JPH11243253A - Growth of nitride-based iii-v compound semiconductor, manufacture of semiconductor device, substrate for growth of nitride-based iii-v compound semiconductor, manufacture of the substrate for growth of nitride-based iii-v compound semiconductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To grow a good quality single-crystalline, nitride-based III-V semiconductor. SOLUTION: A layer of laminated substance is grown on a substrate by a molecular beam epitaxy process or the like, and then a nitride III-V compound semiconductor is grown on the laminated substance layer. As the substrate GaAs substrate 1 or an Si substrate is sued. Dangling bonds on the substrate are terminated beforehand preferably prior to the growth of the laminated substance layer. As the laminated substance a transition metal dichalcogenide such as MoS2 , graphite, mica, or the like is used. The nitride-based III-V compound semiconductor is used in the manufacture of semiconductor lasers, light- emitting diodes, field effect transistors(FET), etc.

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, a method for manufacturing a semiconductor device, a substrate for growing a nitride-based III-V compound semiconductor, and a method for manufacturing a substrate for growing a nitride-based III-V compound semiconductor. It is suitable to be applied to the manufacture of various semiconductor devices such as a light emitting diode, a semiconductor laser or an electron transit element using the same.

[0002]

2. Description of the Related Art A GaN-based semiconductor is a light-emitting device such as a light-emitting diode or a semiconductor laser capable of emitting light in a visible region to an ultraviolet region, or a field-effect transistor (FE).
T) is being researched and developed as a promising material for electronic devices, but it is difficult to produce a large GaN single crystal as a substrate for growing this GaN-based semiconductor (J. Cry).
stal Growth 178 (1997) 174) Therefore, it is currently difficult to use a GaN substrate. Therefore, a sapphire (Al ₂ O ₃ ) substrate, a silicon carbide (SiC) substrate, or the like is used as an alternative substrate.

[0003]

However, these sapphire substrates and SiC substrates have significantly different lattice constants and thermal expansion coefficients from GaN-based semiconductors (J. Vac. Sci. Tec.).
hnol. B 10 (1992) 1237, Table 1, Table 2 and FIG. 1), for example, when GaN is grown on these substrates, a large amount of 10 ⁷ to 10 ¹⁰ cm ⁻² is formed in the growth layer. Threading dislocations are generated, cracks and warpage are also observed. These phenomena cause deterioration in the characteristics of the semiconductor element and difficulty in the element manufacturing process, and are considered to be major problems in device manufacturing.

Table 1 Characteristics of GaN-based semiconductor −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Material Crystal system Lattice constant a ( Å) Coefficient of thermal expansion (K ^-1 ) GaN (W) Hexagonal crystal 3 -------------------------------------------------------------------------- .189 5.59 × 10 ⁻⁶ AlN (W) hexagonal crystal 3.112 4.2 × 10 ⁻⁶ InN (W) hexagonal crystal 3.548 2.85 × 10 ⁻⁶ −−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−− Note) W represents a wurtzite crystal structure.

Table 2 Characteristics of GaN-based semiconductor growth substrate ————————————————————————————— Substrate material Crystal System Lattice constant a (Å) Coefficient of thermal expansion (K ^-1 ) ----------------------------------------------------------- Sapphire hexagon Crystal 4.758 7.5 × 10 ⁻⁶ 6H-SiC hexagonal crystal 3.08 5 × 10 ⁻⁶ ZnO hexagonal crystal 3.252 2.9 × 10 ⁻⁶ GaAs (111) cubic crystal 3.9975 6 × 10 ^{− 6} Si (111) cubic 3.8973 3.59 × 10 ^-6 ------------------------------------------------- Therefore, an object of the present invention is to provide a method for growing a nitride-based III-V compound semiconductor capable of growing a high-quality single-crystal nitride-based III-V compound semiconductor, A method of manufacturing a conductor arrangement is to provide a method of manufacturing a nitride-based III-V group compound semiconductor growth substrate and the nitride-based III-V compound semiconductor growth substrate.

[0006]

Means for Solving the Problems The present inventor has made intensive studies in order to solve the above-mentioned problems of the prior art. The outline is described below.

As described above, a sapphire substrate or a SiC substrate has been used as a substrate for growing a GaN-based semiconductor, but these substrates have a large difference in lattice constant and coefficient of thermal expansion from the GaN-based semiconductor. When a GaN-based semiconductor is grown on these substrates, defects such as dislocations occur in the growth layer, and it is difficult to grow a high-quality single-crystal GaN-based semiconductor. Therefore, the present inventors have searched for a growth substrate that does not cause these problems.

As a result of this search, it was concluded that the use of a substrate made of a substance having a layered structure as a growth substrate is effective in solving the above-mentioned problems. This is because the layered material has a weak layer between Van der Waals.
als) force, not only slippage easily occurs between layers, but also because dangling bonds do not appear on the surface, when growing a GaN-based semiconductor on it, the growth layer due to the lattice constant difference This is because the GaN-based semiconductor may grow without causing defects such as dislocations, cracks, and warpage.

