Solar Energy Storage Using a Cu2 O-TiO2 Photocathode in a Lithium Battery.

A Cu2 O-TiO2 photoelectrode is pr+oposed for simultaneous solar light energy harvesting and storing of electrochemical energy in an adapted lithium coin cell. The p-type Cu2 O semiconductor layer is the light harvester component of the photoelectrode and the TiO2 film performs as the capacitive layer. The rationale of the energy scheme shows that the photocharges generated in the Cu2 O semiconductor induce lithiation/delithiation processes in the TiO2 film as a function of the applied bias voltage and light power. A photorechargeable lithium button cell drilled on one side recharges with visible white light in ≈9 h in open circuit. It provides an energy density of ≈150 mAh g-1 at 0.1 C discharge current in dark, and the overall efficiency is 0.29%. This work draws a new approach for the photoelectrode role to advance in monolithic rechargeable batteries.

Atomic-level understanding of a formamidinium hybrid halide perovskite, FAPbBr3.

Herein, we show how electron microscopy can provide atomic-level understanding of FAPbBr3, where electron diffraction and high-resolution imaging were combined allowing not only the characterization of the pristine material but also the identification of different intermediates upon its structural disintegration. Additionally, a minor tetragonal phase was also identified whose structure was also solved.

Short Photoluminescence Lifetimes Linked to Crystallite Dimensions, Connectivity, and Perovskite Crystal Phases.

Time-correlated single photon counting has been conducted to gain further insights into the short photoluminescence lifetimes (nanosecond) of lead iodide perovskite (MAPbI3) thin films (∼100 nm). We analyze three different morphologies, compact layer, isolated island, and connected large grain films, from 14 to 300 K using a laser excitation power of 370 nJ/cm2. Lifetime fittings from the Generalized Berberan-Santos decay model range from 0.5 to 6.5 ns, pointing to quasi-direct bandgap emission despite the three different sample strains. The high energy band emission for the isolated-island morphology shows fast recombination rate centers up to 4.8 ns-1, compared to the less than 2 ns-1 for the other two morphologies, similar to that expected in a good quality single crystal of MAPbI3. Low-temperature measurements on samples reflect a huge oscillator strength in this material where the free exciton recombination dominates, explaining the fast lifetimes, the low thermal excitation, and the thermal escape obtained.

Inhibition of light emission from the metastable tetragonal phase at low temperatures in island-like films of lead iodide perovskites.

Photonic applications based on halide perovskites, namely CH3NH3PbI3 (MAPbI3), have recently attracted remarkable attention due to the high efficiencies reported for photovoltaic and light emitting devices. Despite these outstanding results, there are many temperature-, laser excitation power-, and morphology-dependent phenomena that require further research to be completely understood. In this work, we have investigated in detail the nature of exciton optical transitions and recombination dynamics below and above the orthorhombic/tetragonal ('O'-/'T'-) temperature phase transition (∼150 K) depending on the material continuity (continuous-like) or discontinuity (island-like) in MAPbI3 films. At low temperatures, continuous thin films of the perovskite can exhibit strain inhomogeneities associated with the formation of different 'T'-defective domains leading to an energy spread of states over more than 200 meV. On the other hand, a single photoluminescence line peak related to the perovskite 'O'-phase (associated with the distortion of the [PbI3]- anion) is observed in the island-like sample that we attribute to strain relaxation for this morphology. Moreover, the predominantly radiative recombination dynamics of the continuous-like sample mainly originates from nongeminate electron-hole formation of excitons in the 'O'-phase and the internal dynamics with carrier trapping levels. This observation is in strong contrast to the free exciton recombination dominantly found in the island-like sample.

Degradation Mechanism and Relative Stability of Methylammonium Halide Based Perovskites Analyzed on the Basis of Acid-Base Theory.

The correct identification of all gases released during hybrid perovskite degradation is of great significance to develop strategies to extend the lifespan of any device based on this semiconductor. CH3X (X = Br/I) is a released degradation gas/low boiling point liquid arising from methylammonium (MA+) based perovskites, which has been largely overlooked in the literature focusing on stability of perovskite solar cells. Herein, we present an unambiguous identification of CH3I release using microwave (rotational) spectroscopy. An experimental back-reaction test demonstrates that the well-known CH3NH2/HX degradation route may not be the ultimate degradation pathway of MAPbX3 in thermodynamic closed systems. Meanwhile, the CH3X/NH3 route cannot back-react selectively to MAX formation as occurred for the former back-reaction. Metadynamics calculations uncover the X halide effect on energy barriers for both degradation reactions showing a better stability of Br based perovskite ascribed to two aspects: (i) lower Brönsted-Lowry acidity of HBr compared to HI and (ii) higher nucleophilic character of CH3NH2 compared to NH3. The latter property makes CH3NH2 molecules stay preferentially attached on the electrophilic perovskite surface (Pb2+) during the dynamic simulation instead of being detached as observed for the NH3 molecule.

