The effects of ion irradiation in the ABO4-type compounds were compared by performing experiments on four materials that include the most common crystal structures (monazite vs. zircon) and chemical compositions (phosphates vs. silicates) for these phases. Pure synthetic single crystals of ZrSiO4, monoclinic ThSiO4, LaPO4 and ScPO4 were irradiated using 800 keV Kr+ ions. Radiation damage accumulation was monitored as a function of temperature in situ in a transmission electron microscope. The activation energies for recrystallization during irradiation were calculated to be 3.1–3.3 eV for the orthosilicates but only 1.0–1.5 eV for the isostructural orthophosphates. For the ion-beam-irradiated samples, the critical temperature, above which the recrystallization processes are faster than damage accumulation and amorphization cannot be induced, is >700°C for ZrSiO4 but it is only 35°C for LaPO4. At temperatures above 600°C, zircon decomposed during irradiation into its component oxides (i.e. crystalline ZrO2 plus amorphous SiO2). The data are evaluated with respect to the proposed use of the orthophosphates and orthosilicates as host materials for the stabilization and disposal of high-level nuclear waste. The results show that zircon with 10 wt.% Pu would have to be maintained at temperatures in excess of 300°C in order to prevent it from becoming completely amorphous. In contrast, a similar analysis for the orthophosphates implies that monazite-based waste forms would not become amorphous or undergo a phase decomposition.

Scintillation properties are often studied by photo-luminescence (PL) andscintillation measurements. In this work, we combine X-ray-induced luminescence(XRIL) spectroscopy [Review of Scientific Instruments 83, 103112 (2012)] with PLand standard scintillation measurements to give insight into the scintillationproperties of un-doped ZnO single crystals. XRIL revealed that ZnO luminescenceproportionally increases with X-ray power and exhibits excellent linearity -indicating the possibility of developing radiation detectors with good energyresolution. By coupling ZnO crystals to fast photomultiplier tubes andmonitoring the anode signal, rise times as fast as 0.9 ns were measured.

Extended abstract of a paper presented at Microscopy and Microanalysis 2006 in Chicago, Illinois, USA, July 30 – August 3, 2006

Extended abstract of a paper presented at Microscopy and Microanalysis 2006 in Chicago, Illinois, USA, July 30 – August 3, 2005

Extended abstract of a paper presented at Microscopy and Microanalysis 2005 in Honolulu, Hawaii, USA, July 31--August 4, 2005

The dielectric response in artificially layered 1x1 KTaO3/KNbO3 perovskite superlattice structures is reported. While KTaO3 and KNbO3 are ferroelectric or paraelectric, respectively, superlattices appear antiferroelectric based on an increase in dielectric constant with applied dc bias. This “positive tunability” in dielectric response occurs at the same temperature region where a structural phase transition is observed. This dielectric behavior is inconsistent with the nonlinear response for either paraelectric or ferroelectric materials. However, an increase in the dielectric constant with applied electric field is consistent with antiferroelectric behavior. The antiferroelectric ordering correlates with cation modulation imposed by the superlattice.

Titanate pyrochlores are candidate host materials for the disposition of plutonium from dismantled nuclear weapons. These pyrochlores also have potential applications as solid electrolytes and oxygen gas sensors. The radiation-induced microstructural evolution of titanate pyrochlores has been characterized using x-ray photoelectron spectroscopy (XPS). XPS analysis of the Ti 2p and O 1s binding energy shifts of REE2Ti2O7 (REE: rare earth) surface layers before and after irradiation shows that the primary manifestations of amorphization are distortions or changes in the coordination number of the titanium polyhedra. A model based on glass network structure was developed, and predictions of the relative susceptibilities for amorphization of the titanate pyrochlores are obtained that are consistent with the experimental results.

The enthalpies of formation for the compounds (RE3+)PO4, (where RE = Sc, Y, La–Nd, Sm–Lu) were determined by oxide-melt solution calorimetry. Calorimetric measurements were performed in a Calvet-type twin microcalorimeter in sodium molybdate (3Na2O · 4MoO3) and lead borate (2PbO · 2B2O3) solvents at 975 K. The experiments were carried out using both powdered single crystals grown by a flux technique and powders synthesized by precipitation. Formation enthalpies were derived from the drop-solution enthalpies for (RE)PO4, RE oxides, and P2O5. Enthalpies of formation for the (RE)PO4 compounds with respect to the oxides at 298 K become more negative with increasing RE3+ ionic radius; i.e., in going from ScPO4 (−209.8 ± 1.0 kJ/mol), to LuPO4 (−263.9 ± 1.9 kJ/mol), to LaPO4 (−321.4 ± 1.6 kJ/mol). From structural considerations, a similar trend is expected for the isostructural RE vanadates and arsenates, as well as for the tetravalent actinide orthosilicates.