As a substance having such a layered structure, a transition metal dichalcogenide (Adv. Phys. 18 (196)
9) 193), graphite, mica, etc. Of these, transition metal dichalcogenides, in particular, not only have a layered structure, but also generally have a smaller lattice constant difference from a GaN-based semiconductor than a sapphire substrate or a SiC substrate. For example, molybdenum sulfide (MoS ₂ ) (known as molybdenite), which is a kind of the transition metal dichalcogenide, is a hexagonal layered compound having a crystal structure as shown in FIG. 800 ° C. 2H-M
The lattice constant of oS ₂ is a = 3.160 °, the difference from the lattice constant of hexagonal GaN a = 3.189 ° is extremely small as 0.9%, and the difference from the lattice constant of AlN is a = 3.112 °. Is also as small as 2.5%. These lattice constant differences show how small the difference between the lattice constant a = 3.189 ° of hexagonal GaN and the lattice constant a = 4.758 ° of sapphire is 16.0%.

FIG. 3 shows (00) of MoS ₂ which is a layered substance.
FIG. 2 schematically shows the atomic arrangement at the interface between GaN layers stacked on the (01) plane (C plane). A gap called a van der Waals gap exists in the MoS ₂ crystal, and slippage between layers is likely to occur along the gap. FIG. 3 indicates that the lattice matching at the MoS ₂ / GaN interface is extremely good. Therefore, as described above, MoS _2, which is a layered substance, is liable to cause slippage between layers, and since dangling bonds do not appear on the surface, when GaN is grown thereon, dislocations and the like appear in the growth layer. The generation of defects, cracks and warpage is effectively prevented, and high-quality single-crystal GaN can be grown. From these facts, it is understood that the MoS ₂ substrate is extremely excellent as a substrate for growing GaN, more generally, a GaN-based semiconductor.

However, it is difficult at present to produce a flat substrate having a large area and a small surface irregularity, as a substrate made of a layered material such as transition metal dichalcogenide, graphite, and mica. There are difficulties in putting it to practical use in the manufacture of

The inventor of the present invention overcomes this difficulty by using a substrate on which these layered materials can be grown, and growing the layered material thereon by vapor phase growth or the like.
We considered using this as a growth substrate. According to this method, it is possible to obtain a substrate of a layered material having a large area and a flat surface with little surface irregularities. Therefore, if this is used as a growth substrate and a GaN-based semiconductor is grown thereon, it is possible to grow a high-quality single-crystal GaN-based semiconductor.

The present invention has been devised based on the above-described study by the present inventors.

That is, in order to achieve the above object, a first aspect of the present invention is to provide a method for manufacturing a semiconductor device, comprising the steps of: growing a layer made of a layered material on a substrate;
A method for growing a nitride-based III-V compound semiconductor, wherein a II-V compound semiconductor is grown.

According to a second aspect of the present invention, after a layer made of a layered material is grown on a substrate, a nitride III-V compound semiconductor is grown on the layer made of the layered material. A method for manufacturing a semiconductor device characterized by the following.

According to a third aspect of the present invention, there is provided a substrate for growing a nitride III-V compound semiconductor, comprising a substrate and a layer made of a layered material grown on the substrate.

According to a fourth aspect of the present invention, a step of growing a layer made of a layered substance on a substrate, a step of growing a nitride III-V compound semiconductor on the layer made of a layered substance, And a process for removing a nitride-based III-V compound semiconductor growth substrate.

In the present invention, the transition metal dichalcogenide, graphite, mica and other various substances are used as the layered substance. Among them, the substrate to be used and the nitride-based III-V compound semiconductor to be grown are used. The most suitable one is used according to the type. The plane orientation of the surface of the layer made of the layered material is typically (000
1). The nitride III-V compound semiconductor is typically hexagonal.

As specific examples of the transition metal dichalcogenide, those having a lattice constant close to the lattice constant a of 3.189 ° of GaN are shown below together with the lattice constant of the a-axis.

Transition metal dichalcogenide a (Å) 2H-MoS ₂ 3.160 3R-MoS ₂ 3.164 2H-WS ₂ 3.154 3R-WS ₂ 3.162 2H-MoSe ₂ 3.288 3R-MoSe _{2 3.292 WSe 2 3.286 ReSe 2 3.30 2H} -TaS 2 3.315 3R-TaS 2 3.32 2H-NbS 2 3.31 3R-NbS 2 3.33 1T-TaS 2 3.346 VSe 2 3.35 In the present invention, as a substrate on which a layer made of a layered material is grown, a nitride II
After growing the group IV-V compound semiconductor, the nitride-based group III-V compound semiconductor can be easily removed without causing damage or the like. An appropriate material is used in consideration of the fact that the coefficient of thermal expansion is close and that dangling bonds on the surface can be terminated.
As a method for removing the substrate, mechanical pulling, etching, lapping, or the like can be used. Specific examples of the substrate include a GaAs substrate and a Si substrate.
In addition to a substrate, a sapphire substrate, a SiC substrate, or the like may be used.

