Patent Application
20100307405
The present invention relates to methods of growing large-scale AlxGa1-xN (0<x≦1, same hereinafter) single crystal of good crystalline quality advantageously employed in semiconductor substrates, etc.
AlxGa1-xN single crystal and other Group III-nitride crystal is extraordinarily useful as a material for forming optoelectronic devices, microelectronic devices, semiconductor sensors, and similar semiconductor devices.
As a means in order to produce such AlxGa1-xN single crystal, vapor-phase deposition, especially sublimation growth, has been proposed from the perspective of obtaining high-quality single crystals whose diffraction-peak full-width at half-maximum in x-ray diffraction rocking curves is narrow. In the specification for U.S. Pat. No. 5,858,086 (Patent Document 1), for example, the growing of AlN single crystal at the high growth rate of 0.5 mm/hr by sublimation or similar vapor-phase deposition techniques is disclosed. And in the specification for U.S. Pat. No. 6,296,956 (Patent Document 2), AlN bulk single crystal whose crystal diameter is 1 inch (25.4 mm) or more and in which the proportion of contained impurities is 450 ppm or less, grown by sublimation onto a seed crystal, is disclosed. Lastly, in the specification for U.S. Pat. No. 6,001,748 (Patent Document 3), AlN crystal of 10 mm or longer length, 10 mm or greater width, and 300 μm or greater thickness, grown by sublimation, is disclosed.
When attempts have been made to produce large-scale (for example, 1-inch (25.4 mm) diameter×2-mm or greater thickness, same hereinafter) AlxGa1-xN single crystal by sublimation, however, the crystal growth has proven to be non-uniform, which has led to such problems as significant increase in dislocations, degradation in the crystal quality, and generation of polycrystal, such that a method of stably growing low-dislocation-density, high-quality AlxGa1-xN single crystal of practically useable size has yet to be proposed.
Patent Document 1: U.S. Pat. No. 5,858,086
Patent Document 2: U.S. Pat. No. 6,296,956
Patent Document 3: U.S. Pat. No. 6,001,748
AlxGa1-xN (0<x≦1) single crystal is generally grown employing sublimation growth. As far as this sublimation growth is concerned, the ways in which crystal is grown fall into a category in which crystal nuclei are created, without employing a template crystal, and the crystal nuclei are grown (hereinafter, “crystal-nuclei growth category”), and a category in which crystal is grown onto a template crystal (hereinafter, “on-template-crystal crystal growth category”). Herein, with the on-template-crystal crystal growth category, due to the difficulty of procuring large-area AlxGa1-xN (0<x≦1) substrates, normative template crystal, such as SiC crystal, whose chemical composition differs from that of the AlxGa1-xN single crystal that is grown, is employed.
With the on-template-crystal crystal growth category employing normative template crystal, while scaling up to comparatively larger sizes is facilitated, the downside is that dislocations and similar defects arise due to the mismatch in lattice constant and thermal expansion coefficient between the normative template crystal and the AlxGa1-xN single crystal grown onto it, as a consequence of which ordinarily only low-quality crystal can be obtained. With the crystal-nuclei growth category, on the other hand, high-quality crystal can be easily obtained, but not employing a template crystal is prohibitive of stably obtaining large-area bulk crystal, which has in general made it difficult to manufacture large-scale, high-quality crystal that can be put to practical use.
Given these circumstances, utilizing as a seed crystal large-area AlyGa1-yN (0<y≦1, same hereinafter) crystal would be desirable, to the extent that it is procurable as template crystal. Even if such AlyGa1-yN seed crystal is procured, however, owing to differences in such factors as the crystal-growth technique, the crystal-growth conditions, the chemical composition (that is, the type and percent-fraction of the atoms constituting the crystal), and the level of impurities, stress develops between the seed crystal and the single crystal grown onto the seed crystal, giving rise to dislocations and like defects, and to cracks, warping, etc. in the single crystal that is grown.
An object of the present invention is to resolve the problematic issues discussed above by making available a method of growing large-scale, high-quality AlxGa1-xN single crystal.
The present invention is an AlxGa1-xN single crystal growth method provided with: a step of preparing an AlyGa1-yN (0<y≦1) seed crystal whose crystal diameter D mm and thickness T mm satisfy the relation T<0.003D+0.15; and a step of growing AlxGa1-xN (0<x≦1) single crystal onto a major surface of the AlyGa1-yN seed crystal by sublimation growth.
In a method, involving the present invention, of growing AlxGa1-xN single crystal, crystal nuclei for the AlyGa1-yN seed crystal may be created by sublimation growth, and the crystal nuclei grown into the AlyGa1-yN seed crystal. Furthermore, the AlyGa1-yN seed crystal can have a (0001) surface as its major surface. In addition, the AlyGa1-yN seed crystal can contain, in mass ratio, 10 ppm or more of at least one type of atoms among the Group IVB elements.
