Sn Vacancies in Photorefractive Sn\u3csub\u3e2\u3c/sub\u3eP\u3csub\u3e2\u3c/sub\u3eS\u3csub\u3e6\u3c/sub\u3e Crystals: An Electron Paramagnetic Resonance Study of an Optically Active Hole Trap

Electron paramagnetic resonance (EPR) is used to identify the singly ionized charge state of the Sn vacancy (V−Sn) in single crystals of Sn2P2S6 (often referred to as SPS). These vacancies, acting as a hole trap, are expected to be important participants in the photorefractive effect observed in undoped SPS crystals. In as-grown crystals, the Sn vacancies are doubly ionized (V2−Sn) with no unpaired spins. They are then converted to a stable EPR-active state when an electron is removed (i.e., a hole is trapped) during an illumination below 100 K with 633 nm laser light. The resulting EPR spectrum has g-matrix principal values of 2.0079, 2.0231, and 1.9717. There are resolved hyperfine interactions with two P neighbors and one Sn neighbor. The isotropic portions of these hyperfine matrices are 167 and 79 MHz for the two 31P neighbors and 8504 MHz for the one Sn neighbor (this latter value is the average for 117Sn and 119Sn). These V−Sn vacancies are shallow acceptors with the hole occupying a diffuse wave function that overlaps the neighboring Sn2+ ion and (P2S6)4− anionic unit. Using a general-order kinetics approach, an analysis of isothermal decay curves of the V−Sn EPR spectrum in the 107–115 K region gives an activation energy of 283 meV

Sulfur Vacancies in Photorefractive Sn\u3csub\u3e2\u3c/sub\u3eP\u3csub\u3e2\u3c/sub\u3eS\u3csub\u3e6\u3c/sub\u3e Crystals

A photoinduced electron paramagnetic resonance (EPR) spectrum in single crystals of Sn2P2S6 (SPS) is assigned to an electron trapped at a sulfur vacancy. These vacancies are unintentionally present in undoped SPS crystals and are expected to play an important role in the photorefractive behavior of the material. Nonparamagnetic sulfur vacancies are formed during the initial growth of the crystal. Subsequent illumination below 100 K with 442 nm laser light easily converts these vacancies to EPR-active defects. The resulting S = 1/2 spectrum shows well-resolved and nearly isotropic hyperfine interactions with two P ions and two Sn ions. Partially resolved interactions with four additional neighboring Sn ions are also observed. Principal values of the g matrix are 1.9700, 1.8946, and 1.9006, with the corresponding principal axes along the a, b, and c directions in the crystal. The isotropic parts of the two primary 31P hyperfine interactions are 19.5 and 32.6 MHz and the isotropic parts of the two primary Sn hyperfine interactions are 860 and 1320 MHz (the latter values are each an average for 117Sn and 119Sn). These hyperfine results suggest that singly ionized sulfur vacancies have a diffuse wave function in SPS crystals, and thus are shallow donors. Before illumination, sulfur vacancies are in the doubly ionized charge state because of compensation by unidentified acceptors. They then trap an electron during illumination. The EPR spectrum from the sulfur vacancy is destroyed when a crystal is heated above 120 K in the dark and reappears when the crystal is illuminated again at low temperature

Dual Role of Sb Ions as Electron Traps and Hole Traps in Photorefractive Sn\u3csub\u3e2\u3c/sub\u3eP\u3csub\u3e2\u3c/sub\u3eS\u3csub\u3e6\u3c/sub\u3e Crystals

Doping photorefractive single crystals of Sn2P2S6 with antimony introduces both electron and hole traps. In as-grown crystals, Sb3+ (5s2) ions replace Sn2+ ions. These Sb3+ ions are either isolated (with no nearby perturbing defects) or they have a charge-compensating Sn2+ vacancy at a nearest-neighbor Sn site. When illuminated with 633 nm laser light, isolated Sb3+ ions trap electrons and become Sb2+ (5s25p1) ions. In contrast, Sb3+ ions with an adjacent Sn vacancy trap holes during illumination. The hole is primarily localized on the (P2S6)4− anionic unit next to the Sb3+ ion and Sn2+ vacancy. These trapped electrons and holes are thermally stable below ∼200 K, and they are observed with electron paramagnetic resonance (EPR) at temperatures below 150 K. Resolved hyperfine interactions with 31P, 121Sb, and 123Sb nuclei are used to establish the defect models. Abstract © 2016 Optical Society of Americ

