上转换发光材料表面修饰羧基的制备与表征

利用表面接枝改性法,丁二酸酐作修饰剂,对上转换无机发光材料进行了表面羧基修饰.傅立叶红外吸收光谱证明了羧基的存在,电导率法定量地检测了羧基的含量,热分析表明修饰羧基后材料的热失重过程,扫描电镜显示了修饰后上转换无机发光材料颗粒有的直径有所增加.沉降试验表明修饰羧基后的上转换发光材料在水溶液中的分散稳定性得到了提高.     

原位聚合法制备水溶性高聚物修饰的NaYF4：Yb,Er

采用原位聚合法,以聚丙烯酸（PAA）和聚乙烯吡咯烷酮（PVP）为壳层材料,对NaYF4上转换发光材料表面进行了PAA和PVP的修饰,傅立叶红外吸收光谱和热重分析证明了NaYF4纳米粒子表面有PAA和PVP的存在,透射电镜显示,当反应温度在0℃,丙烯酸单体含量为8.0wt%,反应时间130min时,PAA修饰的纳米粒子微观形貌最佳;当反应温度在60℃,乙烯基吡咯烷酮单体含量在12.0wt%,反应时间在150min的条件下,PVP修饰的纳米粒子微观形貌最佳。上转换荧光测试结果证明,在对材料进行NaYF4无机壳层包覆后再进行水溶性高聚物修饰,能够使其荧光性能保持不变。     

络合沉淀法合成纳米Y2O3:Yb,Er及其上转换发光性能

以EDTA为螯合剂,采用络合沉淀法合成了纳米级Yb、Er共掺杂的Y2O3上转换发光粉.通过X射线衍射(XRD)、透射电子显微镜(TEM)、光致发光(PL)光谱和红外(IR)光谱对微晶进行了表征.结果表明,经980℃焙烧后的粒子为单一的立方晶相,其颗粒基本为球形,并且其粒径约为30nm.PL谱和IR谱分析结果表明:纳米粒子的表面效应使得表面原子更易吸附空气中的水和二氧化碳,从而增强了4S3/2→4F9/2的无辐射弛豫过程,使得样品所发红光与体材料相比具有更高的荧光分支比.另外,本文还对样品的发光性能作了详细的讨论.     

NaYF_4∶Yb,Er超细纳米晶的合成及单带红色上转换发光研究

通过水热法成功合成了直径约为3 nm的NaYF4∶Yb,Er超细纳米晶。荧光光谱测试表明,其发射波长位于660 nm的单带红光,其杂质光的含量低于1/99.6。机理研究表明超细纳米晶的尺寸效应产生的表面高能量振动声子和激发光子的高表面散射率导致4F7/2能级上的电子通过消耗基质声子能量而向下弛豫到4S3/2和2H11/2的概率大大降低,而主要通过4F7/2+4I11/2-2×2F9/2跃迁过程布居4F9/2能级,从而实现强红光发射。     

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.     

Y2O2S:Er,Yb纳米晶的制备及其上转换和下转换发光

采用共沉淀法,结合固-气硫化工艺制备了平均粒径约40nm的类球形Y2O2S:Er,Yb纳米晶,并对其在980nm红外激发下的上转换和下转换发射进行了较为详细的研究.Er3+的上转换特征发射分别位于530、550和660hm附近.在表面吸附OH-和CO2-3所形成的特殊声子环境下,Er3+的4S3/2→4F9/2和4I11/2→I13/2多声子弛豫显著提高了4F9/2能级的粒子布居,致使纳米晶具有很强的660nm红光发射.并且红绿光荧光分支比会随Yb3+浓度的提高而显著增大.首次报导了Y2O2S纳米晶中Er3+的红外特征发射.源于Er3+离子4I13/2→4O15/2辐射跃迁的较强红外发射,在晶场作用下分化为峰位分别位于1501、1534和1577nm的3个发射峰.由于4I13/2能级是660nm红光发射的主要布居能级之一,该红外发射与红光发射存在明显竞争.但在较高Yb3+掺杂浓度下,高效的Yb3+→Er3+能量传递可有效削弱红外发射的竞争作用.     

上转换发光材料及发光效率研究及展望

综述了上转换发光材料的进展.介绍了上转换发光的基本机制,较新的上转换发光材料,并分析了发光效率的影响因素.对上转换发光材料的发展进行了展望.     

