Perovskite photovoltaic (PV) cells have demonstrated power conversion efficiencies (PCE) that are close to those of monocrystalline silicon cells; however, in contrast to silicon PV, perovskites are ...not limited by Auger recombination under 1‐sun illumination. Nevertheless, compared to GaAs and monocrystalline silicon PV, perovskite cells have significantly lower fill factors due to a combination of resistive and non‐radiative recombination losses. This necessitates a deeper understanding of the underlying loss mechanisms and in particular the ideality factor of the cell. By measuring the intensity dependence of the external open‐circuit voltage and the internal quasi‐Fermi level splitting (QFLS), the transport resistance‐free efficiency of the complete cell as well as the efficiency potential of any neat perovskite film with or without attached transport layers are quantified. Moreover, intensity‐dependent QFLS measurements on different perovskite compositions allows for disentangling of the impact of the interfaces and the perovskite surface on the non‐radiative fill factor and open‐circuit voltage loss. It is found that potassium‐passivated triple cation perovskite films stand out by their exceptionally high implied PCEs > 28%, which could be achieved with ideal transport layers. Finally, strategies are presented to reduce both the ideality factor and transport losses to push the efficiency to the thermodynamic limit.
A method is introduced to experimentally measure the efficiency potential of any neat perovskite film on glass with/without attached transport layers using intensity‐dependent photoluminescence measurements. This approach allows decoupling efficiency losses due to insufficient charge transport, bulk, interface, and surface recombination. These findings also shine light on the ideality factor in perovskite solar cells and thereby fill factor limitations.
Perovskite semiconductors are an attractive option to overcome the limitations of established silicon based photovoltaic (PV) technologies due to their exceptional opto‐electronic properties and ...their successful integration into multijunction cells. However, the performance of single‐ and multijunction cells is largely limited by significant nonradiative recombination at the perovskite/organic electron transport layer junctions. In this work, the cause of interfacial recombination at the perovskite/C60 interface is revealed via a combination of photoluminescence, photoelectron spectroscopy, and first‐principle numerical simulations. It is found that the most significant contribution to the total C60‐induced recombination loss occurs within the first monolayer of C60, rather than in the bulk of C60 or at the perovskite surface. The experiments show that the C60 molecules act as deep trap states when in direct contact with the perovskite. It is further demonstrated that by reducing the surface coverage of C60, the radiative efficiency of the bare perovskite layer can be retained. The findings of this work pave the way toward overcoming one of the most critical remaining performance losses in perovskite solar cells.
Nonradiative recombination induced by C60 is limiting the performance of pin type perovskite solar cells and remains poorly understood. In this manuscript, the possible recombination pathways are systematically examined and it is discovered that across‐interface recombination dominates. A point contact strategy is suggested to circumvent the loss, paving the way to improved pin type perovskite solar cells.
Perovskites offer exciting opportunities to realize efficient multijunction photovoltaic devices. This requires high-V OC and often Br-rich perovskites, which currently suffer from halide ...segregation. Here, we study triple-cation perovskite cells over a wide bandgap range (∼1.5–1.9 eV). While all wide-gap cells (≥1.69 eV) experience rapid phase segregation under illumination, the electroluminescence spectra are less affected by this process. The measurements reveal a low radiative efficiency of the mixed halide phase which explains the V OC losses with increasing Br content. Photoluminescence measurements on nonsegregated partial cell stacks demonstrate that both transport layers (PTAA and C60) induce significant nonradiative interfacial recombination, especially in Br-rich (>30%) samples. Therefore, the presence of the segregated iodide-rich domains is not directly responsible for the V OC losses. Moreover, LiF can only improve the V OC of cells that are primarily limited by the n-interface (≤1.75 eV), resulting in 20% efficient 1.7 eV bandgap cells. However, a simultaneous optimization of the p-interface is necessary to further advance larger bandgap (≥1.75 eV) pin-type cells.
Efficient mixed metal lead‐tin halide perovskites are essential for the development of all‐perovskite tandem solar cells, however they are currently limited by significant short‐circuit current ...losses despite their near optimal bandgap (≈1.25 eV). Herein, the origin of these losses is investigated, using a combination of voltage dependent photoluminescence (PL) timeseries and various charge extraction measurements. It is demonstrated that the Pb/Sn‐perovskite devices suffer from a reduction in the charge extraction efficiency within the first few seconds of operation, which leads to a loss in current and lower maximum power output. In addition, the emitted PL from the device rises on the exact same timescales due to the accumulation of electronic charges in the active layer. Using transient charge extraction measurements, it is shown that these observations cannot be explained by doping‐induced electronic charges but by the movement of mobile ions toward the perovskite/transport layer interfaces, which inhibits charge extraction due to band flattening. Finally, these findings are generalized to lead‐based perovskites, showing that the loss mechanism is universal. This elucidates the negative role mobile ions play in perovskite solar cells and paves a path toward understanding and mitigating a key loss mechanism.
