Scaling Up ITO‐Free Solar Cells

Indium‐tin‐oxide‐free (ITO‐free) polymer solar cells with composite electrodes containing current‐collecting grids and a semitransparent poly(3,4‐ethylenedioxythiophene):polystyrenesulfonate) (PEDOT:PSS) conductor are demonstrated. The up‐scaling of the length of the solar cell from 1 to 6 cm and the effect of the grid line resistance are explored for a series of devices. Laser‐beam‐induced current (LBIC) mapping is used for quality control of the devices. A theoretical modeling study is presented that enables the identification of the most rational cell dimension for the grids with different resistances. The performance of ITO‐free organic solar cells with different dimensions and different electrode resistances are evaluated for different light intensities. The current generation and electric potential distribution are found to not be uniformly distributed in large‐area devices at simulated 1 Sun illumination. The generated current uniformity increases with decreasing light intensities.     

Chemical Consequences of Alkali Inhomogeneity in Cu2ZnSnS4 Thin‐Film Solar Cells

This study offers new insight into the role of Na in Cu₂ZnSnS₄ (CZTS) thin film solar cells by studying samples with a spatially varying alkali distribution. This is achieved by omitting a diffusion barrier between the soda‐lime glass substrate and the Mo back contact, where compositional variations of the glass inherently result in non‐uniform alkali distributions in the CZTS. By correlating light beam induced current (LBIC) maps with secondary ion mass spectrometry composition maps, it is shown that samples containing regions of higher Na concentration (“hot spots”) have corresponding LBIC hot spots on comparable length scales. Samples containing an alkali diffusion barrier have lower LBIC dispersion; thus, LBIC can be used to evaluate non‐uniformity in CZTS devices, where a common cause is Na inhomogeneity. Moreover, it is shown that the Na hot spots are strongly correlated with other compositional variations in the device, including increased Cu in‐diffusion with the underlying MoS₂ layer and decreased diffusion of Cd to the back contact. Neither of these effects are well understood in CZTS devices, and neither have previously been correlated with the presence or absence of Na.     

High‐Efficiency CsPbI2Br Perovskite Solar Cells with Dopant‐Free Poly(3‐hexylthiophene) Hole Transporting Layers

CsPbI₂Br is emerging as a promising all‐inorganic material for perovskite solar cells (PSCs) due to its more stable lattice structure and moisture resistance compared to CsPbI₃, although its device performance is still much behind this counterpart. Herein, a preannealing process is developed and systematically investigated to achieve high‐quality CsPbI₂Br films by regulating the nucleation and crystallization of perovskite. The preannealing temperature and time are specifically optimized for a dopant‐free poly(3‐hexylthiophene) (P3HT)‐based device to target dopant‐induced drastic performance degradation for spiro‐OMeTAD‐based devices. The resulting P3HT‐based device exhibits comparable power conversion efficiency (PCE) to spiro‐OMeTAD‐based devices but much enhanced ambient stability with over 95% PCE after 1300 h. A diphenylamine derivative is introduced as a buffer layer to improve the energy‐level mismatch between CsPbI₂Br and P3HT. A record‐high PCE of 15.50% for dopant‐free P3HT‐based CsPbI₂Br PSCs is achieved by alleviating the open‐circuit voltage loss with the buffer layer. These results demonstrate that the preannealing processing together with a suitable buffer layer are applicable strategies for developing dopant‐free P3HT PSCs with high efficiency and stability.     

Spray‐Cast Multilayer Organometal Perovskite Solar Cells Fabricated in Air

Spray‐coating is a versatile coating technique that can be used to deposit functional films over large areas at speed. Here, spray‐coating is used to fabricate inverted perovskite solar cell devices in which all of the solution‐processible layers (PEDOT:PSS, perovskite, and PCBM) are deposited by ultrasonic spray‐casting in air. Using such techniques, all‐spray‐cast devices having a champion power conversion efficiency (PCE) of 9.9% are fabricated. Such performance compares favorably with reference devices spin‐cast under a nitrogen atmosphere that has a champion PCE of 12.8%. Losses in device efficiency are ascribed to lower surface coverage and reduced uniformity of the spray‐cast perovskite layer.     

