WO2007013257A1 - Dispositif semi-conducteur au nitrure - Google Patents

Dispositif semi-conducteur au nitrure Download PDF

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Publication number
WO2007013257A1
WO2007013257A1 PCT/JP2006/313107 JP2006313107W WO2007013257A1 WO 2007013257 A1 WO2007013257 A1 WO 2007013257A1 JP 2006313107 W JP2006313107 W JP 2006313107W WO 2007013257 A1 WO2007013257 A1 WO 2007013257A1
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layer
nitride
type
carbon
semiconductor layer
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PCT/JP2006/313107
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English (en)
Japanese (ja)
Inventor
Yasutoshi Kawaguchi
Ryo Kato
Yoshiaki Hasegawa
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Matsushita Electric Industrial Co., Ltd.
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Publication of WO2007013257A1 publication Critical patent/WO2007013257A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00—Semiconductor lasers
    • H01S5/30—Structure or shape of the active region; Materials used for the active region
    • H01S5/32—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures
    • H01S5/323—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser
    • H01S5/32308—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser emitting light at a wavelength less than 900 nm
    • H01S5/32341—Structure or shape of the active region; Materials used for the active region comprising PN junctions, e.g. hetero- or double- heterostructures in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser emitting light at a wavelength less than 900 nm blue laser based on GaN or GaP
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/025—Physical imperfections, e.g. particular concentration or distribution of impurities
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H01L33/30—Materials of the light emitting region containing only elements of group III and group V of the periodic system
    • H01L33/32—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00—Semiconductor lasers
    • H01S5/30—Structure or shape of the active region; Materials used for the active region
    • H01S5/305—Structure or shape of the active region; Materials used for the active region characterised by the doping materials used in the laser structure

Definitions

  • the present invention relates to a nitride-based semiconductor device.
  • the nitride semiconductor device according to the present invention is a nitride such as a semiconductor laser, which is expected to be applied to the field of optoelectronic information processing, a light emitting diode, an ultraviolet detector, etc.
  • Nitride-based semiconductors containing nitrogen (N) as a group V element are regarded as promising materials for short-wavelength light-emitting devices because of their large band gap.
  • compound semiconductors nitride-based semiconductors: AlGalnN
  • gallium nitride have been actively studied, and blue light-emitting diodes and green light-emitting diodes have already been put into practical use.
  • semiconductor lasers having an oscillation wavelength in the 400 nm band have been eagerly desired, and semiconductor lasers made of nitride semiconductors have attracted attention and are now reaching a practical level.
  • Nitride-based semiconductors have the characteristics that the band gap is large and the dielectric breakdown electric field is high and the saturation saturation speed of the electron is high. Therefore, high-temperature operation is possible and high power can flow. . For this reason, it is considered that it can be used for a field effect transistor realizing high-speed switching characteristics and a high electron mobility transistor.
  • the performance of such a transistor using a nitride-based semiconductor is expected to exceed the characteristics of silicon (Si), gallium arsenide (GaAs), and indium phosphide (InP), which have been put into practical use. ing.
  • Patent Documents 1 to 8 Conventional structures such as a semiconductor laser device manufactured using a nitride-based semiconductor are disclosed in, for example, Patent Documents 1 to 8 and Non-Patent Documents 1 to 3.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-126006
  • Patent Document 2 JP-A-9 63962
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-264345
  • Patent Document 4 Japanese Patent Laid-Open No. 2002-100837
  • Patent Document 5 Japanese Unexamined Patent Publication No. 2003-69156
  • Patent Document 6 Japanese Patent Laid-Open No. 11-4044
  • Patent Document 7 Patent No. 3505442
  • Patent Document 8 JP 2001-144378 A
  • Non-Patent Document 1 Japanese Journal of Applied Physics, Vol. 38, L226 -L229 (1 999)
  • Non-Patent Document 2 physica status solidi (A) 194, No. 2, 407-413 (2002)
  • Non-Patent Document 3 IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM E
  • Nitride-based semiconductor laser devices are currently required to achieve a high-power operation of, for example, more than 120 mW.
  • the problem with achieving such a high-power operation is that the acceptor
  • the activation rate of Mg doped as an impurity is low.
  • a p-type GaN layer doped with Mg may activate only about 10% of doped Mg. Therefore, in order to form a p-type cladding layer having the same carrier concentration as that of the n-type cladding layer, it is necessary to dope 10 times or more of Mg.
  • the effective mass of holes is 5 to 10 times heavier than the effective mass of electrons, and as a result, the resistivity is increased by about 20 to 50 times. Therefore, the p-type nitride semiconductor layer The resistivity of the semiconductor device tends to be high, and this high resistivity causes a problem that the operating voltage of the semiconductor element increases and heat is easily generated during operation.
  • a mixed crystal layer containing In (for example, an active layer) is generally grown at a lower growth temperature than a GaN layer or an AlGaN mixed crystal layer in order to suppress decomposition of In from the crystal. It is done.
  • nitride-based optical devices ranging from the visible light to the near-ultraviolet region
  • the active layer deteriorates due to heat, causing problems such as disorder of the quantum well structure, segregation of In, contamination due to impurity diffusion, and increased lattice distortion due to impurity contamination.
  • Mg which is a p-type acceptor impurity, also diffuses from the p-type cladding layer to the active layer, which also causes deterioration of the active layer (impurity contamination and introduction of lattice strain due to it).
  • the luminous efficiency decreases.
  • solving these problems is an indispensable condition for realizing a high-power and high-reliability nitride-based semiconductor laser.
  • the increase in operating voltage and heat generation in the p-type cladding layer, and the thermal degradation of the active layer during the temperature rising process during the preparation of the p-type cladding layer adversely affect the reliability of the nitride-based semiconductor element. It is difficult to manufacture highly reliable nitride-based semiconductor elements with high reproducibility.
