EuPO4∶Zn@MCM-41的制备和发光性质

通过微波辅助水热法合成MCM-41介孔材料,经溶胶凝胶组装过程将EuPO₄∶Zn分散到MCM-41表面上和孔道中,制备成以MCM-41为基质的复合发光材料EuPO₄∶Zn@MCM-41粉末。通过XRD、FTIR、氮吸附、SEM、HRTEM、EDS对该材料进行了表征,用单因素法探究了原料配比(Eu(NO₃)₃、Zn(NO₃)₂的加入量和反应条件(煅烧的温度、时间)对EuPO₄∶Zn@MCM-41在593 nm处发光强度的影响,并研究其影响机理。荧光分析发现,EuPO₄∶Zn基本不发射荧光,而EuPO₄∶Zn@MCM-41材料具有蓝光段和红光段的荧光发射,主要发光带以468和593 nm为中心。593 nm处的发射归因于Eu³⁺的4f组内⁵D₀→⁷F₁跃迁,即Eu³⁺中心离子所在晶格格位对称性决定的磁偶极跃迁。研究表明以MCM-41为载体,能够大大降低颗粒的团聚程度,并使EuPO₄:Zn颗粒具有更小的粒径;同时EuPO₄∶Zn@MCM-41中Eu³⁺发光中心具有更大的裂分,MCM-41的纳米孔道使Eu³⁺的发光中心分离,降低了Eu³⁺之间电子云之间的重叠,大大减小了荧光的猝灭,因此MCM-41能有效降低Eu³⁺复合物荧光猝灭。     

白光LED用KCaPO4:Eu3+红色荧光粉制备及其发光特性

采用高温固相法制备了KCaPO4:Eu3+红色发光材料,研究了Eu3+掺杂浓度、电荷补偿剂等对材料发光性质的影响.结果显示,在397 nm近紫外光激发下,材料呈多峰发射,分别由Eu3+的5D0→7FJ(J=0,1,2,3,4)能级跃迁产生,主峰为613 nm;监测613 nm发射峰,所得激发光谱由O2-→Eu3+电荷迁移带(200～350 nm)和f-f高能级跃迁吸收带(350～450 nm)组成,主峰为397 nm.Eu3+离子的最佳掺杂浓度为5%(摩尔分数);浓度猝灭机制为电偶极-电偶极相互作用.添加电荷补偿剂Li+,Na+,K+或Cl-后,可提高KCaPO4:Eu3+材料的发射强度,其中以添加Li+时,效果最明显.     

CaMoO4∶Eu3+发光材料的制备和发光性质的研究

用共沉淀法与高温焙烧法制备了样品CaMoO4:Eu3+.TG-DTA谱图表明:800℃时,样品吸收的能量最大,即形成稳定的CaMoO4:Eu3+结构.用XRD谱图进一步分析表明:800℃时,样品CaMoO4:Eu3+已形成CaMoO4的白钨矿结构.由于2个Eu3+取代3个Ca2+,导致了晶体产生微小的晶体缺陷,从而形成具有p-n结的半导体.经过激发和发射谱图的测试发现:这种缺陷结构不但可以使Eu3+禁戒的4f电子发生跃迁,而且可以使MoO42-的能量高效地传递给Eu3+.尤其使与MoO42-的发射特征峰(488 nm)部分重叠的Eu3+(465 nm)的7F0→5D2电子跃迁得到了极大的加强,进而在λex=465 nm的发射谱图中,自激活荧光体MoO42-的发射强度被大大减弱甚至猝灭,而Eu3+的5D0→7F2(612 nm)跃迁的红光发光强度被大大增强,使该材料成为有潜在应用价值的发光材料.     

Ag@YF3∶Eu3+核壳结构纳米材料的制备与性能研究

采用乙二醇法制备了单质Ag纳米粒子,并通过直接沉淀法合成了均匀球形的Ag@YF3:Eu3+核壳结构复合纳米发光粒子,对产物的结构和性能进行了表征.XRD分析表明:Ag表面包覆上了结晶良好的正交晶系的YF3:Eu3+.TEM照片表明:所得的纳米复合粒子具有明显的核壳结构和均匀的球形,中间Ag粒子的尺寸在80～100 nm之间,Ag@YF3:Eu3+的粒径尺寸约为150～180 nm,表面粗糙且包覆完全.电子衍射表明复合样品为多晶.荧光光谱表明:该纳米复合粒子具有良好的发光性,以593 nm附近的5D0→7F1磁偶极跃迁为最强发射峰,但是比纯的YF3∶Eu3+的发光强度要弱,其荧光寿命有所增强,这表明Ag纳米粒子对外层的YF3:Eu3+的发光有猝灭作用.     

