Optical excitation and emission processes of Si-QD/SiO2 multilayer films with different SiO2 layer thicknesses

Si-rich oxide/SiO₂ multilayer films with different SiO₂ layer thicknesses have been deposited by the plasma enhanced chemical vapor deposition technique, and crystallized Si quantum dot (Si-QD)/SiO₂ multilayer films are obtained after annealing at 1100 ^°C. The photoluminescence (PL) intensity of the multilayer films increases significantly with increasing SiO₂ layer thickness, and the PL peak shifts from 1.25 eV to 1.34 eV. The PL excitation spectra indicate that the maximal PL excitation intensity is located at 4.1 eV, and an excitation–transfer mechanism exists in the excitation processes. The PL decay time for a certain wavelength is a constant when the SiO₂ thickness is larger than 2 nm, and a slow PL decay process is obtained when the SiO₂ layer is 1 nm. In addition, the PL peak shifts toward high energy with decreasing temperature only when the SiO₂ layer is thick enough. Detailed analyses show that the mechanism of PL changes from the quantum confinement effect to interface defects with decreasing SiO₂ layer thickness.     

Temperature behaviour of optical properties of Si+-implanted SiO2

Silicon nanocrystals were prepared by Si⁺-ion implantation and subsequent annealing of SiO₂ films thermally grown on a c-Si wafer. Different implantation energies (20-150 keV) and doses - cm ^-2 ) were used in order to achieve flat implantation profiles (through the thickness of about 100 nm) with a peak concentration of Si atoms of 5, 7, 10 and 15 atomic%. The presence of Si nanocrystals was verified by transmission electron microscopy. The samples exhibit strong visible/IR photoluminescence (PL) with decay time of the order of tens of μs at room temperature. The changes of PL in the range 70-300 K can be well explained by the exciton singlet-triplet splitting model. We show that all PL characteristics (efficiency, dynamics, temperature dependence, excitation spectra) of our Si⁺-implanted SiO₂ films bear close resemblance to those of a light-emitting porous Si and therefore we suppose similar PL origin in both materials. Received 1st September 1998 and Received in final form 7 September 1999     

Si-based nanoscale SiO2 islands and light-emitting source array

A SiO₂ nanoscale island array was fabricated on a Si substrate by using anodic porous alumina as a mask. Transmission electron microscopy observation and the atomic force microscopy pattern show that the arrangement of SiO₂ islands has a quasi-hexagonal symmetry. Ge ions with a dose of 1×10¹⁷ cm^-2 were subsequently implanted into the SiO₂ island array to form Ge-related light-emitting centers. The photoluminescence (PL) spectra of as-implanted and annealed samples show three PL bands at 370, 400 and 415 nm. Their intensities reach maximums in the sample with an annealing temperature of 700 °C. Spectral analysis suggests that the 370 and 415 nm PL bands arise from Ge-Ge and Ge-Si defect centers, while the 400 nm PL is related to GeO color centers in the SiO₂ islands. The existence of these PL bands indicates the formation of a Si-based nanoscale light source array. PACS 78.55.Mb; 42.72.Bj; 68.65.+g     

SiO x -P2O5 films—promising components in photonic structure

We intend to prepare periodic multilayered structures for photonic applications. With this goal we have performed a study of some characteristics of SiO _x -P₂O₅ films deposited by the sol–gel method on glass and ITO (InSnO _x )-coated glass. The as prepared films were annealed to different temperatures (150 and 200°C). The chemical composition of the samples was determined by X-ray Photoelectron Spectroscopy (XPS). The XPS results revealed the presence of P in the as-deposited films. The structural an optical properties were examined by Fourier Transform Infrared Spectroscopy (FTIR), Spectroellipsometry (SE) and UV Transmission Spectroscopy. IR spectra of the deposited films attest the interaction of an amorphous SiO₂ with the H₃PO₄ used as a P-precursor. Refractive indices for individual SiO _x -P₂O₅ determined from SE measurements show a densification of the layer structure with the increasing temperature in the thermal treatment. The UV transmission spectra revealed a lower transmission for the sol-gel SiO _x -P₂O₅ films as compared to ITO/glass substrate. AFM images proved the densification of the films with annealing in agreement with the ellipsometric results. The work was originally presented at “Physics of Photonic Crystals and Metamaterials (PPCM)” Workshop, Brussels, 12–15 June, 2006.     

