Blue photo- and electroluminescence of silicon dioxide layers ion-implanted with group IV elements

The microstructural, optical and electrical properties of Si-, Ge- and Sn-implanted silicon dioxide layers were investigated. It was found, that these layers exhibit strong photoluminescence (PL) around 2.7 eV (Si) and between 3 and 3.2 eV (Ge, Sn) at room temperature (RT), which is accompanied by an UV emission around 4.3 eV. This PL is compared with that of Ar-implanted silicon dioxide and that of Si- and Ge-rich oxide made by rf magnetron sputtering. Based on PL and PL excitation (PLE) spectra we tentatively interpret the blue–violet PL as due to a T₁→S₀ transition of the neutral oxygen vacancy typical for Si-rich SiO₂ and similar Ge- or Sn-related defects in Ge- and Sn-implanted silicon dioxide. The differences between Si, Ge and Sn will be explained by means of the heavy atom effect. For Ge-implanted silicon dioxide layers a strong electroluminescence (EL) well visible with the naked eye and with a power efficiency up to 5×10^-4 was achieved. The EL spectrum correlates very well with the PL one. Whereas the EL intensity shows a linear dependence on the injection current over three orders of magnitude, the shape of the EL spectrum remains unchanged. The I-V dependence exhibiting the typical behavior of Fowler–Nordheim tunneling shows an increase of the breakdown voltage and the tunnel current in comparison to the unimplanted material. Finally, the suitability of Ge-implanted silicon dioxide layers for optoelectronic applications is briefly discussed. Received: 9 March 2000 / Published online: 30 June 2000     

Dislocation-related luminescence in Er-implanted silicon

The behavior of luminescence spectra and structural defects in single crystal Czochralski silicon after erbium implantation at 1–1.8 MeV energies and 1×10¹³ cm⁻² dose with subsequent annealing at 1000–1200°C for 0.25–3 h in argon and a chlorine-containing ambience (CCA) was studied by photoluminescence (PL), transmission electron microscopy and chemical etching/Nomarski microscopy. We have found that annealing in CCA gives rise to dislocation loops and pure edge dislocations with dominant dislocation-related lines in the PL spectrum. Pure edge dislocations are responsible for the appearance of the lines.     

Optical characterization of InGaN/AlGaN/GaN diode grown on silicon carbide

Electroluminescence (EL) properties of In_xGa_1−xN/Al_yGa_1−yN/GaN/SiC diode were studied. The spectral range for which EL spectra were recorded is 1–3.5 eV. Room temperature EL was obtained for forward bias (3.18 V, 220 μA) at 446.067 nm (blue luminescence band), 606.98 nm (yellow luminescence band) and 893.84 nm (Infrared luminescence band). The EL temperature dependence shows that, BL band is mostly given by e–h recombination corresponding to indium composition equal to 0.17 ± 0.01 and 0.14 ± 0.02 obtained theoretically and experimentally, respectively. The yellow band is generally weak and absent at low temperature. The IRL band is more consistent with the DAP recombination and could be explained by the thermal activation of Mg states. The luminescence bands shift to lower energies is due probably to the larger potential fluctuations effect.     

Cathodoluminescence properties of silicon nanocrystallites embedded in silicon oxide thin films

Cathodoluminescence (CL) spectra for the Si nanocrystallites embedded in a matrix of silicon oxide films are measured at room temperature. The CL spectra consist of two principal bands whose peak energies are in a near-infrared (NIR) region (<1.6 eV) and in a blue region (2.6 eV), respectively. The spectral feature of the NIR CL band is similar to the corresponding PL spectra. The strong correlation between the presence of Si nanocrystallites and the formation of the NIR CL band are found as well as the PL spectrum. The peak energy of the blue CL band is slightly lower than that of the luminescence band originating from oxygen vacancies (≡Si–Si≡) in SiO₂. Therefore, the blue CL band is considered to come from Si_n clusters with n3 in the oxide matrix. Under irradiation of electron beams, degradation of the intensity is observed for both the CL bands but the decay characteristics are different.     

