本文選題：紅熒烯及衍生物　切入點(diǎn)：密度泛函理論　出處：《鄭州大學(xué)》2017年碩士論文

【摘要】：紅熒烯(5,6,11,12-四苯基并四苯)是目前熱門的有機(jī)半導(dǎo)體材料之一,常用于研究與制造各種功能材料及器件。但紅熒烯也具有對(duì)光氧敏感等缺點(diǎn),因此近些年,通過在紅熒烯分子中引入不同的取代基設(shè)計(jì)開發(fā)具有優(yōu)良性質(zhì)的紅熒烯衍生物,制備具有良好光電性質(zhì)的功能材料,成為相關(guān)領(lǐng)域研究人員共同關(guān)注的焦點(diǎn)。引入取代基后,分子內(nèi)的結(jié)構(gòu)改變致使電子給體部分的最高被占用軌道(HOMO)與電子受體部分的最低未被占用軌道(LUMO)發(fā)生變化,從而改變能隙,同時(shí)結(jié)構(gòu)變化不但改變分子的光學(xué)性質(zhì),也改變分子內(nèi)的電荷轉(zhuǎn)移程度。本文主要研究紅熒烯及一系列衍生物在不同環(huán)境下的結(jié)構(gòu)變化、譜帶移動(dòng)及光電性能,主要研究內(nèi)容如下:首先介紹了有機(jī)電致發(fā)光材料、有機(jī)光致發(fā)電材料、有機(jī)電子傳輸材料,以及本文所研究的紅熒烯體系和計(jì)算化學(xué)的背景,由于密度泛函理論是采用泛函求解薛定諤方程的電子結(jié)構(gòu)理論方法,計(jì)算速度快且結(jié)果精確,因此適用于本文體系,并在此基礎(chǔ)上運(yùn)用溶劑效應(yīng)理論、激發(fā)態(tài)理論和電子傳輸理論對(duì)本文體系進(jìn)行理論計(jì)算。其次,利用上述理論和方法計(jì)算了紅熒烯及三種衍生物在十二種溶劑中的紅外譜圖。通過添加極化連續(xù)模型(Polarization Continuous Model,PCM),得到四種分子在不同溶劑中的紅外圖譜,通過分析特征峰的移動(dòng)和強(qiáng)度判斷溶劑影響,發(fā)現(xiàn)紅熒烯及衍生物分子在含質(zhì)子溶劑中位移最明顯,在極性官能團(tuán)溶劑中的譜帶位移次之,在醇類溶劑和惰性溶劑的位移較小。同時(shí)選用溶劑電子接受數(shù)AN、溶劑電子給予數(shù)DN、Dimroth溶劑參數(shù)ET(30)和Brownstein溶劑參數(shù)S四個(gè)溶劑參數(shù)分別與(5,12-二氟苯基-6,11-二苯甲氧基)并四苯分子的C-F鍵振動(dòng)頻率進(jìn)行相關(guān)分析,相關(guān)性大小排序?yàn)镾ET(30)ANDN。然后,針對(duì)紅熒烯及衍生物的光學(xué)性能進(jìn)行系統(tǒng)的理論計(jì)算,研究取代基對(duì)分子幾何構(gòu)型、電離勢(shì)、重組能、吸收光譜及發(fā)射光譜的影響。結(jié)果發(fā)現(xiàn)引入烷烴取代基,紅熒烯及衍生物分子的吸收峰和熒光發(fā)射峰發(fā)生藍(lán)移,而引入芳環(huán)取代基發(fā)生紅移。茂基衍生物(R-Cp)分子吸收譜具有500-700 nm和300-500nm兩處強(qiáng)吸收峰,更利于可見光的吸收,適合作為太陽能電池等光致發(fā)電材料。最后計(jì)算了紅熒烯及衍生物分子的電學(xué)性能,分析前線分子軌道及能隙發(fā)現(xiàn)芳環(huán)取代基的引入利于形成激子。主鏈引入取代基有利于增強(qiáng)π共軛,支鏈引入則作用相反,因此主鏈引入芳環(huán)等共軛取代基可以降低分子能隙,得到電學(xué)性能更好的光電材料。分析電離勢(shì)、電子親和能和重組能發(fā)現(xiàn)三種衍生物分子R-Furan,R-Cp和R-OMe3適合做空穴半導(dǎo)體材料,R-F,R-OMe2,R-OMe1三種分子更適合做電子傳輸材料,而R-OMe4和R-Me兩種分子的電子與空穴重組能差別較小,適合作為有機(jī)半導(dǎo)體晶體管中的發(fā)射材料。
[Abstract]:Red fluorene is one of the most popular organic semiconductor materials. It is often used in the research and manufacture of various functional materials and devices. However, red fluorene also has the disadvantages of being sensitive to photooxygen, so in recent years, By introducing different substituents into the red fluorene molecule to design and develop the red fluorene derivatives with excellent properties, the functional materials with good optoelectronic properties have become the common focus of researchers in related fields. Structural changes in the molecule result in changes in the maximum occupied orbital (HOMOO) of the electron donor and the lowest unoccupied orbit (LUMOO) in the electron acceptor, thus changing the energy gap, while the structural change not only changes the optical properties of the molecule, In this paper, the structure changes, band shift and photoelectric properties of red fluorene and a series of derivatives in different environments are studied. The main research contents are as follows: firstly, the organic electroluminescent materials are introduced. Organic photogenerated materials, organic electron transport materials, and the background of red fluorene system and computational chemistry studied in this paper, because density functional theory is an electronic structure theory method to solve Schrodinger