JP3313412B2 - Method and apparatus for manufacturing semiconductor crystal - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention belongs to the field of electronic materials,
The present invention relates to a method and an apparatus for manufacturing a mixed crystal semiconductor crystal in which two kinds of semiconductors are homogeneously mixed at a predetermined ratio.

[0002]

2. Description of the Related Art Advanced technology is required to produce a large, high-quality single crystal by homogeneously mixing two kinds of semiconductors at a predetermined ratio. The Bridgman method, the Czochralski method, the zone melting method, and the like have been developed as techniques for growing such large mixed crystals (bulk mixed crystals). However, these prior arts have many problems, and all of them are at the research stage for the growth of large bulk mixed crystals. In the conventional band melting method, it is not possible to use only one of the two semiconductors constituting the mixed crystal as a raw material. It is essential to produce a raw material crystal having a desired composition ratio. However, in principle, a raw material crystal should be obtained if a homogeneous mixed melt of two semiconductors at a predetermined ratio is solidified by rapid cooling so that segregation does not occur. Since there is a difference in specific gravity between semiconductors, it is difficult to obtain a homogeneously mixed melt, and when the melt is quenched and solidified, segregation of the semiconductor on the high melting point side occurs. Was not obtained. This is a major obstacle to growing a high-quality crystal having a predetermined composition by using the band melting method. On the other hand, in the method of growing a mixed crystal from a melt obtained by melting and mixing two types of semiconductor crystals using the ordinary Bridgman method or Czochralski method, a mixed composition (mixing ratio of the two types of semiconductors) is constant. Crystals cannot grow. This is because a solid phase containing a large amount of a component having a higher segregation coefficient (a semiconductor component having a high melting point among the two semiconductors) is precipitated out of the two types of semiconductors than the melt composition. In the melt, a component having a small segregation coefficient or a semiconductor component having a low melting point increases. Therefore, if mixed crystal growth is continued from this melt,
The growing mixed crystal composition has a distribution such that components having a small segregation coefficient or semiconductor components on the low melting point side increase. In addition, since a solid phase containing more components on the high melting point side than the melt composition is precipitated, the melting point decreases as the growth progresses. It was necessary to gradually lower the temperature near the interface between the metal and the solid phase. This is a problem which is inextricably linked to the fact that a composition gradient is inevitably generated in the grown mixed crystal. These problems are related to the invention (Japanese Patent Application No. 60-143) filed by the present applicant.
693, Published Patent Application (A) 62-3097), that is, of the two types of semiconductors constituting the mixed crystal,
Most of the problems have been solved by a method of performing mixed crystal growth by the Czochralski method while supplying a semiconductor component on the high melting point side (hereinafter, this method is referred to as a solute supply Czochralski method). A similar method was developed by Nakajima et al.
ium Arsenide and Related
Compounds 1991, Inst. Phys. C
onf. Ser. No. 120, chapter 2
pp. FIG. 4 reported at 62-71 explains the prior invention of the prior application. As shown in FIG. 4A, in the prior art, one solution reservoir, ie, a crucible, is filled with a growth solution, and a semiconductor having a high melting point among two semiconductor components constituting a target mixed crystal is contained in the solution. Alternatively, a mixed crystal containing a first semiconductor and a second semiconductor in a predetermined ratio is pulled up from the solution in a state in which a solute-supplying solid phase containing a large amount of the semiconductor component is brought into contact. However, this method had two major problems. First, since the solid phase for solute supply is in direct contact with the growth solution, it is susceptible to the effects of convection and the like in the growth solution, and the supply of solute tends to be excessive, and its control is difficult. That is. FIG. 4B schematically shows the temperature distribution in the solution 3. The vertical axis indicates the vertical position of the solution, and the horizontal axis indicates the temperature. T _a corresponds to the actual temperature profile of the solution. Meanwhile T ₁ corresponds to the saturation temperature of the solute contained in the solution (also referred to as a determined liquid phase temperature in solution composition), its distribution reflects the concentration distribution of the solute. Since the solution is stirred by convection, the solute concentration distribution in the solution becomes substantially uniform except for the vicinity of the solid-liquid interface 23 in the growth part. On the other hand, at the solid-liquid interface 23, the supersaturated component precipitates as a crystal, so that the temperature becomes the saturation temperature. In the case of mixed crystal growth, the composition of the precipitated solid phase has more semiconductor components on the higher melting point side than the liquid phase composition. Therefore saturation temperatures T ₁ in the solid-liquid interface 23 lowers, consistent with the actual temperature T _a in the solid-liquid interface 23. by the way,
When the crystal is pulled up by the Czochralski method, the actual temperature distribution becomes as shown in FIG. 4B, as the temperature gradually decreases from the solid-liquid interface 43 of the raw material crystal 4 to the solid-liquid interface 23 of the crystal growth part. . At this time, the solid-liquid interface 2
Than the actual temperature T _a at near 3, the higher the saturation temperature T _1, portions thereof become constitutional supercooling state was a major problem to cause the occurrence of polycrystalline generation and dendrites. In the prior art, as a method for solving the above problem, there is a method of obtaining an actual temperature distribution such that the temperature difference at both solid-liquid interfaces between the source crystal side and the growth crystal side becomes small as shown in FIG. 5 (a), the contact area between the raw material crystal 4 and the solution 3 is reduced to reduce the amount of solute supplied to the solution, so that the solid-liquid interface on the raw material crystal side is reduced as shown in FIG. 5 (b). and a method of reducing the saturation temperatures T ₁ than the actual temperature T _a at 43. However, FIG.
It is difficult to realize the actual temperature distribution as in (b '). On the other hand, in the method shown in FIG. 5, as the growth proceeds, the raw material crystal 4 is melted and consumed immediately, so that it is difficult to grow a large crystal. A second problem of the prior art is that the amount of the growth solution decreases as the pulling of the crystal proceeds.
This decrease affects the movement of solutes and the actual temperature distribution in the growth solution, and causes a change in the temperature of the solid-liquid interface accompanying a drop in the position of the solid-liquid interface 23 in the growth part. Therefore, this affects the composition, growth rate, diameter, etc. of the crystal to be pulled, making it difficult to obtain a homogeneous and high-quality mixed crystal.

