本文關(guān)鍵詞：有機(jī)太陽(yáng)能電池給體材料設(shè)計(jì)合成與器件優(yōu)化研究　出處：《南開大學(xué)》2014年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 小分子給體 有機(jī)太陽(yáng)能電池 能量轉(zhuǎn)化效率 電子傳輸層 翻轉(zhuǎn)結(jié)構(gòu)器件

【摘要】：本論文設(shè)計(jì)并合成了一系列新型有機(jī)太陽(yáng)能電池的給體材料,并對(duì)它們的熱穩(wěn)定性、吸收光譜、電化學(xué)性能和固態(tài)堆積狀態(tài)進(jìn)行了測(cè)試,同時(shí)詳細(xì)研究了它們作為電子給體材料在有機(jī)太陽(yáng)能電池中的光電轉(zhuǎn)換性能。為了進(jìn)一步提高有機(jī)小分子太陽(yáng)能電池的能量轉(zhuǎn)換效率,我們將研究重點(diǎn)轉(zhuǎn)移至器件優(yōu)化和機(jī)理研究。首先使用各種不同的電子傳輸層,將DR3TBDT作為給體材料的小分子太陽(yáng)能電池的能量轉(zhuǎn)換效率提高至8.32%。然后通過制備并優(yōu)化翻轉(zhuǎn)結(jié)構(gòu)的器件,將以DRCN7T作為給體材料的翻轉(zhuǎn)結(jié)構(gòu)小分子太陽(yáng)能電池的能量轉(zhuǎn)換效率提高至8.84%。在上面的合成及器件優(yōu)化過程中,我們對(duì)光電轉(zhuǎn)換機(jī)理和器件壽命進(jìn)行了初步的研究。最后我們基于本組在過去四年中理論計(jì)算方面的結(jié)果,對(duì)分子結(jié)構(gòu)設(shè)計(jì)和性能預(yù)測(cè)提出了一些觀點(diǎn)和看法。具體各部分內(nèi)容摘要如下： 一、設(shè)計(jì)并合成了兩個(gè)具有相同骨架但側(cè)鏈不同的異硫茚(ITN)和苯并雙噻吩(BDT)的新型醌式交替共聚物PBDT-DEAITN和PBDT-DOAITN,并研究了它們的光電轉(zhuǎn)換性能。這兩個(gè)聚合物有非常窄的光學(xué)帶隙,分別為1.52和1.58eV。將它們與PC61BM共混后制備的器件,在標(biāo)準(zhǔn)太陽(yáng)光下的能量轉(zhuǎn)換效率分別是1.25%和1.20%。通過薄膜X射線衍射和原子力顯微鏡測(cè)試觀察到這兩個(gè)聚合物在固體狀態(tài)下堆積較差,同時(shí)用空間電荷限制電流測(cè)試得到兩個(gè)聚合物都有較低的遷移率；通過理論計(jì)算優(yōu)化對(duì)應(yīng)聚合物單體的結(jié)構(gòu),發(fā)現(xiàn)PBDT-DEAITN和PBDT-DOAITN中相鄰異硫茚和苯并雙噻吩單元之間的二面角分別高達(dá)33.66°和34.35°,較大的二面角會(huì)導(dǎo)致較差的堆積和低的遷移率,進(jìn)而導(dǎo)致低的能量轉(zhuǎn)換效率。通過理論計(jì)算的二面角和偶極矩結(jié)果分析,發(fā)現(xiàn)給體材料具有平面性骨架有利于得到更高的光電轉(zhuǎn)換性能�；诖�,分子的平面性成為本組設(shè)計(jì)給體分子的重要參考依據(jù)。 二、為了獲得更高的開路電壓,我們?cè)O(shè)計(jì)并合成了三個(gè)帶有不同端基的寡聚五噻吩衍生物DCAO5T,DERHD5T和DIN5T,并將這三個(gè)給體分子分別與富勒烯衍生物進(jìn)行共混制備有機(jī)太陽(yáng)能電池器件,測(cè)試了其在標(biāo)準(zhǔn)太陽(yáng)光下的光電轉(zhuǎn)換性能。其中,基于DERHD5T的器件獲得了1.08V的開路電壓和4.63%的能量轉(zhuǎn)換效率,這是有機(jī)太陽(yáng)能電池中為數(shù)不多的開路電壓可以超過1V的給體材料。同時(shí)DCAO5T和DIN5T分別獲得了3.27%和4.00%的能量轉(zhuǎn)換效率,開路電壓分別為0.88V和0.78V。通過理論模擬研究了高開路電壓的原因,發(fā)現(xiàn)DERHD5T與PC61BM之間的電子偶合能力最弱,從而降低了器件的反向飽和電流密度,使得開路電壓有一定的提高,理論預(yù)測(cè)的開路電壓和實(shí)驗(yàn)的結(jié)果趨勢(shì)一致。上述結(jié)果證明,除了通過降低給體HOMO能級(jí)(或者提高受體材料的LUMO能級(jí))來(lái)提高器件開路電壓外,削弱給體與受體之間的電子偶合也是非常重要的途徑。 三、為了提高有機(jī)太陽(yáng)能電池的能量轉(zhuǎn)換效率,制備了基于DR3TBDT:PC71BM作為活性層的小分子太陽(yáng)能電池,分別使用聚芴衍生物(PFN)、氧化鋅納米顆粒和氟化鋰作為電子傳輸層,得到的能量轉(zhuǎn)換效率分別為8.32%、7.30%和7.38%。其中,基于PFN的能量轉(zhuǎn)換效率是目前基于苯并雙噻吩體系小分子太陽(yáng)能電池的最高效率。論文詳細(xì)研究了引入不同的電子傳輸層對(duì)器件性能影響的原因,發(fā)現(xiàn)引入PFN后,能量轉(zhuǎn)換效率明顯提高的原因是減少了器件中的雙分子復(fù)合,同時(shí)增加了活性層的有效吸光。 