Constraints in post-synthesis ligand exchange for hybrid organic (MEH-PPV)–inorganic (CdSe) nanocomposites

For an optimum charge/energy transfer performance of hybrid organic–inorganic colloidal nanocrystals for applications such as photonic devices and solar cells, the determining factors are the distance between the nanocrystal and polymer which greatly depends upon nanocrystal size/nanocrystal ligands. Short chain ligands are preferred to ensure a close contact between the donor and acceptor as a result of the tunnelling probability of the charges and the insulating nature of long alkyl chain molecules. Short distances increase the probability for tunnelling to occur as compared to long distances induced by long alkyl chains of bulky ligands which inhibit tunnelling altogether. The ligands on the as-synthesized nanocrystals can be exchanged for various other ligands to achieve desirable charge/energy transfer properties depending on the bond strength of the ligand on the nanocrystal compared to the replacement ligand. In this work, the constraints involved in post-synthesis ligand exchange process have been evaluated, and these factors have been tuned via wet chemistry to tailor the hybrid material properties via appropriate selection of the nanocrystal capping ligands. It has been found that both oleic acid and oleylamine (OLA)-capped cadmium selenide (CdSe) quantum dots (QDs) as compared with trioctylphosphine oxide (TOPO)-passivated CdSe QDs are of high quality, and they provide better steric stability against coagulation, homogeneity, and photostability to their respective polymer:CdSe nanocomposites. CdSe QDs particularly with OLA capping have relatively smaller surface energies, and thus, lesser quenching capabilities show dominance of photoinduced Forster energy transfer between donors (polymer) and acceptors (CdSe nanocrystals) as compared to charge transfer mechanism as observed in polymer:CdSe (TOPO) composites. It is conjectured that size quantization effects, stereochemical compatibility of ligands (TOPO, oleic acid, and oleyl amine), and polymer MEH-PPV stability greatly influence the photophysics and photochemistry of hybrid polymer–semiconductor nanocomposites.     

Photochemical instability of CdSe nanocrystals coated by hydrophilic thiols

The photochemical instability of CdSe nanocrystals coated by hydrophilic thiols was studied nondestructively and systematically in water. The results revealed that the photochemical instability of the nanocrystals actually included three distinguishable processes, namely the photocatalytic oxidation of the thiol ligands on the surface of nanocrystals, the photooxidation of the nanocrystals, and the precipitation of the nanocrystals. At first, the thiol ligands on the surface of a nanocrystal were gradually photocatalytically oxidized using the CdSe nanocrystal core as the photocatalyst. This photocatalytic oxidation process was observed as a zero-order reaction in terms of the concentration of the free thiols in the solution. The photogenerated holes in a nanocrystal were trapped onto the thiol ligands bound on the surface of the nanocrystal, which initiated the photooxidation of the ligands and protected the nanocrystal from any photooxidation. After nearly all of the thiol ligands on the surface of the nanocrystals were converted into disulfides, the system underwent several different pathways. If the disulfides were soluble in water, then all of the disulfides fell into the solution at the end of this initial process, and the nanocrystals precipitated out of the solution without much variation over their size and size distribution. When the disulfides were insoluble in water, they likely formed a micelle-like structure around the nanocrystal core and kept it soluble in the solution. In this case, the nanocrystals only precipitated after severe oxidation, which took a long period of time. If the system contained excess free thiol ligands, they replaced the photochemically generated disulfides and maintained the stability and solubility of the nanocrystals. The initiation stage of the photooxidation of CdSe nanocrystals themselves increased as the thickness and packing density of the ligand shell increased. This was explained by considering the ligand shell on the surface of a nanocrystal as the diffusion barrier of the oxygen species from the bulk solution into the interface between the nanocrystal and the surface ligands. Experimental results clearly indicated that the initiation stage of the photooxidation was not caused by the chemical oxidation of the system kept in air under dark conditions or the hydrolysis of the cadmium-thiol bonds on the surface of the nanocrystals, both of which were magnitudes slower than the photocatalytic oxidation of the surface ligands if they occurred at all. The results described in this contribution have already been applied for designing new types of thiol ligands which dramatically improved the photochemical stability of CdSe nanocrystals with a ligand shell that is as thin as approximately 1 nm.     