Visible photoluminescence from Ge+-implanted SiO2 films thermally grown on crystalline Si

+ -implanted SiO₂ films is studied as a function of different fabricating conditions (implantation dose, annealing temperature and time). The SiO₂ films containing Ge nanocrystals exhibit two photoluminescence (PL) bands peaked at 600 nm and 780 nm. There are two excitation bands in the PL excitation (PLE) spectra. With variation in Ge nanocrystal size, the PL and PLE peak energies show no appreciable shift. The PL and PLE spectral analyses suggest that during the PL process, electron–hole pairs are generated by the E(l) and E(2) direct transitions inside Ge nanocrystals, which then radiatively recombine via luminescent centers in the matrix or at the interface between the nanocrystal/matrix. Received: 27 January 1998/Accepted: 18 March 1998     

Laser–MBE growth of high-quality ZnO thin films on Al2O3(0001) and SiO2/Si(100) using the third harmonics of a Nd:YAG laser

High-quality ZnO thin films were grown on single-crystalline Al₂O₃(0001) and amorphous SiO₂/Si(100) substrates at 400–640 °C using laser molecular beam epitaxy. For film growth, the third harmonics of a pulsed Nd:YAG laser were illuminated on a ZnO target. The ZnO films were epitaxially grown on Al₂O₃(0001) with the narrow X-ray diffraction full width at half maximum (FWHM) of 0.04° and the films on SiO₂/Si(100) exhibited a preferred c-axis orientation. Furthermore, the films exhibited excellent optical properties in photoluminescence (PL) measurements with very sharp excitonic and weak deep-level emission peaks. At 15 K, PL FWHM values of the films grown on Al₂O₃(0001) and SiO₂/Si(100) were 3 and 18 meV, respectively. Received: 8 May 2001 / Accepted: 18 September 2001 / Published online: 20 December 2001     

Hydrogenation effect on enhancement of photoluminescence of Er and Si nanocrystallites in Er-doped SiO2 synthesized by laser ablation

Significant enhancement of photoluminescence (PL) was attained for Er ions and Si nanocrystallites (nc-Si) in SiO₂ films by two kinds of hydrogenation, using H₂ molecules or H atoms. Er-doped SiO₂ films containing Er impurities and a high density of nc-Si were fabricated by laser ablation of Er films deposited on Si substrate in an O₂ gas atmosphere, followed by annealing at high temperatures in flowing Ar gas. Hydrogenation at 300–500 °C was found to effectively increase the PL intensity of Er ions as well as that of nc-Si. In particular, the hydrogen atom treatment dramatically shortens the hydrogenation time for the enhancement of Er PL compared to the hydrogen molecule treatment. Spectra of electron spin resonance showed a decrease in residual defects, namely, P_b-type defects located at the interfaces between nc-Si and SiO₂ by hydrogenation. These results clearly show the effectiveness of hydrogen passivation for Si nanostructures; i.e., the increase in the Er PL and nc-Si PL due to hydrogen passivation of the nonradiative recombination centers located at the interfaces between nc-Si and SiO₂. PACS 78.67.Bf; 71.20.Eh; 76.30.Mi; 81.15.Fg     

Optical and electrical properties of Ge-implanted SiO2 layers on n-Si and p-Si

Ge ions of 100 keV were implanted into a 120 nm-thick SiO₂ layer on n-Si at room temperature while those of 80 keV were into the same SiO₂ layer on p-Si. Samples were, subsequently, annealed at 500°C for 2 h to effectively induce radiative defects in the SiO₂. Maximum intensities of sharp violet photoluminescence (PL) from the SiO₂/n-Si and the SiO₂/p-Si samples were observed when the samples have been implanted with doses of 1×10¹⁶ and 5×10¹⁵ cm⁻², respectively. According to current–voltage (I–V) characteristics, the defect-related samples exhibit large leakage currents with electroluminescence (EL) at only reverse bias region regardless of the type of substrate. Nanocrystal-related samples obtained by an annealing at 1100°C for 4 h show the leakage at both the reverse and the forward region.     

