EP3384534A1 - Dispositif optoelectronique comportant des structures semiconductrices tridimensionnelles a portion monocristalline elargie - Google Patents
Dispositif optoelectronique comportant des structures semiconductrices tridimensionnelles a portion monocristalline elargieInfo
- Publication number
- EP3384534A1 EP3384534A1 EP16813091.2A EP16813091A EP3384534A1 EP 3384534 A1 EP3384534 A1 EP 3384534A1 EP 16813091 A EP16813091 A EP 16813091A EP 3384534 A1 EP3384534 A1 EP 3384534A1
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- Prior art keywords
- optoelectronic device
- doped
- doped portion
- semiconductor compound
- enlarged
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- H10H20/821—Bodies characterised by their shape, e.g. curved or truncated substrates of the light-emitting regions, e.g. non-planar junctions
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- H10F77/10—Semiconductor bodies
- H10F77/14—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies
- H10F77/143—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies comprising quantum structures
- H10F77/1437—Quantum wires or nanorods
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- H10F71/00—Manufacture or treatment of devices covered by this subclass
- H10F71/127—The active layers comprising only Group III-V materials, e.g. GaAs or InP
- H10F71/1272—The active layers comprising only Group III-V materials, e.g. GaAs or InP comprising at least three elements, e.g. GaAlAs or InGaAsP
- H10F71/1274—The active layers comprising only Group III-V materials, e.g. GaAs or InP comprising at least three elements, e.g. GaAlAs or InGaAsP comprising nitrides, e.g. InGaN or InGaAlN
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- H10F71/127—The active layers comprising only Group III-V materials, e.g. GaAs or InP
- H10F71/1276—The active layers comprising only Group III-V materials, e.g. GaAs or InP comprising growth substrates not made of Group III-V materials
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- H10F77/124—Active materials comprising only Group III-V materials, e.g. GaAs
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- H10F77/124—Active materials comprising only Group III-V materials, e.g. GaAs
- H10F77/1248—Active materials comprising only Group III-V materials, e.g. GaAs having three or more elements, e.g. GaAlAs, InGaAs or InGaAsP
- H10F77/12485—Active materials comprising only Group III-V materials, e.g. GaAs having three or more elements, e.g. GaAlAs, InGaAs or InGaAsP comprising nitride compounds, e.g. InGaN
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- H10F77/10—Semiconductor bodies
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- H10H20/011—Manufacture or treatment of bodies, e.g. forming semiconductor layers
- H10H20/013—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials
- H10H20/0133—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials with a substrate not being Group III-V materials
- H10H20/01335—Manufacture or treatment of bodies, e.g. forming semiconductor layers having light-emitting regions comprising only Group III-V materials with a substrate not being Group III-V materials the light-emitting regions comprising nitride materials
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- H10H20/811—Bodies having quantum effect structures or superlattices, e.g. tunnel junctions
- H10H20/812—Bodies having quantum effect structures or superlattices, e.g. tunnel junctions within the light-emitting regions, e.g. having quantum confinement structures
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- H10H20/822—Materials of the light-emitting regions
- H10H20/824—Materials of the light-emitting regions comprising only Group III-V materials, e.g. GaP
- H10H20/825—Materials of the light-emitting regions comprising only Group III-V materials, e.g. GaP containing nitrogen, e.g. GaN
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- H10H20/811—Bodies having quantum effect structures or superlattices, e.g. tunnel junctions
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- H10H20/80—Constructional details
- H10H20/81—Bodies
- H10H20/822—Materials of the light-emitting regions
- H10H20/824—Materials of the light-emitting regions comprising only Group III-V materials, e.g. GaP
Definitions
- the field of the invention is that of optoelectronic devices comprising three-dimensional semiconductor structures, such as nanowires or microwires, adapted to emit or detect light radiation.
- optoelectronic devices comprising three-dimensional semiconductor structures of nanowires or microwires forming, for example, light-emitting diodes.
- the nanowires or microfilts usually comprise a first doped portion, for example n-type, wire-shaped, and a second doped portion of the opposite conductivity type, for example p-type, between which is located an active zone comprising at least one well quantum.
- the nanowires or microwires may be made in a so-called axial configuration, in which the active zone and the second p-doped portion extend essentially in the extension of the first doped portion, along a longitudinal axis of epitaxial growth, without surrounding the periphery of the the latter. They can also be made in a so-called radial configuration, also called core / shell, in which the active zone and the second p-doped portion surround one end of the first n-doped portion.
- Nanowires or microwires in radial configuration may, however, have a mismatch between the semiconductor compound forming the active zone and the one forming the first doped portion. Such mesh clash is likely to result in degradation of the electronic and / or optical properties of the nanowires or microwires.
- the object of the invention is to remedy at least in part the disadvantages of the prior art.
- the object of the invention is an optoelectronic device, comprising at least one three-dimensional semiconductor structure extending along a longitudinal axis substantially orthogonal to a plane of a substrate on which it rests, and comprising a first doped portion, extending from the substrate along the axis longitudinal, and made of a first semiconductor compound; an active zone comprising at least one quantum well, and extending from the first doped portion; a second doped portion, at least partially covering the active zone.
- the active zone comprises an enlarged monocrystalline portion formed of a single crystal of a second semiconductor compound formed of a mixture of the first semiconductor compound and at least one additional element; extending from an upper face of an end of the first doped portion opposite the substrate; and having a mean diameter greater than that of the first doped portion.
- the active zone is made based on said second semiconductor compound.
- the active zone is made of one or more semiconductor materials which each comprise at least the same elements as those of the second semiconductor compound. It therefore does not include a layer made of the first semiconductor compound.
- it consists of at least one semiconductor compound comprising at least the same elements as the first semiconductor compound and at least the additional element.
- the mesh mismatch in the active zone is limited by the fact that it is made from the same semiconductor compound.
- the most important mismatch is then transferred to the interface between the first semiconductor compound of the first doped portion and the second semiconductor compound of the single crystal. It is then possible to make an active zone of greater thickness and / or greater atomic proportion of the additional element, while the first doped portion is made of the first semiconductor compound.
