WO2014199851A1 - 半導体発光装置 - Google Patents
半導体発光装置 Download PDFInfo
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- WO2014199851A1 WO2014199851A1 PCT/JP2014/064575 JP2014064575W WO2014199851A1 WO 2014199851 A1 WO2014199851 A1 WO 2014199851A1 JP 2014064575 W JP2014064575 W JP 2014064575W WO 2014199851 A1 WO2014199851 A1 WO 2014199851A1
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- Prior art keywords
- light
- light emitting
- semiconductor light
- emitting device
- semiconductor
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- 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
- H01L33/48—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 body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
- H01L33/504—Elements with two or more wavelength conversion materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0083—Periodic patterns for optical field-shaping in or on the semiconductor body or semiconductor body package, e.g. photonic bandgap structures
Definitions
- the present invention relates to a semiconductor light emitting device including a semiconductor light emitting element and a wavelength conversion member.
- LEDs Light emitting diodes
- LEDs which are semiconductor light emitting devices using semiconductor layers, have characteristics such as small size, high power efficiency, and fast on / off response compared to conventional light emitting devices such as conventional fluorescent lamps and incandescent bulbs. It has many advantages such as being strong against vibration and having a long device life because it is all made of solid.
- the LED has a single emission center wavelength, in order to use it as various light sources, the use of the single wavelength can be limited. Therefore, white light is required as the emission light source.
- Patent Document 1 a blue LED and a fluorescent material that absorbs the emitted light and emits yellow fluorescence are combined, and yellow light and blue light that has not been absorbed are mixed to generate white light.
- An invention relating to a semiconductor light emitting device is disclosed.
- Patent Document 2 discloses an invention relating to a white LED lamp having a light-emitting diode chip that emits primary light of UV light to violet light and a transparent resin layer in which a fluorescent material layer is dispersed.
- the fluorescent material powder in the fluorescent material layer emits light (secondary light) such as blue light, green light, yellow light and red light, At this time, the color of the light obtained by mixing the secondary lights of the respective colors is determined to be white.
- Patent Document 3 discloses an invention related to a semiconductor light emitting element which is one configuration of a semiconductor light emitting device.
- a micro-order concavo-convex pattern is provided on the surface of a substrate constituting an LED, and the light guiding direction in the light emitting layer is changed to improve the light extraction efficiency.
- a white light emitting device having high light extraction efficiency can be obtained by forming a fluorescent material containing YAG on the surface of a semiconductor light emitting element by mixing it with a resin. (Refer to [0077] column of Patent Document 3).
- Patent Document 4 discloses an invention relating to a light-emitting device having high light extraction efficiency by forming a concavo-convex structure on a light-emitting exposed surface of a semiconductor light-emitting element and coating it with a coating layer containing a phosphor.
- Patent Document 5 discloses a semiconductor light emitting device in which a light extraction layer made of a resin material having a concavo-convex structure formed on a surface of a laminated semiconductor layer including a light emitting layer is provided.
- Patent Document 6 discloses an invention relating to a semiconductor light emitting element substrate and a semiconductor light emitting element in which a nano-sized pattern is provided on a substrate and a micro-period long period is provided in the pattern. According to Patent Document 6, it is possible to suppress crystal defect dislocations in epitaxial growth during LED manufacturing, increase the internal quantum efficiency of the LED, and increase the light extraction efficiency by providing a micro-period long period. The external quantum efficiency defined by the product of the internal quantum efficiency and the light extraction efficiency is improved.
- the semiconductor light emitting device having the uneven pattern described in Patent Document 3 to Patent Document 6 is used as the white light emitting device that emits the emitted light and the fluorescent light described in Patent Document 1 and Patent Document 2.
- the white light emitting device that emits the emitted light and the fluorescent light described in Patent Document 1 and Patent Document 2.
- Patent Document 3 in order to improve the luminous efficiency of a single LED, a technique of providing a micro-order uneven pattern on the substrate surface constituting the LED is widely applied.
- the factors that determine the external quantum efficiency EQE which indicates the light emission efficiency of the LED, are the electron injection efficiency EIE (Electron Injection Efficiency), the internal quantum efficiency IQE (Internal Quantity Efficiency), and the light extraction efficiency. Is mentioned.
- the internal quantum efficiency IQE depends on the dislocation density caused by the crystal mismatch of the GaN-based semiconductor crystal. Further, the light extraction efficiency LEE is improved by breaking the waveguide mode inside the GaN-based semiconductor crystal by light scattering due to the uneven pattern provided on the substrate.
- the roles (effects) of the concavo-convex pattern provided in the semiconductor light emitting device include (1) improvement of internal quantum efficiency IQE by reducing dislocations in the semiconductor crystal, and (2) light extraction efficiency by eliminating the waveguide mode.
- the improvement of LEE is mentioned.
- a dislocation density of 1 ⁇ 10 9 pieces / cm 2 corresponds to 10 pieces / ⁇ m 2 in terms of nano-order
- a dislocation density of 1 ⁇ 10 8 pieces / cm 2 corresponds to 1 piece / ⁇ m 2 .
- the concavo-convex pattern density is 0.08 ⁇ 10 8 pieces / cm 2
- about 2 concavo-convex patterns are formed on 500 nm ⁇ 500 nm ( ⁇ 500 nm).
- the uneven pattern density is 8 ⁇ 10 8 pieces / cm 2 .
- the above-described crystal defect dislocations in the epitaxial growth during LED manufacturing are suppressed by the nano-sized uneven pattern, and the internal quantum efficiency IQE of the LED is increased. Furthermore, the arrangement of the nano-sized uneven pattern is provided with a micro-order long period, so that the light extraction efficiency LEE is also increased. As a result, the external quantum efficiency EQE defined by the product of the internal quantum efficiency IQE and the light extraction efficiency LEE. It becomes possible to improve.
- the above-described technology focuses on improving the light emission efficiency of the LED itself, and is described in Patent Document 1 or Patent Document 2 using an LED to which the above-described technology is applied.
- a white light emitting device that emits emitted light and fluorescence
- the efficiency is lower than the efficiency of monochromatic light emission.
- color unevenness of white light is observed.
- the light emission distribution of the white light-emitting device has little angle dependency and requires a Lambertian light emission distribution at all visible light wavelengths.
- the above problem is interpreted as follows.
- the micro-order long-period structure provided in the LED is set to be suitable for emitted light. For this reason, it is considered that sufficient light scattering does not function when the fluorescent material absorbs part of the emitted light and fluorescent light having a wavelength different from that of the emitted light is emitted. As a result, the light extraction efficiency with respect to fluorescence is lower than that of the emitted light, and thus the overall efficiency of the white light from the white light emitting device is not improved. Furthermore, since the light scattering property is different between the emitted light and the fluorescence in the same manner as described above, the angle distribution is different, and as a result, the angle dependency at all visible light wavelengths is observed.
- the above problem is interpreted as follows.
- a concavo-convex structure By forming a concavo-convex structure on the light emitting exposed surface of the semiconductor light emitting element, a diffraction or light scattering effect is produced, the waveguide mode inside the semiconductor light emitting element is broken, and the light extraction efficiency of the primary emitted light is improved.
- the refractive index of the coating layer containing the nanoparticle phosphor is approximated by an effective medium approximation because it contains nanoparticles, and the refractive index of the phosphor is higher than the dispersion medium of the coating layer, resulting in coating The refractive index of the layer is high.
- fa and fb are volume fractions of the medium a and the medium b
- ⁇ a, ⁇ b, and ⁇ are the dielectric constants of the medium a, the medium b, and the effective medium, respectively
- n is the refractive index of the effective medium.
- the difference in refractive index between the concavo-convex structure and the coating layer is reduced, and as a result, the diffraction / dispersion effect due to the concavo-convex structure is reduced. It is considered that the light extraction efficiency of the emitted light is lowered.
- the white light emitting device combined with the fluorescent material has a problem in that sufficient light emission efficiency does not appear and the light emission distribution has an angle dependency.
- an object of the present invention is to provide a semiconductor light emitting device capable of increasing light scattering properties and improving light emission efficiency. It is another object of the present invention to provide a semiconductor light-emitting device that has less angle dependency of the light emission distribution and can be easily applied for industrial use.
- the semiconductor light emitting device of the present invention has a laminated semiconductor layer formed by laminating at least two semiconductor layers and a light emitting layer, and emits a first light, and at least the semiconductor light emitting device.
- the semiconductor light-emitting element includes a microstructure layer including dots formed by a plurality of convex portions or concave portions extending in an out-of-plane direction on any main surface constituting the semiconductor light-emitting device.
- the microstructure layer constitutes a two-dimensional photonic crystal controlled at least by the pitch between dots, the dot diameter or the dot height, and the two-dimensional photonic crystal is at least And having more than one period of more than ⁇ _1Myuemu.
- the two-dimensional photonic crystal has at least two periods of 6 times or more of the optical wavelength of the first light and 6 times or more of the optical wavelength of the second light. It is preferable to have.
- a semiconductor light emitting device having a laminated semiconductor layer formed by laminating at least two semiconductor layers and a light emitting layer, emitting a first light, and at least the semiconductor
- a wavelength conversion member that covers a part of the light emitting element, absorbs at least a part of the first light, and emits a second light different from the wavelength of the first light.
- the semiconductor light-emitting element includes a fine structure layer including dots formed by a plurality of convex portions or concave portions extending in an out-of-plane direction on any main surface constituting the semiconductor light-emitting element.
- the fine structure layer constitutes a two-dimensional photonic crystal controlled by at least one of the pitch between dots, the dot diameter, or the dot height, and the two-dimensional photonic crystal First More than six times the optical wavelength of light more than six times and the second optical wavelength of the light, and having at least two or more periods.
- the wavelength conversion member is a first material that is transparent to at least the first light and the second light, and at least a part of the first light. It is preferable to contain the 2nd material which absorbs and emits said 2nd light.
- the fine structure layer is provided as a constituent element at least on the outermost surface of the semiconductor light emitting device, and at least the first light and the second light are provided between the fine structure layer and the wavelength conversion member. It is preferable that the intermediate material which is substantially transparent and does not contain the second material is filled.
- the second material has an average particle diameter smaller than the optical wavelength in the first material of the first light.
- the wavelength conversion member emits the second light and a third light different from each wavelength of the first light and the second light.
- the wavelength converting member absorbs at least a part of the first light, the second material, and the first light that is transparent to the third light, and at least a part of the first light.
- the second material includes a third material that emits the third light, and the two-dimensional photonic crystal has a period of six times or more the optical wavelength of the third light.
- the fine structure layer is provided as a constituent element at least on the outermost surface of the semiconductor light emitting device, and at least the first light and the second light are provided between the fine structure layer and the wavelength conversion member. And an intermediate material which is substantially transparent to the third light and does not contain the second material and the third material.
- At least one of the second material and the third material has an average particle diameter smaller than an optical wavelength of the first light in the first material.
- the wavelength conversion member includes the second light, the third light, the first light, the second light, and the third light. It is configured to emit fourth light different from the wavelength, and the wavelength conversion member is transparent to at least the first light, the second light, the third light, and the fourth light.
- a first material and a fourth material that absorbs at least a part of the first light and emits the fourth light, and the two-dimensional photonic crystal includes the fourth light. It is preferable to have a period of 6 times or more of the optical wavelength.
- the fine structure layer is provided as a constituent element at least on the outermost surface of the semiconductor light emitting device, and at least the first light and the second light are provided between the fine structure layer and the wavelength conversion member.
- an intermediate material that is practically transparent to the third light and the fourth light and does not include the second material, the third material, and the fourth material. preferable.
- At least one of the second material, the third material, and the fourth material has an average particle diameter smaller than the optical wavelength of the first light in the first material.
- the two-dimensional photonic crystal is formed on any two or more main surfaces constituting the semiconductor light-emitting element, and the period of each two-dimensional photonic crystal is Preferably they are different from each other.
- the two-dimensional photonic crystal may have a period at least in one axis direction of the main surface, or the main surface may have at least an independent period of the two-dimensional photonic crystal. It can be configured to have a period in the biaxial direction.
- the two-dimensional photonic crystal constituting the microstructure layer is 1 ⁇ m or more, or 6 times or more of the optical wavelength of the first light and the second light (the first light by the wavelength conversion member).
- Light having a wavelength different from that of the first light emitted by absorbing at least a part of the light has a period of at least two times that is six times or more of the optical wavelength, thereby enhancing the light scattering property rather than the light diffraction property. be able to. Therefore, in the semiconductor light emitting device of the present invention, the light scattering property can be strongly expressed with respect to the light emission from the semiconductor layer and the light emission from the wavelength conversion member, and the waveguide mode is eliminated by this light scattering property.
- the light extraction efficiency LEE can be increased. Furthermore, it is possible to efficiently convert the wavelength of primary light emitted from the semiconductor light emitting device efficiently. As a result, the final luminous efficiency of the semiconductor light emitting device can be improved. Furthermore, it is possible to provide a semiconductor light emitting device that reduces the angle dependency of the light emission distribution and is easily applicable for industrial use.
- the semiconductor light emitting device includes a semiconductor light emitting element that has a laminated semiconductor layer formed by laminating at least two or more semiconductor layers and a light emitting layer, emits first light, and at least the semiconductor.
- a wavelength conversion member that covers a part of the light emitting element, absorbs at least a part of the first light, and emits a second light different from the wavelength of the first light.
- the semiconductor light emitting device of the present embodiment is configured by a schematic cross-sectional view shown in FIG.
- the semiconductor light emitting device 500 has a configuration in which the semiconductor light emitting element 100 is disposed in the housing portion 520 a of the package 520.
- the package 520 is filled with the wavelength conversion member 511. Therefore, each surface except the back surface 100a of the semiconductor light emitting element 100 is covered with the wavelength conversion member 511.
- the wavelength conversion member 511 includes a filler 541 that is a first material substantially transparent with respect to the emission center wavelength of the emitted light (first light) from the semiconductor light emitting device 100, and the filler 541. And a fluorescent material (second material) 531 dispersed therein.
- the fluorescent material 531 has fluorescence characteristics with respect to the emission center wavelength of the first light that is emitted light from the semiconductor light emitting device 100, absorbs at least a part of the first light, and the first light. Fluorescence, which is second light different from the wavelength of, is emitted.
- the filler 541 is substantially transparent to the fluorescence that is the second light, and is also substantially transparent to third light and fourth light described later.
- the term “substantially transparent” in the present invention refers to a state in which there is almost no absorption with respect to light of the corresponding wavelength. Or less, more preferably 2% or less.
- the term “substantially transparent” is defined as a transmittance of light of a corresponding wavelength of 80% or more, preferably 85% or more, and more preferably 90% or more.
- the filler 541 can be organic or inorganic, and can be composed of materials including, for example, epoxy, acrylic polymer, polycarbonate, silicone polymer, optical glass, chalcogenide glass, spiro compound, and mixtures thereof, The material is not particularly limited.
- the filler 541 may also contain fine particles that are substantially transparent to the first light, the second light, the third light, and the fourth light. By containing fine particles, heat resistance, durability, weather resistance, and thermal dimensional stability are improved, which is preferable.
- the fine particles contained in the filler 541 are not particularly limited, and may be metal oxides, metal nitrides, nitridosilicates, and mixtures thereof.
- suitable metal oxides can include calcium oxide, cerium oxide, hafnium oxide, titanium oxide, zinc oxide, zirconium oxide and mixtures thereof.