In the present invention, from the viewpoint of improving the crystallinity of the nitride-based III-V compound semiconductor to be grown, it is preferable that dangling bonds on the surface of the substrate be terminated and then the substrate be formed on the substrate. A layer made of a layered material is grown, and a nitride III-V compound semiconductor is grown on the layer made of the layered material. As a substrate, for example, (11
1) When a GaAs substrate having a plane orientation is used, dangling bonds on the surface can be terminated with sulfur (S) (Appl. Phys. Lett. 56 (1990) 327, Jpn. J. Appl.
Phys. 28 (1989) L340) or selenium (Se). When a Si substrate is used as the substrate, for example, the dangling bond on the surface is
Hydrogen (H) by immersing the i-substrate in a solution containing hydrofluoric acid
(Appl. Phys. Lett. 59 (199
1) 1458).

In the present invention, a layer made of a layered material is typically grown by a molecular beam epitaxy (MBE) method.
It may be grown by a method, and furthermore, in some cases, a sputtering method. When the layer made of the layered material is grown by, for example, a molecular beam epitaxy method, the growth temperature is preferably set to 200 ° C. or higher and lower than the decomposition temperature of the layered material.

In the present invention, the nitride III-V compound semiconductor is typically grown by the molecular beam epitaxy method which requires a relatively low growth temperature, but is grown only by the molecular beam epitaxy method at first. Thereafter, the growth may be performed by a growth method that generally requires a higher growth temperature, such as a metal organic chemical vapor deposition method or a hydride vapor phase epitaxial growth (HVPE) method. In the latter method, the metal-organic chemical vapor deposition method or the hydride vapor phase epitaxial growth method can increase the growth rate as compared with the molecular beam epitaxy method.
This is particularly advantageous when the group IV compound semiconductor is grown thick. Of course, the metalorganic chemical vapor deposition method or the hydride vapor phase epitaxial growth method may be used for the first growth. In the molecular beam epitaxy method, a radio frequency (RF) plasma cell or an electron cyclotron (ECR) plasma cell is typically used as a nitrogen (N) source.

In the present invention, the nitride III-V
From the viewpoint of improving the crystallinity of the group III compound semiconductor, preferably, the nitride II is formed on the layer made of the layered material at a growth temperature lower than the growth temperature of the nitride III-V compound semiconductor.
After growing a buffer layer made of an IV group compound semiconductor, a nitride III-V compound semiconductor is grown on this buffer layer. Specifically, for example, after growing a buffer layer made of a nitride III-V compound semiconductor on a layer made of a layered material at a growth temperature of 200 ° C. or more and 500 ° C. or less, a temperature of 650 ° C. or more and 900 ° C. or less is obtained. A nitride III-V compound semiconductor is grown on the buffer layer at a growth temperature. Similarly, from the viewpoint of similarly improving the crystallinity of the nitride-based III-V compound semiconductor, the supply of the raw material during the growth of the nitride-based III-V compound semiconductor is preferably performed by the following method.
It starts with the supply of the raw material of the group II element.

In the present invention, the layer made of a layered material may be at least one layer that forms a layered structure, and the layer made of the layered material may be used as a substrate and a nitride III-V group. From the viewpoint of sufficiently exhibiting the effect of being interposed between the compound semiconductor and the compound semiconductor, the layer preferably includes two or more units of layers.

In the present invention, the nitride III-V compound semiconductor contains at least one group III element selected from the group consisting of Ga, Al, In and B, and at least N, and optionally further contains As or And V-group elements including P. Specific examples of the nitride III-V compound semiconductor include GaN, AlN, and AlGa.
N, GaInN, AlGaInN and the like.

According to the present invention constructed as described above, by growing a nitride III-V compound semiconductor on a layer made of a layered material, the layer made of this layered material slips between the layers. Due to the fact that dangling bonds do not easily appear on the surface, the occurrence of defects such as threading dislocations, cracks and warpage, etc. is suppressed on the layer made of this layered material, while the nitride III-V compound The semiconductor grows. Further, since the layer made of the layered substance is grown on the substrate, it can have a large area and a flat surface without irregularities.

[0028]

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

FIG. 1 shows a G according to a first embodiment of the present invention.
A method for growing an aN layer will be described.

In the first embodiment, as shown in FIG. 4A, a GaAs substrate 1 having a (111) plane orientation is prepared, and a protective film 2 is formed on the back surface. This protective film 2
The GaAs substrate 1 is eroded by ammonia (NH ₃ ), which may be used as an N material during the growth of a GaN layer by the MBE method or the MOCVD method described later. It is.
For example, Mo, Ti, Hf, Zn
A film of high melting point metal or the like is used, and is formed by a vacuum evaporation method, a sputtering method, or the like.

Next, the surface of the protective film 2 is covered with, for example, a resist (not shown), the natural oxide film (not shown) formed on the surface of the GaAs substrate 1 is removed by wet etching, and furthermore, pure water is removed. And then dried with nitrogen gas. In this wet etching, for example, 2% potassium hydroxide (KOH): hydrogen peroxide solution (H
An etchant of ₂ O ₂ ) = 40: 2 is used.

Next, the GaAs substrate 1 whose surface has been cleaned as described above is replaced with, for example, ammonium sulfide ((N
H ₄ ) ₂ S) to terminate dangling bonds on the surface of the GaAs substrate 1 with S (Appl. Phys. Lett. 56)
(1990) 327, Jpn. J. Appl. Phys. 28 (1989) L340). Thereafter, the GaAs substrate 1 is taken out of ammonium sulfide, and its surface is dried with nitrogen gas.