- the second semiconductor compound is InGaN.
- the active zone may include multiple quantum wells that overlap at least a portion of the enlarged monocrystalline portion.
- Multiple quantum wells may be formed of alternating barrier layers and quantum well forming layers, said barrier layers and quantum wells being made based on the second semiconductor compound.
- the barrier layers have a first nonzero value of atomic proportion to said additional element of the second semiconductor compound.
- the quantum wells have a second atomic proportion value in said additional element greater than the first value.
- the mismatch between the multiple quantum wells made based on the second semiconductor compound and the first doped portion made in the first semiconductor compound is limited.
- the second semiconductor compound of the expanded monocrystalline portion may be doped with the same type of conductivity as that of the first doped portion.
- the first semiconductor compound is gallium nitride and the second semiconductor compound is gallium indium nitride.
- the first atomic proportion value in said additional element of the barrier layers is between 15% and 23%
- the second atomic proportion value in said additional element of the quantum wells is between 22% and 30%.
- the first semiconductor compound is GaN
- the second semiconductor compound of InGaN it is possible to produce quantum wells whose atomic proportion of indium makes it possible to emit light radiation into the green, c. that is to say, whose emission spectrum has a peak intensity at a wavelength of between 495 nm and 50 nm, for example equal to about 530 nm, while having an improved internal quantum efficiency while the first portion doped is made of GaN.
- the monocrystal has an atomic proportion to said additional element equal to that of the barrier layer in contact therewith.
- the mismatch between the single crystal and the barrier layer in contact therewith is limited, the most important mismatch being transferred to the interface between the first semiconductor compound of the first doped portion and the second semiconductor compound. of the single crystal, which limits the mechanical stresses between the single crystal and the barrier layer in contact. It is then possible to make quantum wells of greater thickness and / or greater atomic proportion of the additional element.
- the enlarged monocrystalline portion may have an average thickness, along the longitudinal axis, greater than 10 nm.
- the enlarged monocrystalline portion may have an average diameter greater than 110% of the average diameter of the first doped portion.
- Said quantum well may be made of a semiconductor material based on the second semiconductor compound.
- the first semiconductor compound may be selected from III-V compounds, II-VI compounds and IV elements or compounds, and preferably is a III-N compound.
- the second doped portion may be at least partially surrounded by a bias electrode.
- the expanded monocrystalline portion may form a single quantum well, the second semiconductor compound preferably being unintentionally doped.
- the enlarged monocrystalline portion may have at least two semi-polar faces of different inclinations with respect to the longitudinal axis, said semi-polar faces being covered by at least one quantum well coated by the second doped portion.
- the optoelectronic device may comprise at least two polarization electrodes adapted to each polarize a portion of the second doped portion located at one or other of said semi-polar faces.
- the invention also relates to a method for producing an optoelectronic device according to any one of the preceding features, wherein the three-dimensional semiconductor structure is formed by chemical vapor deposition, the first semiconductor compound being a III-V compound.
- a V / III ratio between a precursor gas stream of element V on a precursor gas stream of element III has a value less than or equal to 100, and wherein during the formation of the expanded monocrystalline portion, said V / III ratio has a value greater than or equal to 500.
- an H 2 / N 2 ratio between a proportion of molar flow of hydrogen over a proportion of molar flow of nitrogen has a value greater than or equal to 60/40, preferably greater than or equal to 60/40. or equal to 70/30, and wherein during formation of the expanded single crystal portion, said H2 / N2 ratio has a value less than or equal to 40/60, preferably less than or equal to 30/70.
- FIG. 1 is a partial and schematic cross-sectional view of an example of an optoelectronic device comprising nanowires or microwires in a radial configuration
- FIG. 2 is a partial schematic cross-sectional view of a first embodiment of an optoelectronic device comprising nanowires or microfilts in a radial configuration and whose active zone comprises an enlarged monocrystalline portion surrounded by multiple quantum wells; ;
- FIG. 3 is a partial diagrammatic cross-sectional view of the optoelectronic device shown in FIG. 2, illustrating the angles of inclination a and ⁇ respectively formed by the lateral and upper edges with respect to the longitudinal axis. ⁇ of the wire;
- FIG. 4 is a partial and schematic cross-sectional view of a variant of the first embodiment of an optoelectronic device
- FIG. 5 is a partial and schematic cross-sectional view of a second embodiment of an optoelectronic device comprising nanowires or microfilts in radial configuration and whose active zone comprises an enlarged monocrystalline portion forming a single quantum well;
- FIGS. 6 and 7 are partial and schematic cross-sectional views of two variants of the optoelectronic device according to the first embodiment in which the second polarization electrode or electrodes are arranged to polarize different parts of the second doped portion resting on semipolar faces of the wires.
- the invention relates to an optoelectronic device comprising three-dimensional semiconductor structures adapted to form light-emitting diodes or photodiodes.
- the three-dimensional semiconducting structures have an elongated shape along a longitudinal axis ⁇ , that is to say whose longitudinal dimension along the longitudinal axis ⁇ is greater than the transverse dimensions.
- the three-dimensional structures are then called "son", “nanowires” or “microfilts".
- the transverse dimensions of the wires that is to say their dimensions in a plane orthogonal to the longitudinal axis ⁇ , may be between 1 ⁇ m and 1 ⁇ m, for example between 1 ⁇ m and 10 ⁇ m, and preferably between 100 nm and 5 ⁇ .
- the height of the wires that is to say their longitudinal dimension along the longitudinal axis ⁇ , is greater than the transverse dimensions, for example 2 times, 5 times and preferably at least 10 times greater.
- the cross section of the son in a plane orthogonal to the longitudinal axis ⁇ , may have different shapes, for example a circular shape, oval, polygonal for example triangular, square, rectangular or hexagonal.
- the diameter is defined here as a quantity associated with the perimeter of the wire at a cross-section. It can be the diameter of a disc having the same surface as the cross section of the wire.
- the local diameter is the diameter of the wire at a given height thereof along the longitudinal axis ⁇ .
