Effect of annealing on the optical absorption of Ni nanoparticles in MgO single crystals

Ni⁺ ion implantation with an energy of 64 keV in MgO single crystals was conducted at room temperature up to a fluence of 1 × 10¹⁷ ion/cm². The as-implanted crystals were annealed isochronally at temperatures up to 900 °C. Optical absorption spectroscopy, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) have been utilized to characterize the changes of optical properties and the microstructure of the annealed samples. XPS results showed that the charge state of implanted Ni was still mainly in metallic Ni⁰ after annealing at 900 °C. TEM analysis revealed metallic Ni nanoparticles with depth-dependant dimensions of 1–10 nm in the annealed sample. Optical absorption spectroscopy indicated that the Ni nanoparticles exhibited a broad surface plasmon resonance absorption band in annealed samples and the band shifted to a longer wavelength with the increasing annealing temperature.     

XPS and optical studies of Xe-implanted and annealed YSZ single crystals

Xe⁺ ion implantation with 200 keV was completed at room temperature up to a fluence of 1 × 10¹⁷ ion/cm² in yttria-stabilized zirconia (YSZ) single crystals. Optical absorption and X-ray photoelectron spectroscopy (XPS) were used to characterize the changes of optical properties and charge state in the as-implanted and annealed crystals. A broad absorption band centered at 522 or 497 nm was observed in the optical absorption spectra of samples implanted with fluences of 1 × 10¹⁶ ion/cm² and 1 × 10¹⁷ ion/cm², respectively. These two absorption bands both disappeared due to recombination of color centers after annealing at 250 °C. XPS measurements showed two Gaussian components of O_1s spectrum assigned to Zr–O and Y–O, respectively, in YSZ single crystals. After ion implantation, these two peaks merged into a single peak with the increasing etching depth. However, this single peak split into two Gaussian components again after annealing at 250 °C. The concentration of Xe decreased drastically after annealing at 900 °C. And the XPS measurement barely detected the Xe. There was no change in the photoluminescence of YSZ single crystals with a fluence of 1 × 10¹⁷ ion/cm² after annealing up to 900 °C.     

Photoluminescence of Au formed in 12CaO · 7Al2O3 single crystal by Au-implantation

Au⁺ ion implantation with fluences from 1 × 10¹⁴ to 3 × 10¹⁶ cm⁻² into 12CaO · 7Al₂O₃ (C12A7) single crystals was carried out at a sample temperature of 600 °C. The implanted sample with the fluence of 1 × 10¹⁵ cm⁻² exhibited photoluminescence (PL) bands peaking at 3.1 and 2.3 eV at 150 K when excited by He–Cd laser (325 nm). This was the first observation of PL from C12A7. These two PL bands are possibly due to intra-ionic transitions of an Au⁻ ion having the electronic configuration of 6s², judged from their similarities to those reported on Au⁻ ions in alkali halides. However, when the concentration of the implanted Au ions exceeded the theoretical maximum value of anions encaged in C12A7 (2.3 × 10²¹ cm⁻³), surface plasmon absorption appeared in the optical absorption spectrum, suggesting Au colloids were formed at such high fluences. These observations indicate that negative gold ions are formed in the cages of C12A7 by the Au⁺ implantation if an appropriate fluence is chosen.     

Structural characterization of amorphous Fe–Si and its recrystallized layers

We have synthesized amorphous Fe–Si thin layers and investigated their microstructure using transmission electron microscopy (TEM). Si single crystals with (1 1 1) orientation were irradiated with 120 keV Fe⁺ ions to a fluence of 4.0 × 10¹⁷ cm⁻² at cryogenic temperature (120 K), followed by thermal annealing at 1073 K for 2 h. A continuous amorphous layer with a bilayered structure was formed on the topmost layer of the Si substrate in the as-implanted specimen: the upper layer was an amorphous Fe–Si, while the lower one was an amorphous Si. After annealing, the amorphous bilayer crystallized into a continuous β-FeSi₂ thin layer.     

