掺铒硅基材料发光的新途径

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Er离子注入的富硅SiO2MOS-LED的可见和红外电致发光特性

通过Er离子和Si离子注入并结合高温退火制备了Er掺杂的富硅SiO2薄膜以及ITO/SiON/富硅SiO2:Er/Si MOS结构电致发光器件.研究了富Si浓度的变化对Er3+离子掺杂的电致发光器件的发光性能和传导特性的影响.发现不同Si含量对Er3+离子的不同能级的电致发光会产生不同作用.在富Si量小于5％的条件下,...     

The excitation mechanism of rare-earth ions in silicon nanocrystals

A detailed investigation on the excitation mechanisms of rare-earth (RE) ions introduced in Si nanocrystals (nc) is reported. Silicon nanocrystals were produced by high-dose 80-keV Si implantation in thermally grown SiO₂ followed by 1100 °C annealing for 1 h. Subsequently some of the samples were implanted by 300-keV Er, Yb, Nd, or Tm at doses in the range 2×10¹²–3×10¹⁵ /cm². The energy was chosen in such a way to locate the RE ions at the same depth where nanocrystals are. Finally an annealing at 900 °C for 5 min was performed in order to eliminate the implantation damage. These samples show intense room-temperature luminescence due to internal 4f shell transitions within the RE ions. For instance, luminescence at 1.54 μm and 0.98 μm is observed in Er-doped nc, at 0.98 μm in Yb-doped nc, at 0.92 μm in nc and two lines at 0.78 μm and 1.65 μm in Tm-doped nc. Furthermore, these signals are much more intense than those observed when RE ions are introduced in pure SiO₂ in the absence of nanocrystals, demonstrating the important role of nanocrystals in efficiently exciting the REs. It is shown that the intense nc-related luminescence at around 0.85 μm decreases with increasing RE concentration and the energy is preferentially transferred from excitons in the nc to the RE ions which, subsequently, emit radiatively. The exact mechanism of energy transfer has been studied in detail by excitation spectroscopy measurements and time-resolved photoluminescence. On the basis of the obtained results a plausible phenomenological model for the energy transfer mechanism emerges. The pumping laser generates excitons within the Si nanocrystals. Excitons confined in the nc can either give their energy to an intrinsic luminescent center emitting at around 0.85 μm nor pass this energy to the RE 4f shell, thus exciting the ion. The shape of the luminescence spectra suggests that excited rare-earth ions are not incorporated within the nanocrystals and the energy is transferred at a distance while they are embedded within SiO₂. Rare-earth excitation can quantitatively be described by an effective cross section σ_eff taking into account all the intermediate steps leading to excitation. We have directly measured σ_eff for Er in Si nc obtaining a value of ≈2×10⁻¹⁷ cm². This value is much higher than the cross section for excitation through direct photon absorption (8×10⁻²¹ cm²) demonstrating that this process is extremely efficient. Furthermore, the non-radiative decay processes typically limiting rare-earth luminescence in Si (namely back-transfer and Auger) are demonstrated to be absent in Si nc further improving the overall efficiency of the process. These data are reported and their implications. Received: 9 April 1999 / Accepted: 10 April 1999 / Published online: 2 June 1999     

Sensitisation of erbium emission by silicon nanocrystals-doped SnO2

SnO₂ thin films undoped and doped with antimony (Sb), erbium (Er) and Si nanocrystals (Si-nc) have been grown on silicon (Si) substrate using sol-gel method. Room-temperature photoluminescence (PL) measurement of undoped SnO₂, under excitation at 280 nm, shows only one broad emission at 395 nm, which is related to oxygen vacancies. The PL of Er³⁺ ions was found to be enhanced after doping SnO₂ with Sb and Si-nc. The excitation process of Er is studied and discussed. The calculation of cross-section suggests a sensitisation of Er PL by Si-nc.     