- the average diameter is the average, for example arithmetic, of local diameters along the wire or a portion thereof.
- FIG. 1 schematically illustrates a partial sectional view of an example of an optoelectronic device 1 comprising three-dimensional semiconductor structures 2 forming wire electroluminescent diodes in a radial configuration.
- a three-dimensional orthonormal reference ( ⁇ , ⁇ , ⁇ ) is defined here and for the rest of the description, in which the plane (X, Y) is substantially parallel to the plane of a substrate of the optoelectronic device, the Z axis being oriented according to a direction substantially orthogonal to the plane of the substrate.
- a first portion 10, doped with a first type of conductivity is in the form of a wire which extends along a longitudinal axis ⁇ , the latter being oriented substantially orthogonal to the plane (X , Y) of a front face 3b of a substrate 3.
- the end 11 of the first doped portion 10, opposite the substrate 3, is covered, at its upper edge 14 and its lateral edge 13, by a layer or stack of layers forming an active zone 30 which comprises at least one quantum well.
- the active zone 30 is itself covered by a layer forming a second portion 20, doped with a second type of conductivity opposite to the first type.
- the first doped portion 10 and the second doped portion 20 respectively form the core and the shell of the wire 2 said core / shell configuration.
- the wire 2 is made based on a first semiconductor compound, for example GaN.
- the first and second doped portions 10, 20 may be made of respectively n-type and p-type doped GaNs.
- the active zone 30 comprises at least one quantum well in the form of a layer located between the first and second doped portions 10, 20, and made of a second semiconductor compound formed of a mixture of the first semiconductor compound and at least one additional element, for example from InGaN, so that its bandgap energy is less than that of the first and second doped portions 10, 20.
- the quantum well forming layer may be disposed between two barrier layers providing better confinement of the charge carriers.
- the inventors have demonstrated a drawback then arising from the mismatch between the first semiconductor compound of the first doped portion, here GaN, and the second semiconductor compound of the active zone, here InGaN. Such clash of mesh may result in the appearance of structural defects at the interface between the first and second semiconductor compounds, defects likely to degrade the electronic and / or optical properties of the active zone.
- the second semiconductor compound increases with a mesh parameter substantially equal to that of the first semiconductor compound but undergoes a deformation of its crystallographic structure which results in the generation of mechanical stresses, in particular in compression or in tension .
- the stresses experienced by the second semiconductor compound can relax and cause the appearance of structural defects, for example so-called disordered mesh dislocations located at the interface between the first and second semiconductor compounds, thereby causing degradation of the electronic and / or optical properties of the wire.
- the mismatch between the first and second semiconductor compounds then introduces a constraint in terms of the thickness of the second semiconductor compound, and / or in terms of the atomic proportion of the additional element in the second semiconductor compound.
- Figures 2 and 3 schematically illustrate a partial sectional view of a first embodiment of an optoelectronic device 1 having three-dimensional semiconductor structures 2 forming wire electroluminescent diodes in radial configuration.
- the optoelectronic device 1 comprises:
- a substrate 3 for example made of a semiconductor material, having two faces, said rear 3a and before 3b, opposite to each other; a first polarization electrode 4, here in contact with the rear face 3a of the substrate;
- nucleation layer 5 made of a material adapted to the epitaxial growth of the three-dimensional semiconducting structures, covering the front face 3b of the substrate;
- At least one three-dimensional semiconductor structure 2 here in the form of a wire, which extends from the nucleation layer 5 along a longitudinal axis ⁇ oriented substantially orthogonal to the plane (X, Y) of the front face 3b of the substrate 3, the wire 2 comprising a first doped portion 10 in contact with the nucleation layer 5, an active zone 30 and a second doped portion 20;
- the wire 2 represented here has a radial configuration, or core / shell configuration, insofar as the second doped portion 20 surrounds and covers at least part of the active zone 30, and in particular the lateral edge thereof. It therefore has a configuration that differs from the axial configuration in which the n-doped portion, the active zone and the p-doped portion are stacked one over the other along the longitudinal axis of the wire, without the lateral edge of the zone. active is substantially covered by the p-doped portion.
- lateral or upper edge is meant a surface of a portion of the wire which extends respectively substantially parallel or orthogonal to the longitudinal axis ⁇ .
- a lateral border may also be called a radial edge, or lateral flank.
- An upper border can also be called an axial border.
- the lateral edges may be inclined when they form a non-zero inclination angle with the longitudinal axis ⁇ .
- the edge 33 of the active zone 30 is here called inclined insofar as it forms an angle of inclination with respect to the longitudinal axis ⁇ other than 0 °, and in particular strictly greater than 0 ° and strictly less than 90 0 , or strictly less than 0 ° and strictly greater than -90 0 .
- an upper edge for example here the edge 34 of the active zone 30, is said to be inclined when it forms an angle of inclination ⁇ with respect to the longitudinal axis ⁇ other than 90 ° , and in particular strictly greater than 90 ° and strictly less than 180 ° , or strictly less than 90 ° and strictly greater than 0 °.
- the substrate 3 is here a semiconductor structure, for example silicon. It may be monoblock or formed of a stack of layers such as a substrate of the SOI type (acronym for Silicon On Insulator). More broadly, the substrate may be of a material semiconductor, for example silicon, germanium, silicon carbide, or a compound III-V or II-VI. It can also be made of a metallic material or an insulating material. It may comprise a layer of graphene, molybdenum sulphide or selenide (MoS2, MoSe2), or any other equivalent material. In this example, the substrate is made of highly doped n-type monocrystalline silicon.
- the first polarization electrode 4 is in contact with the substrate 3, here electrically conductive, for example at its rear face 3a. It can be made of aluminum or any other suitable material.
- the nucleation layer 5 is made of a material that promotes the nucleation and growth of the yarns, for example aluminum nitride (AlN) or aluminum oxide (Al 2 O 3 ), magnesium nitride (MgxN y ), nitride or carbide of a transition metal or any other suitable material.
