JPH0742295B2 - Method for producing organozinc compound - Google Patents
Method for producing organozinc compoundInfo
- Publication number
- JPH0742295B2 JPH0742295B2 JP6475285A JP6475285A JPH0742295B2 JP H0742295 B2 JPH0742295 B2 JP H0742295B2 JP 6475285 A JP6475285 A JP 6475285A JP 6475285 A JP6475285 A JP 6475285A JP H0742295 B2 JPH0742295 B2 JP H0742295B2
- Authority
- JP
- Japan
- Prior art keywords
- adduct
- point component
- producing
- organozinc compound
- boiling point
- 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
Landscapes
- Chemical Vapour Deposition (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、ジアルキル亜鉛（以下R2Znと略す）と、ジア
ルキルセレン（以下R2Seと略す）の付加体、からなる有
機亜鉛化合物の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an organozinc compound comprising a dialkylzinc (hereinafter abbreviated as R 2 Zn) and an adduct of dialkylselenium (hereinafter abbreviated as R 2 Se). Regarding manufacturing method.
さらに詳しくは、半導体薄膜並びに半導体装置の製造技
術であるMO-CVD法の原料として有効なR2ZnとR2Seの付加
体からなる有機亜鉛化合物の製造法に関する。More specifically, it relates to a method for producing an organozinc compound comprising an adduct of R 2 Zn and R 2 Se, which is effective as a raw material for MO-CVD, which is a technique for producing semiconductor thin films and semiconductor devices.
本発明は、青色発光ダイオード、及び薄膜EL素子用材料
であるセレン化亜鉛（ZnSe）及びその混晶薄膜の製造に
有効なMO-CVD法の原料である有機亜鉛化合物に於て、R2
ZnとR2Seとを混合し、反応及び熟成によつてR2ZnとR2Se
の付加体を高純度に、又再現性よく形成させる事によ
り、従来のR2Znに比較してH2Se又はH2S等の水素化物に
対する反応性が低く、従来MO-CVD法に於て問題となつて
いた原料の混合により、基板の上流で生じる不要な前反
応が生じ難く、良質のZnSe及びその混晶薄膜、ひいて
は、高性能半導体装置の実現を可能とする原料の製造法
を提供するものである。The present invention At a blue light-emitting diode, and an organic zinc compound which is a raw material of a valid MO-CVD method for the production of zinc selenide (ZnSe) and mixed crystal thin film is a material for a thin film EL element, R 2
Mixing the Zn and R 2 Se, Yotsute the reaction and aged for R 2 Zn and R 2 Se
By forming the adduct of 1 with high purity and reproducibility, the reactivity with hydrides such as H 2 Se or H 2 S is lower than that of conventional R 2 Zn, and the conventional MO-CVD method is used. It is difficult to cause unnecessary pre-reactions that occur upstream of the substrate due to the mixing of the raw materials, which has been a problem, and a method of manufacturing raw materials that enables the realization of high-quality ZnSe and its mixed crystal thin film, and thus high-performance semiconductor devices. It is provided.
従来、ZnSe及びその混晶薄膜のMO-CVD法による製造に於
て、原料として、亜鉛ソースにジメチル亜鉛：Zn(CH3)2
ジエチル亜鉛：Zn(C2H5)2等の有機亜鉛化合物を用
い、硫化水素：H2S及びセレン化水素：H2Seと反応させ
るのが通例であつた。これらの原料を用いた場合の化学
反応は次式で表わされる。Conventionally, in the production of ZnSe and its mixed crystal thin film by the MO-CVD method, dimethylzinc: Zn (CH 3 ) 2
It is customary to use an organozinc compound such as diethylzinc: Zn (C 2 H 5 ) 2 and react with hydrogen sulfide: H 2 S and hydrogen selenide: H 2 Se. The chemical reaction when these raw materials are used is represented by the following formula.
