Amanda J. Neukirch

High-efficiency solution-processed perovskite solar cells with millimeter-scale grains

Large-crystal perovskite films The performance of organic-inorganic hybrid perovskite planar solar cells has steadily improved. One outstanding issue is that grain boundaries and defects in polycrystalline films degrade their output. Now, two studies report the growth of millimeter-scale single crystals. Nie et al. grew continuous, pinhole-free, thin iodochloride films with a hot-casting technique and report device efficiencies of 18%. Shi et al. used antisolvent vapor-assisted crystallization to grow millimeter-scale bromide and iodide cubic crystals with charge-carrier diffusion lengths exceeding 10 mm. Science, this issue p. 522, p. 519 Solution processing techniques enable the growth of high-quality, large-area perovskite crystals for solar cells. State-of-the-art photovoltaics use high-purity, large-area, wafer-scale single-crystalline semiconductors grown by sophisticated, high-temperature crystal growth processes. We demonstrate a solution-based hot-casting technique to grow continuous, pinhole-free thin films of organometallic perovskites with millimeter-scale crystalline grains. We fabricated planar solar cells with efficiencies approaching 18%, with little cell-to-cell variability. The devices show hysteresis-free photovoltaic response, which had been a fundamental bottleneck for the stable operation of perovskite devices. Characterization and modeling attribute the improved performance to reduced bulk defects and improved charge carrier mobility in large-grain devices. We anticipate that this technique will lead the field toward synthesis of wafer-scale crystalline perovskites, necessary for the fabrication of high-efficiency solar cells, and will be applicable to several other material systems plagued by polydispersity, defects, and grain boundary recombination in solution-processed thin films.

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.

Light-activated photocurrent degradation and self-healing in perovskite solar cells

Solution-processed organometallic perovskite solar cells have emerged as one of the most promising thin-film photovoltaic technology. However, a key challenge is their lack of stability over prolonged solar irradiation. Few studies have investigated the effect of light soaking on hybrid perovskites and have attributed the degradation in the optoelectronic properties to photochemical or field-assisted ion migration. Here we show that the slow photocurrent degradation in thin-film photovoltaic devices is due to the formation of light-activated meta-stable deep-level trap states. However, the devices can self-heal completely by resting them in the dark for <1 min or the degradation can be completely prevented by operating the devices at 0 °C. We investigate several physical mechanisms to explain the microscopic origin for the formation of these trap states, among which the creation of small polaronic states involving localized cooperative lattice strain and molecular orientations emerges as a credible microscopic mechanism requiring further detailed studies.

Colloidal Semiconductor Quantum Dots with Tunable Surface Composition

Colloidal CdS quantum dots (QDs) were synthesized with tunable surface composition. Surface stoichiometry was controlled by applying reactive secondary phosphine sulfide precursors in a layer-by-layer approach. The surface composition was observed to greatly affect photoluminescence properties. Band edge emission was quenched in sulfur terminated CdS QDs and fully recovered when QDs were cadmium terminated. Calculations suggest that electronic states inside the band gap arising from surface sulfur atoms could trap charges, thus inhibiting radiative recombination and facilitating nonradiative relaxation.

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.

Nonadiabatic Ensemble Simulations of cis-Stilbene and cis-Azobenzene Photoisomerization

Structurally, stilbene and azobenzene molecules exist in closed and open cis and trans forms, which are able to transform into each other under the influence of light (photoisomerization). To accurately simulate the photoisomerization processes, one must go beyond ground-state (Born-Oppenheimer) calculations and include nonadiabatic coupling between the electronic and vibrational states. We have successfully implemented nonadiabatic couplings and a surface-hopping algorithm within a density functional theory approach that utilizes local orbitals. We demonstrate the effectiveness of our approach by performing molecular dynamics simulations of the cis-trans photoisomerization in both azobenzene and stilbene upon excitation into the S1 state. By generating an ensemble of trajectories, we can gather characteristic transformation times and quantum yields that we will discuss and compare with ultrafast spectroscopic experiments.

