非共軛聚合物磷光主體材料和延遲熒光材料的理論研究
發(fā)布時間：2018-11-15 18:07
【摘要】：有機電致發(fā)光器件因在平板顯示和固態(tài)照明等領(lǐng)域具有巨大的應(yīng)用潛力,而備受學(xué)術(shù)界關(guān)注。傳統(tǒng)的熒光材料內(nèi)量子效率只能達到25%,而以重金屬為基礎(chǔ)的磷光材料可以同時捕獲單重態(tài)激子和三重態(tài)激子,實現(xiàn)100%的內(nèi)量子效率。對于磷光發(fā)光器件的發(fā)光層來說,擁有比磷光客體材料高的三重態(tài)能是對主體材料的基本要求,同時它還應(yīng)兼具平衡電子空穴注入和快速傳輸激子的能力,來降低能力損失。當(dāng)前,提高器件效率和合成色純度較高的藍色磷光主體材料是這個領(lǐng)域亟待解決的問題。此外,剛興起的熱活化延遲熒光材料,同樣可以捕獲單重態(tài)激子和三重態(tài)激子,而使其內(nèi)量子產(chǎn)率達到100%。尋找具有較小單重態(tài)-三重態(tài)能量差的材料,以及探索內(nèi)部電子和能量的轉(zhuǎn)化機制,是該領(lǐng)域在當(dāng)前的研究中心。當(dāng)前,人們在研究磷光材料和延遲熒光材料上投入了大量的精力,有力的推動了電致發(fā)光器件的發(fā)展。本文采用密度泛函理論和含時密度泛函理論研究了系列非共軛聚合物磷光主體材料和D-A-D結(jié)構(gòu)類型的延遲熒光發(fā)光材料,詳細討論了這些物質(zhì)作為磷光主體材料和延遲熒光發(fā)光材料時的潛在性能,同時構(gòu)建主客體模型,研究主客體之間的能量和電子轉(zhuǎn)移機制。我們希望這些工作能夠為主體材料和延遲熒光材料的設(shè)計研究發(fā)揮出應(yīng)有的貢獻。本論文將從下五個部分進行討論：第一部分,介紹有機電致發(fā)光材料的研究現(xiàn)狀、器件構(gòu)成以及工作原理,闡述磷光主體材料以及延遲熒光材料的基本要求、分子結(jié)構(gòu)及其設(shè)計原理。同時對電致發(fā)光材料的發(fā)展前景進行了展望,并指出本文的研究意義。第二部分,詳細的介紹本文研究所使用的相關(guān)計算理論——分子軌道理論、密度泛函理論、含時密度泛函理論、其他的重要分析方法(例如,自然成鍵軌道分析、Marcus電荷轉(zhuǎn)移理論等)以及發(fā)光理論。第三部分,介紹利用密度泛函理論和含時密度泛函理論方法對以聚苯乙烯為基礎(chǔ)的一系列非共軛聚合物的主體分子性能展開研究。結(jié)果表明非共軛聚合物能夠有效地阻止三重態(tài)激子的離域,使主體材料擁有一個較高的三重態(tài)能,同時通過引入合適的取代基(咔唑、吡咯、三苯胺等)使相關(guān)主體材料兼具好的電荷空穴傳輸能力。另外,結(jié)構(gòu)分析結(jié)果表明,三重態(tài)和基態(tài)之間的結(jié)構(gòu)變化,即三重態(tài)結(jié)構(gòu)的平面化,是造成聚苯乙烯衍生物三重態(tài)能下降的本質(zhì)原因。在主客體能量、主體發(fā)射光譜和客體吸收光譜以及主客體堆積模型的研究中表明,對位咔唑取代的poly(4-vinytriphenylamine)具有較小的單三態(tài)能量差,能夠更好的和發(fā)光體匹配,即擁有更好的主體材料性能。第四部分,利用密度泛函和含時密度泛函以及其它相關(guān)理論對咔唑連接C/Si衍生物進行了詳細的主體性能研究。通過咔唑直接連接C/Si衍生物以及它們中間引入苯環(huán)作為橋體的這兩個系列分子結(jié)構(gòu)的研究表明前一系列分子具有較高的三線態(tài)能、較強的分子軌道相互作用和較小的單三態(tài)能量差,這是由于三重態(tài)激子更容易分布在具有較大平面的區(qū)域,主客體之間存在有效的Forster和Dexter能量轉(zhuǎn)移。通過C和Si的比較發(fā)現(xiàn),Si更容易阻止三線態(tài)激子的離域。對于后一系列分子,我們在咔唑上引入甲基和叔丁基進行了進一步的研究,結(jié)果表明HOMO和LUMO之間出現(xiàn)好的分裂,表現(xiàn)出良好的軌道相互作用和較小的單-三態(tài)能量差。結(jié)合本體系的研究可以得出,咔唑基團直接連接Si原子系列更具備作為主體材料的潛能。第五部分,采用密度泛函理論和含時密度泛函理論研究了以D-A-D結(jié)構(gòu)為基礎(chǔ)的熱活化延遲熒光材料。通過供體(9,9-dimethyl-9,10-dihydroacridine)和受體(2,5-phenyl-5,10-dihydrophenazine)采用鄰、間、對的不同連接形式設(shè)計出一系列分子,預(yù)測它們作為延遲熒光材料的性能。結(jié)果表明供受體相鄰原子之間的相互作用對單重態(tài)-三重態(tài)能量差有很大的影響。通過對激發(fā)態(tài)能量以及自然躍遷軌道方面分析表明供受體之間用C-N鍵相連的分子與主體分子可形成分子間的單重態(tài)-單重態(tài)、單重態(tài)-三重態(tài)和三重態(tài)-三重態(tài)的能量轉(zhuǎn)移方式。
[Abstract]:The organic electroluminescent device has great application potential in the fields of flat panel display and solid state lighting, and has attracted the attention of the academic community. The quantum efficiency of the conventional fluorescent material can only reach 25%, while the phosphorescent material based on the heavy metal can simultaneously capture both the single-heavy-state exciton and the triplet exciton to realize the internal quantum efficiency of 100%. For the light-emitting layer of the phosphorescent light-emitting device, the triplet energy having a higher triplet energy than the phosphorescent guest material can be a basic requirement for the host material, and at the same time it should have the ability to balance the electron-hole injection and the fast-transmission exciton to reduce the power loss. At present, the blue phosphorescent host material with high device efficiency and high synthesis color purity is a problem to be solved in this field. In addition, the newly-developed heat-activated delayed fluorescent material can also capture a single-heavy-state exciton and a triplet exciton to achieve a quantum yield of 100%. The search for materials with a smaller single-to-triplet energy difference, as well as a mechanism to explore the internal electron and energy, is the current research center in this field. At present, a lot of energy is put into the research of the phosphorescent material and the delayed fluorescent