Understanding and control of the erbium non-radiative de-excitation processes in silicon

Erbium doping of silicon has recently emerged as a promising method to tailor the optical properties of Si towards the achievement of a light emission at 1.54 μm. In this paper we will review our recent work on this subject. In particular a detailed investigation of the non-radiative processes, competing with the radiative emission of Er in Si will be presented. Among these processes, an Auger de-excitation with the energy released to free carriers will be demonstrated to be extremely efficient, with an Auger coefficient C_A4.4×10⁻¹³ cm³/s. Moreover, at temperatures above 100 K a phonon-assisted back-transfer decay process, characterized by an activation energy of 0.15 eV is seen to set in. This understanding of the physical properties competing with the radiative light emission allowed us to control them and obtain efficient room temperature luminescence. Two examples will be reported. It will be shown that by exciting Er within the depletion region of reverse biased p⁺–n⁺ Si diodes in the breakdown regime it is possible to avoid Auger quenching and to achieve high efficiency. Moreover, at the switch off of the diode, when the depletion region shrinks, the excited Er ions become suddenly embedded within the neutral heavily doped region of the device. In this region Auger de-excitation with free carriers sets in and quenches rapidly the luminescence. This allows to modulate the light signal at frequencies as high as a few MHz. Furthermore, the introduction of Er within Si nanocrystals is demonstrated to be a promising way to eliminate back-transfer processes by a widening of the bandgap while maintaining the full advantage of the efficient electron-hole mediated excitation present in Si. These data are presented and future perspective discussed.     

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.     

Luminescence of Er-doped silicon oxide-zirconia thin films

Er-doped silicon oxide-zirconia thin film samples were prepared by rf co-sputtering. Chemical composition was determined by energy-dispersive spectroscopy (EDS) and X-ray diffraction (XRD) showed that the films were amorphous. X-ray photoelectron spectroscopy (XPS) measurements showed that the matrix of the films consists of a ZrO₂ main body with pockets of silicon oxide, containing no Si nanoparticles (np) distributed within it. The samples were annealed to 700 °C. Er³⁺: ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, ⁴F_9/2→⁴I_15/2, ⁴I_11/2→⁴I_15/2, and ⁴I_13/2→⁴I_15/2 emissions were observed. Excitation wavelength dependence and excitation photon flux dependence results for the ⁴I_13/2→⁴I_15/2 emission were explained as due to resonant energy transfer from defects in the matrix. ⁴I_11/2→⁴I_15/2 emission dependence on ⁴I_13/2→⁴I_15/2 emission showed that no energy transfer upconversion (ETU) processes were involved and that it was due only to branching from higher levels. ⁴I_13/2→⁴I_15/2 peak intensity decay was interpreted as corresponding to two different populations of Er³⁺ ions. Energy transfer from the defects to the Er ions is very efficient. We concluded that Er-doped silicon oxide-zirconia is a promising material for photonic applications, being excitable at low pumping powers and producing broad-band ⁴I_13/2→⁴I_15/2 emission.     

Electrical and optical analyses of Er-doped silicon grown by liquid-phase epitaxy

We have studied the deep levels present in Er-doped silicon epilayers grown by the liquid-phase epitaxy method by deep level transient spectroscopy (DLTS) and optical DLTS, in order to identify the majority and minority carrier traps and a possible correlation between these traps and the observed photoluminescence (PL) and cathodoluminescence (CL) spectra. Capacitance–voltage analyses have been performed to analyze uniformity and depth distribution of the existing traps and marked differences have been observed between the luminescent and non-luminescent materials.The PL and depth resolved CL revealed the presence of dislocation-related emission lines which can possibly be correlated to the broadened peaks observed in DLTS analyses of luminescent material.     

Photoluminescence from Er-doped silicon rich oxide thin films

 Photoluminescence (PL) properties of Er-doped silicon rich oxide thin films deposited on Si substrate by co-evaporation of silicon monoxide and Er under different atmospheres are investigated. The samples exhibit luminescence peak at 1.54 μm which could be assigned to the recombination in intra-4f Er³⁺ transition. PL shows that this transition is highest when ammonia atmosphere is used during deposition followed by an annealing temperature at 850 °C in 95% N₂+5% H₂ gas (forming gas). In fact, we believe that the presence of the N atoms around Er ions increases the intensity of the 1.54 μm luminescence.     

