Cover Picture: Solution‐Processed Organic Tandem Solar Cells (Adv. Funct. Mater. 14/2006)

The fabrication of a solution‐processed polymer tandem cell by stacking two single cells in series is reported by de Boer and co‐workers on p. 1897. The bottom and top cell are complementary with respect to their absorption spectra and the layer thickness of the bottom cell was optimized in order to create an optical cavity that efficiently transmits the required wavelength for the top cell. The combination of this tandem architecture with more efficient small‐bandgap materials will enable the realization of highly efficient organic solar cells. A solution‐processed polymer tandem cell fabricated by stacking two single cells in series is demonstrated. The two bulk‐heterojunction subcells have complementary absorption maxima at λ_max ～ 850 nm and λ_max ～ 550 nm, respectively. A composite middle electrode is applied that serves both as a charge‐recombination center and as a protecting layer for the first cell during spin‐coating of the second cell. The subcells are electronically coupled in series, which leads to a high open‐circuit voltage of 1.4 V, equal to the sum of each subcell. The layer thickness of the first (bottom) cell is tuned to maximize the optical absorption of the second (top) cell. The performance of the tandem cell is presently limited by the relatively low photocurrent generation in the small‐bandgap polymer of the top cell. The combination of our tandem architecture with more efficient small‐bandgap materials will enable the realization of highly efficient organic solar cells in the near future.     

Efficient tandem polymer photovoltaic cells with two subcells in parallel connection

Tandem polymer photovoltaic cells with the subcells having different absorption characteristics in series connection are widely investigated to enhance absorption coverage over the solar spectrum. Herein, we demonstrate efficient tandem polymer photovoltaic cells with the two stacked subcells comprising different band-gap conjugated polymer and fullerene derivative bulk heterojunction in parallel connection. A semitransparent metal layer combined with inorganic semiconductor compounds is utilized as the intermediate electrode of the two stacked subcells to create the required built-in potential for collecting photo-generated charges. The short-circuit current of the stacked cell is the sum of the subcells and the open-circuit voltage is similar to the subcells.     

Polymeric Alkoxy PBD [2‐(4‐Biphenylyl)‐5‐Phenyl‐1,3,4‐Oxadiazole] for Light‐Emitting Diodes

The syntheses are reported of the title polymeric alkoxyPBD derivative 5 and the dipyridyl analogue 12 using Suzuki coupling reactions of 1,4‐dialkoxybenzene‐2,5‐diboronic acid with 2,5‐bis(4‐bromophenyl)‐1,3,5‐oxadiazole, and its dipyridyl analogue, respectively. Thermal gravimetric analysis shows that polymers 5 and 12 are stable up to 370 °C and 334 °C, respectively. Films of polymer 5 spun from chloroform solution show an absorption at λ_max = 367 nm, and a weaker band at 312 nm, and strong blue photoluminescence at λ_max = 444 nm. The photoluminescence quantum yield (PLQY) was found to be 27 ± 3 %. For polymer 12 , the absorption spectra reveal bands of equal intensity at λ_max = 374 and 312 nm, with PL at λ_max = 475 nm. Device studies using polymer 12 were hampered by its instability under illumination and/or electrical excitation. Polymer 5 is stable under these conditions and acts as an efficient electron‐transporting/hole‐blocking layer. For devices of configuration ITO/PEDOT/MEH‐PPV/polymer 5 /Al an external quantum efficiency of 0.26 % and brightness of 800 cd/m² was readily achieved: orange emission was observed, identical to the MEH‐PPV electroluminescence.     

Graphene Intermediate Layer in Tandem Organic Photovoltaic Cells

One strategy to harvest wide spectral solar energy is to stack different bandgap materials together in a tandem solar cell. Here, it is demonstrated that CVD grown graphene film can be employed as intermediate layer (IML) in tandem solar cells. Using MoO₃‐modified graphene IML, a high open circuit voltage (V_oc) of 1 V and a high short‐circuit current density (J_sc) of 11.6 mA cm^‐2 could be obtained in series and parallel connection, respectively, in contrast to a V_oc of 0.58 V and J_sc of 7.6 mA cm^‐2 in single PV cell. The value of V_oc (J_sc) in the tandem cell is very close to the sum of V_oc (J_sc) attained from two single subcells in series (parallel), which confirms good ohmic contact at the photoactive layer/MoO₃‐modified graphene interface. Work function engineering of the graphene IML with metal oxide is essential to ensure good charge collection from both subcells.     

