PbS colloidal quantum dot/ZnO‐based bulk‐heterojunction solar cells with high stability under continuous light soaking

PbS colloidal quantum dot (CQD)‐based depleted bulk‐heterojunction solar cells were constructed, using the 1.2 μm thick nanowire array infiltrated with PbS QDs bearing Br ligands. The long‐term stability tests were performed on the solar cells without encapsulation in air under continuous light soaking using a Xe lamp with an AM1.5G filter (100 mW cm^?2). Time course of solar cell performances during the tests showed two time periods with distinct behavior, that is, the initial transient time period and the relatively stable region following it. The power conversion efficiency was found to keep approximately 90% of the initial value at the end of the 3000 h light soaking test. The stability tests suggest that the PbS surface modification or passivation reactions play an important role in achieving such a high stability, and demonstrate that PbS CQD/ZnO nanowire array‐based depleted bulk‐heterojunction solar cells are highly stable. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Increased open‐circuit voltage of ZnO nanowire/PbS quantum dot bulk heterojunction solar cells with solution‐deposited Mg(OH)2 interlayer

An ultrathin Mg(OH)₂ layer was solution‐deposited onto the ZnO nanowires to solve the problem of interfacial charge recombination, caused by the increase of interfacial area in bulk heterojunction (BHJ) PbS colloidal quantum dot solar cells (CQDSCs). This Mg(OH)₂ interlayer efficiently passivated the surface defects of ZnO nanowires and provided tunnel barrier at ZnO/PbS interface. As a result, the charge recombination at ZnO/PbS interface was largely suppressed, proved by the significantly elongated electron lifetime and the increased open‐circuit voltage of the Mg(OH)₂‐involved BHJ CQDSCs. Careful thickness optimization of Mg(OH)₂ interlayer finally brought a ～33% increase in V_oc and ～25% improvement in power conversion efficiency.     

Hybrid photoanode films based on sparse ZnO rod array-TiO2 nanoparticles in dye-sensitized solar cells

ZnO-TiO2 hybrid photoanodes were fabricated via the doctor-blade method by integrating vertically-grown sparse ZnO arrays with hydrothermal TiO2 nanoparticles. A special surface-coating technique was developed to deposit a thin TiO2 layer on the surface of ZnO rods. Microstructure, optical and photoelectrochemical performance of the hybrid photoanodes were investigated. The denser ZnO array exhibited bad filling behavior of nanoparticles in the interspace of ZnO rods, strong scattering and low conversion efficiency (0.27%). The sparser array showed a much better integrated microstructure, improved transmittance and high conversion efficiency (2.68%). The surface modification of ZnO rods by the TiO2 thin layer was found useful in improving the interfacial microstructure between the ZnO rod and the TiO2 bulk film, and the total conversion efficiency of 3.01% was achieved, higher than that of the pure TiO2 nanoparticle cell (2.93%). The increased scattering effects on the incident light, the enhanced electron transportation at TiO2/dye/electrolyte interface, and the inhabited recombination were responsible for this improvement.     

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.     

表面配体和器件结构对PbS胶体量子点电池性能的影响

利用吸收光谱、傅里叶变换红外光谱和循环伏安等表征技术,分析了利用四丁基碘化铵(TBAI)和1,2-乙二硫醇(EDT)配体钝化处理的PbS胶体量子点的光学性质、表面化学及其能级结构,并在此基础上分别以PbS-TBAI薄膜、PbS-EDT薄膜和PbS-TBAI/PbS-EDT薄膜作为有源层制备了PbS胶体量子点/Zn O纳米粒子异质结太阳能电池,以比较研究表面配体和器件结构对器件光伏性能及其稳定性的影响。结果表明,TBAI和EDT均能与PbS胶体量子点表面原有的油酸配体实现良好置换,但是配体置换之后量子点表面均残留少量油酸分子; PbS-TBAI薄膜的导带底为-5.12 eV,价带顶为-3. 86 eV,而PbS-EDT薄膜的导带底为-4. 99 eV,价带顶为-3. 74 eV,后者相对前者出现了明显的能带上移; PbS-TBAI/PbS-EDT双配体器件的光伏性能最优,能量转化效率达到4. 43%;随着空气暴露时间的增加,PbS-TBAI/PbS-EDT双配体器件和PbS-TBAI单配体器件表现出相似的性能变化趋势,于3 d后达到最优光伏性能,而PbS-EDT单配体器件的空气稳定性差,3 d后的能量转换效率下降至初始效率的1/4。本工作的研究结果将不仅有助于加深对PbS胶体量子点电池性能变化规律的认识,而且有望促进该类电池制备技术的进一步优化。     

