Hybrid perovskites are emerging as highly efficient materials for optoelectronic applications, however, the operational lifetime has remained a limiting factor for the continued progress of perovskite light emitting devices such as light emitting diodes (LEDs) and perovskite light emitting electrochemical cells (PeLECs). In this work, PeLECs utilizing an optimized fraction of LiPF6 salt additive exhibit enhanced stability. At 0.5 wt% LiPF6, devices exhibit 100 h operation at high brightness in excess of 800 cd/m2 under constant current driving, achieving a maximum luminance of 3260 cd/m2 and power efficiency of 9.1 Lm/W. This performance extrapolates to a 6700 h luminance half-life from 100 cd/m2, a 5.6-fold improvement over devices with no lithium salt additive. Analysis under constant voltage driving reveals three current regimes, with lithium addition strongly enhancing current in the second and third regimes. The third regime correlates degradation of luminance with decreased current. These losses are mitigated by LiPF6 addition, an effect postulated to arise from preservation of perovskite structure. To further understand lithium salt addition, electrochemical impedance spectroscopy with equivalent circuit modeling is performed. Electrical double layer widths from ionic redistribution are minimized at 0.5wt% LiPF6 and inversely correlate with efficient performance.
Halide perovskites have attracted increasing research attention regarding their outstanding optoelectronic applications. Owing to its low activation energy, ion migration is implicated in the long-term stability and many unusual transport behaviors of halide perovskite devices. However, precise control of the ionic transport in halide perovskite crystals remains challenging. Here we visualized and quantified the electric-field-induced halide ion migration in an axial CsPbBr$_3$-CsPbCl$_3$ nanowire heterostructure and demonstrated a solid-state ionic rectification, which is due to the non-unifo…
Recently Cui et al. reported on the fabrication a p-n homojunction perovskite solar cell (PSC) using stoichiometric control of sequentially-deposited perovskite layers. The authors propose that the junction leads to an enhanced electric field in the perovskite absorber resulting in improved charge separation. In this response to Cui et al. 2019 we show that the experimental data presented in the paper does not directly support this claim. Furthermore, Cui et al.'s thesis is not compatible with the large body of existing literature showing that mobile ionic defects present in methyl-ammonium le…
Optimizing selective contact layers in photovoltaics is necessary to yield high performing stable devices. However, this has been difficult for perovskites due to their complex interfacial defects that affect carrier concentrations in the active layer as well as charge transfer and recombination at the interface. Using vacuum thermally-evaporated tin oxide as a case study, we highlight electrochemical tests that are simple yet screen device-relevant contact layer properties, making them useful for process development and quality control. Specifically, we show that cyclic voltammetry and potent…
Perovskite light emitting devices have drawn considerable attention for their favorable optoelectronic properties. High carrier mobilities make perovskites excellent candidates as host materials in electroluminescent devices. To achieve high performance in a simple single layer device, we employed a CsPbBr3 perovskite host and a novel ionic iridium complex guest along with a polyelectrolyte to demonstrate efficient light emitting electrochemical cells (PeLECs). For an optimal guest/host blend, 10600 cd/m2 luminance at 11.6 cd/A and 9.04 Lm/W are achieved at 4.1 V. These devices showed voltage-…
Electrochemical insertion-deintercalation reactions are typically associated with significant change of molar volume of the host compound. This strong coupling between ionic currents and strains underpins image formation mechanisms in electrochemical strain microscopy (ESM), and allows exploring the tip-induced electrochemical processes locally. Here we analyze the signal formation mechanism in ESM, and develop the analytical description of operation in frequency and time domains. The ESM spectroscopic modes are compared to classical electrochemical methods including potentiostatic and galvano…
