1229945 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種紅外光發光元件及其製備方法，特別 係關於一具有含矽發光薄膜之紅外光發光元件及其製備方 法。 【先前技術】 紅外光發光二極體主要係應用於光通訊產業上。惟，隨 著半導體雷射二極體技術漸趨成熟，玻璃光纖使用之發光 二極體光源（波長介於1310奈米及1550奈米間之紅外光） 已逐漸改用雷射二極體以增加傳輸距離。家庭網路及數位 影音等多媒體之連結主要是使用塑膠光纖及波長為650至 670奈米的紅光發光二極體。因此，目前紅外光發光二極體 的應用範圍係鎖定在波長介於850至950奈米之間，例如 感測器及遙控器等市場。現階段，光電元件（特別是發光元 件）之製作主要是採用磊晶技術，並使用具有直接能隙（Direct band-gap)之III-V族或II-VI族等元素作為原料。 1 947年發明電晶體之後，矽材料在積體電路產業就一直 扮演著十分重要的角色。依據摩爾定律（Moore’s Law)之預 測，約每隔1 8個月左右的時間，積體電路之元件尺寸將縮 減為其原來的一半。摩爾定律主要的依據是新技術的不斷 創新以及潛在應用的開發等條件下所導致的結果，而矽材 料就是這個快速進展的一重要基石。經過多年的發展，石夕 材料應用在積體電路之製程技術可說是最完整也是成本最 低廉的，因此若能將矽材料進一步開發成發光元件，便可1229945 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to an infrared light emitting element and a method for preparing the same, and particularly to an infrared light emitting element having a silicon-containing light emitting film and a method for preparing the same. [Previous technology] Infrared light emitting diodes are mainly used in the optical communication industry. However, as semiconductor laser diode technology matures, the light emitting diode light source (infrared light with a wavelength between 1310 nm and 1550 nm) used in glass fiber has gradually switched to laser diodes. Increase transmission distance. The home network, digital video and other multimedia connections are mainly using plastic optical fibers and red light emitting diodes with a wavelength of 650 to 670 nanometers. Therefore, the current application range of infrared light-emitting diodes is locked in the wavelength between 850 and 950 nanometers, such as sensors and remote control markets. At this stage, the production of optoelectronic components (especially light-emitting components) is mainly based on epitaxial technology, and uses elements such as III-V or II-VI with direct band-gap as raw materials. Since the invention of the transistor in 1947, silicon has always played a very important role in the integrated circuit industry. According to the prediction of Moore's Law, the component size of the integrated circuit will be reduced to half its original size every about 18 months. Moore's Law is mainly based on the results of continuous innovation of new technologies and the development of potential applications, and silicon materials are an important cornerstone of this rapid progress. After years of development, the process technology of Shi Xi materials used in integrated circuits can be said to be the most complete and the lowest cost, so if silicon materials can be further developed into light-emitting components, then
H:\HU\HYGV|g 能所 \92834\92834.DOC 1229945 具體地整合發光元件與大型積體電路（VLSI)。 矽材料（IV族元素）在室溫下為一個無效率的發光源，主 要的原因在於它是屬於間接能隙（Indirect band-gap)材料，其光 輻射重合率（Radiative recombination rate)甚低，且内部量子發光 效率（Internal quantum efficiency)僅約為 1 (Γ6 至 10·7，以致於一直 都被排除在作為發光源之角色外。因此，矽材料在光電產 業之應用目前則僅侷限於在偵檢器、電荷藕合元件（Charge Coupled Device，CCD)陣列式影像感測器與太陽電池等光接收 元件上。 1990年英國人L.T.Canham發現在氫氟酸溶液中，利用 陽極電解矽材料所形成的多孔性矽材料（Porous Si，PSi)可產 生高效率的可見光源（參考：CanhamL.T·，Appl· Phys· Lett·，57, 1046 (1990))。此一重要發明啟動了全球各國研究團隊紛紛投入矽 光源之開發。在2000至2003年之間，世界上許多學術研 究機構與研究人員皆紛紛投入矽基材發光二極體之開發， 而且產生許多進展（參考·· Mykola Sopinskyy and Viktoriya Khomchenko, Current Opinion in Solid State and Material Science 7(2003) 97-109.)。惟，目前在矽基材發光二極體之研究開發工作雖 然有不錯的進展，但是迄今仍未有任何商業化的發光二極 體等光電產品。 由於多孔性矽材料具有類似海棉狀之組織結構，因此在 發光元件之應用上具有一些重大的缺點。就機械特性而 言，多孔性矽材料因易碎而不適合整合於標準的半導體製 程之中。另，多孔性矽材料在化學特性上呈現高度的活性，H: \ HU \ HYGV | g Energy Center \ 92834 \ 92834.DOC 1229945 Specifically integrates light-emitting elements and large-scale integrated circuits (VLSI). Silicon material (Group IV element) is an inefficient light source at room temperature. The main reason is that it is an indirect band-gap material. Its radiation recombination rate is very low. And the internal quantum efficiency (Internal quantum efficiency) is only about 1 (Γ6 to 10 · 7, so that it has been excluded from the role as a light source. Therefore, the application of silicon materials in the optoelectronic industry is currently limited to Detectors, Charge Coupled Device (CCD) array image sensors and solar cells and other light-receiving elements. In 1990, the British LT Canham discovered that in a hydrofluoric acid solution, an anode electrolytic silicon material was used. The formed porous silicon material (Porous Si, PSi) can generate a high-efficiency visible light source (Reference: Canham L.T., Appl. Phys. Lett., 57, 1046 (1990)). This