Nanocrystal ligand exchange with 1,2,3,4-thiatriazole-5-thiolate and its facile in situ conversion to thiocyanate

The 1,2,3,4-thiatriazole-5-thiolate anion (TTT(-)) was found to be a strongly binding ligand for CdSe nanocrystals, quantitatively exchanging various long-chain ligands to yield stable colloidal suspensions in common polar solvents. The TTT(-) ligand thermolyzes at <100 °C to produce thiocyanate in situ, resulting in reduced quantum confinement in nanocrystal films. CdSe(TTT) possesses far higher colloidal stability than CdSe(SCN), and that, together with the facile synthesis of TTT(-), implies that this is a useful ligand for nanocrystal applications as a masked thiocyanate.     

Ligand exchange on colloidal CdSe nanocrystals using thermally labile tert-butylthiol for improved photocurrent in nanocrystal films

As-prepared CdSe nanocrystals were ligand exchanged using tert-butylthiol, which yielded stable CdSe nanocrystal inks in the strong donor solvent tetramethylurea. The efficacy of ligand exchange was probed by thermogravimetric analysis (TGA) and FT-IR spectroscopy. By studying sequential exchanges of tetradecylphosphonic acid and then tert-butylthiol, TGA and energy dispersive X-ray spectroscopic evidence clearly demonstrated that the ligand exchange is essentially quantitative. The resulting tert-butylthiol-exchanged CdSe nanocrystals undergo facile thermal ligand expulsion (≤200 °C), which was studied by TGA-mass spectrometry. Mild thermal treatment of tert-butylthiol-exchanged CdSe nanocrystal films was found to induce loss of quantum confinement (as evidenced by UV-vis spectroscopy) and provided for increased electrochemical photocurrent, electron mobility, and film stability. Pyridine-exchanged CdSe nanocrystals were employed as a control system throughout to demonstrate the beneficial attributes of tert-butylthiol exchange; namely, lower organic content, better colloidal stability, improved interparticle coupling, and vastly increased electrochemical photocurrent response upon illumination.     

Chelating ligands for nanocrystals' surface functionalization

A new family of ligands for the surface functionalization of CdSe nanocrystals is proposed, namely alkyl or aryl derivatives of carbodithioic acids (R-C(S)SH). The main advantages of these new ligands are as follows: they nearly quantitatively exchange the initial surface ligands (TOPO) in very mild conditions; they significantly improve the resistance of nanocrystals against photooxidation because of their ability of strong chelate-type binding to metal atoms; their relatively simple preparation via Grignard intermediates facilitates the development of new bifunctional ligands containing, in addition to the anchoring carbodithioate group, a second function, which enables the grafting of molecules or macromolecules of interest on the nanocrystal surface. To give an example of this approach, we report, for the first time, the grafting of an electroactive oligomer from the polyaniline family-aniline tetramer-on CdSe nanocrystals after their functionalization with 4-formyldithiobenzoic acid. The grafting proceeds via a condensation reaction between the aldehyde group of the ligand and the terminal primary amine group of the tetramer. The resulting organic/inorganic hybrid exhibits complete extinction of the fluorescence of its constituents, indicating efficient charge or energy transfer between the organic and the inorganic semiconductors.     

Comparative study on coating CdSe nanocrystals with surfactants

We have synthesized CdSe nanocrystals (NCs) in sizes from 2.2 to 5.1 nm passivated with hydrophobic trioctylphosphine oxide (TOPO) in combination trioctylphosphine (TOP) or tributylphosphine (TBP) to obtain particles of the type CdSe/TOPO/TOP or CdSe/TOPO/TBP. These NCs were then dispersed in aqueous solution of ionic or non-ionic surfactants (such as stearate, oleic acid, Tween) using a biphase (water and chloroform or hexane) transfer method. It is found that both the structure of the surfactant and the native surface of the ligand govern the coating of the NCs with surfactants. More specifically, the hydrophobicity-hydrophilicity balance of the surfactant regulates the coating efficacy, thereby transferring the NC from the organic to the aqueous phase. The type of ligand on the NCs and the kind of coating surfactant also affect photoluminescence (PL). The ratio of PL and absorbance unit (defined as PL per 0.1 AU) was implemented as a tool to monitor changes in PL intensity and wavelength as a function of size, coatings and surface defects. Finally, the distribution of CdSe nanocrystals between pseudophases in cloud point extraction was discussed based on experimental results. It was concluded that the size of CdSe nanocrystal present in an appropriate pseudophase is correlated with the way in which the non-ionic surfactant coats CdSe nanocrystals.

