Laurent Pedesseau

High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells

Three-dimensional organic–inorganic perovskites have emerged as one of the most promising thin-film solar cell materials owing to their remarkable photophysical properties, which have led to power conversion efficiencies exceeding 20 per cent, with the prospect of further improvements towards the Shockley–Queisser limit for a single‐junction solar cell (33.5 per cent). Besides efficiency, another critical factor for photovoltaics and other optoelectronic applications is environmental stability and photostability under operating conditions. In contrast to their three-dimensional counterparts, Ruddlesden–Popper phases—layered two-dimensional perovskite films—have shown promising stability, but poor efficiency at only 4.73 per cent. This relatively poor efficiency is attributed to the inhibition of out-of-plane charge transport by the organic cations, which act like insulating spacing layers between the conducting inorganic slabs. Here we overcome this issue in layered perovskites by producing thin films of near-single-crystalline quality, in which the crystallographic planes of the inorganic perovskite component have a strongly preferential out-of-plane alignment with respect to the contacts in planar solar cells to facilitate efficient charge transport. We report a photovoltaic efficiency of 12.52 per cent with no hysteresis, and the devices exhibit greatly improved stability in comparison to their three-dimensional counterparts when subjected to light, humidity and heat stress tests. Unencapsulated two-dimensional perovskite devices retain over 60 per cent of their efficiency for over 2,250 hours under constant, standard (AM1.5G) illumination, and exhibit greater tolerance to 65 per cent relative humidity than do three-dimensional equivalents. When the devices are encapsulated, the layered devices do not show any degradation under constant AM1.5G illumination or humidity. We anticipate that these results will lead to the growth of single-crystalline, solution-processed, layered, hybrid, perovskite thin films, which are essential for high-performance opto-electronic devices with technologically relevant long-term stability.

Extremely efficient internal exciton dissociation through edge states in layered 2D perovskites

How perovskites have the edge Two-dimensional Ruddlesden-Popper perovskites form quantum wells by sandwiching inorganic-organic perovskite layers used in photovoltaic devices between organic layers. Blancon et al. show that if the perovskite layer is more than two unit cells thick, photogenerated excitons undergo an unusual but highly efficient process for creating free carriers that can be harvested in photovoltaic devices (see the Perspective by Bakr and Mohammed). Lower-energy local states at the edges of the perovskite layer facilitate dissociation into electrons and holes that are well protected from recombination. Science, this issue p.1288; see also p. 1260 Excitons convert spontaneously to free carriers via lower-energy layer-edge states in layered perovskites. Understanding and controlling charge and energy flow in state-of-the-art semiconductor quantum wells has enabled high-efficiency optoelectronic devices. Two-dimensional (2D) Ruddlesden-Popper perovskites are solution-processed quantum wells wherein the band gap can be tuned by varying the perovskite-layer thickness, which modulates the effective electron-hole confinement. We report that, counterintuitive to classical quantum-confined systems where photogenerated electrons and holes are strongly bound by Coulomb interactions or excitons, the photophysics of thin films made of Ruddlesden-Popper perovskites with a thickness exceeding two perovskite-crystal units (>1.3 nanometers) is dominated by lower-energy states associated with the local intrinsic electronic structure of the edges of the perovskite layers. These states provide a direct pathway for dissociating excitons into longer-lived free carriers that substantially improve the performance of optoelectronic devices.

Rashba and Dresselhaus Effects in Hybrid Organic–Inorganic Perovskites: From Basics to Devices

We use symmetry analysis, density functional theory calculations, and k·p modeling to scrutinize Rashba and Dresselhaus effects in hybrid organic-inorganic halide perovskites. These perovskites are at the center of a recent revolution in the field of photovoltaics but have also demonstrated potential for optoelectronic applications such as transistors and light emitters. Due to a large spin-orbit coupling of the most frequently used metals, they are also predicted to offer a promising avenue for spin-based applications. With an in-depth inspection of the electronic structures and bulk lattice symmetries of a variety of systems, we analyze the origin of the spin splitting in two- and three-dimensional hybrid perovskites. It is shown that low-dimensional nanostructures made of CH3NH3PbX3 (X = I, Br) lead to spin splittings that can be controlled by an applied electric field. These findings further open the door for a perovskite-based spintronics.

