WO2018070120A1 - Élément électroluminescent et son procédé de fabrication - Google Patents

Élément électroluminescent et son procédé de fabrication Download PDF

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Publication number
WO2018070120A1
WO2018070120A1 PCT/JP2017/030644 JP2017030644W WO2018070120A1 WO 2018070120 A1 WO2018070120 A1 WO 2018070120A1 JP 2017030644 W JP2017030644 W JP 2017030644W WO 2018070120 A1 WO2018070120 A1 WO 2018070120A1
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substrate
layer
transparent
light
emitting element
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PCT/JP2017/030644
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English (en)
Japanese (ja)
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石崎　順也
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信越半導体株式会社
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • 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
    • H01L33/20—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 particular shape, e.g. curved or truncated substrate
    • H01L33/22—Roughened surfaces, e.g. at the interface between epitaxial layers

Definitions

  • the present invention relates to a light-emitting element in which a transparent substrate is bonded and a manufacturing method thereof.
  • a light-emitting element made of AlGaInP is disclosed in the form of a single-sided two-electrode.
  • the light-emitting element having such a shape is divided into a use with a narrow light distribution angle and a wide use, but in a use with a wide light distribution angle, it is necessary to provide a rough surface on the light extraction surface.
  • Patent Document 1 discloses a technique for bonding a light emitting element on ITO provided on a glass substrate to roughen the glass substrate, but this is difficult to provide a rough surface on the base material sapphire. Is a cause.
  • Patent Document 2 discloses a method of providing a rough surface directly on the substrate side in a light emitting device having a shape having two electrodes on one side. This is because a material capable of providing a rough surface on the substrate is selected. Although it is made of an etching material GaP as a material capable of roughening, it is difficult to increase the diameter of the GaP crystal regardless of whether epitaxial growth is selected or a bulk substrate is selected. Is an unsuitable technology.
  • Patent Document 3 discloses a technique for joining transparent substrates. In this method, since the material of the base material to be joined is not limited, the diameter can be increased.
  • an inexpensive material that can be obtained from a transparent substrate is an oxide, and a substrate material having a processing accuracy enough to pass through a semiconductor process is limited to a sapphire substrate.
  • the sapphire substrate is a difficult-to-etch material, and there is a problem that it is difficult to obtain a rough surface by a wet etching technique.
  • the present invention has been made in view of the above problems, and provides a light-emitting element having a light distribution angle increased and a light-emitting efficiency increased in a light-emitting element formed by bonding a transparent substrate, and a method for manufacturing the light-emitting element. For the purpose.
  • a light emitting device in which a transparent substrate is bonded to the light extraction surface side, provided is a light emitting device characterized in that a transparent film having a refractive index lower than that of the transparent substrate is provided on the light extraction surface side surface of the transparent substrate, and the surface of the transparent film is roughened.
  • the surface of the transparent film is roughened, a light emitting element having an increased light distribution angle and an increased luminous efficiency can be obtained regardless of the material of the transparent substrate. Further, the low refractive index material is formed on the light extraction surface side, so that the total reflection angle is generated, and the luminous efficiency can be further increased.
  • the transparent substrate is a sapphire substrate and the transparent film is a SiO 2 film.
  • a sapphire substrate can be suitably used for the transparent substrate, and a SiO 2 film can be suitably used for the transparent film.
  • a method for manufacturing a light emitting device in which a transparent substrate is bonded to the light extraction surface side, A transparent film having a refractive index lower than that of the transparent substrate is laminated on the surface of the transparent substrate on the light extraction surface side, and the surface of the laminated transparent film is roughened by frost processing by chemical treatment.
  • a method for manufacturing a light emitting device is provided.
  • the transparent substrate is a sapphire substrate and the transparent film is a SiO 2 film.
  • the sapphire substrate which is a material that is difficult to be frosted by chemical treatment
  • the transparent film is made of SiO 2 film, so that the surface of the transparent film can be easily frosted by chemical treatment. It can be carried out.
  • the frost processing is performed by roughening the surface of the transparent film by etching with a liquid in which hydrofluoric acid and a monovalent to tetravalent inorganic acid or organic acid are mixed.
  • Such a method can reliably roughen the surface of the transparent film.
  • the surface of the transparent film is roughened in the light-emitting element of the present invention, a light-emitting element having an increased light distribution angle and increased light emission efficiency can be obtained regardless of the material of the transparent substrate.
  • the low refractive index material is formed on the light extraction surface side, so that the total reflection angle is generated, and the luminous efficiency can be further increased.
  • an inexpensive and high processing precision sapphire substrate can be employ
  • a light-emitting element of the present invention it is relatively easy to roughen the surface regardless of the material of the transparent substrate, and relatively easily manufacture a light-emitting element having an increased light distribution angle and increased light emission efficiency. Can do. Furthermore, a low refractive index material is formed on the light extraction surface side, whereby a total reflection angle is generated, and a light emitting element with higher luminous efficiency can be manufactured.
