【摘要】： 稀土釩酸鹽、硼酸鹽因其在紫外和真空紫外區(qū)有很好的透明性及較強(qiáng)的吸收并能將能量有效地傳遞給激活離子,因此被廣泛地應(yīng)用于光學(xué)、電學(xué)、磁學(xué)等領(lǐng)域。但是,此前該類材料主要采用高溫固相法來生產(chǎn),由于污染嚴(yán)重,投入過高,制備復(fù)雜,熒光粉粒徑較大,形狀難以控制等大大影響了該類熒光粉的商業(yè)應(yīng)用,已經(jīng)越來越不適應(yīng)當(dāng)前社會節(jié)能環(huán)保的需求。尋找污染程度低,造價(jià)低廉,產(chǎn)品發(fā)光性能優(yōu)良的制備方法已經(jīng)成為當(dāng)前發(fā)光材料工業(yè)的主流。熔鹽法(MSS)是近年來發(fā)展較快的一種新型粉體合成工藝,能耗較低,因此在熒光粉的生產(chǎn)領(lǐng)域受到廣泛關(guān)注。如果將熔鹽技術(shù)應(yīng)用到上述材料的合成中,必將取得較好的經(jīng)濟(jì)價(jià)值和社會效益。 本文采用熔鹽法,利用氯鹽或硝酸鹽作為熔鹽合成出了發(fā)光性能優(yōu)異、結(jié)晶性良好的稀土釩酸鹽(YVO4:Eu3+、YVO4:Sm3+、YVO4:Dy3+、YVO4:Dy3+/Tm3+)及硼酸鹽(YBO3:Eu3+、YBO3:Tb3+)熒光材料,合成粉體粒徑均一,平均粒徑在幾百納米左右。具體研究結(jié)果如下： 1、利用氯鹽、硝酸鹽作為熔鹽體系,成功地合成了鋯石結(jié)構(gòu)的YVO4:Eu3+、YVO4:Sm3+、YVO4:Dy3+、YVO4:Dy3+/Tm3+熒光粉。合成的樣品在紫外線照射下,均發(fā)射出摻雜稀土離子的特征發(fā)射,樣品YVO4:Eu3+發(fā)射峰位對應(yīng)于Eu3+的5D0→7Fn(n=0,1,2,3,4)躍遷。其中5D0→7F2躍遷發(fā)射峰為最強(qiáng)發(fā)射峰,粉體平均粒徑為150 nm左右。在YVO4:Eu3+體系中通過Bi3+取代部分Y3+,實(shí)現(xiàn)了發(fā)射峰位強(qiáng)度的調(diào)控。 2、YVO4:Sm3+也能產(chǎn)生Sm3+的特征發(fā)射,但是與其它報(bào)道的摻Sm3+發(fā)光材料相比,熔鹽法合成樣品位于647 nm處Sm3+的4G5/2→6H9/2發(fā)射得到明顯加強(qiáng),從而使得樣品發(fā)出明亮的紅光,而不是通常的橙色光。當(dāng)以硝酸鹽作為熔鹽體系時(shí),最佳合成工藝參數(shù)為：摻雜濃度為1%；保溫溫度為500℃；保溫時(shí)間為5個(gè)小時(shí)。 3、以硝酸鈉作為熔鹽成功地合成了YVO4:Dy3+黃色熒光材料；在此基礎(chǔ)之上通過引入Tm3+合成了YVO4:Dy3+/Tm3+白色熒光材料,并通過調(diào)節(jié)Dy3+/Tm3+的摻雜濃度比例實(shí)現(xiàn)了對材料發(fā)光色度坐標(biāo)的調(diào)控。 4、利用硝酸鹽作為熔鹽體系,成功地合成了六方結(jié)構(gòu)的YBO3:Eu3+、YBO3:Tb3+熒光粉。熒光光譜(PL)分析結(jié)果表明,樣品產(chǎn)生了稀土離子的特征發(fā)射,紅色熒光粉YBO3:Eu3+發(fā)射峰對應(yīng)于Eu3+的5D0→7F1,5D0→7F2躍遷,其中5D0→7F1躍遷略強(qiáng)于5D0→7F2；黃綠色熒光粉YBO3:Tb3+發(fā)射峰位對應(yīng)于Tb3+的5D4→7Fn(n=3,4,5,6)躍遷。其中5D4→7F5躍遷的發(fā)射峰處于主導(dǎo)地位,其他的躍遷表現(xiàn)為相對弱的譜線。 本論文的研究工作為采用熔鹽法合成稀土摻雜熒光材料,提供了一定的理論和工藝支持。
[Abstract]:Rare earth vanadates and borates are widely used in optical, electrical, magnetic and other fields because of their good transparency and strong absorption in the ultraviolet and vacuum ultraviolet regions and the efficient transfer of energy to active ions. However, because of the serious pollution, high investment, complex preparation, large particle size and difficult to control the shape of this kind of phosphor, the commercial application of this kind of phosphor has been greatly affected by the high temperature solid phase method. Has become increasingly unsuited to the current social demand for energy conservation and environmental protection. The preparation of low pollution, low cost and excellent luminescent properties has become the mainstream of the current luminescent materials industry. Molten salt method (MSS) is a new type of powder synthesis technology, which has been developed rapidly in recent years with low energy consumption, so it has been widely concerned in the field of phosphor production. If the molten salt technology is applied to the synthesis of the above-mentioned materials, better economic and social benefits will be obtained. In this paper, rare earth vanadate (YVO4:Eu3, YVO4:Sm3, YVO4:Dy3, YVO4:Dy3 / Tm3) and borate (YBO3:Eu3, YVO4:Dy3 / Tm3) with excellent luminescence and good crystallinity were synthesized by molten salt method using chloride or nitrate as molten salt. YBO3:Tb3) fluorescent material, the particle size is uniform, the average particle size is about several hundred nanometers. The results are as follows: 1. YVO4:Eu3, YVO4:Sm3, YVO4:Dy3, YVO4:Dy3 / Tm3 phosphors with zircon structure were successfully synthesized by using chloride and nitrate as molten salt system. Under UV irradiation, the synthesized samples all emit characteristic emission of doped rare earth ions, and the peak position of YVO4:Eu3 emission corresponds to the transition of 5D0 / 7Fn (n0, 1, 2, 3, 4) of Eu3. The emission peak of 5D0 / 7F2 transition is the strongest, and the average particle size of the powder is about 150 nm. In the YVO4:Eu3 system, partial Y3 was replaced by Bi3, and the intensity of emission peak was regulated. 2. The characteristic emission of Sm3 can also be produced by YVO4 / Sm3, but compared with other reported Sm3-doped luminescent materials, the emission of 4G5/2 / 6H9/2 of Sm3 at 647 nm is significantly enhanced by molten salt synthesis, which makes the sample emit bright red light. Not the usual orange light. When nitrate is used as molten salt system, the optimum synthetic parameters are as follows: doping concentration is 1%, holding temperature is 500 鈩，

本文編號：2430541