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Growth and Raman Spectra of Doped ZnO Single Crystals

Article in Inorganic Materials · June 2011

DOI: 10.1134/S0020168511060070

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ISSN 00201685, Inorganic Materials, 2011, Vol. 47, No. 6, pp. 649–653. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © L.N. Dem’yanets, R.M. Zakalyukin, B.N. Mavrin, 2011, published in Neorganicheskie Materialy, 2011, Vol. 47, No. 6, pp. 727–731.

Growth and Raman Spectra of Doped ZnO Single Crystals

L. N. Dem’yanets†, R. M. Zakalyukin, and B. N. Mavrin
Shubnikov Institute of Crystallography, Russian Academy of Sciences, Leninskii pr. 59, Moscow, 119333 Russia
email: ruslan@[Link]
Received October 28, 2010

Abstract—ZnO:Mn+(Mn+ = Cd2+, Co2+, Ni2+, Sc3+, In3+, Ga3+, Fe3+, Te4+, V5+) single crystals have been
grown under hydrothermal conditions in ZnO–MxOy–KOH–LiOH–H2O systems, and their Raman spectra
have been measured under visible (514.5 nm) and nearIR (1064 nm) excitation. The anomalous band
between 500 and 600 cm–1 in the Raman spectra of ZnO:Mn2+ has A1 symmetry and is due to vibrations
involving Mn2+.
DOI: 10.1134/S0020168511060070

INTRODUCTION EXPERIMENTAL
Zinc oxide is a wellknown widegap semiconduc ZnO:M n+ single crystals were grown under hydro
tor with many practical applications [1, 2]. It has the thermal conditions in ZnO–МxOy–KOH–LiOH–
highest exciton binding energy (60 meV) among II–VI H2O systems. The process was run in autoclaves fitted
semiconductors, which makes it an ideal material for with floating silver inserts. The autoclave and furnace
blue and UV light–emitting diodes and lasers. The configurations were such that there were two tempera
semiconducting and ferromagnetic properties of ZnO ture zones, those of dissolution and crystallization.
doped with 3d transition metals make it an attractive The temperature in the dissolution zone was 320–
candidate for spintronic applications [3].
350°C, the growth zone was maintained at 230–
The theoretical prediction of roomtemperature 300°C, the pressure was 50–250 MPa, and the KOH
ferromagnetism in Mn2+ doped II–VI materials [4] and LiOH concentrations were 5.15 and 1.2 M,
has sparked intense interest in the preparation and respectively. Lithium hydroxide was added to the sys
Raman spectroscopy characterization of crystalline tem in order to improve the stoichiometry of the oxide
ZnO doped with 3d transition metals. The properties and the quality of the crystals through partial Li+ sub
of ZnO are known to depend significantly on the prep stitution for Zn2+. The dopants used were Cd2+, Co2+,
aration procedure, and various Raman results have
Ni2+, Sc3+, In3+, Ga3+, Fe3+, Te4+, and V5+ oxides (1–
been reported to date for ZnO [5–19]. Considerable
research effort has been concentrated on ZnO:Mnn+ 3 wt %). Major attention was paid to Mn2O3. Note that
nano and microcrystalline powders [5–10], films a reducing hydrothermal environment ensured the
[11–15], and bulk crystals grown by various tech Mn3+ (Fe3+) → Mn2+(Fe2+) transition.
niques [16–19]. The size of the grown crystals was determined by
Characteristically, zinc oxide is oxygendeficient, that of the seed plate, which was cut from the growth
independent of the preparation procedure and post pyramid of the positive monohedron, parallel to the
growth processing. The concentration of zinc intersti (0001) face from hydrothermally grown undoped ZnO
tials may reach 1015 to 1019 cm–3 [20]. The deviation single crystals. Typical seed dimensions were 20 mm
from stoichiometry can be reduced by incorporating along the а axis and 5 mm along the с axis. The struc
oxygen (through ion implantation or annealing) or via ture and composition of the crystals were determined
partial substitution of ions with a smaller positive by standard Xray diffraction and energydispersive
charge (Li+, H+) for the excess zinc during crystal Xray spectrometry techniques.
growth. The latter strategy prompted us to choose the
hydrothermal synthesis of zinc oxide [21–23]. Raman spectra were measured under visible excita
tion (514.5 nm, multichannel triplemonochromator
In this paper, we report the hydrothermal growth
Raman spectrometer, Princeton Instruments Spec10
and Raman spectroscopy characterization of bulk
ZnO:Mnn+ single crystals. LNcooled detector) and nearIR excitation (1064 nm,
Bruker RFS 100/S Fouriertransform Raman spec
† trometer).
Deceased.

649
650 DEM’YANETS et al.

