螢光材料已廣泛被使用在日常生活中，如電視機、電漿與場發射等顯示器，以及照明用之螢光燈、發光二極體等，因此螢光材料之基礎研究與深入的探討開發，勢必將對未來人類的生活發展有莫大助益，尤其對於當下地球能源之枯竭及氣候暖化可提供緩解之道。本論文研究之內容包括探討不同過渡金屬離子(Cu、Mn、Cd)，與其摻雜量對於硫化鋅(ZnS)晶體結構、電致發光、光致發光與微結構等的影響。另外，以濺鍍與硫化等方式來製備二元螢光薄膜層(ZnS/ZnO:Mn)，其具有以紫外光激發產生白光之潛力。同時本論文亦探討奈米粒子(nanoparticles, NPs)於螢光粉領域之應用性，包括以ZnS NPs取代傳統螢光粉高溫熱處理製程之助溶劑，ZnS:Mn NPs表面披覆二氧化矽材料之光學表現，及硒化鎘(CdSe)、硫化鎘(CdS)與硫化鋅鎘(Zn1-xCdxS)等奈米粒子的粒徑分析。

由X光繞射(XRD)的結構分析可知，銅摻雜(>200ppm)所產生之CuxS析出相的確能使硫化鋅結構轉換為立方晶，藉此也可知銅於硫化鋅的固溶度約為400ppm。隨著銅摻雜量的增加，觀察到硫化鋅顆粒會逐漸成長，這是由於添加之硫化銅或CuxS析出相會於高溫熔融，因此促進了物質間的傳輸以及擴散。拉曼光譜圖的波峰變化也表示硫化鋅確實隨銅摻雜量發生晶體結構上的轉變，同時由波峰的紅移，可知銅離子的摻雜使硫化鋅晶格產生張應變，且應變量是隨摻雜量增加而增大。除了硫化鋅結構與晶格的變化外，拉曼光譜圖也顯示硫化鋅粉末中(Cu>400ppm)存在著CuxS析出相(~470cm-1)，此與電子微探儀(EPMA)、X光電子光譜儀(XPS)及採用超薄切片技術製作之穿透式電子顯微鏡(TEM)試片的觀察都相同。因此隨銅摻雜量增加(≧400ppm)，硫化鋅於可見光波段的吸收值上升，是CuxS析出物濃度增加所引起。然而雖然所有不同銅摻雜量(40-5000ppm)之硫化鋅都具有放射藍綠光之光致發光現象，但只有銅摻雜量大於200ppm的硫化鋅能在電場激發下發光，主要是因CuxS析出物能於電場下提供激發活化中心所需的載子。

藉由添加錳與鎘離子於上述之硫化鋅銅(ZnS:Cu,Cl)粉末中，可產生化學式為ZnS:Cu,Mn,Cl與 Zn1-xCdxS:Cu,Cl(x=0-0.9)之不同顏色的電致發光螢光粉，研究發現錳離子與鎘離子(x≧0.2)的添加，反而都促使硫化鋅銅的晶體結構轉換為六方晶，不同濃度銅離子(40-104ppm)的添加也無法改變此類合金之晶體結構，亦即其結構都仍保持為六方晶，表示錳與鎘離子的添加將提高硫化鋅晶體結構轉換所需的能量(△Ghex.→cub.)，造成CuxS析出時所釋放的熱量(△HCuxS)無法轉換硫化鋅晶格。掺錳與銅之硫化鋅(Cu:400ppm, Mn/Cu=7、14)的光致發光波峰位於583nm，而掺銅與鎘之硫化鋅(Zn1-xCdxS:Cu,Cl)的光致發光，當鎘摻雜量(x)為0.6與0.7時，光致發光譜圖顯示其放射光波峰已位於紅光波段(614nm與660nm)。另外，掺錳與鎘之硫化鋅銅都具有電致發光現象，此表示試片中的確含有CuxS析出相，但卻無法使硫化鋅產生晶體結構上的轉換。

