WO2010103674A1 - Iii族窒化物半導体素子、エピタキシャル基板、及びiii族窒化物半導体素子を作製する方法 - Google Patents
Iii族窒化物半導体素子、エピタキシャル基板、及びiii族窒化物半導体素子を作製する方法 Download PDFInfo
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- WO2010103674A1 WO2010103674A1 PCT/JP2009/058182 JP2009058182W WO2010103674A1 WO 2010103674 A1 WO2010103674 A1 WO 2010103674A1 JP 2009058182 W JP2009058182 W JP 2009058182W WO 2010103674 A1 WO2010103674 A1 WO 2010103674A1
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- gallium nitride
- layer
- based semiconductor
- nitride based
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 572
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 141
- 239000000758 substrate Substances 0.000 title claims description 69
- 238000000034 method Methods 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229910002601 GaN Inorganic materials 0.000 claims abstract description 411
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims abstract description 397
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 222
- 239000001301 oxygen Substances 0.000 claims abstract description 222
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 222
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 94
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims description 47
- 239000002994 raw material Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 28
- 229910021529 ammonia Inorganic materials 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 230000004888 barrier function Effects 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
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- 230000003287 optical effect Effects 0.000 abstract description 51
- 239000013078 crystal Substances 0.000 abstract description 32
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 26
- 238000005253 cladding Methods 0.000 description 25
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- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 238000001194 electroluminescence spectrum Methods 0.000 description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 6
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- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 5
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- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 238000007740 vapor deposition Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 238000000927 vapour-phase epitaxy Methods 0.000 description 2
- -1 InGaN Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- QBJCZLXULXFYCK-UHFFFAOYSA-N magnesium;cyclopenta-1,3-diene Chemical compound [Mg+2].C1C=CC=[C-]1.C1C=CC=[C-]1 QBJCZLXULXFYCK-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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- H01S5/34333—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser with a well layer based on Ga(In)N or Ga(In)P, e.g. blue laser
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Definitions
- the present invention relates to a group III nitride semiconductor device, an epitaxial substrate, and a method for manufacturing a group III nitride semiconductor device.
- Patent Document 1 describes n-type GaN having an n-type carrier proportional to the oxygen concentration. Oxygen is included in the source gas to epitaxially grow GaN on the GaAs substrate. The GaAs substrate is removed to obtain a GaN free-standing film.
- Patent Document 2 describes a method of growing a gallium nitride single crystal. According to this method, oxygen can be taken in as an n-type dopant.
- Patent Document 3 describes a method for producing a GaN-based compound semiconductor.
- the filling container is filled with ammonia for producing a GaN-based compound semiconductor so that at least a part thereof is liquid.
- the water concentration of ammonia in the liquid phase is 0.5 volppm or less as measured by Fourier transform infrared spectroscopy (FT-IR).
- FT-IR Fourier transform infrared spectroscopy
- JP 2000-044400 A JP 2002-373864 A JP 2004-363622 A
- the epitaxial film has an oxygen concentration used when an n-type GaN substrate is used, if considering that oxygen is an n-type dopant in a gallium nitride-based semiconductor, the electrical characteristics of the semiconductor device It is assumed that the change in characteristics cannot be ignored. For example, in a semiconductor optical device, it is estimated that the light emission efficiency and electrical characteristics of the device cannot be ignored depending on the oxygen doping amount in the n-type gallium nitride semiconductor layer, the light emitting layer, and the p-type gallium nitride semiconductor.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide a group III nitride semiconductor device including a gallium nitride-based semiconductor film having a good surface morphology.
- An object of the present invention is to provide a method for manufacturing a semiconductor device, and further to provide an epitaxial substrate including a gallium nitride based semiconductor film having a good surface morphology.
- a group III nitride semiconductor device includes (a) a group III nitride semiconductor, and is finite with respect to a reference plane orthogonal to a reference axis extending in the c-axis direction of the group III nitride semiconductor.
- a group III nitride semiconductor support having a principal surface forming an angle; and (b) an oxygen concentration of 5 ⁇ 10 16 cm ⁇ 3 to 5 ⁇ 10 18 cm ⁇ 3 , And a gallium nitride based semiconductor region provided on the main surface of the support.
- the main surface shows one of semipolar and nonpolar, and the gallium nitride based semiconductor region includes a first conductivity type gallium nitride based semiconductor layer.
- the gallium nitride based semiconductor region when the gallium nitride based semiconductor region is provided on a semipolar surface or a nonpolar surface and the gallium nitride based semiconductor region contains oxygen of 5 ⁇ 10 16 cm ⁇ 3 or more, The surface morphology of the gallium semiconductor region becomes flat. The surface of the gallium nitride based semiconductor region also exhibits semipolarity or nonpolarity depending on the semipolar surface or nonpolar surface of the main surface of the substrate. When the gallium nitride based semiconductor region contains oxygen exceeding the range of 5 ⁇ 10 18 cm ⁇ 3 or less, the crystal quality of the gallium nitride based semiconductor region is not good. Further, when the gallium nitride based semiconductor region contains oxygen of 1 ⁇ 10 17 cm ⁇ 3 or more, the surface morphology of the gallium nitride based semiconductor region is further flattened.
- a group III nitride semiconductor device comprises (a) a group III nitride semiconductor, and forms a finite angle with respect to a reference plane orthogonal to a reference axis extending in the c-axis direction of the group III nitride semiconductor.
- a group III nitride semiconductor support having a main surface; and (b) an oxygen concentration of 5 ⁇ 10 16 cm ⁇ 3 to 5 ⁇ 10 18 cm ⁇ 3 , A gallium nitride based semiconductor region provided on the main surface; (c) an active layer provided on the gallium nitride based semiconductor region; and (d) a second conductivity type gallium nitride provided on the active layer.
- a semiconductor layer is provided.
- the main surface indicates one of semipolar and nonpolar
- the gallium nitride based semiconductor region includes a first conductivity type gallium nitride based semiconductor layer
- the active layer includes the first conductivity type gallium nitride based.
- the gallium nitride based semiconductor region when the gallium nitride based semiconductor region is provided on a semipolar surface or a nonpolar surface and the gallium nitride based semiconductor region contains oxygen of 5 ⁇ 10 16 cm ⁇ 3 or more, The surface morphology of the gallium semiconductor region becomes flat. The surface of the gallium nitride based semiconductor region also exhibits semipolarity or nonpolarity depending on the semipolar surface or nonpolar surface of the main surface of the substrate. When the gallium nitride based semiconductor region contains oxygen exceeding the range of 5 ⁇ 10 18 cm ⁇ 3 or less, the crystal quality of the gallium nitride based semiconductor region is not good.
- the active layer can be provided on the first conductivity type gallium nitride semiconductor layer having a good surface morphology. Further, when the gallium nitride based semiconductor region contains oxygen of 1 ⁇ 10 17 cm ⁇ 3 or more, the surface morphology of the gallium nitride based semiconductor region is further flattened.
- the oxygen concentration in the active layer may be 5 ⁇ 10 16 cm ⁇ 3 or more. According to this group III nitride semiconductor device, the surface morphology of the active layer becomes flat when the active layer contains oxygen of 5 ⁇ 10 16 cm ⁇ 3 or more. In addition, since oxygen acts as a donor, when the active layer contains oxygen of 5 ⁇ 10 16 cm ⁇ 3 or more, there are effects that the driving voltage of the element is reduced and the piezoelectric field of the active layer is reduced. Furthermore, in the group III nitride semiconductor device according to one aspect of the present invention, the oxygen concentration in the active layer may be 1 ⁇ 10 17 cm ⁇ 3 or more. According to this group III nitride semiconductor device, when the active layer contains oxygen of 1 ⁇ 10 17 cm ⁇ 3 or more, the surface morphology of the active layer is further flattened.
- the oxygen concentration in the active layer may be 5 ⁇ 10 18 cm ⁇ 3 or less.
- the active layer contains oxygen exceeding the range of 5 ⁇ 10 18 cm ⁇ 3 or less, the crystal quality of the active layer is not good. Further, when the active layer contains oxygen exceeding the range of 5 ⁇ 10 18 cm ⁇ 3 or less, the optical loss due to free carrier absorption in the active layer increases.
- the oxygen concentration in the second conductivity type gallium nitride based semiconductor layer may be 5 ⁇ 10 16 cm ⁇ 3 or more.
- the oxygen concentration in the second conductivity type gallium nitride semiconductor layer may be 1 ⁇ 10 17 cm ⁇ 3 or more.
- the group III nitride semiconductor device when the oxygen concentration in the second conductivity type gallium nitride semiconductor layer contains oxygen of 1 ⁇ 10 17 cm ⁇ 3 or more, the surface morphology of the second conductivity type gallium nitride semiconductor layer is increased. Becomes even more flat.
- the oxygen concentration in the second conductivity type gallium nitride based semiconductor layer may be 5 ⁇ 10 18 cm ⁇ 3 or less. According to the group III nitride semiconductor device, when the oxygen concentration in the second conductivity type gallium nitride semiconductor layer exceeds the range of 5 ⁇ 10 18 cm ⁇ 3 or less and contains oxygen, the second conductivity type gallium nitride semiconductor The crystal quality of the layer is not good.
- the conductivity of the second conductivity type gallium nitride based semiconductor layer is not good.
- the carbon concentration of the first conductivity type gallium nitride based semiconductor layer is 5 ⁇ 10 18 cm ⁇ 3 or less
- the second conductivity type gallium nitride based semiconductor layer The carbon concentration of the active layer may be 5 ⁇ 10 18 cm ⁇ 3 or less
- the carbon concentration of the active layer may be 5 ⁇ 10 18 cm ⁇ 3 or less. According to this group III nitride semiconductor device, a stable c-plane facet is likely to appear when the carbon concentration inevitably taken into the gallium nitride semiconductor during growth is high.
- the carbon concentration here excludes contamination formed on the surface after the growth of the gallium nitride semiconductor.
- the group III nitride semiconductor device may further include another second conductivity type gallium nitride based semiconductor layer.
- the band gap of the second conductivity type gallium nitride based semiconductor layer is larger than the band gap of the other second conductivity type gallium nitride based semiconductor layer, and the oxygen concentration of the second conductivity type gallium nitride based semiconductor layer depends on the activity.
- the second conductivity type gallium nitride based semiconductor layer is provided between the other second conductivity type gallium nitride based semiconductor layer and the active layer, and the second conductivity type gallium nitride based semiconductor layer is larger than the oxygen concentration of the layer.
- the gallium semiconductor layer forms a junction with the other second conductivity type gallium nitride semiconductor layer.
- the second conductivity type gallium nitride semiconductor layer since the oxygen concentration of the second conductivity type gallium nitride semiconductor layer is higher than the oxygen concentration of the active layer, the second conductivity type is different from the second conductivity type gallium nitride semiconductor layer.
- the junction surface with the gallium nitride based semiconductor layer becomes flat, and therefore the scattering loss at this interface is reduced.
- the group III nitride semiconductor device may further include a light guide layer made of a gallium nitride semiconductor provided between the active layer and the second conductivity type gallium nitride semiconductor layer.
- the active layer extends along a plane inclined with respect to the reference plane, and the second conductivity type gallium nitride based semiconductor layer is an electron block layer.
