JP2937000B2 - Method for manufacturing compound semiconductor single crystal and PBN container used for manufacturing compound semiconductor single crystal - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a compound semiconductor single crystal and a container made of PBN (Pyrolitic Boron Nitride: pyrolytic boron nitride) used for producing the compound semiconductor single crystal.

[0002]

2. Description of the Related Art A conventional method for producing a compound semiconductor single crystal is described below.
An example of a method for manufacturing gallium arsenide (hereinafter referred to as GaAs) crystals, which has been conducted on the largest scale in both research and development, will be described.

FIG. 1 is a schematic side sectional view of a crystal pulling apparatus widely used as a GaAs single crystal manufacturing apparatus. In the figure, reference numeral 1 denotes a high-temperature furnace (pressure-resistant vessel) for crystal growth, into which a lower shaft 2 is inserted from below, and a susceptor 4 is supported at the tip of the lower shaft 2 via a pedestal 3. Have been. A PBN container (crucible) 5 is arranged in the susceptor 4. A heater 8 is provided around the susceptor 4.
The container 5 can be heated from the surroundings. The lower shaft 2 is connected to a rotation mechanism (not shown) and is rotated at a constant rotation speed. An upper shaft 9 is inserted coaxially with the lower shaft 2 from the upper side of the container 1, and a seed crystal 11 having a desired orientation is placed in a seed crystal holder 10 provided at the lower end thereof (usually (100) as the orientation). Is used)
Is attached. The upper shaft 9 is rotated by a rotating / elevating mechanism (not shown) in a direction opposite to that of the PBN container 5 and is moved up and down. A weight sensor 12 is provided in the middle of the upper shaft 9 so that the weight of the crystal during the growth process can be detected.

At the time of crystal growth, first, a PBN vessel 5
14,000 g of the GaAs polycrystalline raw material 6 and 4,000 g of the B ₂ O ₃ liquid sealing agent 7 are evacuated, and the inside of the high-temperature furnace 1 is evacuated to a vacuum of about 40 atm. The main heater 8 is energized to increase the temperature inside the PBN container 5. Liquid sealant (B ₂ O ₃ ) 7 at around 500 ° C
Softens and melts to cover the GaAs polycrystalline raw material 6. Subsequently, the temperature is increased to make the temperature inside the PBN vessel 5 1,238 ° C. or higher, and the polycrystalline raw material 6 is melted. Next, after the pressure in the high-temperature furnace 1 is reduced to 5 to 20 atm, the seed crystal 11 is lowered, and its tip is immersed in a raw material melt to perform seeding. Then, while lowering the temperature of the main heater 8, the upper shaft 9 is pulled up at a speed of 9 to 12 mm / hr, and while detecting the crystal weight by the weight sensor 12, the output of the main heater is controlled to remove the GaAs single crystal. Let it grow.

[0005]

However, even if a compound semiconductor single crystal is pulled by an automated apparatus as described above, a good single crystal is not always obtained every time. Defects occur. In particular, when obtaining a long crystal having a length exceeding 200 mm, or when the crystal diameter is φ
In the case of obtaining a large-diameter crystal exceeding 4 inches in size, it is extremely difficult to obtain crystal growth conditions with good reproducibility. It was rare that a single crystal was obtained over the entire region from the seeding portion (seed portion) to the crystal growth termination portion (tail portion).

Although not shown in FIG. 1, the high-temperature furnace 1 has a member such as a heat shield tube (called a hot zone, hereinafter H).
Until recently, the arrangement, shape, material, and the like of the HZ were considered to be factors affecting the reproducibility of the growth conditions of the compound semiconductor single crystal. However, with the stabilization of conditions such as the arrangement, shape, and material of HZ,
The cause is not only HZ, but the PBN used
It has become clear that the characteristics of the container are also significantly related. The PBN container does not react with the raw material compound even at high temperatures at which the compound semiconductor single crystal grows, and the Pyrolitic Boro
n Nitride itself has high purity and other advantages,
It is an indispensable tool for the growth of As single crystal, and its substitute is not yet known. Therefore, in order to improve the reproducibility of the growth conditions of the compound semiconductor single crystal and improve the yield, it is essential to improve the characteristics of the PBN container. However, it was not clear what was the most decisive factor in the characteristics of the PBN container.

