200832740 九、發明說明： 【發明所屬之技術領域】 一種ί = 一種發光二極體_)’特別是有關於 製之高發光效率發光二極體結構及其 【先前技術】 近來世界能源的短缺導致油價不斷的㈣，全球 國家莫不積極地投入節能產$的 / 又八即此產0口的開發，例如省電燈泡便是 此一趨勢下的產物。隨著發光二極體（led)技術的進步， 白光或其它顏色（例如：藍光）發光二極體的應用也逐漸開 展，其應用包括：液晶顯示器（LCD)背光板、印表 於電腦之光學連接構件（opticalinterc〇nnectsin __)、指示燈、地面燈、逃生燈、醫療設備光源、 π車儀錶及内裝燈、輔助照明、主照明…等等。簡而言之， 發光二極體係以背光源與照明功能為當前的主要應用。。在 下-世代的照明市場中，將是發光二極體的天下。由於發 光二極體具有輕巧、省電及壽命長等優點，因此，符合； 世界的趨勢潮流。歐、美、曰等國皆以舉國之力投入開發 的行列，而我國的發光二極體產業，在全球市場上，無論 研發以及製造均佔有舉足輕重的角色與地位。所以^ 光二極體領域的下-世代發展巾，台灣勢料會缺席。 目前，發光二極體在白光市場的應用，已將小型照明 市場，帶入另外一個境界。其中，手機的背光源已經被發 光二極體所取代。從早期的黃、綠光發光：極體到現在的 5 200832740 白光或藍光發光二極體，已經將手機點綴的五彩繽紛。至 於個人數位助理（personal digital assistant : PDA)乃至液晶 顯示面板（TFT-LCD)的背光源，也都將成為發光二極體的 天下。其具有輕薄省電的優點將使其具有不可取代的地位。 就現階段而言，距離實際進入白光發光二極體照明時 代，尚有一段距離。若白光發光二極體要取代現階段照明 市場’發光效率至少要達到80 lm/W以上，這個目標也將 成為各國努力的目標之一。 在發光二極體的發光機制中，其發光效率取決於内部 的里子效率以及外部的取光效率，其中内部的量子發光效 率主要係由發光二極體的組成材料及其結晶性來控制。換 二之，發光二極體的發光效率主要係由磊晶的結構以及品 質來決^ ’當蟲晶層中有缺陷存在時，由於結構中的缺陷 係造成光子被吸收的主要因素，因此，發光二極體的發光 效率將會大幅度地降低。 傳統之發光二極體之發光層所形成之光，在經由？型 半導料與透料㈣之界㈣會產生反射，使得該發光 -極體之光取出效率（light extraetiGn力受到影 二，外在發光_極體之發光表面增加粗糙化表面的圖 樣或疋形成光子晶體結構，均是於半導體層上直接加工， ㈣寻發光層被破壞或是造成元件損傷。此 於監實石基板硬度高、耐腐純強，因 一定的困難度，一船的如丁士』 工另 程、兩子μ千/ 式主要係利用微影钱刻製 或讀加工等方式於藍寳石基板製作特定的圖 6 200832740 案又限於上述製程之限制，較難得到奈米級的圖樣及進 行大面積元件的製作，並且上述技術之製造過程較繁複且 設備及製作成本相對的較昂貴。 再者’由於某些發光二極體之半導體層(例如： 射率n>2.4)與空氣（折射率n約略=1〇)之間的折射係數差 異很大，其全反射臨界m 2G〜3G度，造成大部分發 光層所產生的光只能在元件内部全反射，無法有效地出只200832740 IX. Description of the invention: [Technical field to which the invention pertains] A ί = a light-emitting diode _)', in particular, a high luminous efficiency light-emitting diode structure and its [prior art] The oil price is constantly (4), the global countries are not actively investing in energy-saving production / / eight is the development of this product, such as energy-saving bulbs is the product of this trend. With the advancement of LED technology, the application of white light or other color (for example, blue light) LEDs has gradually developed. Applications include: liquid crystal display (LCD) backlights, and opticals for printing on computers. Connecting components (opticalinterc〇nnectsin __), indicator lights, ground lights, escape lights, medical equipment light sources, π car meters and interior lights, auxiliary lighting, main lighting, etc. In short, the light-emitting diode system is currently the main application with backlight and lighting functions. . In the next-generation lighting market, it will be the world of light-emitting diodes. Because the light-emitting diode has the advantages of light weight, power saving and long life, it is in line with the trend of the world. Countries such as Europe, the United States, and China have all invested in the development of the country, and China's LED industry has played a pivotal role and position in both the R&D and manufacturing industries in the global market. Therefore, the next-generation development towel in the field of light diodes will be absent from Taiwan. At present, the application of light-emitting diodes in the white light market has brought the small lighting market to another level. Among them, the backlight of the mobile phone has been replaced by the light-emitting diode. From the early yellow and green light: the polar body to the present 5 200832740 white or blue light emitting diode, has been embellished with colorful colors. As for the personal digital assistant (PDA) and even the backlight of the liquid crystal display panel (TFT-LCD), it will also become the world of light-emitting diodes. Its advantages of light and power saving will make it irreplaceable. At this stage, there is still a distance from the actual lighting age of white light emitting diodes. If the white light emitting diode is to replace the current lighting market, the luminous efficiency should be at least 80 lm/W or more, and this goal will become one of the goals of the countries. In the illuminating mechanism of the light-emitting diode, the luminous efficiency depends on the internal neutron efficiency and the external light-receiving efficiency, and the internal quantum luminescence efficiency is mainly controlled by the constituent materials of the light-emitting diode and its crystallinity. In other words, the luminous efficiency of the light-emitting diode is mainly determined by the structure and quality of the epitaxial crystal. When the defect in the crystal