Enhanced photoluminescence response of Er-Si nanoparticle codoped Al2O3 films by controlled synthesis in the nanoscale and thermal processing

Nanostructured Er³⁺-Si nanoparticles (NPs) codoped Al₂O₃ films were synthesized by a one step laser based deposition process which allows to form the Si NPs in situ at room temperature, and to control their size and separation with the Er ions in the nanoscale. Two different thermal annealing treatments are studied in order to optimize the photoluminescence (PL) emission: rapid thermal annealing (RTA) at 900 °C during 2 min, and conventional furnace step annealing at different temperatures up to 750 °C for 1 h. After RTA process the films show an important enhancement on the photoluminescence lifetime values which is related to a reduction of the non-radiative decay channels. Nevertheless, the Si NPs to Er ions energy transfer is strongly reduced. In contrast after conventional furnace annealing up to 700 °C, although there is only a moderate increase of the photoluminescence lifetime values, the excitation of Er ions through Si NPs is still active and as a consequence a large enhancement of the photoluminescence intensity with respect to the Er-only doped film is achieved. These different behaviours are most likely related to structural and chemical changes in the Er environment upon the different annealing processes.     

Effects of phosphorus doping on structural and optical properties of silicon nanocrystals in a SiO2 matrix

Promise of Si nanocrystals highly depends on tailoring their behaviour through doping. Phosphorus-doped silicon nanocrystals embedded in a silicon dioxide matrix have been realized by a co-sputtering process. The effects of phosphorus-doping on the properties of Si nanocrystals are investigated. Phosphorus diffuses from P-P and/or P-Si to P-O upon high temperature annealing. The dominant X-ray photoelectron spectroscopy P 2p signal attributable to Si-P and/or P-P (130 eV) at 1100 °C indicates that the phosphorus may exist inside Si nanocrystals. It is found that existence of phosphorus enhances phase separation of silicon rich oxide and thereby Si crystallization. In addition, phosphorus has a considerable effect on the optical absorption and photoluminescence properties as a function of annealing temperature.     

Formation of light-emitting Si nanostructures in SiO(2) by pulsed anneals

Intense excimer laser pulses, flash lamp annealing and rapid thermal annealing were used to form Si nanocrystals in thin SiO(2) layers implanted with high doses of Si ions. The pulse durations were 20?ns, 20?ms and 1?s, respectively. Laser annealing produced light sources luminescing in the wavelength range of 400-600?nm. They were attributed to the Si clusters formed as a result of the fast segregation of Si atoms from the SiO(2) network. There were no indications of nanocrystal formation in the as-implanted layers after 20?ns laser pulses; however, nanocrystals formed when, before the laser annealing, the amorphous Si nanoprecipitates were prepared in the oxide layers. Evaluations show that the crystallization may proceed via melting. A photoluminescence band near 800?nm, typical of Si nanocrystals, was found after 20?ms and 1?s anneals. Calculations revealed that the annealing times in both cases were too short to provide the diffusion-limited crystal growth if one uses the values of stationary Si diffusivity in SiO(2). This points toward the existence of a transient rapid growth process at the very beginning of the anneals.     

Effect of ion doping with donor and acceptor impurities on intensity and lifetime of photoluminescence from SiO2 films with silicon quantum dots

