D-A型有机光电材料光物理特性的研究
发布时间：2019-06-19 03:35
【摘要】：近年来，电子给体D（Donor）-电子受体A（Acceptor）共轭结构的光电材料由于具有较好的非线性光学性质、超快的光学响应、较低的加工成本等特殊的光学和化学性质广泛的应用于有机发光二极管、场效应晶体管、双光子吸收材料等领域。它具有诸多优点：D-A分子结构通过π电子的氧化或还原来分别实现P型或N型掺杂；可以有效调节分子的HOMO和LUMO；通过改变给体单元和受体单元来进行改善发光性能；通过电荷转移对分子的带隙进行调节；可以拓宽分子的光吸收范围等。 本论文的主要工作是在有机光电领域中的应用基础上，对三种不同结构单元的D-A型共轭光电材料的结构、光物理性质从理论和实验两方面进行系统的研究，并由此来指导材料的性能。主要的研究内容如下： 1．通过实验和理论方法对PFO和F8BT的光物理特征进行了系统研究。量子化学计算展现了PFO和F8BT的电子跃迁机制，也模拟了二者的吸收光谱。结果证实了单分散系统中的F8BT中出现的链内电荷的离域。飞秒瞬态吸收测量表明局部链内激子在激发的PFO的弛豫过程中占主导地位。链内的电荷离域缺失的中间状态在被激发的F8BT的弛豫过程中出现。此外，位于单分散系统内的PFO和F8BT的基于强度的瞬态吸收曲线表明，虽然链间激子相互作用可影响PFO的弛豫特性，但不能影响激发的F8BT的弛豫特性。位于固态膜中的PFO和F8BT的基于强度的瞬态吸收曲线表明，中间状态可能从F8BT弛豫过程中消失。PFO和F8BT可展示在凝聚相及高激发强度下基于强度的激子--激子淬灭过程。由于良好的链内电荷转移特征，F8BT的弛豫时间比PFO的弛豫时间长。 2.通过赫克反应合成两种基于芴的齐聚物（P-F-P和F-P-F-P-F），其中芴和吩噻嗪基团交替排列。通过实验和理论方法详细研究了他们的光物理性质。其中稳态吸收和发射光谱表明：与吸收峰、发射峰、带隙和Stokes位移有关的光谱特性已被改变。量化计算提供了分子结构和分析电子跃迁机制。此外，双光子荧光和飞秒开放光圈Z-扫描技术证实: F-P-F-P-F的双光子荧光产率和双光子吸收横截面与P-F-P相比显著提高。强度依赖瞬态吸收数据表明:在溶液中，与激发态P-F-P和无芳烃-芳烃的相互作用相比，F-P-F-P-F的激发寿命缩短。所有光学性质的改善都源于π共轭系统的扩展。 3.通过实验和理论方法对三种线性共轭低聚物(F-P、F-P-F和P-F-P-F-P)的光学特性进行了详细研究。稳态光谱测量表明，这些低聚物的吸收和发射带均随着π共轭系统的增强而红移，且其他光学性能均受到调制。双光子荧光和飞秒开孔Z-扫描技术证实，双光子荧光产率和这些低聚物的双光子吸收截面均随着π共轭系统的改进而增强。时间分辨荧光测定显示，弛豫过程会逐渐加速，而基于连续衰减速率分布模型而获得的拟合结果显示，低聚物的衰减速率会逐渐加速，分布宽度从F-P到P-F-P-F-P变得越来越窄。量子化学计算提供了分子结构和分析了电子跃迁机制，指出TPA特性的改善应该依赖于π共轭系统的增强。
[Abstract]:In recent years, the photoelectric material of the electron donor D (Donor)-electron acceptor A (Acceptor) co-conductive structure is widely applied to an organic light emitting diode, a field effect transistor, And the like. The method has the advantages that the molecular structure of the D-A has the advantages that the molecular structure of the D-A can realize the P-type or the N-type doping respectively through the oxidation of the molecular structure of the molecule, the HOMO and the LUMO of the molecule can be effectively adjusted, the light-emitting performance can be improved by changing the donor cell and the acceptor unit, and the band gap of the molecule is regulated by the charge transfer; The light absorption range of the molecules and the like can be broadened. The main work of this thesis is to study the structure and physical properties of the D-A type co-conductive photoelectric material of three different structural units on the basis of the application of the organic photoelectric field, and to guide the material's ability from the theory and the experiment. can. The main content of the study is The physical characteristics of PFO and F8BT were studied by experimental and theoretical methods. The quantum chemical calculation shows the electronic transition mechanism of PFO and F8BT, and also simulates the absorption of both PFO and F8BT. The results confirm the intra-chain charge present in F8BT in a single-dispersion system. The femtosecond transient absorption measurement indicates that the exciton in the local chain is occupied by the relaxation process of the excited PFO. the lead position. The intermediate state of the charge separation in the chain is in the relaxation process of the excited F8BT In addition, the strength-based transient absorption curves of PFO and F8BT in a single-dispersion system show that, while interchain exciton interactions may affect the relaxation properties of the PFO, the relaxation of the excited F8BT cannot be affected The intensity-based transient absorption curve of the PFO and F8BT in the solid film shows that the intermediate state may be relaxed from the F8BT The PFO and F8BT show the intensity-based exciton--exciton quenching at the coacervation phase and the high excitation intensity The relaxation time of F8BT is higher than that of PFO due to the good intra-chain charge transfer characteristic 2. The synthesis of two base-based oligomers (P-F-P and F-P-F-P-F) by the Hector reaction, in which the two groups of the two groups The clusters are arranged alternately. They are studied in detail by means of experimental and theoretical methods. Optical physical properties. The steady-state absorption and emission spectra show that the spectrum, which is related to the absorption peak, the emission peak, the band gap, and the Stokes shift, Sex has been changed. Quantitative calculation provides molecular structure and analysis Sub-transition mechanism. In addition, the two-photon fluorescence and the femtosecond open-aperture Z-scanning technique prove that the two-photon fluorescence yield and the two-photon absorption cross-section of the F-P-F-P-F and the P-F-P phase The ratio of F-P-F-P-F is higher than that of the excited state P-F-P and the non-aromatic-aromatic hydrocarbon in the solution. The lifetime of the hair is shortened. The improvement of all optical properties is derived from the reduction of the lifetime. 3. The extension of the system.3. The optical properties of three linear co-polar oligomers (F-P, F-P-F and P-F-P-F-P) are studied by means of experimental and theoretical methods. A detailed study was carried out. The steady-state spectral measurements show that the absorption and emission bands of these oligomers are redshifted with the enhancement of the confocal system, and other optics Both the two-photon fluorescence and the two-photon absorption cross-section of these oligomers have been confirmed with the two-photon fluorescence and the femtosecond-aperture Z-scanning technique. The time-resolved fluorescence measurement shows that the relaxation process is gradually accelerated, and the fitting results obtained on the basis of the continuous decay rate distribution model show that the decay rate of the oligomer is gradually accelerated and the distribution width is from F-P to P-F-P-F- P becomes more and more narrow. The quantum chemical calculation provides a molecular structure and an analysis of the electronic transition mechanism. It is pointed out that the improvement of the characteristics of the TPA should depend on the structure.