- the emitted light from the semiconductor light emitting device 500 a color mixture of the first light emitted from the semiconductor light emitting element 100 and the second light that is fluorescence from the wavelength conversion member 511 is observed.
- a blue fluorescent material having an emission center wavelength in the vicinity of 450 nm and the second light is a yellow fluorescent material having a dominant wavelength in the vicinity of 590 nm, the emitted light of the semiconductor light emitting device 500 is observed as white.
- the wavelengths of the first light and the second light are not particularly limited, and are arbitrarily selected so that the emission color from the semiconductor light emitting device 500 exhibits a color according to the purpose as described above. However, since the first light is absorbed and second light that is fluorescent light is obtained, the wavelength of the second light is always longer than that of the first light.
- both the first light and the second light need not be visible light, for example, even if the first light is ultraviolet light having a wavelength of 410 nm or less and the second light is green. Good. In this case, only the monochromatic light is observed as the emitted light from the semiconductor light emitting device 500.
- the light emitted from the semiconductor light emitting device 500 can be variously selected according to the purpose, and accordingly, the configuration of the semiconductor light emitting element 100 and the material of the fluorescent material 531 are variously selected.
- Part of the emitted light from the semiconductor light emitting element 100 is absorbed by the fluorescent material 531 and emits fluorescence. Although the fluorescence is led out of the semiconductor light emitting device 500 as it is, a part of the fluorescence is scattered as shown in FIG. 1 and returns to the semiconductor light emitting element 100. At this time, the fluorescence is scattered by a fine structure layer provided in the semiconductor light emitting element 100 described later, and is led out of the semiconductor light emitting device 500.
- the semiconductor light emitting element 100 when the semiconductor light emitting element 100 is not provided with a fine structure layer, the angle of the light returning to the semiconductor light emitting device 500 is not changed, and a part thereof is in a light guide mode, and the semiconductor light emitting device 500 As a result, the light emission efficiency of the semiconductor light emitting device 500 is lowered.
- FIG. 2 is a schematic cross-sectional view showing another example of the semiconductor light emitting device according to the present embodiment.
- the semiconductor light emitting device 501 a part of the light emitting surface of the semiconductor light emitting element 100 installed in the package 520 is covered with the wavelength conversion member 512.
- the package 520 is filled with a sealing material 542.
- the wavelength converting member 512 includes a filler 541 that is substantially transparent to the light emitted from the semiconductor light emitting element 100 and a fluorescent material 531 that is contained and dispersed therein.
- the semiconductor light emitting device 501 shown in FIG. 2 similarly to the semiconductor light emitting device 500 in FIG. 1 described above, emitted light (first light) from the semiconductor light emitting element 100 and fluorescence from the fluorescent material 531 (second light). Light) is scattered by the fine structure layer provided in the semiconductor light emitting element 100 and is efficiently led out of the semiconductor light emitting device 501.
- the volume of the wavelength conversion member 512 is smaller than in the semiconductor light emitting device 500 in FIG. 1, and the emitted light and fluorescence from the semiconductor light emitting element 100 are less susceptible to scattering from the fluorescent material 531. Therefore, the fine structure layer provided in the semiconductor light emitting device 100 needs to have stronger scattering properties.
- the microstructure layer provided in the semiconductor light emitting element 100 can be appropriately designed depending on the configuration, use, and the like of the semiconductor light emitting device.
- the same transparent member as the filler 541 used in the wavelength conversion member 512 can be used.
- FIG. 3 is a schematic cross-sectional view showing another example of the semiconductor light emitting device according to the present embodiment.
- the semiconductor light emitting device 510 has a configuration in which the semiconductor light emitting element 100 is disposed in the housing portion 520 a of the package 520.
- the package 520 is filled with the wavelength conversion member 511, and the semiconductor light emitting element 100 further includes a fine structure including dots formed of concave portions or convex portions on the outermost surface thereof.
- Layer 120 is provided as a component.
- the intermediate material 121 is interposed between the fine structure layer 120 and the wavelength conversion member 511, and the fine structure layer 120 is not in contact with the wavelength conversion member 511. That is, the intermediate material 121 is formed with a thickness between the outermost surface of the fine structure layer 120 and the facing surface of the fine structure layer 120 of the wavelength conversion member 511.
- the intermediate material 121 is filled between dots formed by the convex portions of the fine structure layer 120.
- the intermediate material 121 is filled in the recesses. Therefore, the entire space from the surface of the microstructure layer 120 to the wavelength conversion member 511 is filled with the intermediate material 121.
- the intermediate material 121 shown in FIG. 3 is cured and hardened after application.
- the intermediate material 121 may be formed following the undulation of the surface of the microstructure layer 120, but the surface 121a of the intermediate material 121 (intermediate layer) may be formed as a flat surface as shown in FIG. Good.
- the intermediate material 121 may be filled only between the dots formed by the convex portions of the microstructure layer 120 or only in the dots formed by the concave portions. In such a configuration, at least a portion between the outermost surface of the microstructure layer 120 and the facing surface of the wavelength conversion member 511 facing the microstructure layer 120 is in contact.
- Such a configuration is also defined as a configuration in which the intermediate material 121 is interposed (filled) between the microstructure layer 120 and the wavelength conversion member 511.
- the intermediate material 121 is interposed between the fine structure layer 120 and the wavelength conversion member 511 so that the fine structure layer 120 is not in contact with the wavelength conversion member 511.
- the wavelength conversion member 511 includes a filler 541 that is a substantially transparent first material with respect to the emission center wavelength of the emitted light (first light) from the semiconductor light emitting device 100, and the inclusion and dispersion thereof. And a fluorescent material (second material) 531.
- the fluorescent material 531 has fluorescence characteristics with respect to the emission center wavelength of the first light that is emitted light from the semiconductor light emitting device 100, absorbs at least a part of the first light, and the first light. Fluorescence, which is second light different from the wavelength of, is emitted.
- the filler 541 is substantially transparent to the fluorescence that is the second light, and is also substantially transparent to third light and fourth light described later.
- the intermediate material 121 filled between the dots of the microstructure layer 120 described above is substantially transparent with respect to the emission center wavelength of the emitted light (first light) from the semiconductor light emitting element 100. Furthermore, it is substantially transparent to the fluorescence that is the second light, and is also substantially transparent to third light and fourth light described later.
- the intermediate material 121 can be organic or inorganic, and can be composed of materials including, for example, epoxy, acrylic polymer, polycarbonate, silicone polymer, optical glass, chalcogenide glass, spiro compound, and mixtures thereof, The material is not particularly limited.
- the intermediate material 121 may be either the same material as the filler 541 or a different material. However, it is preferable to use the same material for the intermediate material 121 and the filler 541 because the light emission characteristics can be effectively improved.
- a silicone resin can be selected for the intermediate material 121 and the filler 541.
- the intermediate material 121 may also contain fine particles that are substantially transparent to the first light, the second light, the third light, and the fourth light. By containing fine particles, heat resistance, durability, weather resistance, and thermal dimensional stability are improved, which is preferable.
- the fine particles contained in the intermediate material 121 are not particularly limited, but it is not preferable that the effective refractive index of the intermediate material 121 filled between the dots of the microstructure layer 120 is increased.
- the refractive index is preferably equal to or less than that of the intermediate material 121.
- substantially equivalent means that the difference in refractive index from the intermediate material 121 is 0.1 or less. If the difference in refractive index is 0.1 or less, when the fine particles contained in the intermediate material 121 have a volume fraction within 50%, the effective refractive index of the intermediate material 121 containing the fine particles is only the intermediate material 121. This is preferable because it is equivalent to the refractive index of.
- the fine particles contained in the intermediate material 121 are not particularly limited, and may be metal oxides, metal nitrides, nitridosilicates, and mixtures thereof.
- suitable metal oxides can include silicon oxide, calcium oxide, cerium oxide, hafnium oxide, titanium oxide, zinc oxide, zirconium oxide and mixtures thereof.
- the same material as the fine particles contained in the filler 541 described above may be used.
- the intermediate material 121 is filled between the microstructure layer 120 and the wavelength conversion member 511, but the fluorescent material (second material) 531 is not included.
- the fluorescent material (second material) 531 does not enter between the dots.
- the fluorescent material (second material) 531 is not contained in the dots. Therefore, only the intermediate material 121 is interposed between the microstructure layer 120 and the wavelength conversion member 511, or the intermediate material 121 containing the fine particles is interposed.
- the fluorescent material 531 is not filled between the dots or in the dots of the fine structure layer 120, the effective refractive index between the dots or within the dots does not increase, and the semiconductor light emitting device 100 by the fine structure layer 120 is used.
- the efficiency of diffraction or scattering for the first light from is not reduced.
- the wavelength conversion member 511 is provided so as to cover at least a part of the semiconductor light emitting element 100, it is possible to prevent the light extraction efficiency from the semiconductor light emitting device 500 from being lowered.
- the fluorescent material 531 exists between dots or in dots in the microstructure layer 120 of the semiconductor light emitting device 100, and the effective refractive index between dots or within dots increases, Since the diffraction or scattering efficiency with respect to fluorescence decreases, the phenomenon that the semiconductor light emitting device 510 is led out of the system is suppressed, and as a result, the light emission efficiency of the semiconductor light emitting device 510 decreases.
- FIG. 4 is a schematic cross-sectional view showing another example of the semiconductor light emitting device according to the present embodiment.
- the semiconductor light emitting device 508 a part of the light emitting surface of the semiconductor light emitting element 100 installed in the package 520 is covered with the wavelength conversion member 512.
- the package 520 is filled with a sealing material 542.
- the wavelength converting member 512 includes a filler 541 that is substantially transparent to the light emitted from the semiconductor light emitting element 100 and a fluorescent material 531 that is contained and dispersed therein.
- the semiconductor light emitting device 508 shown in FIG. 4 similarly to the semiconductor light emitting device 510 in FIG. 3 described above, light emitted from the semiconductor light emitting element 100 (first light) and fluorescence from the fluorescent material 531 (second light) Light) is scattered by the fine structure layer 120 provided in the semiconductor light emitting element 100 and is efficiently led out of the semiconductor light emitting device 508.
- the volume of the wavelength conversion member 512 is smaller than that of the semiconductor light emitting device 510 of FIG. Therefore, the fine structure layer 120 provided in the semiconductor light emitting device 100 needs to have a stronger scattering property.
- the microstructure layer 120 provided in the semiconductor light emitting element 100 can be appropriately designed depending on the configuration, use, and the like of the semiconductor light emitting device.
- the intermediate material 121 not including the fluorescent material 531 is interposed between the fine structure layer 120 provided in the semiconductor light emitting element 100 and the wavelength conversion member 512, and the fine structure layer 120 is composed of the wavelength conversion member 512. Not touching.
- the same transparent member as the filler 541 used in the wavelength conversion member 512 can be used.
- FIG. 5 is a schematic cross-sectional view showing another example of the semiconductor light emitting device according to the present embodiment.
- the semiconductor light emitting element 100 installed in the package 520 is covered with a wavelength conversion member 513 as in FIG.
- the wavelength conversion member 513 includes and is dispersed in a filler 541 that is a first material substantially transparent to the emission center wavelength of the emitted light from the semiconductor light emitting element 100 that is the first light. It is composed of a fluorescent material 531 and a fluorescent material 532.
- the fluorescent material 532 has a fluorescence characteristic with respect to the emission center wavelength of the first light that is the emitted light emitted from the semiconductor light emitting element 100, absorbs at least a part of the first light, and the first light. And a third material that emits fluorescence that is third light different from the wavelength of the second light.
- the emitted light from the semiconductor light emitting device 502 is observed as a mixed color of the first light emitted from the semiconductor light emitting element 100, the second light that is fluorescence from the wavelength conversion member, and the third light. .
- the semiconductor light emitting device when the first light is blue having an emission center wavelength near 450 nm, the second light is green having a dominant wavelength near 545 nm, and the third light is red having a dominant wavelength near 700 nm, the semiconductor light emitting device The emitted light 502 is recognized as white.
- the filler 541 described above is substantially transparent to the second light and the third light.
- the wavelengths of the first light, the second light, and the third light are not particularly limited, and as described above, the emission color from the semiconductor light emitting device 502 exhibits a color according to the purpose. Arbitrarily selected. However, since the second light and the third light, which are fluorescent light, are absorbed, the wavelengths of the second light and the third light are always longer than the first light. Become.
- the second light and part of the third light are scattered and returned to the semiconductor light emitting element 100. Then, it is scattered by the fine structure layer provided in the semiconductor light emitting element 100 and led out of the semiconductor light emitting device 502. With such an action, the light emission efficiency of the semiconductor light emitting device 502 can be improved.
- the semiconductor light emitting device 502 shown in FIG. 5 similarly to the semiconductor light emitting device 501 shown in FIG. 2, a part of the light emitting surface of the semiconductor light emitting element 100 is converted into a wavelength conversion in which fluorescent materials 531 and 532 are dispersed in a filler 541.
- the package 520 may be covered with the member 513 and filled with the sealing material 542 in FIG.
- FIG. 6 is a schematic cross-sectional view showing another example of the semiconductor light emitting device according to the present embodiment.
- the semiconductor light emitting element 100 installed in the package 520 is covered with a wavelength conversion member 513 as in FIG.
- the wavelength conversion member 513 includes and is dispersed in a filler 541 that is a first material substantially transparent to the emission center wavelength of the emitted light from the semiconductor light emitting element 100 that is the first light.
- a fluorescent material (second material) 531 and a fluorescent material (third material) 532 are included.
- an intermediate material 121 that does not include the fluorescent materials 531 and 532 is interposed between the microstructure layer 120 provided in the semiconductor light emitting device 100 and the wavelength conversion member 513, and the microstructure layer 120 is wavelength-converted. It is not in contact with the member 513.
- the second light and part of the third light are scattered and returned to the semiconductor light emitting element 100. Then, the light is scattered by the fine structure layer 120 provided in the semiconductor light emitting element 100 and led out of the system of the semiconductor light emitting device 509. With such an action, the light emission efficiency of the semiconductor light emitting device 509 can be improved.
- a part of the light emitting surface of the semiconductor light emitting device 100 is partly replaced by a wavelength conversion member 513 in which fluorescent materials 531 and 532 are dispersed in a filler 541.
- the package 520 may be covered in the same manner as 508, and the package 520 may be filled with the sealing material 542 in FIG.
- the intermediate material 121 that does not include the fluorescent materials 531 and 532 is interposed between the fine structure layer 120 provided on the surface of the semiconductor light emitting element 100 and the wavelength conversion member 513, and the fine structure layer 120.
- the wavelength conversion member 513 are not in direct contact with each other.
- FIG. 7 is a schematic cross-sectional view showing another example of the semiconductor light emitting device according to the present embodiment.
- the semiconductor light emitting device 503 in FIG. 7 has a configuration in which the semiconductor light emitting element 100 installed in the package 520 is covered with a wavelength conversion member 514.
- the wavelength conversion member 514 is contained and dispersed in a filler 541 that is a first material that is substantially transparent to the emission center wavelength of the emitted light from the semiconductor light emitting device 100 that is the first light.
- the fluorescent material 531, the fluorescent material 532, and the fluorescent material 533 are configured.
- the fluorescent material 533 has a fluorescence characteristic with respect to the emission center wavelength of the first light that is the emitted light emitted from the semiconductor light emitting device 100, absorbs at least a part of the first light, and the first light. And fluorescent light that is fourth light different from the wavelength of the second light and the third light.
