Plasmonic‐Enhanced Organic Photovoltaics: Breaking the 10% Efficiency Barrier

Recent advances in molecular organic photovoltaics (OPVs) have shown 10% power conversion efficiency (PCE) for single‐junction cells, which put them in direct competition with PVs based on amorphous silicon. Incorporation of plasmonic nanostructures for light trapping in these thin‐film devices offers an attractive solution to realize higher‐efficiency OPVs with PCE?10%. This article reviews recent progress on plasmonic‐enhanced OPV devices using metallic nanoparticles, and one‐dimensional (1D) and two‐dimensional (2D) patterned periodic nanostructures. We discuss the benefits of using various plasmonic nanostructures for broad‐band, polarization‐insensitive and angle‐independent absorption enhancement, and their integration with one or two electrode(s) of an OPV device.     

Progress and Design Concerns of Nanostructured Solar Energy Harvesting Devices

Integrating devices with nanostructures is considered a promising strategy to improve the performance of solar energy harvesting devices such as photovoltaic (PV) devices and photo‐electrochemical (PEC) solar water splitting devices. Extensive efforts have been exerted to improve the power conversion efficiencies (PCE) of such devices by utilizing novel nanostructures to revolutionize device structural designs. The thicknesses of light absorber and material consumption can be substantially reduced because of light trapping with nanostructures. Meanwhile, the utilization of nanostructures can also result in more effective carrier collection by shortening the photogenerated carrier collection path length. Nevertheless, performance optimization of nanostructured solar energy harvesting devices requires a rational design of various aspects of the nanostructures, such as their shape, aspect ratio, periodicity, etc. Without this, the utilization of nanostructures can lead to compromised device performance as the incorporation of these structures can result in defects and additional carrier recombination. The design guidelines of solar energy harvesting devices are summarized, including thin film non‐uniformity on nanostructures, surface recombination, parasitic absorption, and the importance of uniform distribution of photo‐generated carriers. A systematic view of the design concerns will assist better understanding of device physics and benefit the fabrication of high performance devices in the future.     

Light Management in Organic Photovoltaics Processed in Ambient Conditions Using ZnO Nanowire and Antireflection Layer with Nanocone Array

Low carrier mobility and lifetime in semiconductor polymers are some of the main challenges facing the field of organic photovoltaics (OPV) in the quest for efficient devices with high current density. Finding novel strategies such as device structure engineering is a key pathway toward addressing this issue. In this work, the light absorption and carrier collection of OPV devices are improved by employment of ZnO nanowire (NW) arrays with an optimum NW length (50 nm) and antireflection (AR) film with nanocone structure. The optical characterization results show that ZnO NW increases the transmittance of the electron transporting layer as well as the absorption of the polymer blend. Moreover, the as‐deposited polymer blend on the ZnO NW array shows better charge transfer as compared to the planar sample. By employing PC70BM:PV2000 as a promising air‐stable active‐layer, power conversion efficiencies of 9.8% and 10.1% are achieved for NW devices without and with an AR film, indicating 22.5% and 26.2% enhancement in PCE as compared to that of planar device. Moreover, it is shown that the AR film enhances the water‐repellent ability of the OPV device.     

Design of nanostructured solar cells using coupled optical and electrical modeling

Nanostructured light trapping has emerged as a promising route toward improved efficiency in solar cells. We use coupled optical and electrical modeling to guide optimization of such nanostructures. We study thin-film n-i-p a-Si:H devices and demonstrate that nanostructures can be tailored to minimize absorption in the doped a-Si:H, improving carrier collection efficiency. This suggests a method for device optimization in which optical design not only maximizes absorption, but also ensures resulting carriers are efficiently collected.     

