RAMO4 SUBSTRATE AND NITRIDE SEMICONDUCTOR APPARATUS
20180342644 ยท 2018-11-29
Inventors
Cpc classification
C30B15/00
CHEMISTRY; METALLURGY
H01L21/0262
ELECTRICITY
C30B25/186
CHEMISTRY; METALLURGY
C30B25/183
CHEMISTRY; METALLURGY
International classification
H01L33/00
ELECTRICITY
H01L21/02
ELECTRICITY
Abstract
An RAMO.sub.4 substrate including 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 lanthanide elements, A represents one or more trivalent elements selected from a 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, in which a main plane of the RAMO.sub.4 substrate has an off-angle a tilted a with respect to an M-axis direction from a C-plane and 0.05|a|0.8 is satisfied.
Claims
1. An RAMO.sub.4 substrate comprising 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 lanthanide elements, 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, wherein a main plane of the RAMO.sub.4 substrate has an off-angle a tilted a with respect to an M-axis direction from a C-plane, and 0.05|a|0.8 is satisfied.
2. An RAMO.sub.4 substrate comprising 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 lanthanide elements, 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, wherein a main plane of the RAMO.sub.4 substrate has an off-angle b tilted b with respect to an A-axis direction from a C-plane, and 0.05|b|0.4 is satisfied.
3. The RAMO.sub.4 substrate according to claim 1, wherein the main plane of the RAMO.sub.4 substrate has an off-angle a tilted a with respect to the M-axis direction from the C-plane, and 0.05|a|0.8 is satisfied, and the main plane of the RAMO.sub.4 substrate has an off-angle b tilted b with respect to the A-axis direction from the C-plane, and 0.05|b|0.4 is satisfied.
4. The RAMO.sub.4 substrate according to claim 3, wherein the main plane of the RAMO.sub.4 substrate has the off-angle a and the off-angle b satisfying 0.2|a|0.6 and 0.1|b|0.4, respectively.
5. The RAMO.sub.4 substrate according to claim 2, wherein b0.4.
6. The RAMO.sub.4 substrate according to claim 1, wherein R is Sc, A is Al, and M is Mg in the general formula.
7. The RAMO.sub.4 substrate according to claim 2, wherein R is Sc, A is Al, and M is Mg in the general formula.
8. The RAMO.sub.4 substrate according to claim 1, wherein a group III nitride semiconductor is disposed on the main plane.
9. The RAMO.sub.4 substrate according to claim 8, wherein the group III nitride semiconductor is GaN.
10. The RAMO.sub.4 substrate according to claim 2, wherein a group III nitride semiconductor is disposed on the main plane.
11. The RAMO.sub.4 substrate according to claim 10, wherein the group III nitride semiconductor is GaN.
12. A group III nitride semiconductor apparatus comprising: the RAMO.sub.4 substrate according to claim 1, and a group III nitride semiconductor element disposed on the RAMO.sub.4 substrate.
13. A group III nitride semiconductor apparatus comprising: the RAMO.sub.4 substrate according to claim 2, and a group III nitride semiconductor element disposed on the RAMO.sub.4 substrate.
14. The group III nitride semiconductor apparatus according to claim 12, wherein the group III nitride semiconductor element is an optical device or electronic device.
15. The group III nitride semiconductor apparatus according to claim 13, wherein the group III nitride semiconductor element is an optical device or electronic device.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENTS
[0025] The RAMO.sub.4 substrate and a group III nitride semiconductor apparatus of the present disclosure will be now described, but the present disclosure is not limited to the following embodiments. A minus sign in a Miller index is represented by an overline on the numerical value in accompanying drawings, and is represented by a minus sign in the following description of the embodiments, for convenience of notation.
[0026] 1. RAMO.sub.4 Substrate
[0027] The RAMO.sub.4 substrate of the present disclosure is a substrate comprising a single crystal represented by the general formula RAMO.sub.4 (wherein R represents one or more trivalent elements selected from the group consisting of Sc, In, Y, and lanthanide elements (atomic number 67 to 71), 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), and the main plane thereof has an off-angle tilted with respect to an M-axis direction [1-100] and/or with respect to an A-axis direction [11-20], from a C-plane. In the present disclosure, RAMO.sub.4 substrates of which main plane has a different off-angle have been formed, and a group III nitride semiconductor has been epitaxially grown on each main plane. Then, the performance of the group III nitride semiconductor layers has been evaluated to find an off-angle and an off direction appropriate for the RAMO.sub.4 substrate. The RAMO.sub.4 substrate having an off-angle and an off-direction of the present disclosure is very useful as a hetero substrate for a high-quality group III nitride semiconductor. A ScAlMgO.sub.4 substrate, which is a typical example of the RAMO.sub.4 substrate, will be now described as an example, but the RAMO.sub.4 substrate of the present disclosure is not limited thereto.