- the emitted light from the semiconductor light emitting device 503 includes the first light emitted from the semiconductor light emitting element 100, the second light, the third light, and the fourth light that are fluorescence from the wavelength conversion member 514. Observed as a color mixture.
- the first light is UV light having an emission center wavelength near 360 nm
- the second light is green having a dominant wavelength near 545 nm
- the third light is red having a dominant wavelength near 700 nm
- the fourth light is recognized as white.
- the filler 541 described above is substantially transparent to the second light, the third light, and the fourth light.
- the wavelengths of the first light, the second light, the third light, and the fourth light are not particularly limited, and as described above, the emission color from the semiconductor light emitting device 503 depends on the purpose. Arbitrarily selected to exhibit color. However, since the second light, the third light, and the fourth light that are fluorescent light are absorbed and the wavelengths of the second light, the third light, and the fourth light are obtained. Always be longer than the first light.
- part of the second light, the third light, and the fourth light is scattered and returns to the semiconductor light emitting element 100. Accordingly, the fine structure layer provided in the semiconductor light emitting element 100 is scattered and led out of the semiconductor light emitting device 503. With such an action, the light emission efficiency of the semiconductor light emitting device 503 can be improved.
- FIG. 8 is a schematic cross-sectional view showing another example of the semiconductor light emitting device according to the present embodiment.
- the semiconductor light emitting device 515 in FIG. 8 has a configuration in which the semiconductor light emitting element 100 installed in the package 520 is covered with a wavelength conversion member 514.
- the wavelength conversion member 514 is contained and dispersed in a filler 541 that is a first material that is substantially transparent to the emission center wavelength of the emitted light from the semiconductor light emitting device 100 that is the first light.
- the fluorescent material (second material) 531, the fluorescent material (third material) 532, and the fluorescent material (fourth material) 533 are configured.
- an intermediate material 121 that does not include the fluorescent materials 531, 532, and 533 is interposed between the fine structure layer 120 provided in the semiconductor light emitting element 100 and the wavelength conversion member 514, and the fine structure layer 120 has a wavelength. It is not in contact with the conversion member 514.
- the filler 541 and the intermediate material 121 described above are substantially transparent to the second light, the third light, and the fourth light.
- the semiconductor light emitting device 515 shown in FIG. 8 part of the second light, the third light, and the fourth light is scattered and returns to the semiconductor light emitting element 100. Therefore, the fine structure layer 120 provided in the semiconductor light emitting element 100 is scattered and led out of the semiconductor light emitting device 515. With such an action, the light emission efficiency of the semiconductor light emitting device 515 can be improved.
- the fluorescent material 531, the fluorescent material 532, and the fluorescent material 533 are not particularly limited as long as they absorb at least part of the first light and emit predetermined fluorescence.
- yttrium, aluminum, and garnet. Sulfur-substituted aluminate, unsubstituted aluminate, alkaline earth metal borate halide, alkaline earth metal aluminate, alkaline earth silicate, alkaline earth thiogallate, alkaline earth silicon nitride, germanic acid
- Examples include salts, phosphates, silicates, selenides, sulfides, nitrides, oxynitrides, and mixtures thereof.
- lanthanoid elements such as Ce and Eu can be doped into these materials and activated.
- Ce and Eu one or more selected from Tb, Cu, Ag, Cr, Nd, Dy, Co, Ni, Ti, and Mg may be included.
- Each of the fluorescent materials 531, 532, and 533 preferably has an average particle size smaller than the optical wavelength in the first light filler (first material) 541.
- the so-called nano-particle fluorescent particles having an average particle size smaller than the optical wavelength of the first material of the first light reduces the light scattering property by the fluorescent particles and improves the light extraction efficiency from the semiconductor light-emitting device. Can be improved.
- the primary light emission (first light) emitted from the semiconductor light emitting element can be wavelength-converted efficiently, so that the light extraction efficiency can be further improved.
- the average particle diameter in the present invention is the mass average particle diameter of the primary particles of the fluorescent particles, and can be determined by the method described in JIS Z8827 using a transmission electron microscope (TEM).
- At least one of the fluorescent materials 531 and 532 may have an average particle diameter smaller than the optical wavelength in the first light filler (first material) 541. It is preferable that the fluorescent materials 531 and 532 have an average particle diameter smaller than the optical wavelength in the first light filler (first material) 541.
- At least one of the fluorescent materials 531, 532, and 533 may have an average particle diameter smaller than the optical wavelength in the first light filler (first material) 541. However, it is preferable that all the fluorescent materials 531, 532, and 533 have an average particle diameter smaller than the optical wavelength in the first light filler (first material) 541.
- Each fluorescent material 531, 532, 533 is preferably in the form of particles. However, it is not limited to a spherical shape, and may be a polygonal shape, an ellipsoid or the like.
- FIG. 9 is a schematic cross-sectional view of a semiconductor light emitting element in the semiconductor light emitting device according to this embodiment.
- an n-type semiconductor layer 103, a light emitting layer 104, and a p-type semiconductor are formed on a two-dimensional photonic crystal 102 provided on one main surface of a substrate 101 for a semiconductor light emitting device.
- Layers 105 are sequentially stacked.
- the n-type semiconductor layer 103, the light-emitting layer 104, and the p-type semiconductor layer 105 that are sequentially stacked on the semiconductor light-emitting element substrate 101 are referred to as a stacked semiconductor layer 110.
- the “main surface” refers to a wide surface that constitutes the semiconductor light emitting element substrate 101 and the layer, for example, a laminated surface (formation surface) when the laminated semiconductor layer 110 is laminated or a surface opposite to the laminated surface. is there.
- the “main surface” includes the interface between the substrate for the semiconductor light emitting element and the layer, the interface between the layers, the exposed surface of the semiconductor light emitting element substrate 101 and the layer, and the exposed back surface.
- a photonic crystal is a nanostructure whose refractive index (dielectric constant) changes periodically, and a two-dimensional photonic crystal refers to a two-dimensional periodic structure.
- a transparent conductive film 106 is formed on the p-type semiconductor layer 105.
- a cathode electrode 107 is formed on the surface of the n-type semiconductor layer 103, and an anode electrode 108 is formed on the surface of the transparent conductive film 106.
- the laminated semiconductor layer 110 is formed on the two-dimensional photonic crystal 102 provided on one main surface of the semiconductor light-emitting element substrate 101, but the two-dimensional photo of the semiconductor light-emitting element substrate 101 is formed.
- the laminated semiconductor layer 110 may be formed on another main surface opposite to the surface on which the nick crystal 102 is provided.
- FIG. 10 is a schematic cross-sectional view showing another example of the semiconductor light emitting device according to the present embodiment.
- a p-type semiconductor layer 302 a light emitting layer 303, and an n-type semiconductor layer 304 are sequentially stacked on a semiconductor light emitting device substrate 301.
- a two-dimensional photonic crystal 305 is provided on one main surface (exposed surface) of the n-type semiconductor layer 304.
- an anode electrode 306 is formed on the main surface opposite to the main surface in contact with the p-type semiconductor layer 302 of the semiconductor light emitting element substrate 301, and a cathode electrode 307 is formed on the surface of the n-type semiconductor layer 304. Each is formed.
- an n-type semiconductor layer 304, a light emitting layer 303, and a p-type semiconductor layer 302 are sequentially stacked on a base material (not shown), and then attached to the base material 301 for a semiconductor light emitting element, and the base material is peeled off.
- a method for manufacturing a semiconductor light emitting device is employed. After the substrate is peeled off, the anode electrode 306 and the cathode electrode 307 are respectively formed to obtain the semiconductor light emitting element in the semiconductor light emitting device of this embodiment. After providing the n-type semiconductor layer on the substrate, the two-dimensional photonic crystal 305 is transferred and formed in order to peel off at the interface with the n-type semiconductor layer.
- FIG. 11 is a schematic cross-sectional view showing another example of the semiconductor light emitting device according to the present embodiment.
- a two-dimensional photonic crystal 201 is formed on the main surface (exposed surface) of the transparent conductive film 106 shown in FIG.
- the two-dimensional photonic crystal of the present embodiment needs to have at least two periods. As shown in FIG.
- two-dimensional photonic crystals 102 and 201 are provided as constituent elements on different main surfaces of the semiconductor light emitting device, respectively, and two or more two-dimensional photonic crystals 102, 201, it is not necessary that each two-dimensional photonic crystal 102, 201 has two or more periods, and two or more two-dimensional photonic crystals 102, 201 having different periods are used as constituent elements of the semiconductor light emitting device. It is also good.
- the light emitted from the semiconductor light emitting element and the light emitted from the wavelength conversion member are diffracted at the interface constituting the two-dimensional photonic crystal by transmission, reflection, diffraction, and scattering in the semiconductor light emitting device. , Will receive a scattering effect. This effect does not need to be the same interface, and the same effect can be obtained at different interfaces or the same interface. Therefore, the effect of the present invention can be exhibited by providing two or more periods at different interfaces or by providing them at the same interface.
- the semiconductor light emitting devices 100, 200, and 300 shown in FIGS. 9 to 11 are examples in which the present embodiment is applied to a semiconductor light emitting device having a double hetero structure, but the stacked structure of the stacked semiconductor layers is limited to this. It is not something. Moreover, you may provide the buffer layer which is not shown in figure, and an undoped semiconductor layer between the base material for semiconductor light-emitting devices and an n-type semiconductor layer. Moreover, you may provide the reflection layer which is not shown in the interface of the base material for semiconductor light-emitting devices, and a semiconductor layer.
- FIG. 12 is a schematic perspective view illustrating an example of the substrate 1 for a semiconductor light emitting element according to the first embodiment.
- the substrate 1 for a semiconductor light emitting device has a generally flat plate shape, and a substrate 11 and a microstructure layer 12 (two-dimensional) provided on one main surface of the substrate 11. Photonic crystal).
- the fine structure layer 12 includes a plurality of convex portions 13 (convex portion rows 13-1 to 13-N) protruding upward from the main surface of the substrate 11.
- the convex portions 13 are arranged with specific intervals.
- the fine structure layer 12 may be separately formed on the main surface of the substrate 11 or may be formed by directly processing the substrate 11.
- FIG. 12 shows an example in which the microstructure of the microstructure layer 12 is configured by a plurality of convex portions 13, but is not limited thereto, and the microstructure of the microstructure layer 12 is configured by a plurality of concave portions. It may be.
- FIG. 13 is a schematic perspective view showing another example of the substrate for a semiconductor light emitting element according to the present embodiment.
- the substrate for semiconductor light emitting element 1a has a generally flat plate shape, and a substrate 11a and a microstructure layer 12a (two-dimensional) provided on one main surface of the substrate 11a. Photonic crystal).
- the fine structure layer 12a includes a plurality of concave portions 14 (concave portions 14-1 to 14-N) recessed from the surface S of the fine structure layer 12a toward the back surface of the base material 11a.
- the recesses 14 are arranged with specific intervals.
- the fine structure layer 12a may be separately formed on the main surface of the base material 11a, or may be formed by directly processing the base material 11a.
- the convex part 13 or the concave part 14 constituting the fine structure of the fine structure layers 12 and 12a in the semiconductor light emitting device bases 1 and 1a is referred to as “dot”.
- the diameter and pitch of the dots are on the nano order.
- the semiconductor layer is formed on the surface of the semiconductor light-emitting element substrate 1, 1a by providing a nano-order uneven structure on the surface of the semiconductor light-emitting element substrate 1, 1a, the semiconductor The CVD growth mode of the layer is disturbed, dislocation defects accompanying phase growth collide and disappear, and the effect of reducing dislocation defects can be produced. And by reducing the dislocation defects in the semiconductor crystal, the internal quantum efficiency IQE of the semiconductor light emitting device can be increased.
- a two-dimensional photonic crystal controlled by any one of the pitch between dots, the dot diameter, and the dot height is formed.
- the reflection, transmission, and diffraction characteristics for propagating light inside the crystal can be controlled by the photonic crystal whose refractive index changes periodically.
- the diameter and pitch of the dots formed on one main surface of the substrate for a semiconductor light emitting device of the present embodiment are on the order of nanometers and are approximately the same as the wavelength of propagating light. Therefore, in the present embodiment, the characteristics of the photonic crystal are determined by a periodic change in the effective refractive index distribution obtained by averaging the refractive index due to the structure (effective medium approximation). Since the effective refractive index distribution is repeated in the main surface of the substrate for a semiconductor light emitting element, a two-dimensional photonic crystal is formed.
- the period of the two-dimensional photonic crystal has at least two different periods each of 1 ⁇ m or more. Alternatively, it has at least two periods that are 6 times or more of the optical wavelength of the first light and 6 times or more of the optical wavelength of the second light. Since the two-dimensional photonic crystal has two or more different periods of 1 ⁇ m or more, or more than six times the optical wavelength of the first light and the second light, it is more light scattering than light diffractive. Sex will be strengthened. Therefore, in the semiconductor light emitting device of the present embodiment, the light scattering property can be strongly expressed with respect to the light emission from the semiconductor layer and the light emission from the wavelength conversion member. And the light extraction efficiency LEE can be increased.
- the angle dependency in the light emission characteristic is weakened, and it approaches the Lambertian light emission characteristic that is easier to apply to industrial applications.
- the period of the two-dimensional photonic crystal is 1 ⁇ m or more, 6 times or more of the optical wavelength of the first light, and 6 times or more of the optical wavelength of the second light. More preferably, it has at least two periods.
- the light scattering property can be enhanced more effectively than the light diffraction property, and the light extraction efficiency LEE can be further increased.
- the two-dimensional photonic crystal is not limited to being provided on one main surface of the substrate for a semiconductor light-emitting element, but is provided at one or more places in the semiconductor light-emitting element and also on the outermost surface of the semiconductor light-emitting element. .
- the two-dimensional photonic crystal controlled by the pitch between dots, the dot diameter, and the dot height will be described in more detail with reference to the drawings.
- FIG. 14 is a schematic plan view of the substrate 1 for a semiconductor light emitting device according to the present embodiment, showing a two-dimensional photonic crystal formed on the surface (one main surface) of the substrate 1 for a semiconductor light emitting device. Yes.
- the dots are a plurality of dots in which a plurality of dots are arranged at a pitch Py of indefinite intervals in the first direction D ⁇ b> 1 in the main surface of the substrate 1 for semiconductor light emitting elements.
- Dot rows (convex row 13-1 to 13-N or concave row 14-1 to 14-N; see FIGS. 12 and 13).
- each dot row is arranged at a pitch Px of indefinite intervals in the second direction D2 orthogonal to the first direction D1 within the main surface of the substrate 1 for semiconductor light emitting element.
- the pitch Py with an indefinite interval between the dots periodically increases and decreases.
- the pitch Px at indefinite intervals in the second direction D2 orthogonal to the first direction D1 periodically increases and decreases.
- the pitches Py and Px having indefinite intervals in both the first direction D1 and the second direction D2 may be periodically increased or decreased, and the pitches having indefinite intervals in either the first direction D1 or the second direction D2.
- Py and Px may be configured to periodically increase and decrease.
- the pitch Py with indefinite intervals between the dots periodically increases and decreases. Therefore, the light is periodically increased or decreased by the effective medium approximation. It shows a behavior equivalent to the presence of a larger concavo-convex structure.
- FIG. 15 is a schematic diagram illustrating an arrangement example of dot rows in the second direction D2.