Structural evolution in Fe ion implanted Si upon thermal annealing

We have performed high-dose Fe ion implantation into Si and characterized ion-beam-induced microstructures as well as annealing-induced ones using transmission electron microscopy (TEM) and grazing-incidence X-ray diffraction (GIXRD). Single crystals of Si(1 0 0) substrate were irradiated at 623 K with 120 keV Fe⁺ ions to a fluence of 4 × 10¹⁷ cm⁻². The irradiated samples were then annealed in a vacuum furnace at temperatures ranging from 773 K to 1073 K. Cross-sectional TEM observations and GIXRD measurements revealed that a layered structure is formed in the as-implanted specimen with ε-FeSi, β-FeSi₂ and damaged Si, as component layers. A continuous β-FeSi₂ layer was formed on the topmost layer of the Si substrate after thermal annealing.     

Optical and structural behaviour of Mn implanted sapphire

Sapphire single crystals were implanted at room temperature with 180 keV manganese ions to fluences up to 1.8 × 10¹⁷ cm⁻². The samples were annealed at 1000 °C in oxidizing or reducing atmosphere. Surface damage was observed after implantation of low fluences, the amorphous phase being observed after implantation of 5 × 10¹⁶ cm⁻², as seen by Rutherford backscattering spectroscopy under channelling conditions. Thermal treatments in air annealed most of the implantation related defects and promoted the redistribution of the manganese ions, in a mixed oxide phase. X-ray diffraction studies revealed the presence of MnAl₂O₄. On the contrary, similar heat treatments in vacuum led to enhanced out diffusion of Mn while the matrix remained highly damaged. The analysis of laser induced luminescence performed after implantation showed the presence of an intense red emission.     

Heavy-ion-induced luminescence of amorphous SiO2 during nanoparticle formation

Silica glass was implanted with negative 60 keV Cu ions at an ion flux from 5 to 75 μA/cm² up to a fluence of 1 × 10¹⁷ ions/cm² at initial sample temperatures of 300, 573 and 773 K. Spectra of ion-induced photon emission (IIPE) were collected in situ in the range from 250 to 850 nm. Optical absorption spectra of implanted specimens were ex situ measured in the range from 190 to 2500 nm.

IIPE spectra showed a broad band centered around 560 nm (2.2 eV) that was assigned to Cu⁺ solutes. The band appeared at the onset of irradiation, increased in intensity up to a fluence of about 5 × 10¹⁵ ions/cm² and then gradually decreased indicating three stage of the ion beam synthesis of nanoclusters: accumulation of implants, nucleation and growth nanoclusters. The IIPE intensity normalized on the ion flux is independent on the ion flux below 20 μA/cm²at higher fluences. The intensity of the band increased with increasing samples temperature, when optical absorption spectra reveal the increase of Cu nanoparticles size.     

Study of radiation-induced degradation of RPV steels and model alloys by positron annihilation and Mössbauer spectroscopy

The influence of different microstructural processes on the degradation due to radiation embrittlement has studied by positron annihilation and Mössbauer spectroscopy. The materials studied consisted of WWER-440 base (15Kh2MFA) and weld (10KhMFT) RPV steels which were neutron-irradiated at fluence levels of 0.78 × 10²⁴ m⁻², 1.47 × 10²⁴ m⁻² and 2.54 × 10²⁴ m⁻²; WWER-1000 base (15Kh2NMFAA) and weld (12Kh2N2MAA) irradiated at a fluence level 1.12 × 10²⁴ m⁻²; three different model alloys implanted with protons at two dose levels (up to 0.026 dpa), finally the base metal of WWER-1000 (15Kh2NMFAA) was thermally treated with the intention to simulate the P-segregation process. It has been shown possible to correlate the values of parameters obtained by such techniques and data of mechanical testing (ductile-to-brittle transition temperature and upper shelf energy).     

