Si-nanostructures formation in amorphous silicon nitride SiNx:H deposited by remote PECVD

The formation of silicon nanoclusters embedded in amorphous silicon nitride (SiN_x:H) can be of great interest for optoelectronic devices such as solar cells. Here amorphous SiN_x:H layers have been deposited by remote microwave-assisted chemical vapor deposition at 300 °C substrate temperature and with different ammonia [NH₃]/silane [SiH₄] gas flow ratios (R=0.5−5). Post-thermal annealing was carried out at 700 °C during 30 min to form the silicon nanoclusters. The composition of the layers was determined by Rutherford back scattering (RBS) and elastic recoil detection analysis (ERDA). Fourier transform infrared spectroscopy (FTIR) showed that the densities of SiH (2160 cm⁻¹) and NH (3330 cm⁻¹) molecules are reduced after thermal annealing for SiN:H films deposited at flow gas ratio R>1.5. Breaking the SiH bonding provide Si atoms in excess in the bulk of the layer, which can nucleate and form Si nanostructures. The analysis of the photoluminescence (PL) spectra for different stoichiometric layers showed a strong dependence of the peak characteristics (position, intensity, etc.) on the gas flow ratio. On the other hand, transmission electron microscopy (TEM) analysis proves the presence of silicon nanoclusters embedded in the films deposited at a gas flow ratio of R=2 and annealed at 700 °C (30 min).     

Investigation on preparation and physical properties of nanocrystalline Si/SiO2 superlattices for Si-based light-emitting devices

Structures containing silicon nanocrystals (nc-Si) are very promising for Si-based light-emitting devices. Using a technology compatible with that of silicon, a broader wavelength range of the emitted photoluminescence (PL) was obtained with nc-Si/SiO₂ multilayer structures. The main characteristic of these structures is that both layers are light emitters. In this study we report results on a series of nc-Si/SiO₂ multilayer periods deposited on 200 nm thermal oxide SiO₂/Si substrate. Each period contains around 10 nm silicon thin films obtained by low-pressure chemical vapour deposition at T=625°C and 100 nmSiO₂ obtained by atmospheric pressure chemical vapour deposition T=400°C. Optical and microstructural properties of the multilayer structures have been studied by spectroscopic ellipsometry (using the Bruggemann effective medium approximation model for multilayer and multicomponent films), FTIR and UV–visible reflectance spectroscopy. IR spectroscopy revealed the presence of SiO_x structural entities in each nc-Si/SiO₂ interface. Investigation of the PL spectra (using continuous wave-CW 325 nm and pulsed 266 nm laser excitation) has shown several peaks at 1.7, 2, 2.3, 2.7, 3.2 and 3.7 eV, associated with the PL centres in SiO₂, nc-Si and Si–SiO₂ interface. Their contribution to the PL spectra depends on the number of layers in the stack.     

Thermal annealing dependence of some optical properties of plasma-modified porous silicon

The photoluminescence and reflectance of porous silicon (PS) with and without hydrocarbon (CH_x) deposition fabricated by plasma enhanced chemical vapour deposition (PECVD) technique have been investigated. The PS samples were then, annealed at temperatures between 200 and 800 °C. The influence of thermal annealing on optical properties of the hydrocarbon layer/porous silicon/silicon structure (CH_x/PS/Si) was studied by means of photoluminescence (PL) measurements, reflectivity and ellipsometry spectroscopy. The composition of the PS surface was monitored by transmission Fourier transform infrared (FTIR) spectroscopy. Photoluminescence and reflectance measurements were carried out before and after annealing on the carbonized samples for wavelengths between 250 and 1200 nm. A reduction of the reflectance in the ultraviolet region of the spectrum was observed for the hydrocarbon deposited polished silicon samples but an opposite behaviour was found in the case of the CH_x/PS ones. From the comparison of the photoluminescence and reflectance spectra, it was found that most of the contribution of the PL in the porous silicon came from its upper interface. The PL and reflectance spectra were found to be opposite to one another. Increasing the annealing temperature reduced the PL intensity and an increase in the ultraviolet reflectance was observed. These observations, consistent with a surface dominated emission process, suggest that the surface state of the PS is the principal determinant of the PL spectrum and the PL efficiency.     