[0003]

SUMMARY OF THE INVENTION The present invention relates to the problem of controlling the amount of solute supply, which is a problem of the conventional solute supply Czochralski method, and to the fact that the growth of a mixed crystal proceeds and the growth solution (melt). An object of the present invention is to provide a large-sized and high-quality mixed crystal growth technique having a predetermined composition (mixed crystal ratio) which solves the problem of a change in the position of the solid-liquid interface caused by a decrease in the amount.

[0004]

According to the present invention, one or more crystals of a semiconductor or the like are melted and dissolved in a crystal or a solvent of another kind of a semiconductor or the like having a lower melting point than that of the crystal or a solution or a melt thereof. A partition having a plurality of through holes is provided, and the solution or melt is separated into a crystal growth section and a solute supply section, and the solution of the solute supply section contains a source crystal composed of at least one of two semiconductors. And supplying a solute to the solute supply unit solution, and providing a mechanism such as a piston or a floating crucible so that the crystal growth unit solution becomes a constant amount through a hole provided in the partition wall. The most important feature is that the mixed crystal containing the first semiconductor and the second semiconductor at a predetermined ratio is pulled from the crystal growth part solution by the Czochralski method. The difference from the prior art is that the raw material crystal for solute supply is not in direct contact with the crystal growth section solution, and that the amount of solution in the crystal growth section can be kept constant.

