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JOURNAL OF APPLIED PHYSICS 100, 063701 2006

Effect of fluorine addition on transparent and conducting Al doped


ZnO films
Inho Kim,a Kyeong-Seok Lee, Taek Seong Lee, Jeung-hyun Jeong, Byeong-ki Cheong,
Young-Joon Baik, and Won Mok Kim
Thin Film Materials Research Center, Korea Institute of Science and Technology, 39-1 Hawolgok-dong,
Seongbuk-gu, Seoul 136-791, Korea

Received 10 October 2005; accepted 30 June 2006; published online 20 September 2006
Al doped ZnO AZO films with varying fluorine content were prepared by radio frequency
magnetron sputtering at a room temperature to investigate doping effects of fluorine on the
structural, the optical, and the electrical properties. The small amount of fluorine addition to AZO
films resulted in beneficial effect on the electrical conductivity by improving the direct current dc
Hall mobility, and the minimum specific resistivity was as low as 5.9 104 cm. With increasing
fluorine content in AZO films, the optical absorption loss in the visible range decreased regardless
of carrier concentration in the films. X-ray diffraction and scanning electron micrograph analyses
showed that the crystallinity of AZO films was deteriorated by addition of fluorine. Small amount
of fluorine addition to AZO film resulted in decrease of absorption loss as well as increase in Hall
mobility, and the beneficial effects of fluorine addition was deduced to be caused by killing in-grain
point defects. From the comparison between the dc Hall mobility and the optical mobility, it was
concluded that fluorine excessively added to AZO increased grain boundary scattering, which was
explained using two phase model rather than charge trapping model. 2006 American Institute of
Physics. DOI: 10.1063/1.2347715
I. INTRODUCTION

Transparent conducting oxide TCO films have been


used in many versatile applications such as front electrodes
of solar cells, flat panel display, energy efficient windows,
etc. Recently, among various TCO materials, ZnO thin films
doped with Al, B, or Ga have drawn a great deal of attention
due to their low material cost, nontoxicity, and stability under hydrogen plasma compared to the most widely used Sndoped indium oxide ITO.1 Instead of doping with cations
such as Al, B, or Ga, however, Hu and Gordon obtained a
noteworthy result by doping fluorine to ZnO FZO films
using a chemical-vapor deposition CVD technique, in
which electrical resistivity of 4 104 cm and Hall mobility as high as 40 cm2 / V s were reported.2 The low resistivity
of the FZO films mostly due to their high mobility was attributed to the substituted fluorine in oxygen sites which
mainly perturbs the valence band, thereby leaving the conduction band relatively free of scattering.
Despite the fact that the fluorine could be a promising
anion dopant for achieving TCO with high mobility, there
have not been much subsequent reports regarding fluorine
doped ZnO films. de la L. Olvera et al. studied the doping of
fluorine into ZnO by chemical spray method, but the electrical properties were far from satisfactory.3,4 On the other
hand, Miyata et al.5 and Minami et al.6 reported possibility
of fabricating fluorine doped ZnO and fluorine and gallium
codoped ZnO films with better electrical properties by using
vacuum arc plasma evaporation VAPE, but no detailed
analysis has been given.
Recently, we reported the possibility of obtaining ZnO
a

Electronic mail: inhok@kist.re.kr

0021-8979/2006/1006/063701/6/$23.00

film with high figure of merit by codoping aluminum and


fluorine using radio frequency rf magnetron sputtering.7
The addition of fluorine into Al doped ZnO films resulted in
the reduction of both the resistivity and the optical absorption in the visible range, but the roles of the fluorine could
not be explained clearly. Therefore, in a continued effort of
elucidating the role of the fluorine, aluminum and fluorine
codoped ZnO AFZO films, in which the fluorine content
varied while the aluminum content being maintained at relatively constant level, were fabricated, and the effects of fluorine addition to Al doped ZnO AZO films on the structural,
the optical, and the electrical properties were investigated in
this study. In order to clarify the dominant scattering mechanism in these films, a temperature dependence measurement
of Hall mobility and a comparative examination between the
dc Hall mobility and optical mobility were made and discussed.
II. EXPERIMENTAL DETAILS

AZO films with varying fluorine content were deposited


on glass substrates Corning Eagle 2000 by rf magnetron
sputtering using 2 in. diameter targets. Deposition was carried out at working pressure of 1 mTorr in pure Ar atmosphere. No intentional heating was applied to the substrate.
AZO films with four different fluorine contents were prepared by cosputtering two ZnO targets with different alloying elements and compositions: one is containing 3 wt %
Al2O3 ZnO 3 wt % Al2O3 and the other was selected from
pure ZnO, ZnO targets containing 1.3, 3.0, and 10 wt %
ZnF2. These four films will be referred to hereafter as AZO,
AFZO1, AFZO2, and AFZO3 in the order of increasing fluorine content. The rf power on the ZnO 3 wt % Al2O3 target

100, 063701-1

2006 American Institute of Physics

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Kim et al.

