JP6013743B2 - Manufacturing method of semiconductor device - Google Patents

Description

  The present invention relates to a semiconductor device, a method for manufacturing the same, and a method for manufacturing a free-standing substrate.

  A method for manufacturing a semiconductor device is known in which a semiconductor layer is formed on a processed substrate having fine irregularities formed on the surface of the substrate (for example, Patent Document 1).

GaN whose principal surface is c-plane (hereinafter also referred to as “c-plane GaN”) has a film thickness ranging from the order of 10 ⁻¹ μm to the order of 10 ² μm. It is known that the defect density decreases as the thickness increases (for example, Non-Patent Document 1).

  However, since the c-plane GaN is a c-polar plane, the c-plane GaN has a low luminous efficiency due to spontaneous polarization and piezo-polarization when used in a light-emitting element, and is therefore considered disadvantageous for use in this application. ing.

WO2010 / 023846A1

S.K.Mathis et al. Journal of Crystal 231 (2001) 371-390

  On the other hand, in the case of GaN having a nonpolar or semipolar surface whose principal surface is crystal plane grown on the processed substrate of the sapphire substrate, there is no correlation between the film thickness and the defect density up to the order of 10 μm, There is no effect of reducing the defect density as the film thickness of c-plane GaN increases.

  An object of the present invention is to obtain a III-V group compound semiconductor layer whose main surface is a nonpolar surface or a semipolar surface and whose surface defect density is small.

The present invention uses a base substrate having a substrate surface having a substrate main surface portion and a crystal growth surface portion capable of crystal growth of a III-V compound semiconductor having a different plane orientation from the substrate main surface portion. A III-V group compound semiconductor whose principal surface is a nonpolar plane or a semipolar plane by growing the group III-V compound semiconductor in layers from the crystal growth plane portion on the substrate surface of the base substrate A method of manufacturing a semiconductor device including a semiconductor layer forming step of forming a layer,
In the semiconductor layer forming step is performed to form the above thickness 3 00Myuemu group III-V compound semiconductor layer, and the defect density of the surface of the resulting group III-V compound semiconductor layer is in 1 × 10 7 ^/ cm ² or less There is .

  According to the present invention, the III-V group compound semiconductor layer is formed to a thickness of 100 μm or more, whereby the main surface is a nonpolar plane or a semipolar plane and the surface defect density is small. Can be obtained.

It is explanatory drawing of the manufacturing method of the semiconductor device which concerns on embodiment. (A) And (b) is sectional drawing of a process board | substrate. It is a graph which shows the relationship between the thickness of a GaN layer, and defect density.

  Hereinafter, embodiments will be described in detail based on the drawings.

  As shown in FIG. 1, the manufacturing method of the semiconductor device according to the present embodiment uses a base substrate 10 as a processed substrate, and a III-V group compound semiconductor is crystal-grown in a layer form on the base substrate 10 to make the main surface nonpolar. A semiconductor layer forming step of forming a group III-V compound semiconductor layer 20 (hereinafter referred to as “semiconductor layer”) which is a plane or semipolar plane.

Here, the base substrate 10 is not particularly limited, and examples thereof include a sapphire substrate (a single crystal substrate having a corundum structure of Al ₂ O ₃ ), a ZnO substrate, and a SiC substrate. Of these, sapphire substrates are preferred.

The base substrate 10 is a processed substrate, and examples thereof include a processed substrate in which fine irregularities are formed on the substrate surface 11 as shown in FIG. 2A by etching or the like. The substrate surface 11 has a substrate main surface portion 11a and a crystal growth surface portion 11b that has a different plane orientation from that of the substrate main surface portion 11a and is capable of crystal growth of a group III-V compound semiconductor. As shown in FIG. 2B, the base substrate 10 may be one in which a portion other than the crystal growth surface portion 11b is covered with a crystal growth inhibition layer 12 made of SiO ₂ or the like.

