Efficient ternary polymer solar cells by optimizing photogenerated exciton dissociation and photon harvesting with a short wavelength absorption polymer acceptor as the third component

Ternary blend films, obtained by introducing a third component (a second acceptor as the third component) to a binary polymer solar cell (PSC), are a promising ternary strategy because the light absorption range, surface morphology, and charge carrier transport of the photoactive layer may be optimized, as can the energy level alignment between the donor and the acceptor. In this work, acceptors such as the short-wavelength-absorption polymer N2200 and the long-wavelength-absorption small molecule FOIC were combined with the donor PBDB-T-2F to construct ternary blends. The optimized ternary PSC could achieve a power conversion efficiency (PCE) of 13.98%, which is higher than the efficiencies of binary PSCs based on PBDB-T-2F:FOIC (12.65%) and PBDB-T-2F:N2200 (9.36%). The enhanced PCE of the ternary PSC is based on the high electron mobility, balanced charge transport, optimized surface morphology and charge carrier kinetics and the extended light absorption of the ternary photoactive layer, realized by adjusting the ratio of FOIC:N2200. Our results indicate that mixing a polymer acceptor into a binary photoactive layer to form a ternary blend photoactive layer is a valuable strategy for improving photovoltaic performance.     

Improved efficiency and stability in polymer solar cells using a Tetra-nuclear Zinc(II) complex interfacial layer

Tetra-nuclear Zinc(II) complex Zn₄O(AID)₆ [AID = 7-azaindolate] is a wide band gap luminescent material that exhibits efficient emission matching the absorption spectra of organic donor materials such as polythiophene (P3HT). This work demonstrates polymer solar cells (PSC) based on P3HT:PCBM (phenyl-C₆₁-butyric acid methyl ester) blend active layer with a Zn₄O(AID)₆ cathode interfacial layer achieving a power conversion efficiency (PCE) significantly higher than that of the reference devices. The energy level and impedance spectroscopy analysis show that the Zn₄O(AID)₆ cathode interfacial layer acts as an efficient exciton/hole blocking layer, and reduces charge recombination rate with more efficient electron extraction. The Zn₄O(AID)₆ interfacial layer also helps achieve longer lifetime of PSC devices. The improved efficiency and stability combined with low cost and nontoxicity of Zn₄O(AID)₆ make it a promising cathode interfacial material for high-performance and stable PSC devices.     

Limiting factors of photon-to-current conversion in polymer/nanocrystal bilayer hybrid solar cells: An analytical quantum efficiency model study

This paper introduces an analytical external quantum efficiency (EQE) model of planar hybrid solar cells (HSCs) based on photon-to-current conversion processes and uses this to investigate the factors that limit the maximum EQE (EQE_m) of devices; i.e., the photon absorption coefficient α, exciton diffusion coefficient D_z, exciton lifetime τ_z, exciton dissociation rate k_dis, electron diffusion coefficient D_e, electron lifetime τ_e, nanocrystals thickness d, and thickness of the polymer l. Our simulations indicate that relying solely on modifying k_dis, D_e, or τ_e cannot achieve a breakthrough increase in the EQE_m of planar HSCs. However, increasing α, D_z, or τ_z could potentially lead to a large EQE_m (30–100%), especially in the context of high k_dis values. Moreover, the calculation results indicate that although both D_z and τ_z contribute to the exciton diffusion length (L_z) via the equation L_z² = D_zτ_z, the EQE_m has an asymmetric dependence on these variables. With a small k_dis (i.e., <10⁴ cm/s), an increase in D_z results in an initial increase and then decrease in EQE_m, resulting in a peak value that increases with increasing k_dis. When k_dis is sufficiently large (∼10⁵ cm/s), the EQE_m becomes saturated after the initial increase. Thus, although an increase in D_z can adversely affect device performance when the k_dis is lower than 10⁴ cm/s, increasing τ_z always improves device performance, regardless of large k_dis becomes. This behavior can be attributed to the detrimental effect of excitons accumulating at the D/A interface, and can be used to optimize the material design and device engineering of planar HSCs and related solar cells for maximum photon-to-current conversion performance. In addition, we also demonstrate that the model can fit to the experimental data.     

