發(fā)布時(shí)間：2018-01-11 20:38

  本文關(guān)鍵詞：自組裝嵌段共軛聚合物電解質(zhì)及超支化小分子陰極界面修飾應(yīng)用于聚合物太陽電池　出處：《南昌大學(xué)》2017年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 聚合物太陽能電池 嵌段共軛聚合物電解質(zhì) 自組裝 小分子電解質(zhì) 界面工程

【摘要】：體相異質(zhì)結(jié)聚合物(BHJ)太陽能電池(PSCs)因其具有質(zhì)輕、柔韌性好、便于大面積卷對(duì)卷印刷等優(yōu)點(diǎn)引起了越來越多的關(guān)注。近年來,聚合物太陽能電池取得了較大的進(jìn)步,能量轉(zhuǎn)換效率(PCE)已超過13%。然而,聚合物太陽能電池要實(shí)現(xiàn)商業(yè)化大面積制備還需要解決一些科學(xué)問題,如電荷的分離、傳輸和收集效率低等限制了其大面積商業(yè)化生產(chǎn)。良好的界面接觸和優(yōu)異的界面層和活性層形貌非常重要。因此,需要設(shè)計(jì)一種能同時(shí)調(diào)控界面勢(shì)壘和提高活性層形貌的界面層。共軛聚合物電解質(zhì)(CPEs)由離域的π共軛主鏈和功能化的極性側(cè)鏈組成。由于CPEs和活性層的正交溶解性可避免與憎水性的活性層互混。同時(shí),由于CPEs和金屬電極之間存在靜電相互作用,可在界面形成偶極子,降低陰極的功函(WF),有利于電荷提取和收集,從而提高器件的PCE。嵌段共軛聚合物因其兩端主鏈之間的不相容性和結(jié)晶性差異,嵌段共軛聚合物可自發(fā)自組裝成有序的納米結(jié)構(gòu)。如果將嵌段共軛聚合物和CPEs的在分子水平上結(jié)合,得到嵌段共軛聚合物電解質(zhì)(DBCPEs),它將具有許多新穎的性質(zhì),如能形成有序的納米結(jié)構(gòu)、可降低金屬電極WF、降低界面勢(shì)壘和實(shí)現(xiàn)環(huán)境友好水/醇溶性加工等等。首先,設(shè)計(jì)合成了兩種新型的DBCPEs,分別以芴和噻吩(PFEO-b-PTNBr)以及芴和咔唑(PFEO-b-PCNBr)為主鏈,功能化極性基團(tuán)乙氧基鏈和季銨鹽為側(cè)鏈。將DBCPEs修飾ZnO不僅能夠很好地調(diào)控ZnO的功函,還能提高無機(jī)ZnO和有機(jī)活性層之間的界面相容性。此外,自組裝的DBCPEs PFEO-b-PCNBr和PFEO-b-PTNBr還能作為模板進(jìn)一步誘導(dǎo)上層活性層形成有序的納米纖維和納米柱狀結(jié)構(gòu),促進(jìn)電荷的提取和傳輸。ZnO/DBCPEs雙層電子傳輸層可同時(shí)提高器件的各項(xiàng)參數(shù),包含開路電壓(Voc),短路電流(Jsc),填充因子(FF)和PCE。最終,以聚(3-己基噻吩)(P3HT):(6,6)-苯基-C61丁酸甲酯(PC61BM)活性層,以ZnO為電子傳輸層的器件效率為3.0%,以ZnO/PFEO-b-PCNBr為電子傳輸層的器件效率提升至3.6%。由于ZnO/PFEO-b-PTNBr能形成更大的偶極子和更好的形貌表現(xiàn)出更優(yōu)越的性能,器件效率提高至3.8%。此外,將ZnO/PFEO-b-PTNBr作為電子傳輸層,以PBDB-T:ITIC為活性層的器件效率高達(dá)10.8%。接著,把性能更好的PFEO-b-PTNBr的結(jié)構(gòu)進(jìn)一步優(yōu)化,將側(cè)鏈的季銨鹽陽離子替換成體積更大的咪唑鹽陽離子,得到新的DBCPEs PFEO-b-PTImBr。將兩種PFEO-b-PTNBr和PFEO-b-PTImBr作為電子傳輸層應(yīng)用于聚合物太陽能電池來研究不同末端陽離子對(duì)ITO的功函和上層活性層的形貌和排列的影響。自發(fā)自組裝的PFEO-b-PTNBr和PFEO-b-PTImBr ETLs不僅能在ITO電極和活性層界面產(chǎn)生歐姆接觸,還能自組裝成蜈蚣狀模板進(jìn)一步誘導(dǎo)活性層形成有利的face-on排列。通過電子順磁共振(EPR)測(cè)試,在兩種p-型主鏈的DBCPEs中均可觀察到n-型自摻雜現(xiàn)象,并且PFEO-b-PTImBr比PFEO-b-PTNBr的EPR信號(hào)更強(qiáng)。最終,以P3HT:PC61BM為活性層,基于PFEO-b-PTNBr為ETL的器件效率升至3.1%,而基于PFEO-b-PTImBr的效率為3.5%。以PTB7-Th:PC71BM為活性層時(shí),以ZnO/PFEO-b-PTNBr和ZnO/PFEO-b-PTImBr為電子傳輸層的器件效率分別為9.0%和9.4%�；赯nO/PFEO-b-PTNBr和ZnO/PFEO-b-PTImBr電子傳輸層,以PTB7-Th:PC71BM為活性層的器件效率優(yōu)于傳統(tǒng)的已報(bào)道的經(jīng)典的PFN(8.4%)和PFNBr(8.4%)ETLs器件。小分子電解質(zhì)(SMEs)具有重復(fù)性好、易提純和結(jié)構(gòu)固定等優(yōu)點(diǎn)。通過一步法簡(jiǎn)單反應(yīng),我們首次報(bào)道了一種新型超支化小分子電解質(zhì)PNSO_3Na,并將其作為電子傳輸層應(yīng)用于聚合物太陽能電池。由于一摩爾的PNSO_3Na含有七摩爾的丁基磺酸鈉,超支化PNSO_3Na有機(jī)界面層能提高界面接觸并能調(diào)節(jié)界面能級(jí),提高器件效率。以P3HT:PC61BM為活性層,相對(duì)于ITO器件,以PNSO_3Na為ETL的器件效率從0.8%提高到3.7%。當(dāng)將ZnO/PNSO_3Na作為電子傳輸層時(shí),以PBDB-T:ITIC為活性層的器件效率高達(dá)11.2%。集合超支化小分子電解質(zhì)(SMEs)和高電子親和勢(shì)材料的雙重優(yōu)勢(shì),我們首次設(shè)計(jì)合成了兩種分別以四亞乙基五胺(PDIPN)和丁基磺酸鈉四亞乙基五胺(PDIPNSO_3Na)為支鏈的新型的傒酰亞胺衍生物作為電子傳輸層。由于極性支鏈的存在,兩種傒酰亞胺衍生物PDIPN和PDIPNSO_3Na ETLs均能形成界面偶極,提高界面接觸。因?yàn)閭蒗啺繁旧砭哂械母唠娮佑H和勢(shì),PDIPN和PDIPNSO_3Na均有來自于極化子的EPR信號(hào)峰,表明具有n-型自摻雜效應(yīng)。此外,相對(duì)于PDIPNSO_3Na,PDIPN具有更強(qiáng)的EPR強(qiáng)度,主要?dú)w功于PDIPN中四亞乙基五胺支鏈具有更高的負(fù)電荷密度。因此,相對(duì)于PDIPNSO_3Na,基于PDIPN ETL展現(xiàn)出更優(yōu)異的光伏性能。綜上表明,這些水/醇溶性DBCPEs和超支化小分子ETLs不僅能改善陰極和活性層之間的界面接觸,還能改善活性層形貌,這有利于優(yōu)化PSCs器件效率并能為可印刷大面積PSCs的制備提供寶貴的參考價(jià)值。
