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Optimizing the interfaces in perovskite solar cells (PSCs) is essential for enhancing their performance, improving their stability, and making them commercially viable for large-scale deployment in solar energy harvesting applications. Point defects, like vacancies, have a dual role, as they can inherently provide a proper doping, but they can also reduce the collected current by trap-assisted recombination. Moreover, they can play an active role in ion migration. Using {\it ab initio} density functional theory (DFT) calculations we investigate the changes in the band alignment induced by interfacial vacancy defects in a TiO$_2$/MAPI/Cu$_2$O based PSC. Depending on the type of the vacancy (Ti, Cu, O, Pb, I) in the oxide and perovskite materials, additional doping is superimposed on the already existing background. Their effect on the performance of the PSCs becomes visible, as shown by SCAPS simulations. The most significant impact is observed for $p$ type doping of TiO$_2$ and $n$ type doping of Cu$_2$O, while the effective doping of the perovskite layer affects one of the two interfaces. We discuss these results based on modification of the band structure near the active interfaces and provide further insights concerning the optimization of electron and hole collection., Comment: 7 pages, 8 figures, 4 sections, 44 references

Herein we present a comparative study among different mesoporous electron transporter layers (ETLs), namely nanometric m-TiO2, m-SnO2 and m-SnO2 quantum dots (QDs), deposited by spray coating method. The experimental data correlated with the photovoltaic parameters indicate that the SnO2 mesoporous layer obtained from the spray deposition of the in-house prepared QDs solution is the best candidate between the three used mesoporous ETLs. The use of the in-house prepared SnO2 QDs solution presents smaller agglomerates composed of 3 nm NPs resulting in the formation of a thinner, more uniform, and compact mesoporous ETL, compared with the other two ETL solutions. The formamidinium-methylamonium-potassium (FAMA@10K) perovskite deposited on this m-SnO2 QDs ETL presents a lower RMS, more uniformity and, a higher amount of PbI2. Interestingly, this higher concentration for PbI2 seems to enhance the performance of the perovskite solar cells (PSC), compared to the other two mesoporous ETLs. Our work reveals that SnO2 QDs solution can be easily produced in the laboratory and it is more suited for the deposition of the mesoporous ETL when choosing a FAMA@10K configuration perovskite solar cell with power conversion efficiency (PCE) higher than 10%., Comment: 20 pages, 14 figures, 6 sections

Diffusion models have been recently used for anomaly detection (AD) in images. In this paper we investigate whether they can also be leveraged for AD on multivariate time series (MTS). We test two diffusion-based models and compare them to several strong neural baselines. We also extend the PA%K protocol, by computing a ROCK-AUC metric, which is agnostic to both the detection threshold and the ratio K of correctly detected points. Our models outperform the baselines on synthetic datasets and are competitive on real-world datasets, illustrating the potential of diffusion-based methods for AD in multivariate time series., Comment: Accepted at the AI4TS workshop of the 23rd IEEE International Conference on Data Mining (ICDM 2023), 9 pages, 7 figures, 2 tables

In this work, the effects of $^\text{60}$Co $\gamma$-ray irradiation on high resistivity $p$-type diodes have been investigated. The diodes were exposed to dose values of 0.1, 0.2, 1, and \SI{2}{\mega Gy}. Both macroscopic ($I$--$V$, $C$--$V$) and microscopic (Thermally Stimulated Current~(TSC)) measurements were conducted to characterize the radiation-induced changes. The investigated diodes were manufactured on high resistivity $p$-type Float Zone (FZ) silicon and were further classified into two types based on the isolation technique between the pad and guard ring: $p$-stop and $p$-spray. After irradiation, the macroscopic results of current-voltage and capacitance-voltage measurements were obtained and compared with existing literature data. Additionally, the microscopic measurements focused on the development of the concentration of different radiation-induced defects, including the boron interstitial and oxygen interstitial (B$_\text{i}$O$_\text{i}$) complex, the carbon interstitial and oxygen interstitial C$_\text{i}$O$_\text{i}$ defect, the H40K, and the so-called I$_\text{P}^*$. To investigate the thermal stability of induced defects in the bulk, isochronal annealing studies were performed in the temperature range of \SI{80}{\celsius} to \SI{300}{\celsius}. These annealing processes were carried out on diodes irradiated with doses of 1 and \SI{2}{\mega Gy} and the corresponding TSC spectra were analysed. Furthermore, in order to investigate the unexpected results observed in the $C$-$V$ measurements after irradiation with high dose values, the surface conductance between the pad and guard ring was measured as a function of both dose and annealing temperature.

