Perovskite Solar Cells on the Way to Their Radiative Efficiency Limit – Insights Into a Success Story of High Open‐Circuit Voltage and Low Recombination

Inorganic‐organic lead‐halide perovskite solar cells have reached efficiencies above 22% within a few years of research. Achieved photovoltages of >1.2 V are outstanding for a material with a bandgap of 1.6 eV – in particular considering that it is solution processed. Such values demand for low non‐radiative recombination rates and come along with high luminescence yields when the solar cell is operated as a light emitting diode. This progress report summarizes the developments on material composition and device architecture, which allowed for such high photovoltages. It critically assesses the term “lifetime”, the theories and experiments behind it, and the different recombination mechanisms present. It attempts to condense reported explanations for the extraordinary optoelectronic properties of the material. Amongst those are an outstanding defect tolerance due to antibonding valence states and the capability of bandgap tuning, which might make the dream of low‐cost highly efficient solution‐processed thin film solar cells come true. Beyond that, the presence of photon recycling will open new opportunities for photonic device design.     

Exploring the Limiting Open‐Circuit Voltage and the Voltage Loss Mechanism in Planar CH3NH3PbBr3 Perovskite Solar Cells

Perovskite solar cells based on CH₃NH₃PbBr₃ with a band gap of 2.3 eV are attracting intense research interests due to their high open‐circuit voltage (V_oc) potential, which is specifically relevant for the use in tandem configuration or spectral splitting. Many efforts have been performed to optimize the V_oc of CH₃NH₃PbBr₃ solar cells; however, the limiting V_oc (namely, radiative V_oc:V_oc,rad) and the corresponding ΔV_oc (the difference between V_oc,rad and V_oc) mechanism are still unknown. Here, the average V_oc of 1.50 V with the maximum value of 1.53 V at room temperature is achieved for a CH₃NH₃PbBr₃ solar cell. External quantum efficiency measurements with electroluminescence spectroscopy determine the V_oc,rad of CH₃NH₃PbBr₃ cells with 1.95 V and a ΔV_oc of 0.45 V at 295 K. When the temperature declines from 295 to 200 K, the obtained V_oc remains comparably stable in the vicinity of 1.5 V while the corresponding ΔV_oc values show a more significant increase. Our findings suggest that the V_oc of CH₃NH₃PbBr₃ cells is primarily limited by the interface losses induced by the charge extraction layer rather than by bulk dominated recombination losses. These findings are important for developing strategies how to further enhance the V_oc of CH₃NH₃PbBr₃‐based solar cells.     

Efficient Organic Solar Cells with Extremely High Open‐Circuit Voltages and Low Voltage Losses by Suppressing Nonradiative Recombination Losses

One of the most important factors that limits the efficiencies of bulk‐heterojunction organic solar cells (OSCs) is the modest open‐circuit voltage (V_oc) due to their large voltage loss (V_loss) caused by significant nonradiative recombination loss. To boost the performance of OSCs toward their theoretical limit, developing high‐performance donor: acceptor systems featuring low V_loss with suppressed nonradiative recombination losses (<0.30 V) is desired. Herein, high performance OSCs based on a polymer donor benzodithiophene‐difluorobenzoxadiazole‐2‐decyltetradecyl (BDT‐ffBX‐DT) and perylenediimide‐based acceptors (PDI dimer with spirofluorene linker (SFPDI), PDI4, and PDI6) are reported which offer a high power conversion efficiency (PCE) of 7.5%, 56% external quantum efficiency associated with very high V_oc (>1.10 V) and low V_loss (<0.60 V). A high V_oc up to 1.23 V is achieved, which is among the highest values reported for OSCs with a PCE beyond 6%, to date. These attractive results are benefit from the suppressed nonradiative recombination voltage loss, which is as low as 0.20 V. This value is the lowest value for OSCs so far and is comparable to high performance crystalline silicon and perovskite solar cells. These results show that OSCs have the potential to achieve comparable V_oc and voltage loss as inorganic photovoltaic technologies.     

