Surface Of CdSe Nanocrystals Research Articles

Quantifying Ligand Exchange Reactions at CdSe Nanocrystal Surfaces

The exchange reactions of X-type ligands at the surface of CdSe nanocrystals have been quantified via 1H NMR, absorbance, and emission spectroscopies. 1H NMR was used to quantify displacement reactions of oleate-capped CdSe nanocrystals with carboxylic-acid-, phosphonic-acid-, and thiol-terminated ligands that incorporate terminal alkene functionalities. The alkenyl protons of the native oleate ligand and the vinylic protons of the exchange ligand provide spectroscopic handles to quantify both free and surface-bound forms of these ligands. Undec-10-enoic acid was found to undergo an exchange equilibrium with oleate (Keq = 0.83), whereas phosphonic-acid- and thiol-terminated ligands irreversibly displace native oleate ligands. Absorption and emission experiments indicate that the carboxylic acid exchanges occur solely between surface-bound ligands, whereas exchange reactions with phosphonic acids and thiols alter the surface metal atoms of the nanocrystals, presumably through the displacement of Cd(oleate)...

Controlling the Trap State Landscape of Colloidal CdSe Nanocrystals with Cadmium Halide Ligands

We developed a simple and robust colloidal route for the installation of CdX2 (X = Cl, Br, I) ligands on the surface of CdSe nanocrystals, which effectively displace the native ligands and form stable suspensions. After colloidal ligand exchange, these nanocrystals can be easily solution cast into nanocrystal films. Photoelectrochemical measurements on solution-cast nanocrystal films reveal a striking influence of surface cadmium halide on photocurrent response, with mildly annealed, CdCl2-treated CdSe nanocrystals showing the greatest enhancement in photocurrent to above band gap illumination. The strong dependence of photoresponse on surface halide is thought to result from ligand-induced changes in the electronic structure of the nanocrystal samples. We arrive at this conclusion using a combination of ultrafast transient absorption, time-resolved photoluminescence, and surface photovoltage spectroscopies, which are being applied together for the first time to investigate nanocrystal trap states. From t...

Improving Polymer/Nanocrystal Hybrid Solar Cell Performance via Tuning Ligand Orientation at CdSe Quantum Dot Surface

Achieving superior solar cell performance based on the colloidal nanocrystals remains challenging due to their complex surface composition. Much attention has been devoted to the development of effective surface modification strategies to enhance electronic coupling between the nanocrystals to promote charge carrier transport. Herein, we aim to attach benzenedithiol ligands onto the surface of CdSe nanocrystals in the "face-on" geometry to minimize the nanocrystal-nanocrystal or polymer-nanocrystal distance. Furthermore, the "electroactive" π-orbitals of the benzenedithiol are expected to further enhance the electronic coupling, which facilitates charge carrier dissociation and transport. The electron mobility of CdSe QD films was improved 20 times by tuning the ligand orientation, and high performance poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT):CdSe nanocrystal hybrid solar cells were also achieved, showing a highest power conversion efficiency of 4.18%. This research could open up a new pathway to improve further the performance of colloidal nanocrystal based solar cells.

Facile synthesis of CdSe nanocrystals for bulk-heterojunction solar cells

Oleic acid (OA)-capped cadmium selenide (CdSe) nanocrystals (NCs) have been synthesized via a new high-scale route. X-ray diffraction and transmission electron microscopy confirmed that rod-like hexagonal (wurtzite) CdSe NCs with an average size of 10 nm were obtained via this new route. The obtained CdSe NCs were treated individually with pyridine and tert-butylamine (t-BA) for ligand exchange. Fourier transform infrared spectra of the as-synthesized and treated CdSe NCs confirmed the removal of OA ligands from the surface of CdSe NCs after treatments with pyridine and t-BA. Bulk-heterojunction (BHJ) solar cell devices were prepared using untreated and surface treated CdSe NCs blended with poly (3-hexylthiophene-2,5-diyl) (P3HT) polymer. BHJ solar cell devices made from P3HT:(surface treated CdSe NCs) blends showed greater improvement in photovoltaic performances compared to P3HT:(untreated CdSe NCs) blend. The improvement in photovoltaic performances was due to the increase of electron mobility in P3HT:(CdSe NCs) blends after surface treatment of CdSe NCs.

