JP2003347232A - Method of manufacturing semiconductor and semiconductor element formed by the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method by which a semiconductor having a GaInNAs- based mixed-crystal semiconductor layer having a 1.3-μm light emitting wavelength band and a larger N composition as compared with a conventional one, and to provide a semiconductor element formed by the method. <P>SOLUTION: In the method of manufacturing the semiconductor, the semiconductor having at least one GaInNAs-based mixed-crystal semiconductor layer 34 composed of a mixed-crystal semiconductor containing Ga, In, N, and As elements as main components is manufactured on a III-V semiconductor substrate 31. At the time of growing the semiconductor layer 34 in a crystallized state by the metal-organic vapor phase growth method, at least part of a crystal growing step is performed in an atmosphere containing a halogen gas or a halogen compound gas 15. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a method for manufacturing a semiconductor and a semiconductor device formed by using the same.
The present invention relates to a method for manufacturing a semiconductor having at least one GaInNAs-based mixed crystal semiconductor layer composed of a mixed crystal semiconductor containing a, In, N, and As elements as main components, and a semiconductor element formed by using the method.

[0002]

2. Description of the Related Art In recent years, GInNAs,
4 mainly composed of four elements a, In, N, and As
Former mixed-crystal semiconductors are attracting attention. GaInNAs-based mixed crystal semiconductors can be applied to light emitting devices in the 1.3 μm wavelength band where the chromatic dispersion value is minimized in quartz-based single mode optical fibers by adjusting the In composition and N composition to appropriate values. It is expected as a next-generation device for realizing high-speed optical communication with large capacity.

Another semiconductor that can realize an emission wavelength of 1.3 μm is an InP (indium phosphorus) -based mixed crystal semiconductor. Research is also being conducted on this InP,
Ga commonly used with InP-based mixed crystal semiconductors
Since the lattice constant is significantly different from that of the As substrate, InP
When a system-based mixed crystal semiconductor is formed on a GaAs substrate, lattice distortion increases. Therefore, an InP-based mixed crystal semiconductor must be formed on a high-cost InP substrate in consideration of lattice matching.

On the other hand, a GaInNAs-based mixed crystal semiconductor has an In composition of about 20 to 30% (mol%),
Since lattice distortion with respect to an aAs substrate is relatively small and an emission wavelength of 1.3 μm can be obtained, a GaAs substrate which is lower in cost than an InP substrate can be used.
A device can be supplied at a lower cost than a P-based mixed crystal semiconductor.

Further, GaInNAs-based mixed crystal semiconductors are also expected to be applied to surface emitting lasers. GaInNAs
Surface-emitting lasers based on mixed-crystal semiconductors are GaInNAs
This is realized by forming and arranging a multilayer reflective film made of GaAs and AlAs on the upper and lower surfaces of an active layer made of a mixed-crystal semiconductor, thereby forming a vertical resonator. However, in the case of InP-based mixed crystal semiconductors, there is no suitable material for forming a multilayer reflective film formed and arranged on the upper and lower surfaces of an active layer composed of an InP-based mixed crystal semiconductor. It is almost impossible.

In the calculation of Kondo et al.'S band lineup (see Jpn. J. Appl. Phys. 35 (1996) p1273-1275),
By forming a cladding layer having a larger band gap than GaAs on a GaAs substrate, the band discontinuity of the conduction band is increased. Therefore, the light-emitting element using a GaInNAs-based mixed crystal semiconductor has a small fluctuation in characteristics with respect to temperature change. In normal use, a cooler such as a Peltier element is not required. Therefore, the cost of the entire device can be reduced.

[0007]

As described above, GaIn
Although the NAs-based mixed crystal semiconductor has various features as compared with the InP-based mixed crystal semiconductor, at present, it has the following problems.

