几种稀土掺杂发光材料的制备及其应用研究
发布时间：2018-10-17 20:32
【摘要】：稀土元素由于其独特的电子层结构，具有一般元素无法比拟的化学和物理性质，因而在生物成像、环境催化、照明与显示、光电转换等诸多领域得到了广泛的应用，被誉为新材料的宝库。首先在生物医学领域，癌症是当今人类亟需攻克的医学难题，而稀土纳米材料作为药物载体实现癌症的早期诊断和治疗已经引起了研究人员的广泛重视。特别是稀土掺杂上转换纳米材料，可以通过多光子过程将近红外光转换成可见光和紫外光。上转换过程有其独特的优势，包括对生物组织穿透深度较深，无背景荧光干扰，信噪比较高。此外，氟化物由于具有声子能量较低、电离度高、电阻系数较高等特点而被认为是最有效的上转换发光基质材料。其次，上转换发光由于可产生发光共振能量传递(LRET)，在环境领域也有一些应用。不仅如此，在现代照明、显示等领域，稀土离子掺杂的发光材料也有着重要的应用。通过稀土离子的共激发，基质材料向稀土离子的能量传递以及稀土离子之间的敏化作用，实现了发光颜色可调控的发射，从而用于FED红、绿、蓝全色显示领域。基于稀土离子掺杂的发光材料广泛的应用，本论文主要研究了以下几方面内容： 采用溶剂热法合成了聚乙烯亚胺(PEI)包覆的NaGdF4:Yb/Er上转换发光纳米粒子。在制备过程中添加表面活性剂PEI后，得到的NaGdF4:Yb/Er纳米粒子具有均匀的形貌，良好的水溶性，同时纳米粒子的存在又降低了PEI原本的毒性。对材料进行了相关的细胞毒性和体外细胞成像实验，材料可用于上转换发光(UCL)和核磁共振(MRI)双模式细胞成像，表面的PEI为其应用于基因传递癌症治疗提供了可能性。 采用静电纺丝法制备具有磁性的上转换发光二氧化硅纳米管。首先通过溶剂热法合成具有上转换发光性质的磁性纳米粒子NaYF4:Yb/Er/Gd(MUCNPs)。随后利用静电纺丝法制备MUCNPs掺杂的二氧化硅前驱体纤维。将前驱体纤在600oC高温煅烧，得到最终产物。合成的材料具有规则的管状形貌，良好的生物相容性，以及磁性的同时还具有上转换发光性质。采用阿霉素(DOX)作为抗癌药物模型研究材料的药物负载和缓释效果，材料表现出明显的药物释放pH响应性。材料还可用于上转换发光(UCL)和核磁共振(MRI)双模式细胞成像。 采用温和的溶剂热法合成具有良好结晶性的、单分散的梭形油相HAp:Yb/Er纳米晶，并通过表面活性剂F127将油相纳米晶转换成了水溶性纳米晶。利用TEM观察样品被Hela癌细胞吞噬的全过程。HAp与人体骨成分相似，MTT实验表明制备得到的样品具有出色的生物相容性，在980nm近红外光照射下发出强烈的红色和绿色上转换发光，并研究了材料的体外细胞成像性质。 采用静电纺丝法制备具有不同上转换发光颜色的NaYF4@SiO2纳米管，用于有色废水处理。静电纺丝法的成本低，方法简单，易于工业化批量生产。合成的管状材料具有较大的比表面积和孔径，可通过物理和化学键合来吸附废水中的有色染料，采用亚甲基蓝和罗丹明6G作为废水模型来研究材料的吸附行为和再生循环利用能力。同时，通过向二氧化硅纳米管中掺杂不同种类的上转换发光纳米粒子，产生多种上转换发光颜色的同时会发生荧光共振能量传递(LRET)效应，可用来检测吸附或交联到材料表面的有色染料，，也是判断吸附过程进度的重要参数。 采用高温固相法制备CaGdAlO4: Tb3+/Eu3+发光材料。在紫外光和低压阴极射线激发下，分别研究了Tb3+和Eu3+分别单掺和共掺于CaGdAlO4中的光致发光性能和阴极射线发光性能。通过改变Tb3+和Eu3+的掺杂比例，将最终实现单一白光发射。具体研究了体系中激活离子之间的能量传递作用、能量传递机理和发光颜色的调控，探讨了其在全彩色FED中的应用前景。
[Abstract]:Because of its unique electron layer structure, the rare earth element has the chemical and physical properties of general elemental oxygen, and has been widely used in many fields such as biological imaging, environmental catalysis, illumination and display, photoelectric conversion and so on. It is known as a treasure house of new materials. First of all, in the field of biomedicine, cancer is the medical problem which the human needs to overcome today, and the early diagnosis and treatment of the rare-earth nanometer material as the drug carrier has attracted much attention of researchers. in particular, that rare-earth-doped transition nano material can convert the near-infrared light into visible light and ultraviolet light through the multi-photon process. The up-conversion process has its unique advantages, including deep penetration depth of biological tissue, no background fluorescence interference and high signal-to-noise ratio. In addition, fluoride is considered to be the most effective upconversion luminescent matrix material due to the characteristics of low phonon energy, high ionization degree, high resistance coefficient and the like. Secondly, the upconversion luminescence has some applications in the field of environment due to the generation of luminescence resonance energy transfer (LRSET). Furthermore, in modern illumination, display and other fields, rare-earth ion-doped luminescent materials also have important applications. Through co-excitation of rare earth ions, the energy transfer of the matrix material to the rare earth ions and the sensitization between