Current Applied Physics 12 (2012) 585e588

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Current Applied Physics

journal homepage: www.elsevier.com/locate/cap

Effect of excimer laser annealing on the properties of ZnO thin film prepared
by sol-gel method
Kyoungwon Kima, b, Sangsig Kimb, Sang Yeol Leec, *
a
Electronic Materials Center, Korea Institute of Science and Technology, Seoul 136-791, Republic of Korea
b
Department of Electrical Engineering, Korea University, Seoul 136-701, Republic of Korea
c
Department of Semiconductor Engineering, Cheongju University, Cheonju, Chungbuk, 360-764, Korea

a r t i c l e i n f o a b s t r a c t

Article history: Pristine ZnO thin films have been deposited with zinc acetate [Zn(CH3COO)2], mono-ethanolamine
Received 25 May 2011 (stabilizer), and isopropanol solutions by sol-gel method. After deposition, pristine ZnO thin films have
Received in revised form been irradiated by excimer laser (l ¼ 248, KrF) source with energy density of 50 mJ/cm2 for 30 sec. The
1 September 2011
effect of excimer laser annealing on the optical and structural properties of ZnO thin films are investigated
Accepted 6 September 2011
Available online 23 September 2011
by photoluminescence and field emission scanning electron microscope. As-grown ZnO thin films show
a huge peak of visible region and a wide full width at half maximum (FWHM) of UV region due to low
quality with amorphous ZnO thin films. After KrF excimer laser annealing, ZnO thin films show intense
Keywords:
ZnO
near-band-edge (NBE) emission and weak deep-level emission. The optically improved pristine ZnO thin
Excimer laser films have demonstrated that excimer laser annealing is novel treatment process at room temperature.
Laser annealing Ó 2011 Elsevier B.V. All rights reserved.

1. Introduction In order to deposit high-quality ZnO films, various synthesis

methods are researched including sputtering, spray pyrolysis, metal
ZnO, one of the most attractive semiconductor materials, has organic chemical vapor deposition and sol-gel [2]. The sol-gel
many novel properties due to a wide direct band gap energy (3.3 eV) method is very attractive with distinct potential advantages over
and large exciton binding energy (60 meV) at room temperature (RT) the other methods due to lower crystallization temperature, better
[1e3]. ZnO has potential application in electronics and optoelec- ability to tune the microstructure and large surface area coating
tronics including displays, sensors and solar cells [4]. To realize the capability [10]. However, the sol-gel process requires an annealing
high performance of ZnO optoelectronic device, one important step process for high-quality crystallization film. The great advantages of
is the control of UV/visible luminescence. Many researchers have laser annealing are strongly absorbed by laser radiation at low
reported the control methods of optical properties on UV/visible temperature [11]. Also, the process of laser annealing is a technique
luminescence including chemical reaction, plasma irradiation and of rapid crystallization that has the benefits of being area selective,
heat-treatment [5e7]. These treatments have disadvantages due to requiring no high temperature heating and results in minimal
high temperature and complex process. Therefore, improvement of disturbance to the surrounding area [12].
ZnO quality is very difficult and requires high product cost. Also, Recently, there are a few reports to explain effect of laser
applications of ZnO-based devices in photo-electronic field are very annealing on properties of ZnO thin films. In this work, the effects
limited. Aoki et al. firstly reported control method of single crystal of KrF excimer laser annealing on the optical and structural prop-
ZnO which is improvement of optical property by using excimer laser erties of two ZnO thin films grown by sol-gel method are
treatment instead of heat or complex treatments [8]. Also, Oh et al. investigated.
reported effect of laser treatment on electrical conductivity of ZnO
[9]. However, Aoki and Oh had limited experiment, because they
could control electrical and optical properties of ZnO materials. So, 2. Experimental
we use excimer laser annealing method on ZnO films for increasing
crystal and optical properties. 2.1. Prepared ZnO thin films by sol-gel process

Pristine ZnO thin films on Al2O3 (0001) substrates were

* Corresponding author. deposited by the sol-gel process with different coating speed. Zinc
E-mail address: lsy@kist.re.kr (S.Y. Lee). acetate (Zn(C2H3O2)2, Aldrich e 99.99%) was added in a mixed-

1567-1739/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cap.2011.09.006
586 K. Kim et al. / Current Applied Physics 12 (2012) 585e588

So, we can expose all area of our sample (1  1 cm2 size). Therefore,
we can easily control expose area of excimer laser around
10  10 cm2. And, density and intensity of excimer laser by diffuser
lens uniformly are exposed on the ZnO film. The surface morphology
of ZnO thin films was evaluated by the field emission scanning
electron microscope (FE-SEM) and the photoluminescence (PL). The
PL spectra were measured ranging from 270 to 850 nm by the
HeeCd laser (wavelength of 325 nm) at RT.

