Lattice Engineering via Transition Metal Ions for Boosting Photoluminescence Quantum Yields of Lead-Free Layered Double Perovskite Nanocrystals.

Lead-free layered double perovskite nanocrystals (NCs), i.e., Cs4M(II)M(III)2Cl12, have recently attracted increasing attention for potential optoelectronic applications due to their low toxicity, direct bandgap nature, and high structural stability. However, the low photoluminescence quantum yield (PLQY, <1%) or even no observed emissions at room temperature have severely blocked the further development of this type of lead-free halide perovskites. Herein, two new layered perovskites, Cs4CoIn2Cl12 (CCoI) and Cs4ZnIn2Cl12 (CZnI), are successfully synthesized at the nanoscale based on previously reported Cs4CuIn2Cl12 (CCuI) NCs, by tuning the M(II) site with different transition metal ions for lattice tailoring. Benefiting from the formation of more self-trapped excitons (STEs) in the distorted lattices, CCoI and CZnI NCs exhibit significantly strengthened STE emissions toward white light compared to the case of almost non-emissive CCuI NCs, by achieving PLQYs of 4.3% and 11.4% respectively. The theoretical and experimental results hint that CCoI and CZnI NCs possess much lower lattice deformation energies than that of reference CCuI NCs, which are favorable for the recombination of as-formed STEs in a radiative way. This work proposes an effective strategy of lattice engineering to boost the photoluminescent properties of lead-free layered double perovskites for their future warm white light-emitting applications.

Contactless analysis of surface passivation and charge transfer at the TiO2-Si interface.

Transition metal oxides are pivotal in enhancing surface passivation and facilitating charge transfer (CT) in silicon based photonic devices, improving their efficacy and affordability through interfacial engineering. This study investigates TiO2/Si heterojunctions prepared by atomic layer deposition (ALD) with different pre-ALD chemical and post-ALD thermal treatments, exploring their influence on the surface passivation and the correlation with the CT at the TiO2-Si interface. Surface passivation quality is evaluated by the photoconductance decay method to study the effective carrier lifetime, while CT from Si to TiO2 is examined by transient reflectance spectroscopy. Surprisingly, the as-deposited TiO2 on HF-treated n-Si (without interfacial SiOx) demonstrates superior surface passivation with an effective lifetime of 1.23 ms, twice that of TiO2/SiOx/n-Si, and a short characteristic CT time of 200 ps, tenfold faster than that of TiO2/SiOx/n-Si. Post-ALD annealing at temperatures approaching the TiO2 crystallization onset re-introduces the SiOx layers in HF-treated samples and induces chemical and structural changes in all the samples which decrease passivation and prolong the CT time and are hence detrimental to the photonic device performance.

Halide Engineering in Mixed Halide Perovskite-Inspired Cu2AgBiI6 for Solar Cells with Enhanced Performance.

Cu2AgBiI6 (CABI) is a promising perovskite-inspired absorber for solar cells due to its direct band gap and high absorption coefficient. However, the nonradiative recombination caused by the high extrinsic trap density limits the performance of CABI-based solar cells. In this work, we employ halide engineering by doping bromide anions (Br-) in CABI thin films, in turn significantly improving the power conversion efficiency (PCE). By introducing Br- in the synthetic route of CABI thin films, we identify the optimum composition as CABI-10Br (with 10% Br at the halide site). The tailored composition appears to reduce the deep trap density as shown by time-resolved photoluminescence and transient absorption spectroscopy characterizations. This leads to a dramatic increase in the lifetime of charge carriers, which therefore improves both the external quantum efficiency and the integrated short-circuit current. The photovoltaic performance shows a significant boost since the PCE under standard 1 sun illumination increases from 1.32 to 1.69% (∼30% relative enhancement). Systematic theoretical and experimental characterizations were employed to investigate the effect of Br- incorporation on the optoelectronic properties of CABI. Our results highlight the importance of mitigating trap states in lead-free perovskite-inspired materials and that Br- incorporation at the halide site is an effective strategy for improving the device performance.

Multi-spectroscopic study of electrochemically-formed oxide-derived gold electrodes.

