Swift heavy ion irradiation induced modification of BiFeO3 thin films prepared by sol-gel method

We report the preparation of multiferroic BiFeO₃ thin films on ITO coated glass substrates through sol-gel spin coating method followed by thermal annealing and their modification by swift heavy ion (SHI) irradiation. X-ray diffraction and Raman spectroscopy studies revealed amorphous nature of the as deposited films. Rhombohedral crystalline phase of BiFeO₃ evolved on annealing the films at 550°C. Both XRD and Raman studies indicated that SHI irradiation by 200 MeV Au ions result in fragmentation of particles and progressive amorphization with increasing irradiation fluence. The average crystallite size estimated from the XRD line width decreased from 38 nm in pristine sample annealed at 550°C to 29 nm on irradiating these films by 200 MeV Au ions at 1 × 10¹¹ ions cm⁻². Complete amorphization of the rhombohedral BiFeO₃ phase occurs at a fluence of 1 × 10¹² ions.cm⁻². Irradiation by another ion (200 MeV Ag) had the similar effect. For both the ions, the electronic energy loss exceeds the threshold electronic energy loss for creation of amorphized latent tracks in BiFeO₃.     

Effect of oxidation dynamics on the film characteristics of Ce:YIG thin films deposited by pulsed-laser deposition

Thin films with different compositions of Ce-substituted yttrium iron garnet (Ce:YIG (Y₂CeFe₅O₁₂)), Ga-doped Ce:YIG (Ce:Ga:YIG (Y₂CeFe_4.25Ga_0.75O₁₂)), and Gd-doped Ce:YIG (Ce:Gd:YIG (Y_1.6CeGd_0.4Fe₅O₁₂)) were deposited on gadolinium gallium garnet (GGG (Gd₃Ga₅O₁₂)) substrates in O₂ or Ar background gas by pulsed-laser deposition (PLD) technique. Crystalline films were obtained at a lower O₂ gas pressure of 20 mTorr or at higher Ar gas pressures of more than 100 mTorr. In addition, the behavior of YO molecules was visualized by two-dimensional laser-induced fluorescence (2D-LIF), in order to investigate the oxidation dynamics in the ablation plume. The oxidation dynamics and the crystallinity had close correlation.     

Optical spectroscopy study of modifications induced in cerium dioxide by electron and ion irradiations

UV-visible absorption spectroscopy and Raman spectroscopy were used to study damage production in cerium dioxide epitaxial films and polycrystalline sintered samples after irradiation with electrons for three energies to span the threshold displacement energies of cerium and oxygen atoms, and 2.4-MeV Cu ions. Neither amorphization nor specific colour-centre bands were detected. Evolutions of the refractive index were derived from the interference fringes in the optical transmission spectra of epilayers after irradiation. No significant change of the refractive index occurred for the 1.0-MeV electron irradiation, whereas a maximum decrease by 28?±?8% was deduced for the 1.4-MeV and 2.5-MeV energies. These modifications are consistent with ballistic damage on the cerium sublattice for high electron energies producing Ce³⁺ ions. However, no significant change of refractive index was found for the Cu ion irradiation. This likely stems from the high rate of Frenkel pair recombination in the collision cascades induced by more energetic recoils than for the electron irradiations, combined with electronic excitations and hole capture on Ce³⁺ ions. This study reveals modifications of the electronic structure upon irradiation that could take place in other non-amorphizable oxide systems.     

Thermal decay of stable colour centres in Gd3Ga5O12 crystals

This work is devoted to an analysis of thermal decay processes of the stable colour centres (CC) created in gadolinium gallium garnet (GGG) Gd₃Ga₅O₁₂, crystals under irradiation by gamma-quanta (E=1.25 MeV, D=10⁶ Gy). An analysis of the model of CC accumulation under irradiation as well as an isochronous heating model is presented. The decay activation energy (Δ E) for O^? and F centres in GGG crystals is calculated in accordance with this model.     

