Article

pubs.acs.org/JPCC

Low-Temperature Synthesis of Magic-Sized CdSe Nanoclusters:

Influence of Ligands on Nanocluster Growth and Photophysical
Properties
John C. Newton,†,∥ Karthik Ramasamy,†,∥,⊥ Manik Mandal,‡ Gayatri K. Joshi,† Amar Kumbhar,§
and Rajesh Sardar*,†
†
Department of Chemistry & Chemical Biology, Indiana University Purdue University Indianapolis, 402 N. Blackford Street,
Indianapolis, Indiana 46202, United States
‡
Department of Chemistry, Lehigh University, Seeley Mudd Building, 6 East Packer Avenue, Bethlehem, Pennsylvania 18015, United
States
§
Chapel Hill Analytical and Nanofabrication Laboratory, University of North Carolina, Chapel Hill, North Carolina 27599, United
States
*
S Supporting Information

ABSTRACT: We present a low-temperature (68−70 °C) synthesis of

green light-emitting, trioctylphosphine oxide-capped magic-sized CdSe
nanoclusters from the reaction of trioctylphosphine oxide−cadmium
acetate precursors with trioctylphosphine selenide. We observed
continuous growth of these magic-sized nanoclusters, which displayed a
first absorption peak at 422 nm and broad luminescence covering the
entire visible region. The diameter of the nanoclusters determined by
transmission electron microscopic measurement was ∼1.8 nm. Powder X-
ray diffraction analysis showed a sharp peak at low angle (2θ = 5.3°),
confirming the formation of ultrasmall, magic-sized nanoclusters. The
nanocluster formation was also studied using different purities of
trioctylphosphine oxide. The synthetic protocol was extended to the
preparation of oleylamine-, ethylphosphonic acid-, lauric acid-, and
trioctylamine-stabilized magic-sized CdSe nanoclusters. Importantly, the investigation showed that the nature of the cadmium
precursors plays a crucial role in the nanocluster growth mechanism. The applicability of the trioctylphosphine oxide-capped
nanoclusters was further investigated through a ligand exchange reaction with oleylamine, which displayed an extremely narrow
absorption peak at 415 nm (full width at half-maximum of 14 nm) and a band edge emission peak at 456 nm with a shoulder at
438 nm.

■ INTRODUCTION
Since the discovery of the “hot injection” method of
monodispersed semiconductor nanclusters (SCNCs) synthesis
by Murray, Norris, and Bawendi,1 numerous synthetic
protocols have been developed to produce clusters with 2.0
nm diameter.2−9 SCNCs with diameter below 2.0 nm are an
important class of nanomaterials because, depending on the
surface passivating ligands, these particles display either broad
luminesence or a combination of band edge and broad
luminesence. Such dual emission characteristics are ideal
photophysical properties for fabrication of optoelectronic
devices as well as bridge nanoparticles and molecular
clusters8−12 Moreover, SCNCs with sizes below 2 nm display
a unique stability due to their specific atomic composition and
structure. Indeed, this unique stability is largely attributed to
the cluster-cage structure of the NC, which assemble in
particular sizes [(CdSe)n, n = 13, 19, 33, and 34] producing
“magic-sized” NCs.
Several methods have been developed for synthesizing
magic-sized CdSe NCs.2,13−22 Peng et al.7 were the first to
report a high-temperature method for the preparation of magic-
sized CdSe NCs, where a mixture of tributylphosphine selenide
and trioctylphosphine (TOP) in toluene was injected at 320 °C
into a mixture of cadmium oxide, trioctylphosphine oxide
(TOPO), and tetradecylphosphonic acid. The NCs displayed a
sharp absorption peak at 349 nm, which is a known
characteristic of NCs containing 17 Cd atoms.8 Kasuya and
co-workers synthesized magic-sized CdSe NCs using a low-
temperature reverse micelle protocol, where an aqueous
solution of Na2SeSO3 was added to a Cd−decylamine complex
in toluene.20 They revealed the chemical composition of magic-
sized NCs by mass spectroscopy and X-ray diffraction
measurements and defined the NC compositions as (CdSe)33
Received: September 8, 2011
Revised: January 26, 2012

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The Journal of Physical Chemistry C
and (CdSe)34, which exhibited a sharp absorption peak at 415
nm. A three-dimensional model was inferred from these
experiments which explained the “core-cage” structure of
magic-sized CdSe NCs.20 Later, modifying the “hot-injection”
method developed by Peng at el., Rosenthal and co-workers
synthesized white light-emitting, magic-sized CdSe NCs, which
displayed band edge and broad luminescence covering the
entire visible spectrum and a sharp absorption peak at 414
nm.2,19,23 Kudera et al.14 synthesized different families of magic-
sized CdSe NCs from the high temperature (200 °C)
decomposition of cadmium oxide in the presence of aliphatic
acid and amine, followed by the injection of TOPSe at 80 °C.
Based on their optical spectroscopy analysis, the size of the
NCs was 1.5−2.0 nm. They displayed strong absorption peaks
at 350, 384, 406, 431, and 447 nm and were formed via a
quantized growth process. Ouyang et al.17 developed a single-
step synthesis of magic-sized CdSe NCs at temperatures
between 120 and 240 °C via a noninjection method in which
they combined a cadmium salt, selenium, and fatty acids with
different chain lengths in 1-octadecene as solvent. The method
produced magic-sized CdSe NCs, which exhibited sharp
bandgap adsorptions at 395, 463, and 513 nm. The DOSY
NMR technique was used to determine the size of the NCs,
which was in the range of 1.7−2.2 nm. A few other synthetic
methods, including “greener” syntheses,13,24,25 are known to
produce (CdSe)33 and (CdSe)34 utilizing functional thiols as
capping ligands, and further surface modification of these NCs
for applications such as nanoscale electronics would be
extremely challenging.13−15,21,25,26 In SCNC syntheses,
TOPO is the most widely used coordinating ligand.
