本文選題：盤狀分子 + 盤狀液晶��； 參考：《北京交通大學》2017年博士論文

【摘要】：大環(huán)盤狀液晶分子材料多由較大的芳香中心核組成,并具有一定的自組裝和分子取向傾向,獲得分子取向的盤狀液晶材料,往往具有優(yōu)異的光電物理特性,其高度各向異性的結構可使其在一定方向上的性能得以優(yōu)化,從而獲得高的載流子遷移率、長的激子擴散長度。尤其是其結構缺陷的自我修復能力,可使得其優(yōu)異的性能保持高度的穩(wěn)定性,令人矚目。因而被認為是極具潛力的、新一代的有機光電子材料。本論文圍繞一系列新型盤狀液晶有機材料在光電子器件中的應用,特別是太陽能電池領域的應用,展開了一系列的基礎研究,具體研究內容包括如下幾個方面:1.本論文首先研究了如何采用盤狀液晶材料,制備具有垂面(homeotropic or face-on)分子取向的薄膜。鑒于常規(guī)盤狀液晶垂面分子取向結構的獲得均采用將盤狀液晶材料灌注入標準液晶盒的方式,但是此方法顯然不適用于逐層構造的光電子器件的制作。本論文將探索在單一基片表面制備可應用的大面積分子垂面取向的方法。雖然在液晶盒中獲得垂面分子取向的報道很多,迄今為止,能在單一基片表面上獲得 面積垂面分子取向的材料卻寥寥無幾,這為其在光電子器件中的應用帶了巨大的挑戰(zhàn)。本論文結合偏光顯微鏡和X射線衍射實驗技術,研究了一系列盤狀液晶材料的分子取向。重點研究了具有電雙極性的盤狀液晶苯并菲SK-75和電子傳輸性能的蒽醌類盤狀液晶AQ6兩種新材料的分子取向特性。本研究第一次嘗試通過溫度調控的方法,實現(xiàn)了 SK-75和AQ6在單一襯底表面上的大面積、穩(wěn)定、均勻、六方對稱高度有序的垂面分子取向,并測得其結構參數(shù)。對比H4TP、H5TP、TPT-BAE較為熟悉的盤狀液晶材料的分子取向發(fā)現(xiàn),分子結構,尤其是柔性側鏈的結構是影響苯并菲類盤狀液晶材料取向的關鍵因素,同時還需選擇適當?shù)臏乜貤l件,才能獲得較好的分子取向。本研究還在上述溫度調控垂面分子取向的基礎上上,進一步引入摻雜誘導輔助的方法研究取向效果。實現(xiàn)了給受體復合體系oo-CuPc:AQ6以及同質復合體系H4TP:SK-75的誘導分子取向調控。2.以苯并菲TPT-BAE和蒽醌AQ6盤狀液晶材料為代表,研究了分子取向對光物理特性及載流子遷移率的影響。木論文創(chuàng)新性的采用與實際有機光電子器件制備方法一致的逐層生長法,通過溫度調控在襯底表面上實現(xiàn)了苯并菲TPT-BAE及蒽醌AQ6盤狀分子垂面取向,構建了接近實際應用的器件結構,并分別對兩種分子取向薄膜的光電性能展開了研究,最后展開了初步光伏器件制備的嘗試。研究發(fā)現(xiàn),短波長的吸收光譜與盤狀分子的取向密切相關。分子垂面取向后,TPT-BAE及蒽醌AQ6在短波段的紫外吸收顯著增強;TPT-BAE薄膜材料呈雙極性載流子(空穴和電子)遷移,垂面取向使得薄膜的空穴和電子遷移率均獲得近三個數(shù)量級的提高,分別達到6.25×10-2和4.28×10-2cm2V-1s-1,接近目前已知的苯并菲類盤狀液晶雙極性載流子遷移率的最大值。這是首次嘗試采用飛行時間法研究在單一襯底上垂面取向生長的盤狀液晶的載流子傳輸特性。率先報道了具有分子取向的新型蒽醌類盤狀液晶材料的電子傳輸特性。采用逐層生長法,構建了基于蒽醌AQ6在單一襯底上生長的垂面分子取向薄膜,研究發(fā)現(xiàn),分子取向的蒽醌AQ6薄膜在紫外短波段光吸收顯著增強,有效地提高了吸收截面;通過構造唯電子器件,并用空間電荷限制電流(SCLC)方法研究薄膜的載流子遷移率,分子取向后的電子遷移率可提高兩個數(shù)量級,達到1.2×10-2 cm2V-1-s-1。采用在單一基片上生長的垂面取向結構研究電子傳輸盤狀液晶的載流子傳輸特性,在國際上尚屬首例。3.采用n型蒽醌AQ6盤狀液晶為受體材料,研究了其與給體聚合物制備本體異質結太陽能電池的可行性。研究首次嘗試將蒽醌AQ6分別與p型給體材料MEH-PPV、P3HT共混,制備了相應的本體異質結太陽能電池器件,探索將AQ6作為受體材料應用于聚合物太陽能電池的可行性。研究發(fā)現(xiàn),AQ6與MEH-PPV之間由于存在分子間相互作用,不能有效地產生光伏響應,推測發(fā)生了分子間電荷轉移,使得該組合不能成為有效的給受體組合;而AQ6與P3HT之間的相互作用較小,該組合可以產生光伏輸出,這說明蒽醌類盤狀液晶材料可以作為受體應用于有機聚合物本體異質結太陽能電池器件中。4.以盤狀大分子金屬酞菁作為有機層與非晶硅雜化的結構非晶硅與有機材料的復合或雜化結構的研究極其稀少,本論文第一次創(chuàng)新性地采用非晶硅與盤狀大分子金屬酞菁的簡單復合結構,并制備了太陽能電池,研究該結構的光伏響應特性。研究發(fā)現(xiàn),非晶硅/金屬酞菁可以獲得光伏輸出,器件的光伏性能與金屬酞菁層的厚度密切相關;光電流的貢獻主要來自于非晶硅層。分析表明,金屬酞菁層與非晶硅層之間不平衡的載流子傳輸能力限制了載流子的傳輸和收集效率,這為以后雜化器件的結構和性能優(yōu)化提供了新的方向。全文共圖53幅,表8個,參考文獻277篇。
[Abstract]:The macrocyclic liquid crystal molecular material is composed of large aromatic core nuclei, and has a certain tendency of self-assembly and molecular orientation. The molecular oriented disk liquid crystal materials often have excellent photoelectric physical properties. The highly anisotropic structure can optimize the performance of a certain square up and thus obtain high load current. The migration rate, the long exciton diffusion length, especially the self repair ability of its structural defects can make its excellent performance maintain high stability and attract people's attention. Therefore, it is considered as a potential new generation of organic optoelectronic materials. This paper focuses on a series of new discoid liquid crystal organic materials in optoelectronic devices. A series of basic studies have been carried out, especially in the field of solar cells. The specific research contents include the following aspects: 