Evaluating Zn2SiO4:Mn phosphor for use in medical imaging radiation detectors

2 SiO₄:Mn phosphor was evaluated for use in radiation detectors of medical imaging systems. Zn₂SiO₄:Mn was used in the form of laboratory-prepared fluorescent layers (screens) with coating weights from 18 to 150 mg/cm². The phosphor was excited to luminescence by low-energy X-raysusing X-raytube voltages ranging from 15 to 50 kVp. The number of emitted optical photons per incident X-rayquantum was thus determined for various X-rayenergies and phosphor coating weights. The optical emission spectrum was also measured and it was used to evaluate the spectral compatibility of Zn₂SiO₄:Mn with radiographic films, photocathodes and the Si photodiode. Finally, phosphor optical properties were estimated by fitting a theoretical model to experimental data. Results showed that Zn₂SiO₄:Mn is more efficient for low-energy X-rays. Its intrinsic conversion efficiency was found equal to 0.08, which is comparable to that of actually used phosphors. Zn₂SiO₄:Mn was also adequately compatible with orthochromatic films and the ES-20 photocathode, thus being appropriate for low-voltage radiography and fluoroscopy. Received: 31 July 1998/Accepted: 3 August 1998     

Ferroelectric SrxBa1-xNb2O6 optical waveguiding thin films on SiO2-coated Si(100) substrates

x Ba_1-xNb₂O₆ (x=0.5) films (abbreviated as SBN:0.5) on SiO₂-coated Si substrates are potential components for the application of integrated electro-optics devices. SBN:0.5 optical waveguiding thin films on SiO₂-coated Si substrates with a very thin MgO diffusion buffer have been successfully prepared by pulsed laser deposition. The as-grown films have a refractive index of 2.28, which is close to that of bulk SBN. X-ray analysis showed that the as-grown films have a single-phase tetragonal tungsten bronze structure. The SBN:0.5 thin films prepared by PLD exhibit favorable ferroelectric and optical waveguiding properties. The composition and the morphology of the films were also examined by XPS and by SEM, respectively. Ferroelectric SBN:0.5 optical waveguiding thin films on SiO₂-coated Si substrates are expected to be used in integrated electro-optic devices. Received: 27 February 1997/Accepted: 17 October 1997     

Pure UV photoluminescence from ZnO thin film by thermal retardation and using an amorphous SiO2 buffer layer

ZnO/SiO₂ thin films were fabricated on Si substrates by E-beam evaporation with thermal retardation. The as-prepared films were annealed for 2 h every 100 °C in the temperature range 400-800 °C under ambient air. The structural and optical properties were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL). The XRD analysis indicated that all ZnO thin films had a highly preferred orientation with the c-axis perpendicular to the substrate. From AFM images (AFM scan size is 1 μm×1 μm), the RMS roughnesses of the films were 3.82, 5.18, 3.65, 3.40 and 13.2 nm, respectively. PL measurements indicated that UV luminescence at only 374 nm was observed for all samples. The optical quality of the ZnO film was increased by thermal retardation and by using an amorphous SiO₂ buffer layer.     

Photoluminescence properties of blue-emitting Li4SrCa(SiO4)2:Eu2+ phosphor for solid-state lighting

Blue-emitting Li₄SrCa(SiO₄)₂:Eu²⁺ phosphors have been synthesized by solid-state reaction. The photoluminescence (PL) excitation spectrum shows broad-band absorption and matches well with the emission of a near-UV (n-UV) chip. The PL emission spectrum exhibits a broad-band emission peaking at 430 nm, which is the characteristic emission of the f–d transition of the Eu²⁺ ion. The diffuse reflection spectra, temperature-dependent emission spectra, fluorescence decay, and mechanism of concentration quenching are also studied in detail. Li₄SrCa(SiO₄)₂:Eu²⁺ is a candidate blue phosphor for n-UV excited solid-state lighting.     