3. Results and discussion

Fig. 1 shows a schematic diagram of the sol-gel-based ZnO thin

film process. For depositing ZnO thin films, there are three steps
which are sol-gel, thin film coating and laser treatment. The sol-gel
method is simple and efficient to deposit oxide thin films. It can be
ensured to control the film thickness by managing the rotation
speed, the coating times and the solution viscosity [14]. Fig. 2 shows
tilted top-view SEM images of ZnO thin films with zinc acetate
mixed-solution of 1 mol (zinc acetate:MEA ¼ 1:1 (mol%)) deposited
on sapphire substrate by spin coating at 1000 rpm with/without KrF
excimer laser annealing for crystallization. The SEM is used to
investigate the morphology change including surface roughness and
Fig. 1. A schematic diagram of the sol-gel-based ZnO thin film process. There are three uniformity. After KrF excimer laser annealing on the as-grown ZnO
steps to deposit ZnO thin films including sol-gel, thin films and treatment process. thin films at RT, this sample shows rough and non-uniform surface
morphology compared with initial ZnO thin film, as shown in Fig. 2.
In other words, the KrF excimer laser annealing can change surface
solution of isopropanol ((CH3)2CHOH, Dongwoo chemical e 99.9%) morphology and flatness of the ZnO film. Because, the grain
and ethanolamine (H2NCH2CH2OH, Aldrich e 99%, MEA) [13]. The boundary is partially melted by KrF excimer laser annealing and
molar ratio between MEA and zinc acetate was maintained to 1, then extend into the grains. Therefore, ZnO thin films by KrF excimer
where the amount of zinc acetate was adjusted to 1 mol. The laser annealing become the crystallization. It is indicated that the
mixture was stirred at 60  C for 1 h and then aged at RT for 24 h to structural property of the thin film depends on KrF excimer laser
yield a homogeneous solution. The ZnO thin films were prepared by annealing. Also, the surface morphology of the thin film affects the
spin coating process with aged solution on the sapphire substrate electrical and optical properties of the thin film [15].
with the rotation speed ranging from 1000 rpm to 3000 rpm for The PL spectrum of ZnO thin films shows a strong emission
30 s. And, ZnO thin films were dried on a hotplate at 60  C for centered at about 380 nm caused by free-exciton emission, as shown
30 min. The reason for intermediate excimer laser treatment on the in Fig. 3 [16]. This means 380 nm peak is commonly attributed to the
hotplate is for the condensation of the prepared sol as well as the direct recombination of excitons through an excitoneexciton colli-
surface smoothing of the gel. sion process. It is known that pristine ZnO shows green and orange
visible luminescence depending on the growth temperature and
2.2. KrF excimer laser annealing and analysis availability of oxygen during sample preparation. However, as-
grown ZnO thin film shows strong and broad blue-green emission
The average thicknesses of as-grown ZnO thin films were about peak centered at around 490 nm, as shown in Fig. 3(a). The blue-
200 nm with different spin coating speed [2]. During laser anneal- band emission is peak of intrinsic defects due to O and Zn vacan-
ing, ZnO thin films were irradiated with a KrF excimer laser cies or interstitials in ZnO thin film [17], and the green-band emis-
(wavelength 248 nm). The energy density and repetition rate of the sion is associated from the optical transition in the single-ionized
laser were adjusted to 50 mJ/cm2 and 10 Hz, respectively. The oxygen vacancy (Vþ O ) [18]. From the results, as-grown ZnO thin films
treatment time of excimer laser is 30 s. In order to expand exposure are low quality films because of many defect sites including O and Zn
area of excimer laser, we used diffuser lens in front of our samples. vacancies or interstitials. After KrF excimer laser annealing, the ZnO

Fig. 2. The top-view SEM images of ZnO thin films with zinc acetate of 1 mol (zinc acetate:MEA ¼ 1:1 (mol%)) deposited on sapphire substrate by spin coating at 1000 (a) with and
(b) without KrF excimer laser annealing for crystallization.
 K. Kim et al. / Current Applied Physics 12 (2012) 585e588 587

a as-grown b after annealing

PL intensity (a.u.)

