JP2977484B2 - Barium source material for CVD and film forming method using the same - Google Patents
Barium source material for CVD and film forming method using the sameInfo
- Publication number
- JP2977484B2 JP2977484B2 JP8052635A JP5263596A JP2977484B2 JP 2977484 B2 JP2977484 B2 JP 2977484B2 JP 8052635 A JP8052635 A JP 8052635A JP 5263596 A JP5263596 A JP 5263596A JP 2977484 B2 JP2977484 B2 JP 2977484B2
- Authority
- JP
- Japan
- Prior art keywords
- barium
- cvd
- complex
- organic
- source material
- 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
- 229910052788 barium Inorganic materials 0.000 title claims description 74
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims description 74
- 239000000463 material Substances 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 16
- 238000005229 chemical vapour deposition Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- UZICKDIYFALSHI-UHFFFAOYSA-N 2,2,6,6-tetramethyloctane-3,5-dione Chemical compound CCC(C)(C)C(=O)CC(=O)C(C)(C)C UZICKDIYFALSHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 2
- XCBBNTFYSLADTO-UHFFFAOYSA-N 2,3-Octanedione Chemical compound CCCCCC(=O)C(C)=O XCBBNTFYSLADTO-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 description 21
- 239000010408 film Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 15
- 239000010409 thin film Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000859 sublimation Methods 0.000 description 4
- 230000008022 sublimation Effects 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XMVWWXJDPXBJQG-UHFFFAOYSA-N 2,2,3-trimethylnonane-4,6-dione Chemical compound CCCC(=O)CC(=O)C(C)C(C)(C)C XMVWWXJDPXBJQG-UHFFFAOYSA-N 0.000 description 1
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical group CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Landscapes
- Formation Of Insulating Films (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Vapour Deposition (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は，化学的気相蒸着法
（ＣＶＤ法）によってバリウムまたはバリウム含有物質
を析出させるのに適したＣＶＤ用バリウム源物質に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a barium source material for CVD suitable for depositing barium or a barium-containing material by chemical vapor deposition (CVD).
【０００２】[0002]
【０００３】超電導材料や強誘電体材料などに有用な薄
膜として，バリウムまたはバリウム含有物質の薄膜をＣ
ＶＤ法で成膜することが種々提案されている。バリウム
またはバリウム含有物質をＣＶＤ法によって析出させる
場合の原料化合物として有機バリウム錯体を用いること
が有利である。As a thin film useful for superconducting materials and ferroelectric materials, a thin film of barium or a barium-containing substance is used.
Various proposals have been made to form a film by the VD method. It is advantageous to use an organic barium complex as a raw material compound when depositing barium or a barium-containing substance by a CVD method.
【０００４】従来より，或る金属またはその化合物をＣ
ＶＤ法で成膜するさいの原料化合物としてその金属の有
機錯体が使用されており，かような有機金属錯体を構成
する有機部分（配位子）としては，ジピバロイルメタン
或いはヘキサフルオロアセチルアセトン等のβ−ジケト
ンが一般に知られている。特開平４−７２０６６号公報
および特開平４−７４８６６号公報には周期律表第IIＡ
属金属， IIIＡ属金属，IVＡ属金属，ＩＢ属金属との錯
体を構成する有機化合物として炭素数１〜５の低級アル
キル基をもつ１，３−ジケトン類が記載されている。Conventionally, a metal or its compound has been
An organic complex of the metal is used as a raw material compound when forming a film by the VD method, and the organic portion (ligand) constituting such an organometallic complex is dipivaloylmethane or hexafluoroacetylacetone. Β-diketones are generally known. JP-A-4-72066 and JP-A-4-74866 disclose Periodic Table IIA.
1,3-diketones having a lower alkyl group having 1 to 5 carbon atoms are described as organic compounds forming a complex with a group metal, a group IIIA metal, a group IVA metal, and a group IB metal.
【０００５】なお，ＣＶＤ法には，熱ＣＶＤ法，光ＣＶ
Ｄ法またはプラズマＣＶＤ法などが知られており，いず
れも原料化合物の蒸気を分解させて薄膜を形成するもの
であるが，原料化合物の蒸気を発生させる場合には，固
体状態にある原料化合物からその蒸気を昇華させるのが
一般的である。[0005] The CVD method includes a thermal CVD method and a light CV method.
