TW200903867A - GaN substrate, substrate with an epitaxial layer, semiconductor device, and GaN substrate manufacturing method - Google Patents

Abstract

Affords a GaN substrate from which enhanced-emission-efficiency light-emitting and like semiconductor devices can be produced, an epi-substrate in which an epitaxial layer has been formed on the GaN substrate principal surface, a semiconductor device, and a method of manufacturing the GaN substrate. The GaN substrate is a substrate having a principal surface with respect to whose normal vector the [0001] plane orientation is inclined in two different off-axis directions.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a GaN substrate, an epitaxial layer substrate, a semiconductor device, and a method of fabricating a GaN substrate, and more particularly to a semi-polar surface. A method for producing a G a N substrate, an agglomerated substrate, a semiconductor device, and a GaN substrate. [Prior Art] Previously, a laser diode (LD) and a light emitting diode (LED) using GaN have been known. Heretofore, the above-described LD or LED using GaN is formed by laminating a stray layer on a (0001) surface of a sapphire substrate, a SiC substrate, or a GaN substrate. Among them, since the (0001) plane of the GaN substrate or the like is a polar surface, there is a problem that the light-emitting efficiency of the LED is lowered in a long-wavelength region in which the emission wavelength is larger than 500 nm. In response to the above problems, it has been reported that the luminous efficiency of the long-wavelength region is improved by forming a quantum well structure on the (11-22) plane of the GaN crystal instead of the (000 1) plane (see Non-patent document 1)). Further, a method of manufacturing a GaN substrate in which the semipolar crystal plane is exposed on the main surface has been proposed (for example, see Patent Document 1). [Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-2983 No. 19 [Non-Patent Document 1] "Press Release: Successful Development of LEDs on Semi-Polar Surface Main GaN Substrates", [online], June 30, 2006, Kyoto University, [Search June 1, 2007], Internet (111^://'\¥评'\¥.1<:;/〇1;〇-u. ac.jp/notice/05_news/documents [060] The content of the LED disclosed in the above non-patent document uses a naturally formed semipolar crystal face as a microface, and the crystal face is fixed as (l M2) face, and the size is also small. However, from the viewpoint of efficiently manufacturing LEE^tLD and the like, it is preferable to use a semipolar crystal face exposed on the main surface (that is, having a so-called off angle) which refers to a specific plane orientation (for example, [〇〇 〇ι] direction) The LED f is manufactured by tilting a large-diameter GaN substrate of a specific angular angle of 2 Hz or more with respect to a normal vector of the main surface in a specific direction. Further, it is also considered that it is possible to adjust the plane orientation with respect to The value of the inclination angle of the normal vector of the main surface (that is, by changing the crystal plane exposed on the main surface of the substrate) improves the characteristics of the LED or LD. The present invention has been made to solve the above problems, and provides a A large-diameter GaN substrate having a size larger than 吋, an aegyptic layer substrate on which a worm layer is formed on a main surface of the GaN substrate, a semiconductor device, and (10) a substrate can be made inexpensively in the edifice A semiconductor device such as a light-emitting device having improved luminous efficiency is obtained. [Technical means for solving the problem] The inventors of the present invention have various methods of manufacturing a GaN substrate as shown in the above-mentioned patent document. An off-angle GaN substrate, and an epitaxial layer is formed on the main surface of the (four) substrate, an attempt is made to produce a led, and its characteristics are studied. As a result, it is found that by making the plane orientation [howling relative to the main surface] The line vector is inclined toward one plane orientation (one off-angle direction), so that the crystal plane exposed on the surface of the (10) substrate can be formed as a semi-polar plane, and by making the plane orientation [〇_进-step toward other plane orientations) (Other off-angle direction) tilt 131436.doc 200903867 The tilt controllable (can reduce) the unevenness of the wavelength distribution in the main plane of the GaN substrate. I7 The GaN substrate of the present invention has a main surface with a plane orientation [0001] relative to the main surface The normal vector is inclined in two off-angle directions which are different from each other. Thus, by tilting the plane orientation [0001] toward the off-angle direction, the main surface of the GaN substrate can be formed into a semipolar plane. An epitaxial layer is formed on the main surface. Therefore, compared with the case where an epitaxial layer is formed on a polar surface such as a (10) GaN plane of a GaN substrate to produce a light-emitting element such as an LED, the south-emitting wavelength is included in 5 〇〇. In the long wavelength region above nm The luminous efficiency of the illuminating member reduces the amount of wavelength shift due to the change in the amount of applied current. Further, by tilting the plane orientation (10) further toward the second off-angle direction, the main surface of the GaN substrate can be controlled. As a result, the in-plane wavelength distribution is uneven. As a result, a semiconductor device such as an LED having excellent characteristics can be stably produced by using the GaN substrate. The epitaxial layer substrate of the present invention includes the GaN substrate and the GaN substrate. The epitaxial growth layer on the main surface is formed on the semipolar surface of the GaN substrate, so that the epitaxial layer substrate with the following epitaxial layer can be provided, and the epitaxial layer substrate can be stably manufactured. A semiconductor device such as a light-emitting element in which a light-emitting wavelength is included in a long-wavelength region of 500 nm or more and luminous efficiency is improved. The semiconductor device of the present invention uses the above-described epitaxial layer substrate. In this case, a semiconductor device such as a light-emitting element in which the light-emitting wavelength is included in a long-wavelength region of 5 〇〇 nm or more and the light-emitting efficiency is improved and the amount of wavelength shift due to the change in the amount of applied current is small can be obtained. The method for producing a GaN substrate of the present invention includes the following steps. That is, the first 131436.doc 200903867 first performs a step of preparing a base substrate in which the reference plane orientation is inclined with respect to the normal vector of the main surface toward the two base substrate sides which are different from each other; a step of growing a GaN crystal layer on the surface; and a step of removing the base substrate from the GaN crystal layer, thereby obtaining a GaN substrate containing a GaN crystal layer. The GaN substrate has a main surface, and the plane orientation [0001] is inclined with respect to two normal off-axis directions with respect to the normal vector of the main surface. By changing the inclination angle of the reference plane orientation in the base substrate side in the oblique direction of the base substrate side, the inclination angle of the plane orientation [〇〇〇 1 ] in the off-angle direction of the GaN substrate can be adjusted. Thus, the GaN substrate of the present invention can be easily obtained. Further, it is possible to easily manufacture a GaN substrate which can arbitrarily change the inclination angle in the off-angle direction of the GaN substrate by changing the inclination angle of the reference plane orientation of the base substrate in the tilt direction of the base substrate side. Advantageous Effects of Invention According to the present invention, a GaN substrate, an epitaxial layer substrate, a semiconductor device, and a method of manufacturing a GaN substrate can be obtained, and the GaN substrate can be stably produced on a long wavelength side of an emission wavelength of 500 nm. A semiconductor device such as a light-emitting element in which the light-emitting efficiency is improved in the wavelength region. [Embodiment] Hereinafter, embodiments of the present invention will be described based on the drawings. In the following, the same or corresponding components are denoted by the same reference numerals, and the description thereof is not repeated. Fig. 1 is a schematic perspective view showing a GaN substrate of the present invention. Fig. 2 is a schematic view for explaining the crystal structure of the GaN substrate shown in Fig. 1. Fig. 3 is a schematic view showing the plane orientation and crystal plane of the crystal structure of the GaN substrate shown in Fig. 2, using 131436.doc 200903867. Fig. 4 is a view for explaining the inclination angle of the (10) substrate of the present invention shown in the drawing in the off-angle direction. The GaN substrate of the present invention will be described with reference to Fig. 4 . Referring to FIGS. 1 to 4' of the GaN substrate of the present invention, the specific square can f is a normal vector 2 of the surface orientation of the GaN substrate 1 (see the two directions different from each other in the direction of the drawing). That is, (10) the substrate (10) has a substrate having an off-angle, and the off-angle surface orientation [〇〇〇1] is inclined toward two plane directions or two directions different from each other. As shown, the crystal structure of GaN has a crystal structure of a so-called hexagonal crystal. In FIG. 2, the symmetry of the crystal structure of the hexagonal crystal of (4) is more easily understood, and the crystal structure of GaN is exemplified by a state including a plurality of units. In Fig. 2, a larger white circle indicates a nitrogen atom (N atom), and a smaller circle indicates a gallium atom (Ga atom). On the bottom surface of the crystal structure of Fig. 2, a Ga atom exists at the center, and (The Ga atom is also present at the apex of the positive hexagon at the center of the atom. The direction from the center of the bottom surface is the atomic connection of the six surrounding Ga atoms, and the counterclockwise direction is [2-1-10], [11 -20], [-12-10], [-2110], [_ι·120], π _ 210]. These directions are the directions of the Ga-Ga bonds of GaN, and the direction of the Ga atoms is not [ι_ 1〇〇], etc. observed from the center Ga atoms of the bottom surface. Furthermore, in Fig. 2 and In the crystal structure shown in 3, it can be regarded as a hexagonal column, and the upper surface of the square aa body is called a c-plane. The side wall surface of the hexagonal hexagonal column is called an m-plane. 131436.doc •10- 200903867 In the GaN substrate 1 of the present invention, the plane orientation [〇〇〇1] is oriented in two off-angle directions, i.e., plane orientation [1-100] and plane orientation, which are different from each other with respect to the normal vector 2 (see FIG. 1). [11-20] Directional tilting. Referring to Fig. 4, the tilt state of the plane orientation [0001] of the GaN substrate 1 with respect to the normal vector 2 of the main surface will be described in more detail. First, in Fig. 4, it can be considered that The direction indicated by the vector AB corresponds to the normal vector 2 (refer to FIG. 1) of the main surface of the GaN substrate, and, from the state of the plane orientation [0001] of the board and the state of the vector AB, GaN is made as follows The crystal is inclined, that is, the tilt direction θ 倾斜 is inclined such that the plane orientation [0001] is oriented toward the direction of the vector AE corresponding to the direction of the plane orientation [ιι〇〇]. The name of the GaN surface orientation [〇〇〇1] becomes the direction indicated by the vector Ac. Then, the GaN crystal structure inclined toward the direction indicated by the vector AC is further oriented toward the plane orientation [U_20] The direction of the vector af corresponding to the direction is inclined by the tilt angle Θ 2. As a result, the plane orientation [0001] of the GaN crystal becomes the direction indicated by the vector AD of Fig. 4. Thus, in the GaN substrate 1 of the present invention, the following state is formed. The direction of the plane orientation [0001] of the crystal is inclined with respect to the direction shown by the vector AD of FIG. 4 with respect to the normal vector 2 of the main surface indicated by the vector AB (refer to FIG. 1) (the plane orientation [0001] is relative to The normal vector 2 of the main surface is inclined toward the plane orientation [1-100] direction and the plane orientation [11-20] direction by the inclination angles θι and θ2, respectively).

