Integration of epitaxial LiNbO3thin films with silicon technology.

Development of bulk acoustic wave filters with ultra-wide pass bands and operating at high frequencies for 5thand 6thgeneration telecommunication applications and micro-scale actuators, energy harvesters and sensors requires lead-free piezoelectric thin films with high electromechanical coupling and compatible with Si technology. In this paper, the epitaxial growth of 36°Y-X and 30°X-Y LiNbO3films by direct liquid injection chemical vapour deposition on Si substrates by using epitaxial SrTiO3layers, grown by molecular beam epitaxy, has been demonstrated. The stability of the interfaces and chemical interactions between SrTiO3, LiNbO3and Si were studied experimentally and by thermodynamical calculations. The experimental conditions for pure 36°Y-X orientation growth have been optimized. The piezoelectricity of epitaxial 36°Y-X LiNbO3/SrTiO3/Si films was confirmed by means of piezoelectric force microscopy measurements and the ferroelectric domain inversion was attained at 85 kV.cm-1as expected for the nearly stoichiometric LiNbO3. According to the theoretical calculations, 36°Y-X LiNbO3films on Si could offer an electromechanical coupling of 24.4% for thickness extension excitation of bulk acoustic waves and a comparable figure of merit of actuators and vibrational energy harvesters to that of standard PbZr1-xTixO3films.

Ferroelectric Hf0.5Zr0.5O2 films with improved endurance obtained through low temperature epitaxial growth on seed layers.

Crystallization temperature is a critical parameter in the stabilization of the metastable ferroelectric phase of HfO2. The optimal crystallization temperature used for polycrystalline films is too low to grow epitaxial films. We have developed a new growth strategy, based on the use of an ultrathin seed layer, to obtain high-quality epitaxial films of orthorhombic Hf0.5Zr0.5O2 at a lower temperature. The threshold temperature for epitaxy is reduced from about 750 °C to about 550 °C using a seed layer. Epitaxial films deposited at low temperatures exhibit highly enhanced endurance, and films grown at 550-600 °C show high polarization, no wake-up effect, and greatly reduced fatigue and improved endurance in comparison with the films deposited at high temperatures without a seed layer. We propose that the endurance enhancement is due to a positive effect of the defects, which limits the propagation of pinned ferroelectric domains.

Integration of Li4Ti5O12 Crystalline Films on Silicon Toward High-Rate Performance Lithionic Devices.

The growth of crystalline Li-based oxide thin films on silicon substrates is essential for the integration of next-generation solid-state lithionic and electronic devices including on-chip microbatteries, memristors, and sensors. However, growing crystalline oxides directly on silicon typically requires high temperatures and oxygen partial pressures, which leads to the formation of undesired chemical species at the interface compromising the crystal quality of the films. In this work, we employ a 2 nm gamma-alumina (γ-Al2O3) buffer layer on Si substrates in order to grow crystalline thin films of Li4Ti5O12 (LTO), a well-known active material for lithium-ion batteries. The ultrathin γ-Al2O3 layer enables the formation of a stable heterostructure with sharp interfaces and drastically improves the LTO crystallographic and electrochemical properties. Long-term galvanostatic cycling of 50 nm LTO films in liquid-based half-cells demonstrates a high capacity retention of 91% after 5000 cycles at 100 C. Rate capability tests showcase a specific charge of 56 mA h g-1 at an exceptional C-rate of 5000 C (15 mA cm-2). Moreover, with sub-millisecond current pulse tests, the reported thin-film heterostructure exhibits rapid Li-ion (de)intercalation, which could lead to fast switching timescales in resistive memory devices and electrochemical transistors.

Impact of La Concentration on Ferroelectricity of La-Doped HfO2 Epitaxial Thin Films.

Epitaxial thin films of HfO2 doped with La have been grown on SrTiO3(001) and Si(001), and the impact of the La concentration on the stabilization of the ferroelectric phase has been determined. Films with 2-5 at. % La doping present the least amount of paraelectric monoclinic and cubic phases and exhibit the highest polarization, having a remanent polarization above 20 µC/cm2. The dopant concentration results in an important effect on the coercive field, which is reduced with increasing La content. Combined high polarization, high retention, and high endurance of at least 1010 cycles is obtained in 5 at. % La-doped films.

Electric and Mechanical Switching of Ferroelectric and Resistive States in Semiconducting BaTiO3-δ Films on Silicon.

Materials that can couple electrical and mechanical properties constitute a key element of smart actuators, energy harvesters, or many sensing devices. Within this class, functional oxides display specific mesoscale responses which often result in great sensitivity to small external stimuli. Here, a novel combination of molecular beam epitaxy and a water-based chemical-solution method is used for the design of mechanically controlled multilevel device integrated on silicon. In particular, the possibility of adding extra functionalities to a ferroelectric oxide heterostructure by n-doping and nanostructuring a BaTiO3 thin film on Si(001) is explored. It is found that the ferroelectric polarization can be reversed, and resistive switching can be measured, upon a mechanical load in epitaxial BaTiO3-δ /La0.7 Sr0.3 MnO3 /SrTiO3 /Si columnar nanostructures. A flexoelectric effect is found, stemming from substantial strain gradients that can be created with moderate loads. Simultaneously, mechanical effects on the local conductivity can be used to modulate a nonvolatile resistive state of the BaTiO3-δ heterostructure. As a result, three different configurations of the system become accessible on top of the usual voltage reversal of polarization and resistive states.

Thermoelectric La-doped SrTiO3 epitaxial layers with single-crystal quality: from nano to micrometers.

High-quality thermoelectric La0.2Sr0.8TiO3 (LSTO) films, with thicknesses ranging from 20 nm to 0.7 µm, have been epitaxially grown on SrTiO3(001) substrates by enhanced solid-source oxide molecular-beam epitaxy. All films are atomically flat (with rms roughness < 0.2 nm), with low mosaicity (<0.1°), and present very low electrical resistivity (<5 × 10-4 Ω cm at room temperature), one order of magnitude lower than standard commercial Nb-doped SrTiO3 single-crystalline substrate. The conservation of transport properties within this thickness range has been confirmed by thermoelectric measurements where Seebeck coefficients of approximately -60 µV/K have been recorded for all films. These LSTO films can be integrated on Si for non-volatile memory structures or opto-microelectronic devices, functioning as transparent conductors or thermoelectric elements.

Continuous-wave operation of monolithically grown 1.5-microm optically pumped vertical-external-cavity surface-emitting lasers.

Continuous-wave operation, to as high as 7 degrees C, of 1.5-microm optically pumped vertical-external-cavity surface-emitting lasers is reported. The epitaxial structure, monolithically grown on InP by metal-organic chemical vapor deposition, consists of an InAlAs/GaInAlAs Bragg reflector, an InGaAs/InGaAsP active region, and an InP capping layer. The threshold incident pump intensity is <9 kW/cm2.