Improved efficiency and stability of inverted polymer solar cells with a solution-processed BPhen interlayer and polystyrene beads

We demonstrate improved power conversion efficiency (PCE) and strongly enhanced stability of inverted organic solar cells (OSCs) with Cs halides by solution casting BPhen (4,7-di(phenyl)-1,10-phenanthroline) on the halide layer and ∼100 nm polystyrene beads (PSB) on the blank side of the OSC’s substrate. The PCE of ITO/CsCl/P3HT:PCBM/MoO₃/Al (where P3HT is poly 3-hexylthiophene and PCBM is [6,6]-phenyl-C₆₀-butyric acid methyl ester) improves by up to 46%, from 2.5% to ∼3.7%, by adding a solution-processed BPhen layer between the CsCl and the active layer. For such cells with CsI (PCE ∼3.3–3.4%) the increase was only 6–9%, to 3.5–3.7%. The PCE of cells devoid of the halides but with BPhen was ∼3.3%. The cells were optimized by varying the BPhen concentration in a chlorobenzene solution. The results are consistent with reduced charge recombination at the ITO interface in the presence of the hole blocking BPhen interlayer. The use of hole blocking BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), as a substitute for BPhen, also showed an enhancement (though lower due to its lower electron mobility), verifying the effect of these materials as hole blocking interlayers. Interestingly, the stability of such non-encapsulated devices with CsCl/BPhen or CsI/BPhen improved significantly. For example, the PCE of unencapsulated cells with CsCl/BPhen kept in the dark under ambient conditions dropped by less than 2% after more than 3 weeks; the PCE of similar cells devoid of the BPhen layer dropped by ∼60% during the same period. The PCE of the cell with CsCl/BPhen dropped by ∼16% after 2 months. High humidity, as expected, resulted in faster deterioration in cell performance. The PCE, however, was restored to within ∼10% of the original value for 2 week old cells by solution–application of a PSB layer on the blank side of the cell’s glass substrate. These beads direct and scatter the light to enhance absorption in the active layer. The results demonstrate that a simple approach such as casting a film of ∼100 nm diameter PSB from an aqueous suspension on the blank side of the OSC substrate can improve long-term performance, and that spin coating BPhen is a low-cost and easy approach to reduce charge recombination at the cathode in inverted structures for increased PCE and stability.     

Solution-processed annealing-free ZnO nanoparticles for stable inverted organic solar cells

We report the development and application of high-quality zinc oxide nanoparticles (ZnO NPs) processed in air for stable inverted bulk heterojunction solar cells as an electron extraction layer (EEL). The ZnO NPs (average size ∼11 nm) were dispersed in chloroform and stabilized by propylamine (PA). We demonstrated that the ZnO NP dispersion with 4 vol.% of PA as stabilizer can be used in air directly and remains clear up to one month after preparation. Our inverted solar cells consisted of a blade-coated poly(N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole (PCDTBT) and [6,6]-phenyl C₇₁-butyric acid methyl ester (PC₇₁BM) (1: 4 by weight) active layer sandwiched between a ZnO electron extraction layer and a MoO₃/Ag anode. All solar cells with ZnO films fabricated in air using PA-stabilized ZnO dispersions prepared within a time window of one month exhibited power conversion efficiencies (PCE) above 4%. In contrast, if the ZnO film was prepared in air using regular un-stabilized ZnO NP dispersion, the PCE would drop to 0.2% due to poor film quality. More interestingly, X-ray photoelectron spectroscopy and nuclear magnetic resonance measurements indicated that the PA ligands were not covalently bonded to ZnO NPs and did not exist in the deposited ZnO films. The spin-cast ZnO thin films (without any thermal treatment) are insoluble in organic solvents and can be directly used as an EEL in solar cells. This feature is beneficial for fabricating organic solar cells on flexible polymer substrates. More importantly, our non-encapsulated inverted solar cells are highly stable with their PCEs remaining unchanged after being stored in air for 50 days.     

