JP3221952B2 - Source gas generator for CVD - Google Patents
Source gas generator for CVDInfo
- Publication number
- JP3221952B2 JP3221952B2 JP00213593A JP213593A JP3221952B2 JP 3221952 B2 JP3221952 B2 JP 3221952B2 JP 00213593 A JP00213593 A JP 00213593A JP 213593 A JP213593 A JP 213593A JP 3221952 B2 JP3221952 B2 JP 3221952B2
- Authority
- JP
- Japan
- Prior art keywords
- raw material
- material solution
- vaporizer
- reaction chamber
- supply
- 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.)
- Expired - Lifetime
Links
- 239000002994 raw material Substances 0.000 claims description 144
- 239000006200 vaporizer Substances 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 239000012159 carrier gas Substances 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 description 96
- 239000000843 powder Substances 0.000 description 37
- 239000000758 substrate Substances 0.000 description 24
- 239000002887 superconductor Substances 0.000 description 23
- 239000010408 film Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- 238000003860 storage Methods 0.000 description 15
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000010409 thin film Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229910001882 dioxygen Inorganic materials 0.000 description 8
- 239000003595 mist Substances 0.000 description 8
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002902 organometallic compounds Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910002480 Cu-O Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 description 1
- 229910014454 Ca-Cu Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- -1 cyclopentadienyl compound Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
Landscapes
- 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)
- Inorganic Compounds Of Heavy Metals (AREA)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Vapour Deposition (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、化学気相蒸着法（以
下、ＣＶＤ法という）によって酸化物超電導体などの酸
化物材料を基材上に成膜するＣＶＤ装置に用いられる原
料ガス発生装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a raw material gas generator used in a CVD apparatus for forming an oxide material such as an oxide superconductor on a substrate by a chemical vapor deposition method (hereinafter referred to as a CVD method). It is about.
【０００２】[0002]
【従来の技術】近年、臨界温度（Ｔｃ）が液体窒素温度
（約７７Ｋ）よりも高い酸化物超電導体として、例え
ば、Ｙ-Ｂａ-Ｃｕ-Ｏ系、Ｂｉ-Ｓｒ-Ｃａ-Ｃｕ-Ｏ系、
Ｔｌ-Ｂａ-Ｃａ-Ｃｕ-Ｏ系などの酸化物超電導体が発見
されている。そして、これらの酸化物超電導体を電力輸
送、超電導マグネット、超電導デバイスなどの種々の超
電導機器に応用する目的で種々の研究が進められてい
る。このような酸化物超電導体の製造方法の１つとし
て、化学気相蒸着法（ＣＶＤ法）等の薄膜形成手段によ
って基材表面に酸化物超電導薄膜を成膜する方法が知ら
れている。この種の薄膜形成手段により形成した酸化物
超電導薄膜は、臨界電流密度（Ｊｃ）が大きく、優れた
超電導特性を発揮することが知られている。また、ＣＶ
Ｄ法のなかでも、金属錯体、金属アルコキシドなどの有
機金属化合物を原料として行なうＣＶＤ法は、成膜速度
が速く、短時間でより厚い膜を形成できる手段として注
目されている。2. Description of the Related Art In recent years, as oxide superconductors whose critical temperature (Tc) is higher than liquid nitrogen temperature (about 77 K), for example, Y-Ba-Cu-O-based, Bi-Sr-Ca-Cu-O-based ,
Oxide superconductors such as Tl—Ba—Ca—Cu—O have been discovered. Various studies have been conducted for the purpose of applying these oxide superconductors to various superconducting devices such as power transport, superconducting magnets and superconducting devices. As one of manufacturing methods of such an oxide superconductor, a method of forming an oxide superconducting thin film on a substrate surface by a thin film forming means such as a chemical vapor deposition method (CVD method) is known. It is known that an oxide superconducting thin film formed by this type of thin film forming means has a large critical current density (Jc) and exhibits excellent superconducting properties. Also, CV
Among the methods D, the CVD method using an organic metal compound such as a metal complex or a metal alkoxide as a raw material has attracted attention as a means capable of forming a thicker film in a short time in a short time.
【０００３】このようなＣＶＤ法による酸化物超電導体
の製造方法において通常使用される原料化合物として
は、酸化物超電導体を構成する各元素のβ-ジケトン化
合物やシクロペンタジエニル化合物などの有機金属錯体
が用いられ、例えば、Ｙ-Ｂａ-Ｃｕ-Ｏ系の酸化物超電
導体の製造用には、Ｙ，Ｂａ，Ｃｕの各元素のジピバロ
イルメタン（ＤＰＭ）錯体、即ち、Ｙ（ＤＰＭ）3、Ｂ
ａ（ＤＰＭ）2、Ｃｕ（ＤＰＭ）2などが使用されてい
る。これらの原料錯体は、原料気化装置で加熱気化させ
てキャリアガスとともに反応チャンバに送り込まれ、こ
の反応チャンバ内で化学反応を生じさせ、反応チャンバ
内に設置した基材の表面に反応生成物を堆積させること
で目的のＹ-Ｂａ-Ｃｕ-Ｏ系酸化物超電導体を得ること
ができる。As a raw material compound usually used in such a method for producing an oxide superconductor by the CVD method, an organic metal such as a β-diketone compound or a cyclopentadienyl compound of each element constituting the oxide superconductor is used. A complex is used. For example, for the production of a Y—Ba—Cu—O-based oxide superconductor, a dipivaloylmethane (DPM) complex of each element of Y, Ba, and Cu, ie, Y (DPM ) 3 , B
a (DPM) 2 , Cu (DPM) 2 and the like are used. These raw material complexes are heated and vaporized by a raw material vaporizer, sent into a reaction chamber together with a carrier gas, cause a chemical reaction in the reaction chamber, and deposit a reaction product on a surface of a base material installed in the reaction chamber. By doing so, the desired Y-Ba-Cu-O-based oxide superconductor can be obtained.
【０００４】図５は、従来、酸化物超電導体製造用のＣ
ＶＤ装置に用いられている粉末原料供給装置を示すもの
である。図５において、１は反応チャンバを示し、この
反応チャンバ１には真空ポンプ２と混合チャンバ３が接
続され、混合チャンバ３に気化器４を介してバブラ５と
粉末供給装置６とが接続されている。また、反応チャン
バ１と混合チャンバ３には、流量調整弁７、８を介して
酸素ガス供給源９が接続され、バブラ５と粉末供給装置
６にはそれぞれ流量調整弁１０、１１を介してアルゴン
ガスなどのキャリアガス供給源１２が接続されている。
前記反応チャンバ１の内部には基材１３を保持した基材
ホルダ１４が設けられ、基材ホルダ１４には加熱ヒータ
１５が内蔵されていて、基材１３を所望の温度に加熱で
きるように構成されている。FIG. 5 shows a conventional C for manufacturing an oxide superconductor.
1 shows a powder raw material supply device used in a VD device. 5, reference numeral 1 denotes a reaction chamber. A vacuum pump 2 and a mixing chamber 3 are connected to the reaction chamber 1. A bubbler 5 and a powder supply device 6 are connected to the mixing chamber 3 via a vaporizer 4. I have. An oxygen gas supply source 9 is connected to the reaction chamber 1 and the mixing chamber 3 through flow control valves 7 and 8, and the bubbler 5 and the powder supply device 6 are supplied with argon gas through flow control valves 10 and 11, respectively. A carrier gas supply source 12 such as a gas is connected.
A substrate holder 14 holding a substrate 13 is provided inside the reaction chamber 1, and a heater 15 is built in the substrate holder 14 so that the substrate 13 can be heated to a desired temperature. Have been.
【０００５】更に、前記粉末供給装置６の内部には、酸
化物超電導体を構成する元素の原料粉末１６が収納さ
れ、この原料粉末の上方に供給筒１７が設置され、この
供給筒１７の内部には、流量調整弁１１を介してキャリ
アガス供給源１２に接続された噴出管１７と気化器４に
接続された供給管１８が収納されている。前記噴出管１
７は、図６に示すように、その先端部１７ａからキャリ
アガスを原料粉末１６に吹き付けて舞い上がらせる作用
を行なうとともに、供給管１８は舞い上がった原料粉末
１６とともにキャリアガスを吸引し、これらの混合ガス
を気化器４に送る作用を行なう。Further, a raw material powder 16 of an element constituting the oxide superconductor is accommodated in the powder supply device 6, and a supply tube 17 is provided above the raw material powder. Accommodates an ejection pipe 17 connected to the carrier gas supply source 12 via the flow control valve 11 and a supply pipe 18 connected to the vaporizer 4. The jet tube 1
As shown in FIG. 6, a carrier gas is sprayed from a tip portion 17a of the carrier powder to the raw material powder 16 so that the raw material powder 16 rises, and a supply pipe 18 sucks the carrier gas together with the raw material powder 16 and mixes them. An operation of sending gas to the vaporizer 4 is performed.
