Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2018.

Supporting Information
for Adv. Mater., DOI: 10.1002/adma.201803433

Revealing Driving Forces in Quantum Dot Supercrystal

Assembly
Emanuele Marino, Thomas E. Kodger, Gerard H. Wegdam,
and Peter Schall*
Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2018.

Supporting Information

Revealing Driving Forces in Quantum Dot Supercrystal Assembly

E. Marino, T.E. Kodger, G.H. Wegdam, and P. Schall*

Chemicals: 1-Octadecene (90%, Aldrich), Cadmium oxide (≥99.99%, Aldrich), Ethanol

absolute (99.6%), Hexane (anhydrous 95%, Aldrich), Hexane (anhydrous 95%, Aldrich),
MilliQ water, Oleic acid (90%, Sigma Aldrich), Selenium (≥99.99%, Strem Chemicals),
Trioctylphosphine (TOP, 97% Aldrich), Sodium dodecyl sulfate (SDS, ≥99%, Sigma
Aldrich)., Lead (II) chloride (Alfa Aesar 99.999%), Sulfur (≥99.99%, Aldrich), Oleylamine
(70%, Aldrich).

Nanoparticle synthesis: CdSe quantum dots were synthesized and washed following the
procedure of Chernomordik et al.[1] CdSe and PbS quantum dots were prepared according to
literature reports with minor modifications.[1-2] For CdSe, we added the TOP:Se in ODE
solution at a rate of 10 mL/hour by means of a syringe pump. The flask was quenched by
means of a cold water bath as soon as the injection was completed. For PbS, the reaction was
quenched after 4 minutes both by adding 80 mL cold hexanes and by means of a cold water
bath. PbS quantum dots were synthesized following the procedure of Weidman et al. [2] The
monodispersity of the product was qualitatively and quantitatively addressed by measuring
respectively the full-width half-maximum of the first exciton peak in the absorption spectrum,
electron microscopy and SAXS form factor extracted from dilute dispersions (see below). The
concentration of CdSe and PbS quantum dots was estimated from sizing curves available in
the literature.[3]

Sample preparation: The form factors of quantum dots (CdSe or PbS) were obtained from 5
mg/mL dispersion in cyclohexane or hexane. To prepare the emulsion used in the kinetic
experiments 4 mL dispersion of 5 mg/mL CdSe (or PbS) quantum dots in a nonpolar solvent
(hexane or cyclohexane in this study) was layered on top of a 16 mL solution of 60 g/L SDS
in water. The mixture was emulsified by using a vortex mixer until the emulsion looked
homogeneous (2-3 minutes). The emulsion was dried while stirring gently and controlling the
temperature by means of a thermocouple connected to a hotplate; details are provided in the
following section. After drying, the product was washed twice in a solution of surfactant in
water, 6 g/L, by centrifuging at 3000 g for 20 minutes and resuspending. Finally the washed
product was resuspended in a 4 mL solution of surfactant in water, 6 g/L.

Measurement setup for kinetic experiments: The measurement setup used for kinetic
measurements is described in Figure S3 a. We added a stir bar to the 40ml glass vial
containing the emulsion, and placed it on a hot plate. The stirring speed was set high enough
to obtain a vortex to prevent creaming of the droplets or sedimentation of superstructures. The
temperature of the emulsion was set by a thermocouple connected to the hotplate and
immersed in the sample. The mixture was flowed by means of a peristaltic pump (Masterflex
L/S, slowest speed setting) through fluorinated tubing (Viton, Saint-Gobain). The tubing was
connected to the quartz capillary used for the measurement by means of a connector shown in
Figure S3 b. The quartz capillary was prepared by removing both ends of a standard 2mm

1
quartz capillary with 10μm thick walls for SAXS (Hampton Research) by means of regular
scissors. This operation leaves a quartz cylinder which fits inside of the connector as shown in
Figure S3a. The connection between quartz tubing and connector was sealed by means of 2-
component epoxy (90 minutes recommended curing time).

SEM Imaging. A Verios XHR SEM (FEI) was used for electron microscopy characterization.
The microscope was operated at 20-30 kV and 100 pA in transmission mode using a STEM
detector. Bright field and secondary electron images were simultaneously recorded.
Concerning sample preparation, we washed the supercrystal suspension twice in deionized
water and deposited of suspension on a carbon-coated copper TEM grid (EMS). Prior to
imaging, we dried the TEM grid under vacuum in a desiccator for at least 3 hours.