the rare earth ions, the emission of the light-emitting color can be regulated and controlled, thus being used in the field of FED red, green and blue full color display. Based on the wide application of rare earth ion-doped luminescent materials, the paper mainly studies the following aspects: Synthesis of NaGdF4: Yb/ Er coated NaGdF4: Yb/ Er by solvent thermal method When the surface active agent PEI is added in the preparation process, the obtained NaGdF4: Yb/ Er nanometer particles have uniform morphology and good water solubility, Toxicity. Related cytotoxicity and in vitro cell imaging experiments are performed on materials that can be used for both upconversion luminescence (UCL) and nuclear magnetic resonance (MRI) dual mode cell imaging, and PEI for the surface provides for its application to gene transfer cancer therapy. can be prepared by electrostatic spinning method, Preparation of Magnetic Nanoparticles NaYF4: Yb/ Er/ Gd (MU) with Upconversion Luminescence Properties by Solvent Thermal Method CNPs), followed by the use of an electrostatic spinning process for the preparation of a MUCNPs-doped silica The precursor fiber is prepared from precursor fiber at 600oC high temperature, the resultant material has regular tubular morphology, good biocompatibility, In addition, adriamycin (DOX) was used as the drug loading and slow release effect of anticancer drug model study material, and the material showed obvious drug release. pH responsiveness. Materials can also be used for up-conversion luminescence (UCL) and nuclear magnetic resonance (MRI) dual-mode Using a mild solvent thermal method to synthesize a monodisperse shuttle-shaped oil phase HAp: Yb/ Er nanocrystals, the oil phase nanocrystals were converted by surfactant F127. The water-soluble nano-crystals were formed. The samples were observed by TEM. HAp is similar to human bone composition, and MTT assay shows that the prepared sample has excellent biocompatibility, emits strong red and green conversion luminescence under the irradiation of 980nm near infrared light, In vitro cell imaging properties: NaYF4@SiO2 with different upconversion luminescence colors is prepared by electrostatic spinning The invention relates to an electrostatic spinning method, which is low in cost and simple in method. The synthetic tubular material has larger specific surface area and pore diameter, can adsorb the colored dye in the waste water through physical and chemical bonding, At the same time, by doping different kinds of up-conversion luminescent nanoparticles into the silicon dioxide nanotube, a fluorescence resonance energy transfer (LRSET) effect can occur while producing a plurality of upconversion luminescence colors, The colored dye attached to the surface of the material is also a judgment Preparation of CaGdAlO4 by High Temperature Solid Phase Method Tb3 +/ Eu3 + luminescent materials were used to study the luminescence of Tb3 + and Eu3 + in CaGdAlO4, respectively. Light-emitting and cathode-ray emission properties, by changing the doping of Tb3 + and Eu3 + In this paper, the energy transfer function, energy transfer mechanism and emission color of activated ions in the system are studied.
