WO2010023777A1 - 発光素子 - Google Patents
発光素子 Download PDFInfo
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- WO2010023777A1 WO2010023777A1 PCT/JP2009/000787 JP2009000787W WO2010023777A1 WO 2010023777 A1 WO2010023777 A1 WO 2010023777A1 JP 2009000787 W JP2009000787 W JP 2009000787W WO 2010023777 A1 WO2010023777 A1 WO 2010023777A1
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- WIPO (PCT)
- Prior art keywords
- nitride semiconductor
- type nitride
- semiconductor portion
- light emitting
- axis
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- 239000004065 semiconductor Substances 0.000 claims abstract description 140
- 150000004767 nitrides Chemical class 0.000 claims abstract description 113
- 239000002245 particle Substances 0.000 claims abstract description 69
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims description 24
- 239000000758 substrate Substances 0.000 description 64
- 238000000034 method Methods 0.000 description 43
- 239000010408 film Substances 0.000 description 31
- 239000000463 material Substances 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 14
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 10
- 238000004544 sputter deposition Methods 0.000 description 10
- 229910002601 GaN Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000000927 vapour-phase epitaxy Methods 0.000 description 7
- 150000004820 halides Chemical class 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 229910052594 sapphire Inorganic materials 0.000 description 5
- 239000010980 sapphire Substances 0.000 description 5
- 238000001947 vapour-phase growth Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- NWAIGJYBQQYSPW-UHFFFAOYSA-N azanylidyneindigane Chemical compound [In]#N NWAIGJYBQQYSPW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011824 nuclear material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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
- H01L33/16—Semiconductor devices having potential barriers 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 crystal structure or orientation, e.g. polycrystalline, amorphous or porous
- H01L33/18—Semiconductor devices having potential barriers 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 crystal structure or orientation, e.g. polycrystalline, amorphous or porous within the light emitting region
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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 having potential barriers 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
- H01L33/24—Semiconductor devices having potential barriers 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 of the light emitting region, e.g. non-planar junction
Definitions
- the present invention relates to a direct current drive type electroluminescent device using nitride semiconductor light emitting particles having a wurtzite crystal structure.
- GaN-based semiconductors typified by gallium nitride (GaN), indium nitride / gallium mixed crystal (InGaN), aluminum nitride / gallium mixed crystal (AlGaN) or indium nitride / aluminum / gallium mixed crystal (InAlGaN) as typical semiconductor materials Is attracting attention, and its research and development is actively underway.
- Such a GaN-based semiconductor has been conventionally produced as a single crystal thin film by growing on a substrate using a MOCVD (Metal Organic Chemical Vapor Deposition) method.
- MOCVD Metal Organic Chemical Vapor Deposition
- MOCVD Metal Organic Chemical Vapor Deposition
- organic EL is another candidate for a light-emitting element that operates by direct current.
- Organic EL can be manufactured at low cost because it can use an inexpensive process such as vapor deposition and can use an inexpensive substrate such as glass.
- the reliability of organic EL is a problem.
- an inorganic light-emitting material is handled as particles instead of a thin film, and the light-emitting elements are formed by arranging the particles.
- the merit of the above means is that, for an inorganic thin film type direct current light emitting device, an inorganic light emitter can be generated without being affected by a substrate or the like, so that crystallinity can be increased and a large screen can be easily formed.
- organic EL there is an advantage that reliability can be improved because an inorganic substance can be used for the light emitter.
- an example in which inorganic light-emitting particles are arranged to constitute a light-emitting element has been proposed (for example, see Patent Document 1).
- a light emitting layer made of another nitride semiconductor exists on the surface of a nitride semiconductor serving as a nucleus, and a nitride semiconductor layer is laminated on the light emitting layer, and these nitride semiconductor-light emitting layer A technique is disclosed in which the nitride semiconductor layer forms a quantum well structure.
- an object of the present invention is to provide a light-emitting element that improves the light-emitting efficiency of the light-emitting particles, has high light-emitting efficiency, and can easily increase the area.
- a light emitting device includes a pair of anode and cathode facing each other, A plurality of luminescent particles sandwiched between the pair of anode and cathode from a direction perpendicular to the main surface of the anode and the cathode;
- the light emitting particles are nitride semiconductor light emitting particles having a wurtzite crystal structure including an n-type nitride semiconductor portion and a p-type nitride semiconductor portion, wherein the n-type nitride semiconductor portion is in contact with the cathode, The p-type nitride semiconductor portion is in contact with the anode;
- the c-axis in each crystal structure is parallel to each other, and the n-type nitride semiconductor portion and the p-type nitride semiconductor portion are They are in contact with each other on a
- the light emitting particles may be provided with an insulating film on the n-type nitride semiconductor portion, and a portion of the insulating film may be removed to expose a surface parallel to the c-axis of the n-type nitride semiconductor portion.
