TW201703291A - Substrate and method for manufacturing same, light-emitting element and method for manufacturing same, and device having said substrate or said light-emitting element - Google Patents
Substrate and method for manufacturing same, light-emitting element and method for manufacturing same, and device having said substrate or said light-emitting element Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/20—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular shape, e.g. curved or truncated substrate
- H01L33/22—Roughened surfaces, e.g. at the interface between epitaxial layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
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- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Led Devices (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
本發明關於一種基板與其製造方法以及發光元件與其製造方法,以及具有該基板或發光元件的裝置。 The present invention relates to a substrate and a method of manufacturing the same, a light-emitting element and a method of manufacturing the same, and an apparatus having the substrate or the light-emitting element.
發光二極體(LED:Light Emitting Diode)為使用化合物半導體特性,使電能轉換成光能的EL(Electro Luminescence)元件的一種,利用3-5族化合物半導體使發光二極體實用化。此種3-5族化合物半導體為直接過渡型半導體,相較於使用其他半導體的元件,在高溫可穩定運作。再者,3-5族化合物半導體由於能量轉換效率佳或使用壽命長,因此廣泛用於各種照明設備或照明、電子機器等。 A light-emitting diode (LED) is one of EL (Electro Luminescence) elements that converts electric energy into light energy by using a compound semiconductor characteristic, and a light-emitting diode is practically used by a Group 3-5 compound semiconductor. Such a Group 3-5 compound semiconductor is a direct transition type semiconductor, and is stable at a high temperature compared to an element using other semiconductors. Furthermore, the Group 3-5 compound semiconductors are widely used in various lighting devices, lighting, electronic equipment, and the like because of their excellent energy conversion efficiency or long service life.
此種LED的發光元件(以下,表示為「發光元件」)形成於藍寶石(Al2O3)基板的面上,其構造的示意圖如第17圖所示(例如,參照專利文獻1第3圖)。如第17圖,以往的發光元件100在藍寶石基板101的面上,隔著由GaN系半導體材料所構成的低溫成長緩衝層(未繪示),形成n型GaN接觸層(n-GaN層)102。於n-GaN層102形成n型電極。此n-GaN層102上形成n型AlGaN被覆層(未繪示。視情況省略)、InGaN發光層(活性層)103、p型AlGaN被覆層104,於其上形成p型GaN接觸 層105。再者,於p型GaN接觸層105上形成作為p型電極的ITO(氧化銦錫)透明電極106及金屬電極。InGaN發光層103採用由InGaN井層與InGaN(GaN)障壁層所構成的多重量子井層構造(MQW:Multiple Quantum Well)。此外,在n-GaN層102上未形成有InGaN發光層103的位置,形成n型電極層107。 A light-emitting element of such an LED (hereinafter referred to as a "light-emitting element") is formed on a surface of a sapphire (Al 2 O 3 ) substrate, and a schematic diagram of the structure is shown in FIG. 17 (for example, refer to Patent Document 1 and FIG. 3). ). As shown in Fig. 17, the conventional light-emitting element 100 forms an n-type GaN contact layer (n-GaN layer) on a surface of the sapphire substrate 101 via a low-temperature growth buffer layer (not shown) made of a GaN-based semiconductor material. 102. An n-type electrode is formed on the n-GaN layer 102. An n-type AlGaN coating layer (not shown. omitting), an InGaN light-emitting layer (active layer) 103, and a p-type AlGaN cladding layer 104 are formed on the n-GaN layer 102, and a p-type GaN contact layer 105 is formed thereon. Further, an ITO (Indium Tin Oxide) transparent electrode 106 as a p-type electrode and a metal electrode are formed on the p-type GaN contact layer 105. The InGaN light-emitting layer 103 employs a multiple quantum well layer structure (MQW: Multiple Quantum Well) composed of an InGaN well layer and an InGaN (GaN) barrier layer. Further, a position where the InGaN light-emitting layer 103 is not formed on the n-GaN layer 102 forms an n-type electrode layer 107.
由發光元件100的InGaN發光層103所發出的光,從p型電極及/或藍寶石基板101取出,提升此等的發光效率,成為降低錯位的課題。然而,在藍寶石基板101上所成長的GaN層,在藍寶石的晶格常數與GaN的晶格常數之間產生晶格常數差異,由於此晶格常數差異,作為GaN結晶中高密度的非發光再結合中心運作,產生貫穿錯位。此貫穿錯位為光輸出(內部量子效率)及耐久壽命同時減少的原因,造成漏電流的增加。 The light emitted from the InGaN light-emitting layer 103 of the light-emitting element 100 is taken out from the p-type electrode and/or the sapphire substrate 101, and the light-emitting efficiency is improved to reduce the misalignment. However, the GaN layer grown on the sapphire substrate 101 has a difference in lattice constant between the lattice constant of sapphire and the lattice constant of GaN, and due to the difference in lattice constant, it is a high-density non-light-emitting recombination in GaN crystal. The operation of the center creates a contradiction. This through-dislocation is responsible for the simultaneous reduction of light output (internal quantum efficiency) and endurance life, resulting in an increase in leakage current.
再者,在藍色區域的波長,GaN的折射率約為2.4,藍寶石的折射率約為1.8,空氣的折射率1.0,GaN與藍寶石之間約為0.6,GaN與空氣之間會產生約1.4的折射率差。由於此折射率差,從InGaN發光層103發出的光,在p型電極、GaN與空氣的界面、藍寶石基板101之間反覆全反射。由於此全反射,光閉鎖在InGaN發光層103且在InGaN發光層103中傳播時自我吸收,或被電極等吸收,最終轉換成熱。亦即,因折射率差所引起的全反射的限制的緣故,發生發光元件的光取出效率大幅降低的現象。 Furthermore, in the wavelength of the blue region, the refractive index of GaN is about 2.4, the refractive index of sapphire is about 1.8, the refractive index of air is 1.0, about 0.6 between GaN and sapphire, and about 1.4 between GaN and air. The difference in refractive index. Due to this refractive index difference, the light emitted from the InGaN light-emitting layer 103 is totally totally reflected between the p-type electrode, the interface between GaN and air, and the sapphire substrate 101. Due to this total reflection, the light is self-absorbed when it is propagated in the InGaN light-emitting layer 103 and propagates in the InGaN light-emitting layer 103, or is absorbed by an electrode or the like, and finally converted into heat. That is, the light extraction efficiency of the light-emitting element is greatly reduced due to the limitation of total reflection due to the difference in refractive index.
為了提升光取出效率,揭示一種例如在藍寶石基板面上形成凹凸圖,於此凹凸圖案上形成上述各GaN層102乃至105或形成電極的發光元件。凹凸圖案的形成為在藍寶石 基板表面蝕刻加工的方法。再者,揭示一種作為更加提升凹凸圖案的製造效率的發光元件,由比GaN折射率更小的SiO2、ZrO2、TiO2等電介質所構成的凹凸圖案形成於平坦的藍寶石基板的面上的發光元件(例如,參照專利文獻1的第1圖)。 In order to enhance the light extraction efficiency, for example, a concave-convex pattern is formed on a surface of a sapphire substrate, and the above-described GaN layers 102 to 105 or light-emitting elements are formed on the uneven pattern. The formation of the concavo-convex pattern is a method of etching the surface of the sapphire substrate. Further, a light-emitting element which further improves the manufacturing efficiency of the uneven pattern is disclosed, and a concave-convex pattern composed of a dielectric material such as SiO 2 , ZrO 2 or TiO 2 having a refractive index smaller than that of GaN is formed on the surface of the flat sapphire substrate. Element (for example, refer to FIG. 1 of Patent Document 1).
如第18圖所示專利文獻1揭示的發光元件108係於藍寶石基板101面上,形成由電介質所構成的凸部109的圖案。藉由此種於藍寶石基板101表面形成凸部109的圖案,可於InGaN發光層103的下方形成凹凸狀的折射率界面。因此,可將發生於InGaN發光層103在橫方向傳播而被發光元件108內部所吸收的光的一部份經由凸部109的光散射效果,取出至藍寶石基板101及InGaN發光層103的外部,進而可提升光取出效率。再者,無須在藍寶石基板101的表面蝕刻加工,亦可提升發光元件108的發光效率,同時,可實現FACELO(Facet-Controlled Epitaxial Lateral Overgrowth)的成長模式,可獲得錯位密度減少的GaN系發光元件。 The light-emitting element 108 disclosed in Patent Document 1 shown in Fig. 18 is formed on the surface of the sapphire substrate 101, and forms a pattern of the convex portion 109 made of a dielectric. By forming the pattern of the convex portion 109 on the surface of the sapphire substrate 101, a concave-convex refractive index interface can be formed under the InGaN light-emitting layer 103. Therefore, a portion of the light that has propagated in the lateral direction of the InGaN light-emitting layer 103 and is absorbed by the inside of the light-emitting element 108 can be taken out to the outside of the sapphire substrate 101 and the InGaN light-emitting layer 103 via the light scattering effect of the convex portion 109. In turn, the light extraction efficiency can be improved. Further, it is not necessary to etch the surface of the sapphire substrate 101, and the luminous efficiency of the light-emitting element 108 can be improved. At the same time, a growth mode of FACELO (Facet-Controlled Epitaxial Lateral Overgrowth) can be realized, and a GaN-based light-emitting element with reduced dislocation density can be obtained. .
[先前技術文獻】 [Previous Technical Literature]
[專利文獻] [Patent Literature]
專利文獻1:日本特開2009-54898號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2009-54898
然而,專利文獻1等對於凸部109的圖案形成,使用一般的光蝕刻技術。亦即,在形成凸部109時,成為凸部109的基底的SiO2膜,必須將另外由酚醛樹脂等所形成的光阻膜形成於SiO2膜上,並隔著光罩圖案化形成光阻膜,以圖案 化形成的光阻膜作為新的光罩,將SiO2膜藉由蝕刻而圖案化形成。因此,由於必須有光阻膜的成膜步驟或曝光、顯影步驟、及SiO2膜的蝕刻步驟,因此,製程數增加,隨著製程數增加成本也跟著高漲。 However, in Patent Document 1 and the like, for the pattern formation of the convex portion 109, a general photo etching technique is used. In other words, when the convex portion 109 is formed, the SiO 2 film which is the base of the convex portion 109 must be formed of a photoresist film formed of a phenol resin or the like on the SiO 2 film, and patterned by the photomask. The resist film is formed by patterning a photoresist film as a new mask and etching the SiO 2 film by etching. Therefore, since the film forming step of the photoresist film or the exposure step, the development step, and the etching step of the SiO 2 film are necessary, the number of processes is increased, and the cost increases as the number of processes increases.
此外,以光蝕刻技術及蝕刻加工形成凸部109時,必須經過光阻膜的曝光、顯影的步驟。在此情況下,可形成的凸部109的剖面形狀限制於台形的型態,故可形成的凸部形狀的自由度變低。因此,在實現光取出效率的提升,以及在製作可縮短覆蓋凸部的GaN層的成長時間的具有剖面形狀的凸部時,形成於電介質膜上的光阻膜的光蝕刻技術以及作為其光罩的蝕刻加工變得困難 Further, when the convex portion 109 is formed by photolithography and etching, it is necessary to pass through the step of exposing and developing the photoresist film. In this case, since the cross-sectional shape of the convex portion 109 which can be formed is limited to the shape of the mesa, the degree of freedom of the shape of the convex portion which can be formed becomes low. Therefore, when the light extraction efficiency is improved and the convex portion having a cross-sectional shape capable of shortening the growth time of the GaN layer covering the convex portion is formed, the photoetching technique of the photoresist film formed on the dielectric film and as the light thereof The etching process of the cover becomes difficult
此外,經圖案化形成的SiO2膜作為新的光罩,經由蝕刻加工於藍寶石基板表面進行圖案化形成,終究在過程中的SiO2膜圖案製造步驟必須有光阻膜的光蝕刻技術及蝕刻加工。因此,引起製程數的增加及隨著製程數增加而來的成本高漲。 In addition, the patterned SiO 2 film is formed as a new mask by etching on the surface of the sapphire substrate for patterning. In the end, the SiO 2 film pattern manufacturing step in the process must have photoetching technology and etching of the photoresist film. machining. Therefore, the number of processes is increased and the cost is increased as the number of processes increases.
本發明係鑑於上述事項,提供一種賦予電介質膜組成此等感光性,即使沒有光阻膜也可形成凸部圖案,故可減少製程數,並隨著製程數減少而可低成本化,在面上具有預定圖案的基板與其製造方法,及發光元件與其製造方法。 SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a photosensitive film composition having such a photosensitive property, and a convex pattern can be formed even without a photoresist film, so that the number of processes can be reduced, and the number of processes can be reduced to reduce the cost. A substrate having a predetermined pattern thereon, a method of manufacturing the same, and a light-emitting element and a method of manufacturing the same.
上述課題可透過以下的本發明達成。亦即, The above problems can be achieved by the following invention. that is,
(1)本發明的基板的製造方法,係準備平坦的基板,在上述基板面上形成含有感光劑的電介質,對上述電介質進行圖案化形成,藉以於上述基板面上形成預定圖案的上述電介質。 (1) A method of manufacturing a substrate according to the present invention, wherein a flat substrate is prepared, a dielectric containing a photosensitive agent is formed on the surface of the substrate, and the dielectric is patterned to form a dielectric having a predetermined pattern on the surface of the substrate.
(2)本發明的基板的製造方法的一實施形態,以上述電介質的圖案形成後,對上述電介質進行退火,藉以在上述基板面上形成預定上述圖案的上述電介質。此外,基板的製造方法其他的實施形態,以在上述電介質的圖案形成後,在上述退火前對上述電介質進行後烘(post-baking)為佳。 (2) In one embodiment of the method for producing a substrate of the present invention, after the dielectric pattern is formed, the dielectric is annealed, whereby the dielectric having the predetermined pattern is formed on the substrate surface. Further, in another embodiment of the method of manufacturing a substrate, it is preferable to post-baize the dielectric before the annealing after forming the pattern of the dielectric.
(3)此外本發明的基板的製造方法其他的實施形態,以上述後烘在100℃以上400℃以下的溫度範圍進行為佳。 (3) Further, in another embodiment of the method for producing a substrate of the present invention, it is preferred that the post-baking is performed in a temperature range of from 100 ° C to 400 ° C.
(4)此外本發明的基板的製造方法其他的實施形態,以上述退火在700℃以上1700℃以下的溫度範圍進行為佳。 (4) Further, in another embodiment of the method for producing a substrate of the present invention, it is preferred that the annealing be performed in a temperature range of from 700 ° C to 1700 ° C.
(5)此外本發明的基板的製造方法其他的實施形態,以上述電介質為矽氧烷樹脂組成物、含有氧化鈦的矽氧烷樹脂組成物、含有氧化鋯的矽氧烷樹脂組成物、含有氧化鋁的矽氧烷樹脂組成物的任一者為佳。 (5) In another embodiment of the method for producing a substrate of the present invention, the dielectric material is a siloxane oxide resin composition, a cerium oxide-containing cerium oxide resin composition, a zirconia-containing cerium oxide resin composition, and a composition. Any of the aluminoxane resin compositions of alumina is preferred.