Gas-solid reaction based over one-micrometer thick stable perovskite films for efficient solar cells and modules.

Besides high efficiency, the stability and reproducibility of perovskite solar cells (PSCs) are also key for their commercialization. Herein, we report a simple perovskite formation method to fabricate perovskite films with thickness over 1 µm in ambient condition on the basis of the fast gas-solid reaction of chlorine-incorporated hydrogen lead triiodide and methylamine gas. The resultant thick and smooth chlorine-incorporated perovskite films exhibit full coverage, improved crystallinity, low surface roughness and low thickness variation. The resultant PSCs achieve an average power conversion efficiency of 19.1 ± 0.4% with good reproducibility. Meanwhile, this method enables an active area efficiency of 15.3% for 5 cm × 5 cm solar modules. The un-encapsulated PSCs exhibit an excellent T80 lifetime exceeding 1600 h under continuous operation conditions in dry nitrogen environment.

Spin-Coated Crystalline Molecular Monolayers for Performance Enhancement in Organic Field-Effect Transistors.

In organic field-effect transistors, the first few molecular layers at the semiconductor/dielectric interface are regarded as the active channel for charge transport; thus, great efforts have been devoted to the modification and optimization of molecular packing at such interfaces. Here, we report organic monolayers with large-area uniformity and high crystallinity deposited by an antisolvent-assisted spin-coating method acting as the templating layers between the dielectric and thermally evaporated semiconducting layers. The predeposited crystalline monolayers significantly enhance the film crystallinity of upper layers and the overall performance of transistors using these hybrid-deposited semiconducting films, showing a high carrier mobility up to 11.3 cm2 V-1 s-1. Additionally, patterned transistor arrays composed of the templating monolayers are fabricated, yielding an average mobility of 7.7 cm2 V-1 s-1. This work demonstrates a promising method for fabricating low-cost, high-performance, and large-area organic electronics.

Improved Efficiency and Stability of Perovskite Solar Cells Induced by CO Functionalized Hydrophobic Ammonium-Based Additives.

Because of the rapid rise of the efficiency, perovskite solar cells are currently considered as the most promising next-generation photovoltaic technology. Much effort has been made to improve the efficiency and stability of perovskite solar cells. Here, it is demonstrated that the addition of a novel organic cation of 2-(6-bromo-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)ethan-1-ammonium iodide (2-NAM), which has strong Lewis acid and base interaction (between CO and Pb) with perovskite, can effectively increase crystalline grain size and reduce charge carrier recombination of the double cation FA0.83 MA0.17 PbI2.51 Br0.49 perovskite film, thus boosting the efficiency from 17.1 ± 0.8% to 18.6 ± 0.9% for the 0.1 cm2 cell and from 15.5 ± 0.5% to 16.5 ± 0.6% for the 1.0 cm2 cell. The champion cell shows efficiencies of 20.0% and 17.6% with active areas of 0.1 and 1.0 cm2 , respectively. Moreover, the hysteresis behavior is suppressed and the stability is improved. The result provides a promising route to further elevate efficiency and stability of perovskite solar cells by the fine tuning of triple organic cations.

Progress on Perovskite Materials and Solar Cells with Mixed Cations and Halide Anions.

Organic-inorganic halide perovskite materials (e.g., MAPbI3, FAPbI3, etc.; where MA = CH3NH3+, FA = CH(NH2)2+) have been studied intensively for photovoltaic applications. Major concerns for the commercialization of perovskite photovoltaic technology to take off include lead toxicity, long-term stability, hysteresis, and optimal bandgap. Therefore, there is still need for further exploration of alternative candidates. Elemental composition engineering of MAPbI3 and FAPbI3 has been proposed to address the above concerns. Among the best six certified power conversion efficiencies reported by National Renewable Energy Laboratory on perovskite-based solar cells, five are based on mixed perovskites (e.g., MAPbI1-xBrx, FA0.85MA0.15PbI2.55Br0.45, Cs0.1FA0.75MA0.15PbI2.49Br0.51). In this paper, we review the recent progress on the synthesis and fundamental aspects of mixed cation and halide perovskites correlating with device performance, long-term stability, and hysteresis. In the outlook, we outline the future research directions based on the reported results as well as related topics that warrant further investigation.

