HRTEM study of ZnO thin films deposited by magnetron

sputtering
E. Vasilea), I. Iordacheb) and R. Plugaruc)
a)S.C.
S.C.
b)National

METAVMETAV-Research & Development S.A, C.A.Rosetti Str.

Str. 31, 020011, Bucuresti

Research and Development Institute for Electrical EngineeringEngineering- ICPEICPE-CA, 313 Splaiul Unirii,
Unirii, Bucharest 030138, Romania
c)National

Institute for R&D in MicrotechnologyMicrotechnology-IMT Bucharest, POPO-BOX 3838-160, 023573 Bucharest, Romania,
E-mail: rodica.plugaru@imt.ro

Overwiev
Recent developments in the field of ZnO thin films for optoelectronic
devices have been focused on the optimization of the film structure
structure

ZnO films deposited by DC magnetron sputtering

from Zn target
(a)

(b)

ZnO films deposited by RF magnetron sputtering

from ZnO target
(a)

(b)

since it was found that particularly (002)(002)-oriented ZnO films exhibit

highly enhanced optical and photoluminescence properties.
In this paper we report the results of our investigation on the structure
(c)

of ZnO thin films deposited on glass substrates by using DC and RF

magnetron sputtering.

Experimental
Zinc oxide thin films were prepared by DC and RF magnetron
sputtering technique. Metallic Zn (Aldrich, 99.99%) was used as
target in DC magnetron sputtering process. ZnO target used in RF
magnetron sputtering deposition process was obtained from ZnO
powder (Umicore
(Umicore Zinc Chemicals, 99.99%). The ZnO powder was
mecanically milled, then pressed as a disc with the diameter of
4.5 cm and thickness of 3.5 - 4 mm. The target was sintered at
1200oC for 1 h.

SEM images of ZnO film deposited from Zn metallic target and oxidized in air at 450oC, 3h (a,b). The film thickess in the
SEM cross section image is 92.5 nm (c).

(a)

(b)

(c)

(d)

SEM images of the as deposited ZnO film surface (a). Relative uniform grains size about 22-35 nm
(b).

(a)

(b)

The sputtering processes were carried out in Ar atmosphere. The

sputtering time was 1 min and the deposited film thickness was
about 120 nm. The substrate was glass in both experiments.
ZnO films obtained by oxidation of metallic Zn films are referred as
as
films A
A and ZnO films deposited from ZnO target are reffered ti
as films B
B.

The surface mophology was investigated by using a QUANTA

INSPECT F Scanning Electron Microscope (SEM) with XX-ray energy
dispersive spectrometer (EDAX) and an Alpha 300 S Witec alpha
300S System with Atomic Force Microscopy (AFM).
The film structure was analysed by using a High Resolution
Transmision Electron Microscope (HRTEM) TECNAI F30 and a
X-ray Diffraction System (XRD) - SmartLab Rigaku Corporation,
Japan.

HRTEM, EDX
(c)

(d)

Conclusions
SEM images of films "A" show grains of ~ 100 nm in average size,
size,
with columnar structure and a relative large porosity.
Films "B" present smooth surfaces with spherical grains of ~ 35 nm in
average size.
The characteristics of the films morphology, structure and optooptoelectrical properties related to the two method of deposition were
were
previously reported [1,2].

HRTEM images of crystalline grains in ZnO film

deposited from Zn metallic target (a). Magnified
HRTEM image of grains surrounded by
defective region of grain boundaries (b, c, d).
The ratio IZn/IO intensity in EDAX spectrum is
3.4 (e)
(a)

(a)

HRTEM images of crystalline grains in as

deposited ZnO film (a). Magnified HRTEM image
of crystalline grains surrounded by defective
regions. Crystalline order on the smal volumes
(b, c, d). The ratio IZn/IO intensity in EDAX
spectrum is 3.7 (e).

(b)

(a)

(a)

(b)

HRTEM images of films "A" show nanocrystalline regions of ~10~10-15

nm in size. The nanocrystalline domains have different orientations
and are separated by well defined grain boundaries.
AFM:

Various [0001] tilted grain boundaries may be observed, as previously

previously
revealed in ZnO bicrystals [3].
HRTEM images of the films "B" show small crystalline volumes.
Nanocrystalline domains are surrounded by large and strongly
defective grain boundaries.

EDAX spectra evidence a reduced IZn/IO ratio in films "A" oxidized in

air at 450oC for 3h, that indicates an increased oxygen content
comparatively with the asas-deposited ZnO films (films "B").
The dependence of the crystallinity on the oxygen content was

(c)
(c)
AFM 2D (a) and 3D images (b) of a ZnO film obtained
from Zn metallic target, showing areas of large grains
randomly distributed on the surface, as well as small
grains. Vertical (c) and horizontal (d) profiles. The
grains height is in the range: 30-140 nm.

(d)

AFM 2D (a) and 3D images (b) of an as deposited ZnO

film, showing grains with relatively uniform size all
over the surface. Vertical (c) and horizontal (d) profiles.
The grains height is in the range: 80-120 nm.

(d)

previously reported [4]; it has a strong influence on the structure

structure of
the grain boundaries and electrical properties.

2D and 3D AFM images and topography profiles reveal that regions

5.0e+003

Meas. data:Zn!Q/Data 1
Zn O

5.0e+003
Meas. data:Zn!Q/Data 1
Zn O

4.0e+003

of columnar grains with an abnormal size are randomly distributed

distributed on
the surface of films "A".