The present invention, enables the provision of a method of growing large-scale, high-quality AlxGa1-xN single crystal.
Hereinafter, referring to the accompanying drawings, an explanation of embodiments of the present invention will be made in detail. It should be understood that in describing the drawings, with the same reference marks being used for identical or equivalent features, reduplicating description will be omitted. Furthermore, the dimensional proportions in the drawings do not necessarily agree with what is described.
Reference is made to
Herein, while the mole ratios of the AlyGa1-yN seed crystal and the AlxGa1-xN single crystal that is grown may be the same (i.e., y=x) or may differ (i.e., y≠x), from the perspective of reducing stress that occurs within the crystal during growth of the AlxGa1-xN single crystal, it is preferable that the difference in mole ratios (i.e., |y−x|) be small, and it is more preferable that the mole ratios be the same (i.e., y=x).
Reference is made to
Furthermore, given the considerations discussed above, the thickness T (mm) of the AlyGa1-yN seed crystal preferably is less than 0.25 mm, more preferably is less than 0.2 mm, and still more preferably is less than 0.15 mm. Likewise, from the viewpoint of ease of handling, the thickness T (mm) of the AlyGa1-yN seed crystal preferably is 0.01 mm or greater, and more preferably is 0.05 mm or greater.
There are no particular limitations on the step of preparing the AlyGa1-yN seed crystal; a vapor-phase technique such as sublimation growth, or a liquid-phase technique such as solution growth (including flux growth) can be employed to grow bulk crystal, and then the bulk crystal can be processed in such a way that the crystal diameter D (mm) and thickness T (mm) satisfy the relation T<0.003D+0.15.
And from the perspective of reducing dislocations and like defects within the AlyGa1-yN seed crystal, as well as warpage and cracking, preferably a material is prepared as the seed crystal in which crystal nuclei for the AlyGa1-yN seed crystal are created by sublimation growth, and the crystal nuclei are grown. In addition, from the perspective of reducing dislocations within the seed crystal and reducing dislocation and like defects in the AlxGa1-xN single crystal that is grown, the geometry of the AlyGa1-yN seed crystal obtained by growing the crystal nuclei preferably satisfies the relation D≧3 for crystal diameter D (mm) and thickness T (mm), and more preferably satisfies the relation T<0.003D+0.15.
Fig. is again referred to. An AlxGa1-xN single crystal growth method of the present embodying mode is provided with a step of growing AlxGa1-xN single crystal 5 onto a major surface 4m of the AlyGa1-yN seed crystal 4 by sublimation growth. Growing AlxGa1-xN single crystal onto the major surface of such AlyGa1-yN seed crystal enables the alleviation of stress developing within the AlxGa1-xN single crystal, stopping occurrence of dislocations and like defects, as well as warping and cracks, to yield large-scale, high-quality AlxGa1-xN single crystal.
The sublimation technique is classified by the following two categories of crystal growth. One category, with reference to
The other category, with reference to
For the crystal growth in the sublimation (on-template-crystal crystal growth category and crystal-nuclei growth category), a vertical sublimation furnace 10, as represented in
In a method of growing AlxGa1-xN single crystal in the present embodying mode, the step of growing AlxGa1-xN single crystal 5 onto the major surface 4m of the AlyGa1-yN seed crystal 4 is carried out for example as follows, with reference to
To begin with, AltGa1-tN source material 3 is stowed in the lower part of the crucible body 12q, and the AlyGa1-yN seed crystal 4 described earlier is arranged on the inner side of the crucible lid-plate 12p in such a way that the seed crystal's major surface 4m opposes the AltGa1-tN source material 3. Next, while N2 gas is flowed in the reaction chamber 11 interior, the RF heating coil 14 is employed to heat the heating element 13, whereby the temperature of the crucible 12 interior is ramped up, and by holding the temperature of the crucible 12 at the AltGa1-tN source material 3 higher than the temperature at the AlyGa1-yN seed crystal 4, AlxGa1-xN is sublimed from the AltGa1-tN source material 3 and the AlxGa1-xN re-hardens onto the major surface 4m of the AlyGa1-yN seed crystal 4 to grow AlxGa1-xN single crystal 5. Herein, the Al sublimation temperature and sublimation pressure, and the Ga sublimation temperature and sublimation pressure respectively differ. While the relationship between the atomic fraction t of Al in the AltGa1-tN source material and the atomic fraction x of Al in the AlxGa1-xN that is sublimed from the AltGa1-tN source material therefore varies depending upon the sublimation temperature, at a given sublimation temperature, a given relationship will hold.
