Laboratory Experiment

pubs.acs.org/jchemeduc

A Simple ZnO Nanocrystal Synthesis Illustrating Three-Dimensional

Quantum Confinement
Philip J. Reid,* Bryant Fujimoto, and Daniel R. Gamelin
Department of Chemistry, Box 351700, University of Washington, Seattle, Washington 98195-1700, United States
*
S Supporting Information

ABSTRACT: Semiconductor nanocrystals or “quantum dots” are attractive materials for

exploring quantum confinement effects. For example, band-gap energies of these
materials depend on particle size, and this dependence can be explained using simple,
quantum mechanical models. We outline here an undergraduate physical chemistry
laboratory involving the room-temperature synthesis and absorption spectroscopy of
ZnO nanocrystals. The experimental results are compared with the predictions of a
three-dimensional quantum confinement (or “particle-in-a-sphere”) model. The ease of
synthesis and data collection, the common precursors employed, and the simple
spectroscopic analysis allow facile incorporation of this experiment into essentially any
undergraduate laboratory program.

KEYWORDS: Upper-Division Undergraduate, Inorganic Chemistry, Laboratory Instruction, Physical Chemistry,

Hands-On Learning/Manipulatives, Interdisciplinary/Multidisciplinary, Nanotechnology, Quantum Chemistry, UV-Vis Spectroscopy

T he remarkable growth in materials chemistry over the past

two decades has increased the need to explore this area in
undergraduate chemistry curricula. One class of materials that
relative ease of preparation makes these particles an attractive
target for study.10−13
The laboratory described here involves ZnO nanocrystal
has received substantial interest is semiconductor nanocrystals, syntheses involving common precursors where the growth
or “quantum dots”. These materials have a wide range of kinetics are sufficiently fast that particle growth can be studied
potential applications including single-particle imaging, particle within a three-hour lab period.14 Here, solutions of zinc acetate
tracking, and photovoltaics.1−4 Semiconductor nanocrystals are and tetramethyl ammonium hydroxide in ethanol are prepared
also fundamentally interesting materials in that their electronic and mixed, and particle growth at room temperature is
properties depend on particle size.5,6 Specifically, the difference monitored using UV−Vis absorption spectroscopy. The
in energy between the valence and conduction band edges, or
lowest-energy electronic transition provides a measure of the
“band gap”, of the nanocrystal depends on its size, with a
band-gap energy, which evolves as the particles grow in size.
decrease in particle size increasing the band-gap energy. These
The change in band-gap energy with particle size is measured
so-called quantum confinement effects can be described using
relatively simple “particle-in-a-box” quantum-mechanical mod- and compared to predictions of the “particle-in-a-sphere”
els. Therefore, semiconductor nanocrystals are an excellent model. All of the reagents used in this lab are easily acquired,
venue in which to explore foundational quantum-mechanical and the entire experiment is performed at room temperature
ideas in a modern context. with the majority of particle growth evident in ∼30 min. This
A variety of laboratory experiments have been presented in experiment provides a simple, robust way to incorporate
which students synthesize the quantum dots and then analyze modern materials chemistry and quantum mechanics into the
their properties.7,8 Early experiments focused on CdS and CdSe undergraduate laboratory curriculum.

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quantum dots, but these laboratories involved syntheses that
employed relatively toxic compounds (in particular, Cd THEORY
precursors) and high temperatures.8,9 CdS and CdSe quantum
The simplest quantum-confinement model is the particle in a
dots are now commercially available, so synthesis of these
materials can be avoided altogether.9 However, the relative ease one-dimensional box.15 In this model, the particle is subjected
of nanoparticle synthesis is pedagogically attractive aspect of to a constraining potential resulting in its confinement to the
nanocrystal experiments. An alternative is to study materials region of 0 ≤ x ≤ lx where lx is the “length of the box”.15 The
where synthetic precursors are significantly less toxic than those available energy levels (En) are given by
employed for CdS or CdSe. In particular, ZnO quantum dots
have emerged as an “experimentally friendly” material, and their Published: December 9, 2013
© 2013 American Chemical Society and
Division of Chemical Education, Inc. 280 dx.doi.org/10.1021/ed300693d | J. Chem. Educ. 2014, 91, 280−282
Journal of Chemical Education Laboratory Experiment

n2ℏ2π 2 dehydrate, Zn(C2H3O2)2·2H2O, with tetramethyl ammonium

En = hydroxide pentahydrate, N(CH4)4OH·5H2O. Approximately
2lx2 (1)
0.03 g of Zn(C2H3O2)2·2H2O (98% purity, Sigma-Aldrich) is
The energy levels are quantized, indexed by n where n = 1, 2, ..., dissolved in 7 mL of ethanol (200 proof, Decon Labs). A
∞. The model also predicts that the energy levels depend on tetramethyl ammonium hydroxide solution is made by
the length of the box as En ∝ 1/l2x. A long-standing experiment dissolving 0.07 g of N(CH4)4OH·5H2O (97%, Sigma-Aldrich)
in physical chemistry laboratories is the application of this in 7 mL of ethanol. Formation of the ZnO nanoparticles is
model to describe the absorption spectra of conjugated initiated by adding 0.10 mL of the tetramethyl ammonium
alkenes.16 The electrons residing in the π-conjugated orbitals hydroxide solution to a fused silica cuvette containing 0.25 mL
are treated as residing in a box defined by the conjugation, and of the zinc acetate solution and 1 mL of ethanol. The growth of
a study of conjugated molecules of varying length is performed ZnO nanoparticles is monitored by measuring the UV−vis
to test the validity this model. absorption spectrum from 230 to 390 nm as a function of time.
For semiconductor nanocrystals, a three-dimensional (3D) Absorption spectra are acquired 1, 2, 4, 8, 16, and 32 min after
version of the particle-in-a-box model is used to describe the initiation of the reaction. The solution is transferred from the
change in energy levels with particle size. In semiconductors, cuvette to a sealed vial where it was held for two days after
which a final absorption spectrum is measured.