- AlN aluminum nitride
- Al 2 O 3 aluminum oxide
- MgxN y magnesium nitride
- nitride or carbide of a transition metal or any other suitable material for example aluminum nitride (AlN) or aluminum oxide (Al 2 O 3 ), magnesium nitride (MgxN y ), nitride or carbide of a transition metal or any other suitable material.
- the thickness of the nucleation layer may be of the order of a few nanometers or a few tens of nanometers.
- the nucleation layer is AlN.
- the first doped portion 10 of the wire rests on the substrate 3 at the level of the nucleation layer 5. It has a wire shape which extends along the longitudinal axis ⁇ , and forms the heart of the wire heart / shell configuration. It has an end 11, opposite to the substrate, delimited longitudinally by a so-called upper face 14.
- the upper face 14 extends here substantially orthogonal to the longitudinal axis ⁇ but can be inclined with respect to the axis ⁇ , or even be formed of one or more so-called then elementary faces.
- the first doped portion 10 is made of a first semiconductor compound, which may be chosen from compounds III-V comprising at least one element of column III and at least one element of column V of the periodic table, among the compounds II- VI comprising at least one element of column II and at least one element of column VI, or of elements or compounds IV having at least one element of column IV.
- III-V compounds may be III-N compounds, such as GaN, InGaN, AlGaN, AlN, InN or AlInGaN, or even compounds comprising an arsenic or phosphorus-type V column element, for example. example AsGa or InP.
- compounds II-VI can be CdTe, HgTe, CdHgTe, ZnO, ZnMgO, CdZnO or CdZnMgO.
- elements or compounds IV may be used, such as Si, C, Ge, SiC, SiGe, or GeC.
- the first portion is doped according to a first type of conductivity.
- the first doped portion 10 is made of n-type doped GaN, in particular with silicon.
- the first doped portion 10 here has an average diameter approximately equal to the local diameter.
- the average diameter of the first doped portion 10 can be between 1 m and ⁇ , for example between soonm and 5 ⁇ , and is here substantially equal to ⁇ .
- the height of the first doped portion may be between 1oonm and ⁇ , for example between soonm and 5 ⁇ , and here is substantially equal to 5 ⁇ .
- a dielectric layer 7 here covers the nucleation layer 5 and forms a growth mask allowing the epitaxy of the son from openings opening locally on the nucleation layer, and a second dielectric layer 8 covers the lateral border of the first doped portion 10.
- the active zone 30 is the portion of the wire 2 at which most of the light radiation of the wire is emitted. It comprises at least one quantum well made of a semiconductor compound having a band gap energy lower than that of the first doped portion 10 and the second doped portion 20. It extends from the end 11 of the first portion doped 10 and more precisely from the upper face 14. As detailed below, the active zone 30 may comprise a single quantum well or multiple quantum wells in the form of layers or boxes interposed between barrier layers.
- the active zone 30 comprises a so-called widened monocrystalline portion 31 which extends along the longitudinal axis ⁇ from the upper face 14 of the end 11 of the first doped portion 10.
- the expanded monocrystalline portion 31 is formed of a single crystal of a second semiconductor compound, different from the first semiconductor compound in the sense that it comprises at least one additional element not contained in the first compound.
- the second compound is thus formed of a mixture of the first compound and at least one additional element.
- the atomic proportion of the additional element is chosen as a function of the optical and / or electronic properties sought, and in particular of the emission spectrum of the wire.
- the second compound is preferably InGaN, of general formula In x Ga (i- x ) N, with, for example, an atomic percentage of indium of the order of 18%.
- the second semiconductor compound of the expanded monocrystalline portion 31 may be unintentionally doped or doped according to the same type of conductivity and possibly at the same doping level as the first doped portion 10.
- the enlarged monocrystalline portion 31 is formed of a single crystal of the second semiconductor compound, delimited by a base 32 in contact with the upper face 14 of the first doped portion 10, a lateral edge 33 and an upper edge 34.
- the lateral edges 33 and upper 34 may have semi-polar faces, that is to say faces inclined vis-à-vis the longitudinal axis ⁇ .
- the monocrystalline portion 31 is said to be enlarged insofar as it has a mean diameter greater than the average diameter of the first doped portion 10. It thus has a mean diameter which may be between 1.1 and 20 times the average diameter of the first doped portion 10, for example between 2 and 10 times the average diameter of the first doped portion 10, and is here substantially equal to 5 ⁇ .
- the enlarged monocrystalline portion 31 may have an average thickness greater than 1 ⁇ m which is the order of magnitude of the critical thickness of the second semiconductor compound, here InGaN.
- the local thickness is the thickness of the enlarged monocrystalline portion 31 along a given axis parallel to the longitudinal axis ⁇ from the upper surface of the first doped portion.
- the average thickness is the average, for example arithmetic, of the local thicknesses.
- the average thickness may be between 1 ⁇ m and 2 ⁇ , for example between soonm and ⁇ , and is here substantially equal to 5 ⁇ .
- the active zone 30 comprises at least one quantum well, which here covers at least in part the enlarged monocrystalline portion 31, and in particular its lateral edges 33 and upper 34.
- the active zone comprises multiple quantum wells 35 presenting in the form of a stack of layers, one or more layers forming quantum wells interposed between two barrier layers.
- the layers forming the quantum wells, and preferably also the barrier layers, are made of a semiconductor material based on the second semiconductor compound, that is to say having at least the same elements as the second semiconductor compound, here in InGaN . They are preferably made in the same second semiconductor compound, with different mole fractions for the barrier layers and for the quantum wells.
- the barrier layers can thus be made of In x iGai x iN with an atomic proportion of indium xi of between approximately 15% and 23%, for example equal to approximately 18%, and the layers forming the quantum wells can be produced by In x2 Gai-x 2 N with an atomic proportion of indium x2 of between approximately 22% and 30%, for example equal to approximately 25%, thereby making it possible to obtain an emission wavelength of between 495nm and sôonm about, for example equal to about min.
- the atomic proportion x2 is greater than the atomic proportion xi.
- the light-emitting diode is then to emit light radiation in the green, with a good light output insofar as the internal quantum efficiency is improved by the fact that the mesh mismatch between the monocrystalline portion in InGaN and the wells is limited.