Herein, throughout growth of the AlxGa1-xN single crystal 5, the temperature of the crucible 12 at the AltGa1-tN source material 3 (hereinafter, also referred to as the sublimation temperature) is made some 1600° C. to 2300° C., and by having the temperature of the crucible 12 at the AlyGa1-yN seed crystal 4 (hereinafter, also referred to as the crystal-growth temperature) be some 10° C. to 200° C. lower than the temperature at the AltGa1-tN source material 3 (the sublimation temperature), high-quality AlxGa1-xN single crystal 5 is obtained. Furthermore, also throughout the crystal growth, along the outside of the crucible 12 in the reaction chamber 11 interior, N2 gas is continually flowed in such a way that the gas partial pressure will be some 101.3 hPa to 1013 hPa, whereby mixing of impurities into the AlxGa1-xN single crystal 5 can be reduced.
It should be noted that, throughout elevation of the crucible 12 interior-area temperature, making the temperature of the region of the crucible 12 interior apart from the AltGa1-tN source material 3 higher than the temperature of the crucible 12 at the source material enables exhausting of impurities in the crucible 12 interior area via the ventilation port 12c, making it possible further to reduce mixing of impurities into the AlxGa1-xN single crystal 5.
The AlyGa1-yN seed crystal utilized in a method of manufacturing AlxGa1-xN single crystal in the present embodying mode preferably is AlyGa1-yN seed-crystal crystal nuclei created by sublimation, and those crystal nuclei having been grown (in other words, the crystal-nuclei growth category). By said sublimation growth, high-quality AlyGa1-yN seed crystal whose crystal diameter D (mm) and thickness T (mm) satisfy the relation T<0.003D+0.15 can be obtained.
With reference to
To begin with, AlsGa1-sN source material 2 is stowed in the lower part of the crucible body 12q, and the crucible lid-plate 12p is arranged so as to oppose the AlsGa1-sN source material 2. Next, with reference to
Herein, throughout growth of the AlyGa1-yN seed crystal, the temperature of the crucible 12 at the AlsGa1-sN source material 2 (the sublimation temperature) is made some 1600° C. to 2300° C., and by having the temperature of the crucible 12 at the crucible lid-plate 12p (the crystal-growth temperature) be some 10° C. to 200° C. lower than the temperature at the AlsGa1-sN source material 2 (the sublimation temperature), high-quality AlyGa1-yN seed crystal 4 is obtained. Furthermore, also throughout the crystal growth, along the outside of the crucible 12 in the reaction chamber 11 interior, N2 gas is continually flowed in such a way that the gas partial pressure will be some 101.3 hPa to 1013 hPa, whereby mixing of impurities into the AlyGa1-yN seed crystal 4 can be reduced.
It should be noted that, throughout elevation of the crucible 12 interior-area temperature, making the temperature of the region apart from the AlsGa1-sN source material 2 higher than the temperature of the crucible 12 at the source material enables elimination of impurities in the crucible 12 interior area via the ventilation port 12c, making it possible further to reduce mixing of impurities into the AlyGa1-yN seed crystal 4.
The AlyGa1-yN seed crystal 4 grown in the manner described above has, with reference to
Also, the AlyGa1-yN seed crystal utilized in a method of manufacturing AlxGa1-xN single crystal in the present embodying mode may be AlyGa1-yN seed crystal grown onto a major surface of a template crystal by sublimation growth (i.e., the on-template-crystal crystal growth category). With reference to
To begin with, an AlsGa1-sN source material 2 is stowed the lower part of the crucible body 12q, and an SiC crystal, Al2O3 crystal, Si crystal, Ga crystal, GaN crystal, ZnO crystal or like template crystal 1 of crystal diameter D mm is arranged on the inner side of the crucible lid-plate 12p in such a way that the seed crystal's major surface 1m opposes the AlsGa1-sN source material 2.
Next, while N2 gas is flowed in the reaction chamber 11 interior, the RF heating coil 14 is employed to heat the heating element 13, whereby the temperature of the crucible 12 interior is ramped up, and by holding the temperature of the crucible 12 at the AlsGa1-sN source material 2 higher than the temperature along the template crystal 1, AlyGa1-yN is sublimed from the AlsGa1-sN source material 2 and the AlyGa1-yN re-hardens onto the major surface 1m of the template crystal 1 to grow AlyGa1-yN seed crystal 4. Herein, the Al sublimation temperature and sublimation pressure, and the Ga sublimation temperature and sublimation pressure respectively differ. While the relationship between the atomic fraction of Al in the AlsGa1-sN source material and the atomic fraction y of Al in the AlyGa1-yN that is sublimed from the AlsGa1-sN source material therefore varies depending upon the sublimation temperature, at a given sublimation temperature, a given relationship will hold.
