Er+ implantation in SnO2:SiO2 layers: Structure changes and light emission

Structure changes and light emission behavior in Er⁺ implanted SnO₂:SiO₂ layers are studied, using transmission electron microscopy (TEM), Rutherford backscattering (RBS) and cathodoluminescence (CL). SnO₂:SiO₂ layers of different composition deposited with RF magnetron sputtering on Si wafers were implanted with 200 keV Er⁺ to a fluence of 3 × 10¹⁵ cm^?2 at room temperature. The implanted structures were then annealed at 600–1000 °C for 30 min, resulting in the formation of crystalline SnO₂ nanoclusters. Cross-section TEM revealed a strong reduction of the SnO₂ crystallite size down to several nanometers in the implanted area of the SnO₂:SiO₂ layer as compared to the undoped layer. In addition, a very narrow layer of SnO₂ nanocrystals appears at the SiO₂/Si interface. Several narrow CL emission peaks and wide bands were found which could be related to the decay of SnO₂ free excitons, to oxygen deficiency centers in SiO₂ and to transitions between the energy levels in the Er ions, apparently located at nanoclusters. The mechanisms of nanostructuring as well as the emission process are discussed.     

Nanometer-thick SGOI structures produced by Ge+ ion implantation of SiO2 films and subsequent hydrogen transfer of Si layers

Nanometer-thick silicon-germanium-on-insulator (SGOI) structures have been produced by the implantation of Ge⁺ ions into thermally grown SiO₂ layer and subsequent hydrogen transfer of silicon film on the Ge⁺ ion implanted substrate. The intermediate nanometer-thick Ge layer has been formed as a result of the germanium atom segregation at the Si/SiO₂ bonding interface during annealing at temperatures 800–1100 ^оС. From a thermodynamic analysis of Si/Ge/SiO₂ system, it has been suggested that the growth of the epitaxial Ge layer is provided by the formation of a molten layer at the Si/SiO₂ interface due to the Ge accumulation. The effect of germanium on the hole mobility in modulation-doped heterostructures grown over the 3–20 nm thick SGOI layers was studied. An increase in the Hall hole mobility in SGOI-based structures by a factor of 3–5 was obtained in comparison with that in respective Ge-free SOI structures.     

Effects of MeV Si ions bombardment on the thermoelectric generator from SiO2/SiO2 + Cu and SiO2/SiO2 + Au nanolayered multilayer films

The defects and disorder in the thin films caused by MeV ions bombardment and the grain boundaries of these nanoscale clusters increase phonon scattering and increase the chance of an inelastic interaction and phonon annihilation. We prepared the thermoelectric generator devices from 100 alternating layers of SiO₂/SiO₂ + Cu multi-nano layered superlattice films at the total thickness of 382 nm and 50 alternating layers of SiO₂/SiO₂ + Au multi-nano layered superlattice films at the total thickness of 147 nm using the physical vapor deposition (PVD). Rutherford Backscattering Spectrometry (RBS) and RUMP simulation have been used to determine the stoichiometry of the elements of SiO₂, Cu and Au in the multilayer films and the thickness of the grown multi-layer films. The 5 MeV Si ions bombardments have been performed using the AAMU-Center for Irradiation of Materials (CIM) Pelletron ion beam accelerator to make quantum (nano) dots and/or quantum (quantum) clusters in the multilayered superlattice thin films to decrease the cross plane thermal conductivity, increase the cross plane Seebeck coefficient and cross plane electrical conductivity. To characterize the thermoelectric generator devices before and after Si ion bombardments we have measured Seebeck coefficient, cross-plane electrical conductivity, and thermal conductivity in the cross-plane geometry for different fluences.     