(6)此外本發明的基板的製造方法其他的實施形態,以將上述電介質塗佈於上述基板面上,藉以將上述電介質形成於上述基板面上,接著,對在上述基板面上形成有上述電介質的上述基板進行預烘(pre-baking),接著,使用光罩使上述電介質曝光成期望的上述圖案,接著,對經曝光的上述電介質進行顯影,對上述電介質進行上述退火,使預定上述圖案的上述電介質形成於上述基板面上為佳。 (6) In another embodiment of the method for producing a substrate of the present invention, the dielectric is applied to the surface of the substrate, whereby the dielectric is formed on the surface of the substrate, and then the substrate is formed on the surface of the substrate. The substrate of the dielectric is pre-baking, and then the dielectric is exposed to a desired pattern using a photomask, and then the exposed dielectric is developed, and the dielectric is annealed to form the pattern. Preferably, the dielectric is formed on the surface of the substrate.
(7)此外本發明的基板的製造方法其他的實施形態,以將上述電介質以期望的上述圖案直接圖案化形成於上述 基板面上,接著,對在上述基板面上形成有上述電介質的上述基板進行預烘,接著,對上述電介質進行曝光,對上述電介質進行上述退火,使預定上述圖案的上述電介質形成於上述基板面上為佳。 (7) Further, in another embodiment of the method for producing a substrate of the present invention, the dielectric is directly patterned by using the desired pattern in the above-described pattern. On the substrate surface, the substrate on which the dielectric is formed on the substrate surface is prebaked, and then the dielectric is exposed, and the dielectric is annealed to form the dielectric having the predetermined pattern on the substrate surface. It is better.
(8)此外本發明的基板的製造方法其他的實施形態,以將上述電介質塗佈於上述基板面上,藉以將上述電介質形成於上述基板面上,接著,將模型壓附在上述電介質使上述電介質硬化,對上述電介質進行上述退火,使預定上述圖案的上述電介質形成於上述基板面上為佳。 (8) In another embodiment of the method for producing a substrate of the present invention, the dielectric is applied to the surface of the substrate, whereby the dielectric is formed on the surface of the substrate, and then the mold is pressed onto the dielectric to cause the The dielectric is cured, and the dielectric is annealed so that the dielectric having the predetermined pattern is formed on the surface of the substrate.
(9)此外本發明的基板的製造方法,係準備上述基板,將上述圖案作為光罩,對上述基板的表面進行蝕刻處理,在上述基板的表面形成期望的上述圖案。 (9) In the method of manufacturing a substrate of the present invention, the substrate is prepared, and the surface of the substrate is etched by using the pattern as a mask, and a desired pattern is formed on the surface of the substrate.
(10)此外本發明的發光元件的製造方法,係準備上述基板,於上述凸部及上述基板上形成至少一層GaN層、AlN層、InN層,製造發光元件。 (10) In the method of producing a light-emitting device of the present invention, the substrate is prepared, and at least one GaN layer, an AlN layer, and an InN layer are formed on the convex portion and the substrate to produce a light-emitting element.
(11)此外本發明的基板係在平坦基板的面上具有由島狀的凸部所構成的圖案,同時上述凸部為由電介質所構成。並且,該基板可應用於光源或顯示器或太陽電池中。 (11) Further, the substrate of the present invention has a pattern composed of island-like convex portions on the surface of the flat substrate, and the convex portion is made of a dielectric. Also, the substrate can be applied to a light source or display or a solar cell.
(12)本發明的基板的一實施形態,以上述凸部至少一部份為曲面狀(具有曲面)為佳。 (12) In an embodiment of the substrate of the present invention, it is preferable that at least a portion of the convex portion has a curved surface (having a curved surface).
(13)此外本發明的基板其他的實施形態,以構成上述凸部的電介質以SiO2、TiO2、ZrO2、Al2O3任一者作為主要成分為佳。 (13) In another embodiment of the substrate of the present invention, it is preferable that the dielectric constituting the convex portion has SiO 2 , TiO 2 , ZrO 2 , and Al 2 O 3 as a main component.
(14)此外本發明的基板其他的實施形態,以上述凸部為全體為曲面,頂部及側部無區別,具有不存在平坦面的曲面形狀為佳。 (14) In another embodiment of the substrate of the present invention, the convex portion is a curved surface as a whole, and the top portion and the side portion are indistinguishable, and a curved surface shape having no flat surface is preferable.
(15)此外本發明的基板其他的實施形態,以上述凸部為半球形為佳。 (15) In another embodiment of the substrate of the present invention, it is preferable that the convex portion has a hemispherical shape.
(16)此外本發明的基板其他的實施形態,以上述凸部的平面形狀為圓形或橢圓形為佳。 (16) Further, in another embodiment of the substrate of the present invention, it is preferable that the planar shape of the convex portion is circular or elliptical.
(17)此外本發明的基板,以上述基板的表面具有期望的上述圖案為佳。 (17) Further, in the substrate of the present invention, it is preferred that the surface of the substrate has a desired pattern as described above.
(18)此外本發明的基板在上述基板的表面具有均一間距的上述圖案,且上述間距的上述表面處中未形成有上述圖案的上述圖案缺陷處,以形成有上述間距的情況而言,相對於述表面中上述圖案的全部,以0%以上50%以下為佳。 (18) Further, in the substrate of the present invention, the pattern has a uniform pitch on the surface of the substrate, and the pattern defect portion of the pattern is not formed in the surface of the pitch, and in the case where the pitch is formed, It is preferable that all of the above-mentioned patterns in the surface are 0% or more and 50% or less.
(19)此外本發明的發光元件,係包含上述凸部及形成於上述基板上至少一層的GaN層、AlN層、InN層的發光元件。 (19) The light-emitting element of the present invention includes the convex portion and the light-emitting element of the GaN layer, the AlN layer, and the InN layer formed on at least one of the substrates.
並且,該發光元件以應用於光源或顯示器中為佳。 Also, the light-emitting element is preferably applied to a light source or a display.
依據上述(1)、(9)、(11)(17)中任一者的發明,由於圖案化形成含有感光劑的電介質,無須形成光阻膜,可在基板面上形成由凸部所構成的預定圖案。因此得以實現製程數的減少及步驟的簡化、及隨著製程數減少基板的低成本化。並 且,藉此所得的基板適用於光源或顯示器、基板等。 According to the invention of any one of the above (1), (9), (11), and (17), since the dielectric containing the sensitizer is formed by patterning, it is not necessary to form a photoresist film, and a convex portion can be formed on the substrate surface. Scheduled pattern. Therefore, it is possible to reduce the number of processes, simplify the steps, and reduce the cost of the substrate as the number of processes is reduced. and Further, the substrate obtained thereby is suitable for use in a light source, a display, a substrate, or the like.
再者,依據上述(2)的發明,由於對期望的凸部圖案形成後的電介質施行退火,基板面上的期望的圖案可形成任意的側面形狀。再者,感光劑的成分因退火而被去除,可防止有機成分混入GaN層等的發光元件。 Further, according to the invention of the above (2), since the dielectric after the formation of the desired convex portion pattern is annealed, a desired pattern on the surface of the substrate can be formed into an arbitrary side shape. Further, the components of the photosensitive agent are removed by annealing, and the organic component can be prevented from being mixed into the light-emitting element such as the GaN layer.
再者,依據上述(3)的發明,由於在100℃以上400℃以下的溫度範圍進行後烘,可提高電介質的流動性,電介質的圖案的全部、或頂部/側部的一部份可捲曲成形為曲面狀,故可提升發光元件的光取出效率。再者,當比較剖面形狀為台形形狀或矩形形狀的凸部時,成形為曲面狀的凸部,當GaN層等成膜時GaN層的橫方向成長時間變短,故可縮短GaN層的成長時間。 Further, according to the invention of the above (3), since the post-baking is performed in a temperature range of 100 ° C or more and 400 ° C or less, the fluidity of the dielectric can be improved, and all or a part of the top/side portion of the dielectric pattern can be curled. Since it is formed into a curved shape, the light extraction efficiency of the light-emitting element can be improved. In addition, when the convex portion having a trapezoidal shape or a rectangular shape is compared, the convex portion is formed into a curved shape, and when the GaN layer or the like is formed, the growth time of the GaN layer in the lateral direction is shortened, so that the growth of the GaN layer can be shortened. time.
再者,依據上述(4)的發明,經由在700℃以上1700℃以下的溫度範圍進行退火,將凸部的感光劑成分經由退火而去除,同上述可防止有機成分混入GaN層等的發光元件。再者,可防止凸部上發生GaN層的成長、或使其變得難以發生成長。藉由抑制凸部上的GaN層的成長,可實現FACELO的成長模式,因此可形成錯位密度減少的GaN層。此外、退火後的凸部可具有耐熱性,即使在n-GaN層的成膜時的成膜溫度(約1000℃)下亦可保持凸部的形狀及物性。 In addition, according to the invention of the above (4), annealing is performed in a temperature range of 700 ° C or more and 1700 ° C or less, and the photosensitive material component of the convex portion is removed by annealing, and the organic component is prevented from being mixed into the light-emitting element such as a GaN layer. . Further, it is possible to prevent the growth of the GaN layer from occurring on the convex portion or to make it difficult to grow. By suppressing the growth of the GaN layer on the convex portion, the growth mode of FACELO can be realized, and thus a GaN layer having a reduced dislocation density can be formed. Further, the convex portion after annealing can have heat resistance, and the shape and physical properties of the convex portion can be maintained even at the film formation temperature (about 1000 ° C) at the time of film formation of the n-GaN layer.
再者,依據上述(5)的發明,由於矽氧烷樹脂組成物、含有氧化鈦的矽氧烷樹脂組成物、含有氧化鋯的矽氧烷樹脂組成物、含有氧化鋁的矽氧烷樹脂組成物被覆性良好,因此在無光阻膜成膜的基板表面能夠以均一厚度或高度形成無紊 亂的電介質。再者相較於其他樹脂、含氧化鈦樹脂、含氧化鋯樹脂、含氧化鋁樹脂,硬化收縮小,因此,可易於以如預期的高度與大小及間距將凸部形成於基板面上。此外矽氧烷樹脂組成物、含有氧化鈦的矽氧烷樹脂組成物、含有氧化鋯的矽氧烷樹脂組成物、含有氧化鋁的矽氧烷樹脂組成物,相較於其他樹脂、含氧化鈦樹脂、含氧化鋯樹脂、含氧化鋁樹脂,硬化後不易產生裂痕,因此,凸部的電介質中不易產生空隙,當GaN層成長時,凸部與GaN層的界面變得不易產生間隙(孔洞)。因此可防止發光元件中電特性的惡化。 Further, according to the invention of the above (5), the composition of the decane resin, the cerium oxide resin composition containing titanium oxide, the cerium oxide resin composition containing zirconia, and the cerium oxide resin containing alumina The coating property is good, so that the surface of the substrate formed without the photoresist film can be formed into a uniform thickness or height. Chaotic dielectric. Further, compared with other resins, titanium oxide-containing resins, zirconia-containing resins, and alumina-containing resins, the hardening shrinkage is small, and therefore, the convex portions can be easily formed on the substrate surface at a desired height, size, and pitch. Further, a decane resin composition, a cerium oxide-containing cerium oxide resin composition, a zirconia-containing cerium oxide resin composition, and an alumina-containing cerium oxide resin composition are compared with other resins and titanium oxide-containing compounds. The resin, the zirconia-containing resin, and the alumina-containing resin are less likely to cause cracks after curing. Therefore, voids are less likely to occur in the dielectric of the convex portion, and when the GaN layer is grown, the interface between the convex portion and the GaN layer is less likely to cause a gap (hole). . Therefore, deterioration of electrical characteristics in the light-emitting element can be prevented.
再者,依據上述(6)的發明,以光蝕刻法使用含有感光劑的電介質所構成的期望的圖案化形成,可在無光阻膜成膜的基板面上形成圖案。因而實現製程數減少及步驟的簡化、及隨著製程數減少基板的低成本化。再者,步驟的時間短,故,可在短時間製作在面上具有期望的圖案的基板。 Further, according to the invention of the above (6), a desired pattern formation by a photo-etching method using a dielectric containing a photosensitive agent can be performed, and a pattern can be formed on the surface of the substrate on which the photoresist film is not formed. Therefore, the number of processes is reduced, the steps are simplified, and the number of processes is reduced to reduce the cost of the substrate. Further, since the time of the step is short, the substrate having the desired pattern on the surface can be produced in a short time.
再者,依據上述(7)的發明,在期望的圖案形成使用噴墨法,可直接地進行圖案化形成,故,提高凸部圖案的種類的自由度。 Further, according to the invention of the above (7), the inkjet method is used for the desired pattern formation, and the pattern formation can be directly performed, so that the degree of freedom of the type of the convex portion pattern is improved.
再者,依據上述(8)的發明,在期望的圖案形成使用奈米壓印法,能夠以簡便的設備且低成本地在基板面上形成期望的大小、間距、高度的凸部的圖案。 Further, according to the invention of the above (8), it is possible to form a pattern of convex portions having a desired size, pitch, and height on the substrate surface with a simple apparatus and at a low cost by using a nanoimprint method in a desired pattern formation.
此外,依據上述(10)或(19)的發明,凸部形成於基板的表面上,因此,各凸部有光散射效果。因此,被發光元件內部所吸收的光的一部份可取出至基板及InGaN發光層的外部,可提升發光元件的光取出效率。並且,如此所得的發光元 件可適用於光源或顯示器等。 Further, according to the invention of the above (10) or (19), the convex portion is formed on the surface of the substrate, and therefore, each convex portion has a light scattering effect. Therefore, a part of the light absorbed by the inside of the light-emitting element can be taken out to the outside of the substrate and the InGaN light-emitting layer, and the light extraction efficiency of the light-emitting element can be improved. And the luminescent element thus obtained The piece can be applied to a light source or a display.
再者,圖案化形成含有感光劑的電介質,因此,由凸部所構成的期望的圖案可形成於基板面上,故,可在無光阻膜成膜的基板面上形成圖案。因此,能夠在實現製程數減少與步驟簡化、及隨著製程數減少發光元件的低成本化的同時,製造上述光取出效率被提升的發光元件。 Further, since the dielectric containing the photosensitive agent is formed by patterning, a desired pattern composed of the convex portions can be formed on the substrate surface, so that a pattern can be formed on the surface of the substrate on which the photoresist film is not formed. Therefore, it is possible to manufacture the light-emitting element in which the light extraction efficiency is improved while realizing the reduction in the number of processes and the simplification of the steps, and the reduction in the cost of the light-emitting element as the number of processes is reduced.
再者,依據上述(12)的發明,由於凸部的一部形成為曲面狀,可更提升發光元件的光取出效率。再者,相較於剖面形狀為台形形狀或矩形形狀的凸部,成形為曲面狀的凸部,由於GaN層等成膜時GaN層的橫方向成長時間變短,故可縮短GaN層的成長時間。 Further, according to the invention of the above (12), since one portion of the convex portion is formed in a curved shape, the light extraction efficiency of the light-emitting element can be further improved. In addition, the convex portion having a trapezoidal shape or a rectangular shape is formed into a curved convex portion, and the growth time in the lateral direction of the GaN layer is shortened when a GaN layer or the like is formed, so that the growth of the GaN layer can be shortened. time.
再者,依據上述(13)的發明,構成凸部的材料為以SiO2、TiO2、ZrO2、Al2O3任一者作為主要成分的電介質,可防止凸部上發生GaN層的成長,或難以發生成長。藉由抑制凸部上GaN層的成長,可實現FACELO成長模式,故,可形成錯位密度減少的GaN層。 According to the invention of the above (13), the material constituting the convex portion is a dielectric material containing SiO 2 , TiO 2 , ZrO 2 or Al 2 O 3 as a main component, and the growth of the GaN layer on the convex portion can be prevented. Or it is difficult to grow. By suppressing the growth of the GaN layer on the bump, the FACELO growth mode can be realized, so that a GaN layer having a reduced dislocation density can be formed.