Cathodic multilayer transparent electrodes for ITO-free inverted organic solar cells

We demonstrate cathodic multilayer transparent electrodes based on a ZnS/Ag/TiO_x (ZAT) structure for ITO-free inverted organic solar cells. A quality solution-based TiO_x layer is adopted as an inner dielectric layer to modify the effective work function of Ag, ensuring the ZAT electrode works as a cathode. The effect of the TiO_x layer is seen on the open-circuit voltage of a solar cell incorporating this layer, increasing to 900 mV from 600 mV in the case of a cell with a bare Ag layer for a bulk-heterojunction of poly[N-9″-hepta-decanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) and [6,6]-phenyl C₇₀-butyric acid methyl ester (PCBM70). The results of a joint theoretical and experimental study indicate that the photocurrent of a ZAT-based solar cell can be significantly enhanced by carefully balancing the optical-spacer and cavity-resonance effects, both of which are modulated by the thickness of the WO₃ layer used as a hole-collection layer at the top anode side. ZAT-based inverted solar cells with an optimized structure exhibit a power conversion efficiency as high as 5.1%, which is comparable to that of the ITO-based equivalent.     

Stability of diketopyrrolopyrrole small-molecule inverted organic solar cells

Small-molecule DPP(TBFu)₂-based inverted organic solar cells were fabricated and their stability investigated. The effects of thermal annealing and solvent annealing on device performance and stability were compared. To increase the stability, mix-PCBM (PC₆₁BM and its C₇₀ analogue), which is reported to give higher device stability, was also included. Solvent-annealed devices showed the highest power conversion efficiency (PCE) of 4.62%, whereas thermally annealed devices showed a PCE of 3.94%. After the aging process, which involved thermal stress and exposure to air, thermally annealed and mix-PCBM devices retained a PCE of 3%, whereas solvent-annealed devices had a much lower PCE of 1.7%. Therefore, our results show that in the long-term stability perspective, thermal annealing is better than solvent annealing, and mix-PCBM is better than PC₆₁BM in the case of DPP(TBFu)₂. We fabricated small-molecule inverted organic solar cells that retain their performance in air for 3 weeks without encapsulation.     

Properties of inverted polymer solar cells based on novel small molecular electrolytes as the cathode buffer layer

Novel small-molecule electrolytes were designed and synthesized for use in the cathode interlayer in bulk-heterojunction polymer solar cells (PSCs). The synthesized materials consist of polar quaternary ammonium bromide with the addition of multiple hydroxyl groups, which are N,N,N,N,N,N-hexakis(2-hydroxyethyl)butane-1,4-diaminium bromide (C4) and N,N,N,N,N,N-hexakis(2-hydroxyethyl)hexane-1,6-diaminium bromide (C6). The materials generate a favorable interface dipole through the quaternary ammonium bromide. In addition, the multiple polar hydroxyl groups increased the interface dipole magnitude. The power conversion efficiency of the devices with the interlayer was up to 9.20% with a J_sc of 17.22 mA/cm², a V_oc of 0.75 V, and an FF of 71.3%. The PCE of devices with an interlayer show better long-term stability than a device without an interlayer. Our strategy shows that it is possible to enhance the efficiency of PSCs by simple approaches without complicated syntheses.     

Efficient inverted polymer solar cells incorporating doped organic electron transporting layer

An efficient inverted polymer solar cell is enabled by incorporating an n-type doped wide-gap organic electron transporting layer (ETL) between the indium tin oxide cathode and the photoactive layer for electron extraction. The ETL is formed by a thermal-deposited cesium carbonate-doped 4,7-diphenyl-1,10-phenanthroline (Cs₂CO₃:BPhen) layer. The cell response parameters critically depended on the doping concentration and film thickness of the Cs₂CO₃:BPhen ETL. Inverted polymer solar cell with an optimized Cs₂CO₃:BPhen ETL exhibits a power conversion efficiency of 4.12% as compared to 1.34% for the device with a pristine BPhen ETL. The enhanced performance in the inverted device is associated with the favorable energy level alignment between Cs₂CO₃:BPhen and the electron-acceptor material, as well as increased conductivity in the doped organic ETL for electron extraction. The method reported here provides a facile approach to optimize the performance of inverted polymer solar cells in terms of easy control of film morphology, chemical composition, conductivity at low processing temperature, as well as compatibility with fabrication on flexible substrates.     

