JPH08269717A - Organobismuth compound for forming thin film of bismuth and bismuth oxide by chemical vapor deposition of organo-metallic compound having high vapor pressure - Google Patents
Organobismuth compound for forming thin film of bismuth and bismuth oxide by chemical vapor deposition of organo-metallic compound having high vapor pressureInfo
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- JPH08269717A JPH08269717A JP7075361A JP7536195A JPH08269717A JP H08269717 A JPH08269717 A JP H08269717A JP 7075361 A JP7075361 A JP 7075361A JP 7536195 A JP7536195 A JP 7536195A JP H08269717 A JPH08269717 A JP H08269717A
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- bismuth
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は蒸気圧の高い有機金属化
学蒸着によるビスマス及びビスマス酸化物薄膜形成用有
機ビスマス化合物に係り、特に、超伝導材料、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
ビスマス又はビスマス酸化物薄膜を有機金属化学蒸着法
（Metalorganic Chemical Vapor Deposition：以下「Ｍ
ＯＣＶＤ法」と称す。）により形成するに際して、蒸着
原料として用いるのに適した有機ビスマス化合物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic bismuth compound for forming bismuth and bismuth oxide thin films by high vapor pressure organometallic chemical vapor deposition, and is particularly useful as a superconducting material, a ferroelectric material, a semiconductor thin film material and the like. Bismuth or bismuth oxide thin film having a specific composition such as Metalorganic Chemical Vapor Deposition:
OCVD method ". The present invention relates to an organic bismuth compound suitable for use as a vapor deposition raw material when formed by.
【０００２】[0002]
【従来の技術】従来、超伝導材料、強誘電体材料、半導
体薄膜材料等の各種ビスマス又はビスマス酸化物薄膜を
ＭＯＣＶＤ法により形成するに際して用いられるビスマ
ス蒸着原料としては、下記構造式（Ａ）で表されるトリ
フェニルビスマス又は下記構造式（Ｂ）で表されるトリ
−ｏ−メチルフェニルビスマスからなる有機ビスマス化
合物が知られている。2. Description of the Related Art Conventionally, a bismuth vapor deposition material used for forming various bismuth or bismuth oxide thin films such as superconducting materials, ferroelectric materials and semiconductor thin film materials by the MOCVD method has the following structural formula (A). An organic bismuth compound composed of triphenylbismuth represented or tri-o-methylphenylbismuth represented by the following structural formula (B) is known.
【０００３】[0003]
【化５】 Embedded image
【０００４】[0004]
【化６】 [Chemical 6]
【０００５】このような蒸着原料を用いてＭＯＣＶＤ法
によりビスマス薄膜を形成するには、例えば、図１の概
略説明図に示す如く、反応炉８内に設けたヒーター７上
に基板６を置き、一方、この反応炉８と連接して設けた
加熱炉３内で、気化容器２内の上記有機ビスマス化合物
からなる蒸着原料１を気化させ、得られた蒸気を配管４
から導入されるＡｒ，Ｎ2 等のキャリアガスで反応炉８
内に送給して拡散させ、加熱基板６上にビスマスを析出
させる。この際に反応ガスとしてＯ2 ，Ｎ2 Ｏ，オゾン
等の酸化性ガスを、配管５から反応炉８に導入すること
によりビスマス酸化物を析出させることもできる。な
お、図中、９は真空引配管、Ｐは圧力計である。この方
法は熱分解型ＭＯＣＶＤ法と称される。In order to form a bismuth thin film by MOCVD using such a vapor deposition material, for example, as shown in the schematic explanatory view of FIG. 1, the substrate 6 is placed on a heater 7 provided in a reaction furnace 8, On the other hand, in the heating furnace 3 provided so as to be connected to the reaction furnace 8, the vapor deposition material 1 made of the organic bismuth compound in the vaporization vessel 2 is vaporized, and the obtained vapor is piped.
Carrier gas such as Ar and N 2 introduced from the reactor 8
The bismuth is deposited on the heating substrate 6 by being fed into and diffused therein. At this time, an oxidative gas such as O 2 , N 2 O, or ozone may be introduced as a reaction gas into the reaction furnace 8 from the pipe 5 to precipitate the bismuth oxide. In the figure, 9 is a vacuum piping, and P is a pressure gauge. This method is called a thermal decomposition type MOCVD method.