layer exists, the photon is absorbed due to defects in the structure. The luminous efficiency of the light-emitting diode will be greatly reduced. The light formed by the luminescent layer of the traditional light-emitting diode is passed through? The boundary between the type of semi-conductive material and the transparent material (4) will produce reflection, so that the light extraction efficiency of the light-emitting body (light extraetiGn force is affected by the shadow, the external light-emitting surface of the polar body increases the pattern of the roughened surface or The photonic crystal structure is formed directly on the semiconductor layer, (4) the luminescent layer is destroyed or the component is damaged. This is a high hardness and corrosion resistance of the superficial stone substrate, due to a certain degree of difficulty, such as a ship Ding Shi's work, two sub-micro-types, mainly use lithography money engraving or reading processing to make a specific sapphire substrate. Figure 6 200832740 is limited to the above process limits, it is difficult to get nano-scale The pattern and the fabrication of large-area components, and the manufacturing process of the above technology is complicated and the equipment and manufacturing cost are relatively expensive. Furthermore, 'because of the semiconductor layer of some light-emitting diodes (for example: incidence rate n > 2.4) The difference in refractive index between air and air (refractive index n is approximately 1 〇) is very large, and its total reflection criticality is m 2G to 3G degrees, causing most of the light generated by the luminescent layer to be totally reflected inside the component. Effectively the only
光’所以即使内部的發光效率提高，外部的取光 法改善也是枉然。 …、 因此’基於上述之問題，以及因應趨勢之需求之 程技術來改善發光二極體之取光效率已成為重要的發展^ 向。疋故，本發明將提出一種具有高發光效率之發光二 體結構與其製造方法，其可以提高發光二極體的光取出效 率（light extraction efficiency) ’並可降低發光二極體磊晶 層之晶體缺陷，提高發光效率。 【發明内容】 本發明之目的在於提供一種新穎的具有多孔性光子晶 體結構之發光二極體結構與其製造方法。 曰曰 本發明之再-目的在於提供—種具有（週期性）微米級 孔洞的光子晶體結構之發光二極體。 本發明之目的在於提供一種具有（週期性）奈米級孔洞 的光子晶體結構之發光二極體。Light's, so even if the internal luminous efficiency is improved, the external light extraction method is improved. ..., therefore, it has become an important development to improve the light extraction efficiency of light-emitting diodes based on the above-mentioned problems and the process technology in response to the trend. Therefore, the present invention proposes a light-emitting two-body structure having high luminous efficiency and a manufacturing method thereof, which can improve the light extraction efficiency of the light-emitting diode and can reduce the crystal of the epitaxial layer of the light-emitting diode. Defects improve luminous efficiency. SUMMARY OF THE INVENTION An object of the present invention is to provide a novel light-emitting diode structure having a porous photonic crystal structure and a method of fabricating the same. Further, another object of the present invention is to provide a light-emitting diode of a photonic crystal structure having (periodic) micron-sized pores. SUMMARY OF THE INVENTION An object of the present invention is to provide a light-emitting diode having a photonic crystal structure of (periodic) nano-scale pores.
本發明之另一目的在於將微米級週期性孔洞的光子晶 構建構於基板本身，使呈現規靠週期性排列，此= 7 200832740 以有效地提 方式可以改善磊晶品質以及增加外部取光效率 高發光二極體的發光效率。 本發明之另一目的在於將奈米級週期性孔洞的光子曰 體結構建構於微米級光子晶體結構之上，使呈現規則且= 期性排列’此種方式可以改善蟲日日日品質並降低^時所產 生之缺陷，使發光二極體之電性較佳。 本發明之又-目的在於提供一種可以簡化製程以適用 於大面積元件製造之發光二極體。Another object of the present invention is to construct photonic crystals of micron-order periodic pores on the substrate itself, so that the orientation is periodically arranged, and this = 7 200832740 can effectively improve the epitaxial quality and increase the external light extraction efficiency. Luminous efficiency of high light-emitting diodes. Another object of the present invention is to construct a photonic corpus callosum structure of a nano-scale periodic pore on a micron-scale photonic crystal structure, so as to present a regular and chronological arrangement, which can improve the daily quality of the insect day and reduce it. The defects generated by ^ make the electrical properties of the light-emitting diodes better. Still another object of the present invention is to provide a light-emitting diode that can simplify the process for large-area component fabrication.