Relationship between HOMO energy level and open circuit voltage of polymer solar cells

A series of π-conjugated polymers (PDHF-BT and PDHF-TBT) with 4-(3,4-ethylenedioxythienyl)-2,1,3-benzothiadiazole (BT), 4,7-bis(3,4-ethylenedioxythienyl)-2,1,3-benzothiadiazole (TBT), and 9,9′-dihexylfluorene were synthesized by the Suzuki coupling reaction. The HOMO energy level of PDHF-BT was −5.47 eV, which was lower than that of PDHF-TBT (−5.22 eV), while the LUMO energy level of PDHF-BT (−3.45 eV) was very similar to that of PDHF-TBT (−3.42 eV). These energy levels of PDHF-BT and PDHF-TBT were also supported by a DFT calculation. The power conversion efficiency (PCE) of the polymer solar cell (PSC) with a structure of ITO/PEDOT:PSS/PDHF-BT:PCBM (1:1)/Al was determined as 0.34% and it was larger than that of the device based on PDHF-TBT (0.22%). Correspondingly, the V_oc of the PSC based on PDHF-BT (0.71 V) was much larger than that of the device based on PDHF-TBT (0.40 V). The results support that the V_oc of polymer based PSCs is strongly related to the HOMO energy level of the active polymers.     

Incorporation of diketopyrrolopyrrole dye to improve photovoltaic performance of P3HT:PC71BM based bulk heterojunction polymer solar cells

Ternary blend solar cells have been intensively studied in recent years to harvest more photons over the near-IR region. In this work, the effects of adding a diketopyrrolopyrrole dye (py-DPP) into a conventional P3HT:PC₇₁BM based bulk heterojunction photovoltaic cell are investigated. The near infrared absorption of the blend is enhanced by the doped py-DPP dye, leading to more than 20% increased power conversion efficiency compared to the P3HT:PC₇₁BM binary system. The highest efficiency of 4.05% is achieved for a P3HT:PC₇₁BM blend with 2.4 wt % of py-DPP.     

An insight on oxide interlayer in organic solar cells: From light absorption and charge collection perspectives

A comprehensive study of the effect of oxide interlayer on the performance of bulk-heterojunction organic solar cells (OSCs), based on poly[[4,8-bis[(2-ethylhexyl)oxy] benzo [1,2-b:4,5-b'] dithiophene-2,6- diyl] [3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno [3,4-b] thiophenediyl]] (PTB7): [6,6]-phenyl C71 butyric acid methyl ester (PC₇₀BM) blend system, is carried out by optical simulation, interfacial exciton dissociation and charge collection analyses. It is found that a PTB7:PC₇₀BM blend layer thickness optimized for maximum light absorption in OSCs does not generally give rise to the highest power conversion efficiency (PCE). OSCs, e.g., based on PTB7:PC₇₀BM blend system, can benefit from the oxide interlayer in two ways, (1) to enhance the built-in potential for reducing recombination loss of the photo-generated charges, and (2) to improve charge collection by removal of unfavorable interfacial exciton dissociation. The combined effects result in ∼20% improvement in PCE over an optimized control cell, having an identical layer configuration without an oxide interlayer.     

Effects of exciton blocking layer and cathode electrode work function on the performance of polymer solar cells

In this study the effects of some important processing and post-processing treatments on the performance of poly(3-hexylthiophene-2,5-diyl) (P3HT):[6,6]-phenyl-C₆₁-butyric acid methyl ester ([60]PCBM) solar cells were investigated. These parameters included the active layer film formation period, thermal annealing, electrical treatment, cathode work function modification, and exciton blocking layer type and thickness. Polymer bulk heterojunction solar cells having a glass/indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/P3HT:PCBM/(Ca or LiF)/Al structure were fabricated. The morphology of the active layer was investigated using atomic force microscopy. The results showed that the morphology state of the active layer exactly after spin coating process was very important parameter, which could dictate different responses of solar cells to a certain treatment. Using solvent additives to prolong the film formation period and storing in small dish could reach the morphology of the active layer near its best state in which there was no need to apply common post-treatment processes. A thickness at about 20 nm was required for Ca layer to effectively act as exciton blocking layer while LiF with 1 nm thickness worked better.     

