Interaction of excitons with charge carriers in organic solids: charged excitonic complexes

The coupled states of molecular excitons with charge carriers are considered. In centrosymmetric crystals the attraction of excitons to charge carriers arises mainly from the increase of molecular polarizability on electronic excitation, so that the exciton energy decreases in the electric field of the charge. In noncentrosymmetric crystals, the main contribution to the energy of exciton-charge interaction comes from the change of the static dipole moment of the molecule on excitation. Some physical consequences and possible experimental observations of the above-mentioned coupled states are discussed.     

Fabrication of all-inorganic nanocrystal solids through matrix encapsulation of nanocrystal arrays

A general strategy for low-temperature processing of colloidal nanocrystals into all-inorganic films is reported. The present methodology goes beyond the traditional ligand-interlinking scheme and relies on encapsulation of morphologically defined nanocrystal arrays into a matrix of a wide-band gap semiconductor, which preserves optoelectronic properties of individual nanoparticles while rendering the nanocrystal film photoconductive. Fabricated solids exhibit excellent thermal stability, which is attributed to the heteroepitaxial structure of nanocrystal-matrix interfaces, and show compelling light-harvesting performance in prototype solar cells.     

A facile chemical route to semiconductor metal sulfide nanocrystal superlattices

We report a facile chemical route for the synthesis of monodisperse nanocrystals of various metal sulfides (PbS, Cu(2)S, and Ag(2)S) and their assemblies into nanocrystal superlattices (NCSs); the sulfides NCSs were precipitated by adding ethanol to nanocrystal colloids, which were obtained directly by a reaction between metal thiolate and thioacetamide in a pure dodecanethiol solvent.     

Energy distribution of charge carriers in solids in highly non-equilibrium states considering cascade transitions and inelastic scattering

A study is made of the cascade process, which describes the energy loss and multiplication of highly non-equilibrium secondary electrons and holes in crystalline platinum irradiated by low-energy electrons. The pair-creation scattering rates are evaluated in the framework of statistical model that takes into account the electron band structure of platinum. Kinetic equations for the excited electron and hole energy distributions are solved numerically in the isotropic scattering approximation for some primary (excitation) energies E_p that do not exceed the plasma energy E_F+ℏω_pl.     

Mechanisms of fluorescence blinking in semiconductor nanocrystal quantum dots

The light-induced spectral diffusion and fluorescence intermittency (blinking) of semiconductor nanocrystal quantum dots are investigated theoretically using a diffusion-controlled electron-transfer (DCET) model, where a light-induced one-dimensional diffusion process in energy space is considered. Unlike the conventional electron-transfer reactions with simple exponential kinetics, the model naturally leads to a power-law statistics for the intermittency. We formulate a possible explanation for the spectral broadening and its proportionality to the light energy density, the -32 power law for the blinking statistics of the fluorescence intermittency, the breakdown of the power-law behavior with a bending tail for the "light" periods, a lack of bending tail for the "dark" periods (but would eventually appear at later times), and the dependence of the bending tail on light intensity and temperature. This DCET model predicts a critical time t(c) (a function of the electronic coupling strength and other quantities), such that for times shorter than t(c) the exponent for the power law is -12 instead of -32. Quantitative analyses are made of the experimental data on spectral diffusion and on the asymmetric blinking statistics for the "on" and "off" events. Causes for deviation of the exponent from the ideal value of -32 are also discussed. Several fundamental properties are determined from the present experimental data, the diffusion correlation time, the Stokes shift, and a combination of other molecular-based quantities. Specific experiments are suggested to test the model further, extract other molecular properties, and elucidate more details of the light-induced charge-transfer dynamics in quantum dots.     

A new route to charge distributions in ionic solids

A new empirical route for the calculation of charge distributions in inorganic solids with respect to the formal oxidation state is presented, together with distances and coordination numbers for the respective ions.     

