Glassy-like Transients in Semiconductor Nanomaterials.

Glassy behavior is manifested by three time-dependent characteristics of a dynamic physical property. Such behaviors have been found in the electrical conductivity transients of various disordered systems, but the mechanisms that yield the glassy behavior are still under intensive debate. The focus of the present work is on the effect of the quantum confinement (QC) and the Coulomb blockade (CB) effects on the experimentally observed glassy-like behavior in semiconductor nanomaterials. Correspondingly, we studied the transient electrical currents in semiconductor systems that contain CdSe or Si nanosize crystallites, as a function of that size and the ambient temperature. In particular, in contrast to the more commonly studied post-excitation behavior in electronic glassy systems, we have also examined the current transients during the excitation. This has enabled us to show that the glassy behavior is a result of the nanosize nature of the studied systems and thus to conclude that the observed characteristics are sensitive to the above effects. Following this and the temperature dependence of the transients, we derived a more detailed macroscopic and microscopic understanding of the corresponding transport mechanisms and their glassy manifestations. We concluded that the observed electrical transients must be explained not only by the commonly suggested principle of the minimization of energy upon the approach to equilibrium, as in the mechanical (say, viscose) glass, but also by the principle of minimal energy dissipation by the electrical current which determines the percolation network of the electrical conductivity. We further suggest that the deep reason for the glassy-like behavior that is observed in the electrical transients of the nanomaterials studied is the close similarity between the localization range of electrons due to the Coulomb blockade and the caging range of the uncharged atomic-size particles in the classical mechanical glass. These considerations are expected to be useful for the understanding and planning of semiconductor nanodevices such as corresponding quantum dot memories and quantum well MOSFETs.

Simple holistic solution to Archie's-law puzzle in porous media.

In this paper, we account for the many critical exponents derived from the studies of the electrical conductivity in porous media by applying analysis of the well-known relation known as Archie's law. In spite of its seeming simplicity this law is considered to be "poorly understood," and the question that was and still is debated in the literature is whether there is some "hidden physics" in this law, or if it is "strictly a parametrization use for curve fitting with a priori no physical meaning." Our solution to the corresponding long-debated 78 years old puzzle is based on the classical percolation theory, but it also involves a principle that is based on continuum percolation. This principle is that the electrical properties of a percolation system are determined by the interplay between the connectivity of the conducting objects in that system, and the connectivity of the intersections between pairs of them. We thus propose a general concept that we call an electrically affected connectivity, and we predict the corresponding evolvement of the conductivity critical exponent with the increase of the content of the electrically conducting phase. Then, we show that the zerolike threshold that characterizes Archie's law is what enables the observation of this evolution. Combining the above principle and the latter feature, we provide a holistic, yet simple, solution to the longstanding controversy surrounding this law and its practical applications. In contrast with many previous claims that Archie's law lacks a physical basis, and the commonly suggested experiential explanations for it, we provide a solution that is physically based and thus elucidates Archie's law by showing clearly that it represents a bona fide phase transition phenomenon. This conclusion and its generality are strongly supported by the fact that it also explains the behavior of the electrical conductivity exponents in nonporous systems such as composite materials. The predicted ability to extract the long sought microgeometrical information from Archie's-law data, within the framework of the percolation phase transition, is expected to open a new direction in the understanding and the applications of this law.

On the influence of multiple cations on the in-gap states and phototransport properties of iodide-based halide perovskites.

In-gap states in solar cell absorbers that are recombination centers determine the cell's photovoltaic performance. Using scanning tunneling spectroscopy (STS), temperature-dependent photoconductivity and steady-state photocarrier-grating measurements we probed, directly and indirectly, the energies of such states, both at the surface and in the bulk of two similar, but different halide perovskites, the single cation MAPbI3 (here MAPI) and the mixed cation halide perovskite, FA0.79MA0.16Cs0.05Pb(I0.83Br0.17)3 (here MCHP). We found a correlation between the energy distribution of the in-gap states, as determined by STS measurements, and their manifestation in the photo-transport parameters of the MCHP absorbers. In particular, our results suggest that the in-gap recombination centers in the MCHP are shallower than those of MAPI. This can be one explanation for the better photovoltaic efficiency of the former.

The influence of conjugated alkynyl(aryl) surface groups on the optical properties of silicon nanocrystals: photoluminescence through in-gap states.