水热法制备NaErxYb1-xF4上转换发光材料

利用水热法合成了不同稀土离子含量的NaErxYb1-xF4上转换发光材料,并时所得产物进行了表征.研究了样品在980nm激发下的发光性能与稀土离子浓度变化的关系,探讨了上转换发光机理.     

不同形貌β-NaYF4∶Yb,Er（Tm）的水热法合成和上转换发光研究

采用水热法添加不同的表面活性剂合成了NaYF4∶Yb,Er(Tm),并借助XRD、TEM、FT-IR、上转换发光谱对合成样品的物相、形貌、表面包覆情况、上转换发光强度等进行了分析。结果表明在相同的温度、时间条件下合成样品的物相均为六方相;添加不同表面活性剂所合成样品的形貌各不相同,可以通过控制添加表面活性剂的种类、剂量等条件调控晶体的生长。添加柠檬酸所合成的样品的上转换发光强度较高。     

上转换发光材料的合成与应用

综述了目前国内外上转换发光材料的几种合成方法,包括传统的高温固相合成法、溶胶一凝胶法、水热合成法、共沉淀法等.总结了不同方法的优缺点,对上转换材料合成方法的发展进行了展望.并介绍了上转换技术的一些应用.     

A novel precursor route for Y2Mo4O15:Yb3+,Ho3+ phosphor and investigation of up-conversion luminescence

Hydrothermal reaction of Y(NO₃)₃·6H₂O and (NH₄)₆Mo₇O₂₄·4H₂O at 180 °C for 24 h was performed in this work via systematically varying the solution pH (4–10) and Mo/Y molar ratio (R, 2–5), which produced a NH₄Y(MoO₄)₂·0.19H₂O new compound that yielded phase-pure Y₂Mo₄O₁₅ upon calcination at 500–700 °C. The pH/R window for the compound to crystallize was determined to be 6–7/3 and 6–9/4–5. The products were characterized in detail by XRD, FTIR, elemental analysis, SEM, TEM, STEM and TG to understand chemical composition and the courses of phase/morphology evolution. Applying the above synthesis strategy successfully produced Y₂Mo₄O₁₅:xYb³⁺,yHo³⁺ phosphors that exhibit strong deep-red (630–670 nm, ⁵F₅ → ⁵I₈ transition) and weak green (530–560 nm, ⁵F₄/⁵S₂ → ⁵I₈) emissions under 978 nm laser pumping, where the optimal Yb³⁺ and Ho³⁺ contents were determined to be x = 0.20 for y = 0.01 and y = 0.03 for x = 0.10, respectively. Spectral analysis indicated that the up-conversion luminescence occurred via a two-photon process, with the red/green intensity ratio and also the emission color dependent on Yb³⁺ and Ho³⁺ contents, which were explained by considering ground state excitation, energy transfer, non-radiative relaxation and cross relaxation.     

Er~(3+)/Yb~(3+)共掺四种玻璃中上转换发光效率的比较及研究

计算了在Er3+/Yb3+共掺的硅酸盐、锗酸盐、磷酸盐和氟化物这四种玻璃基质中施主离子归一化荧光线形函数与受主离子归一化吸收线形函数的重叠积分,交叉弛豫几率.通过求解能级跃迁速率方程,得出4S3/2能级的相对布居数.定义了上转换发光效率可以用自发辐射跃迁几率A61和4S3/2能级的相对布居数之积来表征.分析了由于氟化物中4S3/2能级的无辐射跃迁几率较小而自发辐射跃迁几率较大,因此4S3/2能级有较大的相对布居数,在四种Er3+/Yb3+共掺的玻璃中,氟化物具有较好的上转换发光效率.     

超分散剂对纳米TiO2的表面改性研究

采用超分散剂对纳米TiO2粉体进行表面改性,可将超分散剂分子成功地包覆于TiO2表面,对TiO2表面进行非极性修饰,使其表面由极性亲水性变为非极性亲油性。由沉降性实验观测到超分散剂改性后的纳米TiO2粒子可在非极性溶液中稳定悬浮960h以上;透射电镜(TEM)观测到改性后的TiO2粒子在非极性溶剂中呈纳米级分散状态,团聚体的粒径基本控制在100nm以内;通过润湿性测试及红外分析观察到,颗粒表面由亲水性变为疏水性,纳米TiO2颗粒表面增加了-CH2-和C=O-O基团键的振动峰,因而可以判断纳米TiO2表面状态发生了改变,使TiO2与非极性材料具有较好亲和相容性。本实验也证明了TiO2表面亲油改性的可行性。     