material, and the development of the electroluminescent device is strongly promoted. In this paper, a series of non-copolymeric phosphorescent host materials and D-A-D structure types of delayed fluorescent light-emitting materials are studied by using the density functional theory and the time-density functional theory, and the potential properties of these materials as the phosphorescent host material and the delayed fluorescent light-emitting material are discussed in detail. At the same time, the main object model is constructed, and the energy and the electron transfer mechanism between the subject and the object are studied. We hope that these work will have a due contribution to the design study of the bulk material and the delayed fluorescent material. This paper will discuss the following five parts: the first part, the research status of the organic electroluminescent material, the structure of the device and the working principle, the basic requirements, the molecular structure and the design principle of the phosphorescent host material and the delayed fluorescent material. At the same time, the development prospect of the electroluminescent material is prospected, and the significance of this paper is also pointed out. In the second part, the relevant calculation theory _ molecular orbital theory, the density functional theory, the time-density functional theory, other important analytical methods (e.g., the natural-bond-track analysis, the Marcus charge transfer theory, etc.) used by the Institute and the light-emitting theory are introduced in detail. In the third part, the main molecular properties of a series of non-copolymeric polymers based on polystyrene are studied by using the density functional theory and the time-density functional theory. The results show that the non-copolymeric polymer can effectively prevent the off-domain of the triplet exciton, so that the host material has a higher triplet energy, and at the same time, the relevant host material has good charge hole transport capacity by the introduction of a suitable substituent (e.g., triphenyl, triphenylamine, triphenylamine, etc.). In addition, the structural analysis shows that the change of the structure between the triplet state and the ground state, that is, the planarization of the triplet structure, is the essential cause of the degradation of the triplet state of the polystyrene derivative. In the study of the main object energy, the main body emission spectrum and the object absorption spectrum and the main object stacking model, the poly (4-vinyttrium), which is substituted by the contraposition, has a small single tri-state energy difference, and can be better matched with the luminous body, that is, the performance of the main body material is better. In the fourth part, the C/ Si derivatives are studied in detail by using the density functional and the time-time-density functional and other relevant theories. The study on the molecular structure of the two series of molecules which are directly connected to the C/ Si derivative and the intermediate introduced benzene ring as the bridge body shows that the former series of molecules have a high triplet energy, a stronger molecular orbital interaction and a smaller single tristate energy difference, This is because the triplet exciton is more easily distributed in the region with the larger plane, and there is an effective Forster and Dexter energy transfer between the main objects. By comparison of C and Si, Si is more likely to block off-domain of triplet exciton. For the latter series of molecules, we conducted a further study on the introduction of methyl and tert-butyl into the molecular sieve. The results show that a good