【０００６】[0006]
【発明が解決しようとする課題】しかし、上記の熱分解
型ＭＯＣＶＤ法の蒸着原料として従来用いられている有
機ビスマス化合物のうち、前記構造式（Ａ）で示される
有機ビスマス化合物は、気化の際の加熱温度に対して不
安定で、気化における加熱の際に、図１中の気化容器２
内にて、気化の他に有機ビスマス化合物が熱分解反応を
起こすなど、化合物の熱安定性の面で問題がある。ま
た、前記構造式（Ｂ）で示される有機ビスマス化合物
は、構造式（Ａ）で示される有機ビスマス化合物に比べ
て熱安定性に優れるものの、昇華温度、即ち蒸発温度と
分解温度に顕著な差がなく、結果として成膜の際のコン
トロールが困難で、再現性良く均一でかつ安定した成膜
速度が得られないという欠点がある。また、前記構造式
（Ａ），（Ｂ）の化合物を用いてビスマス及びビスマス
酸化物を析出させるためには、基板を５５０℃以上の高
温に加熱することが必要とされる。However, among the organic bismuth compounds conventionally used as vapor deposition raw materials for the above-mentioned thermal decomposition type MOCVD method, the organic bismuth compound represented by the structural formula (A) is used during vaporization. 1 is unstable with respect to the heating temperature of the vaporization container, and the vaporization container 2 in FIG.
In addition to vaporization, there is a problem in terms of thermal stability of the compound, such as an organic bismuth compound causing a thermal decomposition reaction. Further, the organic bismuth compound represented by the structural formula (B) is superior in thermal stability to the organic bismuth compound represented by the structural formula (A), but has a significant difference in sublimation temperature, that is, evaporation temperature and decomposition temperature. As a result, it is difficult to control the film formation, and it is difficult to obtain a uniform and stable film formation rate with good reproducibility. Further, in order to deposit bismuth and bismuth oxide using the compounds of the structural formulas (A) and (B), it is necessary to heat the substrate to a high temperature of 550 ° C. or higher.
【０００７】本発明は上記従来の問題点を解決し、熱分
解型ＭＯＣＶＤ法等のＭＯＣＶＤ法によるビスマス及び
ビスマス酸化物薄膜の形成に際し、気化安定性に優れ、
４５０〜５５０℃という比較的低温で均一かつ安定した
成膜速度を再現性良く得ることができるビスマス及びビ
スマス酸化物薄膜形成用有機ビスマス化合物を提供する
ことを目的とする。The present invention solves the above-mentioned conventional problems and has excellent vaporization stability when forming bismuth and bismuth oxide thin films by MOCVD such as thermal decomposition MOCVD.
An object of the present invention is to provide bismuth and an organic bismuth compound for forming a bismuth oxide thin film, which can obtain a uniform and stable film formation rate at a relatively low temperature of 450 to 550 ° C. with good reproducibility.
【０００８】[0008]
【課題を解決するための手段】本発明の蒸気圧の高い有
機金属化学蒸着によるビスマス及びビスマス酸化物薄膜
形成用有機ビスマス化合物は、下記一般式（Ｉ）で表さ
れることを特徴とする。The organic bismuth compound for forming a bismuth and bismuth oxide thin film by high vapor pressure organometallic chemical vapor deposition of the present invention is characterized by being represented by the following general formula (I).
【０００９】[0009]
【化７】 [Chemical 7]
【００１０】（ただし、上記（Ｉ）式中、Ｒ1 ，Ｒ2
は、炭素数１〜４の直鎖又は分岐状のアルキル基、炭素
数１〜４の直鎖又は分岐状のフッ化アルキル基、水素原
子又はフッ素原子を示し、Ｒ1 とＲ2 とは互いに異なっ
ていても良く、同一であっても良い。） 請求項２の蒸気圧の高い有機金属化学蒸着によるビスマ
ス及びビスマス酸化物薄膜形成用有機ビスマス化合物
は、下記構造式で表されるビス［ジ−ｐ−エチルフェ
ニル］ジビスマス（以下「（Ｄ−ｐ−ＥｔＰｈ）ＤＢ
ｉ」と略記する。）であることを特徴とする。(However, in the above formula (I), R 1 , R 2
Represents a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms, a hydrogen atom or a fluorine atom, and R 1 and R 2 are mutually They may be different or the same. The bismuth and the organic bismuth compound for forming a bismuth oxide thin film by the organometallic chemical vapor deposition having a high vapor pressure according to claim 2 are bis [di-p-ethylphenyl] dibismuth represented by the following structural formula (hereinafter referred to as "(D- p-EtPh) DB
abbreviated as "i". ).