- the p-type nitride semiconductor portion may be grown.
- the luminescent particles are provided with an insulating film on the p-type nitride semiconductor portion, and a part of the insulating film is removed to expose a surface parallel to the c-axis of the p-type nitride semiconductor portion.
- the n-type nitride semiconductor portion may be grown.
- the luminescent particles may be arranged such that the c-axis in the crystal structure of the n-type nitride semiconductor portion and the p-type nitride semiconductor portion is parallel to the main surfaces of the anode and the cathode. .
- the light emitting particles have the following lengths in the direction parallel to the c-axis common to the n-type nitride semiconductor portion and the p-type nitride semiconductor portion, and the shortest width of the bottom surface perpendicular to the c-axis. Relational expression (particle length in c-axis direction) / (shortest width of bottom surface perpendicular to c-axis direction) ⁇ 2 May be satisfied.
- the n-type nitride semiconductor portion and the p-type nitride semiconductor portion are included in one light-emitting particle, light emission is facilitated by the combination of electrons and holes. Will improve.
- the n-type nitride semiconductor portion and the p-type nitride semiconductor portion have the c-axis of each crystal structure parallel to each other, and the n-type nitride semiconductor portion and the p-type nitride are The semiconductor portions are in contact with each other on a plane parallel to the c-axis. Therefore, all the current paths in the luminescent particles can be perpendicular to the c-axis, and high-efficiency light emission can be obtained. As a result, a light-emitting element with high light-emitting efficiency can be obtained.
- the light emitting particles are provided with an insulating film on the n-type nitride semiconductor portion, and a part of the insulating film is removed to expose a surface parallel to the c-axis of the n-type nitride semiconductor portion.
- a physical semiconductor portion may be grown.
- an insulating film is provided on the p-type nitride semiconductor portion, a part of the insulating film is removed to expose a surface parallel to the c-axis of the p-type nitride semiconductor portion, and an n-type nitride semiconductor portion is grown. May be configured.
- the growth surface and the nitride semiconductor portion to be grown can be made into a nitride semiconductor having the same wurtzite crystal structure, and it becomes possible to suppress strain and dislocation during growth, resulting in higher luminous efficiency. Luminescent particles can be obtained.
- the side surfaces of the luminescent particles are brought into contact with one of the electrodes. This makes it easier to increase the light emission luminance.
- FIG. 1 It is a schematic block diagram of the light emitting element which concerns on Embodiment 1 of this invention. It is a figure which shows 1 process of the manufacturing process of the light emitting element which concerns on this Embodiment 1.
- FIG. It is a figure which shows 1 process of the manufacturing process of the light emitting element which concerns on this Embodiment 1.
- FIG. It is a figure which shows 1 process of the manufacturing process of the light emitting element which concerns on this Embodiment 1.
- FIG. It is a figure which shows 1 process of the manufacturing process of the light emitting element which concerns on this Embodiment 1.
- FIG. It is a figure which shows 1 process of the manufacturing process of the light emitting element which concerns on this Embodiment 1.
- FIG. It is a figure which shows 1 process of the manufacturing process of the light emitting element which concerns on this Embodiment 1.
- FIG. It is a figure which shows 1 process of the manufacturing process of the light emitting element which concerns on this Embodiment 1.
- FIG. It is
- FIG. It is a figure which shows 1 process of the manufacturing process of the light emitting element which concerns on this Embodiment 1.
- FIG. It is a figure which shows 1 process of the manufacturing process of the light emitting element which concerns on this Embodiment 1.
- FIG. It is a figure which shows 1 process of the manufacturing process of the light emitting element which concerns on this Embodiment 1.
- FIG. It is a figure which shows 1 process of the manufacturing process of the light emitting element which concerns on this Embodiment 1.
- FIG. It is a figure which shows 1 process of the manufacturing process of the light emitting element which concerns on this Embodiment 1.
- FIG. It is the schematic which shows the structure of the HVPE apparatus for manufacturing the luminescent particle which concerns on this Embodiment 1.
- FIG. 1 shows a schematic configuration of the light emitting element according to Embodiment 1 of the present invention.
- a lower electrode 20 luminescent particles 50, an upper electrode 30, and an upper substrate 40 are disposed in this order on a lower substrate 10.
- FIG. 1 shows a minimum configuration for emitting light, and other members may be further provided.
