Current Collecting Grids for ITO‐Free Solar Cells

Indium‐tin‐oxide (ITO) free polymer solar cells prepared by ink jet printing a composite front electrode comprising silver grid lines and a semitransparent PEDOT:PSS conductor are demonstrated. The effect of grid line density is explored for a large series of devices and a careful modeling study enabling the identification of the most rational grid structure is presented. Both optical and light beam induced current (LBIC) mapping of the devices are used to support the power loss model and to follow the evolution of the performance over time. Current generation is found to be evenly distributed over the active area initially progressing to a larger graduation in areas with different performance. Over time coating defects also become much more apparent in the LBIC images.     

ITO‐Free and Fully Solution‐Processed Semitransparent Organic Solar Cells with High Fill Factors

Organic photovoltaic (OPV) solar cells that can be simply processed from solution are in the focus of the academic and industrial community because of their enormous potential to reduce cost. One big challenge in developing a fully solution‐processed OPV technology is the design of a well‐performing electrode system, allowing the replacement of ITO. Several solution‐processed electrode systems were already discussed, but none of them could match the performance of ITO. Here, we report efficient ITO‐free and fully solution‐processed semitransparent inverted organic solar cells based on silver nanowire (AgNW) electrodes. To demonstrate the potential of these AgNW electrodes, they were employed as both the bottom and top electrodes. Record devices achieved fill factors as high as 63.0%, which is comparable to ITO based reference devices. These results provide important progress for fully printed organic solar cells and indicate that ITO‐free, transparent as well as non‐transparent organic solar cells can indeed be fully solution‐processed without losses.     

Semi‐Transparent Tandem Organic Solar Cells with 90% Internal Quantum Efficiency

Semi‐transparent (ST) organic solar cells with potential application as power generating windows are studied. The main challenge is to find proper transparent electrodes with desired electrical and optical properties. In this work, this is addressed by employing an amphiphilic conjugated polymer PFPA‐1 modified ITO coated glass substrate as the ohmic electron‐collecting cathode and PEDOT:PSS PH1000 as the hole‐collecting anode. For active layers based on different donor polymers, considerably lower reflection and parasitic absorption are found in the ST solar cells as compared to solar cells in the standard geometry with an ITO/PEDOT:PSS anode and a LiF/Al cathode. The ST solar cells have remarkably high internal quantum efficiency at short circuit condition (～90%) and high transmittance (～50%). Hence, efficient ST tandem solar cells with enhanced power conversion efficiency (PCE) compared to a single ST solar cell can be constructed by connecting the stacked two ST sub‐cells in parallel. The total loss of photons by reflection, parasitic absorption and transmission in the ST tandem solar cell can be smaller than the loss in a standard solar cell based on the same active materials. We demonstrate this by stacking five separately prepared ST cells on top of each other, to obtain a higher photocurrent than in an optimized standard solar cell.     

Three‐Dimensional Nanostructured Indium‐Tin‐Oxide Electrodes for Enhanced Performance of Bulk Heterojunction Organic Solar Cells

A three‐dimensional indium tin oxide (ITO) nanohelix (NH) array is presented as a multifunctional electrode for bulk heterojunction organic solar cells for simultaneously improving light absorption and charge transport from the active region to the anode. It is shown that the ITO NH array, which is easily fabricated using an oblique‐angle‐deposition technique, acts as an effective antireflection coating as well as a light‐scattering layer, resulting in much enhanced light harvesting. Furthermore, the larger interfacial area between the electrode and the active layer, together with the enhanced carrier mobility through highly conductive ITO NH facilitate transport and collection of charge carriers. The optical and electrical improvements enabled by the ITO NH electrode result in a 10% increase in short‐circuit current density and power‐conversion efficiency of the solar cells.     

Efficient Polymer Solar Cells on Opaque Substrates with a Laminated PEDOT:PSS Top Electrode

Solution processed polymer:fullerene solar cells on opaque substrates have been fabricated in conventional and inverted device configurations. Opaque substrates, such as insulated steel and metal covered glass, require a transparent conducting top electrode. We demonstrate that a high conducting (900 S cm^?1) PEDOT:PSS layer, deposited by a stamp‐transfer lamination technique using a PDMS stamp, in combination with an Ag grid electrode provides a proficient and versatile transparent top contact. Lamination of large size PEDOT:PSS films has been achieved on variety of surfaces resulting in ITO‐free solar cells. Power conversion efficiencies of 2.1% and 3.1% have been achieved for P3HT:PCBM layers in inverted and conventional polarity configurations, respectively. The power conversion efficiency is similar to conventional glass/ITO‐based solar cells. The high fill factor (65%) and the unaffected open‐circuit voltage that are consistently obtained in thick active layer inverted geometry devices, demonstrate that the laminated PEDOT:PSS top electrodes provide no significant potential or resistive losses.     