Synthesis of non-spherical CdSe nanocrystals

Non-spherical CdSe quantum dots were synthesized through high temperature reduction of cadmium and selenium in the presence of TOP (tri-n-octylphosphine) and TOPO (tri-n-octylphosphine oxide). The high affinity of phosphine oxide to the surface of CdSe nanocrystals typically leads to the formation of spherical particles with diameters between 1.5 and 10 nm. However, with lower temperatures and longer reaction times relative to conventional synthesis techniques, the formation of non-spherical nanocrystals dominated. The three reaction temperatures that were studied were 230, 250, and 270 °C. Results verify the need to quench CdSe nanocrystals immediately following the injection of selenium dissolved in TOP (TOPSe) if spherical particles are the desired shape. Nanocrystal shape evolves from sphere to rectangle to hexagon or triangle as the reaction time is extended regardless of temperature. The highest yield of rectangular particles (~89 %) was achieved while maintaining a temperature of 250 °C for 20 min.

Synthesis of new nanocrystal-polymer nanocomposite as the electron acceptor in polymer bulk heterojunction solar cells

A hydroxyl-coated CdSe nanocrystal (CdSe-OH) and a CdSe-polymer nanocomposite were synthesized and used as the electron acceptors in polymer solar cells (PSCs). The CdSe-polymer composite was prepared via atom transfer radical polymerization (ATRP) of N-vinylcarbazole on functionalized CdSe quantum dots. Physical properties and photovoltaic characteristics of the CdSe-poly( N-vinylcarbazole) (CdSe-PVK) nanocomposite have been investigated. Thermogravimetric analysis (TGA) results displayed higher thermal stability for CdSe-PVK nanohybrid in comparison with the linear-type PVK polymer. Differential scanning calorimetry (DSC) studies indicated that CdSe-PVK had a lower glass-transition temperature ( T g) in comparison with PVK due to the branch effect of the star-shaped polymer hybrid. Cyclic voltammetric (CV) measurements were performed to obtain HOMO and LUMO values of PVK and CdSe-PVK. TEM and SEM micrographs exhibited CdSe nanoparticles were well coated with PVK polymer. Both CdSe-OH and CdSe-PVK were blended with poly(3-hexylthiophene) (P3HT) and used as the active layer in bulk heterojunction solar cells. Polymer solar cell based on CdSe-PVK as acceptor revealed that the photovoltaic properties can be significantly improved when PVK polymer chains were grafted on surfaces of CdSe nanocrystals. In comparison with the P3HT:CdSe-OH system, PSC based on P3HT:CdSe-PVK showed an improved power conversion efficiency (0.02% vs. 0.001%). Film topography studied by AFM further confirmed the better device performance was due to the enhanced compatibility between P3HT and CdSe-PVK.

Synthesis of CdSe–Poly(N‐vinylcarbazole) Nanocomposite by Atom Transfer Radical Polymerization for Potential Optoelectronic Applications

A hybrid inorganic-polymer nanocomposite using CdSe nanocrystals with high electron mobility has been successfully synthesized by atom transfer radical polymerization (ATRP). First the hydroxyl-coated CdSe nanoparticles (i.e., CdSe-OH) were prepared via a wet chemical route. A polymerization initiator was then prepared for ATRP of N-vinylcarbazole. FT-IR, (1) H NMR, and XRD analyses confirmed the successful synthesis of CdSe-poly(N-vinylcarbazole) (PVK) nanohybrid. UV-Vis spectra and photoluminescence data revealed that grafting of PVK onto the surface of CdSe nanocrystals would reduce the band gap of PVK and cause the red shift of emission peak. TEM and SEM micrographs exhibited CdSe nanoparticles that were well-coated with PVK polymer.

