J Sol-Gel Sci Technol (2010) 53:141–147
DOI 10.1007/s10971-009-2067-2
ORIGINAL PAPER
Stabilization of ZnMnO3 phase from sol–gel synthesized nitrate
precursors
L. V. Saraf Æ P. Nachimuthu Æ M. H. Engelhard Æ
D. R. Baer
Received: 23 April 2009 / Accepted: 20 August 2009 / Published online: 3 September 2009
Ó Springer Science+Business Media, LLC 2009
Abstract The stabilization and analysis of pure ZnMnO3
phase may help to understand the solubility limits of Mn in
ZnO in wurtzite and cubic structures. In this report, syn-
thesis and characterization of stable ZnMnO3 phase is
discussed which is extracted from sol–gel synthesis of zinc
and manganese nitrate precursors. The reflections at higher
diffraction angles for this known cubic system with space
group Fd3 m were calculated with the help of JADE 8.0
program. The reliability factor for ZnMnO3 calculated
from Rietveld refinement was 2%. A narrow phase pure
ZnMnO3 stabilization region was identified with the help of
energy dispersive spectroscopy mapping. High resolution
X-ray photoelectron spectroscopy measurements of Mn3p
position of ZnMnO3 compared with ZnMn2O4 showed a
higher binding energy shift *0.85 eV indicating Mn4?
valence state in ZnMnO3.
Keywords Sol–gel synthesis
ZnMnO3
XPS

XRD
1 Introduction
The electrolysis of seawater often results in release of
chlorine which is sometimes not a desired outcome when
oxygen release is preferred. It is because the equilibrium
potential for oxygen release is 700 mV lower than chlorine
release and chloride ions form chlorine rather than water
conversion to oxygen. Oxygen release also gets complicated
L. V. Saraf (&)
P. Nachimuthu
M. H. Engelhard

D. R. Baer
Environmental Molecular Sciences Laboratory, Pacific
Northwest National Laboratory, Richland, WA 99352, USA
e-mail: Lax.Saraf@pnl.gov
due to multistep reaction than a single step chlorine forma-
tion reaction. Some evidence indicate that oxygen evolution
efficiency during seawater electrolysis could be improved by
using materials like zinc manganese oxide, as a coating layer
on electrodes [1]. Unique properties of Zn–Mn–O can be
related to redox potential for conversion between Mn3? and
Mn4? at E = 0.98 eV, which is close to potential for Cl- to
Cl2 and H2O–OH–O2 conversion. H2O molecule/OH- or
Cl- ion may be oxidized to oxygen and chlorine via higher
oxidation state of Mn (Mn4?) at the anode surface. It was
noted that ZnMnO3 formation alters the surface electro-
chemistry of the electrodes affecting the oxygen evolution
process.
In magnetics, secondary phase formation is a great con-
cern for the applications related to dilute magnetic semi-
conductors (DMS). Manganese doping in ZnO has been
predicted to result in formation of DMS [2]. For this par-
ticular system, a lot of different properties such as para-
magnetism, ferromagnetism, spin-glass behavior have been
observed. Mn–ZnO is also of interest because the ionic
radius of Mn and Zn in the two plus valance state are
comparable. It has been observed that existence of Mn2?
and related ordering of magnetic moments facilitates fer-
romagnetism in ZnMnO system [2]. However, lack of phase
pure synthesis due to low dopant solubility has generated a
lot of contradictory results in the literature. There is a gen-
eral agreement that existence of fractional quantity of spinal
phases in DMS usually lead to contradictory results because
some of the ZnMn2O4 related spinal phases have their own
paramagnetic, ferromagnetic and antiferromagnetic prop-
erties which can easily overlap with magnetic properties of
host systems.
The phases in ZnMnO have generally been two types,
ZnMnO3 and spinel ZnMn2O4. Out of these, stable ZnMn2O4
phase is widely observed [3–6]. On the contrary, ZnMnO3
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phase is mostly observed in the form of a phase mixture along
with ZnO and ZnMn2O4 [7–11]. There are few reports of
successful synthesis approaches towards ZnMnO3 (in the
mixed phase form) partly because of its instability, relatively
narrower Mn doping and temperature range for ZnMnO3
formation [12, 13]. The analysis of ZnMnO3 phase becomes
even more important by considering the fact that formation
of this phase will start immediately after surpassing the
solubility limit of Mn in ZnO (in the wurtzite structure form)
reaches its maxima. In this letter, we present a successful
phase pure synthesis of ZnMnO3 and compare its surface and
microstrcture properties with stable phases at opposite ends
i.e. ZnO and ZnMn2O4. We also calculate previously
unknown high angle hkl reflections of Fd3 m cubic ZnMnO3
phase with the help of JADE 8.0 program which matched
very well with hkl reflections in the experimental data taken
with the help of X-ray diffraction (XRD).
2 Experiment
We have used 0.47 M zinc nitrate hexahydrate solution
dissolved in DI water and added 0.1 mL drops of Mn
(NO3) solution in dilute nitric acid to achieve desired

