聚合物多层次结构中稀土络合物的光谱性质(Spectroscopic Properties of Rare Earth Complex Doped in Various Artificial Polymer Structure)(“十一五”国家重点图书)

聚合物多层次结构中稀土络合物的光谱性质(Spectroscopic Properties of Rare Earth Complex Doped in Various Artificial Polymer Structure)(“十一五”国家重点图书)






  Rare earth ions have received great interest due to their intense emission peaks (halfmaximum width <10 nm ) in the visible and nearinfrared region, and have been widely used in a variety of applications. Especially in the application of the optical signal amplification, much interest has been concentrated on rare earth doped inorganic materials because they are compatible with the present communication system.
  Since the mid 90s of last century, photonics polymer has been well developed because polymer optical fiber (POF) was demonstrated in local area communications, and became a promising candidate for fiber to the desktop. Besides POF, many photonics polymers and their devices have been designed and exploited, which can be used in production, transmission, storage, display and modulation of photons, because photonics polymers are of characteristics of light weight, easy process and low price. The increasing awareness of the utility of photonics polymers also led to the work on rare earth complex doped polymers.
  It has been known that luminescence of rare earth complexes is heavily affected by ligand absorption, ligandtoion energy transfer and material structure they doped in. In recent years, controlling luminescence of rare earth complex doped polymer by constructing polymer structure has received more and more interest to meet the need of novel photonics devices, because, there is much unknown that needs to be exploited in this developing field. For example, aggregates of rare earth complexes will be formed in polymer in this developing field, which are resulted from the difference in inherent energy between complexes and polymers. Efficiency of luminescence of rare earth complexes would be heavily quenching by such aggregates due to their quenching action. In order to get high efficiency, it is necessary to investigate the existence and domain size of such aggregates in polymer samples, which depend on fabrication technique and process for the polymers. It has also been realized that microstructure of polymer can control luminescence of rare earth complexes doped in the polymer. That is, by adjusting the microstructure, the luminescence can be modulated, which has potential application in photonics devices.
  Under this circumstance, in the past decade, research on rare earth complex doped polymers was carried out as one of photonics polymers in our group aiming at various photonics devices, such as amplifiers and lasers. Started with synthesis and characterization of rare earth complex doped polymers, research work in our group was mainly focused on spectroscopic properties of rare earth complex doped in polymers, and then gradually went deep into studies on relationship between luminescence and various polymer structures, including nanoparticles, microvesicles and fiber waveguides. During this period, it was gradually realized from the work that structural construction of rare earth containing polymer, from molecular level to waveguide level, is necessary for application in photonics devices. This realization will guide our future work in developing new photonic devices based on rare earth containing polymers.
  This book is composed of 9 chapters, and the content in each chapter is relatively independent with each other, although the main theme is still around of rare earth complex doped polymers. Chapter 1 provides a short description to the synthesis and characterization of rare earth complexes and their doped polymers. Chapter 2 deals with spectroscopic properties of rare earth complex doped polymer using JuddOfelt theory. During measurement of fluorescence, a redshift in excitation was observed, and Chapter 3 presents a quantitative model to rectify this effect when fluorescence is measured. From Chapter 4 to Chapter 9, various unique polymer structures are introduced, with the main point on the modulation of luminescence from rare earth complexes in such unique structures. Most of the work has been published in academic journals, and part unpublished, which is concerned with some details and newly development in the research. These novel exploitations are expected to be published elsewhere, however, related phenomena are so close to the theme of this book, it is reasonable to present them here.
  Photonics polymer is a crossdiscipline that encompasses photonics and polymer science. The challenge in polymer science is the application of photonics theory and its fundamental techniques. It is a demanding task, and requires the best approaches that photonics can provide. I gratefully here acknowledge the beneficial discussion and collaboration from Prof. Guangchan Guo (Photonics), Prof. Chi Wu (Polymer chemical physics), Prof. Hai Ming (Optical information), Prof. Ming Yin (Luminescence), Prof. Yingmei Li (Biophotonics), Prof. Chen Gao (Condensed state physics), Prof. Keyi Wang (Near field optics), and Prof. Bin Zhu (Fiber optics). Without their help, it is impossible to fulfill the work in such a crossdiscipline.
  The research work concerned in this book was financially supported by National Natural Science foundation of China and Chinese Academy of Sciences, which is gratefully acknowledged here. There were many Ph. D candidates who dedicated their talent and endeavor to this creative study. Without their devotion, this work can not be accomplished. They are Hao Liang, Biao Chen, Jie Xu, Hongfang Jiu, Hui Zhao, Youyi Sun, Wei Su, Si Wu, Qing Yan, Yanhua Luo and Wenxuan Wu. Other students in my group also took part in discussion concerning this work. I sincerely express my gratitude here for the diligence and efforts made by all of them.
  Finally, I would like to dedicate this book to my Alma Mater, University of Science and Technology of China, celebrating her 50 anniversary in 2008. In this campus, I have been studying, researching and living for nearly 30 years. This book will constitute a fitting memorial to these days.


