JP5042100B2 - Epitaxial growth substrate, method of manufacturing the same, and group III nitride semiconductor device - Google Patents

Description

  The present invention relates to an epitaxial growth substrate for epitaxially growing a semiconductor device structure using a group III nitride material, a method for manufacturing the same, and a group III nitride semiconductor device.

  Group III nitride semiconductors are used as materials for optical and electronic devices such as light emitting diodes, laser diodes, and field effect transistors.

  There are sapphire, Si, GaN, and the like as a base substrate for group III nitride semiconductor growth, but defects occur in the grown crystal due to lattice mismatch with the base substrate. This defect reduces the performance of the fabricated device. In the case of a light emitting diode (LED), the threading dislocation generated at the interface between the base substrate and the group III nitride semiconductor acts as a non-light emitting center in the light emitting layer, thereby reducing the light emitting efficiency of the LED.

In order to reduce the dislocation density in the light emitting layer, formation of a group III nitride semiconductor using an ELO (Epitaxial Lateral Overgrowth) technique has been proposed. For example, in Patent Document 1, epitaxial growth is performed by selective lateral growth so as to fill the concavo-convex structure on a sapphire substrate having a striped concavo-convex structure formed by a reactive ion etching method using chlorine gas on the surface, An Al _x Ga _y In _z N (x + y + z = 1, x> 0, y, z ≧ 0) film having a region with a low dislocation density formed on at least one of the convex and concave portions of the stripe-shaped uneven structure Patent Document 2 describes that the surface of the AlN film is patterned into an uneven shape by forming an AlN film on sapphire and then performing an etching process through a predetermined mask. It is described.
Japanese Patent Laid-Open No. 2001-210598 Japanese Patent Laid-Open No. 2003-2796

Recently, as LEDs have shorter wavelengths and higher outputs, there has been a strong demand for increased luminous efficiency. However, the epitaxial growth substrate having a striped uneven structure described in Patent Document 1 has a tendency that dislocations still propagate above the convex portion although the dislocation density decreases above the concave portion. The group III nitride semiconductor substrate for ELO described in 2 is used to suppress the occurrence of misfit dislocations with the group III nitride layer on the growth substrate (sapphire) having a flat surface. In this configuration, a low-temperature buffer layer (AlN film) having an uneven surface is formed. According to this configuration, although the dislocation density decreases in the region above the concave portion on the surface of the low-temperature buffer layer, the dislocation is still above the convex portion. Tends to propagate. In any case, when the dislocation density of each part of the unevenness is measured by the cross-sectional TEM, the dislocation density over the entire surface of the substrate cannot be sufficiently reduced, and the inventors have carried out using the cross-sectional TEM. As a result of the measurement, the average was about 10 ⁹ / cm ² (see Comparative Examples 1 to 3). As a difference in dislocation density from the patent document, calculation from the number of etch pits by observation with an electron force electron microscope (AFM) in which the dislocation density is measured at a relatively low level can be considered. The described method could not sufficiently increase the light emission efficiency in the light emitting layer over the entire surface of the substrate.

  In addition, in an LED composed of an underlayer manufactured using the methods of Patent Documents 1 and 2, a flat interface of materials having different refractive indexes, that is, an interface between AlN and a semiconductor layer in Patent Document 1, In Document 2, the light extraction efficiency is further reduced due to total reflection of light incident on the interface between the substrate and the group III nitride underlayer (AlN film), and it is difficult to manufacture an LED having high light emission efficiency.

  An object of the present invention is to provide an epitaxial growth substrate capable of producing an LED structure having a low dislocation density in the entire crystal region and a high light emission efficiency in view of such a current situation.

  The inventors of the present invention have studied to develop a substrate for epitaxial growth capable of producing an LED structure having a low dislocation density throughout the crystal and having a high luminous efficiency, and have obtained the following knowledge.

  That is, an underlayer composed of a first group III nitride crystal having a first surface with an uneven shape is formed on a single crystal substrate processed into an uneven shape, and the second group III nitride crystal is formed thereon. In the case of an epitaxial growth substrate in which an intermediate layer is formed, as in Patent Document 1, a base layer having a flat surface is formed on a substrate having an uneven shape, and a semiconductor layer is epitaxially grown on the base layer Or, as in Patent Document 2, a dislocation density is low in the entire crystal region compared to the case where an underlayer having an uneven surface is formed on a flat substrate and a semiconductor layer is epitaxially grown on the underlayer. I found out that

  Note that the underlying layer grown on the single crystal substrate processed into a concavo-convex shape has a tendency to penetrate the dislocation density immediately above the convex portion of the single crystal substrate, but lateral (horizontal) from the convex portion or the side wall portion. Direction) It is thought that the dislocation density decreased in the grown part. Further, although the principle is not clear, some dislocations bend in the lateral direction even immediately above the convex portion, and the dislocation density decreases according to the film thickness.

