稀土氟化物纳米材料的应用研究进展

氟化物纳米材料由于其独特的光、电、磁等性质,在光学器件、生物标记等领域具有广泛的应用,已成为材料科学领域研究的热点之一,尤其是稀土金属氟化物。合成氟化物纳米材料的方法多种多样,已成功制备出了球形纳米颗粒、纳米线、纳米花、复合结构纳米晶、核壳结构纳米材料等。本文主要列举了几种常见的稀土氟化物,重点对其合成以及应用进行了综述,并结合其特点,进行了展望。     

多级复合半导体纳米材料的制备

金属氧化物、Ⅲ-Ⅴ、Ⅱ-Ⅵ等半导体纳米材料由于其独特的功能性质已广泛应用于光学、电子、太阳能转化、催化等领域,是当今先进材料领域的研究前沿与热点。随着科技的发展,人们对材料的高效、多功能要求已成为必然,对半导体材料发展要求亦如此。多组分复合、多层次结构协同是实现半导体纳米材料多功能化与高效化的有效途径。构筑多级结构组合纳米半导体,不但可以调控其能带结构而提高半导体材料的光电与催化性能,而且由于多级低维纳米结构聚集时形成的空间位阻效应可以有效克服纳米晶“易团聚”难题。本文提出多级结构组合纳米晶的概念、分类,结合近年来该领域的研究实践,较系统地综述了多级复合半导体纳米结构制备的最新研究进展。首先简要介绍了多级复合半导体纳米材料的概念与典型结构; 其次对典型多级复合半导体纳米材料的制备方法进行了重点评述,分别综述了液相法、气相法以及最新发展起来的静电纺丝等方法在多级结构半导体复合纳米材料制备中的应用实践。再其次,对以具有半导体特性的石墨烯及其功能化衍生物为基体的新型多级复合半导体纳米材料的制备做了综述。最后对半导体/半导体多级结构复合纳米材料的发展方向做了展望。     

微纳米稀土氯氧化物的合成研究进展

稀土氯氧化物作为一种重要的发光基质,具有较高的光吸收效率和传能效率,在彩色显示、催化、生物医药、光电转换、气敏等领域均有广泛的应用,已成为光功能材料领域的研究热点之一。目前研究者已用固相法、沉淀法、液相-高温焙烧法、水热与溶剂热法、前驱体热解法、溶胶-凝胶法、静电纺丝法等方法成功地制备了稀土氯氧化物微米颗粒,纳米颗粒、纳米条、纳米片、纳米棒、纳米针、纳米纤维、纳米带、纳米管等稀土氯氧化物微纳米材料。总结了各种制备方法的研究进展及优缺点,并结合本课题组在稀土氯氧化物纳米材料方面的研究工作,对稀土氯氧化物微纳米材料的制备方法的发展方向进行了展望。     

阳极氧化铝模板限域制备一维杂化纳米材料及其多样化应用的研究进展

一维杂化纳米材料以其独特的物理化学性质,在电学、光学、催化等领域得到了广泛的应用。 其制备方法对一维杂化纳米材料性能的改变和调控显得至关重要。 模板法作为一种简单而普适的合成工艺,近几年来被广泛应用于纳米结构和纳米阵列的合成。 本文主要介绍了阳极氧化铝(AAO)模板法制备一维杂化纳米材料整体情况、AAO模板结合其他技术材制备材料的方法、一维杂化纳米材料在刺激响应性器件、能量存储与转换器件、催化等众多领域的应用。     

水溶液法制备CeF3纳米颗粒

氟化铈(CeF3)具有很高的离子电导率［1］和独特的光学特性［2］, 可用于制作化学传感器和光学元器件. CeF3还是良好的固体润滑剂［3］. 近年来的研究结果表明, 与氟化物粗晶材料相比, 纳米尺度的氟化物的性能有显著的提高， 因此, 其制备方法也很受关注. 目前, 制备氟化物纳米颗粒的方法有蒸发法［4］、 微乳液法［2, 5~8］、 水醇混合溶液法［3,9］和微波固相氧化还原合成法［10］等. 但是, 水溶液直接沉淀法作为一种操作简单, 成本低, 适合批量生产的制备方法尚未见用于制备纳米CeF3颗粒.     

