JP2001313254A - Method for growing nitride based iii-v compound semiconductor layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for growing a nitride based III-V compound semiconductor layer which can produce a nitride based III-V compound semiconductor substrate having good crystallinity and no surface roughness nor crack with high productivity. SOLUTION: A thin GaN layer 2 is grown rate of 4 μm/h or less on a c-face sapphire substrate 1 by MOCVD or MBE, and then a sufficiently thick GaN layer 3 is grown on the GaN layer 2 at a rate higher than 4 μm/h but not higher than 200 μm/h by hydride VPE. Subsequently, the c-face sapphire substrate 1 is removed by etching or lapping to obtain a GaN substrate comprising the GaN layers 2, 3. Finally, the surface of the GaN layer 2 or 3 being used as a growth surface is etched or polished to bring about a high quality surface state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
The present invention relates to a method for growing a group-V compound semiconductor layer, which is particularly suitable for manufacturing a semiconductor device using a nitride-based group III-V compound semiconductor, for example, a substrate for a semiconductor laser.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for the development of semiconductor lasers emitting short-wavelength green, blue, or ultraviolet light, for example, due to demands for higher recording and reproducing densities and higher resolution for optical disks and magneto-optical disks. .

[0003] Materials used for manufacturing a semiconductor light emitting device capable of emitting light at such a short wavelength include GaN and AlG.
Nitride III-V represented by aN, GaInN, etc.
Group semiconductors are known to be suitable (eg, Jpn. J. Appl. Phys. 30 (1991) L1998).

Heretofore, nitride-based III-V compound semiconductor layers have been grown by metal organic chemical vapor deposition (MOCVD).
It is performed by a molecular beam epitaxy (MBE) method. In this case, sapphire (Al ₂
O ₃ ) substrates or silicon carbide (SiC) substrates are mainly used.

[0005]

However, the nitride-based II on the sapphire substrate or the silicon carbide substrate described above.
When an IV group compound semiconductor layer is grown, there is a problem that a defect is generated or a crack is generated due to a difference in lattice constant or thermal expansion coefficient between them.
Further, when a nitride-based III-V compound semiconductor layer is grown in multiple layers on such a sapphire substrate or a silicon carbide substrate to produce, for example, a semiconductor laser, it is difficult to form the cavity end face by cleavage. There is a problem.

[0006] These problems can be solved if a nitride III-V compound semiconductor substrate can be obtained. That is, when a nitride-based III-V compound semiconductor layer is grown on a nitride-based III-V compound semiconductor substrate, the lattice constant and the thermal expansion coefficient of the nitride-based III-V compound semiconductor layer match, so that the defect is reduced. There is no problem such as generation or cracking. In the case of manufacturing a semiconductor laser, for example, the cavity end face can be formed by cleavage. In addition to these advantages, the advantage that an electrode can be formed on the back surface of the substrate is combined, so that a highly reliable semiconductor device, for example, a semiconductor laser can be manufactured with a high yield.

However, in order to manufacture a nitride III-V compound semiconductor substrate, a method generally used for manufacturing a Si substrate or a GaAs substrate cannot be used due to a high vapor pressure of nitrogen. .

As a method for growing GaN, a hydride vapor phase epitaxy (VPE) method using hydride (hydride) as a raw material is known in addition to the MOCVD method and the MBE method. According to the hydride VPE method,
Since a GaN layer having a thickness of several to several hundred μm can be grown in one hour, it is considered to be one of effective methods for manufacturing a GaN substrate. Regarding the manufacture of the GaN substrate, there has been a report that a GaN layer is grown on a sapphire substrate, a GaAs substrate, or the like by a hydride VPE method. However, the GaN substrate obtained by this method is:
Since the crystallinity and the surface condition were poor, and the GaN layer grew obliquely instead of perpendicularly to the substrate, the quality was insufficient for use as a substrate.

Accordingly, an object of the present invention is to provide a high-quality nitride-based material having good crystallinity without surface roughness or cracks.
It is an object of the present invention to provide a method for growing a nitride-based III-V compound semiconductor layer capable of manufacturing a -V group compound semiconductor substrate with high productivity.

[0010]

Means for Solving the Problems The present inventor has made intensive studies to achieve the above object. As a result, high-quality nitride III-V having good crystallinity without surface roughness or cracks
In order to manufacture a Group III compound semiconductor substrate with high productivity, first, it is necessary to suppress the occurrence of surface roughness and cracks on a sapphire substrate or the like generally used for growing a nitride III-V compound semiconductor. After growing a nitride-based III-V compound semiconductor layer thinly at a growth rate as small as possible, the nitride-based III-V compound semiconductor layer is grown thereon at a higher growth rate.
The inventors have concluded that it is effective to grow the group IV compound semiconductor layer thickly, and have devised the present invention.

That is, in order to achieve the above object, a method for growing a nitride-based III-V compound semiconductor layer according to the present invention comprises a first vapor-phase growth method on a substrate at a first predetermined growth rate. the first _{B w Al x Ga y in z} N layer (where, 0 ≦ w ≦ 1,0 ≦ x ≦ 1,0 ≦ y ≦ 1,0 ≦ z ≦
1, w + x + y + z = 1) and growing a first _{B w Al x Ga y In z} N is greater than the first predetermined growth rate by the second vapor deposition on the layer a second growth rate in a second _{B w Al x Ga y in z} N layer (where, 0 ≦ w ≦
1, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, w + x + y
+ Z = 1).

[0012] Here, the first _{B w Al x Ga y In z} N
Layer and the second _{B w Al x Ga y In z} N layer, from the viewpoint of surface roughness or cracks without crystallinity also intended good quality, preferably, a first predetermined growth rate 4 [mu] m / h
And the second predetermined growth rate is greater than 4 μm / h and 200 μm / h or less.

In the present invention, a metal organic chemical vapor deposition method, a molecular beam epitaxy method, or the like is used as the first vapor phase growth method, and a hydride vapor phase epitaxy method, an organic metal A chemical vapor deposition method or the like is used. To give a specific example of a combination of the first vapor deposition method and the second vapor deposition method, the first vapor deposition method is a metal organic chemical vapor deposition method, and the second vapor deposition method Is a hydride vapor phase epitaxy method, the first vapor phase epitaxy method and the second vapor phase epitaxy method are metal organic chemical vapor deposition methods respectively, and the first vapor phase epitaxy method is a molecular beam epitaxy method. Where the second vapor phase epitaxy is hydride vapor phase epitaxy, the first vapor phase epitaxy is molecular beam epitaxy, and the second vapor phase epitaxy is metalorganic chemical vapor phase epitaxy. And so on.