一種發光二極體，包括：基板，具有第一孔洞於其中； 光子晶體結構（作為緩衝層）’形成^基板之上光、曰 體結構具有第二孔洞位於至少基板之上與第-孔洞之曰 第-型：晶層，形成於光子晶體結構之上；發光層，形成 :上述第一型磊晶層之上；第二型磊晶層’形成於上述發 、層之上，第一接觸電極，形成於上述該第一型磊晶層之 上；=及，第二接觸電極，形成於上述第二型磊晶層之上。 .一，發光二極體之製造方法，包括：首先，提供一基 ，，接著，移除部份基板以形成第一孔洞於基板之中；接 著’形成-多孔性光子晶體結構於基板之上，其中光子晶 構具有第二孔洞位於至少基板之上與第—孔洞之中； 隨後，形成一第一型磊晶層於上述多孔性光子晶體結構之 ^’、之後，形成一發光層於上述第一型磊晶層之上；然後， 形成一第二型磊晶層於上述發光層之上；接著，形成一第 接觸電極於上述第一型磊晶層之上；之後，形成一第二 接觸電極於上述第二型磊晶層上。 8 200832740 上述基板係藉由微影與㈣製程，以形成第—孔洞於 ^板之中。上述第二孔洞多孔性光子晶體結構係利用純铭 缚膜進行陽極處理餘所形成之纽性氧減薄膜。 【實施方式】 本發明的一些實施例會詳細描述如下。然而，除了詳 」田述的Λ知例外’本發明可以廣泛地在其它的實施例中 施行’並且本發明之保護範圍並不受限於下述之實施例， 其係以後述的申請專利範圍為準。 > 料’為提供更清楚的描述及更易理解本發明，圖示 分並沒有依照其相對尺寸㈣，不相關之細節部分 也未7L全繪出，以求圖示的簡潔。 請參考圖示，其中所顯示僅僅是為了說明本發明之較 佳實施例，並非用以限制本發明。一般降低蟲.晶層之晶格 缺陷的方式係對（藍寶石）基板直接作表面的加工處理，以 形成微米級或奈米級的凹凸結構。 _ 本么月先利用濕蝕刻處理技術（或乾蝕刻、拋光、電子 ^離子-束等技術）在基板之中形成具有週期性晶格係數之 2級—維光子晶體結構’此光子晶體結構可以便利於後 Ά之進行。此種結構不僅可以有效改善蠢晶品質，更 I 乂 θ加内部篁子發光效率，並解決基板與蠢晶層之間的 社全反射之問題以及減少沿著界面產生的側向漏光情形， 結果有效地提昇了發光二極體的外部取光效率。 本發明另外利用陽極處理技術（或電子束轟擊）在第一 層結構（例如A1N、Si〇2、Al2〇3)表面製造一層具有（週期性） 9 200832740 奈米級晶格係數之二維光子晶體結構，此光子晶體結構可 以有效的改善遙晶品質，增加内部量子發光效率。再者， 奈米級晶格係數可以大幅降低i晶生長_產生之缺陷， 亚控制與降低基板與蠢晶層之間所產生之漏電流，使發光 一極體之電性大幅提昇。 务f一實施例中，藉由調整發光層材料，使其發光介於 k光fell ’利用本發明之多孔性氧化銘光子晶體結構所產 生光激發現象，以增加發光二極體之發光強度。 明參閱第，、圖，其係根據本發明之發光二極體結構之 截面圖。上述發光二極體結構，包括：一基板1〇具有微米 級多孔性_光子晶體結構於其中、奈米級多孔性光子晶體結 構14第型磊晶層15、發光層17、第二型磊晶層18、 第一接觸電極19以及第二接觸電極16。舉一實施例而言， 上述基板10之材質可以為藍寶石（sapphire)、氮化鎵 (GaN)、氮化鋁（A1N)、碳化矽（Sic)或氮化鎵鋁_ΑιΝ)。 上述基板10經過一粗糙化的製程而將基板1〇之表面粗糙 化而形成粗糙表面。舉一實施例而言，上述表面粗糙化製 程係在基板1〇之中形成一具有週期性晶格係數之微米級 一維光子晶體結構。 第一圖為本發明之發光二極體基板結構之截面圖。上 述基板1〇之表面形成一正光阻層11，如第一圖所示。光 阻層11經過一曝光（微影製程）之後，形成一具有曝光區與 非曝光區之光阻層12,其中曝光區之光阻層為光阻層 12a，請參考第二圖。之後，再透過一顯影製程，將曝光區 10 200832740 ^光阻層12a移除，結果形成光阻圖案i3，請參考第三圖。 於後續製程。 Π 2 T ^以光阻圖案13作為#刻罩幕’利用濕式姓刻 刻、抛光、、電子束、離子束等技術）將基板ι〇表面 1元成一具有週期性孔洞10a間距之基S 10,如第四圖 i週』!·生孔洞1 〇a之結構大小係透過{阻圖帛13來定A light emitting diode comprising: a substrate having a first hole therein; a photonic crystal structure (as a buffer layer) forming a light on the substrate, the body structure having a second hole on at least the substrate and the first hole曰Type-type: a crystal layer formed on the photonic crystal structure; a light-emitting layer formed on the first type of epitaxial layer; a second-type epitaxial layer formed on the above-mentioned layer, the first contact An electrode is formed on the first type epitaxial layer; and a second contact electrode is formed on the second type epitaxial layer. A method of fabricating a light emitting diode, comprising: first, providing a substrate, and then removing a portion of the substrate to form a first hole in the substrate; then forming a porous photonic crystal structure on the substrate Wherein the photonic crystal structure has a second hole located in at least the substrate and the first hole; subsequently, forming a first type of epitaxial layer on the porous photonic crystal structure, and then forming a light emitting layer on the above a first type epitaxial layer is formed thereon; then, a second epitaxial layer is formed on the light emitting layer; then, a first contact electrode is formed on the first type epitaxial layer; and then a second is formed The contact electrode is on the second type epitaxial layer. 8 200832740 The above substrate is formed by a lithography and (4) process to form a first hole in the plate. The second porous porous photonic crystal structure is a neon oxygen-reduced film formed by performing anodization using a pure ingot film. [Embodiment] Some embodiments of the present invention will be described in detail below. However, the present invention may be widely practiced in other embodiments, and the scope of protection of the present invention is not limited to the following embodiments, which are described below. Prevail. <Material' To provide a clearer description and to more easily understand the present invention, the illustrations are not in accordance with their relative dimensions (4), and the irrelevant details are not fully drawn to illustrate the simplicity of the illustration. The drawings are only for the purpose of illustrating the preferred embodiments of the invention and are not intended to limit the invention. Generally, the lattice defects of the crystal layer are reduced by directly processing the surface of the (sapphire) substrate to form a micron- or nano-scale uneven structure. _ This month first uses wet etching treatment technology (or dry etching, polishing, electron ion-beam technology) to form a second-order photonic crystal structure with periodic lattice coefficients in the substrate. Convenient for the future. Such a structure can not only effectively improve the quality of the stupid crystal, but also improve the efficiency of the internal dice, and solve the problem of total reflection between the substrate and the stray layer and reduce the lateral light leakage along the interface. The external light extraction efficiency of the light emitting diode is effectively improved. The invention additionally utilizes anodization techniques (or electron beam bombardment) to