Furthermore, TOPO-capped SCNCs have shown great
promise due to their ease of surface modification with stronger
ligands, such as amines or phosphonic acids. The high
susceptibility of TOPO to surface modification will provide
the opportunity for a thorough investigation of the nature of
NC surface and photophysical properties and remains an
important option for the synthesis of SCNCs.27−29
Peng et al. showed that TOPO could be used in magic-sized
CdSe NC synthesis; however, the NCs were not isolated and
characterized.7 Therefore, the actual composition of the
TOPO-capped magic-sized CdSe NC remains illusive. With
modification of the “hot-injection” method,7 Rosenthal and co-
workers2 synthesized and characterized the white light-emitting
NCs, and on the basis of optical properties, they defined them
as magic-sized CdSe NCs. In both synthetic protocols, the
reaction mixture contained other strong surface passivating
ligands such as amines and phosphonic acids, and thus the
specific role of TOPO remained unclear. In their recent work,
Rosenthal and co-workers were unable to observe continuous
growth of magic-sized CdSe NCs when TOPO was solely used
as the surface passivating ligand.23 Moreover, the synthetic
methods available in the literature for preparation of magic-
sized CdSe NCs impose a limit on particular coordinating
ligands, as well as different reaction conditions, and thus the
synthesis of well-defined, magic-sized CdSe NCs still remains a
major challenge. Furthermore, it is important to define the
reaction conditions that can routinely produce such NCs using
capping ligand selection as the only variable and then to
investigate their formation mechanism and photophysical
properties.
Here, we demonstrate a low-temperature synthesis of magic-
sized CdSe NCs using TOPO as a stabilizing ligand. To the
best of our knowledge, this is the first example where the utility
B dx.doi.org/10.1021/jp2086818 | J. Phys. Chem. C XXXX, XXX, XXX−XXX
Article
of TOPO as the surface passivating ligand has been
demonstrated at low temperature (<70 °C) for this particular
magic-sized CdSe NCs synthesis. We have also investigated the
purity of TOPO and it is effect on the formation of magic-sized
CdSe NCs. Moreover, we show that the synthetic method can
be extended to preparing oleylamine (OA)-, ethylphosphonic
acid (EPA)-, lauric acid (LA)-, and trioctylamine (TOA)-
stabilized magic-sized CdSe NCs. The formation of magic-sized
CdSe NCs was characterized by UV−vis absorption spectros-
copy. Comparing the first absorption peak to known literature
values,13,25 the compositions of the NCs were identified as
(CdSe)33, (CdSe)34, and, under certain conditions, (CdSe)19.
The synthesis of TOPO-, EPA-, LA-, and TOA-stabilized CdSe
NCs showed a slow and continuous growth of ultrasmall to
“magic-sized”, while OA-capped NCs displayed a quantized
growth of different families. Depending on the ligands used in
synthesis, the magic-sized CdSe NCs displayed either broad
luminescence or a combination of broad luminescence and
band edge emission in photoluminescence (PL) spectroscopy.
The magic-sized CdSe NCs were also analyzed by transmission
electron microscopic (TEM) and X-ray diffraction (XRD)
techniques to determine their size and size dispersity. Tuning of
photophysical properties of magic-sized CdSe NCs was further
demonstrated by simple ligand exchange chemistry.
■ EXPERIMENTAL METHODS
Materials. All chemicals were used as received unless stated
otherwise. Solvents were dried over molecular sieves and
purged with high-purity argon for 30 min before use. Selenium
powder (99.99%), cadmium acetate dihydrate (Cd-
(OAc)2·2H2O, ≥98.0%), trioctylphosphine (TOP 97%, batch
# 41296JM), trioctylphosphine oxide (TOPO, 90%, batch #
04028DJ and 99%, batch # MKBG0500 V), oleylamine (OA,
70%), lauric acid (LA, 98%), trioctylamine (TOA, 98%),
ethylphosphonic acid (EPA, 98%), and Coumarin-153 were
purchased from Aldrich Chemical Co. HPLC grade hexane,
toluene, and acetonitrile were also obtained from Aldrich. The
99% TOPO was purified by successive recrystallization which
produced white needlelike crystals. TOPSe was purified as
follows: 0.99 g of Se powder was dissolved in 17.0 mL of TOP
in a one-neck flask with a receiving flask. The TOPSe mixture
was slowly heated to 195 °C under high vacuum. The initial
12.0 mL of distillant was discarded, and the remaing 5 mL of
TOPSe was used for CdSe NC synthesis.
Measurements. UV−vis absorption spectra were collected
using a Varian Cary 50 UV−vis spectrophotometer scanning
through a range of 800−300 nm. The emission spectra were
collected using a Cary Eclipse fluorescence spectrophotometer
from Varian Instruments. Transmission electron microscopic
(TEM) analysis was performed using a JEOL 2020F FasTEM
at 200 kV accelerating voltage. Powder XRD patterns were
recorded on a Bruker Nanostar U instrument equipped with Cu
Kα radiation source operated as a rotating anode at 50 kV and
24 mA.
The photoluminescence (PL) quantum yield (ΦNC) of
magic-sized CdSe NCs was determined by following the same
protocol described by Schreuder et al.30 The purified sample
was dissolved in toluene, and the optical density of the first
absorption peak at 422 nm of the NCs was adjusted to <0.1 by
diluting the sample with toluene. Next, the optical density of
Coumarin-153 (ΦSTD = 0.53)16 in ethanol was adjusted to
match the intensity of the NC solution. The PL spectra of each
solution were collected at room temperature at the excitation
The Journal of Physical Chemistry C

■
Article

wavelength of 408 nm (two samples absorbed almost RESULTS AND DISCUSSION

identically at this wavelength), and the integrated emission Optical Properties of TOPO-Capped Magic-Sized
intensity of NCs was compared with integrated intensity of CdSe Nanoclusters. The formation of CdSe NCs was
Coumarin-153 emission. The quantum yield of NCs was then monitored by UV−vis absorption spectroscopy at different
calculated using eq 1.30 time intervals. Figure 1A represents time-dependent absorption
⎛ ENC/ANC ⎞⎛ ηNC2 ⎞
Φ NC = ⎜ ⎟⎜ ⎟Φ
⎝ ESTD/ASTD ⎠⎜⎝ ηSTD2 ⎟⎠
STD
(1)
In this equation, ENC is the integrated emission intensity of the
NCs, and ANC is the absorption intensity of NCs at 422 nm.
