JP2000323753A - Fabrication of group iii nitride based compound semiconductor element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To fabricate a group III nitride based compound semiconductor element having good crystal structure by forming an underlying layer containing at least one kind of compound selected from titanium nitride, hafnium nitride, zirconium nitride, and tantalum nitride. SOLUTION: From the results on table 1, a GaN layer excellent in crystal structure is obtained regardless of the thickness of titanium nitride and AlN layer. In other words, an underlying layer containing at least one kind of compound selected from titanium nitride, zirconium nitride, hafnium nitride, and tantalum nitride is formed. When a first group III nitride based compound semiconductor (buffer layer) is formed thereon by MOCVD or sputtering, a second group III nitride based compound semiconductor (element function part) can be grown thereon with good crystallinity regardless of the thickness thereof. When currents of 20, 50, 100 mA are fed to a light emitting diode 10 having structure as shown in Fig. 8, emission (EL spectrum) as shown in Fig. 9 is realized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a group III nitride compound semiconductor device. More specifically, the present invention relates to improvement of an underlayer of a group III nitride compound semiconductor layer.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication (Kokai) No. 9-237938 discloses that, in order to obtain a group III nitride-based compound semiconductor layer having good crystallinity, a metal nitride having a rock salt structure as an underlayer is used.
1) It discloses that a surface is used as a substrate. That is, in this publication, a group III nitride-based compound semiconductor layer is grown on a (111) plane using a metal nitride having a rock salt structure as a substrate.

[0003]

A substrate for a semiconductor device is required to have characteristics (rigidity, impact resistance, etc.) for maintaining the function of the device. When the substrate is formed of metal nitride, it is considered that a thickness of 100 μm or more is required for the substrate to maintain the characteristics. However, a metal nitride having such a thickness has not been provided as a raw material of an industrial product for semiconductor manufacturing. Therefore, when implementing the invention described in the above-mentioned publication, a substrate made of metal nitride is to be self-made (considered to be by a sputtering method or the like), but it takes much time and effort.

It is an object of the present invention to provide a method for forming a group III nitride compound semiconductor layer having a good crystal structure using raw materials which can be easily obtained industrially. Therefore, the semiconductor device of the present invention has a semiconductor layer having a good crystal structure and can be manufactured at low cost. From another viewpoint, another object of the present invention is to provide a group III nitride-based compound semiconductor device having a novel structure and a method of manufacturing the same.

[0005]

Means for Solving the Problems The present inventors have intensively studied to achieve at least one of the above objects.
As a result, the following invention has been reached. That is, a substrate and one or two selected from titanium nitride, hafnium nitride, zirconium nitride and tantalum nitride formed on the substrate
A group III nitride compound semiconductor device comprising: a base layer containing at least one species; and a group III nitride compound semiconductor layer formed on the base layer.

According to the semiconductor device of the present invention configured as described above, an underlayer made of titanium nitride, hafnium nitride, zirconium nitride, or tantalum nitride is formed on a substrate as a metal nitride. The underlayer made of such a metal nitride has a very small lattice mismatch with the group III nitride compound semiconductor layer formed thereon. Therefore,
A group III nitride-based compound semiconductor layer of good crystal can be grown on the underlying layer. On the other hand, since the substrate can have a thickness necessary to maintain the function of the element, the underlayer can be made thinner. Therefore, the underlayer can be formed easily and inexpensively. If a general-purpose substrate such as sapphire is used for the substrate, the device can be manufactured at low cost as a whole.

In the above, sapphire, Si
Hexagonal materials such as C (silicon carbide) and GaN (gallium nitride), and cubic materials such as Si (silicon), GaP (gallium phosphide), and GaAs (gallium arsenide) can be used. In the case of a hexagonal material, an underlayer is grown thereon. In the case of a cubic material, its (111)
Surface is used. When SiC, GaN, silicon, GaP, or GaAs is used as a substrate, conductivity can be added to the substrate. In addition, titanium nitride (TiN), hafnium nitride, zirconium nitride, and tantalum nitride each have conductivity. As a result, electrodes can be formed on both surfaces of the semiconductor element, and the number of element manufacturing steps is reduced, resulting in cost reduction. When an LED is manufactured using sapphire as a substrate, the metal nitride has a metallic luster, and light emitted from the LED is reflected by titanium nitride, hafnium nitride, zirconium nitride, or the like, so that an increase in brightness is expected. This substrate is required to have characteristics (rigidity, impact resistance) for maintaining the function of the element. Therefore, its thickness is set to approximately 100 μm or more. However, it may be thin as long as the rigidity can be maintained.

As the underlayer, titanium nitride, hafnium nitride, zirconium nitride or tantalum nitride is selected from metal nitrides. The method of growing these metal nitrides on a predetermined surface of the substrate is not particularly limited, but a CVD (Chem) such as a plasma CVD, a thermal CVD, or an optical CVD.
(e.g., vapor deposition), sputtering, reactive sputtering, laser ablation, ion plating, vapor deposition, ECR method, etc.
ysical Vapor Deposition)
Etc. can be used. Underlayer thickness is 50Å-10μ
m is preferable.