Herein, throughout growth of the AlyGa1-yN seed crystal 4, the temperature of the crucible 12 at the AlsGa1-sN source material 2 (hereinafter also referred to as sublimation temperature) is made some 1600° C. to 2300° C., and by having the temperature of the crucible 12 along the template crystal 1 (hereinafter also referred to as crystal-growth temperature) be some 10° C. to 200° C. lower than the temperature at the AlsGa1-sN source material 2 (the sublimation temperature), high-quality AlyGa1-yN seed crystal 4 of crystal diameter D (mm) and thickness T0 (mm) is obtained. Furthermore, also throughout the crystal growth, along the outside of the crucible 12 in the reaction chamber 11 interior, N2 gas is continually flowed in such a way that the gas partial pressure will be some 101.3 hPa to 1013 hPa, whereby mixing of impurities into the AlyGa1-yN seed crystal 4 can be reduced.
It should be noted that, throughout elevation of the crucible 12 interior-area temperature, making the temperature of the region of the crucible 12 interior apart from the AlsGa1-sN source material 2 higher than the temperature of the crucible 12 at the source material enables exhausting of impurities in the crucible 12 interior area via the ventilation port 12c, making it possible further to reduce mixing of impurities into the AlyGa1-yN seed crystal 4.
By slicing the AlyGa1-yN seed crystal 4 of crystal diameter D (mm) and thickness T0 (mm), obtained as described above, along planes parallel to its major surface, and by polishing the surfaces where the crystal is sliced, an AlyGa1-yN seed crystal 4 whose crystal diameter D (mm) and thickness T (mm) (herein, T0>7) satisfy the relation T<0.003D+0.15 is obtained.
Herein, the AlyGa1-yN seed crystal 4 utilized in a method of growing AlxGa1-xN single crystal in the present embodying mode preferably has a (0001) face as the major surface. The AlyGa1-yN seed crystal having a (0001) face as the major surface facilitates growth of large-scale AlxGa1-xN single crystal onto the major surface of the AlyGa1-yN seed crystal. From the perspective of growing high-quality AlxGa1-xN single crystal both stably and efficiently, the AlxGa1-xN single crystal preferably is grown onto a (0001) Ga face of the AlyGa1-yN seed crystal.
It is also preferable that the AlyGa1-yN seed crystal 4 utilized in a method of growing AlxGa1-xN single crystal in the present embodying mode contain, in mass ratio, 10 ppm or more of at least one type of atoms among the Group IVB elements. Herein, AlyGa1-yN seed crystal containing 10 ppm (mass ratio) or more of at least one type of atoms among the Group IVB elements readily forms a single-crystal having a (0001) face as the major surface, having a hexagonal flat-platelike or other polygonal flat-platelike geometry, and whose crystal diameter D (mm) and thickness T (mm) satisfy the relation T<0.003D+0.15. Given such considerations, the inclusion ratio of the at least one type of atoms among the Group IVB elements preferably is 10 ppm or more, more preferably is 50 ppm or more, and still more preferably is 100 ppm or more. By the same token, because an excessive amount of impurities would proliferate defects within the crystal, from the perspective of curtailing an excessive amount of impurities, not greater than 5000 ppm is preferable, and not greater than 500 ppm is more preferable. A Group IVB atomic element herein means a Group IVB element in the long-form periodic table, and specifically refers to carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb).
Although there no particular restrictions on how the AlyGa1-yN seed crystal containing 10 ppm (mass ratio) or more of at least one type of atoms among the Group IVB elements is grown herein, it can be by growing a AlsGa1-sN source material 2 stowed into the crucible 12 together with a substance including at least one type of atoms among the Group IVB elements (hereinafter, IVB-element containing substance). Herein, the inclusion quantity of IVB-element containing substance with respect to the AlsGa1-sN source material 2 and the IVB-element-containing-substance total source material is made so that the IVB element—the IVB-element inclusion ratio with respect to the sum of the AlsGa1-sN and IVB element—preferably will be 50 ppm or greater, more preferably 500 ppm or greater.
Another preferable condition is that throughout growth of the AlyGa1-yN seed crystal, the temperature of the crucible 12 at the AlsGa1-sN source material 2 (the sublimation temperature) be 1800° C. to 2300° C. Meanwhile, the temperature of the crucible 12 at the crucible lid-plate 12p (the crystal-growth temperature) preferably is some 10° C. to 250° C. lower than the temperature at the AlsGa1-sN source material 2 (the sublimation temperature)—that is, the crystal-growth temperature preferably is 1550° C. to 2290° C.
