Quantum dots electronic properties

The goal of nanoscience is to understand, and to manipulate, the behavior of objects of reduced dimensionality—structures that are smaller than 100 nm in at least one active dimension. The field is predicated on the assumption that small objects/devices/assemblies acquire new properties and forms of behavior that result from their constrained physical size. For example, in semiconductor quantum dots, electrons are bounded in all three dimensions, placing rather different boundary conditions on the solutions to Schrodinger s equation from those that apply to bulk materials with the consequence that their band structures are very different form those of bulk semiconductors. Nanotechnology relies on the organization of low-dimensional structures into devices or systems. Patterning—the spatial organization of components relative to one another—is thus an activity that is of foundational importance to the entire enterprise. 

Clusters are intennediates bridging the properties of the atoms and the bulk. They can be viewed as novel molecules, but different from ordinary molecules, in that they can have various compositions and multiple shapes. Bare clusters are usually quite reactive and unstable against aggregation and have to be studied in vacuum or inert matrices. Interest in clusters comes from a wide range of fields. Clusters are used as models to investigate surface and bulk properties [2]. Since most catalysts are dispersed metal particles [3], isolated clusters provide ideal systems to understand catalytic mechanisms. The versatility of their shapes and compositions make clusters novel molecular systems to extend our concept of chemical bonding, stmcture and dynamics. Stable clusters or passivated clusters can be used as building blocks for new materials or new electronic devices [4] and this aspect has now led to a whole new direction of research into nanoparticles and quantum dots (see chapter C2.17). As the size of electronic devices approaches ever smaller dimensions [5], the new chemical and physical properties of clusters will be relevant to the future of the electronics industry. 

Chemical and electrochemical techniques have been applied for the dimensionally controlled fabrication of a wide variety of materials, such as metals, semiconductors, and conductive polymers, within glass, oxide, and polymer matrices (e.g., [135-137]). Topologically complex structures like zeolites have been used also as 3D matrices [138, 139]. Quantum dots/wires of metals and semiconductors can be grown electrochemically in matrices bound on an electrode surface or being modified electrodes themselves. In these processes, the chemical stability of the template in the working environment, its electronic properties, the uniformity and minimal diameter of the pores, and the pore density are critical factors. Typical templates used in electrochemical synthesis are as follows ... 

Particle size and the method of nanoparticle preparation (including the capping agent used) determine the physical and electronic properties of the quantum dots produced. This gives chemists the unique ability to change the electronic and chemical properties of a semiconductor material by simply controlling particle size and preparative conditions employed. There are various methods for the preparation of nanoparticles however, not all methods work well for the preparation of compound semiconductor nanocrystallites. 

Owing to their unique (tunable-electronic) properties, semiconductor (quantum dots) nanocrystals have generated considerable interest for optical DNA detection [12], Recent activity has demonstrated the utility of quantum dot nanoparticles for enhanced electrical DNA detection [33, 34, 50], Willner et al. reported on a photoelectrochemical transduction of DNA sensing events in connection with DNA cross-linked CdS nanoparticle arrays [50], The electrostatic binding of the Ru(NH3)63+ electron acceptor to the dsDNA... 

Abstract Silver clusters, composed of only a few silver atoms, have remarkable optical properties based on electronic transitions between quantized energy levels. They have large absorption coefficients and fluorescence quantum yields, in common with conventional fluorescent markers. But importantly, silver clusters have an attractive set of features, including subnanometer size, nontoxicity and photostability, which makes them competitive as fluorescent markers compared with organic dye molecules and semiconductor quantum dots. In this chapter, we review the synthesis and properties of fluorescent silver clusters, and their application as bio-labels and molecular sensors. Silver clusters may have a bright future as luminescent probes for labeling and sensing applications. 

On a somewhat larger scale, there has been considerable activity in the area of nanocrystals, quantum dots, and systems in the tens of nanometers scale. Interesting questions have arisen regarding electronic properties such as the semiconductor energy band gap dependence on nanocrystal size and the nature of the electronic states in these small systems. Application [31] of the approaches described here, with the appropriate boundary conditions [32] to assure that electron confinement effects are properly addressed, have been successful. Questions regarding excitations, such as exdtons and vibrational properties, are among the many that will require considerable scrutiny. It is likely that there will be important input from quantum chemistry as well as condensed matter physics. 

Under electron irradiation (or by other mechanisms) it is possible to generate carbon vacancies leading to the formation of extended defect domains (with the presence of pentagonal and heptagonal, and even four-membered carbon rings) showing semiconductor character. This is the mechanism of formation of semiconductor properties in quantum-dot carbon nanoparticles or graphene nanoribbon. The mechanism... 

Yoffe, A. D. Semiconductor quantum dots and related systems Electronic, optical, luminescence and related properties of low dimensional systems. Adv. Phys. 50, 1-208 (2001). 

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