Solvent engineering of the electron transport layer using 1,8-diiodooctane for improving the performance of perovskite solar cells

In this work, the power conversion efficiency (PCE) of perovskite solar cells (PSCs) was improved by 14.8% (from 11.09% to 12.73%) by using 1,8-diiodooctane (DIO) as a solvent additive during the deposition of phenyl-C61-butyric acid methyl ester (PCBM) layers. The primary reasons for the PCE improvement are the simultaneous increases in the short-circuit current density, fill factor, and open-circuit voltage. The incorporation of DIO improves the morphology of the electron transport layer (PCBM), which plays an important role in charge dissociation, transportation, and collection. Our results indicate that engineering the morphology of the electron transport layer is a simple and effective method for developing high-performance PSCs.     

聚乙二醇阴极修饰层改善聚合物太阳能电池光电性能的研究

通过将聚乙二醇(PEG)掺入活性层制备聚合物太阳 能电池,利用PEG的迁移特性获得阴极修饰层,研 究PEG阴极修饰层对聚合物太阳能电池光电性能的影响。X射线光电子能谱(XPS)分 析表明,掺入活性层中的 PEG迁移到活性层与Al电极之间,形成了阴极缓冲层。吸收光谱、电流密度-电压 特性曲线和外量子 效率谱的分析表明,PEG阴极缓冲层的形成改善了活性层与阴极的界面接触特性, 降低了活性层与电 极之间的能级势垒,有利于载流子传输,因此显著地改善了聚合物太阳能电池的光电性能, 使得器件的开 路电压Voc、短路电流密度Jsc和填充因子(FF)都有明显提高。当P3HT:PCBM 活性层中掺入体积比为0.5%的PEG时,聚合物太阳能电池的能量转换 效率(P CE)最高,达到了3.07%,比未掺杂PEG的参考器件提 高了38.5%。     

Stepwise co-sensitization as a useful tool for enhancement of power conversion efficiency of dye-sensitized solar cells: The case of an unsymmetrical porphyrin dyad and a metal-free organic dye

A tertiary arylamine compound (DC), which contains a terminal cyano-acetic group in one of its aryl groups, and an unsymmetrical porphyrin dyad of the type Zn[Porph]-L-H₂[Porph] (ZnP-H₂P), where Zn[Porph] and H₂[Porph] are metallated and free-base porphyrin units, respectively, and L is a bridging triazine group functionalized with a glycine moiety, and were synthesized and used for the fabrication of co-sensitized dye-sensitized solar cells (DSSCs). The photophysical and electronic properties of the two compounds revealed spectral absorption features and frontier orbital energy levels that are appropriate for use in DSSCs. Following a stepwise co-sensitization procedure, by immersing the TiO₂ electrode in separate solutions of the dyes in different sequence, two co-sensitized solar cells were obtained: devices C (ZnP-H₂P/DC) and D (DC/ZnP-H₂P).The two solar cells were found to exhibit power conversion efficiencies (PCEs) of 6.16% and 4.80%, respectively. The higher PCE value of device C, which is also higher than that of the individually sensitized devices based on the ZnP-H₂P and DC dyes, is attributed to enhanced photovoltaic parameters, i.e. short circuit current (J_sc = 11.72 mA/cm²), open circuit voltage (V_oc = 0.72 V), fill factor (FF = 0.73), as it is revealed by photovoltaic measurements (J–V curves) and by incident photon to current conversion efficiency (IPCE) spectra of the devices, and to a higher total dye loading. The overall performance of device C was further improved up to 7.68% (with J_sc = 13.45 mA/cm², V_oc = 0.76 V, and FF = 0.75), when a formic acid treated TiO₂ ZnP-H₂P co-sensitized photoanode was employed (device E). The increased PCE value of device E has been attributed to an enhanced J_sc value (=13.45 mA/cm²), which resulted from an increased dye loading, and an enhanced V_oc value (=0.76 V), attributed to an upward shift and increased of electron density in the TiO₂ CB. Furthermore, dark current and electrochemical impedance spectra (EIS) of device E revealed an enhanced electron transport rate in the formic acid treated TiO₂ photoanode, suppressed electron recombination at the photoanode/dye/electrolyte interface, as well as shorter electron transport time (τ_d), and longer electron lifetime (τ_e).     