8.91% Power Conversion Efficiency for Polymer Tandem Solar Cells

A power conversion efficiency of up to 8.91% is obtained for a solution‐processed polymer tandem solar cells based on a large‐bandgap polymer, poly(4,4‐dioctyldithieno(3,2‐b:2′,3′‐d)silole)‐2,6‐diyl‐alt‐(2,1,3‐benzothiadiazole)‐4,7‐diyl) with a polymeric interconnecting layer to electrically connect the front and rear subcells, demonstrating that proper device and interface engineering are can improve the performance of polymer tandem solar cells.     

Estimating the Maximum Attainable Efficiency in Dye‐Sensitized Solar Cells

For an ideal solar cell, a maximum solar‐to‐electrical power conversion efficiency of just over 30% is achievable by harvesting UV to near IR photons up to 1.1 eV. Dye‐sensitized solar cells (DSCs) are, however, not ideal. Here, the electrical and optical losses in the dye‐sensitized system are reviewed, and the main losses in potential from the conversion of an absorbed photon at the optical bandgap of the sensitizer to the open‐circuit voltage generated by the solar cell are specifically highlighted. In the first instance, the maximum power conversion efficiency attainable as a function of optical bandgap of the sensitizer and the “loss‐in‐potential” from the optical bandgap to the open‐circuit voltage is estimated. For the best performing DSCs with current technology, the loss‐in‐potential is ～0.75 eV, which leads to a maximum power‐conversion efficiency of 13.4% with an optical bandgap of 1.48 eV (840 nm absorption onset). Means by which the loss‐in‐potential could be reduced to 0.4 eV are discussed; a maximum efficiency of 20.25% with an optical bandgap of 1.31 eV (940 nm) is possible if this is achieved.     

An Efficient Bulk‐Heterojunction Photovoltaic Cell Based on Energy Transfer in Graded‐Bandgap Polymers

It is demonstrated that the energy transfer from low‐conjugated (LC) poly[2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylene vinylene] (MEHPPV) to high‐conjugated (HC) MEHPPV, coupled with significant electron transfer from HC‐MEHPPV to an acceptor species, offers a viable route for an efficient photodiode over a wide spectral range. An enhanced incident‐photon‐to‐current conversion efficiency (IPCE) of 19 % over a wide spectral range and a power‐conversion efficiency (η_P) of 1 % (under monochromatic illumination at λ ～ 530 nm and a power density of ca. 1 mW cm^–2) are achieved in a ternary polymer‐blend film that consists of HC‐MEHPPV (low bandgap), LC‐MEHPPV (high bandgap), and an acceptor polymer, cyanoPPV (CNPPV), in an optimized ratio. The decisive role of the morphology that emerges during phase separation in the polymer blend is demonstrated by wide‐field photocurrent imaging.     

13·9%‐efficient CdTe polycrystalline thin‐film solar cells with an infrared transmission of ∼50%

To fabricate a high‐efficiency polycrystalline thin‐film tandem cell, the most critical work is to make a high‐efficiency top cell ( > 15%) with high bandgap (E_g = 1·5–1·8 eV) and high transmission (T > 70%) in the near‐infrared (NIR) wavelength region. The CdTe cell is one of the candidates for the top cell, because CdTe state‐of‐the‐art single‐junction devices with efficiencies of more than 16% are available, although its bandgap (1·48 eV) is slightly lower for a top cell in a current‐matched dual‐junction device. In this paper, we focus on the development of a: (1) thin, low‐bandgap Cu_xTe transparent back‐contact; and (2) modified CdTe device structure, including three novel materials: cadmium stannate transparent conducting oxide (TCO), ZnSnO_x buffer layer, and nanocrystalline CdS:O window layer developed at NREL, as well as the high‐quality CdTe film, to improve transmission in the NIR region while maintaining high device efficiency. We have achieved an NREL‐confirmed 13·9%‐efficient CdTe transparent solar cell with an infrared transmission of ∼50% and a CdTe/CIS polycrystalline mechanically stacked thin‐film tandem cell with an NREL‐confirmed efficiency of 15·3%. Copyright © 2005 John Wiley & Sons, Ltd.     