In the present invention, the first B _w Al _x Ga
The thickness of the _y an In _z N layer is preferably no occurrence of surface roughness or cracks, good crystallinity may be obtained. Moreover chosen thickness not take time to grow. This first B _w Al _x
The thickness of Ga _y In _z N layer, for example 0.3 to specifically
10 μm, preferably 3 ± 2 μm or 1-5
μm.

In the present invention, the first B _w Al _x G
a _y In _z N layer and the second _{B w Al x Ga y In z} N
The layers may be n-type or p-type as needed. In this case, the n-type impurity is typically IV
At least one element selected from the group consisting of C, Si, Ge, and Sn that are group elements and S, Se, and Te that are group VI elements is used. Group elements C, Si, Ge and Sn
And Group II elements Be, Mg, Ca, Zn and Cd
At least one element selected from the group consisting of As a raw material for these n-type impurities and p-type impurities, any of simple substances, organic compounds and hydrides may be used.

In the present invention, as a raw material of group III elements B, Al, Ga and In, any of a simple substance or an organometallic compound containing these group III elements may be used.

In the present invention, in particular, the hydride gas in the hydride vapor phase epitaxy method includes:
HCl, HF, HBr, HI, or the like can be used.

Further, the first B This hydride vapor phase epitaxy _w Al _x Ga _y In _z N layer or the second
B _w Al _x Ga _y In _z As N material when N layer is grown, other ammonia, hydrazine, dimethyl hydrazine, formula N ₂ R, such as monomethyl hydrazine
₄ A hydrazine-based raw material represented by (where R is H or an alkyl group), an organic amine, or the like can be used. Of these, specific examples of organic amines include primary amines such as propylamine, isopropylamine, butylamine, isobutylamine, tertiarybutylamine, and secondary butylamine. Propylamine, diisopropylamine, dibutylamine, diisobutylamine, ditertiarybutylamine, secondary butylamine, etc., as tertiary amines, tripropylamine, triisopropylamine, tributylamine, triisobutylamine,
Tritertiary butylamine, trisecondary butylamine,
Examples include triallylamine, triethylamine, diisopropylmethylamine, dipropylmethylamine, dibutylmethylamine, diisobutylmethylamine, disecondary butylmethylamine, and ditertiarybutylmethylamine.

In the present invention, the second B_wAl_xG
a_yIn_zWhen growing the N layer, this second B_wAl
_xGa_yIn_zDifference in thermal expansion coefficient between N layer and substrate
This second B_wAl_xGa_yIn_zDefects occur in the N layer
The purpose of preventing formation or cracking
And preferably at least the second B_wAl_xGa_yIn
_zWhen growing the N layer, the thickness of the substrate
Of B_wAl_xGa_yIn_zThe thickness is not more than the thickness of the N layer. Concrete
Specifically, the second B_wAl_xGa_yIn_zThicker than N layer
When a substrate is used, the first B_wAl_xGa_yIn_z
After growing the N layer, a second B_wAl_xGa_yIn_zN
Before growing the layer, etch the substrate from its backside
By lapping or lapping its thickness
B_wAl _xGa_yIn_zThe thickness may be equal to or less than the thickness of the N layer.
Or the second B from the beginning_wAl_xGa_yIn_zN layer
May be used. Typically,
At least the second B_wAl_xGa_yIn_zGrowing N layer
When the thickness of the substrate is, for example, 400 μm or less,
Preferably, it is 200 μm or less.

In the present invention, the nitride III-V
To obtain a substrate made of only group compound semiconductor, after growing the second _{B w Al x Ga y In z} N layer, the substrate is removed by a substrate etching or lapping. At this time, in order to prevent or damage to the second _{B w Al x Ga y In z} N layer surface occurs, the contamination of or cause, preferably, the second B prior to removing the substrate _w Al
The surface of the _x Ga _y In _z N layer previously covered with a protective film.

In the present invention, the first B _w Al _x G
a _y In _z N layer or the second _{B w Al x Ga y In z} N
A good surface condition is obtained by polishing or etching the surface of the layer. Here, the first B _w Al _x G
a _y In _z N layer or the second _{B w Al x Ga y In z} N
Which surface of the layer is to be polished or etched depends on which surface of the nitride-based III-
It depends on whether the group V compound semiconductor layer is grown.

In the present invention, for example, a sapphire substrate, a silicon carbide substrate or a magnesium aluminum spinel substrate is used as the substrate.

According to the present invention configured as described above,
For example, a first predetermined growth is performed on a substrate by a first vapor deposition method.
First B at a growth rate, preferably 4 μm / h or less._w
Al_xGa_yIn_zN layer (however, 0 ≦ w ≦ 1, 0 ≦ x
≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, w + x + y + z = 1)
Is grown, this first B
_wAl_xGa_yIn_zN layer has no surface roughness or crack
Good crystal quality can be obtained. Soshi
This first B_wAl_xGa_yIn_zThe second on the N layer
By a vapor phase growth method, a second growth rate greater than a first predetermined growth rate
2 predetermined growth rate, preferably greater than 4 μm / h
And the second B at a growth rate of 200 μm / h or less._wAl_x
Ga_yIn_zN layer (however, 0 ≦ w ≦ 1, 0 ≦ x ≦ 1,
Growing 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, w + x + y + z = 1)
The first B_wAl_xG
a_yIn_zCrystal without surface roughness and cracks as in the N layer
High quality second B with good properties_wAl_xGa_yIn_zN layer
It can be grown to a sufficient thickness in a short time. Further
After this, these first B_wAl_xGa_yIn_zN
Layer and second B_wAl_xGa_yIn_zFor N layer growth
By removing the substrate,_wAl_xGa_yIn
_zHigh production of N substrates, specifically, for example, GaN substrates
It can be manufactured by the nature.

[0024]

Embodiments of the present invention will be described below with reference to the drawings.

First, G according to the first embodiment of the present invention will be described.
A method for manufacturing an aN substrate will be described.

FIG. 1 is a sectional view showing a method of manufacturing a GaN substrate according to the first embodiment in the order of steps.

In the first embodiment, first, as shown in FIG. 1A, a c-plane sapphire substrate 1 having a thickness of, for example, 450 nm is placed in a reaction tube of an MOCVD apparatus (not shown).
, H ₂ as a carrier gas in the reaction tube.
By flowing a mixed gas of N ₂ and N ₂ and performing a heat treatment at, for example, 1050 ° C. for 20 minutes, the surface of the c-plane sapphire substrate 1 is thermally cleaned. Next, after lowering the substrate temperature to, for example, 510 ° C., ammonia (NH ₃ ) as an N material and trimethylgallium (TMG, Ga (CH ₃ ) ₃ ) as a Ga material are supplied into the reaction tube, and c-plane sapphire is supplied. A GaN buffer layer (not shown) is grown on the substrate 1. Next, the supply of TMG into the reaction tube is stopped, and while the supply of NH ₃ is kept as it is, the growth temperature is raised to, for example, about 1000 ° C., and T is again introduced into the reaction tube.
By supplying MG, the GaN layer 2 is grown at a growth rate of 4 μm / h or less. The thickness of the GaN layer 2 is, for example, 3 μm. The GaN layer 2 thus grown at a growth rate of 4 μm / h or less by the MOCVD method is of good quality, in which the occurrence of surface roughness and cracks is suppressed and the crystallinity is good.