Water splitting on composite plasmonic-metal/semiconductor photoelectrodes: evidence for selective plasmon-induced formation of charge carriers near the semiconductor surface

A critical factor limiting the rates of photocatalytic reactions, including water splitting, on oxide semiconductors is the high rate of charge-carrier recombination. In this contribution, we demonstrate that this issue can be alleviated significantly by combining a semiconductor photocatalyst with tailored plasmonic-metal nanostructures. Plasmonic nanostructures support the formation of resonant surface plasmons in response to a photon flux, localizing electromagnetic energy close to their surfaces. We present evidence that the interaction of localized electric fields with the neighboring semiconductor allows for the selective formation of electron/hole (e(-)/h(+)) pairs in the near-surface region of the semiconductor. The advantage of the formation of e(-)/h(+) pairs near the semiconductor surface is that these charge carriers are readily separated from each other and easily migrate to the surface, where they can perform photocatalytic transformations.     

Thiocyanate-capped nanocrystal colloids: vibrational reporter of surface chemistry and solution-based route to enhanced coupling in nanocrystal solids

Ammonium thiocyanate (NH(4)SCN) is introduced to exchange the long, insulating ligands used in colloidal nanocrystal (NC) synthesis. The short, air-stable, environmentally benign thiocyanate ligand electrostatically stabilizes a variety of semiconductor and metallic NCs in polar solvents, allowing solution-based deposition of NCs into thin-film NC solids. NH(4)SCN is also effective in replacing ligands on NCs after their assembly into the solid state. The spectroscopic properties of this ligand provide unprecedented insight into the chemical and electronic nature of the surface of the NCs. Spectra indicate that the thiocyanate binds to metal sites on the NC surface and is sensitive to atom type and NC surface charge. The short, thiocyanate ligand gives rise to significantly enhanced electronic coupling between NCs as evidenced by large bathochromic shifts in the absorption spectra of CdSe and CdTe NC thin films and by conductivities as high as (2 ± 0.7) × 10(3) Ω(-1) cm(-1) for Au NC thin films deposited from solution. NH(4)SCN treatment of PbTe NC films increases the conductivity by 10(13), allowing the first Hall measurements of nonsintered NC solids, with Hall effect mobilities of 2.8 ± 0.7 cm(2)/(V·s). Thiocyanate-capped CdSe NC thin films form photodetectors exhibiting sensitive photoconductivity of 10(-5) Ω(-1) cm(-1) under 30 mW/cm(2) of 488 nm illumination with I(photo)/I(dark) > 10(3) and form n-channel thin-film transistors with electron mobilities of 1.5 ± 0.7 cm(2)/(V·s), a current modulation of >10(6), and a subthreshold swing of 0.73 V/decade.     

Effect of metal ions on photoluminescence, charge transport, magnetic and catalytic properties of all-inorganic colloidal nanocrystals and nanocrystal solids

Colloidal semiconductor nanocrystals (NCs) provide convenient "building blocks" for solution-processed solar cells, light-emitting devices, photocatalytic systems, etc. The use of inorganic ligands for colloidal NCs dramatically improved inter-NC charge transport, enabling fast progress in NC-based devices. Typical inorganic ligands (e.g., Sn(2)S(6)(4-), S(2-)) are represented by negatively charged ions that bind covalently to electrophilic metal surface sites. The binding of inorganic charged species to the NC surface provides electrostatic stabilization of NC colloids in polar solvents without introducing insulating barriers between NCs. In this work we show that cationic species needed for electrostatic balance of NC surface charges can also be employed for engineering almost every property of all-inorganic NCs and NC solids, including photoluminescence efficiency, electron mobility, doping, magnetic susceptibility, and electrocatalytic performance. We used a suite of experimental techniques to elucidate the impact of various metal ions on the characteristics of all-inorganic NCs and developed strategies for engineering and optimizing NC-based materials.     

Coupled and decoupled dual quantum systems in one semiconductor nanocrystal

Dual quantum systems, 0-dimensional quantum dot, and 2-dimensional quantum wells were constructed in one II-VI semiconductor nanocrystal by the epitaxial growth of a barrier (ZnS) layer between the systems in solution. By alteration of the thickness of the barrier layer, the two quantum systems were controlled to either electronically coupled or decoupled. Evidence of optical coupling between the two band gap emissions was also observed. The position and relative intensity of the two emissions can be independently tuned by reaction conditions. Total photoluminescence quantum efficiency of the dual emitting bands reached as high as 30% at room temperature under synthetic conditions not optimized for high emission.     

