Review Article: Atomic layer deposition of

doped ZnO films

Cite as: J. Vac. Sci. Technol. A 37, 050802 (2019); https://doi.org/10.1116/1.5112777
Submitted: 03 June 2019 . Accepted: 30 July 2019 . Published Online: 16 August 2019

Zhengning Gao, and Parag Banerjee

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Paper published as part of the special topic on Special Topic Collection on Atomic Layer Deposition (ALD)
Note: This paper is part of the 2020 Special Topic Collection on Atomic Layer Deposition (ALD).

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© 2019 Author(s).
Review Article: Atomic layer deposition of doped ZnO films
Zhengning Gao1 and Parag Banerjee1,2
1
Department of Materials Science and Engineering, University of Central Florida, Orlando, Florida 32816
2
Nano Science and Technology Center (NSTC), University of Central Florida, Orlando, Florida 32816

(Received 3 June 2019; accepted 30 July 2019; published 16 August 2019)

This article reviews the process-structure-property relationship in doped ZnO thin films via atomic
layer deposition (ALD). ALD is an important manufacturing-scalable, layer-by-layer, thin film deposi-
tion process that precisely controls dopant type and concentration at the nanoscale. ZnO is an impor-
tant technological material, which can be doped to modulate structure and composition to tailor a
wide variety of optical and electronic properties. ALD doped ZnO is viewed as a transparent conduct-
ing oxide for application in solar cells, flexible transparent electronics, and light-emitting diodes. To
date, there are 22 elements that have been reported as dopants in ZnO via ALD. This article studies
the underlying trends across dopants and establishes generalized relationships for (1) the role of ALD
process parameters, (2) the impact of these parameters on the structure of the ZnO matrix, and (3) the
impact of dopants on the optical and electrical properties. The article ends with a brief discussion on
the limitations of the ALD-based doping scheme, knowledge gaps in the compositional maps,
and a perspective on the future of ALD doped ZnO films. © 2019 Author(s). All article content,
except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license
(http://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1116/1.5112777

I. INTRODUCTION
Atomic layer deposition (ALD) exerts the ultimate control
over film thickness and composition at the nanoscale. The
sequential pulsing of precursor molecules leads to self-
limited chemisorption from the gas phase on to surfaces and
results in monolayer growth of films. Mixing and matching
pulse chemistries results in new tailor-made compositions,
harder to achieve by other deposition techniques. These
process advantages in ALD have been realized through more
than two decades of fundamental and applied research and
highlighted in numerous review articles.1–15 Today, ALD is
a manufacturing-at-scale process, adopted by industry and
projected to reach a market value of $3.01 billion by 2025.16
ZnO is a wide bandgap (3.30 eV) semiconductor that is a
versatile materials platform used in thin film electronics, gas
sensors, light-emitting devices, photodiodes, solar cells, and
catalysts.17–22 These applications are made possible by a rich
compositional diversity achievable by doping ZnO with
various elements. For example, Mg-doped ZnO and Cd-doped
ZnO are two compositions typifying the use of doped ZnO for
bandgap engineering in optoelectronic devices.23,24
Thus, given (1) the process advantages of ALD and (2) the
material importance of ZnO, ALD of ZnO presents immense
opportunities for future devices and technologies. ALD chem-
istry for ZnO was first demonstrated by Tammenmaa et al.
using zinc acetate and water as precursors.25 Since then, a
large body of work has been published, detailing fundamental
mechanisms of ALD of ZnO using diethyl Zn (DEZ) as a pre-
cursor and the ability to dope ZnO using a combination of
various precursor molecules.26–32 There are 22 elements that
have been used to dope ZnO via ALD. This is shown in
Note: This paper is part of the 2020 Special Topic Collection on Atomic
Layer Deposition (ALD).
Fig. 1(a). Applications of ALD doped ZnO have included thin
film transistors, solar cells, light-emitting diodes, and gas
sensors.33–36 The main motivation for developing ALD doped
ZnO as a transparent conducting oxide (TCO) is to replace
currently used TCOs such as tin-doped indium oxide (ITO).
Given that ZnO is a wide bandgap semiconductor metal
oxide, it is easy to appreciate how doping can create excess
charge carriers in ZnO while maintaining optical transpar-
ency.37,38 Group III oxides and, in particular, Al2O3 is used
to synthesize Al-doped ZnO TCOs [Fig. 1(b)]. The Kröger–
Vink reaction can be represented as
2ZnO 1
Al2 O3 ! 2AlZn þ 2OX 
O þ 2e þ O2 " : (1)
2
The two electrons generated in the above reaction are
donated to the conduction band. This results in improved
electronic conductivity. One can extend the rationale to
group IV (e.g., TiO2) and group V oxides (e.g., Ta2O5),
assuming that a higher number of electrons may be avail-
able for conduction. However, the actual scenario is more
complicated than what the above reaction implies. The pres-
ence of intrinsic defects such as O vacancies, Zn intersti-
tials, and hydrogen and charge compensation mechanisms
create a complex electronic environment that has been
extensively studied in the literature.39–44
From a process perspective, the key takeaway is that ALD
represents a powerful platform to realize a range of doping
compositions by (1) elemental type and (2) atomic percent
(at. %), which allows for a systematic investigation of
process-structure-properties relationships of doped films. By
varying the order and ratio of pulsing sequence, the entire
compositional phase space can be mapped, and fundamental
processes related to doping mechanisms can be unraveled. If
the deposition rate (in nanometers/cycle) of the parent film

050802-1 J. Vac. Sci. Technol. A 37(5), Sep/Oct 2019 0734-2101/2019/37(5)/050802/17 © Author(s) 2019. 050802-1
050802-2 Z. Gao and P. Banerjee: Review Article: ALD of doped ZnO films
FIG. 1. (a) There are 22 elements that have been reported as dopants in ZnO via ALD. These are shown as highlighted boxes in the periodic table. (b) Among
the 22 elements, Al is the most widely studied dopant followed by Ga, N, Ti, and In. The other elements are listed on the x-axis as a function of decreasing
number of papers (on y-axis).
and dopant is known, the estimated atomic percent dopant
can be written as
λMOx
at: % ¼ : (2)
λMOx þ Γ  λZnO
Here, λMOx and λZnO are deposition rate per ALD cycle
for the dopant oxide MOx and ZnO, respectively, and Γ is
the cycle ratio of ZnO to MOx. The above formula assumes
no chemical “cross talk” between the parent and dopant
films and is an oversimplification. Yet, a majority of papers
use similar formulae for estimating atomic percent in ALD
doped ZnO films. Because of the ease with which ALD
doped ZnO can be fabricated and their previously stated role
in key applications, there now exists a wealth of literature
that needs to be collectively assessed.
Therefore, the aim of this paper is to review current data
and extract underlying trends in ALD doped ZnO films that
may aid in our understanding to design and synthesize the
next generation of doped ZnO films and other multicompo-
nent films via ALD. Table I provides a comprehensive list of
ALD doped ZnO films from the perspective of TCOs.45–207
This table lists the doped element, the precursor molecules
used, the composition (or cycle ratio) at which the TCO
properties are optimized, the thickness deposited, and the
optical and electrical properties.
With a view to aid practitioners of ALD design better pro-
cesses, this review focusses on the processing-structure-
properties relationships in ALD doped ZnO films. In Sec. II,
we describe the process parameters that are important for pro-
ducing efficiently doped ALD ZnO films. Next, the character-
ization of these films is discussed. In particular, x-ray
diffraction (XRD), x-ray photoelectron spectroscopy (XPS),
and photoluminescence (PL) data are discussed for various
ALD doped ZnO films. Finally, optical and electrical proper-
ties are highlighted. Where there is availability of extensive
data, generalized trends in ALD doped ZnO films are pre-
sented. At the end, limitations in the processing schemes,
knowledge gaps in the compositional maps, and perspectives
on the future of ALD doped ZnO are described.
J. Vac. Sci. Technol. A, Vol. 37, No. 5, Sep/Oct 2019
050802-2
II. EFFECT OF ALD PROCESS PARAMETERS
ALD process parameters strongly dictate properties of
doped ZnO. In this section, the effect of pulsing sequence,
deposition temperature, and choice of dopant precursor mol-
ecules is considered.
A. Effect of pulsing sequence
Dopant distribution can be precisely tuned along the
thickness direction of an ALD film. Injecting a dopant pulse
after a few, fixed cycles of Zn and oxidant precursor mole-
cules is the most common method for synthesizing doped
ZnO.27,89,207 The entire sequence, or “super-cycle,” is then
repeated to achieve the desired thickness. This is schematically
shown in Fig. 2(a) for the cation Al3+ doped in ZnO, although
the efficiency of doping of anions such as N is known to be
sequence dependent as well.134 By considering the “pre”
dopant pulse (Zn or oxidant, “O”), the dopant pulse, and the
“post” dopant pulse (Zn or O), one can see that there are at
least four (i.e., 2 × 2) combinatorial ways of achieving the
pulse sequences. These sequences are represented from n1 to
n5 in Fig. 2(b), based on the recent work by Le Tulzo et al.127
Sequence n1 has two consecutive oxidant pulses that differs
from sequence n5 which has only one postdopant H2O pulse.
Additionally, we have included the pulse sequence “co,” i.e.,
a co-injection pulse where both DEZ and dopant are pulsed
into the reactor simultaneously.90
There are marked differences in electrical properties
observed between these pulse sequences. We specifically
discuss the widely published case of Al-doped ZnO.127
According to Le Tulzo et al., the sequences n1 and n5
described above, where the DEZ pulse immediately precedes
a trimethyl aluminum (TMA) pulse, create lower resistivity
films for films deposited at 200 °C and a TMA:DEZ cycle
ratio of 1:10. This has been suggested to be due to the
etching of TMA on ZnO surfaces, which leads to superior Al
incorporation inside the ZnO film. On the other hand, Pollock
and Lad 99 have shown that sequence of type, n2 lowers film
resistivity for films deposited at 160 °C with a TMA:DEZ
cycle ratio of 1:11. Additionally, the Al-doped ZnO film
 TABLE I. Listing of cation and anion dopants used in ALD doped ZnO along with the precursor chemistry, process parameters, deposition rate, substrate type, and optical and electrical properties. Optical bandgap indicates the largest bandgap of the ALD doped
ZnO, and optical transmittance data are recorded between 400 and 800 nm.