纳米氧化锌硬脂酸改性工艺研究

用硬脂酸作改性剂,对其改性纳米氧化锌的工艺条件进行了研究,并给出了适合工业化生产的最佳工艺条件。     

Up-conversion luminescence of the NaYF4:Yb3+,Er3+ nanomaterials prepared with the solvothermal synthesis

Up-converting NaYF₄:Yb³⁺,Er³⁺ (x_Yb: 0.20, x_Er: 0.02) nanomaterials were prepared with a microwave assisted solvothermal synthesis to study how the synthesis parameters affect the structure and up-conversion luminescence of the materials and thus their usability as labels in biomedical applications. The purity of the materials was studied with Fourier transform infra-red (FT-IR) spectroscopy and the particle size and morphology with transmission electron microscopy (TEM). The crystal structure was characterized with X-ray powder diffraction (XPD) and the crystallite sizes were calculated with the Scherrer formula. Up-conversion luminescence and luminescence decays were studied with near infra-red (NIR) laser excitation at 970 nm.The presence of the oleic acid was observed in the FT-IR spectra. The TEM images showed small quasi-spherical nanoparticles as well as long nanorods. The XPD measurements revealed that both cubic and hexagonal forms of NaYF₄ were present in the materials. The crystallite sizes ranged from ca. 20 to over 150 nm for the cubic and hexagonal phases, respectively. The characteristic up-conversion luminescence of Er³⁺ in red (640–685 nm; ⁴F_9/2 → ⁴I_15/2) and green (515–560 nm; ²H_11/2, ⁴S_3/2 → ⁴I_15/2 transitions) wavelengths was observed. The most intense luminescence and the longest luminescence emission lifetime were obtained with the material annealed for 12 h at 177 °C with 1.8 MPa pressure due to the predominance of the well-crystallized hexagonal form of NaRF₄ (R: Y, Yb, Er).     

阻燃剂水镁石的表面改性研究

使用铝酸酯、钛酸酯、硬脂酸3种偶联剂对水镁石进行表面改性。阐述了改性剂用量、时间和温度等因素对水镁石改性的影响。硬脂酸用量5%,改性温度80℃,改性时间80min条件下,产物性能最优良,活化指数达到96.2%。钛酸酯用量1%,改性温度60℃,改性时间50min条件下,产物性能最优良,活化指数达到98.2%。铝酸酯用量1%,改性温度70℃,改性时间50min条件下,产物性能最最优良,活化指数达到98.8%。使用XRD、FTIR和TG-DSC对改性前后的水镁石进行表征。分析结果表明改性剂对水镁石的改性机理是:改性剂分子与水镁石表面的羟基形成氢键而吸附在水镁石的表面,从而改善了水镁石与聚合物的相容性能。     

纳米SiO2表面改性研究

以乙醇为分散介质,用硅烷偶联剂γ-(2,3-环氧丙基)氧化丙基三甲氧基硅烷(KH-560)对纳米SiO2进行表面改性.讨论了偶联剂用量对SiO2改性的影响,并采用红外光谱、热失重、扫描电镜、表面羟基滴定等手段表征改性效果.结果表明,硅烷偶联剂与纳米SiO2发生化学反应并接到SiO2表面,改性后的SiO2在有机物中的分散性明显改善.     

Enhanced Upconversion Luminescence of Metal‐Capped NaGd0.3Yb0.7F4:Er Submicrometer Particles

Metallic nanostructures are often used to enhance photoluminescence of nanomaterials based on local field enhancement with plasmons at metal surfaces. Here upconversion luminescence (UCL) enhancement of submicrometer‐size NaGd_0.3Yb_0.7F₄:Er particles in cap‐like metal cavities, formed by deposition of a silver film on the particles dispersed on glass substrates, is studied. UCL of the particles is shown to be influenced by not only the plasmon‐enhanced local field but also the cavity modes. By varying the cavity size and location of the particles in the cavities, fluctuant variations of the UCL enhancement and electronic depopulation rate are observed in experiments. Typically, a maximum of 12‐fold enhancement of the UCL intensity is obtained. Combining the results with numerical simulations, the phenomenon is ascribed to effects of metal quenching, plasmonic field enhancement, and the cavity modes for the excitation and emission photons. Finally it is verified that, for the cap‐like submicrometer metal cavities, allocating the particles at the open mouths of the cavities is more advantageous to obtaining stronger enhancements of the particles' UCL. And the demonstrated structure is also convenient to fabricate for applications, e.g., in solar cells.