Charge Transport and Recombination in Low‐Bandgap Bulk Heterojunction Solar Cell using Bis‐adduct Fullerene

Charge transport and recombination are studied for organic solar cells fabricated using blends of polymer poly[(4,4′‐bis(2‐ethylhexyl)dithieno[3,2‐b:2′,3′‐d]silole)‐2,6‐diyl‐alt‐(4,7‐bis(2‐thienyl)‐2,1,3‐benzothiadiazole)‐5,5′‐diyl] (Si‐PCPDTBT) with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (mono‐PCBM) and the bis‐adduct analogue of mono‐PCBM (bis‐PCBM). The photocurrent of Si‐PCPDTBT:bis‐PCBM devices shows a strong square root dependence on the effective applied voltage. From the relationship between the photocurrent and the light intensity, we found that the square‐root dependence of the photocurrent is governed by the mobility‐lifetime (μτ) product of charge carriers while space‐charge field effects are insignificant. The fill factor (FF) and short circuit current density (J_sc) of bis‐PCBM solar cells show a considerable increase with temperature as compared to mono‐PCBM solar cells. SCLC analysis of single carrier devices proofs that the mobility of both electrons and holes is significantly lowered when replacing mono‐PCBM with bis‐PCBM. The increased recombination in Si‐PCPDTBT:bis‐PCBM solar cells is therefore attributed to the low carrier mobilities, as the transient photovoltage measurements show that the carrier lifetime of devices are not significantly altered by using bis‐PCBM instead of mono‐PCBM.     

Burn‐in Free Nonfullerene‐Based Organic Solar Cells

Organic solar cells that are free of burn‐in, the commonly observed rapid performance loss under light, are presented. The solar cells are based on poly(3‐hexylthiophene) (P3HT) with varying molecular weights and a nonfullerene acceptor (rhodanine‐benzothiadiazole‐coupled indacenodithiophene, IDTBR) and are fabricated in air. P3HT:IDTBR solar cells light‐soaked over the course of 2000 h lose about 5% of power conversion efficiency (PCE), in stark contrast to [6,6]‐Phenyl C61 butyric acid methyl ester (PCBM)‐based solar cells whose PCE shows a burn‐in that extends over several hundreds of hours and levels off at a loss of ≈34%. Replacing PCBM with IDTBR prevents short‐circuit current losses due to fullerene dimerization and inhibits disorder‐induced open‐circuit voltage losses, indicating a very robust device operation that is insensitive to defect states. Small losses in fill factor over time are proposed to originate from polymer or interface defects. Finally, the combination of enhanced efficiency and stability in P3HT:IDTBR increases the lifetime energy yield by more than a factor of 10 when compared with the same type of devices using a fullerene‐based acceptor instead.     

High‐Efficiency Polymer Homo‐Tandem Solar Cells with Carbon Quantum‐Dot‐Doped Tunnel Junction Intermediate Layer

The tunnel junction (TJ) intermediate connection layer (ICL), which is the most critical component for high‐efficient tandem solar cell, generally consists of hole conducting layer and polyethyleneimine (PEI) polyelectrolyte. However, because of the nonconducting feature of pristine PEI, photocurrent is open‐restricted in ICL even with a little thick PEI layer. Here, high‐efficiency homo‐tandem solar cells are demonstrated with enhanced efficiency by introducing carbon quantum dot (CQD)‐doped PEI on TJ–ICL. The CQD‐doped PEI provides substantial dynamic advantages in the operation of both single‐junction solar cells and homo‐tandem solar cells. The inclusion of CQDs in the PEI layer leads to improved electron extraction property in single‐junction solar cells and better series connection in tandem solar cells. The highest efficient solar cell with CQD‐doped PEI layer in between indium tin oxide (ITO) and photoactive layer exhibits a maximum power conversion efficiency (PCE) of 9.49%, which represents a value nearly 10% higher than those of solar cells with pristine PEI layer. In the case of tandem solar cells, the highest performing tandem solar cell fabricated with C‐dot‐doped PEI layer in ICL yields a PCE of 12.13%; this value represents an ≈15% increase in the efficiency compared with tandem solar cells with a pristine PEI layer.     

