Investigation of hydrogen concentration and hardness of ion irradiated organically modified silicate thin films

A study of the effects of ion irradiation of organically modified silicate thin films on the loss of hydrogen and increase in hardness is presented. NaOH catalyzed SiNa_wO_xC_yH_z thin films were synthesized by sol–gel processing from tetraethylorthosilicate (TEOS) and methyltriethoxysilane (MTES) precursors and spin-coated onto Si substrates. After drying at 300 °C, the films were irradiated with 125 keV H⁺ or 250 keV N²⁺ at fluences ranging from 1 × 10¹⁴ to 2.5 × 10¹⁶ ions/cm². Elastic Recoil Detection (ERD) was used to investigate resulting hydrogen concentration as a function of ion fluence and irradiating species. Nanoindentation was used to measure the hardness of the irradiated films. FT-IR spectroscopy was also used to examine resulting changes in chemical bonding. The resulting hydrogen loss and increase in hardness are compared to similarly processed acid catalyzed silicate thin films.     

MeV Si ion beam modification effects on the thermoelectric generator from Er0.1Fe1.9SbGe0.4 thin film

Effective thermoelectric materials and devices have a low thermal conductivity and a high electrical conductivity. The performance of the thermoelectric materials and devices is shown by a dimensionless figure of merit, ZT. The purpose of this study is to improve the figure of merit of the single layer of Er_0.1Fe_1.9SbGe_0.4 thin film used as thermoelectric generators. We have deposited the monolayer of Er_0.1Fe_1.9SbGe_0.4 thin film on silicon and silica substrates with thickness of 302 nm using ion beam assisted deposition (IBAD). Rutherford backscattering spectrometry (RBS) was used to determine the total film thickness and stoichiometry. The MeV Si ion bombardments were performed on single layer of Er_0.1Fe_1.9SbGe_0.4 thin films at five different fluences between 5 × 10¹³?5 × 10¹⁵ ions/cm².The defect and disorder in the lattice caused by ion beam modification and the grain boundaries of these nanoscale clusters increase phonon scattering and increase the chance of annihilation of the phonon. The increase of the electron density of states in the miniband of the quantum dot structure formed by bombardment also increases the Seebeck coefficient and the electrical conductivity. We measured the thermoelectric efficiency of the fabricated device by measuring the cross plane thermal conductivity by the 3rd harmonic (3ω) method, the cross plane Seebeck coefficient, and the electrical conductivity using the Van Der Pauw method before and after the MeV ion bombardments.     

Erosion behavior of soft,amorphous deuterated carbon films by heat treatment in air and under vacuum

The erosion of soft a-C:D films by heat treatment in air and under vacuum is studied by ion-beam analysis. When the films are heated in air above 500 K, the film thickness and the areal densities of C and especially D decrease, and oxygen is incorporated in the films. The initial atomic loss rates of carbon and deuterium from the films are 2.6 × 10¹⁷ C atoms cm⁻² h⁻¹ and 4.8 × 10¹⁷ D atoms cm⁻² h⁻¹ at 550 K. However, after D depletion the films show a resistivity against further erosion due to annealing in air. When the films are heated under vacuum erosion starts at about 600 K and all components including D decrease proportionally to the film thickness. Thermal desorption spectroscopy of the films reveals the evolution of C_xD_y type hydrocarbons. Infrared analysis shows that the incorporated oxygen is chemically bonded to carbon. The thermally-activated decomposition of the soft a-C:D films is compared to that of hard a-C:D films and a reaction scheme is suggested.     

