JP2015199663A - Method for manufacturing nitride semiconductor epitaxial substrate and method for manufacturing nitride semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nitride semiconductor epitaxial substrate and nitride semiconductor device, including a group III nitride semiconductor layer low in dislocation and capable of suppressing crack generation.SOLUTION: A method for manufacturing a nitride semiconductor epitaxial substrate 1 comprises the steps of growing a buffer layer 3 on a substrate and growing a group III nitride semiconductor layer 4 on the buffer layer 3. In the step of growing the buffer layer 3, a layer consisting of a group III nitride semiconductor including Al and having an inversion domain 5 on the surface is formed by a vapor phase growth method. In the step of growing the III nitride semiconductor layer 4, a layer grown on the inversion domain 5 is buried by a layer grown on a region except the inversion domain 5, and a surface having a C-plane is formed by a vapor phase growth method.

Description

  The present invention relates to a nitride semiconductor epitaxial substrate having a buffer layer of a group III nitride semiconductor containing Al and a nitride semiconductor device using the same.

  When producing a nitride semiconductor epitaxial substrate in which a group III nitride semiconductor layer such as GaN is grown on a heterogeneous substrate such as a sapphire substrate or SiC substrate, between the heterogeneous substrate and the group III nitride semiconductor layer, A technique is known in which a low temperature buffer layer of AlN or GaN or a high temperature buffer layer of AlN or AlGaN is provided to reduce the dislocation of the group III nitride semiconductor layer.

  As a proposal for a high-temperature buffer layer, Patent Document 1 discloses that dislocations in the group III nitride film formed on the AlN buffer layer are reduced by forming an uneven shape on the surface of the AlN buffer layer (underlying film). It is stated that you can.

JP 2002-222771 A

  However, the conventional method of providing a low-temperature buffer layer such as AlN or a high-temperature buffer layer cannot sufficiently reduce dislocations in the group III nitride semiconductor layer, and cracks occur in the group III nitride semiconductor layer. It was often. In particular, when the thickness of a group III nitride semiconductor layer such as a GaN layer is 5 μm or more, the number of epitaxial substrates on which cracks are generated increases rapidly, and the yield significantly decreases.

  An object of the present invention is to provide a nitride semiconductor epitaxial substrate and a nitride semiconductor device having a group III nitride semiconductor layer that has low dislocations and can suppress generation of cracks.

  A first aspect of the present invention is a nitride semiconductor epitaxial substrate having a group III nitride semiconductor layer having a C-plane as a surface, which is grown on a substrate through a group III nitride semiconductor buffer layer containing Al. The buffer layer is a nitride semiconductor epitaxial substrate having an inversion domain on its surface.

According to a second aspect of the present invention, in the nitride semiconductor epitaxial substrate according to the first aspect, the surface density of the inversion domain on the surface of the buffer layer is 1 × 10 ⁴ cm ⁻² or more and 1 × 10 ¹¹ cm ^−2. It is a nitride semiconductor epitaxial substrate in the following range.

  A third aspect of the present invention is the nitride semiconductor epitaxial substrate according to the first or second aspect, wherein no inversion domain is present on the surface of the group III nitride semiconductor layer.

According to a fourth aspect of the present invention, in the nitride semiconductor epitaxial substrate according to any one of the first to third aspects, the buffer layer is one or more of Cl, S, and B. It is a nitride semiconductor epitaxial substrate added at a concentration of 1 × 10 ¹⁵ cm ⁻³ or more.

According to a fifth aspect of the present invention, in the nitride semiconductor epitaxial substrate according to any one of the first to fourth aspects, a dislocation density on the surface of the group III nitride semiconductor layer is 5 × 10 ⁸ cm ⁻² or less. This is a nitride semiconductor epitaxial substrate.

  According to a sixth aspect of the present invention, in the nitride semiconductor epitaxial substrate according to any one of the first to fifth aspects, (0002) plane diffraction in an X-ray rocking curve measurement of the group III nitride semiconductor layer, (0004) The full width at half maximum of surface diffraction and (10-12) surface diffraction is a nitride semiconductor epitaxial substrate that is 300 seconds or shorter, 300 seconds or shorter, and 500 seconds or shorter, respectively.