【００１１】[0011]
【化８】 Embedded image
【００１２】請求項３の蒸気圧の高い有機金属化学蒸着
によるビスマス及びビスマス酸化物薄膜形成用有機ビス
マス化合物は、下記構造式で表されるビス［ジ−ｍ−
フルオロフェニル］ジビスマス（以下「（Ｄ−ｍ−ＦＰ
ｈ）ＤＢｉ」と略記する。）であることを特徴とする。The bismuth and the organic bismuth compound for forming a bismuth oxide thin film by the organometallic chemical vapor deposition having a high vapor pressure according to claim 3 are represented by the following structural formula: bis [di-m-
Fluorophenyl] dibismuth (hereinafter “(Dm-FP
h) DBi ". ).
【００１３】[0013]
【化９】 [Chemical 9]
【００１４】請求項４の蒸気圧の高い有機金属化学蒸着
によるビスマス及びビスマス酸化物薄膜形成用有機ビス
マス化合物は、下記構造式で表されるビス［ジ−ｐ−
メチル−ｍ−フルオロフェニル］ジビスマス（以下
「（Ｄ−ｐ−Ｍｅ−ｍ−ＦＰｈ）ＤＢｉ」と略記す
る。）であることを特徴とする。The bismuth and the organic bismuth compound for forming a bismuth oxide thin film by metalorganic chemical vapor deposition having a high vapor pressure according to claim 4 are represented by the following structural formula: bis [di-p-
Methyl-m-fluorophenyl] dibismuth (hereinafter abbreviated as “(Dp-Me-m-FPh) DBi”).
【００１５】[0015]
【化１０】 [Chemical 10]
【００１６】即ち、本発明者らは上述の観点から、熱分
解型ＭＯＣＶＤ法を含め、その他のＭＯＣＶＤ法により
ビスマス及びビスマス酸化物薄膜を作製するに際して、
気化速度が均一で、かつ気化の際の安定性に優れた高純
度なビスマス及びビスマス酸化物薄膜形成用蒸着原料を
見出すべく研究を行った結果、上記一般式（Ｉ）で表さ
れる有機ジビスマス化合物を蒸着原料として用いると、
一般の既存化合物として知られている前記構造式
（Ａ），（Ｂ）で表される従来のフェニルモノビスマス
化合物に比べて、優れた揮発性を示し、安定した気化速
度を得ることが可能になると共に、４５０〜５５０℃と
いう低温でビスマス及びビスマス酸化物の成膜が可能と
いう知見を得、本発明を完成させた。That is, from the above-mentioned viewpoints, the present inventors have prepared bismuth and bismuth oxide thin films by other MOCVD methods including the thermal decomposition MOCVD method.
As a result of research to find a high-purity bismuth and vapor deposition raw material for forming a bismuth oxide thin film, which has a uniform vaporization rate and is excellent in stability during vaporization, the organic dibismuth represented by the general formula (I) is obtained. When the compound is used as a vapor deposition material,
Compared with the conventional phenylmonobismuth compounds represented by the structural formulas (A) and (B), which are known as general existing compounds, they exhibit superior volatility and can obtain a stable vaporization rate. At the same time, the inventors have found that it is possible to form a film of bismuth and a bismuth oxide at a low temperature of 450 to 550 ° C., and have completed the present invention.
【００１７】以下に本発明を詳細に説明する。The present invention will be described in detail below.
