201103161 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種自旋注入氮化鎵發光二極體，尤其 是具有稀磁性氧化錳辞層氮化鎵發光二極體。 【先前技術】 第一圖所示’習用技術的氮化鎵發光二極體包括依序 由下而上堆疊的基板l〇、n型氮化鎵（n_GaN)層2〇、主動 層30、p型氮化鎵（p-GaN)層40以及間隔層（Sapcer)50, 其中η型氮化鎵層20連接負極7〇，而p型氮化鎵層4 〇 以及間隔層50連接正極80。主動層30包括複數個相互交 替堆遠的氮化紅與氬化錮鎵多重量子井(Muitipie Quantum Well ， MQW)。 當正極與負極施加正向電壓時，亦即p型氮化鎵層40 與η型氮化鎵層20為順向偏壓（F〇rward Biased)時，主動 層30的氮化鎵與氮化銦鎵量子井會因電子電洞的復合而將 電能轉換成光能’進而朝基板1〇發射出光線，因此主動層 30為主要發光區。 習用技術的缺點是，隨著顧端發光亮度的要求日 益增加’使得習用氮化鎵發光二_已不合需求，而需要 -種具自旋注人載子的氮化鎵發光二極體，可在外加磁場 下大幅提高導通電流，以增加發光亮度，以解決上述習用 技術的缺點。 201103161 【發明内容】 本發明之主要目的在提供—種自旋注人氮化鎵發光 -極體，包括依序由下社堆疊的基板、㈣氮化錄層、 主動層、P型氮化鎵層、間隔層以及氧化鐘辞層，其中η 型氮化鎵層連接負極，而？缝化鎵層、間隔層以及氧化 猛鋅層連接正極，主動層為主要發光區並包括複數個相互 交替堆疊的氮化鎵與氮化銦鎵量子井，由於氧倾鋅層會 • *生額外的自旋注入载子，可增加總電流，進而改善氮化 鎵發光二極體的發光效率，增加整體發光二極體的亮度。 本發明之另一目的在提供一種自旋注入氮化鎵發光 -極體的製作方法，包括制二氣化財作朗來源，以 及ZnCCHsCOO)2為辞的來源，利用液相化學氣相沉積法， 在上間隔上形成具有自旋注入載子的氧化猛辞層 ，以增加 發光二極體的亮度。 【實施方式】 以下配合圖式及元件符號對本發明之實施方式做更 詳細的說明，俾使熟雅概藝者在研讀本賴書後能 據以實施。 自旋相依電子學(Spintronics)簡稱或縮寫為自旋電 子學，或可稱為磁電子學(Magneto-electronics)，是一 項同時使用電子的量子自旋狀態與電荷狀態的前瞻科 技。自旋電子學主要是利用電子的自旋對外加磁場的特 201103161 性，尤其是光電磁的交互作用，傳統的電子元件運作是以 電荷的正負性質、數目以及能量為基礎在速率以及能量 /肖耗方面有其限制，而自旋電子元件運作是以電子自旋的 方向及自旋1¾合為基礎，在非常低的功率時仍能有較快的 速率。 氧化鋅(ΖηΟ)為具有直接能隙的半導體，是能隙為 3.37eV的寬能隙材料’且具有約6〇—的高激子束缚能 • (exciton bindinSenergy)，是重要的光電元件材料。將 猛換入氧化辞中形成磁性半導體的氧化輯(MnZn〇)，氧 化猛鋅為一單相（singlephase)，在(〇〇〇1)平面具有六角 纖維鋅礦結構(hexag〇nai wurtzite structure)的不導電 薄膜，且在室溫鐵磁性下為p型的稀磁性材料。由電激發 光（electroluminescence，EL)的量測顯示，氧化錳鋅具 有自旋注入(Spin-injection)載子的特性，尤其是在外加 • 磁場下。 因此，本發明的自旋注入氮化鎵發光二極體係結合具 有自旋注入載子晚化鑑鋅以及一般的氮化鎵發光二極 體，以加強發光亮度。 參閱第二圖，本發明自旋注入氮化鎵發光二極體的 示意圖。如第一圖所示，本發明的自旋注入氮化鎵發光 二極體包括依序由下而上堆疊的基板10、η型氮化鎵 (n_GaN)層20、主動層30、ρ型氮化鎵（p_GaN)層4〇、 201103161 間隔層（Sapcer)50以及氧化錳鋅(MnZnO)層60。基板1〇 可為藍寶石（Sapphire)基板。η型氮化鎵層20連接負極 70，而Ρ型氮化鎵層40、間隔層50以及氧化盆鋅層6〇 連接正極80。主動層30包括複數個相互交替堆疊的氮化 鎵與氮化銦鎵多重量子井。 由於氧化錳鋅層60為稀磁性半導體層，當作自旋注 入載子的來源，可在順向偏壓時，提供額外的自旋注入 載子，進而提高導通電流，增加發光亮度，尤其是在外 • 加磁場下，氧化錳鋅層60的自旋注入載子效應更加明 顯，如第三圖所示，發光二極體的光輸出功率-電流(L—j) 曲線圖。 在第三圖中，曲線C1為習用氮化鎵發光二極體在無 外加磁場下的光輸出功率-電流曲線，曲線以為本發明 自旋注入氮化鎵發光二極體在無加磁場下的光輸出功率 -電流曲線，曲線C3為習用氮化鎵發光二極體在外加磁 場下的光輸出功率-電流曲線，曲線w為本發明自旋注 瞻入氮化鎵發光二極體在外加磁場下的光輸出功率電流 曲線。由第三圖可知’在注入電流較小時，光輸出功率 都呈現線性增加’且本發明自旋注入氮化鎵發光二極體 無論在加磁場下或無加磁場下都具有較高的光輸出功 率’亦即發光亮度較高。 例如，在無外加磁場下，於20mA的低注入電流時， 本發明自旋注入氮化鎵發光二極體的光輸出功率比習用 氮化鎵發光二極體增加約13%，而在8〇mA的高注入電流 下’更有24%的提升。在外加磁場下，於2〇mA的低注入 電流時，本發明自雜人氮化鎵發光三極_光輪出功 201103161 率可増加約14%，在高注入電流的8〇畝下，光輸出功率 增加約25% ’因此，氧化錳鋅層的自旋注入載子可有效的 提高氮化鎵發光二極體的光功率強度。 ,參閱第四圖，本發明自旋注入氮化鎵發光二極體之 製作方法的流程圖。首先由步驟sl〇開始，配製磊晶用 水溶液，主要疋使用一氣化猛(MnCh)為锰元素的來源， 而以醋酸鋅⑽⑽⑽)2)為辞元素的來源，將二氣化猛 與醋酸鋅加人純水或去離子水巾，經溶解後形成蟲晶用 φ 水溶液。 、田接著進入步驟S20，設定攜帶氣體流量、蟲晶用高 =的溫度餘晶成長咖，其巾攜帶氣體可為氮氣或 氬軋攜▼氣體流量可為5〇至5〇〇 sccm，高溫爐的溫度 可為200至棚。c，且蠢晶成長時間可為2〇分至2小時。 接著進入步驟S30，進行遙晶成長，將具有基板、n型氮 化餘層、主騎、？魏化騎以及間_的氮化鎵晶圓 置入高溫爐内，並將蟲晶用水溶液置入超音波喷霧機 • β ’通入攜帶氣體至超音波噴霧機使蟲晶用水溶液由超 t波噴霧機之噴嘴畅氮化鎵晶圓喷出，而在氮化鎵晶 °的間隔層上形成具自旋注人載子的氧化猛鋅層。 以上所述者僅為用以轉本發明之較佳實施例並 ¥企圖據㈣本發明齡何形式上之關，是以，凡有 相同之發明精神下所作有關本發明之任何修飾或變 ’皆仍應包括在本㈣意圖賴之範脅。 201103161 【圖式簡單說明】 第一圖為習用技術氮化鎵發光二極體的示意圖。 第二圖為本發明自旋注入氮化鎵發光二極體的示意圖。 第三圖為發光二極體的光輸出功率-電流曲線圖。 第四圖為本發明自旋注入氮化鎵發光二極體之製作方法 的流程圖。 【主要元件符號說明】 10基板 ® 20 η型氮化鎵層 30主動層 40 ρ型Ιι化鎵層 50間隔層 60氧化锰鋅層 70負極 80正極 S10配製磊晶用水溶液 # S20設定攜帶氣體流量與高溫爐溫度 S30利用超音波喷霧機與高溫爐進行磊晶成長201103161 VI. Description of the Invention: [Technical Field] The present invention relates to a spin-injected gallium nitride light-emitting diode, in particular, a dilute magnetic manganese oxide layered gallium nitride light-emitting diode. [Prior Art] The gallium nitride light-emitting diode of the conventional technology shown in the first figure includes a substrate stacked sequentially from bottom to top, an n-type gallium nitride (n_GaN) layer 