- the n-type nitride semiconductor portion 52 and the p-type nitride semiconductor portion 53 are included in one light-emitting particle 50, light emission is facilitated by the combination of electrons and holes, so that the light emission efficiency is improved. To do. Further, in one light emitting particle 50, the n-type nitride semiconductor portion 52 and the p-type nitride semiconductor portion 53 have the c-axis of each crystal structure parallel to each other, and the n-type nitride semiconductor portion 52 and The p-type nitride semiconductor portion 53 is in contact with each other on a plane parallel to the c-axis. Therefore, all the current paths in the luminescent particles 50 can be made perpendicular to the c-axis, and high-efficiency light emission can be obtained. As a result, a light-emitting element with high light-emitting efficiency can be obtained.
- the materials of the lower substrate 10 and the upper substrate 40 are not particularly limited. However, when growing the semiconductor in the light emitting particles using the lower substrate 10, it is necessary to select a substrate that can withstand the semiconductor growth process. In order to extract light emitted from the light emitting layer, it is desirable to select a light transmissive material for either the lower substrate 10 or the upper substrate 40. In addition, both substrates are not necessarily required as long as the shape as a light emitting element can be maintained.
- the material of the lower electrode 20 and the upper electrode 30 is not particularly limited as long as the material is conductive. However, when a semiconductor in the luminescent particles is grown on the lower electrode 20, it is necessary to select a substrate that can withstand the process. . However, it is desirable to use a material having a low work function such as aluminum, magnesium or silver as the material used on the cathode side, and a material having a high work function such as gold or ITO is preferable as the material used on the anode side.
- the electrode on the light extraction side is preferably a light transmissive material.
- a non-light transmissive material it is desirable to have a film thickness of 100 nm or less in order to transmit light as much as possible.
- a conductive substrate such as a Si substrate or a metal substrate doped with other elements
- the substrate itself can be used as an electrode, so that it is not always necessary to provide a separate electrode.
- either of the electrodes has flexibility. Since the size of the luminescent particles 50 varies, if one of the electrodes is not a flexible electrode, there are many particles that cannot contact the two electrodes and do not emit light, resulting in a decrease in luminance of the light-emitting element. Invite.
- the luminescent particles 50 and the electrodes 20 and 30 are in direct contact with each other, but may be in contact with each other through a conductor or a semiconductor.
- the light emitting particle 50 includes a nucleus 51, an n-type nitride semiconductor portion 52, a p-type nitride semiconductor portion 53, and an insulating film 54. This shows a minimum configuration, and other members may be further arranged.
- a semiconductor layer having a narrower band gap than the n-type nitride semiconductor 52 and the p-type nitride semiconductor 53 is provided at the interface between the n-type nitride semiconductor 52 and the p-type nitride semiconductor 53 to form a double hetero structure.
- a buffer layer for promoting growth may be provided at the interface between the nucleus 51 and the semiconductor layer.
- the n-type nitride semiconductor 52 and the p-type nitride semiconductor 53 are grown around the nucleus 51, but the growth position is not particularly limited, and may be partially grown around the nucleus 51.
- the n-type nitride semiconductor portion 52 and the p-type nitride semiconductor portion 53 may be in direct contact with each other in a plane parallel to the c-axis, or may be in electrical contact via a conductor or semiconductor.
- the nucleus 51 is necessary for growing the n-type nitride semiconductor portion 52 or the p-type nitride semiconductor portion 53, and preferably has a wurtzite structure, and has a lattice constant as much as possible with the nitride semiconductor to be grown. Closer is better.
- the semiconductor material to be grown is GaN, for example, sapphire, ZnO, AlN, and the like are listed as candidates for the nuclear material.
- the core 51 may naturally be the same material as the semiconductor material to be grown.
- Each of the n-type nitride semiconductor portion 52 and the p-type nitride semiconductor portion 53 is a nitride semiconductor having a wurtzite crystal structure.
- the nitride semiconductor wurtzite type crystal structure for example, AlN, GaN, InN, Al x Ga (1-x) N, etc. In y Ga (1-y) N and the like.
- Each semiconductor portion is preferably a single crystal, and a vapor phase growth method is preferable as a means for generating the single crystal.
- Examples of growth means using vapor phase growth include a halide vapor phase growth (HVPE) method and a metal organic vapor phase growth (MOCVD) method.
- HVPE halide vapor phase growth
- MOCVD metal organic vapor phase growth
- a semiconductor growth method using vapor phase growth particles serving as nuclei are arranged on a substrate, heated to a required temperature, and then a source gas is flowed to grow the semiconductor on the nuclei on the substrate.
- an n-type semiconductor can be formed by doping Si.
- the characteristics of an n-type semiconductor are exhibited even when not doped.
- the characteristics of the p-type semiconductor are exhibited by doping Mg.
- the insulating film 54 is not necessarily required, but it is desirable to be present at a part of the interface between the n-type nitride semiconductor portion 52 and the p-type nitride semiconductor 53.
- the insulating film 54 is not necessarily required, but it is desirable to be present at a part of the interface between the n-type nitride semiconductor portion 52 and the p-type nitride semiconductor 53.
