JP2006049855A - Semiconductor light emitting device and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor light emitting device which is more improved in light extraction efficiency than conventional ones. <P>SOLUTION: Irregularities having a two-dimensionally periodic structure are formed on the surface of a semiconductor multilayered film opposite to its primary surface, and a metal electrode of high reflectance is formed on the other surface. The surface where the irregularities are formed can be improved in light extraction efficiency making use of the diffraction effect of the two-dimensionally periodic structure. Light emitted toward the metal electrode is reflected toward the rugged surface by the metal electrode of high reflectance, so that an effect to be brought about by the two-dimensionally periodic structure is doubled. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a light emitting element using a semiconductor and a method for manufacturing the same.

  Light emitting diodes (LEDs) and semiconductors that output light in the blue to green wavelength band from ultraviolet light, where it has been difficult to obtain sufficient emission intensity by using nitride compound semiconductors typified by AlInGaN Light emitting elements such as lasers have been put into practical use, and research and development have been actively conducted. Among light-emitting elements, LEDs are easier to manufacture and control than semiconductor lasers, and have a longer life than fluorescent lamps, so LEDs using nitride-based compound semiconductors are especially expected as light sources for illumination. Has been.

  FIG. 35 is a perspective view showing a conventional nitride-based compound semiconductor LED. The conventional LED has a configuration in which an n-type GaN layer 1002, an InGaN active layer 1003, and a p-type GaN layer 1004 are sequentially grown on a sapphire substrate 1001. Further, the InGaN active layer 1003 and the p-type GaN layer 1004 are partially removed by etching, and the n-type GaN layer 1002 is exposed. An n-side electrode 1006 is formed on the exposed portion of the n-type GaN layer 1002. A p-side bonding electrode 1007 is provided on the p-type GaN layer 1004.

  This LED operates as follows.

  First, holes injected from the p-side bonding electrode 1007 spread laterally at the p-side transparent electrode 1005 and are injected from the p-type GaN layer 1004 into the InGaN active layer 1003.

  On the other hand, electrons injected from the n-side electrode 1006 are injected into the InGaN active layer 1003 through the n-type GaN layer 1002. Light is emitted by recombination of holes and electrons in the InGaN active layer 1003. This light is emitted outside the LED through the p-side transparent electrode 1005.

  However, such a conventional structure cannot be said to have sufficiently high light extraction efficiency. The light extraction efficiency is the proportion of light generated in the active layer that is emitted from the LED into the air. The reason why the light extraction efficiency is low in the conventional LED is that the refractive index of the semiconductor is larger than that of air, and light from the active layer is confined inside the LED by total reflection at the interface between the semiconductor and air. For example, since the refractive index of GaN is about 2.45 at a wavelength of 480 nm, the critical refraction angle at which total reflection occurs is as small as about 23 degrees. In other words, the light emitted from the active layer at an angle larger than the critical angle as seen from the normal line of the semiconductor-air interface is totally reflected at the semiconductor-air interface, and is eventually emitted from the active layer. Only about 4% of the light can be extracted out of the LED. Therefore, the external quantum efficiency (the efficiency of the light that can be extracted from the LED out of the current input to the LED) is low, and the power conversion efficiency (the efficiency of the light output that can be extracted out of the input power) is lower than that of the fluorescent lamp. there were.

  As a solution to this problem, as disclosed in Patent Document 1, a technique for forming a photonic crystal on the surface of an LED has been proposed.

FIG. 36 is a perspective view showing a conventional LED having a photonic crystal formed on the upper surface. As shown in the figure, two-dimensional periodic irregularities are formed in the p-type GaN layer 1004. In this structure, the light emitted from the active layer at a normal angle larger than the critical refraction angle with respect to the interface between the semiconductor and air can also make the emission direction smaller than the critical refraction angle by diffraction of the periodic unevenness. it can. Therefore, the ratio of the light that is emitted from the LED without being totally reflected is increased, and the light extraction efficiency is improved. Note that in this specification, the term “two-dimensional periodic” means that the structures are formed at regular intervals (constant period) along the first direction on the plane, It shall mean that they are formed at regular intervals (constant periods) along the intersecting second direction.
JP 2000-196152 A

  However, when unevenness is formed on the LED surface close to an active layer such as a p-type GaN layer, the following problems may occur.

  Since the p-type GaN layer 1004 has a high resistivity, the p-type GaN layer 1004 is desired to be as thin as about 0.2 μm in order to reduce the series resistance of the LED and emit light with high efficiency. However, in order to form irregularities on the upper surface of the p-type GaN layer 1004, it is necessary to increase the thickness of the p-type GaN layer 1004. Therefore, in the conventional LED as shown in FIG. 36, the series resistance may increase and the power conversion efficiency may decrease. Further, crystal defects are generated on the surface of the p-type GaN layer 1004 by dry etching for forming irregularities in the p-type GaN layer 1004. Since such crystal defects function as electron donors, in the n-type GaN layer 1002, the electron concentration on the surface increases and the contact resistance decreases. However, in the p-type GaN layer 1004, crystal defects due to etching damage compensate holes, making it difficult to form an ohmic electrode. As a result, the contact resistivity increases and the power conversion efficiency decreases. Furthermore, since the irregularities are close to the active layer, damage due to etching when the irregularities are formed occurs in the active layer, and the internal quantum efficiency in the active layer (of the electron-hole pairs recombined in the active layer is converted to photons. The ratio is reduced, and the light emission efficiency of the LED is likely to decrease.

  In the LED, a surface on which the two-dimensional photonic crystal can be formed includes a main surface side surface and a back surface side surface. In this case, there are two possible positions for forming the photonic crystal: the back surface of the substrate and the interface between the substrate and the semiconductor. However, in any case, the following problems occur when the conventional technique is used. When a photonic crystal is formed on the back side of a substrate, total reflection occurs at the interface between the semiconductor and the substrate. Therefore, the photonic crystal formed on the back side of the substrate has the effect of improving the light extraction efficiency in the case of the photonic crystal formed on the semiconductor. Less than. In addition, when a photonic crystal is formed at the interface between the semiconductor and the substrate, the refractive index difference between the semiconductor and the substrate is small, so the efficiency of diffraction due to periodic unevenness decreases, and the effect of improving the light extraction efficiency is the top surface of the LED This is lower than when a photonic crystal is formed.

  An object of the present invention is to provide a semiconductor light emitting device having improved light extraction efficiency as compared with the prior art.

  A first semiconductor light emitting device of the present invention is a semiconductor light emitting device comprising a multilayer semiconductor layer which is formed on a substrate and then peeled off from the substrate, and is in contact with the substrate among the surfaces of the multilayer semiconductor layer. A two-dimensional periodic structure is formed on the first main surface.

  With this configuration, the back surface of the multilayer semiconductor layer is less likely to be damaged when the element is manufactured, so that the power conversion efficiency can be improved as compared with the related art.

  The substrate may be made of sapphire or the like, but is preferably made of silicon. A silicon substrate has better thermal conductivity than a sapphire substrate. For this reason, the heat generated at the time of peeling (for example, reaction heat when the silicon substrate is removed by wet etching) can be made uniform over the entire two-dimensional periodic structure.

  A second semiconductor light emitting device according to the present invention includes a substrate having a two-dimensional periodic structure on a first main surface, and a multilayer semiconductor layer including an active layer that generates light formed on the first main surface of the substrate, A semiconductor light emitting device having the above structure, wherein the substrate is silicon.

  With this configuration, since the diffraction efficiency can be increased without removing the substrate, the manufacturing becomes easier as compared with the case where the substrate is removed.

  We have found that it is appropriate to use silicon as the substrate as follows.

During crystal growth, the silicon substrate is exposed to a high temperature, but a very thin SiO ₂ film is formed on the surface of the silicon substrate (the surface of the two-dimensional periodic structure) due to residual oxygen in the crystal growth furnace. The refractive index of silicon is about 3.3, whereas the refractive index of SiO ₂ is about 1.4. Since the refractive index of the light emitting semiconductor layer is generally 2.4 to 3.3, the change in the refractive index of the two-dimensional periodic structure is enhanced by this SiO ₂ film. As the refractive index change is larger, the diffraction efficiency is higher, so that the light emission efficiency can be further increased.

  In the method for manufacturing a semiconductor light emitting device of the present invention, a step (a) of forming a first two-dimensional periodic structure on a main surface of a substrate, and a multilayer semiconductor layer is formed on the first two-dimensional periodic structure. And (b).

  By this method, it is possible to form a structure such as a two-dimensional periodic structure without damaging the back surface of the multilayer semiconductor layer. For this reason, it becomes possible to manufacture a semiconductor light emitting device with improved light extraction efficiency.

  Since the semiconductor light emitting device of the present invention has the above-described configuration, it is difficult for the semiconductor constituting the two-dimensional periodic structure to be damaged, so that the light extraction efficiency can be improved. In addition, since a substrate or a semiconductor on which a two-dimensional periodic structure is formed can be used as a mold, a product with uniform characteristics can be manufactured at low cost.

  Hereinafter, the present invention will be described more specifically using embodiments. Note that in this specification, a surface of a semiconductor layer formed by epitaxial growth in a crystal growth direction is referred to as a main surface, and a surface opposite to the main surface is referred to as a back surface.