This study focuses on the properties of the B$_\text{i}$O$_\text{i}$ (interstitial Boron~-~interstitial Oxygen) and C$_\text{i}$O$_\text{i}$ (interstitial Carbon~-~interstitial Oxygen) defect complexes by \SI{5.5}{\mega\electronvolt} electrons in low resistivity silicon. Two different types of diodes manufactured on p-type epitaxial and Czochralski silicon with a resistivity of about 10~$\Omega\cdot$cm were irradiated with fluence values between \SI{1e15}{\per\square\centi\meter} and \SI{6e15}{\per\square\centi\meter}. Such diodes cannot be fully depleted and thus the accurate evaluation of defect concentrations and properties (activation energy, capture cross-section, concentration) from Thermally Stimulated Currents (TSC) experiments alone is not possible. In this study we demonstrate that by performing Thermally Stimulated Capacitance (TS-Cap) experiments in similar conditions to TSC measurements and developing theoretical models for simulating both types of B$_\text{i}$O$_\text{i}$ signals generated in TSC and TS-Cap measurements, accurate evaluations can be performed. The changes of the position-dependent electric field, the effective space charge density $N_\text{eff}$ profile as well as the occupation of the B$_\text{i}$O$_\text{i}$ defect during the electric field dependent electron emission, are simulated as a function of temperature. The macroscopic properties (leakage current and $N_\text{eff}$) extracted from current-voltage and capacitance-voltage measurements at \SI{20}{\celsius} are also presented and discussed

The diffusion of iodine defects has been considered the most important degradation mechanism of methylammonium lead iodine (MAPI) in solar cells. The present study demonstrates the importance of the pressure inside this material on the dynamics of iodine defects, using molecular dynamics simulations. It is known that the diffusion coefficient of an iodine vacancy is an order of magnitude higher than that of interstitial iodine. We show that this difference systematically increases with increased tensile strain and that both diffusion coefficients tend to zero when a compressive strain is applied. This result suggests that compression of the MAPI can be a good solution to reduce its degradation rate. %Also, different methods of determining the diffusion coefficient, including mean squared displacement (MSD) and velocity auto-correlation function, are discussed and applied to the case of ${\rm V}_{\rm I}$. Besides, the statistical aspect of deriving the diffusion coefficient from the mean squared displacement (MSD) is discussed in terms of the initial conditions (positions and velocities) of the atoms and the simulation time, considering different seeds of the pseudo-random number generator used in the simulations performed with the LAMMPS software., Comment: 6 pages 7 figures

Electronic and stability properties of quasi-2D alkylammonium perovskites are investigated using density functional theory (DFT) calculations and validated experimentally on selected classes of compounds. Our analysis is focused on perovskite structures of formula (A)$_2$(A$'$)$_{n-1}$Pb$_n$X$_{3n+1}$, with large cations A = butyl-, pentyl-, hexylammonium (BA, PA, HXA), small cations A$'$ = methylammonium, formamidinium, ethylammonium, guanidinium (MA,FA,EA,GA) and halogens X = I, Br, Cl. The role of the halogen ions is outlined for the band structure, stability and defect formation energies. Two opposing trends are found for the absorption efficiency versus stability, the latter being assessed with respect to possible degradation mechanisms. Experimental validation is performed on quasi-2D perovskites based on pentylammonium cations, namely: (PA)$_2$PbX$_4$ and (PA)$_2$(MA)Pb$_2$X$_7$, synthesized by antisolvent-assisted vapor crystallization. Structural and optical analysis are inline with the DFT based calculations. In addition, the thermogravimetric analysis shows an enhanced stability of bromide and chloride based compounds, in agreement with the theoretical predictions., Comment: 8 pages, 8 figures

