JP5838943B2 - Method for producing group III nitride semiconductor - Google Patents

Description

  The present invention relates to a Group III nitride semiconductor manufacturing method in which a buffer layer made of AlN is formed by sputtering on a sapphire substrate that has been subjected to uneven processing, and then a Group III nitride semiconductor is formed by MOCVD.

  When a group III nitride semiconductor is formed on a sapphire substrate by MOCVD, the lattice constants of sapphire and group III nitride semiconductor are greatly different. Therefore, a buffer layer is formed between the sapphire substrate and group III nitride semiconductor. This relaxes the lattice mismatch and enhances the crystallinity of the group III nitride semiconductor. In general, AlN or GaN grown by MOCVD at a low temperature is used for the buffer layer, but a technique of forming by sputtering is also known.

  Further, in the method of manufacturing a group III nitride semiconductor light emitting device, the light extraction efficiency is increased by forming a group III nitride semiconductor layer through a buffer layer on a sapphire substrate that has been subjected to uneven processing. ing.

  In Patent Document 1, an a-plane sapphire substrate that has been subjected to uneven processing by dry etching is used, and after heat treatment at 1000 to 1500 ° C. in a hydrogen atmosphere, a buffer layer made of AlN is sputtered on the a-plane sapphire substrate. It is described that a group III nitride semiconductor is formed and grown on the buffer layer by MOCVD. It is described that by performing heat treatment under such conditions, a group III nitride semiconductor with good crystallinity can be obtained even when an a-plane sapphire substrate damaged by dry etching is used.

JP 2010-10363

  However, the method of Patent Document 1 requires a heat treatment step at a high temperature, and has a problem in terms of manufacturing cost. Further, since the atomic arrangement of the surface is different between the a-plane and the c-plane of sapphire, the heat treatment conditions for obtaining a group III nitride semiconductor with good flatness and crystallinity should be different. Only the case where a sapphire substrate is used is described, and the case where a c-plane sapphire substrate is used is not described.

  Therefore, the present invention improves the flatness and crystallinity of a group III nitride semiconductor when a buffer layer made of AlN is formed by sputtering on a c-plane sapphire substrate and a group III nitride semiconductor is formed on the buffer layer. The purpose is to let you.

  One aspect of the present invention is a method of manufacturing a group III nitride semiconductor in which a buffer layer made of AlN is formed on a sapphire substrate by sputtering and then a group III nitride semiconductor is grown by MOCVD. A III-nitride semiconductor, comprising: a c-plane sapphire substrate that has been processed by etching, and heat-treating the sapphire substrate at less than 700 ° C. in a nitrogen or hydrogen atmosphere, and then forming a buffer layer. It is a manufacturing method.

  A more desirable heat treatment temperature in the heat treatment before forming the buffer layer is 500 ° C. or higher and lower than 700 ° C. The surface flatness and crystallinity of the group III nitride semiconductor can be further improved. More desirably, the temperature is 500 ° C. or higher and 600 ° C. or lower.

  Further, it is more desirable to perform the heat treatment before forming the buffer layer in a nitrogen atmosphere. This is because the surface flatness of the group III nitride semiconductor becomes better than that in a hydrogen atmosphere.

  In the present invention, the buffer layer is preferably formed by sputtering with a sapphire substrate heated to 200 ° C. or higher and 700 or lower.

In another method described in the specification, a buffer layer made of AlN is formed on a sapphire substrate by sputtering, and then a group III nitride semiconductor is grown by MOCVD. A c-plane sapphire substrate whose surface is roughened by dry etching is used, and the buffer layer is formed by sputtering by heating the sapphire substrate to 200 ° C. or higher and lower than 700 ° C. After forming the buffer layer, a group III nitride is formed. This is a method for producing a group III nitride semiconductor, characterized in that the temperature of the sapphire substrate is set to room temperature until the semiconductor is formed.

  In the above, normal temperature is normal temperature which is not heated or cooled, for example, is 0-40 degreeC.

