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.     

Charge storage and electron/light emission properties of silicon nanocrystals

Monodispersed silicon nanocrystals show novel electrical and optical characteristics of silicon quantum dots, such as single-electron tunneling, ballistic electron transport, visible photoluminescence and high-efficiency electron emission.Single-electron memory effects have been studied using a short-channel MOSFET incorporating Si quantum dots as a floating gate. Surface nitridation of Si nanocrystal memory nodes extends the charge-retention time significantly. Single-electron storage in individual Si dots has been evaluated by Kelvin probe force microscopy.Photoluminescence and electron emission are observed for surface-oxidized silicon nanocrystals. Efficiency of the no-phonon-assisted transition increases with decreasing core Si size. Electron emission efficiency as high as 5% has been achieved for the Si-nanocrystal-based cold electron emitter devices. The non-Maxwellian energy distribution of emitted electrons suggests that the mechanism of electron emission is due to ballistic transport through arrays of surface-oxidized Si nanocrystals. Combined with the ballistic electron emission, the quasi-direct light emission properties can be used for developing Si-based lasers.     

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.     

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.     

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.     

Radiative emission properties of a-SiN : H based nanometric multilayers for light emitting devices

Optical and photoluminescence characterizations were performed on nanometric multilayer structures based on amorphous silicon nitrogen alloys. Evidences are shown that the radiative efficiency of multilayers increases with respect to single-layer structures. This is ascribed to a strong electron–hole pair localization and a low heterointerfaces defect density. Time-resolved photoluminescence measurements yield fast recombination with an energy-dependent lifetime due to hopping processes. Finally, the performance of an electroluminescent device based on multilayers is presented.     

Quantum confinement and disorder in porous silicon: Effects on the optical and transport properties

Summary The striking optical properties of porous silicon (PS) show a twofold aspect typical of an ordered and a disordered material, respectively. Raman, electron microscopy, and resonant photoluminescence studies indicate that the light emission originates from crystalline regions. On the contrary, several features, like the non-exponential decay of photoluminescence (PL), the broad emission spectrum, the photoluminescence fatigue under light exposure etc. are typical of a disordered material and reminiscent of similar effects founde.g. in amorphous semiconductors. These twoapparently conflicting aspects have for a long time hindered the understanding of the basic light emission mechanism. In this paper we report new optical data showing that disorder in porous silicon leads to strong carrier localisation. Light emission in PS is suggested to occur through transitions involving localized states. Paper presented at the III INSEL (Incontro Nazionale sul Silicio Emettitore di Luce), Torino, 12–13 October 1995.     

Photoluminescence studies of Si nanocrystals

Summary We report room temperature time-resolved photoluminescence (PL) and temperature dependence of continuous wave (cw) PL studies of high fluence (from 3·10¹⁶ to 3·10¹⁷ cm⁻²) Si⁺-implanted thermal SiO₂ layers after annealing at high temperature (T=1000°C). Such measurements were related to TEM analysis of samples. Nancocrystals were observed at TEM only a samples implanted at higher fluence. In these samples a near infrared PL signal peaked at approximately 1.5 eV with decay time of about 100 μs is present. Besides, in all samples a light emission is present in the green region of the spectrum. The intensity of the emission shows large variations with ion fluence, and is characterized by 0.4, 2 and 7 ns decay times. Paper presented at the III INSEL (Incontro Nazionale sul Silicio Emettitore di Luce) Torino, 12–13 October 1995.     

