Chapter 2: Theory of Size-Dependent Optical Properties

Summary
Experimental observations of spherical CdSe nanocrystals have shown that as the average radius, R, increases from 0.6 nm to 4.15 nm, the photoluminescence emission color changes from blue to red, and the photon energy of the first absorbance peak, E12, decreases from 3.02 eV to 1.88 eV 24 and eventually approaches the bandgap energy, Eg = 1.7 eV, of bulk CdSe.25 Various theoretical approaches have been developed to explain the relationship between R and E12. The effective mass approximation predicts that a positive, size-dependent energy shift will be proportional to 1/R2, based on quantum confinement,26 while classical physics predicts a positive energy shift will be proportional to1/R, based on the dielectric properties of spheres.27 Complex simulations of the band structure in semiconductor nanocrystals attempt to provide more accurate predictions of the allowed photon transitions for quantum dots of a particular size,28 but these results do not produce analytical expressions for E versus R. Empirically, a positive energy shift proportional to 1/R closely follows experimental observations and is useful for converting observed absorbance spectra into estimates of particle size in order to track quantum dot growth kinetics.

Quantum Confinement Theory

Quantum dots are so named because their tunable luminescent emission may originate from quantum confinement. The number of degrees of freedom equals the

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Chapter 2: Theory of Size-Dependent Optical Properties

dimensionality. Reducing the effective dimensionality of the region that constrains the electrons wave function, from a 3D bulk solid, to a 2D nano-thin plane (in quantum well lasers and high mobility field effect transistors), to 1D quantum wires, and finally to 0D quantum dots, can produce technologically useful properties. As the electron is more confined, its allowed energy states are also more restricted and more size-dependent. Unconfined conduction electrons in a 3D bulk semiconductor experience the seemingly boundless periodic electric potential of the crystal lattice. When electrons in the conduction band recombine radiatively with holes (i.e. missing electrons) in the valence band and essentially return to their ground state, photons are emitted with energies near or just below Eg, which is a material property independent of sample size. However, size-dependent quantum confinement effects develop when the thickness of an electronic layer approaches the de Broglie wavelength of the electron in a quantum well structure,25 and when the radius of a semiconductor sphere is smaller than the bulk-exciton Bohr radius, in a nanocrystal.26 In a quantum dot, the electron and hole wave functions are confined on all sides by the crystal boundaries, where the electric potential is higher. Such constrained electron-hole pairs can only have discrete energies and the transition energy between the first two energy states is higher than Eg by a sizedependent energy shift, En,l. Various theories are used to explain and estimate the magnitude of this energy shift. The effective mass approximation comes from solving the Schrdinger equation for an isolated electron and then for an isolated hole in a sphere, and assuming that the effective masses of carriers in the quantum dot are the same as in a bulk semiconductor. In this case, the discrete energy levels, Enl, are given by Equation (2-1), where h is

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Chapter 2: Theory of Size-Dependent Optical Properties

Plank's constant, mo is the rest mass of an electron, me and mh are the effective masses of electrons in the conduction band and holes in the valence band, respectively, and n,l is a dimensionless series that takes discrete values. The value of 1,0 is equal to for the lowest allowed interband transition between the 1s electron and the 1s hole states. The next values in this sequence, 11=4.4934, 12=5.7635, 20=2 ,26 can be used to predict the structure of an absorbance or excitation spectra for a given sample (with a fixed average R, me, and mh) by noting that En,l/E10=(n,l/)2. This will be examined later in the results section.
E n ,l = E g + E n.l 1 = Eg + 2 R 1 1 h n ,l 2 m + m h 8 e
2 2

(2-1)

To calculate the first photon transition energy, E12, (in eV) it is useful to express Equation (2-1) in the form shown by Equation (2-2). Here is the wavelength of the first absorbance peak (in nm), and c is the speed of light. We note that the product hc has a value of 1239.77 eV nm,25 and that the term h2/(8mo) equals 0.376036 eV nm2. For bulk CdSe, Eg is 1.7 eV, me/mo is 0.13, and mh/mo is 0.45, according to Sze.25 Then the photon energy in eV can be estimated from the radius in nm.
E1s 1s = hc = Eg + 1 mo mo h 2 1 = 1.7 ( eV ) + 2 3.73( eV nm 2 ) + 2 R( nm ) R m e m h 8m o

(2-2)

To test this theory, numerous authors have measured the average radius of colloidal CdSe nanocrystals in each sample using transmission electron microscopy (TEM), and they have also measured the photon energy of the first absorbance peak.24,27,29,28 This experimental data is plotted as symbols in Figure 2-1 and in Figure 2-2.

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Chapter 2: Theory of Size-Dependent Optical Properties

CdSe Quantum Dots 3.1 3 Absorbance Peak Photon Energy (eV) 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2 1.9 1.8 1.7 0 1 2 3 4 5 Nanocrystal Radius (nm) 6
Data: Murray 2000 Data: Murray 1993 Data: Peng 1998 a) E=1.7+3.73/R^2 b) E=1.7+1.5/R^2 c) E=1.7+3.73/R^2 -0.26/R d) E=1.7+0.82/R

Figure 2-1. Size dependent photon transition energy in CdSe quantum dots. Symbols indicate experimental estimates of the radius, R, from TEM images, and the photon energy, E, of each samples primary absorbance peak according to several authors.24,27,29 Curves show the following models for E versus R: a) effective mass approximation, b) parabolic 2-band model, c) effective mass with Coulomb interaction,30 and d) sizedependent capacitance.

