氯化铯甲醇溶液对有机聚合物太阳能电池的影响

研究了氯化铯的甲醇溶液作为阴极修饰层,来提高传统有机聚合物太阳能电池器件性能。通过电容-电压(C-V)测试分析了铝电极和PTB7/PC_(70)BM之间的界面电荷积累情况,同时测试了紫外光电子能谱(UPS),对铝的功函数改变作了研究。结果表明,采用氯化铯的甲醇溶液作阴极修饰层的器件,其短路电流(J_(sc))、开路电压(V_(oc))、填充因子(FF)都有所提高,光电转化效率达到6.36%,与仅用甲醇处理过的器件相比,光电转化效率提高了11%;与未经甲醇处理的器件相比,光电转化效率提高了42.6%。这种一步溶液处理法能够减少电荷积累,同时降低铝电极的功函数,利于电子收集,进而提高器件性能。     

刮涂法制备聚合物薄膜太阳能电池

系统地研究了采用刮涂法制备聚合物薄膜太阳能电池时刮涂速度和基底温度对活性层厚度以及形貌的影响。当刮涂速度增加或者基底温度降低时,由于溶液粘度和表面张力的变化导致活性层厚度增加。与旋涂方法相比,刮涂方法制备的活性层薄膜具有更小的粗糙度和精细的相分离结构,从而减少了光伏电池的漏电流并提高了填充因子。利用刮涂方法制备的聚合物太阳能电池能量转换效率达到了4.2%。     

The effect of post-annealing on the interface between the aluminum electrode and the active layer in polymer/fullerene solar cells

The post-annealing effects on the performance of poly (3-hexylthiophene) (P3HT)/(6,6)-phenyl C₆₁ butyric acid methyl ester (PCBM) solar cells with conventional bulk heterojunction (CBHJ) and layer-evolved bulk heterojunction (LBHJ) have been compared. It is found that contrary to the much better performance obtained from CBHJ cells, the post-annealing deteriorates the performance of LBHJ devices. Aqueous contact angle and X-ray photoelectron spectroscopy measurements show that P3HT is dominant at the top surface of CBHJ film, while PCBM is dominant at the top surface of LBHJ film. The micron-scale morphology evolution of the active layer/Al interface upon post-annealing reveals that the PCBM-rich surface is beneficial for the nucleation and growth of PCBM crystal, which does harm to the contact between the active layer and the electrode and results in the decrease of the fill factor. However, the original P3HT-rich surface prevents the formation of large surface-segregated PCBM clusters upon post-annealing, which is highly desirable for the efficient polymer/fullerene solar cells.     

Improved performance of polymer solar cells by using inorganic,organic, and doped cathode buffer layers

The interface between the active layer and the electrode is one of the most critical factors that could affect the device performance of polymer solar cells. In this work, based on the typical poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methyl ester(P3HT:PCBM) polymer solar cell, we studied the effect of the cathode buffer layer(CBL) between the top metal electrode and the active layer on the device performance. Several inorganic and organic materials commonly used as the electron injection layer in an organic light-emitting diode(OLED) were employed as the CBL in the P3HT:PCBM polymer solar cells. Our results demonstrate that the inorganic and organic materials like Cs_2CO_3, bathophenanthroline(Bphen), and 8-hydroxyquinolatolithium(Liq) can be used as CBL to efficiently improve the device performance of the P3HT:PCBM polymer solar cells. The P3HT:PCBM devices employed various CBLs possess power conversion efficiencies(PCEs) of 3.0%–3.3%, which are ca. 50% improved compared to that of the device without CBL. Furthermore, by using the doped organic materials Bphen:Cs_2CO_3 and Bphen:Liq as the CBL, the PCE of the P3HT:PCBM device will be further improved to 3.5%, which is ca. 70% higher than that of the device without a CBL and ca. 10% increased compared with that of the devices with a neat inorganic or organic CBL.     

Highly crystalline bilayer electron transport layer for efficient conjugated polymer solar cells

Solution processed solar cells are a promising renewable energy technology due to the low fabrication costs. The most commonly used electron transport layer for solution processed organic solar cells is ZnO. However, sol-gel derived ZnO is amorphous, which limits interfacial charge transport. In this study, we demonstrate a ZnO bilayer, composed of a nanoparticle ZnO and sol-gel derived ZnO layer, as the electron transport layer in polymer solar cells incorporating the novel polymer poly [(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3‴-di (2-octyldodecyl)-2,2′; 5′,2″; 5″,2‴-quaterthiophen-5,5‴-diyl)] (PffBT4T-2OD). Compared with the single layer sol-gel ZnO, the bilayer displayed enhanced crystallinity. Consequently, the interfacial transport from the active layer was improved, as evidenced by dark J-V and PL spectroscopy measurements. Solar cells incorporating this bilayer ZnO layer achieved PCE values exceeding 10%, a relative improvement of 25% compared to the sol-gel ZnO devices.     

