Jpn. J. Appl. Phys. Vol. 40 (2001) pp.

6296–6303
Part 1, No. 11, November 2001

2001
c The Japan Society of Applied Physics

Morphology, Structure and Photoluminescence Properties of Zinc Oxide Films

Prepared by Excimer Laser Irradiation of Sol–Gel-Derived Precursors
Toshimi NAGASE, Toshihiko O OIE, Yoji M AKITA, Shuji K ASAISHI,
Masahiro NAKATSUKA1 and Nobuyasu M IZUTANI2
Marine Resources and Environment Institute, National Institute of Advanced Industrial Science and Technology (AIST),
2217-14 Hayashi-cho, Takamatsu, Kagawa 761-0395, Japan
1 Institute of Laser Engineering, Osaka University, 2-6 Yamada-oka, Suita, Osaka 565-0871, Japan
2 Department of Metallurgy and Ceramics Science, Graduate School of Science and Engineering, Tokyo Institute of Technology,

2-12-1 Ookayama, Meguro-ku, Tokyo 152-8552, Japan

(Received April 5, 2001; accepted for publication August 10, 2001)

Morphology, structure and photoluminescence (PL) properties of zinc oxide (ZnO) films prepared by KrF-excimer-laser irra-
diation of sol–gel-derived precursors were studied. The precursors with a film thickness of 100 or 180 nm were irradiated by
the laser at various energy fluences (Ef ). Atomic force microscopy and transmission electron microscopy observations revealed
that the laser irradiation at an Ef ≥ 100 mJ/cm2 produced crystal growth of close-packed ZnO crystals in an upper layer. Laser
irradiation at a high Ef (150 mJ/cm2 ) of the thinner precursor produced a remarkable crystallization throughout the film, result-
ing in larger grain size and smooth film surface. Our observation results suggest that the crystallization proceeds by sintering
or solidification via melting. The films obtained at Ef ≥ 100 mJ/cm2 showed green PL. The PL spectra were not significantly
influenced by the excitation wavelength except for the thinner film irradiated at a high Ef (150 mJ/cm2 ); it showed a striking
increase in the green PL intensity when excited at 275 nm instead of 325 nm. The unique excitation-wavelength dependence
may be related to its characteristic threshold of electron excitation.
KEYWORDS: zinc oxide films, excimer laser irradiation, sol–gel method, morphology, crystal growth, green photoluminescence