(First embodiment)
-Configuration of light emitting element-
FIG. 1 is a perspective view showing a semiconductor light emitting element according to the first embodiment of the present invention. As shown in the figure, the semiconductor light emitting device of this embodiment includes a p-type GaN layer (first semiconductor layer) 3 having a thickness of 200 nm formed by epitaxial growth and a crystal growth surface (mainly) of the p-type GaN layer 3. 1 μm thick highly reflective p-electrode (first electrode) 2 formed by stacking platinum (Pt) and gold (Au), and formed on the lower surface of the highly reflective p-electrode 2. An Au plating layer 1 having a thickness of 10 μm, a non-doped InGaN active layer 4 having a thickness of 3 nm formed on the back surface of the p-type GaN layer 3, and a convex shape on the back surface of the non-doped InGaN active layer 4. An n-type GaN layer (second semiconductor layer) 5 having a thickness of 4 μm on which the two-dimensional periodic structure 6 is formed, and formed on the back surface of the n-type GaN layer 5, and titanium (Ti) and Au are laminated. And an n electrode (second electrode) 7 having a thickness of 1 μm. Here, the lower surface means a surface located on the lower side in FIG. 1 in a certain layer. In the example shown in FIG. 1, the highly reflective p-electrode 2 is provided on the entire main surface of the p-type GaN layer 3, and the n-electrode 7 is provided on a part of the back surface of the n-type GaN layer 5. ing. “Non-doped” means that the corresponding layer is not intentionally doped.

  The semiconductor light emitting device of this embodiment functions as an LED from which light is extracted from the back surface direction of the n-type GaN layer 5, and the PL peak wavelength of the non-doped InGaN active layer 4 is 405 nm. As will be described later, crystal growth methods for nitride compound semiconductors constituting semiconductor light emitting devices include MOCVD (Metal-organic Chemical Vapor Deposition) method, MBE (Molecular Beam Epitaxy). ) Method.

  The period of the two-dimensional periodic structure 6 formed on the back surface of the n-type GaN layer 5, that is, the center interval between adjacent protrusions in the two-dimensional plane is 0.4 μm, and the height of the protrusions is 150 nm.

-Explanation of diffraction on n-type GaN layer surface-
Next, diffraction on the front surface (back surface) of the n-type GaN layer of the semiconductor light emitting device of this embodiment will be described based on simulation results.

  FIG. 2 shows the theoretical calculation of the transmittance of light emitted from the non-doped InGaN active layer and incident on the back surface (upper surface in the figure) of the n-type GaN layer, that is, the incident angle dependence of the amount of light emitted outside the LED. It is a figure which shows a result. Theoretical calculation used numerical analysis by the FDTD method. The incident angle is 0 degree when perpendicularly incident on the back surface of the n-type GaN layer.

  As shown in FIG. 2, when the surface of the n-type GaN layer is smooth, the incident angle is 0 degree to the total reflection critical angle θc (since the refractive index of GaN is about 2.5, θc = sIn−1 (1/2. 5) = about 23 degrees), the transmittance is constant and the value is about 90%. Here, the reason why 10% of the generated light is reflected and returns to the inside of the LED again is Fresnel reflection caused by the difference in refractive index between GaN and air. When the incident angle exceeds the total reflection critical angle, the transmittance becomes almost zero because total reflection occurs at the interface between GaN and air. The reason why the total reflection occurs will be described with reference to FIG.

  FIG. 3A is a diagram showing a configuration in (1) real space in an LED, and FIGS. 3B and 3C are diagrams showing a configuration in (2) wave number space in a light emitting element. FIG. 3B shows a case where the incident angle of light is small, and FIG. 3C shows a case where the incident angle of light is large. The semicircles in FIGS. 3B and 3C are equal frequency surfaces, and the magnitude of the wave vector that the incident wave, reflected wave, and transmitted wave must satisfy in the LED and in the air (wave number k = 2πn / λ; n Represents a refractive index, and λ represents a wavelength in a vacuum). This semicircle means the conservation law of photon energy (hω / 2π, h is Planck's constant). This is because k = ωn / c (c is the speed of light in vacuum). When the configuration of the real space has translational symmetry with respect to the horizontal direction as shown in (1) in FIG. 3A, the wave number component in the horizontal direction is a law that the incident wave, reflected wave, and transmitted wave should follow. (This is related to the phase continuity of electromagnetic waves). The incident angle and the outgoing angle are determined so as to satisfy the above two laws.

  As shown in FIG. 3B, when the incident angle of light is small, there is an exit angle that satisfies the above two laws, so that the light can be emitted into the air. However, when the incident angle of light is large as shown in FIG. 3C, there is no emission angle that satisfies the horizontal wavenumber component, and thus light cannot be emitted into the air. In this case, since the transmittance T is T = 0, when there is no absorption at the LED / air interface, the reflectance R must satisfy the light energy conservation law T + R = 1, and therefore R = 1. . That is, the light is totally reflected at the LED / air interface. By the way, even if a structure that reduces Fresnel reflection, such as a non-reflective film, is introduced at the interface between the LED and air, R = 1 is always obtained under the condition that transmittance T = 0, and total reflection is avoided. I can't.

Next, FIGS. 4A and 4B are diagrams showing the configuration of the wave number space when a two-dimensional periodic structure having a period of 0.1 μm is formed on the n-type GaN surface. Diffraction occurs for the periodic structure is formed on a surface, horizontal wavenumber k _{1 //,} the wave number k _{2 //} diffraction vector G = 2π / Λ (Λ is the period of the horizontal direction of the transmission wave of the incident wave ) Must be consistent with the following conditions.

k _{2 //} = k _{1 //} ± mG (m is the diffraction order, m = 0, ± 1, ± 2...)
When there is a wave number k _{2 //} that satisfies the condition of the above equation and the above-described equal frequency plane, a transmitted wave is generated.

As shown in FIG. 4 (a), when the period of the structure of the incident angle is 0 degrees 0.1 [mu] m, because too large size of the diffraction vector, the transmitted wave is assumed to be diffracted, k 2 _{/ Since /} is larger than the equal frequency surface in air, it is totally reflected. Therefore, no diffraction occurs in this case. Further, as shown in FIG. 4B, in the case of an incident angle of 70 degrees at which the 0th-order transmitted wave is totally reflected, even if the light is diffracted, the condition is that the light is totally reflected. Therefore, in this period, total reflection occurs at an incident angle equal to or greater than the total reflection critical angle as in the case where the surface is flat.

  FIG. 5 is a diagram showing the refractive index in each portion of the semiconductor layer having a periodic structure formed on the surface. As shown in FIG. 5, in the case of a periodic structure having a period smaller than the wavelength of light, the effective refractive index is lowered due to the unevenness in the two-dimensional periodic structure on the surface of the semiconductor layer, and the two-dimensional periodic structure consists of air, LED, It functions as an intermediate refractive index layer. In this case, since the refractive index difference between the air and the LED is relaxed, the Fresnel reflection that occurs when the incident angle is smaller than the total reflection critical angle is suppressed, and the incident angle as shown in FIG. 2 is smaller than the total reflection critical angle. In this case, the light transmittance can be improved.

  Next, a case where there is a two-dimensional periodic structure with a period of 0.2 μm on the front surface (back surface) of the n-type GaN layer will be described. 6A to 6C are diagrams showing the structure of the wave number space when a two-dimensional periodic structure having a period of 0.2 μm is formed on the n-type GaN surface.

Under this condition, as shown in FIG. 6 (a), if the incident angle of light is 0 degree, the k _{2 //} when diffracted is larger than the equal frequency surface in the air, so that it is totally reflected and diffracted. Does not occur. In this case, the 0th-order transmitted wave passes through the interface between the n-type GaN layer and air.

On the other hand, when the incident angle at which total reflection occurs when the surface is flat is 30 degrees or the incident angle is 70 degrees, as shown in FIGS. 6B and 6C, k _{2 //} is equal frequency in the air. A diffracted transmitted wave (diffraction order −1) smaller than the surface can pass through the interface. As a result, as shown in FIG. 2, the transmittance does not become zero even when the total reflection critical angle is exceeded. Since the diffraction efficiency also contributes to the actual transmittance, the transmittance shows a complicated curve. In this case, since the diffraction vector is relatively large, second-order or higher diffraction does not contribute to transmission.

  FIG. 7 is a diagram showing the configuration of the wave number space when a two-dimensional periodic structure having a period of 0.4 μm is formed on the surface of the n-type GaN layer. Since the diffraction vector is relatively small in this period, even when the incident angle of light shown in FIG. 7A is 0 degree, the first-order diffraction is related to transmission. In addition, when the incident angle shown in FIG. 7B is 35 degrees, the first-order and second-order diffractions are performed. When the incident angle shown in FIG. 7C is 70 degrees, the second-order and third-order diffractions are performed. Each contributes to transmission. As a result, as shown in FIG. 2, the transmittance is relatively high even when the total reflection critical angle is exceeded.

  Thus, as the period of the structure formed on the surface of the n-type GaN layer increases, higher-order diffraction is involved, and the behavior of light becomes complicated.

  Based on the above examination, in the semiconductor light emitting device of this embodiment, when the refractive index of the semiconductor layer formed with the two-dimensional periodic structure is N, and the period of the two-dimensional periodic structure is Λ, 0.5λ / N <Λ It is assumed that <20λ / N. At 0.5λ / N> Λ, the angle change due to diffraction is large, and the diffracted light exceeds the critical angle of total reflection, so that it is not emitted outside the semiconductor light emitting device. In this case, the diffraction of the two-dimensional period cannot improve the light extraction efficiency. In addition, when Λ> 20λ / N, since the period is much larger than the wavelength of light emitted from the active layer, almost no diffraction effect can be expected. From the above, in order to make the effect of the two-dimensional periodic structure effective, it is desirable that the condition is 0.5λ / N <Λ <20λ / N.

