三元P3HT:PTB7-Th:PCBM聚合物太阳能电池性能的研究

将窄带隙聚合物PTB7-Th作为第三种物质掺入到P3HT:PCBM中制备了双给体结构的三元聚合物太阳能电池, 并且通过改变PTB7-Th的浓度来研究PTB7-Th对器件性能的影响. 研究发现, 掺入PTB7-Th后, 聚合物太阳能电池的短路电流和填充因子同时获得了提高, 使器件的光电转换效率得到了改善. 进一步分析表明, PTB7-Th的加入能够拓宽活性层的吸收光谱, 增加活性层吸收的光子数目, 有利于短路电流的提升. PTB7-Th与P3HT之间以电荷转移的形式相互作用, 这种作用方式有利于激子的解离, 从而使器件的填充因子得到了提高.     

Highly sensitive polymer photodetectors with a wide spectral response range

A series of highly sensitive polymer photodetectors(PPDs) was fabricated with P3HT100-x:PBDT-TS1x:PC71BM1 as the active layers, where x represents the PBDT-TS1 doping weight ratio in donors. The response range of PPDs can cover from the UV to near-infrared regions by adjusting the PBDT-TS1 doping weight ratio. The best external quantum efficiency(EQE) values of ternary PPDs with P3HT:PBDT-TS1:PC_(71)BM(50:50:1 wt/wt/wt) as the active layers reach 830%, 720%,and 330% under 390-, 625-, and 760-nm light illumination and-10 V bias, respectively. The large EQE values indicate that the photodetectors utilise photomultiplication(PM). The working mechanism of PM-type PPDs can be attributed to interfacial trap-assisted hole tunnelling injection from the external circuit under light illumination. The calculated optical field and photogenerated electron volume density in the active layers can well explain the EQE spectral shape as a function of the PBDT-TS1 doping weight ratio in donors.     

P3HT:PCBM薄膜成膜过程对聚合物太阳能电池性能的影响

P3HT:PCBM薄膜的快速和缓慢成膜过程能显著的改变异质结聚合物太阳能电池性能.通过调节旋转时间以及薄膜退火前的间隔时间,研究了P3HT:PCBM混合薄膜缓慢生长所需最佳时间.结果表明,在转速800 r·min-1下旋涂薄膜,经过50～80 s的旋涂,接着放置样品薄膜30 min以上,然后再对薄膜进行退火处理,电池效...     

Influence of morphology of PCDTBT:PC71BM on the performance of solar cells

Because of the restriction of low energy difference between the highest occupied molecular orbital of P3HT and the lowest unoccupied molecular orbital of PCBM, the obtained power conversion efficiency of P3HT:PCBM solar cells is merely half the ideal value. In this paper, we have fabricated bulk heterojunction solar cells based on PCDTBT and PC71BM (structure: ITO/PEDOT:PSS/PCDTBT:PC71BM/LiF (0.8 nm)/Al (80 nm)). In order to optimize the performance of the cells, the weight ratio of PCDTBT to PC71BM, the thickness of the active layer and thermal annealing are investigated. When the weight ratio of PCDTBT to PC71BM is 1:2 and the thickness of the active layer is 73 nm, a short circuit current density of 10.36 mA/cm², an open-circuit voltage of 0.91 V, a fill factor of 55.06 % and a power conversion efficiency of 5.19 % can be achieved. Moreover, we probe the influence of annealing temperature on the performance of organic solar cells, and find that the thermal treatment methodology (apart from the removal of trapped casting solvent) is of limited benefit.     

二甲基亚砜添加剂对聚合物太阳能电池性能的影响

研究了二甲基亚砜(DMSO)掺杂浓度对基于聚(3-己基噻吩)(P3HT)和(6,6)-苯基碳60丁酸甲酯(PCBM)为有源层的聚合物太阳能电池性能影响。结果表明,掺杂DMSO可以提高聚合物太阳能电池短路电流密度和填充因子。DMSO掺杂质量比为3%时,电池短路电流密度提高到7.88 mA·cm-2,填充因子为55.5%。能量转换效率达到2.54％,相比没有掺杂DMSO的电池,能量转换效率提高了17%。傅里叶变换红外光谱被用于鉴定和分析掺杂DMSO对材料P3HT∶PCBM化学性质的影响。傅里叶变换红外光谱表明,掺杂后P3HT和PCBM的化学性质都没有改变。为分析掺杂DMSO改善器件能量转换效率的原因,通过紫外-可见光谱和电流密度-电压特性曲线分别表征器件的光吸收能力以及电致发光器件的载流子迁移率。与P3HT∶PCBM薄膜相比,P3HT∶PCBM∶DMSO薄膜在可见光范围内的吸收峰有明显红移且吸收强度增强。可见光吸收的改善是实现短路电流密度提高的有力保障。太阳能电池性能的增强是因为DMSO的掺杂提高了P3HT∶PCBM的载流子迁移率和吸收光谱宽度。     

