JPS6128640B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to crystal growth of -intergroup compound semiconductors, and more particularly to a method and a growth apparatus for crystal growth of -intergroup compound semiconductors using a solution. - Intergroup compound semiconductors are direct transition type and have a large forbidden band width, so -
It is an attractive material that can provide properties that cannot be obtained with intergroup compound semiconductors. The table shows the electrical conductivity type and forbidden band width of the crystal obtained.

[Table] - Currently, research on intergroup compound semiconductors is not as advanced as that of intergroup compound semiconductors, so their unique properties are not being fully utilized. The typical crystals are ZnSe and ZnS
Since each crystal has a high vapor pressure of each constituent element and a high melting point of the crystal, it is necessary to optimize the crystal growth conditions even more than for intergroup V compounds in which only one element has a high vapor pressure. There is a reason. However, in conventional methods, crystal growth of intergroup compounds is generally performed by melt growth at high temperature and pressure, and no consideration has been given to deviations from the stoichiometric composition. Furthermore, the melt growth method, which can be grown at relatively low temperatures and has been the mainstream for intergroup compounds, has been slow to develop and has hardly been developed. The reason for this is that, of course, the growth method using the constituent elements as a solution is optimal for obtaining crystals that do not contain extra impurities, but for example, in the case of ZnSe, the solubility of ZnSe is low at low temperatures. Because of this and the relatively high vapor pressure of ZnSe, solution growth using these as solvents could not be used. Therefore, a solution growth method using Te as a solvent was developed because it is an element in the same group as ZnSe, ZnS, etc., and has high solubility and relatively low vapor pressure. However, in this growth method, the grown crystal contains several percent of Te, ZnSe _1-x Te _x or
A mixed crystal having the composition ZnS _1-x Te _x is obtained. Hereinafter, a method for producing a ZnSe single crystal mainly using a liquid phase growth method will be explained. That is, ZnSe has a forbidden band width of 2.8 eV, and if a pn junction can be formed, it can be expected to work as a highly efficient blue light emitting diode.
However, if several percent of Te is contained in ZnSe, it should be considered as a mixed crystal ZnSe _1-x Te _x , and the forbidden band width will decrease, making it impossible to obtain blue light emission.
Since the atomic radii of Te and Se are significantly different, defects are more likely to occur due to non-uniform strain within the crystal. Therefore, it is desirable to obtain a crystal that can be substantially regarded as a ZnSe crystal with as little Te content as possible. Furthermore, even if a ZnSe crystal is actually obtained, many Se vacancies occur in the ZnSe crystal due to the high vapor pressure of Se, and these act as donors, so usually only n-type crystals can be obtained, making it impractical. A good p-n junction cannot be obtained. Furthermore, when Se vacancies and impurities combine, a deep level is formed that acts as a non-luminescent center, so even if a pn junction is formed, high luminous efficiency cannot be expected. Therefore, there is a need for a technique for growing a highly perfect crystal that can form a pn junction. Furthermore, the present inventor, in Japanese Patent Application Laid-Open No. 54-3798,
We have provided a method using Te and Se as solvents for solution growth of ZnSe, but accurate measurement of the crystal composition after growth shows that precipitation occurs even when a solvent containing a small amount of Te is used. For crystals that
The ZnTe _1-x Se _x crystal always contains Te, and if elements other than the constituent elements are used as a solvent, the solvent element will be introduced as an impurity.
It has been extremely difficult to grow crystals with high purity and few crystal defects because the forbidden band width of the grown crystal decreases and lattice distortion occurs in the crystal due to the large atomic radius of Te. The present invention eliminates this drawback, contains no extra impurities and has a small deviation from the stoichiometric composition.
A method and a growth apparatus for growing ZnSe crystals are provided. A detailed explanation of the present invention will be given below. Figure 1 shows the temperature-vapor pressure curves of Zn, Se and Te, and the table shows the melting point, density and thermal conductivity of each element.