FIG. 8 is a diagram for explaining the solid angle used for calculating the light extraction efficiency. As shown in the figure, the actual light extraction efficiency η needs to be integrated at the incident angle in consideration of the effect of the solid angle on the reflectance T (θ) for each incident angle. Specifically, η can be derived from the following equation.
η = ∫2πT (θ) ・ θ ・ dθ
FIG. 9 is a diagram showing a value obtained by normalizing the light extraction efficiency obtained from the above equation with the light extraction efficiency when the surface of the n-type GaN layer is flat. The period Λ and the height h of the unevenness are considered as calculation parameters. As a result, the light extraction efficiency is maximized when the height of the convex portion on the surface of the GaN layer is 150 nm. This is because when the height h of the unevenness is λ / {2 (n2-n1)] (λ is the emission wavelength in air or vacuum, n1 is the refractive index of air, and n2 is the refractive index of the semiconductor) This is because the phase of the light component that passes through the convex portion and the phase of the light component that passes through the concave portion of the light passing through the concave portion are strengthened by interference, and the diffraction efficiency due to the concave and convex portions is maximized. In this case, h = about 130 nm, which is almost the same as the numerical calculation result by FDTD. Thus, in the semiconductor light emitting device of this embodiment, h is most preferably in the vicinity of an integral multiple of λ / {2 (n2−n1)]. Here, h is approximated to λ / {2 (n2-n1)] in consideration of general performance variations due to the manufacturing process.

  Further, from FIG. 9, when the height h of the unevenness is 150 nm, the light extraction efficiency is maximum as compared with the case where the surface of the n-type GaN layer is flat if the period Λ is 0.4 to 0.5 μm. It turns out that it improves 2.6 times. Here, in order to avoid total reflection as the period Λ increases, it is necessary to use higher-order diffraction. However, as the diffraction order increases, the diffraction efficiency decreases, so in the range where the period Λ is 0.4 μm or more. The light extraction efficiency decreases as the period increases. For example, when the period of the structure shown in FIG. 2 is 2.0 μm, the transmittance of light having an incident angle equal to or greater than the total reflection critical angle is lower than the period of 0.4 μm.

  FIGS. 10A and 10B are plan views showing the arrangement of the two-dimensional periodic structure formed on the surface of the n-type GaN layer. As shown in the figure, the two-dimensional periodic structure formed by the semiconductor light emitting device of this embodiment may be a square lattice or a triangular lattice.

-Manufacturing method of light emitting element-
11A to 11F are perspective views showing a method for manufacturing the semiconductor light emitting device of this embodiment shown in FIG.

  First, as shown in FIG. 11A, a sapphire substrate 8 is prepared, and a 1 μm-thickness is formed on the main surface of the sapphire substrate 8 by metal organic chemical vapor deposition (MOCVD). The AlGaN layer 9 is crystal-grown. Here, if the thickness of the AlGaN layer 9 is 1 μm, the occurrence of crystal defects is reduced. The Al composition in the AlGaN layer 9 may be any composition as long as it is transparent with respect to the wavelength of light used in the later laser lift-off, but here the Al composition is 100%.

  Next, as shown in FIG. 11B, the concave two-dimensional periodic structure 10 is patterned on the main surface of the AlGaN layer 9. In this process, the resist of the etching mask is patterned using electron beam exposure or a stepper, and then the RIE (Reactive Ion Etching) method or ion milling is used to etch the nitride compound semiconductor. The AlGaN layer can be etched by using a dry etching technique such as an (Ion Milling) method, or a wet etching technique such as photochemical etching while irradiating ultraviolet rays or etching with a heated acid / alkali solution. In this example, the two-dimensional periodic structure 10 is formed by electron beam exposure and RIE. The period of the two-dimensional periodic structure 10 is 0.4 μm, and the depth of the recess is 150 nm. In addition, although the shape of the two-dimensional periodic structure 10 is not specifically limited, In the example of FIG.11 (b), the recessed part is a column shape.

  Next, as shown in FIG. 11C, an n-type GaN layer 11 (the n-type GaN layer 5 in FIG. 1) is formed on the main surface of the AlGaN layer 9 on which the two-dimensional periodic structure 10 is formed by MOCVD. A non-doped InGaN active layer 12 (non-doped InGaN active layer 4) and a p-type GaN layer 13 (p-type GaN layer 3) are formed in this order. Here, the thicknesses of the n-type GaN layer 11, the non-doped InGaN active layer 12, and the p-type GaN layer 13 are 4 μm, 3 nm, and 200 nm, respectively. In this step, crystal growth of the n-type GaN layer 11 is performed by setting growth conditions so as to embed the two-dimensional periodic structure 10.

  Thereafter, a highly reflective p-electrode 2 made of Pt / Au (a laminated film of Pt and Au) is formed on the main surface of the p-type GaN layer 13 by, for example, electron beam evaporation. Further, an Au plating layer 15 having a thickness of about 50 μm is formed using the Au layer of the highly reflective p-electrode 2 as a base electrode.

  Subsequently, as shown in FIG. 11 (d), a KrF excimer laser (wavelength 248 nm) is irradiated from the back surface of the sapphire substrate 8 while scanning the wafer surface. The irradiated laser light is not absorbed by the sapphire substrate 8 and the AlGaN layer 9, but is absorbed only by the n-type GaN layer 11, so that the bond of GaN is decomposed near the interface with the AlGaN layer 9 due to local heat generation. . Thereby, the AlGaN layer 9 and the sapphire substrate 8 can be separated from the n-type GaN layer 11, and a device structure made of a GaN-based semiconductor can be obtained. The light source used here may be a wavelength that is absorbed by the GaN layer and transparent to the AlGaN layer and the sapphire substrate, and the third harmonic of the YAG laser (wavelength 355 nm) or the mercury lamp emission line (wavelength 365 nm). May be used.

  Next, as shown in FIG. 11E, the sapphire substrate 8 and the AlGaN layer 9 are removed from the state shown in FIG. Thereby, the convex two-dimensional periodic structure 6 is spontaneously formed on the back surface of the n-type GaN layer. Such a semiconductor multilayer film after removing the substrate (that is, a multilayer film including the n-type GaN layer 11, the non-doped InGaN active layer 12, and the p-type GaN layer 13) is a very thin thin film having a thickness of about 5 μm. For this reason, it has been difficult to form a fine structure such as a photonic crystal with a conventional photolithography technique. However, according to the method of the present invention, the semiconductor multilayer film is deposited on the concave two-dimensional periodic structure 10 formed in advance on the substrate, and then the substrate is removed to remove the surface (rear surface) of the semiconductor multilayer film. The microstructure can be easily transferred to the surface.

  Next, as shown in FIG. 11 (f), Ti / Au having a thickness of 1 μm is formed on the region where the two-dimensional periodic structure 6 is not formed on the back surface of the n-type GaN layer 11 by vapor deposition or lithography. An n-electrode 7 made of is formed. As described above, the semiconductor light emitting device of this embodiment can be manufactured.

-Effects of semiconductor light emitting device and manufacturing method thereof-
The characteristics of the semiconductor light emitting device thus obtained are shown in FIG. FIG. 12A is a diagram showing current-voltage characteristics of the semiconductor light emitting device of the conventional and the present embodiment, and FIG. 12B is a diagram showing current-light output characteristics of the semiconductor light emitting device of the conventional and the present embodiment. is there. In the figure, the characteristics of a semiconductor device having a conventional structure in which the LED surface is flat and the sapphire substrate is not removed are shown by dotted lines, and the characteristics of the semiconductor light emitting device of this embodiment are shown by solid lines.

  From the current-voltage characteristics shown in FIG. 12A, it can be seen that the current-voltage characteristics are substantially the same in the present embodiment and the conventional semiconductor light emitting device, including the rise voltages being substantially the same. In contrast to the conventional example in which the surface of the n-type GaN layer is not uneven, the semiconductor light emitting device manufactured by the method of this embodiment has a processing damage to the semiconductor multilayer film due to the formation of the two-dimensional periodic structure. I understand that there is no. In the substrate separation step shown in FIGS. 11D and 11E, the sapphire substrate 8 can be removed by polishing and the AlGaN layer 9 can be removed by etching. However, the method using a laser is shorter. Is more preferable.

  Further, from the current-light output characteristics shown in FIG. 12B, in the current region of 20 mA or less, the semiconductor light emitting device of the present embodiment has a light output at the same current almost five times that of the conventional example. I understand that. This is approximately twice the theoretical calculation value shown in FIG. This is because the light extraction efficiency from the surface is increased by about 2.5 times compared to the conventional flat LED surface due to the two-dimensional periodic structure of the LED surface, and the LED lower surface side (on the back surface of the p-type GaN layer 13). This is because the light radiated from the non-doped InGaN active layer 12 to the highly reflective p-electrode 14 side can be efficiently reflected to the two-dimensional periodic structure 6 side.

