微波水热合成六方相NaYF4以及Yb3＋、Er3＋掺杂NaYF4微米管

为了合成单相以及Yb3+、 Er3+掺杂的六方结构NaYF4,采用微波水热的方法,以稀土硝酸盐、氟化钠、柠檬酸、氢氧化钠、乙酸乙酯和水为原料,合成了六方相NaYF4以及Yb3+、Er3+掺杂的六方相NaYF4 (NaYF4 ∶ Yb3+,Er3+)微米管. 利用XRD、SEM对所得样品的物相和形貌进行了表征. 研究了不同反应条件对产物形貌和物相的影响,并提出了NaYF4微米管的形成机理. 研究发现,采用微波加热的方法可以在较低的温度下快速得到单一六方相的NaYF4. 所制备的Yb3+、 Er3+掺杂NaYF4微米管的上转换发光性能与其体材料类似,具有较高的发光强度.     

热处理温度及EDTA对β-NaYF_4:Yb~(3+),Er~(3+)材料结构与性能的影响

采用共沉淀法合成了Yb3+、Er3+共掺杂的NaYF4粉体,重点研究了热处理温度和螯合剂EDTA对所合成粉体的晶相、表面形貌以及上转换发光性能的影响,并利用X射线衍射、扫描电镜及荧光光谱对其结构组成、晶体表面形貌及发光性能进行了研究。结果表明:随着热处理温度的升高,NaYF4:Yb3+,Er3+粉体由立方相向六方相转变,当温度高于600℃时又从六方相逐渐转变为立方相,而且颗粒的尺寸逐渐变大,从近似球形到无规则形状;NaYF4:Yb3+,Er3+发光强度与热处理温度密切相关,热处理温度对于β-NaYF4:Yb3+,Er3+的发光性能有着重要的影响。经过600℃热处理后的粉体具有较高的发光强度;螯合剂EDTA的添加对所合成粉体的发光性能有着明显的影响,螯合剂的添加降低了其发光强度;在1 000℃以内,NaYF4:Yb3+,Er3+具有良好的热稳定性。     

NaYF4:Er3+和NaYF4:Yb3+/Er3+上转换荧光纳米晶的制备与表征

以EDTA为螯合剂,采用络合共沉淀法合成了NaYF4:Er3+和NaYF4:Yb3+/Er3+纳米晶.分别采用XRD、SEM、荧光分光光度计对合成的样品进行了结构、形貌和上转换荧光分析.XRD结果表明,制备的NaYF4:Er3+和NaYF4:Yb3+/Er3+均为纯立方相;SEM结果显示,制备的NaYF4:Er3+和NaYF4: Yb3+/Er3+晶粒粒径都在100nm左右,与NaYF4:Er3+相比,NaYF4:Yb3+/Er3+晶粒尺寸分布更均匀,分散性更好,符合作为荧光标记材料的要求;上转换荧光分析表明,在980nm激光器激发下,NaYF4:Yb3+/Er3+的发光强度比NaYF4:Er3+提高了1个数量级.     

上转换荧光光子晶体薄膜的制备及包装防伪应用

以热分解法制备的蓝色荧光NaYF4:Yb3+,Tm3+上转换纳米颗粒为核,外延生长一层具有钝化表面缺陷、增强荧光效果的NaYF4壳层,制备得到核壳上转换纳米颗粒(CSNPs).利用反相微乳液法在CSNPs上包覆一层修饰3-(三甲氧基甲硅基)甲基丙烯酸丙酯(MPS)的SiO2,实现上转换纳米颗粒亲水改性的同时,赋予其可参与加成聚合的双键.将CSNPs@SiO2-MPS与苯乙烯单体通过乳液聚合共聚形成镧系掺杂NaYF4/PS复合微球.通过垂直沉积法,利用镧系掺杂NaYF4/PS复合微球自组装构建上转换荧光光子晶体(UCPC)薄膜,并探讨其在包装防伪中的应用.结果表明:该上转换荧光光子晶体薄膜,在可见光下从特定角度可以观察到明显的粉色结构色,在980 nm激光照射下可观察到蓝色荧光,这两种模态下的光学特性可隐藏信息,预期在信息保护、包装防伪等领域有广阔的应用前景.     

