JP2569141B2 - Crystal formation method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for forming a crystal by a vapor phase method used for electronic materials and the like.

[Background Art] In recent crystal formation methods, atomic layer epitaxy (Atomic) is characterized in that the film is grown one atomic layer at a time, and the crystal growth is well controlled and the growth temperature can be kept low.
Layer Epitaxy) method (Usui, Sunakawa Jap.J.Appl.Phys)
25 (1886) 212) have been proposed.

This is a technique in which reactive raw material gases are alternately supplied without being mixed and reacted on the substrate surface to grow a thin film.

However, the above-mentioned atomic layer epitaxy method has a problem that a single crystal substrate must be used, so that the cost is high and it is difficult to increase the area.

On the other hand, experimental results on the selectivity of crystal formation on any substrate are described in Classen, J. Electrochem. Soc. Vol. 127, No.
1, Jan. 1980, 194-202. The contents described in the above documents include a substrate having a surface made of a material (SiN ₄ ) on which a film to be deposited is easily formed and a substrate having a surface made of a material (SiO ₂ ) on which a film to be deposited is difficult to be formed These two types were prepared, and the selectivity of the formation of silicon crystals on those substrates was experimentally confirmed.

By utilizing the selectivity of crystal formation described in the above-mentioned document, it is possible to selectively form a crystalline deposited film on an arbitrary substrate. However, there is no suggestion in the above-mentioned literature as to a method for forming a single crystal at a desired position on the surface of an arbitrary substrate in a deposited film to be formed. Further, the description of the above document does not suggest that a polycrystal is formed by precisely controlling the grain size of the crystal.

Therefore, there has been a strong demand for a technique for forming a single crystal at a desired position on the substrate with good controllability by using an arbitrary substrate capable of suppressing cost.

There is a selective nucleation method proposed by the present applicant as a method of forming a single crystal at a desired particle size at an arbitrary position on a substrate while keeping costs low.

In order to better understand the invention of the present application, a crystal forming method using a selective nucleation method will be described as an example.

The selective nucleation method includes, for example, conceptually, a non-nucleation surface (S _NDS ) having a low nucleation density and the non-nucleation surface (S _NDS ).
_NDS ) and has a surface area small enough to grow crystals more than a single nucleus only, and a nucleation density (ND _L ) greater than the nucleation density (ND _S ) of the non-nucleated surface (S _NDS ) growing from the nucleation surface (S _NDL) above on a substrate having a nucleation surface (S _NDL) having, over the non-nucleating surface (S _NDS) beyond further nucleation surface (S _NDL) This is a method for forming a crystal for growing a single crystal.

Although the above-mentioned crystal formation method has many excellent industrial advantages, when applied to various applications, the monocrystalline perfection, the elimination of the yield, the productivity, the mass productivity, etc. It was desired to further improve.

[Problems to be Solved by the Invention] In view of the above points, the present inventor has proposed a method for forming the above crystal,
As optimized for the creation of crystals used for the formation of high-performance, high-performance various electronic devices, optical devices, etc.,
The aim is to further improve.

That is, the present invention improves the above points to be improved,
It is a main object to provide a crystal forming method applicable to a wider range of applications.

It is another object of the present invention to provide a method for forming crystals that results in more complete single crystallinity.

Another object of the present invention is to provide a method for forming a crystal having excellent productivity and mass productivity.

Still another object of the present invention is to provide a method for forming a crystal capable of producing a high-quality crystal used for forming an electronic device, an optical device, and the like having high performance and high device characteristics.

[Means for Solving the Problems] The first gist of the present invention is to provide a non-nucleation surface (S _NDS ) having a low nucleation density and an area small enough to grow crystals from a single nucleus alone. A crystal formation processing space in which a substrate is disposed adjacent to a nucleation surface (S _NDL ) having a nucleation density (ND _L ) greater than a nucleation density (ND _S ) of a non-nucleation surface (S _NDS ) A crystal growth method in which a single crystal is selectively grown from the single nucleus by alternately supplying two or more reactive source gases, wherein one source gas is switched to another source gas. A method for forming a crystal, wherein the inside of the reaction vessel is once evacuated to 10 ⁻² Torr or less.

