JP2015207587A - Light emitting element and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light emitting element and a manufacturing method of the same, which can transfer a fine concavo-convex structure on an element surface without using etching by a chlorine gas and which improve luminescent efficiency characteristics.SOLUTION: A light emitting element comprises: a p-type semiconductor layer (5) which is an outermost layer on the light radiation side; an inorganic compound layer (8) formed by being layered on the p-type compound layer, in which the inorganic compound layer has a refraction index not less than 0.5 and not more than 1.0 times larger than a refraction index of the p-type semiconductor layer and contains at least one element selected from Cr, Hf, Ni, Mg, Nb, Ta, W, Ti, Zn, Zr and Si; and a fine concavo-convex structure (9) formed on a surface of the inorganic compound layer by using a self-organizing pattern of a resin composition containing block copolymer or graft copolymer.

Description

  The present invention relates to a light emitting device having a fine concavo-convex structure on a radiation side surface of light generated inside the light emitting device and a method for manufacturing the same.

  The luminous efficiency of a light emitting device such as an LED is determined by the product of the internal quantum efficiency when light is emitted from the active layer (light emitting layer) and the light extraction efficiency for extracting light to the outside. Therefore, in order to effectively improve the light emission efficiency, it is preferable to improve both the internal quantum efficiency and the light extraction efficiency.

  Research on internal quantum efficiency has progressed and significant improvements have been seen in recent years. However, with regard to light extraction efficiency, the light-emitting element material generally has a high refractive index, and light is confined in the element due to total reflection or the like. Therefore, it was in a low state, leaving room for improvement.

  Therefore, conventionally, an attempt has been made to prevent reflection by creating a refractive index gradient by forming irregularities of nm level on the surface of the light emitting element by etching or the like, and an attempt to create a diffraction grating on the surface of the light emitting element and extract the first-order diffracted light. Etc. have been made. And, as a processing method for forming a fine concavo-convex structure, electron beam lithography, nanoimprint method, and the like are being studied.

  However, these methods have a problem that the apparatus cost is high, and the nano-sized fine concavo-convex structure must be regularly controlled and manufactured, so that it is difficult to manufacture and practical application is difficult. .

  Further, as a technique for roughening the surface of the light emitting element, generally, a technique for roughening by surface treatment with hydrochloric acid, sulfuric acid, hydrogen peroxide or a mixed solution thereof is known. Under the influence of the crystallinity of the substrate, a surface that can be roughened and a surface that cannot be roughened depending on the orientation of the exposed surface. For this reason, the surface of the light emitting element cannot always be roughened, and there has been a restriction on improving the light extraction efficiency.

Japanese Patent No. 3882357 Japanese Patent No. 4077312 Japanese Patent No. 4455645

  According to the inventions described in Patent Documents 1 to 3, a fine uneven structure is formed on the element surface by performing a roughening treatment using a block copolymer on the element surface (light extraction surface). We are trying to improve the extraction efficiency. At this time, a self-organized pattern is formed from the block copolymer, and the light extraction surface is etched using the self-organized pattern as a mask to form a fine concavo-convex structure.

Specifically, according to Patent Documents 2 and 3, to form a self-assembled pattern on the surface of the Al ₂ O ₃ layer according to the block copolymer, a fine uneven structure on the surface of the Al ₂ O ₃ layer self-assembly pattern as a mask It is formed by dry etching using a chlorine-based gas. Also in Patent Document 1, a fine concavo-convex structure is formed on the surface of a current diffusion layer under a self-organized pattern by a block copolymer by dry etching using a chlorine-based gas.

  However, as shown in each patent document, since a chlorine-based gas is used as an etching gas for forming a fine concavo-convex structure using a self-organized pattern of a block copolymer as a mask, there is a concern about adverse effects such as metal corrosion due to residual chlorine. It was done. For this reason, there existed a problem which manufacturing cost improved, for example, the abatement equipment of chlorine gas was needed.

  The present invention has been made in view of the above points, and provides a light emitting device and a method for manufacturing the same, which can transfer a fine concavo-convex structure on the surface of the device without using etching with a chlorine-based gas and have improved luminous efficiency characteristics. The purpose is to provide.

  The light-emitting element in the present invention has a light emission side outermost layer of a semiconductor layer and an inorganic compound layer formed on the light emission side of the light emission side outermost layer, and the inorganic compound layer has a refractive index. Is not less than 0.5 times and not more than 1.0 times the refractive index of the outermost layer on the light emission side, and is at least any selected from Cr, Hf, Ni, Mg, Nb, Ta, W, Ti, Zn, Zr, and Si The surface of the inorganic compound layer has a fine concavo-convex structure formed by using a self-organized pattern of a resin composition containing a block copolymer or a graft copolymer. It is characterized by being given.

In the present invention, the element contained in the inorganic compound layer is preferably at least one selected from Mg, Nb, Ta, W, and Ti. Specifically, the inorganic compound layer is formed of at least one inorganic compound selected from MgO, Nb ₂ O ₅ , Ta ₂ O ₅ , WO ₃ , TiO, Ti ₃ O ₅ , and TiO _2. Is preferred.

  Moreover, in this invention, the pitch of the said fine uneven structure is 20-1000 nm, the height of the said fine uneven structure is 20-1000 nm, and the thickness of the said inorganic compound layer is 5 of the height of the said fine uneven structure. It is preferable that it is less than twice. Moreover, in this invention, the pitch of the said fine uneven structure is 100-1000 nm, the height of the said fine uneven structure is 50-1000 nm, and the thickness of the said inorganic compound layer is 3 of the height of the said fine uneven structure. It is more preferable that the ratio is not more than twice.

  Further, the present invention is a method for manufacturing a light emitting device according to any one of the above, wherein the refractive index of the semiconductor layer on the light emission side outermost layer is at least 0.5 times the refractive index of the light emission side outermost layer. A step of forming an inorganic compound layer that is 1.0 times or less and includes at least any one element selected from Cr, Hf, Ni, Mg, Nb, Ta, W, Ti, Zn, Zr, and Si; A step of forming a resin composition layer containing a block copolymer or a graft copolymer on the surface of the inorganic compound layer, a step of forming a self-assembly pattern on the resin composition layer, and the self-assembly pattern, And transferring to the surface of the inorganic compound layer by etching to form a fine concavo-convex structure in the inorganic compound layer.

  The present invention includes a step of forming a transfer intermediate layer between the inorganic compound layer and the resin composition layer, and after transferring the self-assembled pattern to the transfer intermediate layer by etching, the transfer intermediate layer It is preferable to transfer the fine concavo-convex structure onto the surface of the inorganic compound layer using the pattern transferred to the mask as a mask. In the present invention, the transfer intermediate layer is made of a material having an etching selection ratio with the inorganic compound layer that is higher in the transfer intermediate layer than in the resin composition layer having the self-assembled pattern. Is preferred.