PL intensity (a.u.)
200 300 400 500 600 700 800 900 200 300 400 500 600 700 800 900
Wavelength Wavelength
Fig. 3. The PL spectrums of sol-gel processed ZnO thin film by spin coating at 1000 rpm (a) without and (b) with KrF excimer laser annealing. After KrF excimer laser annealing ZnO
thin film, blue-green emission is decreased, because intrinsic defects such as O and Zn vacancies or interstitials are removed or filled.

a b
as-grown after annealing
PL Intensity (a.u.)

PL Intensity (a.u.)

200 300 400 500 600 700 800 900 200 300 400 500 600 700 800 900
Wavelength Wavelength

Fig. 4. The PL spectrums of sol-gel processed ZnO thin films at 3000 rpm spin coating speed (a) without laser annealing and (b) with laser annealing treatment measured at RT.

a b
As-grown After annealing
1000 rpm 1000 rpm
Intensity (a.b.)

Intensity (a.b.)

(002)

10 20 30 40 50 60 70 80 90 100 10 20 30 40 50 60 70 80 90 100
2 θ (deg.) 2 θ (deg.)
c d
As-grown After annealing
3000 rpm 3000 rpm
Intensity (a.b.)
Intensity (a.b.)

(002)

10 20 30 40 50 60 70 80 90 100 10 20 30 40 50 60 70 80 90 100
2 θ (deg.) 2 θ (deg.)
Fig. 5. X-ray diffraction patterns of ZnO thin films with and without excimer laser annealing method. The spin coating speed of (a) and (b) is 1000 rpm, and the spin coating speed
of (c) and (d) is 3000 rpm.
588 K. Kim et al. / Current Applied Physics 12 (2012) 585e588

thin films are improved on optical property due to both reduced interstitials. However, the blue-green emission of ZnO thin films by
peak of the visible region and narrow full width at half maximum KrF excimer laser annealing is decreased because intrinsic defects
(FWHM) of UV region, as shown in Fig. 3(b). Especially, blue emis- such as O and Zn vacancies or interstitials are removed or filled.
sion, located at about 3.26 eV, of ZnO thin film by excimer laser Finally, the KrF excimer laser annealing is good treatment process
annealing strongly is decreased. It means that intrinsic defects, such to increase the crystal quality or to change the PL intensity of ZnO
as O and Zn vacancies or interstitials are removed or filled. Winfield thin films. Also, it is very important to note that KrF excimer laser
et al. reported that the optical properties of ZnO thin film by sol-gel annealing is good candidate of low temperature process for the
method were changed by the KrF excimer laser irradiation, which is application of flexible devices.
attributed to the deterioration in the crystalline of the ZnO [19].
Wang et al. investigated the same results by Mg-doped GaN thin
films with after laser annealing [20]. From the results, a KrF excimer Acknowledgments
laser annealing can increase the crystal quality or change the PL
intensity of ZnO thin films. Musat et al. reported that crystal quality This research was supported by a grant (code #: 2011K000208)
of prepared ZnO films by sol-gel method depends on coating speed Center for Nanostructured Materials Technology’ under ‘21st
due to different grain size, grain boundary and surface morphology Century Frontier R&D Programs’ of the Ministry of Education,
[21]. Therefore, ZnO film of 3000 rpm has low intensity of visible Science and Technology, Korea, as well as by the System Integrated
region compared with 1000 rpm speed sample, as shown in Fig. 4. Semiconductor Base Technology Development Program funded
Fig. 4 shows the PL spectrums (a) without laser annealing and (b) from the Ministry of Knowledge and Economy (MKE), South Korea.
with laser annealing treatment measured at RT with 3000 spin
coating speed. It is also obvious that the blue-green emission located
at about 490 nm is decreased by KrF excimer laser annealing, References
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