Stable photogenerated carriers in magnetic semiconductor nanocrystals

We report the preparation and investigation of charged colloidal Co2+:ZnO and Mn2+:ZnO nanocrystals. Although both charged and magnetically doped colloidal semiconductor nanocrystals have been reported previously, colloidal charged and magnetically doped semiconductor nanocrystals as described herein have not. Conduction band electrons were introduced into colloidal ZnO diluted magnetic semiconductor (DMS) nanocrystals photochemically, and the resulting TM2+-e-CB interactions were observed by electron paramagnetic resonance spectroscopy (TM2+ = Co2+ or Mn2+). This new motif of colloidal charged magnetic semiconductor nanocrystals reveals attractive new opportunities for studying spin effects in DMS nanostructures relevant to proposed spintronics technologies.     

Mechanistic study of precursor evolution in colloidal group II-VI semiconductor nanocrystal synthesis

The molecular mechanism of precursor evolution in the synthesis of colloidal group II-VI semiconductor nanocrystals was studied using 1H, 13C, and 31P NMR spectroscopy and mass spectrometry. Tri-n-butylphosphine chalcogenides (TBPE; E = S, Se, Te) react with an oleic acid complex of cadmium or zinc (M-OA; M = Zn, Cd) in a noncoordinating solvent (octadecene (ODE), n-nonane-d20, or n-decane-d22), affording ME nanocrystals, tri-n-butylphosphine oxide (TBPO), and oleic acid anhydride ((OA)2O). Likewise, the reaction between trialkylphosphine selenide and cadmium n-octadecylphosphonic acid complex (Cd-ODPA) in tri-n-octylphosphine oxide (TOPO) produces CdSe nanocrystals, trialkylphosphine oxide, and anhydrides of n-octadecylphosphonic acid. The disappearance of tri-n-octylphosphine selenide in the presence of Cd-OA and Cd-ODPA can be fit to a single-exponential decay (kobs = (1.30 +/- 0.08) x 10-3 s-1, Cd-ODPA, 260 degrees C, and kobs = (1.51 +/- 0.04) x 10-3 s-1, Cd-OA, 117 degrees C). The reaction approaches completion at 70-80% conversion of TOPSe under anhydrous conditions and 100% conversion in the presence of added water. Activation parameters for the reaction between TBPSe and Cd-OA in n-nonane-d20 were determined from the temperature dependence of the TBPSe decay over the range of 358-400 K (deltaH++ = 62.0 +/- 2.8 kJ.mol-1, deltaS++ = -145 +/- 8 J.mol-1.K-1). A reaction mechanism is proposed where trialkylphsophine chalcogenides deoxygenate the oleic acid or phosphonic acid surfactant to generate trialkylphosphine oxide and oleic or phosphonic acid anhydride products. Results from kinetics experiments suggest that cleavage of the phosphorus chalcogenide double bond (TOP=E) proceeds by the nucleophilic attack of phosphonate or oleate on a (TOP=E)-M complex, generating the initial M-E bond.     

Generation and transport of charge carriers in polyvinylcarbazole

The processes of generation and transport of excess charge carriers in polyvinylcarbazole at room temperature and at 353 K were experimentally studied. The polymer was charged with pulses of electrons at energies of 7 and 50 keV, which differed in both linear energy transfer and track structure. A universal method of investigation based on the combination of the time-of-flight technique in the both (surface and bulk) modes with the measurement of radiation-induced conductivity was used. The radiation-chemical yield of free charges was measured using two independent procedures. It was shown that the radiation chemical yield of free charges at 293 K was somewhat smaller for 7-keV than for 50-keV electrons; in the latter case, G = 1.1 in an electric field of 2 × 10⁷ V/m. The parameters of the generalized physical model were determined for polyvinylcarbazole.     