ZnO chemistry Dopant chemistry Optical Electrical

Deposition Deposition Carrier

temperature Optimal Optimal rate Thickness Bandgap Resistivity concentration Mobility Other
Element Zn precursor Oxidant Dopant precursor Oxidant (°C) cycle ratio atomic % (nm/cycle) Substrate (nm) (eV) Transmittance (Ω cm) (cm−3) (cm2/V s) References References

1 Cations H+ Diethyl Zn H2O H-plasma — 200 — — 0.14 Glass 172 3.64 92.5% 7.30 × 10−4 6.00 × 1020 14.0 198 199, 200
2 Mg2+ Diethyl Zn H2O Bis(ethylcyclo-pentadienyl) — 200 1:7 — — Thermal SiO2 50 3.9b 85.0% — — — 203 204b
magnesium
3 Mn2+ Zinc acetate H2O/O3 Mn(thd)3, Mn(acc)3 H2O/O3 230 1:9 — — c-Sapphire, — — — — — — 177 —
c-Sapphire–
GaN

JVST A - Vacuum, Surfaces, and Films

4 Co2+ Diethyl Zn H2O Cobalt (II) acetyloacetonate Cobalt H2O 160 c-Sapphire, 176
Dimethyl Zn (II) chloride hydrate GaAs,Si, Glass
5 B3+ Diethyl Zn H2O B2H6 — 165 — — — Glass 200 3.48b 90.0% 6.40 × 10−4 8.00 × 1020 15.0 131 102b, 130,
132,133
6 Ga3+ Diethyl Zn H2O Hexakis (dimethylamino) gallium H2O 300 1:33 3 — c-Sapphire 54 3.59b 90.0% 3.30 × 10−4 1.38 × 1021 13.0 158 72, 149–157b,
159
7 Al3+ Diethyl Zn H2O Trimethylaluminum H2O 200 — 5 — Glass, 200 3.73a,b 80.0% 6.50 × 10−4 7.90 × 1020 11.8 52 25–27, 45–51,
c-Sapphire 53–88, 89b,
90–129
8 As3+ Diethyl Zn H2O As — 280 — — — GaN/Al2O3 2000 — — — — — 201 —
9 In3+ Diethyl Zn H2O Trimethyl indium H2O 200 — 80 — Thermal SiO2 40–50 — — 3.90 × 10−4 3.00 × 1020 50.0 166 163–165,
167–169
10 Ge4+ Diethyl Zn H2O Tetramethoxy germanium H2O 250 — 1.4 — Glass 300–400 3.62a 78.0% 1.50 × 10−2 1.50 × 1020 11.0 178 —
11 Si4+ Diethyl Zn H2O (N,N-dimethylamino) H2O 300 1:35 2.1 — Si, Glass, 150 3.38a 85.0% 9.20 × 10−4 4.30 × 1020 15.6 184 —
trimethylsilane c-Sapphire
050802-3 Z. Gao and P. Banerjee: Review Article: ALD of doped ZnO films

12 Ti4+ Diethyl Zn H2O Titanium isopropoxide H2O 200 1:20 — — Si, Thermal 100 4.00a 80.0% 8.87 × 10−4 4.80 × 1020 15.0 186 185, 187–193
SiO2, Quartz
13 Zr4+ Diethyl Zn H2O Tetrakis (dimethylamino) H2O 180 — 2 — c-Sapphire 100 3.34 90.0% 1.30 × 10−3 2.20 × 1020 24.0 172 173–175
zirconium
14 Sn4+ Diethyl Zn H2O Tetrakis (dimethylamino) tin H2O 150 1:3 — — Si — — — — — — 206 —
15 Hf4+ Diethyl Zn H2O Tetrakis-ethylmethyl amino H2O 200 — 3.3 — Glass, 100 3.55a 80.0% 6.00 × 10−4 3.00 × 1020 22.0 180 181–183
hafnium c-Sapphire
16 Nb5+ Diethyl Zn H2O Niobium Pentaethoxide H2O 180 — 3.4 — Si 50 — — — — 7.9 205 —
17 Ta5+ Diethyl Zn H2O Pentakis (dimethylamino) tantalum H2O 170 1:40 1.8 — Si, Glass, 30 3.39a 80.0% 4.00 × 10−3 1.20 × 1020 11.0 207 —
Quartz
18 Anions F− Diethyl Zn H2O HF — 140 — 1 — Thermal SiO2 287 3.42a 80.0% 1.88 × 10−3 1.38 × 1020 24.2 194 195–197
19 Cl− Diethyl Zn H2O HCl (33%–40% in Water) — 140 — 0.65 — Thermal SiO2 200 3.36a 80.0% 1.21 × 10−2 5.72 × 1019 31.8 202 —
20 S2− Diethyl Zn H2O H2S — 110 — 1.4 0.2 Thermal SiO2 100 2.65b — 1.00 5.00 × 1015 11.5 160 161, 162b
21 N3− Diethyl Zn H2O NH3 — 190 — 2.5 0.25 Glass 50 2.89b — 2.10 × 10+1 6.00 × 1016 4.0 141 134–140,
142–145, 146b,
147,148
22 P3− Diethyl Zn 2% O3 Trimethyl phosphite 2% O3 250 — 1.4 — Thermal SiO2 150 — — 3.00 × 10−3 1.30 × 1020 18.0 170 72, 171, 172

a
Bandgap due to Burstein–Moss effect.
b
Optical bandgap data are obtained from reference in last column, i.e., other than the electrical data reference.
050802-3
050802-4 Z. Gao and P. Banerjee: Review Article: ALD of doped ZnO films 050802-4