  • the sapphire substrate is a difficult-to-etch material, and there is a problem that it is difficult to obtain a rough surface by a wet etching technique.
  • a transparent film having a refractive index lower than that of the transparent substrate is provided on the surface of the transparent substrate on the light extraction surface side, and the surface of the transparent film is rough.
  • a light emitting element with an increased light distribution angle and increased luminous efficiency can be obtained regardless of the material of the transparent substrate, and a low refractive index material is formed on the light extraction surface side. This has led to the idea that a total reflection angle can be generated and the luminous efficiency can be further increased. And the best form for implementing these was scrutinized and the present invention was completed.
  • FIG. 1 shows a first embodiment of a light emitting device of the present invention.
  • a transparent substrate 110 is bonded to the light extraction surface 115 side.
  • a transparent film 180 having a refractive index lower than that of the transparent substrate 110 is provided on the light extraction surface 115 side of the transparent substrate 110, and the surface of the transparent film 180 is roughened.
  • a transparent substrate 110 made of, for example, sapphire, on which a transparent film 180 made of, for example, an SiO 2 film is formed can be suitably used.
  • the second dielectric film 121 made of, for example, SiO 2 and having a thickness of about 100 nm may be formed on the opposite side of the transparent substrate 110 from the transparent film 180.
  • the surface of the transparent film 180 is roughened, and irregularities are formed.
  • the transparent film 180 is made of a material having a refractive index lower than that of the transparent substrate 110. As described above, if the transparent film 180 having a low refractive index is provided on the transparent substrate 110 and the irregularities are formed on the surface of the transparent film 180, the surface can be easily roughened regardless of the material of the transparent substrate 110. It is possible to obtain a light-emitting element that is planarized and has an increased light distribution angle and increased light emission efficiency. Further, since the low refractive index material is formed on the light extraction surface 115 side, a total reflection angle is generated, and the light emission efficiency can be further increased.
  • a transparent adhesive layer 125 may be formed on the surface of the second dielectric film 121.
  • the transparent adhesive layer 125 can be formed of a plurality of layers, for example, a first adhesive layer 125A and a second adhesive layer 125B.
  • a first dielectric film 120 made of, for example, SiO 2 and having a thickness of about 100 nm is formed on the transparent adhesive layer 125.
  • the surface of the first dielectric film 120 is made of, for example, AlGaAs, GaAsP, GaP, or the like.
  • the current propagation layer 107 can be formed with a thickness of 0.5 to 20 ⁇ m.
  • the second electrode 151 is formed on a part (second surface) of the surface of the current propagation layer 107, and the buffer layer 106 is formed on a region (first surface) where the second electrode 151 is not formed. It can be.
  • the second electrode 151 includes at least one material selected from Au, Ag, Al, Ni, Pd, Ge, Si, and Sn, and has a thickness of 100 nm or more. Is done.
  • the second conductivity type is p-type, it includes at least one material selected from Au, Be, Mg, and Zn and has a thickness of 100 nm or more.
  • a buffer layer 106 that relieves lattice irregularities may be formed on the surface of the current propagation layer 107.
  • the buffer layer 106 is most preferably formed of InGaP or AlInP. Since there is a lattice mismatch between GaAs x P 1-x (x ⁇ 1) and the AlGaInP-based material or AlGaAs-based material, GaAs x P 1-x (x ⁇ 1) has high-density strain and Threading dislocation enters. The threading dislocation density can be adjusted by the composition x.
  • a second semiconductor layer 105 made of AlGaInP or AlGaAs and having a thickness of 0.5 to 1.0 ⁇ m may be formed on the surface of the buffer layer 106.
  • the active layer 104 having a thickness of 0.1 to 10 ⁇ m may be formed on the surface.
  • the active layer 104 has (Al x Ga 1-x ) y In 1-y P (0 ⁇ x ⁇ 1, 0.4 ⁇ y ⁇ 0.6) or Al z Ga 1-z As ( 0 ⁇ z ⁇ 0.45).
  • AlGaInP When it is applied to visible light illumination, it is preferable to select AlGaInP, and when it is applied to infrared illumination, it is preferable to select AlGaAs or InGaAs.
  • the design of the active layer 104 is not limited to the above materials because the wavelength can be adjusted by using a superlattice or the like other than the wavelength resulting from the material composition.
  • the first semiconductor layer 103 made of AlGaInP or AlGaAs and having a thickness of 0.5 to 1.0 ⁇ m may be formed on the surface of the active layer 104.
  • the first electrode 150 may be formed on the surface of the first semiconductor layer 103.
  • a desired layer such as the buffer layer 116 may be provided between the first semiconductor layer 103 and the first electrode 150 as necessary.
  • the first electrode 150 includes at least one material selected from Au, Ag, Al, Ni, Pd, Ge, Si, and Sn and has a thickness of 100 nm or more. Is done.
  • the first conductivity type is p-type, it includes at least one material selected from Au, Be, Mg, and Zn and has a thickness of 100 nm or more.