稀土纳米晶用于近红外区活体成像和传感研究进展

稀土纳米晶具有丰富的激发和发射波长,良好的化学和光稳定性、大Stokes位移等特点.近年来,稀土纳米晶在生物活体成像与传感领域的应用研究取得了迅速进展.通过纳米尺度的材料设计与合成,可以对稀土纳米晶的荧光效率、波长、寿命等光学性质,以及生物相容性、靶向性、响应性等生化性质进行精细调控,使其更好地适应于活体深组织的成像与分析.先概述活体荧光成像的技术特点与要求,然后介绍稀土纳米晶的一般组成、光学性质和荧光机理,随后详细讨论对稀土纳米晶光学和生化性质进行调控的方法,着重展示这些材料的设计和修饰在生物成像与传感领域的一些最新应用.通过总结最近的研究成果,期望能够为下一步的研究提供一些参考思路,以推进基于稀土纳米晶的生物成像与传感技术的临床转化和应用.     

稀土掺杂氟化物纳米材料的上转换发光特征及其生物应用

稀土掺杂氟化物纳米材料由于具有低的声子能,可以获得较高的上转换发光效率,使其在太阳能电池、生物医学、光电子学、信息等领域有着广泛而重要的应用前景。本文就当前稀土氟化物上转换纳米材料的改性、光性能研究,以及在生物检测,生物成像标记,免疫分析,疾病治疗方面的最新研究进展做一综述,并对上转换纳米颗粒在生物应用过程中存在的主要问题进行了讨论。     

稀土纳米材料的制备与组装

稀土元素具有特殊的电子构型，使其在许多领域得到十分广泛的应用。稀土纳米化将有助于发现新性质、开拓新材料，因此，稀土纳米材料已经成为研究的热点。综述了各种形态稀土纳米材料的制备和性质、稀土纳米材料的复合与组装等方面的进展。     

无机半导体纳米晶光学性质的设计、调控及其生物医学应用

半导体纳米晶由于其丰富的能带结构和光学性质,在光电器件和生物医学应用等领域展现出了广阔的应用前景,且在过去的几十年中得到了广泛关注.因此,对其光学性质进行理性设计和精确调控具有重要的研究意义.本文简要综述了本研究组近年来在不同能带隙的无机半导体纳米晶的可控制备技术以及利用DNA纳米技术和蛋白质自组装手段构建具有特异光学性质的纳米结构等方面的相关研究工作,最后对这些纳米晶和纳米结构的独特光学性质及其在生物医学领域的应用研究进行了总结.     

无机纳米稀土发光材料的制备方法*

无机纳米稀土发光材料作为一种重要的发光材料,由于具有独特的光、电和化学性质,使其在高性能磁体、发光器件、显示、生物标记、光学成像和光学治疗等方面得到了广泛的应用。稀土发光材料的这些性质与材料的尺寸和形状密切相关,近年来研究者已经利用多种合成方法制备了不同形状的纳米稀土发光材料,包括纳米线、纳米棒、纳米管、纳米纤维和纳米片等。本文综述了无机纳米稀土发光材料的几种常用的制备方法,包括水热/溶剂热法、有机/无机前驱体热分解法和超声辅助合成法等,评述了这些方法的优缺点,并结合课题组在无机纳米稀土发光材料制备方面的工作,对无机纳米稀土发光材料制备方法的发展进行了展望。     

Surface-treatment of Alkaline Earth Sulfides Based Phosphor

A series of alkaline earth sulfides based phosphors Ca0.8Sr0.2S : Eu^2 , Tm^3 were covered with a layerof protective coating with alkaline earth fluorides by heating the mixture of phosphor and NH4HF2 at elevatedtemperatures. The coatings were characterized by means of XRD and SEM. The optical properties of thecoated phosphors and the influences of the coating on their properties have been discussed extensively. Thestabilities of the coated and uncoated phosphors have been compared.     

Fast Ion Conducting Nanocrystalline Alkaline Earth Fluorides Simply Prepared by Mixing or Manual Shaking

Simple mixing or shaking of alkaline earth hydroxides with ammonium fluoride results in nanocrystalline phase pure metal fluorides MF₂ (M: Ca, Sr, Ba). The formation of the alkaline earth fluorides was investigated by varying the reaction conditions. Evidence was found that just the contact between the starting materials is sufficient for the reaction to take place. X‐ray diffraction, elemental analysis, ¹⁹F MAS NMR spectroscopy, and measurements of DC conductivities were used to characterize the fluorides regarding properties like crystal structure, crystallite sizes, local fluorine coordination, and fluorine ion conductivity. The ¹⁹F MAS NMR spectra of the phase pure fluorides prepared showed several signals, which were assigned to defects, impurities, or geometric distortions. The fluorides prepared by mixing or shaking revealed fluorine ion conductivities several orders of magnitude higher than observed for the respective microcrystalline alkaline earth fluorides. Therefore, the synthesis routine presented in this study may open a path to a very quick and simple synthesis of nanocrystalline fast fluorine ion conductors.     