Fully Solution‐Processed TCO‐Free Semitransparent Perovskite Solar Cells for Tandem and Flexible Applications

Semitransparent perovskite solar cells (st‐PSCs) have received remarkable interest in recent years because of their great potential in applications for solar window, tandem solar cells, and flexible photovoltaics. However, all reported st‐PSCs require expensive transparent conducting oxides (TCOs) or metal‐based thin films made by vacuum deposition, which is not cost effective for large‐scale fabrication: the cost of TCOs is estimated to occupy ≈75% of the manufacturing cost of PSCs. To address this critical challenge, this study reports a low‐temperature and vacuum‐free strategy for the fabrication of highly efficient TCO‐free st‐PSCs. The TCO‐free st‐PSC on glass exhibits 13.9% power conversion efficiency (PCE), and the four‐terminal tandem cell made with the st‐PSC top cell and c‐Si bottom cell shows an overall PCE of 19.2%. Due to the low processing temperature, the fabrication of flexible st‐PSCs is demonstrated on polyethylene terephthalate and polyimide, which show excellent stability under repeated bending or even crumbing.     

Parallelized Nanopillar Perovskites for Semitransparent Solar Cells Using an Anodized Aluminum Oxide Scaffold

Semitransparent solar cells have attracted significant attention for practical applications, such as windows in buildings and automobiles. Here, semitransparent, highly efficient, 1D nanostructured perovskite solar cells are demonstrated employing anodized aluminum oxide (AAO) as a scaffold layer. The parallel nanopillars in the perovskite layer enable construction of haze‐free semitransparent devices without any hysteresis behavior. By controlling the pore size in the AAO, the volume occupied by the perovskite layer can be precisely varied, and the color neutrality of the resulting devices can be achieved. With the incorporation of a transparent cathodic electrode (indium tin oxide) with a buffer layer (MoO_x), a highly efficient semitransparent nanopillared perovskite solar cell is achievable with a power‐conversion efficiency of 9.6% (7.5%) and a whole device average visible light transmittance of 33.4% (41.7%). To determine the role of the scaffold layer in improving the photoelectrical properties of the cell, impedance spectroscopy analyses are performed, revealing that the AAO‐structured perovskite layer suppresses internal ion diffusion and enables critical improvements in long‐term stability under continuous illumination.     

Charge Formation in Pentacene Layers During Solar‐Cell Fabrication: Direct Observation by Electron Spin Resonance

Microscopic characterization of charge carriers in solar cells is useful for high‐performance cell fabrication because the formation and accumulation of charges in cells greatly affect the device performance. Electron spin resonance (ESR) is suitable for such characterization because it can directly observe charge carriers with spins in these cells. In this work, the ESR method is applied to organic thin‐film solar cells to investigate charge formation in such devices. Heterojunction cells of indium tin oxide (ITO)/poly(3,4‐ethylenedioxythiophene):poly(4‐styrenesulfonate) (PEDOT:PSS)/pentacene/C₆₀/bathocuproine (BCP)/Al are investigated. Clear ESR signals are observed by inserting a typical PEDOT:PSS hole buffer layer. From analysis of the dependence of the ESR characteristics on the external magnetic field direction, the bias voltage, and the duration of solar‐simulated irradiation, the charges (mobile holes) in pentacene layers are successfully identified and it can be deduced that these holes are formed at the PEDOT:PSS/pentacene interface during device fabrication. This ESR analysis provides useful knowledge for understanding device operation and improving device performance at the microscopic level.     

Simple,Highly Efficient Vacuum‐Processed Bulk Heterojunction Solar Cells Based on Merocyanine Dyes

In order to be competitive on the energy market, organic solar cells with higher efficiency are needed. To date, polymer solar cells have retained the lead with efficiencies of up to 8%. However, research on small molecule solar cells has been catching up throughout recent years and is showing similar efficiencies, however, only for more sophisticated multilayer device configurations. In this work, a simple, highly efficient, vacuum‐processed small molecule solar cell based on merocyanine dyes – traditional colorants that can easily be mass‐produced and purified – is presented. In the past, merocyanines have been successfully introduced in solution‐processed as well as vacuum‐processed devices, demonstrating efficiencies up to 4.9%. Here, further optimization of devices is achieved while keeping the same simple layer stack, ultimately leading to efficiencies beyond the 6% mark. In addition, physical properties such as the charge carrier transport and the cell performance under various light intensities are addressed.     