喹吖啶酮衍生物/介孔分子筛MCM-41组装体的金属离子传感性能研究

将5,12-二［6-(2-氨基乙基氨基)己基］ 喹吖啶酮(BAEAHQA)组装到介孔分子筛MCM-41的孔道中,制备了金属离子传感材料BEDAHQA /MCM-41. 荧光光谱显示组装体的发光避免了喹吖啶酮固体发光的浓度猝灭现象. 引入不同的金属离子将使BAEAHQA/MCM-41的荧光光谱强度发生不同程度的降低和峰位移动. 尤其是金属钴离子可以使BAEAHQA/MCM-41的发光产生明显的猝灭,猝灭程度可达到92.63％. 通过引入乙二氨基团BAEAHQA达到了发光基团与螯合基团之间的分离,有效地避免了pH值对发光的影响. 实验结果表明,BAEAHQA/MCM-41对于金属离子具有良好的传感特性.     

Ag@YF3:Eu3+核壳结构纳米材料的制备与性能研究

采用乙二醇法制备了单质Ag纳米粒子,并通过直接沉淀法合成了均匀球形的Ag@YF3∶Eu3+核壳结构复合纳米发光粒子,对产物的结构和性能进行了表征。XRD分析表明:Ag表面包覆上了结晶良好的正交晶系的YF3∶Eu3+。TEM照片表明:所得的纳米复合粒子具有明显的核壳结构和均匀的球形,中间Ag粒子的尺寸在80~100 nm之间,Ag@YF3∶Eu3+的粒径尺寸约为150~180 nm,表面粗糙且包覆完全。电子衍射表明复合样品为多晶。荧光光谱表明:该纳米复合粒子具有良好的发光性,以593 nm附近的5D0→7F1磁偶极跃迁为最强发射峰,但是比纯的YF3∶Eu3+的发光强度要弱,其荧光寿命有所增强,这表明Ag纳米粒子对外层的YF3∶Eu3+的发光有猝灭作用。     

Sr2CeO4:Eu,Gd的微波合成与荧光性质

用微波法合成了Gd3 和Eu3 共掺杂的Sr2CeO4荧光体.Gd3 对Sr2CeO4:Eu的发光起不同的作用:当Eu3 浓度较低(掺杂浓度为1 mol%)时,Gd3 离子起猝灭作用;当Eu3 浓度较高(掺杂浓度为8 mol%)时,Gd3 离子起敏化作用,尤其是Gd3 离子掺杂浓度为3 mol%时,Eu3 的5D0→7F2(614 nm)跃迁发射增强为Sr2CeO4:Eu荧光强度的145%.     

棒状LaF3∶Eu3+纳米晶的制备与发光性能

采用一种简单的液相反应法在室温下合成了棒状的LaF3∶Eu3+纳米晶, 对其结构和发光性能进行了表征. XRD分析结果表明, 室温下即可得到结晶良好的六方晶相的LaF3, 灼烧之后样品的衍射峰增强, 没有杂相产生. TEM照片表明, 棒状LaF3∶Eu3+纳米材料的直径为8 nm左右, 长度达到50 nm. 荧光光谱表明, 室温下合成的棒状LaF3∶Eu3+纳米晶的最强发射峰位于589 nm, 对应于Eu3+的5D0-7F1跃迁发射, 说明Eu3+占据LaF3基质中La3+晶格点的C2对称格位上. 同时Eu3+的猝灭摩尔分数为5%, 荧光寿命随着灼烧温度的升高而延长.     

红色发光长余辉材料Ca2SnO4:Eu3+的性能研究

利用高温固相法合成了Ca2nO4:Eu3+色发射长余辉发光材料,对样品进行了X射线衍射分析、荧光光谱分析、形貌分析以及发光寿命测量.分析结果表明,在1350℃下烧结3 h的Ca2SnO4:Eu3+为单相产物,所得Ca2SnO4:Eu3+发光材料具有良好的发光性能,在267 nm紫外线激发下发出最强发射位于617 nm的锐线发射,并且具有明显的长余辉发光性能.     

