1313705 九、發明說明： 【發明所屬之技術領域】 本發明係相關於一種發光二極體（light-emitting diode, LED)’尤指一種内含其化學式為（Cai x yEUxMy)Se之螢光粉 之發光二極體元件及相關螢光粉與製備方法。 【先前技術】 由於具有低耗電、長壽命（約為傳統日光燈的十倍）、以 及最重要的尚演色性(color rendering index, CRI)與可產生 ^對藝術品造成傷害之電磁輻射（visible radiation)等優 •’ 光發光二極體(white-light LED)元件已漸漸成為一種 最文市場、尤其是對演色性有特別要求之高階市場歡迎的 照明元件了。 一種最直覺製作一白光LED元件之方法為將三個分別 毛出藍、紅、及綠光之藍光⑼心丨丨咖）、紅光(red_light)、 及綠光(green-light)LED晶片組合起來、以形成該白光lED 元件。如此一來，該白光LED元件便可發射出該藍光、該 紅光、及該綠光所混合而成之白光。 然而，由於必需包含三個LED晶片，所以，上述之三 合一白光LED元件之製作成本相當高。此外，由於該等 LED之發光效率不盡相同，具體言之，該藍光LED之發光 1313705 ， 效率通常係高於該紅光LED、及該綠光LED之發光效率， 所以，内含該等LED晶片之白光LED元件所發射出之白 光儘具有較差之演色性。 為了克服上述之缺點，日亞化學(Nichia Chemical)提出 -種内含單-LED晶片及—螢絲之白光LED元件，該 勞光粉之化學式為（Ylp_q_rGdpce£}smr)3(A1]SGas)50l2，其 • 中’ P係介於0及〇·8之間、q係介於0.0〇3及0.2之間、r 係介於0.0003及0 08之間、而s係介於〇及1之間。該單 一 LED晶片可發射一激發光而該螢光粉係滲雜於一用來 覆蓋該單[ED晶片之環氧樹脂(ep〇Xy resin)内、並藉由 吸收β亥單—LED晶片所發射之激發光中具有一預定波長之 預定激發光之方式、激發出一發射光。如此一來，該單一 LED晶片所發射之除了該預定激發光以外之激發光與該螢 鲁光粉所激發之發射域可混合成該白光。 由於僅包含該單一 led晶片、及已屬成熟產品故相當 便且之螢光粉，所以，日亞化學所提出之白光LED元件之 ' 製作成本相當低廉。 然而’可用來配合該單一 LED晶片以形成該白光led 干之螢光粉之化學式並不僅限於 (Yi-P-q-rGdpCeqSmr)3(Al】—sGas)5012 -種。 1313705 【發明内容】 因此本發日狀主要目的在於提供—種led元件及相關 螢光粉與製備方法，該LED元件係包含單_ LED晶片及 其化學式係異於(γ—GdpCeqSmf)機_sGas)5C)i2之榮光 粉。 本發明係揭露一種發光二極體元件，其包含一發光晶 片，用來發射一激發光；以及—榮光粉，用來吸收該發光 晶片所發出之部分激糾，並據以激發出波長異於該激發 光波長之第一發射光，該螢光粉之化學式為 (Cai_x-yEuxMy)Se ’其中x係不等於零、y係介於零與壹之 間，而Μ包含鈹(Be)、鎂(Mg)、鳃(Sr)、鋇(Ba)或鋅(zn)。 【實施方式】 請參閱第1圖，第1圖為本發明之較佳實施例中一白光 led元件10之示意圖，元件10可發射一白光LwH。元件 10包含一杯狀殼體12、一設置於杯狀殼體12底部用來發 射激發光lled之LED晶片14、一填充於杯狀殼體12内 用來覆蓋LED晶片14之環氧樹脂(epoxy resin)i6、以及滲 雜於環氧樹脂16内之螢光粉18。螢光粉18可吸收lED晶 片14所發出之部分激發光lled、並據以激發出一發射光 pH〇其中’發射光Lpho之波長係相異於激發光Lled之波長。 1313705 本發明雖然以發射出白光Lwh之元件10作為實施例， 然而’任何發射出以白光LWH為主之光線的LEO元件皆屬 本發明之範_。 在本發明之較佳實施例中，LED晶片14所發射之激發 光 Llee> 之主波長（domination wavelength)係介於 440 至 510 奈米（nanometer)之間，換言之，LED晶片14所發射之激發 光Lled之顏色係介於藍色及綠色之間；螢光粉a之化學 式為（Cabx—yEuJV^Se，其中X係不等於0、y係介於〇與i 之間、而Μ係至少一種以上選自鈹(Be)、鎂（Mg)、锶（sr)、 鋇（Ba)、鋅（Zn)等之元素，μ可以使用一種或一種以上之上 述元素。螢光粉18可吸收LED晶片14所發射之藍光（或 綠光)Lled、並據以激發出其顏色為橘色之發射光LpHO，其 中’ CaSe係充作一主體晶格結構(host)、而Eu、Μ係充作 摻雜(doPing)於該主體晶格結構内之異離子（foreign i〇ns)， 5亥異離子可被結合（inc〇rp〇rated)併入該主體晶格結構内以 形成可激發出發射光LPH0之活化者（activator)。 如此一來’由於LED晶片14所發射之除了被吸收的激 發光 Lled 以外之激發光Lled與螢光粉18所激發出之發射 光LPHO可混合成白光lwh，所以，等效上，元件1 〇可發 射白光 LWh、其色溫（c〇i〇r temperature)約等於 3018K。 1313705 在本發明之較佳實施例中，並了提昇白光lwh之演色性 與均勻性，螢光粉18之粒徑(particle size)係小於20微米 (micrometer)、而其平均粒徑係約等於5微米。 請參閱第2圖至第4圖。第2圖為螢光粉18的激發光 Lex及其所激發出之發射光LPH0之頻譜分佈圖，其中，橫 軸表示激發光LEX&發射光LPHO之波長、縱軸表示激發光 | LEX及發射光LPH0之相對強度、而螢光粉18之化學式中之 X係等於0.005、y係等於0 ;第3圖為元件1〇所發射之白 光LWH之頻譜分佈圖，其中，橫軸表示白光LWH之波長、 縱轴表不白光L^h之相對強度，弟4圖為包含LED晶片 14之激發光Lled、榮光粉18之發射光Lph〇、本發明之白 光LWH、及一真正（genuine)白光LWhg所分別對應之色品座 標值（CIE chromaticity coordinates)之 CIE 色品座標圖（cig chromaticity diagram)，其中’橫軸表示X色品座標、縱轴 .表示 y 色品座標、而 Α(0·0690，0.5483)、B(0.6154，0.3790)、 C(0.4486，0.4307)、及D(0.31 ’ 0.32)四點分別表示其波長 為500奈米之激發光Lled、 被其波長為500奈米之激發光 Lled所激發出之發射光Lpho、由其波長為500奈米之激發 光lled及其所激發出之發射光lpho混合而成之白光lwh、 以及真正白光LWHG所對應之色品座標。 在本發明之較佳實施例中’螢光粉18可選擇性地藉由1313705 IX. Description of the Invention: [Technical Field] The present invention relates to a light-emitting diode (LED), especially a phosphor containing a chemical formula (Cai x yEUxMy) Se Light-emitting diode elements and related phosphor powders and preparation methods. [Prior Art] Due to its low power consumption, long life (about ten times that of traditional fluorescent lamps), and most importantly, color rendering index (CRI) and electromagnetic radiation that can cause damage to art objects (visible Radiation and other 'white-light LED' components have gradually become a popular lighting component in the most popular market, especially for high-end markets with special requirements for