再者,依據上述(14)或(15)的發明,凸部為全部由曲面所形成,故為頂部及側部無區別,無平坦面存在的曲面形狀,因此,可提升發光元件的光取出效率。再者,凸部成形為半球形,可更提升上述光取出效率。承如上述,相較於剖面形狀為台形形狀或矩形形狀的凸部,成形為曲面狀的凸部,在GaN層等成膜時GaN層的橫方向成長時間變短,故,可縮短GaN層的成長時間。 Further, according to the invention of the above (14) or (15), since the convex portions are all formed by the curved surface, there is no difference between the top portion and the side portion, and there is no curved surface shape in which the flat surface exists, and therefore, the light extraction of the light-emitting element can be improved. effectiveness. Furthermore, the convex portion is formed into a hemispherical shape to further enhance the above-described light extraction efficiency. As described above, the convex portion having a trapezoidal shape or a rectangular shape is formed into a curved convex portion, and the growth time in the lateral direction of the GaN layer is shortened when a GaN layer or the like is formed, so that the GaN layer can be shortened. Growth time.
再者,依據上述(16)的發明,由於將凸部的平面形 狀設定為圓形或橢圓形,可簡化電介質層的圖案化步驟。特別是藉由將上述平面形狀設定為圓形,可加乘上述效果,即使發生複數個凸部所引起的光的反射、折射、衰減等彼此的相互作用(例如干涉),該相互作用並無方向性,光為全方向均勻地發出,故,可製作光取出效率高的發光元件。 Furthermore, according to the invention of (16) above, the planar shape of the convex portion is The shape is set to a circular or elliptical shape, which simplifies the patterning step of the dielectric layer. In particular, by setting the planar shape to a circular shape, the above effect can be multiplied, and even if interaction (for example, interference) of reflection, refraction, attenuation, and the like of light caused by a plurality of convex portions occurs, the interaction does not occur. Since the light is emitted uniformly in all directions, it is possible to produce a light-emitting element having high light extraction efficiency.
再者,依據上述(18)的發明,相對於上述基板的表面中全部圖案的比例,全部上述圖案缺陷處設定為0%以上50%以下,因此,可降低相同基板上所製作的發光元件的元件間光輸出的不一致。 According to the invention of the above (18), all of the pattern defects are set to 0% or more and 50% or less with respect to the ratio of all the patterns on the surface of the substrate, so that the light-emitting elements fabricated on the same substrate can be reduced. Inconsistent light output between components.
1‧‧‧在面上具有預定圖案的基板 1‧‧‧Substrate with a predetermined pattern on the surface
1a‧‧‧基板 1a‧‧‧Substrate
2b‧‧‧凸部 2b‧‧‧ convex
2‧‧‧n型GaN接觸層(n-GaN層) 2‧‧‧n-type GaN contact layer (n-GaN layer)
3‧‧‧InGaN發光層(活性層) 3‧‧‧InGaN luminescent layer (active layer)
4‧‧‧p型AlGaN被覆層 4‧‧‧p-type AlGaN coating
5‧‧‧p型GaN接觸層 5‧‧‧p-type GaN contact layer
6‧‧‧p型電極 6‧‧‧p-type electrode
7‧‧‧n型電極層 7‧‧‧n type electrode layer
8‧‧‧LED發光元件 8‧‧‧LED light-emitting components
9‧‧‧金屬電極 9‧‧‧Metal electrode
10‧‧‧光罩 10‧‧‧Photomask
11‧‧‧模型 11‧‧‧ model
12‧‧‧噴嘴 12‧‧‧ nozzle
13‧‧‧台形形狀的凸部 13‧‧‧-shaped convex
14‧‧‧矩形形狀的凸部 14‧‧‧Rectangular convex
100‧‧‧照明裝置 100‧‧‧Lighting device
101‧‧‧光源(發光元件) 101‧‧‧Light source (light-emitting element)
200‧‧‧顯示器裝置 200‧‧‧ display device
201‧‧‧光源(發光元件) 201‧‧‧Light source (lighting element)
300‧‧‧太陽電池 300‧‧‧Solar battery
301‧‧‧基板 301‧‧‧Substrate
第1圖係表示本發明相關的發光元件構造的示意圖。 Fig. 1 is a schematic view showing the configuration of a light-emitting element related to the present invention.
第2圖係表示本發明相關的在面上具有預定圖案的基板的示意圖。 Fig. 2 is a schematic view showing a substrate having a predetermined pattern on a surface according to the present invention.
第3圖(a)係第2圖所示基板的放大側面圖。 Fig. 3(a) is an enlarged side view showing the substrate shown in Fig. 2.
第3圖(b)係放大第2圖所示基板,僅表示凸部的部分的平面圖。 Fig. 3(b) is an enlarged plan view showing a portion of the substrate shown in Fig. 2, showing only the convex portion.
第4圖(a)係表示本發明相關在面上具有平面形狀為橢圓的凸部的圖案的基板的放大側面圖。 Fig. 4(a) is an enlarged side view showing a substrate of a pattern having a convex portion having a planar elliptical shape on the surface according to the present invention.
第4圖(b)係僅表示第4圖(a)所示基板凸部的部分平面圖。 Fig. 4(b) is a partial plan view showing only the convex portion of the substrate shown in Fig. 4(a).
第4圖(c)係第4圖(a)所示基板從90度相異方向所見的放大側面圖。 Fig. 4(c) is an enlarged side view showing the substrate shown in Fig. 4(a) from a 90-degree different direction.
第4圖(d)係僅表示第4圖(c)所示基板的凸部的部分平面圖。 Fig. 4(d) is a partial plan view showing only the convex portion of the substrate shown in Fig. 4(c).
第5圖(a)係僅表示本發明相關平面形狀為三角形的凸部 的部分平面圖。 Fig. 5(a) shows only the convex portion of the present invention in which the plane shape is triangular Part of the floor plan.
第5圖(b)係僅表示本發明相關平面形狀為六角形的凸部的部分平面圖。 Fig. 5(b) is a partial plan view showing only the convex portion in which the planar shape of the present invention is hexagonal.
第6圖係表示本發明相關在面上具有平面形狀為略多邊形的凸部的圖案的基板,係放大側面圖。 Fig. 6 is a perspective view showing a substrate having a pattern having a convex portion having a planar polygonal shape on the surface according to the present invention.
第6A圖係基板的變化例的基板的放大側面圖。 Fig. 6A is an enlarged side view of the substrate of a variation of the substrate.
第6A圖(a)係第3圖(a)所示基板的變化例的基板的放大側面圖。 Fig. 6A(a) is an enlarged side view showing a substrate of a variation of the substrate shown in Fig. 3(a).
第6A圖(b)係第4圖(c)所示基板的變化例的基板的放大側面圖。 Fig. 6A(b) is an enlarged side view showing a substrate of a variation of the substrate shown in Fig. 4(c).
第6A圖(c)係第6圖所示基板的變化例的基板的放大側面圖。 Fig. 6A(c) is an enlarged side view showing a substrate of a variation of the substrate shown in Fig. 6.
第7圖(a)表示台形形狀的凸部中GaN層的成長階段,係凸部放大圖。 Fig. 7(a) is a view showing an enlarged stage of a convex portion of a GaN layer in a convex portion having a mesa shape.
第7圖(b)表示矩形形狀的凸部中GaN層的成長階段,係凸部放大圖。 Fig. 7(b) is a view showing an enlarged stage of a convex portion of a GaN layer in a convex portion having a rectangular shape.
第7圖(c)表示圖案全部成形為曲面狀的凸部中GaN層的成長階段,係凸部放大圖。 Fig. 7(c) is a plan view showing a growth stage of the GaN layer in the convex portion in which all the patterns are formed into a curved shape, and is an enlarged view of the convex portion.
第7圖(d)表示頂部的一部成形為曲面狀的凸部中GaN層的成長階段,係凸部放大圖。 Fig. 7(d) shows a stage in which the GaN layer is formed in a convex portion formed in a curved shape at the top portion, and is an enlarged view of the convex portion.
第8圖係表示本實施形態的製造方法相關的一形態,光蝕刻法的製造步驟的示意圖。 Fig. 8 is a view showing a manufacturing process of the photolithography method according to an embodiment of the manufacturing method of the embodiment.
第9圖係表示本實施形態的製造方法相關的其他形態,壓印法的製造步驟的示意圖。 Fig. 9 is a view showing another embodiment of the manufacturing method of the embodiment, and a manufacturing procedure of the imprint method.
第10圖係表示本實施形態的製造方法相關的其他形態, 噴墨法的製造步驟的示意圖。 Fig. 10 is a view showing another aspect related to the manufacturing method of the embodiment. Schematic diagram of the manufacturing steps of the ink jet method.
第11圖係表示本發明相關發光元件的製造過程的剖面圖。 Figure 11 is a cross-sectional view showing the manufacturing process of the light-emitting element of the present invention.
第12圖係表示本發明的實施例的凸部剖面形狀的AFM像。 Fig. 12 is a view showing an AFM image of a cross-sectional shape of a convex portion of an embodiment of the present invention.
第13圖係表示本發明的實施例的凸部形狀的AFM側視像。 Fig. 13 is a view showing the AFM side view of the convex shape of the embodiment of the present invention.
第14圖係包括具有本發明發光元件的光源的照明裝置。 Fig. 14 is a lighting device including a light source having the light-emitting element of the present invention.
第15圖係包括具有本發明發光元件的光源的顯示器裝置。 Fig. 15 is a view showing a display device including a light source of the light-emitting element of the present invention.
第16圖係包括本發明的基板的太陽電池。 Fig. 16 is a solar cell including the substrate of the present invention.
第17圖係表示習知發光元件的構造的示意圖。 Fig. 17 is a schematic view showing the configuration of a conventional light-emitting element.
第18圖係表示習知其他發光元件的構造的示意圖。 Fig. 18 is a schematic view showing the configuration of a conventional light-emitting element.
以下,參照第1圖至第7圖,說明可用於發光元件用GaN層的形成,在面上具有期望的圖案的基板及使用該基板的發光元件的本實施形態。由第1圖,在面上具有期望的圖案的基板1(以下,表示為「基板1」)為LED發光元件8(以下,表示為「發光元件8」)的基底基板。再者如第2圖所示,基板1在平坦的基板1a的面上具有由島狀的凸部1b所構成的圖案。再者,凸部1b為由電介質所構成。 Hereinafter, a substrate which can be used for formation of a GaN layer for a light-emitting element, a substrate having a desired pattern on the surface, and a light-emitting device using the substrate will be described with reference to FIGS. 1 to 7. In the first embodiment, the substrate 1 having a desired pattern on the surface (hereinafter referred to as "substrate 1") is a base substrate of the LED light-emitting element 8 (hereinafter referred to as "light-emitting element 8"). Further, as shown in Fig. 2, the substrate 1 has a pattern composed of island-like convex portions 1b on the surface of the flat substrate 1a. Further, the convex portion 1b is made of a dielectric.
上述島狀係指在基板1a的厚度方向上,由凸部1b的頂部起至基板1a表面的高度,各個凸部1b具有獨立的凸形狀。因此,由凸部1b的頂部起至基板1a表面的高度為止,只要各個凸部1b為具有獨立的凸形狀,即滿足島狀的圖案,基板1a從基板平面方向(第1圖或第2圖由上朝下的方向)觀看時,各凸部1b彼此分離,或在凸部1b的底面亦即在基板1a表面各凸部1b的側部彼此連接,兩者皆可。 The island shape refers to the height from the top of the convex portion 1b to the surface of the substrate 1a in the thickness direction of the substrate 1a, and each convex portion 1b has an independent convex shape. Therefore, from the top of the convex portion 1b to the height of the surface of the substrate 1a, as long as each convex portion 1b has an independent convex shape, that is, an island-like pattern is satisfied, the substrate 1a is oriented from the substrate plane (Fig. 1 or 2) When viewed from the upper direction, the convex portions 1b are separated from each other, or the bottom surface of the convex portion 1b, that is, the side portions of the convex portions 1b on the surface of the substrate 1a are connected to each other.
凸部1b形成於基板1a的表面上,因此,各凸部1b有光散射效果。因此,發光元件8內部所吸收的光的一部可取出至基板1a及InGaN發光層3的外部,可提升發光元件8的光取出效率。 The convex portion 1b is formed on the surface of the substrate 1a, and therefore, each convex portion 1b has a light scattering effect. Therefore, a part of the light absorbed inside the light-emitting element 8 can be taken out to the outside of the substrate 1a and the InGaN light-emitting layer 3, and the light extraction efficiency of the light-emitting element 8 can be improved.
n型GaN接觸層(n-GaN層)2的成長從凸部1b之間的基板1a表面,亦即沒有凸部1b的平坦部開始,隨著n-GaN層2的厚度變厚,覆蓋凸部1b的側部及頂部。因此,覆蓋基板1a的表面及凸部1b的圖案形成GaN層。 The growth of the n-type GaN contact layer (n-GaN layer) 2 starts from the surface of the substrate 1a between the convex portions 1b, that is, the flat portion having no convex portion 1b, and becomes thicker as the thickness of the n-GaN layer 2 becomes thicker. The side and the top of the part 1b. Therefore, the surface of the cover substrate 1a and the pattern of the convex portion 1b form a GaN layer.
基板1a以藍寶石(Al2O3)、Si、SiC、GaAs、InP、尖晶石等之類,3-5族化合物半導體可成長可能的材料為佳,特別是藍寶石,從3-5族化合物半導體形成的觀點為最佳。以下,以藍寶石基板作為基板1a為例,繼續說明。 The substrate 1a is made of sapphire (Al 2 O 3 ), Si, SiC, GaAs, InP, spinel, etc., and a group 3-5 compound semiconductor can grow as a possible material, particularly sapphire, from a group 3-5 compound. The viewpoint of semiconductor formation is optimal. Hereinafter, the sapphire substrate is used as the substrate 1a as an example, and the description will be continued.
使用藍寶石基板作為基板1a時,基板1a表面由C面、A面、R面等適當選擇,或是傾斜該等表面亦可。 When the sapphire substrate is used as the substrate 1a, the surface of the substrate 1a may be appropriately selected from the C surface, the A surface, the R surface, or the like, or the surfaces may be inclined.
又,從防止n-GaN層2內的結晶成長時發生缺陷的觀點來看,成為n-GaN層2的成長起始處的基板1a的表面為表面粗糙度Ra為1nm以下左右的鏡面狀態為佳。為了使基板1a的表面成為鏡面狀態,例如以實施鏡面研磨為佳。 In addition, from the viewpoint of preventing the occurrence of defects in the growth of the crystals in the n-GaN layer 2, the surface of the substrate 1a at the start of growth of the n-GaN layer 2 has a mirror surface roughness of about 1 nm or less. good. In order to make the surface of the substrate 1a mirror-finished, for example, mirror polishing is preferably performed.
