Journal of ELECTRONIC MATERIALS

DOI: 10.1007/s11664-016-5235-5
Ó 2017 The Minerals, Metals & Materials Society

Structural and Optical Properties of Group III Doped

Hydrothermal ZnO Thin Films

ASAD J. MUGHAL,1,4 BENJAMIN CARBERRY,2 JAMES S. SPECK,1

SHUJI NAKAMURA,1,3 and STEVEN P. DENBAARS1,3

1.—Materials Department, University of California Santa Barbara, Santa Barbara, CA 93106,

USA. 2.—Department of Electrical and Computer Engineering, University of Florida, Gainesville,
FL 33063, USA. 3.—Department of Electrical and Computer Engineering, University of California
Santa Barbara, Santa Barbara, CA 93106, USA. 4.—e-mail: [email protected]

In this work, we employ a simple two-step growth technique to deposit impurity

doped heteroepitaxial thin films of (0001) ZnO onto (111) MgAl2O4 spinel sub-
strates through a combination of atomic layer deposition (ALD) and hydrothermal
growth. The hydrothermal layer is doped with Al, Ga, and In through the addition
of their respective nitrate salts. We evaluated the effect that varying the con-
centrations of these dopants has on both the structural and optical properties of
these films. It was found that the epitaxial ALD layer created a
h111iMgAl2 O4 h0001iZnO out-of-plane orientation and a h1
12i
 
MgAl2 O4 k h0110iZnO in-
plane orientation between the film and substrate. The rocking curve line widths
ranged between 0.75° and 1.80° depending on dopant concentration. The optical
bandgap determined through the Tauc method was between 3.28 eV and 3.39 eV
and showed a Burstein-Moss shift with increasing dopant concentration.

Key words: Hydrothermal deposition, ZnO, TCO, thin films, ALD, Burstein-
Moss Effect

INTRODUCTION conductive films such as indium tin oxide (ITO),

ZnO can typically be deposited at lower costs using a
Zinc oxide (ZnO) is a group II-VI direct band gap
variety of physical and chemical deposition tech-
compound semiconductor material used in a wide
niques. However, using a single deposition method
array of electronic applications.1 Given its wide
to produce high quality ZnO films for device appli-
band gap and ease of doping, ZnO films can
cations can be challenging.
simultaneously achieve high optical transparency
There exist several methods for depositing ZnO
and low electrical resistivity. Transparent elec-
thin films such as pulsed laser deposition (PLD),10
trodes composed of ZnO have been shown to be
molecular beam epitaxy (MBE),11 electron beam
applicable to optoelectronic devices such as light
deposition,12 thermal evaporation,13 and magnetron
emitting diodes,2,3 laser diodes, and photovoltaics.4
sputtering.14 All approaches have benefits and
In addition to those devices, conductive films con-
drawbacks in terms of control over growth rate,
taining zinc oxide can be used in thin film transis-
uniformity, and composition. However, most require
tors, varistors, piezoelectric transducers, as well as
energy intensive high vacuum conditions to operate.
gas, chemical, and biological sensors.5–7 ZnO thin
Atmospheric or near atmospheric deposition
films can be readily made highly conductive through
schemes can drastically reduce the expenses asso-
doping with substitutional atoms such as group
ciated with the deposition of these materials and
three elements (e.g. B, Al, Ga, and In).8,9 ZnO films
allow for wide-spread application. Atomic layer
can also be easily patterned using either wet or dry
deposition (ALD) allows for the precise growth of
etching methods. Additionally, compared to
thin conformal coatings of ZnO on a variety of
substrates, but due to the self-limiting aspect of the
growth mechanism, the thickness is limited for
(Received August 10, 2016; accepted December 15, 2016) practical deposition times.15 If this technique can be
 Mughal, Carberry, Speck, Nakamura, and DenBaars