color rendering. One of the most intuitive ways to make a white LED component is to combine three blue, red, and green blue (9) enamel, red_light, and green-light LED chips. It is formed to form the white light lED element. In this way, the white LED element can emit white light mixed by the blue light, the red light, and the green light. However, since it is necessary to include three LED chips, the above-described three-in-one white LED element is relatively expensive to manufacture. In addition, since the luminous efficiencies of the LEDs are not the same, in particular, the illuminance of the blue LEDs 1313705 is generally higher than that of the red LEDs and the green LEDs, and therefore, the LEDs are included. The white light emitted by the white LED component of the wafer has poor color rendering. In order to overcome the above shortcomings, Nichia Chemical has proposed a single-LED wafer and a white LED component of the filament, the chemical formula of which is (Ylp_q_rGdpce£}smr)3(A1]SGas) 50l2, where • 'P is between 0 and 〇8, q is between 0.0〇3 and 0.2, r is between 0.0003 and 0 08, and s is between 〇 and 1. between. The single LED chip can emit an excitation light and the phosphor powder is immersed in an epoxy resin (ep〇Xy resin) for covering the single [ED wafer], and by absorbing β海单单-LED wafer A predetermined excitation light having a predetermined wavelength is emitted from the emitted excitation light to excite an emitted light. In this way, the excitation light emitted by the single LED chip except the predetermined excitation light and the emission field excited by the phosphor powder can be mixed into the white light. Because it only contains the single led chip and the fluorescent powder which is already a mature product, the white LED component proposed by Nichia Chemical Co., Ltd. is relatively inexpensive to manufacture. However, the chemical formula that can be used to match the single LED wafer to form the white light LED dry phosphor is not limited to (Yi-P-q-rGdpCeqSmr)3(Al)-sGas) 5012. 1313705 [Summary of the Invention] Therefore, the main purpose of the present invention is to provide a LED element and a related fluorescent powder and a preparation method thereof, the LED element comprising a single-LED wafer and its chemical formula is different from (γ-GdpCeqSmf) machine_sGas ) 5C) i2 glory powder. The present invention discloses a light-emitting diode element comprising a light-emitting chip for emitting an excitation light, and a glory powder for absorbing a part of the excitation light emitted by the light-emitting chip, and thereby exciting a wavelength difference The first emitted light of the excitation light wavelength, the chemical formula of the fluorescent powder is (Cai_x-yEuxMy)Se 'where x is not equal to zero, the y is between zero and 壹, and Μ contains beryllium (Be), magnesium ( Mg), strontium (Sr), barium (Ba) or zinc (zn). [Embodiment] Please refer to Fig. 1. Fig. 1 is a schematic view of a white LED element 10 in accordance with a preferred embodiment of the present invention. Element 10 can emit a white light LwH. The component 10 includes a cup-shaped casing 12, an LED chip 14 disposed at the bottom of the cup-shaped casing 12 for emitting the excitation light lled, and an epoxy resin filled in the cup-shaped casing 12 for covering the LED chip 14. Resin) i6, and phosphor powder 18 impregnated in epoxy resin 16. The phosphor powder 18 absorbs a portion of the excitation light lled from the lED wafer 14, and thereby excites an emission light pH 〇 where the wavelength of the emitted light Lpho