We study experimentally the photoconductivity of CdS-CdSe sintered granular films obtained by the screen printing method. We mostly focus on the dependences of photoconductivity on film's microstructure, which varies with changing heat-treatment conditions. The maximum photoconductivity is found for samples with compact packing of individual grains, which nevertheless are separated by gaps. Such a microstructure is typical for films heat-treated during an intermediate (optimal) time. In order to understand whether the dominant mechanism of charge transfer is identical with the one in monocrystals, we perform temperature measurements of photoresistance. Corresponding curves have the same peculiar nonmonotonic shape as in CdSe monocrystals, from which we conclude that the basic mechanism is also the same. It is suggested that the optimal heat-treatment time appears as a result of a competition between two mechanisms: improvement of film's connectivity and its oxidation. Photoresistance is also measured in vacuum and in helium atmosphere, which suppress oxygen and water absorption/chemisorption at intergrain boundaries. We demonstrate that this suppression increases photoconductivity, especially at high temperatures.
The vibrational spectra of CdSe/CdS superlattices (SLs) with different layer thicknesses are calculated from first principles within the density functional theory. It is shown that, along with folded acoustic and confined optical modes, a number of confined acoustic modes appear in SLs. In structures with a minimum thickness of one of the layers, microscopic interface modes similar to local and gap modes in crystals appear. An analysis of projections of the eigenvectors of vibrational modes in SLs onto the orthonormal basis of normal modes in binary compounds enables to establish the details o…
Metal sulfides are emerging as an important class of materials for photocatalytic applications, because of their high photo responsive nature in the wide visible light range. CdS in this class of materials, have a direct band gap of 2.4 eV, have gained special attention due to the relative position of its conduction band minimum, which is very close to the energies of the reduced protons. However, the photogenerated holes in the valence band of CdS are prone to oxidation and destroy its structure during photocatalysis. Thus constructing a CdS based heterostructure would be an effective strateg…
The vibrational spectroscopy of semiconductor nanostructures can provide important information on their structure. In this work, experimental Raman and infrared spectra are compared with vibrational spectra of CdSe/CdS core/shell nanoplatelets calculated from first principles using the density functional theory. The calculations confirm the two-mode behavior of phonon spectra of nanostructures. An analysis of the experimental spectra reveals the absence of modes with a high amplitude of vibrations of surface atoms, which indicates their strong damping. Taking into account the difference in the…
Unveiling the local elemental arrangements across the interfaces inside CdSe/Cd1-xZnxS core-shell and CdSe/CdS/ Cd1-xZnxS core-crown-shell quantum wells
The investigation of the possibility of optical refrigeration (OR) on zinc-blende cadmium selenide/cadmium sulfide (CdSe/CdS) core/shell structure quantum dots (QDs) has been carried out. Quality samples were synthesized in our lab, and significant energy up-conversion photoluminescence (UCPL) was observed in these samples, showing the potential of generating net cooling effects. To better understand and predict the UCPL characteristics of the QDs, a semi-empirical model has been developed, showing good agreement with our experimental results. The model takes into account the corresponding qua…
The interaction between excitons and phonons in semiconductor nanocrystals plays a crucial role in the exciton energy spectrum and dynamics, and thus in their optical properties. We investigate the exciton2 phonon coupling in giant-shell CdSe/CdS core-shell nanocrystals via resonant Raman spectroscopy. The Huang-Rhys parameter is evaluated by the intensity ratio of the longitudinal-optical (LO) phonon of CdS with its first multiscattering (2LO) replica. We used four different excitation wavelengths in the range from the onset of the CdS shell absorption to well above the CdS shell band edge to…
We investigate the time-resolved photocurrent response of CdSe quantum dot (QD) thin films sensitized with zinc beta-tetraaminophthalocyanine (Zn4APc) on three different substrates, namely silicon with 230 nm SiO2 dielectric, glass as well as polyimide. While Si/SiO2(230 nm) is not suitable for any transient photocurrent characterization due to an interfering photocurrent response of the buried silicon, we find that polyimide substrates invoke the larger optical bandwidth with 85 kHz vs. 67 kHz for the same quantum dot thin film on glass. Upon evaluation of the transient photocurrent, we find …
CdSe nanocrystals and aggregates of an aryleneethynylene derivative are assembled into a hybrid thin film with dual fluorescence from both fluorophores. Under continuous excitation, the nanocrystals and the molecules exhibit anti-correlated fluorescence intensity variations, which become periodic at low temperature. We attribute this to a structure-dependent aggregation induced emission of the aryleneethynylene derivative, which impacts the rate of excitation energy transfer between the molecules and nanocrystals. Energy transfer also affects the electric transport properties of the hybrid mat…
Optical and X-ray Photo-emission Spectroscopies of Core/Shell Colloidal CdSe/CdS Quantum Dots: Modeling and Experimental Determination of Band Alignment
Colloidal quantum dots (cQDs) are now a mature nanomaterial with optical properties customizable through varying size and composition. However, their use in optical devices is limited as they are not widely available in convenient forms such as optical fibers. With advances in polymerization methods incorporating nanocrystals, nanocomposite materials suitable for processing into high quality hybrid active fibers can be achieved. We demonstrate a plastic optical fiber fabrication method which ensures homogeneous dispersion of cQDs within a polymer core matrix. Loading concentrations between 10$…
We report the synthesis and optical characterization of fully inorganic gradientshell CdSe/CdZnS nanocrystals (NCs) with high luminescence quantum yield (QY, 50 percent), which were obtained by replacing native oleic-acid (OA) ligands with halide ions (Br and Cl). Absorption, photoluminescence excitation (PLE) and photoluminescence (PL) spectra in solution were unaffected by the ligand-exchange procedure. The halide-capped NCs were stable in solution for several weeks without modification of their PL spectra; once deposited as unprotected thin films and exposed to air, however, they did show s…
The surface ligands on colloidal nanocrystals (NCs) play an important role in the performance of NCs based optoelectronic devices such as photovoltaic cells, photodetectors and light emitting diodes (LEDs). On one hand, the NC emission depends critically on the passivation of the surface to minimize trap states that can provide non-radiative recombination channels. On the other hand, the electrical properties of NC films are dominated by the ligands that constitute the barriers for charge transport from one NC to its neighbor. Therefore, surface modifications via ligandexchange have been emplo…