【０００６】これらの作用により原料粉末をキャリアガ
スとともに気化器４に送ることができ、更に、気化器４
においてバブラ５から送られる原料ガスとともに混合し
て２３０℃程度に加熱することで原料を気化し、原料混
合ガスを形成し、反応チャンバ１に原料混合ガスを送る
ことができるようになっている。更に、反応チャンバ１
の内部は真空ポンプ２により所望の圧力に減圧されるよ
うになっているとともに、混合チャンバ３を介して原料
混合ガスが反応チャンバ１の内部に、また、酸素ガス供
給源９から酸素ガスが反応チャンバ１の内部にそれぞれ
供給されるようになっている。従って、基材１３上に反
応チャンバ１内の減圧雰囲気で原料混合ガスの組成に応
じた反応生成物を堆積させて成膜できるようになってい
る。[0006] By these actions, the raw material powder can be sent to the vaporizer 4 together with the carrier gas.
By mixing with the raw material gas sent from the bubbler 5 and heating to about 230 ° C., the raw material is vaporized to form a raw material mixed gas, and the raw material mixed gas can be sent to the reaction chamber 1. Further, the reaction chamber 1
Is reduced to a desired pressure by a vacuum pump 2, and a raw material mixed gas is supplied into the reaction chamber 1 via a mixing chamber 3, and oxygen gas is supplied from an oxygen gas supply source 9 to the reaction chamber 1. Each is supplied to the inside of the chamber 1. Accordingly, a reaction product according to the composition of the raw material mixed gas is deposited on the substrate 13 in a reduced-pressure atmosphere in the reaction chamber 1 to form a film.
【０００７】[0007]
【発明が解決しようとする課題】図５に示す装置を用い
て原料ガスを気化器４に送る場合、図６に示すように、
キャリアガスを噴出管１７の先端部１７ａから原料粉末
１６に向けて勢い良く噴き出すことになるが、ここで原
料粉末１６を舞い上がらせると、原料粉末１６の上方に
流動空間１６ａを生成することになり、この流動空間１
６ａ内に浮遊している粉末を供給管１８の先端部１８ａ
から吸い込んで排出することになる。ところが、この装
置にあっては、以上のような原理で原料粉末を輸送する
がゆえに、以下に説明する問題を有していた。When the raw material gas is sent to the vaporizer 4 using the apparatus shown in FIG. 5, as shown in FIG.
The carrier gas is spouted vigorously toward the raw material powder 16 from the distal end portion 17a of the jet pipe 17, but when the raw material powder 16 is sowed up here, a flow space 16a is generated above the raw material powder 16. , This flow space 1
The powder floating in the inside 6a is supplied to the tip 18a of the supply pipe 18.
Will be inhaled and discharged. However, this apparatus has the following problems because the raw material powder is transported according to the above principle.
【０００８】原料粉末の水分含有量などに起因する粘
り気に依存して流動空間１６ａにおける原料粉末の舞い
上がり量が変動するので、供給管１８を介して気化器４
に行なう原料粉末の供給量と供給速度の変動が大きく、
安定した原料粉末供給ができない欠点がある。 粒径の小さな原料粉末を輸送することから、供給管１
８はできる限り細く形成する必要があるが、供給管１８
を細く形成すると原料粉末で目詰まりを起こし易くなる
問題がある。特に、原料粉末が湿気を含んでいて粘り気
を有する場合、供給管１８の内部に原料粉末が付着して
堆積し、供給管１８の径を狭めて供給速度を不安定と
し、最悪の場合は目詰まりを引き起こす問題がある。 製造目的とする酸化物超電導体が多成分系の酸化物で
あるので、多くの場合、原料粉末は多成分の粉末の混合
体となる。従って全ての成分の粉末を供給管１８に均一
に送ることは困難であり、均一な成分を反応チャンバ１
に供給できない欠点がある。 原料粉末を収納している粉末供給装置６の容量には限
界があるので、長時間の連続成膜処理を行っていると、
原料粉末量が不足してくるが、原料粉末を追加するため
には成膜処理を一次中断して噴出管１７と供給管１８と
を粉末供給装置６から外す必要がある。よって長時間の
連続成膜処理ができなくなり、長尺の基材に成膜できな
くなる欠点がある。[0008] Since the amount of the raw material powder rising in the flow space 16a fluctuates depending on the viscosity due to the water content of the raw material powder, the vaporizer 4 is supplied through the supply pipe 18.
Large fluctuations in the supply amount and supply speed of the raw material powder to be performed,
There is a disadvantage that stable supply of raw material powder is not possible. Since the raw material powder with a small particle size is transported, the supply pipe 1
8 must be formed as thin as possible.
When the fine particles are formed finely, there is a problem that the raw material powder is apt to be clogged. In particular, when the raw material powder contains moisture and has stickiness, the raw material powder adheres and accumulates inside the supply pipe 18, and the diameter of the supply pipe 18 is narrowed to make the supply speed unstable. There is a problem that causes clogging. Since the oxide superconductor to be manufactured is a multi-component oxide, the raw material powder is often a mixture of multi-component powders. Therefore, it is difficult to uniformly send the powders of all the components to the supply pipe 18, and the uniform components are supplied to the reaction chamber 1.
Has the drawback that it cannot be supplied. Since the capacity of the powder supply device 6 containing the raw material powder is limited, if a long-term continuous film forming process is performed,
Although the amount of the raw material powder becomes insufficient, in order to add the raw material powder, it is necessary to temporarily suspend the film forming process and remove the ejection pipe 17 and the supply pipe 18 from the powder supply device 6. Therefore, there is a disadvantage that a long-time continuous film forming process cannot be performed, and a film cannot be formed on a long base material.
【０００９】また、前記ＣＶＤ装置に原料を供給する装
置として、原料粉末を用いる装置ではなく、原料溶液の
ミストを供給する装置が知られている。図７は、従来、
酸化物超電導体製造用のＣＶＤ装置に用いられている溶
液ミストの供給装置を示すものである。図７において、
符号２０は反応チャンバを示し、この反応チャンバ２０
には真空ポンプ２１が接続され、反応チャンバ２０の内
部には基材２２を保持した基材ホルダ２３が設けられ、
基材ホルダ２３には加熱ヒータが内蔵され、基材２２を
所望の温度に加熱できるように構成されている。反応チ
ャンバ２０の内上部には、基材２２に向けられた供給ノ
ズル２５が設けられ、この供給ノズル２５には酸素ガス
供給源２６と気化器２７とが並列接続されている。Further, as an apparatus for supplying a raw material to the CVD apparatus, an apparatus for supplying a mist of a raw material solution, not an apparatus using a raw material powder, is known. FIG.
1 shows a solution mist supply device used in a CVD device for manufacturing an oxide superconductor. In FIG.
Reference numeral 20 denotes a reaction chamber.
Is connected to a vacuum pump 21, and a substrate holder 23 holding a substrate 22 is provided inside the reaction chamber 20,
The substrate holder 23 has a built-in heater, and is configured to heat the substrate 22 to a desired temperature. A supply nozzle 25 directed toward the substrate 22 is provided in an upper portion of the reaction chamber 20, and an oxygen gas supply source 26 and a vaporizer 27 are connected to the supply nozzle 25 in parallel.
【００１０】前記気化器２７には、ニードル弁２８を組
み込んだ供給管２９を介してミスト発生装置３０が接続
され、このミスト発生装置３０には、アルゴンガスなど
のキャリア供給源３１と原液供給装置３２が接続されて
いる。ミスト発生装置３０は、原液３３を収納した容器
３４とこの容器３４の底部に設けられた超音波発振器３
５とから構成されている。また、原液供給装置３２は、
原液３３を収納した容器３６と、この容器３６および前
記容器３４に接続されたポンプ３７とから構成されてい
る。A mist generator 30 is connected to the vaporizer 27 via a supply pipe 29 in which a needle valve 28 is incorporated. The mist generator 30 has a carrier supply source 31 such as argon gas and a stock solution supply device. 32 are connected. The mist generator 30 includes a container 34 containing a stock solution 33 and an ultrasonic oscillator 3 provided at the bottom of the container 34.