Next, after the GaAs substrate 1 whose dangling bonds on the surface are terminated with S as described above is introduced into the growth chamber of the MBE apparatus, the growth chamber is, for example, 1 × 10 ^-9 P
Evacuate to ultra high vacuum of about a. Next, the temperature of the GaAs substrate 1 is gradually increased and maintained at any temperature in the range of 200 to 800 ° C. At this time, the substrate temperature is 150 ° C.
After passing through, the surface of the GaAs substrate 1 is irradiated with the S molecular beam generated by the Knudsen cell. Then, when the substrate temperature reaches the target growth temperature, Mo molecular beams are also irradiated, as shown in FIG.
A MoS ₂ layer 3 is grown on the surface of a GaAs substrate 1.
The thickness of the MoS ₂ layer 3 is about 1 to 1000 nm. At this time, the outermost surface of the MoS ₂ layer 3 is covered with excess S. The surface of the MoS ₂ layer 3 can be a flat surface with little unevenness over a large area.

Next, the GaAs on which the MoS ₂ layer 3 is grown
After transferring the substrate 1 to a growth chamber of another MBE apparatus, the growth chamber is evacuated to an ultra-high vacuum of about 1 × 10 ⁻⁹ Pa, for example. Next, the temperature of the GaAs substrate 1 is gradually increased to 400 to
After maintaining at any temperature of 1000 ° C. and evaporating excess S covering the outermost surface of the MoS ₂ layer 3, continuously on the clean surface of the MoS ₂ layer 3 as shown in FIG. 4C. Then, a GaN layer 4 is grown by MBE using an RF plasma cell as an N source (hereinafter referred to as “RF-MBE”). During this growth, metal Ga is used as the Ga source, and nitrogen gas or ammonia gas is used as the N source. Even when ammonia is used as the N raw material,
Since the protective film 2 such as a Mo film is formed on the back surface of the GaAs substrate 1, erosion of the GaAs substrate 1 does not occur. The heating temperature of the metal Ga is, for example, 950 ° C. What is important here is that the supply of the raw material during the growth of the GaN layer 4 starts from the supply of the Ga raw material. This is because the introduction of defects such as dislocations into the growth layer can be further suppressed by first setting the surface of the MoS ₂ layer 3 to a Ga surface in the early stage of growth.

FIG. 5 schematically shows the atomic arrangement near the interface between the GaAs substrate 1, the MoS ₂ layer 3, and the GaN layer 4.
FIG. 5 shows that the MoS ₂ layer 3 and the GaN layer 4 are very well lattice-matched.

As described above, according to the first embodiment, the MoS ₂ layer 3, which is a layered material, is grown on the surface of the GaAs substrate 1 in the C-axis orientation.
_The surface composed of the (0001) plane of the _two layers 3 can be made flat with a large area and little unevenness. And this M
By growing the GaN layer 4 on the surface of the oS ₂ layer 2, it is possible to grow a high-quality single-crystal GaN layer 4 while suppressing defects such as dislocations, cracks and warpage.

FIG. 6 shows G according to a second embodiment of the present invention.
A method for growing an aN layer will be described.

In the second embodiment, as shown in FIGS. 6A and 6B, a protective film 2 is formed on the back surface of a GaAs substrate 1 by a process similar to that of the first embodiment. A MoS ₂ layer 3 is grown on the surface of the substrate 1.

Next, as shown in FIG. 6C, the MoS ₂ layer 3
On top, the GaN buffer layer 5 is grown at a growth temperature of 200 to 400 ° C. by the RF-MBE method at a low temperature. During this growth, metal Ga is used as the Ga source, and nitrogen gas or ammonia gas is used as the N source. The thickness of the GaN buffer layer 5 is, for example, 5 to 20 nm. What is important here is that the supply of the raw material during the growth of the GaN buffer layer 5 starts from the supply of the Ga raw material. The reason is as described above.

Next, as shown in FIG. 6D, after growing the GaN buffer layer 5, the growth temperature is raised to 650 to 900 ° C., and the GaN layer 4 is grown at this growth temperature by the RF-MBE method. At the time of growing the GaN layer 4, as in the case of growing the GaN buffer layer 5, metal Ga is used as a Ga source and nitrogen gas or ammonia gas is used as an N source. In this case, the heating temperature of the metal Ga is, for example, 950. ° C.

According to the second embodiment, the same advantages as in the first embodiment can be obtained.

FIGS. 7 to 11 show a method of manufacturing a GaN-based semiconductor laser according to a third embodiment of the present invention.

In the third embodiment, first, as shown in FIG. 7, the protective film 12 is formed on the back surface of the GaAs substrate 11 having the (111) orientation by the same process as in the first and second embodiments. Is formed, and the GaAs substrate 1 is formed.
A MoS ₂ layer 13 is grown in the c-axis orientation on the surface of Sample No. 1 and subsequently, the MoS ₂ layer 13 is formed on the MoS ₂ layer 13 by RF-MBE.
The aN buffer layer 14 and the GaN layer 15 are sequentially grown. In this case, the GaN layer 15 is formed on a GaAs substrate 1 described later.
After removing 1, it plays the role of substrate,
It is grown thick enough to have mechanical strength that can withstand the semiconductor laser manufacturing process. Specifically, the thickness of the GaN layer 15 is generally sufficient if it is about 100 μm or more, but is typically selected to be about several 100 μm.
This GaN layer 15 has n-type conductivity in an undoped state.

