Large Concentration Of Defects Research Articles

Enhanced Mechanical and Electromechanical Properties of Compositionally Complex Zirconia Zr1-x(Gd1/5Pr1/5Nd1/5Sm1/5Y1/5)xO2-δ Ceramics.

Compositionally complex oxides (CCOs) or high-entropy oxides (HEOs) are new multielement oxides with unexplored physical and functional properties. In this work, we report fluorite structure-derived compositionally complex zirconia with composition Zr1-x(Gd1/5Pr1/5Nd1/5Sm1/5Y1/5)xO2-δ (x = 0.1 and 0.2) synthesized in solid-state reaction route and sintered via hot pressing at 1350 °C. We explore the evolution of these oxides' structural, microstructural, mechanical, electrical, and electromechanical properties regarding phase separation and sintering mechanisms. Highly dense ceramics are achieved by bimodal mass diffusion, composing nanometric tetragonal and micrometric cubic grains microstructure. The material exhibits an anomalously large electrostriction response exceeding the M33 value of 10-17 m2/V2 at room temperature and viscoelastic properties of primary creep in nanoindentation measurement under fast loading. These findings are strikingly similar to those reported for doped ceria and bismuth oxide derivates, highlighting the presence of a large concentration of point defects linked to structural distortion and anelastic behavior, which are characteristics of nonclassical ionic electrostrictors.

The Facile Construction of Anatase Titanium Dioxide Single Crystal Sheet-Connected Film with Observable Strong White Photoluminescence

Deposited by a reactive atmospheric pressure non-thermal TiCl4/O2/Ar plasma, anatase TiO2 single crystal sheet-connected film exhibits two large exposed {001} facets and a high concentration of oxygen defects. Strong white photoluminescence centered at 542 nm has been observed with naked eyes, whose internal quantum efficiency is 0.62, and whose intensity is comparable to that of commercial fluorescent lamp interior coatings. Based on the simulation results of a hybrid global–analytical model developed on this atmospheric pressure non-equilibrium plasma system, the mechanism of a self-confined growth of single crystal sheets was proposed. A high concentration of oxygen defects is in situ incorporated into the anatase crystal lattice without damaging its crystallographic orientation. This method opens a new way to construct 3D porous metal-oxide single crystal sheet-connected films with two exposing high energy surfaces and a large concentration of oxygen defects.

Computational prediction of high thermoelectric performance in As2Se3 by engineering out-of-equilibrium defects.

We employed first-principles calculations to investigate the thermoelectric transport properties of the compound As2Se3. Early experiments and calculations have indicated that these properties are controlled by a kind of native defect called antisites. Our calculations using the linearized Boltzmann transport equation within the relaxation time approximation show good agreement with the experiments for defect concentrations of the order of 1019 cm-3. Based on our total energy calculations, we estimated the equilibrium concentration of antisite defects to be about 1014 cm-3. These results suggest that the large concentration of defects in the experiments is due to kinetic and/or off-stoichiometry effects and in principle it could be lowered, yielding relaxation times similar to those found in other chalcogenide compounds. In this case, for relaxation time higher than 10 fs, we obtained high thermoelectric figures of merit of 3 for the p-type material and 2 for the n-type one.

Comprehensive characterization and optoelectronic significance of Ho3+ and Cr3+ Co-doped ZnAl2O4 spinels.

The spinels ZnAl1.99-xHoxCr0.01O4 (with x = 0 and 0.001) were synthesized using a solid-state method, and various techniques were employed for their characterization. X-ray diffraction (XRD) analysis confirmed a cubic spinel structure with the Fd3̄m space group for both spinels. The morphology and homogeneity of the chemical composition were determined using scanning electron microscopy (SEM) and energy dispersive X-ray analysis. Raman and infrared vibrational spectroscopy techniques were also employed for analysis. The optical band gap (Eg) was determined from UV/vis absorption spectra, and the direct transition behavior was confirmed by Tauc's law. The observed large disorder and defect concentration are attributed to the presence of Cr3+ and Ho3+ ions, explaining this behavior. The electron paramagnetic resonance (EPR) measurement presented different types of traps. Room temperature absorption spectra exhibited multiple peaks corresponding to the 3d-3d and 4f-4f transitions of Cr3+ and Ho3+ ions. The results obtained validate the significance of our compounds in optoelectronic device applications.

