WO2010110427A1 - 発光ダイオード素子及びその製造方法 - Google Patents
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- WO2010110427A1 WO2010110427A1 PCT/JP2010/055383 JP2010055383W WO2010110427A1 WO 2010110427 A1 WO2010110427 A1 WO 2010110427A1 JP 2010055383 W JP2010055383 W JP 2010055383W WO 2010110427 A1 WO2010110427 A1 WO 2010110427A1
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Images
Classifications
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- 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
- H01L33/08—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 plurality of light emitting regions, e.g. laterally discontinuous light emitting layer or photoluminescent region integrated within the semiconductor body
-
- 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
-
- 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
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
-
- 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
- H01L33/12—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 stress relaxation structure, e.g. buffer layer
-
- 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
- H01L33/26—Materials of the light emitting region
- H01L33/34—Materials of the light emitting region containing only elements of Group IV of the Periodic Table
- H01L33/343—Materials of the light emitting region containing only elements of Group IV of the Periodic Table characterised by the doping materials
Definitions
- the present invention relates to a light emitting diode element and a method for manufacturing the same.
- an LED light emitting diode
- white LEDs using nitride semiconductors and phosphors have been put into practical use, and in the future, they are highly expected to be used for general lighting applications.
- energy conversion efficiency is insufficient as compared with existing fluorescent lamps, so that significant efficiency improvement is necessary for general lighting applications.
- many problems remain for realizing high color rendering properties, low cost, and high luminous flux LEDs.
- a white LED As a white LED currently on the market, a blue light emitting diode element mounted on a lead frame, a yellow phosphor layer made of YAG: Ce over the blue light emitting diode element, and a transparent material such as an epoxy resin covering them. What is equipped with the mold lens which becomes is known.
- this white LED when blue light is emitted from the blue light emitting diode element, part of the blue light is converted into yellow light when passing through the yellow phosphor. Since blue and yellow are complementary to each other, when blue light and yellow light are mixed, white light is obtained.
- the white LED is required to improve the performance of the blue light-emitting diode element in order to improve efficiency and improve color rendering.
- a buffer layer made of AlGaN, an n-type GaN layer made of n-GaN, a multiple quantum well active layer made of GaInN / GaN, an electron block layer made of p-AlGaN It is known that a p-type contact layer made of p-GaN is continuously laminated in this order from the SiC substrate side. Further, a p-side electrode is formed on the surface of the p-type contact layer, and an n-side electrode is formed on the back surface of the SiC substrate, and a current is applied by applying a voltage between the p-side electrode and the n-side electrode.
- the SiC substrate is conductive, so unlike the blue light-emitting diode element using a sapphire substrate, electrodes can be arranged above and below, simplifying the manufacturing process, and in-plane uniformity of current In addition, it is possible to effectively use the light emitting area with respect to the chip area.
- a light emitting diode element that independently generates white light without using a phosphor has been proposed (see, for example, Patent Document 1).
- a fluorescent SiC substrate having a first SiC layer doped with B and N and a second SiC layer doped with Al and N is used instead of the n-type SiC substrate of the blue light emitting diode element described above.
- Near ultraviolet light is emitted from the multiple quantum well active layer.
- Near-ultraviolet light is absorbed by the first SiC layer and the second SiC layer, and is converted from green to red visible light by the first SiC layer, and from blue to red visible light by the second SiC layer.
- white light close to sunlight is emitted from the fluorescent SiC substrate.
- the present invention has been made in view of the above circumstances, and the object of the present invention is from the emission wavelength range of normal 6H type SiC doped with B and N without doping Al into 6H type SiC. It is another object of the present invention to provide a light emitting diode element capable of obtaining light emission on the short wavelength side and a method for manufacturing the same.
- the present invention comprises a semiconductor light emitting part and a porous single crystal 6H type SiC doped with N and B, and emits visible light when excited by light emitted from the semiconductor light emitting part.
- a light emitting diode device having a porous SiC portion that emits light.
- the light-emitting diode element preferably has a protective film covering the surface of the porous SiC part.
- the light emitting diode element is made of bulk single crystal 6H type SiC to which N and B are added, and emits visible light having a wavelength longer than that of the porous SiC portion when excited by light emitted from the semiconductor light emitting layer. It is preferable to have a SiC part.
- the porous SiC portion is formed by making a part of the bulk SiC portion porous.
- the semiconductor light-emitting portion is formed on the bulk SiC portion that is partially porous.
- a method for manufacturing the light-emitting diode device the electrode forming step of forming an electrode on a bulk single crystal 6H type SiC to which N and B are added, and the single crystal 6H type having the electrode formed thereon.
- a method for manufacturing a light-emitting diode element including an anodic oxidation step of anodizing SiC to form the porous SiC portion.
