JPH0684277B2 - (III) -Group V compound semiconductor single crystal manufacturing method and apparatus thereof - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a III-V compound semiconductor single crystal manufacturing method and an apparatus thereof, and more particularly to a manufacturing method and an apparatus thereof by a reservoir system direct synthesis pulling method. .

[Prior Art] As a method for producing a single crystal of a group III-V compound semiconductor in which a group V element has a high vapor pressure, for example, a single crystal of InP, GaP, GaAs, etc., a group V element is accommodated and only one end thereof is contained. There is known a reservoir type direct synthetic pulling method using a container (hereinafter, referred to as a reservoir) in which the container is opened. When actually manufacturing a single crystal by this method, two methods are conceivable depending on whether the position of the reservoir is fixed or moved for the time of synthesizing the single crystal and the time of pulling.

FIG. 4 is a configuration diagram of a manufacturing apparatus for carrying out the direct synthetic pulling method by the reservoir fixing method in which the reservoir is fixed. An attempt was made to produce an InP single crystal using this production apparatus. In the figure, the left side of the IV-IV line shows the cross-sectional structure of the device at the time of synthesis, and the right side shows the sectional structure of the device at the time of pulling up. First, 2500 g of In42 is placed in a 6-inch (15.2 cm) size quartz crucible 41.
Contains 600 g of B ₂ O ₃ 43 as a liquid sealant, while reservoir 44
800g of red phosphorus 45 was accommodated inside. The reservoir 44 is fixed above the inside of the container 48 by a support rod 46 and a support plate 47. Before synthesizing, the tip of the injection tube 49 is B ₂ O ₃ in the crucible 41.
The crucible 41 is lowered by the operating rod 50 so as not to come into contact with 43.

Next, the inside of the crucible 41 is heated by the crucible heating heater 51 to dissolve In 42 and B ₂ O ₃ 43, and the pressure inside the container 48 is adjusted to Ar.
After controlling the gas to 40 kg / cm ² , raise the crucible 41 and
Insert the tip of 49 into In42. After that, the inside of the reservoir 44 was heated by the heater 52 for heating the reservoir, and the vapor of the red phosphorus 45 was injected into the In 42 for synthesis. At this time, In melt
The temperature of 42 was 1100 ° C.

When the red phosphorus 45 disappears from the reservoir 44,
As shown in the right side of the figure, the position of the crucible 41 was lowered, and heating by the reservoir heating heater 52 was stopped. Furthermore, the pulling shaft
The In crystal synthesized in the crucible 41 by descending the seed crystal 54 by 53
After contacting with the P melt 55, the seed crystal 54 was pulled up.

However, the temperature around the seed crystal 54 was too high, and the seed crystal 54
As a result, phosphorus was volatilized and the surface was roughened, so that the single crystal could not be pulled up.

This is because the position of the crucible 41 during combining and pulling changes as described above, so it is necessary to make the crucible heating heater 51 for heating the crucible 41 long.
Therefore, it is considered that the temperature environment suitable for pulling the single crystal could not be obtained.

On the other hand, fix the position of the crucible containing the group III element,
If a reservoir moving method of moving the reservoir containing the group element is adopted, it is not necessary to lengthen the crucible heating heater and a desired temperature environment can be obtained. However, if the reservoir is fixed to the pull-up shaft and moved by the pull-up shaft, the seeding work cannot be performed after the synthesis is completed, and a drive shaft for supporting the reservoir is newly provided in addition to the pull-up shaft. When the reservoir is moved by the lever drive shaft, the upper part of the device becomes a very complicated mechanism and the device itself becomes expensive.

[Problems to be Solved by the Invention] As described above, conventionally, it is impossible to optimize the temperature environment when pulling a single crystal by the fixed-reservoir method, and is it possible to carry out seeding work by the moving-reservoir method? Alternatively, there is a problem that the upper part of the device becomes complicated and the device becomes expensive.