Another method for manufacturing a compound semiconductor single crystal is a temperature gradient method. According to this method, a temperature region above the melting point of the crystal (melting region) and a temperature region below the melting point (solidification region) are formed in the high-temperature furnace, and a predetermined temperature gradient exists between the melting region and the solidification region. After forming a region (temperature gradient region) and melting the polycrystalline raw material in the PBN container in the melting region, the PBN container is moved through the temperature gradient region to the solidification region side, whereby the temperature gradient is increased. This is a method in which a raw material melt is solidified from the seed crystal side provided at one end of the region container to grow a single crystal, and a compound semiconductor single crystal having fewer defects than the pulling method can be obtained. However, the PB used in this method
There is a problem that the yield of the compound semiconductor single crystal varies depending on the N container, and the compound semiconductor single crystal cannot be obtained with good reproducibility.

An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a method for producing a compound semiconductor single crystal capable of obtaining a compound semiconductor single crystal with good reproducibility, and a PBN used for producing a compound semiconductor single crystal. It is an object of the present invention to provide a container made of a resin.

[0009]

The method of manufacturing a compound semiconductor single crystal according to the present invention is roughly classified into a method belonging to a so-called pulling method and a method belonging to a so-called temperature gradient method.

[0010] The former is a P type containing a raw material melt in a high-temperature furnace.
It is assumed that a BN container is placed and a single crystal is grown by relatively moving the seed crystal and the PBN container while bringing the seed crystal into contact with the raw material melt. The methods can be classified into the following first to fifth methods.

The first method is as follows (1) , (2),
Use a PBN container that satisfies the conditions (3) and (4) at the same time.

The second method uses a PBN container that satisfies the following conditions (5) and (6) simultaneously.

The latter is a P type in which a raw material melt is contained in a high-temperature furnace.
Arranging a BN container and forming a region of a predetermined temperature gradient from a temperature equal to or higher than the melting point of the crystal to a temperature equal to or lower than the melting point,
Move the area relative to the container to
The method is based on a method of growing a single crystal from the side of the seed crystal housed at the lower end, and uses a PBN container that satisfies the following conditions (1) and (2) simultaneously.

(1) The density of the PBN container is in the range of 1.85 g / cm ^{3 to} 2.05 g / cm ³ over the entire area.

(2) X-ray diffraction integrated intensity ratio of the (002) plane and the (100) plane measured on a plane perpendicular to the thickness direction of the PBN plate constituting the PBN container: ΔI (002) / I ( 100) The value of 、
It is in the range of 8 to 30 over the entire area.

(3) The density of the PBN container gradually increases from the bottom to the opening.

(4) The (002) plane and the (10) plane measured on a plane perpendicular to the thickness direction of the PBN plate constituting the PBN container.
The value of the X-ray diffraction integral intensity ratio of the (0) plane: {I (002) / I (100)} gradually increases from the bottom to the opening.

(5) The value of the thermal conductivity measured on a plane perpendicular to the thickness direction of the PBN plate constituting the PBN container is in the range of 50 W / mK to 200 W / mK over the entire region.

(6) The value of the thermal conductivity measured on the plane perpendicular to the thickness direction of the PBN plate constituting the PBN container gradually increases from the bottom to the opening.

[0020]

There is an approximately constant relationship between the density of the PBN plate and the X-ray diffraction integral intensity ratio measured on a plane perpendicular to the thickness direction. The lower the density, the more the measurement is on the plane perpendicular to the thickness direction. The X-ray diffraction integral intensity ratio also tends to decrease. Further, in the PBN container, the density and the X-ray diffraction integrated intensity ratio are not constant from the bottom to the opening.
Variations occur in the N container. Regarding the characteristics of the PBN container, the most crucial factor for obtaining a compound semiconductor single crystal with good reproducibility is considered to be basically the problem of heat flow. Although it is the main line, it is not always easy to measure the thermal conductivity and the like.
Based on such knowledge , the former first and second methods and the latter method use the characteristics of the PBN container in terms of density and X-ray diffraction integral intensity ratio that are easy to measure and related to thermal conductivity and the like. Prescribe,
This is a method of growing a compound semiconductor single crystal using a PBN container having predetermined characteristics with respect to the density and the X-ray diffraction integrated intensity ratio .