FIG. 2. (a) Schematic of Al-doped ZnO film showing one super-cycle consisting of n monolayer ZnO and one Al2O3 monolayer. (b) Schematic of pulse
sequences vs time, used for doping ZnO. (c) Cross-section TEM showing quasi-superlattice-like structure of Al-doped ZnO. Reprinted with permission from
Lee et al., Adv. Funct. Mater. 21, 448 (2011). Copyright 2010, John Wiley and Sons. (d) Auger electron spectroscopy depth profile of 1 at. % Al doping in
ZnO with periodically separated doping sequence. Reprinted with permission from Yuan et al., J. Vac. Sci. Technol. A 30, 01A138 (2012). Copyright 2012,
American Vacuum Society. (e) Atom probe tomography of Al-doped ZnO showing Al doping and mixing with the ZnO matrix. Reprinted with permission
from Wu et al., Chem. Mater. 30, 1209 (2018). Copyright 2018, American Chemistry Society. (f ) Comparison of estimated and measured thickness vs percent-
age of ZnO cycle. Reprinted with permission from Elam and George, Chem. Mater. 15, 1020 (2003). Copyright 2003, American Chemistry Society.
(g) Deposition temperature dependence of resistivity of Al-doped ZnO. Reprinted with permission from Ahn et al., Thin Solid Films 545, 106 (2013).
Copyright 2013, Elsevier. (h) Surface treatment effect on carrier density of Al-doped ZnO. Reprinted with permission from Yanguas-Gil et al., Chem. Mater.
23, 4295 (2011). Copyright 2011, American Chemistry Society. (i) Type of dopant precursor effects doping efficiency of Al-doped ZnO films. Reprinted with
permission from Wu et al., Chem. Mater. 25, 4619 (2013). Copyright 2013, American Chemical Society.

crystallinity and texture is enhanced along the [002] direction.
It is also suggested that the DEZ step after TMA helps to
localize and bind the defect site produced as a result of prior
TMA etching. Variation of pulse sequence has not been tried
for dopants other than Al.
In contrast to periodically layered dopants, homogeneous
dopant distribution can also be achieved using ALD.162,202
The co-injection pulse sequence is labeled as “co” in
Fig. 2(b). Yuan et al.90 have achieved co-injection by tuning
the partial pressure of DEZ and TMA to maintain an appropri-
ate mixture ratio during the precursor pulse. For similarly
doped Al atomic percent, the homogenously doped films
show better crystallinity and mobility as compared to the peri-
odically doped films. Improved electrical performance of
homogeneous Hf-doped ZnO has been reported as well.182
Understanding interaction effects of the precursors with
the film come from both in situ and ex situ analyses of pro-
cesses and films. In situ quartz crystal microbalance,27,87
quadrupole mass spectrometry,207 and in situ conductance
measurements87 provide insights into how the dopant pulse
interacts with the film. Ex situ characterization of films
using TEM has shown the quasi-superlattice-like, periodi-
cally layered microstructure as shown in Fig. 2(c).92 Auger
electron spectroscopy can determine the periodicity of the
dopant layers [Fig. 2(d)].90 Recently, the Kessels group125
has shown the periodicity of Al-doped films using atom
probe tomography [Fig. 2(e)]. Surprisingly, the Al concen-
tration profile along the depth of the film is not as discrete
as previously thought and shows considerable mixing with
the ZnO matrix.

J. Vac. Sci. Technol. A, Vol. 37, No. 5, Sep/Oct 2019

050802-5 Z. Gao and P. Banerjee: Review Article: ALD of doped ZnO films
B. Dopant precursor effect on growth rates
Ideally, the dopant pulse should not interact with the
underlying film. However, in practice there is significant
chemical “cross talk” between the dopant pulse and the
underlying film. Elam et al. were the first to show the impact
of TMA etching on ZnO films. In Fig. 2(f ),27 the thickness
difference of an AZO film between measured and estimated
values based on the “rule of mixtures” is shown. The mea-
sured thickness of Al-doped ZnO is lower than the calculated
thickness. As the Al percentage increases, the difference
between measured and calculated thicknesses increases until
the Al cycle ratio reaches 20% (i.e., 80% ZnO cycle). This
thickness difference is a result of the etching effect of TMA
on ZnO surfaces. Incidentally, trimethyl indium shows a
similar effect as well.166 Phenomenologically, it has been
shown that it takes ∼6 cycles of DEZ + H2O to recover 63%
of the original ZnO deposition rate.89 The etching mecha-
nism is responsible for the Al incorporation into the ZnO
matrix. Recent data show that a cation exchange mechanism,
where Al substitutes Zn in the film, is possible.208
In contrast to TMA, Ti-doped ZnO using tetrakis-
isopropoxide (TTIP) results in enhanced growth rates.185 This
is suggested to be due to the enhanced adsorption of TTIP
molecules on ZnO surfaces. However, the end result is
similar to the TMA case, where excess Ti is detected beyond
the rule of mixtures.
C. Effect of deposition temperature
ALD of ZnO can be performed across a wide temperature
window. For example, the lowest temperature for ZnO deposi-
tion is reported to be 60 °C using DEZ and H2O as
co-reactants.71,209 The highest temperature of ZnO deposition is
reported to be 300 °C using DEZ and H2O as co-reactants.168
The dopant incorporation must be activated between these
two extrema in temperature. However, this is not the only
consideration when choosing a suitable deposition tempera-
ture as highlighted in Fig. 2(g).82 Here, the change in resistiv-
ity is shown as a function of deposition temperature. It is
noted that the nominal temperature for ALD ZnO and Al2O3
using H2O as an oxidant is around 200 °C.27,89,209 However,
in ALD Al-doped ZnO, the lowest resistivity sample is syn-
thesized at 250 °C. The higher deposition temperature
enhances the removal of precursor ligands and carbonaceous
species from the film. Postdeposition annealing to tempera-
tures as high as 550 °C could further improve film resistivity
by redistributing dopant atoms uniformly in ZnO and simulta-
neously increasing the grain size of the film.90,105,158
D. Effect of preconditioning and precursor selection
Dopant incorporation and hence film properties are affected
by preconditioning the surface prior to the dopant pulse or
carefully choosing different precursor molecules. Essentially,
the isotropic and homogeneous distribution of dopants is a key
factor for improved transparency and conductivity of ALD
doped ZnO films. The dopant “effective radius model” can
help explain how surface poisoning and homogeneous doping
JVST A - Vacuum, Surfaces, and Films
050802-5
distribution affect the electrical property and the doping effi-
ciency.92 Here, we focus on ALD process strategies for achiev-
ing isotropic and homogeneous doping.
“Surface poisoning” using alkyl alcohols or passivation
using titanium tetra-isopropoxide210 after each TMA pulse
reduces density of surface reaction sites.93 This implies that
less Al is incorporated in each layer but counterintuitively
helps to increase the carrier density of an Al-doped ZnO film
[Fig. 2(h)].93 Alternately, using a larger Al precursor mole-
cule, such as dimethyl-aluminum isopropoxide (DMAI), can
also affect Al-doped ZnO film resistivity.95 DMAI molecules
are much larger than TMA and have a larger steric hindrance
when attached to the ZnO surface. This leads to less Al con-
centration in a single layer. The doping efficiency using
DMAI is much higher than TMA [Fig. 2(i)].95
III. STRUCTURAL CHARACTERIZATION
In this section, the impact of extrinsic dopants on the struc-
tural characteristics of ALD doped ZnO films will be pre-
sented. Dopant effects on ZnO crystallinity, chemical
bonding, and defects will be discussed while presenting x-ray
diffraction, x-ray photoelectron spectroscopy, and photolumi-
nescence data, respectively.
A. XRD
There are two primary growth directions for ALD ZnO.
ZnO, which has a wurtzite crystal structure, has a (002) plane
which is a charged, polar surface due to alternate layers of
Zn2+ and O2− along the c-axis. The a-axis (100) plane is a
charge neutral surface that consists of alternate rows of Zn2+
and O2− [Fig. 3(a)].92 Atomic layer epitaxy of ZnO on (0002)
sapphire produces a c-axis oriented film. Alternately, it has
been shown that at low temperatures, ALD of intrinsic ZnO
leads to a preferential growth of the (100) plane, while at
high temperatures the (002) plane is favored.211 This is attrib-
uted to the distribution of surface charge which in turn deter-
mines surface energies of the crystal planes during the
sequential surface reactions in ALD. Thus, the prevalence of
either the charged (002) or neutral (100) plane and their sub-
sequent presence as a function of dopant concentration
provide insights into the effectiveness of dopant incorporation
in ALD doped ZnO.
To understand dopant behavior on crystallinity, we look at
ALD doped ZnO films deposited on glass or thermal SiO2 on
Si, except for the case of N-doped ZnO which is conducted
on sapphire. Substrate effects are not considered in our analy-
sis, although it has been shown that carefully chosen sub-
strates can enhance conductivity.88
We have analyzed the effective ionic radius212 r under tet-
rahedral coordination and the charged state (+Z) of the
dopants used in ALD ZnO. The linear charge density which
can be a measure of the strength of interaction of the cation
dopant with the ZnO matrix can be approximated by the
parameter “Z/r,” that is, the charge density per unit length of
the ionic radius. Higher this parameter, stronger the interac-
tion. The linear charge density parameter is plotted as a
050802-6 Z. Gao and P. Banerjee: Review Article: ALD of doped ZnO films 050802-6