Structural, optical and electrical properties of ZnO/Zn2GeO4 porous-like thin film and wires

Zinc oxide/zinc germanium oxide (ZnO/Zn₂GeO₄) porous-like thin film and wires has been fabricated by simple thermal evaporation method at temperature about 1120 °C for 2.5 h. The structural and optical properties of the porous-like-thin film and wires have been investigated by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. Metal semiconductor metal (MSM) photodetector structure was used to evaluate the electrical characteristics by using current-voltage (I-V) measurements. Room temperature photoluminescence spectrum of the sample shows one prominent ultraviolet peak at 378 nm and a shoulder at 370 nm. In addition, broad visible blue emission peak at wavelength 480 nm and green emission peak at 500 nm are also observed. Strong photoelectric properties of the MSM in the UV demonstrated that the porous-like-thin film and wires contribute to its photosensitivity and therefore making ZnO/Zn₂GeO₄ wires potential photodetector in the shorter wavelength applications.     

Visible photoluminescence from silicon nanoclusters embedded in silicon nitride films prepared by remote plasma-enhanced chemical vapor deposition

The photoluminescence (PL) of silicon nanoclusters embedded in silicon nitride films grown by remote plasma-enhanced chemical vapor deposition at 200 °C, using mixtures of SiCl₄/H₂/Ar/NH₃ is investigated. It was found that the color and the intensity of the PL of the as-grown samples depend on the H₂ flow rate, and there is an optimum flow for which a maximum luminescence is obtained. A strong improvement of the PL intensity and change in color was obtained with annealing treatments in the range of 500–1000 °C. The changes in the composition, structure and optical properties of the films, as a function of H₂ flow rate and thermal treatments, were studied by means of Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, ellipsometry and ultraviolet–visible transmission measurements. We conclude that the PL can be attributed to quantum confinement effect in silicon nanoclusters embedded in silicon nitride matrix, which is improved when a better passivation of the nanoclusters surface is obtained.     

Room temperature visible light emission from Si/SiO2 multilayers: Roles of interface electronic states and silicon phase

We have studied luminescence properties and microstructure of 20 patterns Si/SiO₂ multilayers. The photoluminescence spectra consist of two gaussian bands in the visible-infrared spectral region. It has been demonstrated that the strong PL band is caused by the radiative recombination in the Si/SiO₂ interfaces states, whereas the weaker band originates from radiative recombination in the nanosized Si layers. The peak shift of this latter band shows a discontinuity that corresponds to a crystalline-to-amorphous phase change when the Si layers are thinner than 30 Å. The peak energy as a function of the layer thickness is interpreted using a quantum confinement model in the case of amorphous Si layers.     

Structure and luminescent properties of LaNbO4 synthesized by sol-gel process

The luminescence properties of LaNbO₄ synthesized by the citric gel process were investigated. The crystallized orthorhombic and monoclinic biphasic structure forms at temperatures below 1100 °C and well-crystallized monoclinic LaNbO₄ is obtained by heat treatment at a temperature of 1200 °C for 3 h. All of LaNbO₄ phosphors derived from the citric gel method exhibit red-shifted excitation spectra as the calcining temperature increased from 700 to 1200 °C. The effect of the heat treatment conditions on the peak shape and the peak positions of the photoluminescence (PL) emission are undetectable, and the PL spectra excited at 260 nm have a blue emission band maximum at 408 nm, corresponding to the self-activated luminescence center of LaNbO₄. The sample heat treated at 1100 °C for 3 h showed the highest absorption and fluorescence intensities among the prepared samples.     