- the light emitting diode device manufacturing method includes a heat treatment step of performing a heat treatment of the porous SiC portion and a protective film forming step of forming a protective film on the porous SiC portion subjected to the heat treatment.
- a hydrofluoric acid aqueous solution to which an oxidizing aid is added as a solution to be reacted with the single crystal 6H type SiC in the anodizing step.
- the oxidation auxiliary agent is preferably potassium persulfate.
- light emission on the shorter wavelength side than the light emission wavelength region of bulk 6H type SiC doped with B and N can be obtained without doping Al in 6H type SiC.
- FIG. 1 is a schematic cross-sectional view of a light-emitting diode element showing an embodiment of the present invention.
- FIG. 2 is a schematic cross-sectional view of a SiC substrate on which an ohmic electrode is formed.
- FIG. 3 is an explanatory diagram of an anodizing apparatus for making a SiC substrate porous.
- FIG. 4 is a schematic cross-sectional view of a SiC substrate on which a porous layer is formed.
- FIG. 5 is an electron micrograph of a cross section of the produced porous layer.
- FIG. 6 is a schematic cross-sectional view of a bulk SiC substrate in which electrodes are formed on a semiconductor layer according to a modification.
- FIG. 1 is a schematic cross-sectional view of a light-emitting diode element showing an embodiment of the present invention.
- FIG. 2 is a schematic cross-sectional view of a SiC substrate on which an ohmic electrode is formed.
- FIG. 3 is an ex
- FIG. 7 is a schematic cross-sectional view of a light emitting diode element showing a modification.
- FIG. 8 is a graph showing the emission wavelength and emission intensity of the sample body 1.
- FIG. 9 is a graph showing the emission wavelength and emission intensity of the sample body 2.
- FIG. 10 is a graph showing the emission wavelength and emission intensity of the sample body 3.
- FIG. 11 is a graph showing the emission wavelength and emission intensity of the sample body 4.
- FIG. 12 is a graph showing the relationship between the emission intensity and peak wavelength of each sample body and the concentration of potassium persulfate.
- FIGS. 13A and 13B are diagrams for explaining donor-acceptor pair emission.
- FIG. 13A shows a state in a bulk crystal
- FIG. 13B shows a state in a porous crystal.
- FIG. 14 is a graph showing the emission wavelength and emission intensity of the sample body 5.
- FIG. 1 to 5 show an embodiment of the present invention
- FIG. 1 is a schematic cross-sectional view of a light-emitting diode element.
- the light emitting diode element 100 includes a SiC substrate 102 and a nitride semiconductor layer formed on the SiC substrate 102.
- the nitride semiconductor layer as the semiconductor light emitting unit has a coefficient of thermal expansion of 5.6 ⁇ 10 ⁇ 6 / ° C., and the buffer layer 104, the n-type layer 106, the multiple quantum well active layer 108, the electron block layer 110, and the p-type.
- the clad layer 112 and the p-type contact layer 114 are provided in this order from the SiC substrate 102 side.
- a p-side electrode 116 is formed on the p-type contact layer 114, and an n-side electrode 118 is formed on the back side of the SiC substrate 102.
- the SiC substrate 102 is made of single crystal 6H type SiC and has a thermal expansion coefficient of 4.2 ⁇ 10 ⁇ 6 / ° C.
- the SiC substrate 102 includes a bulk layer 122 made of bulk single crystal 6H type SiC to which N and B are added, and a porous layer 124 made of porous single crystal 6H type SiC to which N and B are added.
- a bulk layer 122 made of bulk single crystal 6H type SiC to which N and B are added
- a porous layer 124 made of porous single crystal 6H type SiC to which N and B are added.
- the term “bulk” as used herein refers to a state where there is no interface with another substance inside or a state where a change in physical property value can be ignored even if an interface exists.
- the porous shape here refers to a state in which a porous shape is formed and an interface with the atmosphere exists inside.
- the bulk layer 122 serving as a bulk SiC portion When excited by ultraviolet light, the bulk layer 122 serving as a bulk SiC portion emits visible light of approximately yellow to orange color by donor-acceptor pair emission.
- the bulk layer 122 emits light with a wavelength of 500 nm to 750 nm having a peak at 500 nm to 650 nm, for example.
- the bulk layer 122 is adjusted to emit light having a peak wavelength of 580 nm.
- the doping concentration of B and N in the bulk layer 122 is 10 15 / cm 3 to 10 19 / cm 3 .
- the bulk layer 122 can be excited by light of 408 nm or less.
- the porous layer 124 serving as a porous SiC portion emits visible light of approximately blue to green by donor-acceptor pair emission.
- the porous layer 124 emits light with a wavelength of 380 nm to 700 nm having a peak at 400 nm to 500 nm, for example.
- the porous layer 124 is adjusted to emit light having a peak wavelength of 450 nm.