Thus, the main surface of the GaN substrate 1 of the present invention is formed into a so-called semipolar surface. Compared with the case where a light-emitting element is formed by forming an epitaxial layer on the c-plane of GaN, a layer of GaN 131436.doc 200903867 or InGaN is epitaxially grown on the main surface of such a GaN substrate, and is formed as In the case of a light-emitting element of a semiconductor device, it is possible to suppress an internal electric field from being generated in the active layer. As a result, the influence of the following problem can be reduced: the generation of the internal electric field causes the recombination probability of electrons injected into the active layer to be reduced, and as a result, the luminous efficiency is lowered, or the emission wavelength is applied. The current changes and changes. Therefore, according to the present invention, a light-emitting element having improved luminous efficiency and having a fixed emission wavelength can be obtained. Figure 5 is used to illustrate the figure! A flow chart of a method of manufacturing a GaN substrate shown in the drawing. Figure 6 is a flow chart for explaining the contents of the preparation steps in the flowchart shown in Figure 5. A method of manufacturing a GaN substrate of the present invention will be described with reference to Figs. 5 and 6 . Referring to Figures 5 and 6, the preparation step 〇) is first performed. In this preparation step (S10), a base substrate which forms a base of a GaN worm layer as a GaN substrate is prepared. Specifically, in the preparation step (s 1 〇) (refer to Fig. 5), as shown in Fig. 6, the base substrate fabrication step (sii) is first performed. In the base substrate forming step (S11), a substrate is prepared which is a substrate on which GaN is epitaxially grown on the surface, and a specific surface orientation is normal to a main surface on which GaN is epitaxially grown. The orientation is inclined in two directions (inclination directions on the base substrate side) which are different from each other. Here, as the base substrate, any material can be used as long as GaN can be formed on the surface thereof. As the base substrate, for example, a gallium substrate (GaAs) substrate, a sapphire substrate, a zinc oxide (Zn) substrate, a carbonized carbide (SiC) substrate, or a GaN substrate can be used. Further, in the film forming step described later, 'the base substrate is formed into a substrate having a so-called off angle so as to be able to face the surface orientation of the formed GaN crystal layer [0001] with respect to 131436.doc -12-200903867 The base substrate is formed with a normal vector of the main surface of the GaN crystal layer, and the (4) crystal layer is grown in a state of being inclined in a specific (10) direction (two off-angle directions). Specifically, the base substrate is formed in a state in which a specific reference plane orientation is inclined toward a specific square (four) with respect to a normal vector forming a main surface of the crystal layer. For such a substrate, for example, a base substrate can be prepared by preparing a substrate whose main surface is a specific crystal plane (for example, a hexagonal crystal, the main surface is a c-plane, etc.), with respect to the main surface of the substrate The main surface of the substrate is polished by tilting the tilt direction in a specific direction, or the base substrate is cut from the main body substrate of the main surface of the B-day body material by a special cut angle S. Next, as shown in FIG. 6, a mask pattern forming step (S12) is performed. In the mask pattern forming step (S12), a mask pattern is formed on the main surface of the base substrate on which the GaN crystal layer is formed. Specifically, a mask layer 1 having a pattern as shown in Fig. 8 or Fig. 8 is formed. 7 and 8 are schematic plan views showing a mask pattern of a mask layer formed on the main surface of the base substrate. First, the mask pattern shown in Fig. 7 will be described. As shown in Fig. 7, the mask layer 1 formed on the main surface of the base substrate can be formed in such a manner that a plurality of linear patterns having a width W1 extend in parallel at intervals p. In this case, the pitch p can be, for example, 8 μm, the width wi of the linear pattern is 6 μm, and the interval W2 between the line patterns (the width of the groove-like opening 11 formed between the line patterns) is, for example, 2 Ππι. Further, the thickness of the linear pattern can be, for example, 〇. 1 μηι. Further, as another example of the mask pattern, as shown in Fig. 8, a mask layer 1 具有 having a pattern of the opening portion 12 periodically formed with 131436.doc -13 - 200903867 can be used. Specifically, as shown in Fig. 8, the mask layer 10 in which the opening portion 12 having a quadrangular planar shape is disposed at a predetermined interval is formed on the main surface of the base substrate. As shown in Fig. 8, the opening portion 12 is, for example, a square, and the distance L connecting the lines of the centers thereof may be, for example, 4 μm. Further, the hand W1 and W2 of one side of the opening portion 12 may be two. Further, the opening portion 丨2 may be disposed such that a plurality of the openings 12 are arranged in a so-called thousand-bird grid shape, and when the center points of the adjacent opening portions 12 are connected, one side is formed as a distance [the equilateral triangle . As shown in Fig. 5, a film forming step (S20) is performed on the base substrate on which the mask layer 1 is formed. Specifically, a GaN thin film is formed on the main surface of the base substrate on which the mask layer is formed by a vapor phase growth method. As a vapor phase growth method of a GaN thin film, an HVPE method (Hydride Vap〇r, Epitaxy, hydride vapor phase epitaxy), a sublimation method, an M〇c method (MetaU〇rganic Chloride, an organic metal emulsion gas phase) can be used. Growth method), MOCVD method (^/^&1_organic chemical Vapor Deposition, metal organic chemical vapor deposition method) and the like. In the film forming step (S20), for example, HVPb^ can be used. Fig. 9 is a schematic view showing a film forming apparatus used in the film forming step (S2). Referring to Fig. 9, a film forming apparatus using the hvpe method will be described. As shown in FIG. 9, the film forming apparatus 2 includes a reaction tube 22, a Ga carrier 23 disposed inside the reaction tube 22, and a susceptor 24 for holding the base substrate inside the reaction tube 22 for the reaction tube. 22 internally heated heater 26. Ga metal is disposed inside the Ga carrier 23. Further, a pipe 27 for supplying hydrogen chloride (HC1) gas diluted with hydrogen, nitrogen or argon is disposed toward the carrier 23131.doc -14-200903867. Further, a pipe 28 for supplying ammonia (NH3) gas diluted with hydrogen, nitrogen or argon is provided on the upper portion of the susceptor 24. A heater 26 for heating the reaction tube 22 is disposed at a position opposite to the outer circumference of the reaction tube 22. On the susceptor 24, a base substrate 5 is provided. A GaN crystal layer 3 is formed on the base substrate $ in the following manner. Hereinafter, a method of manufacturing the GaN crystal layer 3 using the film forming apparatus 2 shown in Fig. 9 will be described. First, in the film forming apparatus 2A shown in Fig. 9, the base substrate 5 is placed on the susceptor 24 inside the reaction tube 22. Then, above the susceptor 24, a container of Ga metal inside, that is, a 〇a carrier 23 is disposed. Next, in a state where the entire device is heated by the heater 26, HC1 gas diluted with hydrogen, nitrogen or argon is blown into the carrier 23 via the pipe 27. As a result, the following reaction occurs: - 2GaC1+ H2. Gas-like GaC丨 generated by the reaction is supplied to the base substrate 5. At the same time, 'a gas diluted with hydrogen, nitrogen or argon is supplied to the vicinity of the susceptor 24 via the pipe 28. At this time, on the base substrate 5 The following reaction occurs in the vicinity: 2GaC1+2NH3 - 2 GaN track 2. (10) formed by such a reaction is laminated on the surface of the heated base substrate 5 as a GaN crystal, thereby forming a GaN crystal layer on the surface of the base substrate 5. 3. At this time, a (10) junction is formed on the mask layer 1 as shown in FIG. 7 or FIG. 8 on the surface of the base substrate, and as a result, the dislocation density of the formed GaN crystal layer 3 can be lowered. The base substrate 5 has a so-called off-angle base 2: the formed GaN crystal layer 3 is also in a state in which a specific plane orientation is inclined with respect to a normal vector of a surface opposed to the main surface of the base substrate 5. : 131436.doc 15· 200903867 (four) knot The inclination of the specific plane orientation in the layer 3 with respect to the normal vector and the inclination angle G of G may vary depending on the inclination direction and the inclination angle of the reference plane orientation in the base substrate. Further, 'the GaN crystal layer 3 is formed. It is thick enough to be independently operated after the base substrate 5 is removed as will be described later. The thickness of the GaN and the crystal layer 3 can be, for example, about 10 mm. The base substrate removing step (S30) is performed. In the substrate removing step _, the base substrate 5 is removed from the formed GaN crystal layer 3. As a method of the base substrate 5, a cutting or the like can be used. Any method such as a chemical method, an electrochemistry method such as electrolysis or the like, and as a result, a substrate containing the GaN crystal layer 3 can be obtained. Further, the reference plane orientation is inclined in two directions in the base substrate, whereas The obtained (four) substrate 1 (see FIG. D is formed in a state in which the surface orientation _) is inclined with respect to the two off-angle directions in which the surface of the (four) substrate 1 is different. Thereafter, a post-processing step (S4 〇) is performed. Post-processing step _), For example, a polishing step of the surface of the substrate or a cutting step of cutting the substrate 10 into a specific thickness or the like can be performed. As shown in FIG. H), on the surface of the substrate (10) obtained in the above manner, a crystal of _ is formed. The layer 40, whereby the crystal layer substrate (the epitaxial substrate 41) can be obtained. Figure 10 is a perspective view showing a crystal-attached substrate of the GaN substrate of the present invention shown in Figure 1. Further, the substrate can be formed into a light-emitting element in the manner shown in Fig. U. Fig. 1 is a schematic cross-sectional view showing a light-emitting element using the GaN substrate of the present invention. Fig. 131436.doc •16·200903867 11 ' The light-emitting element using the GaN substrate of the present invention will be described. As shown in FIG. 11, in the light-emitting element 3A of the semiconductor device, an 11-type AK}aN intermediate layer 31 is formed on the QaN substrate 1. A type 11 GaN buffer layer 32 is formed on the n-type AiGaN intermediate layer 31. A light-emitting layer 33 is formed on the GaN buffer layer μ of the type. The light-emitting layer 33 is, for example, an InGaN/InGaN_MQ layer (multiple quantum well layer). A p-type AlGaN layer 34 is formed on the light-emitting layer 33. A GaN buffer layer 35 of the {) type is formed on the p-type A1Ga>^34. Then, an n-electrode is formed on the back side of the GaN substrate (the surface on the side opposite to the surface on which the n-type MG·intermediate layer 31 is formed). Further, a p-electrode 37 is formed on the p-type GaN buffer layer 35. As described above, when the GaN substrate of the present invention is used to form a light-emitting element, since the light-emitting layer 33 is formed on the so-called semipolar surface of the GaN substrate, the piezoelectric field in the light-emitting layer 33 is weakened. Therefore, compared with the light-emitting element in which the previous light-emitting layer is formed on the polar surface of the GaN substrate, the light-emitting efficiency of the light-emitting layer can be improved, and the amount of shift of the light-emitting wavelength due to the change in the amount of applied current can be reduced. Hereinafter, embodiments of the present invention will be described and described, and in the examples, there are portions partially overlapping the above embodiments. In the GaN substrate i of the present invention (the reference substrate has a main surface (4) substrate 1 and the plane orientation [000]] is inclined with respect to the normal vector 2 of the main surface toward two different off-angle directions which are different from each other. The plane orientation [0001] is inclined toward the first off-angle direction, and the epitaxial layer 40 can be formed on the main surface in a state where the main surface of the GaN substrate i is formed into a semipolar plane. Therefore, the GaN substrate is formed on the GaN substrate. 131436.doc • 17- 200903867 (0001) Compared with the case where an epitaxial layer is formed on the surface of the same polarity to produce a light-emitting element such as an LED, the light-emitting wavelength of the long-wavelength region of 5 nm or more can be increased. The luminous efficiency of the piece, or the amount of shift of the light-emitting wavelength due to the change in the amount of applied current. Further, the GaN substrate 1 can be controlled by tilting the plane orientation [0001] further toward the second off-angle direction. The off-angle distribution of the main surface or the unevenness of the in-plane wavelength distribution. The back surface of the GaN substrate also has an off-angle that is substantially the same as the surface. As a result, the contact between the electrodes formed on the front surface and the back surface can be improved. Small comparison Increase the amount of the operating voltage of the beginning of the beginning. Therefore, by using the