  • Patent Document 2 p-type conversion is realized at a high activation rate by carbon doping to the p-type AlGaN cladding layer. It is disclosed that impurity diffusion to the side can be suppressed. Instead of Mg, which is usually used as a p-type dopant, a low-resistance p-type crystal is realized by doping only carbon. However, Patent Document 2 does not disclose an optimal carbon concentration range that can realize good electrical characteristics for the light-emitting element.
  • Patent Document 8 describes the effect of carbon doping on an n-type AlGaN cladding layer with Si doping and a p-type AlGaN cladding layer with Mg doping.
  • the optimum carbon concentration range that can realize good electrical characteristics for the device is not disclosed.
  • the present invention has been made to solve the above problems, and a main object thereof is to provide a nitride semiconductor device having high reliability.
  • a nitride-based semiconductor element wherein the stacked structure includes an n-type nitride-based semiconductor layer, a p-type nitride-based semiconductor layer, the n-type nitride-based semiconductor layer, and the p-type nitride-based device
  • a nitride-based semiconductor layer positioned between the semiconductor layer, the p-type nitride-based semiconductor layer being doped with a p-type impurity other than carbon and carbon, and the p-type nitride Carbon concentration of semiconductor layer The degree is higher than the carbon concentration of the n-type nitride semiconductor layer, which is lower than the concentration of the p-type impurity other than the carbon.
  • the p-type impurity other than carbon doped in the p-type nitride-based semiconductor layer is magnesium.
  • the carbon concentration of the p-type nitride-based semiconductor layer is 8 ⁇ 10 16 cm ⁇ 3 or more and 1 ⁇ 10 18 cm ⁇ 3 or less.
  • the carbon concentration of the p-type nitride semiconductor layer is 0.8 relative to the concentration of p-type impurities other than carbon doped in the p-type nitride semiconductor layer.
  • the substrate includes gallium nitride, aluminum gallium nitride (
  • the average value of threading dislocation density in the substrate is 3 ⁇ 10 6 cm or less.
  • the nitride-based semiconductor layer located between the p-type nitride-based semiconductor layer and the n-type nitride-based semiconductor layer functions as an active layer that emits light, and the n-type
  • Each of the nitride-based semiconductor layer and the p-type nitride-based semiconductor layer functions as a cladding layer for the active layer.
  • the p-type nitride-based semiconductor layer and the n-type nitride-based semiconductor layer contain at least a part of aluminum, and the p-type nitride-based semiconductor layer and the n-type nitride-based layer are included.
  • the nitride-based semiconductor layer located between the semiconductor layer contains indium at least partially.
  • the n-type nitride semiconductor layer is doped with at least one element selected from the group consisting of silicon, germanium, and oxygen.
  • the p-type nitride-based semiconductor layer is doped with p-type impurities (acceptor impurities) other than carbon (C) and carbon. Its carbon concentration The degree is adjusted to be lower than the concentration of P-type impurities other than carbon.
  • carbon doped in the nitride-based semiconductor layer is a group IV element, it functions as a donor impurity if it is replaced with a group III element (for example, Ga) in the crystal. If replaced with some N, it functions as an acceptor impurity.
  • group III element for example, Ga
  • acceptor impurity for example, Ga
  • by doping a p-type impurity other than carbon most of the carbon is replaced with N of the group V element. In other words, since carbon acts as an acceptor impurity at the N site, it has the effect of compensating for residual donors.
  • nitride-based semiconductors have many N vacancies (point defects) that serve as donor sources, but in the present invention, doped C occupies N sites in the crystal, so In order to suppress the generation of, it is possible to greatly reduce the electrical resistivity of the p-type nitride semiconductor layer.
  • FIG. 1 is a cross-sectional view showing a first embodiment (semiconductor laser element) of a nitride-based semiconductor element according to the present invention.
  • FIG. 2 is a graph showing a SIMS profile in the semiconductor laser device shown in FIG.
  • FIG. 3 is a graph showing the relationship between the resistivity of the n-GaN layer and the Si concentration.
  • FIG. 4 is a graph showing the relationship between the resistivity of the p-GaN layer and the Mg concentration.
  • FIG. 5 (a) is a graph showing IL and IV characteristics for a semiconductor laser device having a p-type cladding layer doped with Mg and C, and (b) is a graph showing only Mg doped.
  • p This is a diagram showing IL and IV characteristics of a semiconductor laser device having a type cladding layer.
  • FIG. 6 is a graph showing the relationship between Mg concentration in the light guide layer (p side) / active layer and threading dislocation density in the substrate.
  • P _GaN layer (growth temperature: 900 ° C) is a graph showing the relationship between the resistivity and Mg concentration.
  • FIG. 8 This is a graph showing the relationship between internal quantum efficiency and internal loss and carbon concentration in a nitride semiconductor laser device having a p-type cladding layer doped with carbon.
  • FIG. 9 A sectional view showing a third embodiment (semiconductor laser element) of a nitride-based semiconductor element according to the present invention.
  • FIG. 1 shows a cross-sectional structure of the nitride-based semiconductor laser device of this embodiment.
  • the semiconductor laser device of this embodiment includes an n-GaN substrate 101 and a semiconductor multilayer structure formed on the n_GaN substrate 101.
  • the stacked semiconductor structure consists of the ⁇ —GaN layer 102, n_Al Ga N cladding layer 103, n_GaN light guide layer 1 from the side close to the n_GaN substrate 101.
  • Optical guide layer 106 Non-doped GaN second optical guide layer 107, Non-doped Al Ga N Third optical guide layer 108, p_Al Ga N first cladding layer 109, p_Al Ga N second cladding layer 11
  • a mesa stripe having a width of approximately 1.4 to 1.8 zm is formed on the upper surface of the semiconductor multilayer structure, and a region other than the upper surface of the mesa stripe is covered with an insulating layer (Si layer) 114. It has been broken.