Self‐Assembled 2D Perovskite Layers for Efficient Printable Solar Cells

2D organic–inorganic hybrid Ruddlesden–Popper perovskites have emerged recently as candidates for the light‐absorbing layer in solar cell technology due largely to their impressive operational stability compared with their 3D‐perovskite counterparts. The methods reported to date for the preparation of efficient 2D perovksite layers for solar cells involve a nonscalable spin‐coating step. In this work, a facile, spin‐coating‐free, directly scalable drop‐cast method is reported for depositing precursor solutions that self‐assemble into highly oriented, uniform 2D‐perovskite films in air, yielding perovskite solar cells with power conversion efficiencies (PCE) of up to 14.9% (certified PCE of 14.33% ± 0.34 at 0.078 cm²). This is the highest PCE to date for a solar cell with 2D‐perovskite layers fabricated by nonspin‐coating method. The PCEs of the cells display no evidence of degradation after storage in a nitrogen glovebox for more than 5 months. 2D‐perovskite layer deposition using a slot‐die process is also investigated for the first time. Perovskite solar cells fabricated using batch slot‐die coating on a glass substrate or R2R slot‐die coating on a flexible substrate produced PCEs of 12.5% and 8.0%, respectively.     

Multifunctional Luminescent Down‐Shifting Fluoropolymer Coatings: A Straightforward Strategy to Improve the UV‐Light Harvesting Ability and Long‐Term Outdoor Stability of Organic Dye‐Sensitized Solar Cells

A new multifunctional coating for photovoltaic cells incorporating light‐management, UV‐protection, and easy‐cleaning capabilities is presented. Such coating consists of a new photocurable fluorinated polymer embedding a luminescent europium complex that acts as luminescent down‐shifting (LDS) material converting UV photons into visible light. The combination of this system with ruthenium‐free organic dye‐sensitized solar cells (DSSCs) gives a 70% relative increase in power conversion efficiency as compared with control uncoated devices, which is the highest efficiency enhancement reported to date on organic DSSC systems by means of a polymeric LDS layer. Long‐term (>2000 h) weathering tests in real outdoor conditions reveal the excellent stabilizing effect of the new coating on DSSC devices, which fully preserve their initial performance. This excellent outdoor stability is attributed to the combined action of the luminescent material that acts as UV‐screen and the highly photostable, hydrophobic fluoropolymeric carrier that further prevents photochemical and physical degradation of the solar cell components. The straightforward approach presented to simultaneously improve performance and outdoor stability of DSSC devices may be readily extended to a large variety of sensitizer/luminophore combinations, thus enabling the fabrication of highly efficient and extremely stable DSSCs in an easy and versatile fashion.     

Upscaling of Perovskite Solar Cells: Fully Ambient Roll Processing of Flexible Perovskite Solar Cells with Printed Back Electrodes

A scaling effort on perovskite solar cells is presented where the device manufacture is progressed onto flexible substrates using scalable techniques such as slot‐die roll coating under ambient conditions. The printing of the back electrode using both carbon and silver is essential to the scaling effort. Both normal and inverted device geometries are explored and it is found that the formation of the correct morphology for the perovskite layer depends heavily on the surface upon which it is coated and this has significant implications for manufacture. The time it takes to form the desired layer morphology falls in the range of 5–45 min depending on the perovskite precursor, where the former timescale is compatible with mass production and the latter is best suited for laboratory work. A significant loss in solar cell performance of around 50% is found when progressing to using a fully scalable fabrication process, which is comparable to what is observed for other printable solar cell technologies such as polymer solar cells. The power conversion efficiency (PCE) for devices processed using spin coating on indium tin oxide (ITO)‐glass with evaporated back electrode yields a PCE of 9.4%. The same device type and active area realized using slot‐die coating on flexible ITO‐polyethyleneterphthalate (PET) with a printed back electrode gives a PCE of 4.9%.     

Enhanced Light Harvesting in Perovskite Solar Cells by a Bioinspired Nanostructured Back Electrode

Light management holds great promise of realizing high‐performance perovskite solar cells by improving the sunlight absorption with lower recombination current and thus higher power conversion efficiency (PCE). Here, a convenient and scalable light trapping scheme is demonstrated by incorporating bioinspired moth‐eye nanostructures into the metal back electrode via soft imprinting technique to enhance the light harvesting in organic–inorganic lead halide perovskite solar cells. Compared to the flat reference cell with a methylammonium lead halide perovskite (CH₃NH₃PbI_3?x Cl_x ) absorber, 14.3% of short‐circuit current improvement is achieved for the patterned devices with moth‐eye nanostructures, yielding an increased PCE up to 16.31% without sacrificing the open‐circuit voltage and fill factor. The experimental and theoretical characterizations verify that the cell performance enhancement is mainly ascribed by the broadband polarization‐insensitive light scattering and surface plasmonic effects due to the patterned metal back electrode. It is noteworthy that this light trapping strategy is fully compatible with solution‐processed perovskite solar cells and opens up many opportunities toward the future photovoltaic applications.     