【００１８】本発明の有機ビスマス化合物を示す前記一
般式（Ｉ）において、Ｒ1 としては、好ましくは水素、
メチル基、エチル基等が挙げられる。また、Ｒ2 として
は、好ましくは水素又はフッ素等が挙げられ、Ｒ1 とＲ
2 のいずれか一方が水素である場合、他方は水素以外の
置換基であることが好ましい。In the general formula (I) showing the organic bismuth compound of the present invention, R 1 is preferably hydrogen,
Examples thereof include a methyl group and an ethyl group. Further, R 2 is preferably hydrogen or fluorine, and R 1 and R
When either one of 2 is hydrogen, the other is preferably a substituent other than hydrogen.
【００１９】本発明の有機ビスマス化合物の具体例とし
ては、前記構造式で示される（Ｄ−ｐ−ＥｔＰｈ）Ｄ
Ｂｉ，前記構造式で示される（Ｄ−ｍ−ＦＰｈ）ＤＢ
ｉ，又は、前記構造式で示される（Ｄ−ｐ−Ｍｅ−ｍ
−ＦＰｈ）ＤＢｉが挙げられる。Specific examples of the organic bismuth compound of the present invention include (Dp-EtPh) D represented by the above structural formula.
Bi, (Dm-FPh) DB represented by the structural formula
i, or represented by the structural formula (Dp-Me-m
-FPh) DBi.
【００２０】このような有機ビスマス化合物は、後掲の
実施例に示されるように、三塩化ビスマスと、対応する
置換基Ｒ1 ，Ｒ2 を有するフェニルマグネシウムブロミ
ドとを反応させることにより合成することができる。Such an organic bismuth compound can be synthesized by reacting bismuth trichloride with phenylmagnesium bromide having the corresponding substituents R 1 and R 2, as shown in the examples below. You can
【００２１】このような本発明の有機ビスマス化合物
は、従来の有機ビスマス化合物と同様の操作で熱分解型
ＭＯＣＶＤ法等のＭＯＣＶＤ法によるビスマス及びビス
マス酸化物薄膜蒸着原料として用いることができる。Such an organic bismuth compound of the present invention can be used as a bismuth and bismuth oxide thin film vapor deposition material by MOCVD method such as thermal decomposition type MOCVD method by the same operation as the conventional organic bismuth compound.
【００２２】[0022]
【作用】本発明のビスマス及びビスマス酸化物薄膜形成
用有機ビスマス化合物は、４個のフェニル基を導入し
た、嵩高く、気化安定性の良いテトラフェニルジビスマ
ス化合物であるため、前記構造式（Ａ），（Ｂ）で表さ
れる従来の有機ビスマス化合物よりも安定した気化速度
で気化し、低温でのビスマス及びビスマス酸化物の成膜
が可能となる。The organic bismuth compound for forming a bismuth and bismuth oxide thin film of the present invention is a tetraphenyldibismuth compound having four phenyl groups introduced therein, which is bulky and has good vaporization stability. ) And (B), it vaporizes at a more stable vaporization rate than the conventional organic bismuth compound, and it becomes possible to form bismuth and bismuth oxide films at a low temperature.
【００２３】[0023]
【実施例】以下に実施例を挙げて本発明をより具体的に
説明する。EXAMPLES The present invention will be described in more detail with reference to the following examples.
【００２４】実施例１ ［有機ビスマス化合物の合成］三塩化ビスマス１５．５
６ｇに、氷冷下、十分に窒素脱気を行った乾燥ジエチル
エーテル２００ｍｌを注ぎ、サスペンジョン溶液とし、
この溶液に、ｐ−エチルフェニルマグネシウムブロミド
１５０ｍｌ（０．１５Ｍジエチルエーテル溶液）を撹拌
しながら添加した。更に、水１５０ｍｌを１滴づつ滴下
し、反応系を３０分間撹拌した後、希塩酸１５０ｍｌを
添加した。有機層を分離後、濃縮して、白色粉末６．２
ｇを得た。精製は、昇華により行い（９０℃／２ｔｏｒ
ｒ）、前記構造式で示される（Ｄ−ｐ−ＥｔＰｈ）Ｄ
Ｂｉの白色粉末３．０ｇを得た（融点１４０℃付近）。
得られた有機ビスマス化合物の同定は、ＮＭＲ、ＭＳ及
びＩＲにより行った。Example 1 [Synthesis of Organic Bismuth Compound] Bismuth trichloride 15.5
To 6 g, 200 ml of dry diethyl ether that had been sufficiently degassed with nitrogen under ice cooling was poured to prepare a suspension solution,
To this solution, 150 ml of p-ethylphenyl magnesium bromide (0.15 M diethyl ether solution) was added with stirring. Further, 150 ml of water was added drop by drop, the reaction system was stirred for 30 minutes, and then 150 ml of dilute hydrochloric acid was added. The organic layer was separated and then concentrated to give a white powder 6.2.