[0005]

The features of the present invention will be described with reference to the drawings. FIG. 1A is a sectional structural view schematically showing a portion directly related to crystal growth of a crystal growth apparatus used for carrying out the manufacturing method of the present invention. 1 is a seed crystal, 2 is a growing crystal during pulling, 3 is a solution (melt) for growth, 30 is a solution (melt) in a solute supply section, 4 is a raw material crystal for solute supply, 5 is a crucible, 50 Is a partition wall inserted between the solution 30 and the growth solution 3 in the solute supply section, and the partition wall is provided with one or a plurality of through holes 51. Further, the amount of the growth solution 3 can be controlled by moving the partition 50 up and down by an appropriate method, for example, buoyancy. The holes 51 are for controlling the mass of the melt supplied from the solute supply unit to the growth unit, and the size, position, and number of the holes 51 are, of course, set so as to meet the purpose. The principle of the composition control method for homogeneous bulk mixed crystal growth of the present invention is the same as that of the above-mentioned prior invention (Japanese Patent Application No. 143693). That is, in a binary alloy system, or a pseudo-binary alloy system composed of two compounds having one component element in common among the components constituting each compound, if the liquid phase and the solid phase are in thermal equilibrium, Is based on the fact that the composition of the liquid phase and the solid phase is uniquely determined. Now, as shown in FIG. 1B, the actual temperature distribution in the center of the growth system in the growth axis direction shown in FIG. 1A is such that Ta is constant in the solute supply portion, and the growth crystal in the crystal growth portion. A case will be described where the distribution is such that the temperature gradually decreases as approaching the solid-liquid interface 23 between the solution 2 and the solution 3. By uniformly heating the crucible 5 with an appropriate heating device such as an electric furnace, the solution 30 in the solute supply unit and the solute supply raw material crystal 4 are in a state close to thermal equilibrium. Of course, the supply of the solute from the solution 30 to the growth solution 3 through the through hole 51 lowers the solute concentration of the solution 30 near the through hole 51, but the solute is immediately supplied from the surroundings by diffusion or convection. Further, if the area of the solid-liquid interface 43 between the raw material crystal 4 and the solution 30 is sufficiently larger than the total area of the through holes 51, the supply rate of the solute from the raw material crystals to the solution 30 is increased through the through holes 51. since the can sufficiently larger than the feed rate of the solute in the solution 3, the solute concentration of the solution 30 takes a saturation density corresponding to the actual temperature T _a of the part. Of course, the amount of solute supplied to the solution 3 through the through-hole 51 per unit time and the amount of supply from the raw material crystal 4 to the solution 30 are balanced and coincide. Thus as shown in FIG. 1 (b), is almost consistent with the distribution the saturation temperature distribution T ₁ of the real temperature distribution T _a a solution of the solute supply unit. On the other hand, on the crystal growth part side, a solute is controlled and supplied to the solution 3 in an appropriate amount by the through hole 51 provided in the partition wall.
In the steady state where crystal growth is continued, the supplied solute, and in the case of mixed crystal growth, the crystal component on the high melting point side constituting the mixed crystal is transported to the solid-liquid interface 23 on the growing crystal side by diffusion or convection. , Where they are deposited as growing crystals. In the case of mixed crystal growth, the crystal component on the low melting point side contained in the solution at the time of this precipitation is taken in at a predetermined ratio, and a mixed crystal having a predetermined composition is grown. During crystal growth, the solid-liquid interface 2 on the growing crystal side
The lowest temperature of 3, where the actual temperature T _a is made almost equal to the saturation temperature T ₁ of the solute. Since the portion other than the solid-liquid interface 23 in the process of the present invention can lower the saturation temperature T ₁ of the solute than the actual temperature T _a, except the solid-liquid interface 23 based on the excessive supply of occurrence and solute compositional supercooling state Since the precipitation of crystals at the portion can be prevented, high-quality crystal growth can be performed. This is one of the features of the present invention. In the present invention, a method for controlling the amount of the solution 3 in the crystal growth portion to be constant in order to obtain stable growth is introduced. FIG.
In (a), Levert is used to control the position of the partition 50.
on is the Journal of Applied Ph
ysics Vol. 29, No. 8, (1958) p
p. 1241-1244, that is, utilizing buoyancy. As the crystal growth progresses, the crystal growth part 3
However, since the solution is automatically supplied from the solution 30 in the solute supply section through the through hole 51, the amount of the solution 3 can be kept constant. Of course, a method other than buoyancy may be used to control the position of the partition 50. FIG. 2 (a) detects the relative position between the liquid surface of the solution 3 and the partition wall 50,
The position is controlled by applying a driving force to the partition 50 in the direction of arrow A by a mechanical method. Although FIGS. 1 and 2 have described the case where a movable crucible type partition wall is used, one of the problems is that the solution 3
Is lowered, and the relative position between the liquid level and a heating device such as an electric furnace changes. To prevent this, as the growth progresses, the position of the heating device is moved and the solution 3 is moved.
It is necessary to eliminate the change in the relative position between the liquid surface and the heating device. FIG. 3 shows an example in which a fixed partition 50 and a piston 60 for pushing up the raw material crystal 4 are used. In this example, solution 3
The position of the liquid surface is detected, the piston is operated so that the position of the liquid surface does not change, and the reduced amount of the solution 3 caused by the crystal pulling is supplied from the solution 30 through the through hole provided in the partition. The features of this example are that the position of the liquid surface of the solution 3 and the relative position with respect to the heating device do not change, so that stable growth can be performed. Further, since the cylindrical crucible 5 is used, the charged amount of the solution 30 and Since the size of the solute supply raw material 4 can be changed, it is possible to cope with crystal pulling of an arbitrary size. Although the three examples of FIGS. 1, 2 and 3 have been described above, it is of course possible to implement the present invention in other ways. Further, as a method of directly controlling the melt mass supplied from the solute supply part to the crystal growth part through the through hole 51 provided in the partition wall, a method of providing a plug in the through hole and opening and closing it may be adopted. Direct control of the supply amount is also possible by controlling convection by applying a magnetic field and controlling the migration of ions through a current through the through-hole.