(CH3)2Zn+H2Se→ZnSe+2CH4 … (C2H5)2Zn+H2Se→ZnSe+2C2H6 … しかしこれらの反応は、R2Znが活性であるためMO-CVD反
応装置内に原料ガスを導入すると該水素化物との混合と
同時に室温近傍でも気相中で反応が進行し、基板表面に
原料が到達する以前にZnSe微粒子を生成し、このZnSe微
粒子が薄膜成長用基板表面での成長過程に悪影響を及ぼ
しており、得られる結晶の質はあまり高くなかつた。(CH 3 ) 2 Zn + H 2 Se → ZnSe + 2CH 4 … (C 2 H 5 ) 2 Zn + H 2 Se → ZnSe + 2C 2 H 6 … But these reactions are because R 2 Zn is active. When a raw material gas is introduced into the MO-CVD reactor, the reaction proceeds in the vapor phase even near room temperature when mixed with the hydride, and ZnSe fine particles are generated before the raw material reaches the substrate surface. Has a bad influence on the growth process on the surface of the thin film growth substrate, and the quality of the obtained crystal is not so high.
従来、これらの問題を解決する手段として（１）基板直
前でR2ZnとH2Seを混合する（例えば、J.Cryst Growth 5
9、P1、（1982）記載）、（２）減圧にして、ガス流速
を高める（例えば、Jpn.J.Appl.Phys.23、L360（1984）
記載）等の装置系の対策、並びに、（３）セレン原料と
して、H2Seの代りに、R2Seを用いる。（第45回応用物理
学会学術講演会P629（1984）、講演番号12a-S-3記載）
（４）R2ZnとR2Seを混合し、気相でR2Zn-SeR2なる付
加体を形成後、H2Seと混合して反応管に供給する。（J.
Cryst.Growth.66、（1984）P231記載）等の原料による
対策が公知であつた。Conventionally, as means for solving these problems, (1) mixing R 2 Zn and H 2 Se immediately before the substrate (for example, J. Cryst Growth 5
9 , P1, (1982)), (2) Reduce pressure to increase gas flow rate (eg Jpn.J.Appl.Phys. 23 , L360 (1984).
Wherein) the device type, such measures, and (3) as a selenium raw material, instead of H 2 Se, using the R 2 Se. (The 45th Japan Society of Applied Physics Academic Conference P629 (1984), Lecture No. 12a-S-3)
(4) R 2 Zn and R 2 Se are mixed to form an adduct of R 2 Zn-SeR 2 in the gas phase, and then mixed with H 2 Se and supplied to the reaction tube. (J.
Cryst.Growth. 66 , (1984) P231) and other measures using raw materials have been publicly known.
上述の従来技術に基づくMO-CVD法に於ては、製法上及び
デバイスへの応用上次の如き問題点を有し、解決が望ま
れていた。The MO-CVD method based on the above-mentioned conventional technique has the following problems in terms of manufacturing method and application to devices, and a solution thereof has been desired.
従来技術（１）及び（２）に対して 1.基板直前で混合するために、薄膜の膜厚，組成，ドー
パント分布等の均一性が得にくい。Compared to the prior arts (1) and (2): 1. Uniformity of thin film thickness, composition, dopant distribution, etc. is difficult to obtain because of mixing just before the substrate.
2.大面積、多数枚基板の処理が困難で量産性に乏しい。2. It is difficult to process a large area and a large number of substrates, and mass productivity is poor.
3.結晶の質が悪く、発光特性，電導特性が制御できな
い。3. The quality of the crystal is poor and the emission and conduction characteristics cannot be controlled.
例えば、従来の製造法に於ては、R2ZnとH2Seとを、基板
から2cmの距離で混合吹き付けをしており、これにより
処理できる基板の大きさは高々直径20mm1枚であつた。
又、得られた結晶は多くの欠陥を有し、そのフオトルミ
ネツセンス特性は、高品質な結晶に見られる青色発光の
他に深い準位からの赤い発光も観測され、青色発光ダイ
オードには使用できなかつた。For example, in the conventional manufacturing method, R 2 Zn and H 2 Se are mixed and sprayed at a distance of 2 cm from the substrate, and the size of the substrate that can be processed by this is at most 20 mm in diameter. .
Further, the obtained crystal has many defects, and its photoluminescence property is that, in addition to the blue light emission seen in high-quality crystals, red light emission from a deep level is also observed, and a blue light emitting diode has It was unusable.