FIG. 3. (a) Wurtzite crystal structure along c-axis (left), showing alternate layers of Zn2+ and O2− in the (002) plane and along a-axis (right), showing the
charge neutral (100) plane. (b) Ionic radius under tetrahedral coordination (Ta5+ data extrapolated from Shannon) for various cations used for doping ZnO. The
size of the bubble indicates 1000 × Z/r. Cations marked by blue bubbles (large Z/r, type I) result in loss in crystallinity of the ZnO matrix. Cations marked by
red bubbles (small Z/r, type II) show improved crystallinity at low atomic percent doping, before amorphization or secondary phase formation occurs at higher
atomic percent doping. (c) XRD of Nb-doped ZnO as a function of percent cycle ratio. Reprinted with permission from Shaw et al., Appl. Phys. Lett. 109,
222103 (2016). Copyright 2016, AIP Publishing LLC. (d) XRD of B-doped ZnO as a function of atomic percent. Reprinted with permission from
Garcia-Alonso et al., J. Mater. Chem. C 3, 3095 (2015). Copyright 2015, The Royal Society of Chemistry. (e) XRD of Si-doped ZnO as a function of atomic
percent. Reprinted with permission from Yuan, J. Mater. Sci. Mater. Electron. 23, 2075 (2012). Copyright 2012, Springer Nature. (f ) XRD of Ta-doped ZnO
as a function of atomic percent. Reprinted with permission from Gao et al., Adv. Mater. Interfaces 3, 1600496 (2016). Copyright 2016, John Wiley and Sons.
(g) XRD of Ge-doped ZnO as a function of atomic percent. Reprinted with permission from Chalker et al., J. Mater. Chem. 22, 12824 (2012). Copyright
2012, The Royal Society of Chemistry. (h) XRD of Al-doped ZnO as a function of atomic percent. Reprinted with permission from Banerjee et al., J. Appl.
Phys. 108, 043504 (2010). Copyright 2010, AIP Publishing LLC. (i) XRD of Hf-doped ZnO as a function of atomic percent. Reprinted with permission from
Ahn et al., J. Electrochem. Soc. 159, H384 (2012). Copyright 2012, Electrochemical Society. ( j) XRD of Ga-doped ZnO as a function of atomic percent.
Reprinted with permission from Chalker et al., J. Vac. Sci. Technol. A 31, 01A120 (2013). Copyright 2013, American Vacuum Society. (k) XRD of
Mg-doped ZnO as a function of atomic percent. Reprinted with permission from Kaur et al., Sol. Energy Mater. Sol. Cells 161, 449 (2017). Copyright 2017,
Elsevier. (l) XRD of Zr-doped ZnO as a function of atomic percent. Reprinted with permission from Herodotou et al., Materials 8, 7230 (2015). Copyright
2015, MDPI. (m) XRD of In-doped ZnO as a function of atomic percent. Reprinted with permission from Lee et al., J. Phys. Chem. C 118, 408 (2013).
Copyright 2013, American Chemical Society. (n) XRD of F-doped ZnO as a function of atomic percent. Reprinted with permission from Choi and Park,
J. Mater. Chem. C 2, 98 (2014). Copyright 2014, The Royal Society of Chemistry. (o) XRD of Cl-doped ZnO as a function of atomic percent. Reprinted with
permission from Choi et al., J. Mater. Chem. C 3, 8336 (2015). Copyright 2015, The Royal Society of Chemistry. ( p) XRD of N-doped ZnO as a function of
atomic percent. The film was prepared using plasma enhanced atomic layer deposition and rapid thermally annealed after deposition. Reprinted with permission
from Chien et al., ACS Appl. Mater. Interfaces 4, 3471 (2012). Copyright 2012, American Chemistry Society. (q) XRD of S-doped ZnO as a function of
atomic percent. Reprinted with permission from Frijters et al., Sol. Energy Mater. Sol. Cells 155, 356 (2016). Copyright 2016, Elsevier.