Developing new methods, other than size and shape, for controlling the optoelectronic properties of semiconductor nanocrystals is a highly desired target. Here we demonstrate that the photoluminescence (PL) of silicon nanocrystals (SiNCs) can be tuned in the range 685-800 nm solely via surface functionalization with alkynyl(aryl) (phenylacetylene, 2-ethynylnaphthalene, 2-ethynyl-5-hexylthiophene) surface groups. Scanning tunneling microscopy/spectroscopy on single nanocrystals revealed the formation of new in-gap states adjacent to the conduction band edge of the functionalized SiNCs. PL red-shifts were attributed to emission through these in-gap states, which reduce the effective band gap for the electron-hole recombination process. The observed in-gap states can be associated with new interface states formed via (-Si-C≡C-) bonds in combination with conjugated molecules as indicated by ab initio calculations. In contrast to alkynyl(aryl)s, the formation of in-gap states and shifts in PL maximum of the SiNCs were not observed with aryl (phenyl, naphthalene, 2-hexylthiophene) and alkynyl (1-dodecyne) surface groups. These outcomes show that surface functionalization with alkynyl(aryl) molecules is a valuable tool to control the electronic structure and optical properties of SiNCs via tuneable interface states, which may enhance the performance of SiNCs in semiconductor devices.

Size-dependent donor and acceptor states in codoped Si nanocrystals studied by scanning tunneling spectroscopy.

The electrical and optical properties of semiconductor nanocrystals (NCs) can be controlled, in addition to size and shape, by doping. However, such a process is not trivial in NCs due to the high formation energy of dopants there. Nevertheless, it has been shown theoretically that in the case of B and P (acceptor/donor) codoped Si-NCs the formation energy is reduced relative to that of single type doping. Previous comprehensive measurements on ensembles of such codoped Si-NCs have pointed to the presence of donor and acceptor states within the energy gap. However, such a conjecture has not been directly verified previously. Following that, we investigate here the electronic properties of B and P codoped Si-NCs via Scanning Tunneling Spectroscopy. We monitored the quantum confinement effect in this system, for which the energy gap changed from ∼1.4 eV to ∼1.8 eV with the decrease of NC diameter from 8.5 to 3.5 nm. Importantly, all spectra showed two in-gap band-states, one close to the conduction band edge and the other to the valence band edge, which we attribute to the P and B dopant levels, respectively. The energy separation between these dopants states decrease monotonically with increasing NC diameter, in parallel to the decrease of the conduction-to-valence bands separation. A fundamental quantity that is derived directly for these Si-NCs is the intrinsic like position of the Fermi energy, a non-trivial result that is very relevant for understanding the system. Following the above results we suggest an explanation for the character and the origin of the dopants bands.

Mobility-Lifetime Products in MAPbI3 Films.

Photovoltaic solar cells operate under steady-state conditions that are established during the charge carrier excitation and recombination. However, to date no model of the steady-state recombination scenario in halide perovskites has been proposed. In this Letter we present such a model that is based on a single type of recombination center, which is deduced from our measurements of the illumination intensity dependence of the photoconductivity and the ambipolar diffusion length in those materials. The relation between the present results and those from time-resolved measurements, such as photoluminescence that are commonly reported in the literature, is discussed.

Grafting Poly(3-hexylthiophene) from Silicon Nanocrystal Surfaces: Synthesis and Properties of a Functional Hybrid Material with Direct Interfacial Contact.

Hybrid functional materials (HFMs) comprised of semiconductor nanoparticles and conjugated polymers offer the potential of synergetic photophysical properties. We have developed HFMs based upon silicon nanocrystals (SiNCs) and the conductive polymer poly(3-hexylthiophene) (SiNC@P3HT) by applying surface-initiated Kumada catalyst transfer polycondensation (SI-KCTP). One unique characteristic of the developed SiNC@P3HT is the formation of a direct covalent bonding between SiNCs and P3HT. The presented method for obtaining direct interfacial attachment, which is not accessible using other methods, may allow for the development of materials with efficient electronic communication at the donor-acceptor interfaces. Systematic characterization provides evidence of a core-shell structure, enhanced interfacial electron and/or energy transfer between the P3HT and SiNC components, as well as formation of a type-II heterostructure.

Si-rich Al2O3 films grown by RF magnetron sputtering: structural and photoluminescence properties versus annealing treatment.

Silicon-rich Al2O3 films (Six(Al2O3)1-x) were co-sputtered from two separate silicon and alumina targets onto a long silicon oxide substrate. The effects of different annealing treatments on the structure and light emission of the films versus x were investigated by means of spectroscopic ellipsometry, X-ray diffraction, micro-Raman scattering, and micro-photoluminescence (PL) methods. The formation of amorphous Si clusters upon the deposition process was found for the films with x ≥ 0.38. The annealing treatment of the films at 1,050°C to 1,150°C results in formation of Si nanocrystallites (Si-ncs). It was observed that their size depends on the type of this treatment. The conventional annealing at 1,150°C for 30 min of the samples with x = 0.5 to 0.68 leads to the formation of Si-ncs with the mean size of about 14 nm, whereas rapid thermal annealing of similar samples at 1,050°C for 1 min showed the presence of Si-ncs with sizes of about 5 nm. Two main broad PL bands were observed in the 500- to 900-nm spectral range with peak positions at 575 to 600 nm and 700 to 750 nm accompanied by near-infrared tail. The low-temperature measurement revealed that the intensity of the main PL band did not change with cooling contrary to the behavior expected for quantum confined Si-ncs. Based on the analysis of PL spectrum, it is supposed that the near-infrared PL component originates from the exciton recombination in the Si-ncs. However, the most intense emission in the visible spectral range is due to either defects in matrix or electron states at the Si-nc/matrix interface.