Doping with donor and acceptor impurities is an effective way to control light emission originated from quantum-size effect in Si nanocrystals. Combined measurements of photoluminescence intensity and kinetics give valuable information on mechanisms of the doping influence. Phosphorus, boron, and nitrogen were introduced by ion implantation into Si+ -implanted thermal SiO2 films either before or after synthesis of Si nanocrystals performed at Si excess of about 10 at.% and annealing temperatures of 1000 and 1100 degrees C. After the implantation of the impurity ions the samples were finally annealed at 1000 degrees C. It is found that, independently of ion kind, the ion irradiation (the first stage of the doping process) completely quenches the photoluminescence related to Si nanocrystals (peak at around 750 nm) and modifies visible luminescence of oxygen-deficient centers in the oxide matrix. The doping with phosphorus increases significantly intensity of the 750 nm photoluminescence excited by a pulse 337 nm laser for the annealing temperature of 1000 degrees C, while introduction of boron and nitrogen atoms reduces this emission for all the regimes used. In general, the effective lifetimes (ranging from 4 to 40 micros) of the 750 nm photoluminescence correlate with the photoluminescence intensity. Several factors such as radiation damage, influence of impurities on the nanocrystals formation, carrier-impurity interaction are discussed. The photoluminescence decay is dominated by the non-radiative processes due to formation or passivation of dangling bonds, whereas the intensity of photoluminescence (for excitation pulses much shorter than the photoluminescence decay) is mainly determined by the radiative lifetime. The influence of phosphorus doping on radiative recombination in Si quantum dots is analyzed theoretically.     

Formation of microcrystalline silicon films using rapid crystal aluminum induced crystallization under low-temperature rapid thermal annealing

The process of obtaining thin film solar cells using the method of aluminum-induced crystallization under rapid thermal annealing (RTA) was investigated. 200-nm-thick amorphous Si (a-Si) film was deposited on a glass substrate using an ultra-high vacuum ion beam sputtering system. A 50-nm-thick crystal aluminum layer was then evaporated and deposited onto the a-Si film. In contrast to conventional furnace annealing, RTA can supply rapid thermal energy so that a-Si can be induced into microcrystalline-Si (μc-Si) in a short time at low temperatures. The crystal Al may promote the crystallization reaction because its surface energy is higher than 0.89 N/m, which is the minimum energy required to produce the (111) orientation. Free Si atoms are induced at the interface of the Al and Si sub-layers by the diffusion of Al along the grain boundaries. The Raman spectrum shows that the sample could be induced to crystallize at 350 °C. After the aluminum was etched, the maximum grain size was 4 μm. The carrier mobility was between 6.2 cm²/Vs and 18.8 cm²/Vs. The proposed method can be used to obtain μc-Si with reduced energy and time during the thermal annealing.     

Enhanced luminescence from encapsulated silicon nanocrystals in SiO2 with rapid thermal anneal

It is well known that Si ion implantation into SiO₂ and subsequent high-temperature anneals induce the formation of embedded luminescent Si nanocrystals. In this work, the potentialities of rapid thermal annealing to enhance the photoluminescence intensity have been investigated. Ion implantation was used to synthesize specimens of SiO₂ containing excess Si with different concentrations. Si precipitation to form nanocrystals in implanted samples takes place with a conventional furnace anneal. The photoluminescence intensity and the peak energy of emission from Si nanocrystals depend on implanted ion dose. Moreover, the luminescence intensity is strongly enhanced with a rapid thermal annealing prior to a conventional furnace anneal. The luminescence intensity, however, decreases when rapid thermal annealing follows conventional furnace annealing. It is found that the order of heat treatment is an important factor in intensities of the luminescence and that the luminescence peak energy is found to be dependent, but only by a small factor, on the thermal history of specimens. Enhancement is found to be typical for low dose samples. Furthermore, the observation that the prolonged anneal induces saturation and a blue shift of the luminescence strongly indicates the emission is not simply due to electron-hole recombination inside the Si nanocrystals. Based on our experimental results, we discuss the mechanism for the enhancement of the photoluminescence, together with the mechanism of photoemission.     