[0006]

【Example】

(A) First, a predetermined amount of Ga formed in a crucible 5 of FIG. 1 into a predetermined shape and an oxide film or the like on the surface is removed by etching.
The Sb polycrystalline ingot is inserted as the raw material crystal 4. If the shape of the ingot does not match the shape of the crucible,
An appropriate amount of a liquid capsule material such as boron oxide or sodium chloride is added to the raw material crystal to prevent dissociation of antimony. Next, the GaSb raw material crystal is melted by heating to about 750 ° C. in an atmosphere of high-purity argon gas, nitrogen gas, hydrogen gas or the like, and the GaSb raw material crystal 4 is cast and arranged at the bottom of the crucible. After cooling, the liquid encapsulant is removed using an appropriate method, such as methanol, and a predetermined amount of polycrystalline (In, Ga) Sb for a growth solution having a predetermined composition adjusted in advance is added thereto. For example,
When the purpose is to grow a mixed crystal of (In, Ga) Sb with x = 0.7, (In, Ga) Sb as a raw material of the growth solution is used.
The composition of b may be X = 0.2. Of course, the composition of the polycrystalline (In, Ga) Sb for the growth solution 3 must have practically sufficient uniformity, and an oxide film and contaminants must be sufficiently removed from the surface by etching or the like. The raw material crystals can be charged into the partition walls 50 and melted to leak into the crucible 5 and have a predetermined arrangement. The through hole of the partition wall 50 may be, for example, 4 mm in diameter and 5 mm in length, but may be changed depending on the properties of the solution. If necessary, a material for the liquid capsule 7 such as B ₂ O ₃ is added on the (In, Ga) Sb polycrystal for the growth solution 3. At the time of growth, it is necessary to make the viscosity of the liquid capsule appropriate, and for that purpose, an appropriate amount of an alkali metal fluoride or oxide may be added and used. (In, Ga) Sb for seed crystal 1 required for pulling is formed by processing a (In, Ga) Sb single crystal having a target mixed crystal composition and an axial orientation into a predetermined shape, and then polishing, etching, or the like. , And also sufficiently remove oxide film and contamination on the surface. The seed crystal thus formed is attached to a seed crystal fixing chuck of the growth apparatus. As described above, after the materials are charged into the growth apparatus, high-purity hydrogen is flown in the reaction tube at a predetermined flow rate, and is kept for a certain time, for example, about one hour, to remove residual moisture and oxygen in the reaction tube. The pressure of the gas added into the reaction tube is (In, Ga) Sb at the growth temperature.
Is about 1 atm. Next, an electric current is passed through an electric furnace, and the temperature is raised until the (In, Ga) Sb polycrystal for the growth solution 3 is just dissolved. The temperature is In-G
Although it depends on the a-Sb solution composition X, the temperature is 675 ° C. when X = 0.5. After the temperature is raised, the partition wall 50 is lowered and the growth solution is introduced into the partition wall. Of course, the crucible 50 may be raised with the partition wall 50 fixed. After the temperature in the growth system reaches a steady state, the seed crystal is lowered, the tip of the seed crystal is immersed in the In-Ga-Sb growth solution 3, and the tip is maintained to such an extent that the tip is slightly dissolved in the growth solution. , Start pulling.
It is a matter of course to apply a known technique used in a normal LEC method, such as so-called necking, at the initial stage of pulling up the (In, Ga) Sb mixed crystal. With the progress of crystal pulling, the crucible 5
So that the height of the growth interface 23 in the partition wall 50 and therefore the volume of the growth solution 3 are always constant. A specific example of the (In, Ga) Sb mixed crystal thus pulled will be described. Composition and charge amount of In-Ga-Sb growth solution 3, X = 0.2 and 50 g, polycrystalline GaSb for raw material 4