Fig. 1 A detailed XRD analysis 311

of various samples prepared
220

440
511
from solutions with varying

731*
533*
400

422

444*

751*
Mn concentrations in the range
222

Si Si
of 0.47–0.58 M using copper
X-rays to obtain phase pure
311

ZnMnO3 phase
511
220

440

731*
533*
400

422

444*

751*
222

Si Si

440
311

511

731*
220

533*

751*
Si
422

444*
*
400
222

Si
* *
002 311

440
511
100

731*
220

533*
400

Si
422

751*
444*
101

112
102

203
Si
311
002

440

Si
220

Si
101
100

731*
511

751*
533*
112
400

203
102

422

Si
440
311

Si
002

731*
100

511
110
101
220

112

751*
102

533*

Si
400

203
422

201

114

Si
101
002

Si
100

103
110

112

211
201

203
102

210

*
114

Si
*
Si
101

Si
002
100

112
103
110

Si
004
102

200

201

203
202

210

114
105
101
002
100

112
200
103
110

004
102

201

211
203

212
202
104

210

114

105

Si

20 40 60 80 100 120

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J Sol-Gel Sci Technol (2010) 53:141–147 143

solution concentrations in a very narrow range of series of (a)

solutions ranging from 0.47 to 0.58 M in concentrations.

Intensity (counts)
For gel formation process, equal amount of Triton X100
was added as a surfactant. The solutions with concentra-
tions more than 0.58 M started to form trace quantities of
ZnMn2O4 phase. Film depositions were carried out by
solution spin coating on single crystal silicon substrates
followed by annealing in air at 650 °C/2 h. Scanning
electron microscopy (SEM) images were recorded with a SQR(I) ZnO
LEO 982 field emission microscope. The microscope had a
resolution of 1 nm at 30 kV and 4 nm at 1.0 kV using (b)

Intensity (counts)
multiple detectors. Energy dispersive spectroscopy (EDS)
analysis was performed with the help of INCA system from
Oxford Instruments. X-ray photoelectron spectroscopy
(XPS) measurements were carried out using a Physical
Electronics Quantum 2000 Scanning ESCA Microprobe.
A focused monochromatic Al Ka X-ray (1,486.7 eV)
source with 16-element multichannel detection was used in
SQR(I) ZnMnO3
the experiment. The X-ray beam was 101 W, 107 lm in
diameter, and rastered over an area of 1.4 9 0.2 mm.
High-energy resolution spectra were collected using a pass Intensity (counts) (c)
energy of 23.5 eV. The binding energy scale was calibrated
using the Cu 2p3/2 peak at 932.62 ± 0.05 eV and the Au
4f7/2 peak at 83.96 ± 0.05 eV. XRD measurements were
made using Rigaku as well as Phillips X’pert h-2h dif-
fractometer using Cr as well as Cu anodes. X-ray profile
fitting as well as calculation of hkl phases of Fd3 m
structure were carried out using the JADE 8.0 program. SQR(I) ZnMn2O4