- the doping concentration of B and N in the porous layer 124 is 10 15 / cm 3 to 10 19 / cm 3 .
- the surface of the porous layer 124 is covered with a protective film so that it is not directly exposed to the atmosphere.
- the protective film is made of nitride.
- the buffer layer 104 is formed on the SiC substrate 102 and is made of AlGaN. In the present embodiment, the buffer layer 104 is grown at a lower temperature than an n-type layer 106 described later. The n-type layer 106 is formed on the buffer layer 104 and is made of n-GaN.
- the multiple quantum well active layer 108 is formed on the n-type layer 106, is made of GalnN / GaN, and emits excitation light, for example, by injection of electrons and holes.
- the multiple quantum well active layer 108 is made of Ga 0.95 ln 0.05 N / GaN, and the peak wavelength of light emission is 385 nm. The peak wavelength in the multiple quantum well active layer 108 can be arbitrarily changed.
- the electron block layer 110 is formed on the multiple quantum well active layer 108 and is made of p-AIGaN.
- the p-type cladding layer 112 is formed on the electron block layer 110 and is made of p-AlGaN.
- the p-type contact layer 114 is formed on the p-type cladding layer 112 and is made of p-GaN.
- the buffer layer 104 to the p-type contact layer 114 are formed by epitaxial growth of a group III nitride semiconductor.
- the active layer is formed by recombination of electrons and holes.
- the layer structure of the nitride semiconductor layer is arbitrary.
- the p-side electrode 116 is formed on the p-type contact layer 114 and is made of, for example, Ni / Au, and is formed by a vacuum deposition method, a sputtering method, a CVD (Chemical Vapor Deposition) method, or the like.
- the n-side electrode 118 is formed on the SiC substrate 102 and is made of, for example, Ti / Al / Ti / Au, and is formed by a vacuum evaporation method, a sputtering method, a CVD (Chemical Vapor Deposition) method, or the like.
- FIG. 2 is a schematic cross-sectional view of a SiC substrate on which an ohmic electrode is formed.
- bulk single crystal 6H type SiC doped with B and N is generated by a sublimation method, and an SiC substrate 102 composed of the bulk layer 122 is produced (bulk SiC preparation step).
- the doping concentrations of B and N in the SiC crystal can be controlled by adding an impurity gas to the atmosphere gas during crystal growth and adding an impurity element or compound thereof to the raw material powder.
- the thickness of SiC substrate 102 is arbitrary, it is 250 micrometers, for example.
- the SiC substrate 102 is manufactured through steps such as peripheral grinding, slicing, surface grinding, and surface polishing by preparing a bulk crystal of about 30 mm by bulk growth by a sublimation method.
- an ohmic electrode 201 is formed on one surface of the SiC substrate 102 (electrode forming step).
- the ohmic electrode 201 is made of Ni, and is subjected to heat treatment after being deposited by sputtering.
- the thickness of the ohmic electrode 201 is arbitrary, it is 100 nm, for example, and is heat-treated at about 1000 ° C., for example.
- the porous layer 124 is formed on the (0001) Si surface side of the SiC substrate 102
- the ohmic electrode 201 is formed on the C surface.
- the ohmic electrode 201 may be formed on the Si surface.
- FIG. 3 is an explanatory view of an anodizing apparatus for making a SiC substrate porous.
- the anodizing apparatus 200 includes a stainless steel plate 202 on which the SiC substrate 102 is placed, and a Teflon (registered) that is disposed above the stainless steel plate 202 and formed directly above the SiC substrate 102.
- Teflon registered
- container 206 platinum wire 208 disposed inside container 206, and DC power supply 210 that applies a voltage to SiC substrate 102 and platinum wire 208.
- the container 206 is provided on the stainless steel plate 202 via the hydrofluoric acid resistant sheet 212, and the inside is filled with the solution 214.
- the container 206 has an opening 216 at the top where the ultraviolet light 218 can be incident.
- the solution 214 is a hydrofluoric acid aqueous solution in which hydrofluoric acid is diluted with pure water, and potassium persulfate as an oxidation aid is arbitrarily added.
- the concentration of hydrofluoric acid is arbitrary, but can be, for example, 3% to 10% by mass concentration.
- ethanol or the like can be used in addition to water.
- potassium persulfate is added is arbitrary, and the concentration in the case of adding potassium persulfate is also arbitrary. For example, it can be less than 0.1 mol / l.
- potassium persulfate has a function of promoting the chemical oxidation reaction of the SiC crystal, the formation of the porous layer 124 can be promoted by anodic oxidation.
- sulfuric acid persulfate sulfuric acid, nitric acid and the like can be used as an oxidation aid.