Inkjet Printing of Back Electrodes for Inverted Polymer Solar Cells

Evaporation is the most commonly used deposition method in the processing of back electrodes in polymer solar cells used in scientific studies. However, vacuum‐based methods such as evaporation are uneconomical in the upscaling of polymer solar cells as they are throughput limiting steps in an otherwise fast roll‐to‐roll production line. In this paper, the applicability of inkjet printing in the ambient processing of back electrodes in inverted polymer solar cells with the structure ITO/ZnO/P3HT:PCBM/PEDOT:PSS/Ag is investigated. Furthermore, the limitation of screen printing, the commonly employed method in the ambient processing of back electrode, is demonstrated and discussed. Both inkjet printing and screen printing of back electrodes are studied for their impact on the photovoltaic properties of the polymer solar cells measured under 1000 Wm^?2 AM1.5. Each ambient processing technique is compared with evaporation in the processing of back electrode. Laser beam induced current (LBIC) imaging is used to investigate the impact of the processing techniques on the current collection in the devices. We report that inkjet printing of back electrode delivers devices having photovoltaic performance comparable to devices with evaporated back electrodes. We further confirm that inkjet printing represent an efficient alternative to screen printing.     

Controllable ZnMgO Electron‐Transporting Layers for Long‐Term Stable Organic Solar Cells with 8.06% Efficiency after One‐Year Storage

Currently, one main challenge in organic solar cells (OSCs) is to achieve both good stability and high power conversion efficiencies (PCEs). Here, highly efficient and long‐term stable inverted OSCs are fabricated by combining controllable ZnMgO (ZMO) cathode interfacial materials with a polymer:fullerene bulk‐heterojunction. The resulting devices based on the nanocolloid/nanoridge ZMO electron‐transporting layers (ETLs) show greatly enhanced performance compared to that of the conventional devices or control devices without ZMO or with ZnO ETLs. The ZMO‐based OSCs maintain 84%–93% of their original PCEs over 1‐year storage under ambient conditions. An initial PCE of 9.39% is achieved for the best device, and it still retains a high PCE of 8.06% after 1‐year storage, which represents a record high value for long‐term stable OSCs. The excellent performance is attributed to the enhanced electron transportation/collection, reduced interfacial energy losses, and improved stability of the nanocolloid ZMO ETL. These findings provide a promising way to develop OSCs with high efficiencies and long device lifetime towards practical applications.     

Eco‐Friendly Solvent‐Processed Fullerene‐Free Polymer Solar Cells with over 9.7% Efficiency and Long‐Term Performance Stability

A wide‐bandgap polymer, (poly[(2,6‐(4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)‐benzo[1,2‐b:4,5‐b′]dithiophene))‐alt‐(2,5‐(methyl thiophene carboxylate))]) (3MT‐Th), is synthesized to obtain a complementary broad range absorption when harmonized with 3,9‐bis(2‐methylene‐(3‐(1,1‐dicyanomethylene)‐indanone))‐5,5,11,11‐tetrakis(4‐hexylphenyl)‐dithieno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene (ITIC). The synthesized regiorandom 3MT‐Th polymer shows good solubility in nonhalogenated solvents. A film of 3MT‐Th:ITIC can be employed for forming an active layer in a polymer solar cell (PSC), with the blend solution containing toluene with 0.25% diphenylether as a nonhalogenated additive. The corresponding PSC devices display a power conversion efficiency of 9.73%. Moreover, the 3MT‐Th‐based PSCs exhibit excellent shelf‐life time of over 1000 h and are operationally stable under continuous light illumination. Therefore, methyl thiophene‐3‐carboxylate in 3MT‐Th is a promising new accepting unit for constructing p‐type polymers used for high‐performance nonfullerene‐type PSCs.     

Solution‐Processed Ternary Oxides as Carrier Transport/Injection Layers in Optoelectronics

With the remarkable progress in solution‐processed optoelectronics, high performance is required of the carrier transport/injection layer. Ternary oxides containing a variety of crystal structures, and adjustable composition that results in tunable optical and electrical properties, are one of the promising class of candidates to fulfill the requirements of carrier transport/injection layers for high‐performance and stable optoelectronic devices. Solution‐processed ternary oxides have seen considerable progress in recent decades, due to their advantages in the quest to design low‐cost, high‐performance, large‐scale, and stable optoelectronic devices. Herein, the recent advances of solution‐processed ternary oxides are reviewed. The first section consists of a brief introduction to the topic. In the following section, the fundamentals of the effect of tuning ternary oxide composition are summarized. Section three briefly reviews the synthesis approaches for preparing ternary oxides. Section four discusses the recent progress of solution‐processed ternary oxide as carrier transport/injection layer in optoelectronic devices (such as organic solar cells, perovskite solar cells, organic light emitting diodes, etc.). In this section, the impact of controlling ternary oxide composition on device performance and stability is highlighted. Finally, a brief summary and an outlook are given.     