Black brookite rich in oxygen vacancies as an active photocatalyst for CO2 conversion: Experiments and first-principles calculations

Photocatalytic CO2 conversion is a clean technology to deal with CO2 emissions, and titanium oxide (TiO2) polymorphs are the most investigated photocatalysts for such an application. In this study, black TiO2 brookite is produced by a high-pressure torsion (HPT) method and employed as an active photocatalyst for CO2 conversion. Black brookite with a large concentration of lattice defects (vacancies, dislocations and grain boundaries) showed enhanced light absorbance, narrowed optical bandgap and diminished recombination rate of electrons and holes. The photocatalytic activity of the black oxide for CO2 conversion was higher compared to commercial brookite and benchmark P25 catalyst powders. First-principles calculations suggested that the presence of oxygen vacancies in black brookite is effective not only for reducing optical bandgap but also for providing active sites for the adsorption of CO2 on the surface of TiO2.

Can be metal layered hydroxide an alternative for hydride production by cold H2/Ar plasma treatment?

Layered nickel hydroxide ß-Ni(OH)2 was produced by aqueous precipitation and subsequently exposed to a cold H2/Ar (90/10) plasma, to tentatively reduce nickel hydroxide into nickel hydride by plasma hydrogen ion species interaction/implantation. Due to its open structure nickel hydroxide was expected to be extremely sensitive and reactive toward plasma exposure. Unfortunately, X-ray diffraction and Transmission electron microscopy coupled to hydrogen quantification by thermodesorption evidenced a completely different scenario. Even if nickel nanoparticles were rapidly formed (in 2 h under plasma exposure) the irradiation created atomic displacements and induced significant microstructural alteration, with the generation of large concentrations of defects, including grain boundaries, dislocations, twinnings, and others. As a consequence, hydrogen atoms were irreversibly trapped in those sites and accounts for about 1000 ppm, while for the desired Ni2H or NiH hydrides the expected hydrogen content should be 8513 and 16,881 ppm, respectively.

Surface Capping Layer Prepared from the Bulky Tetradodecylammonium Bromide as an Efficient Perovskite Passivation Layer for High-Performance Perovskite Solar Cells

The power conversion efficiency (PCE) of perovskite solar cells (PSCs) has increased and levels with silicon solar cells; however, their commercialization has not yet been realized because of their poor long-term stability. One of the primary causes of the instability of PSC devices is the large concentration of defects in the polycrystalline perovskite film. Such defects limit the device performance besides triggering hysteresis and device instability. In this study, tetradodecylammonium bromide (TDDAB) was used as a postsurface modifier to suppress the density of defects from the mixed perovskite film (CsFAMA). X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) analyses validated that TDDAB binds to the mixed perovskite through hydrogen bonding. The X-ray diffraction (XRD) and two-dimensional grazing incidence wide-angle X-ray scattering (2D GIWAXS) study uncovered that the TDDAB modification formed a capping layer of (TDDA)2PbI1.66Br2.34 on the surface of the three-dimensional (3D) perovskite. The single charge transport device prepared from the TDDAB-modified perovskite film revealed that both the electron and hole defects were considerably repressed due to the modification. Consequently, the modified device displayed a champion PCE of 21.33%. The TDDAB surface treatment not only enhances the PCE but the bulky cation of the TDDAB also forms a hydrophobic capping surface (water contact angle of 93.39°) and safeguards the underlayer perovskite from moisture. As a result, the modified PSC has exhibited almost no performance loss after 30 days in air (RH ≈ 40%).

Cryogenic Temperature Growth of Sn Thin Films on Ferromagnetic Co(0001)

AbstractTopological electronic materials hold great promise for revolutionizing spintronics, owing to their topological protected, spin‐polarized conduction edge or surface state. One of the key bottlenecks for the practical use of common binary and ternary topological insulator materials is the large defect concentration that leads to a high background carrier concentration. Elemental tin in its α‐phase is a room temperature topological semimetal, which is intrinsically less prone to defect‐related shortcomings. Recently, the growth of ultrathin α‐Sn films on ferromagnetic Co surfaces has been achieved; however, thicker films are needed to reach the 3D topological Dirac semimetallic state. Here, the growth of α‐Sn films on Co at cryogenic temperatures was explored. Very low‐temperature growth holds the promise of suppressing undesired phases, alloying across the interfaces, as well as the formation of Sn pillars or hillocks. Nevertheless, the critical Sn layer thickness of ≈3 atomic layers, above which the film partially transforms into the undesired b‐phase, remains the same as for room‐temperature growth. From ferromagnetic resonance studies, and supported by electron microscopy, it can be concluded that for cryogenic Sn layer growth, the interface between Sn and Co remains sharp and the magnetic properties of the Co layer stay intact.

