II-VI Semiconductor Nanocrystals Research Articles

Thermal Quenching in II-VI Semiconductor Nanocrystals: What Causes It and How to Eliminate It

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Shape-Programmed Nanofabrication: Understanding the Reactivity of Dichalcogenide Precursors

Dialkyl and diaryl dichalcogenides are highly versatile and modular precursors for the synthesis of colloidal chalcogenide nanocrystals. We have used a series of commercially available dichalcogenide precursors to unveil the molecular basis for the outcome of nanocrystal preparations, more specifically, how precursor molecular structure and reactivity affect the final shape and size of II-VI semiconductor nanocrystals. Dichalcogenide precursors used were diallyl, dibenzyl, di-tert-butyl, diisopropyl, diethyl, dimethyl, and diphenyl disulfides and diethyl, dimethyl, and diphenyl diselenides. We find that the presence of two distinctively reactive C-E and E-E bonds makes the chemistry of these precursors much richer and interesting than that of other conventional precursors such as the more common phosphine chalcogenides. Computational studies (DFT) reveal that the dissociation energy of carbon-chalcogen (C-E) bonds in dichalcogenide precursors (R-E-E-R, E=S or Se) increases in the order (R): diallyl<dibenzyl<di-tert-butyl<diisopropyl<diethyl<dimethyl<diphenyl. The dissociation energy of chalcogen-chalcogen (E-E) bonds remains relatively constant across the series. The only exceptions are diphenyl dichalcogenides, which have a much lower E-E bond dissociation energy. An increase in C-E bond dissociation energy results in a decrease in R-E-E-R precursor reactivity, leading to progressively slower nucleation and higher selectivity for anisotropic growth, all the way from dots to pods to tetrapods. Under identical experimental conditions, we obtain CdS and CdSe nanocrystals with spherical, elongated, or tetrapodal morphology by simply varying the identity and reactivity of the dichalcogenide precursor. Interestingly, we find that precursors with strong C-E and weak E-E bond dissociation energies such as Ph-S-S-Ph serve as a ready source of thiol radicals that appear to stabilize small CdE nuclei, facilitating anisotropic growth. These CdS and CdSe nanocrystals have been characterized using structural and spectroscopic methods. An intimate understanding of how molecular structure affects the chemical reactivity of molecular precursors enables highly predictable and reproducible synthesis of colloidal nanocrystals with specific sizes, shapes, and optoelectronic properties for customized applications.

Resonance Raman Overtone Intensities and Electron–Phonon Coupling Strengths in Semiconductor Nanocrystals

For linear electron-phonon coupling, the Huang-Rhys factor, S, gives the intensity ratio of the one-quantum vibronic transition (0 → 1) to the purely electronic origin transition (0 → 0) in a vibrationally resolved, zero-temperature absorption or emission spectrum. It is often assumed that the overtone to fundamental integrated intensity ratio in resonance Raman scattering of semiconductor nanocrystals is equal to or proportional to S, or that S may be determined from the overtone intensity in some other straightforward manner. In fact, this is not generally possible because of different excitation profiles for overtones and fundamentals, differential sensitivity of overtones and fundamentals to electronic dephasing, and interference effects from partially overlapping electronic transitions. Here we examine the relationship between the Huang-Rhys factor and the overtone to fundamental intensity ratio through spectroscopic simulations using parameters appropriate to II-VI semiconductor nanocrystals such as CdSe. A simple equation relating the overtone to fundamental Raman intensity ratio to the Huang-Rhys factor is obtained only in the case of a single resonant electronic state, excitation at the maximum of the inhomogeneously broadened absorption band, and a homogeneous line width small compared with the phonon frequency.

Tunable Infrared Phosphors Using Cu Doping in Semiconductor Nanocrystals: Surface Electronic Structure Evaluation.

In this Letter, we report the study of the effect of ligands on the surface electronic structure of the nanocrystal by exploiting the mechanism of the Cu-related optical transition, obtained by coupling the nanocrystal conduction band to the Cu ion state in Cu-doped II-VI semiconductor nanocrystals. Systematic study of steady-state luminescence and lifetime decay dynamics of this Cu-related emission in cadmium-based chalcogenides shows that the role of oleic acid in surface passivation is unexpectedly quite different for various chalcogenides. Further, using these leads in Cu-doped CdS nanocrystals, we develop near-infrared-emitting phosphor materials that have tunable, high quantum yield (∼35%) emission with a single-exponential lifetime decay. Surprisingly, unlike the emission from other Cu-doped II-VI nanocrystals, emission from Cu doping in CdS nanocrystals is found to exhibit high thermal stability, being essentially unchanged up to 100 °C, making them more viable for use in various practical applications.

