Mechanism of quantum dot luminescence excitation within implanted SiO2:Si:C films

Results of the investigation of photoluminescence (PL) mechanisms for silicon dioxide films implanted with ions of silicon (100 keV; 7 × 10(16) cm(-2)) and carbon (50 keV; 7 × 10(15)-1.5 × 10(17) cm(-2)) are presented. The spectral, kinetic and thermal activation properties of the quantum dots (Si, C and SiC) formed by a subsequent annealing were studied by means of time-resolved luminescence spectroscopy under selective synchrotron radiation excitation. Independent quantum dot PL excitation channels involving energy transfer from the SiO(2) matrix point defects and excitons were discovered. A resonant mechanism of the energy transfer from the matrix point defects (E' and ODC) is shown to provide the fastest PL decay of nanosecond order. The critical distances (6-9 nm) of energy transport between the bulk defects and nanoclusters were determined in terms of the Inokuti-Hirayama model. An exchange interaction mechanism is realized between the surface defects (E(s)'-centres) and the luminescent nanoparticles. The peculiarities of an anomalous PL temperature dependence are explained in terms of a nonradiative energy transfer from the matrix excitons. It is established that resonant transfer to the luminescence centre triplet state is realized in the case of self-trapped excitons. In contrast, the PL excitation via free excitons includes the stages of energy transfer to the singlet state, thermally activated singlet-triplet conversion and radiative recombination.     

The mechanism of emission in the red photoluminescence band of porous silicon

Porous silicon (PS) exhibits several photoluminescence (PL) bands, whose spectral position and intensity depend strongly on the actual conditions of preparation of PS, its treatment, and subsequent use. The PS PL band peaking at about 1.8 eV and usually assigned to the intrinsic emission of silicon nanocrystals was studied. It was shown that the temperature-induced variation of the PL kinetics in the 80 to 300-K interval follows a complex pattern and depends noticeably on the actual point on the band profile. The temperature behavior of PL decay in the 1.8-eV band is determined by the electron-hole recombination rate within a nanocrystal and the cascade carrier transitions from small to large nanocrystals, with an attendant decrease in energy.     

Phonon confinement effects in Raman spectra of porous silicon at non‐resonant excitation condition

Light emitting porous silicon samples with different porosities, i.e. crystalline sizes, were produced from the low level doped p‐type silicon wafers by the anodization process. The effects of strong phonon confinement, redshift and broadening, were found on the O(Γ) phonon mode of the Raman spectra recorded at non‐resonant excitation condition using a near infrared 1064 nm laser excitation wavelength. Similarly, the blueshift of the photoluminescence peak was observed by reducing the crystalline sizes. Vibrational and optical findings were analysed within the existing models of confinement on the vibrational and electronic states of silicon nanocrystals. Since the energy of the photoluminescence peak of small nanocrystals also depends on the oxygen content on the surface of nanocrystals, the surface oxidation states were examined using infrared and energy dispersive spectroscopy. The partial coverage of the surface of nanocrystals was found due to the sample exposure to air. As a consequence, the photoluminescence energy did not increase as would be expected from the quantum confinement model. These results further indicate that the oxygen passivation along with the quantum confinement determines the electronic states of the silicon nanocrystals in porous silicon. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of surface Si-Si dimers on photoluminescence of silicon nanocrystals in the silicon dioxide matrix

The effect of surface states of silicon nanocrystals embedded in silicon dioxide on the photoluminescent properties of the nanocrystals is reported. We have investigated the time-resolved and stationary photoluminescence of silicon nanocrystals in the matrix of silicon dioxide in the visible and infrared spectral ranges at 77 and 300 K. The structures containing silicon nanocrystals were prepared by the high-temperature annealing of multilayer SiO _x /SiO₂ films. The understanding of the experimental results on photoluminescence is underlain by a model of autolocalized states arising on surface Si-Si dimers. The emission of autocatalized excitons is found for the first time, and the energy level of the autolocalized states is determined. The effect of these states on the mechanism of the excitation and the photoluminescence properties of nanocrystals is discussed for a wide range of their dimensions. It is reliably shown that the cause of the known blue boundary of photoluminescence of silicon nanocrystals in the silicon dioxide matrix is the capture of free excitons on autolocalized surface states.     