important invention has been launched in countries around the world Research teams have invested in the development of silicon light sources. Between 2000 and 2003, many academic research institutions and researchers in the world have invested in the development of silicon-based light-emitting diodes. Many advances have been made (see Mykola Sopinskyy and Viktoriya Khomchenko, Current Opinion in Solid State and Material Science 7 (2003) 97-109.). However, the current research and development work on silicon substrate light-emitting diodes has been good. Progress, but so far there have not been any commercial light-emitting diodes and other optoelectronic products. Because porous silicon materials have a sponge-like structure, they have some major shortcomings in the application of light-emitting elements. In terms of mechanical properties In other words, porous silicon materials are not suitable for integration into standard semiconductor processes because they are fragile. In addition, porous silicon materials are highly reactive in chemical properties.
H:\HU、HYG\核能所W2834\92834 D0C 1229945 易於與空氣中氧原子產生化學作用而呈現光電性能退化， 因而難以控制其光電性能隨時間之變化情形。 【發明内容】 本發明之主要目的係提供一種具有含矽發光薄膜之紅外 光發光元件及其製備方法。 為達成上述目的，本發明揭示一種紅外光發光元件及其 製備方法。該紅外光發光元件包含一具有一上表面及一下 表面之基板、一設置於該上表面之二氧化矽薄膜、複數個 分佈於該二氧化矽薄膜中之矽奈米晶體、一設置於該二氧 化矽薄膜上之第一歐姆接觸電極以及一設置於該下表面之 第二歐姆接觸電極。該基板可為一 p_型矽基板或一 n•型矽 基板，該第一歐姆接觸電極可由氧化銦锡構成。該二氧化 矽薄膜之厚度係介於1至1⑻00奈米之間，而該矽奈米晶 體之尺寸係介於5至10奈米之間。 該紅外光發光元件之另一實施例係包含一基板、—設置 於該基板上之合金薄膜、一設置於該合金薄膜之局部表面 之二氧切薄膜、複數個分佈於該二氧切薄膜中之石夕夺 米晶體、-設置於該二氧切薄膜上之第一歐姆接觸電： 、及a置於4合金薄膜之局部表面之第二歐姆接觸電 極。該合金薄膜係由⑪、錄及鎵構成，該第—歐姆接觸電 極係由氧化銦錫構成，而該基板係—石英基板或— 二鋁基板。 —虱化 旦該紅外光發光元件之製備方法首先在—基板形成—次當 1比氣化矽薄膜，*中該次當量比氧化矽薄膜之氧原子： H:\HU\HYG\核能所\92834\92834 Dc>(： -9- 1229945 與石夕原子數之比例小》2。之後，進行至少一熱處理製程以 驅使該次當量比氧切薄财之部㈣料結晶形成複數 個矽奈米晶體。該次當量比氧化矽薄膜係以常壓化學氣相 沈積製程形成於該基板上，其中該常壓化學氣相沈積製程 之溫度係介於700至ll〇〇°C之間且沈積時間係介於1至3〇〇 分鐘。該常壓化學氣相沈積製程係使用流量比介於ι〇:ι至 1:10間之二氣二氫化矽與一氧化二氮，或矽烷與一氧化二 氮為反應氣體。該常壓化學氣相沈積製程係使用氫氣、氮 氣或氬氣為輸送氣體，將反應氣體均勻混合後送入反應室 中。 該熱處理製程包含一第一處理程序及一第二處理程序。 该第一處理程序係於氮氣或氬氣之環境中進行矽奈米晶體 之成長，其處理溫度係介於8〇〇至i3〇〇°C之間且處理時間 係介於1至300分鐘。該第二處理程序係於氫氣之環境中 進行該矽奈米晶體之表面鈍化，其處理溫度係介於5〇〇至 600°C之間且處理時間係介於}至12〇分鐘。 【實施方式】 量子侷限效應（Quantum confinement effect)使材料之能隙間隔 隨著尺寸變小而變寬，因而奈米尺寸之晶體具有不同於一 般大尺寸材料之獨特光電特性。因此，除了利用習知之多 孔性石夕材料之外，研究人員亦嘗試藉由在高穩定性的二氧 化石夕溥膜中形成石夕奈米晶體（SiliC〇n nan〇Crytstal，％NC)來製備 石夕光源。 石夕奈米晶體之製備方法係先利用化學氣相沈積技術形成 -10- 1229945 次當量比氧化矽 氧原子數與矽原 一具有過剩石夕原子（Excess of silicon)成份之 (Si0X)薄膜（Sub-stoichiometric silica film)，其> 子數之比例⑷小於2。隨後進行一高溫的敎處理㈣ 以驅使兩個不同的金屬相（即矽與二氧化矽）彼此分離，用以 同時形成具有秩序（order)的結構之矽奈米晶體與均質結構 (Amorphous)之二氧化矽，其中二氧化矽薄膜係作為矽奈米晶 體寄宿用之母體組織（matrix)。由於二氧化矽材料為均質結 構，因此矽奈米晶體與二氧化矽之間係無應變（Strain_ftee)。 矽奈米晶體之大小與密度可以藉由薄膜沈積溫度與退火溫 度等工作參數來控制。 另一種矽奈米晶體之製備方法就是採用離子佈植技術。 離子佈植技術是發展多年成熟的技術，已經使用在大型半 導體積體電路製程之中。離子佈植技術係將加速的矽離子 直接植入二氧化矽薄膜之中以於二氧化矽薄膜内之局部區 域形成過㈣原子。之後，騎敎處理轉使過剩石夕原 子成核結晶而形成寄宿於二氧化矽薄膜（母體組織）中的矽 奈米晶體。 離子佈植技術可藉由調節植入離子的能量與劑量，而在 一特定的局部區域與深度範圍植入所需的過剩矽原子濃度 (Concentration)與分佈輪廓（pr〇file)。再者，在離子佈植過程中 亦^/成出許夕結構性的缺陷⑻，而這些結構性 缺陷可降低原子擴散之活性能（Activation energy of diffusion)，使 浔執行金屬相分離所需之退火處理的溫度亦隨之相對的降 低Λ、、:而，相較於化學氣相沈積製程，因離子佈植技術形 H:\HU\HYG\核能所\92834\92834 D〇c -11 - 1229945 成過剩矽原子濃度所需時間太長以致於不適合應用於製備 發光二極體之發光薄膜。 廣泛使用於半導體製程之化學氣相沈積法（Chemical VaporH: \ HU, HYG \ Nuclear Energy Institute W2834 \ 92834 D0C 1229945 It is easy to produce chemical reaction with oxygen atoms in the air, which will cause the degradation of photoelectric performance, so it is difficult to control the change of its photoelectric performance with time. [Summary of the Invention] The main object of the present invention is to provide an infrared light-emitting element having a silicon-containing light-emitting film and a preparation method thereof. To achieve the above object, the present invention discloses an infrared light emitting element and a preparation method thereof. The infrared light emitting element includes a substrate having an upper surface and a lower surface, a silicon dioxide film disposed on the upper surface, a plurality of silicon nanocrystals distributed in the silicon dioxide film, and one disposed on the two. A first ohmic contact electrode on the silicon oxide film and a second ohmic contact electrode disposed on the lower surface. The substrate may be a p-type silicon substrate or an n • -type silicon substrate, and the first ohmic contact electrode may be formed of indium tin oxide. The thickness of the silicon dioxide film is between 1 and 100 nanometers, and the size of the silicon nanocrystal