Enhanced Thermal Stability of Planar Perovskite Solar Cells Through Triphenylphosphine Interface Passivation.

While extensive research has driven the rapid efficiency trajectory noted to date for organic-inorganic perovskite solar cells (PSCs), their thermal stability remains one of the key issues hindering their commercialization. Herein, a significant reduction in surface defects (a precursor to perovskite instability) could be attained by introducing triphenylphosphine (TPP), an effective Lewis base passivator, to the vulnerable perovskite/spiro-OMeTAD interface. Not only did TPP passivation enable a high power conversion efficiency (PCE) of 20.22 % to be achieved, these devices also exhibited superior ambient and thermal stability. Unlike the pristine device, which exhibited a sharp descend to 16 % of its initial PCE on storing in relative humidity of 10 %, at 85 °C for more than 720 h, the TPP-passivated devices retained 71 % of its initial PCE. Hence, this study presents a facile yet excellent approach to attain high-performing yet thermally stable PSCs.

Colorful Perovskite Solar Cells: Progress, Strategies, and Potentials.

In the past few years, a large variety of perovskite solar cells (PSCs) with vivid and well-distinguished color hues have been demonstrated. In this Perspective, we compare different strategies employed to realize colorful PSCs both in opaque and semitransparent designs. The approaches used to modulate the PSCs' colorful appearance can be divided into two main categories: the first one based on the modifications of their internal layers (i.e., absorber, electron- and/or hole-transporting layers, and electrodes), while the second is based on the addition of external colored or nanostructured films to the standard PSCs. The advantages and bottlenecks of each strategy are discussed in terms of PSCs' color tunability, transparency, photovoltaic performances, fabrication processes feasibility, and scalability, in view of suitable applications in an urban context for building-integrated photovoltaics.

Bifacial, Color-Tunable Semitransparent Perovskite Solar Cells for Building-Integrated Photovoltaics.

Recently, semitransparent perovskite solar cells (ST-PSCs) have received overwhelming attention due to their potential applications in building-integrated photovoltaics (BIPV) and in tandem solar cells. The best ST-PSCs, despite the high efficiency achieved, still show limited bifacial properties and lack esthetic properties. Here, we have demonstrated efficient bifacial colorful ST-PSCs using copper thiocyanate (CuSCN), as a hole-transporting material, in an n-i-p architecture. The n-i-p ST-PSCs exhibit the highest reported bifacial factor of 93.7% and achieve a bifacial equivalent efficiency of 22.1% when illuminated under 1 sun standard conditions on the front side and with a reflected albedo of ∼54.4% from the back side. We have also demonstrated that the colorful appearance of CuSCN-based ST-PSCs can be easily tuned across the entire visible spectrum by tuning either the indium tin oxide (ITO) or the CuSCN thickness without affecting their final efficiency. The wide colorful tunability and excellent bifacial photovoltaic behavior of CuSCN-based ST-PSCs make them a promising candidate for BIPV applications.

Ultrafast long-range spin-funneling in solution-processed Ruddlesden-Popper halide perovskites.

Room-temperature spin-based electronics is the vision of spintronics. Presently, there are few suitable material systems. Herein, we reveal that solution-processed mixed-phase Ruddlesden-Popper perovskite thin-films transcend the challenges of phonon momentum-scattering that limits spin-transfer in conventional semiconductors. This highly disordered system exhibits a remarkable efficient ultrafast funneling of photoexcited spin-polarized excitons from two-dimensional (2D) to three-dimensional (3D) phases at room temperature. We attribute this efficient exciton relaxation pathway towards the lower energy states to originate from the energy transfer mediated by intermediate states. This process bypasses the omnipresent phonon momentum-scattering in typical semiconductors with stringent band dispersion, which causes the loss of spin information during thermalization. Film engineering using graded 2D/3D perovskites allows unidirectional out-of-plane spin-funneling over a thickness of ~600 nm. Our findings reveal an intriguing family of solution-processed perovskites with extraordinary spin-preserving energy transport properties that could reinvigorate the concepts of spin-information transfer.

Highly Efficient Semitransparent Perovskite Solar Cells for Four Terminal Perovskite-Silicon Tandems.

Tandem solar cells (SCs) based on perovskite and silicon represent an exciting possibility for a breakthrough in photovoltaics, enhancing SC power conversion efficiency (PCE) beyond the single-junction limit while keeping the production cost low. A critical aspect to push the tandem PCE close to its theoretical limit is the development of high-performing semitransparent perovskite top cells, which also allow suitable near-infrared transmission. Here, we have developed highly efficient semitransparent perovskite SCs (PSCs) based on both mesoporous and planar architectures, employing Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 and FA0.87Cs0.13PbI2Br perovskites with band gaps of 1.58 and 1.72 eV, respectively, which achieved PCEs well above 17 and 14% by detailed control of the deposition methods, thickness, and optical transparency of the interlayers and the semitransparent electrode. By combining our champion 1.58 eV PSCs (PCE of 17.7%) with an industrial-relevant low-cost n-type Si SCs, a four-terminal (4T) tandem efficiency of 25.5% has been achieved. Moreover, for the first time, 4T tandem SCs' performances have been measured in the low light intensity regime, achieving a PCE of 26.6%, corresponding to revealing a relative improvement above 9% compared to the standard 1 sun illumination condition. These results are very promising for their implementation under field-operating conditions.