A second aspect of the present invention is to provide a non-nucleation surface (S _NDS ) having a low nucleation density and an area small enough to grow a crystal from a single nucleus alone, and the nucleation of the non-nucleation surface (S _NDS ) A plurality of reactive source gases are respectively placed in a crystal formation processing space in which a substrate is disposed adjacent to a nucleation surface (S _NDL ) having a nucleation density (ND _L ) greater than the density (ND _S ). A single crystal is selectively grown from the single nucleus on the nucleation surface (S _NDL ) as a starting point for crystal growth by alternately supplying the substrate and subjecting the substrate to a crystal forming process by a gas phase method. In the crystal forming method.

[Action] The inventor of the present application has continued research on the selective nucleation method. In the selective nucleation method, since the reactive raw material gas reacts in the gas phase, the following two reciprocal reactions occur. We noticed that there is a problem to be solved.

The first point is that a plurality of nuclei are generated on a micropatterned nucleation surface, and crystal growth occurs with each of the plurality of nuclei as a starting point of crystal growth. In some cases, an abnormal nucleation phenomenon occurs in which nuclei are generated on the non-nucleation surface to disturb the arrangement of crystal islands, which are independent single crystal regions.

The second point is that the crystal island does not grow on the nucleation surface among the nucleation surfaces provided with a large number of nucleation surfaces.

These two phenomena are mutually contradictory, especially when the crystal forming treatment is performed by a vapor phase method, under the parameters for forming selective nuclei. In order to explain this, the following describes two relationships between the probability of occurrence of abnormal nuclei in the formation of selective nuclei in a Si crystal and the percentage of missing nuclei.

FIG. 2 shows that in the selective nucleation, the substrate temperature was 1030 ° C.
Under the conditions of SiH ₂ Cl ₂ introduction amount of 1.2 slm, H ₂ introduction amount of 100 slm, and pressure of 1 Torr, the flow rate of HCl at the time of crystal growth of Si crystal, the probability of occurrence of abnormal nuclei and the probability of occurrence of lack are shown. FIG.

The HCl here has an action of etching a very small initial nucleus of a Si single crystal by a reaction represented by the following chemical formula.

Si + nHCl → SiCl _n ↑ + n / 2H ₂ ↑ Therefore, when the amount of HCl is increased, the nucleation is suppressed and the probability of occurrence of abnormal nuclei decreases, but at the same time, the probability of occurrence of crystal defects tends to increase. Decreasing HCl tends to facilitate nucleation, increase the probability of abnormal nucleation, and decrease the probability of missing crystals.

FIG. 3 shows an example of a result obtained when a plurality of reactive source gases are simultaneously introduced to form a crystal by the selective nucleation method. The pressure is 20 Torr, the substrate temperature is 600 ° C., and AsH ₃ / TMG is used.
The relationship between the probability of occurrence of abnormal nuclei in the H ₂ flow rate and the probability of occurrence of crystal loss when a GaAs crystal is grown under the condition of an introduction amount ratio of 60 is shown.

As is clear from FIG. 3, when the H ₂ flow rate is low, the probability of crystal loss decreases, but the probability of occurrence of abnormal nuclei tends to increase. Conversely, when the H ₂ flow rate is high, the crystal loss probability increases, and The probability of nucleation tends to decrease.

The present inventor has further studied in view of the above points, and as a result, has come to invent the crystal forming method of the present application which suppresses the generation of abnormal nuclei and reduces the probability of crystal missing.

 The crystal forming method of the present invention will be described with reference to FIG.

First, a support 1 made of high-melting glass, quartz, alumina, ceramics, or the like that can withstand high temperatures is prepared.