  In the present invention, the dislocation density immediately above the convex portion of the single crystal substrate can be reduced by forming the irregular shape on the surface of the base layer.

Further, when the refractive indexes of the materials constituting the single crystal substrate, the base layer, and the first base layer are n _1, n ₂ , and n ₃ , respectively, the present inventors have a refractive index of these materials of n If the element is designed to satisfy the relationship ₁ <n ₂ <n ₃ and the light emitting layer is present on the intermediate layer side and light is extracted from the light emitting layer toward the single crystal substrate, the interface should be flat. For example, total reflection occurs at the interface and the light extraction efficiency is small. However, when the interface is uneven and this relationship is established, the effect of improving the light extraction efficiency is remarkably exhibited.

  The threading dislocations that tend to occur above the protrusions constituting the unevenness of the single crystal substrate can be reduced by heat-treating the underlayer at a temperature exceeding the growth temperature. It is presumed that this heat treatment causes dislocation movement and promotes disappearance when the dislocations coalesce. By using the base layer subjected to such heat treatment, as a result, the dislocation density of the film formed above the base layer can be further reduced.

  Further, the dislocation density in the crystal can be further reduced by disposing the uneven shape of the first surface of the underlayer by a half pitch in the lateral direction of the recessed portion with respect to the uneven shape of the main surface of the single crystal substrate. I can expect. Dislocations extending above the convex portions of the single crystal substrate are blocked by the concave portions on the surface of the underlayer, and the flat film formed of crystals that grow laterally from above the convex portions on the first surface of the underlayer has low dislocations throughout the region. Is done.

  Further, the first surface of the underlayer can be formed by superimposing a fine uneven shape in addition to the uneven shape, thereby further reducing the dislocation density over the entire crystal. By forming fine irregularities, dislocations existing at the interface between the fine irregular surface of the underlayer and the intermediate layer formed on the fine irregular surface are laterally grown by the fine irregular surface, and there is no fine irregularities. Compared to the formation, the dislocation density further decreases. In addition, the effect of improving the light extraction efficiency becomes more remarkable.

  And when LED structure was produced using the board | substrate for epitaxial growth (template) of this invention, the emitted light intensity increased compared with the conventional LED. One possible reason is that the internal quantum efficiency is improved by reducing the dislocation density in the light emitting layer. Another reason is considered to be due to an increase in light extraction efficiency of the LED. The light incident at a low angle from the side surface of the uneven surface of the first surface formed in the underlayer is relaxed in the total reflection condition, so that the light emission efficiency is increased, and further, when the fine unevenness is formed, It has been found that the relaxation of the total reflection condition can be further increased and the emission intensity of the LED can be increased, and the present invention has been completed.

That is, the gist of the present invention is as follows.
(1) a single crystal substrate having a concavo-convex main surface, and an underlayer made of a first group III nitride crystal having a concavo-convex first surface formed on the single crystal substrate by epitaxial growth; on the underlayer, formed by epitaxial growth, stripes second at least have the intermediate layer comprising a group III nitride crystal, the unevenness of the single crystal substrate, which is located alternately with the groove bottom and the top surface The groove bottoms of the single crystal substrate have the same width, the top surfaces of the single crystal substrate have the same width, and the unevenness of the foundation layer has a groove bottom and a top surface. The stripe-shaped grooves are alternately arranged, the groove bottoms of the foundation layer have the same width, the top surfaces of the foundation layer have the same width, and the groove bottom of the foundation layer is the single crystal substrate. The top surface of the underlayer is a groove of the single crystal substrate. Epitaxial growth substrate, characterized in that facing the.

(2) When the refractive indexes of the materials constituting the single crystal substrate, the base layer, and the intermediate layer are n _1, n ₂ , and n ₃ , respectively, the refractive indexes of these materials are n ₁ <n ₂ <n _The substrate for epitaxial growth according to the above (1), which satisfies the relationship ₃ above.

(3) The substrate for epitaxial growth according to (1) or (2), wherein the first surface of the base layer is formed by superimposing a fine uneven shape in addition to the uneven shape.

(4) The substrate for epitaxial growth according to (1), (2) or (3), which is obtained by heat-treating the underlayer at a temperature exceeding its growth temperature.