ESTD is the integrated emission intensity of Coumarin-153, and
ASTD is the absorption intensity of Coumarin-153. The
refractive index of toluene and ethanol is ηNC and ηSTD,
respectively. The average ΦNC was determined from five
different batches of CdSe NCs.
Synthesis and Isolation of TOPO-Capped Magic-Sized
CdSe Nanoclusters. In a typical synthesis, a stock solution of
TOPSe was prepared in a two-necked flask by dissolving 0.198
g (2.5 mmol) of selenium powder in 3.4 mL (7.6 mmol) of
TOP at 100 °C for 2 h under an argon atmosphere. Next, 0.5 g
(1.9 mmol) of Cd(OAc)2·2H2O and 5.0 g of TOPO (13.0
mmol) were transferred into a separate two-necked flask fitted
with a temperature probe, and the solid was then heated at 68
to 70 °C under high vacuum. During this period the solid
transformed into an optically transparent liquid. As soon as the
liquid temperature became stabilized at 68−70 °C, the heating
was continued under an argon atmosphere. At this juncture, 3.4
mL of TOPSe was quickly injected into the Cd-TOPO reaction
mixture. Before addition of TOPSe into the Cd-TOPO
precursor, its temperature was reduced to 70 °C. During the
formation of magic-sized CdSe NCs, the color of the reaction Figure 1. (A) Time-dependent absorption spectra of the TOPO-
mixture was initially faint yellow and then yellow. After 36 h of capped magic-sized CdSe NCs. The maximum intensity for the first
reaction it became a bright yellow, viscous liquid. The reaction absorption peak (λmax: 422 nm) was observed after 36 h of reaction at
68−70 °C. The inset shows absorption feature at the early stages of
progress was monitored by UV−vis absorption spectroscopy at the synthesis. (B) Evolution of the emission spectra of CdSe NCs with
different time intervals by transferring small aliquots (75 μL) of respect to the reaction time.
reaction mixture into 2 mL of toluene. After heating for 36 h,
the reaction vessel was removed from heat and allowed to cool spectra of TOPO-capped CdSe NCs synthesized at ∼70 °C.
to room temperature, which resulted a yellow solid. The NCs The spectrum of a sample taken 30 min after TOPSe injection
were purified by dissolving the reaction mixture in 5 mL of showed a broad peak with highest absorption intensity (λmax) at
hexane, stirring for 30 min under argon atmosphere, and then 388 nm. After another 30 min of the reaction, the absorption
adding 20 mL of acetonitrile to precipitate the NCs. The peak red-shifted and appeared at 403 nm. After 5 h, well-
mixture was stirred for another 2 h at room temperature. The defined absorption peaks at 422 and 365 nm with an additional
yellow solid was then centrifuged out and the liquid discarded.
shoulder 398 nm were detected and were assigned as 1S(e)−
The solid was redissolved in a minimum amount of hexane, and
1S3/2(h), 1P(e)−1P3/2(h), and 1S(e)−2S3/2(h) energetic
then 5 mL of acetonitrile was added to reprecipitate the solid,
transitions, respectively.15,22 The absorption peak at 422 nm
which was then isolated by centrifugation, dried under high
vacuum, and stored under argon in dark. Using identical molar continued to increase in intensity with improved sharpness and
amounts of Cd(OAc)2·2H2O, Se, and TOP and similar reaction reached its maximum value at 36 h of heating. The heating was
conditions, magic-sized CdSe NCs were synthesized in the continued for another 12 h, but no additional peak or shoulder
presence of 13.0 mmol of OA (4.28 mL), EPA (1.43 g), LA formation was observed.
(2.57 g), and TOA (5.68 mL) as stabilizing ligands. On the basis of the position of the UV−vis absorption bands,
Surface Modification of TOPO-Capped Magic-Sized we propose that the formation of NCs followed the growth
CdSe Nanoclusters by OA. In a typical experiment, 20 mg of mechanism illustrated in Scheme 1. After the addition of
vacuum-dried, TOPO-capped CdSe NCs was dissolved in 20 TOPO to Cd(OAc)2 and heating to 70 °C, an optically
mL of toluene, producing a yellow solution. The solution was transparent soluble complex, presumably [Cd(OAc)2·TOPO],
then cycled under vacuum and argon at least five times at room is formed. The injection of TOPSe to [Cd(OAc)2·TOPO]
temperature and then heated to 90 °C under an argon resulted in a faint yellow solution, which displayed a broad peak
atmosphere with constant stirring. At this juncture, 2 mL (6.1 (λmax) at 388 nm in the UV−vis spectrum (inset Figure of 1A
mmol) of OA was added to the NC solution. The exchange and Supporting Information Figure 1). The broad peak
reaction was run for 30 min. A 100 μL sample of reaction indicates the generation of ultrasmall NCs (“reactive
mixture was diluted with 2 mL of toluene, and absorption and monomers”) represented as black dots in Scheme 1 along
emission spectra were collected. with a family of magic-sized NCs (purple dots).5,14,31,32 As time
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The Journal of Physical Chemistry C
Scheme 1. Proposed Mechanism for the Formation of
TOPO-Capped Magic-Sized CdSe NCs
progresses, the increase in absorption peak intensity and red-
shift of absorption maximum (inset of Figure 1A and
Supporting Information Figure 1) indicate that the formation
of ultrasmall NCs continues, while previously formed magic-
sized NCs undergo a homogeneous nucleation process leading
to another family of NCs, which displayed a broad peak with
λmax at 403 nm (Scheme 1, blue dots). This gradual red-shift of
the first absorption peak from 388 to 403 nm over the course of
30 min suggests that the NCs are growing in size.14
Approximately 5 h after TOPSe injection, these magic-size
NCs with broad peak and λmax at 403 nm in UV−vis
spectroscopy (Figure 1A) experience additional size-focusing
as well as stabilization steps and reach a critical size (Scheme 1,
red dots), with absorption maxima at 422 nm. Afterward,
concentration of this specific composition of TOPO-capped
magic-sized CdSe NCs continues to increase in the reaction
mixture. In a recent report, Yu et al.18 mentioned that magic-
sized CdSe NCs only form via a nucleation process without any
traditional growth step as required for regular SCNCs
formation. We believe once the magic-sized NCs that displayed
first absorption peak at 422 nm are formed, the dissolution of
these NCs to the active nuclei is unlikely to occur. Moreover,
those magic-sized NCs would not experience any further
growth due to their unusually high stability.20,25
The position and sharpness of the first absorption peak at
422 nm (Figure 1A), with full width at half-maxima (fwhm) of
20 nm, indicate the formation of small-sized NCs of <2.0 nm in
diameter.13,16,20,25 The optical signature of the TOPO-capped
CdSe NCs is very similar to the spectra reported by Park et al.