On the Impact of Contact Selectivity and Charge Transport on the Open‐Circuit Voltage of Organic Solar Cells

The selectivity of electrodes of solar cells is a critical factor that can limit the overall efficiency. If the selectivity of an electrode is not sufficient both electrons and holes recombine at its surface. In materials with poor transport properties such as in organic solar cells, these surface recombination currents are accompanied by large gradients of the quasi‐Fermi energies as the driving force. Experimental results from current–voltage characteristics, advanced photo‐ and electroluminescence as well as charge extraction of three different photoactive materials are shown and compared to drift‐diffusion simulations. It can be concluded that in cases of electrodes with reduced selectivity the decrease of the open‐circuit voltage can be divided into two distinct contributions, the reduction of the overall steady‐state charge carrier density and the gradients of the quasi‐Fermi energies. The results clearly show that for photoactive layers with poor transport properties, the gradient of the quasi‐Fermi energy in the vicinity of the contact is the main contribution to the loss in open‐circuit voltage. For imbalanced mobilities, this gives rise to the phenomenon that it is more challenging to realize a selective contact for the less mobile charge carrier, i.e., the hole contact in most organic solar cells.     

Molecular Understanding of the Open‐Circuit Voltage of Polymer:Fullerene Solar Cells

The origin of open‐circuit voltage (V_OC) was studied for polymer solar cells based on a blend of poly(3‐hexylthiophene) (P3HT) and seven fullerene derivatives with different LUMO energy levels and side chains. The temperature dependence of J–V characteristics was analyzed by an equivalent circuit model. As a result, V_OC increased with the decrease in the saturation current density J₀ of the device. Furthermore, J₀ was dependent on the activation energy E_A for J₀, which is related to the HOMO–LUMO energy gap between P3HT and fullerene. Interestingly, the pre‐exponential term J₀₀ for J₀ was larger for pristine fullerenes than for substituted fullerene derivatives, suggesting that the electronic coupling between molecules also has substantial impact on V_OC. This is probably because the recombination is non‐diffusion‐lmilited reaction depending on electron transfer at the P3HT/fullerene interface. In summary, the origin of V_OC is ascribed not only to the relative HOMO–LUMO energy gap but also to the electronic couplings between fullerene/fullerene and polymer/fullerene.     

Growth Engineering of CH3NH3PbI3 Structures for High‐Efficiency Solar Cells

Controlling the growth of perovskite crystals has been one of the interesting strategies to mold their fundamental properties and exploit their potential in the fabrication of high performance solar cells. Herein, the impact of chloride on the conversion of lead halide into CH₃NH₃PbI₃, morphology, and coverage of perovskite structures using modified two‐step approach is investigated systematically, which eventually dictates the overall performance of the resulting device. Structural and morphological characterization is thoroughly carried out by X‐ray diffraction and field emission scanning electron microscopy, respectively. Various spectroscopic techniques provide ample evidence that CH₃NH₃PbI₃ structures formed in the presence of chloride, in the lead halide precursor solution, exhibit desired properties, such as fewer defects. Moreover, the morphology of CH₃NH₃PbI₃ structures and surface coverage of the resulting layers are considerably different from those obtained in the absence of chloride. After gaining a rational understanding regarding the effect of chloride on the growth, morphology, and optical properties of CH₃NH₃PbI₃ structures, fabrication of devices revealing a power conversion efficiency of over 16% under standard AM 1.5 G illumination is realized. The fundamental understanding and high efficiency reported here distinguishes our results, particularly where chloride based precursors are involved.     