  Conventionally, when a fine concavo-convex structure is formed on the surface of a device using a self-organized pattern of a block copolymer or a graft copolymer, a chlorine-based gas is used as an etching gas.

  However, the present inventors considered the influence on the element when using a chlorine-based gas as a problem, and intensively studied and repeated experiments in order to find an element structure that can be etched without using a chlorine-based gas as an etching gas. As a result, the present invention has been achieved.

  That is, the present inventors use the self-organized pattern of the block copolymer or graft copolymer as a mask to enable etching without using a chlorine-based gas when etching the device surface, so An inorganic compound layer formed on the outer layer was formed of a specific material. In order to improve the luminous efficiency, the refractive index range of the inorganic compound layer was defined in order to sufficiently suppress the loss of light at the interface with the outermost layer on the light emission side. Specifically, the inorganic compound layer is composed of an inorganic compound using at least one element selected from Cr, Hf, Ni, Mg, Nb, Ta, W, Ti, Zn, Zr, and Si. As a result, the refractive index can be adjusted to 0.5 to 1.0 times the refractive index of the outermost layer on the light emitting side, and chlorine-based gas can be used when etching using a self-organized pattern of a block copolymer or graft copolymer as a mask. Even if not used, it is possible to form a fine relief structure on the surface of the inorganic compound layer.

  Conventionally, in order to eliminate the need for chlorine gas during etching, attempts have been made to link a self-organized pattern of a block copolymer or a graft copolymer with an inorganic compound layer made of a specific material presented in the present invention. Absent.

  In the present invention, as a method for producing a light-emitting element, in addition to a method for forming a fine concavo-convex structure by directly transferring a self-assembled pattern to an inorganic compound layer, transfer is performed between the inorganic compound layer and the resin composition layer. A method of providing an intermediate layer and transferring the pattern to the transfer intermediate layer first can also be presented. According to this method, the fine relief structure is transferred onto the surface of the inorganic compound layer using the pattern transferred to the transfer intermediate layer as a mask. When the self-organization pattern is directly transferred to the inorganic compound layer due to the etching selection ratio, the pattern transferability is lowered, and the etching selectivity with the inorganic compound layer is higher than that of the self-assembly pattern (resin composition layer). By providing the transfer intermediate layer, the pattern transfer property to the inorganic compound layer can be improved.

  According to the present invention, it is possible to transfer a fine concavo-convex structure on the element surface without using etching with a chlorine-based gas, and to improve the luminous efficiency characteristics. Further, since it is not necessary to use a chlorine-based gas, a fine uneven structure can be formed at low cost.

It is a cross-sectional schematic diagram of the light emitting element in this invention. It is a cross-sectional schematic diagram of the light emitting element in this invention which a part differs from FIG. It is process drawing for demonstrating the 1st manufacturing method of the light emitting element in this invention. FIG. 4 is a process diagram performed subsequent to FIG. 3. It is process drawing for demonstrating the 2nd manufacturing method of the light emitting element in this invention. It is process drawing performed after FIG. 2 is a SEM photograph of a self-organized pattern in Example 1. ₃ is a SEM photograph of a fine relief structure formed on the surface of an Nb ₂ O ₅ layer in Example 1. It is a schematic diagram of FIG. It is a schematic diagram of FIG.

  Hereinafter, an embodiment of the present invention (hereinafter abbreviated as “this embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

  FIG. 1 is a schematic cross-sectional view of a light-emitting element in the present invention. The light emitting element according to the present invention refers to a light emitting element such as a light emitting diode (LED) or a laser diode (LD).

  As shown in FIG. 1, the light-emitting element 1 has a laminated structure in which an n-type semiconductor layer 3, an active layer (light-emitting layer) 4, and a p-type semiconductor layer 5 are sequentially formed on a substrate 2.

  As shown in FIG. 1, an n-side electrode layer 6 is formed on the back surface of the substrate 2. A p-side electrode layer 7 is formed on the surface of the p-type semiconductor layer 5. As shown in FIG. 1, the n-side electrode layer 6 and the p-side electrode layer 7 are formed in a desired shape. As shown in FIG. 1, the surface 5 a of the p-type semiconductor layer 5 extends around the p-side electrode layer 7. The p-type semiconductor layer 5 is a semiconductor layer on the light emission side, and in the embodiment of FIG. 1, the p-side semiconductor layer 5 corresponds to the outermost layer on the light emission side. However, unlike the embodiment of FIG. 1, for example, a current diffusion layer or a light transmissive electrode may be formed over the surface 5 a of the p-side semiconductor layer 5. In this case, the outermost layer on the light emission side is a current diffusion layer or a light transmissive electrode.

  As shown in FIG. 1, an inorganic compound is superimposed on the surface 5a of the p-side semiconductor layer 5 corresponding to the outermost layer on the light emission side (the surface 5a here refers to an exposed surface where the p-side electrode layer 7 is not formed). A layer (inorganic light transmissive layer) 8 is formed. As shown in FIG. 1, a fine concavo-convex structure 9 is provided on the surface of the inorganic compound layer 8. Here, the state in which the fine concavo-convex structure 9 is provided on the surface of the inorganic compound layer 8 means that when the element surface (light extraction surface) is viewed from the plane, a plurality of nano-order sized protrusions or recesses are formed. In this state, at least one of the flat portion extending around the convex portion or the concave portion is a state composed of the inorganic compound layer 8. This corresponds to FIG. 1 and FIG. 2 described later.

  The material of the board | substrate 2 which comprises the light emitting element 1 which concerns on this Embodiment is not restrict | limited. For example, sapphire, SiC, SiN, GaN, silicon, zinc oxide, magnesium oxide, manganese oxide, zirconium oxide, manganese zinc iron, magnesium aluminum oxide, zirconium boride, gallium oxide, indium oxide, lithium gallium oxide, lithium aluminum oxide Alternatively, neodymium gallium oxide, lanthanum strontium aluminum tantalum, strontium titanium oxide, titanium oxide, hafnium, tungsten, molybdenum, GaP, GaAs, or the like can be used.

  In the light emitting element 1 according to the present embodiment, the material of the n-type semiconductor layer 3 is not particularly limited as long as it can be used as the n-type semiconductor layer 3 suitable for the light emitting element 1. For example, elemental semiconductors such as silicon and germanium, and compound semiconductors such as III-V, II-VI, and VI-VI can be appropriately doped with various elements.