Embodiment 1
[0028] The crystal structure of ScAlMgO.sub.4 is shown in
[0029] As aforementioned, in the ScAlMgO.sub.4 crystal, the step height, profile, and terrace width observed when an off-angle is provided are all different from those of substrate materials conventionally used, such as a GaN substrate and a sapphire substrate. Thus, the range of the off-angle appropriate for growing a group III nitride semiconductor is also different.
[0030] The ScAlMgO.sub.4 substrate of the present embodiment will be now described with reference to the accompanying drawings. A process flow of a production process of the ScAlMgO.sub.4 substrate is shown in
[0031] For example, in the single crystal preparation, a ScAlMgO.sub.4 single crystal ingot produced using a high frequency induction heating type Czochralski furnace is provided. As a method for producing an ingot, for example, Sc.sub.2O.sub.3, Al.sub.2O.sub.3, and MgO as the starting materials are blended at a predetermined molar ratio, placed in an iridium crucible having a diameter of 100 mm, and melted under heating. Next, a ScAlMgO.sub.4 single crystal cut out in the (0001) orientation is used as a seed crystal, which is lowered near the melt in the crucible. The seed crystal is then gradually lowered while rotated at a constant rotational speed. The tip of the seed crystal is brought into contact with the melt, and the seed crystal is raised at a pulling-up speed of 0.5 mm/h while the temperature is gradually lowered. That is, the crystal is grown by pulling it up in the C-axis direction ([0001] direction). After the crystal is pulled up to a desired length, the crystal is cut off from the melt and cooled. This can provide a single crystal ScAlMgO.sub.4 ingot having a diameter of 50 mm and a length of 50 mm.
[0032] Next, the capability of the ScAlMgO.sub.4 single crystal to be cleaved along the (0001) plane is utilized to divide the single crystal ScAlMgO.sub.4 ingot by cleavage into a substrate form (cleavage).
[0033] Subsequently, as off-angle formation, an irregularity profile having a height of 500 nm or more corresponding to the off-angle is formed on the ScAlMgO.sub.4 surface. Then, the applied pressure during polishing is reduced step-wisely to reduce the absolute value of the variation in the applied pressure during polishing. The irregularity profile is gradually reduced while internal cleavage is prevented to form an off-angle on the surface. In off-angle formation, the polishing direction is adjusted so as to bring the off-direction and the off-angle within a desired range.
[0034] One example of the off-angle formation is shown below. First, in processing an irregularity profile of 500 nm or more (irregularity formation), grinding is carried out using diamond fixed abrasive grains having a large abrasive grain size. As the abrasive grains, diamond abrasive grains having a grain size of #600 are used, for example. Use of the grains enables the height difference of the irregularities on the processed surface after grinding to be within 5 M or less. The processing conditions in the irregularity formation can include a grindstone rotation speed of 1,800 min.sup.1, a ScAlMgO.sub.4 substrate rotation speed of 100 min.sup.1, a processing speed of 0.3 mm/second, and an amount of removal by processing of around 20 m, for example. Then, gradually removing the irregularities formed in the irregularity formation is carried out (irregularity removal). In this case, by carrying out polishing with the applied pressure reduced step-wisely, irregularities having a height less than 500 nm can be formed while the irregularities having a height of 500 nm or more formed in the irregularity formation are removed. Specifically, polishing can be carried out using a slurry based on colloidal silica, for example, as the abrasive grains and a non-woven fabric pad as a polishing pad at a rotation speed of 60 min.sup.1 and an amount of slurry to be supplied of 0.5 ml/minute. In this case, reducing the applied pressure step-wisely from a range of around 15,000 Pa initially to a range of around 3,000 Pa in the end leads to formation of a step height and a terrace width depending on a desired off-angle. Reducing the applied pressure step-wisely in this manner enables the irregularities to be removed without causing an internal cleavage.