The GaN substrate 1 can stably manufacture a semiconductor device such as a light-emitting element having excellent characteristics. In the GaN substrate 1, the plane orientation [〇〇〇1] is inclined in two off-angle directions with respect to the normal amount 2 of the main surface, and may be a [heart (8)] direction and a mouth (10) direction. At this time, the main surface of the GaN substrate i can be formed as a semipolar surface, whereby a light-emitting element (semiconductor device) having improved luminous efficiency in a long-wavelength region can be obtained, and can be surely controlled on the main surface of the GaN substrate. The in-plane wavelength distribution is uneven when the insect layer is formed. In the GaN substrate 1, the plane orientation [〇〇〇1] is inclined with respect to the normal direction of the main surface in the [1-100] direction and the inclination angle in the [112〇] direction. Can be 10. Above 4〇. Hereinafter, the other one may be 40 or more. the following. Further, any one of the above two inclination angles may be set to 10. Above 40. Hereinafter, the other is 〇〇2. Above 1〇. the following. In this case, the main surface of the GaN substrate can be formed as a semi-polar surface, whereby a light-emitting element (semiconductor device) having improved luminous efficiency in a long-wavelength region can be obtained, and can be surely reduced by 131436.doc •18·200903867 The unevenness of the in-plane wavelength distribution when the epitaxial layer is formed on the main surface of the GaN substrate is small. The epitaxial layer substrate (the epitaxial substrate 41) of the present invention comprises the GaN substrate 1 and an epitaxial growth layer (the epitaxial layer 40) formed on the main surface of the GaN substrate. Since the epitaxial layer 40 is formed on the semipolar surface of the GaN substrate i, the epitaxial substrate 41 can be supplied with the epitaxial substrate 41, and the emission wavelength can be stably produced to be 500 nm or more. A semiconductor device such as a light-emitting element in which a light-emitting efficiency is improved in a long wavelength region. The semiconductor device (light-emitting element) of the present invention can be manufactured using the above-described epitaxial substrate 41. In this case, a semiconductor device such as a light-emitting element in which the emission wavelength is included in a long wavelength region of 5 〇〇 nm or more and the luminous efficiency is improved and the amount of wavelength shift is small with respect to the applied current value is obtained. The method for producing a GaN substrate of the present invention includes the following steps. That is, first, the step of preparing a base substrate (base substrate forming step (S11)) in which the reference plane orientation is inclined with respect to the normal vector of the main surface toward the two base substrate sides which are different from each other; a step of growing the GaN crystal layer 3 on the main surface of the base substrate 5 (film formation step (S20)); and a step of removing the base substrate 5 from the GaN crystal layer 3, thereby obtaining the GaN substrate 1 containing the GaN crystal layer 3 ( Base substrate removal step (S3〇)). The GaN substrate 1 has a main surface, and the plane orientation [0001] is inclined with respect to the normal vectors of the main surface toward two mutually different off-angle directions. The inclination angle of the plane orientation [0001] in the off-angle direction of the GaN substrate is adjusted by changing the inclination angle of the reference plane orientation in the base substrate side in the oblique direction of the base substrate side. The two base substrate side inclined directions of the base substrate may be orthogonal to each other. 131436.doc -19- 200903867 Further, the two off-angle directions of the GaN substrate may be orthogonal to each other. Further, the GaN substrate 1 can be manufactured by changing the inclination angle of the GaN substrate 1 in the off-angle direction by changing the inclination angle of the reference plane orientation of the base substrate 5 in the oblique direction of the base substrate side. In the above method of manufacturing a GaN substrate, the base substrate 5 may be a GaAs substrate, and the reference plane orientation may be [111]. The inclination direction of the two base substrate sides may be a <1-10> direction and a <11-2> direction. The two off-angle directions of the GaN substrate 1 may be in the [11-20] direction and the [1-100] direction. At this time, the 〇aN substrate i of the present invention can be produced by using a GaAs substrate which is relatively easy to obtain as a base substrate, so that the manufacturing cost of the GaN substrate can be reduced. In the method of manufacturing a GaN substrate, the base substrate 5 may be a sapphire substrate. The reference plane orientation may be [0001]. The inclination direction of the two base substrate sides may be the [11-20] direction and the [1-100] direction. The two off-angle directions of the GaN substrate 1 may also be in the [1-100] direction and the [11-20] direction. At this time, since the GaN substrate of the present invention can be manufactured by using the relatively easy-to-obtain sapphire substrate as the base substrate 5, the manufacturing cost of the GaN substrate can be reduced. In the method for producing a GaN substrate, the base substrate 5 may be a zn〇 substrate. The reference plane orientation may be [0001]. The inclination direction of the two base substrate sides may also be the [1-1 00] direction and the [11-20] direction. The two off-angle directions of the GaN substrate 1 may also be in the [1-100] direction and the [11-20] direction. At this time, since the GaN substrate 1 of the present invention is produced by using the ZnO substrate which is relatively easily obtained as the base substrate 5, the manufacturing cost of the GaN substrate can be reduced. In the method of manufacturing a GaN substrate, the base substrate 5 may be a sic substrate, and the reference plane orientation may be [0001]. The tilting direction of the two base substrate sides is also 131436.doc • 20- 200903867 It can be in the [1-100] direction and [11-20] direction. The two off-angle directions of the GaN substrate 1 may also be in the [1-100] direction and the [11-20] direction. At this time, since the GaN substrate of the present invention can be produced by using a relatively easy-to-obtain SiC substrate as a base substrate, the manufacturing cost of the GaN substrate can be reduced. In the method of manufacturing the GaN substrate, the base substrate 5 may be a GaN-containing substrate. The reference plane orientation may be [〇〇〇 1 ]. The inclination direction of the two base substrate sides may be the [1-100] direction and the [11-20] direction. The two off-angle directions of the GaN substrate can also be the [1-100] direction and the [11_20] direction. In this case, as the base substrate 5 on which the GaN crystal layer to be the GaN substrate 1 is formed, a substrate formed of GaN which is the same material is used, whereby the film quality of the GaN crystal layer 3 can be improved, and the substrate 1 excellent in film quality can be obtained. . In the above method for producing a GaN substrate, the step of forming a mask layer having a plurality of holes on the main surface of the base substrate 5 (mask) may be further included before the step of growing the GaN crystal layer (film formation step (S20)) Pattern forming step (S12)). In this case, when formed on the main surface of the base substrate 5

In the case of GaN, ', Q sa layer 3, the GaN crystal is first grown on the main surface of the base substrate 5 exposed from the hole (opening portion 12) of the mask layer, and then the crystal grows laterally on the mask layer ίο. Further, after the GaN crystals which have grown laterally from the adjacent opening portions 12 collide with each other, they grow in the vertical (upward) direction on the surface of the mask layer 1A. Thereby, the dislocation density of the GaN substrate 1 can be reduced, and a large-diameter GaN substrate which is useful for the slabs of 2 Å or more without cracks can be obtained. In the method of manufacturing a GaN substrate, one of the inclination angles in the oblique direction of the two base substrate sides of the base substrate 5 may be 〇. Above 4〇. The following 131436.doc -21 - 200903867 can be 0.02. Above 40. the following. The two plates 1 are inclined downward in the off-angle direction and 0.02° or more and 40° or less. In time, the formed GaN base angle can be adjusted to be 1 〇〇 or more 40. [Example 1] Next, in order to confirm the effects of the present invention, the experiment described below was carried out. Namely, the GaN substrate of the present invention was produced, and a light-emitting device was produced using the (four) substrate. (4) The relationship between the wavelength of the luminescent light and the amount of current supplied, etc., is measured for the GaN substrate and the light-emitting element in the manner described later. Further, for comparison, a (10) substrate having a major surface and a GaN substrate having a m-plane as a main surface were prepared. Similarly, the (four) substrate was used to form a light-emitting device of a comparative example. Next, the same characteristics of the light-emitting elements of the comparative examples were measured. The experimental contents will be specifically described below. (1) Preparation of GaN substrate (1-1) Preparation of GaN substrate of the present invention Base substrate:

A GaAs substrate is used as the base substrate, wherein a 2-inch GaAs substrate in which the crystal orientation [lu] is oriented with respect to the normal vector of the surface of the base substrate in the direction of <1_1〇> Tilt 18. Further, it is inclined by 0.03 toward the <11-2> direction. And on the surface of the base substrate, a mask layer having a stripe pattern as shown in Fig. 7 is formed. The mask layer is formed of cerium oxide (Si 〇 2). In the mask layer 1 ,, the width of the line pattern was 6 μm, the width W2 of the opening was 2 μm, and the line pitch of the line pattern was set to 8 μm. Further, the thickness of the mask layer 10 is made oj μηι. Film formation conditions: 131436.doc -22- 200903867 Formed on the surface of the above-mentioned substrate under the conditions described below