[Table] Comparing the properties of Zn and Se, the constituent elements of ZnSe, Zn has a lower vapor pressure and Se has a lower melting point. Also, the relationship between the densities d is d _Se <d _{Zo Se} < d _Zo . On the other hand, the saturation solubility of ZnSe crystals for each element has not been reported, but the liquid phase growth temperature region (600
It is estimated that it is less than 1% at temperatures (~800°C), so it is necessary to increase the temperature to increase the growth rate. However, as is clear from Figure 1,
The vapor pressures of Zn and Se are quite high above 800°C. The table shows the temperature-vapor pressure relationship of Zn and Se, determined by extrapolating each curve, and the solubility of ZnSe, determined from the very early phase diagram reported, in a temperature range that deviates from Figure 1. .

【table】

[Table] As is clear from the table, by using Se as a solvent, the temperature at which ZnSe has the same solubility can be lowered by about 200°C than in the case of Zn, and the contamination of impurities can be reduced. Since it can be minimized, high purity crystals can be obtained. An even more important advantage is that, as is clear in Figure 1, in conventional growth methods, the vapor pressure of Se is higher than that of Zn, so crystals grown at high temperatures have a stoichiometry that is deficient in Se. Only crystals with large deviations from the above were obtained. Therefore, by using Se as a solvent, it is possible to compensate for the lack of Se and obtain ZnSe crystals with less deviation from the stoichiometric composition. It also becomes possible to create p-type crystals with low impurity density. However, the problem with using Se as a solvent is that although the growth temperature can be lowered,
The key is to have a high vapor pressure and choose an appropriate temperature difference. To solve this problem, I performed the following operations. If a quartz crucible is manufactured by processing a quartz tube with an inner diameter of about 10 mmφ, even if the wall thickness is about 2 mm, the
Since it can sufficiently withstand internal pressures on the order of atmospheric pressure, it is also possible to control temperature differences relatively easily. However, if the pressure exceeds 10 atmospheres, there is a risk of explosion if the crucible is distorted or has thin walls, so air, Ar, and N ₂ are added double or triple from the outside of the quartz crucible.
It is necessary to reduce the effective pressure applied to the quartz crucible by applying pressure with a gas such as When pressure is applied to the outside of the quartz crucible, the thermal conductivity of the gas increases in proportion to the pressure, so setting the temperature difference between the crystal precipitation area and the source crystal area is important. There is an optimum value for growth conditions for obtaining good crystallinity, which is interrelated with growth temperature - vapor pressure - temperature difference - pressure around the crucible. For example, 800
℃, the quartz tube can withstand even without external pressure applied, so a temperature difference of about 40℃ is sufficient, and 900℃
(Se pressure is 8500 Torr), the most desirable growth conditions are 20°C outside a single pressure vessel, and a temperature difference of about 10°C for growth at 1000°C (20240 Torr). In addition, Se in the solvent in the crucible and the source crystal
There is no strong limit to the amount of ZnSe, and it will grow if a source crystal is present, but the preferred range is about 2 to 20 g of ZnSe per 10 g of Se in the solvent. There are various ways to set the source crystal, but as shown in the table, the relationship of specific gravity is d _Se < d _{Zo Se} < d
Since it is _Zo , when Se is used as a solvent,
Since ZnSe is heavy, it is necessary to devise a source crystal setting. When using a vertical crucible, if the source crystal is placed at the top, the crystal precipitation area at the bottom will contain
Crystals precipitate due to differences in temperature and specific gravity, but since the difference in specific gravity is relatively large, not only the crystals dissolved in the solvent will precipitate, but the source crystal itself will move to the precipitation area, resulting in the formation of large single crystals. This will inhibit its formation. Therefore, the method for precipitating a large single crystal is to take into consideration the properties of Se and ZnSe, create a horizontal structure, arrange two chambers, a crystal precipitation part and a source crystal part, and connect both chambers by Se solvent. ,
By sinking ZnSe into the source crystal part, Se