- a positive voltage is applied to the ohmic electrode 201 by the DC power source 210 while the bulk layer 122 is in contact with the solution 214, and the SiC substrate 102 is placed between the SiC substrate 102 and the platinum wire 208. Apply current. When the current starts to flow, the following chemical reaction proceeds from the surface of SiC substrate 102 toward the inside.
- SiC changes to SiO 2 and CO 2 by an oxidation reaction, and SiO 2 further changes to water-soluble H 2 SiF 6 by fluorine ions and melts into the solution. Since CO 2 is a gas, it disappears as it is by vaporization. This reaction proceeds in a direction in which the SiC atom bond is relatively weak, and a cavity is formed in a direction inclined by a predetermined angle with respect to the surface of the SiC substrate 102.
- FIG. 4 is a schematic cross-sectional view of a SiC substrate on which a porous layer is formed
- FIG. 5 is an electron micrograph of a cross section of the produced porous layer.
- a porous layer 124 is formed from the surface side of the bulk layer 122 by an anodic oxidation reaction (anodic oxidation step).
- FIG. 4 shows the SiC substrate 102 from which the ohmic electrode 201 is removed after the porous layer 124 is formed.
- FIG. 5 it can be seen that also in the actually obtained porous layer 124, a cavity with relatively regularity crosses the cross section.
- the reaction proceeds on the (0001) Si side surface of the SiC substrate 102, a cavity is formed in a direction inclined by 54 degrees with respect to the surface.
- the current density in SiC substrate 102 is arbitrary, but if the current value is too high, the voids in porous layer 124 approach the direction perpendicular to the surface of SiC substrate 102 and the shape thereof becomes nonuniform.
- a lower current density is desirable.
- the current density is desirably less than 10 mA / cm 2 , and typically 2 mA / cm 2 .
- the thickness of the porous layer 124 is proportional to the anodic oxidation time, and is 50 ⁇ m in this embodiment.
- the reaction of the above formula (1) is promoted, and the number of cavities in the porous layer 124 can be increased. As a result, the average size of the crystals remaining and constituting the porous layer 124 can be reduced.
- the SiC substrate 102 is subjected to heat treatment (heat treatment step). Specifically, C that is excessively deposited on the crystal surface of the porous layer 124 can be removed by performing heat treatment at 1000 ° C. to 1400 ° C. in a hydrogen atmosphere.
- a protective film is formed after the heat treatment of the porous layer 124 (protective film forming step). Specifically, by performing heat treatment at 1000 ° C. to 1400 ° C. in an ammonia atmosphere, a protective film of Si 3 N 4 can be formed on the surface of the clean crystal, and the surface level of the porous layer 124 Can be stably reduced.
- the SiC substrate 102 having the porous layer 124 as shown in FIG. 4 is produced. Thereafter, a group III nitride semiconductor is epitaxially grown on the SiC substrate 102.
- a group III nitride semiconductor is epitaxially grown on the SiC substrate 102.
- the buffer layer 104 made of AlGaN by an organic metal compound vapor phase growth method, the n-type layer 106 made of n-GaN, the multiple quantum well active layer 108, the electron block layer 110, p A mold cladding layer 112 and a p-type contact layer 114 are grown.
- the electrodes 116 and 118 are formed and divided into a plurality of light emitting diode elements 100 by dicing, whereby the light emitting diode element 100 is manufactured.
- the SiC substrate 102 shown in FIG. 4 can be used as a phosphor plate instead of the substrate of the light emitting diode element 100.
- the light emitting diode element 100 configured as described above emits ultraviolet light radially from the multiple quantum well active layer 108 when a voltage is applied to the p-side electrode 116 and the n-side electrode 118.
- a voltage is applied to the p-side electrode 116 and the n-side electrode 118.
- most of the ultraviolet light directed to the p-side electrode 116 is reflected by the p-side electrode 116 and travels toward the SiC substrate 102. Therefore, most of the light emitted from the multiple quantum well active layer 108 goes to the SiC substrate 102.
- the ultraviolet light incident on the SiC substrate 102 is converted from blue to green first visible light by the porous layer 124, and the rest is converted from yellow to orange second visible light by the bulk layer 122. These lights are emitted from the SiC substrate 102 to the outside, and white light having high color rendering properties similar to sunlight can be obtained.
- the porous layer 124 emits first visible light having a peak wavelength at 450 nm and the bulk layer 122 emits second visible light having a peak wavelength at 580 nm, almost all of the visible light region is covered.
- a pure white light emitting diode element 100 can be realized.
- the light emission on the shorter wavelength side can be obtained. Therefore, the elements to be doped into the SiC substrate 102 are only B and N, and the SiC substrate 102 can be easily and easily manufactured, thereby reducing the manufacturing cost of the SiC substrate 102 and consequently the manufacturing cost of the light emitting diode element 100. it can.
