Metastable Changes Research Articles

Light induced degradation of CIGS solar cells

Considering warranted lifetimes of PV modules of typically 20-30 years, the performance stability of PV modules is one of the most crucial factors regarding power generation and yield. Long term outdoor performance studies depict realistic operation conditions best, but the correlated nature of e.g. irradiance and temperature impedes the physical interpretation. The possibility to control and tune the conditions in laboratory experiments enables to decompose effects, that are typically overlayed in outdoor experiments. This way, laboratory are crucial to interpret the results obtained in outdoor degradation studies. One driving force of degradation of CIGS modules is light exposure. In literature the focus of light induced degradation (LID) of CIGS modules and solar cells is on metastable changes analyzed on time scales ranging from minutes to hours. In this work we expose industrially produced encapsulated CIGS solar cells for more than 1000 h to light with varied intensity under varied temperature conditions. Such, we aim to study temperature and light intensity dependencies of the observed performance changes. Furthermore, we study the influence of applied bias by comparing LID at short and open circuit. We demonstrate that LID under short circuit conditions leads to VOC degradation, while being temperature assisted and not dependent on the irradiance intensity. CIGS solar cells kept at open circuit conditions appear to be stable under illumination. Exploiting the one diode model, we further connect the observed temperature assisted performance loss to enhanced recombination with lower ideality factor, in comparison to the dominant recombination process before degradation.

X-ray computed tomography analysis of calcium chloride hexahydrate solidification

Latent Thermal Energy Storages (LTESs) are receiving increasing interest, since they offer many advantages to the field of Thermal Energy Storages (TESs), such as a nearly isothermal solid–liquid phase transition and a high energy storage density. To boost the transition towards a climate-neutral future, a lot of work is surely needed on Phase Change Materials (PCMs) which are used inside LTESs. Salt hydrates, a particular class of PCMs, are very attractive in terms of cost and volumetric latent enthalpy but present drawbacks that still limit their effective deployment in real applications, such as supercooling and phase separation (or segregation). The current work assesses the suitability of X-ray Computed Tomography (XCT) as a novel technique in the field of LTESs to study the solidification of phase-change materials. In this study, calcium chloride hexahydrate (CaCl2·6H2O) is chosen as a representative PCM and the results derived are shown to be repeatable. For the first time, the direct measurement of the volumetric liquid fraction is correlated to temperature measurements allowing for the visualisation of supercooling and the validation of an enthalpy-porosity numerical model, which could be useful in the design of LTES. XCT methodology offers unmatchable features as compared to the other method to measure the volumetric liquid fraction. Given its accuracy and the rigorous protocol, it can be considered as a benchmark for new liquid fraction measurement technologies but it also permits to study how the different PCMs melt and solidify, giving new insights on the mechanisms at the basis of the most crucial challenges, among those: subcooling, segregation, and metastable phase change.

Metastability in Dark Current Diode Characteristics of Chalcogenide Photovoltaic Modules

While present trends in commercial photovoltaic (PV) are set on a‐Si/c‐Si heterojunctions and promising perovskites, the chalcogenides still attract interest as an excellent candidate for coming multi‐ and heterojunction devices with perovskites. Continuously enhanced over the years, typical metastabilities in thin‐film devices still cause issues under outdoor operation. Unfortunately, qualitative assessment in commercial PV is solely focused on data at the maximum power point of its operation, whether in simple on‐site PV plant monitoring or following latest standards for certified laboratory testing, thus metastabilities merely register as undefined power fluctuations. Herein, it is shown that dark current characteristics are a simple and yet field‐fit method, to identify metastable changes and take suitable counter measures. With this study, using commercial CdTe and CIGS showcase modules of various manufacturers and production generations, it is demonstrated how dark current characteristics allow to pinpoint physical changes of the individual module, between its pristine state, outdoor operation, dark degradation, and stabilization, like a fingerprint. Using the two‐diode model, it is shown that alterations to respective regimes of the characteristic can be assigned to typical defects, defining the module's current state, and be used to it as a guide to evaluate its recuperation via preconditioning treatments.

Phase transitions and dynamics in ionic liquid crystals confined in nanopores.