GaN crystal layer. That is, a GaN crystal layer is formed on the surface of the base substrate by the HVPE method using the joint 20 shown in Fig. 9. In the growth step of the GaN crystal on the surface of the base substrate, a relatively thin buffer layer is first formed at a relatively low temperature. Thereafter, a thicker G(10) crystal layer is grown on the buffer layer at a relatively high temperature. The film formation conditions of the buffer layer are as follows: the film formation temperature is 500 ° C, the partial pressure of HC1 is lxl 〇 -3 atm (1 〇〇 pa), and the partial pressure of nh3 is ο"atm (1_ Pa), so that The film formation time is called a bell, and the thickness of the buffer layer formed is 60 nm. Further, the film formation conditions of the GaN epitaxial layer formed on the buffer layer are as follows: the film formation temperature is such that the partial pressure of HC1 is 3x10-2 atm (3 〇〇〇pa), and the partial pressure of NH3 is 〇2. Atm (20000 Pa), the surface of one side is doped as an n-type dopant for one hour, and the thickness of the epitaxial layer formed by the film is 1 mm. Thereafter, the GaAs substrate was removed from the formed GaN film using a mechanical grinder. Thereby, an independent GaN substrate having a thickness of 1 〇 mm was obtained. Then, the GaN substrate was cut into a thickness of 400 μm using a wire saw, and the surface was further polished to obtain a one-inch 2 inch GaN substrate. (1-2) Preparation of GaN Substrate of Comparative Example GaN Substrate whose main surface is c-plane: The GaN substrate of the comparative example was basically produced by the same manufacturing method as the above-described GaN substrate of the present invention, but differed in the following points. In the GaAs substrate as the base substrate to be used, the crystal orientation [111] is parallel to the normal vector of the main surface. By using such a base substrate, in the obtained independent GaN substrate, the normal vector of the main surface and the crystal orientation [〇〇〇1] are flat, 131436.doc -23 - 200903867, the main surface and the (0001) plane (C face) parallel. A GaN substrate having an m-plane as a main surface: a GaN substrate having a c-plane from the main surface is formed, and a substrate having a thickness of 400 μm is cut in a direction perpendicular to the main surface thereof, whereby a GaN substrate having an m-plane main surface is prepared. (2) The light-emitting element was formed on the surface of the obtained GaN substrate of the embodiment of the present invention and the comparative example, and an epitaxial layer was deposited to form an electrode, and was divided into respective elements, thereby forming a light emission as shown in FIG. element. Further, the thickness of the n-type AlGaN intermediate layer 31 of the light-emitting element is 50 nm, the thickness of the n-type GaN buffer layer 32 is 2 μm, the thickness of the light-emitting layer 33 is 50 nm, and the thickness of the p-type AlGaN layer 34 is 20 nm. The p-type GaN contact layer 35 has a thickness of 50 nm. Further, Al/Ti was used as the n-electrode 36, and the thicknesses thereof were as follows, A1: 500 nm, Ti: 50 nm. Further, the material of the p electrode 37 is Pt/Ti, and the thickness is as follows, Pt: 500 nm, Ti: 50 nm. As the η electrode, Au/Ge/Ni (each thickness is 500 nm/100 nm/50 nm), Pt/Ti (each thickness is 500 nm/50 nm), and Au/Ti (each thickness is 500 nm/) can also be used. 50 nm), as the ρ electrode, Pt (thickness: 500 nm) and Ni (thickness: 500 nm) can also be used. Since such a light-emitting element contains InGaN as the light-emitting layer 33, light of a green region having a longer wavelength than the blue region is emitted. (3) Measurement contents For the GaN substrate obtained as described above, the off angle of the substrate (the direction of inclination of the plane orientation [0001] with respect to the normal vector of the surface of the GaN substrate and the inclination angle) was measured. Further, the in-plane distribution of the value of the off angle is also measured. In addition, the dislocation density of the GaN substrate was also measured in addition to 131436.doc -24- 200903867. Further, the relationship between the light emission wavelength and the amount of current of the formed light-emitting element was measured. (3-1) Measuring method

Measurement of the distribution of the off-angle and the off-angle value of the GaN substrate: The off-angle of the GaN substrate was measured using an X-ray diffraction (X-ray diffraction) apparatus with an opening size of 200 μm in both vertical and horizontal directions. Further, the distribution of the value of the off angle in the GaN substrate was measured by using the above XRD apparatus on the main surface of the GaN substrate, on the substrate center, and in the <1-100> direction and <11-20> Four points of 20 mm from the center in the direction, that is, an offset angle of 5 points in total, were measured. The maximum value of the absolute value of the difference between the value of 4 points from the center of 20 mm and the value of the center is taken as the distribution value of the deviation angle. Further, the measurement accuracy under XRD was ±0.01°.

Measurement of Dislocation Density of GaN Substrate: For GaN substrate, CL (cathodo luminescence) using SEM (Scanning Electron Microscope), for the same five points as the above XRD, count □ 100 μm inside The dark spot, thereby measuring the dislocation density of the GaN substrate. Measurement of the wavelength of the light emitted from the light-emitting element and the amount of current supplied: The value of the current supplied from the light-emitting element was changed, and the wavelength of the light emitted from the light-emitting element was measured. Specifically, a pulse current was applied to the light-emitting element at room temperature, and the emission spectrum was measured. (4) Measurement results

Deviation angle of GaN substrate:

The off angle of the GaN substrate indicates the plane orientation [0001] with respect to the normal to the surface. 131436.doc -25 - 200903867 The vector is inclined by approximately 18 toward the [11-20] direction. The resulting off angle. Further, it indicates an off angle which is inclined by approximately 0.05 in the [1-100] direction. Further, the in-plane distribution of the off angle in the [11-20] direction is as follows: in the plane of the substrate, the off angle is distributed at ±0.5. Within the range of -17.5 to 18.5°. Further, the in-plane distribution of the off-angle in the direction of fl_100] is such that the distribution of the off-angle is ±0.3 in the plane of the substrate. Within the scope.

Dislocation Density of GaN Substrate: As a result of measuring the dislocation density of the GaN substrate, the dislocation density was 1×10 7 (/cm 2 ) or less in any of the samples. The relationship between the wavelength of the illuminating light of the illuminating element and the amount of current supplied:

L Example 2] The results are shown in Fig. 12. Fig. 12 is a graph showing the relationship between the current supplied to the light-emitting element and the wavelength of the emitted light. As can be seen from FIG. 2, the relationship between the wavelength of the light-emitting element of the embodiment of the present invention and the amount of current is as follows: as the amount of current supplied to the light-emitting element increases, the wavelength of the emitted light shifts toward the short-wavelength side. The offset is about 7 nm. The offset is smaller than the GaN substrate using the first month J, that is, the surface of the substrate is substantially parallel to the e-plane of GaN. In the case of a light-emitting element of a comparative example in which k is a surface, k is a wavelength shift of about 2 Å, and a comparative example produced by using an m-plane substrate as shown in Fig. U is used. The reason is: due to the m-plane

The off-angle direction and deviation of 锒°° were performed as described below. Namely, 70 GaN substrates were produced, and the GaN substrate dimensions and the in-plane distribution of the off-angle were measured, and the bit density was 131436.doc • 26 - 200903867. Further, each of the GaN substrates is used to form a light-emitting element, and the amount of change in the light-emitting wavelength due to the change in the input current value (Blue shift: Δλ) and the increase in the operating voltage at the time of 1000 hours are measured. Δ Vop), the emission wavelength distribution (σ) in the plane of the GaN substrate. The content of the experiment is specified below. (1) Preparation of GaN substrate All samples (sample IDs 1 to 70) were obtained by using a manufacturing method substantially the same as that of the GaN substrate in the above-described first embodiment. Base substrate:

In the sample IDs 1 to 65, a GaAs substrate was used as a base substrate for forming a GaN substrate, and in samples ID 66 to 70, a substrate different from 〇aAs was used as a base substrate. Specifically, in the samples 1〇66 and 7〇, a sapphire substrate was used as the base substrate, and in the samples ID68 to 7〇, a ZnO substrate, a SiC substrate, and a GaN substrate were used as the base substrate, respectively. For each of the base substrates, the plane orientation [〇〇〇1] is appropriately oriented in two directions with respect to the normal direction of the main surface on which the GaN crystal film is formed so that the off-angle direction of the formed GaN substrate is two directions. Tilt angle of the tilt (off angle). Specifically, in the GaAs substrate, the plane orientation is such that the plane orientation [0001] of GaN is inclined with respect to the surface of the formed GaN crystal film toward the [丨^... direction and the [1-100] direction, respectively. In this manner, the normal vector with respect to the main surface of the GaAs substrate is inclined toward the <1-1 〇> direction and the <u_2> direction. The inclination angle in each direction (off-angle direction) is changed corresponding to each sample (<1-10> direction deviation angle Θ1 and <11-2> direction deviation angle 02). 131436.doc 27· 200903867 In addition, in the sapphire substrate, the plane orientation [0001] is such that the plane orientation [0001] of GaN is opposite to the surface of the formed GaN crystal film, and is oriented toward the tl_100] direction and [11-20], respectively. The direction is inclined, and the normal vector with respect to the main surface of the sapphire substrate is inclined toward the [11-20] direction and the [1-100] direction. Set the inclination angle (the deviation angle Θ1 in the [u_ 20] direction and the deviation angle Θ2 in the [1-100] direction) in each direction (off-angle direction) of the sample ID 66 to Θ1=Θ2=26°, and sample The inclination angle in each direction (off-angle direction) of ID67 is set to Θ1=Θ2=40°. Further, in the ΖηΟ substrate, the plane orientation [0001] is inclined with respect to the normal vector of the main surface of the ΖηΟ substrate toward the [1-100] direction and the [11-20] direction. The inclination angle in each direction (off-angle direction) (the deviation angle 01 in the [1-100] direction and the deviation angle Θ2 in the [11-20] direction) is set to Θ1 = Θ2 = 26°. Further, in the SiC substrate, the plane orientation [0001] is inclined with respect to the normal vector of the main surface of the SiC substrate toward the [1-100] direction and the [11-20] direction. The inclination angle (the deviation angle Θ1 in the [1_1〇〇] direction and the deviation angle Θ2 in the [11-20] direction) of the directions (off-angle direction) is set to Θ1=Θ2=26. . Further, in the GaN substrate, the plane orientation [〇〇〇1] is inclined with respect to the [1-1 〇〇] direction and the [11_20] direction with respect to the normal vector of the main surface of the GaN substrate. The inclination angle in each direction (off-angle direction) (the deviation angle Θ1 in the [1-100] direction and the deviation angle Θ2 in the [11-20] direction) is set to Θ1 = Θ2 = 26. . Further, the sample IDs 1 to 70 were all attached to the main surface of the base substrate, and a mask layer having the stripe pattern shown in Fig. 7 was formed in the same manner as in the first embodiment. The thickness of the mask layer, the size of the line pattern, and the like are the same as those of the mask layer in the first embodiment. Film formation conditions: 131436.doc -28- 200903867 A GaN crystal layer was formed on the surface of the above-mentioned base substrate under the conditions of Table 14_heart described later. Namely, a (four) crystal layer was formed on the surface of the base substrate by the HVPE method using the film forming apparatus shown in Fig. 9. In the growth step of the GaN crystal on the surface of the base substrate, first, a relatively thin buffer layer is grown at a relatively low temperature. Thereafter, a relatively thick (4) worm layer is grown on the buffer layer at a relatively high temperature. The film formation conditions of the buffer layer are as shown in Tables i to 14 below. Further, the sample 1〇7〇 using the GaN-containing substrate as the base substrate did not grow the buffer layer, and the GaN epitaxial layer was directly grown on the base substrate. Thereafter, the base substrate such as the substrate is removed from the formed GaN film by polishing. Thus, an independent GaN substrate having a thickness of 1 mm was obtained. Then, the GaN substrate was cut into a thickness of 4 μm by a wire saw, and the surface was polished to obtain a 2-inch GaN substrate of one turn. (2) Formation of light-emitting element A layer of an epitaxial layer was formed on the surface of the obtained GaN substrate of Samples ID 1 to 70, and an electrode was formed and divided into respective elements, whereby a light-emitting element as shown in the figure was formed. Further, the composition, thickness and the like of the respective layers of the light-emitting element are the same as those of the light-emitting element of the first embodiment. (3) Measuring the GaN substrate obtained in the above manner, and measuring the off angle of the substrate (the orientation of the plane orientation [〇〇〇1] with respect to the normal vector of the surface of the GaN substrate in the [1 - 00] direction ( Offset angle 0a), and tilt angle (offset angle Ob) in the [丨丨-20] direction). Further, the in-plane distribution of the value of the off angle is also measured. Further, the dislocation density of the GaN substrate was also measured. Further, the relationship between the emission wavelength and the amount of current of the light-emitting element formed by 131436.doc -29-200903867 was measured. The method of measuring each data is as follows.

Determination of the distribution of the off-angle and off-angle values of the GaN substrate:

The off angle of the GaN substrate was measured by the same method as the measurement method of the off angle in Example 1 using an XRD (x_ray diffracti) apparatus. Further, the distribution of the off-angle in the plane of the GaN substrate was also measured by the same measurement method as in the measurement method of Example 1.

Measurement of Dislocation Density of GaN Substrate: The dislocation density of the GaN substrate was measured using CL' of the SEM on the SEM by the same measurement method as in the measurement of Example 1. Measurement of the amount of change in the emission wavelength of the light-emitting element (blue shift: Αχ): The value of the current supplied from the light-emitting element was changed, and the wavelength of the light emitted from the light-emitting element was measured. The specific measurement method is the same as that in the examples. Further, the difference between the emission wavelength when the value of the current supplied to the light-emitting element is sufficiently large (specifically, 200 mA) and the emission wavelength when the current is 10 mA is taken as a blue shift (Blue shift: Δλ (unit) : nm)). Measurement of the amount of increase in operating voltage (ΔVqP) at 1000 hours after the light-emitting element is measured: For the light-emitting element to be fabricated, the voltage required to pass a current of 100 mA to the light-emitting element is measured at a temperature of 8 (TC). The operating voltage at the beginning of the operation and the operating voltage after 1000 hours of operation are taken as Ανορ (unit: V).

Measurement of emission wavelength distribution (σ) in the plane of the GaN substrate: 131436.doc • 30· 200903867 The wavelength distribution in the plane was measured for a GaN substrate having an epitaxial layer formed on the surface of the light-emitting device. The specific measurement method is as follows: forming an n-electrode on the back surface of the GaN substrate, forming a p-electrode on the epitaxial layer, and then respectively, from the center of the substrate, and in the direction of <1-100> and <11_20> The 4 points of 20 mm are 5 points in total, and the light-emitting elements of 5 〇〇) are taken at 1 point per point. To a total of 5 light-emitting elements obtained by the results, a pulse current was applied at room temperature, and an emission spectrum was measured, and the average values of the emission wavelengths of the respective points were calculated. Further, the average value (5 data) of the above-mentioned light-emitting wavelengths of the center and the other four points is calculated, and the maximum value among the absolute values of the differences of the data is taken as the wavelength distribution (unit: nm). (4) Measurement results The following results are disclosed.

131436.doc • 31 - 200903867 [1<] (Goose ton 苓 °) Hui ¥ C7N Comparative Example GaAs CS 〇500 1 1x10'" I 1—« o § § 1030 3xl0'z CN d 0 0 0 Growth and growth Polymerization Growth Polymerization Polymerization Polymerization Polymerization Polymerization 1 1 00 Example I500 I lxlO_J 1 o § 1030 1 3xl0'2 1 CN 0 0 0 0 39.90 0.02 ±1.4 ±1.6 1.00E+08 0.06 1 ±2.6 Example 〇 500 1 lxlO'J 1 o § § 1030 1 3xl〇·' 1 0 0 0 0 34.19 0.02 +1 ±1.0 i 1.00E+07 in 0.05 1 ΐί v〇Example VO (N 〇500 1 ixi〇"J 1 1—^ os 1030 1 3xl0_z 1 (N 〇0 0 26.12 | 0.02 <N +1 +1 | 1.00E+07 0.04 1 ♦> in 〇〇lxio·3 l-lo § § 1030 1 3xl0'2 1 CN 〇0 0 0 isrf | 25.01 | | 0.00 1 ±2.4 ^±23 | 1.00E+07 | 00 1 0.06 1 00 f 丨 Reference example 00 〇500 lxlO-3 oss 1030 3xl0'2 (N 〇0 0 0 18.40 0.01 ±2.0 ±2.0 1.00E+07 00 1 0.04 1 o Reference example i 〇〇500 lxlO·3 os § 1030 3xl0·2 CN 〇0 0 f > 0 10.05 | 0.00 ±2.0 ±2^ 1.00E+ 07 | 〇1 0.05 i ±5_0 CN ratio Comparative example 500 lxlO·3 o § § 1030 3xl0·2 CN 〇0 0 0 4.95 \ 0.02 | ±1.8 ±1.9 1.00E+07 宕1 0.05 1 On f丨1-^ Comparative example l500 lxlO-3 o § § 1030 3xl0·2 CN 〇0 1 1 1 0 0.01 Γ 〇.〇1 ^ ϊι +1 1.00E+07 CS 1 0.06 1 ΐι Sample ID Classification Material Nw/ V Deviation Direction <l-10> - GaN Corresponding offset direction "11-201 Offset angle Θ1 Offset direction <ll-2> - Corresponding offset direction in GaN Π-1001 Offset angle Θ2 Temperature °c HC1 atm NH3 atm Time min Thickness nm Temperature °c HC1 atm NH3 atm time min thickness nm dopant kk 〇〇Μ 绛i off-angle 0a CN Η _ _ _ Off-angle eb Off-plane in-plane distribution Δθα Off-plane in-plane distribution A0b Dislocation density <"w- 1 &lt 2 inch in-plane wavelength distribution σ -32- 131436.doc 200903867 (N 00 Xinbu {k take i〇 inch m 1—^ fNj % sister 1—« Xin H ΛΧ Sample ID Classification—0 铋龙Η33Ί 〇$ 500 I 1x10'" 1 o § i 1030 1 3x10*' I (N 0 0 0 0 〇〇500 1 lxl0'J I »— 1 o § § ,1030 1 3xl0'2 1 CN 0 0 0 r*"H 0 ^r 〇 to CO 500 lxlO-" T-H oss ,1030 1 3x10'" 1 (N 〇〇〇0 〇 \〇(N 500 lxl0_J dss 1030 3x10^ <N 〇〇〇0 〇vri CS 500 1x10^ >> o § § 1030 3xl0·2 〇〇〇0 〇00 1—1 500 1 ΐχίο·3 1 1 —^ oss ! 1030 3xl0-2 (N 〇〇〇0 w- 〇〇500 lxlO-3 oss 1030 3xl0·2 (N 〇100 0 〇500 lxlO'3 oss 1030 3xl0'2 CN 〇0 0 0 'w/ 〇ο 500 lxlO-3 oss 1030 3xl0'2 0 0 0 0 4- r- 〇^ 13⁄4 2 v$ 53⁄4 Deviation angle 1 Deviation direction <ll-2> - Corresponding offset direction in GaN "1-1001 Off-angle Θ2 temperature °c HC1 atm NH3 atm time min thickness nm temperature °c HC1 atm B m ffi z time min thickness nm dopant (t^)^" $ί $£ [ool-l]€w#