for cysteine- or decylamine-capped NCs.20,25 The sharp peaks
at 422 and 365 nm and the shoulder at 398 nm are consistent
with literature reports and suggest the formation of magic-sized
CdSe NCs with a possible composition of (CdSe)33 and
(CdSe)34. To the best of our knowledge, this is the first
example of low-temperature synthesis of magic-sized CdSe NCs
utilizing TOPO as a stabilizing agent.
The emission spectra of TOPO-capped magic-sized CdSe
NCs prepared at ∼70 °C is shown in Figure 1B. PL spectra of
CdSe NCs after 5 h showed an emission maximum at 482 nm
which red-shifted to 502 nm with increasing intensity upon
prolonged heating for 36 h. Interestingly, the magic-sized CdSe
NCs displayed a sharp absorption peak at 422 nm, but the
emission spectra appeared to be broad and covered the entire
visible region. According to literature reports, the magic-sized
CdSe NCs mostly display a combination of band edge and
broad luminesence.2,13,14,22,23,25,33 Owen and co-workers16
recently reported that the CdSe NCs, which displayed first
absorption peak at 418 nm, also exhibited a broad PL emission
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spectrum centered at 559 nm. Previously, it was reported that
the following three parameters could influence the PL emission
spectra of magic-sized NCs:23 (i) the unique crystal structure of
the NCs, (ii) energetically different midgap states due to the
presence of noncoordinating surface selenium sites, and (iii)
the steric effect of surface passivating ligands. We believe the
broad luminescence is mostly influenced by the nature of the
surface passivating ligand. Bullen et al.28 have reported a
correlation between the size of CdSe NCs and the maximum
surface coverage by surfactant when TOPO was used as the
surface passivating ligand. Based on their theoretical data, a
maximum of 60% of the surface area should be covered by
TOPO for CdSe NCs <2 nm in diameter. Therefore, a
significant amount of the NC surface should remain
unpassivated. The average ΦNC of green light-emitting,
TOPO-capped NCs was low {1.46 (0.12)%}, which is
consistent with the presence of unpassivated surface sites.
The energy-dispersive X-ray (EDX) analysis of the TOPO-
capped CdSe NCs revealed that the ratio of P to total Cd and
Se is 0.4:1.0, which is also consistent with that a large number
of NC surface atoms being unpassivated, resulting in weak trap-
state emission. However, the ΦNC we obtained for TOPO-
capped CdSe NCs was found to be highest for CdSe NCs that
were prepared by a low-temperature synthetic route without
using primary amines or phosphonic acids as the capping
ligand.15
Chemical Structure Determination of TOPO-Capped
Magic-Sized CdSe Nanoclusters. The TOPO-capped CdSe
NCs were analyzed by TEM to determine their size for
correlation with optical properties. According to the empirical
sizing equation provided by Yu et al.,34 the diameter of CdSe
NCs was calculated to be 1.74 nm based on the position of first
absorption peak at 422 nm. Figure 2A illustrates the TEM
image of TOPO-capped magic-sized CdSe NCs. The TEM
analysis showed the presence of spherical NCs with diameter of
∼1.8 nm, which is in good agreement with the diameter
calculated empirically. However, it is extremely challenging to
determine the exact size of such a small NC by TEM analysis.
The sizing equation, which has previously been used to
determine the size of magic-sized metal chalcogenide NCs,
provides greater accuracy for nanoparticles with a diameter
greater than 2.0 nm. However, it still can provide valuable size
information for magic-sized clusters less than 2.0 nm.21,23,25
The high-resolution TEM (HRTEM) analysis (Supporting
Information Figure 2) failed to provide adequate information
regarding the morphology and lattice structure of the NCs due
their extremely small size. Structural information on such small
NCs from TEM analysis remains ellusive, and according to
literature reports, magic-sized NCs could appear in different
geometries.21 However, XRD analysis could highlight valuable
information regarding the structure of the TOPO-capped CdSe
NCs, which is discussed in the following paragraph.
The TOPO-capped magic-sized CdSe NCs were also
analyzed by XRD. It has been shown that XRD analysis of
NCs provides valuable information regarding size, size
distribution, and ordering.20,25,35,36 Figure 2B represents the
XRD profile of TOPO-capped CdSe NCs. The low angle peak
at 5.3° indicates the presence of ultrasmall NCs. The XRD
analysis suggests that the average interparticle distance is 1.67
nm, where TOPO is acting as a spacer. This distance also
indicates CdSe NCs are ∼1.7 nm in diameter,35 which matches
closely with the size (1.74 nm) calculated from the empirical
sizing equation. In addition to the peak at 5.3°, there are two
The Journal of Physical Chemistry C
Figure 2. (A) TEM image of white light-emitting TOPO-capped
magic-sized CdSe NCs with first absorption peak at 422 nm. The NCs
are ∼1.8 nm in diameter. The scale bar is 20 nm. (B) XRD profile of
dried magic-sized CdSe NCs, analyzed using Cu Kα radiation source.
