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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. [ABSTRACT FROM AUTHOR]

Photosystem I (PSI) is a ∼1000 kDa transmembrane protein that enables photoactivated charge separation with ∼1 V driving potential and ∼100% quantum efficiency during the photosynthetic process. Although such properties make PSI a potential candidate for integration into bio-hybrid solar energy harvesting devices, the grand challenge in orchestrating such integration rests on rationally designed 3D architectures that can organize and stabilize PSI in the myriad of harsh conditions in which it needs to function. The current study investigates the optical response and photoactive properties of PSI encapsulated in a highly stable nanoporous metal-organic framework (ZIF-8), denoted here as PSI@ZIF-8. The ZIF-8 framework provides a unique scaffold with a robust confining environment for PSI while protecting its precisely coordinated chlorophyll networks from denaturing agents. Significant blue shifts in the fluorescence emissions from UV-vis measurements reveal the successful confinement of PSI in ZIF-8. Pump-probe spectroscopy confirms the photoactivity of the PSI@ZIF-8 composites by revealing the successful internal charge separation and external charge transfer of P 700 + and F B - even after exposure to denaturing agents and organic solvents. This work provides greater fundamental understanding of confinement effects on pigment networks, while significantly broadening the potential working environments for PSI-integrated bio-hybrid materials., Competing Interests: The authors have no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)