JPS63220514A - Compound semiconductor film and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain a P-type conductivity IIb-VIb compound semiconductor film having high quality by adding one element selected from a group consisting of Cu, Ag and Au as group Ib elements in the element periodic table as an impurity. CONSTITUTION:A compound containing a group IIb, a compound containing a group VIb and a hydrocarbon group compound or a chelate compound containing a group Ib as an impurity introduced to a compound semiconductor as the raw gases of the compound semiconductor are admitted into a reaction vessel in the vapor phase, and a IIb-VIb compound semiconductor film is grown through a chemical vapor phase reaction. The IIb-VIb compound semiconductor film as a compound semiconductor film displays P-type conductivity because it includes one kind of Cu, Ag and Au as group Ib elements as the impurity. ZnS, ZnSe, CdS and CdSe can be cited concretely as the combination of IIb-VIb. Accordingly, the P-type conductivity compound semiconductor film having high quality is acquired.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a compound semiconductor film made of elements of group IIb and group yb of the periodic table of elements, and a method for manufacturing the same.

[Conventional technology]

In recent years, ZnS has attracted attention as a blue-emitting material.

As a method for manufacturing compound semiconductor films such as Zn5e,
A method called metalorganic chemical vapor deposition (MOOVD) has come to be widely adopted.

In this MOCVD method, for example, dimethylzinc C (CH3
) 2 Zn ] and other organometallic compounds containing Group 1IIb elements of the periodic table are subjected to gas phase pyrolysis to produce hydrogen selenide (H2Se
), etc., to grow an Ib-VIb group compound semiconductor film such as ZnSθ on a substrate.

[Problem that the invention seeks to solve]

In order to obtain a compound semiconductor film having p-type conductivity using a nb-vtb group compound, a compound containing N, P, or As, which is a yb group element, is added to the source gas. In order to replace the YB group element with the YB group element in the semiconductor crystal, extra vacancies of the YB group element are likely to be created during the replacement, and the generated vacancies act as electrical donors, and the added YB group element It is known that a so-called compensation effect occurs, which prevents the molecules from acting as acceptors. Due to this compensation effect, the compound semiconductor becomes electrically high in resistance, resulting in a disadvantage that p-type conductivity cannot be obtained. I want to
It has been extremely difficult to achieve p-type conductivity using the conventional method of adding group B elements.

The present invention solves the drawbacks of the prior art and provides a high quality p-type anal-VIb group compound semiconductor film,
The purpose of this invention is to provide a manufacturing method that allows easy growth of linear films.

[Means to solve the problem]

The above purpose is to use a carrier gas (e.g. hydrogen This can be achieved by introducing a gas (gas) into a reaction vessel in a vapor phase and growing a IIb-VIb group compound semiconductor film by a chemical vapor phase reaction. In the compound semiconductor film of the present invention, since the Ib group element is replaced with the IIb group element in the crystal, the generation of VIb group element vacancies is suppressed, and even if extra IIIbIb group element vacancies are generated during the replacement, the Ib group element vacancy is suppressed. Since the vacancies of the element act as acceptors, the added I
There is no doubt that group Ib elements act as acceptors.

[For production]

The IIb-VIb group compound semiconductor film of the compound semiconductor film of the present invention contains Cu, Ag, and Au which are group Ib elements.
By containing one of these as an impurity, p-type conduction is exhibited. As a combination of IIb-VIb, ZnS
.

Zn5e, Ode, C! dse can be specifically mentioned.

In the method for manufacturing a compound semiconductor film of the present invention, the hydrocarbon compound containing a group IIb element as an impurity to be introduced is such that the group Ib element is Cu, Ag, or Au, and the alkyl group is methyl, It is desirable to use a hydrocarbon compound that is any one of hexynyl, isobutenyl, and cyclopentanenyl groups. In order to facilitate the thermal decomposition reaction of the hydrocarbon compound that still contains the Group IIb element, it is also preferable to use a hydrocarbon compound that forms a complex with an amine or phosphine. And, as a q-hybrid compound containing group IIb,
Copper Porefi Scolding Copper Phthalo/Anin, Copper TC! Metal chelates such as IQ can also be used.

All of these compounds are solid at room temperature and pressure, and because they have sublimation properties, they can be stored in a container, heated to a temperature below the melting point or decomposition point, sublimated, and transported to a reaction container by a carrier gas.