Low-indium content bilayer transparent conducting oxide thin films as effective anodes in organic photovoltaic cells

Bilayer In-doped CdO/Sn-doped In₂O₃ (CIO/ITO) transparent conducting oxide (TCO) thin films were prepared by depositing thin ITO films by ion-assisted deposition on CIO films grown by metal-organic chemical vapor deposition. The optical, electrical, and microstructural properties of these bilayer TCO films were investigated in detail. A low sheet resistance of ~ 4.9 Ω/□ is achieved for the CIO/ITO (170/40 nm) bilayers without annealing. With a significantly lower In content (20 vs. ~ 93 at.%) and a much higher conductivity (> 12,000 vs. 3000-5000 S/cm) than commercial ITO, these bilayer films were investigated as anodes in bulk-heterojunction organic photovoltaic (OPV) devices having a poly(2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylenevinylene) + [6,6]-phenyl C₆₁ butyric acid methyl ester active layer. Device performance metrics in every way comparable to those of devices fabricated on commercial ITO are achieved, demonstrating that CIO/ITO bilayers are promising low-In content, highly conductive and transparent electrode candidates for OPV cells.     

Designable Luminescence with Quantum Dot–Silver Plasmon Coupler

We explore a strongly interacting QDs/Ag plasmonic coupling structure that enables multiple approaches to manipulate light emission from QDs. Group II–VI semiconductor QDs with unique surface states (SSs) impressively modify the plasmonic character of the contiguous Ag nanostructures whereby the localized plasmons (LPs) in the Ag nanostructures can effectively extract the non‐radiative SSs of the QDs to radiatively emit via SS–LP resonance. The SS–LP coupling is demonstrated to be readily tunable through surface‐state engineering both during QD synthesis and in the post‐synthesis stage. The combination of surface‐state engineering and band‐tailoring engineering allows us to precisely control the luminescence color of the QDs and enables the realization of white‐light emission with single‐size QDs. Being a versatile metal, the Ag in our optical device functions in multiple ways: as a support for the LPs, for optical reflection, and for electrical conduction. Two application examples of the QDs/Ag plasmon coupler for optical devices are given, an Ag microcavity + plasmon‐coupling structure and a new QD light‐emitting diode. The new QDs/Ag plasmon coupler opens exciting possibilities in developing novel light sources and biomarker detectors.     

Electrical Scanning Probe Microscopy on Active Organic Electronic Devices

Polymer‐ and small‐molecule‐based organic electronic devices are being developed for applications including electroluminescent displays, transistors, and solar cells due to the promise of low‐cost manufacturing. It has become clear that these materials exhibit nanoscale heterogeneities in their optical and electrical properties that affect device performance, and that this nanoscale structure varies as a function of film processing and device‐fabrication conditions. Thus, there is a need for high‐resolution measurements that directly correlate both electronic and optical properties with local film structure in organic semiconductor films. In this article, we highlight the use of electrical scanning probe microscopy techniques, such as conductive atomic force microscopy (c‐AFM), electrostatic force microscopy (EFM), scanning Kelvin probe microscopy (SKPM), and similar variants to elucidate charge injection/extraction, transport, trapping, and generation/recombination in organic devices. We discuss the use of these tools to probe device structures ranging from light‐emitting diodes (LEDs) and thin‐film transistors (TFT), to light‐emitting electrochemical cells (LECs) and organic photovoltaics.     

A UV‐Responsive Multifunctional Photoelectric Device Based on Discotic Columnar Nanostructures and Molecular Motors

Orientation control of ordered materials would not only produce new physical phenomenon but also facilitate the development of fancy devices. Discotic liquid crystals (DLCs) form 1D charge transport pathway by self‐organizing into columnar nanostructures via π–π stacking. However, controlling the electrical properties in such nanostructures with some direct and instant way is a formidable task for their high viscosity and insensitivity to external stimuli. Herein, the arbitrary control over electrical conductivity of such columnar nanostructures is achieved with UV light by incorporating DLCs with molecular motors. Highly ordered DLC microstripe arrays are generated on desired substrate through a capillary bridge dewetting strategy. The conductivity of the microstripes could be continuously modulated by 365 nm light due to the influence of molecular motion under UV irradiation on the electron orbital overlap of columnar nanostructures. This is so because the disorder degree of the DLC molecules is associated with the intensity of UV light and the doping concentration of molecular motors. Moreover, the device shows memory effect and reversible conductivity change. The DLC microstripe arrays are very promising for the applications in UV detectors, memory devices, optical switches, and so on.     