Optical properties of silicon nanocrystal LEDs

In this work, we describe how to fabricate good quality 3 nm nc-Si with low size distribution in thermal SiO₂ oxides. Photoluminescence, excited photoluminescence, and photocurrent measurements are discussed on the basis of theoretical calculations of the quantified levels in nc-Si. The impact of shape and size in quantum dots on transition energies has been highlighted, thanks to 2D symmetrical self-consistent Poisson–Schrödinger simulations. Both direct and indirect gaps in silicon have been considered in order to carry out a better comparison between simulations and optical measurements. A good agreement is found between simulations and experimental data for the indirect gap of 3 nm dots which show a threshold energy around 2 eV. However, the optical recombinations seems to be related to lower energy states probably due to interfacial radiative defects around 1.58 eV. On the basis of highly luminescent nc-Si, we have fabricated an optimized light emitting device (LED) with a calculated design in order to favour both electron and hole injection. Stable red electroluminescence has been obtained at room temperature and the I–V measurements confirm that the current is related to a pure tunnelling process. A modelling of I–V curves confirms a Hopping mechanism with an average trap distance between 1.4 and 1.9 nm. The Fowler–Nordheim process is not observed during light emission for electric fields below 5 MV/cm. Finally, we have not hot carrier injection and thus it seems possible to develop Si-based LEDs with a good reliability.     

Electrical and memory properties of silicon nitride structures with embedded Si nanocrystals

In this work, the electrical and memory behaviour of metal-silicon nitride-silicon structures with an embedded nanocrystalline silicon layer, which either consists of separated silicon nanocrystals, or is a continuous nanocrystalline layer, are presented. The structures were prepared by low-pressure chemical vapour deposition (LPCVD). The effect of the duration of deposition and the structure of the nanocrystalline layer were studied. The writing/erasing behaviour was similar for all the structures, but the retention properties were much worse in the structure with a continuous nanocrystalline layer, than in the structures with separated Si nanocrystals. This indicates that Si nanocrystals play role in charge storage in the studied structures.     

3,4,9,10-Perylenetetracarboxylicdiimide as an interlayer for ultraviolet organic light emitting diodes

Ultraviolet organic light emitting diodes with 3,4,9,10-perylenetetracarboxylicdiimide (PTCDI) interlayer have been achieved. The emission spectrum and intensity were strongly dependent on the thickness of PTCDI interlayer, in spite of the fact that PTCDI has neither much lower HOMO nor much higher LUMO level, which is considered necessary for efficient charge blocking layers. The influence of PTCDI layer was investigated in three different device configurations and obtained results are discussed. For optimal device configuration, OLED with emission centered at 370 nm and turn-on voltage of 4.5 V is obtained.     

Organic light emitting devices

The purpose of this paper is to provide general information about basic physical processes involved in organic electroluminescence and to present the main parameters and advantages of organic light emitting devices (OLEDs).     

X-ray absorption study of light emitting silicon nanocrystals

X-ray absorption spectra obtained by total electron yield (TEY) at the Si absorption K-edge have been measured to have chemical and structural information about Si nanocrystals (Si-nc) produced by plasma-enhanced chemical vapour deposition (PECVD). The TEY technique has been employed to investigate the formation of Si-nc and the modification of the silica matrix as a function of annealing temperature (500–1250°C) and of silicon content in the film (35–46 at%). The amount of silicon present in the Si-nc has been evaluated by TEY. Thanks to Rutherford backscattering spectrometry measurements, the amount of Si atoms bonded to oxygen and to nitrogen, incorporated by PECVD, has been assessed. A compositional model that interprets the experimental findings is presented.     

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.     

Light-emitting nanocrystalline silicon by low-pressure chemical-vapor deposition of disilane

Summary Porous silicon is an attractive material for silicon optoelectronics. The great advantage of porous silicon lies on the simple way of production which makes silicon nanostructures easily available. After several papers have been published on this topic, we are able to identify some disadvantages connected to the porous nature of the material and to the method of fabrication. Other dry processes can be used to produce Si nanostructures. In this paper we present a method fully compatible with the standard semiconductor technology. The optical and structural properties of the nanocrystalline films so far obtained are presented, together with some promising results indicating good electrical properties. Paper presented at the III INSEL (Incontro Nazionale sul Silicio Emettitore di Luce) Torino, 12–13 October 1995.     