Dose-dependent bonding environment of oxygen implanted in GaN

The bonding environment of oxygen implanted in GaN is studied using Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. The implantation of 70 keV O ions in GaN results in the formation of a 200 nm – thick subsurface layer that is highly defective or amorphous depending on the implantation fluence which ranges from 1 × 10¹⁵ to 1 × 10¹⁷ cm^?2. The NEXAFS spectra are simulated using the FEFF8 code assuming models that account for the formation of point defects (various configurations of O interstitial and O substitutional in N and Ga sites) as well as chemical effects such as the formation of various polymorphs of Ga oxides and oxynitrides. The implantation-induced lattice disorder is modeled by displacing atoms from their equilibrium positions by adding to their Cartesian coordinates random numbers that belong to normal distributions. The simulations reveal that when the fluence is 1 × 10¹⁵ cm^?2, the O implants occupy interstitial sites preferentially in the empty channels aligned parallel to the c-axis in the plane that contains the Ga atoms and/or in the columns that consist of Ga and N atoms along the c-axis. When the fluence is equal to 1 × 10¹⁶ cm^?2 the O ions substitute for N while at 1 × 10¹⁷ cm^?2 they participate in the formation of mixed GaO_xN_y phases.     

Depth-profiling of implanted 28Si by (α,α) and (α,p0) reactions

Silicon nanocrystals enclosed in thin films (Si quantum dots or Si QDs) are regarded to be the cornerstone of future developments in new memory, photovoltaic and optoelectronic products. One way to synthesize these Si QDs is ion implantation in SiO₂ layers followed by thermal annealing post-treatment.Depth-profiling of these implanted Si ions can be performed by reactions induced by α-particles on ²⁸Si. Indeed, for high incident energy, nuclear levels of ³²S and ³¹P can be reached, and cross-sections for (α,α) and (α,p₀) reactions are more intense. This can help to increase the signal for surface silicon, and therefore make distinguishing more easy between implanted Si and Si coming from the SiO₂, even for low fluences.In this work, (α,α) and (α,p₀) reactions are applied to study depth distributions of 70 keV ²⁸Si⁺ ions implanted in 200 nm SiO₂ layers with fluences of 1 × 10¹⁷ and 2 × 10¹⁷ cm^?2. Analysis is performed above E_R = 3864 keV to take advantage of resonances in both (α,α) and (α,p₀) cross-sections. We show how (α,p₀) reactions can complement results provided by resonant backscattering measurements in this complex case.     

Photoluminescence induced by Si implantation into Si3N4 matrix

Up to the present, photoluminescence (PL) was obtained from near stoichiometric or amorphous Si nitride films (SiN_x) after annealing at high temperatures. As a consequence, the existence of PL bands has been reported in the 400–900 nm range. In the present contribution, we report the first PL results obtained by Si implantation into a stoichiometric 380 nm Si₃N₄ film. The Si excess is obtained by a 170 keV Si implantation at different temperatures with a fluence of Φ = 10¹⁷ Si/cm². Further, we have annealed the samples in a temperature range between 350 and 900 °C in order to form the Si precipitates. PL measurements were done using an Ar laser as an excitation source, and a broad PL band basically centered at 910 nm was obtained. We show that the best annealing condition is obtained at T_a = 475 °C for the samples implanted at 200 °C, with a PL yield 20% higher than the obtained at room temperature implantation. Finally, we have varied the implantation fluence and, consequently, the Si nanocrystals size. However, no variation was observed nor in the position neither in the intensity of the PL band. We concluded that the PL emission is due to radiative states at the matrix and the Si nanocrystals interface, as previously suggested in the literature.     

Boron lattice site location in (BGa)As and (BGa)P thin films studied using RBS and NRA with a channeled He+ ion beam

In this study the boron lattice site location in ternary B_xGa_1?xAs and B_xGa_1?xP thin films grown on (0 0 1) GaAs and (0 0 1) GaP, respectively, using low pressure metal-organic vapour-phase epitaxy (MOVPE) with boron concentrations between x = 0.8% and x = 3.2% was investigated with RBS and the ¹⁰B(α,p)¹³C nuclear reaction using a 2.3 MeV He⁺ ion beam. For this purpose, the ion beam was aligned with the [0 0 1], [0 1 1] and [1 1 1] axis and the RBS and proton yield from the nuclear reaction compared with random ion incidence. For comparison, theoretical proton yields which assume boron to be located on substitutional lattice sites only were calculated for each sample/axis combination and compared with the experimental yields. The RBS/channeling measurements show a very good crystal quality of the films with χ_min being in the range of 3–5% for the [0 1 1] axis. The best crystal qualities, i.e. the lowest χ_min values and dechanneling rates, are achieved for low boron concentrations. From NRA/channeling it can be deduced that in the B_xGa_1?xAs films the fraction of interstitial boron is approximately 5% for low boron concentrations of x = 1% and 6–10% for concentrations up to x = 3.2%, whereas the fraction of interstitial boron is less than 3% in the B_xGa_1?xP film studied despite a concentration of x = 2.0%. This indicates that antisite effects of the boron incorporation are more likely in GaAs compared to GaP.     