The D method and the plasma CVD method are known, and each method decomposes the vapor of the raw material compound to form a thin film. When the vapor of the raw material compound is generated, the raw material compound in a solid state is used. It is common to sublimate the vapor.
【０００６】[0006]
【発明が解決しようとする課題】従来提案されたβ−ジ
ケトン系有機化合物を配位子とした有機バリウム錯体
は，一般にその融点が高い（ほぼ２２０℃前後）。この
ため，ＣＶＤ法の原料化合物に適用する場合，これを融
点以上の高温に加熱することはせずに，固体状態からの
昇華によって原料蒸気を発生させることが行われてい
る。An organic barium complex using a β-diketone-based organic compound as a ligand generally has a high melting point (about 220 ° C.). For this reason, when applied to a raw material compound of the CVD method, a raw material vapor is generated by sublimation from a solid state without heating it to a high temperature higher than its melting point.
【０００７】固体状態からの昇華の場合には，原料容器
内の原料残量が減少するに従って，原料化合物の表面積
が減少して気化速度が遅くなるという現象が起き，この
蒸気量の減少により，一定した成膜速度を長時間確保す
ることができないという問題がある。また，この気化速
度が変化することにより，バリウムと他の元素とが複合
した物質の薄膜（例えばＹＢａ2Ｃｕ3 Ｏ7 など) を作
製しようとする場合には, その組成の制御が困難になる
という問題もある。In the case of sublimation from the solid state, as the remaining amount of the raw material in the raw material container decreases, a phenomenon occurs in which the surface area of the raw material compound decreases and the vaporization rate slows down. There is a problem that a constant film forming rate cannot be secured for a long time. In addition, when the vaporization rate changes, it is difficult to control the composition of a thin film of a substance in which barium and other elements are combined (for example, YBa 2 Cu 3 O 7 ). There is also a problem.
【０００８】前記の特開平４−７２０６６号公報および
特開平４−７４８６６号公報に記載された有機金属錯体
も高昇華性である点を特徴とするものであり，ＣＶＤ用
原料化合物としては固体状態で蒸発させるものである。
したがって，前記同様の問題がある。The organometallic complexes described in the above-mentioned JP-A-4-72066 and JP-A-4-74866 are also characterized by a high sublimation property. Is to evaporate.
Therefore, there is the same problem as described above.
【０００９】また，ヘキサフルオロアセチルアセトン等
のように分子内にフッ素を含む配位子を用いた有機金属
錯体は，融点は低いが成膜した膜中に不純物としてフッ
化物が混在するおそれがあり，この場合には膜の特性を
著しく損なう結果となる。An organometallic complex using a ligand containing fluorine in the molecule, such as hexafluoroacetylacetone, has a low melting point, but fluoride may be mixed as an impurity in the formed film. In this case, the characteristics of the film are significantly impaired.
【００１０】したがって本発明は，前記のような問題を
解決できるような低融点のＣＶＤ用バリウム源物質を得
ることを課題としたものである。Accordingly, an object of the present invention is to provide a barium source material for CVD having a low melting point which can solve the above-mentioned problems.
【００１１】[0011]
【課題を解決するための手段】本発明者らは斯かる課題
を解決するために鋭意研究したところ，２，２，６，６
−テトラメチル−３，５−オクタンジオンのβ−ジケト
ンを配位子とした有機バリウム錯体は，ＣＶＤ用原料化
合物として液体状態で使用可能な低融点（ほぼ１４０〜
１５０℃）を有し且つ蒸発温度と分解温度がはっきり離
れているというＣＶＤ法の成膜にとって極めて有利な性
質を有することを見いだした。この特性により，これを
ＣＶＤ法のバリウム源物質とした場合，液体状態からの
蒸発を行わせることができ，またバリウムの原料蒸気の
基材への供給と基材上でのバリウムの分解析出を安定し
て行わせることができるので，既述の課題が解決できる
ことがわかった。Means for Solving the Problems The present inventors have conducted intensive studies in order to solve such problems and found that 2,2,6,6
An organic barium complex having β-diketone of tetramethyl-3,5-octanedione as a ligand has a low melting point (approximately 140 to 140) which can be used in a liquid state as a raw material compound for CVD.
