Ligand-mediated modification of the electronic structure of CdSe quantum dots.

X-ray absorption spectroscopy and ab initio modeling of the experimental spectra have been used to investigate the effects of surface passivation on the unoccupied electronic states of CdSe quantum dots (QDs). Significant differences are observed in the unoccupied electronic structure of the CdSe QDs, which are shown to arise from variations in specific ligand-surface bonding interactions.

Evidence for ligand-induced paramagnetism in CdSe quantum dots.

We report evidence that paramagnetism in CdSe QDs can be induced via manipulation of the surface chemistry. Using SQUID magnetometry and X-ray absorption spectroscopy, we demonstrate that the paramagnetic behavior of the CdSe QDs can be varied by changing the ligand end-group functionality of the passivating layer. Contrary to previous reports, no evidence for ferromagnetism was observed. The results suggest that the paramagnetism is induced via pi back-bonding between Cd 4d orbtials and ligands with empty pi* orbitals.

Determination of the exciton binding energy in CdSe quantum dots.

The exciton binding energy (EBE) in CdSe quantum dots (QDs) has been determined using X-ray spectroscopy. Using X-ray absorption and photoemission spectroscopy, the conduction band (CB) and valence band (VB) edge shifts as a function of particle size have been determined and combined to obtain the true band gap of the QDs (i.e., without an exciton). These values can be compared to the excitonic gap obtained using optical spectroscopy to determine the EBE. The experimental EBE results are compared with theoretical calculations on the EBE and show excellent agreement.

Near-edge X-ray absorption fine structure spectroscopy of diamondoid thiol monolayers on gold.

Diamondoids, hydrocarbon molecules with cubic-diamond-cage structures, have unique properties with potential value for nanotechnology. The availability and ability to selectively functionalize this special class of nanodiamond materials opens new possibilities for surface modification, for high-efficiency field emitters in molecular electronics, as seed crystals for diamond growth, or as robust mechanical coatings. The properties of self-assembled monolayers (SAMs) of diamondoids are thus of fundamental interest for a variety of emerging applications. This paper presents the effects of thiol substitution position and polymantane order on diamondoid SAMs on gold using near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS). A framework to determine both molecular tilt and twist through NEXAFS is presented and reveals highly ordered diamondoid SAMs, with the molecular orientation controlled by the thiol location. C 1s and S 2p binding energies are lower in adamantane thiol than alkane thiols on gold by 0.67 +/- 0.05 and 0.16 +/- 0.04 eV, respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different degrees of steric strain and electronic interaction with the substrate. This work demonstrates control over the assembly, in particular the orientational and electronic structure, providing a flexible design of surface properties with this exciting new class of diamond nanoparticles.

Structural development of mercaptophenol self-assembled monolayers and the overlying mineral phase during templated CaCO3 crystallization from a transient amorphous film.

Formation of biomineral structures is increasingly attributed to directed growth of a mineral phase from an amorphous precursor on an organic matrix. While many in vitro studies have used calcite formation on organothiol self-assembled monolayers (SAMs) as a model system to investigate this process, they have generally focused on the stability of amorphous calcium carbonate (ACC) or maximizing control over the order of the final mineral phase. Little is known about the early stages of mineral formation, particularly the structural evolution of the SAM and mineral. Here we use near-edge X-ray absorption spectroscopy (NEXAFS), photoemission spectroscopy (PES), X-ray diffraction (XRD), and scanning electron microscopy (SEM) to address this gap in knowledge by examining the changes in order and bonding of mercaptophenol (MP) SAMs on Au(111) during the initial stages of mineral formation as well as the mechanism of ACC to calcite transformation during template-directed crystallization. We demonstrate that formation of ACC on the MP SAMs brings about a profound change in the morphology of the monolayers: although the as-prepared MP SAMs are composed of monomers with well-defined orientations, precipitation of the amorphous mineral phase results in substantial structural disorder within the monolayers. Significantly, a preferential face of nucleation is observed for crystallization of calcite from ACC on the SAM surfaces despite this static disorder.

Experimental observation of quantum confinement in the conduction band of CdSe quantum dots.

X-ray absorption spectroscopy has been used to characterize the evolution in the conduction band (CB) density of states of CdSe quantum dots (QDs) as a function of particle size. We have unambiguously witnessed the CdSe QD CB minimum (CBM) shift to higher energy with decreasing particle size, consistent with quantum confinement effects, and have directly compared our results with recent theoretical calculations. At the smallest particle size, evidence for a pinning of the CBM is presented. Our observations can be explained by considering a size-dependent change in the angular-momentum-resolved states at the CBM.

