Momentum-resolved electronic structure and band offsets in an epitaxial NbN/GaN superconductor/semiconductor heterojunction.

The electronic structure of heterointerfaces is a pivotal factor for their device functionality. We use soft x-ray angle-resolved photoelectron spectroscopy to directly measure the momentum-resolved electronic band structures on both sides of the Schottky heterointerface formed by epitaxial films of the superconducting NbN on semiconducting GaN, and determine their momentum-dependent interfacial band offset as well as the band-bending profile. We find, in particular, that the Fermi states in NbN are well separated in energy and momentum from the states in GaN, excluding any notable electronic cross-talk of the superconducting states in NbN to GaN. We support the experimental findings with first-principles calculations for bulk NbN and GaN. The Schottky barrier height obtained from photoemission is corroborated by electronic transport and optical measurements. The momentum-resolved understanding of electronic properties of interfaces elucidated in our work opens up new frontiers for the quantum materials where interfacial states play a defining role.

Magnetoelectric Coupling at the Ni/Hf0.5Zr0.5O2 Interface.

Composite multiferroics containing ferroelectric and ferromagnetic components often have much larger magnetoelectric coupling compared to their single-phase counterparts. Doped or alloyed HfO2-based ferroelectrics may serve as a promising component in composite multiferroic structures potentially feasible for technological applications. Recently, a strong charge-mediated magnetoelectric coupling at the Ni/HfO2 interface has been predicted using density functional theory calculations. Here, we report on the experimental evidence of such magnetoelectric coupling at the Ni/Hf0.5Zr0.5O2(HZO) interface. Using a combination of operando XAS/XMCD and HAXPES/MCDAD techniques, we probe element-selectively the local magnetic properties at the Ni/HZO interface in functional Au/Co/Ni/HZO/W capacitors and demonstrate clear evidence of the ferroelectric polarization effect on the magnetic response of a nanometer-thick Ni marker layer. The observed magnetoelectric effect and the electronic band lineup of the Ni/HZO interface are interpreted based on the results of our theoretical modeling. It elucidates the critical role of an ultrathin NiO interlayer, which controls the sign of the magnetoelectric effect as well as provides a realistic band offset at the Ni/HZO interface, in agreement with the experiment. Our results hold promise for the use of ferroelectric HfO2-based composite multiferroics for the design of multifunctional devices compatible with modern semiconductor technology.

On-Chip TaO x -Based Non-volatile Resistive Memory for in vitro Neurointerfaces.

The development of highly integrated electrophysiological devices working in direct contact with living neuron tissue opens new exciting prospects in the fields of neurophysiology and medicine, but imposes tight requirements on the power dissipated by electronics. On-chip preprocessing of neuronal signals can substantially decrease the power dissipated by external data interfaces, and the addition of embedded non-volatile memory would significantly improve the performance of a co-processor in real-time processing of the incoming information stream from the neuron tissue. Here, we evaluate the parameters of TaO x -based resistive switching (RS) memory devices produced by magnetron sputtering technique and integrated with the 180-nm CMOS field-effect transistors as possible candidates for on-chip memory in the hybrid neurointerface under development. The electrical parameters of the optimized one-transistor-one-resistor (1T-1R) devices, such as the switching voltage (approx. ±1 V), uniformity of the R off/R on ratio (∼10), read/write speed (<40 ns), and the number of the writing cycles (up to 1010), are satisfactory. The energy values for writing and reading out a bit ∼30 and ∼0.1 pJ, respectively, are also suitable for the desired in vitro neurointerfaces, but are still far too high once the prospective in vivo applications are considered. Challenges arising in the course of the prospective fabrication of the proposed TaO x -based RS devices in the back-end-of-line process are identified.

Polarization-dependent electric potential distribution across nanoscale ferroelectric Hf0.5Zr0.5O2 in functional memory capacitors.