  • the second electrode 151 is provided in the current propagation layer 107 is illustrated, but the second electrode 151 may be provided in the second semiconductor layer 105.
  • a substrate 101 is prepared as a starting substrate.
  • the substrate 101 it is preferable to use a substrate 101 whose crystal axis is inclined in the [110] direction from the [001] direction.
  • the substrate 101 GaAs or Ge can be preferably used. If the substrate 101 is selected from the above materials, the material of the active layer 104 to be described later can be epitaxially grown in a lattice-matched system, so that the quality of the active layer 104 can be easily improved, and the luminance can be increased and the life characteristics can be improved. .
  • a first conductive type first semiconductor layer 103 (for example, a thickness of 0.5 to 1.0 ⁇ m) having substantially the same lattice constant as that of the substrate 101 and an active layer 104 (for example, a thickness of 0.1 To 1.0 ⁇ m), second conductivity type second semiconductor layer 105 (for example, thickness of 0.5 to 1.0 ⁇ m), buffer layer 106, and current propagation layer 107 (for example, thickness of about 2.0 ⁇ m) are sequentially grown by epitaxial growth. Can be formed. Further, a selective etching layer 102 for removing the substrate 101 may be inserted between the substrate 101 and the first semiconductor layer 103.
  • the selective etching layer 102 has a layer structure of two or more layers, and preferably includes at least a first selective etching layer 102A in contact with the substrate 101 and a second selective etching layer 102B in contact with the first semiconductor layer 103.
  • the first selective etching layer 102A and the second selective etching layer 102B may be made of different materials or compositions.
  • the MOVPE method metal organic chemical vapor deposition method
  • MBE molecular beam epitaxy method
  • the buffer layer 106 and the current propagating layer 107 are formed on the light emitting unit 108 including the first conductive type first semiconductor layer 103, the active layer 104, and the second conductive type second semiconductor layer 105 by CBE (Actinic Epitaxy).
  • CBE Actinic Epitaxy
  • the active layer 104 has (Al x Ga 1-x ) y In 1-y P (0 ⁇ x ⁇ 1, 0.4 ⁇ y ⁇ 0.6) or Al z Ga 1-z As ( 0 ⁇ z ⁇ 0.45).
  • AlGaInP When it is applied to visible light illumination, it is preferable to select AlGaInP, and when it is applied to infrared illumination, it is preferable to select AlGaAs or InGaAs.
  • the design of the active layer 104 is not limited to the above materials because the wavelength can be adjusted by using a superlattice or the like other than the wavelength resulting from the material composition.
  • the material selection is not necessarily the same material system as that of the active layer 104.
  • the first semiconductor layer 103, the light emitting layer 104, and the second semiconductor layer 105 having the simplest structure are exemplified by AlInGaP, which is the same material, but the first semiconductor layer 103 or the second semiconductor layer is exemplified.
  • the layer 105 generally includes a plurality of layers, and the second semiconductor layer 105 is not limited to a single layer.
  • the first semiconductor layer 103 is made of a layer having two or more types of Al composition.
  • the second layer 103B is closer to the active layer 104, and the first layer 103A having lower Al composition is closer to the substrate 101. It can be set as the structure which has.
  • the second layer 103B is a functional layer having a function of a clad layer, and does not mean a single composition or a single condition layer.
  • the current propagation layer 107 AlGaAs, GaAsP, or GaP can be suitably used.
  • the buffer layer 106 is most preferably formed of InGaP or AlInP. Since there is a lattice mismatch between GaAs x P 1-x (x ⁇ 1) and the AlGaInP-based material or AlGaAs-based material, GaAs x P 1-x (x ⁇ 1) has high-density strain and Threading dislocation enters. The threading dislocation density can be adjusted by the composition x.
  • a first dielectric film (first SiO 2 film) 120 is deposited on the current propagation layer 107 in the epitaxial substrate 109.
  • the first dielectric film 120 can be formed by optical CVD, sputtering, or PECVD.
  • a transparent adhesive layer 125 can be formed on the first dielectric film 120 to form the first bonding substrate 126.
  • the transparent adhesive layer 125 can be selected from BCB (benzocyclobutene) or epoxy. It is preferable to select a material that can be formed by a dipping method or a spin coating method.
  • a second dielectric film (second SiO 2 film) 121 can be deposited on the transparent substrate 110 to form the second bonding substrate 131.
  • the second dielectric film 121 can be formed by photo CVD, sputtering, or PECVD. It goes without saying that the same effect can be obtained even if a transparent adhesive layer is provided on the second bonding substrate 131.
  • the first bonding substrate 126 and the second bonding substrate 131 are placed so that the transparent adhesive layer 125 and the second dielectric film 121 face each other and do not come into contact with each other, and a vacuum atmosphere of 10 Pa or less is set. After the vacuum atmosphere, the transparent adhesive layer 125 and the second dielectric film 121 are brought into contact with each other, and are controlled so as to have a pressure of 5000 N and a temperature between 100 to 200 ° C. and held for 5 minutes or more, and then 100 ° C. or more. Then, the first bonding substrate 126 and the second bonding substrate 131 are pressed to form the bonding substrate 140.