1. Introduction very important to investigate the free-carrier concentration,

structure and morphology of the prepared ZnO films.
Zinc oxide (ZnO) is a semiconductor with a wide band
We have successfully prepared novel crystalline ZnO
gap of 3.3 eV, showing attractive optical and electrical prop-
films15) by a method involving KrF excimer laser irradiation
erties. Recently, luminescent ZnO films have been vigorously
of sol–gel-derived precursors. Using this method, a green PL
studied owing to their potential application to low-voltage
ZnO film has been first obtained in air within a short irra-
field emission displays (FEDs),1–11) ultraviolet diode lasers,12)
diation time at a low substrate temperature of 473 K.5) This
and optoelectronic devices.13, 14) In particular, the low-voltage
method is easy, economical and attractive; in addition, it has
FEDs hold great promise for displays requiring high contrast,
the potential for large-area deposition, and for the use of desir-
a wide viewing angle and low power consumption. Green
able but low-thermostable substrates such as polymers. The
luminescent ZnO has attracted attention as a promising phos-
method has a further merit in that the laser beam permits the
phor for low-voltage FEDs, since ZnO powders are known to
easy local manipulation of film characteristics using appro-
show high luminescence efficiency in low-voltage cathodelu-
priate masks.
minescence.1, 2) The phosphors in low-voltage FEDs require
Our preliminary studies5, 15) on the structure of ZnO films
several properties, e.g., low electric resistance, a stable sur-
showed that laser irradiation of sol–gel-derived precursors
face for electron irradiation to minimize outgassing and fine
yields two kinds of crystalline ZnO films; irradiation at a low
particles for high resolution, as well as high luminescence
energy fluence (Ef ) produces low crystallinity with weak ori-
efficiency. These properties should be achievable with the
entation, while irradiation at a high Ef produces high crys-
preparation of a thin phosphor film, since a thin film has the
tallinity with a strong c-axis orientation. The film obtained
advantages of high resolution, low electric resistance across
at an appropriate Ef showed characteristic green PL and low
its section and no need for a binder. Various methods for the
electrical resistivity. The green PL centers are presumed to be
preparation of green luminescent ZnO films have been vig-
present in close-packed columnar crystals in the upper layer
orously studied including sputtering,6, 14) ion-beam-enhanced
of the ZnO film. These studies suggest that the structure, PL
deposition,7) electron beam evaporation,8) and spray pyroly-
and electrical properties of the ZnO films vary markedly de-
sis.9–11) Unfortunately, there has been no report on green lu-
pending on the preparation conditions.
minescent ZnO films that show high efficiency equivalent to
The present paper describes detailed studies on the rela-
that of the green phosphor powders.1, 2) This is probably be-
tionship of preparation conditions with the morphology and
cause the mechanism of the green luminescence in ZnO re-
structure of the ZnO films prepared by excimer laser irradi-
mains a matter of controversy. Vanheusden et al., reported
ation of sol–gel-derived precursor films. We investigated the
that the green photoluminescent (PL) intensity of ZnO phos-
effects of precursor thickness and energy fluence of the laser
phor powders depends on free-carrier concentration and pro-
on the crystallinity and morphology of the prepared films by
posed isolated single-ionized oxygen vacancies as the lumi-
X-ray diffraction (XRD), atomic force microscopy (AFM)
nescence centers.4) Studenikin et al., reported the effect of
and transmission electron microscopy (TEM). A schematic
film morphology on the nature of the PL.9) Thus, for improve-
model for the crystallization induced by laser irradiation is
ment of the green luminescence efficiency of ZnO films, it is
proposed. The green PL properties of the prepared ZnO films