Inset shows the peak at higher angle is centered at 31°.
more peaks at <15°, which indicates the existence of long-range
order of NCs. The XRD analysis for TOPO-capped CdSe NCs
is similar to the previously reported dodecylamine-capped
(CdSe)33 and (CdSe)34 NCs.20 The EDX measurement
(Supporting Information Figure 3) of the TOPO-capped
NCs showed 1.1:1 atomic ratio of Cd to Se, which is in
agreement with the chemical structure assigned from optical
spectroscopic, TEM, and XRD analyses.
We investigated the continuous growth of TOPO-capped
magic-sized CdSe NCs at 85 °C and found that the formation
of magic-sized NCs was strongly dependent on the reaction
temperature. Ten minutes after TOPSe injection into the
TOPO/Cd(OAc)2 precursor, a broad peak at 425 nm was
observed with a broad shoulder at 365 nm, which indicates the
presence of CdSe NCs of less than 2.0 nm in diameter. Two
hours after the TOPSe injection, the absorption peaks
associated with the magic sized NCs became well-defined
with an additional shoulder appearing at 488 nm. This longer
wavelength shoulder is an indication of larger NC formation.
Over the course of 10 h of heating, the peak at 425 nm slowly
disappeared and a pronounced peak at 502 nm become
prominent (Supporting Information Figure 4). These absorp-
tion studies provide valuable information regarding the
continuous growth and stability of the magic-sized CdSe
NCs, which can be identified with three different stages: (i) At
the initial stage of the synthesis, the reaction mixture contains
magic-sized NCs and displayed an absorption peak (425 nm)
which is consistent with particles less than 2.0 nm in
diameter.34 (ii) Over the course of the reaction, the
concentration of the magic-sized NCs increases, and they
experience a second growth process forming larger particles,
which displayed an absorption peak at 488 nm. (iii) The last
stage of the process is the exclusive formation of larger NCs
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from the coalesence of magic-sized NCs. Our investigation is in
agreement with the literature reporting continued growth of
NCs at ∼300 °C in the presence of TOPO as a surface
passivating ligand.23 It is known that a major portion of NC
surface area remains unpassivated when TOPO is used as the
coordinating ligand.23 These unpassivated sites are more
accessible to Cd and Se present in the reaction mixture,
permitting further NC growth. We believe that when the
reaction was performed at 85 °C, the magic-sized NCs
experienced further growth due to the initial high concentration
of the nuclei in the reaction mixture in conjunction with the
weak stabilizing ability of TOPO. Recently, Owen and co-
workers also observed the continuous growth of magic-sized
CdSe NCs into larger NCs after increasing the reaction
temperature from 50 to 80 °C with primary amines serving as
stabilizing ligands.16 In a recent report by Bartl et al., the
authors also observed continuous growth of NCs at the
beginning of the reaction where initially formed clusters were
transformed to larger NCs over the course of the synthesis.37
The previous report and current findings indicate that the
stability of magic-sized CdSe NCs is closely related to the
reaction temperature and the nature of surface passivating
ligands.
We have investigated the role of impurities, presumably
alkylphosphonic and alkylphosphinic acids present in the
TOPO and TOP, on the formation of magic-sized CdSe
NCs. Previously, Wang et al. have reported that the various
impurities present in TOPO could potentially influence SCNCs
growth, reproducibility, and the quality.38 Another report has
also shown the effect of impurities present in TOP, specifically
the presence of dioctylphosphine (DOP), which substantially
influences the composition and optical signature of magic-sized
NCs.39 We have conducted two control experiments to
examine the role of impurities on the formation of magic-
sized CdSe NCs. In the first experiment, technical grade TOPO
(90%) and 97% TOP were used for NC synthesis. The molar
ratios of the reagents were identical to our original TOPO-
capped, magic-sized CdSe NC synthesis. The time-dependent
spectra, with a sharp first absorption peak at 414 nm
(Supporting Information Figure 7A), indicate formation of
thermodynamically stable, magic-sized CdSe NCs with a
diameter of 1.5 nm.2,20 In the second experiment, recrystallized
TOPO and purified TOPSe were used for CdSe NC synthesis
(see Experimental Methods and Supporting Information
Figures 5 and 6). The formation of magic-sized CdSe NCs
was similar to those found with the 99% TOPO and 97%
TOPSe (Supporting Information Figure 7B). The position of
sharp first absorption peak at 424 nm suggests the presence of
∼1.8 nm diameter NCs of the highest quality.
We have observed one noticeable difference in the formation
of magic-sized CdSe NCs when a different purity of TOPO was
used as the surface passivating ligand. In the case of 90%
TOPO and 97% TOPSe, the initial stage of the formation of
magic-sized NCs was slower compared to 99% TOPO and 97%
TOPSe. We believe this could be due to the formation of a low
percentage of relatively stable Cd-precursor formed between
Cd2+ and di-n-octylphosphonic acid, which is present as 1.78
mol % in the 90% TOPO.38 The optical data suggest that
impurities, such as alkylphosphonic or alkylphosphinic acids,
which are present in different TOPO and TOP samples, have a
negligible effect on the formation of magic-sized CdSe NCs.
Synthesis of Magic-Sized CdSe Nanoclusters in the
Presence of Different Surface Passivating Ligands. We
The Journal of Physical Chemistry C
extended our low-temperature synthetic method to the
preparation of OA-, EPA-, LA-, and TOA-capped magic-sized
CdSe NCs in order to both generalize the synthetic protocols
and investigate the optical properties, as compiled in Table 1.