凸部1b的材料為含有感光劑的電介質。藉由含有感光劑的電介質形成凸部1b,即使無如後述的光阻膜(亦即,凸部1b形成膜的蝕刻用光罩),可將凸部1b的圖案形成於基板1a的面上。再者,作為形成凸部1b的電介質,以SiO2、TiO2、ZrO2、Al2O3任一者作為主要成分的電介質中含有結合劑樹脂、感光劑的組成物為佳,以矽氧烷樹脂作為樹脂較佳。作為 電介質組成物,例如可列舉感光性的矽氧烷樹脂組成物、感光性的含氧化鈦的矽氧烷樹脂組成物、感光性的含氧化鋯的矽氧烷樹脂組成物、感光性的含氧化鋁的矽氧烷樹脂組成物。 The material of the convex portion 1b is a dielectric containing a sensitizer. By forming the convex portion 1b by the dielectric containing the photosensitive agent, the pattern of the convex portion 1b can be formed on the surface of the substrate 1a even if there is no photoresist film (that is, the etching mask for forming the film by the convex portion 1b) as will be described later. . Further, as the dielectric material forming the convex portion 1b, a composition containing a binder resin or a sensitizer in a dielectric containing SiO 2 , TiO 2 , ZrO 2 or Al 2 O 3 as a main component is preferable, and oxygen is used. An alkane resin is preferred as the resin. Examples of the dielectric composition include a photosensitive decane resin composition, a photosensitive titanium oxide-containing decane resin composition, a photosensitive zirconia-containing decane resin composition, and a photosensitive content. A hafnium oxide resin composition of alumina.
矽氧烷樹脂組成物係含有具有以矽氧烷鍵結之主要骨架的聚合物。具有以矽氧烷鍵結之主要骨架的聚合物並無特別限制,較佳為以凝膠滲透層析儀(GPC)所測定的換算成聚苯乙烯的重量平均分子量(Mw)為1000~100000,更佳為2000~50000。當Mw小於1000時,塗膜性變差,當大於100000時,對圖案形成時的顯影液的溶解性變差。 The decane resin composition contains a polymer having a main skeleton bonded with a decane. The polymer having a main skeleton bonded by a siloxane is not particularly limited, and preferably has a weight average molecular weight (Mw) of from 1,000 to 100,000 in terms of polystyrene measured by a gel permeation chromatography (GPC). More preferably, it is 2000~50000. When the Mw is less than 1,000, the coating property is deteriorated, and when it is more than 100,000, the solubility in the developer at the time of pattern formation is deteriorated.
由於矽氧烷樹脂組成物、含有氧化鈦的矽氧烷樹脂組成物、含有氧化鋯的矽氧烷樹脂組成物、含有氧化鋁的矽氧烷樹脂組成物被覆性良好,因此,可以在無光阻膜成膜的基板1a表面上以均一厚度或高度形成無紊亂電介質。再者相較於其他樹脂、含氧化鈦樹脂、含氧化鋯樹脂、含氧化鋁樹脂,硬化收縮小,因此,能夠易於以如期望的高度與大小及間距將凸部1b形成在基板1a面上。此外矽氧烷樹脂組成物、含有氧化鈦的矽氧烷樹脂組成物、含有氧化鋯的矽氧烷樹脂組成物、含有氧化鋁的矽氧烷樹脂組成物相較於其他樹脂、含氧化鈦樹脂、含氧化鋯樹脂、含氧化鋁樹脂,在硬化後難以產生裂痕,因此在凸部的電介質中不易發生空隙,在GaN層(2乃至5)成長時,凸部1b與GaN層的界面不易發生間隙(孔洞)。因此,可防止發光元件8中發生電特性的惡化。並且,上述間距係指相鄰的凸部1b彼此的中心間距離的最小距離。 Since the decane resin composition, the cerium oxide-containing cerium oxide resin composition, the zirconia-containing cerium oxide resin composition, and the alumina-containing cerium oxide resin composition have good coating properties, they can be used in the absence of light. The surface of the substrate 1a on which the resist film is formed forms a disorder-free dielectric with a uniform thickness or height. Further, compared with other resins, titanium oxide-containing resins, zirconia-containing resins, and alumina-containing resins, the hardening shrinkage is small, and therefore, the convex portions 1b can be easily formed on the surface of the substrate 1a at a desired height, size, and pitch. . Further, the decane resin composition, the cerium oxide-containing cerium oxide resin composition, the zirconia-containing cerium oxide resin composition, and the alumina-containing cerium oxide resin composition are compared with other resins and titanium oxide-containing resins. The zirconia-containing resin or the alumina-containing resin is less likely to cause cracks after curing, so that voids are less likely to occur in the dielectric of the convex portion, and the interface between the convex portion 1b and the GaN layer is less likely to occur when the GaN layer (2 to 5) is grown. Clearance (hole). Therefore, deterioration of electrical characteristics in the light-emitting element 8 can be prevented. Further, the above-described pitch means the minimum distance between the centers of the adjacent convex portions 1b.
再者,由於構成凸部1b的材料為以SiO2、TiO2、 ZrO2、Al2O3任一者作為主要成分的電介質,可防止凸部1b上發生GaN層成長,或難以發生成長。藉由抑制凸部1b上GaN層的成長,可實現FACELO的成長模式,故可形成錯位密度減少的GaN層。 In addition, since the material constituting the convex portion 1b is a dielectric material containing either SiO 2 , TiO 2 , ZrO 2 or Al 2 O 3 as a main component, growth of the GaN layer on the convex portion 1b can be prevented or growth is less likely to occur. By suppressing the growth of the GaN layer on the convex portion 1b, the growth mode of FACELO can be realized, so that a GaN layer having a reduced dislocation density can be formed.
此外,凸部1b的大小及凸部1b彼此間的間距,從能充分地散射或折射光的觀點來看,當發光元件8的GaN層中發光波長設定為λ時,至少設定為λ/(4n)以上為佳。並且,凸部1b的大小,雖然依凸部1b的平面形狀而有各種設定,然而,以其平面形狀為如後述的圓形的情況而言,以半徑的長度,為橢圓形的情況下,表示為短軸方向的半徑長度,為多角形的情況下,表示為成為凸部1b構成邊當中一邊的長度。此外,n為GaN層的折射率,其中之一為約2.4。並且,基板1a使用於發光元件8中時,電介質的折射率以至少與氮化鎵(GaN)的折射率相異為佳。此外,從防止基板側的光穿透,提升發光元件的亮度的觀點來看,電介質的折射率以小於氮化鎵(GaN)的折射率為佳。 Further, the size of the convex portion 1b and the pitch between the convex portions 1b are set to at least λ/(when the light-emitting wavelength in the GaN layer of the light-emitting element 8 is set to λ from the viewpoint of sufficiently scattering or refracting light. 4n) Above is better. In addition, the size of the convex portion 1b is variously set depending on the planar shape of the convex portion 1b. However, when the planar shape is a circular shape to be described later, when the length of the radius is elliptical, The length of the radius indicated by the short axis direction is a length of one of the sides of the convex portion 1b when it is a polygonal shape. Further, n is a refractive index of the GaN layer, one of which is about 2.4. Further, when the substrate 1a is used in the light-emitting element 8, the refractive index of the dielectric is preferably at least different from the refractive index of gallium nitride (GaN). Further, from the viewpoint of preventing light penetration on the substrate side and improving the luminance of the light-emitting element, the refractive index of the dielectric is preferably smaller than the refractive index of gallium nitride (GaN).
此外,全部的GaN層2至5的總膜厚為30μm以下時,從減少因散射或折射的光的全反射次數的觀點來看,凸部1b間的間距為50μm以下為佳。再者,從提升GaN層的結晶性(亦即防止凹洞發生)的觀點來看,凸部1b間的間距以20μm以下為較佳。更佳為凸部間的間距設定在10μm以下,藉由將上述間距設定在10μm以下,使光散射面增加提高光的散射或折射的發生率,可更提升發光元件8的光取出效率。 When the total thickness of all the GaN layers 2 to 5 is 30 μm or less, the pitch between the convex portions 1b is preferably 50 μm or less from the viewpoint of reducing the total number of times of scattering or refracting light. Further, from the viewpoint of improving the crystallinity of the GaN layer (that is, preventing the occurrence of pits), the pitch between the convex portions 1b is preferably 20 μm or less. More preferably, the pitch between the convex portions is set to 10 μm or less, and by setting the pitch to 10 μm or less, the light scattering surface is increased to increase the incidence of light scattering or refraction, and the light extraction efficiency of the light-emitting element 8 can be further improved.
凸部1b的側面形狀如第3圖(a)、第4圖(a)及第4圖(c)、或第6圖所示,以至少凸部1b的一部份形成為曲面狀 為佳。亦即,凸部1b的至少一部份具有曲面。藉由凸部1b的一部份形成為曲面狀,可提升發光元件8的光取出效率。再者,相較於在與基板垂直的面上的剖面形狀為台形形狀或矩形形狀的凸部,成形為曲面狀的凸部1b,在GaN層(2至5)等成膜時GaN層的橫方向成長時間變短,故可縮短GaN層的成長時間。詳言之,如第7圖(a)側面形狀為台形形狀的凸部13,或如第7圖(b)側面形狀為矩形形狀的凸部14上使GaN層橫方向成長,GaN層如箭頭所表示,一開始成長側部13a、14a,接著成長頂部13b、14b的平面上,必須經歷二階段的成長。另一方面,由於如第7圖(c)圖案全部成形為曲面狀的凸部1b如箭頭所示藉由持續橫方向成長可將GaN層形成於凸部1b上,故可縮短GaN層成長時間。此外,如第7圖(d)頂部的一部份成形為曲面狀的凸部1b,由於在側部1c的GaN層的成長可快速地移往頂部1d,故可縮短GaN層的成長時間。即使只有側部的一部成形為曲面狀的凸部,促進在側部的GaN層的成長,此GaN層的成長可移往頂部,故可縮短GaN層的成長時間。 The side surface shape of the convex portion 1b is formed in a curved shape by at least a part of the convex portion 1b as shown in Fig. 3(a), Fig. 4(a) and Fig. 4(c), or Fig. 6; It is better. That is, at least a portion of the convex portion 1b has a curved surface. The light extraction efficiency of the light-emitting element 8 can be improved by forming a portion of the convex portion 1b into a curved shape. Further, the convex portion 1b formed into a curved shape as compared with the convex portion having a trapezoidal shape or a rectangular cross section on a surface perpendicular to the substrate, and a GaN layer formed when a GaN layer (2 to 5) or the like is formed. Since the growth time in the lateral direction is shortened, the growth time of the GaN layer can be shortened. In detail, as shown in Fig. 7(a), the convex portion 13 having a side shape in the shape of a table or the convex portion 14 having a rectangular shape on the side surface of Fig. 7(b) causes the GaN layer to grow in the lateral direction, and the GaN layer is as an arrow. It is shown that the first growth side portions 13a, 14a, and then the growth of the top portions 13b, 14b, must undergo two stages of growth. On the other hand, since the convex portion 1b which is formed into a curved surface as in the pattern of Fig. 7(c) can be formed on the convex portion 1b by continuing the lateral growth as indicated by the arrow, the growth time of the GaN layer can be shortened. . Further, as a part of the top portion of Fig. 7(d) is formed into a curved convex portion 1b, since the growth of the GaN layer at the side portion 1c can be quickly moved to the top portion 1d, the growth time of the GaN layer can be shortened. Even if only one of the side portions is formed into a curved convex portion, the growth of the GaN layer on the side portion is promoted, and the growth of the GaN layer can be shifted to the top, so that the growth time of the GaN layer can be shortened.
具體的凸部1b的形狀的形態之一,可列舉如平面形狀如第5圖(a)或第5圖(b)所示的略多邊形,且側面形狀為第6圖所示側部1c為傾斜的,且凸部頂部1d形成為曲面的形狀。 One of the shapes of the shape of the specific convex portion 1b is a polygonal shape as shown in Fig. 5(a) or Fig. 5(b), and the side surface shape is the side portion 1c shown in Fig. 6 . It is inclined, and the convex top portion 1d is formed into a curved shape.
當楔角θ為90°時,凸部1b的剖面形狀成為矩形,當為180°時,凸部1b成為完全平的狀態。由於要以GaN層埋覆凸部1b,故楔角θ至少必須為90°以上。 When the wedge angle θ is 90°, the cross-sectional shape of the convex portion 1b becomes a rectangle, and when it is 180°, the convex portion 1b is completely flat. Since the convex portion 1b is to be buried with the GaN layer, the wedge angle θ must be at least 90° or more.
略多邊形係指三角形或六角形,不必非得要幾何學上的完全多角形,包含因加工的緣故等在角或邊帶點圓滑的多 角形在內。由於凸部1b的平面形狀成形為三角形或六角形,可在對於GaN層的成長安定面幾乎平行的面上具有頂點,且與對於GaN層成長安定面幾乎平行的面交叉的直線成為構成邊。 A slightly polygonal shape refers to a triangle or a hexagon. It does not have to be a geometrically complete polygon, including a lot of angles at the corners or side points due to processing. The angle is inside. Since the planar shape of the convex portion 1b is formed into a triangular shape or a hexagonal shape, a vertex having a vertex that is almost parallel to the growth and stability surface of the GaN layer can be formed, and a straight line intersecting with a surface almost parallel to the growth and stability surface of the GaN layer can be a constituent side.
此外,作為凸部1b平面形狀的另外形態,從提升上述光取出效率及縮短GaN層(2至5)的橫方向成長時間的觀點來看,以將凸部1b全部形成為曲面,具有頂部及側部無區別,無平坦面存在的曲面形狀為佳,凸部1b為如第3圖(a)所示的半球形為更佳。因此,在凸部1b的各部位中曲率大於0,除了凸部1b與基板1a連接的位置以外其餘沒有角部存在。此外、上述第3圖(a)、第4圖(c)、以及第6圖中分別表示的基板1a及凸部1b皆可具有如第6A圖所示的變化例。第6A圖(a)及第6A圖(b)所示的變化例,凸部1b全部為以曲面所形成時,其曲面在中途具有反曲點,在此反曲點的前後,具有與頂部曲面的曲率具有相反符號曲率的曲面1f。此外,第6A圖(c)所示的變化例具有一部份為側部1c,在此側部1c的前後,具有與頂部曲面的曲率具有相反符號曲率的曲面1f。在此等變化例中,由於自基板1a起至凸部1b為平順地連續著,故促進GaN層的成長,復可縮短成長時間。並且,第4圖(a)的凸部1b亦可形成同樣的曲面1f。 Further, as another form of the planar shape of the convex portion 1b, from the viewpoint of enhancing the light extraction efficiency and shortening the growth time in the lateral direction of the GaN layers (2 to 5), the convex portions 1b are all formed into a curved surface, and have a top portion and The side portion is indistinguishable, and the curved surface shape in which no flat surface exists is preferable, and the convex portion 1b is preferably a hemispherical shape as shown in Fig. 3(a). Therefore, in each portion of the convex portion 1b, the curvature is larger than 0, and no corner portion exists except for the position where the convex portion 1b is connected to the substrate 1a. Further, the substrate 1a and the convex portion 1b shown in each of Figs. 3(a), 4(c), and 6th, respectively, may have variations as shown in Fig. 6A. In the variation shown in FIGS. 6A(a) and 6A(b), when the convex portions 1b are all formed by curved surfaces, the curved surface has an inflection point in the middle, and the front and back of the inflection point have the top and the top. The curvature of the surface has a curved surface 1f of opposite sign curvature. Further, the modification shown in (c) of Fig. 6A has a portion 1c which is a front surface 1c, and has a curved surface 1f having an opposite sign curvature from the curvature of the top curved surface. In these variations, since the convex portion 1b is smoothly continuous from the substrate 1a, the growth of the GaN layer is promoted, and the growth time can be shortened. Further, the convex portion 1b of Fig. 4(a) may also have the same curved surface 1f.