Mobile ions in hybrid perovskite semiconductors introduce a new degree of freedom to electronic devices suggesting applications beyond photovoltaics. An intuitive device model describing the interplay between ionic and electronic charge transfer is needed to unlock the full potential of the technology. We describe the perovskite-contact interfaces as transistors which couple ionic charge redistribution to energetic barriers controlling electronic injection and recombination. This reveals an amplification factor between the out of phase electronic current and the ionic current. Our findings sug…
Humid hydrophobic ionic liquids, widely used as electrolytes, have narrowed electrochemical windows, because their water, absorbed on the electrode surface, gets involved in electrolysis. In this work, we performed molecular dynamics simulations to explore effects of adding Li-salt in humid ionic liquids on the water adsorbed on the electrode surface. Results reveal that most of water molecules are pushed away from both cathode and anode, by adding salt. The water remained on the electrode is almost bound with Li+, which has significantly lowered activity. The Li+-bonding and re-arrangement of…
Electrochemical strains are a ubiquitous feature of solid state ionic devices ranging from ion batteries and fuel cells to electroresistive and memristive memories. Recently, we proposed a scanning probe microscopy (SPM) based approach, referred as electrochemical strain microscopy (ESM), for probing local ionic flows and electrochemical reactions in solids based on bias-strain coupling. In ESM, the sharp SPM tip concentrates the electric field in a small (10-50 nm) region of material, inducing interfacial electrochemical processes and ionic flows. The resultant electrochemical strains are det…
The electrochemical processes in energy storage materials are generally linked with changes of molar volume of the host compound. Here, the frequency dependent strain response of 1D electrochemically active systems to periodic electric bias is analyzed. The sensitivity and resolution of these electrochemical strain measurements are compared to the current-based electrochemical impedance spectroscopy. The resolution and detection limits of interferometric and atomic force microscopy based systems for probing electrochemical reactions on the nanoscale are analyzed.
Ionic liquids are widely used as electrolytes in electrochemical devices. In this context, many experimental and theoretical approaches have been recently developed for characterizing their interface with electrodes. In this perspective article, we review the most recent advances in the field of computer simulations (mainly molecular dynamics). A methodology for simulating electrodes at constant electrical potential is presented. Several types of electrode geometries have been investigated by many groups in order to model planar, corrugated and porous materials and we summarize the results obt…
Point defects in metal halide perovskites play a critical role in determining their properties and optoelectronic performance; however, many open questions remain unanswered. In this work, we apply impedance spectroscopy and deep-level transient spectroscopy to characterize the ionic defect landscape in methylammonium lead triiodide ($MAPbI_3$) perovskites in which defects were purposely introduced by fractionally changing the precursor stoichiometry. Our results highlight the profound influence of defects on the electronic landscape, exemplified by their impact on the device built-in potentia…
Ion migration in perovskite solar cells is usually analyzed and understood in terms of charge neutrality condition. However, several recent reports indicate possibility of ionic imbalance in the active layer due to external ion migration and/or chemical reactions. In this context, here we explore the influence of ionic charge neutrality on the performance of perovskite solar cells. Our results indicate that ionic imbalance leads to an asymmetry in the device electrostatics, which have interesting implications on the impact of material/interface degradation, hysteresis, and finally on the long-…
Based on the reported ion migration under electric field in hybrid lead halide perovskites we have developed a bright, light emitting electrochemical cell with CH3NH3PbBr3 single crystals directly grown on vertically aligned carbon nanotube (VACNT) forests as contact electrodes. Under the applied electric field, charged ions in the crystal drift and accumulate in the vicinity of the electrodes, resulting in an in operando formed p-i-n heterojunction. The decreased interface energy barrier and the strong charge injection due to the CNT tip enhanced electric field, result in a bright green light…