fabricate a two-dimensional photon having a (periodic) 9 200832740 nanometer lattice coefficient on the surface of the first layer structure (eg, A1N, Si〇2, Al2〇3). Crystal structure, this photonic crystal structure can effectively improve the quality of the telecrystal and increase the internal quantum luminescence efficiency. Furthermore, the nano-scale lattice factor can greatly reduce the defects of the i-crystal growth, sub-control and reduce the leakage current generated between the substrate and the stray layer, so that the electrical properties of the light-emitting body are greatly improved. In an embodiment, by adjusting the material of the light-emitting layer, the light-emitting phenomenon is generated by the porous oxidized crystal structure of the present invention by the light-emitting element of the present invention to increase the light-emitting intensity of the light-emitting diode. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing a structure of a light-emitting diode according to the present invention. The light emitting diode structure comprises: a substrate 1 〇 having a micron-order porosity _ photonic crystal structure therein, a nano-scale porous photonic crystal structure 14 a first type epitaxial layer 15, a light-emitting layer 17, and a second-type epitaxial layer Layer 18, first contact electrode 19, and second contact electrode 16. In one embodiment, the material of the substrate 10 may be sapphire, gallium nitride (GaN), aluminum nitride (A1N), tantalum carbide (Sic) or gallium aluminum nitride (ΑιΝ). The substrate 10 is subjected to a roughening process to roughen the surface of the substrate 1 to form a rough surface. In one embodiment, the surface roughening process forms a micron-scale one-dimensional photonic crystal structure having a periodic lattice coefficient in the substrate 1?. The first figure is a cross-sectional view of the structure of the light-emitting diode substrate of the present invention. A positive photoresist layer 11 is formed on the surface of the substrate 1A as shown in the first figure. After the photoresist layer 11 is subjected to an exposure (lithography process), a photoresist layer 12 having exposed regions and non-exposed regions is formed. The photoresist layer of the exposed regions is the photoresist layer 12a. Please refer to the second figure. Then, through the development process, the exposed region 10 200832740 ^ photoresist layer 12a is removed, and the photoresist pattern i3 is formed. Please refer to the third figure. In the follow-up process. Π 2 T ^ using the photoresist pattern 13 as a #刻幕幕' using wet-type engraving, polishing, electron beam, ion beam, etc.) to make the surface of the substrate ι 1 into a base having a periodic hole 10a spacing S 10, as shown in the fourth figure i week! · The size of the hole 1 〇a is determined by the block diagram
、牛例而5 ’上述孔洞1〇a直徑約〇 5_5微米，孔洞與 間的距離(排列週期）約為1〜10微米，孔洞密度約為 母平方公分具有1〇8〜1012個孔洞。 ，式㈣之_溶液例如為草酸（C2h2〇4)溶液、石舞酸 ^田。舉例而言’酸㈣刻溶液對於氧化銘基板有餘刻 的作用，其可產生下列化學反應： A1203 + 3H2S〇4->2Al(S04)3 + 3H2〇 AI2O3 + 2H3P04^2A1P04 + 3H20 h在Λ施例之中，上述基板蝕刻製程可以在80%的磷 酉夂溶液、5%的石肖酸、5%的醋酸以及2()%的純水中，加敎 ^攝氏35〜45度的溫度環境之下來進行。隨著加熱處理之 又包守間的改變，氧化鋁基板孔洞週期性苴 率約為每分鐘觸〜3_埃（埃纷）。而在另—實施^速 中，上述基版蝕刻製程可以在3:1的酸性溶液中，其溶液 組成包括硫酸（HJO4)溶液（其比例為3)與磷酸（H3p〇4)溶 =(其比例為1)，加熱至攝氏2〇〇〜4〇〇度的溫度環境之下 來進行。隨著加熱處理之浸泡時卩杨改變，氧化基板孔 11 200832740 洞週期性擴大，直到一定的大小為止。 接著，於蝕刻基板10之後，沉積一薄層二氧化矽（si〇2) 蟲晶晶體，其沉積例如係透過蒸鍍（e_gun)、濺鍍 (Sputter)、電漿式化學氣相沉積（pECVD)、化學氣相沉積 (CVD)、物理氣相沉積（pvD)、熱浸鍍所形成。沉積二氧化 夕（Si〇2)蟲晶生長完成之後，於基板上便生長一薄層二氧 化矽晶體，其可作為後續製成週期性孔洞所必要之緩衝層。 ，奴後，利用鏡膜沉積技術（例如蒸鑛、濺鍍、電漿式化 _學氣相^積、化學氣相沉積、物理氣相沉積、熱浸鐘）形成 金屬薄膜於基板10之上，並填滿孔洞1〇a。舉一實施例 而言，金屬薄膜為紹金屬薄膜，其薄膜厚度A 05〜2 米。 · 然後，再利用陽極處理（anodization)技術在基板⑺與 同10a表面形成週期性奈米級多孔性氧化金屬薄膜圖案 14,請參考第五圖。舉例而言，上述多孔性氧化金屬薄膜 馨圖案14包括複數個孔洞形成於基板1〇之上。舉例而言， 形成於孔洞10a區之上的孔洞14b的深度比形成於非孔洞 區之上的14a孔洞的深度還大。 ★舉例而言，對於上述純紹薄膜之陽極處理係在0.2〜0.5 莫耳/辰度（M)的草酸（C2H2〇4)溶液，外加2〇〜5〇伏特之直流 ，£之％ i兄下進行。隨著陽極處理之時間的改變，多孔性 7氧化鋁薄膜厚度逐漸增加，舉例而言，氧化鋁薄膜孔洞直 裣约為5〜400奈米（較佳為3〇〜8〇奈米），孔洞與孔洞之間 的距離（排列週期）約為δ〇〜12〇奈米，孔洞密度約為每平方. 12 200832740 公分具有108〜l〇12個孔洞。 瓶向言 %極處理金屬薄膜後呈現細胞管狀 ㈣War tube)結構。形成此種結構型態的過 開始通電時’㈣極表面的某些部位開始溶解，^:: 增長，銘溶解量增加，㈣極表㈣始呈現凹凸 链度’時間續增，由於凹凸不平造成溶解速率不—千= ===’：溶_離子逐漸形成氫氧二The above-mentioned hole 1〇a has a diameter of about 5_5 μm, the distance between the holes (arrangement period) is about 1 to 10 μm, and the hole density is about 1 to 8 to 1012 holes. The solution of the formula (IV) is, for example, a solution of oxalic acid (C2h2〇4) or a solution of Shisha. For example, an acid (four) engraving solution has a residual effect on the oxidized substrate, which produces the following chemical reactions: A1203 + 3H2S〇4->2Al(S04)3 + 3H2〇AI2O3 + 2H3P04^2A1P04 + 3H20 h In the embodiment, the substrate etching process can be performed in an 80% phosphorous solution, 5% of stearic acid, 5% of acetic acid, and 2% of pure water, and a temperature of 35 to 45 degrees Celsius is added. Under the environment. With the change of the heat treatment, the periodic porosity of the alumina substrate is about ~3 Å per minute. In