Current losses in perovskite solar cells (PSCs) are investigated using transient photoluminescence and charge extraction measurements. Mobile ions cause a substantial current and efficiency loss by accumulating at the perovskite/transport layer interfaces, which screens the internal electric field. This work elucidates the detrimental impact of mobile ions in PSCs and paves the path toward mitigating this key loss mechanism.
Mobile ions in perovskite photovoltaic devices can hinder performance and cause degradation by impeding charge extraction and screening the internal field. Accurately quantifying mobile ion densities ...remains a challenge and is a highly debated topic. We assess the suitability of several experimental methodologies for determining mobile ion densities by using drift-diffusion simulations. We found that charge extraction by linearly increasing voltage (CELIV) underestimates ion density, but bias-assisted charge extraction (BACE) can accurately reproduce ionic lower than the electrode charge. A modified Mott–Schottky (MS) analysis at low frequencies can provide ion density values for high excess ionic densities, typical for perovskites. The most significant contribution to capacitance originates from the ionic depletion layer rather than the accumulation layer. Using low-frequency MS analysis, we also demonstrate light-induced generation of mobile ions. These methods enable accurate tracking of ionic densities during device aging and a deeper understanding of ionic losses.
Static Disorder in Lead Halide Perovskites Zeiske, Stefan; Sandberg, Oskar J.; Zarrabi, Nasim ...
The journal of physical chemistry letters,
08/2022, Letnik:
13, Številka:
31
Journal Article
Recenzirano
Odprti dostop
In crystalline and amorphous semiconductors, the temperature-dependent Urbach energy can be determined from the inverse slope of the logarithm of the absorption spectrum and reflects the static and ...dynamic energetic disorder. Using recent advances in the sensitivity of photocurrent spectroscopy methods, we elucidate the temperature-dependent Urbach energy in lead halide perovskites containing different numbers of cation components. We find Urbach energies at room temperature to be 13.0 ± 1.0, 13.2 ± 1.0, and 13.5 ± 1.0 meV for single, double, and triple cation perovskite. Static, temperature-independent contributions to the Urbach energy are found to be as low as 5.1 ± 0.5, 4.7 ± 0.3, and 3.3 ± 0.9 meV for the same systems. Our results suggest that, at a low temperature, the dominant static disorder in perovskites is derived from zero-point phonon energy rather than structural disorder. This is unusual for solution-processed semiconductors but broadens the potential application of perovskites further to quantum electronics and devices.
With power conversion efficiencies of perovskite-on-silicon and all-perovskite tandem solar cells increasing at rapid pace, wide bandgap (>1.7 eV) metal-halide perovskites (MHPs) are becoming a major ...focus of academic and industrial photovoltaic research. Compared to their lower bandgap (≤1.6 eV) counterparts, these types of perovskites suffer from higher levels of non-radiative losses in both the bulk material and in device configurations, constraining their efficiencies far below their thermodynamic potential. In this work, we investigate the energy losses in methylammonium (MA) free high-Br-content wide bandgap perovskites by using a combination of THz spectroscopy, steady-state and time-resolved photoluminescence, coupled with drift-diffusion simulations. The investigation of this system allows us to study charge-carrier recombination in these materials and devices in the absence of halide segregation due to the photostabilty of formamidinium-cesium based lead halide perovskites. We find that these perovskites are characterised by large non-radiative recombination losses in the bulk material and that the interfaces with transport layers in solar cell devices strongly limit their open-circuit voltage. In particular, we discover that the interface with the hole transport layer performs particularly poorly, in contrast to 1.6 eV bandgap MHPs which are generally limited by the interface with the electron-transport layer. To overcome these losses, we incorporate and investigate the recombination mechanisms present with perovskites treated with the ionic additive 1-butyl-1-methylpipiderinium tetrafluoroborate. We find that this additive not only improves the radiative efficiency of the bulk perovskite, but also reduces the non-radiative recombination at both the hole and electron transport layer interfaces of full photovoltaic devices. In addition to unravelling the beneficial effect of this specific treatment, we further optimise our solar cells by introducing an additional LiF interface treatment at the electron transport layer interface. Together these treatments enable MA-free 1.79 eV bandgap perovskite solar cells with open-circuit voltages of 1.22 V and power conversion efficiencies approaching 17%, which is among the highest reported for this material system.
