Molecular design of interfacial layers based on conjugated polythiophenes for polymer and hybrid solar cells

In the past two decades, bulk heterojunction organic photovoltaic (OPV) devices have emerged as attractive candidates for solar energy conversion due to their lightweight design and potential for low‐cost, high‐throughput, solution‐phase processability. Interfacial engineering is a proven efficient approach to achieve OPV devices with high power conversion efficiencies. This mini‐review provides an overview of the key structural considerations necessary when undertaking the molecular design of conjugated polyelectrolytes, for application as interfacial layers (ILs). The different roles of ILs are outlined, together with the advantages and disadvantages of competing classes of IL materials. Particular emphasis is placed on the design and synthesis of water‐soluble polythiophene‐based IL materials and the influence of their structural characteristics on their performance as a promising class of IL material. Finally, the challenges and opportunities for polythiophenes as IL materials for OPV devices and other solution‐processed solar cell technologies (e.g. perovskite solar cells) are discussed. © 2017 Society of Chemical Industry     

Solid‐state dye‐sensitized and bulk heterojunction solar cells using TiO2 and ZnO nanostructures: recent progress and new concepts at the borderline

In the field of photovoltaic energy conversion, hybrid inorganic/organic devices represent promising alternatives to standard photovoltaic systems in terms of exploiting the specific features of both organic semiconductors and inorganic nanomaterials. Two main categories of hybrid solar cells coexist today, both of which make much use of metal oxide nanostructures based on titanium dioxide (TiO₂) and zinc oxide (ZnO) as electron transporters. These metal oxides are cheap to synthesise, are non‐toxic, are biocompatible and have suitable charge transport properties, all these features being necessary to demonstrate highly efficient solar cells at low cost. Historically, the first hybrid approach developed was the dye‐sensitized solar cell (DSSC) concept based on a nanostructured porous metal oxide electrode sensitized by a molecular dye. In particular, solid‐state hybrid DSSCs, which reduce the complexity of cell assembly, demonstrate very promising performance today. The second hybrid approach exploits the bulk heterojunction (BHJ) concept, where conjugated polymer/metal oxide interfaces are used to generate photocurrent. In this context, we review the recent progress and new concepts in the field of hybrid solid‐state DSSC and BHJ solar cells based on TiO₂ and ZnO nanostructures, incorporating dyes and conjugated polymers. We point out the specificities in common hybrid device structures and give an overview on new concepts, which couple and exploit the main advantages of both DSSC and BHJ approaches. In particular, we show that there is a trend of convergence between both DSSC and BHJ approaches into mixed concepts at the borderline which may allow in the near future the development of hybrid devices for competitive photovoltaic energy conversion. Copyright © 2011 Society of Chemical Industry     

Charge carrier recombination in organic solar cells

Solution deposited bulk heterojunction organic solar cells are viewed as one of the most promising alternative energy sources because of their ease of processing and their potential to be produced using large scale techniques such as roll-to-roll, newspaper style, coating. Since organic materials have a relatively low dielectric constant the dissociation of an excited electron–hole pair into free collectable charge carriers is inefficient in many cases. Often the excited electron–hole pairs recombine back to the ground state in a process known as geminate recombination before they ever fully dissociate into free charge carriers. Even after dissociation, free holes and electrons can encounter each other once more and subsequently recombine back to the ground state in a process known as nongeminate recombination. In both cases the incident photon energy is lost and fewer carriers are collected at the electrodes. Hence, charge carrier recombination is one of the key loss mechanisms in organic solar cells. In this review the latest on geminate and nongeminate recombination is discussed.     

Synthesis, Characterization, and Photovoltaic Properties of Soluble TiOPc Derivatives

We have synthesized soluble TiOPc derivatives containing alkoxy groups for use as additives in dye-sensitized solar cells (DSSCs). The DSSC devices containing these TiOPc derivatives exhibited short-circuit current densities of 8.49~10.04 mA/cm² and power conversion efficiencies of 2.73~3.62 % under AM 1.5 illumination and 100 mW/cm² irradiation.     