A comparative study of ion-induced damages in C60 and C70 fullerenes

The stability of fullerenes (C₆₀ and C₇₀) under swift heavy ion irradiation is investigated. C₆₀ and C₇₀ thin films were irradiated with 120 MeV Ag ions at fluences from 1×10¹² to 3×10¹³ ions/cm². The damage cross-section and radius of damaged cylindrical zone were found to be higher for C₆₀ than C₇₀ as evaluated by Raman spectroscopy, which shows that the C₇₀ molecule is more stable under energetic ion impact. The higher damage cross-section of the C₆₀ molecule compared with that of the C₇₀ molecule is explained on the basis of thermal conductivity in the framework of the thermal spike model. The surface morphology of pristine C₆₀ and C₇₀ films is studied by atomic force microscopy. UV-visible absorption studies revealed that band gap for C₆₀ and C₇₀ fullerenes thin films decreases with increasing ion fluence. Resistivity of C₆₀ and C₇₀ thin films decreases with increasing ion fluence but the decrease is faster for C₆₀ than C₇₀, indicating higher damage in C₆₀. Irradiation at a fluence of 3×10¹³ ions/cm² results in complete damage of fullerenes (C₆₀ and C₇₀) into amorphous carbon.     

Recrystallization of hexagonal silicon carbide after gold ion irradiation and thermal annealing

Silicon carbide (SiC) single crystals with the 6H polytype structure were irradiated with 4.0-MeV Au ions at room temperature (RT) for increasing fluences ranging from 1?×?10¹² to 2?×?10¹⁵ cm^?2, corresponding to irradiation doses from ~0.03 to 5.3 displacements per atom (dpa). The damage build-up was studied by micro-Raman spectroscopy that shows a progressive amorphization by the decrease and broadening of 6H-SiC lattice phonon peaks and the related growth of bands assigned to Si–Si and C–C homonuclear bonds. A saturation of the lattice damage fraction deduced from Raman spectra is found for ~0.8?dpa (i.e. ion fluence of 3?×?10¹⁴ cm^?2). This process is accompanied by an increase and saturation of the out-of-plane expansion (also for ~0.8?dpa), deduced from the step height at the sample surface, as measured by phase-shift interferometry. Isochronal thermal annealing experiments were then performed on partially amorphous (from 30 to 90%) and fully amorphous samples for temperatures from 200 °C up to 1500 °C under vacuum. Damage recovery and densification take place at the same annealing stage with an onset temperature of ~200 °C. Almost complete 6H polytype regrowth is found for partially amorphous samples (for doses lower than 0.8 dpa) at 1000 °C, whereas a residual damage and swelling remain for larger doses. In the latter case, these unrelaxed internal stresses give rise to an exfoliation process for higher annealing temperatures.     

Swift heavy ion provoked structural, optical and electrical properties in SnO2 thin films

SnO₂ thin films grown on glass substrates at 300 ^°C by reactive thermal evaporation and annealed at 600 ^°C were irradiated by 120 MeV Ag⁹⁺ ions. Though irradiation is known to induce lattice disorder and suppression of crystallinity, we observe grain growth at a certain fluence of irradiation. X-ray diffraction (XRD) revealed the crystalline nature of the films. The particle size estimated by Scherrer’s formula for the irradiated films was in the range 10–25 nm. The crystallite size increases with increase in fluence up to 1×10¹² ions?cm^?2, whereas after that the size starts decreasing. Atomic force microscope (AFM) results showed the surface modification of nanostructures for films irradiated with fluences of 1×10¹¹ ions?cm^?2 to 1×10¹³ ions?cm^?2. The UV–visible spectrum showed the band gap of the irradiated films in the range of 3.56 eV–3.95 eV. The resistivity decreases with fluence up to 5×10¹² ions?cm^?2 and starts increasing after that. Rutherford Backscattering (RBS) reveals the composition of the films and sputtering of ions due to irradiation at higher fluence.     

Investigation of structural and optical properties of 100 MeV F7+ ion irradiated Ga10Se90-xAlx thin films

Present work focuses on the effect of swift heavy ion (SHI) irradiation of 100 MeV F⁷⁺ ions by varying the fluencies in the range of 1 × 10¹² to 1 × 10¹³ ions/cm² on the morphological, structural and optical properties of polycrystalline thin films of Ga₁₀Se_90-xAl_x (x = 0, 5). Thin films of ~300 nm thickness were deposited on cleaned Al₂O₃ substrates by thermal evaporation technique. X-ray diffraction pattern of investigated thin films shows the crystallite growth occurs in hexagonal phase structure for Ga₁₀Se₉₀ and tetragonal phase structure for Ga₁₀Se₈₅Al₅. The further structural analysis carried out by Raman spectroscopy and scanning electron microscopy verifies the defects or disorder of the investigated material increases after SHI irradiation. The optical parameters absorption coefficient (α), extinction coefficient (K), optical band gap (E_g) and Urbach’s energy (E_U) are determined from optical absorption spectra data measured from spectrophotometry in the wavelength range 200–1100 nm. It was found that the values of absorption coefficient and extinction coefficient increase while the value of optical band gap decreases with the increase in ion fluence. This post irradiation change in the optical parameters was interpreted in terms of bond distribution model.     