Advances in Solution‐Processed Multijunction Organic Solar Cells

The efficiency of organic solar cells can benefit from multijunction device architectures, in which energy losses are substantially reduced. Herein, recent developments in the field of solution‐processed multijunction organic solar cells are described. Recently, various strategies have been investigated and implemented to improve the performance of these devices. Next to developing new materials and processing methods for the photoactive and interconnecting layers, specific layers or stacks are designed to increase light absorption and improve the photocurrent by utilizing optical interference effects. These activities have resulted in power conversion efficiencies that approach those of modern thin film photovoltaic technologies. Multijunction cells require more elaborate and intricate characterization procedures to establish their efficiency correctly and a critical view on the results and new insights in this matter are discussed. Application of multijunction cells in photoelectrochemical water splitting and upscaling toward a commercial technology is briefly addressed.     

25th Anniversary Article: A Decade of Organic/Polymeric Photovoltaic Research

Organic photovoltaic (OPV) technology has been developed and improved from a fancy concept with less than 1% power conversion efficiency (PCE) to over 10% PCE, particularly through the efforts in the last decade. The significant progress is the result of multidisciplinary research ranging from chemistry, material science, physics, and engineering. These efforts include the design and synthesis of novel compounds, understanding and controlling the film morphology, elucidating the device mechanisms, developing new device architectures, and improving large‐scale manufacture. All of these achievements catalyzed the rapid growth of the OPV technology. This review article takes a retrospective look at the research and development of OPV, and focuses on recent advances of solution‐processed materials and devices during the last decade, particular the polymer version of the materials and devices. The work in this field is exciting and OPV technology is a promising candidate for future thin film solar cells.     

Effects of nanostructured back reflectors on the external quantum efficiency in thin film solar cells

Hydrogenated amorphous Si ( α-Si:H) is a promising material for photovoltaic applications due to its low cost, high abundance, long lifetime, and non-toxicity. We demonstrate a device designed to investigate the effect of nanostructured back reflectors on quantum efficiency in photovoltaic devices. We adopt a superstrate configuration so that we may use conventional industrial light trapping strategies for thin film solar cells as a reference for comparison. We controlled the nanostructure parameters via a wafer-scale self-assembly technique and systematically studied the relation between nanostructure size and photocurrent generation. The gain/loss transition at short wavelengths showed red-shifts with decreasing nanostructure scale. In the infrared region the nanostructured back reflector shows large photocurrent enhancement with a modified feature scale. This device geometry is a useful archetype for investigating absorption enhancement by nanostructures.     

Efficiency enhancement in DIBSQ:PC<Subscript>71</Subscript>BM organic photovoltaic cells by using Liq-doped Bphen as a cathode buffer layer

We have improved the photovoltaic performance of 2,4-bis[4-(N,Ndiisobutylamino)- 2,6-dihydroxyphenyl] squaraine:[6,6]-phenyl C71-butyric acid methyl ester (DIBSQ:PC₇₁BM) organic photovoltaic (OPV) cells via incorporating Liq-doped Bphen (Bphen-Liq) as a cathode buffer layer (CBL). Based on the Bphen-Liq CBL, a DIBSQ:PC₇₁BM OPV cell possessed an optimal power conversion efficiency of 4.90%, which was 13% and 60% higher than those of the devices with neat Bphen as CBL and without CBL, respectively. The enhancement of the device performance could be attributed to the enhanced electron mobility and improved electrode/active layer contact and thus the improved photocurrent extraction by incorporating the Bphen-Liq CBL. Light-intensity dependent device performance analysis indicates that the incorporating of the Bphen-Liq CBL can remarkably improve the charge transport of the DIBSQ:PC₇₁BM OPV cell and thus decrease the recombination losses of the device, resulting in enhanced device performance. Our finding indicates that the doped Bphen-Liq CBL has great potential for high-performance solution-processed small-molecule OPVs.     

