JP2002064249A - Compound semiconductor and method of manufacturing the same, and compound semiconductor light-emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound semiconductor, having proper crystallinity and low resistivity, which could not be achieved by a GaN-based compound semiconductor, and to provide a method of manufacturing the same, and also provide a semiconductor light-emitting device using this compound semiconductor which has superior electrical and optical characteristics. SOLUTION: In this compound semiconductor, Ga1-xAlxN layer (0<=x<=1) is added with In and is doped with donors. By applying compressive strain to the crystal of such a compound semiconductor, an expansion strain in the crystal caused by nitrogen holes can be reduced, thus obtaining a good N type compound semiconductor which has fewer lattice defects and a superior crystallinity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is, Ga _1-x Al _x N layer
(0 ≦ x ≦ 1) or _{In x Ga y Al 1-xy} N layer (0 ≦ x, y ≦
1) a method for growing a compound semiconductor by vapor phase growth,
More specifically, the present invention relates to a method for growing a compound semiconductor having good crystallinity and a low resistivity, a compound semiconductor light emitting device to which the growth method is applied, and a method for manufacturing the same.

[0002]

2. Description of the Related Art GaN (gallium nitride) is a compound semiconductor composed of gallium as a group III element and nitrogen as a group V element, and has a direct transition band structure. Accordingly, the compound semiconductor is an ultraviolet light-emitting device using a transition between a conduction band and a valence band, and is 3.39 eV at room temperature.
It is expected that an ultraviolet light emitting device having a forbidden band width of about 366 nm and a peak wavelength of about 366 nm can be manufactured.

However, to obtain a light emitting device such as a light emitting diode and a semiconductor laser, a so-called PN junction in which a P-type crystal and an N-type crystal are adjacent to each other is required.
It was difficult to produce a P-type crystal composed of aN.
The reason is that GaN has a large forbidden band width, so it should originally be an insulator at room temperature. However, when GaN is manufactured by a conventional process, even if a crystal is not doped with impurities (undoped crystal), it always becomes an N-type crystal, and This is because the free electron concentration becomes extremely high at 10 ¹⁹ cm ⁻³ or more. This is thought to be due to lattice defects, particularly nitrogen vacancies, acting as donors.

Further, in order to obtain a P-type crystal, an acceptor impurity such as Mg is doped so that Ga _1-x Al _x N (0
≦ x ≦ 1) Even if the layer is formed, Mg is inactivated and becomes a crystal having a high resistivity. A lattice defect can be considered for this cause. That is, Ga _1-x Al _x N (0 ≦ x ≦
1) When forming a crystal, vacancies of nitrogen, which is a group V element, are generated, and expandable strain is given to the lattice of the crystal. Due to this expandable strain, a doped acceptor impurity is doped. Is difficult to enter the lattice positions of Ga and Al, and is therefore inactivated.

[0005]

As an improvement method for solving such a problem, for example, Japanese Journal of Appl.
ied Physics 28 (1989) p2112-p2114. It is a method of activating an acceptor impurity by electron beam irradiation, and reports that a P-type crystal was obtained by irradiating an Mg-doped GaN film with an electron beam. m, the hole concentration is still 2 × 10 ¹⁶ cm ^{−3, which} is still high resistance and low carrier concentration. A light emitting diode (LED) device manufactured using this P-type crystal emits light in the ultraviolet region but has low efficiency, and improvement of electrical characteristics is a future subject.

As described above, it is difficult to manufacture (grow) an N-type crystal and a P-type crystal having good crystallinity and low resistivity so as to realize a good PN junction by the conventional technique. At present, it has not been possible to manufacture a compound semiconductor light emitting device such as a light emitting diode device using such crystals, which can obtain sufficient characteristics.

An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a method for growing a compound semiconductor capable of obtaining a good crystal without lattice defects.

It is another object of the present invention to provide a compound semiconductor light emitting device having good electric and optical characteristics and a method for manufacturing the same.

