JP2678737B2 - Organozinc compound - Google Patents

Description

BACKGROUND OF THE INVENTION [0001] Field of the Invention The present invention includes a dialkyl zinc (hereinafter referred to as R2Zn), relates to the adduct or Ranaru organozinc compound dialkyl sulfur (hereinafter abbreviated as R2S). [0002] More specifically, it relates <br/> the organozinc compound consisting adduct valid R2Zn and R2S as raw materials for MO-CVD method is a manufacturing technology of a semiconductor thin film and a semiconductor device. SUMMARY OF THE INVENTION The present invention relates to a blue light emitting diode, zinc sulfide (ZnS) which is a material for a thin film EL element, and an organozinc compound which is a raw material of an MO-CVD method effective for producing a mixed crystal thin film thereof. In this case, by mixing R2Zn and R2S and forming an adduct of R2Zn and R2S with high purity and reproducibility by reaction and thermal formation, H2S can be formed as compared with conventional R2Zn.
The reactivity to hydrides such as (hydrogen sulfide) or H2Se (hydrogen selenide) is low, and mixing of the raw materials, which has been a problem in the conventional MO-CVD method, causes an unnecessary pre-reaction that occurs upstream of the substrate. It is difficult to obtain high-quality ZnS and its mixed crystal thin film, and thus high-performance semiconductor devices.
The fee is provided. [0004] Conventionally, the MO-of ZnS and its mixed crystal thin film
In the production by the CVD method, dimethylzinc: Zn (CH3) 2 and diethylzinc: Zn are used as raw materials in a zinc source.
Using an organic zinc compound such as (C2H5) 2, hydrogen sulfide:
H2S and hydrogen selenide: It was customary to react with H2S. The chemical reaction when these raw materials are used is represented by the following formula. (CH3) 2Zn + H2S → ZnS-12CH4 ... (1) (C2H5) 2Zn + H2S → ZnS + 2C2H6 ... (2) However, these reactions are MO because R2Zn is active.
-When a raw material gas is introduced into the CVD reactor, the reaction proceeds in the gas phase at the same time as the hydride is mixed with the hydride to generate ZnS fine particles before the raw material reaches the substrate surface,
These ZnS fine particles adversely affected the growth process on the surface of the thin film growth substrate, and the quality of the obtained crystals was not very high. Conventionally, as means for solving these problems, (1) R2Zn and H2S are mixed immediately before the substrate (for example, J. Cryst Growth 59, P1.
982)), (2) increase the gas flow rate by reducing the pressure (eg, Jpn. J. Appl. Phys. 22, L).
583 (1983)) and other equipment system measures, and
(3) R2Zn and R2 instead of R2Zn as the zinc raw material
The adduct obtained by equimolar mixing with S is used (4th
Proceedings of the 5th JSAP Academic Lecture, P633 (1)
984) Measures using raw materials such as lecture number 12P-S-4) have been studied. The MO-CVD method based on the above-mentioned prior art has the following problems in terms of manufacturing method and application to devices, and it has been desired to solve the problems. . For the prior arts (1) and (2), 1. Since they are mixed just before the substrate, it is difficult to obtain the uniformity of the thin film thickness, composition, dopant distribution and the like. [0009] 2. Large area and large number of substrates are difficult to process and mass productivity is poor. 3. The quality of the crystals is poor, and the emission and conduction properties cannot be controlled. For example, in the conventional manufacturing method, R2Zn
And H2S were mixed and sprayed at a distance of ˜2 cm from the substrate, and the size of the substrate that could be processed by this was 20 mm in diameter at most. The obtained crystal has many defects,
The fact is that a low-resistance film that can be used as a current element has not been obtained even when doping with a donor impurity, which is necessary when manufacturing a light emitting diode. (Exte
ended Abstracts of the 15t
h Conference on SolidStat
e Devices and Materials 1
983 pp349, B-7-8) With respect to the prior art (3), 1. The reactivity between R2Zn and R2Se is not very high,
R2Zn of the following formula is obtained by simply mixing both in equimolar amounts.
+ R2S → R2Zn-SR2 (3) The reaction could not be completed, and the physical properties such as vapor pressure of the obtained product were
The variation was large, depending on the mixing conditions, history until use in the reaction, etc. 2. In addition, as a result, using the adduct obtained by mixing the equimolar amounts as a raw material, H2S