Another layer can be interposed between the underlayer and the substrate. According to the study of the present inventors, when growing titanium nitride on the (111) plane using silicon as a substrate, it is preferable to interpose an Al layer between the (111) plane and the titanium nitride layer. . The thickness of the Al layer is not particularly limited, but is set to approximately 100 °. The method for forming the Al layer is not particularly limited, but is formed by, for example, vapor deposition or sputtering.

After forming the underlayer on the substrate, it is preferable to heat-treat the underlayer. Titanium nitride (film thickness: about 300) is formed on the a-plane of the sapphire
FIG. 1 shows the heating temperature and the result of X-ray diffraction (φ (PHI) scan) when this was formed and heated. The heating time is 5 minutes. A 4-axis single crystal diffractometer (product name: X-pert) manufactured by Philips was used as an X-ray diffractometer (the same applies to the results of the following (φ (PHI) scan and X-ray rocking curve). For PHI) scans, see Journal of Electronic Materials, Vol. 25,
No. 11, pp. 1740-1747, 1996. φ (P
In the HI) scan, a peak corresponding to the crystal plane is obtained when the sample is rotated by 360 degrees. The vertical axis in FIG. 1 is the average value of the peak intensities (relative values). Since the measurement was performed using a sample in which the thickness of the TiN film was uniform, it is considered that the higher the strength, the better the crystal was obtained. It is considered that if the crystallinity of titanium nitride as the underlayer is good, the crystallinity of the group III nitride compound semiconductor layer grown thereon is also good.

FIG. 2 shows that the titanium nitride grown under the same conditions as described above is heat-treated (5 minutes) in a hydrogen atmosphere, and then MOCVD (growth temperature: 10
(Phi) scan of the GaN layer formed by (00 ° C.).

From the results shown in FIGS. 1 and 2, it is preferable that the heat treatment temperature of the underlayer be 600 to 1200 ° C. It is considered that such heat treatment further improves the crystallinity of the underlayer. A more preferred heat treatment temperature is 8
00-1200 ° C. The atmosphere when the underlayer is subjected to the heat treatment is preferably a hydrogen atmosphere or a vacuum atmosphere from the results of FIG. More preferably, it is a hydrogen atmosphere.

A titanium nitride layer (thickness: about 30) is formed on the (111) plane of the silicon substrate via an Al layer (thickness: about 100 °).
00, a growth method: a reactive sputtering method), and a GaN layer was further formed thereon in the same manner as in FIG. FIG. 3 shows the result of the φ (PHI) scan on the GaN layer. From the results shown in FIG. 3, it is understood that the heat treatment temperature is preferably set to 600 to 1200 ° C. More preferably, it is 800 to 1200 ° C.

The group III nitride-based compound semiconductor has a general formula of Al _X Ga _Y In _1-XY N (0 ≦ X ≦ 1, 0 ≦
Y ≦ 1, 0 ≦ X + Y ≦ 1), and may further contain boron (B) or thallium (Tl) as a group III element. (P), arsenic (As), antimony (Sb), bismuth (Bi) may be substituted. The group III nitride compound semiconductor may contain any dopant.

As is well known, a light emitting element and a light receiving element have a structure in which a plurality of group III nitride-based compound semiconductor layers of different conductivity types are stacked, and employ a super lattice structure, a double hetero structure, or the like. An electronic device represented by an FET structure can also be formed of a group III nitride compound semiconductor. As described above, the group III nitride-based compound semiconductor layer formed on the underlayer has a desired function because a plurality of layers interact with each other.

For example, a titanium layer can be interposed between the underlayer according to the present invention and the group III nitride compound semiconductor layer. It has been found by the present inventors that the crystal structure of the group III nitride compound semiconductor layer formed on the titanium layer is preferable (for example, Japanese Patent Application No.
-287485, applicant's reference number: 980112, agent's reference number: P0105, and the like. ). The thickness and forming method of the titanium layer are not particularly limited.

A buffer layer may be formed between a base layer made of metal nitride and a group III nitride compound semiconductor layer (second group III nitride compound semiconductor) constituting an element functional portion. preferable. The buffer layer is made of a first group III nitride compound semiconductor. Here, the first Group III nitride compound semiconductor _{Al X Ga Y In 1-X} -Y N (0
A quaternary compound semiconductor represented by <X <1, 0 <Y <1, 0 <X + Y <1), Al _X Ga _1-X N (0 <X <
Ternary compound semiconductor represented by 1) and Al
N, GaN, and InN are included. G on metal nitride
When growing aN, a GaN crystal grows without a buffer layer, but a GaN crystal is better with a buffer layer (see FIGS. 4 and 5). FIG. 4 shows that an underlayer (thickness: 3000 °, substrate: sapphire) made of titanium nitride
1N buffer layer (thickness: 600 °, growth temperature:
1000 ° C.) and a GaN layer (film thickness: 1 μm, growth temperature: 1)
000 ° C.) in the order shown by the MOCVD method. FIG.
Is also G when the buffer layer made of AlN is omitted.
It is an X-ray rocking curve of an aN crystal.

