamber installed in the vacuum line. 2. The thin film deposition apparatus according to claim 1, further comprising a throttling valve that keeps the temperature constant, a trap that filters impurities in the vacuum line, and an ion gauge that measures the pressure in the chamber.
法において、 前駆体溶液を用意する段階と、 密閉されたチャンバ内に基板を用意し、前記チャンバを
所定の圧力で保つ段階と、 前記前駆体溶液を液滴噴霧装置に移送する段階と、 前記移送された前駆体溶液を一定の温度で調節する段階
と、 前記液滴噴霧装置で前記移送された前駆体溶液を液滴に
変換させる段階と、 前記液滴を前記チャンバ内に注入させて前記基板上に液
滴を蒸着させる段階と、 前記蒸着された液滴を加熱乾燥させ前記基板上に薄膜を
形成する段階よりなることを特徴とする薄膜蒸着方法。9. A method of depositing a thin film of a chemical compound on a substrate, comprising: providing a precursor solution; providing the substrate in a closed chamber; and maintaining the chamber at a predetermined pressure, Transferring the precursor solution to a droplet spray device, adjusting the transferred precursor solution at a constant temperature, and converting the transferred precursor solution into droplets by the droplet spray device. The steps of injecting the droplets into the chamber to deposit the droplets on the substrate, and heating and drying the deposited droplets to form a thin film on the substrate. And a thin film deposition method.
Ｔｏｒｒに調節することを特徴とする請求項９に記載の
薄膜蒸着方法。10. The pressure in the chamber is 200-700.
The thin film deposition method according to claim 9, wherein the thin film deposition method is adjusted to Torr.
記基板を回転させることを特徴とする請求項９に記載の
薄膜蒸着方法。11. The thin film deposition method of claim 9, wherein the substrate is rotated in the step of injecting the liquid droplets onto the substrate.
を熱処理する段階を含むことを特徴とする請求項９に記
載の薄膜蒸着方法。12. The method of claim 9, further comprising the step of heat treating the thin film after forming the thin film.
炉で行うことを特徴とする請求項１２に記載の薄膜蒸着
方法。13. The thin film deposition method according to claim 12, wherein the heat treatment is performed in a heating furnace at 550 to 850 ° C.
徴とする請求項９に記載の薄膜蒸着方法。14. The thin film deposition method according to claim 9, wherein the thin film is a ferroelectric film.
徴とする請求項９に記載の薄膜蒸着方法。15. The thin film deposition method according to claim 9, wherein the thin film is a superconducting thin film.
（Ｔｉ、Ｚｒ）Ｏ3、（Ｐｂ、Ｌａ）ＴｉＯ3 、（Ｐ
ｂ、Ｌａ）（Ｔｉ、Ｚｒ）Ｏ3 、ＢａＴｉＯ3、ＳｒＴ
ｉＯ3 、（Ｂａ、Ｓｒ）ＴｉＯ3 、ＢｉＳｒ2 Ｔａ2 Ｏ
9 及びＢｉＳｒ 2 Ｎｂ2 Ｏ9 の中から選択された何れか
１つであることを特徴とする請求項１４に記載の薄膜蒸
着方法。16. The ferroelectric film is PbTiO.sub.3.Three, Pb
(Ti, Zr) OThree, (Pb, La) TiOThree, (P
b, La) (Ti, Zr) OThree, BaTiOThree, SrT
iOThree, (Ba, Sr) TiOThree, BiSrTwoTaTwoO
9And BiSr TwoNbTwoO9Any one selected from
15. The thin film vapor according to claim 14, wherein the number is one.
How to wear.
7-x であることを特徴とする請求項１５に記載の薄膜蒸
着方法。17. The superconducting thin film is YBa 2 Cu 3 O.
The thin film deposition method according to claim 15, wherein the thin film deposition method is 7-x .
板上にバリウム−ストロンチウム−チタン酸塩薄膜を形
成する方法において、 前記前駆体溶液はバリウムとストロンチウムの有機金属
溶質等を各々有機溶媒等に混合して有機金属溶液を形成
する段階と、前記有機金属溶液にチタンアルコキシド化
合物を混合する段階よりなることを特徴とするバリウム
−ストロンチウム−チタン酸塩薄膜形成方法。18. A method of forming a barium-strontium-titanate thin film on a substrate by a precursor solution using a droplet chemical vapor deposition method, wherein the precursor solution is an organic metal solute of barium and strontium, etc. A method of forming a barium-strontium-titanate thin film, comprising the steps of: mixing with an organic metal solution to form an organometallic solution; and mixing a titanium alkoxide compound with the organometallic solution.
（ＯＣ2 Ｈ5 ）4 、Ｔｉ（ＯＣ3 Ｈ7 ）4 、Ｔｉ（ＯＣ
4 Ｈ9 ）4 、Ｔｉ（ＯＣ5 Ｈ11）4 及びＴｉ（ＯＣＨ3
ＯＣ2 Ｈ5 ）4 の中から選択された何れか１つであるこ
とを特徴とする請求項１８に記載のバリウム−ストロン
チウム−チタン酸塩薄膜形成方法。19. The titanium alkoxide compound is Ti
(OC 2 H 5 ) 4 , Ti (OC 3 H 7 ) 4 , Ti (OC
4 H 9 ) 4 , Ti (OC 5 H 11 ) 4 and Ti (OCH 3
Barium claim 18, characterized in that OC 2 H 5) is any one selected from among 4 - Strontium - titanate thin film forming method.