Radiative and nonradiative recombination of self-trapped exciton on silicon nanocrystal interface

The theory of the multiphonon and radiative recombination of a self-trapped exciton on the interface of a silicon nanocrystal in a SiO₂ matrix is developed. Self-trapped excitons play a key role in the hot carrier dynamics in nanocrystals under photoexcitation. The ratio of the probabilities of the multiphonon and radiative recombination of the self-trapped exciton is estimated. The probabilities of exciton tunnel transition from the self-trapped state to a nanocrystal are calculated for nanocrystals of various sizes. The infrared range spectrum of the luminescence of the self-trapped exciton is obtained.     

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.     

SiGe superlattice nanocrystal pure and doped with substitutional phosphorus single atom: Density functional theory study

Ab initio density functional theory is used to simulate electronic structure of hydrogenated SiGe nanocrystal superlattice pure and doped with substitutional P single atom. The results of electronic structure calculations are compared to the same size silicon and germanium nanocrystals. The comparison reveals that the energy gap of the three kinds of nanocrystals is nearly the same in non-relativistic and relativistic limits. Because of large width of gap in the present small nanocrystals the relativistic corrections are not as much important as in the case of bulk crystals. The doping of SiGe nanocrystal with P single atom introduced an impurity level at 4 eV below original conduction band edge. This result is much larger than comparable silicon bulk and nanocrystal doping with P atoms. Results also show that the deep internal angles and bonds in SiGe nanocrystals reach approximately the angles and structure of bulk crystals after nearly three surface layers. A double positively charged layer is located at the Ge terminated surface of SiGe nanocrystal. This layer is enhanced and is accompanied with a large increase of the dipole moment of the nanocrystal in the case of P doped nanocrystal. Due to oscillatory lattice potential in SiGe superlattice, density of states show that bands are broken up to sub-bands in comparison with silicon nanocrystal density of states especially at the conduction band.     

Spectrally resolved dynamics of energy transfer in quantum-dot assemblies: towards engineered energy flows in artificial materials

We report on the dynamics of resonant energy transfer in monodisperse, mixed-size, and energy-gradient (layered) assemblies of CdSe nanocrystal quantum dots. Time-resolved and spectrally resolved photoluminescence directly reveals the energy-dependent transfer rate of excitons from smaller to larger dots via electrostatic coupling. The data show a rapid (0.7-1.9 ns) energy transfer directly across a large tens-of-meV energy gap (i.e., between dots of disparate size), and suggest that interdot energy transfer can approach picosecond time scales in structurally optimized systems.     

Erbium excitation in a SiO<Subscript>2</Subscript>: Si-nc matrix under pulsed pumping

The photoluminescence of Er³⁺ ions in a SiO₂ matrix containing silicon nanocrystals 3.5 nm in diameter is studied under resonant and nonresonant pulsed pumping with pulses 5 ns in duration. The effective erbium excitation cross section under pulsed pumping, σ_eff = 8.7 × 10^?17 cm₂, is close to that for nanocrystals. Comparison of the erbium photoluminescence intensity obtained for a SiO₂ matrix with and without nanocrystals made it possible to determine the absolute concentration of optically active nanocrystals capable of exciting erbium ions, the concentration of optically active erbium, and the average number of erbium ions excited by one nanocrystal. The study revealed that excitation transfer from one erbium ion to another is a relatively slow process, which accounts for the low efficiency of erbium ion excitation under pulsed pumping in a SiO₂ matrix containing silicon nanocrystals.     

Photoluminescence of Er<Superscript>3+</Superscript> ions in layers of quasi-ordered silicon nanocrystals in a silicon dioxide matrix

The spectra and kinetics of photoluminescence from multilayered structures of quasi-ordered silicon nanocrystals in a silica matrix were studied for undoped samples and samples doped with erbium. It was shown that the optical excitation energy of silicon nanocrystals could be effectively transferred to Er³⁺ ions, which was followed by luminescence at a wavelength of 1.5 µm. The effectiveness of energy transfer increased as the size of silicon nanocrystals decreased and the energy of exciting light quanta increased. The excitation of erbium luminescence in the structures was explained based on dipole-dipole interaction (the Förster mechanism) between excitons in silicon nanocrystals and Er³⁺ ions in silica surrounding them.     

Enhancement of the photoluminescence of silicon nanocrystals under the influence of electric field

The effect of electric field generated by the application of surface acoustic waves on photoluminescence (PL) of silicon nanocrystals embedded in SiO₂ films is studied. It is shown that the application of electric field results in an increase in the intensity of nanocrystal PL, the increase amounting to 10% at a field amplitude of 6 kV cm⁻¹. The results are discussed within the frame of the self-trapped exciton model.     

