Pt>i_xFexS nanoparticle films grown from acidic chemical bath

Rakesh K. Joshi*, G.V. Subbaraju, Renu Sharma, H.K. Sehgal

Department of Physics, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India
Received in revised form 16 September 2003; accepted 26 March 2004

Abstract

Pbi_xFexS (x — 0:25, 0.50, 0.75) films were grown from an acidic chemical bath. Nanoparticle films were structurally
characterized by XRD and TEM. Optical band gap of films is observed to vary from 1.65 to 1.42 eV with increase in their iron
concentration from x — 0:25 to 0.75 in the films. Increased optical band gap of the ternary films compared to the estimated bulk
value is attributed to quantum confinement in the nanocrystals deposited on solid substrates.

PACS: 81.05.Hd; 81.05.Ys; 81.10.Dn

Keywords: Ternary films; Solution growth

1. Introduction mical bath for the growth of semiconductors films [2].

Growth of semiconductor nanocrystals on solid
substrates is an emerging field of research to study
the utility of a material in different technological
applications. Several chemical methods have been
reported for fabrication of nanostructured thin films.
In chemical methods the growth of particles on sub-
strates depends on dilution, pH and temperature of the
chemical bath and it is also known to depend on the
complexing agent used to control the growth of par-
ticles [1]. It is reported that the preparation of semi-
conductor thin films by chemical bath deposition in
basic medium is based on utilization of ammonia as
complexing agent for metal ions. Potassium or sodium
hydroxides are also used to increase pH of the che-
We have also reported the growth of ternary Pb1 _xFexS
nanopaticle films using a chemical bath with pH > 9:5
[3]. Recently it is reported that the CdS nanocrystals
can be grown from an ammonia-free alkaline chemical
bath using nitrilotriacetic acid as a complexing agent
for the Cd ions, which eliminates the problem of
ammonia volatility and toxicity [2]. Therefore, in this
context we made an attempt to grow nanoparticle thin
films of ternary semiconductors without using an
alkaline bath. In this paper we present, for the first
time, synthesis of nanoparticle films of Pbj_xFexS
from an acidic chemical bath with ethylenediamine
tetraacetic acid (EDTA) as complexing agent. Critical
control of temperature and dilution of the bath are
found necessary to achieve nanocrystallinity in the
films. This method appears relatively easier than
methods reported for the other semiconductor nano-
particle films. Structural and optical properties of the
nanoparticle films grown from acidic chemical bath
are discussed in this paper.
 ARTICLE IN PRESS
R.K. Joshi et al. /Applied Surface Science xxx (2004) xxx-xxx

2. Experimental

The films were grown on glass and quartz substrates

using M/25 lead acetate, M/20 thiourea and M/25
ferrous chloride aqueous solutions. These concentra-
tions were observed to be appropriate for growth of
homogeneous films. Lead acetate and thiourea were
mixed in equal proportions and an appropriate quan-
tity of FeCl2 was used to obtain x = 0:25, 0.50, 0.75 in
the films. EDTA, used as complexing agent for the
metal ions, was mixed so as to achieve pH of 6.0
(±0.1) of the bath solution. Cleaned glass, quartz and uo so
silicon substrates were suspended vertically in the 26(deg.)
solution and the temperature of the bath was main- Fig. 1. XRD traces for Pb^Fe^S nanoparticle films: (a) x = 0:25,
tained at 70 8C (±0.5 8C). The solution was stirred (b) x = 0:50, and (c) x = 0:75.
continuously during growth. Growth of films proceeds
due to thermally generated S2~ ions in the solution that of Pb 2 þ ions (1.20 A). Observed increase in peak
bath. Presence of EDTA provides better adhesion and broadening in the XRD traces with increase in iron
quality to the films. Deposition times were optimized concentrations (x) in the films indicates decrease in
to get film thickness of —70 nm for all values of x. particle size in the films. Average grain sizes estimated
Maximum thickness limit of the films obtained from a from peak broadening using Scherer equation [4] are
single growth step is observed to be less (—90 nm) observed to be 30, 24 and 21 nm in the x of 0.25, 0.50,
from the pH of 6.0 acidic bath as compared to those 0.75 Pbj_xFexS films respectively. Average grain sizes
(—250 nm) from pH of >9.5 from the alkaline bath. in the films estimated by TEM (33, 26 and 24 nm in
This could possibly be due to slow release of metal the x of 0.25, 0.50 and 0.75 Pb^Fe^S films respec-
ions from the EDTA complex. Compositions of films tively) agree well with those computed from XRD
were estimated from X-ray fluorescence spectroscopy data. Typical bright-field image of the PVTEM taken
data. Films were structurally characterized by glan-
cing angle X-ray diffraction. Average grain size in
each film was estimated by transmission electron
microscope (TEM) in plane-view (PVTEM) mode,
using Philips CM20 instrument operating at 200 keV.
Optical transmittance (T) and reflectance (R) of the
films were measured by UV-Vis-NIR spectrophot-
ometer. *

