Cu2S nanocrystals incorporated highly efficient non-fullerene ternary organic solar cells

Here, we report Cu₂S nanocrystals based non-fullerene ternary polymer solar cells by incorporating Cu₂S in conjugated polymer (PBDB-T: poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b′]dithiophene))-alt-(5,5-(1′,3′-di-2-thienyl-5′,7′-bis(2-ethylhexyl) benzo[1′,2′-c:4′,5′-c′]dithiophene-4,8-dione))]) and small molecule non-fullerene compound (ITIC:3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene). The devices were fabricated in inverted configuration i.e. ITO/ZnO/PBDB-T: Cu₂S NCs: ITIC/MoO₃/Ag. Effect of concentration of Cu₂S nanocrystals on the performance parameters of PBDB-T: ITIC based organic solar cells is studied. An enhancement in the power conversion efficiency from 8.24% to 9.53% is achieved for the optimum concentration of Cu₂S nanocrystals in the organic photoactive blend. The cause of improvement in the performance parameters of the device is investigated by means of the light intensity dependent electrochemical impedance spectroscopy and atomic force microscopy. It is found that the devices with Cu₂S nanocrystals have less trap-assisted recombination.     

Bicontinuous network of electron donor-acceptor composites achieved by additive-free sequential deposition for efficient polymer solar cells

We report that sequential deposition of a highly crystalline polymer donor and a soluble fullerene acceptor leads to a well-defined interpenetrating network and enhanced power conversion efficiencies in bilayer polymer solar cells. Even without the use of solvent additives, layered thin films of 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) and [6,6]-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM), as electron donor and acceptor materials, respectively, showed bicontinuous networks similar to those of a PffBT4T-2OD:PC₇₁BM bulk-heterojunction (BHJ) thin film processed with 1,8-diiodooctane (DIO) as a solvent additive. Transmission electron microscopy results confirmed the BHJ-like morphology of the bilayered PffBT4T-2OD/PC₇₁BM thin films. Bilayer solar cells fabricated without the DIO additive produced a power conversion efficiency of η ≈ 7.65%, which is even higher than that of a BHJ solar cell fabricated with the DIO additive (η ≈ 7.04%). These results demonstrate that a highly crystalline polymer donor and an electron-accepting small molecule can be a good combination for efficient bilayer polymer solar cells.     

基于电场调控的高性能紫外无机-有机复合结构光电探测器

通过溶液旋涂制备了结构为ITO/ZnO/P3HT:ITIC/Ag的紫外无机-有机复合结构光电探测器,混合膜中聚合物给体(P3HT)和非富勒烯小分子受体(ITIC)的质量比为100:1.由于载流子传输通道不连续,器件在零偏压下的暗电流密度很小,为5.8×10-10 A·cm-2,为器件实现外加电场可调和光电流倍增提供了条...     

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.     

Study of a ternary blend system for bulk heterojunction thin film solar cells

In this research, we report a bulk heterojunction(BHJ) solar cell consisting of a ternary blend system. Poly(3-hexylthiophene) P3 HT is used as a donor and [6,6]-phenyl C61-butyric acid methylester(PCBM) plays the role of acceptor whereas vanadyl 2,9,16,23-tetraphenoxy-29 H, 31H-phthalocyanine(VOPc Ph O) is selected as an ambipolar transport material. The materials are selected and assembled in such a fashion that the generated charge carriers could efficiently be transported rightwards within the blend. The organic BHJ solar cells consist of ITO/PEDOT:PSS/ternary BHJ blend/Al structure. The power conversion efficiencies of the ITO/ PEDOT:PSS/P3HT:PCBM/Al and ITO/PEDOT:PSS/P3HT:PCBM:VOPcPhO/Al solar cells are found to be 2.3% and 3.4%, respectively.     