Only the crystals dissolved in the solvent move to the crystal precipitation area due to the temperature difference between the two chambers, so growth progresses through a regular crystal growth mechanism, making it possible to grow large single crystals. Become. Examples will be shown below and specifically explained. Example 1 The crystal growth apparatus used in the present invention and the temperature distribution during crystal growth are shown in FIG. For crystal growth, the temperature necessary for crystal growth is provided by a furnace core tube 1, which is the main part of the crystal growth apparatus, and a heater wire 2 wound around the outer circumference of the furnace core tube 1. A quartz ampoule 11 is suspended in a furnace core tube 1 by a heat-resistant wire (not shown) such as a Kanthal wire using a hook 10 at the top of the quartz ampoule. As for the structure of the quartz ampoule 11, the crystal precipitation part 15 at the lower part of the quartz ampoule is formed into a conical shape with an opening angle of about 30° to 60° so that single crystal nuclei can be easily precipitated. Furthermore, a heat sink 14 is formed by welding a solid quartz rod to the tip of the crystal precipitation part so that heat from the upper part of the ampoule flows through the tip of the crystal precipitation part 15 to the outside of the ampoule. In order to increase the effectiveness of the heat sink, it is also effective to arrange a material with high thermal conductivity, such as a heat-resistant mesh, around the outer periphery of the quartz. The dimensions of the quartz ampoule 11 are, for example, an inner diameter of 8 mmφ, an inner thickness of quartz of 2 mm, and a length of 100 mm.
Put 10g of Se13 as a solvent in this, place 5g of the source crystal (small-sized ZnSe polycrystal) 12 on top of this, and open the top of the quartz ampoule with a vacuum better than 10 ^-6 Torr. After sealing, the hook 10 is welded. As for the temperature distribution in the furnace during crystal growth, the temperature of the source crystal part 12 varies depending on the way the heater 2 is wound, as shown in FIG.
Temperature distribution 17 is set such that the temperature is higher than that of temperature 5. The actual temperature during crystal growth is 850 to 950°C in the source crystal part 12 and 800 to 900°C in the crystal precipitation part.
Therefore, the distance between the two regions is approximately 5 cm, but the temperature difference with respect to the growth temperature is 20 °C/cm to 50 °C at 800 °C.
The range of ℃/cm was preferable, and around 40℃/cm was optimal. In addition, when the growth temperature is about 900℃, it is 10 to 30
In the range of ℃/cm, around 20℃/cm was good. The Se pressure during crystal growth is determined by the temperature of the solvent, and by the way, the pressure of Se at 800°C is approximately 3.5 atm.
At 900℃, the pressure is approximately 11 atm. Crystal growth time is approximately 10 days at 800℃, 900℃
After 7 days of growth, a bulk single crystal along the inner wall of the quartz tube could be obtained. By slicing the grown crystal, it can be used as a substrate crystal. As a method of generating single crystal nuclei in the crystal precipitation area in order to make the growing crystal into a single crystal, at the start of growth, pulse the temperature of the crystal precipitation area in the range of 10℃ to 20℃ for about 10 to 60 minutes. By changing the temperature, it is possible to increase the size of the single crystal part of the precipitated crystal. Figure 3 shows a pulsed temperature cycle diagram.
If there are several large and small growth nuclei transferred to the crystal precipitation section 15 at the crystal growth temperature a, crystals will precipitate from each nucleus, and the resulting crystal will become polycrystalline. To prevent this, as shown in b, if the temperature is raised by 10 to 20°C above the crystal growth temperature, the saturation solubility will increase, so the small ones among the growing nuclei will melt and only the large ones will remain. Next, when the temperature is returned to the growth temperature at c, the saturated solubility decreases, so the supersaturated crystals grow on the remaining growth nuclei and enlarge the growth nuclei. By repeating this process several times, only the largest crystal nucleus remains and single crystal growth is performed around this nucleus. A large single crystal can be obtained even with the quartz ampoule having the structure shown in FIG. 2A, but more effective examples are shown in FIGS. 2B and 2C. The problem with the structure shown in Figure 2 A is that when a source crystal with a small particle size close to powder is used, it floats on the surface due to the surface tension of Se, but when a bulk crystal is used, a ZnSe crystal Since the specific gravity of Se is higher than that of Se, the source crystal settles to the bottom due to its own weight during growth, and accumulates in the crystal precipitation area without being dissolved in the solvent, which inhibits single crystal growth due to regular surface migration, and the source crystal Polycrystalline growth on top may occur. In order to prevent this, devices 21 and 22 were added to the intermediate part between the source crystal and the crystal precipitation area to trap large source crystals that would not dissolve in the solvent and would settle directly, as shown in Fig. 2(b).