[Abstract]:Bulk heterojunction polymer solar cell (BHJ) (PSCs) because of its light weight, good flexibility, easy large-area roll to roll printing has attracted more and more attention. In recent years, polymer solar cells have made great progress, the energy conversion efficiency (PCE) has more than 13%. however, polymer solar cells to achieve commercial production of large area still need to solve some scientific problems, such as charge separation, the large scale commercial production limit transmission and collection efficiency is low. Good interface contact and excellent interface layer and active layer morphology is very important. Therefore, we need to design a kind of can also control the interface barrier and improve the interface active layer morphology. Conjugated polymer electrolyte (CPEs) consisting of polar conjugated backbone and side chain from the functional domain. Since the orthogonal solubility of CPEs and the active layer can be avoided and the hydrophobicity of living Of the mixed layer. At the same time, due to the electrostatic interaction between CPEs and metal electrode can be formed at the interface dipole, decrease the cathode work function (WF), which is beneficial to the charge extraction and collection, so as to improve the device PCE. block copolymer between both ends of the main chain is compatibility and crystallization of difference. Block copolymer can self-assembly into ordered nanostructures. If the block conjugate polymer and CPEs binding at the molecular level, block copolymer of conjugated polymer electrolyte (DBCPEs), it will have many novel properties, such as to form nano ordered structure, can reduce the metal electrode WF, reduce the interface the barrier and environmental friendly water / alcohol soluble processing and so on. First of all, two new types of DBCPEs were designed and synthesized, respectively with fluorene and thiophene (PFEO-b-PTNBr) and fluorene and carbazole (PFEO-b-PCNBr) as the main chain and function of polar groups Oxyethylation Chain and quaternary ammonium salt as side chain. The DBCPEs ZnO is not only able to regulate ZnO function, but also improve the inorganic organic active layer ZnO and the interface compatibility. In addition, the self-assembly of DBCPEs PFEO-b-PCNBr and PFEO-b-PTNBr can be used as a template to induce the upper active layer to form ordered nano fibers and nano columnar the structure, promote the charge extraction and transmission of.ZnO/DBCPEs double electron transport layer can also improve the parameters of the device, including open circuit voltage, short circuit current (Voc) (Jsc), fill factor (FF) and PCE., poly (3- has thiophene (P3HT): (6,6) - phenyl methyl butyrate (-C61) PC61BM) active layer, using ZnO as electron transport layer, device efficiency is 3%, with ZnO/PFEO-b-PCNBr as the electron transport layer to enhance the efficiency of the device 3.6%. due to the morphology of ZnO/PFEO-b-PTNBr can form a larger dipole and better superior. Can improve the efficiency of the device, in addition to 3.8%., ZnO/PFEO-b-PTNBr as electron transport layer, using PBDB-T:ITIC as the active layer of the device efficiency is as high as 10.8%. then, to further optimize the structure of the better performance of PFEO-b-PTNBr, the side chain quaternary ammonium cation substitution into larger imidazolium cations, a new DBCPEs PFEO-b-PTImBr. two PFEO-b-PTNBr and PFEO-b-PTImBr as the influence of morphology and arrangement of electron transport