SAXS: Small angle X-ray scattering patterns were collected using a Pilatus 1M detector at
BM26B beamline, DUBBEL at ESRF.[4] The duration of each measurement was set to 100
seconds collection time. The sample to detector distance was set to 2.9 meters, achieving a q-
range of . The beam energy was set to 12 keV. The X-ray beam has an
attenuation length of 16 μm at 12 keV for CdSe,[5] allowing for light to fully probe the
entire volume of the superstructures, yielding a complete structural characterization of the
material which is contained in the two-dimensional scattering patterns. The attenuation length
of a material is defined as: , where is the impinging light
intensity on a slab of thickness x and is the transmitted light. To calculate the attenuation
[5]
length we searched the literature for mass-attenuation coefficients at 12 keV of
2 2
Cadmium ( 83 cm g) and Selenium ( 23 cm g). Therefore for CdSe we obtained
μ 83 23 106 cm2 g. Multiplying for the density of CdSe: μ (μ )
. Finally the attenuation length in microns can be obtained as
. The same calculation for PbS gives .

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Data analysis: The wavevector is defined as q sin( 2), where is the wavelength of
incident X-rays and is the scattering angle.
The form factor was extracted by fitting the experimental scattering patter of diluted CdSe
quantum dots in hexane to a spherical form factor F:

sin qr qrcos(qr)
F q,r 3V(r)
(qr)3

where r is the particle radius, q is the wavevector and V(r) is the volume of a sphere of radius
r.[6]
To account for size dispersion, we averaged over form factors of radius r varying around an
average value r0 where the contribution of each form factor was weighed with a Gaussian
distribution G(r,r0,W) centered around r=r0 and of width W.[6] The result is:

FG q,r0 ,W ∫ F q,r 2 G(r,r0 ,W)dr

0

Fitting procedure was performed either using self-developed code in Matlab, or using Sasfit
software.[7] The polydispersity is calculated as . The measured form factors

2
and related fits are shown in Figure S1 and S8 for, respectively, the CdSe and PbS QD
samples used for the kinetic experiments reported in this work.
For each kinetic measurements, the procedure is as follows:
- After drying the emulsion as described in the main text, we washed the superstructures
twice (3000g, 10 minutes) in 6 g/L SDS in water. The resulting dispersion was added
to a quartz capillary and measured under the X-ray beam. After azimuthal averaging
and solvent background subtraction, we divided the obtained scattering pattern by the
previously obtained form factor S q I q,t FG q,r0 ,W , and obtained the result
shown in Figure 1g. The peak positions qi are consistent with face-centered-cubic,
FCC, ordering (ratios qi/q1= 1, √ ,√ ,√ , 2). We therefore fitted the first 2
peaks with Gaussians. From the fitting parameters related to the first peak (111 FCC
diffraction peak), we extracted the structural parameters related to the FCC lattice:
√
1. Lattice parameter where q111=q1;
√
2. Nearest neighbor surface-to-surface distance ;
3. Crystal size where K is the Scherrer constant (K≈1 for spherical
shaped crystals) and Δq is the full width at half maximum of the 111 peak;[9]
[8]

4. Volume fraction %.
- We then analysed the kinetic measurements. We extracted an effective structure factor
by dividing the azimuthal averaged scattering pattern measured at time t by the pattern
obtained at time 0 under dilute regime: Seff q I q,t I(q,0). This procedure proved
very helpful as it would be complicated to calculate the real form factor including
contributions from polydisperse droplets shrinking in time with nanoparticles
dispersed therein. We noticed the presence of additional peaks consistent with HCP
ordering. HCP has an additional degree of freedom compared to FCC, the ratio
between the height of the unit cell, c, and the lattice parameter, a. The value that best
fits the measured structure factor is c a 1.85, the resulting peak positions of which we
also show in Figure 1g. Clearly, these peak positions describe the additional features
well. By chance, this is a similar value as the one measured for HCP crystals of atomic
zinc, c a 1.86.
We added the contribution of HCP to the fitting procedure and completed the fitting of
kinetic measurements by proceeding from the last to the first time points, and shifting
the bounds imposed on the fitting parameters related to peak positions by an amount
proportional to the shift of the position of the maximum in time. For each time point,
the fitting procedure is as follows: We employ a Gaussian fit to each peak individually
starting with the peaks that overlap the least (on the lower q side HCP(100) and on the
higher q side FCC(200)) and ending with the peaks that overlap the most (FCC(111),
HCP(002)). After fitting each peak, we subtract the fitted curve from the total structure
factor, and proceed with fitting the next peak from the residual structure factor. The
result is shown in Figure 2. We calculated the relative phase fractions by
A
fFCC,HC A FCC,HC where A I111,100 FCC,HC
, where I111,100 is the intensity of the
FCC A HC
111 peak for the FCC crystal or 100 peak for the HCP crystal. Qualitatively this can be
justified as the number of unit cells of a crystal should be proportional to the number
of crystallites (I) times the average crystal size ( ).
Since the determined values of volume fraction are central to this work, we provide an
estimate of their uncertainty. At a single time point, an estimate for the relative
uncertainty on the volume fraction can be given by Δϕ/ϕ, where ϕ is the determined
volume fraction and Δϕ=ϕ(q111 Δq111/2)- ϕ(q111-Δq111/2), represents the uncertainty in