〔Example〕

FIG. 4 is a system diagram showing the configuration of an apparatus for manufacturing a single crystal film of a Zn5e compound semiconductor used in this example. In the figure, liquid diethylzinc C(02H5)2, which is a raw material containing the Zn element constituting the Zn5e compound semiconductor, is shown.
By bubbling hydrogen gas whose flow rate is regulated by a gas flow controller into a bubbler container in which Zn:1 is sealed, hydrogen gas containing the required amount of diethylzinc is formed, and impurities are added to it. As doping compounds for addition, cyclopentanenyl copper (05H50u), which is a type of organometallic compound of copper, and triphenylphosphine P (C6H5, which is a type of tophosphine) are used.
) A predetermined flow rate of hydrogen gas passed through the container 7 containing the complex of 3 is added as a raw material, and on the other hand, hydrogen selenoide (H2E
A required amount of hydrogen gas is supplied from the gas cylinder 2 filled with te) via the gas flow controller/2, and a predetermined flow rate of hydrogen gas is added from the gas flow controller// to the raw materials to produce the above-mentioned diethyl zinc and cyclo It is introduced into the reaction vessel in a gas phase together with the raw material gas containing the pentanenyl copper/triphenylphosphine complex. Inside the reaction vessel, a GaAs substrate 3 is placed on a substrate holder 1, heated to a predetermined temperature by a high-frequency heating coil, and heated to a p-type conductive ZnEie containing copper by a chemical vapor phase reaction.
A compound semiconductor single crystal film is formed on a GaAs substrate. The lattice constant mismatch between GaAS and Zn5e is 7% or less, and a good single crystal film can be formed. If this lattice constant mismatch is allowed up to ~j%, nP, Si, etc. can be used as the substrate. In the formation of this Zn5e single crystal, the doping compound cyclopentanenyl copper triphenylphosphine complex is a solid that sublimes at normal temperature and normal pressure, and hydrogen passing through the gas flow controller 10 while heating the container 7 Since the gas containing the vapor of the doping compound can be easily obtained by simply passing the gas through the container 7, the temperature of the container 7 can be kept constant and the gas flow rate can be precisely and easily controlled by the gas flow controller 10. is possible.

Here, cyclopentanenyl copper in the raw material complex is Zn5
e It can be easily thermally decomposed in the range of the single crystal film growth temperature (approximately 300-600'C), but on the other hand, triphenylphosphine in the complex is hardly thermally decomposed in the above temperature range and is exhausted. No, copper can be added selectively.

Using the compound semiconductor single crystal film growth apparatus described above,
Passed through a pub 7' container of diethylzinc at a temperature of 1°C. 2 J″cc/min of hydrogen gas and 7.20′c-
〇 - 10 cc/min of hydrogen gas passed through the container 7 of the diclopentadienyl copper/triphenylphosphine complex heated to /ρ/min was mixed and diluted with the hydrogen gas, and the raw material gas was added to the reaction vessel/. Lead inward. At the same time, the raw material gas for 100 cc of hydrogen thylenide gas diluted with hydrogen gas was further mixed and diluted with 117 volumes of hydrogen gas, introduced into the reaction vessel, and heated to a temperature of 1 ltOO'C.
Zn5 containing copper is sprayed onto the aAs substrate 3.
e Single crystal films were grown at a rate of 2 μm per 7 h.

During growth, it is important to adopt conditions that suppress the generation of Se vacancies, and for this purpose, it is necessary to supply a sufficiently large amount of raw material containing Se and to ensure that the growth is always carried out by supplying the raw material containing Zn. However, such conditions could be easily achieved by increasing the supply amount of the Se-containing raw material to at least three times the molar ratio of the Zn-containing raw material supply amount. These conditions are also applied when growing other IIb-VIb group compound semiconductor films. The surface of the obtained ZNSE single crystal film had a good surface, and the crystallinity was the same as that without adding copper, so there were no problems. Also, Zn5
eThe resistance of the single crystal film is the same when no additive is included and when yb
When the group elements P and As are included, the resistance value is as high as 106Ω・m or more, whereas when copper is added as a raw material for the cyclopentanenyl copper/triphenylphosphine complex, the resistance value is several +Ω・m. It showed the following low resistance value.

The p-type carrier concentration was 1017/crA, and the hole mobility was approximately /00cnI/V'' at room temperature, indicating good p-type can conductivity.Furthermore, the photoluminescence properties were similar to those of the conventional one. When P and As, which are Group B elements, are added, light emission other than blue becomes dominant as shown in the curve in Figure 2, whereas in the case of this example, the sample to which copper was added As shown in the curve/B of Figure 2, the emission spectrum of is shown in Fig. 2. In the above examples of the present invention, very good results were obtained where only the blue emission (near about 4170 nm) was strong. The example of cyclopentanenyl copper/triphenylphosphine complex has been given, but in addition to this, hydrocarbons having copper, silver, or gold as group IIb elements and methyl, hexynyl, or isobutenyl groups as alkyl groups or carbonized Complexes of hydrogen and amines, such as hexynyl copper [C4Hg O= CCu ”
J, isobutenyl silver [(c)13)2cm=cH
Ag], trimethyl gold/ethylenediamine complex [:
, 2 hu (cI(3)3・NH2CH2CH2NH
2), copper-containing metal chelate compounds such as copper porphyrin, copper phthalo/anine, and copper TONQ.
It was confirmed that group IIb impurities can be added using these materials as raw materials in the same manner as in this example.