晶体硅表面纳米孔减反光结构的制备及其性能表征

利用金属辅助硅化学刻蚀法在晶体硅表面制备 了 大面积有序硅纳米结构,并基于金属辅助硅化学刻蚀的机理,实现了硅纳米结构从线阵列到 孔阵列转变。漫反射光谱的测试结果表 明,相对于平面、金字塔结构,硅纳米孔织构的晶体硅具有卓越的减反光性能,在300100nm 光谱范围内的AM1.5G太阳光子的光反射损失比低于3.6%。硅纳米孔阵列减反光性能优异, 制备方法简单、快速,且其孔壁互连,有益于晶体硅太阳电池的后续制备工艺及其表面结构 机械稳定,可作为减反光结构应用于晶体硅太阳电池。     

Progress towards fully spray-coated semitransparent inverted organic solar cells with a silver nanowire electrode

We demonstrated a fully spray-coated semitransparent organic solar cell, from the lowermost organic layer to the uppermost top electrode. The fabricated devices based on a poly (3-hexylthiophene):[6,6]-phenyl-C61 butyric acid methyl ester (P3HT:PCBM) are semitransparent (∼70% transparency at long wavelength beyond 650 nm), fully spray-coated from organic layer to top electrode, highly efficient (∼80% of that of a device with a conventional metal electrode).     

Efficient and stable inverted polymer solar cells using TiO2 nanoparticles and analysized by Mott-Schottky capacitance

The performance of both inverted and conventional polymer solar cells (PSCs) were examined with a low-temperature, solution-processed synthesized TiO₂ nanoparticles (TiO₂ NPs) as the electron extraction layer. The performance of inverted PSCs based on P3HT:PCBM bulk-heterojunction with a TiO₂ NPs layer was dramatically improved and the highest power conversion efficiency (PCE) of 4.56% was achieved via 24 h exposure in air, which is one of the highest PCEs for P3HT:PCBM bulk-heterojunction PSCs using TiO₂ as electron extraction layer. Meanwhile, the performance of inverted PSCs was superior to regular PSCs. Mott-Schottky capacitance analysis was carried out for both inverted and regular PSCs to obtain the built-in potential, the depletion width, as well as the doping level of the active layer, which all support the performance improvement of PSCs devices with inverted structure. In addition, inverted PSCs show excellent stability in air without encapsulation. The PCE can retain 87% of its original values after 400 h exposure in air, which is much better than that of regular PSCs. The results indicate that solution-processed TiO₂ NPs shows great potential applications in the fabrication of highly efficient and stable inverted PSCs as well as large-area, flexible printed PSCs.     

Polyacetylene-based polyelectrolyte as a universal interfacial layer for efficient inverted polymer solar cells

Here we report that poly(N-dodecyl-2-ethynylpyridiniumbromide) (PDEPB) interlayers between electron-collecting zinc oxide (ZnO) layers and bulk heterojunction (BHJ) layers act as a universal interfacial layer for improving the performances of inverted-type polymer:fullerene solar cells. Three different BHJ layers, poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM), poly[(4,8-bis(2-ethylhexyloxy)-benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-alt-(N-2-ethylhexylthieno[3,4-c]pyrrole-4,6-dione)-2,6-diyl]] (PBDTTPD):PC₆₁BM, and 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) and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM), were employed so as to prove the role of the PDEPB interlayers. Results showed that the power conversion efficiency (PCE) of polymer:fullerene solar cells with the three different BHJ layers increased in the presence of the PDEPB interlayers prepared from 0.5 mg/ml solutions. The improved PCE was attributed to the conformal coating of the PDEPB layers on the ZnO layers (by atomic force microscopy measurement), lowered work functions of ZnO induced by the PDEPB layers (by Kelvin probe measurement), and reduced interface resistance (by impedance spectroscopy measurement), as supported by the noticeable change in the atom environments of both the ZnO and PDEPB layers (by X-ray photoelectron spectroscopy measurement).     

