WO2005106979A1 - Élément luminescent semi-conducteur à nitrure - Google Patents

Élément luminescent semi-conducteur à nitrure Download PDF

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Publication number
WO2005106979A1
WO2005106979A1 PCT/JP2005/008389 JP2005008389W WO2005106979A1 WO 2005106979 A1 WO2005106979 A1 WO 2005106979A1 JP 2005008389 W JP2005008389 W JP 2005008389W WO 2005106979 A1 WO2005106979 A1 WO 2005106979A1
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Prior art keywords
layer
type
concentration
light emitting
thickness
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PCT/JP2005/008389
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English (en)
Japanese (ja)
Inventor
Hiromitsu Kudo
Tomoo Yamada
Kazuyuki Tadatomo
Yoichiro Ouchi
Hiroaki Okagawa
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Mitsubishi Cable Industries, Ltd.
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Priority to JP2006512867A priority Critical patent/JP5082444B2/ja
Publication of WO2005106979A1 publication Critical patent/WO2005106979A1/fr

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    • 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
    • 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
    • H01L33/14—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 with a carrier transport control structure, e.g. highly-doped semiconductor layer or current-blocking structure
    • 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
    • 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
    • H01L33/12—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 with a stress relaxation structure, e.g. buffer layer

Definitions

  • the present invention relates to a nitride semiconductor light emitting device such as a light emitting diode (LED) or a laser diode (LD), which is composed of a nitride semiconductor as a material of a light emitting layer, and more particularly to a p-type semiconductor in the light emitting device structure. It relates to the configuration of the part.
  • a nitride semiconductor light emitting device such as a light emitting diode (LED) or a laser diode (LD), which is composed of a nitride semiconductor as a material of a light emitting layer, and more particularly to a p-type semiconductor in the light emitting device structure. It relates to the configuration of the part.
  • LED light emitting diode
  • LD laser diode
  • the composition ratios of the group III elements constituting the nitride semiconductor, such as ⁇ , ⁇ , and ⁇ in the above formula are also referred to as A 1 ratio, I ⁇ ratio, and Ga ratio, respectively.
  • nitride semiconductor is also referred to as “GaN based light emitting device”.
  • nitride semiconductor light emitting device is also referred to as “GaN based light emitting device”. explain.
  • FIG. 3 is a diagram showing an example of a general element structure of a GaN-based LED, which is one of the GaN-based light-emitting elements, in which a G-N LED is formed on a crystal substrate 100 such as a sapphire substrate.
  • the laminated body S1 composed of the GaN-based crystal layer is formed via the aN-based low-temperature growth buffer layer 100b.
  • the laminate S1 has a pn junction structure including an n-type layer and a p-type layer, and a light emitting layer 120 is formed at the junction.
  • an n-type cladding layer 110 also serving as an n-type contact layer in this example
  • a light-emitting layer (a multilayer structure such as a multiple quantum well) are used.
  • a p-type cladding layer 130, and a p-type contact layer 140 are stacked by vapor phase growth.
  • P 10 and P 20 are an n-side electrode and a p-side electrode, respectively.
  • the light-emitting layer 120 has a II-type cladding layer 110 and a p-type cladding layer. It is made of a crystal having a smaller band gap than that of the layer 130.
  • a light emitting element having a double hetero structure has a light emission output that is at least 10 times higher than that of a light emitting element having a homojunction (for example, Reference 1: Japanese Patent Application Laid-Open No. H8-33069). .
  • the n-type cladding layer 110 is formed to have n-type conductivity by adding an n-type impurity.
  • the p-type cladding layer 130 and the p-type contact layer 140 are doped with a p-type impurity and, if necessary, subjected to a resistance reduction treatment such as a p-type annealing treatment. , Formed into p-type conductivity.
  • the light-emitting layer 120 can be formed to have either n-type conductivity or p-type conductivity, or a mode in which these conductive layers are mixed. In some cases, the layer is undoped without intentionally adding impurities (an undoped layer that does not contain any impurities usually shows weak n-type conductivity).
  • Mg is used as a preferred p-type impurity for making the GaN-based crystal layer p-type conductive.
  • the lower the operating voltage of the light emitting element the more practically desirable.
  • To lower the operating voltage it is better to lower the series resistance of the p-type layer.
  • the mobility deteriorates due to the deterioration of the hole mobility, and the resistance does not decrease sufficiently. Therefore, it is preferable that the amount of Mg added is such that the hole concentration is sufficiently high and the crystallinity is not significantly reduced.
  • the p-type cladding layer is made of AI GaN having an A 1 ratio of 8% or more, so that the above-mentioned band gap is enlarged, and the wavelength of the absorbed light is increased. Is reduced to less than 430 nm, and the thickness of the p-type cladding layer and p-type contact layer is reduced, thereby reducing the problem of light absorption as described above. In order to achieve this, it is known to reduce the thickness of the p-type layer (the entire p-type conductive layer formed above the light-emitting layer, including the p-type cladding layer and the p-type contact layer).
  • the present inventors consider that it is most important to reduce the thickness of the p-type contact layer, and formed a p-type contact layer doped with Mg at a high concentration to a thickness of 10 nm or less, and formed the p-type A GaN-based LED with a rapidly reduced Mg concentration in the layer was fabricated and its evaluation was attempted.
  • the operating voltage of such a GaN LED increases.
  • the reason is considered to be that the Mg concentration in the surface layer of the p-type contact layer decreases due to diffusion due to the concentration gradient, and the contact resistance with the p-side electrode increases.
