JP3231835B2 - Production method of thin film using organometallic complex - Google Patents
Production method of thin film using organometallic complexInfo
- Publication number
- JP3231835B2 JP3231835B2 JP12012392A JP12012392A JP3231835B2 JP 3231835 B2 JP3231835 B2 JP 3231835B2 JP 12012392 A JP12012392 A JP 12012392A JP 12012392 A JP12012392 A JP 12012392A JP 3231835 B2 JP3231835 B2 JP 3231835B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- organometallic complex
- complex
- metal
- metal thin
- 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 - Fee Related
Links
- 239000010409 thin film Substances 0.000 title claims description 41
- 125000002524 organometallic group Chemical group 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 9
- 239000012159 carrier gas Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007858 starting material Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 238000001947 vapour-phase growth Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000010408 film Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000000859 sublimation Methods 0.000 description 7
- 230000008022 sublimation Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 3
- AGWRAAIQXVWVLJ-UHFFFAOYSA-N 1,2,3,4,5-pentaethylcyclopenta-1,3-diene Chemical compound CCC1C(CC)=C(CC)C(CC)=C1CC AGWRAAIQXVWVLJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 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 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- -1 inorganic acid salt Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Chemical Vapour Deposition (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、気相成長法によって薄
膜を製造する方法に関し、さらに詳しくは、超電導材
料、強誘電体材料、半導体薄膜材料等として有用な特定
組成を有する金属薄膜を製造することができるシクロペ
ンタジエン系有機化合物の金属錯体を用いる薄膜の製造
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thin film by a vapor deposition method, and more particularly, to a method for producing a metal thin film having a specific composition useful as a superconducting material, a ferroelectric material, a semiconductor thin film material, and the like. The present invention relates to a method for producing a thin film using a metal complex of a cyclopentadiene-based organic compound.
【０００２】[0002]
【従来の技術】単結晶薄膜や多結晶薄膜の形成方法とし
ては、ドライプロセスとウエットプロセスといった２種
類の方法があるが、一般にウエットプロセスと比べてド
ライプロセスによって形成された薄膜のほうが品質面で
優れるため、ドライプロセスが多用さているのが現状で
ある。2. Description of the Related Art There are two types of methods for forming a single crystal thin film or a polycrystalline thin film, a dry process and a wet process. Generally, a thin film formed by a dry process has a higher quality than a wet process. At present, dry processes are frequently used because of their superiority.
【０００３】上記ドライプロセスには、真空蒸着法、イ
オンプレーティング法およびスパッタリング法等の物理
的成膜法と、化学的気相蒸着法（ＣＶＤ法）等の化学的
成膜法とがあるが、中でもＣＶＤ法は、成膜速度の制御
が容易である上、成膜を高真空下で行う必要がなく、し
かも高速成膜が可能であることなどから量産向きである
ため広く用いられている。The dry process includes a physical film forming method such as a vacuum evaporation method, an ion plating method and a sputtering method, and a chemical film forming method such as a chemical vapor deposition method (CVD method). Above all, the CVD method is widely used because it is easy to control the film formation rate, does not need to perform film formation under a high vacuum, and is suitable for mass production because high-speed film formation is possible. .
【０００４】このようなＣＶＤ法においては、有機金属
錯体の蒸気を分解させて金属薄膜を形成する場合、熱Ｃ
ＶＤ法、光ＣＶＤ法またはプラズマＣＶＤ法などが採用
され、原料化合物としては、一般的に有機部分（配位
子）がジピバロイルメタン、ヘキサフルオロアセチルア
セトンまたは1,1,1,2,2-ペンタフルオロ-8,6- ジメチル
-3,5- ヘキサンジオン等である1,3-ジケトン系有機金属
錯体が使用されてきた。In such a CVD method, when a metal thin film is formed by decomposing vapor of an organometallic complex, heat C
A VD method, a photo CVD method, a plasma CVD method, or the like is employed, and as a raw material compound, generally, an organic portion (ligand) is dipivaloylmethane, hexafluoroacetylacetone or 1,1,1,2,2. -Pentafluoro-8,6-dimethyl
1,3-diketone organometallic complexes such as -3,5-hexanedione have been used.