A GaInNAs-based mixed crystal semiconductor has an In composition of 20 to 40% (mol%) and an N composition of 1 to 2% (mo
1%), light emission with a wavelength of 1.3 μm is obtained (Masao
Kawaguchi, Tomoyuki Miyamoto, Eric Gouardes, Dietmar
Schlenker, Takashi Kondo, Fumi Koyama and Kenichi Ig
a: Jpn.J.Appl.Phys.Vol.40 (2001) pp.L744-L746).
Here, although the chromatic dispersion value is minimized in the wavelength band of 1.3 μm, the loss is minimized at the wavelength of 1.55 μm. Therefore, of the 1.3 μm band, a longer wavelength having a smaller loss is preferable. . To achieve a longer wavelength, the In composition and N
It is clear that the composition should be increased. However, if the In composition of the GaInNAs-based mixed crystal semiconductor is too large, the lattice strain increases, and it becomes difficult to grow the GaAs substrate. Therefore, an attempt has been made to increase the composition of N, which can increase the wavelength by a small amount,
GaInNAs-based mixed crystal semiconductors have a problem that they are grown in a non-equilibrium system, so that the efficiency of taking in N is low, and that it is difficult to increase the N composition.

As a method for solving this problem, the supply amount of the N raw material is remarkably increased with respect to the supply amount of the As raw material.
The method of compensating for the low acquisition efficiency of N is common. But,
The method of increasing the supply amount of the N raw material while maintaining the supply amount of the As raw material is impractical because the supply amount of the N raw material is too large. Conversely, when the supply amount of the As source is reduced while the supply amount of the N source is maintained, 0.9% of the group V composition of the III-V mixed crystal semiconductor is obtained.
The supply amount of the As element occupying the above ratio is significantly reduced, and the crystal quality of the GaInNAs-based mixed crystal semiconductor is reduced. In this method, since the supply amount of the As source becomes 1/100 or less of the supply amount of the N source, a slight change in the supply amount of the source significantly changes the source ratio in the growth atmosphere. There has been a problem that accurate control of the composition cannot be performed, and a decrease in throughput is caused.

An object of the present invention, which has been made in view of the above circumstances, is to manufacture a semiconductor having a GaInNAs-based mixed crystal semiconductor layer having an emission wavelength of 1.3 μm band and a large N composition as compared with the conventional one. An object of the present invention is to provide a method and a semiconductor device formed using the method.

[0011]

In order to achieve the above object, a method of manufacturing a semiconductor according to the present invention is provided on a III-V group semiconductor substrate by mixing a Ga, In, N, and As element as a main component. In the method of manufacturing a semiconductor having at least one GaInNAs-based mixed crystal semiconductor layer made of a crystalline semiconductor, when growing the GaInNAs-based mixed crystal semiconductor layer by metal organic chemical vapor deposition, at least one of the crystal growth steps is performed. A part is performed in an atmosphere containing a halogen gas or a halogen compound gas.

More specifically, chlorine gas or bromine gas is used as the halogen gas. Further, a chlorine compound gas or a bromine compound gas is used as the halogen compound gas.

Further, as the N raw material, at least one of monomethylhydrazine, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, tertiarybutylamine, tertiarybutylhydrazine, and ammonia is used as the N raw material. Is supplied. According to a fifth aspect of the present invention, a gas containing at least one of arsine, tert-butylarsine, and trimethylarsenic is supplied as an As material.

Thus, during the crystal growth, the halogen gas suppresses the generation of the GaAs bond and the InAs bond, and etches the generated GaAs bond and the InAs bond. For this reason, the ratio of the GaN bond and the InN bond in the GaInNAs-based mixed crystal semiconductor layer relatively increases,
The efficiency of taking in N is improved. As a result, the emission wavelength is 1.3.
G is in the μm band and has a large N composition compared to the prior art.
An aInNAs-based mixed crystal semiconductor layer can be formed.

On the other hand, a semiconductor device according to the present invention is a semiconductor device having a light emitting layer, wherein at least the light emitting layer is formed of a GaInNAs-based mixed crystal semiconductor layer using the above-described semiconductor manufacturing method.

Thus, it is possible to obtain a semiconductor element having a GaInNAs-based mixed crystal semiconductor layer having an emission wavelength in the 1.3 μm band and a large N composition as compared with the related art on a III-V semiconductor substrate. it can.

[0017]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred embodiment of the present invention will be described below with reference to the accompanying drawings.

(First Embodiment) FIG. 1 shows a material supply sequence of a semiconductor manufacturing method according to a first embodiment.