Lastly, it is preferable that the diffraction-peak full-width at half-maximum in an x-ray diffraction rocking curve of the AlyGa1-yN seed crystal 4 utilized in a method of growing AlxGa1-xN single crystal in the present embodying mode be not greater than 150 arcsec, and more preferably, not greater than 50 arcsec. Also, the dislocation density of the AlyGa1-yN seed crystal 4 preferably is not greater than 1×106 cm−2. While the method of characterizing the dislocation density of the crystal herein is not particularly limited, it can be for example by determining the density of pits (the “EPD,” or etch-pit density) produced by carrying out an etching process on the surface of the crystal. Onto the major surface of high-quality AlyGa1-yN seed crystal whose diffraction-peak full-width at half-maximum in an x-ray diffraction rocking curve is not greater than 150 arcsec or whose dislocation density is not greater than 1×106 cm−2, high-quality AlxGa1-xN single crystal can be grown.
Reference is made to
Next, with reference to
Next, the temperature of the crucible 12 at the AlsGa1-sN source material 2 (sublimation temperature) was brought to 1700° C. and the temperature along the crucible lid-plate 12p (crystal-growth temperature), to 1600° C., to sublime AlN and Si from the source materials and, onto the (0001) Si face (major surface 1m) of the SiC template crystal 1 arranged on the inner side of the crucible lid-plate 12p, re-harden the AlN to grow AlN seed crystal (AlyGa1-yN seed crystal 4). During the growth of the AlN seed crystal (AlyGa1-yN seed crystal 4) as well, N2 gas was continually flowed along the outside of the crucible 12 in the reaction chamber 11 interior, and the amount of N2 gas introduced and the amount of N2 gas exhausted were controlled in such a way that the gas partial pressure along the outside of the crucible 12 in the reaction chamber 11 interior would be some 101.3 hPa to 1013 hPa. After AlN seed crystal (AlyGa1-yN seed crystal 4) was grown 80 hours under the crystal-growth conditions just described, it was cooled to room temperature (25° C.), and the crucible lid-plate 12p was taken off, whereupon an AlN seed crystal (AlyGa1-yN seed crystal 4) whose crystal diameter D was 40 mm and whose T0 thickness was 1 mm had been grown onto the (0001) Si face (major surface 1m) of the SiC template crystal 1.
Next the AlN seed crystal was sliced along planes parallel to its major surface, and the surfaces where the crystal was sliced were polished, to yield an AlN seed crystal (AlyGa1-yN seed crystal 4) whose crystal diameter D was 40 mm and whose thickness T was 0.21 mm. The inclusion ratio of Si (Group IVB atoms) in the AlN seed crystal was determined by secondary-ion mass spectroscopy (SIMS), whereat it was 80 ppm. The rocking curve in x-ray diffraction of the AlN seed crystal was determined, whereat the diffraction-peak full-width at half-maximum was 180 arcsec.
Reference is made to
Next, while N2 gas was flowed in the reaction chamber 11 interior, the RF heating coil 14 was employed to ramp up the temperature of the crucible 12 interior. Throughout elevation of the crucible 12 interior temperature, the temperature of the crucible 12 at the crucible lid-plate 12p was made higher than the temperature at the AltGa1-tN source material 3 to clean the surfaces of the crucible lid-plate 12p and the AlN seed crystal (AlyGa1-yN seed crystal 4) during the temperature elevation by etching it, and at the same time to eliminate via the ventilation port 12c impurities released from the crucible 12 interior area during the temperature elevation.
Next, the temperature of the crucible 12 at the AltGa1-tN source material 3 (sublimation temperature) was brought to 1900° C. and the temperature at the AlyGa1-yN seed crystal 4 (crystal-growth temperature), to 1800° C., to sublime AlN from the source material, and re-harden the AlN onto the AlN seed crystal (AlyGa1-yN seed crystal 4) in the upper part of the crucible 12 to grow AlN single crystal (AlxGa1-xN single crystal 5). During the growth of the AlN single crystal (AlxGa1-xN single crystal 5) as well, N2 gas was continually flowed along the outside of the crucible 12 in the reaction chamber 11 interior, and the amount of N2 gas introduced and the amount of N2 gas exhausted were controlled in such a way that the gas partial pressure along the outside of the crucible 12 in the reaction chamber 11 interior would be some 101.3 hPa to 1013 hPa. After AlN single crystal (AlxGa1-xN single crystal 5) was grown 30 hours under the crystal-growth conditions just described, it was cooled to room temperature (25° C.), and the crucible lid-plate 12p was taken off, whereupon an AlN single crystal (AlxGa1-xN single crystal 5) had been grown onto the major surface 4m of the AlN seed crystal (AlyGa1-yN seed crystal 4).