【０００５】しかしながら、上記のように1,3-ジケトン
系有機金属錯体を原料化合物とし、気相成長法（熱ＣＶ
Ｄ法など）によって薄膜の製造を行うと、満足な薄膜形
成速度を得ることができず、量産化ベースの薄膜を形成
することができないという問題点があった。また、該有
機金属錯体は、昇華性が低くしかも熱安定性が悪いた
め、成膜制御のコントロールが難しかった。そのため満
足な薄膜が形成される前に分解してしまうことがあり、
均一な薄膜を再現性良く成膜することが極めて困難であ
るという問題点があった。However, as described above, a 1,3-diketone-based organometallic complex is used as a starting compound, and a vapor phase growth method (thermal CV
When a thin film is manufactured by the D method or the like, there is a problem that a satisfactory thin film formation rate cannot be obtained and a thin film based on mass production cannot be formed. In addition, since the organometallic complex has low sublimability and poor thermal stability, it is difficult to control film formation control. Therefore, it may decompose before a satisfactory thin film is formed,
There is a problem that it is extremely difficult to form a uniform thin film with good reproducibility.
【０００６】一方、上記低昇華性の改善を図るため、有
機部分（配位子）の水素を弗素で置換した有機金属錯体
を原料化合物として用いた薄膜の製造方法が開発されて
いるが、有機部分（配位子）の水素を弗素で置換した有
機金属錯体を用いると、成膜中に弗化物が生成するた
め、薄膜の電気的特性が劣化してしまうという問題点が
あった。On the other hand, in order to improve the low sublimation property, a method for producing a thin film using an organometallic complex in which hydrogen of an organic portion (ligand) has been replaced with fluorine has been developed. The use of an organometallic complex in which a part (ligand) of hydrogen is replaced with fluorine has a problem that the electrical characteristics of the thin film are deteriorated because fluoride is generated during film formation.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、上述従来の
技術の問題点を解決し、優れた電気的特性を有し、かつ
再現性の良い均一な薄膜を容易に成膜することができる
有機金属錯体を用いる薄膜の製造方法を提供することを
目的する。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and can easily form a uniform thin film having excellent electric characteristics and good reproducibility. An object is to provide a method for producing a thin film using an organometallic complex.
【０００８】[0008]
【課題を解決するための手段】本発明者等は、上記課題
を解決するため鋭意研究した結果、ペンタメチルシクロ
ペンタジエンまたはペンタエチルシクロペンタジエンと
IIＡ族金属との錯体が、高昇華性を有し、しかも蒸発温
度（昇華温度）と分解温度とが大きく離れていることを
見い出し、本発明を達成することができた。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that pentamethylcyclopentadiene or pentaethylcyclopentadiene
The inventors have found that a complex with a Group IIA metal has a high sublimation property and that the evaporation temperature (sublimation temperature) and the decomposition temperature are far apart from each other, and the present invention has been achieved.
【０００９】 すなわち、本発明は、気相成長法による
金属薄膜の製造方法であって、化２で示されるシクロペ
ンタジエン系有機化合物とIIＡ族金属との有機金属錯体
を原料化合物として用いて不活性キャリアーガスに同
伴、昇華させ、次いで基板を配置した２５０〜７５０℃
の反応管内に該有機金属錯体を同伴した不活性キャリア
ーガスを導入して熱分解させることにより該基板上に該
IIＡ族金属の金属薄膜を均一に生成することを特徴とす
る金属薄膜の製造法を提供するものである。That is, the present invention relates to a method for producing a metal thin film by a vapor phase growth method, wherein an inert metal is prepared by using an organometallic complex of a cyclopentadiene-based organic compound represented by Chemical Formula 2 and a Group IIA metal as a raw material compound. 250-750 ° C. where the substrate is placed along with the carrier gas and sublimated
By introducing an inert carrier gas accompanied by the organometallic complex into the reaction tube of the above and thermally decomposing the carrier gas,
An object of the present invention is to provide a method for producing a metal thin film, characterized in that a metal thin film of a Group IIA metal is uniformly formed.
