Ferroelectric hafnia-based thin films are promising candidates for emerging high-density embedded nonvolatile memory technologies, thanks to their compatibility with silicon technology and the possibility of 3D integration. The electrode–ferroelectric interface and the crystallization annealing temperature may play an important role in such memory cells. The top interface in a TiN/Hf0.5Zr0.5O2/TiN metal–ferroelectric–metal stack annealed at different temperatures was investigated with X-ray photoelectron spectroscopy. The uniformity and continuity of the 2 nm TiN top electrode was verified by photoemission electron microscopy and conductive atomic force microscopy. Partial oxidation of the electrode at the interface is identified. Hf is reduced near the top interface due to oxygen scavenging by the top electrode. The oxygen vacancy (VO) profile showed a maximum at the top interface (0.71%) and a sharp decrease into the film, giving rise to an internal field. Annealing at higher temperatures did not affect the VO concentration at the top interface but causes the generation of additional VO in the film, leading to a decrease of the Schottky Barrier Height for electrons. The interface chemistry and n-type film doping are believed to be at the origin of several phenomena, including wake-up, imprint, and fatigue. Our results give insights into the physical chemistry of the top interface with the accumulation of defective charges acting as electronic traps, causing a local imprint effect. This may explain the wake-up behavior as well and also can be a possible reason of the weaker endurance observed in these systems when increasing the annealing temperature.
We present a hard and soft x-ray photoelectron spectroscopy study of the interface chemistry in pristine TiN/La-doped Hf0.5Zr0.5O2/TiN capacitors. An oxynitride phase (∼1.3 nm) is formed at the top interface, while a TiO2−δ phase was detected near the bottom interface. The oxygen vacancy (VO) concentration is higher at the top interface than in the film due to oxygen scavenging by the top electrode. The VO concentration was also found to increase from ∼1.5 to 1.9 × 1020 cm−3 when increasing La doping from 1.7 to 2.7 mol. %. Two La dopants are compensated by the formation of one positively charged VO.
Polythiophene molecules adsorbed on a highly oriented pyrolytic graphite surface were studied by combined dynamic scanning tunneling microscopy (STM) and frequency modulation atomic force microscopy (FM-AFM) with a quartz tuning fork sensor operating in Qplus mode and equipped with a Pt/Ir tip. Upon completing a careful sub-angström oscillation amplitude calibration of the probe, experiments were conducted in an ultra high vacuum at room temperature. By selecting the tip/surface distance regulation parameter, one can select the type of simultaneous information obtained in an area. For distance regulation based on the mean tunneling current, dynamic STM images together with maps of tip/surface force gradient were obtained. FM-AFM images with maps of the tunneling current were also acquired when the distance regulation was based on the frequency shift. Comparison between these images reveals interesting features. For example the tip which operates in STM mode with ultra low current (<10 pA) generates different interaction forces above molecules or graphite. Changes in energy dissipation processes as small as tens of millielectronvolts per cycle were recorded when the tip oscillates above the polymer or on the graphite surface. Hence data demonstrates that a stiff piezoelectric tuning fork of several kilonewtons/meters working as an AFM/STM probe with sub-angström amplitude can characterize weakly adsorbed molecules.
We have used energy-filtered photoemission electron microscopy (PEEM) at the photoemission threshold to carry out a microscopic scale characterization of the surface charge and domain structure of the (001) surface in BaTiO3. Signatures of ferroelectric and ferroelastic domains, and tweed, dominate the surface structure of BaTiO3 at room temperature. The surface ferroic signatures are maintained on heating to temperature (~550 K), well above the transition temperature (393 K). This surface proximity effect provides the mechanism for memory of the bulk ferroelectric domain arrangement up to 150 K above TC and thus can be considered as a robust fingerprint of the ferroelectric state near the surface. Self-reversal of polarization is observed for the tweed below TC and for the surface domains above TC. Annealing at higher temperature triggers the dynamic tweed which in turn allows a full reorganization of the ferroic domain configuration.
By using an atomic force microscope based on a quartz tuning fork sensor, a 3-dimensional description of the interface between liquid hexadecane and a highly oriented pyrolytic graphite surface can be achieved at room temperature. The C16H34 monolayer in contact with the substrate surface exhibits a lamellar structure whereas no observation at the liquid/graphite interface by scanning tunnelling microscopy was reported for this alkane. The second layer shows very weak corrugations corresponding to lamella boundaries. Force/distance curves show at least four oscillations separated by 0.4 nm except for the first period with a 0.38 nm distance that corresponds to the layer closer the substrate. Such a description agrees well with molecular dynamics results obtained on alkane/solid interfaces.
Significant progress in the understanding of surfaces and interfaces of materials for new technologies requires operando studies, i.e., measurement of chemical, electronic, and magnetic properties under external stimulus (such as mechanical strain, optical illumination, or electric fields) applied in situ in order to approach real operating conditions. Electron microscopy attracts much interest, thanks to its ability to determine semiconductor doping at various scales in devices. Spectroscopic photoelectron emission microscopy (PEEM) is particularly powerful since it combines high spatial and energy resolution, allowing a comprehensive analysis of local work function, chemistry, and electronic structure using secondary, core level, and valence band electrons, respectively. Here we present the first operando spectroscopic PEEM study of a planar Si p-n junction under forward and reverse bias. The method can be used to characterize a vast range of materials at near device scales such as resistive oxides, conducting bridge memories and domain wall arrays in ferroelectrics photovoltaic devices.
Sharp Pt/Ir tips have been reproducibly etched by an electrochemical process using an inverse geometry of an electrochemical cell and a dedicated electronic device which allows us to control the applied voltages waveform and the intensity of the etching current. Conductive tips with a radius smaller than 10 nm were routinely produced as shown by field emission measurements through Fowler-Nordheim plots. These etched tips were then fixed on a quartz tuning fork force sensor working in a qPlus configuration to check their performances for both scanning tunneling microscopy (STM) and atomic force microscopy (AFM) imaging.Their sharpness and conductivity are evidenced by the resolution achieved in STM and AFM images obtained of epitaxial graphene on 6H-SiC(0001) surface. The structure of an epitaxial graphene layer thermally grown on the 6H-SiC(0001) ) 3 6 3 6 ( × R30° reconstructed surface, was successfully imaged at room temperature with STM, dynamic STM and by frequency modulated AFM.
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