We identify the limiting factors of wide bandgap metal halide perovskite solar cells. To overcome these losses, we developed an efficient optimisation strategy and outline the necessary steps for the continued development of these perovskites.
Approaches to boost the efficiency and stability of perovskite solar cells often address one singular problem in a specific device configuration. In this work, we utilize a poly(ionic liquid) (PIL) ...to introduce a multi-functional interlayer to improve the device efficiency and stability for different perovskite compositions and architectures. The presence of the PIL at the perovskite surface reduces the non-radiative losses down to 60 meV already in the neat material, indicating effective surface trap passivation, thereby pushing the external photoluminescence quantum yield up to 7%. In devices, the PIL treatment induces a bi-functionality of the surface where insulating areas act as a blocking layer reducing interfacial charge recombination and increasing the
V
OC
, whereas, at the same time, the passivated neighbouring regions provide more efficient charge extraction, increasing the FF. As a result, these solar cells exhibit outstanding
V
OC
and FF values of 1.17 V and 83% respectively, with the best devices reaching conversion efficiencies up to 21.4%. The PIL-treated devices additionally show enhanced stability during maximum power point tracking (>700 h) and unchanged efficiencies after 10 months of shelf storage. By applying the PIL to small and wide bandgap perovskites, and to nip cells, we corroborate the generality of this methodology to improve the efficiency in various cell architectures and perovskite compositions.
In this work, we demonstrate how the use of a poly(ionic liquid) interlayer in combination with perovskite solar cells provides a bi-functionality of the surface allowing to concomitantly reduce the energy losses, enhance the charge extraction and improve the device stability all at once.
Combining high efficiency with good radiation tolerance, perovskite solar cells (PSCs) are promising candidates to upend expanding space photovoltaic (PV) technologies. Successful employment in a ...Near-Earth space environment, however, requires high resistance against atomic oxygen (AtOx). This work unravels AtOx-induced degradation mechanisms of PSCs with and without phenethylammonium iodide (PEAI) based 2D-passivation and investigates the applicability of ultrathin silicon oxide (SiO) encapsulation as AtOx barrier. AtOx exposure for 2 h degraded the average power conversion efficiency (PCE) of devices without barrier encapsulation by 40% and 43% (w/o and with 2D-PEAI-passivation) of their initial PCE. In contrast, devices with a SiO-barrier retained over 97% of initial PCE. To understand why 2D-PEAI passivated devices degrade faster than less efficient non-passivated devices, various opto-electrical and structural characterications are conducted. Together, these allowed to decouple different damage mechanisms. Notably, pseudo-J-V curves reveal unchanged high implied fill factors (pFF) of 86.4% and 86.2% in non-passivated and passivated devices, suggesting that degradation of the perovskite absorber itself is not dominating. Instead, inefficient charge extraction and mobile ions, due to a swiftly degrading PEAI interlayer are the primary causes of AtOx-induced device performance degradation in passivated devices, whereas a large ionic FF loss limits non-passivated devices.
Understanding performance losses in all‐perovskite tandem photovoltaics is crucial to accelerate advancements toward commercialization, especially since these tandem devices generally underperform in ...comparison to what is expected from isolated layers and single junction devices. Here, the individual sub‐cells in all‐perovskite tandem stacks are selectively characterized to disentangle the various losses. It is found that non‐radiative losses in the high‐gap subcell dominate the overall recombination in the baseline system, as well as in the majority of literature reports. Through a multi‐faceted approach, the open‐circuit voltage (VOC) of the high‐gap perovskite subcell is enhanced by 120 mV. Employing a novel (quasi) lossless indium oxide interconnect, this enables all‐perovskite tandem solar cells with 2.00 V VOC and 23.7% stabilized efficiency. Reducing transport losses as well as imperfect energy‐alignments boosts efficiencies to 25.2% and 27.0% as identified via subcell selective electro‐ and photo‐luminescence. Finally, it is shown how, having improved the VOC, improving the current density of the low‐gap absorber pushes efficiencies even further, reaching 25.9% efficiency stabilized, with an ultimate potential of 30.0% considering the bulk quality of both absorbers measured using photo‐luminescence. These insights not only show an optimization example but also a generalizable evidence‐based optimization strategy utilizing optoelectronic sub‐cell characterization.
Understanding and minimizing performance losses in all‐perovskite tandem solar cells is crucial to accelerate advancements toward commercialization, yet challenging, since the individual subcells cannot be assessed directly in a monolithic interconnection. Thorough subcell‐selective characterizations provide crucial feedback to improve monolithic all‐perovskite tandem solar cells with optimized subcells and a lossless interconnect toward their true material potential.
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