SHI induced re-crystallization of Ge implanted SiO2 films

Ge nanocrystals embedded in SiO₂ matrix have been synthesized by swift heavy ion irradiation of Ge implanted SiO₂ films. In the present study, 400 keV Ge⁺ ions were implanted into SiO₂ films at dose of 3 × 10¹⁶ ions/cm² at room temperature. The as-implanted samples were irradiated with 150 MeV Ag¹²⁺ ions with various fluences. Similarly 400 keV Ge⁺ ions implanted into Silicon substrate at higher fluence at 573 K have been irradiated with 100 MeV Au⁸⁺ ions at room temperature (RT). These samples were subsequently characterized by XRD and Raman to understand the re-crystallization behavior. The XRD results confirm the presence of Ge crystallites in the irradiated samples. Rutherford backscattering spectrometry (RBS) was used to quantify the concentration of Ge in the SiO₂ matrix. Variation in the nanocrystal size as a function of ion fluence is presented. The basic mechanism of ion beam induced re-crystallization has been discussed.     

Homogeneously size distributed Ge nanoclusters embedded in SiO2 layers produced by ion beam synthesis

500 nm SiO₂ layers were implanted with 450 keV (F=3 × 10¹⁶ at./cm²) and 230 keV (F=1.8 × 10¹⁶ at./cm²) Ge ions at room temperature to obtain an almost constant Ge concentration of about 2.5 at.% in the insulating layer. Subsequently, the specimens were annealed at temperatures between 500°C and 1200°C for 30 min in a dry N₂ ambient atmosphere. Cross-sectional TEM analysis reveal homogeneously distributed Ge nanoclusters arranged in a broad band within the SiO₂ layer. Their mean cluster size varies between 2.0 and 6.5 nm depending on the annealing conditions. Cluster-free regions are always observed close to the surface of the specimens independent of the annealing process, whereas a narrow Ge nanocluster band appears at the SiO₂/Si interface at high annealing temperatures, e.g. ⩾1000°C. The atomic Ge redistribution due to the annealing treatment was investigated with a scanning TEM energy dispersive X-ray system and Rutherford back scattering (RBS).     

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.     

High-speed processing with Cl2 cluster ion beam

Cluster ion beam processes can produce high rate sputtering with low damage compared with monomer ion beam processes. Cl₂ cluster ion beams with different size distributions were generated with controlling the ionization conditions. Size distributions were measured using the time-of-flight (TOF) method. Si substrates and SiO₂ films were irradiated with the Cl₂ cluster ions at acceleration energies of 10–30 keV and the etching ratio of Si/SiO₂ was investigated. The sputtering yield increased with acceleration energy and was a few thousand times higher than that of Ar monomer ions. The sputtering yield of Cl₂ cluster ions was about 4400 atoms/ion at 30 keV acceleration energy. The etching ratio of Si/SiO₂ was above eight at acceleration energies in the range 10–30 keV. Thus, SiO₂ can be used as a mask for irradiation with Cl₂ cluster ion beam, which is an advantage for semiconductor processing. In order to keep high sputtering yield and high etching ratio, the cluster size needs to be sufficiently large and size control is important.     

Epitaxial 3C-SiC nanocrystal formation at the SiO2/Si interface after carbon implantation and subsequent annealing in CO atmosphere

3C-SiC nanocrystallites were epitaxially formed on a single crystalline Si surface covered by a 150 nm thick SiO₂ capping layer after low dose carbon implantation and subsequent high temperature annealing in CO atmosphere. Carbon implantation is used to introduce nucleation sites by forming silicon–carbon clusters at the SiO₂/Si interface facilitating the growth of 3C-SiC nanocrystallites.     

Light particle irradiation effects in Si nanocrystals

Si nanocrystals, formed by Si ion implantation into SiO₂ layers and subsequent annealing at 1150°C, were irradiated at room temperature either with He⁺ions at energies of 30 or 130 keV, or with 400 keV electrons. Transmission electron microscopy (TEM) and photoluminescence (PL) studies were performed. TEM experiments revealed that the Si nanocrystals were ultimately amorphized (for example at ion doses ∼10¹⁶ He cm⁻²) and could not be recrystallized by annealing up to 775°C. This contrasts with previous results on bulk Si, in which electron- and very light ion-irradiation never led to amorphization. Visible photoluminescence, usually ascribed to quantum-size effects in the Si nanocrystals, was found to decrease and vanish after He⁺ ion doses as low as 3 × 10¹²–3 × 10¹³ He cm⁻² (which produce about 1 displacement per nanocrystal). This PL decrease is due to defect-induced non-radiative recombination centers, possibly situated at the Si nanocrystal/SiO₂ interface, and the pre-irradiation PL is restored by a 600°C anneal.     

