Method of Manufacturing GaN Crystal Substrate
Affords a method of manufacturing GaN crystal substrate in which enlargement of pit size in the growing of GaN crystal is inhibited to enable GaN crystal substrate with a high substrate-acquisition rate to be produced. The method of manufacturing GaN crystal substrate includes a step of growing GaN crystal (4) by a vapor growth technique onto a growth substrate (1), the GaN-crystal-substrate manufacturing method being characterized in that in the step of growing the GaN crystal (4), pits (6) that define facet planes (5F) are formed in the crystal-growth surface, and being characterized by having the pit-size increase factor of the pits (6) be 20% or less.
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1. Technical Field
The present invention relates to methods of manufacturing GaN monocrystalline substrates used in light-emitting devices, such as light-emitting diodes (LEDs) and laser diodes (LDs), made from Group III-V semiconductor compounds.
2. Description of the Related Art
As a way of manufacturing large-scale, low-dislocation-density GaN-crystal thick films for application as substrates in LEDs, LDs and other light-emitting devices made from Group III-V semiconductor compounds, one method that has been proposed is, when growing GaN crystal onto a base substrate using a vapor growth technique, to form in the crystal-growth surface pits that define facet planes and to confine the dislocations to, or quench the dislocations along, the boundary lines of the facet planes of the pits, to grow GaN substrates of large area and slight dislocation density. (Cf. Japanese Unexamined Pat. App. Pub. No. 2001-102307, for example.)
A problem with this pit-employing method of manufacturing GaN crystal substrates, however, has been that along with the GaN crystal growth the pits grow too, enlarging diametrically, which lessens the effective GaN crystal portion that can be obtained by separating off the grown GaN crystal in thin, platelike form.
BRIEF SUMMARY OF THE INVENTIONIn view of the foregoing circumstances, an object of the present invention is to make available a method of manufacturing GaN crystal substrate that efficiently yields a great amount GaN crystal substrate (that is, in which the substrate-acquisition rate is high) by, in the growing of GaN crystal, inhibiting enlargement of pit size to increase the effective GaN crystal portion in which the grown GaN crystal, separated off in thin, platelike form, is usable as a GaN crystal substrate.
In order to address the foregoing objective, the present invention is a method of manufacturing GaN crystal substrate that includes a step of growing GaN crystal by a vapor growth technique onto a base (growth) substrate, the GaN-crystal-substrate manufacturing method being characterized in that in the step of growing GaN crystal, facet-plane-defining pits are formed in the crystal-growth surface, and being characterized by having the pit-size increase factor of the pits be 20% or less.
In addition, the present invention is a method of manufacturing GaN crystal substrate that includes a step of forming an aperture-window-defining mask layer onto a growth substrate, and a step of growing GaN crystal by a vapor growth technique onto the mask layer, the GaN-crystal-substrate manufacturing method being characterized in that facet-plane-defining pits are formed in the crystal-growth surface, and being characterized by having the pit-size increase factor of the pits be 20% or less.
In a GaN-crystal-substrate manufacturing method involving the present invention, it is preferable that, in the step of growing GaN crystal, the temperature at which the GaN crystal is grown be 1000° C. or less.
As set forth above, the present invention affords a method of manufacturing GaN crystal substrate in which enlargement of pit size in the growing of GaN crystal is inhibited to enable GaN crystal substrate with a high substrate-acquisition rate to be produced.
From the following detailed description in conjunction with the accompanying drawings, the foregoing and other objects, features, aspects and advantages of the present invention will become readily apparent to those skilled in the art.
Reference is made to
Preferable examples of the base substrate herein include, although they are not particularly limited to, a GaN substrate, which is a native substrate that is free from lattice mismatches with the GaN crystal, and foreign substrates that have small lattice mismatches, such as GaAs substrates, sapphire substrates, and SiC substrates. The base substrate is not limited to one with a single layer construction; a base substrate on which a GaN layer is formed on a sapphire substrate or SiC substrate, which are foreign substrates, may also be used as a native substrate.
Referring to
Examples of vapor phase deposition techniques include, but are not particularly limited to, techniques such as HVPE (hydride vapor phase epitaxy), MOCVD (metal-organic chemical vapor deposition), MOC (metal-organic chloride vapor phase epitaxy), and sublimation. Among these, HVPE, which has a high growth rate, is preferable for obtaining a GaN substrate with considerable thickness.
The term “facet plane” refers to a plane other than the plane that is perpendicular to the crystal growth orientation (growth surface). Herein, the c-plane 5C is the growth surface since the crystal growth takes place along the c-axis orientation, and the facet planes are those planes other than the c-plane. GaN crystal has a hexagonal structure, so the c-plane, which is the growth surface, is represented as (0001). In the GaN crystal, the facet planes that appear frequently are the {1
The reason why the crystal dislocation density is reduced by forming facet-plane-defining pits in the crystal growth surface and carrying out crystal growth will be explained. With reference to
The formation of facet-plane-defining pits on the crystal growth surface as described above is dependent on crystal growth conditions such as growth temperature, growth rate, and the partial pressure of the precursor gas. For example, the lower the growth temperature is, the more raised the growth rate is, and the more raised the partial pressure of the precursor gas is, the more the formation of the above-noted pits tends to be promoted.