Photoconductivity of a Low‐Bandgap Conjugated Polymer

The photoconductive properties of a novel low‐bandgap conjugated polymer, poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)], PCPDTBT, with an optical energy gap of E_g ～ 1.5 eV, have been studied. The results of photoluminescence and photoconductivity measurements indicate efficient electron transfer from PCPDTBT to PCBM ([6,6]‐phenyl‐C61 butyric acid methyl ester, a fullerene derivative), where PCPDTBT acts as the electron donor and PCBM as the electron acceptor. Electron‐transfer facilitates charge separation and results in prolonged carrier lifetime, as observed by fast (t > 100 ps) transient photoconductivity measurements. The photoresponsivities of PCPDTBT and PCPDTBT:PCBM are comparable to those of poly(3‐hexylthiophene), P3HT, and P3HT:PCBM, respectively. Moreover, the spectral sensitivity of PCPDTBT:PCBM extends significantly deeper into the infrared, to 900 nm, than that of P3HT. The potential of PCPDTBT as a material for high‐efficiency polymer solar cells is discussed.     

Perovskite‐Based Tandem Solar Cells: Get the Most Out of the Sun

Tandem solar cells (TSCs) comprising stacked narrow‐bandgap and wide‐bandgap subcells are regarded as the most promising approach to break the Shockley–Queisser limit of single‐junction solar cells. As the game‐changer in the photovoltaic community, organic–inorganic hybrid perovskites became the front‐runner candidate for mating with other efficient photovoltaic technologies in the tandem configuration for higher power conversion efficiency, by virtue of their tunable and complementary bandgaps, excellent photoelectric properties, and solution processability. In this review, a perspective that critically dilates the progress of perovskite material selection and device design for perovskite‐based TSCs, including perovskite/silicon, perovskite/copper indium gallium selenide, perovskite/perovskite, perovskite/CdTe, and perovskite/GaAs are presented. Besides, all‐inorganic perovskite CsPbI₃ with high thermal stability is proposed as the top subcell in TSCs due to its suitable bandgap of ≈1.73 eV and rapidly increasing efficiency. To minimize the optical and electrical losses for high‐efficiency TSCs, the optimization of transparent electrodes, recombination layers, and the current‐matching principles are highlighted. Through big data analysis, wide‐bandgap perovskite solar cells with high open‐circuit voltage (V_oc) are in dire need in further study. In the end, opportunities and challenges to realize the commercialization of TSCs, including long‐term stability, area upscaling, and mitigation of toxicity, are also envisioned.     

Polymer Solar Cells Based on a Low‐Bandgap Fluorene Copolymer and a Fullerene Derivative with Photocurrent Extended to 850 nm

Polymer solar cells have been fabricated from a recently synthesized low band‐gap alternating polyfluorene copolymer, APFO‐Green2, combined with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) from organic solutions. External quantum efficiencies (EQEs) of the solar cells show an onset at 850 nm and a peak of > 10 % located at 650 nm, which corresponds to the extended absorption spectrum of the polymer. Photocurrent of 3.0 mA cm^–2, photovoltage of 0.78 V, and power conversion efficiency of 0.9 % have been achieved in solar cells based on this new low‐bandgap polymer under the illumination of air mass 1.5 (AM 1.5) (1000 W m^–2) from a solar simulator.     

Multijunction solar cell design revisited: disruption of current matching by atmospheric absorption bands

This paper re‐examines the impact of atmospheric absorption bands on series‐connected multijunction cell design, motivated by the numerous local efficiency maxima that appear as the number of junctions is increased. Some of the local maxima are related to the bottom subcell bandgap and are already well understood: As the bottom subcell bandgap is varied, a local efficiency maximum is produced wherever the bottom cell bandgap crosses an atmospheric absorption band. The optimal cell designs at these local maxima are generally current matched, such that all subcells have nearly the same short‐circuit current. Here, we systematically describe additional local maxima that occur wherever an upper subcell bandgap encounters an atmospheric absorption band. These local maxima are not current matched and become more prevalent as the number of junctions increases, complicating the solution space for five‐junction and six‐junction designs. A systematic framework for describing this complexity is developed, and implications for numerical convergence are discussed. Copyright © 2017 John Wiley & Sons, Ltd.     

