Ultrafast Calorimetry Research Articles

Controlling glass forming kinetics in 2D perovskites using organic cation isomers.

The recent discovery of glass-forming metal halide perovskites (MHPs) provides opportunities to broaden the application domain beyond traditionally celebrated optoelectronic research fueled by associated crystalline counterparts. In this regard, it is crucial to diversify the compositional space of glass-forming MHPs and introduce varied crystallization kinetics via synthetic structural engineering. Here, we compare two MHPs with slightly varying structural attributes, utilizing isomer organic cations with the same elemental composition, and demonstrate how this change in functional group position impacts the kinetics of glass formation and subsequent crystallization by multiple orders of magnitude. (S)-(-)-1-(1-Naphthyl)ethylammonium lead bromide (S(1-1)NPB) exhibits a lower melting point (Tm) of 175 °C and the melt readily vitrifies under a critical cooling rate (CCR) of 0.3 °C s-1. In contrast, (S)-(-)-1-(2-naphthyl)ethylammonium lead bromide (S(1-2)NPB) displays a Tm ∼193 °C and requires a CCR of 2500 °C s-1, necessitating the use of ultrafast calorimetry for glass formation and study of the underlying kinetics. The distinct Tm and glass-formation kinetics of the isomer MHPs are further understood through a combination of calorimetric and single-crystal X-ray diffraction studies on their crystalline counterparts, highlighting the influence of altered organic-inorganic hydrogen bonding interactions and entropic changes around melting, providing insights into the factors driving their divergent behaviors.

Study of Glass Formation and Crystallization Kinetics in a 2D Metal Halide Perovskite Using Ultrafast Calorimetry.

While crystalline 2D metal halide perovskites (MHPs) represent a well-celebrated semiconductor class, supporting applications in the fields of photovoltaics, emitters, and sensors, the recent discovery of glass formation in an MHP opens many new opportunities associated with reversible glass-crystalline switching, with each state offering distinct optoelectronic properties. However, the previously reported [S-(-)-1-(1-naphthyl)ethylammonium]2PbBr4 perovskite is a strong glass former with sluggish glass-crystal transformation time scales, pointing to a need for glassy MHPs with a broader range of compositions and crystallization kinetics. Herein we report glass formation for low-melting-temperature 1-MeHa2PbI4 (1-MeHa = 1-methyl-hexylammonium) using ultrafast calorimetry, thereby extending the range of MHP glass formation across a broader range of organic (fused ring to branched aliphatic) and halide (bromide to iodide) compositions. The importance of a slight loss of organic and hydrogen iodide components from the MHP in stabilizing the glassy state is elucidated. Furthermore, the underlying kinetics of glass-crystal transformation, including activation energies, crystal growth rate, Angell plot, and fragility index, is studied using a combination of kinetic, thermodynamic, and rheological modeling techniques. An inferred fast crystal growth rate of 0.21 m/s for 1-MeHa2PbI4 shows promise toward suitability in extended application spaces, for example, in metamaterials, nonvolatile memory, and optical and neuromorphic computing devices.

Kinetically Controlled Structural Transitions in Layered Halide-Based Perovskites: An Approach to Modulate Spin Splitting.

Two-dimensional hybrid organic-inorganic perovskite (HOIP) semiconductors with pronounced spin splitting, mediated by strong spin-orbit coupling and inversion symmetry breaking, offer the potential for spin manipulation in future spintronic applications. However, HOIPs exhibiting significant conduction/valence band splitting are still relatively rare, given the generally observed preference for (near)centrosymmetric inorganic (especially lead-iodide-based) sublattices, and few approaches are available to control this symmetry breaking within a given HOIP. Here, we demonstrate, using (S-2-MeBA)2PbI4 (S-2-MeBA = (S)-(-)-2-methylbutylammonium) as an example, that a temperature-induced structural transition (at ∼180 K) serves to change the degree of chirality transfer to and inversion symmetry breaking within the inorganic layer, thereby enabling modulation of HOIP structural and electronic properties. The cooling rate is shown to dictate whether the structural transition occurs─i.e., slow cooling induces the transition while rapid quenching inhibits it. Ultrafast calorimetry indicates a minute-scale structural relaxation time at the transition temperature, while quenching to lower temperatures allows for effectively locking in the metastable room-temperature phase, thus enabling kinetic control over switching between distinct states with different degrees of structural distortions within the inorganic layers at these temperatures. Density functional theory further highlights that the low-temperature phase of (S-2-MeBA)2PbI4 shows more significant spin splitting relative to the room-temperature phase. Our work opens a new pathway to use kinetic control of crystal-to-crystal transitions and thermal cycling to modulate spin splitting in HOIPs for future spintronic applications, and further points to using such "sluggish" phase transitions for switching and control over other physical phenomena, particularly those relying on structural distortions and lattice symmetry.