The size of the AlN single crystal (AlxGa1-xN single crystal 5) was 40 mm in crystal diameter and 4 mm in thickness. The rocking curve in x-ray diffraction of the AlN single crystal was determined, whereat the diffraction-peak full-width at half-maximum was a narrow 220 arcsec. Further, the dislocation density of the AlN single crystal was calculated from an EPD (etch-pit density) measurement, whereat it was a low 5×106 cm−2. In other words, the AlN single crystal of Embodiment 1 was of high quality. The results are tabulated in Table I.
In the same manner as in Embodiment 1, AlN seed crystal whose crystal diameter D was 40 mm and whose T0 thickness was 1 mm was grown. The AlN seed crystal was sliced along planes parallel to its major surface, and the surfaces where the crystal was sliced were polished, to yield an AlN seed crystal whose crystal diameter D was 40 mm and whose thickness T was 0.24 mm. The inclusion ratio of Si (Group IVB atoms) in the AlN seed crystal was 80 ppm. And the diffraction-peak full-width at half-maximum in an x-ray-diffraction rocking curve characterization of the AlN seed crystal was 180 arcsec.
Next, apart from utilizing the just-described AlN seed crystal (AlyGa1-yN seed crystal) of 40 mm crystal diameter D and 0.24 mm thickness T, AlN single crystal (AlxGa1-xN single crystal 5) was grown in the same manner as in Embodiment 1. The size of the obtained AlN single crystal was 40 mm in crystal diameter and 4 mm in thickness. The diffraction-peak full-width at half-maximum in an x-ray-diffraction rocking curve characterization of the AlN single crystal was a narrow 230 arcsec. Meanwhile, the dislocation density of the AlN single crystal was a low 6×106 cm−2. In other words, the AlN single crystal of Embodiment 2 was of high quality. The results are tabulated in Table I.
With the exception of employing an SiC template crystal whose crystal diameter was 20 mm, AlN seed crystal whose crystal diameter D was 20 mm and whose T0 thickness was 1 mm was grown in the same manner as in Embodiment 1. The AlN seed crystal was sliced along planes parallel to its major surface, and the surfaces where the crystal was sliced were polished, to yield an AlN seed crystal whose crystal diameter D was 20 mm and whose thickness T was 0.25 mm. The inclusion ratio of Si (Group IVB atoms) in the AlN seed crystal was 80 ppm. And the diffraction-peak full-width at half-maximum in an x-ray-diffraction rocking curve characterization of the AlN seed crystal was 160 arcsec.
Next, apart from using the just-described AlN seed crystal (AlyGa1-yN seed crystal) of 20 mm crystal diameter D and 0.25 mm thickness T, AlN single crystal (AlxGa1-xN single crystal 5) was grown in the same manner as in Embodiment 1. The size of the obtained AlN single crystal was 20 mm in crystal diameter and 4 mm in thickness. The diffraction-peak full-width at half-maximum in an x-ray-diffraction rocking curve characterization of the AlN single crystal was a large 350 arcsec. Meanwhile, the dislocation density of the AlN single crystal was a high 5×107 cm−2. In other words, the AlN single crystal of Embodiment 2 was of low quality. The results are tabulated in Table I.
With the exception of using only the powdered AlN (AlsGa1-sN source material 2) as a source material, AlN seed crystal whose crystal diameter D was 40 mm and whose T0 thickness was 1 mm was grown in the same manner as in Embodiment 1. The AlN seed crystal was sliced along planes parallel to its major surface, and the surfaces where the crystal was sliced were polished, to yield an AlN seed crystal whose crystal diameter D was 40 mm and whose thickness T was 0.32 mm. And the diffraction-peak full-width at half-maximum in an x-ray-diffraction rocking curve characterization of the AlN seed crystal was a large 280 arcsec.
Next, apart from using the just-described AlN seed crystal (AlyGa1-yN seed crystal) of 40 mm crystal diameter D and 0.32 mm thickness T, AlN single crystal (AlxGa1-xN single crystal 5) was grown in the same manner as in Embodiment 1. The size of the obtained AlN single crystal was 40 mm in crystal diameter and 4 mm in thickness. The diffraction-peak full-width at half-maximum in an x-ray-diffraction rocking curve characterization of the AlN single crystal was a large 460 arcsec. Meanwhile, the dislocation density of the AlN single crystal was a high 1×108 cm−2. In other words, the AlN single crystal of Comparative Example 2 was of low quality. The results are tabulated in Table I.