We investigate the phase-transition behavior of ionic liquid crystals, namely 1-methyl-3-alkylimidazolium tetrafluoroborate, [Cnmim]BF4, confined in cylindrical nanopores using differential scanning calorimetry, x-ray scattering, and dielectric relaxation spectroscopy. Here, n is the number of carbon atoms in the alkyl part of this ionic liquid crystal. For n = 10 and 12, the isotropic liquid phase changes to the smectic phase and then to a metastable phase for the cooling process. During the subsequent heating process, the metastable phase changes to the isotropic phase via crystalline phases. The transition temperatures for this ionic liquid crystal confined in nanopores decrease linearly with the increase in the inverse pore diameter, except for the transitions between the smectic and isotropic phases. In the metastable phase, the relaxation rate of the α-process shows the Vogel-Fulcher-Tammann type of temperature dependence for some temperature ranges. The glass transition temperature evaluated from the dynamics of the α-process decreases with the decrease in the pore diameter and increases with the increase in the carbon number n. The effect of confinement on the chain dynamics can clearly be observed for this ionic liquid crystal. For n = 10, the melting temperature of the crystalline phase is slightly higher than that of the smectic phase for the bulk, while, in the nanopores, the melting temperature of the smectic phase is higher than that of the crystalline phase. This suggests that the smectic phase can be thermodynamically stable, thanks to the confinement effect.

Tetrabutylammonium lactate semiclathrate hydrate phase equilibria and polymorphs

Clathrate hydrates can be used as a way of storing and separating gases at elevated pressures. Ionic semiclathrate formers, miscible in water, can promote the formation of hydrates, allowing for milder conditions in potential industrial applications such as cold energy storage and carbon sequestration. However, understanding semiclathrate formation has been difficult due to the complexity associated with the numerous stable and metastable phase changes possible. Using tetrabutylammonium lactate (TBAL) and differential scanning calorimetry, here we show that the formation of polymorphs with different dissociation temperatures is highly sensitive to the TBAL concentration - with gradual transitions from one phase to the next over small concentration increments. Furthermore, we show that the cooling rate may influence the formation/dissociation of a polymorph, leading to complexities such as recrystallization on warming. Given the discrepancies between reported semiclathrate thermodynamic properties, such as dissociation temperature and latent heat, this work highlights the need for caution when using calorimetry (and other methods) to determine semiclathrate properties. This caution is needed to ensure that the same polymorph is referred to when reporting thermodynamic properties. Precise reference to polymorph conditions is also important but also when projecting such data to potential future applications where a different polymorph/polymorph mixture may form with different properties than those anticipated.

Reverse-bias behaviour of thin-film solar cells: effects of measurement-induced heating

When a solar cell is subjected to a negative voltage bias, it locally heats up due to the deposited electrical power. Therefore, every investigation of cell characteristics in the negative voltage regime faces the challenge that the measurement itself changes the state of the cell in a way that is difficult to quantify: On the one hand, the reverse breakdown is known to be strongly temperature dependent. On the other hand, negative voltages lead to metastable device changes which are also very sensitive to temperature. In the current study, we introduce a new approach to suppress this measurement-induced heating by inserting time delays between individual voltage pulses when measuring. As a sample system we use thin-film solar cells based on Cu(In,Ga)Se2 (CIGS) absorber layers. First we verify that with this approach the measurement-induced heating is largely reduced. This allows us to then analyse the impact of the heating on two characteristics of the cells: (i) the reverse breakdown behaviour and (ii) reverse-bias-induced metastable device changes. The results show that minimising the measurement-induced heating leads to a significant increase of the breakdown voltage and effectively slows down the metastable dynamics. Regarding the reverse breakdown, the fundamental tunneling mechanisms that are believed to drive the breakdown remain qualitatively unchanged, but the heating affects the quantitative values extracted for the associated energy barriers. Regarding the reverse-bias metastability, the experimental data reveal that there are two responsible mechanisms that react differently to the heating: Apart from a charge redistribution at the front interface due to the amphoteric (VSe–VCu) divacancy complex, the modification of a transport barrier is observed which might be caused by ion migration towards the back interface. The findings in this study demonstrate that local sample heating due to reverse-bias measurements can have a notable impact on device behaviour which needs to be kept in mind when developing models of the underlying physical processes.