Oxide-derived metals are produced by reducing an oxide precursor. These materials, including gold, have shown improved catalytic performance over many native metals. The origin of this improvement for gold is not yet understood. In this study, operando non-resonant sum frequency generation (SFG) and ex situ high-pressure X-ray photoelectron spectroscopy (HP-XPS) have been employed to investigate electrochemically-formed oxide-derived gold (OD-Au) from polycrystalline gold surfaces. A range of different oxidizing conditions were used to form OD-Au in acidic aqueous medium (H3PO4, pH = 1). Our electrochemical data after OD-Au is generated suggest that the surface is metallic gold, however SFG signal variations indicate the presence of subsurface gold oxide remnants between the metallic gold surface layer and bulk gold. The HP-XPS results suggest that this subsurface gold oxide could be in the form of Au2O3 or Au(OH)3. Furthermore, the SFG measurements show that with reducing electrochemical treatments the original gold metallic state can be restored, meaning the subsurface gold oxide is released. This work demonstrates that remnants of gold oxide persist beneath the topmost gold layer when the OD-Au is created, potentially facilitating the understanding of the improved catalytic properties of OD-Au.

Surface and optical properties of phase-pure silver iodobismuthate nanocrystals.

The study of surface defects is one of the forefronts of halide perovskite research. In the nanoscale regime, where the surface-to-volume ratio is high, the surface plays a key role in determining the electronic properties of perovskites. Perovskite-inspired silver iodobismuthates are promising photovoltaic absorbers. Herein, we demonstrate the colloidal synthesis of phase pure and highly crystalline AgBiI4 nanocrystals (NCs). Surface-sensitive spectroscopic techniques reveal the rich surface features of the NCs that enable their impressive long-term environmental and thermal stabilities. Notably, the surface termination and its passivation effects on the electronic properties of AgBiI4 are investigated. Our atomistic simulations suggest that a bismuth iodide-rich surface, as in the case of AgBiI4 NCs, does not introduce surface trap states within the band gap region of AgBiI4, unlike a silver iodide-rich surface. These findings may encourage the investigation of surfaces of other lead-free perovskite-inspired materials.

Antimony-Bismuth Alloying: The Key to a Major Boost in the Efficiency of Lead-Free Perovskite-Inspired Photovoltaics.

The perovskite-inspired Cu2 AgBiI6 (CABI) material has been gaining increasing momentum as photovoltaic (PV) absorber due to its low toxicity, intrinsic air stability, direct bandgap, and a high absorption coefficient in the range of 105  cm-1 . However, the power conversion efficiency (PCE) of existing CABI-based PVs is still seriously constrained by the presence of both intrinsic and surface defects. Herein, antimony (III) (Sb3+ ) is introduced into the octahedral lattice sites of the CABI structure, leading to CABI-Sb with larger crystalline domains than CABI. The alloying of Sb3+ with bismuth (III) (Bi3+ ) induces changes in the local structural symmetry that dramatically increase the formation energy of intrinsic defects. Light-intensity dependence and electron impedance spectroscopic studies show reduced trap-assisted recombination in the CABI-Sb PV devices. CABI-Sb solar cells feature a nearly 40% PCE enhancement (from 1.31% to 1.82%) with respect to the CABI devices mainly due to improvement in short-circuit current density. This work will promote future compositional design studies to enhance the intrinsic defect tolerance of next-generation wide-bandgap absorbers for high-performance and stable PVs.

Influence of the photodeposition sequence on the photocatalytic activity of plasmonic Ag-Au/TiO2 nanocomposites.

Bimetallic Ag-Au/TiO2 nanocomposites were synthesized by sequential photodeposition in order to investigate the effect of surface plasmon resonance (SPR) properties on photocatalytic activity for solar water splitting and methylene blue (MB) degradation. The photodeposition times were optimized for monometallic Ag/TiO2 and Au/TiO2 nanocomposites to yield maximum SPR absorption in the visible range. It was found that the photocatalytic activity of bimetallic Ag-Au/TiO2 nanocomposites outperformed monometallic nanocomposites only when Au was photodeposited first on TiO2, which was attributed to Au-core-Ag-shell nanoparticle morphology. In contrast, reversing the photodeposition order resulted in Ag-Au alloy nanoparticle morphology, which was mediated by the galvanic replacement reaction during the second photodeposition. Alloying was not beneficial to the photocatalytic activity. These results demonstrate alloying during sequential photodeposition providing new insights for the synthesis of TiO2-based photocatalysts with plasmon-enhanced absorption in the visible range.

Enhancing the Microstructure of Perovskite-Inspired Cu-Ag-Bi-I Absorber for Efficient Indoor Photovoltaics.