2, an active layer 30, p A gallium nitride (p-GaN) layer 40 and a spacer layer 50, wherein the n-type gallium nitride layer 20 is connected to the negative electrode 7〇, and the p-type gallium nitride layer 4 and the spacer layer 50 are connected to the positive electrode 80. The active layer 30 includes a plurality of mutually divergent red nitride and argon-doped gallium multi-quantum wells (Muitipie Quantum Well, MQW). When a forward voltage is applied to the positive and negative electrodes, that is, when the p-type gallium nitride layer 40 and the n-type gallium nitride layer 20 are forward biased, the gallium nitride and nitride of the active layer 30 are used. Indium gallium quantum wells convert electrical energy into light energy due to the recombination of electron holes, and then emit light toward the substrate 1〇, so the active layer 30 is the main light-emitting region. The disadvantage of the conventional technology is that with the increasing requirements of the brightness of the light-emitting end, the conventional gallium nitride light-emitting diode _ has been out of demand, and a GaN light-emitting diode with a spin-injector carrier is required. The on-current is greatly increased under an applied magnetic field to increase the luminance of the light to solve the disadvantages of the above conventional techniques. 201103161 SUMMARY OF THE INVENTION The main object of the present invention is to provide a spin-injected gallium nitride light-emitting body, comprising a substrate stacked in sequence, (4) a nitride recording layer, an active layer, and a P-type gallium nitride. Layer, spacer layer and oxidized clock layer, wherein the n-type gallium nitride layer is connected to the negative electrode, and ? The gallium layer, the spacer layer and the oxidized zinc layer are connected to the positive electrode, and the active layer is the main light-emitting region and includes a plurality of gallium nitride and indium gallium nitride quantum wells which are alternately stacked, because the oxygen-dip zinc layer will be extra The spin injection carrier can increase the total current, thereby improving the luminous efficiency of the gallium nitride light-emitting diode and increasing the brightness of the overall light-emitting diode. Another object of the present invention is to provide a method for fabricating a spin-injected gallium nitride light-emitting body, comprising a source of two gasification sources, and a source of ZnCCHsCOO)2, using liquid chemical vapor deposition. An oxidized layer having a spin-injecting carrier is formed on the upper spacer to increase the brightness of the light-emitting diode. [Embodiment] Hereinafter, the embodiments of the present invention will be described in more detail with reference to the drawings and the reference numerals, and the skilled person can implement the book after studying the book. Spintronics, abbreviated or abbreviated as spintronics, or Magneto-electronics, is a forward-looking technology that uses both the quantum spin state and the charge state of electrons. Spintronics mainly uses the spin of electrons to the external magnetic field of 201103161, especially the interaction of light and electromagnetic. The traditional electronic components operate based on the positive and negative properties of charge, the number and the energy at the rate and energy / Xiao There are limitations in terms of power consumption, and the operation of the spintronic components is based on the