Tuned photoluminescence from Si-implanted SiO2 films with rapid and conventional thermal annealing

In this study, by using a conventional thermal annealing (CTA), the obviously near-infrared shift and intensity amplification of room-temperature photoluminescence (PL) spectrum could be observed from the 3 × 10¹⁶ cm⁻² Si⁺-implanted 400-nm-thick SiO₂ films after rapid thermal annealing (RTA) at 1150 °C in dry nitrogen. For isothermal RTA durations ≥20 s at the heating rate of 100 °C/s, the PL peaks from the only RTA-treated films were detected around 1.7 eV and, for 1050 °C CTA durations between 1 and 3 h, no significant PL could be found from the only CTA-treated films. However, when annealing the RTA-treated films with the CTA for only 1 h, then, we varied the terminal PL-peak from 1.7 to 1.5 eV and obviously increased their respective intensities from the films. These results are attributed to the variation of silicon nano-crystals embedded in SiO₂ film.     

Influence of rapid thermal annealing on the process of aluminum induced crystallization of amorphous Si

The effects of annealing methods on the crystallization process and microstructure of polycrystalline silicon (poly-Si) films obtained by aluminum-induced crystallization (AIC) of amorphous Si (a-Si) films were comparatively investigated. Glass/Al/a-Si structures were annealed by rapid thermal annealing (RTA) and conventional furnace at 500 °C for different times in Ar. As compared to furnace annealing, AIC of a-Si films annealed by RTA possesses a shorter period of nucleation time, a higher nucleation density and reduces the process time to form continuous poly-Si films. It is revealed that the continuous Si films obtained by both RTA and conventional furnace annealing are polycrystalline in nature, exhibiting good microstructures with Raman peaks at 518 cm^?1 and full-width at half-maximums of 6.43–6.48 cm^?1.     

Diamond nanocrystals and amorphous SiOx nanowires formed by rapid thermal annealing of carbon film

Rapid thermal annealing (RTA) has been performed on the carbon films prepared by radio frequency plasma-enhanced chemical vapor deposition on Si substrate. The RTA at 800 °C for 60 s leads to the formation of many diamond nanocrystallites agglomerating on the film surface. Higher temperature RTA at 1100 °C for 60 s induces the high-density amorphous SiO_x (x = 1.2) nanowires on the film surface without diamond nanocrystallites. At both the RTA temperatures, a well-oriented SiC interlayer is also formed simultaneously. The sp³ sites in the carbon film and the oxygen during the RTA treatment as well as the RTA temperature are considered to play important roles in determining the final reaction products.     

Ge/Si heterojunction photodetector for 1.064 µm laser pulses

Isotype and anisotype heterojunction Ge/Si photodetectors have been made by depositing Ge layer onto monocrystalline Si using vacuum evaporation technique. These detectors before and after annealing were utilized to detect 1.064 μm Nd:YAG laser pulses. The study also includes determination of the optimum Ge thickness and annealing conditions. The experimental results show that the photoresponse highly improve after classical thermal annealing (CTA) and rapid thermal annealing (RTA).The voltage responsivity and rise time results are strongly dependent on annealing type and conditions. It is found that the optimum conditions can be obtained for n-Ge/p-Si photodetector prepared with 200 nm Ge thick and annealed with RTA at 500°C/25 sec.     

Ion irradiation induced amorphization of SnO2 nanoparticles embedded in SiO2

SnO₂ nanoparticles (NPs) of average diameter of ∼10.5 nm, synthesized in SiO₂ using Sn⁻ ions implantation combined with thermal annealing, were irradiated with 1.5 MeV Au²⁺ ions at room temperature. The NP structure was studied as a function of ion fluence by transmission electron microscopy and micro-Raman spectroscopy. Prior to ion irradiation, SnO₂ NPs have been found to exhibit the rutile crystal structure. Upon irradiation, amorphization in the nanocrystals has been seen to increase with increase in ion fluence. In particular, at a fluence of 1 × 10¹⁴ ions cm⁻² we argue for the presence of an amorphous SnO₂ phase. Beyond this fluence, the NPs have been found to dissolve in the matrix. The observed results are explained in the frame work of ion irradiation induced defects production in the NPs as well as in the NP/matrix interface.     