  From FIG. 12B, it can be seen that the light output is saturated under a large current in the conventional structure, but the light output is not saturated even at a large current exceeding 100 mA in the element of the present embodiment. This is because in the conventional structure, heat generated in the active layer is dissipated through a thick n-type semiconductor layer of several μm and a sapphire substrate with poor heat dissipation. Further, in the light emitting device of this embodiment, the heat of the active layer can be radiated from the sub-μm thin p-type semiconductor side through the Au plating layer having high thermal conductivity, so that the heat dissipation is excellent. is there.

  In this manner, the Au plating layer 15 can maintain the improvement in light extraction efficiency due to the two-dimensional periodic structure 6 even at a large current.

  FIGS. 13A, 13B, 14 and 15A, 15B are perspective views showing modifications of the semiconductor light emitting device of this embodiment. FIGS. 16A and 16B are perspective views showing a modification of the method for manufacturing the semiconductor light emitting device of this embodiment.

  In the semiconductor light emitting device of this embodiment, the convex two-dimensional periodic structure 6 is formed on the LED surface using the concave two-dimensional periodic structure 10 formed on the surface of the AlGaN layer 9 on the sapphire substrate 8 as a “template”. As shown in FIGS. 13A and 13B, the convex two-dimensional periodic structure 16 is formed on the surface of the AlGaN layer 9, so that the concave two-dimensional periodic structure 17 is formed on the LED surface. An effect is obtained. That is, even if the structure on the LED surface is convex or concave, it can diffract incident light as long as it is formed two-dimensionally.

  Further, as shown in FIG. 14, in addition to the method of forming irregularities in the AlGaN layer 9, a part of the sapphire substrate 8 is removed by laser lift-off or the like, and the main surface of the sapphire substrate 8 is convex or concave two-dimensional. Even if the periodic structure 16 is formed, it is possible to realize a semiconductor light emitting device in which a convex or concave two-dimensional periodic structure is formed on the surface of the AlGaN layer 9 by using the periodic structure 16 as a template.

Alternatively, as shown in FIG. 15A, an oxide film such as a SiO ₂ film or a SiN film or a nitride film, or a metal film such as a tungsten (W) film is formed on the sapphire substrate 8. Then, the convex two-dimensional periodic structure 16 can be formed by patterning. Further, as shown in FIG. 15B, the semiconductor light emission of the present embodiment can also be achieved by forming a convex two-dimensional periodic structure 16 made of an oxide film, a nitride film, or a metal film on the main surface of the AlGaN layer 9. A light-emitting element having characteristics similar to those of the element can be manufactured.

  If a SiC substrate is used instead of the sapphire substrate, the substrate can be removed by selective dry etching of SiC and GaN. If a Si substrate is used, the substrate can be easily removed by wet etching. Details of using the Si substrate will be described separately below.

  Further, when the depth of the concave two-dimensional periodic structure 17 formed on the back surface (front surface) of the n-type GaN layer 11 formed by removing the substrate is shallow, or when the inclination of the inner slope of the concave portion is not vertical. The shape of the recess can be adjusted by performing the processing shown in FIGS. 16A and 16B after removing the substrate.

  That is, as shown in FIG. 16A, an LED structure and a counter electrode such as Pt are immersed in an electrolyte solution such as an aqueous KOH solution, and a voltage is applied between the LED and the counter electrode with the p side of the LED being positive. To do. Then, as shown in FIG. 16B, GaN is etched by anodic oxidation. However, since the electric field is concentrated on the recess, only the recess is etched, and the depth of the recess can be increased. In addition, the anodic oxidation etching proceeds vertically due to the concentration of the electric field in the recesses. Therefore, even if the inner slope of the recess after removing the substrate is not vertical, a recess having a vertical slope can be formed by anodic oxidation etching.

  FIG. 17 is a diagram illustrating a theoretical calculation result of the dependence of the light extraction efficiency on the inclination angle of the recess. Here, the inclination angle is assumed to be obtained by subtracting the angle formed by the side surface of the concave portion and the upper surface of the n-type GaN layer 11 from 180 degrees as shown in the left diagram of FIG. From the results shown in FIG. 17, it can be seen that the light extraction efficiency rapidly decreases when the inclination angle is 50 degrees or less. That is, when the inclination angle of the two-dimensional periodic structure that can be formed after removing the substrate is small, the inclination angle can be increased by the above-described anodic oxidation etching, and high light extraction efficiency can be realized. Thus, in the semiconductor light emitting device of this embodiment, the inclination angle of the two-dimensional periodic structure is preferably 50 degrees or more. Even when the two-dimensional periodic structure is convex, it is preferable that the inclination angle is 50 degrees or more because the light extraction efficiency is improved.

-Manufacturing method of light emitting element using silicon substrate-
18A to 18F are perspective views showing a second manufacturing method of the semiconductor light emitting device of this embodiment shown in FIG.

  First, as shown in FIG. 18B, the concave two-dimensional periodic structure 10 is patterned on the main surface of the Si substrate 51. In this step, the resist serving as an etching mask is patterned using electron beam exposure or a stepper. After that, in this process, dry etching techniques such as RIE (Reactive Ion Etching) and ion milling (Ion Milling), photochemical etching performed while irradiating ultraviolet rays, etching with heated acid / alkaline solution Etching of the Si substrate 51 can be performed by using a wet etching technique such as the above. In this example, the two-dimensional periodic structure 10 is formed on the Si substrate 51 by electron beam exposure and RIE. The period of the two-dimensional periodic structure 10 is 0.4 μm, and the depth of the recess is 150 nm. In addition, although the shape of the two-dimensional periodic structure 10 is not specifically limited, In the example shown in FIG.18 (b), the recessed part is a cylindrical shape.

  Next, as shown in FIG. 18C, the n-type GaN layer 11 (the n-type GaN layer 5 in FIG. 1) is formed on the main surface of the Si substrate 51 on which the two-dimensional periodic structure 10 is formed by MOCVD. A non-doped InGaN active layer 12 (non-doped InGaN active layer 4 in FIG. 1) and a p-type GaN layer 13 (p-type GaN layer 3 in FIG. 1) are formed in this order. Here, the thicknesses of the n-type GaN layer 11, the non-doped InGaN active layer 12, and the p-type GaN layer 13 are 4 μm, 3 nm, and 200 nm, respectively. In this step, crystal growth of the n-type GaN layer 11 is performed by setting growth conditions so as to embed the two-dimensional periodic structure 10.

  Thereafter, as shown in FIG. 18D, a highly reflective p-electrode 14 made of Pt / Au (a laminated film of Pt and Au) is formed on the main surface of the p-type GaN layer 13 by, for example, electron beam evaporation. Further, an Au plating layer 15 having a thickness of about 50 μm is formed using the Au layer of the highly reflective p-electrode 14 as a base electrode.

Next, as shown in FIG. 18E, the Si substrate 51 is removed using an etchant containing HF / HNO ₃ . Thereby, the convex two-dimensional periodic structure 6 is spontaneously formed on the back surface of the n-type GaN layer 11. Such a semiconductor multilayer film after removing the substrate (that is, a multilayer film composed of the n-type GaN layer 11, the non-doped InGaN active layer 12, and the p-type GaN layer 13) has a total film thickness of about 4 to 5 μm. Since it is a very thin film, it has been difficult to form a fine structure like a photonic crystal with a conventional photolithography technique. However, according to the method of the present invention, the semiconductor multilayer film is deposited on the concave two-dimensional periodic structure 10 formed in advance on the substrate, and then the substrate is removed to remove the surface (rear surface) of the semiconductor multilayer film. The microstructure can be easily transferred to the surface.

  Next, as shown in FIG. 18 (f), Ti / Au having a thickness of 1 μm is formed on a region where the two-dimensional periodic structure 6 is not formed on the back surface of the n-type GaN layer 11 by vapor deposition or lithography. An n-electrode 7 made of is formed. As described above, the semiconductor light emitting device of this embodiment can be manufactured.

-Effect of using Si substrate-
Si has excellent thermal conductivity. For this reason, the heat generated at the time of peeling (for example, reaction heat when the Si substrate is removed by wet etching) can be made uniform over the entire two-dimensional periodic structure. As a result, it is possible to prevent the chemical reaction at the time of peeling the Si substrate 51 from occurring evenly and damage the two-dimensional periodic structure 6 at the time of peeling.

  In general, a semiconductor light emitting element is made of a III-V group semiconductor, does not lattice match with Si, and has a thermal expansion coefficient different from that of Si. For this reason, an extremely minute defect is generated at the uneven interface, and the semiconductor multilayer film and the Si substrate 51 can be easily separated by this defect.

  Further, since the Si substrate is not flat but has a concavo-convex structure, at least two crystal planes exist at the concavo-convex interface. Si has different wet etching rates depending on crystal planes. Therefore, a periodic change in the etching rate occurs in the two-dimensional periodic structure 10, minute stirring occurs, and etching can be performed at a higher speed.

  As described above, the productivity of the semiconductor light emitting device can be improved by using the Si substrate as the substrate for forming the two-dimensional periodic structure.

(Second Embodiment)
FIG. 19A is a perspective view showing a semiconductor light emitting device according to the second embodiment of the present invention, and FIG. 19B is a plan view of the semiconductor light emitting device of the second embodiment as viewed from above. . The semiconductor light emitting device of this embodiment is different from the semiconductor light emitting device of the first embodiment in that the convex two-dimensional periodic structure 18 formed on the upper surface (back surface) of the n-type GaN layer 5 has a polygonal pyramid shape. ing.

