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Thin Solid Films 516 (2008) 8702 – 8706

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Temperature dependent photoluminescence characteristics of nanocrystalline

ZnO films grown by sol–gel technique
S. Mandal, M.L.N. Goswami, K. Das, A. Dhar, S.K. Ray⁎
Department of Physics and Meteorology, IIT Kharagpur 721 302, India
Received 30 April 2007; received in revised form 11 March 2008; accepted 15 May 2008
Available online 22 May 2008

Abstract

The structural as well as optical properties of nanocrystalline ZnO films, with hexagonal shaped particles of size 30–35 nm grown on p-Si
(100) substrates by sol–gel technique, are investigated. Selected-area electron diffraction and X-ray diffraction patterns of annealed films reveal
the formation of wurtzite structure. The mechanism of ultraviolet (UV) and green emission from ZnO thin films, post-annealed at various
temperatures, is investigated using photoluminescence spectra. The oxygen content in annealed ZnO films plays an important role to suppress the
green band emission. Temperature dependent photoluminescence spectra are recorded in the temperature range 10 K to 300 K to investigate
different excitonic peaks in the UV-region.
© 2008 Elsevier B.V. All rights reserved.

Keywords: ZnO; sol–gel synthesis; Photoluminescence; X-ray diffraction

1. Introduction Stoichiometric zinc oxide is an insulator with the wurtzite

structure. The structure contains large voids, which can easily
Zinc oxide, an II–VI semiconductor with a wide direct band accommodate interstitial atoms. Consequently, it is virtually
gap of 3.3 eV and large exciton binding energy of ~ 60 meV at impossible to prepare pure crystals; also, they tend to lose
room temperature [1], is especially attractive for optoelectronic, oxygen when heated to a very high temperature [14]. For these
nonlinear optics and electro-optics [2] applications. ZnO based reasons, ZnO exhibits n-type semiconducting properties with
films have been used for several applications in transparent inherent defects, such as the lack of O and the excess of Zn. In
conductive layer, solar cell windows, and bulk acoustic wave this regard, the study of the photoluminescence (PL) character-
devices [3–6]. The optical properties of ZnO make it one of the istics of ZnO is interesting because it can provide valuable
most promising materials for photonic devices in the ultraviolet information on the quality and purity of the materials. Moreover
(UV) range. Moreover, the binding energy of the exciton of the low temperature PL study also shows the interactions of the
ZnO (60 meV) is larger than its competitor GaN (25 meV) at nano-confined trapping states and lattice sub-systems [15]. It is
room temperature making it attractive [7–9] for exciton-related well agreed that the UV emission of ZnO is attributed to the
device applications. Several techniques have been used to exciton emission originating from the recombination of free
fabricate ZnO films, including chemical vapor deposition [10], excitations through an exciton–exciton collision process
molecular beam epitaxy [11], sputtering [12], pulsed laser [16,17], while the mechanism of the blue-green emission re-
deposition [8] and sol–gel technique [13]. Of these techniques, lates to the oxygen vacancy or Zn interstitials [18,19]. It has
the sol–gel route is very attractive with excellent control over been reported that the singly ionized oxygen vacancy is res-
composition and relatively easier fabrication of a large area film ponsible for the green emission, since the emission results from
at a low cost. the recombination of a photo generated hole with the singly
charged oxygen vacancy [18]. These oxygen vacancies have
⁎ Corresponding author. comparatively low formation enthalpy [19] and are dependent
E-mail address: [email protected] (S.K. Ray). on the oxygen deficiency in the film.
0040-6090/$ - see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2008.05.016
 S. Mandal et al. / Thin Solid Films 516 (2008) 8702–8706 8703