equation, The calculation speed is fast and the result is accurate, so it is suitable for the system in this paper. On this basis, the solvent effect theory, the excited state theory and the electron transport theory are used to calculate the system. The infrared spectra of red fluorene and three derivatives in 12 solvents were calculated by using the above theory and method. The infrared spectra of four kinds of molecules in different solvents were obtained by adding polarization continuous model Polarization Continuous Model-PCM. By analyzing the shift and strength of the characteristic peaks, it is found that the shift of the red fluorene and its derivatives is the most obvious in the proton containing solvent, followed by the band shift in the polar functional group solvent. The displacements of alcohol and inert solvents were small. The solvent electron acceptors ANs, the solvent electron giving number DNN Dimroth solvent parameter ET30) and the Brownstein solvent parameter S were chosen to be different from the other four solvent parameters, respectively, which were 55-difluorophenyl-611-diphenylmethoxy). The vibrational frequency of C-F bond of tetraphenyl molecule was analyzed by correlation analysis. The order of correlation is set 30 and ANDN.Then, the theoretical calculation of the optical properties of red fluorene and its derivatives is carried out, and the geometric configuration, ionization potential and recombination energy of substituent pairs are studied. The influence of absorption and emission spectra. It was found that the absorption peak and fluorescence emission peak of red fluorene and its derivatives were blue shifted with the introduction of alkyl substituted groups. The absorption spectra of the chiral derivatives of R-Cp have strong absorption peaks at 500-700nm and 300-500nm, which is more favorable for visible light absorption. It is suitable for photovoltaic materials such as solar cells. Finally, the electrical properties of red fluorene and its derivatives are calculated. It is found that the introduction of substituents to aromatic rings is beneficial to the formation of excitons. The introduction of substituents in the main chain is beneficial to the enhancement of 蟺 conjugation, while the introduction of branched chains has the opposite effect. Therefore, the introduction of conjugated substituents such as aromatic rings in the main chain can reduce the molecular energy gap. By analyzing the ionization potential, electron affinity energy and recombination energy, it was found that the three derivative molecules, R-Furann, R-Cp and R-OMe3, were more suitable to be used as hole-semiconductor materials. However, the electron and hole recombination energies of R-OMe4 and R-Me have little difference, so they can be used as emitters in organic semiconductor transistors.
【學(xué)位授予單位】：鄭州大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O649.5

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相關(guān)期刊論文 前1條

1 馮琳琳;顧鵬程;姚奕帆;董煥麗;胡文平;;高遷移率聚合物半導(dǎo)體材料[J];科學(xué)通報(bào);2015年23期

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本文編號(hào)：1655761