(Invited) Advancements in Vertical GaN p-n Junction Structures Via p-Type Ion Implantation

Vertical GaN power devices have emerged to become promising candidates for next-generation high power applications due to superior material properties such as high breakdown voltage, low on-resistance, and high mobility compared to devices based on Si and SiC. GaN-based p-n junction switching devices enable higher voltage power with significantly higher efficiencies with added advantages of reduced size and weight systems. A technological limitation of GaN, however, has been the inability to achieve high p-type doping in a planar, vertical device. Here, we will focus on recent developments to achieve high p-type efficiency though ion implantation, novel high temperature annealing schemes, and the importance of defects and morphology in native substrates and epitaxial layersGaN epitaxial layers for subsequent p-type ion implantation can be grown on sapphire substrates but vertical devices are optimal when using GaN homoepitaxial structures. Unlike most other semiconductor substrates, GaN substrates are not grown from the melt. Hydride vapor phase epitaxy or ammonothermal growth are predominantly used to produce substrates and these substrates will experience higher temperatures during subsequent epitaxy and ion implant activation annealing than occurs during substrate formation. In both types of substrates, the threading dislocation distribution can vary by orders of magnitude – these variations correlate well with leakage currents in vertical devices.The activation of the implanted p-type dopants requires high temperature annealing. For most semiconductors, an annealing temperature of ~ 2/3 the melting point leads to a high activation fraction (> 95%) of the implanted species. The implantation process introduces large concentrations of native defects as well as the p-type implant (typically Mg), so it is necessary to remove the defects and for the dopants to locate on substitutional sites (Ga sites for Mg). We demonstrate how the formation of inverted domain defects at temperatures below 1400 °C correlate with Mg-compound formation, whereas annealing temperatures 1400 °C and above do not lead to the formation of such compounds but rather high Mg activation efficiencies.These recent developments, partly through the ARPA-E PNDIODES program as well as international efforts, have brought understanding of the key processing steps and substrate requirements to achieve high activation efficiency p-type doping for planar, vertical device structures in a scalable framework.

Realization of volatile and non-volatile resistive switching with N-TiO2 nanorod arrays based memristive devices through compositional control

It is attractive to manipulate the volatile and non-volatile resistive switching behaviors of memristors to create genuine neuromorphic systems such as artificial neural networks (ANNs) and spiking neural networks (SNNs). To investigate the above behaviors, nitrogen has been introduced into TiO2 nanorod arrays (TiO2 NRAs) by hydrothermal processing. X-ray photoelectron spectroscopy (XPS) analysis shows that both lattice and interstitial nitrogen are incorporated into the TiO2 NRAs. Nitrogen doped TiO2 NRAs (N-TiO2 NRAs) based memristive devices with different contents of lattice nitrogen were investigated systematically. The results show that non-volatile restive switching is achieved at up to a relative lattice nitrogen content of 21%, with volatile switching behavior above this value. The volatile memristive devices show similar spiking and decay features to the Leaky Integrate-and-Fire (LIF) model. The lifetime of the decay process of the volatile devices rang from 0.029 to 1.835 s. The longest lifetime is obtained when the relative content of lattice nitrogen is about 70%. The volatile behavior is related to the large defect concentration, caused by nitrogen doping. The proposed nitrogen engineered memristive devices could pave the way to achieving a physical neuromorphic system.

Multispectral photon-counting for medical imaging and beam characterization — A project review

Central focus of the MPMIB project – funded via the Academy of Finland’s RADDESS 2018–2021 programme – has been research towards a next-generation radiation detection system operating in a photon-counting (PC) multispectral mode: The extraction of energy spectrum per detector pixel data will lead to better efficacy in medical imaging with ionizing radiation. Therefore, it can be an important asset for diagnostic imaging and radiotherapy, enabling better diagnostic outcome with lower radiation dose as well as more versatile characterization of the radiation beam, leading for example to more accurate patient dosimetry.We present our approach of fabricating direct-conversion detectors based on cadmium telluride (CdTe) semiconductor material hybridized with PC mode capable application-specific integrated circuits (ASICs), and will give a review on our achievements, challenges and lessons learned. The CdTe crystals were processed at Micronova, Finland’s national research infrastructure for micro- and nanotechnology, employing techniques such as surface passivation via atomic layer deposition, and flip chip bonding of processed sensors to ASIC. Although CdTe has excellent photon radiation absorption properties, it is a brittle material that can include large concentrations of defects. We will therefore also emphasize our quality assessment of CdTe crystals and processed detectors, and present experimental data obtained with prototype detectors in X-ray and Co-60 beams at a standards laboratory.