In particular, in growing a GaN crystal by HVPE, in order to form the facet-plane-defining pits as described above, it is preferable that the growth temperature be about 850° C. to 1100° C., the growth rate be about 50 μm/hr to 200 μm/hr, the GaCl gas partial pressure be about 0.5 kPa to 4 kPa, and the NH3 gas partial pressure be about 5 kPa to 50 kPa.
In the present invention the pit-size increase factor of the above-described pits is rendered 20% or less. Herein, the term “pit-size increase factor” means the proportion of increase in the pit diameter with respect to the thickness of the GaN crystal, and is defined, with reference to
pit-size increase factor (%)=100×L/H (1)
wherein the thickness of the GaN crystal is H (μm) and the pit size is L (μm).
By having the pit-size increase factor be 20% or less, more GaN crystal substrates can be obtained from a GaN crystal. For example,
Thus, it will be appreciated that the substrate acquisition rate improves with lessening pit-size increase factor, as demonstrated by the following equation (2), which defines the substrate acquisition rate (%):
substrate acquisition rate(%)=100×He/H (2)
wherein when a GaN crystal is grown to a thickness of H (μm), the usable thickness of the GaN crystal that can be separated off as a GaN crystal substrate is He (μm).
Herein, referring to
Accordingly, an effective technique to reduce the pit-size increase factor includes both reducing the growth rate of the c-plane with respect to the growth rate of a facet plane so that VC<VF sin θ, and not supplying the crystal growth energy at which the pits would coalesce. To achieve these results, it is preferable that the growth temperature for GaN crystal be 1000° C. or lower in the step of growing the GaN crystal. Reducing the growth temperature for the GaN crystal lowers the growth rate of the c-plane with respect to the growth rate of a facet plane and reduces crystal growth energy, which inhibits coalescence of the pits, thereby reducing the pit-size increase factor. By restricting the growth temperature for the GaN crystal to 1000° C. or lower, the pit-size increase factor can easily be made to be 20% or less. In light of this fact, the growth temperature for the GaN crystal is preferably 950° C. or lower, and still more preferably 900° C. or lower.
In conjunction with the lowering of the growth temperature for the GaN crystal, it is preferable that the growth rate of the GaN crystal be small. The growth rate of the GaN crystal should preferably be 150 μm/hr or less, more preferably 120 μm/hr or less, and still more preferably 100 μm/hr or less.
In view of reducing the growth rate of the GaN crystal, it is preferable that partial pressures of the source gases in growing the GaN crystal be small. With an HVPE technique, the GaCl gas partial pressure should preferably be from 0.5 kPa to 2.0 kPa or lower, and more preferably 0.5 kPa to 1.5 kPa. The NH3 gas partial pressure should preferably be 5 kPa to 15 kPa, and more preferably 5 kPa to 10 kPa.
With reference to
In this case as well, preferable examples of the growth substrate include, but are not particularly limited to, a GaN substrate, which is a native substrate that is free from lattice mismatches with the GaN crystal, and foreign substrates that have small lattice mismatches, such as a sapphire substrate and a SiC substrate. Referring to
The aperture-window-defining mask layer is formed by coating the growth substrate with a mask material and thereafter forming the aperture windows by photolithography. Herein, examples of the mask material include SiO2 and Si3N4.
Also, there are no restrictions on the way in which the aperture windows of the mask layer are provided, and it is possible to employ either a dotted pattern or a striped pattern. The dotted pattern refers to one in which isolated dots having a circular shape, a square shape, or the like are distributed regularly; when growing the GaN crystal along the c-plane orientation, it is preferable that three adjacent aperture windows be arranged to sit at the vertexes of equilateral triangles. The striped pattern refers to one in which a multiplicity of striplike covering portions and aperture window portions are provided alternately.
With reference to
With reference to
With the HVPE technique, GaN crystals were grown to a thickness of about 2 mm on growth substrates at the growth temperatures, GaCl partial pressures, NH3 partial pressures, and growth rates set forth in Table I. Then, the GaN crystals were sliced with a wire saw or an internal-diameter saw and the surfaces were polished to obtain GaN crystal substrates of predetermined thickness. The dislocation densities, pit-size increase factors, and substrate acquisition rate of the GaN crystals are summarized in Table I.
Examples 5 through 8, Comparative Example 2With reference to
Each aperture-window-defining mask layer was formed by forming a 100 nm-thick SiO2 layer by CVD, and thereafter forming by photolithography aperture windows that are arrayed in a dotted pattern in which three adjacent aperture windows (squares 2 μm to a side) sit at the vertexes of equilateral triangles (the distance between the adjacent aperture windows being 4 μm).
By an HVPE technique, GaN crystals were grown to a thickness of about 2 mm on growth substrates at the growth temperatures, GaCl partial pressures, NH3 partial pressures, and growth rates set forth in Table I. Then, the GaN crystals were sliced with a wire saw or an internal-diameter saw and the surfaces were polished to obtain GaN crystal substrates having a predetermined thickness. The dislocation densities, pit-size increase factors, and substrate acquisition rates of the GaN crystals are summarized in Table I.