Characterization of high-k gate dielectric/silicon interfaces

We have shown that, for thermally evaporated Ta₂O₅ or ZrO₂ thin films on Si(1 0 0), O₂ annealing at 300–500 °C causes the formation of an interfacial silicon oxide layer as thin as 1–2 nm which can be interpreted in terms of their high permeability to oxygen. And we have demonstrated how useful the energy loss spectra of photoexcited electrons from core levels such as O 1s are to measure the energy bandgaps of very thin insulators. With the combination of measured bandgaps and valence band lineups determined for X-ray photoelectron spectroscopy valence band spectra, we have determined the energy band alignments of Ta₂O₅ and ZrO₂ with Si(1 0 0) before and after the O₂ annealing at 500 °C. In addition, we have demonstrated that total photoelectron yield spectroscopy provides us direct information to quantify the energy distributions of both the defect states in the high-k dielectrics and the dielectric/Si(1 0 0) interface states over nearly entire Si bandgap.     

Tunable photoluminescence and electroluminescence of size-controlled silicon nanocrystals in nanocrystalline-Si/SiO2 superlattices

We present photoluminescence and electroluminescence of silicon nanocrystals deposited by plasma-enhanced chemical vapor deposition (PECVD) using nanocrystalline silicon/silicon dioxide (nc-Si/SiO₂) superlattice approach. This approach allows us to tune the nanocrystal emission wavelength by varying the thickness of the Si layers. We fabricate light emitting devices (LEDs) with transparent indium tin oxide (ITO) contacts using these superlattice materials. The current-voltage characteristics of the LEDs are measured and compared to Frenkel-Poole and Fowler-Nordheim models for conduction. The EL properties of the superlattice material are studied, and tuning, similar to that of the PL spectra, is shown for the EL spectra. Finally, we observe the output power and calculate the quantum efficiency and power conversion efficiency for each of the devices.     

The effect of annealing under hydrostatic pressure on the visible photoluminescence from si-ion implanted SiO2 films

We have studied the influence of the hydrostatic pressure during annealing on the intensity of the visible photoluminescence (PL) from thermally grown SiO₂ films irradiated with Si⁺ ions. Post-implantation anneals have been carried out in an Ar ambient at temperatures T_a of 400°C and 450°C for 10 h and 1130°C for 5 h at hydrostatic pressures of 1 bar–15 kbar. It has been found that the intensity of the 360, 460 and 600 nm PL peaks increases with rising hydrostatic pressure during low-temperature annealing. The intensity of the short-wavelength PL under conditions of hydrostatic pressure continues to rise even at T_a=1130°C. Increasing T_a leads to a shift in the PL spectra towards the ultraviolet range. The results obtained have been interpreted in terms of enhanced, pressure-mediated formation of ≡Si–Si≡ centres and small Si clusters within metastable regions of the ion-implanted SiO₂.     

Comparative study of the oxidation of thin porous silicon layers studied by reflectometry, spectroscopic ellipsometry and secondary ion mass spectroscopy

We present a systematic study on ultrathin porous silicon (PS) layers (40–120 nm) of different porosities, formed by electrochemical etching and followed by thermal oxidation treatment (300°C and 600°C) and by electrochemical oxidation. The oxidised and non-oxidised PS layers have been analysed by spectroscopic reflectometry (SR), spectroscopic ellipsometry (SE) and secondary ion mass spectroscopy (SIMS). The SR and SE spectra were fitted by a multiparameter fit program and the composition and the thickness of the PS layers were evaluated by different optical models. PS layers, formed electrochemically in the outermost layer of a p/n⁺ monocrystalline silicon junction were successfully evaluated using a gradient porosity optical model. The non-oxidised PS, formed in p-type silicon, can be well described by a simple optical model (one-layer of two-components, silicon and voids). The spectra of the oxidised PS layers can be fitted better using an optical model with three interdependent components (crystalline-silicon, silicon-dioxide, voids). The SIMS results give a strong support for the optical model used for SR and SE.     

