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.

Composite bilayer multiferroics combining ferroelectric (FE) and ferromagnetic (FM) thin‐film materials in a heterostructure and exhibiting magnetoelectric (ME) coupling effect are of great scientific and technological interest. In particular, electronically driven ME coupling implies that the FE polarization orientation affects the magnetic properties of FM at the interface with FE. Unlike metals, where the electric field penetrates over distances of 1–2 unit cells only, magnetic semiconductors, particularly doped EuS, with a ≈10 nm screening length appear a viable alternative. In addition, EuS exhibits a metal–insulator transition, thus offering new functionalities in nanoelectronics. Meanwhile, ultrathin polycrystalline films of doped HfO2, such as Hf0.5Zr0.5O2 (HZO), stabilized in the noncentrosymmetric orthorhombic phase, are identified as a novel class of robust FE materials. In this work, FM EuS integrated with FE HZO in a bilayered structure is promoted as a prospective composite multiferroic. The functionality of both ultrathin FM‐EuS and FE‐HZO layers as well as their compatibility in a capacitor configuration is demonstrated. The comprehensive information on the structural, chemical, and electronic properties of EuS/HZO interface endorses it as a promising medium for magnetoelectric coupling phenomena, particularly, the effect of polarization reversal in FE‐HZO on the magnetic and transport properties in EuS.

Multiferroic materials with coexisting ferroelectric and ferromagnetic orders have attracted much attention due to the magnetoelectric coupling opening alternative prospects for electronic devices. Composite multiferroics containing separate ferroelectric and ferromagnetic components are a promising alternative to the single‐phase counterparts. Composite multiferroic structures comprising HfO2‐based ferroelectrics are potentially feasible for technological applications. Here, this study reports on the experiments aiming at the manifestation of magnetoelectric coupling at Fe/Hf0.5Zr0.5O2 (HZO) interface. Using synchrotron based 57Fe Mössbauer spectroscopy technique in operando, this study probes element‐selectively the local magnetic properties of a nanometer‐thick enriched 57Fe marker layer in functional Pt/57Fe/HZO/TiN capacitors and demonstrates the evidence of the ferroelectric polarization effect on the α‐Fe magnetic response. Besides α‐Fe exhibiting a magnetoelectric coupling, both ferromagnetic and superparamagnetic Fe3O4 components are found in the Mössbauer spectra, apparently originating from the oxygen or OH− ions penetrating ultrathin Pt overlayer during crystallization annealing of HZO. The observed effect as well as the electronic band lineup of the Fe/HZO interface elucidated from synchrotron based hard X‐ray photoemission spectroscopy measurements are interpreted in terms of charge‐mediated magnetoelectric coupling at the Fe/HfO2 interface driven by ferroelectric HZO polarization reversal.

The crystallization of as‐grown amorphous Hf0.5Zr0.5O2 (HZO) thin films to the metastable ferroelectric phase by pulsed laser annealing (PLA) is investigated. PLA experiments are conducted using a Nd:YAG laser operating in two regimes: Q‐switched mode with a pulse duration of τ ≈ 16 ns and free‐running mode (τ ≈ 1 ms). The crystallization of a ferroelectric orthorhombic phase in the annealed films is confirmed by X‐ray diffraction, polarization versus electric field (P–E) measurements, and piezoresponse force microscopy (PFM) analyses. Remnant polarization up to 2P r ≈ 50 μC cm−2 is achieved in the TiN/HZO/W capacitor structures grown on the Si substrate and subjected to millisecond PLA. In contrast, the use of laser annealing in a 10 ns pulse duration range is found ineffective for the crystallization of any HZO phase in capacitor structures. Detailed PFM analysis across a capacitor device area reveals the effect of the local temperature on the sample surface during PLA on the resulting ferroelectric domain structure. The lower thermal impact on the substrate during PLA opens the possibility of creating local areas of the ferroelectric phase in HZO films using reflecting copper masks.