本文選題：有機(jī)本體異質(zhì)結(jié)太陽(yáng)電池 + 亞納秒級(jí)瞬態(tài)光電導(dǎo)　； 參考：《華南理工大學(xué)》2014年博士論文

【摘要】：有機(jī)太陽(yáng)電池是目前太陽(yáng)能研究領(lǐng)域的熱點(diǎn)研究方向。相比起已發(fā)展成熟的無(wú)機(jī)半導(dǎo)體太陽(yáng)電池技術(shù)，有機(jī)太陽(yáng)電池有一些獨(dú)特的優(yōu)點(diǎn)，但是效率偏低,是限制其大規(guī)模應(yīng)用的主要因素。為了讓有機(jī)太陽(yáng)電池成為真正能實(shí)際大規(guī)模應(yīng)用推廣的產(chǎn)品，必須進(jìn)一步提高其能量轉(zhuǎn)換效率，而為了做到這一點(diǎn)，必須深入了解有機(jī)太陽(yáng)電池的工作機(jī)理。太陽(yáng)電池的工作機(jī)理最重要的問(wèn)題取決于三個(gè)物理過(guò)程：光生載流子的產(chǎn)生、光生載流子的復(fù)合以及光生載流子的輸運(yùn)。 以上三個(gè)過(guò)程的時(shí)間尺度在數(shù)百飛秒到數(shù)納秒的范疇，本論文的研究目的在于運(yùn)用各種快速響應(yīng)實(shí)驗(yàn)技術(shù)探明有機(jī)太陽(yáng)電池材料在這些時(shí)間尺度上的超快速光生載流子動(dòng)力學(xué)過(guò)程。本論文的研究主要通過(guò)亞納秒級(jí)瞬態(tài)光電導(dǎo)測(cè)量技術(shù)以及飛秒級(jí)瞬態(tài)光致吸收光譜測(cè)量技術(shù)這兩種實(shí)驗(yàn)手段，對(duì)小分子體異質(zhì)結(jié)太陽(yáng)電池以及聚合物體異質(zhì)結(jié)太陽(yáng)電池兩類(lèi)高效率有機(jī)太陽(yáng)電池材料體系的載流子生成，復(fù)合以及輸運(yùn)三方面問(wèn)題進(jìn)行詳細(xì)研究。除此之外，本論文還涉及新型負(fù)電極修飾層的研究以及其在有機(jī)光致發(fā)光器件以及有機(jī)太陽(yáng)電池器件中的應(yīng)用。本論文分為五大部分。 第一部分研究通過(guò)亞納秒級(jí)瞬態(tài)光電導(dǎo)實(shí)驗(yàn)測(cè)量了兩種使用小分子給體的高效率體異質(zhì)結(jié)材料體系的瞬態(tài)光電導(dǎo)特性及其在不同溫度的表現(xiàn)。研究發(fā)現(xiàn)小分子體異質(zhì)結(jié)薄膜的無(wú)序程度與聚合物體異質(zhì)結(jié)薄膜相差不大，但是載流子輸運(yùn)可以更長(zhǎng)時(shí)間保持高遷移率的自由輸運(yùn)，，對(duì)有機(jī)太陽(yáng)電池的效率提高有利。另外發(fā)現(xiàn)小分子材料體系與聚合物材料體系的載流子在陷阱能級(jí)中的弛豫過(guò)程完全不同，小分子材料體系的載流子遷移率衰減明顯慢于聚合物材料體系，這一特性有可能對(duì)小分子有機(jī)太陽(yáng)電池器件的高效率有積極貢獻(xiàn)。 第二部分進(jìn)一步研究有機(jī)太陽(yáng)電池材料體系的超快速電荷分離過(guò)程，通過(guò)飛秒級(jí)瞬態(tài)光致吸收光譜實(shí)驗(yàn)方法考察了一種高效可溶液加工小分子給體材料的體異質(zhì)結(jié)薄膜以及雙層結(jié)構(gòu)薄膜的光生載流子動(dòng)力學(xué)特性。本部分研究結(jié)果進(jìn)一步驗(yàn)證了超快速電荷分離模型的正確性，并表明超快速電荷分離過(guò)程產(chǎn)生的根本原因是有機(jī)半導(dǎo)體材料激發(fā)態(tài)的波函數(shù)在數(shù)百飛秒的時(shí)間尺度內(nèi)是量子相干疊加的，本征具有離域性。本部分研究提出了提高有機(jī)太陽(yáng)電池性能的新思路，即延長(zhǎng)有機(jī)太陽(yáng)電池材料的量子退相干時(shí)間。 第三部分工作改進(jìn)了飛秒級(jí)瞬態(tài)光致吸收光譜測(cè)量系統(tǒng)用以測(cè)量瞬態(tài)光致反射光譜，并考察了五種高效有機(jī)太陽(yáng)電池體異質(zhì)結(jié)材料體系的實(shí)際太陽(yáng)電池器件的瞬態(tài)光致反射光譜，從中獲得了實(shí)際器件中的載流子動(dòng)力學(xué)過(guò)程以及這一過(guò)程與電場(chǎng)強(qiáng)度的相關(guān)性。研究發(fā)現(xiàn)這些高效材料體系中不存在明顯的孿生對(duì)復(fù)合現(xiàn)象。另外本部分研究結(jié)果表明超快電荷分離過(guò)程的確存在于實(shí)際太陽(yáng)電池器件中，且器件樣品中的載流子生成過(guò)程與薄膜樣品類(lèi)似。 第四部分工作將兩種新型非離子型可交聯(lián)水/醇溶聚合物作為單獨(dú)負(fù)電極修飾層材料應(yīng)用于倒裝有機(jī)電致發(fā)光器件中。發(fā)現(xiàn)使用新型負(fù)電極修飾層材料的倒裝有機(jī)電致發(fā)光器件的效率非常高，可以和最好的普通結(jié)構(gòu)器件相媲美，從而證明了非離子型可交聯(lián)水/醇溶聚合物作為負(fù)電極修飾層的巨大價(jià)值，值得將其推廣到有機(jī)太陽(yáng)電池應(yīng)用領(lǐng)。 第五部分工作系統(tǒng)研究了五種不同離子型的水/醇溶共軛聚合物作為聚合物太陽(yáng)電池的負(fù)電極修飾層的性能。研究發(fā)現(xiàn)全部材料都能不同程度提高普通結(jié)構(gòu)以及倒裝結(jié)構(gòu)聚合物太陽(yáng)點(diǎn)器件的性能，其中以?xún)尚噪x子型材料以及非離子型材料在普通結(jié)構(gòu)器件中性能最佳，自由陰離子型材料在倒裝結(jié)構(gòu)器件中表現(xiàn)最佳，而自由陽(yáng)離子型材料在倒裝結(jié)構(gòu)器件中反而降低器件性能。我們從兩個(gè)理論模型出發(fā)考察水/醇溶共軛聚合物材料作為負(fù)電極修飾層的機(jī)理：離子重新分布理論以及界面電偶極子理論。最終證明兩方面都對(duì)水/醇溶共軛聚合物材料作為負(fù)電極修飾層的性能有貢獻(xiàn)，而且自由陰離子型水/醇溶共軛聚合物理論上最適合作為負(fù)電極修飾層材料。
[Abstract]:Organic solar cells are the hot research fields in the field of solar energy research. Compared with the mature inorganic semiconductor solar cell technology, organic solar cells have some unique advantages, but the efficiency is low, which is the main factor limiting the large-scale application of the solar cells. In order to make the solar cells of the machine truly practical and large-scale application In order to achieve this, we must further understand the working mechanism of the organic solar cell. The most important problem of the working mechanism of the solar cell depends on three physical processes: the generation of the optical carrier, the recombination of the photogenerated carrier, and the transport of the light carrier.
The time scale of the above three processes is in the range of hundreds of femtosecond to nanosecond. The purpose of this paper is to explore the ultra fast optical carrier dynamics process of organic solar cell materials on these time scales by using various fast response experiments. In addition to the two experimental methods, such as the carrier generation, recombination and transport of two kinds of high efficiency organic solar cell materials, such as small molecular body heterojunction solar cells and two kinds of polymer heterojunction solar cells, the two experimental means are also studied in detail. The new negative electrode modified layer and its application in organic light emitting devices and organic solar cell devices are divided into five parts.