Optical dynamics of energy-transfer from a CdZnO quantum well to a proximal Ag nanostructure

We studied photoluminescence (PL) and energy-transfer dynamics in a hybrid structure comprising a Cd(0.08)Zn(0.92)O quantum well (QW) and an Ag nanostructure. The observed PL quenching was dependent on the electronic states in the QW. Quenching occurred at low temperature where excited carriers recombined radiatively because of excitonic localization, which disappeared with increasing temperature due to delocalization of excitons. Furthermore, nanostructured Ag surfaces produced local surface plasmon (LSP) absorption that was resonant with the PL peak energy of the QW emission. These results indicate that the recombination energy of excitons transfers nonradiatively to induce LSP excitation, which was revealed using time-resolved PL measurements.     

Importance of ligands on TiO_2 nanocrystals for perovskite solar cells

The fabrication of high-quality electron-selective layers at low temperature is a prerequisite to realizing efficient flexible and tandem perovskite solar cells(PSCs). A colloidal-quantum-dot ink that contains TiO_2 nanocrystals enables the deposition of a flat film with matched energy level for PSCs; however, the selection of ligands on the TiO_2 surface is still unexplored. Here, we systematically studied the effect of the titanium diisopropoxide bis(acetylacetonate)(TiAc_2)ligand on the performance of PSCs with a planar n-i-p architecture. We prepared TiO_2 nanocrystals from TiCl4 and ethyl alcohol with Cl~- ligands attached on its surface and we found that a tiny amount of TiAc_2 treatment of as-prepared TiO_2 nanocrystals in a mixed solution of chloroform and methyl alcohol can enhance PSC power conversion efficiency(PCE)from 14.7% to 18.3%. To investigate the effect of TiAc_2 ligand on PSCs, TiO_2 samples with different TiAc_2 content were prepared by adding TiAc_2 into the as-obtained TiO_2 nanocrystal solution. We use x-ray photoelectron spectroscopy to identify the content of Cl so as to reveal that Cl ligands can be substituted by TiAc_2. We speculate that the improvement in PCE originates from amorphous TiO_2 formation on the TiO_2 nanocrystal surface, whereby a single-molecule layer of amorphous TiO_2 facilitates charge transfer between the perovskite film and the TiO_2 electronic transport layer, but excessive TiAc_2 lowers the PSC performance dramatically. We further prove our hypothesis by x-ray diffraction measurements. We believe the PCE of PSCs can be further improved by carefully choosing the type and changing the content of surface ligands on TiO_2 nanocrystal.     

Influence of preparation and storage conditions on photoluminescence of porous silicon powder with embedded Si nanocrystals

The time changes of photoluminescence (PL) characteristics of porous silicon (porSi) powder during storing in different ambients have been reported. A porous silicon material with embedded Si nanocrystals of size of few nanometers was prepared by an electrochemical method from 10 to 20 Ωcm p-type Si wafers, and both constant and pulse current anodization regimes were used. A powder with a submicron average particle size was obtained by simple mechanical lift-off of the porous layer followed by additional manual milling. The air, hexane, and water as storage media were used, and modification by a nonionic surfactant (undecylenic acid) of the porSi surface was applied in the latter case. Dependence of PL characteristics on preparation and storage conditions was then studied. A remarkable blue shift of a position of PL maximum was observed in time for porSi powders in each storage media. In water suspension a many-fold build-up (10–30) of PL intensity in a time scale of few days was accompanied by an observed blue shift. Photoluminescence time behavior of porSi powders was described by a known mechanism of the change of porSi PL from free exciton emission of Si nanocrystals to luminescence of localized oxidized states on the Si nanocrystal surface.     