- the dot rows in the second direction D2 are arranged at specific intervals (pitch Px) by eight rows, and eight dot rows are repeatedly arranged.
- a unit composed of a plurality of (z) dot rows is referred to as a long cycle unit Lxz (where z is a positive integer and x indicates the x direction).
- the long period unit Lxz needs to be 1 ⁇ m or more, or 6 times or more of the optical wavelength emitted from the semiconductor light emitting element.
- the dots in the first direction D1 arranged at indefinite intervals at different pitches Py can also be arranged in the same manner as described below using the long period unit Lyz.
- the pitch Px is a distance between adjacent dot rows.
- each dot is smaller than the pitch Pxn.
- the length from the pitch Px1 to Pxn constitutes the long cycle unit Lxz.
- the relationship of the following formula (2) is established in the pitch Pxn between the dot rows in the long cycle unit L1.
- the pitch Px in the long cycle unit Lxz has a maximum phase shift ⁇ represented by the difference between the maximum value (Px (max)) and the minimum value (Px (min)) of the pitch Px, (Px (min) ) ⁇ 0.01 ⁇ ⁇ (Px (min)) ⁇ 0.66, preferably (Px (min)) ⁇ 0.02 ⁇ ⁇ (Px (min)) ⁇ 0.5, more preferably It is set to satisfy (Px (min)) ⁇ 0.1 ⁇ ⁇ (Px (min)) ⁇ 0.4.
- the pitch Pxn between the dot rows is expressed as follows.
- Px1 Px (min)
- Px2 Px (min) + ⁇ a
- Px4 Px (min) + ⁇ c
- Px5 Px (min) + ⁇ d
- Px6 Px (min) + ⁇ e
- Px7 Px (min) + ⁇ f
- the maximum value of z in the long cycle unit Lxz or the long cycle unit Lyz is set so as to satisfy 4 ⁇ z ⁇ 1000, preferably 4 ⁇ z ⁇ 100, and more preferably 4 ⁇ z ⁇ 20. Yes.
- At least one dot group having the long cycle unit Lyz is arranged, and in the second direction D2, the long cycle unit described above is arranged. It is preferable that at least one dot row group having Lxz is arranged.
- the arrangement arranged at irregular intervals of the pitch Py is defined by replacing the dot arrangement with dots in the arrangement example of the dot arrangement in the second direction D2 arranged at irregular intervals with the different pitch Px described above. Is done.
- the dots constituting the fine structure of the fine structure layer 12 (12a) are indefinite as described above in both the first direction D1 and the second direction D2.
- the pitches Px and Py may be arranged at intervals (see FIG. 14), or only one of the first direction D1 and the second direction D2 may be arranged at an indefinite interval pitch as described above, and the other Can also be arranged at regular intervals (see FIG. 16).
- FIG. 16 is a schematic plan view showing another example of the base material for a semiconductor light emitting device according to the present embodiment. In FIG. 16, dots in the first direction D1 are arranged at an infinite interval pitch, and dot rows in the second direction D2 are arranged at a constant interval pitch.
- the two-dimensional photonic crystal illustrated in FIGS. 14 and 16 is a two-dimensional photonic crystal formed from non-periodic dots (dot rows).
- the pattern of dots constituting the two-dimensional photonic crystal may be periodic. Since the periodicity of individual dots is canceled by approximation of the effective medium as described above, the long period unit Lxz is necessary for expressing the effect of the substrate for a semiconductor light emitting device of the present embodiment.
- the dot period / non-period is not critical.
- FIG. 17, FIG. 18, FIG. 19 and FIG. 20 are given as examples of periodic dot patterns.
- adjacent dot rows FIGGS. 19 and 20
- every other dot row FIGGS. 17 and 18
- FIGS. 17 to 20 are schematic plan views showing other examples of the substrate for a semiconductor light emitting element according to the present embodiment.
- the two-dimensional photonic crystal having a dot pattern is composed of at least the first light and the first light in the uniaxial direction of any main surface constituting the semiconductor light emitting device. It is preferable to have a period of 6 times or more of the optical wavelength of the second light different from the period, and specifically, a two-dimensional photonic crystal as shown in FIGS.
- the period of the two-dimensional photonic crystal is periodic in at least two independent biaxial directions.
- the two-dimensional photonic crystal is as shown in FIGS.
- the two-dimensional photonic crystal formed by the density of dots can be a triangular lattice arrangement.
- the ratio of the pitch of the indefinite interval to the constant interval pitch is specified. It is preferable to be within the range.
- the ratio of the pitch Px with indefinite intervals to the pitch Pyc with constant intervals is in the range of 85% to 100%. It is preferable that the ratio of the pitch Px of the indefinite interval to the pitch Pyc of the constant interval is 85% or more because the overlap between adjacent dots is reduced. In addition, it is preferable that the ratio of the pitch Px of the indefinite interval to the pitch Pyc of the constant interval is 100% or less because the filling rate of the convex portions 13 constituting the dots is improved. It is more preferable that the ratio of the irregularly spaced pitch Px to the regularly spaced pitch Pyc is in the range of 90% to 95%.
- one long-period unit Lxz or Lyz is preferable because a long-period fluctuation in the refractive index of light generated in the light-emitting layer moves away from the nano-order and light scattering is likely to occur.
- the long-period unit Lxz or Lyz is preferably composed of 1001 or less dots (the pitch Px or Py to which it belongs is 1000 or less).
- a two-dimensional photonic crystal that satisfies the above-described microstructure relationship of the microstructure layer 12 (12a) is formed on the substrate 1 (1a) for a semiconductor light emitting device according to the present embodiment.
- the light scattering effect is sufficient, and the interval between the dots (the convex portion 13 or the concave portion 14) becomes small, so that an effect of reducing dislocation defects is produced.
- the dislocation defects in the semiconductor layer are reduced by the nano-order irregularities, and at the same time, the nano-order periodicity is disturbed, and the light scattering property can be strongly expressed against the light emission from the semiconductor layer.
- the dot shape (uneven structure) constituting the two-dimensional photonic crystal of the fine structure layer 12 (12a) of the substrate 1 for semiconductor light emitting device 1 (1a) according to the present embodiment will be described.
- the shape of the convex part 13 and the recessed part 14 will not be specifically limited if it is a range with which the effect of this invention is acquired, It can change timely according to a use.
- the two-dimensional photonic crystal in the present embodiment is configured with a dot interval, but may be configured with a large or small dot diameter.
- the diameter of each dot is The pitch Py and / or the pitch Px is preferably increased or decreased.
- the dot diameter Dyn (3 ⁇ n ⁇ 2a) constituting at least four adjacent and m or less pitches.
- the long period unit Lxz or Lyz is 1 ⁇ m or more, or 6 times or more of the optical wavelength of the first light and the second light emitted from the semiconductor light emitting element.
- Lxz it is the same also about Lyz.
- the dot diameter decreases as the distance between adjacent dots increases, and the dot diameter increases as the dot distance decreases. If the increase / decrease range of the dot diameter to be increased / decreased is too large, the adjacent dot comes into contact with the adjacent dots. Within ⁇ 20% of the average dot diameter within the same long period unit Lxz, the light extraction efficiency LEE increases, which is preferable.
- the volume of the dot is increased or decreased by the long period unit Lxz, and a two-dimensional photonic crystal is configured.
- the effective medium approximation can be simply expressed by the volume fraction of the dielectric constant distribution, and the dielectric constant is the square of the refractive index. That is, when the volume of the medium changes in the long cycle unit Lxz, the effective refractive index changes in the long cycle unit Lxz.
- the light scattering property with respect to the emitted light is large.
- the light extraction efficiency LEE in the semiconductor light emitting device is increased.
- each of the dot shapes constituting the fine structure of the fine structure layer 12 (12a) in synchronization with the two-dimensional pattern described above. It is preferable that the height of each dot increases or decreases with respect to the pitch Py and / or the pitch Px.
- the pitch Py is an indefinite interval
- the dot group constituted by the dot heights Hy1 to Hyn is repeatedly arranged in the long cycle unit Lyz, and the pitch Px is an indefinite interval, at least four adjacent and constitute m or less pitch.
- the dot height in the second direction Dot group consisting of x1 ⁇ Hxn it is preferably repeatedly arranged in long period units Lxz.
- the long period unit Lxz or Lyz is 1 ⁇ m or more, or 6 times or more of the optical wavelength of the first light and the second light emitted from the semiconductor light emitting element.
- Lxz it is the same also about Lyz.
- FIG. 22 is a schematic diagram illustrating an arrangement example of dots in the second direction D2 of the semiconductor light-emitting element substrate according to the present embodiment.
- the dot height decreases as the interval between adjacent dots increases, and the dot height increases as the dot interval decreases. If the increase / decrease range of the dot height to be increased / decreased is too large, the unevenness of the light extraction efficiency LEE at that portion becomes large, which is not preferable. Absent. Within ⁇ 20% of the average dot height within the same long period unit Lxz, the light extraction efficiency LEE is preferably increased without unevenness.
- the volume of the dot is increased or decreased by the long period unit Lxz, and a two-dimensional photonic crystal is configured.
- the effective medium approximation can be simply expressed by the volume fraction of the dielectric constant distribution, and the dielectric constant is the square of the refractive index. That is, when the volume of the medium changes in the long cycle unit Lxz, the effective refractive index changes in the long cycle unit Lxz.
- the light scattering property with respect to the emitted light is large.
- the light extraction efficiency LEE in the semiconductor light emitting device is increased.
- the above is a case of a two-dimensional photonic crystal having one period in the same main surface. As illustrated in FIG. 11, two-dimensional photons having different periods are formed on any main surface constituting the semiconductor light emitting device. By providing at least two or more nick crystals 102 and 201, the semiconductor light-emitting device of this embodiment can be obtained.
- FIG. 23 is a schematic plan view of a two-dimensional photonic crystal composed of dots having a long dot interval as in FIG.
- the long periods constituted by the pitch Py in the D1 direction and the pitch Px in the D2 direction that are orthogonal to each other are different.
- the period in the D1 direction is 1 ⁇ m or more, or 6 times or more of the optical wavelength of the first light
- the period in the D2 direction is 1 ⁇ m or more, or the optical wavelength of the second light. It can be set to 6 times or more, and becomes a two-dimensional photonic crystal having two or more different periods in the same main surface.
- the D1 direction can have a long period suitable for diffraction and scattering of the first light
- the D2 direction can have a long period suitable for diffraction and scattering of the second light. be able to.
- FIG. 24 is another schematic plan view of a two-dimensional photonic crystal having two or more periods in the same main surface.
- two types of long periods overlap the long period of the pitch Py in the D1 direction. Therefore, it becomes possible to form a two-dimensional photonic crystal having a period of 1 ⁇ m or more, or a period of 6 or more times the optical wavelength of the first light and the second light, and the first light and the second light.
- the pitch Py in the D1 direction and the pitch Px in the D2 direction are the same, but in the semiconductor light emitting device of the present embodiment, they are not necessarily the same and can be changed as appropriate.
- the long period in the D1 direction and the D2 direction can be changed. 1) Two or more long periods are formed only in the D1 direction, and 1 in the D2 direction. 2) Two or more long periods are formed in the D1 direction and the D2 direction, and only one long period is the same among the long periods.
- each long period is set to 2 Form one or more.
- the semiconductor light emitting device of the present embodiment can be obtained by appropriately selecting, for example, forming a long cycle in the D1 direction and the D2 direction, or forming two or more long cycles in the D1 direction. .
- the pitch Px and the pitch Py are preferably 100 nm or more and 1000 nm or less, respectively.
- the pitches Px and Py are within this range, nano-order irregularities are provided on the surface of the semiconductor light-emitting element substrate constituting the semiconductor light-emitting device of the present embodiment.
- a semiconductor layer is provided on the surface, the number of dislocation defects in the semiconductor layer can be reduced.
- the pitches Px and Py are 100 nm or more, the light extraction efficiency LEE of the semiconductor light emitting device is improved, and the effect of reducing dislocation defects contributing to the improvement of the light emission efficiency appears. Further, when the pitches Px and Py are 1000 nm or less, the effect of reducing the number of dislocation defects is maintained.
- the semiconductor light emitting element includes a fine structure layer as a constituent element, and the fine structure layer constitutes a two-dimensional photonic crystal.
- the two-dimensional photonic crystal has a period of 1 ⁇ m or more, or at least two times that is 6 times or more of the optical wavelength of the first light and 6 times or more of the optical wavelength of the second light.
- the first light is emitted from the semiconductor light emitting element, and the second light is emitted by absorbing at least part of the first light by the wavelength conversion member, and having a wavelength different from that of the first light.
- the third light, the fourth light,... are present as in the embodiments of FIGS. 5 to 8, the two-dimensional photonic crystal has a light scattering property of 1 ⁇ m or more. It has an optimal period or two or more periods that are six times or more the optical wavelength of each light.
- a waveguide mode is eliminated by light scattering by providing a two-dimensional photonic crystal composed of a nano-order unevenness (dot) microstructure layer at any interface that forms a semiconductor light emitting device.
- a two-dimensional photonic crystal composed of a nano-order unevenness (dot) microstructure layer at any interface that forms a semiconductor light emitting device.
- the same effect will be produced.
- the behavior of light can be explained by an average refractive index distribution (effective medium approximation), so if the average refractive index distribution in space is calculated, it is as if long-period unit Lxz
- the plurality of dots act on light as if repeated as one unit. In this way, the plurality of dots arranged in the long-period unit Lxz exhibit a light scattering effect.
- the light scattering property with respect to the emitted light can be increased, and the light extraction efficiency LEE in the semiconductor light emitting element is increased.
- the light emission efficiency of the semiconductor light emitting device can be improved. Furthermore, it is possible to provide a semiconductor light emitting device that reduces the angle dependency of the light emission distribution and is easily applicable for industrial use.
- a semiconductor light emitting device having a two-dimensional photonic crystal of 1 ⁇ m or more, or 6 times or more of the optical wavelength of each light, as shown in the experimental results described later, It has been found that a high light emission efficiency as a semiconductor light emitting device can be obtained as compared with a conventional structure having no period of 6 times or more of the optical wavelength. Furthermore, it was found that there was almost no angle dependency in the light emission characteristics, and it was found that a semiconductor light emitting device suitable for industrial practical use could be obtained.
- the period of the two-dimensional photonic crystal is preferably 200 times or less. If the period of the two-dimensional photonic crystal exceeds 200 times, the two-dimensional photonic crystal is not sufficiently smaller than the outer shape of the semiconductor light-emitting element constituting the semiconductor light-emitting device. The difference becomes large, which is not preferable. This is because the density of the two-dimensional photonic crystal formed on the semiconductor light emitting element is likely to vary between the semiconductor light emitting elements.
- the diameter of each dot can be increased or decreased according to the pitch. Since the average refractive index distribution of the space changes depending on the volume fraction of the structural unit, the change in the average refractive index distribution increases as the volume of each dot changes in a plurality of dots in the long period unit Lxz. Even in the same long period unit Lxz, the light scattering effect is further enhanced. This effect becomes more prominent by increasing the dot diameter when the pitch between dots is narrow and decreasing the dot diameter when the dot pitch is wide.
- the dot height can be increased or decreased according to the pitch between the dots.
- the pitch between dots when the pitch between dots is narrow, the dot height is increased, and when the pitch between dots is wide, when the dot height is decreased, the average refractive index distribution in the long period unit Lxz is This will increase the light scattering effect.