The conditions (1) and (2) in the former first method and the latter method are as follows:
It is based on the finding that when only a line diffraction integral intensity ratio is considered, the reproducibility of a compound semiconductor single crystal is highest when a PBN container that satisfies these two conditions is used at the same time. That is, the density is 1.85g /
If more cm ³ of larger than the small or 2.05 g / cm ^3, the above X
The reproducibility of the compound semiconductor single crystal obtained is low regardless of the X-ray diffraction integrated intensity ratio, and a good compound semiconductor single crystal is obtained regardless of the density even when the X-ray diffraction integrated intensity ratio is smaller than 8 or larger than 30. Low reproducibility.

In the first method, (3) and
The condition (4) is obtained by further adding two conditions relating to the distribution of the density and the X-ray diffraction integrated intensity ratio from the bottom to the opening of the container. That is, the lifting method
Even when (1) and (2) are simultaneously satisfied in the above, when the condition that the density and the X-ray diffraction integrated intensity ratio gradually increase from the bottom to the opening is not satisfied, these conditions were satisfied. The reproducibility of obtaining a good compound semiconductor single crystal is lower than when a PBN container having characteristics is used.

The condition (5) in the second method is that when only the thermal conductivity of the whole container is considered,
This is because the reproducibility of obtaining a compound semiconductor single crystal is highest when the growth is carried out using a PBN container satisfying this condition. That is, when a PBN container having a thermal conductivity of less than 50 W / mK was used, the reproducibility of obtaining a compound semiconductor single crystal was low, and a PBN container having a thermal conductivity of more than 200 W / mK was used. Also in this case, the reproducibility of obtaining a good compound semiconductor single crystal is low.

The condition (6) in the second method
Is a further plus the condition of the distribution of the thermal conductivity of toward the opening from the bottom of the container. That is, even when the thermal conductivity satisfies the condition of 50 W / mK to 200 W / mK, a good compound semiconductor single crystal can be obtained when the condition that the thermal conductivity gradually increases from the container bottom to the opening is satisfied. The reproducibility obtained is the highest.

The measurement conditions for determining the X-ray diffraction integrated intensity of the PBN plate constituting the PBN container are as follows.

Measurement conditions X-ray source: Cu Ka line Voltage / current: 40 KV / 30 mA Slit: DSI, RS0.3, SSI Scan speed: 1 ° / min Scan width (2θ): (002) 24 ° to 28 ° ° (100) 40 ° to 50 °

[0027]

EXAMPLES Next, examples of the method for producing a compound semiconductor single crystal of the present invention will be described.

Example 1 An example in which the method of the present invention is applied to the production of a GaAs single crystal by the pulling method will be described. The overall configuration of the manufacturing apparatus used in the following Examples 1-1 to 1-5 is the same as that in FIG.

[0029] [Example 1-1] distribution range of the density of the entire container is ^{1.87g / cm 3 ~2.00g / cm 3} , the X-ray diffraction integrated intensity ratio measured with a plane perpendicular to the thickness direction 14 Using a PBN container with a diameter of 9 inches and a characteristic of 20
A crystal growth of 300 mm in crystal length of φ3 inch size of s crystal
I went 10 times. As a result, from the seed part to the tail part of the crystal, 10 single crystals in the entire region (hereinafter referred to as All Single) were obtained. In the result of the other one, about 80% of the entire crystal length was a single crystal. Further, another P9 container of φ9 inch size having a density of 1.85 g / cm ^{3 to} 2.05 g / cm ³ and a characteristic of the X-ray diffraction integral intensity of 8 to 30 was used.
Crystal growth of an inch size and a crystal length of 300 mm was performed 100 times. As a result, All Single was obtained with a probability of 90% or more. The high probability of 90% or more was the same when a PBN container other than the φ9 inch size was used and when the φ3 inch size crystal was grown.

Comparative Example 1-1-1 Crystal growth was performed under the same conditions as in Example 1 except that a PBN container having a lower limit of the distribution range of the density of the entire container smaller than 1.85 g / cm ³ was used. As a result, regardless of the X-ray diffraction integral intensity ratio, All Single
Was less than 60% of the time.