Correlation between microstructure and optical properties of nano-crystalline TiO2 thin films prepared by sol-gel dip coating

Titanium dioxide thin films have been prepared from tetrabutyl-orthotitanate solution and methanol as a solvent by sol-gel dip coating technique. TiO₂ thin films prepared using a sol-gel process have been analyzed for different annealing temperatures. Structural properties in terms of crystal structure were investigated by Raman spectroscopy. The surface morphology and composition of the films were investigated by atomic force microscopy (AFM). The optical transmittance and reflectance spectra of TiO₂ thin films deposited on silicon substrate were also determined. Spectroscopic ellipsometry study was used to determine the annealing temperature effect on the optical properties and the optical gap of the TiO₂ thin films. The results show that the TiO₂ thin films crystallize in anatase phase between 400 and 800 °C, and into the anatase-rutile phase at 1000 °C, and further into the rutile phase at 1200 °C. We have found that the films consist of titanium dioxide nano-crystals. The AFM surface morphology results indicate that the particle size increases from 5 to 41 nm by increasing the annealing temperature. The TiO₂ thin films have high transparency in the visible range. For annealing temperatures between 1000 and 1400 °C, the transmittance of the films was reduced significantly in the wavelength range of 300-800 nm due to the change of crystallite phase and composition in the films. We have demonstrated as well the decrease of the optical band gap with the increase of the annealing temperature.     

Ion-beam irradiation effect on solid-phase growth of β-FeSi2

Effects of Ar⁺ ion-beam irradiation on solid-phase growth of β-FeSi₂ have been investigated. Fe (10 nm)/Si structures were irradiated with 25 keV Ar⁺ (5.0×10¹⁵ cm⁻²) at a temperature of 25°C (sample A) or 400°C (sample B), and subsequently annealed at 800°C. A reference was obtained after annealing without irradiation (sample C). X-ray diffraction results indicated that β-FeSi₂ was formed after annealing at 800°C for 5 h, and the formation rate was the fastest for sample A and the slowest for sample C, i.e., A>BC. However, Auger electron spectroscopy measurements showed that atomic mixing at Fe/Si interface before annealing was B>AC. These results suggested that amorphization of Si substrate, in addition to atomic mixing, enhanced the solid-phase growth of β-FeSi₂, which was confirmed experimentally. Moreover, a direct band gap of 0.89 eV was observed for the sample with pre-amorphization by the Fourier-transform infrared (FT-IR) spectroscopy measurements. These enhancement effects were attributed to that the phase transition to β-FeSi₂ was accelerated by atomic arrangement induced during annihilation of excess vacancies. These enhancement effects can be utilized for nano-fabrication of β-FeSi₂ by using focused ion-beam irradiation.     

Annealing effect on the optical properties in Si delta-doped Al0.24Ga0.76As/In0.15Ga0.85As/GaAs pseudomorphic high electron mobility transistor structures

The optical properties of Si delta-doped Al_0.24Ga_0.76As/In_0.15Ga_0.85As/GaAs pseudomorphic high electron mobility transistor structure (PHEMTs) are estimated after the process of rapid thermal annealing (RTA) in the temperature range 500–750°C. After layer intermixing and decrease of 2DEG densities of PHEMTs just occurs around the annealing temperature of 650°C, the 12H transition peak at 1.354 eV above the annealing temperature of 650°C is newly observed from the photoluminescence (PL) and photoreflectance (PR) spectra. From the results of PL and PR measurements in the annealed PHEMTs, it is found that remarkable modification of band profile in InGaAs QW occur at annealing temperature above 650°C.     

Luminescent silicon nanocrystal dots fabricated by SiCl4/H2 RF plasma-enhanced chemical vapor deposition

Luminescent nanocrystalline Si dots were fabricated directly on thermally grown SiO₂ at 120°C by conventional RF plasma-enhanced chemical vapor deposition using tetrachlorosilane, SiCl₄ and H₂. As-deposited Si dot exhibits photoluminescence (PL) in the visible region, consisting of two broad bands corresponding to photon energies of 1.38 and 1.48 eV. Storage in air enhances PL and shifts the PL peak energy to higher wavelengths for dots of diameter less than 10 nm. Fourier transform attenuated total reflection absorption spectroscopy (FTIR-ATR) study reveals that the spontaneous oxidation proceeds until saturation after 70 h at dot sizes of 3–5 nm. The relationship between PL intensity, blueshift of PL peak energy, and surface termination species during oxidation indicates that these changes are attributed to the increased density of radiative centers at the Si nanocrystal dot/SiO₂ interface and enhancement of the quantum confinement effect.     