  The active layer 4 is not particularly limited as long as the light emitting element 1 has light emission characteristics. For example, as the active layer 4, a semiconductor layer such as AsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGaInP, or ZnO can be applied.

  In the light-emitting element 1 according to the present embodiment, the material of the p-type semiconductor layer 5 is not particularly limited as long as it can be used as a p-type semiconductor layer suitable for the light-emitting element. For example, elemental semiconductors such as silicon and germanium, and compound semiconductors such as III-V, II-VI, and VI-VI can be appropriately doped with various elements.

  The material of the electrode layers 6 and 7 was selected from, for example, Ni, Pd, Co, Fe, Ti, Cu, Rh, Au, Ru, W, Zr, Mo, Ta, Pt, Ag, and oxides and nitrides thereof. An alloy containing at least one kind or a multilayer film can be used.

  The inorganic compound layer 8 will be described. The inorganic compound layer 8 has a refractive index of 0.5 to 1.0 times the refractive index of the p-type semiconductor layer 5, and Cr, Hf, Ni, Mg, Nb, Ta, W, Ti, Zn, Zr And an inorganic compound containing at least one element selected from Si.

  By making the refractive index of the inorganic compound layer 8 0.5 times or more and 1.0 times or less than the refractive index of the p-type semiconductor layer 5, light at the interface between the p-type semiconductor layer 5 and the inorganic compound layer 8 is reflected. Loss can be suppressed sufficiently. Incidentally, the p-type semiconductor layer 5 has a refractive index of about 2.0 to 4.0, and the inorganic compound layer 8 has a refractive index of about 1.0 to 4.0.

  In addition, Cr, Hf, Ni, Mg, Nb, Ta, W, Ti, Zn, Zr, and Si are elements that are preferably used from the viewpoints of refractive index, etching property, film formability, and light transmittance. . The element contained in the inorganic compound layer 8 is more preferably at least one selected from Mg, Nb, Ta, W, and Ti.

As the inorganic compound, those that can be easily formed by sputtering or vapor deposition and have high light transmittance are desirable from the viewpoint of the manufacturing process. The inorganic compounds that are preferably used are oxides or nitrides of the elements listed above, for example, Cr ₂ O ₃ , HfO ₂ , NiO, MgO, Nb ₂ O ₅ , Ta ₂ O ₅ , WO ₃ , TiO, Examples thereof include Ti ₃ O ₅ , TiO ₂ , ZnO, ZrO ₂ , Si ₃ N _4, and mixtures thereof. Among these, MgO, Nb ₂ O ₅ , Ta ₂ O ₅ , WO ₃ , TiO, Ti ₃ O ₅ and TiO ₂ are preferably used from the viewpoint of etching property.

  These inorganic compounds can be formed on the surface 5a of the p-type semiconductor layer 5 corresponding to the outermost layer on the light emission side shown in FIG. 1 with a thickness in the range of 20 nm to 5000 nm by sputtering or vapor deposition. As a method for measuring the film thickness, it can be obtained by a contact method in which a film is scratched and a terminal is brought into contact with the surface to measure the step, or a non-contact method using ellipsometry.

  The shape of the fine concavo-convex structure 9 shown in FIG. 1 is not particularly limited, such as a dot shape, a hole shape, or a line shape. The pitch of the fine concavo-convex structure 9 is 20 to 1000 nm, preferably 100 to 1000 nm. The pitch can be measured by the distance between the centers of adjacent convex portions (distance between centroids) or the distance between centers of adjacent concave portions (distance between centroids). Thus, by setting the pitch to 20 to 1000 nm, preferably 100 to 1000 nm, it acts as a diffraction grating for visible light, and the ability to improve luminance for visible light can be improved.

  Moreover, the height of the fine relief structure 9 is 20 to 1000 nm, preferably 50 to 1000 nm. When the height of the fine concavo-convex structure 9 is 20 to 1000 nm, preferably 20 to 1000 nm, the fabrication becomes easy and the luminance enhancement ability can be improved. Moreover, the thickness of the inorganic compound layer 8 is 5 times or less, preferably 3 times or less the height of the fine relief structure 9 formed on the surface. By making the thickness of the inorganic compound layer 8 5 times or less, preferably 3 times or less the height of the fine concavo-convex structure 9, it is possible to improve the luminance improving ability. In the embodiment of FIG. 1, since the thickness of the inorganic compound layer 8 = the height of the fine concavo-convex structure 9, the thickness of the inorganic compound layer 8 is one time the height of the fine concavo-convex structure 9.

  The fine uneven structure 9 is a random fine pattern. That is, the above-described pitch is not substantially constant between the convex portions or the concave portions, and varies. Therefore, the fine concavo-convex structure 9 in the present invention is distinguished from the regularly arranged fine concavo-convex structure. The pitch of the fine concavo-convex structure 9 described above can be expressed as an average pitch of a predetermined number of fine concavo-convex structures 9. For example, the average pitch can be obtained from the pitch between 10 convex portions.

  In the embodiment shown in FIG. 1, when viewed in cross section, the inorganic compound layer 8 includes a fine concavo-convex structure 9 in which a large number of convex portions 10 are formed on the surface 5 a of the p-type semiconductor layer 5 at intervals. For this reason, between the convex parts 10, the surface 5a of the p-type semiconductor layer 5 is exposed.

  On the other hand, FIG. 2 shows a configuration in which the fine concavo-convex structure 9 is formed only on the surface layer of the lower layer portion 8a and the surface layer constituting the inorganic compound layer 8. Therefore, in the embodiment shown in FIG. 1, the surface 5a of the p-type semiconductor layer 5 is not exposed. 2, the same reference numerals as those in FIG. 1 indicate the same layers as those in FIG.

  According to the configuration of FIG. 2, the etching effect when the fine uneven structure 9 is formed in the inorganic compound layer 8 does not reach the p-type semiconductor layer 5.

  The fine concavo-convex structure 9 shown in FIGS. 1 and 2 is formed using a self-organized pattern of a resin composition containing a block copolymer or a graft copolymer.

  A block copolymer is a polymer having a structure in which two homopolymers are chemically bonded at one place. The graft copolymer is a polymer having a structure in which a polymer made of another kind of monomer is branched and bonded to a polymer chain.

  When these polymers are made into a thin film and heated, microphase separation occurs and the same polymers aggregate to form a nano-level sea-island structure. This is self-organization. The two polymers constituting the block copolymer or graft copolymer have different etching resistances. Therefore, the polymer aggregated in the island shape or the polymer aggregated in the sea shape can be selectively removed by etching. Thereby, the self-organization pattern (fine uneven | corrugated pattern) by a block copolymer or a graft copolymer can be formed.