break between the HOMO and the LUMO shows good orbital interaction and a small single-state energy difference. According to the study of this system, the direct connection of the Si atom series to the Si atom series is the potential of the main material. In the fifth part, the thermal activation delayed fluorescent material based on D-A-D structure is studied by the density functional theory and the time-density functional theory. A series of molecules were designed by means of a donor (9, 9-dimetyl-9, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-di@@ The results show that the interaction between the adjacent atoms of the receptor has a great effect on the single-state-triplet energy difference. By analyzing the energy of the excited state and the natural transition orbit, it is shown that the molecule and the host molecule which are connected by the C-N bond between the acceptor and the acceptor can form the energy transfer mode between the single-state, the single-state, the singlet-triplet state and the triplet-triplet state between the molecules.
【學(xué)位授予單位】：西南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TN383.1
本文編號：2334046
[Abstract]:The organic electroluminescent device has great application potential in the fields of flat panel display and solid state lighting, and has attracted the attention of the academic community. The quantum efficiency of the conventional fluorescent material can only reach 25%, while the phosphorescent material based on the heavy metal can simultaneously capture both the single-heavy-state exciton and the triplet exciton to realize the internal quantum efficiency of 100%. For the light-emitting layer of the phosphorescent light-emitting device, the triplet energy having a higher triplet energy than the phosphorescent guest material can be a basic requirement for the host material, and at the same time it should have the ability to balance the electron-hole injection and the fast-transmission exciton to reduce the power loss. At present, the blue phosphorescent host material with high device efficiency and high synthesis color purity is a problem to be solved in this field. In addition, the newly-developed heat-activated delayed fluorescent material can also capture a single-heavy-state exciton and a triplet exciton to achieve a quantum yield of 100%. The search for materials with a smaller single-to-triplet energy difference, as well as a mechanism to explore the internal electron and energy, is the current research center in this field. At present, a lot of energy is put into the research of the phosphorescent material and the delayed fluorescent material, and the development of the electroluminescent device is strongly promoted. In this paper, a series of non-copolymeric phosphorescent host materials and D-A-D structure types of delayed fluorescent light-emitting materials are studied by using the density functional theory and the time-density functional theory, and the potential properties of these materials as the phosphorescent host material and the delayed fluorescent light-emitting material are discussed in detail. At the same time, the main object model is constructed, and the energy and the electron transfer mechanism between the subject and the object are studied. We hope that these work will have a due contribution to the design study of the bulk material and the delayed fluorescent material. This paper will discuss the following five parts: the first part, the research status of the organic electroluminescent material, the structure of the device and the working principle, the basic requirements, the molecular structure and the design principle of the phosphorescent host material and the delayed fluorescent