  • the substrate 101 is removed from the bonded substrate 140 by etching.
  • etching can be performed with a mixed solution of ammonia water and hydrogen peroxide water.
  • an etching stop layer (first selective etching layer 102A) made of a material different from that of the substrate 101, etching using a mixed solution of ammonia water and hydrogen peroxide water can be selectively stopped.
  • AlInP can be used as the first selective etching layer 102A.
  • the first selective etching layer 102A is removed. Since AlInP is used for the etching stop layer 102A, removal is performed using hydrochloric acid. Since the second selective etching layer 102B stops etching with hydrochloric acid, GaAs can be used.
  • the first electrode 150 in contact with the first semiconductor layer 103 is formed.
  • the first electrode 150 includes at least one material selected from Au, Ag, Al, Ni, Pd, Ge, Si, and Sn and has a thickness of 100 nm or more. can do.
  • the first conductivity type is p-type, it can include at least one material selected from Au, Be, Mg, and Zn and have a thickness of 100 nm or more.
  • the second selective etching layer 102B may be left.
  • a pattern in which the first semiconductor layer 103 and the active layer 104 in the region 160 are cut out is formed by etching using a dry method or a wet method.
  • FIG. 5 illustrates an example in which the current propagation layer 107 is cut out, the same function is obtained even if the etching is stopped with the second semiconductor layer 105 or the buffer layer 106 exposed.
  • a region other than the region 160 is not limited to a flat surface, and a region other than the region 160 may be a rough surface or an uneven surface.
  • an insulating layer 170 covering at least part of the first semiconductor layer 103 can be formed. Insulating layer 170, SiO 2, SiNx or the like can be selected.
  • a light emitting element substrate 171 in which the second electrode 151 is formed in a part of the region 160 is formed.
  • the second conductivity type is n-type, it can include at least one material selected from Au, Ag, Al, Ni, Pd, Ge, Si, and Sn and have a thickness of 100 nm or more.
  • the second conductivity type is p-type, it can include at least one material selected from Au, Be, Mg, and Zn and have a film thickness of 100 nm or more.
  • a transparent film 180 having a refractive index lower than that of the transparent substrate 110 is laminated on the light extraction surface 115 side of the transparent substrate 110 of the light emitting element substrate 171. Then, the surface of the laminated transparent film 180 is roughened by frost processing by chemical treatment.
  • the transparent substrate 110 is preferably a sapphire substrate
  • the transparent film 180 is preferably an SiO 2 film.
  • the transparent film 180 is made of an SiO 2 film while using a sapphire substrate that is a material that is inexpensive and has high processing accuracy as the transparent substrate 110 but is difficult to be frosted by chemical treatment. Frost processing by chemical treatment can be easily performed on the surface of the steel.
  • the SiO 2 film as the transparent film 180 is subjected to frost processing on the surface with a mixed solution of hydrofluoric acid and monovalent to tetravalent inorganic acid or organic acid, and the frost having the uneven layer 181 on the surface of the SiO 2 film.
  • the processed substrate 182 can be manufactured. With such a method, it is possible to surely roughen the surface of the transparent film 180 to form irregularities.
  • the inorganic acid is composed of at least one of sulfuric acid, hydrochloric acid, and phosphoric acid
  • the organic acid is composed of at least one of malonic acid, acetic acid, citric acid, and tartaric acid. it can. If an inorganic acid or an organic acid as described above is used, irregularities can be more reliably formed on the surface of the transparent film.
  • the dice are fixed to the stem, and a light emitting diode sealed with an epoxy resin can be manufactured.
  • the surface of the transparent film 180 laminated on the transparent substrate 110 is roughened, the surface is easily roughened regardless of the material of the transparent substrate 110, and the light distribution angle is increased and the luminous efficiency is increased.
  • a light emitting element can be manufactured relatively easily.
  • the low refractive index material is formed on the light extraction surface 115 side, thereby generating a total reflection angle and further improving the light emission efficiency.
  • FIG. 9 shows a second embodiment of the light emitting device of the present invention.
  • a transparent substrate 210 is bonded to the light extraction surface 215 side.
  • a transparent film 280 having a refractive index lower than that of the transparent substrate 210 is provided on the light extraction surface 215 side of the transparent substrate 210, and the surface of the transparent film 280 is roughened.
  • a transparent substrate 210 made of, for example, sapphire, on which a transparent film 280 made of, for example, a SiO 2 film is formed can be suitably used.
  • the second dielectric film 221 made of, for example, SiO 2 and having a thickness of about 100 nm may be formed on the opposite side of the transparent substrate 210 from the transparent film 280.
  • the surface of the transparent film 280 is roughened, and irregularities are formed.