FIG. 6 shows a case where a buffer layer (600 °) made of AlN is formed by MOCVD on a base layer (thickness: 3000 °, substrate: sapphire) made of titanium nitride by changing the growth temperature. GaN layer formed on the buffer layer (film thickness: 1 μm, growth temperature: 100
0 ° C.) (vertical axis: X-ray diffraction intensity (average value of PHI scan)) and the growth temperature of the buffer layer. As can be seen from FIG. 6, the higher the growth temperature when the buffer layer is formed by the MOCVD method, the better (FIG. 6). In general-purpose MOCVD, the first group III nitride compound semiconductor layer (buffer layer) such as AlN or GaN
Was formed directly on a substrate such as sapphire at a low temperature of about 400 ° C. However, when an underlayer made of a metal nitride is formed on a substrate, a suitable crystal can be obtained by growing the first group III nitride compound semiconductor at a high temperature of about 1000 ° C. Accordingly, the crystallinity of the second group III nitride compound semiconductor layer formed on the buffer layer having good crystallinity is also improved.

The above-mentioned temperature of about 1000 ° C. corresponds to the growth of the second group III nitride compound semiconductor layer (element function constituting layer) formed on the first group III nitride compound semiconductor layer (buffer layer). Substantially equal to temperature. Therefore, the first III
The growth temperature at the time of forming the group nitride-based compound semiconductor by the MOCVD method is preferably 600 to 1200 ° C, more preferably 800 to 1200 ° C. When the growth temperatures of the first group III nitride compound semiconductor layer (buffer layer) and the second group III nitride compound semiconductor (element functional constituent layer) are equal, when MOCVD is performed, Temperature control becomes easy.

The first III is formed on the underlayer by sputtering.
Even when a buffer layer made of a group III nitride compound semiconductor layer is formed, a crystalline buffer layer having a crystalline property that is equal to or better than that obtained when the buffer layer is formed by the MOCVD method (growth temperature: 1000 ° C.) can be obtained. . Therefore, the crystallinity of the second group III nitride compound semiconductor layer formed on the first group III nitride compound semiconductor layer is also improved (see FIG. 7). Furthermore, when a first group III nitride compound semiconductor layer (buffer layer) is formed by sputtering, the MOCV
Compared with the method D, raw materials do not require expensive organic metals such as TMA and TMI. Therefore, an element can be formed at low cost.

Hereinafter, the first group III nitride compound semiconductor described in the above paragraph and the second group III nitride compound semiconductor formed thereon
An experimental example for evaluating the improvement in the crystallinity of a group III nitride compound semiconductor will be described. (Experimental example 1) An underlayer made of titanium nitride on a sapphire substrate by a reactive DC magnetron sputtering method by introducing nitrogen gas with titanium as a target (film thickness: 3000 °)
Was formed, and the target was replaced with aluminum, and a reactive DC magnetron sputtering method was performed to form a buffer layer (thickness: 600 °) made of AlN.

From the results of the φ (PHI) scan of the X-ray diffractometer measured for the (200) plane of the underlayer (titanium nitride), and the φ (PHI) of the (10-12) plane of the buffer layer (AlN) From the results of the scan, six-fold symmetrical peaks were confirmed, and TiN and AlN having a single crystal or crystallinity close to a single crystal could be formed. To extend this, metal nitrides: titanium nitride, zirconium nitride,
A first group III nitride-based compound semiconductor layer formed by a sputtering method on an underlayer containing one or more selected from hafnium nitride and tantalum nitride,
Crystals having favorable crystallinity for growing a second group III nitride compound semiconductor constituting an element functional portion thereon are obtained.

Similarly, the evaluation using a silicon substrate was performed, and will be described below. (Experimental example 2) An Al layer (1) was deposited on a silicon substrate by vapor deposition.
00Å). Thereafter, an underlayer (thickness: 30) made of titanium nitride is formed on the Al layer by reactive DC magnetron sputtering by introducing nitrogen gas with titanium as a target.
00Å), the target was replaced with aluminum, and a reactive DC magnetron sputtering method was performed.
A buffer layer (film thickness: 600 °) made of 1N was formed.

Six times from the results of the φ (PHI) scan of the (200) plane of the underlayer (titanium nitride) in the sample and the φ (PHI) scan of the (10-12) plane of the buffer layer (AlN) in the sample. A symmetrical peak can be confirmed, and it can be seen that the crystal of the buffer layer made of titanium nitride and AlN is a c-axis oriented single crystal or a crystal close to this. To extend this, a first layer formed by sputtering on a metal nitride, that is, an underlayer containing at least one selected from titanium nitride, zirconium nitride, hafnium nitride, and tantalum nitride, is used. The group III nitride-based compound semiconductor layer has crystallinity suitable for growing a second group III nitride-based compound semiconductor constituting an element functional portion thereon. In addition, it can be seen from these results that the material of the substrate is not limited.

FIG. 7 shows the X of the GaN layer when GaN (film thickness: 2.5 μm) was further formed on the sample obtained in Experimental Example 1 by MOCVD (growth temperature: 1100 ° C.).
It is a line rocking curve. The half width is 19 s, which indicates that the GaN layer is of high quality.

In Experimental Example 1, the thickness of the titanium nitride and AlN layers was changed, a GaN layer was formed thereon under the above conditions, and the X-ray rocking curve of the GaN layer was measured.
Table 1 shows the results.