Phonon-induced pure-dephasing of luminescence, multiple exciton generation, and fission in silicon clusters

The size and temperature dependence of the pure-dephasing processes involved in luminescence, multiple exciton generation (MEG), and multiple exciton fission (MEF) are investigated for Sin clusters (n = 5-10, 15) using ab initio molecular dynamics and optical response function theory. The cluster bandgaps correlate with two types of binding energy, indicating that bandgaps can be used to characterize cluster stability. Ranging from 5 to 100 fs, the dephasing times are found to be longest for MEF and shortest for MEG, with luminescence falling in the middle range. Generally, the dephasing is fast, if the orbitals supporting the pair of states involved in the superpositions differ in energy, atomic localization, and number of nodes. The dephasing accelerates with temperature, because more phonon modes are activated, and lower frequency acoustic modes are able to explore the anhamonic part of the potential energy surface. The temperature dependence is stronger for larger clusters, since they possess a wider range of low-frequency anharmonic modes. Our research indicates that rapid dephasing in Si clusters favors generation of independent charge carriers from single and multiple excitons, making the clusters a promising material for photon energy conversion. The simulations of the dephasing processes reported in this work assist in understanding of the exciton evolution pathways in inorganic semiconductor clusters and other nanoscale materials.

Calculated photo-isomerization efficiencies of functionalized azobenzene derivatives in solar energy materials: azo-functional organic linkers for porous coordinated polymers

Recently, we used a local orbital density functional theory code called FIREBALL, to study the photoisomerization process in azobenzene derivatives for solar energy materials. Azobenzene functional groups undergo photoisomerization upon light irradiation or application of heat. Zhou et al (2012 J. Am. Chem. Soc. 134 99-102) showed that these azobenzenes can then be introduced into metal-organic frameworks via an organic linker in order to create a reversible switch for CO2 adsorption. In this manuscript, we examined how the addition of organic linkers (isophthalic acid) changes the relaxation times, isomerization mechanism, and quantum yield for both the cis↔trans pathways. We then tuned these properties by substituting functional groups, finding an increase in quantum yield as well as improved optical properties.

Excited-state vibrational dynamics toward the polaron in methylammonium lead iodide perovskite

Hybrid organic–inorganic perovskites have attractive optoelectronic properties including exceptional solar cell performance. The improved properties of perovskites have been attributed to polaronic effects involving stabilization of localized charge character by structural deformations and polarizations. Here we examine the Pb–I structural dynamics leading to polaron formation in methylammonium lead iodide perovskite by transient absorption, time-domain Raman spectroscopy, and density functional theory. Methylammonium lead iodide perovskite exhibits excited-state coherent nuclear wave packets oscillating at ~20, ~43, and ~75 cm−1 which involve skeletal bending, in-plane bending, and c-axis stretching of the I–Pb–I bonds, respectively. The amplitudes of these wave packet motions report on the magnitude of the excited-state structural changes, in particular, the formation of a bent and elongated octahedral PbI64− geometry. We have predicted the excited-state geometry and structural changes between the neutral and polaron states using a normal-mode projection method, which supports and rationalizes the experimental results. This study reveals the polaron formation via nuclear dynamics that may be important for efficient charge separation.Elucidating electron-phonon coupling in hybrid organic-inorganic perovskites may help us to understand the high photovoltaic efficiency. Here, the authors observe low-frequency Raman modes and related nuclear displacements of the Pb–I framework, indicating how these vibrational motions lead to polaron formation in perovskites.

Slow Relaxation of Surface Plasmon Excitations in Au55: The Key to Efficient Plasmonic Heating in Au/TiO2

Gold nanoparticles distinguish themselves from other nanoparticles due to their unique surface plasmon resonance properties that can be exploited for a multiplicity of applications. The promise of plasmonic heating in systems of Au nanoparticles on transition metal oxide supports, for example, Au/TiO2, rests with the ability of the surface plasmon in Au nanoparticles to effectively transfer energy into the transition metal oxide. Here, we report a critical observation regarding Au nanoparticle (Au55) surface plasmon excitations, that is, the relaxation of the surface plasmon excitation is very slow, on the order of several picoseconds. Starting from five plasmon states in Au55 nanoparticles using nonadiabatic molecular dynamics simulations, we find that the relaxation time constant resulting from these simulations is ∼6.8 ps, mainly resulting from a long-lived intermediate state found at around -0.8 eV. This long-lived intermediate state aligns with the conduction band edge of TiO2, thereby facilitating energy transfer injection from the Au55 nanoparticle into the TiO2. The current results rule out the previously reported molecular-like relaxation dynamics for Au55.