Surface-Functionalization-Dependent Optical Properties of II–VI Semiconductor Nanocrystals

We report a study of the surface-functionalization-dependent optical properties of II-VI zinc-blende semiconductor nanocrystals on the basis of ligand-exchange chemistry, isomaterial core/shell growth, optical spectroscopy, transmission electron microscopy, and X-ray powder diffraction. Our results show that the transition energy and extinction coefficient of the 2S(h3/2)1S(e) excitonic band of these nanocrystals can be strongly modified by their surface ligands as well as ligand associated surface atomic arrangement. The oleylamine exchange of oleate-capped zinc-blende II-VI nanocrystals narrows the energy gap between their first and second excitonic absorption bands, and this narrowing effect is size-dependent. The oleylamine exchange results in the quenching, subsequent recovery, and even enhancing of the photoluminescence emission of these II-VI semiconductor nanocrystals. In addition, the results from our X-ray powder diffraction measurements and simulations completely rule out the possibility that oleate-capped zinc-blende CdSe nanocrystals can undergo zinc-blende-to-wurtzite crystal transformation upon ligand exchange with oleylamine. Moreover, our theoretical modeling results suggest that the surface-functionalization-dependent optical properties of these semiconductor nanocrystals can be caused by a thin type II isomaterial shell that is created by the negatively charged ligands (e.g., oleate and octadecyl phosphonate). Taking all these results together, we provide the unambiguous identification that II-VI semiconductor nanocrystals exhibit surface-functionalization-dependent excitonic absorption features.

Synthesis and characterization of hybrid CdS/MEH-PPV nanocomposites for photovoltaic applications

ABSTRACTInorganic-organic nanocomposites, with II-VI or III-V semiconductor nanocrystals (NCs) embedded in semiconducting polymer matrix, are very promising materials for photovoltaic applications.Here, we present an effective and easy synthesis procedure to obtain a hybrid nanocomposite with CdS NCs dispersed in poly[2-methoxy-5-(2-(2’-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) conjugated polymer. CdS NCs are synthesized directly within the matrix through the decomposition of a suitable unimolecular precursor dispersed homogeneously in the polymer.We show that CdS NCs are formed at low annealing temperature avoiding structural damages and without affecting the functional properties of the MEH-PPV polymer. The NCs diameter ranges between 1.5nm and 4nm depending on the annealing temperature. In addition, no coalescence phenomena of CdS NCs were noticed in TEM observations even at very high particle density (40 wt %).

Doping Transition Metal (Mn or Cu) Ions in Semiconductor Nanocrystals

Following growth doping strategy and using dopant oxides nanocrystals as dopant sources, we report here two different transition-metal ions doped in a variety of group II-VI semiconductor nanocrystals. Using manganese oxide and copper oxide nanocrystals as corresponding dopant sources, intense photoluminescence emission over a wide range of wavelength has been observed for different host nanocrystals. Interestingly, this single doping strategy is successful in providing such highly emissive nanocrystals considered here, in contrast with the literature reports that would suggest synthesis strategies to be highly specific to the particular dopant, host, or both. We investigate and discuss the possible mechanism of the doping process, supporting the migration of dopant ions from dopant oxide nanocrystals to host nanocrystals as the most likely scenario.

Phase Transition of II−VI Semiconductor Nanocrystals

The phase transition is fundamental for understanding physical and chemical properties of materials. The phase transition at the nanometer scale is usually distinguished from that of the bulk counterpart. It is essential to pursue the basic physics involved in the phase transition on nanoscale for applications of nanomaterials. Herein, we have established an analytical thermodynamic model at the nanometer scale to study the phase transition of II-VI semiconductor nanocrystals, and revealed the size-dependent polymorphism behaviors of the phase transition. The physical origin of the size effects on the polymorphism behaviors of II-VI semiconductor nanocrystals was addressed on the basis of the contributions of surface energy and surface stress of nanocrystals to the total Gibbs free energy. It was found that the low surface energy and the small surface stress always predominate the thermal stability of nanostructures with the metastable phase. These results provided new insight into the fundamental understanding of the phase transition of II-VI semiconductor nanocrystals.

Optical Properties of Single Semiconductor Nanocrystals

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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.

Surface Study of P-Type MBE Gallium Nitride Growth over CdSe Quantum Dots

The objective of our current work is to observe the effects of MBE p-GaN growth over II-VI semiconductor nanocrystals on an MOCVD n-GaN template. The starting material was approximately 2 microns of n-type GaN MOCVD material atop a sapphire wafer. CdSe quantum dots were applied through drop and spin casting. A p-type MBE GaN layer of 2500 A was grown using a nitrogen plasma source. MBE allowed precise growth while SIMS analysis showed the relatively low temperature associated with this method, versus MOCVD, preserved the quantum dots. The surface was investigated using atomic force microscopy in tapping mode for samples at various high/low substrate and magnesium cell temperatures.

On the Size-Dependent Behavior of Nanocrystal−Ligand Bonds

Recent experiments have indicated that 3-mercapto-1-propanol ligands display a size-dependent binding energy of attachment to the surface of II-VI semiconductor nanocrystals. Using semiempirical calculations, we exhaustively calculate the energy of this bond at each surface site, for CdSe and CdSe/CdS core/shell nanocrystals ranging from 1.8 to 4.1 nm in diameter. Our results suggest that the experimentally observed changes in binding energy are due to the distribution of surface facets on the nanocrystals, and not related to the band gap, as proposed in the experimental paper.