Effects of adding GPLs dispersed at different sonication times on the thermal and electrical conductivities of spark plasma sintered silicon carbide

This study has investigated the effects of adding 1 wt % graphene platelets (GPLs) dispersed at different probe-sonication times such as 1, 2, 4 and 6 h on the microstructure, thermal and electrical conductivities of the spark plasma sintered (SPSed) silicon carbide (SiC) matrix. According to scanning electron microscope (SEM), size measurement and Raman analyses, the dispersion of the GPLs increased, the platelet sizes decreased, and the defect concentrations on the structure of GPLs increased as the sonication time increased. While the size reduction was only around 2–5% up to 2 h sonication time, it increased to 25–30% at the 4 and 6 h sonication times. 2 h sonicated GPLs provided the highest contribution among all GPLs, increasing the thermal and electrical conductivity of the SiC matrix by 24 % and ∼106 times, respectively due to having a combination of large lateral size, good dispersion, and low defect concentration characteristics. Anisotropic effect on thermal and electrical conductivities of GPLs-SiC composites decreased with increasing probe-sonication time since the reduction in platelet size of GPLs led to a decrease in their orientation degree within the matrix microstructure.

Implanted gallium impurity detection in silicon by impedance spectroscopy

The results of determining the energy levels of boron-doped silicon implanted with gallium ions by impedance spectroscopy are reported. In the as-implanted sample the boron level remains the same and a second level appears close to the Ga-level reported in literature. In the sample annealed at 1000 °C, two levels are observed neither of which corresponds to the literature values for boron and gallium. It is assumed that in the as-implanted sample this method detects levels of gallium atoms located at a depth where ions penetrate due to the channeling effect, since a large concentration of defects at shallower depths does not allow detection of energy levels due to the Fermi level pinning. Explaining the results for the sample annealed after implantation requires additional research. The main result of this work is to establish the possibility of detecting impurity levels in ion-implanted silicon by impedance spectroscopy even in the absence of subsequent annealing.

(Invited) Developments in Vertical GaN p-n Junction Structures Via p-Type Ion Implantation

Vertical GaN power devices have emerged to become promising candidates for next-generation high power applications due to superior material properties such as high breakdown voltage, low on-resistance, and high mobility compared to devices based on Si and SiC. Silicon is now used for most power switches, but silicon-based devices lose efficiency under high power demands. GaN-based p-n junction switching devices enable higher voltage power with significantly higher efficiencies with added advantages of reduced size and weight systems. A technological limitation of GaN, however, has been the inability to achieve high p-type doping in a planar, vertical device. Here, we will focus on recent developments to achieve high p-type efficiency though ion implantation, novel high temperature annealing schemes, and the importance of defects and morphology in native substrates and epitaxial layers with an emphasis on x-ray scattering and electron microscopy measurements.GaN epitaxial layers for subsequent p-type ion implantation can be grown on sapphire substrates but vertical devices are optimal when using GaN homoepitaxial structures. Unlike most other semiconductor substrates, GaN substrates are not grown from the melt. Hydride vapor phase epitaxy or ammonothermal growth are predominantly used to produce substrates and these substrates will experience higher temperatures during subsequent epitaxy and ion implant activation annealing than occurs during substrate formation. We have developed x-ray topography techniques and combined these with electron microscopy and x-ray diffraction to understand how strain and defects in the substrates and epitaxial layers evolve during subsequent high temperature processing steps.The activation of the implanted p-type dopants requires high temperature annealing. For most semiconductors, an annealing temperature of ~ 2/3 the melting point leads to a high activation fraction (> 95%) of the implanted species. The implantation process introduces large concentrations of native defects as well as the p-type implant (typically Mg), so it is necessary to remove the defects and for the dopants to locate on substitutional sites (Ga sites for Mg). We demonstrate how high resolution x-ray scattering and transmission electron microscopy are used to understand the defect-induced strain recovery process and to mitigate the formation of defects such as dislocation loops, stacking faults, and other non-equilibrium defect structures that cause a degradation in dopant activation efficiency.These recent developments, partly through the ARPA-E PNDIODES program as well as international efforts, have brought understanding of the key processing steps and substrate requirements to achieve high activation efficiency p-type doping for planar, vertical device structures in a scalable framework.