Swift heavy ion-induced effects in Ce-doped nickel ferrite nanoparticles

Swift heavy ions of various energies are being used for material modifications. The induced modifications depend on the kind of defects produced during interaction of ions with the target material. In the present work, irradiation of 200 MeV Ag beam-induced effects in NiFe₂O₄ and NiCe_0.04Fe_1.96O₄ nanoparticles are studied at two different fluences, 2×10¹² and 1×10¹³ ions/cm². Nanoparticles of nickel ferrite and Ce-doped nickel ferrite were prepared by chemical route. X-ray diffraction pattern shows peaks corresponding to pure spinel structure in both the systems, NiFe₂O₄ and NiCe_0.04Fe_1.96O₄. The pristine as well as irradiated nanoparticles were characterized by high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, electron paramagnetic resonance spectroscopy (EPR) and vibrating sample magnetometer (VSM). Raman spectra show bands corresponding to spinel structure. After irradiation, the position of the bands does not change significantly for both samples. The widths corresponding to the same band in both the systems show opposite trend with fluence. VSM results show that after irradiation, the magnetization decreases from 40 to 32 A m²/kg for NiFe₂O₄ and from 39 to 31 A m²/kg for NiCe_0.04Fe_1.96O₄. EPR results show that after doping with Ce as well as irradiation, the EPR line width is reduced, making samples important for applications.     

LPE-like growth of YIG ferrimagnetic thin films by pulsed laser ablation with molten droplets

Yttrium iron garnet (YIG) films were grown by pulsed laser ablation (PLA) on (111) Gadolinium Gallium Garnet (GGG) substrates. The second harmonic of YAG laser (532 nm) with a high laser fluence was employed to produce YIG droplets efficiently. It was found that YIG films prepared at RT substrates have a large number of solidified droplets of various sizes. Highly oriented YIG crystals were grown on the (111) GGG substrate heated at 860 °C by PLA using a large number of molten droplets, suggesting an LPE-like growth. This YIG film shows a small ferrimagnetic resonance linewidth of 7.5 Oe. This value is quite small for films prepared by vapor-phase epitaxy techniques.     

Exchange coupling in ultrathin epitaxial yttrium iron garnet films

Magnetic exchange coupling has been observed for ultrathin films of yttrium iron garnet (Y₃Fe₅O₁₂ or YIG). Single-crystalline YIG films were prepared on yttrium aluminium garnet (Y₃Al₅O₁₂ or YAG) substrates by pulsed laser deposition. (111) and (110) oriented substrates were used. Film thicknesses were varied from 180 ? to 4600 ?. Epitaxial growth of YIG on YAG was obtained in spite of the lattice mismatch of 3%. Magnetic hysteresis loops recorded for ultrathin YIG films have a “bee-waist” shape and show a coupling between two different magnetic phases. The first phase is magnetically soft YIG. A composition study by secondary ion mass spectroscopy shows the second phase to be Y₃Fe_5-xAl_xO₁₂ due to the interdiffusion of Fe and Al at the film/substrate interface. This compound is known to be magnetically harder and to have weaker magnetization than YIG. The coupling of the two phases leads to a hysteresis loop displacement at low temperatures. This displacement varies differently with film thickness for two substrate orientations. Assuming an interfacial coupling, the maximal interaction energy is estimated to be about 0.17 erg/cm² at 5 K for (111) oriented sample. Received 3 June 2002 / Received in final form 7 October 2002 Published online 27 January 2003 RID="a" ID="a"Presently at LPM, Université H. Poincaré, BP 239, 54506 Vandœuvre-lès-Nancy e-mail: popova@lpm.u-nancy.fr     

Studies of some physical properties of PrFe0.7Ni0.3O3 thin films after 200 MeV Ag15+ irradiation