(5) A step of forming a concavo-convex shape on the main surface of the single crystal substrate, and an underlying layer made of the first group III nitride crystal is formed on the single crystal substrate by epitaxial growth, and the first surface, which is the upper surface, is concavo-convex forming such a shape, on the underlying layer by epitaxial growth and the step of forming an intermediate layer made of a second III-nitride crystal at least chromatic, unevenness of the single crystalline substrate, the groove bottom And the top surface of the single crystal substrate have the same width, and the unevenness of the underlayer is the groove bottom. And the bottom surface of the bottom layer has the same width, the top surface of the base layer has the same width, and the bottom surface of the bottom layer has the groove bottom of the single crystal substrate. The top surface of the underlayer Method for manufacturing an epitaxial growth substrate, wherein Rukoto to face the groove bottom of the single crystalline substrate.

(6) A group III nitride semiconductor device using the epitaxial growth substrate according to any one of (1) to (4).

The effects of the present invention are as follows.
In the above configuration (1), it is possible to lower the dislocation density of the epitaxial growth substrate itself in the entire crystal region by forming an uneven shape on the surface of the underlayer (first effect) . The unevenness of the single crystal substrate is a striped groove in which the groove bottom and the top surface are alternately positioned. The groove bottoms of the single crystal substrate have the same width, and the top surfaces of the single crystal substrate are equal to each other. The underlayer has a width, and the unevenness of the underlayer is a striped groove in which the groove bottom and the top surface are alternately arranged. The groove bottom of the underlayer has the same width and the top surface of the underlayer is the same. It has a width, and the bottom of the groove of the underlayer faces the top surface of the single crystal substrate, and the top surface of the underlayer faces the bottom of the groove of the single crystal substrate, so that further reduction of dislocation density in the crystal can be expected. . Dislocations extending above the convex portions of the single crystal substrate are blocked by the concave portions on the surface of the underlayer, and the flat film formed of crystals that grow laterally from above the convex portions on the first surface of the underlayer has low dislocations throughout the region. Because it is done. For this reason, when the light emitting device structure is produced using the epitaxial growth substrate of the present invention, the dislocation density of the epitaxial growth substrate itself is low throughout the crystal, so that the internal quantum efficiency can be improved and the leakage current can be reduced. And the formation of the surface irregularities of the underlayer can realize high light extraction efficiency by relaxing the total reflection condition at the interface (second effect).

  By adopting the configuration (2), the flat portion of the interface can be further reduced, so that both the first and second effects can be further enhanced.

  In addition to the configuration of (1) or (2) above, by adding the configuration of (3) above, the dislocation density in the underlayer can be further reduced, and a semiconductor element structure is formed thereon. The first effect can be further enhanced.

  In addition, although all the above effects are described only when the epitaxial growth substrate of the present invention is applied to a light emitting device, the same effects can be expected when applied to other semiconductor elements. For example, in the case of a light receiving element device, the internal quantum efficiency can be improved and the dark current can be reduced by the first effect. In the case of an electronic device, the mobility can be improved and the leakage current can be improved by the first effect.

Next, an embodiment of a substrate for epitaxial growth according to the present invention will be described below.
FIG. 1 shows a light emitting diode (LED) structure manufactured using a substrate for epitaxial growth according to a reference example of the present invention.

  An epitaxial growth substrate 2 used in the light emitting diode (LED) structure 1 shown in FIG. 1 is composed of at least a single crystal substrate 3, an underlayer 4, and an intermediate layer 5.

  The term “epitaxial growth” as used herein refers to a growth mode in which crystal planes are aligned with each other when a crystal is grown on a substrate or an underlying crystal, and “epitaxial growth substrate” is defined on the substrate 2. This means a base substrate used for epitaxial growth of the device layer 6, but is not limited to a single substrate in a state where the device layer 6 is not formed, but an intermediate generation for continuously forming the device layer It also includes objects (for example, the underlayer 4 and the intermediate layer 5).

  Single crystal substrate 3 has an uneven main surface 3a. The single crystal substrate 3 can be freely selected depending on the semiconductor element to be manufactured, such as sapphire, SiC, AlN, AlGaN, and GaN. In particular, when used for a light-emitting element, a substrate material that does not have absorption due to a band structure or impurities at an emission wavelength is preferable. For example, in an AlGaN-based ultraviolet light-emitting device, a material that does not absorb due to a band structure or impurities in the emission wavelength band is preferable, and sapphire, AlN, or AlGaN is particularly preferable. The concavo-convex shape of the main surface 3a of the single crystal substrate 3 is not particularly limited as long as it is a surface shape in which there is a recess in which dislocations do not easily propagate upward from the main surface 3a. As for the arrangement of the concavo-convex shape, various concavo-convex shapes such as a stripe shape, an island shape, a hole shape, and a zigzag shape are possible, and the entire surface is not necessarily the same shape. Even in the case of an island shape, various shapes such as a circle and a polygon are possible.