- crystals grow from various locations in the plane of the substrate, but crystals that grow in the horizontal direction with respect to the substrate interfere with each other and often cause dislocations. .
- an insulator on which a crystal does not grow on the substrate, growth is not inhibited, so that dislocations can be reduced.
- the insulating film 54 is provided so as to cover the n-type nitride semiconductor portion 52 or the p-type nitride semiconductor portion 53, and the insulating film is exposed so that only a part of the plane parallel to the c-axis is exposed. A portion of 54 is removed. By exposing only a part of the surface parallel to the c-axis as the growth surface, it is possible to suppress the growth in the horizontal direction on the growth surface and to suppress the inhibition of the growth of the entire crystal.
- the material of the insulating film 54 include Al 2 O 3 , SiO 2 , TiO 2 , and BaTiO 3 .
- the means for manufacturing the light emitting element is not limited, but an example thereof will be described with reference to FIGS. 2a to 2j.
- a growth mask 62 is formed on a growth substrate 61 for growing luminescent particles as shown in FIG.
- the growth substrate 61 at this time needs to be able to withstand the process of forming the n-type nitride semiconductor portion 52 and the p-type nitride semiconductor portion 53 to be formed later.
- HVPE halide vapor phase epitaxy
- MOCVD metal organic vapor phase epitaxy
- a substrate on which a GaN semiconductor is epitaxially grown in the c-axis direction is preferable.
- materials include a sapphire substrate with a plane orientation (0, 0, 0, 1), a plane orientation (1, 1, 1) silicon substrate, and the like.
- the growth mask 62 may be made of any material that can withstand the nucleation process and is easy to remove. Examples include SiO 2 and the like.
- the method of forming the hole portion of the growth mask 62 includes a method of forming by a lift-off method using a photoresist material, a method of directly forming other than the hole portion by using an ink jet method or the like, and a hole using a forming mask. For example, a method of directly forming the portion other than the portion.
- nuclei 51 are formed.
- the means for generating the nuclear material is not particularly limited, but a sputtering method, a halide vapor deposition (HVPE) method, a metal organic chemical vapor deposition (MOCVD) method, or the like is preferable.
- the mask 62 is removed as shown in FIG. In the process of removing the mask 62 at this time, it is necessary to use means that does not affect the nucleus 51.
- the nucleus 51 may be formed directly on the growth substrate 61 without using a growth mask. For example, if the means introduced in non-patent literature (Jpn. J. Appl. Phys. Vol.
- n-type nitride semiconductor portion 52 is formed on the nucleus 51 as shown in FIG.
- the means is preferably a halide vapor phase epitaxy (HVPE) method or a metal organic vapor phase epitaxy (MOCVD) method as described above.
- HVPE halide vapor phase epitaxy
- MOCVD metal organic vapor phase epitaxy
- E As shown in FIG. 2 e, the particles in which the n-type nitride semiconductor portion 52 is formed on the nucleus 51 are separated from the growth substrate 61.
- a means for separating for example, a mechanical means such as a means for applying vibration or a means for scraping off with a sharp object, or a chemical means such as dissolving a substrate may be used.
- particles including the nucleus 51 and the n-type nitride semiconductor portion 52 are arranged on the lower substrate 10 including the lower electrode 20.
- the particles it is more desirable to vibrate the lower substrate 10 because the longitudinal direction of each particle, that is, the c-axis direction is easily oriented parallel to the surface.
- an insulating film 54 is formed on the particles.
- the forming means is not particularly limited, and for example, a sputtering method can be mentioned.
- H Further, as shown in FIG. 2h, a part of the insulating film 54 is removed. In this case, the surface parallel to the c-axis of the particles is exposed.
- the means for removing the insulating film 54 is not limited, and examples thereof include a mechanical polishing method, a wet etching method, and a dry etching method.
- I As shown in FIG.
- a p-type nitride semiconductor portion 53 is formed on a surface parallel to the c-axis of the n-type nitride semiconductor portion 52 that is exposed by removing a part of the insulating film 54.
- the halide vapor phase epitaxy (HPVE) method, the organometallic vapor phase epitaxy (MOCVD) method or the like is preferable as described above. In these processes, when the p-type nitride semiconductor portion is formed, both the lower electrode 20 and the lower substrate 10 must have heat resistance of 1000 ° C. or higher in an NH 3 atmosphere.
- Examples of the material of the lower substrate 10 include a sapphire substrate and a silicon substrate, and examples of the material of the lower electrode 20 include molybdenum and tantalum. (J) Thereafter, the upper electrode 30 and the upper substrate 40 are sequentially disposed as shown in FIG.
- Example 1 A method for manufacturing the light emitting device according to Example 1 will be described below.