The method of manufacturing a semiconductor according to the present embodiment
Ga, I on a GaAs substrate (III-V semiconductor substrate)
A GaInNAs-based mixed crystal semiconductor layer composed of a mixed crystal semiconductor containing n, N, and As elements as main components is at least one layer.
When the crystal is grown by the metal organic chemical vapor deposition method,
As shown in FIG. 5, a Ga source 11, an In source 12, an N source 13, and an As source 14 are supplied as source gases, and the entire crystal growth process is performed under an atmosphere containing a halogen gas (or a halogen compound gas) 15. Is what you do.

Specifically, first, the G disposed in the growth furnace
A desired epitaxial layer is formed on each of the aAs substrates. Then, a Ga source (eg, TE) is placed in the growth furnace.
Ga, TMGa) 11, In material (for example, TMIn)
12, an N source (for example, DMHy) 13 and an As source (for example, TBAs) 14 are simultaneously supplied, and a halogen gas 15 and a carrier gas are supplied as atmosphere gases. Thereafter, the inside of the growth furnace is maintained at a predetermined pressure and temperature, and GaInNA
An s-based mixed crystal semiconductor layer is formed.

At this time, by growing the crystal in an atmosphere containing the halogen gas 15, the halogen gas 15
Etch aAs and InAs bonds (DCHay
s, CRAbernathy, WSHobsons, SJPearton, J.Han, RJ
Shul, H.Cho, KBJung, F.Ren, and YBHahn: Mater.Res.S
oc.Symp.Proc., vol. 573, 281-286 (1999))
The GaN bond and the InN bond as well as the GaAs bond and the InAs bond are etched by the halogen gas 15. However, the binding energies of the GaAs bond and the InAs bond are 71.4 kJ / mol and 58.8 kJ / m, respectively.
ol (Tatsushi Hashimoto, Takeshi Tanaka, Mineo Wajima: Hitachi Cable No.20 (20
01-1) and pp37-pp42), whereas the binding energy of the GaN bond and the InN bond is 745 kJ / m2, respectively.
ol, 861 kJ / mol (Ji-Myon Lee, Sang-Woo Kim and Seo
ng-Ju Park: Journal of The Electrochemical Society,
148 (5) G254-G257 (2001)), which is about 10 times as large.
Therefore, in an atmosphere where these bonds are simultaneously present,
What is mainly etched by the halogen gas 15 is G
aAs bond and InAs bond, GaN bond and IAs bond.
nN bonds are hardly etched. That is, the GaAs bond and the InAs bond are selectively etched by the halogen gas 15.

Therefore, by performing the crystal growth of the GaInNAs-based mixed crystal semiconductor layer in an atmosphere containing the halogen gas 15, the generation of the GaAs bond and the InAs bond is suppressed by the halogen gas 15, and the generated Ga
The As bond and the InAs bond are etched (decomposed). For this reason, the ratio of the GaN bond and the InN bond in the GaInNAs-based mixed crystal semiconductor layer is relatively increased, and as a result, the efficiency of taking in N is improved.

Thereafter, a desired epitaxial layer is formed on the GaInNAs-based mixed crystal semiconductor layer, respectively.
By forming an electrode portion and performing wire bonding, a semiconductor element, for example, a light emitting element can be obtained.

Here, the composition of the group V element in the GaInNAs-based mixed crystal semiconductor layer can be controlled by adjusting the ratio of the halogen gas 15 to the atmospheric gas and the type of the halogen gas 15. More specifically, the ratio of the halogen gas 15 to the atmospheric gas is 1 to 50%,
Preferably it is 1 to 10%.

The type of the halogen gas 15 is not particularly limited. However, considering the results of reactive ion etching and the like, chlorine (Cl ₂ ), hydrogen chloride (HCl), carbon tetrachloride (CCl ₄ ), carbon trichloride (CHCl ₃ ), boron trichloride (BCl ₃ ), bromine (Br
₂ ), hydrogen bromide (HBr), carbon tetrabromide (CBr ₄ ), boron tribromide (BBr ₃ ), carbon tetrafluoride (CF ₄ ), or nitrogen trifluoride (NF ₃ ) is preferred. These halogen gases or halogen compound gases need not necessarily be used alone, and a mixed gas obtained by mixing two or more kinds of halogen gases or halogen compound gases may be used. Further, a hydrogen gas, a nitrogen gas, or the like may be mixed with these simple gases or a mixed gas.

