We have analyzed a limited sample set of 120 GHz, and 150 GHz time-resolved millimeter wave (mmW) photoconductive decay (mmPCD) signals of 300 nm thick air-stable encapsulated perovskite film (methyl-ammonium lead halide) excited using a pulsed 532-nm laser with fluence 10.6 micro-Joules per cm-2. We correlated 12 parameters derived directly from acquired mmPCD kinetic-trace data and its step-response, each with the sample-age based on the date of the experiment. Five parameters with a high negative correlation with sample age were finally selected as predictors in the Gaussian Process Regression (GPR) machine learning model for prediction of the age of the sample. The effects of aging (between 0 and 40,000 hours after film production) are quantified mainly in terms of a shift in peak voltage, the response ratio (conductance parameter), loss-compensated transmission coefficient, and the radiofrequency (RF) area of the transient itself (flux). Changes in the other step-response parameters and the decay length of the aging transients are also shown. The GPR model is found to work well for a forward prediction of the age of the sample using this method. It is noted that the Matern-5 over 2 GPR kernel for supervised learning provides the best realistic solution for age prediction with R squared around 0.97.
Efficient charge separation at the interfaces between the perovskite and with the carrier transport layers is crucial for perovskite solar cells to achieve high power conversion efficiency. We systematically investigate the hole injection dynamics from MAPbI$_3$ perovskite to three typical hole transport materials (HTMs) PEDOT:PSS, PTAA and NiO$_x$ by means of pump-probe transmission measurements. We photoexcite only near the MAPbI$_3$/HTM interface or near the back surface, and measure the differential transient transmission between the two excitation configurations to extract the carrier dyn…
While transient photoluminescence measurements are a very popular tool to monitor the charge-carrier dynamics in the field of halide perovskite photovoltaics, interpretation of data obtained on multilayer samples is highly challenging due to the superposition of various effects that modulate the charge-carrier concentration in the perovskite layer and thereby the measured PL. These effects include bulk and interfacial recombination, charge transfer to electron or hole transport layers and capacitive charging or discharging. Here, numerical simulations with Sentauraus TCAD, analytical solutions…
Solar cells based on organic-inorganic metal halide perovskites show efficiencies close to highly-optimized silicon solar cells. However, ion migration in the perovskite films leads to device degradation and impedes large scale commercial applications. We use transient ion-drift measurements to quantify activation energy, diffusion coefficient, and concentration of mobile ions in methylammonium lead triiodide (MAPbI3) perovskite solar cells, and find that their properties change close to the tetragonal-to-orthorhombic phase transition temperature. We identify three migrating ion species which …
The extraction of photogenerated charge carriers and the generation of a photovoltage belong to the fundamental functionalities of any solar cell. These processes happen not instantaneously but rather come with finite time constants, e.g., a time constant related to the rise of the externally measured open circuit voltage following a short light pulse. The present paper provides a new method to analyze transient photovoltage measurements at different bias light intensities combining rise and decay times of the photovoltage. The approach uses a linearized version of a system of two coupled diff…
Transient microscopy is of vital importance in understanding the dynamics of optical excited states in optoelectronic materials, as it allows for a direct visualization of the movement of energy carriers in space and time. Important information on the influence of trap-states can be obtained using this technique, typically observed as a slow-down of the energy transport as carriers are trapped at defect sites. To date, however, studies of the trap-state dynamics have been mostly limited to phenomenological descriptions of the early time-dynamics. In this report, we show how long-acquisition-ti…
Determination of the device performance parameters of perovskite solar cells is far from trivial as transient effects may cause large discrepancies in current-voltage measurements as a function of scan rate and pre-conditioning. Maximum power point tracking, MPPT, enables to determine the steady-state maximum power conversion efficiency. However, the MPPT does not provide any information on the device performance parameters, which are reliable only if extracted from current-voltage curves collected under steady-state conditions. We show that is possible to determine the shorter settling or del…
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…