Polaron Stabilization by Cooperative Lattice Distortion and Cation Rotations in Hybrid Perovskite Materials

Solution-processed organometallic perovskites have rapidly developed into a top candidate for the active layer of photovoltaic devices. Despite the remarkable progress associated with perovskite materials, many questions about the fundamental photophysical processes taking place in these devices, remain open. High on the list of unexplained phenomena are very modest mobilities despite low charge carrier effective masses. Moreover, experiments elucidate unique degradation of photocurrent affecting stable operation of perovskite solar cells. These puzzles suggest that, while ionic hybrid perovskite devices may have efficiencies on par with conventional Si and GaAs devices, they exhibit more complicated charge transport phenomena. Here we report the results from an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies using both periodic boundary conditions and isolated structures. Using the hybrid density functional theory, we found that volumetric strain in a CsPbI3 cluster creates a polaron with binding energy of around 300 and 900 meV for holes and electrons, respectively. In the MAPbI3 (MA = CH3NH3) cluster, both volumetric strain and MA reorientation effects lead to larger binding energies at around 600 and 1300 meV for holes and electrons, respectively. Such large reorganization energies suggest appearance of small polarons in organometallic perovskite materials. The fact that both volumetric lattice strain and MA molecular rotational degrees of freedom can cooperate to create and stabilize polarons indicates that in order to mitigate this problem, formamidinium (FA = HC(NH2)2) and cesium (Cs) based crystals and alloys, are potentially better materials for solar cell and other optoelectronic applications.

Electronic model for self-assembled hybrid organic/perovskite semiconductors: Reverse band edge electronic states ordering and spin-orbit coupling

Based on density functional theory, the electronic and optical properties of hybrid organic/perovskite crystals are thoroughly investigated. We consider the monocrystalline 4F-PEPI as material model and demonstrate that the optical process is governed by three active Bloch states at the Gamma point of the reduced Brillouin zone with a reverse ordering compared to tetrahedrally bonded semiconductors. Giant spin-orbit coupling effects and optical activities are subsequently inferred from symmetry analysis.

Understanding Quantum Confinement of Charge Carriers in Layered 2D Hybrid Perovskites

Layered hybrid organic perovskites (HOPs) structures are a class of low-cost two-dimensional materials that exhibit outstanding optical properties, related to dielectric and quantum confinement effects. Whereas modeling and understanding of quantum confinement are well developed for conventional semiconductors, such knowledge is still lacking for 2D HOPs. In this work, concepts of effective mass and quantum well are carefully investigated and their applicability to 2D HOPs is discussed. For ultrathin layers, the effective-mass model fails. Absence of superlattice coupling and importance of non-parabolicity effects prevents the use of simple empirical models based on effective masses and envelope function approximations. An alternative method is suggested in which 2D HOPs are treated as composite materials, and a first-principles approach to the calculation of band offsets is introduced. These findings might also be relevant for other classes of layered 2D functional materials.

Correction: Interplay of spin–orbit coupling and lattice distortion in metal substituted 3D tri-chloride hybrid perovskites

Correction for ‘Interplay of spin–orbit coupling and lattice distortion in metal substituted 3D tri-chloride hybrid perovskites’ by C. Katan et al., J. Mater. Chem. A, 2015, 3, 9232–9240.

Evaluation of InGaPN and GaAsPN materials lattice-matched to Si for multi-junction solar cells

We compare the potentiality of bulk InGaPN and GaAsPN materials quasi-lattice-matched to silicon (Si), for multi-junction solar cells application. Bandgaps of both bulk alloys are first studied by a tight-binding model modified for nitrogen incorporation in diluted regimes. The critical thicknesses of those alloys are then calculated for various compositions. For the same lattice-mismatch and nitrogen amount, the bandgap of bulk GaAsPN is found to be closer to the targeted gap value of 1.7 eV for high efficiency tandem solar cell. GaPN and GaAsPN epilayers are then grown by molecular beam epitaxy on GaP substrate and studied by photoluminescence and X-ray diffraction. A GaAsPN bulk alloy emitting light at 1.77 eV at room temperature is obtained, demonstrating promising properties for further use in III-V/Si photovoltaic multijunction solar cells.

On the entanglement of electrostriction and non-linear piezoelectricity in non-centrosymmetric materials

An extended and complete thermodynamical model of third-order electro-elastic coupling is proposed with symmetry analyses and density functional theory (DFT) calculations to evaluate consistently the various linear and non-linear coefficients. It is shown that in non-centrosymmetric materials, electrostrictive and non-linear piezoelectric phenomena are strongly coupled, except for materials crystallizing in a cubic lattice associated to the 432 point group. Thorough numerical results are given for GaN and AlN compounds in the Wurtzite structure. Electrostriction dominates, but non-linear elasticity and non-linear piezoelectricity must be taken into account for strain evaluation whereas non-linear piezoelectricity yields a significant correction for electric field.

Semianalytical evaluation of linear and nonlinear piezoelectric potentials for quantum nanostructures with axial symmetry

A model is proposed to describe the linear and quadratic piezoelectric potentials in quantum nanostructures with axial symmetry. Semianalytical expressions of the charge densities are given to illustrate the symmetry reduction. The results for InAs∕InP quantum dots (QDs) are compared to previous full three-dimensional calculation and to the full isotropic elastic model. The model is well adapted to study various effects for QD: the lattice mismatch, the QD materials composition or alloying, and the QD size or shape. Special emphasis is put on variations of the vertical aspect ratio and the role of the wetting layer.