3. Results and discussion

I
Analysis of the XRD data from the films indicates
the presence of a single-phase ternary alloy of the type
Pb!_xFexS in the films. Fig. 1 shows X-ray diffraction
(XRD) trace for the Pb^Fe^S (x = 0:25, 0.50, 0.75)
films. All XRD peaks are observed to shift towards
higher value of y resulting from the smaller lattice
parameters for films with higher iron concentrations.
Decrease in lattice parameter with x attributed to the
f
smaller ionic radii of Fe 2 þ (0.74 A) in comparison to Fig. 2. TEM micrograph for Pb0.5Fe0.5S nanoparticle film.
 ARTICLE IN PRESS
R.K. Joshi et al. /Applied Surface Science xxx (2004) xxx-xxx

with the electron beam direction close to the (1 10)-
zone axis in a strongly underfocused conditions for
films with iron concentration x = 0 : 50 is shown in
Fig. 2.
Optical transmittance (T) and reflectance (R) of the
films measured by UV-Vis-NIR spectrophotometer
were used to estimate the absorption coefficient a
(cm ) for the films. Fig. 3a shows the typical varia-
tion of reflectance and transmittance with wavelength
n
for the Pb0.75Fe0.25S films. (ahn) versus hn plots for
n = 2, 1/2, and 1/3 show linear behavior for n = 2,
only indicating presence of direct optical band gaps in
2
films with all x. Fig. 3b shows hn versus (ahn) plots
for the x of 0.25, 0.50, 0.75 Pb^Fe^S films. Optical

50 i . i I . I .

40
J Reflectance (R)

J •
Transmittance (T)
30
08 •
•• ;

20 • -
• ^ •
•
• • n. •
f
10 .•• •• ^ -
** •
•
•
0
500 1000 1500 2000250030 2500 3000
(a) Wavelength(nm)