High-energy physics detectors, like Low Gain Avalanche Detectors (LGADs) that will be used as fast timing detectors in the High Luminosity LHC experiments, have to exhibit a significant radiation tolerance. Thereby the impact of radiation on the highly boron-doped gain layer that enables the internal charge multiplication, is of special interest, since due to the so-called Acceptor Removal Effect (ARE) a radiation-induced deactivation of active boron dopants takes place. In this paper we present defect-spectroscopy measurements (Deep-Level Transient Spectroscopy and Thermally Stimulated Current technique) on neutron irradiated p-type silicon pad diodes of different resistivity as well as LGADs irradiated at fluences up to 1 x 10^15 neq/cm2. Thereby we show that while for the silicon pad diodes irradiated with electrons, neutrons or protons the determination of defect electronic properties and defect introduction rates is straightforward, DLTS and TSC measurements on LGADs are strongly influenced by the impact of the gain layer. It is shown that the measurability of the capacitance of the gain layer shows a strong frequency and temperature dependence leading to a capacitance drop in DLTS and non-reliable measurement results. With TSC defects formed in the LGADs can be very nicely observed and compared to the defects formed in the silicon pad diodes. However the exact assignment of defects to the gain layer or bulk region remains challenging and the charge amplification effect of the LGADs impacts the exact determination of defect concentrations. Additionally, we will demonstrate that depending on the TSC measurement conditions defect induced residual internal electric fields are built up in the irradiated LGADs that are influencing the current signal of carriers emitted from the defect states.

Dynamic hysteresis effects have been long known to occur in the J-V characteristics of perovskite solar cells (PSCs), with the ionic migration being identified as the primary factor. The hysteretic effects impacted early studies by the uncertainty in the evaluation of the power conversion efficiency, while currently, potential links to degradation mechanisms are in the focus. Therefore, understanding ion migration is a central goal, typically addressed by performing a combined large- and small signal analysis. The reported large capacitive and inductive effects created controversies with respect to the underlying mechanisms, yielding essentially two classes of models, one based on large accumulation capacitances and the other based on ionic modulation of the collected current. We introduce here an equivalent circuit model and interpret these phenomena in terms of recombination current modulation, identifying the distinct contributions from ion current and ionic charge accumulations. These contributions to the recombination current are associated with capacitive and inductive effects, respectively, and we corroborate the numerical simulations with electrochemical impedance spectroscopy (EIS) measurements. These show the role of the recombination currents of photogenerated carriers in producing both capacitive and inductive effects as the illumination is varied. Moreover, we provide a bridging point between the two classes of models and suggest a framework of investigation of defect states based on the observed inductive behavior, which would further aid the mitigation of the degradation effects., Comment: 20 pages

We investigate in how far the hysteresis-free behavior of perovskite solar cells can be reproduced using particular pre-conditioning and measurement conditions. As there are currently more and more reports of perovskite solar cells without J-V hysteresis it is crucial to distinguish between genuine performance improvements and measurement artifacts. We focus on two of the parameters that influence the dynamic J-V scans, namely the bias scan rate and and the bias poling voltage, and point out measurement conditions for achieving a hysteresis-free behavior. In this context we discuss the suitability of defining a hysteresis index (HI) for the characterization of dynamic J-V scans. Using HI, aging effects are also investigated, establishing a potential connection between the sample degradation and the variation of the maximal hysteresis on one hand, and relaxation time scale of the slow process, on the other hand. Pre-poling induced recombinations effects are identified. In addition, our analysis based on sample pre-biasing reveals potential indication regarding two types of slow processes, with two different relaxation time scales, which provides further insight regarding ionic migration., Comment: 11 pages, 11 figures

Non-ionising energy loss of radiation produces point defects and defect clusters in silicon, which result in a signifcant degradation of sensor performance. In this contribution results from TSC (Thermally Stimulated Current) defect spectroscopy for silicon pad diodes irradiated by electrons to fluences of a few $10^{14}$ cm$^{-2}$ and energies between 3.5 and 27 MeV for isochronal annealing between 80 and 280{\deg}C, are presented. A method based on SRH (Shockley-Read-Hall) statistics is introduced, which assumes that the ionisation energy of the defects in a cluster depends on the fraction of occupied traps. The dfference of ionisation energy of an isolated point defect and a fully occupied cluster, $\Delta E_a$, is extracted from the TSC data. For the VOi (vacancy-oxygen interstitial) defect $\Delta E_a = 0$ is found, which cofirms that it is a point defect, and validates the method for point defects. For clusters made of deep acceptors the $\Delta E_a$ values for different defects are determined after annealing at 80{\deg}C as a function of electron energy, and for the irradiation with 15 MeV electrons as a function of annealing temperature. For the irradiation with 3.5 MeV electrons the value $\Delta E_a = 0$ is found, whereas for the electron energies of 6 to 27 MeV $\Delta E_a > 0$. This agrees with the expected threshold of about 5 MeV for cluster formation by electrons. The $\Delta E_a$ values determined as a function of annealing temperature show that the annealing rate is different for different defects. A naive diffusion model is used to estimate the temperature dependencies of the diffusion of the defects in the clusters., Comment: 13 pages, 12 figures, 4 tables