シエタノールであることを特徴とする請求項１８に記載
のバリウム−ストロンチウム−チタン酸塩薄膜形成方
法。20. The method for forming a barium-strontium-titanate thin film according to claim 18, wherein the organic solvent is acetic acid and 2-methoxyethanol.
セトンであることを特徴とする請求項１８に記載のバリ
ウム−ストロンチウム−チタン酸塩薄膜形成方法。21. The method for forming a barium-strontium-titanate thin film according to claim 18, wherein the organic solvent is acetic acid and acetylacetone.
前記有機金属溶液に炭素数の大きな有機溶媒を希釈する
段階をさらに具備することを特徴とする請求項１８に記
載のバリウム−ストロンチウム−チタン酸塩薄膜形成方
法。22. The barium-strontium-titanate acid according to claim 18, further comprising a step of diluting the organic metal solution with an organic solvent having a large carbon number after the step of forming the organic metal solution. Salt thin film forming method.
トキシエタノール、ベンゼン、１−ブタノール及び１−
プロパノールの中から選択された何れか１つであること
を特徴とする請求項２２に記載のバリウム−ストロンチ
ウム−チタン酸塩薄膜形成方法。23. The organic solvent having a large carbon number is 2-methoxyethanol, benzene, 1-butanol and 1-butanol.
The method for forming a barium-strontium-titanate thin film according to claim 22, wherein the method is any one selected from propanol.
時または混合後に有機金属溶質の反応を促進させるため
に前記有機金属溶液に付加剤を添加する段階をさらに具
備することを特徴とする請求項１８に記載のバリウム−
ストロンチウム−チタン酸塩薄膜形成方法。24. The method according to claim 18, further comprising the step of adding an additive agent to the organic metal solution in order to accelerate the reaction of the organic metal solute during or after the mixing of the titanium alkoxide compound. Barium
Method for forming strontium-titanate thin film.
特徴とする請求項２４に記載のバリウム−ストロンチウ
ム−チタン酸塩薄膜形成方法。25. The method for forming a barium-strontium-titanate thin film according to claim 24, wherein the additive is DMF.
用することを特徴とする請求項２４に記載のバリウム−
ストロンチウム−チタン酸塩薄膜形成方法。26. The barium according to claim 24, wherein the additive is ethylene glycol.
Method for forming strontium-titanate thin film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR96P2080 | 1996-01-30 | ||
| KR1019960002080A KR970059323A (en) | 1996-01-30 | 1996-01-30 | Thin film deposition apparatus and thin film deposition method using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09213643A true JPH09213643A (en) | 1997-08-15 |
Family
ID=19450358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8243666A Withdrawn JPH09213643A (en) | 1996-01-30 | 1996-09-13 | Thin film depositing device and method for depositing thin film utilizing it |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH09213643A (en) |
| KR (1) | KR970059323A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001036030A (en) * | 1999-06-28 | 2001-02-09 | Hyundai Electronics Ind Co Ltd | Semiconductor device and its manufacture |
| US6825131B2 (en) | 2002-01-16 | 2004-11-30 | Murata Manufacturing Co., Ltd. | Method for forming dielectric thin film and dielectric thin film formed thereby |
| WO2019004299A1 (en) * | 2017-06-30 | 2019-01-03 | 株式会社シンクロン | Film forming device |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990073223A (en) * | 1999-06-23 | 1999-10-05 | 천웅기 | Thin film deposition system and process for fabrication of organic light-emitting devices |
| KR20020019753A (en) * | 2000-09-07 | 2002-03-13 | 이희영 | The method of synthesis of SNTO and LTO precursor solutions for making thin films for non-volatile memory device applications |
| US6729041B2 (en) * | 2000-12-28 | 2004-05-04 | Tokyo Electron Limited | Substrate processing apparatus and substrate processing method |
| KR100430104B1 (en) * | 2001-09-18 | 2004-05-03 | 디지웨이브 테크놀러지스 주식회사 | Vacuum plating apparatus and its plating method with linear plating and indirect heating |
| KR100418931B1 (en) * | 2001-12-19 | 2004-02-14 | 주식회사 하이닉스반도체 | Method for Forming of Electrode Material |
| KR100559792B1 (en) * | 2003-08-29 | 2006-03-15 | 한국과학기술원 | The method for producing thin film or powder array using liquid source misted chemical deposition process |
| JP4956939B2 (en) * | 2005-08-31 | 2012-06-20 | Ｔｄｋ株式会社 | Dielectric film and manufacturing method thereof |
| KR100805930B1 (en) * | 2006-09-27 | 2008-02-21 | 한국표준과학연구원 | A precursor vapor pressure measuring device for semiconductor manufacturing process and method thereof |
-
1996
- 1996-01-30 KR KR1019960002080A patent/KR970059323A/en not_active Application Discontinuation
- 1996-09-13 JP JP8243666A patent/JPH09213643A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001036030A (en) * | 1999-06-28 | 2001-02-09 | Hyundai Electronics Ind Co Ltd | Semiconductor device and its manufacture |
| US6825131B2 (en) | 2002-01-16 | 2004-11-30 | Murata Manufacturing Co., Ltd. | Method for forming dielectric thin film and dielectric thin film formed thereby |
| WO2019004299A1 (en) * | 2017-06-30 | 2019-01-03 | 株式会社シンクロン | Film forming device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR970059323A (en) | 1997-08-12 |
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