The present invention relates to a semiconductor growth substrate, a semiconductor element, a semiconductor light emitting element, and a method for manufacturing the semiconductor element, and more particularly, to a semiconductor growth substrate, a semiconductor element, a semiconductor light emitting element, and a method for manufacturing the semiconductor element for growing an a-plane GaN crystal layer.
In recent years, as an LED that emits a blue light from a purple light used for illumination use, proposed is an LED in which an active layer is formed with a GaN-based material whose main plane is a non-polar or semi-polar plane orientation. In a GaN-based semiconductor layer, an a-plane and an m-plane are a non-polar plane, and an r-plane is a representative example of a semi-polar plane.
Patent Literature JP-A-2008-214132 discloses a technique for growing an a-plane GaN layer on the r-plane of a sapphire substrate by using a metal organic chemical vapor deposition (MOCVD) method. In the GaN-based semiconductor layer using the non-polar plane and the semi-polar plane, a droop characteristic can be improved by reducing the influence of a piezoelectric field in a stacking direction.
In a related art, when a nitride semiconductor layer is grown on a c-plane sapphire substrate, a technique for reducing the defect density of the nitride semiconductor layer is used by forming an uneven structure on a sapphire substrate (PSS: Patterned Sapphire Substrate). In a PSS substrate whose main plane is a c-plane, since the main plane of the growing semiconductor layer is also the c-plane having small in-plane anisotropy, isotropic growth is performed, and a dislocation is bent in the semiconductor layer growing in a lateral direction on the uneven structure, such that the dislocation and defect that continue up to the surface of the semiconductor layer are reduced.
However, in the a-plane GaN layer 2 formed on the r-plane sapphire substrate 1, since a ±c-axis direction and an m-axis direction exist in a growth plane, abnormal growth occurs due to in-plane anisotropy even though the PSS substrate having the r-plane as the main plane is used, such that it is difficult to obtain the high-quality a-plane GaN layer 2 having good crystallinity and excellent surface flatness.
Also in the r-plane sapphire substrate 1, for example, a size of the convex shape 4 is set to a nano size of less than 1 μm, thereby making it possible to suppress the abnormal growth and form the a-plane GaN layer 2 having the excellent surface flatness. However, with respect to a defect growing directly upward from a flat part formed between the convex shapes 4 adjacent to each other, as the convex shape 4 becomes lower, an effect of allowing the defect to be concentrated in the vicinity of the apex is reduced, such that there is also a limit to reducing the density of the defect 3 (defect density).
Therefore, the present invention has been made in consideration of the above-described problems of a related art, and an object thereof is to provide a semiconductor growth substrate, a semiconductor element, a semiconductor light emitting element, and a method for manufacturing the semiconductor element that are capable of growing a high-quality a-plane GaN layer having good crystallinity and excellent surface flatness.
In order to solve the above-described problems, a semiconductor growth substrate of the present invention includes: an r-plane of a sapphire as a main plane; and a plurality of convex shapes formed on the main plane, in which the convex shape has a length of 2000 nm or less in a predetermined first direction among in-plane directions of the main plane, and heights of the convex shapes adjacent to each other are different.
In the above-described semiconductor growth substrate of the present invention, by allowing the convex shapes of the size having different heights to be adjacent to each other, defects concentrated at an apex of a small convex shape grow again in a lateral direction and are concentrated again at an apex of a large convex shape. Accordingly, defect density is further reduced, thereby making it possible to grow a high-quality a-plane GaN layer having good crystallinity and excellent surface flatness.
In one aspect of the present invention, a maximum dimension of the convex shape in the in-plane direction of the main plane is less than 1 μm.
In one aspect of the present invention, at least three or more types of heights of the convex shape exist in the main plane.
In one aspect of the present invention, the convex shapes having the same height are formed along a c-axis direction of the sapphire.
In one aspect of the present invention, the convex shapes adjacent to each other and having different heights are integrated.
In order to solve the above-described problems, a semiconductor growth substrate of the present invention includes: an r-plane of a sapphire as a main plane; and a plurality of convex shapes formed on the main plane, in which the convex shape is formed along a c-axis direction of the sapphire, the convex shape has a width D of 1200 nm or less, which is a length in a direction orthogonal to the c-axis in a plane of the main plane, and an aspect ratio of H to D, which is a ratio of a height H of the convex shape to the width D thereof, is in a range of 1 or more and 4 or less.