The speed of sound and elastic properties of single crystals of inorganic and hybrid lead-free iodide perovskites obtained by femtosecond transient optical reflectivity
Halide perovskites are a versatile class of semiconductors employed for high performance emerging optoelectronic devices, including flexoelectric systems, yet the influence of their ionic nature on their mechanical behaviour is still to be understood. Here, a combination of atomic-force, optical and compositional X-ray microscopy techniques is employed to shed light on the mechanical properties of halide perovskite films at the nanoscale. We reveal mechanical domains within and between morphological grains, enclosed by mechanical boundaries of higher Young's Modulus than the bulk parent materi…
The ideality factor determined by measuring the open circuit voltage (VOC) as function of light intensity is often used as a means to identify the dominant recombination mechanism in solar cells. However, applying this Suns-VOC technique to perovskite cells is problematic since the VOC evolves with time in a way which depends on the previously applied bias (Vpre), the light intensity, and the device architecture/processing. Here we show that the dominant recombination mechanism in two structurally similar CH3NH3PbI3 devices containing either mesoporous Al2O3 or TiO2 layers can be identified fr…
The long-term stability of halide perovskite solar cells (PSCs) remains the critical problem of this photovoltaic technology. Different structural defects formed in the thin-film perovskite films were considered as a main trigger for the decomposition of the absorber and corrosion of the interfaces in the device structure. The changes in the stability performance of the PSCs require a detailed analysis of the defects generated under external stress (light and heat). Using admittance, deep-level transient spectroscopy (DLTS) and reverse DLTS we determined the evolution of the defect energy leve…
Transient Ferromagnetism in Ultrafast Phase Transitions in Perovskites under XUV Irradiation: A Comparative Study of SrTiO3 and KTaO3
Institute of Physics, Czech Academy of Sciences（捷克科学院物理研究所）；Faculty of Nuclear Sciences and Physical Engineering, Czech Technical University in Prague（布拉格捷克理工大学核科学与物理工程学院）；Institute of Plasma Physics, Czech Academy of Sciences（捷克科学院等离子体物理研究所）
We report the application of femtosecond four-wave mixing (FWM) to the study of carrier transport in solution-processed CH3NH3PbI3. The diffusion coefficient was extracted through direct detection of the lateral diffusion of carriers utilizing the transient grating technique, coupled with simultaneous measurement of decay kinetics exploiting the versatility of the boxcar excitation beam geometry. The observation of exponential decay of the transient grating versus interpulse delay indicates diffusive transport with negligible trapping within the first nanosecond following excitation. The in-pl…
Semiconductor doped glasses had been used by the research and engineering communities as color filters or saturable absorbers well before it was realized that their optical properties were defined by tiny specs of semiconductor matter known presently as quantum dots (QDs). Nowadays, the preferred type of QD samples are colloidal particles; however, there is still a number of applications that would benefit from the availability of high-quality glass-based QD samples. These applications include fiber optics, optically pumped lasers and amplifiers, and luminescent solar concentrators. Here we co…
Photoinduced metastable cation disorder in metal halide double perovskites
Yale University（耶鲁大学）；Argonne National Laboratory（阿贡国家实验室）；The University of Toledo（托莱多大学）；University of Pennsylvania（宾夕法尼亚大学）；Cornell University（康奈尔大学）；Brookhaven National Laboratory（布鲁克海文国家实验室）
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）
Perovskite-based optoelectronic devices have gained significant attention due to their remarkable performance and low processing cost, particularly for solar cells. However, for perovskite light-emitting diodes (LEDs), non-radiative charge carrier recombination has limited electroluminescence (EL) efficiency. Here we demonstrate perovskite-polymer bulk heterostructure LEDs exhibiting record-high external quantum efficiencies (EQEs) exceeding 20%, and an EL half-life of 46 hours under continuous operation. This performance is achieved with an emissive layer comprising quasi-2D and 3D perovskite…
Millimeter size single crystals of double perovskite La2NiMnO6 (LNMO) were grown by the High Temperature Solution Growth Method. The magnetic measurements and polarized Raman spectra between 5 and 350K provide evidence that the crystals have high degree of Ni(2+)/Mn(4+)ordering, small amount of lattice defects and highest Tc = 288K reported so far for ferromagnetic double perovskites. At a microscopic level the crystals are heavily twinned and the effect of twinning on the Raman spectra is analyzed in detail.