Next, as shown in FIG. 8, the n-type AlGaN cladding layer 16 and the n-type GaN optical waveguide layer 17 are grown on the GaN layer 15 by RF-MBE at a growth temperature of 650 to 900 ° C. Ga _1-x In _x N / Ga _1-y In _y N
Active layer 18 of multiple quantum well structure, p-type GaN optical waveguide layer 1
9. A p-type AlGaN cladding layer 20 and a p-type GaN contact layer 21 are sequentially grown. To give an example of the thickness of these layers, the n-type AlGaN cladding layer 16 has a thickness of 0.1 mm.
5 μm, n-type GaN optical waveguide layer 17 is 0.1 μm, p-type G
The aN optical waveguide layer 19 is 0.1 μm, the p-type AlGaN cladding layer 20 is 0.5 μm, and the p-type GaN contact layer 21 is 0.5 μm. Also, the n-type AlGaN cladding layer 1
6 and the n-type GaN optical waveguide layer 17 are doped with, for example, Si as an n-type impurity (donor), and the p-type GaN optical waveguide layer 19, the p-type AlGaN cladding layer 20, and the p-type GaN
The contact layer 21 is doped with, for example, Mg as a p-type impurity (acceptor).

Next, as shown in FIG.
1 is removed from the GaN layer 15. This GaAs substrate 11
Can be removed in various ways. In particular,
For example, a mechanical tensile force is applied between the GaN layer 15 and the GaAs substrate 11, or the MoS ₂ layer 13 is etched with an etching solution (for example, nitric acid: sulfuric acid: water = 1: 1: 3 or phosphoric acid). : Nitric acid = 1: 1), or the GaAs substrate 11 may be etched with an etchant (eg,
Etching with sulfuric acid: hydrogen peroxide solution: water = 3: 1: 1) or lapping.

Next, as shown in FIG. 10, a stripe-shaped p-side electrode 22 is formed on the p-type GaN contact layer 21 by, for example,
The n-side electrode 23 is formed on the back surface of the N-buffer layer 14 as an entire surface electrode. Here, as the p-side electrode 22, for example, Ni
/ Au film, Ni / Pt / Au film, etc., and n-side electrode 2
For example, Ti / Al film or Ti / Al / Pt / A
A u film or the like is used.

Next, the GaN layer 15 on which the laser structure is formed as described above is cleaved into a bar shape to form both resonator end faces, and after coating the end faces, the bar is cleaved to form a chip. Become Thus, the intended GaN-based semiconductor laser is manufactured as shown in FIG.

As described above, according to the third embodiment, the MoS ₂ layer 13 is grown on the GaAs substrate 11,
Further, since a sufficiently thick GaN layer 15 is grown thereon via the GaN buffer layer 14, a high-quality single-crystal GaN layer 15 can be obtained. And this GaN
Since the GaN-based semiconductor layers forming the laser structure are grown on the layer 15, these GaN-based semiconductor layers can also be made of high-quality single crystals. As a result, a GaN-based semiconductor laser having high luminous efficiency, good characteristics of low threshold current density, and long life can be realized. In addition, since the GaN-based semiconductor layer forming the laser structure is stacked on a substrate made of a sufficiently thick GaN layer 15, unlike a conventional GaN-based semiconductor laser using a sapphire substrate, which is an insulating substrate, heat dissipation properties are different. And the necessity of mesa etching for patterning the GaN-based semiconductor layer forming the laser structure into the shape of the laser resonator is not required.
By being formed on the back surface of the aN layer 15,
An electrode structure similar to that of a GaAs-based semiconductor laser or the like can be obtained, so that the manufacturing process can be simplified and manufacturing equipment can be shared. Further, in this GaN-based semiconductor laser, since both the substrate and the semiconductor layer forming the laser structure are GaN-based semiconductor layers, the cavity end face can be easily formed by cleavage.

Next, G according to the fourth embodiment of the present invention will be described.
A method for manufacturing an aN-based semiconductor laser will be described.

In the fourth embodiment, the GaN-based semiconductor layer forming the laser structure is formed not by MBE but by MBE.
It is grown by MOCVD. Specifically, after the GaN buffer layer 14 and the GaN layer 15 are sequentially grown on the MoS ₂ layer 13 by the RF-MBE method as in the third embodiment, the GaAs substrate 11 is removed from the growth chamber of the MBE apparatus. It is preferably transferred to a growth chamber of an MOCVD apparatus by vacuum transfer, and a GaN-based semiconductor layer for forming a laser structure is grown on the GaN layer 15 in the growth chamber. In this case, after growing the uppermost p-type GaN contact layer 21, p
Heat treatment for electrical activation of the
This is performed at a temperature of 0 to 900 ° C. Other points are the same as those of the third embodiment, and the description is omitted.

According to the fourth embodiment, the same advantages as those of the third embodiment can be obtained. In addition, the GaN-based semiconductor layer forming the laser structure can be formed by the MOCVD method having a higher growth rate than the MBE method. As a result, the productivity of the GaN-based semiconductor laser can be improved.

