Sustainability pathways for perovskite photovoltaics.

Solar energy is the fastest-growing source of electricity generation globally. As deployment increases, photovoltaic (PV) panels need to be produced sustainably. Therefore, the resource utilization rate and the rate at which those resources become available in the environment must be in equilibrium while maintaining the well-being of people and nature. Metal halide perovskite (MHP) semiconductors could revolutionize PV technology due to high efficiency, readily available/accessible materials and low-cost production. Here we outline how MHP-PV panels could scale a sustainable supply chain while appreciably contributing to a global renewable energy transition. We evaluate the critical material concerns, embodied energy, carbon impacts and circular supply chain processes of MHP-PVs. The research community is in an influential position to prioritize research efforts in reliability, recycling and remanufacturing to make MHP-PVs one of the most sustainable energy sources on the market.

Room-temperature spin injection across a chiral perovskite/III-V interface.

Spin accumulation in semiconductor structures at room temperature and without magnetic fields is key to enable a broader range of optoelectronic functionality1. Current efforts are limited owing to inherent inefficiencies associated with spin injection across semiconductor interfaces2. Here we demonstrate spin injection across chiral halide perovskite/III-V interfaces achieving spin accumulation in a standard semiconductor III-V (AlxGa1-x)0.5In0.5P multiple quantum well light-emitting diode. The spin accumulation in the multiple quantum well is detected through emission of circularly polarized light with a degree of polarization of up to 15 ± 4%. The chiral perovskite/III-V interface was characterized with X-ray photoelectron spectroscopy, cross-sectional scanning Kelvin probe force microscopy and cross-sectional transmission electron microscopy imaging, showing a clean semiconductor/semiconductor interface at which the Fermi level can equilibrate. These findings demonstrate that chiral perovskite semiconductors can transform well-developed semiconductor platforms into ones that can also control spin.

Chiral-structured heterointerfaces enable durable perovskite solar cells.

Mechanical failure and chemical degradation of device heterointerfaces can strongly influence the long-term stability of perovskite solar cells (PSCs) under thermal cycling and damp heat conditions. We report chirality-mediated interfaces based on R-/S-methylbenzyl-ammonium between the perovskite absorber and electron-transport layer to create an elastic yet strong heterointerface with increased mechanical reliability. This interface harnesses enantiomer-controlled entropy to enhance tolerance to thermal cycling-induced fatigue and material degradation, and a heterochiral arrangement of organic cations leads to closer packing of benzene rings, which enhances chemical stability and charge transfer. The encapsulated PSCs showed retentions of 92% of power-conversion efficiency under a thermal cycling test (-40°C to 85°C; 200 cycles over 1200 hours) and 92% under a damp heat test (85% relative humidity; 85°C; 600 hours).

Structural Asymmetry and Chiral-Induced Spin Selectivity in Chiral Palladium-Halide Semiconductors.

Chiral Pb-free metal-halide semiconductors (MHSs) have attracted considerable attention in the field of spintronics due to various interesting spin-related properties and chiral-induced spin selectivity (CISS) effect. Despite their excellent chemical and structural tunability, the material scope and crystal structure of Pb-free chiral MHSs exhibiting the CISS effect are still limited; chiral MHSs that have metal-halide structures of octahedra and tetrahedra are only reported. Here, we report a new class of chiral MHSs, of which palladium (Pd)-halides are formed in 1D square-pyramidal structures or 0D square-planar structures, with a general formula of ((R/S-MBA)2PdBr4)1-x((R/S-MBA)2PdCl4)x (MBA = methylbenzylammonium; x = 0, 0.25, 0.5, 0.75, and 1) for the first time. The crystals adopt the 1D helical chain of Pd-halide square-pyramid (for x = 0, 0.25, 0.5, and 0.75) and 0D structure of Pd-halide square-plane (for x = 1). All the Pd-halides are distorted by the interaction between the halide and the chiral organic ammonium and arranged in a noncentrosymmetric position. Circular dichroism (CD) for ((R/S-MBA)2PdBr4)1-x((R/S-MBA)2PdCl4)x indicates that chirality was transferred from chiral organic ammonium to Pd-halide inorganics. ((R-MBA)2PdBr4)1-x((R-MBA)2PdCl4)x (x = 0, 0.25, 0.5, and 0.75) shows a distortion index of 0.127-0.128, which is the highest value among the previously reported chiral MHSs to the best of our knowledge. We also find that (R/S-MBA)2Pd(Br1-xClx)4 crystals grow along the out-of-plane direction during spin coating and have high c-axis orientation and crystallinity, and (R/S-MBA)2Pd(Br1-xClx)4 (x = 0 and 0.5) crystals exhibit a CISS effect in polycrystalline bulk films. These results demonstrate the possibility of a new metal-halide series with square-planar structures or square-pyramidal structures for future spintronic applications.