And 5. In addition, the stock solution supply device 32
It comprises a container 36 containing a stock solution 33 and a pump 37 connected to the container 36 and the container 34.
【００１１】前記構成の装置にあっては、原液供給装置
３２から容器３４に供給した原液を超音波発振器３５で
ミスト状にした後、このミストをキャリアガスとともに
供給管２９を介して気化器２７に送って気化し、この後
に酸素ガスとともに反応チャンバ２０に送ることで基材
２２上に減圧雰囲気で原料混合ガスの組成に応じた反応
生成物を堆積させて成膜できるようになっている。In the apparatus having the above-described structure, the undiluted solution supplied from the undiluted solution supply device 32 to the container 34 is formed into a mist by the ultrasonic oscillator 35, and the mist is mixed with the carrier gas through the supply pipe 29 through the vaporizer 27. Then, by sending it to the reaction chamber 20 together with the oxygen gas, a reaction product corresponding to the composition of the raw material mixed gas is deposited on the substrate 22 in a reduced pressure atmosphere to form a film.
【００１２】この例の装置においては、先に説明した装
置で用いる原料粉末を使用しないので、原料粉末の性状
に起因する供給不安定性の問題を生じない利点はあるも
のの、以下に説明する問題があった。原液３３をミスト
化して気化器２７に送り出す場合に、それらの経路にお
ける圧力を考えた場合、反応チャンバ２０に接続された
気化器２７の内部は減圧雰囲気であり、原液３３が収納
された容器３４は大気圧にされている。従って気化器２
７と容器３４とを接続している接続管２９において、ニ
ードル弁２８を境界として、気化器２７側の供給管２９
の内部２９ａは減圧雰囲気であるのに対し、容器３４側
の供給管２９の内部２９ｂは大気圧となっている。この
ため、ミスト状にした原液３３の中の溶媒のみが選択的
に気化してしまい、特に、ニードル弁２８の部分で気化
していない原料の目詰まりを引き起こし易い欠点があっ
た。The apparatus of this example does not use the raw material powder used in the above-described apparatus, and thus has the advantage of not causing the problem of supply instability due to the properties of the raw material powder, but has the following problem. there were. When the undiluted solution 33 is mist-formed and sent to the vaporizer 27, considering the pressure in those paths, the interior of the vaporizer 27 connected to the reaction chamber 20 is in a depressurized atmosphere, and the container 34 in which the undiluted solution 33 is stored. Is at atmospheric pressure. Therefore vaporizer 2
In the connecting pipe 29 connecting the container 7 and the container 34, the supply pipe 29 on the vaporizer 27 side with the needle valve 28 as a boundary
Of the supply pipe 29 on the container 34 side is at atmospheric pressure. For this reason, only the solvent in the mist-like stock solution 33 is selectively vaporized, and in particular, there is a disadvantage that the raw material which has not been vaporized at the needle valve 28 is easily clogged.
【００１３】本発明は前記事情に鑑みてなされたもので
あり、原料溶液を細粒の液滴状にしてから気化して反応
チャンバに供給するとともに、供給経路の途中で目詰ま
りを生じさせることがなく、原料溶液の連続供給のでき
る新規な構造のＣＶＤ用原料ガス発生装置を提供するこ
とを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a method of forming a raw material solution into fine droplets, vaporizing the raw material solution, supplying the raw material solution to a reaction chamber, and causing clogging in the middle of a supply path. It is an object of the present invention to provide a CVD source gas generator having a novel structure capable of continuously supplying a source solution without any problem.
【００１４】[0014]
【課題を解決するための手段】請求項１記載の発明は前
記課題を解決するために、内部に原料溶液とキャリアガ
スが供給される容器状の供給器と、この供給器に毛細管
を介して接続され、減圧雰囲気の反応チャンバに接続さ
れる気化器とを具備し、前記毛細管の供給器内の先端部
の開口面を供給器内の原料溶液の液面上方近傍に配置し
てなるものである。According to the first aspect of the present invention, there is provided a container-like supply device in which a raw material solution and a carrier gas are supplied, and a capillary tube connected to the supply device. And a vaporizer connected to a reaction chamber in a reduced-pressure atmosphere, wherein an opening surface of a tip portion of the capillary in the supply device is disposed near a liquid level of the raw material solution in the supply device. is there.
【００１５】請求項２記載の発明は前記課題を解決する
ために、請求項１記載の毛細管の先端部に傾斜した開口
面を形成してなるものである。According to a second aspect of the present invention, in order to solve the above-mentioned problem, an inclined opening surface is formed at the tip of the capillary tube according to the first aspect.
【００１６】[0016]
【作用】内部に原料溶液とキャリアガスとが供給される
供給器と、この供給器に毛細管を介し接続され、減圧雰
囲気の反応チャンバに接続される気化器とを具備し、前
記毛細管の供給器内の先端部の開口面を供給器内の原料
溶液の液面上方近傍に配置したので、反応チャンバを減
圧雰囲気とした場合、毛細管から気化器に向かう急激な
キャリアガスの流れを自然に形成することができ、この
急激なキャリアガスの流れに沿って原料溶液を毛細管の
開口面で細粒の液滴状にして一定量気化器に供給するこ
とができる。よって気化器において細粒の液滴状の原料
溶液を確実に気化することができ、これにより反応チャ
ンバに所定量のキャリアガスと原料溶液気化ガスを確実
に供給することができ、反応チャンバ内の基材上に所望
の組成の反応生成物の薄膜を形成することができる。A supply device for supplying a raw material solution and a carrier gas therein; and a vaporizer connected to the supply device via a capillary tube and connected to a reaction chamber in a reduced-pressure atmosphere. When the reaction chamber is set to a reduced pressure atmosphere, a sharp flow of the carrier gas from the capillary to the vaporizer is naturally formed when the opening surface of the tip of the inside is arranged near the liquid level of the raw material solution in the supply device. According to the rapid flow of the carrier gas, the raw material solution can be supplied to the vaporizer in the form of fine droplets at the opening surface of the capillary in the form of fine droplets. Therefore, the raw material solution in the form of fine droplets can be reliably vaporized in the vaporizer, whereby a predetermined amount of the carrier gas and the raw material solution vaporized gas can be reliably supplied to the reaction chamber. A thin film of a reaction product having a desired composition can be formed on a substrate.
【００１７】毛細管の先端部を傾斜した開口面とするこ
とで、この傾斜した開口面からキャリアガスを原料溶液
とともに毛細管を介して気化器に送ることができる。傾
斜した開口面であると、開口面の下端部に原料溶液の液
面が位置した時点でキャリアガスの急激な流れにより原
料溶液が容易に細粒状になって気化器に送られる。ま
た、原料溶液の液面位置が多少上下に変動しても傾斜し
た開口面であると、原料溶液の毛細管への吸引作用が円
滑になされて細粒状の原料溶液が気化器に供給される。By forming the tip of the capillary tube with an inclined opening surface, the carrier gas can be sent from the inclined opening surface together with the raw material solution to the vaporizer via the capillary tube. With the inclined opening surface, the raw material solution is easily formed into fine particles by the rapid flow of the carrier gas and sent to the vaporizer when the liquid surface of the raw material solution is located at the lower end of the opening surface. In addition, if the opening surface is inclined even if the liquid surface position of the raw material solution fluctuates slightly up and down, the action of sucking the raw material solution into the capillary is performed smoothly, and the fine granular raw material solution is supplied to the vaporizer.