- multiple quantum then same as the first doped portion is made of GaN.
- the monocrystalline portion of InGaN has an atomic proportion equal to that of the barrier layer which is in contact with it.
- the second doped portion 20 forms a layer that covers and at least partially surrounds the active zone 30, that is to say here the expanded single crystal portion 31 and the multiple quantum wells. It is made of a d-doped semiconductor compound. a second type of conductivity opposite to the first type.
- the semiconductor compound may be the first semiconductor compound, namely here GaN, or preferably the second semiconductor compound, namely here InGaN. It may also include one or more additional elements.
- the second doped portion 20 is made of InGaN, and is p-type doped, in particular with magnesium.
- the thickness of the second doped portion may be between 20 nm and 500 nm, for example of the order of 150 nm.
- the second doped portion 20 may comprise an electron-blocking layer (not shown) located at the interface with the active zone 30.
- the electron-blocking layer can here be formed of a ternary compound III-N, for example example of AlGaN or ⁇ , advantageously doped p. It makes it possible to increase the rate of radiative recombinations within the active zone.
- the second polarization electrode 6 here covers the second doped portion 20 and is adapted to apply an electrical polarization to the wire 2. It is made of a substantially transparent material vis-à-vis the light radiation emitted by the wire, for example the indium tin oxide (ITO, for Indium Tin Oxide). It has a thickness of a few nanometers to a few tens or hundreds of nanometers.
- ITO indium tin oxide
- the wire 2 when a potential difference is applied to the wire 2 in a direct direction via the two polarization electrodes, the wire 2 emits light radiation whose emission spectrum has a peak intensity at a length of wave depending mainly on the composition of the quantum well.
- the wire in radial configuration, comprises a quantum well active zone comprising an enlarged monocrystalline portion, the latter lying on an upper face of the first doped portion, this upper face thus forming a nucleation seed for the portion expanded monocrystalline.
- the latter has a substantially relaxed, i.e. unconstrained, crystallographic structure. mesh being substantially identical to the parameter natural mesh of the compound. This is explained by the fact that unlike the wire described with reference to Figure 1, the area for nucleation of the expanded monocrystalline portion is reduced and less than the average diameter of the monocrystalline portion.
- the expanded monocrystalline portion then has a good crystalline quality, with a limited density of structural defects.
- the density of structural defects that is to say the number of defects per unit volume, decreases in particular with the increase in the volume of the expanded monocrystalline portion.
- the structural defects, of the dislocation type are essentially derived from a plastic relaxation of the second semiconductor compound in the nucleation zone from the upper face of the first doped portion, and are not substantially generated by the enlargement. of the enlarged monocrystalline portion.
- the active zone may comprise at least one quantum well, made of a material based on the second semiconductor compound, and which rests on the enlarged monocrystalline portion or is formed by it.
- the effects of the mismatch between the first semiconductor compound of the first doped portion and the semiconductor material forming the quantum well (s) are thus limited.
- the quantum well (s) then have an improved crystalline quality and thus an increased internal quantum yield.
- the multiple quantum wells cover and surround at least in part the enlarged monocrystalline portion, which makes it possible to obtain a larger emission area.
- This increased emission surface combined with optimized internal quantum efficiency, also increases the optical performance of the wire, the latter being defined as the ratio of the light flux emitted on the absorbed electrical power.
- the active area is formed based on the second semiconductor compound, for example based on InGaN
- the first doped portion is made of the first semiconductor compound, for example GaN. This improves the best quantum efficiency. It is possible to make an active zone of greater thickness and / or to incorporate more additional element of the second semiconductor compound, for example indium in the case of InGaN.
- the active zone is formed of multiple quantum wells 35 which cover at least a portion of the enlarged monocrystalline portion 31, formed of an alternation of barrier layers having a first non-zero value In xi of indium atomic proportion and of quantum well forming layers having a second value In x2 of indium atomic proportion higher than the first value In xl , it is possible to make an active zone whose value xi is between 15% and 23% and whose value x2 is between 22% and 30%, even though the first doped portion is made of GaN.
- the diode is able to emit light radiation in the green, with a good light output as far as the internal quantum efficiency is improved.
- the yarn 2 is made by epitaxial growth by chemical vapor deposition organometallic (MOCVD, for Metal-Organic Chemical Vapor Deposition, in English) and here are made based on GaN.
- MOCVD chemical vapor deposition organometallic
- the parameters influencing the epitaxial growth are in particular:
- the nominal V / III ratio defined as the ratio between the molar flow of elements of column V on the molar flow of elements of column III, that is to say here the N / Ga ratio during the growth of the first doped portion made of GaN, and the ratio N / (Ga + In), during the growth of the expanded monocrystalline portion and the multiple quantum wells, made in InGaN;
- the ratio H 2 / N 2 defined as the ratio between the proportion of molar flux of H 2 in the carrier gas of H 2 and N 2 , namely ⁇ ⁇ 2 / ( ⁇ 2 + ⁇ 2 ), on the proportion molar flow of N 2, namely ⁇ 2 / ( ⁇ 2 + ⁇ 2) and ⁇ ⁇ 2 ⁇ 2 being respectively the mole ratios of hydrogen and nitrogen stream;
- the growth temperature T measured here at the substrate.
- the first doped portion 10 is formed by epitaxial growth from the nucleation layer 5.
- the epitaxy can be performed from openings formed in a growth mask 7 of a dielectric material, by example of Si 3 N 4 , previously deposited on the nucleation layer 5.
- the growth temperature is brought to a first value ⁇ , for example between 950 ° C and noo ° C, and especially between 990 ° C and io6o ° C.
- the nominal V / III ratio here the N / Ga ratio, has a first value (V / III) i of between 10 and approximately 100, for example substantially equal to 30.
- the elements of group III and of group V come from precursors injected into the epitaxial reactor, for example the trimethylgallium (TMGa) or triethylgallium (TEGa) for gallium, and ammonia (NH 3 ) for nitrogen.