  • N electrode 113 is formed.
  • Gain occurs at 5, and laser oscillation occurs at a wavelength of 410 nm.
  • the most characteristic feature of the semiconductor laser of the present embodiment is that the p-AlGaN first cladding layer 1
  • the p-type nitride semiconductor layer from 09 to the p-GaN contact layer 111 is doped with carbon (C) together with Mg, which is an acceptor impurity.
  • the above semiconductor stacked structure can be suitably formed by metal organic vapor phase epitaxy (MOVPE), but other methods such as hydride vapor phase epitaxy (HVPE) and molecular beam epitaxy (MBE).
  • MOVPE metal organic vapor phase epitaxy
  • HVPE hydride vapor phase epitaxy
  • MBE molecular beam epitaxy
  • the compound semiconductor crystal growth method can be used.
  • the MOVPE method is used for crystal growth, but the atmosphere during crystal growth may be a reduced pressure or a pressure higher than atmospheric pressure. The pressure may be switched to an optimum pressure depending on the composition of the semiconductor layer to be grown. Also, to supply the growth layer material to the substrate As the carrier gas, a gas containing an inert gas such as nitrogen (N) or hydrogen (H) is used.
  • N nitrogen
  • H hydrogen
  • an n-GaN substrate 101 is prepared, and the surface of the n-GaN substrate 101 is cleaned with an organic solvent or acid. After that, the n_GaN substrate 101 is placed on the susceptor in the growth chamber of the MOVPE apparatus, and the atmosphere gas in the growth chamber is sufficiently replaced with N. N substitution finished
  • the n-GaN substrate 101 is heated in an N atmosphere, and the temperature rise rate is 10 ° C / 10 seconds.
  • n-GaN layer 102 is grown. Subsequently, trimethylaluminum (TMA) is removed and 1. A thick n_AlGaN cladding layer 103 is grown.
  • TMA trimethylaluminum
  • the supply of TMA is stopped, and the n-GaN optical guide layer 104 is grown to a thickness of 0.1 ⁇ m.
  • the carrier gas is switched to H force N, NH
  • a In N well layer thickness is 5 nm
  • Ga In N barrier layer thickness is 6 nm
  • the number of well layers is 2
  • the active layer 105 is not intentionally doped with impurities.
  • a non-doped Ga In N first optical guide layer 106 having a thickness of 25 nm and a thickness of 50 nm
  • Cp Mg biscyclopentagenenyl magnesium
  • Methane (CH 3) was added as a p-AlGaN first cladding layer 109 by lOnm growth.
  • the The p—Al Ga N first cladding layer 109 is composed of Ga In N / Ga In N—quantum well actives.
  • Laminate. Mg and C are doped under the same conditions as those for the p-AlGaN first cladding layer 109.
  • the ⁇ -GaN substrate 101 on which the laminated structure is formed is taken out of the MOVPE apparatus, and a microfabrication process using photolithography and etching techniques is performed. Specifically, P-A1 Ga N first cladding layer 109, p_Al Ga N first
  • Cladding layer 110 and p-GaN contact layer 111 are processed into stripes as shown in FIG. 1 to form mesa stripes.
  • the upper surface of the mesa stripe that is, the upper surface of the p-GaN contact layer 111 processed into the stripe shape is exposed at a portion (opening portion of the SiO layer 114) covered with the SiO layer 114.
  • the stripe width is about 1 ⁇ 4 ⁇ :! ⁇ 8 / im.
  • the upper surface of the N contact layer 111 is in contact with the upper surface of the Si layer 114.
  • the N contact layer 111 in order to reduce the contact resistance with the p electrode 112, the concentration 1 X 10 2 ° cm- 3 from 2 X 10 2 ° cm- 3 of Mg is doped.
  • the n-GaN substrate 101 is polished on the back side to reduce the thickness of the n-GaN substrate 101 to about 90 ⁇ m, and then an n-electrode 113 is formed on the back surface of the n-GaN substrate 101. To do.
  • the supply of TMG is temporarily stopped, and N and NH are The temperature is quickly raised in the supplied state, and the carrier gas is changed to a mixed gas of N and H on the way.
  • TMG and TMA can be supplied and the temperature can be raised while the A1 GaN third light guide layer 108 is crystal-grown. If the method does not generate defects that cause non-radiative recombination centers in the crystal, Such a temperature raising method may be adopted.
  • FIG. 2 is a graph showing a SIMS profile for the semiconductor laser of the present embodiment.
  • the “carbon concentration” in 07 is 8 ⁇ 10 16 cm ⁇ 3 to l ⁇ 10 17 cm ⁇ 3 . Since these semiconductor layers 1 05 to 107 are not intentionally doped with carbon, their carbon concentration is extremely low.
  • n_AlGaN cladding layer 103 containing A1 is shown in FIG. 2, n_AlGaN cladding layer 103 containing A1, and
  • the carbon concentration in the Al Ga N third light guide layer 108 is 1 to 3 ⁇ 10 17 cm ⁇ 3 .
  • These semiconductor layers 103 and 808 contain a trace amount of C even though they are not intentionally carbon-doped because C is auto-doped from the raw material TMA.
  • the carbon concentration also depends on the growth rate of the nitride-based semiconductor layer, and that the carbon concentration further decreases when the growth rate is decreased. Compared to the example in Fig. 2, when the growth rate is reduced to about 70%, the carbon concentration in these nitride-based semiconductor layers decreases to 7 x 10 16 cm 3 or less.
  • the carbon concentration in the N second cladding layer 110 and the p-GaN contact layer 111 was in the range of about 7 ⁇ 10 17 to 1 ⁇ 10 18 cm 3 . In the case of these nitride semiconductor layers as well, the carbon concentration decreases from 8 ⁇ 10 16 cm 3 to 8 ⁇ 10 17 cm ⁇ 3 when the growth rate is reduced to about 70%.