150 ° C.), and has a very advantageous property for film formation by the CVD method, in which the evaporation temperature and the decomposition temperature are clearly separated. Due to this characteristic, when this is used as a barium source material in the CVD method, evaporation from a liquid state can be performed. In addition, barium raw material vapor is supplied to the substrate and barium is decomposed and deposited on the substrate. Can be performed stably, so that the above-mentioned problem can be solved.
【００１２】すなわち，本発明によれば，ＣＶＤ法によ
りバリウムまたはバリウム含有物質を析出させるのに使
用するＣＶＤ用バリウム源物質であって，２，２，６，
６−テトラメチル−３，５−オクタンジオンをバリウム
の配位子とした有機バリウム錯体からなるＣＶＤ用バリ
ウム源物質を提供する。That is, according to the present invention, there is provided a barium source material for CVD used for depositing barium or a barium-containing material by a CVD method.
Provided is a barium source material for CVD comprising an organic barium complex having 6-tetramethyl-3,5-octanedione as a barium ligand.
【００１３】また本発明によれば，ＣＶＤ法によりバリ
ウムまたはバリウム含有物質を基材上に析出させるさい
に，バリウム源物質として２，２，６，６−テトラメチ
ル−３，５−オクタンジオンをバリウムの配位子とした
有機バリウム錯体を使用し，この有機バリウム錯体を融
点以上の温度に加熱し，当該錯体の液相から当該錯体を
蒸発させることを特徴とするＣＶＤ法によるバリウムま
たはバリウム含有物質の成膜法を提供する。According to the present invention, 2,2,6,6-tetramethyl-3,5-octanedione is used as a barium source material when depositing barium or a barium-containing material on a substrate by a CVD method. Using an organic barium complex as a barium ligand, heating the organic barium complex to a temperature equal to or higher than the melting point, and evaporating the complex from a liquid phase of the complex; Provided is a method for forming a substance.
【００１４】本発明に従う有機バリウム錯体は化１の一
般式で表されるものであり，新規化合物であると思われ
る。The organic barium complex according to the present invention is represented by the general formula (1) and is considered to be a novel compound.
【００１５】[0015]
【化１】 Embedded image
【００１６】[0016]
【発明の実施の形態】本発明に従うβ−ジケトン系有機
バリウム錯体は，金属バリウムと，配位子の２，２，
６，６−テトラメチル−３，５−オクタンジオンを，ト
ルエン溶液中で加熱攪拌し，溶媒を留去して析出した固
体を，再結晶，蒸留等の精製法で精製するという方法で
得ることができる。BEST MODE FOR CARRYING OUT THE INVENTION The β-diketone-based organic barium complex according to the present invention comprises metal barium and ligands 2,2,2.
A method in which 6,6-tetramethyl-3,5-octanedione is heated and stirred in a toluene solution, and the solvent is distilled off. A precipitated solid is obtained by a purification method such as recrystallization or distillation. Can be.
【００１７】このようにして得られた本発明の有機バリ
ウム錯体をＣＶＤ法の原料化合物として使用し，ＣＶＤ
法で該バリウムまたはバリウム含有物質を成膜するに
は，例えば図１に示したように，該有機バリウム錯体１
を入れた原料容器２を恒温槽３内で所定の温度（融点よ
り高い温度，例えば１８０〜１９０℃）に保持し，不活
性キャリアガス（例えばアルゴンガス）４を流量計５に
よって流量を調整しながら（例えば５〜５００ミリリッ
トル／分）原料容器２内に導入することよって，有機バ
リウム錯体を同伴したガス流を該容器２から発生させ
る。The organic barium complex of the present invention thus obtained is used as a starting compound in a CVD method,
In order to form a film of the barium or barium-containing material by the method, for example, as shown in FIG.
Is maintained at a predetermined temperature (a temperature higher than the melting point, for example, 180 to 190 ° C.) in a thermostat 3, and the flow rate of an inert carrier gas (eg, argon gas) 4 is adjusted by a flow meter 5. The gas flow accompanied by the organic barium complex is generated from the container 2 by introducing the gas into the raw material container 2 (for example, 5 to 500 ml / min).