NiO_x作为空穴传输层对有机太阳能电池光吸收的影响

基于多层膜系模型的传输矩阵方法、麦克斯韦方程和光子吸收方程,研究了NiOx作为替代3,4-乙撑二氧噻吩:聚苯乙烯磺酸盐(PEDOT:PSS)的空穴传输材料对聚3-己噻吩(P3HT)和富勒烯衍生物([6,6]-phenyl-C61-butyric acid methyl ester,PC61BM)共混体异质结有机太阳能电池器件内部光电场分布和光吸收特性的影响.分别制备了以NiOx和PEDOT:PSS为空穴传输层,P3HT:PCBM为活性层的有机太阳能电池,并通过数值模拟的方法比较了NiOx和PEDOT:PSS两种空穴传输材料对器件光伏特性的影响.结果表明:10 nm的NiOx空穴传输层器件比40 nm的PEDOT:PSS器件获得了更大的短路电流和填充因子,并具有更高的能量转化效率.     

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。     

A fullerene silirane derivative to improve the open circuit voltage in a polymer–fullerene solar cell: a theoretical study

In this letter quantum chemical calculations are performed on fullerene derivatives with varying reduction potentials, successfully used as electron acceptor in bulk heterojunction solar cells with the aim to investigate the energy levels of the frontier orbitals. We have successfully correlated the theoretical lowest unoccupied molecular orbital (LUMO) levels of different fullerenes with the open circuit voltage of the photovoltaic device based on the polymer–fullerene blend. We have also proposed a new fullerene silirane derivative with a raised LUMO level useful to increase the open circuit voltage of a polymer solar cell. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

MEH-PPV与TiO2共混体系太阳电池性能分析

以MEH-PPV(poly(2-methoxy-5-(2′-ethylhexoxy)-1,4-phenylene vinylene)为电子给体材料(Donor,D), TiO₂纳米线为电子受体材料(Acceptor,A),制成了共混体系太阳电池. 从D/A材料共混体系的紫外可见吸收光谱(UV-vis)、光荧光谱(PL)、器件的电荷传输的光导J-V图等方面,分析了MEH-PPV∶TiO₂体系器件性能变化的原因. 得出了当在纯MEH-PP 关键词： 太阳电池 聚合物 性能     

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%.     

纳米银增强聚合物太阳能电池光吸收的研究

基于共轭聚合物给体材料P3HT和富勒烯衍生物受体材料PCBM共混的体异质结结构 的聚合物太阳能电池因其空穴载流子迁移率低而限制了P3HT:PCBM功能层厚度, 从而影响了器件对入射光的吸收. 在聚合物功能层内引入金属纳米颗粒可以利用金属表面等离子体效应增强器件内电场并改善器件的光吸收. 本文基于时域有限差分法(finite difference time domain, FDTD)方法模拟得到了聚合物功能层内包含了直径为50 nm纳米银球并且球间距为50 nm的聚合物太阳能 电池器件在波长分别为400 nm和500 nm照射时的二维光电场分布以及入射角分别为15°, 45°, 60°时包覆纳米银聚合物功能层横截面内的光电场强度分布; 计算得到了银纳米颗粒尺寸分别为10 nm, 20 nm和50 nm时以及分布在空穴传输层PEDOT:PSS的纳米银器件的光吸收; 并计算了斜入射时包覆纳米银的聚合物功能层光吸收. 理论分析表明: 聚合物功能层加入纳米银球后, 因为纳米银球的表面等离子体效应使入射光在功能层内散射增强而使器件内的光电场重新分布; 直径较大的纳米银颗粒能产生大角度的光散射, 更有利于聚合物功能层对光的吸收. 这里, 基于有机银盐还原法制备了纳米银颗粒并制备了银等离子体增强的聚合物太阳能电池, 其结构为: glass/ITO (～100 nm)/PEDOT:PSS (40 nm)/P3HT:PCBM (～100 nm)(nano-Ag)/LiF (1 nm)/Al (120 nm). 该器件与平板器件的性能对比实验证实: 通过在聚合物功能层内上引入纳米银颗粒可以有 效增加器件光吸收并改善器件电学性能, 器件外量子效率在520 nm处最大增加了17.9%. 关键词： 纳米银 表面等离子体共振 时域有限差分 聚合物太阳能电池     

Raman spectroscopic identification of fullerene inclusions in polymer/fullerene blends