Shape Control of II–VI Semiconductor Nanomaterials

Anisotropic II-VI semiconductor nanocrystals and nanoparticles have become important building blocks for (potential) nanotechnological applications. Even though a wide variety of differently shaped nanoparticles of this class can be prepared, the underlying mechanisms are mostly not fully understood. This Review article provides a brief overview of the currently studied shape-evolution mechanisms and the most prominent synthesis methods for such particles, with an aim to provide a fundamental understanding on how different morphologies evolve, and to function as a tool to aid in the preparation of specific nanocrystals.

Optical properties of single semiconductor nanocrystals

We present an overview of the current progress in the understanding of the (steady state) optical properties of individual II-VI semiconductor nanocrystals. We begin with a presentation of the conceptual development of the theory required to model the electronic structure of these systems. This is followed by an overview of the current experimental results obtained from the spectroscopy of individual semiconductor nanocrystals, and in particular, we focus on the study of photoluminescence intermittency (blinking) and spectral diffusion. Where possible, we link the experimental observations to the predictions of current theories. We conclude that the surface of small semiconductor crystals plays an important role in determining their optical properties.

Time-resolved intraband relaxation of strongly confined electrons and holes in colloidal PbSe nanocrystals

The relaxation of strongly-confined electrons and holes between 1P and 1S levels in colloidal PbSe nanocrystals has been time-resolved using femtosecond transient absorption spectroscopy. In contrast to II-VI and III-V semiconductor nanocrystals, both electrons and holes are strongly confined in PbSe nanocrystals. Despite the large electron and hole energy level spacings (at least 12 times the optical phonon energy), we consistently observe picosecond time-scale relaxation. Existing theories of carrier relaxation cannot account for these experimental results. Mechanisms that could possibly circumvent the phonon bottleneck in IV-VI quantum dots are discussed.

Syntheses and Applications of Mn-Doped II-VI Semiconductor Nanocrystals

Luminescent Mn-doped II-VI semiconductor nanocrystals have been intensively investigated over the last ten years. Several semiconductor host materials such as ZnS, CdS, and ZnSe have been used for Mn-doped nanocrystals with different synthetic routes and surface passivation. Beyond studies of their fundamental properties including photoluminescence and size, these luminescent nanocrystals have now been tested for practical applications such as electroluminescent displays and biological labeling agents (biomarkers). Here, we first review ZnS:Mn, CdS:Mn/ZnS core/shell, and ZnSe:Mn nanocrystal systems in terms of their synthetic chemistries and photoluminescent properties. Second, based on ZnS:Mn and CdS:Mn/ZnS core/shell nanocrystals as electroluminescent components, direct current electroluminescent devices having a hybrid organic/inorganic multilayer structure are reviewed. Highly luminescent and photostable CdS:Mn/ZnS nanocrystals can further be used as the luminescent biomarkers and some preliminary results are also discussed here.

Optically Detected Magnetic Resonance Studies of Colloidal Semiconductor Nanocrystals

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Emission intermittency in silicon nanocrystals

We present detailed results of blinking studies on individual silicon nanocrystals. The experiments show, that similar to II-VI semiconductor nanocrystals, the blinking process obeys a power law statistics. An excitation intensity dependence of the power law exponent is found for the off time probability distribution. The intensity dependence is interpreted in terms of an intensity dependent tunneling rate due to Auger assisted processes. Further we demonstrate a relation of the off time distribution to the bleaching and recovery of the emission of nanocrystal ensembles, which gives further insight in the blinking behavior according to ensemble studies. The experimental data is discussed in terms of two alternative blinking models. Evidence is provided for the existence of self-trapped polaron-like states for the ejected charge.

Optically detected magnetic resonance studies of colloidal semiconductor nanocrystals.

The review describes the studies of the magneto-optical properties of II-VI and III-V semiconductor nanocrystals (NCs) capped with organic or inorganic epitaxial shells. The investigations focused on the chemical identification of localization sites (core, shell, or interface) of photogenerated carriers in spherical NCs and elucidated the influence of the surface/interface quality on the optical properties of the materials. Optically detected magnetic resonance (ODMR) spectroscopy was used for the study of the proposed physical properties. The ODMR method provides the means to identify the surface/interface sites and correlate them with specific optical transition. In addition, this method reveals information about the spin multiplicity of band edge and trapped states and the electron-hole exchange interaction, determines the spectroscopic g-factors, distinguishes between the radiative and nonradiative characteristic of a trapping site, and evaluates the spin-lattice relaxation times.

Evolution of the electronic structure with size in II-VI semiconductor nanocrystals

In order to provide a quantitatively accurate description of the band gap variation with sizes in various II-VI semiconductor nanocrystals, we make use of the recently reported tight-binding parametrization of the corresponding bulk systems. Using the same tight-binding scheme and parameters, we calculate the electronic structure of II-VI nanocrystals in real space with sizes ranging between 5 and 80 {\AA} in diameter. A comparison with available experimental results from the literature shows an excellent agreement over the entire range of sizes.