  • the magnitude relationship among the carbon concentrations of the n-type cladding layer, the active layer, and the p-type cladding layer was such that the active layer was n-type cladding layer ⁇ p-type cladding layer.
  • a semiconductor layer having a thickness of 1 ⁇ m was grown and carbon doping was performed.
  • Carbon concentration 3 Several samples were prepared in the range of X 10 17 cm— 3 to 5 X 10 18 cm— 3 , and the electrical characteristics of each sample were evaluated.
  • the resistivity immediately after fabrication is IX 10 7 ⁇ cm or higher, regardless of n-type or p-type, and it exhibits very high resistance and n-type conductivity. I understand.
  • the concentration of Si remaining in the crystal of the obtained GaN layer is about 1 to 2 X 10 16 cm 3 .
  • the resistivity of the GaN layer was about 10 ⁇ cm.
  • n-type cladding layer cannot be obtained even if only carbon doping is performed on the cladding layer, and a p-type cladding layer can also be obtained. You can see that you can't.
  • C is a group IV element, so if C substitutes Ga in the GaN crystal, it functions as a donor impurity, and substitutes N Then, it functions as an acceptor impurity.
  • C when only carbon doping was performed under the growth conditions in this embodiment, a GaN layer showing n-type conductivity having a very high resistance was obtained compared to a GaN layer without doping. Based on this, it is considered that most of the added C is replaced with N in the GaN crystal and acts as an acceptor impurity to compensate the residual donor.
  • the GaN crystal has many N vacancies (point defects) that serve as donor sources. It is doped, but occupying N in the GaN crystal suppresses the generation of N vacancies. Conceivable.
  • FIG. 3 is a graph showing the change in resistivity of the n-GaN layer, where the vertical axis represents the resistivity and the horizontal axis represents the Si concentration.
  • “ ⁇ ” indicates data with a carbon concentration of 1 ⁇ 10 17 cm ⁇ 3
  • “ ⁇ ” indicates data with a carbon concentration of 8 ⁇ 10 17 cm ⁇ 3
  • Fig. 4 is a graph showing the change in resistivity of the ⁇ -GaN layer, where the vertical axis represents the resistivity and the horizontal axis represents the Mg concentration.
  • “ki” is carbon. Data with a concentration of 1 X 10 17 cm- 3 are shown, and “ ⁇ ” indicates data with a carbon concentration of 8 X 10 17 cm 3 .
  • the growth conditions are as described in the above embodiment.
  • the carbon concentration of 1 X 10 17 cm 3 corresponds to the data without intentional C doping.
  • the resistivity is about 50 when the carbon concentration is 8 X 10 17 cm 3 compared to 1 X 10 17 cm- 3. It was getting high. This is because most of the doped C replaces N in the GaN crystal and acts as an acceptor impurity, thus compensating for the Si donor.
  • the p_GaN layer doped with Mg as the p-type impurity has a resistivity of about 10 by performing carbon doping. Decreased about / o. This is because doped C replaced N in the GaN crystal, resulting in compensation of residual donors and reduction of N vacancies.
  • This force is a force that can reduce the resistivity by co-doping carbon and magnesium into the p-type nitride semiconductor layer. Simultaneous carbon and silicon doping into the n-type nitride semiconductor layer It was clear that the resistivity increased at one bing. Therefore, it is desirable to keep the carbon concentration of the n-type nitride semiconductor layer as low as possible.
  • the carbon concentration is preferably adjusted to a range of 0.8% to 10% of the Mg concentration.
  • Mg is replaced with Ga. Since it acts as an acceptor impurity, C can effectively replace N and act as an acceptor impurity. By substituting N for C instead of Ga, the residual donor can be compensated, and crystal defects caused by N vacancies can be reduced.
  • N p-type impurities
  • carbon has not been doped at a concentration sufficiently lower than that of other p-type impurities (Mg), and it is known that the resistivity of p-type nitride semiconductors can be effectively reduced. It was not done.
  • Fig. 5 (a) is a graph showing the IL and IV characteristics obtained for a semiconductor laser (this embodiment) having a carbon-doped p-type cladding layer.
  • Fig. 5 (b) 4 is a graph showing IL characteristics and IV characteristics obtained for a semiconductor laser (comparative example) having a p-type cladding layer without carbon doping.
  • the resistivity of the p_AlGaN second cladding layer 110 is reduced, and the series resistance component in the IV characteristics is reduced.
  • the efficiency of hole injection into the active layer is increased, and the threshold current is reduced. Specifically, it was reduced to about 37 mA by performing threshold current force doping that exceeded 50 mA in the absence of C doping.
  • the carrier gas at the time of doping contains not only H but N It is preferable. This is because the presence of N gas in the atmosphere makes it easier for C to be taken into N sites in nitride-based semiconductor crystals. In order to increase the efficiency of C incorporation into the N site, it is effective to increase the growth pressure higher than the conventional conditions and lower the ⁇ ratio within a range that does not affect the electrical characteristics of the semiconductor laser. It is.
  • the ⁇ ratio is 3000 or less, the residual donor concentration increases due to the decrease in crystallinity, and as a result, it becomes difficult to realize a low-resistance ⁇ -type cladding layer. Desirably 0 or more.
  • the ⁇ -type Mg doped in the p-type semiconductor layer or the p-type semiconductor layer positioned thereon diffuses to the light guide layer (p side) and the active layer during the crystal growth process.
  • the diffusion of Mg causes light absorption loss near the active layer / light guide layer (P side) and adversely affects the reliability of the laser.
  • Mg diffusion is achieved from Ga In N / Ga In N—quantum well active layer 105 to non-doped G
  • Mg diffusion can also occur in various situations, such as the subsequent heat treatment step or current application during laser operation. Such Mg diffusion occurs as a diffusion path by dislocations penetrating the semiconductor multilayer structure (threading dislocations) and N vacancies generated in the semiconductor multilayer structure.