another implementation, the above-mentioned radical etching process can be carried out in an acidic solution of 3:1, and the solution composition thereof includes a solution of sulfuric acid (HJO4) (in a ratio of 3) and a solution of phosphoric acid (H3p〇4). The ratio is 1) and is heated to a temperature of 2 to 4 degrees Celsius. As the sputum is changed during the immersion in the heat treatment, the hole of the oxidized substrate hole 11 200832740 is periodically expanded until a certain size. Next, after etching the substrate 10, a thin layer of cerium oxide (si〇2) crystals are deposited, which are deposited, for example, by evaporation (e_gun), sputtering, and plasma chemical vapor deposition (pECVD). ), chemical vapor deposition (CVD), physical vapor deposition (pvD), hot dip plating. After the deposition of the cerium (Si〇2) crystallites is completed, a thin layer of cerium oxide crystal is grown on the substrate, which serves as a buffer layer necessary for subsequent periodic holes. After the slave, a metal film is formed on the substrate 10 by a mirror deposition technique (such as steaming, sputtering, plasma chemistry, chemical vapor deposition, physical vapor deposition, hot dip clock). And fill the hole 1〇a. In one embodiment, the metal film is a thin metal film having a film thickness of A 05 to 2 meters. Then, an anodization technique is used to form a periodic nano-scale porous oxidized metal film pattern on the surface of the substrate (7) and the same 10a. Please refer to the fifth figure. For example, the porous oxidized metal thin film pattern 14 includes a plurality of holes formed on the substrate 1A. For example, the depth of the hole 14b formed over the area of the hole 10a is greater than the depth of the hole 14a formed above the non-hole area. ★ For example, for the above-mentioned pure film, the anode treatment is in the solution of 0.2~0.5 mol/min (M) of oxalic acid (C2H2〇4), plus 2〇~5〇V of DC, £% i brother Go on. As the time of the anode treatment changes, the thickness of the porous 7-alumina film gradually increases. For example, the pores of the alumina film are about 5 to 400 nm (preferably 3 to 8 nm), and the pores are holes. The distance from the hole (arrangement period) is about δ〇~12〇N, and the hole density is about every square. 12 200832740 cm has 108~l〇12 holes. After the bottle is treated with the metal film, it exhibits a tubular (War tube) structure. When the formation of this type of structure is started, some parts of the surface of the (four) pole begin to dissolve, ^:: growth, the amount of dissolved is increased, and (4) the surface of the pole (four) begins to show the degree of concave and convex chain 'time continues to increase, due to unevenness The dissolution rate is not - thousand = ===': the dissolved ion gradually forms hydrogen and oxygen
進行，m 是仍留有孔隙以供溶解反應繼續 又打間之後，堆積的沉澱即形成管壁，管 =土含水氧化鋁或膠狀氫氧化鋁，其中愈接近管壁 央含水量愈少’愈接近純氧化ls，而接 銘溶解沉積的區域’沉積愈久則愈緻密。成即為 叙入H H讀進行陽極處理時，酸性電解質會分解純 至屬表面’並且開始成長氧化層。純I呂金屬表面分解造 2 j孔/同的產生’同時孔洞底部會形成阻障層使得氧化 層與金屬！㈣離，當孔洞形成趨於穩定時，則將以一定速 率開”成長’形成類似蜂巢結構的氧化鋁層。 =極處理時操作電壓會影響孔洞、孔距與細胞的大 】匕們之間的關係是成正比的。換言之，施加的電壓越 大，其孔洞、孔距與細胞也相對的較大。 g理娜上，陽極氧化鋁膜的孔洞可以規則性的排列，但 疋通吊其fe圍不會超過幾微米。在孔洞形成之初，無次序 的孔洞生成將造成陽極氧化膜正面孔洞不規則，而孔洞 生成4«定柑’杈板背面才可以看到規則的孔洞排列。為了 13 200832740 得到大範圍的規則孔洞，可以利用二次陽極處理（tw〇_Mep an〇dlZati〇n)或在鋁金屬層表面預置圖案（pre-pattern)等兩 種方法。After the m is still left with pores for the dissolution reaction to continue, the deposited precipitate forms the tube wall, and the tube = soil aqueous alumina or colloidal aluminum hydroxide, wherein the closer to the tube wall, the less water there is. The closer to the pure oxidation of ls, and the area where the deposit is dissolved, the longer the deposition, the denser it is. When the anodic treatment is carried out for the H H reading, the acidic electrolyte decomposes to the surface of the genus and begins to grow the oxide layer. The surface of pure I-Lu metal is decomposed to create 2 j holes/same generation. At the same time, a barrier layer is formed at the bottom of the hole to make the oxide layer and the metal! (4) When the pore formation tends to be stable, it will “grow” at a certain rate to form an alumina layer similar to the honeycomb structure. The operating voltage will affect the pores, the pore spacing and the cell size when the pole is processed. The relationship is proportional. In other words, the larger the applied voltage, the larger the hole, the hole distance and the cell. On the Li Na, the pores of the anodized aluminum film can be regularly arranged, but The fe circumference will not exceed a few microns. At the beginning of the hole formation, the unordered hole formation will cause the front hole of the anodized film to be irregular, and the hole will form the regular hole arrangement on the back of the 4«Dangan's slab. 13 200832740 A wide range of regular holes can be obtained, either by secondary anodization (tw〇_Mep an〇dlZati〇n) or by pre-patterning on the surface of the aluminum metal layer.