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I ^00 [ο''ιι] φ^玑獾qe pyridin βθν pity φε喵砚 wrong hit qev^^Mfly锩痤(Λ)αΟΛν ^ s ^ ^ ^ ^ ^ ^ (H ton N6) 荽¥ 131436 .doc •33· 200903867 In each of the base substrates of samples ID1 to 18, the reference plane orientation [111] is oriented in only one direction with respect to the normal vector of the main surface (<1-10> direction or <11- 2> Direction) Tilt. Therefore, in the formed GaN substrate, the plane orientation [0001] is also substantially inclined with respect to the normal vector of the main surface toward the [11-20] direction or the [1-100] direction. As can be seen from Tables 1 and 2, when the off angle Θ1 or Θ2 of the base substrate is set to −10° or more and 40° or less (that is, the off angle 0a or 0b of the GaN substrate is set to 10° or more and 40°). In the following cases, the value of the blue shift is reduced. [Table 3] Sample ID 19 20 21 22 Classification Example Embodiment Example Example Base substrate material GaAs size (English) 2 Deviation direction <1-10> - Corresponding offset direction in GaN Π 1-201 Off angle Θ1 10 10 10 10 Deviation direction <ll-2>—Corresponding offset direction in GaNΓ1-100] Offset angle Θ2 0.03 0.05 5 10 Growth condition buffer layer temperature °c 500 500 500 500 HC1 atm lxlO'J 1x10' "1x10'" lxl〇·3 NH3 atm 0.1 0.1 0.1 0.1 time min 60 60 60 60 thickness nm 60 60 60 60 from daytime layer temperature °C 1030 1030 1030 1030 HC1 atm 3x10-2 3xl0'2 3xl0_" 3x1 O'" NH3 atm 0.2 0.2 0.2 0.2 time min 100 100 100 100 thickness nm 10 10 10 10 dopant 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) product (GaN crystal) size (English leaf Offset t direction 丨Μ001 Offset angle Θ a 9.80 10.22 10.15 10.10 Off direction "11-201 Offset angle 0b 0.02 0.05 5.01 5.01 Offset in-plane distribution Δθα ±0.7 ±0.6 ±0·6 ±0_6 Off-plane in-plane distribution A0b ±0.9 ±0.5 ±0_5 ±0_5 Dislocation Density 1.00 Ε+07 1.00E+07 1.00Ε+07 1.00Ε+07 Blue shift (Δλ) 8 8 9 9 △Vop(V) 0.005 0.004 0.003 0.003 2 inch in-plane wavelength distribution σ ±2_5 ±2_8 ±3 ±2.9 - 34-131436.doc 200903867 [Table 4] Sample ID 23 24 25 26 Classification Example Embodiment Example Example Base substrate material GaAs size (English pair) 2 Off direction <l-10> - Corresponding offset in GaN Direction [11-201 Offset angle 0.01 0.03 0.05 5 10 Deviation direction <ll-2> - Corresponding offset direction in GaN [1-1001 Offset angle 10 2 10 10 10 10 Growth condition Buffer layer temperature °c 500 500 500 500 HC1 atm 1x10—J lxlO'3 lxlO'J lxlO'J NH3 atm 0.1 0.1 0.1 0.1 time min 60 60 60 60 thickness nm 60 60 60 60 insect day layer temperature °c 1030 1030 1030 1030 HC1 atm 3x10'" 3xl0 '2 3xl0-2 3x10'2 NH3 atm 0.2 0.2 0.2 0.2 time min 100 100 100 100 thickness nm 10 10 10 10 dopant 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) product (GaN crystal) Dimensions (English 0 inch) Deviation direction [1-100] Deviation angle 0.03 0.05 4.99 10.12 Deviation direction [11-20] Deviation angle eb 9.90 10.12 10.12 10.11 Off-plane distribution A0a ±0.6 ±0.6 ±0.6 ±0.7 Off-plane in-plane distribution ±0_5 ±0.5 ±0.5 ±0.9 Dislocation density 1.00E+07 1.00E+07 1.00E+07 1.00Ε+07 Blue shift (Δλ) 8 9 δ 8 △Vop(V) 0.004 0.005 0.006 0.005 2 In-plane wavelength distribution σ ±2.5 ±2·1 ±2.8 ±2.7 Table 3 and Table 4 show the off-angle of the base substrate Θ1 and One of Θ2 is fixed at 10. When the other is set to 0.03° or more and 10° or less (that is, one of the off-angles 0a and 0b of the GaN substrate is fixed to about 10°, and the other is set to 0.02° or 0.03° or more. The measurement result in the case of 10° or less. It can be seen that, compared with the samples of the comparative examples and the reference examples shown in Tables 1 and 2, the samples of the examples shown in Tables 3 and 4 have an off-plane in-plane of the GaN substrate -35-131436.doc 200903867 Distribution A0a And A0b, the amount of increase in the operating voltage (Δνορ), and further the in-plane wavelength distribution (σ) decreases. The reason is not clear, but the reason is also considered to be: When a GaN crystal layer is grown using a base substrate (GaAs substrate) having an off angle in two directions, 'a part of the base substrate is released from the base substrate to the outside. (For example, when a GaAs substrate is used, the phenomenon that As is released from the base substrate) is suppressed, and as a result, strain of the crystal of the formed GaN crystal layer can be suppressed. As a result, the in-plane distribution A0a and Δθϊ of the obtained GaN substrate and the in-plane wavelength distribution (σ) are reduced. [Table 5] Sample 27 28 29 30 Classification Example Example Example Example Base substrate material GaAs size (English leaf) 2 Deviation direction <1-10> - Corresponding offset direction in GaN Γ 11-20] Off angle Θ1 18 18 18 18 Deviation direction <ll-2>-> corresponding offset direction in GaN [1-1001 Offset angle 0.02 0.03 0.05 5 10 Growth condition buffer layer temperature °c 500 500 500 500 HC1 atm lxlO'J lxlO'J lxl 0'" lxlO'J NH3 atm 0.1 0.1 0.1 0.1 time min 60 60 60 60 thickness nm 60 60 60 60 layer temperature °C 1030 1030 1030 1030 HC1 atm 3χ10·ζ 3x10'" 3x1 O'&quot ; 3χ1〇·" NH3 atm 0.2 0.2 0.2 0.2 time min 100 100 100 100 thickness nm 10 10 10 10 dopant 〇 (oxygen) 〇 (oxygen) 〇 氧 oxygen (oxygen) product (GaN crystal) size ( English leaf) Deviation direction Π-1001 Deviation angle 0a 18.15 17.88 18.15 17.88 Deviation direction 丨11-201 Deviation angle eb 0.03 0.05 5.00 9.92 Off-plane in-plane distribution AGa ±0.7 ±0.6 ±0_6 ±0_6 Off-plane in-plane distribution A0b ±0.9 ±0.5 ±0.5 ±0_5 Dislocation density 1.00Ε+07 1.00 E+07 1.00Ε+07 1.00Ε+07 Blue shift (ΔΑ) 6 7 6 6 △Vop(V) 0.002 0.003 0.004 0.004 2 inch in-plane wavelength distribution σ ±2.5 ±2·1 Soil 2.8 ±2.6 -36- 131436.doc 200903867 [Table 6] Sample ID 31 32 33 34 Classification Example Embodiments Example Base substrate material GaAs size (English) 2 Deviation from the square fee j<1-10>--GaN Offset direction 11-201 Offset angle 0.01 0.03 0.05 5 10 Offset direction <ll-2>-> Corresponding offset direction in GaN "1-1001 Offset angle 182 18 18 18 18 Growth condition buffer layer temperature °c 500 500 500 500 HC1 atm lxlO'J lxlO'J 1x10'"lxlO"3 NH3 atm 0.1 0.1 0.1 0.1 time min 60 60 60 60 thickness nm 60 60 60 60 remote solar layer temperature °C 1030 1030 1030 1030 HC1 atm 3x10 ^ 3χ1〇·" 3χ10-2 3x10*" NH3 atm 0.2 0.2 0.2 0.2 time min 100 100 100 100 thickness nm 10 10 10 10 push matter 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) Product (GaN crystal) Dimensions (inch) Deviation direction [1-100] Deviation angle 0.02 0.05 5.01 10.17 Deviation direction [11-2 0] Offset angle eb 18.16 17.88 18.08 18.08 Off-plane in-plane distribution ±0.6 ±0.6 ±0.7 ±0.6 Off-plane in-plane distribution A0b ±0.5 ±0.5 ±0.9 ±0.5 Dislocation density 1.00E+07 1.00Ε+07 1.00Ε+ 07 1.00E+07 Blue shift (Δλ) 6 6 7 7 △Vop(V) 0.005 0.005 0.004 0.004 2 inch in-plane wavelength distribution σ ±2_5 ±2.1 ±2.5 ±2.6 Table 5 and Table 6 show the deviation of the base substrate One of the corners 1 and 2 is fixed at 18. When the other is set to 0.03° or more and 10° or less (that is, one of the off-angles 0a and 0b of the GaN substrate is fixed to about 18°, and the other is set to 0.02° or 0.03° or more. The measurement result in the case of 10° or less. 37-131436.doc 200903867 [Table 7] Sample ID 35 36 37 38 Classification Example Embodiment Example Example Base substrate material GaAs size (English) 2 Deviation direction <11〇> - Corresponding offset in GaN Direction Π1-201 Deviation angle 251 25 25 25 25 Deviation direction <ll-2> - Corresponding offset direction in GaN [1-1001 Deviation angle 0.02 0.03 0.05 5 10 Growth condition buffer layer temperature °c 500 500 500 500 HC1 Atm 1x10'" lxlO'J lxlO'J lxlO'J NH3 atm 0.1 0,1 0.1 0.1 time min 60 60 60 60 thickness nm 60 60 60 60 daily layer temperature °C 1030 1030 1030 1030 HC1 atm 3x10'2 3xl 〇·2 3χ10·2 3xl0_/ NH3 atm 0.2 0.2 0.2 0.2 time min 100 100 100 100 thickness nm 10 10 10 10 dopant 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) product (GaN crystal) Dimensions (English) Deviation direction [1-100] Deviation angle 0a 24.97 24.85 24.88 24.95 Deviation direction [11-20] Deviation angle 0b 0.02 0.05 4.97 9.97 Deviation in-plane distribution ±0·7 ±0.6 ±0.6 ±0.6 Deviation angle In-plane distribution Aeb ±0·9 ±0_5 ±0.5 ±0·5 Dislocation density 1.00 Ε+07 1.00E+07 1.00E+07 1.00E+07 Blue shift (Δλ) 4 4 4 4 AVop(V) 0.003 0.004 0.005 0.005 2 inch in-plane wavelength distribution σ ±2.4 ±2.1 ±2.5 ±2.3 38- 131436.doc 200903867 [Table 8] Sample ID 39 40 41 42 Classification Example Embodiment Example Example Base substrate material GaAs size (English leaf) 2 Deviation direction <11〇> - Corresponding offset direction in GaN [ 11-20] Deviation angle 0.01 0.03 0.05 5 10 Deviation direction <ll-2>—Corresponding offset direction in GaN [1-1001 Deviation angle Θ2 25 25 25 25 into -3⁄4. Conditional buffer layer temperature °c 500 500 500 500 HC1 atm lxlO'J lxlO·3 1x10—3 lxlO'3 NH3 atm 0.1 0.1 0.1 0.1 time min 60 60 60 60 thickness nm 60 60 60 60 daily layer temperature °C 1030 1030 1030 1030 HC1 atm 3xl0'2 3xl0 '2 3x10'" 3x1 O'" NH3 atm 0.2 0.2 0.2 0.2 time min 100 100 100 100 thickness nm 10 10 10 10 dopant 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) product ( GaN crystal) Dimensions (English 0 inch) Deviation direction [1-100] Deviation angle ea 0.02 0.05 4.98 9.98 Deviation direction [11-20] Angle eb 24.87 24.85 24.84 24.81 Off-plane in-plane distribution A0a ±0.7 Soil 0.6 ±0.6 ±0.6 Off-plane in-plane distribution A0b ±0.9 ±0_5 ±0.5 Earth 0.5 Dislocation density 1.00E+07 1.00E+07 1.00E+07 1.00 E+07 Blue shift (Δλ) 5 5 4 4 AVop(V) 0.003 0.002 0.005 0.005 2 inch in-plane wavelength distribution σ ±2.4 ±2.2 ±2.5 ±2_6 Table 7 and Table 8 show the off-angle of the base substrate Θ1 and One of Θ2 is fixed at 25. , set the other to 0.03. Above 10. In the following cases (i.e., one of the off angles Ga and ΘΙ of the GaN substrate) is fixed at about 25°, and the other is set to 0.02. The measurement result when the above 10° or less. -39-131436.doc 200903867 [Table 9] Sample ID 43 44 45 46 Classification Example Embodiment Example Example Base substrate material GaAs size (English time) 2 Deviation direction <1-10> - Corresponding partiality in GaN Shift direction [11-20] Deviation angle 281 28 28 28 28 Deviation direction <ll-2>-> Corresponding offset direction in GaN [1-100] Offset angle 0.02 0.03 0.05 5 10 into 13⁄4 Condition buffer layer temperature . C 500 500 500 500 HC1 atm lxl〇·3 lxlO'3 lxlO'3 lxlO'3 NH3 atm 0.1 0.1 0.1 0.1 time min 60 60 60 60 thickness nm 60 60 60 60 day layer temperature °C 1030 1030 1030 1030 HC1 atm 3x10'2 3xl0'2 3x10'2 3xl0'2 NH3 atm 0.2 0.2 0.2 0.2 time min 100 100 100 100 thickness nm 10 10 10 10 dopant 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) product (GaN crystal) Dimensions (inch) Deviation direction [1-100] Deviation angle Ga 28.12 28.03 28.31 28.16 Deviation direction [11-20] Deviation angle 0b 0.03 0.05 5.02 10.02 Off-plane in-plane distribution A0a ±0_6 ±0.6 ±0.6 ± 0.6 Off-plane in-plane distribution ±0.5 ±0.5 ±0_5 ±0_5 Dislocation density 1.00Ε+07 1.00E+07 1.00E+07 1.00E+07 Blue shift (Δλ) 4 5 4 4 AVop(V) 0.003 0.002 0.001 0.001 2 in-plane in-plane wavelength distribution σ ± 2.6 ± 2.0 ± 2_0 ± 1·9 40-131436.doc 200903867 [Table 〇] Sample ID 47 48 49 50 51 Classification Example Embodiment Example Embodiment Example Base substrate material GaAs Dimensions (English pair) 2 Deviation direction <l-10> - Corresponding offset direction in GaN [11-20] Deviation Θ1 0 0.03 0.05 5 10 Deviation from Fang Luzhong # ]<ll-2>-GaN • Should be offset 1-1001 Offset angle 282 28 28 28 28 28 Growth condition buffer layer temperature °c 500 500 500 500 500 HC1 Atm lxlO'J lxlO'J lxlO'J lxlO'J lxlO'J NH3 atm 0.1 0.1 0.1 0.1 0.1 time min 60 60 60 60 60 thickness nm 60 60 60 60 60 day layer temperature °C 1030 1030 1030 1030 1030 HC1 atm 3x10'2 3x10'2 3x10'2 3xl0'2 3x10'" NH3 atm 0.2 0.2 0.2 0.2 0.2 Time min 100 100 100 100 100 Thickness nm 10 10 10 10 10 Dopant 〇 (oxygen) 〇 (oxygen) 〇 ( Oxygen) Oxide (oxygen) 〇 (oxygen) product (GaN crystal) Dimensions (English) Deviation direction [1-100] Deviation angle 0a 0.01 0.02 0.05 4.99 10.10 Deviation direction [11-20] Deviation angle 0b 28.22 27.80 27.55 28.16 28.04 Off-plane distribution A0a ±0.6 Soil 0.6 ±0.6 ±0.6 ±0·6 Off-plane in-plane distribution A0b ±0.5 ±0.5 ±0.5 ±0_5 ±0.5 Dislocation density 1.00Ε+07 1.00Ε+07 1.00Ε+07 1.00 E+07 1.00E+07 Blue shift (Δλ) 5 4 5 4 4 AVop(V) 0.02 0.003 0.002 0.001 0.001 2 in-plane wavelength distribution σ ±7 ±3 ± 2·8 ± 2.3 ± 2.2 Tables 9 and 10 show that one of the off-angles Θ1 and Θ2 of the base substrate is fixed to 28. , set the other to 0.03. When the above is 10° or less (that is, when one of the off-angles 0a and 0b of the GaN substrate is fixed to about 28°, and the other is set to 0.02° or 0.03 or more and 10° or less) result. -41 - 131436.doc 200903867 [Table 11] Sample ID 52 53 54 55 Classification Example Embodiment Example Example Base substrate material GaAs size (English) 2 Deviation direction <l-10> Shift direction [11-20] Offset angle 401 40 40 40 40 Offset direction <ll-2>^ corresponding offset direction in GaN [1-100] Offset angle 0.02 0.03 0.05 5 10 Conditioned buffer layer temperature °c 500 500 500 500 HC1 atm lxlO'3 lxlO'3 lxl 0'3 lxlO·3 NH3 atm 0.1 0.1 0.1 0.1 time min 60 60 60 60 thickness nm 60 60 60 60 suppressing B layer temperature °C 1030 1030 1030 1030 HC1 atm 3xl 〇·2 3xl〇·2 3xl0'2 3xl0'2 NH3 atm 0.2 0.2 0.2 0.2 time min 100 100 100 100 thickness nm 10 10 10 10 dopant 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) Product (GaN crystal) Dimensions (English leaves) Deviation direction [1-100] Deviation angle 39.81 40.13 39.88 39.88 Deviation direction [11-20] Deviation angle eb 0.03 0.05 5.02 10.02 Off-plane in-plane distribution ΔΘ3 ±0.6 ±0.6 ±0_6 ± 0.6 Off-plane distribution of soil 0.5 soil 0.5 ±0_5 ±0.5 dislocation density 1.00E+07 1.00E+07 1.00E+07 1.00E+07 Blue shift (ΔΑ) 4 4 4 4 △Vop(V) 0.005 0.002 0.005 0.005 2 inch in-plane wavelength distribution σ ±2.6 ±2_9 ±2.0 ±2.1 42- 131436. Doc 200903867 [Table 12] Sample ID 56 57 58 59 Classification Example Embodiment Example Example Base substrate material GaAs size (English) 2 Deviation direction <11〇>^ The corresponding offset direction in GaN Π1-201 Offset angle 0.01 0.03 0.05 5 10 Offset direction <ll-2> - Corresponding offset direction in GaN [1-1001 Offset angle 402 40 40 40 40 Growth condition buffer layer temperature °c 500 500 500 500 HC1 atm lxlO'J lxlO'3 lxlO'J lxlO'3 NH3 atm 0.1 0.1 0.1 0.1 time min 60 60 60 60 thickness nm 60 60 60 60 from daytime temperature °C 1030 1030 1030 1030 HC1 atm 3xl0·2 3χ1〇·" 3xl0· 2 3x10'" NH3 atm 0.2 0.2 0.2 0.2 time min 100 100 100 100 thickness nm 10 10 10 10 dopant 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) product (GaN crystal) size (English)吋) Deviation direction [1-100] Deviation angle 0a 0.02 0.05 4.99 10.01 Deviation direction [11-20] Deviation Angle 0b 39.89 39.86 39,91 39.94 Off-angle in-plane distribution ±0.6 ±0.6 ±0.6 ±0_6 Off-plane in-plane distribution Aeb ±0_5 ±0.5 ±0_5 ±0.5 Dislocation density 1.00E+07 1.00Ε+07 1.00E+07 1.00E+07 Blue shift (ΔΑ) 3 3 4 4 AVop(V) 0.005 0.003 0.005 0.005 2 inch in-plane wavelength distribution σ ±2.7 ±3_0 ±2.0 ±2·1 Table 11 and Table 12 show the deviation of the base substrate One of the corners 1 and 2 is fixed at 40°, and the other is set to be 0.03° or more and 10° or less (that is, one of the off-angles 0a and eb of the GaN substrate is fixed to about 40°, The measurement result when the other is set to 0.02° or 0.03° or more and 10° or less. -43 - 131436.doc 200903867 [Table 13] Sample ID 60 61 62 63 64 65 Classification Example Embodiment Example Comparative Example Comparative Example Base substrate material GaAs size (English 0 inch) 2 Deviation direction <1-1 〇>—Corresponding offset direction in GaN [11-20] Offset angle 261 26 26 40 40 40 45 Offset direction <11-2> - Corresponding offset direction in GaN [1-100] Offset angle Θ2 26 40 26 40 45 40 Growth condition buffer layer temperature °c 500 500 500 500 500 500 HC1 atm 1x10-3 lxlO-3 lxlO'3 lxlO'3 lxlO'3 lxlO'3 NH3 atm 0.1 0.1 0.1 0.1 0.1 0.1 time min 60 60 60 60 60 60 Thickness nm 60 60 60 60 60 60 Daily layer temperature °C 1030 1030 1030 1030 1030 1030 HC1 atm 3x10-2 3xlO·2 3xl0-2 3xl0'2 3xl0.2 3xl〇-2 NH3 atm 0.2 0.2 0.2 0.2 0.2 0.2 Time min 100 100 100 100 100 100 Thickness nm 10 10 10 10 10 10 Dopant 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) 〇 (oxygen) product (GaN crystal ) Dimensions (English) In the deviation direction [1-100] Deviation angle 25.85 26.06 40.08 40.04 Growth polymerization growth polymerization Deviation direction [11-20] Deviation angle eb 25.93 39.78 25.98 40.02 Growth Polymerization Polymerization Deviation in-plane distribution ±0.6 ±0.6 ±0.6 ±0_6 Growth Polymerization Polymerization Deviation Off-plane Distribution A0b ±0.5 Soil 0.5 ±0.5 ±0.5 Growth Polymerization Growth Polymerization Dislocation Density 1.00E+07 1.00E+07 1.00E+07 1.00E+07 Growth Polymerization Growth Polymerization Blue Shift (Δλ) 4 4 3 3 - - AVop(V) 0.003 0.003 0.003 0.003 - - 2 English In-plane wavelength distribution σ ±2.7 ±2.7 +2.5 ±2.7 - - • 44 - 131436.doc 200903867 Table 13 shows 45 above 45°. In the following (specifically, 26, 40, 45.), the deviation angles Θ1 and Θ2 of the base substrate are changed (that is, the deviation angle 0a of the GaN substrate is changed within a range of 26° or more and 45 degrees or less). The case of 0b). As is clear from Table 13, when any one of the off angles Θ1 and Θ2 of the base substrate is set to 40° or more (specifically, 45°), the GaN crystal layer cannot be formed. On the other hand, when the off angles Θ1 and Θ2 of the base substrate are set to 40° or less (that is, when the off angles 0a and 0b of the GaN substrate are set to 40° or less), the GaN substrate is The off-plane in-plane distribution and Δθϊ), the increase in the operating voltage (AVop), and the in-plane wavelength distribution (σ) are smaller than the comparative examples and reference examples shown in Tables 1 and 2. Compared with the samples of the comparative examples or the examples shown in Tables 1 and 2, the samples of the examples shown in Tables 3 to 13 above (specifically, the off-angles 0a and ΘΙ of the GaN substrate) are One is set to 1 0. Above 40°, set the other to 0.〇2. Above 40. In the following sample), the off-plane in-plane distribution Δ0a and ΔΘΙ?, the increase in the operating voltage (Δνορ), and the in-plane wavelength distribution (σ) are reduced. 131436.doc -45- 200903867 [Table 14] Sample ID 66 67 68 69 70 Classification Example Examples Examples Embodiments Base substrate material Sap. Sap. ZnO SiC GaN Dimensions (English) 2 Deviation direction <ll对应>^ corresponding offset direction in GaN [11-20] Offset angle 261 26 40 26 26 26 Offset direction <ll-2> - Corresponding offset direction in GaN [1-1001 Offset angle 26 2 26 40 26 26 26 Conditional buffer layer temperature °c 500 500 500 500 - HC1 atm lxlO'J lxlO·4 lxlO'5 lxlO-6 - NH3 atm 0.1 0.1 0.1 0.1 - time min 60 60 60 60 - thickness nm 60 60 60 60 -曰日层温度°c 1030 1030 1030 1030 1030 HC1 atm 3xl0·2 3x10'" 3xl0-2 3x10'" 3xl0·2 NH3 atm 0.2 0.2 0.2 0.2 0.2 Time min 100 100 100 100 100 Thickness nm 10 10 10 10 10 Doping Si Si Si Si Si product (GaN crystal) Dimensions (inch) Deviation direction [1-100] Offset angle 0a 26.03 39.94 26.05 25.95 26.05 Deviation direction [11-20] Deviation angle eb 25.98 40.02 26.03 25.91 25.88 Deviation In-plane distribution A0a ±0.6 ±0.6 ±0_6 ±0_6 ±0,6 partial Off-plane in-plane distribution A0b ±0_5 ±0.5 ±0_5 Soil 0.5 ±0.5 Dislocation density 1.00E+07 1.00E+07 1.00E+07 1.00E+07 2.00E+06 Blue shift (Δλ) 5 5 5 4 4 △ Vop(V) 0.004 0.005 0.005 0.005 0.003 2 inch in-plane wavelength distribution σ ±2.8 ±2·8 ±2.4 ±2.1 ±2.2 Table 14 shows samples using a substrate made of a material other than GaAS as a base substrate. Film formation conditions and measurement results of GaN. As a result of measurement of the sample IDs 66 to 70, it is understood that the substrate (sapphire substrate, ZnO substrate, SiC substrate, and GaN substrate) other than the GaAs substrate can be used as the base substrate, and the same as when the GaAs substrate is used as the base substrate. The surface orientation [0001] is GaN-46-131436.doc 200903867 plate which is inclined toward two off-angle directions. Further, the obtained GaN substrate and the light-emitting element produced by using the GaN substrate exhibited the same characteristics as the GaN substrate produced by using the ffiGaAs substrate as the base substrate and the light-emitting element produced by using the GaN substrate. Further, a GaN substrate prepared by using a sapphire substrate, a ZnO substrate, a siC substrate, or a GaN substrate having the same off-angle as GaAs, and a light-emitting device manufactured using the GaN substrate, which are not described in the table, are also shown. 1 to Table 13 have the same characteristics. The embodiments and examples disclosed above are to be considered in all respects as illustrative and not restrictive. The scope of the present invention is defined by the scope of the claims, and not the above-described embodiments and examples, and all modifications within the meaning and scope of the claims. [Industrial Applicability] The present invention is advantageously applied to a GaN substrate used for emitting a light-emitting element or the like having a relatively long wavelength (wavelength region of 500 nm or more), and