Early stage of the crystallization in amorphous Fe–Si layers: Formation and growth of metastable α-FeSi2

Crystallization processes of amorphous Fe–Si layers have been investigated using transmission electron microscopy (TEM). Si(1 1 1) substrates were irradiated with 120 keV Fe ions at ?150 °C to a fluence of 1.0 × 10¹⁷ cm². An Fe-rich amorphous layer embedded in an amorphous Si was formed in the as-irradiated sample. Plan-view TEM observations revealed that a part of the amorphous Fe–Si layer crystallized to the metastable α-FeSi₂ after thermal annealing at 350 °C for 8 h. The lattice parameter of c-axis decreased with thermal annealing. It was considered that the change in the lattice parameter originates from the decrease of the Fe occupancy at (0, 0, 1/2) and its equivalent positions in the unit cell of the metastable α-FeSi₂.     

Cerium and neodymium co-precipitation in molten chloride by wet argon sparging

Co-precipitations of cerium (III) and neodymium (III) at 10 wt.% in LiCl–CaCl₂ (30-70 mol%) molten salt at 705 °C have been achieved using an original way of precipitation, wet argon sparging. Several CeCl₃/NdCl₃ ratios have been studied, and the isolated powders were analyzed using different characterization methods including XRD investigations. The lanthanides precipitation yields have been determined around 99.9% using ICP-AES analysis. XRD demonstrated that the precipitates mainly contained mixed oxychloride (Ce_1?xNd_x)OCl and a small amount of the mixed oxide Ce_1?yNd_yO_2?0.5y. Calcination of these precipitates has resulted in the cerium and neodymium mixed oxides. For the precipitation with a Ce/Nd = 50/50 ratio, an hydroxychloride Ln(OH)₂Cl and the oxychloride Ce^IV(Nd_0.7Ce_0.3)^IIIO₃Cl have been identified as unexpected intermediate compounds.     

Effects of BF2+ implantation on the strain-relaxation of pseudomorphic metastable Ge0.06Si0.94 alloy layers

Metastable pseudomorphic Ge_0.06Si_0.94 alloy layers grown by molecular beam epitaxy (MBE) on Si (1 0 0) substrates were implanted at room temperature by 70 keV BF₂⁺ ions with three different doses of 3 × 10¹³, 1 × 10¹⁴, and 2.5 × 10¹⁴ cm⁻². The implanted samples were subsequently annealed at 800°C and 900°C for 30 min in a vacuum tube furnace. Observed by MeV ⁴He channeling spectrometry, the sample implanted at a dose of 2.5 × 10¹⁴ BF₂⁺ cm⁻² is amorphized from surface to a depth of about 90 nm among all as-implanted samples. Crystalline degradation and strain-relaxation of post-annealed Ge_0.06Si_0.94 samples become pronounced as the dose increases. Only the samples implanted at 3 × 10¹³ cm⁻² do not visibly degrade nor relax during anneal at 800°C . In the leakage current measurements, no serious leakage is found in most of the samples except for one which is annealed at 800°C for 30 min after implantation to a dose of 2.5 × 10¹⁴ cm⁻². It is concluded that such a low dose of 3 × 10¹³ BF₂⁺ cm⁻² can be doped by implantation to conserve intrinsic strain of the pseudomorphic GeSi, while for high dose regime to meet the strain-relaxation, annealing at high temperatures over 900°C is necessary to prevent serious leakages from occuring near relaxed GeSi/Si interfaces.     