Following the growth of the GaN layer 2, for example, diethyl sulfur (DES, S (C
_An S film (not shown) is grown on the GaN layer 2 using ₂ H ₅ ) ₂ ) as a raw material to cover the surface of the GaN layer 2. Thereafter, the c-plane sapphire substrate 1 is taken out of the reaction tube. Here, the reason for covering the surface of the GaN layer 2 with the S film before taking out the c-plane sapphire substrate 1 from the reaction tube is as follows.
When the c-plane sapphire substrate 1 is taken out of the reaction tube and exposed to the atmosphere with the surface of the GaN layer 2 exposed, the GaN layer 2
This is to prevent the surface of the GaN layer from being contaminated, which may adversely affect the subsequent growth of the GaN layer on the GaN layer 2 by the hydride VPE method.

Next, the c-plane sapphire substrate 1 is wrapped from the back side so that the thickness of the c-plane sapphire substrate 1 is set to be equal to or less than the thickness of the GaN layer grown by the hydride VPE method in the next step. deep. This is c
This is to prevent a defect or crack from being generated in the GaN layer due to a difference in thermal expansion coefficient between the planar sapphire substrate 1 and the GaN layer. Thereafter, as shown in FIG. 1B, G on the c-plane sapphire substrate 1
A GaN layer 3 having a sufficient thickness (for example, 200 μm) is homoepitaxially grown on the aN layer 2 by a hydride VPE method.

The growth of the GaN layer 3 is specifically performed as follows using a hydride VPE apparatus shown in FIG. That is, the c-plane sapphire substrate 1 on which the GaN layer 2 has been grown is placed on a susceptor 12 installed in a quartz glass reaction tube 11 of a hydride VPE apparatus shown in FIG. The upstream part of the reaction tube 11 is separated into upper and lower parts by a partition plate 13, and a boat 15 containing Ga 14 as a single raw material is placed on the partition plate 13 in the upper part thereof. The reaction tube 11 where this boat 15 is placed
In the upper part of the partition plate 13, H
In addition to supplying Cl gas, N ₂ gas can be supplied as a carrier gas via the pipe 17. Further, the lower portion of the partition plate 13 of the reaction tube 11 can be supplied with NH ₃ gas via a pipe 18 and N ₂ gas as a carrier gas via a pipe 19. ing. Here, the reaction tube 11 is heated by a heater 20 installed outside so that a required temperature gradient is provided in the longitudinal direction. Reference numerals 21 to 24 denote mass flow controllers for controlling the gas flow rate.

Prior to the growth of the GaN layer 3, first, the c-plane sapphire substrate 1 is heated to the growth temperature in the reaction tube 11, whereby the S film on the surface of the GaN layer 2 is evaporated and removed. At this time, the GaN layer 2
Is prevented from being desorbed in the reaction tube 11.
₃ Let the gas flow.

After removing the S film in this manner, HCl gas and N ₂ gas as a carrier gas are supplied to the upper portion of the partition plate 13 of the reaction tube 11, and the lower portion of the partition plate 13 of the reaction tube 11 is supplied. An NH ₃ gas and an N ₂ gas as a carrier gas are supplied to the side portion. At this time,
In the upper part of the partition plate 13 of the reaction tube 11, H
The reaction between Cl and Ga 14 produces GaCl, and the GaCl and NH ₃ supplied to the lower portion of the partition plate 13 of the reaction tube 11 merge above the susceptor 12, thereby forming the c-plane sapphire substrate 1. G on the upper GaN layer 2
The aN layer 3 grows. The growth rate of this GaN layer 3 is 4
The size is selected as large as possible within a range larger than 200 μm / h and 200 μm / h or less unless there is another trouble. As an example of typical growth conditions at this time, HCl flow rate is 20 μmol / min, NH ₃ flow rate is 1 SLM, N ₂ flow rate is 0.5 SLM, temperature near Ga 14 in boat 15 is 800 ° C., susceptor 12 The temperature of the portion of the c-plane sapphire substrate 1 placed thereon is 980 ° C. The gas supplied into the reaction tube 11 is finally sent to the abatement apparatus to perform the abatement process.

Next, after taking out the c-plane sapphire substrate 1 on which the GaN layer 3 has been grown in this manner from the reaction tube 11, as shown in FIG.
An SiO ₂ film 4 is formed on the layer 3 to cover the surface of the GaN layer 3.

Next, as shown in FIG. 1D, c-plane sapphire
A substrate 1 is etched, for example, by wet etching.
Removed. This wet etching is performed, for example, by using H_Three
PO _Four-H_TwoSO_FourSystem etchant (eg, H_ThreeP
O_Four: H_TwoSO_Four= 1: 1) at 285 ° C.
Further, for example, wet using an HF-based etchant
SiO by etching method_TwoEtch and remove film 4
You.

Thereafter, when the surface of GaN layer 3 is used as a growth surface, the surface of GaN layer 3 is
When the surface of the N layer 2 is used as a growth surface, the Ga
The surface of the N layer 2 is flattened by performing etching or polishing using a vapor phase etching method, a liquid phase chemical etching method, a mechanical chemical polishing method, or the like, and has a good surface state.

As described above, as shown in FIG.
A single crystal GaN substrate comprising a thin GaN layer 2 grown by the VD method and a sufficiently thick GaN layer 3 grown thereon by the hydride VPE method is manufactured.

As described above, according to the first embodiment, 4 μm is formed on the c-plane sapphire substrate 1 by MOCVD.
By growing the thin GaN layer 2 at a growth rate of m / h or less, the generation of surface roughness and cracks of the GaN layer 2 can be suppressed, and the crystallinity can be improved. Then, a sufficiently thick GaN layer 3 serving as a main part of the substrate is grown on the high-quality GaN layer 2 at a growth rate of more than 4 μm / h and 200 μm / h or less by a hydride VPE method. The generation of surface roughness and cracks in the GaN layer 3 can be suppressed, and the crystallinity can be improved. Thereby, a high-quality GaN substrate can be obtained by removing the c-plane sapphire substrate 1 thereafter. Since the thick GaN layer 3 constituting the main part of the GaN substrate is grown by the hydride VPE method having a very high growth rate,
The time required to grow a 00 μm GaN layer 3 is:
Although it depends on the growth rate used, it takes only a few hours, for example, several hours, and the productivity is high. Furthermore, this GaN substrate
Depending on the diameter of the c-plane sapphire substrate 1 to be used, for example, 2
It can have a large area of an inch diameter or more.