On the surface of the GaN substrate, an epitaxial layer substrate having an epitaxial layer is formed, and a semiconductor device such as the GaN substrate is further used. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view showing a GaN substrate of the present invention. Fig. 2 is a schematic view for explaining the crystal structure of the GaN substrate shown in Fig. 1. Fig. 3 is a schematic view for explaining the plane orientation and the crystal plane in the crystal structure of the (10) substrate shown in Fig. 2. Fig. 4 is a view for explaining the inclination angle of the GaN substrate of the present invention in the off-angle direction of Fig. 1 Φ > 丄μ 。. 131436.doc -47- 200903867 Fig. 5 is a flow chart for explaining a method of manufacturing the GaN substrate shown in Fig. 1. Fig. 6 is a flow chart for explaining the contents of the preparation steps in the flowchart shown in Fig. 5. Fig. 7 is a plan view schematically showing a mask pattern of a mask layer formed on a main surface of a base substrate. Fig. 8 is a plan view schematically showing a mask pattern of a mask layer formed on a main surface of a base substrate. Fig. 9 is a view showing a film forming apparatus used in the film forming step (S2). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view showing the use of an epitaxial layer substrate of the GaN substrate of the present invention shown in Fig. 1. Fig. 11 is a cross-sectional view showing a light-emitting element using the GaN substrate of the present invention. Fig. 1 is a graph showing the relationship between the current supplied to the light-emitting element and the skin length of the emitted light. [Description of main component symbols] 1 GaN substrate 2 Normal vector 3 GaN crystal layer 5 Base substrate 10 Mask layer 11 Groove opening portion 12 Opening portion 131436.doc -48. 200903867 20 Film forming device 22 Reaction tube 23 Ga carrier 24 pedestal 26 heater 27' 28 pipe 30 light-emitting element 31 n-type AlGaN intermediate layer 32 n-type GaN buffer layer 33 light-emitting layer 34 p-type AlGaN layer 35 p-type GaN contact layer 36 n-electrode 37 ρ electrode 40 worm layer 41 Insect crystal substrate 131436.doc -49-