- a 2-inch (5.08 cm) sapphire substrate having a plane orientation (0, 0, 0, 1) is used as a growth substrate.
- a SiO 2 film having a thickness of 10 ⁇ m was formed on the sapphire substrate using a sputtering method through a formation mask. The diameter of the hole was 2 ⁇ m.
- the target was formed by sputtering using an SiO 2 target in an Ar gas atmosphere.
- An AlN film was formed thereon as a nucleus by a sputtering method. The target was formed by sputtering using an Al target in an N 2 gas atmosphere.
- AlN grew in the c-axis direction and had a thickness of 10 ⁇ m.
- C The growth substrate on which the growth mask and nuclei were formed was immersed in a 3% aqueous hydrofluoric acid solution to remove the growth mask.
- a non-doped GaN layer was formed as an n-type nitride semiconductor layer on a growth substrate on which only nuclei were formed, using a halide vapor phase epitaxy (HVPE) method. Details will be described below with reference to FIG.
- HVPE halide vapor phase epitaxy
- the particle bottom width was 6 ⁇ m
- the particle height was 12 ⁇ m.
- E After forming the n-type nitride semiconductor layer, mechanical growth is applied to the growth substrate, and particles having nuclei and n-type nitride semiconductor are taken out of the growth substrate and boron-doped n-type Si substrate Arranged while applying mechanical vibration on the top. At this time, the n-type Si substrate serves as a lower substrate and a lower electrode.
- n-type Si substrate on which particles having nuclei and an n-type nitride semiconductor were disposed was attached to a sputtering apparatus, and an Al 2 O 3 film was formed as an insulating film by a sputtering method.
- the target was formed by using an Al 2 O 3 target and performing sputtering in Ar gas. The thickness was 0.2 ⁇ m.
- Ar plasma was generated on the substrate side in the sputtering apparatus, and the surface of the insulating film was dry etched. As a result, a part of the surface parallel to the c-axis of the n-type nitride semiconductor was exposed.
- the n-type Si substrate on which the particles having the nucleus, the n-type nitride semiconductor, and the insulating film are arranged is taken out and attached again to the HVPE apparatus, and parallel to the exposed c-axis of the n-type nitride semiconductor
- a p-type nitride semiconductor layer was formed on a smooth surface. This will also be described with reference to FIG.
- HCl was supplied at 3 cc / min and N 2 was supplied at 250 cc / min, and Ga metal 75 was disposed in the middle.
- the gas line B73 was provided with MgCl 2 powder 76, and N 2 gas was supplied at 250 cc / min.
- Example 2 a light-emitting element was produced in the same manner as in Example 1 except that an insulating film of luminescent particles was not formed.
- the luminance was 520 cd / m 2 and the light emission efficiency was 1.11 m / W.
- Example 1 Compared to Example 2, the thickness of the SiO 2 film that is the formation mask is changed to 1 ⁇ m, the diameter of the hole is changed to 2 ⁇ m, and the thickness of the AlN film that is the nucleus is changed to 1 ⁇ m. No mechanical vibration was applied when the particles having the above were taken out and placed on an n-type Si substrate doped with boron. As a result, most of the luminescent particles had the c-axis of the luminescent particles perpendicular to the substrate. When this light emitting element was made to emit light by applying a voltage in the same manner as the light emitting element of Example 1, the luminance was 320 cd / m 2 and the luminous efficiency was 0.6 lm / W.
- Comparative Example 2 A light emitting device was produced in the same manner as in Comparative Example 1 except that the p-type semiconductor layer of the light emitting particles was not formed, but an n-type semiconductor layer was formed to 4 ⁇ m. Similarly, when a light was applied to the light emitting element to emit light, the luminance was 80 cd / m 2 and the light emission efficiency was 0.15 lm / W.