Non-nucleating surface made of a material having a small nucleation density on the support 1 (S _NDS) and non-nucleation surface (S _NDS) larger nucleation density than the crystal growth takes place a single nucleus as a starting point, a single crystal A nucleation surface (S _NDL ) having a surface area small enough to form 4-1 and 4-2 is provided.

As a material for forming the non-nucleation surface (S _NDS ), for example, silicon oxide is preferable if a silicon crystal is formed.

However, not limited to the above silicon oxide, a material that does not substantially cause nucleation can be used from the relationship between the material, size, arrangement, and growth conditions of the nucleation surface. Of course, the material of the support 1 may be a material forming the non-nucleation surface (S _NDS ). In this case, a film made of the material forming the non-nucleation surface (S _NDS ) is not formed on the support 1. May be.

For example, to deposit a SiO ₂ film as a material for forming a non-nucleation surface (S _NDS ) on the support 1, a normal CVD method (chemical vapor phase) using silane (SiH ₄ ) and oxygen (O ₂ ) is used. The SiO ₂ film 2 may be deposited by a deposition method).

The size of the nucleation surface (S _NDL ) is an area small enough for a crystal to grow from a single nucleus, and usually has a diameter of several μm.
m, the area is 16 μm ² or less, more preferably the diameter is 2 μm
Hereinafter, the area is 4 μm ² or less, optimally, the diameter is 1 μm or less, and the area is 1 μm ² or less.

It is desirable that the material providing the nucleation surface (S _NDL ) is amorphous.

The method for forming the nucleation surface (S _NDL ) is based on the non-nucleation surface (S _NDS )
There are a method of forming the film by ion implantation and a method of forming a thin film of a material to be a nucleation surface (S _NDL ) having a high nucleation density and patterning the thin film by photolithography. However, the method of forming the nucleation surface ( _SNDL ) in the present invention is not limited to these.

An example of a method for forming a nucleation surface (S _NDL ) will be described with reference to FIG.

First, a non-nucleation surface (S _NDS ) is provided to a desired pattern with a photoresist, for example, the surface of the SiO ₂ film 2 is masked (not shown).

For example, As ^3- ions are implanted using an ion implanter. That is, As ³⁻ ions are implanted only into the film 2 from the surface of the film 2 exposed from the mask (FIG. 1 (A)). The crystal nucleation density (ND _S ) remains small on the surface of the membrane 2 where the ions are not implanted, and this part provides a non-nucleation surface (S _NDS ). On the other hand, the regions 3-1 and 3-2 into which ions are implanted have a nucleation density (ND _L ) higher than the non-nucleation surface (S _NDS ), and this portion has a nucleation surface (S _NDL ).
give.

As an element to be implanted into the non-nucleation surface (S _NDS ) as an ion, when growing a II-VI compound crystal, an element belonging to Group II and an element belonging to Group VI of the periodic table such as S,
Elements such as Se, Te, Zn, and Cd are given.

When growing a group III-V compound crystal, an element belonging to Group III and an element belonging to Group V of the periodic table,
For example, elements such as N, P, As, Sb, Al, Ga, In and the like can be mentioned.

In order for the nucleation surface (S _NDL ) to have a sufficiently large nucleation density than the non-nucleation surface (S _NDS ), the ion implantation amount is preferably 1 × 10 ¹⁵ / cm ³ or more, preferably 1 × 10 ¹⁶ / cm ³ or more is more preferable.

After forming the nucleation surface (S _NDL ), the surface is cleaned and a crystal formation treatment is applied to the substrate.

First, the substrate is heated to a predetermined temperature. The substrate temperature is generally preferably from 200 to 950 ° C., but is not limited to this, and an appropriate temperature range may be selected depending on the type of crystal to be grown.

Then, after evacuating the inside of the reaction vessel (crystal processing space),
A plurality of source gases are simultaneously introduced into the reaction vessel and alternately supplied to the surface so that general mixing does not occur. At this time, when introducing another source gas (B) instead of the already introduced source gas (A), the source gas (B)
It is preferable that the inside of the reaction vessel is once evacuated to 10 ^-2 Torr or less before introducing the
The present invention is not limited to this. For example, the concentration of the source gas may be changed alternately.