SiO2 films fabricated by F2 laser-induced chemical deposition using silicone rubber

Silicon dioxide (SiO₂) films were selectively fabricated on a Si substrate at room temperature by illuminating both the silicone rubber target and the substrate with an F₂ laser (157 nm). The laser fluence was much less than the ablation threshold. Absorption due to absorbed water (H₂O) and hydrogen-bonded silanol (SiOH) groups were observed in addition to absorption due to Si-O-Si stretching mode in the Fourier transform infrared spectroscopy (FT-IR) spectra of the films. The illumination with higher laser fluence caused an increase of Si-O-Si/OH peak ratio in the FT-IR spectra, a decrease of etching rate in hydrofluoric acid (HF) solution, and an increase in the refractive index close to the value of a thermal SiO₂ film. These results indicate that the quality of the grown SiO₂ films was improved. The high photon energy of F₂ laser induced photodissociation of main chains and side chains of silicone and oxygen (O₂), and bonds between the ejected gaseous molecules including Si and O(¹D) to form SiO₂ films. PACS 61.80.Ba; 81.15.Fg; 82.50.Hp     

Excitation of Er atoms by energy transfer from Si nanocrystallites embedded in SiO2 matrices fabricated by laser ablation

We have investigated excitation of Er³⁺ ions via energy transfer from Si nanocrystallites embedded in SiO₂ films. The Er-doped films were fabricated using a laser ablation technique. We found that a photoluminescence (PL) excitation spectra of Er³⁺ ions coincides with that of Si nanocrystallites. Thus, it is evident that Er³⁺ ions are excited via the luminescent singlet state in Si nanocrystallites. Furthermore, we obtained the results that support the energy transfer mechanism. PL intensity of Er³⁺ ions increases with Er concentration while that of Si nanocrystallites decrease inversely. PL intensity of Er³⁺ ions increases with temperature from cryogenic to room temperature under photo-excitation at power density higher than 110 mW/cm². The increase is characteristic of the luminescent state in Si nanocrystallites but not any state in Er³⁺ ions. PACS 61.72.Ww; 61.46.+w; 81.15Fg     

Optical properties of amorphous Si/SiO2superlattice

Amorphous Si/SiO₂(a-Si/SiO₂) superlattices have been fabricated by the magnetron sputtering technique. The superlattice with an Si layer thickness of 1.8 nm has been characterized by transmission electron microscopy (TEM). The result indicates that most of the regions in the Si layer consist of amorphous phase, while regular structure appears in some local regions. This is in agreement with the Raman scattering spectroscopy. The optical absorption spectrum and photoluminescence (PL) spectrum have been measured. Moreover, the third-order optical nonlinearity χ⁽³⁾of this superlattice has been measured. To our knowledge, this is the first investigation of the nonlinear absorption and refractive index of an a-Si/SiO₂superlattice using the Z -scan technique. The real and imaginary parts of χ⁽³⁾have been found to be 1.316  ×  10 ^− 7eus and  − 5.596  ×  10 ^− 7eus, respectively, which are about two orders of magnitude greater than those of porous silicon. The results may be attractive for potential application in electro-optics devices.     

Coupling between Ge-nanocrystals and defects in SiO2

Room temperature photoluminescence (PL) at around 600 nm from magnetron-sputtered SiO₂ films co-doped with Ge is reported. The PL signal is observed in pure SiO₂, however, its intensity increases significantly in the presence of Ge-nanocrystals (Ge-nc). The PL intensity has been optimized by varying the temperature of heat treatment, type of gas during heat treatment, concentration of Ge in the SiO₂ films, and gas pressure during deposition. Maximum intensity occurs when Ge-nc of around 3.5 nm are present in large concentration in SiO₂ layers deposited at fairly high gas pressure. Based on time resolved PL, and PL measurements after α-particle irradiation or H passivation, we attribute the origin of the PL to a defect in SiO₂ (probably an O deficiency) that is excited through an energy transfer from Ge-nc. There is no direct PL from the Ge-nc; however, there is a strong coupling between excitons created in the Ge-nc and the SiO₂ defect.     

