本文關(guān)鍵詞：可見光長余輝材料的設(shè)計合成及其余輝特性的研究　出處：《蘭州大學(xué)》2016年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 長余輝 陷阱 熱釋光

【摘要】：長余輝發(fā)光材料因其在弱光緊急照明等領(lǐng)域的廣泛應(yīng)用而受到人們關(guān)注。隨著長余輝材料的不斷發(fā)展,人們對長余輝材料的余輝性能及顏色提出更高的要求。同時長余輝發(fā)光機理尚未取得共識。針對上述問題,設(shè)計合成了多種可見光長余輝材料,并系統(tǒng)研究其發(fā)光、余輝特性。本論文主要涉及以下幾個方面內(nèi)容:一.采用分離陷阱中心和發(fā)光中心在不同基質(zhì),利用Ca Al2O4:Eu2+,Nd3+(CA)優(yōu)越的儲能能力和Y3Al5O12:Ce3+(YAG)高效的黃光發(fā)射的特點,制備了CA/YAG復(fù)合長余輝材料,通過輻射能量傳遞方式實現(xiàn)了余輝顏色從藍到黃可調(diào),復(fù)合樣品的余輝時間較純CA的有很大提高,由原來的19h達到48h,提高到原來的2.8倍。復(fù)合樣品的余輝初始亮度也得到提高,達到3200 mcd/m2,提高到原來的2.7倍,復(fù)合樣品余輝性能提高可能是YAG的500nm到700nm的寬帶發(fā)射光激勵CA中的深陷阱,使其釋放深陷阱中的載流子,與熱擾動下釋放的載流子共同對余輝起作用。同時,YAG把CA發(fā)出的藍光轉(zhuǎn)換為黃光時,雖然輻射量Φe(λ)降低,但是由于黃光的光視效率V(λ)要比藍光的要高很多,綜合的結(jié)果就是復(fù)合樣品的余輝亮度提高,余輝時間增長。采用該方法制備的白色長余輝材料余輝時間達到45h,克服三基色復(fù)合得到白色長余輝材料要求衰減、強度和激發(fā)波長一致的兩個難點。二.單一基質(zhì)余輝可調(diào):采用高溫固相法制備了藍色到白色可調(diào)的新型長余輝材料(Ca0.65-xSr0.35-x)7(Si O3)6Cl2:Eu3+x,Tm3+x(0.01≤x≤0.08),獲得藍色長余輝材料余輝時間達27h,初始亮度1275mcd/m2。白色余輝材料余輝時間超過22h,比目前最長的白色余輝Cd Si O3:Dy3+要長17h。熱釋光曲線表明共摻Tm3+后引入了三個深度不同深度的陷阱中心,分別由Tm3+替代不同格位上的陽離子所產(chǎn)生的缺陷聚集而成,即:[Tm·sr],[Tm·Ca-Tm·sr],[Tm·Ca]。通過分析衰減不同時間熱釋光曲線表明,[Tm·sr],對余輝起主導(dǎo)作用,[Tm·Ca-Tm·sr]和[Tm·Ca]在室溫下難以釋放。通過研究不同溫度下的余輝光譜,證明陷阱的非隨機分布。由于[Tm·sr]離Eu1近,更易捕獲來自Eu1的電子,[Tm·Ca-Tm·sr]離Eu2近,所以易捕獲Eu2的電子。[Tm·Ca]離兩個發(fā)光中心的距離相當(dāng),所以捕獲概率相差不大。對比不同激發(fā)源下的熱釋光曲線表明,254nm激發(fā)下,電子被激發(fā)到導(dǎo)帶,然后,電子再被陷阱捕獲。365nm激發(fā)下,電子被激發(fā)到Eu2+激發(fā)態(tài),隨后直接通過遂穿到陷阱能級。三.開發(fā)了新型藍色長余輝材料Ca3Al2O6:Ce3+、綠色長余輝材料Sr3Al2O5Cl2:Tb3+、黃色長余輝材料Ba3P4O13:Eu2+,Ga3+、橙色長余輝材料Ca3Si O4Cl2:Eu2+,R3+(R=Dy,Ce,Nd)、紅色長余輝材料Ca4(PO4)2O:Eu2+,R3+(R=Y,Tm,Ce,Gd,La,Lu),拓寬了基質(zhì)和激活劑的選擇。合成了Ce3+摻雜的Ca3Al2O6的系列樣品,發(fā)射光譜為400nm到600nm的非對稱寬帶發(fā)射,發(fā)射主峰在485nm,歸屬于Ce3+占據(jù)Ca3Al2O6中2個不同Ca離子格位所引起5d→4f躍遷發(fā)射。熱釋光曲線表明33℃的熱釋峰所對應(yīng)的陷阱對長余輝有直接的關(guān)系。合成了綠色長余輝材料Sr3Al2O5Cl2:Tb3+,最佳余輝時間達1h。通過改變激發(fā)時間,發(fā)現(xiàn)綠色長余輝材料Sr3Al2O5Cl2:Tb3+中不同深度陷阱的填充規(guī)律。在黃色長余輝材料Ba3P4O13:Eu2+發(fā)現(xiàn)共摻非稀土Ga3+對余輝性能提升起重要作用,余輝時間達8.5h,而共摻稀土離子并不能有效提高余輝性能,甚至反而降低了余輝時間。該研究拓展了共摻離子的選擇。開發(fā)了新型近橙色長余輝發(fā)光材料Ca3Si O4Cl2:Eu2+,R3+(R=Dy,Ce,Nd)。系列樣品在380nm激發(fā)下呈現(xiàn)主峰在615nm的一個寬帶發(fā)射。單摻Eu2+樣品余輝只有2min,共摻稀土離子Dy,Ce,Nd使得樣品余輝性能提高,效果最好的是共摻Dy,余輝時間達到40min。合成了新型近紅外長余輝發(fā)光材料Ca4(PO4)2O:Eu2+,R3+(R=Y,Tm,Ce,Gd,La,Lu)。系列樣品在467nm激發(fā)下呈現(xiàn)主峰在690nm的一個寬帶發(fā)射。共摻稀土離子Y,Tm,Ce,Gd,La,Lu均有余輝,Eu2+,Y3+共摻的余輝時間最長,可達2h。這種新型的紅長余輝發(fā)光材料拓寬了基質(zhì)和激活劑的選擇。