  In the present invention, the sputtering method for forming the buffer layer may be a method such as magnetron sputtering.

  The present invention is particularly effective when the area etched by dry etching is larger than the area not etched (area protected by the mask).

  According to the present invention, a group III nitride semiconductor having good surface flatness and crystallinity is formed on a c-plane sapphire substrate subjected to uneven processing through a buffer layer made of AlN formed by sputtering. Can do. In addition, since the manufacturing method of the present invention does not require high-temperature heat treatment, the manufacturing cost can be reduced.

The figure shown about the manufacturing process of the group III nitride semiconductor of Example 1. FIG. The graph which showed the relationship between heat processing temperature and crystallinity. The graph which showed the relationship between heat processing temperature and crystallinity. A photograph of the surface of GaN. Photograph of RHEED pattern of sapphire substrate.

  Hereinafter, specific examples of the present invention will be described with reference to the drawings. However, the present invention is not limited to the examples.

  First, a sapphire substrate 10 having a c-plane as a main surface was prepared, and one surface was subjected to uneven processing by ICP dry etching (FIG. 1A). The uneven pattern is, for example, a pattern in which dot-like concave portions or convex portions are periodically arranged, or a stripe-like pattern. In the case of a dot shape, it is a flat pattern such as a hexagon, a quadrangle, a triangle, a circle, etc., and the three-dimensional shape is a pyramid, cone, prism, cylinder, pyramid, frustum, etc. with the plane pattern as the top surface .

  The depth of the unevenness processing (the height of the dot-like convex part, the depth of the dot-like concave part, or the depth of the stripe groove) is preferably 0.1 to 10 μm. When the thickness is less than 0.1 μm, the light extraction efficiency is not sufficiently improved due to the uneven shape when a light emitting device is produced using the present invention. On the other hand, if the thickness exceeds 10 μm, the group III nitride semiconductor formed on the sapphire substrate 10 cannot be embedded in the recesses and projections, and a flat group III nitride semiconductor cannot be obtained.

  Next, the sapphire substrate 10 subjected to the uneven processing was heat-treated at less than 700 ° C. in a hydrogen or nitrogen atmosphere. The pressure was normal pressure. In this heat treatment, immediately after heating to a predetermined temperature, heating was stopped and the temperature was lowered to room temperature. This heat treatment may be performed using a magnetron sputtering apparatus used in the next step, or another apparatus may be used. Moreover, the minimum of heat processing temperature is normal temperature.

  Next, the sapphire substrate 10 subjected to the uneven processing was set in a magnetron sputtering apparatus. Then, with the sapphire substrate 10 heated to 200 ° C. or higher and lower than 700 ° C., a buffer layer 20 made of AlN was formed by magnetron sputtering on the surface of the sapphire substrate 10 on which the concavo-convex processing was performed (FIG. 1 ( b)). In magnetron sputtering, high-purity metallic aluminum was used as a target, and AlN was deposited by introducing nitrogen gas.

  As a sputtering method for forming the buffer layer 20, sputtering methods such as DC sputtering, RF sputtering, ion beam sputtering, and ECR sputtering can be used in addition to magnetron sputtering.

Next, the sapphire substrate 10 was taken out of the sputtering apparatus and set in the MOCVD apparatus, and a group III nitride semiconductor layer 30 having a c-plane as a main surface was grown on the buffer layer 20 by MOCVD (FIG. 1). (C)). Raw material gas used in the MOCVD method, as the nitrogen source, ammonia (NH _3), as a Ga source, trimethyl gallium _{(Ga (CH 3) 3)} , as an In source, trimethylindium _{(In (CH 3) 3)} , Al source As trimethylaluminum (Al (CH ₃ ) ₃ ), Si dopant gas as silane (SiH ₄ ), Mg dopant gas as biscyclopentadienylmagnesium (Mg (C ₅ H ₅ ) ₂ ), and carrier gas as H ₂ , N ₂ . The group III nitride semiconductor layer 30 is a layer in which an n-type layer, a light-emitting layer, and a p-type layer are stacked in this order when the present invention is applied to a method for manufacturing a light-emitting element.