The GaN substrate thus manufactured is
It is suitable for use in the manufacture of various semiconductor devices using a nitride III-V compound semiconductor. That is, the nitride II is formed on the GaN substrate by MOCVD or the like.
By growing an IV group compound semiconductor layer, various semiconductor devices can be manufactured. In particular, this Ga
When a nitride-based III-V compound semiconductor layer is grown on an N substrate to produce a semiconductor laser, the nitride-based III-V compound semiconductor layer is cleaved together with a GaN substrate to form a semiconductor laser. Can easily be formed. Further, the GaN layers 2 and 3 are
N type GaN substrate can be obtained.
If the layers 2 and 3 are p-type, a p-type GaN substrate can be obtained. In these cases, there is an advantage that an n-type electrode or a p-type electrode can be formed on the back surface of the GaN substrate. it can. This makes it possible to manufacture a highly reliable semiconductor laser with a high yield.

Next, a second embodiment of the present invention will be described.

In the second embodiment, the GaN layer 3 constituting the main part of the GaN substrate is
As shown in FIG. 3, a hydride VPE apparatus for growing by the method is used. Other points are the same as in the first embodiment, and a description thereof will be omitted.

As shown in FIG. 3, this hydride VP
In the E apparatus, a c-plane sapphire substrate 1 on which a GaN layer 2 has been grown is placed on a susceptor 32 installed in a reaction tube 31 made of quartz glass. Is separated into upper and lower parts. In this case, TMG 34 which is an organometallic compound is used as a Ga raw material, and N ₂ gas is supplied as a carrier gas through a pipe 36 into a bubbler 35 containing the TMG 34, and TMG generated by bubbling thereby is generated.
The gas is supplied to the upper part of the partition plate 33 of the reaction tube 31 through a pipe 37, and N ₂ gas is supplied through a pipe 38.
The gas is supplied as a carrier gas. Reference numeral 39 indicates a bypass pipe. Switching of the TMG gas supplied from the bubbler 35 between the pipe 37 and the bypass pipe 39 is as follows.
This is performed by opening and closing the valves 40 and 41. Further, HCl gas is supplied to the upper part of the partition plate 33 of the reaction tube 31 through a pipe 42, and N gas is supplied through a pipe 43.
_Two gases can be supplied as carrier gas. On the other hand, the lower portion of the partition plate 33 of the reaction tube 31 can be supplied with the NH ₃ gas via the pipe 44 and the N ₂ gas as the carrier gas via the pipe 45. ing. Here, the reaction tube 31 is heated by a heater 46 provided outside so that a required temperature gradient is provided in the longitudinal direction. Reference numerals 47 to 52 denote mass flow controllers for controlling the gas flow rate.

According to the second embodiment, advantages similar to those of the first embodiment can be obtained.

Next, a third embodiment of the present invention will be described. In the first and second embodiments, the case of manufacturing a GaN substrate has been described.
In the third embodiment, a case where a Ga _1-x In _x N substrate (where 0 <x ≦ 1) is manufactured will be described.

In the third embodiment, first, FIG.
As shown in FIG. 4A, similar to the first embodiment,
For example, by MOCVD, G
a_{1- x}In_xThe N layer 62 is formed at a growth rate of 4 μm / h or less.
Lengthen. Here, this Ga _1-xIn_xSmell in N layer 62
Therefore, 0 <x ≦ 1.

Following the growth of the Ga _1-x In _x N layer 62, for example, DES
The S film (not shown) on the Ga _1-x In _x N layer 62 as a raw material is grown to cover the surface of the Ga _1-x In _x N layer 62. Thereafter, the c-plane sapphire substrate 61 is taken out of the reaction tube. The reason why the surface of the Ga _1-x In _x N layer 62 is covered with the S film before the c-plane sapphire substrate 61 is taken out of the reaction tube is that the c-plane sapphire substrate 1 is reacted in the first embodiment. This is for the same reason that the surface of the GaN layer 2 is covered with the S film before being taken out of the tube.

Next, the c-plane sapphire substrate 61 is placed on its back surface.
By wrapping from the side, this c-plane sapphire
The thickness of the substrate 61 is changed to the hydride VPE method in the next step.
Ga to grow more_1-xIn_xN layer thickness or less
Good. This is because the c-plane sapphire substrate 61 and the Ga_1-xI
n_xDue to the difference in the coefficient of thermal expansion between the N
_1-xIn_xDefects or cracks occur in the N layer
This is to prevent the Thereafter, as shown in FIG.
As shown, Ga on the c-plane sapphire substrate 61_1-xIn_x
A sufficient thickness is formed on the N layer 62 by a hydride VPE method.
Ga (for example, 200 μm)_1-xIn_xN layer 63
Let it grow.

The growth of the Ga _1-x In _x N layer 63 is specifically performed as follows using a hydride VPE apparatus shown in FIG. That is, the c-plane sapphire substrate 61 on which the Ga _1-x In _x N layer 62 has been grown is placed on a susceptor 72 installed in a quartz glass reaction tube 71 of a hydride VPE apparatus shown in FIG. The upstream portion of the reaction tube 71 is separated into three portions by partition plates 73 and 74. A boat 76 containing In75, which is a single raw material, is placed on the partition plate 74 in the uppermost portion, and a middle portion is provided. Ga7 which is a single raw material on the partition plate 73
7. Put boat 78 containing 7. The boat 76 was placed,
A pipe 79 is provided above the partition plate 74 of the reaction tube 71.
, And N ₂ gas can be supplied as a carrier gas through a pipe 80. The partition plate 73 of the reaction tube 71
And a partition plate 74, H
In addition to supplying Cl gas, N ₂ gas can be supplied as a carrier gas through a pipe 82. Further, an NH ₃ gas is supplied to the lowermost portion of the reaction tube 71 through a pipe 83, and
4, N ₂ gas can be supplied as a carrier gas. Here, the reaction tube 71 is heated by a heater 85 installed outside so that a required temperature gradient is provided in the longitudinal direction. Symbols 86 to 9
Reference numeral 1 denotes a mass flow controller for controlling a gas flow rate.

Prior to the growth of the Ga _1-x In _x N layer 63,
First, in the reaction tube 71, the c-plane sapphire substrate 61
Is heated to the growth temperature, thereby evaporating and removing the S film on the surface of the Ga _1-x In _x N layer 62. At this time, in order to prevent N from being desorbed from the Ga _1-x In _x N layer 62 during this heating, an NH ₃ gas is flowed in the reaction tube 71.