In one aspect of the present invention, a space S between the convex shapes is in a range of 200 nm or more and 500 nm or less.
In one aspect of the present invention, the convex shape includes:
a side wall surface part formed by rising from the main plane; and
a curved surface part formed at an upper portion of the side wall surface part.
In one aspect of the present invention, the curved surface part is formed with a curvature different from that of a circle having the width D of the convex shape as a diameter, and a ridge part where the two curved surface parts intersect is formed on a top part of the convex shape.
In order to solve the above-described problems, a semiconductor element of the present invention uses the semiconductor growth substrate according to any one of the above descriptions, and includes a functional layer on the semiconductor growth substrate.
In order to solve the above-described problems, a semiconductor light emitting element of the present invention uses the semiconductor growth substrate according to any one of the above descriptions, and includes an active layer on the semiconductor growth substrate.
In order to solve the above-described problems, a method for manufacturing a semiconductor element according to the present invention, includes: a step of forming a plurality of convex shapes having a length of 2000 nm or less in a predetermined first direction among in-plane directions of a main plane on a sapphire having an r-plane as the main plane so that heights of the convex shapes adjacent to each other are different; and a step of growing a nitride semiconductor layer on the main plane.
In the above-described method for manufacturing the semiconductor element according to the present invention, by allowing the nano-sized convex shapes having different heights to be adjacent to each other, defects concentrated at an apex of a small convex shape grow again in a lateral direction and are concentrated again at an apex of a large convex shape. Accordingly, defect density is further reduced, thereby making it possible to grow a high-quality a-plane GaN layer having good crystallinity and excellent surface flatness.
The present invention can provide a semiconductor growth substrate, a semiconductor element, a semiconductor light emitting element, and a method for manufacturing the semiconductor element that are capable of growing a high-quality a-plane GaN layer having good crystallinity and excellent surface flatness.
Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. The same or similar components, members, and processing illustrated in each drawing shall be denoted by the same reference signs, and redundant description will be appropriately omitted.
As illustrated in
The a-plane GaN layer 12 is a base layer grown so that the main plane becomes the a-plane, and is a layer for epitaxially growing a nitride semiconductor layer thereon. As a method for forming the a-plane GaN layer 12, a well-known method such as a MOCVD method and an HVPE method (Hydride Vapor Phase Epitaxy) can be used, and it is desirable to use the MOCVD method. A film thickness of the a-plane GaN layer 12 is not particularly limited, and is desirably formed to be equal to or greater than 1 μm.
An AlN buffer layer for alleviating lattice mismatching may be formed between the r-plane sapphire substrate 11 and the a-plane GaN layer 12. A thickness of the AlN buffer layer is desirably in a range of 5 to 300 nm, more desirably in a range of 5 to 90 nm, and even more desirably in a range of 5 to 30 nm because crystal quality of the a-plane GaN layer 12 deteriorates when the thickness thereof is too thick.
The convex shapes 14a and 14b are protrusions formed by processing the main plane of the r-plane sapphire substrate 11, and an example thereof includes the one in which a plurality of conical protrusions are regularly arranged is described. The convex shapes 14a and 14b have a length of 2000 nm or less in a predetermined first direction (for example, an m-axis direction) among in-plane directions of the main plane. The convex shapes 14a and 14b are desirably nano-sized. Here, a fact that the convex shapes 14a and 14b are nano-sized indicates that a maximum dimension in the in-plane direction of a convex part forming the convex shapes 14a and 14b is less than 1 μm. Here, while a conical shape is described as an example of a shape of the convex shapes 14a and 14b, a quadrangular pyramid and a triangular pyramid may be used.
As a size of the convex shapes 14a and 14b, a bottom plane is desirably in a range of 300 nm or more and 2000 nm or less in diameter and in a range of 350 nm or more and 2000 nm or less in height, and more desirably in a range of 300 nm or more and less than 1000 nm in diameter and in a range of 400 nm or more and less than 1000 nm in height. A height difference between the convex shapes 14a and 14b is desirably in a range of 100 to 1000 nm, and a space between the convex shapes 14a and 14b adjacent to each other is desirably 30 to 400 nm. As a specific size of the convex shapes 14a and 14b, for example, the convex shape 14a has a diameter of 900 nm and a height of 800 nm, and the convex shape 14b has a diameter of 900 nm and a height of 400 nm. The space between the convex shape 14a and the convex shape 14b is set to 100 nm.