  The above is the method for producing a group III nitride semiconductor of Example 1. In this manufacturing method, after the sapphire substrate 10 is processed to be uneven and before the buffer layer 20 is formed, heat treatment is performed under the above temperature conditions. Therefore, even when the c-plane sapphire substrate 10 subjected to the uneven processing is used, the group III nitride semiconductor layer 30 having excellent surface flatness and crystallinity via the buffer layer 20 on the sapphire substrate 10. Can be formed. Moreover, in the manufacturing method of the group III nitride semiconductor of Example 1, the heat treatment is performed at a relatively low temperature of less than 700 ° C., and the high-temperature heat treatment is not required, so that the manufacturing cost can be reduced.

  In the manufacturing method of the group III nitride semiconductor of Example 1, the unevenness pattern of the sapphire substrate 10 is such that the surface area of the sapphire substrate 10 etched by dry etching is larger than the area protected by the mask and not etched. This is particularly effective when In such a concavo-convex pattern, the proportion of the group III nitride semiconductor growing on the roughened region by dry etching is large, and the conventional group III nitride semiconductor layer 30 having good crystallinity could not be obtained. By using the present invention, it is possible to obtain a group III nitride semiconductor layer 30 having good crystallinity even in the case of such an uneven pattern.

In the heat treatment before the formation of the buffer layer 20, the heat treatment temperature is more preferably 500 ° C. or higher and lower than 700 ° C. This is because the surface flatness and crystallinity of the group III nitride semiconductor layer 30 can be further improved. More desirably, the temperature is 500 ° C. or higher and 600 ° C. or lower. Further, it is desirable to perform heat treatment in a nitrogen atmosphere rather than a hydrogen atmosphere. This is because the surface flatness of the group III nitride semiconductor layer 30 becomes better .

[Comparative example]
The manufacturing method of the Group III nitride semiconductor of the comparative example is the same except that the heat treatment before forming the buffer layer 20 in Example 1 is not performed. In other words, after the sapphire substrate 10 is processed to be uneven, the buffer layer 20 made of AlN is formed by magnetron sputtering while keeping the room temperature without performing heat treatment.

The Group III nitride semiconductor manufacturing method of this comparative example also forms the Group III nitride semiconductor layer 30 with good surface flatness and crystallinity, similar to the method of manufacturing the Group III nitride semiconductor of Example 1. be able to. Further, since heat treatment is not performed, the manufacturing process can be simplified and the manufacturing cost can be reduced. This is presumably because the heating of the sapphire substrate 10 in the magnetron sputtering method replaces the heat treatment before the buffer layer 20 is formed. Therefore, the temperature of the sapphire substrate 10 when the buffer layer 20 is formed by magnetron sputtering is more preferably 500 ° C. or higher and lower than 700 ° C., and further preferably 500 ° C. or higher and 600 ° C. or lower.

In Example 1 and the comparative example , the process of removing the charge of the buffer layer 20 (the process of making the buffer layer 20 electrically neutral) is performed before the sapphire substrate 10 is taken out from the sputtering apparatus and set in the MOCVD apparatus. It is desirable to do. The buffer layer 20 formed by sputtering is charged and exposed to the atmosphere when the sapphire substrate 10 is transferred from the sputtering apparatus to the MOCVD apparatus. Therefore, fine dust is adsorbed on the buffer layer 20 and the group III nitride semiconductor layer is exposed. 30 crystallinity etc. will be affected. Therefore, if the buffer layer 20 is subjected to charge removal, adsorption of fine dust can be prevented, and the crystallinity of the group III nitride semiconductor layer 30 can be improved. The neutralization process is performed, for example, by supplying air ionized by an ionizer to the surface of the buffer layer 20.

[Experimental example]
Hereinafter, various experimental examples supporting Example 1 and Comparative Examples will be described.