successfully combined with a deposition method

with faster grow rate, then it would be possible to
practically grow transparent and conductive ZnO
thin films on a variety of substrates for various
applications. Hydrothermal growth,16 also referred
to as chemical bath or aqueous solution deposition,
allows for the deposition of relatively thick films of
ZnO at relatively fast growth rates in comparatively
mild conditions of less than 100°C at atmospheric or
autogenous pressures. The composition and mor-
phology of the film growth through this method can
easily be changed through modifying the precursors
in the growth solution. The growth of ZnO occurs in
the presence of supersaturated Zn ions at elevated
temperatures due to the retrograde solubility of Zn
in aqueous solutions.17 These films can be readily
doped through the addition of impurities in the
growth solution such as the salts of group III Fig. 1. SEM cross sectional micrograph of a typical ALD/hy-
elements. Doped hydrothermal ZnO films have been drothermal ZnO thin film on spinel substrate.
demonstrated for In,18 Ga,19 and In/Ga co-doping.20
However, no systematic study on the effect of
dopants on structural and optical properties of
hydrothermal ZnO films exists to date. spectra, while a double axis, rocking curve config-
In the present study, we present a method for uration was used for on axis omega scans and off
depositing and doping thin films of ZnO through a axis phi scans. An Agilent Cary 500 spectropho-
two-step ALD and hydrothermal deposition proce- tometer was used to carry out normal incident
dure. The structural and optical properties of these transmission measurements on the ZnO thin films.
films are characterized and studied with respect to Film morphology was observed using JEOL 7600F a
type and concentration of dopant added to the film. field emission scanning electron microscope
(FESEM).
EXPERIMENTAL DETAILS
RESULTS AND DISCUSSION
Prior to deposition 1 cm2 (111) MgAl2O4 spinel
substrates were cleaned by 3 min dips in acetone SEM
and isopropanol followed by an 18 MX cm deionized The thin films that resulted from hydrothermal
(DI) water rinse and 5 min dip in a 1:1 solution of growth of doped ZnO on an ALD seed layer had
HCl and H2O. The substrates were then rinse again thicknesses which ranged between 1 and 3 lm. A
with DI water and dried under N2. A 5 nm thick cross sectional SEM micrograph of a typical ZnO
seed layer was deposited onto the substrate at thin film on a spinel substrate is shown in Fig. 1.
200°C using an Oxford Instruments FlexAl ALD The nanoscale pores form during the second anneal-
system with diethylzinc and water as precursors. ing step and can be caused by either the coalescence
This layer was then annealed at 600°C for 10 min in of zinc vacancies21 or the result of a phase change
air using an AET RX6 rapid thermal anneal (RTA) that occurs from the dehydration of less dense
system. Following this, the substrates were placed Zn(OH)2 to the denser ZnO phase.22 The porosity of
in a reaction vessel containing a 25 ml solution these films decreased with increasing dopant con-
composed of 25 mmol/L zinc nitrate (Zn(NO3)2), centrations with films doped at 1 mM generally
5 mmol/L trisodium citrate (Na3C6H5O7), and 0 to showing very little porosity, cross sectional SEM
1 mmol/L of either aluminum nitrate (Al(NO3)3), micrographs are provided in supplementary
gallium nitrate (Ga(NO3)3), or indium nitrate materials.
(In(NO3)3). Prior to submerging the substrates into
solution, 1.3 ml of 29 wt.% ammonium hydroxide XRD
(NH3OH) was added to achieve a pH of 10.5. The
reaction vessel was capped, placed in 90°C oven, Figure 2 displays a log scale plot of a 2theta/
and allowed to react for 2 h, after which the samples omega scan of an unintentionally doped (UID) ZnO
were rinsed with DI water. The samples then thin film. Although the (0002) reflection of the ZnO
underwent a second RTA at 300°C for 10 min in film and the (111) reflection of the MgAl2O4 are the
air prior to characterization. major features, the scans show a weak reflection
X-ray diffraction spectra were collected using a  plane of ZnO as well. This feature is
from the (1011)
Panalytical MRD PRO high resolution x-ray diffrac- also found in several, but not all the doped samples.
tometer with a Cu ka1 (1.5405 Å) source. A triple It indicates that the film and substrate have a
axis configuration was used to acquire on axis 2h/x h111iMgAl2 O4 h0001iZnO out-of-plane orientation.
Structural and Optical Properties of Group III Doped Hydrothermal ZnO Thin Films

Their in-plane alignment was determined by off-

axis phi scans of the (10–11) ZnO and (400)
MgAl2O4 peaks, shown in Fig. 3. The respective
peaks of the substrate and film line up, meaning
that they have h1 12i
 h0110i
 and
MgAl2 O4 ZnO
   