- both the diameter of each dot and the height of the dot are increased or decreased according to the pitch, which is described by effective medium approximation.
- the difference in refractive index distribution is further increased.
- the dot pitch is narrow, the dot diameter and dot height are increased, and when the dot pitch is wide, the dot diameter and dot height are reduced.
- the difference in the volume fraction of the structural units is increased, and the light scattering effect is further increased.
- the material of the base material for the semiconductor light emitting element to be applied is not particularly limited as long as it can be used as the base material for the semiconductor light emitting element.
- a substrate for a semiconductor light emitting element such as neodymium gallium oxide, lanthanum strontium aluminum tantalum, strontium titanium oxide, titanium oxide, hafnium, tungsten, molybdenum, GaP, or GaAs can be used.
- a substrate for sapphire GaN, GaP, GaAs, SiC semiconductor light emitting element, or the like.
- it may be used alone or as a substrate for a semiconductor light emitting element having a heterostructure in which another semiconductor light emitting element base is provided on the semiconductor light emitting element base body using these.
- the material of the n-type semiconductor layer is not particularly limited as long as it can be used as an n-type semiconductor layer suitable for the semiconductor light-emitting device.
- elemental semiconductors such as silicon and germanium
- compound semiconductors such as III-V, II-VI, and VI-VI can be appropriately doped with various elements.
- the material of the p-type semiconductor layer is not particularly limited as long as it can be used as a p-type semiconductor layer suitable for the semiconductor light emitting device.
- elemental semiconductors such as silicon and germanium
- compound semiconductors such as III-V, II-VI, and VI-VI can be appropriately doped with various elements.
- the material of the transparent conductive film is not particularly limited as long as it can be used as a transparent conductive film suitable for the semiconductor light emitting device.
- a metal thin film such as a Ni / Au electrode or a conductive oxide film such as ITO, ZnO, In 2 O 3 , SnO 2 , IZO, or IGZO can be applied.
- ITO is preferable from the viewpoints of transparency and conductivity.
- the semiconductor light emitting element according to the semiconductor light emitting device of this embodiment will be described.
- the base material for a semiconductor light emitting element according to the present embodiment described above is included in the configuration.
- the substrate for a semiconductor light emitting device according to this embodiment it is possible to improve internal quantum efficiency IQE, electron injection efficiency EIE, and light extraction efficiency LEE.
- the semiconductor light emitting device has, for example, a laminated semiconductor layer formed by laminating at least two semiconductor layers and a light emitting layer on the main surface of the substrate for a semiconductor light emitting device.
- the laminated semiconductor layer includes two dots including a plurality of convex portions or concave portions extending in the out-of-plane direction (for example, a direction substantially orthogonal to the main surface) from the main surface of the semiconductor layer located on the outermost surface.
- a two-dimensional photonic crystal is provided, and the two-dimensional photonic crystal corresponds to the two-dimensional photonic crystal structure of the substrate for a semiconductor light emitting device according to the above-described embodiment.
- the stacked semiconductor layer is as described with reference to FIGS. 9, 10, and 11.
- the semiconductor layer is not particularly limited as long as it can be used as a semiconductor layer suitable for the semiconductor light emitting device.
- elemental semiconductors such as silicon and germanium, compound semiconductors such as III-V group, II-VI group, VI-VI group, and the like can be appropriately doped with various elements.
- an n-type cladding layer and a p-type cladding layer (not shown) can be appropriately provided in the n-type semiconductor layer and the p-type semiconductor layer.
- the light emitting layer is not particularly limited as long as it has a light emitting characteristic as a semiconductor light emitting element.
- a semiconductor layer such as AsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlHaInP, or ZnO can be used as the light emitting layer.
- the light emitting layer may be appropriately doped with various elements according to characteristics.
- These laminated semiconductor layers can be formed on the surface of a semiconductor light-emitting element substrate by a known technique.
- a metal organic chemical vapor deposition method MOCVD
- HVPE hydride vapor phase epitaxy method
- MBE molecular beam epitaxy method
- the method for manufacturing a semiconductor light emitting element according to the present embodiment includes at least the step of providing a semiconductor layer on the substrate for a semiconductor light emitting element of the present embodiment.
- the n-type semiconductor layer, the light-emitting layer, and the p-type semiconductor layer are formed on the main surface side having the two-dimensional photonic crystal of the base material for the semiconductor light-emitting element having the two-dimensional photonic crystal on the main surface.
- FIG. 25 is a schematic cross-sectional view showing each step of the method of manufacturing a semiconductor light emitting element according to this embodiment.
- an n-type semiconductor layer 30, a light-emitting layer 40, and a p-type semiconductor layer 50 are sequentially laminated on the substrate 1 for a semiconductor light-emitting element. Further, a p-electrode layer 60 and a support 70 are sequentially stacked on the p-type semiconductor layer 50.
- the support 70 a conductive substrate made of Si, Ge, GaAs, Fe, Ni, Co, Mo, Au, Cu, Cu—W, or the like can be used.
- the laminated semiconductor layer 123 is configured to conduct in a direction perpendicular to the element surface, but may be a parallel electrode type.
- the support 70 may be an insulating substrate.
- a metal eutectic such as Au—Sn, Au—Si, Ag—Sn—Cu, Sn—Bi or the like, which is a low melting point metal, or a low melting point metal is not used.
- An Au layer, a Sn layer, a Cu layer, or the like can also be used.
- the support 70 may be formed by directly forming a metal layer on the p-electrode layer 60 by plating, sputtering, vapor deposition, or the like. Furthermore, you may provide the back surface electrode which is not shown in the surface which does not face the p electrode layer 60 of the support body 70. As shown in FIG.
- the two-dimensional photonic crystal 20 is inverted on the separation surface of the n-type semiconductor layer 30 by peeling (lifting off) the semiconductor light-emitting element substrate 1 from the laminated semiconductor layer 123.
- a semiconductor light emitting device 600 having the photonic crystal 80 is obtained.
- the structure of the two-dimensional photonic crystal 20 serving as the inversion source is appropriately designed so that the inverted two-dimensional photonic crystal 80 has a structure suitable for the obtained semiconductor light emitting device 600.
- laser lift-off For example, laser lift-off, chemical lift-off, or the like is employed for peeling the semiconductor light-emitting element substrate 1.
- the irradiated laser has a wavelength that passes through the semiconductor light emitting element substrate 1 but does not pass through the n-type semiconductor layer 30.
- chemical lift-off a method of laminating a thin etching layer on the two-dimensional photonic crystal 20 and peeling the substrate 1 for a semiconductor light emitting element by chemical etching can be mentioned.
- an n-electrode layer 90 is provided on the surface of the n-type semiconductor layer 30 including the two-dimensional photonic crystal 80, as shown in FIG. 25C.
- the manufacturing method shown below is an example, and the manufacturing method of the base material for semiconductor light emitting elements is not limited to this.
- FIG. 26 is a schematic explanatory view showing an example of a method for manufacturing the substrate for semiconductor light emitting element 1 (1a) of the present embodiment.
- the exposure apparatus 400 holds a roll-shaped member 401 coated with a resist layer by a roll holding unit (not shown), and includes a rotation control unit 402, a processing head unit 403, and a moving mechanism unit 404. And an exposure control unit 405.
- the rotation control unit 402 rotates the roll member 401 around the center of the roll member 401.
- the processing head unit 403 irradiates a laser beam to expose the resist layer of the roll-shaped member 401.
- the moving mechanism unit 404 moves the processing head unit 403 at a control speed along the long axis direction of the roll-shaped member 401.
- the exposure control unit 405 controls a pulse signal for laser exposure by the processing head unit 403 based on a reference signal synchronized with the rotation of the roll-shaped member 401 by the rotation control unit 402.
- the processing of the roll-shaped member 401 by the exposure apparatus 400 is performed by irradiating a pulse laser from the processing head unit 403 while the roll-shaped member 401 is rotated.
- the processing head unit 403 is moved along the long axis direction of the roll-shaped member 401 by the moving mechanism unit 404 while irradiating the pulse laser.
- the pattern 406 is recorded at an arbitrary pitch on the resist layer on the outer peripheral surface of the roll-shaped member 401 in the rotation direction. This is the pitch Py in the first direction D1 in the roll-to-roll nanoimprint mold.
- the processing head portion 403 is displaced in the long-axis direction.
- the pitches Py and Px of the pattern 406 are very small on the order of nanometers, so that the first direction when viewed in the major axis direction while maintaining the pitch Py in the first direction D1.
- a columnar pattern in which the shift amount in the direction D1 is shifted can be formed.
- the pitches Py and Px of the pattern 406 are very small compared to the circumferential length of the roll-shaped member 401, the first direction D1 and the second direction D2 are substantially orthogonal.
- the roll-shaped member 401 is a member formed in a cylindrical shape and provided with a rotation shaft, and as a material, a metal, a carbon core, glass, quartz, or the like can be applied. Since the roll-shaped member 401 requires processing accuracy capable of high rotation, the material is preferably a metal, a carbon core, or the like. Furthermore, only the cylindrical surface portion to be laser-exposed can be coated with a different material. In particular, when using a heat-reactive resist, it is preferable to apply a material having a lower thermal conductivity than metal in order to enhance the heat insulation effect, and examples thereof include glass, quartz, oxide, and nitride. It is also possible to use the layer covering the cylindrical surface as an etching layer for etching using a resist layer described later as a mask.
- the resist that covers the roll-shaped member 401 is not particularly limited as long as it is exposed by laser light, and a photo-curing resist, a light amplification resist, a thermal reaction resist, or the like can be applied.
- a heat-reactive resist is preferable because a pattern can be formed at a wavelength smaller than the wavelength of laser light.
- the heat-reactive resist is preferably an organic resist or an inorganic resist.
- the resist layer formed of these resists may have a single layer structure or a multilayer structure in which a plurality of resist layers are combined.
- the type of resist to be selected can be changed as appropriate depending on the process, required processing accuracy, and the like.
- an organic resist can be applied with a roll coater or the like when forming a resist layer that covers the roll-shaped member 401, thereby simplifying the process.
- it since it is applied on the sleeve, there is a limit to the viscosity of the resist, and it is difficult to apply coating thickness accuracy and control, or to coat multiple layers.
- the inorganic resist is preferably provided with a resist layer covering the roll-like member 401 by a vapor phase method such as a resistance heating vapor deposition method, an electron beam sputtering method, or a CVD method. Since these methods are basically vacuum processes, it takes a lot of man-hours to form them on the sleeve, but the film thickness can be controlled with high accuracy and can be easily laminated in multiple layers.
- a vapor phase method such as a resistance heating vapor deposition method, an electron beam sputtering method, or a CVD method. Since these methods are basically vacuum processes, it takes a lot of man-hours to form them on the sleeve, but the film thickness can be controlled with high accuracy and can be easily laminated in multiple layers.
- the inorganic resist material can be variously selected depending on the reaction temperature.
- examples of the inorganic resist material include Al, Si, P, Ni, Cu, Zn, Ga, Ge, As, Se, In, Sn, Sb, Te, Pb, Bi, Ag, Au, and alloys thereof.
- the inorganic resist materials are Mg, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Sr, Y, Zr, Nb, Mo.
- pre-heating for processing the resist at a temperature lower than that at the time of pattern formation may be performed before exposure for forming the following pattern.
- the pattern resolution at the time of pattern formation can be improved.
- the details of the mechanism by which the pattern resolution is improved by preheating are unknown, but if the change in the material that forms the resist layer due to the thermal energy of the heat-reactive resist material is based on multiple reactions, the preheating causes a reaction other than the reaction during pattern formation. It is presumed that the pattern formation reaction is simplified and the pattern resolution is improved by terminating in advance.
- the method of preheating the resist covering the roll-shaped member 401 is not particularly limited, and the output is lower than the method of heating the entire roll-shaped member 401 or patterning the roll-shaped member 401 with a laser. Examples include a method of scanning the entire roll surface and irradiating the resist with thermal energy.
- the diameter of each dot forming the pattern is The pitch Py and / or the pitch Px is preferably increased or decreased corresponding to the pitch Px.
- the clear mechanism by which the dot diameter increases or decreases corresponding to the pitch is unknown, but is estimated as follows.
- the material forming the resist layer is changed by the thermal energy of the laser irradiated to the irradiated portion, and the pattern is formed by changing the etching characteristics.
- the irradiated heat is not completely used for the change of the resist layer, but a part of the heat is stored and transferred to an adjacent region. Therefore, the heat energy in the adjacent region is added with the heat transfer energy from the adjacent region in addition to the irradiation energy.
- the contribution of this heat transfer energy cannot be ignored, and the contribution of heat transfer is inversely proportional to the distance between dots forming the pattern, so the resulting pattern diameter is the distance between adjacent dots. Affected by.
- the inter-dot distance changes due to phase modulation, the above-mentioned contribution of heat transfer energy differs from dot to dot. If the inter-dot distance is wide, the contribution of heat transfer energy becomes small and the dot diameter becomes small. Thus, if the distance between dots is narrow, the contribution of heat transfer energy increases, and the dot diameter increases.
- the processing depth of the pattern is controlled, as described above, based on the reference signal synchronized with the rotation.
- the height of each dot forming a pattern is preferably increased or decreased corresponding to the pitch Py and / or the pitch Px.
- the etching depth increases or decreases according to the dot diameter.
- the etching depth increases, and when the dot diameter decreases, the etching depth tends to decrease.
- the etching technique is remarkable in dry etching. This is presumably because the etchant is not exchanged or the etching product is not rapidly removed.
- the dot diameter decreases when the inter-dot distance is wide, and the dot diameter increases when the inter-dot distance is narrow. Since the etching depth tends to increase or decrease depending on the dot diameter, as a result, when the inter-dot distance is large, the dot depth becomes shallow, and when the inter-dot distance is narrow, the dot depth becomes deep.
- a roll-to-roll nanoimprint mold may be applied as it is using a resist layer covering roll-shaped member 401, or the surface of roll-shaped member 401 is etched using the resist layer as a mask. A pattern may be formed.
- the processing depth of the pattern can be freely controlled, and the thickness of the heat-reactive resist layer can be selected to an optimum thickness for processing. That is, the processing depth can be freely controlled by controlling the thickness of the etching layer. Further, since the processing depth can be controlled by the etching layer, the heat-reactive resist layer may be selected to have a thickness that can be easily exposed and developed.
- the laser used for the processing head unit 403 that performs exposure preferably has a wavelength of 150 nm to 550 nm. Moreover, it is preferable to use a semiconductor laser from the viewpoint of miniaturization of wavelength and availability.
- the wavelength of the semiconductor laser is preferably 150 nm or more and 550 nm or less. This is because when the wavelength is shorter than 150 nm, the output of the laser becomes small and it is difficult to expose the resist layer covering the roll-shaped member 401. On the other hand, when the wavelength is longer than 550 nm, the laser spot diameter cannot be made 500 nm or less, and it is difficult to form a small exposed portion.
- gas lasers of XeF, XeCl, KrF, ArF, and F 2 are preferable because the wavelengths are as short as 351 nm, 308 nm, 248 nm, 193 nm, and 157 nm and can be condensed into a very small spot size.
- a second harmonic, a third harmonic, and a fourth harmonic of an Nd: YAG laser can be used as a laser used for the processing head unit 403.
- the wavelengths of the second harmonic, third harmonic, and fourth harmonic of the Nd: YAG laser are 532 nm, 355 nm, and 266 nm, respectively, and a small spot size can be obtained.