In the first part, the transient photoconductivity of two high efficiency bulk heterojunction materials using small molecule donor and its performance at different temperatures were measured by the subnanosecond transient photoconductivity test. It is beneficial to improve the efficiency of organic solar cells for the free transport of high mobility for longer time. In addition, it is found that the relaxation process of the carrier in the trap level of the small molecular material system and the polymer material system is completely different, and the decay of the carrier migration rate of the small molecular material system is obviously slower than that of the polymer material system. One characteristic may contribute positively to the efficiency of small molecule organic solar cell devices.
In the second part, the ultra fast charge separation process of the organic solar cell material system is further studied. By the femtosecond transient photoinduced absorption spectroscopy, a high efficiency solution processing small molecular donor body heterojunction film and the photodynamic characteristic of the two-layer structure film are investigated. One step is to verify the correctness of the ultra fast charge separation model and show that the fundamental reason for the ultra fast charge separation process is that the wave function of the excited state of the organic semiconductor material is superposed by quantum coherency in the time scale of hundreds of femtosecond, and the eigenvalue is off domain. This part of the study proposes a new method to improve the performance of organic solar cells. The idea is to extend the quantum decoherence time of organic solar cell materials.
The third part has improved the femtosecond transient photoinduced absorption spectrum measurement system to measure transient photoinduced reflectance spectroscopy, and investigated the transient photoinduced reflectance spectra of the actual solar cell devices of five kinds of high efficient organic solar cell heterojunction materials. The relationship between the process and the strength of the electric field has been found. It is found that there are no obvious twin pairs in these high efficiency materials. In addition, the results show that the ultrafast charge separation process does exist in the actual solar cell devices, and the carrier generation in the device samples is similar to that of the film samples.
In the fourth part, two new nonionic crosslinked water / alcohol soluble polymers are used as separate negative electrode modified layer materials in the inverted organic electroluminescent devices. It is found that the efficiency of the inverted organic electroluminescent devices using the new negative electrode modified layer material is very high and can be compared with the best common structural devices. It is proved that the nonionic crosslinkable water / alcohol soluble polymer as a negative electrode modification layer has great value, and is worthy of being extended to the application of organic solar cells.
The fifth part of the work system studies the performance of five different ionic type water / alcohol soluble conjugated polymers as the negative electrode modification layer of the polymer solar cells. It is found that all materials can improve the properties of the common structure and the inverted structure polymer solar point devices in varying degrees, in which the amphoteric ion type materials and non ions are used. The performance of the type material is the best in the common structural device, and the free anion type material is the best in the reverse structure device, and the free cation type material reduces the performance of the device in the reverse structure device. We study the mechanism of the water / alcohol soluble conjugated polymer as the negative electrode modified layer from two theoretical models: ion weight. The new distribution theory and the interfacial electric dipole theory prove that the two aspects have contributed to the performance of the water / alcohol soluble conjugated polymer as the negative electrode modified layer, and the free anionic water / alcohol soluble conjugated polymer is the most suitable for the negative electrode modified layer material.

【學(xué)位授予單位】：華南理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類(lèi)號(hào)】：TM914.4

【共引文獻(xiàn)】

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