J. Appl. Phys. 100, 063701 2006

FIG. 2. a Carrier concentration, Hall mobility, and resistivity of Al and F


doped ZnO films.

FIG. 1. The atomic ratios of Al/ Zn and F / Zn in ZnO films as a function of


expected ZnF2 content.

was fixed at 30 W, and on the other target it was adjusted to


yield the same deposition rate as that from the ZnO 3 wt %
Al2O3 target.
The chemical composition was analyzed by Auger electron spectroscopy AES. Electrical resistivity, Hall mobility,
and carrier concentration were obtained by a Hall effect measurement equipment using a van der Pauw method. The
structural analysis was carried out by an x-ray diffraction
measurement Cu K wavelength= 1.540 562 , -2 scan
mode and a field emission scanning electron microscopy
FE-SEM. The optical transmittance and the reflectance of
the films were measured using a spectrophotometer Cary
5G in the wavelength range from 250 to 2600 nm.

showed only one strong crystalline peak located at 2 position of 34.4, indicating 002 preferred orientation of ZnO
wurtzite structure. The intensity of 002 crystalline peak decreased rapidly with increasing fluorine content, and eventually that of AFZO3 film went down to only 3% of that of
AZO film, indicating that the addition of fluorine to AZO
film deteriorates the crystallinity of the films severely. Such a
microstructural change of the AZO films due to fluorine addition is more pronounced in the SEM images presented in
Fig. 4. AZO and AFZO1 films revealed very dense morphology and columnar structure, whereas with increasing fluorine
content, the columnar structure was lost and the grain boundary width was widened. This microstructural evolution with
fluorine content decreasing grain size and reducing crystallinity is seemingly related to the deterioration of electrical
resistivity, except the case of very small amount of fluorine
doping AFZO1.

III. RESULTS AND DISCUSSIONS


A. Effects of fluorine addition on electrical
and structural properties

In Fig. 1, the chemical composition ratios of Al/ Zn and


F / Zn determined from AES are shown as a function of ZnF2
content. The ZnF2 content was calculated from deposition
rate of each target by assuming that the fluorine exists in the
form of ZnF2 in the films and that the ideal density of each
cosnstituent ZnF2: 4.95 g / cm3, ZnO: 5.606 g / cm3 is preserved. The estimated ZnF2 contents were 0, 0.65, 1.49, and
4.91 wt % for AZO, AFZO1, AFZO2, and AFZO3 films, respectively, and the corresponding Al2O3 contents were 1.50,
1.50, 1.51, and 1.53 wt %, respectively. Since, in AES analysis, the elemental sensitivity factors were used, the values of
composition ratios shown in Fig. 1 have to be regarded only
as an indicator that the experimental intention of obtaining
ZnO films with varying fluorine content while maintaining
aluminum content at constant level was satisfied.
Shown in Fig. 2 are electrical resistivity, carrier concentration, and Hall mobility of the four films. Among the four
films studied, AFZO1 film yielded the lowest resistivity of
5.9 104 cm, which is stemming from its increased Hall
mobility of 20 cm2 / V s and high carrier concentration of
5.15 1020 cm3. AFZO2 and AFZO3 films with higher
fluorine content than AFZO1 film yielded higher resistivity
than AZO film. The x-ray diffraction profiles of the corresponding four films are shown in Fig. 3. All four films

B. Effects of fluorine addition on optical properties

The optical properties of the fluorine doped AZO films


were investigated in terms of optical absorption coefficient
from the measurement of transmittance and reflectance
by spectrophotometer in the wavelength range of 300
1500 nm, and the coefficients were plotted in Fig. 5. Here,
the optical absorption coefficients were evaluated using the
following relation:

FIG. 3. X-ray diffraction profiles of Al and F doped ZnO films.

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Kim et al.

which increases gradually with wavelength.8 A distinctive


feature of the absorption coefficients shown in Fig. 5 is that
the absorption is greatly reduced with increasing fluorine
content, which is pronounced especially in visible range. The
lowering of absorption observed in AFZO2 and AFZO3 films
can be attributed to the reduced free carrier concentration as
shown in Fig. 2, because the absorption in the visible range
is proportional primarily to the number of free carriers. However, even if AFZO1 film had slightly higher carrier concentration than AZO film, the absorption of AFZO1 films in
visible range is rather much lower than that of AZO film.
This indicates that, besides free carriers, other scattering centers, such as point defects of interstitial zinc metals or oxygen vacancies which are easily formed within ZnO films,9
may also possibly be influencing absorption source to a large
extent.
C. Scattering mechanisms

FIG. 4. FE-SEM surface and cross-section images of a AZO, b AFZO1,


c AFZO2, and d AFZO3 films.

