RAMO4 monocrystalline substrate
10304740 ยท 2019-05-28
Assignee
Inventors
Cpc classification
H01L21/7813
ELECTRICITY
C30B25/186
CHEMISTRY; METALLURGY
International classification
H01L33/00
ELECTRICITY
C30B29/40
CHEMISTRY; METALLURGY
H01L21/02
ELECTRICITY
Abstract
An RAMO.sub.4 substrate that includes an RAMO.sub.4 monocrystalline substrate formed of a single crystal represented by general formula RAMO.sub.4, wherein R represents one or more trivalent elements selected from the group consisting of Sc, In, Y, and lanthanoid elements, A represents one or more trivalent elements selected from the group consisting of Fe(III), Ga, and Al, and M represents one or more divalent elements selected from the group consisting of Mg, Mn, Fe(II), Co, Cu, Zn, and Cd. The RAMO.sub.4 monocrystalline substrate has a principal surface with a plurality of grooves. The principal surface has an off-angle with respect to a cleaving surface of the single crystal. The RAMO.sub.4 monocrystalline substrate satisfies tan Wy/Wx, where Wx is the width at the top surface of a raised portion between the grooves, and Wy is the height of the raised portion.
Claims
1. A RAMO.sub.4 substrate comprising a RAMO.sub.4 monocrystalline substrate formed of a single crystal represented by a general formula RAMO.sub.4, wherein R represents one or more trivalent elements selected from a group consisting of Sc, In, Y, and a lanthanoid element, A represents one or more trivalent elements selected from a group consisting of Fe(III), Ga, and Al, M represents one or more divalent elements selected from a group consisting of Mg, Mn, Fe(II), Co, Cu, Zn, and Cd, and O represents Oxygen, the RAMO.sub.4 monocrystalline substrate having a principal surface with a plurality of grooves, the principal surface having an off-angle with respect to a cleaving surface of the single crystal, wherein is selected such that upon cleaving a group III nitride crystal formed on the RAMO.sub.4 substrate, the cleavage does not extend beyond the raised portions and detachment does not occur at non-grooved regions of the substrate.
2. The RAMO.sub.4 substrate according to claim 1, wherein a width Wx at a top surface of a raised portion between the grooves, a height Wy of the raised portion, and the off-angle satisfy 1 mWx360 m, 0.36 mWy1,000 m, and 0<20, respectively.
3. The RAMO.sub.4 substrate according to claim 1, wherein a width Wx at a top surface of a raised portion between the grooves, a height Wy of the raised portion, and the off-angle satisfy 16.6 mWx301.1 m, 0.88 mWy28.7 m, and 0<11.1, respectively.
4. The RAMO.sub.4 substrate according to claim 1, further comprising a group III nitride seed crystal layer on the top surface of the raised portion of the RAMO.sub.4 monocrystalline substrate.
5. The RAMO.sub.4 substrate according to claim 1, wherein, in the general formula, R is Sc, A is Al, and M is Mg.
6. The RAMO.sub.4 substrate according to claim 1, wherein the RAMO.sub.4 monocrystalline substrate satisfying tan Wy/Wx, wherein Wx is a width at a top surface of a raised portion between the grooves, and Wy is a height of the raised portion.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DESCRIPTION OF EMBODIMENTS
(15) An embodiment of the present disclosure is described below with reference to the accompanying drawings. The embodiment described is a ScAlMgO.sub.4 substrate as an exemplary example of an RAMO.sub.4 substrate.
(16) The following first describes the findings that led to the present disclosure. A ScAlMgO.sub.4 single crystal has a structure in which a rock salt (111) planar ScO.sub.2 layer, and a hexagonal (0001) planar AlMgO.sub.2 layer are alternately laminated. Two hexagonal (0001) planar layers are more planar than the wurtzite-form structure, and the vertical interlayer bond is longer than the in-plane bond by a length of about 0.03 nm, and is weaker than in-plane bonding. This allows the ScAlMgO.sub.4 single crystal to be cleaved at the (0001) plane. By taking advantage of this characteristic, a bulk material can be cut by cleavage to prepare a plate-shaped seed substrate (ScAlMgO.sub.4 monocrystalline substrate) for the production of, for example, a group III nitride crystal. When using such a seed substrate, the group III nitride crystal grown on the seed substrate (ScAlMgO.sub.4 monocrystalline substrate) can be separated from the seed substrate by taking advantage of the easily cleavable nature of the ScAlMgO.sub.4 single crystal.
(17) The following describes the challenges involved in the production of a group III nitride crystal using the ScAlMgO.sub.4 single crystal as a seed substrate.