従来技術（３）に対して、 1.混合に伴う室温でのZnSe微粒子の堆積は抑制できる
が、逆にR2Seが分解しにくいため、十分な成長速度を得
るため450℃程度の高温が必要であり、得られた結晶は
多くの欠陥を有する。Compared with the conventional technology (3), 1. Although the deposition of ZnSe fine particles at room temperature due to mixing can be suppressed, conversely, since R 2 Se is difficult to decompose, a high temperature of about 450 ° C. is required to obtain a sufficient growth rate. It is necessary and the obtained crystals have many defects.
2.膜の成長は500℃以下では反応律速であり、成長基板
上の温度分布等によりバラ付きが大きい。2. The film growth is reaction-limited at temperatures below 500 ° C, and there are large variations due to temperature distribution on the growth substrate.
従来技術（４）に対して、 1.気相中での混合ではR2ZnとR2Seの反応は不完全であ
り、又その度合は、ガス流速，配管の長さ，温度等にも
影響を受け、完全に不要な前反応を抑制する事はでき
ず、又、データのバラツキも大きかつた。特に、赤外線
吸収スペクトルにより反応管内のガスを分析した所、R2
Zn-SeR2という付加体は形成されていないという報告
（J.Cryst.Growth.68（1984）P656記載）が為されてい
る。Compared to the conventional technology (4), 1. The reaction of R 2 Zn and R 2 Se is not complete in the gas phase mixing, and the degree of the reaction depends on the gas flow rate, the length of the pipe, the temperature, etc. It was affected, and it was not possible to completely suppress unnecessary pre-reactions, and there were large variations in the data. Especially, when the gas in the reaction tube was analyzed by infrared absorption spectrum, R 2
It has been reported that an adduct called Zn-SeR 2 is not formed (described in J. Cryst. Growth. 68 (1984) P656).
上記R2Zn-SeR2付加体をZn原料に使う方法は、両者をは
じめから等モル量混合して得られる付加体を用いる事に
より、より向上するが、この場合にも次の如き問題点を
有する。The method of using the R 2 Zn-SeR 2 adduct as a Zn raw material is further improved by using an adduct obtained by mixing both of them in an equimolar amount, but in this case also the following problems Have.
1.R2ZnとR2Seとの反応性はあまり高く無く、単に両者を
等モル量混合しただけでは、次式の R2Zn+R2Se→R2Zn-SeR2 … 反応を完結できず、得られたものの蒸気圧等の物性も、
混合条件，反応に用いる迄の履歴等により異り、バラ付
きが大きかつた。1. The reactivity between R 2 Zn and R 2 Se is not very high, and simply mixing both in equimolar amounts will complete the reaction of R 2 Zn + R 2 Se → R 2 Zn-SeR 2 ... I could not do it, and the physical properties such as vapor pressure of the obtained one,
The variation was large, depending on the mixing conditions and the history of the reaction.
2.又その結果として、該等モル量混合による付加体を原
料として、MO-CVD法によりH2Seと反応させて、ZnSeエピ
タキシヤル成長を行うと、エピタキシヤル薄膜の成長速
度並びにその物性の再現性が悪かつた。2. As a result, when the ZnSe epitaxial growth is carried out by reacting with H 2 Se by the MO-CVD method using the adduct obtained by mixing the equimolar amounts as a raw material, the growth rate of the epitaxial thin film and its physical properties are The reproducibility was bad.
本発明の目的は、かかる問題点を解決すべく、Zn原料と
して、H2Se又はH2Sとの反応性がR2Znに比べて低く、室
温での基板の上流で生じる不要な前反応をより完全に抑
制でき、且つ200℃以上の比較的低温に於ても十分反応
し、MO-CVD法にZn原料として用いる事で、良質の結晶薄
膜を大面積上に、多数枚上に成長可能であり、深い欠陥
準位からの発光の無いデバイスレベルの品質を有するZn
Se結晶及びその混晶薄膜を再現性よく実現する高純度な
有機亜鉛化合物の製造法を提供する点にある。The object of the present invention is to solve such problems, as a Zn raw material, the reactivity with H 2 Se or H 2 S is lower than that of R 2 Zn, and an unnecessary pre-reaction that occurs upstream of the substrate at room temperature. Can be completely suppressed, and it reacts well even at a relatively low temperature of 200 ° C or higher, and by using it as a Zn raw material in the MO-CVD method, a good quality thin crystal film can be grown on a large area and on a large number of sheets. Zn with possible device-level quality without emission from deep defect levels
The point is to provide a method for producing a high-purity organozinc compound that can realize Se crystals and mixed crystal thin films thereof with good reproducibility.