Thin films of the conjugated polymer poly(3‐hexylthiophene) (P3HT) and blends of the soluble fullerene derivative[6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) with P3HT—a well studied but not completely understood donor–acceptor system for organic solar cells—have been studied by means of UV–visible absorption and resonant Raman spectroscopy. Additionally, we have employed atomic force microscopy phase imaging to characterize the nanomorphology of the P3HT : PCBM thin film, revealing a close intermixing of two phases with domain sizes ranging from a few to several tens of nanometers. A systematic analysis of pristine polymer and blend Raman spectra provides evidence that features attributable to PCBM, possibly even depending on the charge state of the fullerene molecule, can be observed. Hence our results suggest that fullerene inclusions in polymer/fullerene blends can be identified via Raman spectroscopy. Copyright © 2011 John Wiley & Sons, Ltd.     

有机共混结构叠层太阳电池的研究进展

有机太阳电池由于质轻、价廉、柔性,受到人们的广泛关注.单个有机材料只能吸收部分太阳光,叠层结构的太阳电池将不同吸收带隙的有机材料通过中间层连接起来,既能充分吸收太阳光,又能提高太阳电池的开路电压或短路电流.本文综述了近年来有机共混结构叠层太阳电池的研究进展,介绍了各种叠层有机太阳电池的结构、原理及性能,阐述了国内外有机叠层太阳电池研究的现状及存在问题,为高性能有机太阳电池的研究提供有价值的参考.     

Fullerene solubility–current density relationship in polymer solar cells

During the last decade polymer solar cells have undergone a steady increase in overall device efficiency. To date, essential efficiency improvements of polymer–fullerene solar cells require the development of new materials. Whilst most research efforts aim at an improved or spectrally extended absorption of the donor polymer, not so much attention has been paid to the fullerene properties themselves. We have investigated a number of structurally related fullerenes, in order to study the relationship between chemical structure and resulting polymer–fullerene bulk heterojunction photovoltaic properties. Our study reveals a clear connection between the fullerene solubility as material property on one hand and the solar cells short circuit photocurrent on the other hand. The tendency of the less soluble fullerene derivates to aggregate was accounted for smaller current densities in the respective solar cells. Once a minimum solubility of approx. 25 mg/ml in chlorobenzene was overcome by the fullerene derivative, the short circuit current density reached a plateau, of about 8–10 mA/cm². Thus the solubility of the fullerene derivative directly influences the blend morphology and displays an important parameter for efficient polymer–fullerene bulk heterojunction solar cell operation. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of C<Subscript>60</Subscript> on methyl red and crystal violet dye-doped photovoltaic device

The potential of dye sensitization of organic photovoltaic devices has been investigated. The photoelectrical properties of such devices have been studied. With the help of spin-coating method, single layer and double layer structures are prepared with the help of both methyl red and crystal violet dye at a time. Methyl red and crystal violet dye are dispersed in polyvinyl alcohol used as an inert polymer binder and polyethylene oxide complexed with LiClO₄ ion salt as a solid electrolyte. Ethylene carbonate and propylene carbonate are used as plasticizers. A layer of this blend is sandwitched between two electrodes, one of which is indium tin oxide (ITO)-coated glass plate and another is Al electrodes. In this study, the use of a C₆₀ layer over the previously prepared blend is done. ITO-coated glass plate and Al electrodes are taken as counter electrodes. Use of C₆₀ molecule over the polymer blend in a heterojunction increased the efficiency of photovoltaic devices. In this type of device, the polymer blend acts as an electron donor to the second layers, whereas C₆₀ plays the role of an electron acceptor.     

Field-enhanced charge flow in nanorod heterostructure solar cells

Recent studies on organic heterostructure solar cells have indicated that interface morphology plays an important role in determining the quantum efficiency. Hybrid heterostructure mixing donor and acceptor semiconductors appear to offer the best opportunity in achieving superior performance and there are indications that a network of percolated heterojunctions can be quite effective in promoting light absorption and exciton quenching. Charge transport and collection efficiency, however, appear to be more complex in the bulk heterostructure and the nature of charge flow depends largely on the type of current paths in existence. We report in this work the possible existence of field-assisted charge flow in the nanorod heterostructure solar cells when carriers of different polarity move in close proximity. The field-effect associated with the charge density gradients can exert a force on the nearby carriers resulting in an increase in the short-circuit current. The model is used to explain data reported in the literature on solar cells composed of TiO₂ nanorods embedded in a conjugated polymer.     

