We address the behavior in which a bias voltage can be used to switch on and off the photoluminescence of a planar film of methylammonium lead triiodide perovskite (MAPbI3) semiconductor with lateral symmetric electrodes. It is observed that a dark region advances from the positive electrode at a slow velocity of order of 10 μm s–1. Here we explain the existence of the sharp front by a drift of ionic vacancies limited by local saturation, that induce defects and drastically reduce the radiative recombination rate in the film. The model accounts for the time dependence of electrical current due to the ion-induced doping modification, that changes local electron and hole concentration with the drift of vacancies. The analysis of current dependence on time leads to a direct determination of the diffusion coefficient of iodine vacancies and provides detailed information of ionic effects over the electrooptical properties of hybrid perovskite materials.

Organic-inorganic metal-halide perovskites (e.g. CH3NH3PbI3-xClx) emerged as a promising opto-electronic material. However, the Shockley-Queisser Limit for the power conversion efficiency (PCE) of perovskite-based photovoltaic devices has still not been reached, which was attributed to non-radiative recombination pathways, as suggested by photoluminescence (PL) inactive (or dark) areas on perovskite films. Although these observations have been related to the presence of ions/defects, the underlying fundamental physics and detailed microscopic processes, concerning trap/defect status, ion migration, etc., still remain poorly understood. Here we utilize correlated wide-field PL microscopy and impedance spectroscopy (IS) on perovskite films to in-situ investigate both the spatial and temporal evolution of these PL inactive areas under external electrical fields. We attribute the formation of PL inactive domains to the migration and accumulation of iodine ions under external fields.Hence we are able to characterize the kinetic processes and determine the drift velocities of these ions. In addition, we show that I2 vapor directly affects the PL quenching of a perovskite film, which provides evidence that the migration/segregation of iodide ions plays an important role in the PL quenching and consequently limits the PCE of organometal halide based perovskite photovoltaic devices.

In this Letter, we investigate the temperature dependence of the optical properties of methylammonium lead iodide (MAPbI3 = CH3NH3PbI3) from room temperature to 6 K. In both the tetragonal (T > 163 K) and the orthorhombic (T < 163 K) phases of MAPbI3, the band gap (from both absorption and photoluminescence (PL) measurements) decreases with decrease in temperature, in contrast to what is normally seen for many inorganic semiconductors, such as Si, GaAs, GaN, etc. We show that in the perovskites reported here, the temperature coefficient of thermal expansion is large and accounts for the positive temperature coefficient of the band gap. A detailed analysis of the exciton line width allows us to distinguish between static and dynamic disorder. The low-energy tail of the exciton absorption is reminiscent of Urbach absorption. The Urbach energy is a measure of the disorder, which is modeled using thermal and static disorder for both the phases separately. The static disorder component, manifested in the exciton line width at low temperature, is small. Above 60 K, thermal disorder increases the line width. Both these features are a measure of the high crystal quality and low disorder of the perovskite films even though they are produced from solution.

Regenerated cellulose (RC) films coated with copper (Cu) nanoparticles were prepared from cellulose-cuprammonium solution through coagulation in aq. NaOH and subsequent reduction in aq. NaBH4. Structure and morphology of the nanocomposite films were characterized with X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The results established the migration of Cu(2+) from the inner to the surface of the RC films during the coagulation of cellulose-cuprammonium solution and the reduction from Cu(2+) to Cu(0). Cu nanoparticles were found to be firmly embedded on the surface of the RC films. The RC films coated with Cu nanoparticles showed efficient antibacterial activity against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). The dramatic reduction of viable bacteria could be observed within 0.5 h of exposure, and all of the bacteria were killed within 1 h.

The power conversion efficiency of inorganic–organic hybrid lead halide perovskite solar cells (PSCs) is approaching that of those made from single crystalline silicon; however, they still experience problems such as hysteresis and photo/electrical‐field‐induced degradation. Evidences consistently show that ionic migration is critical for these detrimental behaviors, but direct in‐situ studies are still lacking to elucidate the respective kinetics. Three different PSCs incorporating phenyl‐C61‐butyric acid methyl ester (PCBM) and a polymerized form (PPCBM) is fabricated to clarify the function of fullerenes towards ionic migration in perovskites: 1) single perovskite layer, 2) perovskite/PCBM bilayer, 3) perovskite/PPCBM bilayer, where the fullerene molecules are covalently linked to a polymer backbone impeding fullerene inter‐diffusion. By employing wide‐field photoluminescence imaging microscopy, the migration of iodine ions/vacancies under an external electrical field is studied. The polymerized PPCBM layer barely suppresses ionic migration, whereas PCBM readily does. Temperature‐dependent chronoamperometric measurements demonstrate the reduction of activation energy with the aid of PCBM and X‐ray photoemission spectroscopy (XPS) measurements show that PCBM molecules are viable to diffuse into the perovskite layer and passivate iodine related defects. This passivation significantly reduces iodine ions/vacancies, leading to a reduction of built‐in field modulation and interfacial barriers.