[0035] A micrograph of the surface of the ScAlMgO.sub.4 substrate according to the present embodiment photographed with an atomic force microscope (AFM) is shown in
[0036] Here, in
[0037] The ScAlMgO.sub.4 substrate of the present embodiment has an off-angle a but has no off-angle b. The off-angle of the ScAlMgO.sub.4 substrate according to the present embodiment obtained in
[0038] Here, in the present embodiment, the range of the off-angle a of the ScAlMgO.sub.4 substrate is preferably 0.05|a|0.8, more preferably 0.2a|0.6. Hereinbelow, the reason will be described.
[0039] The off-angle a of the ScAlMgO.sub.4 substrate of the present embodiment was evaluated by forming a group III nitride semiconductor layer on the ScAlMgO.sub.4 substrate. In the case of forming the group III nitride semiconductor layer, as shown in
[0040] Buffer layer 102 and group III nitride semiconductor layer 103 in
[0041] In
[0042] In
[0043] As aforementioned, considering the surface flatness and crystallinity of the GaN film, it is preferred to satisfy 0.05|a|0.8 when an off-angle a is provided. In the present embodiment, an investigation was made by using GaN as the group III nitride semiconductor and setting the growth temperature of the GaN to 1,125 C. In the case where AlGaInN is used as the group III nitride semiconductor or the like, the growth temperature is adjusted depending on the composition, and for example, a temperature around 700 to 1,170 C. will be the appropriate growth temperature. When the group III nitride semiconductor layer is grown at a low growth temperature of 700 C., for example, the diffusion length of the raw material is more suppressed compared with the case of a high temperature. Thus, when the off-angle a (a) becomes smaller than 0.2, that is, when the terrace width broadens, the raw material may not reach the step edge, nuclei may be formed on the terrace, and a surface having large grains as seen from
Embodiment 2
[0044] Subsequently, the ScAlMgO.sub.4 substrate of Embodiment 2 will be described. In the ScAlMgO.sub.4 substrate of the present embodiment, the main plane has an off-angle b (b) in a direction substantially parallel to the M-plane (1-100) from the C-plane (0001) plane but has no off-angle a, that is, the main plane has an off-angle b tilted b with respect to the A-axis direction [11-20] from the C-plane (0001). A method for producing a ScAlMgO.sub.4 substrate having such an off-angle b is the same as the method for producing a ScAlMgO.sub.4 substrate of Embodiment 1 aforementioned. However, in the aforementioned off-angle formation, the off-direction and the off-angle are adjusted.
[0045] The preferable range of the off-angle b in the ScAlMgO.sub.4 substrate of the present embodiment is 0.05|b|0.4, more preferably 0.1|b|0.4, still more preferably 0.1|b|0.4. Hereinbelow, the reason will be described.
[0046] As in Embodiment 1, a group III nitride semiconductor layer (GaN film) was epitaxially grown on the main plane of the ScAlMgO.sub.4 substrate by a MOCVD method. The epitaxial growth conditions were the same as in Embodiment 1 (thickness of buffer layer 102: 30 nm, thickness of group III nitride semiconductor layer 103: 2 m). In
Embodiment 3
[0047] Subsequently, the ScAlMgO.sub.4 substrate of Embodiment 3 will be described. In the ScAlMgO.sub.4 substrate of the present embodiment, the main plane is tilted a with respect to the M-axis direction and b with respect to the A-axis direction, from the C-plane (0001 plane). That is, the substrate includes the compound off-angle of the off-angle a and the off-angle b. A method for producing a ScAlMgO.sub.4 substrate having such an off-angle a and an off-angle b is the same as in Embodiment 1 aforementioned. However, in the aforementioned off-angle formation, the off-direction and the off-angle are adjusted.
[0048] In the ScAlMgO.sub.4 substrate of the present embodiment, the range of the off-angle a is preferably 0.05|a|0.8, more preferably 0.2|a|0.6. The range of the off-angle b is preferably 0.05|b|0.4, more preferably 0.1|b|0.4, still more preferably 0.1|a|<0.4. Hereinbelow, the reason will be described.
[0049] As in Embodiment 1, group III nitride semiconductor layer (GaN film) 103 was epitaxially grown on the main plane of the ScAlMgO.sub.4 substrate by a MOCVD method. The epitaxial growth conditions, film thickness and the like were the same as in Embodiment 1. The a and b investigated and surface morphology results are shown in the following Table 1.