Thus, the object of the present invention is to solve the above-mentioned problems of the prior art and to enable direct pulling of a synthetic single crystal with a simple structure II
An object of the present invention is to provide a method and an apparatus for manufacturing a group IV compound semiconductor single crystal.

[Means for Solving Problems] In the method for producing a III-V compound semiconductor single crystal according to the present invention, the III-V compound semiconductor single crystal is located above the crucible in the III element heated and melted in the crucible arranged in the pressure vessel. After introducing the vaporized Group V element vapor that has been heated and vaporized in the closed container to carry out the synthesis reaction, the closed container is allowed to stand up and the seed crystal carried on the tip of the pulling shaft is lowered from above the crucible. In the method for producing a III-V compound semiconductor single crystal in which the single crystal is pulled by bringing it into contact with the synthetic melt in the crucible and then raising the seed crystal, it is provided on the pulling shaft during the synthesis reaction. The closed container is supported by a locking member, and after the completion of the synthesis reaction, the pulling shaft is raised and the closed container is transferred from the locking member to a holding member provided above the crucible to wait. Characteristic, This is intended to achieve the above object.

According to this manufacturing method, a crucible for containing a heated and melted group III element is provided in a pressure vessel, and the crucible is provided so as to be able to move up and down and the group V element is heated and vaporized to form a melt II.
A closed container for introducing into the group I element to carry out the synthetic reaction, and a pulling shaft for supporting the seed crystal at the tip and pulling the single crystal by contacting the synthesized melt with the seed crystal. In a III-V compound semiconductor single crystal manufacturing apparatus equipped with
A locking member for supporting the closed container during the synthesis reaction is provided on the pulling shaft, and the closed container is moved up from the locking member by raising together with the pulling shaft after the completion of the synthesis reaction. This can be carried out by a III-V compound semiconductor single crystal manufacturing apparatus characterized in that a holding member for standing by is provided above the crucible.

[Operation] By using the manufacturing apparatus configured as described above, during synthesis, the closed vessel is lowered to introduce the vapor of the group V element into the crucible to synthesize with the group III element, and then by the elevating means. It is possible to pull up the single crystal by moving the closed container upward, making it stand by by the standby means, and further seeding by the elevating means.

Further, by using a pulling shaft having a locking member for locking the closed container as the elevating means, and a holding member positioned above the crucible and holding the closed container as the standby means when the closed container is raised, the pulling shaft can be used. It is possible to raise / lower the closed container, stand by above, and seed / pull up only by the operation of, and the upper part of the device becomes a very simple mechanism.

Further, since the position of the crucible is fixed during the synthesis and the pulling, it is not necessary to lengthen the crucible heating heater, and a desired temperature environment can be formed when pulling the single crystal.

EXAMPLES Examples of the present invention will be described below with reference to the accompanying drawings.

FIG. 1 is a configuration diagram of a III-V group compound semiconductor single crystal manufacturing apparatus according to an embodiment of the present invention, in which the left side of the line I-I in the drawing is for synthesis and the right side is for pulling up. A cross-sectional configuration is shown. The crucible 1 has a size of 6 inches (15.2 cm), is made of quartz, and is held by a crucible susceptor 3 installed at the bottom of the pressure vessel 2. A crucible heating heater 4 is provided on the outer peripheral portions of the crucible 1 and the crucible susceptor 3 so as to surround them. Further, a greenhouse 5 containing the crucible 1, the susceptor 3 for the crucible and the heater 4 for heating the crucible and having an upper opening is formed from a heat insulating material. On the other hand, a pull-up shaft 6 is inserted into the pressure container 2 from above the pressure container 2, and a reservoir susceptor 7 is provided rotatably around the pull-up shaft 6 and vertically movable along the pull-up shaft 6. Has been. The reservoir susceptor 7 has three receiving portions 8 around the pull-up shaft 6 as shown in FIGS.
And each of them holds a reservoir 9. Further, a locking member 10 having three radial arms is provided on the lower side of the pulling shaft 6, and the arms of the locking member 10 are received by the reservoir susceptor 7 as shown in FIG. The reservoir susceptor 7 can be supported by the pull-up shaft 6 by being positioned below the portion 8. A cylindrical holding member 11 that surrounds the reservoir susceptor 7 when the reservoir susceptor 7 descends is provided on the upper part of the greenhouse 5 and the receiving portion when the reservoir susceptor 7 rises is provided on the inner peripheral portion of the holding member 11. Three convex portions 12 for locking and holding 8 are formed. Further, a reservoir heating heater 13 is arranged on the outer peripheral portion of the holding member 11 so as to surround the holding member 11. Further, each reservoir 9 is provided with an injection pipe 14 extending downward to inject the vapor of the V group element contained therein into the crucible 1.