【００１８】発生した有機バリウム錯体蒸気は熱分解炉
６の反応管７内に導かれる。反応管（例えば石英管）７
はヒータ８によって加熱され，管内に設置した基板９を
所定の温度（例えば４００〜８００℃）に加熱保持する
ことによって，該有機バリウム錯体が熱分解して基板９
上にバリウムが析出し，成膜する。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１
０または加熱保温手段によって１８５〜１９５℃に保温
維持するのがよい。反応管７から出る排ガスは冷却トラ
ップ１１を経て排出される。図中の１２はバルブを，ま
た１３はロータリーポンプを示している。なお，バリウ
ムの酸化物を成膜するさいには，酸素容器１４から流量
計１５およびバルブ１６を経て反応雰囲気中（例えば反
応管７内）に適量の気体酸素を送気する。また，他の元
素との複合物質を成膜するには，図示されてはいない
が，当該他の物質の原料化合物を同時に反応管７内に導
くようにする。The generated organic barium complex vapor is led into the reaction tube 7 of the thermal decomposition furnace 6. Reaction tube (for example, quartz tube) 7
Is heated by a heater 8, and the substrate 9 placed in the tube is heated and maintained at a predetermined temperature (for example, 400 to 800 ° C.).
Barium is deposited on the film to form a film. The piping from the raw material container 2 to the thermal decomposition furnace 6 is provided with a heat insulating layer 1 to prevent condensation.
It is preferable to keep the temperature at 185 to 195 ° C. by 0 or a heating and keeping means. Exhaust gas from the reaction tube 7 is discharged through a cooling trap 11. In the figure, reference numeral 12 denotes a valve, and reference numeral 13 denotes a rotary pump. In forming the barium oxide film, an appropriate amount of gaseous oxygen is supplied from the oxygen container 14 to the reaction atmosphere (for example, in the reaction tube 7) via the flow meter 15 and the valve 16. In addition, in order to form a film of a composite material with another element, a raw material compound of the other material is simultaneously introduced into the reaction tube 7 although not shown.
【００１９】[0019]
〔実施例１〕図１のＣＶＤ設備を用いて，ステンレス鋼
製の原料容器２内に，バリウム源としての原料化合物と
して，化１に示したビス（２，２，６，６−テトラメチ
ル−３，５−オクタンジオナト）バリウムを入れ，基板
９には酸化マグネシウム基板を用いてその上に成膜する
操作を行った。Example 1 Using the CVD equipment shown in FIG. 1, a bis (2,2,6,6-tetramethyl-) compound represented by Chemical Formula 1 was placed in a stainless steel material container 2 as a raw material compound as a barium source. (3,5-Octandionato) barium was added, and a magnesium oxide substrate was used as the substrate 9 to form a film thereon.
【００２０】なお，化１のビス（２，２，６，６−テト
ラメチル−３，５−オクタンジオナト）バリウムは，次
のようにして製造した。まず，窒素雰囲気下で，金属バ
リウム２ｇにトルエン１００ミリリットルを加え，これ
に２，２，６，６−テトラメチル−３，５−オクタンジ
オン２０ｇを加えて１３０℃で攪拌し，金属バリウムが
完全に溶解した後，溶媒を減圧留去し，さらに減圧乾燥
したのち昇華精製によって７ｇのビス（２，２，６，６
−テトラメチル−３，５−オクタンジオナト）バリウム
を得た。得られた錯体の融点測定を行ったところ１４０
〜１５０℃であった。The bis (2,2,6,6-tetramethyl-3,5-octandionato) barium of Chemical formula 1 was produced as follows. First, under a nitrogen atmosphere, 100 ml of toluene was added to 2 g of metal barium, 20 g of 2,2,6,6-tetramethyl-3,5-octanedione was added thereto, and the mixture was stirred at 130 ° C. to completely remove metal barium. The solvent was distilled off under reduced pressure, dried under reduced pressure and purified by sublimation to obtain 7 g of bis (2,2,6,6).
-Tetramethyl-3,5-octandionato) barium was obtained. The melting point of the obtained complex was 140.
１５０150 ° C.