J. Vac. Sci. Technol. A, Vol. 37, No. 5, Sep/Oct 2019

050802-7 Z. Gao and P. Banerjee: Review Article: ALD of doped ZnO films
bubble graph in Fig. 3(b) for Zn2+, Mg2+, In3+, Ga3+, Zr4+,
Hf4+, Al3+, Ta5+, Ge4+, Nb5+, Si4+, and B3+, where the size of
the bubble equals 1000 × Z/r. Independent of the effective
ionic radius (i.e., y-axis), there are two regions that can be
demarcated by the bubble size. The bubbles of Type I indicate
linear charge densities of cations with 1000 × Z/r > 90, signifi-
cantly higher than Zn2+(1000 × Z/r = 33). The bubbles of
Type II indicate linear charge densities of cations with
1000 × Z/r ≤ 77 and similar to Zn2+(1000 × Z/r = 33). This
demarcation using linear charge density is a useful way to
analyze the XRD data as will be shown below.
In Figs. 3(c)–3(g), XRD of doped ZnO films as a function
of atomic percent of type I cations is shown. In all the cases,
the crystallinity of the ZnO matrix monotonically degrades as
atomic percent doping increases for Nb5+ (Ref. 205), B3+
(Ref. 102), Si4+ (Ref. 184), Ta5+ (Ref. 207), and Ge4+ (Ref. 178).
The XRD peaks shift to higher 2θ, implying that lattice con-
stants decrease with atomic percent. The peak intensities
decrease and the full-width-at-half-maximum (FWHM) widens.
Irrespective of the effective ionic radius, the strong electrostatic
interaction of these cations disturbs the charge state of the ZnO
matrix and hinders crystalline growth of doped ZnO films.
In contrast, in Figs. 3(h)–3(m), XRD of doped ZnO films
as a function of atomic percent of type II cations is shown.
Here, the crystallinity of the ZnO matrix initially improves.
Peak intensities increase and FWHM narrows, before film
crystallinity starts to degrade. For example, for Al3+, the
primary peak intensity maximizes at 3 at. %,89 Hf4+ at
6.7 at. %,180 Ga3+ at 1.1 at. %,150 Mg2+ at 10 at. %,204 Zr4+ at
6.7 at. %,173 and In3+ at 4.7 at. %.166 It is noted that the linear
charge density (Z/r) of the type II cations is similar to Zn2+.
Thus, the type II cations initially improve crystallinity of the
films. At high dopant percent, past solubility limit, intercon-
nected islands of amorphous or secondary phase oxides in
the ZnO matrix, degrade ZnO crystallinity.180
For anionic dopants such as F− (Ref. 194), Cl− (Ref. 202),
N (Ref. 142), and S2− (Ref. 162), the trends in crystallinity
3−
differ from cationic dopants.142 The anionic dopants are incor-
porated in the oxygen vacancies (VO†† ) or substitute oxygen
sites. In general, peak intensities shift to lower 2θ degrees,
indicating the presence of tensile stress and an increase in
lattice constants. For F− doping [Fig. 3(n)],194 a change in
crystallinity is not observed though film texture appears to
change with increasing atomic percent doping. Since the ionic
radii of F− (1.31 Å) and O2− (1.38 Å) are almost the same, no
change in the lattice constants is observed. For Cl− doped
ZnO [Fig. 3(o)],202 the crystallinity of the film remains intact
as Cl− concentration increases to a maximum of 0.65 at. %.
The crystalline orientation of the film changes from a-axis to
c-axis. Further, the c-axis and a-axis lattice parameters
increase. This is expected as the ionic radius of Cl− is 1.81 Å,
while O2− is 1.38 Å. For N3− doping [Fig. 3(p)],142 the peak
intensity appears to diminish rapidly for post rapid thermally
annealed films and at 12.9 at. %, formation of Zn3N2 is
observed. A shift of the peak to lower 2θ is observed. Finally
for S2− doping [Fig. 3(q)],162 the entire phase space from ZnO
to ZnS has been explored. Pure ZnO starts as wurtzite with
diminishing peak intensities and shifts to lower 2θ as S atomic
JVST A - Vacuum, Surfaces, and Films
050802-7
percent increase. Fully amorphous films are observed for
>31 at. %. However, at 77 at. %, ZnS (111) with zinc blende
structure is observed.
B. XPS
XPS is a powerful surface analysis technique to study the
oxidation state of the Zn and dopant cation in doped ZnO. By
studying the perturbation of the charged state (i.e., “2+” for
the Zn cation), one can understand the degree to which the
dopant is incorporated into the ZnO matrix. Alternately, by
studying the XPS fine spectra of oxygen, the impact of
dopants on the anionic sublattice can be understood. In partic-
ular, the variation of VO†† can be monitored as a function of
dopant concentration. This is important because VO†† deter-
mines, to varying degrees, electrical properties of doped ZnO
films. Herein, we will present XPS data as a function of
dopant atomic percent for the Zn 2p and O 1s fine spectra.
In pure ZnO, Zn 2p3/2 is between 1021.8 and 1022.5 eV
and Zn 2p1/2 is 22.97 eV higher than 2p3/2.213 We find that
there is a consistent trend in the Zn peak when a dopant is
added via ALD. This trend depends on the oxidation state of
the dopant cation. In Fig. 4(a), the shift in the binding energy
(BE) is plotted (z-axis) as a function of dopant atomic
percent (x-axis) and the oxidation state (Z) of the dopant
cation (y-axis). The dopant cations for which data are avail-
able as a function of atomic percent are Z = +2 for Mg;204
Z = +3 for Al and In;31,119 Z = +4 for Zr, and Z = +5 for Ta
and Nb,205,207 whereas, for Z = +2 and Z = +3, the Zn 2p
peaks do not shift in their B.E. (i.e., shift = 0 eV), for Z = +4
and Z = +5, the shifts to higher BE are measurable. This
implies that Zn2+ loses part of its valence electrons in the
presence of these highly charge cations, namely, Zr4+, Ta5+,
and Nb5+. An example of Zn 2p3/2 peak unperturbed with
increasing dopant concentration is presented in Fig. 4(b) for
Al-doped ZnO.119 Alternately, in Fig. 4(c), Ta-doped ZnO
shows a consistent trend of peak shifts to higher BE as the
atomic percent Ta increases.207 Thus, based on the results
above, we find that the Zn 2p spectra responds to the dopant
cation for Z ≥ +4.
O1s spectrum in ZnO XPS can be deconvo-
luted119,180,195,202,205,207 into three peaks, namely, O associ-
ated with ZnO (i.e., O2−) at 529.6 eV, O in the vicinity of
VO†† at 531.8 eV, and adsorbed oxygen at 532.8 eV. For
Al-doped ZnO, systematically increasing Al concentration
leads to an initial increase of VO†† till 3.41 at. % [Fig. 4(d)].119
A subsequent increase in Al concentration leads to a decrease
in VO†† .119 Al3+ creates more VO†† at low doping and this
helps in improving film conductivity. However, other cation
dopants have a different influence on VO†† in ZnO. For
example, in Ta-doped ZnO the strong VO†† initially observed
in intrinsic ZnO [Fig. 4(e)] is clearly reduced at 5.2 at. %. As
the Ta percentage further increases, the shoulder defect peak
reappears.207 In Nb-doped ZnO shown in Fig. 4(f), the VO††
decreases from bulk ZnO to 3.8 at. % and then increases for
12.6 at. % Nb doping.205 For Hf-doped ZnO shown in
Fig. 4(g), the concentration of VO†† reaches its lowest value at
6.7 at. % and increases again as Hf concentration increases.180
050802-8 Z. Gao and P. Banerjee: Review Article: ALD of doped ZnO films 050802-8

FIG. 4. (a) BE shift of the Zn 2p core level as a function of atomic percent and charge state of the dopant. (b) Zn 2p core level spectra in Al-doped ZnO as a
function of atomic percent. Reprinted with permission from Li et al., ACS Appl. Mater. Interfaces 9, 11711 (2017). Copyright 2017, American Chemistry
Society. (c) Zn 2p core level spectra in Ta-doped ZnO as a function of atomic percent. Reprinted with permission from Gao et al., Adv. Mater. Interfaces 3,
1600496 (2016). Copyright 2016, John Wiley and Sons. (d) O 1s core level spectra in Al-doped ZnO as a function of atomic percent. Reprinted with permis-
sion from ACS Appl. Mater. Interfaces 9, 11711 (2017). Copyright 2017, American Chemistry Society. (e) O 1s core level spectra in Ta-doped ZnO as a func-
tion of atomic percent. Reprinted with permission from Gao et al., Adv. Mater. Interfaces 3, 1600496 (2016). Copyright 2016, John Wiley and Sons. (f ) O 1s
core level spectra in Nb-doped ZnO as a function of atomic percent. Reprinted with permission from Shaw et al., Appl. Phys. Lett. 109, 222103 (2016).
Copyright 2016, AIP Publishing LLC. (g) O 1s core level spectra in Hf-doped ZnO as a function of atomic percent. Reprinted with permission from Ahn
et al., J. Electrochem. Soc. 159, H384 (2012). Copyright 2012, Electrochemical Society. (h) O 1s core level spectra in Cl-doped ZnO as a function of atomic
percent. Reprinted with permission from Choi et al., J. Mater. Chem. C 3, 8336 (2015). Copyright 2015, The Royal Society of Chemistry. (i) Variation of VO††
and OH as a function of Cl atomic percent. Reprinted with permission from Choi et al., J. Mater. Chem. C 3, 8336 (2015). Copyright 2015, The Royal Society
of Chemistry. ( j) O 1s core level spectra in F-doped ZnO as a function of atomic percent. Reprinted with permission from Choi et al., Sol. Energy Mater. Sol.
Cells 132, 403 (2015). Copyright 2015, Elsevier. (k) Variation of VO†† and OH as a function of F atomic percent. Reprinted with permission from Choi et al.,
Sol. Energy Mater. Sol. Cells 132, 403 (2015). Copyright 2015, Elsevier.

One possible explanation about differences in vacancy
behavior between Al3+ compared to Ta5+, Nb5+, and Hf4+
dopants could be that the corresponding oxides of these
cations, Ta2O5, Nb2O5, and HfO2, provide a more oxygen
rich environment than Al2O3. Thus, the intrinsic VO†† asso-
ciated with ZnO is annihilated by use of the higher oxidation
state (Z ≥ 4+) dopants. However, at higher concentrations of
these dopants, density functional theory calculations predict
acceptor like metal vacancies to form.207 The acceptor like
nature of these defects implies their energy levels to be closer
to the valence band of ZnO, and thus the defects perturb the
O orbitals.
For anion dopants, the changes to VO†† are straightfor-
ward. In both Cl-doped ZnO and F-doped ZnO, the con-
centration of VO†† monotonically decreases with increasing
Cl and F concentration. The fine spectra and the trends for
Cl-doped ZnO are shown in Figs. 4(h) and 4(i), respec-
tively.202 The fine spectra and the trends for F-doped ZnO
are shown in Figs. 4( j) and 4(k), respectively.195 The
likeliest explanation for this behavior is that the direct