Recombination in Polymer:Fullerene Solar Cells with Open‐Circuit Voltages Approaching and Exceeding 1.0 V

Polymer:fullerene solar cells are demonstrated with power conversion efficiencies over 7% with blends of PBDTTPD and PC₆₁BM. These devices achieve open‐circuit voltages (V_oc) of 0.945 V and internal quantum efficiencies of 88%, making them an ideal candidate for the large bandgap junction in tandem solar cells. V_oc’s above 1.0 V are obtained when the polymer is blended with multiadduct fullerenes; however, the photocurrent and fill factor are greatly reduced. In PBDTTPD blends with multiadduct fullerene ICBA, fullerene emission is observed in the photoluminescence and electroluminescence spectra, indicating that excitons are recombining on ICBA. Voltage‐dependent, steady state and time‐resolved photoluminescence measurements indicate that energy transfer occurs from PBDTTPD to ICBA and that back hole transfer from ICBA to PBDTTPD is inefficient. By analyzing the absorption and emission spectra from fullerene and charge transfer excitons, we estimate a driving free energy of –0.14 ± 0.06 eV is required for efficient hole transfer. These results suggest that the driving force for hole transfer may be too small for efficient current generation in polymer:fullerene solar cells with V_oc values above 1.0 V and that non‐fullerene acceptor materials with large optical gaps (>1.7 eV) may be required to achieve both near unity internal quantum efficiencies and values of V_oc exceeding 1.0 V.     

Understanding Open‐Circuit Voltage Loss through the Density of States in Organic Bulk Heterojunction Solar Cells

The field of organic photovoltaics has recently produced highly efficient single‐junction cells with power conversion efficiency >10%, yet the open‐circuit voltage (V_OC) remains relatively low in many high performing systems. An accurate picture of the density of states (DOS) in working solar cells is crucial to understanding the sources of voltage loss, but remains difficult to obtain experimentally. Here, the tail of the DOS is characterized in a number of small molecule bulk heterojunction solar cells from the charge density dependence of V_OC, and is directly compared to the disorder present within donor and acceptor components as measured by Kelvin probe. Using these DOS distributions, the total energy loss relative to the charge transfer state energy (E_CT)—ranging from ≈0.5 to 0.7 eV—is divided into contributions from energetic disorder and from charge recombination, and the extent to which these factors limit the V_OC is assessed.     

Achieving High Open‐Circuit Voltages up to 1.57 V in Hole‐Transport‐Material‐Free MAPbBr3 Solar Cells with Carbon Electrodes

An open‐circuit voltage (V_oc) of 1.57 V under simulated AM1.5 sunlight in planar MAPbBr₃ solar cells with carbon (graphite) electrodes is obtained. The hole‐transport‐material‐free MAPbBr₃ solar cells with the normal architecture (FTO/TiO₂/MAPbBr₃/carbon) show little hysteresis during current–voltage sweep under simulated AM1.5 sunlight. A solar‐to‐electricity power conversion efficiency of 8.70% is achieved with the champion device. Accordingly, it is proposed that the carbon electrodes are effective to extract photogenerated holes in MAPbBr₃ solar cells, and the industry‐applicable carbon electrodes will not limit the performance of bromide‐based perovskite solar cells. Based on the analysis of the band alignment, it is found that the voltage (energy) loss across the interface between MAPbBr₃ and carbon is very small compared to the offset between the valence band maximum of MAPbBr₃ and the work function of graphite. This finding implies either Fermi level pinning or highly doped region inside MAPbBr₃ layer exists. The band‐edge electroluminescence spectra of MAPbBr₃ from the solar cells further support no back‐transfer pathways of electrons across the MAPbBr₃/TiO₂ interface.     