[Abstract]:Long afterglow materials attracted attention because of the wide application in the weak light of emergency lighting and other fields. With the continuous development of long afterglow materials, afterglow properties and color of long afterglow materials put forward higher requirements. At the same time long afterglow mechanism has not yet been agreed. Aiming at the above problems, the design and synthesis of a variety of visible light long afterglow materials, and systematically study the light, afterglow characteristics. This paper mainly involves the following several aspects: 1. The separation of trap center and luminescence centers in different matrix, using Ca Al2O4:Eu2+ Nd3+ (CA) superior energy storage capacity and Y3Al5O12:Ce3+ (YAG), yellow light emission characteristics of CA/YAG composite the afterglow materials were prepared, the afterglow color from blue to yellow can be adjusted by radiation energy transfer, afterglow time of composite samples was higher than pure CA has greatly improved, from 19h to 48h, improve To the original 2.8 times. The afterglow initial brightness composite sample is also improved, reached 3200 mcd/m2, increased to 2.7 times the original, composite luminescent performance improvement may be YAG to 700nm 500nm broadband emission light excitation deep traps in CA, the release of carriers in deep traps, and the release of heat carrier disturbance under the common role of Yu Huiqi. At the same time, YAG put the blue light from the CA converted to yellow light, although the amount of radiation with E (lambda) decreased, but due to the yellow light luminous efficiency V (lambda) to be much higher than the blue, comprehensive is the result of the composite sample to improve the brightness, afterglow time growth. The preparation method of the white long afterglow afterglow time reached 45h, overcome three color composite white long afterglow materials require attenuation, intensity and excitation wavelength of two points consistent. Two. Single matrix afterglow adjustable: the high temperature solid phase method Blue to white adjustable new long afterglow materials were prepared (Ca0.65-xSr0.35-x) 7 (Si O3) 6Cl2:Eu3+x, Tm3+x (x = 0.01 ~ 0.08), get the blue long afterglow materials afterglow time of 27h, the initial brightness white 1275mcd/m2. afterglow afterglow time is more than 22h, than the long white Cd Si O3:Dy3+ long afterglow 17h. thermoluminescence curves show that Co doped Tm3+ after the introduction of the three depth of trap center, shortcomings were replaced by Tm3+ cation on different sites have gathered together, namely: [Tm, sr], [Tm, Ca-Tm, sr], [Tm and Ca].. Through the analysis of different attenuation time thermoluminescence curves show that [Tm, sr], the leading role of Yu Huiqi, [Tm Ca-Tm sr] and [Tm Ca] to release at room temperature. Through the study of afterglow spectra under different temperatures, non random distribution of proof trap. Because the [Tm sr] near Eu1, more easily capture electrons from Eu1, [Tm Ca-Tm. Sr] closer to Eu2, so easy to capture Eu2.