g was obtained. Purification is performed by sublimation (90 ° C / 2tor
r), (Dp-EtPh) D represented by the structural formula
3.0 g of white powder of Bi was obtained (melting point: about 140 ° C.).
The obtained organic bismuth compound was identified by NMR, MS and IR.
【００２５】1H-NMR(CDCl3);δ(CH2)2.31,δ(CH3)0.52,
δ(o-C6H4)6.05, δ(m-C6H4)6.65 MS(m/z):836 IR(cm-1):3050-2850,2000-1660,1210-1190,1125,1050,8
10 また、ｐ−エチルフェニルマグネシウムブロミドの代り
に、ｍ−フルオロフェニルマグネシウムブロミドを用い
たこと以外は同一の条件で、前記構造式で示される
（Ｄ−ｍ−ＦＰｈ）ＤＢｉの微黄色粉末を得た（融点６
２℃付近）。 1 H-NMR (CDCl 3 ); δ (CH 2 ) 2.31, δ (CH 3 ) 0.52,
δ (oC 6 H 4 ) 6.05, δ (mC 6 H 4 ) 6.65 MS (m / z): 836 IR (cm -1 ): 3050-2850,2000-1660,1210-1190,1125,1050,8
10 A slightly yellow powder of (Dm-FPh) DBi represented by the above structural formula was obtained under the same conditions except that m-fluorophenylmagnesium bromide was used instead of p-ethylphenylmagnesium bromide. (Melting point 6
(Around 2 ° C).
【００２６】1H-NMR(CDCl3);δ(p-C6H4)6.52, δ(o-C6H
4)6.99, δ(m-C6H4)6.92 MS(m/z):797 IR(cm-1):1210,1580,1470,840,780,680 また、ｐ−エチルフェニルマグネシウムブロミドの代り
に、ｐ−メチル−ｍ−フルオロフェニルマグネシウムブ
ロミドを用いたこと以外は同一の条件で、前記構造式
で示される（Ｄ−ｐ−Ｍｅ−ｍ−ＦＰｈ）ＤＢｉの白色
粉末を得た（融点１１０℃付近）。 1 H-NMR (CDCl 3 ); δ (pC 6 H 4 ) 6.52, δ (oC 6 H
4 ) 6.99, δ (mC 6 H 4 ) 6.92 MS (m / z): 797 IR (cm -1 ): 1210, 1580, 1470, 840, 780, 680 In addition, p-methylphenylmagnesium bromide was replaced by p-methyl- Under the same conditions except that m-fluorophenylmagnesium bromide was used, a white powder of (Dp-Me-m-FPh) DBi represented by the above structural formula was obtained (melting point: about 110 ° C).
【００２７】1H-NMR(CDCl3);δ(CH3)2.10,δ(o-C6H3)6.
95, δ(m-C6H3)6.69 MS(m/z):853 IR(cm-1):3200-2830,1560,1480-1460,1390,1220,990,86
0,810 また、比較の目的で、上記の各種置換フェニルマグネシ
ウムブロミドの代りに、ブロモベンゼン及びｏ−ブロモ
トルエンを用いたこと以外は同一の条件で、前記構造式
（Ａ）及び（Ｂ）で示される従来の有機ビスマス化合物
をそれぞれ合成した。 1 H-NMR (CDCl 3 ); δ (CH 3 ) 2.10, δ (oC 6 H 3 ) 6.
95, δ (mC 6 H 3 ) 6.69 MS (m / z): 853 IR (cm -1 ): 3200-2830,1560,1480-1460,1390,1220,990,86
For the purpose of comparison, the compounds are represented by the structural formulas (A) and (B) under the same conditions except that bromobenzene and o-bromotoluene were used instead of the various substituted phenylmagnesium bromides. Conventional organic bismuth compounds were synthesized respectively.