Fabrication of [110]-aligned Si quantum wires embedded in SiO2 by low-energy oxygen implantation

Si quantum wires (QWRs) embedded in SiO₂ are successfully fabricated by low-energy oxygen implantation on a V-groove patterned substrate. Si QWRs aligned to [1 1 0] appeared at the bottom-center of the V-groove. The [1 1 0] cross-section of the Si QWR is a hexagon encompassed by four Si {1 1 1} and two Si {0 0 1} lateral facets.     

Combined Rietveld refinement of Zn2SiO4:Mn2+ using X-ray and neutron powder diffraction data

The behavior of Mn²⁺ ions doped into the crystal lattice of Zn₂SiO₄ is closely related to the luminescent properties of Zn₂SiO₄:Mn²⁺ as a color-emitting phosphor. The combined Rietveld refinement using X-ray and neutron powder diffraction was used to determine the site preference and the amount of Mn²⁺ ions in Zn₂SiO₄:Mn²⁺. Of possible cation-disorder models, the best Rietveld refinement was obtained from the model that Mn²⁺ ions partially substituted for Zn²⁺ ions in two crystallographically non-equivalent Zn sites. The final converged weighted R-factor, R_wp, and the goodness-of-fit indicator, S (=R_wp/R_e) were 8.12% and 2.28, respectively. The occupancy of Mn²⁺ ions for the two non-equivalent Zn sites was 0.034(4) and 0.003(2), respectively. The refined model described the crystal structure in space group R?3 (No. 148) with Z = 18, a (=b) = 13.9612(1) Å, c = 9.3294(1) Å and γ = 120°.     

Low temperature formation of luminescent Si nanocrystals with combined process of excimer UV-light irradiation and RTA

Si ion implantation was widely used to synthesize specimens of SiO₂ containing supersaturated Si and subsequent high temperature annealing induces the formation of embedded luminescent Si nanocrystals. In this work, the potentialities of excimer UV-light (172 nm, 7.2 eV) irradiation and rapid thermal annealing (RTA) to achieve low temperature (below 1000 °C) formation of luminescent Si nanocrystals in SiO₂ have been investigated. The Si ions were introduced at acceleration energy of 180 keV to fluences of 7.5 × 10¹⁶ and 1.5 × 10¹⁷ ions/cm². The implanted samples were subsequently irradiated with an excimer-UV lamp for 2 h. After the process, the samples were rapidly thermal annealed at 1050 °C for 5 min before furnace annealing (FA) at 900 °C. Photoluminescence spectra were measured at various stages at the process. Effective visible photoluminescence is found to be observed even after FA at 900 °C, only for specimens treated with excimer-UV lamp and RTA, prior to a low temperature FA process. Based on our experimental results, we discuss the mechanism for the initial formation process of the luminescent Si nanocrystals in SiO₂, together with the effects with excimer lamp irradiation and RTA process on the luminescence.     

Ion beam mixing in uranium nitride thin films studied by Rutherford Backscattering Spectroscopy

Thickness, composition, concentration depth profile and ion irradiation effects on uranium nitride thin films deposited on fused silica have been investigated by Rutherford Backscattering Spectroscopy (RBS) using 2 MeV He⁺ ions. The films were prepared by reactive DC sputtering at the temperatures of ?200 °C, +25 °C and +300 °C. A perfect 1U:1N stoichiometry with a layer thickness of 660 nm was found for the film deposited at ?200 °C. An increase of the deposition temperature led to an enhancement of surface oxidation and an increase of the thickness of the mixed U–N–Si–O layers at the interface. The sample irradiation by 1 MeV Ar⁺ ion beam with ion fluence of about 1.2–1.7 × 10¹⁶ ions/cm² caused a large change in the layer composition and a large increase of the total film thickness for the films deposited at ?200 °C and at +25 °C, but almost no change in the film thickness was detected for the film deposited at +300 °C. An enhanced mixing effect for this film was obtained after further irradiation with ion fluence of 2.3 × 10¹⁶ ions/cm².     