以射頻濺渡法製作之ZnO:Mn螢光層包含兩放射光波峰，一為位於大約400nm之近能帶邊緣放射光，另ㄧ為由錳離子4T1(4G)→6A1(6S)躍遷所產生之藍光(465nm)。經三十小時的硫化可將厚度約450nm之ZnO:Mn螢光層轉換為顆粒狀的ZnS:Mn，其光致發光波峰位置則由465nm紅移至573nm，這是由於錳離子之4T1(4G)→6A1(6S)躍遷能量(△E)受主體材料的結晶場強度影響。經由其光致發光譜圖的能量分佈計算可知，ZnO:Mn的色度座標位於(0.13,0.06)，ZnS:Mn則位於(0.46,0.54)，兩者連線將通過色度坐標圖上的白光區域，表示此二元螢光材料(ZnS/ZnO:Mn)可藉由其厚度控制來混成白光。

以化學溶液共沉法合成之ZnS NPs於TEM下顯示粒徑介於10-30nm，熱分析(DTA/TG)可發現其相轉換溫度降低至大約600oC，而熔點約在884oC，ZnS NPs之XRD圖譜亦顯示相同結果。藉由添加不同比例(0-100wt%)上述之ZnS NPs於ZnS:Mn螢光粉製程，發現1wt%之添加量能有效地提升ZnS:Mn的光致發光強度，推測這是由於ZnS NPs能在高溫熔融，因此促進發光中心(Mn2+)的擴散，而避免了濃度淬滅效應的發生。XRD與TEM顯示立方晶結構之ZnS:Mn NPs(D111~3.1nm)經四乙基矽(TEOS)等溶液反應後，能散佈在粒徑約50-100nm的無晶微顆粒中，藉由特性X光(EDS)與位於105eV之 Si L2,3電子能量損失近邊緣結構(ELNES)的分析，得知這無晶材料為SiO2。利用XRD建立之ZnS:Mn/SiO2檢量線，可知隨著ZnS:Mn NPs的添加量增加，表面的SiO2披覆量會減少。其中以添加量為2g之試片具有最佳的光致發光強度。藉由漫射實驗可知SiO2的披覆能降低ZnS:Mn NPs表面之缺陷濃度，避免能量消散在此些淬滅中心，同時也知SiO2是以化學鍵結方式披覆於ZnS:Mn NPs，並非只是物理式吸附。

CdSe NPs的LO拉曼位置分別為204.78cm-1與201.39cm-1，由聲子侷限效應可知其粒徑應分別為3.52nm與2.26nm，此結果與TEM及吸收光譜圖(UV-vis)之第一激子吸收峰的推導結果相符。另外也可由CdSe NPs之拉曼位置偏移得知試片存在著壓應力(ε<0)，而這壓應力推測是由VSe或VCd等空缺所導致的，此相同於光致發光所觀察到的寬廣放射峰。然而本實驗製備之CdS NPs的拉曼偏移量卻隨不同量測位置而改變，有的拉曼位置是介於293.97cm-1至300.69cm-1，表示其粒徑分佈在3.5nm~8nm。TEM的觀察也顯示這些奈米粒子確實存在著寬廣的粒徑分佈，就如同在光致發光與UV-vis等光譜圖所發現之寬廣與不對稱的波峰。Zn1-xCdxS合金NPs的拉曼位置除了受粒徑大小產生偏移外，同時合金的組成也會改變其位置，實驗發現合金所造成的效應大於粒徑，故導致合金NPs成長時其拉曼位置會紅移。

Phosphor materials have been widely used in solid state lighting, displays and medical imaging by doping with transition or rare-earth metals. Here we studied the influence of transition metals (Cu, Mn, Cd) on the structure and optical properties of electroluminescent ZnS powders, the preparation of two-band emission of ZnS/ZnO:Mn film for the white light usage, and the Raman properties of ZnS, CdSe, CdS and Zn1-xCdxS nanoparticles (NPs).