The origin of photoluminescence in Ge-implanted SiO2 layers

Ge ions were implanted at 100 keV with 3×10¹⁶ cm⁻² into a 300  nm thick SiO₂ layer on Si. Visible photoluminescence (PL) around 2.1 eV from an as-implanted sample is observed, and faded out by subsequent annealing at 900°C for 2 h. However, PL shows up again after annealing above 900°C at the same peak position. Compared with the as-implanted sample, significant increase of Ge–Ge bonds is measured in X-ray photoelectron spectroscopy, and the formation of Ge nanocrystals with a diameter of 5 nm are observed in transmission electron microscopy from the sample annealed at 1100°C. We conclude that the PL peak from the sample annealed above 900°C is caused by the quantum confinement effects from Ge nanocrystals, while the luminescence from the as-implanted sample is due to some radiative defects formed by Ge implantation.     

EXAFS analysis of Er sites in Er–O and Er–F co-doped crystalline Si

We present extended X-ray absorption fine structure (EXAFS) and photoluminescence (PL) analyses of Er–O and Er–F co-doped Si. Samples were prepared by multiple implants at 77 K of Er and co-dopant (O or F) ions resulting in the formation of a2 μm thick amorphous layer uniformly doped with 1×10¹⁹ Er/cm³ and 3×10¹⁹ O/cm³, 1×10²⁰ O/cm³ or 1×10²⁰ F/cm³. EXAFS measurements show that the local environment of the Er sites in the amorphous layers consists of 6 Si first neighbors. After epitaxial regrowth at 620°C for 3 h, Er is fully coordinated with 8 F ions in the Er–F samples, while Si and O ions are concomitantly present in the first shell of O co-doped samples. Post regrowth thermal treatments at 900°C leave the coordination unchanged in the Er+F, while the Er+O (ratio 1 : 10) doped samples present Er sites with a fully O coordinated shell with an average of 5 O atoms and 4 O atoms after 30 s and 12 h, respectively. We have also found that the fine structure and intensity of the high-resolution PL spectra are strongly dependent on the Er-impurity ratio and on thermal process parameters in the Er–O co-doped samples, while this is not observed for the F-doped samples. The most intense PL response at 15 K was obtained for the 1 : 3 E : O ratio, suggesting that an incomplete O shell around Er is particularly suitable for optical excitation.     

Ellipsometric spectroscopy study of photoluminescent Si/SiO2 systems obtained by magnetron co-sputtering

Si nanograins embedded in silica matrix were obtained by magnetron cosputtering of both Si and SiO₂ at different substrate temperature (200–700°C) and thermal annealing at 1100°C. The samples were characterized by ellipsometric spectroscopy, high-resolution electron microscopy observations and photoluminescence. The highest excess of Si atoms was found to be incorporated for deposition temperature near 400–500°C, giving rise to a maximum PL and a shift of the peak position towards lower energy. These features might be interpreted in terms of quantum size effects and of density of grains, even though the interface states seem to be involved in the improvement of the photoluminescence efficiency.     

Effects of precursors on nucleation in atomic layer deposition of HfO2

Atomic layer deposition of hafnium dioxide (HfO₂) on silicon substrates was studied. It was revealed that due to low adsorption probability of HfCl₄ on silicon substrates at higher temperatures (450–600 °C) the growth was non-uniform and markedly hindered in the initial stage of the HfCl₄–H₂O process. In the HfI₄–H₂O and HfI₄–O₂ processes, uniform growth with acceptable rate was obtained from the beginning of deposition. As a result, the HfI₄–H₂O and HfI₄–O₂ processes allowed deposition of smoother, more homogeneous and denser films than the HfCl₄–H₂O process did. The crystal structure developed, however, faster at the beginning of the HfCl₄–H₂O process.     