1.54 μm Light emission from Er/O and Er/F doped Si p–i–n diodes grown by molecular beam epitaxy

Various light emitting devices (LED) have been processed using Er/O- and Er/F-doped Si layered structures grown by molecular beam epitaxy (MBE) at low temperature. A comparative study has been carried out in order to provide more understanding of the electroluminescence (EL) excitation and de-excitation mechanisms in particular at a high injection current regime. Comparing the experimental results with model calculations the values of excitation cross section, σ_ex, and effective Auger coefficient, C_A, have been determined for various devices operated at different biases. Time-resolved EL measurements of these Er/O- and Er/F-doped MBE Si structures, using an experimental set-up with a time response of 200 ns, have been performed with different excitation conditions. Besides the spontaneous Er emission (700 μs), some fast EL decay processes associated with the Auger energy transfer via free carriers (4 μs), and the hot carrier effects (200 ns) have been identified.     

Erbium-doped Si nanocrystals: optical properties and electroluminescent devices

In the last decade, a strong effort has been devoted towards the achievement of efficient light emission from silicon. Among the different approaches, rare-earth doping and quantum confinement in Si nanostructures have shown great potentialities. In the present work, the synthesis and properties of low-dimensional silicon structures in SiO₂ will be analyzed. All of these structures present a strong room temperature optical emission, tunable in the visible by changing the crystal size. Moreover, Si nanocrystals (nc) embedded in SiO₂ together with Er ions show a strong coupling with the rare earth. Indeed each Si nc absorbs energy which is then preferentially transferred to the nearby Er ions. The signature of this interaction is the strong increase of the excitation cross section for an Er ion in the presence of Si nc with respect to a pure oxide host. We will show the properties of Er-doped Si nc embedded within Si/SiO₂ Fabry–Pérot microcavities. Very narrow, intense and highly directional luminescence peaks can be obtained. Moreover, the electroluminescence (EL) properties of Si nc and Er-doped Si nc in MOS devices are investigated. It is shown that an efficient carrier injection at low voltages and quite intense room temperature EL signals can be achieved, due to the sensitizing action of Si nc for the rare earth. These data will be presented and the impact on future applications discussed.     

利用高压拉曼散射研究Ge/SiO_2/Si纳米系统的压力/张力(英文)

pacc:7830,8100 WereportthepressuredependenceofGe nanocrystalsembeddedinSiO2filmmatrixonSi substrateusingRamanscatteringandfiniteele mentanalysis.DelaminationofSiO2filmfromthe Sisubstrateoccursat～23kbarduetothelarge differencebetweenthecompressibilityoft…     

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.     

铒掺杂富硅热化SiO2／Si发光薄膜的显微结构

利用金属蒸气真空弧(MEVVA)离子源将稀土元素Er离子掺杂到富硅热氧化SiO2/Si薄膜中.卢瑟福背散射(RBS)和X-射线电子能谱仪(XPS)分析表明,Er浓度可达原子百分数(x)～10,即Er的原子体浓度为～1021·     

Spherical growth and surface-quasifree vibrations of Si nanocrystallites in Er-doped Si nanostructures

Si-based Er-doped Si nanostructures were fabricated for exploring efficient light emission from Er ions and Si nanocrystallites. High-resolution transmission electron microscopy observations reveal that Si nanocrystallites are spherically embedded in the SiO2 matrix. Energy-dispersive x-ray analysis indicates that the Er centers are distributed at the surfaces of nanocrystallites surrounded by the SiO2 matrix. Low-frequency Raman scattering investigation shows that Lamb's theory can be adopted to exactly calculate the surface vibration frequencies from acoustic phonons confined in spherical Si nanocrystallites and the matrix effects are negligible.     