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)     

不同受体对PTB7聚合物太阳能电池的性能影响的研究

使用两种或者更多种类的富勒烯衍生物作为受体可以使poly(3-己基噻吩)(P3TH)系的混合异质结太阳能电池效率明显提升。这样的提升源于当受体使用富勒烯多重加合物的最低未占轨道(LUMO)提升而使其开路电压升高。虽然其他聚合物也同样能获得高的开路电压,但是大多数的聚合物却不像P3TH一样获得性能提升,在与像苯基-C61-丁酸甲酯 (bis-PCBM)或者the indene-C60 bis-adduct (ICBA)混合后表现出下降的光电流。在此,我们研究这些性能改变的原因。使用[6,6]-苯基C₇₀-丁酸甲酯(PC₇₀BM), ICBA和bis-PC₇₀BM作为受体并且PTB7作为给体,其结构为：ITO/PEDOT：PSS/活性层/LiF/Al,聚合物太阳能电池的表现的性能分别为7.29%, 4.92% 和3.33%。性能的改变可能主要归因于不同受体影响器件激子产生和电荷收集。     

Highly stable inverted poly (3-hexylthiophene):methano-fullerene [6,6]-phenyl C71-butyric acid methyl ester bulk heterojunction solar cell with thin oxide nano particle layer using solution process

We have investigated the inverted poly (3-hexylthiophene):methano-fullerene [6,6]-phenyl C71-butyric acid methyl ester (P3HT:PC₇₁BM) bulk heterojunction (IBHJ) solar cell with various n-type metal oxide nano particle layers on ITO and MoO₃ anode buffer layer underneath Al. The IBHJ solar cell with a tin oxide nano particle layer shows the power conversion efficiency (PCE) of 3.1% and better stability compared to conventional BHJ solar cell. The PCE of this cell decreases by 3% after 2 months in ambient air while the other cells show more degradation.     

紫外臭氧处理超薄银修饰ITO电极的高效柔性有机太阳能电池

以紫外臭氧处理超薄Ag复合MoO₃或PEDOT：PSS修饰ITO电极的高效柔性有机太阳能电池。通过优化紫外臭氧处理Ag薄膜的时间,提高了以P3HT：PCBM为有源层的器件的功率转换效率,从1.68%（未经过紫外臭氧处理）提高到2.57%（紫外臭氧处理Ag 1 min）。提高的原因推测是紫外臭氧处理形成了AgO_x薄膜,提高了电荷提取并使器件具有高光学透明度、低串联电阻和优异的表面功函数等一些性能。并且,紫外臭氧处理Ag薄膜与MoO₃或者PEDOT：PSS复合修饰ITO的器件效率分别得到提高,Ag薄膜与MoO₃复合修饰ITO的器件效率从2.02%（PET/ITO/MoO₃）提高到2.97%（PET/ITO/AgO_x/MoO₃）,Ag薄膜与PEDOT：PSS复合修饰ITO的器件效率从2.01%（PET/ITO/PEDOT：PSS）提高到2.93%（PET/ITO/AgO_x/PEDOT：PSS）。此外,以PBDTTT-EFT：PC₇₁BM为有源层的柔性聚合物太阳能电池效率可达6.21%。基于ITO的柔性光电器件效率的提高主要归于ITO被Ag/PEDOT：PSS或Ag/MoO₃修饰后功函数的提高。     

免光学间隔层的高效聚合物太阳能电池

使用相对聚(3乙基噻吩)(P3HT)具有更低能带结构的聚{[9-(1辛基壬基)-9H-咔唑-2,7-2基]-2,5-噻吩二基-2,1,3-苯并噻二唑-4,7-二基-2,5噻吩二基}(PCDTBT)作为电子给体材料和较C60衍生物(PC60BM)具有更广光谱吸收能力的C70衍生物(PC70BM)作为电子受体材料构建共混体系活性层,制备有机聚合物太阳能电池。通过控制活性层薄膜生长速度、环境得出在N2环境中静置10min时聚合物电池达到了5.65%的高光电转换效率(PCE)。然后,通过进一步优化活性层薄膜厚度短路电流密度大幅提升至14.2mA/cm2,PCE达到5.84%。结果表明,在不使用TiOx等光学间隔层的情况下,通过控制活性层薄膜生长过程和优化活性层薄膜厚度也可以大幅增加短路电流密度,获得高的PCE。     

Performance and stability studies of inverted polymer solar cells with TiO2 film as a buffer layer