Improved efficiency of ternary the blend polymer solar cells by doping a narrow band gap polymer material

A series of P3HT:PC71BM polymer solar cells(PSCs)with different PIDTDTQx doping concentrations were fabricated to investigate the effect of the PIDTDTQx as a complementary electron donor on the performance of PSCs.The power conversion efficiency(PCE)of the optimized ternary blend PSCs(with 2 wt%PIDTDTQx)reached 3.87%,which is 28%higher than that of the PSCs based on P3HT:PC71BM(control cells).The short-circuit current density(Jsc)was increased to 10.20 m A/cm2compared with the control cells.The PCE improvement could be attributed to more photon harvest and charge carrier transport by appropriate doping PIDTDTQx.The energy transfer from P3HT to PIDTDTQx was demonstrated from the 650 nm emission intensity decrease and the red-shifted emission peaks from 725 nm to 737 nm along with the increase of PIDTDTQx doping concentrations.     

Ab Initio Simulation of Charge Transfer at the Semiconductor Quantum Dot/TiO2 Interface in Quantum Dot‐Sensitized Solar Cells

Quantum dot‐sensitized solar cells (QDSSCs) have emerged as a promising solar architecture for next‐generation solar cells. The QDSSCs exhibit a remarkably fast electron transfer from the quantum dot (QD) donor to the TiO₂ acceptor with size quantization properties of QDs that allows for the modulation of band energies to control photoresponse and photoconversion efficiency of solar cells. To understand the mechanisms that underpin this rapid charge transfer, the electronic properties of CdSe and PbSe QDs with different sizes on the TiO₂ substrate are simulated using a rigorous ab initio density functional method. This method capitalizes on localized orbital basis set, which is computationally less intensive. Quite intriguingly, a remarkable set of electron bridging states between QDs and TiO₂ occurring via the strong bonding between the conduction bands of QDs and TiO₂ is revealed. Such bridging states account for the fast adiabatic charge transfer from the QD donor to the TiO₂ acceptor, and may be a general feature for strongly coupled donor/acceptor systems. All the QDs/TiO₂ systems exhibit type II band alignments, with conduction band offsets that increase with the decrease in QD size. This facilitates the charge transfer from QDs donors to TiO₂ acceptors and explains the dependence of the increased charge transfer rate with the decreased QD size.     

Polymer heterostructures with embedded carbon nanotubes for efficient photovoltaic cells

Polymer photovoltaic cells (PVC) are intensely investigated because of their potential advantages over Si-based PVCs. Their present drawbacks are low conversion efficiency, limited exciton diffusion length, poor hole carriers transport and short lifetime. The highest conversion efficiency achieved so far in spin-coated polymer blends is close to 5%. Recently, efficiency growing has been demonstrated in multilayer architectures involving a donor/acceptor bulk heterojunction. Alternatively, a nanomaterial has been added to the polymer active layer to facilitate excitons dissociation and carriers transport through the polymer matrix. In this work we investigate both these approaches, first embedding single wall Carbon Nanotubes (SWCNT) in the polymeric matrix to improve the electrical transport and second studying the optical absorption of different polymer thin films to optimize the spectral response of the donor/acceptor heterojunction.     

基于光学与光—电转换模型对聚合物电池功能层厚度与性能相关性分析

本文基于Forouhi-Bloomer 模型得到了这种功能层的光学常数.根据菲涅耳系数矩阵法计算了这种器件内的光电场分布,并计算了不同厚度的聚合物功能层的光子吸收数.同时,通过Onsager-Braun理论,分析了在无外加电场下聚合物功能层厚度对激子分离概率的影响.理论分析和实验结果证明:在特定的薄膜制备工艺下,器件结构为ITO/PEDOT/ P3HT:PC₆₀BM /LiF/Al时,聚合物功能层厚度在100 nm左右时,可以使器件的光子吸收数最大化,同时避免了激子分离概率的降低. 关键词： 光学常数 激子 聚合物太阳能电池