Comparative Example 1-1-2 Crystal growth was performed under the same conditions as in Example 1 except that a PBN container having an upper limit of the distribution range of the density of the entire container larger than 2.05 g / cm ³ was used. As a result, regardless of the X-ray diffraction integral intensity ratio, All Single
Was less than 40%.

[Comparative Example 1-1-3] A crystal was grown under the same conditions as in Example 1 except that a PBN container having a lower limit of the distribution range of the X-ray diffraction integrated intensity ratio smaller than 8 was used. As a result, the probability of All Single was 50% or less regardless of the density of the PBN container.

Comparative Example 1-1-4 Crystal growth was performed under the same conditions as in Example 1 except that a container made of PBN was used, in which the upper limit of the distribution range of the X-ray diffraction integrated intensity ratio was larger than 30. As a result, the probability of All Single was 40% or less regardless of the density of the PBN container.

Example 1-1 and Comparative Example 1-1-1
Taken together, the results of ～1-1-4, density of 1.85g / cm ³ ~
2.05 g / cm ³ , and the X-ray diffraction integrated intensity ratio is 8
When crystal growth is performed using a PBN container having a range of ~ 30, the probability of obtaining All Single is 90% or more,
It can be seen that the reproducibility of obtaining a GaAs single crystal is greatly improved.

Example 1-2 The density of the whole container and the X-ray diffraction integrated intensity ratio were 1.87 g / cm ^3-, respectively, as in Example 1.
2.00 g / cm ³ , in the range of 14 to 20 and a PBN container of φ9 inch size satisfying the condition that the density and the X-ray diffraction integrated intensity ratio gradually increase from the bottom to the opening. A GaAs crystal having a diameter of 3 inches and a crystal length of 300 mm was grown 10 times. As a result, All
All 10 Singles were obtained. Further, the X-ray diffraction integral intensity ratio is in the range of 8 to 30, and the density is 1.85 g / cm ^{3 to} 2.05 g / cm ³
Using another φ9 inch PBN container satisfying the condition that the X-ray diffraction integrated intensity ratio and the density gradually increase from the bottom toward the opening,
As crystal of φ3 inch size, crystal length 300mm, crystal growth of 10
As a result of performing 0 times, All Single was obtained with a probability of 95% or more. The high probability of 95% or more was the same even when a PBN container having a size other than φ9 inches was used and when a crystal having a size other than φ3 inches was grown.

[Comparative Example 1-2-1] Crystal growth was carried out in the same manner as in Example 1-2, using a PBN container having a PBN plate density of less than 1.85 g / cm ³ constituting the PBN container. As a result, regardless of the X-ray diffraction integral intensity ratio, All Single
Was less than 60% of the time.

Comparative Example 1-2-2 Crystal growth was carried out in the same manner as in Example 1-2, using a PBN container having a PBN plate density of more than 2.05 g / cm ³ constituting the PBN container. As a result, regardless of the X-ray diffraction integral intensity ratio, All Single
Was less than 40%.

Comparative Example 1-2-3 Crystal growth was carried out in the same manner as in Example 1-2, using a PBN container having the X-ray diffraction integrated intensity ratio of less than 8 of the PBN plate constituting the PBN container. As a result, regardless of density, the probability of All Single is
It was less than 50%.

Comparative Example 1-2-4 Crystal growth was carried out in the same manner as in Example 1-2 using a PBN container having a ratio of X-ray diffraction integrated intensity of 30 or more of the PBN plate constituting the PBN container. As a result, regardless of density, the probability of All Single is 40
% Or less.

Comparative Example 1-2-5 The ratio of the integrated X-ray diffraction intensity of the PBN plate constituting the container made of PBN was in the range of 8 to 30, and the density was 1.85 g / cm ^{3 to} 2.05 g /. Crystal growth was carried out in the same manner as in Example 1-2, using a PBN container in the range of cm ³ , where the X-ray diffraction integrated intensity ratio did not gradually increase from the bottom to the opening of the container. Result, PBN
The probability of All Single is 80 irrespective of the density distribution in the container.
% Or less.

Comparative Example 1-2-6 The XBN diffraction integral intensity ratio of the PBN plate constituting the PBN container is in the range of 8 to 30, and the density is 1.85 g / cm ^{3 to} 2.05 g /. The crystal growth was performed in the same manner as in Example 1-2 using a PBN container whose density was in the range of cm ³ but the density did not gradually increase from the bottom to the opening of the container. Regardless of the distribution of the X-ray diffraction integral intensity ratio, the probability of All Single was 85% or less.