【００１０】[0010]
【化２】 （ただし、式中Ｒはメチル基またはエチル基を表す。）Embedded image (However, R represents a methyl group or an ethyl group in the formula.)
【００１１】[0011]
【作用】本発明の有機金属錯体を用いる薄膜の製造法に
ついて、熱ＣＶＤ法を利用した場合を例にあげ、図１を
用いて以下に説明する。なお、図１は熱ＣＶＤ法の概略
を模式的に示した図である。The method for producing a thin film using the organometallic complex of the present invention will be described below with reference to FIG. FIG. 1 is a diagram schematically showing an outline of the thermal CVD method.
【００１２】まず、恒温槽３内にあって、シクロペンタ
ジエン系有機金属錯体１が充填された原料容器２（50〜
250℃の恒温に保持）に、不活性キャリアーガス４をフ
ローメーター５を経て流量を 5〜 500ml／min に調節し
て導入し、このガス４に有機金属錯体１を同伴、昇華さ
せ、熱分解炉６内に設けた石英反応管７に導入させる。
上記石英反応管７は、ヒーター８によって所定の温度
（ 250〜 750℃）に加熱保持されており、その内部には
基板９が載置されている。First, a raw material container 2 (50 to 50) in a thermostat 3 filled with a cyclopentadiene-based organometallic complex 1 is provided.
(Maintained at a constant temperature of 250 ° C.), an inert carrier gas 4 was introduced through a flow meter 5 while adjusting the flow rate to 5 to 500 ml / min. It is introduced into a quartz reaction tube 7 provided in a furnace 6.
The quartz reaction tube 7 is heated and maintained at a predetermined temperature (250 to 750 ° C.) by a heater 8, and a substrate 9 is placed inside the quartz reaction tube 7.
【００１３】上記のようにして石英反応管７に導入され
た有機金属錯体同伴ガスは、基板９上において有機金属
錯体を熱分解し、金属薄膜を生成させる。なお、原料容
器２から熱分解炉６までの配管は、凝縮を防ぐために保
温層１０または加熱保温手段により50〜 250℃に保温維
持されている。また、図中１１は冷却トラップ、１２は
バルブ、１３はロータリーポンプであり、矢印は昇華し
た有機金属錯体が移送される方向あるいは分解ガスの排
出方向を示している。The organometallic complex accompanying gas introduced into the quartz reaction tube 7 as described above thermally decomposes the organometallic complex on the substrate 9 to form a metal thin film. In addition, the piping from the raw material container 2 to the thermal decomposition furnace 6 is kept at a temperature of 50 to 250 ° C. by the heat insulating layer 10 or a heat insulating means in order to prevent condensation. In the figure, 11 is a cooling trap, 12 is a valve, 13 is a rotary pump, and the arrows indicate the direction in which the sublimated organometallic complex is transferred or the direction in which the decomposition gas is discharged.
【００１４】本発明法において原料化合物として用いら
れるシクロペンタジエン系有機金属錯体（シクロペンタ
ジエン系有機金属錯体付加物を含む）は、高昇華性であ
り、しかも昇華温度と分解温度とがかなり離れているた
め、不活性ガスに同伴される錯体量が従来品よりも多
い。そのため、不純物混入のない均質な膜が、速い成膜
速度で得られるようになる。また、上記シクロペンタジ
エン系有機金属錯体は、従来の技術において原料化合物
として用いられていた有機金属錯体のように、弗素によ
る置換部分を有していないため、電気的特性が劣化する
ことはない。The cyclopentadiene-based organometallic complex (including the cyclopentadiene-based organometallic complex adduct) used as a starting compound in the method of the present invention is highly sublimable, and the sublimation temperature and the decomposition temperature are far apart. Therefore, the amount of the complex entrained by the inert gas is larger than that of the conventional product. Therefore, a uniform film free of impurities can be obtained at a high film forming rate. Further, the above-mentioned cyclopentadiene-based organometallic complex does not have a fluorine-substituted portion unlike the organometallic complex used as a raw material compound in the prior art, so that the electrical characteristics do not deteriorate.