is between 5 and 10 nanometers. Another embodiment of the infrared light emitting element includes a substrate, an alloy thin film disposed on the substrate, a dioxygen thin film disposed on a partial surface of the alloy thin film, and a plurality of distributed in the dioxygen thin film. The stone oscillating rice crystal, the first ohmic contact electrode provided on the dioxy-cut film, and a second ohmic contact electrode placed on a partial surface of the 4 alloy film. The alloy thin film is composed of gadolinium, aluminum, and gallium, the first ohmic contact electrode is composed of indium tin oxide, and the substrate is a quartz substrate or an aluminum substrate. —The method of preparing the infrared light-emitting element is firstly formed on the substrate—the secondary silicon oxide film with a ratio of one to one, in which the oxygen atom of the silicon oxide film with the equivalent ratio is: H: \ HU \ HYG \ Nuclear Energy Institute \ 92834 \ 92834 Dc > (: -9-1229945 and the ratio of the number of atoms in Shixi is small> 2. Then, at least one heat treatment process is performed to drive this time equivalent to cut the material of the thin section of oxygen to crystallize to form a plurality of silicon nanometers Crystal. The silicon oxide film of this equivalent ratio is formed on the substrate by an atmospheric pressure chemical vapor deposition process, wherein the temperature of the atmospheric pressure chemical vapor deposition process is between 700 and 100 ° C and the deposition time is It is between 1 and 300 minutes. The atmospheric pressure chemical vapor deposition process uses a two-gas silicon dihydrogen and nitrous oxide, or a silane and nitric oxide with a flow ratio between ι0: ι and 1:10. Dinitrogen is the reaction gas. The atmospheric pressure chemical vapor deposition process uses hydrogen, nitrogen, or argon as the transport gas, and the reaction gas is uniformly mixed and sent to the reaction chamber. The heat treatment process includes a first processing program and a first Second processing program. The first processing program is based on nitrogen. The growth of silicon nanocrystals is carried out in an atmosphere of gas or argon. The processing temperature is between 800 and 300 ° C and the processing time is between 1 and 300 minutes. The second processing program is The surface passivation of the silicon nanocrystals is performed in a hydrogen atmosphere, and the processing temperature is between 500 and 600 ° C and the processing time is between} and 120 minutes. [Embodiment] Quantum confinement effect (Quantum confinement effect) makes the energy gap interval of the material widen as the size becomes smaller, so nano-sized crystals have unique optoelectronic properties that are different from general large-sized materials. Therefore, in addition to using the conventional porous stone material, Researchers have also attempted to prepare Shixi light sources by forming Shixinan crystals (% NC) in high-stability SiO2 films. Shixi nanocrystals are prepared by a method First use chemical vapor deposition technology to form -10- 1229945 sub-stoichiometric silica film (Sub-stoichiometric silica film) with silicon oxide atomic number and silicon original with excess excess of silicon (Excess of silicon) component. t; the ratio of the number of subunits is less than 2. Subsequently, a high-temperature sublimation treatment is performed to drive two different metal phases (that is, silicon and silicon dioxide) to be separated from each other to form an orderly structured silicon at the same time. Nanocrystalline silicon and homogeneous structure (Amorphous) silicon dioxide, of which the silicon dioxide film is used as the matrix of silicon nanocrystalline boarding (matrix). Because the silicon dioxide material is a homogeneous structure, the silicon nanocrystalline and the There is no strain between the silicon oxides (Strain_ftee). The size and density of silicon nanocrystals can be controlled by working parameters such as film deposition temperature and annealing temperature. Another method for preparing silicon nanocrystals is ion implantation. Ion implantation technology is a mature technology that has been developed for many years, and has been used in large semiconductor volume circuit manufacturing processes. Ion implantation technology implants accelerated silicon ions directly into