Daniel Hiller

Charge transport in Si nanocrystal/SiO2 superlattices

Size-controlled silicon nanocrystals in silicon oxynitride matrix were prepared using plasma-enhanced chemical vapor deposition following the superlattice approach. A combination of current transport and charge trapping studies is carried out on a number of samples with varied structural configuration. We demonstrate that at low electric fields, trapping of injected carriers dominates, if the coupling between the silicon nanocrystals is strong. In contrast, we show that at higher electric fields, the charge distribution within the films is essentially governed by charge separation within the superlattice. This effect can be well explained by a two-step electric field ionization of silicon nanocrystals that proceeds via defect-assisted band-to-band tunneling of silicon valence electrons to the conduction band and is mediated by silicon surface dangling bonds. The defects are dominating the charge transport even if the defect density is reduced to a minimum by efficient hydrogen passivation.

Phosphorus doping of Si nanocrystals embedded in silicon oxynitride determined by atom probe tomography

Silicon nanocrystals (SiNCs) embedded in a silicon oxide matrix were studied by 3D atom probe tomography (APT). The distribution of the SiNC diameter was found to have a mean value of 3.7 ± 0.8 nm. The elemental composition of these particles was determined by employing two different approaches: (i) The proximity histogram method and (ii) a cluster identification algorithm based on maximum-atom separations. Both approaches give very similar values in terms of the amount of P, O, and Si within the SiNCs: the mean atomic concentrations are cP = 0.77% ± 0.4%, cO = 12.3% ± 2.1%, and cSi = 85.3% ± 2.1%. A detailed cluster analysis implies that, on average, a 4.5-nm SiNC would contain around 30 P atoms, whereas a 2.0-nm SiNC would contain only around 3 P atoms. Radial concentration profiles obtained for these SiNCs indicate that the P content is inhomogeneous and possibly enhanced at the boundary as compared to the interior of the NCs. About 20% of the P atoms are found to be incorporated into the SiNCs, wherea...

Pb(0) centers at the Si-nanocrystal/SiO2 interface as the dominant photoluminescence quenching defect

The correlation of paramagnetic defects and photoluminescence (PL) of size controlled Si nanocrystals (NCs) has been studied as a function of annealing ambient (Ar or N2) and subsequent H2 treatment. The dominant defects measured by electron spin resonance are interfacial Pb(0) and Pb1 centers. Whereas the latter appears to play only a minor role in PL quenching, a pronounced correlation between Pb(0) density and PL intensity is demonstrated. Annealing in N2 is found to be superior over Ar both in terms of PL performance and defect densities. The origin of the PL blueshift found for N2 annealing compared to Ar was previously interpreted as a growth suppression of the Si clusters due to incorporation of N atoms or a silicon consuming nitridation at the NC/SiO2 interface. The results presented here, demonstrate the blueshift to be more pronounced for small NCs (∼2 nm) than for larger ones (∼4.5 nm). Therefore, we suggest an alternative interpretation that is based on the influence of the polarity of surface...

Location and Electronic Nature of Phosphorus in the Si Nanocrystal--SiO2 System.

Up to now, no consensus exists about the electronic nature of phosphorus (P) as donor for SiO2-embedded silicon nanocrystals (SiNCs). Here, we report on hybrid density functional theory (h-DFT) calculations of P in the SiNC/SiO2 system matching our experimental findings. Relevant P configurations within SiNCs, at SiNC surfaces, within the sub-oxide interface shell and in the SiO2 matrix were evaluated. Atom probe tomography (APT) and its statistical evaluation provide detailed spatial P distributions. For the first time, we obtain ionisation states of P atoms in the SiNC/SiO2 system at room temperature using X-ray absorption near edge structure (XANES) spectroscopy, eliminating structural artefacts due to sputtering as occurring in XPS. K energies of P in SiO2 and SiNC/SiO2 superlattices (SLs) were calibrated with non-degenerate P-doped Si wafers. results confirm measured core level energies, connecting and explaining XANES spectra with h-DFT electronic structures. While P can diffuse into SiNCs and predominantly resides on interstitial sites, its ionization probability is extremely low, rendering P unsuitable for introducing electrons into SiNCs embedded in SiO2. Increased sample conductivity and photoluminescence (PL) quenching previously assigned to ionized P donors originate from deep defect levels due to P.

Doping efficiency of phosphorus doped silicon nanocrystals embedded in a SiO2 matrix

Strongly size controlled silicon nanocrystals in silicon oxynitride matrix were prepared using plasma enhanced chemical vapor deposition following the superlattice approach. Doping was achieved by adding diluted phosphine as a precursor gas. Phosphorus quantification was done by secondary ion mass spectrometry. A model based on Poissonian distributions of interface defects and dopants is proposed to calculate the defects and the dopants per silicon nanocrystal as a function of phosphorus concentration. The model requires the comparison between the photoluminescence spectra from passivated and unpassivated samples. Finally, the doping efficiency of silicon nanocrystals embedded in silicon oxynitride is estimated to be >20%.

