Spectator Exciton Effects in Nanocrystals III: Unveiling the Stimulated Emission Cross Section in Quantum Confined CsPbBr3 Nanocrystals.

Quantifying stimulated emission in semiconductor nanocrystals (NCs) remains challenging due to masking of its effects on pump-probe spectra by excited state absorption and ground state bleaching signals. The absence of this defining photophysical parameter in turn impedes assignment of band edge electronic structure in many of these important fluorophores. Here we employ a generally applicable 3-pulse ultrafast spectroscopic method coined the "Spectator Exciton" (SX) approach to measure stimulated-emission efficiency in quantum confined inorganic perovskite CsPbBr3 NCs, the band edge electronic structure of which is the subject of lively ongoing debate. Our results show that in 5-6 nm CsPbBr3 NCs, a single exciton bleaches more than half of the intense band edge absorption band, while the cross section for stimulated emission from the same state is nearly 6 times weaker. Discussion of these findings in light of several recent electronic structure models for this material proves them unable to simultaneously explain both measures, proving the importance of this new input to resolving this debate. Along with femtosecond time-resolved photoluminescence measurements on the same sample, SX results also verify that biexciton interaction energy is intensely attractive with a magnitude of ∼80 meV. In light of this observation, our previous suggestion that biexciton interaction is repulsive is reassigned to hot phonon induced slowdown of carrier relaxation leading to direct Auger recombination from an excited state. The mechanism behind the extreme slowing of carrier cooling after several stages of exciton recombination remains to be determined.

In Situ Intrinsic Self-Healing of Low Toxic Cs2 ZnX4 (X = Cl, Br) Metal Halide Nanoparticles.

This study reports on the intrinsic and fast self-healing ability of all inorganic, low-toxic Cs2 ZnX4 (X = Cl, Br) metal halide nanoparticles (NPs) when subjected to local heating by electron beam irradiation in high-resolution transmission electron microscopy (HR-TEM). The local heating induces the creation of nanoshells (NSs) following the template of the corresponding NPs, which are subsequently healed back to their original state within several minutes. Energy dispersive spectroscopy (EDS) and fast Fourier transform (FFT) analysis reveal that the composition, phase, and crystallographic structure of the original NPs are restored during the self-healing process, with a thin crystalline layer observed at the bottom of the NSs acting as the healing template. The inelastic scattering of the electron beam energy generates local heat that causes rapid atomic displacement, resulting in atomic mobility that lowers the density of the material and leads to NS formation. A unique insitu TEM heating stage measurement demonstrates the appearance of identical damage and self-healing to those induced by the electron beam. The NPs exhibit excellent stability under ambient conditions for up to a month, making them suitable for self-healing scintillators and other optoelectronic applications that require atomic-scale stability and healing.

Phase Segregation Mechanisms in Mixed-Halide CsPb(BrxI1-x)3 Nanocrystals in Dependence of Their Sizes and Their Initial [Br]:[I] Ratios.

Phase segregation in inorganic CsPb(BrxI1-x)3 nanoparticles (NPs) exhibiting originally a homogeneous [Br]:[I] mixture was investigated by means of in situ transmission electron microscopy (TEM) and evaluated by using multivariate analyses. The colloidal synthesis of the NPs offers good control of the halide ratios on the nanoscale. The spatially resolved TEM investigations were correlated with integral photoluminescence measurements. By this approach, the halide-segregation processes and their spatial distributions can be described as being governed by the interaction of three partial processes: electron- and photon-irradiation-induced iodide oxidation, local differences in band gap energy, and intrinsic lattice strain. Since the oxidation can be induced by both electron-beam and light irradiation, both irradiation types can induce phase segregation in CsPb(BrxI1-x)3 compounds. This makes in situ TEM a valuable tool to monitor phase transformation in corresponding NPs and thin films on the sub-nm scale.

Enhanced LED Performance by Ion Migration in Multiple Quantum Well Perovskite.

Here we study the effect of ion migration on the performance of perovskite light emitting diodes (PeLEDs). We compared aromatic and linear barrier molecules in Ruddlesden-Popper and Dion-Jacobson two-dimensional perovskites having multiple quantum well (MQW) structures. PeLED devices were fabricated by using the same conditions and architecture, while their electroluminescence properties and ion migration behavior were investigated. Impedance spectroscopy measurements were used to analyze the PeLEDs, which found a direct link between the barrier molecule type, the device efficiency, and ion migration. The best performing LEDs were based on the aromatic barriers, which present dominant inductive impedance, indicating an earlier onset voltage of radiative recombination. These findings present an approach of how to control radiative emission in perovskite LEDs which opens the way for further improvement in PeLEDs and memristors.