  • the p-type contact layer in order to sufficiently increase the Mg concentration in the surface layer of the p-type contact layer and reduce the contact resistance with the p-side electrode, the p-type contact layer must be thickened to a certain degree or more. Inevitably, light absorption was involved.
  • An object of the present invention is to solve the above-mentioned problems of the p-type layer and reduce the total amount of Mg added to the p-type layer while maintaining a high Mg concentration in the surface layer of the p-type contact layer.
  • An object of the present invention is to provide a GaN-based light emitting device with a p-type layer structure that can reduce light absorption due to Mg while suppressing an increase in operating voltage.
  • the inventors of the present invention have proposed the unique change of the composition of the GaN-based material, the change of the Mg concentration in the stacking direction, and the thickness of each layer from the p-type contact layer to the layer closest to the light emitting layer in the p-type layer. It has been found that the above object can be achieved by adding a limitation, and the present invention has been completed.
  • the present invention has the following features.
  • (1) It has a stacked body composed of a nitride semiconductor crystal layer, and the stacked body includes an n-type layer, a light-emitting layer, and a p-type layer in order from the lower layer side, and the p-type layer contains Mg as a p-type impurity.
  • a doped nitride semiconductor light emitting device
  • a p-type cladding layer composed of A 1 X G a X N (0 ⁇ x ⁇ 1), and above the p-type cladding layer via one or more heterointerfaces.
  • a 1 y G a x _ y N consists (0 ⁇ y ⁇ l) M g high concentration layer is provided on the upper straight of the Mg-rich layer!
  • Type contact layer is provided,
  • the p-type contact layer has a thickness of 10 nm or less, a Mg concentration a of 5 ⁇ 10 19 cm ⁇ 3 ⁇ a,
  • Mg high concentration layer has a thickness of 5 nm ⁇ 20 nm, M g concentration b is 2 X 10 19 cm one 3 B
  • Mg concentration c is 1 X 10 1 9 cm- 3 ⁇ c ⁇ b
  • a nitride semiconductor light emitting device characterized in that the average value of the Mg concentration of the p-type layer excluding the p-type contact layer is less than 5 ⁇ 10 19 cm— 3 .
  • the Mg-rich layer includes a portion having a Mg concentration of 5 ⁇ 10 19 cm- 3 or more at least on a side in contact with the p-type contact layer.
  • a layer between the Mg-rich layer and the light-emitting layer in the p-type layer includes a portion having a Mg concentration of less than 2 ⁇ 10 19 cm ⁇ 3. element.
  • p-type contact layer has a thickness of 0. 5 ⁇ : 1 0 nm, Mg concentration a is 5 X 10 1 9 cm _3 ⁇ a ⁇ 1 X 10 21 cm - 3, and
  • Mg high concentration layer has a thickness is 5 to 20 nm, 1 ⁇ concentration 1> is 2 1 0 19 cm- 3 ⁇ ( 0. 5 X a) ⁇ b ⁇ 1 X 10 21 cm- 3,
  • nitride semiconductor light-emitting device wherein a layer between the high Mg concentration layer and the light emitting layer among the p-type layers has a Mg concentration c of (0.2 X b) ⁇ c ⁇ b.
  • FIG. 1 is a schematic view showing an element structure of a GaN-based light emitting element according to the present invention. C Touching is performed for the purpose of distinguishing the areas.
  • FIG. 2 is a graph showing the relationship between the thickness of the Mg high-concentration layer, V f, and emission output.
  • FIG. 3 is a schematic diagram showing the element structure of a conventional GaN-based light emitting element.
  • FIG. 1 Each symbol in FIG. 1 indicates the following, respectively. 1; undoped layer, 2; n-type layer, 3; light-emitting layer, 4; p-type layer, 41; p-type cladding layer, 42; low Mg concentration layer, 43; high Mg concentration layer, 44 ; P- type contact layer
  • GaN-based LED which is one of the GaN-based light-emitting elements, as an example.
  • the aspect of the semiconductor laser will be referred to as necessary.
  • the GaN-based LED device structure according to the present invention has a device structure in which a GaN-based crystal layer is sequentially grown on a crystal substrate B1 to form a laminate S, as shown in an example in FIG.
  • the laminate S includes an undoped layer 1, an n-type layer 2, a light-emitting layer 3, and a p-type layer 4 in this order from the lower layer side.
  • the p-type impurity doped into the p-type layer is Mg.
  • the n-type layer 2 includes an n-type contact layer and an n-type cladding layer independently, but in the example shown in the figure, only one layer is used for both layers.
  • the light-emitting layer 3 is a layer for generating light emission due to recombination of carriers, and may have not only a single-layer form but also a laminated structure as described later.
  • P-type layer 4 has at least the bottom; type cladding layer 4 1, M above it g high-concentration layer 43, and directly above the layer 43; a type contact layer 44 is included.
  • the characteristics of the P-type layer composed of the p-type cladding layer 41, the Mg-rich layer 43, and the p-type contact layer 44 are as described in (1) above.
  • the Mg low concentration layer exists between the p-type cladding layer 41 and the Mg high concentration layer 43, which will be described later.
  • the upper surface of the crystal substrate may be flat as in the example of FIG. 3, in the example of the element structure of FIG. 1, irregularities (described later) are formed on the upper surface of the crystal substrate B1, and G a N A buffer layer B2 made of a base material is formed, and an undoped GaN layer 1 and an n-type GaN cladding layer (also serving as an n-type contact layer) 2 are grown to cover the irregularities.