[0050] The investigation was carried out on (a, b)=(0.1, 0.05), (0.1, 0.1), (0.2, 0.05), (0.2, 0.1), (0.4, 0.05), (0.4, 0.1), (0.6, 0.05), (0.6, 0.1), (0.8, 0.05), (0.8, 0.1), (1.2, 0.1), (0.05, 0.4), (0.1, 0.4), and (0.1, 0.6). The surface morphology of the GaN film obtained was also observed. The case where the surface morphology was satisfactory even if the epitaxial growth temperature was 700 to 1,170 C. is represented by A, the case where the surface morphology was slightly degraded at an epitaxial growth temperature of 700 C. or 1,170 C. but the surface morphology was satisfactory at 1,125 C. is represented by B, and the case where corrugated rough morphology was observed is represented by C. From Table 1, it was confirmed that a satisfactory GaN film can be obtained on a ScAlMgO.sub.4 substrate having an off-angle a and an off-angle b provided that the substrate had a compound off-angle within the range specified in Embodiments 1 and 2.
TABLE-US-00001 TABLE 1 a b () () Surface morphology 0.1 0.05 B 0.1 0.1 B 0.2 0.05 B 0.2 0.1 A 0.4 0.05 B 0.4 0.1 A 0.6 0.05 B 0.6 0.1 A 0.8 0.05 B 0.8 0.1 B 1.2 0.1 C 0.05 0.4 B 0.1 0.4 B 0.1 0.6 C
[0051] As shown in Table 1, no influence of magnitude relation between an off-angle a and an off-angle b was observed. This suggests that, in GaN growth on a ScAlMgO.sub.4 substrate having a compound off-angle, incorporation of adsorbed atoms into M-plane steps existing in the direction substantially perpendicular to the M-plane ((1-100) plane) from the C-plane ((0001) plane) is approximately equivalent to incorporation of adsorbed atoms into A-plane steps existing in the direction substantially parallel to the M-plane ((1-100) plane) from the C-plane ((0001) plane).
[0052] In
[0053] The results of
[0054] (Others)
[0055] In each of Embodiments 1 to 3 aforementioned, the performance of a ScAlMgO.sub.4 substrate was verified by forming a GaN film having a thickness of 2 m. When the thickness of a group III nitride semiconductor layer to be formed on the main plane of the ScAlMgO.sub.4 substrate is 1 m or more, the surface of the group III nitride semiconductor layer is flattened, and thus, a similar effect can be obtained. It is also possible to form a GaN thick film having a thickness of 0.1 mm or more on the main plane of the ScAlMgO.sub.4 substrate using an HVPE method or the like.
[0056] In Embodiments 1 to 3 aforementioned, the ScAlMgO.sub.4 substrate surface is subjected to whole-surface off-angle processing, and a group III nitride semiconductor is epitaxially grown thereon. After whole-surface off-angle processing is carried out, a partial region of the ScAlMgO.sub.4 substrate may be masked with SiNx or SiO.sub.2, an irregularity profile may be additionally processed on the ScAlMgO.sub.4 substrate, or the like. Even with such a substrate, when the main plane on which a group III nitride semiconductor layer is to be grown has been off-angle processed, it is possible to achieve a similar effect in the case where a group III nitride semiconductor is epitaxially grown.
[0057] In Embodiments 1 to 3 aforementioned, the group III nitride semiconductor layer has been formed by the MOCVD method. As the epitaxial growth method, any of an HYPE method, OVPE method, sputtering method, MBE method and the like may be used. One of these methods may be carried out singly or two or more of these may be used in combination. In any case, it is possible to achieve a similar effect as described above.
[0058] In Embodiments 1 to 3 aforementioned, of substrates comprising a single crystal represented by the general formula RAMO.sub.4, only the substrate obtained from a ScAlMgO.sub.4 single crystal has been described. The present disclosure is not limited thereto. The substrate of the present disclosure may be any substrates comprising a substantially single crystal material represented by the general formula RAMO.sub.4. The term substantially single crystal material refers to crystalline solid that contains 90 at % or more of RAMO.sub.4 constituting the main plane (epitaxial growth surface of the group III nitride semiconductor layer) and in which, when a crystal axis is focused on, the axis has the same orientation in any portion of the epitaxial growth surface. However, crystals in which the orientation of a crystal axis is locally altered and crystals including local lattice defects are also treated as single crystals. Note that O is oxygen. It is desirable that R be Sc, A be Al, and M be Mg.