Next, G according to the fifth embodiment of the present invention will be described.
A method for manufacturing an aN-based semiconductor laser will be described.

In the fifth embodiment, the GaN layer 15 excluding the initial growth layer and the Ga forming the laser structure are formed.
An N-based semiconductor layer is grown by MOCVD. Specifically, a GaN buffer layer 14 and a G layer are formed on the MoS ₂ layer 13 by RF-MBE in the same manner as in the third embodiment.
The aN layer 15 is sequentially grown. However, in this case, the thickness of the GaN layer 15 is thin (for example, about 1 μm). Next, the GaAs substrate 11 is moved from the growth chamber of the MBE apparatus to the growth chamber of the MOCVD apparatus.
By growing the GaN layer 15 by growing it by the VD method, a sufficient thickness, for example, a thickness of about several 100 μm is obtained. Thereafter, a GaN-based semiconductor layer for forming a laser structure is grown on the GaN layer 15 by MOCVD. Other points are the same as those of the third embodiment, and the description is omitted.

According to the fifth embodiment, the same advantages as those of the third embodiment can be obtained. In addition to the GaN-based semiconductor layer forming the laser structure, the thick GaN layer 15 can be formed by MOCVD. By growing,
The advantage that the productivity of the GaN-based semiconductor laser can be further improved can be obtained.

Next, G according to the sixth embodiment of the present invention will be described.
A method for manufacturing an aN-based semiconductor laser will be described.

In the sixth embodiment, the GaN layer 15 excluding the initial growth layer is formed by HVPE instead of MBE.
Grow by the method. Specifically, Ga is formed on the MoS ₂ layer 13 by RF-MBE in the same manner as in the third embodiment.
After sequentially growing the N buffer layer 14 and the thin GaN layer 15, the GaAs substrate 11 is removed from the growth chamber of the MBE apparatus by H
The GaN layer 15 is added to the growth chamber of the VPE apparatus and grown by the HVPE method in this growth chamber to have a sufficient thickness, for example, about 100 μm. Next, a GaN-based semiconductor layer for forming a laser structure is grown on the GaN layer 15 by MOCVD. Other points are the same as those of the third embodiment, and the description is omitted.

According to the sixth embodiment, the same advantages as those of the third embodiment can be obtained.
The layer 15 is made of HV having a higher growth rate than the MOCVD method.
By growing by the PE method, the advantage that the productivity of the GaN-based semiconductor laser can be greatly improved can be obtained.

Next, G according to the seventh embodiment of the present invention will be described.
A method for manufacturing an aN-based semiconductor laser will be described.

In the seventh embodiment, GaAs
After growing the MoS ₂ layer 13 on the substrate 11,
Thick Ga on the S ₂ layer 13 via the GaN buffer layer 14
The N layer 15 is grown. The GaN layer 15 is preferably grown by HVPE, which has a high growth rate.

Next, as in the third embodiment, Ga
The GaAs substrate 11 is removed from the N layer 15. As a result, as shown in FIG. 12, a GaN layer 15 having a sufficient thickness to be a growth substrate is obtained. Thereafter, the GaN layer 15
Is used as a growth substrate, and MBE or M
A GaN-based semiconductor layer forming a laser structure is grown by the OCVD method. Other points are the same as those of the third embodiment, and the description is omitted.

According to the seventh embodiment, the same advantages as in the third embodiment can be obtained.

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 concept of the present invention are possible.

For example, the numerical values, structures, substrates, processes, growth methods, and the like described in the above-described first to seventh embodiments are merely examples, and different numerical values, structures, substrates, and processes may be used as necessary. Alternatively, a growth method or the like may be used.

Specifically, in the above-described first to seventh embodiments, the MoS ₂ layer 3 is grown by MBE. However, the MoS ₂ layer 3 may be grown by, for example, the MOCVD method.

In the fifth and sixth embodiments, the GaN-based semiconductor layer forming the laser structure is
Although grown by the OCVD method, this GaN-based semiconductor layer may be grown by the MOCVD method.

In the third to seventh embodiments, the case where the present invention is applied to the manufacture of a GaN-based semiconductor laser has been described. However, the present invention is applicable to the manufacture of a GaN-based light-emitting diode. And GaN
The present invention can also be applied to the manufacture of a GaN-based electron traveling device such as a system FET.

[0067]

As described above, according to the method for growing a nitride III-V compound semiconductor according to the present invention,
Since the nitride-based III-V compound semiconductor is grown on the layer made of the layered material, a high-quality single-crystal nitride-based III-V compound semiconductor can be grown.

According to the method of manufacturing a semiconductor device according to the present invention, a nitride-based III-V compound semiconductor is grown on a layer made of a layered material. A group V compound semiconductor can be grown, and a semiconductor device having good characteristics can be manufactured using the nitride III-V compound semiconductor.

According to the substrate for growing a nitride III-V compound semiconductor according to the present invention, since the layer made of the layered material is laminated on the substrate, the surface thereof has a large area and a flat surface with little unevenness. Therefore, by growing a nitride-based III-V compound semiconductor thereon, a good-quality single-crystal nitride-based III-V
A group compound semiconductor can be grown.