- the ratio H 2 / N 2 has a first value (H 2 / N 2 ) i greater than or equal to 60/40, preferably greater than or equal to 70/30, or even more, for example substantially equal to 90/10.
- the pressure can be set at about 8mbar.
- first doped portion 10 which has the shape of a wire which extends along the longitudinal axis ⁇ .
- the first semiconductor compound of the first doped portion 10, namely here GaN, is n-doped with silicon.
- the first doped portion 10 here has a height of approximately 5 ⁇ and an average diameter of ⁇ approximately. It has an upper face 14, opposite the substrate 3 and oriented along the crystallographic axis c, substantially flat. This upper face 14 forms the axial face 14 of the end of the first doped portion, and provides the nucleation surface function for the formation of the enlarged monocrystalline portion.
- a dielectric layer 8 covering the lateral edge 13 of the first doped portion 10 can be performed simultaneously with the formation of the first doped portion.
- a precursor of an additional element for example silane (SiH 4 ) in the case of silicon, is injected with the precursors mentioned above, with a ratio of the molar flows of the gallium precursor on the silicon precursor preferably. between about 500 and 5000.
- a layer 8 of silicon nitride, for example Si 3 N 4 of a thickness of the order of 1 ⁇ m which covers the lateral edge 13 of the first doped portion, here over its entire height.
- the enlarged monocrystalline portion 31 is formed by epitaxial growth from the upper face 14 of the first doped portion 10.
- the growth temperature is brought to a second value T 2 lower than the value ⁇ , for example between 700 ° C. and 8oo ° C., here equal to about 750 ° C.
- T 2 lower than the value ⁇
- ⁇ for example between 700 ° C. and 8oo ° C.
- a precursor of the additional element for example trimethylindium
- TMIn in the case of indium.
- the nominal V / III ratio has a second value (V / III) 2 greater than the value (V / III), for example between about 500 and 5000, here substantially equal to 1500.
- the ratio H 2 / N 2 has a second value (H 2 / N 2 ) 2 less than the value (H 2 / N 2 ) i and less than or equal to 40/60, preferably less than or equal to 30/70, or even more, for example substantially equal to 3/97. Furthermore, the pressure can remain unchanged, and the injection of the silicon precursor is previously stopped.
- a monocrystalline portion 31 of the second semiconductor compound, here of InGaN with an atomic proportion of indium of the order of 18%, is obtained by epitaxial growth. from the upper face 14 of the first doped portion 10.
- the expanded monocrystalline portion may be unintentionally doped, but is advantageously doped according to the same type of conductivity and preferably at the same doping level as the first doped portion 10, thus limiting the series resistance associated with the portions 10, 31.
- multiple quantum wells are formed by epitaxial growth from the expanded monocrystalline portion 31, here at the lateral border 33 and the upper border 34.
- a stack of barrier layers and at least one layer forming a quantum well is formed, said layers being alternated in the direction of epitaxial growth.
- the layers forming the quantum wells and the barrier layers are advantageously made in a semiconductor compound which comprises the same elements as the second semiconductor compound, namely here InGaN, with different atomic proportions for the quantum well layers and the barrier layers.
- the barrier layers are made in the second semiconductor compound, here In x Ga (i- x ) N with x equal to about 18 atomic%
- the quantum well layers are also made in y Ga (i- y ) N, with y greater than x, for example of the order of 25 atomic%, so as to improve the quantum confinement of the charge carriers in the quantum wells.
- the formation of the barrier layers and quantum well layers can be carried out at a growth temperature value T 3 substantially equal to the value T 2 , namely here 750 ° C.
- the ratio V / III has a value (V / III) 3 substantially equal to the value (V / III) 2 .
- the ratio H 2 / N 2 has a value substantially equal to the value (H 2 / N 2 ) 2 during the formation of the barrier layers and has a value substantially lower than the value (H 2 / N 2 ) 2 during the formation of quantum well layers, for example 1/99.
- the pressure can remain unchanged.
- InGaN barrier layers with about 18 atomic% indium and InGaN quantum well layers are obtained with about 25 atomic% of indium.
- the second doped portion 20 is formed by epitaxial growth so as to cover and surround at least part of the active zone 30.
- the growth temperature can be increased to a fourth value T 4 greater than the value T 3 , for example of the order of 885 ° C.
- the ratio V / III may be increased to a fourth value (V / III) 4 greater than the value (V / III) 3 , for example of the order of 4000.
- the ratio H 2 / N 2 is increased to a fourth value (H 2 / N 2 ) 4 greater than the value (H 2 / N 2 ) 2 , for example of the order of 15/85.
- the pressure can be decreased to a value of the order of 300mbar.
- a second doped portion 20 is thus obtained, for example p-type doped GaN or InGaN, which continuously covers and surrounds here the active zone 30, that is to say the multiple quantum wells as well as the enlarged monocrystalline portion.
- the second doped portion 20 thus forms the shell of the core / shell configuration wire.
- the second polarization electrode 6 may be deposited so as to be in contact with at least a portion of the second doped portion 20.
- the second electrode 6 is made of an electrically conductive material and transparent to the light radiation emitted by the son.
- the application of a direct potential difference to the wires by the two polarization electrodes leads to the emission of light radiation whose properties of the emission spectrum depends on the composition of the quantum well or quantum wells. active area.
- the enlarged monocrystalline portion 31 has semi-polar faces, formed by the lateral 33 and upper 34 edges.
- the lateral and upper edges form faces inclined vis-à- screws of the longitudinal axis ⁇ and correspond to semi-polar crystalline planes.
- the inclined lateral edge corresponds to adjacent crystalline planes of the type (3 o -3 -2) inclined at an angle ⁇ of about 20 ° relative to the longitudinal axis ⁇
- the inclined upper edge corresponds to planes neighboring crystalline type (1 o -1 3) inclined at an angle ⁇ of about 120 0 relative to the longitudinal axis ⁇ .