[Tm Ca] from the two electronic luminescence center distance, so the capture probability difference. Comparing the different excitation sources under the thermoluminescence curves show that under 254nm excitation, electrons are excited into the conduction band, then, is electron trap under the excitation of.365nm, electrons are excited to the Eu2+ excited state, followed by tunneling to trap energy directly. Three. The development of a new type of blue long afterglow materials Ca3Al2O6:Ce3+, Sr3Al2O5Cl2:Tb3+ yellow green long afterglow materials, long afterglow materials Ba3P4O13:Eu2+, Ga3+, orange long afterglow phosphor Ca3Si O4Cl2:Eu2+, R3+ (R=Dy, Ce, Nd), red phosphor Ca4 (PO4) 2O:Eu2+, R3+ (R=Y, Tm, Ce, Gd, La, Lu), broaden the substrate and activator. The samples with Ce3+ doped Ca3Al2O6 was synthesized, the emission of 400nm to asymmetric broadband 600nm, emission peak at 485nm, belonging to Ce3+ occupy C A3Al2O6 in 2 different Ca ion site caused by emission 5D to 4f transition. The thermoluminescence curve shows that 33 degrees of pyroelectric peaks corresponding to the trap has a direct bearing on the long afterglow. Green long afterglow phosphor Sr3Al2O5Cl2:Tb3+ was synthesized, the best afterglow time of 1h. by changing the excitation time, the different depth of trap green long afterglow in Sr3Al2O5Cl2:Tb3+ filling rule. Found Co doped rare earth Ga3+ on non afterglow properties play an important role in the promotion of yellow long afterglow phosphor Ba3P4O13:Eu2+, afterglow time of 8.5H and Co doped rare earth ions and can effectively improve the afterglow properties, but reduces the afterglow time. Even the study extends the selection of doped metal ions. The development of the a new near orange phosphor Ca3Si O4Cl2:Eu2+, R3+ (R=Dy, Ce, Nd). A series of samples showed a peak in the broadband 615nm emission under the excitation of 380nm doped Eu2+ samples. Only Yu Hui 2min, Co doped rare earth ions Dy, Ce, Nd improves the luminescent performance, is the best effect of Co doped Dy, the afterglow time reached 40min. synthesis of new near infrared luminescent materials Ca4 (PO4) 2O:Eu2+, R3+ (R=Y, Tm, Ce, Gd, La, Lu). A series of samples showing peak in a broadband 690nm emission in 467nm Co doped rare earth ions under excitation. Y, Tm, Ce, Gd, La, Eu2+, Lu have the afterglow, the afterglow time of Y3+ Co doped 2h. was the longest, the red long afterglow luminescent material model broadens the matrix and activator.

【學(xué)位授予單位】：蘭州大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：O482.31

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