Strong,conductive carbon nanotube fibers as efficient hole collectors

We present the photovoltaic properties of heterojunctions made from single-walled carbon nanotube (SWNT) fibers and n-type silicon wafers. The use of the opaque SWNT fiber allows photo-generated holes to transport along the axis direction of the fiber. The heterojunction solar cells show conversion efficiencies of up to 3.1% (actual) and 10.6% (nominal) at AM1.5 condition. In addition, the use of strong, environmentally benign carbon nanotube fibers provides excellent structural stability of the photovoltaic devices.     

Low-bandgap poly(4H-cyclopenta[def]phenanthrene) derivatives with 4,7-dithienyl-2,1,3-benzothiadiazole unit for photovoltaic cells

A series of conjugated polymer bearing 4H-cyclopenta[def]phenanthrene (CPP) unit have been synthesized and was evaluated in bulk heterojunction solar cell. The alternating copolymers with CPP unit were incorporated with 4,7-dithienyl-2,1,3-benzothiadiazole (DTBT) unit by Suzuki conditions. The newly synthesized copolymers, poly(2,6-((4,4-bis(2-ethylhexyl)-4H-cyclopenta[def]phenanthrene))-alt-(4,7-((2-thienyl)-2,1,3-benzothiadiazole))) (PCPP-DTBT), and poly(2,6-(4,4-bis(4-((2-ethylhexyl)oxy)phenyl)-4H-cyclopenta[def]phenanthrene)-alt-(4,7-((2-thienyl)-2,1,3-benzothiadiazole))) (PBEHPCPP-DTBT), contain dialkyl and bis(alkoxyphenyl) groups in the CPP unit, respectively. The HOMO-LUMO energy bandgaps of these materials, estimated from UV-vis spectroscopy and cyclic voltammetry (CV), were 2.00 eV for PCPP-DTBT and 1.80 eV for PBEHPCPP-DTBT. Bulk heterojunction solar cells based on the blends of the polymers with [6,6]phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) gave power conversion efficiencies as 1.00% for PCPP-DTBT and 1.12% for PBEHPCPP-DTBT under AM 1.5, 100 mW/cm².     

Hybrid solar cells from MDMO-PPV and silicon nanocrystals

Solution-processed bulk heterojunction solar cells from silicon nanocrystals (Si NCs) and poly(3-hexylthiophene) (P3HT) have shown promising power conversion efficiencies. Here we report on an attempt to enhance the performance of Si NC-polymer hybrid solar cells by using poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) as a hole conductor, which is expected to yield a higher open circuit voltage than P3HT due to its lower highest occupied molecular orbital (HOMO). Bulk heterojunction solar cells consisting of 3-5 nm silicon nanocrystals (Si NCs) and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) have been fabricated. The properties of the hybrid Si NC/MDMO-PPV devices were studied as a function of the Si NC/MDMO-PPV weight ratio. Cells of 58 wt% 3-5 nm Si NCs showed the best overall performance under simulated one-sun AM 1.5 global illumination (100 mW cm(-2)). Compared to composite films of Si NCs and poly(3-hexylthiophene), we indeed observed an improved open circuit voltage but a lower power conversion efficiency from the Si NC/MDMO-PPV devices. The lower efficiency of Si NC/MDMO-PPV is correlated to the lower hole mobility and narrower absorption spectrum of MDMO-PPV compared to P3HT.     

Investigation of bulk hybrid heterojunction solar cells based on Cu(In,Ga)Se2 nanocrystals

This work presents the systematic studies of bulk hybrid heterojunction solar cells based on Cu(In, Ga)Se₂ (CIGS) nanocrystals (NCs) embedded in poly(3-hexylthiophene) matrix. The CIGS NCs of approximately 17 nm in diameter were homogeneously blended with P3HT layer to form an active layer of a photovoltaic device. The blend ratios of CIGS NCs to P3HT, solvent effects on thin film morphologies, interface between P3HT/CIGS NCs and post-production annealing of devices were investigated, and the best performance of photovoltaic devices was measured under AM 1.5 simulated solar illumination (100 mW/cm²).     