Organometallic lead halide perovskites are highly efficient materials for solar cells and other optoelectronic applications due to their high quantum efficiency and exceptional semiconducting properties. A peculiarity of these perovskites is the substantial ionic motion under external forces. Here, we reveal that electric field-and light-induced ionic motion in MAPbX3 crystals (X=Cl, Br, I and MA=CH3NH3) leads to unexpected piezoelectric-like response, an order of magnitude larger than in ferroelectric perovskite oxides. The nominal macroscopic symmetry of the crystals is broken by redistribut…
Biredox ionic liquids are a new class of functionalized electrolytes that may play an important role in future capacitive energy storage devices. By allowing additional storage of electrons inside the liquids, they can improve device performance significantly. However current devices employ nanoporous carbons in which the diffusion of the liquid and the adsorption of the ions could be affected by the occurrence of electron-transfer reactions. It is therefore necessary to understand better the thermodynamics and the kinetics of such reactions in biredox ionic liquids. Here we perform ab initio …
Perovskites have proven to be a promising candidate for highly-efficient solar cells, light-emitting diodes, and X-ray detectors, overcoming limitations of inorganic semiconductors. However, they are notoriously unstable. The main reason for this instability is the migration of mobile ions through the device during operation, as they are mixed ionic-electronic conductors. Here we show how measuring the capacitance in both the frequency and the time domain can be used to study ionic dynamics within perovskite-based devices, quantifying activation energy, diffusion coefficient, sign of charge, c…
Contrary to the common belief that light-induced halide ion segregation in a mixed halide al-loy occurs within the illuminated area, we find that the Br ions released by light diffuse away from the area, which generates a counter-balancing Coulombic force between the anion deficit and surplus region, together resulting in a macro/mesoscopic size anion ring surrounding the center, showing a photoluminescence ring. Upon removing the illumination, the displaced anions return to the illuminated area, and the restoring force leads to a damped ultra-low-frequency oscillatory ion motion, which may be…
Metallization of initially insulating VO2 via ionic liquid electrolytes (electrolyte gating) has recently been a topic of much interest. It is clear that the metallization takes place electrochemically and there has previously been extensive evidence for the removal of small amounts of oxygen during ionic liquid gating. Hydrogen intercalation has also been proposed, but the source of the hydrogen has remained unclear. In this work, solid-state magic angle spinning NMR spectroscopy is used to investigate the thermal metal-insulator transition in VO2, before progressing to catalytically hydrogen…
One of the key challenges for future development of efficient and stable metal halide perovskite solar cells is related to the migration of ions in these materials. Mobile ions have been linked to the observation of hysteresis in the current--voltage characteristics, shown to reduce device stability against degradation and act as recombination centers within the band gap of the active layer. In the literature one finds a broad spread of reported ionic defect parameters (e.g. activation energies) for seemingly similar perovskite materials, rendering the identification of the nature of these spe…
In this paper we investigated the influence of the rare-earth ionic radii on the spin-phonon coupling in RE2NiMnO6 double perovskites by Raman spectroscopy. Spin-phonon in dense Nd2NiMnO6 and Gd2NiMnO6 ceramics were investigated by Raman spectroscopy at low temperatures. The magnitude of the coupling observed in comparison with other isostructural compounds shows that it is not influenced by the rare-earth ionic radius, as well as the deviation of the position of the stretching phonon in the ferromagnetic phase with relation to the anharmonic contributions follows a power law.
Perovskite solar cells (PSC) are shown to behave as coupled ionic-electronic conductors with strong evidence that the ionic environment moderates both the rate of electron-hole recombination and the band offsets in planar PSC. Numerous models have been presented to explain the behavior of perovskite solar cells, but to date no single model has emerged that can explain both the frequency and time dependent response of the devices. Here we present a straightforward coupled ionic-electronic model that can be used to explain the large amplitude transient behavior and the impedance response of PSC.