Lead-free perovskite-inspired materials (PIMs) are gaining attention in optoelectronics due to their low toxicity and inherent air stability. Their wide bandgaps (≈2 eV) make them ideal for indoor light harvesting. However, the investigation of PIMs for indoor photovoltaics (IPVs) is still in its infancy. Herein, the IPV potential of a quaternary PIM, Cu2 AgBiI6 (CABI), is demonstrated upon controlling the film crystallization dynamics via additive engineering. The addition of 1.5 vol% hydroiodic acid (HI) leads to films with improved surface coverage and large crystalline domains. The morphologically-enhanced CABI+HI absorber leads to photovoltaic cells with a power conversion efficiency of 1.3% under 1 sun illumination-the highest efficiency ever reported for CABI cells and of 4.7% under indoor white light-emitting diode lighting-that is, within the same range of commercial IPVs. This work highlights the great potential of CABI for IPVs and paves the way for future performance improvements through effective passivation strategies.

Moisture-Assisted near-UV Emission Enhancement of Lead-Free Cs4CuIn2Cl12 Double Perovskite Nanocrystals.

Lead-based halide perovskite nanocrystals (NCs) are recognized as emerging emissive materials with superior photoluminescence (PL) properties. However, the toxicity of lead and the swift chemical decomposition under atmospheric moisture severely hinder their commercialization process. Herein, we report the first colloidal synthesis of lead-free Cs4CuIn2Cl12 layered double perovskite NCs via a facile moisture-assisted hot-injection method stemming from relatively nontoxic precursors. Although moisture is typically detrimental to NC synthesis, we demonstrate that the presence of water molecules in Cs4CuIn2Cl12 synthesis enhances the PL quantum yield (mainly in the near-UV range), induces a morphological transformation from 3D nanocubes to 2D nanoplatelets, and converts the dark transitions to radiative transitions for the observed self-trapped exciton relaxation. This work paves the way for further studies on the moisture-assisted synthesis of novel lead-free halide perovskite NCs for a wide range of applications.

Interface Engineering of TiO2 Photoelectrode Coatings Grown by Atomic Layer Deposition on Silicon.

Titanium dioxide (TiO2) can protect photoelectrochemical (PEC) devices from corrosion, but the fabrication of high-quality TiO2 coatings providing long-term stability has remained challenging. Here, we compare the influence of Si wafer cleaning and postdeposition annealing temperature on the performance of TiO2/n+-Si photoanodes grown by atomic layer deposition (ALD) using tetrakis(dimethylamido)titanium (TDMAT) and H2O as precursors at a growth temperature of 100 °C. We show that removal of native Si oxide before ALD does not improve the TiO2 coating performance under alkaline PEC water splitting conditions if excessive postdeposition annealing is needed to induce crystallization. The as-deposited TiO2 coatings were amorphous and subject to photocorrosion. However, the TiO2 coatings were found to be stable over a time period of 10 h after heat treatment at 400 °C that induced crystallization of amorphous TiO2 into anatase TiO2. No interfacial Si oxide formed during the ALD growth, but during the heat treatment, the thickness of interfacial Si oxide increased to 1.8 nm for all of the samples. Increasing the ALD growth temperature to 150 °C enabled crystallization at 300 °C, which resulted in reduced growth of interfacial Si oxide followed by a 70 mV improvement in the photocurrent onset potential.

Octahedral distortion driven by CsPbI3 nanocrystal reaction temperature - the effects on phase stability and beyond.

Cesium lead iodide (CsPbI3) perovskite nanocrystals (NCs) suffer from a known transformation at room temperature from their red-emitting (black) to non-emitting (yellow) phase, induced by the tilting of PbI6 octahedra. While the reported attempts to stabilize CsPbI3 NCs mainly involve Pb2+-site doping as well as compositional and/or NC surface engineering, the black phase stability in relation only to the variation of the reaction temperature of CsPbI3 NCs is surprisingly overlooked. We report a holistic study of the phase stability of CsPbI3 NCs, encompassing dispersions, films, and even devices by tuning the hot-injection temperature between 120-170 °C. Our findings suggest that the transition from the black to the yellow phase occurs after over a month for NCs synthesized at 150 °C (150@NCs). Structural refinement studies attribute the enhanced stability of 150@NCs to their observed lowest octahedral distortion. The 150@NCs also lead to stable unencapsulated solar cells with unchanged performance upon 26 days of shelf storage in dry air. Our study underlines the importance of scrutinizing synthesis parameters for designing stable perovskite NCs towards long-lasting optoelectronic devices.

Comparison of the heat-treatment effect on carrier dynamics in TiO2 thin films deposited by different methods.