Synthesis and characterization of a hexagonal polymorph of GdAlO3

The structure and basic properties of a hexagonal polymorph of GdAlO3 aluminate (GAH) were studied using a set of experimental methods (XRD, FTIR, Raman spectroscopy, diffuse reflectance spectroscopy, luminescence spectroscopy, magnetic susceptibility, and TEM). The GAH crystallized at 900 °C from an amorphous precursor and decomposed into perovskite GdAlO3 (GAP) at 1000 °C. XRD pattern of polycrystalline GAH could be indexed in P63/mmc space group with unit cell parameters a = 0.3734 nm, c = 1.0535 nm, following literature data. The electron diffraction revealed, however, the presence of well-defined superstructure reflections due to defects ordering. Contrary to a recent report suggesting the presence of CO3 groups in the structure of similar hexagonal YAlO3, we did not observe such groups in the FTIR spectra of GAH. On the other hand, the stoichiometry of GAH differs from ideal GdAlO3, with Al/Gd atomic ratio close to 1.2, similar to reported for hexagonal YAlO3. GAH exhibits paramagnetic behavior over 1.8–300 K temperature range, with the effective Gd magnetic moment μeff = 7.90 μB, close to the theoretical value for free Gd3+ ion. No paramagnetic – antiferromagnetic phase transition at ~4 K, characteristic for perovskite-type GdAlO3, was observed. The reason is probably a less "dense" structure of GAH, with longer Gd-Gd and Gd-O-Gd interatomic distances. Emission spectra of Dy doped (~1 at%) GAH and GAP revealed dramatic differences in Dy3+ emission bands, despite similar mean crystallite size of the host material. An almost structureless 4F9/2→6H13/2 and 4F9/2→6H15/2 emission bands, observed for GAH, indicate, following TEM data, that Dy ions occupy numerous nonequivalent sites due to the presence of a large concentration of crystal defects.

Influence of nickel ion concentration on the free volume defects entrenched in an alkali sulphophosphate glass system by means of positron annihilation characterization technique

In this study we have evaluated the concentration of defect centers like voids, their size (up to nanoscale) and the fraction of free volume space integrated in Li2SO4−MgO−P2O5:NiO glass system as a function of NiO content. Positron annihilation lifetime (PAL) technique with 22Na positron source of radio activity 100 kBq is used for this study. The size, shape and the concentration of entrenched defects in the glass matrix are predicted to influence profoundly the physical properties of the glass. Cavity radius (R) and the entrenched free volume fraction (fv) are found to be the maximal in the sample doped with 0.8 mol% of NiO. This observation suggested that Ni2+ ions predominantly occupied octahedral positions (acted as modifiers along with SO42– ions) and induced large concentration of structural defects. The obtained information is found to be in concurrent with inferences drawn from dielectrics and spectroscopic studies of these glasses reported earlier.

Thickness-Independent Semiconducting-to-Metallic Conversion in Wafer-Scale Two-Dimensional PtSe2 Layers by Plasma-Driven Chalcogen Defect Engineering.

Platinum diselenide (PtSe2) is an emerging class of two-dimensional (2D) transition-metal dichalcogenide (TMD) crystals recently gaining substantial interest, owing to its extraordinary properties absent in conventional 2D TMD layers. Most interestingly, it exhibits a thickness-dependent semiconducting-to-metallic transition, i.e., thick 2D PtSe2 layers, which are intrinsically metallic, become semiconducting with their thickness reduced below a certain point. Realizing both semiconducting and metallic phases within identical 2D PtSe2 layers in a spatially well-controlled manner offers unprecedented opportunities toward atomically thin tailored electronic junctions, unattainable with conventional materials. In this study, beyond this thickness-dependent intrinsic semiconducting-to-metallic transition of 2D PtSe2 layers, we demonstrate that controlled plasma irradiation can "externally" achieve such tunable carrier transports. We grew wafer-scale very thin (a few nm) 2D PtSe2 layers by a chemical vapor deposition (CVD) method and confirmed their intrinsic semiconducting properties. We then irradiated the material with argon (Ar) plasma, which was intended to make it more semiconducting by thickness reduction. Surprisingly, we discovered a reversed transition of semiconducting to metallic, which is opposite to the prediction concerning their intrinsic thickness-dependent carrier transports. Through extensive structural and chemical characterization, we identified that the plasma irradiation introduces a large concentration of near-atomic defects and selenium (Se) vacancies in initially stoichiometric 2D PtSe2 layers. Furthermore, we performed density functional theory (DFT) calculations and clarified that the band-gap energy of such defective 2D PtSe2 layers gradually decreases with increasing defect concentration and dimensions, accompanying a large number of midgap energy states. This corroborative experimental and theoretical study decisively verifies the fundamental mechanism for this externally controlled semiconducting-to-metallic transition in large-area CVD-grown 2D PtSe2 layers, greatly broadening their versatility for futuristic electronics.