100 g, pulling shaft orientation (111), rotation speed 20 rpm, pulling speed 5 mm / h, growth temperature 595 ° C.
As a result, a (In, Ga) Sb mixed crystal having a diameter of 25 mm, a length of 10 cm, and a mixed crystal composition x = 0.7 was obtained. (B) GaAs is used as the raw material polycrystal 4, and the growth solution 3 has a predetermined composition, for example, X = 0.35 (In,
Ga) As polycrystal is charged and (In, Ga) As mixed crystal having a predetermined solid phase composition, for example, x = 0.85 and a pulling-up axis direction, for example, (111), is used as the seed crystal 1. As a result of raising at a temperature of, for example, 1100 ° C., (In, Ga) As having a composition x = 0.85 is obtained.
A ternary mixed crystal could be grown. In this case, the reaction tube was filled with a high-purity nitrogen gas at 1.5 atm in order to prevent dissociation of arsenic. Although mixed crystals of any composition could be grown by this study, high-quality mixed crystals were obtained especially in the composition range of x ≧ 0.6, indicating that this method was effective. (C) A solution for growth 3 using GaP as the raw material polycrystal 4
A (In, Ga) P polycrystal having a predetermined liquid phase composition, for example, X = 0.2, is prepared, and a predetermined solid phase composition, for example, x = 0.75, and an axial direction, for example, as a seed crystal. Pulling was performed using (In, Ga) P having (111), and a ternary mixed crystal of In _0.25 Ga _0.75 P could be pulled. The applied gas pressure was 30 atm. Although a mixed crystal having an arbitrary composition could be grown by this method, a mixed crystal having a homogeneous composition was obtained particularly in a composition range of x ≧ 0.5, which proved that the method was effective. (D) A growth solution 3 using GaP as the raw material polycrystal 4
As a seed crystal, a predetermined solid phase composition, for example, x = 0.35, and a growth axis direction are prepared as seed crystals by preparing a predetermined liquid phase composition, for example, Ga (As, P) polycrystal having X = 0.15. For example, pulling was performed using a Ga (As, P) mixed crystal having (100), and a ternary mixed crystal of GaAs _0.65 P _0.35 was grown. In this embodiment, since the dissociation pressure of phosphorus is high, a pulling device capable of applying a gas pressure of 30 to 50 atm to the entire growth system was used. Although a mixed crystal of an arbitrary composition could be grown by this method, a high-quality mixed crystal was obtained particularly in a composition range of x ≧ 0.2, which proved that this method was effective. Of course, when a high pressure is required as in this case, it is needless to say that a mixed crystal having a uniform composition can be pulled by the present method by applying a pressure application method similar to that of a normal LEC apparatus. (E) AlAs is used as the raw material polycrystal 4, and a (Ga, Al) As polycrystal having a predetermined liquid phase composition, for example, X = 0.1, is charged as the growth solution 3 and a predetermined seed crystal is prepared. Solid phase composition, eg, x = 0.5, and axial direction,
For example, pulling was performed using (Ga, Al) As having (111), and a Ga _0.5 Al _0.5 As ternary mixed crystal could be pulled. The applied gas pressure was 3 atm. Although a mixed crystal of an arbitrary composition could be grown by this method, a high-quality mixed crystal was obtained particularly in a composition range of x ≦ 0.7, which proved that this method was effective. (F) Si is used as a raw material polycrystal, a predetermined composition, for example, GeSi polycrystal having X = 0.15, is charged as a growth solution 3, and a predetermined solid phase composition, for example, x = 0.4, is used as a seed crystal 1. , And the lifting axis direction, for example, (11
1), and pulled up at a predetermined temperature, for example, 1100 ° C., as a result of composition x = 0.
Thus, a GeSi mixed crystal of No. 4 could be grown. Although a mixed crystal having an arbitrary composition could be grown by this method, a high-quality mixed crystal was obtained particularly in a composition range of x ≧ 0.4, which proved that this method was effective.