  • the transparent film 280 is made of a material having a refractive index lower than that of the transparent substrate 210. As described above, if the transparent film 280 having a low refractive index is provided on the transparent substrate 210 and the surface of the transparent film 280 is uneven, the surface can be easily roughened regardless of the material of the transparent substrate 210. It is possible to obtain a light-emitting element that is planarized and has an increased light distribution angle and increased light emission efficiency. Further, since the low refractive index material is formed on the light extraction surface 215 side, a total reflection angle is generated, and the light emission efficiency can be further increased.
  • irregularities are also formed on the surface of the transparent substrate 210 on the light extraction surface 215 side.
  • the transparent substrate 210 is lapped and polished to adjust the thickness.
  • polishing since polishing has a long processing time, it is advantageous in cost to perform lapping only.
  • the lapping surface is an uneven surface, but the unevenness is small because Ra (roughness) of the unevenness cannot be controlled due to processing restrictions.
  • the transparent film 280 By forming the transparent film 280 and forming rough irregularities on the surface, the transparent film 280 has a roughness that can advantageously extract light.
  • a transparent adhesive layer 225 may be formed on the surface of the second dielectric film 221.
  • the transparent adhesive layer 225 can be formed of a plurality of layers, for example, a first adhesive layer 225A and a second adhesive layer 225B.
  • a first dielectric film 220 made of, for example, SiO 2 and having a thickness of about 100 nm is formed on the transparent adhesive layer 225.
  • the surface of the first dielectric film 220 is made of, for example, AlGaAs, GaAsP, GaP, or the like.
  • the current propagation layer 207 can be formed with a thickness of 0.5 to 20 ⁇ m.
  • the second electrode 251 is formed on a part (second surface) of the surface of the current propagation layer 207, and the buffer layer 206 is formed on a region (first surface) where the second electrode 251 is not formed. It can be.
  • the second electrode 251 includes at least one material selected from Au, Ag, Al, Ni, Pd, Ge, Si, and Sn, and has a thickness of 100 nm or more. Is done.
  • the second conductivity type is p-type, it includes at least one material selected from Au, Be, Mg, and Zn and has a thickness of 100 nm or more.
  • a buffer layer 206 that relieves lattice irregularities may be formed on the surface of the current propagation layer 207.
  • the buffer layer 206 is most preferably formed of InGaP or AlInP. Since there is a lattice mismatch between GaAs x P 1-x (x ⁇ 1) and the AlGaInP-based material or AlGaAs-based material, GaAs x P 1-x (x ⁇ 1) has high-density strain and Threading dislocation enters. The threading dislocation density can be adjusted by the composition x.
  • a second semiconductor layer 205 made of AlGaInP or AlGaAs and having a thickness of 0.5 to 1.0 ⁇ m may be formed on the surface of the buffer layer 206.
  • An active layer 204 having a thickness of 0.1 to 10 ⁇ m may be formed on the surface.
  • This active layer 204 has (Al x Ga 1-x ) y In 1-y P (0 ⁇ x ⁇ 1, 0.4 ⁇ y ⁇ 0.6) or Al z Ga 1-z As ( 0 ⁇ z ⁇ 0.45).
  • AlGaInP When it is applied to visible light illumination, it is preferable to select AlGaInP, and when it is applied to infrared illumination, it is preferable to select AlGaAs or InGaAs.
  • the design of the active layer 204 is not limited to the above materials because the wavelength can be adjusted to other than the wavelength resulting from the material composition by using a superlattice or the like.
  • the first semiconductor layer 203 made of AlGaInP or AlGaAs and having a thickness of 0.5 to 1.0 ⁇ m may be formed on the surface of the active layer 204.
  • the first electrode 250 may be formed on the surface of the first semiconductor layer 203.
  • a desired layer such as the buffer layer 216 may be provided between the first semiconductor layer 203 and the first electrode 250 as necessary.
  • the first electrode 250 includes at least one material selected from Au, Ag, Al, Ni, Pd, Ge, Si, and Sn, and has a thickness of 100 nm or more. Is done.
  • the first conductivity type is p-type, it includes at least one material selected from Au, Be, Mg, and Zn and has a thickness of 100 nm or more.
  • the second electrode 251 is provided in the current propagation layer 207 is illustrated, but the second electrode 251 may be provided in the second semiconductor layer 205.
  • a substrate 201 is prepared as a starting substrate.
  • the substrate 201 it is preferable to use a substrate 201 whose crystal axis is inclined in the [110] direction from the [001] direction.
  • the substrate 201 GaAs or Ge can be preferably used. If the substrate 201 is selected from the above materials, the material of the active layer 204 to be described later can be epitaxially grown in a lattice-matched system, so that the quality of the active layer 204 can be easily improved, and the luminance and life characteristics can be improved. .
  • a first semiconductor layer 203 (for example, having a thickness of 0.5 to 1.0 ⁇ m) of the first conductivity type having substantially the same lattice constant as that of the substrate 201 and an active layer 204 (for example, having a thickness of 0.1).