(18) There are also cases where an off-angle is given to the ScAlMgO.sub.4 monocrystalline substrate. An off-angle is a small angle created by the cleaving surface ((0001) plane) and the epitaxial growth surface (the principal surface) of the ScAlMgO.sub.4 single crystal. For example, as shown in
(19) When the group III nitride crystal is epitaxially grown on the seed substrate ScAlMgO.sub.4 single crystal having an off-angle in the manner shown in
(20) Detachment at the cleaving surface with an off-angle also becomes a problem when reusing the ScAlMgO.sub.4 monocrystalline substrate. If naturally detached, the ScAlMgO.sub.4 monocrystalline substrates 32 and 42 should be reusable as seed substrates. When detachment occurs with =0 as shown in
(21) This becomes more problematic with large off-angles , or when the size of the group III nitride crystal becomes larger. For example, when =0.8, L=150 mm, and a=100 m in the ScAlMgO.sub.4 monocrystalline substrate 42 shown in
(22) The ScAlMgO.sub.4 substrate of the present embodiment addresses these drawbacks by disposing a plurality of grooves in the principal surface (epitaxial growth surface) of a ScAlMgO.sub.4 monocrystalline substrate. In the ScAlMgO.sub.4, group III nitride crystals form on the raised portions between the grooves of the ScAlMgO.sub.4 monocrystalline substrate. With the ScAlMgO.sub.4 substrate of the present embodiment, the ScAlMgO.sub.4 single crystal that remains on the group III nitride crystal can have a considerably smaller thickness when the group III nitride crystal is separated from the ScAlMgO.sub.4 substrate (ScAlMgO.sub.4 monocrystalline substrate) by cooling using the difference of the linear coefficients of expansion. This makes it possible to efficiently produce a quality group III nitride crystal that involves little residual stress.
(23) The ScAlMgO.sub.4 substrate of the present embodiment may be solely a ScAlMgO.sub.4 monocrystalline substrate 51, or may have a group III nitride seed crystal layer (hereinafter, also referred to as seed layer; will be described later) 71 on the raised portions between grooves of the ScAlMgO.sub.4 monocrystalline substrate 51.
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(25) As shown in
(26) The ScAlMgO.sub.4 monocrystalline substrate of the present embodiment has an off-angle . The off-angle , Wx, and Wy satisfy the following formula (1).
tan Wy/Wx(1)
(27) When the ScAlMgO.sub.4 monocrystalline substrate having an off-angle has periodic grooves (raised portions and recessed portions) satisfying the relation represented by the formula (1), the ScAlMgO.sub.4 monocrystalline substrate that remains on the group III nitride crystal after the group III nitride crystal is formed and detached can have a considerably small thickness. In the RAMO.sub.4 substrate of the present embodiment, stress is applied to the raised portions upon cooling the group III nitride crystal produced. Accordingly, the cleavage of the ScAlMgO.sub.4 monocrystalline substrate occurs at the raised portions. Here, when the raised portions are shaped to satisfy the formula (1), the cleavage does not extend beyond the raised portions, and detachment does not occur at the non-grooved regions (hereinafter, also referred to as base portion) of the ScAlMgO.sub.4 monocrystalline substrate. This makes it possible to minimize the detachment of the ScAlMgO.sub.4 monocrystalline substrate.
(28) Preferably, Wx, Wy, and satisfy 1 mWx360 m, 0.36 mWy1,000 m, and 0<20. Crystal planes of different orientations occur when the off-angle is excessively large. This tends to cause a mismatch at the interface, and the off-angle needs to be confined within the foregoing range. More preferably, 0.36 m Wy 100 m. The grooves can be formed by a quick laser process when Wy is 100 m or less. When Wy exceeds 100 m, variation may occur in Wx by the effect of the laser heat.
(29) Particularly, Wx, Wy, and the off-angle will preferably satisfy 16.6 mWx301.1 m, 0.88 mWy28.7 m, and 0<11.1, as will be described in the evaluation results below. With these ranges, the epitaxial growth of a group III nitride on the ScAlMgO.sub.4 monocrystalline substrate takes place more easily, and it becomes easier to obtain a substrate formed of a quality group III nitride crystal.
(30) A ScAlMgO.sub.4 monocrystalline substrate having a predetermined off-angle (9.3 in this example) was prepared, and the Wx, Wy, and off-angle of the ScAlMgO.sub.4 monocrystalline substrate, and the quality of the group III nitride crystal formed on the ScAlMgO.sub.4 monocrystalline substrate were confirmed. A plurality of straight-line grooves (raised portions and recessed portions), as shown in
(31) The groove shape was specified with a non-contact, optical three-dimensional measurement device, such as a Mitaka Kohki NH3-SP for example (measurement resolution for flat surface: 0.01 m, measurement resolution for height: 0.001 m). Specifically, the measurement surface was scanned in a 1-m pitch across the top surface of the raised portions, using a 50 times objective lens, and data regarding the shape of the raised and recessed portions were obtained.
(32) Separately, a plurality of ScAlMgO.sub.4 substrates was produced in the same manner as above, except that the off-angle , Wx, and Wy were varied as shown in the Table 1 below. Each ScAlMgO.sub.4 substrate was then observed to confirm the quality of the group III nitride crystal formed on the raised portions. The group III nitride crystal had high quality in all examples. That is, a substrate having improved quality can be obtained when Wx, Wy, and satisfy 16.6 mWx301.1 m, 0.88 mWy28.7 m, and 0<11.1, respectively.