h110iMgAl2 O4 h2110iZnO in-plane orientation. This
indicates that the closed packed oxygen planes of
both ZnO and MgAl2O4 are aligned with a lattice
mismatch of 13.6%,23 similar MBE grown films.24
Sputtered and hydrothermal ZnO seed layers on
MgAl2O4 typically have a 30° rotation between the
closed packed oxygen directions, resulting in a
much lower lattice strain of 1.6%.25 The well-
defined sixfold symmetry found in the off-axis phi
scan, shown in Fig. 3, of the (1011) peak of ZnO is
also indicative of a highly c-plane oriented film.
The large lattice mismatch between film and
Fig. 2. 2theta/omega scans of UID ZnO film. substrate results in films with high degree of
mosaicity. A representative rocking curve scan,
shown in Fig. 4a, was fitted to a Gaussian function
from which line widths were determined. The line
widths of films doped in the hydrothermal growth
solution at various concentrations of Al, Ga, and In
are shown in Fig. 4b. The line widths of these films
range between 0.8° and 1.8°, which is much higher
than films grown using techniques such as MBE.23
The overall trend shows that increasing the con-
centration of dopant initially increases the films
mosaic spread, but at a certain concentration the
films crystal quality improves. It is believed that the
group III elements in the hydrothermal growth
solution undergo a similar dehydration reaction
from a hydroxide phase to an oxide during film
formation.26 At certain concentrations, the lattice
strain that is formed by the incorporation of a
dopant of a different ionic radius into the film may
offset the strain due to the lattice mismatch
between film and substrate. This may allow for the
growth of ZnO films with a lower defect density.
However, actual incorporation of the group III
dopants in the film may not be linearly proportional
Fig. 3. Off-axis phi scans for Spinel (400) and ZnO (101) reflections. to the concentration of nitrate salts added to the
solution during growth.

Fig. 4. (a) Rocking curve scan of the (002) ZnO reflection and (b) FWHM of rocking curve scans for doped ZnO films.
 Mughal, Carberry, Speck, Nakamura, and DenBaars

Fig. 5. (a) Tauc plot for UID ZnO and (b) optical bandgap for doped ZnO films.

This could account for the deviation in the trend also exhibited the Burstein-Moss effect due to the
seen at lower dopant salt concentrations. incorporation of dopant atoms into the film. The
ability to produce high quality thin films of ZnO
Optical Bandgap using a scalable deposition method with control of
optical, electrical, and structural properties through
UV–Vis-NIR transmission spectra were taken on
control over process parameters and doping could
the same set of samples and were used to determine
enable further application of this material for
their optical bandgap. (ahm)2 versus hm Tauc
electronic, optoelectronic, and sensing applications.
plots27,28 were calculated from those spectra, and
Future work will address the dopant concentrations
the linear portion of the absorption edge was
within the ZnO films, as well as their electrical
extrapolated to the energy axis, as shown in Fig. 5a
properties.
for a UID ZnO film. Optical bandgap of ZnO is
typically measured to be 3.3 eV.29 As seen in ACKNOWLEDGEMENTS
Fig. 5b, the optical bandgap of ZnO can be substan-
This work was funded in part by the Solid-State
tially influenced by the addition of dopants in the
Lighting Program (SSLP), a collaboration between
hydrothermal growth solution, ranging from 3.28 to
King Abdulaziz City for Science and Technology
3.39 eV depending on the type and concentration of
(KACST), King Abdullah University of Science and
dopants. For Ga and Al doped films, there was a
Technology (KAUST), and University of California,
general broadening of optical bandgap, likely due to
Santa Barbara. A portion of this work was carried
the Burstein-Moss effect.30 As the addition of
out in the UCSB nanofabrication facility, with
dopants increases the materials carrier density,
support from the NSF National Nanotechnology
the Fermi level enters the conduction band affecting
Infrastructure Network (NNIN) (ECS-03357650), as
band gap absorption by forcing excited carriers to go
well as the UCSB Materials Research Laboratory
into states above the Fermi level. Carrier scattering
(MRL), which is supported by the NSF Materials
may also play a part in this change in the optical
Research Science and Engineering Centers
bandgap. Microstructural defects, ionized impuri-
(MRSEC) Program (DMR-1121053).
ties, and lattice strain can all influence the absorp-
tion band edge of the film. In the case of In doped
films, the addition of greater concentrations of
dopants in solution does not results in a broadening
of the optical band gap after 0.4 mM. This is likely ELECTRONIC SUPPLEMENTARY
due to issues with the incorporation of In in the MATERIAL
films and the conversion of In(OH)3 into In2O3.
The online version of this article (doi:
CONCLUSIONS 10.1007/s11664-016-5235-5) contains supplemen-
In summary, we have successfully synthesized tary material, which is available to authorized
epitaxial ZnO thin films on MgAl2O4 spinel sub- users.
strates using a two-step growth method involving
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