Guided acoustic waves in thin epitaxial films: Experiment and inverse problem solution for NiTi.

Despite the fundamental and technological importance of the elastic constants, a suitable method for their full characterization in epitaxial films is missing. Here we show that transient grating spectroscopy (TGS) with highly k-vector-selective generation and detection of acoustic waves is capable of determination of all independent elastic coefficients of an epitaxial thin film grown on a single-crystalline substrate. This experimental setup enables detection of various types of guided acoustic waves and evaluation of the directional dependence of their speeds of propagation. For the studied model system, which is a 3µm thin epitaxial film of the NiTi shape memory alloy on an MgO substrate, the TGS angular maps include Rayleigh-type surface acoustic waves as well as Sezawa-type and Love-type modes, delivering rich information on the elastic response of the film under different straining modes. The resulting inverse problem, which means the calculation of the elastic constants from the TGS maps, is subsequently solved using the Ritz-Rayleigh numerical method. Using this approach, tetragonal elastic constants of the NiTi film and their changes with the austenite→martensite phase transition are analyzed.

Growth and martensitic transformation of ferromagnetic Co-Cr-Ga-Si epitaxial films.

During cooling, conventional martensitic transformation can only be realized from austenite to martensite. Recently, a so-called reentrant martensitic transformation attracted much interest due to an additional transformation from martensite to austenite during further cooling. Obviously, materials with this reentrant transformation will increase the number of physical effects and possible applications. However, until now, only bulk samples have been available, which are not suitable for applications in micro-devices. In this work, we focus on the Co-Cr-Ga-Si system and examine the suitability of this system for the growth of thin films. We observed that the films grow epitaxially on MgO (100) substrates and exhibit a martensitic transformation if deposited at a sufficiently high temperature or with an additional heat treatment. Films within the austenite state are ferromagnetic while films within the martensitic state just exhibit a very low ferromagnetic order.

What is the speed limit of martensitic transformations?

Structural martensitic transformations enable various applications, which range from high stroke actuation and sensing to energy efficient magnetocaloric refrigeration and thermomagnetic energy harvesting. All these emerging applications benefit from a fast transformation, but up to now their speed limit has not been explored. Here, we demonstrate that a thermoelastic martensite to austenite transformation can be completed within 10 ns. We heat epitaxial Ni-Mn-Ga films with a nanosecond laser pulse and use synchrotron diffraction to probe the influence of initial temperature and overheating on transformation rate and ratio. We demonstrate that an increase in thermal energy drives this transformation faster. Though the observed speed limit of 2.5 × 1027 (Js)1 per unit cell leaves plenty of room for further acceleration of applications, our analysis reveals that the practical limit will be the energy required for switching. Thus, martensitic transformations obey similar speed limits as in microelectronics, as expressed by the Margolus - Levitin theorem.

Can gadolinium compete with La-Fe-Co-Si in a thermomagnetic generator?

A thermomagnetic generator is a promising technology to harvest low-grade waste heat and convert it into electricity. To make this technology competitive with other technologies for energy harvesting near room temperature, the optimum thermomagnetic material is required. Here we compare the performance of a state of the art thermomagnetic generator using gadolinium and La-Fe-Co-Si as thermomagnetic material, which exhibit strong differences in thermal conductivity and type of magnetic transition. gadolinium is the established benchmark material for magnetocaloric cooling, which follows the reverse energy conversion process as compared to thermomagnetic energy harvesting. Surprisingly, La-Fe-Co-Si outperforms gadolinium in terms of voltage and power output. Our analysis reveals the differences in thermal conductivity are less important than the particular shape of the magnetization curve. In gadolinium an unsymmetrical magnetization curve is responsible for an uncompensated magnetic flux, which results in magnetic stray fields. These stray fields represent an energy barrier in the thermodynamic cycle and reduce the output of the generator. Our detailed experiments and simulations of both, thermomagnetic materials and generator, clearly reveal the importance to minimize magnetic stray fields. This is only possible when using materials with a symmetrical magnetization curve, such as La-Fe-Co-Si.

Influencing Martensitic Transition in Epitaxial Ni-Mn-Ga-Co Films with Large Angle Grain Boundaries.