- the rotational position accuracy of the roll-shaped member 401 is very high, and the optical of the laser is set so that the surface of the member is first within the depth of focus. Manufacture is easy if the system is adjusted. However, it is very difficult to maintain roll dimensional accuracy and rotational accuracy that are suitable for nanoimprinting. Therefore, it is preferable that the laser used for exposure is focused by the objective lens and the surface of the roll-shaped member 401 is autofocused so that it is constantly present in the depth of focus.
- Rotation control unit 402 is not particularly limited as long as it is a device having a function of rotating roll-shaped member 401 about the center of the roll, and a spindle motor or the like is suitable, for example.
- the moving mechanism unit 404 that moves the processing head unit 403 in the major axis direction of the roll-shaped member 401 is not particularly limited as long as the processing head unit 403 can be moved at a controlled speed, and a linear servo motor or the like is preferable. Can be mentioned.
- the exposure pattern formed on the surface of the roll-shaped member 401 is phase-modulated based on a reference signal synchronized with the rotation of the rotation control unit 402 (for example, the rotation of the spindle motor).
- the position of the exposure unit is controlled by the exposure control unit 405 based on the pulse signal.
- the reference signal an output pulse from an encoder synchronized with the rotation of the spindle motor can be used.
- the pulse signal phase-modulated based on the reference signal synchronized with the rotation can be controlled as follows, for example.
- FIG. 27 is an explanatory diagram for explaining an example in which the reference pulse signal and the modulation pulse signal are set using the Z-phase signal of the spindle motor as the reference signal in the exposure apparatus for forming the semiconductor light emitting device substrate according to the present embodiment.
- the relationship between the Z-phase signal of the spindle motor, the reference pulse signal, and the modulation pulse signal will be described with reference to FIGS. 27A to 27C.
- a pulse signal with a frequency of m times (an integer of m> 2) is a reference pulse signal with a Z-phase signal as a reference, and a pulse signal with a frequency of n times (an integer of m / n> k and k> 1). It becomes a modulated pulse signal. Since both the reference pulse signal and the modulation pulse signal are integer multiples of the frequency of the Z-phase signal, an integer pulse signal exists within the time that the roll-shaped member 401 makes one rotation around the central axis.
- FIG. 28 is an explanatory diagram for explaining an example in which a phase modulation pulse signal is set from a reference pulse signal and a modulation pulse signal in an exposure apparatus for forming a semiconductor light emitting element substrate according to the present embodiment.
- the relationship between the reference pulse signal, the modulation pulse signal, and the phase modulation pulse signal will be described with reference to FIG.
- a phase modulation pulse signal is obtained.
- the reference pulse frequency fY0 Asin ( ⁇ 0t + ⁇ 0)
- fYL Bsin ( ⁇ 1t + ⁇ 1)
- fY Asin ( ⁇ 0t + ⁇ 0 + Csin ( ⁇ 1t)) (9)
- the phase modulation pulse signal fY ′ can also be obtained by adding a sine wave obtained from the modulation pulse signal to the reference pulse frequency fY0.
- fY ′ fY0 + C′sin (t ⁇ fYL / fY0 ⁇ 2 ⁇ ) (10)
- the wavelength LY of the phase modulation pulse signal can be obtained by adding a sine wave obtained from the wavelength LYL of the modulation pulse signal to the pulse wavelength LY0 of the reference pulse.
- the obtained phase modulation pulse signal is a signal in which the pulse interval of the reference pulse signal is periodically increased or decreased according to the signal interval of the modulation pulse signal.
- a sine wave obtained from a modulation pulse signal having two periods is added to the reference pulse frequency fY0 to obtain a phase modulation pulse signal fY ′′.
- the two modulation frequencies fYL in Expression (11). , FYL ′ are two long periods in the semiconductor light emitting device of the present embodiment.
- the modulation pulse signal is adjusted so as to have a long period of 1 ⁇ m or more, or 6 times or more of the optical wavelength of the first light and 6 times or more of the optical wavelength of the second light. Control to obtain a phase modulated pulse signal.
- the pulse signal of the laser exposure by the processing head unit 403 is controlled using the reference pulse signal having a constant frequency, not the phase-modulated pulse signal, and the processing head unit 403 of the moving mechanism unit 404 is controlled. It is good also as a structure which increases / decreases a moving speed periodically. In this case, for example, as shown in FIG. 29, the moving speed of the machining head unit 403 is periodically increased or decreased.
- FIG. 29 is an explanatory diagram illustrating an example of the moving speed of the processing head unit that irradiates the laser beam in the exposure apparatus that forms the substrate for a semiconductor light emitting device according to the present embodiment.
- the movement speed illustrated in FIG. 29 is an example of the movement speed of the reference movement speed ⁇ ⁇ .
- This moving speed is preferably synchronized with the rotation of the roll-shaped member 401.
- the moving speed is controlled so that the speed in the Z-phase signal becomes the speed shown in FIG.
- the pattern 406 (see FIG. 26) is controlled by periodic phase modulation, but the pattern 406 can also be formed by random phase modulation instead of periodic.
- the pitch Py is inversely proportional to the pulse frequency. Therefore, when random frequency modulation is performed on the pulse frequency so that the maximum phase shift is 1/10, the pitch Py is 1 / of the pitch Py. It is possible to obtain a pattern having ten fluctuation ranges ⁇ 1 (maximum fluctuation range) with the pitch Py increasing or decreasing randomly.
- the modulation pulse signal may be controlled by a reference signal having a frequency of a plurality of times such as every roll, or only by the initial reference signal set at the initial stage of exposure. May be.
- the control is performed only with the initial reference signal
- the rotation number of the rotation control unit 402 is modulated
- the exposure pulse signal is phase-modulated. This is because nano-order rotation control is performed, and even a slight potential fluctuation of the rotation control unit 402 causes nano-order pitch fluctuation and is integrated.
- a pattern pitch of 500 nm pitch if the roll outer peripheral length is 250 mm, the laser exposure is 500,000 times, and even if the deviation is 1 nm every 10,000 times, the deviation is 50 nm.
- the fine structure having the arrangement shown in FIGS. 14 and 17 can be created by adjusting the control frequency of the reference signal.
- the control frequency of the reference signal is lowered, and when the fine structure having the arrangement shown in FIG. 17 is formed, the control frequency of the reference signal is increased.
- the phase (position) of the corresponding dot in the second direction is aligned, and in the arrangement shown in FIG. 14, the phase (position) of the corresponding dot in the second direction is shifted.
- Arise The arrangement relationship shown in FIGS. 16 and 18 is the same.
- the exposure apparatus 400 develops the roll-shaped member 401 on which the resist layer provided on the surface is exposed, and etches the etching layer by dry etching using the developed resist layer as a mask. When the residual resist layer is removed after etching, a roll-to-roll nanoimprint mold can be obtained.
- the pattern 406 obtained as described above is not particularly limited as a method for transferring the pattern 406 to a predetermined substrate for a semiconductor light emitting element to obtain a substrate for a semiconductor light emitting element.
- the pattern 406 can be transferred to the semiconductor light emitting device substrate by transferring the pattern onto the surface of the semiconductor light emitting device substrate and etching the semiconductor light emitting device substrate by dry etching using the transfer pattern portion as a mask.
- the roll-shaped member 401 on which the pattern 406 is formed is used as a cylindrical mold (roll-to-roll nanoimprint mold).
- a resist layer made of an organic material is formed on the surface side of the substrate for a semiconductor light emitting element, a cylindrical mold is pressed against the resist layer, and the pattern 406 is transferred to the resist layer.
- a fine concave structure layer can be formed on the surface side of the substrate for a semiconductor light emitting element, and a substrate for a semiconductor light emitting element can be obtained.
- the pattern 406 is once transferred to a film to form a resin mold, and then the resin mold is used.
- a method of obtaining a substrate for a semiconductor light emitting device by forming a pattern on the substrate for a semiconductor light emitting device by a nanoimprint lithography method may also be mentioned. According to this method, the mold utilization efficiency can be increased and the flatness of the semiconductor light emitting device substrate can be absorbed. Therefore, as a method for transferring the pattern to the semiconductor light emitting device substrate, a nanoimprint lithography method using a resin mold is used. More preferred.
- the method for transferring the pattern 406 from the cylindrical mold to the resin mold is not particularly limited, and for example, a direct nanoimprint method can be applied.
- a direct nanoimprint method thermal nanoimprint is performed by filling the pattern 406 of the cylindrical mold with a thermosetting resin while heating at a predetermined temperature, releasing the cured thermosetting resin after cooling the cylindrical mold, and transferring it.
- the photocurable resin filled in the cylindrical mold pattern 406 is irradiated with light of a predetermined wavelength to cure the photocurable resin, and then the cured photocurable resin is released from the cylindrical mold. And photo-nanoimprinting method for transfer.
- cylindrical mold (roll-shaped member 401) is a seamless cylindrical mold, it is particularly suitable for continuously transferring a resin mold by roll-to-roll nanoimprint.
- an electroformed mold is produced by electroforming from a resin mold to which the pattern 406 is transferred, and a pattern is formed by nanoimprint lithography using this electroformed mold.
- the electroformed mold it is preferable in terms of extending the life of the cylindrical mold as the original mold, and even in the method of forming the electroformed mold once, the flatness of the substrate for the semiconductor light emitting element can be absorbed.
- a method of forming a resin mold is preferred.
- the resin mold method is preferable because repeated transfer is easy.
- “repetitive transfer” means (1) producing a plurality of transferred concavo-convex pattern transfer products from a resin mold (+) having a concavo-convex pattern shape, or (2) a curable resin composition in particular.
- a transfer material When used as a transfer material, obtain an inverted transfer body (-) from the resin mold (+), and then use the transfer body (-) as a resin mold (-) to obtain an inverted transfer body (+).
- (+) indicates a male type
- (-) indicates a female type.
- a pattern is formed on the surface side of the substrate for a semiconductor light emitting element by the resist layer, and then irregularities are formed on the substrate for the semiconductor light emitting element by etching using the resist layer as a mask.
- the etching method is not particularly limited as long as irregularities can be formed on the substrate for a semiconductor light emitting device using the resist layer as a mask, and wet etching, dry etching, and the like can be applied.
- the dry etching method is preferable because the unevenness of the substrate for a semiconductor light emitting device can be formed deeply.
- anisotropic dry etching is preferable, and ICP-RIE and ECM-RIE are preferable.
- the reaction gas used for dry etching is not particularly limited as long as it reacts with the material of the substrate for a semiconductor light emitting device, but BCl 3 , Cl 2 , CHF 3 , or a mixed gas thereof is preferable, and appropriately , Ar, O 2 and the like can be mixed.
- a pattern is transferred to the surface of a predetermined transparent conductive film by nanoimprint lithography, and the pattern 406 is formed into a transparent conductive film by etching the transparent conductive film by etching using the transfer pattern portion as a mask. Can be transferred.
- a film having a refractive index substantially equivalent to that of the transparent conductive film is formed on the surface of the transparent conductive film, and the pattern 406 is transferred to the film in the same manner as described above, so that the semiconductor in the semiconductor light emitting device of this embodiment A light emitting element can be obtained.
- Example 1 Cylindrical mold production (preparation of resin mold production mold)
- a cylindrical quartz glass roll having a diameter of 80 mm and a length of 50 mm was used as the substrate for the semiconductor light emitting device of the cylindrical mold.
- a fine structure fine concavo-convex structure was formed on the surface of this cylindrical quartz glass roll by the direct drawing lithography method using a semiconductor pulse laser by the following method.
- a resist layer was formed on the fine structure of the quartz glass surface by a sputtering method.
- the sputtering method was performed using CuO as a target (resist layer) with a power of RF 100 W.
- the film thickness of the resist layer after film formation was 20 nm.
- the target pitch Py and the effective pitch Py ′ are Py ⁇ Py ′, but since L / Py ⁇ 10 7 ,
- / Py′ ⁇ 10 ⁇ 7 , which is substantially Can be treated as equivalent to Similarly, for the long period unit PyL, the effective long period unit PyL ′ is obtained by the following equation (14) so that L / PyL is an integer. L / PyL ′ n (n is an integer) (14)
- the pulse frequency fy at the elapsed time t from the Z-phase signal of the spindle motor is determined as in equation (17).
- fy fy0 + ⁇ 1 ⁇ sin (t ⁇ (fyL / fy0) ⁇ 2 ⁇ ) (17)
- Vx Vx0 + V ⁇ 2 ⁇ sin (Px / PxL ⁇ t ⁇ 2 ⁇ ) (19)
- V ⁇ 2 is a speed fluctuation width in the long cycle unit PxL in the x-axis direction
- the following formula is obtained by the pitch fluctuation width ⁇ 2 in the long cycle unit PxL, the pitch Px in the X-axis direction, and the reference feed speed Vx0 in the axial direction.
- V ⁇ 2 ⁇ 2 ⁇ Vx0 / Px
- Durasurf registered trademark, the same applies hereinafter
- HD-1101Z (Daikin Chemical Industry Co., Ltd.) was applied to the obtained two types of cylindrical quartz glass roll surfaces (transfer mold) and heated at 60 ° C. for 1 hour. Then, it was left still at room temperature for 24 hours and fixed. Thereafter, it was washed 3 times with Durasurf HD-ZV (manufactured by Daikin Chemical Industries, Ltd.) and subjected to mold release treatment.
- a reel-shaped resin mold was produced from the obtained cylindrical mold.
- OPTOOL registered trademark, hereinafter the same
- DAC manufactured by Daikin Industries
- trimethylolpropane triacrylate manufactured by Toagosei Co., Ltd., M350
- Irgacure registered trademark, hereinafter the same
- Ciba manufactured by Ciba
- this photo-curing resin is applied to the easily adhesive surface of a PET film (A4100, manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 ⁇ m) by microgravure coating (manufactured by Yasui Seiki Co., Ltd.) so that the coating film thickness becomes 6 ⁇ m. Applied.
- a PET film coated with a photocurable resin is pressed against a cylindrical mold (cylindrical mold) with a nip roll (0.1 MPa), and integrated in the air at a temperature of 25 ° C. and a humidity of 60% under the center of the lamp.
- UV curing is performed continuously using a UV exposure device (H bulb, manufactured by Fusion UV Systems Japan Co., Ltd.), and the surface has a fine structure.
- a reel-shaped transparent resin mold (length 200 m, width 300 mm) that was reversely transferred was obtained.
- Resin mold A X-axis direction pitch Px: 398 nm Variation width ⁇ 2 with respect to pitch Px in the X-axis direction: 40 nm Long period unit PxL in the X-axis direction of the fluctuation range ⁇ 2: 3.98 ⁇ m Y-axis direction pitch Py: 460 nm Variation width ⁇ 1: 46 nm with respect to the pitch Py in the Y-axis direction Long period unit PyL in the Y-axis direction of the fluctuation width ⁇ 1: 4.60 ⁇ m
- Resin mold B X-axis direction pitch Px: 398 nm Variation width ⁇ 2 with respect to pitch Px in the X-axis direction: 40 nm Long period unit PxL in the X-axis direction of the fluctuation width ⁇ 2: 1.99 ⁇ m Y-axis direction pitch Py: 460 nm Variation width ⁇ 1: 46 nm with respect to the pitch Py in the Y-axis direction Long period unit
- This photo-curing resin was applied to the easily adhesive surface of a PET film (A4100, manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 ⁇ m) by microgravure coating (manufactured by Yurai Seiki Co., Ltd.) so as to have a coating film thickness of 2 ⁇ m.