  • FIG. 6 is a graph showing the relationship between the threading dislocation density in the substrate and the Mg concentration present in the light guide layer (p side) / active layer.
  • the data in this graph is based on the evaluation results performed on the wafer immediately after crystal growth before the heat treatment step and the like.
  • the carbon concentration of the p-type cladding layer is at three levels. Mg and carbon concentrations were measured by SIMS analysis.
  • the threading dislocation density in the light guide layer (p side) / active layer is Is almost equal to the threading dislocation density in. This is also confirmed from a comparison of dark spot density (spots correspond to threading dislocations) by active sword luminescence between the active layer and the substrate. Since the Mg concentration in the light guide layer (p-side) / active layer that is not doped with Mg during crystal growth is due to Mg diffusion, the extent of Mg diffusion is evaluated by the Mg concentration. be able to.
  • Mg diffusion can be suppressed by carbon doping the p-type cladding layer.
  • N vacancies functioning as Mg diffusion paths are filled with C, so that N vacancies can be formed even at high temperatures during crystal growth. Mg diffusion as a path This is because it becomes difficult.
  • instrument threading dislocation density is to use a substrate of threading dislocation density is 3 X 10 6 cm- 2 or less is 1 X 10 6cm- 2 below substrate More preferably, is used.
  • carbon doping is performed only on the p-type cladding layer. However, if the magnitude relationship of the carbon concentration is within the range satisfying the relationship of active layer ⁇ n-type cladding layer ⁇ p-type cladding layer. Also, carbon doping may be applied to the active layer and the n-type layer. However, since carbon doping in the active layer may cause an increase in light absorption loss, it is preferable not to perform carbon doping in the active layer.
  • carbon doping into the n-type cladding layer may cause an increase in resistivity, so even when carbon doping into the n-type cladding layer is performed, the carbon concentration is 3 ⁇ 10 17 cm ⁇ 3 or less, More preferably, it is preferably adjusted to 0 ⁇ 7 ⁇ 10 17 cm ⁇ 3 or less.
  • AlGaN is used for both the n-type cladding layer and the p-type cladding layer, but AlGaN / GaN superlattice is provided in at least one of the n-type cladding layer and the p-type cladding layer.
  • a structural layer may be used.
  • the cladding layer has a structure that can effectively confine light and carriers even if it contains In, boron (B), arsenic (As), phosphorus (P), and / or antimony (Sb). Any other configuration may be used.
  • a Ga In N / Ga In N—quantum well active layer having two well layers is used as the active layer.
  • the number of well layers may be 3 or more.
  • a combination of a GalnN well layer and a GaN barrier layer, or a combination of a GalnN well layer and an AlGalnN barrier layer may be used, and any configuration capable of realizing high luminous efficiency with low power consumption can be used. These are also true for other embodiments described later.
  • the semiconductor laser of this embodiment has the same configuration as the semiconductor laser shown in FIG.
  • Clad layer 109 0.01 0.99 0.20 0.80 Clad layer 109, p-Al Ga N second clad layer 110, p-GaN contact layer 111 growth
  • the growth temperature of these layers is 1000 ° C. In this embodiment, it is 900 ° C.
  • FIG. 7 is a graph showing the relationship between the resistivity of the p-GaN layer (growth temperature: 900 ° C.) and the Mg concentration.
  • the resistivity of the carbon-doped p_GaN layer increased by about 6% due to the lower growth temperature.
  • the resistivity of the p_GaN layer is thought to increase.
  • the resistivity of the p_GaN layer obtained in this embodiment is almost the same as that produced at a growth temperature of 1000 ° C. and without carbon doping. That is, according to the present embodiment, the effect of carbon doping can be obtained even when the growth temperature is lowered.
  • FIG. 8 is a graph showing the relationship between the internal quantum efficiency (77) and internal loss ( ⁇ .) And the carbon concentration obtained for the semiconductor laser of this embodiment and the semiconductor laser of Embodiment 1.
  • ⁇ and ⁇ indicate the internal quantum efficiency (77.) and internal loss ( ⁇ ), respectively, in the semiconductor laser of Embodiment 1, and “ ⁇ ” and “ ⁇ ” indicate the actual values, respectively.
  • the internal quantum efficiency (77) and internal loss ( ⁇ ) in the semiconductor laser of the embodiment are shown.
  • the hole injection efficiency into the active layer is increased, and the internal quantum efficiency is improved.
  • the growth temperature of the ⁇ -type cladding layer to 900 ° C, it is possible to suppress thermal degradation of the active layer that is likely to occur during the crystal growth process of the p-type cladding layer, thereby further improving the internal quantum efficiency.
  • the carbon concentration exceeds 2 X 10 18 cm 3 , the surface flatness of the growth layer deteriorates and a mirror surface cannot be obtained, so even if carbon doping is applied, the internal quantum efficiency is rather lowered. For this reason, it is preferable to control the carbon concentration to 2 ⁇ 10 18 cm ⁇ 3 or less.
  • the main cause of internal loss in the semiconductor laser of the present embodiment is non-doped Al Ga This is the optical absorption loss due to the N third optical guide layer 108 and the p-AlGaN first cladding layer 109.
  • the growth temperature of the p-type cladding layer is 1000 ° C (corresponding to Embodiment 1)
  • the crystal characteristics deteriorate unless carbon doping is performed, so that the light absorption loss increases.
  • the internal loss increases about twice as high as the growth temperature of 1000 ° C.
  • the electrical characteristics of the p-AlGaN first cladding layer 109 are improved as described above, and the result is Since crystal characteristics are also improved, light absorption loss is reduced and internal loss is also improved.