  Substrate main surface portion 11a includes a-plane <{11-20} plane>, c-plane <{0001} plane>, m-plane <{1-100} plane>, and r-plane <{1-102} plane>. Any of them may be used, and the crystal plane may have another plane orientation. The crystal growth surface portion 11b includes an a plane <{11-20} plane>, a c plane <{0001} plane>, an m plane <{1-100} plane>, and an r plane <{1-102} plane>. Any of them may be used, and the crystal plane may have another plane orientation. A group III-V compound semiconductor is grown from the crystal growth surface portion 11b on the substrate surface 11 of the base substrate 10, and the group III elements in the group III-V compound semiconductor are aluminum (Al) and gallium (Ga). Indium (In), group V elements include nitrogen (N), phosphorus (P), arsenic (As), and antimony (Sb). The group III-V compound semiconductor typically includes a group III nitride semiconductor, and specifically includes GaN, AlGaN, InGaN, InAlGaN, InAlN, InN, and the like. Of these, GaN is preferred.

  The main surface of the semiconductor layer 20 is a nonpolar plane or a semipolar plane, and is a plane <{11-20} plane>, m plane <{1-100} plane>, and r plane <{1-102} plane. >, Or a crystal plane of another plane orientation such as {10-11} plane, {11-22} plane, {20-21} plane. Of these, the {10-11} plane of the semipolar plane is particularly preferable because the effect of reducing dislocation when the semiconductor layer 20 is 100 μm or more in thickness is remarkable. The crystal growth of the III-V compound semiconductor on the base substrate 10 is preferably epitaxial growth.

  Examples of the crystal growth means include vapor phase growth means such as hydride vapor phase epitaxy (HVPE), metal organic chemical vapor deposition (MOCVD), and molecular beam epitaxy (MBE). From the viewpoint that a high-quality semiconductor layer 20 having a high thickness can be formed at high speed, a hydride vapor phase growth method is preferable. Crystal growth may be performed by a single means or a combination of a plurality of means. For example, first, a template in which a thin semiconductor layer is formed by growing a group III-V compound semiconductor on the base substrate 10 by metal organic chemical vapor deposition is manufactured. It can be considered that the semiconductor layer 20 is formed by crystal growth of a group III-V compound semiconductor by a hydride vapor phase growth method having a high growth rate.

As the crystal growth conditions, for example, when GaN of a III-V group compound semiconductor is grown on a sapphire substrate as the base substrate 10 by hydride vapor phase epitaxy, the pressure in the reaction vessel is 10 to 120 kPa, and the sapphire substrate The temperature of the gas is 900 to 1150 ° C., and hydrogen gas, nitrogen gas or a mixed gas thereof is used as the carrier gas, and the flow rate ratio of hydrogen chloride gas for forming GaCl and ammonia gas of the nitrogen source (NH ₃ / HCl) is 2 to 100. Before forming the semiconductor layer 20, a low-temperature buffer layer made of a group III-V compound semiconductor having a thickness of about 20 to 30 nm and / or 1 to 10 μm is formed on the surface of the base substrate 10 by metal organic chemical vapor deposition or the like. A III-V compound semiconductor may be provided.

  And in the manufacturing method of the semiconductor device concerning this embodiment, in the semiconductor layer formation process, semiconductor layer 20 is formed in thickness of 100 micrometers or more. Thus, by forming the semiconductor layer 20 with a thickness of 100 μm or more, it is possible to obtain the semiconductor layer 20 whose main surface is a nonpolar surface or semipolar surface and whose surface defect density is small. The thickness of the semiconductor layer 20 is a dimension from the upper end surface of the convex portion in the fine unevenness on the surface of the base substrate 10 to the surface of the semiconductor layer 20.

  From the viewpoint of the above effects, the thickness of the semiconductor layer 20 formed by crystal growth of a group III-V compound semiconductor is preferably 300 μm or more, more preferably 400 μm or more. In addition, although the upper limit of the thickness of the semiconductor layer 20 is not specifically limited, For example, it is 10 cm or less.

The defect density of the obtained semiconductor layer 20 is preferably 1 × 10 ⁷ / cm ² or less, more preferably 1 × 10 ⁶ / cm ² or less. The defect density can be calculated by dark spot measurement by cathodoluminescence or pit density measurement by KHO etching.