The pressure range in the reaction vessel during the crystal formation treatment is preferably 10 ^-1 to 10 ¹ Torr when the source gas is introduced, and preferably 10 ^-5 to 10 ^-2 Torr when the introduction of the source gas is switched.

The time for introducing the source gas into the reaction vessel during the crystal forming treatment is preferably 5 seconds to 1 minute, and the time for exhausting the source gas is preferably 20 seconds to 3 minutes.

Further, it is preferable that the time for introducing the gas is shorter than the time for exhausting the gas.

The above operation is repeated until the crystal forming process is completed to grow the crystal.

As the raw material gas used in the present invention, when growing a II-VI compound, an organic metal compound containing a Group II element and an organic metal compound containing a Group VI element,
Or a hydride of a Group VI element. The specific example is as follows.

Dimethyl zinc Zn (CH ₃ ) ₂ Diethyl zinc Zn (C ₂ H ₅ ) ₂ヂ Methyl cadmium Cd (CH ₃ ) ₂ Diethyl cadmium Cd (C ₂ H ₅ ) ₂ Hydrogen selenide H ₂ Se Dimethyl selenium Se (CH ₃ ) ₂ diethyl selenium Se (C ₂ H ₅ ) ₂ dimethyl tellurium Te (CH ₃ ) ₂ diethyl tellurium Te (C ₂ H ₅ ) ₂ hydrogen sulfide H ₂ S and the like.

In the case of growing a crystal of a group III-V compound, as a source gas, an organic metal compound containing a group III element and an organic metal compound containing a group V element, or a hydride of a group V element may be used. Is raised. The specific example is as follows.

Trimethyl aluminum Al (CH ₃ ) ₃ Triethyl aluminum Al (C ₂ H ₅ ) ₃ Triisobutyl aluminum Al (i-C ₄ H ₉ ) ₃ Trimethyl gallium Ga (CH ₃ ) ₃ Triethyl gallium Ga (C ₂ H ₅ ) ₃ Trimethyl Indium In (CH ₃ ) ₃ Triethylindium In (C ₂ H ₅ ) ₃ Tripropylindium In (C ₃ H ₇ ) ₃ Tributylindium In (C ₄ H ₉ ) ₃ Phosphine PH ₃ t-Butylphosphine t-C ₄ H ₉ PH ₂ arsine AsH ₃ trimethylarsine As (CH ₃ ) ₃ triethylarsine As (C ₂ H ₅ ) ₃ diethylarsine (C ₂ H ₅ ) ₂ AsH t-butylarsine t-C ₄ H ₉ AsH ₂ trimethylantimony Sb ( CH ₃ ) ₃ tripropylantimony Sb (C ₃ H ₇ ) ₃ tributylantimony Sb (C ₄ H ₉ ) _{3 and the} like.

When the source gas is introduced into the reaction vessel, it may be diluted with a carrier gas such as H ₂ , He, or Ar as necessary.

Example 1 Example 1 A method of forming a GaAs crystal on SiO ₂ will be described as an example of the present invention with reference to FIGS. 1A to 1D.

First, an SiO ₂ film 2 was deposited on the high-melting glass support 1 by a CVD method (chemical vapor deposition method) using silane (SiH ₄ ) and oxygen (O ₂ ) as source gases at a thickness of 1000 °. The nucleation density (ND _S ) of GaAs on the SiO ₂ film is small, and the surface of this SiO ₂ film 2 provides a non-nucleation surface (S _NDS ).

Next, the surface of the SiO ₂ film 2 was masked with a photoresist so as to form 50 × 50 1 μm square regions.