(33) TABLE-US-00001 TABLE 1 Off-angle () tan Wx (m) Wy (m) Wy/Wx Example 1 Within 3.0 0.052 16.6 0.88 0.053 Example 2 Within 11.1 0.196 21.4 4.19 0.196 Example 3 Within 9.2 0.162 92.9 15.1 0.163 Example 4 Within 1.3 0.023 95.0 2.2 0.023 Example 5 Within 5.4 0.095 301.1 28.7 0.095
(34) The following describes an exemplary method of production of the ScAlMgO.sub.4 substrate having a straight-line structure (grooves) in planar view as shown in
(35) Thereafter, the ScAlMgO.sub.4 monocrystalline substrate 72, and the seed layer 71 are patterned. Specifically, as shown in
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(37) The following describes a method for producing a group III nitride crystal using the ScAlMgO.sub.4 substrate of the embodiment. The group III nitride crystal producing method is basically the same as the method described above (the method shown in
(38) The width of the grooves of the ScAlMgO.sub.4 substrate 70 is preferably 1 m or more and 1,000 m or less. When the groove width is too wide, the group III nitride crystals formed on the raised portions cannot easily join each other.
(39) The next step is a cooling process, which is performed to remove the group III nitride crystal 73. Here, the structure experiences internal stress due to the differences in the linear coefficients of expansion of the group III nitride crystal 73, the seed layer 71, and the ScAlMgO.sub.4 monocrystalline substrate 72. The ScAlMgO.sub.4 monocrystalline substrate 72 has desirable detachability at the (0001) plane and the base portion. With the grooves (irregularities), the break strength of the ScAlMgO.sub.4 monocrystalline substrate 72 under internal stress is the smallest at the raised portions. Accordingly, the ScAlMgO.sub.4 monocrystalline substrate 72 cleaves at the raised portions before cleavage occurs at the base portion of the ScAlMgO.sub.4 monocrystalline substrate 72. For example, when the ScAlMgO.sub.4 monocrystalline substrate 72 does not have an off-angle , the ScAlMgO.sub.4 monocrystalline substrate 72 naturally detaches itself at the raised portions, as shown in
(40) In the present embodiment, the principal surface (epitaxial growth surface) of the ScAlMgO.sub.4 monocrystalline substrate 72 has an off-angle . The following describes how detachment occurs at the cleaving surface of the ScAlMgO.sub.4 monocrystalline substrate 72 when it has an off-angle . On the ScAlMgO.sub.4 monocrystalline substrate 72 having an off-angle , crystals of group III nitride grow on the raised portions of the ScAlMgO.sub.4 substrate 70, and join each other to form a single sheet of group III nitride crystal 73 in the manner described above (
(41) Other
(42) The foregoing embodiment was described through the case where the RAMO.sub.4 substrate includes the ScAlMgO.sub.4 monocrystalline substrate. However, the disclosure is not limited to this. The monocrystalline substrate included in the RAMO.sub.4 substrate may be any substrate, as long as it is configured from a substantially monocrystalline material represented by general formula RAMO.sub.4. In the general formula, R represents one or more trivalent elements selected from Sc, In, Y, and lanthanoid elements (atomic numbers 67 to 71), A represents one or more trivalent elements selected from Fe(III), Ga, and Al, and M represents one or more divalent elements selected from Mg, Mn, Fe(II), Co, Cu, Zn, and Cd. As used herein, substantially monocrystalline material refers to a crystalline solid that contains at least 90 at % of a structure represented by RAMO.sub.4, and in which an arbitrarily chosen crystal axis has the same orientation in any part of the epitaxial growth surface. Materials with a locally different orientation of the crystal axis, and containing local lattice defects are also regarded as a single crystal. The symbol O means oxygen. R is particularly preferably Sc, M is particularly preferably Mg, and A is particularly preferably Al, as stated above.
(43) The type of the group III nitride crystal epitaxially grown on the RAMO.sub.4 substrate is not particularly limited. In the present disclosure, the group III nitride may be a secondary, a ternary, or a quaternary compound containing a group III element (Al, Ga, or In) and nitrogen, for example, a compound represented by general formula Al.sub.1xyGa.sub.yIn.sub.xN (wherein x and y satisfy 0x1, 0y1, and 01xy1). The group III nitride may contain p-type or n-type impurities. The seed layer may be any of the compounds above.
(44) For example, the group III element (Al, Ga, or In) may be replaced, at least in part, with elements such as boron (B), and thallium (Tl). The nitrogen (N) also may be replaced, at least in part, with elements such as phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi). The p-type impurity (acceptor) added to the group III nitride may be, for example, a known p-type impurity such as magnesium (Mg), and calcium (Ca). The n-type impurity (donor) may be, for example, a known n-type impurity such as silicon (Si), sulfur (S), selenium (Se), tellurium (Te), oxygen (O), and germanium (Ge). Two or more of the impurity elements (acceptor or donor) may be added at the same time. Crystals of such group III nitrides also can be produced in the manner described above. The foregoing different forms of the disclosure may be appropriately combined, and can exhibit their effects in combination.
(45) The disclosure is applicable to a seed substrate for crystal growth in white LEDs and semiconductor laser diodes used in applications such as lights, and headlights of automobiles.