【００１５】本発明法において原料化合物として用いら
れるシクロペンタジエン系有機金属錯体は、ペンタメチ
ルシクロペンタジエン（化３）、またはペンタエチルシ
クロペンタジエン（化４）と、Ｃａ、Ｓｒ、Ｂａ等のII
Ａ族元素とから構成されたものが好ましい。The cyclopentadiene-based organometallic complex used as a starting compound in the method of the present invention includes pentamethylcyclopentadiene (Chemical Formula 3) or pentaethylcyclopentadiene (Chemical Formula 4) and an II such as Ca, Sr or Ba.
Those composed of a group A element are preferred.
【００１６】[0016]
【化３】 Embedded image
【００１７】[0017]
【化４】 上記シクロペンタジエン系有機金属錯体は、上記シクロ
ペンタジエン系有機化合物と、IIＡ族金属の無機酸塩
（ハロゲン化物、硝酸塩、硫化物等）とを、例えばエー
テル系化合物等の溶媒系内で反応させ、得られた金属錯
体付加物（例えばエーテル付加体）から付加物を解離す
ることにより得ることができる。なお、上記金属錯体付
加物を薄膜材料として使用しても、優れた電気的特性を
有し、かつ再現性の良い均一な薄膜が得られることが確
認されている。Embedded image The cyclopentadiene-based organic metal complex is obtained by reacting the cyclopentadiene-based organic compound with an inorganic acid salt of a Group IIA metal (e.g., a halide, a nitrate, or a sulfide) in a solvent system such as an ether-based compound. It can be obtained by dissociating the adduct from the obtained metal complex adduct (for example, an ether adduct). It has been confirmed that even when the metal complex adduct is used as a thin film material, a uniform thin film having excellent electrical characteristics and good reproducibility can be obtained.
【００１８】以下、実施例により本発明をさらに詳細に
説明する。しかし本発明の範囲は、以下の実施例により
制限されるものではない。Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the following examples.
【００１９】[0019]
【実施例１】本発明法の一実施例として、熱ＣＶＤ法に
よる薄膜の製造方法を以下に示す。なお、図１は熱ＣＶ
Ｄ法の概略を模式的に示した図である。Embodiment 1 As an embodiment of the method of the present invention, a method of manufacturing a thin film by a thermal CVD method will be described below. FIG. 1 shows the thermal CV
It is the figure which showed the outline | summary of the method D typically.
【００２０】まず、恒温槽３内にあって、シクロペンタ
ジエン系有機金属錯体１（ビス−ペンタメチルシクロペ
ンタジエニルＳｒ錯体）１ｇが充填された原料容器２
（SUS316製、 100℃の恒温に保持）に、不活性キャリア
ーガス４（アルゴンガス）を、フローメーター５を経て
流量を 200ml／min に調節して導入し、このガス４に上
記有機金属錯体１を同伴、昇華させた。次いで、この有
機金属錯体１を同伴、昇華させたガスを、熱分解炉６内
に設けられ内部に基板９を載置した石英反応管７（ヒー
ター８によって 500℃に加熱保持されている）に導入さ
せ、基板９上への金属薄膜の成膜を行った（図１）。First, a raw material container 2 in a thermostat 3 filled with 1 g of a cyclopentadiene-based organometallic complex 1 (bis-pentamethylcyclopentadienyl Sr complex)
(Made of SUS316, kept at a constant temperature of 100 ° C.), an inert carrier gas 4 (argon gas) was introduced into the gas 4 at a flow rate of 200 ml / min through a flow meter 5. Accompanied by sublimation. Subsequently, the sublimated gas accompanying the organometallic complex 1 is supplied to a quartz reaction tube 7 (heated and held at 500 ° C. by a heater 8) provided in a pyrolysis furnace 6 and having a substrate 9 mounted therein. Then, a metal thin film was formed on the substrate 9 (FIG. 1).