Metastable phase separation and duplex metallic glass formation of liquid Zr<sub>35</sub>Al<sub>23</sub>Ni<sub>22</sub>Gd<sub>20</sub> alloy

Duplex metallic glass with two amorphous phases has been extensively investigated for desirable strength and plasticity. In this paper, the metastable phase separation and dual amorphous phase formation of liquid Zr<sub>35</sub>Al<sub>23</sub>Ni<sub>22</sub>Gd<sub>20</sub> alloy under substantial undercooling condition and rapid cooling condition are studied by drop tube technology. The equilibrium solidification structure consists of three crystalline phases, while the critical undercooling temperature of metastable phase separation is determined to be 516 K (0.37<i>T</i><sub>L</sub>). The separated Zr-rich liquid phase undergoes amorphous transition and becomes amorphous AM-Zr phase with the composition of Zr<sub>45</sub>Ni<sub>23</sub>Al<sub>23</sub>Gd<sub>9</sub> when alloy undercooling is increased to 624 K (0.45<i>T</i><sub>L</sub>). After that, the Gd-rich liquid phase forms amorphous AM-Gd phase with the composition of Gd<sub>39</sub>Al<sub>22</sub>Ni<sub>20</sub>Zr<sub>19</sub> at larger undercooling of 714 K (0.52<i>T</i><sub>L</sub>). With the increase of liquid undercooling and cooling rate, the kinetic mechanism of metastable phase separation changes from nucleation and growth type to spinodal decomposition type, and consequently the microstructure of dual amorphous phases transforms from a spherical morphology to a reticular structure. The average hardness and Young’s modulus, which are influenced by free volume, phase volume fraction and structure of dual amorphous phases, exhibit a complex variation of first increasing and then decreasing with the decrease of alloy droplet size. The formation of dual amorphous phases is in favor of the energy dissipation and the generation of multiple shear bands during mechanical compression, which improves the plasticity for this kind of amorphous alloy.

Resistive switching effect in the n-InGaAs/GaAs heterostructures with double tunnel-coupled quantum wells

The electric conductivity behavior in the single and double tunnel-coupled quantum wells (QW) with different doping profile caused by the impact of short pulses of the strong longitudinal (in the quantum wells plane) electric field has been investigated. It is established that at low temperatures (4 K) after such an impact the long-term metastable state with increased electric conductance may be observed in the case of the asymmetric QW couple with the impurity delta shaped-layer in the narrower QW. It is not observed in the structures with other configurations. The observed effect is explained by the model accounting for metastable changes in the electron energy states spectrum in the studied structures caused by the strong electric field pulses.

Patterned crystal growth and heat wave generation in hydrogels

The crystallization of metastable liquid phase change materials releases stored energy as latent heat upon nucleation and may therefore provide a triggerable means of activating downstream processes that respond to changes in temperature. In this work, we describe a strategy for controlling the fast, exothermic crystallization of sodium acetate from a metastable aqueous solution into trihydrate crystals within a polyacrylamide hydrogel whose polymerization state has been patterned using photomasks. A comprehensive experimental study of crystal shapes, crystal growth front velocities and evolving thermal profiles showed that rapid growth of long needle-like crystals through unpolymerized solutions produced peak temperatures of up to 45˚C, while slower-crystallizing polymerized solutions produced polycrystalline composites and peaked at 30˚C due to lower rates of heat release relative to dissipation in these regions. This temperature difference in the propagating heat waves, which we describe using a proposed analytical model, enables the use of this strategy to selectively activate thermoresponsive processes in predefined areas.

Metastable transition temperature in undercooled hypereutectic Al-Si alloys

The present study proposes a novel approach to predict the transition temperature at which the metastable zone changes to the labile zone during the undercooling of hypereutectic Al-Si alloys. The results show that the silicon content and the undercooling strongly affect the transition temperature and the energy barrier to start the spontaneous nucleation. The energy barrier predicted at the transition temperature was in the order of 10−19J. Mixing of two precursor alloys, Ostwald-Miers diagram, and transition temperature were employed to design conditions at which the microstructure of Al-14 and Al-17 wt%Si alloys forming with free primary silicon or small size primary silicon compared with conventional microstructure without adding a grain refiner.

Perturbative solution of a propagating interface in the phase field model

When a stable ordered phase and a metastable disordered phase are separated by a flat interface, the metastable state changes to the stable state through the propagation of the interface. For cases in which latent heat is generated, the interface displacement during some time interval is proportional to the square root of the time interval when the extent of supercooling is less than a certain value. We demonstrate this behavior by deriving a perturbative solution for a propagating interface in the phase field model. We calculate the leading-order contribution explicitly, and find that the interface temperature deviates from the equilibrium transition temperature in proportion to the interface velocity.

An analytical model to predict the depth of sub-surface damage for grinding of brittle materials

This paper proposes an analytical model for predicting grinding-induced sub-surface damage depth in a silicon wafer. The model integrates the dislocation kinetics for crack initiation and fracture mechanics for crack propagation for the first time. Unlike other conventional models, the proposed model considers the effects of strain rate on damage depth and the dynamically changing metastable phase change properties. The model is verified by grinding experiments and a comparison of theoretical and experimental results shows a good quantitative agreement. It is found that increasing grinding speed and decreasing depth of cut cause a higher strain rate so as to enhance material brittleness, which is favorable to achieving low sub-surface damage. These findings will pave a way towards optimizing the grinding parameters and greatly improving the production efficiency of hard and brittle materials.