Luminescent CdSe/CdS core/shell nanocrystals in dendron boxes: superior chemical,photochemical and thermal stability

The surface ligands, generation-3 (G3) dendrons, on each semiconductor nanocrystal were globally cross-linked through ring-closing metathesis (RCM). The global cross-linking of the dendron ligands sealed each nanocrystal in a dendron box, which yielded box-nanocrystals. Although the dendron ligands coated CdSe nanocrystals (CdSe dendron-nanocrystals) were already quite stable, the stability of CdSe box-nanocrystals against chemical, photochemical, and thermal treatments were dramatically improved in comparison to that of the original dendron-nanocrystals. Furthermore, the box structure of the ligands monolayer coupled with the stable inorganic CdSe/CdS core/shell nanocrystals resulted in a class of extremely stable nanocrystal/ligands complexes. The band edge photoluminescence of the core/shell dendron-nanocrystals and box-nanocrystals were partially remained, and could be further brightened through controlled chemical oxidation or photooxidation. Practically, the stability of the box-nanocrystals is sufficient for most fundamental studies and technical applications. The box-nanocrystals may represent a general solution for the commonly encountered instability for many types of colloidal nanocrystals. The size distribution of the empty dendron boxes formed by the dissolution of the inorganic nanocrystals in concentrated HCl was very narrow. The empty boxes as new types of polymer capsules are soluble in solution, mesoporous, and with a very thin but stable peripheral. Those nanometer-sized cavities should be of interest for many purposes in the field of solution host-guest chemistry.     

Effect of P-Containing Ligands on the Structural and Optical Properties of (CdSe)<Subscript>n</Subscript> (n = 3, 6, 10) Clusters

The effect of phosphorus-containing ligands on the structure, energetics and properties of the (CdSe)_n clusters (n = 3, 6, and 10) with different number of PH₃ and PMe₃ ligands were studied by using density functional theory calculations. The P atom in the ligand interacts with Cd and forms a strong Cd–P coordination bond. The introduction of ligands does not change the cluster architecture, but leads to considerable changes in Cd–Se bondlength, charge distribution, binding energy, HOMO–LUMO gap and optical absorption. The ligand influence is enhanced with increasing ligand coverage. A blueshift in absorption band was predicted for the clusters with increasing ligands, resulting from the electron donating characteristics of the ligands that hamper electron transition from Se to Cd. As P-containing ligands are often used in the preparation of CdSe nanocrystals, our calculations reveal the influence of ligand-cluster interaction on the cluster geometrical and electronic properties, which would be helpful for the nanocrystal design and synthesis.     

Surface Stoichiometry of CdSe Nanocrystals Determined by Rutherford Backscattering Spectroscopy

Rutherford backscattering spectroscopy has been applied to study the surface stoichiometry of CdSe nanocrystals prepared by the high temperature pyrolysis of organometallics in trioctylphosphine oxide (TOPO). The diameter of the nanocrystals was varied from 22 to 56 Å. For all nanocrystal sizes we find the nanocrystals are Cd rich with an average Cd:Se ratio of 1.2±0.1. The Cd:Se stoichiometry is independent of the Cd:Se starting ratio used for the nanocrystal synthesis, indicating the excess Cd is not associated with the initial abundance of Cd but is an intrinsic property of nanocrystals prepared by this method. The surface coverage of the passivating TOPO ligands has also been determined and is larger than reported in previous X-ray photoelectron spectroscopy (XPS) studies of Bowen Katari et al.[1] The origin and structural implications of nonstoichiometric nanocrystals are discussed.     