  According to a seventh aspect of the present invention, in the nitride semiconductor epitaxial substrate according to any one of the first to sixth aspects, the group III nitride semiconductor layer has a thickness of 5 μm or more and has no cracks on the surface. It is a nitride semiconductor epitaxial substrate.

An eighth aspect of the present invention is a nitride semiconductor device in which a device structure is formed on the nitride semiconductor epitaxial substrate of any of the first to seventh aspects.
Another aspect of the present invention is a method for manufacturing a nitride semiconductor epitaxial substrate, comprising: growing a buffer layer on a substrate; and growing a group III nitride semiconductor layer on the buffer layer, In the step of growing the buffer layer, a step of growing the group III nitride semiconductor layer by forming a layer made of a group III nitride semiconductor containing Al and having an inversion domain on the surface thereof by vapor deposition. Then, a nitride semiconductor epitaxial layer in which a layer grown on the inversion domain is buried by a layer grown on a region other than the inversion domain, and a layer whose surface is a C plane is formed by a vapor phase growth method. A method for manufacturing a substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the nitride semiconductor epitaxial substrate and nitride semiconductor device which have a group III nitride semiconductor layer which is a low dislocation and can suppress generation | occurrence | production of a crack are obtained.

It is sectional drawing which shows the manufacturing process which manufactures the nitride semiconductor epitaxial substrate which concerns on one Embodiment of this invention. It is sectional drawing which shows the nitride semiconductor device which concerns on one Embodiment of this invention. It is a graph which shows the relationship between the ID surface density of an AlN buffer layer, and the half value width of the rocking curve of the X-ray diffraction of a GaN layer in the nitride semiconductor epitaxial substrate of the Example and comparative example of this invention. It is a graph which shows the relationship between the ID surface density of an AlN buffer layer, and the dislocation density of the surface of a GaN layer in the nitride semiconductor epitaxial substrate of the Example of this invention, and a comparative example. It is a graph which shows the relationship between the thickness of a GaN layer, and the crack yield in the nitride semiconductor epitaxial substrate of the Example and comparative example of this invention.

  Embodiments of a nitride semiconductor epitaxial substrate and a nitride semiconductor device according to the present invention will be described below.

(Nitride semiconductor epitaxial substrate)
FIG. 1 is a cross-sectional view showing a manufacturing process for manufacturing a nitride semiconductor epitaxial substrate according to an embodiment of the present invention. The nitride semiconductor epitaxial substrate of this embodiment will be described with reference to FIG. 1 showing this manufacturing process.

  FIG. 1C shows a nitride semiconductor epitaxial substrate 1 to be manufactured. A nitride semiconductor epitaxial substrate 1 is a group III nitride semiconductor such as GaN (gallium nitride) on a substrate 2 for growing a nitride semiconductor via a buffer layer 3 of a group III nitride semiconductor containing Al (aluminum). The layer 4 is epitaxially grown, and the buffer layer 3 has an inversion domain (ID) 5 on its surface. Here, the inversion domain (ID) is a region in which the polarity is inverted from the surrounding crystal, and the polarity is in the group III nitride semiconductor crystal (in group III polarity such as Ga polarity and Al polarity). A region having an inverted N polarity or a region where an N polarity plane is generated.

First, as shown in FIG. 1A, a substrate 2 to be a substrate for growing a group III nitride semiconductor is prepared. As the substrate 2, for example, various substrates suitable for the epitaxial growth of a group III nitride semiconductor such as a sapphire substrate, a ZnO substrate, a SiC substrate, a Si substrate, a GaAs substrate, a GaN substrate, an AlN substrate, and an AlGaN substrate can be used. .
Further, as the surfaces of these substrates, the surfaces of various substrates suitable for growth with the group III surface of the group C nitride semiconductor as the surface may be used. For example, in a non-polar sapphire substrate, a C-plane or a surface inclined by 0 to 2 ° from the C-plane toward the A-axis, M-axis, or the middle thereof may be used. In addition, the ZnO substrate has a C-plane Zn plane, the SiC substrate has a C-plane Si plane, a GaN substrate, an AlN substrate, and an AlGaN substrate has a C-plane group III plane, and from these C planes to the A-axis, M-axis, or intermediate A surface inclined by 0 to 2 ° in the direction may be used. In the case of a Si substrate, a (111) plane, in the case of a GaAs substrate, a (111) A plane or a (111) B plane, and a surface inclined by 0 to 2 ° in any direction from these planes may be used.