Example 1-2 and Comparative Example 1-2-1
Taken together the results of ～1-2-6, density is 1.85g / cm ³ ~2.05g / cm ³ range over the vessel throughout the value of density gradually increases toward the opening from the bottom of the container Yes,
And the value of the X-ray diffraction integral intensity ratio of the PBN plate constituting the PBN container is in the range of 8 to 30 over the entire region of the container,
When a PBN container having such characteristics that its value gradually increases from the bottom to the opening of the container is used, the reproducibility of obtaining a compound semiconductor single crystal can be greatly improved.

Example 1-3 The density of the PBN plate forming the side wall of the PBN container was 1.98 g / cm ³ , and the value of the X-ray diffraction integrated intensity ratio of the PBN plate forming the side wall of the PBN container was Using 21 PBN containers, the other conditions were the same as before, and the GaAs crystal was 3 inches in size and 300 m in length.
The crystal growth of m was performed 10 times. As a result, eight All Single crystals were obtained. About 85% of the remaining two were single crystals.

Comparative Example 1-3-1 The density of the PBN plate constituting the side wall of the PBN container is higher than 2.05 g / cm ^3.
As a result of crystal growth using a BN container under the same conditions as in Example 1-3, the crystallization ratio (yield) was 60% or less regardless of the value of the X-ray diffraction integrated intensity ratio. there were.

Comparative Example 1-3-2 The density of the PBN plate constituting the side wall of the PBN container is 2.05 g / cm ³ or less,
As a result of crystal growth using a PBN container having a value of the X-ray diffraction integrated intensity ratio smaller than 20 and the other conditions being the same as in Example 1-3, the crystallization ratio (yield) was 80% or less. Met.

The above Examples 1-3 and Comparative Examples 1-3
The graph of FIG. 2 is obtained based on the results of 1, 1-3-2 and the like. That is, curves such as L1 and L2 are drawn depending on the CVD conditions of the PBN plate constituting the side wall of the PBN container. The conventional method is close to the L1 curve, in which case only the B region (Comparative Example 1-3-1) and the C region (Comparative Example 1-3-2) can be obtained, and the yield is up to about 80%. . In contrast, when a PBN container having the characteristics of the A region is used,
A dramatic improvement in yield of over 90% was observed.

Example 1-4 A thermal conductivity value measured in a plane direction perpendicular to a thickness direction of a PBN plate constituting a PBN container has a characteristic of 60 W / mK to 90 W / mK over the entire region of the container. A GaAs crystal with a diameter of 3 mm and a crystal length of 300 mm was grown 10 times using a PBN container having a diameter of 9 inches and satisfying the same conditions as in the conventional case. As a result, Al
All 10 single crystals were obtained. In addition, another φ9 having a thermal conductivity value of 50 W / mK to 200 W / mK.
Using an inch-sized PBN container, the φ of GaAs crystal
As a result of 100 times of crystal growth of 300 mm in length and 3 inches in size, all single crystals were obtained with a probability of 90% or more. The high probability of 90% or more was the same even when a PBN container having a size other than φ9 inches was used and when a crystal having a size other than φ3 inches was grown.

[Comparative Example 1-4-1] The PBN plate constituting the side wall of the PBN container uses a PBN container having a characteristic in which the value of the thermal conductivity is less than 50 W / mK. As a result of performing crystal growth in the same manner as in Example 1-4, Al
The probability of l Single was less than 60%.

[Comparative Example 1-4-2] The PBN plate constituting the side wall of the PBN container had a thermal conductivity value of more than 200 W / mK. As a result of performing crystal growth in the same manner as in Example 1-4,
The probability of All Single was less than 40%.

When the results of Example 1-4, Comparative Examples 1-4-1 and 1-4-2 are combined, the value of the thermal conductivity of the PBN plate constituting the side wall of the PBN container is 50 W / mK ~ 200W
When a PBN container satisfying / mK is used, the reproducibility of obtaining a compound semiconductor single crystal can be greatly improved.

