Ferroelectric switching is unambiguously demonstrated for the first time in a III-V semiconductor based material: Al_1-xSc_xN—A discovery which could help to satisfy the urgent demand for thin film ferroelectrics with high performance and good technological compatibility with generic semiconductor technology which arises from a multitude of memory, micro/nano-actuator, and emerging applications based on controlling electrical polarization. The appearance of ferroelectricity in Al_1-xSc_xN can be related to the continuous distortion of the original wurtzite-type crystal structure towards a layered-hexagonal structure with increasing Sc content and tensile strain, which is expected to be extendable to other III-nitride based solid solutions. Coercive fields which are systematically adjustable by more than 3 MV/cm, high remnant polarizations in excess of 100 μC/cm²—which constitute the first experimental estimate of the previously inaccessible spontaneous polarization in a III-nitride based material, an almost ideally square-like hysteresis resulting in excellent piezoelectric linearity over a wide strain interval from −0.3% to + 0.4% and a paraelectric transition temperature in excess of 600 °C are confirmed. This intriguing combination of properties is to our knowledge as of now unprecedented in the field of polycrystalline ferroelectric thin films and promises to significantly advance the commencing integration of ferroelectric functionality to micro- and nanotechnology, while at the same time providing substantial insight to one of the central open questions of the III-nitride semiconductors—that of their spontaneous polarization.

Through its dependence on low symmetry crystal phases, ferroelectricity is inherently a property tied to the lower temperature ranges of the phase diagram for a given material. This paper presents conclusive evidence that in the case of ferroelectric Al_1−xSc_xN, low temperature has to be seen as a purely relative term, since its ferroelectric-to-paraelectric transition temperature is confirmed to surpass 1100 °C and thus the transition temperature of virtually any other thin film ferroelectric. We arrived at this conclusion through investigating the structural stability of 0.4–2 μm thick Al_0.73Sc_0.27N films grown on Mo bottom electrodes via in situ high-temperature x-ray diffraction and permittivity measurements. Our studies reveal that the wurtzite-type structure of Al_0.73Sc_0.27N is conserved during the entire 1100 °C annealing cycle, apparent through a constant c/a lattice parameter ratio. In situ permittivity measurements performed up to 1000 °C strongly support this conclusion and include what could be the onset of a diverging permittivity only at the very upper end of the measurement interval. Our in situ measurements are well-supported by ex situ (scanning) transmission electron microscopy and polarization and capacity hysteresis measurements. These results confirm the structural stability on the sub-μm scale next to the stability of the inscribed polarization during the complete 1100 °C annealing treatment. Thus, Al_1−xSc_xN, there is the first readily available thin film ferroelectric with a temperature stability that surpasses virtually all thermal budgets occurring in microtechnology, be it during fabrication or the lifetime of a device—even in harshest environments.

This work presents the first atomic scale evidence for ferroelectric polarization inversion on the unit cell level in a wurtzite-type material based on epitaxial Al_0.75Sc_0.25N thin films. The electric field induced formation of Al-polar inversion domains in the originally N-polar film is unambiguously determined by atomic resolution imaging using aberration-corrected scanning transmission electron microscopy (STEM). Anisotropic etching supports STEM results confirming a complete and homogenous polarization inversion at the film surface for the switched regions and the virtual absence of previous inversion domains in as-deposited regions. Local evidence of residual N-polar domains at the bottom electrode interface is observed and can be explained by both stress gradients and electric field deflection. The epitaxial relationship of the sapphire/AlN/Mo/AlScN multilayer stack is discussed in detail. Selected-area electron diffraction experiments and XRD pole figures reveal a Pitsch–Schrader type orientation relation between the Mo electrode and the AlScN film.

Analog switching in ferroelectric devices promises neuromorphic computing with the highest energy efficiency if limited device scalability can be overcome. To contribute to a solution, one reports on the ferroelectric switching characteristics of sub‐5 nm thin Al_0.74Sc_0.26N films grown on Pt/Ti/SiO₂/Si and epitaxial Pt/GaN/sapphire templates by sputter‐deposition. In this context, the study focuses on the following major achievements compared to previously available wurtzite‐type ferroelectrics: 1) Record low switching voltages down to 1 V are achieved, which is in a range that can be supplied by standard on‐chip voltage sources. 2) Compared to the previously investigated deposition of ultrathin Al_1−xSc_xN films on epitaxial templates, a significantly larger coercive field (E_c) to breakdown field ratio is observed for Al_0.74Sc_0.26N films grown on silicon substrates, the technologically most relevant substrate‐type. 3) The formation of true ferroelectric domains in wurtzite‐type materials is for the first time demonstrated on the atomic scale by scanning transmission electron microscopy (STEM) investigations of a sub‐5 nm thin partially switched film. The direct observation of inversion domain boundaries (IDB) within single nm‐sized grains supports the theory of a gradual domain‐wall driven switching process in wurtzite‐type ferroelectrics. Ultimately, this should enable the analog switching necessary for mimicking neuromorphic concepts also in highly scaled devices.

The recent emergence of wurtzite‐type nitride ferroelectrics such as Al_1‐xSc_xN has paved the way for the introduction of all‐epitaxial, all‐wurtzite‐type ferroelectric III‐N semiconductor heterostructures. This paper presents the first in‐depth structural and electrical characterization of such an epitaxial heterostructure by investigating sputter deposited Al_1‐xSc_xN solid solutions with x between 0.19 and 0.28 grown over doped n‐GaN. The results of detailed structural investigations on the strain state and the initial unit‐cell polarity with the peculiarities observed in the ferroelectric response are correlated. Among these, a Sc‐content dependent splitting of the ferroelectric displacement current into separate peaks, which can be correlated with the presence of multiple strain states in the Al_1‐xSc_xN films is discussed. Unlike in previously reported studies on ferroelectric Al_1‐xSc_xN, all films thicker than 30 nm grown on the metal (M)‐polar GaN template feature an initial multidomain state. The results support that regions with opposed polarities in as‐grown films do not result as a direct consequence of the in‐plane strain distribution, but are rather mediated by the competition between M‐polar epitaxial growth on an M‐polar template and a deposition process that favors nitrogen (N)‐polar growth.

Wurtzite‐type Al_1−xSc_xN solid solutions grown by metal organic chemical vapor deposition are for the first time confirmed to be ferroelectric. The film with 230 nm thickness and x = 0.15 exhibits a coercive field of 5.5 MV cm⁻¹ at a measurement frequency of 1.5 kHz. The single crystal quality and homogeneous chemical composition of the film are confirmed by X‐ray diffraction and spectroscopic methods such as time of flight secondary ion mass spectrometry. Annular bright field scanning transmission electron microscopy serves to prove the ferroelectric polarization inversion at the unit cell level. The single crystal quality further allows to image the large‐scale domain pattern of a wurtzite‐type ferroelectric for the first time, revealing a predominantly cone‐like domain shape along the c‐axis of the material. As in previous work, this again implies the presence of strong polarization discontinuities along this crystallographic axis, which can be suitable for current transport. The domains are separated by narrow domain walls, for which an upper thickness limit of 3 nm is deduced but which can potentially be atomically sharp. The authors are confident that these results will advance the commencement of the integration of wurtzite‐type ferroelectrics to GaN as well as generally III‐N‐based heterostructures and devices.