[Table 1]

From the results shown in Table 1, a GaN layer having good crystallinity was obtained regardless of the thickness of the titanium nitride and AlN layers. To be more specific, the MOCVD method (growth temperature: 600 to 1200 ° C.) is performed on an underlayer containing one or two or more selected from metal nitrides, that is, titanium nitride, zirconium nitride, hafnium nitride and tantalum nitride. Or, when the first group III nitride compound semiconductor layer (buffer layer) is formed by the sputtering method or the same growth temperature as the second group III nitride compound semiconductor, regardless of the film thickness of both. Instead, a second group III nitride compound semiconductor (device functional portion) can be grown thereon with good crystallinity.

Next, an embodiment of the present invention will be described. (First Embodiment) This embodiment is a light-emitting diode 10, and its structure is shown in FIG.

The specifications of each layer are as follows. Layer: Composition: Dopant (thickness) P-cladding layer 18: p-GaN: Mg (0.3 μm) Emitting layer 17: Superlattice structure Quantum well layer: In _0.15 Ga _0.85 N (35 °) Barrier layer: GaN (35 °) Number of repetitions of quantum well layer and barrier layer: 1 to 10 n cladding layer 16: n-GaN: Si (4 μm) buffer layer 15: AlN (600 °) TiN layer 14: TiN single crystal (3000 °) substrate 11a: Sapphire (300μm)

The n-cladding layer 16 can have a two-layer structure including a low electron concentration n− layer on the light emitting layer 17 side and a high electron concentration n + layer on the buffer layer 15 side. The light emitting layer 17 is not limited to the super lattice structure. As a structure of the light emitting element, a single hetero type, a double hetero type, a homo junction type, or the like can be used. Wide _Al X bandgap doped with an acceptor of magnesium or the like between the light emitting layer 17 and the p-cladding layer _{18 In Y Ga 1-X-} Y N
(Including X = 0, Y = 0, X = Y = 0) layers can be interposed. This is to prevent electrons injected into the light emitting layer 17 from diffusing into the p clad layer 18. The p-cladding layer 18 may have a two-layer structure including a low hole concentration p− layer on the light emitting layer 17 side and a high hole concentration p + layer on the electrode side.

A TiN14 layer is formed on the a-plane of the sapphire substrate by a reactive DC magnetron sputtering method. Further, the target is replaced with Al, and an AlN layer is formed by a reactive DC magnetron sputtering method. Then A
The 1N, TiN / sapphire sample is transferred from the sputtering apparatus into the chamber of the MOCVD apparatus. While flowing hydrogen gas into this chamber, the sample is
Heat to 0 ° C. and maintain for 5 minutes.

Thereafter, while maintaining the temperature at 1100 ° C., a second group III nitride-based compound semiconductor layer after the n-cladding layer 16 is formed according to a conventional method (MOCVD method). In this growth method, ammonia gas and an alkyl compound gas of a group III element, for example, trimethylgallium (TMG), trimethylaluminum (TMA) or trimethylindium (TMI) are supplied onto a substrate heated to an appropriate temperature. A thermal decomposition reaction is performed to grow a desired crystal on the substrate. The second II of the present embodiment thus formed
The crystallinity of the group I nitride-based compound semiconductor layer is preferable.

The translucent electrode 19 is a thin film containing gold.
The cladding layer 18 is laminated so as to cover substantially the entire upper surface. The p-electrode 20 is also made of a material containing gold, and is formed on the translucent electrode 19 by vapor deposition. The n-electrode 21 is formed by vapor deposition on the surface of the n-GaN layer 16 exposed by etching.

When current values of 20, 50 and 100 mA are passed through the light emitting diode 10 having the structure shown in FIG. 8, the light emission (EL) shown in FIG.
Spectrum). When sealed in a shell-type case, the light emission intensity was 1 cd or more.

(Second Embodiment) FIG. 10 shows a light emitting diode 22 according to a second embodiment. The same elements as those in the first embodiment are denoted by the same reference numerals, and description thereof will be omitted. Layer: Composition: Dopant (thickness) P-cladding layer 18: p-GaN: Mg (0.3 μm) Emitting layer 17: Superlattice structure Quantum well layer: In _0.15 Ga _0.85 N (35 °) Barrier layer: GaN (35 °) Number of repetitions of quantum well layer and barrier layer: 1 to 10 n clad layer 16: n-GaN: Si (4 μm) buffer layer 15: AlN (600 °) TiN layer 14: TiN single crystal (3000 °) Al layer 12 : Al (100 mm) substrate 11: Si (111) (300 μm)

The Al layer formed on the Si (111) plane is epitaxially grown by a general-purpose deposition method or sputtering method. The growth method after the TiN layer 14 is the same as in the first embodiment. Note that the Si substrate layer 11 becomes an n-electrode. Then, a wire is bonded at the desired position.