【学位授予单位】：吉林大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TB34
[Abstract]:Because of its unique electron layer structure, the rare earth element has the chemical and physical properties of general elemental oxygen, and has been widely used in many fields such as biological imaging, environmental catalysis, illumination and display, photoelectric conversion and so on. It is known as a treasure house of new materials. First of all, in the field of biomedicine, cancer is the medical problem which the human needs to overcome today, and the early diagnosis and treatment of the rare-earth nanometer material as the drug carrier has attracted much attention of researchers. in particular, that rare-earth-doped transition nano material can convert the near-infrared light into visible light and ultraviolet light through the multi-photon process. The up-conversion process has its unique advantages, including deep penetration depth of biological tissue, no background fluorescence interference and high signal-to-noise ratio. In addition, fluoride is considered to be the most effective upconversion luminescent matrix material due to the characteristics of low phonon energy, high ionization degree, high resistance coefficient and the like. Secondly, the upconversion luminescence has some applications in the field of environment due to the generation of luminescence resonance energy transfer (LRSET). Furthermore, in modern illumination, display and other fields, rare-earth ion-doped luminescent materials also have important applications. Through co-excitation of rare earth ions, the energy transfer of the matrix material to the rare earth ions and the sensitization between the rare earth ions, the emission of the light-emitting color can be regulated and controlled, thus being used in the field of FED red, green and blue full color display. Based on the wide application of rare earth ion-doped luminescent materials, the paper mainly studies the following aspects: Synthesis of NaGdF4: Yb/ Er coated NaGdF4: Yb/ Er by solvent thermal method When the surface active agent PEI is added in the preparation process, the obtained NaGdF4: Yb/ Er nanometer particles have uniform morphology and good water solubility, Toxicity. Related cytotoxicity and in vitro cell imaging experiments are performed on materials that can be used for both upconversion luminescence (UCL) and nuclear magnetic resonance (MRI) dual mode cell imaging, and PEI for the surface provides for its application to gene transfer cancer therapy. can be prepared by electrostatic spinning method, Preparation of Magnetic Nanoparticles NaYF4: Yb/ Er/ Gd (MU) with Upconversion Luminescence Properties by Solvent Thermal Method CNPs), followed by the use of an electrostatic spinning process for the preparation of a MUCNPs-doped silica The precursor fiber is prepared from precursor fiber at 600oC high temperature, the resultant material has regular tubular morphology, good biocompatibility, In addition, adriamycin (DOX) was used as the drug loading and slow release effect of anticancer drug model study material, and the material showed obvious drug release. pH responsiveness. Materials can also be used for up-conversion luminescence (UCL) and nuclear magnetic resonance (MRI) dual-mode Using a mild solvent thermal method to synthesize a monodisperse shuttle-shaped oil phase HAp: Yb/ Er nanocrystals, the oil phase nanocrystals were converted by surfactant F127. The water-soluble nano-crystals were formed. The samples were observed by TEM. HAp is similar to human bone composition, and MTT assay shows that the prepared sample has excellent biocompatibility, emits strong red and green conversion luminescence under the irradiation of 980nm near infrared light, In vitro cell imaging properties: NaYF4@SiO2 with different upconversion luminescence colors is prepared by electrostatic spinning The invention relates to an electrostatic spinning method, which is low in cost and simple in method. The synthetic tubular material has larger specific surface area and pore diameter, can adsorb the colored dye in the waste water through physical and chemical bonding, At the same time, by doping different kinds of up-conversion luminescent nanoparticles into the silicon dioxide nanotube, a fluorescence resonance energy transfer (LRSET) effect can occur while producing a plurality of upconversion luminescence colors, The colored dye attached to the surface of the material is also a judgment Preparation of CaGdAlO4 by High Temperature Solid Phase Method Tb3 +/ Eu3 + luminescent materials were used to study the luminescence of Tb3 + and Eu3 + in CaGdAlO4, respectively. Light-emitting and cathode-ray emission properties, by changing the doping of Tb3 + and Eu3 + In this paper, the energy transfer function, energy transfer mechanism and emission color of activated ions in the system are studied.
【学位授予单位】：吉林大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TB34
【共引文献】
相关期刊论文 前10条
1 胡伟汉,张国义,刘立志,吴湖炳,李立,高远红,潘q
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