鋁金屬陽極處理所使用的電解液可以包括报多種，其 中母種電解液的主要化學成份不同，經其處理後的薄膜 組織不同，孔洞性質也因之有所差異。舉例而言，上述電 解液包括：（1)硫酸液，例如15〜20%硫酸，操作電壓為 14 22伏特、電流密度為、環境溫度18〜25它、 處理時間1G〜6G分鐘’其可以形成薄膜厚度為3〜35微米。 硫酸溶液製程所得到的薄膜抗録良好，而且抗磨耗性 佳’此製程若將操作溫度降至5。〇以下，硫酸濃度降至7 %左右’處理電壓提高i 23〜12〇伏特，可以長時間處理 以獲得厚度200微米以上的相對硬質陽極薄臈；⑺鉻酸 液，例如包括5〜10%鉻酸，操作電壓為4〇伏特、電流宓 ^為〇.15〜Ο.30·2、環境溫度饥、處理時間3〇分鐘山， 2以形成薄膜厚度約為2〜3微米，鉻酸溶液製程所得到 的_亦具有良好抗錄；（3)草酸液，例如包含仏 或3〜5wt%草酸（C2H2〇4)，電屢為4〇〜6〇伏特、電流穷、 為1〜2A/dm2、環境溫产】只忐 山又 / 一衣兄，皿度18〜2〇C、處理時間4〇〜6〇分鐘， ，、可以形成薄膜厚度約為1 〇〜65 降至3〜5。。，經長時門,：：卡此外，當環境溫度 牛王、、工長日守間處理可以獲得厚度6 (4)磷酸液，例如含10%磷酸， 的溥膜， 千口夂私座為10〜12伏特、環 溫度23〜25〇C、處理時間2〇〜3〇 衧衣扰 产約為丨2忾半蛛撕 其可以形成薄膜厚 又力為1〜2彳政未，秘酸液處理之薄膜孔隙較大。 200832740 明舉出解液之成分組成以及其操作條件僅係本發 形成薄膜時，發明。這四種電解液中 以形成薄膜，同；其薄臈:有一：的二:;金屬持續溶出 以持續成長至其溶解速度與成長:度:等:止因膜： 種電解液如韻液、酒石酸液等，其生成的薄膜較敏/ 許紹金屬經由電解溶出，因此適合使用於形⑽ 长舉—實施例而言，多孔性氧化金屬薄膜例如為多孔性 氧化銘，膜。然'後，再透過—熱處理製程，其可以利用氧 化石夕爐管執行，爐管内抽真空使其真空度達卜的⑽，處 理溫度於攝氏500〜1100度底下進行，時間為4小時。經 由熱處理製程完成後’二氧化鋁(AW。晶體生長完成之 後’其於氧化銘薄膜圖案14之上形成二氧化铭多晶狀態蠢 晶體，可以作為週期性孔洞之緩衝層。 此外，本發明之發光二極體包括一 N型半導體層15， 形成於基板10與多孔性氧化金屬薄膜14之上。N型半導 體磊晶層15可以透過化學氣相沉積（CVD)、有機金屬化學 氣相沉積（MOCVD)方式形成。另外，一發光層17，形成於 上述N型半導體層15之上。上述發光層17為一主動層 (active layer) ’其可以由複數個井層（weu iayer)與複數個阻 障層（barrier layer)交互堆疊而形成。一 p型半導體磊晶層 18，形成於上述發光層17之上，同樣地，p型半導體層 18可以透過化學氣相沉積、有機金屬化學氣相沉積 15 200832740 (MOCVD)方式形成。上述p型半導體層18或n型半導體 層15之材質可以選自氮化鎵（GaN)、氮化銦鎵（InGaN)、氮 化鎵系或氮基（nitride-based)半導體蠢晶之一。 弟一接觸電極19，形成於上述p型半導體層18之表 面，其係用以作為P型接點或N型接點。另外，一第二接 觸電極16，形成於上述N型半導體層15之上，其係用以 作為N型接點或P型接點。上述二接觸電極，其材質可以 遥自鈦/紹（TiAl)、鈦/紹/鈦/金（Ti/Al/Ti/Au)及鈦/紹/鎳/金 • (Ti/Al/Ni/Au)合金之一。 此外，本發明亦提供發光二極體之製造方法，其主要 步驟包括·首先，k供一基板10。接著，形成一光阻層P 於基板10之上，藉由微影與蝕刻製程以圖案化基板〗〇以 得到孔洞圖案10a。隨後，形成金屬薄膜於基板1〇之上並 填入孔洞10a。接著，針對金屬薄膜進行陽極處理製程而 形成奈米級多孔性氧化金屬薄膜孔洞結構14，此即為本發 ❿明之多孔性光子晶體結構。舉一實施例而言，上述基板工〇 之材質包括藍寶石（sapphire)、氮化鎵（GaN)、氮化鋁 (A1N)、碳化石夕（SiC)或氮化鎵紹（GaAiN)。 然後，形成一 N型半導體層15於多孔性光子晶體結 構14之上。之後，形成發光層u於上述n型半導體層μ 之上上述务光層17為一主動層（acuve iayer)，其可以由 複數個井層（well layer)與複數個阻障層（barder layer)交互 堆豐而形成。接著，形成一 P型半導體層18於發光層17 之上。 16 200832740 然後’形成一第一電極丨6於N型半導體層15之表面， 其係用來作為N型接觸電極。之後，形成一第二電極 於P型半導體層18上，其係用來作為p型接觸電極。上 述二電極，其材質可以選自氮化鈦、鈦/鋁（TiAl)、鈦/鋁/ 鈦 /金（Ti/Al/Ti/Au)及鈦 /銘 /鎳 / 金（Ti/A1/Ni/Au)合金之一。 利用上述多孔性氧化銘薄膜之特性，使得上述發光層 Π所形成之發光路徑在N型半導體層15與基板1()之界^ 之間降低反射率，使得大部分激發之光可以轄射至元件之 外部。結果使得本發明之發光二極體之取光效率⑴咖 >·的文D磊aa品質，增加内部量子發光效率。 本發明的主要優點如下： 性規式敍刻製程於（藍寳石）基板上達到形成週期 以提n w的效果’能大幅提昇外部取光效率，更可 以挺幵發光二極體内部發光 m ^ 擗备151制j 九文羊，同日寸亦可以簡化製程， 避免口製程加工所造成的損害。 2·利用陽極處理製程於（誌索 ΛΑ ^ ^ ^ 貝石）基板上達到表面粗化 磊晶生县眛新# 4H 1炙先放率之外，也可以降低 乂、斤產生的缺陷，避免因^ ^ ^ ^ ^ ^ ^ ^ 屬電，爪對發光二極體所造成的損害。 3 ·利用光子晶體效麻，γ ,. W 可以有效的改善遙晶口皙以及 側向漏光問題，而紝槿太红、 人〇猫日日口口貝以及 m 形，增加光的取出效率。 4·利用光子晶體本身且右h , w 、有先激叙特性，可以增加發光 200832740 二極體之發光強度。 本毛月之製私簡易且適合用於大面積元件的製造。 本發明以較佳實施例說明如上，然其並非用以限定本 主張之專利權利範圍。其專利保護範圍當視後附之 專利範圍及其等同領域而定。凡熟悉此領域之技藝 於屬在不脫離本專利精神或範圍内，所作之更動或潤飾， =於本發明所揭示精神下所完成之等效改變或設計，且 應包含在下述之申請專利範圍内。 _ 【圖式簡單說明】 彳：以下詳細之描述結合所附圖示，將可輕易的了解 上述内容及此項發明之諸多優點，其中： 圖 第-圖為根據本發明之形成光阻層於基板上之截面 $二圖為根據本發明之曝光於光阻上之截面圖。 圖。 第四圖為根據本發明之形成圖案化基板之截面圖。 槿根據本發明之形成奈米級多孔性光子晶體結 構於圖案化基板上之截面圖。 第六圖為根據本發明之具有奈米級多孔性光子晶體結 構之發光二極體之截面圖。 口 【主要元件符號說明】 基板1 〇 孔洞10a 第三圖為根據本發明之形成光阻圖案於基板上之截面 18 200832740 光阻層π 曝光後之光阻層12 曝光區之光阻層12a 光阻圖案13 多孔性氧化金屬薄膜14 孔洞 14a、14b N型半導體層15 第一電極16 發光層17 P型半導體層18 第二電極19The electrolyte used for the anodizing of the aluminum metal may include a plurality of types, in which the main chemical components of the mother electrolyte are different, and the structure of the film after the treatment is different, and the pore properties are also different. For example, the above electrolyte solution comprises: (1) a sulfuric acid liquid, for example, 15 to 20% sulfuric acid, an operating voltage of 14 22 volts, a current density of, an ambient temperature of 18 to 25, and a treatment time of 1 G to 6 G minutes, which can be formed. The film thickness is 3 to 35 microns. The film obtained by the sulfuric acid solution process has good recording resistance and good abrasion resistance. If the process is reduced to 5, the operating temperature is lowered. 