Zirconia Single Crystals Research Articles

Highly efficiency up and down -conversion photoluminescence in Er/Tm/Yb co-doped lutecia-stabilized zirconia single crystals

High-quality transparent cubic lutecia-stabilized zirconia and LSZ:Yb1Er0.05Tm0.5 single crystals were grown by the optical floating zone method for the first time. For comparison, YSZ and YSZ:Yb1Er0.05Tm0.5 single crystals were also grown. No absorption peaks were observed in the 200 ∼1100 nm range in the transmission and absorption spectra of LSZ and YSZ, indicating that both crystals are excellent matrix crystals. The absorption spectra of LSZ:Yb1Er0.05Tm0.5 and YSZ:Yb1Er0.05Tm0.5 crystals exhibit several absorption peaks at 377, 408, 462, 488, 516, 679, 785 nm and a strong broad absorption band in the 836 ∼ 1050 nm range. The up-conversion photoluminescence of the LSZ:Yb1Er0.05Tm0.5 crystal excited by a 980 nm laser exhibited several distinct emission peaks at 300, 372, 476, 531, 548, 642 and 798 nm; similar emission peaks were observed in the up-conversion photoluminescence spectrum of the YSZ:Yb1Er0.05Tm0.5 crystal, except for the absence of the 300 nm peak. The intensity of the emission peaks of the former was higher than that of the corresponding peaks of the latter. Power curves indicated that the 300 nm emission is a four-photon up-conversion process, the 372 nm and 476 nm emissions are three-photon processes, and the 548 nm and 642 nm emissions are two-photon processes. Under excitation at 379 nm, the down-conversion photoluminescence spectra of the LSZ:Yb1Er0.05Tm0.5 and YSZ:Yb1Er0.05Tm0.5 crystals showed emission peaks at 450, 457, 511, 531 and 637 nm, the peak intensities of the former are higher than those of the latter, which is due to the former with higher density and lower phonon energy as compare to the latter. These results indicate that LSZ:Yb1Er0.05Tm0.5 single crystal has advantages over YSZ:Yb1Er0.05Tm0.5 single crystal for luminescence in photonic devices.

Variation of surface morphology of material uplift near flash-healed Vickers indents under direct-current electric field in cubic zirconia single crystals

Variation of surface morphology of material uplift near flash-healed Vickers indents under direct-current electric field in cubic zirconia single crystals

Ultraviolet and White Light Emissions from Multiphoton Upconversion Transitions in Yb/Tm/Ho Codoped Cubic Zirconia Single Crystals Excited by NIR

Ultraviolet and White Light Emissions from Multiphoton Upconversion Transitions in Yb/Tm/Ho Codoped Cubic Zirconia Single Crystals Excited by NIR

Microstructural analysis of flash-healed Vickers-indented microcracks near positive/negative electrodes on the (001) surface of cubic zirconia single crystals under direct current electric fields

Flash healing is a technique that uses power spikes to rapidly repair microcracks on ceramic surfaces. In this study, the microstructures of flash-healed Vickers-indented microcracks near the positive/negative electrodes under a DC electric field were examined by scanning transmission electron microscopy. The microstructural morphology near the positive electrode was almost identical to that of the microcracks located between both electrodes, as previously reported. However, a decrease in the degree of healing was observed near the negative electrode. This was attributed to the insufficient recovery of dislocations generated at the indentation state, which should have occurred in the initial stage of healing. The delay in dislocation recovery prevented contact between the inner surfaces of the microcracks and is possibly related to the increase in oxygen vacancies near the negative electrode.

Highly efficient ultraviolet and visible light emissions from upconversion transitions in Ho/Tm/Yb co-doped lutecia-stabilized zirconia single crystals excited by a 980 nm laser

High-quality LSZ and LSZ:Yb0.25Tm0.5Ho0.03 single crystals were grown for the first time. Under 980 nm excitation, LSZ:Yb0.25Tm0.5Ho0.03 crystal has high efficiency over YSZ:Yb0.25Tm0.5Ho0.03 crystal in ultraviolet and visible light emissions.