Defect versus nanocrystal luminescence emitted from room temperature and hot-implanted SiO2 layers

Silicon nanocrystals have been synthesized in SiO₂ matrix using Si ion implantation. Si ions were implanted into 300-nm-thick SiO₂ films grown on crystalline Si at energies of 30–55 keV, and with doses of 5×10¹⁵, 3×10¹⁶, and 1×10¹⁷ cm⁻². Implanted samples were subsequently annealed in an N₂ ambient at 500–1100°C during various periods. Photoluminescence spectra for the sample implanted with 1×10¹⁷ cm⁻² at 55 keV show that red luminescence (750 nm) related to Si-nanocrystals clearly increases with annealing temperature and time in intensity, and that weak orange luminescence (600 nm) is observed after annealing at low temperatures of 500°C and 800°C. The luminescence around 600 nm becomes very intense when a thin SiO₂ sample is implanted at a substrate temperature of 400°C with an energy of 30 keV and a low dose of 5×10¹⁵ cm⁻². It vanishes after annealing at 800°C for 30 min. We conclude that this luminescence observed around 600 nm is caused by some radiative defects formed in Si-implanted SiO₂.     

Oxygen tracer diffusion in La1 − xSrxCoO3

Tracer diffusion of ¹⁸O in dense, polycrystalline La_1−xSr_xCoO₃ for x = 0.1 has been measured in the temperature range 400 to 600 °C and at 500 °C for x = 0.2 at an oxygen partial pressure of 1 × 10⁵ Pa. Depth profiles were obtained by secondary ion mass spectrometry. The diffusion coefficient for La_0.9Sr_0.1CoO₃ is given by D = (17–247) exp[(−232 ± 8 kJ/mole)/RT] cm²/s. This value is several orders of magnitude lower than D extrapolated from the results for x = 0.2 measured in the 700–900 °C temperature range. One possible explanation for the discrepancy is that the two measurements reflect different diffusion paths. As expected, La_0.8Sr_0.2CoO₃ exhibits a higher diffusivity at 500 °C than does La_0.9Sr_0.1CoO₃.     

Structural and optical features of nanoporous silicon prepared by electrochemical anodic etching

Nanoporous silicon (NPS) samples were prepared by electrochemical anodic etching of p-type (0 0 1) silicon wafers in HF solution, and some of them were aged in air. The nanostructural, optical and chemical features of the NPS were investigated in terms of etching and aging conditions. The surface of the porous Si exhibits an etched layer with a thickness of 30–40 nm; this layer appears to consist of aggregates of 5–10 nm size nano-crystallites. The NPS exhibited broad photoluminescence (PL) spectra with its peak in the red light region (740 nm). After aging the porous samples for 4 weeks in air, we observed the PL intensity became approximately a fifth of that of the as-prepared one, along with a blue shift. It is very likely that the blue shift of the PL peak was caused by the shrinkage of the Si nano-crystallites due to the oxidation in the surface of the nano-crystallites.     

Analysis of temperature and 1 MeV proton irradiation effects on the light emission in bulk silicon (npn) emitter-base bipolar junctions

In this work, we present the temperature and 1 MeV irradiation proton effects on the light emission in bulk silicon emitter-base junctions for direct and reverse polarizations. Our samples were exposed at room temperature to 5.3 × 10⁸, 5.3 × 10¹⁰, 5 × 10¹¹, 5 × 10¹² and 5 × 10¹³ p cm⁻². The spectral range for which electroluminescence spectrums were recorded for forward and reverse polarizations is 0.6–2 eV. For forward bias, EL maximum intensity occurs at 1.0923 ± 0.0001 eV (structure (a)) which decreases as function of irradiation fluencies. For reverse bias, the spectra contain two structures (b) and (c). The first structure (c) occurred at 1.6243 ± 0.0013 eV is independent of irradiation while the second structure (b) decreases as function of fluencies irradiation. The Gaussian deconvolution of (b) shows two sub-structures (b₁) and (b₂) which are located, respectively, at 0.8064 ± 0.0004 eV and 0.9917 ± 0.0016 eV. We studied temperature dependence of full width at half-maximum (FWHM) and we found that the phonons involved in (a), (b₁) and (b₂) on the one hand and (c) on the other hand are not the same. Moreover, we obtained from the study of EL intensity temperature dependence that the activation energies of (a), (b₁) and (b₂) are identical and differ from that of (c). These effects enable us to conclude that visible light emission does not have the same origin as that in infra-red. From these observations, we can attribute the structures (a) and (b) to indirect inter-bands transitions and (c) to a direct intra-band transitions.     