Semiconductor nanocrystals with multifunctional polymer ligands

In this letter, we describe the preparation of a versatile polymer ligand, which can be attached to CdSe/ZnS semiconductor nanocrystals via a phase transfer reaction. The ligand is based on a chain of reactive esters, which can, in principle, be substituted by any compound containing amino-functionalities. The polymer/nanocrystal complexes are characterized in terms of structure and photostability.     

Large-scale synthesis of nearly monodisperse CdSe/CdS core/shell nanocrystals using air-stable reagents via successive ion layer adsorption and reaction

Successive ion layer adsorption and reaction (SILAR) originally developed for the deposition of thin films on solid substrates from solution baths is introduced as a technique for the growth of high-quality core/shell nanocrystals of compound semiconductors. The growth of the shell was designed to grow one monolayer at a time by alternating injections of air-stable and inexpensive cationic and anionic precursors into the reaction mixture with core nanocrystals. The principles of SILAR were demonstrated by the CdSe/CdS core/shell model system using its shell-thickness-dependent optical spectra as the probes with CdO and elemental S as the precursors. For this reaction system, a relatively high temperature, about 220-240 degrees C, was found to be essential for SILAR to fully occur. The synthesis can be readily performed on a multigram scale. The size distribution of the core/shell nanocrystals was maintained even after five monolayers of CdS shell (equivalent to about 10 times volume increase for a 3.5 nm CdSe nanocrystal) were grown onto the core nanocrystals. The epitaxial growth of the core/shell structures was verified by optical spectroscopy, TEM, XRD, and XPS. The photoluminescence quantum yield (PL QY) of the as-prepared CdSe/CdS core/shell nanocrystals ranged from 20% to 40%, and the PL full-width at half-maximum (fwhm) was maintained between 23 and 26 nm, even for those nanocrystals for which the UV-vis and PL peaks red-shifted by about 50 nm from that of the core nanocrystals. Several types of brightening phenomena were observed, some of which can further boost the PL QY of the core/shell nanocrystals. The CdSe/CdS core/shell nanocrystals were found to be superior in comparison to the highly luminescent CdSe plain core nanocrystals. The SILAR technique reported here can also be used for the growth of complex colloidal semiconductor nanostructures, such as quantum shells and colloidal quantum wells.     

Temperature- and field-dependent energy transfer in CdSe nanocrystal aggregates studied by magneto-photoluminescence spectroscopy

The influence of temperature and applied magnetic fields on photoluminescence (PL) emission and electronic energy transfer (ET) of both isolated and aggregated CdSe nanocrystals was investigated. Following 400-nm excitation, temperature-dependent, intensity-integrated and energy-resolved PL measurements were used to quantify the emission wavelength and amplitude of isolated CdSe nanocrystals. The results indicated an approximately three-fold increase in PL intensity upon decreasing the temperature from 300 K to 6 K; this was attributed to a reduction of charge carrier access to nanocrystal surface trap states and suppression of thermal loss channels. Temperature-dependent PL measurements of aggregated CdSe nanocrystals, which included both energy-donating and -accepting particles, were analyzed using a modified version of F?rster theory. Temperature-dependent ET efficiency increased from 0.55 to 0.75 upon decreasing the sample temperature from 225 K to 6 K, and the ET data contained the same trend observed for the PL of isolated nanoclusters. The application of magnetic fields to increase nanocrystal ET efficiency was studied using magneto-photoluminescence measurements recorded at a sample temperature of 1.6 K. We demonstrated that the exciton fine structure population of the donor was varied using applied magnetic fields, which in turn dictated the PL yield and the resultant ET efficiency of the CdSe nanocrystal aggregate system. The experimental data indicated an ET efficiency enhancement of approximately 7%, which was limited by the random orientation of the spherical nanocrystals in the thin film.     