Surface Ligand Dynamics in Growth of Nanocrystals

Amine ligands were identified to bond on the surface of CdSe nanocrystals in a dynamic fashion under elevated temperatures in the reproducible growth domain of the specific designed growth reactions. The surface ligand dynamics was found to strongly depend on the growth temperature, the ligand concentration, and the ligand chain length. The strong chain-length dependence was originated from the interligand interactions in the ligand monolayer of a nanocrystal, provided fatty amines being weak ligands for CdSe nanocrystals. When the growth reaction was above the boiling point of an amine ligand, the surface ligand dynamics was violent, a quasi-gas-phase state, indicated by strong temperature-dependent and fast growth rates of the nanocrystals. Approximately below its boiling point, a significantly weak temperature dependence of the growth rate of the nanocrystals associated with the quasi-liquid state of the surface ligands was observed. A direct result of studying the surface ligand dynamics of this well-established nanocrystal system was the formation of high-quality CdSe nanocrystals under much reduced temperature, 150 degrees C, in comparison to the standard 250-350 degrees C temperature range. This was achieved by using fatty amines with a short hydrocarbon chain at a low ligand concentration in the solution. Preliminary results indicate that a similar temperature (160 degrees C) also worked for the growth of InP nanocrystals.

Carbodithioate-Containing Oligo- and Polythiophenes for Nanocrystals' Surface Functionalization

Organic ligands containing the chelating carbodithioate group are excellent candidates for the surface functionalization of various semiconductor and metal nanoparticles or flat substrates. We provide a simple synthetic scheme for the preparation of a series of regioregular oligo- and polythiophenes containing this functional group. In the first step, 3-[4-(bromomethyl)phenyl]-2,5-dibromothiophene is coupled either to 3-n-octylthiophene or to 3,3‘ ‘-dioctyl-2,2‘:5‘,2‘ ‘-terthiophene, leading to quasisymmetric thiophene trimers or heptamers, respectively. In the second step, these oligomers are submitted to oxidative polymerization, and finally the carbodithioic acid function is introduced. This procedure can be generalized for the preparation of a large number of functional oligo- and polythiophenes by simply varying the chemical structure of the thiophene precursors used. We illustrate the grafting of these compounds on the surface of CdSe nanocrystals with the example of 4-thiophen-3-yldithiobenzoic aci...

Study of colloidal quantum-dot surfaces using an innovative thin-film positron 2D-ACAR method

Nanosized inorganic particles are of great interest because their electronic properties can be easily tailored, providing a tremendous potential for applications in optoelectronic devices, light-emitting diodes, solar cells and hydrogen storage. Confinement of electrons and holes to dimensions comparable to their wavelength leads to quantum-well states with modified wavefunctions and density of states. Surface phenomena are crucial in determining nanoparticle properties in view of their large surface-to-volume ratio. Despite a wealth of information, many fundamental questions about the nature of the surface and its relationship with the electronic structure remain unsolved. Ab initio calculations on CdSe nanocrystals suggest that passivating the ligands does not produce the ideal wurtzite structure and that Se atoms relax outwards irrespective of passivation. Here we show that implanted positrons are trapped at the surface of CdSe nanocrystals. They annihilate mostly with the Se electrons, monitor changes in composition and structure of the surface while hardly sensing the ligand molecules, and we thus unambiguously confirm the predicted strong surface relaxation.

Ligand Effects on Optical Properties of CdSe Nanocrystals

We report effects of various organic and inorganic ligands on optical properties of CdSe nanocrystals (NCs) by changes in their photoluminescence and absorbance spectra. Surface ligand loss occurring during dilution and purification of solutions of CdSe NCs leads to a decrease of photoluminescence intensity. The complex of trioctylphosphine with Se atoms on the surface of CdSe NCs is found responsible for the trap emission band that is red-shifted relative to the photoluminescence band edge.

PHOTOBRIGHTENING AND PHOTODARKENING IN CdSe NANOCRYSTAL/POLYMER THIN FILMS

The change in the photoluminescence intensity of CdSe nanocrystal/polymer thin films with duration of illumination is investigated. The choice of polymer has an influence on photobrightening and photodarkening. In particular, photodarkening in CdSe nanocrystal/poly(vinyl carbazole) thin film occurs immediately upon illumination, in contrast to the slow changes observed with polystyrene and poly(2-vinylpridine). We discuss the mechanisms of this phenomenon in comparison with interaction between surface of CdSe nanocrystals and polymer side chain.