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.     

Thermally Stable All‐Polymer Solar Cells with High Tolerance on Blend Ratios

Tuning the blend composition is an essential step to optimize the power conversion efficiency (PCE) of organic bulk heterojunction (BHJ) solar cells. PCEs from devices of unoptimized donor:acceptor (D:A) weight ratio are generally significantly lower than optimized devices. Here, two high‐performance organic nonfullerene BHJ blends PBDB‐T:ITIC and PBDB‐T:N2200 are adopted to investigate the effect of blend ratio on device performance. It is found that the PCEs of polymer‐polymer (PBDB‐T:N2200) blend are more tolerant to composition changes, relative to polymer‐molecule (PBDB‐T:ITIC) devices. In both systems, short‐circuit current density (J_sc) is tracked closely with PCE, indicating that exciton dissociation and transport strongly influence PCEs. With dilute acceptor concentrations, polymer‐polymer blends maintain high electron mobility relative to the polymer‐molecule blends, which explains the dramatic difference in PCEs between them as a function of D:A blend ratio. In addition, polymer‐polymer solar cells, especially at high D:A blend ratio, are stable (less than 5% relative loss) over 70 d under continuous heating at 80 °C in a glovebox without encapsulation. This work demonstrates that all‐polymer solar cells show advantage in operational lifetime under thermal stress and blend‐ratio resilience, which indicates their high potential for designing of stable and scalable solar cells.     

Visibly‐Transparent Organic Solar Cells on Flexible Substrates with All‐Graphene Electrodes

Portable electronic devices have become increasingly widespread. Because these devices cannot always be tethered to a central grid, powering them will require low‐cost energy harvesting technologies. As a response to this anticipated demand, this study demonstrates transparent organic solar cells fabricated on flexible substrates, including plastic and paper, using graphene as both the anode and cathode. Optical transmittance of up to 69% at 550 nm is achieved by combining the highly transparent graphene electrodes with organic polymers that primarily absorb in the near‐IR and near‐UV regimes. To address the challenge of transferring graphene onto organic layers as the top electrode, this study develops a room temperature dry‐transfer technique using ethylene‐vinyl‐acetate as an adhesion‐promoting interlayer. The power conversion efficiency achieved for flexible devices with graphene anode and cathode devices is 2.8%–3.8% at for optical transmittance of 54%–61% across the visible regime. These results demonstrate the versatility of graphene in optoelectronic applications and it is important step toward developing a practical power source for distributed wireless electrical systems.     

Is the Cu/Zn Disorder the Main Culprit for the Voltage Deficit in Kesterite Solar Cells?

Photovoltaic thin film solar cells based on kesterite Cu₂ZnSn(S_x,Se_1–x)₄ compounds (CZTSSe) have reached >12% sunlight‐to‐electricity conversion efficiency. This is still far from the >20% record devices known in Cu(In_1–y,Ga_y)Se₂ and CdTe parent technologies. A selection of >9% CZTSSe devices reported in the literature is examined to review the progress achieved over the past few years. These devices suffer from a low open‐circuit voltage (V_oc) never better than 60% of the V_{oc max}, which is expected from the Shockley‐Queisser radiative limit (S‐Q limit). The possible role of anionic (S/Se) distribution and of cationic (Cu/Zn) disorder on the V_oc deficit and on the ultimate photovoltaic performance of kesterite devices, are clarified here. While the S/Se anionic distribution is expected to be homogeneous for any ratio x, some grain‐to‐grain and other non‐uniformity over larger area can be found, as quantified on our CZTSSe films. Nevertheless, these anionic distributions can be considered to have a negligible impact on the V_oc deficit. On the Cu/Zn order side, even though significant bandgap changes (>10%) can be observed, a similar conclusion is brought from experimental devices and from calculations, still within the radiative S‐Q limit. The implications and future ways for improvement are discussed.     