Flash healing of Vickers microcracks formed on the (001) surface of cubic zirconia single crystals

Flash healing, a technique for microcrack healing using a flash event, has recently attracted attention for effective microcrack healing of ceramics. To investigate the diffusion-accelerated phenomena that occur during flash healing, the flash-healing behavior of Vickers indentation microcracks on (001) zirconia single crystals was investigated, mainly from the viewpoint of microstructure analysis of the healed microcracks. Scanning electron microscopy and atomic force microscopy showed that the surface microcracks were rapidly healed. However, scanning transmission electron microscopy showed that a row of pores remained along the original microcrack inside the crystal, and the crystallographic orientation relationship on both sides of the microcrack was restored to that of the original single crystal. Compared with the findings for healing without an electric field, the distance from the pore closest to the surface was larger and the total pore volume was smaller for flash healing. These results suggest that flash treatment increases lattice diffusion.

Design and preparation of white light emission from up-conversion transitions in Er3+/Tm3+/Yb3+ co-doped cubic zirconia single crystals

High-quality cubic YSZ crystals were designed with various contents of Er3+, Tm3+ and Yb3+ to produce white light emission, and grown by the optical floating zone method. The up-conversion luminescence spectra of the crystals under 980 nm laser irradiation show three distinct groups of emission peaks at ∼473 nm (blue) generated by the Tm3+1G4→3H6 transition, 531 and 547 nm (green) from the Er3+2H11/2 → 4I15/2 and 4S3/2 → 4I15/2 transitions, and 640 and 662 nm (red) from the Er3+4F9/2 → 4I15/2 transition. The optical power curve obtained by plotting the up-conversion luminescence intensity against the laser power shows that the blue emission involves a three-photon process, whilst both the green and red emissions are the results of two-photon processes. Overall white light emission was observed with the crystal prepared with 0.05 mol% Er2O3, 0.5 mol% Tm2O3 and 2.0 mol% Yb2O3, and this crystal is suitable for use in highly efficient white light emission devices.

Microcrack healing in single-crystal cubic zirconia by thermal annealing

Thermally healed Vickers microcracks perpendicular to (001) surface of cubic zirconia single crystals were investigated mainly with scanning transmission electron microscopy. The orientational relationship of areas containing healed microcracks was completely restored to that of the original single crystal, but a row of pores corresponding to the unhealed state remained where the original microcrack was located. Isolated pore formation proceeded from dislocation recovery via heat treatment, which brought the inner surfaces of the microcrack into contact, followed by diffusion bonding via surface diffusion. Once isolated pores were formed, the total pore volume did not significantly change by increasing the healing temperature, although pore sizes increased and the number of pores decreased. Ostwald ripening became pronounced in pore microstructure evolution when pore elimination was dominated by lattice diffusion after complete crystallographic restoration to a single crystal.

White light luminescence in Dy/Tm co-doped yttria stabilized zirconia single crystals

A series of high quality Dy2O3 and Tm2O3 co-doped yttria stabilized zirconia (YSZ) single crystals was synthesized. These crystals have a single cubic structure, and exhibit the characteristic of Dy3+ (blue and yellow emissions) and Tm3+ (blue emission) under excitation with NUV light. Importantly, the hue can be varied between blue and white by modifying the Tm3+/Dy3+ ratio. The photoluminescence and decay curves are consistent with the existence of resonance-type energy transfer from Tm3+ to Dy3+ ions via an electric multipole interaction mechanism. Maximum luminescence intensity is observed in YSZ doped with 0.50 mol% Tm2O3 and 0.75 mol% Dy2O3, and this sample has CIE coordinates (x = 0.33, y = 0.33) in accordance with those for white chromaticity. Thus, the outstanding luminescence properties of these single crystals suggest potential applications in white light emission devices.

Ferromagnetism in defective yttria-stabilized zirconia

Significant research attention has been devoted to identifying and synthesizing new magnetic materials via doping of non-magnetic materials. The material defects offer an approach to stabilize ferromagnetism in non-magnetic materials such as oxygen-deficient HfO2 and oxygen-deficient ZrO2. In this study, we demonstrated room-temperature ferromagnetism via nitrogen ion implantation on yttria-stabilized zirconia (YSZ) single crystals. The results of structural and chemical analyses indicate the formation of a distinct surface layer through the implantation of nitrogen ions and potential oxygen vacancies. The lattice constant in this surface layer increased by 0.6% compared to the bulk value. Nitrogen ions were observed in this region, and their concentration was estimated to be 2.32 atoms per unit cell. In contrast to the lack of magnetic hysteresis in a YSZ single crystal, ferromagnetic hysteresis was observed in the ion-implanted YSZ crystals, owing to defects—nitrogen ions and oxygen vacancies in the surface layer.