A systematic discrepancy between the short circuit current and the integrated quantum efficiency in perovskite solar cells.

Halide perovskites solar cells are now approaching commercialisation. In this transition from academic research towards industrialisation, standardized testing protocols and reliable dissemination of performance metrics are crucial. In this study, we analyze data from over 16,000 publications in the Perovskite Database to investigate the assumed equality between the integrated external quantum efficiency and the short circuit current from JV measurements. We find a systematic discrepancy with the JV-values being on average 4% larger. This discrepancy persists across time, perovskite composition, and device architecture, indicating the need to explore new perovskite physics and update reporting protocols and assumptions in the field.

Formamidinium Halide Perovskite and Carbon Nitride Thin Films Enhance Photoreactivity under Visible Light Excitation.

Photochemical and photocatalytic activity of adsorbates on surfaces is strongly dependent on the nature of a given substrate and its resonant absorption of the (visible) light excitation. An observation is reported here of the visible light photochemical response of formamidinium lead bromide (FAPbBr3) halide perovskite and carbon nitride (CN) thin-film materials (deposited on a SiO2/Si(100) substrate), both of which are known for their photovoltaic and photocatalytic properties. The goal of this study was to investigate the role of the substrate in the photochemical reactivity of an identical probe molecule, ethyl chloride (EC), when excited by pulsed 532 nm laser under ultrahigh vacuum (UHV) conditions. Postirradiation temperature-programmed desorption (TPD) measurements have indicated that the C-Cl bond dissociates following the visible light excitation to form surface-bound fragments that react upon surface heating to form primarily ethane and butane. Temperature-dependent photoluminescence (PL) spectra of the FAPbBr3 films were recorded and decay lifetimes were measured, revealing a correlation between length of PL decay and the photoreactivity yield. We conclude that the FAPbBr3 material with its absorption spectrum in resonance with visible light excitation (532 nm) and longer PL lifetime leads to three times faster (larger cross-section) photoproduct formation compared with that on the CN substrate. These results contrast the behavior under ambient conditions where the CN materials are photochemically superior due, primarily, to their stability within humid environments.

Critical Role of Removing Impurities in Nickel Oxide on High-Efficiency and Long-Term Stability of Inverted Perovskite Solar Cells.

The performance enhancement of inverted perovskite solar cells applying nickel oxide (NiOx ) as the hole transport layer (HTL) has been limited by impurity ions (such as nitrate ions). Herein, we have proposed a strategy to obtain high-quality NiOx nanoparticles via an ionic liquid-assisted synthesis method (NiOx -IL). Experimental and theoretical results illustrate that the cation of the ionic liquid can inhibit the adsorption of impurity ions on nickel hydroxide through a strong hydrogen bond and low adsorption energy, thereby obtaining NiOx -IL HTL with high conductivity and strong hole-extraction ability. Importantly, the removal of impurity ions can effectively suppress the redox reaction between the NiOx film and the perovskite film, thus slowing down the deterioration of device performance. Consequently, the modified inverted device shows a striking efficiency exceeding 22.62 %, and superior stability maintaining 92 % efficiency at a maximum power point tracking under one sun illumination for 1000 h.

Electrical and chemical properties of vacancy-ordered lead free layered double perovskite nanoparticles.