Soft X-ray fluorescence measurements of irradiated polymer films

Fluorescent soft X-ray carbon Kα emission spectra (XES) have been used to characterize the bonding of carbon atoms in polyimide (PI) and polycarbosilane (PCS) films. The PI films have been irradiated with 40 keV nitrogen or argon ions, at fluences ranging from 1 × 10¹⁴ to 1 × 10¹⁶ cm⁻². The PCS films have been irradiated with 5 × 10¹⁵ carbon ions cm⁻² of 500 keV and/or annealed at 1000°C. We find that the fine structure of the carbon XES of the PI films changes with implanted ion fluence above 1 × 10¹⁴ cm⁻² which we believe is due to the degradation of the PI into amorphous C:N:O. The width of the forbidden band as determined from the high-energy cut-off of the C Kα X-ray excitation decreases with the ion fluence. The bonding configuration of free carbon precipitates embedded in amorphous SiC which are formed in PCS after irradiation with C ions or combined treatments (irradiation and subsequent annealing) is close to either to that in diamond-like films or in silicidated graphite, respectively.     

Effect of implanted Si concentration on the Si nanocrystal size and emitted PL spectrum

Implantation of Si⁺ in excess into SiO₂ followed by annealing produces Si nanocrystals (Si-nc) embedded in the SiO₂ layer, which can emit a strong photoluminescence (PL) signal. Several samples have been characterized by means of ellipsometry and transmission electron microscopy (TEM). For local Si concentrations in excess of ∼2.4 × 10²² Si⁺/cm³, the Si-nc diameter ranges from ∼2 to ∼22 nm in the whole sample, the Si-nc in the middle region of the implanted layer being bigger than those near the surface or the bottom of the layer. The depth distribution of the Si-nc agrees relatively well with the SRIM simulation as well as with the depth distribution of the n and k components of the complex refractive index. For SiO₂ layers thermally grown on a Si wafer, the PL spectrum is modulated by optical interference of the pump laser and of the light emitted by the Si-nc in this layer. The good agreement between the results of the model calculations and experimental measurements indicates that for low and moderate Si concentration in excess (<8 × 10²¹ cm⁻³) the PL light emitters are localized in a layer situated at the same depth as the Si-nc depth distribution. However, for a Si concentration in excess of ∼2.3 × 10²² cm⁻³, the depth distribution of light emitters is narrow and situated mostly in the first half (relative to the surface) of the Si-nc depth distribution. This observation indicates that the recombination of the electron–hole pair at the interfaces could be responsible for the emitted PL spectrum.     

Effect of H+ and O+ implantation on electrical properties of SrBi2Ta2O9 ferroelectric thin films

The effect on the crystalline structure and ferroelectric properties of ion implantation in SrBi₂Ta₂O₉(SBT) ferroelectric thin films has been investigated. 25 keV H⁺, 140 keV O⁺ with doses from 1 × 10¹⁴/cm² to 3 × 10¹⁵/cm² were implanted into the Sol–Gel prepared SBT ferroelectric thin films. The X-ray diffraction patterns of SBT films show that no difference appears in the crystalline structure of as-H⁺-implanted SBT films compared with as-grown films, H⁺ and O⁺ co-implanted SBT films show an obvious degradation of crystalline structure. Ferroelectric properties measurements indicate that both remnant polarization and coercive electric field of H⁺ implanted SBT films decrease with increasing the implantation dose. The disappearance of ferroelectricity was found in the H⁺, O⁺ co-implanted SBT films at room temperature. The great recovery of hydrogen-induced degradation in SBT films was obtained with O⁺ implantation using a heat-target-implantation technique.     

