In the Laboratory

Quantum Dots in a Polymer Composite:

A Convenient Particle-in-a-Box Laboratory Experiment
Charles V. Rice* and Guinevere A. Giffin
Department of Chemistry and Biochemistry, The University of Oklahoma, Norman, OK 73019; *[email protected]

Numerous laboratory exercises seek to increase student Theory

understanding of quantum mechanics and the interpretation
of spectroscopic data. For decades, UV–vis spectroscopy has Ultraviolet light promotes electrons from the valence
been used to study organic dyes, whose absorption spectra are band into the conduction band where they are delocalized in
directly related to the electron delocalization in conjugated three dimensions. In a bulk semiconductor, the energy levels
π-bond networks (1, 2). Quantum mechanical calculations in the valence and conduction bands are continuous (9). An
employ a 1-D particle-in-a-box model, which can be difficult electron excited into the conduction band results in a hole in
for students to grasp (2). Semiconductor nanocrystals provide the valence band. This electron–hole pair is called an exciton.
an opportunity to demonstrate quantum mechanics with a 3-D The electron–hole pair separates to a distance characteristic of
particle-in-a-box model (3, 4). In the classroom, semiconductor the material and is known as the exciton Bohr radius. In CdSe
nanocrystals provide a mechanism to explain solid-state crystal- the exciton Bohr radius is 56 Å (10).When the radius of the
lography, inorganic chemistry, and nanotechnology (4–7). The quantum dot is smaller than the exciton Bohr radius, the energy
background material presented in the cited reports is thorough of the exciton increases because it is confined within the physical
and not repeated here. Building on these efforts, we have devel- dimensions of the quantum dot nanocrystal. The energy of the
oped a quick and safe laboratory experiment that records photo- excited electron is dependent on the size of the quantum dot,
luminescence spectra of semiconductor nanocrystals embedded where the valence and conduction bands exist as discrete energy
in a polymer matrix. This experiment provides a fresh alternative levels (9, 10). Charge recombination results in the emission of
to the classical quantum mechanics experiments typically done light via fluorescence. In bulk materials, numerous energy levels
in a third- or fourth-year physical chemistry laboratory. are available and subsequent transitions between these states
Imbedding nanocrystals consisting of a CdSe core sur- gives rise to a broad emission peak. In quantum dots, only a few
rounded by a layer of ZnS in a matrix of polyurethane/acrylic states are allowed, thus the energy transitions are discrete and
acid provides a durable sample, resistant to surface oxidation. yield a narrower emission peak compared to the bulk material.
Oxidation of CdSe alters the size of the quantum “box” and The quantum dot emission wavelength is directly related to the
leads to sample degradation over time. This core–shell arrange- exciton energy and therefore size of the quantum dot, which can
ment also reduces surface defects, forming a true nanocrystalline be modeled with a 3-D box.
quantum box (8). Such a robust sample is resistant to photo- Energy levels of a particle confined a 1-D box are given by
bleaching and can be used repeatedly without damage. Previ- n2 h 2
ous laboratory exercises to synthesize semiconductor quantum En 
dots require dangerous chemicals, high temperatures, and inert 8 m r2
atmospheres (4, 7). where n is the quantum number related to the energy eigenstate,
The photoluminescence spectrum consists of a single line, h is Planck’s constant, m is the mass of the particle, and r is the
whose frequency is directly related to the particle size. A labora- nanoparticle radius. In an orthogonal 3-D system, the energy
tory experiment with analysis of quantum-sized metal sulfide levels are described by
particles by UV–vis spectrophotometry has been previously
published in this Journal (4). These types of experiments are n2 h 2 1 1 1
En  2
 2
 2 (1)
awkward, and the absorption spectra have several broad, overlap- 8m Lx Ly Lz
ping lines. Fitting a tangential line near the onset of absorption
is required to measure the particle size. Problems mount if the where L x, Ly, and Lz are the dimensions in each direction.
samples decompose from surface oxidation or the student-led A similar expression was developed by Brus to describe the
synthesis is imperfect. discrete energy levels that exist due to confinement within a
Simplifying the laboratory exercise allows teaching efforts spherical nanocrystal, the quantum dot (10).The energy of the
to be expanded to discuss spectroscopy and line broadening first excited state is
mechanisms. The fluorometer used is a low-cost modular
setup that provides students with a hands-on experience of h2 1  1
E  (2)
spectrophotometer operation. Calculation of particle size is 8r 2
me mh
straightforward using the peak maximum, while the line width
can be used to illustrate the effect of a particle-size distribution. The effective electron mass within the exciton is me*. For CdSe,
Even for laboratories without a fluorescence spectrophotometer, me* = 0.13me where me is the electron mass in kg. The effective
the polymer composite sample eliminates sample preparation mass of the hole in the exciton is given by mh*, which is 0.45me
needed to collect absorption spectra. (10). The effective masses are only a fraction of the mass of an

842 Journal of Chemical Education  •  Vol. 85  No. 6  June 2008  •  www.JCE.DivCHED.org  •  © Division of Chemical Education 
 In the Laboratory

gated
electron because the Coulombic attraction between the hole
spectrofluorometer
and the electron is screened (11). The emission wavelength
from the semiconductor nanocrystal can then be related to the
particle size using
cuvette holder
h 2 1 1 LED
%E r
 E gap   (3) source
8 r2 me mh
hc samples
 hO 
M
which adds the band gap energy of the bulk semiconductor, Egap,
to the quantum confinement term. ΔE(r) is the fluorescence
emission peak energy in Joules and Egap for CdSe = 1.74 eV. Figure 1. Ocean Optics modular spectrophotometer.