3
 volume fraction defined by the full-width at half-maximum Δq111 of the FCC(111)
peak. We measure Δϕ/ϕ to lie in the range of 0.2-0.5%. Therefore, we can
conservatively assume Δϕ/ϕ ≤1%.

Influence of system properties on the supercrystal quality:

- Choice of hydrophobic solvents. We have used pentane, hexane, cyclohexane and
chloroform as the dispersed emulsion phase. We have investigated how the use of a specific
solvent affects the crystallinity of QD supercrystals while driving the assembly at a fixed
temperature (20 °C). While the overall FCC symmetry is unaffected, we find that cyclohexane
yields the largest crystals, followed by chloroform, hexane and pentane. To first
approximation, the rate of change in particle volume fraction will depend on the solubility of
the hydrophobic solvent in the aqueous phase and on the solvent’s boiling point. Our findings
suggest that the solvent’s boiling point is the main contributing factor, with pentane (bp 36°C)
yielding the smallest crystals and cyclohexane (bp 81°C) the largest. This is quite interesting
especially considering that the solvent solubility in water varies over almost two orders of
magnitude among the considered solvents (pentane, hexane, cyclohexane with solubility in
water less than 1 mM, while for chloroform 67 mM). To illustrate these claims, a new figure
has been added to the Supporting Information file (Figure S9 a,c-e), showing the structure
factor for QD supercrystals prepared by using different hydrophobic solvents (a), together
with electron micrographs of the supercrystals (c-e).

- Particle polydispersity. For a fixed temperature (20 °C), and average size of QDs (5.5 ± 0.1
nm), we find that the particle polydispersity greatly affects the structural properties of QD
supercrystals. For polydispersity values ≤7.8 % the FCC symmetry is retained, with the most
monodisperse sample yielding the largest crystals. However for the more polydisperse
sample, 11.1 %, we find a fully amorphous, or glassy, superstructure. Figure S9 b shows the
structure factor for QD supercrystals prepared by using QDs differing in polydispersity.

- Surfactant concentration. The surfactant SDS stabilizes the droplets of hydrophobic solvent
in water. We find that increasing the concentration of SDS also increases the crystallite size.
Increasing surfactant concentration in the bulk of the aqueous phase likely causes an increase
in concentration of surfactant molecules bound to the surface of the droplet, decreasing the
surface tension. This decrease make the liquid-liquid interface more flexible allowing QDs to
rearrange more readily at the curved interface which acts as a defect or hindrance to crystal
formation; we speculate that this is causes an improvement in crystal quality . Figure S10
shows the structure factor of QD supercrystals prepared using different surfactant
concentrations.

Model: The model represents a competition between a repulsive steric hindrance term Ust and
an attractive van der Waals term UvdW. We followed the discussion provided in a recent
publication to calculate the effective potential .[10]
Briefly:
- The attractive van der Waals interaction is described by:[10-11]

where A is the Hamaker constant, r is the nanocrystal radius, and d is the interparticle
separation.
The Hamaker constant is given by

4
 (√ ) (√ )
√ ((√ ) )

and are, respectively, the plasma frequencies of the QD material and of

the dielectric (hexane) and n is the refractive index of the dielectric. For CdSe QDs in
hexane we have , , .
- The repulsive steric repulsion interaction is described by:[10, 12]

where is the ligand grafting density,[13] is the ligand length,

is the length of one carbon-carbon bond and is the number of
carbon-carbon bonds in an oleate ligand. This description refers to the ligand as a N-
mer brush of length and monomer length .
From the modeled potentials shown in Figure 3g, we extracted the second virial coefficient
according to:[14]
d
2 d,T ∫ {1 exp( U(r) kT)}r2 dr (1)
The idea is to calculate the second virial coefficient from the process of taking a particle from
a distance distance to a away from another particle, where d is the surface to
surface distance between quantum dots cores. The comparison between modeled and
measured B2 is shown in Figure 3h. We show the potentials and B’s modeled as a function of
ligand length in Figure S6. We show the potential U extracted from the data for the slow
quench (Figure 3 c) in Figure S7 compared to the modeled potential for =1.3 nm.