四、在上述器件優(yōu)化工作的基礎(chǔ)上,我們制備了基于DRCN7T:PC71BM作為活性層的翻轉(zhuǎn)結(jié)構(gòu)小分子太陽(yáng)能電池,在標(biāo)準(zhǔn)太陽(yáng)光照射下,器件的能量轉(zhuǎn)換效率為8.84%,對(duì)應(yīng)的開路電壓為0.91V,短路電流密度為14.28mA cm-2,填充因子為0.68,這也是目前基于翻轉(zhuǎn)結(jié)構(gòu)小分子太陽(yáng)能電池的世界紀(jì)錄。在相同條件下制備的正常結(jié)構(gòu)器件,開路電壓和填充因子沒有明顯變化,能量轉(zhuǎn)換效率為8.06%,短路電流密度為13.07mA cm-2.通過變光強(qiáng)實(shí)驗(yàn)證實(shí)了正常結(jié)構(gòu)和翻轉(zhuǎn)結(jié)構(gòu)器件中,電荷的復(fù)合機(jī)制基本接近,因此后者短路電流密度增加的原因主要是增加了活性層的有效吸光,這也與光學(xué)模擬的結(jié)果一致。經(jīng)過封裝后,制備的翻轉(zhuǎn)結(jié)構(gòu)器件在空氣中存放103天后,器件的能量轉(zhuǎn)換效率仍然在8%以上,顯示了小分子太陽(yáng)能電池具有良好的發(fā)展前景。 五、本章比較了各種泛函和基組在光電功能材料預(yù)測(cè)方面的優(yōu)點(diǎn)與缺點(diǎn),發(fā)現(xiàn)B3LYP/6-31G*和PBE1PBE/6-31G*基本可以滿足有機(jī)半導(dǎo)體的結(jié)構(gòu)優(yōu)化、HOMO能級(jí)、吸收光譜和電荷傳輸重組能等參數(shù)的預(yù)測(cè)。尤其是PBE1PBE/6-31G*的結(jié)果與實(shí)驗(yàn)結(jié)果吻合的較好�；贛arcus電子轉(zhuǎn)移方程,我們將理論計(jì)算得到的給體空穴重組能與對(duì)應(yīng)器件能量轉(zhuǎn)換效率進(jìn)行關(guān)聯(lián),發(fā)現(xiàn)給體分子的空穴重組能越小,越有利于給體與受體界面的激子分離和給體中空穴的傳輸與收集,進(jìn)而得到更高的能量轉(zhuǎn)換效率。這對(duì)以后的光電分子設(shè)計(jì)具有重大的指導(dǎo)意義。
[Abstract]:This paper designed and synthesized a series of novel organic solar cell material, and the thermal stability of their absorption spectra, electrochemical properties and solid state accumulation were tested, and studied them as a photoelectric conversion electron donor material in organic solar cell performance. In order to further improve the energy conversion efficiency of organic small molecular solar cells, we will study the focus to the device optimization and mechanism research. First, using a variety of different electron transport layer, DR3TBDT as the energy conversion efficiency was improved to 8.32%. for small molecule solar cell materials and devices through the preparation and optimization of flip structure, with DRCN7T as synthesis and device the optimization process to the turnover structure of small molecule material solar energy conversion efficiency was improved to 8.84%. in the above, we on the photoelectric The mechanism of conversion and the lifetime of devices have been preliminarily studied. Finally, based on the results of theoretical calculations in the past four years, we put forward some viewpoints and opinions on molecular structure design and performance prediction.