Experimental
Seven samples of CdSe/ZnS nanocrystals dispersed in a
composite of polyurethane/acrylic acid, each containing differ-
ent sized crystals, were used as received from Evident Technolo- 250 red–orange
Mmax = 617.8 nm
gies (Troy, NY). The nanocrystal concentration was < 3%. A
sample of polymer composite without nanocrystals was used to 200
obtain a background spectrum. Fluorescence spectra were taken green #1
using a modular spectrophotometer (USB 2000 FLG, Ocean Intensity 150 Mmax = 524.0 nm
Optics Inc., FL), as shown in Figure 1. The setup consisted of a FWHM
gated spectrofluorometer (350–1000 nm), a 380 nm LED exci- 100 = 30.3 nm
tation light source (45 mW output), two fiber-optic cables, and FWHM
= 35.5 nm
a cuvette holder with four optical windows. The optical cables 50
were positioned at a 90° angle on the cuvette holder. Each spec-
trum was collected in a few seconds. The peak maximum and 0
line width were determined using the Ocean Optics software 400 450 500 550 600 650 700
(OOIBase32). Wavelength / nm

Figure 2. Photoluminescence spectrum of two core–shell CdSe/

Hazards ZnS quantum dots. The nanocrystals are embedded in a matrix
of polyurethane/acrylic acid. Peak maximum and line width are
The matrix of polyurethane/acrylic acid removes many
determined by the Ocean Optics software.
hazards associated with the handling of semiconductor nano-
crystals. Evident Technologies provides small vials filled with
CdSe in the matrix, eliminating any danger posed by in-house
synthetic procedures. Although the light source is low power,
appropriate eyewear should be used at all times, and the light
source turned off when moving the fiber-optic cables. Table 1. Peak Frequency and Line Width Data
for CdSe Quantum Dot Samples

Results Color λ/(nm) FWHM/(nm) Diameter/(Å)

The peak frequency and full-width at half-maximum Blue 488.0 37.5 43

(FWHM) are easily determined from the photoluminescence
Green #1 524.0 35.5 48
spectrum (Figure 2). The CdSe quantum dot radius was calcu-
lated using eq 3, and the results for the samples, each containing Green #2 549.0 34.7 53
different sized quantum particles, are presented in Table 1. Over
80 students, in 7 lab sections, have performed this laboratory Yellow 565.9 32.0 57
exercise over 4 semesters. The student data gave diameters that Orange #1 586.5 31.2 63
are within 5% of those provided by the manufacturer, Evident
Technologies, Inc. The diameters given by Evident Technologies Orange #2 600.8 30.8 67
were estimates based on sizing curves generated from TEM
measurements and the first absorption maximum of CdSe nano- Red–orange 617.8 30.3 74
crystals by Yu, Qu, Guo, and Peng (12). Many students noted Note: Dot samples were excited with the same wavelength. Data were
that the concepts of quantum mechanics are quite abstract, calculated using eq 3.

© Division of Chemical Education  •  www.JCE.DivCHED.org  •  Vol. 85  No. 6  June 2008  •  Journal of Chemical Education 843
 In the Laboratory

particularly a 1-D box and the differences between adsorp- 4. Nedeljkovic, J. M.; Patel, R. C.; Kaufman, P.; Joycepruden, C.;
tion and emission of energy. Students also struggle to grasp Oleary, N. J. Chem. Educ. 1993, 70, 342–344.
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system under investigation. The transition between two energy 79, 1094–1100.
levels should, in theory, be a very narrow delta function with 6. Lagally, M. G. J. Chem. Educ. 1998, 75, 277–279.
infinitesimal line width. The quantum dot/polymer composite 7. Lasher, D. P.; DeGraff, B. A.; Augustine, B. H. J. Chem. Educ.
samples studied have minimal line broadening from rotational 2000, 77, 1201–1203.
or vibrational perturbations (10). The observed line width arises 8. Reiss, P.; Bleuse, J.; Pron, A. Nano. Lett. 2002, 2, 781–784.
from the effects of inhomogeneity, mainly a distribution of par- 9. Klimov, V. I. J. Phys. Chem. B. 2006, 110, 16827–16845.
ticle sizes. Students tend to overlook the distribution of particle 10. Nirmal, M.; Brus, L. Acc. Chem. Res. 1999, 32, 407–414.
sizes within the quantum dot samples and therefore struggle to 11. Brus, L. E. J. Chem. Phys. 1984, 80, 4403–4409.
explain the line width. Using 3-D quantum dots, particularly 12. Yu, W. W.; Qu, L. H.; Guo, W. Z.; Peng, X. G. Chem. Mater.
those with current technological relevance, we have been able 2003, 15, 2854–2860.
to clarify these concepts.
Supporting JCE Online Material
Acknowledgment
http://www.jce.divched.org/Journal/Issues/2008/Jun/abs842.html
This work is supported by The University of Oklahoma
Abstract and keywords
and a CAREER Award from the National Science Foundation
(CHE-0449622). Full text (PDF)
Links to cited JCE articles
Literature Cited
Color figures
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liams, R. R. Chem. Educ. 2004, 9, 159–162. Instructor notes

844 Journal of Chemical Education  •  Vol. 85  No. 6  June 2008  •  www.JCE.DivCHED.org  •  © Division of Chemical Education