material. At the same time, the development prospect of the electroluminescent material is prospected, and the significance of this paper is also pointed out. In the second part, the relevant calculation theory _ molecular orbital theory, the density functional theory, the time-density functional theory, other important analytical methods (e.g., the natural-bond-track analysis, the Marcus charge transfer theory, etc.) used by the Institute and the light-emitting theory are introduced in detail. In the third part, the main molecular properties of a series of non-copolymeric polymers based on polystyrene are studied by using the density functional theory and the time-density functional theory. The results show that the non-copolymeric polymer can effectively prevent the off-domain of the triplet exciton, so that the host material has a higher triplet energy, and at the same time, the relevant host material has good charge hole transport capacity by the introduction of a suitable substituent (e.g., triphenyl, triphenylamine, triphenylamine, etc.). In addition, the structural analysis shows that the change of the structure between the triplet state and the ground state, that is, the planarization of the triplet structure, is the essential cause of the degradation of the triplet state of the polystyrene derivative. In the study of the main object energy, the main body emission spectrum and the object absorption spectrum and the main object stacking model, the poly (4-vinyttrium), which is substituted by the contraposition, has a small single tri-state energy difference, and can be better matched with the luminous body, that is, the performance of the main body material is better. In the fourth part, the C/ Si derivatives are studied in detail by using the density functional and the time-time-density functional and other relevant theories. The study on the molecular structure of the two series of molecules which are directly connected to the C/ Si derivative and the intermediate introduced benzene ring as the bridge body shows that the former series of molecules have a high triplet energy, a stronger molecular orbital interaction and a smaller single tristate energy difference, This is because the triplet exciton is more easily distributed in the region with the larger plane, and there is an effective Forster and Dexter energy transfer between the main objects. By comparison of C and Si, Si is more likely to block off-domain of triplet exciton. For the latter series of molecules, we conducted a further study on the introduction of methyl and tert-butyl into the molecular sieve. The results show that a good break between the HOMO and the LUMO shows good orbital interaction and a small single-state energy difference. According to the study of this system, the direct connection of the Si atom series to the Si atom series is the potential of the main material. In the fifth part, the thermal activation delayed fluorescent material based on D-A-D structure is studied by the density functional theory and the time-density functional theory. A series of molecules were designed by means of a donor (9, 9-dimetyl-9, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-dihydro-5, 10-di@@ The results show that the interaction between the adjacent atoms of the receptor has a great effect on the single-state-triplet energy difference. By analyzing the energy of the excited state and the natural transition orbit, it is shown that the molecule and the host molecule which are connected by the C-N bond between the acceptor and the acceptor can form the energy transfer mode between the single-state, the single-state, the singlet-triplet state and the triplet-triplet state between the molecules.