Femtosecond Laser-Induced Anisotropic Structure and Nonlinear Optical Response of Yttria-Stabilized Zirconia Single Crystals with Different Planes.

Nonlinear optical properties have been extensively studied due to their promising nonlinear effects and various applications. With ultrashort duration and ultrahigh intensity, a femtosecond laser can fabricate various superior-quality micro-/nanostructures to improve the nonlinearity of materials, which are promising for stable and high-performance nonlinear devices. In this contribution, yttria-stabilized zirconia (YSZ) with fs laser-induced micro-/nanostructures is demonstrated to exhibit unique anisotropic light-material interaction and nonlinear optical response on [100], [110], and [111] planes. Time-resolved reflectivity of YSZ after fs laser excitation is investigated by a pump-probe experiment, which is consistent with simulations through the plasma model combined with a two-temperature model. These results indicate two early ablation mechanisms: Coulomb explosion and melting. Anisotropic crack structures are formed due to thermal stress, which is always ignored in fs laser fabrication and is verified by Raman mapping and analysis of slip systems on different crystal planes. Through the z-scan measurement, the nonlinear absorption (NLA) of crack structures is effectively improved, and a nearly 18 times enhancement of the NLA coefficient is acquired in [100] samples, while a 2 times enhancement in [110] and [111] samples. Such great enhancement of NLA is mainly due to the abundant presence of crack structures and the increase of fs laser-induced oxygen vacancies in [100] YSZ. These results provide a potential way of utilizing fs laser to improve the nonlinearity for the technological development in nonlinear devices.

Phase transformation and incompatibility at grain boundaries in zirconia-based shape memory ceramics: a micromechanics-based simulation study

Zirconia-based shape memory ceramics (SMCs) exhibit anisotropic mechanical response when undergoing elastic deformations as well as during austenite–martensite phase transformation. This behavior results in different types of strain incompatibility at grain boundaries, which we study here using a micromechanical model. A single-crystal model is implemented to provide a full mechanistic three-dimensional description of the anisotropic elastic as well as martensitic transformation stress–strain response, including non-Schmid behavior caused by the significant volume change during martensitic transformation. This model was calibrated to and validated against compression tests of single-crystal zirconia micro-pillars conducted previously, and then used to model bi-crystals. Upon the introduction of a grain boundary, the simulation provides detailed information on the nucleation and evolution of martensite variants and stress distribution at grain boundaries. We identify bi-crystal configurations which result in very large stress concentrations at very low deformations due to elastic incompatibility, as well as others where the elastic incompatibility is relatively low and stress concentrations only occur at large transformation strains. We also show how this approach can be used to explore the misorientation space for quantifying the level of elastic and transformation incompatibility at SMCs grain boundaries.Graphical abstractMicromechanics models provide insights on grain boundary elastic and phase transformation strain incompatibility in shape memory zirconia

Microstructural modifications induced in Si+-implanted yttria-stabilised zirconia: a combined RBS-C, XRD and Raman investigation.

The structural differences in (100)-, (110)- and (111)-oriented cubic yttria-stabilised zirconia (YSZ) single crystals after implantation with 2 MeV Si+ ions at the fluences of 5 × 1015, 1 × 1016 and 5 × 1016 cm-2 were studied using Rutherford backscattering spectrometry in the channelling mode (RBS-C), X-ray diffraction (XRD) and Raman spectroscopy. The RBS-C results show that the damage accumulation in the 〈110〉 direction exhibits a lower level of disorder (<0.3) than the other orientations (<0.6) and it seems that the (110) crystallographic orientation is the most resistant to radiation damage. The experimental results from the RBS measurement were compared with the results from the XRD measurements. The XRD data were analysed using the standard two-beam dynamical X-ray diffraction theory and the pure isotropic strain was deduced from the fit for the fluence of 5 × 1015 cm-2. It was shown that the maximum value of the isotropic strain does not depend on the surface orientation. The increase in signal intensity at ∼689 cm-1 is probably related to an increase in implantation defects such as oxygen vacancies.