  • the laminate S is etched from the p-type layer side so that the n-type GaN cladding layer 2 is partially exposed, and the exposed portion is provided with an n-side electrode P1 made of A1 (aluminum).
  • a p-side electrode P2 formed by laminating Ni (nickel) and Au (gold) in this order from the side in contact with the upper surface is provided.
  • the p-type cladding layer, the (1> type) ⁇ 18 high-concentration layer, and the p-type contact layer are formed in order from the lower layer side as a stacked structure of the p-type layer ⁇ .
  • the structure is included.
  • Other layers may be present between the Mg-rich layer and the p-type cladding layer (described later).
  • the material composition, Mg addition concentration, layer thickness, etc. of these layers are defined as described in (1) above (preferable embodiments are defined as in (2) to (7) above). The above purpose is achieved by generating the following three effects.
  • the p-type cladding layer is a binary or ternary crystal of A 1 X G a, -X N (0 ⁇ x ⁇ 1), M g High-concentration layer is binary or ternary crystal A 1 y G ay N (0 ⁇ y ⁇ 1), p-type contact layer is ternary crystal A 1 Z G a i_ z N (y ⁇ z ⁇ 1) because it is easy to obtain high-quality crystals with low dislocation density.
  • the mobility of holes is improved by reducing the dislocation density, the resistance of the p-type layer is reduced, and the operating voltage of the light-emitting element can be reduced. In addition, the diffusion of Mg along the dislocation defect region is suppressed.
  • the A1 ratio of the Mg-rich layer is set higher than y because the p-type contact layer formed at the top of the p-type layer is formed by increasing the ratio of A1, which has a stronger binding force with nitrogen than Ga. This is because, during crystal growth, during cooling after crystal growth, during p-type annealing, during electrode annealing, and the like, nitrogen is prevented from being released when exposed to a high-temperature atmosphere.
  • the nitrogen release is suppressed, and the increase in the contact resistance with the electrode and the increase in the series resistance in the layer are suppressed.
  • the Mg concentration a of the layer is set to 5 ⁇ 10 19 cm— 3 ⁇ a, a preferable ohmic contact with the p-side electrode can be achieved within this concentration range, and the contact with the electrode can be achieved. This is because the resistance can be made sufficiently low.
  • Mg-added p-type layer is Mg This is because the higher the concentration, the longer the wavelength of Mg to form a deeper level, and the longer the absorption wavelength, the more easily the light generated in the light emitting layer is absorbed.
  • the amount of Mg contained in the p-type layer is reduced while preventing an increase in the contact resistance of the p-type contact layer by devising the configuration of the entire p-type layer.
  • at least two hetero interfaces which are bonding interfaces of crystals having different compositions, are provided between the p-type cladding layer and the p-type contact layer. That is, at least one provided are hetero interface between the p-type cladding layer and the Mg-enriched layer, and, A l y Ga! _ Y N and Mg high concentration layer made of (0 ⁇ y ⁇ 1), A l z G ai - is a hetero-interface is at least one formed between the z N (y ⁇ z ⁇ 1) made of p-type contact layer.
  • the Mg concentration b of the Mg-rich layer is set to 2 ⁇ 10 19 cm ⁇ 3 ⁇ b
  • the layer thickness is set to 5 nm to 20 nm
  • the p-type conduction layer (p-type
  • the Mg concentration c of the p-type conductive layer between the high Mg concentration layer and the light emitting layer is set to 1 ⁇ 10 19 cm ⁇ 3 ⁇ c ⁇ b.
  • This inequality c ⁇ b means that the Mg concentration b in the Mg-rich layer is higher than the Mg concentration in such a portion of the p-type conduction layer between the Mg-rich layer and the light emitting layer. I have.
  • the average value of the Mg concentration of the p-type layer excluding the p-type contact layer is 5 ⁇ 10 19 cm less than 3 cm.
  • the crystal substrate may be any as long as a GaN-based crystal can be grown.
  • Preferred crystal substrates include, for example, sapphire (C-plane, A-plane, R-plane), SiC (6H, 4H, 3C), GaN, A1N, Si, spinel, ZnO, GaAs, NGO, etc. No. Further, a substrate having these crystals as a surface layer may be used.
  • the plane orientation of the substrate is not particularly limited, and may be a just substrate or a substrate having an off angle.
  • Preferred buffer layers include GaN-based buffer layers.
  • the material, formation method, and formation conditions of the buffer layer may refer to a known technique.
  • Examples of GaN-based buffer layer materials include GaN, AlGaN, A1N, InN, and the like. It is sufficient that the temperature is lower than the growth temperature of the GaN-based crystal layer grown thereon, for example, 300 ° C. to 700 ° C.
  • the thickness of the buffer layer is preferably 10 nm to 50 nm, particularly preferably 20 nm to 40 nm. It is preferable to use GaN as the material of the buffer layer because the dislocation density of the crystal layer grown upward is lowest and the optimum thickness range of the buffer layer is wide.
  • the buffer layer is not essential.
  • the GaN-based crystal layer may be grown on a flat crystal substrate, but a structure for reducing the dislocation density in the crystal may be appropriately introduced on the crystal substrate surface. Along with this, a portion made of a different material such as SiO 2 may be included in the laminate composed of the GaN-based crystal layer.
  • a structure for reducing the dislocation density (i) a mask layer (for example, Sio 2 is used) is formed on a top surface of a crystal substrate by a stripe pattern so that a conventionally known selective growth method (ELO method) can be performed.