Example 1-5 The value of the thermal conductivity of the PBN plate constituting the side wall of the PBN container is 60 W / mK to 90 W / mK as in Example 1-4, and the value is the container. A 9-inch PBN container that satisfies the characteristics of gradually increasing from the bottom to the opening is used.
Crystal growth of 0 mm was performed 10 times. As a result, all 10 All Single crystals were obtained. Also, the value of thermal conductivity is
A 9 inch PBN container satisfying the characteristics of 50 W / mK to 200 W / mK and the value gradually increases from the bottom to the opening of the container is used. As a result of performing the crystal growth 100 times, All Single crystals were obtained with a probability of 90% or more. The high probability of 90% or more was the same even when a PBN container having a size other than φ9 inches was used and when a crystal having a size other than φ3 inches was grown.

[Comparative Example 1-5-1] The PBN plate constituting the side wall of the PBN container uses a PBN container having a characteristic that the value of the thermal conductivity is less than 50 W / mK. As a result of performing crystal growth in the same manner as in Example 1-5, Al
The probability of l Single was less than 60%.

[Comparative Example 1-5-2] The PBN plate constituting the side wall of the PBN container had a thermal conductivity value of more than 200 W / mK. As a result of performing crystal growth in the same manner as in Example 1-5,
The probability of All Single was less than 40%.

[Comparative Example 1-5-3] The value of the thermal conductivity of the PBN plate constituting the side wall of the PBN container was 50 W / mK to 20 W / mK.
0 W / mK, but using a PBN container whose value does not satisfy the characteristic of gradually increasing from the bottom to the opening of the container, and using other conditions as in Example 1-5 for crystal growth. As a result, the probability of All Single was 80% or less.

The above Examples 1-5 and Comparative Examples 1-5
When the results of 1-1-5-3 are combined, the value of the thermal conductivity of the PBN plate constituting the side wall of the PBN container is from 50 W / mK to 20 W / mK.
PB that satisfies the condition that it is 0 W / mK and the value gradually increases from the bottom to the opening of the container.
When an N container is used, the reproducibility of obtaining a compound semiconductor single crystal can be greatly improved.

Example 2 An example in which the method of the present invention is applied to the production of a GaAs single crystal by the temperature gradient method will be described. As shown in FIG. 3, the PBN container used here has an inverted conical part 15 formed at the lower end of a cylindrical straight body part 14 and a bottomed cylindrical body at the lower end of the inverted conical part 15. The seed crystal accommodating section 16 is formed. The diameter of the straight body 14 is 52 mm , the height is 200 mm ,
The angle of inclination of the inverted conical part is 45 °, and the diameter of the seed crystal part is 10 mm . As shown in FIG. 1A, after a GaAs seed crystal 17 is mounted in a seed crystal accommodating portion 16 in a PBN container 13, 1000 g of a GaAs polycrystalline raw material 18 and a B ₂ O ₃ liquid sealant 19 are provided. Were sequentially charged in an amount of 100 g. P containing this crystal raw material
The BN container 13 is placed in a high-temperature furnace (temperature gradient furnace) (not shown) to melt the GaAs polycrystalline raw material 18 and the B ₂ O ₃ liquid sealant 19, as shown in FIG. Liquid 2
0 and the liquid sealant layer 21. Next, Ga is placed in a high-temperature furnace.
A region of a predetermined temperature gradient from a temperature higher than the melting point of As to a temperature lower than the melting point of As is formed, a temperature gradient of 30 deg / min is set, and the PBN container 13 is lowered at a speed of 5 mm / hr to perform crystal growth. went.

Example 2-1 The distribution range of the density of the entire container was 1.87 g / cm ^{3 to} 2.00 g / cm ³ , and the X-ray diffraction integral intensity ratio measured on a plane perpendicular to the thickness direction was as follows. Crystal growth was performed 10 times by the above method using a PBN container satisfying the characteristics of 14 to 20. As a result, all 10 All Singles were obtained from the seed part to the tail part. Further, using another PBN container satisfying the characteristics that the distribution range of the density of the whole container is 1.85 g / cm ^{3 to} 2.05 g / cm ³ , and the distribution range of the X-ray diffraction integral intensity ratio is 8 to 30, Crystal growth of 100 by the above method
As a result, All Single was obtained with a probability of 95% or more.