30 40 50 60 70 80 90 100 110 120 130 140

3 Results and discussion 2 θ (deg)

The data in Fig. 1 represents a detailed XRD analysis using
copper X-ray anode to reach phase pure ZnMnO3 structure.
The individual XRD images correspond to various annealed
(650 °C/2 h) samples generated from solution concentra-
tions range of 0.47–0.58 M. A detailed phase transformation
from Zn1-xMnxO to ZnMnO3 with mixed phases in-between
is evident in the data. The hkl indices in black and red rep-
resent Zn1-xMnxO and ZnMnO3 phases, respectively. The
red stars without identified hkl indices represent possible
trace quantities of ZnMnO3 phase. The black stars without
identified hkl indices represent possible trace quantities of
Zn1-xMnxO phase. The red hkl indices with stars represent
calculated hkl indices using JADE 8.0 program. The sub-
strate silicon peak is evident in some data. The XRD data of
pure ZnO powder is also shown for comparison.
Due to the longer wavelength generated from Cr X-rays,
there is a higher spread in 2h diffraction angles which is
important to analyze the hkl reflections with much higher
resolution. A major advantage is identification and separa-
tion of possible weak reflections related to secondary phases
which otherwise would be overlapping with major hkl
Fig. 2 XRD scans using chromium X-rays indicating phase pure
a ZnO, b ZnMnO3 and c ZnMn2O4 samples
reflections corresponding to primary phase. The XRD
images using Cr anode in Fig. 2a–c represent a comparison
among pure ZnO, ZnMnO3 and ZnMn2O4 phases. The dif-
fraction in Fig. 2b represents ZnMnO3 phase. No diffraction
signals related to ZnO or ZnMn2O4 were detected in it. The
lattice parameters of ZnMnO3 cubic structure were calcu-
lated using JADE 8.0 program were a = b = c = 8.34 Å
with structure in the category Fd3 m. The details of calcu-
lated d values of ZnMnO3 phase with hkl indices for the
scanned range in our case are shown in Table 1. The cal-
culated d and hkl values match very well with experimen-
tally observed diffraction parameters.
The powder XRD pattern used in Rietveld refinement
procedure in the case of ZnMnO3 shown in Fig. 3 was
collected at room temperature using Cr Ka1 X-ray radia-
tion at a wavelength of 2.2897 Å. The step size during the
measurement was chosen at 0.0113°. The 2h range for all
the calculation of Rietveld refinement was chosen from 25

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Table 1 Calculated lattice spacing (d) and hkl parameters with other
details for ZnMnO3 phase using JADE 8.0
2h d(Å) I(f) (hkl) h 1/(2d) 2u/d n2

27.493 4.8179 6.6 (1 1 1) 13.747 0.1038 1.3041 3

45.666 2.9503 35.6 (2 2 0) 22.833 0.1695 2.1296 8
54.133 2.5161 100.0 (3 1 1) 27.066 0.1987 2.4972 11
56.752 2.4089 6.7 (2 2 2) 28.376 0.2076 2.6083 12
66.566 2.0862 14.1 (4 0 0) 33.283 0.2397 3.0118 16
73.456 1.9144 0.8 (3 3 1) 36.728 0.2612 3.2820 19
84.461 1.7034 12.5 (4 2 2) 42.230 0.2935 3.6886 24
90.940 1.6060 39.6 (5 1 1) 45.470 0.3113 3.9124 27
101.808 1.4752 56.0 (4 4 0) 50.904 0.3389 4.2593 32
108.515 1.4105 1.0 (5 3 1) 54.258 0.3545 4.4545 35
110.806 1.3908 0.5 (4 4 2) 55.403 0.3595 4.5177 36
120.383 1.3194 8.6 (6 2 0) 60.192 0.3789 4.7620 40
128.222 1.2726 25.8 (5 3 3) 64.111 0.3929 4.9374 43
131.023 1.2580 9.3 (6 2 2) 65.511 0.3974 4.9945 44
143.798 1.2045 9.3 (4 4 4) 71.899 0.4151 5.2165 48
Radiation = Cr Ka1 k = 2.28973 Å; 2h = 27.493–143.798 I/Ic(RIR) =
Cubic, Fd3m (227) Z = 12 mp = Cell: 8.34485 9 8.34485 9 8.34485
\ 90.0 9 90.0 9 90.0 [ P.S = Density(c) = 5.771 Density(m) = Mwt =
Vol = 581.1; Strong lines: 2.52/X 1.48/6 1.61/4 2.95/4 1.27/3 2.09/1 1.70/1
1.20/1

40k
(311)

Observed
Calculated
30k Bragg Position
(220)
Intensity (counts)

(440)
(111)

20k
(511)

(533)
(222)

(422)
(400)

(444)
(620)

(622)

10k

0
Observed -Calculated

20 40 60 80 100 120 140 160

2θ -degrees

Fig. 3 Rietveld refinement of powder XRD pattern of ZnMnO3

Fig. 4 SEM images of sol–gel synthesized a ZnO, b ZnMnO3 and
c ZnMn2O4 nanoparticles after annealing at 650 °C/2 h
to 150 degrees. All the calculations were done using JADE
8.0 program. From the space group of Fd3 m (227), the
cubic structure was found to be ZnMnO3 and the atomic refinement and expected residual error of refinement was
positions at unit cell of a = b = c = 8.34507 Å with 1.97. For all calculations, we have used P (total no. of
a = b = c = 90° with a unit cell volume of 581.2 Å3 and refined parameters) as 12 with EPS value, which is mini-
a density of 5.7708 gm/cm3. By using these values, the mum value set for convergence as 0.5. As seen in Fig. 3,
reliability factor R was obtained at 2%. The expected the experimentally observed XRD spectrum and calculated
residual error of refinement parameter was calculated as XRD spectrum matches very well. The difference spectrum
1.02%. Thus, value of R/E as weighted residual error of shown at the bottom of Fig. 3 also stays near zero.