  When the uneven shape of the main surface 3a is a stripe shape, the width W1 and the depth d1 of the concave portion (groove) 7 of the main surface 3a are 100 nm to 100 μm and 10 nm or more, respectively, and the width W2 of the convex portion 8 of the main surface 3a. Is set to 100 nm to 100 μm, and the groove pitch W3 is set to 100 nm to 100 μm to reduce the dislocation density above the main surface 3a, particularly above the recesses, and to reduce the total dislocation density at the interface between the substrate 3 and the base layer 4. This is preferable for relaxing the reflection conditions.

The underlayer 4 is formed by epitaxial growth on the single crystal substrate 3 and is made of a first group III nitride crystal having a first surface 4a having an uneven shape.
Examples of the first group III nitride crystal include AlN, GaN, InN, BN, and mixed crystals thereof. Further, Si, Ge, Be, Mg, Zn, As, P may be used as necessary. , B or a transition metal component may be included. However, as with the selection of the material of the substrate 3, it is preferable that the material does not have absorption due to the band structure or impurities at the emission wavelength.

  Here, the width (lateral dimension) W4 of the concave portion 9 of the first surface 4a of the base layer 4 is appropriately selected from the light emission wavelength in the case of a device size and a light emitting element, but is formed by a photolithographic technique. About 100 nm to 100 μm, which is a possible range, is preferable. The upper limit of the depth (longitudinal dimension) d2 of the concave portion 9 of the first surface 4a is not particularly limited, but is preferably 10 nm or more. This is because if the uneven step is too small, the first and second effects described above are not exhibited. The unevenness angle is appropriately selected. In the case where the underlayer 4 is formed of a multilayer structure, the unevenness of the first surface 4a of each layer may be overlapped in a plurality of stages.

  Regarding the arrangement of the uneven shape of the first surface 4a of the underlayer 4, various surface shapes such as a stripe shape, an island shape, a hole shape, and a zigzag shape are possible, and the entire surface is not necessarily the same shape. Even in the case of an island shape, various shapes such as a round shape and a polygonal shape are possible.

  As long as the effect of the present invention can be exhibited between the single crystal substrate 3 and the base layer 4 or in the base layer 4, it is possible to dispose a single layer or a plurality of buffer layers. For example, a low-temperature buffer layer can be formed on the substrate surface, a substrate surface modification treatment such as nitriding, a superlattice layer having a strain buffering effect, a composition gradient, or the like can be performed.

The position of the unevenness of the first surface 4a of the underlayer 4 is not particularly limited in relation to the position of the unevenness of the main surface 3a of the single crystal undersubstrate. For example, the first surface 4a of the underlayer 4 is not limited. irregularities disposed position, shown in Figure 1, and if provided corresponding to the arrangement position of the unevenness of the main surface 3a of the single-crystal substrate 3, as in the present invention shown in FIG. 2, the single-crystal substrate 3 The main surface 3a of the main surface 3a can be shifted by a half pitch with respect to the uneven position.

  Further, the first surface 4a of the underlayer 4 is preferably reduced as much as possible to improve both the first and second effects. For example, the first surface 4a of the underlayer 4 has an uneven shape on the first surface 4a. In addition, it is preferable to superimpose fine uneven shapes as shown in FIG. Here, the “fine concavo-convex shape” means that only the lateral (width direction) period of the concavo-convex structure of the first surface 4a is narrower than the concavo-convex shape of the first surface 4a shown in FIG. There is no restriction in the longitudinal direction (the depth direction of the recess).

The arrangement pitch W5 between the convex portions and the arrangement pitch W6 between the concave portions of the fine uneven shape are both
A range of 100 nm to 100 μm is preferable.

  The intermediate layer 5 is formed by epitaxial growth on the underlayer 4 and is made of a second group III nitride crystal. Examples of the second group III nitride crystal include AlN, GaN, InN, BN, and mixed crystals thereof. Further, if necessary, Si, Ge, Be, Mg, Zn, As, P , B or a transition metal component may be included. This layer may be a layer that functions as a conductive layer.