  Next, as shown in FIG. 1B, a buffer layer 3 of a group III nitride semiconductor (AlN, AlGaN, etc.) containing Al is formed on the substrate 2 by vapor phase growth. As the vapor phase growth method, HVPE method (hydride vapor phase growth method), MOVPE method (metal organic vapor phase growth method), or the like is used.

  When the buffer layer 3 containing a large amount of Al is grown on the substrate 2 at a high temperature of 900 ° C. or higher, the Al surface of the AlN crystal is much more stable than the N surface. The group N polar region (ID) is not generated on the surface of the buffer layer 3.

In the present embodiment, by adding impurities into the buffer layer 3 such as AlN, ID is generated and introduced into the buffer layer 3 such as AlN, and this grows and continues without being embedded in the group III polar layer. There is an ID that reaches the surface of the layer 3. When the impurity concentration added to the buffer layer 3 such as AlN is increased, the stress in the buffer layer 3 is increased, and ID is introduced in order to relieve the stress. It is thought that it will survive without disappearing.
As impurities in the buffer layer 3, any one or more of Cl (chlorine), S (sulfur), and B (boron) is 1 × 10 ¹⁵ cm ⁻³ or more and 1 × 10 ¹⁹ cm ⁻³ or less. In the concentration of. Thereby, although it depends on the type of impurities to be added, the surface density (number density) of IDs on the surface of the buffer layer 3 is in the range of approximately 1 × 10 ⁴ cm ^{−2 to} 1 × 10 ¹¹ cm ^−2. Can be adjusted.
As shown in FIG. 1B, ID5 is present on the surface of the buffer layer 3, and the surface of the buffer layer 3 is a predetermined surface in a group III polar surface (Al polar surface in the case of an AlN buffer layer) 3a. An N-polar surface 3b of ID5 appears by density.

In the vapor phase growth of the buffer layer 3, in the case of the HVPE method, as an example, the pressure is 500 Torr (about 66661 Pa) to 760 Torr (about 101325 Pa, normal pressure), the V / III ratio is 10 or less, and the growth temperature is 900 ° C. to 1200 ° C. And In the case of the MOVPE method, for example, the pressure is 500 Torr or less, the V / III ratio is 10 or less, and the growth temperature is 900 ° C. to 1200 ° C. As the source gas, in the HVPE method, for example, NH ₃ is used as the N source, AlCl ₃ is used as the Al source, GaCl is used as the Ga source, InCl is used as the In source, and Cl, S, and B impurity gases are used. Use HCl, H ₂ S, and BCl ₃ , respectively. In the case of the MOVPE method, for example, the source gas is NH ₃ for the N source, TMA (trimethylaluminum) for the Al source, TMG (trimethylgallium) for the Ga source, and TMI (trimethylindium) for the In source. HCl, H ₂ S, and B ₂ H ₆ are used as impurity gases for Cl, S, and B, respectively. In addition, H ₂ or N ₂ is used as the carrier gas in both cases of the HVPE method and the MOVPE method.
The growth rate is 5 to 100 nm / min in the case of HVPE, and 1 to 30 nm / min in the case of MOVPE.

The group III nitride semiconductor containing Al in the buffer layer 3 is Al _x Ga _1-x N (0.5 ≦ x ≦ 1), more preferably Al _x Ga _1-x N (0.9 ≦ x ≦ 1). ) Is good. That is, the buffer layer 3 is preferably an AlN layer or an AlGaN layer having a high Al composition.

  The surface density (number density) of IDs on the surface of the buffer layer 3 and the group III nitride semiconductor layer 4 is measured by, for example, convergent electron diffraction using a transmission electron microscope (TEM). This can be done by determining the polarity using the difference (CBED) method.