【００２１】この有機バリウム錯体１ｇを容器２内に装
填し，恒温槽３を２００℃の恒温に設定保持した。酸化
マグネシウム基板９をヒータ８によって８００℃に加熱
保持した状態で，キャリヤーガスとしてアルゴンガスを
１００ミリリットル／分を通流して該化合物を石英反応
管７に導いた。容器２から熱分解炉６までの配管は２１
０℃に保持されるように保温した。1 g of the organic barium complex was charged into the container 2 and the temperature of the constant temperature bath 3 was kept at 200 ° C. With the magnesium oxide substrate 9 heated and maintained at 800 ° C. by the heater 8, argon gas as a carrier gas was passed at 100 ml / min to guide the compound to the quartz reaction tube 7. The piping from vessel 2 to pyrolysis furnace 6 is 21
The temperature was kept at 0 ° C.
【００２２】この条件下で６０分間の成膜操作を行った
ところ，厚さ１１００オングストロームの均一なバリウ
ムの薄膜が得られた。When a film forming operation was performed under these conditions for 60 minutes, a uniform barium thin film having a thickness of 1100 angstroms was obtained.
【００２３】容器２に装填したビス（２，２，６，６−
テトラメチル−３，５−オクタンジオナト）バリウムの
量を２ｇに変更した以外は，前記と全く同じ条件で成膜
操作を繰り返した。この場合にも同じく厚さが１１００
オングストロームの均一なバリウムの薄膜が得られた。
すなわち，容器２に装填する原料化合物量を変えても同
厚の成膜ができた。このことは，原料化合物からの蒸発
量が処理時間中一定であり，且つ分解量も一定であるこ
とを示している。The screws (2,2,6,6-
The film forming operation was repeated under exactly the same conditions as above, except that the amount of tetramethyl-3,5-octandionato) barium was changed to 2 g. In this case, the thickness is also 1100.
A uniform barium thin film of Angstrom was obtained.
That is, even when the amount of the raw material compound charged in the container 2 was changed, a film having the same thickness was formed. This indicates that the amount of evaporation from the starting compound is constant during the treatment time and the amount of decomposition is also constant.
【００２４】〔実施例２〕気体酸素を酸素源１４から流
量計１５および弁１６を経て反応管７内に１００ミリリ
ットル／分の流量で追加した以外は，実施例１と同様の
処理を同じく６０分間行った。その結果，原料装填量が
１ｇと２ｇの両方とも１４００オングストロームの同じ
厚さの酸化バリウムの薄膜が得られた。Example 2 The same processing as in Example 1 was repeated except that gaseous oxygen was added from the oxygen source 14 via the flow meter 15 and the valve 16 to the reaction tube 7 at a flow rate of 100 ml / min. Minutes. As a result, a barium oxide thin film having the same thickness of 1400 angstroms was obtained for both the raw material loading amounts of 1 g and 2 g.
【００２５】〔比較例１〕ビス（２，２，６，６−テト
ラメチル−３，５−オクタンジオナト）バリウムに代え
て，融点が２１６〜２１８℃のビス（ジピバロイルメタ
ナト）バリウムを使用した以外は，実施例１と同様な条
件で成膜した。その結果，６０分後に原料充填量１ｇの
ものは厚さが１５００オングストローム，また，原料充
填量２ｇのものは厚さが２１００オングストロームのバ
リウムの薄膜が得られた。このことは，容器内原料の容
積変化にともなって，蒸発量も経時変化したことを示し
ている。COMPARATIVE EXAMPLE 1 Bis (dipivaloylmethanato) barium having a melting point of 216 to 218 ° C., instead of bis (2,2,6,6-tetramethyl-3,5-octandionato) barium A film was formed under the same conditions as in Example 1 except that was used. As a result, a barium thin film having a thickness of 1500 angstroms was obtained for the material with a loading of 1 g and a thin film of barium having a thickness of 2100 angstroms with a loading of 2 g after 60 minutes. This indicates that the evaporation amount also changed over time with the change in the volume of the raw material in the container.
【００２６】〔比較例２〕気体酸素を酸素源１４から流
量計１５および弁１６を経て反応管７内に１００ミリリ
ットル／分の流量で追加した以外は，比較例１と同様の
処理を同じく６０分間行った。その結果，原料充填量１
ｇのものは厚さが１９００オングストローム，また原料
充填量２ｇのものは厚さが２７００オングストロームの
酸化バリウムの薄膜が得られた。Comparative Example 2 The same process as in Comparative Example 1 was repeated except that gaseous oxygen was added from the oxygen source 14 via the flowmeter 15 and the valve 16 into the reaction tube 7 at a flow rate of 100 ml / min. Minutes. As a result, the raw material charge 1
g had a thickness of 1900 angstroms, and a material with a loading of 2 g had a barium oxide thin film having a thickness of 2700 angstroms.