Reference is made to
Next, with reference to
Next, the temperature of the crucible 12 at the AlsGa1-sN source material 2 (sublimation temperature) was brought to 2200° C. and the temperature along the crucible lid-plate 12p (crystal-growth temperature), to 2150° C., to sublime AlN and Si from the source materials, and re-harden the AlN onto the crucible lid-plate 12p in the upper part of the crucible 12 to grow AlN seed crystal (AlyGa1-yN seed crystal 4). During the growth of the AlN seed crystal (AlyGa1-yN seed crystal 4) as well, N2 gas was continually flowed along the outside of the crucible 12 in the reaction chamber 11 interior, and the amount of N2 gas introduced and the amount of N2 gas exhausted were controlled in such a way that the gas partial pressure along the outside of the crucible 12 in the reaction chamber 11 interior would be some 101.3 hPa to 1013 hPa. After AlN seed crystal (AlyGa1-yN seed crystal 4) was grown 15 hours under the crystal-growth conditions just described, it was cooled to room temperature (25° C.), and the crucible lid-plate 12p was taken off, whereupon a plurality of hexagonal flat-platelike AlN seed crystals (AlyGa1-yN seed crystals 4) had been grown onto the inner side of the crucible lid-plate 12p.
The size of a single AlN seed crystal among the plurality AlN seed crystals (AlyGa1-yN seed crystals 4) just described was 25 mm in crystal diameter D and 0.16 mm in thickness T. The inclusion ratio of Si (Group IVB atoms) in the AlN seed crystal was 150 ppm. The diffraction-peak full-width at half-maximum in an x-ray-diffraction rocking curve characterization of the AlN seed crystal was a remarkably narrow 70 arcsec. In other words, the AlN seed crystal of Embodiment 3 was of tremendously high quality.
Next, apart from utilizing the just-described AlN seed crystal (AlyGa1-yN seed crystal) of 25 mm crystal diameter D and 0.16 mm thickness T, AlN single crystal (AlxGa1-xN single crystal 5) was grown in the same manner as in Embodiment 1. The size of the obtained AlN single crystal was 25 mm in crystal diameter and 4 mm in thickness. The diffraction-peak full-width at half-maximum in an x-ray-diffraction rocking curve characterization of the AlN single crystal was a remarkably narrow 70 arcsec. Meanwhile, the dislocation density of the AlN single crystal was a very low 6×105 cm−2. In other words, the AlN single crystal of Embodiment 3 was of tremendously high quality. The results are tabulated in Table I.
Apart from having the AlN seed crystal (AlyGa1-yN seed crystal) growth time be 10 hours, in the same manner as in Embodiment 3, a plurality of AlN seed crystals was grown. The size of a single AlN seed crystal among these AlN seed crystals was 14 mm in crystal diameter D and 0.18 mm in thickness T. The inclusion ratio of Si (Group IVB atoms) in the AlN seed crystal was 120 ppm. The diffraction-peak full-width at half-maximum in an x-ray-diffraction rocking curve characterization of the AlN seed crystal was a very narrow 80 arcsec. In other words, the AlN seed crystal of Embodiment 4 was of tremendously high quality.
Next, apart from utilizing the just-described AlN seed crystal (AlyGa1-yN seed crystal) of 14 mm crystal diameter D and 0.18 mm thickness T, AlN single crystal (AlxGa1-xN single crystal 5) was grown in the same manner as in Embodiment 1. The size of the obtained AlN single crystal was 14 mm in crystal diameter and 4 mm in thickness. The diffraction-peak full-width at half-maximum in an x-ray-diffraction rocking curve characterization of the AlN single crystal was a remarkably narrow 80 arcsec. Meanwhile, the dislocation density of the AlN single crystal was a very low 8×105 cm−2. In other words, the AlN single crystal of Embodiment 3 was of tremendously high quality. The results are tabulated in Table I.
Apart from using powdered carbon (C) of 400 ppm inclusion ratio as a Group IVB element within the source materials, and from having the AlN seed crystal (AlyGa1-yN seed crystal) growth time be 20 hours, in the same manner as in Embodiment 3, a plurality of AlN seed crystals was grown. The size of a single AlN seed crystal among these AlN seed crystals was 22 mm in crystal diameter D and 0.14 mm in thickness T. The inclusion ratio of C (Group IVB atoms) in the AlN seed crystal was determined by secondary-ion mass spectroscopy (SIMS), whereat it was 120 ppm. The diffraction-peak full-width at half-maximum in an x-ray-diffraction rocking curve characterization of the AlN seed crystal was an extremely narrow 25 arcsec. In other words, the AlN seed crystal of Embodiment 5 was of exceedingly high quality.
