Denis Machon

Pressure-temperature phase diagram of SrTiO3 up to 53 GPa

We investigate the cubic to tetragonal phase transition in the pressure-temperature phase diagram of strontium titanate SrTiO 3 STO by means of Raman spectroscopy and x-ray diffraction on single-crystal samples. X-ray diffraction experiments are performed at room temperature, 381 and 467 K up to 53 GPa, 30 GPa, and 26 GPa, respectively. The observation of the superstructure reflections in the x-ray patterns provides evidence that the crystal undergoes at all investigated temperatures a pressure-induced transition from cubic to the tetragonal I4 / mcm phase, identical to the low-temperature phase. No other phase transition is observed at room temperature up to 53 GPa. Together with previously published data, our results allow us to propose a linear phase boundary in the pressure-temperature phase diagram. The data are analyzed in the framework of the Landau theory of phase transitions. With a revised value of the coupling coefficient between the order parameter and the volume spontaneous strain, the model built from pressure-independent coefficients reproduces satisfactorily the boundary in the phase diagram, but fails at reflecting the more pronounced second-order character of the pressure-induced phase transition as compared to the temperature-induced transition. We propose a Landau potential suitable for the description of the pressure-induced phase transition. Finally, we show that particular attention has to be paid to hydrostatic conditions in the study of the high-pressure phase transition in STO.

Pressure-Mediated Doping in Graphene

Exfoliated graphene and few layer graphene samples supported on SiO(2) have been studied by Raman spectroscopy at high pressure. For samples immersed on a alcohol mixture, an electron transfer of ∂n/∂P ∼ 8 × 10(12) cm(-2) GPa(-1) is observed for monolayer and bilayer graphene, leading to giant doping values of n ∼ 6 × 10(13) cm(-2) at the maximum pressure of 7 GPa. Three independent and consistent proofs of the doping process are obtained from (i) the evolution of the Raman G-band to 2D-band intensity ratio, (ii) the pressure coefficient of the G-band frequency, and (iii) the 2D band components splitting in the case of the bilayer sample. The charge transfer phenomena is absent for trilayer samples and for samples immersed in argon or nitrogen. We also show that a phase transition from a 2D biaxial strain response, resulting from the substrate drag upon volume reduction, to a 3D hydrostatic compression takes place when going from the bilayer to the trilayer sample. By model calculations we relate this transition to the unbinding of the graphene-SiO(2) system when increasing the number of graphene layers and as function of the surface roughness parameters. We propose that the formation of silanol groups on the SiO(2) substrate allows for a capacitance-induced substrate-mediated charge transfer.

Pressure-temperature phase diagram ofSrTiO3up to 53 GPa

We investigate the cubic to tetragonal phase transition in the pressure-temperature phase diagram of strontium titanate SrTiO 3 STO by means of Raman spectroscopy and x-ray diffraction on single-crystal samples. X-ray diffraction experiments are performed at room temperature, 381 and 467 K up to 53 GPa, 30 GPa, and 26 GPa, respectively. The observation of the superstructure reflections in the x-ray patterns provides evidence that the crystal undergoes at all investigated temperatures a pressure-induced transition from cubic to the tetragonal I4 / mcm phase, identical to the low-temperature phase. No other phase transition is observed at room temperature up to 53 GPa. Together with previously published data, our results allow us to propose a linear phase boundary in the pressure-temperature phase diagram. The data are analyzed in the framework of the Landau theory of phase transitions. With a revised value of the coupling coefficient between the order parameter and the volume spontaneous strain, the model built from pressure-independent coefficients reproduces satisfactorily the boundary in the phase diagram, but fails at reflecting the more pronounced second-order character of the pressure-induced phase transition as compared to the temperature-induced transition. We propose a Landau potential suitable for the description of the pressure-induced phase transition. Finally, we show that particular attention has to be paid to hydrostatic conditions in the study of the high-pressure phase transition in STO.

Metastable phase transitions and structural transformations in solid-state materials at high pressure

We use a combination of diamond anvil cell techniques and large volume (multi-anvil press, piston cylinder) devices to study the synthesis, structure and properties of new materials under high pressure conditions. The work often involves the study of structural and phase transformations occurring in the metastable regime, as we explore the phase space determined as a function of the pressure, temperature and chemical composition. The experimental studies are combined with first principles calculations and molecular dynamics simulations, as we determine the structures and properties of new phases and the nature of the transformations between them. Problems currently under investigation include structural studies of transition metal and main group nitrides, oxides and oxynitrides at high pressure, exploration of new solid-state compounds that are formed within the C-N-O system, polyamorphic low- to high-density transitions among amorphous semiconductors such as a-Si, and transformations into metastable forms of the element that occur when its “expanded” clathrate polymorph is compressed.