Next, a method of manufacturing an InP single crystal using such a manufacturing apparatus will be described.

First, 2500 g of In15 was added to the crucible 1 and B ₂ O was used as a liquid sealant.
₃ 16 600g housed, in contrast the reservoir 9 to the red phosphorus 17 meter 800g accommodated. The tip of the injection tube 14 is located inside the crucible 1.
The reservoir susceptor 7 is locked onto the convex portion 12 of the holding member 11 by the pull-up shaft 6 so as not to contact the B ₂ O ₃ 16. A seed crystal 18 is attached to the lower end of the pulling shaft 6.

Next, the crucible 1 is heated by the crucible heater 4 to melt In 15 and B ₂ O ₃ 16 and the pressure in the pressure vessel ² is controlled to 40 kg / cm ^{2 of} Ar gas. Thereafter, while keeping the arm of the locking member 10 engaged with the lower portion of the receiving portion 8 of the reservoir susceptor 7, the pull-up shaft 6 is slightly raised to separate the reservoir susceptor 7 from the convex portion 12 of the holding member 11. As shown in FIG. 2, the pull-up shaft 6 is rotated so that the receiving portion 8 does not come into contact with the convex portion 12 of the holding member 11, and then the pull-up shaft 6 is lowered to move the injection pipe 14
The pulling shaft 6 is held when the tip of is inserted into the In melt 15 in the crucible 1. Then, the inside of the reservoir 9 is heated by the heater 13 for heating the reservoir to vaporize the red phosphorus 17, and the vapor is injected into the In melt 15 through the injection pipe 14 to perform synthesis (left side in FIG. 1). The temperature of the In melt 15 at this time is set to 1100 ° C.

In this way, when all the red phosphorus 17 in the reservoir 9 is injected into the In melt 15, the pull-up shaft 6 is pulled up to raise the susceptor 7 for the reservoir, and this is rotated above the holding member 11. Then, the receiving portion 8 of the reservoir susceptor 7 is a holding member.
After being positioned directly above the convex portion 12 of 11, the pull-up shaft 6 is lowered to hold the reservoir susceptor 7 as shown in FIG.
To hold. Further, only the pull-up shaft 6 is slightly lowered, and then the pull-up shaft 6 and the crucible 1 are rotated around the line I-I at a predetermined rotation speed. Then, the pulling shaft 6 is further lowered, and the seed crystal 18 attached to the lower end of the pulling shaft 6 is brought into contact with the synthetic melt 19 in the crucible 1 for seeding (right side in FIG. 1), and then the pulling shaft 6 To raise the InP single crystal.

The InP single crystal was produced by the above method under the following conditions: growth direction <111>, seed crystal rotation speed 3 rpm, crucible rotation speed 5 rpm, and pulling speed 10 mm / h. Maximum diameter 80mm, weight 2k without crystal roughening
A single crystal with g and length of 160 mm could be pulled up.