As illustrated in
As a method for forming the convex shapes 14a and 14b on the surface of the r-plane sapphire substrate 11, well-known nanoimprint and patterning can be used. As an example, a resist film is applied on the r-plane sapphire substrate 11, a mold on which a pattern corresponding to the convex shapes 14a and 14b is formed is used, and the pattern is transferred to the resist film by using the nanoimprint technology. Next, the resist film to which the pattern is transferred and the r-plane sapphire substrate 11 are subjected to anisotropic etching by using a chlorine-based gas, such that the convex shapes 14a and 14b are formed on the r-plane sapphire substrate 11.
Next, for example, the AlN buffer layer having a film thickness of about 30 nm is formed on the r-plane sapphire substrate 11 (NPSS) on which the plurality of convex shapes 14a and 14b are formed with a sputtering method. As the sputtering method for forming the AlN buffer layer, it is more desirable to use Ar gas with AlN as a target material. The AlN serving as the target material may be a single crystal substrate or a powder-sintered body, and the state and form thereof are not limited.
Next, after cleaning the surface of the AlN buffer layer, the a-plane GaN layer 12 is grown with the MOCVD method by using hydrogen and nitrogen as a carrier gas, ammonia (NH3) as a group V raw material, and trimethylgallium (TMG) as a group III raw material. As an example of growth conditions, a two-stage growth sequence is used in which a growth temperature is kept constant after a temperature is raised up to 1010° C., and a reactor pressure, a ratio of V to III, and a growth time are changed. For example, first, the ratio of V to III is maintained at about 4000 to 5000 and the pressure is maintained at 900 to 1000 hPa for about 10 to 20 minutes, after which the ratio of V to III is maintained at about 100 to 200 and the pressure is maintained at 100 to 150 hPa for 90 to 120 minutes. The plurality of the convex shapes 14a and 14b are formed on the main plane of the r-plane sapphire substrate 11 by cooling the a-plane GaN layer 12 up to a room temperature after growing the a-plane GaN layer 12 and by taking out the cooled a-plane GaN layer 12, thereby making it possible to obtain the semiconductor growth substrate of the embodiment in which the AlN buffer layer and the a-plane GaN layer 12 are formed.
As illustrated in
By allowing the heights of the convex shapes 14a and 14b formed on the r-plane sapphire substrate 11 to be different in this manner, the defect 13a existing in the a-plane GaN layer 12 finally becomes the defect 13b concentrated in the vicinity of the apex of the large convex shape 14a. Therefore, density of the defect 13b continuing up to an outermost surface of the a-plane GaN layer 12 becomes smaller than density of the whole convex shapes 14a and 14b. Accordingly, the semiconductor growth substrate of the embodiment can grow a high-quality a-plane GaN layer having good crystallinity and excellent surface flatness.
In the arrangement of the square lattice shape illustrated in
In the arrangement of the triangular lattice shape illustrated in
While
As described above, in the semiconductor growth substrate according to the embodiment, since the plurality of convex shapes 14a and 14b having the above-described size are formed on the main plane of the r-plane sapphire substrate 11, and the heights of the convex shapes 14a and 14b adjacent to each other are different, the defects 13b can be concentrated in the large convex shape 14a, thereby making it possible to reduce the defect density. The crystallinity of the a-plane GaN layer 12 growing thereon is excellent, and abnormal growth is suppressed, thereby forming the high quality a-plane GaN layer 12 having excellent surface flatness.
Next, a second embodiment of the present invention will be described with reference to
In the same manner as that of the first embodiment, the r-plane sapphire substrate 11 is prepared, the convex shapes 14a and 14b having the above-described size are formed thereon, and the a-plane GaN layer 12 is epitaxially grown with the MOCVD method. Continuously, the active layer 15 and the p-type semiconductor layer 16 are sequentially grown with the MOCVD method, thereby obtaining a semiconductor substrate.
Next, a part of the p-type semiconductor layer 16 and the active layer 15 is removed by photolithography and etching, such that a part of the a-plane GaN layer 12 is exposed. Next, an electrode material is formed on an exposed plane of the a-plane GaN layer 12 and the p-type semiconductor layer 16 by vapor deposition, and the LED 10 is obtained by performing dicing and individual chip formation.