Coherent Spin and Quasiparticle Dynamics in Solution-Processed Layered 2D Lead Halide Perovskites.

Layered 2D halide perovskites with their alternating organic and inorganic atomic layers that form a self-assembled quantum well system are analogues of the purely inorganic 2D transition metal dichalcogenides. Within their periodic structures lie a hotbed of photophysical phenomena such as dielectric confinement effect, optical Stark effect, strong exciton-photon coupling, etc. Detailed understanding into the strong light-matter interactions in these hybrid organic-inorganic semiconductor systems remains modest. Herein, the intricate coherent interplay of exciton, spin, and phonon dynamics in (C6H5C2H4NH3)2PbI4 thin films using transient optical spectroscopy is explicated. New insights into the hotly debated origins of transient spectral features, relaxation pathways, ultrafast spin relaxation via exchange interaction, and strong coherent exciton-phonon coupling are revealed from the detailed phenomenological modeling. Importantly, this work unravels the complex interplay of spin-quasiparticle interactions in these layered 2D halide perovskites with large spin-orbit coupling.

Tunable room-temperature spin-selective optical Stark effect in solution-processed layered halide perovskites.

Ultrafast spin manipulation for opto-spin logic applications requires material systems that have strong spin-selective light-matter interaction. Conventional inorganic semiconductor nanostructures [for example, epitaxial II to VI quantum dots and III to V multiple quantum wells (MQWs)] are considered forerunners but encounter challenges such as lattice matching and cryogenic cooling requirements. Two-dimensional halide perovskite semiconductors, combining intrinsic tunable MQW structures and large oscillator strengths with facile solution processability, can offer breakthroughs in this area. We demonstrate novel room-temperature, strong ultrafast spin-selective optical Stark effect in solution-processed (C6H4FC2H4NH3)2PbI4 perovskite thin films. Exciton spin states are selectively tuned by ~6.3 meV using circularly polarized optical pulses without any external photonic cavity (that is, corresponding to a Rabi energy of ~55 meV and equivalent to applying a 70 T magnetic field), which is much larger than any conventional system. The facile halide and organic replacement in these perovskites affords control of the dielectric confinement and thus presents a straightforward strategy for tuning light-matter coupling strength.

Modulating carrier dynamics through perovskite film engineering.

Precise morphological control in perovskite films is key to high performance photovoltaic and light emitting devices. However, a clear understanding of the interplay of morphological effects from substrate/perovskite antisolvent treatments on the charge dynamics is still severely lacking. Through detailed ultrafast optical spectroscopy, we correlate the morphology-kinetics relationship in a combination of substrate/film treated samples (i.e., plasma-cleaned vs. piranha-etched substrates and solvent (toluene)-engineered (or toluene anti-solvent treated) perovskite films). Our findings reveal that toluene-dripped treatment has a more pronounced influence on the morphology of perovskite films prepared on plasma-cleaned substrates over those on piranha-etched substrates. Surprisingly, the highly effective toluene-dripping/washing approach reported in the literature increases the surface trap densities of perovskite films. Despite the marked improvements in the surface morphology of the toluene-dripped films, there is only a slight improvement in the carrier relaxation lifetimes - likely due to the competition between the morphology improvements and the increased surface trap densities. In addition, the injection of photoexcited holes to spiro-OMeTAD from toluene-dripped films on piranha-etched substrates is inhibited, possibly due to a realignment of the energy bands. Nonetheless, piranha-etching of the substrates could possibly offer an approach to improve the balance between the electron and hole diffusion lengths in the perovskite film. Importantly, our findings would help unravel the complex relationship of substrate/film treatments on the morphology and charge kinetics in perovskite thin films.

Spectral Features and Charge Dynamics of Lead Halide Perovskites: Origins and Interpretations.