Polycrystalline titanium dioxide thin films are routinely used in a broad range of applications where charge carrier lifetime is essential for their performance but the effects of the fabrication method are rarely considered. Here we compare three popular deposition methods, atomic layer deposition (ALD), ion beam sputtering (IBS), and spray pyrolysis deposition (SPD). In all three cases, 30 nm thin films of TiO2 are prepared, and the as-deposited films show no defined crystal structure and can be classified as amorphous films. Heat treatment (HT) of the films converts all of them to polycrystalline anatase TiO2 as revealed by XRD measurements. A photophysical study was carried out by pico- to nano-second transient absorption pump-probe spectroscopy in transmittance and reflectance modes which allows taking into account the effects due to the photoinduced refractive index changes. This study shows that the HT increases the lifetime of the photo-carriers gradually to a nanosecond time domain (approx. 4 ns) as compared to a few picoseconds of the as-deposited samples. The photo-carrier dynamics of the samples become very similar after heat-treatment, though the topographical features and texture of the films observed with AFM and XRD are quite different. The measured transient absorption spectra of the samples also indicate that the photo-carrier relaxation pathway involves electron and hole trap states with the longest-lived being the hole traps. To evaluate the photoactivity of thin films, methylene blue (MB) photodegradation was tested for all the as-deposited and HT samples and the results showed a 20% higher degradation rate for the IBS HT sample due to the more textured surface.

Lead-Free Cesium Titanium Bromide Double Perovskite Nanocrystals.

Double perovskites are a promising family of lead-free materials that not only replace lead but also enable new optoelectronic applications beyond photovoltaics. Recently, a titanium (Ti)-based vacancy-ordered double perovskite, Cs2TiBr6, has been reported as an example of truly sustainable and earth-abundant perovskite with controversial results in terms of photoluminescence and environmental stability. Our work looks at this material from a new perspective, i.e., at the nanoscale. We demonstrate the first colloidal synthesis of Cs2TiX6 nanocrystals (X = Br, Cl) and observe tunable morphology and size of the nanocrystals according to the set reaction temperature. The Cs2TiBr6 nanocrystals synthesized at 185 °C show a bandgap of 1.9 eV and are relatively stable up to 8 weeks in suspensions. However, they do not display notable photoluminescence. The centrosymmetric crystal structure of Cs2TiBr6 suggests that this material could enable third-harmonic generation (THG) responses. Indeed, we provide a clear evidence of THG signals detected by the THG microscopy technique. As only a few THG-active halide perovskite materials are known to date and they are all lead-based, our findings promote future research on Cs2TiBr6 as well as on other lead-free double perovskites, with stronger focus on currently unexplored nonlinear optical applications.

Manganese Doping Promotes the Synthesis of Bismuth-based Perovskite Nanocrystals While Tuning Their Band Structures.

The doping of halide perovskite nanocrystals (NCs) with manganese cations (Mn2+ ) has recently enabled enhanced stability, novel optical properties, and modulated charge carrier dynamics of the NCs host. However, the influence of Mn doping on the synthetic routes and the band structures of the host has not yet been elucidated. Herein, it is demonstrated that Mn doping promotes a facile, safe, and low-hazard path toward the synthesis of ternary Cs3 Bi2 I9 NCs by effectively inhibiting the impurity phase (i.e., CsI) resulting from the decomposition of the intermediate Cs3 BiI6 product. Furthermore, it is observed that the deepening of the valence band level of the host NCs upon doping at Mn concentration levels varying from 0 to 18.5% (atomic ratio) with respect to the Bi content. As a result, the corresponding Mn-doped NCs solar cells show a higher open-circuit voltage and longer electron lifetime than those employing the undoped perovskite NCs. This work opens new insights on the role of Mn doping in the synthetic route and optoelectronic properties of lead-free halide perovskite NCs for still unexplored applications.

Copper Oxide Microtufts on Natural Fractals for Efficient Water Harvesting.

Hierarchical surfaces that aid in the droplet nucleation, growth, and removal is highly desirable for fog and moisture harvesting applications. Taking inspiration from the unique architecture of leaf skeletons, we present a multiscale surface capable of rapidly nucleating, growing, and directional transport of the water droplets. Copper oxide microtufts were fabricated onto the Ficus religiosa leaf skeletons via electroplating and chemical oxidation techniques. The fabricated surfaces with microtufts had high wettability and very good fog harvesting ability. CuO surfaces tend to become hydrophobic over time because of the adsorption of the airborne species. The surfaces were efficient in fog harvesting even when the hydrophobic coating is present. The overall water collection efficiencies were determined, and the role of the microtufts, fractal structures, and the orientation of leaf veins was investigated. Compared to the planar control surfaces, the noncoated and hydrophobic layer-coated copper oxide microtufts on the leaf skeletons displayed a significant increase in the fog harvesting efficiency. For superhydrophilic skeleton surfaces, the water collection rate was also observed to slightly vary with the vein orientation. The CuO microtufts along with high surface area fractals allowed an effective and sustainable way to capture and transport water. The study is expected to provide valuable insights into the design and fabrication of sustainable and efficient fog harvesting systems.