Polarization-controlled volatile ferroelectric and capacitive switching in Sn2P2S6

Smart electronic circuits that support neuromorphic computing on the hardware level necessitate materials with memristive, memcapacitive, and neuromorphic- like functional properties; in short, the electronic response must depend on the voltage history, thus enabling learning algorithms. Here we demonstrate volatile ferroelectric switching of Sn _2 P _2 S _6 at room temperature and see that initial polarization orientation strongly determines the properties of polarization switching. In particular, polarization switching hysteresis is strongly imprinted by the original polarization state, shifting the regions of non-linearity toward zero-bias. As a corollary, polarization switching also enables effective capacitive switching, approaching the sought-after regime of memcapacitance. Landau–Ginzburg–Devonshire simulations demonstrate that one mechanism by which polarization can control the shape of the hysteresis loop is the existence of charged domain walls (DWs) decorating the periphery of the repolarization nucleus. These walls oppose the growth of the switched domain and favor back-switching, thus creating a scenario of controlled volatile ferroelectric switching. Although the measurements were carried out with single crystals, prospectively volatile polarization switching can be tuned by tailoring sample thickness, DW mobility and electric fields, paving way to non-linear dielectric properties for smart electronic circuits

Photoinduced Trapping of Charge at Sulfur Vacancies and Copper Ions in Photorefractive Sn\u3csub\u3e2\u3c/sub\u3eP\u3csub\u3e2\u3c/sub\u3eS\u3csub\u3e6\u3c/sub\u3e Crystals

Electron paramagnetic resonance (EPR) is used to monitor photoinduced changes in the charge states of sulfur vacancies and Cu ions in tin hypothiodiphosphate. A Sn2P2S6 crystal containing Cu+ (3d10) ions at Sn2+ sites was grown by the chemical vapor transport method. Doubly ionized sulfur vacancies (V2+S) are also present in the as-grown crystal (where they serve as charge compensators for the Cu+ ions). For temperatures below 70 K, exposure to 532 or 633 nm laser light produces stable Cu2+ (3d9) ions, as electrons move from Cu+ ions to sulfur vacancies. A g matrix and a 63,65Cu hyperfine matrix are obtained from the angular dependence of the Cu2+ EPR spectrum. Paramagnetic singly ionized (V+S) and nonparamagnetic neutral (V0S) charge states of the sulfur vacancies, with one and two trapped electrons, respectively, are formed during the illumination. Above 70 K, the neutral vacancies (V0S) are thermally unstable and convert to V+S vacancies by releasing an electron to the conduction band. These released electrons move back to Cu2+ ions and restore Cu+ ions. Analysis of isothermal decay curves acquired by monitoring the intensity of the Cu2+ EPR spectrum between 74 and 82 K, after removing the light, gives an activation energy of 194 meV for the release of an electron from a V0S vacancy. Warming above 120 K destroys the V+S vacancies and the remaining Cu2+ ions. The photoinduced EPR spectrum from a small concentration of unintentionally present Ni+ ions at Sn2+ sites is observed near 40 K in the Sn2P2S6 crystal

Near-infrared-sensitive Photorefractive Sn\u3csub\u3e2\u3c/sub\u3eP\u3csub\u3e2\u3c/sub\u3eS\u3csub\u3e6\u3c/sub\u3e Crystals Grown by the Bridgman Method

Ferroelectric tin hypothiodiphosphate (Sn2P2S6) crystals are well-known for their significant piezoelectric, electro-optic, and nonlinear optical properties. These crystals have usually been grown by a vapor transport technique. We report in this paper on the first study of photorefractive nonlinearity in Sn2P2S6 crystals grown by the Bridgman method. Pronounced photorefraction is observed in the near-infrared region of the spectrum even with no preliminary optical sensitizing