Thermodynamics of Nanoparticles: Experimental Protocol Based on a Comprehensive Ginzburg-Landau Interpretation

The effects of surface and interface on the thermodynamics of small particles require a deeper understanding. This step is crucial for the development of models that can be used for decision-making support to design nanomaterials with original properties. On the basis of experimental results for phase transitions in compressed ZnO nanoparticles, we show the limitations of classical thermodynamics approaches (Gibbs and Landau). We develop a new model based on the Ginzburg-Landau theory that requires the consideration of several terms, such as the interaction between nanoparticles, pressure gradients, defect density, and so on. This phenomenological approach sheds light on the discrepancies in the literature as it identifies several possible parameters that should be taken into account to properly describe the transformations. For the sake of clarity and standardization, we propose an experimental protocol that must be followed during high-pressure investigations of nanoparticles in order to obtain coherent, reliable data that can be used by the scientific community.

Biaxial Strain Transfer in Supported Graphene

Understanding the mechanism and limits of strain transfer between supported 2D systems and their substrate is a most needed step toward the development of strain engineering at the nanoscale. This includes applications in straintronics, nanoelectromechanical devices, or new nanocomposites. Here, we have studied the limits of biaxial compressive strain transfer among SiO2, diamond, and sapphire substrates and graphene. Using high pressure-which allows maximizing the adhesion between graphene and the substrate on which it is deposited-we show that the relevant parameter governing the graphene mechanical response is not the applied pressure but rather the strain that is transmitted from the substrate. Under these experimental conditions, we also show the existence of a critical biaxial stress beyond which strain transfer become partial and introduce a parameter, α, to characterize strain transfer efficiency. The critical stress and α appear to be dependent on the nature of the substrate. Under ideal biaxial strain transfer conditions, the phonon Raman G-band dependence with strain appears to be linear with a slope of -60 ± 3 cm-1/% down to biaxial strains of -0.9%. This evolution appears to be general for both biaxial compression and tension for different experimental setups, at least in the biaxial strain range -0.9% < ε < 1.8%, thus providing a criterion to validate total biaxial strain transfer hypotheses. These results invite us to cast a new look at mechanical strain experiments on deposited graphene as well as to other 2D layered materials.

Pressure-Dependent Photoluminescence Study of Wurtzite InP Nanowires

The elastic properties of InP nanowires are investigated by photoluminescence measurements under hydrostatic pressure at room temperature and experimentally deduced values of the linear pressure coefficients are obtained. The pressure-induced energy shift of the A and B transitions yields a linear pressure coefficient of αA = 88.2 ± 0.5 meV/GPa and αB = 89.3 ± 0.5 meV/GPa with a small sublinear term of βA = βB = -2.7 ± 0.2 meV/GPa(2). Effective hydrostatic deformation potentials of -6.12 ± 0.04 and -6.2 ± 0.04 eV are derived from the results for the A and B transitions, respectively. A decrease of the integrated intensity is observed above 0.5 GPa and is interpreted as a carrier transfer from the first to the second conduction band of the wurtzite InP.

Absence of pressure-induced amorphization in LiKSO4

Angle-resolved synchrotron radiation diffraction was used to investigate lithium potassium sulfate (LiKSO(4)) crystals under high pressure. We confirm that the title compound undergoes three phase transitions, α →β, β → γ and γ →δ, observed at around 0.8 GPa, 4.0 GPa and 7.0 GPa, respectively. Two competitive structures are proposed for the β-phase after powder diffraction data Rietveld refinements: an orthorhombic (space group Cmc 2(1)) or a monoclinic (space group Cc) structure. These structures correspond to the models of the low temperature phases. The γ-phase is indexed by a monoclinic structure. Finally, the δ-phase is found to be highly disordered. No evidence of any pressure-induced amorphous phase was observed up to 24 GPa, even under imposed highly non-hydrostatic conditions, contrary to previous propositions.

Symmetry-induced collapse of ferromagnetism at the α-ε phase transition in iron

The magnetostructural bcc-to-hcp phase transition in iron is analysed theoretically in the framework of the Landau theory of phase transitions. In contrast to recent interpretations which emphasize the driving role of magnetism at the transition, the collapse of the ferromagnetic order in ε-Fe is interpreted as resulting from the large spontaneous strains and the magnitude of the displacive order-parameter involved in the Burgers reconstructive transition mechanism. It yields a direct first-order transition from the ferromagnetic α-phase to the non-magnetic ε-phase, without going across an intermediate magnetic structure.

Semiconductor clathrates: In situ studies of their high pressure, variable temperature and synthesis behavior

In situ studies have provided valuable new information on the synthesis mechanisms, low temperature properties and high pressure behavior of semiconductor clathrates. Here we review work using synchrotron and laboratory X-ray diffraction and Raman scattering used to study mainly Si-based clathrates under a variety of conditions. During synthesis of the Type I clathrate Na8Si46 by metastable thermal decomposition from NaSi in vacuum, we observe an unusual quasi-epitaxial process where the clathrate structure appears to nucleate and grow directly from the Na-deficient Zintl phase surface. Low temperature X-ray studies of the guest-free Type II clathrate framework Si136 reveal a region of negative thermal expansion behavior as predicted theoretically and analogous to that observed for diamond-structured Si. High pressure studies of Si136 lead to metastable production of the β-Sn structured Si-II phase as well as perhaps other metastable crystalline materials. High pressure investigations of Type I clathrates show evidence for a new class of apparently isostructural densification transformations followed by amorphization in certain cases.