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050802-9 Z. Gao and P. Banerjee: Review Article: ALD of doped ZnO films 050802-9

substitution of VO†† by Cl or F in ZnO leads to the annihi-
lation of VO†† .
C. PL
Photoluminescence spectroscopy is another way to inves-
tigate ALD doped ZnO films. The near band edge (NBE)
emission of ZnO at 385 nm (=3.22 eV) corresponds to its
direct bandgap. The sharpness of this peak reflects the crys-
tallinity of the doped ZnO film. Shift in the peak position
represents changes to the bandgap. At the same time, the
broad emission on the low energy side correlates with the
defects in the ZnO due to the doping process. Thus PL, in
conjunction with XRD and XPS, can be used to study the
structure of doped ZnO films and its impact on optical and
electronic properties.214 Figure 5 shows PL spectra of ALD
doped ZnO with different dopants. For cationic dopants and
specifically in Fig. 5(a) for Al-doped ZnO,91 Fig. 5(b) for
Hf-doped ZnO,180 Fig. 5(c) for Zr-doped ZnO,173 and
Fig. 5(d) for Ta-doped ZnO;207 as the doping percentage
increases, the intensity of NBE of ZnO is quenched and the
peaks become broader. The broader shape of NBE indicates
a degradation in film crystallinity. This crystallinity change
due to the high percentage of cation doping is in line with
the XRD data, though a quantitative analysis is harder to
interpret. Furthermore, as the cation doping percentage
increases, the NBE position shifts to higher energy.
Besides NBE emission, green band emission (502 nm,
2.47 eV) is also observed. The green band emission is sug-
gested to be a result of VO†† .41,42 In Hf-doped ZnO [Fig. 5(b)]
and Ta-doped ZnO [Fig. 5(d)], the green band emission
decreases first at low doping percentage. As the doping per-
centage is increased, the green band emission reappears again.
This phenomenon indicates that VO†† is annihilated first, when
the cation dopants are introduced into ZnO. Continued increase
in the cation concentration leads to regeneration of defects.
For anion dopants, Cl-doped ZnO [Fig. 5(e)]202 and
F-doped ZnO [Fig. 5(f )],194 the change of NBE is not as
strong as for the cationic dopants. Similarly, there is little
change in NBE observed in ALD F and Ga co-doped ZnO
in Fig. 5(g) with varying F− atomic percent.215 However,
the quenching of NBE in N-doped ZnO is stronger than
Cl-doped ZnO and F-doped ZnO as shown in Fig. 5(h).213
One hypothesis for stronger NBE quenching of N-doped
ZnO would be the high negatively charged state of the N3−
compared to Cl− and F− which could strongly perturb the
anionic lattice of ZnO.213
The substitution of oxygen by chlorine and fluorine
causes the intensity of VO†† to reduce to the minimum as
shown in Figs. 5(e)–5(g). The higher the doping percent-
age, the lower the intensity of VO†† peak. This reduction of
VO†† in anion doped ZnO is similar to XPS data presented
earlier. The effect of N-doping on the defect band has not
been reported.
Thus, the cation dopants and anion dopants behave differ-
ently in the ZnO matrix and affect crystalline quality and
defect. Whereas the cations degrade the crystalline quality,
anions such as the halides do not affect the crystalline
quality. On the other hand, cations reduce VO†† concentration
at low atomic percent doping, before increasing defect con-
centration at high atomic percent doping. Anionic dopants
universally reduce VO†† .

FIG. 5. (a) PL spectra of Al-doped ZnO as a function of atomic percent. Reprinted with permission from Geng et al., J. Phys. Chem. C 115, 12317 (2011).
Copyright 2011, American Chemistry Society. (b) PL spectrum of Hf-doped ZnO as a function of atomic percent. Reprinted with permission from Ahn et al.
J. Electrochem. Soc. 159, H384 (2012). Copyright 2012, Electrochemical Society. (c) PL spectrum of Zr-doped ZnO as a function of atomic percent.
Reprinted with permission from Herodotou et al., Materials 8, 7230 (2015).Copyright 2015, MDPI. (d) PL spectrum of Ta-doped ZnO as a function of atomic
percent. Reprinted with permission from Gao et al., Adv. Mater. Interfaces 3, 1600496 (2016). Copyright 2016, John Wiley and Sons. (e) PL spectrum of
Cl-doped ZnO as a function of at%. Reprinted with permission from Choi et al., J. Mater. Chem. C 3, 8336 (2015). Copyright 2015, The Royal Society of
Chemistry. (f ) PL spectrum of F-doped ZnO as a function of atomic percent. Reprinted with permission from Choi and Park, J. Mater. Chem. C 2, 98 (2014).
Copyright 2014, The Royal Society of Chemistry. (g) PL spectrum of Ga- and F-doped ZnO as a function of atomic percent. Reprinted with permission from
Thin Solid Films 660, 913 (2018). Copyright 2018, Elsevier. (h) PL spectrum of N-doped ZnO as a function of atomic percent. Reprinted with permission
from Chien et al., Appl. Mater. Interfaces 4, 3471 (2012). Copyright 2012, American Chemistry Society.