Improving the Performance and Stability of Inverted Planar Flexible Perovskite Solar Cells Employing a Novel NDI‐Based Polymer as the Electron Transport Layer

A new naphthalene diimide (NDI)‐based polymer with strong electron withdrawing dicyanothiophene (P(NDI2DT‐TTCN)) is developed as the electron transport layer (ETL) in place of the fullerene‐based ETL in inverted perovskite solar cells (Pero‐SCs). A combination of characterization techniques, including atomic force microscopy, scanning electron microscopy, grazing‐incidence wide‐angle X‐ray scattering, near‐edge X‐ray absorption fine‐structure spectroscopy, space‐charge‐limited current, electrochemical impedance spectroscopy, photoluminescence (PL), and time‐resolved PL decay, is used to demonstrate the interface phenomena between perovskite and P(NDI2DT‐TTCN) or [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM). It is found that P(NDI2DT‐TTCN) not only improves the electron extraction ability but also prevents ambient condition interference by forming a hydrophobic ETL surface. In addition, P(NDI2DT‐TTCN) has excellent mechanical stability compared to PCBM in flexible Pero‐SCs. With these improved functionalities, the performance of devices based on P(NDI2DT‐TTCN) significantly outperform those based on PCBM from 14.3 to 17.0%, which is the highest photovoltaic performance with negligible hysteresis in the field of polymeric ETLs.     

Integrated Design of Organic Hole Transport Materials for Efficient Solid‐State Dye‐Sensitized Solar Cells

A series of triphenylamine‐based small molecule organic hole transport materials (HTMs) with low crystallinity and high hole mobility are systematically investigated in solid‐state dye‐sensitized solar cells (ssDSCs). By using the organic dye LEG4 as a photosensitizer, devices with X3 and X35 as the HTMs exhibit desirable power conversion efficiencies (PCEs) of 5.8% and 5.5%, respectively. These values are slightly higher than the PCE of 5.4% obtained by using the state‐of‐the‐art HTM Spiro‐OMeTAD. Meanwhile, transient photovoltage decay measurement is used to gain insight into the complex influences of the HTMs on the performance of devices. The results demonstrate that smaller HTMs induce faster electron recombination in the devices and suggest that the size of a HTM plays a crucial role in device performance, which is reported for the first time.     

The Role of Antireflective Coating CYTOP,Immersion Oil,and Sensitizer Selection in Fabricating a 2.3 V, 10% Power Conversion Efficiency SSM‐DSC Device

Sequential series multijunction dye‐sensitized solar cells (SSM‐DSCs) can power solar‐to‐fuel processes with a single illuminated area device. Dye selection and strategies limiting photon losses are critical in SSM‐DSC devices for higher performance systems. Herein, an efficient and readily applicable spin coating protocol on glass surfaces with an antireflective fluoropolymer (CYTOP) is applied to an SSM‐DSC architecture. Combining CYTOP with the use of an immersion oil between glass spacers in a three subcell SSM‐DSC with judiciously selected TiO₂ photoanode sensitizers and thicknesses, an overall power conversion efficiency (PCE) of 10.1% is obtained with an output of 2.3 V. Without external bias, this SSM‐DSC configuration shows an impressive overall solar‐to‐fuel conversion efficiency of 6% when powering IrO₂ and Au₂O₃ electrocatalysts for CO₂ and H₂O to CO and H₂ conversion in aqueous solution. The role of CYTOP, immersion oil, sensitizer selection, and film thickness on SSM‐DSC devices is discussed along with the stability of this system.     

On the Origin of the Ideality Factor in Perovskite Solar Cells

The measurement of the ideality factor (n_id) is a popular tool to infer the dominant recombination type in perovskite solar cells (PSC). However, the true meaning of its values is often misinterpreted in complex multilayered devices such as PSC. In this work, the effects of bulk and interface recombination on the n_id are investigated experimentally and theoretically. By coupling intensity‐dependent quasi‐Fermi level splitting measurements with drift diffusion simulations of complete devices and partial cell stacks, it is shown that interfacial recombination leads to a lower n_id compared to Shockley–Read–Hall (SRH) recombination in the bulk. As such, the strongest recombination channel determines the n_id of the complete cell. An analytical approach is used to rationalize that n_id values between 1 and 2 can originate exclusively from a single recombination process. By expanding the study over a wide range of the interfacial energy offsets and interfacial recombination velocities, it is shown that an ideality factor of nearly 1 is usually indicative of strong first‐order non‐radiative interface recombination and that it correlates with a lower device performance. It is only when interface recombination is largely suppressed and bulk SRH recombination dominates that a small n_id is again desirable.     