6296
 Jpn. J. Appl. Phys. Vol. 40 (2001) Pt. 1, No. 11
(a)
Ef =
150mJ x1
100mJ x5
50mJ x 20
Dried x 20
32 33 34 35 36 37
2 (deg)
Fig. 1. XRD patterns of dried films and laser-irradiated films obtained at various energy fluences. (a) film thickness 100 nm, (b) film
thickness 180 nm. (●) and (■) denote the (002) and (101) peaks of wurtzite-type ZnO crystal, respectively.
are discussed in terms of their morphology and electronic
structure.
2. Experimental
Zinc oxide films were prepared in a way similar to that de-
scribed in previous works.5, 15) A coating solution, containing
0.6 mol/l zinc acetate dihydrate and 0.6 mol/l 2-aminoethanol
in 2-methoxyethanol, was spun on a quartz glass substrate to
form a wet film and dried at 473 K. The coating-drying proce-
dure was repeated three or six times to obtain film thicknesses
of approximately 100 nm and 180 nm, respectively. The resul-
tant dried films were designated according to their film thick-
ness as DF (100nm) or DF (180 nm).
The dried-film precursors were set on a 473 K hot plate
attached to a moving stage in air. Then the films were
subjected to irradiation by KrF excimer laser [λ = 248 nm,
22 ns full-width at half maximum (FWHM)] using a
Lambda-Physik LPX-305icc laser source. A rectangular area
of approximately 0.6 × 0.75 cm2 was illuminated at any one
time with a uniform energy distribution smoothed using an
Optec beam homogenizer. The entire surface of the film was
evenly irradiated by adjusting the total number of impinging
shots at any given location to five shots by controlling the
scan rate of the moving stage. The frequency of the laser was
fixed at 1 Hz, while the Ef of the laser was varied at 50, 100
and 150 mJ/cm2 . The laser-irradiated films were designated
according to their film thickness and irradiated Ef , e.g., LI
(100 nm/150 mJ), where the former number is film thickness
and the latter Ef .
The prepared films were subjected to XRD analysis with
CuKα radiation using a Rigaku RINT-1200 diffractometer.
Minute profiles around the (002) peak of wurtzite-type ZnO
crystals were also measured in order to determine the c-axis
lattice constants and crystallite sizes of the films. AFM
and TEM observations were carried out using a Digital In-
T. NAGASE et al. 6297
(b)
Ef =
150mJ x 4
100mJ x 4
50mJ x 10
Dried x 10
32 33 34 35 36 37
2 (deg)
struments NanoScope IIIa, and a Hitachi H-9000NAR TEM
or JEOL JEM-2010 TEM, respectively. Photoluminescence
spectra were obtained using a JASCO SS-25 spectrometer at
room temperature. Normal transmittance and near-normal
(5◦ ) reflectance spectra in the ultraviolet-visual (UV-vis) re-
gion were obtained at room temperature using a Shimadzu
UV-3100PC spectrometer in order to determine the absorp-
tion coefficients of the ZnO films.16) The transmittance and
reflectance spectra in the near-IR region were also obtained
to evaluate free-carrier concentration in the films.
3. Results and Discussions
3.1 Crystallinity of the laser-irradiated films
All XRD patterns of the dried films and laser-irradiated
films showed the (002) peak of wurtzite-type ZnO crystal as
a main peak, suggesting that all of the films contain a pre-
dominance of wurtzite-type ZnO crystals with a c-axis ori-
entation. Films LI (100 nm/100 mJ) and LI (180 nm/150 mJ)
showed two very small (100) and (101) peaks of wurtzite-type
structure in addition to the (002) peak. The XRD patterns
around the (002) peaks are given in Fig. 1. The (002)
peaks are weak and broad for the films DF (100 nm) and LI
