Solution grown PbS nanoparticle films

Rakesh K. Joshia,*, Aloke Kanjilalb, H.K. Sehgala

aDepartment of Physics, Indian Institute of Technology, Hauz Khas, New Delhi 110016, India
1
Department of Physics and Astronomy, University of Aarhus, DK 8000 Aarhus C, Denmark
Received 6 April 2003; received in revised form 6 April 2003; accepted 24 July 2003

Abstract

Lead sulfide (PbS) nanoparticle films were chemically grown on glass, quartz and silicon substrates. Structure and size of PbS
nanoparticles were characterized by X-ray diffraction and transmission electron microscopy (TEM), respectively. Large optical
band gap has been observed in these films. The decreases in dc-conductivity, Hall mobility and carrier concentration with
reducing grain size were also examined. Heterojunctions of p-PbS/n-Si were fabricated and photovoltaic effect was observed in
these self-assembled heterojunctions.

PACS: 73.40.Lq; 73.61.Tm; 81.05.Hd; 81.10.Dn

Keywords: Lead sulfide; Nanoparticle films; Heterojunction

1. Introduction A variety of different methods have been employed to

Nanotechnology deals with nanometer size objects.
Size dependent new physical aspects have been gen-
erating a continuous thrust for new practical applica-
tions [1]. Recently, lead sulfide (PbS) nanocrystals
with dimension in the range of 1-20 nm are of tech-
nological interest for advanced optoelectronic appli-
cations. They show a strong quantum confinement
effect when the crystallite size becomes equal to
the dimension of Bohr exciton [2,3]. Earlier investiga-
tions into the fundamental limits of the performance
of PbS nanoparticle based devices confirm their
ability to become a versatile technological platform
for the creation of better optoelectronic devices [1-3].
grow the PbS nanoparticles on different substrates [4].
Growth of the nanoparticle films for device applica-
tions is still an emerging field of research. In this paper
we report the optical and electrical properties of PbS
nanoparticle films grown by chemical bath deposition
(CBD) method. Photovoltaic effect in p-PbS/n-Si
heterojunctions is also demonstrated.
2. Experimental
Nanoparticle films of PbS were grown on glass,
quartz and n-type silicon (Si) substrates, respectively
from an alkaline chemical bath. M/40 lead acetate and
M/30 thiourea were mixed in equal proportions. Initi-
ally, cleaned substrates were dipped in the solution.
The chemical bath was maintained at an optimized
temperature and pH (given in Table 1) and solution
44 R.K. Joshi et al./Applied Surface Science 221 (2004) 43-47

Table 1
Effect of pH and temperature on grain size, band gap and transport properties of PbS nanoparticle films
1
pH Grain size (nm) Band gap (eV) a (Q cm ^ ( x l O - 3 ) u (cm2 V"1 Nc (xlO 15 ) (cm"3)

20 8C 35 8C 20 8C 35 8C 20 8C 35 8C 20 8C 35 8C 20 8C 35 8C

9.25 12 14 2.32 2.15 1.05 1.45 4 6 1.60 1.50

9.75 15 19 2.05 1.80 1.25 1.95 5 8 1.56 1.52
10.25 17 23 1.95 1.52 1.85 2.50 7 11 1.65 1.42

was stirred continuously the solution was stirred con- close to (10 0) zone axis in strongly underfocused
tinuously. Films were allowed to grow for an optimum condition. Under this condition, the black/gray contrasts
time to achieve a thickness of 150 nm. Heterojunc- in white background represent the PbS nanoparticles.
tions were fabricated between p-type PbS film and n- The average grain size in the prepared films is
single crystal silicon substrate. observed to be increased with increase in pH and
These films were structurally characterized by X- temperature, respectively (Table 1). Samples are
ray diffraction (XRD) using a Philips X-pert X-ray found to be crystalline both by TEM and XRD studies.
powder diffractometer with Cu Ka (1=1:54 A) The grain size measured by TEM is very much similar
radiation at a glancing angle of 38 and transmission to the size calculated from the XRD peak widths. The
electron microscopy (TEM) of plan view geometry fcc phase is detected for all the nanoparticle films from
with a Philips CM20 instrument operating at 200 keV, XRD data. Typical XRD patterns for films grown in
respectively. The optical transmittance and reflec- two different pH values are shown in Fig. 2.
tance were measured with the help of a UV-Vis- Absorption coefficient a (cm ~h) for the films
NIR spectrophotometer. To study the junction char- is calculated using the experimentally observed re-
acteristics of the heterojunctions, the films were flectance (R) and transmittance (T) of the films.
chemically dissolved from the edges and also from The (ahn)m versus hn plots for m = 2, 1/2, 1/3 show
the back side of the n-Si substrate. Indium dots (1 mm linear behavior for m = 2 indicating presence of direct
in diameter) were used to make electrical contacts
between the p-type film and n-type Si. The S1 10
Kiethley Hall Measurement setup was used for the
resistivity and Hall measurements on these nanopar-
ticle films.
The current-voltage (I—V) characteristics of the p-n
junctions were studied with the help of a program-
mable curve tracer (Tektronix 370). I—V characteristic
was studied in dark and under illumination of light
(AM 1.5 sunlight), respectively. Junction capacitance
as a function of the applied forward bias voltage
was measured at 1 MHz by using MDC, RM-1600
capacitance-voltage/conductance-voltage (C—V/G—V)
analysis system and Keithley Quasi static system.