[0009]

The compound semiconductor of the present invention is characterized in that a Ga _1-x Al _x N layer (0 ≦ x ≦ 1) is doped with In and donor impurities. Thereby, the above object is achieved. Further, the donor impurity is Si.
It is desirable that In has a concentration range of 1 × 10 ¹⁷ cm ⁻³ to 7 × 10 ²² cm ⁻³ . Also, the compound semiconductor of the present _{invention, In x Ga y Al 1-} xy N layer (0 ≦ x ≦ 1,0 ≦
It is characterized in that a group V element having an atomic radius larger than N is added to y ≦ 1) and Si is doped. A group V element having an atomic radius larger than N is 1 × 10 ¹⁷
It is desirable that the concentration range be from cm ⁻³ to 7 × 10 ²² cm ⁻³ .

Further, there is provided a compound semiconductor light emitting device using the compound semiconductor. The compound semiconductor light-emitting device is a semiconductor light-emitting device having an N-type cladding layer, an active layer, and a P-type cladding layer on a substrate, wherein at least one of the N-type cladding layer or the active layer includes the compound semiconductor. Is used.

Further, method of producing a compound semiconductor of the present invention, in the Ga _1-x Al x N layer (0 ≦ x ≦ 1) compound semiconductors growth method for growing a, to the Ga _1-x Al x N layer ,
At least one of In, P, As, and Sb is added, and Si is doped.

[0012] The production method of a compound semiconductor of the present _{invention, In x Ga y Al 1-} xy N layer (0 ≦ x ≦ 1,0 ≦ y ≦
In the compound semiconductor growth method for growing a 1), in the _{In x Ga y Al 1-xy} N layer, P, As, with the addition of at least one of Sb, characterized by doping the Si.

As described above, the Ga _1-x Al _x N layer (0 ≦ x ≦
If a group III element having an atomic radius larger than that of Ga and Al, for example, In is added when forming the crystal of 1), compressive strain is given to the growing crystal. Thereby, the extensible strain in the crystal due to the nitrogen vacancies can be reduced. As a result, a compound semiconductor having good crystallinity with few lattice defects (point defects) can be obtained. In the above semiconductor, if a donor impurity is further added, a good N-type crystal with low resistance can be obtained.

The PN comprising the crystal thus obtained
The junction has good electrical and optical properties. This PN
By using the junction, a light emitting element such as a light emitting diode (LED) and a semiconductor laser (LD) in a range from ultraviolet to blue can be realized.

[0015]

[Embodiment 1] Ga _1-x Al _x N layer
In order to vapor-grow (0 ≦ x ≦ 1), a MOCVD (metal organic chemical vapor deposition) apparatus is used, and TMG (trimethylgallium) is used as a Ga material gas, and TMA (trimethylaluminum) is used as an Al material gas. ), NH ₃ (ammonia) or N ₂ (nitrogen gas) was used as the N material.

Further, a group III element having an atomic radius larger than that of Ga and Al was used as an element to be added to the Ga _1-x Al _x N layer. Table 1 below shows the covalent radius of the group III element. In the first embodiment, In is selected based on the covalent radius of the group III element shown in Table 1, and T is used as an In material gas.
MI (trimethylindium) was used.

[0017]

[Table 1]

First, the case of producing (growing) an undoped crystal will be described.

In a MOCVD apparatus, a TM is deposited on a GaAs substrate.
G, TMA and NH ₃ are supplied, and at the same time TMI is supplied, and the concentration range of In is 1 × 10 ¹⁶ cm ^-3 to 1 × 10 ²³ cm.
^A Ga _1-x Al _x N layer (x = 0.50) of ^-3 was grown.

FIG. 1 shows the relationship between the free electron concentration and the In concentration in the obtained crystal. As is clear from FIG. 1, the free electron concentration decreases when the In concentration is in the range of 1 × 10 ¹⁷ cm ⁻³ to 1 × 10 ²³ cm ⁻³ . When the In concentration is 1 × 10 ²¹ cm ⁻³ , the free electron concentration is 1 × 10 ¹⁶
cm ^-3 , which was the minimum value. This result indicates that, considering that the free electron concentration without adding In was 1 × 10 ¹⁹ cm ⁻³ or more, the residual donor concentration caused by nitrogen vacancies was reduced to 1/1000 or less. Means. That is, a good Ga _1-x Al _x N layer with few lattice defects (x =
0.50) was obtained.