1. this paper first studied how to use disk like liquid crystal materials to prepare thin films with homeotropic or face-on molecular orientation. This method is obviously not suitable for the fabrication of optoelectronic devices with layer by layer structure. This paper will explore the method for the preparation of large area molecular vertical orientation on the surface of a single substrate. Although there are many reports on the orientation of the vertical surface in the liquid crystal box, we have so far So far, few materials can be obtained on the surface of a single substrate. This is a great challenge for its application in optoelectronic devices. In this paper, the molecular orientation of a series of disk like liquid crystal materials is studied by polarizing microscope and X ray diffraction technique. The molecular orientation properties of two new materials, discoid benzo phenanthrene SK-75 and electron transport properties of anthraquinone discoid liquid crystal AQ6. The first attempt to achieve a large area, stable, uniform, six square symmetrical and highly ordered vertical surface molecular orientation on the surface of a single substrate by the method of temperature regulation, and the structure of SK-75 and AQ6 The molecular orientation of the H4TP, H5TP, and TPT-BAE discoid liquid crystals is found to be the key factor affecting the orientation of the phenanthrene discoid liquid crystal material, especially the structure of the flexible side chain, and a suitable temperature control condition is needed to obtain better molecular orientation. On the basis of surface molecular orientation, the effect of orientation was further introduced by doping inducement. The induced molecular orientation of oo-CuPc:AQ6 and H4TP:SK-75 in the homogenous complex system was controlled by.2., which was substituted by phenanthrene TPT-BAE and anthraquinone AQ6 discoid liquid crystal. The influence of carrier mobility. The paper innovatively adopts the layer by layer growth method consistent with the actual organic optoelectronic device preparation method. Through the temperature regulation, the vertical surface orientation of phenanthrene TPT-BAE and anthraquinone AQ6 disk molecules is realized on the substrate surface, and the device structure close to the actual application is constructed, and two kinds of molecular oriented films are made respectively. It is found that the short wavelength absorption spectrum is closely related to the orientation of the disc molecules. After the vertical plane orientation, the UV absorption of TPT-BAE and anthraquinone AQ6 increases significantly in the short band, and the TPT-BAE thin film materials migrate in the bipolar carrier (hole and electron). The vertical plane orientation makes the cavitation and electron mobility of the thin films increase nearly three orders of magnitude, reaching 6.25 * 10-2 and 4.28 x 10-2cm2V-1s-1 respectively. It is close to the maximum value of the known phenanthrene discoid liquid crystal bipolar carrier mobility. This is the first attempt to study the vertical surface orientation growth on a single substrate by the flight time interval method. The