- the active layer, the light guide layer, and the second conductivity type gallium nitride based semiconductor layer are provided on the semipolar plane and the nonpolar plane, and therefore the piezoelectric field in these semiconductor layers is c Smaller than the piezoelectric field in the semiconductor layer on the surface. Since carrier overflow hardly occurs on the main surface due to the small piezoelectric polarization, oxygen acting as a donor can be added to the p-type semiconductor layer to obtain a planarization effect. Therefore, in addition to the p-type semiconductor layer having a flat surface morphology due to oxygen addition, high carrier injection efficiency can be provided.
- the active layer includes well layers and barrier layers that are alternately arranged, and the oxygen concentration of the well layer may be 6 ⁇ 10 17 cm ⁇ 3 or less.
- the oxygen concentration in the active layer when the oxygen concentration in the active layer is high, the optical loss due to free carrier absorption increases. Since the oxygen concentration of the well layer is 6 ⁇ 10 17 cm ⁇ 3 or less, an effective optical loss can be avoided, and a decrease in luminous efficiency due to a decrease in crystal quality of the well layer can be avoided.
- an angle formed between the normal of the main surface and the reference axis may be 10 degrees or more and 170 degrees or less. According to this group III nitride semiconductor device, the contribution due to nonpolarity is appropriately exhibited. This nonpolarity represents semipolar and nonpolar.
- an angle formed between the normal line of the main surface and the reference axis is 10 degrees or more and 80 degrees or less, or the normal line of the main surface and the reference axis
- the angle formed by can be 100 degrees or more and 170 degrees or less. According to this group III nitride semiconductor element, the contribution by semipolarity or nonpolarity is appropriately exhibited.
- an angle formed between the normal line of the main surface and the reference axis is 63 degrees or more and 80 degrees or less, or the normal line of the main surface and the reference axis
- the angle formed by can be 100 degrees or more and 117 degrees or less.
- piezo polarization is particularly small when the off-angle is in the above range. Therefore, carrier overflow is unlikely to occur.
- the epitaxial wafer is made of (a) a group III nitride semiconductor, and a group III nitride having a main surface that forms a finite angle with respect to a reference plane orthogonal to a reference axis extending in the c-axis direction of the group III nitride semiconductor.
- a semiconductor substrate and (b) a first oxygen electrode having an oxygen concentration of 5 ⁇ 10 16 cm ⁇ 3 to 5 ⁇ 10 18 cm ⁇ 3 and provided on the main surface of the group III nitride semiconductor substrate.
- a conductive gallium nitride based semiconductor layer (c) a light emitting layer provided on the first conductive gallium nitride based semiconductor layer; and (d) a second conductive gallium nitride based semiconductor provided on the light emitting layer. And a layer.
- the main surface shows one of semipolar and nonpolar.
- the first conductivity type gallium nitride based semiconductor layer is provided on a semipolar surface or a nonpolar surface, and the first conductivity type gallium nitride based semiconductor layer contains oxygen of 5 ⁇ 10 16 cm ⁇ 3 or more.
- the surface morphology of the first conductivity type gallium nitride based semiconductor layer becomes flat.
- the light emitting layer can be provided on the first conductivity type gallium nitride based semiconductor layer having a good surface morphology.
- the surface of the first conductivity type gallium nitride based semiconductor layer also exhibits nonpolarity.
- the first conductivity type gallium nitride based semiconductor layer contains oxygen exceeding the range of 5 ⁇ 10 18 cm ⁇ 3 or less, the crystal quality of the first conductivity type gallium nitride based semiconductor layer is not good.
- the epitaxial wafer according to another aspect of the present invention may further include another second conductivity type gallium nitride based semiconductor layer.
- the band gap of the second conductivity type gallium nitride based semiconductor layer is larger than the band gap of the other second conductivity type gallium nitride based semiconductor layer, and the oxygen concentration of the second conductivity type gallium nitride based semiconductor layer is the light emission.
- the second conductivity type gallium nitride based semiconductor layer is provided between the second second conductivity type gallium nitride based semiconductor layer and the light emitting layer, and the second conductivity type gallium nitride based semiconductor layer is larger than the oxygen concentration of the layer.
- the gallium semiconductor layer forms a junction with the other second conductivity type gallium nitride semiconductor layer.
- the band gap of the second conductivity type gallium nitride semiconductor layer is larger than the band gap of another second conductivity type gallium nitride semiconductor layer, and the second conductivity type gallium nitride semiconductor layer is different. Since it is provided between the second conductivity type gallium nitride semiconductor layer and the light emitting layer, the second conductivity type gallium nitride semiconductor layer functions as an electron block layer, and another second conductivity type gallium nitride semiconductor layer is a cladding. Work as a layer.
- the flatness of the junction between the second conductivity type gallium nitride semiconductor layer and another second conductivity type gallium nitride semiconductor layer Is excellent. This flatness reduces light scattering by the interface between the second conductivity type gallium nitride semiconductor layer and another second conductivity type gallium nitride semiconductor layer.
- the oxygen concentration of the second conductivity type gallium nitride based semiconductor layer is 5 ⁇ 10 16 cm ⁇ 3 or more, and the oxygen concentration of the second conductivity type gallium nitride based semiconductor layer. Is 5 ⁇ 10 18 cm ⁇ 3 or less.
- the second conductivity type gallium nitride based semiconductor layer is an electron block layer
- the light emitting layer includes an active layer having well layers and barrier layers arranged alternately, and the light emitting layer is made of a gallium nitride based semiconductor.
- the light guide layer is further provided between the active layer and the second conductivity type gallium nitride based semiconductor layer, and the light guide layer of the light emitting layer is arranged with respect to the reference plane. It extends along an inclined plane.
- the second conductivity type gallium nitride based semiconductor layer may have an oxygen concentration of 1 ⁇ 10 17 cm ⁇ 3 or more.
- the piezo electric field in these semiconductor layers is a semiconductor on the c plane. Small compared to the piezoelectric field in the layer. From the viewpoint of carrier compensation, it is preferable not to add oxygen as a donor impurity to the p-type semiconductor layer, but carrier overflow is reduced on the main surface of the substrate due to small piezoelectric polarization due to a semipolar surface or a nonpolar surface. Therefore, although the oxygen concentration of the second conductivity type gallium nitride based semiconductor layer is 5 ⁇ 10 16 cm ⁇ 3 or more and 5 ⁇ 10 18 cm ⁇ 3 or less, it is possible to avoid a decrease in carrier injection efficiency.
- an angle formed between the normal line of the main surface and the reference axis is 10 degrees or more and 80 degrees or less, or a line formed between the normal line of the main surface and the reference axis.
- the angle can be not less than 100 degrees and not more than 170 degrees.
- an angle formed between a normal line of the main surface and the reference axis is 63 degrees or more and 80 degrees or less with respect to the reference plane, or a method of the main surface
- the angle formed by the line and the reference axis is not less than 100 degrees and not more than 117 degrees with respect to the reference plane.
- Yet another aspect of the present invention is a method of fabricating a group III nitride semiconductor device.
- This method includes (a) a step of preparing a group III nitride semiconductor substrate made of a group III nitride semiconductor and having a main surface, and (b) supplying a group III material and a nitrogen material to a growth reactor, Growing a first conductivity type gallium nitride based semiconductor layer having an oxygen concentration of 10 16 cm ⁇ 3 or more and 5 ⁇ 10 18 cm ⁇ 3 or less on the main surface of the group III nitride semiconductor substrate; (c) Supplying a Group III material and a nitrogen material to the growth furnace to grow a light emitting layer on the first conductivity type gallium nitride semiconductor layer; and (d) supplying a Group III material and a nitrogen material to the growth furnace.
- a step of growing a second conductivity type gallium nitride based semiconductor layer on the light emitting layer The main surface shows one of semipolar and nonpolar, and oxygen of the first conductivity type gallium nitride based semiconductor layer is provided as an impurity contained in at least one of the group III material and the nitrogen material
- the main surface of the group III nitride semiconductor substrate forms a finite angle with respect to a reference plane orthogonal to a reference axis extending in the c-axis direction of the group III nitride semiconductor.
- the gallium nitride semiconductor layer grown on the semipolar plane or the nonpolar plane contains oxygen of 5 ⁇ 10 16 cm ⁇ 3 or more
- the surface morphology of the gallium nitride semiconductor layer is flat. become.
- the c-plane does not appear on the surface of the first conductivity type gallium nitride semiconductor layer, and the surface of the gallium nitride semiconductor layer also exhibits a polarity corresponding to the main surface of the substrate.
- the gallium nitride based semiconductor layer grown on the semipolar plane contains oxygen exceeding the range of 5 ⁇ 10 18 cm ⁇ 3 or less, the crystal quality of the gallium nitride based semiconductor layer is not good.
- the light emitting layer can be grown on the first conductivity type gallium nitride based semiconductor layer having a good surface morphology. Further, when the gallium nitride based semiconductor layer contains oxygen of 1 ⁇ 10 17 cm ⁇ 3 or more, the surface morphology of the gallium nitride based semiconductor layer becomes flatter.
- the nitrogen material includes ammonia, and the nitrogen material includes water as an impurity.
- the oxygen concentration in the light emitting layer is 5 ⁇ 10 16 cm ⁇ 3 or more, the oxygen concentration in the light emitting layer is 5 ⁇ 10 18 cm ⁇ 3 or less, and the oxygen concentration in the second conductivity type gallium nitride based semiconductor layer is 5 ⁇ and the 10 16 cm -3 or more, the oxygen concentration in the second conductive type gallium nitride semiconductor layer is 5 ⁇ 10 18 cm -3 or less.
- the oxygen concentration of the second conductivity type gallium nitride based semiconductor layer is preferably higher than the oxygen concentration of the light emitting layer.
- the oxygen concentration in the light emitting layer may be 1 ⁇ 10 17 cm ⁇ 3 or more. Furthermore, in the method according to the present invention, the oxygen concentration in the light emitting layer is 5 ⁇ 10 18 cm ⁇ 3 or less, and the oxygen concentration in the second conductivity type gallium nitride based semiconductor layer is 1 ⁇ 10 17 cm ⁇ 3 or more. Can be. According to these methods, the surface morphology is further flattened.
- the growth temperature of the second conductivity type gallium nitride based semiconductor layer is preferably lower than the growth temperature of the first conductivity type gallium nitride based semiconductor layer. According to this method, since the growth temperature of the second conductivity type gallium nitride based semiconductor layer is lowered, the thermal stress on the light emitting layer is reduced.
- the light emitting layer may include an InAlGaN layer.
- the oxygen concentration can be adjusted by the aluminum composition, and an appropriate band gap can be obtained by adjusting the In composition.
- the light emitting layer may include an InGaN layer.
- ammonia having a water content of 500 ppb% or less can be used as the nitrogen raw material.
- ammonia having a water content of 50 ppb% or less can be used as the nitrogen raw material.
- ammonia having a water content of 1 ppb% or less can be used as the nitrogen material.
- the nitrogen raw material is supplied to the growth furnace.
- the nitrogen source may be made of ammonia.
- the moisture concentration of the nitrogen raw material may be 1 ppb% or less.