本発明の有機亜鉛化合物の製造法は、ア）ジアルキル亜
鉛とジアルキルセレンのうちの低沸点成分のモル量が両
者のうちの高沸点成分のモル量に対して過剰となるよう
に、前記ジアルキル亜鉛と前記ジアルキルセレンとを混
合する工程と、イ）前記ア）工程で混合されたジアルキ
ル亜鉛とジアルキルセレンとの混合物を加熱する工程
と、ウ）前記イ）工程の後、前記高沸点成分の量に対し
て過剰量となる前記低沸点成分を溜出除去する工程と、
を有することを特徴とする。The method for producing an organozinc compound of the present invention comprises: a) adjusting the amount of the low boiling point component of the dialkyl zinc and the dialkyl selenium to be in excess of the molar amount of the high boiling point component of both; And a step of mixing the dialkyl selenium with each other, a) a step of heating the mixture of the dialkyl zinc and the dialkyl selenium mixed in the step a), and c) an amount of the high boiling point component after the step a). A step of distilling and removing the low boiling point component which becomes an excessive amount with respect to
It is characterized by having.
また、前記ア）工程において、ジアルキル亜鉛とジアル
キルセレンのうちの低沸点成分が両者のうちの高沸点成
分に対して1.05〜1.2当量比となるように、前記ジアル
キル亜鉛と前記ジアルキルセレンとを混合することを特
徴とする。また、前記混合物を加熱する工程が、０℃〜
40℃で10分〜３時間反応させる工程、徐々に昇温する工
程、30℃〜80℃で10分〜２時間熟成させる工程からなる
ことを特徴とする。In the step a), the dialkylzinc and the dialkylselenium are mixed so that the low-boiling point component of the dialkylzinc and the dialkylselenium has a 1.05-1.2 equivalent ratio to the high-boiling point component of the both. It is characterized by doing. In addition, the step of heating the mixture is from 0 ° C to
It is characterized by comprising a step of reacting at 40 ° C for 10 minutes to 3 hours, a step of gradually raising the temperature, and a step of aging at 30 ° C to 80 ° C for 10 minutes to 2 hours.
本発明に適用可能なR2Zn及びR2Seを表１にまとめて示す
が、この限りでない事は明らかである。Table 1 summarizes R 2 Zn and R 2 Se applicable to the present invention, but it is obvious that this is not the case.
R2ZnとR2Seの付加体は、電子受容体としてのR2Znと、電
子供与体としてのR2Seとの、１対１の酸−塩基反応の結
果得られるもので、式 R2Zn-SeR2 … の構造からなる。該付加体の製造法としては、各成分の
等モル量の混合によつても原理的には可能であるが、反
応を完結し、高純度で再現性のある物性を有する付加体
を製造するには以下の工程が必要である。 Adducts of R 2 Zn and R 2 Se has a R 2 Zn as an electron acceptor, and R 2 Se as an electron donor, one-to-one acid - those resulting from the base reaction, wherein R 2 Zn-SeR 2 ... structure. As a method for producing the adduct, it is possible in principle to mix the components in equimolar amounts, but the reaction is completed to produce an adduct having high purity and reproducible physical properties. Requires the following steps.