There are several reports [16–22] on photoluminescence resulting in an improvement in the quality and crystallinity of
characteristics of bulk and nanocrystalline ZnO films grown by the films.
different techniques. However, only a few reports [23,24] are Typical TEM micrograph of nanocrystalline ZnO film
available on the temperature dependent photoluminescence annealed at 600 °C and the corresponding selected-area electron
characteristics of sol–gel derived nanocrystalline ZnO films. diffraction (SAED) pattern are presented in Fig. 2(a) and (b),
Reported results discussed the behavior of different excitonic respectively. The micrograph shows particles are homoge-
peaks as well as longitudinal optical (LO) phonon replicas in the neously spaced with narrow size distribution varying within the
UV-region. In this paper, we report the growth and optical range 30–35 nm. The porosity level is approximately 15–20%
characteristics of nanocrystalline ZnO films on p-Si (100) sub- (from the TEM image). The SAED pattern exhibits all the
strates deposited by sol–gel technique. The effect of post- diffraction rings corresponding to wurtzite structure of ZnO,
deposition annealing treatment on the mechanism of UV and corroborating the XRD results.
green emissions of nanocrystalline ZnO thin films are studied. For the film annealed at 600 °C, we have found out the
Temperature dependent photoluminescence spectra of the films crystallite size from the XRD results. In order to distinguish the
have also been investigated. contribution of crystallite size-induced and strain-induced
broadening of XRD peaks, the Williamson–Hall plot [25] is
2. Experimental details presented in Fig. 3. The crystallite size and micro-strain can be
obtained from the intercept at the y-axis and the slope of the
Zinc acetate dihydrate (Zn(CH3COO)2, 2H2O) and 2-propanol plot, respectively, which is represented by
were chosen as starting materials to coat ZnO films on p-Si (100)
Ck
substrates by sol–gel method. Initially, zinc acetate was dissolved b cos h ¼ þ 2e sin h ð1Þ
into 2-propanol. Since zinc acetate has low solubility in 2- d
propanol, diethanolamine (DEA) was added to obtain a trans- where β is the full width at half maxima of XRD peak, d is the
parent solution and to keep the solution stable. The particle size crystallite size, ε is the micro-strain, λ is the X-ray wavelength,
depends on the molar quantity of zinc acetate and diethanolamine and C is a correction factor taken as 0.89. The extracted crys-
(DEA). The molar ratio of zinc acetate and diethanolamine (DEA) tallite size from the XRD spectrum of the ZnO film is 35 ± 5 nm,
was maintained at 1:2. The solution was stirred at a constant in agreement with the TEM results and the micro-strain is about
temperature of 65 °C for 1 h followed by aging for about half an 1.19 × 10− 3, which is very small in the film annealed at 600 °C.
hour to make it cool and stable. Multilayer films were deposited
on p-Si substrates by spin coating method with a spin coating
speed of 2500 rpm for 5 times. After each coating, the films were 3.2. Photoluminescence characteristics
dried at 250 °C for 5 min. The films thus formed were annealed at
different temperatures in oxygen environment. The thickness of Photoluminescence (PL) is an important property, which
the film is 150 ± 10 nm. The properties of ZnO films annealed at provides information on the optically active defects and
an optimized temperature of 600 °C were studied in detail. The relaxation pathways of excited states. The study is useful to
microstructure and morphology of ZnO films were characterized identify the origin of sub-band-gap luminescence. Fig. 4 shows
by an X-ray diffractometer (Philips X-Pert MRD) using CuKα room temperature photoluminescence spectra of as-grown and
radiation of wavelength 1.5418 Å at grazing incidence mode and a annealed ZnO thin films. With the increase of annealing tempe-
transmission electron microscope (TEM) operated at 200 kV. rature up to 600 °C, the intensity of UV (3.389–3.271 eV) to
Photoluminescence in the temperature ranging from 10–300 K
was measured using a He–Cd laser as an excitation source,
operating at 325 nm with an output power of 50 mW and TRIAX
320 monochromator fitted with a cooled Hamamatsu R928
photomultiplier detector.

3. Results and discussion

3.1. Microstructural properties

Fig. 1 shows the intensity versus 2θ X-ray diffraction (XRD)

pattern of nanocrystalline ZnO film prepared by sol–gel
technique annealed at different temperatures. As indexed in
the figure, all diffraction peaks are attributed to the wurtzite
structure of ZnO. The as deposited film shows amorphous
nature and after annealing, the samples develop different dif-
fraction peaks of ZnO. The intensity of all diffraction peaks
increases at higher annealing temperature, because higher tem- Fig. 1. Grazing incidence XRD pattern of ZnO film of (a) as deposited and
perature provides more energy to enhance the adatom mobility annealed at (b) 450 °C, (c) 600 °C, (d) 750 °C.
8704 S. Mandal et al. / Thin Solid Films 516 (2008) 8702–8706

Fig. 2. (a) TEM images of a grown ZnO film annealed at 600 °C. The figure in the inset shows a magnified micrograph. (b) Selected-area electron diffraction (SAED)
pattern for the ZnO film annealed at 600 °C.

green emissions (2.52–2.36 eV) of ZnO films is increased, but temperature of 600 °C. PL spectrum of nanocrystalline ZnO
the intensity ratio decreases at a temperature of 750 °C. The film annealed at 600C °C recorded in the temperature range
variation of intensity ratio with post-deposition annealing tem- from 10 K to 300 K in the energy region 2.95–3.55 eV is plotted
perature is presented in the inset of Fig. 4. It has been reported in Fig. 5. The shrinkage of band gap as well as a redshift of near
earlier that the intensity of green emission becomes stronger on band-edge (UV) emission is evident on increasing the tem-
post annealing treatment at 800 °C in oxygen ambient for 1 h, perature. Fine structures of the UV emission are revealed in the
but annealing at low temperatures results in the suppression of temperature range 10 K to 150 K. To identify the origin of PL
green emission [26]. In our case, the green emission gradually emission, the broad band in the region 2.95–3.55 eV has been
decreases with an increase in temperature and minimum at fitted using six different peaks. Fig. 6 shows the best fitting
600 °C. It may be noted that UV emission is not related with the results of PL band at 10 K for the nanocrystalline ZnO film. The
defect states and a post-deposition annealing is essential to peak at 3.360 eV, which exists throughout the studied tem-
suppress the green band emission, which may appear due to perature, is attributed to free exciton (FX) recombination. Our
zinc interstitial or oxygen vacancy defect states. result is in agreement with the observation of free exciton peak
To study the near band edge emission in the UV-region, at low temperatures for ZnO nanorods [27], nanoparticles [28],
hereafter we present PL characteristics of the sample annealed at and ZnO nanocrystalline films [29]. The free exciton transition
600 °C, with minimum defect state emission. We have under- for the nanocrystalline ZnO films at 10 K, which is generally not
taken a temperature dependent PL study to have more insight on
the origin of emission from the sample annealed at an optimized