【００１８】[0018]
【実施例】以下、図面を参照して本発明の実施例につい
て説明する。図１は本発明に係る原料ガス発生装置を備
えたＣＶＤ装置の一例を示すもので、図中符号３０は原
料溶液３１が供給される容器状の供給器を示し、この供
給器３０の下部には、容器状の気化器３２が供給器３０
に対して上下になるように一体化されている。前記供給
器３０と気化器３２は隔壁３３により隔てられ、供給器
３１と気化器３２の内部には、隔壁３３を貫通して両者
を接続する毛細管３５が設けられ、この毛細管３５の先
端部３５ａは供給器３１内に収納されている原料溶液３
１の液面上方近傍に出され、その先端部３５ａには傾斜
した開口面３５ｂが形成されている。また、供給器３０
の上部には細径のニードル３６が挿通され、このニード
ル３６の下端部３６ａは、毛細管３５の先端部３５ａよ
りも下方に位置されている。前記毛細管３５は、例えば
内径数分の１ｍｍ程度の注射針状のものであり、前記ニ
ードル３６は、例えば内径１ｍｍ程度の注射針状のもの
である。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows an example of a CVD apparatus provided with a source gas generator according to the present invention. In the figure, reference numeral 30 denotes a container-like supply unit to which a source solution 31 is supplied. Means that the container-shaped vaporizer 32 is
It is integrated so as to be up and down. The supply device 30 and the vaporizer 32 are separated by a partition wall 33. Inside the supply device 31 and the vaporizer 32, a capillary tube 35 that penetrates through the partition wall 33 and connects them is provided. Is the raw material solution 3 stored in the supply device 31
1 is provided in the vicinity of the upper side of the liquid surface, and a slanted opening surface 35b is formed at the tip 35a. In addition, the supply device 30
A needle 36 having a small diameter is inserted into the upper portion of the capillary 35, and the lower end 36 a of the needle 36 is located below the tip 35 a of the capillary 35. The capillary tube 35 is, for example, an injection needle having an inner diameter of about a fraction of a millimeter, and the needle 36 is, for example, an injection needle having an inner diameter of about 1 mm.
【００１９】前記供給器３０には、原液供給装置３７が
ニードル３６とチューブ３８とを介し接続されている。
原液供給装置３７は、チューブポンプ３９と収納容器４
０を具備し、収納容器４０の内部には原料溶液３１が収
納されている。収納容器４０は、ガラス瓶などの耐薬品
性に優れたものが使用される。この収納容器４０に収納
されている原料溶液３１は、成膜するべき目的化合物の
構成金属元素の有機金属錯体、金属アルコキシドなどの
金属有機化合物を、目的化合物の組成比となるように複
数種混合して有機溶媒に溶解したものである。これらの
金属有機化合物および有機溶媒の具体例を明示するなら
ば、Ｙ-Ｂａ-Ｃｕ-Ｏ系酸化物超電導体を成膜する場合
に用いられるＹ（ＤＰＭ）3、Ｂａ（ＤＰＭ）2、Ｃｕ
（ＤＰＭ）2などの有機金属錯体、および、テトラヒド
ロフラン（ＴＨＦ）、ＤＰＭ、エタノールなどの有機溶
媒である。A stock solution supply device 37 is connected to the supply device 30 via a needle 36 and a tube 38.
The stock solution supply device 37 includes a tube pump 39 and a storage container 4.
0, and the raw material solution 31 is stored in the storage container 40. As the storage container 40, a container having excellent chemical resistance such as a glass bottle is used. The raw material solution 31 stored in the storage container 40 is obtained by mixing plural kinds of metal organic compounds such as an organic metal complex and a metal alkoxide of a constituent metal element of the target compound to be formed into a film so as to have a composition ratio of the target compound. And dissolved in an organic solvent. If specific examples of the metal organic compound and the organic solvent are specified, Y (DPM) 3 , Ba (DPM) 2 , Cu used when forming a Y—Ba—Cu—O-based oxide superconductor are formed.
(DPM) 2 and organic solvents such as tetrahydrofuran (THF), DPM and ethanol.
【００２０】前記チューブポンプ３９は、図２（ｂ）に
拡大して示すように、大ローラ４２の外周部に可撓性の
チューブ４３を沿わせて設け、このチューブ４３の外部
に複数の小ローラ４５を回転自在に設けて構成されたも
ので、図示略の駆動源からの伝達動力により各小ローラ
４５を回転させることにより小ローラ４５…で可撓性の
チューブ４３を順次押圧し、チューブ４３内の原料溶液
を一定流量で排出できるようになっている。このチュー
ブポンプ３９の流量設定は、小ローラの回転速度によっ
て容易かつ正確に行なうことができる。As shown in FIG. 2B, the tube pump 39 is provided with a flexible tube 43 along the outer periphery of a large roller 42, and a plurality of small tubes outside the tube 43. The rollers 45 are rotatably provided, and the small tubes 45 are rotated by transmission power from a drive source (not shown) to sequentially press the flexible tubes 43 with the small rollers 45. The raw material solution in 43 can be discharged at a constant flow rate. The flow rate of the tube pump 39 can be set easily and accurately by the rotation speed of the small roller.
【００２１】この装置では、原料溶液を毎分数ｍｌ〜数
１０ｍｌの割合で容易に供給可能な能力がある。なお、
可撓性のチューブ４３としては耐薬品性に優れたフッ素
樹脂製チューブなどを用いることが好ましい。また、収
納容器４０と供給器３０との間のチューブ３８と、チュ
ーブポンプ３９のチューブ４３とを一体のチューブとし
て構成しても良く、別体のチューブで構成し、別体のチ
ューブどうしをジョイント部材で接続して用いても良
い。This apparatus has a capability of easily supplying a raw material solution at a rate of several ml to several tens ml per minute. In addition,
As the flexible tube 43, it is preferable to use a tube made of fluororesin having excellent chemical resistance. Further, the tube 38 between the storage container 40 and the supply device 30 and the tube 43 of the tube pump 39 may be formed as an integral tube, or may be formed as separate tubes, and the separate tubes are jointed. It may be used by connecting with members.
【００２２】前記構成のチューブポンプ３９は、小ロー
ラ４５…により可撓性のチューブ４３を押圧しながら回
転してチューブ４３内の原料溶液を一定量押し出す構成
なので、チューブポンプ上流側（収納容器４０）では大
気圧状態であって、ポンプ下流側（供給器３０）側では
多少低圧状態であっても支障なく一定量の原料溶液を送
ることができる。前記チューブポンプ３９でニードル３
６を介して供給器３１に送られる原料溶液は、供給器３
０の内部に一定量供給されるが、ここで供給される原料
溶液３１の液面は、毛細管３５の上端の傾斜した開口面
３７ｂの下端部とほぼ同一の高さになるように調整され
る。The tube pump 39 having the above-described structure is configured to rotate while pressing the flexible tube 43 by the small rollers 45 to push out a fixed amount of the raw material solution in the tube 43, so that the upstream side of the tube pump (the storage container 40) ) Is at atmospheric pressure, and a certain amount of the raw material solution can be sent to the downstream side of the pump (supply unit 30) without any problem even if the pressure is somewhat low. Needle 3 with the tube pump 39
The raw material solution sent to the feeder 31 through the feeder 6
0, the liquid level of the raw material solution 31 supplied here is adjusted to be substantially the same height as the lower end of the inclined opening surface 37b at the upper end of the capillary tube 35. .
【００２３】一方、前記供給器３０には、接続管４６を
介してアルゴンガスなどのキャリアガス供給源４８が接
続されていて、供給器３０の内部に所定量のキャリアガ
スを供給できるように構成されている。On the other hand, a carrier gas supply source 48 such as argon gas is connected to the supply unit 30 through a connection pipe 46 so that a predetermined amount of carrier gas can be supplied into the supply unit 30. Have been.
【００２４】次に、前記気化器３２の外周部には、気化
器３２の内部を加熱するためのヒータ４９が付設されて
いて、このヒータ４９により原料溶液を所望の温度に加
熱させて気化できるようになっている。前記気化器３２
は、接続管５０を介して反応チャンバ５１に接続されて
いる。この反応チャンバ５１は、図７に示す従来装置の
反応チャンバ２０とほぼ同等の構成であり、基材２２を
備えた基材ホルダ２３とノズル２５を備え、更に真空ポ
ンプ２１が接続され、ノズル２５に前記気化器３２が接
続されている。また、反応チャンバ５１のノズル２５に
は、接続管５２を介して酸素ガス供給源５３が接続され
ていて、反応チャンバ５１に酸素ガスを供給できるよう
になっている。Next, a heater 49 for heating the inside of the vaporizer 32 is provided on the outer peripheral portion of the vaporizer 32, and the raw material solution can be heated to a desired temperature by the heater 49 and vaporized. It has become. The vaporizer 32
Is connected to the reaction chamber 51 via the connection pipe 50. The reaction chamber 51 has substantially the same configuration as the reaction chamber 20 of the conventional apparatus shown in FIG. 7, and includes a substrate holder 23 having a substrate 22 and a nozzle 25, and is further connected to a vacuum pump 21. Is connected to the vaporizer 32. An oxygen gas supply source 53 is connected to the nozzle 25 of the reaction chamber 51 via a connection pipe 52 so that oxygen gas can be supplied to the reaction chamber 51.