After removing the S film in this manner, the reaction tube
HCl gas and gas are applied to the upper part of the partitioning plate 74 of FIG.
N as carrier gas_TwoGas is supplied and the reaction tube 71 is
HCl gas and the like between the cut plate 73 and the partition plate 74.
And N as carrier gas _TwoThe gas is supplied to the reaction tube 7
NH on the lower part of the first partition plate 73_ThreeGas and cap
N as rear gas_TwoSupply gas. At this time, the reaction
In the upper part of the partition plate 74 of the tube 71, HCl
InCl is produced by the reaction of
Between the partition plate 73 and the partition plate 74 of the reaction tube 71.
In the part, Ga is reacted by HCl with Ga77.
Cl is produced. And these InCl and G
aCl and supply to lower part of partition plate 73 of reaction tube 71
NH_ThreeAnd merge above the susceptor 72
The Ga on the c-plane sapphire substrate 61_1-xIn_xN layer
Ga on 62_1-xIn_xAn N layer 63 grows. This Ga
_{1- x}In_xThe growth rate of the N layer 63 is greater than 4 μm / h.
Within the range of 200 μm / h or less.
Choose as large as possible. Typical growth at this time
As an example of conditions, the HCl flow rate is 20 μmol / m
in, NH_ThreeFlow rate is 1 SLM, N_TwoFlow rate is 0.5SL
M, the temperature near In75 in the boat 76 is 750 ° C,
The temperature near Ga77 in boat 78 is 800 ° C,
Of the portion of the c-plane sapphire substrate 61 placed on the
The temperature is 980 ° C. In addition, it is supplied into the reaction tube 71.
Gas is ultimately sent to the abatement equipment for abatement treatment.
Is

Next, the c-plane sapphire substrate 61 on which the Ga _{1 -x} In _x N layer 63 has been grown as described above is placed on the reaction tube 71.
After being removed from the substrate, as shown in FIG.
By law Ga _1-x In and a SiO ₂ film 64 on the _x N layer 63 covers the surface of the Ga _1-x In _x N layer 63.

Next, as shown in FIG. 4D, the c-plane sapphire substrate 61 is etched away by, for example, a wet etching method. This wet etching is performed, for example, by using H
₃ PO ₄ -H ₂ SO ₄ based etchant (e.g., H ₃
PO ₄ : H ₂ SO ₄ = 1: 1) at 285 ° C. Further, the SiO ₂ film 64 is removed by, for example, a wet etching method using an HF-based etchant.

[0052] Thereafter, the surface of the Ga _1-x In x This Ga _1-x In the case of using the surface of the N layer 63 as a growth surface an In _x N layer 63, also, Ga _1-x In x N layer 62 in the case of using the surface of the growth surface of the surface of the Ga _1-x in _x N layer 62, vapor-phase etching, liquid phase chemical etching, by performing etching or polishing by using a chemical mechanical polishing method And a good surface state.

As described above, as shown in FIG.
Single-crystal Ga comprising a thin Ga _{1- x} In _x N layer 62 grown by the VD method and a sufficiently thick Ga _1-x In _x N layer 63 grown thereon by the hydride VPE method.
_{A 1-x} In _x N substrate is manufactured.

As described above, according to the third embodiment,
For example, on the c-plane sapphire substrate 61 by MOCVD,
thin Ga at a growth rate of μm / h or less_1-xIn_xN layer 62
Is growing, Ga_1-xIn_xN layer 62
Surface roughness and cracks are suppressed and crystallinity is good
It can be. And this good quality Ga_1-xIn
_xOn the N layer 62, 4 μm /
h and at a growth rate of 200 μm / h or less,
Ga that is sufficiently thick to be the main part of the substrate_1-xIn_xN layer 63
Is grown, this Ga_1-xIn_xN layer
Suppresses surface roughening and cracking of 63 and has good crystallinity
And thereby a high quality Ga_1-x
In_xAn N substrate can be obtained. In addition, this Ga_1-x
In_xThick Ga forming the main part of N substrate_1-xIn_xN
A hydride having a very high growth rate is used for the growth of the layer 63.
Since the VPE method is used, for example, a 200 μm thick G
a _1-xIn_xThe time required to obtain N substrate is used
Although it depends on the growth rate, it takes only a few hours, for example,
High productivity. Furthermore, this Ga_1-xIn_xN board
Is an example according to the diameter of the c-plane sapphire substrate 61 to be used.
For example, it can be a large area with a diameter of 2 inches or more.
You.

The Ga _1-x In _x thus manufactured
The N substrate is suitable for use in manufacturing various semiconductor devices using a nitride III-V compound semiconductor. That is, by the Ga _1-x In _x N on a substrate by MOCVD or the like growing a nitride III-V compound semiconductor layer, it is possible to manufacture various semiconductor devices. In particular, the Ga _1-x In _x N nitride on the substrate I
When a semiconductor laser is manufactured by growing a group II-V compound semiconductor layer, these nitride-based group III-V compound semiconductor layers are cleaved together with a Ga _1-x In _x N substrate, whereby the semiconductor laser is manufactured. The resonator end face can be easily formed. Further, Ga _1-x In _x N layers 62 and 63
Is n-type, an n-type Ga _1-x In _x N substrate can be obtained. If the Ga _1-x In _x N layers 62 and 63 are p-type, p-type Ga _1-x In _x N A substrate can be obtained, and in these cases, an advantage that an n-type electrode or a p-type electrode can be formed on the back surface of the Ga _1-x In _x N substrate can be obtained. This makes it possible to manufacture a highly reliable semiconductor laser with a high yield.

Next, a fourth embodiment of the present invention will be described. In the first embodiment and the second embodiment, the case of manufacturing a GaN substrate is described. In the third embodiment, the case of manufacturing a Ga _1-x In _x N substrate is described. in embodiments, more _{generally, B w Al x Ga y in} z N ( However, 0 ≦ w ≦ 1,0 ≦ x ≦ 1,0 ≦ y ≦ 1,0 ≦ z ≦
1, w + x + y + z = 1) A case of manufacturing a substrate will be described.

[0057] In this fourth embodiment, first, as shown in FIG. 6A, in the same manner as in the first embodiment, for example, by MOCVD, B _w on the c-plane sapphire substrate 101 Al _x Ga _y In _{A zN} layer 102 is grown. However, in this _{B w Al x Ga y In z} N layer 102,
0 ≦ w ≦ 1, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, w
+ X + y + z = 1.