The glass transition of water, insight from phase change materials

The calorimetric features that have been broadly used to assign a glass transition temperature Tg of 136 K to amorphous water are qualitatively reproduced with a phase change material. Annealing treatments and ultrafast calorimetry measurements indicate that this feature is only a shadow-Tg and that the real Tg lies at higher temperature above the glass transition. A Kissinger analysis of the crystallization kinetics confirms that crystallization occurs below Tg from the glassy state at conventional heating rates. These results strongly suggest that the amorphous water endotherm at 136 K is indeed a shadow-Tg and that the real Tg lies at higher temperature as predicted from structural relaxation considerations.

Disordered interfaces enable high temperature thermal stability and strength in a nanocrystalline aluminum alloy

Lightweighting of structural materials has proven indispensable in the energy economy, predicated on alloy design with high strength-to-weight ratios. Modern aluminum alloys have made great strides in ambient temperature performance and are amenable to advanced manufacturing routes such as additive manufacturing, but lack elevated temperature robustness where gains in efficiency can be obtained. Here, we demonstrate the intentional design of disorder at interfaces, a notion generally associated with thermal runaway in traditional materials, in a segregation-engineered ternary nanocrystalline Al–Ni–Ce alloy that exhibits exceptional thermal stability and elevated temperature strength. In-situ transmission electron microscopy in concert with ultrafast calorimetry and X-ray total scattering point to synergistic co-segregation of Ce and Ni driving the evolution of amorphous intergranular films separating sub-10 nm Al-rich grains, which gives rise to emergent thermal stability. We ascribe this intriguing behavior to near-equilibrium interface conditions followed by kinetically sluggish intermetallic precipitation in the confined disordered region. The resulting outstanding mechanical performance at high homologous temperatures lends credence to the efficacy of promoting disorder in alloy design and discovery.

Enhancement and maximum in the isobaric specific-heat capacity measurements of deeply supercooled water using ultrafast calorimetry

Knowledge of the temperature dependence of the isobaric specific heat (Cp) upon deep supercooling can give insights regarding the anomalous properties of water. If a maximum in Cp exists at a specific temperature, as in the isothermal compressibility, it would further validate the liquid-liquid critical point model that can explain the anomalous increase in thermodynamic response functions. The challenge is that the relevant temperature range falls in the region where ice crystallization becomes rapid, which has previously excluded experiments. Here, we have utilized a methodology of ultrafast calorimetry by determining the temperature jump from femtosecond X-ray pulses after heating with an infrared laser pulse and with a sufficiently long time delay between the pulses to allow measurements at constant pressure. Evaporative cooling of ∼15-µm diameter droplets in vacuum enabled us to reach a temperature down to ∼228 K with a small fraction of the droplets remaining unfrozen. We observed a sharp increase in Cp, from 88 J/mol/K at 244 K to about 218 J/mol/K at 229 K where a maximum is seen. The Cp maximum is at a similar temperature as the maxima of the isothermal compressibility and correlation length. From the Cp measurement, we estimated the excess entropy and self-diffusion coefficient of water and these properties decrease rapidly below 235 K.

Crystallization behavior of an Au based metallic glass at high temperature

The crystallization behavior of Au50Cu25.5Ag7.5Si17 metallic glass after isothermal treatment at different temperatures throughout the entire supercooled liquid region is investigated by ultra-fast calorimetry. The isothermal crystallization products of the glass, especially in the relatively high temperature region, where was difficult to reach via conventional techniques, are identified. Based on the microscopic analysis of the crystallization products, the crystallization mechanisms of the glass at different temperatures are clarified. The grain size evolution of the crystalline phases upon isothermal treatment are discussed through the comparison of the theoretical calculation and experimental results.