Table 1. Summary of Absorption and Emission Spectra
Characterizing of CdSe NCs Synthesized in the Presence of
Different Surface Passivating Ligandsa,b
surface passivating ligand absorption peak (nm)c emission peak (nm)d
TOPO 422 502
OAe 404 (424) 451, 592
EPA 407 (429) 483
LA 418 530
TOA 413 (453) 584
a
The syntheses were carried out at 68−70 °C using 0.5 g (1.9 mmol)
of Cd(OAc)2·2H2O, 13.0 mmol of surface passivating ligand, and 3.4
mL of TOPSe. bAbsorption and emission spectra were collected in
toluene. cThe number in parentheses indicates the presence of an
additional shoulder at higher wavelength. dThe excitation wavelength
was 365 nm. eThe spectrum contains both band edge and broad
luminesence.
The OA-stabilized magic-sized CdSe NC synthesis was carried
out under identical reaction conditions, as described for
TOPO-capped NC synthesis. The formation of NCs was
monitored by UV−vis spectroscopy at different stages
throughout the reaction, as shown in Figure 3A. Thirty
Figure 3. (A) Time-dependent absorption spectra of the OA-capped
magic-sized CdSe NCs. (B) Emission spectra of CdSe NCs with
respect to the reaction time.
minutes after the TOPSe injection, two shoulders at 332 and
350 nm appeared, indicating the formation of ultrasmall CdSe
NCs. After 3 h, two additional shoulders were observed at 380
and 404 nm along with the shoulders at 332 and 350 nm. After
10 h of reaction, the shoulders at 380 and 404 nm became well-
defined peaks, where as shoulders at 332 and 350 nm became
less distinct. Over time, higher energy shoulders observed at
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332 and 350 nm disappeared and the peaks at 380 and 404 nm
became more pronounced. Around 36 h, another shoulder at
424 nm was visible along with the peaks at 380 and 404 nm.
After prolonged heating for 45 h, the position of peaks at 380
and 404 nm remained constant while the shoulder at 424 nm
became more prominent. In a recent report by Parak and co-
workers,40 the authors mentioned that in the case of the
quantized growth of magic-sized SCNCs, positions of the
absorption peaks remained constant while their intensities
increased over the time, which we observed for OA-capped
CdSe NCs.
The time-dependent absorption spectra provide valuable
insight regarding the quantized growth of different families of
magic-sized CdSe NCs in the presence of OA as the surface
passivating ligand. We propose following quantized growth of
magic-sized CdSe NCs with different families. Unlike regular
SCNCs, where both nucleation and growth steps control size
and shape, the formation of magic-sized NCs is predominantly
governed by a nucleation step without any additional growth
step.18,25 Considering there is no growth process in magic-sized
NC formation, we assume that the nuclei never reach the
supersaturation point or equilibrium concentration. Therefore,
the propose model is involved with only formation and
nucleation steps. The initial appearance of two shoulders at 332
and 350 nm indicates the formation of ultrasmall NCs, along
with one specific family7,8,14 of magic-sized NCs. With further
reaction, two additional shoulders at 380 and 404 nm appeared,
which suggests that another two families14 of NC are generated.
The formation of these two new families could possibly occur
by additional nucleation of the previously formed ultrasmall
NCs or partial conversion of the 350 nm family by molecular
addition of ultrasmall NCs on their surface. Afterward, the slow
disappearance of the higher energy shoulder at 332 nm
indicates the reaction mixture does not produce fresh ultrasmall
NCs while it is converted to one of the families of NCs, which
displayed a peak at 380 or 404 nm. The decrease in intensity of
the peak at 350 nm and the increase in intensity of lower
energy peaks (380 and 404 nm) also suggest that the 350 nm
family is undergoing slow conversion to different families of
magic-sized NCs. At the end of the synthesis, the peak at 350
nm completely disappeared while a new shoulder at 424 nm
appeared, which is an indication of the formation of a new
family of magic-sized CdSe NC. The formation of this new
family could be rationalized as molecular addition of the family
represented by the 350 nm band to the families represented by
380 and 404 nm. Previously, Kudera et al.14 also observed
similar optical behavior for nonanoic acid- and dodecylamine-
stabilized families of different magic-sized CdSe NCs. The
authors proposed a growth model based on the absorption
spectra that the magic-sized NCs are extremely stable, and once
they reach a particular composition, only further growth can be
experienced, but no dissolution.
At present, no literature is available regarding real-time in situ
characterizations of CdSe to identify the formation of ultrasmall
NCs at different stages of the synthesis. In most cases,
continuous and quantized growths of magic-sized SCNCs were
rationalized from the time-dependent absorption spec-
tra.14,16,18,23,40,41 However, the growth mechanism is still not
clear. Nevertheless, on the basis of our time-dependent UV−vis
spectroscopic analyses, we believe three different families of
magic-sized NCs were formed when OA was used as a surface
passivating ligand. We have confirmed the presence of two
The Journal of Physical Chemistry C
families of magic-sized CdSe NCs through XRD analysis, which
is discussed later.
The PL spectra of magic-sized OA-capped NCs is shown in
Figure 3B, where two different emission (λex = 365 nm) bands
are observed. The 5 h reaction mixture exhibited a sharp band
edge emission at 451 nm along with a broad emission covering
the entire visible region, centered at 592 nm. The intensity of
the band edge emission increased over time, and the peak
became narrow. After 45 h, a sharp band edge emission peak at
453 nm was observed with a very broad emission at 502 nm.
Similar emission behaviors for cystein- and fatty acid-capped
magic-sized CdSe NCs were reported earlier.13,14,25 The band
edge emission peak of our OA-stabilized CdSe NCs displayed
fwhm of 18 nm, which is an excitonic emission characteristic of
the magic-sized CdSe NCs.25 The narrowing of the band edge
emission peak over the course of synthesis also suggests an
improvement of crystalline character of the NCs. The broad
luminescence emission can be attributed to the recombination
of excitons at the low-energy surface states.25
The OA-capped magic-sized CdSe NCs were analyzed by
TEM (Figure 4) to determine particle size, providing NC
Figure 4. TEM image of white light-emitting, magic-sized CdSe NCs.