Claims (1)

200903867 X. Patent application scope: 1. A GaN substrate having a main surface, and a plane orientation [0001] is inclined with respect to two normal off-angle directions with respect to a normal vector of the main surface. 2. The GaN substrate according to claim 1, wherein the two off-angle directions in which the plane orientation [〇〇〇1] is inclined with respect to a normal vector of the main surface are [Bu 100] direction and [11-20] direction. 3. The GaN substrate according to claim 2, wherein an inclination angle of said surface orientation [0001] with respect to a normal to said main surface in said [i-iOO] direction and said [11-20] direction Any of the upper tilt angles is 1〇. Above 40. Hereinafter, the other one is 〇·〇20 or more 40. the following. 4. A substrate with a stupid crystal layer, comprising: the GaN substrate of claim 1, and a crystal growth layer formed on the main surface of the GaN substrate. 5. A semiconductor device using the epitaxial layer substrate as claimed in claim 4. (6) A method of manufacturing a GaN substrate, comprising the steps of: preparing a base substrate in which a reference plane orientation is inclined with respect to a normal vector of the main surface toward two base substrate sides that are different from each other; a GaN crystal layer is grown on the main surface of the base substrate; the base substrate is removed from the GaN crystal layer, thereby obtaining a GaN substrate containing a GaN crystal layer; and the GaN substrate has a main surface with a plane orientation [0001] relative The normal vector of the main surface of the above-mentioned 131436.doc 200903867 is inclined toward two different off-angle directions; the GaN is adjusted by changing the inclination angle of the reference plane orientation in the base substrate side in the oblique direction of the base substrate side. The method of manufacturing the GaN substrate according to claim 6, wherein the base substrate is a GaAs substrate, and the reference plane orientation is [111], wherein the substrate has a tilt angle in the off-angle direction. The two base substrate side tilt directions are <1 _ 1 〇> direction and <丨丨_2> direction, the above two GaN substrates The off-angle direction is the [11-20] direction and the [1-100] direction. The method of manufacturing the GaN substrate according to claim 6, wherein the base substrate is a sapphire substrate, and the reference plane orientation is [0001], the above 2 The inclination direction of the base substrate side is the [11-20] direction and the [1-100] direction, and the two off-angle directions of the GaN substrate are the [1-100] direction and the [11-20] direction. The method of manufacturing a GaN substrate according to Item 6, wherein the base substrate is a ZnO substrate, the reference plane orientation is [0001], and the two base substrate sides are inclined in a [1-1 00] direction and a [11-20] direction. The two off-angle directions of the GaN substrate are the [1-1 〇〇] direction and the direction of the 131436.doc 200903867 [11-20]. The method of manufacturing the GaN substrate according to claim 6, wherein the base substrate In the case of the SiC substrate, the reference plane orientation is [0001], the two base substrate sides are inclined in the [Κι〇〇] direction and the [u_2〇] direction, and the two off-angle directions of the GaN substrate are & (7)... Direction and [11-20] direction. 11 . The method of manufacturing a GaN substrate according to claim 6, wherein The base substrate is a GaN-containing substrate, the reference plane orientation is [0001], the two base substrate side tilt directions are [uoo] direction and [112〇] direction, and the two off-angle directions of the GaN substrate are ^丨(9)] direction and [11 -20] direction. 12. The method of manufacturing a GaN substrate according to claim 6, wherein the step of growing the GaN ruthenium layer further comprises the step of forming a mask layer having a plurality of holes on the main surface of the base substrate. 13. The method of manufacturing a GaN substrate according to claim 6, wherein one of the inclination angles in the oblique direction of the two base substrate sides in the base substrate is ten. Above 40. Hereinafter, the other one is 〇·〇20 or more 40. the following. 131436.doc