(Third Embodiment) FIG. 11 shows a semiconductor device according to a third embodiment of the present invention. The semiconductor device of this embodiment is a light emitting diode 32. The same elements as those in FIG. 10 are denoted by the same reference numerals, and description thereof will be omitted. The specifications of each layer are as follows. Layer: Composition: Dopant (thickness) n-cladding layer 28: n-GaN: Si (0.3 μm) Light-emitting layer 17: superlattice structure Quantum well layer: In _0.15 Ga _0.85 N (35 °) Barrier layer: GaN (35 °) Number of repetitions of quantum well layer and barrier layer: 1 to 10 p cladding layer 26: p-GaN: Mg (4 μm) buffer layer 15: AlN (600 °) TiN layer 14: TiN single crystal (3000 °) Al layer 12 : Al (100 mm) substrate 11: Si (111) (300 μm)

As shown in FIG. 11, a p-cladding layer 26, a light-emitting layer 17, and an n-cladding layer 28
Are sequentially grown to form the light emitting diode 32. In the case of the element 32, since the n-cladding layer 28 having a low resistance value is the uppermost surface, the light-transmitting electrode (see reference numeral 19 in FIG. 10) can be omitted. Reference numeral 30 in the figure denotes an n-electrode. The Si substrate 11 can be used as it is as a p-electrode.

In the above embodiment, the buffer layer is formed by the DC magnetron sputtering method, but it can be formed by the MOCVD method or the like (however, the growth temperature is as high as 1000 ° C.). The element to which the present invention is applied is not limited to the light emitting diode described above, and other light elements such as a light receiving diode, a laser diode, and a solar cell, as well as rectifiers, bipolar elements such as thyristors and transistors,
It is also applicable to electronic devices such as unipolar devices such as FETs and microwave devices. The present invention is also applicable to a laminate as an intermediate of these elements.

The present invention is not limited to the description of the above-described embodiments and examples, but includes various modifications that can be made by those skilled in the art without departing from the scope of the claims.