the silicon dioxide film to form plutonium atoms in local areas in the silicon dioxide film. Later, the riding process turned to nucleate and crystallize the excess Shi Xi atoms to form silicon nanocrystals hosted in a silicon dioxide film (parent tissue). Ion implantation technology can adjust the concentration and distribution of excess silicon atoms (pr0file) required for implantation in a specific local area and depth range by adjusting the energy and dose of implanted ions. Furthermore, Xu Xi's structural defects 亦 are also formed during the ion implantation process, and these structural defects can reduce the activation energy of diffusion, which enables 浔 to perform metal phase separation. The temperature of the annealing treatment is also relatively reduced accordingly. Compared with the chemical vapor deposition process, the shape of the ion implantation technology is H: \ HU \ HYG \ Nuclear Energy Institute \ 92834 \ 92834 D〇c -11- 1229945 The time required for the concentration of excess silicon atoms is too long to be suitable for the application of light-emitting films for light-emitting diodes. Chemical Vapor method widely used in semiconductor processes
Deposition，CVD)依據工作溫度範圍（從1 〇〇至1 〇〇〇。〇)與工作 壓力範圍（從大氣壓力至7Pa等變化）可分為常壓化學氣相 沈積法（APCVD)、低壓化學氣相沈積法（LPCVD)與電漿強 化化學氣相沈積法（PECVD)等三種。相較於離子佈植技 術’化學氣相沈積法具有可精準的控制沈積薄膜之組成與 結構、均勻且快速的沈積速率、高產量及低製作成本等優 點。 低壓化學氣相沈積法與電漿強化化學氣相沈積法等低溫 沈積製程所形成的含矽薄膜之金相結構較為鬆散，且具有 較多會抑制結晶成長之結構性缺陷與雜質。本發明係選擇 使用高溫之常壓化學氣相沈積製程來製備發光二極體之含 石夕發光薄膜。由於高溫環境下製備之含矽發光薄膜具有較 少的結構性缺陷及雜質，且複雜的矽-氮·氧（si_N_〇)複合物 可形成高緻密性與高密度分佈之矽奈米晶體。如此，矽奈 米曰a體之榮光光譜具有高清晰度、高亮度及較窄的光譜半 寬度。 圖1係一书壓化學氣相沈積裝置100之示意圖。如圖1 所示’該常壓化學氣相沈積裝置100包含一反應室10、一 Λ置於4反應至10外圍之高頻振盪電源、一設置於該反 應至10中之石墨塊14、—進氣岐管16以及一出氣岐管18。 石土 A 14係用以承載欲進行薄膜沈積之基板22。較佳地，Deposition (CVD) can be divided into atmospheric pressure chemical vapor deposition (APCVD) and low pressure chemistry according to the working temperature range (from 100 to 100.00) and the working pressure range (from atmospheric pressure to 7Pa, etc.) Vapor deposition (LPCVD) and plasma enhanced chemical vapor deposition (PECVD). Compared with the ion implantation technology, the chemical vapor deposition method has the advantages of accurately controlling the composition and structure of the deposited film, uniform and fast deposition rate, high yield, and low production cost. The metallographic structure of the silicon-containing thin film formed by low-temperature deposition processes such as low-pressure chemical vapor deposition and plasma-enhanced chemical vapor deposition is relatively loose, and it has many structural defects and impurities that inhibit crystal growth. In the present invention, a high temperature atmospheric pressure chemical vapor deposition process is selected to prepare a light-emitting diode-containing luminescent film. Because the silicon-containing light-emitting film prepared under high temperature environment has fewer structural defects and impurities, and the complex silicon-nitrogen-oxygen (si_N_〇) complex can form silicon nanocrystals with high density and high density distribution. In this way, the glare spectrum of the Si nanometer a body has high definition, high brightness, and a narrow spectral half width. FIG. 1 is a schematic diagram of a book pressure chemical vapor deposition apparatus 100. As shown in FIG. 1 'The atmospheric pressure chemical vapor deposition device 100 includes a reaction chamber 10, a high-frequency oscillating power source Λ located at the periphery of 4 reactions to 10, a graphite block 14 disposed in the reaction 10,- An intake manifold 16 and an exhaust manifold 18. Stone and soil A 14 is used to carry the substrate 22 for thin film deposition. Preferably,
H:\HU\HYG\核能所 \928M\92834.DOC •12- 1229945 石墨塊14本身已事先沈積—層由碳化石夕及二氧化石夕構成之 薄膜15，以避免氧分子對石墨塊14之侵蝕。 圖2至圖4例示本發明紅外光發光二極體之製備方法。 本發明製備發光二極體50時首先將基板22置放於反應室 1〇之石墨塊14上，再利用高頻振盪電源12將石墨塊14 加熱到沈積溫度TD。該基板22可為一 p_型矽基板或一 & 型矽基板，且具有一上表面23A及一下表面23B。之後， 藉由運送氣體（可選用氫氣、氬氣或氮氣）u將一定摩爾數 或體積比例之反應氣體17經由進氣岐管16均勻混合後送 入反應s ίο巾。反應氣艘17可為二氣二氮化邦iH2Ci2) 與一氧化二氣（乂〇)之混合氣體，且二者之流量比或體積比 例係介於nu)至1〇:1之間。此外，反應氣體17亦可為 或石夕燒卿4)與N2〇之混合氣體，且二者之流量比或體積 比例係介於1 : 1 〇至1 〇 : 1之間。 將該反應室10維持在沈積溫度Td 一預定時間b，以形 成-具有㈣㈣子之次當量比氧切（Si〇x)薄膜2〇於基 板22之上表面23A，其中氧原子數與矽原子數之比例 小於2。其它反應副產物19，例如氮氣（Ν2)與氣化氫（hci) 等^體則經由排氣岐管18連續排出。之後，輸入氮氣（或 氮氣）至反應室10之中以形成一氮氣（或氬氣）環境，並將反 應室10之溫度升高至一處理溫度Tp，且保持一預定時間 tP以進行一熱處理程序。該反應室丨〇之環境將驅使該次當 量比氧化矽薄膜20内之過剩矽原子進行晶體成長及熟化等 反應程序，以將該次當量比氧化矽薄膜2〇轉化成一具有矽 H:\_HYG\核能所\92834\92834.DOC -13- 1229945 奈米晶體24之二氧化石夕薄膜26。 