- a group III nitride semiconductor device including a gallium nitride-based semiconductor film having a good surface morphology can be provided. Further, according to another aspect of the present invention, a method for producing this group III nitride semiconductor device can be provided. Furthermore, according to still another aspect of the present invention, an epitaxial substrate including a gallium nitride based semiconductor film having a good surface morphology can be provided.
- FIG. 1 is a drawing schematically showing a group III nitride semiconductor optical device according to the present embodiment.
- FIG. 2 is a drawing schematically showing a group III nitride semiconductor optical device according to the present embodiment.
- FIG. 3 is a diagram showing band diagrams in the active layer, the light guide layer, and the p-type gallium nitride based semiconductor layer on the c-plane and the semipolar plane.
- FIG. 4 is a diagram showing products in main steps in the manufacturing method of the present embodiment.
- FIG. 5 is a diagram showing products in main steps in the manufacturing method of the present embodiment.
- FIG. 6 is a drawing showing products in main steps in the manufacturing method of the present embodiment.
- FIG. 7 is a diagram showing products in main steps in the manufacturing method of the present embodiment.
- FIG. 8 shows the semiconductor laser LD1 in the first embodiment.
- FIG. 9 is a drawing showing a differential interference microscope image representing the surface morphology of the p-type contact layer of the laser structure in the semiconductor laser LD1 and the semiconductor laser LDC1.
- FIG. 10 is a diagram showing a semiconductor laser LD2 in the second embodiment.
- FIG. 11 is a drawing showing EL spectra measured at an absolute temperature of 300 degrees and an absolute temperature of 10 degrees.
- FIG. 12 is a view showing a light emitting diode in Example 3.
- FIG. 13 is a drawing showing the structure of a laser diode in Example 4.
- FIG. 14 is a drawing showing surface morphology in the p-type contact layer of Example 4 and Comparative Example.
- FIG. 15 is a drawing showing the structure of a laser diode in Example 5.
- FIG. 16 is a diagram showing IV characteristics of laser diodes in Example 4 and its comparative example.
- FIG. 1 is a drawing schematically showing a group III nitride semiconductor optical device according to the present embodiment.
- the group III nitride semiconductor optical device shown in FIG. 1 has a structure applicable to, for example, a light emitting diode.
- the group III nitride semiconductor optical device 11 a includes a group III nitride semiconductor support 13, a gallium nitride based semiconductor region 15, an active layer 17, and a gallium nitride based semiconductor region 19.
- the group III nitride semiconductor support 13 is made of a group III nitride semiconductor such as GaN, InGaN, or AlGaN.
- Group III nitride semiconductor support 13 includes a main surface 13a and a back surface 13b. Main surface 13a of group III nitride semiconductor support 13 exhibits nonpolarity. This non-polarity represents either semipolar or nonpolar.
- the main surface 13a can be an a-plane or m-plane of a group III nitride semiconductor, or a by rotation about the c-axis. It can be a plane or a plane inclined from the m-plane.
- the group III nitride semiconductor support 13 has the semipolar main surface 13a
- the main surface 13a of the group III nitride semiconductor support 13 has a semipolarity inclined with respect to the reference plane Sc perpendicular to the reference axis Cx.
- the reference axis Cx extends in the c-axis direction of the group III nitride semiconductor.
- the reference plane Sc shows a typical c-plane, for example.
- the reference plane Sc is orthogonal to the c-axis vector VC, and the normal vector VN is shown on the main surface 13a.
- the c-axis vector VC forms an angle A off with respect to the normal vector VN. This angle A off is called an off angle with respect to the c-plane.
- a crystal coordinate system CR indicating a hexagonal crystal axis a-axis, m-axis and c-axis of a group III nitride semiconductor, and the c-plane in the hexagonal crystal is expressed as “(0001)”.
- the plane orientation expressed as “(000-1)” is opposite to the (0001) plane.
- the orthogonal coordinate system S indicates geometric coordinate axes X, Y, and Z.
- the direction of the inclination can be, for example, the a axis or the m axis.
- the gallium nitride based semiconductor region 15, the active layer 17, and the gallium nitride based semiconductor region 19 are arranged along the axis Ax on the nonpolar main surface.
- the angle formed between the normal vector VN of the main surface 13a and the reference axis Cx can be 10 degrees or more and 170 degrees or less with respect to the reference plane Sc.
- the gallium nitride based semiconductor region 15 is provided on the main surface 13a.
- the gallium nitride based semiconductor region 15 has an oxygen concentration of 5 ⁇ 10 16 cm ⁇ 3 or more and 5 ⁇ 10 18 cm ⁇ 3 or less.
- the oxygen concentration can be controlled by, for example, the impurity concentration in the raw material, the off-angle of the substrate, the growth temperature, the mixed crystal composition, and the like. Further, the oxygen concentration of the gallium nitride based semiconductor region 15 is more preferably 1 ⁇ 10 17 cm ⁇ 3 or more.
- the gallium nitride based semiconductor region 15 can include one or a plurality of gallium nitride based semiconductor layers.
- the gallium nitride based semiconductor region 15 includes a first conductivity type gallium nitride based semiconductor layer 21 and a gallium nitride based semiconductor layer 23.
- the gallium nitride based semiconductor layer 21 can be, for example, an n-type semiconductor layer, and the gallium nitride based semiconductor layer 23 can be, for example, a buffer layer.
- the first conductivity type gallium nitride based semiconductor layer 21 is made of, for example, an n-type gallium nitride based semiconductor, and an n-type dopant such as silicon is added to the n-type gallium nitride based semiconductor.
- the n-type gallium nitride based semiconductor can be made of, for example, GaN, AlGaN, InGaN, InAlGaN, or the like.
- the gallium nitride based semiconductor layer 23 is made of, for example, an undoped gallium nitride based semiconductor.
- the gallium nitride based semiconductor can be made of, for example, InGaN, InAlGaN, GaN, or the like.
- the gallium nitride based semiconductor layer 23 has an oxygen concentration of 5 ⁇ 10 16 cm ⁇ 3 or more, the crystal quality of the active layer 17 subsequently grown on the main surface of the gallium nitride based semiconductor layer 23 becomes good.
- the interface between the gallium nitride based semiconductor layer 23 and the gallium nitride based semiconductor grown on the main surface of the semiconductor layer is improved.
- the gallium nitride based semiconductor layer 23 has an oxygen concentration of 1 ⁇ 10 17 cm ⁇ 3 or more, the crystal quality of the active layer 17 subsequently grown on the main surface of the gallium nitride based semiconductor layer 23 is further improved. .
- the gallium nitride based semiconductor region 19 may include one or a plurality of gallium nitride based semiconductor layers.
- the gallium nitride based semiconductor region 19 includes the gallium nitride based semiconductor layer 25 and the second conductivity type gallium nitride based layer. It consists of a semiconductor layer 27.
- the gallium nitride based semiconductor layer 25 can be made of, for example, an undoped or p-type gallium nitride based semiconductor.
- the second conductivity type gallium nitride semiconductor layer 27 is made of, for example, a p-type gallium nitride semiconductor, and a p-type dopant such as magnesium is added to the p-type gallium nitride semiconductor.
- the p-type gallium nitride based semiconductor can be made of, for example, GaN, AlGaN, InAlGaN, InGaN, or the like.
- the second conductivity type gallium nitride based semiconductor layer 25 can be, for example, an electron block layer, and the gallium nitride based semiconductor layer 27 can be, for example, a p-type contact layer.
- An active layer 17 is provided between the gallium nitride based semiconductor layer 21 and the gallium nitride based semiconductor layer 27.
- the active layer 17 is provided on the gallium nitride based semiconductor region 15, and the gallium nitride based semiconductor region 19 is provided on the active layer 17.
- this group III nitride semiconductor optical device 11a when the gallium nitride based semiconductor region 15 is provided on the main surface 13a and the gallium nitride based semiconductor region 15 contains oxygen of 5 ⁇ 10 16 cm ⁇ 3 or more, nitriding is performed. The surface morphology of the main surface 15a of the gallium semiconductor region 15 becomes flat. Further, when the gallium nitride based semiconductor region 15 contains oxygen of 1 ⁇ 10 17 cm ⁇ 3 or more, the surface morphology of the main surface 15a becomes further flat.
- the c-face facet does not appear on the surface 15a of the gallium nitride based semiconductor region 15, and the entire surface 15a of the gallium nitride based semiconductor region 15 corresponds to the polar characteristics (semipolar and nonpolar) of the substrate main surface 13a. Shows the polarity characteristics.
- the gallium nitride based semiconductor region 15 contains oxygen exceeding the range of 5 ⁇ 10 18 cm ⁇ 3 or less, the crystal quality of the gallium nitride based semiconductor region 15 is not good.
- the active layer 17 can be provided on the gallium nitride semiconductor region 15 having a good surface morphology. Therefore, the interface 31a between the gallium nitride based semiconductor region 15 and the active layer 17 becomes flat.
- the addition of oxygen stabilizes the generation of the non-c plane. Therefore, in the growth of the gallium nitride based semiconductor region 15 on the main surface, crystal growth can be performed while maintaining the nonpolarity (either semipolar or nonpolar) of the growth surface. As a result, the surface morphology is improved.
- As an oxygen supply source intentional addition as a dopant is not excluded, but impurities in the source gas can be used by controlling the amount of impurities contained in the source gas. By controlling the amount of oxygen taken into the semipolar plane and the nonpolar plane, the surface morphology of the gallium nitride based semiconductor region that is the base of the active layer 17 can be flattened.
- the surface morphology of the active layer 17 becomes flat.
- the crystal quality of the active layer 17 is good.
- the active layer 17 of the group III nitride semiconductor optical device 11a may have a quantum well structure 29 including well layers 29a and barrier layers 29b arranged alternately.
- the well layer 29a can be made of, for example, GaN, AlGaN, InGaN, InAlGaN, or the like
- the barrier layer 29b can be made of, for example, GaN, AlGaN, InGaN, InAlGaN, or the like.
- the oxygen concentration of the well layer 29a of the active layer 17 can be 6 ⁇ 10 7 cm ⁇ 3 or less. When the oxygen concentration in the well layer 29a is high, optical loss due to free carrier absorption increases.
- the oxygen concentration of the well layer 29a is 6 ⁇ 10 7 cm ⁇ 3 or less, an optical loss can be avoided, and a decrease in luminous efficiency due to a decrease in crystal quality of the well layer 29a can be avoided. Further, when the oxygen concentration of the barrier layer 29b is equal to or higher than the oxygen concentration of the well layer 29a, the surface morphology of the barrier layer 29b is improved.
- the well layer 29a can be grown on the barrier layer 29b having a good surface morphology.
- the active layer 17 can include an InAlGaN layer, and this InAlGaN layer is used as the well layer 29a and / or the barrier layer 29b.
- the oxygen concentration can be adjusted by the aluminum composition, and an appropriate band gap can be obtained by adjusting the In composition.
- the active layer 17 can include an InGaN layer, and this InGaN layer is used as the well layer 29a and / or the barrier layer 29b.
- the band gap can be easily adjusted in the InGaN layer, and the oxygen concentration is adjusted according to the growth conditions such as the impurity concentration of the raw material and the growth temperature.