This is the growth apparatus shown in Fig. That is, as shown in FIG. 2B and C, it is desirable to insert a slit-like material between the source crystal part and the precipitation part. In FIG. 2B, a constriction with an inner diameter of, for example, about 3 mm is inserted into the inside of the quartz ampoule, and in FIG. FIG. 2 H-2 shows an example of the shape of a plan view of the grating. The dimensions of this square depend on the size of the source crystal, but in this example, it is 4 x 4 x 4 mm ^.
Since several source crystals of about 100 mL are inserted, it is sufficient if the grid size is large enough to prevent the source crystals from passing through. The material is preferably one that is easy to work with, such as quartz or carbon, and has little reactivity with Se. The shapes of the other regions are almost the same as the example shown in FIG. 2A. In the cases shown in FIG. 2 (b) and (c), the single crystal portion in the bulk crystal grew larger. Example 2 It has already been mentioned that the specific gravity of Se and ZnSe has a relationship of d _Se <d _ZoSe , and by actively utilizing this relationship, a product with good crystallinity was obtained. That is, when ZnSe crystals are placed in a Se solvent, the crystals settle to the bottom of the solution before being dissolved in the solvent. Therefore, FIGS. 4A and 4B show examples of ampules having a vertical structure, and FIG. 4C shows an example of a horizontal structure. Figure 4 E-1,
Ro-1 and Ha-1 are front views of the ampoule, Fig. 4
2. Row 2 is a cross-sectional view of the source crystal part, Figure 4 E.
3, R-3 and H-3 are temperature distribution charts in the horizontal plane of the ampoule, and FIG. 4 A-4 and H-4 are temperature distribution charts in the vertical direction of the ampoule. In case of vertical structure,
When setting the source crystal 12 on the opposite surface of the crystal precipitation part 15, some effort is required, and E-1 is the crystal precipitation part 15.
A quartz tube with an inner diameter larger than that is connected to form a source crystal chamber 25 in the region with the larger inner diameter, and the source crystal is placed in this chamber. In addition, in Row 1, a container 26 containing source crystals is suspended from the inner wall of the quartz tube.
There are methods such as covering with Se solvent. In either case, means is provided to prevent the source crystals from settling in the crystal precipitation section 15 without being dissolved in the solvent. However, as a method of effectively utilizing the difference in specific gravity, the horizontal type shown in Fig. H-1 is more effective. Two chambers are provided in the horizontal type, and the source crystal 12 is submerged in the lower part of the source crystal chamber 25 in one, and the source crystal 12 is immersed in the other side. The precipitation section 15 is used as the precipitation section 15, and both chambers are filled with solvent.
More preferred is a format in which it is linked with Se13.