  • the internal loss at a growth temperature of 900 ° C is about 20 times that at a growth temperature of 1000 ° C. This difference is almost insignificant compared to the effect of improving internal quantum efficiency. That is, when the carbon concentration force is in the range of 3 ⁇ 4 X 10 17 cm— 3 to 8 X 10 17 cm— 3 , the growth temperature of the p-type cladding layer is lowered to about 900 ° C., and the threshold current and operating voltage are reduced. Reduction can be achieved.
  • the growth temperature of the p-type cladding layer is reduced by 100 ° C. from the conventional value, but it is also possible to reduce the growth temperature by more than 100 ° C.
  • carbon doping makes it possible to increase the internal quantum efficiency by lowering the growth temperature of the p-clad layer while realizing a low resistivity of the p-type cladding layer. If the growth temperature of the p-type cladding layer is lower than the growth temperature of the active layer, the residual donor concentration increases significantly, and the resistance of the p-type cladding layer increases. For this reason, it is preferable to set the growth temperature of the p-type cladding layer in a range between the active layer growth temperature and the n-type cladding layer growth temperature.
  • the semiconductor laser of this embodiment has substantially the same configuration as that of the semiconductor laser of Embodiment 1, and the first difference is that the p_AlGaN second cladding layer 110 as shown in FIG. P
  • carbon doping is also applied to the n-AlGaN cladding layer 103.
  • the second cladding layer 1210 has a lower [C supply / Group III material supply] ratio than carbon doping.
  • Ga N first cladding layer 109 and p-Al Ga N / p_GaN_ SLS second cladding layer 12
  • the growth temperatures for all 10 are set to 1000 ° C.
  • the carbon concentration is higher in the N layer and the AlGaN layer.
  • the carbon concentration is the steady carbon concentration of the GaN layer (or AlGaN layer).
  • the average Al composition of the Al Ga N / GaN— SLS layer is 5%
  • the carbon concentration in the Al Ga N layer is the same [C supply / Group III raw material supply] ratio.
  • the [C supply amount / III in the n-AlGaN cladding layer 103 is determined.
  • Carbon doping is carried out at a low ratio of the amount of group raw material supplied]. However, if the relationship between the active layer, the n-type cladding layer, and the p-type cladding layer can be achieved, the ratio of [C supply amount / Group III material supply amount] may be increased.
  • the carbon concentration in the n-Al Ga N clad layer 103 is 3 X 10 17 cm 3 or less
  • the drag rate only increases by about 10% compared to when carbon doping was not performed, and there was no problem in practical use.
  • the carbon concentration in the n_AlGaN cladding layer 103 is 3 X
  • the resistivity of the / p—GaN—SLS second cladding layer 1210 can be reduced. As a result, the series resistance component in the IV characteristics is reduced, and low voltage driving becomes possible.
  • the amount of heat generated in the high current injection state can be suppressed, and a 150 mW optical output can be realized under continuous oscillation conditions at room temperature.
  • the growth temperature of the p-type cladding layer is made equal to the growth temperature of the n-type cladding layer (1000 ° C.). However, as described in the embodiment 2, the growth of the p-type cladding layer is performed.
  • the temperature may be 900 ° C or less, and may be in the range of 900 ° C to 1000 ° C.
  • the semiconductor laser according to the present embodiment has substantially the same configuration as that of the semiconductor laser according to the second embodiment. The difference is that the n-AlGaN cladding layer 103 is also carbon-doped.
  • Group II raw material supply ratio is determined by the p-AlGaN first cladding layer 109 and p-AlGaN first
  • the growth temperature of the n-Al Ga N cladding layer 103 is 1000 ° C, and the first cladding layer of p-Al Ga N
  • the growth temperature of the cladding layer 109 and the p-AlGaN second cladding layer 110 is 920 ° C. Crystal
  • the growth rate is higher than the Al Ga N layer with a growth temperature of 1000 ° C.
  • the directional carbon concentration of the AlGaN layer at 920 ° C is increased.
  • the carbon concentration in the n-Al Ga N clad layer 103 is 3 ⁇ 10 17 cm 3 or less
  • the resistivity is increased only to the extent that there is no practical problem, and the device characteristics are not greatly affected.
  • the C supply amount was controlled so that the carbon concentration in the n-AlGaN cladding layer 103 was 3 ⁇ 10 17 cm ⁇ , the p-AlGaN first cladding layer 109 and the p-AlGaN first layer
  • the carbon concentration in the two cladding layers 110 was 8 ⁇ 10 17 cm 3 , and a P-type cladding layer having a lower resistance than that without carbon doping could be formed.
  • the concentration of hydrogen necessary to activate the Mg acceptor can be reduced as compared with the case where carbon doping is not performed.
  • heat treatment, electron beam irradiation treatment, plasma irradiation, etc. are required, but in the case of p-type cladding layer with carbon doping, Mg and It is possible to activate with a lower hydrogen bond energy than usual. This effect becomes significant by applying carbon doping to the n-type cladding layer.
  • the resistivity of the p-AlGaN first cladding layer 109 and the p-AlGaN second cladding layer 110 can be reduced, and the series resistance component in the IV characteristics is reduced. To do.
  • laser operation with low power consumption is possible.
  • the amount of heat generated in the high current injection state can also be suppressed, so that an optical output of 150 mW was achieved under room temperature continuous oscillation conditions.
  • the growth temperature of the p-type cladding layer is set to 920 ° C.
  • the growth temperature of the p-type cladding layer may be 900 ° C. or less, or may be in the range of 900 ° C. to 1000 ° C.