The following table shows the characteristics of typical compounds. Both are solid at room temperature and pressure and have sublimation properties. Substances without melting points are those that decompose before melting. These raw materials are placed in the container 7 shown in the previous example, sublimated while being maintained at a temperature below the melting point or decomposition temperature, and introduced into the reaction container by a carrier gas.

Each compound decomposes in the reaction vessel, and group IIb elements are converted into IIb group elements.
b - Added to the VIb group compound semiconductor film. The ease with which these compounds decompose within the reaction vessel determines the efficiency of Group IIb addition. For compounds with a high minM temperature, it is necessary to increase the flow rate of the carrier gas flowing into the container 7 in order to compensate for the decrease in efficiency.

Table: Compounds that can be used for addition of Group IIb elements In the above example, Zn5e was given as an example of a Group IIb-VIb compound, but other compound semiconductors comprising Group IIb and Yb group elements include ZnS and ZnTe.

It goes without saying that the method of the present invention can also be applied to the production of binary or higher compound semiconductor films such as 0clS, 0dSe, and CdTe.

〔Effect of the invention〕

As explained in detail above, according to the method for manufacturing a IIb-VIb group compound semiconductor film of the present invention, a Group IIb element is used as an impurity to be added, and a Group VIb raw material is sufficiently supplied during film growth. It is possible to suppress the compensation effect due to the generation of group VIb vacancies, which is problematic when a group element is used as an impurity.

As a result, the compound semiconductor film of the present invention becomes a commercial quality p-type can conductive compound semiconductor film that emits blue light.

[Brief explanation of drawings]

FIG. 1 is a system diagram showing the configuration of the manufacturing apparatus for the ZnS e single crystal film used in the example of the present invention, and FIG. 2 is a photograph of the ZnS e single crystal film formed in the example of the present invention at a temperature of FIG. 3 is a diagram showing luminescence characteristics. /... reaction container, 2... substrate holder, 3... ci
aAs substrate, G...high frequency heating coil, j...bubbler container, -row B...to hydrogen selenide gas cylinder, 7...container. 10. //, /, 2...Gas flow controller, /3...Exhaust port, /G...Hydrogen gas, /j・
...Emission spectrum of sample with P concentration of 1015 pieces/ctI, /B...Cu concentration of 101 pieces/ctI

Claims (7)

[Claims] (1) A group consisting of Zn and Cd, which are Group IIb elements of the Periodic Table of Elements, and a group consisting of S, Se, and Te, which are Group VIb elements of the Periodic Table, on a semiconductor substrate having consistency in lattice constant, respectively. A single-crystalline compound semiconductor film consisting of a combination of selected elements, in which an element selected from the group consisting of Cu, Ag, and Au, which are group Ib elements of the periodic table of elements, is added as an impurity. A compound semiconductor film characterized by: (2) A compound containing an element selected from the group consisting of Zn and Cd, which are elements of group IIb of the periodic table, and an element selected from the group consisting of S, Se, and Te, which are elements of group VIb of the periodic table, in the reaction vessel. In the method of manufacturing a IIb-VIb group compound semiconductor film on a substrate placed in the reaction vessel by introducing a compound containing one element in the gas phase in the reaction vessel and then thermally decomposing it in the reaction vessel, In addition, a compound containing an element selected from the group consisting of Cu, Ag, and Au, which are Group Ib elements of the Periodic Table of Elements, is introduced in a gas phase, and the Group IIb-VIb compound semiconductor is added with the Group Ib element. A method for manufacturing a compound semiconductor film, the method comprising manufacturing a film. (3) The method for manufacturing a compound semiconductor film according to claim 2, wherein the raw material containing the group VIb element is supplied in excess of the raw material containing the group IIb element. (4) The method for producing a compound semiconductor film according to claim 2 or 3, wherein the compound containing the Ib group element is solid at room temperature and pressure and has sublimation properties. (5) The compound containing a Group Ib element is a hydrocarbon compound of a Group Ib element having one group selected from the group consisting of a methyl group, a hexynyl group, an isobutenyl group, and a cyclopentanenyl group. Characteristic Claim 2
A method for manufacturing a compound semiconductor film according to any one of Items 1, 3, and 4. (6) A hydrocarbon compound of a Group Ib element in which the compound containing a Group Ib element has one group selected from the group consisting of a methyl group, a hexynyl group, an isobutenyl group, and a cyclopentanenyl group, and an amine or Claims 2 and 3, characterized in that it is a complex with phosphine.
4. A method for manufacturing a compound semiconductor film according to any one of Item 4. (7) Compounds containing Group Ib elements include porphyrins, phthalocyanines, and tetracyanoquinodimethane (TCN
The method for manufacturing a compound semiconductor film according to any one of claims 2, 3, and 4, characterized in that the metal chelate compound is a metal chelate compound of one selected from the group consisting of Q) and Cu.