Further, when the refractive indexes of the materials constituting the single crystal substrate 3, the base layer 4 and the intermediate layer 5 are n _1, n ₂ and n ₃ , the refractive indexes of these materials are n ₁ <n ₂ It is preferable to satisfy the relationship of <n ₃ in order to further improve the light extraction efficiency.

Next, an example of a method for manufacturing an epitaxial growth substrate according to the present invention will be described below.
Figure 4 (a) ~ (f) are all SANYO showing main steps constituting a typical production method of the present invention, FIG. 4 (g) ~ (i) is, as a reference example of the present invention Ru der shows the main steps constituting the process for producing.

  In the method for manufacturing a substrate for epitaxial growth according to the present invention, first, an uneven shape is formed on the main surface 3a of the single crystal substrate 3 as shown in FIG.

  As a manufacturing method of the single crystal substrate 3, for example, by using a normal photolithography technique, patterning is performed according to the target unevenness and etching is performed. As an etching method, dry etching such as RIE, liquid layer etching using a chemical solution, heat treatment, or the like can be used. It is also possible to adopt a method of forming the same material as the material of the single crystal substrate 3 in a convex shape.

  Next, the base layer 4 made of the first group III nitride crystal is formed on the single crystal substrate 3 by epitaxial growth (FIG. 4B).

  Examples of the method for producing the underlayer 4 include various thin film production techniques such as MOCVD, MBE, and sputtering. It is also possible to select the material of the single crystal substrate 3 as appropriate and to produce it by nitriding.

  The underlayer 4 is formed so that the first surface 4a, which is the upper surface thereof, has an uneven shape.

  As a method for producing a concavo-convex shape on the first surface 4a of the underlayer 4, for example, a method of forming by growing while reflecting the concavo-convex shape of the main surface 3a of the single crystal substrate 3 during the thin film production, A method of forming the underlying layer 4 as a thin film by epitaxial growth and then manufacturing it by the same processing as the method of manufacturing the concavo-convex shape of the main surface 3a of the single crystal substrate 3 can be mentioned. It is also possible to fabricate under conditions that promote planarization.

  Further, as another method for producing the uneven shape on the first surface 4a of the underlayer 4, as shown in FIG. 2, the uneven shape of the first surface 4a of the underlayer 4 is changed to the main surface 3a of the single crystal substrate 3. In the case where the concave / convex shape is shifted by a half pitch in the lateral direction of the concave portion 7, first, a mask 11 is formed at a position corresponding to the convex portion 8 of the main surface 3a of the single crystal substrate 3 (see FIG. 4 (c)), and then the first group III nitride crystal is further epitaxially grown between the masks 11 on the first surface 4a of the underlayer 4 (FIG. 4D), and then the mask 11 is removed. As a result (FIG. 4E), an uneven shape can be formed on the first surface 4a of the foundation layer 4, and then the intermediate layer 5 and the device layer 6 are formed (FIG. 4F).

  In the present invention, “the first surface of the concavo-convex shape of the underlayer” means that the convex portion 4c of the underlayer 4 is the base portion 4b of the other underlayer 4 as shown in FIG. In addition to the same group III nitride crystal, a material different from the base portion 4b of the underlayer 4 is disposed on the first surface 4a of the underlayer 4 so that the first surface of the underlayer 4 The case where it becomes an uneven shape is also included.

  Specifically, after forming the base layer 4 on the single crystal substrate 3, the mask 11 is placed at a predetermined position on the first surface 4a of the base layer 4 as shown in FIGS. 4 (g) to 4 (i). After forming, the first surface 4a of the underlayer 4 may be formed into an uneven shape by leaving a mask.

  In addition, an example of a method for forming a fine uneven shape 12 in addition to the uneven shape of the first surface 4a of the base layer 4 is shown in FIGS. 5A to 5D. It can also be obtained by growing a group III nitride crystal at a low temperature at which facets are formed, or by once forming a concavo-convex shape, followed by etching, heat treatment and the like.

  Furthermore, in order to further reduce the dislocation of the first group III nitride as the underlayer 4, after the underlayer 4 is formed, a temperature exceeding the temperature at the time of formation, preferably 1200 to 2000 ° C., more preferably. Is preferably subjected to heat treatment at 1200 to 1800 ° C.

  And a step of forming an intermediate layer made of the second group III nitride crystal on the underlayer 4 by epitaxial growth.

  Next, the intermediate layer 5 made of the second group III nitride crystal is formed on the underlayer by epitaxial growth.