Local Multimodal Dynamics in Mixed Ionic-Electronic Conductors and Their Fingerprints in Organic Electrochemical Transistor Operation
Institut de Bioenginyeria de Catalunya (IBEC), The Barcelona Institute of Science and Technology (BIST)（巴塞罗那生物工程研究所，巴塞罗那科学技术研究院）；Center for Nano Science and Technology, Istituto Italiano di Tecnologia（意大利理工学院纳米科学和技术中心）；Laboratory of Organic Electronics, Department of Science and Technology (ITN), Linköping University（林雪平大学科技学院有机电子实验室）；Department d'Enginyeria Electrònica i Biomèdica, Universitat de Barcelona（巴塞罗那大学生物医学电子工程系）；Center for Nanophase Materials Sciences, Oak Ridge National Laboratory（橡树岭国家实验室纳米相材料科学中心）
Normal operations of electrochemical devices such as solid oxide fuel cells (SOFC), solid oxide electrolyzer cells (SOEC) and lithium ion batteries (LIB) sometimes fail because of unexpected formation of internal phases. These phases include oxygen bubbles at grain boundaries inside the zirconia electrolyte of SOEC, isolated Li metal islands inside the (garnet type) Li7La3Zr2O12 electrolyte of all-solid-state LIB, and similar Na metal islands inside the Na-beta-alumina and NASICON electrolytes of Na-S batteries. Remarkably, although the devices can operate in both polarities, the propensity fo…
Methylene blue (MB) is often used in textile industries and is actively present in the wastewater runs-off. Recently, mediated electrochemical oxidation (MEO) offers a fast, reliable and promising results for environmental remediation. Thus, we aimed to evaluate the electro-degradation potential of MB by MEO using Ce(IV) ionic mediator. Furthermore, we also observed the influence of addition Ag(I) ion catalyst in MEO for degradation of MB. The electro-degradation of MB was evaluated by cyclic voltammetry technique and was confirmed by UV-Vis spectrophotometry, high performance liquid chromatog…
Reliable first-principles calculations of electrochemical processes require accurate prediction of the interfacial capacitance, a challenge for current computationally-efficient continuum solvation methodologies. We develop a model for the double layer of a metallic electrode that reproduces the features of the experimental capacitance of Ag(100) in a non-adsorbing, aqueous electrolyte, including a broad hump in the capacitance near the Potential of Zero Charge (PZC), and a dip in the capacitance under conditions of low ionic strength. Using this model, we identify the necessary characteristic…
We report the synthesis and characterization of a novel class of ionic semiconductor materials- inorganic chalcogenide perovskites. Several different compounds including BaZrS3, CaZrS3, SrTiS3 and SrZrS3 were synthesized by high temperature sulfurization of their oxide counterparts. Their crystal structures were identified by XRD and composition by EDX. UV-vis and photoluminescence measurements confirmed that they are direct gap semiconductors with band gap values consistent with theoretical predictions. By adopting an anion alloying approach, we demonstrate widely tunable band gap from 1.73 e…
Ionic migration has been proposed as a possible cause of photovoltaic current-voltage hysteresis in hybrid perovskite solar cells. However, a major objection to this hypothesis is that hysteresis can be reduced by changing the interfacial contact materials, which are unlikely to significantly influence the behaviour of ionic defects within the perovskite phase. Here we use transient optoelectronic measurements, combined with device simulations, to show that the primary effects of ionic migration can in fact be observed both in devices with hysteresis, and with hysteresis free type contact mate…
Hybrid organic-inorganic perovskites (HOIPs) have recently emerged as highly promising solution-processable materials for photovoltaic (PV) and other optoelectronic devices. HOIPs represent a broad family of materials with properties highly tuneable by the ions that make up the perovskite structure as well as their multiple combinations. Interestingly, recent high-efficiency PV devices using HOIPs with substantially improved long-term stability have used combinations of different ionic compositions. The structural dynamics of these systems are unique for semiconducting materials and are curren…
Nonylphenol ethoxylate (NPE 10) is a non ionic surfactant which is synthesized from alkylphenol ethoxylate. The accumulation of NPE-10 in wastewater will endanger the ecosystem as well as human being. At present, by an advancement of technology NPE 10 can be degraded indirectly by using an electrochemically treatment. Thus, this study aimed to evaluate the potential electrodegradation of NPE 10 by mediated electrochemical oxidation (MEO) using Ce(IV) ionic mediator. In addition, the influence of Ag(I) ionic catalyst in the performance of MEO for degradation of NPE 10 was also observed. The pot…