As ions were implanted using an ion implanter. As
Ions are implanted only on the exposed surface (FIG. 1A). The driving amount at this time was 1 × 10 ¹⁵ pieces / cm ³ . The nucleation density (ND _S ) of GaAs remains low on the SiO ₂ surface where As ions are not implanted, and this part provides a non-nucleation surface (S _NDS ). On the other hand, regions 3-1 and 3-2 into which As ions have been implanted have a nucleation density (ND _L ) higher than the non-nucleation surface (S _NDS ), and this portion provides a nucleation surface (S _NDL ).

After the photoresist is removed, about a substrate with H ₂ atmosphere
Heat treatment was performed at 900 ° C. for about 10 minutes to clean the surface.

Then, while heating the substrate to 600 ° C.,
And evacuated to 0 ^-6 Torr trimethylgallium together with a carrier gas H ₂ (TMG) was introduced at a pressure 1Torr after 5 minutes, pressure was reduced to 5 × 10 ^-5 Torr by exhaust after 1 second. 5 × 10 ^-5 Torr
Is maintained for 5 seconds, arsine (AsH ₃ ) is introduced together with the carrier gas H ₂ to a pressure of 1 Torr, and after 1 second, the gas is exhausted.
The pressure was reduced to × 10 ⁻⁵ Torr. After this TMG with again H ₂
And a GaAs crystal was grown while repeating the above operation alternately.

As shown in FIG. 1B, the GaAs crystals 4-1 and 4-2 are A
Nucleation surface (S _NDL ) 3-1,3- formed by implanting s ions
2 only on the non-nucleated surface ( _SNDS ), ie As
No GaAs crystal was formed on the surface of the SiO ₂ where the ions were not implanted.

As the growth is further continued, as shown in FIG.
The crystals 4-1 and 4-2 came into contact with each other. At that stage, the growth was stopped, the surface was polished, and the grain boundaries 5 were etched to obtain GaAs 4-1 and 4-2 crystals as shown in FIG. 1 (D).

When 50 × 50 single crystal islands were grown in this manner, no crystal was missing and abnormal nucleus growth was observed for 10 crystals.

FIG. 4 shows abnormal nucleation of the ultimate pressure in the reaction vessel when using a plurality of different source gases and switching between the introduction of one source gas and the introduction of the other source gas in the crystal formation process by the vapor phase method. The relationship between the probability and the occurrence probability of crystal loss is shown.

The abnormal nucleation probability has a critical point at 10 ^-2 Torr, and the abnormal nucleation probability is kept low at ultimate pressures below this pressure, and tends to increase at ultimate pressures above this pressure. There is.

In addition, the probability of occurrence of crystal vacancies has a critical point at 2.5 × 10 ⁻⁵ Torr, and the probability of occurrence of crystal vacancies is kept low at ultimate pressures above this pressure. The probability of occurrence of crystal defects tends to increase beyond the probability of occurrence of abnormal nuclei when the ultimate pressure is a constant pressure of 1 × 10 ⁻⁵ Torr or more.

As is clear from FIG. 4, the probability of occurrence of abnormal nuclei and the probability of occurrence of crystal defects were able to be suppressed low by the crystal forming method of the present invention.

Compared with the abnormal nucleation probability and the crystal missing probability of the optimum values (H ₂ flow rate of 360 sccm) when different kinds of source gases are simultaneously introduced as shown in FIG. 3, the present invention has the controllability of selective single crystal growth. It can be seen that is improved.

Example 2 A method for forming a ZnSe crystal will be described as another example of the present invention with reference to FIGS. 5 (A) to 5 (D).

First, an SiO ₂ film 7 was deposited on the alumina support 6 by a CVD method using SiH ₄ and O ₂ as source gases at a thickness of 1000 °.

Next, using SiH ₄ and NH ₃ as source gases, a SiN _x film was deposited at 300 ° by a plasma CVD method. SiH ₄ and NH ₃
Supply ratio is 2: 1, reaction pressure is 0.15 Torr, high frequency output is 1.6
× 10 ^-2 W / cm ² .

Further, the SiN _X film was patterned into a 1 μm square to form nucleation surfaces (S _NDL ) 8-1, 8-2 (FIG. 5 (A)).