Rational Tuning of Molecular Interaction and Energy Level Alignment Enables High‐Performance Organic Photovoltaics

The performance of organic photovoltaics (OPVs) has rapidly improved over the past years. Recent work in material design has primarily focused on developing near‐infrared nonfullerene acceptors with broadening absorption that pair with commercialized donor polymers; in the meanwhile, the influence of the morphology of the blend film and the energy level alignment on the efficiency of charge separation needs to be synthetically considered. Herein, the selection rule of the donor/acceptor blend is demonstrated by rationally considering the molecular interaction and energy level alignment, and highly efficient OPV devices using both‐fluorinated or both‐nonfluorinated donor/acceptor blends are realized. With the enlarged absorption, ideal morphology, and efficient charge transfer, the devices based on the PBDB‐T‐F/Y1‐4F blend and PBDB‐T‐F/Y6 exhibit champion power conversion efficiencies as high as 14.8% and 15.9%, respectively.     

Dielectric core-shell optical antennas for strong solar absorption enhancement

We demonstrate a new light trapping technique that exploits dielectric core-shell optical antennas to strongly enhance solar absorption. This approach can allow the thickness of active materials in solar cells lowered by almost 1 order of magnitude without scarifying solar absorption capability. For example, it can enable a 70 nm thick hydrogenated amorphous silicon (a-Si:H) thin film to absorb 90% of incident solar radiation above the bandgap, which would otherwise require a thickness of 400 nm in typical antireflective coated thin films. This strong enhancement arises from a controlled optical antenna effect in patterned core-shell nanostructures that consist of absorbing semiconductors and nonabsorbing dielectric materials. This core-shell optical antenna benefits from a multiplication of enhancements contributed by leaky mode resonances (LMRs) in the semiconductor part and antireflection effects in the dielectric part. We investigate the fundamental mechanism for this enhancement multiplication and demonstrate that the size ratio of the semiconductor and the dielectric parts in the core-shell structure is key for optimizing the enhancement. By enabling strong solar absorption enhancement, this approach holds promise for cost reduction and efficiency improvement of solar conversion devices, including solar cells and solar-to-fuel systems. It can generally apply to a wide range of inorganic and organic active materials. This dielectric core-shell antenna can also find applications in other photonic devices such as photodetectors, sensors, and solid-state lighting diodes.     

Multi-layer deposition of conformal, transparent, conducting oxide films for device applications

Conformal, high conductivity thin films of indium tin oxide (ITO) have been deposited utilizing a relatively low temperature, ambient, multi-layer dip coating process. Using standard alcohol solutions of indium chloride and stannic chloride to form ultra-thin layers, consecutive multi-layer deposition of ITO onto telecommunications grade glass fibers (as a model system) showed excellent control over grain morphology in the film as determined by electron microscopy, and a linear relationship between thickness and overall fiber conductivity. Ray tracing coupled with a transfer matrix formalism was used to numerically simulate the effects of film thickness on the optical waveguiding nature of the conducting layer. The simulations, carried out for a generic film morphology, show that a significant fraction of the optical energy coupled into the fiber face, is transmitted into the film at the thicknesses studied. These results were then used to estimate an upper limit of optical power transmission provided for the generic system. From this a comparison between the optical performance of sputter deposited and multi-layer conducting oxide films in a device configuration could be made. Organic photovoltaic devices, using both sputter deposited and multi-layer conductors on optical grade fibers, were fabricated and tested. Both compared favorably to the numerical simulations, suggesting that the overall, long range performance between the multi-layer deposited and sputtered films are comparable as cathodes for such conformal devices.     

