QUANTUM DOTS NANOCRYSTALS

Definition: QUANTUM CONFINEMENT

. Unlike the particle in a box {ie: infinite well} where electrons are confined in 1D a quantum dot is a semiconductor whose excitons are in 3-D confinement.

The concepts of energy levels, bandgap, conduction band and valence band still apply. However, there is a major difference. Excitons have an average physical separation between the electron and hole, referred to as the Exciton Bohr Radius this physical distance is different for each material. In bulk, the dimensions of the semiconductor crystal are much larger than the Exciton Bohr Radius, allowing the exciton to extend to its natural limit. However, if the size of a semiconductor crystal becomes small enough that it approaches the size of the material's Exciton Bohr Radius, then the electron energy levels can no longer be treated as continuous - they must be treated as discrete, meaning that there is a small and finite separation between energy levels.

This situation of discrete energy levels is called quantum confinement , and under these conditions, the semiconductor material ceases to resemble bulk, and instead can be called a quantum dot. This has large repercussions on the absorptive and emissive behavior of the semiconductor material. This new material is now termed as a nanocrystal, whose shape and size govern the discrete eigenenergy levels of the semiconductor. Generally the smaller the size of the crystal, the larger the band gap, the greater the difference in energy between the highest valence band and the lowest conduction band becomes, therefore more energy is needed to excite the dot, and concurrently, more energy is released when the crystal returns to its resting state. Source : http://www.evidenttech.com/quantum-dotsexplained/how-quantum-dots-work.html

Exiton Bohr Radius eExiton Pair

3-Dimensional Nanocrystal

Mathematics for Bohr Radius the NanoCrystals 3D or Quantum Dots This different behaviour can be explained using quantum physics, because at these dimensions, comparable to de-Broglies wavelenght of electrons in a solid (= h/p), the quantum nature of matter becomes relevant. The main mechanism that triggers these properties is quantum confinement. Quantum confinement becomes visible when the particles dimensions are comparable to the excitons Bohr radius (the natural separation between an electron that leaves the valence band and the hole left behind, this electron-hole pair usually called an exciton). Using the hydrogen atom model this radius can be estimated: rex = 0 r h 2 / e2

As you can see, the excitons Bohr radius has different values for different materials ( and r ) differ from material to material). Usual values for this radius are in the nanometer range, for example in the case of GaAs {rex = 11.5 nm .} When the particles dimensions become smaller than this radius, the carriers movement is restricted.

In a semiconductor crystal, the conduction electrons are free to move in the volume, so the spectrum is almost continous and the density of states is proportional to the square root of the energy. In the case of a nanocrystal, because of the quantum confinement, the spectrum becomes discrete and the bandgap increases. Quantum dots

The absorbtion spectrum continous for bulk (black continous line) and discrete for a quantum dot.

Quantum Confinement Theory

According to the quantum confinement theory, electrons in the conduction band and holes in the valence band are confined spatially by the potential barrier of the surface. Because of the confinement of both the electrons and the holes, the lowest energy optical transition from the valence to the conduction band increases in energy, effectively increasing the band gap. In the semiconductor crystal, the exciton Bohr radius is determined by the extension in the electrons and holes wave-functions. When the particles dimensions become smaller, reaching the Bohr radius, these wave functions are confined by the nanocrystals limits and the carriers kinetic energy increses. This leads to a blue shift of the spectrum. A very common quantum dot of CdSe, the bandgap shifts from 1.7eV to 2.4eV when the crystal diameter passes from 20nm to 2nm.

The first model that describes the relation between the bandgap energy and the particles dimensions is based on the particle in a box model { ie: En = h2n2 / 8 me L2} leading to this equation: E = Eg + h2 / 8 R2 (1/ me + 1/ mh ) 1.8 e2 / 4R Where Eg is the bandgap energy of the bulk semiconductor the second term describes the energy due to confinement effects {1/ R2} , while the 3rd term describes the decrease in energy due to Coulomb attaction b/w the electron and the hole.{ 1/R} . The 2nd and 3rd terms define the exitonic levels This equation gives a good fit of the experimentally observed relation between E and R for the weak confinement regime but cannot explain the observations in the strong confinement regime where the effective mass approximation with infinite barriers breaks down

In addition to a change in the absorbtion energy, the reduction in size gives rise to the appearance of discrete energy levels at the band edge. The density of states in the quasi-continuum of energy levels increases rapidly above the conduction band edge and below the valence band edge. For semiconductor quantum dots the situation is different. Due to the limited number of atoms in the quantum dot (typically 100-10 000) discrete atomic like energy levels appear at the edges of the bands (Fig. 3). This quantum size effect is reflected in the absorption spectra (Fig.1) by the appearance of discrete absorption bands. As the particles dimensions go smaller, this structure becomes more pronounced, because the separation between energy levels increases.

Band structure for a bulk semiconductor (left) and for a semiconductor nanocrystal in the quantum size regime (right).

Another characteristic of these quantum dots comming from the reduced dimensionality is a high surface-to-volume ratio, so a high number of atoms are at the surface, meaning that the surface effects are more important. It leads to some surface states called traps that develop a series of allowed levels in the bandgap. These levels can rettain charges, allowing nonradiative recombination, leading to a degradation in electronic and optical properties.
We can conclude that all the above presented properties place nanocrystals between atoms and bulk semiconductors. These properties are: a larger bandgap than bulk semiconductors, blue shift, discrete energy levels of spectrum and finally higher surface-to-volume ratio.

Sources: Background on slides: http://www.physorg.com/newman/gfx/news/hires/couplingofsi.jpg

http://www.kprc.se/Framed/Main/Pics/QuantumDots.jpg
Written Sources: http://www.cmmip.ro/nanocrystalnet/about.html