  Subsequently, as shown in FIG. 1C, a group III nitride semiconductor layer 4 such as GaN is epitaxially grown on the buffer layer 3 having ID5 on the surface. When crystal growth is performed on the buffer layer 3 having ID5 on the surface, even if the surface of the buffer layer 3 is flat, at the initial stage of crystal growth, as shown in FIG. Pits (dents) are generated on the crystal growth surface f1 of the group III nitride semiconductor layer 4. This is because the growth rate of the N polarity (ID5) of the group III nitride semiconductor layer 4 grown on the N polarity surface 3b (ID5) on the surface of the buffer layer 3 is higher than the growth rate of the group III polarity (Ga polarity, etc.). Because it is slow.

In the growth of a group III nitride semiconductor layer such as GaN having a C-plane ((0001) plane) as a surface, dislocations usually propagate in the C-axis direction perpendicular to the surface, so that dislocations associate and disappear. There is no threading dislocation. However, when ID5 is provided on the surface of the buffer layer 3 as in the present embodiment, pits are generated on the crystal growth surface. Therefore, when dislocations in the crystal meet the slopes of the pits, the propagation direction of the dislocations changes ( The probability of dislocations meeting increases and the dislocations decrease. For this reason, when the group III nitride semiconductor layer 4 such as GaN is grown on the buffer layer 3 such as AlN containing ID, the surface of the group III nitride semiconductor layer 4 is larger than the case of the buffer layer not including ID on the surface. Thus, the dislocation density is reduced, and the group III nitride semiconductor layer 4 having good crystallinity with a small half-value width of the rocking curve of X-ray diffraction can be obtained.
Specifically, the dislocation density of the surface of the group III nitride semiconductor layer 4 is 5 × 10 ⁸ cm ⁻² or less, and the (0002) plane in the X-ray diffraction rocking curve measurement of the group III nitride semiconductor layer 4 , (0004) plane, and (10-12) plane have a half width of 300 seconds or less, 300 seconds or less, and 500 seconds or less, respectively. The X-ray diffraction half-width measurement conditions were as follows. Using CuKα1 as the X-ray source, X-rays were generated at 40 kV and 45 mA, the X-ray beam was made parallel by the four-crystal method, and the irradiation area of the X-ray beam was The beam was narrowed to 30 μm square with a slit and measured.

  Pits are formed on the crystal growth surface f1 in the initial stage of crystal growth of the group III nitride semiconductor layer 4, but the growth rate of the group III polarity (Ga polarity in the GaN layer) is faster than the N polarity. The N-polar layer (ID5) is embedded by the III-polar layer, and as shown in FIG. Does not appear.

The group III nitride semiconductor layer 4 of the present embodiment is a group III nitride semiconductor layer having a group C polarity (Ga polarity, etc.) C surface used for a device as a surface, and the surface of the group III nitride semiconductor layer 4 Does not have ID5. The group III nitride semiconductor layer 4 is made of Al _x Ga _y In _z N (x + y + z = 1) such as GaN, AlN, InN, AlGaN, InGaN. These group III nitride semiconductor layers 4 may be any of an undoped layer, an n-type layer, and a p-type layer, or may be a laminate thereof.

  Even if the surface of the buffer layer is uneven, when there is no ID on the surface of the buffer layer, the crystal growth surface of the group III nitride semiconductor layer grown on the buffer layer immediately becomes flat, as described above. As a result of the formation of pits, dislocations do not associate or disappear, and the surface dislocation of the group III nitride semiconductor layer 4 cannot be lowered, and the half width of the rocking curve cannot be reduced.