再者,凸部1b的平面形狀,以如第3圖(b)所示的圓形,或如第4圖(b)及第4圖(d)所示的橢圓形為佳。但是,因形成為圓形,即使發生由於複數個凸部1b,1b,所引起的光反射、折射、衰減等彼此相互作用(例如干涉),因該等相互作用無方向性,光為全方向均勻發射,故可製作光取出效率高的 發光元件8。因此,以圓形的平面形狀的凸部1b為更佳。此外,平面形狀設定為圓形或橢圓形時,可簡化電介質層如後述的圖案化步驟。 Further, the planar shape of the convex portion 1b is preferably a circular shape as shown in Fig. 3(b) or an elliptical shape as shown in Figs. 4(b) and 4(d). However, since it is formed in a circular shape, light reflection, refraction, attenuation, and the like caused by the plurality of convex portions 1b, 1b interact with each other (for example, interference), and the light is omnidirectional due to the non-directionality of the interactions. Uniform emission, so it can produce high light extraction efficiency Light-emitting element 8. Therefore, the convex portion 1b having a circular planar shape is more preferable. Further, when the planar shape is set to a circular shape or an elliptical shape, the dielectric layer can be simplified as described later in the patterning step.
希望形成於基板1a表面的全部的凸部1b為相同大小、形狀,然而,每一凸部1b的大小、形狀、或上述曲率多少有些差異亦可。此外,凸部1b的排列形態亦無特別限制,可以如格子狀排列構造般,以規則的間距排列形態,以不規則的間距的排列形態亦可。或是,作為凸部1b的平面形狀,在一個基板1a面上併用圓形或橢圓形與略多邊形形狀亦可。 It is desirable that all the convex portions 1b formed on the surface of the substrate 1a have the same size and shape. However, the size, shape, or curvature of each convex portion 1b may be somewhat different. Further, the arrangement of the convex portions 1b is not particularly limited, and may be arranged in a regular pitch as in a lattice-like arrangement, and may be arranged in an irregular pitch. Alternatively, as the planar shape of the convex portion 1b, a circular or elliptical shape and a slightly polygonal shape may be used in combination on the surface of one substrate 1a.
但是,希望凸部1b的圖案其大小、高度、形狀、間距,以均一地、週期地形成於基板1a的表面。若此週期構造由凸部1b的一部份脫軌時,製作在基板1a的發光元件的元件間的光輸出會發生不一致。因此,在應該以均一間距形成有凸部1b的基板1a的表面處中,未形成有凸部1b圖案的位置(凸部1b的圖案的缺損處)的全部,在以均一的間距形成有凸部1b圖案的情況下,相對於基板1a的表面上圖案的全部,希望在0%以上50%以下的範圍內。藉由此種構成,可降低同一基板1a上所製作的發光元件8的元件間中光輸出的不一致。相對於上述基板1a的表面上的全部圖案,上述圖案缺陷處的全部的比例(上述圖案缺陷處的全部/上述基板1a表面上圖案的全部),必要時在以下記載為「圖案缺損」。當圖案缺損的比例超過50%時,基板1a表面上凸部1b的數目因GaN層橫方向成長而並得不足,變得易於在GaN層中導入結晶缺陷。 However, it is desirable that the pattern of the convex portion 1b is formed uniformly and periodically on the surface of the substrate 1a in terms of its size, height, shape, and pitch. If the periodic structure is derailed by a portion of the convex portion 1b, the light output between the elements fabricated in the light-emitting element of the substrate 1a may be inconsistent. Therefore, in the surface of the substrate 1a where the convex portion 1b should be formed at a uniform pitch, all of the positions where the pattern of the convex portion 1b is not formed (the defect of the pattern of the convex portion 1b) are formed with a uniform pitch. In the case of the portion 1b pattern, it is desirable to be in the range of 0% or more and 50% or less with respect to all of the patterns on the surface of the substrate 1a. According to this configuration, the inconsistency in light output between the elements of the light-emitting element 8 fabricated on the same substrate 1a can be reduced. The ratio of all the pattern defects (all of the pattern defects or all of the patterns on the surface of the substrate 1a) to all the patterns on the surface of the substrate 1a is described below as "pattern defect". When the ratio of the pattern defect exceeds 50%, the number of the convex portions 1b on the surface of the substrate 1a is insufficient due to the growth of the GaN layer in the lateral direction, and it becomes easy to introduce crystal defects into the GaN layer.
再者,藉由使圖案缺損的比例為0%以上至30%以 下的範圍內製作,使GaN層的橫方向成長變得更容易,不易有結晶缺陷導入,因此,可改善發光元件的靜電放電的收率因而較佳。再者,藉由在圖案缺損的比例為0%以上15%以下的範圍內製作,降低n-GaN層成膜時的表面粗糙度,可使得之後在InGaN發光層形成時的In導入量在基板1a面內變得均一,可更降低發光元件的波長不一致,因而更佳。 Furthermore, by making the ratio of pattern defects 0% to 30% The production in the lower range makes it easier to grow the GaN layer in the lateral direction, and it is less likely to introduce crystal defects. Therefore, the yield of electrostatic discharge of the light-emitting element can be improved, which is preferable. In addition, by making the ratio of the pattern defect in the range of 0% or more and 15% or less, the surface roughness at the time of film formation of the n-GaN layer can be reduced, and the amount of In introduced at the time of forming the InGaN light-emitting layer can be made on the substrate. It is preferable that the surface of 1a becomes uniform, and the wavelength of the light-emitting element is further reduced.
如上述,於基板1的面上所形成的凸部1b及於基板1a上形成2層以上的GaN層2至5以及p型電極6與n型電極層7,藉以製造發光元件8。p型電極6於p型GaN接觸層5上與金屬電極一同形成,n型電極層7形成於n-GaN層2上未形成有InGaN發光層3處。2層以上的GaN層,例如可列舉如第1圖所示,n型GaN接觸層(n-GaN層)2、InGaN發光層(活性層)3、p型AlGaN被覆層4、及p型GaN接觸層5,但不限於此種構造。以至少具有具有n型導電性的層、具p型導電性的層、挾持於其間的發光層的由3-5族氮化物化合物半導體的層所構成者為佳。作為活性層3,以Inx Gay Alz N(惟,0≦x≦1、0≦y≦1、0≦z≦1、x+y+z=1)所表示的3-5族氮化物化合物半導體所構成的層為佳。 As described above, the light-emitting element 8 is manufactured by forming the two or more GaN layers 2 to 5 and the p-type electrode 6 and the n-type electrode layer 7 on the convex portion 1b formed on the surface of the substrate 1 and on the substrate 1a. The p-type electrode 6 is formed on the p-type GaN contact layer 5 together with the metal electrode, and the n-type electrode layer 7 is formed on the n-GaN layer 2 where the InGaN light-emitting layer 3 is not formed. Examples of the GaN layer having two or more layers include an n-type GaN contact layer (n-GaN layer) 2, an InGaN light-emitting layer (active layer) 3, a p-type AlGaN cladding layer 4, and p-type GaN as shown in Fig. 1 . The contact layer 5 is, but not limited to, such a configuration. It is preferable that it is composed of a layer of a group 3-5 nitride compound semiconductor having at least a layer having n-type conductivity, a layer having p-type conductivity, and a light-emitting layer sandwiched therebetween. As the active layer 3, a group 3-5 nitride compound semiconductor represented by Inx Gay Alz N (only, 0≦x≦1, 0≦y≦1, 0≦z≦1, x+y+z=1) The layer formed is preferred.
形成於上述基板1上的3-5族氮化物化合物半導體不限於GaN層,以至少包含AlN層或InN層任何一層的方式予以變更亦可。具體而言,可列舉如在形成於基板1上由AlN等所構成的緩衝層上形成n-GaN層2。並且上述緩衝層亦可使用由GaN而成的層。 The group 3-5 nitride compound semiconductor formed on the substrate 1 is not limited to the GaN layer, and may be modified so as to include at least one layer of the AlN layer or the InN layer. Specifically, the n-GaN layer 2 is formed on a buffer layer formed of AlN or the like formed on the substrate 1. Further, a layer made of GaN may be used as the buffer layer.
接著,參照第8圖~第11圖說明基板1的製造方 法。第8圖為本實施形態的上述製造方法相關的一形態,係表示利用光蝕刻法由含有感光劑的電介質所構成的凸部的製造步驟的示意圖。第9圖為本實施形態的上述製造方法相關的其他形態,係表示壓印法的製造步驟的示意圖。第10圖為本實施形態的上述製造方法相關的其他形態,係表示噴墨法的製造步驟的示意圖。 Next, the manufacturing side of the substrate 1 will be described with reference to FIGS. 8 to 11 law. Fig. 8 is a schematic view showing a manufacturing process of a convex portion composed of a dielectric containing a photosensitive agent by photolithography according to an aspect of the above-described production method of the embodiment. Fig. 9 is a view showing another embodiment of the above-described manufacturing method of the embodiment, showing a manufacturing procedure of the imprint method. Fig. 10 is a view showing another embodiment of the above-described production method of the embodiment, showing a manufacturing procedure of the ink jet method.
如第8圖(a)、第9圖(a)、第10圖(a)所示,首先準備平坦的基板1a,接著如第8圖(b)、第9圖(b)、第10圖(b)所示,將含有感光劑、具有感光性的電介質1e形成於基板1a面上,圖案化形成電介質1e,將由期望的圖案的電介質所構成的上述凸部1b形成於基板1a面上。第8圖及第9圖所示的製造方法中,將電介質1e形成為特定厚度的膜,第10圖的製造方法中,形成複數個凸形狀。並且,基板1a為平坦係指圖案化形成有電介質1e的基板1a的表面為鏡面狀態,表面粗糙度Ra為1nm以下左右。此外,期望的圖案係指由島狀的凸部1b所構成的圖案。 As shown in Fig. 8 (a), Fig. 9 (a), and Fig. 10 (a), first, a flat substrate 1a is prepared, and then, as shown in Fig. 8 (b), Fig. 9 (b), and Fig. 10 (b), the photosensitive medium 1e containing a photosensitive agent and photosensitive is formed on the surface of the substrate 1a, the dielectric 1e is patterned, and the convex portion 1b composed of a dielectric of a desired pattern is formed on the surface of the substrate 1a. In the manufacturing method shown in Figs. 8 and 9, the dielectric 1e is formed into a film having a specific thickness, and in the manufacturing method of Fig. 10, a plurality of convex shapes are formed. Further, the substrate 1a is flat, and the surface of the substrate 1a on which the dielectric 1e is patterned is mirror-finished, and the surface roughness Ra is about 1 nm or less. Further, the desired pattern refers to a pattern composed of island-like convex portions 1b.
由於圖案化形成含有感光劑的電介質,由上述凸部1b所構成的期望的圖案形成於基板1a面上,故能夠無光阻膜(凸部1b形成膜的蝕刻用光罩)成膜而在基板1a面上形成圖案。因此,可實現製程數減少與步驟簡化、及隨著製程數減少基板1的低成本化。 Since a dielectric material containing a photosensitive agent is formed by patterning, a desired pattern formed by the convex portion 1b is formed on the surface of the substrate 1a, so that a film can be formed without a photoresist film (the etching mask for forming the film by the convex portion 1b). A pattern is formed on the surface of the substrate 1a. Therefore, it is possible to reduce the number of processes and simplify the steps, and to reduce the cost of the substrate 1 as the number of processes is reduced.
再者,作為上述電介質1e,以上述矽氧烷樹脂組成物為例,詳細說明每個步驟。以下,以基板1a為藍寶石製(以下,表示為「藍寶石基板1a」)的情況為例,進行說明。 Further, as the dielectric 1e, each step of the above-described decane resin composition will be described in detail. Hereinafter, a case where the substrate 1a is made of sapphire (hereinafter referred to as "sapphire substrate 1a") will be described as an example.
作為上述第8圖(a)、第9圖(a)、第10圖(a)的前置步驟,將藍寶石基板1a以UV/O3洗淨,之後進行水洗、脫水烘乾。再者,對藍寶石基板1a施行六甲基二矽氮烷(HMDS)步驟,進行烘乾,如第8圖(a)、第9圖(a)、第10圖(a)所示,準備作為平坦的基板的藍寶石基板1a。 As a pre-step of the above-mentioned Fig. 8 (a), Fig. 9 (a), and Fig. 10 (a), the sapphire substrate 1a is washed with UV/O 3 , and then washed with water and dehydrated and dried. Further, the sapphire substrate 1a is subjected to a hexamethyldioxane (HMDS) step and dried, as shown in Fig. 8 (a), Fig. 9 (a), and Fig. 10 (a), prepared as A sapphire substrate 1a of a flat substrate.
接著,第8圖(b)或第9圖(b)中,在此藍寶石基板1a的面上以旋轉器均勻塗佈矽氧烷樹脂組成物。 Next, in Fig. 8(b) or Fig. 9(b), a decane resin composition is uniformly applied to the surface of the sapphire substrate 1a by a rotator.
由於矽氧烷樹脂組成物用於凸部1b的形成材料中,因此被覆性良好,故可在基板1a表面以均一厚度或高度形成無紊亂電介質。再者,相較於其他樹脂、含氧化鈦樹脂、含氧化鋯樹脂、含氧化鋁樹脂,硬化收縮小,故可易於以如期望的高度與大小及間距,將凸部1b形成於基板1a面上。此外,矽氧烷樹脂組成物相較於其他樹脂、含氧化鈦樹脂、含氧化鋯樹脂、含氧化鋁樹脂,硬化後不易產生裂痕,故凸部的電介質中不易產生空隙,在GaN層(2至5)成長時,凸部1b與GaN層的界面不易產生間隙(孔洞)。因此,可防止發光元件8的電特性的惡化。 Since the rhodium oxide resin composition is used for the material for forming the convex portion 1b, the coating property is good, so that a disorder-free dielectric can be formed on the surface of the substrate 1a with a uniform thickness or height. Further, since the hardening shrinkage is small compared to other resins, titanium oxide-containing resins, zirconia-containing resins, and alumina-containing resins, the convex portions 1b can be easily formed on the substrate 1a at a desired height, size, and pitch. on. In addition, the rhodium oxide resin composition is less prone to cracking after hardening than other resins, titanium oxide-containing resins, zirconia-containing resins, and alumina-containing resins, so that voids are less likely to occur in the dielectric of the convex portion, and the GaN layer (2) When the growth is 5), a gap (hole) is less likely to occur at the interface between the convex portion 1b and the GaN layer. Therefore, deterioration of the electrical characteristics of the light-emitting element 8 can be prevented.
將矽氧烷樹脂組成物形成於基板1a面上後,將由此矽氧烷樹脂組成物而成的上述期望的圖案形成於基板1a面上的方法有好幾種,例如可列舉上述的光蝕刻法、壓印法、及噴墨法3種方法。 After the rhodium oxide resin composition is formed on the surface of the substrate 1a, the desired pattern obtained by using the composition of the decane resin is formed on the surface of the substrate 1a. For example, photolithography described above may be mentioned. Method, imprint method, and inkjet method.