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.     

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.     

MeV Si ions bombardment effects on the thermoelectric properties of Co0.1SbxGey thin films

We have grown three different monolayer Co_0.1Sb_xGe_y (x = 2, 4, 11 and y = 15, 7, 15) thin films on silica substrates with varying thickness between 100 and 200 nm using electron beam deposition. The high-energy (in the order of 5 MeV) Si ion bombardments have been performed on samples with varying fluencies of 1 × 10¹², 1 × 10¹³, 1 × 10¹⁴ and 1 × 10¹⁵ ions/cm². The thermopower, electrical and thermal conductivity measurements were carried out before and after the bombardment on samples to calculate the figure of merit, ZT. The Si ions bombardment caused changes on the thermoelectric properties of films. The fluence and temperature dependence of cross plane thermoelectric parameters were also reported. Rutherford backscattering spectrometry (RBS) was used to analyze the elemental composition of the deposited materials and to determine the layer thickness of each film.     

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.     

Self-organized formation of layered carbon–copper nanocomposite films by ion deposition

The quasi-simultaneous deposition of low energy-mass-selected C⁺ and metal⁺ ions leads to the formation of metal–carbon nanocomposites. In the case of C⁺ and Cu⁺ deposition, a homogeneous distribution of small copper clusters in an amorphous carbon matrix is expected. However, at a certain C⁺/Cu⁺ fluence ratio and energy range, alternately metal-rich and metal-deficient layers in an amorphous carbon matrix with periods in the nm range develop have been observed. The metal-rich layers consist of densely distributed crystalline Cu particles while the metal-deficient layers are amorphous and contain only few and small Cu clusters. The formation of multilayers can be described by an interplay of sputtering, surface segregation, ion induced diffusion, and the stability of small clusters against ion bombardment. This formation has been investigated for the a-C:Cu system with respect to the ion energy and the C⁺/Cu⁺ fluence ratio. The sputter coefficient S_M = r_f S_CCu + S_CuCu is the parameter to switch between layer growth (S_M < 1) and homogeneous cluster distribution (S_M > 1).     

Optical and electrical characterizations of Mn doped p-type β-FeSi2

β-FeSi₂ has attracted increasing attention as a promising material for optoelectronic and thermoelectronic devices due to a high optical absorption coefficient (α) of about 10⁵ cm⁻¹ near 1.0 eV and its chemical stability at higher temperatures. For the future practical use of this material in devices, the control of each electrical conductivity type and the improvement of the material quality are highly required. Although unintentionally doped β-FeSi₂ layers formed on n-type Si(1 0 0) by the conventional electron-beam deposition (EBD) have typically shown n-type conductivity, the p-type β-FeSi₂ layers were formed by the introduction of Mn impurity using ion-implantation at room temperature (RT) and subsequent annealing procedures. In this study, we aimed to make p-type β-FeSi₂ by implantation of ⁵⁵Mn⁺ ions into EBD-grown n-type β-FeSi₂ layers/n-Si, where ⁵⁵Mn⁺ ions were implanted at two different temperatures (T_sub) of RT and 250°C using an energy and a dose of 300 keV and 2.68 × 10¹⁵ cm⁻², respectively. Their optical and electrical properties, which ought to be affected by implantation and annealing temperatures (T_a2), were investigated by Raman scattering, optical transmittance, reflectance and van der Pauw measurements. The results showed that the ⁵⁵Mn⁺ doping with T_sub=RT and higher thermal annealing at T_a2=900°C produced p-type layers of good quality with maximum hole mobility of 454.5 cm²/Vs at about 65 K.     

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.