Electroluminescence properties of light emitting devices based on silicon nanocrystals

We have fabricated MOS devices where the dielectric layer consists of a substoichiometric SiO_x (x<2) thin film, annealed at 1100°C for 1 h to induce the separation of the Si and SiO₂ phases, with the formation of silicon nanocrystals (nc) embedded in the insulating matrix. We have studied the electroluminescence (EL) properties of such devices as a function of the current density and of the temperature. We have evaluated the excitation cross section of Si nc under electrical pumping at room temperature and at low temperature (12 K). Moreover, we have used the experimental EL intensities and decay times to evaluate the radiative rate as a function of the temperature.     

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.     

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.     

Si-based erbium-doped light-emitting devices

We report on the fabrication and performance of Si-based light sources. The devices consist of MOS structures with erbium (Er)-doped silicon rich oxide (SRO) film as gate dielectric. The devices exhibit electroluminescence (EL) at 1.54 μm at room temperature with a 0.2% external quantum efficiency. These devices show a high stability due to the silicon excess in the film. The Er-doped SRO films have been introduced in a Si/SiO₂ Fabry-Perot Microcavity in order to increase the spontaneous emission rate, the extraction efficiency and the spectral purity at the resonant wavelength. The active medium in the cavity has been electrically pumped and the conduction mechanisms have been analyzed. The EL spectra have also been acquired and compared with photoluminescence (PL) ones for the same resonant cavity light-emitting device (RCLED). The EL and PL peak intensities of the on-axis emission at the resonant wavelength are over 20 times above that of the similar Er-doped SRO film without a cavity. The Si-based RCLEDs exhibit different quality factors, ranging from 60 to 170. The spectra shape and intensity have been correlated with the quality factor. A high directionality of the emitted light, due to the presence of the resonant cavity, has also been observed: the overall luminescence is confined within 10° cone from the sample normal.     

Correlations of a bound interface over a random substrate

The effects of Si nanocluster (Si-nc) size on the energy transfer rate to Er ions were investigated through studies made on appropriate configurations of mutilayers (MLs) consisting in about 20 periods of Er-doped Si-rich SiO₂/SiO₂. These MLs were deposited by reactive magnetron sputtering at 650 °C and subsequently annealed at 900 °C. For Si-rich layer thickness or Si-nc larger than about 4 nm, the sensitizing effect of Si-nc towards rare earth ions is highly lowered because of the weak confinement of carriers and the loss of resonant excitation of Er through the upper levels (second, third, ...). The latter is liable to prevent the energy back transfer process, while the weak confinement reduces strongly the probability of no phonon radiative recombination necessary for the energy transfer from Si-nc to Er ions.     

掺饵氢化非晶氧化硅1.54μm发光性质的研究

采用等离子体增强化学汽相沉积技术生长不同氧含量的氢化非晶氧化硅薄膜(a-SiO_{x∶H),离子注入铒及退火后在室温观察到很强的光致发光.当材料中氧硅含量比约为1和 1.76时,分别对应77Ｋ和室温测量时最强的1.54μm光致发光.从15到250Ｋ的变温实验显示 出三个不同的强度与温度变化关系,表明氢化非晶氧化硅中铒离子的能量激发和发光是一个 复杂的过程.提出氢化非晶氧化硅薄膜中发光铒离子来自于富氧区,并对实验现象进行了解 释.氢化非晶氧化硅中铒发光的温度淬灭效应很弱.从15到250Ｋ,光致发光强度减弱约1/2. 关键词： 铒 光致发光 氧含量}     

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     

Electroluminescence of silicon nanocrystals in MOS structures

We have studied the structural, electrical and optical properties of MOS devices, where the dielectric layer consists of a substoichiometric SiO_x (x<2) thin film deposited by plasma-enhanced chemical vapor deposition. After deposition the samples were annealed at high temperature (>1000 °C) to induce the separation of the Si and the SiO₂ phases with the formation of Si nanocrystals embedded in the insulating matrix. We observed at room temperature a quite intense electroluminescence (EL) signal with a peak at ∼850 nm. The EL peak position is very similar to that observed in photoluminescence in the very same device, demonstrating that the observed EL is due to electron–hole recombination in the Si nanocrystals and not to defects. The effects of the Si concentration in the SiO_x layer and of the annealing temperature on the electrical and optical properties of these devices are also reported and discussed. In particular, it is shown that by increasing the Si content in the SiO_x layer the operating voltage of the device decreases and the total efficiency of emission increases. These data are reported and their implications discussed. Received: 31 August 2001 / Accepted: 3 September 2001 / Published online: 17 October 2001     

Er-doped edge emitting devices with a SiGe waveguide

Er-doped Si edge emitting devices have been fabricated using layer structures grown by molecular beam epitaxy (MBE). Both oxygen and carbon were used as co-dopant in the Er-doped layer. In order to achieve a waveguiding effect, a SiGe layer has been placed next to the Er-doped layer. Intense electroluminescence (EL) at 1.54 μm has been observed from edge emission of such a device at room temperature and even up to 50°C at low excitation power under reverse bias. The value of an activation energy (125 meV) for dominating luminescence intensity quenching, as derived from temperature-dependent EL measurements, was 30 meV lower than that observed from our previous Er/O-doped structures (155 meV), which is likely caused by the band gap narrowing induced by C-doping. The estimated external quantum efficiency of these Er-doped Si edge emitting LEDs is 5×10⁻⁵ at room temperature.     