Recent Progress of Innovative Perovskite Hybrid Solar Cells

Recently, innovative perovskite hybrid solar cells have attracted great interest in solar cell research fields, such as dye-sensitized solar cells, organic photovoltaics, thin-film solar cells, and silicon solar cells, because their device efficiencies are gradually approaching those of crystalline Si solar cells, and they can be fabricated by cheap low-temperature solution processes. Here, we review the recent progress of innovative perovskite hybrid solar cells. The introduction includes the general concerns about solar cells and why we need innovative solar cells. The second part explains the structure and the material properties of hybrid perovskite materials. We focus on why the hybrid perovskite materials can exhibit excellent solar cell properties, such as high open-circuit voltage. The third part introduces recent progress in innovative perovskite hybrid solar cells, in terms of device architecture and deposition methods for dense perovskite thin films with full surface coverage. The device architecture is important in attaining high power conversion efficiency; the device operating mechanism is dependent on the device structure; and the pinhole-free dense perovskite thin films with full surface coverage are crucial for achieving high efficiency. Finally, we summarize the recent progress in perovskite hybrid solar cells, and the issues to be solved, in the summary and outlook section.     

Tri-metallic quantum dot under the influence of solvent additive for improved performance of polymer solar cells

CdTeSe colloidal quantum dot (QD) was used to enhance photon capture in thin film polymer solar cells (TFPSC). The QDs were synthesized in aqueous media from two different precursors. Bulk heterojunction (BHJ) polymer blends composed of P3HT and PCBM were used as an absorber layer of the solar cell to investigate the effect of QDs. Different concentrations of QDs were used in the polymer matrix, which significantly impacted the power conversion efficiency (PCE) of the doped devices. More device performance growth was recorded by employing a small amount of solvent additives to disperse the QDs and increase the polymer's crystallinity in the medium. Hence, the addition of 1, Chloronaphthalene (CN) solvent additive in the QD-doped bulk heterojunction film further enhanced the overall performance of the TFPSC due to improved film morphology that has significantly influenced the charge transport processes. Consequently, the PCE of the solar cell increased by nearly 50% compared to the pristine TFPSC due to the effect of solvent additives.     

ZnO/PbS异质结量子点太阳能电池的界面修饰及稳定性研究

对ZnO/PbS异质结量子点太阳能电池的界面修饰及稳定性进行研究,采用ZnO电子传输层掺杂金属Mg及引入电子阻挡层两种界面修饰方法,制备了不同的量子点太阳能电池器件,并对其进行伏安特性测试。结果表明,界面修饰可调整界面能级结构、减少缺陷复合、增强电荷传输。经过界面修饰的器件获得了9.46%的光电转换效率（PCE）,分别比未掺杂的器件（PCE为5.41%）和无电子阻挡层结构的器件（PCE为1.60%）提升了约75%和491%。此外,经过30 d的空气暴露后,界面修饰后的器件仍能保持原有PCE的95%以上。     

Optimization and simplification of polymer–fullerene solar cells through polymer and active layer design

Polymer–fullerene bulk heterojunction (BHJ) solar cells have consistently been at the forefront of the growing field of organic photovoltaics (OPV). The enduring vision of OPV is the promise of combining a simple, low-cost approach with an efficient, flexible, lightweight platform. While efficiencies have improved remarkably over the last decade through advances in device design, mechanistic understanding, and evolving chemical structural motifs, steps forward have often been tied to a loss of simplicity and a deviation from the central vision of OPV. Within the context of active layer optimization, our focus is to target high efficiency while maintaining simplicity in polymer design and active layer processing. To highlight this strategy, this feature article focuses on our work on random poly(3-hexylthiophene) (P3HT) analogs and their application in binary and ternary blend polymer–fullerene solar cells. These random conjugated polymers are conceptually based on combining simple monomers strategically to influence polymer properties as opposed to the synthesis of highly tailored and synthetically complex monomers. The ternary blend approach further exemplifies the focus on device simplicity by targeting efficiencies that are competitive with complex tandem solar cells, but within the confines of a single active-layer processing step. These research directions are described within the broader context of recent progress in the field of polymer–fullerene BHJ solar cells.     