According to the method of manufacturing a substrate for growing a nitride III-V compound semiconductor according to the present invention, a layer made of a layered material is grown on the substrate, and a nitride III-V is grown on the layer made of the layered material. After growing the group V compound semiconductor,
By removing the substrate, it is possible to manufacture a nitride-based III-V compound semiconductor growth substrate composed of a nitride-based III-V compound semiconductor having a large area and a flat surface with less surface irregularities. .

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a lattice constant and a thermal expansion coefficient of a GaN-based semiconductor and a material of a substrate used for growing the GaN-based semiconductor.

FIG. 2 is a schematic diagram showing a crystal structure of MoS ₂ .

FIG. 3 is a schematic diagram schematically showing an atomic arrangement at an MoS ₂ / GaN interface.

FIG. 4 is a cross-sectional view for explaining a method of growing a GaN layer according to the first embodiment of the present invention.

FIG. 5 is a schematic diagram schematically showing an atomic arrangement at an interface of a GaAs substrate / MoS ₂ layer / GaN layer according to the first embodiment of the present invention.

FIG. 6 is a cross-sectional view for explaining a method of growing a GaN layer according to a second embodiment of the present invention.

FIG. 7 is a cross-sectional view for explaining the method for manufacturing the GaN-based semiconductor laser according to the second embodiment of the present invention.

FIG. 8 is a cross-sectional view for explaining the method for manufacturing the GaN-based semiconductor laser according to the second embodiment of the present invention.

FIG. 9 is a cross-sectional view for explaining the method for manufacturing the GaN-based semiconductor laser according to the second embodiment of the present invention.

FIG. 10 is a cross-sectional view for explaining the method for manufacturing the GaN-based semiconductor laser according to the second embodiment of the present invention.

FIG. 11 is a cross-sectional view for explaining the method for manufacturing the GaN-based semiconductor laser according to the second embodiment of the present invention.

FIG. 12 is a cross-sectional view for explaining the method for manufacturing the GaN-based semiconductor laser according to the seventh embodiment of the present invention.

[Explanation of symbols]

1,11 ··· GaAs substrate, 3,13 ··· MoS ₂
, GaN layer, 5, 14 GaN buffer layer, 16 n-type AlGaN cladding layer, 17
... n-type GaN optical waveguide layer, 18 ... active layer, 19
..P-type GaN optical waveguide layer, 20 ... p-type AlGaN cladding layer, 21 ... p-type GaN contact layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H01L 29/812 H01L 29/80 B 33/00 (72) Inventor Katsuhiro Akimoto 1-1-1, Tennodai, Tsukuba-shi, Ibaraki, Tsukuba College of Materials Engineering

Claims (39)