  As a method for producing the group III nitride crystal of the intermediate layer 5, the same method as that for the underlayer 4 can be used. When the uneven shape of the first surface 4 a of the underlayer 4 can be obtained only by the thin film production method. The intermediate layer 5 can also be formed continuously with the base layer 4.

  The above description only shows an example of the embodiment of the present invention, and various modifications can be made within the scope of the claims.

Next, reference examples of the present invention will be described below.
( Reference example 1) Grooved sapphire substrate / AlGaN LED structure on uneven surface underlayer
Reference Example 1 uses a c-plane sapphire substrate 3 as a substrate. Striped grooves (recesses 7) having a width of 2 μm and a depth of 500 nm are formed on the main surface 3a of the substrate 3 by a reactive ion etching method using a fluorine-based gas at an arrangement pitch of 2 μm. Source gas trimethylaluminum (TMA), ammonia (NH _3). An AlN film was grown as the underlayer 4 by MOCVD using hydrogen as a carrier gas. The growth temperature was 1200 ° C. and the growth pressure was 15 torr. The flow rate ratio NH ₃ / TMA was 450. The thickness of the grown AlN film 4 was 1 μm. The underlayer 4 was formed so as to have a concavo-convex first surface 4a reflecting the groove of the substrate. Next, an n-AlGaN layer (thickness: 1 μm, Si doping amount: 5 × 10 ¹⁸ ), an AlGaN multiple quantum well layer (MQW), and p-AlGaN (thickness) are formed on the substrate on which the AlN film 5 is epitaxially grown. AlGaN-based LED structures 6 having 20 nm and Mg doping amount of 5 × 10 ¹⁹ / cm ³ ) were sequentially formed by MOCVD. The refractive index was measured using an ellipsometer, and as a result, sapphire (n = 1.76), AlN (n = 2.15), and AlGaN (n = 2.21) were obtained.

  Thereafter, the obtained substrate was taken out from the MOCVD apparatus, and a p-side electrode made of Ni (lower layer) / Au (upper layer) was formed.

  Etching was performed by reactive ion etching to form an n-side electrode made of Ti (lower layer) / Al (upper layer). Thereafter, annealing was performed at 700 ° C. for 5 minutes. Thereafter, element separation was performed by grinding, polishing, scribing, and braking to obtain a 1 mm square LED chip. A Philip chip having the sapphire substrate side as a light extraction surface was used, and electrical connection was performed using Au bumps.

The dislocation density of the fabricated LED chip was measured by cross-sectional observation using a transmission electron microscope (TEM). As a result, the AlGaN light-emitting layer above the recess formed on the sapphire surface was 1 × 10 ⁸ / cm ² above the protrusion. It was 5 × 10 ⁸ / cm ² . The internal quantum efficiency was measured to investigate the increase in luminous efficiency due to the decrease in dislocation density. A commonly used photoluminescence (PL) method was used as a method for measuring the internal quantum efficiency. In addition, light extraction efficiency was used as an index for evaluating the effect of reducing the total reflectance of light at the interface between different crystals. The light extraction efficiency was obtained by dividing the external quantum efficiency by the internal quantum efficiency. The external quantum efficiency is a value obtained by dividing the input power P1 (W) from the LED light emission output P0 (W) measured by measuring the spectral radiation intensity using an integrating sphere. As a result, the fabricated LED had an internal quantum efficiency of 35% and a light extraction efficiency of 70%.

( Reference example 2) Grooved sapphire substrate / AlGaN LED structure on fine uneven surface underlayer
Reference Example 2, on the first surface 4a of the irregularities of the underlying layer 4 of Reference Example 1, to grow the AlN film at a low temperature (1050 ° C.), except for forming a finer uneven surface 12 reference An LED structure was fabricated in the same manner as in Example 1. The refractive index was measured using an ellipsometer, and as a result, sapphire (n = 1.76), AlN (n = 2.15), and AlGaN (n = 2.21) were obtained. The angle in the normal direction of the fine uneven facets formed by low-temperature growth was 60 °, and the pitch interval was 0.08 μm. The dislocation density of the AlGaN light emitting layer was 5 × 10 ⁷ / cm ² throughout the crystal. The LED structure fabricated using the substrate fabricated in Reference Example 2 had an internal quantum efficiency of 40% and a light extraction efficiency of 75%.