Organic-inorganic metal halide perovskite devices have generated significant interest for LED, photodetector, and solar cell applications due to their attractive optoelectronic properties and substrate-choice flexibility1-4. These devices exhibit slow time-scale response, which have been explained by point defect migration5-6. In this work, we report the discovery of a room temperature intrinsic amplification process in methylammonium lead iodide perovskite (MAPbI3) that can be triggered by few photons, down to a single photon. The electrical properties of the material, by way of photoresponse…
In a recent work by Jiang et al. [J. Phys. Chem. Solids 67 (2006) 1531-1536], the interrelationship between lattice constant, ionic radii and tolerance factor of cubic perovskites has been established and an empirical equation was obtained. However, the assumption of incorrect ionic coordination led to an incorrect mathematical expression even though the average relative errors between predicted and observed lattice constants of 132 materials were below 1%. Here, corrected coefficients for that empirical expression are obtained, which would likely be useful for investigation of general perovsk…
Ionic-instability induced color tuning in lead-based, mixed-halide perovskites
Chromatic Lighting（色度照明）；University of Notre Dame, Department of Physics and Astronomy（圣母大学物理与天文系）；University of Notre Dame, Department of Chemistry and Biochemistry（圣母大学生物化学系）；I-LAMP and Dipartimento di Matematica e Fisica, Università Cattolica del Sacro Cuore（天主教大学数学与物理系及I-LAMP）；PY Materials（PY材料公司）；Notre Dame Radiation Laboratory（圣母大学辐射实验室）
Overcoming Transport Layer Bottlenecks to Quantify Ionic Parameters from Transient Ion Current Measurements of Perovskite Solar Cells
Zhejiang University（浙江大学）；Zurich University of Applied Sciences (ZHAW)（苏黎世应用科学大学）；ETH Zürich（苏黎世联邦理工学院）；University of Zurich（苏黎世大学）；Fluxim AG（Fluxim公司）；Empa – Swiss Federal Laboratories for Materials Science and Technology（瑞士联邦材料科技研究所）；Institute of Computational Physics, Zurich University of Applied Sciences (ZHAW)（苏黎世应用科学大学计算物理研究所）；Department of Chemistry and Applied Biosciences, ETH Zürich（苏黎世联邦理工学院化学与应用生物学系）；Department of Mathematical Modeling and Machine Learning, University of Zurich（苏黎世大学数学建模与机器学习系）；Laboratory for Thin Films and Photovoltaics, Empa – Swiss Federal Laboratories for Materials Science and Technology（瑞士联邦材料科技研究所薄膜与光伏实验室）；Physik-Institut, University of Zurich（苏黎世大学物理学院）
We present low-temperature anelastic and dielectric spectroscopy measurements on the perovskite ionic conductor BaCe(1-x)Y(x)O(3-x/2) in the protonated, deuterated and outgassed states. Three main relaxation processes are ascribed to proton migration, reorientation about an Y dopant and tunneling around a same O atom. An additional relaxation maximum appears only in the dielectric spectrum around 60 K, and does not involve H motion, but may be of electronic origin, e.g. small polaron hopping. The peak at the lowest temperature, assigned to H tunneling, has been fitted with a relaxation rate pr…
Kinetics of electrochemical reactions are several orders of magnitude slower in solids than in liquids as a result of the much lower ion diffusivity. Yet, the solid state maximizes the density of redox species, which is at least two orders of magnitude lower in liquids because of solubility limitations. With regard to electrochemical energy storage devices, this leads to high-energy batteries with limited power and high-power supercapacitors with a well-known energy deficiency. For such devices the ideal system should endow the liquid state with a density of redox species close to the solid st…
Investigation of the inherent field-driven charge transport behaviour of 3D lead halide perovskites has largely remained a challenging task, owing primarily to undesirable ionic migration effects near room temperature. In addition, the presence of methylammonium in many high performing 3D perovskite compositions introduces additional instabilities, which limit reliable room temperature optoelectronic device operation. Here, we address both these challenges and demonstrate that field-effect transistors (FETs) based on methylammonium-free, mixed-metal (Pb/Sn) perovskite compositions, that are wi…
Hybrid halide perovskites such as methylammonium lead iodide (CH3NH3PbI3) exhibit unusually low free carrier concentrations despite being processed at low-temperatures from solution. We demonstrate, through quantum mechanical calculations, that the origin of this phenomenon is a prevalence of ionic over electronic disorder in stoichiometric materials. Schottky defect formation provides a mechanism to self-regulate the concentration of charge carriers through ionic compensation of charged point defects. The equilibrium charged vacancy concentration is predicted to exceed 0.4% at room temperatur…
We present a simple ionic model which successfully reproduces the various types of compositional long-range order observed in a large class of complex insulating perovskite alloys. The model assumes that the driving mechanism responsible for the ordering is simply the electrostatic interaction between the different ionic species. A possible new explanation for the anomalous long-range order observed in some Pb relaxor alloys, involving the proposed existence of a small amount of Pb^4+ on the B sublattice, is suggested by an analysis of the model.