R2ZnとR2Seとを、両者のうち低沸点成分を過剰に、好ま
しくは、低沸点成分対高沸点成分の比率を1.05〜1.2当
量比として混合し、両者を低沸点成分の沸点以下で、お
よそ０℃〜40℃で10分〜３時間、好ましくは10〜35℃で
30分〜１時間、充分に反応させる。And R 2 Zn and R 2 Se, an excess of low-boiling component of the two, preferably, the ratio of the low-boiling component to the high-boiling components were mixed as 1.05 to 1.2 equivalent ratio, both low-boiling components boiling below At about 0 to 40 ° C for 10 minutes to 3 hours, preferably at 10 to 35 ° C.
Allow sufficient reaction for 30 minutes to 1 hour.
その後反応を完結するために、徐々に昇温し、30〜80℃
で10分〜２時間、好ましくは10〜15℃／時間の割で昇温
し、30〜70℃で30分〜１時間熟成させる。After that, to complete the reaction, gradually raise the temperature to 30-80 ° C.
The temperature is raised for 10 minutes to 2 hours, preferably 10 to 15 ° C./hour, and aged at 30 to 70 ° C. for 30 minutes to 1 hour.
最後に過剰成分を蒸留により除去する。Finally, excess components are removed by distillation.
付加体の生成は以下の事実により確認できる。The formation of the adduct can be confirmed by the following facts.
（１）両者の混合により発熱する。(1) Heat is generated by mixing the two.
（２）生成した付加体の蒸気圧−温度曲線は、出発原料
のR2Zn及びR2Seのいずれとも異なる。(2) The vapor pressure-temperature curve of the produced adduct is different from that of R 2 Zn and R 2 Se which are the starting materials.
（３）原料の仕込み量、生成物及び溜出過剰成分の量か
ら、反応がR2ZnとR2Seの1:1で生じている。(3) The reaction takes place at a ratio of R 2 Zn and R 2 Se of 1: 1 due to the charged amount of the raw materials, the amount of the product and the excess distillate component.
（４）NMRによる解析 以下実施例に従い、本発明に基づく有機亜鉛化合物、並
びにその製造法を説明する。(4) Analysis by NMR The organozinc compound according to the present invention and the method for producing the same will be described below with reference to Examples.
〔実施例１〕 (CH3)2Zn-Se(CH3)2 300ml丸底フラスコに(CH3)2Seを63.5g（0.583モル）仕
込み、攪拌しながら(CH3)2Zn58.5g（0.613モル）を滴下
ロートにより滴下して反応させた。反応は発熱反応で、
発熱量は大であつた。EXAMPLE 1 (CH 3) 2 Zn-Se (CH 3) 2 300ml round bottom flask (CH 3) 2 Se and 63.5 g (0.583 mol) were charged, under stirring (CH 3) 2 Zn58.5g ( 0.613 mol) was added dropwise with a dropping funnel and reacted. The reaction is exothermic,
The calorific value was large.
反応温度を８〜15℃に制御し、40分間反応を行つた。そ
の後15℃／時間の割で徐々に昇温し、45℃で１時間熟成
した。その後蒸留により不要な過剰分を溜出除去した。
生成物は118gであつた。The reaction temperature was controlled at 8 to 15 ° C and the reaction was carried out for 40 minutes. Thereafter, the temperature was gradually raised at a rate of 15 ° C./hour and aging was carried out at 45 ° C. for 1 hour. After that, unnecessary excess was distilled off by distillation.
The product weighed 118 g.
第１図は得られた付加体の蒸気圧−温度特性を示す。横
軸が温度、縦軸が蒸気圧である。FIG. 1 shows the vapor pressure-temperature characteristics of the obtained adduct. The horizontal axis is temperature and the vertical axis is vapor pressure.
実線が付加体の、又、破線が各々、原料であるSe
(CH3)2及び(CH3)2Znの蒸気圧特性を示す。The solid line is the adduct and the broken line is the raw material Se.
2 shows vapor pressure characteristics of (CH 3 ) 2 and (CH 3 ) 2 Zn.
又、表（２）に代表的温度に於ける蒸気圧の値を示す。Table (2) shows the vapor pressure values at typical temperatures.
第２図にNMRによる生成物の(CH3)2Znのメチル基のプロ
トンによるシグナルを示す。 FIG. 2 shows the signal by the proton of the methyl group of (CH 3 ) 2 Zn of the product by NMR.