Emission of 1.53 microm originating from the lattice site of Er3+ ions incorporated in TiO2 nanocrystals

Er(3+)-ion-doped anatase TiO(2) nanocrystals were prepared by simple wet chemical synthesis. Very sharp and intense near-infrared luminescence at approximately 1.53 microm was observed that originated from the lattice site of Er(3+) ions incorporated in TiO(2) nanocrystals. Based on the high-resolution emission and excitation spectra at 10 K, an efficient energy transfer from the TiO(2) host to Er(3+) ions was verified. The luminescence decay for the I13/24-->I15/24 transition at 1.53 microm showed nonexponential characteristics, indicating a nonradiative relaxation to the defects in the nanocrystals, and the intrinsic lifetime of the I13/24 state was determined to be 1.56 ms.     

Interrelation between microstructure and optical properties of erbium-doped nanocrystalline thin films

Nanocrystalline silicon thin films codoped with erbium, oxygen and hydrogen have been deposited by co-sputtering of Er and Si. Films with different crystallinity, crystallite size and oxygen content have been obtained in order to investigate the effect of the microstructure on the photoluminescence properties. The correlation between the optical properties and microstructural parameters of the films is investigated by spectroscopic ellipsometry. PL response of the discussed structures covers both the visible wavelength range (a crystallite size-dependent photoluminescence detected for 5–6 nm sized nanocrystals embedded in a SiO matrix) and near IR range at 1.54 μm (Er-related PL dominating in the films with 1–3 nm sized Si nanocrystals embedded in a-Si:H). It is demonstrated that the different PL properties can be also discriminated on the basis of ellipsometric spectra.     

Donor-state-enabling Er-related luminescence in silicon: direct identification and resonant excitation

We conclusively establish a direct link between formation of an Er-related donor gap state and the 1.5 microm emission of Er in Si. The experiment is performed on Si/Si:Er nanolayers where a single type of Er optical center dominates. We show that the Er emission can be resonantly induced by direct pumping into the bound exciton state of the identified donor. Using two-color spectroscopy with a free-electron laser we determine the ionization energy of the donor-state-enabling Er excitation as E(D) approximately 218 meV. We demonstrate quenching of the Er-related emission upon ionization of the donor.     

Nanostressors and the nanomechanical response of a thin silicon film on an insulator

Pseudomorphic three-dimensional Ge nanocrystals (quantum dots) grown on thin silicon-on-insulator substrates can induce significant bending of the silicon template layer that is local on the nanometer scale. We use molecular dynamics simulations and analytical models to confirm the local bending of the Si template and to show that its magnitude approaches the maximum value for a freestanding membrane. The requisite greatly enhanced viscous flow of SiO2 underneath the Si layer is consistent with the dependence of the viscosity of SiO2 on shear stress.     

Effect of high-pressure water-vapor annealing on energy transfer in dye-impregnated porous silicon

We have studied the effect of high-pressure water-vapor annealing (HWA) on the excitation energy transfer from Si nanocrystals to dye molecules in porous Si layers. Efficient photoluminescence, originating from both RhB molecules and Si nanocrystals, was observed. The behavior of the polarization memory of the photoluminescence showed the presence of energy transfer from the surface-passivated Si nanocrystals to RhB molecules. The fact that HWA, which is an effective method to stabilize and enhance the emission from Si nanocrystals in porous Si, does not suppress the energy transfer is an important result since it makes possible the realization of stable Si/dye-nanocomposite functional devices.     

The mechanism of energy transfer from Si nanocrystals to Er ions in SiO2

The mechanism of energy transfer from silicon nanocrystals (Si-nc’s) to erbium (Er) ions is studied by analyzing time transient of Er photoluminescence at 1.54 μm. It is shown that two different energy transfer mechanisms, i.e., fast and slow, exist in SiO₂ films containing Si-nc’s and Er ions, and that the ratio of slow to fast processes depends on size of Si-nc’s and Er concentration. A quantitative analysis reveals that Er ions located within about 1.5 nm from the surface of Si-nc’s are excited by the fast process, and those located within about 2.5 nm by the slow process if no Er ions exist within 1.5 nm from the surface. Er ions staying outside these regions cannot be sensitized by Si-nc’s.     