After thoroughly cleaning the substrate thus formed, the substrate was heat-treated at about 900 ° C. for 10 minutes in an H ₂ atmosphere to clean the surface.

Then, while heating the substrate to 450 ° C.,
After exhausting to 0 ^-6 Torr, 5 minutes later, diethyl zinc (Zn (C ₂ H ₅ ) ₂ ) was introduced together with carrier gas H ₃ to a pressure of 1 Torr, and after 1 second, the pressure was reduced to 10 ^-5 Torr. 10 ^-5 Torr
Was maintained for 5 seconds, diethyl selenium (Se (C ₂ H ₅ ) ₂ ) was introduced together with the carrier gas H ₂ to a pressure of 1 Torr, and after 1 second, the pressure was reduced to 10 ⁻⁵ Torr. After this, flow H ₂ and diethyl zinc again, and repeat the above operation alternately.
Grow ZnSe crystals.

As shown in FIG. 5 (B), the ZnSe single crystals 9-1, 9-2
Grows from the nuclei formed on the nucleation surfaces (S _NDL ) 8-1 and 8-2 formed of SiN _X , and grows on the non-nucleation surface (S _NDS ), that is, on the surface of the SiO ₂ film 7. The crystal grew until. When the crystal growth treatment was further continued, as shown in FIG. 5C, the ZnSe crystals 9A-1 and 9A-2 collided with each other and grew largely until a polycrystal was formed. When the surface of the formed crystal is polished and the grain boundaries 10 are etched, Zn as shown in FIG.
Se single crystals 9B-1 and 9B-2 were obtained.

Also in the present invention, the nucleation probability and the crystal missing probability were suppressed to a low value as in Example 1.

According to the present invention, the following effects can be obtained.

Since a reactive gas does not meet in the gas phase, a chemical reaction in the gas phase does not occur, and it is possible to provide a crystal forming method in which an addition reaction in the gas phase such as reducing crystallinity is suppressed. it can.

Since only one gas reaches the substrate on which the nucleation surface (S _NDL ) and the non-nucleation surface (S _NDS ) are arranged, the reaction is suppressed and the mobility of the source gas on the substrate surface is large. The gas molecules that have moved on the substrate surface form a nucleation surface (S
_NDL ) can provide a crystal formation method that forms a thin adsorption layer of several molecular layers or less by being caught on it and forms a crystal by chemical reaction when another reactive gas is supplied. .

Since crystal growth proceeds by the reaction between adatoms having a thickness of several atomic layers or less, the growth rate is determined by the shape, density, and arrangement of the nucleation surface (S _NDL ) pattern as in the conventional selective nucleation. Can be provided without being influenced by the crystal formation method.

[Brief description of the drawings]

1 (A) to 1 (D) are process diagrams showing a crystal forming method by a selective nucleation method of the present invention. FIG. 2 is a graph showing the relationship between the HCl flow rate, the probability of occurrence of abnormal nuclei, and the probability of occurrence of crystal defects in the growth of Si single crystal by the selective nucleation method. FIG. 3 is a graph showing the relationship between the H ₂ flow rate and the probability of occurrence of abnormal nuclei and crystal defects in GaAs single crystal growth by the selective nucleation method. FIG. 4 is a graph showing the relationship between the probability of occurrence of abnormal nuclei of the ultimate pressure in the exhausted reaction chamber and the probability of occurrence of crystal loss when switching to a different kind of source gas in the present invention. 5 (A) to 5 (D) are process cross-sectional views showing Embodiment 2 of the crystal forming method according to the present invention. 1 ...... support, 2 ...... SiO ₂ film, 3-1, 3-2 ...... nucleation surface, 4-1, 4-2 ...... monocrystalline, 5 ...... grain boundary, 6 ...... alumina support , 7 ...... SiO ₂ film, 8-1, 8-2 ...... nucleation surface, 9-1,9-2,9A-1,9A-2,9B-1,9B -2 ...... ZnSe crystal, 10 ... grain boundaries.