【００２８】得られた本発明有機ビスマス化合物及び従
来有機ビスマス化合物（Ａ）（トリ−ｏ−メチルフェニ
ルビスマス）の気化特性を評価する目的で熱重量曲線
（昇温速度１０℃／ｍｉｎ，乾燥アルゴン雰囲気）を図
２〜５に示した。For the purpose of evaluating the vaporization characteristics of the obtained organic bismuth compound of the present invention and the conventional organic bismuth compound (A) (tri-o-methylphenylbismuth), a thermogravimetric curve (heating rate 10 ° C./min, dry argon) was used. The atmosphere) is shown in FIGS.
【００２９】［ビスマス酸化物薄膜の蒸着］本発明有機
ビスマス化合物及び従来有機ビスマス化合物を各々用い
て、図１に示す装置により、熱分解型ＭＯＣＶＤ法に従
って、下記条件にて酸化ビスマス薄膜の作製を行い、１
０分毎の膜厚を測定した。膜厚は、膜の断面ＳＥＭ像か
ら測定した。この測定結果を表１，２に示した。[Deposition of Bismuth Oxide Thin Film] Using the organic bismuth compound of the present invention and a conventional organic bismuth compound, a bismuth oxide thin film was prepared by the apparatus shown in FIG. 1 according to the thermal decomposition MOCVD method under the following conditions. Done 1
The film thickness was measured every 0 minutes. The film thickness was measured from a cross-sectional SEM image of the film. The measurement results are shown in Tables 1 and 2.
【００３０】基板；１インチ角のＳｉ基板 基板温度；４５０℃，５５０℃ 気化温度；１００℃ 圧力；２ｔｏｒｒ キャリアガスの流量；１００ｃｃｍのＡｒ 反応ガスの流量；１００ｃｃｍのＯ２ Substrate: 1-inch square Si substrate Substrate temperature: 450 ° C., 550 ° C. Vaporization temperature; 100 ° C. pressure; 2 torr carrier gas flow rate; 100 ccm Ar reaction gas flow rate; 100 ccm O 2
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】［考察］図２〜５に示される結果から次の
ことが明らかである。即ち、本発明有機ビスマス化合物
は室温から約３４０℃までの温度で完全に気化させるこ
とが可能であるが、一方、従来有機ビスマス化合物は気
化終了の際、約１０％程の残留物が生成している。この
ことから、本発明有機ビスマス化合物は、気化安定性に
優れることが明らかである。[Discussion] The following is clear from the results shown in FIGS. That is, the organic bismuth compound of the present invention can be completely vaporized at a temperature from room temperature to about 340 ° C., while the conventional organic bismuth compound produces about 10% of a residue at the end of vaporization. ing. From this, it is clear that the organic bismuth compound of the present invention is excellent in vaporization stability.
【００３４】また、表１，２より、次のことが明らかで
ある。即ち、本発明有機ビスマス化合物は、成膜時間に
対しほぼ一定の割合で膜厚が増加し、かつ、その成膜速
度も従来有機ビスマス化合物に比べて速いのに対し、従
来有機ビスマス化合物の場合は、基板温度４５０℃の低
温では成膜不可能であり、また、基板温度５５０℃で
は、成膜時間において４０分を超えた頃から成膜量の減
少傾向が顕著になる。Further, from Tables 1 and 2, the following is clear. That is, in the organic bismuth compound of the present invention, the film thickness increases at a substantially constant rate with respect to the film formation time, and the film formation rate is faster than that of the conventional organic bismuth compound, whereas in the case of the conventional organic bismuth compound, Does not allow film formation at a low substrate temperature of 450 ° C., and at a substrate temperature of 550 ° C., the tendency for the amount of film formation to decrease becomes prominent when the film formation time exceeds 40 minutes.