Size and ligand effects on the electrochemical and spectroelectrochemical responses of CdSe nanocrystals

The electrochemical properties of CdSe quantum dots with electrochemically inactive surface ligands (TOPO) have been investigated in comparison with the analogous nanocrystals containing electrochemically active oligoaniline ligands. The TOPO-capped nanocrystals have been studied in a wide size range (from 3 to 6.5 nm) with the goal to amplify the influence of the quantum confinement effect on the electrochemical response. The determined HOMO and LUMO levels have been found in good agreement with the ones obtained from photoluminescence studies and those predicted theoretically. Ligand exchange with aniline tetramer significantly influences the voltammetric peaks associated with the HOMO oxidation and the LUMO reduction of the quantum dots, which are shifted to higher and lower potentials, respectively. These shifts are interpreted in terms of the positive ligand charging which precedes the oxidation of the nanocrystals and the insulating nature of the ligand in the case of the nanocrystal reduction. The ligand-nanocrystal interactions have also been studied by UV-Vis-NIR and Raman spectroelectrochemistry in comparison with a specially prepared model compound which, apart from the anchoring function is identical to the grafted oligoaniline ligand. Both spectroelectrochemical techniques clearly indicate the same nature of the oxidation/reduction pathway for both the model compound and the grafted ligand. The influence of the grafting is manifested by a shift in the onset of the ligand oxidation as compared to the case of the "free" model compound. Since both components (ligands and nanocrystals) mutually influence their electrochemical and spectroelectrochemical properties, the newly developed system can be considered as a true molecular hybrid. Such hybrids are of interest because the potential zone of the ligand electroactivity is well separated from that of the nanocrystals and, as a result, the organic part can be electrochemically switched between the semiconducting and the conducting states with no change in the oxidation state of the nanocrystal. The newly developed system offers therefore the possibility of an electrical addressing of individual nanocrystals via the conducting ligands.     

Colloidal CdSe nanocrystals synthesized in noncoordinating solvents with the addition of a secondary ligand: exceptional growth kinetics

The addition of a secondary ligand, trioctylphosphine oxide, in the synthesis of cadmium selenide nanocrystals performed in a system with oleic acid as the primary ligand and octadecene as the noncoordinating solvent gives rise to the improvement of nanocrystal size distribution. This phenomenon, which is more significant in the nucleation process than in the growth process, demonstrates that the existence of trioctylphosphine oxide allows for superior nucleation control and permits the facile and reproducible production of extremely small CdSe nanocrystals with narrow size distribution. A systematic study of the nanocrystal formation processes shows that the well-established colloidal nanocrystal growth mechanism, in which nucleation is followed by focusing of size distribution and ended with defocusing of size distribution, cannot be applied to our reactions. Instead, we observed an exceptional type of growth mechanism in which, after nucleation, clear defocusing instead of focusing follows; then slight focusing occurs.     

Size-dependent dissociation pH of thiolate ligands from cadmium chalcogenide nanocrystals

A method, pseudo steady-state titration, is introduced for determining the precipitation pH of nanocrystals coated by electron-donating ligands. CdSe nanocrystals coated with hydrophilic deprotonated thiol (thiolate) ligands were studied systematically. For comparison, CdTe and CdS nanocrystals coated with the same types of ligands were also examined. The results show that the precipitation of the nanocrystals is caused by the dissociation of the nanocrystal-ligand coordinating bonds from the nanocrystal surface. The ligands are removed from the surface due to protonation in a relatively low pH range, between 2 and 7 depending on the size, approximately within the quantum confinement size regime, and chemical composition (band gap) of the nanocrystals. In contrast, the redispersion of the nanocrystals was found to be solely determined by the deprotonation of the ligands. The size-dependent dissociation pH of the ligands was tentatively used as a means for determining the size-dependent free energy associated with the formation of a nanocrystal-ligand coordinating bond.     

Application of a microfluidic reaction system for CdSe nanocrystal preparation: their growth kinetics and photoluminescence analysis

We used a microreactor for CdSe nanocrystal preparation and explored the effects of experimental conditions on the properties of the products. The particle growth kinetics and photoluminescence properties of the nanocrystals showed identical trends to previous reports, indicating the efficiency of the current method for analysis of rapid nanocrystal synthesis as well as industrial production of CdSe nanocrystals.     