Claims (38)

(57) [Claims] 1. A non-nucleated surface having a low nucleation density (S _NDS )
And a nucleation surface (S) having an area small enough for crystal growth than a single nucleus alone and having a nucleation density (ND _L ) greater than the nucleation density (ND _S ) of the non-nucleation surface (S _NDS ). Crystal growth in which a single crystal is selectively grown from the single nucleus by alternately supplying two or more reactive source gases to a crystal formation processing space in which a substrate disposed adjacent to _NDL is disposed. A method for forming a crystal, comprising: once changing one source gas to another source gas, evacuating the reactor to 10 ⁻² Torr or less. 2. The method according to claim 1, wherein the temperature range of the substrate is 200 ° C. to 950 ° C. 3. The pressure range in the reaction vessel exhausted when switching the source gas to a different source gas is 10 ⁻² Torr to
The method of claim 1, wherein the pressure is 10 ^-5 Torr. 4. The crystal forming method according to claim 1, wherein the pressure range at the time of introducing the source gas is 10 ^-1 Torr to 10 Torr. 5. The crystal forming method according to claim 1, wherein the time for introducing the source gas is from 5 seconds to 1 minute. 6. The crystal forming method according to claim 1, wherein the time for exhausting the source gas is from 20 seconds to 3 minutes. 7. A substrate temperature range of 200 ° C. to 950 ° C.,
2. The crystal forming method according to claim 1, wherein a pressure range in the reaction vessel exhausted when the source gas is switched to a different type of source gas is 10 ⁻² Torr to 10 ⁻⁵ Torr. 8. A substrate temperature range of 200 ° C. to 950 ° C.,
2. The crystal forming method according to claim 1, wherein the pressure range at the time of introducing the raw material gas is 10 ^-1 Torr to 10 Torr. 9. The substrate temperature range is from 200 ° C. to 950 ° C.,
2. The crystal forming method according to claim 1, wherein the time period for introducing the source gas is from 5 seconds to 1 minute. 10. The crystal forming method according to claim 1, wherein the temperature range of the substrate is 200 ° C. to 950 ° C., and the time period for exhausting the source gas is 20 seconds to 3 minutes. 11. A pressure range in the reaction vessel exhausted when switching the source gas to another source gas is 10 ⁻² Torr to 10 ⁻² Torr.
10 ^-5 Torr, and the pressure range when the source gas is introduced is 10 ^-1 To
2. The method according to claim 1, wherein the pressure is from rr to 10 Torr. 12. A pressure range in the reaction vessel exhausted when switching the source gas to another source gas is 10 ⁻² Torr to 10 ⁻² Torr.
10 ^-5 Torr and the time range for exhausting the source gas is 20
2. The crystal forming method according to claim 1, wherein the time is from 2 seconds to 3 minutes. 13. A pressure range at the time of introduction of a source gas is 10 ^-1 Torr.
2. The crystal forming method according to claim 1, wherein the pressure is from 10 Torr to 10 Torr, and the time for introducing the source gas is from 5 seconds to 1 minute. 14. The crystal forming method according to claim 1, wherein the area of the nucleation surface is 16 μm ² or less. 15. The method according to claim 1, wherein the source gas is selected from an organometallic compound containing a Group II element and an organometallic compound containing a Group VI element or a hydride of a Group VI element. . 16. The crystal forming method according to claim 1, wherein the source gas is selected from an organic metal compound containing a group III element and an organic metal compound containing a group V element or a hydride of a group V element. . 17. The crystal forming method according to claim 1, wherein the nucleation surface is formed by ion implantation, and the amount of implanted ions is 1 × 10 ¹⁵ / cm ³ or more. 18. The nucleation surface is formed by ion implantation, and the elements providing the implanted ions are group II, II
The crystal forming method according to claim 1, wherein the crystal is an element selected from Group I, Group V, and Group VI. 19. The method according to claim 1, wherein the material providing the nucleation surface is amorphous. 20. Non-nucleated surface (S _NDS ) with low nucleation density