- SiC substrate 102 when manufacturing the SiC substrate 102 having the bulk layer 122 and the porous layer 124, it is not necessary to devise any special device for the manufacturing apparatus, the raw material, and the like, which is extremely advantageous in practical use.
- SiC substrate 102 does not require epitaxial growth, SiC substrate 102 can be manufactured at a relatively high speed.
- the SiC substrate 102 on which the porous layer 124 is formed is heat-treated in a hydrogen atmosphere, and then heat-treated in an ammonia atmosphere to form a protective film on the surface of the porous layer 124. Therefore, the surface state density can be greatly reduced. Thereby, in the porous layer 124, the ratio of non-radiative recombination due to surface recombination can be increased, and the recombination probability of the donor-acceptor pair can be prevented from lowering, thereby preventing the emission intensity from decreasing. In the porous layer 124, the smaller the average crystal size is, the greater the ratio of non-radiative recombination due to surface recombination increases as the crystal size becomes smaller. Thus, it can be said that the present embodiment in which the protective film is formed on the porous layer 124 has solved a new problem caused by SiC porous formation in donor-acceptor pair light emission.
- the porous layer 124 of the SiC substrate 102 is formed and then the semiconductor layer is stacked on the SiC substrate 102.
- the porous layer is formed after the semiconductor layer is stacked on the SiC substrate 102.
- 124 may be formed.
- the SiC substrate 102 made of the bulk layer 122 is produced, and a group III nitride semiconductor is epitaxially grown on the SiC substrate 102 to form the p-side electrode 116.
- a porous layer 124 is formed on the SiC substrate 102 as shown in FIG. May be.
- the light emitting diode device 300 of FIG. 7 has a porous layer 124 on the opposite side of the growth surface of the semiconductor layer of the SiC substrate 102. Furthermore, the ohmic electrode 201 may not be formed on the SiC substrate 102, but a conductor substrate may be attached to perform anodization. A semiconductor layer may be formed on the conductor substrate to form a light emitting diode element.
- the bulk SiC substrate 102 is obtained by sublimation recrystallization.
- the SiC substrate 102 may be obtained by a CVD method or the like.
- the method of making porous is arbitrary, for example, you may carry out by vapor phase etching.
- porous SiC is used as the substrate of the light emitting diode element 100.
- it can be used as a phosphor separate from the light source.
- Porous single crystal 6H type SiC to which B and N are added may be used as a powder or as a fluorescent plate for wavelength conversion.
- porous SiC can be used not only for visible light but also for emitting ultraviolet light.
- the light emitting diode element 100 which emits white light was shown using the SiC substrate 102 which has the bulk layer 122 and the porous layer 124, for example, as the SiC substrate 102 which has only the porous layer 124, for example, A light emitting diode element that emits green light may be used.
- the porous layer 124 is formed in the entire region on the surface side of the bulk layer 122.
- the porous layer 124 is formed in a partial region on the surface side of the bulk layer 122. It may be what has been done.
- the porous layer 122 is partly made porous to form the porous layer 124, SiC having the bulk layer 122 and SiC having the porous layer 124 are separately formed. Also good.
- the protective film of the porous layer 124 is shown to be a nitride, it may be made of other materials, for example, may be composed of an oxynitride, or a specific heat treatment process, protective film formation process, etc. Of course, the general conditions can be changed as appropriate.
- a single crystal 6H type SiC doped with B and N was prepared by a sublimation method, and a plurality of sample bodies made porous by anodization were prepared.
- the concentration of B and N in SiC was 3 ⁇ 10 18 for the concentration of B and 5 ⁇ 10 18 for the concentration of N so that stable light emission was obtained.
- the hydrofluoric acid aqueous solution was set to 5% by mass concentration, and the concentration of potassium persulfate was changed from 0 to 0.03 mol / l to obtain the emission wavelength and emission intensity data.
- the anodic oxidation was performed under the conditions that the current density was 2 mA / cm 2 , the energization time was 120 minutes, and the resulting porous SiC thickness was 10 ⁇ m.
- FIG. 8 is a graph showing the emission wavelength and emission intensity of the sample body 1.
- the emission wavelength and emission intensity were obtained at room temperature using a 325 nm He—Cd laser as excitation light under the condition of 8 mW (beam diameter 1 mm).
- the emission wavelength and emission intensity of bulk SiC before being made porous are shown as comparative examples.
- the sample body 1 was prepared without adding potassium persulfate to the hydrofluoric acid aqueous solution (that is, 0 mol / l).
- the peak wavelength of the sample body 1 was 491 nm, and light emission having a wavelength shorter than 578 nm, which was the peak wavelength before being porous, was observed. The emission intensity is lowered due to the porous structure.
- FIG. 9 is a graph showing the emission wavelength and emission intensity of the sample body 2.