In this work we synthesized vacancy-ordered lead-free layered double perovskite (LDP) nanoparticles. This structure consists of two layers of trivalent metal halide octahedra [B(III)X6]3- separated by a layer of divalent metal [B(II)X6]4- (B is a divalent or trivalent metal). The chemical formula of this structure is based on A4B(II)B(III)2X12 where A is Cs, B(III) is Bi, X is Cl and B(II) is a different ratio between Mn2+ and Cd2+. Well-defined colloidal nanoplates of Cs4CdxMn1-xBi2Cl12 were successfully synthesized. These nanoplates show photoluminescence (PL) in the orange to red region that can be tuned by changing the Cd/Mn ratio. High resolution scanning transmission electron microscopy (HR-STEM) and atomic resolution elemental analysis were performed on these lead free LDP nanoplates revealing two different particle compositions that can be controlled by the Cd/Mn ratio. Ultraviolet Photoelectron Spectroscopy (UPS) and scanning tunneling spectroscopy (STS) reveal the band gap structure of these LDP nanoplates. Density functional theory (DFT) calculations show the existence of [MnCl6]4- in-gap states. While the absorption occurs from the valence band maximum (VBM) to the conduction band minimum (CBM), the emission may occur from the CBM to an in-gap band maximum (IGM), which could explain the PL in the orange to red region of these nanoplates. This work provides a detailed picture of the chemical and electronic properties of LDP nanoparticles.

Semitransparent Perovskite Solar Cells with > 13% Efficiency and 27% Transperancy Using Plasmonic Au Nanorods.

Semitransparent hybrid perovskites open up applications in windows and building-integrated photovoltaics. One way to achieve semitransparency is by thinning the perovskite film, which has several benefits such as cost efficiency and reduction of lead. However, this will result in a reduced light absorbance; therefore, to compromise this loss, it is possible to incorporate plasmonic metal nanostructures, which can trap incident light and locally amplify the electromagnetic field around the resonance peaks. Here, Au nanorods (NRs), which are not detrimental for the perovskite and whose resonance peak overlaps with the perovskite band gap, are deposited on top of a thin (∼200 nm) semitransparent perovskite film. These semitransparent perovskite solar cells with 27% average visible transparency show enhancement in the open-circuit voltage (Voc) and fill factor, demonstrating 13.7% efficiency (improved by ∼6% compared to reference cells). Space-charge limited current, electrochemical impedance spectroscopy (EIS), and Mott-Schottky analyses shed more light on the trap density, nonradiative recombination, and defect density in these Au NR post-treated semitransparent perovskite solar cells. Furthermore, Au NR implementation enhances the stability of the solar cell under ambient conditions. These findings show the ability to compensate for the light harvesting of semitransparent perovskites using the plasmonic effect.

Fabrication of Perovskite Solar Cells with Digital Control of Transparency by Inkjet Printing.

Semitransparency is an attractive and important property in solar cells since it opens new possibilities in a variety of applications such as tandem cell configuration and building-integrated photovoltaics. Metal halide perovskite has the optimal properties to function as the light harvester in solar cells and can be made as a thin film, while its chemical composition can change its band gap. However, achieving high transparency usually compromises the solar cell's efficiency. Here we report on a unique approach to fabricating semitransparent perovskite solar cells that does not rely on their composition or their thickness. The approach is based on a scalable process, inkjet printing of arrays of transparent pillars, which are composed of inert photopolymerizable liquid compositions and are partly covered by the perovskite. This material can be printed at specific locations and array densities, thus providing a digital control of both the transparency and efficiency of the solar cells. The new semitransparent device structure shows 11.2% efficiency with 24% average transparency without a top metal contact. Further development including deposition of a transparent contact enabled the fabrication of fully semitransparent devices with an efficiency of 10.6% and average transparency of 19%.

Unusually Strong Biexciton Repulsion Detected in Quantum Confined CsPbBr3 Nanocrystals with Two and Three Pulse Femtosecond Spectroscopy.

Transient absorption measurements were conducted on pristine and monoexciton saturated CsPbBr3 nanocrystals varying in size within the regime of a strong quantum confinement. Once the difference spectra were translated to absolute transient changes in absorption cross section, a single exciton is shown to completely bleach the band edge absorption peak and induce a new absorption roughly two times weaker ∼100 meV to the blue. Difference spectra obtained during Auger recombination of biexciton demonstrate that the addition of a second exciton, rather than double the effect of a first, bleaches the blue-induced absorption band without producing a net stimulated emission at the band edge. Accompanied by high time resolution transient absorption spectra pumping at the lowest exciton band, these results identify the blue-induced absorption as the second transition to 1Se1Sh which is shifted in energy due to unusually strong and promptly rising biexciton repulsion. Possible mechanisms giving rise to this repulsion and prospects for applying it to enhance optical gain applications of these particles are discussed.

Green energy by recoverable triple-oxide mesostructured perovskite photovoltaics.