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Abstract
Description
前記一対の陽極と陰極との間に、前記陽極及び前記陰極の主面に垂直な方向から挟持された複数の発光粒子と、
を備え、
前記発光粒子は、n型窒化物半導体部分とp型窒化物半導体部分とを含むウルツ型結晶構造を有する窒化物半導体発光粒子であって、前記n型窒化物半導体部分が陰極と接しており、前記p型窒化物半導体部分が陽極と接していると共に、
前記n型窒化物半導体部分と前記p型窒化物半導体部分とは、それぞれの結晶構造におけるc軸が互いに平行であって、前記n型窒化物半導体部分と前記p型窒化物半導体部分とは、前記c軸と平行な面で互いに接していることを特徴とする。
(c軸方向の粒子長さ)/(c軸方向に垂直な底面の最短幅)≧2
を満たしてもよい。
20 下部電極
30 上部電極
40 上部基板
50 発光粒子
51 核
52 n型半導体
53 p型半導体
54 絶縁膜
61 成長用基板
62 成長用マスク
71 反応炉
72 ガスラインA
73 ガスラインB
74 ガスラインC
75 Ga金属
76 MgCl2
77 基板ホルダ
図1は、本発明の実施の形態1に係る発光素子の概略構成を表すものである。この発光素子は、下部基板10の上に下部電極20、発光粒子50、上部電極30、上部基板40が順に配設されている。なお、図1は発光させるにあたって最低限の構成を示しており、他の部材がさらに配設されていてもよい。
<下部基板及び上部基板>
下部基板10および上部基板40の材料は特に限定されないが、下部基板10を用いて発光粒子中の半導体を成長させる場合は、半導体成長プロセスに耐えうる基板を選択する必要がある。また、発光層からの発光を取り出すために下部基板10もしくは上部基板40のいずれかは光透過性の材料を選択することが望ましい。また、発光素子としての形を維持できれば、必ずしも両方の基板を必要としない。
下部電極20および上部電極30の材料も導電性があれば特には問われないがが、下部電極20上に発光粒子中の半導体を成長させる場合は、プロセスに耐えうる基板を選択する必要がある。ただし、陰極側に用いる材料はアルミニウム、マグネシウム、銀などの仕事関数の低い材料を用いることが望ましく、陽極側に用いる材料は、金やITOなど仕事関数の高い材料が好ましい。
発光粒子50は、核51、n型窒化物半導体部分52、p型窒化物半導体部分53、絶縁膜54から構成されている。これは最低限の構成を示しており、他の部材がさらに配設されていてもよい。例えば、n型窒化物半導体52とp型窒化物半導体53との界面にn型窒化物半導体52およびp型窒化物半導体53よりもバンドギャップの狭い半導体層を設けてダブルへテロ構造にしてもよい。他には、核51と半導体層の界面に成長を促進するためのバッファ層を設けてもよい。また、n型窒化物半導体52およびp型窒化物半導体53を核51のまわりに成長させるが、成長位置は特に限られるものではなく、核51の周りに部分的に成長させてもよい。n型窒化物半導体部分52とp型窒化物半導体部分53はc軸に対して平行な面において直接接しているか、あるいは導体若しくは半導体を介して電気的に接していればよい。
核51は、n型窒化物半導体部分52もしくはp型窒化物半導体部分53を成長させるために必要なものであり、ウルツ型構造であることが望ましく、成長させる窒化物半導体と格子定数が出来るだけ近い方がよい。成長させる半導体材料が、例えばGaNである場合には、サファイア、ZnO、AlNなどが核材料の候補として挙げられる。また、核51は、当然に成長させる半導体材料と同一材料であってもよい。
n型窒化物半導体部分52およびp型窒化物半導体部分53は、それぞれウルツ型結晶構造の窒化物半導体である。ウルツ型結晶構造の窒化物半導体としては、例えば、AlN、GaN、InN、AlxGa(1-x)N、InyGa(1-y)Nなどが挙げられる。各半導体部分は単結晶体であることが好ましく、単結晶体を生成する手段としては気相成長法が好ましい。気相成長を用いた成長手段としては、ハライド気相成長(HVPE)法、有機金属気相成長(MOCVD)法などが挙げられる。気相成長を用いた半導体の成長方法では、核となる粒子を基板上に配置し、所要温度まで加熱した後に原料ガスを流して基板上の核の上に半導体を成長させる。n型半導体にする場合には、Siをドープすることによりn型半導体にすることも可能である。なお、窒化物半導体の場合はノンドープでもn型半導体の特性を示す。一方、p型半導体にする場合には、Mgをドープすることによりp型半導体の特性を示す。