- the emission wavelength and emission intensity were obtained at room temperature using a 325 nm He—Cd laser as excitation light under the condition of 8 mW (beam diameter 1 mm).
- the light emission wavelength and light emission intensity of the bulk SiC before making porous are shown as a comparative example.
- Sample body 2 was prepared by adding potassium persulfate having a concentration of 0.01 mol / l to an aqueous hydrofluoric acid solution. As shown in FIG.
- the peak wavelength of the sample body 2 was 449 nm, and light emission having a wavelength shorter than 580 nm, which was the peak wavelength before being porous, was observed. In the sample body 2 as well, although slightly, the emission intensity is lowered due to the porous structure.
- FIG. 10 is a graph showing the emission wavelength and emission intensity of the sample body 3.
- the emission wavelength and emission intensity were obtained at room temperature using a 325 nm He—Cd laser as excitation light under the condition of 8 mW (beam diameter 1 mm).
- the light emission wavelength and light emission intensity of the bulk SiC before making porous are shown as a comparative example.
- Sample body 3 was prepared by adding potassium persulfate having a concentration of 0.02 mol / l to an aqueous hydrofluoric acid solution.
- the peak wavelength of the sample body 3 was 407 nm, and light emission having a wavelength shorter than 583 nm, which was the peak wavelength before being porous, was observed.
- the emission intensity is increased due to the porous structure.
- FIG. 11 is a graph showing the emission wavelength and emission intensity of the sample body 4.
- the emission wavelength and emission intensity were obtained at room temperature using a 325 nm He—Cd laser as excitation light under the condition of 8 mW (beam diameter 1 mm).
- the light emission wavelength and light emission intensity of the bulk SiC before making porous are shown as a comparative example.
- the sample body 4 was prepared by adding potassium persulfate having a concentration of 0.03 mol / l to an aqueous hydrofluoric acid solution.
- the peak wavelength of the sample body 4 was 394 nm, and light emission having a wavelength shorter than 582 nm, which was the peak wavelength before being porous, was observed.
- the emission intensity is significantly increased due to the porous structure.
- FIG. 12 is a graph showing the relationship between the emission intensity and peak wavelength of each sample body and the concentration of potassium persulfate. As shown in FIG. 12, it is understood that when the concentration of potassium persulfate is increased, the peak wavelength is shortened and the emission intensity is increased. It has also been confirmed by observation with an electron microscope that the average size of the porous SiC crystals decreases as the concentration of potassium persulfate increases. Then, it is considered that the shortening of the wavelength and the increase of the emission intensity due to the increase of the concentration of potassium persulfate are due to the quantum size effect.
- FIGS. 13A and 13B are diagrams for explaining donor-acceptor pair emission.
- FIG. 13A shows a state in a bulk crystal
- FIG. 13B shows a state in a porous crystal.
- the transition energy E DA due to the recombination of the donor-acceptor pair is generally It is represented by Here, E g is the band gap energy of the crystal, E D is the ionization energy of the donor, E A is the ionization energy of the acceptor, e is the electron charge, epsilon is the dielectric constant, R DA is the distance between the average donor-acceptor is there. As the crystal size decreases, Eg increases as is generally known.
- the actual distance between the donor and acceptor is unchanged, but the electrons captured by the donor and the holes captured by the acceptor go around an orbit with a Bohr radius centered on each impurity. As shown in FIG. 13B, the trajectory is affected by the reduction in crystal size.
- both the electrons captured by the donor and the holes captured by the acceptor circulate around a spherical orbit around each impurity.
- the overlap of electron and hole trajectories is proportional to the recombination probability of the donor-acceptor pair.
- the porous crystal as shown in FIG. 13B, the crystal partially disappears, so that the electrons captured by the donor and the holes captured by the acceptor cannot maintain a spherical shape, and the impurity has a center of gravity. It becomes an elliptical orbit deviated from.
- the overlap of both trajectories increases and the recombination probability increases.
- the potassium persulfate concentration is relatively lowered.
- the concentration of potassium persulfate is lowered, surface recombination is dominant and the luminous efficiency is not relatively high. Therefore, in order to reduce the surface level that causes surface recombination, the sample body 1 was subjected to heat treatment to obtain the sample body 5.
- FIG. 14 is a graph showing the emission wavelength and emission intensity of the sample body 5.
- the emission wavelength and emission intensity were obtained at room temperature using a 325 nm He—Cd laser as excitation light under the condition of 8 mW (beam diameter 1 mm).
- the emission wavelength and emission intensity of bulk SiC before being made porous are shown as comparative examples.
- the sample body 5 was heat-treated with respect to the sample body 1 at 1300 ° C. for 10 minutes in a hydrogen atmosphere, and then heat-treated at 1300 ° C. for 5 minutes in an ammonia atmosphere to form Si 3 on the surface of the porous SiC.