The GaInNAs-based mixed crystal semiconductor layer comprises:
It is not always necessary to be composed only of the four elements of Ga, In, N and As, but a p-type dopant such as Mg (magnesium) and Zn (zinc) or an n-type dopant such as C (carbon) and Si (silicon) It may contain a dopant. Also,
If necessary, an element such as Sb (antimony) or P (phosphorus) may be added, and GaInNAsSb or GaInNAsP or the like may be added.
An elementary mixed crystal semiconductor, or a mixed elementary semiconductor having six or more elements may be used.

As the N raw material 13, monomethyl hydrogen
Drazine (molecular formula CH_ThreeNHNH_Two), 1,1-dimethyl
Hydrazine (molecular formula (CH_Three)_TwoNNH_Two), 1,2-di
Methylhydrazine (molecular formula (CH_Three) NHNH (C
H_Three)), Tertiary butylamine (molecular formula (CH_Three)_Three
CNH_Two), Tertiary butyl hydrazine (molecular formula (C
H_Three) _ThreeCNHNH_Two) Or ammonia (molecular formula NH_Three)
Gas containing at least one of the above.

The As raw material 14 includes arsine (molecular formula AsH ₃ ), tertiary butyl arsine (molecular formula C ₄ H ₁₁ As), or trimethyl arsenic (molecular formula (C
Gases containing at least one of H ₃ ) ₃ As) are mentioned.

As the III-V semiconductor substrate, G
It is not limited to only the aAs substrate.
Any substrate that is commonly used when forming an s-based mixed crystal semiconductor layer can be applied. Further, the group III-V semiconductor substrate may include an n-type dopant such as Si (silicon).

According to the method of manufacturing a semiconductor according to the present embodiment, when a GaInNAs-based mixed crystal semiconductor layer is grown on a III-V semiconductor substrate, Ga is used as a source gas.
Raw material 11, In raw material 12, N raw material 13, and As raw material 1
4 as well as performing the entire crystal growth process in an atmosphere containing the halogen gas 15, thereby suppressing the occurrence of GaAs and InAs bonds, and
The aAs bond and the InAs bond are etched, whereby the GaN in the GaInNAs-based mixed crystal semiconductor layer is removed.
The ratio of the bond and the InN bond relatively increases. At this time,
By adjusting the ratio of the halogen gas 15 to the atmospheric gas and the type of the halogen gas 15, the composition of the group V element in the GaInNAs-based mixed crystal semiconductor layer can be controlled. GaI with large
An nNAs-based mixed crystal semiconductor layer can be formed.

The semiconductor manufacturing method according to the present embodiment is a conventional manufacturing method (a method in which the supply amount of the N raw material is significantly increased with respect to the supply amount of the As raw material, or a method in which the supply amount of the N raw material is maintained. Method to reduce the supply of As raw material)
The crystal growth is performed only in an atmosphere containing the halogen gas 15 without changing the supply amounts of the N raw material 13 and the As raw material 14, and the ratio of the halogen gas 15 to the atmospheric gas and the type of the halogen gas 15 are adjusted. And Ga
The composition of the group V element in the InNAs-based mixed crystal semiconductor layer is controlled. For this reason, the composition of the GaInNAs-based mixed crystal semiconductor layer can be accurately controlled without being affected by the change in the raw material supply amount. As a result, the N of the GaInNAs-based mixed crystal semiconductor layer grown in a non-equilibrium system can be controlled. The take-up efficiency can be increased. Also, there is no reduction in throughput.

The light emitting device formed by using the manufacturing method of the present embodiment does not necessarily need to be a laser, and can be applied to, for example, a light emitting diode (LED). Further, the laser does not necessarily need to be used in a single chip, and may be a laser diode array as needed. Further, the structure of the laser resonator does not necessarily have to be a vertical resonator using a multilayer reflector or a resonator using a cleavage surface as a reflector. For example, a periodic structure (grating) provided in an element may be a resonator. Alternatively, a photonic crystal may be used as the resonator.

The light emitting device formed by using the manufacturing method of the present embodiment can be applied to, for example, a laser diode for optical communication using a quartz single mode optical fiber.

Next, another embodiment of the present invention will be described with reference to the accompanying drawings.