NaYF_4∶Yb,Er/Tm上转换发光强度的影响因素

含有稀土离子的上转换发光材料因具有巨大的应用价值而受到人们的广泛研究,特别是六方相NaYF4已被公认为是迄今为止发光强度最大的上转换基质材料.以稀土离子Yb和Er或Yb和Tm的共掺杂NaYF4上转换材料为研究对象,讨论了几种不同因素对其上转换发光强度的影响,并对这种上转换材料的应用与研究前景提出了几点建议.     

凝胶网络模板法可控制备NaYF_4:Yb~(3+),Er~(3+)稀土上转换纳米颗粒

采用水凝胶空间网孔结构作为纳米级反应容器可控制备了NaYF4:Yb3+,Er3+稀土上转换发光纳米颗粒。通过控制交联剂密度可以改变网络凝胶网孔结构,用不同网孔结构的凝胶模板可以控制合成纳米颗粒。通过XRD、TEM、PL等方法研究了不同凝胶模板对颗粒的尺寸、发光性能的影响。结果表明,利用高分子交联后形成的凝胶网络,可以制得粒径在10 nm左右的NaYF4:Yb3+,Er3+纳米颗粒。随着交联剂浓度的升高,颗粒粒径及荧光强度都有所下降。本研究为稀土上转换发光纳米颗粒的制备提供了工艺简单、绿色环保的新方法。     

色彩可调Yb, Er共掺杂NaYF4上转换荧光材料的 合成及包装防伪应用

采用阴离子表面活性剂柠檬酸三钠和阳离子表面活性剂氯代十六烷基吡啶共同调介下的水热法,合成Yb,Er共掺杂NaYF_4上转换荧光材料(NaYF_4:Yb~(3+),Er~(3+));研究敏化剂Yb~(3+)和激活剂Er~(3+)在NaYF_4中的掺杂原子百分数(掺杂量)对NaYF_4:Yb~(3+),Er~(3+)上转换材料荧光性能的影响;以合成的NaYF_4:Yb~(3+),Er~(3+)为荧光填料,聚乙烯醇(PVA)为基材,通过流延法,制备了一系列不同荧光特性的复合薄膜。研究结果表明:随着Yb~(3+)含量的提高,NaYF_4:Yb~(3+),Er~(3+)上转换材料发光强度先增大后减小,当Yb~(3+)掺杂量为30%时,荧光强度达到最大;另外,随着Yb~(3+)掺杂量从10%提高到98%,绿色荧光与红色荧光强度的比值(绿红比)逐渐减小,上转换材料发光颜色由绿色变为黄色再变为橙色。随着Er~(3+)掺杂量的增加,荧光强度同样先增大后减小,当Er~(3+)掺杂量为1%时,荧光强度达到最大;且Er~(3+)掺杂量的增加同样会使绿红比降低。所制备的复合薄膜透明性好,且具有易调控、易识别、难察觉的上转换荧光特性,预期在包装防伪领域有很好的应用前景。     

超重力反应沉淀法制备NaYF_4∶Er~(3+)及上转换发光性能

采用重力反应沉淀法合成了Er3+掺杂的NaYF4上转换发光剂,分别用X射线衍射(XRD)、扫描电子显微镜(SEM)和荧光分光光度计(FL)对试样的晶体结构、表面形貌及发光性能进行了表征,研究了不同煅烧温度对材料结构、形貌和发光的影响。结果表明:NaYF4∶Er3+为立方相和六方相混合的晶体,经过煅烧后,颗粒具有很好的结晶性,含有少量的杂相。分别用650nm的红光和808nm的近红外光激发,测试样品的上转换发光,观察到了紫色、蓝色、绿色上转换发光。     

Yb3+/Er3+共掺杂BaY2F8纳米颗粒的水热合成与上转换发光

采用水热方法合成了Yb3+/Er3+共掺杂BaY2F8纳米颗粒,并对其进行了不同温度的热处理,热处理温度为200℃-800℃。研究了热处理温度对纳米粒子的晶相、粒径和上转换发光强度的影响。结果发现随着热处理温度的升高,纳米粒子的粒径和上转换发光强度明显增加。讨论了BaY2F8:Yb3+,Er3+纳米粒子的上转换发光机理。     