Er emission from Er-doped Si-rich silicon oxide layers synthesised by hydrogen reactive magnetron co-sputtering

Among the systems used as optical amplifiers, we propose an original way to elaborate photoluminescent materials. The method is based on the reactive RF magnetron co-sputtering of SiO₂ and Er₂O₃ controlled by the hydrogen dilution rate in the plasma gas. The relationship between the photoluminescence properties and the structural characteristics is evidenced through the variation of two parameters in the deposition process: the hydrogen partial pressure within the plasma and the sputtered surface ratio of Er₂O₃ and SiO₂ targets.     

Erbium-doped silicon epilayers grown by liquid-phase epitaxy

Liquid-phase epitaxy from an Si–In–Er solution at an average temperature of 950°C has been used to grow 2–4 μm thick epilayers of erbium-doped silicon onto CZ and FZ silicon substrates in an oxygen-free hydrogen atmosphere. Most of the samples grown on CZ substrates presented detectable, but feeble photoluminescence at 2 K in the spectral range of emission of the Er³⁺ manifold at 0.8 eV. However, some of the samples presented intense photoluminescence, characterized by two bands at 0.807 (at 10 K) and 0.873 eV, of which the first falls almost at the same energy of the Er³⁺ line, but whose intensity presents a quite remarkable persistence up to 250 K. From the energy position of the two bands, from their temperature dependence and from the levels found by deep level transient spectroscopy measurements, associated to TEM examinations, it was possible to attribute these bands, labelled D1 and D2, to dislocation luminescence. It will be shown in this paper that the presence of erbium enhances the D1 luminescence, possibly due to the fact that in these samples erbium is gettered at dislocations in an Er–O local configuration, as it results from EXAFS measurements. Apparently, also, a competition occurs with the Er-induced radiative recombination at dislocations, which is a fast process, and the indirect excitation of the Er manifold, which is the predominant process in dislocation-free materials.     

New efficient mechanism of excitation of electroluminescence from erbium ions in crystalline silicon

In p–n junctions based on c-Si : Er we have realized highly efficient excitation of erbium electroluminescence at 1.54 μm with an efficiency close to unity. A possible mechanism is Auger recombination of electrons occupying the upper subband of the conduction band with free holes in the valence band whereas the energy of the recombination process is transferred by Coulomb interaction to 4f-electrons of an erbium ion transmitting it to the second excited state ⁴I_11/2 (excitation energy 1.26 eV). The observed three-level excitation of erbium ions is promising for development of a Si : Er laser.     

Si-based materials and devices for light emission in silicon

We report on the fabrication and performances of extremely efficient Si-based light sources. The devices consist of MOS structures with erbium (Er) implanted in the thin gate oxide. The devices exhibit strong 1.54 μm electroluminescence (EL) at 300 K with a 10% external quantum efficiency, comparable to that of standard light-emitting diodes using III–V semiconductors. Er excitation is caused by hot electrons impact and oxide wearout limits the reliability of the devices. Much more stable light-emitting MOS devices have been fabricated using Er-doped silicon rich oxide (SRO) films as gate dielectric. These devices show a high stability, with an external quantum efficiency reduced to 1%. In these devices, Er pumping occurs by energy transfer from the Si nanostructures to the rare-earth ions. Finally, we have also fabricated MOS structures with Tb- and Yb-doped SiO₂ which show room temperature EL at 540 nm (Tb) and 980 nm (Yb) with an external quantum efficiency of a 10% and 0.1%, respectively.     

The study of the influence of uniaxial stress on impurity complexes in silicon

The influence of external uniaxial stress on the different indium-donor complexes in silicon has been studied using the perturbed γ –γ angular correlation (PAC) method. Such effect of an applied stress is detected by means of the probe atoms situated at different complexes in the sample. The current results showed that the responses of the probes in an extrinsic silicon samples are found to be dissimilar for the same value of stress. Such change in the local environments of the probe atoms could be associated with the various strain field created by the implantations of varied size of impurities. The phosphorous implantation in silicon has even lead to the complete absence of observable effect of the applied stress suggesting significant lose of the elasticity of the sample.     

