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.
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
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.
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 varied from 1.52 to 2.32 eV when the grain size
typical (ahn)2 versus hn plots for PbS nanoparticle film reduces form 23 to 12 nm.
grown at pH 9.75 and temperature 20 8C is shown in Resistivity and Hall measurements are performed at
Fig. 3. The optical band gap is observed to decrease room temperature on these samples. Resistivity of the
with increase in pH and temperature of the chemical films is found to be increased with decrease in grain
bath. It is evident from Table 1 that the band gap (Eg) is 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
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 acterized by I—V and C—V measurements. The I—V
grain size. Transport parameters for the nanoparticle characteristic for p-PbS/n-Si is shown in Fig. 4. From
films are given in Table 1. Hall mobility of PbS the I—V characteristic it is observed that the current in
nanoparticle films is also observed to be decreased forward bias regime is greater than that of reverse bias
with reducing grain size. regime. It is depicted from Fig. 4 that the forward
The heterojunctions between p-type nanoparticle current is increased exponentially with the applied
films and n-type Si substrate is fabricated and char- bias voltage. It is also examined that the current in
forward direction increases with a decrease in average films. Crystalline PbS nanoparticle formation is exam-
grain size. This phenomenon is very distinct in Fig. 4(a) ined by TEM and XRD investigations. Enhancement
and (b), where (b) is of larger grain size as compared to of optical band gap with reducing grain size is observed
(a). The increase in forward current can be attributed to in the films. Hall measurements show a decrease
the increase in surface area contact with reducing grain in carrier mobility and consequent decrease in con-
size in the nanoparticle films [5]. ductivity with reducing average grain size. Finally,
The high frequency C—V measurements are carried photovoltaic effect is exhibited in the p-PbS/n-Si
out on the heterojunctions at a frequency of 1 MHz. heterojunctions.
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 Acknowledgements
applied forward bias voltage. Linear fitting curve for
experimentally observed data points implies the forma- Authors are grateful to the scientists of Solid
tion of abrupt junctions [5] for these nanoparticle films. State Physics Laboratory, Timarpur, Delhi, India
Moreover, room temperature photovoltaic effect is for receiving help in electrical and optical measure-
detected in the heterojunctions. Typical I-V character- ments.
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) References
and short circuit current (Isc ~ 5 mA) are found in these
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