Nanophase precipitates of CdS formed in amorphous SiO2 by ion implantation and thermal processing have recently been found to exhibit a “hollow-particle” or “shell-like” microstructure. The present investigations show that this hollow-particle microstructure can be reproduced for a variety of materials other than CdS, and these results provide new insight into the mechanisms responsible for the formation of hollow precipitates embedded in solid hosts. Various elemental metal nanocrystals were formed in (100)-oriented crystalline Si hosts by ion implantation coupled with thermal treatments in which the annealing parameters were varied to investigate the “hollow-particle” formation conditions. The results indicate that depending on the melting points and vapor pressure of the precipitates or on the initial state of the host material, several processes acting either independently or in concert can lead to hollow precipitate formation. First, the implantation of materials having a high vapor pressure, either at the implant temperature or when heated during annealing, can lead to the formation of cavities in the crystalline host. Hollow precipitates can then form by a partial filling and coating of the cavity walls by the implanted species in a diffusion-based gettering/ripening process. Internal void formation can also occur or be enhanced by volume contraction during cooling if the particle solidifies from a liquid phase.

Oriented ferromagnetic FePt nanoparticles with the face-centered tetragonal L10 structure were produced in Al2O3 single crystal hosts by ion implantation and annealing. Both the orientation and particle-size of the FePt particles depend strongly on the implantation conditions. The magnetic coercivities are extremely high, reaching values in excess of 20 kOe for Pt concentrations of ∼45% in the FePt alloy. Ferromagnetic FePt nanoparticles were also produced in amorphous SiO2 by ion implantation and annealing.

Ion implantation has become a versatile and powerful technique for synthesizing nanometer-scale clusters and crystals embedded in the near-surface region of a variety of hosts. The resulting nanocomposite materials often show unique optical, magnetic, and electronic properties. Here we review some of the principal features of this nanophase materials synthesis technique and discuss the outstanding experimental difficulties that currently hamper the development of devices based on the many unique properties of these nanocomposite materials. Possible solutions to these problems and future research directions are discussed.

Irradiation-induced amorphization of Cd2Nb2O7 pyrochlore was investigated by means of in-situ temperature-dependent ion-irradiation experiments in a transmission electron microscope, combined with ex-situ ion-implantation (at ambient temperature) and RBS/channeling analysis. The in-situ experiments were performed using Ne or Xe ions with energies of 280 and 1200 keV, respectively. For the bulk implantation experiments, the incident ion energies were 70 keV (Ne+) and 320 keV (Xe2+). The critical amorphization temperature for Cd2Nb2O7 is ∼480 K (280 keV Ne+) or ∼620 K (1200 keV Xe2+). The dose for in-situ amorphization at room temperature is 0.22 dpa for Xe2+, but is 0.65 dpa for Ne+ irradiation. Both types of experiments suggest a cascade overlap mechanism of amorphization. The results were analyzed in light of available models for the crystalline-to-amorphous transformation and were compared to previous ionirradiation experiments on other pyrochlore compositions.

Ion implantation has become a versatile and powerful technique for synthesizing nanometer-scale clusters and crystals embedded in the near-surface region of a variety of hosts. The resulting nanocomposite materials often show unique optical, magnetic, and electronic properties. Here we review some of the principal features of this nanophase materials synthesis technique and discuss the outstanding experimental difficulties that currently hamper the development of devices based on the many unique properties of these nanocomposite materials. Possible solutions to these problems and future research directions are discussed.

Ion implantation was used to form compound semiconductor nanocrystal precipitates of ZnS, CdS, and PbS in both glass and crystalline matrices. The precipitate microstructures and size distributions were investigated by cross-sectional transmission electron microscopy techniques. Several unusual features were observed, including strongly depth-dependent size variations of the ZnS precipitates and central void features in the CdS nanocrystals. The morphology and crystal structure of the nanocrystal precipitates could be controlled by selection of the host material. The size distribution and microstructural complexity were significantly reduced by implanting a low concentration of ions into a noncrystalline host, and by using multi-energy implants to give a flat concentration profile of the implanted elements.

Crystallographically coherent precipitates of vanadium dioxide (VO2) have been formed in the near-surface region of single crystals of sapphire (Al2O3) using a combination of ion implantation and thermal treatments. As in the case of either bulk VO2 single crystals or thin films of VO2, the thermally induced semiconductor-to-metal phase transition of the embedded VO2 precipitates is accompanied by a large hysteretic change in the infrared optical transmission. The VO2 precipitate transition temperature (Tc = 72 to 85 °C) is higher than that of bulk VO2 (Tc = 68 °C) and is sensitive to the implantation conditions. The present results show that the damage resulting from the coimplantation of vanadium and oxygen into an Al2O3 host lattice dictates the final microstructure of the VO2 precipitates and, consequently, affects the transition temperature, as well as the optical quality of the VO2/Al2O3 surface-nanocomposite precipitate system.