Light emitting devices based on silicon nanostructures

In this paper, we summarize the results of an extensive investigation on the properties of MOS-type light emitting devices based on silicon nanostructures. The performances of crystalline, amorphous and Er-doped Si nanostructures are presented and compared. We show that all devices are extremely stable and robust, resulting in an intense room temperature electroluminescence (EL) at around 900 nm or at 1.54 μm. Amorphous nanostructures may constitute an interesting system for the monolithic integration of optical and electrical functions in Si ULSI technology. In fact, they exhibit an intense room temperature EL with the advantage to be formed at a temperature of only 900 °C, remarkably lower than the temperature needed for the formation of Si nanocrystals (1100 °C or higher). To improve the extraction of the light, we coupled the emitting system with a 2D photonic crystal structure properly fabricated with ULSI technology to reduce the total internal reflection of the emitted light. We demonstrate that the extraction efficiency is increased by a factor of 4. Finally, the light emission from devices based on Er-doped Si nanoclusters has been studied and in particular we have investigated the luminescence quenching processes limiting quantum efficiency in these devices. In fact the carrier injection, that determines the excitation of Er ions through electron–hole recombination, at the same time produces an efficient non-radiative Auger de-excitation with trapped carriers. These data are presented and the implications on the device performances discussed.     

Rate equation modelling of erbium luminescence dynamics in erbium-doped silicon-rich-silicon-oxide

Erbium doped silicon-rich silica offers broad band and very efficient excitation of erbium photoluminescence (PL) due to a sensitization effect attributed to silicon nanocrystals (Si-nc), which grow during thermal treatment. PL decay lifetime measurements of sensitised Er³⁺ ions are usually reported to be stretched or multi exponential, very different to those that are directly excited, which usually show a single exponential decay component.In this paper, we report on SiO₂ thin films doped with Si-nc's and erbium. Time resolved PL measurements reveal two distinct 1.54 μm Er decay components; a fast microsecond component, and a relatively long lifetime component (10 ms). We also study the structural properties of these samples through TEM measurements, and reveal the formation of Er clusters. We propose that these Er clusters are responsible for the fast μs decay component, and we develop rate equation models that reproduce the experimental transient observations, and can explain some of the reported transient behaviour in previously published literature.     

Relative enhancement of photoluminescence intensity of passivated silicon nanocrystals in a silicon dioxide matrix

Photoluminescence (PL) intensity of passivated silicon nanocrystals (Si NCs) embedded in a SiO 2 matrix is compared with that of unpassivated Si NCs. We investigate the relative enhancement of PL intensity (I R ) as a function of annealing temperature and implanted Si ion dose. The I R increases simultaneously with the annealing temperature. This demonstrates an increase in the number of dangling bonds (DBs) with the degree of Si crystallization varying via the annealing temperature. The increase in I R with implanted Si ion dose is also observed. We believe that the near-field interaction between DBs and neighboring Si NCs is an additional factor that reduces the PL efficiency of unpassivated Si NCs.     

Photo-modification and synthesis of semiconductor nanocrystals

Both photo-oxidation and photosynthesis manifest a strong interaction between nanoparticles and photons due to the large surface area-to-volume ratio. The final sizes of the semiconductor nanocrystals are determined by the photon energy during these phenomena. The photosynthesis is demonstrated in a Si-rich oxide and is similar to thermal synthesis, which involves the decomposition of SiO_x into Si and SiO₂, that is well known and often employed to form Si or Ge nanocrystals embedded in SiO₂ by annealing SiO_x at high temperature. However, photosynthesis is much faster, and allows the low-temperature growth of Si nanocrystals and is found to be pronounced in the SiO nanopowder, which is made by thermal CVD using SiH₄ and O₂. The minimum laser power required for the photosynthesis in the SiO nanopowder is much lower than in the Si-rich oxide formed by the co-sputtering of Si and SiO₂. This is attributed to the weak bond strength of Si-Si and Si-O in the SiO nanopowder. Photosynthesis, which can control the size and position of Si nanocrystals, is a novel nanofabrication technique making the best use of the strong interaction between photons and nanoparticles.