Structured ZnO-based contacts deposited by non-reactive rf magnetron sputtering on ultra-thin SiO2/Si through a stencil mask

In this paper, we study the localized deposition of ZnO micro and nanostructures deposited by non-reactive rf-magnetron sputtering through a stencil mask on ultra-thin (10 nm) SiO₂ layers containing a single plane of silicon nanocrystals (NCs), synthetized by ultra-low energy ion implantation followed by thermal annealing. The localized ZnO-deposited areas are reproducing the exact stencil mask patterns. A resistivity of around 5 × 10^− 3 Ω cm is measured on ZnO layer. The as-deposited ZnO material is 97% transparent above the wavelength at 400 nm. ZnO nanostructures can thus be used as transparent electrodes for Si NCs embedded in the gate-oxide of MOS devices.     

Si-rich a-SiC:H thin films: Structural and optical transformations during thermal annealing

Amorphous hydrogenated silicon-rich silicon carbide (a-Si_0.8C_0.2:H) thin films were prepared by plasma enhanced chemical vapour deposition and were thermally annealed in a conventional resistance heated furnace at annealing temperatures up to 1100 °C. The annealing temperatures were varied and the samples were characterised with Auger electron spectroscopy, glancing incidence X-ray diffraction, Raman spectroscopy, Fourier transformed infrared spectroscopy, transmission electron microscopy and photoluminescence (PL) spectroscopy. As-deposited a-Si_0.8C_0.2:H thin films contain a large amount of hydrogen and are amorphous. When annealing the films, the onset of Si crystallisation appears at 700 °C. For higher annealing temperatures, we observed SiC crystallites in addition to the Si nanocrystals (NCs). The crystallisation of SiC correlates with the occurrence of a strong PL band, which is strongly reduced after hydrogen passivation. Thus PL signal originates from the SiC matrix. Si NCs exhibit no PL yield due to their inhomogeneous size distribution.     

Formation and optical properties of nanocrystalline selenium on Si substrate

We report on the formation of nanocrystalline selenium (NC-Se) on Si substrate by ultra-high vacuum physical deposition combined with rapid thermal annealing (RTA). NC-Se in a trigonal phase with an average diameter around 20 nm was formed during RTA on the amorphous selenium film at 180 °C. The NC-Se exhibits a broad and strong photoluminescence at ~ 1.7 eV at room temperature. Systematic optical investigations were carried out, and the emission was ascribed to the recombination between donor- and acceptor-like states at the NC-Se/a-Se interface.     

Electron microscopy study of ion beam synthesized β-FeSi2

β-FeSi₂ embedded in a Si matrix was prepared by ion beam synthesis (IBS). Two step implantation, with energies 60 and 20 keV, of two different doses of the iron ions, 5 × 10¹⁵ and 5 × 10¹⁶ cm⁻¹, was performed. After the implantation, the samples were subjected to rapid thermal annealing (RTA) at 900 °C. The crystal structure of the resulting material was studied using cross-sectional transmission electron microscopy (XTEM), including high-resolution electron microscopy (HREM). The comparison of the XTEM images with the initial iron ions implantation profiles, simulated by SRIM (Stopping and Range of Ions in Matter) demonstrate that the process of IBS, followed by RTA, preserves the initial implantation profile, implying a negligible Fe atoms diffusion velocity in comparison with the one of the chemical reaction between Fe and Si. The XTEM images show that continuous β-FeSi₂ layers are fabricated when there is a stoichiometric region in the initial implantation profile. Fe concentration lower than the stoichiometric one in the whole implantation range results in formation of β-FeSi₂ nanocrystallites embedded in the Si matrix. The behavior of the absorption coefficient energy dependences, obtained from the optical transmittance and reflectance measurements, reflects the different crystal structures forming in the two types of samples.     