著通入氫氣至反應室1〇之中，並將反應室10之溫 高t —氫鈍化溫度TPH且保持一預定時間tpH，以進行 石夕不米晶體24之表面鈍化程序。熱處理程序及表面純化程 序將該次當量比氧化石夕薄媒2〇轉化成一具有石夕奈米晶體 7之二氧化矽薄膜26。該二氧化矽薄膜26係作為矽奈米 ^ 寄宿用之母體組織，且該二氧化矽薄膜26之厚度 係介於1至1GG()()奈米之間，而該硬奈米晶體24之尺寸係 介於5至1〇奈米之間。 考圖4在一氧化石夕薄膜26上形成一層由氧化銦錫 (indiUm如_ ’ IT0)構成之透明歐姆接觸電極28,且在基板 22之下表面23Β形成一歐姆接觸電極3〇,以完成該發光二 極體5〇之製作°若在透明歐姆接觸電極28上施加正電壓 並在歐姆接觸電極3G上施加負電壓，該發光二極體50將 由電流激發而發射出紅外光4〇。 圖5例示本發明之沈㈣序、熱處理程序及表面鈍化程 序之操作溫度及時間。如圖5所示，沈積溫度L係介於川〇 °0至11GG°C之間’且沈積時間tD係介於！至3⑻分鐘。熱 處理程序之溫度Tp係介於8〇〇至13〇〇t：之間，且處理時間 tP係介於1至300分鐘。表面鈍化程序之溫度係介於 500至600 C ’工作時間tPH係介於1至丨2〇分鐘。 圖6係本發明二氧化矽薄膜26之矽奈米晶體24的光激 螢光（Photolummescence，PL)光譜圖。該光激螢光光譜圖係以氬 氣雷射光束（波長為488奈米）直接照射該二氧化矽薄膜 H:\HU\HYG\ 核能所\92834\92834.DOC -14- 1229945 ι再量測發奈米晶體24發出之光激螢光。如圖6所示， 氧化夕薄膜26之石夕奈米晶體24所發出之光激勞光的波 長係"於7〇0至900奈米之間，波峯波長約4 800至850 奈米左右，即一紅外光。 -圖7例不本發明第二實施例之發光二極體％。如圖7所 示，該發光二極體70包含一基板33、一設置於該基板33 上之合金薄膜60、一設置於該合金薄膜⑽之局部表面之二 氧化矽薄膜26、一設置於該二氧化矽薄膜％上之透明電極 28、一設置於該合金薄膜6〇之局部表面之歐姆接觸電極 “。該二氧化矽薄膜26係以前述之方法製備，因而具有可 發出紅外光之矽奈米晶體24。該合金薄膜6〇係由矽、鎳及 嫁構成’且為型，即一 n+_GaNiSi薄膜。該歐姆接觸電 極64可由鈦-鋁合金構成。該基板33可為一石英幻基 板或一二氧化二紹（Al2〇3，Sapphire)基板。 本發明係採用高溫之常壓化學氣相沈積製程來製備該次 當量比氧化矽薄膜20，其化學反應式為：H: \ HU \ HYG \ Nuclear Energy Institute \ 928M \ 92834.DOC • 12-1229945 The graphite block 14 itself has been deposited in advance—a thin film 15 of carbonized carbide and dioxide dioxide is used to prevent the oxygen molecules from blocking the graphite block 14 Erosion. 2 to 4 illustrate a method for preparing the infrared light emitting diode of the present invention. When preparing the light-emitting diode 50 according to the present invention, the substrate 22 is first placed on the graphite block 14 in the reaction chamber 10, and then the graphite block 14 is heated to the deposition temperature TD by using the high-frequency oscillation power source 12. The substrate 22 may be a p-type silicon substrate or an & type silicon substrate, and has an upper surface 23A and a lower surface 23B. After that, a certain number of moles or a volume ratio of the reaction gas 17 is uniformly mixed through the intake manifold 16 by the transport gas (optionally hydrogen, argon, or nitrogen) and sent to the reaction towel. The reaction gas vessel 17 may be a mixed gas of two gases, iH2Ci2) and nitrous oxide (乂 〇), and the flow ratio or volume ratio of the two is between nu) and 10: 1. In addition, the reaction gas 17 may also be a mixed gas of or Shi Xi Shao Qing 4) and N2O, and the flow ratio or volume ratio of the two is between 1:10 and 10: 1. The reaction chamber 10 is maintained at a deposition temperature Td for a predetermined time b to form a second-equivalent specific oxygen cut (Siox) film 20 having a rafter on the upper surface 23A of the substrate 22, wherein the number of oxygen atoms and silicon atoms The ratio of the number is less than 2. Other reaction byproducts 19, such as nitrogen (N2) and hydrogen gas (hci), are continuously discharged through the exhaust manifold 18. After that, nitrogen (or nitrogen) is input into the reaction chamber 10 to form a nitrogen (or argon) environment, and the temperature of the reaction chamber 10 is increased to a processing temperature Tp, and maintained for a predetermined time tP to perform a heat treatment. program. The environment of the reaction chamber 〇 will drive the excess silicon atoms in the silicon oxide film 20 of this equivalent ratio to perform crystal growth and aging processes, so as to convert the silicon oxide film 20 of the secondary equivalent ratio to a silicon H: \ _ HYG \ Nuclear Energy Institute \ 92834 \ 92834.DOC -13- 1229945 Nano-crystal 24 SiO 2 thin film 26. By passing hydrogen gas into the reaction chamber 10, the temperature of the reaction chamber 10 is increased by t—the hydrogen passivation temperature TPH and maintained for a predetermined time tpH, to perform the surface passivation process of the crystal 24. The heat treatment procedure and the surface purification procedure convert the equivalent weight of the second oxide oxide thinner medium 20 to a silicon dioxide thin film 26 having the stone latex crystal 7. The silicon dioxide film 26 is used as a mother tissue of silicon nanometer ^ boarding, and the thickness of the silicon dioxide film 26 is between 1 and 1 GG () () nanometer, and the hard nanocrystal 24 The dimensions are between 5 and 10 nanometers. Consider FIG. 4 to form a transparent ohmic contact electrode 28 