In the crystal growth of the group III nitride semiconductor layer 4, the density at which pits are generated on the crystal growth surface is considered to correspond to the surface density of ID5 on the surface of the buffer layer 3. That is, in the group III nitride semiconductor layer 4 on the buffer layer 3 having ID5, a number of pits (valleys) corresponding to the number of ID5 are generated, and between ID5 and ID5 adjacent to each other, the ID5 It is thought that the number of island-like crystals (grown from one or a plurality of growth nuclei) corresponding to the number is generated.
As described above, the dislocation is reduced by the existence of the slope of the island (pit). For this reason, when the pit density (that is, ID density) is extremely low (for example, less than 1 × 10 ⁴ cm ⁻² ), the surface of the group III nitride semiconductor layer 4 during the growth is almost flat. Since the pit sparsely exists on the C-plane, the ratio of the slope on the surface is low, and the dislocation reduction effect of the present invention cannot be obtained. In addition, when the pit density is extremely high (for example, larger than 1 × 10 ¹¹ cm ⁻² ), since the pits to be formed are small, the surface is formed when the growth thickness of the group III nitride semiconductor layer 4 is small. It will be flattened. Also in this case, since the duration of the pit is short, the effect of reducing dislocations according to the present invention cannot be obtained.
When the pit density is appropriate (for example, 1 × 10 ⁴ cm ⁻² or more and 1 × 10 ¹¹ cm ⁻² or less), a slope is formed at a sufficient ratio on the surface of the group III nitride semiconductor layer 4 during the growth. Since it exists and lasts for a relatively long period of the growth process, the dislocation density can be reduced as compared with the conventional case. In particular, the pit density (ID density) is preferably 1 × 10 ⁵ cm ^{−2 to} 1 × 10 ¹⁰ cm ^−2, more preferably 1 × 10 ⁶ cm ^{−2 to} 1 × 10 ⁹ cm ^−2. It is preferable to reduce the dislocation.

Further, in the nitride semiconductor epitaxial substrate 1 of the present embodiment, since ID5 exists in the group III nitride semiconductor layer 4 on the buffer layer 3 and substrate 2 side, the stress of the group III nitride semiconductor layer 4 is relieved.
Since there is a large difference in thermal expansion coefficient between the substrate 2 made of sapphire or the like and the group III nitride semiconductor layer 4 made of GaN or the like, when the group III nitride semiconductor layer 4 is grown and returned to room temperature, The nitride semiconductor epitaxial substrate 1 is warped due to the difference in thermal expansion coefficient, and compressive stress is applied to the group III nitride semiconductor layer 4. The compressive stress generated in the group III nitride semiconductor layer 4 causes cracks on the surface of the group III nitride semiconductor layer 4 such as GaN. When there is no ID on the surface of the conventional buffer layer, the number of cracks suddenly increased when the thickness of the group III nitride semiconductor layer 4 such as GaN was 5 μm or more.
However, in the nitride semiconductor epitaxial substrate 1 of this embodiment, since ID5 exists in the buffer layer 3 and the group III nitride semiconductor layer 4 on the substrate 2 side, compared to the case of only a group III polar crystal, III The behavior such as expansion / contraction deformation during compression / tension changes between the group polarity crystal and the N polarity crystal, particularly at the boundary between the group III polarity and the N polarity. For this reason, compared with the case of only the group III polar crystal, the buffer layer 3 and the group III nitride semiconductor layer 4 on the substrate 2 side due to compressive stress are reduced, and the stress in the vicinity of the substrate 2 in particular is alleviated. It is estimated that In the nitride semiconductor epitaxial substrate 1 of this embodiment in which ID5 exists in the buffer layer 3 and the group III nitride semiconductor layer 4 on the substrate 2 side, the thickness of the group III nitride semiconductor layer 4 such as GaN is set to 5 μm or more. Even in this case, a nitride semiconductor epitaxial substrate having no cracks on the surface of the group III nitride semiconductor layer 4 can be manufactured with high yield.

(Nitride semiconductor devices)
A nitride semiconductor device according to an embodiment of the present invention uses the nitride semiconductor epitaxial substrate 1 of the above-described embodiment, and forms a device structure such as a group III nitride semiconductor layer or an electrode on the nitride semiconductor epitaxial substrate 1. It is a nitride semiconductor device to be manufactured. In this nitride semiconductor device, the surface of the group III nitride semiconductor layer 4 of the nitride semiconductor epitaxial substrate 1 of the above embodiment has low dislocations, and the half width of the X-ray rocking curve is also small. A nitride semiconductor device having excellent characteristics can be manufactured as compared with the case where a substrate is used.