The following items are disclosed below: (11) Including a substrate and one or more selected from titanium nitride, zirconium nitride, hafnium nitride and tantalum nitride formed on the substrate A laminate comprising: a base layer formed of: a group III nitride-based compound semiconductor layer formed on the base layer; (12) The laminate according to (11), wherein the substrate is sapphire, silicon carbide, gallium nitride, silicon, gallium phosphide, or gallium arsenide. (13) The substrate is made of a cubic material, and (11)
1) The laminate according to (11) or (12), wherein the underlayer is formed on a surface. (14) The laminate according to any one of (11) to (13), wherein a titanium layer is interposed between the underlayer and the group III nitride compound semiconductor layer. (15) The method according to any one of (11) to (14), wherein the underlayer is heat-treated at 600 to 1200 ° C. before the formation of the group III nitride compound semiconductor layer. Laminate. (16) The laminate according to any one of (11) to (15), wherein the group III nitride-based compound semiconductor layer is a buffer layer. (17) A second group III nitride-based compound semiconductor layer constituting an element functional portion is formed on the buffer layer, and the buffer layer has a growth temperature of the second group III nitride-based compound semiconductor layer. MOCV at substantially the same or high temperature
The laminate according to (16), which is formed by Method D. (18) The laminate according to (16), wherein the buffer layer is formed by a sputtering method, an evaporation method, or an ion plating method. (21) An underlayer containing one or more selected from titanium nitride, hafnium nitride, zirconium nitride, and tantalum nitride is formed on a substrate, and
A heat treatment at 0 to 1200 ° C. to form a group III nitride compound semiconductor layer on the underlayer.
A method for producing a group III nitride compound semiconductor device. (22) The method according to (21), wherein the heat treatment temperature is 800 to 1200 ° C. (23) The method according to (21) or (22), wherein the heat treatment is performed in a hydrogen atmosphere. (24) The method according to (21) or (22), wherein the heat treatment is performed in a vacuum. (31) a substrate, an underlayer containing one or more selected from titanium nitride, zirconium nitride, hafnium nitride and tantalum nitride formed on the substrate; A group III nitride-based compound semiconductor layer formed, wherein the underlayer is heat-treated at 600 to 1200 ° C. element. (32) The device according to (31), wherein the heat treatment temperature is 800 to 1200 ° C. (33) The device according to (31) or (32), wherein the heat treatment is performed in a hydrogen atmosphere. (34) The device according to (31) or (32), wherein the heat treatment is performed in a vacuum. (41) An underlayer containing one or more selected from titanium nitride, hafnium nitride, zirconium nitride, and tantalum nitride is formed on a substrate, and
A method for producing a laminated body, comprising heat-treating at 0 to 1200 ° C. to form a group III nitride compound semiconductor layer on the underlayer. (42) The method according to (41), wherein the heat treatment temperature is 800 to 1200 ° C. (43) The method according to (41) or (42), wherein the heat treatment is performed in a hydrogen atmosphere. (44) The method according to (41) or (42), wherein the heat treatment is performed in a vacuum. (51) a substrate, an underlayer containing one or more selected from titanium nitride, zirconium nitride, hafnium nitride and tantalum nitride formed on the substrate; and And a formed group III nitride compound semiconductor layer, wherein the underlayer is heat-treated at 600 to 1200 ° C. (52) The laminate according to (51), wherein the heat treatment temperature is 800 to 1200 ° C. (53) The laminate according to (51) or (52), wherein the heat treatment is performed in a hydrogen atmosphere. (54) The laminate according to (51) or (52), wherein the heat treatment is performed under vacuum. (61) A substrate having an underlayer containing at least one selected from titanium nitride, zirconium nitride, hafnium nitride, and tantalum nitride is prepared, and the substrate is formed on the underlayer by MOCVD. A buffer layer made of the first group III nitride compound semiconductor at a temperature substantially equal to or higher than the growth temperature of the second group III nitride compound semiconductor layer forming the element functional portion to be formed Forming a group III nitride compound semiconductor device by MOCVD. (62) A substrate having an underlayer containing at least one selected from titanium nitride, zirconium nitride, hafnium nitride and tantalum nitride is prepared, and a first group III is formed on the underlayer. MOCV at a growth temperature of 600 to 1200 ° C. using a buffer layer made of a nitride-based compound semiconductor.
D method, and forming a second group III nitride compound semiconductor layer on the buffer layer. II
A method for manufacturing a group I nitride compound semiconductor device. (63) The growth temperature of the buffer layer is 800 to 120.
The method according to (62), wherein the temperature is 0 ° C. (64) The method according to (62), wherein the growth temperature of the buffer layer is about 1000 ° C. (65) The buffer layer is made of Al _a Ga _1-a N (0 ≦
a ≦ 1), (61) to (6).
The production method according to any one of 4). (66) The method according to any one of (61) to (64), wherein the buffer layer is made of AlN. (67) The base layer is made of titanium nitride, and the buffer layer is made of AlN.
(64) The production method according to any of (64). (68) The manufacturing method according to any one of (61) to (67), wherein the underlayer is heat-treated before forming the buffer layer. (69) The method according to (68), wherein the heat treatment is performed in a hydrogen atmosphere or a vacuum atmosphere. (71) A substrate having an underlayer containing one or more selected from titanium nitride, zirconium nitride, hafnium nitride and tantalum nitride, and a first group III formed on the underlayer A buffer layer comprising a nitride-based compound semiconductor layer, and a second group III nitride-based compound semiconductor layer constituting an element functional portion on the buffer layer, wherein the buffer layer is the second A group III nitride compound semiconductor device formed by MOCVD at a temperature substantially equal to or higher than the growth temperature of a group III nitride compound semiconductor layer. (72) a substrate having an underlayer containing one or more selected from titanium nitride, zirconium nitride, hafnium nitride and tantalum nitride, and a first group III formed on the underlayer A buffer layer made of a nitride-based compound semiconductor layer, and a second group III nitride-based compound semiconductor layer constituting an element functional portion on the buffer layer, wherein the buffer layer is at 600 to 1200 ° C. A group III nitride compound semiconductor device formed by MOCVD at a growth temperature of III. (73) The growth temperature of the buffer layer is 800 to 120.
The device according to (72), wherein the temperature is 0 ° C. (74) The device according to (72), wherein the growth temperature of the buffer layer is about 1000 ° C. (75) The buffer layer is made of Al _a Ga _1-a N (0 ≦
a ≦ 1), wherein (71) to (7)
The device according to any one of 4). (76) The device according to any one of (71) to (74), wherein the buffer layer is made of AlN. (77) The base layer is made of titanium nitride, and the buffer layer is made of AlN.
The element according to any one of (74). (78) The element according to any one of (71) to (77), wherein the underlayer is heat-treated before forming the buffer layer. (79) The device according to (78), wherein the heat treatment is performed in a hydrogen atmosphere or a vacuum atmosphere. (81) A substrate having an underlayer containing one or two or more selected from titanium nitride, zirconium nitride, hafnium nitride and tantalum nitride is prepared, and is then formed on the underlayer by MOCVD. A buffer layer made of the first group III nitride compound semiconductor at a temperature substantially equal to or higher than the growth temperature of the second group III nitride compound semiconductor layer constituting the element functional portion to be formed Is formed by a MOCVD method. (82) A substrate having an underlayer containing one or more selected from titanium nitride, zirconium nitride, hafnium nitride, and tantalum nitride is prepared, and a first group III is formed on the underlayer. MOCV at a growth temperature of 600 to 1200 ° C. using a buffer layer made of a nitride-based compound semiconductor.