Unraveling radiation damage and healing mechanisms in halide perovskites using energy-tuned dual irradiation dosing.

Perovskite photovoltaics have been shown to recover, or heal, after radiation damage. Here, we deconvolve the effects of radiation based on different energy loss mechanisms from incident protons which induce defects or can promote efficiency recovery. We design a dual dose experiment first exposing devices to low-energy protons efficient in creating atomic displacements. Devices are then irradiated with high-energy protons that interact differently. Correlated with modeling, high-energy protons (with increased ionizing energy loss component) effectively anneal the initial radiation damage, and recover the device efficiency, thus directly detailing the different interactions of irradiation. We relate these differences to the energy loss (ionization or non-ionization) using simulation. Dual dose experiments provide insight into understanding the radiation response of perovskite solar cells and highlight that radiation-matter interactions in soft lattice materials are distinct from conventional semiconductors. These results present electronic ionization as a unique handle to remedying defects and trap states in perovskites.

Stabilized hole-selective layer for high-performance inverted p-i-n perovskite solar cells.

P-i-n geometry perovskite solar cells (PSCs) offer simplified fabrication, greater amenability to charge extraction layers, and low-temperature processing over n-i-p counterparts. Self-assembled monolayers (SAMs) can enhance the performance of p-i-n PSCs but ultrathin SAMs can be thermally unstable. We report a thermally robust hole-selective layer comprised of nickel oxide (NiOx) nanoparticle film with a surface-anchored (4-(3,11-dimethoxy-7H-dibenzo[c,g]carbazol-7-yl)butyl)phosphonic acid (MeO-4PADBC) SAM that can improve and stabilize the NiOx/perovskite interface. The energetic alignment and favorable contact and binding between NiOx/MeO-4PADBC and perovskite reduced the voltage deficit of PSCs with various perovskite compositions and led to strong interface toughening effects under thermal stress. The resulting 1.53-electron-volt devices achieved 25.6% certified power conversion efficiency and maintained >90% of their initial efficiency after continuously operating at 65 degrees Celsius for 1200 hours under 1-sun illumination.

Introduction to halide perovskite optoelectronics.

An introduction to the Nanoscale themed collection on halide perovskite nanomaterials for optoelectronic applications, featuring a variety of articles that highlight the latest developments to address ongoing challenges in the field.

Ultrafast Carrier Drift Transport Dynamics in CsPbI3 Perovskite Nanocrystalline Thin Films.

We study the early time carrier drift dynamics in CsPbI3 nanocrystal thin films with a sub 25 ps time resolution. Prior to trapping, carriers exhibit band-like transport characteristics, which is similar to those of traditional semiconductor solar absorbers including Si and GaAs due to optical phonon and carrier scattering at high temperatures. In contrast to the popular polaron scattering mechanism, the CsPbI3 nanocrystal thin film demonstrates the strongest optical phonon scattering mechanism among other inorganic-organic hybrid perovskites, Si, and GaAs. This ultrafast dynamics study establishes a foundation for understanding the fundamental carrier drift properties that drive perovskite nanocrystal optoelectronics.

Electrochemical Doping of Halide Perovskites by Noble Metal Interstitial Cations.

Metal halide perovskites are an attractive class of semiconductors, but it has proven difficult to control their electronic doping by conventional strategies due to screening and compensation by mobile ions or ionic defects. Noble-metal interstitials represent an under-studied class of extrinsic defects that plausibly influence many perovskite-based devices. In this work, doping of metal halide perovskites is studied by electrochemically formed Au+ interstitial ions, combining experimental data on devices with a computational analysis of Au+ interstitial defects based on density functional theory (DFT). Analysis suggests that Au+ cations can be easily formed and migrate through the perovskite bulk via the same sites as iodine interstitials (Ii + ). However, whereas Ii + compensates n-type doping by electron capture, the noble-metal interstitials act as quasi-stable n-dopants. Experimentally, voltage-dependent, dynamic doping by current density-time (J-t), electrochemical impedance, and photoluminescence measurements are characterized. These results provide deeper insight into the potential beneficial and detrimental impacts of metal electrode reactions on long-term performance of perovskite photovoltaic and light-emitting diodes, as well as offer an alternative doping explanation for the valence switching mechanism of halide-perovskite-based neuromorphic and memristive devices.

Thermal tolerance of perovskite quantum dots dependent on A-site cation and surface ligand.

