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arXiv:2412.12029 · Journal of Applied Physics

Epitaxial strain tuning of Er3+ in ferroelectric thin films

Rafaela M. Brinn, Peter Benjamin Meisenheimer, Medha Dandu, Elyse Barré, Piush Behera, Archana Raja, R. Ramesh, Paul Stevenson

Published Apr 2, 2025• 1 citation
arXivHTMLPDF

Abstract

Er 3 + color centers are promising candidates for quantum science and technology due to their long electron and nuclear spin coherence times, as well as their desirable emission wavelength. By selecting host materials with suitable, controllable properties, we introduce new parameters that can be used to tailor the Er3+ emission spectrum. PbTiO3 is a well-studied ferroelectric material with known methods of engineering different domain configurations through epitaxial strain. By distorting the structure of Er3+-doped PbTiO3 thin films, we can manipulate the crystal fields around the Er3+ dopant. This is resolved through changes in the Er3+ resonant fluorescence spectra, tying the optical properties of the defect directly to the domain configurations of the ferroelectic matrix. Additionally, we are able to resolve a second set of peaks for films with in-plane ferroelectric polarization. We hypothesize these results to be due to either the Er3+ substituting different sites of the PbTiO3 crystal, differences in charges between the Er3+ dopant and the original substituent ion, or selection rules. Systematically studying the relationship between the Er3+ emission and the epitaxial strain of the ferroelectric matrix lays the pathway for future optical studies of spin manipulation by altering ferroelectric order parameters.