A design, and two have the same skeleton but isothianaphthene different side chains were synthesized (ITN) and benzo (BDT) thiophene double novel quinone alternating copolymer PBDT-DEAITN and PBDT-DOAITN, and studied their photoelectric conversion properties. These two polymers have very narrow optical band gap, respectively 1.52 and they will be 1.58eV. and PC61BM in the blends prepared in the standard device, the sun's light energy conversion efficiency were 1.25% and 1.20%. thin films by X ray diffraction and atomic force microscopy observed the two polymer poor accumulation in the solid state, at the same time with the space charge limited current test two polymers have migration low rate; through theoretical calculation and optimization structure of the corresponding polymer monomer, PBDT-DEAITN and PBDT-DOAITN found that the dihedral angle between adjacent isothianaphthene and benzo bithiophene units were as high as 33.66 degrees and 34.35 degrees, The larger dihedral angle will lead to poor accumulation and low mobility, which leads to low energy conversion efficiency. Through the theoretical calculation and analysis of the dihedral angle and the dipole moment results, found that donor materials with planar skeleton to obtain higher photoelectric conversion performance. Based on this, the plane of the divided sub group to design an important reference molecule.
Two, in order to obtain a higher open circuit voltage, we design and three different end groups with oligomeric five thiophene derivatives synthesized by DCAO5T, DERHD5T and DIN5T, and the three donor molecules respectively and fullerene derivatives were prepared by blending organic solar cell device, the photoelectric conversion in the standard sun performance test. The DERHD5T device based on 1.08V was obtained in the open circuit voltage and energy conversion efficiency of 4.63%, which is the organic solar cell open circuit voltage for a few more than 1V to the bulk material. The energy conversion efficiency at DCAO5T and DIN5T respectively won the 3.27% and 4%, respectively 0.88V and 0.78V. open circuit voltage study on the causes of high open circuit voltage through theoretical simulation, found between DERHD5T and PC61BM of the electronic coupling weakest, thereby reducing the device reverse saturation current density, the open circuit voltage is To some extent, the results of theoretical and experimental prediction of open circuit voltage of the same trend. The results show that, except by reducing the donor HOMO level (or increase the LUMO level of receptor materials) to improve the device open circuit voltage, weaken the way to electronic coupling between the donor and acceptor is also very important.
Three, in order to improve the energy conversion efficiency of organic solar cells, DR3TBDT:PC71BM were prepared as small molecular solar cells based on the active layer, respectively using polyfluorene derivatives (PFN), Zinc Oxide nano particles and lithium fluoride as an electron transport layer, the energy conversion efficiency were 8.32%, 7.30% and 7.38%., PFN energy conversion efficiency is the highest efficiency based on benzo bithiophene system of small molecular solar cells based on the reasons. This paper made a detailed research into the influence of different electron transport layer on the device performance, found that after the introduction of PFN, significantly improve the efficiency of energy conversion reason is to reduce the double molecular devices in the composite, while increasing the effective absorption activity layer.
Four, based on the optimization of the device, we prepared the turnover structure of small molecular solar cells DRCN7T:PC71BM as active layer based on the standard in the sunlight, the energy conversion efficiency of the device is 8.84%, the open circuit voltage corresponding to the 0.91V, the short-circuit current density was 14.28mA cm-2, the fill factor of 0.68 and the is currently the turnover structure of small molecular solar cells based on the world record. The normal structure of devices prepared under the same conditions, the open circuit voltage and the fill factor did not change significantly, the energy conversion efficiency of 8.06%, short circuit current density of 13.07mA cm-2. by changing the light intensity experiment confirmed the normal structure and turning structure device, the basic mechanism of composite charge close, so the reason for the latter to increase the short circuit current density is mainly to increase the effective absorption of the active layer, this also with the optical simulation results. After packaged, The energy conversion efficiency of the device is still more than 8% after storing for 103 days in air, showing that the small molecule solar cell has good prospects for development.
Five, this chapter compares the various functionals and basis sets in photoelectric materials forecast the advantages and disadvantages of B3LYP/6-31G* and PBE1PBE/6-31G* can meet the basic structure optimization, organic semiconductor HOMO level, prediction of absorption and charge transfer reorganization energy and other parameters. Especially the PBE1PBE/6-31G* results and the experimental results agree well with the Marcus. Based on the equation of electron transfer, we will give the calculated body hole reorganization energy and corresponding device energy conversion efficiency of the association, found that recombinant molecules can hole smaller, more conducive to the exciton separation donor and acceptor interface and to transmit and collect in the hole, and then get the higher energy conversion efficiency. Is of great significance to the photoelectric molecular design in the future.

【學(xué)位授予單位】：南開大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2014
【分類號(hào)】：TM914.4

【共引文獻(xiàn)】

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