(Second Embodiment) FIG. 2 shows a raw material supply sequence in a semiconductor manufacturing method according to a second embodiment. Note that the same members as those in FIG. 1 are denoted by the same reference numerals, and detailed description of these members will be omitted.

In the manufacturing method of the above embodiment, Ga
The entire crystal growth process of the InNAs-based mixed crystal semiconductor layer is performed in an atmosphere containing a halogen gas (or a halogen compound gas) 15.

On the other hand, in the semiconductor manufacturing method according to the second embodiment, as shown in FIG. 2, a part of the crystal growth step is performed by using a halogen gas (or a halogen compound gas).
15, and the remainder of the crystal growth step is performed in an atmosphere containing no halogen gas 15.

Specifically, GaAs placed in a growth reactor
A desired epitaxial layer is formed on the substrate in advance. After that, a GaInNAs-based mixed crystal semiconductor layer is formed. This crystal growth step includes a plurality of steps (three steps in FIG. 2).

In the first step A (time 0 to t1), a Ga source (eg, TEGa, TM
Ga) 11, an In material (for example, TMIn) 12, an N material (for example, DMHy) 13, and an As material (for example,
TBAs) 14 are supplied simultaneously, and only the carrier gas is supplied as the atmospheric gas. Thereafter, the inside of the growth furnace is maintained at a predetermined pressure and temperature, and the GaI is removed under an atmosphere containing no halogen gas 15 (under an atmosphere containing only a carrier gas).
An nNAs-based mixed crystal semiconductor layer is formed. Next, in step B (time t1 to t2), the same conditions as in step A are used except that the halogen gas 15 is supplied together with the carrier gas.
An As-based mixed crystal semiconductor layer is formed. Next, step A (time t2 to t3) is performed again, and a GaInNAs-based mixed crystal semiconductor layer is formed in an atmosphere containing no halogen gas 15.

At this time, in the step B, the GaInNAs-based mixed crystal semiconductor layer is grown in an atmosphere containing the halogen gas 15 so that the generation of the GaAs bond and the InAs bond is suppressed and the generated Ga is formed.
As and InAs bonds are etched. For this reason, the ratio of the GaN bond and the InN bond in the GaInNAs-based mixed crystal semiconductor layer is relatively increased, and as a result, a layer B having a high N taking-in efficiency is formed. In step A, GaIn is performed in a normal state, that is, in a non-equilibrium system.
Since the NAs-based mixed crystal semiconductor layer grows, a layer A having a low efficiency of taking in N is formed.

Thereafter, desired epitaxial layers are formed on the GaInNAs-based mixed crystal semiconductor layers, respectively.
By forming an electrode portion and performing wire bonding, a semiconductor element, for example, a light emitting element can be obtained.

Here, the growth / formation time of the layer A and the growth / formation time of the layer B, that is, the ratio between the supply stop time (t1-0 or t3-t2) of the halogen gas 15 and the supply time, and the length of each time Is adjusted, the composition of the group V element in the GaInNAs-based mixed crystal semiconductor layer can be controlled. More specifically, the ratio between the supply stop time and the supply time of the halogen gas 15 is 10: 1 to 1:10, preferably 2: 1 to 1: 2. The supply stop time is, for example, 1 to
60 (sec), preferably 1 to 10 (sec), and the supply time is, for example, 1 to 60 (sec), preferably 1 to 10 (sec).

The thickness of the layer A grown and formed in one step A is 1 to 100 (nm), preferably 1 to 10 (nm). The layer B to be formed has a layer thickness of 1 to 100 (nm), preferably 1 to 10 (nm).

The relationship between the number of insertions of step B in the entire crystal growth process and the halogen gas supply time (t2-t1 in FIG. 2) in step B is not particularly limited, but the desorption of the raw material from the surface is not limited. Considering
It is preferable to shorten the halogen gas supply time and increase the number of insertions in step B.

In the manufacturing method of the present embodiment, the same operation and effect as in the manufacturing method of the previous embodiment can be obtained.

Further, according to the method of manufacturing a semiconductor according to the present embodiment, GaInNA is formed on a III-V semiconductor substrate.
When the s-based mixed crystal semiconductor layer is grown, the step A and the step B are used together to grow and form the GaInNAs-based mixed crystal semiconductor layer. A layered structure with the layer B grown and formed by B. At this time, the growth and formation time of the layer A and the growth and formation time of the layer B, that is, the ratio between the supply stop time and the supply time of the halogen gas 15 and the length of each time are adjusted to adjust the GaInNAs-based mixed crystal semiconductor layer. It becomes possible to control the composition of the group V element at higher accuracy.