Structure and properties of nano-confined poly(3-hexylthiophene) in nano-array/polymer hybrid ordered-bulk heterojunction solar cells

The ordered-bulk heterojunction (BHJ) photovoltaic device comprising a semiconducting donor polymer incorporated into pristine/unmodified vertically aligned arrays of metal oxide acceptor nanotubes/nanorods is widely perceived as being structurally ideal for energy conversion but the power conversion efficiencies of such devices remain relatively low (in the order of η = 0.6%) when compared with bilayer or non-ordered bulk heterojunction systems. We explain the incongruity by investigating the morphology and microstructure of regio-regular poly(3-hexyl thiophene) (P3HT) infiltrated and confined within the cavities of TiO(2) nanotube arrays. A series of TiO(2) nanotube arrays with different nanotube diameters and inter-nanotube spacings are fabricated by the liquid-phase atomic layer deposition (LALD) technique, and P3HT is infiltrated into the array cavities via a vacuum-annealing technique. X-Ray diffraction studies reveal that the P3HT chains in both nano-confined and non-confined (i.e. planar film) environments are well-aligned and oriented edge-on with respect to the underlying substrate. Up to 2.5-fold improvement in the incident-photon-to-converted-electron efficiency (IPCE) is observed in ordered-BHJ structures over benchmark planar devices which we attribute to the increase in interfacial area resulting from the use of the nanostructures. However, the large effective surface area conferred by the nano-arrays (up to 9.5 times that of the planar system) suggests that much higher efficiencies could be harnessed. Our study shows that the morphology and orientation of the infiltrated polymer play a critical role in the charge transport of the device, and suggests that better understanding and control of polymer morphology under nano-confinement in the nano-array will be the key to fully reaping the promised benefit of ordered-BHJ devices.     

Carbon nanotube incorporation: A new route to improve the performance of organic–inorganic heterojunction solar cells

Incorporation of oxidized camphoric multi-walled carbon nanotubes (MWCNs) in the polymer layer of regioregular poly(3-octylthiophene)/n-Si heterojunction solar cell is observed to improve the performance of the device by many folds. We report power conversion efficiency, open circuit voltage, short-circuit current density, and fill factor of 0.175%, 0.22 V, 2.915 mA/cm², 0.27 respectively, for an un-optimized cell containing MWCNs. Reference cells without MWCNs show much lower performance. Improved device performance is due to better hole transport, easy exciton splitting and suppression of charge carrier recombination as a result of incorporation of MWCNs. MWCNs, being low cost materials, seem to be promising materials for improving device performance of organic–inorganic heterojunction solar cells.     

Ultrathin microcrystalline hydrogenated Si/Ge alloyed tandem solar cells towards full solar spectrum conversion

Thin film solar cells have been proved the next generation photovoltaic devices due to their low cost, less material consumption and easy mass production. Among them, micro-crystalline Si and Ge based thin film solar cells have advantages of high efficiency and ultrathin absorber layers. Yet individual junction devices are limited in photoelectric conversion efficiency because of the restricted solar spectrum range for its specific absorber. In this work, we designed and simulated a multi-junction solar cell with its four sub-cells selectively absorbing the full solar spectrum including the ultraviolet, green, red as well as near infrared range, respectively. By tuning the Ge content, the record efficiency of 24.80% has been realized with the typical quadruple junction structure of a-Si:H/a-Si_0.9Ge_0.1:H/µc-Si:H/µc-Si_0.5Ge_0.5:H. To further reduce the material cost, thickness dependent device performances have been conducted. It can be found that the design of total thickness of 4 mm is the optimal device design in balancing the thickness and the PCE. While the design of ultrathin quadruple junction device with total thickness of 2 mm is the optimized device design regarding cost and long-term stability with a little bit more reduction in PCE. These results indicated that our solar cells combine the advantages of low cost and high stability. Our work may provide a general guidance rule of utilizing the full solar spectrum for developing high efficiency and ultrathin multi-junction solar cells.     