Lead halide perovskite solar cells are presently the forerunner among the third generation solution-processed photovoltaic technologies. With efficiencies exceeding 20% and low production costs, they are prime candidates for commercialization. Critical insights into their light harvesting, charge transport, and loss mechanisms have been gained through time-resolved optical probes such as femtosecond transient absorption spectroscopy (fs-TAS), transient photoluminescence spectroscopy, and time-resolved terahertz spectroscopy. Specifically, the discoveries of long balanced electron-hole diffusion lengths and gain properties in halide perovskites underpin their significant roles in uncovering structure-function relations and providing essential feedback for materials development and device optimization. In particular, fs-TAS is becoming increasingly popular in perovskite characterization studies, with commercial one-box pump-probe systems readily available as part of a researcher's toolkit. Although TAS is a powerful probe in the study of charge dynamics and recombination mechanisms, its instrumentation and data interpretation can be daunting even for experienced researchers. This issue is exacerbated by the sensitive nature of halide perovskites where the kinetics are especially susceptible to pump fluence, sample preparation and handling and even degradation effects that could lead to disparate conclusions. Nonetheless, with end-users having a clear understanding of TAS's capabilities, subtleties, and limitations, cutting-edge work with deep insights can still be performed using commercial setups as has been the trend for ubiquitous spectroscopy instruments like absorption, fluorescence, and transient photoluminescence spectrometers. Herein, we will first briefly examine the photophysical processes in lead halide perovskites, highlighting their novel properties. Next, we proceed to give a succinct overview of the fundamentals of pump-probe spectroscopy in relation to the spectral features of halide perovskites and their origins. In the process, we emphasize some key findings of seminal photophysical studies and draw attention to the interpretations that remain divergent and the open questions. This is followed by a general description into how we prepare and conduct the TAS characterization of CH3NH3PbI3 thin films in our laboratory with specific discussions into the potential pitfalls and the influence of thin film processing on the kinetics. Lastly, we conclude with our views on the challenges and opportunities from the photophysical perspective for the field and our expectations for systems beyond lead halide perovskites.

Lead-Free MA2CuCl(x)Br(4-x) Hybrid Perovskites.

Despite their extremely good performance in solar cells with efficiencies approaching 20% and the emerging application for light-emitting devices, organic-inorganic lead halide perovskites suffer from high content of toxic, polluting, and bioaccumulative Pb, which may eventually hamper their commercialization. Here, we present the synthesis of two-dimensional (2D) Cu-based hybrid perovskites and study their optoelectronic properties to investigate their potential application in solar cells and light-emitting devices, providing a new environmental-friendly alternative to Pb. The series (CH3NH3)2CuCl(x)Br(4-x) was studied in detail, with the role of Cl found to be essential for stabilization. By exploiting the additional Cu d-d transitions and appropriately tuning the Br/Cl ratio, which affects ligand-to-metal charge transfer transitions, the optical absorption in this series of compounds can be extended to the near-infrared for optimal spectral overlap with the solar irradiance. In situ formation of Cu(+) ions was found to be responsible for the green photoluminescence of this material set. Processing conditions for integrating Cu-based perovskites into photovoltaic device architectures, as well as the factors currently limiting photovoltaic performance, are discussed: among them, we identified the combination of low absorption coefficient and heavy mass of the holes as main limitations for the solar cell efficiency. To the best of our knowledge, this is the first demonstration of the potential of 2D copper perovskite as light harvesters and lays the foundation for further development of perovskite based on transition metals as alternative lead-free materials. Appropriate molecular design will be necessary to improve the material's properties and solar cell performance filling the gap with the state-of-the-art Pb-based perovskite devices.

Interaction and charge transfer between isolated thylakoids and multi-walled carbon nanotubes.

Charge separation in photosynthetic light reactions has gained much interest in an attempt to fabricate biological photovoltaic devices through integration of photosynthetic material and conducting electrodes. Direct interaction between thylakoids, as representatives of photosynthetic materials, and multi-walled carbon nanotubes (MWCNTs) is expected to increase charge transfer. Thylakoids are isolated from spinach leaf chloroplasts and pristine MWCNTs are dispersed in Triton X-100 (TX-100) as a surfactant to retain their electronic properties through non-covalent interactions. The Raman and UV-Vis spectra suggest close interactions between the thylakoids and the MWCNTs. Stable thylakoids including the embedded protein subunits and light harvesting antennas can be detected from the non-shifted 680 nm absorbance peak. The 50% fluorescence quenching in the MWCNTs-thylakoids preparation as compared to thylakoids alone using single wavelength excitation suggests charge transfer between the thylakoids and the MWCNTs.

Incorporation of Cl into sequentially deposited lead halide perovskite films for highly efficient mesoporous solar cells.

Organic-inorganic lead halide perovskites have been widely used as absorbers on mesoporous TiO2 films as well as thin films in planar heterojunction solar cells, yielding very high photovoltaic conversion efficiencies. Both the addition of chloride and sequential deposition methods were successfully employed to enhance the photovoltaic performance. Here, both approaches are combined in a sequential method by spincoating PbCl2 + PbI2 on a mesoporous TiO2 film followed by the perovskite transformation. The role of Cl in determining the optical, electrical, structural and morphological properties is correlated with the photovoltaic performance. The highest photovoltaic efficiency of 14.15% with the V(oc), FF and J(sc) being 1.09 V, 0.65 and 19.91 mA cm(-2) respectively was achieved with 10 mol% of PbCl2 addition due to an increase of the film conductivity induced by a better perovskite morphology. This is linked to an improvement of the hysteresis and reproducibility of the solar cells.