生成物のケミカルシフトは、δ＝−0.63ppmであり、(CH
3)2Znの単一成分ではδ＝−0.67ppmである事から(CH3)2
Zn-Se(CH3)2付加体の生成を認めた。The chemical shift of the product is δ = -0.63 ppm,
3 ) 2 Zn has a single component of δ = −0.67 ppm, so (CH 3 ) 2
The formation of Zn-Se (CH 3 ) 2 adduct was observed.
又同様の工程を経る事により、表３に示す付加体が得ら
れた。Also, the adducts shown in Table 3 were obtained through the same steps.
又、得られた付加体の蒸気圧特性等物性値の異なるロツ
ト間のバラ付きは検出以下であり、又、NMRの結果から
も原料の(CH3)2Znの単独成分の存在は認められず極めて
高純度であつた。 Further, the variation between the rods having different physical properties such as vapor pressure characteristics of the obtained adduct was less than the detection, and the existence of the single component of the starting material (CH 3 ) 2 Zn was also confirmed from the result of NMR. It was extremely pure.
次に上記実施例により得られた付加体を用いて、常圧の
横型MO-CVD装置によりZnSe結晶薄膜をGaAs単結晶基板上
に形成したところ、いずれの付加体に於ても良質の単結
晶薄膜が得られた。Next, using the adducts obtained in the above examples, a ZnSe crystal thin film was formed on a GaAs single crystal substrate by a horizontal MO-CVD device at atmospheric pressure. A thin film was obtained.
（１）従来問題となつていた混合と同時に生じる気相中
でのR2ZnとH2Seとの前反応に伴う白濁粒子の流れ、薄膜
成長基板の上流での粒子の堆積は認められず、本発明に
基づく付加体及びH2SeをH2ガスをキヤリアーガスとし
て、反応管の直前で混合し、導入口から200mm離れたGaA
s単結晶基板上に表面状態が滑めらかな鏡面のZnSe単結
晶薄膜が得られた。(1) The flow of cloudy particles due to the pre-reaction of R 2 Zn and H 2 Se in the gas phase, which occurred at the same time as the conventional mixing, and the deposition of particles upstream of the thin film growth substrate were not observed. , H 2 gas as a carrier gas was mixed with the adduct according to the present invention and H 2 Se immediately before the reaction tube, and GaA separated from the inlet by 200 mm.
A ZnSe single crystal thin film with a smooth surface was obtained on the s single crystal substrate.
（２）膜厚の分布は、ガスの流れ方向に並べて置いた３
枚の２インチGaAs基板上で±５％以内であつた。(2) The film thickness distribution was set to 3 in the gas flow direction.
Within ± 5% on a 2-inch GaAs substrate.
（３）得られた単結晶薄膜の（400）面×線ロツキング
カーブの半値巾は約0.1°と極めて良い結晶の配向性を
有し、又高圧Hgランプの365nmの光を照射する事によ
り、室温で4610Åの鋭いバンド端近傍の発光が得られ、
赤色領域の発光は認められなかつた。(3) The (400) plane x line locking curve of the obtained single crystal thin film has a half-value width of about 0.1 ° and has a very good crystal orientation, and by irradiating the high-pressure Hg lamp with 365 nm light. At room temperature, emission near the sharp band edge of 4610Å is obtained,
No emission in the red region was observed.
（４）Zn原料であるR2Zn-SeR2付加体の供給量に対し、H
2Seリツチな条件で、膜の成長速度は、該付加体の供給
律速であり、その温度依存性は極めて小さかつた。(4) For the supply amount of R 2 Zn-SeR 2 adduct which is a Zn raw material, H
Under 2 Se-rich conditions, the growth rate of the film was the rate-determining supply of the adduct, and its temperature dependence was extremely small.
（５）成長速度及び発光特性等結晶品質の再現性は、MO
-CVDのバツチ間、並びに付加体のバツチ間に対して、非
常に安定していた。(5) The reproducibility of crystal quality such as growth rate and emission characteristics is
-It was very stable between CVD batches and between adduct batches.