Electrochemical properties of TiO2 nanoparticle/nanorod composite photoanode for dye-sensitized solar cells

A unique composite of TiO₂ nanoparticles (NPs) and nanorods (NRs) has been used to fabricate a photoelectrode for developing dye-sensitized solar cells (DSSCs) with higher sensitivity. The TiO₂ nanorods were synthesized using a mechanical process, in which electrospun TiO₂ nanofibers was grinded in a controlled way to obtain uniform size distribution. The characteristics of electron transport, recombination lifetime and charge collection were investigated by intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS). Photoelectrodes prepared with the composites of NRs and NPs showed significant improvements in electron transportation compared to only NP photoelectrodes, which would enhance the photovoltaic performance of DSSCs. IMPS and IMVS measurements show that fast electron transport and slightly decreased recombination lifetime resulted in the improvement of efficiency. The highest energy conversion efficiency obtained from the photoelectrodes fabricated with the as-prepared rutile TiO₂ nanofibers at 5 wt% NR content was up to 6.1% under AM1.5G solar illumination. The results demonstrate that the composite nanostructure can take advantage of both the fast electron transport of the nanorods and the high surface area of the nanoparticles.     

Light Trapping and Down‐Shifting Effect of Periodically Nanopatterned Si‐Quantum‐Dot‐Based Structures for Enhanced Photovoltaic Properties

Periodically nanopatterned Si structures have been prepared by using a nanosphere lithography technique. The formed nanopatterned structures exhibit good anti‐reflection and enhanced optical absorption characteristics. The mean surface reflectance weighted by AM1.5 solar spectrum (300–1200 nm) is as low as 5%. By depositing Si quantum dot/SiO₂ multilayers (MLs) on the nanopatterned Si substrate, the optical absorption is higher than 90%, which is significantly improved compared with the same multilayers deposited on flat Si substrate. Furthermore, the prototype n‐Si/Si quantum dot/SiO₂ MLs/p‐Si heterojunction solar cells has been fabricated, and it is found that the external quantum efficiency is obviously enhanced for nanopatterned cell in a wide spectral range compared with the flat cell. The corresponding short‐circuit current density is increased from 25.5 mA cm^?2 for flat cell to 29.0 mA cm^?2 for nano‐patterned one. The improvement of cell performance can be attributed both to the reduced light loss and the down‐shifting effect of Si quantum dots/SiO₂ MLs by forming periodically nanopatterned structures.     

Hybrid silver nanoparticle and transparent conductive oxide structure for silicon solar cell applications

Transparent conductive oxides (TCOs) have been widely used as electrodes for various solar cell structures. For heterojunction silicon wafer solar cells, the front TCO layer not only serves as a top electrode (by enhancing the lateral conductance of the underlying amorphous silicon film), but also as an antireflection coating. These requirements make it difficult to simultaneously achieve excellent conductance and transparency, and thus, only high‐quality indium tin oxide (ITO) has as yet found its way into industrial heterojunction silicon wafer solar cells. In this Letter, we present a cost‐effective hybrid structure consisting of a TCO layer and a silver nano‐particle mesh. This structure enables the separate optimization of the electrical and optical requirements. The silver nanoparticle mesh provides high electrical conductance, while the TCO material is optimized as an antireflection coating. Therefore, this structure allows the use of cost‐effective (and less conductive) TCO materials, such as aluminium‐doped zinc oxide. The performance of the hybrid structure is demonstrated to achieve a similar visible transmission (～86% in the 380–780 nm range) as an 80 nm thick ITO layer, but with 10 times better lateral conductance. The presented hybrid structure thus seems well suited for a variety of photovoltaic devices. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Evidence of two‐photon absorption in strain‐free quantum dot GaAs/AlGaAs solar cells

We report the fabrication procedure and the characterization of an Al_0.3Ga_0.7As solar cell containing high‐density GaAs strain‐free quantum dots grown by droplet epitaxy. The production of photocurrent when two sub‐bandgap energy photons are absorbed simultaneously is demonstrated. The high quality of the quantum dot/barrier pair, allowed by the high quality of nanostructured strain‐free materials, opens new opportunities for quantum dot based solar cells.