Understanding the Role of Cesium and Rubidium Additives in Perovskite Solar Cells: Trap States,Charge Transport,and Recombination

Adding cesium (Cs) and rubidium (Rb) cations to FA_0.83MA_0.17Pb(I_0.83Br_0.17)₃ hybrid lead halide perovskites results in a remarkable improvement in solar cell performance, but the origin of the enhancement has not been fully understood yet. In this work, time‐of‐flight, time‐resolved microwave conductivity, and thermally stimulated current measurements are performed to elucidate the impact of the inorganic cation additives on the trap landscape and charge transport properties within perovskite solar cells. These complementary techniques allow for the assessment of both local features within the perovskite crystals and macroscopic properties of films and full devices. Strikingly, Cs‐incorporation is shown to reduce the trap density and charge recombination rates in the perovskite layer. This is consistent with the significant improvements in the open‐circuit voltage and fill factor of Cs‐containing devices. By comparison, Rb‐addition results in an increased charge carrier mobility, which is accompanied by a minor increase in device efficiency and reduced current–voltage hysteresis. By mixing Cs and Rb in quadruple cation (Cs‐Rb‐FA‐MA) perovskites, the advantages of both inorganic cations can be combined. This study provides valuable insights into the role of these additives in multiple‐cation perovskite solar cells, which are essential for the design of high‐performance devices.     

Charge Carrier Extraction in Organic Solar Cells Governed by Steady‐State Mobilities

Charge transport in organic photovoltaic (OPV) devices is often characterized by steady‐state mobilities. However, the suitability of steady‐state mobilities to describe charge transport has recently been called into question, and it has been argued that dispersion plays a significant role. In this paper, the importance of the dispersion of charge carrier motion on the performance of organic photovoltaic devices is investigated. An experiment to measure the charge extraction time under realistic operating conditions is set up. This experiment is applied to different blends and shows that extraction time is directly related to the geometrical average of the steady‐state mobilities. This demonstrates that under realistic operating conditions the steady‐state mobilities govern the charge extraction of OPV and gives a valuable insight in device performance.     

Flexible and Semitransparent Organic Solar Cells

Flexible and semitransparent organic solar cells (OSCs) have been regarded as the most promising photovoltaic devices for the application of OSCs in wearable energy resources and building‐integrated photovoltaics. Therefore, the flexible and semitransparent OSCs have developed rapidly in recent years through the synergistic efforts in developing novel flexible bottom or top transparent electrodes, designing and synthesizing high performance photoactive layer and low temperature processed electrode buffer layer materials, and device architecture engineering. To date, the highest power conversion efficiencies have reached over 10% of the flexible OSCs and 7.7% with average visible transmittance of 37% for the semitransparent OSCs. Here, a comprehensive overview of recent research progresses and perspectives on the related materials and devices of the flexible and semitransparent OSCs is provided.     

Constructing High‐Performance All‐Small‐Molecule Ternary Solar Cells with the Same Third Component but Different Mechanisms for Fullerene and Non‐fullerene Systems

Two types of all‐small‐molecule ternary solar cells consisting of two small‐molecule donors and one acceptor (fullerene/non‐fullerene) are developed. Interestingly, both these devices have a common component: a carefully designed medium bandgap small molecule, which possesses appropriate energy levels and displays good compatibility with the host donor. In the fullerene system, the charge‐relaying role of the additive donor is confirmed by the improved charge transportation and suppressed charge recombination. While in the non‐fullerene system, the mixed face‐on and edge‐on orientation of the ternary film induced by the additive donor dominates the promotion of charge transportation. Accordingly, both ternary devices deliver higher short‐circuit current density, fill factor, and power conversion efficiencies of over 10% compared to binary ones. This work offers a promising guideline on the construction of high‐performance all‐small‐molecule ternary solar cells by incorporating a miscible small‐molecule donor.