Effect of ring substitution position on the structural conformation of mercaptobenzoic acid self-assembled monolayers on Au(111).

Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, photoemission spectroscopy (PES), and contact angle measurements have been used to examine the structure and bonding of self-assembled monolayers (SAMs) prepared on Au(111) from the positional isomers of mercaptobenzoic acid (MBA). The isomer of MBA and solvent chosen in SAM preparation has considerable bearing upon film morphology. Carbon K-edge NEXAFS measurements indicate that the monomers of 2-, 3-, and 4-MBA have well-defined orientations within their respective SAMs. Monomers of 3- and 4-MBA assume an upright orientation on the Au substrates in monolayers prepared using an acetic acid in ethanol solvent. The aryl ring and carboxyl group of these molecules are tilted from the surface normal by a colatitudal angle of approximately 30 degrees . Preparation of 4-MBA SAMs using pure ethanol solvent, a more traditional means of synthesis, had no appreciable effect upon the monomer orientation. Nonetheless, S(2p) PES measurements illustrate that it results in extensive bilayer formation via carboxyl group hydrogen-bonding between 4-MBA monomers. In 2-MBA monolayers prepared using acetic acid/ethanol solvent, the monomers adopt a more prostrate orientation on the Au substrates, in which the aryl ring and carboxyl group of the molecules are tilted approximately 50 degrees from the surface normal. This configuration is consistent with an interaction between both the mercaptan sulfur and carboxyl group of 2-MBA with the underlying substrate. S(2p) and C(1s) PES experiments provide supporting evidence for a bidentate interaction between 2-MBA and Au(111).

Surface structure and chemical switching of thioctic acid adsorbed on Au(111) as observed using near-edge X-ray absorption fine structure.

Thioctic acid (alpha-lipoic acid) is a molecule with a large disulfide-containing base, a short alkyl chain with four CH2 units, and a carboxyl termination. Self-assembled monolayer (SAM) films ofthioctic acid adsorbed on Au(111) have been investigated with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS) to determine film quality, bonding, and morphology. Using standard preparation protocols for SAMs, that is, dissolving thioctic acid in ethanol and exposing gold to the solution, results in poor films. These films are highly disordered, contain a mixture of carboxyl and carboxylate terminations, have more than monolayer coverage, and exhibit unbound disulfide. Conversely, forming films by dissolving 1 mmol thioctic acid into 5% acetic acid in ethanol (as previously reported with carboxyl-terminated alkanethiols) forms ordered monolayers with small amounts of unbound sulfur. NEXAFS indicates tilted over endgroups with the carboxyl group normal on average 38 degrees from the surface normal. Slight angle-dependent intensity modulations in other features indicate alkyl chains statistically more upright than prostrate on the surface. Reflection-absorption Fourier transform infrared (RA-FTIR) spectra indicate hydrogen bonding between neighboring molecules. In such well-formed monolayers, a stark reorientation occurs upon deprotonation of the endgroup by rinsing in a KOH solution. The carboxylate plane normal is now about 66 degrees from sample normal, a much more upright orientation. Data indicate this reorientation may also cause a more upright orientation to the alkyl portion of the molecules.

Functionalized silicon membranes for selective bio-organism capture.

Membranes with various pore size, length, morphology and density have been synthesized from diverse materials for size-exclusion-based separation. An example is the sterilization of intravenous lines by exclusion of bacteria and viruses using polyvinylidene fluoride membranes with 0.1-microm-diameter pores. Chemically specific filtration has recently been addressed for small molecules. Nevertheless, specific bio-organism immobilization and detection remains a great technical challenge in many biomedical applications, such as decontamination or analysis of air and liquids such as drinking water and body fluids. To achieve this goal, materials with controlled pore diameter, length and surface chemistry are required. In this letter, we present the first functionalized silicon membranes and demonstrate their ability to selectively capture simulated bio-organisms. These extremely versatile and rigid devices open the door to a new class of materials that are able to recognize the external fingerprints of bio-organisms-such as size and outer membrane proteins-for specific capture and detection applications.

Quantum confinement and fullerenelike surface reconstructions in nanodiamonds.

We present x-ray absorption and emission experiments and ab initio calculations showing that the size of carbon diamond must be reduced to at least 2 nm, in order to observe an increase of its optical gap, at variance with Si and Ge where quantum confinement effects persist up to 6-7 nm. In addition, our calculations show that the surface of nanodiamond particles larger than approximately 1 nm reconstructs in a fullerenelike manner, giving rise to a new family of carbon clusters: bucky diamonds. Signatures of these surface reconstructions are compatible with pre-edge features observed in measured absorption spectra.