When ZnS epitaxial growth was carried out by reacting with, the growth rate of the epitaxial thin film and the reproducibility of its physical properties were poor. In order to solve the above problems, the object of the present invention is that the reactivity with a hydrogen compound such as H2S or H2Se as a Zn raw material is lower than that of R2Zn, the gas phase reaction at room temperature can be suppressed, and MO-CVD. By using it as a Zn raw material in the method, it is possible to grow a good quality thin crystal film on a large area and on a large number of thin films. Also, by doping impurities, it has a desired light emitting property and conductivity, and has a device-level crystal quality. The point is to provide a high-purity organozinc compound that achieves reproducibility with high reproducibility. The organozinc compound of the present invention comprises a mixture of dialkylzinc and dialkylsulfur, and is represented by the general formula R ₂ Zn-S in which excess components thereof are not present.
It is characterized by comprising an adduct represented by R ₂ (wherein R represents an alkyl group). Specifically, in order to ensure high-purity and reproducible physical properties of the adduct, R ₂ Zn-obtained by removing unnecessary components after the reaction and aging by mixing excessively low-boiling components out of them It is an adduct of SR ₂ . As a highly pure and reproducible method for producing the same, low-boiling components are generally mixed in an excess amount, and reaction conditions vary depending on the combination of individual alkyl groups, but the range is from 0 ° C to 40 ° C. It comprises a step of reacting at 10 ° C. for 10 minutes to 3 hours, gradually raising the temperature, aging at 30 ° C. to 80 ° C. for 10 minutes to 2 hours, and then distilling off excess components. Although R2Zn and R2S applicable to the present invention are summarized in Table 1, it is obvious that the present invention is not limited to this. [Table 1] The adduct of R2Zn and R2S includes R2Zn as an electron acceptor and R2S as an electron donor.
It is obtained as a result of a one-to-one acid-base reaction, and has the structure of the formula (4) R2Zn-SR2 (4). As a method for producing the adduct, it is possible in principle to mix each component in equimolar amounts,
(Proceedings of the 45th JSAP Academic Lecture Meeting P633 (1
984) Lecture No. 12P-S-4), the following steps are required to complete the reaction and produce an adduct having high purity and reproducible physical properties. R2Zn and R2S are mixed in a low boiling point component in an excessive amount, preferably in a low boiling point component to a high boiling point component at a ratio of 1.1 to 1.2 equivalents to obtain a low boiling point component. Below the boiling point of the component, approximately 0 ℃ ~ 40 ℃ 10 minutes ~
Sufficiently react for 3 hours, preferably 10 to 35 ° C. for 1 to 2 hours. After that, in order to complete the reaction, the temperature is gradually raised to 30 minutes to 80 ° C. for 10 minutes to 2 hours, preferably 10 minutes.
The temperature is raised at a rate of 15 ° C./hour and 30 minutes to 1 at 30 to 70 ° C.
Let it mature for hours. Finally, excess components are removed by distillation. The formation of the adduct can be confirmed by the following facts. (1) Heat is generated by mixing the two. (2) The vapor pressure-temperature curve of the produced adduct is different from that of the starting materials R2Zn and R2S. (3) The reaction takes place at a ratio of R2Zn and R2S of 1: 1 due to the charged amount of the raw materials, the amount of the product and the excess distillate component. (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. EXAMPLES Example 1 (CH3) 2Zn-S (C2H5) 2 S (C2H5) 2 109.
5 g (1.2166 mol) was charged, and 122.0 g (1.279 mol) of (CH3) 2Zn was added dropwise with stirring with a dropping funnel to react. The reaction was exothermic and the exotherm was large. The reaction temperature was controlled at 10 to 15 ° C. and the reaction was carried out for 1 hour. After that, the temperature was gradually raised at a rate of 10 ° C./hour and aged at 38 ° C. for 30 minutes. After that, unnecessary excess was distilled off by distillation. The product was 227 g. FIG. 1 shows the vapor pressure-temperature characteristics of the obtained adduct. The horizontal axis 1 is temperature and the vertical axis 2 is vapor pressure. Solid line 3
Is the adduct, and broken lines 4 and 5 are the raw materials S, respectively.
2 shows vapor pressure characteristics of (C2H5) 2 and (CH3) 2Zn. FIG. 2 shows the product (CH3) 2 by NMR.
The signal by the proton of the methyl group of Zn is shown. The chemical shift of the product is δ = -0.6
0 ppm, and for a single component of (CH3) 2Zn δ =
Since it is -0.67 ppm, (CH3) 2Zn-S
Formation of (C2H5) 2 adduct was observed. The variation between lots having different physical properties such as vapor pressure characteristics was less than the detection. In addition, from the result of NMR, the presence of a single component of (CH3) 2Zn as a raw material was not recognized, and the purity was extremely high. (Example 2) (C2H5) 2Zn-S (C2H5) 2 In the same manner as in Example 1, a 300 ml round bottom flask was charged with S.
56.3 g (0.6255 mol) of (C2H5) 2 was charged, and with stirring, (C2H5) Zn 75.4 g
