本文選題：高分子凝聚態(tài)結(jié)構(gòu) + 有序　； 參考：《吉林大學(xué)》2017年碩士論文

【摘要】：共軛高分子由于具有良好的成膜性、可以實(shí)現(xiàn)大面積、加工成本較低,廣泛應(yīng)用在有機(jī)太陽(yáng)能電池,有機(jī)發(fā)光二極管和有機(jī)場(chǎng)效應(yīng)晶體管領(lǐng)域。共軛高分子的光電理論知識(shí)已日漸成熟,其實(shí)際應(yīng)用價(jià)值也非常巨大。提高載流子遷移率進(jìn)而提高器件效率是眾多研究者努力的目標(biāo)。提高高分子材料的有序聚集,并且使其形成互穿網(wǎng)絡(luò)結(jié)構(gòu),可以大幅度提高材料的載流子遷移率。高分子材料具有軟物質(zhì)特性,對(duì)外場(chǎng)刺激響應(yīng)強(qiáng)烈。高分子性能不完全取決于化學(xué)結(jié)構(gòu),不同凝聚態(tài)結(jié)構(gòu)顯示不同的性質(zhì)。本論文旨在研究外場(chǎng)(溶劑,濃度,轉(zhuǎn)速,溫度,電場(chǎng))對(duì)共軛高分子凝聚態(tài)結(jié)構(gòu)的影響。進(jìn)而通過(guò)外場(chǎng)調(diào)控共軛高分子的有序凝聚態(tài)結(jié)構(gòu)達(dá)到提高載流子遷移率,最終提高器件效率的目的。高分子前體溶液中分子鏈的構(gòu)象和聚集狀態(tài)以及成膜過(guò)程會(huì)影響形成薄膜的凝聚態(tài)結(jié)構(gòu),最終影響器件性能。通過(guò)系統(tǒng)的研究濃度,旋涂轉(zhuǎn)速,溫度和溶劑對(duì)PTB7薄膜凝聚態(tài)結(jié)構(gòu)的影響,發(fā)現(xiàn):隨濃度降低(低纏結(jié)度)轉(zhuǎn)速增加(解纏結(jié)),PTB7主鏈共軛長(zhǎng)度增加,π-π相互作用增強(qiáng),有序聚集尺寸增大,主要是由鏈內(nèi)相互作用誘導(dǎo)有序聚集,分子鏈纏結(jié)不利于有序聚集,降低有序度;不良溶劑1,2二氯乙烷使PTB7主鏈纏結(jié),卷曲,而形成無(wú)定型態(tài)。當(dāng)繼續(xù)降低溶劑的溶解性,分子鏈間吸引力增強(qiáng),鏈段間的距離減小,部分鏈段間π-π相互作用增強(qiáng),產(chǎn)生局部有序聚集,增加主鏈共軛長(zhǎng)度。我們得出結(jié)論:PTB7主要存在3種聚集態(tài)結(jié)構(gòu):1、由分子鏈內(nèi)相互作用驅(qū)使分子鏈自折疊形成的有序聚集;2、分子鏈間纏結(jié)形成的無(wú)定型態(tài);3、分子鏈纏結(jié)密度達(dá)到一定時(shí),部分鏈段間π-π相互作用增強(qiáng),產(chǎn)生局部有序聚集。由于高分子具有分子量和分子尺寸的多分散性和物質(zhì)結(jié)構(gòu)多層次性的特點(diǎn),PTB7的三種聚集態(tài)結(jié)構(gòu)在成膜過(guò)程中可能同時(shí)存在。結(jié)合已有文獻(xiàn)報(bào)道,我們推測(cè)增加分子鏈自折疊形成的小尺寸有序聚集,減少分子鏈纏結(jié)形成的無(wú)定型態(tài),可以提高載流子遷移率,達(dá)到提高器件效率的目的。這對(duì)提高光電器件效率具有重要的理論與實(shí)際意義。電場(chǎng)對(duì)共軛高分子凝聚態(tài)結(jié)構(gòu)影響的研究非常少,但是具有方向性的電場(chǎng)對(duì)共軛高分子鏈取向的作用不容忽視。我們通過(guò)在玻璃化轉(zhuǎn)變溫度以上退火的過(guò)程中加電場(chǎng),研究電場(chǎng)對(duì)不同極性高分子鏈取向的影響,發(fā)現(xiàn):電場(chǎng)增強(qiáng)P3HT主鏈π-π相互作用,并且增大其結(jié)晶度;電場(chǎng)使MEH-PPV主鏈共軛長(zhǎng)度有微弱增加,并使其聚集減少。得出結(jié)論:P3HT主鏈S原子具有較強(qiáng)的電負(fù)性,偶極矩較大,在電場(chǎng)作用下響應(yīng)更加明顯。MEH-PPV雖然含有兩個(gè)電負(fù)性較強(qiáng)的O原子,但由于其處在對(duì)稱位置上,所以整體偶極矩較小,在電場(chǎng)作用下響應(yīng)微弱。極性高分子在電場(chǎng)作用下,有序度增加。并且偶極矩(極性)越大,電場(chǎng)對(duì)其調(diào)控作用越顯著。
[Abstract]:Conjugated polymers are widely used in the fields of organic solar cells, organic light emitting diodes and field effect transistors due to their good film-forming properties, large area and low processing cost. The photoelectric theory of conjugated polymer has matured and its practical application value is very great. Increasing carrier mobility and thus improving device efficiency is the goal of many researchers. The carrier mobility can be greatly improved by increasing the ordered aggregation of polymer materials and forming an interpenetrating network structure. The polymer material has the soft matter characteristic, the external field stimulates the response to be strong. The properties of polymer are not completely dependent on the chemical structure, and different condensed matter structures show different properties. In this paper, the effects of external field (solvent, concentration, rotation speed, temperature, electric field) on the condensed structure of conjugated polymers are studied. Furthermore, the ordered condensed matter structure of conjugated polymer is controlled by external field to improve the carrier mobility and the device efficiency. The conformation and aggregation of molecular chains in polymer precursor solution and the process of film