5
Figure S1 Azimuthally averaged scattering pattern for a 5 mg/mL dispersion of oleate-capped CdSe
quantum dots dispersed in hexane. The intensity decay has been fit to a spherical form factor accounting
for particle polydispersity 𝑭𝑮 .

Figure S2 Light microscope image of an polydisperse hexane in water emulsion droplets

(20% hexane) stabilized by sodium dodecyl sulfate (6 g/L). The image was taken immediately
after preparing the emulsion.

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Figure S3 (a) Schematic of the custom-built setup used for the kinetic SAXS measurements.
The prepared emulsion is flowed by means of a peristaltic pump through tubing in a closed
cycle ending in a temperature-controlled reservoir. The temperature of the vial is controlled
by means of a thermocouple connected to the hot plate. To ensure uniform heating, the
emulsion was gently stirred during the whole duration of the experiment. The tubing is
connected to the central portion of a quartz capillary for SAXS (therefore a quartz cylinder)
by means of the connector shown in inset in (b). The X-ray beam impinges on the sample
flowing through the capillary and is thereby scattered on the detector. (b) Photograph of the
experimental setup. (i) Hotplate, (ii) vial containing the emulsion, (iii) thermocouple, (iv)
peristaltic pump, (v) sample position, (vi) connector mounted on a magnetic base to be place
in position (v), (vii) vacuum tube at the end of which the SAXS detector was placed (sample-
to-detector distance 2.9 m).

Figure S4 (a) Electron microscopy low-resolution image of the prepared supercrystals and
measured distribution of diameters (b).

7
Figure S5 (a) Three-dimensional plot of the raw scattered light intensity as a function of
wavevector and time for CdSe QDs dispersed in hexane droplets shrinking in time. (b)
Semilogarithmic plot showing the evolution of the effective structure factor as a function of
time around the detected time of nucleation (full colored lines). The fits for the HCP and FCC
peaks are shown (dotted lines) for measurement times 250 min (dark gray) and 290 min (light
gray). The broad signal observed around 250 minutes is much sharper than what would be
expected for a dense liquid according to the Percus Yevick equation calculated for a volume
fraction of ϕ=30% and for a hard sphere diameter of eff=QD 2ℓ (dashed black line).

Figure S6 (a) Total particle-particle interaction potential as a function of interparticle

distance and ligand length . From the potentials we can calculate the second virial
coefficient according to equation 1.

8
Figure S7 Comparison of measured and simulated ( ) interparticle potential. The
measured potential is derived from the second virial coefficient by inverting equation 1.

9
Figure S8 SAXS kinetic data for PbS QDs crystallizing into FCC supercrystals. (a) Scattering
pattern from a dilute 5 mg/mL dispersion of PbS QDs in hexane. The pattern is fit to a
spherical form factor accounting for particle polydispersity . (b) STEM graph of PbS
nanocrystals on a carbon-coated copper grid. (c) Azimuthally averaged scattering pattern as a
function of time, as the QDs transit from a colloidal gaseous to a solid phase. (d) Effective
structure factor of PbS QDs during crystallization. (e) Effective FCC volume fraction in time
for PbS QDs crystallizing into a FCC crystal. (f) STEM graph of PbS nanocrystals assembled
in supercrystals.

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Figure S9 Influence on crystallinity of CdSe QD supercrystals of basic colloidal parameters.
(a) Supercrystal structure factor measured for supercrystals prepared from 5.4 nm CdSe QDs
at the same temperature (20 °C), for different hydrophobic solvents. While the overall FCC
symmetry is retained for all samples, we observe the broadest peaks (smallest crystals) for the
solvent with the lowest boiling point (pentane, 36 °C) and the sharpest peaks (largest crystals)
for the solvent with the highest boiling point (cyclohexane, 81 °C). (b) Supercrystal structure
factor measured for supercrystals prepared from CdSe QDs of the same size (5.5 ± 0.1 nm)
and different polydispersity, While the FCC symmetry is retained for the samples of
polydispersity ≤7.8 %, the sample with 11.1 % polydispersity appears completely amorphous.

11
(c-f) Representative SEM images of supercrystals prepared by using different hydrophobic
solvents.

Figure S10 Influence on crystallinity of CdSe QD supercrystals of SDS surfactant

concentration. Increasing surfactant concentration causes an increase in supercrystal size
(sharpening of diffraction peaks).

12
Figure S11 Full-scale duplicate image of Figure 1e. Scanning electron microscope image of
an 800 nm spherical supercrystal showing highly ordered 5.4 nm quantum dots. Scale bar
indicates 200 nm. Inset: fast-Fourier-transform of the SEM image displaying six-fold
symmetry.

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