Surfactant assisted electrochemical growth of ultra-thin CuSCN nanowires for inverted perovskite solar cell applications

In this report, a simple surfactant-assisted electrodeposition method is developed to obtain ultra-thin CuSCN nanowires with controlled thickness and diameter. The morphology and thickness of the CuSCN nanowires are controlled by changing the electrochemical potential and deposition time. The phase pure β-CuSCN is confirmed from XRD and Raman analysis. The packing fraction and diameter of the CuSCN nanowires are confirmed using FESEM micrographs. The formation of tetragonal shaped ultra-thin CuSCN nanowire is observed at 3 min deposition time for all the applied potentials. The chemical composition and oxidation state of the grown CuSCN nanowires are confirmed from XPS spectra. The maximum short circuit current of 21.09 mA/cm² and power conversion efficiency of 16.99% is achieved for the thickness of 186 nm and packing fraction of 3067 nanowires/μm². The low hysteresis and high charge transfer nature of the CuSCN nanowire boost the device efficiency more than 60% comparing with CuSCN nanowire grown at short deposition time and low applied potential. The large-area (0.75 cm²) device showed excellent stability up to 1400 h with CuSCN nanowires and carbon back contact. It is observed that the packing fraction and thickness of the CuSCN nanowire significantly influences the photovoltaic performance of the device. The present investigation provides a pathway for the application of CuSCN nanowire and carbon back contacts for efficient large-area solar cell fabrication.     

Efficiency-limiting defects in silicon solar cell material

The precipitation rate of intentionally introduced iron during low-temperature heating is studied among a variety of single-crystal and polycrystalline silicon solar cell materials. A correlation exists between the iron precipitation rate and the carrier recombination rate in dislocation-free as-grown material, suggesting that diffusion-length-limiting defects in as-grown material are structural defects which accelerate iron precipitation. Phosphorous diffusion gettering was found to be particularly ineffective at improving diffusion length after intentional iron contamination in materials with high iron precipitation rates. We propose that intragranular structural defects in solar cell silicon greatly enhance transition metal precipitation during cooling from the melt and become highly recombination-active when decorated with these impurities. The defects then greatly impair diffusion length improvement during phosphorus gettering and limit carrier lifetimes in as-grown material.     

Enhanced photovoltaic performance in inverted polymer solar cells using Li ion doped ZnO cathode buffer layer

We have proposed an approach to improve the photovoltaic performance of inverted polymer solar cells (i-PSC) using lithium ion doped ZnO (LiZnO) as cathode buffer layer (CBL). The LiZnO CBL was prepared using the diffusion technique, performed by inducing the Li ion of 8-hydroxyquinolatolithium (Liq) to diffuse into ZnO film through annealing the bi-layer ZnO/Liq film. Doping concentration of Li ion was controlled by using various thickness of Liq film and annealing temperature. Based on LiZnO CBL, the poly (3-hexylthiophene) [6,6]:-phenyl C61-butyric acid methyl ester (P3HT:PCBM) i-PSC device possessed a optimal power conversion efficiency (PCE) of 4.07%, which was 30% improved than that of the device with neat ZnO as CBL. The enhancement of the device performance could be attributed to the enhanced electron mobility and better band matching of the LiZnO CBL. Our finding indicates that the LiZnO film fabricated with relatively low temperature treatment has great potential for high-performance i-PSCs.     

Indium tin oxide-free semi-transparent inverted polymer solar cells using conducting polymer as both bottom and top electrodes

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is investigated as a transparent cathode to replace indium tin oxide (ITO) in inverted polymer solar cells. Increasing the thickness of the PEDOT:PSS electrode leads to a reduction in transparency and sheet resistance which lowers the photocurrent but increases the fill factor of the solar cells. The offset of photocurrent and fill factor as the thickness is increased leads to a saturation of the power conversion efficiency to 3%. These electrodes were applied to flexible substrates showing similar device performance to glass based devices. Cyclic bending test of these flexible polymer electrodes show improved conversion efficiency retention (92%) when compared to flexible ITO based electrodes (50%) after 300 bend cycles. In addition to using PEDOT:PSS as a cathode replacement for ITO in inverted solar cells, its use as a semi-transparent anode replacement to Ag is also examined. Semi-transparent inverted solar cells fabricated with ITO as the cathode and PEDOT:PSS as the top anode electrode were demonstrated showing efficiencies of 2.51% while replacement of both ITO and Ag with PEDOT:PSS as both the cathode and anode show efficiencies of 0.47%.     