Fig. 4. Room temperature photoluminescence of ZnO films of (a) as deposited

Fig. 3. Williamson–Hall plot of the ZnO film annealed at 600 °C. The error bars and annealed at (b) 450 °C, (c) 600 °C, (d) 750 °C. The inset shows the variation
represent the contribution of the experimental measurement error on evaluation of intensity ratio of ultraviolet (IUV) and green (Igreen) emission with the
of β cosθ. annealing temperature.
 S. Mandal et al. / Thin Solid Films 516 (2008) 8702–8706 8705

assisted transitions located at 3.248 eV, 3.176 eV, 3.109 eV and

3.037 eV are assigned to FX-BX-1LO, FX-BX-2LO, FX-BX-
3LO and FX-BX-4LO emissions, respectively.
Fig. 7 shows the temperature dependent energies of the
different peak positions. Both FX and BX emissions system-
atically shift to lower energy with increasing temperature. The
numerical fittings of free exciton energy (EFX) vs. temperature
data have been reported by several researchers invoking either
Varshni's model [34]:

aT 2
EFX ðT Þ ¼ EFX ð0Þ þ ð2Þ
T þb
representing the limiting regimes of either extremely large
dispersion (Δ ~ 1) or completely vanishing dispersion (Δ ~ 0),
respectively. The α and β are constants in Eq. (2). In our case
the studied temperature range (10–300 K) is significantly less
Fig. 5. Temperature dependent photoluminescence spectrum of ZnO film
annealed at 600 °C. than the reported Debye temperature of ZnO (θD = 920 K [35]),
for which Varshni's equation is not satisfactory [36]. The
temperature dependent free excitonic peak position from our PL
noticed in bulk, indicates a good optical quality of our films. data is fitted with the model predicted by Manoogian and
Another near band edge emission line is observed at 3.318 eV Woolley [37], for groups II–VI semiconductors:
accompanied by four different phonon replicas at 3.248 eV,    
3.177 eV, 3.099 eV and 3.027 eV at 10 K. The energy difference h
EFX ðT Þ ¼ EFX ð0Þ þ UT þ V h coth
S
1 ð3Þ
between the two peaks (3.318 and 3.248 eV) is very close to that 2T
of LO-phonon of ZnO [30] around 72 meV. The peak at
3.318 eV, the most dominant peak at low temperature range where S is the exponent, V the temperature gradient, θ the tem-
(10–150 K) is assigned to the bound exciton (BX) recombina- perature coefficient and U ≈ −3B(∂Eg/∂P)bαLN, where B is the
tion, because the difference between 3.360 and 3.318 eV is close bulk modulus, (∂Eg/∂P) is the band gap pressure coefficient, and
to the activation energy of BX, in consistent with the reported bαLN is the mean thermal expansion coefficient. In the above
value [31,32]. On increasing the temperature (above 150 K), the equation, the first term represents the free exciton energy at 0 K,
emission peak 3.318 eV and its corresponding replicas dis- the second term the lattice dilatation and the electron–phonon
appear. It may be noted that the thermal energy at room interaction is represented by the third term. By fitting the tem-
temperature is enough to release a BX, because its binding perature dependent free exciton PL peak data with Eq. (3), as
energy is only a few meV [33]. Therefore, we conclude that the shown in Fig. 7, we estimated the following parameters: EFX
emission peaks at 3.360 eV, 3.318 eV are originated from the FX (0 K) = 3.362 eV, U = − 5.3 × 10 − 5 eVK − 1 , S = 1.15, V =
emission and the BX emission, respectively. The phonon-

Fig. 7. Temperature dependence of different PL peak positions. The solid line

denotes the theoretical simulation for temperature dependent FX peak position
Fig. 6. The best fitting results of PL band at 10 K for the nanocrystalline ZnO with the model predicted by Manoogian and Woolley. The error bars represent
film annealed at 600 °C. the contribution of the experimental measurement error on the peak position.
8706 S. Mandal et al. / Thin Solid Films 516 (2008) 8702–8706

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