Determining the crystalline degree of silicon nanoclusters/SiO2 multilayers by Raman scattering

We use Raman scattering to investigate the size distribution, built-in strains and the crystalline degree of Si-nanoclusters (Si-nc) in high-quality Si-rich oxynitride/SiO2 multilayered samples obtained by plasma enhanced chemical vapor deposition and subsequent annealing at 1150 °C. An initial structural characterization of the samples was performed by means of energy-filtered transmission electron microscopy (EFTEM) and X-ray diffraction (XRD) to obtain information about the cluster size and the presence of significant amounts of crystalline phase. The contributions to the Raman spectra from crystalline and amorphous Si were analyzed by using a phonon confinement model that includes the Si-nc size distribution, the influence of the matrix compressive stress on the clusters, and the presence of amorphous Si domains. Our lineshape analysis confirms the existence of silicon precipitates in crystalline state, in good agreement with XRD results, and provides also information about the presence of a large com...

Effects of inter-nanocrystal distance on luminescence quantum yield in ensembles of Si nanocrystals

The absolute photoluminescence (PL) quantum yield (QY) of multilayers of Silicon nanocrystals (SiNCs) separated by SiO2 barriers were thoroughly studied as function of the barrier thickness, excitation wavelength, and temperature. By mastering the plasma-enhanced chemical vapor deposition growth, we produce a series of samples with the same size-distribution of SiNCs but variable interlayer barrier distance. These samples enable us to clearly demonstrate that the increase of barrier thickness from ∼1 to larger than 2 nm induces doubling of the PL QY value, which corresponds to the change of number of close neighbors in the hcp structure. The temperature dependence of PL QY suggests that the PL QY changes are due to a thermally activated transport of excitation into non-radiative centers in dark NCs or in the matrix. We estimate that dark NCs represent about 68% of the ensemble of NCs. The PL QY excitation spectra show no significant changes upon changing the barrier thickness and no clear carrier multipli...

Rapid thermal annealing of size-controlled Si nanocrystals: Dependence of interface defect density on thermal budget

Photoluminescence properties of size-controlled Si nanocrystals (NCs) formed by various annealings have been studied in detail. The thermal treatments involve rapid thermal annealing (RTA, 10 to 180 s) as well as conventional tube furnace annealing (1h) at 1100 °C. Whereas the photoluminescence (PL) peak positions and the TEM images indicate only minor changes in NC size, the PL intensity varies over more than two orders of magnitude. A correlation between the total thermal budget applied by the different annealing treatments and the PL intensity is demonstrated. In addition, the PL improvement of interface defect passivation by post-annealing in H2 ambient is investigated. RTA with H2 passivation is not able to achieve the PL intensity and NC interface quality of conventionally annealed and passivated samples. The combination of these results with our previous electron spin resonance studies allows to estimate the interface defect densities. Tube furnace annealed samples after H2 treatment have less than...

Absence of quantum confinement effects in the photoluminescence of Si3N4–embedded Si nanocrystals

Superlattices of Si-rich silicon nitride and Si3N4 are prepared by plasma-enhanced chemical vapor deposition and, subsequently, annealed at 1150 °C to form size-controlled Si nanocrystals (Si NCs) embedded in amorphous Si3N4. Despite well defined structural properties, photoluminescence spectroscopy (PL) reveals inconsistencies with the typically applied model of quantum confined excitons in nitride-embedded Si NCs. Time-resolved PL measurements demonstrate 105 times faster time-constants than typical for the indirect band structure of Si NCs. Furthermore, a pure Si3N4 reference sample exhibits a similar PL peak as the Si NC samples. The origin of this luminescence is discussed in detail on the basis of radiative defects and Si3N4 band tail states in combination with optical absorption measurements. The apparent absence of PL from the Si NCs is explained conclusively using electron spin resonance data from the Si/Si3N4 interface defect literature. In addition, the role of Si3N4 valence band tail states as...

Intense green-yellow electroluminescence from Tb+-implanted silicon-rich silicon nitride/oxide light emitting devices

High optical power density of 0.5 mW/cm2, external quantum efficiency of 0.1%, and population inversion of 7% are reported from Tb+-implanted silicon-rich silicon nitride/oxide light emitting devices. Electrical and electroluminescence mechanisms in these devices were investigated. The excitation cross section for the 543 nm Tb3+ emission was estimated under electrical pumping, resulting in a value of 8.2 × 10−14 cm2, which is one order of magnitude larger than one reported for Tb3+:SiO2 light emitting devices. These results demonstrate the potentiality of Tb+-implanted silicon nitride material for the development of integrated light sources compatible with Si technology.