  As shown in FIGS. 19A and 19B, the semiconductor light emitting device of this embodiment includes a p-type GaN layer 3 having a thickness of 200 nm formed by epitaxial growth, and a crystal growth surface (mainly) of the p-type GaN layer 3. 1 μm thick high-reflection p-electrode 2 formed by stacking platinum (Pt) and gold (Au), and 10 μm-thick Au plating formed on the lower surface of high-reflection p-electrode 2. 2 formed on the back surface of the layer 1, the non-doped InGaN active layer 4 having a thickness of 3 nm formed on the back surface of the p-type GaN layer 3, and the hexagonal pyramid protrusions on the back surface of the non-doped InGaN active layer 4. An n-type GaN layer 5 having a thickness of 4 μm on which the dimensional periodic structure 18 is formed, and an n-electrode 7 having a thickness of 1 μm formed on the back surface of the n-type GaN layer 5 and laminated with titanium (Ti) and Au. And. Further, as in the first embodiment, the PL peak wavelength of the non-doped InGaN active layer 4 is 405 nm. The side surface of the protrusion structure on the back surface of the n-type GaN layer 5 is made of a {10-1-1} plane of GaN. Further, the period of the two-dimensional periodic structure 18, that is, the center interval between adjacent protrusions in the two-dimensional plane is 1.0 μm, and the height of the protrusion is 950 nm.

  FIG. 20A shows the theoretical calculation of the transmittance T of light emitted from the active layer and incident on the surface of the n-type GaN layer when a hexagonal pyramidal protrusion is formed on the surface (rear surface) of the n-type GaN layer. It is a figure which shows a result, (b) is a figure which shows the relationship between the period of a two-dimensional periodic structure, and light extraction efficiency. In FIG. 20B, the case where the surface of the n-type GaN layer is flat is 1, and for comparison, the case where the two-dimensional periodic structure is a protrusion and the case where it is uneven (the same shape as in the first embodiment). Show.

  From the results shown in FIG. 20A, it can be seen that even when the period of the two-dimensional periodic structure is as long as 1.0 μm, the protrusion structure exhibits a high transmittance when the incident angle is around 45 degrees. Thus, in the case of the semiconductor light emitting device of the present embodiment in which the cross-sectional shape of the two-dimensional periodic structure is a triangular wave shape, the two-dimensional shape is obtained when the angle incident from the active layer to the two-dimensional periodic structure on the surface of the semiconductor light emitting device is large. Since the angle of the inclined surface of the periodic structure and the angle of the incident light approach perpendicularly, the diffraction efficiency increases. Since light having a large incident angle accounts for a large proportion of light emitted from the active layer, high light extraction efficiency is realized.

  Further, from the result shown in FIG. 20B, it can be seen that the protrusion structure exhibits the same high light emission efficiency as that of the concavo-convex structure, and in particular, the effect of increasing the light extraction efficiency is maintained even when the period is long. In the 1.0 μm period, the light extraction efficiency from the surface on which the two-dimensional periodic structure is formed is increased by 2.7 times.

  Next, a method for manufacturing the semiconductor light emitting device of this embodiment will be described below.

  21A to 21F are perspective views showing a method for manufacturing the semiconductor light emitting device of this embodiment. In the manufacturing method of the present embodiment, the steps shown in FIGS. 21A to 21E are substantially the same as the manufacturing method of the first embodiment shown in FIG. However, the concave two-dimensional periodic structure 10 formed on the main surface of the AlGaN layer 9 has a period of 1.0 μm and a recess depth of 150 nm.

  That is, in the manufacturing method of the present embodiment, the sapphire substrate 8 is removed from the light emitting element main body in the steps up to FIG. 21E, and the two-dimensional periodic structure 6 configured by, for example, cylindrical convex portions is spontaneous. The n-type GaN layer 11 is formed on the back surface.

  Next, in the step shown in FIG. 21F, the n-type GaN layer 11 on which the convex two-dimensional periodic structure 6 is formed is wet-etched with a KOH aqueous solution. In etching with KOH, it is known that there are conditions in which the etching rate varies depending on the crystal plane. Under such conditions, the convex two-dimensional periodic structure 6 as described above is changed into a hexagonal pyramid-shaped two-dimensional periodic structure 18 as shown in FIG. In the embodiment shown here, etching is performed in a KOH aqueous solution having a concentration of 0.1 M to form a hexagonal pyramid two-dimensional periodic structure 18 having a crystal plane {10-1-1} as an inclined surface. Since a specific crystal plane is used as an inclined surface, it is a feature of the manufacturing method that a two-dimensional periodic structure having a triangular cross section can be easily formed with good reproducibility.

  In the semiconductor light emitting device of this embodiment, since the light extraction efficiency can be reflected from the highly reflective p-electrode 2 as compared with the case where the surface of the n-type GaN layer is flat, the theoretical calculation result shown in FIG. About twice that of the conventional example (about 5.3 times that of the conventional example). Further, heat generated in the active layer can be radiated through the sub-μm thin p-type GaN layer 13 and the Au plating layer 15 having high thermal conductivity. Therefore, in the semiconductor light emitting device of this embodiment, the effect of improving the light extraction efficiency by the two-dimensional periodic structure is maintained even when a large current of 100 mA flows. The highly reflective p-electrode 2 may be made of a material other than the laminated film of the Pt film and the Au film, but has a reflectance of 80% or more with respect to the peak wavelength of light generated in the active layer. It is practically preferable. Specifically, the highly reflective p-electrode 2 is preferably a metal film including at least one of an Au film, a Pt film, a Cu film, an Ag film, and an Rh film.

  And in order to keep heat dissipation favorable, it is preferable that the thickness of Au plating layer 15 is 10 micrometers or more. As the material of the Au plating layer 15, Au is most preferable. However, since the thermal conductivity is relatively high, any metal such as Cu or Ag can be used.

  In addition, according to the above-described manufacturing method, damage to the n-type GaN layer can be reduced as compared with a method in which a two-dimensional periodic structure is formed by direct etching. Therefore, current-voltage characteristics are almost the same as when a two-dimensional periodic structure is not formed. It is the same.

  Also, FIGS. 22A to 22C, FIGS. 23A and 23B, FIGS. 24A and 24B, FIGS. 25A and 25B, and FIGS. 26A to 26C. () Is a figure which shows the modification of the manufacturing method of the semiconductor light-emitting device of this embodiment, respectively.

  For example, in the manufacturing method of the present embodiment, a sapphire substrate 8 or an AlGaN layer 9 having a concave two-dimensional periodic structure is used to form a two-dimensional periodic structure having a triangular longitudinal section on the surface of the semiconductor (n-type GaN layer 11). The concave two-dimensional periodic structure 17 is transferred to the semiconductor surface using the sapphire substrate 8 or the AlGaN layer 9 on which the convex two-dimensional periodic structure 16 is formed as shown in FIGS. May be. In this method, the concave two-dimensional periodic structure 19 having a triangular longitudinal section can be formed on the semiconductor surface by using the above-described wet etching. Even in the case where the two-dimensional periodic structure 19 has a shape in which the concave portion is a hexagonal pyramid, high light extraction efficiency can be realized in the same manner as the semiconductor light emitting device of this embodiment.

  Further, as shown in FIGS. 23A, 23B, 24A, and 24B, the longitudinal section of the two-dimensional periodic structure 20 formed in advance on the surface of the AlGaN layer 9 is triangular. If formed, when the sapphire substrate 8 and the AlGaN layer 9 are removed, the two-dimensional periodic structures 18 and 19 having convex portions or concave portions having a triangular longitudinal section on the semiconductor surface can be spontaneously formed. .

  If the material of the layer forming the two-dimensional periodic structure is a hexagonal semiconductor such as AlGaN, a hexagonal pyramid with a specific crystal plane can be formed by the same method as described above. . For example, as shown in FIG. 25A, when a Ti film having an opening to be processed into a concave shape as an etching mask 21 is formed on the AlGaN surface and then etched with a 100 ° C. aqueous KOH solution, a two-dimensional periodic structure is formed. 20 is formed on the surface of the AlGaN layer 9. Also in this case, since a specific crystal plane forms a slope as in {10-1-1}, a two-dimensional periodic structure can be formed with good reproducibility.

  Further, when a cubic semiconductor is used as a substrate for forming a two-dimensional periodic structure, such as Si having a (001) plane as a main surface, an etching mask 21 made of Ti is used as shown in FIG. Are formed in a square lattice in a two-dimensional cycle and etched with a 70 ° C. aqueous KOH solution. Then, as shown in FIG. 26B, the quadrangular pyramid-shaped two-dimensional periodic structure 20 can be easily formed on the substrate with good reproducibility, and as shown in FIG. And a two-dimensional periodic structure 18 composed of quadrangular pyramidal holes can be transferred.

(Third embodiment)
FIG. 27 is a perspective view showing a semiconductor light emitting device according to the third embodiment of the present invention. In the semiconductor light emitting device of this embodiment, the semiconductor light emitting element according to the first or second embodiment is mounted on the mounting substrate 22, and then the periphery of the light emitting element is molded with a semicircular dome-shaped resin 23. This is a sealed semiconductor light emitting device. In FIG. 27, the same components as those in FIG. 1 among the constituent members of the semiconductor light emitting element are denoted by the same reference numerals.

  Thus, by sealing the light emitting element with the resin molded into a dome shape, the light extraction efficiency in the semiconductor light emitting element can be improved as described below.