(100 nm/50 mJ), while the laser irradiation at higher Ef results
in marked crystallization of c-axis-oriented ZnO [samples LI
(100 nm/100 mJ) and LI (100 nm/150 mJ) in Fig. 1(a)]. The
(002) peak shifts to a slightly higher 2θ value with increasing
Ef , indicating that the c-axis constants of the ZnO films de-
crease with increasing Ef (Table I). The decrease in the c-axis
lattice constant may be related to the creation of oxygen va-
cancies,5, 15) or to the lattice distortion due to the thermal ex-
pansion of ZnO being larger than that of the quartz glass sub-
strate. Similar tendencies are also observed in the case of laser
irradiation of thicker films, as is shown in Fig. 1(b). Among
all of the profiles shown in Fig. 1, film LI (100 nm/150 mJ)
shows a characteristic (002) peak profile: the strongest in-
6298 Jpn. J. Appl. Phys. Vol. 40 (2001) Pt. 1, No. 11
Table I. Crystallite sizes and c-axis lattice constants of ZnO crystals in the prepared films.
LI (100 nm LI (100 nm
Sample DF (100 nm)
/50 mJ) /100 mJ)
Crystallite
13 15 49
sizea)
c-Axis lattice
5.236 5.230 5.212
constant (Å)
a) Crystallite sizes were calculated by reference to the value of integral width of ZnO powders (average grain size: 7.5 µm).
tensity, the shortest c-axis lattice constant and an asymmetric
peak profile with a tailing at higher degrees.
Crystallite sizes of the ZnO films derived using Scherrer’s
equation are summarized in Table I. The dried films
DF (100 nm) and DF (180 nm) have crystallite sizes of
11–13 nm. The laser irradiation at an Ef of 50 mJ/cm2 does
not show a clear change in crystal size, but irradiation at an
Ef ≥ 100 mJ/cm2 shows a significant increase in the crystal-
lite size to around 50 nm. This indicates that marked crystal
growth is produced by irradiation at an Ef ≥ 100 mJ/cm2 .
3.2 Morphology of the laser-irradiated films
AFM images for the dried films DF (100 nm) and DF
(180 nm) show that they are composed of loosely packed
round particles of 30 nm in size, regardless of the film thick-
ness (Fig. 2). Laser irradiation at a low energy fluence has
little effect on the particle morphology; LI (100 nm/50 mJ)
retains a morphology similar to that of DF (100 nm). Laser
irradiation at an Ef ≥ 100 mJ/cm2 , however, produces a
significant change in the AFM images, to show unique sur-
face morphology. In film LI (100 nm/100 mJ), the small
particles disappear and a rough sintered surface with clear
grain boundaries appears (grain size is 30–100 nm). The
sintered grains with polyhedral shapes are closely bound to
each other, although a considerable number of pores smaller
than 200 nm in size are formed in the sintered solid. Film
LI (100 nm/150 mJ) has yet a different surface morphology;
the surface is macroscopically smooth and dense compared
to that of LI (100 nm/100 mJ). Striking crystal growth is ob-
served and the grain size reaches above 250 nm, suggesting
that melting and solidification of ZnO occurs over the ZnO
phase. AFM images for thicker films LI (180 nm/100 mJ) and
LI (180 nm/150 mJ) resemble that for LI (100 nm/100 mJ);
sintered grains of 20–200 nm in size are closely bound to
each other and rough sintered surfaces are formed. The
film surface is less rough and larger pores are formed for
LI (180 nm/150 mJ) than for LI (180 nm/100 mJ), suggest-
ing that sintering progresses more remarkably with increas-
ing Ef . However, surface morphology similar to that for
LI (100 nm/150 mJ) is not observed for LI (180 nm/150 mJ),