  • ELO method selective growth method
  • the structure in which the above-mentioned surface roughness is applied to the upper surface of the substrate does not use a mask layer, so the diffusion of the mask layer material contaminates the GaN crystal. This is preferred because it is prevented.
  • a GaN crystal is grown so as to bury the convexity
  • a crystal substrate made of a material different from the GaN material, such as a sapphire substrate is used, a crystal substrate having a different refractive index is used. a Since the interface with the N-based crystal becomes light-scattering, a favorable effect of improving the light extraction efficiency of the LED (an effect independent of dislocation density reduction) is produced.
  • the GaN-based crystal grown by embedding the irregularities is GaN, especially undoped GaN, it grows upward because it is easy to obtain high-quality crystals with good growth surface flatness and low dislocation density. ! ) It is preferable for improving the quality of the mold layer.
  • the method of processing the unevenness on the upper surface of the crystal substrate, the arrangement pattern of the unevenness, the cross-sectional shape of the unevenness, the growth process of the GaN-based crystal on the unevenness, etc. are described in JP-A-2000-331947, JP-A-2002-164296. References may be referred to.
  • the longitudinal direction of the grooves, the width of the grooves, the width of the convex ridges, the amplitude of the unevenness (the depth of the grooves), and the like are also described in these documents and publicly known. You may refer to the technology.
  • GaN-based crystal layer growth methods include HVPE, MOVPE, and MBE.
  • the MO VPE method is particularly preferable because a high-quality crystal thin film can be formed at a practical growth rate.
  • the light-emitting layer has a multilayer structure such as a single quantum well (SQW) structure or a multiple quantum well (MQW) structure consisting of multiple layers with different band gaps, even if it has a structure composed of a single composition crystal layer.
  • a quantum well structure light emission occurs
  • the entire stacked structure of the barrier layer and the well layer is referred to as a light emitting layer as one unit.
  • the composition of the GaN crystal used for the light emitting layer may be appropriately selected from compositions having a band gap according to the wavelength of the light to be generated, but the band gap is wider than that of the P-type cladding layer and the n-type cladding layer. It is particularly preferable to use a composition having a small value because a double hetero structure is obtained.
  • the band gap of the well layer may be smaller than the band gap of the p-type cladding layer and the n-type cladding layer.
  • the emission wavelength can be widened from about 360 nm (zero In-ratio) to the infrared wavelength range by adjusting the In ratio of the crystal. It can be controlled throughout.
  • the emission wavelength can also be controlled by adding an n-type impurity or a p-type impurity to the light-emitting layer.
  • the light-emitting layer is composed of InGaN, a region in which In is locally distributed at a high concentration is formed, and the region functions as a luminescence recombination center, so that the light-emitting layer has a relatively high dislocation density. , High luminous efficiency can be obtained.
  • the In ratio is reduced to reduce the emission wavelength to a range of less than 420 nm in the violet-ultraviolet region, such effects are unlikely to occur, and the dislocation density in the emission layer greatly affects luminous efficiency. I will do it. Therefore, when the emission wavelength is in such a short wavelength region, it is preferable to employ a structure effective for reducing the dislocation density described above in a structure below the light emitting layer.
  • Carriers can be effectively confined in the light emitting layer by using a material having a larger band gap than the material of the light emitting layer as the material of the n-type cladding layer.
  • a material having a larger band gap than the material of the light emitting layer as the material of the n-type cladding layer.
  • the current density during use is relatively small, it is not necessary to make the difference in the gap between the light emitting layer and the light emitting layer too large. It is also possible to use one with no gap difference (of the same composition) or one with a smaller band gap.
  • the reason is that the injection from the p-type cladding layer into the light-emitting layer
  • the diffusing holes recombine with the electrons with a high probability before reaching the n-type cladding layer, because the diffusing holes have a lower mobility than the electrons diffusing in the opposite direction.
  • the material of the n-type cladding layer includes a binary crystal G aN, a ternary crystal A 1 G a N It is preferable to use InG aN, and particularly preferable to use G aN.
  • the crystallinity tends to decrease when the A 1 ratio is increased. Therefore, the A 1 ratio is preferably set to 0.2 or less, more preferably 0.1 or less.
  • the p-type cladding layer is composed of binary crystal GaN or ternary crystal A 1 GaN. It is desirable to select the composition of the p-type cladding layer so that the band gap is larger than that of the light emitting layer. Specifically, in order to effectively confine electrons diffusing in the light emitting layer in the direction of the p-type cladding layer into the light emitting layer, a band gap with the light emitting layer (or a well layer when the light emitting layer has a quantum well structure) is used. The composition is preferably such that the difference is 0.3 eV or more.
  • the preferable band gap of the p-type cladding layer is 3.4 eV or more.
  • the A 1 ratio X of the mold clad is 0.06 or more.
  • a l holeG ai Since the crystallinity of XN tends to decrease, X is preferably 0.2 or less, more preferably 0.1 or less. As described above, when the crystallinity is lowered, Mg is easily diffused along dislocation defects.
  • the thickness of the p-type cladding layer is not particularly limited, and may be determined by appropriately referring to a known technique, but is preferably 10 nm to 100 nm, and more preferably 20 ⁇ ! ⁇ 70 nm.
  • the Mg-rich layer can be said to be the second contact layer located immediately below the thin p-type contact layer.