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J Sol-Gel Sci Technol (2010) 53:141–147
HKL reflections of ZnMnO3 structure were previously
observed by H. Toussaint [14]. However, these hkl reflec-
tions were observed only up to (440) [d = 1.475]. In our
case, as shown in Table 1, we have calculated and exper-
imentally observed higher angle reflections such as (620)
[d = 1.3194], (533) [d = 1.2726], (622) [d = 1.2580] and
(444) [d = 1.2045]. As shown in pure ZnMnO3 spectrum
of Fig. 1 and due to shorter Cu Ka wavelength (compared
to Cr Ka), the last two reflections (731) [d = 1.0871] and
(751) [d = 0.9642] could be visible by using Cu Ka as a X
-ray source. When Cr Ka X-ray source was used, the 2h
value of (444) [d = 1.2045] reaches *143.8°. This creates
instrument scanning limitation for effective higher 2h angle
measurements. The calculated reflections such as (531)
[d = 1.4105] and (442) [d = 1.3908] were experimentally
not detected due to very low calculated peak intensity I(f)
values of 1 and 0.5, respectively.
Fig. 5 a SEM and b Zn and Mn EDS mapping overlapped on SEM
image indicating a typical sample with a phase mixture. Red and
green colors indicate X-ray signals from Mn and Zn, respectively.
The dominating red and green color regions directly correspond to
different phase regions. (Color figure online)
145
SEM images of phase pure ZnO, ZnMnO3 and
ZnMn2O4 are shown in Fig. 4a–c, respectively. It was
observed that the average grain size reduces from ZnO to
ZnMnO3 to ZnMn2O4. The grains are observed more
clustered in the ZnMn2O4 case. The average grain size for
ZnMnO3 is observed in the range of *30 nm. Detailed
analyses of all of the samples were carried out using EDS
mapping. The atomic concentrations of Zn were directly
compared with Mn concentration. A typical representative
SEM and EDS mapping of Zn and Mn image corre-
sponding to phase mixture sample is shown in Fig. 5a, b,
respectively. The red and green colors represent Mn and Zn
X-ray signals, respectively. The phase separated regions
can be clearly identified in the maps. A detailed analysis of
the Mn EDS atomic concentration data generated from all
the samples prepared from the solution concentration range
of 0.47–0.58 M is presented in Fig. 6. The red data points
represent the highest observed Mn concentration anywhere
on a particular sample. The blue data point represents the
lowest observed Mn concentration on the same sample.
Thus, it is safe to assume that, for a sample with a phase
mixture, Mn atomic concentration falls in between this
range. As expected, lowest and highest extreme values
represent phase pure Zn1-xMnxO and ZnMnO3. Since EDS
peak intensities for Mn and Zn have different energy and
sensitivity dependence, the direct stoichiometric conversion
of atomic concentrations of Mn and Zn into Zn1-xMnxO or
ZnMnO3 structures is difficult and thus all the comparisons
need to be relative to each other.
The high-resolution XPS spectra at Mn 3p, Zn 2p and O
1s positions for ZnO, ZnMnO3 and ZnMn2O4 are shown in
45
40
35
30
25
20
15
10
0
0.48 0.50 0.52 0.54 0.56 0.58
Fig. 6 A detailed analysis of the Mn EDS atomic concentration data
generated from samples in the solution concentration range of 0.47–
0.58 M. The red and blue data points represent the highest and lowest
observed Mn concentration anywhere on a particular sample. (Color
figure online)
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146 J Sol-Gel Sci Technol (2010) 53:141–147