等の事実により、本発明に基づくR2Zn-SeR2の付加体か
らなる有機亜鉛化合物が、MO-CVD法に於て有効な事が明
らかである。From the above facts, it is clear that the organozinc compound comprising the R 2 Zn—SeR 2 adduct according to the present invention is effective in the MO-CVD method.
以上述べた様に、本発明によれば、R2Zn及びR2Seを両者
のうち低沸点成分を過剰に混合し、加熱により反応及び
熟成を行つた後、過剰成分を溜出除去する事により、高
純度で、蒸気圧等物性定数の再現性を有するR2ZnとR2Se
の付加体からなる有機亜鉛化合物を提供する効果を有す
る。As described above, according to the present invention, R 2 Zn and R 2 Se are excessively mixed with low-boiling components of both, and after reaction and aging by heating, excess components are distilled off. Shows that R 2 Zn and R 2 Se have high purity and reproducibility of physical constants such as vapor pressure.
It has the effect of providing an organozinc compound consisting of an adduct of
これにより、青色に限らず可視発光ダイオード、半導体
レーザー及び薄膜EL素子等の製造に対し本発明の果す役
割が絶大なものである事を確信する。From this, it is convinced that the role of the present invention is great for manufacturing not only blue light but also visible light emitting diodes, semiconductor lasers, thin film EL elements and the like.
第１図は、有機亜鉛化合物の蒸気圧−温度特性図。 １……温度、２……蒸気圧 ３……付加体、４……Se(CH3)2 ５……(CH3)2Zn 第２図は、生成物のメチル基のプロトンによるシグナル
図。 ６……ケミカルシフト、７……シグナル強度 ８……TMS、９……生成物FIG. 1 is a vapor pressure-temperature characteristic diagram of an organozinc compound. 1 ... Temperature, 2 ... Vapor pressure, 3 ... Adduct, 4 ... Se (CH 3 ) 2 5 ... (CH 3 ) 2 Zn Fig. 2 is a signal diagram by the proton of the methyl group of the product. 6 ... Chemical shift, 7 ... Signal intensity 8 ... TMS, 9 ... Product
───────────────────────────────────────────────────── フロントページの続き (72)発明者 水本 照之 長野県諏訪市大和３丁目３番５号 株式会 社諏訪精工舎内 (72)発明者 藤沢 正男 山口県防府市大字勝間３丁目１番 (72)発明者 市川 明宏 山口県徳山市大字徳山287番155号 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Teruyuki Mizumoto, Inventor Teruyuki Mizumoto, 3-3-5 Yamato, Suwa City, Nagano Stock Company, Suwa Seikosha Co., Ltd. (72) Masao Fujisawa, 3-1-1 Katsuma, Hofu, Yamaguchi Prefecture (72) Inventor Akihiro Ichikawa 287-155 Tokuyama, Tokuyama City, Yamaguchi Prefecture
Claims (3)
うちの低沸点成分のモル量が両者のうちの高沸点成分の
モル量に対して過剰となるように、前記ジアルキル亜鉛
と前記ジアルキルセレンとを混合する工程と、 イ）前記ア）工程で混合されたジアルキル亜鉛とジアル
キルセレンとの混合物を加熱する工程と、 ウ）前記イ）工程の後、前記高沸点成分の量に対して過
剰量となる前記低沸点成分を溜出除去する工程と、 を有するジアルキル亜鉛とジアルキルセレンの付加体か
らなる有機亜鉛化合物の製造法。1. A) The dialkyl zinc and the dialkyl selenium are mixed so that the molar amount of the low boiling point component of the dialkyl zinc and the dialkyl selenium becomes excessive with respect to the molar amount of the high boiling point component of the both. Mixing step, a) heating the mixture of dialkylzinc and dialkylselenium mixed in step a), and c) an excess amount after the step a) with respect to the amount of the high boiling point component. And a step of distilling and removing the low-boiling-point component. The method for producing an organozinc compound comprising an adduct of dialkylzinc and dialkylselenium having:
ジアルキルセレンのうちの低沸点成分が両者のうちの高
沸点成分に対して1.05〜1.2当量比となるように、前記
ジアルキル亜鉛と前記ジアルキルセレンとを混合するこ
とを特徴とする特許請求の範囲第１項記載の有機亜鉛化
合物の製造法。2. The dialkylzinc and the dialkylselenium so that the low-boiling point component of the dialkylzinc and the dialkylselenium has a ratio of 1.05 to 1.2 equivalent to the high-boiling point component of the both in the step a). The method for producing an organozinc compound according to claim 1, characterized in that
で10分〜３時間反応させる工程、徐々に昇温する工程、
30℃〜80℃で10分〜２時間熟成させる工程からなること
を特徴とする特許請求の範囲第１項または第２項記載の
有機亜鉛化合物の製造法。3. The step of heating the mixture comprises 0 ° C. to 40 ° C.