EPR study of porous silicon

An anisotropic EPR signal was observed in porous Si. According to its symmetry andg value, the EPR signal can be attributed to silicon dangling bonds located on the surface of a porous Si skeleton. The evolution of the EPR signal at room temperature in air was measured. The annealing temperature dependence of the EPR and the PL of porous Si in oxygen and the effects of gamma irradiation on the EPR and the PL spectra of porous Si were studied. The changes of the EPR signal and the PL intensity induced in atmosphere by ethyl alcohol and acetone were discovered. The dangling bond is only one of the factors which affect the PL.This project is supported by the National Natural Science Foundation of China.     

Visible and infrared photoluminescence from Er-doped SiOx

The annealing behaviors of photoluminescence of SiO_x and Er-doped SiO_x grown by molecular beam epitaxy in the wavelength range of visible and infrared light are studied. For SiO_x, four PL bands located at 510, 600, 716 and 810 nm, respectively, are observed. For Er-doped SiO_x, the 716 nm band, which is believed to be originated from the electron–hole recombination at the interface between crystalline Si and amorphous SiO₂, disappears in the annealing temperature range of 500–900°C. It is suggested the enhancement of Er luminescence is partially due to the energy transfer from the recombination at the interface between crystalline Si and SiO₂ to Er ions.     

EPR investigation of the trivalent chromium complexes in SrTiO3

The trivalent chromium centers were investigated by means of electron paramagnetic resonance (EPR) in SrTiO₃ single crystals grown using the Verneuil technique. It was shown that the charge compensation of the Cr³⁺-V_O dominant centers in octahedral environment is due to the remote oxygen vacancy located on the axial axis of the center. In order to provide insight into spin-phonon relaxation processes the studies of axial distortion of Cr³⁺-V_O centers have been performed as function of temperature. The analysis of the trigonal Cr³⁺ centers found in SrTiO₃ indicates the presence of the nearest-neighbor strontium vacancy. The next-nearest-neighbor exchange-coupled pairs of Cr³⁺ in SrTiO₃ has been analyzed from the angular variation of the total electron spin of S=2 resonance lines.     

XPS and RBS investigations of Si–Er–O interactions on a Si(1 0 0)-2x1 surface

The interactions among erbium, oxygen and silicon atoms on a Si(1 0 0)-2x1 reconstructed surface have been studied by means of X-ray photoelectron spectroscopy and Rutherford backscattering spectrometry. Erbium and oxygen were deposited at 600 °C on the Si surface and their behavior has been observed after different thermal processes. It was found that at 600 °C, the formation of a stable surface complex Er–O–Si is obtained together with Si oxidation; after an 800 °C annealing, the amount of oxygen bound to Si decreases and the remaining O atoms are mainly bonded to Er. An abrupt change was observed after 900 and 1000 °C annealings, which bury the Er atoms about 60 Å below the substrate surface. Our results give some hints to hypotise the O diffusion towards the Si bulk.     

Efficient silicon light emitting diodes made by dislocation engineering

Efficient silicon-based light emitting diodes have been fabricated using the dislocation engineering method. Crucially this technique uses entirely conventional ULSI processes. The devices were fabricated by conventional low-energy boron implantation into silicon substrates followed by high-temperature annealing, and strong silicon band edge luminescence was observed. Dislocation engineering is also shown to reduce the thermal quenching for other material systems. Dislocation engineered β-FeSi₂ and Er light emitting devices were fabricated and room temperature electroluminescence at 1.5 μm was observed in both cases.     