The dynamic effects observed in the J-V measurements represent one important hallmark in the behavior of the perovskite solar cells. Proper measurement protocols (MPs) should be employed for the experimental data reproducibility, in particular for a reliable evaluation of the power conversion efficiency (PCE), as well as for a meaningful characterization of the type and magnitude of the hysteresis. We discuss here several MPs by comparing the experimental J-V characteristics with simulated ones using the dynamic electrical model (DEM). Pre-poling conditions and bias scan rate can have a dramatic influence not only on the apparent solar cell performance, but also on the hysteretic phenomena. Under certain measurement conditions, a hysteresis-free behavior with relatively high PCEs may be observed, although the J-V characteristics may be far away from the stationary case. Furthermore, forward-reverse and reverse-forward bias scans show qualitatively different behaviors regarding the type of the hysteresis, normal and inverted, depending on the bias pre-poling. We emphasize here that correlated forward-reverse or reverse-forward bias scans are essential for a correct assessment of the dynamic hysteresis. In this context, we define a hysteresis index which consistently assigns the hysteresis type and magnitude. Our DEM simulations, supported by experimental data, provide further guidance for an efficient and accurate determination of the stationary J-V characteristics, showing that the type and magnitude of the dynamic hysteresis may be affected by unintentional pre-conditioning in typical experiments., Comment: 11 pages 7, figures

Hysteretic effects are investigated in perovskite solar cells in the standard FTO/TiO$_2$/CH$_3$NH$_3$PbI$_{3-x}$Cl$_x$/spiro-OMeTAD/Au configuration. We report normal (NH) and inverted hysteresis (IH) in the J-V characteristics occurring for the same device structure, the behavior strictly depending on the pre-poling bias. NH typically appears at pre-poling biases larger than the open circuit bias, while pronounced IH occurs for negative bias pre-poling. The transition from NH to IH is marked by a intermediate mixed hysteresis behavior characterized by a crossing point in the J-V characteristics. The measured J-V characteristics are explained quantitatively by the dynamic electrical model (DEM). Furthermore, the influence of the bias scan rate on the NH/IH hysteresis is discussed based on the time evolution of the non-linear polarization. Introducing a three step measurement protocol, which includes stabilization, pre-poling and measurement, we put forward the difficulties and possible solutions for a correct PCE evaluation., Comment: 11 pages, 10 figures

A dynamic electrical model is introduced to investigate the hysteretic effects in the I-V characteristics of perovskite based solar cells. By making a simple ansatz for the polarization relaxation, our model is able to reproduce qualitatively and quantitatively detailed features of measured I-V characteristics. Pre-poling effects are discussed, pointing out the differences between initially over- and under-polarized samples. In particular, the presence of the current over-shoot observed in the reverse characteristics is correlated with the solar cell pre-conditioning. Furthermore, the dynamic hysteresis is analyzed with respect to changing the bias scan rate, the obtained results being consistent with experimentally reported data: the hysteresis amplitude is maximum at intermediate scan rates, while at very slow and very fast ones it becomes negligible. The effects induced by different relaxation time scales are assessed. The proposed dynamic electrical model offers a comprehensive view of the solar cell operation, being a practical tool for future calibration of tentative microscopic descriptions., Comment: 8 pages, 6 figures, Supplemental material, to appear in Solar Energy Materials & Solar Cells

A systematic experimental study of the main challenges for silicon-pixel sensors at the European XFEL is presented. The high instantaneous density of X-rays and the high repetition rate of the XFEL pulses result in signal distortions due to the plasma effect and in severe radiation damage. The main parameters of X-ray-radiation damage have been determined and their impact on p+n sensors investigated. These studies form the basis of the optimized design of a pixel-sensor for experimentation at the European XFEL.