〇The following, the sulfuric acid concentration is reduced to about 7%. The treatment voltage is increased by 23 to 12 volts, which can be treated for a long time to obtain a relatively hard anode thin layer having a thickness of 200 μm or more; (7) a chromic acid solution, for example, including 5 to 10% chromium. Acid, operating voltage is 4 volts, current 宓^ is 15.15~Ο.30·2, ambient temperature hunger, treatment time 3 〇 minute mountain, 2 to form a film thickness of about 2~3 microns, chromic acid solution process The obtained _ also has good anti-recording; (3) oxalic acid liquid, for example, containing strontium or 3~5wt% oxalic acid (C2H2〇4), electric repeatedly 4〇~6〇V, current poor, 1~2A/dm2 , environmental temperature and production] only the mountain and / brother, the degree of 18 ~ 2 〇 C, processing time 4 〇 ~ 6 〇 minutes, , can form a film thickness of about 1 〇 ~ 65 to 3 ~ 5. . After the long time door, :: card In addition, when the ambient temperature Niu Wang, the foreman, the day-to-day treatment can obtain a thickness of 6 (4) phosphoric acid solution, such as 10% phosphoric acid, the sputum film, 10~12 volts, ring temperature 23~25〇C, treatment time 2〇~3〇衧 扰 扰 丨 忾 忾 忾 忾 忾 忾 忾 忾 忾 忾 忾 忾 忾 其 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以 可以The treated film has a large pore. 200832740 The invention discloses that the composition of the solution and the operating conditions thereof are only the film formed by the present invention. The four electrolytes form a thin film, the same; the thin enthalpy: one: two:; the metal continues to dissolve to continue to grow to its dissolution rate and growth: degree: et al: stop film: an electrolyte such as rhyme, The tartaric acid or the like, which is formed by a relatively sensitive film, is eluted by electrolysis, and is therefore suitable for use in the form (10). For example, the porous oxidized metal film is, for example, a porous oxide film. Then, after the heat treatment process, it can be carried out by using a oxidized stone furnace tube, vacuuming the inside of the furnace tube to make the vacuum degree (10), and the treatment temperature is performed at 500 to 1100 degrees Celsius for 4 hours. After the completion of the heat treatment process, 'dia-alumina (AW. After crystal growth is completed), it forms a oxidized polycrystalline state stupid crystal on the oxidized film pattern 14, which can serve as a buffer layer for periodic pores. Further, the present invention The light emitting diode includes an N-type semiconductor layer 15 formed on the substrate 10 and the porous metal oxide film 14. The N-type semiconductor epitaxial layer 15 can be subjected to chemical vapor deposition (CVD) or organometallic chemical vapor deposition ( In addition, a light-emitting layer 17 is formed on the N-type semiconductor layer 15. The light-emitting layer 17 is an active layer 'which can be composed of a plurality of well layers and a plurality of layers A barrier layer is formed by alternately stacking a p-type semiconductor epitaxial layer 18 formed on the light-emitting layer 17. Similarly, the p-type semiconductor layer 18 can be permeable to chemical vapor deposition or organometallic chemical vapor phase. The material of the p-type semiconductor layer 18 or the n-type semiconductor layer 15 may be selected from gallium nitride (GaN), indium gallium nitride (InGaN), gallium nitride or nitrogen. One of the nitride-based semiconductor electrodes. A contact electrode 19 is formed on the surface of the p-type semiconductor layer 18, and is used as a P-type contact or an N-type contact. In addition, a second contact electrode 16 Formed on the N-type semiconductor layer 15, which is used as an N-type contact or a P-type contact. The above two contact electrodes can be made of TiAl, Ti/Ti/Ti/ One of gold (Ti/Al/Ti/Au) and titanium/sand/nickel/gold• (Ti/Al/Ni/Au) alloys. In addition, the present invention also provides a method for manufacturing a light-emitting diode, the main steps of which include First, k is supplied to a substrate 10. Then, a photoresist layer P is formed on the substrate 10, and the substrate pattern is patterned by a lithography and etching process to obtain a hole pattern 10a. Subsequently, a metal film is formed on the substrate 1. The hole 10a is filled in the crucible. Then, the nano-porous oxidized metal film hole structure 14 is formed by performing an anodizing process on the metal thin film, which is the porous photonic crystal structure of the present invention. The material of the above substrate process includes sapphire, gallium nitride (GaN), Aluminum nitride (A1N), carbon carbide (SiC) or gallium nitride (GaAiN). Then, an N-type semiconductor layer 15 is formed on the porous photonic crystal structure 14. Thereafter, a light-emitting layer u is formed on the above n The above-mentioned optical layer 17 on the semiconductor layer μ is an active layer, which may be formed by a plurality of well layers and a plurality of barrier layers interposed. Then, a layer is formed. A P-type semiconductor layer 18 is over the luminescent layer 17. 