Luminescence from porous silicon doped with erbium–ytterbium complexes

The study of photoluminescence (PL) from porous silicon (PS) containing complexes of gadolinium oxychloride with Er³⁺- and Er³⁺–Yb³⁺ is reported. The concentration dependencies of PL intensity of PS with Er³⁺ containing complex have been studied. The dependencies have retained the main features that are characteristic of the pure complex for both IR and visible regions of the PL spectra. This allows interpretation of PL processes in complex-containing PS lthrough the concept of multiplication of low-energy electron excitations and cross-relaxation degradation of higher excited states. It has been shown that introducing Yb³⁺ ions into the complex significantly increases the PL intensity. Mechanisms associated with defect formation, the intrinsic conversion of excitation energy within Yb³⁺, and the conversion within Er³⁺ ions followed by transferring of excitation energy to the Yb³⁺ ions has been considered. The PL polarization with excitation in the visible is reported as well.     

Fabrication of NdFeB microstructures using a silicon molding technique for NdFeB/Ta multilayered films and NdFeB magnetic powder

The silicon molding technique is described for patterning of NdFeB/Ta multilayered magnetic films and NdFeB magnetic powder at the micron scale. Silicon trenches are seamlessly filled by 12-μm-thick NdFeB/Ta multilayered magnetic films with a magnetic retentivity of 1.3 T. The topography image and magnetic field distribution image are measured using an atomic force microscope and a magnetic force microscope, respectively. Using a silicon molding technique complemented by a lift-off process, NdFeB magnetic powder is utilized to fabricate magnetic microstructures. Silicon trenches as narrow as 20 μm are filled by a mixture of magnetic powder and wax powder. The B-H hysteresis loop of the patterned magnetic powder is characterized using a vibrating sample magnetometer, which shows a magnetic retentivity of approximately 0.37 T.     

Preparation and characterization of silicon oil based ferrofluid

Stable silicon oil based ferrofluid was prepared in the present investigation. Silicon oil surfactant ethoxy terminated polydimethylsiloxane was used to modify the Fe₃O₄ nanoparticles. The Fe₃O₄ nanoparticles were firstly coated with a SiO₂ layer by the hydrolysis of tetraethoxysilane. Then using the active hydroxyl groups on the surface of the SiO₂, silicon oil surfactant was covalently grafted onto the Fe₃O₄ nanoparticles surface. The ethoxy terminated polydimethylsiloxane has similar molecular chain structure and good compatibility with that of the carrier liquid, thus ensuring stable dispersion of modified Fe₃O₄ in the carrier silicon oil. The interaction between Fe₃O₄ and the modifier was characterized by IR and XPS. The crystal structure and the magnetic properties of the Fe₃O₄ nanoparticles were determined by XRD and VSM, respectively. The size and morphology of the particles were observed using TEM. The properties of the silicon oil based ferrofluid were characterized by Gouy magnetic balance. The results indicated that the ferrofluid had high magnetism and good stability. The rheological properties and thermostability of the ferrofluid were also investigated.     

Enhancement of the emission yield of silicon nanocrystals in silica due to surface passivation

The ability of surface passivation to enhance the photoluminescence (PL) emission of Si nanocrystals in SiO₂ has been investigated. Silicon precipitation in implanted samples takes place in a time scale of few minutes at 1100°C. For longer annealing at the same temperature, the PL intensity of the Si nanocrystals increases and eventually reaches saturation, while it correlates inversely with the amount of Si dangling bonds at the Si–SiO₂ interface (P_b centers), as measured by electron spin resonance. This combined behavior is independent on the silica matrix properties, implantation profiles and annealing atmosphere and duration. The observation that the light emission enhancement is directly related to the annealing of P_b centers is confirmed by treatment in forming gas. This mild hydrogenation at much lower temperature (450°C) leads to a complete passivation of the P_b defects, increasing at the same time the PL yield and the lifetime.     

A tight-binding study of LUMO states in ellipsoidal silicon nanocrystals

In this paper we report on tight-binding calculations of lowest unoccupied molecular orbitals states for silicon ellipsoidal nanocrystals. The electronic structure has been calculated for different nanocrystal shapes either keeping constant or varying the number of silicon atoms. We have found that changing the ellipsoid aspect ratio a non-obvious energy level structure is obtained. The implications for the infrared optical transitions and their relationship with the polarization of the radiation involved are discussed.