When a wafer was formed by slicing this InP single crystal and the crystal characteristics were evaluated, the hole measurement result by the Van der Pauw method was n = 4 to 8 × 10 ¹⁵ cm ⁻³ , μ = 4100 to 4400c
m ² / v · sec, and EPD measurement results show an average value of 4 × 10 ⁴ cm ^-2 and a maximum value of 8 × 10 ⁴ cm ^-2, and it has excellent properties that are unparalleled as undoped InP single crystals. confirmed.

Note that the present invention is not limited to InP and other II such as GaP and GaAs.
It goes without saying that it can be applied to the production of a single crystal of a IV compound semiconductor.

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

(1) Since the position of the crucible is fixed, it is not necessary to lengthen the heater for heating the crucible, the temperature of the crucible can be easily controlled, and an optimum temperature environment can be formed when pulling the single crystal.

(2) As a result, it is possible to manufacture a single crystal of extremely excellent quality.

(3) Since the operation of raising and lowering the reservoir (closed container), waiting at the upper side, and seeding / pulling up can be performed with only one pulling shaft, the mechanism of the device, especially the mechanism of the upper part of the device becomes simple, Therefore, the manufacturing cost of the device can be reduced.

[Brief description of drawings]

FIG. 1 is a sectional view of a III-V compound semiconductor single crystal manufacturing apparatus according to an embodiment of the present invention at the time of synthesis and pulling, and FIGS. 2 and 3 respectively explain the manufacturing method of the present invention. FIG. 4 is a cross-sectional configuration diagram of a manufacturing apparatus for carrying out a direct synthetic pulling-up method using a reservoir fixing method at the time of synthesis and pulling up. In the figure, 1 is a crucible, 2 is a pressure vessel, 4 is a heater for heating the crucible, 6 is a pulling shaft, 9 is a reservoir, 10 is a locking member, 11 is a holding member, 13 is a reservoir heating heater, and 15 is In. , 17 is red phosphorus, and 18 is a seed crystal.

Claims (4)

[Claims] 1. A synthetic reaction in which a group V element heated and melted in a crucible arranged in a pressure vessel is introduced with a group V element vapor heated and vaporized in a closed vessel located above the crucible. After performing the above, the closed container is raised and waited and the seed crystal carried on the tip of the pulling shaft is lowered from above the crucible to bring it into contact with the synthetic melt in the crucible, and then the seed crystal is Raise and pull single crystal II
In the IV compound semiconductor single crystal manufacturing method, the closed container is supported by a locking member provided on the pull-up shaft during the synthesis reaction, and the pull-up shaft is raised after completion of the synthesis reaction and the crucible A method for producing a III-V compound semiconductor single crystal, characterized in that the hermetically sealed container is transferred from the locking member to a holding member provided above, and is made to stand by. 2. A crucible for containing a heated and melted Group III element in a pressure vessel, and a crucible which is vertically movable and which heats and vaporizes a Group V element and introduces it into the molten Group III element. III-V equipped with a closed container for carrying out the synthetic reaction and carrying a seed crystal at the tip and for pulling a single crystal by bringing the synthesized melt into contact with the seed crystal In the compound semiconductor single crystal manufacturing apparatus, a locking member for supporting the closed container during the synthesis reaction is provided on the pull-up shaft, and the locking member is raised together with the pull-up shaft after the completion of the synthesis reaction. An apparatus for producing a III-V compound semiconductor single crystal, characterized in that a holding member for waiting the closed container transferred from the above is provided above the crucible. 3. A susceptor having a plurality of receiving portions at predetermined intervals around the pulling shaft is rotatably provided, and each of the receiving portions of the susceptor holds a plurality of the closed containers. III according to claim 2
-V compound semiconductor single crystal manufacturing apparatus. 4. The holding member comprises a cylindrical body having an inner wall surface provided with projections of the same number as the receiving portions of the susceptor at predetermined intervals, and each receiving portion of the susceptor has a predetermined rotation angle of the pulling shaft. The apparatus for producing a III-V compound semiconductor single crystal according to claim 3, characterized in that the apparatus is held by the convex portion of the holding member only in.