Fig. 7a–c, respectively. A higher energy shift of *0.85 eV seen in Zn 2p and O 1s spectra, no substantial shifts were
in ZnMnO3 represents Mn4? valence state. The stronger observed which is justifiable because during a transition
XPS position, Mn 2p3/2 was not considered to avoid from ZnO–ZnMnO3–ZnMn2O4 phases, the 2 ? valence
overlapping effects from AES peak position L2M23N23 state of Zn and 2- valence state of oxygen are not expected
which is related to zinc. By choosing Mn 3p position, the to change. XPS based literature work related to Mn 2p
shifts in XPS peaks could be conclusively confirmed. As valence positions for manganese oxide system could also
be taken in to account [15–17]. It is generally observed that
in the materials ranging from MnO–Mn2O3–Mn3O4–
0.85 eV MnO2, a shift in XPS Mn 2p position occur ranging from
640.5–642.5 eV, with 642.5 eV corresponding to MnO2
(a) ZnO
[17]. The shift corresponds to increase in Mn valence from
(b) ZnMnO 3 2 ? (MnO) to 4 ? (MnO2). This is consistent with higher
Mn 3p
(c) ZnMn2O4 eV shift in our case for ZnMnO3 phase where the valence
state is expected to increase from 3 ? (ZnMn2O4) to
(c) 4 ? (ZnMnO3).
By taking a general overview of the literature for
ZnMnO3 and related phases, the existence of ZnMnO3 in
the form of a mixed phase was clear. The origin of spin-
(b)
glass behavior was correlated to the presence of ZnMnO3
(a) [7]. By using nitrate precursors, it was noticed that ZnMnO3
peaks started appearing when the amount of Mn dopant was
reached at x = 0.07 at 500 °C [8]. It was predicted that
54 52 50 48 46
solubility limit of Mn in ZnO is 10%. Observation of
ZnMn2O4 was seen above that level predicting that for-
Zn 2p mation of ZnMnO3 phase may not happen due to high
synthesis temperatures [9]. A study also concludes that
Intensity (c/s)

solubility of Mn in ZnO is in between 10 and 15% after

which ZnMnO3 phase starts to appear in the form of a mixed
phase [10]. It was noted by Cong etal [11] that ZnMnO3
forms as an impurity and XRD peak intensities of it
increases up to 650 °C. The report where successful syn-
thesis approach of ZnMnO3 was discussed using oxalate
(c) (a) precursors, it was noticed that ZnMnO3 phase forms after
(b) annealing at 400 °C. ZnMnO3 was reported as a mixed
phase throughout the composition and annealing changes.
1026 1025 1024 1023 1022 1021 1020 1019 1018
The authors have observed that increase in the temperature
up to 800 °C increases the concentration of the ZnMnO3
O 1S
phase followed by decrease in it which was correlated to
decomposition of ZnMnO3. However, better stability of
ZnMnO3 was reported below 400 °C [12]. When some of
the ZnMnO3 type phases like ZnCoO3 and ZnMgO3 are
considered, it was noted that phases like ZnCoO3 were hard
to find [18]. While studying Mg–ZnO system, a mixed
(b) phase region with possible cubic structure was predicted as
ZnMgO3 related [19]. Considering the literature review, it
becomes clear that synthesis of ZnMnO3 in the phase pure
(c)
(a) form is often a challenge due variety of conditions related to
stability and its formation in a relatively narrow doping-
534 532 530 528 526
temperature window. A representative view of phase
Binding Energy (eV) transformations from pure ZnO to ZnMn2O4 as a function
Fig. 7 High resolution XPS spectra of a ZnO, b ZnMnO3, c ZnMn2O4 of Mn doping concentration are shown in the schematics of
at Mn 3p position. A higher binding energy shift of *0.85 eV Fig. 8 where a predicted narrow doping window range
corresponds to formation of Mn4? valence state in ZnMnO3 phase for phase pure ZnMnO3 synthesis is envisioned under our

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J Sol-Gel Sci Technol (2010) 53:141–147
Fig. 8 A representative schematic view of phase transformations
from pure ZnO to ZnMn2O4 as a function of Mn doping concentration
synthesis conditions. The doping window range is also
expected to change as a function of various experimental
conditions as well as processing methods.
4 Conclusions
In conclusion, synthesis of stable ZnMnO3 phase is formed
which is synthesized using sol–gel growth from zinc and
manganese nitrate precursors. The reflections at higher
diffraction angles for d in the range of 1.4105–1.2045 were
calculated with the help of JADE 8.0 program. The cal-
culated values matched very well with observed experi-
mental data. The reliability factor for ZnMnO3 calculated
from Rietveld refinement was 2%. Under our experimental
conditions, a narrow phase pure ZnMnO3 stabilization
region was identified with the help of energy dispersive
spectroscopy mapping. High resolution XPS measurements
147
of Mn3p position of ZnMnO3 compared to ZnMn2O4
sample showed a higher binding energy shift of *0.85 eV
indicating Mn4? valence state in ZnMnO3. Since ZnMnO3
phase formation may come immediately after reaching the
Mn doping saturation conditions in ZnO in wurtzite
structure which is important for magnetic applications,
further analysis of phase pure ZnMnO3 could be well
justified.
Acknowledgments The authors would like to thank PNNL/UW/
WSU nano-course participants as a source of motivation. The
research was performed at EMSL, a national scientific user facility
sponsored by the Department of Energy’s Office of Biological and
Environmental Research and located at Pacific Northwest National
Laboratory (PNNL). PNNL is operated by Battelle for the US
Department of Energy.
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