【００２７】[0027]
【発明の効果】以上のように，本発明に従うβ−ジケト
ン系有機バリウム錯体は低融点で，高気化性であり，か
つ蒸発温度と分解温度がはなれていることから，ＣＶＤ
法によってバリウムまたはバリウム含有物質の薄膜を製
造するためのバリウム源物質として使用する場合に，液
体状態で使用できるという優れた利点があり，またこの
ために蒸発速度が一定となるので安定した成膜速度が得
られ，しかも高速で且つ均質な成膜ができるという特徴
がある。As described above, the β-diketone-based organic barium complex according to the present invention has a low melting point, a high vaporization property, and a separation between the evaporation temperature and the decomposition temperature.
When used as a barium source material for producing a thin film of barium or a barium-containing material by the method, it has an excellent advantage that it can be used in a liquid state. The feature is that a high speed can be obtained, and high-speed and uniform film formation can be achieved.
【００２８】したがって，本発明によれば，超電導材料
や強誘電体材料などに有用なバリウムまたはバリウム含
有物質の成膜技術に多大の貢献ができる。Therefore, according to the present invention, a great contribution can be made to the technique of forming barium or a barium-containing substance useful for a superconducting material or a ferroelectric material.
【図１】熱ＣＶＤ法を実施する設備の機器配置例を示し
た略断面図である。FIG. 1 is a schematic sectional view showing an example of equipment arrangement of equipment for performing 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 流量計 ６ 熱分解炉 ７ 石英反応管 ８ ヒータ 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 １４ 酸素源 REFERENCE SIGNS LIST 1 organic metal complex 2 raw material container 3 constant temperature bath 4 inert carrier gas 5 flow meter 6 pyrolysis furnace 7 quartz reaction tube 8 heater 9 substrate 10 heat retaining layer 11 cooling trap 12 valve 13 rotary pump 14 oxygen source
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ３０Ｂ 29/22 ５０１ Ｃ３０Ｂ 29/22 ５０１Ｅ // Ｃ０７Ｆ 3/04 Ｃ０７Ｆ 3/04 Ｈ０１Ｌ 21/314 Ｈ０１Ｌ 21/314 Ａ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C30B 29/22 501 C30B 29/22 501E // C07F 3/04 C07F 3/04 H01L 21/314 H01L 21/314 A
Claims (4)
含有物質を析出させるのに使用するＣＶＤ用バリウム源
物質であって，２，２，６，６−テトラメチル−３，５
−オクタンジオンをバリウムの配位子とした有機バリウ
ム錯体からなるＣＶＤ用バリウム源物質。A barium source material for CVD used for depositing barium or a barium-containing material by a CVD method, comprising 2,2,6,6-tetramethyl-3,5.
-A barium source material for CVD comprising an organic barium complex having octanedione as a barium ligand.
項１に記載のＣＶＤ用バリウム源物質。 【化１】 2. The barium source material for CVD according to claim 1, wherein the organic barium complex is represented by Chemical Formula 1. Embedded image
０℃のものである請求項１または２に記載のＣＶＤ用バ
リウム源物質。3. The organic barium complex has a melting point of 140 to 15.
The barium source material for CVD according to claim 1 or 2, which is at 0 ° C.
含有物質を基材上に析出させるさいに，バリウム源物質
として２，２，６，６−テトラメチル−３，５−オクタ
ンジオンをバリウムの配位子とした有機バリウム錯体を
使用し，この有機バリウム錯体を融点以上の温度に加熱
し，当該錯体の液相から当該錯体を蒸発させることを特
徴とするＣＶＤ法によるバリウムまたはバリウム含有物
質の成膜法。4. When barium or a barium-containing substance is deposited on a substrate by a CVD method, 2,2,6,6-tetramethyl-3,5-octanedione is used as a barium source substance as a barium ligand. A method for forming a barium or barium-containing material by a CVD method, comprising heating the organic barium complex to a temperature equal to or higher than its melting point and evaporating the complex from the liquid phase of the complex. .
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| Publication Number | Publication Date |
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