16 200832740 Then a first electrode 丨 6 is formed on the surface of the N-type semiconductor layer 15, which is used as an N-type contact electrode. Thereafter, a second electrode is formed on the P-type semiconductor layer 18, which serves as a p-type contact electrode. The above two electrodes may be made of titanium nitride, titanium/aluminum (TiAl), titanium/aluminum/titanium/gold (Ti/Al/Ti/Au), and titanium/ing/nickel/gold (Ti/A1/Ni). /Au) One of the alloys. By utilizing the characteristics of the porous oxidized film, the light-emitting path formed by the light-emitting layer 降低 reduces the reflectance between the N-type semiconductor layer 15 and the substrate 1 (), so that most of the excited light can be conditioned to The outside of the component. As a result, the light-receiving efficiency of the light-emitting diode of the present invention (1) is improved, and the internal quantum light-emitting efficiency is increased. The main advantages of the present invention are as follows: The performance of the characterization process on the (sapphire) substrate to achieve a cycle of formation to improve the effect of nw can greatly enhance the external light extraction efficiency, and can also be quite radiant LED internal light m ^ 擗Prepare 151 system j ninth sheep, the same day can also simplify the process, to avoid damage caused by the mouth process. 2. Using the anodizing process to achieve surface roughening on the substrate of (Zhisuo ^ ^ ^ Beishi). In addition to the pre-release rate of 4H 1炙, it can also reduce defects caused by sputum and jin, and avoid Because ^ ^ ^ ^ ^ ^ ^ ^ is the electric power, the damage caused by the claw to the light-emitting diode. 3 ·Using photonic crystals to effect γ, γ, W can effectively improve the problem of remote crystal 皙 and lateral light leakage, while 纴槿 too red, human 〇 cat daily mouth and mouth and m shape, increase the efficiency of light extraction. 4. Using the photonic crystal itself and the right h, w, with the first characterization, can increase the luminous intensity of the illuminating 200832740 diode. The manufacturing of this month is simple and suitable for the manufacture of large-area components. The present invention has been described above in terms of preferred embodiments, and is not intended to limit the scope of the claims. The scope of patent protection is subject to the scope of the patents attached and their equivalent fields. Any changes or designs made in the spirit of the present invention, which are included in the spirit of the present invention, are included in the following claims. Inside. _ [Simple Description of the Drawings] 彳: The following detailed description, together with the accompanying drawings, will readily explain the above and many advantages of the invention, wherein: Figure 1 is a diagram of forming a photoresist layer according to the present invention. A cross-sectional view of the substrate on the substrate is shown in cross section in accordance with the present invention. Figure. The fourth figure is a cross-sectional view of a patterned substrate in accordance with the present invention. A cross-sectional view of a nano-scale porous photonic crystal structure formed on a patterned substrate in accordance with the present invention. Fig. 6 is a cross-sectional view showing a light-emitting diode having a nano-scale porous photonic crystal structure according to the present invention. Port [Major component symbol description] Substrate 1 pupil hole 10a The third diagram shows the cross section of the photoresist pattern formed on the substrate according to the present invention. 1832732740 Photoresist layer π exposed photoresist layer 12 exposed region photoresist layer 12a light Resistive pattern 13 Porous oxidized metal film 14 Holes 14a, 14b N-type semiconductor layer 15 First electrode 16 Light-emitting layer 17 P-type semiconductor layer 18 Second electrode 19
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