Crystallization Behavior of an Au Based Metallic Glass at High Temperature

The crystallization behavior of Au50Cu25.5Ag7.5Si17 metallic glass after isothermal treatment at different temperatures throughout the entire supercooled liquid region is investigated by ultra-fast calorimetry. The isothermal crystallization products of the glass, especially in the relatively high temperature region, where was difficult to reach via conventional techniques, are identified. Based on the microscopic analysis of the crystallization products, crystallization process and mechanism of the glass at different temperatures are clarified. The grain size evolution of the crystalline phases upon isothermal treatment are discussed through the comparison of theoretical calculation and experimental results.

Intermediate crystallization kinetics in Germanium-Tellurides

Germanium-Telluride has been widely studied as a phase-change material due to its fast crystallization speed. The understanding of the crystallization kinetics is important to evaluate the potential applications of the material, but this is limited by the conventional calorimetry with low heating rate and narrow temperature range. We here employed an ultrafast calorimetry method, named flash differential scanning calorimetry, to investigate the crystallization kinetics of GexTe100-x in a wide compositional range (15 ≤ x ≤ 55). By means of the X-ray diffraction, we found the complicated competition between crystalline GeTe and Te (or Ge) phases in these binary alloys. The crystallization kinetics of first crystalline phase were estimated and it was found that, GexTe100-x generally has intermediate crystal growth speed and fragility, which is ascribed to the border between covalent and metallic properties. Component dependences of maximum crystal growth rate (Umax) and fragility were investigated, revealing the component in x = 20.4 has the lowest Umax of 1.22 × 10−3 m s−1 with the smallest fragility of 42.2, and the component in x ≈ 50 possesses the largest Umax of 3.5 m s−1. It confirms that, GeTe is the most suitable phase-change material for information storage and GeTe4 is the best media for information transparency in Ge-Te binary. Moreover, a tri-counter pattern was carried out for obtaining the crystal growth rate directly in studied supercooled GexTe100-x liquids (15 ≤ x ≤ 55). In addition, we first found a peculiar component Ge22Te78 with terrible thermal properties, i.e., phase separation, low crystallization temperature, ultrahigh fragility and anomalous crystallization kinetics. More importantly, together with the crystallization kinetics parameters of other glass formers, it was found a specific relation between reduced glass temperature (Trg) and Umax for which can be benefit to simplify material screenings and performance optimizations.

Investigating the equilibrium melting temperature of linear polyethylene using the non-linear Hoffman-Weeks approach

The melting behavior of three linear polyethylene fractions with number average molecular weights of 11, 29, and 100.5 kg/mol was studied as a function of crystallization time with conventional and ultra-fast calorimetry. The initial melting temperatures of non-thickened lamellae formed under isothermal conditions over a range of crystallization temperatures were analyzed with the non-linear Hoffman-Weeks method to determine the equilibrium melting temperature. Tmeq values of 138.4±0.9°C, 139.7.4±0.9°C, and 140.9±0.8°C were estimated for PE 11K, PE 29K, and PE 100K, respectively, in close agreement with those reported in the literature for the melting of extended-chain crystals or with the Gibbs-Thomson analysis. The Lauritzen-Hoffman theory and the non-linear Hoffman-Weeks treatment were modified to account for the effect of the tilt angle, θ, of the crystallized stems of linear polyethylene on the initial average lamellar thickness. Accuracy of the non-linear Hoffman-Weeks method was examined using initial lamellar thickness, ℓg∗ , data reported for PE 29K in the literature at different crystallization temperatures. The equilibrium melting temperature obtained by the Gibbs-Thomson approach and the C2 value extracted from the ℓg∗vs.1/ΔT plot were similar within the limits of experimental error to those obtained here through the non-linear Hoffman-Weeks method. Using the Huggins equation, the equilibrium melting temperature of an infinitely long linear polyethylene chain is found to be equal to 141.4±0.8°C, the same value proposed by Wunderlich.

Ultra-fast hadronic calorimetry

Calorimeters for particle physics experiments with integration time of a few ns will substantially improve the capability of the experiment to resolve event pileup and to reject backgrounds. In this paper the time development of hadronic showers induced by 30 and 60 GeV positive pions and 120 GeV protons is studied using Monte Carlo simulation and beam tests with a prototype of a sampling steel-scintillator hadronic calorimeter. In the beam tests, scintillator signals induced by hadronic showers in steel are sampled with a period of 0.2 ns and precisely time-aligned in order to study the average signal waveform at various locations with respect to the beam particle impact. Simulations of the same setup are performed using the MARS15 code. Both simulation and test beam results suggest that energy deposition in steel calorimeters develop over a time shorter than 2 ns providing opportunity for ultra-fast calorimetry. Simulation results for an “ideal” calorimeter consisting exclusively of bulk tungsten or copper are presented to establish the lower limit of the signal integration window.