In high performance perovskite based solar cells, CH3NH3PbI3 is the key material. We carried out a study on charge diffusion in spin-coated CH3NH3PbI3 perovskite thin film by transient fluorescent spectroscopy. A thickness-dependent fluorescent lifetime was found. By coating the film with an electron or hole transfer layer, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) or 2,2,7,7-tetrakis(N,N-di-p-methoxyphenylamine)-9,9-spirobifluorene (Spiro-OMeTAD) respectively, we observed the charge transfer directly through the fluorescence quenching. One-dimensional diffusion model was applied to ob…
Non-toxicity and stability make two-dimensional (2D) bismuth halide perovskites better alternatives to lead-based ones for optoelectronic applications and catalysis. In this work, we synthesize sub-micron size colloidal quasi-2D Cs3Bi2I9 perovskite nanosheets and study their generation and relaxation of charge carriers. Steady-state absorption spectroscopy reveals an indirect bandgap of 2.07 eV, which is supported by the density functional theory calculated band structure. The nanosheets do not show detectable photoluminescence at room temperature at band-edge excitation which is attributed to…
Although it has been recently demonstrated that the laser-assisted (LA) crystallization process leads to the formation of perovskite absorber films of superior photovoltaic performance compared to conventional thermal annealing (TA), the physical origin behind this important discovery is missing. In this study, CH$_3$NH$_3$PbI$_3$ perovskite thin films have been synthesized by means of LA and TA crystallization on the surface of two hole transport layers (HTL) namely poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) and poly(triarylamine) (PTAA). A systematic study of the eff…
Hot-carrier cooling (HCC) in metal halide perovskites in the high-density regime is significantly slower compared to conventional semiconductors. This effect is commonly attributed to a hot-phonon bottleneck but the influence of the lattice properties on the HCC behaviour is poorly understood. Using pressure-dependent transient absorption spectroscopy (fs-TAS) we find that at an excitation density below Mott transition, pressure does not affect the HCC. On the contrary, above Mott transition, HCC in methylammonium lead iodide (MAPbI3) is around two times as fast at 0.3 GPa compared to ambient …
Metal-halide perovskites are a versatile material platform for light-harvesting and light-emitting applications as their variable chemical composition allows the optoelectronic properties to be tailored to specific applications. Halide mixing is one of the most powerful techniques to tune the optical bandgap of metal-halide perovskites across wide spectral ranges. However, halide mixing has commonly been observed to result in phase segregation, which reduces excited-state transport and limits device performance. While the current emphasis lies on the development of strategies to prevent phase …
Metal halide perovskites (MHPs) are known to undergo several structural phase transitions, from lower to higher symmetry, upon heating. While structural phase transitions have been investigated by a wide range of optical, thermal and electrical methods, most measurements are quasi-static and hence do not provide direct information regarding the fundamental timescale of phase transitions in this emerging class of semiconductors. Here we investigate the timescale of the orthorhombic-to-tetragonal phase transition in the prototypical metal halide perovskite, methylammonium lead triiodide (CH3NH3P…
We report on the exciton formation and relaxation dynamics following photocarrier injection in a single-layer two-dimensional lead-iodide perovskite. We probe the time evolution of four distinct exciton resonances by means of time-resolved photoluminescence and transient absorption spectroscopies, and find that at 5\,K a subset of excitons form on a $\lesssim$ 1-ps timescale, and that these relax subsequently to lower-energy excitons on $\sim$ 5--10\,ps with a marked temperature dependence over $<$ 100\,K. We implement a mode projection analysis that determines the relative contribution of all…