Methylammonium Lead Bromide Perovskite Light-Emitting Diodes by Chemical Vapor Deposition.

Organo-lead-halide perovskites are promising materials for optoelectronic applications. Perovskite solar cells have reached power conversion efficiencies of over 22%, and perovskite light-emitting diodes have recently achieved over 11% external quantum efficiency. To date, most research on perovskite light-emitting diodes has focused on solution-processed films. There are many advantages of a vapor-based growth process to prepare perovskites, including ease of patterning, ability to batch process, and material compatibility. We investigated an all-vapor perovskite growth process by chemical vapor deposition and demonstrated luminance up to 560 cd/m2.

Recombination reduction on lead halide perovskite solar cells based on low temperature synthesized hierarchical TiO2 nanorods.

Intensive research on the electron transport material (ETM) has been pursued to improve the efficiency of perovskite solar cells (PSCs) and decrease their cost. More importantly, the role of the ETM layer is not yet fully understood, and research on new device architectures is still needed. Here, we report the use of three-dimensional (3D) TiO2 with a hierarchical architecture based on rutile nanorods (NR) as photoanode material for PSCs. The proposed hierarchical nanorod (HNR) films were synthesized by a two-step low temperature (180 °C) hydrothermal method, and consist of TiO2 nanorod trunks with optimal lengths of 540 nm and TiO2 nanobranches with lengths of 45 nm. Different device configurations were fabricated with TiO2 structures (compact layer, NR and HNR) and CH3NH3PbI3, using different synthetic routes, as the active material. PSCs based on HNR-CH3NH3PbI3 achieved the highest power conversion efficiency compared to PSCs with other TiO2 structures. This result can be ascribed mainly to lower charge recombination as determined by impedance spectroscopy. Furthermore, we have observed that the CH3NH3PbI3 perovskite deposited by the two-step route shows higher efficiency, surface coverage and infiltration within the structure of 3D HNR than the one-step CH3NH3PbI(3-x)Cl(x) perovskite.

Polymer/Perovskite Amplifying Waveguides for Active Hybrid Silicon Photonics.

The emission properties of hybrid halide perovskites are exploited to implement a stable and very low power operation waveguide optical amplifier integrated in a silicon platform. By optimizing its design with a poly(methyl methacrylate) (PMMA) encapsulation, this novel photonic device presents a net gain of around 10 dB cm(-1) and 3-4 nm linewidth with an energy threshold as low as 2 nJ pulse(-1) and exhibiting no degradation after one year.

Effect of Mesostructured Layer upon Crystalline Properties and Device Performance on Perovskite Solar Cells.

One of the most fascinating characteristics of perovskite solar cells (PSCs) is the retrieved obtainment of outstanding photovoltaic (PV) performances withstanding important device configuration variations. Here we have analyzed CH3NH3PbI3-xClx in planar or in mesostructured (MS) configurations, employing both titania and alumina scaffolds, fully infiltrated with perovskite material or presenting an overstanding layer. The use of the MS scaffold induces to the perovskite different structural properties, in terms of grain size, preferential orientation, and unit cell volume, in comparison to the ones of the material grown with no constraints, as we have found out by X-ray diffraction analyses. We have studied the effect of the PSC configuration on photoinduced absorption and time-resolved photoluminescence, complementary techniques that allow studying charge photogeneration and recombination. We have estimated electron diffusion length in the considered configurations observing a decrease when the material is confined in the MS scaffold with respect to a planar architecture. However, the presence of perovskite overlayer allows an overall recovering of long diffusion lengths explaining the record PV performances obtained with a device configuration bearing both the mesostructure and a perovskite overlayer. Our results suggest that performance in devices with perovskite overlayer is mainly ruled by the overlayer, whereas the mesoporous layer influences the contact properties.

General working principles of CH3NH3PbX3 perovskite solar cells.