composed of indium tin oxide (indiUm such as _ 'IT0) on a stone oxide film 26, and form an ohmic contact electrode 30 on the lower surface 23B of the substrate 22 to complete Production of the light-emitting diode 50 ° If a positive voltage is applied to the transparent ohmic contact electrode 28 and a negative voltage is applied to the ohmic contact electrode 3G, the light-emitting diode 50 will be excited by a current to emit infrared light 40. Figure 5 illustrates the operating temperature and time of the immersion sequence, heat treatment procedure and surface passivation procedure of the present invention. As shown in Fig. 5, the deposition temperature L is between 0 ° 0 to 11GG ° C 'and the deposition time tD is between! To 3 minutes. The temperature Tp of the thermal treatment program is between 800 and 1300 t :, and the treatment time tP is between 1 and 300 minutes. The temperature of the surface passivation process is between 500 and 600 C, and the working time tPH is between 1 and 20 minutes. FIG. 6 is a photoluminescence (PL) spectrum diagram of the silicon nanocrystal 24 of the silicon dioxide film 26 of the present invention. The photoluminescence fluorescence spectrum is directly irradiated to the silicon dioxide film with an argon laser beam (wavelength of 488 nm). H: \ HU \ HYG \ Nuclear Energy Institute \ 92834 \ 92834.DOC -14-1229945 The light-emitting fluorescence emitted by the nanocrystal 24 was measured. As shown in FIG. 6, the wavelength range of the laser-excited light emitted by the iris nanocrystal 24 of the oxidized thin film 26 is between 700 and 900 nanometers, and the peak wavelength is about 4 800 to 850 nanometers. , That is, an infrared light. -Fig. 7 illustrates a light emitting diode% according to the second embodiment of the present invention. As shown in FIG. 7, the light emitting diode 70 includes a substrate 33, an alloy thin film 60 disposed on the substrate 33, a silicon dioxide film 26 disposed on a partial surface of the alloy thin film ⑽, and A transparent electrode 28 on the silicon dioxide film%, an ohmic contact electrode provided on a local surface of the alloy film 60. The silicon dioxide film 26 is prepared by the method described above, and therefore has silicon dioxide that emits infrared light. Rice crystal 24. The alloy thin film 60 is composed of silicon, nickel, and silicon, and is a type, that is, an n + _GaNiSi thin film. The ohmic contact electrode 64 may be made of titanium-aluminum alloy. The substrate 33 may be a quartz magic substrate Or Al2O3 (Sapphire) substrate. The present invention uses a high-temperature atmospheric pressure chemical vapor deposition process to prepare the sub-equivalent ratio silicon oxide film 20, and the chemical reaction formula is:
SiH2Cl2+ xN20~> SiOx+ xN2+ 2HC1 在沈積溫度（TD)介於700至ll〇〇°C之高溫環境下，藉由 運送氣體將預定摩爾數或體積比例之SiH2Cl2與N2〇氣體 均勻混合後送入高溫反應室1 〇之中。在高溫反應室1 〇之 中，SiHaCh與N2〇兩氣體將分別被高溫解離成原子態後， 再重組形成次當量比之氧化矽並沈積於該基板22上。沈積 於該基板22上之氧化石夕包含過剩矽原子成份，而過剩石夕原 子成份之多寡可利用非破壞檢測方法測得其氧原子數與過 HAHU\HYG\核能所 \92834\92834.DOC -15- 1229945 剩矽原子數（O/Si)之相對比例。例如，藉著量測其相對於標 準二氧化矽（Si〇2)之光折射率大小即可推知氧原子數與過 剩矽原子數（O/Si)之相對比例。 矽之熔點（TM)約為1430°C，其結晶成核溫度（Tn)約為〇 6 X TmS858°C。該次當量比氧化矽薄膜2〇之沈積溫度h係 介於700。(：至ll〇(TC，已明顯高於結晶成核溫度，因此在 該次當量比氧化矽薄膜20之沈積過程中，反應室1〇内之 高溫亦同時驅使該次當量比氧化矽薄膜2〇中之大部份過剩 矽原子形成矽奈米晶體核（Nucleus),並形成矽奈米晶體核與 母體（由二氧化矽構成）間之介面（Interstate)結構。矽奈米晶體 核與母體間之介面結構主要是由矽奈米晶體周邊之懸掛鍵 (dangling bonds)與氮-氧鍵所構成。例如，矽-氮鍵⑻_n bonds)、矽-氧鍵（Si_0bonds)及矽_氮_氧鍵（Si_Nx_〇y^該介面 結構是主要的螢光中心（luminescence centers)。 之後，在氮氣或氬氣環境中進行矽奈米晶體24之成長與 熟化等退火製程。該次當量比氧化矽薄膜2〇之主要的結構 組成包含均質結構（Amorphous)之氧化矽與過剩矽原子形成 之羣聚物（Clusters)，其中過剩矽原子羣聚物大部份已形成矽 奈米晶體核。將該次當量比氧化矽薄膜2〇置於熱處理溫度 (TP)之高溫環境中，並保持一段時間tp以完成所有矽奈米 晶體之成長及介面結構之熟化，亦即將該次當量比氧化矽 薄膜20轉化成具有矽奈米晶體24之二氧化矽薄膜％。 此外，若該次當量比氧化矽薄膜2〇内之過剩矽原子未在 該沈積製程中形成矽晶體核，該熱處理程序之高溫則進一 H:\KU\HYG、核能所\92834\92834.DOC -16- 1229945 步地驅使該次當量比氧化矽薄膜20内之過剩矽原子成核。 之後，將具有矽奈米晶體24之二氧化矽薄膜26置於氣氣 環境中，並維持在一預定溫度TPH與時間tPH以進行石夕奈米 晶體24之表面氫純化處理passivati〇n)。完成該表面 純化處理後，具有矽奈米晶體24之二氧化矽薄膜26即形 成穩定的紅外光發光薄膜。 相較於習知之技藝，本發明係利用高溫之常壓化學氣相 沈積技術以及熱處理技術製備具有含矽發光薄膜（即具有 矽奈米晶體24之二氧化矽薄膜26)之紅外光發光二極體 5 0，具有下列之優點： 1 ·本發明不需使用繁複的磊晶製程與昂貴的製程設備，僅 需沈積一層次當量比氧化矽薄膜2〇與熱處理製程，具 有製程簡單與快速之優點。 2·本發明係利用常壓化學氣相沈積製程製備該次當量氧 化矽薄膜20，而常壓化學氣相製程可整合於標準化的 半導體製程之中，因而本發明具有大量生產發光二極體 之優點。 3 ·習知技藝利用ln_V族化合物製備發光元件之發光薄膜 因而製造成本昂貴。本發明係使用氧化矽來製備發光二 極體50之含矽發光薄膜，因而材料與製作成本均相對 地較低廉。 4·習知技術使用之III-V族化合物會產生有毒化學物質。 本發明係使用氧化矽製備發光元件之含矽發光薄膜，並 無化學與有毒重金屬之使用與排放問題，為綠色環保製 H:\HU\HYG\ 核能所 \92834\92834.DOC -17- 1229945 程。 