Magnetocaloric materials based on field-induced first order transformations such as Ni-Mn-Ga-Co are promising for more environmentally friendly cooling. Due to the underlying martensitic transformation, a large hysteresis can occur, which in turn reduces the efficiency of a cooling cycle. Here, we analyse the influence of the film microstructure on the thermal hysteresis and focus especially on large angle grain boundaries. We control the microstructure and grain boundary density by depositing films with local epitaxy on different substrates: Single crystalline MgO(0 0 1), MgO(1 1 0) and Al2O3(0 0 0 1). By combining local electron backscatter diffraction (EBSD) and global texture measurements with thermomagnetic measurements, we correlate a smaller hysteresis with the presence of grain boundaries. In films with grain boundaries, the hysteresis is decreased by about 30% compared to single crystalline films. Nevertheless, a large grain boundary density leads to a broadened transition. To explain this behaviour, we discuss the influence of grain boundaries on the martensitic transformation. While grain boundaries act as nucleation sites, they also lead to different strains in the material, which gives rise to various transition temperatures inside one film. We can show that a thoughtful design of the grain boundary microstructure is an important step to optimize the hysteresis.

Reversible tuning of magnetocaloric Ni-Mn-Ga-Co films on ferroelectric PMN-PT substrates.

Tuning functional properties of thin caloric films by mechanical stress is currently of high interest. In particular, a controllable magnetisation or transition temperature is desired for improved usability in magnetocaloric devices. Here, we present results of epitaxial magnetocaloric Ni-Mn-Ga-Co thin films on ferroelectric Pb(Mg1/3Nb2/3)0.72Ti0.28O3 (PMN-PT) substrates. Utilizing X-ray diffraction measurements, we demonstrate that the strain induced in the substrate by application of an electric field can be transferred to the thin film, resulting in a change of the lattice parameters. We examined the consequences of this strain on the magnetic properties of the thin film by temperature- and electric field-dependent measurements. We did not observe a change of martensitic transformation temperature but a reversible change of magnetisation within the austenitic state, which we attribute to the intrinsic magnetic instability of this metamagnetic Heusler alloy. We demonstrate an electric field-controlled entropy change of about 31 % of the magnetocaloric effect - without any hysteresis.

Magnetic domain pattern in hierarchically twinned epitaxial Ni-Mn-Ga films.

Magnetic shape memory alloys exhibit a hierarchically twinned microstructure, which has been examined thoroughly in epitaxial Ni-Mn-Ga films. Here we analyze the consequences of this 'twin within twins' microstructure on the magnetic domain pattern. Atomic and magnetic force microscopy are used to probe the correlation between the martensitic microstructure and magnetic domains. We examine the consequences of different twin boundary orientations with respect to the substrate normal as well as variant boundaries between differently aligned twinned laminates. A detailed micromagnetic analysis is given which describes the influence of the finite film thickness on the formation of magnetic band domains in these multiferroic materials.

Magnetic nanostructures by adaptive twinning in strained epitaxial films.

We exploit the intrinsic structural instability of the Fe(70)Pd(30) magnetic shape memory alloy to obtain functional epitaxial films exhibiting a self-organized nanostructure. We demonstrate that coherent epitaxial straining by 54% is possible. The combination of thin film experiments and large-scale first-principles calculations enables us to establish a lattice relaxation mechanism, which is not expected for stable materials. We identify a low twin boundary energy compared to a high elastic energy as key prerequisite for the adaptive nanotwinning. Our approach is versatile as it allows to control both, nanostructure and intrinsic properties for ferromagnetic, ferroelastic, and ferroelectric materials.

Electric field-induced modification of magnetism in thin-film ferromagnets.

A large electric field at the surface of a ferromagnetic metal is expected to appreciably change its electron density. In particular, the metal's intrinsic magnetic properties, which are commonly regarded as fixed material constants, will be affected. This requires, however, that the surface has a strong influence on the material's properties, as is the case with ultrathin films. We demonstrated that the magnetocrystalline anisotropy of ordered iron-platinum (FePt) and iron-palladium (FePd) intermetallic compounds can be reversibly modified by an applied electric field when immersed in an electrolyte. A voltage change of -0.6 volts on 2-nanometer-thick films altered the coercivity by -4.5 and +1% in FePt and FePd, respectively. The modification of the magnetic parameters was attributed to a change in the number of unpaired d electrons in response to the applied electric field. Our device structure is general and should be applicable for characterization of other thin-film magnetic systems.