  2 and 3 are graphs showing the relationship between the temperature of the heat treatment performed before the formation of the buffer layer 20 and the crystallinity of the group III nitride semiconductor layer 30. FIG. Crystallinity was evaluated by X-ray rocking curve (XRC) measurement. 2 shows the XRC half width of the (10-10) plane (the (100) plane for the three indices), and FIG. 3 shows the XRC half width of the (0002) plane (the (002) plane for the three indices). Yes. The XRC half-value width is measured for each of the case where the heat treatment is performed in a hydrogen atmosphere and the case where the heat treatment is performed in a nitrogen atmosphere. The group III nitride semiconductor layer 30 was a 3 μm non-doped GaN layer. The sapphire substrate 10 used was an ICP dry-etched whole surface. The heating temperature of the sapphire substrate 10 during the formation of the buffer layer 20 was 450 ° C. For comparison, the XRC half-value width is also obtained when the heat treatment is not performed before the buffer layer 20 is formed (corresponding to Example 2) and when the surface of the sapphire substrate 10 is not subjected to dry etching and heat treatment is not performed. It was measured. The crystallinity in the case where neither dry etching nor heat treatment is performed is a target, and it can be evaluated that the closer to this, the better the crystallinity.

  As shown in FIG. 2, the crystallinity of the (10-10) plane of GaN is good crystallinity with a narrow XRC half-value width in both a hydrogen atmosphere and a nitrogen atmosphere in the heat treatment temperature range of 500 ° C. to 1100 ° C. It was. This is approximately the same degree of crystallinity as when sapphire substrate 10 is not heat-treated, and slightly worse than when neither dry etching nor heat treatment is performed. However, at temperatures between 700 ° C. and 800 ° C., pits were generated in GaN. It was also found that at temperatures higher than 1100 ° C., the XRC half-width increased in a nitrogen atmosphere and the crystallinity deteriorated. Further, in the hydrogen atmosphere, the XRC half-width was slightly increased at a temperature higher than 1100 ° C.

  Further, as shown in FIG. 3, the XRC half-value width of the (0002) plane of GaN when heat treatment is performed in a hydrogen atmosphere is gradually increased in the range of 500 to 700 ° C., and is 800 ° C. or more. Thus, the XRC half-value width was reduced. At temperatures of 700 ° C. or higher and 800 ° C. or lower, the XRC half width is wide, and the crystallinity of the (0002) plane of GaN is poor. On the other hand, when the heat treatment was performed in a nitrogen atmosphere, the XRC half-value width was almost constant up to 700 ° C., and the XRC half-value width was increased above 700 ° C., and the XRC half-value width was decreased above 800 ° C. As in the case of the hydrogen atmosphere, at temperatures higher than 700 ° C. and lower than 800 ° C., the XRC half-value width was wide and the crystallinity was poor. In the range of 500 to 900 ° C., the XRC half-width was narrower in the nitrogen atmosphere than in the hydrogen atmosphere, and the XRC half-width was narrower in the hydrogen atmosphere above 900 ° C. Moreover, when not heat-processing, it was a XRC half value width comparable as the case where it heat-processed at 500-700 degreeC by nitrogen atmosphere. Further, when neither dry etching nor heat treatment of the sapphire substrate 10 was performed, the XRC half-value width was 200 arcsec lower than when heat treatment was performed at 500 to 700 ° C. in a nitrogen atmosphere.

  FIG. 4 is a photograph of the surface of GaN formed in the experiments of FIGS. FIG. 4A shows a case where heat treatment is not performed, and FIGS. 4B to 4E show cases where heat treatment temperatures of 800 ° C., 700 ° C., 600 ° C., and 500 ° C. are set in a hydrogen atmosphere, respectively. FIGS. 4F to 4I show cases where the heat treatment temperatures are 800 ° C., 700 ° C., 600 ° C., and 500 ° C., respectively, in a nitrogen atmosphere. As shown in FIG. 4, in a hydrogen atmosphere or a nitrogen atmosphere, when the heat treatment temperature is set to 500 ° C. and 600 ° C., the surface of the GaN surface is more than when the heat treatment temperature is set to 700 ° C. and 800 ° C. It can be seen that the flatness is high. Further, it was confirmed that pits were generated when the heat treatment temperature was 700 ° C. and 800 ° C. Even when the heat treatment was not performed, the GaN surface was flat as in the case where the heat treatment was performed at 500 ° C. and 600 ° C.