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Chapter 2: Theory of Size-Dependent Optical Properties

The effective mass approximation significantly overestimates the first absorbance peak energy for quantum dots with a radius smaller than 4 nm, as shown in Figure 2-1 curve a). Noting this discrepancy, Murray et. al proposed that the effective masses of carriers in quantum dots may be different than those in the bulk semiconductor.24 However, if the effective masses are adjusted to improve the energy estimate in this size range, as shown by curve b) in Figure 2-1, the assumption of two parabolic bands in E-k space (one valence band and one conduction band) produces a 1/R2 dependence that just does not follow observations very well. Since the effective mass approximation treats the electron and the hole independently, it ignores any interaction between them. The 1/R2 behavior in Equations (2-1) and (2-2) approximates only the kinetic energy contribution to the electron-hole (e-h) pair energy.26 Since the oppositely charged electron and hole attract each other, confining them closer together lowers their net potential energy. Therefore, this Coulomb interaction energy decreases proportional to 1/R.26 Because it is difficult to solve the Schrdinger equation with an added 1/R potential energy term defined into the problem, some authors use perturbation theory26 to justify tacking it onto the solution energy,30,31 as seen in Equation (2-3), where e is the charge of the electron, o is the permittivity of free space, and r is the relative dielectric constant of the semiconductor. For CdSe, r is 10.25 When evaluated, the negative 1/R term only reduces the energy by about 0.1 eV, as shown in Figure 2-1 curve c). Even including Coulomb interaction, the effective mass approximation still diverges from observations for smaller quantum dots.
E n ,l = E g + 1 R2
2 2 mo mo h n ,l 1 1.8e 2 + m 2 e mh 8 mo R 4 o r

(2-3)

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Chapter 2: Theory of Size-Dependent Optical Properties

Another possible energy correction factor also has 1/R dependence. Holding some number, z, of like elemental charges on the surface of a small spherical capacitor would increase the electric potential by Vcapacitance as shown in Equation (2-5).27,32

z e2 Vcapacitan ce = + R 8o r

z = + R (0.072(eV nm) ) ( nm)

(2-5)

Empirically, the photon energy of the first absorbance peak, E, seems to increase as 1/R above the bandgap energy of CdSe, as described in Equation (2-6). By comparison with Equation (2-5), this behavior could be interpreted as arising from the size-dependent capacitance of a sphere with about eleven or twelve elemental units of surface charge.
E1s 1s = hc 1.7 ( eV ) + 0.82 ( eV nm ) R( nm ) z e2 ~ Eg + R 8 o r

(2-6)

This capacitive interpretation presents a dilemma. Can quantum confinement still yield discrete energy states without a significant size-dependent contribution to the first photon transition energy? Band simulation models are providing increasingly more rigorous and accurate estimates of allowed transitions between electronic energy states. When valence band interaction and degeneracy is numerically simulated, the effective mass approximation is improved enough to closely predict the first excited state energy of CdSe quantum dots as a function of R, as shown by Figure 2-2. The differences between data sets from different sources may illustrate the need for more consistent calibrated methods of estimating nanocrystal size using TEM. The details of the band structure yield slight deviations from 1/R2 behavior, so that most features of the absorbance spectra for CdSe quantum

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Chapter 2: Theory of Size-Dependent Optical Properties

dots have been reasonably estimated.28,31 The main difficulty with this approach is that the final E versus R relationships are not analytical.

CdSe Quantum Dots 3.1 3 Absorbance Peak Photon Energy (eV) 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2 1.9 1.8 1.7 0 1 2 3 4 5 Nanocrystal Radius (nm) 6
Data: Norris 1996 Data: Murray 2000 Data: Murray 1993 Data: Peng 1998 e) Band degeneracy model

Figure 2-2. Comparison of band degeneracy model predictions with experimental data. The primary photon transition energy as a function of CdSe quantum dot radius is predicted by the band degeneracy model of Norris and Bawendi,28 as shown by the grey line e). Their model follows their data, labeled Data: Norris 1996. However there are significant differences between the data sets from different sources.24,27,29

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Chapter 2: Theory of Size-Dependent Optical Properties

Although quantum confinement predicts discrete energy levels, continuous Gaussian energy peaks are observed. Individual CdSe quantum dots show extremely photoluminescence emission. Phonon and Coulomb scattering of an electron in a quantum dot may produce a small degree of homogeneous line broadening around the allowed energy states.26 In the laboratory, quantum dot suspensions are characterized by a mean nanocrystal size and a standard distribution rather than by a single radius. Thus inhomogeneous line broadening is also expected, due to the superposition of billions of discrete quantum dot spectra.26 Of course, the slit width of the spectrophotometer can also contribute to the observed line width, but this contribution can be controlled, and it can usually be made small enough to be ignored, compared to the dominant inhomogeneous broadening. As in standard error analysis, the net squared standard deviation in the PL emission wavelength is the sum of the squared contributions. Often the observed emission width is determined primarily by the quantum dot size distribution. When the absorbance peak wavelength, , is monitored as a function of reaction time and synthesis temperature, solving Equation (2-6) for R is a convenient way to estimate changes in the average nanocrystal radius, thereby providing a tool to study synthesis kinetics.

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