  In the present invention, the fine concavo-convex structure 9 shown in FIGS. 1 and 2 can be formed in a random pattern on the inorganic compound layer 8 using the self-organization pattern. In the present invention, the inorganic compound layer 8 is formed of an inorganic compound containing at least one element selected from Cr, Hf, Ni, Mg, Nb, Ta, W, Ti, Zn, Zr, and Si. For this reason, when a fine concavo-convex structure is formed by etching on the surface of the inorganic compound layer 8 using the self-assembled pattern as a mask, the etching can be performed without using a chlorine-based gas. Therefore, it is possible to suppress the influence of the chlorine-based gas on the element such as metal corrosion. And the fine uneven structure 9 can be formed in a random pattern on the surface of the inorganic compound layer 8 using a self-organization pattern such as a block copolymer, and the refractive index of the inorganic compound layer 8 corresponds to the outermost layer on the light emission side By setting the p-type semiconductor layer 5 to be 0.5 times or more and 1.0 times or less that of the p-type semiconductor layer 5, the light emission efficiency characteristics can be improved. As described above, in the present invention, the fine uneven structure can be transferred to the inorganic compound layer 8 without using etching with a chlorine-based gas, and the luminous efficiency characteristics can be improved.

  Next, the manufacturing method of the light emitting element in this invention is demonstrated. FIG. 3 is a process diagram for explaining a first method for manufacturing a light emitting device according to the present invention, and FIG. 4 is a process diagram performed after FIG.

  In FIG. 3A, the n-type semiconductor layer 3, the active layer 4, and the p-type semiconductor layer 5 are stacked on the substrate 2. 3 to 6, the substrate 2, the n-type semiconductor layer 3, and the active layer 4 are not shown.

  Next, in the process of FIG. 3B, the inorganic compound layer 8 is formed on the surface (upper surface) 5 a of the p-type semiconductor layer 5. The inorganic compound layer 8 is formed with a thickness in the range of 20 nm to 5000 nm by sputtering or vapor deposition.

In the present invention, the inorganic compound layer 8 has a refractive index of 0.5 to 1.0 times that of the p-type semiconductor layer 5, and Cr, Hf, Ni, Mg, Nb, Ta, W, It is formed of an inorganic compound containing at least one element selected from Ti, Zn, Zr, and Si. Of these elements, the element contained in the inorganic compound layer 8 is more preferably at least one selected from Mg, Nb, Ta, W, and Ti. Specifically, the inorganic compound layer 8 may be formed of at least one inorganic compound selected from MgO, Nb ₂ O ₅ , Ta ₂ O ₅ , WO ₃ , TiO, Ti ₃ O ₅ or TiO _2. Is preferred.

  Next, in the step shown in FIG. 3C, the resin composition layer 20 containing a block copolymer or a graft copolymer is formed on the surface 8 b of the inorganic compound layer 8. The resin composition layer 20 will be described in detail.

  In the present invention, a block copolymer or graft copolymer containing an aromatic ring-containing polymer and poly (meth) acrylate as a block part or graft part is preferred as the block copolymer or graft copolymer.

  The resin composition further includes an aromatic ring-containing homopolymer comprising monomers constituting the aromatic ring-containing polymer contained in the block copolymer or graft copolymer as a block portion or graft portion, and a block copolymer or graft copolymer. It is preferable to contain a poly (meth) acrylate homopolymer composed of monomers constituting the poly (meth) acrylate contained as a part. A block copolymer or a graft copolymer alone usually has a fine structure with a pitch of 100 nm or less, but an aromatic ring-containing homopolymer composed of monomers constituting an aromatic ring-containing polymer contained in the block copolymer or graft copolymer as a block part or a graft part. In addition, the block copolymer or graft copolymer contains a poly (meth) acrylate homopolymer composed of monomers constituting the poly (meth) acrylate contained as a block part or graft part, thereby forming a fine structure with a pitch exceeding 100 nm. It becomes possible to do.

  The aromatic ring-containing polymer contained as a block part of a block copolymer or a graft part of a graft copolymer is a homopolymer of a vinyl monomer having a heteroaromatic ring such as an aromatic ring or a pyridine ring as a side chain. PS), polymethylstyrene, polyethylstyrene, polyt-butylstyrene, polymethoxystyrene, polyN, N-dimethylaminostyrene, polychlorostyrene, polybromostyrene, polytrifluoromethylstyrene, polytrimethylsilylstyrene, Polydivinylbenzene, polycyanostyrene, poly α-methylstyrene, polyvinyl naphthalene, polyvinyl biphenyl, polyvinyl pyrene, polyvinyl phenanthrene, polyisopropenyl naphthalene, polyvinyl pyridine It can be mentioned. The aromatic ring-containing polymer most preferably used here is polystyrene from the viewpoint of availability of raw material monomers and ease of synthesis.

  The poly (meth) acrylate, which is another constituent component contained as a block part of the block copolymer or a graft part of the graft copolymer, is at least one homopolymer selected from the group consisting of the following acrylate monomers and methacrylate monomers or It is a copolymer. Examples of the group consisting of acrylate monomers and methacrylate monomers that can be used here include methyl methacrylate (hereinafter also referred to as MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid. Isobutyl acid, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid t -Butyl, n-hexyl acrylate, cyclohexyl acrylate and the like. The poly (meth) acrylate most preferably used here is a methyl methacrylate homopolymer polymethyl methacrylate (hereinafter also referred to as PMMA) from the viewpoint of availability of raw material monomers and ease of synthesis.

  The number average molecular weight of the block copolymer or graft copolymer used in the present invention is preferably 30,000 or more, more preferably 50,000 or more, from the viewpoint of phase separation. On the other hand, from the viewpoint of molecular weight controllability at the time of synthesis and viscosity suppression when used as a composition, 5 million or less is preferable, and 3 million or less is more preferable. As the composition of the block copolymer or graft copolymer, the ratio of the aromatic ring-containing polymer to the poly (meth) acrylate can be arbitrarily changed within the range of 1: 9 to 9: 1. In addition, other blocks or graft units such as polyethylene oxide may be contained within a range not exceeding 50% by mass.

  Aromatic ring-containing homopolymer composed of monomers constituting an aromatic ring-containing polymer contained as a block part of a block copolymer or a graft part of a graft copolymer, and poly (meth) acrylate contained as a block part of a block copolymer or a graft part of a graft copolymer The number average molecular weight of the poly (meth) acrylate homopolymer composed of the monomers constituting is preferably 1000 or more from the viewpoint of phase separability, preferably 500,000 or less, and 300,000 or less from the viewpoint of viscosity suppression of the resin composition. More preferred. From the viewpoint of compatibility with the block copolymer or graft copolymer, the molecular weights of the aromatic ring-containing homopolymer and the poly (meth) acrylate homopolymer are the aromatic rings contained as the block portion of the block copolymer or the graft portion of the graft copolymer, respectively. It is desirable that the molecular weight of the containing polymer part and the poly (meth) acrylate part be lower.