5·本發明選擇高溫條件形成含有過剩矽原子之次當量 比氧化矽薄膜20，再經熱處理而轉化成具有矽奈米晶 體24之二氧化矽薄膜26，因而具有較高的溫度穩定 性’且製備之發光薄膜具有窄寬幅的紅外光光譜分佈。 6·高溫TP熱處理後之當量比二氧化矽薄膜26具有較高緻 密性、較高密度分佈之矽奈米晶體24以及較低的雜 質’因而矽奈米晶體24與其介面結構經激發可產生較 清晰與高亮度之光譜。 本發明之技術内容及技術特點已揭示如上，然而熟悉本 項技術之人士仍可能基於本發明之教示及揭示而作種種不 背離本發明精神之替換及修飾。因此，本發明之保護範圍 應不限於實施例所揭示者，而應包括各種不背離本發明之 替換及修飾，並為以下之申請專利範圍所涵蓋。 【圖式簡要說明】 圖1係一常壓化學氣相沈積裝置之示意圖； 圖2至圖4例示本發明之發光二極體之製備方法； 圖5例示本發明之沈積程序、熱處理程序及表面鈍化程 序之操作溫度及時間； 圖6係本發明之二氧化矽薄膜之矽奈米晶體的光激螢光 光譜圖；以及 圖7例示本發明第二實施例之發光二極體。 【元件符號說明】 10反應室 11運送氣體 【\HU\HYG\核能所\92S34\92834 DOC 18- 1229945 12 高頻振盪電源 14 石墨塊 15 薄膜 16 進氣岐管 17 反應氣體 18 出氣岐管 19 反應副產物 20 次當量比氧化矽薄膜 22 基板 23A上表面 23B 下表面 24 矽奈米晶體 26 二氧化矽薄膜 28 歐姆接觸電極 30 歐姆接觸電極 40 紅外光 33 基板 50 發光二極體 60 合金薄膜 64 歐姆接觸電極 70 發光二極體 100 化學氣相沈積裝置 H:\HU\HYG\核能所\92834\92834.DOC - 19 -SiH2Cl2 + xN20 ~ > SiOx + xN2 + 2HC1 In a high-temperature environment with a deposition temperature (TD) of 700 to 100 ° C, a predetermined number of moles or volume ratio of SiH2Cl2 and N2O gas are mixed by transporting the gas and sent in. High-temperature reaction chamber 10. In the high-temperature reaction chamber 10, the SiHaCh and N2O gases are dissociated into atomic states at high temperatures, and then recombined to form silicon oxide with a sub-equivalent ratio and deposited on the substrate 22. The oxidized stone deposited on the substrate 22 contains excess silicon atomic components, and the amount of excess stone atomic components can be measured by a non-destructive detection method and its oxygen atom number and excess HAHU \ HYG \ Nuclear Energy Institute \ 92834 \ 92834.DOC -15- 1229945 Relative ratio of the number of remaining silicon atoms (O / Si). For example, the relative ratio of the number of oxygen atoms to the number of excess silicon atoms (O / Si) can be inferred by measuring its light refractive index relative to standard silicon dioxide (Si02). The melting point (TM) of silicon is about 1430 ° C, and its crystallization nucleation temperature (Tn) is about 0 6 X TmS858 ° C. The deposition temperature h of the second equivalent to the silicon oxide film 20 is between 700. (: To 110 ° C, which has been significantly higher than the crystallization nucleation temperature, so during the deposition of the silicon dioxide film 20 of this time, the high temperature in the reaction chamber 10 also drives the silicon dioxide film 2 of the time 〇 Most of the excess silicon atoms form nucleus and form the interstate structure between the nucleus of silicon nanocrystals and the parent (consisting of silicon dioxide). The core of crystalline silicon nanocrystals and the parent The interface structure is mainly composed of dangling bonds and nitrogen-oxygen bonds around the silicon nanocrystal. For example, silicon-nitrogen bonds ⑻_n bonds, silicon-oxygen bonds (Si_0bonds), and silicon_nitrogen_oxygen Bond (Si_Nx_〇y ^ This interface structure is the main luminescence centers. After that, annealing and growth processes such as growth and aging of silicon nanocrystals 24 are performed in a nitrogen or argon atmosphere. This sub-equivalent ratio is higher than that of silicon oxide. The main structural composition of the thin film 20 includes clusters formed by amorphous silicon oxide and excess silicon atoms, and most of the excess silicon atom clusters have formed silicon nanocrystalline nuclei. Sub-equivalent ratio silicon oxide film 20 placed in a high temperature environment of heat treatment temperature (TP), and maintained for a period of time tp to complete the growth of all silicon nanocrystals and the maturation of the interface structure, that is, to convert the equivalent silicon oxide film 20 to silicon nanometers % Of silicon dioxide film of crystal 24. In addition, if the excess equivalent of silicon atoms within 20% of the silicon oxide film does not form a silicon crystal core in the deposition process, the high temperature of the heat treatment process is further increased by H: \ KU \ HYG The nuclear power plant \ 92834 \ 92834.DOC -16- 1229945 step by step to nucleate the excess silicon atoms in the silicon oxide film 20 with the equivalent ratio. Then, the silicon dioxide film 26 with the silicon nanocrystal 24 is placed in the gas. In a gas environment, and maintained at a predetermined temperature TPH and time tPH for the surface hydrogen purification treatment (passivati) of the shixi nano crystal 24. After the surface purification treatment is