The effect of Si surface nitridation on the interfacial structure and electrical properties of (La2O3)0.5(SiO2)0.5 high-k gate dielectric films

Thermal stability, interfacial structures and electrical properties of amorphous (La₂O₃)_0.5(SiO₂)_0.5 (LSO) films deposited by using pulsed laser deposition (PLD) on Si (1 0 0) and NH₃ nitrided Si (1 0 0) substrates were comparatively investigated. The LSO films keep the amorphous state up to a high annealing temperature of 900 °C. HRTEM observations and XPS analyses showed that the surface nitridation of silicon wafer using NH₃ can result in the formation of the passivation layer, which effectively suppresses the excessive growth of the interfacial layer between LSO film and silicon wafer after high-temperature annealing process. The Pt/LSO/nitrided Si capacitors annealed at high temperature exhibit smaller CET and EOT, a less flatband voltage shift, a negligible hysteresis loop, a smaller equivalent dielectric charge density, and a much lower gate leakage current density as compared with that of the Pt/LSO/Si capacitors without Si surface nitridation.     

Photoluminescence of GeSi/Si(0 0 1) self-assembled islands with dome and hut shape

The photoluminescence spectra of GeSi/Si (0 0 1) self-assembled islands produced by solid source molecular beam epitaxy in a wide range (460–700°C) of growth temperatures were investigated. The results showed a blue shift of the island-related photoluminescence peak with a growth temperature lowering from 600°C to 550°C. The observed blue shift of the island photoluminescence peak is associated with a sharp decrease in the average height of the island, which occurs through a change of its shape from dome to hut as the growth temperature lowers from 600°C to 550°C.     

Influence of the SiO thickness on the photoluminescence properties of Er-doped SiO/SiO2 multilayers

Er-doped SiO single layer and Er-doped SiO/SiO₂ multilayers with different SiO thicknesses were prepared by evaporation. In the as-deposited samples, the erbium ions exhibit a very weak photoluminescence emission at 1.54 μm. This luminescence is strongly enhanced after annealing treatments between 500 and 1050 °C, with an optimal annealing temperature which is dependent from the SiO thickness. For the SiO single layer, this optimal temperature is around 700 °C while it is shifted at highest temperature for the multilayers. The origin of the higher luminescence intensity in the SiO layer is also discussed.     

Preparation and electrical properties of a pyrochlore-related Ce2Zr2O8−x phase

A pyrochlore-related Ce₂Zr₂O_8−x phase has been prepared in a reduction reoxidation process from Ce_0.5Zr_0.5O₂ powders. Ce₂Zr₂O_8−x, based on a cubic symmetry with a=1.053 nm, decomposes in nitrogen at 800 °C, but remains stable up to 900 °C in air. It shows mixed oxygen ionic and electronic conductivity. The bulk conductivity at 700 °C is 4×10⁻⁴ S cm⁻¹ in air and 1×10⁻² S cm⁻¹ in nitrogen, and the activation energy is 1.27 eV in air. In nitrogen, the Arrhenius law is not obeyed, and a curved plot was obtained from 400 to 700 °C; then, the conductivity decreased rapidly due to the thermal decomposition of Ce₂Zr₂O_8−x.     

Generation of optically active states in a-SiNx by thermal treatment

Amorphous silicon nitride (a-SiN_x) films were deposited using plasma-enhanced chemical-vapor deposition (PECVD) and subsequently, thermal annealing processes were performed at 700-1000 °C in the ultra-high vacuum (UHV) condition. A strong photoluminescence (PL) peak induced by luminescent defect centers was observed at 710 nm for the as-deposited sample. When the sample was annealed at 700-1000 °C, the PL peak intensity became about 3-12 times stronger with no shift of the PL peak. To investigate the origin of the change in PL peak intensity after the thermal annealing, Si 2p and N 1s core-level spectra were systematically analyzed by high-resolution photoemission spectroscopy (HRPES) using synchrotron radiation. In particular, N 1s spectra were decomposed with three characteristic nitrogen-bonding states. It is revealed that the nitrogen bonding state with N-Si and NSi₂ configurations (denoted as N3) contributes mainly to the change in PL peak intensity. We note that luminescent nitrogen related defect centers such as N₄⁺ and N₂° are localized in the state N3. Detailed analysis of the experimental results shows that the state N3 is located in the interface bounded by the region of the nano-sized stoichiometric silicon nitride Si₃N₄ (denoted as N1) and is considerably influenced by the thermal annealing, which is an appropriate process to cause strong photoluminescence of the related samples as mentioned above.     