TiO₂ based inverted polymer solar cells (PSCs) with a structure of fluorine-doped tin oxide (FTO)/TiO₂/P3HT:PCBM/PEDOT:PSS/Ag presented excellent air stabilities,; the power conversion efficiency (PCE) of devices exhibited only 15 % decay as compared to the highest value while being exposed in air-condition for more than 20 days. Interestingly, an overall enhancement of PCE from 3.5 % to 3.9 % was observed while the PSCs were exposed in air-condition up to 3 days; the improvement of performance was attributed to the TiO₂ films’ oxygen and water protection effect and the oxidation of Ag, which will benefit to form an effective work function match with the HOMO of P3HT leading to improved ohmic contact. However, the performance slowly decreased when the exposure time remains longer due to the physical adsorbed oxygen. UV–ozone treatment on the TiO₂ films’ leads to the formation of a metal-deficient oxide that results in a decreased PCE for the devices. Finally, X-ray photo-emission spectroscopy (XPS) was used to analyze the compositional changes of the TiO₂ films while they were exposed in air-condition or treated by UV–ozone.     

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.     

Bathocuproine/Ag复合电极对于聚合物光伏器件效率和稳定性的影响

采用Bathocuproine/Ag (BCP/Ag)复合电极代替Ca/Al复合电极, 制备PTB7:PC71BM 作为光敏层的聚合物光伏器件, 并通过改变BCP薄膜厚度来研究BCP/Ag复合电极对于器件光电转换器和稳定性的影响. 研究发现: 在光敏层和金属电极之间插入BCP修饰层后, 器件性能得到了显著的改善, 在BCP厚度为5 nm时, 器件的效率达到了6.82%, 且略高于Ca/Al复合电极的器件效率; 相比于采用Ca/Al复合电极的器件, BCP/Ag复合电极增大了器件的短路电流和外量子效率, 使器件效率得到提高; 同时器件的稳定性得到了显著的改善, BCP/Ag 复合电极器件的衰减速率几乎和未插入BCP的器件衰减速率相同, 相对于Ca/Al复合电极器件大幅提高.     

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)     

UV-ozone-treated MoO_3 as the hole-collecting buffer layer for high-efficiency solution-processed SQ:PC_(71) BM photovoltaic devices

The enhanced performance of a squaraine compound, with 2,4-bis[4-（N,N-diisobutylamino）-2,6-dihydroxyphenyl] squaraine as the donor and [6,6]-phenyl-C71-butyric acid methyl ester （PC71BM） as the acceptor, in solution-processed or- ganic photovoltaic devices is obtained by using UV-ozone-treated MoO3 as the hole-collecting buffer layer. The optimized thickness of the MoO3 layer is 8 nm, at which the device shows the best power conversion efficiency （PCE） among all devices, resulting from a balance of optical absorption and charge transport. After being treated by UV-ozone for 10 min, the transmittance of the MoO3 film is almost unchanged. Atomic force microscopy results show that the treated surface morphology is improved. A high PCE of 3.99% under AM 1.5 G illumination （100 mW/cm2） is obtained.     

Au nanorods-incorporated plasmonic-enhanced inverted organic solar cells

The effect of Au nanorods(NRs) on optical-to-electric conversion efficiency is investigated in inverted polymer solar cells, in which Au NRs are sandwiched between two layers of Zn O. Accompanied by the optimization of thickness of Zn O covered on Au NRs, a high-power conversion efficiency of 3.60% and an enhanced short-circuit current density(J SC) of10.87 m A/cm2 are achieved in the poly(3-hexylthiophene): [6,6]-phenyl-C61-butyric acid methyl ester(P3HT:PC60BM)-based inverted cell and the power conversion efficiency(PCE) is enhanced by 19.6% compared with the control device. The detailed analyses of the light absorption characteristics, the simulated scattering induced by Au NRs, and the electromagnetic field around Au NRs show that the absorption improvement in the photoactive layer due to the light scattering from the longitudinal axis and the near-field increase around Au NRs induced by localized surface plasmon resonance plays a key role in enhancing the performances.     