Ion beam enhanced etching of LiNbO3

Single crystals of z- and x-cut LiNbO₃ were irradiated at room temperature and 15 K using He⁺- and Ar⁺-ions with energies of 40 and 350 keV and ion fluences between 5 × 10¹² and 5 × 10¹⁶ cm⁻². The damage formation investigated with Rutherford backscattering spectrometry (RBS) channeling analysis depends on the irradiation temperature as well as the ion species. For instance, He⁺-irradiation of z-cut material at 300 K provokes complete amorphization at 2.0 dpa (displacements per target atom). In contrast, 0.4 dpa is sufficient to amorphize the LiNbO₃ in the case of Ar⁺-irradiation. Irradiation at 15 K reduces the number of displacements per atom necessary for amorphization. To study the etching behavior, 400 nm thick amorphous layers were generated via multiple irradiation with He⁺- and Ar⁺-ions of different energies and fluences. Etching was performed in a 3.6% hydrofluoric (HF) solution at 40 °C. Although the etching rate of the perfect crystal is negligible, that of the amorphized regions amounts to 80 nm min⁻¹. The influence of the ion species, the fluence, the irradiation temperature and subsequent thermal treatment on damage and etching of LiNbO₃ are discussed.     

Radiation effects on MgAl2O4–yttria stabilized ZrO2 composite material irradiated with Ne ions at high temperatures

Spinel (MgAl₂O₄) and yttria stabilized ZrO₂ (YSZ) are candidates for fuel materials for use in nuclear reactors and the optical and insulating materials for fusion reactors. In our previous studies, the amorphization of spinel under 60 keV Xe ion irradiation at RT was observed. On the other hand, amorphization could not be confirmed in YSZ single crystals under the same irradiation conditions. In the present study, the damage evolution process of polycrystalline spinel–YSZ composite materials has been studied by in situ TEM observation during ion irradiation. The irradiation was performed with 30 keV Ne⁺ ions at a flux of 5 × 10¹³ ions cm⁻² s⁻¹ at 923 K and 1473 K, respectively. The observed results revealed a clear difference in morphology of damage depending on irradiation temperature and crystal grains. In the irradiation at 923 K, defect clusters and bubbles were formed homogeneously in YSZ grains. On the other hand, at 1473 K, only bubble formation was observed. The bubbles grew remarkably with increasing ion fluence in both grains. Even though the growth of the bubbles was observed in both grains, the average diameter of grown bubbles in spinel grains was larger than those in YSZ ones. The bubbles tended to form along the grain boundary at both temperatures.     

Structure and optical properties of sapphire implanted with boron at room temperature and 1000 °C

Many previous studies of ion-implanted sapphire have used gas-forming light ions or heavier metallic cations. In this study, boron (10¹⁷ cm⁻², 150 keV) was implanted in c-axis crystals at room temperature, 500 and 1000 °C as part of a continuing study of cascade density and “chemical” effects on the structure of sapphire. Rutherford backscattering-ion channeling (RBS-C) of the RT samples indicated little residual disorder in the Al-sublattice to a depth of 50–75 nm but almost random scattering at the depth of peak damage energy deposition. The transmission electron micrographs contain “black-spot” damage features. The residual disorder is much less at all depths for samples implanted at 1000 °C. The TEM photographs show a coarse “black-spot damage” microstructure. The optical absorption at 205 nm is much greater than for samples implanted with C, N, or Fe under similar conditions.     

Magnetic force microscopy studies on the magnetic ordering in organic materials induced by high-energy proton irradiation

In this study, ferromagnetic microstructures in highly oriented pyrolytic graphite and superparamagnetic spots in polyimide foils were created by 2.25 MeV proton microbeam irradiation and characterized using atomic and magnetic force microscopy. For this purpose, graphite samples were irradiated with cross-like patterns of 15 μm × 15 μm size using ion fluences in the range of (0.003–2.5) × 10¹⁸ cm⁻². The irradiated crosses showed strong magnetic signals and a complex domain structure in the magnetic images depending on the geometrical dimensions of the crosses. Furthermore, polyimide foils were irradiated with microspots and fluences in the range of (0.016–3.1) × 10¹⁹ cm⁻². Magnetic force microscopy shows very strong phase shifts in these irradiated areas.     