JVST A - Vacuum, Surfaces, and Films

050802-10 Z. Gao and P. Banerjee: Review Article: ALD of doped ZnO films
IV. TRANSPARENT CONDUCTING OXIDE
PROPERTIES
Optical properties of ALD doped ZnO films will be dis-
cussed using UV-vis spectroscopy data. The electrical prop-
erties consisting of resistivity, carrier concentration, type,
and mobility will be discussed presenting data from Hall
measurements.
A. Optical properties
The bandgap is an important TCO property to ensure that
ALD doped ZnO is transparent to incoming visible light
(400–800 nm) while maintaining sufficient electrical conduc-
tivity. Thus, optical bandgap and transmittance of the film
are the two main parameters of interest. These data are
obtained via UV-vis spectroscopy of the ALD films, which
measures the spectral response of optical transmittance. The
resulting Tauć plot for direct allowed transitions (as is the
case for ZnO) yields the bandgap.216 The room temperature
direct bandgap of ALD ZnO is reported to lie between
3.19 and 3.30 eV.89,102,146,157,162,172,178,180,184,186,194,202,204,207
This corresponds to a photon wavelength of 390–377 nm. As
a result, ZnO is transparent across the entire visible spectrum.
The addition of dopant atoms leads to a change in the
bandgap. This change is a function of dopant type and the
atomic percent doping.
Because ALD can systematically dope ZnO, trends of
bandgap change with atomic percent doping can be obtained.
Here, it is noted that the Burstein–Moss effect, which causes
apparent bandgap increase due to increased carrier concentra-
tion, will be discussed under the section on electrical prop-
erty. In the absence of any phase segregation, the change in
bandgap is a continuous function of composition and can be
empirically modeled as217
Eg (c) ¼ (1  c)EgjZnO þ c EgjAOx –bc(1  c), (3)
where Eg(c) is the bandgap of the alloy semiconductor, c is the
atomic fraction of the alloy AOx, and b is the bowing parame-
ter that depends on the electronegativities of ZnO and AOx.
In Fig. 6(a), conduction and valence band edges and
bandgap of ZnO and the cationic oxides and anionic Zn
compounds are compared. The bandgap (Eg ∼ 1.23 eV) of
Zn3N2 is noted to be particularly different. The bandgap of
ZnS ∼3.56 eV, ZnF2 between 7 and 8 eV, ZnCl2 ∼3.74 eV,
MgO ∼7.8 eV, Al2O3 ∼8.7 eV, Ga2O3 ∼4.85 eV, SiO2
∼8.9 eV, GeO2 between 5.35 and 6.00 eV, ZrO2 ∼5.1 eV, HfO2
∼5.9 eV, and Ta2O5 ∼3.9 eV, which are larger than ZnO.218–227
Because the conduction band edge position of ZnF2 and B2O3
is unclear, the band structure of these is not shown.
In order to observe the effect a dopant has on the ZnO
bandgap, we plot the bandgap change as a function of
atomic percent doping. Figure 6(b) shows the atomic percent
doping from 0% to 10% for Cl− (Ref. 202), F− (Ref. 194),
B3+ (Ref. 102), Si4+ (Ref. 184), and Zr4+ (Ref. 172). All
dopants, except for Si4+, show a linear increase in bandgap
with atomic percent. For Si4+, the peak in bandgap change
(from 3.25 to 3.55 eV at 2.1 at. %) is attributed to a
J. Vac. Sci. Technol. A, Vol. 37, No. 5, Sep/Oct 2019
050802-10
maximum in the carrier concentration. Subsequently, as the
atomic percent Si4+ increases, the carrier concentration
drops and a drop in bandgap is also observed. This is attrib-
uted to the Burstein–Moss effect.
In Fig. 6(c), the effect of S2− (Ref. 162), N3− (Ref. 146),
Mg2+ (Ref. 204), Al3+ (Ref. 89), Ga3+ (Ref. 157), Ge4+
(Ref. 178), Ti4+ (Ref. 186), Hf4+ (Ref. 180), and Ta5+
(Ref. 207) on ZnO bandgap is shown and the x-axis scale
varies from 0 to 100 at. %. Because of the completeness in
data, we take the case of S2−, first.162 The two compositional
edges of ZnO and ZnS were found to have bandgaps of 3.2
and 3.4 eV, respectively. From the XRD shown previously,
the films undergo a transformation from wurtzite (ZnO) to
amorphous (ZnO + ZnS) to zinc blende (ZnS) structure.
Frijters et al.162 have used appropriate adjustments in their
Tauć plots to account for these structural changes. Using the
formula presented above, a good fit to the variation of
bandgap as a function of S doping (c) can be obtained. This
is given as Eg(c) = 3.20(1 − c) + 3.4c − 3.02(1 − c)c. N3−
addition to ZnO is the only other dopant that produces a
decrease in bandgap. This is to be expected as the bandgap
of zinc nitride (Zn3N2) is 1.23 eV.227
The case for Hf4+ deserved attention as well. Here, it is
reported that the bandgap initially increases and reaches a
maximum at 6.7 at. %.180 As the Hf4+ atomic percent increases
further, the bandgap starts to decrease. When the Hf atomic
percent is about 39.3 at. %, two clear bandgaps are observed in
transmittance spectrum. It is proposed that these two bandgaps
are due to the phase separation as a result of heavy Hf4+
doping. It is reasonable to hypothesize that this effect would
manifest in other ALD doped ZnO systems, though the sepa-
rated bandgaps have not been observed in other dopants. In all
other instances of doping ZnO, a monotonous increase in
bandgap is obtained as a function of dopant atomic percent.
In Fig. 6(d), we present the maximum change in bandgap
obtained for various dopants and their atomic percent at
which these changes are observed. It can be seen that S2−
and Ti4+ are the two most effective dopants to induce
decrease and increase in the bandgap of ZnO, respectively.
Lastly, the transmittance of ALD doped ZnO needs to be
mentioned. It is reported that the average transmittance in the
visible wavelength range is 80%–85%. Thicknesses are in the
range between 30 and 400 nm. High doping does not appear
to have a strong effect on the transmittance of the film.
B. Electrical properties
In this section, we will discuss the electrical properties of
ALD doped ZnO with respect to the following parameters:
(1) resistivity (ρ), (2) electron concentration (n), and (3)
mobility (μ); noting that electrical resistivity is given as
ρ = (neμ)−1. We only discuss single dopants even though
several papers show improved electrical properties of ALD
doped ZnO with multidopants (i.e., more than one dopant). For
example, the resistivity of Al and Ga co-doped ZnO is
7.6 × 10−5 Ω cm for a 30–40 nm film.228 We further limit our
data to published reports that have comprehensive electrical data
via Hall measurements without post-treatment of the sample.
050802-11 Z. Gao and P. Banerjee: Review Article: ALD of doped ZnO films 050802-11

FIG. 6. (a) Bandgaps and band edge alignments of various cationic oxides and anionic Zn compounds used to dope ALD ZnO. (b) The variation of bandgap vs
atomic percent doping, varying from 0 to 10 at. %. (c) The variation of bandgap vs atomic percent doping, varying from 0 to 100 at. %. Here, the variation of
bandgap with S2− addition has been fitted to the model described in the text. (d) The maximum change in bandgap is summarized as a bar chart for various
dopants. The atomic percent at which the maximum change in bandgap is measured is also listed.

Figure 7(a) illustrates the resistivity (ρ) of ALD doped
ZnO with various dopants as a function of atomic percent.
With the exception of N-doped ZnO, the trend in ρ shares
similar behavior.89,94,144,158,166,174,178,180,184,186,194,202,207 The
ρ decreases first as the dopants are introduced and reaches a
minimum. However, the specific atomic percent at which
ρ is minimized varies among dopants [Al3+ = 3 at. %,89
Ga3+ = 3 at. %,158 Si4+ = 2.1 at. %,184 Ge4+ = 1.3 at. %,178
Ti4+ = 1.2 at. %,186 Zr4+ = 4.8 at. %,174 Hf4+ = 6.7 at. %,180
and Ta5+ = 5.2 at. % (Ref. 207)]. Among all dopants, Ga-doped
ZnO has the lowest ρ of 3.30 × 10−4 Ω cm at 53 nm thick-
ness.158 We also note that Lee et al. report In-doped ZnO with
a ρ of 3.9 × 10−4 Ω cm.166 However, this doping is for 80 at. %
indium doping; which should be considered as Zn-doped
In2O3 and not In-doped ZnO.166 Finally, for N-doped ZnO the
n-type ZnO switches to p-type semiconductor as the N percent-
age increases, which leads to a monotonous increase in ρ.144
The carrier concentration (n) of ALD doped ZnO is shown
in Fig. 7(b). The n increases first as the dopant percentage
increases and reaches a maximum value (except N-doped
ZnO). The highest n is 1.37 × 1021 cm−3, which is obtained in
Ga-doped ZnO.158 It is also observed that ZnO with cation
dopants have generally higher carrier concentration as com-
pared to anion doped ZnO.
Figure 7(c) illustrates the change in the mobility (μ) of
ALD doped ZnO as a function of atomic percent doping. In
cation doped ZnO, μ decreases severely from ∼25 cm2/V s
for undoped ALD ZnO to <5 cm2/V s, as the atomic
percent doping increases. This is true for Al3+ (Ref. 89),
Ga3+ (Ref. 158), In3+ (Ref. 166), Si4+ (Ref. 184), Ge4+
(Ref. 178), Ti4+ (Ref. 186), Zr4+ (Ref. 174), Hf4+ (Ref. 180),
and Ta5+ (Ref. 207). The μ loss is particularly strong for
Ge3+ and Ti4+.178,186 It is known that μ is affected by (1)
electron-electron scattering, (2) ionized impurity scattering,
and (3) grain boundary scattering in the film. At lower atomic
percent, the electron-electron scattering will be enhanced due
to an increase in n. Dopants due to their highly charged state
are considered ionized impurities in the film, which lead to
strong scattering as the atomic percent increases. Grain boun-
dary scattering is a little difficult to assess due to the variabil-
ity in grain sizes observed in the XRD data in Fig. 3. On the
other hand, anionic dopants individually behave quite

JVST A - Vacuum, Surfaces, and Films

050802-12 Z. Gao and P. Banerjee: Review Article: ALD of doped ZnO films 050802-12

FIG. 7. (a) Resistivity of ALD doped ZnO with different dopants as a function of the atomic percent. (b) Carrier concentration of ALD doped ZnO with dif-
ferent dopants as a function of the atomic percent. (c) Mobility of the ALD doped ZnO with different dopants as a function of the atomic percent. For
clarity, insets in the above graphs show the trends in Cl, F, and P at low atomic percent. (d) Burstein–Moss plots (n)2/3 vs ΔEg, of the ALD doped ZnO
with different dopants. The m* is the reduced effective mass obtained directly from the slope of the plots. m* = 0.72 corresponds to Ti whereas, m* = 0.45
corresponds to Si.