Multipeak-structured photoluminescence mechanisms of as-prepared and oxidized Si nanoporous pillar arrays

Silicon dominates the electronic industry, but its poor optical properties mean that it is not preferred for photonic applications. Visible photoluminescence (PL) was observed from porous Si at room temperature in 1990, but the origin of these light emissions is still not fully understood. This paper reports that an Si nanocrystal, silicon nanoporous pillar array (Si-NPA) with strong visible PL has been prepared on a Si wafer substrate by the hydrothermal etching method. After annealing in O₂ atmosphere, the hydride coverage of the Si pillar internal surface is replaced by an oxide layer, which comprises of a great quantity of Si nanocrystal (nc-Si) particles and each of them are encapsulated by an Si oxide layer. Meanwhile a transition from efficient triple-peak PL bands from blue to red before annealing to strong double-peak blue PL bands after annealing is observed. Comparison of the structural, absorption and luminescence characteristics of the as-prepared and oxidized samples provides evidence for two competitive transition processes, the band-to-band recombination of the quantum confinement effect of nc-Si and the radiative recombination of excitons from the luminescent centres located at the surface of nc-Si units or in the Si oxide layers that cover the nc-Si units because of the different oxidation degrees. The sizes of nc-Si and the quality of the Si oxide surface are two major factors affecting two competitive processes. The smaller the size of nc-Si is and the stronger the oxidation degree of Si oxide layer is, the more beneficial for the luminescent centre recombination process to surpass the quantum confinement process is. The clarification on the origin of the photons may be important for the Si nanoporous pillar array to control both the PL band positions and the relative intensities according to future device requirements and further fabrication of optoelectronic nanodevices.     

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.     

Excitonic photoluminescence characteristics of amorphous silicon nanoparticles embedded in silicon nitride film

We have investigated the photoluminescence (PL) properties of amorphous silicon nanoparticles (a-Si NPs) embedded in silicon nitride film (Si-in-SiN_x) grown by helicon wave plasma-enhanced chemical vapor deposition (HWP-CVD) technique. The PL spectrum of the film exhibits a broad band constituted of two Gaussian components. From photoluminescence excitation (PLE) measurements, it is elucidated that the two PL bands are associated with the a-Si NPs and the silicon nitride matrix surrounding a-Si NPs, respectively. The existence of Stokes shift between PL and absorption edge indicates that radiative recombination of carriers occurs in the states at the surface of the Si NPs, whereas their generation takes place in the a-Si NPs cores and the silicon nitride matrix, respectively. The visible PL of the film originates from the radiative recombination of excitons trapped in the surface states. At decreasing excitation energy (E_ex), the PL peak energy was found to be redshifted, accompanied by a narrowing of the bandwidth. These results are explained by surface exciton recombination model taking into account there existing a size distribution of a-Si NPs in the silicon nitride matrix.     

Trap states in oxidation layer of nanocrystal Si

The photoluminescence （PL） of nanocrystal present in porous silicon shifts from the near infrared to the ultraviolet depending on the size when the surface is passivated with Si-H bonds. After oxidation, the centre wavelength of PL band is pinned in a region of 700-750 nm and its intensity increases obviously. Calculation shows that trap electronic states appear in the band gap of a smaller nanocrystal when Si = O bonds or Si-O-Si bonds are formed. The changes in PL intensity and wavelength can be explained by both quantum confinement and trap states in an oxidation layer of nanocrystal. In the theoretical model, the most important factor in the enhancement and the pinning effects of PL emission is the relative position between the level of the trap states and the level of the photoexcitation in the silicon nanocrystal.     

Efficient Integration of Single-Photon Emitters in Thin InSe Films into Resonance Silicon Waveguides

A concept of the optimal design of a silicon waveguide based on optically coupled Mie-resonant nanoantennas for efficient inputting of light from point emitters associated with excitons localized at defects in a thin InSe film is proposed. Numerical calculations demonstrate that the efficiency of coupling between a dipole emitter and a resonant silicon waveguide is four orders of magnitude greater than that for a conventional ridge waveguide.

     

Spin Physics of Excitons in Colloidal Nanocrystals

We present a review of spin-dependent properties of excitons in semiconductor colloidal nanocrystals. The photoluminescences (PL) properties of neutral and charged excitons (trions) are compared. The mechanisms and the polarization of radiative recombination of a “dark” (spin-forbidden) exciton that determines the low-temperature PL of colloidal nanocrystals are discussed in detail. The radiative recombination of a dark exciton becomes possible as a result of simultaneous flips of the surface spin and electron spin in a dark exciton that leads to admixture of bright exciton states. This recombination mechanism is effective in the case of a disordered state of the spin system and is suppressed if the polaron ferromagnetic state forms. The conditions and various mechanisms of formation of the spin polaron state and possibilities of its experimental detection are discussed. The experimental and theoretical studies of magnetic field-induced circular polarization of PL in ensembles of colloidal nanocrystals are reviewed.