Organometal halide perovskite-based solar cells have recently realized large conversion efficiency over 15% showing great promise for a new large scale cost-competitive photovoltaic technology. Using impedance spectroscopy measurements we are able to separate the physical parameters of carrier transport and recombination in working devices of the two principal morphologies and compositions of perovskite solar cells, viz. compact thin films of CH3NH3PbI(3-x)Clx and CH3NH3PbI3 infiltrated on nanostructured TiO2. The results show nearly identical spectral characteristics indicating a unique photovoltaic operating mechanism that provides long diffusion lengths (1 µm). Carrier conductivity in both devices is closely matched, so that the most significant differences in performance are attributed to recombination rates. These results highlight the central role of the CH3NH3PbX3 semiconductor absorber in carrier collection and provide a new tool for improved optimization of perovskite solar cells. We report for the first time a measurement of the diffusion length in a nanostructured perovskite solar cell.

Role of the Selective Contacts in the Performance of Lead Halide Perovskite Solar Cells.

The effect of electron- and hole-selective contacts in the final cell performance of hybrid lead halide perovskite, CH3NH3PbI3, solar cells has been systematically analyzed by impedance spectroscopy. Complete cells with compact TiO2 and spiro-OMeTAD as electron- and hole-selective contacts have been compared with incomplete cells without one or both selective contacts to highlight the specific role of each contact. It has been described how selective contacts contribute to enhance the cell FF and how the hole-selective contact is mainly responsible for the high Voc in this kind of device. We have determined that the recombination rate is mainly governed by the selective contacts. This fact has important implication for the future optimization of perovskite solar cells. Finally, we have developed a method to analyze the results obtained, and it has been applied for three different electron-selecting materials: TiO2, ZnO, and CdS.

Photoinduced Giant Dielectric Constant in Lead Halide Perovskite Solar Cells.

Organic-inorganic lead trihalide perovskites have emerged as an outstanding photovoltaic material that demonstrated a high 17.9% conversion efficiency of sunlight to electricity in a short time. We have found a giant dielectric constant (GDC) phenomenon in these materials consisting on a low frequency dielectric constant in the dark of the order of ε0 = 1000. We also found an unprecedented behavior in which ε0 further increases under illumination or by charge injection at applied bias. We observe that ε0 increases nearly linearly with the illumination intensity up to an additional factor 1000 under 1 sun. Measurement of a variety of samples of different morphologies, compositions, and different types of contacts shows that the GDC is an intrinsic property of MAPbX3 (MA = CH3NH3(+)). We hypothesize that the large dielectric response is induced by structural fluctuations. Photoinduced carriers modify the local unit cell equilibrium and change the polarizability, assisted by the freedom of rotation of MA. The study opens a way for the understanding of a key aspect of the photovoltaic operation of high efficiency perovskite solar cells.

Mechanism of carrier accumulation in perovskite thin-absorber solar cells.

Photovoltaic conversion requires two successive steps: accumulation of a photogenerated charge and charge separation. Determination of how and where charge accumulation is attained and how this accumulation can be identified is mandatory for understanding the performance of a photovoltaic device and for its further optimization. Here we analyse the mechanism of carrier accumulation in lead halide perovskite, CH3NH3PbI3, thin-absorber solar cells by means of impedance spectroscopy. A fingerprint of the charge accumulation in high density of states of the perovskite absorber material has been observed at the capacitance of the samples. This is, as far as we know, the first observation of charge accumulation in light-absorbing material for nanostructured solar cells, indicating that it constitutes a new kind of photovoltaic device, differentiated from sensitized solar cells, which will require its own methods of study, characterization and optimization.

Metallacarboranes and their interactions: theoretical insights and their applicability.

This tutorial review will deal with the study of metallacarboranes and their interactions with other molecules from a theoretical point of view. This contribution is devoted to guide experimental chemists through calculations that some years ago were reserved to theoretical specialists. The widespread availability of fast computers enables nowadays studies of complex compounds (e.g. metallacarboranes) from different perspectives including simulation of NMR, infrared or Raman spectra and calculation of other properties such as atomic charges or inter-/intramolecular interactions. The insights gained on the basis of theoretical calculations are crucial for either finding novel or improving existing applications of metallacarboranes. For example, in the case of enzyme inhibitors, the interactions of the metallacarboranes with the surrounding protein and how the interaction affects the efficiency are difficult problems to study experimentally. The use of theoretical tools can provide a detailed understanding of the physico-chemical basis of the interactions and thus offers a chance to control the overall process.