Parameterization of photobleaching and photodarkening in-situ kinetics in thermally deposited GeSe2 thin films

Thermally evaporated chalcogenide glass thin films are known to be highly photosensitive revealing both metastable and transient photoinduced changes of optical transmission at the fundamental absorption edge region. In-situ kinetics of metastable photobleaching and transient photodarkening as well as following light-off relaxations for as-deposited GeSe2 thin films were studied and fitted with the stretched exponential function. Dependences of kinetic parameters β and τ on film thickness, temperature, sample prehistory and wavelength of light irradiation were analyzed. The obtained results were discussed within current approaches to mechanisms of photoinduced kinetic phenomena and structural relaxation in glasses.

Photochromism and influence of point defect charge states on optical absorption in aluminum nitride (AlN)

In this work, we study the absorption properties of AlN in the range of 1.5–5.5 eV, as well as the metastable change in absorption induced by ultraviolet (UV) irradiation (photochromism). We also study the restoration of the initial state under the action of the irradiation of 2–4 eV or elevated temperatures. UV irradiation results in a decrease of the absorption coefficient from 110 to 55 cm−1 at 4.7 eV, while in the visible range, the absorption coefficient increases from values below 5 to ∼35 cm−1. Measurements with two linear polarizations, E ∥ c and E ⊥ c, provide the determination of several different absorption bands at 2.6, 2.8, 3.4, 4.0, 4.5, and 4.8 eV. The bands at 2.6 and 3.4 eV identify the defect levels near the valence band, while the band peaking at 2.8 eV is related to the conduction band. Photochromism allows for controlling the absorption of light in two related spectral ranges, because the decrease of UV absorption and increase of visible absorption are related to switching the charge state of the same defects.

Histone Modification ChIP-seq on Arabidopsis thaliana Plantlets.

Characterizing the molecular mechanisms regulating gene expression is crucial for understanding the regulatory processes underlying physiological responses to environmental and developmental signals in eukaryotes. The covalent modification of histones contributes to the compaction levels of chromatin, as well as the recruitment of the transcriptional machinery to specific loci, facilitating metastable changes in gene activity. ChIP-seq (Chromatin Immunoprecipitation followed by sequencing) has become the gold standard method for determining histone modification profiles among different organisms, tissues, and genotypes. In the current protocol, we describe a highly robust method for performing ChIP-seq of histone modifications in Arabidopsis thaliana plantlets. Besides its robustness, this method uses in-house-prepared buffers for chromatin extraction, immunoprecipitation, washing, and elusion, making it cost-effective in contrast to commercial kits.

Electrically Tailored Metachrosis in ZnO-C Nanowires.

Carbon incorporated zinc oxide (ZnO:C) nanowires (NWs) are found to be remarkable morphing NWs. We show that the physical properties of ZnO:C NWs are engineered via the passage of electric current to produce fluorescence differences and negative differential resistance as well as electroluminescence. When a ZnO:C NW is subjected to an applied voltage bias and under ultraviolet (UV) excitation, electron-hole separation due to the voltage biasing suppresses their fluorescence at low voltages. At medium voltages, the NW exhibits metastable chemical changes that translates to tunable and reversible optical alterations akin to metachrosis found in chameleons. Concurrently, the NW displays electrical alterations with negative differential resistance behaviors. At higher voltages, these NWs are permanently modified with distinct heterogeneous chemical stoichiometry, fluorescence, and electronic properties. Such heterogeneity within the NW allows for emergence of junctions capable of electroluminescence.

Current-voltage and capacitance study of light-induced metastabilities in CuZnSnSSe thin film solar cells