[0007]

As a result of separating the crystal growth system of the present invention into a solute supply section and a crystal growth section by a partition wall having a through-hole, first, the raw material crystal and the solution are brought into contact with each other in the solute supply section to obtain a predetermined solution. Since a solute can be dissolved at a temperature in a saturated manner, a stable solution for supplying a solute having a predetermined composition can be obtained. Next, by appropriately setting the size, number, and arrangement of the through holes, the solute can be supplied at a constant rate from the solute supply unit to the crystal growth unit. Furthermore, in the crystal growth part, the saturation temperature (liquidus temperature determined by the composition) can be made lower than the actual temperature, preventing the composition from supercooling in the solution and the generation of dendrites due to excess solute. Now you can. Further, the amount of solution in the growth portion can be kept constant during the growth period by a mechanism such as a piston, and the growth conditions for crystals and mixed crystals can be strictly fixed. This enables not only uniformity of the mixed crystal composition but also qualitative uniformity of the crystal. By the above-described various effects of the present invention, a method for growing a binary alloy crystal such as GeSi having a predetermined composition and high quality and a ternary mixed crystal of a III-V compound has been established. An apparatus for implementing the method has been realized. The effect of the present invention is not only to enable the growth of mixed crystals other than the above-described mixed crystals, for example, mixed crystals of II-VI compounds or element semiconductors such as Ge-GaAs and compound semiconductors, but also KTP and BBO. It has a great effect on the uniform composition of oxide crystals.

[Brief description of the drawings]

FIG. 1 is an example of a sectional structural view of an apparatus used for carrying out a manufacturing method of the present invention.

FIG. 2 is an example of a sectional structural view of an apparatus used for carrying out the manufacturing method of the present invention.