[Comparative Example 2-1-1] P constituting container
The lower limit of the distribution range of BN density is less than 1.85 g / cm ³ P
Crystal growth was performed using a BN container under the same conditions as in Example 2-1 except for the above. As a result, the probability of All Single was 60% or less regardless of the X-ray diffraction integrated intensity ratio.

[Comparative Example 2-1-2] P constituting container
The upper limit of the distribution range of BN density is greater than 2.05 g / cm ³
Crystal growth was performed using a BN container under the same conditions as in Example 2-1 except for the above. As a result, the probability of All Single was 40% or less regardless of the X-ray diffraction integrated intensity ratio.

[Comparative Example 2-1-3] A PBN container having a lower limit of the distribution range of the X-ray diffraction integrated intensity ratio smaller than 8 was used, and the crystal growth was carried out under the same conditions as in Example 2-1. As a result, regardless of the density of the PBN container, All Single
Was less than 50%.

Comparative Example 2-1-4 Crystal growth was performed under the same conditions as in Example 1 except that a PBN container having an upper limit of the distribution range of the X-ray diffraction integrated intensity ratio larger than 30 was used. As a result, the probability of All Single was 40% or less regardless of the density of the PBN container.

Example 2-1 and Comparative Example 2-1-1
Taken together the results of ～2-1-4, in the range of 1.85g / cm ³ ~2.05g / cm ³ distribution range of density over the entire container, the distribution range of the X-ray diffraction析積component intensity ratio container 8 ~
When crystal growth is performed using a PBN container that satisfies the condition of 30, the probability of obtaining All Single is 95% or more, and the reproducibility of obtaining GaAs single crystal is greatly improved. Recognize.

In the second embodiment, Ga is placed in a high-temperature furnace.
A region having a predetermined temperature gradient from a temperature above the melting point of As to a temperature below the melting point of As is formed.
Of the temperature gradient method of growing the crystal by relatively moving the PBN container 13 into which the PBN container 13 is filled. However, the method and the PBN container according to the present invention have a melting point higher than the melting point of GaAs in the high-temperature furnace. A PBN container that forms a temperature distribution having a peak temperature and contains a polycrystalline raw material is disposed, and the polycrystalline raw material in the PBN container is moved while moving the peak temperature position with respect to the PBN container. It is also applicable to a so-called zone melting method (zone melting method) in which a single crystal is grown by melting and solidifying from the seed crystal side.

In the first and second embodiments, the GaAs
Although the method for producing s single crystal growth has been described, the method for producing a compound semiconductor single crystal of the present invention is based on InP, GaP, and InA.
Similar effects can be obtained by applying the present invention to the production of other compound semiconductor single crystals such as s.

[0065]

(1) According to the method of claim 1 , P
The density of the BN container is 1.85 g / cm ^{3 to} 2.05 g / cm
³ , the density of which is gradually increasing from the bottom to the opening.
The (002) plane and the (100) plane measured on the plane perpendicular to the thickness direction of the N plate
X-ray diffraction integrated intensity ratio of the surface: The value of {I (002) / I (100)} is in the range of 8 to 30 over the entire region, and the value of the X-ray diffraction integrated intensity ratio is from the bottom to the opening. argument of the compound semiconductor single crystal by using a PBN made container gradually increases toward
By performing the growth, the reproducibility of obtaining a long crystal and a large-diameter crystal of the compound semiconductor single crystal can be greatly improved.

(2) According to the method of claim 2 , PB
The value of the thermal conductivity measured on a plane perpendicular to the thickness direction of the PBN plate constituting the N container is in the range of 50 W / mK to 200 W / mK over the entire region, and the PBN plate constituting the PBN container is The value of the thermal conductivity measured on a plane perpendicular to the thickness direction is gradually increased from the bottom to the opening, and the compound semiconductor single crystal is pulled and grown using a PBN container.
The reproducibility of obtaining a long crystal and a large diameter crystal of a compound semiconductor single crystal can be greatly improved.