Beyond Langevin Recombination: How Equilibrium Between Free Carriers and Charge Transfer States Determines the Open‐Circuit Voltage of Organic Solar Cells

Organic solar cells lag behind their inorganic counterparts in efficiency due largely to low open‐circuit voltages (V_oc). In this work, a comprehensive framework for understanding and improving the open‐circuit voltage of organic solar cells is developed based on equilibrium between charge transfer (CT) states and free carriers. It is first shown that the ubiquitous reduced Langevin recombination observed in organic solar cells implies equilibrium and then statistical mechanics is used to calculate the CT state population density at each voltage. This general result permits the quantitative assignment of V_oc losses to a combination of interfacial energetic disorder, non‐negligible CT state binding energies, large degrees of mixing, and sub‐ns recombination at the donor/acceptor interface. To quantify the impact of energetic disorder, a new temperature‐dependent CT state absorption measurement is developed. By analyzing how the apparent CT energy varies with temperature, the interfacial disorder can be directly extracted. 63–104 meV of disorder is found in five systems, contributing 75–210 mV of V_oc loss. This work provides an intuitive explanation for why qV_oc is almost always 500–700 meV below the energy of the CT state and shows how the voltage can be improved.     

Efficient CH3NH3PbI3 Perovskite Solar Cells Based on Graphdiyne (GD)‐Modified P3HT Hole‐Transporting Material

Novel large π‐conjugated carbon material, graphdiyne (GD), as a dopant to poly(3‐hexylthiophene) (P3HT) hole‐transporting material (HTM) layer, is introduced into perovskite solar cells for the first time. Raman spectroscopy and ultraviolet photoelectron spectroscopy measurements reveal that relatively strong π–π stacking interaction occurs between GD particles and P3HT (so‐called P3HT/GD composite HTM), favorable for the hole transportation and improvement of the cell performance. On the other hand, some GD aggregates exhibit a scattering nature, and thus help to increase the light absorption of the perovskite solar cells in the long wavelength range. As high as 14.58% light‐to‐electricity conversion efficiency is achieved, superior to the pristine P3HT‐based devices. Additionally, the devices exhibit good stability and reproducibility. Time‐resolved photoluminescence decay measurements reveal that the P3HT/GD HTM can accelerate the hole extraction compared with pristine P3HT.     

Inverted Current–Voltage Hysteresis in Mixed Perovskite Solar Cells: Polarization,Energy Barriers,and Defect Recombination

Organic‐inorganic metal halide perovskite solar cells show hysteresis in their current–voltage curve measured at a certain voltage sweep rate. Coinciding with a slow transient current response, the hysteresis is attributed to a slow voltage‐driven (ionic) charge redistribution in the perovskite solar cell. Thus, the electric field profile and in turn the electron/hole collection efficiency become dependent on the biasing history. Commonly, a positive prebias is beneficial for a high power‐conversion efficiency. Fill factor and open‐circuit voltage increase because the prebias removes the driving force for charge to pile‐up at the electrodes, which screen the electric field. Here, it is shown that the piled‐up charge can also be beneficial. It increases the probability for electron extraction in case of extraction barriers due to an enhanced electric field allowing for tunneling or dipole formation at the perovskite/electrode interface. In that case, an inverted hysteresis is observed, resulting in higher performance metrics for a voltage sweep starting at low prebias. This inverted hysteresis is particularly pronounced in mixed‐cation mixed‐halide systems which comprise a new generation of perovskite solar cells that makes it possible to reach power‐conversion efficiencies beyond 20%.     

Record Open‐Circuit Voltage Wide‐Bandgap Perovskite Solar Cells Utilizing 2D/3D Perovskite Heterostructure

In this work, the authors realize stable and highly efficient wide‐bandgap perovskite solar cells that promise high power conversion efficiencies (PCE) and are likely to play a key role in next generation multi‐junction photovoltaics (PV). This work reports on wide‐bandgap (≈1.72 eV) perovskite solar cells exhibiting stable PCEs of up to 19.4% and a remarkably high open‐circuit voltage (V_OC) of 1.31 V. The V_OC‐to‐bandgap ratio is the highest reported for wide‐bandgap organic?inorganic hybrid perovskite solar cells and the V_OC also exceeds 90% of the theoretical maximum, defined by the Shockley–Queisser limit. This advance is based on creating a hybrid 2D/3D perovskite heterostructure. By spin coating n‐butylammonium bromide on the double‐cation perovskite absorber layer, a thin 2D Ruddlesden–Popper perovskite layer of intermediate phases is formed, which mitigates nonradiative recombination in the perovskite absorber layer. As a result, V_OC is enhanced by 80 mV.     

