Size-Dependent Lattice Dynamics of Atomically Precise Cadmium Selenide Quantum Dots
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An epitaxial cubic 350-nm-thick cadmium selenide has been grown on silicon for the first time by the method of evaporation and condensation in a quasi-closed volume. It is revealed that, in this method, the optimum substrate temperature is 590°C, the evaporator temperature is 660°C, and the growth time is 2 s. To avoid silicon etching by selenium with formation of amorphous SiSe{sub 2}, a high-quality ~100-nm-thick buffer silicon carbide layer has been synthesized on the silicon surface by substituting atoms. The powder diffraction pattern and the Raman spectrum unambiguously correspond to cubic cadmium selenide crystal. The ellipsometric, Raman, and electron diffraction analyses demonstrate high structural perfection of the cadmium selenide layer and the absence of a polycrystalline phase.
The paper presents high-resolution electron microscopy investigations of the structure and morphology of cadmium selenide nanocrystals and nanoplatelets, and nanoplatelets having cadmium selenide core/crown nanostructure. These nanocrystals and nanoplatelets are obtained by the colloid technology and are deposited onto carbon substrates using the Langmuir–Blodgett method. It is shown that two-dimensional structures of nanocrystals and nanoplatelets can be formed on carbon substrates. The quantity specifications of these structures are determined in this paper.
Accurate vapor pressures are determined through direct weight loss measurements using the Knudsen effusion technique. The experimental data are evaluated by establishing the mode of vaporization and determining the heat capacity of cadmium selenide at elevated temperatures. Additional information is obtained through a second- and third-law evaluation of data, namely, the heat of formation and the absolute entropy of cadmium selenide. A preferential loss of selenium during the initial heating of CdSe is observed, which leads to a deviation in stoichiometry.
In situ electron microscopy is used to observe the morphological evolution of cadmium selenide nanorods as they sublime under vacuum at a series of elevated temperatures. Mass loss occurs anisotropically along the nanorod’s long axis. At temperatures close to the sublimation threshold, the phase change occurs from both tips of the nanorods and proceeds unevenly with periods of rapid mass loss punctuated by periods of relative stability. At higher temperatures, the nanorods sublime at a faster, more uniform rate, but mass loss occurs from only a single end of the rod. Furthermore, we propose a mechanism that accounts for the observed sublimation behavior based on the terrace–ledge–kink (TLK) model and how the nanorod surface chemical environment influences the kinetic barrier of sublimation.
The effect of cadmium selenide quantum dots (CdSe QDs) on the dielectric relaxation and material constants of a ferroelectric liquid crystal (FLC) has been investigated. Along with the characteristic Goldstone mode, a new relaxation mode has been induced in the FLC material due to the presence of CdSe QDs. This new relaxation mode is strongly dependent on the concentration of CdSe QDs but is found to be independent of the external bias voltage and temperature. The material constants have also been modified remarkably due to the presence of CdSe QDs. The appearance of this new relaxation phenomenon has been attributed to the concentration dependent interaction between CdSe QDs and FLC molecules.
The effect of cadmium-selenide quantum dots addition on the electrical and photoelectric properties of nanocrystalline indium oxide with nanocrystal dimensions in the range from 7 to 40 nm is studied. By impedance spectroscopy, it is shown that the addition of quantum dots substantially influences the resistance of interfaces between In{sub 2}O{sub 3} crystals. A change in the character of the photoconductivity spectrum of In{sub 2}O{sub 3} upon the addition of CdSe quantum dots is detected, and it is established that this change depends on the In{sub 2}O{sub 3}-nanocrystal dimensions. An energy band diagram is proposed to explain the observed change in the photoconductivity spectrum of In{sub 2}O{sub 3} upon the addition of CdSe quantum dots.
Metal-oxide-semiconductor capacitors made of the nanocrystalline cadmium selenide nc-CdSe embedded Zr-doped HfO{sub 2} high-k stack on the p-type silicon wafer have been fabricated and studied for their charge trapping, detrapping, and retention characteristics. Both holes and electrons can be trapped to the nanocrystal-embedded dielectric stack depending on the polarity of the applied gate voltage. With the same magnitude of applied gate voltage, the sample can trap more holes than electrons. A small amount of holes are loosely trapped at the nc-CdSe/high-k interface and the remaining holes are strongly trapped to the bulk nanocrystalline CdSe site. Charges trapped to the nanocrystals caused the Coulomb blockade effect in the leakage current vs. voltage curve, which is not observed in the control sample. The addition of the nanocrystals to the dielectric film changed the defect density and the physical thickness, which are reflected on the leakage current and the breakdown voltage. More than half of the originally trapped holes can be retained in the embedded nanocrystals for more than 10 yr. The nanocrystalline CdSe embedded high-k stack is a useful gate dielectric for this nonvolatile memory device.
We report bulk heterojunction solar cells based on blends of solution-processed small molecule [7,7′-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b′]dithiophene-2,6-diyl) bis(6-fluoro-4-(5′-hexyl-[2,2′-bithiophen]-5yl)benzo[c] [1,2,5] thiadiazole)] p-DTS(FBTTh{sub 2}){sub 2}: Cadmium Selenide (CdSe) (70:30, 60:40, 50:50, and 40:60) in the device configuration: Indium Tin Oxide /poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/p-DTS(FBTTh{sub 2}){sub 2}: CdSe/Ca/Al. The optimized ratio of p-DTS(FBTTh{sub 2}){sub 2}:CdSe::60:40 leads to a short circuit current density (J{sub sc}) = 5.45 mA/cm{sup 2}, open circuit voltage (V{sub oc}) = 0.727 V, and fill factor (FF) = 51%, and a power conversion efficiency = 2.02% at 100 mW/cm{sup 2} under AM1.5G illumination. The J{sub sc} and FF are sensitive to the ratio of p-DTS(FBTTh{sub 2}){sub 2}:CdSe, which is a crucial factor for the device performance.