Formation of charge transfer complexes significantly improves the electron transfer process of polymer solar cells

A fluorescent inhibitor, 1-Bromo-4-Nitrobenzene (1-Br-4-NB, C₆H₄BrNO₂), is introduced to poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) active layer of polymer solar cells (PSCs). When the amount of 1-Br-4-NB added is 25 wt%, the device performance of PSCs is optimal. To investigate the means by which the power conversion efficiency (PCE) is improved, external quantum efficiency (EQE), fluorescence spectrum, transient absorption spectroscopy and dynamics photoresponse, X-ray diffraction (XRD) patterns are measured and density functional theory (DFT) calculations are carried out. The results indicate that excitonic recombination to the ground state is reduced and excitonic dissociation at the donor–acceptor interface is enhanced, which explains the inhibitory effect on the generation of fluorescence. Moreover, the electron transfer complexes (P3HT–C₆H₄BrNO₂) is demonstrated to be formed after the addition of 1-Br-4-NB. The PCE of PSCs achieves an improvement of more than 57% compared to the reference solar cell without 1-Br-4-NB.     

Synthesis and characterization of triphenylamine flanked thiazole-based small molecules for high performance solution processed organic solar cells

Two new small molecules, 5,5-bis(2-triphenylamino-3-decylthiophen-2-yl)-2,2-bithiazole (M1) and 2,5-bis(2-triphenylamino-3-decylthiophen-2-yl)thiazolo[5,4-d]thiazole (M2) based on an electron-donor triphenylamine unit and electron-acceptor thiophene-thiazolothiazole or thiophene-bithiazole units were synthesized by a palladium(0)-catalyzed Suzuki coupling reaction and examined as donor materials for application in organic solar cells. The small molecules had an absorption band in the range of 300-560 nm, with an optical band gap of 2.22 and 2.25 for M1 and M2, respectively_. As determined by cyclic voltammetry, the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of M1 were −5.27 eV and −3.05 eV, respectively, which were 0.05 eV and 0.02 eV greater than that of M2. Photovoltaic properties of the small molecules were investigated by constructing bulk-heterojunction organic solar cell (OSC) devices using M1 and M2 as donors and fullerene derivatives, 6,6-phenyl-C61-butyric acid methyl ester (PC₆₁BM) and 6,6-phenyl-C71-butyric acid methyl ester (PC₇₁BM) as acceptors with the device architecture ITO/PEDOT:PSS/M1 or M2:PCBM/LiF/Al. The effect of the small molecule/fullerene weight ratio, active layer thickness, and processing solvent were carefully investigated to improve the performance of the OSCs. Under AM 1.5 G 100 mW/cm² illumination, the optimized OSC device with M1 and PC₇₁BM at a weight ratio of 1:3 delivered a power conversion efficiency (PCE) of 1.30%, with a short circuit current of 4.63 mA/cm², an open circuit voltage of 0.97 V, and a fill factor of 0.29. In contrast, M2 produced a better performance under identical device conditions. A PCE as high as 2.39% was recorded, with a short circuit current of 6.49 mA/cm², an open circuit voltage of 0.94 V, and a fill factor of 0.39.     