光蝕刻法的步驟如下。如上述,將電介質1e塗佈於基板1a的面上,將電介質1e的膜形成於基板1a的面上(參照第8圖(b))。之後,將電介質1e的膜形成於基板1a面上的基板1a預烘,接著,如第8(c)圖所示,使用光罩10將電介質 1e的膜曝光成期望的圖案。再者,對已曝光的電介質1e顯影(參照第8圖(d)),對經顯影的電介質1e進行後烘。再者,如第8圖(e)所示,對後烘後的電介質1e進行退火,使期望的圖案的電介質1e(在第8圖(e)的時間點,電介質1e成為凸部1b)形成於基板1a面上。並且,雖然上述例對經顯影的電介質1e進行後烘後,對電介質1e進行退火,然而並不限定於此,亦可不進行後烘,對僅經顯影的電介質1e直接進行退火亦可。 The steps of the photolithography method are as follows. As described above, the dielectric 1e is applied onto the surface of the substrate 1a, and the film of the dielectric 1e is formed on the surface of the substrate 1a (see Fig. 8(b)). Thereafter, the substrate 1a on which the film of the dielectric 1e is formed on the surface of the substrate 1a is pre-baked, and then, as shown in Fig. 8(c), the dielectric is used using the photomask 10. The film of 1e is exposed to the desired pattern. Further, the exposed dielectric 1e is developed (see Fig. 8(d)), and the developed dielectric 1e is post-baked. Further, as shown in Fig. 8(e), the dielectric 1e after the post-baking is annealed to form a dielectric 1e of a desired pattern (at the time point of Fig. 8(e), the dielectric 1e becomes the convex portion 1b). On the surface of the substrate 1a. Further, although the dielectric 1e is annealed after the post-baking of the developed dielectric 1e in the above example, the dielectric 1e is not limited thereto, and the dielectric 1e which is only developed may be directly annealed without post-baking.
壓印法的步驟如下。如上述,將電介質1e塗佈於基板1a的面上,使電介質1e的膜形成於基板1a的面上(參照第9圖(b))。之後,將模型11壓附於電介質1e的膜,藉由對上述電介質光照射而使其硬化(參照第9圖(c))。接著,對電介質1e進行後烘(參照第9圖(d)),再者,如第9圖(e)所示,對後烘後的電介質1e進行退火,使期望的圖案的電介質1e(在第9圖(e)的時間點,電介質1e成為凸部1b)形成於基板1a面上。 The steps of the imprint method are as follows. As described above, the dielectric 1e is applied onto the surface of the substrate 1a, and the film of the dielectric 1e is formed on the surface of the substrate 1a (see FIG. 9(b)). Thereafter, the mold 11 is pressed against the film of the dielectric 1e, and is cured by irradiation with the dielectric light (see Fig. 9(c)). Next, the dielectric 1e is post-baked (see FIG. 9(d)), and as shown in FIG. 9(e), the dielectric 1e after the post-baking is annealed to form a dielectric 1e of a desired pattern (in At the time point of Fig. 9(e), the dielectric 1e is formed on the surface of the substrate 1a as the convex portion 1b).
噴墨法的步驟如下。取代上述以旋轉器塗佈矽氧烷樹脂組成物的方式,將電介質1e由噴嘴12直接於基板1a面上,圖案化形成為期望的圖案(參照第10圖(b))。接著,對在面上形成有電介質1e的基板1a進行預烘,接著對電介質1e進行曝光後,進行後烘(參照第10圖(c))。接著,如第10圖(d)所示,對後烘後的電介質1e進行退火,將期望的圖案的電介質1e(在第10圖(d)的時間點,電介質1e成為凸部1b)形成於基板1a面上。並且,不論壓印法或噴墨法,皆可不進行後烘,對電介質1e直接退火亦可。 The steps of the ink jet method are as follows. Instead of the above-described rotator coating of the siloxane resin composition, the dielectric 1e is directly formed on the surface of the substrate 1a by the nozzle 12, and patterned into a desired pattern (see FIG. 10(b)). Next, the substrate 1a on which the dielectric 1e is formed is prebaked, and then the dielectric 1e is exposed, followed by post-baking (see FIG. 10(c)). Next, as shown in FIG. 10(d), the post-baking dielectric 1e is annealed to form a dielectric 1e of a desired pattern (at the time point of FIG. 10(d), the dielectric 1e is a convex portion 1b). On the surface of the substrate 1a. Further, regardless of the imprint method or the inkjet method, post-baking may not be performed, and the dielectric 1e may be directly annealed.
光蝕刻法中,作為曝光的光源,從形成微細圖案 的觀點來看,以高壓水銀燈的g線(波長436nm)、h線(波長405nm)、i線(波長365nm)、KrF準分子雷射(波長248nm)、ArF準分子雷射(波長193nm)等為佳。此外,作為電介質1e的膜,有正型與負型,從圖案的微細化,亦即解析度高的觀點,再者,從後烘時、退火時容易回焊,圖案的形狀容易圓滑的觀點來看,以正型為佳。正型的情況,在曝光後,不用烘乾,需要顯影。曝光後,在60℃以上烘乾時,曝光部的矽氧烷有縮合反應,對顯影液的溶解性不佳,無法形成圖案,因而不佳。 In the photoetching method, as a light source for exposure, a fine pattern is formed From the point of view, the g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), etc. of a high-pressure mercury lamp, etc. It is better. In addition, as the film of the dielectric 1e, there are a positive type and a negative type, and from the viewpoint of miniaturization of the pattern, that is, a high resolution, and further, it is easy to reflow from the post-baking and annealing, and the shape of the pattern is easy to be smooth. Look, it is better to be positive. In the case of a positive type, after exposure, there is no need to dry and development is required. After the exposure, when drying at 60 ° C or higher, the oxime of the exposed portion has a condensation reaction, and the solubility in the developer is not good, and a pattern cannot be formed, which is not preferable.
對於正型感光性矽氧烷,作為感光劑,以使用二叠氮化萘醌-5-磺酸酯(naphthoquinone diazide-5-sulfonic acid ester)為佳。從可圖案微細化的觀點來看,曝光裝置以可縮小投影曝光手法的裝置為佳。 For the positive photosensitive siloxane, a naphthoquinone diazide-5-sulfonic acid ester is preferably used as the sensitizer. From the viewpoint of pattern refinement, the exposure apparatus is preferably a device capable of reducing the projection exposure method.
此外,光蝕刻法的顯影液,使用可溶解矽氧烷樹脂組成物的藥劑,當為有機溶劑時,會有有機鹼或無機鹼的情況。然而,從無法避免對後續步驟混入氫氧化鉀(KOH)等無機鹼的觀點來看,以有機鹼的四甲基氫氧化銨(Tetra-methyl-ammonium-hydroxyde,簡稱為TMAH)為最佳。 Further, in the developing solution of the photolithography method, a chemical which can dissolve the composition of the decane resin is used, and when it is an organic solvent, there may be an organic base or an inorganic base. However, from the viewpoint of avoiding the incorporation of an inorganic base such as potassium hydroxide (KOH) in the subsequent step, an organic base of Tetra-methyl-ammonium-hydroxyde (TMAH) is preferred.
如上述,光蝕刻法、壓印法、噴墨法皆在電介質1e的圖案化形成後,更對電介質1e進行後烘。經由後烘,可將附著於基板1a及電介質1e的沖洗液因加熱而去除。接著在後烘後對電介質1e進行退火,期望的圖案的電介質1e形成於基板1a面上。 As described above, in the photolithography method, the imprint method, and the inkjet method, after the patterning of the dielectric 1e is formed, the dielectric 1e is further post-baked. After the post-baking, the rinse liquid adhering to the substrate 1a and the dielectric 1e can be removed by heating. Next, after the post-baking, the dielectric 1e is annealed, and a dielectric 1e of a desired pattern is formed on the surface of the substrate 1a.
經由在100℃以上400℃以下的溫度範圍進行後烘,可提高電介質1e的流動性,故電介質1e的圖案的全部、 或頂部/側部的一部份可成形為捲曲曲面狀,可提升發光元件8的光取出效率。再者,相較於剖面形狀為台形形狀或矩形形狀的凸部(例如凸部109),成形為曲面狀的凸部1b,在GaN層(2至5)等成膜時,GaN層的橫方向成長時間變短,故可縮短GaN層的成長時間。並且,未達100℃時,電介質1e的流動性變得不充分,電介質1e的圖案的全部、或頂部/側部的一部份無法成形為曲面狀。此外,超過400℃時,電介質1e的流動性變大,無法得到期望的解析度圖案。 By performing post-baking in a temperature range of 100 ° C or more and 400 ° C or less, the fluidity of the dielectric 1e can be improved, so that the pattern of the dielectric 1e is all Or a portion of the top/side portion may be formed into a curved curved shape to improve the light extraction efficiency of the light-emitting element 8. Further, compared with the convex portion (for example, the convex portion 109) having a trapezoidal shape or a rectangular cross-sectional shape, the convex portion 1b is formed into a curved shape, and when the GaN layer (2 to 5) or the like is formed, the transverse direction of the GaN layer is formed. Since the growth time in the direction is shortened, the growth time of the GaN layer can be shortened. Further, when the temperature is less than 100 ° C, the fluidity of the dielectric 1e is insufficient, and all of the pattern of the dielectric 1e or a part of the top portion or the side portion cannot be formed into a curved shape. Further, when it exceeds 400 ° C, the fluidity of the dielectric 1e becomes large, and a desired resolution pattern cannot be obtained.
對期望的圖案形成後的電介質1e施行退火,可在無光阻膜(凸部1b形成膜的蝕刻用光罩)成膜的基板1a面上成形任意側面形狀的期望的圖案。再者,感光劑的成分經由退火而去除,故可防止有機成分混入至GaN層(2至5)等發光元件8。且,去除感光劑成分係指經由退火使感光劑液化、蒸發而去除。 The dielectric 1e after the formation of the desired pattern is annealed, and a desired pattern of any side shape can be formed on the surface of the substrate 1a formed without the photoresist film (the etching mask for forming the film by the convex portion 1b). Further, since the components of the photosensitive agent are removed by annealing, it is possible to prevent the organic component from being mixed into the light-emitting elements 8 such as the GaN layers (2 to 5). Further, the removal of the sensitizer component means that the sensitizer is liquefied and evaporated by annealing.
再者,藉由在期望的圖案化形成時使用光蝕刻法,可在無光阻膜(亦即,凸部1b形成膜的蝕刻用光罩)成膜的基板1a面上形成圖案。因此,可實現製程數的減少及步驟的簡化、及隨著製程數減少的基板1的低成本化。再者,光蝕刻法步驟的時間短,故能夠以短時間製作在面上具有期望的圖案的基板1。 Further, by using a photolithography method at the time of formation of a desired pattern, a pattern can be formed on the surface of the substrate 1a on which the photoresist film (that is, the etching mask for forming the film of the convex portion 1b) is formed. Therefore, it is possible to reduce the number of processes, simplify the steps, and reduce the cost of the substrate 1 as the number of processes decreases. Further, since the time of the photolithography step is short, the substrate 1 having a desired pattern on the surface can be produced in a short time.
更詳細地說明壓印法。作為模型11材,例如以使用石英製等之類紫外線的穿透率佳的材料為佳。石英模型的作成方法,首先準備石英,接著在石英基板上塗佈光阻劑,藉由一般的光蝕刻法或電子束微影法將島狀的圖案曝光並顯影。接著,蒸鍍100nm左右的Al,然後剝離,接著以Al作為光罩,以使用三氟甲烷(CHF3)的RIE(Reactive Ion Etching:反應性離 子蝕刻)裝置對石英進行蝕刻加工至預定的深度為止。預定的深度為與凸部1b的高度相同。以磷酸去除蝕刻加工後剩餘的Al,最後以純水洗淨並使其乾燥,完成石英模型。 The imprint method will be described in more detail. As the material of the model 11, for example, a material having a good transmittance of ultraviolet rays such as quartz or the like is preferable. In the method of preparing the quartz model, quartz is first prepared, and then a photoresist is coated on the quartz substrate, and the island-shaped pattern is exposed and developed by a general photolithography method or electron beam lithography. Next, Al is deposited to a thickness of about 100 nm, and then peeled off. Then, using Al as a mask, the quartz is etched to a predetermined depth by a RIE (Reactive Ion Etching) apparatus using trifluoromethane (CHF 3 ). until. The predetermined depth is the same as the height of the convex portion 1b. The Al remaining after the etching process is removed with phosphoric acid, and finally washed with pure water and dried to complete the quartz model.
將此模型11壓附在電介質1e,通過模型11照射紫外線使電介質1e硬化。此時照射紫外線的方向可由模型11側,由於藍寶石基板1a本身為透明體,因此亦可從藍寶石基板1a側照射紫外線。並且,當從基板1a側照射紫外線時,模型11的材料不一定必須是透明體,故亦可使用石英以外的材質,例如亦可使用矽等不透明體。此外,作為透明的材料,可將藍寶石用於模型11。 This mold 11 is pressed against the dielectric 1e, and the dielectric 11e is cured by irradiating ultraviolet rays by the mold 11. At this time, the direction in which the ultraviolet rays are irradiated can be on the side of the mold 11, and since the sapphire substrate 1a itself is a transparent body, ultraviolet rays can be irradiated from the side of the sapphire substrate 1a. Further, when the ultraviolet ray is irradiated from the side of the substrate 1a, the material of the mold 11 does not necessarily have to be a transparent body. Therefore, a material other than quartz may be used. For example, an opaque body such as ruthenium may be used. Further, as a transparent material, sapphire can be used for the model 11.
並且,將模型11壓附於電介質1e時,為了使氣泡不會進入各個電介質1e內,亦可在真空環境中進行。並且,雖然在此以光奈米壓印法作為壓印法的一例舉例,亦可使用其他以熱方式使電介質1e硬化的熱奈米壓印法。 Further, when the mold 11 is pressed against the dielectric 1e, it may be carried out in a vacuum environment so that bubbles do not enter the respective dielectrics 1e. Further, although the photon imprint method is exemplified here as an example of the imprint method, other thermal imprint methods in which the dielectric 1e is hardened by heat may be used.
使島狀的電介質1e硬化後,從模型11分離,剩下相當於模型11的凸部的部分(島狀的電介質1e以外的部分),將多餘的電介質經由氧RIE裝置去除。 After the island-shaped dielectric 1e is cured, it is separated from the mold 11, and a portion corresponding to the convex portion of the mold 11 (portion other than the island-shaped dielectric 1e) is left, and the excess dielectric is removed by the oxygen RIE device.
如上,藉由在期望的圖案化形成時使用奈米壓印法,能夠以簡便的設備且低成本在基板1a面上形成期望的大小、間距、高度的凸部1b的圖案。此電介質圖案在之後的步驟中不會完全去除,保留由電介質所形成的突起並作成裝置,以此突起能永久保留至最終製品為佳。 As described above, by using the nanoimprint method at the time of formation of a desired pattern, it is possible to form a pattern of the convex portion 1b having a desired size, pitch, and height on the surface of the substrate 1a with a simple apparatus and at a low cost. This dielectric pattern is not completely removed in the subsequent steps, retaining the protrusions formed by the dielectric and forming the device, so that the protrusions can be permanently retained to the final article.
又,藉由在期望的圖案化形成時使用噴墨法,可直接圖案化形成,故提高凸部1b的圖案種類的自由度。此電 介質圖案在之後的步驟中不會完全去除,保留由電介質所形成的突起並作成裝置,以此突起能永久保留至最終製品為佳。 Further, since the ink jet method is used in the formation of a desired pattern, the pattern can be formed directly, so that the degree of freedom of the pattern type of the convex portion 1b is improved. This electric The dielectric pattern is not completely removed in the subsequent steps, the protrusions formed by the dielectric are retained and the device is formed, so that the protrusions can be permanently retained to the final article.
並且,上述光蝕刻法、壓印法、及噴墨法當中,從泛用性高的觀點,以光蝕刻法為佳。電介質圖案在之後的步驟中不會完全去除,保留由電介質所形成的突起並作成裝置,以此突起能永久保留至最終製品為佳。 Further, among the photoetching method, the imprint method, and the inkjet method, photolithography is preferred from the viewpoint of high generality. The dielectric pattern is not completely removed in the subsequent steps, the protrusions formed by the dielectric are retained and the device is formed, so that the protrusions can be permanently retained to the final article.