probably due to incomplete melting.
Cross-sectional TEM images for the dried and laser-
irradiated films are shown in Fig. 3. Both dried films show
similar porous structures, consisting of loosely packed crys-
tals 10–20 nm in size. This crystal size closely agreed with
those (11–13 nm) derived from XRD analysis. The TEM im-
age [Fig. 3(b)] for sample LI (100 nm/100 mJ) shows that it
has a unique structure consisting of two layers, close-packed
columnar crystals in the upper layer and a porous structure
T. NAGASE et al.
LI (100 nm LI (180 nm LI (180 nm LI (180 nm
DF (180 nm)
/150 mJ) /50 mJ) /100 mJ) /150 mJ)
46 11 14 44 60
5.204 5.244 5.237 5.222 5.218
with loosely packed crystals near the substrate face. The
columnar crystals consist of single crystals approximately
75 nm in height and 50 nm width, and are closely packed in
a parallel arrangement perpendicular to the substrate. The
porous structure near the substrate surface resembles that of
the dried film [Fig. 3(a)], consisting of loosely packed parti-
cles 10–30 nm in size. On the other hand, the TEM image
[Fig. 3(c)] for LI (100 nm/150 mJ) shows that it consists of
densely packed crystals of approximately 85 nm in height and
100 nm width. An amorphous thin layer is formed near the
substrate face instead of the porous layer with loosely packed
particles.
Films LI (180 nm/100 mJ) and LI (180 nm/150 mJ)
also have two-layer structures similar to that of LI
(100 nm/100 mJ). The height of the upper layer increases with
Ef : reaching approximately 55 nm for LI (180 nm/100 mJ)
[Fig. 3(e)], and approximately 100 nm for LI (180 nm/150 mJ)
[Fig. 3(f)]. For LI (180 nm/100 mJ), the particles near the
substrate surface remain as small as those in the dried films.
However, slight crystal growth of the substrate particles is
observed for film LI (180 nm/150 mJ), probably due to the
stronger thermal effect.
3.3 Model for crystallization induced by excimer laser irra-
diation
The above results show that laser irradiation at an Ef higher
than the threshold (between 50 and 100 mJ/cm2 ) produces the
marked crystal growth of fine particles resulting in strongly
c-axis orientated crystals. The morphology of the crystal
phase varies depending on Ef and film thickness. Laser irradi-
ation at relatively high Ef results in the formation of two-layer
films with a closely packed upper layer and a porous lower
layer, while irradiation at much higher Ef of a thin precursor
produces a film consisting almost entirely of large densely
packed crystals with a smooth film surface.
A schematic model for the crystallization by laser irradi-
ation is given in Fig. 4. We assume that the characteristic
crystallization is caused mainly by the instantaneous thermal
effect induced by pulsed laser irradiation. The simulation
of temperature profiles by pulse-laser irradiation by Szörényi
et al. (for indium tin oxide films on glass substrates) shows a
steep (about 30 ns) temperature rise at the surface of the film,
accompanied by a relatively slow (about 100 ns) and small
temperature rise near the substrate interface caused by ther-
mal conduction from the surface into the substrate.18) The
two-layer structure, which is observed at relatively high Ef ,
is caused by limited but intense sintering of the surface layer
due to the steep temperature increase. Subsequent thermal
flow toward the inside of the film produces homogenous crys-
 Jpn. J. Appl. Phys. Vol. 40 (2001) Pt. 1, No. 11 T. NAGASE et al. 6299