Ligand bonding and dynamics on colloidal nanocrystals at room temperature: the case of alkylamines on CdSe nanocrystals

With CdSe nanocrystals stabilized with very weak ligands (pyridine) as the starting materials, NMR techniques were applied to distinguish the bonded and free alkylamine ligands in an equilibrated adsorption/desorption system for the CdSe-amine nanocrystal-ligand pair. NMR and photoluminescence (PL) measurements were further correlated to identify the linear relationship between PL intensity and the surface ligand coverage of the amine-coated CdSe nanocrystals. For 3.5 nm CdSe nanocrystals and octylamine ligands, the chemical equilibrium constant (K) of the CdSe-amine nanocrystal-ligand adsorption/desorption process was found to be around 50-100, and the corresponding Delta(r)G(o) was calculated as 9.8-11.5 kJ/mol. With a proposed mathematic method, the corresponding chemical kinetic constants for the desorption (kd) and adsorption (ka) processes were measured to be 0.01 s(-1) and 0.5 L mol(-1) s(-1), respectively. K, kd, and ka obtained here are generally 2-4 magnitudes different from those estimated in literature. Analysis indicates that these constants are well consistent with the existing experimental observations.     

Alkyl chains of surface ligands affect polytypism of cdse nanocrystals and play an important role in the synthesis of anisotropic nanoheterostructures

We show that the length of the alkyl chain of surface ligands can shift the equilibrium between the wurtzite and zinc blende polytypes of CdSe nanocrystals. In-situ wide-angle X-ray scattering measurements reveal that short-chain (e.g., propyl) phosphonic acids stabilize CdSe nanocrystals with the zinc blende phase whereas octadecylphosphonic acid stabilize nanocrystals with the wurtzite phase. We also demonstrate how this effect can be used to improve the shape selectivity in the synthesis of anisotropic CdSe/CdS and ZnSe/CdS nanoheterostructures.     

The effects of chemisorption on the luminescence of CdSe quantum dots

We report on the effects of Lewis bases and other ligands on radiative recombination in CdSe quantum dots (QDs) in several solvents. Long-chain primary amines are found to be the most efficacious capping agents for CdSe QDs in nonpolar solvents. Primary alkylamines are superior to secondary and tertiary alkylamines. The kinetics of chemisorption and desorption in less polar solvents, such as hexane or chloroform, are temperature controlled and obey a Langmuir isotherm. Mercaptan adsorption also obeys a Langmuir isotherm, and alkylmercaptans rapidly displace amines, leading to luminescence quenching. In more polar solvents, such as toluene, ligands desorb, leading to luminescence quenching. It is proposed that surface Cd vacancies function as nonradiative recombination centers. The adsorption of a Lewis base to the QD raises the surface vacancy energy close to, or above, the conduction band edge and eliminates electron capture by the surface vacancies. Solvent polarity has a strong effect on luminescence since the solvent determines the extent of ligand adsorption to the QD surface.     

CdSe Spherical Quantum Dots Stabilised by Thiomalic Acid: Biphasic Wet Synthesis and Characterisation

CdSe quantum dots stabilised by thiomalic acid have been synthesised by an aqueous biphasic ligand exchange reaction in air. The materials are completely water‐soluble and were found to be stable over a long time. X‐ray diffraction and transmission electron microscopy reveal the formation of CdSe nanocrystals with cubic structure (a=0.6077 nm; spatial group: F‐43m). The average particle size is about 5 nm. Energy dispersive X‐ray analysis shows that the nanocrystals are nonstoichiometric, with a Cd/Se ratio varying between 60/40 and 70/30, and indicates the presence of Cd²⁺ ions at the nanocrystal surface. Diffuse reflectance infrared Fourier transform measurements suggest that thiomalic acid chelates CdSe through the thiol group and one carboxylic function, while the second COOH group is semi‐free. A complex‐like structure is proposed, in which thiomalic acid forms a five‐membered chelate ring with the Cd²⁺ ions present on the nanocrystal surface. Chelate effect accounts for the easiness of ligand exchange and is expected to additionally stabilise the nanosystem.