接著,藉由在700℃以上1700℃以下的溫度範圍進行退火,可去除凸部1b的感光劑成分,故可防止有機成分混入至GaN層(2至5)等的發光元件8。再者,可防止凸部1b上發生GaN層的成長,或是使成長難以發生。藉由抑制凸部1b上GaN層的成長,可實現FACELO的成長模式,故可形成錯位密度減少的GaN層。再者,退火後的凸部1b具有耐熱性,即使在n-GaN層成膜時的成膜溫度(約1000℃)中,亦可保持凸部1b的形狀及物性。並且,在未達700℃時,無法以SiO2、TiO2、ZrO2、Al2O3任一者作為主要成分。此外,超過1700℃時,由於超過作為凸部1b主要成分的SiO2、TiO2、ZrO2、Al2O3任一者的熔點,導致凸部1b的形狀歪曲等,因而不佳。 Then, by annealing at a temperature of 700 ° C or more and 1700 ° C or less, the photosensitive agent component of the convex portion 1b can be removed, so that the organic component can be prevented from being mixed into the light-emitting element 8 such as the GaN layer (2 to 5). Further, it is possible to prevent the growth of the GaN layer from occurring on the convex portion 1b or to make growth difficult. By suppressing the growth of the GaN layer on the convex portion 1b, the growth mode of FACELO can be realized, so that a GaN layer having a reduced dislocation density can be formed. Further, the convex portion 1b after annealing has heat resistance, and the shape and physical properties of the convex portion 1b can be maintained even in the film formation temperature (about 1000 ° C) at the time of film formation of the n-GaN layer. Further, when it is less than 700 ° C, either SiO 2 , TiO 2 , ZrO 2 or Al 2 O 3 cannot be used as a main component. In addition, when it exceeds the melting point of any of SiO 2 , TiO 2 , ZrO 2 , and Al 2 O 3 which are main components of the convex portion 1b, the shape of the convex portion 1b is distorted or the like, which is not preferable.
此外,藉由將退火的溫度範圍設訂在超過1000℃至1700℃以下的溫度範圍,降低圖案中所含的雜質,可降低對裝置特性的影響,因而較佳。再者,藉由將退火的溫度範圍設定在1100℃以上至1700℃以下的溫度範圍,可提升基板1a與圖案之間的密著性,因而較佳。藉由提升基板1a與圖案的密著性,可防止圖案脫落,可降低所製作的發光元件的波長不一致、亮度不一致等對收率的不良影響。 Further, by setting the annealing temperature range to a temperature range of more than 1000 ° C to 1700 ° C or less, it is preferable to reduce the impurities contained in the pattern to reduce the influence on the device characteristics. Further, by setting the annealing temperature range to a temperature range of 1100 ° C or more to 1700 ° C or less, the adhesion between the substrate 1a and the pattern can be improved, which is preferable. By improving the adhesion between the substrate 1a and the pattern, it is possible to prevent the pattern from falling off, and it is possible to reduce the adverse effect on the yield such as the wavelength difference of the produced light-emitting elements and the inconsistency in brightness.
接著,說明關於發光元件8的製造方法。首先,準備經由至目前為止說明的製造方法所製造的在面上具有期望的圖案的基板1,在凸部1b及基板1a上形成至少一層GaN層、AlN層、InN層,製造發光元件8。 Next, a method of manufacturing the light-emitting element 8 will be described. First, the substrate 1 having a desired pattern on the surface manufactured by the manufacturing method described so far is prepared, and at least one GaN layer, AlN layer, and InN layer are formed on the convex portion 1b and the substrate 1a to fabricate the light-emitting element 8.
如第1圖所示的GaN層2至5,例如磊晶成長法等習知的方法成長,或GaN層2至5各層採用不同的成膜方法及/或成膜條件進行成膜亦可。磊晶成長包含同質磊晶成長、異質磊晶成長。作為成膜法,亦可列舉其他鍍覆法等液相成膜法,然而,以使用濺鍍法或CVD法(Chemical Vapor Deposition)等氣相成膜法為佳。再者,以發光元件8的製造為目的,將3-5族氮化物化合物半導體層等半導體層成膜時,以利用MOCVD法(Metal Organic Chemical Vapor Deposition)、MOVPE法(Metal Organic Vapor Phase Epitaxy)、HVPE法(Hydride vapor phase epitaxy)、MBE法(Molecular Beam Epitaxy)等氣相成膜法為更佳。基板1b所使用的材料為藍寶石等無機材料時,構成各半導體層的材料也為金屬材料、金屬氧化物材料、無機半導體材料等無機材料為佳,希望全部的層為由此等無機材料所構成。但是,使用MOCVD法作為成膜法時,半導體層的無機材料中含有來自有機金屬的有機物亦可。 The GaN layers 2 to 5 shown in FIG. 1 may be grown by a conventional method such as an epitaxial growth method, or the GaN layers 2 to 5 may be formed by using different film formation methods and/or film formation conditions. Epitaxial growth includes homogenous epitaxial growth and heterogeneous epitaxial growth. As the film formation method, a liquid phase film formation method such as another plating method may be used. However, a vapor phase film formation method such as a sputtering method or a CVD method (Chemical Vapor Deposition) is preferably used. In the case of forming a semiconductor layer such as a Group 3-5 nitride compound semiconductor layer for the purpose of producing the light-emitting element 8, the MOCVD method (Metal Organic Chemical Vapor Deposition) and the MOVPE method (Metal Organic Vapor Phase Epitaxy) are used. A vapor phase film formation method such as HVPE method (Hydride vapor phase epitaxy) or MBE method (Molecular Beam Epitaxy) is more preferable. When the material used for the substrate 1b is an inorganic material such as sapphire, the material constituting each semiconductor layer is preferably an inorganic material such as a metal material, a metal oxide material or an inorganic semiconductor material, and it is desirable that all the layers be composed of such inorganic materials. . However, when the MOCVD method is used as the film formation method, the inorganic material of the semiconductor layer may contain an organic substance derived from an organic metal.
首先,在藍寶石製的基板1的凸部1b側的面上,成膜由GaN或AlN所構成的緩衝層,依n-GaN層2、InGaN發光層(活性層)3、p型AlGaN被覆層4、及p型GaN接觸層5的順序成膜形成。之後,進行預定的後加工,獲得發光元件8。 First, a buffer layer made of GaN or AlN is formed on the surface of the sapphire substrate 1 on the convex portion 1b side, and the n-GaN layer 2, the InGaN light-emitting layer (active layer) 3, and the p-type AlGaN coating layer are formed. 4. The p-type GaN contact layer 5 is formed in a film formation order. Thereafter, predetermined post-processing is performed to obtain the light-emitting element 8.
由於凸部1b為由電介質所構成,凸部1b表面並 未露出特定面方位的結晶面,不易生成作為n-GaN層2的成長的始點的核。亦即,在凸部1b的側部並未露出特定面方位的結晶面,故抑制從凸部1b側部開始的GaN層的結晶成長。此外,凸部1b至少一部份(例如,頂部)形成為曲面狀幾乎無平的部分由於非常窄,故GaN層無法成長。但是基板1的面上全面露出特定面方位的結晶面(例如,藍寶石的C面等),故容易生成GaN的核,n-GaN層2能夠成長。 Since the convex portion 1b is composed of a dielectric, the surface of the convex portion 1b is The crystal surface of the specific surface orientation is not exposed, and it is difficult to form a core which is the starting point of the growth of the n-GaN layer 2. In other words, since the crystal surface of the specific surface orientation is not exposed at the side portion of the convex portion 1b, the crystal growth of the GaN layer from the side portion of the convex portion 1b is suppressed. Further, at least a portion (for example, the top portion) of the convex portion 1b is formed into a curved surface, and the almost flat portion is extremely narrow, so that the GaN layer cannot grow. However, since the crystal surface of the specific surface orientation (for example, the C surface of sapphire or the like) is entirely exposed on the surface of the substrate 1, the nucleus of GaN is easily formed, and the n-GaN layer 2 can grow.
因此,如第11圖(a)所示,n-GaN層2的成長從凸部1b間的基板1a表面,亦即從非凸部1b的平坦部開始,隨著n-GaN層2的厚度變厚,n-GaN層2在橫方向(水平方向)成長,如第11圖(b)所示覆蓋凸部1b的側部及頂部。最終n-GaN層2的厚度至凸部1b的高度以上時,基板1a的表面與凸部1b的圖案如第11圖(c)所示被n-GaN層2所覆蓋,從平面方向觀察時,只看到平的n-GaN層2的表面。 Therefore, as shown in Fig. 11(a), the growth of the n-GaN layer 2 starts from the surface of the substrate 1a between the convex portions 1b, that is, from the flat portion of the non-convex portion 1b, with the thickness of the n-GaN layer 2 The n-GaN layer 2 is thickened in the lateral direction (horizontal direction), and covers the side and the top of the convex portion 1b as shown in Fig. 11(b). When the thickness of the n-GaN layer 2 is higher than the height of the convex portion 1b, the pattern of the surface of the substrate 1a and the convex portion 1b is covered by the n-GaN layer 2 as shown in FIG. 11(c), when viewed from the plane direction. Only the surface of the flat n-GaN layer 2 is seen.
因此,由於凸部1b的側部成為n-GaN層2的橫方向成長領域,故可防止從凸部1b的側部開始的錯位發生。再者,藉由凸部1b的至少一部份(例如頂部)形成為曲面狀,幾乎無平的部分可以非常窄。因此,由於抑制或防止從凸部1b開始的n-GaN層2的成長,故可防止凸部1b附件的n-GaN層2內的錯位發生。藉由以上方式,比起在平坦的基板上成長的GaN層,有較少的貫穿錯位數量。 Therefore, since the side portion of the convex portion 1b becomes the lateral growth region of the n-GaN layer 2, the occurrence of the displacement from the side portion of the convex portion 1b can be prevented. Further, at least a portion (for example, the top portion) of the convex portion 1b is formed into a curved shape, and the almost flat portion can be extremely narrow. Therefore, since the growth of the n-GaN layer 2 from the convex portion 1b is suppressed or prevented, occurrence of misalignment in the n-GaN layer 2 of the attachment of the convex portion 1b can be prevented. In the above manner, there is less penetration misalignment than the GaN layer grown on a flat substrate.
再者,藉由形成由GaN或AlN而成的緩衝層,可防止n-GaN層2的膜厚方向上膜質或膜厚的不平整等。 Further, by forming a buffer layer made of GaN or AlN, unevenness of the film quality or film thickness in the film thickness direction of the n-GaN layer 2 can be prevented.
再者,以習知方法成膜GaN層3至5後,藉由電 子束蒸鍍法形成p型電極6。接著,在n-GaN層2上未形成有InGaN發光層3處,使用ICP-RIE進行蝕刻加工使n-GaN層2露出。然後,在露出的n-GaN層2上藉由電子束蒸鍍法形成由Ti/Al積層構造而成的n型電極層7,在p型電極6上形成由Ti/Al而成的p型的金屬電極9,製作發光元件8。並且,p型電極6及n型電極層7可使用Ni、Au、Pt、Pd、Rh等金屬。 Furthermore, after the GaN layers 3 to 5 are formed by a conventional method, by electricity The p-type electrode 6 is formed by a beam evaporation method. Next, the InGaN light-emitting layer 3 is not formed on the n-GaN layer 2, and the n-GaN layer 2 is exposed by etching using ICP-RIE. Then, an n-type electrode layer 7 made of a Ti/Al laminated layer is formed on the exposed n-GaN layer 2 by electron beam evaporation, and a p-type formed of Ti/Al is formed on the p-type electrode 6. The metal electrode 9 is used to fabricate the light-emitting element 8. Further, as the p-type electrode 6 and the n-type electrode layer 7, a metal such as Ni, Au, Pt, Pd, or Rh can be used.
因凸部1b形成於基板1a的表面上,各凸部1b可獲得光散射效果。因此,被發光元件8內部所吸收的光的一部份,變得可取出至基板1a及InGaN發光層3的外部,可提升發光元件8的光取出效率。 Since the convex portion 1b is formed on the surface of the substrate 1a, each convex portion 1b can obtain a light scattering effect. Therefore, a part of the light absorbed by the inside of the light-emitting element 8 can be taken out to the outside of the substrate 1a and the InGaN light-emitting layer 3, and the light extraction efficiency of the light-emitting element 8 can be improved.
再者,由於將含有感光劑的電介質圖案化形成,由凸部1b構成的期望的圖案可形成於基板1a面上,故可在無光阻膜(凸部1b形成膜的蝕刻用光罩)成膜的基板1a面上形成圖案。因此,可實現製程數的減少與步驟的簡化、及隨著製程數減少發光元件8的低成本化,同時可製造上述光取出效率提升的發光元件8。 Further, since the dielectric material containing the photosensitive agent is patterned, the desired pattern composed of the convex portion 1b can be formed on the surface of the substrate 1a, so that the photoresist can be formed without the photoresist film (the mask for etching the convex portion 1b). A pattern is formed on the surface of the film-formed substrate 1a. Therefore, it is possible to reduce the number of processes, simplify the steps, and reduce the cost of the light-emitting elements 8 as the number of processes is reduced, and at the same time, the light-emitting elements 8 having improved light extraction efficiency can be manufactured.
又,接著將由電介質而成的凸部1b的圖案當作光罩,在基板1a表面進行乾式蝕刻或濕式蝕刻處理,在基板1a表面直接形成島狀圖案亦可。 Further, the pattern of the convex portion 1b made of a dielectric material is used as a photomask, and dry etching or wet etching treatment is performed on the surface of the substrate 1a, and an island-like pattern may be directly formed on the surface of the substrate 1a.
以下,舉例實施例1說明本發明,然而,本發明並不限定於以下的實施例1。 Hereinafter, the present invention will be described by way of Example 1, but the present invention is not limited to the following Example 1.
(實施例1) (Example 1)
[製造方法] [Production method]
首先,準備基板表面為C面且表面粗糙度Ra為1nm的鏡 面狀態的平坦的藍寶石基板。此藍寶石基板進行5分鐘的UV/O3洗淨,之後水洗,以熱板在130℃進行3分鐘的脫水烘乾。接著,在脫水烘乾後的藍寶石基板表面將HMDS(hexamethyldisilazane:六甲基二矽氮烷)藥劑,藉由旋轉器以300rpm10秒鐘接著以700rpm10秒鐘的2階段的步驟進行塗佈。之後,藍寶石基板以熱板在120℃進行50秒鐘烘乾。 First, a flat sapphire substrate having a mirror surface of a C surface and a surface roughness Ra of 1 nm was prepared. This sapphire substrate was subjected to UV/O 3 washing for 5 minutes, then washed with water, and dehydrated and dried at 130 ° C for 3 minutes with a hot plate. Next, HMDS (hexamethyldisilazane) was applied to the surface of the sapphire substrate after dehydration and drying, and the coating was applied by a rotator at 300 rpm for 10 seconds followed by a two-step procedure at 700 rpm for 10 seconds. Thereafter, the sapphire substrate was dried by a hot plate at 120 ° C for 50 seconds.