Recent Progress in Interface Engineering of Nanostructures for Photoelectrochemical Energy Harvesting Applications

With rapid and continuous consumption of nonrenewable energy, solar energy can be utilized to meet the energy requirement and mitigate environmental issues in the future. To attain a sustainable society with an energy mix predominately dependent on solar energy, photoelectrochemical (PEC) device, in which semiconductor nanostructure-based photocatalysts play important roles, is considered to be one of the most promising candidates to realize the sufficient utilization of solar energy in a low-cost, green, and environmentally friendly manner. Interface engineering of semiconductor nanostructures has been qualified in the efficient improvement of PEC performances including three basic steps, i.e., light absorption, charge transfer/separation, and surface catalytic reaction. In this review, recently developed interface engineering of semiconductor nanostructures for direct and high-efficiency conversion of sunlight into available forms (e.g., chemical fuels and electric power) are summarized in terms of their atomic constitution and morphology, electronic structure and promising potential for PEC applications. Extensive efforts toward the development of high-performance PEC applications (e.g., PEC water splitting, PEC photodetection, PEC catalysis, PEC degradation and PEC biosensors) are also presented and appraised. Last but not least, a brief summary and personal insights on the challenges and future directions in the community of next-generation PEC devices are also provided.     

1 cm2 Organic Photovoltaic Cells for Indoor Application with over 20% Efficiency

Organic photovoltaic (OPV) technologies have the advantages of fabricating larger‐area and light‐weight solar panels on flexible substrates by low‐cost roll‐to‐toll production. Recently, OPV cells have achieved many significant advances with power conversion efficiency (PCE) increasing rapidly. However, large‐scale solar farms using OPV modules still face great challenges, such as device stability. Herein, the applications of OPV cells in indoor light environments are studied. Via optimizing the active layers to have a good match with the indoor light source, 1 cm² OPV cells are fabricated and a top PCE of 22% under 1000 lux light‐emitting diode (2700 K) illumination is demonstrated. In this work, the light intensities are measured carefully. Incorporated with the external quantum efficiency and photon flux spectrum, the integral current densities of the cells are calculated to confirm the reliability of the photovoltaic measurement. In addition, the devices show much better stability under continuous indoor light illumination. The results suggest that designing wide‐bandgap active materials to meet the requirements for the indoor OPV cells has a great potential in achieving higher photovoltaic performance.     

Solution‐Processed Semitransparent Organic Photovoltaics: From Molecular Design to Device Performance

Recent research efforts on solution‐processed semitransparent organic solar cells (OSCs) are presented. Essential properties of organic donor:acceptor bulk heterojunction blends and electrode materials, required for the combination of simultaneous high power conversion efficiency (PCE) and average visible transmittance of photovoltaic devices, are presented from the materials science and device engineering points of view. Aspects of optical perception, charge generation–recombination, and extraction processes relevant for semitransparent OSCs are also discussed in detail. Furthermore, the theoretical limits of PCE for fully transparent OSCs, compared to the performance of the best reported semitransparent OSCs, and options for further optimization are discussed.     

Fast photonic switches based on GaAs nanostructures

Fast photonic switches, in which light controls light, can be created based on high-voltage GaAs nanostructures with a thin (nanodimensional) surface dielectric layer. The switches offer a high operation speed that ensures optical data recording and transmission at a rate of 10⁴-10⁵ cps, possess a large modulation amplitude, and can operate at a relatively low optical control signal power (I<1 W/cm²). These devices can be used in systems of optical data processing, optical computation systems, all-optical communication lines with optical addressing of informative signals, etc.     

Design Considerations for Plasmonic Photovoltaics

This paper reviews the recent research progress in the incorporation of plasmonic nanostructures with photovoltaic devices and the potential for surface plasmon enhanced absorption. We first outline a variety of cell architectures incorporating metal nanostructures. We then review the experimental fabrication methods and measurements to date, as well as systematic theoretical studies of the optimal nanostructure shapes. Finally we discuss photovoltaic absorber materials that could benefit from surface plasmon enhanced absorption.