共轭聚合物作为有机光电池电子受体的特性研究

以聚3-已基噻吩(P3HT)和聚对苯亚乙烯衍生物(MDMO-PPV)作为电子给体,聚 (TQ1)作为电子受体,制备并研究了聚合物给体/聚合物受体有机光伏电池性能。当给体P3HT、受体TQ1共混质量比为1∶1时,器件性能最佳。热处理会改变薄膜形貌,导致激子扩散到达界面的距离增加和激子分离界面数量下降,进而引起器件性能下降。溶剂效应对器件性能影响不明显。研究了相似能带结构给体聚合物对MDMD-PPV光电池性能的影响,发现结晶程度较低的给体材料会进一步导致器件性能降低。     

Correlation of band electronic structure with efficiency in perovskite solar cells with vanadium (Ⅳ) oxide thin film buffers

Perovskite solar cells have been studied extensively in the area of perovskite solar cells because they have a comparatively free hysteresis. Through fabrication of a perovskite solar cell based on a vanadium oxide buffer, this study clarified the mechanism of electron and hole transport in the laminated layer upon irradiation with light. The power conversion efficiency (PCE) of the Vanadium (Ⅳ) oxide (VO₂) sputtering process device was approximately 13% and with the spin-coating process was 8.5%. To investigate the physicochemical origin of such PCE differences depending on the process type, comprehensive band alignment and band structure analyses of the actual cell stacks were performed using X-ray photoelectron spectroscopy depth measurements. Accordingly, it was found that the inconsistent valence band offset between the perovskite absorption layer and V₂O₅ layer as a function of the VO₂ process type caused a difference in the hole transport, resulting in the difference in the efficiency.     

基于Al_2O_3/MoO_3复合阳极缓冲层的倒置聚合物太阳能电池的研究

采用旋涂Al_2O_3前驱体溶液和低温退火的方法在活性层上形成Al_2O_3薄膜,并与MoO_3结合形成Al_2O_3/MoO_3复合阳极缓冲层,制备了以聚3-己基噻吩:[6.6]-苯基-C_(61)-丁酸甲酯(P3HT:PC_(61)BM)为活性层的倒置聚合物太阳能电池,并通过改变Al_2O_3前驱体溶液的浓度来分析复合阳极缓冲层对器件性能的影响.结果发现,Al_2O_3/MoO_3复合阳极缓冲层能有效调控倒置聚合物太阳能电池的光电性能及其稳定性.当Al_2O_3前驱体溶液的浓度为0.15%时,器件光伏性能达到最优值,与MoO_3单缓冲层的器件相比,光电转换效率(PCE)由3.85%提高到4.64%;经过80天老化测试后,具有复合阳极缓冲层的器件PCE保留为初始值的76%,而单缓冲层的器件PCE已经下降到50%以下.器件性能得到改善的原因是Al_2O_3/MoO_3复合阳极缓冲层增强了倒置太阳能电池器件阳极对空穴的收集能力,同时钝化了器件活性层,从而提升了太阳能电池器件的光伏性能及其稳定性.     

退火处理ZnPc(OC_8H_(17)OPyCH_3I)_8阴极缓冲层的倒置有机太阳能电池

制备了以Zn Pc(OC8H17OPy CH3I)8为阴极缓冲层、P3HT∶PCBM为有源层的有机太阳能电池。对阴极缓冲层Zn Pc(OC8H17OPy CH3I)8薄膜分别进行了溶剂蒸汽退火和过渡舱惰性气体流退火处理,并利用原子力显微镜(AFM)对缓冲层表面形貌进行了表征。结果表明:这两种退火方法都使缓冲层形貌得以改善。电池效率从2.14%提高到3.76%,电流密度从8.12 m A/cm2提高到10.71 m A/cm2,填充因子从0.45提高到0.61。与传统器件相比,退火处理的阴极缓冲层器件的稳定性也得到了改善,器件寿命延长了1.4倍。这种简单阴极界面处理方法为改善聚合物太阳能电池性能提供了有效途径。     

Dual plasmonic‐enhanced bulk‐heterojunction solar cell incorporating gold nanoparticles into solution‐processed anode buffer layer and active layer