絶縁膜54は、必ずしも必要なものではないが、n型窒化物半導体部分52とp型窒化物半導体53との界面の一部に存在させることが望ましい。一般的にエピタキシャル成長させる際には、基板の面内の様々な場所から結晶が成長するが、基板に対して水平方向に成長する結晶同士が成長を阻害しあい、その結果として転位を生じることが多い。前記課題を解決するために、基板上に結晶が成長しない絶縁物を介在させることにより、成長が阻害されなくなるため、転位を減少させることができる。ここでは、絶縁膜54は、n型窒化物半導体部分52又はp型窒化物半導体部分53の上を覆うように設けられ、そのc軸に平行な面の一部のみを露出させるように絶縁膜54の一部が除去される。成長面としてc軸に平行な面の一部のみを露出させることによって、成長面に水平方向の成長を抑制でき、結晶全体の成長が阻害されることを抑制できる。絶縁膜54の材料としてはAl2O3、SiO2、TiO2、BaTiO3などが挙げられる。
発光素子の製造プロセスに関しても手段は限定されないが、その一例を図2a-図2jを用いて説明をする。
(a)発光粒子を成長させるための成長用基板61上に、成長用マスク62を図2aに示すように形成する。この時の成長用基板61は、後に形成されるn型窒化物半導体部分52やp型窒化物半導体部分53を形成するプロセスに耐えうるものであることが必要である。また、ハライド気相成長(HVPE)法や有機金属気相成長(MOCVD)法を用いる場合は、NH3雰囲気にて1000℃以上の耐熱性を持つことが必要である。さらに、GaN半導体がc軸方向にエピタキシャル成長する基板が好ましい。材料例としては、面方位(0,0,0,1)のサファイア基板、面方位(1,1,1)シリコン基板等が挙げられる。
(c)その後、図2cに示すようにマスク62を除去する。この時のマスク62を除去するプロセスにおいて、核51に影響を与えない手段を用いる必要がある。あるいは、成長用マスクを用いることなく成長用基板61上に、核51を直接に林立させるように形成してもよい。例えば、非特許文献(Jpn. J. Appl. Phys. Vol.38 (1999) pp6873-6877)にて紹介されている手段を用いれば、核51となるZnOを基板61上に直接に林立して形成できる。
(d)その後、図2dに示すように核51の上にn型窒化物半導体部分52を形成する。その手段は、前述のようにハライド気相成長(HVPE)法や有機金属気相成長(MOCVD)法などが好ましい。
(e)図2eに示すように、核51の上にn型窒化物半導体部分52が形成された粒子を成長用基板61から分離する。分離する手段としては、例えば、振動を与える手段や鋭利な物を用いてそぎ落とす手段などの機械的手段もしくは、基板を溶解させる等の化学的手段を用いればよい。
(g)次いで、図2gに示すように、粒子の上に絶縁膜54を形成する。形成手段は特には問わないが、例えばスパッタリング法が挙げられる。
(h)さらに、図2hに示すように絶縁膜54の一部を除去する。この場合、粒子のc軸に平行な面が露出するようにする。絶縁膜54の除去方法についても手段は限定されないが、例えば、機械研磨法、ウェットエッチング法、ドライエッチング法などが挙げられる。
(i)図2iに示すように、絶縁膜54の一部を除去して露出させたn型窒化物半導体部分52のc軸に平行な面の上にp型窒化物半導体部分53を形成させる。p型窒化物半導体部分53の形成手段としては、前述のようにハライド気相成長(HPVE)法や有機金属気相成長(MOCVD)法などが好ましい。また、それらのプロセスにおいて、p型窒化物半導体部分を形成する場合は、下部電極20、下部基板10ともにNH3雰囲気にて1000℃以上の耐熱を持つことが必要である。下部基板10の材料例としては、サファイア基板、シリコン基板等が挙げられ、下部電極20の材料例としては、モリブデン、タンタルなどが挙げられる。
(j)その後、図2jに示すように上部電極30と上部基板40を順に配設して発光素子を得る。
以下に実施例1に係る発光素子の製造方法を説明する。
(a)面方位(0,0,0,1)である2インチ(5.08cm)のサファイア基板を成長用基板として用いる。前記サファイア基板上に形成用マスクを介してスパッタリング法を用いてSiO2膜を10μmの厚みで形成した。孔部の直径は2μmであった。ターゲットはSiO2ターゲットを使用し、Arガス雰囲気中で、スパッタリングを行い形成した。
(b)その上に核としてAlN膜をスパッタリング法にて形成した。ターゲットはAlターゲットを使用し、N2ガス雰囲気中でスパッタリングを行い形成した。AlNはc軸方向に成長し、その厚みは10μmであった。
(c)成長用マスクと核が形成されている成長用基板を3%フッ酸水溶液に浸漬して、成長用マスクを除去した。
ガスラインA72にはHClを3cc/分およびN2を250cc/分で流し、途中にGa金属75を配設した。ガスラインB73には何にも流さず、ガスラインC74にはNH3を250cc/分流した。また炉内全体にN2を3000cc/分流した。反応炉の温度は1000℃にして2分間成長させて、ノンドープのGaN膜を2μmの膜厚で形成した。この時、粒子底面幅は6μmであり、粒子の高さは12μmであった。
(e)n型窒化物半導体層を形成後、成長用基板に機械的振動を与えて、成長用基板から核とn型窒化物半導体を有する粒子を取り出して、ホウ素をドープしたn型Si基板上に機械的振動を与えながら配設した。この時、n型Si基板は下部基板と下部電極を兼ねている。