【００２１】なお、原料容器２から熱分解炉６までの配
管は、凝縮を防ぐために保温層１０または加熱保温手段
により50〜 250℃に保温維持されている。また、図中１
１は冷却トラップ、１２はバルブ、１３はロータリーポ
ンプであり、矢印は昇華した有機金属錯体が移送される
方向あるいは分解ガスの排出方向を示している。The piping from the raw material container 2 to the thermal decomposition furnace 6 is kept at a temperature of 50 to 250 ° C. by a heat insulating layer 10 or a heat insulating means in order to prevent condensation. Also, 1 in the figure
1 is a cooling trap, 12 is a valve, 13 is a rotary pump, and the arrows indicate the direction in which the sublimated organometallic complex is transferred or the direction in which the decomposition gas is discharged.
【００２２】上記のようにして１時間成膜を行い、基板
９上に厚さ2000オングストロームの再現性の良い均一な
Ｓｒ薄膜を得た。The film was formed for one hour as described above, and a uniform reproducible Sr thin film having a thickness of 2000 Å was obtained on the substrate 9.
【００２３】[0023]
【実施例２】ビス−ペンタメチルシクロペンタジエニル
Ｓｒ錯体に代えてビス−ペンタメチルシクロペンタジエ
ニルＣａ錯体を用いたこと以外は実施例１と同様にして
薄膜の成膜を行ったところ、基板上に厚さ2100オングス
トロームの再現性の良い均一なＣａ薄膜が得られた。Example 2 A thin film was formed in the same manner as in Example 1 except that a bis-pentamethylcyclopentadienyl Ca complex was used instead of the bis-pentamethylcyclopentadienyl Sr complex. A uniform reproducible Ca thin film having a thickness of 2100 angstroms was obtained on the substrate.
【００２４】[0024]
【実施例３】ビス−ペンタメチルシクロペンタジエニル
Ｓｒ錯体の代わりにビス−ペンタメチルシクロペンタジ
エニルＳｒ錯体のエーテル付加物を用いたこと以外は実
施例１と同様にして薄膜の成膜を行ったところ、基板上
に厚さ1800オングストロームの再現性の良い均一なＳｒ
薄膜が得られた。Example 3 A thin film was formed in the same manner as in Example 1 except that an ether adduct of a bis-pentamethylcyclopentadienyl Sr complex was used instead of the bis-pentamethylcyclopentadienyl Sr complex. As a result, a uniform Sr of 1800 angstroms thick with good reproducibility
A thin film was obtained.
【００２５】[0025]
【比較例】ビス−ペンタメチルシクロペンタジエニルＳ
ｒ錯体の代わりに、従来より用いられてきたビス−ジパ
ロイルメタナトＳｒ錯体を用いたこと以外は実施例１と
同様にして薄膜の成膜を行ったところ、基板上に厚さ 9
00オングストロームのＳｒ薄膜が得られた。しかしなが
ら、この薄膜は再現性が悪く、薄膜形成速度も遅かっ
た。Comparative Example Bis-pentamethylcyclopentadienyl S
A thin film was formed in the same manner as in Example 1 except that a conventionally used bis-diparoylmethanato Sr complex was used instead of the r complex.
A Sr thin film of 00 Å was obtained. However, the reproducibility of this thin film was poor, and the film formation speed was low.
【００２６】[0026]
【発明の効果】本発明法において原料化合物として用い
られるシクロペンタジエン系有機金属錯体は、高昇華性
である上、昇華温度と分解温度とが明らかに離れている
ため、速い成膜速度で、均質かつ再現性に優れた薄膜を
得ることができるようになった。また、本発明法による
と、成膜中に弗化物が生成してしまうことがないため、
薄膜の電気的特性劣化がない。The cyclopentadiene-based organometallic complex used as a starting compound in the method of the present invention has a high sublimation property, and its sublimation temperature and decomposition temperature are clearly separated from each other. In addition, a thin film having excellent reproducibility can be obtained. In addition, according to the method of the present invention, fluoride is not generated during film formation.