  2 to 4, it was found that GaN having good surface flatness and crystallinity can be obtained by performing heat treatment at a temperature below 700 ° C. in a hydrogen atmosphere or a nitrogen atmosphere. It was also found that GaN having good surface flatness and crystallinity can be obtained even when heat treatment is not performed.

  FIG. 5 is a photograph of the RHEED (reflection high energy electron diffraction) pattern of the sapphire substrate 10 after the heat treatment. The sapphire substrate 10 has a c-plane as a main surface, and is subjected to ICP dry etching on the entire surface as in the case of FIGS. For comparison, the RHEED pattern was photographed in the case where neither dry etching nor heat treatment was performed and in the case where heat treatment was performed only with dry etching. The heat treatment was performed in a hydrogen atmosphere, and the heat treatment temperatures were 500 ° C., 700 ° C., 800 ° C., and 1160 ° C. In addition, the incident direction of the electron beam was set to two types, [11-20] direction and [10-10] direction of the c-plane sapphire substrate 10.

  As shown in FIG. 5A, when neither dry etching nor heat treatment is performed, the surface of the sapphire substrate 10 is not roughened by dry etching, and thus a clear pattern is obtained. On the other hand, as shown in FIG. 5B, it can be seen that when the heat treatment is not performed after the dry etching, the pattern is blurred and the surface is roughened. Further, as shown in FIGS. 5C to 5F, it can be seen that the pattern becomes clearer as the heat treatment temperature is higher, and the surface roughness gradually recovers.

  The reason why the surface flatness and crystallinity of GaN are not good by heat treatment at 700 ° C. to 800 ° C. can be inferred from the experimental results of FIGS. When the heat treatment temperature is less than 700 ° C., the roughness of the surface of the sapphire substrate 10 becomes approximately uniform, and GaN grows uniformly from the rough surface of the sapphire substrate 10. As a result, the surface flatness and crystallinity of GaN are good. Further, when the heat treatment temperature is higher than 800 ° C., the surface roughness of the sapphire substrate 10 is sufficiently recovered and GaN grows uniformly on the recovered surface, so that the surface flatness and crystallinity are good. However, when the heat treatment temperature is 700 to 800 ° C., the roughness of the surface of the sapphire substrate 10 recovers to some extent, but it does not recover uniformly, and the area where the roughness is recovered and the rough area are mixed. For this reason, GaN grows on the roughened region and the roughened region and becomes a mixed crystal, which is thought to deteriorate the surface flatness and crystallinity of GaN.

  The method for producing a group III nitride semiconductor of the present invention can be used for a method for producing a light-emitting element made of a group III nitride semiconductor.

10: Sapphire substrate 20: Buffer layer 30: Group III nitride semiconductor layer

Claims (4)

In a method of manufacturing a group III nitride semiconductor, a buffer layer made of AlN is formed on a sapphire substrate by sputtering, and then a group III nitride semiconductor is grown by MOCVD.
As the sapphire substrate, a c-plane sapphire substrate whose surface has been processed by dry etching is used.
Forming the buffer layer after heat-treating the sapphire substrate at less than 700 ° C. in a nitrogen or hydrogen atmosphere;
A method for producing a group III nitride semiconductor.   The method for producing a group III nitride semiconductor according to claim 1, wherein the heat treatment is performed at a temperature of 500 ° C or higher and lower than 700 ° C.   The method of manufacturing a group III nitride semiconductor according to claim 1 or 2, wherein the heat treatment is performed in a nitrogen atmosphere.   4. The group III nitride semiconductor according to claim 1, wherein the buffer layer is formed by sputtering the sapphire substrate by heating to 200 ° C. or more and less than 700 ° C. 5. Production method.