Highly conductive Zinc-Tin-Oxide buffer layer for inverted polymer solar cells

Thin-films of Zinc Tin Oxide (ZTO) with an extremely high charge carrier mobility and superior optical transmittance are synthesized using a simple solution method. These ZTO films have been systematically studied for the application in inverted polymer solar cells (PSCs). The Hall effects measurements show that the charge mobility of the ZTO semiconductor is over 16.5 cm².V⁻¹.S⁻¹, which is the highest mobility value ever reported for oxide buffer made by using solution process. By applying the ZTO buffer layer in the inverted PSCs of P3HT:PC₆₁BM, the power conversion efficiency of the device is 30% higher than that of the devices made with other common buffer layers such as ZnO and TiO₂. Light intensity-dependent JV studies and PL measurements also indicate that ZTO buffer layer reduces surface recombination. This work demonstrates that the solution-synthesized ZTO is a promising new buffer layer with superior electron extraction capability for the solar cells.     

非晶硅太阳电池的衰减与退火

讨论了影响非晶硅太阳电池稳定性的因素,介绍了改善非晶硅材料稳定性的方法,进行了非晶硅太阳电池光致衰减测试.描述了电流注入退火和热退火对非晶硅太阳电池性能的改善.     

A new alcohol-soluble electron-transporting molecule for efficient inverted polymer solar cells

A new electron-transporting material 4,7-diphenyl-1,10-phenanthroline-2,9-dicarboxylic acid (DPPA) was synthesized by modifying a n-type small molecule bathocuproine (BCP). The introduced carboxyl groups make DPPA soluble in polar solvent and compatible with large-scale solution-processing techniques. The anchoring of carboxyl on ZnO (or ITO) substrates helps to form a DPPA electron transporting layer, building an improved interfacial contact between the substrate and active layer. Furthermore, the highest occupied molecular orbital level of DPPA shifts to ?6.45 eV, which is 0.38 eV deeper than that of BCP, suggesting enhanced hole-blocking. Inverted polymer solar cells using P3HT:PCBM blend as the active layer and DPPA modified ZnO as the electron transporting layer were fabricated. A power conversion efficiency (PCE) of 3.55% was obtained, which is about 10% higher than that of the conventional ZnO buffered devices (3.25%). The DPPA was also used to replace ZnO as the sole electron-extracting layer, resulting in an improved PCE of 3.46%, which indicates that DPPA-ETL/ITO forms a better cathode than conventional ZnO/ITO.     

Improved performance of inverted polymer solar cells by utilizing alcohol-soluble oligofluorenes as efficient cathode interlayers

Two star-shaped oligofluorenes with hexakis(fluoren-2-yl)benzene as core are designed and synthesized, namely Tn0 and Tn1. Diethylamino groups are attached to the side chain of fluorene units of Tn0 and Tn1 and enable them alcohol solubility, additional hydrophobic nhexyl chains are grafted on the π-extended fluorene arms of Tn1. Power conversion efficiency (PCE) as high as 8.62% and 8.80% are achieved when utilizing Tn0 and Tn1 as cathode interlayers in inverted polymer solar cells, respectively. The work function of ITO effectively decreased by introducing interlayer, resulting in high Voc of the device, besides, the wetting properties of the interlayers can be tuned by modifying the oligofluorenes with π-extended structure, and the more hydrophobic interlayer will benefit the device performance with enhanced Jsc and FF.     

倒金字塔结构的黑硅PIN光电探测器的研究

由于晶体硅间接带隙的本质,光的吸收系数较低 ,影响了硅基光电探测器的量子效率。倒金字塔结构被证明是能够使得单晶硅片的光吸收效 率接近Yablonovitch limit的有效陷光结构。本论文采用金属催化腐蚀技术在单晶硅上制备具有随机分布的 倒金字塔陷光结构,并将其应用 到PIN光电探测器。结果显示具有倒金字塔结构的黑 硅PIN光电探测器加权平均反射率从20.18%降低至4.77%,探测器的漏电流仅0.9 nA, 光谱响应度达到0.64 A/W,较常规硅探测器提高33%。这些结果表明金属催化腐蚀技 术形成的倒金字塔结果能有效降低器件的表面反射率,从而提高探测器的光谱响应度。