Preparation and luminescent characteristic of Li3NbO4 nanophosphor

Synthesis and luminescence properties of Li₃NbO₄ oxides by the sol-gel process were investigated. The products were characterized by the X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy and absorption spectra. The PL spectra excited at 247 nm have a broad and strong blue emission band maximum at 376 nm, corresponding to the self-activated luminescence of the niobate octahedra group [NbO₆]⁷⁻. The optical absorption spectra of the samples sintered at temperatures of 600 and 700 °C exhibited the band-gap energies of 4.0 and 4.08 eV.     

Thermoluminescent and stuctural properties of BaAl2O4:Eu,Nd,Gdphosphors prepared by combustion method

BaAl₂O₄:Eu²⁺,Nd³⁺,Gd³⁺ phosphors were prepared by a combustion method at different initiating temperatures (400–1200 °C), using urea as a comburent. The powders were annealed at different temperatures in the range of 400–1100 °C for 3 h. X-ray diffraction data show that the crystallinity of the BaAl₂O₄ structure greatly improved with increasing annealing temperature. Blue-green photoluminescence, with persistent/long afterglow, was observed at 498 nm. This emission was attributed to the 4f⁶5d¹–4f⁷ transitions of Eu²⁺ ions. The phosphorescence decay curves were obtained by irradiating the samples with a 365 nm UV light. The glow curves of the as-prepared and the annealed samples were investigated in this study. The thermoluminescent (TL) glow peaks of the samples prepared at 600 °C and 1200 °C were both stable at ∼72 °C suggesting that the traps responsible for the bands were fixed at this position irrespective of annealing temperature. These bands are at a similar position, which suggests that the traps responsible for these bands are similar. The rate of decay of the sample annealed at 600 °C was faster than that of the sample prepared at 1200 °C.     

Photoluminescence spectra of laser-synthesized Si/C/N ultrafine powders

Ultrafine Si/C/N ceramic powders were synthesized by a CO₂-laser-induced reaction between silane (SiH₄), ammonia (NH₃) and acetylene (C₂H₂). The powders were characterized by infrared (IR) reflection and photoluminescence (PL) spectroscopy. From the infrared reflection spectra of Si/C/N powders, we have identified the causes of the strong photoluminescence present in these powders. The photoluminescence spectra of Si/C/N powders originate from the presence of hydroxylated and amorphous silicon (a-SiO₂) formed at the porous surface of these powders. We have shown that different chemical bonding between Si, C and N atoms, the degree of crystallinity of ternary powders and their porosity strongly influence the processes at their surface, i.e. the formation of amorphous silicon and silanole. Received: 16 June 2000 / Accepted: 24 June 2000 / Published online: 9 November 2000     

Effect of BiFeO3 addition on Bi2O3–ZnO–Nb2O5 based ceramics

In this paper, low temperature sintering of the Bi₂(Zn_1/3Nb_2/3)₂O₇ (β-BZN) dielectric ceramics was studied with the use of BiFeO₃ as a sintering aid. The effects of BiFeO₃ contents and the sintering temperature on the phase structure, density and dielectric properties were investigated. The results showed that the sintering temperature could be decreased and the dielectric properties could be retained by the addition of BiFeO₃. The structure of BiFeO₃ doped β-BZN was still the monoclinic pyrochlore phase. The sintering temperature of BiFeO₃ doped β-BZN ceramics was reduced from 1000 °C to 920 °C. In the case of 0.15 wt.% BiFeO₃ addition, the β-BZN ceramics sintered at 920 °C exhibited good dielectric properties, which were listed as follows: ε_r = 79 and tan δ = 0.00086 at a frequency of 1 MHz. The obtained properties make this composition to be a good candidate for the LTCC application.