[0058] _{B w Al x Ga y In z} N layer subsequently to 102 growth, _{B w Al x Ga y In z} N layer 10 in the reaction tube of the MOCVD apparatus, for example, the DES as a raw material
An S film (not shown) is grown on the _Bw Al _x G
The surface of the a _y In _z N layer 102 is covered. Thereafter, the c-plane sapphire substrate 101 is taken out of the reaction tube. Thus c
Before removing the planar sapphire substrate 101 from the reaction tube, B _w
Why the surface of the Al _x Ga _y In _z N layer 102 previously covered with S film, in the first embodiment, covered with S film the surface of the GaN layer 2 before removing the c-plane sapphire substrate 1 from the reaction tube For the same reason.

Next, the thickness of the c-plane sapphire substrate 101 is reduced in the next step by lapping the c-plane sapphire substrate 101 from the back side thereof.
Keep the following thickness of the _{B w Al x Ga y In z} N layer is grown by law. This is due to the difference in thermal expansion coefficient between the _{B w Al x Ga y In z} N layer of c-plane sapphire substrate 101 Toko, defects are generated in the _{B w Al x Ga y In z} N layer This is to prevent cracking or the occurrence of cracks. Thereafter, as shown in FIG. 6B, B _w on c-plane sapphire substrate 101 Al _x Ga _y In _z N layer 102
Above, by hydride VPE, sufficient thickness (e.g., 200 [mu] m) of the _{B w Al x Ga y In z} N layer 103
Grow.

This B_wAl_xGa_yIn_zOf the N layer 103
Specifically, the growth was performed using a hydride VPE device shown in FIG.
The procedure is as follows using a device. That is, B_wAl_xGa
_yIn_zC-plane sapphire substrate 1 on which N layer 102 is grown
01 is the quartz glass of the hydride VPE device shown in FIG.
On the susceptor 112 installed in the reaction tube 111 made of
Put. The upstream part of the reaction tube 111 is provided with partition plates 113 and 11
Divided into five parts by 4, 115, 116
You. In this case, the raw material B is an organometallic compound.
Liethylboron (TEB, B (C_TwoH_Five)_Three) 117
Used as an Al raw material is an organometallic compound,
Aluminum (TMA, Al (CH_Three) _Three) 118
Used. And bubbler 11 with TEB117
9 through piping 120_TwoGas as carrier gas
And TEB generated by the bubbling thereby
The gas is supplied to the partition plate 1 of the reaction tube 111 through the pipe 121.
16 to the upper part. Partition of this reaction tube 111
The upper part of the strip 116 is further connected via a pipe 122.
To supply HCl gas. In addition, TMA118
N through a pipe 123 in the bubbler 120 '_TwoGas
Supply as carrier gas and bubbling
The generated TMA gas is supplied to the reaction tube 1 via a pipe 124.
11 between the partition 115 and the partition 116
Supply. Reference numerals 125 and 126 indicate bypass piping.
Here, distribution of TEB gas supplied from the bubbler 119 is described.
Switching between the pipe 121 and the bypass pipe 125
The opening and closing of the lugs 127 and 128 are performed. Also Bubbler
120, a TMA gas bypass pipe 126 supplied from
Is switched by opening and closing valves 129 and 130.
Do it. Partition plate 114 and partition plate 11 of reaction tube 111
5 on the partition plate 114 at the portion between
The boat 132 containing the In131 which is a charge is placed. this
The partition plate 11 of the reaction tube 111 on which the boat 132 is placed
4 and a partition plate 115 through a pipe 133.
And supply HCl gas through
And N_TwoGas can be supplied as carrier gas
It has become. Further, the partition plate 11 of the reaction tube 111
Partition plate 11 in the portion between 3 and partition plate 114
3 is a boat 1 containing Ga135 as a single raw material
Place 36. The reaction tube 11 where the boat 136 is placed
In the portion between the first partition plate 113 and the first partition plate 114
Supply HCl gas through a pipe 137
And N through the pipe 138_TwoGas as carrier gas
Can be supplied. In addition, the reaction
A pipe 13 is provided below the partition plate 113 of the pipe 111.
NH through 9_ThreeWhile supplying gas, piping 140
Through N_TwoGas can be supplied as carrier gas
I can do it. Here, the reaction tube 111 is
In the longitudinal direction by the heater 141 installed in the section
Heat to the required temperature gradient. Reference numeral 142
151 is a mass flow controller for gas flow control
Shows the ruler.

B_wAl_xGa_yIn_zGrowth of N layer 103
First, in the reaction tube 111, a c-plane saf
By heating the ear substrate 101 to the growth temperature, B_w
Al _xGa_yIn_zEvaporating the S film on the surface of the N layer 102
To remove. At this time, B_wAl_xGa_y
In_zIn order to prevent N from desorbing from the N layer 62,
NH in the reaction tube 111_ThreeLet the gas flow.

After removing the S film in this manner, TEB gas and HCl gas are supplied to the upper portion of the partition plate 116 of the reaction tube 111, and the partition plate 115 of the reaction tube 111 is supplied.
And TMA gas and HC
1 gas is supplied, and HCl gas and N ₂ gas as a carrier gas are supplied to a portion between the partition plate 114 and the partition plate 115 of the reaction tube 111, so that the partition plate 113 and the partition plate 114 of the reaction tube 111 HCl gas and N ₂ gas as a carrier gas are supplied to
An NH ₃ gas and a N ₂ gas as a carrier gas are supplied to a lower portion of one partition plate 113. At this time, in a portion between the partition plate 114 and the partition plate 115 of the reaction tube 111, I
While nCl is generated, HC is formed in a portion of the reaction tube 111 between the partition plate 113 and the partition plate 114.
GaCl is generated by the reaction between 1 and Ga135.
Then, these InCl and GaCl are mixed with the reaction tube 1.
TEB supplied to the upper part of the eleventh partition 116
The gas, the partition plate 115 of the reaction tube 111 and the partition plate 11
6 and the TMA gas supplied to the portion between
By and NH ₃ supplied to the lower part of the first partition plate 113 are joined above the susceptor 112, on the c-plane sapphire substrate _{101 B w Al x Ga y In} z N layer 1
_{02 B w Al x Ga y In} z N layer 103 on the growth. The growth rate of the _{B w Al x Ga y In z} N layer 103, within larger and less 200 [mu] m / h than 4 [mu] m / h, chosen as large as possible unless hinder other.
An example of typical growth conditions at this time is TEB
Flow rate is 40 μmol / min, TMA flow rate is 50 μmo
l / min, HCl flow rate is 20 μmol / min, NH
₃ flow rate is 1 SLM, N ₂ flow rate is 0.5 SLM, boat 1
The temperature near In131 in 322 is 750 ° C, and the boat 1
The temperature around Ga135 in 36 is 800 ° C., and the temperature of the portion of c-plane sapphire substrate 101 placed on susceptor 112 is 980 ° C.