Erbium doping of crystalline and amorphous silicon for optoelectronic applications

Summary In this work we demonstrate that efficient light emission at 1.54 μm can be achieved when Er ions are incorporated into crystalline Si or in heavily oxygen-doped amorphous and polycrystalline Si films (SIPOS). We have found that temperature quenching of photo- and electroluminescence, which is the major limitation towards the achievement of room temperature luminescence, can be strongly reduced by codoping these films with oxygen. This impurity is already present in as-prepared SIPOS and it is introduced by ion-implantation in crystalline Si. Er luminescence is obtained under both optical and electrical excitation and we demonstrate that excitation occurs through a carrier-mediated process. Electrical excitation is obtained by incorporating Er in properly designed device structures. It is found that this excitation can occur both through the recombination of hole-electron pairs and through impact excitation of the Er ions by hot electrons. These two mechanisms have different efficiencies and impact excitation is shown to prevail at room temperature. These data are presented and possible future developments are discussed. Paper presented at the III INSEL (Incontro Nazionale sul Silicio Emettitore di Luce), Torino, 12–13 October 1995.     

Si nanocrystals in silicon nitride: An ellipsometric study using parametric semiconductor models

Low-pressure chemical vapour deposited Si₃N₄/nc-Si/Si₃N₄ layers prepared on Si substrates were characterized by spectroscopic ellipsometry. Model Dielectric Function (MDF) was applied to obtain the thickness and the dielectric spectra of the middle nc-Si layer. Sensitive effect of the deposition time was obtained on the MDF parameters. A comparison is presented between the studied samples and reference materials.     

Charge transport along luminescent oxide layers containing Si and SiC nanoparticles

The electrical conductivity of silicon oxides containing silicon and silicon-carbon nanoparticles has been investigated. By use of sequential Si⁺ and C⁺ ion implantations in silicon oxide followed by an annealing at 1100 °C, luminescent Si nanocrystals and SiC nanoparticles were precipitated. The characterization of the electrical transport has been carried out on two kinds of structures, allowing parallel or perpendicular transport, with respect to the substrate. The first type of samples were elaborated by means of a focus-ion-beam technique: electrical contacts to embedded nanoparticles were made by milling two nanotrenches on the sample surface until reaching the buried layer, then filling them with tungsten. The distance between the electrodes is about 100 nm. The second type of samples correspond to 40 nm thick typical MOS capacitors.The electron transport along the buried layer has shown a dramatic lowering of the electrical current, up to five orders of magnitude, when applying a sequence of voltages. It has been related to a progressive charge retention inside the nanoparticles, which, on its turn, suppresses the electrical conduction along the layer. On the other hand, the MOS capacitors show a reversible carrier charge and discharge effect that limits the current at low voltage, mostly due to the presence of C in the layers. A typical Fowler-Nordheim injection takes place at higher applied voltages, with a threshold voltage equal to 23 V.     

AC conductivity of porous silicon: A fractal and surface transport mechanism?

Summary In this paper we report on the frequency dependence of the AC conductivity of porous silicon in the range 10 Hz-100 kHz. Two types of testing devices have been fabricated on three different series of samples formed electrochemically using as a starting materialptype,n ⁻-type andn ⁺-type silicon substrates. For frequencies less than 20-40 kHz the conductivity is found to follow a sublinear frequency dependence. This behaviour is typical of a carrier transport mechanism determined by an anomalous diffusion process. At higher frequencies we find that surface states influence the transport mechanism. This suggests a double-channel transport mechanism: one related to porous-silicon “volume” properties and the other more connected to the “surface” itself. Paper presented at the III INSEL (Incontro Nazionale sul Silicio Emettiore di Luce) Torino, 12–13 October 1995.     

Light emitting diode structure based on Si nanocrystals formed by implantation into thermal oxide

Light emitting diodes (LED), continuously operable at room temperature, have been fabricated by Si⁺ ion implantation into SiO₂ and subsequent annealing in order to form Si nanocrystals. A highly doped poly-Si layer was used to enhance injection into nanocrystals. Visible electroluminescence (EL) was observed from the LEDs with oxide thickness 180 Å for bias voltages above 8 V. The EL decay transient was similar to stretched-exponential decays observed for photoluminescence (PL) from Si nanocrystals.