A dual plasmonic resonance effect on the performance of poly(3‐hexylthiophene) (P3HT):phenyl C61‐butyricacid methyl ester (PC61BM) based polymer solar cells (PSCs) has been demonstrated by selectively incorporating 25 nm colloidal gold nanoparticles (Au NPs) in a solution‐processed molybdenum oxide (MoO₃) anode buffer layer and 5 nm colloidal Au NPs in the active P3HT:PCBM layer. The devices exhibit up to ～20% improvement in power conversion efficiency which is attributed to the dual effect of localized surface plasmon resonance (LSPR) of Au NPs with enhanced light absorption and exciton generation. Our report shows a guideline on the usage of dual LSPR effect for the solution‐processed polymer solar cells to achieve high efficiencies. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

微波退火对聚合物太阳能电池性能的提高

利用微波对基于poly(3-hexylthiophene) (P3HT)和 -phenyl-C61-buytyric acid methyl ester (PCBM) 的体异质结太阳能电池进行退火处理,提高了器件的效率。使用的微波频率为2.45 GHz,当处理时间为10 min时,获得的短路电流为9.13 mA/cm²,开路电压为0.63 V,能量转化效率为3.21%,其性能参数完全可以与普通真空干燥箱退火相比拟。研究了微波对活性层的作用,从微波退火处理后的UV-Vis吸收谱和SEM图发现,微波退火主要改善了活性层的粗糙度,提高了相分离程度,有利于激子在界面处的解离和载流子的传输。     

The effect of various solvent additives on the power conversion efficiency of polymer-polymer solar cells

We investigated the effect of three different additives (1-chloronaphthalene, 1,8-diiodooctane, diphenylether) on the performance of polymer-polymer solar cells based on a BHJ blend consisting of poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene-alt-3-fluorothieno[3,4-b]thiophene-2-carboxylate] (PTB7-Th) as a donor and poly[[N,N′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)] (P(NDI2OD-T2)) as an acceptor. A direct comparison of the efficiency of the solar cells with and without additive indicated that the device using the additive exhibited slightly improved performance. However, the efficiency enhancement was not significant. The optimal ratio of additive differed depending on the properties of the additive. In addition, the performances of polymer-polymer solar cells were not significantly dependent on the type of additive. Identifying the optimal fabrication condition was critical for achieving the highest performance. It is known that the general role of an additive in polymer solar cells based on a BHJ active layer was to induce good phase separation between the donor and acceptor by morphology modification. However, grazing-incidence wide-angle X-ray scattering results showed that no significant morphology change in polymer-polymer active layer was caused by the additive. Rather, our modulated impedance spectroscopy study showed that the performance enhancement in polymer-polymer solar cells with additive was because of improved recombination properties rather than improvements in crystalline morphology.     

掺杂石墨烯量子点对P3HT:PCBM太阳能电池性能的影响

为研究掺杂石墨烯量子点(GQDs)对聚合物电池的影响,采用溶剂热法制备了GQDs,掺杂到聚3-己基噻吩和富勒烯衍生物(P3HT∶PCBM)中作光敏层制备了聚合物太阳能电池。掺杂不同浓度的GQDs后,聚合物电池的开路电压和填充因子都比未掺杂器件高。GQDs掺杂质量分数为0.15%时,形成的掺杂薄膜平整、均匀,填充因子提高了17.42%。GQDs经还原后,随还原时间的延长,填充因子FF增大。到45 min时,电池的FF基本稳定,从31.57%提高至40.80%,提高了29.24%。退火后,获得了最佳的掺杂GQDs的聚合物太阳能电池,开路电压Voc为0.54 V,填充因子FF为55.56%,光电转换效率为0.75%。     

Titania surface modification and photovoltaic characteristics with tungsten oxide

WO₃-coated TiO₂ film was prepared by depositing TiO₂ suspension containing small amounts of ammonium tungstate solution. The morphology and structure of the samples were characterized with high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and photoluminescence (PL) emission spectrum. The results showed that WO₃ formed a coating layer on surface of TiO₂ and significantly reduced the surface traps of TiO₂ nanoparticles. Transient photovoltage and electrochemical impedance measurements (EIS) were employed to study the charge separation/recombination process. The results revealed that the charge recombination was greatly retarded and the electron lifetime was increased due to the coating layer of WO₃. These observations showed good correlation with current-voltage analyses of dye-sensitized solar cell fabricated from these films, with WO₃ overlayer resulting in an increase in open-circuit voltage of up to 37 mV and 11% improvement in overall device efficiency.     