When a GaN layer and an AlN layer were grown under the same conditions, the concentration of free electrons was 1 × 10 ¹⁶ cm.
^-3 to 3 × 10 ¹⁶ cm ⁻³ . Therefore, for Ga _1-x Al _x N layers of all composition ratios (0 ≦ x ≦ 1), In
It can be said that there is an effect by the addition of.

Next, the case of manufacturing an N-type crystal will be described.

Under the same conditions as above, while adding In, G
When growing the a _1-x Al _x N layer, SiH ₄ gas was doped as a donor impurity so that the Si concentration was about 1 × 10 ¹⁹ cm ^−3, and the transfer rate was 2000 cm ² / V · S. N-type crystal (N-type conductivity type crystal) having
The mobility was significantly improved as compared with the N-type crystal obtained without adding n.

Next, a case of manufacturing a P-type crystal (P-type conduction type crystal) will be described.

In a MOCVD apparatus, a TM is formed on a GaAs substrate.
G and NH ₃ are supplied, and at the same time, the concentration range of In is 1 × 1.
0 ¹⁶ cm ^-3 supplying TMI to be 1 × 10 ²³ cm ^-3 from the time further, DMZn as an acceptor impurity
(Dimethylzinc).

FIG. 2 shows that activated P-type crystals were obtained.
4 shows the relationship between the acceptor concentration and the In concentration. Figure 2
As can be seen, the In concentration is 1 × 10¹⁷cm^-3From 7 × 1
0^{twenty two}cm^-3The activated acceptor concentration increases up to
Has been added. The In concentration is 1 × 10^{twenty one}cm^-3At the time
Activated acceptor concentration is 5 × 10¹⁸cm^-3And maximum
showed that. The resistivity of the GaN layer having this In concentration is 5
Ωm, mobility is 80cm ^Two/ V · S, and In
Significantly lower resistance than crystals obtained without the addition of
It was able to appear.

This is because the group III element In having a large atomic radius
It is presumed that the addition of the compound mitigated the lattice distortion caused by the nitrogen vacancies, and facilitated the activation of the acceptor impurity of the group II element into the lattice position of the group III element.

Further, other group II elements such as Mg and Be may be used as acceptor impurities other than Zn. When a GaN layer was grown under the same conditions, a low-resistance P-type crystal was obtained.

The AlN layer and the Ga _1-x Al _x N layer (x
(0.50) was grown under the same conditions, a good P-type crystal was obtained by adding the acceptor impurity and In. Therefore, Ga _1-x Al of all composition ratios (0 ≦ x ≦ 1)
_It can be said that the _xN layer has an effect due to the addition of In.

[Embodiment 2] In this embodiment 2, Ga _1-x A
In order to vapor-grow the l _x N layer (0 ≦ x ≦ 1), MOMB
Using an E (organometallic molecular beam epitaxy) device,
TMG as the material gas for a and T as the material gas for Al
MA used NH ₃ or N ₂ as the N material.

As the element added to the Ga _1-x Al _x N layer, a group V element having an atomic radius larger than that of N was used.
Table 2 below shows the covalent bond radius of group V elements. Example 2
In the examples, P, As, and Sb were selected based on the covalent radius of the group V element shown in Table 2, and PH ₃ , AsH ₃ , and Sb were used as material gases, respectively.

[0032]

[Table 2]

First, the case of producing an undoped crystal will be described.

In a MOMBE apparatus, TMG, TMA and NH ₃ are supplied on a GaAs substrate at a growth temperature of 600 ° C. to generate G.
a _1-x Al _x N layer is grown (x = 0.30) and the V
Group element (P, As or Sb) concentration range is 1 × 10 ¹⁶ cm
^-3 to 1 × 10 ²³ cm ^-3 , PH ₃ , AsH ₃ ,
Alternatively, Sb was supplied.