Combining a molecular thiomolybdate cluster, [Mo 3 S 13 ] 2− , with cadmium selenide quantum dots capped with amphiphilic ligands results in a highly active photocatalytic system for the production of hydrogen under visible light irradiation.
In this project, we develop a bifacial tandem design for monolithic metal halide perovskite-cadmium selenide telluride (CST) tandem solar cells. The bifacial tandem design not only enables the monolithic integration of perovskite-CST tandems but also delivers high efficiency by harvesting the albedo light. It also allows better current match and thus enables higher power output of the tandem devices than conventional tandem cells. We worked on understanding the critical factors limiting bifacial CST cells and developing strategies to improve their bifaciality. We also developed efficient wide-bandgap perovskite subcells and interconnecting layers that enable the monolithic perovskite-CST tandem solar cells. We successfully demonstrated prototype monolithic bifacial perovskite-CST tandem solar cells with bifacial equivalent efficiencies of more than 25% under an albedo of 0.4. Additionally, we optimized the wide-bandgap perovskite to realize four-terminal perovskite-CST tandem devices with efficiencies of 25.5% under monofacial illumination. The team disseminated these results to stakeholders in the PV academic and industry and discussed the challenges and major technical barriers for their market entry. The technologies developed in the project are promising but are not yet ready for immediate commercialization. Future fundamental study and R&D work are needed to advance these promising technologies.
The temperature and size dependences of the energy gap in CdSe quantum dots with diameters of 2.4, 4.0, and 5.2 nm embedded in fluorophosphate glasses are investigated. It is shown that the temperature coefficient of the band gap dE{sub g}/dT in the quantum dots differs from the bulk value and depends strictly on the dot size. It is found that, furthermore, the energy of each transition in these quantum dots is characterized by an individual temperature coefficient dE/dT.
In the present study, it is predicted that the band gap energy of a three-dimensional quantum dot assembly exhibits a red shift when the dispersion of the crystal size distribution is enlarged, even at a fixed average value thereof. The effect is manifested when the size quantization regime in individual quantum dots constituting the assembly has been entered. Under the same conditions, the sub-band gap absorption tails are characterized with large Urbach energies, which could be one or two orders of magnitude larger than the value characteristic for the non-quantized case. - Graphical abstract: Band gap shifts due to size-distribution of nanoparticles in 3D assemblies built up by quantum dots in size-quantization regime. Display Omitted - Highlights: • Optical absorption of 3D QD assemblies in size-quantization regime is modeled. • Band gap energy of the QD solid depends on the size-distribution of the nanoparticles. • QD solid samples with same 〈R〉 exhibit band gap shift depending on size distribution. • QD size distribution leads to large Urbach energies.
In terms of producing new advances in sustainable nanomaterials, cation exchange (CE) of post-processed colloidal nanocrystals (NCs) has opened new avenues towards producing non-toxic energy materials via simple chemical techniques. The main processes governing CE can be explained by considering hard/soft acid/base theory, but the detailed mechanism of CE, however, has been debated and has been attributed to both diffusion and vacancy processes. In this work, we have performed in situ x-ray absorption spectroscopy to further understand the mechanism of the CE of copper in solution phase CdSe NCs. The x-ray data indicates clear isosbestic points, suggestive of cooperative behavior as previously observed via optical spectroscopy. Examination of the extended x-ray absorption fine structure data points to the observation of interstitial impurities during the initial stages of CE, suggesting the diffusion process is the fundamental mechanism of CE in this system.
Colloidal quantum wells, or nanoplatelets, show among the lowest thresholds for amplified spontaneous emission and lasing among solution-cast materials and among the highest modal gains of any known materials. Using solution measurements of colloidal quantum wells, this work shows that under photoexcitation, optical gain increases with pump fluence before rolling off due to broad photoinduced absorption at energies lower than the band gap. Despite the common occurrence of gain induced by an electron–hole plasma found in bulk materials and epitaxial quantum wells, under no measurement conditions was the excitonic absorption of the colloidal quantum wells extinguished and gain arising from a plasma observed. Instead, like gain, excitonic absorption reaches a minimum intensity near a photoinduced carrier sheet density of 2 × 10 13 cm –2 above which the absorption peak begins to recover. To understand the origins of these saturation and reversal effects, measurements were performed with different excitation energies, which deposit differing amounts of excess energy above the band gap. Across many samples, it was consistently observed that less energetic excitation results in stronger excitonic bleaching and gain for a given carrier density. Transient and static optical measurements at elevated temperatures, as well as transient X-ray diffraction of the samples, suggest that the origin of gain saturation and reversal is a heating and disordering of the colloidal quantum wells which produces sub-gap photoinduced absorption.
UV-Vis spectroscopy and PL data show that structural incorporation of Eu 3+ has an effect on the optical properties of CdSe QDs via energy transfer from host to dopant. This allows for QDs with tunable optical properties via numerous pathways.
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