HfO 2 , a simple binary oxide, holds ultra-scalable ferroelectricity integrable into silicon technology. Polar orthorhombic (Pbc2 1 ) form in ultra-thin-films ascribes as the plausible rootcause of the astonishing ferroelectricity, which has thought not attainable in bulk crystals.Though, perplexities remain primarily due to the polymorphic nature and the characterization challenges at small-length scales. Herein, utilizing a state-of-the-art Laser-Diode-heated Floating Zone technique, we report ferroelectricity in bulk singlecrystalline HfO 2 :Y as well as the presence of anti-polar Pbca phase at different Y concentrations. Neutron diffraction and atomic imaging demonstrate (anti-)polar crystallographic signatures and abundant 90 o /180 o ferroelectric domains in addition to the switchable polarization with little wake-up effects. Density-functional theory calculations suggest that the Yttrium doping and rapid cooling are the key factors for the desired phase. Our observations provide new insights into the polymorphic nature and phase controlling of HfO 2 , remove the upper size limit for ferroelectricity, and also pave a new road toward the next-generation ferroelectric devices.

A quantum spin liquid is a state of matter where unpaired electrons' spins, although entangled, do not show magnetic order even at the zero temperature. The realization of a quantum spin liquid is a long-sought goal in condensed-matter physics. Although neutron scattering experiments on the two-dimensional spin-1/2 kagome lattice ZnCu 3 (OD) 6 Cl 2 and triangular lattice YbMgGaO 4 have found evidence for the hallmark of a quantum spin liquid at very low temperature (a continuum of magnetic excitations), the presence of magnetic and non-magnetic site chemical disorder complicates the interpretation of the data. Recently, the three-dimensional Ce 3+ pyrochlore lattice Ce 2 Sn 2 O 7 has been suggested as a clean, effective spin-1/2 quantum spin liquid candidate, but evidence of a spin excitation continuum is still missing. Here, we use thermodynamic, muon spin relaxation and neutron scattering experiments on single crystals of Ce 2 Zr 2 O 7 , a compound isostructural to Ce 2 Sn 2 O 7 , to demonstrate the absence of magnetic ordering and the presence of a spin excitation continuum at 35 mK. With no evidence of oxygen deficiency and magnetic/non-magnetic ion disorder seen by neutron diffraction and diffuse scattering measurements, Ce 2 Zr 2 O 7 may be a three-dimensional pyrochlore lattice quantum spin liquid material with minimum magnetic and non-magnetic chemical disorder.

The direct domain coupling of spontaneous ferroelectric polarization and net magnetic moment can result in giant magnetoelectric (ME) coupling, which is essential to achieve mutual control and practical applications of multiferroics. Recently, the possible bulk domain coupling, the mutual control of ferroelectricity (FE) and weak ferromagnetism (WFM) have been theoretically predicted in hexagonal LuFeO 3 . Here, we report the first successful growth of highly-cleavable Sc-stabilized hexagonal Lu 0.6 Sc 0.4 FeO 3 (h-LSFO) single crystals, as well as the first visualization of their intrinsic cloverleaf pattern of vortex FE domains and large-loop WFM domains. The vortex FE domains are on the order of 0.1-1 μm in size. On the other hand, the loop WFM domains are~100 μm in size, and there exists no interlocking of FE and WFM domain walls. These strongly manifest the decoupling between FE and WFM in h-LSFO. The domain decoupling can be explained as the consequence of the structure-mediated coupling between polarization and dominant in-plane antiferromagnetic spins according to the theoretical prediction, which reveals intriguing interplays between FE, WFM, and antiferromagnetic orders in h-LSFO. Our results also indicate that the magnetic topological charge tends to be identical to the structural topological charge. This could provide new insights into the induction of direct coupling between magnetism and ferroelectricity mediated by structural distortions, which will be useful for the future applications of multiferroics.

Spin liquid ground states are predicted to arise within several distinct scenarios in condensed matter physics. The observation of these disordered magnetic states is particularly pervasive amongst a class of materials known as frustrated magnets, in which the competition between various magnetic exchange interactions prevents the system from adopting long-range magnetic order at low temperatures. Spin liquids continue to be of great interest due to their exotic nature and the possibility that they may support fractionalised excitations, such as Majorana fermions. Systems that allow for such phenomena are not only fascinating from a fundamental perspective but may also be practically significant in future technologies based on quantum computation. Here we show that the underlying antiferromagnetic sublattice in TbInO3 undergoes a crystal field induced triangular-to-honeycomb dilution at low temperatures. The absence of a conventional magnetic ordering transition at the lowest measurable temperatures indicates that another critical mechanism must govern in the ground state selection of TbInO3. We propose that anisotropic exchange interactionsmediated through strong spin-orbit coupling on the emergent honeycomb lattice of TbInO3give rise to a highly frustrated spin liquid.One notable example of a spin liquid 1,2 is that of the S = ½ Heisenberg antiferromagnet on a two-dimensional kagome lattice, a frustrated network of corner-sharing triangles. It is now widely considered that this magnetic system displays a quantum spin liquid ground state 3 and there is recent experimental evidence to suggest that a gapped quantum spin liquid state is likely realised in the Cu 2+ -based kagome antiferromagnet, herbertsmithite. 4 The two-dimensional honeycomb net, on the other hand, is a bipartite lattice and, therefore, does not give rise to frustrated ground states in the presence of conventional nearest-

Hafnia (HfO2) is a promising material for emerging chip applications due to its high-κ dielectric behavior, suitability for negative capacitance heterostructures, scalable ferroelectricity, and silicon compatibility. The lattice dynamics along with phononic properties such as thermal conductivity, contraction, and heat capacity are under-explored, primarily due to the absence of high quality single crystals. Herein, we report the vibrational properties of a series of HfO2 crystals stabilized with yttrium (chemical formula HfO2: xY, where x = 20, 12, 11, 8, and 0%) and compare our findings with a symmetry analysis and lattice dynamics calculations. We untangle the effects of Y by testing our calculations against the measured Raman and infrared spectra of the cubic, antipolar orthorhombic, and monoclinic phases and then proceed to reveal the signature modes of polar orthorhombic hafnia. This work provides a spectroscopic fingerprint for several different phases of HfO2 and paves the way for an analysis of mode contributions to high-κ dielectric and ferroelectric properties for chip technologies.