direction of the electron spin and the spin, which can still have a faster rate at very low power. Zinc oxide (ΖηΟ) is a semiconductor having a direct energy gap, is a wide bandgap material with an energy gap of 3.37 eV and has an exciton bindin Senergy of about 6 〇, and is an important photovoltaic element material. It will be replaced by an oxide series (MnZn〇) which forms a magnetic semiconductor in the oxidation, oxidized zinc is a single phase, and has a hexagonal fiber zincite structure in the (〇〇〇1) plane (hexag〇nai wurtzite structure) A non-conductive film and a p-type dilute magnetic material under room temperature ferromagnetism. Measurements by electroluminescence (EL) show that manganese zinc oxide has the characteristics of a spin-injection carrier, especially under an applied magnetic field. Therefore, the spin-injected gallium nitride light-emitting diode system of the present invention is combined with a spin-injecting carrier for latezing zinc and a general gallium nitride light-emitting diode to enhance the luminance. Referring to the second figure, a schematic diagram of a spin-injected gallium nitride light-emitting diode of the present invention is shown. As shown in the first figure, the spin-injected gallium nitride light-emitting diode of the present invention comprises a substrate 10 stacked sequentially from bottom to bottom, an n-type gallium nitride (n_GaN) layer 20, an active layer 30, and a p-type nitrogen. Gallium gallium (p_GaN) layer 4〇, 201103161 spacer layer (Sapcer) 50 and manganese manganese zinc (MnZnO) layer 60. The substrate 1 〇 may be a sapphire substrate. The n-type gallium nitride layer 20 is connected to the negative electrode 70, and the germanium-type gallium nitride layer 40, the spacer layer 50, and the oxidized pot zinc layer 6 are connected to the positive electrode 80. Active layer 30 includes a plurality of gallium nitride and indium gallium nitride multiple quantum wells stacked alternately. Since the manganese-zinc oxide layer 60 is a dilute magnetic semiconductor layer, as a source of the spin-injecting carrier, an additional spin-injecting carrier can be provided in the forward biasing, thereby increasing the on-current and increasing the luminance, especially Under the external magnetic field, the spin-injection carrier effect of the manganese-zinc oxide layer 60 is more obvious, as shown in the third figure, the light output power-current (L-j) curve of the light-emitting diode. In the third figure, the curve C1 is the light output power-current curve of the conventional gallium nitride light-emitting diode in the absence of an external magnetic field, and the curve is the spin injection of the gallium nitride light-emitting diode of the present invention in the absence of an applied magnetic field. Light output power-current curve, curve C3 is the light output power-current curve of the conventional gallium nitride light-emitting diode under an applied magnetic field, and the curve w is the spin-in view of the GaN light-emitting diode in the external magnetic field The lower light output power current curve. It can be seen from the third figure that the light output power increases linearly when the injection current is small, and the spin-injected gallium nitride light-emitting diode of the present invention has high light regardless of the applied magnetic field or the no-magnetic field. The output power' is also the higher the brightness of the light. For example, in the absence of an external