Further, only in a part of the crystal growth process, the GaInNA
By forming the s-based mixed crystal semiconductor layer, a light confinement layer and a multilayer reflective film required for a light emitting element can be easily formed by using a conventional GaAs-based compound semiconductor growth technique.

As described above, the embodiments of the present invention are not limited to the above-described embodiments, and it is needless to say that various other embodiments are also conceivable.

[0049]

Next, the present invention will be described based on examples, but the present invention is not limited to these examples.

(First Embodiment) FIG. 3 is a schematic cross-sectional view of a light emitting device (semiconductor device) according to the first embodiment, and FIG. 4 shows an emission spectrum of the light emitting device of FIG.

On a silicon-doped n-type GaAs substrate 31 by a metal organic chemical vapor deposition method, a 95-nm-thick Si-doped n-type GaAs layer 32a and a 108-nm-thick Si-doped n-type Al
A lower multilayer reflective film 32 in which As layers 32b are alternately stacked for 30 periods, a Si-doped n-type GaAs cavity layer 33 having a thickness of 190 nm, a GaInNAs active layer 34 having a thickness of 10 nm, and a thickness 19
0 nm Mg-doped p-type GaAs cavity layer 35, thickness 9
5 nm Mg-doped p-type GaAs layer 36a and 108 nm thick
The upper multilayer reflective film 36 in which the Mg-doped p-type AlAs layers 36b are alternately stacked for 25 periods, and the Mg-doped p-type GaAs contact layer 37 having a thickness of 20 nm are sequentially formed.

Here, when forming the lower multilayer reflective film 32 except the GaInNAs active layer 34, the cavity layers 33 and 35, the upper multilayer reflective film 36, and the contact layer 37, trimethylgallium (TMGa), Al Trimethyl aluminum (TMAl) was used as a raw material, and arsine (AsH ₃ ) was used as an As raw material. These source gases were supplied into a growth furnace together with hydrogen gas as a carrier gas, and were vapor-phase grown in a hydrogen atmosphere. The pressure inside the growth furnace is 6.65
× 10 ³ Pa (50 Torr), and the growth temperature was 650 ° C.

When forming the GaInNAs active layer 34, triethyl gallium (TEGa) as a Ga raw material,
Trimethyl indium (TMIn) was used as the In raw material, and tertiary butyl arsine (TBA) was used as the As raw material.
s), Dimethylhydrazine (DMHy) was used as the N raw material. TEGa, TMIn, TBAs, and DMHy
Are 2.3 × 10 ⁻³ mol / min and 3.0, respectively.
4.times.10.sup.- ⁴ mol / min, 2.2.times.10.sup.- ³ mol / min.
It was 0 × 10 ⁻³ mol / min. These source gases were converted to hydrogen gas (flow rate: 1.5 liter /
) And a chlorine gas (flow rate: 0.5 l / min) as a halogen gas. The pressure in the growth furnace was 6.65 × 10 ³ Pa (50 Torr), and the growth temperature was 515 ° C.

Next, an epitaxial wafer formed by growing and forming each epitaxial layer on the GaAs substrate 31
The chip was processed into a 0 μm square chip, and an upper electrode 38 made of an Au—Zn alloy and a lower electrode 39 made of an Au—Ge—Ni alloy were formed on the upper and lower surfaces of the chip, respectively. The upper electrode 38 is a ring-shaped electrode having a circular hole 38a having a diameter of 10 μm.
Further, a portion of the upper multilayer reflective film 36 located immediately below the portion where the upper electrode 38 is formed is selectively oxidized in advance,
It was formed so as to cause current constriction. Further, the upper electrode 3
8, a surface emitting laser having a vertical cavity was manufactured by bonding an Au wire 40 thereto.

When a direct current was applied to the surface emitting laser and the emission spectrum at an emission output of 5 mW was measured by an optical spectrum analyzer, an emission spectrum as shown in FIG. 4 was obtained. FIG. 4 shows that the surface emitting laser of the first embodiment oscillates at a wavelength of 1.310 μm.