layer used in polymer solar cells to study different cationic ions on ITO at the end of the work function and the upper active layer. The self-assembly of PFEO-b-PTNBr and PFEO-b-PTImBr ETLs can not only produce ohmic contact on ITO electrode and the active layer interface, can self assemble into shape template to induce the centipede the active layer is conducive to the formation of the face-on array. By electron paramagnetic resonance (EPR) test in two types of p- DBCPEs in main chain Observed the self doping phenomenon of type n-, PFEO-b-PTImBr and EPR PFEO-b-PTNBr. The signal is stronger than the final, with P3HT:PC61BM as the active layer, based on the PFEO-b-PTNBr ETL device efficiency rose to 3.1%, while the efficiency of PFEO-b-PTImBr based on 3.5%. with PTB7-Th:PC71BM as the active layer, using ZnO/PFEO-b-PTNBr and ZnO/PFEO-b-PTImBr as electron transport layer, device efficiency was 9% based on 9.4%. and ZnO/PFEO-b-PTNBr and ZnO/PFEO-b-PTImBr with PTB7-Th:PC71BM as electron transport layer, an active layer of the device is more efficient than the traditional reported classic PFN (8.4%) and PFNBr (8.4%) ETLs devices. Small molecule electrolyte (SMEs) has good repeatability, easy purification and fixed structure etc. through one-step simple reaction, we we first reported a novel hyperbranched small molecule electrolyte PNSO_3Na, and its application as an electron transport layer in polymer solar cells. In a molar PNSO_3Na containing seven mol butyl sulfonate, PNSO_3Na hyperbranched organic interface layer can improve the interface contact and can adjust the interface level, improve the efficiency of the device. With P3HT:PC61BM as the active layer, relative to the ITO device, PNSO_3Na ETL device efficiency increased from 0.8% to 3.7%. when ZnO/PNSO_3Na as electron transport layer. With PBDB-T:ITIC as the active layer of the device efficiency is as high as 11.2%. collection of hyperbranched small molecule electrolyte (SMEs) and high electron affinity material advantages, we first designed and synthesized two four ethylene five amine (PDIPN) and butyl sulfonate four ethylene five amine (PDIPNSO_3Na) as Xi imide derivatives the new branch as an electron transport layer. Due to the polarity of branched, two Xi imide derivatives PDIPN and PDIPNSO_3Na ETLs can improve the interface contact interface dipole formation, because Xi imide. High electron affinity amine itself with the EPR signal peak of PDIPN and PDIPNSO_3Na were from that of polarons, with n- type self doping effects. In addition, compared with PDIPNSO_3Na, EPR PDIPN has stronger strength, mainly due to four ethylene amines five branched PDIPN with negative charge density higher. Therefore, compared with PDIPNSO_3Na PDIPN, ETL showed more excellent photovoltaic properties. Based on summing up that the water / alcohol soluble hyperbranched molecules DBCPEs and ETLs not only can improve the interface contact between the cathode and the active layer can improve the morphology of active layer, which is conducive to the optimization of PSCs device efficiency and for the preparation of large area PSCs printing to provide a valuable reference value.

【學(xué)位授予單位】：南昌大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O631;TM914.4

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