As an example of the nitride semiconductor device, a blue LED (light emitting diode) shown in FIG. 2 manufactured using the nitride semiconductor epitaxial substrate 1 of the above embodiment will be described.
The nitride semiconductor epitaxial substrate 1 is obtained by forming a GaN layer as a group III nitride semiconductor layer 4 on a substrate 2 that is a sapphire substrate, with a buffer layer 2 that is an AlN layer having ID. The epitaxial substrate 1 is set in a MOVPE apparatus, and a blue LED laminated semiconductor is grown on the epitaxial substrate 1. The laminated semiconductor of the blue LED structure is an n-type GaN clad layer 21, an active layer 22 of an InGaN / GaN multiple quantum well structure, and a p-type AlGaN, which are sequentially grown on the GaN group III nitride semiconductor layer 4. The cladding layer 23 and the p-type GaN contact layer 24 are included.
After the above laminated semiconductor is grown, the LED substrate is taken out from the MOVPE apparatus, and the obtained laminated semiconductor layer of the LED substrate is partially etched away by RIE (Reactive Ion Etching), and the n-type GaN cladding layer 21 is formed. Expose part. The n-side electrode 25 is formed on the exposed n-type GaN clad layer 21 and the p-side electrode 26 is formed on the p-type GaN contact layer 24. Thereafter, the structure shown in FIG. A blue LED is produced. A nitride semiconductor epitaxial substrate 1 having an n-type GaN cladding layer 21, an active layer 22, and a p-type AlGaN cladding layer 23 is formed on a group III nitride semiconductor layer 4 made of a GaN layer having good crystallinity. The LED had a large light output and a low driving voltage.

  As another example of the nitride semiconductor device, a Schottky barrier diode (SBD) will be described. The nitride semiconductor epitaxial substrate used for SBD is formed by forming a GaN layer on a sapphire substrate via an AlN buffer layer having ID, similarly to the LED. An SBD was fabricated by forming a Schottky electrode and an ohmic electrode around the Schottky electrode so as to surround the Schottky electrode on the GaN layer of the nitride semiconductor epitaxial substrate, but an SBD with good characteristics was obtained.

  Next, a nitride semiconductor epitaxial substrate according to an embodiment of the present invention will be described.

The nitride semiconductor epitaxial substrate of the example has the same cross-sectional structure as the nitride semiconductor epitaxial substrate 1 of the above embodiment shown in FIG. 1C, and is on a C-plane sapphire substrate (4 inch diameter) as the substrate 2. In addition, a GaN layer as the group III nitride semiconductor layer 4 is formed through an AlN buffer layer as the buffer layer 3 having ID on the surface.
The AlN buffer layer has a thickness of 50 nm, and Cl, S, or B as an impurity is included in the AlN buffer layer in a concentration range of about 1 × 10 ¹⁵ cm ⁻³ to 1 × 10 ²⁰ cm ⁻³ , and the surface ID A plurality of AlN buffer layers having different areal densities were formed. Then, an undoped GaN layer (thickness 8 μm) was formed on these AlN buffer layers. The AlN buffer layer and the GaN layer were formed by the HVPE method. The growth of the GaN layer was performed at 1050 ° C. under the conditions of a growth rate of 1 μm / min and a V / III ratio of 20. As the carrier gas, a mixed gas of hydrogen and nitrogen was used.

  Further, a nitride semiconductor epitaxial substrate of a comparative example was fabricated in the same manner as the nitride semiconductor epitaxial substrate of the above example, except that no impurities were added to the AlN buffer layer.

The surface density of the ID of the surface of the AlN buffer layer in the nitride semiconductor epitaxial substrate of the example and the comparative example was measured by the CBED method. In the embodiment, when the impurity concentration in the AlN buffer layer is 1 × 10 ¹⁹ cm ⁻³ or less, the ID of 1 × 10 ⁴ cm ⁻² to 1 × 10 ¹¹ cm ⁻² is formed on the surface of the AlN buffer layer. It existed in a range of areal densities. On the other hand, when the impurity concentration in the AlN buffer layer was higher than 1 × 10 ¹⁹ cm ⁻³ , the ID density was higher than 1 × 10 ¹¹ cm ⁻² . No ID was detected on the surface of the AlN buffer layer to which the impurity of the comparative example was not added. Also, no ID was detected on the surface of the GaN layer in the epitaxial substrates of the examples and comparative examples.