【學(xué)位授予單位】：西南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TN383.1
【共引文獻】
相關(guān)期刊論文 前5條
1 龔文亮;熊祖勁;朱明強;;六芳基聯(lián)咪唑分子開關(guān)的研究進展[J];影像科學(xué)與光化學(xué);2014年01期
2 楊科;張艷;徐建華;;電子轉(zhuǎn)移光氧化反應(yīng)在有機合成中的應(yīng)用[J];影像科學(xué)與光化學(xué);2014年05期
3 徐海兵;何亭;唐明靜;彭雪峰;鄧建國;;光致變色金屬(Ru,Pt,Ln)-二芳基乙烯分子開關(guān)[J];科學(xué)通報;2014年30期
4 趙明星;高穎;孟躍;倪生良;;配合物Zn(C_3H_4N_2)_2(C_8H_6O_2Br)_2的水熱合成、晶體結(jié)構(gòu)及性質(zhì)[J];化學(xué)通報;2014年11期
5 張平;劉杰;黃建炎;楊家祥;;3-氨基-6-(2-(4-吡啶基)乙烯基)-9-丁基咔唑的合成及性質(zhì)[J];應(yīng)用化學(xué);2014年10期
相關(guān)博士學(xué)位論文 前10條
1 丁力;基于噻噸酮和芴的熒光化學(xué)傳感器[D];華東理工大學(xué);2014年
2 王麗娟;有機光電功能材料的電荷傳輸性質(zhì)和光物理性質(zhì)的理論研究[D];吉林大學(xué);2014年
3 元勇軍;金屬銥配合物在光致析氫中的性能研究[D];南京大學(xué);2014年
4 劉岸杰;吡唑啉酮類席夫堿光致變色化合物的理論研究[D];新疆大學(xué);2014年
5 張曉光;光譜特性可調(diào)控材料及共軛體系激光限幅材料研究[D];北京科技大學(xué);2015年
6 楊寧;小分子有機電致熒光器件研究及其驅(qū)動系統(tǒng)的設(shè)計[D];西北工業(yè)大學(xué);2014年
7 王野;激發(fā)態(tài)分子間質(zhì)子轉(zhuǎn)移氫鍵動力學(xué)的理論研究[D];吉林大學(xué);2015年
8 潘玉鈺;熱激子反系間竄越實現(xiàn)高效率有機電致發(fā)光材料的分子設(shè)計原理[D];吉林大學(xué);2015年
9 陳先凱;有機光電材料中的電子—振動耦合：在電荷傳輸以及發(fā)光性質(zhì)中的作用[D];吉林大學(xué);2015年
10 金會義;新型光致變色電致變色化合物的合成及性能研究[D];天津大學(xué);2014年
相關(guān)碩士學(xué)位論文 前10條
1 李亞婧;功能性鈦酸酯催化己內(nèi)酯常溫活性開環(huán)聚合[D];華中科技大學(xué);2013年
2 蔡建光;基于雙苯并咪唑的銥配合物合成及其光催化還原水出氫氣[D];南京理工大學(xué);2014年
3 張露瓊;高效磷光功能配體鉑（Ⅱ）配合物的分子設(shè)計和理論研究[D];西南大學(xué);2014年
4 左陳;改性二氧化硅的合成與提高鄰菲咯啉釕在硅膠中的分散及應(yīng)用研究[D];華南理工大學(xué);2014年
5 王志遠;新型非貴金屬光催化制氫材料的制備及其光解水制氫性能的研究[D];鄭州大學(xué);2014年
6 林宏;基于一種鉑配合物的有機電致磷光及激光特性研究[D];上海大學(xué);2014年
7 張玉巾;兩種有機化合物（光致/化學(xué)）發(fā)光性能的優(yōu)化及應(yīng)用[D];北京交通大學(xué);2014年
8 段小偉;1,4-二氫吡嗪及其四氮雜四星烷的合成研究[D];北京工業(yè)大學(xué);2014年
9 歐陽冰;含雜原子的共軛分子體系激發(fā)態(tài)結(jié)構(gòu)動力學(xué)和衰變機制[D];浙江理工大學(xué);2015年
10 唐佳;藍磷光金屬配合物的理論研究和分子設(shè)計[D];吉林大學(xué);2015年
，本文編號：2334046
本文鏈接：http://sikaile.net/kejilunwen/dianzigongchenglunwen/2334046.html
最近更新
教材專著