  The resin composition is dissolved in a solvent to form a solution, and then applied to the surface of the inorganic compound layer 8. Subsequently, the resin composition is dried and the solvent is volatilized to form the resin composition layer 20.

  Any solvent can be used as long as it can dissolve the above resin composition. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, cyclopentanone, Cyclohexanone, isophorone, N, N-dimethylacetamide, dimethylimidazolinone, tetramethylurea, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMEA), methyl lactate, ethyl lactate, butyl lactate, Chill-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl 3-methoxypropionate and the like. These can be used alone or in admixture of two or more. More preferred specific examples include N-methylpyrrolidone, cyclopentanone, cyclohexanone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, PGMEA and the like. The mass ratio of the resin composition in the solution is preferably 1 to 30% by mass.

  As a method of applying the resin composition solution to the surface 8b of the inorganic compound layer 8, a spin coater, a bar coater, a blade coater, a curtain coater, a spray coater, a method of applying by an ink jet method, a screen printing machine, a gravure printing machine, an offset. A method of printing with a printing machine or the like can be given.

  Next, the obtained coating film is heat-dried or vacuum-dried by air drying, oven, hot plate or the like to volatilize the solvent. The film thickness of the resin composition layer 20 after volatilization of the solvent is preferably about 20 to 1000 nm. This is from the viewpoint of obtaining a self-organized pattern with a pitch of 20 to 1000 nm. As described above, in the present invention, the pattern pitch is usually equal to or greater than the film thickness. The film thickness of the resin composition layer 20 can be determined by a contact method in which a film is scratched and a terminal is brought into contact with the surface to measure the step, or a non-contact method using ellipsometry.

  Next, in FIG. 3D, the resin composition layer 20 is heated in the presence of oxygen or nitrogen. As a method for heating the resin composition layer 20 for each base material for light emitting elements, a method of roughly transferring heat from the lower side of the base material like a hot plate and a method of convection of a high-temperature gas like an oven are used. Can be mentioned.

  The temperature of the step of volatilizing the solvent is preferably in the range of 100 ° C. lower than the boiling point of the solvent to the boiling point of the solvent, and the temperature of the subsequent heating step is preferably in the range of 130 ° C. or higher and 280 ° C. or lower. Heating may be performed in air or under nitrogen, but when heated to 200 ° C. or higher in air, thermal decomposition occurs and the pitch of the self-assembled pattern increases.

  By heating the resin composition layer 20, the aromatic ring-containing polymer portion and the poly (meth) acrylate portion are microphase-separated and self-organized. FIG. 3D shows a self-organizing structure 20a. The self-assembled structure 20 a is an island sea structure composed of an aromatic ring-containing polymer portion 21 and a poly (meth) acrylate portion 25. At this time, in the dry etching, the poly (meth) acrylate portion 25 is more easily etched than the aromatic ring-containing polymer portion 21 regardless of the type of gas, so only the poly (meth) acrylate portion 25 is selected by dry etching. Thus, only the aromatic ring-containing polymer portion 21 can be selectively left. Further, when irradiated with UV light, poly (meth) acrylate is selectively decomposed to lower the molecular weight, so that it becomes soluble in polar organic solvents such as acetic acid. By utilizing this property and developing with a polar organic solvent after UV irradiation, only the poly (meth) acrylate portion 25 can be selectively removed, leaving only the aromatic ring-containing polymer portion 21.

  FIG. 4A shows a self-assembled pattern 20b in which only the aromatic ring-containing polymer portion 21 is left by dry etching or development. The self-organized pattern 20b is a fine unevenness obtained by removing one polymer portion from a self-organized structure 20a having an island-sea structure of an aromatic ring-containing polymer portion 21 and a poly (meth) acrylate portion 25 by the action of microphase separation. Refers to the pattern. Although the self-assembled pattern 20b is left as a random pattern, the pattern pitch is 20 to 1000 nm on average, preferably about 100 to 1000 nm. In particular, in the present invention, by adding a homopolymer to the block portion or graft portion of the block copolymer or graft copolymer as the resin composition, the degree of freedom in adjusting the pitch width can be improved. The pitch can be adjusted freely.

Next, in the step shown in FIG. 4B, the fine concavo-convex structure 22 is transferred onto the inorganic compound layer 8 using the self-assembled pattern 20b shown in FIG. 4A as a mask. When the etching selectivity between the aromatic ring-containing polymer portion 21 (see FIG. 4A) and the inorganic compound layer 8 is high, the inorganic compound layer 8 is directly dry-etched or masked using the aromatic ring-containing polymer portion 21 as a mask (resist). By performing wet etching, pattern transfer of the fine concavo-convex structure 22 is performed on the inorganic compound layer 8. Here, dry etching is preferably used. Examples of the gas used for dry etching include fluorine-based gases such as CF ₄ , C ₃ F ₈ , CHF ₃ , and SF ₆ , O ₂ , Ar, H _{2, and the} like, and mixtures thereof. In the present invention, the etching gas does not contain a chlorine-based gas such as Cl ₂ or BCl ₃ .

  In the process shown in FIG. 4B, the fine concavo-convex structure 22 formed on the surface of the inorganic compound layer 8 is in a state where the concave portion penetrates to the surface 5a of the p-type semiconductor layer 5 and the surface 5a is exposed.

  On the other hand, in FIG. 4C, the fine uneven structure 23 is formed partway through the inorganic compound layer 8 without penetrating the inorganic compound layer 8. Therefore, in FIG. 4C, the surface 5a of the p-type semiconductor layer 5 is not exposed, and the p-type semiconductor layer 5 is not exposed to etching.

  The self-assembled pattern 20b is removed during or after the etching of the inorganic compound layer 8.

  FIG. 5 is a process diagram for explaining a second method for manufacturing a light emitting device according to the present invention, and FIG. 6 is a process diagram performed after FIG.

  5A, the inorganic compound layer 8 is formed on the surface of the p-type semiconductor layer 5, and the transfer intermediate layer (pattern transfer layer) 31 is formed on the surface 8b of the inorganic compound layer 8. 5B, the resin composition layer 20 containing a block copolymer or a graft copolymer is formed on the surface 31a of the transfer intermediate layer 31.