Scale bar is 20 nm.
diameters of 1.3 and 1.9 nm. Previously, Kudera et al.14 and Yu
et al.17 reported that magic-sized NCs exist with broad size
ranges in families with diameters from 1.5 to 2.0 nm and 1.7 to
2.2 nm. In recent reports, authors also mentioned that the NCs
could aggregate during TEM sample preparation18 and
consequently appear like ribbon structures.23 Our magic-sized
CdSe NCs sample was also analyzed by XRD to investigate the
composition (Supporting Information Figure 8). The broad
peak centered at 25° indicates that these NCs are extremely
small in size. In addition, peaks at 4.8° and 7.1° suggest that the
diameter of OA-capped particles are 1.84 and 1.25 nm,
respectively,24,35 which is in agreement with the NC size
determined from the TEM analysis and also indicates the
presence of two different families of magic-sized CdSe NCs.42
The XRD peak at 4.8° of our OA-capped CdSe NCs is in close
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proximity to the previously published work by Park et al.25 of
cysteine-capped magic-sized (CdSe)33 and (CdSe)34 NCs. In
addition, the XRD peak at 7.1° suggests the presence of
(CdSe)19 NCs.22 On the basis of TEM and XRD analyses, we
believe that the OA-capped NCs consist of three different
families: (CdSe)19, (CdSe)33, and (CdSe)34.14,22 Therefore,
TEM analysis along with XRD results provides information
confirming the presence of different families of magic-sized
NCs, which is consistent with the absorption characteristic of
the NCs discussed previously.
It is important to note that under identical reaction
conditions (mole ratio of reagents and temperature) TOPO-
capped, magic-sized CdSe NCs grew by continuous growth,
whereas quantized growth of NCs occurred when OA was used
as a stabilizing ligand. Previously, Siy et al.37 mentioned that
growth of high-quality NCs is dependent on both the binding
ability of the coordinating ligands and the reaction temperature.
In particular, when the synthesis is carried out at lower
temperature and in the presence of alphatic amines, which bind
strongly to the initially formed NCs, the transformation of
these thermodynamically stable NCs to the larger NCs would
be exceedingly slow. The authors mentioned that at low
temperature early stages of NC formation follow the stepwise
growth mechanism. According to literature reports,18,25 the
magic-sized NCs are only formed via a nucleation step without
additional growth. Therefore, the continuous and quantized
growth we observed for TOPO- and OA-capped NCs,
respectively, were completely nucleation driven processes and
were regulated by the nature of stabilizing ligand. We believe
the different growth processes we observed are due to the
stability and solubility of precursors formed between Cd(OAc)2
and ligands (X = TOPO and OA). As represented in eq 2a (X
= TOPO), addition of TOPO to the Cd(OAc)2 would likely
result in a Cd-TOPO complex, and upon addition of TOPSe at
70 °C (eq 2b), magic-sized CdSe NCs of a particular family
form via a continuous growth mechanism.
Cd(OAc)2 + X → [Cd(OAc)2 X] (2a)
70 °C
[Cd(OAc)2 X] + TOPSe ⎯⎯⎯⎯⎯⎯→ CdSe (magic‐NC) (2b)
X=TOPO or OA
In constrast, a different precursor would likely form between
OA and Cd(OAc)2 other than that formed between Cd(OAc)2
and TOPO, due to the phase state of the two coordinating
ligands. As shown in eq 2a, when X = OA yields a compound
with different solubility than X = TOPO due to strong
interactions between amine and Cd2+ and different phase states
of TOPO and OA. The addition of TOPSe to the complex in
eq 2b (X = OA) leads to the formation of magic-sized NCs
with different families.
Present literature reports do not explain the reasons for
continuous and discontinuous (quantized) growth of magic-
sized CdSe NCs.14,16,20,25 Moreover, both growth processes
were observed under unidentical reaction conditions and in the
presence of different coordinating ligands. In the present
investigation, we now have the ability to examine the growth of
magic-sized NC, which were prepared under identical
conditions while only modifying the nature of the ligand. Our
results indicate that the different growth processes of magic-
sized NCs are definitely controlled by the nature of the Cd-
ligand precursor. When OA is present, the complex that is
formed in the reaction mixture dissociates slowly relative to Cd-
The Journal of Physical Chemistry C
TOPO, resulting in the slow liberation of Cd2+ in the process of
CdSe NC generation. The slow liberation of Cd2+ generates
small nuclei over a certain perioid of time, as evidenced by the
initial appearance of the peak at 322 nm (Figure 3A). Because
the entire process is slow, the reaction medium generates nuclei
at different time points. Therefore, independent growth of
different nuclei takes place at various time points, resulting in
different families of magic-sized NCs.
Our synthetic process was also extended to other capping
agents such as EPA, LA, and TOA. As illustrated in Figure 5A,
Figure 5. (A) Absorbance (red) and emission (blue) spectra of EPA-
stabilized CdSe NCs. (B) LA-stabilized CdSe NCs.