A method for manufacturing a laminated body, comprising: forming a second group III nitride compound semiconductor layer on the buffer layer by a method D; (83) The growth temperature of the buffer layer is 800 to 120.
The production method according to (82), wherein the temperature is 0 ° C. (84) The method according to (82), wherein a growth temperature of the buffer layer is about 1000 ° C. (85) The buffer layer is made of Al _a Ga _1-a N (0 ≦
a ≦ 1), wherein (81) to (8)
The production method according to any one of 4). (86) The method according to any one of (81) to (84), wherein the buffer layer is made of AlN. (87) The base layer is made of titanium nitride, and the buffer layer is made of AlN.
The production method according to any one of (84). (88) The method according to any one of (81) to (87), wherein the underlayer is heat-treated before forming the buffer layer. (89) The method according to (88), wherein the heat treatment is performed in a hydrogen atmosphere or a vacuum atmosphere. (91) A buffer layer made of a first group III nitride compound semiconductor layer formed on the underlayer, and a second group III nitride for forming an element functional portion on the buffer layer Wherein the buffer layer is formed by MOCVD at substantially the same temperature as or higher than that of the second group III nitride-based compound semiconductor layer. A laminate characterized by the above. (92) a substrate having an underlayer containing one or more selected from titanium nitride, zirconium nitride, hafnium nitride and tantalum nitride, and a first group III formed on the underlayer A buffer layer made of a nitride-based compound semiconductor layer, and a second group III nitride-based compound semiconductor layer for forming an element functional portion on the buffer layer, wherein the buffer layer is 600 to 1200
A laminate formed by MOCVD at a growth temperature of ° C. (93) The growth temperature of the buffer layer is 800 to 120.
The laminate according to (92), wherein the temperature is 0 ° C. (94) The laminate according to (92), wherein the growth temperature of the buffer layer is about 1000 ° C. (95) The buffer layer is made of Al _a Ga _1-a N (0 ≦
a ≦ 1), wherein (91) to (9)
The laminate according to any one of 4). (96) The laminate according to any one of (91) to (94), wherein the buffer layer is made of AlN. (97) The base layer is made of titanium nitride, and the buffer layer is made of AlN.
The laminate according to any one of (94). (98) The laminate according to any one of (91) to (97), wherein the underlayer is heat-treated before forming the buffer layer. (99) The laminate according to (98), wherein the heat treatment is performed in a hydrogen atmosphere or a vacuum atmosphere. (101) A substrate having an underlayer containing one or two selected from titanium nitride, zirconium nitride, hafnium nitride and tantalum nitride is prepared, and a first group III nitride compound is placed on the underlayer. Forming a buffer layer made of a semiconductor layer by a method other than the MOCVD method, and forming a second group III nitride-based compound semiconductor layer serving as an element functional portion on the buffer layer; For manufacturing a compound semiconductor device. (102) said buffer layer is _{Al a Ga 1-a N (} 0
≦ a ≦ 1), the production method according to (101), wherein (103) The method according to (101), wherein the buffer layer is made of AlN. (104) The underlayer is made of titanium nitride, and the buffer layer is made of AlN.
The production method according to 1). (105) The manufacturing method according to (101), wherein the buffer layer is formed by a DC magnetron sputtering method. (106) Before forming the buffer layer, the substrate having the underlayer is heat-treated.
The method according to any one of 1) to (105). (107) The method according to (106), wherein the heat treatment is performed in a hydrogen atmosphere or a vacuum atmosphere. (108) heat-treating the buffer layer formed on the underlayer in an atmosphere of a mixed gas of hydrogen gas and ammonia gas, and thereafter forming the second group III nitride-based compound semiconductor layer. Features (101) to (10)
The production method according to any one of 7). (111) A substrate having an underlayer made of metal nitride, a buffer layer made of a first group III nitride compound semiconductor layer formed on the underlayer, and formed on the buffer layer A second group III nitride-based compound semiconductor layer serving as an element functional portion, and wherein the buffer layer is formed by a method other than the MOCVD method.
A group III nitride-based compound semiconductor device, comprising: (112) said buffer layer is _{Al a Ga 1-a N (} 0
≦ a ≦ 1), the device according to (111), wherein (113) The device according to (111), wherein the buffer layer is made of AlN. (114) The underlayer is made of titanium nitride, and the buffer layer is made of AlN.
The device according to 1). (115) The device according to (111), wherein the buffer layer is formed by a DC magnetron sputtering method. (116) Before the formation of the buffer layer, the substrate having the base layer is heat-treated.
The device according to any one of 1) to (115). (117) The element according to (116), wherein the heat treatment is performed in a hydrogen atmosphere or a vacuum atmosphere. (118) heat treating the buffer layer formed on the underlayer in an atmosphere of a mixed gas of hydrogen gas and ammonia gas, and thereafter forming the second group III nitride compound semiconductor layer. Features (111) to (11)
The element according to any one of 7). (121) One or two selected from titanium nitride, zirconium nitride, hafnium nitride and tantalum nitride
Preparing a substrate having an underlayer containing at least one species, forming a buffer layer comprising a first group III nitride compound semiconductor layer on the metal nitride layer by a method other than the MOCVD method, the buffer Forming a second group III nitride-based compound semiconductor layer serving as an element functional portion on the layer. (122) said buffer layer is _{Al a Ga 1-a N (} 0
≦ a ≦ 1), the production method according to (121), wherein (123) The manufacturing method according to (121), wherein the buffer layer is made of AlN. (124) The underlayer is made of titanium nitride, and the buffer layer is made of AlN.
The production method according to 1). (125) The manufacturing method according to (121), wherein the buffer layer is formed by a DC magnetron sputtering method. (126) Before forming the buffer layer, the substrate having the underlayer is heat-treated.
The production method according to any one of 1) to (125). (127) The method according to (126), wherein the heat treatment is performed in a hydrogen atmosphere or a vacuum atmosphere. (128) heat treating the buffer layer formed on the underlayer in an atmosphere of a mixed gas of hydrogen gas and ammonia gas, and thereafter forming the second group III nitride compound semiconductor layer. Features (121) to (12)
The production method according to any one of 7). (131) A substrate having an underlayer containing one or more selected from titanium nitride, zirconium nitride, hafnium nitride and tantalum nitride, and a first group III formed on the underlayer A buffer layer made of a nitride-based compound semiconductor layer, and a second group III nitride-based compound semiconductor layer serving as an element functional part formed on the buffer layer, wherein the buffer layer is formed by MOCVD. A laminate formed by a method other than the above. (132) said buffer layer is _{Al a Ga 1-a N (} 0
≦ a ≦ 1), wherein the laminate according to (131), wherein (133) The laminate according to (131), wherein the buffer layer is made of AlN. (134) The underlayer is made of titanium nitride, and the buffer layer is made of AlN.
The laminate according to 1). (135) The laminate according to (131), wherein the buffer layer is formed by a DC magnetron sputtering method. (136) Before forming the buffer layer, the substrate having the base layer is heat-treated.
The laminate according to any one of 1) to (135). (137) The laminate according to (136), wherein the heat treatment is performed in a hydrogen atmosphere or a vacuum atmosphere. (138) heat treating the buffer layer formed on the underlayer in an atmosphere of a mixed gas of hydrogen gas and ammonia gas, and thereafter forming the second group III nitride compound semiconductor layer; Features (131) to (13)
The laminate according to any one of 7).