[0059] The group III element metal constituting a group III nitride semiconductor to be formed on the RAMO.sub.4 substrate is most preferably gallium (Ga), but may be, for example, aluminum (Al), indium (In), thallium (Tl) or the like. One of these may be used singly or two or more of these may be used in combination. For example, as the group III element metal, at least one selected from the group consisting of aluminum (Al), gallium (Ga), and indium (In) may be used. In this case, the composition of the group III nitride semiconductor crystal to be produced is represented by Al.sub.sGa.sub.tIn.sub.{1(s+t)}N (wherein 0s1, 0t1, s+t1). The group III element metal may be subject to reaction in the presence of, for example, a dopant material or the like. Examples of the dopant include, but are not particularly limited to, monosilane (SiH.sub.4), germanium oxide (for example, Ge.sub.2O.sub.3, Ge.sub.2O, and the like), and cyclopentadienyl magnesium (CP2Mg).
[0060] 2. Group III Nitride Semiconductor Apparatus
[0061] A group III nitride semiconductor apparatus including the RAMO.sub.4 substrate aforementioned will be described. The group III nitride semiconductor apparatus may be a group III nitride semiconductor LED device as shown in
[0062] An LED device produced actually using the RAMO.sub.4 substrate (ScAlMgO.sub.4 substrate) described above will be now described. First, on ScAlMgO.sub.4 substrate 101 having an off-angle a and/or an off-angle b, buffer layer 102 was formed by a MOCVD method, and undoped GaN layer (group III nitride semiconductor layer) 103 was further formed by epitaxial growth. Furthermore, n-GaN layer (n-group III nitride semiconductor layer) 104, InGaN active layer 105, p-GaN layer (p-group III nitride semiconductor layer) 106, and p-contact layer 107 were sequentially layered. As Si raw material, which is a donor impurity, monosilane (SiH.sub.4) was used, and as Mg raw material, which is an acceptor impurity, cyclopentadienyl magnesium (CP2Mg) was used. The thicknesses of buffer layer 102 and undoped GaN layer 103 were set to 30 nm and 3 m, respectively. The thicknesses of n-GaN layer 104, p-GaN layer 106, and p-contact layer 107 were set to 3 m, 100 nm, and 50 nm, respectively. As InGaN active layer 105, an InGaN quantum well was used. Epitaxial growth was carried out by setting the growth temperature to 717 C. and the film thickness to 3 nm such that the emission wavelength was around 450 nm. On the produced LED device, n-electrode 108 was formed on n-GaN layer 104 and p-electrode 109 was formed on p-contact layer 107, respectively from the surfaces. The size of the LED was set to 0.8 mm.
[0063] The off-angles of ScAlMgO.sub.4 substrates 101 having an off-angle were (a, b)=(0.1, 0.1), (0.4, 0.1), (0.8, 0.1), (0.4, 0), and (0, 0.1). In
[0064] The performance of the group III nitride semiconductor apparatus was confirmed using an LED in the above, and laser diodes (LDs) can be similarly allowed to have higher performance using the RAMO.sub.4 substrate aforementioned. Electronic devices also can be allowed to have higher performance because it is possible to produce devices having a high-quality group III nitride semiconductor layer having a low dislocation density as shown in
INDUSTRIAL APPLICABILITY
[0065] The substrate having an off-angle according to the present disclosure can be produced as a hetero substrate which has a small lattice mismatch with a group III nitride semiconductor and with which a high-quality group III nitride semiconductor film can be produced. Production of a group III nitride device on the substrate enables a high-quality and high-performance group III nitride device to be provided.
REFERENCE SIGNS LIST
[0066] 101 RAMO.sub.4 (ScAlMgO.sub.4) substrate [0067] 102 Buffer layer [0068] 103 Group III nitride semiconductor layer (undoped GaN layer) [0069] 104 n-Group III nitride semiconductor layer (n-GaN layer) [0070] 105 InGaN active layer [0071] 106 p-Group III nitride semiconductor layer (p-GaN layer) [0072] 107 p-Contact layer [0073] 108 n-Electrode [0074] 109 p-Electrode