  The transfer intermediate layer 31 can be formed by sputtering or vapor deposition. The transfer intermediate layer 31 is made of a material having an etching selectivity with respect to the inorganic compound layer 8 that is higher in the transfer intermediate layer 31 than in the resin composition layer having a self-organized pattern. For example, the transfer intermediate layer 31 can be formed of a metal thin film such as Al or Cr.

  When the etching selectivity between the aromatic ring-containing polymer portion 21 and the inorganic compound layer 8 is low in the step of FIG. 4A describing the first manufacturing method, a fine concavo-convex structure is accurately formed on the surface of the inorganic compound layer 8. I can't.

For this reason, the transfer intermediate layer 31 having a high etching selection ratio with the inorganic compound layer 8 is formed, and the fine pattern is first transferred to the transfer intermediate layer 31. That is, in the step shown in FIG. 5C, the resin composition layer 20 is self-assembled as in FIG. 3D, and in FIG. 6A, as in FIG. 4A, the self-assembled pattern 20b composed of the aromatic ring-containing polymer portion 21 by dry etching or development. 6B, in the process of FIG. 6B, the fine pattern 31b is first transferred to the transfer intermediate layer 31 by dry etching or wet etching using the aromatic ring-containing polymer portion 21 as a mask (resist). The etching gas used at that time is, for example, CF ₄ . In the step of FIG. 6B, the aromatic ring-containing polymer portion 21 may or may not remain. The fine concavo-convex structure 33 is transferred to the inorganic compound layer 8 by dry etching or wet etching using the fine pattern 31b formed in the transfer intermediate layer 31 as a mask. The fine pattern 31b is removed during or after etching the inorganic compound layer 8.

  First, after transferring the fine pattern 31b to the transfer intermediate layer 31 having a high etching selectivity of the inorganic compound layer 8 using the self-assembled pattern 20b, the inorganic compound layer 8 is used with the fine pattern 31b as a mask. By transferring the fine concavo-convex structure 33 to the pattern, the fine concavo-convex structure 33 can be accurately formed in the inorganic compound layer 8. Further, by providing the transfer intermediate layer 31, the degree of freedom in selecting the material for the inorganic compound layer 8 and the resin composition layer 20 can be expanded.

  In the present invention, the pattern pitch of the fine concavo-convex structure formed in the inorganic compound layer 8 is transferred from the pitch of the self-organized pattern of the resin composition layer 20 containing a block copolymer or a graft copolymer. At this time, the block copolymer or graft copolymer alone as the resin composition can only have a pitch pattern of about 20 to 200 nm, but a homopolymer composed of monomers constituting the polymer contained as the block portion or graft portion is added thereto. Thus, the pitch can be increased to about 1000 nm. Further, when thermal decomposition occurs during heating in the air after application, a pattern having a larger pitch can be obtained as the thermal decomposition proceeds.

  The height of the fine concavo-convex structure is determined by the etching selectivity between the resin composition layer containing the block copolymer or graft copolymer and the inorganic compound layer, or the etching selectivity between the transfer intermediate layer and the inorganic compound layer. The height of the fine concavo-convex structure increases as the etching selection ratio increases, and the height of the fine concavo-convex structure decreases as the etching selection ratio decreases.

According to the above-described method for manufacturing an optical element of the present invention, when a fine concavo-convex structure is pattern-transferred to an inorganic compound layer using a self-organized pattern, the etching gas does not contain a chlorine-based gas such as Cl ₂ or BCl _3. . When using chlorinated gas, waste gas must be recovered through a scrubber, and it is thought that it will be expensive, such as measures to prevent leakage from chlorinated gas cylinders and pipes. In the present invention, chlorinated gas is used. Therefore, the fine concavo-convex structure can be pattern transferred at low cost.

  In the present invention, by utilizing a self-organized pattern, a fine uneven structure formed in an inorganic compound layer can be formed with a nano-level random pattern, and an optical element having excellent optical characteristics can be manufactured at low cost. it can.

  Moreover, in this invention, the transfer intermediate | middle layer can be provided between an inorganic compound layer and a resin composition layer, and the method of first transferring a pattern to a transfer intermediate | middle layer can also be shown. According to this method, the fine relief structure is transferred onto the surface of the inorganic compound layer using the pattern transferred to the transfer intermediate layer as a mask. When the self-organization pattern is directly transferred to the inorganic compound layer due to the etching selection ratio, the pattern transferability is lowered, and the etching selectivity with the inorganic compound layer is higher than that of the self-assembly pattern (resin composition layer). By providing the transfer intermediate layer, the pattern transfer property to the inorganic compound layer can be improved.

  Hereinafter, the present invention will be described in more detail based on examples carried out to clarify the effects of the present invention. In addition, the material in the following Example, use composition, a process process, etc. are illustrations, and can be implemented changing suitably. Other modifications can be made without departing from the scope of the present invention. Therefore, the present invention is not limited at all by the following examples.

  First, synthesis examples of a block copolymer, an aromatic ring-containing homopolymer and a poly (meth) acrylate homopolymer comprising the block component are shown.

<Synthesis of block copolymer>
[Synthesis Example 1]
980 g of tetrahydrofuran (THF) dehydrated and degassed as a solvent in a 2 L flask, 0.8 ml of hexane solution (about 0.16 mol / L) of n-butyllithium (n-BuLi) as an initiator, and dehydrated and dehydrated as a monomer 20 g of styrene was added and stirred for 30 minutes while cooling to −78 ° C. in a nitrogen atmosphere. Then, 34 g of methyl methacrylate dehydrated and degassed as the second monomer was added and stirred for 4 hours. Thereafter, the reaction solution was added to a container containing 3 L of denatured alcohol (Solmix (registered trademark) AP-1 manufactured by Nippon Alcohol Sales Co., Ltd.) while stirring, and the precipitated polymer was vacuum-dried overnight at room temperature.

  The dried polymer was filled into a Soxhlet extractor, and by-product polystyrene was extracted using cyclohexane as a solvent. From the analysis by GPC, this byproduct polystyrene was identified as polystyrene having a number average molecular weight (Mn) of 366,000 in terms of standard polystyrene. This byproduct polystyrene is the one in which the terminal is inactivated at the end of polymerization of the block copolymer during synthesis of the block copolymer and cannot react with methyl methacrylate, and is the same as the molecular weight of the polystyrene block part in the block copolymer. is there.