FIG. 3 is an example of a sectional structural view of an apparatus used for carrying out the manufacturing method of the present invention.

FIG. 4 is an explanatory view of the invention of the prior application.

FIG. 5 is an explanatory view of the invention of the prior application.

[Explanation of symbols]

1 is a seed crystal 2 is a growth crystal 3 is a growth solution 4 is a solute supply material crystal 5 is a crucible 23 is an interface between a growth crystal and a growth solution 30 is a solute supply solution 43 is a source crystal and a solute supply solution 50 is a partition wall 51 is a through hole 60 is a piston T ₁ is a liquid phase temperature (saturation temperature) _Ta is an actual temperature

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-26594 (JP, A) JP-A-1-208389 (JP, A) JP-A-62-3097 (JP, A) JP-A 61-26 174189 (JP, A) JP-A-58-91098 (JP, A) JP-A-5-213689 (JP, A) JP-A-5-85877 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C30B 1/00-35/00

Claims (4)

(57) [Claims] 1. A plate-like solid-liquid of a growth solution and a grown crystal
Source for solute supply with a sufficiently large surface area compared to the surface area of the interface
A crucible having a material crystal fixing part at the bottom for fixing the raw material crystal, a cup-shaped partition wall provided inside the crucible so as to be relatively movable with respect to the crucible, and having a through hole ; said growth solution in the interior of the partition wall, while accommodating the solute supply unit solution in the interior of the crucible outside of the partition wall, the surface of the growth solution, holding the seed crystal so that the solid-liquid interface A seed crystal fixed chuck, and in a state where the solute supply unit solution and the growth solution are stored inside the crucible, the actual temperature of the solute supply unit solution and the growth solution is constant except near the solid-liquid interface. A heating device for heating the crucible so as to have a temperature distribution in which the actual temperature of the growth solution decreases as approaching the solid-liquid interface. 2. The semiconductor crystal manufacturing apparatus according to claim 1, wherein the raw material crystal fixing section is capable of fixing the solute supply raw material crystal having a maximum dimension substantially equal to the inner diameter of the crucible. . 3. A plate selected as a solute supply raw material crystal so as to have a sufficiently large surface area as compared with a surface area of a solid-liquid interface between a growth solution and a growth crystal in a raw material crystal fixing portion at a bottom portion of the crucible. Fixing a polycrystal of a first semiconductor in a shape of a solid; mounting a polycrystal of a mixed crystal of the first semiconductor and the second semiconductor inside the crucible; Raising the temperature until the polycrystal of the crystal is melted, and using the melted polycrystal as a solute supply section solution; and in the elevated temperature state, a cup-shaped partition wall having a through hole for the solute supply section solution. relatively moving said septum
Introducing the melted polycrystal that becomes the growth solution into the interior of a wall ; maintaining the temperature rising state in a state in which the first semiconductor polycrystal is fixed, and increasing the concentration of the solute supply solution. However, by always maintaining a substantially constant saturated concentration corresponding to the actual temperature of the solute supply unit solution, and controlling the supply amount of the solute by the through hole, the saturation temperature of the growth solution A step of bringing into a steady state having a concentration profile lower than the actual temperature of the solution; and, in the steady state, immersing a tip of the seed crystal in the growth solution, and dissolving a part of the tip in the growth solution. A step of obtaining the grown crystal by pulling up the seed crystal after a part of the tip is dissolved in the growth solution in the steady state. Method of manufacturing a crystal. 4. A step of mounting a polycrystal of the first semiconductor having a shape and a dimension not conforming to the shape of the raw crystal fixing part on the raw crystal fixing part, and heating the polycrystal of the first semiconductor. Melting the polycrystal of the first semiconductor to cast and arrange the polycrystal of the first semiconductor in the raw material crystal fixing portion; and polycrystal of the cast first semiconductor. 4. The method of manufacturing a semiconductor crystal according to claim 3, comprising a step of cooling the semiconductor crystal.