The Influence of TiO2 Particle Size in TiO2/CuInS2 Nanocomposite Solar Cells

The recently developed CuInS₂/TiO₂ 3D nanocomposite solar cell employs a three‐dimensional, or “bulk”, heterojunction to reduce the average minority charge‐carrier‐transport distance and thus improve device performance compared to a planar configuration. 3D nanocomposite solar‐cell performance is strongly influenced by the morphology of the TiO₂ nanoparticulate matrix. To explore the effect of TiO₂ morphology, a series of three nanocomposite solar‐cell devices are studied using 9, 50, and 300 nm TiO₂ nanoparticles, respectively. The photovoltaic efficiency increases dramatically with increasing particle size, from 0.2 % for the 9 nm sample to 2.8 % for the 300 nm sample. Performance improvements are attributed primarily to greatly improved charge transport with increasing particle size. Other contributing factors may include increased photon absorption and improved interfacial characteristics in the larger‐particle‐size matrix.     

Enhanced Photocurrent Spectral Response in Low‐Bandgap Polyfluorene and C70‐Derivative‐Based Solar Cells

Plastic solar cells have been fabricated using a low‐bandgap alternating copolymer of fluorene and a donor–acceptor–donor moiety (APFO‐Green1), blended with 3′‐(3,5‐bis‐trifluoromethylphenyl)‐1′‐(4‐nitrophenyl)pyrazolino[70]fullerene (BTPF70) as electron acceptor. The polymer shows optical absorption in two wavelength ranges, λ < 500 nm and 600 < λ < 1000 nm. The BTPF70 absorbs light at λ < 700 nm. A broad photocurrent spectral response in the wavelength range 300 < λ < 1000 nm is obtained in solar cells. A photocurrent density of 3.4 mA cm^–2, open‐circuit voltage of 0.58 V, and power‐conversion efficiency of 0.7 % are achieved under illumination of AM1.5 (1000 W m^–2) from a solar simulator. Synthesis of BTPF70 is presented. Photoluminescence quenching and electrochemical studies are used to discuss photoinduced charge transfer.     

17.87% Efficiency All-Polymer Tandem Solar Cell Enabled by Complementary Absorbing Polymer Acceptors

All-polymer solar cells (all-PSCs) possess distinguished advantages of excellent morphology stability, thermal stability, and mechanical flexibility. Tandem solar cells, by stacking two sub-cells, can absorb more photons in a wider wavelength range and can reduce thermal losses. However, limitation of polymer acceptors with suitable bandgaps hinders the development of tandem all-PSCs. Herein, highly efficient tandem all-PSCs are fabricated by employing two polymerized small molecular acceptors (PSMAs) of wide bandgap PIDT (1.66 eV) in the front cell and narrow bandgap PY-IT (1.4 eV) in the rear cell. The two sub-cells with the polymer donors of PM7 in front cell and PM6 in rear cell show high open circuit voltage (V_oc) of 1.10 V for the front cell and 0.94 V for the rear cell. By rational device optimizations, the best power conversion efficiency of 17.87% is achieved for the tandem all-PSCs with high V_oc of 2.00 V. 17.87% is one of the highest efficiency for the all-PSCs, and 2.00 V is one of the highest V_oc for all the tandem organic solar cells. Moreover, the tandem all-PSCs show excellent thermal and light-soaking stability compared with their small-molecule counterparts. The results provide insight to the potential of bandgap tuning in PSMAs, and indicate that the tandem architecture is an effective strategy to boost performance of the all-PSCs.     

Measuring the External Quantum Efficiency of Two‐Terminal Polymer Tandem Solar Cells

Tandem configurations, in which two cells are stacked and connected in series, offer a viable approach to further increase the power conversion efficiency (PCE) of organic solar cells. To enable the future rational design of new materials it is important to accurately assess the contributions of individual subcells. Such accurate measurement of the external quantum efficiency (EQE) of the subcells of two‐terminal organic or polymer tandem solar cells poses specific challenges, caused by two characteristics of these cells, i.e. a sub‐linear light intensity dependence of the current and a field‐assisted charge collection. These properties necessitate that EQE experiments are carried out under representative illumination conditions and electrical bias to maintain short‐circuit conditions for the addressed subcell. We describe a method to determine the magnitudes of the bias illumination and bias voltage during EQE measurements, based on the behavior of single junction cells and optical modeling. The short‐circuit current densities of the subcells obtained by convolution of the EQE with the AM1.5G solar spectrum are consistent with those obtained from optical modeling and correctly predict the current density–voltage characteristics of the tandem cell under AM1.5G conditions.     