A detailed picture of temperature dependent behavior of CsxFA1-xPbI3 perovskite quantum dots across the composition range is constructed by performing in situ optical spectroscopic and structural measurements, supported by theoretical calculations that focus on the relation between A-site chemical composition and surface ligand binding. The thermal degradation mechanism depends not only on the exact chemical composition, but also on the ligand binding energy. The thermal degradation of Cs-rich perovskite quantum dots is induced by a phase transition from black γ-phase to yellow δ-phase, while FA-rich perovskite quantum dots with higher ligand binding energy directly decompose into PbI2. Quantum dot growth to form large bulk size grain is observed for all CsxFA1-xPbI3 perovskite quantum dots at elevated temperatures. In addition, FA-rich quantum dots possess stronger electron-longitudinal optical phonon coupling, suggesting that photogenerated excitons in FA-rich quantum dots have higher probability to be dissociated by phonon scattering compared to Cs-rich quantum dots.

Metal Halide Perovskite Heterostructures: Blocking Anion Diffusion with Single-Layer Graphene.

The development of metal halide perovskite/perovskite heterostructures is hindered by rapid interfacial halide diffusion leading to mixed alloys rather than sharp interfaces. To circumvent this outcome, we developed an ion-blocking layer consisting of single-layer graphene (SLG) deposited between the metal halide perovskite layers and demonstrated that it effectively blocks anion diffusion in a CsPbBr3/SLG/CsPbI3 heterostructure. Spatially resolved elemental analysis and spectroscopic measurements demonstrate the halides do not diffuse across the interface, whereas control samples without the SLG show rapid homogenization of the halides and loss of the sharp interface. Ultraviolet photoelectron spectroscopy, DFT calculations, and transient absorbance spectroscopy indicate the SLG has little electronic impact on the individual semiconductors. In the CsPbBr3/SLG/CsPbI3, we find a type I band alignment that supports transfer of photogenerated carriers across the heterointerface. Light-emitting diodes (LEDs) show electroluminescence from both the CsPbBr3 and CsPbI3 layers with no evidence of ion diffusion during operation. Our approach provides opportunities to design novel all-perovskite heterostructures to facilitate the control of charge and light in optoelectronic applications.

Regulating surface potential maximizes voltage in all-perovskite tandems.

The open-circuit voltage (VOC) deficit in perovskite solar cells is greater in wide-bandgap (over 1.7 eV) cells than in perovskites of roughly 1.5 eV (refs. 1,2). Quasi-Fermi-level-splitting measurements show VOC-limiting recombination at the electron-transport-layer contact3-5. This, we find, stems from inhomogeneous surface potential and poor perovskite-electron transport layer energetic alignment. Common monoammonium surface treatments fail to address this; as an alternative, we introduce diammonium molecules to modify perovskite surface states and achieve a more uniform spatial distribution of surface potential. Using 1,3-propane diammonium, quasi-Fermi-level splitting increases by 90 meV, enabling 1.79 eV perovskite solar cells with a certified 1.33 V VOC and over 19% power conversion efficiency (PCE). Incorporating this layer into a monolithic all-perovskite tandem, we report a record VOC of 2.19 V (89% of the detailed balance VOC limit) and over 27% PCE (26.3% certified quasi-steady state). These tandems retained more than 86% of their initial PCE after 500 h of operation.

Temperature-Dependent Carrier Extraction and the Effects of Excitons on Emission and Photovoltaic Performance in Cs0.05FA0.79MA0.16Pb(I0.83Br0.17)3 Solar Cells.

The photovoltaic parameters of triple cation perovskite [Cs0.05FA0.79MA0.16Pb(I0.83Br0.17)3] solar cells are investigated focusing on the electro-optical properties and differences in performance at low and high temperatures. The signature of a parasitic barrier to carrier extraction is observed at low temperatures, which results in a loss of performance at T < 200 K. Intensity-dependent measurements indicate extraction across this parasitic interface is limited by a combination of the exciton binding energy and thermionic emission. However, the photovoltaic performance of the device is recovered at low intensity─where the photocarrier generation rate threshold is lower than the thermionic extraction rate. Loss of solar cell performance is also observed to be strongly correlated to an increase in photoluminescence intensity, indicating inhibited carrier extraction results in strong radiative recombination and that these systems do not appear to be limited by significant thermally activated non-radiative processes. Evidence of limited carrier extraction due to excitonic effects is also observed with a strong anti-correlation in photoluminescence and carrier extraction observed at lower temperatures.

Area-Scalable Zn2SnO4 Electron Transport Layer for Highly Efficient and Stable Perovskite Solar Modules.

