8 Search Results

Mixtures of layered perovskite quantum wells with different sizes form prototypical light-harvesting antenna structures in solution-processed films. Gradients in the bandgaps and energy levels are established by concentrating the smallest and largest quantum wells near opposing electrodes in photovoltaic devices. Whereas short-range energy and charge carrier funneling behaviors have been observed in layered perovskites, our recent work suggests that such light-harvesting processes do not assist long-range charge transport due to carrier trapping at interfaces between quantum wells and interstitial organic spacer molecules. Here, we apply a two-pulse time-of-flight technique to a family of layered perovskite systems to explore the effectsmore » that interstitial organic molecules have on charge carrier dynamics. In these experiments, the first laser pulse initiates carrier drift within the active layer of a photovoltaic device, whereas the second pulse probes the transient concentrations of photoexcited carriers as they approach the electrodes. The instantaneous drift velocities determined with this method suggest that the rates of trap-induced carrier deceleration increase with the concentrations of organic spacer cations. Overall, our experimental results and model calculations suggest that the layered perovskite device efficiencies primarily reflect the dynamics of carrier trapping at interfaces between quantum wells and interstitial organic phases.« less

Interest in layered organohalide perovskites is motivated by their potential for use in optoelectronic devices. In these systems, the smallest and largest quantum wells are primarily concentrated near the glass and air interfaces of a film, thereby establishing a gradient in the average values of the bandgaps. It has been suggested that this layered architecture promotes the funneling of electronic excitations through space in a manner similar to light-harvesting processes in photosynthetic antennae. Whereas energy and charge transfer are difficult to distinguish by conventional transient absorption techniques, it has recently been shown that these competing relaxation mechanisms may be separatelymore » targeted with nonlinear fluorescence (NLFL) and photocurrent “action spectroscopies.” Here, we present perturbative rate functions to describe NLFL experiments conducted on layered perovskite systems. The formulas reproduce the patterns of resonances observed in experimental measurements and show how signatures of energy transfer manifest in two-dimensional spectra. Overall, this work suggests that NLFL spectroscopy may be used to fully reveal the trajectories of electronic excitations by correlating ultrafast energy transfer pathways to fluorescence emission from the thickest quantum wells.« less

The direction of electron flow in molecular optoelectronic devices is dictated by charge transfer between a molecular excited state and an underlying conductor or semiconductor. For those devices, controlling the direction and reversibility of electron flow is a major challenge. We describe here a single-molecule photodiode. It is based on an internally conjugated, bichromophoric dyad with chemically linked (porphyrinato)zinc(II) and bis(terpyridyl)ruthenium(II) groups. On nanocrystalline, degenerately doped indium tin oxide electrodes, the dyad exhibits distinct frequency-dependent, charge-transfer characters. Variations in the light source between red-light (∼1.9 eV) and blue-light (∼2.7 eV) excitation for the integrated photodiode result in switching of photocurrentsmore » between cathodic and anodic. The origin of the excitation frequency-dependent photocurrents lies in the electronic structure of the chromophore excited states, as shown by the results of theoretical calculations, laser flash photolysis, and steady-state spectrophotometric measurements.« less

Phenethylammonium (PEA)-based 2D perovskite is an interesting example of 2D perovskites, serving as the gateway for further introduction of functional conjugated organic cations into 2D perovskites for a variety of applications, for example, photovoltaics. However, the efficiency of photovoltaic devices based on PEA 2D perovskites only achieved ≈7% for = 3, which was significantly lower than that achieved for other cation-based 2D perovskites. In this work, by introducing propyl ammonium (C3A) into the PEA-based 2D perovskites, the device efficiency is improved to ≈10% for 1:1 C3A:PEA-based 2D perovskites ( = 3). Further investigation reveals that tuning the CH···π interaction (betweenmore » C3A and PEA or between two PEA molecules) can have multiple beneficial impacts on such modified 2D perovskites, including a) removal of undesirable n = 1 phase, b) lowering the density of trap states, and c) achieving larger crystalline grains. Additionally, after substitution with 50% C3A, other aromatic ammonium cation-based 2D perovskites ( = 3) also show similar efficiency enhancement in their photovoltaic devices, thus exhibiting the general applicability of this method. The results of this study highlight that the strategic tuning of non-covalent interactions (such as CH···π interaction) is a viable and important method to further develop 2D perovskites for photovoltaics.« less

The efficiencies of green and red perovskite light-emitting diodes (PeLEDs) have been increased close to their theoretical upper limit, while the efficiency of blue PeLEDs is lagging far behind. Here we report enhancing the efficiency of sky-blue PeLEDs by overcoming a major hurdle of low photoluminescence quantum efficiency in wide-bandgap perovskites. Blending phenylethylammonium chloride into cesium lead halide perovskites yields a mixture of two-dimensional and three-dimensional perovskites, which enhances photoluminescence quantum efficiency from 1.1% to 19.8%. Adding yttrium (III) chloride into the mixture further enhances photoluminescence quantum efficiency to 49.7%. Yttrium is found to incorporate into the three-dimensional perovskite grain,more » while it is still rich at grain boundaries and surfaces. The yttrium on grain surface increases the bandgap of grain shell, which confines the charge carriers inside grains for efficient radiative recombination. Record efficiencies of 11.0% and 4.8% were obtained in sky-blue and blue PeLEDs, respectively.« less

Layered perovskites have been shown to improve the stability of perovskite solar cells while its operation mechanism remains unclear. Here we investigate the process for the conversion of light to electrical current in high performance layered perovskite solar cells by examining its real morphology. The layered perovskite films in this study are found to be a mixture of layered and three dimensional (3D)-like phases with phase separations at micrometer and nanometer scale in both vertical and lateral directions. This phase separation is explained by the surface initiated crystallization process and the competition of the crystallization between 3D-like and layered perovskites.more » We further propose that the working mechanisms of the layered perovskite solar cells involve energy transfer from layered to 3D-like perovskite network. The impact of morphology on efficiency and stability of the hot-cast layered perovskite solar cells are also discussed to provide guidelines for the future improvement.« less

Two-dimensional perovskites have emerged as more intrinsically stable materials for solar cells. Chemical tuning of spacer organic cations has attracted great interest due to their additional functionalities. However, how the chemical nature of the organic cations affects the properties of two-dimensional perovskites and devices is rarely reported. Here we demonstrate that the selection of spacer cations (i.e., selective fluorination of phenethylammonium) affects the film properties of two-dimensional perovskites, leading to different device performance of two-dimensional perovskite solar cells (average n = 4). Structural analysis reveals that different packing arrangements and orientational disorder of the spacer cations result in orientational degeneracymore » and different formation energies, largely explaining the difference in film properties. This work provides key missing information on how spacer cations exert influence on desirable electronic properties and device performance of two-dimensional perovskites via the weak and cooperative interactions of these cations in the crystal lattice.« less