The emergence of ferroelectricity in nanometer-thick films of doped hafnium oxide (HfO2) makes this material a promising candidate for use in Si-compatible non-volatile memory devices. The switchable polarization of ferroelectric HfO2 controls functional properties of these devices through the electric potential distribution across the capacitor. The experimental characterization of the local electric potential at the nanoscale has not so far been realized in practice. Here, we develop a new methodology which allows us, for the first time, to experimentally quantify the polarization-dependent potential profile across few-nanometer-thick ferroelectric Hf0.5Zr0.5O2 thin films. Using a standing-wave excitation mode in synchrotron based hard X-ray photoemission spectroscopy, we depth-selectively probe TiN/Hf0.5Zr0.5O2/W prototype memory capacitors and determine the local electrostatic potential by analyzing the core-level line shifts. We find that the electric potential profile across the Hf0.5Zr0.5O2 layer is non-linear and changes with in situ polarization switching. Combined with our scanning transmission electron microscopy data and theoretical modeling, we interpret the observed non-linear potential behavior in terms of defects in Hf0.5Zr0.5O2, at both interfaces, and their charge state modulated by the ferroelectric polarization. Our results provide an important insight into the intrinsic electronic properties of HfO2 based ferroelectric capacitors and are essential for engineering memory devices.

Ferroelectric Second-Order Memristor.

While the conductance of a first-order memristor is defined entirely by the external stimuli, in the second-order memristor it is governed by the both the external stimuli and its instant internal state. As a result, the dynamics of such devices allows to naturally emulate the temporal behavior of biological synapses, which encodes the spike timing information in synaptic weights. Here, we demonstrate a new type of second-order memristor functionality in the ferroelectric HfO2-based tunnel junction on silicon. The continuous change of conductance in the p+-Si/Hf0.5Zr0.5O2/TiN tunnel junction is achieved via the gradual switching of polarization in ferroelectric domains of polycrystalline Hf0.5Zr0.5O2 layer, whereas the combined dynamics of the built-in electric field and charge trapping/detrapping at the defect states at the bottom Si interface defines the temporal behavior of the memristor device, similar to synapses in biological systems. The implemented ferroelectric second-order memristor exhibits various synaptic functionalities, such as paired-pulse potentiation/depression and spike-rate-dependent plasticity, and can serve as a building block for the development of neuromorphic computing architectures.

Effect of Polarization Reversal in Ferroelectric TiN/Hf0.5Zr0.5O2/TiN Devices on Electronic Conditions at Interfaces Studied in Operando by Hard X-ray Photoemission Spectroscopy.

Because of their compatibility with modern Si-based technology, HfO2-based ferroelectric films have recently attracted attention as strong candidates for applications in memory devices, in particular, ferroelectric field-effect transistors or ferroelectric tunnel junctions. A key property defining the functionality of these devices is the polarization dependent change of the electronic band alignment at the metal/ferroelectric interface. Here, we report on the effect of polarization reversal in functional ferroelectric TiN/Hf0.5Zr0.5O2/TiN capacitors on the potential distribution across the stack and the electronic band line-up at the interfaces studied in operando by hard X-ray photoemission spectroscopy. By tracking changes in the position of Hf0.5Zr0.5O2 core-level lines with respect to those of the TiN electrode in both short- and open-circuit configurations following in situ polarization reversal, we derive the conduction band offset to be 0.7 (1.0) eV at the top and 1.7 (1.0) eV at the bottom interfaces for polarization, pointing up (down), respectively. Energy dispersive X-ray spectroscopy profiling of the sample cross-section in combination with the laboratory X-ray photoelectron spectroscopy reveal the presence of a TiOx/TiON layer at  both interfaces. The observed asymmetry in the band line-up changes in the TiN/Hf0.5Zr0.5O2/TiN memory stack is explained by different origin of these oxidized layers and effective pinning of polarization at the top interface. The described methodology and first experimental results are useful for the optimization of HfO2-based ferroelectric memory devices under development.

Crossbar Nanoscale HfO2-Based Electronic Synapses.

Crossbar resistive switching devices down to 40 × 40 nm(2) in size comprising 3-nm-thick HfO2 layers are forming-free and exhibit up to 10(5) switching cycles. Four-nanometer-thick devices display the ability of gradual switching in both directions, thus emulating long-term potentiation/depression properties akin to biological synapses. Both forming-free and gradual switching properties are modeled in terms of oxygen vacancy generation in an ultrathin HfO2 layer. By applying the voltage pulses to the opposite electrodes of nanodevices with the shape emulating spikes in biological neurons, spike-timing-dependent plasticity functionality is demonstrated. Thus, the fabricated memristors in crossbar geometry are promising candidates for hardware implementation of hybrid CMOS-neuron/memristor-synapse neural networks.