【００３５】なお、本発明有機ビスマス化合物を用いた
場合は、図１に示す装置の気化容器内には分解ビスマス
の生成が見られなかったのに対し、従来有機ビスマス化
合物の場合には分解ビスマスの生成が認められた。これ
より、本発明有機ビスマス化合物は、気化容器内で分解
することなしに成膜時間に対し一定の速度で気化し、ま
た、従来有機ビスマス化合物より４５０〜５５０℃とい
う低温で成膜可能な有機ビスマス化合物であることを示
している。When the organic bismuth compound of the present invention was used, no generation of decomposed bismuth was observed in the vaporization vessel of the apparatus shown in FIG. 1, whereas in the case of the conventional organic bismuth compound, the decomposed bismuth compound was used. Was observed to be generated. As a result, the organic bismuth compound of the present invention is vaporized at a constant rate with respect to the film formation time without decomposing in the vaporization container, and the organic bismuth compound capable of forming a film at a lower temperature of 450 to 550 ° C. than the conventional organic bismuth compound. It shows that it is a bismuth compound.
【００３６】[0036]
【発明の効果】以上詳述した通り、本発明の蒸気圧の高
い有機金属化学蒸着によるビスマス及びビスマス酸化物
薄膜形成用有機ビスマス化合物は、高蒸気圧で気化安定
性に優れ、安定な気化速度を有しており、ＭＯＣＶＤ法
により４５０〜５５０℃という低温で均一かつ緻密なビ
スマス及びビスマス酸化物薄膜を成膜可能な原料として
極めて有用であり、超伝導材料、強誘電体材料、半導体
薄膜材料等として有用な特定組成のビスマス含有薄膜の
製造にも有効に利用することができる。As described in detail above, the organic bismuth compound for forming a bismuth and bismuth oxide thin film by high vapor pressure organometallic chemical vapor deposition of the present invention is excellent in vaporization stability at a high vapor pressure and has a stable vaporization rate. And is extremely useful as a raw material capable of forming a uniform and dense bismuth and bismuth oxide thin film at a low temperature of 450 to 550 ° C. by the MOCVD method, and is a superconducting material, a ferroelectric material, a semiconductor thin film material. It can also be effectively used for the production of a bismuth-containing thin film having a specific composition that is useful as the above.
【図１】熱分解型ＭＯＣＶＤ法を説明する装置の概略断
面図である。FIG. 1 is a schematic sectional view of an apparatus for explaining a thermal decomposition MOCVD method.
【図２】本発明有機ビスマス化合物（Ｄ−ｐ−ＥｔＰ
ｈ）ＤＢｉの熱重量曲線を示すグラフである。FIG. 2 is an organic bismuth compound (Dp-EtP) of the present invention.
h) A graph showing a thermogravimetric curve of DBi.
【図３】本発明有機ビスマス化合物（Ｄ−ｍ−ＦＰｈ）
ＤＢｉの熱重量曲線を示すグラフである。FIG. 3 is an organic bismuth compound (Dm-FPh) of the present invention.
It is a graph which shows the thermogravimetric curve of DBi.
【図４】本発明有機ビスマス化合物（Ｄ−ｐ−Ｍｅ−ｍ
−ＦＰｈ）ＤＢｉの熱重量曲線を示すグラフである。FIG. 4 is an organic bismuth compound (Dp-Me-m) of the present invention.
-FPh) is a graph showing a thermogravimetric curve of DBi.
【図５】従来有機ビスマス化合物の熱重量曲線を示すグ
ラフである。FIG. 5 is a graph showing a thermogravimetric curve of a conventional organic bismuth compound.