The GPC apparatus, column, and standard polystyrene used are as follows.
Device: HLC-8020 manufactured by Tosoh Corporation
Eluent: Tetrahydrofuran 40 ° C
Column: Tosoh Co., Ltd. TSK (registered trademark) gel G5000HHR / G4000HHR / G3000HHR / G2500HHR In-line flow rate: 1.0 ml / min
Reference material for molecular weight calibration: TSK (registered trademark) standard polystyrene (12 samples) manufactured by Tosoh Corporation

From the result of the nuclear magnetic resonance (NMR) analysis, the molar ratio of the PS portion and the PMMA portion of the block copolymer was 2.13. The NMR apparatus and solvent used are as follows.
Apparatus: JNM-GSX400 FT-NMR manufactured by JEOL Ltd.
Solvent: deuterated chloroform

  Combined with the GPC results, the block copolymer, the main product, was identified as having a PS moiety Mn of 366,000 and a PMMA moiety Mn of 778,000. This was designated as BC-1.

<Synthesis of aromatic ring-containing homopolymer>
[Synthesis Example 2]
In a 500 ml flask, 180 g of methyl ethyl ketone (hereinafter also referred to as MEK) as a solvent, 2.36 g (0.0144 mol) of AIBN as an initiator, and 30.0 g (0.288 mol) of styrene as a monomer were heated to 70 ° C. in a nitrogen stream. The mixture was stirred for 6 hours and then allowed to cool to room temperature. The reaction mixture was added to 2 L of a mixed solution of Solmix AP-1 and water having a weight ratio of 2: 1 with stirring to precipitate a polymer. The mixture was stirred for 1 hour and then filtered using a filter paper, and the solid content was vacuum-dried overnight. The molecular weight and molecular weight distribution were measured by GPC under the same conditions as in Synthesis Example 1. As a result, Mw (weight average molecular weight) was 3,200, and molecular weight distribution (Mw / Mn) was 1.38. This was designated as PS-1.

<Synthesis of poly (meth) acrylate homopolymer>
[Synthesis Example 3]
In a 1 L flask, 390 g of MEK as a solvent, 37.4 g (0.16 mol) of 2,2′-azobis (dimethyl isobutyrate) as an initiator, and 65 g (0.65 mol) of methyl methacrylate as a monomer were placed in a nitrogen stream. The mixture was stirred for 5 hours while heating to 70 ° C., and then allowed to cool to room temperature.

  The reaction mixture was added to 3 L of hexane with stirring to precipitate a polymer. After stirring this for 1 hour, it filtered using the filter paper and solid content was vacuum-dried at room temperature overnight. As a result of measuring the molecular weight and molecular weight distribution by GPC, Mw (weight average molecular weight) was 4,000, and molecular weight distribution (Mw / Mn) was 1.70 (in this case, GPC was the same as in Synthesis Example 1) Although measured, standard PMMA MH-10 (10 samples) manufactured by Polymer Laboratories was used as a molecular weight calibration substance). This was designated as PMMA-1.

  Next, a light emitting element was produced, and an inorganic compound layer and a resin composition layer containing a block copolymer were sequentially formed on the surface of the light emitting side outermost layer. Subsequently, the self-organized pattern formed by self-assembly in the resin composition layer was transferred to the inorganic compound layer to form a fine concavo-convex structure on the surface of the inorganic compound layer. A change in light emission intensity of the light emitting element thus formed was measured. Hereinafter, each Example and a comparative example are demonstrated.

[Example 1]
(Production of light emitting element)
An n-AlInP clad layer, an AlGaInP active layer, a p-AlInP clad layer, and a p-type current diffusion layer were formed on the n-GaAs substrate by MOCVD. Subsequently, an Au thin film was formed on the back surface of the n-GaAs substrate by vacuum deposition to form an n-side electrode layer. Further, an Au thin film was also formed on the surface of the p-type current diffusion layer by vacuum deposition to form a p-side electrode layer. Thereafter, the n-side electrode layer and the p-side electrode layer are processed into desired shapes, respectively, and then heat-treated in a nitrogen atmosphere, whereby the interface between the n-side electrode layer and the n-GaAs substrate, and the p-side electrode layer And ohmic contact was formed at the interface between the p-type current diffusion layer.

(Formation of inorganic compound layer)
After forming a resist layer on the surface of the p-side electrode layer, an Nb ₂ O ₅ layer as an inorganic compound layer was sputtered to a thickness of 150 nm on the surface (upper surface) of the p-type current diffusion layer. Here, the p-type current diffusion layer corresponds to the outermost layer on the light emission side of the semiconductor layer. The refractive index of the p-type current spreading layer was 3.5, and the refractive index of the Nb ₂ O ₅ layer was 2.3. Therefore, the refractive index of the Nb ₂ O ₅ layer was 0.66 times the refractive index of the p-type current diffusion layer.

(Self-organized pattern formation of resin composition containing block copolymer)
BC-1, PS-1, and PMMA-1 obtained in the previous synthesis example were weighed 5 g, 2.5 g, and 5 g, respectively, and PGMEA was added to prepare a 6.26% by mass solution as a resin composition. . This solution was spin-coated at 1600 rpm for 30 seconds on the inorganic compound layer formed on the light emitting element, and pre-baked at 110 ° C. for 90 seconds. It was 350 nm when the film thickness of the obtained resin composition layer was measured using Nanometrics Japan Co., Ltd. Nanospec AFT3000T. Next, nitrogen and air were heated at 250 ° C. for 8 hours while adjusting the ratio of nitrogen and air to a cure oven (CHL-21CD-S type manufactured by Koyo Thermo System Co., Ltd.) so that the oxygen concentration was 2400 ppm. . Thereafter, the mixture was cooled to room temperature, and the pattern of the resin composition layer was observed by SEM. As shown in FIGS. . FIG. 9 is a schematic diagram of FIG. When this self-organized pattern (sea-island structure pattern) was analyzed using image analysis software A image-kun (manufactured by Asahi Kasei Engineering Co., Ltd.), the average distance (pitch) between adjacent islands and islands was 690 nm. It was.

(Transfer formation of fine relief structure on inorganic compound layer)
The resin composition having a self-assembled pattern formed thereon was irradiated with an excimer lamp having a wavelength of 172 nm in air for 1 minute, and then the substrate was selectively removed by dipping in acetic acid for 1 minute. . After that, using a plasma etching apparatus, the Nb ₂ O ₅ layer is etched for 4 minutes 30 seconds using the PS portion (self-assembled pattern) as a mask under the conditions of power 300 W, pressure 1 Pa, gas SF ₆ 50 SCCM, and the pitch A fine concavo-convex structure made of Nb ₂ O ₅ having a thickness of 700 nm and a height of 150 nm was formed on the surface of the p-type current diffusion layer that is the outermost layer on the light emission side. FIG. 8 is an SEM photograph of a fine relief structure formed on the surface of Nb ₂ O ₅ , and FIG. 10 is a schematic diagram of FIG.