  • the present invention is characterized in that at least one hetero interface is provided between the p-type cladding layer and the Mg-rich layer.
  • the A1 ratio X of the p-type cladding layer should be different from the A1 ratio y of the Mg-rich layer. .
  • the difference between X and y is preferably 0.01 or more, more preferably 0.03 or more, More preferably, it is 0.05 or more.
  • the difference between X and y is preferably 0.2 or less, more preferably 0.15 or less. Preferably it is 0.1 or less.
  • y is preferably set to 0.2 or less. Further, the A 1 ratio y of the Mg-rich layer may be smaller than the A 1 ratio X of the p-type clad layer. As y becomes smaller, the band gap of the Mg-rich layer becomes smaller, so that it becomes easier to activate as a Mg-force Sp-type impurity, and a decrease in series resistance due to an increase in carrier concentration can be expected. Therefore, the more preferable range of y is 0 ⁇ y ⁇ 0.05, and it is more preferable to form the Mg-rich layer with G a N.
  • the material composition of the p-type contact layer A l z G ai - a z N (y ⁇ z ⁇ 1) , A 1 ratio z of that is larger than A 1 ratio y of Mg high concentration layer, the As described in Effect of the Invention, the effect of suppressing nitrogen release from the surface in a high-temperature atmosphere and the effect of suppressing Mg diffusion by the hetero interface are generated. From the viewpoint of suppressing nitrogen elimination in a high-temperature atmosphere, 0.01 ⁇ z is preferable, and particularly preferably 0.03 ⁇ z.
  • z is preferably 0.2 or less, and more preferably z. 0.1 or less, more preferably 0.05 or less.
  • the Mg concentration a of the p-type contact layer may be set to a concentration high enough to form a good ohmic contact with the electrode, and a known technique can be referred to. Specifically, if 5 x 10 19 cm- 3 ⁇ a, especially 1 x 10 2 ° cm- 3 ⁇ a, the distance between various electrodes known as p-type common electrodes As a result, a good ohmic contact is formed.
  • the Mg concentration a is preferably 5 ⁇ 10 19 cm— 3 to 1 ⁇ 10 21 cm— 3 , more preferably 5 ⁇ 10 21 cm— 3. 19 cm— 3 to 5 X 10 2 . cm- 3, and particularly preferably 5 X 1 0 19 cm one 3 to 1 X 10 20 cm one 3.
  • the thickness of the p-type contact layer is 0.5 nm or more, the operating voltage of the light-emitting device will be lower than in the case where the p-side electrode is formed directly on the Mg-rich layer, probably due to the reduction in contact resistance.
  • the p-type contact layer is added with a high concentration of Mg, light absorption due to Mg is suppressed as the layer thickness is reduced.
  • the layer thickness of the p-type contact layer is preferably from 0.5 nm to 10 nm, more preferably from 0.5 11111 to 5 11111.
  • the p-type layer is formed by the MOVP E method, if a large amount of hydrogen that inhibits activation of Mg as a p-type impurity enters the p-type layer during crystal growth, the series resistance of the p-type layer increases. And the operating voltage of the device is estimated to increase due to an increase in the contact resistance between the P- type contact layer and the p-side electrode. Alternatively, it is necessary to perform a process such as annealing for activating Mg under more severe conditions, and there is a possibility that the device may be deteriorated due to the process.
  • an inert gas such as nitrogen among the gases supplied into the reaction vessel during the growth of the p-type layer, except for the carrier gas used as the organometallic compound raw material.
  • the growth rate of the material is significantly reduced.
  • the thickness of the p-type layer is large, the time required for the growth is long, and as a result, the time required for the crystal layer to be exposed to high temperatures is prolonged. Degradation is promoted, and the device characteristics tend to deteriorate. Reducing the thickness of the Mg-rich layer or the ⁇ -type contact layer is also preferable in suppressing such a decrease in device characteristics.
  • the Mg concentration b of the Mg-rich layer should be 2 ⁇ 10 19 cm— 3 ⁇ b.
  • the Mg concentration at the part in contact with the p-type contact layer should be 5 ⁇ 10 19 cm— 3 or more. Is preferred.
  • the Mg concentration b of the Mg high concentration layer be lower than that of the p-type contact layer. Since the Mg-rich layer is formed of a GaN-based crystal with a smaller A1 ratio than the p-type contact layer, that is, a GaN-based crystal with a smaller bandgap, the Mg-rich layer and the p-type If the same layer is doped with the same concentration of Mg, the light absorption in the Mg-rich layer becomes larger than that in the p-type contact layer.
  • the layer thickness of the high Mg concentration layer is 5 nm to 20 nm. 5x10 Mg high concentration layer If a part containing Mg at a concentration of 19 cm- 3 or more is included, only the side of the Mg-rich layer that is in contact with the p-type contact layer has the Mg concentration, since light absorption by Mg is suppressed. it is preferable that the 5 X 1 0 19 cm one 3 or more. When this is done, the p-type layer of the lower than the p-type contact layer, the thickness of the portion is Mg concentration 5 X 1 0 19 cm one 3 or more, and 20 nm or less. A more preferred range for this thickness is 5 nrr! 1515 nm, more preferably 5 nrr! ⁇ 10 nm.
  • the Mg concentration and thickness in terms of providing the M g high concentration layer specified as described above, p-type conductive layer between the Mg-enriched layer and the light-emitting layer in the p-type layer (e.g., in Figure 1
  • the Mg concentration c of the p-type cladding layer 31 and the Mg low concentration layer 32) is set to 1 X 10 19 c'm 1-3 ⁇ c, so that the p-type The diffusion of Mg from the surface of the contact layer is suppressed, and the rise in operating voltage of the device is suppressed.