High-mobility In and Ga co-doped ZnO nanowires for high-performance transistors and ultraviolet photodetectors.

Due to their unique properties, ZnO nanostructures have received considerable attention for application in electronics and optoelectronics; however, intrinsic ZnO nanomaterials usually suffer from large concentrations of lattice defects, such as oxygen vacancies, which restricts their material performance. Here, for the first time, highly-crystalline In and Ga co-doped ZnO nanowires (NWs) are achieved by ambient-pressure chemical vapor deposition. In contrast to conventional elemental doping, this In and Ga co-doping can not only enhance the carrier concentration, but also suppresses the formation of oxygen vacancies within the host lattice of ZnO NWs. Importantly, this co-doping is also believed to effectively minimize the generation of lattice strain defects due to the optimal ionic sizes of both In and Ga dopants. When configured into field-effect transistors (FETs), these co-doped NWs exhibit an enhanced average electron mobility of 315 cm2 V-1 s-1 and an impressive on/off current ratio of 1.87 × 108, which are already higher than those of other previously reported ZnO NW devices. In addition, these NW devices demonstrate efficient ultraviolet photodetection at under 261 nm irradiation with an improved responsivity of 1.41 × 107 A W-1, an excellent EQE of up to 6.72 × 109 and a fast response time down to 0.32 s. Highly-ordered NW parallel array thin-film transistors and photodetectors are also constructed to demonstrate the promising potential of the NWs for high-performance device applications.

Critical-field slope reduction and upward curvature of the phase-transition lines of thin disordered superconducting [formula omitted] films in strong magnetic fields

We report the effect of disorder on superconducting phase transition of YBa2Cu3O7−x epitaxial thin films in external magnetic fields. The disorder was produced by several successive acts of oxygen ion implantation. Controlling a total accumulated dose of implanted ions nD, we carried out transport measurements in ab-plane for temperatures T below 91 K and external magnetic fields H up to 11 T. Temperature-field dependencies of in-plane resistivity allow us to analyze H−T phase diagrams for primary compound as well as for disordered structure. Considering the upper critical field Hc2 as the magnetic field which corresponds to a local resistivity drop at the onset of superconducting transition, we found out the following results. By gradual increasing of nD, the phase-transition line Hc2(T) suffers an unconventional critical-field slope reduction, while larger defect concentrations usually enhance the upper critical field in the vicinity of Tc0. Besides, for rather large nD, the curvature of Hc2(T) becomes upward for temperatures close to Tc0. Theoretical interpretation of the experimental data is developed in the framework of linearized Ginzburg-Landau theory with an inhomogeneous superconducting coherence length. A simple expression for the critical temperature Tc is obtained: Tc=Tc0(1−h+αh3/2), where h is the dimensionless magnetic field and α is a constant which describes the defects in a specimen. The formula nicely fits our experimental results.

Reversible Tuning of Ca Nanoparticles Embedded in a Superionic CaF2 Matrix

Controlling the size and shape of metallic colloids is crucial for a number of nanotechnological applications ranging from medical diagnosis to electronics. Yet, achieving tunability of morphological changes at the nanoscale is technically difficult and the structural modifications made on nanoparticles generally are irreversible. Here, we present a simple nonchemical method for controlling the size of metallic colloids in a reversible manner. Our strategy consists of applying hydrostatic pressure on a Ca cationic sublattice embedded in the irradiated matrix of CaF2 containing a large concentration of defects. Application of our method to CaF2 along with in situ optical absorption of the Ca plasmon shows that the radii of the Ca nanoparticles can be reduced with an almost constant rate of −1.2 nm/GPa up to a threshold pressure of ∼9.4 GPa. We demonstrate recovery of the original nanoparticles upon decompression of the irradiated matrix. The mechanisms for reversible nanocolloid-size variation are analyzed...