JPS63139100A - Member for producing compound semiconductor single crystal and production thereof - Google Patents

Abstract

PURPOSE:To produce the titled member causing no cracking and producing a small strain on the interface between the layers by forming a coating layer of BN, AlN or Al2O3 on the surface of a quartz member especially with an intermediate layer in-between. CONSTITUTION:A high frequency coil 2 is placed in an ion plating vessel 1 and a quartz member 9 is set in the coil 2 with the open end downward. Si in a crucible 3 is evaporated by heating with an electron gun 5 and O2 is introduced from a pipe 6 and ionized by high frequency plasma. N2 is further introduced from a pipe 7 and ionized and B or Al in a crucible 4 is evaporated by heating to form an intermediate layer of Si-O-B-N and/or Si-O-Al-N whose coeffts. of thermal expansion is between the coeffts. of thermal expansion of quartz and BN, AlN or Al2O3. The evaporation of Si is then stopped and a coating layer of BN, AlN or Al2O3 is formed.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a member for producing a compound semiconductor single crystal and a method for producing the same, and particularly relates to a boat, a liner tube, and a reaction tube used for RF synthesis of an IT-V group compound. Boat support stand 2 This relates to reaction tubes, crucibles, containers, etc.

[Prior Art] Conventionally, containers for producing single crystals of this type have been used to
Quartz glass, which has excellent heat resistance and workability, is mainly used. However, quartz glass undergoes a reaction with Ga or GaAs according to the following equation (1), and 81 is mixed into GaAs.

SiO2+4Ga −+ Si+ 2Ga20↑ −
(+) Furthermore, when a quartz reaction tube is used, quartz and Ga or Si in GaAs undergo a reaction according to the following equation (2) to generate SiO gas, which causes Si to be mixed into GaAs.

Si+Si02→2SiO↑ ・・・ (2)
To prevent this Si contamination, B was used instead of quartz glass.
A container consisting of N, AQN, Ajh03 is considered.

Especially semiconductor single crystals! P-BN was used as the material for boats and crucibles used in II construction.

However, reaction vessels and boats made of BN, AlN, and M2O3 have the disadvantage that welding is difficult and expensive.

Therefore, BN, AQN or IV is applied to the surface of the quartz glass.
! A method of coating GaAs with 203 to prevent Si from being mixed into GaAs has been proposed in the following publications (1) to (2).

■ Japanese Patent Publication No. 49-42419 ■ Japanese Patent Application Publication No. 77748-198 ■ Japanese Patent Publication No. 217700-1970 ■ Japanese Patent Publication No. 59-227800278 00 ■ Publication No. 0-255698 However, BN, MLN, M2O3 SiO2
GaAs has a thermal expansion coefficient significantly different from that of GaAs.
When subjected to thermal cycles due to single crystal growth, cracks occurred in the coating film and sufficient effects could not be achieved.

Conventionally, attempts have been made to coat intermediate compounds in order to solve this problem. For example, JP-A-60-1416
In Japanese Patent No. 96, the applicant proposed a method in which 8N is formed through Si3N4, which is effective in preventing the occurrence of cracks.

However, it was still observed that cracks appeared after repeated thermal cycles.

Quartz members and their coating materials are expensive;
It was hoped that the number of times it could be used would increase.

[Problems to be solved by the invention] In this way, BN, AQN, and Al2O are used in the quartz member.
Even if a No. 3 coating is applied, there is a problem in that when subjected to thermal cycles due to GaAs crystal growth, cracks are likely to occur due to the difference in thermal expansion coefficient between the quartz and the coating film.

In particular, conventional methods such as CVD or plasma CVD have been used to
8. Since compound films such as AQN, SiC, and Si3N4 were formed directly on quartz, Si02-BN,
Si02-AlN, Si02-3iC, Si02-
Strain was concentrated at the interface of 8i3N4, etc., and cracks were likely to occur.

Therefore, it has been difficult to produce semiconductor single crystals with low Si contamination with good reproducibility.

SUMMARY OF THE INVENTION Thus, an object of the present invention is to solve the problems of the prior art described above and to provide a member for manufacturing a compound semiconductor single crystal and a method for manufacturing the same, which can produce 1 q of compound semiconductor single crystals free from Si contamination.

[Means for Solving the Problems] In order to achieve the above object, the compound semiconductor single crystal manufacturing member of the present invention includes BN on the surface of the quartz member.

In a compound semiconductor single crystal production member provided with a coating layer made of At1N or Al2O3, the thermal expansion coefficient between the quartz member and the coating layer is the same as that of quartz and BN, AfLN or M2O3 forming the coating layer. Si-0-B-N material with intermediate value, Si-0-
An intermediate layer made of an M--N type material or a composite composition thereof is provided.

In addition, such a member includes a Si-0-B-N-based material, Si-0-, on the surface of the quartz member, whose coefficient of thermal expansion is intermediate between that of quartz, BN, AlN, or M2O3.
After forming an intermediate layer made of an A1-N material or a composite composition of these materials by an ion plating method,
It is manufactured by providing a coating layer made of ON, AfLN or M2O3 on the intermediate layer.

[Function] As described above, by forming an intermediate layer between the quartz member and the covering layer using the ion plating method, the intermediate layer has a coefficient of thermal expansion intermediate between the two, thereby applying a thermal cycle due to GaAs crystal growth. In this case, it becomes possible to reduce the strain that occurs at the interface between each layer, and as a result, the occurrence of cracks is prevented.

Note that the composition of the intermediate layer preferably changes continuously in the direction perpendicular to the layer surface from the viewpoint of preventing cracks due to the coefficient of thermal expansion, and may be composed of a multilayer film.

[Example] Embodiments of the present invention will be described below with reference to the accompanying drawings.