     

Improved exciton dissociation efficiency by a carbon-quantum-dot doped workfunction modifying layer in polymer solar cells

In addition to the phase-separated morphology of donor and acceptor, the internal field created by work-function difference between cathode and anode can also influence the exciton dissociation probability. In this study, we have demonstrated enhanced photovoltaic performance by increasing exciton dissociation efficiency. To improve both work-function modification effect and charge transport properties, we have incorporated novel carbon quantum dots (CQD) having NH₂ ligands into the polyethyleneimine (PEI) work-function modifying layer as a dopant. A study of net photocurrent density as a function of effective voltage showed that devices with a CQD-doped PEI layer had a much higher charge separation probability compared to devices with a pristine PEI layer. A Kelvin-probe force microscopy study demonstrated that a CQD-doped PEI layer induced lower work-function of ITO than that of ITO with a pristine PEI, which induced a stronger internal field. This strengthened internal field induced better exciton dissociation efficiency, thereby improving solar cell performance.     

制膜工艺对聚合物太阳电池性能影响的研究

用渡越时间法（TOF）分别测试了采用旋涂和滴涂方法制备的poly［2-methoxy-5-（2′-ethylhexyloxy）-1,4- phenylenevinylene］（MEH-PPV）薄膜的空穴迁移率,用原子力显微镜对这两种方法制备的薄膜表面形貌进行了研究.结果表明使用滴涂法有利于聚合物形成有序薄膜结构,能有效提高空穴迁移率.用滴涂法制备的基于MEH-PPV：phenyl C61- butyric acid methyl ester（PCBM）共混薄膜的太阳电池,对比用旋涂法制备的太阳电池,其能量 关键词： 太阳电池 聚合物 迁移率     

A high efficiency 3D photovoltaic microwire with carbon nanotubes (CNT)‐quantum dot (QD) hybrid interface

An innovative hybrid QD sensitized photovoltaic carbon nanotubes microyarn has been developed using thermally‐stable and highly conductive carbon nanotubes yarns (CNYs). These CNYs are highly inter‐aligned, ultrastrong and flexible with excellent electrical conductivity, mechanical integrity and catalytic properties. The CNYs are coated with a QD‐incorporated TiO₂ microfilm and intertwined with a second set of CNYs as a counter electrode (CE). The maximum photon to current conversion efficiency (η_AM1.5) achieved with prolonged‐time stability was 5.93%. These cells are capable of efficiently harvesting incident photons regardless of direction and generating photocurrents with high efficiency and operational stability.

     

ZnO/Ag/ZnO multilayer transparent electrode for highly-efficient ITO-Free polymer solar cells

Ultrathin metal film (UTMF) with a ZnO/Ag/ZnO hybrid structure was used as transparent electrode in a high-efficiency bulk heterojunction system for the fabrication of ITO-free polymer solar cells. The performance of the devices was carefully tuned through optical simulation using transfer matrix method by varying the thickness of ZnO seed layer and thin absorber layer. By employing appropriate device architecture, polymer solar cells fabricated using this UTMF-based electrode show efficiency as high as 9.49%, which is slightly higher compared to that of ITO-based device. From good agreement between the external quantum efficiency and optical modeling, it was found that the optimized microcavity configuration formed in UTMF-based device can greatly enhance the absorbance of the BHJ layer at longer wavelength as well as the favored exciton distribution for better charge transport and collection.     