- the crystal quality of the second conductivity type gallium nitride semiconductor layers 25 and 27 that are continuously grown on the main surface of the active layer 17 becomes good. . Further, the interface between the active layer 17 and the gallium nitride based semiconductor grown on the main surface of the semiconductor layer becomes flat. Further, when the oxygen concentration of the active layer 17 is 1 ⁇ 10 17 cm ⁇ 3 or more, the crystal quality of the second conductivity type gallium nitride based semiconductor layers 25 and 27 and the above-described interface flatness are further improved.
- the gallium nitride based semiconductor layer 25 contains oxygen of 5 ⁇ 10 16 cm ⁇ 3 or more, the surface morphology of the gallium nitride based semiconductor layer 25 becomes flat. Further, when the gallium nitride based semiconductor layer 25 contains oxygen of 1 ⁇ 10 17 cm ⁇ 3 or more, the surface morphology of the gallium nitride based semiconductor layer 25 is further flattened.
- the oxygen concentration of the gallium nitride based semiconductor layer 25 can be 5 ⁇ 10 18 cm ⁇ 3 or less. An oxygen concentration exceeding 5 ⁇ 10 18 cm ⁇ 3 may deteriorate the crystal quality of the gallium nitride based semiconductor layer 25.
- the gallium nitride based semiconductor layer 27 contains oxygen of 5 ⁇ 10 16 cm ⁇ 3 or more, the surface morphology of the gallium nitride based semiconductor layer 27 becomes flat. Further, when the gallium nitride based semiconductor layer 27 contains oxygen of 1 ⁇ 10 17 cm ⁇ 3 or more, the surface morphology of the gallium nitride based semiconductor layer 27 becomes further flat.
- the oxygen concentration of the gallium nitride based semiconductor layer 27 can be 5 ⁇ 10 18 cm ⁇ 3 or less. An oxygen concentration exceeding 5 ⁇ 10 18 cm ⁇ 3 deteriorates the crystal quality of the gallium nitride based semiconductor layer 27.
- the surface morphology of the gallium nitride based semiconductor layer 25 becomes flat, so that the gallium nitride based semiconductor layer 27 formed thereon is flat.
- the crystal quality is excellent.
- the oxygen concentration of the gallium nitride based semiconductor layer 25 is smaller than the oxygen concentration of the gallium nitride based semiconductor layer 27, the influence of the compensation of p-type conduction by oxygen is reduced in the gallium nitride based semiconductor layer 25, and the carrier injection efficiency is excellent. become.
- the carbon concentration of the gallium nitride based semiconductor layers 21 and 23 is preferably 5 ⁇ 10 18 cm ⁇ 3 or less.
- the gallium nitride based semiconductor layers 25 and 27 may have a carbon concentration of 5 ⁇ 10 18 cm ⁇ 3 or less, and the active layer 17 may have a carbon concentration of 5 ⁇ 10 18 cm ⁇ 3 or less.
- carbon is supplied from an organic metal raw material. The carbon concentration can be controlled by the impurity concentration in the raw material, the raw material gas for doping carbon, the off-angle of the substrate, the growth temperature, the growth pressure, and the like.
- the band gap of the gallium nitride based semiconductor layer (for example, the electron block layer) 25 is larger than the band gap of the gallium nitride based semiconductor layer (for example, the p-type contact layer) 27.
- the gallium nitride based semiconductor layer 25 is provided between the gallium nitride based semiconductor layer 27 and the active layer 17.
- the gallium nitride based semiconductor layer 25 forms a junction 31b with the gallium nitride based semiconductor layer 27. Since the oxygen concentration of the gallium nitride based semiconductor layer 25 is higher than the oxygen concentration of the active layer 17, the junction surface 31b becomes flat.
- a first electrode (for example, an anode) 33 is provided on the gallium nitride based semiconductor layer 27. Since the gallium nitride based semiconductor layer 25 is provided on the flat bonding surface 31a, the gallium nitride based semiconductor layer 25 has good crystal quality. Hence, good contact characteristics are provided.
- the angle A off of the main surface 13a can be not less than 10 degrees and not more than 80 degrees with respect to the reference plane Sc.
- the angle A off of the main surface 13a can be 100 degrees or more and 170 degrees or less with respect to the reference plane Sc.
- a second electrode (for example, cathode) 35 is provided on the back surface 13 b of the support base 13.
- the main surface 13a can be a nonpolar surface. According to this group III nitride semiconductor optical device 11a, the contribution due to nonpolarity is appropriately exhibited.
- the active layer 17 and the gallium nitride based semiconductor layer 27 are provided on the main surface 13a. Is smaller than the piezoelectric field in the semiconductor layer on the c-plane. Since oxygen acts as a donor, it is preferable not to add it to the p-type semiconductor layer. However, addition of an appropriate range of oxygen provides good contact characteristics.
- the inclination angle A off can be not less than 63 degrees and not more than 80 degrees with respect to the reference plane Sc. Further, the angle A off may be 100 degrees or more and 117 degrees or less with respect to the reference plane A off . According to this group III nitride semiconductor optical device 11a, piezo polarization is particularly small when the off-angle is in the above range.
- FIG. 2 is a drawing schematically showing a group III nitride semiconductor optical device according to the present embodiment.
- the group III nitride semiconductor optical device shown in FIG. 2 has a structure applicable to, for example, a semiconductor laser.
- the group III nitride semiconductor optical device 11 b includes a group III nitride semiconductor support 13, a gallium nitride based semiconductor region 15, a light emitting layer 37, and a gallium nitride based semiconductor region 19.
- the light emitting layer 37 can include the active layer 17 and the first and second light guide layers 39 and 41.
- the active layer 17 is provided between the first light guide layer 39 and the second light guide layer 41.
- the light guide layers 39 and 41 are made of a gallium nitride based semiconductor, and the gallium nitride based semiconductor can be undoped, for example.
- the active layer 17, the light guide layers 39 and 41, and the gallium nitride based semiconductor layer 19 are provided on the semipolar surface and the nonpolar surface.
- the electric field is smaller than the piezoelectric field in the semiconductor layer on the c-plane. Since oxygen acts as a donor, it is preferable not to add it to the p-type semiconductor layer. However, carrier overflow hardly occurs on a semipolar surface or a nonpolar surface due to small piezoelectric polarization. Therefore, although the oxygen concentration is high, a decrease in carrier injection efficiency is suppressed.
- Each of the first and second light guide layers 39 and 41 preferably has an oxygen concentration of 5 ⁇ 10 16 cm ⁇ 3 or more based on the reasons already described.
- Each of the first and second light guide layers 39 and 41 may have an oxygen concentration of 5 ⁇ 10 18 cm ⁇ 3 or less based on the reason already described.
- the gallium nitride based semiconductor region 19 can include another second conductivity type gallium nitride based semiconductor layer 43 in addition to the gallium nitride based semiconductor layers 25 and 27.
- the gallium nitride based semiconductor layer 43 is made of, for example, a p-type gallium nitride based semiconductor, and a p-type dopant such as magnesium is added to the p-type gallium nitride based semiconductor.
- the p-type gallium nitride based semiconductor can be made of, for example, GaN, AlGaN, InAlGaN, or the like.
- the gallium nitride based semiconductor layer 43 can be, for example, a p-type cladding layer.
- the gallium nitride based semiconductor region 15 can include a gallium nitride based semiconductor layer 45.
- the gallium nitride semiconductor layer 45 is made of, for example, an n-type gallium nitride semiconductor, and an n-type dopant such as silicon is added to the n-type gallium nitride semiconductor.
- the n-type gallium nitride based semiconductor can be made of, for example, GaN, AlGaN, InAlGaN, or the like.
- the gallium nitride based semiconductor layer 45 can be, for example, an n-type cladding layer.
- a light emitting layer 37 is provided between the gallium nitride based semiconductor layer (for example, n-type cladding layer) 45 and the gallium nitride based semiconductor layer (for example, p-type cladding layer) 43.
- the refractive indexes of the gallium nitride based semiconductor layer 45 and the gallium nitride based semiconductor layer 43 are smaller than the refractive indexes of the light guide layers 39 and 41.
- the gallium nitride based semiconductor layer 45 and the gallium nitride based semiconductor layer 43 confine light in the light emitting layer 37.
- the band gap of the gallium nitride based semiconductor layer 25 is larger than the band gap of the gallium nitride based semiconductor layer 43.
- the gallium nitride based semiconductor layer 25 forms a junction 45a with the gallium nitride based semiconductor layer 43.
- the junction surface 45a becomes flat, and therefore, the scattering loss at the interface 45a is reduced.
- the light emitting layer 37 forms a junction 45 c with the gallium nitride based semiconductor region 19.
- the gallium nitride based semiconductor region 15 forms a light emitting layer 37 and a junction 45b. Since the oxygen concentration in the gallium nitride based semiconductor region 15 is higher than the oxygen concentration in the light emitting layer 37, the surface morphology of the gallium nitride based semiconductor region 15 is good and the junction 45b becomes flat. Therefore, the scattering loss at the interface 45b is reduced.
- an insulating film 47 for protection is provided on the gallium nitride based semiconductor layer 27.
- the insulating film 47 has a stripe-shaped opening 47a.
- a first electrode (for example, an anode) 49a is provided on the insulating film 47 and the opening 47a.
- a second electrode (for example, a cathode) 49b is provided on the back surface 13b of the support base 13. Since the gallium nitride based semiconductor layer 27 is provided on the flat morphological gallium nitride based semiconductor layer 43, the gallium nitride based semiconductor layer 27 has good crystal quality and provides good contact characteristics.
- the gallium nitride based semiconductor layer 43 forms a junction 45d with the gallium nitride based semiconductor layer 27. This joining surface 45d is flat.
- the group III nitride semiconductor optical device 11b has, for example, a gain guide type laser diode structure.
- the group III nitride semiconductor optical device 11b can have a pair of end faces 50a and 50b.
- the end faces 50a and 50b are preferably cleaved faces to form a resonator.
- Laser light L from group III nitride semiconductor optical device 11b is emitted from one of end faces 50a and 50b.
- An epitaxial structure of a light emitting device was fabricated by metal organic vapor phase epitaxy.
- Trimethylgallium (TMG), trimethylaluminum (TMA), trimethylindium (TMI), and ammonia (NH 3 ) were used as raw materials.
- Silane (SiH 4 ) and biscyclopentadienyl magnesium (CP 2 Mg) were used as dopant gases.
- a hexagonal semipolar gallium nitride substrate can be used as a group III nitride semiconductor substrate having a semipolar main surface.
- a hexagonal nonpolar gallium nitride substrate can be used as a group III nitride semiconductor substrate having a nonpolar main surface.
- oxygen as an n-type dopant is provided as an impurity contained in at least one of a group III material and a nitrogen material. The following description will be made with reference to a hexagonal semipolar gallium nitride substrate.
- a gallium nitride substrate was prepared as shown in part (a) of FIG.
- the main surface of the gallium nitride substrate is inclined at an angle of 10 to 80 degrees from the c-plane in the m-plane direction or the a-plane direction.
- the area of the main surface of the gallium nitride substrate is, for example, 25 square millimeters or more, and this size corresponds to, for example, a 5 millimeter square.
- the size of the main surface 51a of the gallium nitride substrate 51 is preferably 2 inches or more, for example.
- a source gas G1 containing a group III source and a nitrogen source is supplied to the growth reactor 10, and an n-type is formed on the main surface 51a of the GaN substrate 51.