PrFe_0.7Ni_0.3O₃ thin films (thickness ~ 200 nm) were prepared by pulsed laser ablation technique on LaAlO₃ substrate. These films were irradiated with 200?MeV Ag¹⁵⁺ ions at various fluencies, ranging from 1 × 10¹¹ to 1 × 10¹² ions/cm². These irradiated thin films were characterized by using X-ray diffraction, dc conductivity, dc magnetization and atomic force microscopy. These films exhibit orthorhombic structure and retain it even after irradiations. The crystallite size (110–137?nm), micro strain (1.48 × 10^?2–1.75 × 10^?2 line^?2?m^?4) and dislocation density (79.7 × 10¹⁴–53.2 × 10¹⁴ line/m²) vary with ion fluencies. An enhancement in resistivity at certain fluence and then a decrease in its value (0.22175–0.21813?Ω?cm) are seen. A drastic change in observed magnetism after ion irradiation is seen. With ion irradiation, an increase in surface roughness, due to the formation of hillocks and other factors, is observed. Destruction of magnetic domains after irradiation can also be visualized with magnetic force microscopy and is in close agreement with magnetization data. The impact on various physical properties in these thin films after irradiation indicates a distortion in the lattice structure and consequently on single-particle band width caused by stress-induced defects.     

Phase transformation in Ni–Mn–Sn ferromagnetic shape memory alloy thin films induced by dense ionization

The effects of 200 MeV Au ions irradiation on the structural and magnetic properties of Ni–Mn–Sn ferromagnetic shape memory alloy (FSMA) thin films have been systematically investigated. In order to understand the role of initial microstructure and phase of the film with respect to high energy irradiation, the two types of Ni–Mn–Sn FSMA films having different phases at room temperature were irradiated, one in martensite phase (Ni_58.9Mn_28.0Sn_13.1) and other in austenite phase (Ni₅₀Mn_35.6Sn_14.4). Transmission electron microscope (TEM) and scanning electron microscope (SEM) images along with the diffraction patterns of X-rays and electrons confirm that martensite phase transforms to austenite phase at a fluence of 6×10¹² ions/cm² and a complete amorphization occurs at a fluence of 3×10¹³ ions/cm², whereas ion irradiation has a minimal effect on the austenitic structure (Ni₅₀Mn_35.6Sn_14.4). Thermo-magnetic measurements also support the above mentioned behaviour of Ni–Mn–Sn FSMA films with increasing fluence of 200 MeV Au ions. The results are explained on the basis of thermal spike model considering the core and halo regions of ion tracks in FSMA materials.     

Optical characterization of thermal-stress induced by spin waves in thin-film ferrimagnetic structures

It is shown that intense spin-dipole waves (SDWs) excited in thin yttrium iron garnet (YIG) films induce an in-plane thermal stress (σ) of 1-2 MPa in a YIG/GGG structure (where GGG is gadolinium gallium garnet). In YIG/GGG with normal magnetization, σ shifts its ferromagnetic resonance frequency by ≈1 MHz, which is comparable to the linewidth of the absorption curve of YIG/GGG resonators. The effect was characterized by an optical technique that detects σ in the GGG substrate. It was also demonstrated that this effect can be used for the optical-microwave spectroscopy of spin waves in thin ferromagnetic films, by using thermal mapping of SDWs in the substrate. We have shown that this opens up the possibility of determining the contribution of the two-particle magneto-elastic interaction to the microwave heating of the sample.     

Optical and structural properties of Pr:GGG crystalline thin film waveguides grown by pulsed-laser deposition

Crystalline Pr³⁺ doped Gd₃Ga₅O₁₂ (Pr:GGG) thin films were grown by pulsed laser deposition (PLD) on yttrium aluminium garnet (YAG) substrates. The chemical composition and structural properties of the films were studied using Rutherford backscattering and X-ray diffraction, respectively. A strong influence of the oxygen pressure on the gallium content in the films as well as in the target surface was found. Films deposited at lower temperature or lower oxygen pressure are amorphous or Ga deficient. Well crystallised and stoichiometric GGG films were fabricated at 800 °C in the 5 to 10 Pa oxygen pressure range. These films present blue, orange and red fluorescence emissions from ³P₀ and ¹D₂ levels of Pr³⁺ ions and fluorescence decay times which are similar to those of the bulk single crystal. Their refractive index of 1.964 close to the bulk crystal value and their waveguiding propagation attenuation of 1.0±0.3 dB/cm measured at 632.8 nm wavelength indicate promising waveguiding properties. PACS 81.15 Fg; 78.55 Hx; 68.55 a     

Induced absorption in yttrium aluminium perovskite crystals irradiated by 12C and 235U ions

The present work is devoted to investigation of optical absorption in pure and neodymium-doped YAlO₃ (YAP) single crystals in the spectral range 0.2–1.1 μm induced by the influence of ¹²C ions irradiation with energy 4.50 MeV/u (MeV per nucleon) and a fluence 2 × 10⁹ cm^?2 or of ²³⁵U ion irradiation with energy 9.35 MeV/u and a fluence 5 × 10¹¹ cm^?2. The induced absorption in the case of ¹²C ions irradiation is caused by recharging of point growth defects and impurities under the radiation influence. After irradiation by ²³⁵U ions with fluence 5 × 10¹¹ cm^?2 the strong absorption rise is probably caused by contribution of the lattice destruction as a result of heavy ion bombardment.     