Chapter 1 Synthesis and characterizationof rare earth complex doped polymers

1.1 Synthesis of rare earth complex doped polymer

1.2 Uniformity and thermal stability of rare earth complex doped polymer

Chapter 2 Spectroscopic properties of rare earth complex doped PMMA and their Judd-Ofelt treatment

2.1 The theory of spectroscopic analysis

2.2 Spectroscopic analysis of Nd(DBM)3Phen and Nd(DBM)3(TPPO)2 in PMMA

2.3 Spectroscopic analysis of Eu complexes in PMMA

2.4 Spectroscopic analysis of Er complexes in PMMA

2.5 Spectroscopic analysis of Pr complexes in PMMA

2.6 Spectroscopic analysis of Sm complexes in PMMA

Chapter 3 Rectification of excitation with bathochromic shift during emission measurement of Eu complexes

3.1 Bathochromic shift during fluorescence measurement

3.2 Theoretical model for treatment of Bathochromic shif

3.3 Prediction of best exciting wavelength for fluorescence measurement

Chapter 4 Fluorescence enhancing of rare earth complexes in PMMA

4.1 Fluorescence enhancement of Eu(DBM)3Phen codoped with the other rare earth complexes in PMMA

4.2 Fluorescence enhancement of Sm(DBM)3Phen  codoped with other rare earth complexes in PMMA

4.3 Model for luminescence enhancement in PMMA codoped with two kinds of rare earth complexes

Chapter 5 Effects of synergetic ligands on radiative properties of Eu(TTA)3nL doped PMMA and LB films

5.1 The radiative properties of Eu(TTA)3nL doped PMMA

5.2 The radiative properties of Eu(TTA)3nL doped LB films

Chapter 6 Three dimensional memory through submicrometer voids formed  within Sm(DBM)3Phen doped PMMA

6.1 Material and equipment for multiphoton recording by femtosecond laser

6.2 Recording and reading of three-dimentional optical storage in Sm(DBM)3Phen doped PMMA

Chapter 7 Nanocomposites composed of rare earth complexes and silver nanoparticles

7.1 J-aggregates of rare earth complexes formed on the surface of silver nanoparticles

7.2 Effects of Ag colloidal nanoparticles on luminescent properties of Eu(Ⅲ) β-diketone

7.3 Nanocomposite composed of Eu(TTA)3Bipy/Tb(TTA)3Bipy /Silver Nanoparticles

Chapter 8 Modulation in luminescence of rare earth complexes doped in photo-responsive polymer

8.1 Photo-induced optical anisotropy and polarized emission of europium complex doped azobenzene polymer film

8.2 Reversible modulation in fluorescence intensity of a single vesicle composed of diblock azo-copolymer and Eu(DBM)3

Chapter 9 Polymer optical fibers doped with rare earth complexe

9.1 Gradient refractive index distribution of POF

9.2 Design and fabrication of SCPOF preform doped with rare earth complexes

9.3 Optical amplification of rare earth complexes doped SI POF



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