１ 蒸着原料 ２ 気化容器 ３ 加熱炉 ４ キャリアガス導入配管 ５ 反応ガス導入配管 ６ 基板 ７ ヒーター ８ 反応炉 ９ 真空引配管 1 Vapor Deposition Material 2 Vaporization Container 3 Heating Furnace 4 Carrier Gas Introducing Pipe 5 Reactive Gas Introducing Pipe 6 Substrate 7 Heater 8 Reactor 9 Vacuum Evacuating Pipe
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｌ 39/12 ＺＡＡ Ｈ０１Ｌ 39/12 ＺＡＡＣ 39/24 ＺＡＡ 39/24 ＺＡＡＢ (72)発明者 小木 勝実 埼玉県大宮市北袋町１丁目297番地 三菱 マテリアル株式会社中央研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI Technical display location H01L 39/12 ZAA H01L 39/12 ZAAC 39/24 ZAA 39/24 ZAAB (72) Inventor Katsumi Ogi 1-297 Kitabukuro-cho, Omiya City, Saitama Prefecture Mitsubishi Materials Corporation Central Research Laboratory
Claims (4)
い有機金属化学蒸着によるビスマス及びビスマス酸化物
薄膜形成用有機ビスマス化合物。 【化１】 （ただし、上記（Ｉ）式中、Ｒ1 ，Ｒ2 は、炭素数１〜
４の直鎖又は分岐状のアルキル基、炭素数１〜４の直鎖
又は分岐状のフッ化アルキル基、水素原子又はフッ素原
子を示し、Ｒ1 とＲ2 とは互いに異なっていても良く、
同一であっても良い。）1. An organic bismuth compound represented by the following general formula (I) for forming a thin film of bismuth and a bismuth oxide by high vapor pressure organometallic chemical vapor deposition. Embedded image (However, in the formula (I), R 1 and R 2 are each a carbon number of 1 to
4 represents a linear or branched alkyl group, a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms, a hydrogen atom or a fluorine atom, and R 1 and R 2 may be different from each other,
It may be the same. )
有機ビスマス化合物が、下記構造式で表されるビス
［ジ−ｐ−エチルフェニル］ジビスマスであることを特
徴とする請求項１に記載の蒸気圧の高い有機金属化学蒸
着によるビスマス及びビスマス酸化物薄膜形成用有機ビ
スマス化合物。 【化２】 2. The vapor pressure according to claim 1, wherein the organic bismuth compound for forming bismuth and a bismuth oxide thin film is bis [di-p-ethylphenyl] dibismuth represented by the following structural formula. Organic bismuth compounds for forming bismuth and bismuth oxide thin films by high metalorganic chemical vapor deposition. Embedded image
有機ビスマス化合物が、下記構造式で表されるビス
［ジ−ｍ−フルオロフェニル］ジビスマスであることを
特徴とする請求項１に記載の蒸気圧の高い有機金属化学
蒸着によるビスマス及びビスマス酸化物薄膜形成用有機
ビスマス化合物。 【化３】 3. The vapor pressure according to claim 1, wherein the bismuth and the organic bismuth compound for forming a bismuth oxide thin film are bis [di-m-fluorophenyl] dibismuth represented by the following structural formula. Organic bismuth compounds for forming bismuth and bismuth oxide thin films by high metalorganic chemical vapor deposition. Embedded image
有機ビスマス化合物が、下記構造式で表されるビス
［ジ−ｐ−メチル−ｍ−フルオロフェニル］ジビスマス
であることを特徴とする請求項１に記載の蒸気圧の高い
有機金属化学蒸着によるビスマス及びビスマス酸化物薄
膜形成用有機ビスマス化合物。 【化４】 4. The organic bismuth compound for forming bismuth and a bismuth oxide thin film is bis [di-p-methyl-m-fluorophenyl] dibismuth represented by the following structural formula. An organic bismuth compound for forming a bismuth and a bismuth oxide thin film by metalorganic chemical vapor deposition having a high vapor pressure according to the description. [Chemical 4]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07075361A JP3106898B2 (en) | 1995-03-31 | 1995-03-31 | Method for forming bismuth-containing film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07075361A JP3106898B2 (en) | 1995-03-31 | 1995-03-31 | Method for forming bismuth-containing film |
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| Publication Number | Publication Date |
|---|---|
| JPH08269717A true JPH08269717A (en) | 1996-10-15 |
| JP3106898B2 JP3106898B2 (en) | 2000-11-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07075361A Expired - Fee Related JP3106898B2 (en) | 1995-03-31 | 1995-03-31 | Method for forming bismuth-containing film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2429201A (en) * | 2003-02-05 | 2007-02-21 | Univ Cambridge Tech | The use of bismuth (methoxy methyl propanolate)3 as a precursor in forming a ferroelectric material |
-
1995
- 1995-03-31 JP JP07075361A patent/JP3106898B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2429201A (en) * | 2003-02-05 | 2007-02-21 | Univ Cambridge Tech | The use of bismuth (methoxy methyl propanolate)3 as a precursor in forming a ferroelectric material |
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| Publication number | Publication date |
|---|---|
| JP3106898B2 (en) | 2000-11-06 |
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