In addition, as for the temperature distribution during crystal growth, in the case of Figure 4A, as shown in A-3, in the source crystal 25, the temperature is lowered at the center as indicated by 27', and the temperature is increased from the periphery to the center. The former source crystal 12 facilitates thermal diffusion. In addition, in the crystal precipitation area 15, the temperature distribution is set to 27'' so that the crystal grows at a constant temperature in the horizontal direction.Also, in the vertical direction, the temperature of the crystal precipitation area is adjusted as shown in Fig. 4-4. It is desirable to have a temperature distribution 28 in which the temperature is almost constant and the temperature is higher above it.Such a temperature distribution can be achieved by using a single-temperature zone furnace. , crystal precipitation part 15, source crystal part 2
A two-temperature zone furnace using a separate furnace is also effective. The same applies to FIG. 4B, but as for the lateral temperature distribution of the source crystal part 26, it is desirable to make the central part higher as shown in 29 in FIG. If it is difficult, 2
Even at the same temperature such as 9', the source crystal can diffuse due to the density difference. The temperature distribution in the longitudinal direction is similar to that shown in Fig. 4-4. In the case of the horizontal format shown in FIG. 4C, setting the temperature distribution is more important than in the cases of FIGS. 4A and 4B, in which the ampoule is vertical. The temperature distribution in the lateral direction requires that the temperature of the source crystal part 25 be higher than the temperature of the crystal precipitation part 15, as shown in 36 in FIG. It is necessary to create a temperature difference between the upper and lower portions of the crystal precipitation area 15 as shown in FIG. As a heating furnace to satisfy this condition, it is desirable to use a furnace 37 as shown in FIG. Growth was carried out using a vertical furnace with heaters 39 and 39' arranged vertically and independently at the connection point 38' to achieve the temperature distributions shown in FIG. 4, H-3 and H-4. The shape of the upper part of the crystal precipitation part 15 is a cylinder with an inner diameter of 8 mmφ, and the lower part is a conical shape with an apex angle of about 60°, and the height is 40 mm.
It is. The inner diameter of the connecting pipe 40 is 4mmφ and the length is 50mm.
For the source crystal 12, put about 5g of bulk crystal cut into a size of ^about 4 x 4 x 4 mm, and add Se13.
I put in about 10g. The sealed portion is near the source crystal charging chamber 25. In this case, in order to create a vertical temperature difference in the solution and promote the precipitation of crystals, a heat sink 14 installed in the crystal precipitation section 15 is installed at the bottom of the crystal precipitation section 15 with a thermal conductivity. The growth rate can be increased by placing oxidation-resistant materials such as high heat-resistant steel or nickel plates and extending them to the cold side of the furnace. As a result, a large single crystal with good crystallinity can be obtained. Example 3 At a low temperature of about 800°C, the saturation solubility of ZnSe in Se is low, so even with the temperature difference liquid phase growth method described above, the growth rate is extremely slow and it is difficult to obtain a practical product. It is. Therefore, it is desirable to raise the temperature to increase its solubility, but if the temperature is raised, the vapor pressure of Se will reach tens of atmospheres, which exceeds the pressure limit of the quartz tube and poses a risk of explosion. It is effective to perform operations like this. As shown in FIG. 5A, the growth ampoule 11
This is a method of lowering the relative pressure of the growth ampoule by placing the whole in a pressure-resistant container 51 such as a quartz tube and applying an inert gas pressure 52 to the container 51. For example, when the Se pressure in the quartz ampoule 11 is 10 to 20 atm, Ar or air is added to the pressure vessel 5 made of quartz or heat-resistant steel such as stainless steel.