(g)その後、そのスパッタリング装置内にて、今度は基板側にArプラズマを発生させて、絶縁膜の表面をドライエッチングした。これによってn型窒化物半導体のc軸に平行な面の一部を露出させた。
ガスラインA72にはHClを3cc/分およびN2を250cc/分流し、途中にGa金属75を配設した。ガスラインB73にはMgCl2粉末76を配設し、N2ガスを250cc/分流した。ガスラインC74にはNH3を250cc/分で流した。また炉内全体にN2を3000cc/分流した。反応炉の温度は1000℃にして2分間成長させて、MgドープのGaN膜を2μmの膜厚で形成した。反応後は炉内全体にN2を3000cc/分流したままま温度を降下させ、700℃に降下させた時点で温度を1時間保持し、その後に再度炉内温度を降下させた。
(i)その後ITOペーストを2μmの厚みで塗布したガラス製の上部基板をペースト面を下にして、下部基板に押し付けて発光素子とした。
(j)上部基板の上側には、ZnS:Cu,Al蛍光体をアクリル樹脂に分散させたペーストを2μm塗布した。
以上によって発光素子を得た。
実施例2では、発光粒子の絶縁膜を製膜しない他は実施例1と同様の方法で発光素子を作成した。
得られた発光素子に実施例1と同様に電圧をかけて発光させたときの輝度は520cd/m2であり、発光効率は1.11m/Wであった。
実施例2に対して、形成用マスクであるSiO2膜の膜厚を1μm、孔部の直径を2μmと変更し、さらに核であるAlN膜の厚みを1μmと変更し、核とn型半導体を有する粒子を取り出して、ホウ素をドープしたn型Si基板上に配設する際には機械的振動を与えなかった。その結果、発光粒子のc軸が基板に対して垂直になっている発光粒子が大半を占めた。
この発光素子に実施例1の発光素子と同様に電圧をかけて発光させたときの輝度は320cd/m2であり、発光効率は0.6lm/Wであった。
比較例1に対して、発光粒子のp型半導体層を製膜しないかわりに、n型半導体層を4μm製膜させた他は比較例1と同様にして発光素子を作成した。
発光素子に同様に電圧をかけて発光させたときの輝度は80cd/m2であり、発光効率は0.15lm/Wであった。
Claims (5)
- 互いに対向する一対の陽極と陰極と、
前記一対の陽極と陰極との間に、前記陽極及び前記陰極の主面に垂直な方向から挟持された複数の発光粒子と、
を備え、
前記発光粒子は、n型窒化物半導体部分とp型窒化物半導体部分とを含むウルツ型結晶構造を有する窒化物半導体発光粒子であって、前記n型窒化物半導体部分が陰極と接しており、前記p型窒化物半導体部分が陽極と接していると共に、
前記n型窒化物半導体部分と前記p型窒化物半導体部分とは、それぞれの結晶構造におけるc軸が互いに平行であって、前記n型窒化物半導体部分と前記p型窒化物半導体部分とは、前記c軸と平行な面で互いに接していることを特徴とする発光素子。 - 前記発光粒子は、前記n型窒化物半導体部分の上に絶縁膜を設け、前記絶縁膜の一部を除去して前記n型窒化物半導体部分のc軸に平行な面を露出させて、前記p型窒化物半導体部分を成長させて構成された、請求項1に記載の発光素子。
- 前記発光粒子は、前記p型窒化物半導体部分の上に絶縁膜を設け、前記絶縁膜の一部を除去して前記p型窒化物半導体部分のc軸に平行な面を露出させて、前記n型窒化物半導体部分を成長させて構成された、請求項1に記載の発光素子。
- 前記発光粒子は、前記n型窒化物半導体部分と前記p型窒化物半導体部分の結晶構造におけるc軸が前記陽極及び前記陰極の主面に平行となるように配置されている、請求項1から3のいずれか一項に記載の発光素子。
- 前記発光粒子は、前記n型窒化物半導体部分と前記p型窒化物半導体部分とにおいて共通する前記c軸に平行な方向についての長さと、前記c軸に垂直な底面の最短幅について下記関係式
(c軸方向の粒子長さ)/(c軸方向に垂直な底面の最短幅)≧2
を満たすことを特徴とする請求項1から4のいずれか一項に記載の発光素子。
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JP2002512734A (ja) * | 1997-02-14 | 2002-04-23 | オーバーマン、デビッド | オプトエレクトロニクス半導体ダイオード及びそれを備えた装置 |
WO2004023569A1 (ja) * | 2002-09-06 | 2004-03-18 | Sony Corporation | 半導体発光素子およびその製造方法、集積型半導体発光装置およびその製造方法、画像表示装置およびその製造方法ならびに照明装置およびその製造方法 |
JP2006245564A (ja) * | 2005-02-07 | 2006-09-14 | Matsushita Electric Ind Co Ltd | 半導体装置 |
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US8309985B2 (en) | 2012-11-13 |
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