- a PET film coated with a photocurable resin is pressed onto the reel-shaped resin mold with a nip roll (0.1 MPa), and the integrated exposure amount under the center of the lamp is 600 mJ in the air at a temperature of 25 ° C. and a humidity of 60%. / Cm 2 , UV curing is performed using a UV exposure device (Fusion UV Systems Japan Co., Ltd., H bulb), and photocuring is performed continuously. Resin mold A and resin mold B are formed on the surface. The sheet-like transparent resin mold A and the sheet-like transparent resin mold B (length: 200 mm, width: 300 mm) were obtained.
- a mask material was applied by spin coating (2000 rpm, 20 seconds) onto a substrate for a C-plane sapphire semiconductor light-emitting element having a ⁇ 2 ”thickness of 0.33 mm, and a resist layer was formed.
- Photosensitive resin composition As the photosensitive resin composition, 3-ethyl-3 ⁇ [(3-ethyloxetane-3-yl) methoxy] methyl ⁇ oxetane (OXT-221, manufactured by Toagosei Co., Ltd.) 20 parts by weight, 3 ′, 4′- Epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl (manufactured by Wako Pure Chemical Industries) 80 parts by weight, phenoxydiethylene glycol acrylate (Aronix (registered trademark, hereinafter the same) M-101A, manufactured by Toagosei Co., Ltd.) 50 parts by weight, ethylene oxide modified 50 parts by weight of bisphenol A diacrylate (Aronix M-211B, manufactured by Toa Gosei Co., Ltd.), 8 parts by weight of DTS-102 (manufactured by Midori Chemical Co., Ltd.), 1,9-dibutoxyanthracene
- the transparent resin mold B was cut into 70 mm ⁇ 70 mm ( ⁇ 70 mm) and bonded onto the sapphire semiconductor light-emitting element substrate on which the resist layer was formed.
- a film bonding apparatus (TMS-S2) manufactured by Suntech Co., Ltd. was used, and bonding was performed with a bonding nip force of 90 N and a bonding speed of 1.5 m / s.
- the pasted and integrated transparent resin mold / resist layer / sapphire semiconductor light emitting element substrate was sandwiched between two transparent silicone plates (hardness 20) of 70 mm ⁇ t10 mm.
- GaN low-temperature buffer layer (2) n-type GaN layer, (3) n-type AlGaN cladding layer, (4) InGaN light-emitting layer (MQW) on the obtained sapphire semiconductor light-emitting element substrate by MOCVD (5)
- a p-type AlGaN cladding layer, (6) a p-type GaN layer, and (7) an ITO layer were successively laminated.
- Irregularities on the substrate for a sapphire semiconductor light-emitting element were (2) film-forming conditions for filling and planarizing when the n-type GaN layer was laminated.
- a mask material was applied to the ITO layer formed on the surface by a spin coating method (2000 rpm, 20 seconds) to form a resist layer.
- a coating solution was prepared by diluting with a propylene glycol monomethyl ether so that the solid content of the photosensitive resin composition was 5% by weight.
- the transparent resin mold A was cut into 70 mm ⁇ 70 mm ( ⁇ 70 mm) and pasted on the ITO on which the resist layer was formed.
- a film bonding apparatus (TMS-S2) manufactured by Suntech Co., Ltd. was used, and bonding was performed with a bonding nip force of 90 N and a bonding speed of 1.5 m / s.
- the transparent resin mold / resist layer / ITO layer / laminated semiconductor layer / sapphire semiconductor light-emitting device base material bonded and integrated was sandwiched between two transparent silicone plates (hardness 20) of 70 mm ⁇ t10 mm.
- the optical wavelength in the ITO layer (refractive index: 2.0) with respect to 460 nm emitted from the semiconductor layer of the ITO layer was 230 nm. Further, the electrode pad was attached by etching.
- the semiconductor light emitting device obtained as described above was placed in a package and electrically connected to the electrode pad via an Au wire. Next, the inside of the package was filled with a wavelength conversion member in which CaAlSiN 3 : Eu (fluorescent material) having a dominant wavelength of 650 nm was mixed with silicone resin.
- Example 1 shows the light emission output ratio when the light emission output from the semiconductor light emitting device of Comparative Example 1 is 1.
- Example 1 as compared with Comparative Example 1, it was found that no variation specific to diffraction was observed in the light emission from the semiconductor light emitting element, and there was almost no emission angle dependency.
- Cylindrical mold C Semiconductor laser wavelength for exposure: 405 nm Exposure laser power: 3.5mW Pitch Px in the X axis direction: 260 nm Variation width ⁇ 2 with respect to pitch Px in the X-axis direction: 26 nm Long period unit PxL1 in the X-axis direction of the fluctuation width ⁇ 2: 2.60 ⁇ m Y-axis direction pitch Py: 300 nm Variation width ⁇ 1: 30 nm with respect to pitch Py in the Y-axis direction Long cycle unit PyL1 in the Y-axis direction of the fluctuation width ⁇ 1: 2.60 ⁇ m Long-period unit PyL2 in the Y-axis direction of the fluctuation width ⁇ 1: 1.30 ⁇ m
- the target pitch Py and the effective pitch Py ′ are Py ⁇ Py ′, but since L / Py ⁇ 10 7 ,
- L / PyL1 ′ n (n is an integer) (21)
- L / PyL2 ′ m (m is an integer) (22)
- the reference pulse frequency fy0 and the modulation frequency fyL are calculated by the equations (15), (23), and (24).
- fy0 s / Py ′
- fyL1 s / PyL1 ′
- fyL2 s / PyL2 ′
- the pulse frequency fy at the elapsed time t from the Z-phase signal of the spindle motor is determined as the equation (25).
- fy fy0 + ⁇ 1 ⁇ sin (t ⁇ (fyL1 / fy0) ⁇ 2 ⁇ + t ⁇ (fyL2 / fy0) ⁇ 2 ⁇ ) (25)
- Resin mold C Semiconductor laser wavelength for exposure: 405 nm Exposure laser power: 3.5mW Pitch Px in the X axis direction: 260 nm Variation width ⁇ 2 with respect to pitch Px in the X-axis direction: 26 nm Long period unit PxL1 in the X-axis direction of the fluctuation width ⁇ 2: 2.60 ⁇ m Y-axis direction pitch Py: 300 nm Variation width ⁇ 1: 30 nm with respect to pitch Py in the Y-axis direction Long cycle unit PyL1 in the Y-axis direction of the fluctuation width ⁇ 1: 2.60 ⁇ m Long-period unit PyL2 in the Y-axis direction of the fluctuation width ⁇ 1: 1.30 ⁇ m
- the pattern of the resin mold C was transferred to the surface of the base material for the sapphire semiconductor light emitting device to produce a semiconductor light emitting device.
- the semiconductor light emitting device obtained as described above was placed in a package and electrically connected to the electrode pad via an Au wire.
- the inside of the package was filled with a wavelength conversion member in which CaAlSiN 3 : Eu (fluorescent material) having a dominant wavelength at 650 nm and ⁇ -SiAlON: Eu (fluorescent material) having a dominant wavelength at 530 nm were mixed in silicone resin.
- Table 4 shows the light emission output ratio of Example 2 at 20 mA. As in Example 1, no luminescence with glare peculiar to diffraction was observed, and there was almost no emission angle dependency.
- Example 3 A semiconductor light emitting device similar to that of Example 2 was placed in a package and electrically connected to the electrode pad via an Au wire. Next, the inside of the package was filled with a wavelength conversion member in which a fluorescent material having the following main wavelength was mixed with silicone resin. 530 nm ⁇ -SiAlON: Eu 580 nm Ca- ⁇ -SiAlON: Eu 650 nm CaAlSiN 3 : Eu
- Table 4 shows the light emission output ratio of Example 3 at 20 mA.
- Example 3 as in Example 1 and Example 2, no luminescence with glare peculiar to diffraction was observed, and there was almost no emission angle dependency.
- Example 2 In the same manner as in Example 1, a nano-patterned fine structure (fine concavo-convex structure) was formed on the quartz glass surface by a direct writing lithography method using a semiconductor laser.
- the pitches in the X-axis direction and the Y-axis direction are the same, and the hexagonal array has no pitch variation.
- Example 2 Thereafter, a semiconductor light emitting device was formed by the same method as in Example 1, and the light emission output was measured. In light emission from the obtained semiconductor light emitting device, diffracted light peculiar to the diffraction structure was strongly observed, and the light emission angle distribution was large.
- Example 2 Thereafter, a semiconductor light emitting device was formed by the same method as in Example 1, and the light emission output was measured. In light emission from the obtained semiconductor light emitting device, diffracted light peculiar to the diffraction structure was strongly observed, and the light emission angle distribution was large.
- the optical wavelength had a period of 6 times or more and two or more periods.
- Table 4 shows the light emission output ratio of each sample when the output of Comparative Example 1 is 1. From Table 4, according to the semiconductor generator according to the present embodiment (Examples 1 to 3), the conventional flat substrate for a sapphire semiconductor light emitting device (Comparative Example 1), 6 times the conventional optical wavelength The number of dislocation defects in the semiconductor layer formed on the sapphire semiconductor light-emitting element substrate is reduced as compared to the base material for sapphire semiconductor light-emitting element (Comparative Example 2) having a two-dimensional photonic crystal without the above period. In addition, the light extraction efficiency can be improved by eliminating the waveguide mode by light scattering caused by the irregular pattern with disordered periodicity, and thus a semiconductor light emitting device having high light emission efficiency can be obtained. all right. Further, it is found that there is almost no angle dependency in the light emission characteristics from the light emitting element, which is a light emitting element suitable for industrial practical use.
- the angle dependency was evaluated as x when the light emission state at 20 mA was visually observed and strong light emission was observed at a specific angle, or when the light emission color changed depending on the observation angle, as the angle dependency was strong.
- Example 4 (Formation of laminated semiconductor) (1) GaN low-temperature buffer layer, (2) n-type GaN layer, (3) n-type AlGaN cladding layer, (4) InGaN light-emitting layer (MQW), (5) ) A p-type AlGaN cladding layer, (6) a p-type GaN layer, and (7) an ITO layer were successively laminated.
- MQW InGaN light-emitting layer
- a mask material was applied to the ITO layer formed on the surface by a spin coating method (2000 rpm, 20 seconds) to form a resist layer.
- a coating solution was prepared by diluting with a propylene glycol monomethyl ether so that the solid content of the photosensitive resin composition was 5% by weight.
- the transparent resin mold C was cut into 70 mm ⁇ 70 mm ( ⁇ 70 mm) and pasted on the ITO on which the resist layer was formed.
- a film bonding apparatus (TMS-S2) manufactured by Suntech Co., Ltd. was used, and bonding was performed with a bonding nip force of 90 N and a bonding speed of 1.5 m / s.
- the pasted and integrated transparent resin mold / resist layer / ITO layer / laminated semiconductor layer / sapphire semiconductor light emitting device substrate was sandwiched between two transparent silicone plates (hardness 20) of 70 mm ⁇ t10 mm.
- the semiconductor light emitting device obtained as described above was placed in a package and electrically connected to the electrode pad via an Au wire.
- the surface of the microstructure layer is sealed with a silicone resin (refractive index of 1.53) as an intermediate material so as to cover only the surface of the microstructure layer of the semiconductor light emitting element disposed in the package, and then The silicone resin was cured.
- the inside of the package was filled with a wavelength conversion member in which a silicone resin (refractive index) as a first material and a fluorescent material having the following main wavelength were mixed.
- the average particle size of the fluorescent material used was 200 nm.
- CaAlSiN 3 Eu
- Example 5 When the semiconductor light-emitting device obtained in the same manner as in Example 4 was sealed in a package, CaAlSiN 3 : Eu (fluorescent material) having a dominant wavelength of 650 nm in the silicone resin (refractive index of 1.5) used in Example 4 ) was mixed only with the wavelength conversion member mixed.
- Table 5 shows the light emission output ratio of each sample when the output of Comparative Example 4 is 1. From Table 5, Example 4 in which a silicone resin as an intermediate material is interposed between the fine structure layer and the wavelength conversion member is more semiconductor than Example 5 in which the fine structure layer is formed in contact with the wavelength conversion member. Since the waveguide mode in the light emitting element can be eliminated, the scattering property of fluorescent light can be increased, and the light extraction efficiency can be increased, a semiconductor light emitting element having high light emission efficiency can be obtained. Furthermore, by forming a two-dimensional photonic crystal having two different periods, the waveguide mode is eliminated and the scattering property is increased, so that it is possible to obtain a semiconductor light emitting device with further improved light extraction efficiency. The light emitting device is suitable for industrial use.
- the internal quantum efficiency IQE is improved in the emitted light by reducing the number of dislocation defects in the semiconductor layer by the fine structure layer provided in the semiconductor light emitting element, and the emitted light In fluorescence, the waveguide mode is eliminated by light scattering, and the light extraction efficiency LEE can be increased. Furthermore, it is possible to efficiently convert the wavelength of primary light emitted from the semiconductor light emitting device efficiently. With these effects, the final light emission efficiency of the semiconductor light emitting device can be improved, and furthermore, the angle dependency of the light emission distribution can be reduced, so that it can be easily applied to industrial practical uses. In addition, the semiconductor light emitting device of the present invention has high luminous efficiency, can effectively use electric power, and can greatly contribute to energy saving.