The field of lead halide perovskites for solar cell applications has recently reported impressive power conversion (PCE) above 22 % using complex mixed cation formulations. Very importantly, highest PCE have been obtained using totally dry environmental conditions increasing the processing costs (i.e. use of glovebox). In this work devices processed in air under different ambient conditions are prepared with PCE approaching 19 % for the simplest lead halide perovskite (MAPbI 3 , MA= Methyl ammonium). It is shown that the PbI 2 :MAI:additive complex needs to be generated in the correct stoichiometry (1:1:1) where additives are any highly polar molecule able to stabilize the complex (i.e. H 2 O or Dimethylsulphoxide (DMSO)). At high humidity conditions H 2 O is incorporated into the complex and only small concentrations of further additives are needed. Precursor formulations not adequately balanced for the humidity conditions lead to films with poor morphology as evidenced by SEM. These films show negative multiiodide plumbate chemical defects as observed by absorbance measurements. These chemical defects act as recombination centers reducing the photocurrent and Fill Factor in photovoltaic devices. In addition, it is shown the undesirable high conductivity of the perovskite hydrates (8x10 -1 Scm -1 ), up to seven orders of magnitude higher than the pure MAPbI 3 , indicating that the presence of hydrates may act as shunting pathways that can significantly reduce the open circuit potential.

Inorganic–organic halide organometal perovskites, such as CH3NH3PbI3 and CsPbI3, etc, have been an unprecedented rising star in the field of photovoltaics since 2009, owing to their exceptionally high power conversion efficiency and simple fabrication processability. Despite its relatively short history of development, intensive investigations have been concentrating on this material; these have ranged from crystal structure analysis and photophysical characterization to performance optimization and device integration, etc. Yet, when applied in photovoltaic devices, this material suffers from hysteresis, that is, the difference of the current–voltage (I–V) curve during sweeping in two directions (from short-circuit towards open-circuit and vice versa). This behavior may significantly impede its large-scale commercial application. This Review will focus on the recent theoretical and experimental efforts to reveal the origin and mechanism of hysteresis. The proposed origins include (1) ferroelectric polarization, (2) charge trapping/detrapping, and (3) ion migration. Among them, recent evidence consistently supports the idea that ion migration plays a key role for the hysteretic behavior in perovskite solar cells (PSCs). Hence, this Review will summarize the recent results on ion migration such as the migrating ion species, activation energy measurement, capacitive characterization, and internal electrical field modulation, etc. In addition, this Review will also present the devices with alleviation/elimination of hysteresis by incorporating either large-size grains or phenyl-C61-butyric acid methyl ester molecules. In a different application, the hysteretic property has been utilized in photovoltaic and memristive switching devices. In sum, by examining these three possible mechanisms, it is concluded that the origin of hysteresis in PSCs is associated with a combination of effects, but mainly limited by ion/defect migration. This strong interaction between ion motion and free charge carrier transport can be modulated by the prevalent crystalline structure, chemical passivation, and an external photo/electrical field.

Stability of organic photovoltaic devices (OPVs) is a limiting factor for their commercialization and still remains a major challenge whilst power conversion efficiencies are now approaching minimum requirements. The inverted organic solar cell (iOSC) architecture shows promising potential for improving significantly the cell's working lifetime. However, when solution processed ZnO is used as electron extraction layer, an undesirable light‐soaking step is commonly required before the device reaches a non‐permanent maximum performance. This work investigates the use of Sr and Ba doped ZnO films, ZnSrO and ZnBaO, formed by sol‐gel deposition using molecular alkoxide precursor solutions, as electron extraction layers in a model iOSCs with poly [3‐hexylthiophene] (P3HT): [6, 6]‐phenyl C60 butyl acid methyl ester (PCBM) as the active layer. We show that using these ternary oxides the light‐soaking step can be circumvented by preventing a dipole forming between the oxide and the active organic layer as supported by electroabsorption spectroscopy measurements of the device built‐in field. It is suggested that Sr or Ba doping results in suppression/reduction of the oxygen adsorption at mobile oxygen vacancy sites on the metal oxide surface. Like in thin film transistor (TFT) applications, where materials like InGaZnO are rapidly becoming an important technology, the use of amorphous, mixed metal oxides allows improving the performance and stability of interfacial charge extraction layers for organic solar cells.