Next, on the Si-doped n-type GaAs substrate 31 under the same conditions as for the GaInNAs active layer 34 described above,
A nm GaInNAs layer was grown and formed, and SIMS analysis was performed. As a result, the N concentration was about 4.1 × 10 ²⁰ atoms / cm ³ . The N concentration is such that the N composition is about 2.0% (mol
%) Of GaInNAs. From the N concentration and the lattice constant of the GaInNAs layer obtained by the X-ray diffraction method, the In composition was about 25%.
(Mol%). That is, the GaInNAs active layer 34 of the surface emitting laser obtained in the present embodiment is Ga _0.75 In _0.25
It was found to have a composition of N _0.02 As _0.98 . That is, according to the present embodiment, Ga _0.75 In _0.25 N _0.02 A
A surface emitting laser having a wavelength of 1.3 μm and having an active layer of s _0.98 was obtained.

(Second Embodiment) FIG. 5 is a schematic cross-sectional view of a light emitting device (semiconductor device) according to a second embodiment, and FIG. 6 shows an emission spectrum of the light emitting device of FIG.

A 500 nm-thick Si-doped n-type GaAs buffer layer 52 and a 1500 nm-thick Si-doped n-type Al _0.75 Ga _0.25 As clad on a Si-doped n-type GaAs substrate 51 by metal organic chemical vapor deposition. Layer 53, thickness 5
0 nm Si-doped n-type GaAs light guide layer 54, thickness 6n
m undoped GaInNAs quantum well layer 55a and thickness 6 nm
Of undoped GaAs barrier layer 55b
InNAs / GaAs 3-MQW layer 55, 50 nm thick Mg doped p
-Type GaAs optical guide layer 56, Mg-doped p-type Al _0.75 Ga _0.25 As clad layer 57 having a thickness of 1500 nm, and a thickness of 2
A 0 nm Mg-doped p-type GaAs contact layer 58 was formed in order.

Here, the GaInNAs / GaAs 3-MQW layer 55 is excluded.
GaAs buffer layer 52, Al_0.75Ga _0.25As cladding layer
53, 57, GaAs light guide layers 54, 56, GaAs contact
When the gate layer 58 is formed, the Ga source is TMGa or Al source.
Using TMAl as a raw material and AsH as an As material_ThreeWas used. This
These source gases are combined with the carrier gas, hydrogen gas.
It was supplied into a growth furnace and vapor-phase grown in a hydrogen atmosphere. growth
The pressure inside the furnace is 6.65 × 10^ThreePa (50 Torr),
The growth temperature was 650 ° C.

In the GaInNAs / GaAs 3-MQW layer 55,
The GaInNAs quantum well layer 55a is made of GaInN in the first embodiment.
It was grown and formed under exactly the same growth conditions as the As active layer 34. one
On the other hand, when forming the GaAs barrier layer 55b, T
EGa, AsH raw material AsH _ThreeGaInNAs amount except using
It was grown and formed under exactly the same growth conditions as the sub well layer 55a.
From the growth of the GaInNAs quantum well layer 55a, the GaAs barrier layer 5
In transition to the growth of 5b, the GaInNAs quantum well layer 55a
The chlorine gas used in growing the GaAs barrier layer 55b
The flow rate is 2 liters so as not to affect the growth
To supply hydrogen gas per minute into the growth furnace for 30 seconds.
Was provided.

Next, an epitaxial wafer formed by growing and forming each epitaxial layer on the GaAs
After cleaving to a chip of 0 μm square, Mg-doped p-type Al _0.75 G was formed by reactive ion etching (RIE).
a _0.25 Surface layer of As clad layer 57 and Mg-doped p-type
The GaAs contact layer 58 was processed into a stripe section 65 having a width of 5 μm. Thereafter, an upper electrode 59 made of an Au-Zn alloy was formed on the upper surface of the stripe portion 65, and a lower electrode 60 made of the Au-Ge-Ni alloy was formed on the lower surface of the chip. Thereafter, an Au wire 61 was bonded to the upper electrode 59 to produce an edge-emitting laser having a resonator having a cleavage surface (a surface parallel to the drawing in FIG. 5) of the chip as a reflection surface.