Fig. 2. AFM images of films DF (100 nm) (a), LI (100 nm/50 mJ) (b), LI (100 nm/100 mJ) (c), LI (100 nm/150 mJ) (d), DF (180 nm) (e),
LI (180 nm/100 mJ) (f), and LI (180 nm/150 mJ) (g).

tal growth from the upper part to the inside. On the other Film LI (100 nm/150 mJ), obtained from a thin precursor at
hand, the temperature rise near the substrate face is insuffi- a much higher Ef , has a unique morphology with much larger
cient to produce anything more than slight sintering, resulting grain size and a smooth film surface. Since the simulation of
in retention of the porous structure. temperature profiles by laser irradiation also shows that the
6300 Jpn. J. Appl. Phys. Vol. 40 (2001) Pt. 1, No. 11 T. NAGASE et al.

Fig. 3. TEM images of cross sections of films DF (100 nm) (a), LI (100 nm/100 mJ) (b), LI (100 nm/150 mJ) (c), DF (180 nm) (d), LI
(180 nm/100 mJ) (e), and LI (180 nm/150 mJ) (f), The bars denote a length of 50 nm.
 Jpn. J. Appl. Phys. Vol. 40 (2001) Pt. 1, No. 11
Laser irradiation
Relatively low temp.
at low Ef
in the upper layer
Laser irradiation
at relatively high Ef
Relatively high temp.
in the upper layer
Laser irradiation
at much higher Ef
of a thin Film
Extremely Melting
high temp. throughout the film
Fig. 4. Schematic model for the crystallization induced by laser irradiation.
interface and consequently the entire film reach higher tem-
peratures with a decrease in the film thickness,19) a greater
thermal effect on LI (100 nm/150 mJ) is expected in compar-
ison to that on LI (180 nm/150 mJ). The thermal effect on LI
(100 nm/150 mJ) is probably sufficient to raise the tempera-
ture above the melting point, not only in the upper part of the
film but also in the lower part, resulting in complete melting
throughout the film. The complete melting causes a decrease
in crystal nucleation, since complete melting consumes even
residual crystal clusters which otherwise easily transform into
the crystal nuclei. The decrease in crystal nucleation results in
the formation of a large-grain film. The shortest c-axis lattice
constant and the asymmetric peak profile in the XRD patterns
of LI (100 nm/150 mJ) indicate that the significant tempera-
ture rise and rapid solidification result in considerable lattice
distortion.
The maximum thickness of the layer that undergoes intense
sintering or solidification via melting is evaluated as 100 nm
from the result of LI (180 nm/150 mJ). This value correlates
with the absorption length (the reciprocal of the absorption
coefficient, approximately 60 nm) of the precursor films at a
wavelength of 248 nm corresponding to the KrF excimer laser
wavelength.
3.4 Photoluminescence properties of the laser-irradiated
films
Laser-irradiated films showed visible PL in addition to the
near-UV band around 380 nm. We have reported in a previous
work that the dried, laser-irradiated, and heat-treated films ex-
hibited three visible PL bands centered around 510, 600 and
740 nm,5) depending on the preparation method and condi-
tions. The three visible PL bands have also been reported in
previous works.3, 6, 8–11, 14, 19)
Visible PL spectra excited at 275 or 325 nm are given in
T. NAGASE et al. 6301
LI (100nm/50mJ)
LI (180nm/50mJ)
Weak orange PL
Slight sintering
LI (100nm/100mJ)
LI (180nm/100mJ)
LI (180nm/150mJ)
Green PL
(+ weak red PL)
Intense sintering Relatively low temp. Slight sintering
near the substrate face
LI (100nm/150mJ)
Green PL with excitation-
wavelength dependence
Crystals with
Solidification
large grain size
Fig. 5. The dried films and laser-irradiated films at 50 mJ/cm2
show weak orange PL with maximums around 600 nm. Laser
irradiation at Ef ≥ 100 mJ/cm2 produces green PL, although
their PL properties vary depending on the morphology of the
film. The films [LI (100 nm/100 mJ), LI (180 nm/100 mJ), and
LI (180 nm/150 mJ)] with a two-layer structure show strong
green PL with peaks between 510 and 555 nm. The green
PL intensities rarely change with the excitation wavelength.
The film [LI (100 nm/150 mJ)] with large crystallites also
shows green PL, but the PL spectra depend strongly on ex-
citation wavelength. The spectrum excited at 325 nm has
very low intensity, but that excited at 275 nm shows a re-
markable increase in peak intensity, comparable to that for
LI (100 nm/100 mJ). Since films with marked crystallization
show strong green PL, we can assume that the green PL cen-
ters are located in the closely packed crystals of ZnO.
Such a compact structure is markedly different from the
morphology of the green PL film prepared using the spray py-
rolysis method by Studenikin et al., which showed a porous
structure throughout the film.9) They have concluded that the
film with maximum porosity has maximum green PL, be-
cause the reducing gas is able to create oxygen vacancies,
i.e., green PL centers in a layer immediately below the crys-
tallite surface. On the other hand, our method involves the
instantaneous and strong thermal effect induced by pulsed
laser irradiation. This effect may cause the dissipation of oxy-
gen atoms, accompanied by the formation of closely packed
crystals, producing green PL centers throughout the closely
packed crystals. We believe that our method is advantageous
for the preparation of a thin phosphor film in low-voltage
FEDs, since a compact structure gives low electric resistance
compared with a porous structure.
LI (180 nm/150 mJ) has an additional band peaking around
720 nm corresponding to a red luminescence, which appears
6302 Jpn. J. Appl. Phys. Vol. 40 (2001) Pt. 1, No. 11 T. NAGASE et al.

Fig. 5. Photoluminescence spectra of the films excited at 275 (black lines) and 325 nm (gray lines): (a) film thickness 100 nm, (b) film
thickness 180 nm.

more clearly in the spectrum excited at 275 nm. For LI 1

(180 nm/100 mJ), a similar band is observed, though just 1
barely, in the spectrum excited at 275 nm. Such a red lumines-
cence band from ZnO has seldom been reported,19) although
our previous work reported that the heat-treated film showed
Normalized intensity

a broad band peaking around 740 nm.