- a protective film of N 4 was formed. Thereby, as shown in FIG. 14, the light emission intensity increased significantly.
- SYMBOLS 100 Light emitting diode element 102 SiC substrate 104 Buffer layer 106 N-type layer 108 Multiple quantum well active layer 110 Electron block layer 112 p-type cladding layer 114 p-type contact layer 116 p-side electrode 118 n-side electrode 200 Anodizing device 202 Stainless steel plate 204 Opening 206 Container 208 Platinum wire 210 DC power supply 212 Hydrofluoric acid resistant sheet 214 Solution 216 Opening 218 Ultraviolet light 300 Light emitting diode element
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Abstract
Description
図3に示すように、陽極酸化装置200は、SiC基板102が載置されるステンレス板202と、ステンレス板202の上方に配置されSiC基板102の直上に形成された開口204を有するテフロン(登録商標)容器206と、容器206の内部に配置される白金ワイヤ208と、SiC基板102及び白金ワイヤ208に電圧を印加する直流電源210と、を備えている。容器206は、耐フッ酸性シート212を介してステンレス板202の上に設けられ、内部が溶液214で満たされている。また、容器206は、内部へ紫外光218を入射可能な開口216が上部に形成されている。
図4に示すように、陽極酸化反応により、バルク層122の表面側からポーラス層124が形成されていく(陽極酸化工程)。尚、図4には、ポーラス層124を形成した後に、オーミック電極201を除去したSiC基板102を図示している。また、図5に示すように、実際に得られたポーラス層124においても、比較的規則性のある空洞が断面を横切っていることがわかる。ここで、SiC基板102の(0001)Si側面にて反応が進行する場合は、表面に対して54度傾いた方向に空洞が形成される。
昇華法によりB及びNがドーピングされた単結晶6H型SiCを作製し、陽極酸化によりポーラス化した試料体を複数作製した。ここで、SiC中のB及びNの濃度は、安定した発光が得られるように、Bの濃度については3×1018とし、Nの濃度については5×1018とした。陽極酸化にあたり、フッ化水素酸水溶液は質量濃度で5%とし、過硫酸カリウムの濃度を0~0.03mol/lまで変化させて、発光波長及び発光強度のデータを取得した。ここで、陽極酸化は、電流密度を2mA/cm2、通電時間を120分、得られるポーラス状SiCの厚さが10μmの条件により行った。
図8は、試料体1の発光波長と発光強度を示すグラフである。ここで、発光波長及び発光強度の取得は、励起光として325nmのHe-Cdレーザを用い、8mW(ビーム径1mm)の条件で、室温にて行った。尚、図8中には、比較例としてポーラス化前のバルクSiCの発光波長及び発光強度を示している。
試料体1は、フッ化水素酸水溶液に過硫酸カリウムを加えず(すなわち0mol/l)に作製した。図8に示すように、試料体1のピーク波長は491nmであり、ポーラス化前のピーク波長である578nmよりも短波長の発光が観測された。発光強度は、ポーラス化により下がっている。
図9は、試料体2の発光波長と発光強度を示すグラフである。ここで、発光波長及び発光強度の取得は、励起光として325nmのHe-Cdレーザを用い、8mW(ビーム径1mm)の条件で、室温にて行った。尚、図9中には、比較例としてポーラス化前のバルクSiCの発光波長及び発光強度を示している。
試料体2は、フッ化水素酸水溶液に0.01mol/lの濃度の過硫酸カリウムを加えて作製した。図9に示すように、試料体2のピーク波長は449nmであり、ポーラス化前のピーク波長である580nmよりも短波長の発光が観測された。試料体2においても、僅かではあるが、発光強度がポーラス化により下がっている。
図10は、試料体3の発光波長と発光強度を示すグラフである。ここで、発光波長及び発光強度の取得は、励起光として325nmのHe-Cdレーザを用い、8mW(ビーム径1mm)の条件で、室温にて行った。尚、図10中には、比較例としてポーラス化前のバルクSiCの発光波長及び発光強度を示している。
試料体3は、フッ化水素酸水溶液に0.02mol/lの濃度の過硫酸カリウムを加えて作製した。図10に示すように、試料体3のピーク波長は407nmであり、ポーラス化前のピーク波長である583nmよりも短波長の発光が観測された。試料体3においては、発光強度は、ポーラス化により上がっている。