LED用Sr_((1-1.5x))Mo_(0.8)Si_(0.2)O_(3.8)∶Eu_x~(3+)红色荧光粉的制备及其荧光性能

通过高温固相法合成了LED用红色荧光粉Sr(1-1.5x)Mo0.8Si0.2O3.8∶Eu3x+(x=0.1,0.2,0.3,0.4,0.5)。通过XRD、激发光谱和发射光谱测试了材料的物相组成以及发光性能。x=0.1样品的XRD谱与JCPDS 08-0482(SrMoO4)的标准卡片相同。Eu3+代替晶格中Sr2+的位置成为发光中心。随着Eu3+含量x的增加,593 nm处的5D0-7F1跃迁和614 nm处的5D0-7F2跃迁发射强度会相互转换:当x≤0.4时,以磁偶极5D0-7F1跃迁为主,发射橙色光;而当x=0.5时,以电偶极5D0-7F2跃迁发射为主,发射红光。可能是过量掺杂的Eu3+离子,只能存在于晶格空位形成缺陷,无法占据SrMoO4中Sr2+的格位中,Eu3+在晶格中占据非对称中心的格位,导致电偶极跃迁变成允许跃迁,从而增加了5D0-7F2跃迁,减弱了5D0-7F1跃迁。因此,可以通过调节激活剂的含量获得不同发光色的荧光粉。Eu3+掺杂的硅钼酸锶体系,614 nm激发下,在368 nm处出现宽的基质吸收峰和467 nm处7 F0-5 D2的跃迁峰,且这2处的吸收峰在x=0.5时比x=0.4时...     

Preparation, characterization and photoluminescence properties of BaB2O4: Eu3+ red phosphor

A new red emitting BaB2O4: Eu3+ phosphor was synthesized by solid-state reaction method. X-ray powder diffraction (XRD) analysis confirmed the monoclinic formation of BaB2O4. Field-emission scanning electron-microscopy (FE-SEM) observation indicated that the microstructure of the phosphor consisted of irregular grains with heavy agglomerate phenomena. Upon excitation with 394 nm light, the BaB2O4: Eu3+ phosphor shows bright red emissions with the highest photoluminescence (PL) intensity at 611 nm due to 5D0→7F2 transitions of Eu3+ ions. The CIE chromaticity coordinates are calculated from the emission spectrum to be x=0.64, y=0.35. The effects of the Eu3+ concentration on the PL were investigated. The results showed that the optimum concentration of Eu3+ in BaB2O4 host is 6 mol% and the dipole-dipole interaction plays the major role in the mechanism of concentration quenching of Eu3+ in BaB2O4: Eu3+ phosphor. The effect of charge compensation on the emission intensity was also studied. The charge compensations of Li+, Na+ and K+ anions all increased the luminescent intensity of BaB2O4: Eu3+. K+ anion gave the best improvement to enhance the intensity of the emission, indicating K+ is the optimal charge compensator. All properties show that this phosphor could serve as a potential candidate for application as a red phosphor for NUV chip LED.     

X-Ray storage luminescence of BaFCl:Eu2+ single crystals

Temperature behaviors of X-ray luminescence (XL), photoluminescence (PL), photostimulated luminescence, and thermoluminescence (TL) were studied in BaFCl:Eu2+ single crystals from room temperature to liquid nitrogen temperature. Six emissions at 275, 315, 365, 385, 435, and 500 nm were observed in the XL spectra and are attributed to Cl excitons, V(k)(Cl2-), the 4f65d1 (2e(g)) --> 4f7 (8S(7/2)) transition of Eu2+, and oxygen vacancies, respectively. Three emission peaks at 315, 365, and 390 nm were observed in the PL and TL measurements. These three emissions are from the transitions of 4f7(6I(7/2)) --> 4f7(8S(7/2)), 4f7(6P(7/2)) --> 4f7(8S(7/2)), and 4f65d1 (2e(g)) --> 4f7(8S(7/2)) of Eu2+, respectively. In our measurements, we observed that the emission of Eu2+ increases in intensity upon beta-irradiation and did not see any signals related to Eu3+ ions, which indicates that Eu2+ ions might not be oxidized to Eu3+ upon X-ray or beta-irradiation. Instead, the color centers, Cl excitons, and oxygen defects are created and are stable at room temperature, and they might play a key role in the storage luminescence.     