  • the carbon concentration of the p-type cladding layer is adjusted to 3 ⁇ 10 17 cm 3 or more. Adjusting force In that case, the growth rate of the p-type cladding layer was about 10 nm / min. According to the experiments of the present inventors, when this growth rate is reduced to about 6 to 7 nm / min, the preferable range of the carbon concentration in the p-cladding layer is 8 ⁇ 10 16 cm ⁇ 3 or more and 1 ⁇ 10 18 cm ⁇ 3 In the following, it was found that the more preferable range was 1 ⁇ 10 17 cm 3 or more and 1 ⁇ 10 18 cm ⁇ 3 or less. However, the concentration of p-type impurities such as Mg is maintained at the value in the above-described embodiment. Therefore, the carbon concentration of the p-type cladding layer is preferably in the range of 0.8% to 10% with respect to the concentration of p-type impurities other than carbon, and preferably in the range of 1% to 10%. Is more preferable.
  • a GaN substrate is used.
  • the substrate may be formed of a nitride-based semiconductor such as AlGaN, InGaN, or AlGalnN, which does not need to be formed.
  • a substrate in which a nitride semiconductor layer such as GaN is formed on a substrate (sapphire substrate, SiC substrate, ZnO substrate, Si substrate, GaAs substrate, etc.) formed from a material other than a nitride semiconductor is used. May be.
  • the n electrode is formed on the back surface of the substrate.
  • a substrate having low conductivity or an insulating substrate is used. Moyore.
  • a part of the semiconductor multilayer structure formed on the substrate surface is etched to the n-GaN layer, and an n-electrode is formed on the etched surface.
  • a conductive substrate for example, an n-GaN substrate
  • both the n electrode and the p electrode may be formed on the semiconductor stacked structure.
  • TMG is used as the Ga material
  • TMA is used as the A1 material
  • TMI is used as the In material
  • Cp Mg is used as the Mg material
  • NH is used as the N material
  • CH is used as the C material.
  • Force Other raw materials may be used.
  • triethylaluminum (TEA) as raw materials for A1
  • N-dimethylaluminum hydride DMAH
  • dimethylaluminum chloride DMAC1
  • trimethylaminealane TMAA
  • triethylindium TEI
  • EtCp Mg bisethylcyclopentadienylmagnesium
  • MeCp Mg Bismethylcyclopentadienylmagnesium
  • NH hydrazine
  • CBr Cylhydrazine
  • DMH Dimethylhydrazine
  • the p-type acceptor impurity that can be used in the present invention is not limited to Mg, and other p-type impurities such as zinc (Zn), beryllium (Be), and cadmium (Cd) may be used.
  • the nitride-based semiconductor element of the present invention is not limited to a semiconductor laser element, but is applied to all nitride-based semiconductor elements having a P-type nitride-based semiconductor layer such as a light-emitting diode element and a light-receiving element.
  • Nitride semiconductors widely include BAlGalnN mixed crystal semiconductors and AlGalnNAsPSb mixed crystal compound semiconductors containing As, P, and Sb.
  • the present invention is suitably used for semiconductor laser elements for optical disk devices, light emitting diodes for illumination, bipolar electronic elements for communication / information processing, and the like.

Abstract

La présente invention concerne un dispositif semi-conducteur au nitrure comprenant un substrat (101) et une structure à couches multiples formée sur le substrat (101). La structure à couches multiples comporte une couche semi-conductrice en nitrure de type n (103), une couche semi-conductrice en nitrure de type p (109), et une couche semi-conductrice en nitrure (105) disposée entre la couche semi-conductrice en nitrure de type n (103) et la couche semi-conductrice en nitrure de type p (109). La couche semi-conductrice en nitrure de type p (109) est dopée au carbone et une impureté de type p différente du carbone. La concentration en carbone de la couche semi-conductrice en nitrure de type p (109) est inférieure à la concentration en impureté de type p différente du carbone, mais supérieure à la concentration en carbone de la couche semi-conductrice en nitrure de type n (103).
PCT/JP2006/313107 2005-07-29 2006-06-30 Dispositif semi-conducteur au nitrure WO2007013257A1 (fr)

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Cited By (20)

* Cited by examiner, † Cited by third party
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JP2009026865A (ja) * 2007-07-18 2009-02-05 Toyoda Gosei Co Ltd Ｉｉｉ族窒化物系化合物半導体発光素子の製造方法
WO2012053331A1 (fr) * 2010-10-19 2012-04-26 昭和電工株式会社 Elément semi-conducteur au nitrure du groupe iii, couche semi-conductrice au nitrure du groupe émettant dans des longueurs d'ondes multiples et procédé de formation d'une couche semi-conductrice au nitrure du groupe iii émettant dans des longueurs d'ondes multiples
CN102544293A (zh) * 2010-12-28 2012-07-04 夏普株式会社 发光装置及其制造方法、透明导电膜的形成方法及电子设备
US8541816B2 (en) 2007-11-02 2013-09-24 Sumitomo Electric Industries, Ltd. III nitride electronic device and III nitride semiconductor epitaxial substrate