Next, in this way in the B _w Al _x Ga _y I
n _z N layer 103 c-plane sapphire substrate 101 is grown
After removal from the reaction tube 111, as shown in FIG 6C, for example, B, CVD _w Al _x Ga _y In _z N This was a SiO ₂ film 104 on the layer 103 B _w Al _x
The surface of the Ga _y In _z N layer 104 is covered.

Next, as shown in FIG. 6D, the c-plane sapphire substrate 101 is removed by, for example, a wet etching method. This wet etching, for example,
H ₃ PO ₄ -H ₂ SO ₄ based etchant (eg, H
₃ PO ₄ : H ₂ SO ₄ = 1: 1) at 285 ° C. Thereafter, the SiO ₂ film 104 is removed by, for example, a wet etching method using an HF-based etchant.

Thereafter, B_wAl_xGa_yIn_zN layer 10
3 is used as the growth surface._wAl
_xGa_yIn_zThe surface of the N layer 103 is_wAl_x
Ga _yIn_zUsing the surface of the N layer 102 as a growth surface
In this case this B_wAl_xGa _yIn_zSurface of N layer 102
The gas phase etching method, liquid phase chemical etching method, mechanical
Etching or polishing using chemical polishing
Performs flattening and provides good quality
Surface condition.

As described above, as shown in FIG.
Thin B _w grown by VD method Al _x Ga _y In _z N
_{B w Al x Ga y In z} N substrate made of a sufficiently thick _{B w Al x Ga y In z} N layer 103 which is grown by hydride VPE single crystal is produced layers 102 and thereon.

As described above, according to the fourth embodiment,
For example, by MOCVD on the c-plane sapphire substrate 101
Thin B at a growth rate of 4 μm / h or less_wAl_xGa_yIn
_zBy growing the N layer 102, B_wAl_x
Ga_yIn_zThe surface roughness and cracks of the N layer 102
It can be suppressed, and the crystallinity can be improved. And
This good quality B_wAl_xGa_yIn_zHigh on N layer 102
Thick enough to be the main part of the substrate by the dry VPE method
B_wAl_xGa_yIn_zThe growth of the N layer 103
By this, this B_wAl_xGa_yIn_zTable of N layer 103
It suppresses surface roughness and cracks and has good crystallinity.
Which allows for good quality B _wAl_xGa_y
In_zAn N substrate can be obtained. Also, this B_wAl
_xGa_yIn_zThick B constituting the main part of N substrate_wAl
_xGa_yIn_zThe growth rate of the N layer 103 is extremely high.
Since a large hydride VPE method is used, for example,
The time required to obtain a 200 μm thick GaN substrate is:
Depending on the growth rate used, for example, a few hours
It takes less time and productivity is high. Furthermore, this B_wAl_xGa
_yIn_zThe N substrate is a c-plane sapphire substrate 101 to be used.
Depending on the diameter of the large area of, for example, 2 inches or more
can do.

The B manufactured as described above_wAl_xGa
_yIn_zN substrate is a nitride III-V compound semiconductor
Is suitable for use in the manufacture of various semiconductor devices using
is there. That is, this B_wAl_xGa_yIn_zOn N board
Nitride-based III-V compounds by MOCVD
Various semiconductor devices can be manufactured by growing semiconductor layers.
Can be manufactured. In particular, this B_wAl_xGa_yI
n_zNitride III-V compound semiconductor layer on N substrate
When growing semiconductor lasers, these
The nitride III-V compound semiconductor layer is formed of B_wAl_xGa
_yIn_zBy cleaving with the N substrate,
The resonator end face of the laser can be easily formed. Further
And B_wAl_xGa_yIn_zN layers 102 and 103 are n-type
Then n-type B_wAl_xGa_yIn_zGet N substrate
And B_wAl_xGa_yIn _zN layers 102 and 103
Is p-type, then p-type B_wAl_xGa_yIn_zN board
And in these cases B_wAl_xGa_yI
n_zForm an n-type electrode or a p-type electrode on the back surface of the N-substrate
Can be obtained. This
To manufacture highly reliable semiconductor lasers with high yield
It is possible.

Although the embodiments of the present invention have been specifically described above, the present invention is not limited to the above embodiments, and various modifications based on the technical idea of the present invention are possible.

For example, the numerical values, the substrate, and the raw material gas described in the first to fourth embodiments are merely examples, and different numerical values, the substrate, and the raw material gas may be used as needed. Specifically, c-plane sapphire substrate 1,
Instead of 61,101, of course it may also be a sapphire substrate of another face orientation, SiC substrate and MgAl ₂ O
_Four substrates or the like may be used. Further, as a Ga raw material,
TEG may be used instead of TMG.

In the first embodiment described above,
After growing the GaN layer 2 on the c-plane sapphire substrate 1, the c-plane sapphire substrate 1 is wrapped from the back side so that the c-plane sapphire substrate 1 is thinner than the thick GaN layer 3 that is subsequently grown by the hydride VPE method. Although it is made thin, a c-plane sapphire substrate 1 thinner than the GaN layer 3 may be used from the beginning, and the GaN layer 2 and the GaN layer 3 may be grown thereon. The same applies to the third and fourth embodiments.

The Ga in the first embodiment described above is used.
N layer 2, Ga _1-x In _x N layer 6 in the second embodiment
B _w Al _x Ga _y In the second and third embodiments
_For growth of the zN layer 102, an MBE method may be used. Also, instead of the SiO ₂ films 4, 64, and 104 as protective films, for example, S
An iN film or the like may be used.

Further, in the above-described first embodiment, the S film for covering the surface of the GaN layer 2 is grown by MOCVD, but this S film is formed on the c-plane on which the GaN layer 2 is grown. It is also possible to form the sapphire substrate 1 by immersing it in ammonium sulfide ((NH ₄ ) ₂ S _x ) for an appropriate time, for example, about 1 minute. In this case, after forming the S film, the film is washed with pure water and then dried by blowing N ₂ . For the S film for covering the surface of the Ga _1-x In _x N layer 62 in the third embodiment, B _w Al _x Ga _y I in the fourth embodiment
For the S film for covering the surface of the n _z N layer 102 is the same.

Further, in some cases, in the first embodiment, the c-plane sapphire substrate 1 is taken out without forming the S film in the reaction tube of the MOCVD apparatus, and the hydride V
In some cases, a clean surface can be obtained only by thermally cleaning the surface by heating it to a growth temperature in a reaction tube of a PE apparatus.

Further, as the carrier gas, an inert gas other than N ₂ may be used, and if necessary, hydrogen gas may be used.