- the gallium nitride based semiconductor region 53 is grown epitaxially.
- the source gas G1 includes, for example, TMG, TMA, NH 3 , SiH 4 .
- As the gallium nitride based semiconductor region 53 for example, a Si-doped AlGaN cladding layer is grown at a temperature of 1050 degrees Celsius. The thickness of this AlGaN layer is 2 ⁇ m, for example.
- the oxygen concentration of the gallium nitride based semiconductor region 53 is, for example, in the range of 5 ⁇ 10 16 cm ⁇ 3 to 5 ⁇ 10 18 cm ⁇ 3 . According to this method, when a gallium nitride-based semiconductor containing oxygen is grown on a semipolar plane, a specific facet plane that does not match the semipolar plane is suppressed from appearing during the growth. For this reason, the surface morphology becomes flat. Also in the subsequent growth, the addition of oxygen can suppress the appearance of a specific facet surface during the growth. Further, when the carbon concentration of the gallium nitride based semiconductor region 53 is 5 ⁇ 10 18 cm ⁇ 3 or less, generation of facets in the gallium nitride based semiconductor can be avoided. In addition, when the oxygen concentration of the gallium nitride based semiconductor region 53 is, for example, 1 ⁇ 10 17 cm ⁇ 3 or more, more flat surface morphology and facet surface suppression are provided.
- a source gas G2 containing a group III source and a nitrogen source is supplied to the growth reactor 10, An undoped InGaN optical guide layer 55a is grown epitaxially.
- the source gas G2 includes, for example, TMG, TMI, and NH 3 .
- the oxygen concentration of the InGaN light guide layer 55a is, for example, in the range of 5 ⁇ 10 16 cm ⁇ 3 to 5 ⁇ 10 18 cm ⁇ 3 .
- the thickness of the InGaN light guide layer 55a is 100 nm.
- the oxygen concentration of the InGaN light guide layer 55a is preferably 1 ⁇ 10 17 cm ⁇ 3 or more, for example.
- step S105 as shown in part (b) of FIG. 5, a source gas G3 containing a group III source and a nitrogen source is supplied to the growth reactor 10, and the GaN barrier layer 57 is formed at a substrate temperature of 840 degrees Celsius. It grows on the InGaN light guide layer 55a.
- the source gas G2 includes, for example, TMG and NH 3 .
- the thickness of the GaN layer 57 is, for example, 15 nm.
- a source gas G4 containing a group III source and a nitrogen source is supplied to the growth reactor 10, An undoped InGaN well layer 59 is epitaxially grown on the GaN barrier layer 57.
- the source gas G4 includes, for example, TMG, TMI, and NH 3 .
- the oxygen concentration of the InGaN well layer 59 is preferably 6 ⁇ 10 17 cm ⁇ 3 or less, for example.
- the thickness of the well layer 59 is 3 nm, for example.
- a GaN barrier layer 57 having a thickness of 15 nm is grown. If necessary, the growth of the barrier layer 57 and the growth of the well layer 59 are repeated. Further, in step S107, a source gas G5 containing a group III source and a nitrogen source is supplied to the growth reactor 10 at a substrate temperature of 840 degrees Celsius, and the undoped InGaN optical guide layer 55b is epitaxially formed in the same manner as the optical guide layer 55a. As shown in FIG. 6A, an active layer 61 and a light emitting layer 63 are produced. When the carbon concentration of the light emitting layer 63 is 5 ⁇ 10 18 cm ⁇ 3 or less, generation of facets can be avoided in the gallium nitride based semiconductor.
- a Group III material and a nitrogen material are supplied to the growth furnace to grow a second conductivity type gallium nitride based semiconductor region on the light emitting layer 63. Therefore, in step S108, after the substrate temperature is raised to 1000 degrees Celsius, a source gas G6 containing a group III source material and a nitrogen source material is introduced into the growth reactor 10, and as shown in FIG. Further, the electron block layer 65 is epitaxially grown on the light emitting layer 63.
- the source gas G6 contains, for example, TMG, TMA, NH 3 , CP 2 Mg.
- the thickness of the electron block layer 65 is 20 nm, for example.
- a source gas G7 containing a group III source and a nitrogen source is introduced into the growth reactor 10, and the p-type cladding layer is formed on the electron block layer 65 as shown in FIG. 67 is grown epitaxially.
- the source gas G7 includes, for example, TMG, TMA, NH 3 , CP 2 Mg.
- the thickness of the p-type cladding layer 67 is 400 nm, for example.
- a source gas G8 containing a group III source material and a nitrogen source material is introduced into the growth reactor 10, and a p-type contact is formed on the p-type cladding layer 67 as shown in FIG. Layer 69 is grown epitaxially.
- the source gas G8 includes, for example, TMG, NH 3 , CP 2 Mg.
- the thickness of the p-type contact layer 69 is, for example, 50 nm.
- the oxygen concentration of the gallium nitride based semiconductor layers 65, 67, and 69 is 5 ⁇ 10 16 cm ⁇ 3 or more, and the oxygen concentration of the gallium nitride based semiconductor layers 65, 67, and 69 is 5 ⁇ 10 18 cm ⁇ 3 or less. Further, the oxygen concentration can be 1 ⁇ 10 17 cm ⁇ 3 or more.
- the oxygen concentration of the gallium nitride based semiconductor layers 65, 67 and 69 is preferably larger than the oxygen concentration of the light emitting layer 63. Further, when the carbon concentration of the gallium nitride based semiconductor region 70 is 5 ⁇ 10 18 cm ⁇ 3 or less, generation of facets in the gallium nitride based semiconductor can be avoided.
- the morphology and oxygen doping of the light emitting layer and the n-type gallium nitride based semiconductor layer will be described. Since the growth temperature of the InGaN well layer is low and atoms are difficult to migrate, it tends to grow in an island shape. On the other hand, since the growth temperature of gallium nitride semiconductors such as n-type GaN and AlGaN is high, it is easy to obtain step flow growth. The effect of flattening the morphology by oxygen doping is different from the above-described growth modes such as islands and step flow growth. The semipolar plane is stabilized by oxygen doping.
- the c-plane is considered to be a stable surface in the gallium nitride crystal growth, and the c-plane is likely to be generated as a facet surface in the gallium nitride crystal growth on the semipolar plane.
- the generation of the c-plane deteriorates the morphology in the epitaxial growth on the semipolar plane. Oxygen doping can suppress the generation of facet planes that deteriorate morphology during epitaxial growth on a semipolar plane.
- the epitaxial substrate EP1 After the substrate temperature is lowered to room temperature, the epitaxial substrate EP1 is taken out from the growth furnace.
- the epitaxial substrate EP1 includes a group III nitride semiconductor substrate 51, a first conductivity type gallium nitride based semiconductor region 53, a light emitting layer 63, and a second conductivity type gallium nitride based semiconductor region 70.
- the gallium nitride based semiconductor regions 53 and 70 contain oxygen of 5 ⁇ 10 16 cm ⁇ 3 or more, the surface morphology of the gallium nitride based semiconductor regions 53 and 70 becomes flat.
- the c-plane does not appear on the surfaces of the gallium nitride based semiconductor regions 53 and 70, and the surfaces of the gallium nitride based semiconductor regions 53 and 70 are also semipolar.
- the gallium nitride based semiconductor regions 53 and 70 contain oxygen of 1 ⁇ 10 17 cm ⁇ 3 or more, the above technical contribution becomes excellent.
- the gallium nitride based semiconductor regions 53 and 70 contain oxygen exceeding the range of 5 ⁇ 10 18 cm ⁇ 3 or less, the crystal quality of the gallium nitride based semiconductor regions 53 and 70 is not good.
- the light emitting layer 63 can be provided on the gallium nitride based semiconductor region 53 having a good surface morphology.
- An anode electrode is formed on the p-type gallium nitride semiconductor region 70 of the epitaxial substrate EP1 to make an electrical connection to the p-type contact layer 69, and the back surface 51b of the substrate 51 is polished if necessary, and then the cathode is formed on the polished back surface.
- An electrode is formed. These electrodes are produced by vapor deposition, for example.
- the semiconductor region 53 is the thickest in the epitaxial film stack of the light emitting element. The contribution to is great. Since oxygen is an n-type dopant, carrier addition does not occur due to the addition of oxygen. When the oxygen concentration of the light emitting layer 63 is low, the light emission efficiency of the light emitting layer 63 is improved. Since the oxygen concentration is an n-type dopant, when the oxygen concentration of the p-type gallium nitride based semiconductor region 70 is low, the influence of carrier compensation due to the addition of oxygen is small.
- the morphology improvement of the light emitting layer 63 contributes to the improvement of the crystal quality of the p-type gallium nitride semiconductor region 70.
- the carrier concentration is high.
- the planarity is easily impaired by the addition of magnesium (Mg). Can be improved.
- the oxygen concentration of the light emitting layer 63 is low, the light emission efficiency of the light emitting layer 63 is improved.
- the growth temperature of the p-type gallium nitride based semiconductor region 70 is lowered to increase the oxygen concentration in the semiconductor region 70, thermal stress on the light emitting layer 63 is reduced.
- the planarity of the semiconductor region 70 can be improved by adding oxygen.
- the oxygen concentration is increased by increasing Al in the p-type gallium nitride based semiconductor region 70, the optical confinement in the laser diode is improved.
- the growth temperature of the p-type gallium nitride based semiconductor region 70 is lowered to increase the oxygen concentration in the semiconductor region 70, thermal stress on the light emitting layer 63 is reduced.
- Example 1 A laser diode LD1 was produced.
- a GaN substrate 71 having a semipolar principal surface inclined at an angle ⁇ 1 of 75 degrees in the m-axis direction was prepared. This semipolar principal surface corresponds to the (20-21) plane.
- ammonia (NH 3 ) and hydrogen (H 2 ) were supplied to the growth furnace to hold the GaN substrate 71 in an atmosphere of 1050 degrees Celsius. The retention time was 10 minutes.
- a raw material gas was supplied to the growth furnace to produce the following laser structure.
- an n-type Al0.04Ga0.96N cladding layer 72 was grown at 1050 degrees Celsius.
- the In 0.03 Ga 0.97 N optical guide layer 73a was grown.
- a quantum well active layer 74 was grown on the In 0.03 Ga 0.97 N optical guide layer 73a.
- an In 0.03 Ga 0.97 N optical guide layer 73b was grown on the active layer 74 at a substrate temperature of 840 degrees Celsius.
- an Al 0.12 Ga 0.88 N electron blocking layer 78, a p-type Al 0.06 Ga 0.94 N cladding layer 75, and a p-type GaN contact layer 76 were grown.
- the photoluminescence wavelength of this laser structure was in the 450 nm band.
- a cladding layer located directly above the GaN substrate 71 and having a large film thickness.
- the oxygen concentration of the cladding layer 72 was 3 ⁇ 10 17 cm ⁇ 3 .
- An anode is formed on the contact layer 76 through the opening of the insulating film 77, and a cathode is formed on the back surface 71b of the GaN substrate 71, so that the semiconductor laser LD1 shown in FIG.
- FIG. 9A shows the surface morphology of the p-type GaN contact layer of the laser structure in the semiconductor laser LD1.
- FIG. 9B the p-type contact layer of the laser structure in the semiconductor laser LD0 also shows the surface morphology.