Ohmic contacts on n-type layers formed in GaN/AlGaN/GaN by dual-energy Si ion implantation

Electrical properties of Si-implanted n-type GaN/AlGaN/GaN layers and contact resistances of ohmic electrodes (TiAl) formed on these layers have been examined. Experimental results have clearly shown that ohmic electrodes with a low specific-contact resistance of 1.4 × 10^?7 Ω cm² can be fabricated on the n-type layer having a low sheet resistance of 145 Ω/sq, which has been formed by the dual-energy Si ion implantation (80 keV:1.01 × 10¹⁵/cm² + 30 keV:1.6 × 10¹⁴/cm²) and subsequent annealing at 1200 °C for 2 min using a Si₃N₄ layer as an encapsulant.     

Doping of 6H–SiC pn structures by proton irradiation

The influence of proton irradiation on current–voltage characteristics, N_d − N_a values and parameters of deep centres in 6H–SiC pn structures grown by sublimation epitaxy has been studied. The irradiation was carried out with 8 MeV protons in the range of doses from 10¹⁴ to 10¹⁶ cm⁻². Irradiation with a dose of 3.6 × 10¹⁴ cm⁻² leaves the voltage drop at high forward currents (10 A/cm²) practically unchanged. For higher irradiation dose of 1.8 × 10¹⁵ cm⁻², the forward voltage drop and the degree of compensation in the samples increased ; partial annealing of the radiation defects and partial recovery of the electrical parameters occurred after annealing at T∼400–800 K. Irradiation with a dose of 5.4 × 10¹⁵ cm⁻² resulted in very high resistance in forward biased pn structures which remained high even after heating to 500°C. It is suggested that proton irradiation causes decreasing of the lifetime and formation of an i- or an additional p-layer.     

Ion beam synthesis of SiC by C implantation into SIMOX(1 1 1)

We report the conversion of a 65 nm Si(1 1 1) overlayer of a SIMOX(1 1 1) into 30–45 nm SiC by 40 keV carbon implantation into it. High temperature implantation (600 °C) through a SiO₂ cap, 1250 °C post-implantation annealing under Ar ambient (with 1% of O₂), and etching are the base for the present synthesis. Sequential C implantations (fluence steps of about 5 × 10¹⁶ cm^?2), followed by 1250 °C annealing, has allowed to estimate the minimum C fluence to reach the stoichiometric composition as ～2.3 ×  10¹⁷ cm^?2. Rutherford Backscattering Spectrometry was employed to measure layer composition evolution. A two-sublayers structure is observed in the synthesized SiC, being the superficial one richer in Si. Transmission electron microscopy has shown that a single-step implantation up to the same minimum fluence results in better structural quality. For a much higher C fluence (4 × 10¹⁷ cm^?2), a whole stoichiometric layer is obtained, with reduction of structural quality.     

Nickel,Zn and Cd localisation in seeds of metal hyperaccumulators using μ-PIXE spectroscopy

Metal hyperaccumulators are a rare group of plant species that accumulate exceptionally high concentrations of metals in above ground tissues without showing symptoms of phytotoxicity. Quantitative localisation of the accumulated metals in seed tissues is of considerable interest to help understand the eco-physiology of these unique plant species. We investigated the spatial localisation of metals within seeds of Ni hyperaccumulating Hybanthus floribundus subsp. adpressus, H. floribundus subsp. floribundus and Pimelea leptospermoides and dual-metal (Cd and Zn) hyperaccumulating Thlaspi caerulescens using quantitative micro-proton induced X-ray emission (μ-PIXE) spectroscopy. Intact seeds were hand-sectioned, sandwiched between Formvar films and irradiated using the 3 MeV high energy heavy ion microprobe at ANSTO. Elemental maps of whole H. floribundus subsp. adpressus seeds showed an average Ni concentration of 5.1 × 10³ mg kg^?1 dry weight (DW) with highest Ni concentration in cotyledonary tissues (7.6 × 10³ mg kg^?1 DW), followed by the embryonic axis (4.4 × 10³ mg kg^?1 DW). Nickel concentration in whole H. floribundus subsp. floribundus seeds was 3.5 × 10² mg kg^?1 DW without a clear pattern of Ni localisation. The average Ni concentration in whole P. leptospermoides seeds was 2.6 × 10² mg kg^?1 DW, and Ni was preferentially localised in the embryonic axis (4.3 × 10² mg kg^?1 DW). In T. caerulescens, Cd concentrations were similar in cotyledon (4.5 × 10³ mg kg^?1 DW) and embryonic axis (3.3 × 10³ mg kg^?1 DW) tissues, whereas Zn was highest in cotyledonary tissues (1.5 × 10³ mg kg^?1 DW). In all species, the presence of the accumulated metal within the cotyledonary and embryonic axis tissues indicates that the accumulated metal was able to move apoplastically within the seed.     