NaYF_4:Yb,Er-Fe_3O_4纳米复合颗粒的制备与表征

以NaYF4∶Yb,Er纳米颗粒作为种晶,选用二氨基十二烷等双官能团配体作为偶联剂,采用直接偶联法制备了NaYF4∶Yb,Er-Fe3O4纳米复合颗粒。通过透射电镜、X射线衍射仪和能量色散X射线光谱仪对NaYF4∶Yb,Er-Fe3O4纳米复合颗粒的结构、形貌以及组成进行了表征,比较了不同双官能团配体对纳米复合结构形成的影响。结果表明,双官能团配体的使用对纳米复合结构的形成至关重要;配体所具有官能团的种类以及NaYF4∶Yb,Er种晶粒径会影响NaYF4∶Yb,Er与Fe3O4纳米颗粒之间的偶联作用。     

Synthesis and characterization of upconverting NaYF4:Er3+, Yb3+ nanocrystals via thermal decomposition of stearate precursor

Er3+-Yb3+ codoped hexagonal NaYF4 nanocrystals were prepared via a method of thermal decomposition of stearate precursor. Their crystal structure, morphologies and photoluminescence (PL) properties were characterized by XRD, SEM, and fluorescence spectra. The hexagonal NaYF4:Er3+, Yb3+ nanocrystals could be well dispersed in cyclohexane to form a clear solution. Under 980 nm excitation, the solution of Er3+-Yb3+ codoped NaYF4 nanocrystals emits bright green upconversion fluorescence.     

An efficient and user-friendly method for the synthesis of hexagonal-phase NaYF(4):Yb, Er/Tm nanocrystals with controllable shape and upconversion fluorescence

Hexagonal-phase NaYF(4):Yb, Er/Tm nanocrystals are the best IR-to-visible upconverting materials to date, but user-friendly methods for making pure hexagonal-phase NaYF(4):Yb, Er/Tm nanocrystals with upconversion fluorescence are still lacking. Most of the methods reported so far require excess fluoride reactants in a high-temperature reaction which are very unfriendly to users and raise safety concerns. In this work, an efficient and user-friendly method was developed for the synthesis of uniform hexagonal-phase NaYF(4):Yb, Er/Tm nanocrystals with upconversion fluorescence, by forming small solid-state crystal nuclei and further growth and ripening of the nuclei. NaYF(4):Yb, Er/Tm nanoplates, nanospheres and nanoellipses were also selectively produced by varying the concentration of the surfactant. All the nanocrystals showed strong upconversion fluorescence, and fluorescence from the nanoplates was observed even when the laser power density was reduced to about 50?mW?cm(-2). These nanocrystals have great potential for use in biology and medicine as fluorescent labels or imaging probes.     

Synthesis of colloidal upconverting NaYF4: Er3+/Yb3+ and Tm3+/Yb3+ monodisperse nanocrystals

The synthesis, characterization, and spectroscopy of upconverting lanthanide-doped NaYF4 nanocrystals (NCs) is presented. The monodisperse cubic NaYF4 NCs were synthesized via a thermal decomposition reaction of trifluoroacetate precusors in a mixture of technical grade chemicals, octadecene and the coordinating ligand oleic acid. In this straightforward method, the dissolved precursors are added slowly to the reaction solution through a stainless-steel canula resulting in highly luminescent nanocrystals with an almost monodisperse particle size distribution. The NCs were characterized through the use of transmission electron microscopy, selected area electron diffraction, 1H NMR, powder X-ray diffraction, and high-resolution luminescence spectroscopy. The NaYF4 NCs are capable of being of dispersed in nonpolar organic solvents thus forming colloidally stable solutions. The colloids of the Er3+, Yb3+ and Tm3+, Yb3+ doped NCs exhibit green/red and blue upconversion luminescence, respectively, under 980 nm laser diode excitation with low power densities.     