Ion-implantation and thermal-processing methods have been used to form nanophase magnetic precipitates of metallic cobalt that are embedded in the near-surface region of single crystals of Al2O3. The Co precipitates are isolated, single-crystal particles that are crystallographically oriented with respect to the host Al2O3 lattice. Embedded nanophase Co precipitates were formed by the implantation of Co+ at an energy of 140 keV and a dose of 8 × 1016 ions/cm2 followed by annealing in a reducing atmosphere. The implanted/annealed Co depth profile, particle size distributions and shapes, and the orientational relationship between the nanophase precipitates and the host crystal lattice were determined using RBS/channeling, transmission electron microscopy, and x-ray diffraction. Magneto-optical effects arising from Co precipitates formed in the near-surface region of Al2O3 were observed and characterized using magnetic circular dichroism. Magnetic properties of the Co-particle/host nanocomposites were investigated in the temperature range of 77 to 295 K in applied fields of up to 10 kG using a superconducting quantum interference device (SQUID) magnetometer. Implantation of the Co particles by Pt or Xe ions produced a large anisotropic increase in their coercivity. Accordingly, these magnetic nanoparticle systems may be of interest for magnetic data storage applications. Details of the magnetic properties of the Co/Al2O3 nanocomposites including their retentivity, coercivity, saturation field, and magnetic anisotropy are presented.

Several groups have irradiated single crystals of synthetic and natural zircon (ZrSiO4) with a wide range of ions (from He to Bi) over a wide range of temperatures. The results of these studies show that amorphization in zircon is controlled by a variety of parameters and is a more complex process than previously thought. The critical dose for amorphization increases with temperature, similar to other materials. However, the critical displacement dose (in dpa) for amorphization is significantly higher at lower temperatures (below 500 K) for very heavy ions, such as Pb and Bi. This unusual dependence on the damage energy density has not been observed previously in other materials. Possible explanations for this behavior in terms of amorphization mechanisms are discussed. In addition, there is a significant difference in the temperature dependence of the critical dose in synthetic and natural zircons, which suggests that the impurities in natural zircons may affect the kinetics of recovery processes.

Synthetic LaPO4, ScPO4, and crystalline natural zircon (ZrSiO4) from Mud Tanks, Australia were irradiated by 1.5 MeV Kr+ ions until complete amorphization occurred as indicated by the absence of electron-diffraction maxima. The resulting amorphous materials were subsequently irradiated by an 80 to 300 keV electron beam in the transmission electron microscope at temperatures between 130 and 800 K, and the resulting microstructural changes were monitored in situ. Thermal anneals in the range of 500 to 600 K were also conducted to compare the thermally induced microstructural development with that produced by the electron irradiations. Amorphous LaPO4 and ScPO4 annealed to form a randomly oriented polycrystalline assemblage of the same composition as the original material, but zircon recrystallized to ZrO2 (zirconia) + amorphous SiO2 for all beam energies and temperatures investigated. The rate of crystallization increased in the order: zircon, ScPO4, LaPO4. Submicrometer tracks of crystallites having a width equal to that of the electron beam could be “drawn” on the amorphous substrate. In contrast, thermal annealing resulted in epitaxial recrystallization from the thick edges of the TEM samples. Electron-irradiation-induced nucleation and growth in these materials can be explained by a combination of radiation-enhanced diffusion as a result of ionization processes and a strong thermodynamic driving force for crystallization. The structure of the amorphous orthophosphates may be less rigid than that of their silicate analogues because of the lower coordination across the PO4 tetrahedron, and thus a lower energy is required for reorientation and recrystallization. The more highly constrained monazite structure-type recovers at a lower electron dose than the zircon structure-type, consistent with recent models used to predict the crystalline-to-amorphous transition as a result of ion irradiation.

We have conducted a series of experiments using laser spectroscopy and analytic electron microscopy (AEM) to study the microscopic effects of radiation damage in single crystals of LuPO4 doped with 244Cm3+ ions. The crystals (body-centered tetragonal, zircon-type structure) were grown in 1980 using a flux method with an initial 244Cm(t1/2 =18.1 y) concentration of ∼1% by weight. The dimensions of the single crystals of Cm3+:LuPO4 are about 0.5×1.0×4.0 mm3. After 17 years, the crystals are no longer transparent. Dark brown to gray straps along the crystal c-axis are observable under an optical microscope. Macroscopic fractures are not obvious on the natural surfaces of the a- and b-planes. However, due to alpha-particle emission of 244Cm, significant microscopic structural damage, including microscopic cavities, has accumulated in this end member of the xenotime minerals

Several perovskite-structure oxide compounds, including CaTiO3, SrTiO3, BaTiO3, KNbO3, and KTaO3 were irradiated by 800 keV Kr+ ions in order to investigate and compare their response to heavy-ion irradiation. The critical amorphization temperature Tc, above which amorphization could not be induced, was found to increase in the order SrTiO3 → CaTiO3 → BaTiO3 → KNbO3 → KTaO3. No single physical parameter explains the observed sequence, although Tc correlates well with the melting temperatures. The well-known solid state phase transformations in these materials did not have a significant effect on the dose required for amorphization. Domain boundaries were observed in the pristine samples; however, after only a low dose, the boundaries became poorly defined and, with increasing dose, eventually disappeared. Dislocation loops were observed to aggregate at the domain boundaries.