EP2743996A2 (fr) * 2011-08-08 2014-06-18 Iljin Led Co., Ltd. Élément électroluminescent semi-conducteur au nitrure donnant un meilleur étalement d'intensité de courant et son procédé de fabrication
JP2014154837A (ja) * 2013-02-13 2014-08-25 Ushio Inc 窒化物半導体発光素子
JP2015005534A (ja) * 2013-06-18 2015-01-08 学校法人立命館 縦型発光ダイオードおよび結晶成長方法
JP2015061050A (ja) * 2013-09-20 2015-03-30 ウシオ電機株式会社 窒化物半導体発光素子
JP2016149458A (ja) * 2015-02-12 2016-08-18 ウシオ電機株式会社 半導体発光素子
JP2017135426A (ja) * 2012-11-19 2017-08-03 新世紀光電股▲フェン▼有限公司 窒化物半導体構造及び半導体発光デバイス
US9842967B2 (en) 2014-06-13 2017-12-12 Ushio Denki Kabushiki Kaisha Nitride semiconductor light emitting element
USRE47088E1 (en) 2012-11-19 2018-10-16 Genesis Photonics Inc. Nitride semiconductor structure and semiconductor light emitting device including the same
US10147845B2 (en) 2012-11-19 2018-12-04 Genesis Photonics Inc. Semiconductor structure
US10153394B2 (en) 2012-11-19 2018-12-11 Genesis Photonics Inc. Semiconductor structure
WO2019106931A1 (fr) * 2017-12-01 2019-06-06 ソニーセミコンダクタソリューションズ株式会社 Dispositif électroluminescent à semi-conducteur
US10319879B2 (en) 2016-03-08 2019-06-11 Genesis Photonics Inc. Semiconductor structure
US10468549B2 (en) 2016-09-19 2019-11-05 Genesis Photonics Inc. Semiconductor device containing nitrogen
US20210143612A1 (en) * 2018-12-11 2021-05-13 Nuvoton Technology Corporation Japan Nitride-based semiconductor light-emitting element and manufacturing method thereof, and manufacturing method of nitride-based semiconductor crystal
JP2021182597A (ja) * 2020-05-19 2021-11-25 豊田合成株式会社 ｐ型ＩＩＩ族窒化物半導体の製造方法、半導体装置
JP7478205B2 (ja) 2017-05-01 2024-05-02 ヌヴォトンテクノロジージャパン株式会社 窒化物系発光装置

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JP2002029897A (ja) * 2000-07-10 2002-01-29 Sumitomo Electric Ind Ltd 単結晶ＧａＮ基板の製造方法と単結晶ＧａＮ基板

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009026865A (ja) * 2007-07-18 2009-02-05 Toyoda Gosei Co Ltd Ｉｉｉ族窒化物系化合物半導体発光素子の製造方法
US8541816B2 (en) 2007-11-02 2013-09-24 Sumitomo Electric Industries, Ltd. III nitride electronic device and III nitride semiconductor epitaxial substrate
WO2012053331A1 (fr) * 2010-10-19 2012-04-26 昭和電工株式会社 Elément semi-conducteur au nitrure du groupe iii, couche semi-conductrice au nitrure du groupe émettant dans des longueurs d'ondes multiples et procédé de formation d'une couche semi-conductrice au nitrure du groupe iii émettant dans des longueurs d'ondes multiples
CN102544293A (zh) * 2010-12-28 2012-07-04 夏普株式会社 发光装置及其制造方法、透明导电膜的形成方法及电子设备
EP2743996A2 (fr) * 2011-08-08 2014-06-18 Iljin Led Co., Ltd. Élément électroluminescent semi-conducteur au nitrure donnant un meilleur étalement d'intensité de courant et son procédé de fabrication
EP2743996A4 (fr) * 2011-08-08 2015-04-08 Iljin Led Co Ltd Élément électroluminescent semi-conducteur au nitrure donnant un meilleur étalement d'intensité de courant et son procédé de fabrication
US9099600B2 (en) 2011-08-08 2015-08-04 Iljin Led Co., Ltd. Nitride semiconductor light-emitting element having superior current spreading effect and method for manufacturing same
USRE47088E1 (en) 2012-11-19 2018-10-16 Genesis Photonics Inc. Nitride semiconductor structure and semiconductor light emitting device including the same
US10381511B2 (en) 2012-11-19 2019-08-13 Genesis Photonics Inc. Nitride semiconductor structure and semiconductor light emitting device including the same
US10153394B2 (en) 2012-11-19 2018-12-11 Genesis Photonics Inc. Semiconductor structure
JP2017135426A (ja) * 2012-11-19 2017-08-03 新世紀光電股▲フェン▼有限公司 窒化物半導体構造及び半導体発光デバイス
US10147845B2 (en) 2012-11-19 2018-12-04 Genesis Photonics Inc. Semiconductor structure
JP2014154837A (ja) * 2013-02-13 2014-08-25 Ushio Inc 窒化物半導体発光素子
TWI577048B (zh) * 2013-02-13 2017-04-01 Ushio Electric Inc Nitride semiconductor light emitting device and manufacturing method thereof
JP2015005534A (ja) * 2013-06-18 2015-01-08 学校法人立命館 縦型発光ダイオードおよび結晶成長方法
JP2015061050A (ja) * 2013-09-20 2015-03-30 ウシオ電機株式会社 窒化物半導体発光素子
US9842967B2 (en) 2014-06-13 2017-12-12 Ushio Denki Kabushiki Kaisha Nitride semiconductor light emitting element
JP2016149458A (ja) * 2015-02-12 2016-08-18 ウシオ電機株式会社 半導体発光素子
US10319879B2 (en) 2016-03-08 2019-06-11 Genesis Photonics Inc. Semiconductor structure
US10468549B2 (en) 2016-09-19 2019-11-05 Genesis Photonics Inc. Semiconductor device containing nitrogen
JP7478205B2 (ja) 2017-05-01 2024-05-02 ヌヴォトンテクノロジージャパン株式会社 窒化物系発光装置
WO2019106931A1 (fr) * 2017-12-01 2019-06-06 ソニーセミコンダクタソリューションズ株式会社 Dispositif électroluminescent à semi-conducteur
JPWO2019106931A1 (ja) * 2017-12-01 2020-11-26 ソニーセミコンダクタソリューションズ株式会社 半導体発光素子
US20210143612A1 (en) * 2018-12-11 2021-05-13 Nuvoton Technology Corporation Japan Nitride-based semiconductor light-emitting element and manufacturing method thereof, and manufacturing method of nitride-based semiconductor crystal
JP2021182597A (ja) * 2020-05-19 2021-11-25 豊田合成株式会社 ｐ型ＩＩＩ族窒化物半導体の製造方法、半導体装置
JP7265108B2 (ja) 2020-05-19 2023-04-26 豊田合成株式会社 ｐ型ＩＩＩ族窒化物半導体の製造方法、半導体装置

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