Effect of homogeneous coating on K+-doped NaGdF4:Er3+,Yb3+ upconversion materials

Journal of Materials Science: Materials in Electronics - The K+-doped (Na1?xKx)GdF4:Er3+,Yb3+ upconversion materials were successfully synthesized by solvothermal method. The doping of K+ was...     

NaYF4:Er3+六棱柱的水热合成及上转换发光性能

以氟化钠、硝酸钇、硝酸铒为原料,利用水热法合成NaYF4:Er3+材料。利用X射线粉末衍射仪(XRD)、场扫描电子显微镜(SEM)、红外吸收(FT-IR)以及发光光谱等手段对产物的物相结构、形貌和荧光性能进行分析。结果表明,NaYF4:Er3+为六角棱柱晶体,属于六方晶系,具有P63/m(176)空间点群结构。在980nm光激发下,NaYF4:Er3+展现出强的上转换光,波长在520nm和539nm为绿光发射,对应为Er3+离子的2 H11/2→4/I15/2和4S3/2→4/I15/2跃迁发射,而652nm为红光发射,则对应于Er3+离子的4F9/2→4/I15/2跃迁发射。     

Upconversion emission from Yb3+ and Tm3+ codoped NaYF4 thin film prepared by thermal evaporation

Yb3+ and Tm3+ codoped fluoride thin film, with intense ultraviolet and visible upconversion emissions under 980 nm excitation, has been deposited on an Al2O3 ceramic substrate by thermal evaporation under high vacuum. NaY(0.835)Yb(0.15)Tm(0.015)F4 bulk material synthesized by high temperature solid-state reaction was used as target in preparing the thin film. Yb3+ and Tm3+ codoped system, which had been reported before, had been studied. Compared with the unannealed thin film, the annealed film showed better upconversion emission properties, especially in the ultraviolet region, given in the normalized upconversion emission spectra, due to the structure changed from amorphous to hexagonal NaYF4 (beta-NaYF4) during the annealing process. The upconversion mechanism of the thin film was also discussed in this paper.     

A novel approach from infrared to ultraviolet emission enhancement in Yb3+, Er3+:CaF2 nanofilms

Under 978 nm excitation, we explored the infrared-to-ultraviolet upconversion properties in the nanofilms with the nanoparticles of Yb3+, Er3+ codoped calcium fluoride (CaF2:Yb3+, Er3+). The strong enhancement of ultraviolet emission was observed. The result is attributed to the optical performance characteristics of the nanostructure materials. Furthermore, a novel upconversion approach explains well the UV-enhanced emission.     

Direct imaging the upconversion nanocrystal core/shell structure at the subnanometer level: shell thickness dependence in upconverting optical properties

Lanthanide-doped upconversion nanoparticles have shown considerable promise in solid-state lasers, three-dimensional flat-panel displays, and solar cells and especially biological labeling and imaging. It has been demonstrated extensively that the epitaxial coating of upconversion (UC) core crystals with a lattice-matched shell can passivate the core and enhance the overall upconversion emission intensity of the materials. However, there are few papers that report a precise link between the shell thickness of core/shell nanoparticles and their optical properties. This is mainly because rare earth fluoride upconversion core/shell structures have only been inferred from indirect measurements to date. Herein, a reproducible method to grow a hexagonal NaGdF(4) shell on NaYF(4):Yb,Er nanocrystals with monolayer control thickness is demonstrated for the first time. On the basis of the cryo-transmission electron microscopy, rigorous electron energy loss spectroscopy, and high-angle annular dark-field investigations on the core/shell structure under a low operation temperature (96 K), direct imaging the NaYF(4):Yb,Er@NaGdF(4) nanocrystal core/shell structure at the subnanometer level was realized for the first time. Furthermore, a strong linear link between the NaGdF(4) shell thickness and the optical response of the hexagonal NaYF(4):Yb,Er@NaGdF(4) core/shell nanocrystals has been established. During the epitaxial growth of the NaGdF(4) shell layer by layer, surface defects of the nanocrystals can be gradually passivated by the homogeneous shell deposition process, which results in the obvious enhancement in overall UC emission intensity and lifetime and is more resistant to quenching by water molecules.