  • setting (0.2 Xb) ⁇ c is one of preferred embodiments for achieving the object of the present invention.
  • Mg concentration stepwise between the high Mg concentration layer and the p-type conductive layer immediately below it is preferable to change the Mg concentration stepwise between the high Mg concentration layer and the p-type conductive layer immediately below.
  • l X 10 19 cm one 3 or more further can be provided with 3 X 10 19 cm one 3 or more Mg concentration difference.
  • Contact name by the condition that c ⁇ b, formed in the step of such a Mg concentration is also essential for a not, for example, a p-type cladding layer toward M g high concentration layer, Mg concentration linearity to increase Is also acceptable.
  • the Mg concentration c it is preferably Ri yo an upper limit value of 5 X 10 19 cm one 3, because, in the p-type conductive layer doped with Mg, the Mg concentration 5 X 10 19 cm one If the concentration is higher than 3 (preferable Mg concentration for the p-type contact layer), light absorption caused by Mg becomes a particular problem.
  • the P-type layer between the Mg-rich layer and the light-emitting layer contains a portion where the Mg concentration is less than 2 ⁇ 10 19 cm- 3. preferably to so that Re, further more preferably an average value of the Mg concentration in the!) type layer is made to be less than 2 X 10 19 cm one 3.
  • the p-type contact layer, the Mg-rich layer, and the p-type cladding layer may be continuous three layers, but between the Mg-rich layer and the p-type cladding layer, another Mg-rich layer is provided.
  • a low Mg concentration layer having a lower Mg concentration may be further provided.
  • the Mg low concentration layer is preferably provided so that the entire p-type layer has a thickness of 100 nm or more, preferably 100 nm to 30 O nm, and more preferably 100 nm to 200 nm. It is preferable that the total thickness of the p-type layer is larger than 100 nm because the balance with the n-type layer is improved, during cooling after crystal growth, during p-type annealing, and during electrode formation. This is because deterioration of the light emitting layer at the time of annealing treatment or the like is suppressed.
  • the total thickness of the p-type layer is larger than 30 O nm, these effects are saturated, and if the layer thickness is further increased, the problem of light absorption by Mg increases, and the manufacturing time increases. Problems such as reduced efficiency and wasted material occur. Also, if the growth time of the p-type layer is too long, there is a problem that the device is deteriorated due to the high temperature during the growth.
  • the composition of the low Mg concentration layer may be determined so that the interface with the high Mg concentration layer and / or the p-type cladding layer is a hetero interface.
  • the A 1 ratio is preferably 0.2 or less, particularly preferably 0.1 or less.
  • M g low concentration layer directly above the M g high concentration layer material having the same crystal composition as A l y G ai _ y N a (0 ⁇ y ⁇ 1) may be used. If the low Mg concentration layer has the same crystal composition as the Mg high concentration layer directly above, or has a superlattice structure, the crystallinity of the Mg high concentration layer immediately above and, by extension, the P-type contact layer above it Can be expected to improve This is preferable from the viewpoint of lowering the resistance of the Mg-rich layer or the p-type contact layer and suppressing the diffusion of Mg that occurs along dislocation defects.
  • An additional layer may be inserted between the Mg-rich layer and the p-type cladding layer, if necessary, in view of the element structure.
  • a surface emitting laser a laser in which the emission direction ′ matches the emission direction and the stacking direction
  • a plug reflection layer as one reflection layer of the resonator
  • an edge emission laser an oscillation direction ⁇ A light confinement layer in the case of forming a laser whose emission direction is perpendicular to the lamination direction).
  • the Bragg reflection layer or the light confinement layer may be an independent layer, or may be a layer partially or entirely serving as a high Mg concentration layer or a low Mg concentration layer.
  • a binary crystal GaN or a ternary crystal A 1 GaN it is preferable to use a binary crystal GaN or a ternary crystal A 1 GaN, and to use A 1 GaN when using A 1 GaN.
  • the A 1 ratio of the GaN crystal is preferably 0.2 or less, particularly preferably 0.1 or less.
  • each of the layers such as the p-type contact layer, the Mg-rich layer, the Mg-poor layer, and the p-type clad layer is provided that the crystal composition and the Mg concentration fall within a predetermined range defined by the present invention.
  • a multilayer structure (including a superlattice structure) may be used.
  • the GaN-based LED as an actual example of the GaN-based light emitting device of the present invention, including an experiment for specifying the preferable thickness of the p-type contact layer and the Mg concentration of the Mg-rich layer, will be described. A specific configuration will be described.
  • the Mg concentration and film thickness of the Mg-doped layer shown in the following experiments are all design values, and the measured values of the actually obtained product may include manufacturing errors.
  • the growth of the Mg-doped layer having a specific Mg concentration (design value) in each experiment was performed by the following procedure.
  • Mg concentration of predetermined design value sought [Mg Roh group III ratio], while supplying the Mg raw material and group III material at its [M g / group III ratio], MOVPE A GaN-based crystal layer is grown by the method.
  • the film thickness of each layer was controlled by determining the growth time required to grow the film to a predetermined thickness from the growth rate when the film having the composition was grown alone, and growing the film for the growth time.