When 5 to 10 atmospheres of pressure is applied to the quartz ampoule 11, the effective pressure applied to the quartz ampoule 11 becomes 5 to 10 atmospheres, which is well within the pressure resistance of quartz. When this method is applied to the growth ampoules described in Examples 1 and 2, the growth rate is greatly accelerated, and a large single crystal can be obtained in about 2 to 3 days. As the pressurization method, the case where inert gas pressure is applied is shown. Using the inert gas cylinder 53, the pressurizing pump 54 and the quartz tube 51 can be easily connected using a pressure-resistant connector 55 made of stainless steel or the like. Further, the preservative activated gas pressure 52 in the pressure container 51 is adjusted by a pressure regulator 56 directly connected to the cylinder 53. Furthermore, by providing a three-way stop valve 57 in series with a pressure regulator between the cylinder 53 and the pressure vessel 54, it is effective to reduce the pressure 52 in the pressure tube 51 after crystal growth is completed. Although a method using a gas cylinder has been described as a pressurizing method, a similar operation is also possible by applying compressed air pressure using a compressor instead of a gas cylinder. Figure 5A shows an example of one-stage pressure application;
Pressure-resistant operation is also possible with the same concept for the second and third stages of pressure application. Examples are shown in Figure 5 B and C. In order to simplify the explanation, only the structures of the quartz ampoule 11 and the pressure tube are shown, but the other parts are exactly the same as in FIG. 5A. FIG. 5B shows an example of two-stage pressurization, in which a second pressure-resistant tube 61 is arranged outside the pressure-resistant tube 51 in the case of one-stage pressurization. When crystal growth is performed at a pressure in the quartz ampule 11 of 30 atm, if the pressure 52 in the first pressure tube 61 is 20 atm and the pressure 62 in the second pressure tube 61 is 10 atm, the pressure at each part will be Each has a pressure of 10 atm, which is within the pressure limit of the quartz tube. Figure 5 C shows an example of three-stage application, with quartz ampoule 1
When crystal growth is carried out at a pressure of 40 atm inside the pressure tube 63, an additional pressure tube 63 is added to the pressure tube structure shown in Figure 5B.
If a pressure 64 is further applied inside this, 10 atmospheres will be applied to each part as shown in FIG. 5B. Although the method for spontaneously precipitating crystals has been described above, a bulk single crystal with better crystallinity can be obtained by inserting a single crystal into the location where the crystal is precipitated. Since each embodiment is the same, a typical example will be shown in which a quartz ampoule shown in FIG. 2A is used, but the same applies to other structures. Example 4 Bulk crystal was analyzed by X-ray diffraction to determine the angle of ±2 with respect to the <111> or <100> crystal plane of ZnSe.
Slice with an accuracy of about 100°, polish with #4000 Al ₂ O ₃ , mirror polish on a buffing plate using, for example, a polishing material with the trade name FM4 (alumina polishing material for polishing), and then perform ultrasonic cleaning. Do enough, Br
- Etch for a few minutes with methanol or CicaClean (a choline-based etching liquid) to create a mirror finish. Since this crystal becomes a seed crystal 71, it is set at the bottom of the crystal precipitation part 15 so that the mirror-like crystal plane faces upward, as shown in FIG. 6A. The setting method is to use a container made of quartz or graphite, etc., in which the crystals are stored, so that they are perpendicular to the growth direction, or to set the crystals at the bottom of the container, and to store the crystals in a container made of quartz or graphite. This can be done appropriately by pressing the crystal with a nail-like object. Before the start of growth, the solution 13 and the seed crystal 71 are
Separate the solutions so that they do not come into contact with each other and carry out the alloying for several hours at the growth temperature to reach a saturation solubility of Se13.
After the ZnSe 12 is dissolved, the solution 13 and the seed crystal 71 are brought into contact with each other to start growth, as shown in FIG. 6B. After several days of growth at 800°C, we were able to obtain a bulk single crystal with a height of about 2 cm. Example 5 As an application example of Example 4, as shown in FIG.
Insert an n-type single crystal substrate 82 of about μm and heat to 900°C.
After alloying for about 1 to 3 hours at a temperature of
By immersing the Se solution 13, the substrate crystal 8
2. Epitaxial growth is performed on the 2nd layer. If the alloying time is short, the substrate crystal 82 will be melted immediately after immersion in the solution, so sufficient alloying temperature and time are required. At 800°C, it will take 8 to 12 hours, and at 850°C, it will take 5 to 10 hours.
It takes about an hour. Further, the temperature difference between the substrate crystal 82 and the source crystal 12 is between 20°C/cm and 100°C/cm.
The most desirable temperature is approximately 50°C/cm. If the temperature difference is too large, crystallinity deteriorates, making it impossible to manufacture good devices. On the other hand, if the temperature difference is too small, mutual compatibility of crystals will occur between the substrate crystal and the solution, and there is a great risk of melting the substrate crystal 82 in the initial stage of growth, so there is an appropriate temperature difference for growth. The thickness of the growth layer is 0.1 to 0.33 at 800℃.