The development of a scalable chemical bath deposition (CBD) process facilitates the realization of electron-transporting layers (ETLs) for large-area perovskite solar modules (PSMs). Herein, a method to prepare a uniform and scalable thick Zn2SnO4 ETL by CBD, which yielded high-performance PSMs, is reported. This Zn2SnO4 ETL exhibits excellent electrical properties and enhanced optical transmittance in the visible region. Moreover, the Zn2SnO4 ETL influences the perovskite layer formation, yielding enhanced crystallinity, increased grain size, and a smoother surface, thus facilitating electron extraction and collection from the perovskite to the ETL. Zn2SnO4 thereby yields PSMs with a remarkable photovoltaic performance, low hysteresis index, and high device reproducibility. The champion PSM exhibited a power conversion efficiency (PCE) of 22.59%, being among the highest values published so far. In addition, the CBD Zn2SnO4-based PSMs exhibit high stability, retaining more than 88% of initial efficiency over 1000 h under continuous illumination. This demonstrates that CBD Zn2SnO4 is an appropriate ETL for high-efficiency PSMs and a viable new process for their industrialization.

Perovskite solar cells can take the heat.

Layered surface structure adds durability to packaged perovskite cells.

Colloidal Quantum Dot Solar Cells: Progressive Deposition Techniques and Future Prospects on Large-Area Fabrication.

Colloidally grown nanosized semiconductors yield extremely high-quality optoelectronic materials. Many examples have pointed to near perfect photoluminescence quantum yields, allowing for technology-leading materials such as high purity color centers in display technology. Furthermore, because of high chemical yield, and improved understanding of the surfaces, these materials, particularly colloidal quantum dots (QDs) can also be ideal candidates for other optoelectronic applications. Given the urgent necessity toward carbon neutrality, electricity from solar photovoltaics will play a large role in the power generation sector. QDs are developed and shown dramatic improvements over the past 15 years as photoactive materials in photovoltaics with various innovative deposition properties which can lead to exceptionally low-cost and high-performance devices. Once the key issues related to charge transport in optically thick arrays are addressed, QD-based photovoltaic technology can become a better candidate for practical application. In this article, the authors show how the possibilities of different deposition techniques can bring QD-based solar cells to the industrial level and discuss the challenges for perovskite QD solar cells in particular, to achieve large-area fabrication for further advancing technology to solve pivotal energy and environmental issues.

Probing the Origin of the Open Circuit Voltage in Perovskite Quantum Dot Photovoltaics.

Perovskite quantum dots (PQDs) have many properties that make them attractive for optoelectronic applications, including expanded compositional tunability and crystallographic stabilization. While they have not achieved the same photovoltaic (PV) efficiencies of top-performing perovskite thin films, they do reproducibly show high open circuit voltage (VOC) in comparison. Further understanding of the VOC attainable in PQDs as a function of surface passivation, contact layers, and PQD composition will further progress the field and may lend useful lessons for non-QD perovskite solar cells. Here, we use photoluminescence-based spectroscopic techniques to understand and identify the governing physics of the VOC in CsPbI3 PQDs. In particular, we probe the effect of the ligand exchange and contact interfaces on the VOC and free charge carrier concentration. The free charge carrier concentration is orders of magnitude higher than in typical perovskite thin films and could be tunable through ligand chemistry. Tuning the PQD A-site cation composition via replacement of Cs+ with FA+ maintains the background carrier concentration but reduces the trap density by up to a factor of 40, reducing the VOC deficit. These results dictate how to improve PQD optoelectronic properties and PV device performance and explain the reduced interfacial recombination observed by coupling PQDs with thin-film perovskites for a hybrid absorber layer.

Combined Precursor Engineering and Grain Anchoring Leading to MA-Free, Phase-Pure, and Stable α-Formamidinium Lead Iodide Perovskites for Efficient Solar Cells.

α-Formamidinium lead iodide (α-FAPbI3 ) is one of the most promising candidate materials for high-efficiency and thermally stable perovskite solar cells (PSCs) owing to its outstanding optoelectrical properties and high thermal stability. However, achieving a stable form of α-FAPbI3 where both the composition and the phase are pure is very challenging. Herein, we report on a combined strategy of precursor engineering and grain anchoring to successfully prepare methylammonium (MA)-free and phase-pure stable α-FAPbI3 films. The incorporation of volatile FA-based additives in the precursor solutions completely suppresses the formation of non-perovskite δ-FAPbI3 during film crystallization. Grains of the desired α-phase are anchored together and stabilized when 4-tert-butylbenzylammonium iodide is permeated into the α-FAPbI3 film interior via grain boundaries. This cooperative scheme leads to a significantly increased efficiency close to 21 % for FAPbI3 perovskite solar cells. Moreover, the stabilized PSCs exhibit improved thermal stability and maintained ≈90 % of their initial efficiency after storage at 50 °C for over 1600 hours.