【００２５】次に前記装置を用いて原料溶液３１の気化
ガスを反応チャンバ５１に送り、反応チャンバ５１にお
いて基材２２上に酸化物超電導体の薄膜を形成する場合
について説明する。まず、原料の金属有機化合物の気化
ガスを得るには、まず、成膜するべき目的化合物の構成
金属元素の有機金属錯体、金属アルコキシドなどの金属
有機化合物を、目的化合物の組成比となるように複数種
混合し、ＴＨＦ、ＤＰＭ、エタノールなどの有機溶媒に
溶解させて原料溶液３１を作成する。Next, a case where the vaporized gas of the raw material solution 31 is sent to the reaction chamber 51 using the above-described apparatus and a thin film of an oxide superconductor is formed on the base material 22 in the reaction chamber 51 will be described. First, in order to obtain a vaporized gas of a raw material metal organic compound, first, a metal organic compound such as an organic metal complex or a metal alkoxide of a constituent metal element of a target compound to be formed into a film is formed so as to have a composition ratio of the target compound. A plurality of kinds are mixed and dissolved in an organic solvent such as THF, DPM, and ethanol to prepare a raw material solution 31.
【００２６】この原料溶液３１を収納容器４０に入れ、
チューブポンプ３９を作動させて所定量の原料溶液を供
給器３１の内部に送液する。また、気化器３２の内部温
度を前記原料のうちの最も気化温度の高い原料の最適温
度に合わせて調節し、ＣＶＤ装置の反応チャンバ５１を
スタンバイする。即ち、反応チャンバ５１の内部に基材
２２をセットし、反応チャンバ５１の内部を所定の気圧
に減圧し、前記基材２２を反応に適した温度に加熱して
おく。更に、キャリアガス供給源４８からアルゴンガス
などのキャリアガスを供給器３０の内部に所定量供給す
る。The raw material solution 31 is put in a storage container 40,
The tube pump 39 is operated to send a predetermined amount of the raw material solution into the supply device 31. Further, the internal temperature of the vaporizer 32 is adjusted in accordance with the optimum temperature of the raw material having the highest vaporization temperature among the raw materials, and the reaction chamber 51 of the CVD apparatus is on standby. That is, the substrate 22 is set inside the reaction chamber 51, the pressure inside the reaction chamber 51 is reduced to a predetermined pressure, and the substrate 22 is heated to a temperature suitable for the reaction. Further, a predetermined amount of a carrier gas such as an argon gas is supplied from the carrier gas supply source 48 into the supply device 30.
【００２７】前記の操作により気化器３２の内部は減圧
状態になるので、大気圧状態の供給器３０の内部から減
圧状態の気化器３２に向けて毛細管３５を介してキャリ
アガスが自然に急激な速度で吸引され、この際に原料溶
液３１が細粒の液滴状になって気化器３２に吸引され
る。即ち、図２（ａ）に示すように原料溶液３１の液面
部分において、毛細管３５の傾斜した開口面３５ｂから
この開口面３５ｂの内部側に、供給器３０と気化器３１
との気圧差によって自然にキャリアガスが急激に吸引さ
れるので、原料溶液３１はこのキャリアガスの急激な流
れにより液滴状に飛ばされつつ毛細管３５の内部に吸引
される結果、原料溶液３１の細粒状の液滴を気化器３２
に正確に送ることできる。また、キャリアガスの急激な
流れで原料溶液３１を細粒の液滴状にするために、毛細
管３５の途中で原料溶液３１が滞留しようとしても、こ
の液滴は滞留することなく容易に気化器３２の内部側に
搬送される。よって、毛細管３５の内部が目詰まりする
ことはない。Since the inside of the vaporizer 32 is depressurized by the above-described operation, the carrier gas naturally spontaneously flows from the inside of the supply unit 30 at atmospheric pressure to the vaporizer 32 under reduced pressure via the capillary tube 35. The raw material solution 31 is sucked into the vaporizer 32 in the form of fine droplets at this time. That is, as shown in FIG. 2A, at the liquid surface portion of the raw material solution 31, the supply device 30 and the vaporizer 31 are provided from the inclined opening surface 35b of the capillary tube 35 to the inside of the opening surface 35b.
The carrier solution is naturally rapidly aspirated due to the pressure difference between the carrier solution 31 and the raw material solution 31. The fine droplets are vaporized 32
Can be sent accurately. Further, in order to make the raw material solution 31 into fine droplets by the rapid flow of the carrier gas, even if the raw material solution 31 tries to stay in the middle of the capillary tube 35, the droplets are easily evaporated without staying. 32. Therefore, the inside of the capillary tube 35 is not clogged.
【００２８】なお、原料溶液３１の細粒の液滴を定量、
正確に気化器３２に送るためには、供給器３０内の原料
溶液の液面を一定の高さに保持することが重要である。
ここで、毛細管３５の先端部を斜めに切断して傾斜した
開口面３５ｂとしておくならば、原料溶液３１の液面が
多少上下しても原料溶液３１を確実に液滴状として気化
器３２に送ることができる。これに対して毛細管３５の
先端部を水平な開口面にすると、原料溶液３１の液面が
多少上下しても細粒の液滴の供給状態が不安定になるの
で好ましくない。The fine droplets of the raw material solution 31 are quantified,
In order to accurately send the raw material solution to the vaporizer 32, it is important to maintain the liquid level of the raw material solution in the supply device 30 at a constant level.
Here, if the tip of the capillary tube 35 is cut obliquely to form an inclined opening surface 35b, the raw material solution 31 is surely formed into droplets even if the liquid surface of the raw material solution 31 slightly rises and falls, Can be sent. On the other hand, if the tip of the capillary tube 35 has a horizontal opening surface, it is not preferable because the supply state of the fine droplets becomes unstable even if the liquid surface of the raw material solution 31 slightly rises and falls.
【００２９】気化器３２内に供給された原料溶液３１の
液滴は、気化器３２の内部で気化される。この際に原料
溶液３１内の溶媒も気化されるので、この気化溶媒もキ
ャリアガスの一部を構成する。このような原料溶液３１
の気化したガスと溶媒の気化したガスとキャリアガスの
混合ガスは、反応チャンバ５１に送られ、別途に酸素供
給源５３から供給された酸素ガスとともに混合されて所
定のガス反応位置で加熱され、各金属成分と酸素とが反
応して複合酸化物などの反応生成物を生じ、その反応正
生物が基材２２の表面に堆積する。The droplets of the raw material solution 31 supplied into the vaporizer 32 are vaporized inside the vaporizer 32. At this time, since the solvent in the raw material solution 31 is also vaporized, this vaporized solvent also constitutes a part of the carrier gas. Such a raw material solution 31
The mixed gas of the vaporized gas, the vaporized gas of the solvent, and the carrier gas is sent to the reaction chamber 51, mixed with the oxygen gas separately supplied from the oxygen supply source 53, and heated at a predetermined gas reaction position, Each metal component reacts with oxygen to produce a reaction product such as a composite oxide, and the reaction products deposit on the surface of the substrate 22.
【００３０】以上の成膜操作を所定時間継続して行なう
ことにより、基材２２上に所望の厚さの生成物層を形成
することができる。この生成物層を必要に応じて熱処理
することで、所望の酸化物超電導体を得ることができ
る。また、長尺基材の表面に連続して成膜するには、反
応チャンバ５１の内部で長尺の基材を移動させながら成
膜処理を行えば良い。例えば、反応チャンバ５１の内部
に長尺基材の巻取装置と送出装置を組み込み、基材ホル
ダ２３上に連続的に基材を送り出し、基材ホルダ２３の
上で連続成膜処理を行えば良い。By continuously performing the above film forming operation for a predetermined time, a product layer having a desired thickness can be formed on the substrate 22. By subjecting this product layer to heat treatment as needed, a desired oxide superconductor can be obtained. Further, in order to continuously form a film on the surface of the long base material, the film formation process may be performed while moving the long base material inside the reaction chamber 51. For example, if a winding device and a sending device for a long base material are incorporated in the reaction chamber 51, the base material is continuously sent out onto the base material holder 23, and a continuous film forming process is performed on the base material holder 23. good.