Ligand‐Free Synthesis of Aluminum‐Doped Zinc Oxide Nanocrystals and their Use as Optical Spacers in Color‐Tuned Highly Efficient Organic Solar Cells

The color of polymer solar cells using an opaque electrode is given by the reflected light, which depends on the composition and thickness of each layer of the device. Metal‐oxide‐based optical spacers are intensively studied in polymer solar cells aiming to optimize the light absorption. However, the low conductivity of materials such as ZnO and TiO₂ limits the thickness of such optical spacers to tenths of nanometers. A novel synthesis route of cluster‐free Al‐doped ZnO (AZO) nanocrystals (NCs) is presented for solution processing of highly conductive layers without the need of temperature annealing, including thick optical spacers on top of polymer blends. The processing of 80 nm thick optical spacers based on AZO nanocrystal solutions on top of 200 nm thick polymer blend layer is demonstrated leading to improved photocurrent density of 17% compared to solar cells using standard active layers of 90 nm in combination with thin ZnO‐based optical spacers. These AZO NCs also open new opportunities for the processing of high‐efficiency color tuned solar cells. For the first time, it is shown that applying solution‐processed thick optical spacer with polymer blends of different thicknesses can process solar cells of similar efficiency over 7% but of different colors.     

Control of Solid‐State Dye‐Sensitized Solar Cell Performance by Block‐Copolymer‐Directed TiO2 Synthesis

Hybrid dye‐sensitized solar cells are typically composed of mesoporous titania (TiO₂), light‐harvesting dyes, and organic molecular hole‐transporters. Correctly matching the electronic properties of the materials is critical to ensure efficient device operation. In this study, TiO₂ is synthesized in a well‐defined morphological confinement that arises from the self‐assembly of a diblock copolymer—poly(isoprene‐b‐ethylene oxide) (PI‐b‐PEO). The crystallization environment, tuned by the inorganic (TiO₂ mass) to organic (polymer) ratio, is shown to be a decisive factor in determining the distribution of sub‐bandgap electronic states and the associated electronic function in solid‐state dye‐sensitized solar cells. Interestingly, the tuning of the sub‐bandgap states does not appear to strongly influence the charge transport and recombination in the devices. However, increasing the depth and breadth of the density of sub‐bandgap states correlates well with an increase in photocurrent generation, suggesting that a high density of these sub‐bandgap states is critical for efficient photo‐induced electron transfer and charge separation.     

Organic Tandem and Multi‐Junction Solar Cells

The emerging field of stacked layers (double‐ and even multi‐layers) in organic photovoltaic cells is reviewed. Owing to the limited absorption width of organic molecules and polymers, only a small fraction of the solar flux can be harvested by a single‐layer bulk heterojunction photovoltaic cell. Furthermore, the low charge‐carrier mobilities of most organic materials limit the thickness of the active layer. Consequently, only part of the intensity of the incident light at the absorption maximum is absorbed. A tandem or multi‐junction solar cell, consisting of multiple layers each with their specific absorption maximum and width, can overcome these limitations and can cover a larger part of the solar flux. In addition, tandem or multi‐junction solar cells offer the distinct advantage that photon energy is used more efficiently, because the voltage at which charges are collected in each sub‐cell is closer to the energy of the photons absorbed in that cell. Recent developments in both small‐molecule and polymeric photovoltaic cells are discussed, and examples of photovoltaic architectures, geometries, and materials combinations that result in tandem and multi‐junction solar cells are presented.     

Achieving an Efficiency Exceeding 10% for Fullerene‐based Polymer Solar Cells Employing a Thick Active Layer via Tuning Molecular Weight

Recently, the influence of molecular weight (M_n) on the performance of polymer solar cells (PSCs) is widely investigated. However, the dependence of optimal thickness of active layer for PSCs on M_n is not reported yet, which is vital to the solution printing technology. In this work, the effect of M_n on the efficiency and especially optimal thickness of the active layer for PBTIBDTT‐S‐based PSCs is systematically studied. The device efficiency improves significantly as the M_n increases from 12 to 38 kDa, and a remarkable efficiency of 10.1% is achieved, which is among the top efficiencies of wide‐bandgap polymer:fullerene PSCs. Furthermore, the optimal thickness of the active layer is also greatly increased from 62 to 210 nm with increased M_n. Therefore, a device employing a thick (>200 nm) active layer with power conversion efficiency exceeding 10% is achieved by manipulating M_n. This exciting result is attributed to both the improved crystallinity, thus hole mobility, and preferable polymer orientation, thus morphology of active layer. These findings, for the first time, highlight the significant impact of M_n on the optimal thickness of active layer for PSCs and provide a facile way to further improve the performance of PSCs employing a thick active layer.