Synthesis and characterization of a new perylene bisimide (PBI) derivative and its application as electron acceptor for bulk heterojunction polymer solar cells

A symmetrical perylene bisimide derivative (PBI) with 2-(4-nitrophenyl)acrylonitrile groups at the 1,7 bay positions of perylene and solubilizing cyclohexyl units was synthesized and characterized. The absorption spectrum of PBI was broad with the most prominent peak at 655 nm and optical band gap of 1.72 eV. The electrochemical investigation indicates that PBI has a LUMO energy level of −3.9 eV which is similar to that of PCBM or PC₇₀BM. Bulk heterojunction solar cell fabricated using a blend of poly(3-hexylthiophene) (P3HT) and PBI (1:1 w/w) as active layer cast from THF exhibited power conversion efficiency (PCE) at 1.56%. However, the device with P3HT:PBI blend deposited from mixed solvent (DIO/THF) improved the PCE to 2.78% which further increased to 3.17% on using the thermal annealed active layer. The improvement in the PCE is attributed to the enhanced crystallinity of the blend (particularly P3HT) and increase in hole mobility leading to balanced charge transport.     

Effects of defect states on the performance of CuInGaSe2 solar cells

Device modeling has been carried out to investigate the effects of defect states on the performance of ideal CulnGaSe2 （CIGS） thin film solar cells theoretically. The varieties of defect states （location in the band gap and densities） in absorption layer CIGS and in buffer layer CdS were examined. The performance parameters： open-circuit voltage, short-circuit current, fill factor, and photoelectric conversion efficiency for different defect states were quantitatively analyzed. We found that defect states always harm the performance of CIGS solar cells, but when defect state density is less than 10 14 cm-3 in CIGS or less than 10 18 cm-3 in CdS, defect states have little effect on the performances. When defect states are located in the middle of the band gap, they are more harmful. The effects of temperature and thickness are also considered. We found that CIGS solar cells have optimal performance at about 170 K and 2 μm of CIGS is enough for solar light absorption.     

钛硅氧化物修饰对染料敏化太阳能电池性能影响研究

用溶胶-凝胶法配制了Ti-Si溶胶,并利用浸泡和煅烧法对染料敏化太阳能电池TiO2多孔光阳极进行了修饰处理,研究了Ti-Si氧化物修饰中Si含量对光阳极染料吸附量、TiO2/染料/电解质界面电荷传输电阻、电子寿命和光电转化性能的影响。发现Ti-Si氧化物修饰钝化了光阳极的表面态,改善了电极的电子寿命,促进了电荷的有效传输,提高了光生电子向TiO2中的注入效率;当Si含量为摩尔分数10%时,电池获得最高的光电转化效率7.11%。     

Dependence of opto-electric properties of (semi-)conducting films in polymer based solar cells on viscous shear during the coating process

Organic photovoltaic is a promising technology for low-cost energy conversion. One of its major challenges is the transfer of the manufacturing process to a continuous roll-to-roll process. Previous research showed that the coating method has a significant impact on film properties, which may be explained by a shear-rate induced crystallization of the polymer–fullerene-blend.In this paper we report on a controlled variation of the shear-rate during slot-die coating of photoactive and conductive layers for polymer solar cells. Light absorption of photoactive layers increased towards higher coating speed and thus higher shear-rate by up to 28% from 0.6 m/min to 12 m/min. The currently lower performance of roll-to-roll processed solar cells, compared to laboratory scale devices may be increased by intentionally applying a high shear rate during the coating process. In contrast, a shear induced crystallization is insignificant for conductive (PEDEOT:PSS and Ag-nanoparticle) films, where conductivity decreased when the operating point approached the stability limit. Thus, a low capillary number is desirable for PEDOT:PSS layers, whereas the performance of the photoactive layer increased within the investigated velocity range. These tendencies, shown here for a standard material system (P3HT:PCBM), are substantial for the design of a roll-to-roll process for efficient polymer solar cells.     