  FIG. 28A is a view showing the theoretical calculation result of the light transmittance when the semiconductor light emitting element is molded with resin, and FIG. 28B shows the light extraction efficiency of 2 in the semiconductor light emitting device of this embodiment. It is a figure which shows the theoretical calculation result of the dependence with respect to the period of a three-dimensional periodic structure. For comparison, FIG. 28A also shows the case where the semiconductor light emitting element is not molded with resin, or the surface of the semiconductor light emitting element is flat. In the calculations shown in these figures, the refractive index of the resin is 1.5. In the calculation of FIG. 28 (b), it is assumed that the irregularities with vertical slopes are arranged in a two-dimensional periodic structure, and the height of the convex portion is 150 nm.

  From the result shown in FIG. 28 (a), in the case of having a two-dimensional periodic structure with a period of 0.4 μm, the semiconductor light emitting element sealed with resin is incident at almost all angles as compared with the one not sealed with resin. It turns out that the transmittance | permeability with respect to light is improving. In addition, since light transmittance can be improved by resin sealing even in a semiconductor light-emitting element that does not have a two-dimensional periodic structure, light can be obtained by sealing with resin regardless of the period of the two-dimensional periodic structure. It can be seen that the transmittance can be greatly improved.

  Here, even when the surface of the semiconductor light emitting device is flat, the total reflection critical angle is expanded by molding with resin, and the incident light is below the total reflection critical angle. This is because Fresnel reflection is also reduced at the corners. That is, since the difference in refractive index between the inside (refractive index 2.5) and the outside (refractive index 1.5) of the semiconductor light emitting device is reduced, the light transmittance is improved.

  Further, from the result shown in FIG. 28B, by molding with resin, the effect of improving the light extraction efficiency by the two-dimensional periodic structure can be further enhanced, and the light extraction efficiency is 3. It turns out that it reaches 8 times. This is because the resin to be molded is a semi-spherical dome shape, so that the light extracted from the semiconductor light emitting element by the two-dimensional periodic structure on the surface of the semiconductor light emitting element is incident on the interface between the resin and air perpendicularly. This is because it is radiated into the air with an efficiency of almost 100%. Thus, in the semiconductor light emitting device of this embodiment, the light extraction efficiency is greatly improved by resin-sealing the light emitting element having the two-dimensional periodic structure in a dome shape.

  Since the semiconductor light-emitting device of this embodiment can also use reflection from the back surface on which the two-dimensional periodic structure is formed by the high-reflection p-electrode 2 than the case of the surface where the light extraction efficiency is flat, the actual measurement value of the light extraction efficiency is The theoretical calculation result of FIG. 28B was improved to 7.5 times (compared with the conventional example), which is about twice. Further, this light extraction efficiency enhancement effect is excellent in heat dissipation from the sub-μm and thin p-type semiconductor side through the Au plating layer having high thermal conductivity, so that a large current of 100 mA flows to the electrode. In addition, the improvement of the light extraction efficiency by the two-dimensional periodic structure can be maintained.

  Next, a method for manufacturing the semiconductor light emitting device of this embodiment will be described.

  29A to 29D are perspective views showing a method for manufacturing the semiconductor light emitting device of this embodiment.

  First, as shown in FIG. 29 (a), the method for manufacturing the semiconductor light emitting device of the first embodiment shown in FIG. 11 or the method of manufacturing the semiconductor light emitting device of the second embodiment shown in FIG. The semiconductor light emitting device of the first embodiment or the second embodiment is manufactured.

  Next, as illustrated in FIG. 29B, the semiconductor light emitting element is mounted on the mounting substrate 22. Thereafter, the resin 23 is dropped on the semiconductor light emitting device.

  Next, as shown in FIG. 29C, after the resin 23 covers the semiconductor light emitting element and before the resin 23 is cured, the resin 23 is formed with a mold 24 provided with a hemispherical cavity. Press. As a result, as shown in FIG. 29 (d), the resin 23 is molded into a semicircular dome shape. Thereafter, the resin is cured with ultraviolet rays. The semiconductor light emitting device of this embodiment is manufactured by the above method.

  Although it has been difficult to form a resin shape in a semi-spherical shape with good reproducibility by the conventional technique of simply applying resin and molding, it is possible to stably mold a resin of the same shape by the manufacturing method of this embodiment. It becomes possible.

  Note that the method for molding a resin into a semispherical shape using a mold as described above is also applicable to semiconductor light emitting devices according to embodiments other than the first and second embodiments of the present invention. Can do.

(Fourth embodiment)
FIG. 30 is a cross-sectional view showing a part of a semiconductor light emitting element according to the fourth embodiment of the present invention. The semiconductor light emitting device of this embodiment is different from the first and second semiconductor light emitting devices in that the sapphire substrate 8 and the AlGaN layer 9 are mounted on the mounting substrate 22 without being removed, and the highly reflective p-electrode 2 That is, the n-electrode 7 and the n-type GaN layer 5 are formed on the same side.

  That is, the semiconductor light emitting device of this embodiment shown in FIG. 30 is formed on a p-type GaN layer 3 having a thickness of 200 nm formed by epitaxial growth and a crystal growth surface (main surface) of the p-type GaN layer 3, A highly reflective p-electrode 2 having a thickness of 1 μm formed by stacking (Pt) and gold (Au), a non-doped InGaN active layer 4 having a thickness of 3 nm formed on the back surface of the p-type GaN layer 3, and an undoped InGaN active An n-type GaN layer 5 having a thickness of 4 μm formed on the back surface of the layer 4; an n-electrode 7 having a thickness of 1 μm formed by laminating Ti and Au formed under the n-type GaN layer 5; AlGaN layer 9 provided on the back surface of type GaN layer 5 and having a convex two-dimensional periodic structure 16 formed on the main surface (the surface facing n-type GaN layer 5), and disposed on the back surface of AlGaN layer 9 And a sapphire substrate 8. In the example shown in FIG. 30, the semiconductor light emitting device is mounted on the mounting substrate 22, and in particular, the highly reflective p-electrode 2 and the n-electrode 7 are connected to the mounting substrate 22 via bumps 25 made of Au. The period of the two-dimensional periodic structure 16, that is, the center interval between adjacent protrusions in the two-dimensional plane is 0.4 μm, and the height of the protrusions and recesses is 150 nm. In the example shown in FIG. 30, the n-type GaN layer 5 is formed so as not to be embedded in the two-dimensional periodic structure 16, but if it is formed so as to be embedded, the light extraction efficiency is lowered. It is preferable to do this.

  As described above, by mounting the substrate made of sapphire or the like while leaving the substrate, the light emitted from the non-doped InGaN active layer 4 has almost no refractive index difference up to the AlGaN layer 9, so there is no loss due to total reflection or Fresnel reflection. Propagates through the light emitting element. However, since the refractive index difference between the sapphire substrate (refractive index 1.6) and the AlGaN layer (refractive index 2.5) is large in the conventional configuration, light having a large incident angle is reflected at the interface between the sapphire substrate and the AlGaN layer. It was totally reflected, returned to the semiconductor multilayer film again, and could not be taken out of the LED. On the other hand, if a two-dimensional periodic structure is formed on the back surface of the AlGaN layer as in the semiconductor light emitting device of this embodiment, the propagation direction is changed by diffraction of the two-dimensional periodic structure. As a result, when the back surface of the AlGaN layer is flat, the light having a large incident angle and a large proportion of the solid angle that has been totally reflected at the interface between the sapphire substrate and the AlGaN layer is not totally reflected. It can be incident on the sapphire substrate. Since the sapphire substrate is transparent and has a small refractive index difference with air, most of the light incident on the sapphire substrate is emitted into the air.

  In addition, when molded with resin, the difference in refractive index between the sapphire substrate and the resin (refractive index of about 1.5) is further reduced, and if the shape of the resin is a hemispherical dome, the light extraction efficiency is further improved. be able to.

  Next, a method for manufacturing the semiconductor light emitting device of this embodiment will be described. 31A to 31E are cross-sectional views illustrating a method for manufacturing the semiconductor light emitting device of this embodiment.

  First, as shown in FIG. 31A, an AlGaN layer 9 is crystal-grown on the sapphire substrate 8 by MOCVD, for example. Here, the thickness of the AlGaN layer 9 is 1 μm in order to reduce crystal defects. The Al composition in the AlGaN layer 9 may be any composition as long as it is transparent to the wavelength of light used in later laser lift-off, but here the composition of Al is 100%. Next, the concave or convex two-dimensional periodic structure 16 is patterned on the AlGaN layer by exposure with a stepper and RIE. Here, the period of the two-dimensional periodic structure 16 is 0.4 μm, and the depth of the concave portion (or the height of the convex portion) is 150 nm.

  Next, as shown in FIG. 31 (b), the n-type GaN layer 5, the non-doped InGaN active layer 4, and the p-type GaN layer are formed on the main surface of the AlGaN layer 9 on which the two-dimensional periodic structure 16 is formed using the MOCVD method. 3 are formed in this order. Crystal growth of the n-type GaN layer 11 is performed by setting growth conditions so that the two-dimensional periodic structure 16 is not embedded.

  Thereafter, as shown in FIG. 31 (c), after etching a part of the region so that the main surface of the n-type GaN layer 5 is exposed, the main surface of the p-type GaN layer 3 is formed by electron beam evaporation. A highly reflective p-electrode 2 made of Pt / Au and an n-electrode 7 made of Ti / Au are formed on the exposed portion of the main surface of the n-type GaN layer 5.