is different from the wavelength of the excitation light Lled. 1313705 Although the present invention has an element 10 for emitting white light Lwh as an embodiment, any LEO element that emits light mainly based on white light LWH is an embodiment of the present invention. In a preferred embodiment of the invention, the domination wavelength of the excitation light Llee > emitted by the LED wafer 14 is between 440 and 510 nanometers, in other words, the excitation of the LED chip 14 is emitted. The color of light Lled is between blue and green; the chemical formula of fluorescent powder a is (Cabx-yEuJV^Se, where X is not equal to 0, y is between 〇 and i, and at least one is The above elements are selected from the group consisting of beryllium (Be), magnesium (Mg), strontium (sr), barium (Ba), zinc (Zn), etc., and one or more of the above elements may be used for μ. The phosphor powder 18 can absorb the LED chip. 14 emitted blue light (or green light) Lled, and according to the emission of orange color LpHO, where 'CaSe is used as a host lattice structure (host), while Eu, lanthanum is used for doping Doping (foreign i〇ns) in the host lattice structure, 5 hex ions can be incorporated (inc〇rp〇rated) into the host lattice structure to form an excitable emission light LPH0 The activator. As a result, the excitation light Lle emitted by the LED chip 14 is absorbed. The excitation light Lled other than d and the emission light LPHO excited by the phosphor powder 18 can be mixed into white light lwh, so, equivalently, the element 1 〇 can emit white light LWh, and its color temperature (c〇i〇r temperature) is approximately equal to 3018K. 1313705 In the preferred embodiment of the present invention, the color rendering and uniformity of the white light lwh are improved, and the particle size of the phosphor powder 18 is less than 20 micrometers, and the average particle size thereof is It is approximately equal to 5 μm. Please refer to Fig. 2 to Fig. 4. Fig. 2 is a spectrum distribution diagram of the excitation light Lex of the phosphor powder 18 and the emitted light LPH0 excited by the phosphor powder 18, wherein the horizontal axis represents the excitation light LEX& The wavelength of the emitted light LPHO, the vertical axis represents the relative intensity of the excitation light | LEX and the emitted light LPH0, and the X of the chemical formula of the fluorescent powder 18 is equal to 0.005, and the y system is equal to 0; FIG. 3 is the emission of the element 1〇 A spectrum distribution diagram of white light LWH, wherein the horizontal axis represents the wavelength of the white light LWH, and the vertical axis represents the relative intensity of the white light L^h, and the middle view 4 shows the excitation light Lled of the LED chip 14 and the emitted light Lph of the glory powder 18 , the white light LWH of the present invention, and a real white light LWhg Corresponding CIE chromaticity coordinates CIE chromaticity diagram, where 'horizontal axis indicates X chromaticity coordinates, vertical axis. indicates y chromaticity coordinates, and Α (0·0690, 0.5483) ), B (0.6154, 0.3790), C (0.4486, 0.4307), and D (0.31 '0.32) indicate the excitation light Lled with a wavelength of 500 nm and the excitation light Lled with a wavelength of 500 nm. The emitted light Lpho, the white light lwh mixed by the excitation light lled having a wavelength of 500 nm and the emitted light lpho, and the chromaticity coordinates corresponding to the true white light LWHG. In a preferred embodiment of the invention, the phosphor powder 18 is selectively