【００３１】このようなＣＶＤ法によって成膜される超
電導材料は、Ｙ-Ｂａ-Ｃｕ-Ｏ系、Ｂｉ-Ｓｒ-Ｃａ-Ｃｕ
-Ｏ系、Ｔｌ-Ｂａ-Ｃａ-Ｃｕ-Ｏ系などの酸化物超電導
体の他、チタン酸バリウム系材料、ＰＺＴなどの各種セ
ラミックス材料などである。The superconducting material formed by such a CVD method is a Y-Ba-Cu-O-based, Bi-Sr-Ca-Cu
In addition to oxide superconductors such as -O-based and Tl-Ba-Ca-Cu-O-based, various ceramic materials such as barium titanate-based materials and PZT are used.
【００３２】前記した装置によれば、供給器３０から気
化器３２に毛細管３５により細粒状の原料溶液の液滴を
所定量安定状態で供給できるので、長時間の運転におい
ても安定した原料溶液の供給ができる。また、原料溶液
３１を用いることで、容器４０から反応チャンバ５１ま
での間の接続管やチューブに原料の目詰まりを引き起こ
すことがなくなり、反応チャンバ５１に対する原料溶液
３１の安定供給ができる。更に、収納容器４０内の原料
溶液３１は、大気圧下にあり、密封されていないため
に、収納容器４０の内部に対する原料溶液３１の供給、
あるいは、収納容器４０と原料溶液３１の交換を反応チ
ャンバ５１の運転中に任意の段階で容易に行うことがで
きる。よって、収納容器４０内の原料溶液３１を交換す
ることで反応チャンバ５１に対する原料溶液３１の無期
限供給が容易にできるようになり、長尺の基材に成膜す
る場合に特に有効である。According to the above-mentioned apparatus, since a predetermined amount of fine droplets of the raw material solution can be supplied from the supply device 30 to the vaporizer 32 by the capillary tube 35 in a stable state, the stable raw material solution can be supplied even during a long operation. Can supply. Further, by using the raw material solution 31, clogging of the raw material in the connecting pipe or tube between the container 40 and the reaction chamber 51 does not occur, and the raw material solution 31 can be stably supplied to the reaction chamber 51. Further, since the raw material solution 31 in the storage container 40 is under atmospheric pressure and is not sealed, supply of the raw material solution 31 to the inside of the storage container 40 is performed.
Alternatively, the exchange of the raw material solution 31 with the storage container 40 can be easily performed at any stage during the operation of the reaction chamber 51. Therefore, by exchanging the raw material solution 31 in the storage container 40, the raw material solution 31 can be easily supplied to the reaction chamber 51 indefinitely, which is particularly effective when forming a film on a long base material.
【００３３】なお、前記構成の装置によれば、目的化合
物の構成元素を含む複数種の金属有機化合物を目的化合
物の元素組成が得られるように混合して溶媒に溶かして
原料溶液３１とし、この原料溶液３１をチューブポンプ
３９によって、加熱状態の気化器３２に一定流量で送り
出す構成としたので、常時一定組成の気化混合ガスを長
時間安定的に反応チャンバ５１に供給可能であるので、
基材２２上に高品質の薄膜を得ることができる。また、
原料溶液３１を気化する際に同時に気化した溶媒気化ガ
スをキャリアガスの一部として代用できるので、キャリ
アガス供給系などの設備を簡略化でき、付属設備を小型
化できる。また、複数の原料を混合して溶媒に溶かした
原料溶液３１を用いるので、原料供給系を１系統に統一
することができ、多数の系統の原料供給系が必要であっ
た従来装置よりもキャリアガスの供給源や原料加熱条件
などのパラメータを大幅に減少させることができる。According to the apparatus having the above structure, a plurality of types of metal organic compounds containing the constituent elements of the target compound are mixed so as to obtain the elemental composition of the target compound and dissolved in a solvent to form a raw material solution 31. Since the raw material solution 31 is supplied to the vaporizer 32 in a heated state at a constant flow rate by the tube pump 39, a vaporized mixed gas having a constant composition can be constantly supplied to the reaction chamber 51 stably for a long time.
A high-quality thin film can be obtained on the substrate 22. Also,
When the raw material solution 31 is vaporized, the vaporized solvent vaporized at the same time can be used as a part of the carrier gas, so that the equipment such as the carrier gas supply system can be simplified and the attached equipment can be downsized. In addition, since the raw material solution 31 in which a plurality of raw materials are mixed and dissolved in a solvent is used, the raw material supply system can be unified into one system, and the carrier is more carrier than the conventional apparatus which requires a large number of raw material supply systems. Parameters such as a gas supply source and raw material heating conditions can be greatly reduced.
【００３４】更に、原料溶液３１の送液ポンプとしてチ
ューブポンプ３９を用いるならば、大気圧下の収納容器
４０から、減圧状態の気化器３２に接続された供給器３
０に一定量の原料溶液３１をスムーズに送ることができ
る。Further, if a tube pump 39 is used as a pump for feeding the raw material solution 31, the supply device 3 connected to the vaporizer 32 under reduced pressure from the storage container 40 under atmospheric pressure.
A constant amount of the raw material solution 31 can be smoothly sent to zero.
【００３５】一方、図３と図４は実際のＣＶＤ反応装置
に組み込むことを考慮して設計した供給器の一例の詳細
構造を示すものである。この例の供給器６０は、筒状で
先窄まり状の供給部６１とこの供給部６１の底部６２の
近くまで挿入された注射針状のニードル６３と前記底部
６２を貫通して設けられた毛細管６４と前記供給部６１
の底部側を覆う筒状の吸引部６５とこの吸引部６５の側
部に接続された吸引管６６を主体として構成され、主要
部は透明ガラスで構成されたものであり、吸引部６５の
下端部に気化器３２’が接続できるように構成されてい
る。On the other hand, FIGS. 3 and 4 show a detailed structure of an example of a supply unit designed in consideration of being incorporated in an actual CVD reactor. The supply device 60 of this example is provided so as to penetrate a cylindrical, tapered supply portion 61, an injection needle-like needle 63 inserted close to a bottom portion 62 of the supply portion 61, and the bottom portion 62. Capillary tube 64 and supply section 61
The main part is made of a transparent glass, and the main part is made of a transparent glass. The lower end of the suction part 65 is mainly composed of a cylindrical suction part 65 covering the bottom side of the suction part 65 and a suction pipe 66 connected to the side part of the suction part 65. It is configured such that a vaporizer 32 'can be connected to the section.
【００３６】図３に示す供給器６０において、供給部６
１の上端部から吸引管６６の上端までの距離ａを約１０
ｍｍ、吸引管６の内径を約８ｍｍ、供給部６１の下端部
から吸引部６５の下端部までの距離ｃを約１５ｍｍ、供
給部６１の底部の外径ｄを約７ｍｍ、図４に示す供給部
６１の底部６２から毛細管６４の上端部までの距離ｅを
約１５ｍｍ、供給部６１の底部６２から毛細管６４の下
端部までの距離を約２０ｍｍにそれぞれ設定した。ま
た、ニードル６３の外径を１ｍｍ、毛細管６４の外径を
０.３ｍｍとした。この例の供給器６０は、吸引部６５
の下端部内側に気化器３２’の入口部を接続し、吸引管
６６に反応チャンバを接続することで使用することがで
きる。In the supply unit 60 shown in FIG.
The distance a from the upper end of the suction pipe 66 to the upper end of the suction pipe 66 is about 10
4 mm, the inner diameter of the suction tube 6 is about 8 mm, the distance c from the lower end of the supply section 61 to the lower end of the suction section 65 is about 15 mm, and the outer diameter d of the bottom of the supply section 61 is about 7 mm. The distance e from the bottom 62 of the part 61 to the upper end of the capillary 64 was set to about 15 mm, and the distance from the bottom 62 of the supply part 61 to the lower end of the capillary 64 was set to about 20 mm. The outer diameter of the needle 63 was 1 mm, and the outer diameter of the capillary 64 was 0.3 mm. The supply device 60 in this example includes a suction unit 65.