( Reference example 3) AlGaN LED structure with sapphire with groove / irregular surface underlayer heated at high temperature
Reference Example 3 is the same as Reference Example 1 except that an AlN film as the underlayer 4 having the first surface 4a having a concavo-convex shape is subjected to heat treatment at 1650 ° C. for 600 minutes on the grooved sapphire substrate 3. The LED structure was fabricated by the method. The refractive index was measured using an ellipsometer, and as a result, sapphire (n = 1.76), AlN (n = 2.15), and AlGaN (n = 2.21) were obtained. The dislocation density of the AlGaN light emitting layer was 9 × 10 ⁶ / cm ² throughout the crystal. The internal quantum efficiency of the LED structure fabricated using the template fabricated in Comparative Example 3 was 60 [%], and the light extraction efficiency was 70 [%].

(Comparative Example 1) Grooved sapphire substrate / AlGaN LED structure on flat underlayer Comparative Example 1 is the same method as Reference Example 1 except that an AlN film having a flat surface is formed as an underlayer on grooved sapphire. An LED structure was fabricated. The refractive index was measured using an ellipsometer, and as a result, sapphire (n = 1.76), AlN (n = 2.15), and AlGaN (n = 2.21) were obtained. The dislocation density of the AlGaN light emitting layer was 5 × 10 ⁸ / cm ² above the concave portion and 2 × 10 ⁹ / cm ² above the convex portion. In order to compare with the dislocation density in the patent literature, the dislocation density was calculated from the etch pit density obtained by observing the AlGaN surface using an electron force microscope (AFM). As a result, about 1 × 10 ⁶ / cm ² over the entire AlGaN surface. Met. The internal quantum efficiency of the LED structure fabricated using the epitaxial growth substrate fabricated in Comparative Example 1 was 20%, and the light extraction efficiency was 60%.

Comparative Example 2 Flat Surface Sapphire Substrate / Uneven Surface Underlayer AlGaN LED Structure Comparative Example 2 epitaxially grows an underlayer composed of an AlN film having an uneven surface on a flat sapphire substrate without grooves. An LED structure was fabricated using the epitaxial growth substrate thus fabricated. The refractive index was measured using an ellipsometer, and as a result, sapphire (n = 1.76), AlN (n = 2.15), and AlGaN (n = 2.21) were obtained. The unevenness of the AlN film was formed by etching through a mask. The dislocation density of the AlGaN light emitting layer was 5 × 10 ⁸ / cm ² above the concave portion and 2 × 10 ⁹ / cm ² above the convex portion. The LED structure fabricated using the template fabricated in Comparative Example 2 has an internal quantum efficiency of 20% and a light extraction efficiency of 25%.

(Comparative Example 3) Flat Surface Sapphire Substrate / AlGaN LED Structure on Flat Surface Underlayer As shown in FIG. 7, in Comparative Example 3, an underlayer having a flat surface is formed on an AlN film on a flat sapphire substrate without forming grooves. An LED structure was fabricated using an epitaxial growth substrate fabricated by epitaxial growth. The refractive index was measured using an ellipsometer, and as a result, sapphire (n = 1.76), AlN (n = 2.15), and AlGaN (n = 2.21) were obtained. The dislocation density of the AlGaN light emitting layer was 5 × 10 ⁹ / cm ² throughout the crystal. The internal quantum efficiency of the LED structure manufactured using the template manufactured in Comparative Example 3 was 8%, and the light extraction efficiency was 20%.

In the above configuration (1), it is possible to lower the dislocation density of the epitaxial growth substrate itself in the entire crystal region by forming an uneven shape on the surface of the underlayer (first effect) . The unevenness of the single crystal substrate is a striped groove in which the groove bottom and the top surface are alternately positioned. The groove bottoms of the single crystal substrate have the same width, and the top surfaces of the single crystal substrate are equal to each other. The underlayer has a width, and the unevenness of the underlayer is a striped groove in which the groove bottom and the top surface are alternately arranged. The groove bottom of the underlayer has the same width and the top surface of the underlayer is the same. It has a width, and the bottom of the groove of the underlayer faces the top surface of the single crystal substrate, and the top surface of the underlayer faces the bottom of the groove of the single crystal substrate, so that further reduction of dislocation density in the crystal can be expected. . Dislocations extending above the convex portions of the single crystal substrate are blocked by the concave portions on the surface of the underlayer, and the flat film formed of crystals that grow laterally from above the convex portions on the first surface of the underlayer has low dislocations throughout the region. Because it is done. For this reason, when the light emitting device structure is produced using the epitaxial growth substrate of the present invention, the dislocation density of the epitaxial growth substrate itself is low throughout the crystal, so that the internal quantum efficiency can be improved and the leakage current can be reduced. And the formation of the surface irregularities of the underlayer can realize high light extraction efficiency by relaxing the total reflection condition at the interface (second effect).