Metal halide perovskites possess many physical properties amenable to optoelectronic applications, whereas the realization of these potentials has been hampered by their environmental and electronic instabilities. The morphological and molecular low dimensional perovskites and perovskite related materials have shown much promise in enhancing the chemical stability due to their unique molecular structures. Here we report on robust and reproducible four-terminal (4T) electrical measurements in a one-dimensional (1D) organic metal halide hybrid, (R)-α-methylbenzylammonium lead triiodide ((R-α-MBA…
Confinement-induced Ultrafast Conductivity in 2D Perovskites resolved by correlative Terahertz-NIR Spectroscopy
University of Bayreuth（拜罗伊特大学）；Ulm University（乌尔姆大学）；Bayreuth Institute of Macromolecular Research (BIMF)（拜罗伊特大分子研究所）；Bavarian Polymer Institute (BPI)（巴伐利亚聚合物研究所）；The University of Melbourne（墨尔本大学）
Optoelectronic phenomena in materials such as organic/inorganic hybrid perovskites depend on a complex interplay between light induced carrier generation and fast (electronic) and slower (ionic) processes, all of which are known to be strongly affected by structural inhomogeneities such as interfaces and grain boundaries. Here, we develop a time resolved Kelvin probe force microscopy (KPFM) approach, based on the G-Mode SPM platform, allowing quantification of surface photovoltage (SPV) with microsecond temporal and nanoscale spatial resolution. We demonstrate the approach on methylammonium le…
Temperature dependent (4K-300K) photoluminescence and transmission spectra are analyzed to study the effect of changing the different components of a perovskite compound, be it A, B, or X. Four different films are compared: FAMAPbSnI3, FAPbI3, FAMAPbI3, and FAPbBr3. The low temperature results highlight the changes that occur especially, underlying ones that are easily masked at room temperature. The overall Stokes shift is of similar magnitude at room temperature for the 3 Pb only based samples. This is governed by the interaction strength GammaLO, phonon energy ELO, and the exciton binding e…
A negative kink in excess conductivity is observed in p-type non-degenerate (moderate dopant concentration) silicon wafers when excited by a very narrow pulse of 532 nm laser appearing just after the complete positive decay of dark conductivity voltage. Most of the Si samples are pristine, and 3 of them are irradiated with gamma, proton, and chlorine ion beams respectively. These transients were examined using a time-resolved millimeter-wave conductivity apparatus (TRmmWC ) and the radiofrequency (RF) voltage response (after laser cut-off) consistently reveals a positive peak with nominal deca…
The relationship between the magnetic interaction and photoinduced dynamics in antiferromagnetic perovskites is investigated in this study. In La${}_{1/3}$Sr${}_{2/3}$FeO${}_{3}$ thin films, commensurate spin ordering is accompanied by charge disproportionation, whereas SrFeO${}_{3}$ thin films show incommensurate helical antiferromagnetic spin ordering due to increased ferromagnetic coupling compared to La${}_{1/3}$Sr${}_{2/3}$FeO${}_{3}$. To understand the photoinduced spin dynamics in these materials, we investigate the spin ordering through time-resolved resonant soft X-ray scattering. In …
$ \mathrm{Sr}_{4}\mathrm{Al}_{2}\mathrm{O}_{7}$: A New Sacrificial Layer with High Water Dissolution Rate for the Synthesis of Freestanding Oxide Membranes
Cs2AgBiBr6 (CABB) has been proposed as a promising non-toxic alternative to lead halide perovskites. However, low charge carrier collection efficiencies remain an obstacle for the incorporation of this material in optoelectronic applications. In this work, we study the optoelectronic properties of CABB thin films using steady state and transient absorption and reflectance spectroscopy. We find that optical measurements on such thin films are distorted as a consequence of multiple reflections within the film. Moreover, we discuss the pathways behind conductivity loss in these thin films, using …