And a nucleation surface (S) having an area small enough for crystal growth than a single nucleus alone and having a nucleation density (ND _L ) greater than the nucleation density (ND _S ) of the non-nucleation surface (S _NDS ) _NDL ) and a plurality of reactive source gases are alternately supplied to a crystal formation processing space in which a substrate disposed adjacent to the substrate is disposed, and a crystal formation process is performed on the substrate by a gas phase method, A crystal forming method characterized in that a single crystal is selectively grown on a nucleation surface ( _SNDL ) using a single nucleus as a starting point of crystal growth. 21. The method for forming a crystal according to claim 20, wherein the substrate temperature range is from 200 ° C. to 950 ° C. 22. The crystal forming method according to claim 20, wherein the pressure in the reaction vessel exhausted when the source gas is switched to a different source gas is 10 ⁻² Torr to 10 ⁻⁵ Torr. 23. The pressure range at the time of introduction of the source gas is 10 ^-1 Torr.
21. The crystal forming method according to claim 20, wherein the pressure is from 10 to 10 Torr. 24. The crystal forming method according to claim 20, wherein the time for introducing the source gas is 5 seconds to 1 minute. 25. The method of forming a crystal according to claim 20, wherein the time for exhausting the source gas is 20 seconds to 3 minutes. 26. A temperature range of the substrate is 200 ° C. to 950 ° C., and a pressure range in the reaction vessel exhausted when the source gas is switched to a different source gas is 10 ⁻² Torr to 10 ⁻⁵ Torr.
21. The crystal forming method according to claim 20, wherein 27. The temperature range of the substrate is 200 ° C. to 950 ° C., and the pressure range at the time of introducing the source gas is 10 ⁻¹ Torr to 10 Torr.
21. The crystal forming method according to claim 20, wherein 28. The crystal forming method according to claim 20, wherein the temperature range of the substrate is 200 ° C. to 950 ° C., and the time period for introducing the source gas is 5 seconds to 1 minute. 29. The crystal forming method according to claim 20, wherein the substrate temperature range is from 200 ° C. to 950 ° C., and the time period for exhausting the source gas is from 20 seconds to 3 minutes. 30. A pressure range in the reaction vessel exhausted when switching the source gas to another source gas is 10 ⁻² Torr to
10 ^-5 Torr, and the pressure range when the source gas is introduced is 10 ^-1 To
21. The method according to claim 20, wherein the pressure is rr to 10 Torr. 31. A pressure range in the reaction vessel exhausted when switching the source gas to another source gas is 10 ⁻² Torr to
10 ^-5 Torr and the time range for exhausting the source gas is 20
21. The crystal forming method according to claim 20, wherein the time is from 2 seconds to 3 minutes. 32. A pressure range at the time of introduction of the source gas is 10 ^-1 Torr.
21. The crystal forming method according to claim 20, wherein the pressure is from 10 Torr to 10 Torr, and the time for introducing the source gas is from 5 seconds to 1 minute. 33. The crystal forming method according to claim 20, wherein the area of the nucleation surface is 16 μm ² or less. 34. The crystal forming method according to claim 20, wherein the source gas is selected from an organometallic compound containing a Group II element and an organometallic compound containing a Group VI element or a hydride of a Group VI element. . 35. The crystal forming method according to claim 20, wherein the source gas is selected from an organometallic compound containing a Group III element and an organometallic compound containing a Group V element or a hydride of a Group V element. . 36. The crystal forming method according to claim 20, wherein the nucleation surface is formed by ion implantation and the amount of ion implantation is 1 × 10 ¹⁵ / cm ³ or more. 37. The nucleation surface is formed by ion implantation, and the elements providing the implanted ions are group II, II
2. The element selected from Group I, Group V, and Group VI.
0. The crystal forming method according to 0. 38. The crystal forming method according to claim 20, wherein the material providing the nucleation surface is amorphous.