[0076]

As described above, according to the present invention,
For example, a first predetermined growth is performed on a substrate by a first vapor deposition method.
First B at speed_wAl_xGa_yIn_zGrow N layer
Process and the first B_wAl_xGa_yIn_zThe second on the N layer
By a vapor phase growth method, a second growth rate greater than a first predetermined growth rate
2 at a predetermined growth rate of 2_wAl_xGa_yIn_zN
And a step of growing a layer.
1 B_wAl_xGa_yIn _zN layer and second B_wAl
_xGa_yIn_zN layer is crystalline without surface roughness or cracks
Can also be of good quality. Also, the second
B_wAl_xGa_yIn_zN layer is formed to a sufficient thickness
Can be lengthened. And after this, these first
Of B_wAl_xGa_yIn_zN layer and second B_wAl_x
Ga_yIn_zTo remove the substrate used to grow the N layer
Than B_wAl_xGa_yIn_zN-substrate, specifically
GaN substrates etc. can be manufactured with high productivity
You.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view for explaining a method for manufacturing a GaN substrate according to a first embodiment of the present invention.

FIG. 2 is a schematic diagram illustrating an example of a hydride VPE device used for manufacturing a GaN substrate according to the first embodiment of the present invention.

FIG. 3 is a schematic diagram illustrating an example of a hydride VPE device used for manufacturing a GaN substrate according to a second embodiment of the present invention.

FIG. 4 shows a Ga _1-x In according to a third embodiment of the present invention.
FIG. 5 is a cross-sectional view for describing the method for manufacturing the _xN substrate.

FIG. 5 shows a Ga _1-x In according to a third embodiment of the present invention;
FIG. 3 is a schematic diagram illustrating an example of a hydride VPE apparatus used for manufacturing an _xN substrate.

FIG. 6 shows B _w Al _x G according to a fourth embodiment of the present invention.
method for producing a _y In _z N substrate is a sectional view for explaining the.

FIG. 7 shows B _w Al _x G according to a fourth embodiment of the present invention.
FIG. 3 is a schematic diagram illustrating an example of a hydride VPE apparatus used for manufacturing an a _y In _z N substrate.

[Explanation of symbols]

1, 61, 101... C-plane sapphire substrate, 2, 3,.
·· GaN layer, 4,64,104 ··· SiO ₂ film, 1
1, 71, 111 ... reaction tube, 62, 63 ... Ga
_1-x In _x N layer, 102, 103... B _w Al _x Ga
_y In _z N layer

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Satoshi Tomioka 6-35 Kita Shinagawa, Shinagawa-ku, Tokyo Sony Corporation F-term (reference) 5F045 AA03 AA04 AA05 AB09 AB14 AC08 AC12 AF02 AF09 BB09 CA11 DA53

Claims (18)

[Claims] 1. A first _{B w Al x Ga y In z} N layer at a first predetermined growth rate by the first vapor deposition on the substrate (where, 0 ≦ w ≦ 1,0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦
a step of z ≦ 1, w + x + y + z = 1) the growth, the greater than the first predetermined growth rate by the first _{B w Al x Ga y In z} N second vapor deposition onto layer in second predetermined growth rate second _{B w Al x Ga y in z} N
Layer (however, 0 ≦ w ≦ 1, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0
≦ z ≦ 1, w + x + y + z = 1). A method for growing a nitride-based III-V compound semiconductor layer. 2. The first predetermined growth rate is 4 μm / h.
2. The method for growing a nitride III-V compound semiconductor layer according to claim 1, wherein the second growth rate is not less than 4 μm / h and not more than 200 μm / h. 3. The method according to claim 1, wherein said first vapor deposition method is a metal organic chemical vapor deposition method, and said second vapor deposition method is a hydride vapor phase epitaxy method. A method for growing a nitride III-V compound semiconductor layer. 4. The nitride group III-V according to claim 1, wherein said first vapor deposition method and said second vapor deposition method are each a metal organic chemical vapor deposition method. A method for growing a compound semiconductor layer. 5. The nitride-based system according to claim 1, wherein said first vapor deposition method is a molecular beam epitaxy method, and said second vapor deposition method is a hydride vapor phase epitaxy method. A method for growing a group III-V compound semiconductor layer. 6. The method according to claim 1, wherein the first vapor deposition is a molecular beam epitaxy, and the second vapor deposition is a metal organic chemical vapor deposition. Of growing a compound III-V compound semiconductor layer. 7. The first _{B w Al x Ga y In z} N layer thickness nitride III-V compound semiconductor layer according to claim 1, characterized in that the 0.3~10μm of Growth method. 8. Growth of the first _{B w Al x Ga y In z} N nitride III-V according to claim 1, wherein the thickness is 1~5μm of layer compound semiconductor layer Method. 9. The first B_wAl_xGa_yIn_zN layer
And the second B _wAl_xGa_yIn_zN layer is n-type
C, Si, G which are Group IV elements as n-type impurities
e and Sn and group VI elements S, Se and Te
Contains at least one element selected from the group consisting of
The nitride-based group III-V according to claim 1, characterized in that:
Method for growing compound semiconductor layer. 10. The first _{B w Al x Ga y In z} N
Layer and said second _{B w Al x Ga y In z} N layer is p-type, a group IV element as the p-type impurity C, Si,
Ge and Sn and the group II elements Be, Mg, Ca,
2. The method for growing a nitride-based III-V compound semiconductor layer according to claim 1, comprising at least one element selected from the group consisting of Zn and Cd. 11. The method for growing a nitride III-V compound semiconductor layer according to claim 9, wherein the source of the n-type impurity is a simple substance, an organic compound or a hydride. 12. The p-type impurity raw material is a simple substance, an organic compound or a hydride.
A method for growing a nitride-based III-V compound semiconductor layer as described above. 13. The nitride group III-V according to claim 1, wherein a single substance or an organometallic compound containing said group III element is used as a raw material of group III elements B, Al, Ga and In. A method for growing a compound semiconductor layer. 14. The nitride-based II according to claim 1, wherein the substrate is a sapphire substrate, a silicon carbide substrate, or a magnesium aluminum spinel substrate.
A method for growing an IV group compound semiconductor layer. 15. At least the second B _w Al _x Ga
_y an In _z N thickness the second of the substrate at the time of growing the layer _{B w Al x Ga y In z} N nitride according to claim 1, wherein a is less than the thickness of the layer III -V
A method for growing a group III compound semiconductor layer. 16. At least the second B _w Al _x Ga
_y an In _z N layer growth method of claim 1 nitride III-V compound semiconductor layer according to the thickness of the substrate at the time of growing is characterized in that at 400μm or less. 17. At least the second B _w Al _x Ga
_{2. The method} for growing a nitride III-V compound semiconductor layer according to claim 1, wherein the thickness of the substrate when growing the _y In _z N layer is 200 [mu] m or less. 18. The first _{B w Al x Ga y In z} N
Layer and said second _{B w Al x Ga y In z} N layer is Ga
2. The nitride-based I according to claim 1, wherein the nitride-based I is an N layer.
A method for growing a II-V compound semiconductor layer.