the EPA-stabilized CdSe NCs displayed two pronounced
absorption peaks at 407 and 357 nm. These white light-
emitting NCs showed broad luminesence emission at 483 nm,
along with a weak shoulder at 433 nm, presumably due to the
band edge emission. As shown in Figure 5B, when the synthesis
was carried out using LA as the capping agent, the absorption
spectra showed features similar to TOPO-capped CdSe NCs
with narrow absorption peaks at 418 and 362 nm. The emission
spectra of LA-capped CdSe NCs showed broad emission at 530
nm, similar to TOPO-capped CdSe NCs. It is important to
mention that the TOPO-, LA-, and TOA-stabilized magic-sized
CdSe NCs emit green light, whereas OA- and EPA-stabilized
NCs emit white light. The PL properties due to different ligand
stabilization of these NCs can be explained based on the
binding energy of the ligands to Cd and Se sites. It has been
reported that phosphonic acids and primary amines bind more
strongly to Cd and Se sites, compared to phosphine oxides,
fatty acids, or tertiary amines. The binding energy trend of
various ligands to Cd and Se sites follows the order NH3 >
OP(OH)2CH3 > H2O > NH2CH3 > CH3COOH > HCOOH >
OP(CH3)3 > N(CH3)3 > P(CH3)3.43 Therefore, in the case of
TOPO-, LA-, and TOA-capped NCs, a large number of
noncoordinating Se sites would be available, allowing for the
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Article
recombination of excitons and producing the observed broad
luminesence in the PL emission spectra.13,21According to the
trend in binding energies, EPA-stabilized NCs should display
sharp band edge emission, followed by broad luminesence. In
this current investigation, we observed a weak band edge
emission and more pronounced broad luminesence centered at
483 nm. The absence of distinct band edge emission can likely
be attributed to the bulky nature of the EPA headgroup
(OP(OH)2). The larger headgroup present in EPA would allow
for a significant number of either Cd or Se sites to remain
unpassivated. These unpassivated surface sites allow for an
increased rate in electron−hole recombination, which would
result in a broad luminesence in the PL spectra. Broad
luminesence of white light-emitting CdSe from EPA capping is
not uncommon.15,16
Study of the Ligand Exchange Chemistry of TOPO-
Capped Magic-Sized CdSe Nanoclusters by OA. We were
also interested in investigating the absorption and emission
properties of magic-sized CdSe NCs by modifying their surface
through ligand exchange reactions. The ligand exchange or
place exchange chemistry of TOPO-capped CdSe NCs has
been studied with great detail because of their colloidal stability
in a wide range of nonpolar organic solvents and ease of surface
modification with various ligands.5,27−29,44−46 It has been
shown that the optical properties of the CdSe NCs can be
tuned via ligand exchange reactions, which is an ideal system to
study the surface chemistry of NCs in the presence of a
particular ligand as well as in mixed ligand states.28,29,44,45 To
the best of our knowledge, very few reports are available in
which place exchange reactions were carried out on magic-sized
CdSe NCs and their optical properties studied.15,29,47 In this
present investigation, the ligand exchange reaction was carried
out on TOPO-capped magic-sized CdSe NCs with the
relatively strong surface passivating ligand, OA. In our
experiment, vacuum-dried TOPO-capped magic-sized NCs
were dissolved in toluene and slowly heated to 90 °C under
an argon atmosphere (see Experimental Methods). At this
juncture, OA was added to the NC solution. The extent of
exchange reaction was monitored by UV−vis absorption and
emission spectroscopy. The TOPO-capped magic-sized NCs
displayed two distinct peaks at 422 and 365 nm with an
additional shoulder at 398 nm, as shown in Figure 6A. The
exchange reaction was run for 30 min, and at this time three
distinct peaks at 415, 362, and 388 nm appeared. Interestingly,
the first absorption peak of the exchange product blue-shifted
and became narrower (fwhm 14 nm) than the initial TOPO-
capped NCs (fwhm 20 nm). Previously, Landes et al.29
reported similar behavior in a butylamine exchange reaction
with TOPO-capped 1.6 nm CdSe NCs. According to their
report, the blue-shift of the absorption peak was attributed to
the structural changes of the NCs. Amines are known to be
stronger coordinating ligands in comparison to TOPO28,29 due
to the presence of a nonbonding pair of electrons, which results
in their ability to replace TOPO from the NC surface. During
the exchange reaction, the amount of energy released could
potentially break the Cd−Se bonds and allow NC reorganiza-
tion into a more stable structure.29 Figure 6B illustrates the PL
spectra of magic-sized CdSe NCs before and after surface
modification. The TOPO-capped CdSe NCs displayed a PL
emission peak at 502 nm and, after ligand exchange, a sharper
peak at 456 nm with a fwhm of ∼50 nm and a shoulder at 438
nm, which could be due to the band edge emission. The blue-
shift of the emission peak also indicates structural changes of
The Journal of Physical Chemistry C
Figure 6. (A) Absorption spectra of magic-sized CdSe NCs in toluene
before (blue) and after (red) ligand exchange. (B) Corresponding
emission spectra of NCs in toluene.
the NCs due to the OA exchange and supports the absorption
peak shifts. The real time monitoring of the exchange reaction
by absorption and emission spectroscopy could provide further
insights into structural changes of the magic-sized CdSe NCs
caused by ligand replacement. This part of the research is
currently under investigation.
■
CONCLUSIONS
In conclusion, we have demonstrated an efficient method for
synthesizing TOPO-capped magic-sized CdSe NCs. Our
optical and X-ray diffraction spectroscopic analyses as well as
electron microscopy confirmed the formation of ultrasmall
NCs. The reaction temperature played an important role in the
selective growth of TOPO-capped magic-sized NCs. The
impurities present in three different grades of TOPO had no
effect on magic-sized CdSe NCs composition, and in each case,
a continuous growth of the magic-sized NCs was observed. The
versatility of the synthetic method was further demonstrated by
performing syntheses with a wide range of surface passivating
ligands, such as OA, EPA, LA, and TOA. Depending on the
ligands used in the protocol, the NCs displayed either broad
luminesence or a combination of band edge and broad
luminesence. The TOPO-capped CdSe NCs exhibited
continuous growth, whereas OA-stabilized NCs underwent
quantized growth. We have also shown that the optical
properties of TOPO-capped magic-sized CdSe NCs can be
tuned via surface modification, which should provide better
understanding of the photophysical properties of such ultra-
small NCs and a means of identifying additional potential
applications in optoelectronics.
■
*
ASSOCIATED CONTENT
S Supporting Information
Additional absorption, emission, XRD, and EDX spectra;
HRTEM images; 31P{1H} NMR spectra of 90%, 99%,
recrystallized TOPO, and vacuum-distilled TOPSe. This
I dx.doi.org/10.1021/jp2086818 | J. Phys. Chem. C XXXX, XXX, XXX−XXX
Article
material is available free of charge via the Internet at http://
pubs.acs.org.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: rsardar@iupui.edu.
Present Address
⊥
Center for Materials for Information Technology, The
University of Alabama, Tuscaloosa, AL 35487.
Author Contributions
∥
These authors contributed equally.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This research was supported by Start-up Funds provided by
IUPUI. We also thank Professor Barry Muhoberac for helpful
discussions.
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