JP5031674B2 - Nitride semiconductor laser device and method for manufacturing nitride semiconductor laser device - Google Patents

Nitride semiconductor laser device and method for manufacturing nitride semiconductor laser device Download PDF

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JP5031674B2
JP5031674B2 JP2008150908A JP2008150908A JP5031674B2 JP 5031674 B2 JP5031674 B2 JP 5031674B2 JP 2008150908 A JP2008150908 A JP 2008150908A JP 2008150908 A JP2008150908 A JP 2008150908A JP 5031674 B2 JP5031674 B2 JP 5031674B2
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nitride semiconductor
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JP2008273835A (en
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吉裕 上田
茂稔 伊藤
健作 元木
貴之 湯浅
元隆 種谷
善平 谷
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シャープ株式会社
住友電気工業株式会社
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  The present invention relates to a nitride semiconductor laser element configured by laminating a nitride semiconductor layer on a nitride semiconductor substrate and a method for manufacturing the same.

A nitride III-V semiconductor (hereinafter referred to as “GaN-based semiconductor”) composed of a compound of a group III element such as Al, Ga, and In and a group V element N has a band structure, It has been expected to be used as a light emitting device or a power device because of its chemical stability, and its application has been attempted. For example, many attempts have been made to fabricate a nitride semiconductor laser element that emits a blue laser by laminating a GaN-based semiconductor on a sapphire substrate (Al 2 O 3 ) or SiC substrate.

  However, when a GaN crystal thin film is grown on a sapphire substrate or SiC substrate, many defects such as dislocations are introduced into the epitaxial layer due to the difference in lattice constant between GaN and the substrate material. Therefore, in the case of a nitride semiconductor laser device that allows a high-density current to flow, there is a risk that the defects are triggered, the lattice structure is disturbed, and the defects proliferate. Further, when the nitride semiconductor laser element is formed on the sapphire substrate, there is a problem in terms of life. It is considered that high-density dislocations limit the lifetime of the nitride semiconductor laser device.

  From these points, the substrate used for the GaN-based semiconductor device is ideally a GaN single crystal. Therefore, there is no difference in lattice constant between the substrate and each layer stacked on the substrate. Also, since GaN has a cleavage property, the process of cutting the wafer into chips is facilitated. Furthermore, the GaN crystal is conductive and simplifies electrode placement. In this respect, it is optimal to use a GaN single crystal for the substrate.

Non-Patent Document 1 reports a nitride semiconductor laser element that oscillates in the ultraviolet to visible region, using such a GaN substrate of GaN single crystal. In this nitride semiconductor laser element, a SiO 2 mask pattern having periodic stripe-shaped openings is formed on a GaN substrate, and a nitride semiconductor laminate having a stripe-shaped waveguide (ridge stripe structure) is formed thereon. It is constructed by forming a structure.

The following method is used for manufacturing this GaN substrate. A GaN layer having a thickness of 15 μm is formed by MOCVD (Metalorganic Chemical Vapor Deposition) on a seed crystal serving as a base on which an SiO 2 mask pattern having stripe-shaped openings having a period of 20 μm is formed, and the surface is flat. A wafer was obtained. This is a technique called ELOG (Epitaxially Lateral Overgrown), which is a technique for reducing defects by utilizing lateral growth. Further, a GaN substrate having a thickness of 200 μm was formed by a normal HVPE method (Hydride Vapor Phase Epitaxy), and the base was removed to manufacture a GaN substrate. The lifetime characteristic of the obtained semiconductor laser was an estimated lifetime of 15000 hours under an output condition of 30 mW at 60 ° C.
Japanese = Journal = Of = Applied = Physics 39 No.L647-L650 (Jpn. J. Appl. Phys. Vol.39 (2000) pp.L647-650)

  However, in the above-described nitride semiconductor laser device, the GaN substrate manufacturing method requires three crystal growths (HVPE growth, MOCVD underlayer growth, and MOCVD laser structure growth), which is complicated and has a problem in productivity. It was. In addition, the life characteristics are not yet sufficient, and the life characteristics under the conditions of higher temperature and higher output (for example, 70 ° C. and 60 mW) are not sufficient. In addition, there is a case where the yield is lowered due to a crack appearing on the surface of the grown film after the growth of the laminated structure, which leads to a decrease in the yield during manufacturing.

These problems are caused by crystal defects (= dislocations) existing in the nitride semiconductor laser element. This crystal defect is usually about 5 × 10 7 cm −2 in the GaN substrate. Has been confirmed to exist. If a means such as bending or eliminating the crystal defects is used, a region with a low defect density can be obtained, and a sufficient device life can be ensured under the high power condition which is a problem. In addition, if the crystal growth layer formed in the GaN substrate or on the GaN substrate has a mechanism to relieve strain structurally, the probability of cracking decreases, and the yield due to cracks decreases. Does not occur.

  The present invention has been made in view of these points, and an object of the present invention is to provide a nitride semiconductor laser device in which internal crystal defects are reduced and stress is relaxed, and a simple manufacturing method thereof.

The nitride semiconductor laser device has a growth suppression film for suppressing the growth of nitride semiconductor crystals at the position of the dislocation concentration region on the surface of the nitride semiconductor substrate of (A1) below, and the growth suppression film is provided. A nitride semiconductor layer is stacked on the nitride semiconductor substrate thus formed, and a ridge stripe portion is above the nitride semiconductor layer formed between the growth suppression films.
(A1) a nitride semiconductor substrate including a nitride semiconductor formed using a substrate,
The following (1) dislocation concentration region, (2) low dislocation region, and (3) high luminescence region are included,
(1) A mask is formed by growing a base after forming a striped mask on the base.
The top of the bottom is a stripe-shaped high-density defect area and both sides of the bottom
A V-shaped slope consisting of facet surfaces other than the surface perpendicular to the growth direction
By maintaining the growth, the slope of the facet surface is maintained.
It becomes a boundary that distinguishes the surrounding area from the upper surface to the lower surface of the substrate in a striped manner by concentrating crystal defects at the bottom of the slope,
Furthermore, the dislocation concentration region in any of the following (a) to (c)
(A) Polycrystalline state
(B) In a single crystal state and inclined with respect to the surrounding low dislocation region
(C) Reversing the c-axis in the [0001] direction with respect to the surrounding low dislocation region
(2) Low dislocation region which is a region excluding the dislocation concentration region (3) Facet plane {0001} plane is exposed and grows at the center of the low dislocation concentration region
Boundary that can be distinguished from the surroundings by emitting light.
High luminescence region serving as a boundary A nitride semiconductor substrate in which the surface of the nitride semiconductor substrate has an off angle in the range of 0.2 ° to 1 ° from the (0001) plane.

Further, the nitride semiconductor laser element has a growth suppression film that suppresses the growth of the nitride semiconductor crystal at the position of the dislocation concentration region on the surface of the nitride semiconductor substrate of (A2) below, and the growth suppression film A nitride semiconductor layer is stacked on the nitride semiconductor substrate provided with a ridge stripe portion above the nitride semiconductor layer formed between the growth suppression films.
(A2) a nitride semiconductor substrate including a nitride semiconductor formed using a base,
The following (4) dislocation concentration region, (5) low dislocation region, and (6) high luminescence region are included,
(4) After forming a dot-shaped mask on the substrate, the substrate is grown, so that
The top face of the pit-like high-density defect area is the bottom, the pit is surrounded, and the growth of the facet surface, which is a surface other than the surface perpendicular to the growth direction, is maintained to maintain the slope of the facet surface. While growing, the crystal defects are concentrated at the lower part of the slope, forming a dot-like pattern that extends from the upper surface to the lower surface of the substrate, and becomes a boundary that distinguishes from the surrounding area.
Furthermore, the dislocation concentration region in any of the following (a) to (c)
(A) Polycrystalline state
(B) In a single crystal state and inclined with respect to the surrounding low dislocation region
(C) The c-axis in the [0001] direction is reversed with respect to the surrounding low dislocation region.
State (5) Low dislocation region which is a region excluding the dislocation concentration region (6) Facet plane {0001} plane appears and grows at the center of the low dislocation concentration region
Boundary that can be distinguished from the surroundings by emitting light.
High luminescence region serving as a boundary A nitride semiconductor substrate in which the surface of the nitride semiconductor substrate has an off angle in the range of 0.2 ° to 1 ° from the (0001) plane.

  In addition, it is desirable that the stripe-shaped dislocation concentration region is substantially parallel to the [1-100] direction. The width of the stripe-shaped dislocation concentration region is preferably 10 μm to 40 μm. Further, it is desirable that the portion including the stripe-shaped dislocation concentration region is depressed on the surface of the nitride semiconductor substrate.

  Note that the off-angle is desirably 0.4 ° to 0.8 °. The material to be doped is preferably oxygen. In addition, it is desirable that the nitride semiconductor substrate has n-type conductivity due to the doped oxygen.

  The nitride semiconductor substrate preferably has a plurality of dislocation concentration regions, and the distance between the dislocation concentration regions is preferably 100 μm or more and 600 μm or less.

Further, in the method for manufacturing a nitride semiconductor laser device, a nitride semiconductor crystal is grown at a position of a dislocation concentration region on the surface of the nitride semiconductor substrate manufactured by the following method for manufacturing a nitride semiconductor substrate (B1). A step of forming a growth suppression film for suppressing the growth, a step of laminating a nitride semiconductor layer on the nitride semiconductor substrate provided with the growth suppression film, and a ridge stripe portion formed between the growth suppression films Forming above the nitride semiconductor layer.
(B1) A method of manufacturing a nitride semiconductor substrate,
Forming a mask on a substrate made of GaAs, sapphire, SiC, quartz, NdGaO 3 , ZnO, GaN, AlN, ZnB 2 , Si, spinel, MgO, or GaP;
After forming a striped mask on the substrate, the substrate is grown so that the stripe-shaped high-density defect region is directly above the mask, and both sides of the bottom are other than the surface perpendicular to the growth direction. By making the slope of the facet surface, which is the face of the surface, into a V shape and sustaining the growth, it is grown while maintaining the slope of the facet surface, and the crystal defects are concentrated in the lower part of the slope to form a stripe shape. In addition, a dislocation-concentrated region that grows from one of the following states (a) to (c) is formed as a boundary that distinguishes from the surrounding region while forming a series from the upper surface to the lower surface of the substrate. A process of
(A) Polycrystalline state
(B) In a single crystal state and inclined with respect to the surrounding low dislocation region
(C) The c-axis in the [0001] direction is reversed with respect to the surrounding low dislocation region.
A step of polishing so that the surface of the nitride semiconductor substrate has an off angle in the range of 0.2 ° to 1 ° from the (0001) plane;
Have
In the center of the low dislocation concentration region, there is formed a high luminescence region which is a stripe shape generated by the growth of the facet plane {0001} surface and becomes a boundary which is distinguished from the surrounding by emitting light. A method for manufacturing a nitride semiconductor substrate.

The nitride semiconductor laser device is manufactured by growing a nitride semiconductor crystal at a position of a dislocation concentration region on the surface of the nitride semiconductor substrate manufactured by the nitride semiconductor substrate manufacturing method of (B2) below. A step of forming a growth suppression film for suppressing the growth, a step of laminating a nitride semiconductor layer on the nitride semiconductor substrate provided with the growth suppression film, and a ridge stripe portion formed between the growth suppression films Forming above the nitride semiconductor layer.
(B2) A method of manufacturing a nitride semiconductor substrate,
Forming a mask on a substrate made of GaAs, sapphire, SiC, quartz, NdGaO 3 , ZnO, GaN, AlN, ZnB 2 , Si, spinel, MgO, or GaP;
After forming a dot-shaped mask on the substrate, the substrate is grown so that the pit-shaped high-density defect area is directly above the mask and the pits are surrounded by a surface other than the surface perpendicular to the growth direction. By maintaining the growth of the facet surface, it is grown while maintaining the slope of the facet surface, and crystal defects are concentrated at the bottom of the slope to form dots and from the top surface to the bottom surface of the substrate And a step of growing a dislocation-concentrated region that becomes a boundary that is distinguished from the surrounding region and that is in any of the following states (a) to (c):
(A) Polycrystalline state
(B) In a single crystal state and inclined with respect to the surrounding low dislocation region
(C) The c-axis in the [0001] direction is reversed with respect to the surrounding low dislocation region.
A step of polishing so that the surface of the nitride semiconductor substrate has an off angle in the range of 0.2 ° to 1 ° from the (0001) plane;
Have
In the center of the low dislocation concentration region, there is formed a high luminescence region which is a stripe shape generated by the growth of the facet plane {0001} surface and becomes a boundary which is distinguished from the surrounding by emitting light. A method for manufacturing a nitride semiconductor substrate.

  Further, in the method for manufacturing a nitride semiconductor substrate, it is desirable that stripe-like dislocation concentration regions are formed substantially parallel to the [1-100] direction. Further, it is desirable to form a stripe-shaped dislocation concentration region having a width of 10 μm to 40 μm. Further, it is desirable that a stripe-shaped dislocation concentration region is formed and a portion including the stripe-like dislocation concentration region is recessed on the surface of the nitride semiconductor substrate.

  In the method for manufacturing a nitride semiconductor substrate, it is desirable that the off angle is 0.4 ° to 0.8 °. Further, it is desirable to dope oxygen. In addition, it is desirable to produce n-type conductivity by doping oxygen.

  In the method for manufacturing a nitride semiconductor substrate, it is preferable that a plurality of dislocation concentrated regions are formed and the distance between the dislocation concentrated regions is 100 μm or more and 600 μm or less.

  According to the present invention, it is possible to provide a nitride semiconductor laser device in which internal crystal defects are reduced and stress is relaxed, and a simple manufacturing method thereof.

Embodiments of the present invention will be described below with reference to the drawings. In this specification, the nitride semiconductor layer stacked on the nitride semiconductor substrate (GaN substrate) means at least Al x Ga y In z N (0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦). 1, x + y + z = 1). In the nitride semiconductor layer, about 10% or less of the nitrogen element constituting the nitride semiconductor layer (provided that the nitride semiconductor layer is hexagonal) is at least one element of the element group of As, P, and Sb. May be substituted with.

The nitride semiconductor layer may be doped with at least one of the impurity groups of Si, O, Cl, S, C, Ge, Zn, Cd, Mg, and Be. The total amount of impurities added is preferably 5 × 10 17 cm −3 or more and 5 × 10 20 cm −3 or less. The impurity for causing the nitride semiconductor layer to have n-type conductivity is particularly preferably Si, Ge, S, or Se among the impurity group, and the impurity for having p-type conductivity is Mg, Cd, or Be. Is particularly preferred.

  Moreover, the active layer in this specification refers to the generic name of the layer comprised from the well layer or the well layer, and the barrier layer. For example, an active layer having a single quantum well structure is composed of only one well layer, or is composed of a barrier layer / well layer / barrier layer. The active layer having a multiple quantum well structure includes a plurality of well layers and a plurality of barrier layers.

  Since GaN is hexagonal, a notation using four indices is used to represent the axial direction and plane orientation. The a-axis and b-axis are 120 degrees, and the lengths are equal (a = b). The c-axis orthogonal to these is a singular axis and not equal to the a-axis (c ≠ a). Since only the a-axis and the b-axis have no symmetry in expressing the direction of the ab plane, another axis is assumed. Let this be the d-axis. Note that the a, b, and d axes can be sufficiently specified with only the a and b axes, but since an extra d axis is introduced so as not to impair symmetry, they are not independent of each other.

  If one parallel plane group is expressed by four indices (klmn), this means that the distance from the origin at the point where the first plane is cut from the a-axis, b-axis, d-axis, and c-axis when counted from the origin. a / k, b / l, d / m, c / n. This is the same definition as in other crystal systems. However, since the a, b, and d axes are redundant coordinates included in the plane, k, l, and m are not independent and are always k + 1 + m = 0. The c-axis is the same as in the case of cubic crystals. When there are n equivalent parallel surfaces in the c-axis unit length, the index in the c direction is n. So the previous three of the four indices have rotational symmetry, but the c-axis indices are independent.

  Each plane orientation is represented by (...). The collective plane orientation is represented by {...}. Collective means a set of all plane orientations that can be reached by all symmetry operations that the crystal system allows a plane orientation. The crystal orientation is also expressed by the same index. The crystal orientation uses the same index as the index of the plane perpendicular to it. The individual direction is represented by [...]. The set direction is expressed by <...>. These are common sense of crystallography, but explained to avoid confusion. The negative index is indicated by a horizontal line above the number, which is intuitive and easy to understand. However, since a horizontal line cannot be drawn on the number, a negative number is indicated by adding a minus sign before the number.

<Method for producing GaN substrate>
First, a method for manufacturing a GaN substrate in which a nitride semiconductor layer is formed on the surface of a nitride semiconductor laser device for manufacturing the nitride semiconductor laser device will be described with reference to FIG. FIG. 1 is a diagram showing a manufacturing process of an n-type GaN substrate.

  In the crystal growth when manufacturing this n-type GaN substrate, it grows with an inclined surface composed of a facet plane. The facet plane means a plane other than a plane (growth plane) perpendicular to the growth direction. By maintaining the inclined surface that serves as the facet surface, the dislocations can be propagated in the growth direction and gathered at a predetermined position. The region where the facet plane has grown becomes a low dislocation region due to the movement of crystal defects (= dislocations). In addition, a growth having a high-density defect region having a clear boundary is formed at the lower part of the slope serving as the facet surface. Since dislocations gather at the boundary of the high-density defect region (corresponding to a “dislocation concentration region” described later) or inside thereof, the dislocation disappears or accumulates in the high-density defect region.

  At this time, the shape of the facet surface varies depending on the shape of the high-density defect region. When the high-density defect area has a dot shape, the facet surface is formed so as to surround the high-density defect area, and a pit composed of the facet surface is formed. Further, when the high-density defect region is in a stripe shape, the slopes of facet surfaces are formed on both sides of the high-density defect region with the stripe portion of the high-density defect region at the bottom. It becomes a letter shape.

  In order to form this high-density defect region, a seed for dislocation formation, which is an amorphous or polycrystalline layer, is preliminarily formed on a support base serving as a base substrate in a place where the high-density defect region is to be formed. It is necessary to form. By growing GaN on the support substrate on which the dislocation-forming species are formed on the surface in this way, a high-density defect region is formed in a region immediately above the dislocation-forming species. Then, by growing the GaN layer having this high-density defect region, it is possible to advance the growth while maintaining the facet surface without embedding the facet surface.

  That is, when the n-type GaN layer 22 is grown on the support substrate 21 by the hydride vapor phase epitaxy (HVPE) method, the growth is performed so that the facet surface {11-22} surface 23 is mainly exposed on the growing surface. To do. As a result, as shown in FIG. 1 (a), the cross-sectional pattern of the surface becomes a serrated uneven shape. However, a portion where the {0001} surface 26 is exposed is slightly formed in the vicinity of the apex of the convex portion.

Here, the HVPE method is to provide a Ga boat in the upstream part of the hot wall type reactor and to inject HCl gas into the heated Ga melt to grow the GaN layer 22 in the downstream part of the reactor. The base 21 is provided, and NH 3 is blown in advance. Then, HCl is blown into the heated Ga metal (melt) to synthesize GaCl, which is then sent downward, reacted with NH 3 below to synthesize GaN, and GaN is deposited on the substrate.

The base 21 was a 2 inch (111) GaAs wafer. The unevenness has a periodic structure with a pitch P = 400 μm, and has a shape extending like a bowl in the depth direction of the drawing. This GaAs wafer is more suitable than a sapphire wafer or the like because it can be easily removed when GaN is grown and then removed after producing an ingot of an n-type GaN layer 22 described later. Thus, in order to define the position of the unevenness, a SiO 2 mask having an opening corresponding to the recess is formed on the base 21 in advance (the opening corresponds to the above-mentioned “dislocation formation seed”). In addition, crystal growth may be performed with the facet surface exposed.

  That is, the openings of the mask are arranged in stripes at a pitch P = 400 μm so as to be parallel to the [1-100] direction of the GaN crystal, and the shape of the mask is a continuous stripe, or The arrangement may be such that individual dots are arranged on the line. Hereinafter, in this example, an example in which a GaN substrate is manufactured by forming a stripe shape with an interval of 400 μm will be described, but the interval between the openings need not be limited to 400 μm. Desirably, this interval is 100 μm or more, and more desirably 200 μm or more and 600 μm or less.

  A method (growth condition) for sustaining crystal growth with the facet surface {11-22} surface 23 exposed is disclosed in detail in Japanese Patent Application Laid-Open No. 2001-102307 filed earlier by the present applicant. is doing. Note that the crystal to grow is made n-type by doping oxygen during growth.

  In this way, the crystal growth is continued in a state where the facet surface {11-22} surface 23 is exposed, and further, the formation of the GaN crystal is continued, so that the height on the substrate 21 is increased as shown in FIG. An ingot with a 30 mm n-type GaN layer 22 is produced. At this time, a facet surface corresponding to the shape of the seed mask is formed on the surface. That is, when the mask has a dot-like pattern, pits composed of facet surfaces are regularly formed. When the mask has a stripe-like pattern, a V-shaped facet surface is formed.

  The ingot made of the n-type GaN layer 22 is sliced and cut by a slicer to obtain a thin piece (n-type GaN substrate). Further, this thin piece is polished, and the n-type GaN substrate having a flat surface with a diameter of 2 inches and a thickness of 350 μm as shown in the sectional view of FIG. 1C and the top view of FIG. 10 is obtained. Thereafter, by grinding and polishing the surface of the n-type GaN substrate 10, the surface can be flattened to be usable. That is, in this n-type GaN substrate 10, the surface for epitaxial growth is mirror-polished.

  Although this surface is almost (0001) plane, in order for the morphology of the nitride semiconductor layer epitaxially grown thereon to be flat and good, 0.2-1 in any direction from the (0001) plane. It is desirable to have an off-angle in the range of °, and in order to minimize the flatness of the surface in particular, the range of 0.4 to 0.8 ° is preferable.

  The surface of the n-type GaN substrate 10 thus configured was observed in detail with a microscope. The polished surface is not necessarily flat and has irregularities. That is, the region corresponding to the region 24 where the bottom of the concave portion was generated during crystal growth in FIG. 1 is slightly depressed.

  Further, the n-type GaN substrate 10 as a sample was immersed in a solution obtained by heating a mixed acid of sulfuric acid and phosphoric acid to 250 ° C., and etching was performed so that etch pits where facet surfaces gathered appeared on the surface. As a result, many etch pits appeared in the region corresponding to the region 24, and it was found that dislocations were extremely concentrated in this region. Since the above-described region 24 is highly concentrated in dislocations, it is considered that the region 24 is more easily eroded than other portions in the polishing process, and is generated by forming a recess.

The width | variety of the area | region 24 where this hollow was produced was about 10-40 micrometers. The region other than the region 24 is a low dislocation region of EPD (etch pit density) of 10 4 to 10 5 cm −2, and the EPD of the region 24 is three orders of magnitude larger than this. As described above, the region 24 where the depression is generated is a portion where the crystal defect density (= dislocation density) is several orders of magnitude larger than the surroundings, and is a region corresponding to the above-described high-density defect region. In the specification, it is hereinafter referred to as “dislocation concentration region”.

  Unlike the other regions on the substrate, the dislocation concentration region 24 sometimes has a reversed polarity. That is, at the surface position of the n-type GaN substrate 10, the surface other than the dislocation concentrated region 24 has a plane orientation from which Ga (gallium) is exposed, and the surface of the dislocation concentrated region 24 has a surface orientation from which N (nitrogen) is exposed. There was a case. The dislocation concentration region 24 has several states including such a state. That is, for example, when it is made of polycrystal, it is a single crystal but is slightly inclined with respect to the surrounding low defect region, or in the [0001] direction with respect to the surrounding low defect region as described above. There are cases where the c-axis is inverted. Such a dislocation concentration region 24 has a clear boundary and is distinguished from the surrounding region.

  Further, the n-type GaN substrate 10 as a sample was irradiated with ultraviolet rays (a Hg lamp 365 nm emission line can be used), and luminescence from the surface was observed with a fluorescence microscope using a microscope. As a result, a stripe-like region having a relatively distinct boundary and having a contrast different from the surroundings is observed at the center of the low dislocation region sandwiched between the dislocation concentration regions 24. This region is a region where light emission (luminescence) observed with the naked eye is stronger than the surroundings, and light emission slightly yellowish is observed brightly.

  The observed bright region 25 of light emission is a portion where the {0001} plane has been exposed during crystal growth. The reason for being observed differently from the surroundings as described above may be the reason that the incorporation of the dopant is different from the surroundings. Therefore, hereinafter, this region 25 is referred to as a “high luminescence region”. Further, during crystal growth, the portion where the {0001} plane has been exposed does not necessarily proceed uniformly with the same width, and thus the width of the high luminescence region 25 is slightly fluctuated but 0 μm. To about 30 μm.

  The crystal growth method for forming such an n-type GaN substrate 10 may be vapor phase growth other than the HVPE method, such as MOCVD method (Metalorganic Chemical Vapor Phase Deposition), MOVPE method (Metalorganic Chloride Vapor Phase Epitaxy), and sublimation method. Etc. can also be carried out.

As the substrate 21 used for the growth for forming the n-type GaN substrate 10, a single crystal substrate having six-fold symmetry or three-fold symmetry around the axis can be used in addition to GaAs. That is, the crystal system is a hexagonal or cubic (Cubic symmetry) single crystal. In the case of the cubic system, there is a three-fold symmetry if the (111) plane is used. A hexagonal single crystal such as sapphire, SiC, SiO 2 , NdGaO 3 , ZnO, GaN, AlN, or ZrB 2 can be used. A cubic (111) plane substrate such as Si, spinel, MgO, or GaP can also be used. These grow GaN on the (0001) plane.

  Further, there are two ways of providing a mask for forming the n-type GaN substrate 10. One is a method of forming a mask directly on the substrate 21. In this case, it is necessary to devise such as depositing a GaN buffer layer on the exposed surface of the substrate inside the window prior to the epi layer. The other is a method in which a thin GaN layer is formed in advance on the substrate 21 and a mask is formed thereon. The latter is more preferable because the growth proceeds smoothly.

<First Embodiment>
A first embodiment of a nitride semiconductor laser device formed as described above and manufactured using an n-type GaN substrate having a dislocation concentration region and a high luminescence region will be described below with reference to the drawings. FIG. 2 is a cross-sectional view showing the configuration of the nitride semiconductor laser device of the present invention. In FIG. 2, the high luminescence region is omitted.

1. Formation of Growth Suppression Film First, the growth suppression film 13 as shown in FIG. 2 is formed on the surface of the n-type GaN substrate 10. The growth suppression film 13 is formed on the surface of the n-type GaN substrate 10 so as to cover the transition concentration region 11 (corresponding to the transition concentration region 24 in FIG. 2). The growth suppression film 13 serves to prevent dislocations from being taken over in the growth film on the n-type GaN substrate 10 when a nitride semiconductor laser device is formed by laminating a nitride semiconductor layer on the n-type GaN substrate 10. I do. Therefore, a material that makes it difficult to epitaxially grow a normal nitride semiconductor from the growth suppression film 13 is used for the growth suppression film 13. In the present embodiment, SiO 2 (silicon oxide) is used as the material of the growth suppression film 13.

The n-type GaN substrate 10 was placed in an electron beam evaporator, after the internal pressure has reached a predetermined degree of vacuum, is controlled such that the SiO 2 to a thickness of 0.2 [mu] m, the SiO 2 film n It is formed on the surface of the type GaN substrate 10. Thereafter, the deposited SiO 2 film is etched using simple photolithography so as to cover only the dislocation concentrated region 11 on the surface of the n-type GaN substrate 10, thereby forming the growth suppressing film 13. Since the width of the dislocation concentration region 11 is 40 μm or less, the width of the growth suppressing film 13 to be coated is set to 50 μm. By doing so, the GaN crystal grows from the low dislocation region 12.

In the present embodiment, SiO 2 is used as the growth suppression film 13, but similarly, a silicon compound such as Si 3 N 4 or a metal such as tungsten (W) or titanium (Ti) may be used. Moreover, although the film thickness of the growth suppressing film 13 to be coated is 0.2 μm, a sufficient effect can be obtained if it is about 0.05 μm to 1 μm. Further, the width of the growth suppressing film 13 to be coated is 50 μm, but it is wider if the dislocation concentration region 11 is covered and the low dislocation region 12 has a width for performing normal epitaxial semiconductor epitaxial growth. It doesn't matter.

2. Epitaxial growth of nitride semiconductor layer Using an MOCVD apparatus, NH 3 as a group V material, TMGa (trimethyl gallium) or TEGa (triethyl gallium) as a group III material, and SiH 4 as a dopant material are deposited on an n-type GaN substrate 10. The n-type GaN layer 101 having a film thickness of 3 μm is formed at a substrate temperature of 1050 ° C. using hydrogen or nitrogen as a source carrier gas. Next, TMIn (trimethylindium) as a group III material is added to the above material at a substrate temperature of 800 ° C. to form an n-type In 0.07 Ga 0.93 N crack preventing layer 102 of 40 nm.

Next, the substrate temperature is raised to 1050 ° C., and a 1.2 μm thick n-type Al 0.1 Ga 0.9 N cladding layer 103 is formed using a group III material of TMAl (trimethylaluminum) or TEAl (triethylaluminum). The dopant raw material was adjusted so that Si would be 5 × 10 17 cm −3 to 1 × 10 19 cm −3 as the n-type impurity. Subsequently, an n-type GaN light guide layer 104 (Si impurity concentration 1 × 10 16 to 1 × 10 18 cm −3 ) is formed to a thickness of 0.1 μm.

Thereafter, the substrate temperature is lowered to 750 ° C., and an active layer (multi-quantum well structure) composed of three periods of an In 0.1 Ga 0.9 N well layer having a thickness of 4 nm and an In 0.01 Ga 0.99 N barrier layer having an thickness of 8 nm. 105 is formed in the order of barrier layer / well layer / barrier layer / well layer / barrier layer / well layer / barrier layer. At that time, SiH 4 (Si impurity concentration is 1 × 10 16 to 1 × 10 18 cm −3 ) is introduced only when the barrier layer is formed or when both the barrier layer and the well layer are formed. When switching between the formation of the barrier layer and the well layer, if the growth is interrupted for 1 second or more and 180 seconds or less, the flatness of each layer is improved, and the half width of light emission is preferably reduced.

When As is added to such an active layer 105, AsH 3 (arsine) or TBAs (tertiarybutylarsine) or TMAs (trimethylarsine) is used. When P is added to the active layer 105, PH 3 (phosphine) is added. ) Or TBP (tertiarybutylphosphine) or TMP (trimethylphosphine), and when Sb is added to the active layer 105, TMSb (trimethylantimony) or TESb (triethylantimony) may be added. Further, when the active layer 105 is formed, as the N raw material, a hydrazine raw material such as N 2 H 4 (hydrazine) or C 2 N 2 H 8 (dimethylhydrazine), or an azide raw material such as ethyl azide is used in addition to NH 3. It doesn't matter.

When the active layer 105 has a plurality of In x Ga 1-x N quantum wells, and when As or P is added to the active layer 105 to form a quantum well active layer, if there are threading dislocations in the quantum well, the In It is known that segregates in the dislocation part. Therefore, in the case where a quantum well containing In x Ga 1-x N as a main constituent element is used for the active layer, it is necessary to reduce dislocations (crystal defects) as much as possible in order to obtain good laser characteristics. It is.

Next, the substrate temperature is again raised to 1050 ° C., and a 20 nm thick p-type Al 0.3 Ga 0.7 N carrier blocking layer 106, a 0.1 μm p-type GaN light guide layer 107, a 0.5 μm p-type Al 0.1 layer. A Ga 0.9 N cladding layer 108 and a 0.1 μm p-type GaN contact layer 109 are sequentially formed. At this time, EtCP 2 Mg (bisethylcyclopentadienylmagnesium) is used as a raw material as a p-type impurity, and the Mg is adjusted to 1 × 10 18 cm −3 to 2 × 10 20 cm −3 . As the Mg raw material, other cyclopenta-based Mg raw materials such as cyclopentadienyl magnesium and bismethylcyclopentadienyl magnesium may be used.

  The p-type impurity concentration of the p-type GaN contact layer 109 is preferably increased in the direction of the p-electrode 15. This reduces the contact resistance when the p-electrode 15 is formed. Further, in order to remove residual hydrogen in the p-type layer that hinders activation of Mg, which is a p-type impurity, a trace amount of oxygen may be mixed during the growth of the p-type layer.

After forming the p-type GaN contact layer 109 in this way, the entire reactor in the MOCVD apparatus is changed to nitrogen carrier gas and NH 3 , and the substrate temperature is lowered at a rate of 60 ° C./min. When the substrate temperature reaches 800 ° C., the supply amount of NH 3 is stopped, the substrate temperature is maintained at 800 ° C. for 5 minutes, and the substrate temperature is lowered to room temperature. The standby temperature is preferably between 650 ° C. and 900 ° C., and the standby time is preferably 3 minutes or more and 10 minutes or less. Further, the arrival speed when lowering the substrate temperature is preferably 30 ° C./min or more.

  As a result of evaluating the nitride semiconductor layer thus fabricated by Raman measurement, Mg is activated even if p-type annealing is not performed after removing the wafer from the MOCVD apparatus by the above-described method. Therefore, p-type characteristics are already exhibited after growth. Further, the contact resistance due to the formation of the p electrode 15 is also reduced. Further, it is preferable to perform conventional p-type annealing in combination because the Mg activation rate is further improved.

The n-type In 0.07 Ga 0.93 N crack prevention layer 102 may have an In composition ratio other than 0.07, or the n-type InGaN crack prevention layer 102 itself may be omitted. However, when the lattice mismatch between the n-type AlGaN cladding layer 103 and the n-type GaN substrate 10 becomes large, it is preferable to insert the n-type InGaN crack prevention layer 102 to prevent cracks. In order to prevent cracks, Ge may be used instead of Si as an n-type impurity.

  In addition, the active layer 105 has a configuration starting with a barrier layer and ending with a barrier layer, but may have a configuration starting with a well layer and ending with a well layer. Further, the number of well layers is not limited to the above-described three layers, and if it is 10 layers or less, the threshold current density is low and continuous oscillation at room temperature is possible. In this case, in particular, when the number of layers is 2 or more and 6 or less, the threshold current density is preferably low. Furthermore, the active layer 105 may contain Al.

Further, although the active layer 105 has a configuration in which a required amount of Si is added to both the well layer and the barrier layer, the active layer 105 may have a configuration in which no impurity is added. However, the emission intensity becomes stronger when an impurity such as Si is added to the active layer 105. The impurity added in this way may be at least one of the impurity groups of O, C, Ge, Zn and Mg in addition to Si. The total amount of impurities added is preferably about 1 × 10 17 to 8 × 10 18 cm −3 . Furthermore, the layer to which the impurity is added is not limited to both the well layer and the barrier layer, and may be only one layer.

The p-type Al 0.3 Ga 0.7 N carrier block layer 106 may have a different composition. For example, if In is added, the p-type is formed at a lower temperature growth, so that the substrate temperature can be reduced and the damage to the active layer 105 during crystal growth is reduced. Although the p-type AlGaN carrier block layer 106 may not be provided, the threshold current density is lower when the p-type AlGaN carrier block layer 106 is provided. This is because the p-type AlGaN carrier block layer 106 has a function of confining carriers in the active layer 105.

  Also, it is preferable to increase the Al composition ratio of the p-type AlGaN carrier block layer 106 because the carrier confinement becomes strong. At this time, it is more preferable to reduce the Al composition ratio to such an extent that carrier confinement is maintained, because the carrier mobility in the p-type AlGaN carrier block layer 106 increases and the electrical resistance decreases.

In addition, although Al 0.1 Ga 0.9 N crystals are used as the n-type AlGaN cladding layer 103 and the p-type AlGaN cladding layer 108, AlGaN ternary crystals having an Al composition ratio other than 0.1 may be used. When the mixed crystal ratio of Al increases, the energy gap difference and the refractive index difference with the active layer 105 increase, and carriers and light can be efficiently confined in the active layer 105, so that the laser oscillation threshold current density can be reduced. it can. Further, if the Al composition ratio is reduced to such an extent that the confinement of carriers and light is maintained, the carrier mobility in each of the n-type AlGaN cladding layer 103 and the p-type AlGaN cladding layer 108 increases, and the operating voltage of the device is lowered. can do.

  At this time, by setting the thickness of the n-type AlGaN cladding layer 103 to 0.7 μm to 1.5 μm, the unimodal vertical transverse mode and the light confinement efficiency are increased, the optical characteristics of the laser are improved, and the laser threshold current density is increased. Can be reduced. Further, although the n-type cladding layer 103 and the p-type cladding layer 108 are AlGaN ternary mixed crystals, they may be quaternary mixed crystals such as AlInGaN, AlGaNP, and AlGaNAs. Further, the p-type cladding layer 108 is configured with a superlattice structure composed of a p-type AlGaN layer and a p-type GaN layer or a superlattice structure composed of a p-type AlGaN layer and a p-type InGaN layer in order to reduce electric resistance. It doesn't matter.

  Further, when the nitride semiconductor layer is stacked on the n-type GaN substrate 10, the crystal growth method using the MOCVD apparatus is used. However, the molecular beam epitaxy method (MBE) or the HVPE method described above is used. It doesn't matter.

Subsequently, after removing the epitaxial wafer in which each layer of the nitride semiconductor layer is formed on the n-type GaN substrate 10 as described above from the MOCVD apparatus, each process step to be described later is processed into a nitride semiconductor laser element chip. Is made. Here, as shown in FIG. 2, the p-type Al 0.1 Ga 0.9 N clad layer 108 is a convex ridge stripe portion, which is a shape processed by a process step described later.

  In this way, the surface of the epi-wafer after the fabrication of the nitride semiconductor laser element is flat except for the portion directly above the growth suppression film 13. In addition, the nitride semiconductor layer is not epitaxially grown and is in a concave state immediately above the growth suppression film 13. In the nitride semiconductor layer obtained in this way, no cracks were observed in the portion other than directly above the growth suppression film 13 where the epitaxial growth was performed (hereinafter referred to as “epitaxial growth portion”).

  This is because the recess formed just above the growth suppression film 13 relaxes the stress, so that the residual stress is reduced in the epitaxial growth portion in the direction perpendicular to the ridge stripe portion (left-right direction in FIG. 2). It is considered a thing. In addition, since the dislocation propagating to the surface of the GaN substrate 10 is prevented from diffusing into the epitaxially grown portion located above the GaN substrate 10 by the growth suppressing film 13, the nitride semiconductor layer is low in the substrate. The dislocation density is lower than that using the normal GaN substrate 10 without exceeding the dislocation density in the defect region.

  Further, in the dislocation concentration region 11, it has been described that the polarity of the surface of the GaN substrate 10 may be reversed to the nitrogen surface. However, the growth suppression film 13 is formed on the dislocation concentration region 11 to grow the nitride semiconductor layer. Thus, when the nitrogen surface coexists on the surface of the GaN substrate 10, the growth on the normal Ga surface is not inhibited. Therefore, as the characteristics of the nitride semiconductor laser device, the effect of reducing crystal defects and relaxing stress can be confirmed as in the case where the polarity of the dislocation concentration region 11 is not reversed.

3. Elementization Process A ridge stripe portion for confining light in the horizontal direction with respect to the n-type GaN substrate 10 was formed on the surface of the flat portion of the nitride semiconductor layer. However, when the n-type GaN substrate 10 having the high luminescence region 25 (FIG. 1) is used, it is desirable that the ridge stripe portion is not formed at a position directly above the high luminescence region 25. This is because the high luminescence region 25 has a smaller dopant content or degree of activation and a higher resistivity than other regions, so that the drive current and device voltage injected into the nitride semiconductor laser device are high. This is because it is not preferable that a drive current flows in the high luminescence region 25.

  The ridge stripe part is produced by etching from the surface of the epi-wafer to the middle of the p-type AlGaN cladding layer 108 leaving a stripe-like part. Here, the stripe width was 1 to 3 μm, preferably 1.3 to 2 μm, and the distance from the p-type GaN guide layer 107 on the etching bottom surface was 0 to 0.1 μm. Thereafter, an insulating film 110 is formed in a portion other than the ridge stripe portion. Here, AlGaN is used as the insulating film 110. Since the p-type GaN contact layer 109 remaining without being etched is exposed, the p-electrode 15 is deposited on the surfaces of the p-type GaN contact layer 109 and the insulating film 110 in the order of Pd / Mo / Au. Been formed.

  Here, as the insulating film 110, oxides or nitrides such as silicon, titanium, zirconia, tantalum, and aluminum may be used in addition to the above. Further, any of Pd / Pt / Au, Pd / Au, or Ni / Au may be used as the material of the p-electrode 15.

  Further, by polishing the back side (substrate side) of the epi-wafer on which the p-electrode 15 is formed in this way, the thickness of the epi-wafer is adjusted to 80 to 200 μm so that the epi-wafer can be easily divided later.

  Then, the n electrode 16 is formed on the back side of the n-type GaN substrate 10 in the order of Hf / Al. As the material of the n-electrode 16, Hf / Al / Mo / Au, Hf / Al / Pt / Au, Hf / Al / W / Au, Hf / Au, Hf / Mo / Au, and Hf from these are used. An electrode material or the like replaced with Ti or Zr may be used.

  Finally, the epi-wafer provided with the n-electrode 16 is cleaved in a direction perpendicular to the ridge stripe direction, thereby producing a Fabry-Perot resonator having a resonator length of 600 μm. The resonator length is preferably 300 μm to 1000 μm. By this process, the epi-wafer was formed into a bar shape in which individual nitride semiconductor laser elements were connected side by side. The cavity facet of the nitride semiconductor laser element in which the stripe direction is formed along the <1-100> direction is the {1-100} plane of the nitride semiconductor crystal. Cleavage is not performed after the scriber marks are scratched on the entire surface of the epi wafer, but only a part of the epi wafer, for example, both ends of the epi wafer, is scored by the scriber. Is done.

In the bar-shaped Fabry-Perot resonator obtained in this way, as a feedback method, in addition to the feedback method using the resonator end face obtained by cleaving as described above, a generally known diffraction grating is used. A DFB (Distributed Feedback) provided in the resonator and a DBR (Distributed Bragg Reflector) provided with a diffraction grating outside the resonator may be used. After the epi-wafer is cleaved to form a resonator end face of a bar-shaped Fabry-Perot resonator, SiO 2 and TiO 2 dielectric films having a reflectivity of 70% are alternately deposited on the end face. A body multilayer reflective film is formed. As the dielectric multilayer reflective film, SiO 2 / Al 2 O 3 may be used as the dielectric multilayer reflective film.

  The bar-shaped Fabry-Perot resonator obtained in this way has a nitride semiconductor layer thickness or growth conditions stacked on the n-type GaN substrate 10 (substrate temperature during growth, pressure in the reactor, etc.). The configuration differs depending on the difference. For example, when the nitride semiconductor layer is thin, as shown in FIG. 3, the nitride semiconductor layer 402 is not coupled directly above the growth suppression film 13, and the region 403 immediately above the growth suppression film 13 is separated. It becomes a state. At this time, the portion formed in the region between the growth suppression films 13 constitutes one nitride semiconductor laser element 401.

  Further, when the thickness of the nitride semiconductor layer is made thicker than in the case of FIG. 3, it becomes as shown in FIG. 4 or FIG. That is, in FIG. 4, the nitride semiconductor layer 502 is bonded immediately above the growth suppression film 13, but there is a crack reaching the surface of the nitride semiconductor layer 502 in the region 503 immediately above the growth suppression film 13. . Further, in this region 503, there may be a case where a cavity 504 is formed on the surface of the growth suppression film 13 as shown in FIG. At this time, the portion formed in the region between the growth suppression films 13 constitutes the nitride semiconductor laser element 501.

  Further, in FIG. 5, the nitride semiconductor layer 602 is completely coupled immediately above the growth suppressing film 13. Therefore, unlike FIG. 4, the presence of cracks reaching the surface of the nitride semiconductor layer 602 is not confirmed in the region 603 immediately above the growth suppression film 13. Further, in this region 603, there may be a case where a cavity 604 is formed on the surface of the growth suppression film 13 as shown in FIG. At this time, the portion formed in the region between the growth suppression films 13 constitutes the nitride semiconductor laser element 601.

  Further, after that, the above bar-shaped Fabry-Perot resonator is divided to obtain a nitride semiconductor laser device having a configuration as shown in FIG. At this time, the laser light waveguide region 14 (located immediately below the ridge stripe portion) is disposed in the center of the nitride semiconductor laser element, and is divided so that the lateral width W of the nitride semiconductor laser element is 400 μm. Originally, the dislocation concentration region 24 (FIG. 1) is arranged on the n-type GaN substrate 10 at a pitch P = 400 μm. When a bar-shaped Fabry-Perot resonator is divided to obtain a nitride semiconductor laser element, the lateral width W of the nitride semiconductor laser element is an integral multiple of the pitch P of the dislocation concentration region 24 or an integral multiple of an integral multiple. It is convenient to divide into

  The nitride semiconductor laser device chip shown in FIG. 2 is manufactured in this way, so that the n-type GaN substrate 10 in which dislocations that are crystal defects are intentionally controlled is used, and the dislocation concentration region 11 is formed as a growth suppression film 13. As a result, a laser beam waveguide region 14 that is a current confinement portion of the nitride semiconductor laser device is formed in a region of low dislocation and low stress. Therefore, a laser oscillation lifetime of 5000 hours or longer was achieved under the conditions of a laser output of 60 mW and an ambient temperature of 70 ° C.

  In the present embodiment, the thickness of the growth suppression film 13 is 0.2 μm, but the present invention is not limited to this. When the nitride semiconductor laser device is configured by changing the film thickness of the growth suppressing film 13 from 0.01 μm to 2 μm, if the film thickness of the growth suppressing film 13 is less than 0.05 μm, Damage is caused by the temperature rise, and the effect as the growth suppressing film 13 cannot be obtained.

  Further, when the thickness of the growth suppression film 13 is thicker than 0.1 μm, the temperature rise before the nitride semiconductor layer stacking is caused by the difference in thermal expansion coefficient between the n-type GaN substrate 10 and the growth suppression film 13. The growth suppressing film 13 itself may be damaged. At this time, even if the growth suppression film 13 itself is not damaged, a nitride semiconductor layer that grows directly on the surface of the GaN substrate 10 other than the growth suppression film 13 is between the growth suppression film 13 and the GaN substrate 10. Abnormal growth occurs in the vicinity of the step due to the inhibition of raw material diffusion due to the effect of the step. The occurrence of such abnormal growth is referred to as “edge effect”. Due to this edge effect, trouble may occur in the process step, the oscillation wavelength of the laser may fluctuate, or the threshold for oscillation may increase.

  Therefore, the effect of manufacturing the growth suppression film 13 is obtained by manufacturing the growth suppression film 13 under the condition of 0.05 μm or more and 1 μm or less, and the nitride semiconductor laser having such a growth suppression film 13 is obtained. In the device, a good device life at high output aging can be obtained.

<Second Embodiment>
A second embodiment of a nitride semiconductor laser device formed as described above and manufactured using an n-type GaN substrate having a dislocation concentration region and a high luminescence region will be described below with reference to the drawings. Note that the epitaxial growth of the nitride semiconductor layer and the element fabrication process are the same as those in the first embodiment, and therefore the detailed description thereof will be omitted with reference to the first embodiment.

In the present embodiment, unlike the first embodiment, the growth suppressing film is formed in the shape of a scissors formed on the surface of the n-type GaN substrate 10 so as to cover the dislocation concentration region 24 (FIG. 1). It is formed. That is, as in the first embodiment, first, the n-type GaN substrate 10 is placed in an electron beam evaporation apparatus, and after the internal pressure reaches a predetermined degree of vacuum, SiO 2 is formed to a thickness of 0.2 μm. Under such control, an SiO 2 film is formed on the surface of the n-type GaN substrate 10. Thereafter, the deposited SiO 2 film is formed by using a simple photolithography, as shown in FIG. 6A, the growth suppressing film 301 having an interval of 5 μm and a width of 10 μm is formed every three n-type GaN substrates. 10 is formed so as to cover the dislocation concentration region 11 on 10.

  Thus, as shown in FIG. 6A, when the growth suppression film 301 having a film thickness of 0.2 μm is formed in the dislocation concentration region 11 of the GaN substrate 10 by the above-described method, the MOCVD apparatus is used. An n-type GaN film is grown at a pressure and a substrate temperature of 1000 ° C. Therefore, as shown in FIG. 6B, the GaN crystal 302 grows in the [0001] direction from the 5 μm window between the growth suppression films 301. At this time, the cross-sectional shape of the GaN crystal 302 becomes a completely convex triangular shape. Then, the pressure in the reactor of the MOCVD apparatus is lowered to 70 Torr, and the GaN crystal 302 is grown again at the substrate temperature of 1080 ° C.

  At this time, in FIG. 6B, the n-type GaN crystal 304 is a growth portion from a portion not covered with the growth suppression film 301, and dislocations in the n-type GaN substrate 10 are included in the n-type GaN film 304. There is only a dislocation density comparable to the dislocation density in regions other than the concentrated region 11. In the GaN crystal 302, dislocations 303 are taken over in a direction parallel to the growth axis in the [0001] direction. However, when the growth in the lateral direction perpendicular to the growth axis in the [0001] direction starts, the dislocation 303 bends in the direction perpendicular to the [0001] direction. At this time, the (11-22) plane and (-1-122), which are facet planes, grow at the leading edge.

  In this way, lateral growth is promoted from the portion where the GaN crystal 302 is grown in a convex shape as shown in FIG. 6B, and as shown in FIG. Combined with each other, it grows further upward. Further, the n-type GaN film 304 having low dislocations grows in the lateral direction, whereby the n-type GaN film 305 covering the GaN epitaxial film formed by growing the GaN crystal 302 is formed. The GaN epitaxial layer covered with the n-type GaN film 305 has dislocations 306 bent by lateral growth. Further, a small amount of dislocations concentrates on the junction 307 where the GaN crystal 302 and the n-type GaN film 304 are connected by lateral growth.

  About this, the JSPS Short-wavelength Optical Device No. 162 Committee, Optoelectronic Mutual Conversion No. 125 Committee No. 171 Joint Research Group Document (December 15-16, 2000), pages 25-32 Are listed. Thus, when a GaN crystal was grown on the surface of the n-type GaN substrate 10, the surface of the GaN film 305 grown to a total film thickness of about 8 μm was completely flat. After the n-type GaN film 305 was grown, the layer structure constituting the nitride semiconductor laser device was sequentially grown by the same method as in the first embodiment. Therefore, the nitride semiconductor layer 308 is formed on the n-type GaN film 305.

  Thereafter, by etching, a ridge stripe portion 309 is formed, and a laser element is manufactured. The position where the ridge stripe 309 of the nitride semiconductor laser element is formed may be above the low dislocation region 12 other than the region directly above the dislocation concentration region 11 or directly above the growth suppression film 303. Thus, also in this embodiment, a nitride semiconductor laser device having the same characteristics as those of the first embodiment can be obtained due to the effect of reducing crystal defects and the effect of relaxing strain. .

  In this embodiment, the width of the growth suppression film 301 is 10 μm and the interval is 5 μm. However, if the width of the growth suppression film 301 is a width and an interval capable of selective growth and lateral growth, nitrides are used. The superiority in the characteristics of the semiconductor laser device was recognized. However, when the width of the growth suppressing film 301 is not less than 1 μm and not more than 10 μm and the distance from the adjacent growth suppressing film 301 is not less than 1 μm and not more than 10 μm, a nitride semiconductor laser device having the most desirable characteristics can be obtained. it can. Further, the film thickness of the GaN film 305 formed so as to cover the growth suppression film 301 is 8 μm, but by setting the film thickness to 1 to 20 μm, the growth suppression film 301 is formed with respect to the nitride semiconductor layer to be stacked. The influence of can be reduced.

Furthermore, although SiO 2 is used as the material of the growth suppression film 301, a silicon compound such as Si 3 N 4 or a metal such as tungsten (W) or titanium (Ti) is used as in the first embodiment. It doesn't matter. Further, although the thickness of the growth suppressing film 301 to be coated is 0.2 μm, it may be about 0.05 μm to 1 μm. In addition, the saddle-like growth suppression film 301 is configured such that the total width of the width and the interval covers the dislocation concentration region 11.

  In the first and second embodiments, the nitride semiconductor laser element having the ridge stripe structure has been described. However, the present invention is not limited to this. Moreover, although the example which formed the electrode on both surfaces of the back surface of an n-type GaN substrate and the surface of the nitride semiconductor film produced by growing on the surface of an n-type GaN substrate was described, both p-type and n-type electrodes were described. It may be provided on the surface side of the n-type GaN substrate.

(When the active layer contains an element group of As, P and Sb)
The semiconductor laser device having the configuration as shown in FIG. 2 manufactured as in the first or second embodiment has a configuration in which an active layer 105 is laminated with an InGaN well layer and an InGaN barrier layer. Such an active layer 105 may contain at least one of the As, P, and Sb element groups.

  At this time, at least one of the As, P, and Sb element groups is contained in at least the well layer of the active layer 105 constituting the nitride semiconductor laser element. At this time, if the total composition ratio of the element groups of As, P, and Sb contained in the well layer is X and the N element composition ratio of the well layer is Y, X is smaller than Y. , X / (X + Y) is 0.3 or less. Further, X / (X + Y) is preferably 0.2 or less.

The lower limit of the total sum of the element groups is 1 × 10 18 cm −3 or more. When the total composition ratio X of the above element group becomes higher than 0.2, concentration separation with different composition ratios of the elements gradually starts to occur in the well layer. Further, when the total composition ratio X of the above element group becomes higher than 0.3, the crystallinity of the well layer is lowered due to the shift from the above-mentioned concentration separation to the crystal separation in which hexagonal system and cubic system are mixed. start. On the other hand, when the total addition amount of the above-described element group is smaller than 1 × 10 18 cm −3, it is difficult to obtain the effect due to the inclusion of the above-described elements in the well layer.

  As described above, by containing the elements of the element group of As, P, and Sb in the active layer 105, the effective mass of electrons and holes in the well layer is reduced, and the mobility of electrons and holes in the well layer is reduced. growing. Therefore, in the case of a nitride semiconductor laser element, the effect of obtaining a carrier inversion distribution for laser oscillation with a smaller amount of current injection is obtained in the former, and electrons and holes disappear in the active layer by recombination due to light emission. Even so, the effect that electrons and holes are newly diffused and injected at high speed can be obtained.

  It has been found that these effects are particularly prominent when there are no crystal defects in the quantum well. That is, when the active layer 105 contains any element of these element groups as compared with the InGaN-based nitride semiconductor laser element that does not contain any of the element groups of As, P, and Sb, the threshold current is increased. A nitride semiconductor laser device having a low density and excellent self-oscillation characteristics (excellent noise characteristics) can be manufactured.

<Application example to semiconductor optical device>
The case where the above-described nitride semiconductor laser element according to the present invention is applied to a semiconductor optical device such as an optical pickup system will be described below with reference to the drawings. FIG. 7 is a block diagram showing the internal configuration of the semiconductor optical device in this example. In this example, it is assumed that the nitride semiconductor laser element is used for an optical disk device.

  The optical disk apparatus shown in FIG. 7 includes a spindle motor 702 for rotating the optical disk 701 in the circumferential direction, an optical pickup 703 that reads information by irradiating the optical disk 701 with laser light, and a control circuit 704 that controls the entire apparatus. Have The optical pickup 703 is moved in the radial direction of the optical disc 701 by an actuator (not shown) driven by the control circuit 704.

  In such an optical disc apparatus, the optical pickup 703 detects the laser light from the laser device 705 having a nitride semiconductor laser element that outputs laser light, the laser light from the laser device 705 and the tracking mirror 708. A beam splitter 706 guided to the optical device 707, a photodetector 707 for detecting the laser light from the beam splitter 706 and providing a detection signal to the control circuit 704, and guiding the laser light from the laser device 705 to the optical disc 701 and the optical disc 701. A tracking mirror 708 that guides the laser light reflected from the tracking mirror 706 to the beam splitter 706, and an objective lens 709 that focuses the laser light from the tracking mirror 708 on the optical disk 701.

  At this time, the nitride semiconductor laser device (oscillation wavelength of 330 to 550 nm) according to the present invention provided in the laser device 705 operates stably in a high output (30 mW) and high temperature atmosphere (60 ° C.) as described above. In addition, the laser oscillation lifetime is long. Therefore, since the shorter the oscillation wavelength, the higher the density of recording / reproduction is possible, so that the optical disk apparatus is highly suitable for high-density recording / reproduction with high reliability.

  In the optical disk apparatus having such a configuration, when information is recorded, the laser beam output from the laser apparatus 705 is modulated in accordance with the input information from the control circuit 704, passes through the beam splitter 706, and then passes through the tracking mirror 708. Information is recorded on the optical disk 703 by being reflected and irradiated onto the optical disk 703 through the objective lens 709. Alternatively, the magnetic field applied to the recording surface of the optical disc 703 is modulated according to the input information from the control circuit 704, and the information is recorded on the disc.

  When reproducing information, the laser beam optically changed by the pit arrangement on the optical disk 701 is reflected by the tracking mirror 708 through the objective lens 709 and then detected by the photodetector 707 through the beam splitter 706. Thus, a reproduction signal is obtained. These operations are controlled by the control circuit 704. The power of the laser beam output from the semiconductor laser element is, for example, 30 mW during recording and about 5 mW during reproduction.

  The nitride semiconductor laser device according to the present invention is used in, for example, a laser printer, a bar code reader, a projector using three primary colors (blue, green, and red) lasers in addition to the optical disk device having such an optical pickup system. Is available.

<Another expression of invention>
The present invention can also be expressed as follows.

  The nitride semiconductor laser device of the present invention is a nitride semiconductor laser device comprising a nitride semiconductor substrate and a nitride semiconductor layer laminated on the nitride semiconductor substrate, wherein the nitride semiconductor substrate is a crystal A substrate having a stripe-like dislocation concentration region in which defects are concentrated and a low dislocation region excluding the dislocation concentration region, and is nitrided at a position covering the dislocation concentration region on the surface of the nitride semiconductor substrate. The nitride semiconductor layer is stacked by growing the nitride semiconductor crystal on the nitride semiconductor substrate on which the growth suppression film is provided. It is characterized by that.

  In this way, when the nitride semiconductor layer is stacked on the surface of the nitride semiconductor substrate, the propagation of dislocations, which are crystal defects from the dislocation concentration region, is suppressed by the growth suppressing film, and the nitride semiconductor layer is formed. It prevents the high-density crystal defects from spreading. Therefore, the crystal defect density in the nitride semiconductor layer can be lowered.

  In such a nitride semiconductor laser element, the growth suppression film is linear, and a plurality of the growth suppression films are provided so as to form a scissors shape with respect to each of the dislocation concentration regions. Each dislocation concentration region may be covered with a plurality of growth suppression films. By doing so, the nitride semiconductor crystal grown from the low dislocation region is easily bonded, and a plate-like growth suppression film is provided, and the nitride semiconductor crystal from the low dislocation region is nitrided without being bonded. Cleavage is easier than in the case where a physical semiconductor layer is stacked.

  At this time, each of the plurality of growth suppression films provided for each dislocation concentration region has a width of 1 μm or more and 10 μm or less, and is parallel with an interval between adjacent growth suppression films of 1 μm or more and 10 μm or less. The regions including the width and the interval of each of the plurality of growth suppression films cover the dislocation concentration regions.

  Further, a GaN film having n-type conduction characteristics is formed on the surface of the nitride semiconductor substrate so that the nitride semiconductor substrate has n-type conduction characteristics and covers the growth suppression film. By doing so, a GaN film having a flat surface can be formed, so that propagation of high-density crystal defects to the nitride semiconductor layer can be prevented. In addition, since the nitride semiconductor substrate is an n-type conductive substrate having a high resistance, the nitride semiconductor layers are stacked in the order of n-type and p-type. The flatness is further improved, and the current threshold for outputting the laser can be reduced. At this time, the film thickness of the GaN film having the n-type conductivity is set to 1 μm or more and 20 μm or less.

  Further, by setting the thickness of the growth suppression film to 0.05 μm or more and 1 μm or less, the effect of the growth suppression film is given and the influence of the growth suppression film is prevented. The growth suppression film is a silicon compound film or a metal film. Further, at this time, the growth suppressing film is any one of a SiO 2 film, a Si 3 N 4 film, a titanium film, and a tungsten film.

In the nitride semiconductor laser device described above, the nitride semiconductor layer includes a quantum well active layer, and the active layer includes a well layer composed of In x Ga 1-x N (0 <x <1). In addition, at least one of the As, P, and Sb element groups may be contained in the active layer. The nitride semiconductor substrate is preferably a GaN substrate.

  A method for manufacturing a nitride semiconductor laser element according to the present invention is a method for manufacturing a nitride semiconductor laser element comprising a nitride semiconductor substrate and a nitride semiconductor layer stacked on the nitride semiconductor substrate. On the surface of the nitride semiconductor substrate having a stripe-like dislocation concentration region where crystal defects are concentrated and a low dislocation region excluding the dislocation concentration region, a position covering the dislocation concentration region is formed on the surface of the nitride semiconductor crystal. The nitride semiconductor layer is stacked by growing the nitride semiconductor crystal on the nitride semiconductor substrate provided with the growth suppression film after forming a growth suppression film for suppressing growth. To do.

  At this time, after the growth suppression film is provided over the entire surface of the nitride semiconductor substrate, etching may be performed so that only the dislocation concentration region is covered with the growth suppression film. . The nitride semiconductor substrate has n-type conductivity, and the dislocation concentration region is coated with the growth suppressing film, and then the growth suppressing film is covered with the nitride semiconductor substrate. The nitride semiconductor layer may be stacked by forming a GaN film having n-type conductivity on the surface and growing the nitride semiconductor crystal on the surface of the formed GaN film. Absent.

  The semiconductor optical device of the present invention is characterized by using the nitride semiconductor laser element as described above as a light source.

The figure which shows the manufacturing process of an n-type GaN substrate. Sectional drawing which shows the internal structure of a nitride semiconductor laser element. Sectional drawing which shows a mode that the nitride semiconductor layer was laminated | stacked on the n-type GaN substrate. Sectional drawing which shows a mode that the nitride semiconductor layer was laminated | stacked on the n-type GaN substrate. Sectional drawing which shows a mode that the nitride semiconductor layer was laminated | stacked on the n-type GaN substrate. The figure which shows the growth process of the GaN crystal in 2nd Embodiment. The block diagram which shows the internal structure of the semiconductor optical apparatus which has the nitride semiconductor laser element of this invention.

Explanation of symbols

10 n-type GaN substrate
11 Dislocation concentration region
12 Low dislocation region
13 Growth suppression film
14 Laser light guide region
15 p-type electrode
16 n-type electrode
21 Support base
22 n-type GaN layer
23 Faceted surface
24 Dislocation concentration region
25 High luminescence area
26 {0001} face
101 n-type GaN layer
102 Crack prevention layer
103 n-type cladding layer
104 n-type GaN optical guide layer
105 Active layer
106 Carrier block layer
107 p-type GaN optical guide layer
108 p-type cladding layer
109 p-type contact layer

Claims (18)

  1. The following (A1) has a growth suppressing film for suppressing the growth of the nitride semiconductor crystal at the position of the dislocation concentration region on the surface of the nitride semiconductor substrate,
    A nitride semiconductor layer is stacked on the nitride semiconductor substrate provided with the growth suppression film,
    A nitride semiconductor laser element, wherein a ridge stripe portion is formed above the nitride semiconductor layer formed between the growth suppressing films and avoiding a position directly above the high luminescence region .
    (A1) A nitride semiconductor substrate including a nitride semiconductor formed by using a substrate to which a dopant is added during crystal growth ,
    Dislocation-concentrated regions of the following (1), includes a high luminescent Tsu sense region of the low dislocation region of (2), and (3),
    (1) A mask is formed by growing a base after forming a striped mask on the base.
    The top of the bottom is a stripe-shaped high-density defect area and both sides of the bottom
    A V-shaped slope consisting of facet surfaces other than the surface perpendicular to the growth direction
    By maintaining the growth, the slope of the facet surface is maintained.
    The substrate is elongated and the crystal defects are concentrated at the lower part of the slope, and the substrate is striped.
    Distinguishes from surrounding areas, starting from the top to the bottom
    A boundary,
    Furthermore, the dislocation concentration region in any of the following (a) to (c)
    (A) Polycrystalline state
    (B) In a single crystal state and inclined with respect to the surrounding low dislocation region
    (C) Reversing the c-axis in the [0001] direction with respect to the surrounding low dislocation region
    In the center of the state (2) low dislocation region (3) which is a region excluding the dislocation concentrated region of the low dislocation area that are growing facets {0001} plane is exposed
    The removal of dopants that are striped due to
    High luminescence area that becomes a boundary that distinguishes from the surroundings by emitting light
    The nitride semiconductor substrate, wherein the surface of the nitride semiconductor substrate has an off angle in the range of 0.2 ° to 1 ° from the (0001) plane.
  2. The following (A2) has a growth suppressing film that suppresses the growth of the nitride semiconductor crystal at the position of the dislocation concentration region on the surface of the nitride semiconductor substrate,
    A nitride semiconductor layer is stacked on the nitride semiconductor substrate provided with the growth suppression film,
    A nitride semiconductor laser element, wherein a ridge stripe portion is formed above the nitride semiconductor layer formed between the growth suppressing films and avoiding a position directly above the high luminescence region .
    (A2) A nitride semiconductor substrate including a nitride semiconductor formed by using a substrate to which a dopant is added during crystal growth ,
    Dislocation-concentrated regions of the following (4), includes a high luminescent Tsu sense region of low dislocation region (5) and (6),
    (4) After forming a dot-shaped mask on the substrate, the substrate is grown, so that
    The top is the pit-like high-density defect area and the pit is surrounded.
    By maintaining the growth of the facet surface, which is a surface other than the surface perpendicular to the growth direction,
    , Grow while maintaining the faceted slope, and crystal
    A series of dots from the top surface to the bottom surface of the substrate, with defects concentrated.
    Becoming a distinct boundary for the surrounding area,
    Furthermore, the dislocation concentration region in any of the following (a) to (c)
    (A) Polycrystalline state
    (B) In a single crystal state and inclined with respect to the surrounding low dislocation region
    (C) The c-axis in the [0001] direction is reversed with respect to the surrounding low dislocation region.
    Condition (5) In the center of the dislocation is an area excluding the centralized region low dislocation region (6) the low dislocation area, growth facets {0001} plane is exposed
    The removal of dopants that are striped due to
    High luminescence area that becomes a boundary that distinguishes from the surroundings by emitting light
    The nitride semiconductor substrate, wherein the surface of the nitride semiconductor substrate has an off angle in the range of 0.2 ° to 1 ° from the (0001) plane.
  3.   2. The nitride semiconductor laser device according to claim 1, wherein the dislocation concentration region in a stripe shape is substantially parallel to the [1-100] direction.
  4.   4. The nitride semiconductor laser device according to claim 1, wherein a width of the stripe-shaped dislocation concentration region is 10 μm to 40 μm.
  5.   5. The nitride semiconductor laser element according to claim 1, wherein a portion including the stripe-shaped dislocation concentration region is recessed on a surface of the nitride semiconductor substrate.
  6.   The nitride semiconductor laser element according to claim 1, wherein the off angle is 0.4 ° to 0.8 °.
  7.   The nitride semiconductor laser device according to claim 1, wherein the material to be doped is oxygen.
  8.   The nitride semiconductor laser element according to claim 7, wherein the nitride semiconductor laser element has n-type conductivity due to doped oxygen.
  9. There are multiple dislocation concentration areas,
    9. The nitride semiconductor laser device according to claim 1, wherein a distance between dislocation concentration regions is not less than 100 μm and not more than 600 μm.
  10. Forming a growth suppressing film for suppressing growth of nitride semiconductor crystals at a position of a dislocation concentration region on the surface of the nitride semiconductor substrate manufactured by the following method for manufacturing a nitride semiconductor substrate of (B1);
    Laminating a nitride semiconductor layer on the nitride semiconductor substrate provided with the growth suppressing film;
    Forming a ridge stripe portion above the nitride semiconductor layer formed between the growth suppression films and avoiding a position directly above the high luminescence region ;
    A method for manufacturing a nitride semiconductor laser device comprising:
    (B1) A method for manufacturing a nitride semiconductor substrate in which a dopant is added during crystal growth ,
    GaAs, sapphire, SiC, quartz, NdGaO 3 , ZnO, GaN, AlN
    Forming a mask on a substrate made of ZnB 2 , Si, spinel, MgO, or GaP;
    After forming a striped mask on the substrate, the substrate is grown so that the stripe-shaped high-density defect region is directly above the mask, and both sides of the bottom are other than the surface perpendicular to the growth direction. By making the slope of the facet surface, which is the face of the surface, into a V shape and sustaining the growth, it is grown while maintaining the slope of the facet surface, and crystal defects are concentrated in the lower part of the slope to form a stripe shape. In addition, a dislocation-concentrated region that grows from one of the following states (a) to (c) is formed as a boundary that distinguishes from the surrounding region while forming a series from the upper surface to the lower surface of the substrate. A process of
    (A) Polycrystalline state
    (B) In a single crystal state and inclined with respect to the surrounding low dislocation region
    (C) The c-axis in the [0001] direction is reversed with respect to the surrounding low dislocation region.
    A step of polishing so that the surface of the nitride semiconductor substrate has an off angle in the range of 0.2 ° to 1 ° from the (0001) plane;
    Have
    The center of the low dislocation area is a stripe caused by facets {0001} plane grows exposed, and the boundary is distinguished from the surroundings by emitting the different dopant incorporation with the surrounding A method for manufacturing a nitride semiconductor substrate in which a high luminescence region is formed.
  11. A step of forming a growth suppressing film for suppressing the growth of the nitride semiconductor crystal at the position of the dislocation concentration region on the surface of the nitride semiconductor substrate manufactured by the nitride semiconductor substrate manufacturing method of (B2) below;
    Laminating a nitride semiconductor layer on the nitride semiconductor substrate provided with the growth suppressing film;
    Forming a ridge stripe portion above the nitride semiconductor layer formed between the growth suppression films and avoiding a position directly above the high luminescence region ;
    A method for manufacturing a nitride semiconductor laser device comprising:
    (B2) A method for manufacturing a nitride semiconductor substrate in which a dopant is added during crystal growth ,
    GaAs, sapphire, SiC, quartz, NdGaO 3 , ZnO, GaN, AlN
    Forming a mask on a substrate made of ZnB 2 , Si, spinel, MgO, or GaP;
    After forming a dot-shaped mask on the substrate, the substrate is grown so that the pit-shaped high-density defect area is directly above the mask and the pits are surrounded by a surface other than the surface perpendicular to the growth direction. By maintaining the growth of the facet surface, the growth is performed while maintaining the slope of the facet surface, and the crystal defects are concentrated on the lower part of the slope to form dots and from the top surface to the bottom surface of the substrate. And a step of growing a dislocation-concentrated region that becomes a boundary that is distinguished from the surrounding region and that is in any of the following states (a) to (c):
    (A) Polycrystalline state
    (B) In a single crystal state and inclined with respect to the surrounding low dislocation region
    (C) The c-axis in the [0001] direction is reversed with respect to the surrounding low dislocation region.
    A step of polishing so that the surface of the nitride semiconductor substrate has an off angle in the range of 0.2 ° to 1 ° from the (0001) plane;
    Have
    The center of the low dislocation area is a stripe caused by facets {0001} plane grows exposed, and the boundary is distinguished from the surroundings by emitting the different dopant incorporation with the surrounding A method for manufacturing a nitride semiconductor substrate in which a high luminescence region is formed.
  12. The method for manufacturing a nitride semiconductor laser element according to claim 10, wherein the dislocation concentration region in the form of stripes is formed substantially parallel to the [1-100] direction.
  13. The method for manufacturing a nitride semiconductor laser element according to claim 10 or 12, wherein the dislocation concentration region in a stripe shape having a width of 10 µm to 40 µm is formed.
  14. The stripe-like dislocation concentration region is formed, and a portion including the stripe-like dislocation concentration region is recessed on the surface of the nitride semiconductor substrate. The manufacturing method of the nitride semiconductor laser element of description.
  15. The method for manufacturing a nitride semiconductor laser element according to claim 10, wherein the off-angle is 0.4 ° to 0.8 °.
  16. The method for manufacturing a nitride semiconductor laser element according to claim 10, wherein oxygen is doped.
  17. The method of manufacturing a nitride semiconductor laser element according to claim 16, wherein n-type conductivity is generated by doping oxygen.
  18. While forming a plurality of dislocation concentration regions,
    The method for manufacturing a nitride semiconductor laser element according to any one of claims 10 to 17, wherein an interval between dislocation concentration regions is set to 100 µm or more and 600 µm or less.
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