Interplay between Bimolecular Recombination and Carrier Transport Distances in Bulk Heterojunction Organic Solar Cells

In this work, it is demonstrated that bimolecular recombination depends on the distance that free carriers are required to travel in transit to the electrodes in bulk heterojunction organic solar cells. By employing semi‐transparent devices, the carrier transport distance can be controlled via the local light absorption profile with an appropriate choice of the illumination side and incident wavelength. Using a series of light intensity‐dependent measurements, bimolecular recombination is shown to depend on the distance electrons or holes are required to transit the active layer. This effect is demonstrated for three different bulk heterojunction blends, where the restrictive carrier that causes the onset of recombination is identified. The mobility‐lifetime products of the limiting carriers are also estimated using a simple model for carrier extraction, where similar values are obtained regardless of the absorption profile. Implications for 1‐sun performance are also discussed, which provide guidelines for fabricating devices with thicker active layers capable of maximizing light absorption without succumbing to recombination losses.     

Square‐Centimeter‐Sized High‐Efficiency Polymer Solar Cells: How the Processing Atmosphere and Film Quality Influence Performance at Large Scale

Organic solar cells based on two benzodithiophene‐based polymers (PTB7 and PTB7‐Th) processed at square centimeter‐size under inert atmosphere and ambient air, respectively, are investigated. It is demonstrated that the performance of solar cells processed under inert atmosphere is not limited by the upscaling of photoactive layer and the interfacial layers. Thorough morphological and electrical characterizations of optimized layers and corresponding devices reveal that performance losses due to area enlargement are only caused by the sheet resistance of the transparent electrode reducing the efficiency from 9.3% of 7.8% for PTB7‐Th in the condition that both photoactive layer and the interfacial layers are of high layer quality. Air processing of photoactive layer and the interfacial layers into centimeter‐sized solar cells lead to additional, but only slight, losses (<10%) in all photovoltaic parameters, which can be addressed to changes in the electronic properties of both active layer and ZnO layers rather than changes in layer morphology. The demonstrated compatibility of polymer solar cells using solution‐processed photoactive layer and interfacial layers with large area indicates that the introduction of a standard active area of 1 cm² for measuring efficiency of organic record solar cells is feasible. However electric standards for indium tin oxides (ITO) or alternative transparent electrodes need to be developed so that performance of new photovoltaic materials can be compared at square centimeter‐size.     

The Physics of Small Molecule Acceptors for Efficient and Stable Bulk Heterojunction Solar Cells

Organic bulk heterojunction solar cells based on small molecule acceptors have recently seen a rapid rise in the power conversion efficiency with values exceeding 13%. This impressive achievement has been obtained by simultaneous reduction of voltage and charge recombination losses within this class of materials as compared to fullerene‐based solar cells. In this contribution, the authors review the current understanding of the relevant photophysical processes in highly efficient nonfullerene acceptor (NFA) small molecules. Charge generation, recombination, and charge transport is discussed in comparison to fullerene‐based composites. Finally, the authors review the superior light and thermal stability of nonfullerene small molecule acceptor based solar cells, and highlight the importance of NFA‐based composites that enable devices without early performance loss, thus resembling so‐called burn‐in free devices.     

Conductive and Stable Magnesium Oxide Electron‐Selective Contacts for Efficient Silicon Solar Cells

A high Schottky barrier (>0.65 eV) for electrons is typically found on lightly doped n‐type crystalline (c‐Si) wafers for a variety of contact metals. This behavior is commonly attributed to the Fermi‐level pinning effect and has hindered the development of n‐type c‐Si solar cells, while its p‐type counterparts have been commercialized for several decades, typically utilizing aluminium alloys in full‐area, and more recently, partial‐area rear contact configurations. Here the authors demonstrate a highly conductive and thermally stable electrode composed of a magnesium oxide/aluminium (MgO_x/Al) contact, achieving moderately low resistivity Ohmic contacts on lightly doped n‐type c‐Si. The electrode, functionalized with nanoscale MgO_x films, significantly enhances the performance of n‐type c‐Si solar cells to a power conversion efficiency of 20%, advancing n‐type c‐Si solar cells with full‐area dopant‐free rear contacts to a point of competitiveness with the standard p‐type architecture. The low thermal budget of the cathode formation, its dopant‐free nature, and the simplicity of the device structure enabled by the MgO_x/Al contact open up new possibilities in designing and fabricating low‐cost optoelectronic devices, including solar cells, thin film transistors, or light emitting diodes.