magnetic field, the light output power of the spin-injected gallium nitride light-emitting diode of the present invention is increased by about 13% compared to the conventional gallium nitride light-emitting diode at a low injection current of 20 mA, and at 8 〇. At mA's high injection current, there is a 24% increase. Under the applied magnetic field, the low-injection current of 2〇mA, the self-man-made GaN light-emitting three-pole _ light wheel work 201103161 rate can be increased by about 14%, at a high injection current of 8 〇 mu, light output The power is increased by about 25%. Therefore, the spin injection carrier of the manganese oxide zinc layer can effectively increase the optical power intensity of the gallium nitride light-emitting diode. Referring to the fourth figure, a flow chart of a method for fabricating a spin-injected gallium nitride light-emitting diode of the present invention. First, starting from step sl1, prepare an aqueous solution for epitaxy, mainly using a gasification violent (MnCh) as the source of manganese, and using zinc acetate (10) (10) (10)) 2) as the source of the element, the two gasification and zinc acetate Add pure water or deionized water towel, and dissolve to form φ aqueous solution for insect crystal. Then, the process proceeds to step S20, and the flow of the gas is carried out, and the temperature of the insect crystal is increased by the temperature of the residual crystal. The gas carried by the towel can be nitrogen or argon. The gas flow rate can be 5 〇 to 5 〇〇 sccm. The temperature can range from 200 to shed. c, and the growth time of the stupid crystal can be 2 to 2 hours. Next, proceeding to step S30, the crystal growth is performed, and the substrate, the n-type nitrogen nitride layer, and the main ride are provided. Weihua rides and the gallium nitride wafers are placed in a high-temperature furnace, and the insect crystals are placed in an ultrasonic sprayer with an aqueous solution. • β 'passes the carrier gas to the ultrasonic sprayer to make the aqueous solution of the insect crystals super The nozzle of the t-wave sprayer is sprayed with a gallium nitride wafer, and an oxidized zinc layer having a spin-injector carrier is formed on the spacer layer of the gallium nitride crystal. The above description is only for the preferred embodiment of the present invention and is intended to be based on (4) the age of the present invention, and any modifications or changes relating to the present invention in the spirit of the same invention. All should still be included in this (four) intention to rely on the threat. 201103161 [Simple description of the diagram] The first picture is a schematic diagram of a conventional technology of gallium nitride light-emitting diodes. The second figure is a schematic view of the spin-injected gallium nitride light-emitting diode of the present invention. The third figure is a graph of the light output power-current of the light-emitting diode. The fourth figure is a flow chart of a method for fabricating a spin-injected gallium nitride light-emitting diode according to the present invention. [Major component symbol description] 10 substrate® 20 η-type gallium nitride layer 30 active layer 40 ρ-type Ι 化 化 gallium layer 50 spacer layer 60 manganese Zn layer 70 negative electrode 80 positive S10 preparation of epitaxial aqueous solution # S20 set carrier gas flow Epitaxial growth with high temperature furnace S30 using ultrasonic sprayer and high temperature furnace