- the p-type contact layer having a laser structure in the semiconductor laser LD0 exhibits good surface morphology.
- the semiconductor laser LD1 including the n-type AlGaN cladding layer having a high oxygen concentration it is considered that the semipolar plane is stabilized. By comparing these laser structures, the laser structure in the semiconductor laser LD1 showed a flatter morphology.
- Example 2 A laser diode was fabricated.
- a GaN substrate 81 having a semipolar principal surface inclined at an angle ⁇ 2 of 75 degrees in the m-axis direction was prepared. This semipolar principal surface corresponds to the (20-21) plane.
- ammonia (NH 3 ) and hydrogen (H 2 ) were supplied to the growth furnace to hold the GaN substrate 81 in an atmosphere of 1050 degrees Celsius. The retention time was 10 minutes.
- the source gas was supplied to the growth furnace to produce the following laser structure.
- an n-type Al 0.04 Ga 0.96 N cladding layer 82 was grown at 1050 degrees Celsius.
- an In 0.02 Ga 0.98 N optical guide layer 83a having a thickness of 100 nm was grown.
- a quantum well active layer 84 was grown on the light guide layer 83.
- an In 0.02 Ga 0.98 N optical guide layer 83b was grown on the active layer 84 at a substrate temperature of 840 degrees Celsius.
- an Al 0.12 Ga 0.88 N electron blocking layer 85, a p-type Al 0.06 Ga 0.94 N cladding layer 86, and a p-type GaN contact layer 87 were grown.
- the photoluminescence wavelength of this laser structure was in the 405 nm band.
- an anode 89 a was formed through a stripe window (width: 10 ⁇ m) of an insulating film (for example, SiO 2) 88 and a cathode 89 b was formed on the back surface 81 a of the GaN substrate 81. Thereafter, cleavage was performed on the a-plane at intervals of 800 ⁇ m to produce a gain guide type semiconductor laser LD2 shown in FIG.
- the oxygen concentration of the n-type cladding layer was 3 ⁇ 10 17 cm ⁇ 3 .
- the oxygen concentration of the quantum well active layer 84 was 2 ⁇ 10 17 cm ⁇ 3 .
- the oxygen concentration of the p-type electron blocking layer 85 was 1 ⁇ 10 18 cm ⁇ 3 .
- the oxygen concentration of the p-type cladding layer 86 was 7 ⁇ 10 17 cm ⁇ 3 . In this structure, the oxygen concentration of the p layer is higher than that of the light emitting layer.
- an LD structure was also fabricated on a c-plane GaN substrate under the same film formation conditions.
- the amount of oxygen taken into the GaN-based semiconductor was different, and the oxygen concentration was 1 ⁇ 10 17 cm ⁇ 3 or less in all epitaxial layers.
- cleavage at the m-plane was performed to manufacture a gain guide type semiconductor laser LDC2 having a resonator mirror.
- a current of 2 mA was applied to these semiconductor lasers LD2 and LDC2, and electroluminescence (EL) was measured at an absolute temperature of 300 degrees (300K) and an absolute temperature of 10 degrees (10K).
- Part (a) of FIG. 11 shows an EL spectrum measured at an absolute temperature of 300 degrees
- part (b) of FIG. 11 shows an EL spectrum measured at an absolute temperature of 10 degrees.
- EL spectra ELS (300) and ELS (10) were measured in the semiconductor laser LD2 of the example
- EL spectra ELC (300) and ELC (10) were measured in the semiconductor laser LDC2 of the comparative example.
- the EL spectra at temperatures 300K and 10K were compared.
- the EL spectra ELS (300) and ELC (300) of any of the semiconductor lasers LD2 and LDC2 have a peak due to MQW near 405 nm.
- the EL spectrum of the semiconductor laser LD2 of the example showed a single peak, but the semiconductor laser LDC2 of the comparative example has a donor-acceptor pair (DAP) in the p-type semiconductor layer in addition to the MQW peak.
- DAP donor-acceptor pair
- oxygen acting as a donor is doped in the p-type semiconductor layer at a higher concentration than the light emitting layer, but exhibits good carrier injection efficiency.
- the flatness of the p-type semiconductor layer is easily impaired by the addition of Mg.
- adding oxygen in the proper range provides both surface flatness and carrier injection efficiency. Improving the flatness of the p-type semiconductor layer and increasing the steepness of the interface of the electron block layer / cladding layer leads to a reduction in scattering loss of light propagating through the resonator of the semiconductor laser.
- Example 3 A light emitting diode was produced.
- a GaN substrate 91 having a semipolar principal surface inclined at an angle ⁇ 3 of 18 degrees in the a-axis direction was prepared. After the GaN substrate 91 was placed in the growth furnace, ammonia (NH 3 ) and hydrogen (H 2 ) were supplied to the growth furnace to hold the GaN substrate 91 in an atmosphere of 1050 degrees Celsius. The retention time was 10 minutes. After this thermal cleaning, a source gas was supplied to the growth furnace to produce the following light emitting diode structure. First, an n-type GaN layer 92 having a thickness of 2 ⁇ m was grown at 1050 degrees Celsius.
- the In 0.04 Ga 0.96 N buffer layer 93 was grown.
- a quantum well active layer 94 was grown on the buffer layer 93 having a thickness of 100 nm. Specifically, a GaN barrier layer 94a having a thickness of 15 nm is grown at a substrate temperature of 840 degrees Celsius and an InAlGaN well layer 94b having a thickness of 3 nm is grown at a substrate temperature of 700 degrees Celsius to form an active layer 94. .
- a p-type Al 0.18 Ga 0.82 N electron blocking layer 95 having a thickness of 20 nm and a p-type GaN contact layer 96 having a thickness of 50 nm were grown on the active layer 94.
- An anode (Ni / Au) 97 and a pad electrode 99a were formed on the contact layer 96, and a cathode (Ti / Al) was formed on the back surface 91b of the substrate 91 to produce the light emitting diode LED1 shown in FIG.
- Light emitting diode structures having InAlGaN well layers with different indium compositions were fabricated. The relationship between the oxygen concentration in the well layer and the light output was investigated.
- LED structure In composition, Al composition, oxygen concentration (cm ⁇ 3), light output LED1: 0.18, 0, 2 ⁇ 10 17 , 1 LED2: 0.19, 0.03, 4 ⁇ 10 17 , 0.85 LED3: 0.20, 0.06, 1 ⁇ 10 18 , 0.54.
- the In composition of the well layer was changed so as to obtain an emission wavelength near 450 nm. As the oxygen concentration in the well layer increased, the light emission output decreased. This is considered that the addition of oxygen deteriorates the crystal quality of the well layer.
- the oxygen concentration in the well layer was controlled by taking advantage of the fact that Al in the well layer easily adsorbs oxygen and that oxygen adsorbed at a low temperature (a temperature at which In is taken into the well layer) is difficult to desorb.
- Example 4 A GaN substrate having an m-plane principal surface was prepared.
- a laser diode LD3 was fabricated on the GaN substrate.
- FIG. 13 is a drawing showing the structure of a laser diode in Example 4. After the GaN substrate 101 is placed in the growth furnace, ammonia (NH 3 ) and hydrogen (H 2 ) are supplied to the growth furnace and thermal cleaning is performed in an atmosphere of 1050 degrees Celsius, and then the same as in Example 1. The following laser structure was fabricated on the nonpolar main surface 101a of the GaN substrate 101.
- NH 3 ammonia
- H 2 hydrogen
- Al 0.04 Ga 0.96 N clad layer 102 n-type, 2 ⁇ m, In 0.03 Ga 0.97 N light guide layer 103a: undoped, 100 nm, Active layer 104: In 0.18 Ga 0.82 N well layer (thickness 3 nm) / GaN barrier layer (thickness 15 nm), In 0.03 Ga 0.97 N light guide layer 103b: undoped, 100 nm, Al 0.12 Ga 0.88 N electron blocking layer 105: p-type, 20 nm, Al 0.06 Ga 0.94 N clad layer 106: p-type, 400 nm, GaN contact layer 107: p-type, 50 nm.
- An anode 109 a was formed on the insulating film (for example, SiO 2 ) 108 having a stripe window (width 10 ⁇ m) and the contact layer 107, and a cathode 109 b was formed on the back surface 101 b of the GaN substrate 101. Thereafter, a gain guide type semiconductor laser LD3 was fabricated by cleavage.
- the insulating film for example, SiO 2
- a cathode 109 b was formed on the back surface 101 b of the GaN substrate 101.
- FIG. 14 is a drawing showing the surface morphology of the p-type contact layer 107 of Example 4 and the p-type contact layer of the comparative example.
- the surface of the p-type contact layer shown in FIG. 14 (a) is compared with the surface of the p-type contact layer shown in FIG. 14 (b), the surface of the epitaxial film of Example 4 is relatively flat. The morphology was shown.
- Example 4 it is considered that there is an effect of stabilization by oxygen even on a nonpolar surface.
- FIG. 15 is a drawing showing the structure of a laser diode in Example 5.
- a GaN substrate 111 having a semipolar principal surface inclined at an angle ⁇ 4 of 68 degrees in the m-axis direction was prepared. After the GaN substrate 111 was placed in the growth furnace, ammonia (NH 3 ) and hydrogen (H 2 ) were supplied to the growth furnace to hold the GaN substrate 111 in an atmosphere of 1050 degrees Celsius. After this pretreatment, a source gas was supplied to the growth furnace to produce the following laser structure. First, an n-type Al 0.04 Ga 0.96 N cladding layer 112 was grown at 1050 degrees Celsius.
- the In 0.03 Ga 0.97 N optical guide layer 113a was grown.
- An active layer 114 was grown on the In 0.03 Ga 0.97 N optical guide layer 113a.
- an In 0.03 Ga 0.97 N optical guide layer 113b was grown on the active layer 114 at a substrate temperature of 840 degrees Celsius.
- an Al 0.12 Ga 0.88 N electron blocking layer 115, a p-type Al 0.06 Ga 0.94 N cladding layer 116, and a p-type GaN contact layer 117 were grown.
- the photoluminescence wavelength of this laser structure was in the 450 nm band.
- a purification device was provided between the nitrogen raw material supply source and the growth furnace. This refiner was used to purify and supply ammonia as a nitrogen raw material to the growth reactor. Using the refining apparatus, ammonia having a water content of 500 ppb% or less can be supplied to the growth furnace as the nitrogen raw material. In addition, ammonia having a water content of 50 ppb% or less can be used as a nitrogen raw material using a purification apparatus. Furthermore, ammonia having a water content of 1 ppb% or less can be supplied to the growth reactor as a nitrogen raw material using a purification apparatus. In this example, ammonia having a water concentration of 50 ppb% was supplied to the growth reactor as a nitrogen raw material.
- the oxygen concentration of the p-type Al 0.06 Ga 0.94 N cladding layer was 2 ⁇ 10 17 cm ⁇ 3 .
- ammonia having a water concentration of 1 ppm% was used as a nitrogen raw material.
- the oxygen concentration of this p-type AlGaN layer was 8 ⁇ 10 18 cm ⁇ 3 .
- An SiO 2 film was formed on the surface of the p-type GaN contact layer 117 in the LD structure of the example, and then a protective window 118 was formed by forming a stripe window having a width of 10 ⁇ m by wet etching.