[Brief description of the drawings]

FIG. 1 shows the heat treatment temperature and φ (PHI) of titanium nitride.
FIG. 4 is a graph showing a relationship with a scan peak intensity.

FIG. 2 is a graph showing a relationship between a heat treatment temperature of a TiN layer formed on a sapphire substrate and a peak intensity of a GaN crystal φ (PHI) scan.

FIG. 3 shows a heat treatment temperature of a TiN layer formed on a Si (111) substrate via Al and a GaN crystal φ (PH);
It is a graph which shows the relationship with I) the peak intensity of a scan.

FIG. 4 is an X-ray rocking curve of a GaN crystal when a GaN crystal is grown after a buffer layer is interposed on TiN.

FIG. 5 is an X-ray rocking curve of a GaN crystal when a GaN crystal is grown directly on TiN.

FIG. 6 is a graph showing the relationship between the growth temperature of a buffer layer on TiN and the peak intensity of a GaN crystal φ (PHI) scan thereon.

FIG. 7 shows an X-ray rocking curve of a GaN layer formed by MOCVD on the AlN layer of Experimental Example 1.

FIG. 8 is a diagram showing a configuration of a light emitting diode according to an embodiment of the present invention.

FIG. 9 shows emission characteristics of the light emitting diode of FIG.

FIG. 10 is a diagram showing a configuration of a light emitting diode according to another embodiment of the present invention.

FIG. 11 is a diagram showing a configuration of a light emitting diode according to another embodiment of the present invention.

[Explanation of symbols]

 10, 22, 32 Light emitting diode 11, 11a Substrate 15 Buffer layer 16, 26 Cladding layer 17 Light emitting layer 18, 28 Cladding layer 19 Translucent electrode

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Naoki Shibata 1 Ochiai Ogata, Kasuga-cho, Nishi-Kasugai-gun, Aichi Prefecture Inside Toyoda Gosei Co., Ltd. (72) Inventor Taishi Watanabe 1 Ochiai-Ogata, Kasuga-cho, Nishi-Kasugai-gun, Aichi Inside Toyoda Gosei Co., Ltd. (72) Inventor Shizuyo Nori 1 Ochiai Nagahata, Kasuga-machi, Nishi-Kasugai-gun, Aichi Prefecture Inside Toyoda Gosei Co., Ltd. (72) Inventor Shinya Asami 1 Ochiai Nagahata, Kasuga-cho, Nishi-Kasugai-gun, Aichi Prefecture Toyota Synthetic Co., Ltd. F term (reference) 5F041 AA31 AA40 CA05 CA23 CA33 CA37 CA40 CA46 CA65 CA73 5F073 AA74 CA07 CB02 CB04 CB05 CB07 DA05 DA16 DA35

Claims (8)

[Claims] 1. A substrate, an underlayer containing one or more selected from titanium nitride, zirconium nitride, hafnium nitride and tantalum nitride formed on the substrate; A group III nitride compound semiconductor device comprising: a group III nitride compound semiconductor layer formed thereon. 2. The method according to claim 1, wherein the substrate is sapphire, silicon carbide,
The device according to claim 1, wherein the device is gallium nitride, silicon, gallium phosphide, or gallium arsenide. 3. The device according to claim 1, wherein the substrate is made of a cubic material, and the underlayer is formed on a (111) plane. 4. The device according to claim 1, wherein a titanium layer is interposed between the underlayer and the group III nitride compound semiconductor layer. 5. The method according to claim 1, wherein the underlayer is heat-treated at 600 to 1200 ° C. before the formation of the group III nitride compound semiconductor layer. Element. 6. The device according to claim 1, wherein said group III nitride compound semiconductor layer is a buffer layer. 7. A second group III nitride compound semiconductor layer forming an element function part is formed on the buffer layer, and the buffer layer is formed by growing the second group III nitride compound semiconductor layer. MOC at substantially the same or higher temperature
The device according to claim 6, wherein the device is formed by a VD method. 8. The device according to claim 6, wherein the buffer layer is formed by a sputtering method, an evaporation method, or an ion plating method.