Optimization of Photogenerated Charge Carrier Lifetimes in ALD Grown TiO2 for Photonic Applications.

Titanium dioxide (TiO2) thin films are widely employed for photocatalytic and photovoltaic applications where the long lifetime of charge carriers is a paramount requirement for the device efficiency. To ensure the long lifetime, a high temperature treatment is used which restricts the applicability of TiO2 in devices incorporating organic or polymer components. In this study, we exploited low temperature (100-150 °C) atomic layer deposition (ALD) of 30 nm TiO2 thin films from tetrakis(dimethylamido)titanium. The deposition was followed by a heat treatment in air to find the minimum temperature requirements for the film fabrication without compromising the carrier lifetime. Femto-to nanosecond transient absorption spectroscopy was used to determine the lifetimes, and grazing incidence X-ray diffraction was employed for structural analysis. The optimal result was obtained for the TiO2 thin films grown at 150 °C and heat-treated at as low as 300 °C. The deposited thin films were amorphous and crystallized into anatase phase upon heat treatment at 300-500 °C. The average carrier lifetime for amorphous TiO2 is few picoseconds but increases to >400 ps upon crystallization at 500 °C. The samples deposited at 100 °C were also crystallized as anatase but the carrier lifetime was <100 ps.

B-Site Co-Alloying with Germanium Improves the Efficiency and Stability of All-Inorganic Tin-Based Perovskite Nanocrystal Solar Cells.

Colloidal lead-free perovskite nanocrystals have recently received extensive attention because of their facile synthesis, the outstanding size-tunable optoelectronic properties, and less or no toxicity in their commercial applications. Tin (Sn) has so far led to the most efficient lead-free solar cells, yet showing highly unstable characteristics in ambient conditions. Here, we propose the synthesis of all-inorganic mixture Sn-Ge perovskite nanocrystals, demonstrating the role of Ge2+ in stabilizing Sn2+ cation while enhancing the optical and photophysical properties. The partial replacement of Sn atoms by Ge atoms in the nanostructures effectively fills the high density of Sn vacancies, reducing the surface traps and leading to a longer excitonic lifetime and increased photoluminescence quantum yield. The resultant Sn-Ge nanocrystals-based devices show the highest efficiency of 4.9 %, enhanced by nearly 60 % compared to that of pure Sn nanocrystals-based devices.

Diversity of TiO2: Controlling the Molecular and Electronic Structure of Atomic-Layer-Deposited Black TiO2.

Visually black, electrically leaky, amorphous titania (am-TiO2) thin films were grown by atomic layer deposition (ALD) for photocatalytic applications. Broad spectral absorbance in the visible range and exceptional conductivity are attributed to trapped Ti3+ in the film. Oxidation of Ti3+ upon heat treatment leads to a drop in conductivity, a color change from black to white, and crystallization of am-TiO2. ALD-grown black TiO2, without any heat treatment, is subject to dissolution in alkaline photoelectrochemical conditions. The best photocatalytic activity for solar water splitting is obtained for completely crystalline white TiO2.

Improved Stability of Atomic Layer Deposited Amorphous TiO2 Photoelectrode Coatings by Thermally Induced Oxygen Defects.

Amorphous titanium dioxide (a-TiO2) combined with an electrocatalyst has shown to be a promising coating for stabilizing traditional semiconductor materials used in artificial photosynthesis for efficient photoelectrochemical solar-to-fuel energy conversion. In this study we report a detailed analysis of two methods of modifying an undoped thin film of atomic layer deposited (ALD) a-TiO2 without an electrocatalyst to affect its performance in water splitting reaction as a protective photoelectrode coating. The methods are high-temperature annealing in ultrahigh vacuum and atomic hydrogen exposure. A key feature in both methods is that they preserve the amorphous structure of the film. Special attention is paid to the changes in the molecular and electronic structure of a-TiO2 induced by these treatments. On the basis of the photoelectrochemical results, the a-TiO2 is susceptible to photocorrosion but significant improvement in stability is achieved after heat treatment in vacuum at temperatures above 500 °C. On the other hand, the hydrogen treatment does not increase the stability despite the ostensibly similar reduction of a-TiO2. The surface analysis allows us to interpret the improved stability to the thermally induced formation of O- species within a-TiO2 that are essentially electronic defects in the anionic framework.