(0.611 mol) was added dropwise to react. The reaction was exothermic and the amount of heat generated was large. The reaction temperature was controlled at 35 to 40 ° C. and the reaction was carried out for 2 hours. After that, the temperature is gradually raised to 45 ° C.,
Aged for 1 hour in the natural state. Next, unnecessary excess was distilled off by distillation. The product was 130 g. FIG. 1 shows the vapor pressure of the adduct obtained by the solid line 6. The broken lines 4 and 7 are S (C2H), which is the raw material, respectively.
5) shows vapor pressures of 2 and (C2H5) 2Zn. (Example 3) (CH3) 2Zn-S (CH3) 2 In the same manner, (CH3) which is approximately equivalent to or less than S (CH3) 2 is used.
The above-mentioned adduct was produced by the dropwise reaction of 2Zn. A solid line 8 in FIG. 1 shows the vapor pressure of the adduct, and a broken line 9 and a broken line 5 show the vapor pressures of S (CH3) 2 and (CH3) 2Zn, which are the respective raw materials. (Example 4) (C2H5) 2Zn-S (CH3) 2 In the same manner, the above adduct was produced using S (CH3) 2 and (C2H5) 2Zn. The solid line 10 in FIG. 1 shows the vapor pressure of the adduct. Table 2 exemplifies the vapor pressures of the organozinc compounds comprising the adduct of R2Zn and R2S according to the present invention with respect to typical temperatures. [Table 2] Next, using the adduct obtained in the above embodiment, a ZnS crystal thin film was formed into a G by using a MO-CVD apparatus under normal pressure.
When formed on the aAS and GaP substrates, good quality single crystal thin films were obtained with any of the adducts. The flow of white turbid particles due to the pre-reaction of R2Zn and H2S 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. And H2S were mixed in advance using He gas as a carrier and then introduced into the reaction tube, and ZnS single crystal having a smooth surface state on a GaAs and GaP single crystal substrate placed at a position 200 mm away from the introduction port. Since the thin film was obtained, it became clear that the adduct according to the present invention suppressed the pre-reaction and had a great effect in terms of productivity. Also, A
By doping a donor impurity such as l, Ga, Cl, or I, n-type conductivity with a specific resistance of 0.1 to 1 Ωcm was obtained after the growth. In addition, the xenon lamp has a wavelength of 250
Strong blue emission of 470 nm was obtained by ultraviolet irradiation up to 350 nm. These facts show that the crystal formed by using the organozinc compound according to the present invention has high quality. Further, the adduct according to the present invention has the following effects as compared with the conventional adduct obtained by simply mixing the same molar amount. (1) Using the same bubbler, the physical properties of the crystal thin film, in particular, the specific resistance, the emission wavelength, and the production of device characteristics such as emission wavelength and intensity in the production of a light emitting diode using the crystal. There was almost no change with time, and the variation was extremely small. (2) Even if the different adducts between lots were used, the variation was extremely small. As described above, according to the present invention, an organozinc compound comprising an adduct of R2Zn and R2S with high purity and reproducibility of physical constants such as vapor pressure is provided. to provide
Can be . 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.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a vapor pressure-temperature characteristic diagram of an organozinc compound. FIG. 2 is a signal diagram of a methyl group proton of a product. [Explanation of symbols] 1 ... Temperature 2 ... Vapor pressure 3 ... (CH3) 2-S (C2H5) 2 4 ... (C2H5) 2S 5 ... (CH3) 2Zn 6 ... ) 2 7 ·· (C2H5) 2Zn 8 ·· (CH3) 2Zn—S (CH3) 2 9 ·· (CH3) 2S 10 · (C2H5) 2Zn—S (CH3) 2 11 · TMS 12 · Product 13 · Chemical shift 14, signal strength

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Takashi Shimobayashi               Shares 3-3-5 Yamato, Suwa City, Nagano Prefecture               Inside the company Suwa Seikosha (72) Inventor Teruyuki Mizumoto               Shares 3-3-5 Yamato, Suwa City, Nagano Prefecture               Inside the company Suwa Seikosha (72) Inventor Masao Fujisawa               3-1-1 Katsuma, Hofu-shi, Yamaguchi Prefecture (72) Inventor Akihiro Ichikawa               No.287-155 Tokuyama, Tokuyama City, Yamaguchi Prefecture                    Examiner Zenichi Wakimura                (56) References JOURNAL DE CHIMIE                 PHYSIQUE ET DE PH               YSICO-CHIMIE BIOLO               GIQUE, 1972, 69 (4), 601-604

Claims (1)

(57) [Claims] Dialkyl zinc and dialkyl sulfur are mixed
The general formula R ₂ Zn-S in which these excess components do not exist
An organozinc compound comprising an adduct represented by R ₂ (wherein R represents an alkyl group).