(3) According to the method of claim 3 , PB
The density of the container made of N is 1.85 g / cm ^{3 to} 2.05 g / cm ³
Of the PBN plate constituting the PBN container.
X of (002) plane and (100) plane measured on the plane perpendicular to the thickness direction
Line diffraction integrated intensity ratio: {I (002) / I (100)}
Using a PBN container ranging from 8 to 30 over the area,
Compound semiconductor single crystal from the seed crystal side housed in the lower end of the vessel
In this manner, a compound semiconductor single crystal of a single crystal in the entire region from the seed portion of the crystal to the final end of the crystal growth can be obtained with good reproducibility.

(4) If the compound semiconductor single crystal is pulled and grown using the PBN container according to the fourth aspect , the crystal growth from the seeding portion of the crystal to the final stage of crystal growth can be performed for the reasons described in (1) and (2) above. It is possible to obtain a compound semiconductor single crystal of the entire region single crystal with good reproducibility up to the end.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing an example of an apparatus configuration used for manufacturing a compound semiconductor single crystal.

FIG. 2 is a graph showing the relationship between the density of a PBN container and the X-ray diffraction integrated intensity ratio (degree of orientation).

FIG. 3 is a cross-sectional view of a PBN container for explaining an example of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 High temperature furnace 5 PBN container (crucible) 6 Polycrystalline raw material 7 Liquid sealant 11 seed crystal 13 PBN container 17 Seed crystal 18 Polycrystalline raw material 19 Liquid sealant 20 Raw material melt 21 Liquid sealant layer

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shuichi Tahara Sachi, 5-1-1 Hidaka-cho, Hitachi City, Ibaraki Prefecture Inside the Hidaka Factory, Hitachi Cable Co., Ltd. 5-1-1, Hachimachi, Hidaka Electric Cable Co., Ltd. (56) References JP-A-6-122504 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C30B 1 / 00-21/06

Claims (4)

(57) [Claims] 1. A PBN container containing a raw material melt is placed in a high-temperature furnace, and a single crystal is grown by relatively moving the seed crystal and the PBN container while contacting the seed crystal with the raw material melt. In the method, the compound semiconductor single crystal is grown using a PBN container that simultaneously satisfies the following conditions (1), (2), (3) and (4). Production method. (1) The density of the PBN container is 1.85 g / cm ³ over the entire area.
It is in the range of ~2.05g / cm ^3. (2) X-ray diffraction integrated intensity ratio of (002) plane and (100) plane measured on a plane perpendicular to the thickness direction of the PBN plate constituting the PBN container: {I (002) / I (100)} Is 8
It is in the range of ~ 30. (3) The density of the PBN container gradually increases from the bottom to the opening. (4) X-ray diffraction integrated intensity ratio of the (002) plane and the (100) plane measured on a plane perpendicular to the thickness direction of the PBN plate constituting the PBN container: ｛I (002) / I (100) ) The value of｝ gradually increases from the bottom to the opening. 2. A PBN container containing a raw material melt is placed in a high-temperature furnace, and a single crystal is grown by relatively moving the seed crystal and the PBN container while contacting the seed crystal with the raw material melt. A method for producing a compound semiconductor single crystal, comprising growing a compound semiconductor single crystal using a PBN container that satisfies the following conditions (5) and (6) simultaneously. (5) The value of the thermal conductivity measured on a plane perpendicular to the thickness direction of the PBN plate constituting the PBN container is 50 W / mK over the entire area.
It is in the range of ~ 200W / mK. (6) The value of the thermal conductivity measured on a plane perpendicular to the thickness direction of the PBN plate constituting the PBN container gradually increases from the bottom to the opening. 3. A PBN vessel containing a raw material melt is disposed in a high-temperature furnace, and a region having a predetermined temperature gradient from a temperature higher than the melting point of the crystal to a temperature lower than the melting point is formed . meet in the method from the seed crystal side is relatively moved and housed in the lower end portion of the PBN made containers <br/> device to the container growing a single crystal, the following conditions (1) and (2) at the same time A method for producing a compound semiconductor single crystal, comprising growing a compound semiconductor single crystal using a PBN container. (1) The density of the PBN container is 1.85 g / cm ³ over the entire area.
It is in the range of ~2.05g / cm ^3. (2) X-ray diffraction integrated intensity ratio of (002) plane and (100) plane measured on a plane perpendicular to the thickness direction of the PBN plate constituting the PBN container: {I (002) / I (100)} Is 8
It is in the range of ~ 30. 4. A container made of PBN according to claim 1 or 2 .