Photogeneration and transport of charge carriers in polysilylenes

The attachment of π-conjugated chromophores that absorb the radiation with long wavelengths to poly(methylphenylsilylene) ( 1 ) via reactions of its formylated derivative is described. Some of the polymers obtained show improved photostability and higher quantum photogeneration efficiency in comparison with the parent polymer. Photoconductive ultra-thin layers can be prepared from polar derivatives of ( 1 ) by the Langmuir–Blodgett technique.     

Photoinduced charge separation and recombination in a conjugated polymer-semiconductor nanocrystal composite

Semiconductor nanocrystals and conjugated polymers are classes of well-known materials with optoelectronic properties. We demonstrate that in a nanocrystalline TiO₂/poly(p-phenylene vinylene) (PPV) composite, excitons photogenerated in the polymer can be dissociated at the interface between the components, with electrons transferred to the nanocrystals. We show this and also follow the subsequent recombination using a time-resolved microwave conductivity technique. Recombination proceeds in a complex manner with roughly half of the initial amplitude decaying in 600 ns and the remainder in a biexponential process with time constants and relative amplitudes of 4.3 (0.7) and 80 μs (0.3). Photovoltaic devices were made from the composite films and their properties are discussed in light of the measured recombination rate and a simple carrier transport model.     

Finite-difference time-domain simulation of light induced charge dynamics in silver nanoparticles

We use a finite-difference time-domain (FDTD) approach to describe and control light-induced charge dynamics via two constructs consisting of nanoscale silver cylinders. The charge dynamics is found to be significantly different from the energy dynamics intensively studied in the past in similar systems. It is shown that two-color sources with a tunable relative phase introduce the opportunity to control the charge dynamics via a simple and interesting control mechanism, namely, the time evolution of the charge is directly tied to the instantaneous value of the source fields. Hence, our ability to shape laser pulses and tailor their relative phases and amplitudes translates directly into the possibility of manipulating charge oscillations within metal nanoparticle arrays.     

Direct spectrometry of solids in view of information characteristics

The development of atomic spectrometric methods in recent years is characterized by a remarkable orientation towards direct analysis of solids using various sample introduction techniques in connection with inductively coupled plasma excitation. The old-fashioned direct-current arc excitation with computer-controlled arc current vs. time programming has been studied as an alternative to the above mentioned methods. The influence of different electrode material, different sample preparation mode and working atmosphere on the main figures of merit (precision of the method, dynamic concentration range, determination limit, etc.) have been studied using an evaluation procedure based on the information theory. Received: 3 June 1998 / Revised: 15 July 1998 / Accepted: 18 July 1998     

Bimolecular recombination of charge carriers in molecularly doped polycarbonate

The general problems of the bimolecular recombination of charge carriers in molecularly doped polycarbonate are discussed. Experimental studies are performed via the transient radiation-induced conductivity method. Transient-current curves are numerically calculated via the multiple trapping model. The calculated and experimental curves are in good agreement. It is shown that the studied molecularly doped polymer undergoes bimolecular recombination via the Langevin mechanism.     

Sano-Tachiya-Noolandi-Hong versus Onsager modelling of charge photogeneration in organic solids

We have studied the electric field dependence of charge photogeneration efficiency in organic solids for various radial distribution functions (Dirac delta, Gaussian, exponential) of initial e-h pairs in the framework of Sano-Tachiya-Noolandi-Hong (STNH) theory assuming that the final recombination (capture reaction) proceeds on a sphere of finite radius (a) with a finite velocity (κ). We compare the STNH results with the conventional Onsager theory assuming a = 0. We show that charge photogeneration is more enhanced, especially in low-electric field range, for broader initial pair distributions and for smaller final recombination velocities. We compare theoretical results with experimental data taken from electromodulation of photoluminescence (EML) for two archetypical organic photoconductors, Alq₃ and Ir(ppy)₃, commonly used as emitters in organic LEDs. From analysis of our results we infer the lower limit of final recombination velocity, κ = 0.2-2 cm/s, in vacuum evaporated films of Alq₃ and Ir(ppy)₃ which compares favorably with an evaluation of this quantity in amorphous solids.