Light-emitting structures based on nanocrystalline (Si/CaF2) multiquantum wells

Periodic nanocrystalline (Si/CaF₂) multilayers, deposited on (111) silicon by Molecular Beam Epitaxy (MBE) at room temperature, were used to fabricate simple light emitting structures and to study their electrical and optoelectronic properties. Photoluminescence (PL) and electroluminescence (EL) spectra from the same area of the devices are approximately the same, indicative of the same emission mechanism. Current–voltage characteristics reveal important phenomena in vertical carrier transport. Regions of negative differential resistance and current oscillations were observed and were tentatively attributed to resonant tunneling at high electric fields under field domain formation.     

Amorphous Si/insulator multilayers grown by vacuum deposition and electron cyclotron resonance plasma treatment

a-Si/insulator multilayers have been deposited on (0 0 1) Si by electron gun Si evaporation and periodic electron cyclotron resonance plasma oxidation or nitridation. Exposure to an O or N plasma resulted in the formation of a thin SiO₂ and SiN_x layer whose thickness was self-limited and controlled by process parameters. For thin-layer (2 nm) Si/SiO₂ and Si/SiN_x multilayers no visible photoluminescence (PL) was observed in most samples, although all exhibited weak “blue” PL. For the nitride multilayers, annealing at 750°C or 850°C induced visible PL that varied in peak energy with Si layer thickness. Depth profiling of a-Si caps on thin insulating layers revealed no detectable contamination for the SiN_x layers, but substantial O contamination for the SiO₂ films.     

INFLUENCE OF C+-IMPLANTATION DOSE ON BLUE EMISSION AND MICROSTRUCTURES OF Si-BASED POROUS β-SIC

Crystal Si were implanted with different doses of C⁺ from 10¹¹ to 10¹⁷ cm^-2 at an energy of 50 keV. β-SiC precipitates were formed by thermal annealing at 1050 ℃ for 1 h and porous structures were prepared by electrochemical anodization. Under the excitation of ultraviolet, the samples, with C⁺ dose ≥10¹⁵ cm^-2 have intense blue emission which is stronger than the photoluminescence (PL) intensity of reference porous silicon (PS), and increases as C⁺ dose increases; the samples with C⁺ dose ≤10¹⁴ cm^-2 show similar PL spectra to those of PS. The blue peak intensity in PL spectra is correlated with the TO phonon absorption strength of β-SiC in infrared absorption spectra. The transmission electron microscopy study shows that the blue peak is also correlated with the microstructures. Because porous β-SiC is nanometer in size, it is suggested that the quantum confinement effect be responsible for the blue light emission.     

Interface states and impurities in MOS structures with very thin tunneling barriers

Electron tunneling spectroscopy was used to investigate MOS junctions with very thin silicon oxide or silicon oxynitride layers (2–5 nm) as tunneling barriers. For the tunneling measurements at 4.2 K highly degenerate P-doped (3×10²⁰ cm^-3) Si substrates, oxidized in dry oxygen at 600°C were used. Silicon oxynitride layers were prepared by plasma nitridation in an NH₃ discharge. As gate electrodes evaporated films of Al, Au or Pb were utilized. Changes in the tunneling conductivity were attributed to changes in the density of interface states, caused by hydrogen annealing or by high field stress. The results indicate a correlation between the generation of interface states and the removal of Si-H configurations. Vibrational modes of phonons, dopants and impurities were detected by inelastic electron tunneling spectroscopy.