1
100 R
ln
,
d
T

where d is the film thickness and T and R are the optical


transmittance and the optical reflectance, respectively. The
absorption curves exhibit a typical characteristic of TCO,
showing the minimum in visible wavelength region. This
minimum absorption in visible region occurs due to the
trade-off between the fundamental absorption mode located
at and stronger toward ultraviolet UV range and the absorption mode from various scattering centers such as free carriers, ionized impurities, phonon, and neutral impurities,

The relationship between the absorption coefficient and


the wavelength in near infrared NIR range has been reported to follow p, where the exponent p is dependent
on the dominant optical scattering mechanism.10 The solid
lines overlaid in the wavelength range from 900 to 1500 nm
in Fig. 5 are the best fit lines according to the relationship
p, which represent the experimental data well in that
specific region. The values of exponent p of AZO, AFZO1,
AFZO2, and AFZO3 films were almost identical by showing
3.8, 3.9, 4.0, and 3.8, respectively, implying that there are a
lot of ionized impurities in the films which act as dominant
scattering centers in the near infrared range. However, as the
wavelength is decreased toward visible range the plasma
wavelength, the optical absorption gets influenced by more
absorption centers such as free carriers and other structural
defects as well as the ionized impurities. In this regard, the
consistency between absorption coefficient and free carrier
concentration broken at AFZO1 film implies that there is
appreciable change in other absorption centers. Thus we
came to the logical deduction that small amount of fluorine
added to AZO film removes the ionized point defects such as
oxygen vacancies and/or zinc interstitials by substituting the
oxygen vacancies and/or by reacting with zinc interstitials.
This reduction of scattering centers would lead to reduction
of optical absorption as well as increase of the Hall mobility
as observed in AFZO1 film because the substituted fluorine
ions would not act as strong scattering centers unlike oxygen
vacancies or zinc interstitials.
D. Temperature dependence of Hall mobility

FIG. 5. Optical absorption coefficient vs wavelength. The overlaid solid


lines in near IR region are the fitted curves according to the relationship
p.

In order to explore the above-mentioned hypothesis on


the role of fluorine killing the scattering centers within AZO,
the electrical and optical transports were studied in terms of
electrical and optical mobilities. First of all, for the purpose
of finding dominant mobility limiting mechanism in these
films, Hall mobility of each film was measured with temperature and the results are plotted in Fig. 6. The Hall mobilities of AZO and AFZO1 films show a negative dependence on temperature whereas AFZO3 film exhibits positive
dependence on temperature, typical for thermally activated

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= 1

2p
,
2 + i/

where is the high frequency dielectric constant, is the


relaxation time of free electrons, and p is the plasma frequency which is a function of free electron concentrations N
and effective mass m*,

p =

FIG. 6. Temperature dependence of dc Hall mobility of AZO, AFZO1,


AFZO2, and AFZO3 films.

Hall mobility having comparable grain boundary potential


barrier. Compared to this, AFZO2 film with less fluorine
shows a changeover in Hall mobility from positive to negative dependence at about 167 K, which means that the film
has low grain boundary potential barrier.11 This trend of the
added fluorine strengthening thermally activated Hall mobility gives us a clue that grain boundary scattering is the dominant mobility limiting mechanism. Thus, the decreased Hall
mobility values found in the AFZO2 and AFZO3 films are
attributed to the increased contribution from the grain boundary scattering. For low doping of fluorine, on the other hand,
AFZO1 has higher Hall mobility than AZO despite the worse
crystallinity of AFZO1 than AZO film Figs. 3 and 4, which
excludes the grain boundary scattering from dominant scattering in AZO and AFZO1 films. Therefore, the improved
Hall mobility observed in AFZO1 film can be ascribed to the
reduced scattering centers within grains as discussed in the
optical absorption.

E. Optical mobility versus Hall mobility

Reduced scattering within grains in AFZO1 films can be


confirmed from the comparison of Hall mobility and optical
mobility. The in-grain mobility of free electrons, indicative
of in-grain scattering, can be evaluated by utilizing the
Drude free electron model in n-type degenerate semiconductors such as TCO materials. The optical transmittance and
the optical reflectance in the near infrared ray range are
strongly dependent on the scattering of free electrons, because the light absorption is induced by the scattering of free
electrons within the conduction band. According to the
Drude free electron model, the dielectric function of a film is
described by12