Understanding the fast crystallization kinetics of In–Sb–Te by using ultrafast calorimetry

The crystal growth rates of supercooled liquids In–Sb–Te can be well characterized by ultrafast DSC, and it benefits to the optimization for phase-change materials.

Resolving Crystallization Kinetics of GeTe Phase-Change Nanoparticles by Ultrafast Calorimetry.

Chalcogenide-based phase change materials (PCMs) are promising candidates for the active element in novel electrical nonvolatile memories and have been applied successfully in rewritable optical disks. Nanostructured PCMs are considered as the next generation building blocks for their low power consumption, high storage density, and fast switching speed. Yet their crystallization kinetics at high temperature, the rate-limiting property upon switching, faces great challenges due to the short time and length scales involved. Here we present a facile method to synthesize highly controlled, ligand-free GeTe nanoparticles, an important PCM, with an average diameter under 10 nm. Subsequent crystallization by slow and ultrafast rates allows unravelling of the crystallization kinetics, demonstrating the breakdown of Arrhenius behavior for the crystallization rate and a fragile-to-strong transition in the viscosity as well as the overall crystal growth rate for the as-deposited GeTe nanoparticles. The obtained results pave the way for further development of phase-change memory based on GeTe with sub-lithographic sizes.

Understanding the importance of the temperature dependence of viscosity on the crystallization dynamics in the Ge2Sb2Te5 phase-change material

The crystallization dynamics in the phase-change material Ge2Sb2Te5 is modelled using the more detailed Master equation method over a wide range of heating rates commensurate with published ultrafast calorimetry experiments. Through the attachment and detachment of monomers, the Master rate equation naturally traces nucleation and growth of crystallites with temperature history to calculate the transient distribution of cluster sizes in the material. Both the attachment and detachment rates in this theory are strong functions of viscosity, and thus, the value of viscosity and its dependence on temperature significantly affect the crystallization process. In this paper, we use the physically realistic Mauro−Yue−Ellison−Gupta−Allan viscosity model in the Master equation approach to study the role of the viscosity model parameters on the crystallization dynamics in Ge2Sb2Te5 under ramped annealing conditions with heating rates up to 4 × 104 K/s. Furthermore, due to the relatively low computational cost of the Master equation method compared to atomistic level computations, an iterative numerical approach was developed to fit theoretical Kissinger plots simulated with the Master equation system to experimental Kissinger plots from ultrafast calorimetry measurements at increasing heating rates. This provided a more rigorous method (incorporating both nucleation and growth processes) to extract the viscosity model parameters from the analysis of experimental data. The simulations and analysis revealed the strong coupling between the glass transition temperature and fragility index in the viscosity and crystallization models and highlighted the role of the dependence of the glass transition temperature on the heating rate for the accurate estimation of the fragility index of phase-change materials from the analysis of experimental measurements.

Unraveling the Crystallization Kinetics of Supercooled Liquid GeTe by Ultrafast Calorimetry

Crystallization kinetics of phase change materials (PCMs) at high temperatures is of key importance for the extreme speed of data writing and erasing. In this work, the crystallization behavior of one of the typical PCMs, GeTe, has been studied using ultrafast differential scanning calorimetry (DSC) at high heating rates up to 4 × 104 K s–1. A strong non-Arrhenius temperature-dependent viscosity has been observed. We considered two viscosity models for estimating the crystal growth kinetics coefficient (Ukin). The results showed that the MYEGA model was more suitable to describe the temperature-dependent viscosity and the crystal growth kinetics for supercooled liquid GeTe. The glass transition temperature (Tg) and fragility m were estimated to be 432.1 K and 130.7, respectively. The temperature-dependent crystal growth rates, which were extrapolated by the MYEGA model, were in line with the experimental results that were measured by in situ transmission electron microscopy at a given temperature. The cry...

Crystallization Kinetics of GeSbTe Phase-Change Nanoparticles Resolved by Ultrafast Calorimetry.