Photoconductivity as loss mechanism in organic solar cells

We observe that the reverse current under illumination in solar cells containing C₆₀ and ZnPc is dominated by a photoshunt. This shunt, not present in the dark, causes a linear current–voltage relation under illumination showing no saturation. Although observable in bulk heterojunctions, this effect is more pronounced in the presence of a pristine C₆₀ layer. An internal quantum efficiency larger than unity under an applied negative voltage and in the spectral range where C₆₀ absorbs identifies charges which are injected in addition to those photogenerated. The photoshunt is also present in the power‐generating region and represents a loss mechanism limiting the fill factor in particular for flat heterojunction devices. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Morphology controlled open circuit voltage in polymer solar cells

We report a strong dependence of open circuit voltage on the altered morphology of block copolymer (P3HT‐b ‐PPerAcr) based solar cells. The open circuit voltage increases dramatically by about 300 mV by increasing the amount of acceptor homopolymer within the block copolymer/homopolymer blends. The change in open circuit voltage is found to be in correlation with the enrichment of acceptor moiety at the film surface as identified by Atomic force microscopy (AFM) and X‐ray photoelectron spectroscopy (XPS). Based on this fact, an additional increase in open circuit voltage to its maximum values is achieved by introducing an acceptor buffer layer at the cathode interface. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of interface modification on the performance of polymer/Bi2S3 nanorods bulk heterojunction solar cells

In this paper, bulk heterojunction photovoltaic devices based on the poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV):Bi₂S₃ nanorods hybrid material were present. To optimize the performance of the devices, the interface modification of the hybrid material that has a significant impact on the exciton dissociation efficiency was studied. An improvement in the device performance was achieved by modifying the Bi₂S₃ surface with a thin dye layer. Moreover, modifying the Bi₂S₃ surface with anthracene-9-carboxylic acid can enhance the performance further. Compared with the solar cells with Bi₂S₃ nanorods hybrid with the MDMO-PPV as the active layer, the anthracene-9-carboxylic acid modified devices are better in performance, with the power conversion efficiency higher by about one order in magnitude.     

Al纳米颗粒增强微晶硅薄膜太阳电池光吸收的模拟研究

利用价格低廉、性能优良的金属纳米颗粒增强太阳电池的光吸收具有广阔的应用前景. 通过建立三维数值模型, 模拟了微晶硅薄膜电池前表面周期性分布的Al纳米颗粒阵列对电池光吸收的影响, 并对其结构参数进行了优化. 模拟结果表明: 对于球状Al纳米颗粒阵列, 影响电池光吸收的关键参数是周期P与半径R的比值, 或者说是颗粒的表面覆盖度; 当P/R=4–5时, 总的光吸收较参考电池提高可达20%. 与球状颗粒相比, 优化后的半球状Al纳米颗粒阵列可获得更好的陷光效果, 但后者对颗粒半径R的变化较敏感. 另外, 结合电场分布, 对电池光吸收增强的物理机理进行了分析.     

MoO3/Ag/Al/ZnO intermediate layer for inverted tandem polymer solar cells

We report an MoO3/Ag/Al/ZnO intermediate layer connecting two identical bulk heterojunction subcells with a poly(3-hexylthiophene) and [6,6]-phenyl-C61-butyric acid methyl ester(P3HT and PCBM) active layer for inverted tandem polymer solar cells. The highly transparent intermediate layer with an optimized thickness realizes an Ohmic contact between the two subcells for effective charge extraction and recombination. A maximum power conversion efficiency of 3.76% is obtained for the tandem cell under 100 mW/cm2 illumination, which is larger than that of a single cell(3.15%).The open-circuit voltage of the tandem cell(1.18 V) approaches double that of the single cell(0.61 V).     

MoO3/Ag/AI/ZnO intermediate layer for inverted tandem polymer solar cells

We report an MoO3/Ag/Al/ZnO intermediate layer connecting two identical bulk heterojunction subcells with a poly（3-hexylthiophene） and [6,6]-phenyl-C61-butyric acid methyl ester （P3HT and PCBM） active layer for inverted tan- dem polymer solar cells. The highly transparent intermediate layer with an optimized thickness realizes an Ohmic contact between the two subcells for effective charge extraction and recombination. A maximum power conversion efficiency of 3.76% is obtained for the tandem cell under 100 mW/cm2 illumination, which is larger than that of a single cell （3.15%）. The open-circuit voltage of the tandem cell （1.18 V） approaches double that of the single cell （0.61 V）.