  In the method for manufacturing a semiconductor device according to this embodiment, the semiconductor device may be manufactured by providing various functional layers on the semiconductor layer 20 formed on the base substrate 10. In this case, as a semiconductor device, the substrate surface 11 includes a substrate main surface portion 11a and a crystal growth surface portion 11b capable of crystal growth of a group III-V compound semiconductor while having a different plane orientation from the substrate main surface portion 11a. And a main surface formed by crystal growth of a group III-V compound semiconductor in layers from the crystal growth surface portion 11b on the substrate surface 11 of the base substrate 10 is a nonpolar surface or a semipolar surface. The semiconductor layer 20 is provided, and the semiconductor layer 20 having a thickness of 100 μm or more can be obtained.

  In the method for manufacturing a semiconductor device according to the present embodiment, all or part of the semiconductor layer 20 is separated from the base substrate 10 to manufacture a self-supporting substrate (substrate separation process), and various functional layers are formed on the self-supporting substrate. May be provided to manufacture a semiconductor device.

  As the semiconductor device manufactured in the present embodiment, the semiconductor layer 20 with a low defect density is obtained. Therefore, if a light emitting layer is provided on the semiconductor layer, high light emission efficiency can be obtained. A semiconductor light emitting device such as is suitable.

(Formation of semiconductor layer)
On the surface of the r-plane sapphire substrate, n-plane sapphire substrate ({11-23} plane sapphire substrate), {22-43} plane sapphire substrate, there is a crystal growth surface portion perpendicular to the c-axis and near the c-plane on the side surface. A processed substrate was produced in which grooves were formed in stripes so as to be exposed, and the main surface portion of the substrate was coated with a crystal growth inhibiting layer made of SiO ₂ . The protrusion width and groove width between the grooves were both 2 μm, and the groove depth was 1 μm.

A GaN template in which a GaN layer having a main surface of {11-22} plane and a GaN layer having a thickness of 5 μm is formed on the processed substrate by metalorganic chemical vapor deposition using a crystal growth surface portion as a base point; A GaN template in which a GaN layer having a thickness of 5 μm whose main surface is a {10-11} plane and a GaN template in which a GaN layer having a thickness of 8 μm whose main surface is a {20-21} plane were formed were prepared. . The defect density on the surface of the GaN layer of these GaN templates was about 2.0 to 3.0 × 10 ⁸ / cm ² .

  And about each GaN template, GaN was crystal-grown and thickness was changed, the GaN layer was formed, and the defect density of the surface was measured about each.

  The GaN layer was formed as follows.

  First, the GaN template was set on a carbon sample fixing base in a reaction furnace of a vertical hydride vapor phase epitaxy (HVPE) apparatus (FH702-F type) so that the GaN layer faced upstream of the gas. Next, the substrate region was heated while maintaining the furnace pressure at 101.3 kPa. Thereafter, supply of ammonia gas was started when the substrate temperature exceeded 500 ° C., and after the substrate temperature reached 1040 to 1100 ° C. of the crystal growth temperature, the state was maintained for 25 minutes to stabilize the substrate temperature. . Subsequently, while supplying hydrogen gas and nitrogen gas as a carrier gas, hydrogen chloride gas is supplied at a flow rate of 0.8 slm and ammonia gas at a flow rate of 8 to 24 slm (flow rate ratio: 10 to 30) to grow GaN crystals. Went. Thereafter, the supply of hydrogen chloride gas is stopped, the substrate is naturally cooled while supplying ammonia gas, the supply of ammonia gas is stopped after the substrate temperature becomes 200 ° C. or less, and then the substrate on which the GaN layer is formed from the reactor. Was taken out.

  Similarly, c-plane GaN layers were formed on the sapphire substrate with different thicknesses, and the surface defect density was measured for each.

(Defect density evaluation)
About the obtained GaN layer, the GaN layer surface was observed using the scanning electron microscope / cathode luminescence (SEM * CL) apparatus. At this time, the acceleration voltage was 5 kV, the observation range was 20 μm × 20 μm, and the defect density was calculated from the total number of dark spots observed in the observation range.

