SUPERLATTICES BASED ON LEAD SULFIDE QUANTUM DOTS

Oskolkov E.O., Ushakova E.V., Golubkov V.V., Litvin A.P., Parfenov P.S., Baranov A.V.

1) ITMO University, 49 Kronverkskiy pr., Saint-Petersburg, Russia.

2)Institute of Silicate Chemistry of Russian Academy of Sciences, 2 Adm. Makarova emb., Saint-Petersburg, Russia

Experimental

Introduction
For the past few years a lot of studies have been held on semiconductor nanocrystals absorbing and
emitting in near-infrared region of spectrum, such as lead-chalcogenide quantum dots (QDs). These QDs
can self-assemble into superstructures, namely, superlattices (QDSLs) [1]. The properties of the materials
based on QDSLs depend strongly on distances between QDs. Therefore the establishment of the
parameters of self-assembly process, which affects the morphology of superstructures based on QDs, is
of great importance. This is the key to the ability of fabricating materials with definite and controllable
parameteres and properties, for improving the photovoltaic devices in near-IR region of spectrum.
Colloidal lead sulfate (PbS) quantum dots stand out due to their specific properties as large extinction
coefficients, a large overlap of absorption spectrum with solar radiation spectrum, small effective masses
of charge carriers, possibility of multiple exciton generation and hot-carrier extraction [3].
Despite large number of studies in this field, our knowledge of QD self-assembly is still far from being
complete. The most important parameters, affecting this process are QD concentration, QD size, type and
quantity of ligands and type of solvents. Studiyng these parameters effect on self-assembly leads to need
for carrying out complex experimental data analysis and restrains the possibility of using of self-organized
structures in advanced technology. Thus more detailed studies must be held to clarify some unknown
aspects of QD self-assembly process and to get precise control of it.
In this work we experimentally investigate the influence of the type and amount of ligands, together with
temperature dependence, on QDSL period.

Figure 1. Scheme of setup for SAXS measurements

To determine the diameters of QDs and to study the superlattices spatial

geometry the Small-Angle X-ray Scattering (SAXS) method was used.
SAXS range: from 6 to 250 arcmin
Setup: slit collimation geometry defining a beam of effectively infinite length
Radiation: CuK radiation at wavelength of 1.54
Filter: Ni
Angle resolution: ~1 arcmin
The general scheme of this method is shown on Fig.1

QDSLs formation

Period of QDSLs

Figure 5 presents a comparison of the SAXS

patterns. The obtained results indicate that
the removal of the ligands leads to the shift
of peaks positions to larger angles. At the
same time, peaks become narrower as a
higher ordering of QDSL takes place. Optical
microscopy images (Figure 3) of QDSLs
formed from QDs treated by acetone or
isopropanol show that the obtained
superstructures look more homogeneous
than untreated. However, the attempt to
remove ligands from the QD surface did not
give us the ability to form close-packed
QDSLs. The distance between the surfaces of
the QDs was from 0.4 to 0.8 nm. This shows
that the ligands were removed only partially.

Figure 4. Correlation between QDs diameters and period of QDSLs

onclusions
The morphology of QDSLs depends type and amount of ligands on QDs
surfaces. Our study has shown that treatment with isopropanol provides
formation of the most homogenous SLs with the minimal lattice period
compared to other solvents used.
The method of annealing of the QDSLs proved to be inefficient for QDSL
improving, as the structures become less ordered along with the
increasing of annealing time.

Acknowledgement
This work was funded by grant 14.25.31.0002 and Government
Assignment No. 3.109.2014/K of the Ministry of Education and Science of
the Russian Federation. A.P.L. and E.V.U. thank the Ministry of Education
and Science of the Russian Federation for support via the Scholarships of
the President of the Russian Federation for Young Scientists and Graduate
Students (20132015).

PbS1575 on glass
initial
aceton
methanol
isopropanol

1,0

0,5

0,0

20

40

60

80

100

120

140

Scattering angle (arcmin)

6,0

Figure 5. SAXS of treated PbS QDs

QDSLs initial

5,5

SAXS intensity (imp/sec)

As it was investigated earlier[4], the distances between QDs in superlattices

depend linearly on QD diameter. The geometrical assembly of the structures does
not depend on the QDs size. The period of ordering is of the same order as the
QD diameter. The dependence slope shown in the Figure 4 by a dashed line is
1.28 1.1, though for the close-packed structures the slope should be strictly 1.
The difference is likely caused by layer of organic molecules on the QD surface.
This layer thickens as the QDs diameter increases. Thus the direct contact
between QDs does not occur. The red line (x+1.8) shows the dependence of the
layer thickness of ligands. The value of 1.8 nm corresponds to the oleic acid
molecule size. The distances between QDs go up to ~3.4 nm for the larger-sized
dots. This indicates an excessive amount of oleic acid molecules on QDs surface.

Figure 3. Images of fabricated QDSLs from

confocal microscope (Renishaw)

Period of QDSLs after treatment

SAXS intensity

Figure 2. Formation of close-packed structure

PbS QDs were synthesized by hot-injection method.

QD Diameters: 2.8 to 8.9 nm.
Solvent: tetrachlormethane.
The superlattices were obtained by the QD colloidal solution evaporation on the substrate.
Substrate: a glass coverslide.
To study the ligands influence on interparticle distances QDs with diameters of 6.3 nm were used. The stock QD
solutions were treated the following way:
1) 100 l (acetone/isopropanol/methanol) + 50 l (QD stock solution),
2) stirring in the ultrasound bath.
3) centrifuging (to precipitate the nanocrystals)
4) redispersing in 50 l of TCM
5) stirring in the ultrasonic bath for 5-10 minutes
6) 15 l of obtained QD solution dripped on the glass substrate and dried in an ambient atmosphere at room
temperature

annealing
1 min
10 min
30 min

5,0
4,5
4,0
3,5
3,0
2,5
2,0
1,5
1,0
0,5
0

20

40

60

80

100

Scattering angle (arcmin)

120

The annealing treatment of QDSLs was being held in vacuum

at temperature of 380 C for periods of 1, 10 and 30 minutes.
The QDSLs were fabricated by the method described in
previous section. The given temperature and time intervals
allow to vaporize the ligands from the QDs surfaces. The
analysis of the the SAXS data for treated SLs showed that an
increasing of the annealing time leads to more and more
disordering in the initial QDSLs. And for the 30 minute
annealing the QDSLs were destroyed completely and the
sample represented the ensemble of isolated QDs on a
substrate.
This indicates that thermal treatment does not improve the
QDSLs parameters such as ordering and homogenity. It is also
can be assumed that complete ligand removal from the QD
surface leads to disordering of the QD assemblies. Hence, the
surface ligands affect much the QDSL formation process.

Figure 6. SAXS of treated PbS QDSLs

References
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