DOI
10.1063/5.0253357

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Er 3 + color centers are promising candidates for quantum science and technology due to their long electron and nuclear spin coherence times, as well as their desirable emission wavelength. By selecting host materials with suitable, controllable properties, we introduce new parameters that can be used to tailor the Er3+ emission spectrum. PbTiO3 is a well-studied ferroelectric material with known methods of engineering different domain configurations through epitaxial strain. By distorting the structure of Er3+-doped PbTiO3 thin films, we can manipulate the crystal fields around the Er3+ dopant. This is resolved through changes in the Er3+ resonant fluorescence spectra, tying the optical properties of the defect directly to the domain configurations of the ferroelectic matrix. Additionally, we are able to resolve a second set of peaks for films with in-plane ferroelectric polarization. We hypothesize these results to be due to either the Er3+ substituting different sites of the PbTiO3 crystal, differences in charges between the Er3+ dopant and the original substituent ion, or selection rules. Systematically studying the relationship between the Er3+ emission and the epitaxial strain of the ferroelectric matrix lays the pathway for future optical studies of spin manipulation by altering ferroelectric order parameters.
Rare-earth ion dopants in solid-state hosts are ideal candidates for quantum communication technologies, such as quantum memories, due to the intrinsic spin–photon interface of the rare-earth ion combined with the integration methods available in the solid state. Erbium-doped cerium oxide (Er:CeO2) is a particularly promising host material platform for such a quantum memory, as it combines the telecom-wavelength (∼1.5μm) 4f–4f transition of erbium, a predicted long electron spin coherence time when embedded in CeO2, and a small lattice mismatch with silicon. In this work, we report on the epitaxial growth of Er:CeO2 thin films on silicon using molecular beam epitaxy, with controlled erbium concentration between 2 and 130 parts per million (ppm). We carry out a detailed microstructural study to verify the CeO2 host structure and characterize the spin and optical properties of the embedded Er3+ ions as a function of doping density. In as-grown Er:CeO2 in the 2–3 ppm regime, we identify an EPR linewidth of 245(1) MHz, an optical inhomogeneous linewidth of 9.5(2) GHz, an optical excited state lifetime of 3.5(1) ms, and a spectral diffusion-limited homogeneous linewidth as narrow as 4.8(3) MHz. We test the annealing of Er:CeO2 films up to 900 °C, which yields narrowing of the inhomogeneous linewidth by 20% and extension of the excited state lifetime by 40%.
Erbium-doped TiO2 materials are promising candidates for advancing quantum technologies, necessitating a thorough understanding of their electronic and crystal structures to tailor their properties and enhance coherence times. This study explored epitaxial erbium-doped rutile TiO2 films deposited on r-sapphire substrates using molecular beam epitaxy. Photoluminescence excitation spectroscopy demonstrated decreasing photoluminescence lifetimes with erbium doping, indicating limited optical coherence times. Lattice distortions associated with Er3+ were probed by x-ray absorption spectroscopy, indicating that erbium primarily occupies Ti4+ sites and influences oxygen vacancies. Significant lattice distortions in the higher-order shells and apparent full coordination around erbium suggest that additional defects are likely prevalent in these regions. These findings indicate that defects contribute to limited coherence times by introducing alternative decay pathways, leading to shorter photoluminescence lifetimes.
Erbium-doped solid-state crystals present an attractive platform for quantum communication, combining the telecom C-band spin–photon interface and long coherence times of erbium (Er3+) with the versatility of solid-state hosts. However, across commonly investigated materials, Er3+ is a “dim” ion, with low optical emission rates of kilohertz at most. This makes implementing quantum information transfer protocols (e.g., quantum teleportation) at usable rates a major challenge. One route to increasing Er3+ radiative rates is by careful selection of crystal hosts: the crystal field around an Er3+ ion may hybridize states of different parity, potentially increasing the radiative rate of its telecom transition. Here, using high-throughput computational methods, the radiative rates of Er3+ embedded in 9215 materials are estimated. The computation shows that careful host selection could increase Er3+ radiative rates by an order of magnitude compared to commonly studied hosts. Calculated results are compared with experimental radiative rates in a subset of materials, finding notable clustering but weak correlation. Nevertheless, the “brightest” candidates combined with suitable nanophotonics engineering could push Er3+-based quantum memories into the megahertz bandwidth regime.
Rare-earth ions (REIs) have incomplete 4f shells and possess narrow optical intra-4f transitions due to shielding from electrons in the 5s and 5p orbitals, making them good candidates for solid-state optical quantum memory. The emission of Er3+ in the telecom C-band (1530 nm–1565 nm) makes it especially attractive for this application. In order to build practical, scalable devices, the REI needs to be embedded in a non-interacting host material, preferably one that can be integrated with silicon. In this paper, we show that Er3+ can be isovalently incorporated into epitaxial Y2O3 thin films on Si (111). We report on the synthesis of epitaxial, single-crystalline Er:Y2O3 on Si with a narrow inhomogeneous linewidth in the photoluminescence (PL) spectra, 5.1 GHz (<100 mK), and an optical excited state lifetime of 8.1 ms. The choice of Y2O3 was driven by its low nuclear spin and small lattice mismatch with Si. Using PL and electron paramagnetic resonance, we show that Er3+ substitutes for Y in the crystal lattice. The role of interfacial SiOx, diffusion of silicon into the film, and the effect of buffer layers on the inhomogeneous PL linewidth are examined. We also find that the linewidth decreased monotonically with film thickness but surprisingly exhibits no correlation with the film crystalline quality, as measured by the x-ray rocking curve scans, suggesting other factors at play that limit the inhomogeneous broadening in Y2O3 films.
Erbium-doped \ch{TiO2} materials are promising candidates for advancing quantum technologies, necessitating a thorough understanding of their electronic and crystal structures to tailor their properties and enhance coherence times. This study explored epitaxial erbium-doped rutile \ch{TiO2} films deposited on r-sapphire substrates using molecular beam epitaxy. Photoluminescence excitation spectroscopy demonstrated decreasing fluorescence lifetimes with erbium doping, indicating limited coherence times. Lattice distortions associated with \ch{Er^{3+}} were probed by X-ray absorption spectroscopy, indicating that erbium primarily occupies \ch{Ti^{4+}} sites and influences oxygen vacancies. Significant lattice distortions in the higher-order shells and full coordination around erbium suggest that additional defects are likely prevalent in these regions. These findings indicate that defects contribute to limited coherence times by introducing alternative decay pathways, leading to shorter fluorescence lifetimes.
We grow single crystal erbium-oxide (Er2O3) epitaxially on a Si (111) substrate by using molecular beam epitaxy and investigate the population dynamics in Er3+ ions for the coherent manipulation of the population in Er2O3. Sharp and discrete Stark energy levels of the 4I13/2 manifold as small as 200 μeV are observed with inhomogeneous broadening caused by the uniform crystal field of the epitaxial Er2O3. We also experimentally determine the time constant of the resonant population transfer between spatially distant Er3+-ion sites, which is limited to the manipulation time of the population in the Er2O3 crystals. Using selective excitation of the Stark level in the 4I13/2 manifold, we obtain the energy transfer times between spatially distant Er3+ ions, and they are about 2 μs between sites whose crystallographic symmetry is different and 10 μs between sites whose symmetry is the same.