carrier transmission characteristics of the disk like liquid crystal have been reported. The electron transport characteristics of the novel anthraquinone discoid liquid crystal materials with molecular orientation are reported. A layer by layer growth method is used to construct the pendant surface molecular oriented film based on the anthraquinone AQ6 on a single substrate. The study shows that the molecular oriented anthraquinone AQ6 thin film is absorbed in the UV short band light absorption. The absorption cross section is significantly enhanced and the carrier mobility of the film is studied by constructing a electronic only device and using the space charge limited current (SCLC) method. The electron mobility of the molecule can be increased by two orders of magnitude, and the vertical structure of a 1.2 x 10-2 cm2V-1-s-1. which is grown on a single substrate is used to study the electron transfer. The carrier transmission characteristics of disk like liquid crystals are the first example of.3. using N type anthraquinone AQ6 disk liquid crystal as the receptor material. The feasibility of preparing bulk heterojunction solar cells with donor polymers was studied. The first attempt was to blend the anthraquinone AQ6 with the P donor MEH-PPV and P3HT, and the corresponding bulk heterostructure was prepared. A solar cell device is used to explore the feasibility of applying AQ6 as a receptor material to polymer solar cells. It is found that the interaction between AQ6 and MEH-PPV can not produce the photovoltaic response effectively because of the intermolecular interaction. It is presumed that the charge transfer between molecules has occurred, making the combination not an effective donor combination; and AQ6 The interaction between P3HT is smaller and the combination can produce photovoltaic output, which shows that the anthraquinone discoid liquid crystal material can be used as a receptor in the organic polymer bulk heterojunction solar cell devices, and.4. is used as the composite or heterozygous of amorphous silicon and organic materials. The study of chemical structure is very rare. In this paper, the simple composite structure of amorphous silicon and disk macromolecular metal phthalocyanine was first used in this paper. The solar cell was prepared and the photovoltaic response characteristics of the structure were studied. It was found that the photovoltaic output of the amorphous silicon / metal phthalocyanine can be obtained. The photovoltaic performance of the device and the thickness of the metal phthalocyanine layer are also found. The contribution of the optical current mainly comes from the amorphous silicon layer. The analysis shows that the unbalanced carrier transport capacity between the metal phthalocyanine layer and the amorphous silicon layer restricts the transport and collection efficiency of the carrier, which provides a new direction for the structure and performance optimization of the hybrid devices. The full text is 53, 8, and 277 references. Article.

【學位授予單位】：北京交通大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O753.2

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