Study of Er+ ion-implanted lithium niobate structure after an annealing procedure by RBS and RBS/channelling

Erbium-doped lithium niobate (Er:LiNbO₃) is a prospective photonics component, operating at λ = 1.5 μm, which could be used as an optical amplifier or waveguide laser. We have focused on the structure of Er:LiNbO₃ layers created by 330 keV erbium ion implantation (fluences 1.0 × 10¹⁵, 2.5 × 10¹⁵ and 1.0 × 10¹⁶ cm^?2 1) in the X, Z and two various Y crystallographic cuts of LiNbO₃. Five hours annealing at 350 °C was applied to recrystallize the as-implanted layer and to avoid clustering of Er. Depth distribution of implanted Er has been measured by Rutherford Backscattering Spectroscopy (RBS) using 2 MeV He⁺ ions. Defects distribution and structural changes have been described using the RBS/channelling method. Data obtained made it possible to reveal the relations between the crystallographic orientation of the implanted crystal and the behaviour during the restoration process. The deepest modified layer has been observed in the perpendicular Y cut, which also exhibits the lowest reconstruction after annealing. The shallowest depth of modification and good recovery after annealing were observed in the Z cut of LiNbO₃. Since Er-depth profiles changed significantly in the perpendicular Y cut, we suppose that the crystal structure recovery inhibits Er mobility in the crystalline structure.     

Photoluminescence induced from hot Ge implantation into SiO2

Up to the present, by using the ion implantation technique, photoluminescence (PL) from Ge nanocrystals (Ge NCs) was obtained by room temperature (RT) Ge implantation into a SiO₂ matrix followed by a high temperature anneal. In this way two PL bands were observed, one at 310 nm and the second, with much higher yield at 390 nm. In the present work we have used another experimental approach. We have performed the Si implantation at high temperature (T_i) and then, we have done a higher temperature anneal (T_a) in order to nucleate the Ge NCs. With this aim we have changed T_i between RT and 600 °C. By performing the implantation at T_i = 350 °C we found a PL yield four times higher than the one obtained from the usual RT implantation at the same fluence. Moreover, by changing the implantation fluence between Φ = 0.25 × 10¹⁶ and 2.2 × 10¹⁶ Ge/cm² we observed that Φ = 0.5 × 10¹⁶ Ge/cm² induces a PL yield three times higher as compared to the usual RT implantation fluence. In conclusion, using a hot Ge implantation plus an optimal Ge atomic concentration, we were able to gain more than one order of magnitude in the 390 nm PL yield as compared with previous ion implantation results.     

Heteroepitaxial Er0.49Gd0.51Si1.7 layers formed by channeled ion beam synthesis

Epitaxial ternary silicide Er_0.49Gd_0.51Si_1.7 layers with a good crystalline quality (χ_min of Er and Gd is 3.7%) have been formed by 60 keV Er and Gd ion implantation into Si(1 1 1) substrates to a total dose of 1.0 × 10¹⁷/cm² at 450°C using channeled ion beam synthesis (CIBS). The composition, the structure, the strain and the thermal stability of these layers have been studied using energy dispersive spectroscopy (EDS), Rutherford backscattering (RBS)/channeling and X-ray diffraction (XRD). It is shown that the perpendicular and parallel elastic strains of the Er_0.49Gd_0.51Si_1.7 epilayer are e^⊥=−0.46% ± 0.02% and e⁶=+0.73% ± 0.19%. The layer is stable up to 900°C. Annealing at 950°C results in a phase transformation.