A series of ZnS:Cu,Cl powders with Cu additions ranging from 40 to 5000ppm were studied by firing at 750-1050oC for 2h in the atmosphere of 3%H2/Ar. X-ray diffraction (XRD) and Raman analyses showed that ZnS:Cu,Cl samples with Cu additions of ≥400ppm exhibited a structure transformation from hexagonal to cubic, which was supposed to result from the Cu incorporation or CuxS precipitation (470cm-1). The red shift of the longitudinal optical (LO) mode in ZnS:Cu,Cl with the increased Cu suggested that Cu ions entered ZnS lattice interstitially and created a tensile strain. The whole series of ZnS:Cu,Cl samples showed significant photoluminescence (PL) in the region of 400-600nm; however, only the samples with Cu additions of ≥400ppm revealed measurable electroluminescence (EL). This difference was supposed to be a result of nano-sized CuxS precipitation in ZnS during the firing treatment, where CuxS acted as the electron emission source to induce the activation of luminescent centers.

Red electroluminescent phosphor powders of ZnS:Cu,Mn,Cl and Zn1-xCdxS:Cu,Cl (x=0-0.9) were also prepared by a solid state reaction at 900oC for 2h in a reducing atmosphere. XRD showed that the structure of Zn1-xCdxS:Cu,Cl (Cu:800ppm) transformed from cubic to hexagonal as x increased to 0.2. Similarly, the addition of Mn preferred to the formation of hexagonal ZnS. This unavailability of CuxS to induce the cubic structure transformation in ZnS:Cu,Mn,Cl and Zn1-xCdxS:Cu,Cl may be due to the fact that Mn tends to bond to S in the hexagonal and Zn1-xCdxS stabilizes in a hexagonal structure. EL measurements revealed broad emission bands at 583nm and 614nm for ZnS:Cu,Mn,Cl and Zn0.4Cd0.6S:Cu,Cl, respectively.

ZnO:Mn capped with ZnS:Mn (ZnS/ZnO:Mn) phosphor layers were prepared by thermal sulfidation of ZnO:Mn films deposited on Si(100) substrate with the method of RF magnetron sputtering. The PL of the ZnS/ZnO:Mn layer showed a three-band emission, i.e. UV, blue (465nm) and orange (573nm) bands. The chromaticity coordinate of the two-component ZnS/ZnO:Mn phosphor layer, which was estimated from the peak and width of each emission band, showed the potential of producing white light emission.

PL measurements revealed that ZnS:Mn powders fired with 1wt% ZnS NPs showed the optimal luminescence intensity when compared to those without or with more ZnS NPs (>1wt%). An appropriate amount of ZnS NPs (1wt%) acting as the flux in the firing process was inferred to avoid the inhomogeneous distribution of Mn2+ as well as the migration of excitation energy to quenching sites and therefore to result in the enhanced PL intensity.

ZnS:Mn NPs (~3.1nm) of a cubic structure were prepared by a co-precipitation method and then dispersed with various weights (0.5-8g) into a solution containing ammonium hydroxide, ethanol and tetraethyl orthosilicate (TEOS) for surface coating. The optical properties of PL and diffuse reflection of the SiO2-coated ZnS:Mn powders were found to depend on the quantity of ZnS:Mn NPs in the coating solution. The increased PL intensity of ZnS:Mn at 590nm after SiO2 coating was proposed to result from the inhibition of excitation energy transfer to quenching centers or surface states based on the observation of the reduced absorption in the region of 370-450nm. CdSe, CdS and Zn1-xCdxS NPs were prepared by the TOP process and studied with a Raman spectrometer, revealing very homogeneous size distributions and comparable sizes with the transmission electron microscope (TEM) and UV-vis measurements.

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