(Measurement of light emitting element output)
When the output measurement of the light-emitting element of Example 1 formed as described above was performed, the light output when the Nb ₂ O ₅ layer having the fine concavo-convex structure is not provided on the surface (conventional example) is 1. Compared with the case, the light output could be improved by 1.50 times.

Further, as described above, when the fine concavo-convex structure was transferred and formed on the inorganic compound layer, SF ₆ was used as an etching gas, and the fine concavo-convex structure could be appropriately transferred to the inorganic compound layer without using a chlorine-based gas.

[Example 2]
The inorganic compound layer has the same configuration as in Example 1 except that TiO ₂ is used instead of Nb ₂ O ₅ . The refractive index of the TiO ₂ layer was 2.5. Therefore, the refractive index of the TiO ₂ layer was 0.71 times the refractive index of the p-type current diffusion layer. And when the output measurement of the light emitting element in Example 2 was performed, the light output was 1 as compared with the case where the light output was 1 when the TiO ₂ layer having the fine uneven structure was not provided on the surface (conventional example). It was improved 61 times.

[Comparative Example 1]
In Comparative Example 1, the same structure as in Example 1 was used except that Al ₂ O ₃ which is a compound containing a Group 3 element was used instead of Nb ₂ O ₅ as the inorganic compound layer. The refractive index of Al ₂ O ₃ was 1.7. However, when the fine concavo-convex structure is transferred and formed on the inorganic compound layer using the self-organized pattern as a mask, the fluorine-based gas used in the examples cannot properly etch Al ₂ O ₃ , so Cl _{2 is used} instead. Etching of Al ₂ O ₃ was performed using / BCl ₃ gas.

When the output of the light emitting device in Comparative Example 1 was measured, the light output was compared with the case where the light output in the case where the Al ₂ O ₃ layer having the fine uneven structure was not provided on the surface (conventional example) was set to 1. Although it could be improved by 1.23 times, chlorine-based gas was required for etching the inorganic compound layer.

[Comparative Example 2]
In Comparative Example 2, the same configuration as in Example 1 was used except that the inorganic compound layer was not formed and the resin composition layer was directly formed on the surface of the p-type current diffusion layer. However, in Comparative Example 2, an attempt was made to transfer and form a fine concavo-convex structure on the surface of the p-type current diffusion layer using the self-assembled pattern as a mask, but the p-type current diffusion layer could be etched with the fluorine-based gas used in the example. Therefore, the p-type current diffusion layer was etched using Cl ₂ / BCl ₃ gas instead. And when the output measurement of the light emitting element in Comparative Example 2 was performed, the light output was 1.75 times as compared with the case where the light output was 1 when the fine uneven structure was not formed on the surface of the p-type current diffusion layer. However, a chlorine-based gas was required for etching the p-type current diffusion layer.

  The present invention can be effectively applied to light emitting elements such as LEDs. According to the present invention, a fine concavo-convex structure formed on the surface of an inorganic compound layer using self-organized lithography of a block copolymer or a graft copolymer can be formed without using etching with a high-cost chlorine-based gas. And the light emission efficiency characteristics can be improved. As a result, it is possible to improve the luminance when the light emitting element is formed into a chip.

DESCRIPTION OF SYMBOLS 1 Light emitting element 2 Substrate 3 N type semiconductor layer 4 Active layer 5 P type semiconductor layer 6 N side electrode layer 7 P side electrode layer 8 Inorganic compound layer 9, 22, 23, 33 Fine uneven structure 10 Convex part 20 Resin composition layer 20a Self-assembled structure 20b Self-assembled pattern 21 Aromatic ring-containing polymer part 25 Poly (meth) acrylate part 31 Transfer intermediate layer 31a Fine pattern

Claims (8)

A light emitting side outermost layer of the semiconductor layer, and an inorganic compound layer formed to overlap the light emitting side of the light emitting side outermost layer,
The inorganic compound layer has a refractive index of not less than 0.5 times and not more than 1.0 times the refractive index of the outermost layer on the light emitting side, Cr, Hf, Ni, Mg, Nb, Ta, W, Ti, Zn, Formed of an inorganic compound containing at least one element selected from Zr and Si;
A light-emitting element, wherein the surface of the inorganic compound layer is provided with a fine concavo-convex structure formed using a self-organized pattern of a resin composition containing a block copolymer or a graft copolymer.   The light-emitting element according to claim 1, wherein the element contained in the inorganic compound layer is at least one selected from Mg, Nb, Ta, W, and Ti. The inorganic compound layer is formed of at least one inorganic compound selected from MgO, Nb ₂ O ₅ , Ta ₂ O ₅ , WO ₃ , TiO, Ti ₃ O ₅ , and TiO _2. Item 3. A light emitting device according to Item 2.   The pitch of the fine uneven structure is 20 to 1000 nm, the height of the fine uneven structure is 20 to 1000 nm, and the thickness of the inorganic compound layer is 5 times or less the height of the fine uneven structure. The light emitting device according to claim 1, wherein the light emitting device is a light emitting device.   The pitch of the fine concavo-convex structure is 100 to 1000 nm, the height of the fine concavo-convex structure is 50 to 1000 nm, and the thickness of the inorganic compound layer is three times or less the height of the fine concavo-convex structure. The light emitting device according to claim 1, wherein the light emitting device is a light emitting device. A method for manufacturing a light emitting device according to any one of claims 1 to 5,
The outermost layer on the light emission side of the semiconductor layer has a refractive index of 0.5 to 1.0 times the refractive index of the outermost layer on the light emission side, and Cr, Hf, Ni, Mg, Nb, Ta, W, A step of stacking and forming an inorganic compound layer containing at least one element selected from Ti, Zn, Zr, and Si;
Forming a resin composition layer containing a block copolymer or a graft copolymer on the surface of the inorganic compound layer;
Forming a self-assembled pattern in the resin composition layer;
Transferring the self-assembled pattern to the surface of the inorganic compound layer by etching to form a fine relief structure on the inorganic compound layer;
A method for manufacturing a light-emitting element, comprising: Including a step of forming a transfer intermediate layer between the inorganic compound layer and the resin composition layer,
The fine concavo-convex structure is transferred to the inorganic compound layer using the pattern transferred to the transfer intermediate layer as a mask after the self-assembled pattern is transferred to the transfer intermediate layer by etching. 6. A method for producing a light emitting device according to 6. The transfer intermediate layer is made of a material having an etching selectivity with respect to the inorganic compound layer that is higher in the transfer intermediate layer than in the resin composition layer having the self-assembled pattern. Item 8. A method for producing a light emitting device according to Item 7.