- a p electrode 119a made of Ni / Au and a pad electrode made of Ti / Au were formed by vapor deposition.
- An n electrode 119b made of Ti / Al and a pad electrode made of Ti / Au were formed on the back surface 111b of the substrate by vapor deposition.
- an SiO 2 film and an electrode were formed as in this example. Thereafter, cleavage to the a-plane was performed at 800 ⁇ m intervals to produce a gain guide type laser.
- FIG. 16 is a diagram showing IV characteristics of laser diodes in Example 4 and a comparative example. Characteristic lines IV1 and IVC indicate the IV characteristics for Example 5 and the comparative example, respectively.
- the drive voltage in the laser diode of the comparative example is significantly higher than the drive voltage in the laser diode of the fifth embodiment. This is presumably because in the laser diode of the comparative example, the oxygen concentration in the p-type contact layer was increased due to the low ammonia purity, and the p-type conductivity was impaired.
- a group III nitride semiconductor optical device including a gallium nitride based semiconductor film having a good surface morphology. Further, according to the present embodiment, it is possible to provide a method for manufacturing this group III nitride semiconductor optical device. Furthermore, according to the present embodiment, an epitaxial substrate including a gallium nitride based semiconductor film having a good surface morphology can be provided.
- the present embodiment has been described with reference to a semiconductor optical device.
- the present invention can also be applied to a group III nitride semiconductor electronic device as an example of a semiconductor device. Accordingly, a group III nitride semiconductor electronic device including a gallium nitride based semiconductor film having a good surface morphology can be provided. Further, according to the present embodiment, it is possible to provide a method for manufacturing this group III nitride semiconductor electronic device. Furthermore, according to the present embodiment, an epitaxial substrate including a gallium nitride based semiconductor film having a good surface morphology can be provided.
- the present invention is not limited to the specific configuration disclosed in the present embodiment.
- the growth of a nitride semiconductor using metal organic vapor phase epitaxy is described as an example.
- the present invention describes a nitride semiconductor using a molecular beam epitaxy method with oxygen uptake. It can also be applied to growth. We therefore claim all modifications and changes that come within the scope and spirit of the following claims.
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Abstract
Description
レーザダイオードLD1を作製した。m軸方向に75度の角度θ1で傾斜させた半極性主面を有するGaN基板71を準備した。この半極性主面は(20-21)面に相当する。GaN基板71を成長炉に配置した後に、成長炉にアンモニア(NH3)及び水素(H2)を供給して、摂氏1050度の雰囲気にGaN基板71を保持した。保持時間は10分であった。この前処理(サーマルクリーニング)の後に、原料ガスを成長炉に供給して以下のレーザ構造を作製した。まず、n型Al0.04Ga0.96Nクラッド層72を摂氏1050度で成長した。摂氏840度に基板温度を下げた後にIn0.03Ga0.97N光ガイド層73aを成長した。In0.03Ga0.97N光ガイド層73a上に量子井戸活性層74を成長した。さらに、摂氏840度に基板温度で、この活性層74上にIn0.03Ga0.97N光ガイド層73bを成長した。摂氏1000度に基板温度を上昇した後に、Al0.12Ga0.88N電子ブロック層78、p型Al0.06Ga0.94Nクラッド層75及びp型GaNコンタクト層76を成長した。このレーザ構造のフォトルミネッセンス波長は450nm帯にあった。このレーザ構造において表面モフォロジに最も大きく影響するものは、GaN基板71の直上に位置しかつ大きな膜厚のクラッド層である。この実施例ではクラッド層72の酸素濃度は3×1017cm-3であった。コンタクト層76には絶縁膜77の開口を介してアノードを形成すると共にGaN基板71の裏面71bにカソードを形成して、図8に示される半導体レーザLD1を作製した。
レーザダイオードを作製した。m軸方向に75度の角度θ2で傾斜させた半極性主面を有するGaN基板81を準備した。この半極性主面は(20-21)面に相当する。GaN基板81を成長炉に配置した後に、成長炉にアンモニア(NH3)及び水素(H2)を供給して、摂氏1050度の雰囲気にGaN基板81を保持した。保持時間は10分であった。このサーマルクリーニングの後に、原料ガスを成長炉に供給して以下のレーザ構造を作製した。まず、n型Al0.04Ga0.96Nクラッド層82を摂氏1050度で成長した。摂氏840度に基板温度を下げた後に、厚さ100nmのIn0.02Ga0.98N光ガイド層83aを成長した。光ガイド層83上に量子井戸活性層84を成長した。さらに、摂氏840度に基板温度で、この活性層84上にIn0.02Ga0.98N光ガイド層83bを成長した。摂氏1000度に基板温度を上昇した後に、Al0.12Ga0.88N電子ブロック層85、p型Al0.06Ga0.94Nクラッド層86及びp型GaNコンタクト層87を成長した。このレーザ構造のフォトルミネッセンス波長は405nm帯にあった。
発光ダイオードを作製した。a軸方向に18度の角度θ3で傾斜させた半極性主面を有するGaN基板91を準備した。GaN基板91を成長炉に配置した後に、成長炉にアンモニア(NH3)及び水素(H2)を供給して、摂氏1050度の雰囲気にGaN基板91を保持した。保持時間は10分であった。このサーマルクリーニングの後に、原料ガスを成長炉に供給して以下の発光ダイオード構造を作製した。まず、厚さ2μmのn型GaN層92を摂氏1050度で成長した。摂氏840度に基板温度を下げた後にIn0.04Ga0.96N緩衝層93を成長した。厚さ100nmの緩衝層93上に量子井戸活性層94を成長した。具体的には、摂氏840度の基板温度で厚さ15nmのGaN障壁層94aを成長すると共に摂氏700度の基板温度で厚さ3nmのInAlGaN井戸層94bを成長して、活性層94を形成した。摂氏1000度に基板温度を上昇した後に、この活性層94上に厚さ20nmのp型Al0.18Ga0.82N電子ブロック層95及び厚さ50nmのp型GaNコンタクト層96を成長した。コンタクト層96にはアノード(Ni/Au)97とパッド電極99aを形成すると共に基板91の裏面91bにカソード(Ti/Al)を形成して、図12に示される発光ダイオードLED1を作製した。異なるインジウム組成のInAlGaN井戸層を有する発光ダイオード構造を作製した。井戸層の酸素濃度と光出力との関係を調べた。
LED構造、In組成、Al組成、酸素濃度(cm-3)、光出力
LED1 :0.18、0、 2×1017、 1
LED2 :0.19、0.03、4×1017、 0.85
LED3 :0.20、0.06、1×1018、 0.54。
450nm付近の発光波長を得るように、井戸層のIn組成を変更した。井戸層中の酸素濃度が増加するに従い、発光出力は低下した。これは、酸素の添加が井戸層の結晶品質を低下させたと考えられる。井戸層のAlは酸素を吸着しやすくまた低温(井戸層にInが取り込まれるような温度)で吸着した酸素が脱離しにくいことを利用して、井戸層の酸素濃度を制御した。
m面主面を有するGaN基板を準備した。このGaN基板上にレーザダイオードLD3を作製した。図13は、実施例4におけるレーザダイオードの構造を示す図面である。GaN基板101を成長炉に配置した後に、成長炉にアンモニア(NH3)及び水素(H2)を供給して、摂氏1050度の雰囲気でサーマルクリーニングを行った後に、実施例1と同様にして、以下のレーザ構造をGaN基板101の無極性主面101a上に作製した。
Al0.04Ga0.96Nクラッド層102:n型、2μm、
In0.03Ga0.97N光ガイド層103a:アンドープ、100nm、
活性層104:In0.18Ga0.82N井戸層(厚さ3nm)/GaN障壁層(厚さ15nm)、
In0.03Ga0.97N光ガイド層103b:アンドープ、100nm、
Al0.12Ga0.88N電子ブロック層105:p型、20nm、
Al0.06Ga0.94Nクラッド層106:p型、400nm、
GaNコンタクト層107:p型、50nm。
ストライプ窓(幅10μm)を有する絶縁膜(例えばSiO2)108及びコンタクト層107上にアノード109aを形成すると共に、GaN基板101の裏面101bにカソード109bを形成した。この後に、へき開によりゲインガイド型半導体レーザLD3を作製した。
レーザダイオードLD4を作製した。図15は、実施例5におけるレーザダイオードの構造を示す図面である。m軸方向に68度の角度θ4で傾斜させた半極性主面を有するGaN基板111を準備した。GaN基板111を成長炉に配置した後に、成長炉にアンモニア(NH3)及び水素(H2)を供給して、摂氏1050度の雰囲気にGaN基板111を保持した。この前処理の後に、原料ガスを成長炉に供給して以下のレーザ構造を作製した。まず、n型Al0.04Ga0.96Nクラッド層112を摂氏1050度で成長した。摂氏840度に基板温度を下げた後にIn0.03Ga0.97N光ガイド層113aを成長した。In0.03Ga0.97N光ガイド層113a上に活性層114を成長した。さらに、摂氏840度に基板温度で、この活性層114上にIn0.03Ga0.97N光ガイド層113bを成長した。摂氏1000度に基板温度を上昇した後に、Al0.12Ga0.88N電子ブロック層115、p型Al0.06Ga0.94Nクラッド層116及びp型GaNコンタクト層117を成長した。このレーザ構造のフォトルミネッセンス波長は450nm帯にあった。
Claims (29)
- III族窒化物半導体からなり、該III族窒化物半導体のc軸方向に延びる基準軸に直交する基準平面に対して有限の角度をなす主面を有するIII族窒化物半導体支持体と、
5×1016cm-3以上5×1018cm-3以下の酸素濃度を有しており、前記III族窒化物半導体支持体の前記主面上に設けられた窒化ガリウム系半導体領域とを備え、
前記主面は半極性及び無極性のいずれか一方を示し、
前記窒化ガリウム系半導体領域は、第1導電型窒化ガリウム系半導体層を含む、ことを特徴とするIII族窒化物半導体素子。 - 前記窒化ガリウム系半導体領域上に設けられた活性層と、