The active layer 15 is a semiconductor layer epitaxially grown on the a-plane GaN layer 12 and having the a-plane as the main plane. The LED 10 emits light when an electron and a positive hole emit light and are recombined in the layer of the active layer 15. The active layer 15 is formed of a material having a bandgap smaller than that of the a-plane GaN layer 12 and the p-type semiconductor layer 16, and includes, for example, InGaN and AlInGaN. The active layer 15 may be a non-doped layer intentionally not containing an impurity, or may be an n-type containing an n-type impurity and a p-type containing a p-type impurity. Since the active layer 15 is the semiconductor layer having the a-plane as the main plane, spatial separation of the electron and the positive hole caused by a piezoelectric field is hard to occur even though the film is thickened, and the electron and the positive hole can efficiently emit light and be recombined even though current density is increased.
The p-type semiconductor layer 16 is a semiconductor layer epitaxially grown on the active layer 15 and having the a-plane as the main plane. The p-type semiconductor layer 16 is a layer in which a positive hole is injected from the p-side electrode 18, and the positive hole is supplied to the active layer 15.
Here, while the a-plane GaN layer 12 and the p-type semiconductor layer 16 are respectively described as a single layer, each of the a-plane GaN layer 12 and the p-type semiconductor layer 16 may include a plurality of layers having different materials and compositions. For example, the a-plane GaN layer 12 and the p-type semiconductor layer 16 may include a clad layer, a contact layer, a current diffusion layer, an electron block layer, and a waveguide layer. While the active layer 15 is also described as a single layer, the active layer 15 may be formed of a plurality of layers such as a multi quantum well (MQW) structure.
Also in the embodiment, the a-plane GaN layer 12, the active layer 15, and the p-type semiconductor layer 16 are epitaxially grown on the r-plane sapphire substrate 11 (NPSS) on which the convex shapes 14a and 14b having different heights are formed to be adjacent to each other. Therefore, as described in the first embodiment, the a-plane GaN layer 12 also has good crystallinity and surface flatness, and defect density is also reduced. Therefore, the active layer 15 and the p-type semiconductor layer 16 grown on the a-plane GaN layer 12 whose defect density is reduced also have the good crystallinity and surface flatness. Accordingly, characteristics of the active layer 15 and the p-type semiconductor layer 16 are also improved, such that external quantum efficiency of the LED is expected to be improved.
As described above, the LED, which is the semiconductor device of the present embodiment, has the small droop caused by the piezoelectric field, has the small anisotropy in the a-plane, and has the good crystal quality, thereby making it possible to realize high luminance. As a result, the semiconductor device according to the present embodiment is used for lighting equipment such as vehicle lighting equipment, thereby making it possible to reduce the number of chips and increase output. The semiconductor device is not limited to the LED, may be a semiconductor laser, and may be used for another application such as a high electron mobility transistor (HEMT) including a functional layer for generating a two-dimensional electron gas.
Next, a third embodiment of the present invention will be described with reference to
Also in the embodiment, when the a-plane GaN layer 12 grows, the defects 13a generated on a flat plane between the convex shapes 14a to 14c are concentrated at an apex of the smallest convex shape 14c by growth in a lateral direction. Next, after the a-plane GaN layer 12 grows enough to bury the convex shape 14c, the growth in the lateral direction is directed toward the medium-sized convex shape 14b. Accordingly, the defects 13a existing around a periphery of the apex of the convex shape 14c are further bent in a direction of an apex of the convex shape 14b and concentrated. After the a-plane GaN layer 12 grows enough to bury the convex shape 14b, the growth in the direction is directed toward the largest convex shape 14a, and the defects 13a existing around a periphery of the apex of the convex shape 14b are further bent in a direction of an apex of the convex shape 14a and concentrated in the defect 13b.
In the embodiment, the defects 13a can be concentrated in the defect 13b in the vicinity of the apex of the highest convex shape 14a by three or more types of convex shapes 14a to 14c having different heights. Therefore, the a-plane GaN layer 12 further reduces defect density to improve crystallinity, and abnormal growth is suppressed, thereby forming the high quality a-plane GaN layer 12 having excellent surface flatness.
Next, a fourth embodiment of the present invention will be described with reference to
In the example illustrated in
In the example illustrated in
Here, while
Next, a fifth embodiment of the present invention will be described with reference to
As a specific size of the convex shapes 14a and 14b, for example, the convex shape 14a has a diameter of 700 nm and a height of 800 nm, and the convex shape 14b has a diameter of 400 nm and a height of 400 nm. A space between apexes of the convex shapes 14a and 14b is set to 100 nm, such that the apex of the convex shape 14b is within a range of the convex shape 14a, and the two convex shapes 14a and 14b are integrated while being adjacent to each other.