Experiments at the European X-ray Free Electron Laser (XFEL) require silicon pixel sensors which can withstand X-ray doses up to 1 GGy. For the investigation of X-ray radiation damage up to these high doses, MOS capacitors and gate-controlled diodes built on high resistivity n-doped silicon with crystal orientations <100> and <111> produced by two vendors, CiS and Hamamatsu, have been irradiated with 12 keV X-rays at the DESY DORIS III synchrotron light source. Using capacitance/conductance-voltage, current-voltage and thermal dielectric relaxation current measurements, the surface densities of oxide charges and interface traps at the Si-SiO2 interface, and the surface-current densities have been determined as function of dose. Results indicate that the dose dependence of the surface density of oxide charges and the surface-current density depend on the crystal orientation and producer. In addition, the influence of the voltage applied to the gates of the MOS capacitor and the gate-controlled diode during X-ray irradiation on the surface density of oxide charges and the surface-current density has been investigated at doses of 100 kGy and 100 MGy. It is found that both strongly depend on the gate voltage if the electric field in the oxide points from the surface of the SiO2 to the Si-SiO2 interface. Finally, annealing studies have been performed at 60 and 80 degree C on MOS capacitors and gate-controlled diodes irradiated to 5 MGy and the annealing kinetics of oxide charges and surface current determined., Comment: 10 pages, 6 figures, 3 tables

The European X-ray Free Electron Laser (XFEL) will deliver 30,000 fully coherent, high brilliance X-ray pulses per second each with a duration below 100 fs. This will allow the recording of diffraction patterns of single complex molecules and the study of ultra-fast processes. Silicon pixel sensors will be used to record the diffraction images. In 3 years of operation the sensors will be exposed to doses of up to 1 GGy of 12 keV X-rays. At this X-ray energy no bulk damage in silicon is expected. However fixed oxide charges in the insulating layer covering the silicon and interface traps at the Si-SiO2 interface will be introduced by the irradiation and build up over time. We have investigated the microscopic defects in test structures and the macroscopic electrical properties of segmented detectors as a function of the X-ray dose. From the test structures we determine the oxide charge density and the densities of interface traps as a function of dose. We find that both saturate (and even decrease) for doses between 10 and 100 MGy. For segmented sensors the defects introduced by the X-rays increase the full depletion voltage, the surface leakage current and the inter-pixel capacitance. We observe that an electron accumulation layer forms at the Si-SiO2 interface. Its width increases with dose and decreases with applied bias voltage. Using TCAD simulations with the dose dependent parameters obtained from the test structures, we are able to reproduce the observed results. This allows us to optimize the sensor design for the XFEL requirements.

Imaging experiments at the European X-ray Free Electron Laser (XFEL) require silicon pixel sensors with extraordinary performance specifications: Doses of up to 1 GGy of 12 keV photons, up to 10^5 12 keV photons per pixel of 200 \mum \times 200 \mum arriving within less than 100 fs, and a time interval between XFEL pulses of 220 ns. To address these challenges, in particular the question of radiation damage, the properties of the SiO_2 layer and of the Si-SiO_2 interface using MOS capacitors manufactured on high resistivity n-type silicon irradiated to X-ray doses between 10 kGy and 1 GGy, have been studied. Measurements of Capacitance/Conductance-Voltage (C/G-V) at different frequencies, as well as Thermal Dielectric Relaxation Current (TDRC) have been performed. The data can be described by a radiation dependent oxide charge density and three dominant radiation-induced interface states with Gaussian-like energy distributions in the silicon band gap. It is found that the densities of the fixed oxide charges and of the three interface states increase up to dose values of approximately 10 MGy and then saturate or even decrease. The shapes and the frequency dependences of the C/G-V measurements can be quantitatively described by a simple model using the parameters extracted from the TDRC measurements., Comment: 14 pages and 7 figures

Aluminum oxide (Al2O3) has been grown by atomic layer deposition on n-type 4H-SiC with and without a thin silicon dioxide (SiO2) intermediate layer. By means of Capacitance Voltage and Thermal Dielectric Relaxation Current measurements, the interface properties have been investigated. Whereas for the samples with an interfacial SiO2 layer the highest near-interface trap density is found at 0.3 eV below the conduction band edge, Ec, the samples with only the Al2O3 dielectric exhibit a nearly trap free region close to Ec. For the Al2O3/SiC interface, the highest trap density appears between 0.4 to 0.6 eV below Ec. The results indicate the possibility for SiC-based MOSFETs with Al2O3 as the gate dielectric layer in future high performance devices., Comment: 3 figures. Applied Physics Letters, accepted for publication