  By adopting the configuration (2), the flat portion of the interface can be further reduced, so that both the first and second effects can be further enhanced.

  In addition to the configuration of (1) or (2) above, by adding the configuration of (3) above, the dislocation density in the underlayer can be further reduced, and a semiconductor element structure is formed thereon. The first effect can be further enhanced.

  In addition, although all the above effects are described only when the epitaxial growth substrate of the present invention is applied to a light emitting device, the same effects can be expected when applied to other semiconductor elements. For example, in the case of a light receiving element device, the internal quantum efficiency can be improved and the dark current can be reduced by the first effect. In the case of an electronic device, the mobility can be improved and the leakage current can be improved by the first effect.

It is sectional drawing which shows the LED structure produced using the board | substrate for epitaxial growth which is a reference example of this invention. It is sectional drawing which shows another embodiment of the board | substrate for epitaxial growth according to this invention. It is sectional drawing which shows other embodiment of the board | substrate for epitaxial growth which is a reference example of this invention. It is a flowchart which shows embodiment of the manufacturing method of the substrate for epitaxial growth according to this invention, and the manufacturing method of the substrate for epitaxial growth which is a reference example of this invention . It is a flowchart which shows other embodiment of the manufacturing method of the board | substrate for epitaxial growth which is a reference example of this invention. 6 is a cross-sectional view showing an LED structure of Comparative Example 1. FIG. It is sectional drawing which shows the LED structure of the comparative example 2.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Light emitting diode (LED) structure 2 Epitaxial growth substrate 3 Single crystal substrate 4 Underlayer 5 Intermediate layer 6 Device layer 6a n Clad layer 6b Active layer 6c p Clad layer 7 Recess 8 on the main surface of the single crystal substrate Main of the single crystal substrate Surface convex part 9 Concave part 10 on the first surface of the underlayer Protrusion part 11 on the first surface of the base layer Mask 12 Fine irregular surface 13 p electrode 14 n electrode

Claims (6)

A single crystal substrate having an uneven main surface;
An underlayer composed of a first group III nitride crystal having an uneven first surface formed by epitaxial growth on the single crystal substrate;
On the underlayer, formed by epitaxial growth, at least it has the intermediate layer made of a second III-nitride crystal,
The unevenness of the single crystal substrate is a stripe-like groove in which the groove bottom and the top surface are alternately positioned, the groove bottoms of the single crystal substrate have the same width, and the top surfaces of the single crystal substrate are mutually Have equal width,
The unevenness of the underlayer is a striped groove in which groove bottoms and top surfaces are alternately positioned, the groove bottoms of the underlayer have the same width, and the top surfaces of the underlayer have the same width. Have
An epitaxial growth substrate, wherein a groove bottom of the underlayer faces a top surface of the single crystal substrate, and a top surface of the underlayer opposes a groove bottom of the single crystal substrate. When the refractive indexes of the materials constituting the single crystal substrate, the base layer, and the intermediate layer are n ₁ , n ₂ , and n ₃ , respectively, the refractive indexes of these materials have a relationship of n ₁ <n ₂ <n ₃ The substrate for epitaxial growth according to claim 1 , wherein:   3. The epitaxial growth substrate according to claim 1, wherein the first surface of the underlayer is formed by superimposing a fine uneven shape in addition to the uneven shape. 4. The substrate for epitaxial growth according to claim 1, 2 or 3 obtained by heat-treating the underlayer at a temperature exceeding its growth temperature. Forming a concavo-convex shape on the main surface of the single crystal substrate;
On the single crystal substrate by epitaxial growth, an underlying layer made of a first III-nitride crystal, comprising the steps of first surface which is the upper surface is formed so that the uneven shape,
Onto the underlying layer by epitaxial growth, at least organic and forming an intermediate layer made of a second III-nitride crystal,
The unevenness of the single crystal substrate is a striped groove in which the groove bottom and the top surface are alternately positioned, the groove bottom of the single crystal substrate has the same width, and the top surface of the single crystal substrate has the same width. ,
The unevenness of the foundation layer is a striped groove in which groove bottoms and top surfaces are alternately positioned, the groove bottoms of the foundation layer have the same width, and the top surfaces of the foundation layer have the same width,
The groove bottom of the underlayer to face the top surface of the single crystalline substrate, the underlayer top manufacturing method of the epitaxial growth substrate, wherein Rukoto to face the groove bottom of the single crystal substrate.   A group III nitride semiconductor device using the epitaxial growth substrate according to claim 1.

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