  Next, as shown in FIG. 31D, the semiconductor light emitting element is mounted on the mounting substrate 22 on which the bumps 25 for the n electrode and the highly reflective p electrode are formed. Thereby, the semiconductor light emitting device according to the fourth embodiment of the present invention shown in FIG.

  In the semiconductor light-emitting device fabricated in this way, reflection from the lower surface side of the LED by the highly reflective p-electrode 2 can be used as compared with the case where the main surface of the AlGaN layer 9 is flat. The theoretical calculation result shown in (b) is improved to about twice (four times that of the conventional light emitting device).

  In addition, since heat generated in the active layer can be radiated from the sub-μm and thin p-type GaN layer 3 side through the bump 25 having high thermal conductivity, an excessive temperature rise is prevented in the semiconductor light emitting device of this embodiment. ing. The rate of increase of the light output of the semiconductor light emitting element with respect to the input current is the same as when the input current is small even when a large current of 100 mA flows through the electrodes.

  In the present invention, a two-dimensional periodic structure is formed on the main surface of the AlGaN layer 9 on the sapphire substrate 8, but a two-dimensional periodic structure may be formed on the main surface of the sapphire substrate 8. Moreover, even if a board | substrate is other than sapphire, it should just consist of a material transparent with respect to the light radiated | emitted from an active layer.

  Furthermore, when the back surface (main surface) of the sapphire substrate 8 is a rough surface, the light extraction efficiency is enhanced 4.5 times that of the conventional structure. This is because the loss due to total reflection at the interface between the sapphire substrate and air is reduced due to the rough back surface. Regarding the roughness of the back surface, the autocorrelation distance T of the in-plane distribution of the back surface of the sapphire substrate 8 is 0.5λ / N <T <20λ / N, and the height distribution D in the vertical direction is 0.5λ / N <D <. 20λ / N is preferable because the loss can be sufficiently reduced.

  Furthermore, when it is molded with a semi-spherical resin, the light extraction efficiency is improved 6 times as compared with the conventional structure. This is because the loss due to total reflection at the interface between the sapphire substrate and the resin is reduced because the difference in refractive index between the resin and the sapphire substrate is small.

  In the semiconductor light emitting device of this embodiment, a substrate made of one selected from GaAs, InP, Si, SiC, and AlN can be used instead of the sapphire substrate.

In the example shown in FIG. 30, the example in which the two-dimensional periodic structure 16 is formed on the main surface of the AlGaN layer 9 is shown. However, when a Si substrate is used instead of the sapphire substrate, the two-dimensional periodic structure is formed on the main surface of the Si substrate. A structure may be formed. During crystal growth, the Si substrate is exposed to a high temperature, but a very thin SiO ₂ film is formed on the surface of the Si substrate (the surface of the two-dimensional periodic structure) due to residual oxygen in the crystal growth furnace. The refractive index of Si is about 3.3, whereas the refractive index of SiO ₂ is about 1.4. Since the refractive index of the light emitting semiconductor layer is generally 2.4 to 3.3, the change in the refractive index of the two-dimensional periodic structure is enhanced by this SiO ₂ film. As the refractive index change is larger, the diffraction efficiency is higher, so that the light emission efficiency can be further increased.

(Fifth embodiment)
32A to 32E are perspective views showing a method for manufacturing a semiconductor light emitting device according to the fifth embodiment of the present invention. The manufacturing method of the present embodiment is a method for forming a two-dimensional periodic structure on the main surface of a substrate using a nanoprint method.

  First, as shown in FIGS. 32 (a) and 32 (b), a Si substrate, a SiC substrate, or the like, which is formed of a convex portion having a height of 400 nm and has a two-dimensional periodic structure with a period of 0.4 μm, is prepared. Next, this substrate is used as a mold 26 and pressed against the main surface of the sapphire substrate 8 coated with a 600 nm-thickness resist 27.

  Thereafter, as shown in FIG. 32 (c), when the mold 26 is separated from the sapphire substrate 8, a concave two-dimensional periodic structure (hole depth 400 nm, period 0.4 μm) is transferred to the resist 27.

Next, as shown in FIG. 32D, the resist remaining at the bottom of the hole of the resist 27 is removed by O ₂ dry etching.

  Next, as shown in FIG. 32 (e), after performing dry etching using the resist 27 as an etching mask, the resist 27 is removed to form a concave portion with a depth of 150 nm on the main surface of the sapphire substrate 8, and the period is A two-dimensional periodic structure of 0.4 μm is formed.

  As described above, when the nanoprint method is used, patterning of a fine structure on the order of submicron can be performed without using an expensive manufacturing apparatus such as a stepper or an EB exposure apparatus. In addition, according to the manufacturing method of the present embodiment, patterning can be performed at high speed because it can be performed simply by pressing the mold. If the substrate manufactured as described above is used as a mold, the semiconductor light emitting devices of the first to fourth embodiments of the present invention can be manufactured at low cost.

(Sixth embodiment)
33A to 33G are perspective views illustrating a method for manufacturing a semiconductor light emitting device according to the sixth embodiment of the present invention. The manufacturing method of the semiconductor light emitting device of this embodiment is a method for forming a two-dimensional periodic structure on the main surface of a semiconductor thin film using a soft mold method.

  First, as shown in FIG. 33A, a soft mold used for microfabrication is manufactured. In this step, a period constituted by a hole (concave portion) having a depth of 400 nm formed on a resin 30 such as polysilane applied on a substrate 29 such as a Si substrate or a SiC substrate by photolithography, EB lithography, or nanoprinting method. A two-dimensional periodic structure 31 of 0.4 μm is formed. The resin-coated substrate thus produced is used as a soft mold for a subsequent fine processing step.

  Next, as shown in FIG. 33B, a thin-film semiconductor multilayer film having the Au plating layer 15 is formed by the method described in the first embodiment. However, since the surface of the substrate used for forming the semiconductor multilayer film is flat in the method of this embodiment, the surface of the semiconductor multilayer film is also flat.

  Next, as shown in FIG. 33C, a resist 27 is applied on the main surface of the semiconductor multilayer film. However, the volatilization of the solvent in the resist 27 by baking is not performed here. The soft mold described above is placed on the resist 27. In this case, the soft mold is placed so as not to apply pressure as much as possible so that the semiconductor multilayer film having a thickness of several μm is not destroyed.

  Then, as shown in FIG. 33 (d), the resin 30 absorbs the solvent of the resist 27 to cause a capillary phenomenon, and the resist 27 penetrates so as to fill the holes of the two-dimensional period of the soft mold resin.

  Thereafter, as shown in FIG. 33E, when the mold is separated from the semiconductor multilayer film, a convex two-dimensional periodic structure (convex height 400 nm, period 0.4 μm) is transferred to the resist 27.

Next, as shown in FIG. 33F, the resist 27 remaining at the bottom of the resist hole is removed by O ₂ dry etching.

  Thereafter, as shown in FIG. 33G, the main surface of the semiconductor multilayer film is dry-etched using the resist 27 as an etching mask, and then the resist is removed, whereby a two-dimensional periodic structure ( And a convex portion having a height of 150 nm and a period of 0.4 μm).

  As described above, when the soft mold method is used, fine processing on the order of submicron is possible even for a thin film that is extremely difficult to handle, such as a semiconductor multilayer film having a thickness of about several μm. In this case, since the substrate used for crystal growth of the semiconductor multilayer film may be flat, the crystal growth is easier than in the case of crystal growth on a substrate having irregularities.

  In the embodiment described so far, it is difficult to process a nitride-based compound semiconductor that is difficult to process, or a micro-fabrication that has a concave / convex period that corresponds to a short oscillation wavelength of blue or purple. Although specifically described, the design of the present invention can be applied to an infrared or red semiconductor light emitting device using AlGaAs (refractive index 3.6) or AlGaInP (refractive index 3.5) as a semiconductor. .

(Seventh embodiment)
FIG. 34 is a perspective view showing a semiconductor light emitting element according to the seventh embodiment of the present invention. As shown in the figure, the semiconductor light emitting device of this embodiment is formed on a p-type AlGaN layer 43 having a thickness of 200 nm formed by epitaxial growth, and a crystal growth surface (main surface) of the p-type AlGaN layer 43. A highly reflective p-electrode (first electrode) 42 made of Al having a thickness of 0.5 μm, an Au plating layer 41 having a thickness of 10 μm formed on the lower surface of the highly reflective p-electrode 2, and a p-type GaN layer 43. A 3 nm thick non-doped AlInGaN active layer 44 formed on the back surface, and a 4 μm thick n-type AlGaN formed on the back surface of the non-doped AlInGaN active layer 44 and having a convex two-dimensional periodic structure 46 formed on the back surface. A layer (second semiconductor layer) 45 and an n-electrode (second electrode) 47 having a thickness of 1 μm formed on the back surface of the n-type GaN layer 5 and laminated with titanium (Ti) and Au. I have. Here, the lower surface means a surface located on the lower side in FIG. 34 in a certain layer.

  The semiconductor light emitting device of this embodiment functions as an ultraviolet LED from which light is extracted from the back surface direction of the n-type AlGaN layer 45, and the PL peak wavelength of the non-doped AlInGaN active layer 44 is 350 nm.

  The period of the two-dimensional periodic structure 46 formed on the back surface of the n-type AlGaN layer 45, that is, the center interval between adjacent protrusions in the two-dimensional plane is 0.3 μm, and the height of the protrusions is 130 nm.