  • the thickness of the A 1 G aN layer and G a N layer fabricated in each experiment was measured to be approximately the designed values by measuring the distribution of G a and A 1 in the depth direction by using SIMS. confirmed. Especially when the film thickness was small, XPS (X-ray Photoelectron Spectroscopy), which is an analysis method with higher resolution in the thickness direction, was also confirmed.
  • XPS X-ray Photoelectron Spectroscopy
  • the thickness of the p-type contact layer or the high-concentration Mg layer When the thickness of the p-type contact layer or the high-concentration Mg layer is small, the influence of the diffusion and outflow of Mg into the adjacent layer or the inflow of Mg from the adjacent layer becomes large. Was sometimes inclined. In some cases, the thickness of the Mg-rich layer was smaller than the design value due to the outflow of Mg to the adjacent Mg-poor layer.
  • a GaN LED having the structure shown in Fig. 1 was fabricated.
  • the MOVP E method was used to grow the GaN-based crystal layer.
  • the thickness of the contact layer is assumed to be A, and the p-type GaN layer (Mg low concentration layer 42 and M
  • the light emission characteristics were evaluated by setting the layer thickness of the high-concentration layer 43 as one layer) as B, and changing the thicknesses A and B of both layers.
  • each layer of the GaN-based LED fabricated in this experiment is shown in order from the upper layer to the lower layer.
  • the p-type GaN layer should be divided into a high-concentration Mg layer and a low-concentration Mg layer.
  • the Mg concentration was set to 5 ⁇ 10 19 (cm ⁇ 3 ) over the entire layer.
  • the layer thickness is B (nm).
  • An MQW structure is used in which a GaN barrier layer and an In GaN well layer (emission wavelength: 405 nm) are stacked for six periods.
  • the top layer was a GaN barrier layer.
  • the layer thickness is 100 (nm). (N-type cladding layer)
  • GaN also used as n-type contact layer, layer thickness is 4 (m).
  • the layer thickness is 2 ⁇ m), which is the thickness of the part above the top surface of the projection of the substrate.
  • the surface of the C-plane sapphire substrate was subjected to a stripe-shaped pattern and processed to have a rectangular wave-shaped cross section.
  • a GaN buffer layer was grown on the top surface of the projection and the bottom surface of the depression in the irregularities.
  • the upper limit of the thickness of the p-type contact layer should be 10 nm.
  • the Vf forward voltage required to pass a forward current of 2 OmA when the thickness of the p-type contact layer was 10 nm was 3.5 V.
  • the thickness of the p-type contact layer was fixed at 1 O nm.
  • the layer thickness was 9 Onm, and the Mg concentration was 1 ⁇ 10 19 (cm " 3 ) to further suppress light absorption by Mg.
  • the cause is that Mg diffuses and flows out from the p-type contact layer to the p-type GaN layer immediately below, thereby lowering the Mg concentration in the surface layer of the p-type contact layer. This is presumed to be because the contact resistance with the p-side electrode increased. Since the p-type contact layer is as thin as 1 O nm, the total amount of Mg retained in this layer is small, and it is probable that the effect of the outflow of Mg appears remarkably.
  • the aspect of the Mg addition to the p-type GaN layer was changed. Specifically, the Mg concentration at the bottom of the p-type GaN layer (the region in contact with the p-type cladding layer) is 1 ⁇ 10 19 cm 3, and the Mg concentration at the top (the region in contact with the p-type contact layer) is 5 ⁇ 5.
  • Mg concentration at the bottom of the p-type GaN layer is 1 ⁇ 10 19 cm 3
  • the Mg concentration at the top is 5 ⁇ 5.
  • Mg concentration at the top is 5 ⁇ 5.
  • Mg concentration was varied so that to increase substantially continuously towards the layer from a lower portion to an upper portion layer (gradient doped).
  • Vf decreased to the same level as in Experiment 1, and it is considered that the suppression of the diffusion outflow of Mg from the p-type contact layer was achieved.
  • the light emission output dropped to the same level as in Experiment 1, suggesting that the Mg-gradient doping in Experiment 3 may not sufficiently suppress the light absorption caused by Mg.
  • the thickness of the high concentration layer is preferably 5 to 20 nm.
  • the design value of the Mg concentration of the p-type contact layer is set to a higher concentration, the problem of insufficient Mg concentration does not occur, so that similarly low V f can be obtained.
  • the design value is set to a lower concentration, the concentration difference between the p-type contact layer and the p-type high concentration layer becomes smaller, and the diffusion and outflow of Mg from the p-type contact layer are more effectively suppressed. Therefore, a similarly low V f is obtained.
  • the upper side is a Mg high concentration layer (layer thickness 5 nm, Mg concentration 5 ⁇ 10 19 cm- 3 ), and the remaining lower side is M g low concentration layer (thickness 85 nm, M g concentration 1 X 10 19 cm- 3) is fixed to, changes in the thickness of the p-type co Ntakuto layer T (nm) of the various thin range than 10 nm I let it.
  • the flow rate ratio of hydrogen gas to the hydrogen gas, ammonia, and nitrogen gas supplied to the reaction vessel was 30% or less.
  • the growth rate of the p-type contact layer was about one-fifth of that in Experiments 1 to 4 in which the flow rate of hydrogen gas was about 60%. Except for this change, a GaN LED was manufactured with the same specifications as in Experiment 4, and V f and emission output were measured.
  • the layer thickness X of the Mg-rich layer was fixed at 5 nm, and the layer thickness Y of the Mg-low layer was 8511 m.