With reference to
For the GaN buffer layers 3, amorphous layers having a thickness of about 70 nm were formed, using an HVPE technique, by heating and holding the growth substrate 1 to 500° C. at a GaCl partial pressure of 0.2 kPa and a NH3 partial pressure of 15 kPa.
With an HVPE technique, GaN crystals were grown to a thickness of about mm over the GaN buffer layers 3 at the growth temperatures, GaCl partial pressures, NH3 partial pressures, and growth rates set forth in Table II. Then, the GaAs substrates were removed by etching in aqua regia, and thereafter the GaN crystals were sliced with a wire saw or an internal-diameter saw and their surfaces polished to obtain GaN crystal substrates having a predetermined thickness. The dislocation densities, pit-size increase factors, and substrate acquisition rates of the GaN crystals are summarized in Table II.
Examples 13 through 16, Comparative Example 4With reference to
Each of the aperture-window-defining mask layers 2 was formed in the same manner as the mask layers in Examples 4 through 6. Each of the GaN buffer layers 3 were formed in the same manner as the buffer layers in Examples 7 through 9.
With an HVPE technique, GaN crystals were grown to a thickness of about 2 mm over the GaN buffer layers 3 at the growth temperatures, GaCl partial pressures, NH3 partial pressures, and growth rates set forth in Table II. Then, the GaAs substrates were removed by etching in aqua regia, and thereafter, the GaN crystals were sliced with a wire saw or an internal-diameter sawand their surfaces polished to obtain GaN crystal substrates having a predetermined thickness. The dislocation densities, pit-size increase factors, and substrate acquisition rates of the GaN crystals are summarized in Table II.
As is evident from Tables I and II, the substrate acquisition rate was 83% or higher at a pit-size increase factor of 20% or less, and was 91% or higher at a pit-size increase factor of 10% or less, which proves that reducing the pit-size increase factor improves the substrate acquisition rate. Moreover, the provision of the aperture-window-defining mask layer further reduced dislocations in the GaN crystal.
As described in the foregoing, because the present invention efficiently yields a great amount GaN crystal substrate, it will find broad utilization as a method of manufacturing GaN crystal substrates.
The presently disclosed embodiments and implementation examples should in all respects be considered to be illustrative and not limiting. The scope of the present invention is set forth not by the foregoing description but by the scope of the patent claims, and is intended to include meanings equivalent to the scope of the patent claims and all modifications within the scope.
Claims
1. A method of growing GaN crystal onto a growth substrate by a vapor growth technique, the method comprising:
- a step of reacting GaCl with NH3, wherein the GaCl has a gas partial pressure ranging from 0.5 kPa to 4.0 kPa, and the NH3 has a gas partial pressure ranging from 5.0 kPa to 50 kPa.
2. The method of growing GaN crystal according to claim 1, wherein:
- the GaCl has a gas partial pressure ranging from 0.5 kPa to 2.0 kPa; and
- the NH3 has a gas partial pressure ranging from 5.0 kPa to 15 kPa.
3. The method of growing GaN crystal according to claim 1, wherein:
- the GaCl has a gas partial pressure ranging from 0.5 k Pa to 2.0 kPa; and
- the NH3 has a gas partial pressure ranging from 5.0 kPa to 10 kPa.
4. The method of growing GaN crystal according to claim 1, wherein:
- the GaCl has a gas partial pressure ranging from 0.5 kPa to 1.5 kPa; and
- the NH3 has a gas partial pressure ranging from 5.0 kPa to 10 kPa.
5. The method of growing GaN crystal according to claim 1, wherein:
- the GaN crystal has a substrate acquisition rate of 83% or higher.
6. The method of growing GaN crystal according to claim 2, wherein:
- the GaN crystal has a substrate acquisition rate of 83% or higher.
7. The method of growing GaN crystal according to claim 3, wherein:
- the GaN crystal has a substrate acquisition rate of 83% or higher.
8. The method of growing GaN crystal according to claim 4, wherein:
- the GaN crystal has a substrate acquisition rate of 83% or higher.
9. The method of growing GaN crystal according to claim 1, wherein:
- the GaN crystal has a substrate acquisition rate ranging from 83 to 96%.
10. The method of growing GaN crystal according to claim 2, wherein:
- the GaN crystal has a substrate acquisition rate ranging from 83 to 96%.
11. The method of growing GaN crystal according to claim 3, wherein:
- the GaN crystal has a substrate acquisition rate ranging from 83 to 96%.
12. The method of growing GaN crystal according to claim 4, wherein:
- the GaN crystal has a substrate acquisition rate ranging from 83 to 96%.
Type: Application
Filed: Dec 19, 2008
Publication Date: Apr 23, 2009
Applicant: SUMITOMO ELECTRIC INDUSTRIES, LTD. (Osaka-shi)
Inventor: Takuji Okahisa (Itami-shi)
Application Number: 12/339,087
International Classification: C30B 25/00 (20060101);