[Claims] After growing a layer made of a layered material on a substrate, a nitride III-V is formed on the layer made of the layered material.
A method for growing a nitride III-V compound semiconductor, comprising growing a group III compound semiconductor. 2. The method for growing a nitride III-V compound semiconductor according to claim 1, wherein the plane orientation of the surface of the layer made of the layered material is (0001). 3. Terminating dangling bonds on the surface of the substrate, growing a layer made of the layered material on the substrate, and forming the nitride-based layer on the layer made of the layered material.
2. The method for growing a nitride-based III-V compound semiconductor according to claim 1, wherein the II-V compound semiconductor is grown. 4. The method for growing a nitride III-V compound semiconductor according to claim 1, wherein said nitride III-V compound semiconductor is hexagonal. 5. The method of growing a nitride III-V compound semiconductor according to claim 1, wherein the layer made of the layered material is grown by a molecular beam epitaxy method. 6. The nitride-based II according to claim 5, wherein the layer made of the layered material is grown at a growth temperature of 200 ° C. or higher and lower than the decomposition temperature of the layered material.
A method for growing an IV group compound semiconductor. 7. The method for growing a nitride III-V compound semiconductor according to claim 1, wherein said nitride III-V compound semiconductor is grown by molecular beam epitaxy. 8. After growing a buffer layer made of a nitride III-V compound semiconductor on a layer made of the layered material at a growth temperature lower than a growth temperature of the nitride III-V compound semiconductor. 2. The method for growing a nitride III-V compound semiconductor according to claim 1, wherein said nitride III-V compound semiconductor is grown on said buffer layer. 9. After growing a buffer layer made of a nitride III-V compound semiconductor on a layer made of the above-mentioned layered substance at a growth temperature of 200 ° C. or more and 500 ° C. or less, 650 ° C.
The nitride III- according to claim 1, wherein the nitride III-V compound semiconductor is grown on the buffer layer at a growth temperature of 900C or less.
A method for growing a group V compound semiconductor. 10. The nitride-based compound according to claim 1, wherein the supply of the material during the growth of the nitride-based III-V compound semiconductor is started from the supply of the group-III element material. A method for growing a III-V compound semiconductor. 11. The nitride-based III-V compound semiconductor according to claim 8, wherein the supply of the raw material during the growth of the buffer layer is started from the supply of a raw material of a group III element. Growth method. 12. The method for growing a nitride III-V compound semiconductor according to claim 1, wherein said layered material is a transition metal dichalcogenide. 13. After growing a layer made of a layered material on a substrate, a nitride-based layer is formed on the layer made of the layered material.
A method for manufacturing a semiconductor device, wherein a group V compound semiconductor is grown. 14. The method according to claim 13, wherein the plane orientation of the surface of the layer made of the layered material is (0001). 15. Terminating dangling bonds on the surface of the substrate, growing a layer made of the layered material on the substrate, and depositing the nitride III-V compound on the layer made of the layered material. 14. The method according to claim 13, wherein the semiconductor is grown. 16. The method according to claim 13, wherein said nitride III-V compound semiconductor is hexagonal. 17. The method for manufacturing a semiconductor device according to claim 13, wherein the layer made of the layered material is grown by a molecular beam epitaxy method. 18. The method of manufacturing a semiconductor device according to claim 13, wherein the layer made of the layered material is grown at a growth temperature of 200 ° C. or higher and lower than the decomposition temperature of the layered material. 19. The method of manufacturing a semiconductor device according to claim 13, wherein said nitride III-V compound semiconductor is grown by molecular beam epitaxy. 20. After growing a buffer layer made of a nitride III-V compound semiconductor on a layer made of the layered material at a growth temperature lower than a growth temperature of the nitride III-V compound semiconductor. 14. The method according to claim 13, wherein the nitride III-V compound semiconductor is grown on the buffer layer. 21. After growing a buffer layer made of a nitride III-V compound semiconductor on a layer made of the above layered material at a growth temperature of 200 ° C. or more and 500 ° C. or less, 650
14. The method according to claim 13, wherein the nitride III-V compound semiconductor is grown on the buffer layer at a growth temperature of not less than 900C and not more than 900C. 22. The semiconductor device according to claim 13, wherein the supply of the raw material during the growth of the nitride III-V compound semiconductor is started from the supply of the raw material of the group III element. Production method. 23. The method of manufacturing a semiconductor device according to claim 20, wherein the supply of the raw material during the growth of the buffer layer is started from the supply of a raw material of a group III element. 24. The method according to claim 13, wherein the layered substance is a transition metal dichalcogenide. 25. A substrate for growing a nitride III-V compound semiconductor, comprising: a substrate; and a layer made of a layered material grown on the substrate. 26. The substrate for growing a nitride III-V compound semiconductor according to claim 25, wherein the layer made of the layered material is grown by a molecular beam epitaxy method. 27. The nitride III-V according to claim 25, wherein the layer made of the layered material is grown at a growth temperature of 200 ° C. or higher and lower than the decomposition temperature of the layered material.
For growing group III compound semiconductors. 28. The substrate for growing a nitride III-V compound semiconductor according to claim 25, wherein said layered material is a transition metal dichalcogenide. 29. A step of growing a layer from a layered material on a substrate, and a step of growing a nitride-based layer on the layer comprising the layered material.
A method for manufacturing a nitride-based III-V compound semiconductor growth substrate, comprising: a step of growing a group V compound semiconductor; and a step of removing the substrate. 30. The nitride III- according to claim 29, wherein, after terminating dangling bonds on the surface of said substrate, a layer made of said layered material is grown on said substrate. A method for manufacturing a substrate for growing a group V compound semiconductor. 31. The method for producing a nitride III-V compound semiconductor growth substrate according to claim 29, wherein said nitride III-V compound semiconductor is hexagonal. 32. The method of manufacturing a nitride III-V compound semiconductor growth substrate according to claim 29, wherein the layer made of the layered material is grown by a molecular beam epitaxy method. 33. The nitride III-V compound semiconductor according to claim 29, wherein the layer made of the layered material is grown at a growth temperature of 200 ° C. or higher and lower than the decomposition temperature of the layered material. Manufacturing method of growth substrate. 34. The nitride III-V according to claim 29, wherein said nitride III-V compound semiconductor is grown by molecular beam epitaxy.
A method for manufacturing a substrate for growing a group III compound semiconductor. 35. After growing a buffer layer made of a nitride III-V compound semiconductor on a layer made of the layered material at a growth temperature lower than a growth temperature of the nitride III-V compound semiconductor. 30. The nitride III-V according to claim 29, wherein said nitride III-V compound semiconductor is grown on said buffer layer.
A method for manufacturing a substrate for growing a group III compound semiconductor. 36. After growing a buffer layer made of a nitride III-V compound semiconductor on the layer made of the layered material at a growth temperature of 200 ° C. or more and 500 ° C. or less, 650
30. The nitride-based II according to claim 29, wherein the nitride-based III-V compound semiconductor is grown on the buffer layer at a growth temperature of not less than 900C and not more than 900C.
A method of manufacturing a substrate for growing a group IV compound semiconductor. 37. The nitride-based semiconductor device according to claim 29, wherein the supply of the raw material during the growth of the nitride-based III-V compound semiconductor is started from the supply of the raw material of the group-III element. A method for manufacturing a substrate for growing a III-V compound semiconductor. 38. The nitride III-V according to claim 35, wherein the supply of the raw material during the growth of the buffer layer is started from the supply of a raw material of a group III element.
A method for manufacturing a substrate for growing a group III compound semiconductor. 39. The method according to claim 29, wherein the layered material is a transition metal dichalcogenide.