- the difference in inclination between the different semi-polar faces 33, 34 leads to the formation of quantum well layers which differ mutually by the thickness and / or the atomic proportion of the elements. Indeed, in the case of a quantum well forming layer made of InGaN, the incorporation rate of indium and / or the thickness of the layer formed is different depending on whether the deposition is carried out on one side more or less inclined vis-à-vis the longitudinal axis ⁇ . This then results in differences in optical properties, including a difference in emission wavelength, between the quantum wells resting on the semi-polar faces. The light radiation emitted by such a wire can then have an expanded emission spectrum when it comes from the quantum wells located on the different semi-polar faces.
- FIG. 4 schematically illustrates a partial sectional view of a variant of the first embodiment of an optoelectronic device 1 comprising structures 3-dimensional semiconductors 2 forming wired light emitting diodes in radial configuration and with multiple quantum wells.
- the optoelectronic device 1 differs from that shown in Figure 2 essentially in that the dielectric layer 8 covering the lateral edge 13 of the first doped portion 10 does not extend over the entire height of the latter.
- the dielectric layer 8 extends from the nucleation layer 5 over a height H x less than the height H 2 of the first doped portion 10.
- height we mean the longitudinal extent, according to the longitudinal axis ⁇ , of a layer or portion.
- a so-called upper zone 13I1 of the lateral edge 13 of the first doped portion 10 which extends from the height H x to the height H 2 , is not covered by the dielectric layer 8, and is called free zone.
- a second enlarged portion 36 may be formed from the lateral edge 13 of the first doped portion 10 at the free zone 13I1.
- This second enlarged portion 36 is also made of the second semiconductor compound and has a mean diameter greater than the average diameter of the first doped portion.
- it is covered by the multiple quantum wells 35, the second doped portion 20 and the second polarization electrode 6.
- This second enlarged portion 36 is formed by epitaxial growth from the free zone 13I1 of the lateral edge 13 of the first doped portion 10, and as such, undergone mechanical stresses related to the mismatch with the first semiconductor compound, in the extent that it has a large nucleation surface with the first doped portion 10. Also, the crystalline quality of the second enlarged portion 36 is less than that of the enlarged monocrystalline portion 31.
- the wire 2 may not have a dielectric layer 8 covering at least part of the lateral edge 13 of the first doped portion 10.
- the second enlarged portion 36 can then cover the lateral edge 13 of the first portion doped over substantially the entire height H 2 .
- the growth mask 7, advantageously dielectric, then provides electrical isolation between the second bias electrode and the conductive substrate.
- FIG. 5 schematically illustrates a partial cross-sectional view of a second embodiment of an optoelectronic device 1 comprising three-dimensional semiconductor structures 2 forming wire electroluminescent diodes in radial configuration and with a single quantum well.
- the optoelectronic device 1 differs from that shown in FIG. 2 essentially in that the active zone 30 comprises a single quantum well formed by the enlarged monocrystalline portion 31.
- the active zone 30 thus comprises a single quantum well made in the second semiconductor compound, here InGaN, formed of the first semiconductor compound, here GaN, in which is incorporated at least one additional element, here indium.
- the atomic proportion of the elements of the second In x Ga (i- x ) N semiconductor compound is preferably substantially homogeneous within the quantum well, and the second semiconductor compound is preferably unintentionally doped.
- the single quantum well of InGaN forms a monocrystal 31 which extends from the upper face 14 of the first doped portion 10 and has a mean diameter greater than the average diameter of the first doped portion 10. It comprises a base 32 in contact with the upper face 14 of the first doped portion 10, a lateral edge 33 and an upper edge 34.
- the lateral edges 33 and upper 34 have in this example semi-polar faces, that is to say, inclined faces vis-à-vis the longitudinal axis ⁇ .
- the enlarged monocrystalline portion 31 is covered at least in part by the second doped portion 20, which here covers the lateral edge 33 and the upper edge 34.
- the second doped portion 20 is in contact with the second polarization electrode 6.
- the expanded monocrystalline portion 31 is made of InGaN with an atomic proportion of indium of the order of 18% making it possible to obtain an emission wavelength centered on 420 nm at 440 nm or even 25% for obtain a transmission wavelength of the order of soonm.
- the mean diameter of the enlarged monocrystalline portion 31 is of the order of 5 ⁇ and its average thickness is of the order of 5 ⁇ .
- the expanded monocrystalline portion 31 thus has, by its epitaxy from a reduced nucleation surface, namely the upper face 14 of the first doped portion 10, a good crystalline quality whose density of structural defects decreases with its volume.
- FIGS. 6 and 7 schematically illustrate partial sectional views of two variants of the polarization of an optoelectronic device 1 comprising three-dimensional semiconductor structures 2 similar to that shown in FIG. 4.
- the yarns 2 comprise an active zone 30 with an enlarged monocrystalline portion 31 coated at least in part by multiple quantum wells 35, themselves being coated by the second doped portion 20.
- the expanded monocrystalline portion 31 is formed of a single crystal of the second semiconductor compound, here of InGaN, having semi-polar faces formed by the borders Lateral 33 and higher 34.
- quantum wells do not have the same optical properties due to differences in thickness and / or atomic proportion of indium, depending on whether they are arranged on the semi-polar face of the upper edge 34 or on the semi-polar face of the lateral edge 33.
- the wires 2 differ from that shown in FIG. 4 essentially in that the second polarization electrode 6 is no longer in the form of a layer continuously covering the second doped portion 20 , but in the form of a layer arranged to substantially polarize the quantum wells located at the inclined upper edge 34.
- the optoelectronic device comprises a thick layer 9 of a dielectric material, disposed between the wires 2 to a height such that it covers the first doped portion 10 and the portion of the second doped portion 20 located at the edge
- the dielectric material is at least partly transparent with respect to the emission spectrum of the wires and has a refractive index chosen so as to allow the light radiation to be extracted from the wires.
- the dielectric material may be, inter alia, a silicon oxide or an aluminum or silicon nitride.
- the second polarization electrode 6 On the thick dielectric layer 9 is deposited the second polarization electrode 6, in the form of a layer of a conductive material and transparent vis-à-vis the emission spectrum of the son, this conductive layer covering the portion of the second portion doped 20 located at the inclined upper edge 34.