X-ray diffraction was performed on the GaN layers of the epitaxial substrates of Examples and Comparative Examples, and the half widths of the rocking curves on the (0002) plane, (0004) plane, and (10-12) plane were measured. FIG. 3 shows the result.
As shown in FIG. 3, in the GaN layer of the comparative example (with no ID on the surface of the AlN buffer layer), the half widths of the rocking curves of the (0002) plane and the (0004) plane both slightly exceed 300 seconds. The half width of the rocking curve on the (10-12) plane was slightly over 500 seconds. On the other hand, in the GaN layer of the example, in the range where the ID surface density on the surface of the AlN buffer layer is 1 × 10 ⁴ cm ⁻² or more and 1 × 10 ¹¹ cm ⁻² or less, the rocking curves of the (0002) plane and the (0004) plane are used. The half-value width of each was 300 seconds or less, and the half-value width of the rocking curve of the (10-12) plane was 500 seconds or less. Further, in the range where the ID surface density on the AlN buffer layer surface is 1 × 10 ⁵ cm ⁻² or more and 1 × 10 ¹⁰ cm ⁻² or less, the full widths at half maximum of the rocking curves of the (0002) plane and the (0004) plane are both The full width at half maximum of the rocking curve on the (10-12) plane was as small as 300 seconds or less.

Further, the dislocation density on the surface of the GaN layer in the epitaxial substrates of Examples and Comparative Examples was measured. FIG. 4 shows the measurement result of the dislocation density.
As shown in FIG. 4, the dislocation density on the surface of the GaN layer of the comparative example exceeded 5 × 10 ⁸ cm ⁻² . In contrast, in the GaN layer of the example, the dislocation density on the surface of the GaN layer is 5 × 10 5 when the ID surface density on the surface of the AlN buffer layer is in the range of 1 × 10 ⁴ cm ^{−2 to} 1 × 10 ¹¹ cm ^{−2. 8} cm ^-2 or less, further, the ID surface density of 1 × ¹⁰ 6 ^{cm -2} or more 1 × ¹⁰ 9 ^{cm -2} or less in the range of AlN buffer layer surface, the dislocation density 1 × 10 ⁸ of the GaN layer surface It was as low as cm ⁻² .

An experiment similar to the above was performed by changing the thickness of the AlN buffer layer in the range of 10 nm to 300 nm, and almost the same result was obtained.
Further, under the growth conditions of the GaN layer, the growth rate is 0.1 μm / min to 10 μm / min, the V / III ratio is 1 to 1000, the growth temperature is 900 ° C. to 1100 ° C., and the H ₂ / N ₂ ratio in the carrier gas. When the experiment similar to the above was performed by changing the value in the range of 0 to 100, almost the same result was obtained.

Next, in the nitride semiconductor epitaxial substrate of the example, the ID surface density of the AlN buffer layer surface is about 1 × 10 ⁷ cm ⁻² , and the thickness of the GaN layer is changed in the range of about 1 μm to 10 μm. An epitaxial substrate was produced. In addition, also in the nitride semiconductor epitaxial substrate of the comparative example, epitaxial substrates having various GaN layer thicknesses were produced. In the nitride semiconductor epitaxial substrates of these examples and comparative examples, the presence or absence of cracks on the surface of the GaN layer was examined. FIG. 5 shows the relationship between the thickness of the GaN layer and crack yield (ratio (%) at which no crack is generated in the GaN layer).
As shown in FIG. 5, in both the epitaxial substrate of the comparative example and the epitaxial substrate of the example, no crack is generated on the surface of the GaN layer until the thickness of the GaN layer is about 3 μm, and the crack yield is almost 100%. %Met. However, in the epitaxial substrate of the comparative example, when the thickness of the GaN layer was approximately 5 μm or more, the crack yield rapidly decreased. On the other hand, in the epitaxial substrate of the example, the decrease in crack yield was small even when the thickness of the GaN layer exceeded 5 μm, and there was about 60% crack yield even when the thickness of the GaN layer was 10 μm.
The same experiment was performed on various AlN buffer layers having an ID surface density in the range of 1 × 10 ⁴ cm ⁻² to 1 × 10 ¹¹ cm ⁻² , and almost the same results were obtained.