Recent advances in high performance donor-acceptor polymers for organic photovoltaics

Organic photovoltaic cells made with semiconducting polymers remain one of the most promising technologies for low-cost solar energy due to their compatibility with roll-to-roll printing techniques. The development of new light-absorbing polymers has driven tremendous advances in the power conversion efficiency of these devices. In particular, the use of alternating electron rich (donor) and electron poor (acceptor) segments along the polymer backbone can produce low optical bandgap materials that capture more of the solar spectrum. As a result, power conversion efficiencies over 10% are increasingly common for this technology. This review summarizes the recent advances in donor-acceptor polymer design and synthesis, highlighting the structural features that are key to providing high efficiency, scalable and stable devices.     

Organic solar cells based on conjugated polymers : History and recent advances

Organic solar cells have attracted huge attention because of their potential in the low-cost manufacturing of plastic solar modules featuring flexible, lightweight, ultrathin, rollable and bendable shapes. The power conversion efficiency of organic solar cells is now passing ~10%, which is a critical sign toward commercialization because organic solar cells surpass any other types of solar cells in terms of development speed. The encouraging efficiency enhancement could be realized by introducing a ‘bulk heterojunction’ concept that overcomes the weakness of organic semiconductors by minimizing their charge transport paths through making effective p-n junctions inside bulk organic films. However, there are several hurdles for commercialization, including stability and lifetime issues, owing to the bulk heterojunction concept. This review summarizes the important aspects of organic solar cells, particularly focusing on conjugated polymers as an active layer component.     

Fluorinated conjugated polymers in organic bulk heterojunction photovoltaic solar cells

The photovoltaic technology represents a major renewable energy source to harnes the solar power. Over the last two decades, the development of solution-processed bulk heterojunction polymer solar cells has attracted a considerable interest. This has resulted in a significant efficiency improvement through innovation of device architectures and molecular structure design of donor polymers. In this regard, the introduction of fluorinated units along the conjugated backbone has emerged as a successful strategy for further fine-tuning the physical and chemical properties of conducting polymers. In this review, we highlight recent strategies aiming at improving the solar cell performance by variable fluorine substitution of repeating units. Fluorination was found to achieve a modulation of HOMO and LUMO energy levels and optical properties to some extent. Moreover, intermolecular interactions involving fluorine atoms have a significant influence on blend film morphology. The resulting organic photovoltaic solar cells endowed some of the highest power conversion efficiency values reported to date.     

Selenium-Containing π-Conjugated Polymers for Organic Solar Cells

Organic solar cell research has attracted scientific and commercial interest in the last decade due to a rapid increase in power conversion efficiencies (PCEs). Today, PCEs in the range of 8–10 % have been obtained using conjugated polymers as electron-donor materials in combination with fullerene/other acceptors. However, to enable commercial applications, the efficiencies and lifetimes of organic solar cells still need to be improved significantly. In recent years, due to the potential advantages of Se-containing conjugated materials, namely, lower band gaps, rigidity, and strong Se⋅⋅⋅Se integration, have attracted surprising attention for use in organic solar cells. In this review, we focus on the synthesis and applications of Se-containing conjugated polymers for organic solar cells and throughout compare them with S- and O-containing analogues where applicable. The relationships between the chemical structures and properties, such as absorptions, energy levels, mobilities, and photovoltaic behavior, are also discussed.     

Effect of CdSe quantum dots on the performance of hybrid solar cells based on ZnO nanorod arrays

This paper reports the fabrication and interface modification of hybrid inverted solar cells based on ZnO nanorod arrays and poly (3-hexylthiophene). CdSe quantum dots (QDs) are grafted to the ZnO nanorod array successfully by bifunctional molecule mercaptopropionic acid to enhance the device performance. The power conversion efficiency of the device is increased by 109% from 0.11% to 0.23% under simulated 1 sun AM 1.5 solar illumination at 100 mW/cm² after the modification. The grafting of CdSe QDs effectively enhanced the excition generation and dissociation on the organic/inorganic interface. This work may provide a general method for increasing the efficiency of organic–inorganic hybrid solar cells by interface modification.