1.0x10

0.0
01.5 2.0 2.5 3.0 2.5 3.0 3.5 4.0
(b) hν(eV)
Fig. 3. (a) Reflectance and transmittance vs. wavelength for Pb0.75Fe0.25S nanoparticle films. (b) hn vs. (ahn)2 plot for the Pb1_J.FeIS
nanoparticle films: (&) x = 0 : 25; ( * ) x = 0:50; ( * ) x = 0:75.
 ARTICLE IN PRESS
R.K. Joshi et al. /Applied Surface Science xxx (2004) xxx-xxx
band gap EgN of Pbi_xFexS nanoparticle films was
observed to decrease with an increase in iron concen-
tration x in the films. Values of E gN for the x of 0.25,
0.50 and 0.75 films are observed to be 1.65, 1.51 and
1.42 eV respectively. Decrease in optical band gap
of the ternary alloys with increase in iron concentra-
tion suggests alloying between FeS nanoparticles
(bulk Eg = 0:04 eV [5]) with PbS nanoparticles (bulk
Eg = 0:41 eV; 2 nm average grain size Eg = 5:4 eV
[6]) to form the ternary Pbj_xFexS nanoparticles. The
larger optical band gap in the Pbj_xFexS nanoparticle
films, like that reported for PbS nanoparticles [7-9]
and CdSe, CdS, ZnSe, and ZnS nanoparticles [10], is
attributed to the quantum confinement effect [10,11].
The ratio EgN/Eg, which suggests the extent of quan-
tum size effect, is observed to increase with increase in
iron concentration (x) in the nanoparticle films. The
particle size effect on optical band gap is observed to
be more pronounced in the ternary Pbj_xFexS nano-
particle films in comparison to that reported for the
PbS nanoparticle films with same crystallite size. A
band gap of E gN 1.4 eV reported from electrodepos-
ited PbS nanoparticles (24 nm) [8] is 3.4 times the
band gap of bulk PbS (0.41 eV), whereas 24 nm
average grain size (estimated by TEM) Pb0.25Fe0.75S
films have an E gN of 1.42 eV which is 10.31 times the
estimated bulk value (using Vegard's law) of 0.137 eV.
The experimental data from PbS nanoparticle films [8]
interpreted on the basis of hyperbolic band model
[7,11] using the expression
,2,., .2 , 2h2Eg(n/r)2
ml
(where Eg is the band gap of for the bulk semicon-
ductor, r the particle radius and m* the effective mass
of electron) gives m*/me value of 5:8 x 10~4 (using
EgðrÞ = 1:4 eVand r = 24 nm). The same model used
for Pb0.25Fe0.75S nanoparticle films gives the value of
ml/me of 1:7 x 10~4. This extremely low values of
ml/me could possibly be due to nonparabolicity of the
conduction band, finite value of the barrier potential
and difference between electron masses inside and
outside the nanocrystals [12-14].
(ahn)2 versus hn curves in Fig. 3b do not show a
normal Urbach tail on the lower energy side of the
absorption threshold. The absorption band whose
intensity increases with increase in iron concentration
in the films just next to the absorption threshold on the
lower energy side is possibly due to excitons in the
nanocrystals. Excitons have also been reported from
CdSe [15], CdS, ZnSe and ZnS nanocrystallites [9].
4. Conclusions
In summary, Pb^Fe^S (x = 0:25, 0.50, 0.75) films
have been successfully grown from an acidic chemical
bath. Optical band gap E gN of films can be varied from
1.65 to 1.42 eV with increase in iron concentration
from x = 0:25-0.75 in the films. Increase in optical
band gap of the ternary films is attributed to quantum
confinement in the nanocrystals.
Acknowledgements
Authors are grateful to Dr. Aloke Kanjilal of
Department of Physics and Astronomy, University
of Aarhus, Denmark, for the TEM measurements.
References
[1] P. Nemec, I. Nemec, P. Nahalkova, K. Knieek, P. Maly, J.
Cryst. Growth 240 (2002) 484.
[2] M.B. Ortuno Lopez, J.J. Valenzuela-Jauregui, M. Sotelo-
Lerma, A. Mendoza-Galvan, R. Ramirez-Bon, Thin solid
Film 403/404 (2002) 9.
[3] R.K. Joshi, H.K. Sehgal, J. Cryst. Growth 247 (2003) 425.
[4] B.D. Cullity, Elements of X-ray Diffraction, Addison-Wesley,
1967.
[5] J.R. Gosselin, M.G. Townsend, R.J. Trembly, Solid State
Commun. 19 (1976) 799.
[6] R. Thielsch, T. Bohme, R. Reiche, D. Schlafer, H.D. Bauer,
H. Bottcher. Nanostruct. Mater. 10 (1998) 131.
[7] K.K. Nanda, F.E. Kruis, H. Fissan, M. Acet, J. Appl. Phys. 91
(2002) 2315.
[8] K.K. Nanda, S.N. Sahu, Appl. Phys. Lett. 79 (2001) 2743.
[9] R.K. Joshi, A. Kanjilal, H.K. Sehgal, Appl. Surface Sci. 221
(2004) 43.
[10] N. Chestnoy, R. Hull, L.E. Brus, J. Chem. Phys. 85 (1986)
2237.
[11] Y. Wang, A. Suna, W Mahler, R. Kawoski, J. Chem. Phys. 87
(1987) 7315.
[12] Y. Kayanumma, Momiji, Phys. Rev. B 41 (1990) 10261.
[13] D.B. Tran Thoai, Y.Z. Hu, S.W. Koch, Phys. Rev. B 42 (1990)
11261.
[14] P. Lavallard, J. Cryst. Growth 184 (1998) 352.
[15] P.E. Lippens, M. Lannoo, Phys. Rev. B 41 (1990) 6079.