From the above results, impurities such as Cl are contained in the AlN buffer layer at a concentration of about 1 × 10 ¹⁵ cm ⁻³ to 1 × 10 ¹⁹ cm ⁻³ , and the ID of the AlN buffer layer surface is 1 × 10 ⁴ cm ^{−. By} making it exist at a surface density of ² to 1 × 10 ¹¹ cm ^−2, the FWHM of the rocking curve of the GaN layer can be reduced, the dislocation density on the surface (outermost surface) of the GaN layer can be reduced, and the GaN layer can be 5 μm. It has been found that cracking of the GaN layer can be suppressed even when it is thicker than above.

DESCRIPTION OF SYMBOLS 1 Nitride semiconductor epitaxial substrate 2 Substrate 3 Buffer layer 3a Group III polar surface 3b N polar surface 4 Group III nitride semiconductor layer 5 Inversion domain (ID)
f1-f5 crystal growth surface

Claims (8)

A method for producing a nitride semiconductor epitaxial substrate, comprising: growing a buffer layer on a substrate; and growing a group III nitride semiconductor layer on the buffer layer,
In the step of growing the buffer layer, a layer made of a group III nitride semiconductor containing Al and having an inversion domain on its surface is formed by a vapor phase growth method.
In the step of growing the group III nitride semiconductor layer, a layer grown on the inversion domain is embedded by a layer grown on a region other than the inversion domain, and a layer whose surface is a C-plane, A method for manufacturing a nitride semiconductor epitaxial substrate, characterized by forming by a vapor deposition method. In the step of forming the buffer layer,
2. The nitride semiconductor according to claim 1, wherein the buffer layer having a surface density of the inversion domain on a surface in a range of 1 × 10 ⁴ cm ^{−2 to} 1 × 10 ¹¹ cm ⁻² is formed. Epitaxial substrate manufacturing method. In the step of forming the group III nitride semiconductor layer,
The method for producing a nitride semiconductor epitaxial substrate according to claim 1, wherein the group III nitride semiconductor layer having no inversion domain on the surface is formed. In the step of forming the buffer layer,
4. The buffer layer according to claim 1, wherein one or more of Cl, S, and B are added at a concentration of 1 × 10 ¹⁵ cm ⁻³ or more. A method for producing a nitride semiconductor epitaxial substrate according to claim 1. In the step of forming the group III nitride semiconductor layer,
5. The method for producing a nitride semiconductor epitaxial substrate according to claim 1, wherein the group III nitride semiconductor layer having a surface dislocation density of 5 × 10 ⁸ cm ⁻² or less is formed. In the step of forming the group III nitride semiconductor layer,
The group III nitride semiconductor having half-widths of (0002) plane diffraction, (0004) plane diffraction, and (10-12) plane diffraction in X-ray rocking curve measurement of 300 seconds or less, 300 seconds or less, and 500 seconds or less, respectively. The method for producing a nitride semiconductor epitaxial substrate according to claim 1, wherein a layer is formed. In the step of forming the group III nitride semiconductor layer,
The method for producing a nitride semiconductor epitaxial substrate according to claim 1, wherein the group III nitride semiconductor layer having a thickness of 5 μm or more and having no cracks on the surface is formed. A step of growing a buffer layer on the substrate; a step of growing a group III nitride semiconductor layer on the buffer layer; and a step of forming a device structure on the group III nitride semiconductor layer. A device manufacturing method comprising:
In the step of growing the buffer layer, a layer made of a group III nitride semiconductor containing Al and having an inversion domain on its surface is formed by a vapor phase growth method.
In the step of growing the group III nitride semiconductor layer, a layer grown on the inversion domain is embedded by a layer grown on a region other than the inversion domain, and a layer whose surface is a C-plane, A method of manufacturing a nitride semiconductor device, characterized by forming by a vapor deposition method.

Images