Rapid Thermal Annealing of ZnO Nanocrystalline Films for Dye-Sensitized Solar Cells

Nanocrystalline ZnO thin films were prepared by the sol–gel method and annealed at 600 °C by conventional (CTA) and rapid thermal annealing (RTA) processes on fluorine-doped tin oxide (FTO)-coated glass substrates for application as the work electrode for a dye-sensitized solar cell (DSSC). ZnO films were crystallized using a conventional furnace and the proposed RTA process at annealing rates of 5 °C/min and 600 °C/min, respectively. The ZnO thin films were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM) analyses. Based on the results, the ZnO thin films crystallized by the RTA process presented better crystallization than films crystallized in a conventional furnace. The ZnO films crystallized by RTA showed higher porosity and surface area than those prepared by CTA. The results show that the short-circuit photocurrent (J _sc) and open-circuit voltage (V _oc) values increased from 4.38 mA/cm² and 0.55 V for the DSSC with the CTA-derived ZnO films to 5.88 mA/cm² and 0.61 V, respectively, for the DSSC containing the RTA-derived ZnO films.     

Rapid thermal annealing of rare earth implanted ZnO epitaxial layers

Zinc oxide epilayers grown by metal organic vapour phase epitaxy on (0 0 0 1) sapphire substrates were doped with Praseodymium and Europium by ion implantation. The as-implanted samples were either annealed in air for 20 min in a tube furnace or rapid thermal annealing (RTA) was performed, for 2 min, in a nitrogen atmosphere. The samples were characterized by Rutherford Backscattering Spectrometry/Channelling and photoluminescence. The presented results indicate that in the as-implanted samples the majority of the rare earth (RE) ions are incorporated into substitutional Zn-sites. Furnace annealing at 1000 °C recovers the crystal quality of the samples but leads to an out-diffusion of the RE. RTA suppresses diffusion but lattice damage is not fully recovered at 1000 °C. More importantly, during RTA the RE ions are driven from the substitutional site and are now found mainly on random interstitial sites and no optical activation could be achieved.     

Laser annealing of neutron irradiated boron-10 isotope doped diamond

¹⁰B isotope doped p-type diamond epilayer grown by chemical vapor deposition on (110) oriented type IIa diamond single crystal substrate was subjected to neutron transmutation at a fluence of 2.4 × 10²⁰ thermal and 2.4 × 10²⁰ fast neutrons. After neutron irradiation, the epilayer and the diamond substrate were laser annealed using Nd–YAG laser irradiation with wave length, 266 nm and energy, 150 mJ per pulse. The neutron irradiated diamond epilayer and the substrate were characterized before and after laser annealing using different techniques. The characterization techniques include optical microscopy, secondary ion mass spectrometry, X-ray diffraction, Raman, photoluminescence and Fourier Transform Infrared spectroscopy, and electrical sheet conductance measurement. The results indicate that the structure of the irradiation induced amorphous epilayer changes to disordered graphite upon laser annealing. The irradiated substrate retains the (110) crystalline structure with neutron irradiation induced defects.     

Study of the damage produced in 6H-SiC by He irradiation

Lattice damage and evolution in 6H-SiC under He⁺ ion irradiation have been investigated by the combination of Rutherford backscattering in channeling geometry (RBS/C), Raman spectroscopy, UV–visible spectroscopy and transmission electron microscopy (TEM). 6H-SiC wafers were irradiated with He ions at a fluence of 3 × 10¹⁶ He⁺cm⁻² at 600 K. Post-irradiation, the samples were annealed in vacuum at different temperatures from 873 K to 1473 K for isochronal annealing (30 min). Thermally annealed He irradiated 6H-SiC exhibited an increase in damage or reverse annealing behavior in the damage peak region. The reverse annealing effect was found due to the nucleation and growth of He bubbles. This finding was consistent with the TEM observation. The thermal annealing brought some recovery of lattice defects and therefore the intensities of Raman peaks increased and the absorption coefficient decreased with increasing annealing temperature. The intensity of Raman peak at 789 cm⁻¹ as a function of annealing temperature was fitted in terms of a thermally activated process which yielded activation energy of 0.172 ± 0.003 eV.