(Relationship between semiconductor layer thickness and defect density)
FIG. 3 shows the relationship between the thickness of the GaN layer and the defect density.

  According to FIG. 3, it can be seen that in the c-plane GaN of the polar plane, the defect density decreases as the film thickness increases from the order of 1 μm to 100 μm. On the other hand, in the {11-22} plane GaN, {10-11} plane GaN, and {20-21} plane GaN, which are semipolar planes, a film having a defect density in the order of 1 μm to 10 μm. Although no thickness dependency is observed, it can be seen that when the film thickness is on the order of 100 μm, the defect density decreases as the film thickness increases. In particular, in {10-11} plane GaN, a remarkable effect of reducing the defect density with an increase in film thickness in the order of 100 μm is observed.

  The present invention is useful for a semiconductor device, a method for manufacturing the same, and a method for manufacturing a free-standing substrate.

10 Base substrate 11 Substrate surface 11a Substrate main surface portion 11b Crystal growth surface portion 20 III-V group compound semiconductor layer (semiconductor layer)

Claims (7)

A base substrate having a substrate surface having a substrate main surface portion and a crystal growth surface portion capable of crystal growth of a group III-V compound semiconductor while having a plane orientation different from that of the substrate main surface portion. The III-V group compound semiconductor layer having a main surface that is a nonpolar plane or a semipolar plane is formed by growing the group III-V compound semiconductor in layers from the crystal growth plane portion of the substrate surface of the substrate. A method of manufacturing a semiconductor device having a semiconductor layer forming step,
In the semiconductor layer forming step is performed to form the above thickness 3 00Myuemu group III-V compound semiconductor layer, and the defect density of the surface of the resulting group III-V compound semiconductor layer is in 1 × 10 7 ^/ cm ² or less A method of manufacturing a semiconductor device. In the manufacturing method of the semiconductor device according to claim 1,
A method for manufacturing a semiconductor device, wherein the III-V compound semiconductor is GaN. In the manufacturing method of the semiconductor device according to claim 1 or 2,
A method for manufacturing a semiconductor device, wherein the main surface of the III-V compound semiconductor layer is a {10-11} plane. In the manufacturing method of the semiconductor device according to any one of claims 1 to 3,
A method for manufacturing a semiconductor device, wherein the base substrate is a sapphire substrate. In the manufacturing method of the semiconductor device according to any one of claims 1 to 4,
A method of manufacturing a semiconductor device, further comprising a substrate separation step of separating all or part of the III-V compound semiconductor layer formed in the semiconductor layer formation step from a base substrate as a free-standing substrate. A base substrate having a substrate surface having a substrate main surface portion and a crystal growth surface portion capable of crystal growth of a group III-V compound semiconductor having a different plane orientation from the substrate main surface portion;
A III-V group compound in which the principal surface formed by crystal growth of the III-V compound semiconductor in a layered manner starting from the crystal growth surface portion on the substrate surface of the base substrate is a nonpolar plane or a semipolar plane A semiconductor layer;
A semiconductor device comprising:
The group III-V compound semiconductor layer has a thickness of 3 00Myuemu least der is, and the semiconductor device defect density of the surface is 1 × ¹⁰ 7 / cm ² or less. A base substrate having a substrate surface having a substrate main surface portion and a crystal growth surface portion capable of crystal growth of a group III-V compound semiconductor while having a plane orientation different from that of the substrate main surface portion. The III-V group compound semiconductor layer having a main surface that is a nonpolar plane or a semipolar plane is formed by growing the group III-V compound semiconductor in layers from the crystal growth plane portion of the substrate surface of the substrate. A semiconductor layer forming step;
A substrate separating step for separating all or part of the III-V compound semiconductor layer formed in the semiconductor layer forming step from the base substrate as a free-standing substrate;
A self-supporting substrate manufacturing method comprising:
In the semiconductor layer forming step is performed to form the above thickness 3 00Myuemu group III-V compound semiconductor layer, and the defect density of the surface of the resulting group III-V compound semiconductor layer is in 1 × 10 7 ^/ cm ² or less A method of manufacturing a free-standing substrate.

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