  • ⁇ A ⁇ concentration 1 ⁇ high concentration layer with 5 X 10 19 cm- 3 was varied between 1 X 10 1 9 cm one 3.
  • a GaN-based LED was manufactured with the same specifications as in Experiment 4, and V f was measured.
  • V f was at the same level as in Experiment 2 when the Mg concentration in the Mg-rich layer was between 1 ⁇ 10 19 cm— 3 (corresponding to Experiment 2 above) and 2 ⁇ 10 19 cm— 3 .
  • Mg started to decrease with the concentration of more than 2 X 10 19 cm one 3, close to the 5 X 10 19 cm- is a value at 3 3. 5 V.
  • the thickness of the Mg-enriched layer is provided immediately below the p-type contact layer 5 nm or more, if the Mg concentration is 2 X 10 19 cm one 3 above, the thickness of the p-type contact layer It has been found that there is an effect of suppressing an increase in operating voltage at the time.
  • the light emitting element does not simply have to have a high output, but there is a demand for low power consumption from the device / apparatus side in which the element is incorporated. 9 Further, the operating voltage of a light emitting element is directly related to the amount of heat generated by the element, and thus greatly affects the life of the element. In addition, since there is a need for a mounting structure that gives priority to heat radiation as the heat generation increases, there is also a problem that various design restrictions are generated.
  • the problem of light absorption can be improved by effectively reducing the total amount of Mg in the p-type layer while suppressing an increase in the operating voltage of the GaN-based semiconductor light emitting device. .

Abstract

Dans un élément luminescent à base GaN utilisant du Mg comme impureté de type p d’une couche de type p, une couche de revêtement de type p (31) composé de AlxGa1-xN (0≤x≤1) est prévue à la partie la plus basse de la couche de type p, une couche de concentration élevée de Mg (33) composée d'un AlyGa1-yN (0≤y≤1) est prévue sur une partie supérieure de la couche de revêtement par le biais d’au moins une interface avec celle-ci, et juste au-dessus de la couche de concentration élevée Mg, une couche de contact de type p (34) composée de AlzGa1-zN (y<z≤1) est prévue. La couche de contact de type p a une épaisseur de couche inférieure ou égale à 10 nm et une concentration de Mg (a) de 5×1019cm-3≤(a), la couche de concentration élevée de Mg a une épaisseur de film comprise entre 5 nm et 20 nm et une concentration de Mg (b) de 2×1019cm-3<(b), et une couche située entre la couche de concentration élevée de Mg et une couche luminescent a une concentration de Mg (c) de 1×1019cm-3≤(c)<(b). Une concentration moyenne de Mg des couches de type p à l’exclusion de la couche de contact de type p est inférieure à 5×1019cm-3. L'absorption de lumière causée par Mg peut être réduite, tout en supprimant une augmentation d’une tension d’exploitation, en réduisant la quantité totale de Mg ajoutée à la couche de type p, tout en maintenant la concentration élevée de Mg d’une couche avant de la couche de contact de type p.
PCT/JP2005/008389 2004-04-28 2005-04-26 Élément luminescent semi-conducteur à nitrure WO2005106979A1 (fr)

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JP2009021424A (ja) * 2007-07-12 2009-01-29 Opnext Japan Inc 窒化物半導体発光素子及びその製造方法
WO2015029578A1 (fr) * 2013-08-27 2015-03-05 富士電機株式会社 Procédé de fabrication de dispositif à semi-conducteur, et dispositif à semi-conducteur
CN105304777A (zh) * 2014-07-18 2016-02-03 丰田合成株式会社 第iii族氮化物半导体发光器件及其制造方法
JP2017050439A (ja) * 2015-09-03 2017-03-09 豊田合成株式会社 紫外発光素子およびその製造方法
JP2017139447A (ja) * 2016-02-01 2017-08-10 パナソニック株式会社 紫外線発光素子
CN114038958A (zh) * 2021-08-05 2022-02-11 重庆康佳光电技术研究院有限公司 发光芯片外延片及其制作方法、发光芯片
US11302845B2 (en) 2017-07-27 2022-04-12 Nikkiso Co., Ltd. Semiconductor light-emitting element

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JP2009272380A (ja) * 2008-05-01 2009-11-19 Sumitomo Electric Ind Ltd Ｉｉｉ族窒化物結晶およびその表面処理方法、ｉｉｉ族窒化物積層体およびその製造方法、ならびにｉｉｉ族窒化物半導体デバイスおよびその製造方法

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JP2009021424A (ja) * 2007-07-12 2009-01-29 Opnext Japan Inc 窒化物半導体発光素子及びその製造方法
WO2015029578A1 (fr) * 2013-08-27 2015-03-05 富士電機株式会社 Procédé de fabrication de dispositif à semi-conducteur, et dispositif à semi-conducteur
CN105304777A (zh) * 2014-07-18 2016-02-03 丰田合成株式会社 第iii族氮化物半导体发光器件及其制造方法
JP2016025196A (ja) * 2014-07-18 2016-02-08 豊田合成株式会社 Ｉｉｉ族窒化物半導体発光素子とその製造方法
JP2017050439A (ja) * 2015-09-03 2017-03-09 豊田合成株式会社 紫外発光素子およびその製造方法
JP2017139447A (ja) * 2016-02-01 2017-08-10 パナソニック株式会社 紫外線発光素子
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CN114038958A (zh) * 2021-08-05 2022-02-11 重庆康佳光电技术研究院有限公司 发光芯片外延片及其制作方法、发光芯片

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