Embodiment 1 FIG. 1 is a configuration diagram of an ion plating apparatus for carrying out a method for manufacturing a member for manufacturing a compound semiconductor single crystal according to an embodiment of the present invention.

A high frequency coil 2 is provided in an ion plating container 1, and two crucibles 3 and 4 are arranged side by side below the high frequency coil 2. Furthermore, an electron gun 5 is provided below these crucibles 3 and 4, and an oxygen introduction pipe 6 and a nitrogen introduction pipe 7 are led from outside of the ion plating container 1 to the upper parts of the crucibles 3 and 4, respectively. Further, a heater 8 is arranged along the inner surface of the ion plating container 1.

Ion plating was performed on the inner surface of a quartz reaction tube for boat-method GaAs growth using such an ion plating apparatus.

First, Si, which will be the vapor deposition element, is placed in the crucibles 3 and 4, respectively.
(purity 99.999%) and 8 (purity 99.999%)
), and a quartz reaction tube 9 was placed inside the high-frequency coil 2 with its open end facing downward. In this state, the Si in the crucible 3 was heated and evaporated with the electron gun 5, and 02 was introduced through the oxygen introduction tube 6 to cause an ionization reaction with high frequency plasma, thereby producing a transparent amorphous \'j rfJ film. Next, the output of the electron gun 5 was increased while keeping the pressure of 02 constant, and the Si
By increasing the amount of evaporated, a Si ridge of Si-0 was fabricated.

Next, N2 is introduced from the nitrogen introduction tube 7 and an ionization reaction is carried out to produce a Si-0-N film. Si3N
4) was produced. Next, 8 in the crucible 4 is heated and evaporated with an electron gun 5 to create a Si-B-N film, then the evaporation of Si is stopped and a B-N film is created, and finally the BN film is Created.

The GaAs single crystal grown using the quartz reaction tube 9 and the P-BN boat produced in this way has a dislocation density of 10310I2, which is almost the same as when using a conventional quartz boat, and has no Si contamination. 1/10 to 1/ of conventional
It had been reduced to 100. Furthermore, no cracks were observed even when the quartz reaction tube 9 was used several times for growth.

Example 2 Ion plating was performed on the inner surface of a quartz boat for boat-method GaAs growth using the ion plating apparatus shown in FIG.

First, Si, which is an evaporation element, was heated and evaporated with an electron gun 5, and 02 was introduced through an oxygen introduction tube 6, and an ionization reaction was caused by high frequency plasma to produce a transparent amorphous thin film.

Next, increase the output of the electron gun 5 while keeping the pressure of 02 constant.
A Si-rich Si-OWA was fabricated by increasing the amount of Si vapor deposited.

Next, N2 is introduced from the nitrogen introduction tube 7 to cause an ionization reaction to produce a Si-0-N film.Furthermore, the introduction of 02 is stopped while N2 is introduced, and a 5t-N film (partially Si3
N4) was produced, and finally a BN film was produced.

As a result of growing GaAS crystals using the boat manufactured in this manner and the quartz reaction tube manufactured in Example 1, the contamination of Sl was reduced to 1/10 to 1/100 of the conventional amount, and A single crystal with a dislocation density of 10 3 /cm 2 similar to that of 10 3 /cm 2 was obtained.

Note that the number of evaporation sources is not limited to two, and multiple types of evaporation sources may be used to evaporate multi-component substances.

In particular, by using a member for growing a GaAs single crystal, a member on which a compound of group V elements other than Ga and hesium, and a multi-element substance of group V is used, the purity of the GaAs single crystal can be increased. It becomes possible.

[Effects of the Invention] As explained above, according to the present invention, the following excellent effects are exhibited.

It is possible to prevent Si from being mixed into n+ GaAs, and GaAs with high insulation resistance can be obtained efficiently.

(2) By forming an intermediate layer having a coefficient of thermal expansion intermediate between the quartz member and the outermost coating layer using the ion plating method, generation of cracks due to a difference in thermal expansion is prevented.

(3) Since the compound semiconductor single crystal manufacturing member of the present invention has a quartz member as its main body, it can be manufactured at low cost, and interface control can be easily performed during crystal growth, making it possible to obtain high-quality single crystals.

[Brief explanation of the drawing]

FIG. 1 is a configuration diagram of an ion plating apparatus for carrying out a method for manufacturing a member for manufacturing a compound semiconductor single crystal according to an embodiment of the present invention. In the figure, 2 is a high frequency coil, 3 and 4 are crucibles, 5 is an electron gun, 6 is an oxygen introduction tube, 7 is a nitrogen introduction tube, and 9 is a quartz reaction tube.

Claims (3)

[Claims] (1) BN, AlN or Al_2 on the surface of the quartz member
In a compound semiconductor single crystal manufacturing member provided with a coating layer made of O_3, the thermal expansion coefficient between the quartz member and the coating layer is the same as that of quartz and BN, Al, which forms the coating layer.
Si- with a value intermediate between N or Al_2O_3
1. A member for manufacturing a compound semiconductor single crystal, characterized in that an intermediate layer is formed of an O-B-N based material, a Si-O-Al-N based material, or a composite composition thereof. (2) On the surface of the quartz member, the thermal expansion coefficient is different from that of quartz and BN.
, AlN or Al_2O_3, after forming an intermediate layer consisting of a Si-O-B-n-based material, a Si-O-Al-N-based material, or a composite composition thereof by an ion plating method. , B on top of the intermediate layer
A method for manufacturing a member for manufacturing a compound semiconductor single crystal, characterized in that a coating layer made of N, AlN or Al_2O_3 is provided. (3) The manufacturing method according to claim 2, wherein the coating layer is formed by an ion plating method.