  • second conductivity type second semiconductor layer 205 (for example, thickness of 0.5 to 1.0 ⁇ m), buffer layer 206, and current propagation layer 207 (for example, thickness of about 2.0 ⁇ m) are sequentially grown by epitaxial growth.
  • a selective etching layer 202 for removing the substrate 201 may be inserted between the substrate 201 and the first semiconductor layer 203.
  • the selective etching layer 202 has a layer structure of two or more layers, and preferably includes at least a first selective etching layer 202A in contact with the substrate 201 and a second selective etching layer 202B in contact with the first semiconductor layer 203.
  • the first selective etching layer 202A and the second selective etching layer 202B may be made of different materials or compositions.
  • the substrate 201 on the selective etching layer 202 when the selective etching layer 202 is provided, for example, MOVPE (metal organic chemical vapor deposition) or MBE (molecular beam epitaxy).
  • MOVPE metal organic chemical vapor deposition
  • MBE molecular beam epitaxy
  • the buffer layer 206 and the current propagation layer 207 are formed on the light emitting portion 208 including the first conductive type first semiconductor layer 203, the active layer 204, and the second conductive type second semiconductor layer 205 by CBE (chemical beam epitaxy).
  • CBE chemical beam epitaxy
  • the epitaxial substrate 209 epitaxially grown in this order can be manufactured.
  • the active layer 204 has (Al x Ga 1-x ) y In 1-y P (0 ⁇ x ⁇ 1, 0.4 ⁇ y ⁇ 0.6) or Al z Ga 1-z As ( 0 ⁇ z ⁇ 0.45).
  • AlGaInP When it is applied to visible light illumination, it is preferable to select AlGaInP, and when it is applied to infrared illumination, it is preferable to select AlGaAs or InGaAs.
  • the design of the active layer 204 is not limited to the above materials because the wavelength can be adjusted to other than the wavelength resulting from the material composition by using a superlattice or the like.
  • the material selection is not necessarily the same material system as that of the active layer 204.
  • the first semiconductor layer 203, the light emitting layer 204, and the second semiconductor layer 205 having the simplest structure are exemplified by the same material, but the first semiconductor layer 203 or the second semiconductor layer is exemplified.
  • 205 generally includes a plurality of layers in order to improve characteristics, and the second semiconductor layer 205 is not limited to a single layer.
  • the first semiconductor layer 203 is composed of a layer having two or more types of Al composition.
  • the second layer 203B is closer to the active layer 204, and the first layer 203A having lower Al composition is closer to the substrate 201. It can be set as the structure which has.
  • the second layer 203B is a functional layer having the function of a cladding layer, and does not mean a single composition or a single condition layer.
  • the current propagation layer 207 AlGaAs, GaAsP, or GaP can be suitably used.
  • the buffer layer 206 is most preferably formed of InGaP or AlInP. Since there is a lattice mismatch between GaAs x P 1-x (x ⁇ 1) and the AlGaInP-based material or AlGaAs-based material, GaAs x P 1-x (x ⁇ 1) has high-density strain and Threading dislocation enters. The threading dislocation density can be adjusted by the composition x.
  • a first dielectric film (first SiO 2 film) 220 is deposited on the current propagation layer 207 in the epitaxial substrate 209.
  • the first dielectric film 220 can be formed by optical CVD, sputtering, or PECVD.
  • a transparent adhesive layer 225 can be formed on the first dielectric film 220 to form the first bonding substrate 226.
  • BCB benzocyclobutene
  • epoxy can be selected. It is preferable to select a material that can be formed by a dipping method or a spin coating method.
  • a second dielectric film (second SiO 2 film) 221 can be deposited on the transparent substrate 210 to form the second bonding substrate 231.
  • the second dielectric film 221 can be formed by optical CVD, sputtering, or PECVD. It goes without saying that the same effect can be obtained even if a transparent adhesive layer is provided on the second bonding substrate 231.
  • the first bonding substrate 226 and the second bonding substrate 231 are placed so that the transparent adhesive layer 225 and the second dielectric film 221 face each other and are not in contact with each other, and a vacuum atmosphere of 10 Pa or less is set. After the vacuum atmosphere, the transparent adhesive layer 225 and the second dielectric film 221 are brought into contact with each other, controlled to be a pressure of 5000 N and a temperature between 100 to 200 ° C. and held for 5 minutes or more, and then 100 ° C. or more. Then, the first bonding substrate 226 and the second bonding substrate 231 are pressure-bonded to form the bonding substrate 240.
  • the uneven surface 212 is formed on the light extraction surface 215 side of 210.
  • the uneven surface 212 can be mirror-finished by processing such as polishing, it requires processing for a long time, so it is preferable not to perform it here in order to prevent damage to the epitaxial substrate 209. Moreover, it can be advantageous in cost by performing only lapping.
  • the substrate 201 is removed from the bonding substrate 240 by etching.
  • etching can be performed with a mixed solution of ammonia water and hydrogen peroxide water.
  • first selective etching layer 202A By using a material different from that of the substrate 201 for the etching stop layer (first selective etching layer 202A), etching using a mixed solution of ammonia water and hydrogen peroxide water can be selectively stopped.