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Abstract
Description
fa(εa-ε)/(εa+2ε)+fb(εb-ε)/(εb+2ε)=0(A)
n=√ε(B)
Px1<Px2<Px3<…<Pxa>…>Pxn (1)
Px1<Px2<Px3>Px4>Px5>Px6>Px7 (2)
Px1=Px(min)
Px2=Px(min)+δa
Px3=Px(min)+δb=Px(max)
Px4=Px(min)+δc
Px5=Px(min)+δd
Px6=Px(min)+δe
Px7=Px(min)+δf
Dy1<Dy2<Dy3<…<Dya>…>Dyn (3)
Dx1<Dx2<Dx3<…<Dxa>…>Dxn (4)
Hy1<Hy2<Hy3<…<Hya>…>Hyn (5)
Hx1<Hx2<Hx3<…<Hxa>…>Hxn (6)
fY0=Asin(ω0t+φ0) (7)
fYL=Bsin(ω1t+φ1) (8)
fY=Asin(ω0t+φ0+Csin(ω1t)) (9)
fY´=fY0+C´sin(t・fYL/fY0×2π) (10)
fY”=fY0+C”sin(t・fYL/fY0×2π+t・fYL’/fY0×2π) (11)
(円筒状金型作製(樹脂モールド作製用鋳型の作製))
円筒状金型の半導体発光素子用基材としては、直径80mm、長さ50mmの円筒型石英ガラスロールを用いた。この円筒型石英ガラスロール表面に、次の方法により半導体パルスレーザを用いた直接描画リソグラフィ法により微細構造(微細凹凸構造)を形成した。
露光レーザパワー:3.5mW
円筒状金型A:
X軸方向のピッチPx:398nm
X軸方向のピッチPxに対する変動幅δ2:40nm
変動幅δ2のX軸方向の長周期単位PxL :3.98μm
Y軸方向のピッチPy:460nm
Y軸方向のピッチPyに対する変動幅δ1:46nm
変動幅δ1のY軸方向の長周期単位PyL :4.60μm
円筒状金型B
X軸方向のピッチPx:398nm
X軸方向のピッチPxに対する変動幅δ2:40nm
変動幅δ2のX軸方向の長周期単位PxL :1.99μm
Y軸方向のピッチPy:460nm
Y軸方向のピッチPyに対する変動幅δ1:46nm
変動幅δ1のY軸方向の長周期単位PyL :2.33μm
L=T×s (12)
L/Py’=m (mは整数) (13)
L/PyL’=n (nは整数) (14)
fy0=s/Py’ (15)
fyL=s/PyL’ (16)
fy=fy0+δ1×sin(t×(fyL/fy0)×2π)(17)
Vx0=Px/T (18)
Vx=Vx0+Vδ2・sin(Px/PxL×t×2π)(19)
Vδ2=δ2×Vx0/Px (20)
得られた2種類の円筒状の石英ガラスロール表面(転写用モールド)に対し、デュラサーフ(登録商標、以下同じ)HD-1101Z(ダイキン化学工業社製)を塗布し、60℃で1時間加熱後、室温で24時間静置、固定化した。その後、デュラサーフHD-ZV(ダイキン化学工業社製)で3回洗浄し、離型処理を施した。
X軸方向のピッチPx:398nm
X軸方向のピッチPxに対する変動幅δ2:40nm
変動幅δ2のX軸方向の長周期単位PxL :3.98μm
Y軸方向のピッチPy:460nm
Y軸方向のピッチPyに対する変動幅δ1:46nm
変動幅δ1のY軸方向の長周期単位PyL :4.60μm
樹脂モールドB:
X軸方向のピッチPx:398nm
X軸方向のピッチPxに対する変動幅δ2:40nm
変動幅δ2のX軸方向の長周期単位PxL :1.99μm
Y軸方向のピッチPy:460nm
Y軸方向のピッチPyに対する変動幅δ1:46nm
変動幅δ1のY軸方向の長周期単位PyL :2.33μm
装置;HITACHI s-5500
加速電圧;10kV
MODE;Normal
次に、OPTOOL DAC HP(ダイキン工業社製)、トリメチロールプロパントリアクリレート(東亞合成社製 M350)、及びIrgacure 184(Ciba社製)を重量部で10:100:5の割合で混合して光硬化性樹脂を調製した。この光硬化性樹脂をPETフィルム(A4100、東洋紡社製:幅300mm、厚さ100μm)の易接着面にマイクログラビアコーティング(廉井精機社製)により、塗布膜厚2μmになるように塗布した。
φ2”厚さ0.33mmのC面サファイア半導体発光素子用基材上に、マスク材料をスピンコーティング法(2000rpm、20秒)により塗布し、レジスト層を形成した。マスク材料は、感光性樹脂組成物の固形分を5重量%になるようにプロピレングリコールモノメチルエーテルで希釈した塗布溶液を作成した。
感光性樹脂組成物としては、3-エチル-3{[(3-エチルオキセタン-3-イル)メトキシ]メチル}オキセタン(OXT-221、東亜合成社製)20重量部、3’、4’-エポキシシクロヘキサンカルボン酸3、4-エポキシシクロヘキシルメチル(和光純薬社製)80重量部、フェノキシジエチレングリコールアクリレート(アロニックス(登録商標、以下同じ)M-101A、東亜合成社製)50重量部、エチレンオキサイド変性ビスフェノールAジアクリレート(アロニックスM-211B、東亜合成社製)50重量部、DTS-102(みどり化学社製)8重量部、1、9-ジブトキシアントラセン(アントラキュア(登録商標)UVS-1331、川崎化成社製)1重量部、Irgacure 184(Ciba社製)5重量部及びOPTOOL DAC HP(20%固形分、ダイキン工業社製)4重量部、を混合して使用した。
反応性イオンエッチング装置(RIE-101iPH、サムコ株式会社製)を用い、下記エッチング条件でサファイア半導体発光素子用基材をエッチングした。
エッチングガス:Cl2/(Cl2+BCl3)=0.1
ガス流量:10sccm
エッチング圧力:0.1Pa
アンテナ:50w
バイアス:50w
得られたサファイア半導体発光素子用基材上に、MOCVDにより、(1)GaN低温バッファ層、(2)n型GaN層、(3)n型AlGaNクラッド層、(4)InGaN発光層(MQW)、(5)p型AlGaNクラッド層、(6)p型GaN層、(7)ITO層を連続的に積層した。サファイア半導体発光素子用基材上の凹凸は、(2)n型GaN層の積層時に埋められて、平坦化する製膜条件とした。上記構成により、半導体層からの発光は460nmであり、GaN層(屈折率:2.46)中の光学波長は、187nmであった。
次に、表面に形成されたITO層に、マスク材料をスピンコーティング法(2000rpm、20秒)により塗布し、レジスト層を形成した。マスク材料は、前記感光性樹脂組成物の固形分を5重量%になるようにプロピレングリコールモノメチルエーテルで希釈した塗布溶液を作成した。
反応性イオンエッチング装置(RIE-101iPH、サムコ株式会社製)を用い、下記エッチング条件でITO層をエッチングした。
ガス流量:10sccm
エッチング圧力:0.1Pa
アンテナ:50w
バイアス:50w
上記のように得られた半導体発光素子をパッケージに配置し、電極パッドにAuワイヤを介して電気的に接続した。次に、パッケージ内をシリコーン樹脂に650nmの主波長を有するCaAlSiN3:Eu(蛍光材)を混合した波長変換部材で充填した。
実施例1と同様に作成した円筒状金型を線速度s=1.0m/secで回転させながら、以下の条件で露光した。
露光用半導体レーザ波長:405nm
露光レーザパワー:3.5mW
X軸方向のピッチPx:260nm
X軸方向のピッチPxに対する変動幅δ2:26nm
変動幅δ2のX軸方向の長周期単位PxL1 :2.60μm
Y軸方向のピッチPy:300nm
Y軸方向のピッチPyに対する変動幅δ1:30nm
変動幅δ1のY軸方向の長周期単位PyL1 :2.60μm
変動幅δ1のY軸方向の長周期単位PyL2 :1.30μm
L=T×s (12)
L/Py’=m (mは整数) (13)
L/PyL1’=n (nは整数) (21)
L/PyL2’=m (mは整数) (22)
fy0=s/Py’ (15)
fyL1=s/PyL1’ (23)
fyL2=s/PyL2’ (24)
fy=fy0+δ1×sin(t×(fyL1/fy0)×2π+t×(fyL2/fy0)×2π) (25)
露光用半導体レーザ波長:405nm
露光レーザパワー:3.5mW
X軸方向のピッチPx:260nm
X軸方向のピッチPxに対する変動幅δ2:26nm
変動幅δ2のX軸方向の長周期単位PxL1 :2.60μm
Y軸方向のピッチPy:300nm
Y軸方向のピッチPyに対する変動幅δ1:30nm
変動幅δ1のY軸方向の長周期単位PyL1 :2.60μm
変動幅δ1のY軸方向の長周期単位PyL2 :1.30μm
実施例2と同様の半導体発光素子をパッケージに配置し、電極パッドにAuワイヤを介して電気的に接続した。次に、パッケージ内を、シリコーン樹脂に下記の主波長を有する蛍光材を混合した波長変換部材で充填した。
530nm β-SiAlON:Eu
580nm Ca-α―SiAlON:Eu
650nm CaAlSiN3:Eu
実施例1と同様の条件で通常のフラットなサファイア半導体発光素子用基材上に半導体発光素子を形成した後、実施例1と同様の波長変換部材で封止し発光出力を測定した。
実施例1と同様の方法で、半導体レーザを用いた直接描画リソグラフィ法によりナノパターンの微細構造(微細凹凸構造)を石英ガラス表面に形成した。X軸方向、Y軸方向のピッチは同じで、ピッチ変動がない六方配列とした。
X軸方向のピッチPx:398nm
Y軸方向のピッチPy:460nm
実施例1と同様の方法で、半導体レーザを用いた直接描画リソグラフィ法によりナノパターンの微細構造(微細凹凸構造)を石英ガラス表面に形成した。X軸方向、Y軸方向のピッチは同じで、ピッチ変動がない六方配列とした。
X軸方向のピッチPx:260nm
Y軸方向のピッチPy:300nm
(積層半導体の形成)
サファイア半導体発光素子用基材上に、MOCVDにより、(1)GaN低温バッファ層、(2)n型GaN層、(3)n型AlGaNクラッド層、(4)InGaN発光層(MQW)、(5)p型AlGaNクラッド層、(6)p型GaN層、(7)ITO層を連続的に積層した。上記構成により、半導体層からの発光は460nmであり、ITO層の膜厚は、600nmとした。
次に、表面に形成されたITO層に、マスク材料をスピンコーティング法(2000rpm、20秒)により塗布し、レジスト層を形成した。マスク材料は、前記感光性樹脂組成物の固形分を5重量%になるようにプロピレングリコールモノメチルエーテルで希釈した塗布溶液を作成した。
反応性イオンエッチング装置(RIE-101iPH、サムコ株式会社製)を用い、下記エッチング条件でITO層をエッチングした。
エッチングガス:BCl3
ガス流量:10sccm
エッチング圧力:0.2Pa
アンテナ:150w
バイアス:50w
530nm β-SiAlON:Eu
580nm Ca-α―SiAlON:Eu
650nm CaAlSiN3:Eu
実施例4と同様に得られた半導体発光素子をパッケージ内に封止する際、実施例4に使用したシリコーン樹脂(屈折率1.5)に650nmの主波長を有するCaAlSiN3:Eu(蛍光材)を混合した波長変換部材のみで充填した。
実施例4と同様の条件でサファイア半導体発光素子用基材上に半導体発光素子を形成した後、ITO層表面に微細構造層を設けずに、実施例1と同様の波長変換部材で封止し発光出力を測定した。
Claims (15)
- 少なくとも2層以上の半導体層と、発光層とを積層して構成される積層半導体層を有し、第一の光を発光する半導体発光素子と、
少なくとも前記半導体発光素子の一部を覆い、前記第一の光の少なくとも一部を吸収し、前記第一の光の波長とは異なる第二の光を発光する波長変換部材と、を有して構成される半導体発光装置であって、
前記半導体発光素子は、前記半導体発光素子を構成するいずれかの主面において、面外方向に延在する複数の凸部又は凹部から構成されるドットを含む微細構造層を構成要素として備え、
前記微細構造層は、少なくとも前記ドット間のピッチ、ドット径又はドット高さのいずれかにより制御された二次元フォトニック結晶を構成し、
前記二次元フォトニック結晶は少なくとも、各々1μm以上の2つ以上の周期を有することを特徴とする半導体発光装置。 - 前記二次元フォトニック結晶は、前記第一の光の光学波長の6倍以上及び前記第二の光の光学波長の6倍以上の、少なくとも2つ以上の周期を有することを特徴とする請求項1に記載の半導体発光装置。
- 少なくとも2層以上の半導体層と、発光層とを積層して構成される積層半導体層を有し、第一の光を発光する半導体発光素子と、
少なくとも前記半導体発光素子の一部を覆い、前記第一の光の少なくとも一部を吸収し、前記第一の光の波長とは異なる第二の光を発光する波長変換部材と、を有して構成される半導体発光装置であって、
前記半導体発光素子は、前記半導体発光素子を構成するいずれかの主面において、面外方向に延在する複数の凸部又は凹部から構成されるドットを含む微細構造層を構成要素として備え、
前記微細構造層は、少なくとも前記ドット間のピッチ、ドット径又はドット高さのいずれかにより制御された二次元フォトニック結晶を構成し、
前記二次元フォトニック結晶は、前記第一の光の光学波長の6倍以上及び前記第二の光の光学波長の6倍以上の、少なくとも2つ以上の周期を有することを特徴とする半導体発光装置。 - 前記波長変換部材が、少なくとも前記第一の光及び前記第二の光に対し透明である第一の材料、及び、前記第一の光の少なくとも一部を吸収し、前記第二の光を発光する第二の材料を含有することを特徴とする請求項1から請求項3のいずれかに記載の半導体発光装置。
- 前記微細構造層を、少なくとも、前記半導体発光素子の最表面に構成要素として備え、
前記微細構造層と前記波長変換部材との間には、少なくとも前記第一の光及び前記第二の光に対し実質的に透明であり、前記第二の材料を含まない中間材料が充填されていることを特徴とする請求項4に記載の半導体発光装置。 - 前記第二の材料が、前記第一の光の第一の材料における光学波長よりも小さい平均粒子径であることを特徴とする請求項5に記載の半導体発光装置。
- 前記波長変換部材は、前記第二の光と、前記第一の光及び前記第二の光の各波長とは異なる第三の光とを発光する構成であり、
前記波長変換部材が、少なくとも前記第一の光と前記第二の光及び前記第三の光に対し透明である第一の材料、及び、前記第一の光の少なくとも一部を吸収し、前記第三の光を発光する第三の材料を含有し、
前記二次元フォトニック結晶は、前記第三の光の光学波長の6倍以上の周期を有することを特徴とする請求項4に記載の半導体発光装置。 - 前記微細構造層を、少なくとも、前記半導体発光素子の最表面に構成要素として備え、
前記微細構造層と前記波長変換部材との間には、少なくとも前記第一の光と前記第二の光及び前記第三の光に対し実質的に透明であり、前記第二の材料及び前記第三の材料を含まない中間材料が充填されていることを特徴とする請求項7に記載の半導体発光装置。 - 前記第二の材料及び第三の材料の少なくとも一つが、前記第一の光の前記第一の材料における光学波長よりも小さい平均粒子径であることを特徴とする請求項8に記載に半導体発光装置。
- 前記波長変換部材は、前記第二の光と、前記第三の光と、前記第一の光、前記第二の光及び前記第三の光の各波長とは異なる第四の光とを発光する構成であり、
前記波長変換部材が、少なくとも前記第一の光と前記第二の光と前記第三の光及び前記第四の光に対し透明である第一の材料、及び、前記第一の光の少なくとも一部を吸収し、前記第四の光を発光する第四の材料を含有し、
前記二次元フォトニック結晶は、前記第四の光の光学波長の6倍以上の周期を有することを特徴とする請求項7に記載の半導体発光装置。 - 前記微細構造層を、少なくとも、前記半導体発光素子の最表面に構成要素として備え、
前記微細構造層と前記波長変換部材との間には、少なくとも前記第一の光と前記第二の光と前記第三の光及び前記第四の光に対し実質的に透明であり、前記第二の材料、前記第三の材料及び前記第四の材料を含まない中間材料が充填されていることを特徴とする請求項10に記載の半導体発光装置。 - 前記第二の材料、前記第三の材料及び前記第四の材料の少なくとも一つが、前記第一の光の前記第一の材料における光学波長よりも小さい平均粒子径であることを特徴とする請求項11に記載の半導体発光装置。
- 前記二次元フォトニック結晶が、前記半導体発光素子を構成するいずれか異なる二つ以上の主面に構成され、各々の二次元フォトニック結晶の前記周期が互いに異なることを特徴とする請求項1から請求項12のいずれかに記載の半導体発光装置。
- 前記二次元フォトニック結晶の周期が少なくとも前記主面の一軸方向に周期を有することを特徴とする請求項1から請求項12のいずれかに記載の半導体発光装置。
- 前記二次元フォトニック結晶の周期が少なくとも独立する前記主面の二軸方向に周期を有することを特徴とする請求項1から請求項12のいずれかに記載の半導体発光装置。
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