Ionic liquids (ILs) are salts that are liquid close to room temperature. Their possible applications are numerous, e.g., as solvents for green chemistry in various electrochemical devices, and even for such "exotic" purposes as spinning-liquid mirrors for lunar telescopes. Here we concentrate on their use for new advancements in energy-storage and -conversion devices: Batteries, supercapacitors or fuel cells using ILs as electrolytes could be important building blocks for the sustainable energy supply of tomorrow. Interestingly, ILs show glassy freezing and the universal, but until now only po…
The properties of AMO3 perovskite oxides, where M is a 3d transition metal, depend strongly on the level of covalency between the metal d and oxygen p orbitals. With their complex spin orders and metal-insulator transition, rare-earth nickelates verge between dominantly ionic and covalent characters. Accordingly, the nature of their ground state is highly debated. Here, we reconcile the ionic and covalent visions of the insulating state of nickelates. Through first-principles calculations, we show that it is reminiscent of the ionic charge disproportionation picture (with strictly low-spin 4+ …
With the rapid evolution of lead halide perovskite solar cells, there are considerable evidences that the mobile ions strongly impact their properties. However, except the activation energy, the other properties of ionic migration are mostly explored with first principle calculations. Here we investigate the migration of halide ion (vacancy) in lead bromide perovskite single crystalline microplates. In contrast to conventional studies with external bias voltages, we introduce built-in potentials into the microplates via low-energy electron beams and study the corresponding ionic migrations. By…
We study the oxo-hexametallate Li$_7$TaO$_6$ with first-principles and classical molecular dynamics simulations, obtaining a low activation barrier for diffusion of $\sim$0.29 eV and a high ionic conductivity of $5.7 \times 10^{-4}$ S cm$^{-1}$ at room temperature (300 K). We find evidence for a wide electrochemical stability window from both calculations and experiments, suggesting its viable use as a solid-state electrolyte in next-generation solid-state Li-ion batteries. To assess its applicability in an electrochemical energy storage system, we performed electrochemical impedance spectrosc…
The assembly of aligned carbon nanotubes (CNT) into fibers (CNTF) is a convenient approach to exploit and apply the unique physico-chemical properties of CNTs in many fields. CNT functionalization has been extensively used for their implementation into composites and devices. However, CNTF functionalization is still in its infancy, due to the challenges associated with preservation of CNTF morphology. Here, we report a thorough study of the gas-phase functionalization of CNTF fabrics using ozone that was generated in situ from a UV-source. By contrast with liquid-based oxidation methods, this …
Next-generation implantable computational devices require long-term stable electronic components capable of operating in, and interacting with, electrolytic surroundings without being damaged. Organic electrochemical transistors (OECTs) emerged as fitting candidates. However, while single devices feature impressive figures of merit, integrated circuits (ICs) immersed in a common electrolytes are hard to realize using electrochemical transistors, and there is no clear path forward for optimal top-down circuit design and high-density integration. The simple observation that two OECTs immersed in…
The emergence of halide perovskites in photovoltaics has diversified the research on this material family and extended their application towards several fields in the optoelectronics, such as photo- and ionizing-radiation-detectors. One of the most basic characterization protocols consist on measuring the dark current-voltage (J-V) curve of symmetrically contacted samples for identifying the different regimes of space-charge-limited current (SCLC). Customarily, J=C*V^n curves indicate the Mott-Gurney law when n=2, or the Child-Langmuir ballistic regime of SCLC when n=3/2. The latter can be oft…