An epitaxial growth layer with good crystallinity can be obtained at a growth rate of about 0.2 to 0.6 μm/hr at 900° C. It was found that the growth thickness is proportional to the temperature difference and time. With the above temperature difference, when the growth temperature is 900° C., a growth rate in the range of 0.05 μm/hr to 0.3 μm/hr can be obtained. As for the characteristics of the grown crystal, a crystal without addition of impurities has p-type conduction and an impurity density of 1×10 ¹⁵ /cm ³ . Na,
Group elements such as Li, Au, Ag, Cu, P, As, Sb
By adding group elements such as Ga, In, Al, etc., or group elements such as F, Cl, Br, I, etc., a low resistance P-type growth layer can be obtained. A shaped low resistance layer was obtained. The substrate crystal 82 may be placed on top of the solution 13 as shown in FIG. 7C, and after alloying, the substrate crystal 82 may be turned over as shown in FIG. 6D. Almost the same results are obtained with this method. Epitaxial growth is not limited to this example, but epitaxial growth is also possible by setting the substrate crystal above the solution and heating the bottom of the solution to a high temperature. As explained above, the present invention provides a method and apparatus for growing semiconductor crystals such as ZnSe and ZnSSe, which are Se-based intergroup compounds having a high vapor pressure at a relatively low temperature.

[Brief explanation of the drawing]

Fig. 1 is a graph of vapor pressure versus temperature of Se, Zn, and Te, and Fig. 2 is a diagram for explaining each example of Embodiment 1 of the present invention. figure,
A-2 is a graph of temperature distribution, H-2 is a top view of a slatted member, FIG. 3 is an example of a temperature cycle at the start of crystal growth, and FIG. 4 is a graph of each example of Example 2 of the present invention. This is a diagram for explaining,
1, H-1 is a side view, A-2, R-2, H-2 is a sectional view, E-3, E-4, R-3, H-3, H-2
4 is a graph of temperature distribution, FIGS.
B is a schematic sectional view for explaining Embodiment 4, FIG. 7A,
B, C, and D are schematic cross-sectional views for explaining an application example of the fourth embodiment. 11...Ampoule, 12...Source crystal 13...
...Se, 14... Heat sink, 15... Crystal precipitation section, 17... Temperature distribution, 21, 22... Device for stopping large source crystal, 25, 26...
Source crystal chamber, 27... Lateral temperature distribution, 28
...Temperature distribution in the vertical direction, 29...Temperature distribution in the horizontal direction, 35...Temperature distribution in the longitudinal direction, 36...Temperature distribution in the horizontal direction, 37...Vertical growth furnace, 38...Furnace core tube.

Claims (1)

[Claims] 1 Se is used as a solvent, a temperature difference is provided in the solvent, and the high temperature side of the solvent is arranged as a source crystal part and the low temperature side as a crystal precipitation part, and the source crystal part is in the source crystal part. is arranged, the crystal precipitation part and the source crystal part are maintained at a constant temperature, and the ZnSe crystal is deposited in the crystal precipitation part.
ZnSe crystal growth method. 2. The ZnSe crystal growth method according to claim 1, characterized in that a ZnSe single crystal is placed in advance in the crystal precipitation area, and an epitaxial growth layer is grown on the single crystal. 3. The ZnSe crystal growth method according to claim 1 or 2, wherein the crystal growth is performed in a pressure-resistant container. 4. It has a crystal precipitation part and a source crystal part, and has a heating means for keeping the crystal precipitation part and the source crystal part at a constant temperature.
ZnSe crystal growth equipment. 5. It houses a growth device having a crystal precipitation section and a source crystal section, and is characterized by having a pressure-resistant tube for applying high-pressure gas from the outside of the growth device.
ZnSe liquid phase growth equipment.