Computer modelling of mixed metal fluorides for optical applications

This paper describes a new computational method for predicting the optical behaviour of doped inorganic materials. There is considerable interest in using inorganic materials in photonic devices, and in many cases, the optical properties of these materials depend on doping by ions such as those from the rare earth series. Among the inorganic materials of interest are the mixed metal fluorides (e.g. BaLiF(3), BaY(2)F(8), YLiF(4), LiCaAlF(6), LiSrAlF(6)), doped with trivalent rare earth ions. The paper describes the use of Mott-Littleton calculations to determine the optimum location for dopant ions, followed by crystal field calculations which make direct use of the output of the Mott-Littleton calculations to calculate the optical properties of the dopant ion taking into account its symmetry and the positions of the surrounding ions, including any vacancies or interstitial ions present by virtue of charge compensation. It is then possible to predict whether a given dopant ion at a particular site in a material will have favourable optical properties.     

XAFS analyses of molten metal fluorides

X-ray absorption fine structure studies of molten metal fluorides containing the materials related to nuclear engineering are intensively summarized. By using XAFS spectra data of divalent and trivalent cation metal fluorides in molten state which have been collected by authors’ group for a few years, local structure have been extracted and discussed systematically in conjunction with other spectroscopic studies and numerical calculations. In molten divalent fluorides, tetrahedral coordination of fluorides around a cation is predominant. In the case of pure molten trivalent fluorides, structure with more than 6-coordination has been suggested in some cases, but octahedral coordination structure is much stabilized at heavier rare earth metal fluorides. By mixing with alkali metal fluorides, it is a general trend that inter-ionic distances keep constant, but coordination number of fluorides decreases. In experimental chapter, all the details of sample preparation, furnace installation, X-ray optics setups and data analyses procedures are explained. Finally, future expectations of XAFS technique are also suggested.     

The distillation behavior of fluorides in LiCl–KCl molten salt

Journal of Radioanalytical and Nuclear Chemistry - The distillation behaviors of some fission product fluorides in LiCl–KCl system were investigated. For rare earth element, the corresponding...     

Flame synthesis of calcium-, strontium-, barium fluoride nanoparticles and sodium chloride

Non-oxidic salts such as NaCl, CaF2, SrF2 and BaF2 were synthesised using a flame spray method; optional doping of such fluorides with rare earth elements suggests possible applications in optics.     

An easy access to nanocrystalline alkaline earth metal fluorides – just by shaking

High energy ball milling as fast, direct and solvent free method allows an easy access to nanocrystalline alkaline earth metal fluorides MF₂ (M: Mg, Ca, Sr, Ba). Comparable metal sources (acetates, carbonates, hydroxides, alkoxides) were used for the reaction with NH₄F as fluorinating agent. Even very simple manual shaking experiments between NH₄F and the corresponding hydroxides in the stoichiometric ratio (M:F = 1:2, M: Ca, Sr, Ba) give phase pure fluorides. Moreover, comparable classical thermal reactions in closed crucibles at higher temperatures provide phase pure crystalline fluorides in nearly all cases as well.     

Alkaline earth fluoride and Eu3+ doped thin films obtained by electrochemical processing

Journal of Solid State Electrochemistry - In this study, alkaline earth fluorides (MF2) and MF2:Eu3+ doped (M = Mg, Ca, Sr) thin films were obtained by electrochemical processing. In...     

Novel synthetic route to fluorofullerenes: reaction with binary and complex lead fluorides

We have recently developed methods of preparation of fluorofullerenes with specific fluorine content. Our previous successful synthesis of C₆₀F₃₆ and C₆₀F₁₈ with the use of transition metal fluorides inspired us to probe other high oxidation metal fluorides. In this work we report on the use of the binary lead fluorides (PbF₂, PbF₄, Pb₂F₆) and their complexes with alkali metal and alkaline earth metal fluorides (M₂PbF₆, M₃PbF₇ and M′PbF₆) as fluorinating reagents for fullerenes.     

Preparation and stabilization of aluminium trifluoroacetate fluoride sols for optical coatings

For the first time, aluminium fluorides in liquid phase are available for optical applications. By modifying the conditions of the fluorolytic sol-gel synthesis of aluminium fluorides transparent sols with low viscosities were obtained. These sols consist mainly of small oligomeric or cluster units of aluminium fluoride which are not measurable by DLS, WAXS, SAXS and show unusual narrow signals in solid state NMR. Isolated particles with diameters up to five nanometers can be identified by TEM measurements and allow the use of their sols in optical and anti reflecting coatings. The sol particles were modified by trifluoroacetic acid to prevent agglomeration, and as a result, the obtained xerogels can be re-dispersed transparently in organic solvents.