Synthesis, characterization and photoluminescence properties of CaSiO3:Eu3+ red phosphor

CaSiO3:Eu3+ (1-5 mol%) red emitting phosphors have been synthesized by a low-temperature solution combustion method. The phosphors have been well characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and optical spectroscopy. PXRD patterns reveal monoclinic CaSiO3 phase can be obtained at 900°C. The SEM micrographs show the crystallites with irregular shape, mostly angular. Upon 254 nm excitation, the phosphor show characteristic fluorescence 5D0→7FJ (J=0, 1, 2, 3, 4) of the Eu3+ ions. The electronic transition located at 614 nm corresponding to 5D0→7F2 of Eu3+ ions, which is stronger than the magnetic dipole transition located at 593 nm corresponding to 5D0→7F1 of Eu3+ ions. Different pathways involved in emission process have been studied. Concentration quenching has been observed for Eu3+ concentration>4 mol%. UV-visible absorption shows an intense band at 240 nm in undoped and 270 nm in Eu3+ doped CaSiO3 which is attributed to oxygen to silicon (O-Si) ligand-to-metal charge-transfer (LMCT) band in the SiO3(2-) group. The optical energy band gap is widened with increase of Eu3+ ion dopant.     

退火温度对PLD法制备ZnO:Eu3+,Li+薄膜结构和发光性质的影响

采用脉冲激光沉积(PLD)法在Si(111)衬底上制备了Eu3+,Li+共掺杂的ZnO薄膜,分别在450,500,550和600℃条件下进行退火,退火气氛为真空。利用X射线衍射(XRD)仪和荧光分光光度计研究了退火温度对薄膜结构和光致发光(PL)的影响。研究结果表明,Eu3+,Li+共掺杂的ZnO薄膜具有c轴择优取向,Eu3+,Li+没有单独形成结晶的氧化物,均以离子形式掺入ZnO晶格中。PL谱中有较宽的ZnO基质缺陷发光,ZnO基质与稀土Eu3+之间存在能量传递,但没有有效的能量传递。随着退火温度的增加,薄膜发光先增强后减弱,退火温度为550℃时发光最强。当用395 nm的激发光激发样品时,仅观察到稀土Eu3+在594 nm附近的特征发光峰,但发光强度随退火温度变化不明显。     

New Routes to the Synthesis of Mesoporous Materials and Their Properties

The factors that influence the hydrothermal synthesis of MCM-41 were investigated, and it was found that compared with those from high H₂O/SiO₂ systems(designated MCM-41-A), the products from low H₂O/SiO₂ systems(designated MCM-41-B) exhibited a less-defined X-ray powder diffraction (XRD) pattern with a broader main reflection peak at a lower 2θ diffraction angle. MCM-41-B possesses a smaller surface area but a larger pore size than MCM-41-A. New routes including direct thermal treatment, room-temperature crystallization and microwave heating were developed for the formation of MCM-41, and the properties of the products prepared from these new routes were compared with those of the MCM-41 hydrothermally synthesized. The pore sizes of MCM-41 materials are uniformly distributed with an effective pore diameter that falls into the range of 2-4 nm, where as the products from wet-gel thermal treatment possess two kinds of mesopores:the well-defined smaller pores distributed at 3 nm and the larger one within 8-20 nm. The MAS NMR spectroscopy revealed that after calcination to remove the organic template in Al-containing MCM-41, a small part of the tetrahedrally-coordinated framework aluminum atoms became octahedrally-coordinated and a considerable amount of Si-OH species were generated.     

Optical spectra of a novel polyoxometalate occluded within modified MCM-41

The novel polyoxometalate ([(Eu2PW10O38)4(W3O8(H2O)2(OH)4)]22-), also referred to herein as Eu8P4W43, has been immobilized inside the channels of MCM-41 mesoporous molecular sieve material by means of the incipient wetness method. For proper host-guest interaction, amine groups were introduced into the system as a result of an aminosilylation procedure. A stable and integrated Eu8P4W43 polyoxometalate was shown to be formed inside the channels of the modified MCM-41. The products were characterized by XRD, UV-vis absorption, emission, Raman excitation, Raman, and 31P solid-state NMR measurements. Infrared and Raman spectra of the polyoxometalate/MCM-41 composite systems are interpreted as showing spectral shifts due to site induced electrostatic interactions. The photoluminescent behavior of the composite at room temperature indicates a characteristic Eu3+ emission pattern corresponding to 5D0- 7F(J) transitions. A strong photoluminescence suggests the potential utility of the polyoxometalate as a luminescent material.     