  • AlInP can be used as the first selective etching layer 202A.
  • the first selective etching layer 202A is removed. Since AlInP is used for the etching stop layer 202A, removal is performed using hydrochloric acid. Since the second selective etching layer 202B stops etching with hydrochloric acid, GaAs can be used.
  • the first electrode 250 in contact with the first semiconductor layer 203 is formed.
  • the first electrode 250 includes at least one material selected from Au, Ag, Al, Ni, Pd, Ge, Si, and Sn, and has a thickness of 100 nm or more. can do.
  • the first conductivity type is p-type, it can include at least one material selected from Au, Be, Mg, and Zn and have a thickness of 100 nm or more.
  • the second selective etching layer 202B may be left behind.
  • a pattern in which the first semiconductor layer 203 and the active layer 204 in the region 260 are cut out is formed by etching using a dry method or a wet method.
  • FIG. 13 shows an example in which the current propagation layer 207 is cut out, the same function is obtained even if the etching is stopped with the second semiconductor layer 205 or the buffer layer 206 exposed.
  • a region other than the region 260 is not limited to a flat surface, and a region other than the region 260 may be a rough surface or an uneven surface.
  • Insulating layer 270 that covers at least a part of the first semiconductor layer 203 can be formed.
  • Insulating layer 270 is, SiO 2, SiNx or the like can be selected.
  • a light emitting element substrate 271 in which the second electrode 251 is formed in a part of the region 260 is formed.
  • the second conductivity type is n-type, it can include at least one material selected from Au, Ag, Al, Ni, Pd, Ge, Si, and Sn and have a thickness of 100 nm or more.
  • the second conductivity type is p-type, it can include at least one material selected from Au, Be, Mg, and Zn and have a film thickness of 100 nm or more.
  • a transparent film 280 having a refractive index lower than that of the transparent substrate 210 is laminated on the light extraction surface 215 side surface of the transparent substrate 210 of the light emitting element substrate 271. Then, the surface of the laminated transparent film 280 is roughened by frost processing by chemical treatment.
  • the transparent substrate 210 is preferably a sapphire substrate and the transparent film 280 is preferably an SiO 2 film.
  • the transparent film 280 is preferably an SiO 2 film.
  • the frost processing is performed on the surface of the SiO 2 film, which is the transparent film 280, with a mixed solution of hydrofluoric acid and monovalent to tetravalent inorganic acid or organic acid, and the frosted layer 281 is provided on the surface of the SiO 2 film.
  • a processed substrate 282 can be manufactured. With such a method, the surface of the transparent film 280 can be reliably roughened to form irregularities.
  • the inorganic acid is composed of at least one of sulfuric acid, hydrochloric acid, and phosphoric acid
  • the organic acid is composed of at least one of malonic acid, acetic acid, citric acid, and tartaric acid. it can. If an inorganic acid or an organic acid as described above is used, irregularities can be more reliably formed on the surface of the transparent film.
  • the dice are fixed to the stem, and a light emitting diode sealed with an epoxy resin can be manufactured.
  • the surface of the transparent film 280 laminated on the transparent substrate 210 is roughened, the surface is easily roughened regardless of the material of the transparent substrate 210, and the light distribution angle is increased and the luminous efficiency is increased.
  • a light emitting element can be manufactured relatively easily.
  • the low refractive index material is formed on the light extraction surface 215 side, so that the total reflection angle is generated and the luminous efficiency can be further increased.
  • the unevenness is also formed on the surface of the transparent substrate 210, light extraction can be performed by laminating a transparent film on the transparent substrate 210 to form rough unevenness on the surface. It has the roughness which can be made more advantageous.
  • the refractive index of the transparent substrate on the light extraction surface side is higher than that of the transparent substrate.
  • the transparent film having a low thickness is laminated and the surface of the transparent film is roughened.
  • the present invention is not limited to this.
  • a transparent film may be laminated in advance on the transparent substrate before bonding, and the first bonding substrate may be bonded to the surface of the laminated transparent film subjected to the roughening treatment.
  • Example 1 As shown in FIG. 2, a GaAs substrate (substrate 101) having a crystal axis inclined in the [110] direction from the [001] direction was prepared as a starting substrate. Next, an n-type cladding layer (first semiconductor layer 103) having a thickness of 1.0 ⁇ m made of AlGaInP, an active layer 104, and a thickness of 1.0 ⁇ m are formed on the GaAs substrate 101 by MOVPE (metal organic chemical vapor deposition). The p-type cladding layer (second semiconductor layer 105) was epitaxially grown, and a buffer layer 106 made of InGaP and a current propagation layer 107 made of GaP having a thickness of 2.0 ⁇ m were sequentially formed by epitaxial growth. A selective etching layer 102 (also called an etching stop layer) composed of an AlInP layer and a GaAs layer was formed between the GaAs substrate and the n-type cladding layer.