It can be used by connecting the inlet of the vaporizer 32 ′ to the inside of the lower end and connecting the reaction chamber to the suction pipe 66.
【００３７】（実験例）図１に示す構成のＣＶＤ装置を
用いてＹ-Ｂａ-Ｃｕ-Ｏ系の酸化物超電導体の成膜実験
を行った。反応チャンバは熱ＣＶＤ装置の反応チャンバ
を用い、供給器は図３と図４に示す形状のものを用い
た。原料溶液として、Ｙ（ＤＰＭ）3、Ｂａ（ＤＰ
Ｍ）2、Ｃｕ（ＤＰＭ）2をモル比でＹ：Ｂａ：Ｃｕ＝
１：２.５：３に混合したもの０.３ｇを用い、テトラヒ
ドロフラン１０ｍｌの溶媒に溶かしたものを収納容器に
貯留して用いた。この原料溶液をチューブポンプにより
０.１ｍｌ／分の流速で、口径１ｍｍの注射針状のニー
ドルから供給器に連続的に供給した。この際、供給器の
内部に約１５ｍｍの深さになるように原料溶液を貯留
し、気化器を２６０℃に加熱し、反応チャンバの内部を
約１０Ｔｏｒｒに減圧し、供給器の内部にキャリアガス
としてのアルゴンガスを４００ｍｌ／分の割合で供給し
た。(Experimental Example) A film-forming experiment of a Y-Ba-Cu-O-based oxide superconductor was performed using a CVD apparatus having the structure shown in FIG. A reaction chamber of a thermal CVD apparatus was used as a reaction chamber, and a supply device having a shape shown in FIGS. 3 and 4 was used. As raw material solutions, Y (DPM) 3 , Ba (DP
M) 2 , Cu (DPM) 2 in a molar ratio of Y: Ba: Cu =
0.3 g mixed in a ratio of 1: 2.5: 3 was used, and a solution dissolved in a solvent of 10 ml of tetrahydrofuran was stored in a storage container and used. This raw material solution was continuously supplied to the supply device from a 1 mm-diameter syringe needle at a flow rate of 0.1 ml / min by a tube pump. At this time, the raw material solution is stored to a depth of about 15 mm inside the supply device, the vaporizer is heated to 260 ° C., the pressure inside the reaction chamber is reduced to about 10 Torr, and the carrier gas is supplied inside the supply device. Was supplied at a rate of 400 ml / min.
【００３８】以上の操作により、供給器内部の原料溶液
を内径０.３ｍｍの毛細管先端部の斜めに切断された開
口面から勢い良く気化器側に吸引することができ、細粒
状の液滴の原料溶液をキャリアガスとともに気化器に供
給することができた。反応チャンバの内部にはハステロ
イＣー２７６からなる基板とこの基板上にＹＳＺ（イッ
トリウム安定化ジルコニア）の中間層を皮膜したものを
用いた。約６０分の成膜処理と５００℃に２時間加熱す
る熱処理によって前記基材上に厚さ約１.５μｍのＹ-Ｂ
ａ-Ｃｕ-Ｏ系の超電導層を形成することできた。このＹ
-Ｂａ-Ｃｕ-Ｏ系の酸化物超電導体の超電導特性を測定
したところ、Ｔｃ＝９１Ｋ、Ｊｃ＝５.２×１０5Ａ／ｃ
ｍ2の優れた特性を発揮した。また、前記と同様の操作
を行う際に、原料溶液の収納容器に順次原料溶液を追加
してゆくことで、連続的に原料溶液の供給が可能であ
り、酸化物超電導体の連続成膜が可能であり、また、収
納容器ごと原料容器を交換しても成膜に支障なく連続運
転ができた。By the above operation, the raw material solution in the feeder can be vigorously sucked into the vaporizer side from the obliquely cut opening surface of the tip of the capillary having an inner diameter of 0.3 mm. The raw material solution could be supplied to the vaporizer together with the carrier gas. Inside the reaction chamber, a substrate made of Hastelloy C-276 and an intermediate layer of YSZ (yttrium stabilized zirconia) coated on the substrate were used. Y-B having a thickness of about 1.5 μm is formed on the base material by a film forming process for about 60 minutes and a heat treatment of heating to 500 ° C. for 2 hours.
An a-Cu-O-based superconducting layer could be formed. This Y
When the superconducting characteristics of the -Ba-Cu-O-based oxide superconductor were measured, Tc = 91 K and Jc = 5.2 × 10 5 A / c.
Excellent properties of m 2 were exhibited. Further, when performing the same operation as described above, by successively adding the raw material solution to the storage container for the raw material solution, the raw material solution can be continuously supplied, and the continuous film formation of the oxide superconductor can be performed. It was possible, and even if the raw material container was replaced with the storage container, continuous operation could be performed without any trouble in film formation.
【００３９】[0039]
【発明の効果】以上説明したように本発明によれば、反
応チャンバを減圧雰囲気とすると、毛細管から気化器に
向かう急激なキャリアガスの流れを自然に形成すること
ができるので、この急激なキャリアガスの流れに沿って
原料溶液を毛細管の開口面で細粒の液滴状にして同時に
キャリアガスとともに一定量気化器に供給することがで
きる。よって気化器において、細粒の液滴状の原料溶液
を確実に気化することができ、これにより反応チャンバ
に所定量のキャリアガスと原料溶液気化ガスを確実に供
給することができ、反応チャンバ内の基材上に所望の組
成の反応生成物の薄膜を形成することができる。As described above, according to the present invention, when the reaction chamber is set to a reduced pressure atmosphere, a sharp flow of the carrier gas from the capillary to the vaporizer can be naturally formed. The raw material solution can be formed into fine droplets at the opening surface of the capillary along the flow of the gas, and at the same time, can be supplied to the vaporizer in a fixed amount together with the carrier gas. Therefore, in the vaporizer, the raw material solution in the form of fine droplets can be reliably vaporized, whereby a predetermined amount of the carrier gas and the raw material solution vaporized gas can be reliably supplied to the reaction chamber. A thin film of a reaction product having a desired composition can be formed on the base material.
【００４０】また、原料溶液を用いるので、粉末原料を
用いる場合とは異なり、途中の配管に目詰まりを引き起
こすことはなく、多成分系の混合粉末原料に比較して制
御するべきパラメータも少ないので規定成分供給の場合
の再現性が良好である。更に、供給器と気化器を接続す
るのは毛細管であり、この毛細管を細粒化した原料溶液
の液滴がキャリアガスとともに通過するので、毛細管の
途中に原料溶液が万が一目詰まりしようとしても、キャ
リアガスの流れにより気化器側に強制的に移動されるの
で、従来のニードル弁を用いる場合とは異なり、途中で
目詰まりを起こすことがない。一方、気化器の内部を減
圧雰囲気としても、供給器の内部を大気圧状態とするこ
とができ、原料溶液を供給器内の大気圧下に収納できる
ので、原料溶液を供給器内に容易に追加することができ
る。従って供給器に対する原料溶液の追加により、どの
ような長時間の原料溶液供給でも可能であり、反応チャ
ンバにおける長時間の成膜運転が可能である。Further, since the raw material solution is used, unlike the case of using the powder raw material, no clogging is caused in the piping on the way, and the number of parameters to be controlled is smaller than that of the multi-component mixed powder raw material. Good reproducibility in the case of supply of specified components. Further, it is a capillary that connects the supply device and the vaporizer, and since the droplets of the raw material solution that has been finely divided through the capillary pass together with the carrier gas, even if the raw material solution is clogged in the middle of the capillary, Since the carrier gas is forcibly moved to the vaporizer side, unlike the case of using a conventional needle valve, clogging does not occur on the way. On the other hand, even if the inside of the vaporizer is in a reduced-pressure atmosphere, the inside of the supply unit can be kept at atmospheric pressure, and the raw material solution can be stored under the atmospheric pressure in the supply unit. Can be added. Therefore, by adding the raw material solution to the supply device, any long-time supply of the raw material solution is possible, and a long-term film forming operation in the reaction chamber is possible.