There is no deterioration in electrical characteristics of the thin film.
【図１】熱ＣＶＤ法の概略を模式的に示す図である。FIG. 1 is a view schematically showing an outline of a thermal CVD method.
１‥‥‥有機金属錯体 ２‥‥‥原料容器 ３‥‥‥恒温槽 ４‥‥‥不活性キャリヤーガス ５‥‥‥フローメーター ６‥‥‥熱分解炉 ７‥‥‥石英反応管 ８‥‥‥ヒーター ９‥‥‥基板 １０‥‥保温層 １１‥‥冷却トラップ １２‥‥バルブ １３‥‥ロータリーポンプ 1 Organometallic complex 2 Raw material container 3 Thermostat 4 Inert carrier gas 5 Flow meter 6 Pyrolysis furnace 7 Quartz reaction tube 8 {Heater 9} Substrate 10} Heat insulation layer 11} Cooling trap 12} Valve 13} Rotary pump
───────────────────────────────────────────────────── フロントページの続き (72)発明者 坂本 陵 東京都千代田区丸の内１丁目８番２号 同和鉱業株式会社内 (56)参考文献 特開 平２−225317（ＪＰ，Ａ) 特開 平２−69389（ＪＰ，Ａ) 特開 平１−165774（ＪＰ，Ａ) 特開 平３−197302（ＪＰ，Ａ) 特開 平１−265511（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 16/18 ＪＩＣＳＴファイル（ＪＯＩＳ)──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Ryo Sakamoto 1-8-2 Marunouchi, Chiyoda-ku, Tokyo Dowa Mining Co., Ltd. (56) References JP-A-2-225317 (JP, A) JP-A-2 -69389 (JP, A) JP-A-1-165774 (JP, A) JP-A-3-197302 (JP, A) JP-A-1-265511 (JP, A) (58) Fields investigated (Int. . 7, DB name) C23C 16/18 JICST file (JOIS)
Claims (1)
あって、化１で示されるシクロペンタジエン系有機化合
物とIIＡ族金属との有機金属錯体を原料化合物として用
いて不活性キャリアーガスに同伴、昇華させ、次いで基
板を配置した２５０〜７５０℃の反応管内に該有機金属
錯体を同伴した不活性キャリアーガスを導入して熱分解
させることにより該基板上に該IIＡ族金属の金属薄膜を
均一に生成することを特徴とする金属薄膜の製造法。 【化１】 （ただし、式中Ｒはメチル基またはエチル基を表す。）A method for producing a metal thin film by a vapor phase growth method, wherein an organometallic complex of a cyclopentadiene-based organic compound represented by Chemical Formula 1 and a Group IIA metal is used as a starting compound.
Entrain and sublimate with an inert carrier gas
The organic metal is placed in a reaction tube at 250 to 750 ° C.
Thermal decomposition by introducing inert carrier gas with complex
To form a metal thin film of the Group IIA metal on the substrate.
A method for producing a metal thin film, wherein the metal thin film is formed uniformly . Embedded image (However, R represents a methyl group or an ethyl group in the formula.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12012392A JP3231835B2 (en) | 1992-04-14 | 1992-04-14 | Production method of thin film using organometallic complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12012392A JP3231835B2 (en) | 1992-04-14 | 1992-04-14 | Production method of thin film using organometallic complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05287534A JPH05287534A (en) | 1993-11-02 |
| JP3231835B2 true JP3231835B2 (en) | 2001-11-26 |
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|---|---|---|---|
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|---|---|---|---|---|
| JP3547471B2 (en) * | 1994-03-09 | 2004-07-28 | 富士通株式会社 | Vapor phase growth method of dielectric film |
| US6180190B1 (en) | 1997-12-01 | 2001-01-30 | President And Fellows Of Harvard College | Vapor source for chemical vapor deposition |
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- 1992-04-14 JP JP12012392A patent/JP3231835B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
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