- the second doped portion 20 has a portion located at the inclined upper edge 34 which is in contact with the second bias electrode 6, and a portion at the inclined lateral edge 33 which is in contact with the the dielectric thick layer 9.
- the electrical resistance of this portion 20 is such that the electric field lines are oriented substantially rectilinearly in the thickness. of the second doped portion 20 from the electrode 6, and do not extend substantially in the transverse directions, in the thickness of the portion 20. Also, only the portion of the second doped portion 20 in contact with the 6 is able to be polarized, the portion of the second doped portion located at the inclined lateral edge 33 and which is not in contact with the electrode 6 being substantially not polarized by the electrode 6.
- the optoelectronic device 1 comprises two second polarization electrodes, called the upper 6h and the lower 6b electrodes, arranged in such a way as to polarize, for the upper electrode 6h, essentially the portion of the second doped portion 20 located at the inclined upper edge 34, and for the electrode lower 6b, essentially the portion of the second doped portion 20 located at the inclined lateral edge 33.
- the electrode 6b rests on a dielectric layer 9b and the electrode 6h rests on a dielectric layer 9I1.
- the second upper 6h and lower 6b electrodes are adapted to apply a distinct or identical electrical potential to the two parts of the second doped portion 20, according to the desired properties of the emission spectrum.
- the two parts of the second doped portion 20 are polarized by one and / or the other upper 6h and lower 6b electrodes, substantially without interference or crosstalk (in English), because of the electrical resistance of the portion 20.
- the second biasing electrode can be arranged in the form of not a substantially flat layer, but structured layers as illustrated in US8937297.
- Three-dimensional semiconductor structures adapted to emit light radiation from an electrical signal have been described, thereby forming light-emitting diodes.
- the structures may be adapted to detect incident light radiation and to respond to an electrical signal thereby forming a photodiode.
- Applications may be in the field of optoelectronics or photovoltaics.
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Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1561587A FR3044469B1 (fr) | 2015-11-30 | 2015-11-30 | Dispositif optoelectronique comportant des structures semiconductrices tridimensionnelles a portion monocristalline elargie |
| PCT/FR2016/053121 WO2017093645A1 (fr) | 2015-11-30 | 2016-11-28 | Dispositif optoelectronique comportant des structures semiconductrices tridimensionnelles a portion monocristalline elargie |
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| Publication Number | Publication Date |
|---|---|
| EP3384534A1 true EP3384534A1 (fr) | 2018-10-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP16813091.2A Withdrawn EP3384534A1 (fr) | 2015-11-30 | 2016-11-28 | Dispositif optoelectronique comportant des structures semiconductrices tridimensionnelles a portion monocristalline elargie |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US11049997B2 (fr) |
| EP (1) | EP3384534A1 (fr) |
| FR (1) | FR3044469B1 (fr) |
| WO (1) | WO2017093645A1 (fr) |
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| US11101418B1 (en) | 2019-09-10 | 2021-08-24 | Facebook Technologies, Llc | Spacer for self-aligned mesa |
| US11164995B2 (en) | 2020-02-20 | 2021-11-02 | Facebook Technologies, Llc | 3-D structure for increasing contact surface area for LEDs |
| CN112289883B (zh) * | 2020-10-30 | 2023-03-28 | 华中科技大学 | 一种三维半导体雪崩光电探测芯片及其制备方法 |
| KR20250012344A (ko) * | 2023-07-17 | 2025-01-24 | 삼성전자주식회사 | 발광 소자 및 그 제조 방법 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101019941B1 (ko) * | 2006-03-10 | 2011-03-09 | 에스티씨. 유엔엠 | Gan 나노선의 펄스 성장 및 ⅲ 족 질화물 반도체 기판 물질과 디바이스에서의 어플리케이션 |
| SG183650A1 (en) * | 2011-02-25 | 2012-09-27 | Agency Science Tech & Res | A photonic device and method of making the same |
| FR2973936B1 (fr) | 2011-04-05 | 2014-01-31 | Commissariat Energie Atomique | Procede de croissance selective sur une structure semiconductrice |
| US8937297B2 (en) | 2011-12-02 | 2015-01-20 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Optoelectronic device including nanowires with a core/shell structure |
| US8785905B1 (en) * | 2012-01-19 | 2014-07-22 | Sandia Corporation | Amber light-emitting diode comprising a group III-nitride nanowire active region |
| JP2015532014A (ja) | 2012-09-18 | 2015-11-05 | グロ アーベーGlo Ab | ナノピラミッドサイズ光電構造及びそれを製造するための方法 |
| FR3000611B1 (fr) * | 2012-12-28 | 2016-05-06 | Aledia | Dispositif optoelectronique a microfils ou nanofils |
| FR3039004B1 (fr) * | 2015-07-16 | 2019-07-12 | Universite Grenoble Alpes | Dispositif optoelectronique a elements semiconducteurs tridimensionnels et son procede de fabrication |
-
2015
- 2015-11-30 FR FR1561587A patent/FR3044469B1/fr active Active
-
2016
- 2016-11-28 EP EP16813091.2A patent/EP3384534A1/fr not_active Withdrawn
- 2016-11-28 WO PCT/FR2016/053121 patent/WO2017093645A1/fr not_active Ceased
- 2016-11-28 US US15/779,727 patent/US11049997B2/en active Active
Non-Patent Citations (1)
| Title |
|---|
| A. SYRKIN ET AL: "First all-HVPE grown InGaN/InGaN MQW LED structures for 460-510 nm", PHYSICA STATUS SOLIDI (C), vol. 5, no. 6, 1 May 2008 (2008-05-01), DE, pages 2244 - 2246, XP055733034, ISSN: 1610-1634, DOI: 10.1002/pssc.200778647 * |
Also Published As
| Publication number | Publication date |
|---|---|
| FR3044469B1 (fr) | 2018-03-09 |
| WO2017093645A1 (fr) | 2017-06-08 |
| US11049997B2 (en) | 2021-06-29 |
| FR3044469A1 (fr) | 2017-06-02 |
| US20200313042A1 (en) | 2020-10-01 |
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