Reducing Voltage Losses in Cascade Organic Solar Cells while Maintaining High External Quantum Efficiencies

High photon energy losses limit the open‐circuit voltage (V_OC) and power conversion efficiency of organic solar cells (OSCs). In this work, an optimization route is presented which increases the V_OC by reducing the interfacial area between donor (D) and acceptor (A). This optimization route concerns a cascade device architecture in which the introduction of discontinuous interlayers between alpha‐sexithiophene (α‐6T) (D) and chloroboron subnaphthalocyanine (SubNc) (A) increases the V_OC of an α‐6T/SubNc/SubPc fullerene‐free cascade OSC from 0.98 V to 1.16 V. This increase of 0.18 V is attributed solely to the suppression of nonradiative recombination at the D–A interface. By accurately measuring the optical gap (E_opt) and the energy of the charge‐transfer state (E_CT) of the studied OSC, a detailed analysis of the overall voltage losses is performed. E_opt – qV_OC losses of 0.58 eV, which are among the lowest observed for OSCs, are obtained. Most importantly, for the V_OC‐optimized devices, the low‐energy (700 nm) external quantum efficiency (EQE) peak remains high at 79%, despite a minimal driving force for charge separation of less than 10 meV. This work shows that low‐voltage losses can be combined with a high EQE in organic photovoltaic devices.     

Open‐Circuit Voltage in Organic Solar Cells: The Impacts of Donor Semicrystallinity and Coexistence of Multiple Interfacial Charge‐Transfer Bands

In organic solar cells (OSCs), the energy of the charge‐transfer (CT) complexes at the donor–acceptor interface, E _CT, determines the maximum open‐circuit voltage (V _OC). The coexistence of phases with different degrees of order in the donor or the acceptor, as in blends of semi‐crystalline donors and fullerenes in bulk heterojunction layers, influences the distribution of CT states and the V _OC enormously. Yet, the question of how structural heterogeneities alter CT states and the V _OC is seldom addressed systematically. In this work, we combine experimental measurements of vacuum‐deposited rubrene/C₆₀ bilayer OSCs, with varying microstructure and texture, with density functional theory calculations to determine how relative molecular orientations and extents of structural order influence E _CT and V _OC. We find that varying the microstructure of rubrene gives rise to CT bands with varying energies. The CT band that originates from crystalline rubrene lies up to ≈0.4 eV lower in energy compared to the one that arises from amorphous rubrene. These low‐lying CT states contribute strongly to V _OC losses and result mainly from hole delocalization in aggregated rubrene. This work points to the importance of realizing interfacial structural control that prevents the formation of low E _CT configurations and maximizes V _OC.     

Organic Salts as a Route to Energy Level Control in Low Bandgap,High Open‐Circuit Voltage Organic and Transparent Solar Cells that Approach the Excitonic Voltage Limit

A new series of organic salts with selective near‐infrared (NIR) harvesting to 950 nm is reported, and anion selection and blending is demonstrated to allow for fine tuning of the open‐circuit voltage. Extending photoresponse deeper into the NIR is a significant challenge facing small molecule organic photovoltaics, and recent demonstrations have been limited by open‐circuit voltages much lower than the theoretical and practical limits. This work presents molecular design strategies that enable facile tuning of energy level alignment and open‐circuit voltages in organic salt‐based photovoltaics. Anions are also shown to have a strong influence on exciton diffusion length. These insights provide a clear route toward achieving high efficiency transparent and panchromatic photovoltaics, and open up design opportunities to rapidly tailor molecules for new donor–acceptor systems.