The free electron concentration in the crystal obtained in FIG.
The relationship between P, As, and Sb concentrations is shown. As is clear from FIG. 3, the free electron concentration decreases when the P, As, and Sb concentrations range from 1 × 10 ¹⁶ cm ⁻³ to 1 × 10 ²³ cm ⁻³ . In the case of P, when the concentration was 4 × 10 ²¹ cm ⁻³ , the free electron concentration was 1 × 10 ¹⁶ cm ⁻³ , which was the minimum value. Considering that the free electron concentration was 1 × 10 ¹⁹ cm ⁻³ or more when no Group V element having an atomic radius larger than N was added, the result shows that the residual donor concentration caused by nitrogen vacancies was 1000 × 10 ¹⁹ cm ⁻³ or more. This means that it has been reduced by a factor of 1 or less. That is, good Ga _1-x Al _x N with few lattice defects
This shows that crystals of the layer (x = 0.30) were obtained.

When a GaN layer and an AlN layer were grown under the same conditions, the P, As, and Sb concentrations were 1 × 10 ¹⁶ cm ^−3.
The free electron concentration was able to be reduced in the range of from 1 × 10 ²³ cm ^-3 . Therefore, it can be said that the effect of adding a group V element having an atomic radius larger than N is obtained for the Ga _1-x Al _x N layers having all composition ratios (0 ≦ x ≦ 1).

Next, the case of manufacturing an N-type crystal will be described.

When growing a Ga _{1- x} Al _x N layer under the same conditions as above while adding a group V element having an atomic radius larger than N, SiH ₄ gas is used as a donor impurity and the Si concentration is 1 When doping was performed at about × 10 ¹⁹ cm ⁻³ , an N-type crystal having a mobility of 2000 cm ² / V · S was obtained, and was obtained without adding a group V element having an atomic radius larger than N. The mobility was significantly improved as compared with the N-type crystal.

Next, the case of manufacturing a P-type crystal will be described.

In a MOMBE apparatus, a T
By supplying MG, TMA and NH ₃ , the Ga _1-x Al _x N layer (x
= 0.30), and at the same time, the concentration range of P, As or Sb in the Ga _1-x Al _x N layer is 1 × 10 ¹⁶ cm ⁻³ to 1 ×.
PH ₃ , AsH ₃ , or Sb solid was supplied so as to be 10 ²³ cm ⁻³ . At this time, Zn was further doped as an acceptor impurity.

FIG. 4 shows the activated crystals in the obtained crystal.
The relationship between the sceptor concentration and the P, As and Sb concentrations is shown.
You. As can be seen from FIG. 4, the P, As, and Sb concentrations are 1
× 10 ¹⁶cm^-3From 1 × 10^{twenty three}cm^-3Activation up to the range
Acceptor concentration has increased. And the place of P
If the concentration is 1 × 10^{twenty two}cm^-3Activated at the time of
-Density is 1.1 × 10¹⁹cm^-3And showed the maximum value. This P
Ga with concentration_1-xAl_xThe resistivity of the N layer is 5Ωm, moving
The degree is 80cm^Two/ V · S, which is half as large as N under similar conditions.
Compared to a crystal obtained without adding a large diameter Group V element,
Significantly lower resistance was achieved.

This is because, by adding a group V element having an atomic radius larger than N, lattice strain caused by nitrogen vacancies is reduced, and acceptor impurities of a group II element can easily enter lattice positions of a group III element. It is considered that it became easy to be activated.

When a Ga _1-x Al _x N layer is grown under similar conditions using other group II elements such as Mg and Be in addition to Zn as acceptor impurities, P, As or Sb Was added to obtain a low-resistance P-type crystal.

When the AlN layer and the GaN layer are grown under the same conditions, the acceptor impurities and the P, A
Good P-type crystals were obtained by adding s or Sb.
Therefore, it can be said that the effect of adding a group V element having an atomic radius larger than N is obtained for the Ga _1-x Al _x N layers having all composition ratios (0 ≦ x ≦ 1).