3.5 Excitation and optical absorption spectra

Excitation and optical absorption spectra of the green PL
LI (100 nm/100 mJ) and LI (100 nm/150 mJ) were measured
in order to evaluate their electronic structures. Excitation
spectra for LI (100 nm/100 mJ) and LI (100 nm/150 mJ) de-
tected at 540 nm are given in Fig. 6. Although both spectra
show an additional peak around 370 nm, which results from 2
excitonic absorption, and a small peak around 400 nm, the
two spectra present different behaviors at excitation wave- 0
lengths below approximately 380 nm. The spectrum of LI 250 300 350 400 450
(100 nm/100 mJ) resembles the typical excitation spectrum Wavelength (nm)
of ZnO films prepared by the spray pyrolysis method.9) The
excitation efficiency is nearly constant for photon energies Fig. 6. Excitation spectra detected at 540 nm for films LI (100 nm/100 mJ)
higher than the typical ZnO band gap (E g = 3.3 eV), sug- (1), and LI (100 nm/150 mJ) (2).
gesting that the main excitation mechanism for green PL is
electron–hole pair generation by interband absorption. In
contrast, the spectrum of LI (100 nm/150 mJ) shows unique (100 nm/150 mJ) are given in Fig. 7. LI (100 nm/100 mJ)
excitation-wavelength-dependent excitation efficiency; low shows a typical ZnO absorption spectrum. On the other hand,
excitation efficiency at excitation wavelengths from 380 LI (100 nm/150 mJ) exhibits a remarkably deformed spectrum
to 320 nm, but when excited below 320 nm, the film LI and has a considerably lower absorption coefficient from (ap-
(100 nm/150 mJ) shows a striking increase in excitation ef- proximately) 380 to 300 nm than does LI (100 nm/100 mJ).
ficiency. This result suggests that the unique excitation-wavelength de-
UV-vis absorption spectra of LI (100 nm/100 mJ) and LI pendence of PL intensity observed for LI (100 nm/150 mJ) is
 Jpn. J. Appl. Phys. Vol. 40 (2001) Pt. 1, No. 11 T. NAGASE et al. 6303

As shown in Figs. 1–3, 5 and Table I, LI (180 nm/150 mJ)

2.5
obtained by laser irradiation at a high Ef (150 mJ/cm2 ) of a
Absorption coefficient (x105 cm-1)

thicker precursor, demonstrated structural characteristics and

2 green PL properties similar to that of LI (100 nm/100 mJ)
rather than those of LI (100 nm/150 mJ). LI (180 nm/150 mJ)
1.5 has high green PL intensity than does LI (180 nm/100 mJ)
2 1 (Fig. 5). These results show that the appropriate Ef for prepar-
ing green PL films depends on the film thickness of the pre-
1 cursors. The green PL as well as crystallization is most likely
produced mainly by the thermal effect induced by laser irra-
0.5 diation.

4. Conclusion
0
3 The excimer laser irradiation of sol–gel-derived precur-
sors is a unique method of producing green PL ZnO films
200 250 300 350 400 450 with a compact structure. It has the potential to control
the free-carrier concentration by manipulating the preparation
Wavelength (nm)
conditions, i.e., energy fluence of the laser and film thick-
Fig. 7. UV-vis absorption spectra of films LI (100 nm/100 mJ) (1), LI ness of the precursors. This method encourages future studies
(100 nm/150 mJ) (2), and the quartz glass substrate (thickness: 1 mm) (3). on the practical creation of efficient green luminescent ZnO
films.

0.1 Acknowledgent
This work was supported by Industrial Technology
0.08 Research Grant Program in ’00 from the New Energy and
Industrial Technology Development Organization (NEDO) of
Japan.
0.06
2
Optical density

1) L. E. Shea: Interface 7 (1998) 24.

0.04
0.02
0 Mizutani: Jpn. J. Appl. Phys. 39 (2000) L713.
-0.02
1000 1500
Wavelength (nm)
Fig. 8. Near-IR absorption spectra of films LI (100 nm/100 mJ) (1), LI
(100 nm/150 mJ) (2), and the quartz glass substrate (3).
related to the threshold of electron excitation from the va-
lence band to the conduction band. Such deformation of the
band structure of LI (100 nm/150 mJ) is probably caused by
a Burstein-Moss shift, i.e., increasing concentration of free
carriers.20) The presence of a high concentration of free car-
riers in LI (100 nm/150 mJ) is confirmed in its absorption
spectrum in the near-IR region (Fig. 8). LI (100 nm/150 mJ)
has a higher optical density due to free carriers, while LI
(100 nm/100 mJ) has an optical density almost as low as that
of the substrate. The high concentration of free carriers in LI
(100 nm/150 mJ) may result from the creation of high-density
oxygen vacancies.
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