Ne2
.
0 m *

Using Eq. 2 and the relation between the dielectric function


and the refractive index, two Drude parameters and p can
be extracted from the measured optical data. In this study,
assuming equals 4, the simulation on optical transmittance and reflectance was carried out using commercially
available software, FILM WIZARD, in the wavelength range
of from 500 to 2600 nm.12 The simulation results and obtained parameters are shown in Figs. 7a7d. The effective
mass was determined using Eq. 3 from the plasma frequency and the carrier concentration value obtained from the
dc Hall measurement. Using the extracted values of the effective mass and the relaxation time, optical mobility was
evaluated by the following relation:

opt =

e
.
m*

Since the optical mobility represents the oscillating motion


of free carriers in high frequency 1014 Hz electric field,
their motion is confined within the grains of several tens of
nanometers and thus the effect of the grain boundary on the
optical mobility is avoided.13 Therefore, the comparison of
the dc Hall mobility and the optical mobility can provide
some insight into the influence of the grain boundaries on the
free carrier mobility.
In Fig. 8, the dc Hall mobility and the optical mobility of
AZO, AFZO1, AFZO2, and AFZO3 films are compared. Unlike the dc Hall mobility, the optical mobility values of
AFZO2 and AFZO3 films are comparable to that of AZO
film, suggesting that there is not much difference in in-grain
mobility in these films. The differences between the dc Hall
mobility and the optical mobility became larger in AFZO2
and AFZO3 films than in AZO and AFZO1 films, amounting
up to one order of magnitude for AFZO3 film. This implies
that, for films with large fluorine content, the grain boundary
scattering comes into playing dominant role as the mobility
limiting mechanism. This is in good agreement with the results observed from the x-ray diffraction measurement and
the SEM images, in which AFZO2 and AFZO3 films with
larger fluorine content revealed poorer crystallinity. At this
moment, we tried to understand the nature of grain boundary
scattering on the mobility. First we applied a charge trapping
model. According to the charge trapping model, the grain
boundary effective mobility for the degenerate semiconductors can be expressed by the following equation:11

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Kim et al.

FIG. 7. Measured solid lines and Drude-fitted dashed lines optical transmittances and reflectances of a AZO, b AFZO1, c AFZO2, and d AFZO3
films m*: effective mass, : relaxation time, and p: plasma wavelength.

= BT1 exp

Ea
,
k BT

where Ea is an activation energy for grain boundary potential


energy barrier and B is a constant. The estimated activation
energy barrier for AFZO3 film, which was estimated using
the above relation, was 19 meV. But the obtained energy
barrier was lower than even the thermal energy of a free

electron at room temperature, and thus the charge trapping


model cannot account for the large drop of the dc Hall mobility observed in AFZO2 and AFZO3 films. On the contrary,
the dc Hall mobility drop in AFZO2 and AFZO3 films can be
explained by two phase model at the grain boundary for
these particular films.14,15 Considering the limited solubility
of ZnF2 in ZnO films, the large amount of fluorine addition
would increase the segregation of highly resistive ZnF2 at the
grain boundaries, which would reduce the dc Hall mobility
in proportion to the fluorine content in the films.
Different from the cases of high fluorine content, dc Hall
mobility in the AFZO1 film with low fluorine doping shows
the same trend as the optical mobility, i.e., increased dc Hall
mobility and optical mobility with small amount of fluorine
addition. This means that with small amount of fluorine addition, the electrical transport is affected primarily by defect
density within grains, not by grain boundary, and fluorine
addition can remove the defect sites. As a result, it can be
concluded that the optimal addition of fluorine to AZO film
can be beneficial to the electrical and the optical properties of
AZO film by providing in-grain defect killers.
IV. CONCLUSIONS

FIG. 8. Comparison of dc Hall mobility and optical mobility of AZO,


AFZO1, AFZO2, and AFZO3 films.

In this study, the effects of fluorine addition to Al doped


ZnO films on the electrical, the optical, and the structural

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063701-6

properties were examined and the dominant mechanism of


free electrons transport in these films was discussed. The
optimal addition of fluorine to AZO films increased both the
dc Hall mobility and the free carrier concentration and also
decreased the optical absorption in the visible and near IR
wavelength ranges. By comparing the dc Hall mobility with
the optical mobility and by analyzing temperature dependent
dc Hall mobility behavior, the small amount of fluorine
added to AZO film was deduced to act as a point defect
killer, resulting in the removal of the in-grain scattering centers. But further increase in fluorine content caused a severe
deterioration of crystallinity, making the grain boundary scattering become the mobility limiting mechanism. And the
grain boundary scattering in these films was explained better
by the two phase model than by the charge trapping model.
In conclusion, the fluorine, when an optimal amount is added
to Al doped ZnO film, can yield beneficial effects on both the
electrical properties and the optical properties.
T. Minami, MRS Bull. 25, 38 2000.
J. Hu and R. G. Gordon, Sol. Cells 30, 437 1991.

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