_{Further, In x Ga y Al 1-} xy N layer (0 ≦ x, y
≦ 1) was grown under the same conditions with the addition of a Group V element having an atomic radius larger than N, and the Ga _1-x Al _x N layer
A better crystal was obtained than in the case of (0 ≦ x ≦ 1). That is, the result in the second embodiment is Ga _1-x A
l _x N layer (0 ≦ x ≦ 1) In x Ga y Al 1-xy N layer (0 ≦ x,
It is further improved by substituting y ≦ 1).

In the first and second embodiments, the MOCVD apparatus or the MONBE apparatus is used. However, another apparatus such as an MBE (molecular beam epitaxy) apparatus may be used. Materials of Ga, Al and N, materials of group III elements having an atomic radius larger than Ga and Al, and materials of group V elements having an atomic radius larger than N can also be obtained by using other compounds other than this example. Good. As for the substrate, other than GaAs substrate, Si, InP, Ga
It goes without saying that the use of another semiconductor substrate such as P and a sapphire substrate is also effective.

Example 3 Using the compound semiconductor obtained in Example 2, a semiconductor laser device shown in FIGS. 5A and 5B was manufactured. The manufacturing method will be described below.

First, the N-type GaAs substrate 301 is heated to a temperature of 600 ° C. in a MOMBE apparatus, and TMG, N ₂ ,
By supplying SiH ₄ and PH ₃ , the buffer layer 302 made of N-type GaN is grown to a thickness of 0.2 μm. Here, the buffer layer 302 may be a superlattice of two or more types of semiconductor layers.

Next, as shown in FIG.
Further supply of TMA while supplying N ₂ , SiH ₄ and PH ₃
Is started, and an N-type Ga _1-x Al _x N layer (x = 0.30) is grown to a thickness of 1 μm to form an N-type cladding layer 303.

Next, TMG, N_TwoAnd PH_ThreeSupplied
Until TMA and SiH_FourSupply of GaN and stop GaN layer
The active layer is grown to a thickness of 0.1 μm.
Form 304. Here, the active layer 304 is simultaneously
Ga obtained by supplying MA _1-XAl_xEven in the N layer,
SiH_Four, Obtained by supplying a dopant such as DEZn
It may be a crystal.

Next, while supplying TMG, N ₂ and PH ₃ , supply of TMA and DEZn was further started to form a P-type Ga _{1 -x} Al _x N layer (x = 0.30) having a thickness of 1 μm. To form a P-type cladding layer 305.

Next, as shown in FIG.
The supply of TMA is stopped while N ₂ , PH ₃ and DEZn are supplied, and a P-type GaN layer is grown to a thickness of 0.5 μm to form a P-type contact layer 306.

Subsequently, the P-type electrode 310 and the N-type electrode 31
1 are laminated, thereby producing the semiconductor laser device shown in FIG. Here, PH ₃ was supplied such that its concentration was about 1 × 10 ²² cm ⁻³ during the growth of all the layers.

Although the present embodiment has been described with reference to an example of a full-surface electrode type semiconductor laser device, it is also possible to manufacture a semiconductor laser device having a stripe structure by using a similar manufacturing method. It is also possible to fabricate a waveguide using two or more growths.

Needless to say, the composition ratio x of the Ga _1-x Al _x N layer can be changed as appropriate, and the conductivity types may be all reversed. At the same time as the growth of the Ga _1-x Al _x N layer, the In
By supplying a material _{gas, In x Ga y Al 1-} xy N layer (0 ≦
x, y ≦ 1).

Further, the G of the cladding layers 303 and 305
a_1-xAl_xN layer or In_xGa_yAl _1-xyComposition ratio of N layer
X and / or y vary along the stacking direction
SCH structure and GDIN-SCH structure are also possible.
You. The active layer 304 also has a quantum well structure and
A quantum well structure may be used.