Study of 160 MeV Ni ion irradiation effects on electrodeposited polypyrrole films

Conducting polymer polypyrrole thin films doped with LiCF₃SO₃, [CH₃(CH₂)₃]₄NBF₄ and [CH₃(CH₂)₃]₄NPF₆ have been electrodeposited potentiodynamically on ITO coated glass substrate. The polymer films are irradiated with 160 MeV Ni¹²⁺ ions at three different fluences of 5 × 10¹⁰, 5 × 10¹¹ and 3 × 10¹² ions cm⁻². An increase in dc conductivity of polypyrrole films from 100 S/cm to 170 S/cm after irradiation with highest fluence is observed in four-probe measurement. X-ray diffractogram shows increase in the crystallinity of the polypyrrole films upon SHI irradiation, which goes on increasing with the increase in fluence. Absorption intensity increase in the higher wavelength region is observed in the UV–Vis spectra. The SEM studies show that the cauliflower like flaky microstructure of the surface of polypyrrole films turns globular upon SHI irradiation at fluence 5 × 10¹¹ ions cm⁻² and becomes smooth and dense at the highest fluence used. The cyclic voltammetry studies exhibit that the redox properties of the polypyrrole films do not change much on SHI irradiation.     

Large conductivity enhancement in polycrystalline 12CaO · 7Al2O3 thin films induced by extrusion of clathrated O ions by hot Au implantation and ultraviolet light illumination

Large enhancement in electrical conductivity from <10⁻¹⁰ S cm⁻¹ to 4 × 10⁻² S cm⁻¹ was achieved in polycrystalline 12CaO · 7Al₂O₃ (p-C12A7) thin films by hot Au⁺ implantation at 600 °C and subsequent ultraviolet (UV) light illumination. Although the as-implanted films were transparent and insulating, the subsequent UV-light illumination induced persistent electronic conduction and coloration. A good correlation was found between the concentration of photo-induced F⁺-like centers (a cage trapping an electron) and calculated displacements per atom, indicating that the hot Au⁺ implantation extruded free O²⁻ ions from the cages in the p-C12A7 films by kick-out effects and left electrons in the cages. These results suggest that H⁻ ions are formed by the Au⁺ implantation through the decomposition of preexisting OH⁻ ions. Subsequent UV-light illumination produced F⁺-like centers via photoionization of the H⁻ ions, which leads to the electronic conduction and coloration.     

Radiation damage induced by 5 keV Si ion implantation in strained-Si/Si0.8Ge0.2

The damage distributions induced by ultra low energy ion implantation (5 keV Si⁺) in both strained-Si/Si_0.8Ge_0.2 and normal Si are measured using high-resolution RBS/channeling with a depth resolution better than 1 nm. Ion implantation was performed at room temperature over the fluence range from 2 × 10¹³ to 1 × 10¹⁵ ions/cm². Our HRBS results show that the radiation damage induced in the strained Si is slightly larger than that in the normal Si at fluences from 1 × 10¹⁴ to 4 × 10¹⁴ ions/cm² while the amorphous width is almost the same in both strained and normal Si.     

Vacancy defects induced in the track region of 132 MeV C irradiated SiC

Positron annihilation lifetime spectroscopy (PALS) and electron paramagnetic resonance (EPR) have been used in this work to investigate vacancy defects induced in the track region of 132 MeV ¹²C irradiated silicon carbide. Irradiations have been performed at room temperature at a fluence of 2.5 × 10¹⁴ cm⁻² in N-low doped 6H–SiC and 3C–SiC monocrystals. Silicon monovacancies have been detected in both polytypes using EPR. Their charge state and concentration have been determined in the track and cascade region of the C⁺ ions. PALS measurements performed as a function of temperature have shown the presence of V_Si–C divacancies in the track region for both polytypes.     

Effects of 160 MeV Ni ion irradiation on polypyrrole conducting polymer electrode materials for all polymer redox supercapacitor

Electronically conducting polymers are suitable electrode materials for high performance supercapacitors, for their high specific capacitance and high dc conductivity in the charged state. Supercapacitors and batteries are energy storage and conversion systems which satisfies the requirements of high specific power and energy in a complementary way. Ion beam {energy > 1 MeV} irradiation on the polymer is a novel technique to enhance or alter the properties like conductivity, density, chain length and solubility.