【００４１】よって原料溶液として例えば、Ｙ-Ｂａ-Ｃ
ｕ-Ｏ系などの酸化物超電導体の構成元素の金属有機化
合物を溶媒に溶解したものを用いるならば、反応チャン
バの内部に設けた基材上に、Ｙ-Ｂａ-Ｃｕ-Ｏ系の酸化
物超電導体の薄膜を形成することができる。しかも、連
続成膜が容易にできるので、長尺の基材上に酸化物超電
導体の薄膜を生成できる利点がある。Therefore, as a raw material solution, for example, Y-Ba-C
If a metal organic compound as a constituent element of an oxide superconductor such as u-O is dissolved in a solvent, a Y-Ba-Cu-O-based oxidizer is formed on a substrate provided inside the reaction chamber. A thin film of a superconductor can be formed. In addition, since continuous film formation can be easily performed, there is an advantage that a thin film of an oxide superconductor can be formed on a long base material.
【００４２】一方、毛細管の先端部を傾斜した開口面と
することで、この傾斜した開口面からキャリアガスを原
料溶液とともに毛細管を介して気化器に送ることができ
る。傾斜した開口面であると、開口面の下端部に原料溶
液の液面が位置した時点でキャリアガスの急激な流れに
より原料溶液が容易に細粒状になって気化器に送られる
ので、細粒の原料溶液を気化器に供給し、気化器で確実
に気化することができる。また、原料溶液の液面位置が
多少上下に変動しても傾斜した開口面であると、原料溶
液の毛細管への吸引作用が円滑になされるので細粒状の
原料溶液を気化器に確実に供給できる。On the other hand, by forming the tip of the capillary tube with an inclined opening surface, the carrier gas can be sent from the inclined opening surface together with the raw material solution to the vaporizer via the capillary tube. When the opening surface is inclined, the raw material solution is easily formed into fine particles by the rapid flow of the carrier gas when the liquid surface of the raw material solution is located at the lower end of the opening surface and is sent to the vaporizer. Is supplied to the vaporizer, and can be reliably vaporized by the vaporizer. Also, even if the liquid level of the raw material solution fluctuates slightly up and down, if the opening surface is inclined, the suction action of the raw material solution to the capillary is performed smoothly, so that the fine granular raw material solution is reliably supplied to the vaporizer. it can.
【図１】図１は本発明に係る供給装置の一実施例を示す
構成図である。FIG. 1 is a configuration diagram showing one embodiment of a supply device according to the present invention.
【図２】図２（ａ）は図１に示す装置の毛細管の拡大
図、図２（ｂ）は図１に示す装置のチューブポンプを示
す拡大図である。2A is an enlarged view of a capillary tube of the apparatus shown in FIG. 1, and FIG. 2B is an enlarged view showing a tube pump of the apparatus shown in FIG.
【図３】図３は図１に示す装置の一具体例の要部を示す
側面図である。FIG. 3 is a side view showing a main part of a specific example of the apparatus shown in FIG. 1;
【図４】図４は図３に示す要部の一部拡大図である。FIG. 4 is a partially enlarged view of a main part shown in FIG. 3;
【図５】図５は従来の原料粉末を供給する装置の一例を
示す構成図である。FIG. 5 is a configuration diagram showing an example of a conventional apparatus for supplying raw material powder.
【図６】図６は図５に示す装置の一部拡大図である。FIG. 6 is a partially enlarged view of the device shown in FIG. 5;
【図７】図７は従来の原料ミスト供給装置の一例を示す
構成図である。FIG. 7 is a configuration diagram showing an example of a conventional raw material mist supply device.
【図８】図８は図７に示す装置の一部拡大図である。FIG. 8 is a partially enlarged view of the device shown in FIG. 7;
２１ 真空ポンプ、 ２２ 基材、 ２３ 基材ホルダ、 ３０ 供給器、 ３１ 原料溶液、 ３２ 気化器、 ３５ 毛細管、 ３５ａ 先端部、 ３５ｂ 開口面、 ３６ ニードル、 ３７ 原料溶液供給装置、 ４８ キャリアガス供給源、 ５１ 反応チャンバ、 Reference Signs List 21 vacuum pump, 22 base material, 23 base material holder, 30 feeder, 31 raw material solution, 32 vaporizer, 35 capillary tube, 35a tip end, 35b opening surface, 36 needle, 37 raw material solution supply device, 48 carrier gas supply source , 51 reaction chambers,
───────────────────────────────────────────────────── フロントページの続き (72)発明者 香川 昭 東京都江東区木場一丁目５番１号 株式 会社フジクラ内 (72)発明者 河野 宰 東京都江東区木場一丁目５番１号 株式 会社フジクラ内 (72)発明者 長屋 重夫 愛知県名古屋市緑区大高町字北関山20番 地の１ 中部電力株式会社 電力技術研 究所 (72)発明者 井上 俊夫 愛知県名古屋市緑区大高町字北関山20番 地の１ 中部電力株式会社 電力技術研 究所 (56)参考文献 特開 平６−24895（ＪＰ，Ａ) 特開 平５−117862（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C30B 1/00 - 35/00 C23C 16/448 ＣＡ（ＳＴＮ) ＷＰＩ（ＤＩＡＬＯＧ)────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Akira Kagawa 1-5-1, Kiba, Koto-ku, Tokyo Inside Fujikura Co., Ltd. (72) Inventor Satoshi Kono 1-5-1, Kiba, Koto-ku, Tokyo Fujikura Co., Ltd. (72) Inventor Shigeo Nagaya 20-1, Kitakanyama, Odaka-cho, Midori-ku, Nagoya-shi, Aichi Electric Power Engineering Laboratory, Chubu Electric Power Co., Inc. (72) Inventor Toshio Inoue Odaka-cho, Midori-ku, Nagoya-shi, Aichi Electricity Research Institute, Chubu Electric Power Co., Inc., 20-20 Kita-Sekiyama (56) References JP-A-6-24895 (JP, A) JP-A-5-117862 (JP, A) (58) Fields surveyed (Int.Cl. 7 , DB name) C30B 1/00-35/00 C23C 16/448 CA (STN) WPI (DIALOG)
Claims (2)
れる容器状の供給器と、この供給器に毛細管を介し接続
されて減圧雰囲気の反応チャンバに接続される気化器と
を具備し、前記毛細管の供給器内の先端部の開口面を供
給器内の原料溶液の液面近傍上方に配置してなることを
特徴とするＣＶＤ用原料ガスの発生装置。1. A container-like supply device into which a raw material solution and a carrier gas are supplied, and a vaporizer connected to the supply device through a capillary tube and connected to a reaction chamber in a reduced-pressure atmosphere. An apparatus for generating a raw material gas for CVD, wherein an opening surface of a tip portion of a capillary tube inside a supply device is disposed above and near a liquid surface of a raw material solution in the supply device.
た開口面を形成してなることを特徴とするＣＶＤ用原料
ガスの発生装置。2. An apparatus for generating a raw material gas for CVD, wherein an inclined opening surface is formed at the tip of the capillary tube according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00213593A JP3221952B2 (en) | 1993-01-08 | 1993-01-08 | Source gas generator for CVD |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00213593A JP3221952B2 (en) | 1993-01-08 | 1993-01-08 | Source gas generator for CVD |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06206796A JPH06206796A (en) | 1994-07-26 |
| JP3221952B2 true JP3221952B2 (en) | 2001-10-22 |
Family
ID=11520899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00213593A Expired - Lifetime JP3221952B2 (en) | 1993-01-08 | 1993-01-08 | Source gas generator for CVD |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3221952B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3415862B2 (en) * | 1992-07-06 | 2003-06-09 | 株式会社フジクラ | CVD raw material vaporizer |
| JP2704705B2 (en) * | 1994-05-23 | 1998-01-26 | 株式会社トリケミカル研究所 | Solutions used in chemical vapor deposition |
| EP0814177A3 (en) * | 1996-05-23 | 2000-08-30 | Ebara Corporation | Vaporizer apparatus and film deposition apparatus therewith |
| JP4787170B2 (en) * | 2004-10-21 | 2011-10-05 | 双葉電子工業株式会社 | Evaporation source device |
| JP5374373B2 (en) * | 2007-09-10 | 2013-12-25 | 株式会社アルバック | Organic material vapor generating device, film forming source, organic EL film forming device |
-
1993
- 1993-01-08 JP JP00213593A patent/JP3221952B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06206796A (en) | 1994-07-26 |
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