Perovskite solar cells have developed into a promising branch of renewable energy. A combination of feasible manufacturing and renewable modules can offer an attractive advancement to this field. Herein, a screen-printed three-layered all-nanoparticle network was developed as a rigid framework for a perovskite active layer. This matrix enables perovskite to percolate and form a complementary photoactive network. Two porous conductive oxide layers, separated by a porous insulator, serve as a chemically stable substrate for the cells. Cells prepared using this scaffold structure demonstrated a power conversion efficiency of 11.08% with a high open-circuit voltage of 0.988 V. Being fully oxidized, the scaffold demonstrated a striking thermal and chemical stability, allowing for the removal of the perovskite while keeping the substrate intact. The application of a new perovskite in lieu of a degraded one exhibited a full regeneration of all photovoltaic performances. Exclusive recycling of the photoactive materials from solar cells paves a path for more sustainable green energy production in the future.

Effect of Perovskite Thickness on Electroluminescence and Solar Cell Conversion Efficiency.

A hybrid organic-inorganic perovskite in a diode structure can lead to multifunctional device phenomena exhibiting both a high power conversion efficiency (PCE) of a solar cell and strong electroluminescence (EL) efficiency. Nonradiative losses in such multifunctional devices lead to an open circuit voltage (Voc) deficit, which is a limiting factor for pushing the efficiency toward the Shockley-Queisser limit. In this work, we analyze and quantify the radiative limit of Voc in a perovskite solar cell as a function of its absorber thickness. We correlate PCE and EL efficiency at varying thicknesses to understand the limiting factors for a high Voc. With a certain increase in perovskite thickness, PCE improves but EL efficiency is compromised and vice versa. Thus, correlating these two figures of merit of a solar cell guides the light management strategy together with minimizing nonradiative losses. The results demonstrate that maximizing absorption and emission processes remains paramount for optimizing devices.

Electrical Characterization of Individual Cesium Lead Halide Perovskite Nanowires Using Conductive AFM.

Perovskite nanostructures have attracted much attention in recent years due to their suitability for a variety of applications such as photovoltaics, light-emitting diodes (LEDs), nanometer-size lasing, and more. These uses rely on the conductive properties of these nanostructures. However, electrical characterization of individual, thin perovskite nanowires has not yet been reported. Here, conductive atomic force microscopy characterization of individual cesium lead halide nanowires is presented. Clear differences are observed in the conductivity of nanowires containing only bromide and nanowires containing a mixture of bromide and iodide. The differences are attributed to a higher density of crystalline defects, deeper trap states, and higher inherent conductivity for nanowires with mixed bromide-iodide content.

Affecting an Ultra-High Work Function of Silver.

An ultra-high increase in the WF of silver, from 4.26 to 7.42 eV, that is, an increase of up to circa 3.1 eV is reported. This is the highest WF increase on record for metals and is supported by recent computational studies which predict the potential ability to affect an increase of the WF of metals by more than 4 eV. We achieved the ultra-high increase by a new approach: Rather than using the common method of 2D adsorption of polar molecules layers on the metal surface, WF modifying components, l-cysteine and Zn(OH)2 , were incorporated within the metal, resulting in a 3D architecture. Detailed material characterization by a large array of analytical methods was carried out, the combination of which points to a WF enhancement mechanism which is based on directly affecting the charge transfer ability of the metal separately by cysteine and hydrolyzed zinc(II), and synergistically by the combination of the two through the known Zn-cysteine finger redox trap effect.

Dion-Jacobson Two-Dimensional Perovskite Solar Cells Based on Benzene Dimethanammonium Cation.

Organic-inorganic perovskite structured compounds have recently emerged as attractive materials in the fields of photovoltaic due to their exciting optical properties and easy syntheses, as well as exceptional structural and optical tunability. This work presents a Dion-Jacobson two-dimensional (2D) perovskite using diammonium as the barrier molecule. We show that the diammonium barrier molecule is responsible for the perovskite layers' orientation supported by Hall Effect measurements, which results in a high efficiency solar cell for 2D perovskite without the need for additives or any additional treatment. The 2D perovskite cells achieved an efficiency of 15.6%, which was one of the highest reported for low-dimensional perovskite. Charge extraction, voltage decay, and charge collection efficiency measurements show the beneficial alignment of the 2D perovskites related to the selective contacts. Stability characterization shows that the stability for the 2D perovskite was enhanced compared with their 3D counterparts.