Structural and optical properties of Ge nanocrystals obtained by hot ion implantation into SiO2 and further ion irradiation

In this work, SiO₂ layers containing Ge nanocrystals (NCs) obtained by the hot implantation approach were submitted to an ion irradiation process with different 2 MeV Si⁺ ion fluences. We have investigated the photoluminescence (PL) behavior and structural properties of the irradiated samples as well as the features of the PL and structural recovery after an additional thermal treatment. We have shown that even with the highest ion bombardment fluence employed (2×10¹⁵ Si/cm²) there is a residual PL emission (12% from the original) and survival of some Ge NCs is still observed by transmission electron microscopy analysis. Even though the final PL and mean diameter of the nanoparticles under ion irradiation are independent of the implantation temperature or annealing time, the PL and structural recovery of the ion-bombarded samples have a memory effect. We have also observed that the lower the ion bombardment fluence, the less efficient is the PL recovery. We have explained such behavior based on current literature data.     

Defect reduction and surface passivation of SiO2/Si by heat treatment with high-pressure H2O vapor

Heat treatment with high-pressure H₂O vapor was applied to improve interface properties of SiO₂/Si and passivate the silicon surface. Heat treatment at 180–420 °C with high-pressure H₂O vapor changed SiO_x films, 150 nm thick formed at room temperature by thermal evaporation in vacuum, into SiO₂ films with a Si-O-Si bonding network similar to that of thermally grown SiO₂ films. Heat treatment at 130 °C with 2.8×10⁵ Pa H₂O for 3 h reduced the recombination velocity for the electron minority carriers from 405 cm/s (as-fabricated 150-nm-thick SiO_x/Si) to 5 cm/s. Field-effect passivation was demonstrated by an additional deposition of defective SiO_x films on the SiO₂ films formed by heat treatment at 340 °C with high-pressure H₂O vapor. The SiO_x deposition reduced the recombination velocity from 100 cm/s to 48 cm/s. Received: 1 March 1999 / Accepted: 28 March 1999 / Published online: 24 June 1999     

Quantum confined luminescence in Si/SiO2 superlattices

Amorphous Si/SiO₂ superlattices with periodicities between 2 and 5 nm have now been grown on (1 00) Si wafers by several different techniques: molecular beam epitaxy, magnetron sputtering, and plasma enhanced chemical vapor deposition (PECVD). With the first two methods little or no hydrogen is incorporated during growth and visible photo-luminescence (PL) is obtained at wavelengths from 520 to 800 nm. The shift in the PL peak position with Si layer thickness is consistent with quantum confined band-to-band recombination. Annealing the sputtered superlattices at temperatures up to 1100°C results in a very bright red PL that is similar in intensity to that observed in porous Si samples. For large numbers of periods (e.g., 425) the PL is strongly modulated in intensity owing to optical interference within the superlattice. Similar quantum confined, but defect induced, PL is also observed in the PECVD grown superlattices, where the amorphous Si layers are heavily hydrogenated.     

Silicon negative ion implantation induced vacancy defects in thermally grown SiO2 thin films

ABSTRACT

Thermally grown SiO₂ thin films on a silicon substrate implanted with 100?keV silicon negative ions with fluences varying from 1?×?10¹⁵ to 2?×?10¹⁷ ions cm^?2 have been investigated using Electron spin resonance, Fourier transforms infrared and Photoluminescence techniques. ESR studies revealed the presence of non-bridging oxygen hole centers, E′-centers and P_b-centers at g-values 2.0087, 2.0052 and 2.0010, respectively. These vacancy defects were found to increase with respect to ion fluence. FTIR spectra showed rocking vibration mode, stretching mode, bending vibration mode, and asymmetrical stretching absorption bands at 460, 614, 800 and 1080?cm^?1, respectively. The concentrations of Si–O and Si–Si bonds estimated from the absorption spectra were found to vary between 11.95?×?10²¹ cm^?3 and 5.20?×?10²¹ cm^?3 and between 5.90?×?10²¹ cm^?3 and 3.90?×?10²¹ cm^?3, respectively with an increase in the ion fluence. PL studies revealed the presence of vacancies related to non-bridging oxygen hole centers, which caused the light emission at a wavelength of 720?nm.