The semiconductor laser manufactured by the manufacturing method of this embodiment has continuous oscillation at room temperature, and has a peak wavelength of 37.
It was around 0 nm. Although the light output was 3 mW, an ultraviolet light emitting device was realized.

When the thickness of the active layer 304 was made to be about 1 μm by the same manufacturing method, a light emitting element which emitted light at a peak wavelength of 367 nm and could be used as an LED (light emitting diode) was obtained.

[0059]

According to the method for growing a compound semiconductor of the present invention, a compound semiconductor having no point defects, good crystallinity and low resistivity can be manufactured. Further, the compound semiconductor light emitting device of the present invention can provide a compound semiconductor light emitting device having good electrical characteristics and optical characteristics.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the In concentration and the free electron concentration in a Ga _1-x Al _x N layer (x = 0.50).

FIG. 2 shows I in a GaN layer doped with an acceptor impurity.
9 is a graph showing the relationship between n concentration and activated acceptor concentration.

[3] _{In x Ga y Al 1-xy} N layer (x = 0.30) in P, A
9 is a graph showing a relationship between s and Sb concentrations and free electron concentrations.

[Figure 4] and the acceptor impurities added an In _x Ga _y Al
₉ is a graph showing the relationship between the concentrations of P, As, and Sb in a _1-xy N layer (x = 0.30) and the concentration of activated acceptors.

FIG. 5 is a sectional view of a compound semiconductor laser device manufactured by the method of the present invention.

[Explanation of symbols]

 301 GaAs substrate 302 Buffer layer 303 Cladding layer 304 Active layer 305 Cladding layer 306 Contact layer 310, 311 Electrode

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor ▲ Yoshi ▼ Tomohiko 22-22, Nagaikecho, Abeno-ku, Osaka-shi, Osaka Inside Sharp Corporation (72) Inventor Shinji Kaneiwa 22-Nagaikecho, Abeno-ku, Osaka-shi, Osaka No. 22 Inside Sharp Corporation (72) Inventor Masafumi Kondo 22-22 No. 22 Nagaikecho, Abeno-ku, Osaka City, Osaka Prefecture Inside (72) Inventor Toshio Hata 22-22 Nagaikecho, Abeno-ku, Osaka City, Osaka Prefecture (72) Inventor Takeshi Obayashi 22-22 Nagaikecho, Abeno-ku, Osaka-shi, Osaka F-term (reference) 5F041 AA40 CA04 CA34 CA35 CA40 CA65 5F045 AA04 AB09 AB14 AB17 AB18 AC01 AC08 AC12 AC15 AF04 BB12 CA11 CA12 5F073 AA46 CA17 CB02 CB19 DA05

Claims (7)

[Claims] 1. The method according to claim 1, wherein the Ga _1-x Al _x N layer (0 ≦ x ≦ 1) has
A compound semiconductor, wherein n is added and a donor impurity is doped. 2. The compound semiconductor according to claim 1, wherein said donor impurity is Si. 3. _{In x Ga y Al 1-xy} N layer (0 ≦ x ≦
1, 0 ≦ y ≦ 1). A compound semiconductor, wherein a group V element having an atomic radius larger than N is added and Si is doped. 4. A compound semiconductor light-emitting device using the compound semiconductor according to claim 1. 5. An N-type clad layer, an active layer, a P-type
A semiconductor light emitting device provided with a mold cladding layer, wherein the N
At least one of the mold cladding layer or the active layer,
A compound semiconductor light-emitting device using the compound semiconductor according to claim 1. 6. A compound semiconductor growing method for growing a Ga _1-x Al _x N layer (0 ≦ x ≦ 1), wherein the Ga _1-x A
A method for manufacturing a compound semiconductor, comprising adding at least one of In, P, As, and Sb to an l _x N layer and doping with Si. 7. _{In x Ga y Al 1-xy} N layer (0 ≦ x ≦
In 1,0 ≦ y ≦ 1) compound semiconductors growth method for growing a, said an In _x Ga _y to Al _1-xy N layer, P, As,
A method for manufacturing a compound semiconductor, comprising adding at least one of Sb and doping Si.