前記活性層上に設けられた第2導電型窒化ガリウム系半導体層と
を更に備え、
前記活性層は、前記第1導電型窒化ガリウム系半導体層と前記第2導電型窒化ガリウム系半導体層との間に設けられる、ことを特徴とする請求項1に記載されたIII族窒化物半導体素子。 - 前記活性層における酸素濃度は5×1016cm-3以上であり、前記活性層における酸素濃度は5×1018cm-3以下である、ことを特徴とする請求項2に記載されたIII族窒化物半導体素子。
- 前記第2導電型窒化ガリウム系半導体層における酸素濃度は5×1016cm-3以上であり、前記第2導電型窒化ガリウム系半導体層における酸素濃度は5×1018cm-3以下である、ことを特徴とする請求項2または請求項3に記載されたIII族窒化物半導体素子。
- 前記第1導電型窒化ガリウム系半導体層の炭素濃度は5×1018cm-3以下であり、
前記第2導電型窒化ガリウム系半導体層の炭素濃度は5×1018cm-3以下であり、
前記活性層の炭素濃度は5×1018cm-3以下である、ことを特徴とする請求項2~請求項4のいずれか一項に記載されたIII族窒化物半導体素子。 - 前記第2導電型窒化ガリウム系半導体層の酸素濃度は5×1016cm-3以上であり、
前記活性層の酸素濃度は5×1016cm-3以上である、ことを特徴とする請求項2~請求項5のいずれか一項に記載されたIII族窒化物半導体素子。 - 前記活性層は、交互に配列された井戸層及び障壁層を含み、
前記井戸層の酸素濃度は6×1017cm-3以下である、ことを特徴とする請求項2~請求項6のいずれか一項に記載されたIII族窒化物半導体素子。 - 別の第2導電型窒化ガリウム系半導体層を更に備え、
前記第2導電型窒化ガリウム系半導体層のバンドギャップは前記別の第2導電型窒化ガリウム系半導体層のバンドギャップよりも大きく、
前記第2導電型窒化ガリウム系半導体層の酸素濃度は、前記活性層の酸素濃度よりも大きく、
前記第2導電型窒化ガリウム系半導体層は前記別の第2導電型窒化ガリウム系半導体層と前記活性層との間に設けられており、
前記第2導電型窒化ガリウム系半導体層は前記別の第2導電型窒化ガリウム系半導体層と接合を形成する、ことを特徴とする請求項2~請求項7のいずれか一項に記載されたIII族窒化物半導体素子。 - 前記活性層と前記第2導電型窒化ガリウム系半導体層との間に設けられ窒化ガリウム系半導体からなる光ガイド層を更に備え、
前記活性層は、前記基準平面に対して傾斜する平面に沿って延在しており、
前記第2導電型窒化ガリウム系半導体層は電子ブロック層である、ことを特徴とする請求項2~請求項8のいずれか一項に記載されたIII族窒化物半導体素子。 - 前記主面の法線と前記基準軸との成す角度は10度以上170度以下である、ことを特徴とする請求項2~請求項9のいずれか一項に記載されたIII族窒化物半導体素子。
- 前記主面の法線と前記基準軸との成す角度は10度以上80度以下及び100度以上170度以下の範囲にある、ことを特徴とする請求項2~請求項10のいずれか一項に記載されたIII族窒化物半導体素子。
- 前記主面の法線と前記基準軸との成す角度は63度以上80度以下及び100度以上117度以下の範囲にある、ことを特徴とする請求項2~請求項11のいずれか一項に記載されたIII族窒化物半導体素子。
- III族窒化物半導体素子のためのエピタキシャルウエハであって、
III族窒化物半導体からなり、該III族窒化物半導体のc軸方向に延びる基準軸に直交する基準平面に対して有限の角度をなす主面を有するIII族窒化物半導体基板と、
5×1016cm-3以上5×1018cm-3以下の酸素濃度を有しており、前記III族窒化物半導体基板の前記主面上に設けられた第1導電型窒化ガリウム系半導体層と、
前記第1導電型窒化ガリウム系半導体層上に設けられた発光層と、
前記発光層上に設けられた第2導電型窒化ガリウム系半導体層と
を備え、
前記主面は半極性及び無極性のいずれか一方を示す、ことを特徴とするエピタキシャルウエハ。 - 別の第2導電型窒化ガリウム系半導体層を更に備え、
前記第2導電型窒化ガリウム系半導体層のバンドギャップは前記別の第2導電型窒化ガリウム系半導体層のバンドギャップよりも大きく、
前記第2導電型窒化ガリウム系半導体層の酸素濃度は、前記発光層の酸素濃度よりも大きく、
前記第2導電型窒化ガリウム系半導体層は前記別の第2導電型窒化ガリウム系半導体層と前記発光層との間に設けられており、
前記第2導電型窒化ガリウム系半導体層は前記別の第2導電型窒化ガリウム系半導体層と接合を形成する、ことを特徴とする請求項13に記載されたエピタキシャルウエハ。 - 前記第2導電型窒化ガリウム系半導体層の酸素濃度は5×1016cm-3以上であり、前記第2導電型窒化ガリウム系半導体層の酸素濃度は5×1018cm-3以下であり、
前記第2導電型窒化ガリウム系半導体層は電子ブロック層であり、
前記発光層は、交互に配列された井戸層及び障壁層を有する活性層を含み、
前記発光層は、窒化ガリウム系半導体からなる光ガイド層を更に備え、該光ガイド層は、前記活性層と前記第2導電型窒化ガリウム系半導体層との間に設けられ、
前記発光層の前記光ガイド層は、前記基準平面に対して傾斜する平面に沿って延在している、ことを特徴とする請求項13または請求項14に記載されたエピタキシャルウエハ。 - 前記主面の法線と前記基準軸との成す角度は10度以上170度以下である、ことを特徴とする請求項13~請求項15のいずれか一項に記載されたエピタキシャルウエハ。
- 前記主面の法線と前記基準軸との成す角度は10度以上80度以下及び100度以上170度以下の範囲にある、ことを特徴とする請求項13~請求項16のいずれか一項に記載されたエピタキシャルウエハ。
- 前記主面の法線と前記基準軸との成す角度は63度以上80度以下及び100度以上117度以下の範囲にある、ことを特徴とする請求項13~請求項17のいずれか一項に記載されたエピタキシャルウエハ。
- III族窒化物半導体素子を作製する方法であって、
III族窒化物半導体からなり、主面を有するIII族窒化物半導体基板を準備する工程と、
III族原料及び窒素原料を成長炉に供給して、5×1016cm-3以上5×1018cm-3以下の酸素濃度を有する第1導電型窒化ガリウム系半導体層を前記III族窒化物半導体基板の前記主面上に成長する工程と、
III族原料及び窒素原料を前記成長炉に供給して、前記第1導電型窒化ガリウム系半導体層上に発光層を成長する工程と、
III族原料及び窒素原料を前記成長炉に供給して、第2導電型窒化ガリウム系半導体層を前記発光層上に成長する工程と
を備え、
前記主面は半極性及び無極性のいずれか一方を示し、
前記第1導電型窒化ガリウム系半導体層の酸素は、前記III族原料及び前記窒素原料の少なくともいずれか一つに含まれる不純物として提供され、
前記III族窒化物半導体基板の前記主面は、該III族窒化物半導体のc軸方向に延びる基準軸に直交する基準平面に対して有限の角度をなす、ことを特徴とする方法。 - 前記窒素原料はアンモニアを含み、
前記窒素原料は不純物として水を含み、
前記発光層における平均酸素濃度は5×1016cm-3以上であり、前記発光層における酸素濃度は5×1018cm-3以下であり、
前記第2導電型窒化ガリウム系半導体層における酸素濃度は5×1016cm-3以上であり、前記第2導電型窒化ガリウム系半導体層における酸素濃度は5×1018cm-3以下であり、
前記第2導電型窒化ガリウム系半導体層の酸素濃度は、前記発光層の酸素濃度よりも大きい、ことを特徴とする請求項19に記載された方法。 - 前記第2導電型窒化ガリウム系半導体層の成長温度は前記第1導電型窒化ガリウム系半導体層の成長温度よりも低い、ことを特徴とする請求項19または請求項20に記載された方法。
- 前記発光層はInGaN層を含む、ことを特徴とする請求項19~請求項21のいずれか一項に記載された方法。
- 前記主面の法線と前記基準軸との成す角度は10度以上170度以下である、ことを特徴とする請求項19~請求項22のいずれか一項に記載された方法。
- 前記主面の法線と前記基準軸との成す角度は63度以上80度以下及び100度以上117度以下の範囲にある、ことを特徴とする請求項19~請求項23のいずれか一項に記載された方法。
- 前記窒素原料の原料源と前記成長炉との間に設けられた精製装置を用いて前記窒素原料の水分濃度を調整した後に、前記成長炉に前記窒素原料を供給し、
前記窒素原料はアンモニアからなる、ことを特徴とする請求項19~請求項24のいずれか一項に記載された方法。 - 前記窒素原料として、水分含有量500ppb%以下のアンモニアを用いる、ことを特徴とする請求項19~請求項25のいずれか一項に記載された方法。
- 前記窒素原料として、水分含有量50ppb%以下のアンモニアを用いる、ことを特徴とする請求項19~請求項26のいずれか一項に記載された方法。
- 前記窒素原料として、水分含有量1ppb%以下のアンモニアを用いる、ことを特徴とする請求項19~請求項27のいずれか一項に記載された方法。
- 前記窒素原料の前記水分濃度は1ppb%以下である、ことを特徴とする請求項25に記載された方法。
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EP09812406.8A EP2410580A4 (en) | 2009-03-11 | 2009-04-24 | GROUP III NITRIDE SEMICONDUCTOR DEVICE, EPITAXIAL SUBSTRATE AND METHOD FOR PRODUCING THE GROUP III NITRIDE SEMICONDUCTOR DEVICE |
CN2009801008614A CN101919076B (zh) | 2009-03-11 | 2009-04-24 | Ⅲ族氮化物半导体器件、外延衬底及ⅲ族氮化物半导体器件的制作方法 |
US12/714,049 US7851821B2 (en) | 2009-03-11 | 2010-02-26 | Group III nitride semiconductor device, epitaxial substrate, and method of fabricating group III nitride semiconductor device |
US12/940,879 US8053806B2 (en) | 2009-03-11 | 2010-11-05 | Group III nitride semiconductor device and epitaxial substrate |
US13/112,714 US8304269B2 (en) | 2009-03-11 | 2011-05-20 | Method of fabricating group III nitride semiconductor device |
US13/243,516 US8207556B2 (en) | 2009-03-11 | 2011-09-23 | Group III nitride semiconductor device and epitaxial substrate |
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JP2013026452A (ja) * | 2011-07-21 | 2013-02-04 | Sumitomo Electric Ind Ltd | Iii族窒化物半導体発光素子、及びiii族窒化物半導体発光素子を作製する方法 |
CN103748749A (zh) * | 2011-07-21 | 2014-04-23 | 住友电气工业株式会社 | Iii族氮化物半导体发光元件及iii族氮化物半导体发光元件的制作方法 |
US8872156B2 (en) | 2011-07-21 | 2014-10-28 | Sumitomo Electric Industries, Ltd. | Group III nitride semiconductor light emitting device and method of fabricating group III nitride semiconductor light emitting device |
WO2016017506A1 (ja) * | 2014-07-29 | 2016-02-04 | 住友化学株式会社 | 窒化物半導体ウエハおよびその製造方法 |
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CN101919076B (zh) | 2012-10-17 |
KR101151953B1 (ko) | 2012-06-04 |
US20100230690A1 (en) | 2010-09-16 |
US8304269B2 (en) | 2012-11-06 |
KR20100115701A (ko) | 2010-10-28 |
CN101919076A (zh) | 2010-12-15 |
EP2410580A4 (en) | 2013-11-06 |
JP4375497B1 (ja) | 2009-12-02 |
US8053806B2 (en) | 2011-11-08 |
US7851821B2 (en) | 2010-12-14 |
US20120086015A1 (en) | 2012-04-12 |
US20110223701A1 (en) | 2011-09-15 |
EP2410580A1 (en) | 2012-01-25 |
JP2010212493A (ja) | 2010-09-24 |
TW201034054A (en) | 2010-09-16 |
US20110057200A1 (en) | 2011-03-10 |
US8207556B2 (en) | 2012-06-26 |
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