  • MOVPE metal organic chemical vapor deposition
  • the first semiconductor layer 103 is composed of two or more types of Al compositions, and the first layer 103A having a low Al composition is formed on the side close to the substrate 101.
  • a first SiO 2 film (first dielectric film 120) was formed on the current propagation layer 107 made of GaP by PECVD using TEOS and O 2 as raw materials.
  • a transparent adhesive layer 125 was formed on the first dielectric film 120, and a first bonding substrate 126 was formed.
  • cycloten was dropped and spin coating was performed at a rotational speed of 1,000 rpm. After spin coating, the solvent was volatilized by maintaining on a hot plate at a temperature of 100 ° C. for 60 seconds.
  • a sapphire substrate was prepared as the transparent substrate 110, and a second SiO 2 film (second dielectric film 121) was deposited on the transparent substrate 110 to form a second bonded substrate 131.
  • the second dielectric film 121 was formed by PECVD using TEOS and O 2 as raw materials.
  • the first bonding substrate 126 and the second bonding substrate 131 were placed so that the transparent adhesive layer 125 and the second dielectric film 121 face each other and were not in contact with each other, and a vacuum atmosphere of 10 Pa or less was set. After the vacuum atmosphere, the transparent adhesive layer 125 and the second dielectric film 121 are brought into contact with each other and controlled to a pressure of 5000 N and a temperature of 100 ° C. for 10 minutes, and then heat of 100 ° C. or higher is applied. The first bonded substrate 126 and the second bonded substrate 131 were pressure bonded to form the bonded substrate 140. Thereafter, in order to obtain a desired thickness, lapping and polishing were performed on the surface of the sapphire substrate.
  • the substrate 101 was removed from the bonding substrate 140 by etching with a mixed solution of ammonia water and hydrogen peroxide solution. After removing the substrate 101, the first selective etching layer 102A was removed. Since the first selective etching layer 102A used AlInP, hydrochloric acid was used for removal. Next, a first electrode 150 having a thickness of 500 nm made of an AuGeNi alloy in contact with the first semiconductor layer 103 was formed.
  • a pattern in which the first semiconductor layer 103, the active layer 104, the second semiconductor layer 105, and the buffer layer 106 in the region 160 were cut out was formed by etching using a dry method.
  • an insulating layer 170 covering the first semiconductor layer 103, the active layer 104, the second semiconductor layer 105, and the buffer layer 106 was formed.
  • the insulating layer 170 was formed by PECVD using TEOS and O 2 as raw materials.
  • the film thickness was 100 nm.
  • a second electrode 151 made of an AuBe alloy and having a thickness of 500 nm was formed in part of the region 160, and a light emitting element substrate 171 was formed.
  • a SiO 2 film was formed as a transparent film 180 on the light extraction surface 115 side surface of the transparent substrate 110 of the light emitting element substrate 171.
  • the transparent film 180 was subjected to a frost treatment on the surface with a mixed solution of hydrofluoric acid and acetic acid, so that a frosted substrate 182 having an uneven layer 181 on the surface of the transparent film 180 was produced.
  • the dice were fixed to the stem, and a light emitting diode sealed with an epoxy resin was manufactured.
  • Example 2 After joining the sapphire substrate, thin film processing is performed on the sapphire substrate to a specified thickness by lapping, and subsequent polishing is not performed. Manufactured.
  • Example 2 A light emitting diode was manufactured in the same manner as in Example 1 except that the SiO 2 film was not formed on the surface of the sapphire substrate.
  • FIG. 17 shows the difference in light distribution characteristics of the light emitting diodes manufactured in Example 1, Example 2, and Comparative Example.
  • the comparative example has a light distribution angle of around ⁇ 30 degrees, while the first and second embodiments have a relative light distribution angle of 50% or more with respect to the light distribution angle of ⁇ 60 degrees. It has light distribution intensity, and it can be seen that the light distribution angle is widened.
  • FIG. 18 shows current-luminance characteristics of the light-emitting diodes manufactured in Example 1, Example 2, and Comparative Example. It can be seen that Example 1 and Example 2 maintain the linearity of the current-luminance characteristics, although the luminance is generally high compared to the comparative example.
  • the present invention is not limited to the above embodiment.
  • the above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Abstract

La présente invention concerne un élément électroluminescent ayant un substrat transparent lié à un côté surface d'extraction de lumière de celui-ci, l'élément électroluminescent étant caractérisé en ce qu'un film transparent, ayant un indice de réfraction inférieur à celui du substrat transparent, est disposé sur la surface externe du côté surface d'extraction de lumière du substrat transparent, et la surface externe du film transparent est rugueuse. Par conséquent, l'invention concerne : l'élément électroluminescent formé par liaison du substrat transparent, l'angle de distribution lumineuse étant augmenté et l'efficacité lumineuse étant augmentée ; et un procédé de fabrication de l'élément électroluminescent.
PCT/JP2017/030644 2016-10-12 2017-08-28 Élément électroluminescent et son procédé de fabrication WO2018070120A1 (fr)

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