Formation of charge‐transfer complexes significantly improves the performance of polymer solar cells based on PBDTTT‐C‐T: PC71BM

By adding appropriate proportions of nitrobenzene (C₆H₅NO₂) to the blended solution of poly{[4,8‐bis‐(2‐ethyl‐hexyl‐thiophene‐5‐yl)‐benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl]‐alt‐[2‐(2′‐ethyl‐hexanoyl)‐thieno[3,4‐b]thiophen‐4,6‐diyl]}:[6,6]‐phenyl‐C71‐butyric acid methyl ester (PBDTTT‐C‐T: PC₇₁BM), we substantially improved the power conversion efficiency from the best reported value of 7.48–8.88%. Experiments and simulations show that nitrobenzene and PBDTTT‐C‐T form stable coplanar charge‐transfer complexes through hydrogen bonds. Formation of the PBDTTT‐C‐T‐C₆H₅NO₂ complex simultaneously increases the external quantum efficiency. The underlying mechanisms of increased external quantum efficiency are attributed to the following: (i) higher lowest unoccupied molecular orbital (LUMO) of PBDTTT‐C‐T‐C₆H₅NO₂ for more efficient photoinduced electron transfer to the LUMO of PC₇₁BM and (ii) efficient quenching of fluorescence in the active layers due to formation of the PBDTTT‐C‐T‐C₆H₅NO₂ complex. This discovery clearly illustrates the potential of hydrogen‐bonded complexes as a new route for efficient polymer‐based photovoltaic devices. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and photophysical properties of semiconductor molecules D1-A-D2-A-D1-type structure based on derivatives of quinoxaline and dithienosilole for organics solar cells

A novel small molecule with D1-A-D2-A-D1 structure denoted as DTS(QxHT₂)₂ based on quinoxaline acceptor and dithienosilone donor units was synthesized and its optical and electrochemical properties were investigated. The thin film of DTS(QxHT₂)₂ showed a broad absorption profile covering the solar spectrum from 350 nm to 780 nm with an optical bandgap of 1.63 eV. The energy levels estimated from the cyclic voltammetry indicate that this small molecule is suitable as donor along with PC₇₁BM as acceptor for the fabrication solution processed bulk heterojunction solar cells for efficient exciton dissociation and high open circuit voltage. The organic solar cells based on optimized DTS(QxHT2)2:PC₇₁BM active layers processed with chloroform and DIO/CF showed overall power conversion efficiency of 3.16% and 6.30%, respectively. The higher power conversion efficiency of the solar cell based on the DIO/CF processed active layer is attributed to enhanced short circuit photocurrent and fill factor may be related to better phase separation between donor and acceptor in the active layer and more balanced charge transport, induced by the solvent additive. The power conversion efficiency of the organic solar cell was further improved up to 7.81% based on active layer processed with solvent additive, using CuSCN as hole transport layer instead of PEDOT:PSS and mainly attributed to increased fill factor and open circuit voltage due the formation of better Ohmic contact between the active layer and the CuSCN layer.     

Titanium wire engineering and its effect on the performance of coil type cylindrical dye sensitized solar cells

This paper reports a comparative study of the photovoltaic characteristics of titanium (Ti) metal wires with different diameter and surface treatments towards their utilization as photoanodes for coil-based dye-sensitized solar cells. The surface property of the Ti wire, especially oxidized overlayer and surface treatments have been found to greatly influence the adhesion as well as optimum electrical contact between coated nanoporous titanium oxide (TiO₂) and Ti-wires. Implication of adhesion of nanoporous TiO₂ on the titanium wire and its influence on photovoltaic performance was analyzed using electrochemical impedance spectroscopy. Results of X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy reveals the formation of anatase TiO₂ nanosheets after the H₂O₂ surface treatment on the titanium wire resulting into enhancement in the extent of dye loading leading to enhanced photoconversion efficiency of 4.71% under simulated solar irradiation.