Intensity(cps)

3.0e+003

Integrated Intensity(cps deg)

related with the surface morphology [5].

ZnO, (112)

ZnO, (103)

ZnO, (201)

ZnO, (200)

0.0e+000
100
90
80
70
60
50
40

ZnO, (110)

(a)

1.0e+004
8.0e+003

ZnO, (102)

1.0e+003

ZnO, (101)

ZnO, (100)

2.0e+003
ZnO, (002)

Zn O, (1 12)

Zn O, (20 1)

ZnO, (20 0)

Zn O, (1 03)

Zn O, (1 10)

0.0e+000

Zn O, (10 2)

Zn O, (1 00)

1.0e+003

Grains with more uniform size distribution are present in films "B". A
mechanism for the grain growth in ZnO films was proposed and

Zn O, (1 0 1)

2.0e+003

Zn O, (00 2)

Intensity (cps)

4.0e+003

3.0e+003

Zn O

30

6.0e+003

20

4.0e+003
10

2.0e+003
0.0e+000
20

30

40

50

60

70

2-theta(deg)

20

30

40

50

60

(a)

70

2-theta(deg)

The XRD pattern of film "A" reveals their polycrystalline structure

structure

REFLECTIVITY PROFILE
10

10
10

Reflectivity (a.u.)

10

10

The XRD pattern of asas-deposited film "B" shows that the film has a
poor crystallinity,
crystallinity, with (002) preferential orientation. The nanocrystalls

10

10

10

size is ~ 11.7 nm.

10

(b)

-1

10
-3

X-ray diffraction: pattern

(a), Reflectivity profile (b),
Density distribution (c) of
ZnO film deposted from Zn
metallic target.

-4

-5

-6

10
10
10
10

-7
0.0000

5.0000
Density
Distr.
2theta
angle (deg.)

6.00000

The reflectivity profiles reveal the increased porosity and surface

surface

10

-2

Reflectivity (a.u.)

with (100), (002) and (101) oriented nanocrystalls.

nanocrystalls. The nanocrystalls
size is ~ 10.5 nm.

10

10.0000
Density distr.

10

5.00000

[1] W. Gao,
Gao, Z. Li, ZnO thin films produced by magnetron sputtering, Ceramics Internat.
Internat.
30, 11551155-1159 (2004).
[2] M. Suchea,
Suchea, S. Christoulakis,
Christoulakis, K. Moschovis,
Moschovis, N. Katsarakis,
Katsarakis, G. Kiriakidis,
Kiriakidis, ZnO
transparent thin films for gas sensor applications, Thin Solid Films
Films 515, 551 (2006).
[3] Y. Sato, T. Yamamoto, Y. Ikuhara,
Ikuhara, Atomic Structures and Electrical properties of
ZnO Grain Boundaries, J. Am. Ceram.
Ceram. Soc. 90(2), 337 (2007).

X-ray diffraction: pattern

(a), Reflectivity profile (b),
Density distribution (c) of
ZnO film deposted from
ZnO target.

-2
-3
-4
-5
-6

(b)

-7
-8
0.0000

5.0000
2theta angle (deg.)

10.0000

Density Distr.
Density distr.

5.00000

Density (g/cm3)

4.00000

1.00000

0.00000

-1

(c)

3.00000

2.00000

References

Meas. data
Simulation

6.00000

4.00000
Density (g/cm3)

roughness of films "A" comparatively with the asas-deposited ZnO films

"B".

REFLECTIVITY PROFILE

Meas. data
Simulation

3.00000

2.00000

0.000

50.000
Depth (nm)

100.000

1.00000

(c)
0.00000

No.
Layer
Func.
-----2
1
0

Thickness

Density

Roughness

----------

(nm)
------------

(g/cm3)
--------------

(nm)
------------

ZnO
ZnO
GLASS

1.63(2)
89.9(19)
0.000[--]

1.55435[--]
1.32(4)
2.21000[--]

0.422(5)
3.0(2)
4(3)

Period
No.
-------Linear
Linear
Const.

--2
1
0

0.000

Layer
-------------ZnO
ZnO
GLASS

50.000

Thickness
(nm)
-------------1.244(14)
102.0(2)
0.000[--]

Depth (nm)

100.000

Density
Roughness
(g/cm3)
(nm)
----------------1.03385[--] 2.79(6)
1.17(2)
1.41(3)
2.21000[--] 0.0(16)

150.000

Period Func.
------------Linear
Linear
Const.

[4] B. Wang, J. Min, Y. Zhao, W. Sang, C. Wang, The grain boundary

boundary related pp-type
conductivity in ZnO films prepared by ultrasonic spray pyrolysis,
pyrolysis, Appl.
Appl. Phys. Lett.
Lett. 94,
192101 (2009).
[5] J.M. Yuk, J.Y. Lee, Y.S. No, T.W. Kim, W.K. Choi,
Choi, Evolution mechanisms of the
surface morphology of grains in ZnO thin films grown on p-InP substrates due to
thermal annealing, Appl.
Appl. Phys. Lett.
Lett. 93, 021904 (2008).

Acknowledgments
This work was supported by Project 1111- 048/2007048/2007-2010 Financed by MECI Romania.
RP acknowledges with thanks the support received from Dr. C.Kusko for AFM films
morphology characterzation and from M. Danila for XRD analyses.

EMRS 2009 Strasbourg France