図11は、試料体4の発光波長と発光強度を示すグラフである。ここで、発光波長及び発光強度の取得は、励起光として325nmのHe-Cdレーザを用い、8mW(ビーム径1mm)の条件で、室温にて行った。尚、図11中には、比較例としてポーラス化前のバルクSiCの発光波長及び発光強度を示している。
試料体4は、フッ化水素酸水溶液に0.03mol/lの濃度の過硫酸カリウムを加えて作製した。図11に示すように、試料体4のピーク波長は394nmであり、ポーラス化前のピーク波長である582nmよりも短波長の発光が観測された。試料体4においては、発光強度は、ポーラス化により大幅に上がっている。
図12に示すように、過硫酸カリウムの濃度が増加すると、ピーク波長が短波長化するとともに、発光強度が増大することが理解される。また、電子顕微鏡による観察により、過硫酸カリウムの濃度が増加すると、ポーラス化したSiC結晶の平均サイズが小さくなることも確認されている。そうすると、過硫酸カリウムの濃度の増加による短波長化及び発光強度の増大は、量子サイズ効果によるものであると考えられる。
ドナー・アクセプタ・ペアの再結合による遷移エネルギーEDAは、一般に、
一方、ポーラス結晶では、図13(b)に示すように、結晶が部分的に消失するために、ドナーに捕獲された電子とアクセプタに捕獲された正孔が球状を維持できなくなり、不純物が重心からずれた楕円球状の軌道となる。その結果、両者の軌道の重なりが大きくなり、再結合確率が増加する。そして、ポーラス化前においては上式のRDAはR1DAであったところ、ポーラス化によりRDAは、実質的にはR1DAより小さなR2DAとなる。これにより、ポーラス化によって遷移エネルギーは一層大きくなる。試料体1~4の実験結果は、このような理論的背景によって引き起こされていると思われる。
図14は、試料体5の発光波長と発光強度を示すグラフである。ここで、発光波長及び発光強度の取得は、励起光として325nmのHe-Cdレーザを用い、8mW(ビーム径1mm)の条件で、室温にて行った。尚、図14中には、比較例としてポーラス化前のバルクSiCの発光波長及び発光強度を示している。
試料体5は、試料体1に対して、水素雰囲気中にて1300℃で10分間熱処理を行った後、アンモニア雰囲気中にて1300℃で5分間熱処理を行い、ポーラスSiCの表面上にSi3N4の保護膜を形成した。これにより、図14に示すように、発光強度が大幅に増大した。
102 SiC基板
104 バッファ層
106 n型層
108 多重量子井戸活性層
110 電子ブロック層
112 p型クラッド層
114 p型コンタクト層
116 p側電極
118 n側電極
200 陽極酸化装置
202 ステンレス板
204 開口
206 容器
208 白金ワイヤ
210 直流電源
212 耐フッ酸性シート
214 溶液
216 開口
218 紫外光
300 発光ダイオード素子
Claims (9)
- 半導体発光部と、
N及びBが添加されたポーラス状の単結晶6H型SiCからなり、前記半導体発光部から発せられる光により励起されると可視光を発するポーラスSiC部と、を有する発光ダイオード素子。 - 前記ポーラスSiC部の表面を覆う保護膜を有する請求項1に記載の発光ダイオード素子。
- N及びBが添加されたバルク状の単結晶6H型SiCからなり、前記半導体発光層から発せられる光により励起されると前記ポーラスSiC部より波長の長い可視光を発するバルクSiC部を有する請求項2に記載の発光ダイオード素子。
- 前記ポーラスSiC部は、前記バルクSiC部の一部をポーラス化して形成される請求項3に記載の発光ダイオード素子。
- 前記半導体発光部は、一部がポーラス化された前記バルクSiC部上に形成される請求項4に記載の発光ダイオード素子。
- 請求項1から5のいずれか1項に記載の発光ダイオード素子の製造方法であって、
N及びBが添加されたバルク状の単結晶6H型SiCに電極を形成する電極形成工程と、
前記電極が形成された単結晶6H型SiCに対して、陽極酸化を行って前記ポーラスSiC部を形成する陽極酸化工程と、を含む発光ダイオード素子の製造方法。 - 前記ポーラスSiC部の熱処理を行う熱処理工程と、
熱処理が行われた前記ポーラスSiC部に保護膜を形成する保護膜形成工程と、を含む請求項6に記載の発光ダイオード素子の製造方法。 - 前記陽極酸化工程にて、前記単結晶6H型SiCと反応させる溶液として、酸化補助剤が加えられたフッ化水素酸水溶液を用いる請求項7に記載の発光ダイオード素子の製造方法。
- 前記酸化補助剤は、過硫酸カリウムである請求項8に記載の発光ダイオード素子の製造方法。
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CN102369605A (zh) | 2012-03-07 |
JP5330880B2 (ja) | 2013-10-30 |
DE112010001379B4 (de) | 2021-07-22 |
JP2010232556A (ja) | 2010-10-14 |
CN102369605B (zh) | 2014-07-02 |
US20120037923A1 (en) | 2012-02-16 |
DE112010001379T5 (de) | 2012-05-10 |
US9099597B2 (en) | 2015-08-04 |
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