Conducting polymer polypyrrole thin films doped with LiClO₄ are synthesized electrochemically on ITO coated glass substrate and are irradiated with 160 MeV Ni¹²⁺ ions at different fluence 5 × 10¹⁰, 5 × 10¹¹ and 3 × 10¹² ions cm⁻². Dc conductivity measurement of the irradiated films showed 50–60% increase in conductivity which is may be due to increase of carrier concentration in the polymer film as observed in UV–Vis spectroscopy and other effects like cross-linking of polymer chain, bond breaking and creation of defects sites. X-ray diffractogram study shows that the degree of crystallinity of polypyrrole increases in SHI irradiation and is proportionate to ion fluence. The capacitance of the irradiated films is lowered but the capacitance of the supercapacitors with irradiated films showed enhanced stability compared to the devices with unirradiated films while characterized for cycle life up to 10,000 cycles.     

Helium retention of vanadium alloy after energetic helium ion irradiation

Helium irradiation experiments of V–4Ti alloy were conducted in an ECR ion irradiation apparatus by using helium ions with energy of 5 keV. The ion fluence was in the range from 1 × 10¹⁷ He/cm² to 8 × 10¹⁷ He/cm². After the helium ion irradiation, the helium retention was examined by using a technique of thermal desorption spectroscopy (TDS). After the irradiation, the blisters with a size of about 0.1 μm were observed at the surface, and the blister density increased with the ion fluence. Two desorption peaks were observed at approximately 500 and 1200 K in the thermal desorption spectrum. When the ion fluence was low, the retained helium desorbed mainly at the higher temperature regime. As increase of the ion fluence, the desorption at the lower temperature peak increased and the retained amount of helium saturated. The saturated amount was approximately 2.5 × 10¹⁷ He/cm². This value was comparable with those of the other plasma facing materials such as graphite.     

Formation processes of nickel oxide nanoparticles in SiO2 by metal-ion implantation combined with thermal oxidation

Formation processes of nickel oxide (NiO) nanoparticles (NPs) in silica glass (SiO₂) by implantation of 60 keV Ni⁻ ions combined with thermal oxidation are studied using cross-sectional transmission electron microscopy (XTEM) and Rutherford backscattering spectrometry. In as-implanted state, Ni metallic NPs form within the surface layer of 80 nm thick. The mean depth z and the standard deviation (Δz)^21/2 of Ni atom distribution determined by XTEM were 43 and 15 nm, respectively. After the oxidation at 800 °C for 1 h, z and (Δz)^21/2 became 47 nm and 20 nm, respectively, i.e. the distribution was almost the same except a small diffusional shift to the deeper region. Mean volume of Ni- and NiO-NPs after heat treatments at 800 °C were 27 and 43 nm³, respectively. The larger mean volume of NiO-NPs is explained from the fact that NiO-NPs include both Ni and O atoms, i.e. approximately 2N atoms, while Ni-NPs include Ni atoms only, i.e. N atoms. Both the Ni- and NiO-NPs include 2.4 × 10³ Ni atoms per NP in average. These results indicate that NiO-NPs are formed by oxidation of Ni-NPs without pronounced redistribution of Ni atoms.     

Optical nonlinearity of Cu:SrTiO3 composite fabricated by negative ion implantation

Optical nonlinearity and dispersion were studied for Cu nanoparticle composite. Negative Cu⁻ ions with 60 keV were applied for implanting into SrTiO₃ at a flux of 10 μA/cm² up to a total fluence of 1 × 10¹⁷ ions/cm². The steady-state optical spectrum of Cu-implanted SrTiO₃ showed a surface plasmon resonance resulting from the formation of nanoparticles. Transient transmission and reflection were measured by the pump–probe method with a femtosecond laser system. Optical nonlinearity originated from Cu:SrTiO₃ nanoparticle composite and from SrTiO₃ matrix overlap, in measured transient spectra. The nonlinear component of Cu:SrTiO₃ composite was extracted from the transient spectra with the difference of time response. Nonlinear dielectric coefficient and dispersion around the surface plasmon resonance were derived from extracted transient spectra. The dispersion was compared with a local electric field factor.