【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】：O437
本文编号：2502046
[Abstract]:In recent years, the photoelectric material of the electron donor D (Donor)-electron acceptor A (Acceptor) co-conductive structure is widely applied to an organic light emitting diode, a field effect transistor, And the like. The method has the advantages that the molecular structure of the D-A has the advantages that the molecular structure of the D-A can realize the P-type or the N-type doping respectively through the oxidation of the molecular structure of the molecule, the HOMO and the LUMO of the molecule can be effectively adjusted, the light-emitting performance can be improved by changing the donor cell and the acceptor unit, and the band gap of the molecule is regulated by the charge transfer; The light absorption range of the molecules and the like can be broadened. The main work of this thesis is to study the structure and physical properties of the D-A type co-conductive photoelectric material of three different structural units on the basis of the application of the organic photoelectric field, and to guide the material's ability from the theory and the experiment. can. The main content of the study is The physical characteristics of PFO and F8BT were studied by experimental and theoretical methods. The quantum chemical calculation shows the electronic transition mechanism of PFO and F8BT, and also simulates the absorption of both PFO and F8BT. The results confirm the intra-chain charge present in F8BT in a single-dispersion system. The femtosecond transient absorption measurement indicates that the exciton in the local chain is occupied by the relaxation process of the excited PFO. the lead position. The intermediate state of the charge separation in the chain is in the relaxation process of the excited F8BT In addition, the strength-based transient absorption curves of PFO and F8BT in a single-dispersion system show that, while interchain exciton interactions may affect the relaxation properties of the PFO, the relaxation of the excited F8BT cannot be affected The intensity-based transient absorption curve of the PFO and F8BT in the solid film shows that the intermediate state may be relaxed from the F8BT The PFO and F8BT show the intensity-based exciton--exciton quenching at the coacervation phase and the high excitation intensity The relaxation time of F8BT is higher than that of PFO due to the good intra-chain charge transfer characteristic 2. The synthesis of two base-based oligomers (P-F-P and F-P-F-P-F) by the Hector reaction, in which the two groups of the two groups The clusters are arranged alternately. They are studied in detail by means of experimental and theoretical methods. Optical physical properties. The steady-state absorption and emission spectra show that the spectrum, which is related to the absorption peak, the emission peak, the band gap, and the Stokes shift, Sex has been changed. Quantitative calculation provides molecular structure and analysis Sub-transition mechanism. In addition, the two-photon fluorescence and the femtosecond open-aperture Z-scanning technique prove that the two-photon fluorescence yield and the two-photon absorption cross-section of the F-P-F-P-F and the P-F-P phase The ratio of F-P-F-P-F is higher than that of the excited state P-F-P and the non-aromatic-aromatic hydrocarbon in the solution. The lifetime of the hair is shortened. The improvement of all optical properties is derived from the reduction of the lifetime. 3. The extension of the system.3. The optical properties of three linear co-polar oligomers (F-P, F-P-F and P-F-P-F-P) are studied by means of experimental and theoretical methods. A detailed study was carried out. The steady-state spectral measurements show that the absorption and emission bands of these oligomers are redshifted with the enhancement of the confocal system, and other optics Both the two-photon fluorescence and the two-photon absorption cross-section of these oligomers have been confirmed with the two-photon fluorescence and the femtosecond-aperture Z-scanning technique. The time-resolved fluorescence measurement shows that the relaxation process is gradually accelerated, and the fitting results obtained on the basis of the continuous decay rate distribution model show that the decay rate of the oligomer is gradually accelerated and the distribution width is from F-P to P-F-P-F- P becomes more and more narrow. The quantum chemical calculation provides a molecular structure and an analysis of the electronic transition mechanism. It is pointed out that the improvement of the characteristics of the TPA should depend on the structure.
【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】：O437
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