Characterization of interactive up-conversion luminescence mechanisms in Tm3+/Ho3+/Yb3+ doped yttria stabilized zirconia single crystals

Yttria stabilized zirconia (YSZ) single crystals doped with Tm2O3, Ho2O3, and Yb2O3 were prepared by the optical floating zone method in order to investigate the effects of varying the Tm3+, Ho3+, Yb3+ contents on the luminescence properties. All samples were shown by powder X-ray diffractometry (XRD) to be in the cubic phase at room temperature with good crystallinity, and the optical bandwidth of about 4.63 eV indicates their suitability for the development of luminescence products. The blue emission peaks from Tm3+ following excitation with a 980 nm (1.33 eV) laser increased with Tm3+ content reached a maximum in the crystal with 0.30 mol% Tm2O3, and then decreased with higher Tm3+ concentrations as a result of quenching caused by electric dipole interactions. The ratio of the integral intensities of the green emission peaks at 2.42 eV (539 nm) and 2.36 eV (552 nm) indicate that the probability of the non-radiative transition from the 5F4 level of Ho3+ to the 5S2 level decreases with increasing Tm3+ concentration. This research also demonstrates that there was competition between Ho3+ and Tm3+ for the transfer of energy from excited Yb3+, and that there was also direct transfer of energy from Ho3+ to Tm3+. Thus, in YSZ doped with a combination of rare earth ions, the luminescence properties are determined by a combination of energy transfer processes between the different types of rare earth ions, as well as those for the individual ions, and thus presents an opportunity for fine tuning emissions from such crystals to produce a new generation of materials with intense luminescence properties.

Phase Transformation and Incompatibility at Grain Boundaries in Zirconia-Based Shape Memory Ceramics: A Micromechanics-Based Simulation Study

Zirconia-based shape memory ceramics (SMCs) exhibit anisotropic mechanical response when undergoing elastic deformations as well as during austenite-martensite phase transformation. This behavior results in different types of strain incompatibility at grain boundaries, which we study here using a micromechanical model. A single-crystal model is developed to provide a full mechanistic three-dimensional description of the anisotropic elastic as well as martensitic transformation stress-strain response, including non-Schmid behavior caused by the significant volume change during martensitic transformation. This model was calibrated to and validated against compression tests of single-crystal zirconia micro-pillars, prior to being used to model bi-crystals. Upon the introduction of a grain boundary, the simulation provides detailed information on the nucleation and evolution of martensite variants and stress distribution at grain boundaries. We identify bicrystal configurations which result in very large stress concentrations at very low deformations due to elastic incompatibility, as well as others where the elastic incompatibility is relatively low and stress concentrations only occur at large transformation strains. We also show how this approach can be used to explore the misorientation space for quantifying the level of elastic and transformation incompatibility at SMCs grain boundaries.

Three-dimensional phase field modeling of fracture in shape memory ceramics

Despite the vast applications of transformable ceramics, such as zirconia-based ceramics, in different areas from biomedical to aerospace, the fundamental knowledge about their mechanical degradation procedure is limited. The interaction of the phase transformation and crack growth is crucial as the essential underlying mechanism in fracture of these transformable ceramics, also known as shape memory ceramics. This study develops a three-dimensional (3D) multiphysics model that couples the variational formulation of brittle crack growth to the Ginzburg-Landau equations of martensitic transformation. We parameterized the model for the 3D single crystal zirconia, which experienced stress- and thermal-induced tetragonal to monoclinic transformation. The developed 3D model considers all 12 monoclinic variants, making it possible to acquire realistic microstructures. Surface uplifting, self-accommodated martensite pairs formation, and transformed zone fragmentation were observed by the model, which agrees with the experimental observations. The influence of the crystal lattice orientation is investigated in this study, which reveals its profound effects on the transformation toughening and crack propagation path.

Crystal growth, structure and optical properties of Pr3+-doped yttria-stabilized zirconia single crystals* *Project supported by the National Natural Science Foundation of China (Grant No. 11975004) and the Key Research and Development Plan Project of Guangxi, China (Grant No. Guike AB18281007).