Although nanostructured phase-change materials (PCMs) are considered as the building blocks of next-generation phase-change memory and other emerging optoelectronic applications, the kinetics of the crystallization, the central property in switching, remains ambiguous in the high-temperature regime. Therefore, we present here an innovative exploration of the crystallization kinetics of Ge2Sb2Te5 (GST) nanoparticles (NPs) exploiting differential scanning calorimetry with ultrafast heating up to 40 000 K s–1. Our results demonstrate that the non-Arrhenius thermal dependence of viscosity at high temperature becomes an Arrhenius-like behavior when the glass transition is approached, indicating a fragile-to-strong (FS) crossover in the as-deposited amorphous GST NPs. The overall crystal growth rate of the GST NPs is unraveled as well. This unique feature of the FS crossover is favorable for memory applications as it is correlated to improved data retention. Furthermore, we show that methane incorporation during NP production enhances the stability of the amorphous NP phase (and thereby data retention), while a comparable maximum crystal growth rate is still observed. These results offer deep insight into the crystallization kinetics of nanostructured GST, paving the way for designing nonvolatile memories with PCM dimensions smaller than 20 nm.

Crystallization kinetics of an Au-based metallic glass upon ultrafast heating and cooling

The crystallization behavior of Au50Cu25.5Ag7.5Si17 metallic glass during continuous heating/cooling and isothermal treatment is investigated by ultrafast calorimetry. The relationship between the transformation and the time/temperature scales of the alloy is established experimentally in a wide temperature range from glass transition temperature to the melting point. Temperature-dependent viscosity in the expanded supercooled liquid region is derived from the thermodynamic and kinetic analysis of the crystallization behavior of the metallic glass. The nucleation rate and growth velocity for crystallization of the supercooled liquid are analyzed by applying classical nucleation theory and diffusion-controlled growth theory.

Study of melting processes in semicrystalline polymers using a combination of ultrafast chip calorimetry and nanofocus synchrotron X-ray diffraction

This work is devoted to the development and application of a new experimental method that combines in situ ultrafast calorimetry on a chip with nanofocus synchrotron X-ray diffraction. In the present work, this method is used to study the melting mechanisms of samples of semicrystalline polymers with the mass of a few tens of nanograms. Such studies are relevant when working with materials that are characterized by complex phase behavior, for example, prone to transitions into metastable states or demonstrating fast processes of structural adjustment during thermal treatment.

Crystallization Kinetics of Supercooled Liquid Ge–Sb Based on Ultrafast Calorimetry

The crystallization kinetics of phase-change materials (PCMs) entails a crucial aspect of phase-change memory technology, and their study is also of interest to advance the understanding of crystallization in general. Research on crystallization of PCMs remains challenging because of the short (nanosecond) time and small (nanometer) length scales involved. Ultrafast differential scanning calorimetry (DSC) offers a powerful tool to study crystallization via ultrahigh heating rates. Here, we used this tool to study the crystallization kinetics of growth-dominant Ge7Sb93. Two models describing the viscosity of the undercooled liquid were used to interpret the data and were subsequently crosschecked by independent growth-rate data. With both models the data in Kissinger plots could be fitted well, but one of the models resulted in a large discrepancy with the independent data. These results demonstrate that great care is needed when deriving crystal-growth rates from ultrafast DSC measurements because orders ...

Fragile‐to‐Strong Crossover in Supercooled Liquid Ag‐In‐Sb‐Te Studied by Ultrafast Calorimetry

Phase‐change random‐access memory relies on the reversible crystalline‐glassy phase change in chalcogenide thin films. In this application, the speed of crystallization is critical for device performance: there is a need to combine ultrafast crystallization for switching at high temperature with high resistance to crystallization for non‐volatile data retention near to room temperature. In phase‐change media such as nucleation‐dominated Ge2Sb2Te5, these conflicting requirements are met through the highly “fragile” nature of the temperature dependence of the viscosity of the supercooled liquid. The present study explores, using ultrafast‐heating calorimetry, the equivalent temperature dependence for the growth‐dominated medium Ag‐In‐Sb‐Te. The crystallization shows (unexpectedly) Arrhenius temperature dependence over a wide intermediate temperature range. Here it is shown that this is evidence for a fragile‐to‐strong crossover on cooling the liquid. Such a crossover has many consequences for the interpretation and control of phase‐change kinetics in chalcogenide media, helping to understand the distinction between nucleation‐ and growth‐dominated crystallization, and offering a route to designing improved device performance.