Study of SHI-induced ion beam mixing in Y3+: YIG employing X-ray diffraction and Mössbauer spectroscopy

The consequences of swift heavy ion (SHI) irradiation (Li^3?+?, 50 MeV, fluence =?5 × 10¹³ ions/cm²) on the structural and microscopic magnetic properties of Y^3?+?-substituted yttrium iron garnet (Y_3?+?x Fe_5???x O₁₂, x = 0.0, 0.2 and 0.4) have been studied at 300 K. It is found that an additional YFeO₃-phase observed along with bcc garnet phase, is completely removed for x = 0.2 composition while its percentage formation considerably reduces for x = 0.4 composition after irradiation. Similar effect has been observed for specimens sintered at 1,500°C. The SHI-induced ion beam mixing has been revealed through X-ray diffraction and Mössbauer spectroscopy.     

On the effect of SHI irradiation on dielectric properties of Y3+xFe5−xO12 (x=0.0–0.6) system

The present work aims to investigate the pre- and post-effect of 50 MeV Li³⁺ ion irradiation at a fluence of 5×10¹³ ions/cm² on the dielectric properties of Y_3+xFe_5?xO₁₂, x=0.0, 0.2, 0.4 and 0.6, garnet system over broad temperature, 300–673 K, and frequency, 100 Hz–13 MHz, ranges. Thermal variation of ac resistivity measurements suggests that the mechanism responsible for conduction in the system is polaron hopping. The observed modifications in dielectric properties after swift heavy ion irradiation are mainly due to the modifications of the metal–insulator contacts due to radiation damage-induced disorder and irradiation-induced point/cluster of defects in the material and also compressive strain generated in the lattice structure. The electric modulus presentation and the complex impedance spectral analysis have been employed to study the relaxation process. The YFeO₃ phase is found to be irradiation hard phase as compared with the garnet phase.     

Mixing of Au in Si induced by secondary and high-order recoil implantation

The mixing of Au in Si induced by secondary and high-order recoil implantation was investigated using 350 keV Ar⁺ and 350 keV Kr⁺ ions to fluences from 1?×?10¹⁶ to 3?×?10¹⁶ ions/cm² at room temperature. The thickness of the Au layer evaporated on Si substrate was ～2400 Å.The ranges of the Ar and Kr ions were chosen to be lower than the thickness of the Au layer in order to avoid the ballistic mixing produced by the primary knock-on atoms. Rutherford backscattering spectrometry (RBS) experiments were carried out to study the effects induced by Ar and Kr irradiation at the interface of Au–Si system. We observed that in the case of the irradiation with Ar⁺ ions, a broadening of the Au–Si interface occurred only at the fluence of 3?×?10¹⁶ Ar⁺/cm² and it is attributed to the surface roughening induced by ion bombardment. In contrast, the RBS analysis of a sample irradiated with 2?×?10¹⁶ Kr⁺/cm² clearly showed, in addition to the broadening effect, the formation of a mixed zone of Au and Si atoms at the interface. The mixing of Au in Si atoms can be explained by the secondary and high-order recoil implantation followed by subsequent collision cascades.     

Effect of Si ion irradiation on polycrystalline CdS thin film grown from novel photochemical deposition technique

CdS thin films have been deposited from aqueous solution by photochemical reactions. The solution contains Cd(CH₃COO)₂ and Na₂S₂O₃, and pH is controlled in an acidic region by adding H₂SO₄. The solution is illuminated with light from a high-pressure mercury-arc lamp. CdS thin films are formed on a glass substrate by the heterogeneous nucleation and the deposited thin films have been subjected to high-energy Si ion irradiations. Si ion irradiation has been performed with an energy of 80 MeV at fluences of 1×10¹¹, 1×10¹², 1×10¹³ and 1×10¹⁴ ions/cm² using tandem pelletron accelerator. The irradiation-induced changes in CdS thin films are studied using XRD, Raman spectroscopy and photoluminescence. Broadening of the PL emission peak were observed with increasing irradiation fluence, which could be attributed to the band tailing effect of the Si ion irradiation. The lattice disorder takes place at high Si ion fluences.