When a direct current was applied to this laser and the emission spectrum at an emission output of 5 mW was measured by an optical spectrum analyzer, an emission spectrum as shown in FIG. 6 was obtained. FIG. 6 shows that the Fabry-Perot laser of the second embodiment oscillates at a wavelength of 1.35 μm.

GaInNA of edge emitting laser obtained in this example
The growth condition of the s quantum well layer 55a is G in the first embodiment.
Since the growth conditions of the aInNAs active layer 34 are exactly the same, the GaInNAs / GaAs 3-MQW layer 55 of the present embodiment has a Ga _0.75
It can be said that In _0.25 N _0.02 As _0.98 / GaAs MQW. That is, the present _{examples, Ga 0.75 In 0.25 N 0.0 2} A
An edge-emitting laser having a wavelength of 1.3 μm and having an s _0.98 / GaAs 3-MQW active layer was obtained.

[0064]

In summary, according to the present invention, GaIn
When the crystal growth of the NAs-based mixed crystal semiconductor layer is performed, at least a part of the crystal growth step is performed in an atmosphere containing a halogen gas or a halogen compound gas, so that during the crystal growth, the GaAs bond and the InAs In addition to suppressing the generation of the bond, the generated GaAs bond and InA
Since the s bond is etched, the ratio of the GaN bond and the InN bond in the GaInNAs-based mixed crystal semiconductor layer is relatively increased, and an excellent effect of improving the efficiency of taking in N is exhibited.

[Brief description of the drawings]

FIG. 1 shows a semiconductor manufacturing method according to a first embodiment;
It is a figure which shows a raw material supply sequence.

FIG. 2 illustrates a method of manufacturing a semiconductor according to a second embodiment;
It is a figure which shows a raw material supply sequence.

FIG. 3 is a schematic cross-sectional view of the semiconductor device of the first embodiment in the embodiment.

FIG. 4 is a diagram showing an emission spectrum of the semiconductor device of FIG. 3;

FIG. 5 is a schematic cross-sectional view of a semiconductor device according to a second embodiment in the embodiment.

6 is a diagram showing an emission spectrum of the semiconductor device of FIG.

[Explanation of symbols]

15 Halogen gas or halogen compound gas 31, 51 Si-doped n-type GaAs substrate (III-V semiconductor substrate) 34 Undoped GaInNAs active layer (GaInNA)
s-based mixed crystal semiconductor layer) 55 Undoped GaInNAs / GaAs 3-MQW layer (GaInNA
s-based mixed crystal semiconductor layer)

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Naoki Niguchi             1-6-1 Otemachi, Chiyoda-ku, Tokyo Sun             Standing wire company F term (reference) 5F045 AA04 AB18 AB19 AC01 AC07                       AC08 AC09 AF04 AF05 CA10                       CA12                 5F073 AA13 AA73 AA74 AB17 BA02                       CA17 CB02 DA05

Claims (6)

[Claims] 1. A semiconductor device comprising a group III-V semiconductor substrate and Ga, I
In a method for manufacturing a semiconductor having at least one GaInNAs-based mixed crystal semiconductor layer composed of a mixed crystal semiconductor containing n, N, and As as main components, the GaInNAs-based mixed crystal semiconductor layer is formed by metal organic chemical vapor deposition. When growing a crystal, at least a part of the crystal growth process,
A method for manufacturing a semiconductor, which is performed in an atmosphere containing a halogen gas or a halogen compound gas. 2. The method according to claim 1, wherein chlorine gas or bromine gas is used as the halogen gas. 3. The method according to claim 1, wherein a chlorine compound gas or a bromine compound gas is used as the halogen compound gas. 4. Monomethylhydrazine as N raw material,
4. The semiconductor manufacturing device according to claim 1, wherein a gas containing at least one of 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, tertiarybutylamine, tertiarybutylhydrazine, or ammonia is supplied. Method. 5. The method of manufacturing a semiconductor according to claim 1, wherein a gas containing at least one of arsine, tertiary butylarsine, and trimethylarsenic is supplied as the As raw material. 6. A semiconductor device having a light emitting layer, wherein at least the light emitting layer is formed of a GaInNAs-based mixed crystal semiconductor layer using the method of manufacturing a semiconductor according to any one of claims 1 to 5. element.