Spectroscopic properties and intense red-light emission of (Ca, Eu, M)WO4 (M=Mg, Zn, Li)

The red-emitting phosphors of (Ca, Eu, M)WO4 (M=Mg, Zn, Li) were prepared through solid-state reactions, and their spectroscopic properties were studied. After the addition of a small amount of Mg2+, Zn2+ or Li+ in (Ca, Eu)WO4, the red-light emission intensity of Eu3+ increases obviously. In the luminescence spectra of the phosphors, the predominant transition emission is 5D0-->7F2 (616nm), whereas the other emissions are very weak. The excitation spectra are composed of interweaved ligand-to-metal charge-transfer bands (CTB) of W6+-O(2-) and Eu3+-O(2-), and a few 4f excitation transitions of Eu3+. Among the 4f excitation transitions of Eu3+, there are three strong excitation lines corresponding to 7F0-->5L6, 7F0-->5D2 and 7F0-->5D1 transitions, whose relative excitation intensity ratio is seriously affected when Li+ doped in the host. The new phosphors may be applied as red-emitting phosphors for white light emitting diodes.     

(Ca1-x-yLuy)MoO4∶xEu3+红色荧光粉的化学共沉淀合成与光致发光

使用NH4HCO3-NH3.H2O混合沉淀剂,采用化学共沉淀法合成(Ca1-x-yLuy)MoO4:xEu3+红色荧光粉,通过XRD、EDS、荧光光谱和CIE色度图研究该荧光粉的晶体结构、成分组成及发光性能。结果表明,实验按照理论化学计量比成功合成了(Ca1-x-yLuy)MoO4:xEu3+红色荧光粉,该荧光粉为CaMoO4白钨矿结构;(Ca1-x-yLuy)MoO4:xEu3+具有7F0→5L6(394 nm)和7F0→5D2(465 nm)的强电子吸收,且在613 nm处可发射高强度红光,其色坐标为(0.666 5,0.332 9),明显优于传统的Y2O2S:Eu3+红色荧光粉;此外,当Lu含量为30mol%时,荧光粉发光强度最佳。     

高温固相法合成R_(2-x)(MoO_4)_3∶xEu~(3+)(R=Y,Gd)红色荧光粉的研究

采用高温固相法合成R2-x(MoO4)3∶xEu3+(R=Y,Gd)系列红色荧光粉.研究了煅烧温度、助熔剂的含量和Eu3+的掺杂量对样品发光性能的影响,并对样品的物相组成、激发和发射光谱进行分析.结果表明,样品Gd0.6(MoO4)3∶1.4Eu3+在800℃左右煅烧时呈单斜晶结构,当煅烧温度提高到950℃左右,呈正交斜晶结构;样品Y0.2(MoO4)3∶1.8Eu3+在800℃左右煅烧时已经完全形成了正交结构,当煅烧温度升高到1000℃左右时,其正交结构得到保持,没有发生相变.其中,助熔剂NH4Cl的含量占样品总量的3%,煅烧温度为1000℃,保温3h得到的样品Gd0.6(MoO4)3∶1.4Eu3+和Y0.2(MoO4)3∶1.8Eu3+的发光性能达到最佳.另外,由激发和发射光谱分析表明,该荧光粉可以被近紫外光(395nm)和蓝光(465nm)有效激发,发射峰值位于612nm的红光,对应于Eu3+离子的5 D0→7 F2跃迁,是一种可应用在紫外光和蓝光芯片激发产生白光LED的红色荧光粉.     

新型无机-有机杂化中孔发光材料(phen)_2Eu/MCM-41的合成与表征

合成出了担载稀土有机配合物的无机 -有机杂化中孔发光材料 ( phen) 2 Eu/MCM-4 1 ,用 X射线衍射、红外光谱、荧光光谱和紫外 -可见漫反射光谱对所得样品进行了表征 ,并与相应的纯稀土配合物进行了比较 .结果表明 ,所得杂化材料具有典型的中孔材料 MCM-4 1的结构 ,且经组装后孔结构保持不变 ,在紫外光照射下 ,发出稀土离子的特征谱线 ,但与纯稀土配合物相比 ,其激发光谱发生蓝移 ,稀土 Eu3 所处的格位对称性降低 ,荧光寿命延长 .另外 ,对光谱性质进行了讨论 .