differently. We highlight the case of Cl− doped ZnO,202 Here, h is Planck’s constant and m* is the reduced effec-
where the μ increases as the atomic percent increases. This tive mass. It can be seen that the slope of the linear relation-
effect is attributed to the fact that Cl− substitutes the O2− sites ship contains information on m* which can be given as
and oxygen vacancies, passivating dangling bonds. Further, 1 1 1
the Cl− substitution does not perturb the conduction band, *
¼ * þ * : (5)
m meV meC
which is primarily made of Zn 2p orbitals.
Finally, we discuss the apparent increase in bandgap mea-
Here, m*eV and m*eC are conduction and valence band
sured with UV-vis spectroscopy with improved electrical
density-of-states effective masses. Thus, used effectively, the
conductivity. This effect is called the Burstein–Moss
Burstein–Moss plot can provide estimates on how strongly a
effect.229,231 The effect manifests itself in degenerate semi-
dopant is able to electronically perturb the band structure in
conductors where the Fermi level is pushed beyond the con-
a host lattice. To illustrate this, in Fig. 7(d) the highest slope
duction band edge. Thus, electronic band-to-band excitations
(for Ti4+) at m* = 0.72 and the lowest slope (for Si4+) at
must energetically surpass the intrinsic bandgap of the mate-
m* = 0.45 are illustrated. This can be compared to the
rials and the excess filled states in the conduction band as a
undoped ZnO reduced effective mass of only m* = 0.17
result of the degeneracy. While details of this phenomenon
obtained using m*eV = 0.59 and m*eC = 0.24.231
are well covered in the literature, in Fig. 7(d) the relation
We note that care must be taken when interpreting optical
between carrier concentration change (n 2/3) and the optical
properties of ALD doped ZnO and discerning between
bandgap change (ΔEg) is plotted for ALD doped ZnO. For
chemical effects that lead to a change in bandgap and the
identifying the Burstein–Moss effect, this trend must be
Burstein–Moss effect.
linear. This is because the linearized form between n 2/3 and
ΔEg is given as
  2=3 V. CONCLUSIONS AND OUTLOOK
8Π 2 1
n2=3 ¼ m* ΔEg : (4) In this review article, the current state-of-the-art in ALD
h2 3π 2 doped ZnO films has been surveyed. From a materials

J. Vac. Sci. Technol. A, Vol. 37, No. 5, Sep/Oct 2019

050802-13 Z. Gao and P. Banerjee: Review Article: ALD of doped ZnO films
perspective, doped ZnO films are potentially strong candidates
as TCOs. While ITO is the most widely used TCO due to its
high conductivity [1–2 × 10−4 Ω cm for polycrystalline ITO
(Refs. 232 and 233) and 0.77 × 10−4 Ω cm for epitaxial ITO
(Ref. 234)]; polycrystalline Al-doped ZnO and Ga-doped ZnO
synthesized via RF-magnetron sputtering can achieve compara-
ble resistivities of 2.0 × 10−4 Ω cm and 2.7 × 10−4 Ω cm, respec-
tively.235,236 Similarly, epitaxially grown [via pulsed laser
deposition (PLD)], Al-doped ZnO and Ga-doped ZnO can
reach resistivities of 0.85 × 10−4 Ω cm and 0.51 × 10−4 Ω cm,
respectively.237,238 Thus, doped ZnO films have comparable
resistivities with ITO films.
From a process perspective, the lowest reported ALD
film resistivity is 3.30 × 10 −4 Ω cm for epitaxially grown
Ga-doped ZnO on c-axis sapphire. 158 The next lowest
resistivity reported is for an amorphous In-doped ZnO
film (or rather Zn-doped In 2 O 3 ) with a value of
3.90 × 10−4 Ω cm.166 Thus, PLD doped ZnO films are ∼6×
lower in resistivity than ALD doped ZnO films. Precursor
molecules with cleaner chemistries and low residual C and
N impurities, and postdeposition treatment of films can
help narrow this performance gap. On the other hand, the
process advantages that ALD has over other deposition
techniques may offset the higher resistivity of ALD doped
ZnO films. These process advantages include (1) pin hole-
free films at ultrathin (a few nanometers) thicknesses, (2)
superb conformality in high aspect ratio nanostructures, (3)
low deposition temperatures, (4) monolayer fidelity over
thickness control, (5) flexibility and ease of tuning film
composition, and (6) manufacturing scalability.
Based on the current review of the ALD doped ZnO lit-
erature, we believe that there remain knowledge gaps in
the synthesis and choice of dopants. Some of these are
listed below:
1. As was shown in Fig. 1(a), a limited set of 22 elements
have been used to dope ALD ZnO films. However,
ALD chemistries for metal oxides are widely available.2
For example, dopants such as Cd2+ have shown to
reduce ZnO bandgap and work as an n-type with
increased conductivity.239 Thus, there are opportunities
to rationally screen and explore more dopants and inte-
grate them with ALD ZnO films. The descriptor, linear
charge density (Z/r), can be a valuable metric for ini-
tially screening dopants that lead to improved crystallin-
ity of ALD doped ZnO films.
2. It is becoming increasingly important to synthesize
new molecules, specifically tailored for dopant incor-
poration in parent films. This is an often-overlooked
requirement. However, current precursors are limited
in their ability to effectively dope ZnO. For example,
the use of dimethyl-aluminum isopropoxide—a con-
siderably larger molecule than trimethyl aluminum—
results in 54% lower film resistivity.95 The idea of
adding steric hindrance, thereby spatially separating
the dopant centers can be extended to Ga- and
In-based chemistries which may result in even lower
film resistivities than currently reported.
JVST A - Vacuum, Surfaces, and Films
050802-13
3. We have intentionally limited our reporting on multido-
pants in ALD ZnO due to the relative infancy of this sub-
field. However, initial reports are promising. For example,
when 2 at. % Al-doped ZnO is deposited on epitaxially
grown GaN, the Ga diffusion into the Al-doped ZnO
results in a film resistivity of 7.6 × 10−5 Ω cm.228 On the
other hand, mixed InGaZnO have been deposited as
amorphous semiconductors for thin film transistor appli-
cations.84 These reports suggest a highly complex, mixed
metal oxide environment where the cationic sublattice
plays a crucial role in determining structure-property rela-
tionships in the films.
4. Doped ALD films usually form nanolaminate struc-
tures. On the other hand, there is a growing body of
work that shows dopant activation is most effective if
the dopants are homogeneously distributed through the
film. As a result, a high temperature postdeposition
anneal is commonly employed to redistribute dopants.
This step is not compatible for applications involving
transparent conducting ZnO films on flexible, polymeric
substrates. Thus, co-injection of dopants should be
widely adopted as means to dope ZnO.90 This is not a
trivial process to control. It implies that precursor deliv-
ery characteristics (volatility, vapor pressure, and chemi-
cal compatibility) of various molecules need to be
closely matched, monitored in situ and, reliably dosed to
achieve precise but homogeneous doping in the film.
5. Finally, we observe that there is a lack of modeling
work for ALD doped ZnO films. ALD reaction model-
ing from ab initio principles is important, as experimen-
tal data suggest that there is significant chemical cross
talk between the chemisorbed dopant molecule and the
ZnO surface (and vice versa). As more complex precur-
sor molecules are formulated, reaction modeling will be
increasingly critical to understand surface reactions and
substrate interactions a priori. At the same time, dopant
incorporation into the ZnO matrix results in significant
changes to the electronic band structure. An important
issue not extensively discussed in the surveyed papers is
the impact of the dopant atoms on point defects, espe-
cially oxygen vacancies.
Here, it is noted that apart from ab initio modeling,
there currently exists two models to explain the impact
of dopants in ALD ZnO films. The first model is the
“effective radius model” by Lee et al.92 and adopted by
various groups.81,93,95,102 The second model is by Saha
et al.,116 who propose a dimensionless parameter, KFle
(KF is the Fermi wave number and le is the elastic mean
free path of electrons) to evaluate the doping perfor-
mance of ALD doped ZnO. Work should continue on
testing the validity and refinements to the models.
In conclusion, therefore, ALD doped ZnO films show
promising transparent conducting properties when compared
to doped ZnO films via other deposition methods. The mate-
rials “palette” for designing new ALD doped ZnO films
remains extensive and continues to grow. In addition to the
traditional process advantages of ALD over other deposition
050802-14 Z. Gao and P. Banerjee: Review Article: ALD of doped ZnO films 050802-14

37
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