Cell refinement of CsPbBr3 perovskite nanoparticles and thin films.

In this work, we performed a detailed study of the phase transformations and structural unit cell parameters of CsPbBr3 nanoparticles (NPs) and thin films. In situ X-ray diffraction patterns were acquired as a function of temperature, where the positions and widths of the diffraction peaks were systematically tracked upon heating and cooling down to room temperature (RT). Scanning electron microscopy provides physical insight on the CsPbBr3 thin films upon annealing and transmission electron microscopy gives physical and crystallographic information for the CsPbBr3 NPs using electron diffraction. The secondary phase(s) CsPb2Br5 (and CsPb4Br6) are clearly observed in the XRD patterns of both nanoparticles and thin films upon heating to 500 K, whilst from 500 K to 595 K, these phases remain in small amounts and are kept like this upon cooling down to RT. However, in the case of thin films, the CsPb2Br5 secondary phase disappears completely above 580 K and pure cubic CsPbBr3 is observed up to 623 K. The CsPbBr3 phase is then kept upon cooling down to RT, achieving pure CsPbBr3 phase. This study provides detailed understanding of the phase behavior vs. temperature of CsPbBr3 NPs and thin films, which opens the way to pure CsPbBr3 phase, an interesting material for optoelectronic applications.

CsPbBr3 and CH3NH3PbBr3 promote visible-light photo-reactivity.

Inorganic and organic lead halide perovskite materials attract great interest in the scientific community because of their potential for low-cost, high efficiency solar cells. In this report we add a new property of these materials, namely their photochemical activity in the visible light range. Both inorganic (CsPbBr3) and organic (CH3NH3PbBr3-MAPbBr3) perovskite thin films were demonstrated to promote photo-dissociation of adsorbed ethyl chloride (EC), employing 532 nm pulsed laser irradiation under ultra-high vacuum (UHV) conditions. From the post-irradiation temperature programmed desorption (TPD) analysis, the yield of photoproduct formation was found to be up to two orders of magnitude higher than for UV light-excited EC molecules on metallic and oxide surfaces. Photo-reactivity on top of the CsPbBr3 surface is almost an order of magnitude more efficient than on the CH3NH3PbBr3 surface, apparently due to the lower density of defect and surface states. A direct correlation was found between electron-induced luminescence and photoluminescence intensities and the photoreactivity cross-sections. We conclude that both the intense luminescence and the well-known photovoltaic properties associated with these halide perovskite materials are consistent with the efficiency of photo-reactivity in the visible range, reported here for the first time.

Fine-tuning of the metal work function by molecular doping.

A new approach for fine tuning of the metal work function (WF) in the range of 1 eV is described. WF control is achieved by 3D molecular doping of the metal rather than the classical 2D adsorption. Both small molecules (Congo red, thionine) and polymers (Nafion, poly(vinylbenzyltrimethylammonium)chloride) were shown to affect the work function of gold and silver. The in situ reaction of the dopants within the metallic matrix is a further tool for altering the WF, confirming that this effect is dopant-dependent. We attribute this effect to the charge transfer interactions between the dopant molecule and the surrounding 3D metallic cage.

Reflectivity Effects on Pump-Probe Spectra of Lead Halide Perovskites: Comparing Thin Films versus Nanocrystals.

Due to the sizable refractive index of lead halide perovskites, reflectivity off their interface with air exceeds 15%. This has prompted a number of investigations into the prominence of photoreflective contributions to pump-probe data in these materials, with conflicting results. Here we report experiments aimed at assessing this by comparing transient transmission from lead halide perovskite films and weakly quantum confined nanocrystals of cesium lead iodide (CsPbI3) perovskite. By analyzing how complex refractive index changes impact the two experiments, results demonstrate that changes in absorption and not reflection dominate transient transmission measurements in thin films of these materials. None of the characteristic spectral signatures reported in such experiments are exclusively due to or even strongly affected by changes in sample reflectivity. This finding is upheld by another experiment where a methyl ammonium lead iodide (MAPbI3) perovskite film was formed on high-index flint glass and probed after pump irradiation from either face of the sample. We conclude that interpretations of ultrafast pump-probe experiments on thin perovskite films in terms of photoinduced changes in absorption alone are qualitatively sound, requiring relatively minor adjustments to factor in photoreflective effects.