不同环境压强下溶剂退火对聚合物太阳能电池性能的影响

通过改变溶剂退火时的环境压强控制溶剂的蒸发速率,在不同压强下进行加压溶剂退火制备了基于聚-3己基噻吩:富勒烯衍生物(P3HT:PCBM)的体异质结聚合物太阳能电池。X射线衍射(XRD)、紫外-可见吸收光谱(UV-Vis)以及原子力显微镜(AFM)的测试结果表明,增大溶剂退火的环境气压改善了薄膜的结晶度,增强了有源层的光吸收,提高了P3HT和PCBM的相分离程度,更有利于激子的解离和载流子传输。与在常压下溶剂退火相比,在2.0 MPa压强下对有源层进行溶剂退火的器件的光电转换效率提高了29%,达到了3.69%。     

采用高传导率银铜镍网格电极的柔性聚合物太阳能电池

采用一种新的阳极材料:银、铜、镍的复合金属网格阳极,利用旋涂法制成了活性层为P3HT (poly(3-hexylthiophene)):PCBM([6,6]-phenylC61-butyricacidmethylester)的柔性衬底聚合物太阳能电池.制备了5种不同结构的柔性聚合物太阳能电池器件,将采用新型阳极材料的柔性衬底聚合物太阳能电池与传统ITO(Indium tin oxide)阳极的柔性衬底聚合物太阳能电池进行对比,发现新型阳极材料所制成的器件性能得到大幅度的提高,其电池器件在50 mW/cm~2强度光照下,开路电压(V_(oc))为0.54 V,短路电流密度(J_(sc))为5.39 mA/cm~2,能量转换效率为2.060%.     

利用阴极修饰层提高有机光伏电池的性能及稳定性

分别制备了以苯甲酸锂、碳酸铯和聚氧化乙烯为阴极修饰层的基于P3HT∶PCBM体系的本体异质结有机光伏电池。比较了3种阴极修饰层对器件性能及稳定性的影响。结果表明:选择合适的阴极修饰层材料是提高光电转换效率、延长电池使用寿命的可行性途径之一。纯无机阴极修饰层不能有效地阻挡氧气和水进入活性层,对于减缓器件的性能衰退效果不如有机阴极修饰层材料。有机聚合物材料可以减小漏电流的产生,开路电压和填充因子都得到很大提高,有利于提高器件的性能及稳定性。合成可溶液加工的具有极性基团的共轭聚合物材料是未来阴极修饰层的发展方向。     

Hybrid polymer/inorganic nanoparticle blended ternary solar cells

Hybrid polymer/inorganic nanoparticle blended ternary solar cells are reported. These solar cells have an active layer consisting of PbS colloidal quantum dots (CQDs), poly (3‐hexylthiophene) (P3HT), and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM). Power conversion efficiency (PCE) was improved by incorporating PbS CQDs in the active layer of P3HT:PCBM‐based organic solar cells. As the concentration of PbS CQDs in the hybrid solar cells was increased, PCE was also increased. This improvement resulted from improved charge transfer and also extended light absorption into the near‐infrared. The PCE of the hybrid solar cells was 47% higher than that for reference organic solar cells on average under air mass 1.5 global illumination. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

基于聚多巴胺/氧化锌复合阴极缓冲层的倒置聚合物太阳能电池的研究

利用多巴胺氧化自聚合形成聚多巴胺(PDA)与ZnO结合形成PDA/ZnO复合阴极缓冲层,制备了以P3HT:PC_(61)BM为活性层的倒置结构聚合物太阳能电池,通过改变PDA的自聚合时间来分析复合阴极缓冲层对器件性能的影响.实验发现,随着PDA的自聚合时间的增加,聚合物太阳能电池的光电转换效率先增大后减小,当自聚合时间为10 min时,相应器件光伏性能达到最优值,其开路电压V_(OC)为0.66 V,短路电流密度J_(SC)为9.70 mA/cm~2,填充因子FF为68.06%,光电转换效率PCE为4.35%.器件性能改善的原因是由于PDA/ZnO复合阴极缓冲层减小了ZnO与ITO之间的接触电阻,同时PDA中存在大量的氨基有利于倒置太阳能电池阴极对电子的收集.     

胆甾液晶掺杂活性层对有机太阳能电池性能的影响

以poly(3-hexylthiophene)(P3HT)为电子给体,indene-C60bisadduct(ICBA)为电子受体,通过掺杂不同浓度胆甾液晶氯化胆甾醇制备了有机体异质结太阳能电池.结果表明,适当浓度掺杂使器件的开路电压提高到了0.78 V,但短路电流密度却有所降低,填充因子几乎不变,能量转换效率提高了10%.利用X射线、光致发光、原子力显微镜及紫外-可见吸收光谱进行表征,发现液晶掺杂对活性层的结晶度、分子内部排列情况、薄膜表面形貌和光吸收特性等都有明显影响.