基于苯并二噻吩聚合物所制备的三元光电探测器的特性

本文采用P3HT∶PTB7∶PC⁶¹BM为活性层,制备了覆盖可见光范围的三元体异质结有机光电探测器(organic photodetectors,OPDs).利用原子力显微镜、紫外可见吸收光谱和荧光光谱等手段研究了PTB7添加到P3HT∶PC61BM体系中对OPDs光学和电学性质的影响,发现当P3HT∶PTB7∶PC61BM的质量比为8∶2∶10时,三元混合层的响应光谱扩展到780 nm,OPDs的响应度R在630,530,460 nm的光照和–1 V偏压下分别达到178,291,241 mA/W,比探测率D^*达到10¹² Jones,并与课题组之前成果P3HT∶PBDT-TT-C∶PC61BM为活性层的三元有机光电探测器做了对比.分析了两种基于苯并[1,2-b∶4,5-b]二噻吩(BDT)单元的聚合物PTB7与PBDT-TT-C分别添加到同一体系P3HT∶PC₆₁BM中产生的器件性能差距的现象,解释了PTB7由于氟原子的引入,对混合薄膜微观形貌的影响和对薄膜中光生载流子迁移率的提升的原因.这为制备性能更好的有机光电探测器提供了理论依据和方法.     

基于PTB7,Bis-PC_(70)BM,PC_(70)BM的高效率有机三元太阳能电池

我们将Bis-PC_(70)BM作为第二种电子受体混入基于PTB7:PC_(70)BM的聚合物太阳能电池中,制备了三元混合聚合物太阳能电池.相比于PC_(70)BM,Bis-PC_(70)BM的最低未占分子轨道(lowest unoccupied molecular orbital,LUMO)能级更高,所以掺入Bis-PC_(70)BM后器件的开路电压(V_(oc))得到了提升.Bis-PC_(70)BM在PTB7和PC_(70)BM之间起到桥梁的作用,因此在给体/受体界面创造了更多的电荷传递通道.而且从原子力显微镜中得到的结果来看,当混入质量比为3%的Bis-PC_(70)BM后薄膜的表面形貌更为平整,平均粗糙度从原来的1.87 nm降到了1.80 nm.能量转换效率(power conversion efficiency,PCE)达到7.00%,其中器件的V_(OC)为0.77 V,短路电流(J_(SC))为13.92 mA·cm~(-2),比PTB7:PC_(70)BM的器件效率6.07%提高了15%.     

Microwave-reduced graphene oxide for efficient and stable hole extraction layers of polymer solar cells

Microwave-assisted reduced graphene oxide (MR-GO) layer was applied to hole extraction layer (HEL) of polymer solar cells (PSCs) and was compared with the widely used poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) in bulk hetero-junction (BHJ) solar cells. The power conversion efficiency (PCE) of 3.57% was achieved with the MR-GO layer, which is 21% higher than that of PSCs with the conventional PEDOT:PSS HEL material. This enhancement of PCE is mainly attributed to the increase of short-circuit current density originated from the hydrophobic surface of the MR-GO layer. The hydrophobic graphene oxide surface is believed to improve wetting property and physical contact of active blends. In addition, the MR-GO interfacial layer is found to show the excellent device stability in atmospheric condition. The PCE of conventional PEDOT:PSS based PSCs showed total degradation when the device was exposed to atmospheric condition for 1000 h without any encapsulation, while that of MR-GO based PSC showed over 85% of PCE.     

Influence of small-molecule material on performance of polymer solar cells based on MEH-PPV:PCBM blend

In this work,the influence of a small-molecule material,tris(8-hydroxyquinoline) aluminum (Alq 3),on bulk het-erojunction (BHJ) polymer solar cells (PSCs) is investigated in devices based on the blend of poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) and [6,6]-phenyl-C 61-butyric acid methyl ester (PCBM).By dop-ing Alq 3 into MEH-PPV:PCBM solution,the number of MEH-PPV excitons can be effectively increased due to the energy transfer from Alq 3 to MEH-PPV,which probably induces the increase of photocurrent generated by excitons dissociation.However,the low carrier mobility of Alq 3 is detrimental to the efficient charge transport,thereby blocking the charge collection by the respective electrodes.The balance between photon absorption and charge transport in the active layer plays a key role in the performance of PSCs.For the case of 5 wt.% Alq 3 doping,the device performance is deteriorated rather than improved as compared with that of the undoped device.On the other hand,we adopt Alq 3 as a buffer layer instead of commonly used LiF.All the photovoltaic parameters are improved,yielding an 80% increase in power conversion efficiency (PCE) at the optimum thickness (1 nm) as compared with that of the device without any buffer layer.Even for the 5 wt.% Alq 3 doped device,the PCE has a slight enhancement compared with that of the standard device after modification with 1 nm (or 2 nm) thermally evaporated Alq 3.The performance deterioration of Alq 3-doped devices can be explained by the low solubility of Alq 3,which probably deteriorates the bicontinuous D-A network morphology;while the performance improvement of the devices with Alq 3 as a buffer layer is attributed to the increased light harvesting,as well as blocking the hole leakage from MEH-PPV to the aluminum (Al) electrode due to the lower highest occupied molecular orbital (HOMO) level of Alq 3 compared with that of MEH-PPV.