White, red and blue light-induced metastabilities in Cu2ZnSnS4(Se4) solar cells were investigated by temperature dependent current-voltage measurements, drive level capacitance profiling, impedance and thermal admittance spectroscopy. A set of devices were studied where white and blue light soaking at room temperature led to degradation of the device performance, while after red light soaking the solar cell efficiency did not change.We observed a significant effect of light soaking on capacitance data measured in both low and high-temperature ranges for these devices. In particular, the net doping concentration extracted from drive-level capacitance profiling substantially increased after light soaking treatments.Low and high-temperature capacitance steps observed in the reference capacitance-frequency spectra were assigned to Fermi level pinning and bulk defects, correspondingly. Light soaking with different-wavelength light led to a shift of both steps toward the high-frequency range, and hence a decrease in the thermal admittance activation energies.A low-frequency ‘inductive’ loop was detected in the impedance spectra after light soaking, regardless of wavelength. It was proposed that the appearance of the ‘inductive’ loop is due to the formation of a negative electric field at the highly defected CdS/Cu2ZnSnS4(Se4) hetero-interface. This result also leads us to conclude that such electric field is responsible for the metastable behaviour of these devices at room temperature, while the low temperature metastable changes might have a different origin.We also discuss the methodology for electrical characterization of the metastable solar cells in detail.

Metastable Refractive Index Manipulation in Hydrogenated Amorphous Silicon for Reconfigurable Photonics

AbstractHydrogenated amorphous silicon (a‐Si:H) is known for exhibiting light‐induced metastable properties that are reversible upon annealing. While these are commonly associated with the well‐known deleterious Staebler–Wronski effect in the field of thin‐film silicon solar cells, the associated changes in optical properties have not been well studied. Emerging reconfigurable photonic devices and applications can benefit from metastable optical properties where two states of the material are reversibly accessible without the need for continuous stimulation. The study demonstrates a light‐induced 0.3% increase of the metastable refractive index of a‐Si:H that is reversed upon annealing over several cycles using a highly sensitive Fabry–Pérot interferometric technique. Utilizing this technique, a metastable optical switch based on a micro‐ring resonator is demonstrated with reversible distinct switching states separated by 0.3 nm between the light‐soaked and annealed states, a switching extinction exceeding 20 dB and an unchanged Q‐factor, suggesting no excess discernible optical loss. Furthermore, metastable strain changes in a‐Si:H‐based freestanding membrane structures are linked to the observed metastable optical properties and present a possible route to stable photonic devices. Our proof‐of‐concept demonstration showcases a‐Si:H‐based reconfigurable photonics that support multiple purpose photonic integrated circuits, reconfigurable metamaterials, and advanced optomechanical devices.

Metastable Phase Equilibrium in the Reciprocal Quaternary System LiCl+MgCl2+Li2SO4+MgSO4+H2O at 348.15 K and 0.1 MPa

The metastable solubilities and the physicochemical properties including density and pH of the reciprocal quaternary system(LiCl+MgCl2+Li2SO4+MgSO4+H2O) at 348.15 K and 0.1 MPa were determined using the isother-mal evaporation method. The dry-salt diagram and water-phase diagram were plotted based on the experimental data. There are five invariant points, eleven univariant curves, and seven crystallization zones corresponding to hexahy-drite, tetrahydrite, kieserite, bischofite, lithium sulfate monohydrate, lithium chloride monohydrate and lithium car-nallite. Comparison between the stable and metastable diagrams at 348.15 K indicates that the metastable phenome-non of magnesium sulfate is obvious, and the crystallization regions of hexahydrite and tetrahydrite disappear in the stable phase diagram. A comparison of the metastable dry-salt phase diagrams at 308.15, 323.15 and 348.15 K shows that with the increasing of temperature the epsomite crystallization zone disappears from the dry-salt phase diagram of 303.15 K, and a new kieserite crystallization zone is presented at 348.15 K. The density and pH in the metastable equilibrium solution present regular change with the increasing of Janecke index J(2Li+), and the calculated densities using the empirical equation agree well with the experimental values.

Doping properties of cadmium-rich arsenic-doped CdTe single crystals: Evidence of metastable AX behavior

Cd-rich composition and group-V element doping are of interest for simultaneously maximizing the hole concentration and minority carrier lifetime in CdTe, but the critical details concerning point defects are not yet fully established. Herein, we report on the properties of arsenic doped CdTe single crystals grown from Cd solvent by the travelling heater method. The photoluminescence spectra and activation energy of 74 ± 2 meV derived from the temperature-dependent Hall effect are consistent with AsTe as the dominant acceptor. Doping in the 1016 to 1017/cm3 range is achieved for measured As concentrations between 1016 and 1020/cm3 with the highest doping efficiency of 40% occurring near 1017 As/cm3. We observe persistent photoconductivity, a hallmark of light-induced metastable configuration changes consistent with AX behavior. Additionally, quenching experiments reveal at least two mechanisms of increased p-type doping in the dark, one decaying over 2–3 weeks and the other persisting for at least 2 months. These results provide essential insights for the application of As-doped CdTe in thin film solar cells.