Also in the semiconductor growth substrate of the embodiment, since a plurality of nano-sized convex shapes 14a and 14b are formed on the main plane of the r-plane sapphire substrate 11, and the heights of the convex shapes 14a and 14b adjacent to each other are different, the defects 13b can be concentrated in the large convex shape 14a, thereby making it possible to reduce the defect density. The crystallinity of the a-plane GaN layer 12 growing thereon is excellent, and abnormal growth is suppressed, thereby forming the high quality a-plane GaN layer 12 having excellent surface flatness.
Next, a sixth embodiment of the present invention will be described with reference to
Also in the example illustrated in
Since the side wall surface part 33 is approximately perpendicular to the main plane of the r-plane sapphire substrate 31, the crystal growth is not performed from the surface of the side wall surface part 33 when the crystal growth of the a-plane GaN layer 12 is performed. Since the curved surface part 34 is formed at the upper portion of the side wall surface part 33 and the curved surface part 34 is formed with a predetermined curvature, a specific crystal plane orientation in the sapphire is not exposed. Accordingly, the crystal growth of the a-plane GaN layer 12 is hard to be performed even from the surface of the curved surface part 34. Therefore, the crystal growth of the a-plane GaN layer 12 is performed from the main plane exposed between the convex shapes 32. Particularly, in the example illustrated in
When the space S between the convex shapes 32 is too narrow, the supply of a raw material is inhibited during the crystal growth of the a-plane GaN layer 12 such that it becomes difficult to desirably perform the crystal growth, whereas when the space S therebetween is too wide, an area of the main plane where the crystal growth starts becomes large such that a region where a penetrating dislocation and a defect occur becomes large. Therefore, the space S is desirably in a range of 200 nm or more and 500 nm or less, and more desirably in a range of 300 nm or more and 400 nm or less.
When the height H of the convex shape 32 is too low, as illustrated in
When the width D of the convex shape 32 is too large, it is not desirable because it is required to have a thickness which is thick enough for the a-plane GaN layer 12 to grow and bury the whole convex shapes 32 with the growth in the lateral direction, whereas when the width D thereof is too small, it is not desirable because the growth in the lateral direction of the a-plane GaN layer 12 above the convex shape 32 is not continued such that the defect is not sufficiently reduced. Therefore, the width D is desirably in a range of 300 nm or more and 1200 nm or less, and more desirably in a range of 500 nm or more and less than 1000 nm.
The aspect ratio of H to D is required to be 1 or more so that the growth in the lateral direction of the a-plane GaN layer 12 allows the penetrating dislocation and the defect to reach the side wall surface part 33, whereas when the aspect ratio thereof is too large, the supply of the raw material is inhibited during the crystal growth of the a-plane GaN layer 12 such that it becomes difficult to perform the desirable crystal growth. Therefore, the aspect ratio of H to D is desirably in a range of 1 or more and 4 or less, and more desirably in a range of 1 or more and 2 or less.
As described above, in the semiconductor growth substrate according to the embodiment, the plurality of convex shapes 32 having the above-described size are formed on the main plane of the r-plane sapphire substrate 31, the convex shape 32 is formed along the c-axis direction of the sapphire, and the aspect ratio of H to D, which is the ratio of the height H to the width D, is in the range of 1 or more and 4 or less, thereby making it possible to reduce the defect density by allowing the defect to reach the side wall surface part of the convex shape 32 with the growth in the lateral direction. The crystallinity of the a-plane GaN layer 12 growing thereon is excellent, the abnormal growth is suppressed, thereby forming the high quality a-plane GaN layer 12 having the excellent surface flatness.
The present invention is not limited to the above-described respective embodiments, various modifications can be made within the scope of the claims, and an embodiment obtained by appropriately combining technical methods respectively disclosed in the different embodiments is also included in the technical scope of the present invention.
This application is based upon Japanese Patent Application No. 2018-107594, filed on Jun. 5, 2018, and Japanese Patent Application No. 2019-95079, filed on May 21, 2019, the entire contents of which are incorporated herein by reference.
Number | Date | Country | Kind |
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2018-107594 | Jun 2018 | JP | national |
2019-095079 | May 2019 | JP | national |
Filing Document | Filing Date | Country | Kind |
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PCT/JP2019/022117 | 6/4/2019 | WO | 00 |