3. Result and discussion

A typical bright field plan view TEM image of

nanoparticle film grown from a chemical bath with Fig. 1. TEM micrograph of PbS nanoparticle film grown at pH
pH 9.75 and temperature 35 8C is shown in Fig. 1. The 9.75 and temperature 35 8C. The black/gray contrasts represent the
micrographs are taken with an electron beam direction randomly oriented crystalline PbS nanoparticles.
 R.K. Joshi et al./Applied Surface Science 221 (2004) 43-47 45

CO 50 60 70
20(deg.)
Fig. 2. XRD patterns for PbS nanoparticle films grown at temperature 20 8C and (a) pH 9.25 (b) pH 10.25, respectively.

optical band gap in the present nanoparticle films. A
typical (ahn)2 versus hn plots for PbS nanoparticle film
grown at pH 9.75 and temperature 20 8C is shown in
Fig. 3. The optical band gap is observed to decrease
with increase in pH and temperature of the chemical
bath. It is evident from Table 1 that the band gap (Eg) is
varied from 1.52 to 2.32 eV when the grain size
reduces form 23 to 12 nm.
Resistivity and Hall measurements are performed at
room temperature on these samples. Resistivity of the
films is found to be increased with decrease in grain
size. This increase in resistivity is attributed to the

1.0x10

0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5

Fig. 3. hn vs. (ahn)2 plot for the PbS nanoparticle film grown at pH 9.75 and temperature 20 8C.
46 R.K. Joshi et al./Applied Surface Science 221 (2004) 43-47

20
35

30
1
3 25-
1 20- Dark %
| 15 Illumination /

10 /

-1 ooo 1000 5

Bias Voltage (mv) : ;

-100(5 :Boo ^i 1 ..,.-•• 500 1000
"&" Bias Voltage (mv)
-10

(a) ] L!^ I (b) -15

Fig. 4. I—V characteristic of p-PbS/n-Si heterojunction; PbS film grown at (a) pH 9.25 and temperature 35 8C (b) pH 10.25 and temperature 35 8C.

decrease in particle packing density with decrease in
grain size. Transport parameters for the nanoparticle
films are given in Table 1. Hall mobility of PbS
nanoparticle films is also observed to be decreased
with reducing grain size.
The heterojunctions between p-type nanoparticle
films and n-type Si substrate is fabricated and char-
acterized by I—V and C—V measurements. The I—V
characteristic for p-PbS/n-Si is shown in Fig. 4. From
the I—V characteristic it is observed that the current in
forward bias regime is greater than that of reverse bias
regime. It is depicted from Fig. 4 that the forward
current is increased exponentially with the applied
bias voltage. It is also examined that the current in

0.2 0.4 0.6 0.8 1.0 1.2

Forward bias voltage (V)
Fig. 5. Junction capacitance vs. forward bias voltage for the p-PbS/n-Si; PbS film grown at pH 10.25 and temperature 35 8C.
 R.K. Joshi et al./Applied Surface Science 221 (2004) 43-47
forward direction increases with a decrease in average
grain size. This phenomenon is very distinct in Fig. 4(a)
and (b), where (b) is of larger grain size as compared to
(a). The increase in forward current can be attributed to
the increase in surface area contact with reducing grain
size in the nanoparticle films [5].
The high frequency C—V measurements are carried
out on the heterojunctions at a frequency of 1 MHz.
Fig. 5 shows the typical plot of 1/C2 versus forward bias
voltage. It is clear from Fig. 5 that the junction capa-
citance for the heterojunction is increased with the
applied forward bias voltage. Linear fitting curve for
experimentally observed data points implies the forma-
tion of abrupt junctions [5] for these nanoparticle films.
Moreover, room temperature photovoltaic effect is
detected in the heterojunctions. Typical I-V character-
istics for two heterojunctions are shown in Fig. 4, where
the junction is illuminated by AM 1.5 sunlight from the
PbS film side. An open circuit voltage (Voc ~ 500 mV)
and short circuit current (Isc ~ 5 mA) are found in these
diodes.
4. Conclusions
In conclusion, we demonstrate a chemical bath
deposition method to fabricate the PbS nanoparticle
47
films. Crystalline PbS nanoparticle formation is exam-
ined by TEM and XRD investigations. Enhancement
of optical band gap with reducing grain size is observed
in the films. Hall measurements show a decrease
in carrier mobility and consequent decrease in con-
ductivity with reducing average grain size. Finally,
photovoltaic effect is exhibited in the p-PbS/n-Si
heterojunctions.
Acknowledgements
Authors are grateful to the scientists of Solid
State Physics Laboratory, Timarpur, Delhi, India
for receiving help in electrical and optical measure-
ments.
References
[1] S.B. Qadri, J. Yang, B.R. Ratna, F.E. Skelton, J.H. Hu, Appl.
Phys. Lett. 69 (1996) 2205.
[2] R. Thielsch, T. Bohme, R. Reiche, D. Schlafer, H.D. Bauer, H.
Bottcher, Nanostruct. Mater. 10 (1998) 131.
[3] Y. Wang, A. Suna, W. Mahler, R. Kawoski, J. Chem. Phys. 87
(1987) 7315.
[4] K.K. Nanda, S.N. Sahu, Appl. Phys. Lett. 79 (2001) 2743.
[5] R.L. Anderson, Solid-State Electron. 5 (1962) 341.