The development of blue semiconductor light-emitting diodes (LEDs) has produced potential applications for Pr-doped materials that can absorb blue light, especially crystals, and we now report structure and optical properties for high-quality Pr-doped single crystals of yttria-stabilized zirconia (YSZ) grown by the optical floating zone (FZ) method. X-ray diffraction (XRD) and Raman spectroscopy showed that all of the single crystal samples were in the cubic phase, whereas the corresponding ceramic samples contained a mixture of monoclinic and cubic phases. X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) spectroscopy showed that Pr was present as the Pr3+ ion in ceramic rods and single crystals after heating to high temperatures. The absorption and photoluminescence excitation (PLE) spectra of the Pr-doped YSZ crystals measured at room temperature showed strong absorption of blue light, while their photoluminescence (PL) spectra showed five emission peaks at 565 nm, 588 nm, 614 nm, 638 nm, and 716 nm under 450 nm excitation. The optimum luminescence properties were obtained with the crystal prepared using 0.15 mol% Pr6O11, and those with higher concentrations showed evidence of quenching of the luminescence properties. In addition, the color purity of Pr-doped YSZ single crystal reached 98.9% in the orange–red region.

The effect of atomic polarization on the diffusion coefficient of oxygen ions in cubic zirconia

We study single crystal zirconia using molecular dynamics method. We calculate the diffusion coefficient of oxygen ions in the temperature range from the occurrence of diffusion at our calculation parameters to the loss of stability of the crystal. In the potential of interatomic interactions, in addition to conventional terms, we introduce into our model the interaction due to the polarization of atoms. These interactions turned out to be crucial for the correspondence between the calculations and available experimental data.

Optical properties of gadolinia-doped cubic yttria stabilized zirconia single crystals

Cubic zirconia single crystals stabilized with yttria and doped with Gd2O3 (0.10–5.00 mol%) were prepared by the optical floating zone method, and characterized by a combination of X-ray diffraction (XRD), and Raman, electron paramagnetic resonance (EPR), ultraviolet–visible (UV–Vis), photoluminescence excitation (PLE) and photoluminescence (PL) spectroscopic techniques. XRD and Raman spectroscopy showed that the crystal samples were all in the cubic phase, whereas the ceramic sample consisted of a mixture of monoclinic and cubic phases. The absorption spectrum showed four peaks at 245, 273, 308, and 314 nm in the ultraviolet region, and the optical band gap differed between samples with ≤3.00 mol% and those with >3.00 mol% Gd2O3. The emission spectrum showed a weak peak at 308 nm and a strong peak at 314 nm, which are attributed to the 6P5/2 → 8S7/2 and 6P7/2 → 8S7/2 transitions of Gd3+, respectively. The intensities of the peaks in the excitation and emission spectra increased with Gd3+ concentration, reached a maximum at 2.00 mol%, then decreased with higher concentrations. This quenching is considered to be the result of the electric dipole-dipole interactions, and this interpretation is supported by the Gd3+ EPR spectra, which showed progressive broadening with increasing Gd3+ concentration throughout the concentration range investigated.

Semi-organic nonlinear optical material: (((4-sulfonatophenyl)ammonio)oxy)zirconium for dielectric and photonics applications

Abstract This article discusses the growth and characterization of (((4-sulfonatophenyl) ammonio)oxy) zirconium (SAOZ) single crystals. Sulphanilic acid incorporated zirconium oxychloride semi-organic single crystals have been synthesized by slow evaporation technique. From the X-ray studies, lattice parameters a = 7.31 Å, b = 7.51 Å, c = 13.92 Å, volume = 765 Å3 have been found and so the crystal has been identified as orthorhombic with non-centrosymmetric space group P212121. The powder XRD examination demonstrated the quality and high crystalline nature of the grown crystal. The presence of functional groups was confirmed by FT-IR technique. The chemical structure of the compound was established by 1H and 13C NMR spectra. The optical transmittance window and the low cutoff wavelength of SAOZ have been identified by UV-Vis-NIR studies. Photoluminescence studies showed a wide blue light emission. TG and DTA examinations were carried out to characterize the thermal behavior of the grown crystal. The mechanical strength of the grown crystal was analyzed by the Vickers microhardness test. The elemental analysis was done by EDAX. The dielectric response of the crystals was analyzed in the frequency range of 50 Hz to 5 MHz at various temperatures and the outcomes were discussed. The SHG efficiency was estimated in correlation with KDP by employing powder Kurtz method.