For 10 minutes to 3 hours, a step of gradually raising the temperature,
The method for producing an organozinc compound according to claim 1 or 2, comprising a step of aging at 30 ° C to 80 ° C for 10 minutes to 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6475285A JPH0742295B2 (en) | 1985-03-28 | 1985-03-28 | Method for producing organozinc compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6475285A JPH0742295B2 (en) | 1985-03-28 | 1985-03-28 | Method for producing organozinc compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61225188A JPS61225188A (en) | 1986-10-06 |
| JPH0742295B2 true JPH0742295B2 (en) | 1995-05-10 |
Family
ID=13267214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6475285A Expired - Lifetime JPH0742295B2 (en) | 1985-03-28 | 1985-03-28 | Method for producing organozinc compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0742295B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4944522B2 (en) * | 2006-07-07 | 2012-06-06 | 住友電気工業株式会社 | Laser optical component made of polycrystalline zinc selenide and method for producing the same |
-
1985
- 1985-03-28 JP JP6475285A patent/JPH0742295B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61225188A (en) | 1986-10-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7238596B2 (en) | Method for preparing Ge1-x-ySnxEy (E=P, As, Sb) semiconductors and related Si-Ge-Sn-E and Si-Ge-E analogs | |
| US3224913A (en) | Altering proportions in vapor deposition process to form a mixed crystal graded energy gap | |
| US20030013222A1 (en) | Process for producing an epitaxial layer of gallium nitride by the HVPE method | |
| JPH0217193A (en) | Cyclic organometal compound | |
| US6207844B1 (en) | Compounds and methods for depositing pure thin films of gallium nitride semiconductor | |
| JPH06252057A (en) | Manufacture of semiconductor device | |
| KR101250153B1 (en) | A trimethylgallium, a method for producing the same and a gallium nitride thin film formed from the trimethylgallium | |
| Han et al. | Synthesis and characterization of novel zinc precursors for ZnO thin film deposition by atomic layer deposition | |
| JPH02163930A (en) | Manufacture of epitaxial | |
| JPH0742295B2 (en) | Method for producing organozinc compound | |
| JP2678736B2 (en) | Organozinc compound | |
| JP2678737B2 (en) | Organozinc compound | |
| KR100319389B1 (en) | Organogallium compound, process for the preparation thereof and preparation of gallium nitride film using same | |
| JPH0742296B2 (en) | Method for producing organozinc compound | |
| KR100385634B1 (en) | Metal-organic chemical vapor deposition of zinc oxide thin films exhibiting lasers | |
| Pernot et al. | Photo‐assisted chemical vapor deposition of gallium sulfide thin films | |
| JPH0463040B2 (en) | ||
| JP2706337B2 (en) | Method for manufacturing compound semiconductor thin film | |
| KR20020066324A (en) | New methods of fabricating devices and semiconductor layers comprising cadmium mercury telluride, mercury telluride, and cadmium telluride | |
| US20060288933A1 (en) | Chemical vapor deposition reactor | |
| JPS63283032A (en) | Application of allyl telluride and ii-vi epitaxial film in growth of mocvd | |
| JPS63220528A (en) | Compound semiconductor film and manufacture thereof | |
| JP2740681B2 (en) | Method for manufacturing compound semiconductor thin film | |
| JP4201969B2 (en) | Method for producing group III nitride film | |
| JPH07118453B2 (en) | Manufacturing method of semiconductor superlattice |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |