JP5732952B2 - Method for fabricating group III nitride semiconductor device - Google Patents

Method for fabricating group III nitride semiconductor device Download PDF

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JP5732952B2
JP5732952B2 JP2011065935A JP2011065935A JP5732952B2 JP 5732952 B2 JP5732952 B2 JP 5732952B2 JP 2011065935 A JP2011065935 A JP 2011065935A JP 2011065935 A JP2011065935 A JP 2011065935A JP 5732952 B2 JP5732952 B2 JP 5732952B2
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group iii
iii nitride
nitride semiconductor
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JP2012204474A (en
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晋 吉本
晋 吉本
史典 三橋
史典 三橋
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住友電気工業株式会社
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Description

  The present invention relates to a method for manufacturing a group III nitride semiconductor device.

Non-Patent Document 1 describes a laser diode that oscillates at 520 nm. Patent Document 1 describes a group III nitride semiconductor device, and this group III nitride semiconductor device has a gallium nitride system having an oxygen concentration of 5 × 10 16 cm −3 or more and 5 × 10 18 cm −3 or less. Includes semiconductor regions.

JP 2010-21249 A

Yusuke Yoshizumi, Masahiro Adachi, Yohei Enya Takashi Kyono, Shinji Tokuyama, Takamichi Sumitomo, Katsushi Akita, Takatoshi Ikegami, Masaki Ueno, Koji Katayama, and Takao Nakamura, "Continuous-Wave Operation of 520nm Green InGaN-Based Laser Diodes on Semi-Polar (20-21) GaN Substrates, "Applied Physics Express 2 (2009) 092101

  As understood from Non-Patent Document 1, semipolar group III nitride is an attractive target for group III nitride semiconductor devices. According to the knowledge of the inventors, the reactivity of the epitaxial film on the semipolar plane is higher than that of the c-plane, and therefore an oxide film is easily formed on the surface of the epitaxial film. Further, the oxide film is formed thicker than the c-plane. Although the inventors have made various attempts to provide a good electrical contact with the semipolar surface having such properties, they have not yet obtained a good contact resistance. In this respect, the semipolar surface is different from the m-plane and the c-plane, which can form an electrode having better contact resistance than the semipolar plane.

  The present invention has been made in view of such circumstances, and provides a method for producing a group III nitride semiconductor device capable of providing good contact resistance to a semipolar group III nitride. Objective.

  One aspect of the present invention relates to a method for fabricating a group III nitride semiconductor device. The method includes: (a) placing an epitaxial substrate including a substrate and a gallium nitride based semiconductor layer formed on the substrate in a vacuum chamber of a processing apparatus; and (b) placing the epitaxial substrate in the vacuum chamber. (C) after raising the temperature of the epitaxial substrate in the vacuum chamber, modifying the surface of the gallium nitride based semiconductor layer of the epitaxial substrate in the vacuum chamber; Forming an epitaxial product having a modified surface; and depositing a conductive film on the modified surface of the epitaxial product to form an interface between the gallium nitride based semiconductor layer and the conductive film. Forming a step. The modification treatment includes one of gallium flux irradiation and nitrogen radical irradiation without simultaneously performing gallium flux irradiation and nitrogen radical irradiation, and the surface of the gallium nitride based semiconductor layer is formed of the gallium nitride based semiconductor. The semipolarity inclined at an inclination angle of more than 61 degrees with reference to a first reference plane orthogonal to a reference axis extending in the c-axis direction of the layer, wherein the modified surface has the modified surface A first portion extending along a first surface inclined at a first angle with respect to two reference planes and a second surface inclined at a second angle with respect to the second reference plane. And the second portion is present.

  According to this manufacturing method, after the temperature of the epitaxial substrate is increased in the vacuum chamber, the surface of the gallium nitride based semiconductor layer is subjected to a modification process in the vacuum chamber. This reforming treatment includes one of gallium flux irradiation and nitrogen radical irradiation without simultaneously performing gallium flux irradiation and nitrogen radical irradiation. By performing gallium flux irradiation or nitrogen radical irradiation treatment on the semipolar surface so that film formation does not occur, the surface of the gallium nitride based semiconductor layer is composed of several plane orientations different from the original semipolar surface. It is changed to the modified surface containing. Although the grown gallium nitride based semiconductor layer has a semipolar surface, the modified surface extends along the first surface inclined at a first angle with respect to the first reference plane by the modification process. And a second portion extending along a second surface inclined at a second angle with respect to the first reference plane. When the surface of the gallium nitride based semiconductor layer has a semipolarity inclined at an inclination angle exceeding 61 degrees with reference to a first reference plane orthogonal to a reference axis extending in the c-axis direction of the gallium nitride based semiconductor layer, At least a portion of the surface formed by the modification process can provide good contact resistance. Although the electrode is formed on the gallium nitride based semiconductor layer, a part of the electrode is in contact with a partial surface that can provide good contact resistance. Therefore, the contact resistance of the entire electrode is better than that of an electrode that is in direct contact with the semipolar surface. Preferably, one of the first portion and the second portion has an m-plane or substantially m-plane orientation.

In the manufacturing method according to one aspect of the present invention, the degree of vacuum in the vacuum chamber is preferably 1 × 10 −6 Torr or less in the reforming process. According to this manufacturing method, the migration of atoms on the surface of the gallium nitride semiconductor occurs in the above vacuum range, so that the surface is more easily changed to a desired surface.

  In the manufacturing method according to one aspect of the present invention, the substrate temperature in the modification treatment is preferably 500 degrees Celsius or more. According to this manufacturing method, according to the above temperature range, migration of atoms on the surface of the gallium nitride semiconductor occurs, so that a desired surface can be obtained more easily.

  In the manufacturing method according to one aspect of the present invention, the modified surface may have a step structure including the first portion and the second portion. According to this manufacturing method, the contact of the electrode with one of the two portions in the step structure is better than the contact of the electrode with the other.

  In the manufacturing method according to one aspect of the present invention, the surface of the gallium nitride based semiconductor layer is inclined in the m-axis direction of the gallium nitride based semiconductor layer, and one of the first portion and the second portion is {10 -10} planes can be included. According to this manufacturing method, migration of atoms on the surface of the gallium nitride semiconductor occurs in the modification treatment, and a {10-10} plane is formed.

  In the manufacturing method according to one aspect of the present invention, the other of the first part and the second part may include a {10-11} plane. When the {10-10} plane is formed by the modification treatment, the {10-11} plane may appear on the modified surface.

  In the manufacturing method according to one aspect of the present invention, the surface of the gallium nitride based semiconductor layer is inclined in the m-axis direction of the gallium nitride based semiconductor layer, and the step structure has a (10-10) plane and (10− 11) It can include a surface. According to this manufacturing method, since the step structure includes the m-plane, contact with the m-plane can provide good contact resistance.

  In the manufacturing method according to one aspect of the present invention, each of the first portion and the second portion may extend in a direction intersecting with the direction of inclination of the surface of the gallium nitride based semiconductor layer. According to this manufacturing method, the first portion and the second portion are modified by performing the reforming process on the semipolar surface inclined at an inclination angle in the angle range of the inclination angle exceeding 61 degrees with respect to the first reference plane. Are formed so as to extend in a direction crossing the above-described inclination direction.

  The manufacturing method according to one aspect of the present invention includes a step of disposing a substrate having a main surface made of a group III nitride semiconductor in a growth apparatus, and one or a plurality of gallium nitride-based semiconductor layers on the main surface of the substrate. And the step of growing with the growth apparatus to form the epitaxial substrate, and the step of taking the epitaxial substrate out of the growth apparatus and exposing the surface of the gallium nitride based semiconductor layer to the atmosphere. The main surface of the substrate has an angle exceeding 61 degrees in the m-axis direction of the group III nitride semiconductor with reference to a third reference plane orthogonal to a reference axis extending in the c-axis direction of the group III nitride semiconductor. The gallium nitride based semiconductor layer can extend along a fourth reference plane orthogonal to the normal axis of the main surface of the substrate.

  According to this manufacturing method, the morphology of the surface of the gallium nitride based semiconductor layer can be controlled by using the substrate having the semipolar surface as described above. Since the surface of the gallium nitride based semiconductor layer is exposed to the atmosphere when the epitaxial substrate is taken out from the growth apparatus, the surface of the gallium nitride based semiconductor layer is placed in an atmosphere containing oxygen.

The manufacturing method according to one aspect of the present invention may further include a step of providing a vacuum degree of 1 × 10 −10 Torr or less to the vacuum chamber prior to the reforming process of the epitaxial product.

  According to this manufacturing method, the epitaxial product is placed in the high vacuum prior to the reforming process. During this period, the surface of the gallium nitride based semiconductor layer is cleaned due to the vapor pressure.

  In the manufacturing method according to one aspect of the present invention, the conductive film can include at least one of Au, Pd, Ni, Rh, Al, Ti, Zn, Cu, In, Ta, Pt, and Tl. According to this manufacturing method, an electrode can be formed using the above electrode material.

  The manufacturing method according to one aspect of the present invention may further include a step of processing the electrode film to form an electrode on the substrate product. It is preferable not to alloy the electrode in forming the electrode. According to this production method, a non-alloy electrode can be produced.

  In the manufacturing method according to one aspect of the present invention, in the modification treatment, gallium flux irradiation can be performed without performing nitrogen radical irradiation. Alternatively, in the manufacturing method according to one aspect of the present invention, the radical treatment can be performed without performing the gallium flux irradiation in the modification treatment. According to these manufacturing methods, unwanted by-products may be formed by simultaneously performing gallium flux irradiation and nitrogen radical irradiation. Since gallium flux irradiation and nitrogen radical irradiation are not performed simultaneously, the formation of by-products can be avoided.

  In the manufacturing method according to one aspect of the present invention, the group III nitride semiconductor device may include a group III nitride semiconductor light emitting device, and the epitaxial substrate may include an active layer that generates light by carrier injection. According to this manufacturing method, the driving voltage of the light emitting element can be reduced by providing good contact resistance.

  In the manufacturing method according to one aspect of the present invention, the active layer of the epitaxial substrate is provided so as to generate light having a wavelength range of 500 nm or more and 540 nm or less. According to this manufacturing method, good contact resistance can be provided to the green light-emitting element formed using the semipolar plane, and the driving voltage of the light-emitting element can be reduced.

  The above and other objects, features, and advantages of the present invention will become more readily apparent from the following detailed description of preferred embodiments of the present invention, which proceeds with reference to the accompanying drawings.

  As described above, according to one aspect of the present invention, there is provided a method for producing a group III nitride semiconductor device that can provide good contact resistance to semipolar group III nitride.

FIG. 1 is a drawing schematically showing main steps in a method for manufacturing a group III nitride semiconductor light emitting device according to the present embodiment. FIG. 2 is a drawing schematically showing main steps in the method of manufacturing the group III nitride semiconductor light emitting device according to the present embodiment. FIG. 3 is a drawing schematically showing main steps in the method for manufacturing a group III nitride semiconductor light emitting device according to the present embodiment. FIG. 4 is a drawing schematically showing main steps in the method for manufacturing a group III nitride semiconductor light emitting device according to the present embodiment. FIG. 5 is a drawing schematically showing the structure of a nitride laser device. FIG. 6 is an atomic force microscope (AFM) image of the modified surface.

  The knowledge of the present invention can be easily understood by considering the following detailed description with reference to the accompanying drawings shown as examples. Subsequently, referring to the attached drawings, a method of manufacturing an epitaxial substrate and a group III nitride semiconductor device, a method of manufacturing a group III nitride semiconductor light emitting device, and a method of forming an electrode for a group III nitride semiconductor device Embodiments relating to Group III nitride semiconductor devices and epitaxial substrates will be described. Where possible, the same parts are denoted by the same reference numerals.

  With reference to FIGS. 1 to 4, an embodiment relating to a method of manufacturing an epitaxial substrate and a group III nitride semiconductor device, a method of manufacturing a group III nitride semiconductor light emitting device, and a method of forming an electrode will be described. Do. 1 to 4 are drawings schematically showing main steps in the method of manufacturing a group III nitride semiconductor device according to the present embodiment. In the following description, a method for manufacturing a group III nitride semiconductor device will be described with reference to a group III nitride semiconductor light emitting device.

  As shown in FIG. 1A, the substrate 11 is prepared in step S101. The substrate 11 has a main surface 11a made of a group III nitride semiconductor, and the main surface 11a extends in the direction of the c-axis of the group III nitride semiconductor (the <0001> axis in the present embodiment). Tilted at an angle ANGLE greater than 61 degrees with respect to a plane Rc orthogonal to the reference axis (indicated by the vector VC), and thus exhibits semipolarity. The substrate 11 can be made of, for example, a group III nitride semiconductor. The group III nitride semiconductor of the substrate 11 can be made of, for example, GaN. The main surface 11a is preferably inclined in the m-axis direction of the gallium nitride based semiconductor layer, but the inclination direction may be a small angle range of −1 degree or more and +1 degree or less around the m-axis direction. When the inclination direction of the m-axis is within this angle range, good contact resistance can be provided to the group III nitride semiconductor device.

  As shown in part (b) of FIG. 1, in step S102 (S102-1), a semiconductor stack 13 for a semiconductor light emitting element is grown on a substrate 11 by a growth apparatus 10a. Subsequently, an embodiment will be described. After the substrate 11 is placed in the growth apparatus 10a, ammonia and hydrogen are supplied to the growth apparatus 10a to perform pretreatment (for example, thermal cleaning) of the main surface 11a of the substrate 11. After the pretreatment, a plurality of group III nitride semiconductor layers are epitaxially grown in order on the main surface 11a of the substrate 11 using the growth apparatus 10a. This growth is performed by a growth method such as a metal organic chemical vapor deposition method.

  In the formation of the semiconductor stack 13, a group III nitride semiconductor layer of the first conductivity type such as the n-type group III nitride semiconductor region 15 is grown by the growth apparatus 10 a and then activated on the n-type group III nitride semiconductor region 15. Layer 17 is grown. If necessary, a light guide layer may be grown on the n-type group III nitride semiconductor region 15 prior to the growth of the active layer 17. The n-type group III nitride semiconductor region 15 can be made of, for example, GaN, AlGaN, InAlGaN, or the like. The active layer 17 includes a gallium nitride based semiconductor layer containing indium as a group III constituent element. The active layer 17 has, for example, a quantum well structure 21, and the quantum well structure 21 can include alternately arranged barrier layers 23 and well layers 25. The band gap of the barrier layer 23 is larger than the band gap of the well layer 25. The barrier layer 23 can be made of, for example, GaN, InGaN, InAlGaN, or the like, and the well layer 25 can be made of, for example, GaN, InGaN, InAlGaN, or the like. The active layer 17 is provided so as to have a peak emission wavelength in a wavelength range of, for example, 480 nm or more and 560 nm or less. In a preferred embodiment, the active layer 17 is provided so as to have a peak emission wavelength in a wavelength range of, for example, 500 nm or more and 540 nm or less. If necessary, a light guide layer can be grown on the active layer 17 by the growth apparatus 10a before the second conductivity type gallium nitride based semiconductor region is grown. Through these steps, the semiconductor stack 12 is grown on the substrate 11.

  As shown in part (c) of FIG. 1, in step S102-2, a second conductivity type gallium nitride based semiconductor region such as a p-type group III nitride semiconductor region 19 is grown by a growth apparatus 10a, and a semiconductor stack is formed. 13 is formed. In this embodiment, a p-type group III nitride semiconductor region 19 is formed on the active layer 17. The p-type group III nitride semiconductor region 19 can be made of, for example, GaN, AlGaN, InAlGaN, or the like.

  For the p-type group III nitride semiconductor region 19, an electron block layer 27, a p-type cladding layer 29 and a gallium nitride based semiconductor layer 31 are grown on the active layer 17 in order. The electron block layer 27 has a band gap larger than that of the barrier layer 23. The p-type cladding layer 29 has a band gap larger than that of the barrier layer 23 and a refractive index smaller than that of the active layer 17. In the present embodiment, a gallium nitride based semiconductor layer 31 for a p-type contact layer is grown at the end of several film formations in the formation of the semiconductor stack 13. The p-type group III nitride semiconductor region 19 can include a p-type gallium nitride based semiconductor layer 31. The surface 31a of the gallium nitride based semiconductor layer 31 is semipolar, and this surface 31a is orthogonal to a reference axis Bx extending in the c-axis direction (<0001> axis in the present embodiment) of the gallium nitride based semiconductor layer 31. It inclines at an inclination angle exceeding 61 degrees with respect to the reference plane Rb. The surface 31 a is inclined, for example, in the m-axis direction of the gallium nitride based semiconductor layer 31 according to the inclination of the c-axis of the substrate 11. The p-type group III nitride semiconductor region 19 can include an electron block layer 27, a p-type cladding layer 29, and a gallium nitride based semiconductor layer (p-type contact layer) 31. The electron block layer 27 is made of, for example, Mg-doped AlGaN, and the p-type cladding layer 29 is made of, for example, Mg-doped InAlGaN. The p-type contact layer can be made of, for example, Mg-doped GaN, Mg-doped InGaN, or the like.

  When the semiconductor stack 13 is grown on the main surface 11a of the substrate 11 to form the epitaxial substrate E1, the main surface 11a of the substrate 11 has a c-axis of the group III nitride semiconductor (<0001 in this embodiment). It is preferable to incline at an angle ANGLE in the range of more than 61 degrees and 80 degrees or less from a plane orthogonal to the reference axis Cx extending in the> axis) direction. When there is an inclination angle ANGLE within this angle range, the semipolar plane of the gallium nitride semiconductor is rich in oxygen bonding. Therefore, it is important to reduce oxygen during the formation of the ohmic electrode.

  In addition, the main surface of the epitaxial substrate E1 is in a range greater than 61 degrees and less than 80 degrees from a plane orthogonal to the reference axis Bx extending in the c-axis (<0001> axis in the present embodiment) direction of the gallium nitride based semiconductor layer 31. It is preferable to incline at this angle. The semipolar plane in this angular range provides a step structure that can achieve good contact resistance by the modification process shown by the following description. The main surface 31a of the gallium nitride based semiconductor layer 31 is preferably tilted in the m-axis direction of the gallium nitride based semiconductor layer 31, but the c-axis tilt direction is not less than −1 degree and not more than +1 degree with respect to the m-axis direction. It may be a small angle range.

  Further, when the c-axis (<0001> axis in this embodiment) of the gallium nitride semiconductor of the substrate 11 and the gallium nitride semiconductor layer 31 is inclined in the direction of the m-axis of the group III nitride semiconductor, The inclination angle of the main surface of the substrate E1 is inclined at an angle in the range of 63 degrees or more and 80 degrees or less from a plane orthogonal to the reference axis extending along the c-axis (<0001> axis) of the group III nitride semiconductor. Is preferred. This manufacturing method provides good indium uptake suitable for green light emission.

  As shown in FIG. 2A, in step S103, when the epitaxial substrate E1 is taken out from the growth apparatus 10a, the epitaxial substrate E1 is exposed to the atmosphere containing oxygen. As a result, native oxide gallium oxide 14 is formed on the gallium nitride based semiconductor surface exposed on the surface of the epitaxial substrate E1.

  After the epitaxial substrate E1 is taken out from the growth apparatus 10a, in step S104, the epitaxial substrate E1 is placed in the processing apparatus 10b prior to the next film formation. After the epitaxial substrate E1 is taken out from the growth apparatus 10a and before the next growth apparatus is disposed, the epitaxial substrate E1 is processed by the processing apparatus 10b as shown in FIG. 2 (b). Can be washed. When the surface of the epitaxial substrate E1 is exposed to the atmosphere when taken out from the growth apparatus 10a, the surface is contaminated. In particular, oxygen is adsorbed on the surface of the epitaxial substrate E1. For this reason, impurities relating to oxygen remain on the surface of the epitaxial substrate E1.

  As shown in FIG. 2C, in step S105, after the gallium nitride based semiconductor layer 31 is grown, the epitaxial substrate E1 is disposed in the processing apparatus 10c. The modification process is performed on the main surface of the epitaxial substrate E1 by using the processing apparatus 10c.

As shown in part (a) of FIG. 3, in step S106, after the temperature of the epitaxial substrate E (for example, 500 degrees Celsius to 900 degrees Celsius) is increased in the vacuum chamber, the epitaxial substrate E1 is reformed. Prior to achieving a high vacuum level of 1 × 10 −10 Torr or less in the vacuum chamber, the vacuum level of 1 × 10 −10 Torr is converted as 1.33322 × 10 −8 Pascal. Prior to the reforming process, the epitaxial substrate E1 is placed in the high vacuum. During this period, the surface 31a of the gallium nitride based semiconductor layer 31 is cleaned in accordance with the vapor pressure of the surface residue.

As shown in part (b) of FIG. 3, in step S107, the reforming process is performed by forming a reforming atmosphere in the vacuum chamber of the processing apparatus 10c. The substrate product SP1 is formed by the modification process. In this reforming process, the degree of vacuum in the vacuum chamber is preferably 1 × 10 −6 Torr or less. In this vacuum range, atom migration occurs on the surface 31a of the gallium nitride based semiconductor layer 31, so that the surface can be changed to a desired surface more easily. Formation of the atmosphere for reforming may include irradiation with a flux 18 of either a gallium flux or a nitrogen radical, for example. In this modification flux irradiation, the main surface of the epitaxial substrate E1 in the vacuum chamber of the processing apparatus 10c may be irradiated with, for example, gallium flux or nitrogen flux without simultaneously performing both gallium flux irradiation and nitrogen radical irradiation. preferable. According to this method, the irradiation of the flux 18 while heating causes migration on the surface of the gallium nitride based semiconductor layer 31 (the surface of the epitaxial substrate E1) 31a, and the surface 31a of the gallium nitride based semiconductor layer 31 is modified. The As a result, the gallium nitride based semiconductor layer 31 has a modified surface 31b.

  In a preferred embodiment, in the modification treatment, gallium flux irradiation can be performed without performing nitrogen radical irradiation. Alternatively, in the modification treatment, nitrogen radical irradiation can be performed without performing gallium flux irradiation. By performing gallium flux irradiation and nitrogen radical irradiation simultaneously, unwanted by-products may be formed. According to these manufacturing methods, since gallium flux irradiation and nitrogen radical irradiation are not performed at the same time, formation of by-products can be avoided.

  In step S107, the epitaxial substrate E1 is also heated by the processing apparatus 10c. In an example of the heating conditions, the heating temperature is, for example, 720 degrees Celsius, the heat treatment time is 30 minutes, and the modification treatment is, for example, irradiation with gallium flux. This temperature range can be, for example, 500 degrees Celsius or more. According to the above temperature range, migration of atoms on the surface of the gallium nitride semiconductor occurs, so that a desired surface can be formed. Also, this temperature range can be, for example, 900 degrees Celsius or less, in order to avoid damage to the active layer 17. Further, this temperature range can be, for example, 600 degrees Celsius or higher. According to this temperature range, atom migration on the surface of the gallium nitride based semiconductor becomes active, so that a desired surface can be obtained more easily. After this reforming process, the epitaxial substrate E1 is taken out from the processing apparatus 10c. In addition, it is preferable that the substrate temperature for this modification | reformation process is below the lowest temperature of the film-forming temperature in formation of the epitaxial substrate E. FIG. According to this temperature range, it is possible to reduce thermal stress on the active layer that may occur due to the modification treatment. When the active layer includes an InGaN layer, the substrate temperature of the epitaxial substrate E1 is preferably equal to or lower than the growth temperature of the InGaN well layer of the active layer, for example. It can be avoided that the quality of the InGaN layer of the active layer 17 is deteriorated by the heat treatment in the modification step.

  Referring to FIG. 3B, the crystal coordinate system is shown, and the c-axis Bx is inclined in the direction of the m-axis. The modification process is performed so that the modified surface 31b includes a first portion (partial surface) 32a and a second portion (partial surface) 32b. The first portion (partial surface) 32 a extends along the first surface R 1, and the first surface R 1 is the second relative to the reference plane Rb orthogonal to the c-axis VC 31 (reference axis Bx) of the gallium nitride based semiconductor layer 31. Inclined at an angle AG1 of 1. The second portion (partial surface) 32b extends along the second surface R2, and the second surface R2 is inclined at the second angle AG2 with respect to the reference plane Rb.

  In the steps so far, after the epitaxial substrate E is placed in the vacuum chamber of the growth apparatus 10c, the substrate product SP1 is produced by performing a modification process by flux irradiation. The modified surface 31b of the gallium nitride based semiconductor layer 31 may have a step structure including a first portion (partial surface) 32a and a second portion (partial surface) 32b. Each of the first portion 32 a and the second portion 32 b can extend in a direction crossing the direction of inclination of the surface 31 a of the gallium nitride based semiconductor layer 31. By performing the reforming process on the semipolar surface inclined at the inclination angle ANGLE in the angle range of the inclination angle exceeding 61 degrees, each of the first portion 32a and the second portion 32b extends in a direction intersecting the inclination direction. Formed to exist. When the surface 31a of the gallium nitride based semiconductor layer 31 is inclined in the m-axis direction of the gallium nitride based semiconductor layer 31, the step surfaces constituting the above step structure (for example, the partial surfaces 32a and 32b) are arranged in one direction, The step surface extends in the direction of the a-axis, for example. An electrode manufactured in a later process makes good contact with the first portion 32a and the second portion 32b. The contact resistance of the electrode to one of the two partial surfaces in this step structure (contact resistance per unit area) is smaller than the contact resistance of the electrode to the other (contact resistance per unit area). In a preferred embodiment, the step structure can include a {10-10} plane. Since the step structure includes an m-plane, contact with the m-plane can provide good contact resistance. Further, the step structure can include a {10-11} plane. The {10-11} plane is a plane orientation inclined at an angle of approximately 61 degrees in the m-axis direction of the gallium nitride based semiconductor layer 31 with reference to a reference plane orthogonal to the c-axis of the gallium nitride based semiconductor layer 31. This can provide a relatively stable surface.

  By the modification process, the surface 31a of the gallium nitride based semiconductor layer 31 is modified to the surface 31b, the first angle AG1 is smaller than the inclination angle ANGLE of the semipolar plane, and the second angle AG2 is the semipolar plane. It can be larger than the inclination angle ANGLE.

  The surface 31a of the gallium nitride based semiconductor layer 31 is inclined within an angle range exceeding 61 degrees in the m-axis direction of the gallium nitride based semiconductor layer 31 with reference to a reference plane orthogonal to the c axis of the gallium nitride based semiconductor layer 31. When the semipolarity defined by the corners is shown, the modification treatment for the surface 31a can provide the modified surface 31b to the substrate product SP1, and the modified surface 31b can be formed of a plurality of surfaces (eg, inclined surfaces). A partial surface along the first surface R1 defined by the first angle AG1 smaller than the angle ALGLE, and a partial surface along the second surface R2 defined by the second angle AG2 larger than the inclination angle ALGLE). Is done.

  The semiconductor stack 13 including the gallium nitride based semiconductor layer 31 in contact with the electrode is preferably grown using the metal organic vapor phase epitaxy method with the growth apparatus 10a. As the processing apparatus 10c for the modification process, a molecular beam epitaxy apparatus can be used.

The gallium nitride based semiconductor layer 31 serves as a contact layer when an electrode is formed on the layer 31 in a subsequent process. Also, in a preferred embodiment, this contact layer can have p conductivity. In this embodiment, since a metal for an electrode is deposited on the gallium nitride based semiconductor layer 31 in a later step, the gallium nitride based semiconductor layer 31 has a desired conductivity type dopant such as magnesium or zinc. It is preferable to add such a p-type dopant. The p-type dopant concentration can be, for example, 1 × 10 16 cm −3 or more and 1 × 10 21 cm −3 or less. According to this manufacturing method, an electrode that is in ohmic contact with the p-type gallium nitride based semiconductor layer 31 can be formed. Reduction of the oxygen concentration in the surface layer of the p-type gallium nitride based semiconductor layer 31 in contact with the electrode is effective in reducing the drive voltage.

  Next, after removing the substrate product SP1 from the growth apparatus 10c and placing it on the growth apparatus 10d, as shown in FIG. 3C, in step S108, the substrate product SP1 is processed in the vacuum chamber of the processing apparatus 10d. An insulating film 35 for surface protection is formed on the main surface. In order to form a protective layer having a contact film (a protective layer 35a in FIG. 4A), the insulating film 35 is processed to form a substrate product SP2. The insulating film 35 can be made of, for example, silicon oxide. If necessary, prior to the formation of the substrate product SP2, the substrate product SP1 or the epitaxial substrate E1 can be processed to have an element structure such as a ridge structure.

  Thereafter, as shown in part (a) of FIG. 4, in step S109, an electrode film 37 is formed on the main surface of the protective layer 35a of the substrate product SP2 in the vacuum chamber of the growth apparatus 10e. SP3 is formed. The conductive film 37 can include, for example, at least one of Au, Pd, Ni, Rh, Al, Ti, Zn, Cu, In, Ta, Pt, and Tl. According to this method, an electrode can be formed using the above electrode material. After the conductive film 37 is formed, an electrode is formed. For example, lift-off or etching can be used to form the electrodes.

  Next, as shown in part (b) of FIG. 4, in step S109, the electrode film 37 is processed to form the electrode 38 on the substrate product SP3. In a preferred embodiment, the pattern can be transferred to the conductive film 37 using lift-off or etching to form the electrode 38 that is in contact with the surface 31 b of the gallium nitride based semiconductor layer 31. In the substrate product SP4, the electrode 38 is in ohmic contact with the p-type gallium nitride based semiconductor layer 33 through an opening for electrical connection provided in the insulating layer 35a. Further, after polishing as necessary, an electrode 39 is formed on the back surface of the substrate product SP3. Thereby, the substrate product SP4 is formed. In a preferred embodiment, the p-type gallium nitride based semiconductor layer 33 can be made of p-type GaN, and the electrode 38 can be made of palladium (Pd).

  According to this manufacturing method, after increasing the temperature of the epitaxial substrate E1 in the vacuum chamber of the processing apparatus 10c, the surface 31a of the gallium nitride based semiconductor layer 31 is subjected to a modification process in the vacuum chamber. This modification process includes one of gallium flux irradiation and nitrogen radical irradiation. The surface 31a of the gallium nitride based semiconductor layer 31 is in the m-axis direction of the gallium nitride based semiconductor layer with reference to a first reference plane orthogonal to the reference axis Bx extending in the c-axis direction of the gallium nitride based semiconductor layer 31. Since the surface 31b modified by the modification process has a structure suitable for electrical contact since it has a semipolarity inclined at an inclination angle exceeding 61 degrees, the gallium nitride based semiconductor layer 31, the electrode 38, The interface 36 formed by the above contact also maintains substantially the same configuration as the step structure of the modified surface 31b. With respect to the structure of the interface 36, the structure of the interface 36 will be described using the same reference numerals as those in the part (b) of FIG. 3 while referring to the part (b) of FIG. The electrode 38 makes contact with each of the first portion 32a and the second portion 32b of the modified surface 31b. The first portion 32 a extends along the first surface inclined at the first angle with respect to the second reference plane, and makes contact with the electrode 38. The second portion 32 b extends along the second surface inclined at the second angle with respect to the second reference plane, and makes contact with the electrode 38. One of the first portion 32a and the second portion 32b has an m-plane or substantially m-plane orientation. From the shape of the interface, the electrode 38 can be contacted with a step surface including an m-plane or a step surface including a partial surface with a substantially m-plane orientation.

  The surface 31a of the gallium nitride based semiconductor layer 31 is different from the original semipolar surface by performing either treatment of gallium flux irradiation or nitrogen radical irradiation on the semipolar surface so that film formation does not occur. It is changed to the modified surface including the constituent surface of the plane orientation. Although the grown gallium nitride based semiconductor layer 31 has a semipolar surface 31a, in the range of the angle ANGLE in the present embodiment, at least a part of the surface 31b formed by the modification process is the original semipolar surface. Compared with this, a low contact resistance can be provided to the semiconductor element. Although the electrode 38 is formed on the gallium nitride based semiconductor layer 31, a part of the electrode 38 is in contact with a partial surface that can provide good contact resistance. Therefore, the contact resistance of the electrode as a whole is improved by applying the modification treatment, as compared with an electrode that directly contacts a semipolar surface close to the surface form as grown.

  In this method, for example, the alloy for the electrode 38 may not be performed after the conductive film 37 is formed. By not performing alloying for the electrode 38, there is an advantage that electrode deterioration due to heating and deterioration of the interface between the electrode and the semiconductor can be reduced.

  In the next step, the substrate product SP4 is separated to obtain a group III nitride semiconductor light emitting device 41. The group III nitride semiconductor light emitting device 41 includes a first conductivity type group III nitride semiconductor layer 43, an active layer 45 provided on the main surface of the first conductivity type group III nitride semiconductor layer 43, and an active layer. Group III nitride semiconductor layer 49 provided on the main surface of 45 and an electrode 53 provided on the main surface of Group III nitride semiconductor layer 49. The uppermost layer of the group III nitride semiconductor layer 49 is a contact layer, and the group III nitride semiconductor layer 49 forms a first junction J1 with the active layer 45. The electrode 53 forms a second junction J2 with the group III nitride semiconductor layer 51. Group III nitride semiconductor layer 51 has the second conductivity type. The active layer 45 generates light by carrier injection.

  The first and second junctions J1 and J2 are inclined at an angle ANGLE within the above angle range with respect to a reference plane orthogonal to the c-axis VC51 of the group III nitride semiconductor layer 51. The main surface of the active layer 45 is inclined at an angle ANGLE within the above angle range with respect to a reference plane orthogonal to the c-axis VC 43 of the first conductivity type group III nitride semiconductor layer 43. Each of the well layer 45b and the barrier layer 45a constituting the active layer 45 extends along a plane inclined with respect to a reference plane orthogonal to the c-axis VC43 of the first conductivity type group III nitride semiconductor layer 43.

  According to this group III nitride semiconductor light emitting device 41, since the second junction J2 is inclined with respect to the reference plane orthogonal to the c-axis VC43, the electrode 53 is connected to the first through the opening 50a of the insulating layer 50. Bonded to the modified surface 51 a of the second group III nitride semiconductor layer 51. Since the electrode 53 forms a junction with the modified surface 51a, the second junction J2 exhibits good ohmic characteristics. The first joint J1 is substantially parallel to the main surface 55a, and the second joint J2 is substantially parallel to the main surface 55a except for fine unevenness due to the step structure. It is preferable that the first and second joints J1 and J2 are inclined in the angle range already described with reference to a plane orthogonal to the reference axis.

  The group III nitride semiconductor light emitting device 41 can further include a support base 55, and the support base 55 has a main surface 55a made of a group III nitride semiconductor. The gallium nitride based semiconductor layer 51 extends along a third reference plane perpendicular to the normal axis of the major surface 55a of the support base 55. The first conductivity type group III nitride semiconductor layer 43 and the group III nitride semiconductor layer 49 also extend along respective reference planes orthogonal to the normal axis of the main surface 55a of the support base 55. The main surface 55a of the support base 55 is inclined at an angle of 61 degrees or more from a plane orthogonal to a reference axis extending along the c-axis VC55 of the group III nitride semiconductor. The group III nitride semiconductor layer 43, the active layer 45, the first group III nitride semiconductor layer 49, and the second group III nitride semiconductor layer 51 are in the direction of the normal line Nx of the main surface 55a of the support base 55. Arranged. The main surface 55a of the support base 55 is preferably inclined at an angle in the range of not less than 63 degrees and not more than 80 degrees from a plane orthogonal to the reference axis extending along the c-axis of the group III nitride semiconductor.

  The contact between the surface 51a of the gallium nitride semiconductor layer 51 formed by modifying the deposited gallium nitride semiconductor layer 51 and the electrode 53 provides good ohmic properties. The active layer 45 includes a gallium nitride based semiconductor layer containing indium as a group III constituent element, and the active layer 45 is provided to have a peak emission wavelength in a wavelength range of, for example, 500 nm or more and 540 nm or less.

(Experimental example 1)
In this embodiment, a nitride semiconductor laser as shown in FIG. 5 is fabricated on the {20-21} plane. First, a process for producing an epi product by metal organic chemical vapor deposition (MOCVD) is performed. A {20-21} GaN substrate is prepared. This GaN substrate is set in the chamber of the MOCVD apparatus. As raw materials, trimethylgallium (TMG), trimethylaluminum (TMA), trimethylindium (TMI), cyclopentadienylmagnesium (Cp 2 Mg), monosilane (SiH 4 ), and ammonia (NH 3 ) are used. The substrate temperature is maintained at 1050 degrees Celsius, and ammonia and hydrogen are supplied to the growth apparatus to perform thermal cleaning for 10 minutes. The following semiconductor stack is then grown: An n-type Al 0.04 Ga 0.96 N cladding layer having a thickness of 2 micrometers is grown at 1050 degrees Celsius. After lowering the substrate temperature to 840 degrees Celsius, an n-side In 0.03 Ga 0.97 N optical guide layer is grown. An InGaN / InGaN quantum well active layer is grown. The growth temperature of the InGaN well layer is 790 degrees Celsius, and the growth temperature of the InGaN barrier layer is 840 degrees Celsius. The thickness of the InGaN well layer is 3 nm, and the thickness of the InGaN barrier layer is 15 nm. If necessary, the growth of the barrier layer and the growth of the well layer are repeated alternately. After raising the substrate temperature to 840 degrees Celsius, a p-side In 0.03 Ga 0.97 N optical guide layer is grown. A p-type Al 0.12 Ga 0.88 N electron blocking layer having a thickness of 20 nm and a p-type Al 0.06 Ga 0.94 N cladding layer having a thickness of 400 nm are grown at a substrate temperature of 1000 degrees Celsius. Next, a p-type GaN contact layer is grown on the p-type Al 0.06 Ga 0.94 N cladding layer having a thickness of 50 nm.

After the substrate temperature is lowered to room temperature, the epitaxial substrate is taken out from the growth apparatus. Next, the surface treatment of the p-type GaN contact layer is performed with an MBE apparatus. Prior to placement in the MBE apparatus, it is washed with sulfuric acid / hydrogen peroxide. In this growth, gallium flux (K-cell), magnesium flux (K-cell), and nitrogen radical (RF-plasma) are used as raw materials. After this epitaxial substrate is set in the MBE apparatus, the degree of vacuum in the vacuum chamber of the MBE apparatus is evacuated to a value of 1 × 10 −10 Torr or less using a rotary pump, a turbo molecular pump, and a cryopump. After this treatment, the substrate temperature is set to 720 degrees Celsius using a heater. The epitaxial substrate is held at this temperature for 30 minutes. After the substrate temperature is lowered to room temperature, the modified epitaxial product is removed from the MBE apparatus. This epi product is referred to as “A”.

  In order to manufacture another device, the next electrode formation step is performed without performing the modification process using the MBE apparatus after the epitaxial substrate is taken out of the growth apparatus. This epi product is called “C”.

  A device is formed using these epi products A and C. A palladium electrode film is deposited on the entire surface of the epi products A and C by using a resistance heating type vapor deposition apparatus to form a substrate product. These substrate products are removed from the resistance heating vapor deposition apparatus. A resist is uniformly coated on the substrate product using a spin coater. Thereafter, exposure is performed using a photomask and an exposure apparatus. A resist mask having a stripe pattern with a width of 2 μm is formed by developing the exposed resist film. Using the resist mask, the resist mask pattern is transferred to the electrode film using a reactive ion etching apparatus to form a striped Pd electrode. After polishing the back surface of the GaN substrate, a back electrode is formed. The substrate products produced by these electrode processes are separated by a width of 600 μm to form laser bars LBA and LBC for the laser devices LDA and LDC, respectively.

  When the laser devices LDA and LDC manufactured by the above process are energized, the laser oscillation wavelengths of the laser devices LDA and LDC are 523.3 nm and 520.1 nm, respectively. The drive voltage of the laser device LDA is 8.4 volts, and the drive voltage of the laser device LDC is 9.6 volts.

(Experimental example 2)
An epitaxial substrate is produced in the same manner as in Experimental Example 1. After this epitaxial substrate is placed in the MBE apparatus, the nitrogen substrate is irradiated with nitrogen radical flux for 30 minutes. For the generation of the nitrogen radical flux, an RF radical gun is used, and a condition of an RF power of 250 W and a nitrogen flow rate of 1.3 cc (1.3 cm 3 in SI unit system) is used. Thereafter, electrodes are formed in the same manner as in Experimental Example 1 to form a laser device LDB. When the laser device LDB manufactured by the above process is energized, the laser oscillation wavelength of the laser device LDB is 522.5 nm. The drive voltage of the laser device LDB is 8.2 volts.

  When observing the change of the surface of the contact layer due to the modification treatment, the initial surface (p-type GaN surface) of the epitaxial substrate showed the (20-21) plane, but as the irradiation of nitrogen radical flux progressed The (10-10) plane and the (10-11) plane appear.

(Experimental example 3)
An epitaxial substrate is produced in the same manner as in Experimental Example 1. After this epitaxial substrate is placed in the MBE apparatus, the epitaxial substrate is irradiated with gallium flux for 30 minutes. The gallium flux is irradiated under the condition of 1.4 × 10 −5 Torr. Thereafter, electrodes are formed in the same manner as in Experimental Example 1 to form a laser device LDD. When the laser device LDD manufactured by the above process is energized, the laser oscillation wavelength of the laser device LDD is 522.1 nm. The drive voltage of the laser device LDD is 8.2 volts.

  Observe the change in the surface of the contact layer due to the modification treatment. The surface of the epitaxial substrate (p-type GaN surface) showed the (20-21) plane, but the (10-10) plane and the (10-11) plane appear as the gallium flux irradiation proceeds.

(Experimental example 4)
When a Pd film is formed on the modified GaN surface by the electron beam evaporation method and the contact resistance is evaluated using the TLM method, the measured value of the contact resistance is 1 × 10 −4 cm −2, which is favorable. Indicates ohmic contact. On the other hand, when a Pd film is formed on the GaN surface formed by epitaxial growth (GaN surface without modification treatment) by the electron beam evaporation method and the contact resistance is evaluated using the TLM method, the contact resistance is measured. The value is 2 × 10 −3 cm −2 .

(Experimental example 5)
FIG. 6 is a diagram showing a measurement using an atomic force microscope (AFM) of a GaN surface (modified GaN surface) formed by modifying a {20-21} GaN surface. Part (a) of FIG. 6 shows an AFM image of the modified surface. Part (b) of FIG. 6 shows the result of measuring the surface morphology of the modified surface using AFM. Referring to part (b) of FIG. 6, the step structure has a ridge and a valley, and two side surfaces inclined to form a ridge are observed, and two side surfaces inclined to form a valley are observed. Is observed. Referring to part (a) of FIG. 6, the two surfaces constituting the step structure extend in one direction in a striped manner (the direction of the a axis in this experimental example), and ridges and valleys are alternately arranged. Is done. According to the measurement by the inventors, one of the two surfaces constituting the step structure is an m-plane, that is, approximately {10-10} plane, and the other is approximately {10-11} plane.

  While the principles of the invention have been illustrated and described in the preferred embodiments, it will be appreciated by those skilled in the art that the invention can be modified in arrangement and detail without departing from such principles. The present invention is not limited to the specific configuration disclosed in the present embodiment. We therefore claim all modifications and changes that come within the scope and spirit of the following claims.

  As described above, according to the present embodiment, there is provided a method for manufacturing a group III nitride semiconductor device that can provide good contact resistance to semipolar group III nitride.

DESCRIPTION OF SYMBOLS 10a, 10c ... Growth apparatus, 10b ... Processing apparatus, 11 ... Substrate, 12 ... Semiconductor lamination, 13 ... Semiconductor lamination, 13a ... Surface of semiconductor lamination, 14 ... Natural oxide gallium oxide, E1 ... Epitaxial substrate, 15 ... n-type Group III nitride semiconductor region, 17 ... active layer, 19 ... p-type group III nitride semiconductor region, 21 ... quantum well structure, 23 ... barrier layer, 25 ... well layer, 27 ... electron blocking layer, 29 ... p-type cladding Layer 31. Gallium nitride semiconductor layer (contact layer) 37. Conductive film 41. Group III nitride semiconductor light emitting element 43. First conductivity type group III nitride semiconductor layer 45. First conductivity type group III Nitride semiconductor layer, 47 ... active layer, 49 ... second conductivity type group III nitride semiconductor layer, 51 ... group III nitride semiconductor layer, 53 ... electrode, J1, J2 ... junction, 55 ... support base.

Claims (14)

  1. A method for producing a group III nitride semiconductor device, comprising:
    Placing an epitaxial substrate including a substrate and a gallium nitride based semiconductor layer formed on the substrate in a vacuum chamber of a processing apparatus;
    Increasing the substrate temperature of the epitaxial substrate in the vacuum chamber;
    After raising the temperature of the epitaxial substrate in the vacuum chamber, a modification process is performed on the surface of the gallium nitride based semiconductor layer of the epitaxial substrate in the vacuum chamber to obtain a substrate product having a modified surface. Forming, and
    Depositing a conductive film on the modified surface of the substrate product to form a bond between the gallium nitride based semiconductor layer and the conductive film;
    The modification treatment includes any one treatment of gallium flux irradiation and nitrogen radical irradiation without simultaneously performing gallium flux irradiation and nitrogen radical irradiation,
    The surface of the gallium nitride based semiconductor layer exhibits semipolarity inclined at an inclination angle exceeding 61 degrees with respect to a first reference plane orthogonal to a reference axis extending in the c-axis direction of the gallium nitride based semiconductor layer. ,
    The reforming treatment includes a first portion extending along a first surface inclined at a first angle with respect to the first reference plane and a second angle with respect to the first reference plane. A method of fabricating a group III nitride semiconductor device, wherein the modified surface includes a step structure including a second portion extending along the second surface.
  2. 2. The method for producing a group III nitride semiconductor device according to claim 1, wherein the degree of vacuum in the vacuum chamber is 1 × 10 −6 Torr or less in the modification treatment.
  3.   The method for producing a group III nitride semiconductor device according to claim 1 or 2, wherein a substrate temperature in the modification treatment is 500 degrees Celsius or higher.
  4. The surface of the gallium nitride based semiconductor layer is inclined in a direction from the c axis to the m axis of the gallium nitride based semiconductor layer,
    4. The method for producing a group III nitride semiconductor device according to claim 1, wherein one of the first portion and the second portion includes a {10-10} plane. 5.
  5.   The method for producing a group III nitride semiconductor device according to claim 4, wherein the other of the first portion and the second portion includes a {10-11} plane.
  6. Each of the said 1st part and the said 2nd part is extended in the direction which cross | intersects the direction of the inclination of the said surface of the said gallium nitride type-semiconductor layer, It is described in any one of Claims 1-5. A method for producing a group III nitride semiconductor device.
  7. Arranging a substrate having a main surface made of a group III nitride semiconductor in a growth apparatus;
    Growing one or more gallium nitride based semiconductor layers on the main surface of the substrate with the growth apparatus to form the epitaxial substrate;
    Removing the epitaxial substrate from the growth apparatus, and further exposing the surface of the gallium nitride based semiconductor layer to the atmosphere,
    The main surface of the substrate has an angle exceeding 61 degrees in the m-axis direction of the group III nitride semiconductor with respect to a second reference plane orthogonal to a reference axis extending in the c-axis direction of the group III nitride semiconductor. Indicates semi-polarity,
    7. The group III according to claim 1 , wherein the gallium nitride based semiconductor layer extends along a third reference plane orthogonal to a normal axis of the main surface of the substrate. A method of manufacturing a nitride semiconductor device.
  8. 8. The III according to claim 1 , further comprising a step of providing a vacuum degree of 1 × 10 −10 Torr or less to the vacuum chamber prior to the modification treatment of the epitaxial substrate. A method for manufacturing a group nitride semiconductor device.
  9. The said electrically conductive film is described in any one of Claims 1-8 containing at least any one of Au, Pd, Ni, Rh, Al, Ti, Zn, Cu, In, Ta, Pt, and Tl. A method for producing a group III nitride semiconductor device.
  10. Further comprising a step of processing the conductive film to form an electrode on the substrate product;
    The method for producing a group III nitride semiconductor device according to any one of claims 1 to 9 , wherein the electrode is not alloyed.
  11. The method for producing a group III nitride semiconductor device according to any one of claims 1 to 10 , wherein in the modification treatment, gallium flux irradiation is performed without performing nitrogen radical irradiation.
  12. The method for producing a group III nitride semiconductor device according to any one of claims 1 to 10 , wherein in the modification treatment, nitrogen radical irradiation is performed without performing gallium flux irradiation.
  13. The group III nitride semiconductor device includes a group III nitride semiconductor light emitting device,
    The method for producing a group III nitride semiconductor device according to any one of claims 1 to 12 , wherein the group III nitride semiconductor light-emitting device includes an active layer that generates light by carrier injection.
  14. The method for producing a group III nitride semiconductor device according to claim 13 , wherein the active layer is formed to generate light in a wavelength range of 500 nm or more and 540 nm or less.
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