formation will affect the condensed structure of the film and ultimately affect the performance of the device. The effects of concentration, spin-coating speed, temperature and solvent on the condensed structure of PTB7 thin films were systematically studied. It was found that the 蟺-蟺 interaction increased with the decrease of concentration (low entanglement degree) and the increase of conjugation length of the main chain of PTB7. The ordered aggregation size is increased, which is mainly induced by intrachain interaction, the molecular chain entanglement is not conducive to the ordered aggregation, and the order degree is reduced, and the bad solvent 1 ~ (2) dichloroethane makes the PTB7 main chain entangled, curled, and forms an amorphous state. When the solubility of the solvent continues to decrease, the attraction between chains increases, the distance between segments decreases, and the 蟺-蟺 interaction between some segments increases, resulting in a local ordered aggregation and an increase in the conjugate length of the main chain. We draw the conclusion that there are three kinds of aggregation structure: 1, the ordered aggregation of molecular chains driven by intra-chain interaction, the formation of interchain entanglement, and the formation of interchain entanglement, when the molecular chain entanglement density reaches a certain degree. The 蟺-蟺 interaction between partial segments is enhanced, resulting in local ordered aggregation. Due to the polydispersity of molecular weight and molecular size and the multilevel structure of PTB7, the three aggregates of PTB7 may exist simultaneously in the process of film formation. Combined with the previous reports, we speculate that increasing the small size ordered aggregation of molecular chain self-folding and reducing the amorphous state formed by molecular chain entanglement can increase the carrier mobility and achieve the purpose of improving the device efficiency. It is of great theoretical and practical significance to improve the efficiency of optoelectronic devices. The effect of electric field on conjugated polymer structure is very little, but the effect of directional electric field on the orientation of conjugated polymer chain can not be ignored. We study the effect of electric field on the orientation of different polarity polymer chains by adding electric field in the process of annealing above glass transition temperature. It is found that the electric field enhances the 蟺-蟺 interaction of the main chain of P3HT and increases its crystallinity. The electric field increases the conjugate length of the main chain of MEH-PPV slightly and reduces its aggregation. It is concluded that the S atom of the W P3HT main chain has strong electronegativity, larger dipole moment, and more obvious response under electric field. Although there are two O atoms with strong electronegativity, the whole dipole moment is smaller because of its symmetrical position. The response is weak under the action of electric field. The order of polar polymer increases under the action of electric field. The greater the dipole moment (polarity) is, the more significant the electric field is.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O631.1

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