Long lifetime and efficient emission from Er ions coupled to Si nanoclusters in Si-rich SiO2 layers

Reactive magnetron co-sputtering of two confocal SiO₂ and Er₂O₃ cathodes in argon-hydrogen plasma was used to deposit Er-doped Si-rich SiO₂ layers. The effects of the deposition conditions (such as RF power applied on each cathode and total plasma pressure) and annealing treatment (temperature and duration) on structural, compositional and photoluminescence (PL) properties of the layers were examined. It was found that a significant enhancement of both Er³⁺ PL intensity and emission lifetime up to 9 ms have been reached through monitoring of the conditions of both deposition process and annealing treatment. The effective absorption cross section and the fraction of Er ions coupled to Si clusters were analyzed. It was shown an increase of the fraction of Er³⁺ ions coupled to Si up to 11%.     

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     

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     

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     

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.     

The effects of ambient oxygen pressure on the 1.54 μm photoluminescence of Er-doped silicon-rich silicon oxide films grown by laser ablation of a Si+Er target

We fabricated Er-doped silicon-rich silicon oxide (SRSO:Er) films by pulsed laser deposition. A Si+Er target consisting of an Er metallic strip and a silicon disk was adopted with a goal to achieve a convenient control of the Er and oxygen density in the film. We found that the photoluminescence (PL) at 1.54 m is highly dependent on the ambient oxygen pressure, which determines the relative ratio of Si-Si, SiO_x, and SiO₂ phase in the film. The PL intensity increased drastically with increase in the annealing temperature and reached the maximum intensity at 500 °C. PACS 81.15.Fg; 81.07.-b     

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.     

Photoluminescence of Er-doped Si-SiO2 and Al–Si-SiO2 sputtered thin films

Er-doped Si-SiO₂ and Al–Si-SiO₂ films have been deposited by rf-sputtering being annealed afterwards. Annealing behavior of the Er³⁺: ⁴I_13/2→⁴I_15/2 emission of Er-doped Si-SiO₂ yields a maximum intensity for annealing at 700–800 °C. ⁴I_13/2→⁴I_15/2 peak emission for Er-doped Al–Si-SiO₂ at 1525 nm is shifted from that for Er-doped Si-SiO₂ at 1530 nm and the bandwidth increases from 29 to 42 nm. ⁴I_13/2→⁴I_15/2 emission decays present a fast decaying component related to Er ions coupled to Si nanoparticles, defects, or other ions, and a slow decaying component related to isolated Er ions. Excitation wavelength dependence and excitation power dependence for the ⁴I_13/2→⁴I_15/2 emission correspond with energy transfer from Si nanoparticles. Populating of the ⁴I_11/2 level in Er-doped Si-SiO₂ involves branching and energy transfer upconversion involving two or more Er ions. Addition of Al reduces the populating of this level to an energy transfer upconversion involving two ions.     

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.     

镶嵌在氧化硅薄膜中纳米晶硅的可见光荧光谱与发光机制的研究

采用对非晶氧化硅薄膜退火处理方法，获得纳米晶硅与氧化硅的镶嵌结构．室温下观察到峰位为2.40eV光致发光．系统地研究了不同退火温度对薄膜的Raman谱、光荧光谱及光电子谱的影响．结果表明，荧光谱可分成两个不随温度变化的峰位为1.86和2.30eV的发光带．Si2p能级光电子谱表明与发光强度一样Si⁴⁺强度随退火温度增加而增加．Si平均晶粒大小为4.1—8.0nm，不能用量子限制模型解释蓝绿光的发射．纳米晶硅与SiO₂界面或SiO₂中与氧有关的缺陷可能是蓝绿光发射的主要原因 关键词：     

The role of microstructure in luminescent properties of Er-doped nanocrystalline Si thin films

In this contribution, we present a structural and photoluminescence (PL) analysis of Er-doped nanocrystalline silicon thin films produced by rf magnetron sputtering method. We show the strong influence of the presence of nanocrystalline fraction in films on their luminescence efficiency at 1.54 μm studied on a series of specially prepared samples with different crystallinity, i.e., percentage and sizes of Si nanocrystals. A strong increase, by about two orders of magnitude, of Er-related PL intensity in these samples with lowering of the Si nanocrystal sizes from 7.9 to about 1.5 nm is observed. The results are discussed in terms of the sensitization effect of Si nanocrystals on Er ions. From Fizika Tverdogo Tela, Vol. 46, No. 1, 2004, pp. 114–118. Original English Text Copyright ? 2004 by Stepikhova, Cerqueira, Losurdo, Giangregorio, Alves, Monteiro, Soares. This article was submitted by the authors in English.