接著,將含有折射率小於GaN的折射率2.4,且作為感光劑的含有二叠氮化萘醌-5-磺酸酯的電介質,將由矽氧烷樹脂組成物而成的膜,藉由旋轉器以700rpm、10秒鐘接著以1500rpm、30秒鐘的2階段步驟,形成於藍寶石基板面上。結果,形成厚度1.55μm的矽氧烷樹脂組成物膜。並且,矽氧烷樹脂組成物採用Toray股份有限公司製正型感光性矽氧烷ER-S2000(預烘膜的折射率1.52(632.8nm)棱鏡耦合法)。 Next, a film containing a composition of a naphthylquinone-5-sulfonate having a refractive index lower than that of GaN and having a refractive index of 2.4 as a sensitizer is used as a sensitizer. The sapphire substrate surface was formed at 700 rpm for 10 seconds followed by a two-stage step of 1500 rpm for 30 seconds. As a result, a film of a rhodium oxide resin composition having a thickness of 1.55 μm was formed. Further, the rhodium oxide resin composition was a positive photosensitive decane ER-S2000 manufactured by Toray Co., Ltd. (refractive index 1.52 (632.8 nm) prism coupling method of prebaked film).
本實施例中,採用光蝕刻法作為將由上述矽氧烷樹脂組成物膜而成的期望的圖案形成於藍寶石基板面上的方法。將面上形成有矽氧烷樹脂組成物膜的藍寶石基板藉由熱板在110℃預烘3分鐘,接著使矽氧烷樹脂組成物膜圖案化曝光。本實施例中,以形成凸部的平面形狀為圓形,其圓形的直徑為4.9μm,且凸部間的間距為6.0μm的圖案的方式製作正型用光罩,將矽氧烷樹脂組成物膜曝光。曝光的光源為以光照射能量經由i-line換算為65mJ/cm2,使用由g、h、i線而成的寬光(g線=436nm、h線=405nm、i線=365nm)。此外,以正型作為矽氧烷樹脂組成物膜,曝光裝置使用接觸曝光裝置。 In the present embodiment, a photolithography method is employed as a method of forming a desired pattern of a film of the above-described naphthene resin film on a surface of a sapphire substrate. The sapphire substrate on which the film of the decane resin composition was formed was prebaked at 110 ° C for 3 minutes by a hot plate, and then the film of the siloxane oxide resin composition was patterned and exposed. In the present embodiment, a positive-type photomask is produced in such a manner that a planar shape in which the convex portion is formed is a circular shape, a circular diameter is 4.9 μm, and a pitch between the convex portions is 6.0 μm, and a siloxane resin is used. The composition film is exposed. The light source to be exposed was converted into light of 65 mJ/cm 2 by i-line, and wide light (g line = 436 nm, h line = 405 nm, i line = 365 nm) using g, h, and i lines was used. Further, a positive type is used as a film of a decane resin composition, and an exposure apparatus uses a contact exposure apparatus.
接著,將經曝光的矽氧烷樹脂組成物膜顯影。顯 影液使用2.38wt%-TMAH,將矽氧烷樹脂組成物膜浸泡於此顯影液中60秒鐘。之後,藍寶石基板及經顯影的矽氧烷樹脂組成物在230℃以熱板進行後烘3分鐘。 Next, the exposed siloxane oxide resin composition film was developed. Display The film solution was immersed in the developing solution for 60 seconds using 2.38 wt%-TMAH. Thereafter, the sapphire substrate and the developed decane resin composition were post-baked at 230 ° C for 3 minutes with a hot plate.
接著,在後烘後藍寶石基板上的經顯影的矽氧烷樹脂組成物在大氣環境中在1000℃進行退火1小時,在藍寶石基板的面上形成期望的圖案及側面形狀的凸部。 Next, the developed decane resin composition on the sapphire substrate after post-baking was annealed at 1000 ° C for 1 hour in an atmospheric environment to form a desired pattern and a side-shaped convex portion on the surface of the sapphire substrate.
[凸部] [protrusion]
確認由以上步驟所製造的凸部,確認有如下述的圖案及含有SiO2的凸部。 The convex portion produced by the above procedure was confirmed, and the following pattern and the convex portion containing SiO 2 were confirmed.
平面形狀:圓形 Plane shape: round
圓形的直徑:4.9μm Diameter of the circle: 4.9μm
高度:0.47μm Height: 0.47μm
間距:6.0μm Spacing: 6.0μm
側面形狀:全部為由曲面所形成的曲面形狀(參照第12圖及第13圖) Side shape: All are curved shapes formed by curved surfaces (refer to Figures 12 and 13)
凸部的圖案缺損的比例:10% Proportion of pattern defects in the convex part: 10%
(實施例2) (Example 2)
[製造方法] [Production method]
將矽氧烷樹脂組成物為Toray股份有限公司製正型感光性矽氧烷ER-S2000變更為Toray股份有限公司製正型感光性含有氧化鈦的矽氧烷ER-S3000,其餘與實施例1相同,在藍寶石基板的面上形成期望的圖案及側面形狀的凸部。預烘膜的折射率1.78(632.8nm)採用棱鏡耦合法。 The rhodium oxide resin composition was changed to a positive photosensitive methoxy olefin ER-S2000 manufactured by Toray Co., Ltd., and changed into a positive-type photosensitive oxytane ER-S3000 containing a titanium oxide manufactured by Toray Co., Ltd. Similarly, a convex portion having a desired pattern and a side surface shape is formed on the surface of the sapphire substrate. The pre-baked film has a refractive index of 1.78 (632.8 nm) using a prism coupling method.
[凸部] [protrusion]
確認由以上步驟所製造的凸部,確認有如下述的圖案及含有TiO2的凸部。 The convex portion produced by the above procedure was confirmed, and the following pattern and the convex portion containing TiO 2 were confirmed.
平面形狀:圓形 Plane shape: round
圓形的直徑:4.9μm Diameter of the circle: 4.9μm
高度:1.00μm Height: 1.00μm
間距:6.0μm Spacing: 6.0μm
側面形狀:全部為由曲面所形成的曲面形狀(參照第12圖及第13圖) Side shape: All are curved shapes formed by curved surfaces (refer to Figures 12 and 13)
凸部的圖案缺損的比例:12% Proportion of pattern defects in the convex part: 12%
(實施例3) (Example 3)
[製造方法] [Production method]
將矽氧烷樹脂組成物為Toray股份有限公司製正型感光性矽氧烷ER-S2000變更為Toray股份有限公司製正型感光性含有氧化鋯的矽氧烷ER-S3100,其餘與實施例1相同,在藍寶石基板的面上形成期望的圖案及側面形狀的凸部。預烘膜的折射率1.64(632.8nm)採用棱鏡耦合法。 The oxime resin composition was changed to a positive photosensitive methoxy olefin ER-S2000 manufactured by Toray Co., Ltd., and changed into a positive photosensitive zirconia-containing oxirane ER-S3100 manufactured by Toray Co., Ltd., and the remaining Example 1 Similarly, a convex portion having a desired pattern and a side surface shape is formed on the surface of the sapphire substrate. The refractive index of the prebaked film of 1.64 (632.8 nm) was measured by a prism coupling method.
[凸部] [protrusion]
確認由以上步驟所製造的凸部,確認有如下述的圖案及含有ZrO2的凸部。 The convex portion produced by the above procedure was confirmed, and the following pattern and the convex portion containing ZrO 2 were confirmed.
平面形狀:圓形 Plane shape: round
圓形的直徑:4.9μm Diameter of the circle: 4.9μm
高度:1.50μm Height: 1.50μm
間距:6.0μm Spacing: 6.0μm
側面形狀:全部為由曲面所形成之曲面形狀(參照第12圖 及第13圖) Side shape: all are curved shapes formed by curved surfaces (refer to Figure 12) And Figure 13)
凸部的圖案缺損的比例:14% Proportion of pattern defects in the convex part: 14%
(比較例) (Comparative example)
以下說明比較例。比較例將SiO2膜以電漿CVD法成膜,之後SiO2膜上形成光阻膜,與實施例1相同將上述光阻膜曝光、顯影,與實施例1記載的圖案的方式圖案化形成上述光阻膜。圖案化形成的光阻膜當作光罩,進行SiO2膜的乾式蝕刻。 The comparative example will be described below. In the comparative example, a SiO 2 film was formed by a plasma CVD method, and then a photoresist film was formed on the SiO 2 film. The photoresist film was exposed and developed in the same manner as in Example 1, and patterned in the same manner as in the pattern described in Example 1. The above photoresist film. The patterned photoresist film is used as a photomask to perform dry etching of the SiO 2 film.
確認所得凸部的圖案及SiO2含有量,獲得與實施例1的凸部相同的結果。 The pattern of the obtained convex portion and the content of SiO 2 were confirmed, and the same results as those of the convex portion of Example 1 were obtained.
<評估> <evaluation>
關於實施例1及比較例,評估至凸部形成為止所需製程數及交貨時間。其結果為實施例1獲得所需製程數為8,交貨時間為70分的評估結果。另一方面,比較例所需製程數為9,交貨時間為110分。由以上的評估結果,確認本實施例可實現減少製程數及縮短交貨時間。大量生產的情況或基板為大口徑時,比較例依SiO2膜的成膜步驟或SiO2膜的乾式蝕刻步驟的設備大小晶圓處理個數受到限制,再者交貨時間的差異更顯著。 With respect to Example 1 and Comparative Example, the number of processes required for forming the convex portion and the delivery time were evaluated. As a result, the evaluation results of the required number of processes of 8 and the delivery time of 70 minutes were obtained in Example 1. On the other hand, the number of processes required for the comparative example was 9, and the delivery time was 110 points. From the above evaluation results, it was confirmed that the present embodiment can achieve a reduction in the number of processes and a shortened delivery time. Or the case where mass production of large-diameter substrate, the number of Comparative Example limited by the size of the wafer processing step of forming a SiO 2 film or the step of dry etching of SiO 2 film, addition of more significant difference in delivery time.
上述基板及發光元件可適用於以下的裝置或機器等。舉例而言,包括該發光元件,如第14圖所示,適用於照明100的光源101或機器等作為組合光源。此等光源,當該發光元件為V族元素內的氮(N)所構成時,特別是從藍色的可視光至紫外光,可利用於必須發出藍色的可視光或紫外光的機器等。舉例而言,發出藍色光(短波長)的照明、信號機、投光器、 內視鏡等的光源、相機顯示器200的三原色的1個光源201(參照第15圖)、用於光檢選的光源,及可作為用來發出紫外光的殺菌庫、冷藏庫等的光源利用。此外,與螢光塗料的塗佈面組合生成白色或電燈色,作為螢光燈等的照明機器(例如,植物育成用照明)、顯示器的背光、車輛用的燈光、投影機、相機用閃光燈等的光源利用。當然,本申請案的發光元件並不限定於氮化物系的化合物半導體,其適用範圍亦不限定於上述。 The substrate and the light-emitting element can be applied to the following devices, apparatuses, and the like. For example, the light-emitting element is included as a combined light source suitable for the light source 101 or the machine of the illumination 100 as shown in FIG. When the light-emitting element is composed of nitrogen (N) in the group V element, particularly from blue visible light to ultraviolet light, it can be used in a device that must emit blue visible light or ultraviolet light. . For example, blue light (short wavelength) illumination, signal, light projector, A light source such as an endoscope, a light source 201 of three primary colors of the camera display 200 (see FIG. 15), a light source for light detection, and a light source that can be used as a sterilization library or a refrigerator for emitting ultraviolet light. . In addition, it is combined with a coated surface of a fluorescent paint to produce white or electric light, as an illumination device such as a fluorescent lamp (for example, illumination for plant growth), a backlight for a display, a light for a vehicle, a projector, a flash for a camera, etc. The use of light sources. Needless to say, the light-emitting element of the present application is not limited to the nitride-based compound semiconductor, and the scope of application is not limited to the above.
此外,如第16圖所示,本申請案的基板不僅作為發光元件,作為接收來自各方向的光的受光元件,可作為光二極體的基板、太陽電池或太陽光發電面板300的基板301利用。 Further, as shown in Fig. 16, the substrate of the present application can be used not only as a light-emitting element but also as a light-receiving element that receives light from each direction, and can be used as a substrate of a photodiode or a substrate 301 of a solar cell or solar photovoltaic panel 300. .
並且,本發明不限於舉例用的實施例或適用例,可依不脫離申請專利範圍的各項所述的內容的範圍的構成實施。亦即,本發明以關於主要特定的實施形態,特別以圖示加以說明,然而,只要不脫離本發明的技術的思想及目的的範圍,對於上述的實施形態,數量、其他的詳細構成,所屬技術領域具有通常知識者可加以各種變化。 Further, the present invention is not limited to the embodiments or the applicable examples, and can be implemented in accordance with the scope of the content described in the claims. In other words, the present invention has been described with reference to the specific embodiments, and the present invention is described in detail with reference to the embodiments of the present invention. Those skilled in the art can make various changes.
1‧‧‧在面上具有預定圖案的基板 1‧‧‧Substrate with a predetermined pattern on the surface
1a‧‧‧基板 1a‧‧‧Substrate
2b‧‧‧凸部 2b‧‧‧ convex
Claims (23)
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US11211527B2 (en) * | 2019-12-19 | 2021-12-28 | Lumileds Llc | Light emitting diode (LED) devices with high density textures |
RU2747132C1 (en) * | 2020-08-21 | 2021-04-28 | Федеральное государственное бюджетное учреждение науки Физико-технический институт им. А.Ф. Иоффе Российской академии наук | Method for producing nitride light-emitting diode |
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US5260163A (en) * | 1992-05-07 | 1993-11-09 | E. I. Du Pont De Nemours And Company | Photoenhanced diffusion patterning for organic polymer films |
JP4106972B2 (en) * | 2002-06-06 | 2008-06-25 | Jsr株式会社 | Composition for forming photosensitive dielectric, dielectric and electronic component |
JP4218339B2 (en) * | 2002-12-24 | 2009-02-04 | パナソニック株式会社 | Method for manufacturing plasma display panel |
JP2004273671A (en) * | 2003-03-07 | 2004-09-30 | Kyocera Chemical Corp | Internal electrode material for stacked ceramic capacitor |
JP3804016B2 (en) * | 2003-05-23 | 2006-08-02 | 富士フイルムエレクトロニクスマテリアルズ株式会社 | Inorganic material film, inorganic material film structure, method for producing the same, and transfer film |
KR100610639B1 (en) * | 2005-07-22 | 2006-08-09 | 삼성전기주식회사 | Vertically structured gan type led device and method of manufacturing the same |
JP4462249B2 (en) * | 2005-09-22 | 2010-05-12 | ソニー株式会社 | Light emitting diode manufacturing method, integrated light emitting diode manufacturing method, and nitride III-V compound semiconductor growth method |
JP4925651B2 (en) * | 2005-11-29 | 2012-05-09 | 京セラ株式会社 | Optical imprint stamper and light emitting device manufacturing method using the same |
WO2008081717A1 (en) * | 2006-12-22 | 2008-07-10 | Showa Denko K.K. | Method for producing group iii nitride semiconductor layer, group iii nitride semiconductor light-emitting device, and lamp |
JP5592479B2 (en) * | 2009-04-29 | 2014-09-17 | エスエヌユー アールアンドディービー ファウンデーション | Method for manufacturing a substrate on which a pattern is formed |
JP2011091374A (en) * | 2009-09-11 | 2011-05-06 | Samco Inc | Method of etching sapphire substrate |
KR101726897B1 (en) * | 2009-09-29 | 2017-04-13 | 도레이 카부시키가이샤 | Positive photosensitive resin composition, cured film obtained using same, and optical device |
JP4718652B2 (en) * | 2009-10-21 | 2011-07-06 | パナソニック株式会社 | Solar cell and method for manufacturing the same |
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