  The nitride-based compound semiconductor constituting the semiconductor light-emitting device of this embodiment is formed using the MOCVD method, the MBE method, or the like in the same manner as the nitride-based compound semiconductor constituting the semiconductor light-emitting device according to the first embodiment. be able to.

  Also in the semiconductor light emitting device of this embodiment, high light extraction efficiency and excellent heat dissipation are realized as in the semiconductor light emitting device of the first embodiment. In particular, since the high reflectivity p-electrode 42 is made of Al, light generated in the non-doped AlInGaN active layer 44 can be reflected with high efficiency.

  Thus, the structure of the semiconductor light emitting device according to the present invention is also effectively applied to a light emitting device having an emission wavelength peak in the ultraviolet region.

  The semiconductor light emitting device of the present invention is useful as a light source with high luminous efficiency.

1 is a perspective view showing a semiconductor light emitting element according to a first embodiment of the present invention. It is a figure which shows the theoretical calculation result of the incident angle dependence of the light quantity radiated | emitted outside the semiconductor light-emitting device. (A) is a figure which shows the structure in real space in LED, (b) and (c) are figures which show the structure in the wave number space in a light emitting element. (A), (b) is a figure which shows the structure of wave number space in case the 2-dimensional periodic structure of a 0.1 micrometer period is formed in the n-type GaN surface. It is a figure which shows the refractive index in each part of the semiconductor layer in which the periodic structure was formed in the surface. (A)-(c) is a figure which shows the structure of wave number space in case the 2-dimensional periodic structure of a 0.2 micrometer period is formed in the n-type GaN surface. It is a figure which shows the structure of wave number space when the two-dimensional periodic structure of a 0.4 micrometer period is formed in the surface of an n-type GaN layer. It is a figure for demonstrating the solid angle used for calculation of light extraction efficiency. It is a figure which shows the value which normalized the light extraction efficiency calculated | required using the calculation formula with the light extraction efficiency in case the surface of an n-type GaN layer is flat. (A), (b) is a top view which shows the arrangement | sequence of the two-dimensional periodic structure formed in the n-type GaN layer surface. (A)-(f) is a perspective view which shows the manufacturing method of the semiconductor light-emitting device based on 1st Embodiment. (A) is a figure which shows the current-voltage characteristic of the semiconductor light-emitting device which concerns on the conventional and 1st embodiment, (b) is the current-light output characteristic of the semiconductor light-emitting device which concerns on the conventional and 1st embodiment. FIG. (A), (b) is a perspective view which shows the modification of the semiconductor light-emitting device which concerns on 1st Embodiment, respectively. It is a perspective view which shows the modification of the semiconductor light-emitting device which concerns on 1st Embodiment, respectively. (A), (b) is a perspective view which shows the modification of the semiconductor light-emitting device which concerns on 1st Embodiment, respectively. (A), (b) is a perspective view which shows the modification of the semiconductor light-emitting device which concerns on 1st Embodiment, respectively. It is a figure which shows the theoretical calculation result of the dependence with respect to the inclination-angle of a recessed part of light extraction efficiency. (A)-(f) is a perspective view which shows the 2nd manufacturing method of the semiconductor light-emitting device of this embodiment shown in FIG. (A) is a perspective view which shows the semiconductor light-emitting device based on the 2nd Embodiment of this invention, (b) is the top view which looked at the semiconductor light-emitting device of 2nd Embodiment from the top. (A) is a figure which shows the theoretical calculation result of the transmittance | permeability T of the light which injects into the surface of an n-type GaN layer at the time of forming a hexagonal pyramid-shaped protrusion in the surface (back surface) of an n-type GaN layer, (B) is a figure which shows the relationship between the period of a two-dimensional periodic structure, and light extraction efficiency. (A)-(f) is a perspective view which shows the manufacturing method of the semiconductor light-emitting device which concerns on 2nd Embodiment. (A)-(c) is a figure which shows the modification of the manufacturing method of the semiconductor light-emitting device which concerns on 2nd Embodiment. (A), (b) is a figure which shows the modification of the manufacturing method of the semiconductor light-emitting device based on 2nd Embodiment. (A), (b) is a figure which shows the modification of the manufacturing method of the semiconductor light-emitting device based on 2nd Embodiment. (A), (b) is a figure which shows the modification of the manufacturing method of the semiconductor light-emitting device based on 2nd Embodiment. (A)-(c) is a figure which shows the modification of the manufacturing method of the semiconductor light-emitting device which concerns on 2nd Embodiment. It is a perspective view which shows the semiconductor light-emitting device concerning the 3rd Embodiment of this invention. (A) is a figure which shows the theoretical calculation result of the light transmittance at the time of molding a semiconductor light-emitting device with resin, (b) is a figure of light extraction efficiency in the semiconductor light-emitting device which concerns on 3rd Embodiment. It is a figure which shows the theoretical calculation result of the dependence with respect to the period of a two-dimensional periodic structure. (A)-(d) is a perspective view which shows the manufacturing method of the semiconductor light-emitting device concerning 3rd Embodiment. It is sectional drawing which shows a part of semiconductor light-emitting device based on the 4th Embodiment of this invention. (A)-(e) is sectional drawing which shows the manufacturing method of the semiconductor light-emitting device based on 4th Embodiment. (A)-(e) is a perspective view which shows the manufacturing method of the semiconductor light-emitting device based on the 5th Embodiment of this invention. (A)-(g) is a perspective view which shows the manufacturing method of the semiconductor light-emitting device based on the 6th Embodiment of this invention. It is a perspective view which shows the semiconductor light-emitting device concerning the 7th Embodiment of this invention. It is a perspective view which shows the conventional semiconductor light-emitting device. It is a perspective view which shows the conventional semiconductor light-emitting device in which the photonic crystal was formed in the upper surface.

Explanation of symbols

1, 15, 41 Au plating layer 2, 14, 42 High reflection p electrode 3, 13 p-type GaN layer 4, 12 Non-doped InGaN active layer 5, 11 n-type GaN layer 6, 10, 16, 17, 18, 19, 20, 31, 46 Two-dimensional periodic structure 7, 47 n electrode 8 sapphire substrate 9 AlGaN layer 21 etching mask 22 mounting substrate 23, 30 resin 24 mold 25 bump 26 mold 27 resist 29 substrate 43 p-type AlGaN layer 44 non-doped AlInGaN active Layer 45 n-type AlGaN layer 51 Si substrate

Claims (14)

  A semiconductor light emitting device including a multilayer semiconductor layer formed on a substrate and then peeled off from the substrate, wherein a two-dimensional periodic structure is formed on a first main surface of the surface of the multilayer semiconductor layer that is in contact with the substrate A semiconductor light emitting element characterized in that is formed.   The semiconductor light emitting element according to claim 1, wherein the substrate is made of silicon. A first electrode provided on the second main surface of the multilayer semiconductor layer and having a reflectance of 80% or more with respect to a peak wavelength of light generated in the active layer;
2. The semiconductor light emitting element according to claim 1, further comprising: a second electrode provided on a region of the first main surface of the multilayer semiconductor layer where the two-dimensional periodic structure is not formed. .   A semiconductor comprising: a substrate having a two-dimensional periodic structure on a main surface; and a multilayer semiconductor layer formed on the main surface of the substrate and having an active layer for generating light, wherein the substrate is silicon. Light emitting element. A substrate having a two-dimensional periodic structure on a main surface; and a multilayer semiconductor layer formed on the main surface of the substrate and having an active layer for generating light,
An air gap is formed in a part between the main surface of the substrate and the first main surface of the multilayer semiconductor layer. Forming a first two-dimensional periodic structure on a main surface on a substrate;
Forming a multilayer semiconductor layer on the first two-dimensional periodic structure (b);
A method of manufacturing a semiconductor light emitting device, comprising the step (c) of separating the substrate and the multilayer semiconductor layer.   The step (b) includes a step of forming a shape complementary to the first two-dimensional periodic structure on the first main surface of the multilayer semiconductor layer. A method for manufacturing a semiconductor device. The shape complementary to the first two-dimensional periodic structure formed in the step (b) is composed of a concave portion,
8. The method according to claim 7, further comprising a step of deepening the concave portion or changing a cross-sectional shape of the concave portion by flowing electricity to the multilayer semiconductor layer in an electrolytic solution after the step (c). The manufacturing method of the semiconductor light-emitting device of description.   The method of manufacturing a semiconductor light emitting element according to claim 6, wherein the substrate is made of silicon.   The method of manufacturing a semiconductor light emitting element according to claim 6, wherein the step (c) is performed by at least one of polishing the substrate and wet etching the substrate.   The method of manufacturing a semiconductor light emitting element according to claim 6, wherein the step (c) is performed by laser lift-off.   The method of manufacturing a semiconductor light emitting device according to claim 6, wherein the substrate removed in the step (c) is reusable.   After the step (c), wet etching is performed under conditions where the etching rate varies depending on the crystal plane, whereby a second two-dimensional periodic structure composed of polygonal pyramid-shaped convex portions or concave portions is formed in the multilayer semiconductor layer. The method of manufacturing a semiconductor light emitting element according to claim 7, further comprising a step of forming on one main surface.   The said process (b) forms the said multilayer semiconductor layer so that a space | gap may arise in the one part area | region of the interface of the main surface of the said board | substrate, and the back surface of the said multilayer semiconductor layer. A method for manufacturing a semiconductor light emitting device.

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