Next, apart from utilizing the just-described AlN seed crystal (AlyGa1-yN seed crystal) of 22 mm crystal diameter D and 0.14 mm thickness T, AlN single crystal (AlxGa1-xN single crystal 5) was grown in the same manner as in Embodiment 1. The size of the obtained AlN single crystal was 22 mm in crystal diameter and 4 mm in thickness. The diffraction-peak full-width at half-maximum in an x-ray-diffraction rocking curve characterization of the AlN single crystal was an extremely narrow 20 arcsec. Meanwhile, the dislocation density of the AlN single crystal was an extremely low 5×104 cm−2. In other words, the AlN single crystal of Embodiment 5 was of exceedingly high quality. The results are tabulated in Table I.
Apart from using powdered C of 600 ppm inclusion ratio as a Group IVB element within the source materials, and from having the AlN seed crystal (AlyGa1-yN seed crystal) growth time be 40 hours, in the same manner as in Embodiment 3, a plurality of AlN seed crystals was grown. The size of a single AlN seed crystal among these AlN seed crystals was 40 mm in crystal diameter D and 0.17 mm in thickness T. The inclusion ratio of C (Group IVB atoms) in the AlN seed crystal was 140 ppm. The diffraction-peak full-width at half-maximum in an x-ray-diffraction rocking curve characterization of the AlN seed crystal was an extremely narrow 20 arcsec. In other words, the AlN seed crystal of Embodiment 5 was of exceedingly high quality.
Next, apart from utilizing the just-described AlN seed crystal (AlyGa1-yN seed crystal) of 40 mm crystal diameter D and 0.17 mm thickness T, AlN single crystal (AlxGa1-xN single crystal) was grown in the same manner as in Embodiment 1. The size of the obtained AlN single crystal was 40 mm in crystal diameter and 4 mm in thickness. The diffraction-peak full-width at half-maximum in an x-ray-diffraction rocking curve characterization of the AlN single crystal was an extremely narrow 15 arcsec. Meanwhile, the dislocation density of the AlN single crystal was an extremely low 9×103 cm−2. In other words, the AlN single crystal of Embodiment 6 was of exceedingly high quality. The results are tabulated in Table I.
In addition, the relationship between the crystal diameter D (mm) and thickness T (mm) of the AlN seed crystal in Embodiment 1 through Embodiment 6 and Comparative Examples 1 and 2 in the foregoing Table I was plotted in
Reference is made to Table I and
Furthermore, compared with Embodiment 1 (E1) through Embodiment 4 (E4), for which the crystal diameter D (mm) and thickness T (mm) of the AlN seed crystal (AlyGa1-yN seed crystal) satisfied the relation 0.002D+0.1<T<0.003D+0.15, with Embodiment 5 (E5) and Embodiment 6 (E6), for which the crystal diameter D (mm) and thickness T (mm) of the AlN seed crystal (AlyGa1-yN seed crystal) satisfied the relation T<0.002D+0.1, still higher-quality AlN single crystals (AlxGa1-xN single crystals), wherein the diffraction-peak full-width at half-maximum in the x-ray-diffraction rocking curve characterizations was even narrower and the dislocation density was even lower, were obtained.
Meanwhile, in Embodiment 1 (E1) through Embodiment 4 (E4), for which the crystal diameter D (mm) and thickness T (mm) of the AlN seed crystal (AlyGa1-yN seed crystal) satisfied the relation 0.002D+0.1<T<0.003D+0.15, compared with Embodiment 1 (E1) and Embodiment 2 (E2), in which AlN seed crystal (AlyGa1-yN seed crystal) grown onto an SiC template crystal (template crystal) was utilized, with Embodiment 3 (E3) and Embodiment 4 (E4), in which AlN seed crystal wherein AlN-seed-crystal (AlyGa1-yN seed-crystal) crystal nuclei were created and the crystal nuclei were grown was utilized, even higher-quality AlN single crystals (AlxGa1-xN single crystals), wherein the diffraction-peak full-width at half-maximum in the x-ray-diffraction rocking curve characterizations was even narrower and the dislocation density was even lower, were obtained.
It should be understood that although in the foregoing embodiments and comparative examples an explanation of AlN seed crystal and AlN single crystal has been made, in respect also of AlyGa1-yN (0<y≦1) seed crystal and AlxGa1-xN (0<x≦1) single crystal, as long as Al is included as a constituent element of the crystal and the growth methods involving the present invention are applicable, similar results can of course be obtained.
The presently disclosed embodying modes and embodiment 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.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2008-021477 | Jan 2008 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2008/073365 | 12/24/2008 | WO | 00 | 7/30/2010 |