completed, the silicon dioxide film with the silicon nano crystal 24 26 is to form a stable infrared light-emitting film. Compared with the conventional technology, the present invention uses a high-temperature atmospheric pressure chemical vapor deposition technology and heat treatment technology to prepare a silicon-containing light-emitting film (that is, a silicon nanocrystal). The silicon dioxide film 26 of the body 24, the infrared light emitting diode 50, has the following advantages: 1. The invention does not require the use of complicated epitaxial processes and expensive process equipment, and only needs to deposit a layer of equivalent ratio oxide The silicon thin film 20 and the heat treatment process have the advantages of simple and fast process. 2. The present invention uses the atmospheric pressure chemical vapor deposition process to prepare the equivalent silicon oxide film 20, and the atmospheric pressure chemical vapor phase process can be integrated into the standardized In the semiconductor manufacturing process, the present invention has the advantage of mass producing light emitting diodes. 3. Known techniques The use of ln_V group compounds to produce light-emitting films of light-emitting elements is therefore expensive to manufacture. The present invention uses silicon oxide to prepare the silicon-containing light-emitting film of the light-emitting diode 50, so the materials and manufacturing costs are relatively low. 4. Group III-V compounds used in conventional technology can produce toxic chemicals. The invention is a silicon-containing light-emitting film for preparing light-emitting elements by using silicon oxide, and has no use and emission problems of chemical and toxic heavy metals. It is a green and environmentally friendly H: \ HU \ HYG \ Nuclear Energy Institute \ 92834 \ 92834.DOC -17-1229945 Cheng. 5. The present invention selects high temperature conditions to form a silicon oxide film 20 containing a second equivalent ratio of excess silicon atoms, and then heat-treated to convert it into a silicon dioxide film 26 having silicon nanocrystals 24, thus having high temperature stability 'and The prepared light-emitting film has a narrow and wide infrared light spectrum distribution. 6. After high temperature TP heat treatment, the equivalent weight of silicon nanocrystal 24 is higher than that of silicon dioxide film 26, and it has higher density distribution and lower impurities. Clear and bright spectrum. The technical content and technical features of the present invention have been disclosed as above. However, those skilled in the art may still make various substitutions and modifications based on the teaching and disclosure of the present invention without departing from the spirit of the present invention. Therefore, the protection scope of the present invention should not be limited to those disclosed in the embodiments, but should include various substitutions and modifications that do not depart from the present invention, and are covered by the following patent application scope. [Brief description of the drawings] Figure 1 is a schematic diagram of an atmospheric pressure chemical vapor deposition device; Figures 2 to 4 illustrate the preparation method of the light-emitting diode of the present invention; Figure 5 illustrates the deposition process, heat treatment process and surface of the present invention Operating temperature and time of the passivation process; FIG. 6 is a light-induced fluorescence spectrum of a silicon nanocrystal of the silicon dioxide film of the present invention; and FIG. 7 illustrates a light-emitting diode of a second embodiment of the present invention. [Description of component symbols] 10 reaction chamber 11 transport gas [\ HU \ HYG \ Nuclear Energy Institute \ 92S34 \ 92834 DOC 18- 1229945 12 High-frequency oscillation power source 14 Graphite block 15 Thin film 16 Intake manifold 17 Reactive gas 18 Outlet manifold 19 Reaction by-products 20 equivalents of silicon oxide film 22 Substrate 23A upper surface 23B lower surface 24 silicon nano crystal 26 silicon dioxide film 28 ohmic contact electrode 30 ohmic contact electrode 40 infrared light 33 substrate 50 light emitting diode 60 alloy film 64 Ohm contact electrode 70 Light-emitting diode 100 Chemical vapor deposition device H: \ HU \ HYG \ Nuclear Energy Institute \ 92834 \ 92834.DOC-19-