Microscopic evidence for the modification of the electronic structure at grain boundaries of Cu(In(1-x),Ga(x))Se2 films.

We investigated the electronic properties around grain boundaries of polycrystalline Cu(In(1-x),Ga(x)Se(2)) films as a function of Ga content, using scanning tunneling spectroscopy. Spectra acquired on samples with low Ga content (x=0 and 0.33) reveal downward band bending with respect to adjacent p-type grains, suggesting type inversion at the surface of grain boundaries. Such a behavior was not observed for samples with high Ga contents. These results are consistent with our atomic force microscopy data and may shed light on the origin of the x-dependent efficiency for polycrystalline Cu(In(1-x),Ga(x)Se(2))-based solar cells.

Transparent conductive coatings by printing coffee ring arrays obtained at room temperature.

We report here a concept for utilization of the "coffee ring effect" and inkjet printing to obtain transparent conductive patterns, which can replace the widely used transparent conductive oxides, such as ITO. The transparent conductive coating is achieved by forming a 2-D array of interconnected metallic rings. The rim of the individual rings is less than 10 microm in width and less than 300 nm in height, surrounding a "hole" with a diameter of about 150 microm; therefore the whole array of the interconnected rings is almost invisible to the naked eye. The rims of the rings are composed of self-assembled, closely packed silver nanoparticles, which make the individual rings and the resulting array electrically conductive. The resulting arrays of rings have a transparency of 95%; resistivity of 0.5 cm(2) was 4 +/- 0.5 Omega/, which is better than conventional ITO transparent thin films. The silver rings and arrays are fabricated by a very simple, low cost process, based on inkjet printing of a dispersion of 0.5 wt % silver nanoparticles (approximately 20 nm diameter) on plastic substrates. The performance of this transparent conductive coating was demonstrated by using it as an electrode for a plastic electroluminescent device, demonstrating the applicability of this concept in plastics electronics. It is expected that such transparent conductive coatings can be used in a wide range of applications such as displays (LCD, plasma, touch screens, e-paper), lighting devices (electroluminescence, OLED), and solar cells.

Electrical transport phenomena in systems of semiconductor quantum dots.

While a fairly good understanding of optical and transport properties that are associated with single quantum dots has emerged in recent years the understanding of the relation between these properties and the observed macroscopic optical and electrical properties of solid ensembles of such dots is still at a very rudimentary level. This is in particular so in regard to the transport properties where the interplay between inter-dot conduction and the connectivity of the dots network determines the macroscopic observations. Reviewing the basic concepts and issues associated with these two essential ingredients, and considering some recent experimental observations on quantum dot ensembles of CdSe and Si, an effort is made here to derive a whole-but-simple physical basis for the understanding of the transport and the optoelectronic properties of solid state ensemble of semiconductor quantum dots.

Observation of current reversal in the scanning tunneling spectra of fullerene-like WS2 nanoparticles.

Current-voltage characteristics measured using STM on fullerene-like WS2 nanoparticles show zero-bias current and contain segments in which the tunneling current flows opposite to the applied bias voltage. In addition, negative differential conductance peaks emerge in these reversed current segments, and the characteristics are hysteretic with respect to the change in the voltage sweep direction. Such unusual features resemble those appearing in cyclic voltammograms, but are uniquely observed here in tunneling spectra measured in vacuum, as well as in ambient and dry atmosphere conditions. This behavior is attributed to tunneling-driven electrochemical processes.

Ring stain effect at room temperature in silver nanoparticles yields high electrical conductivity.

We demonstrate that metallic rings formed spontaneously at room temperature via evaporation of aqueous drops containing silver nanoparticles (20-30 nm in diameter) exhibit high electrical conductivity (up to 15% of that for bulk silver). The mechanism underlying this self-assembly phenomena is the "ring stain effect", where self-pinning is combined with capillary flow to form a ring consisting of close-packed metallic nanoparticles along the perimeter of a drying droplet. Our macroscopic and microscopic (applying conductive atomic force microscopy) transport measurements show that the conductivity of the ring, which has a metallic brightness, is orders of magnitude larger than that of corresponding aggregates developed without the ring formation, where high conductivity is known to appear only after annealing at high temperature.