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absorption of a photon promotes an electron from the valence
band to the conduction band, leaving a “hole” in the valence
band. The electron−hole pair is referred to as an exciton. In the HAZARDS
bulk, the electron and hole occupy a volume characterized by Safety goggles should be worn at all times during the
the exciton Bohr radius, which depends on the electronic experiment. Ethanol is flammable and should not be used
structure and dielectric constant of the semiconductor. For around open flames. Tetramethyl ammonium hydroxide is
example, this radius is 56 Å for CdSe9 and 24 Å for ZnO.12 highly toxic by ingestion, and somewhat toxic by skin
When the nanocrystal radius is comparable to the Bohr radius, absorption. Disposable gloves should be worn when handling
confinement effects are observed corresponding to an increase this material. Zinc acetate is reactive with oxidizing agents.
in the band gap energy. The confinement of an electron (or
hole) in the nanocrystal can be modeled assuming spherical
symmetry, or the “particle-in-a-sphere” model. In spherical
■ RESULTS
The absorption spectrum of the ZnO nanoparticle solution as a
polar coordinates, the time-independent Schrodinger equation function of time is shown in Figure 1. After 1 min, a transition
is
ℏ2 ⎛ ∂ 2 2 ∂⎞ 1 ̂2
− ⎜ 2 + ⎟ψ (r , θ , ϕ) + L ψ (r , θ , ϕ)
2m ⎝ ∂r r ∂r ⎠ 2mr
+ V (r )ψ (r , θ , ϕ) = Eψ (r , θ , ϕ) (2)
The potential energy term is defined as V(r) = 0 when the
particle is inside the sphere of radius a (0 ≤r ≤ a) and V(r) =
∞ everywhere else. The band gap energy derived from this
model depends on the nanocrystal radius (R):8,13
ℏ2π 2 ⎛ 1 1 ⎞
bulk
E bg = E bg + ⎜ + ⎟
2R2 ⎝ me* mh* ⎠ (3)
Here, Ebg is band-gap energy of a nanocrystal with radius R,
eg is the band-gap energy of the bulk semiconductor, and m*
Ebulk e
and m*h are the electron and hole effective masses. Due to
dielectric screening, the electron and hole effective masses are
smaller than that of a free electron. Because the photogenerated Figure 1. UV−vis absorption spectra collected during of ZnO
electron and hole have opposite charges, they attract one nanocrystal growth. Spectra were taken at various times after initiation
another via Coulomb interaction such that the band-gap energy of the reaction as indicated. The lowest-energy absorption band
of the semiconductor is less than expected from eq 3. This provides a measure of the band-gap energy.
stabilization is referred to as the exciton binding energy, and a
correction term is added to eq 4 to account for this effect:
ℏ2π 2 ⎛ 1 1 ⎞ 1.8e 2 centered at ∼290 nm is observed corresponding to the band
bulk
E bg = E bg + ⎜ + ⎟ −
2R2 ⎝ me* mh* ⎠ 4πεε0R (4) gap of the semiconductor. As the particles grow, this transition
shifts to longer wavelengths (lower energy) ultimately reaching
Here, ε is the dielectric constant of the semiconductor and ε0 is ∼340 nm in 48 h.
the vacuum permittivity. The central prediction of eq 5 is that Data analysis involves determining the band-gap energy from
the band-gap energy should scale as 1/R2.

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the electronic absorption spectrum by identifying the wave-
length at which the rising edge of the absorption band edge is
EXPERIMENT half of the bend maximum (λhalf) and converting this
Students typically perform this experiment individually. ZnO wavelength to energy. Next, the particle diameter is determined
nanocrystals are formed through the reaction of zinc acetate using the following empirical relationship:11
281 dx.doi.org/10.1021/ed300693d | J. Chem. Educ. 2014, 91, 280−282
Journal of Chemical Education

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Laboratory Experiment

⎛ 1240 ⎞ AUTHOR INFORMATION

⎜ − a⎟D2 + cD + b = 0 Corresponding Author
⎝ λhalf ⎠ (5)
*E-mail: pjreid@uw.edu.
where D is the diameter of the particles in angstroms (Å). The Notes
empirical constants in eq 5 are taken from the literature: a =
The authors declare no competing financial interest.

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3.301, b = −294.0, and c = −1.09.11 With the constants and λhalf
values, the quadratic equation is solved to determine D. With ACKNOWLEDGMENTS
particle diameters in hand, a plot of band-gap energy versus
(radius)−2, or (D/2)−2, is constructed (Figure 2). The This work was supported by the National Science Foundation
(PJR: DMR 1005819, DRG: CHE 1151726).

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prediction of the particle-in-a-sphere model is that the band
gap of the ZnO nanoparticle scale as R−2, and the data are in
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(16) Shoemaker, D. P.; Garland, C. W.; Nibler, J. W. Experiments in
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Over 200 students have successfully performed this experiment
over the past 5 years. This laboratory is typically performed
after coursework in quantum mechanics to reinforce concepts
encountered in a more theoretical context.

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*
ASSOCIATED CONTENT
S Supporting Information

A complete description of the laboratory including instructions

for students performing the lab. This material is available via
the Internet at http://pubs.acs.org.
282 dx.doi.org/10.1021/ed300693d | J. Chem. Educ. 2014, 91, 280−282