D-A型有機(jī)光電材料光物理特性的研究
發(fā)布時(shí)間：2019-06-19 03:35
【摘要】：近年來，電子給體D（Donor）-電子受體A（Acceptor）共軛結(jié)構(gòu)的光電材料由于具有較好的非線性光學(xué)性質(zhì)、超快的光學(xué)響應(yīng)、較低的加工成本等特殊的光學(xué)和化學(xué)性質(zhì)廣泛的應(yīng)用于有機(jī)發(fā)光二極管、場(chǎng)效應(yīng)晶體管、雙光子吸收材料等領(lǐng)域。它具有諸多優(yōu)點(diǎn)：D-A分子結(jié)構(gòu)通過π電子的氧化或還原來分別實(shí)現(xiàn)P型或N型摻雜；可以有效調(diào)節(jié)分子的HOMO和LUMO；通過改變給體單元和受體單元來進(jìn)行改善發(fā)光性能；通過電荷轉(zhuǎn)移對(duì)分子的帶隙進(jìn)行調(diào)節(jié)；可以拓寬分子的光吸收范圍等。 本論文的主要工作是在有機(jī)光電領(lǐng)域中的應(yīng)用基礎(chǔ)上，對(duì)三種不同結(jié)構(gòu)單元的D-A型共軛光電材料的結(jié)構(gòu)、光物理性質(zhì)從理論和實(shí)驗(yàn)兩方面進(jìn)行系統(tǒng)的研究，并由此來指導(dǎo)材料的性能。主要的研究內(nèi)容如下： 1．通過實(shí)驗(yàn)和理論方法對(duì)PFO和F8BT的光物理特征進(jìn)行了系統(tǒng)研究。量子化學(xué)計(jì)算展現(xiàn)了PFO和F8BT的電子躍遷機(jī)制，也模擬了二者的吸收光譜。結(jié)果證實(shí)了單分散系統(tǒng)中的F8BT中出現(xiàn)的鏈內(nèi)電荷的離域。飛秒瞬態(tài)吸收測(cè)量表明局部鏈內(nèi)激子在激發(fā)的PFO的弛豫過程中占主導(dǎo)地位。鏈內(nèi)的電荷離域缺失的中間狀態(tài)在被激發(fā)的F8BT的弛豫過程中出現(xiàn)。此外，位于單分散系統(tǒng)內(nèi)的PFO和F8BT的基于強(qiáng)度的瞬態(tài)吸收曲線表明，雖然鏈間激子相互作用可影響PFO的弛豫特性，但不能影響激發(fā)的F8BT的弛豫特性。位于固態(tài)膜中的PFO和F8BT的基于強(qiáng)度的瞬態(tài)吸收曲線表明，中間狀態(tài)可能從F8BT弛豫過程中消失。PFO和F8BT可展示在凝聚相及高激發(fā)強(qiáng)度下基于強(qiáng)度的激子--激子淬滅過程。由于良好的鏈內(nèi)電荷轉(zhuǎn)移特征，F(xiàn)8BT的弛豫時(shí)間比PFO的弛豫時(shí)間長。 2.通過赫克反應(yīng)合成兩種基于芴的齊聚物（P-F-P和F-P-F-P-F），其中芴和吩噻嗪基團(tuán)交替排列。通過實(shí)驗(yàn)和理論方法詳細(xì)研究了他們的光物理性質(zhì)。其中穩(wěn)態(tài)吸收和發(fā)射光譜表明：與吸收峰、發(fā)射峰、帶隙和Stokes位移有關(guān)的光譜特性已被改變。量化計(jì)算提供了分子結(jié)構(gòu)和分析電子躍遷機(jī)制。此外，雙光子熒光和飛秒開放光圈Z-掃描技術(shù)證實(shí): F-P-F-P-F的雙光子熒光產(chǎn)率和雙光子吸收橫截面與P-F-P相比顯著提高。強(qiáng)度依賴瞬態(tài)吸收數(shù)據(jù)表明:在溶液中，與激發(fā)態(tài)P-F-P和無芳烴-芳烴的相互作用相比，F(xiàn)-P-F-P-F的激發(fā)壽命縮短。所有光學(xué)性質(zhì)的改善都源于π共軛系統(tǒng)的擴(kuò)展。 3.通過實(shí)驗(yàn)和理論方法對(duì)三種線性共軛低聚物(F-P、F-P-F和P-F-P-F-P)的光學(xué)特性進(jìn)行了詳細(xì)研究。穩(wěn)態(tài)光譜測(cè)量表明，這些低聚物的吸收和發(fā)射帶均隨著π共軛系統(tǒng)的增強(qiáng)而紅移，且其他光學(xué)性能均受到調(diào)制。雙光子熒光和飛秒開孔Z-掃描技術(shù)證實(shí)，雙光子熒光產(chǎn)率和這些低聚物的雙光子吸收截面均隨著π共軛系統(tǒng)的改進(jìn)而增強(qiáng)。時(shí)間分辨熒光測(cè)定顯示，弛豫過程會(huì)逐漸加速，而基于連續(xù)衰減速率分布模型而獲得的擬合結(jié)果顯示，低聚物的衰減速率會(huì)逐漸加速，分布寬度從F-P到P-F-P-F-P變得越來越窄。量子化學(xué)計(jì)算提供了分子結(jié)構(gòu)和分析了電子躍遷機(jī)制，指出TPA特性的改善應(yīng)該依賴于π共軛系統(tǒng)的增強(qiáng)。
[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.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：O437
本文編號(hào)：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.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：O437
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