Table 1. Doping effect on the crystal growth of zinc oxide (solvent: 5.15 M KOH + 1.2 M LiOH)
Growth rate, mm/day
tgrowth, °C/tdissol’n, °C Dopant (wt % in the charge) wt % Mn+ *
(0001) ( 000 1 ) (10 10)
270/330 – – 0.35 0.20 0.11
280/320 NiO (1.5) 0.01 0.18 0.11 0.05
280/320 CoO (3.3) 0.26 0.14 0.02 0.01
280/330 Sc2O3 (2.9) 0.05 0.05 0.04 0.05
255/305 In2O3 (0.9) 0.04 0.14 0.02 0.15
280/320 Fe2O3 (1.2) 0.04 0.21 0.07 0.06
280/320 Mn2O3 (3) 0.76 0.09 0.02 0.02
270/310 Zn (4, 7, 9) – 0.12 0.07 0.03
* Inferred from the energydispersive Xray analysis data for samples cut from the growth sector of the positive monohedron 〈0001〉.

RESULTS AND DISCUSSION reduces the growth rate of the monohedra, resulting in
a tabular habit. In3+ doping significantly increases the
The grown ZnO crystals had the wurtzite structure growth rate of the hexagonal prism faces, which enables
accelerated growth in the [10 1 0] , direction. Mn2+
4
(sp. gr. C 6v , Z = 2) and were faceted by the positive and
negative monohedra (0001) and ( 000 1 ) , the {10 10} reduces V[0001] by a factor of ~2 (0.05–0.09 mm/day) in
comparison with undoped ZnO. The crystals are
hexagonal prism, and the {10 11} hexagonal pyramid. orange or red in color, depending on Mn2+ concentra
Under the experimental conditions of this study, the tion. In control experiments, no reduction of Te4+ or
highest growth rate was observed in the [1000] direc V5+ was detected. All of the crystals were found to con
tion. The growth rate of the negative monohedron was tain excess zinc (Zn/O atomic ratio in the range 1.01–
several times slower, and that of the hexagonal prism 1.15), which could be removed by annealing in lithium
was nearly zero. The addition of oxides (0.9–3.3 wt %) carbonate.
to the growth charge (Table 1) influences the growth
rates of the main crystallographic faces, the crystal Raman scattering in ZnO has been studied in
habit, and, in some cases (doping with Fe2+, Co2+, detail. The Ramanactive modes in ZnO crystals are
A1 + E1 + 2E2 [24–26]. The А1 and Е1 modes are polar
Ni2+, and Mn2+), the color of the crystals. Fe doping and are thus split into transverse (TO) and longitudinal
causes hexagonal pyramid faces to develop, and the (LO) components.
crystals take a pyramidal habit. The incorporation of
Mn2+, Ni2+, or In3+ into the host lattice considerably In this study, the Raman spectra of oriented ZnO
single crystals (undoped and doped with Fe2+, Mn2+,
In3+, Sc3+, and V5+) were obtained in the following
backscattering geometries: 180°: z ( xx ) z, z ( yy ) z,
z ( yx ) z, x ( yy ) x, z ( zz ) x , and x ( yz ) x. This allowed us
z(yx)z, E2 to detect all of the modes in the crystals studied.
Manganesedoped ZnO has a hexagonal structure,
and the Mn atoms substitute on the Zn site [5, 6, 14].
The frequencies observed in the spectra of ZnO:Mn2+
Intensity

z(yy)z, A1(LO) + E2
(Fig. 1) were compared to those in ZnO (Table 2). Mn
doping is seen to have little effect on the A1(TO),
A1(LO), E1(TO), E 21, and E 22 fundamentals. Moreover,
×5 x(zz)x, A1(TO)
the polarization of the Raman lines remains almost
unchanged in the spectra of ZnO:Mn2+. This indicates
x(yz)x, E1(TO)
×5 that the single crystals are of high optical quality and
that the inhomogeneities associated with the presence
0 200 400 600 800 1000 1200 of manganese in ZnO have a weak effect on the quality
Frequency, cm–1 of the crystals. The observed secondorder Raman
lines (overtones and combination modes (Table 2)) are
Fig. 1. Raman spectra of ZnO:Mn2+ single crystals in dif
strongest in the scattering geometries where modes of
ferent backscattering geometries. А1 symmetry are active. The 334cm–1 line—even

INORGANIC MATERIALS Vol. 47 No. 6 2011

 GROWTH AND RAMAN SPECTRA OF DOPED ZnO SINGLE CRYSTALS 651

though its intensity is comparable to that of the funda Table 2. Frequencies and symmetries of Raman lines in
ZnO:Mn2+ and assignment of secondorder Raman lines in ZnO
mentals—arises from the E 22 – E 21 combination, as
supported by firstprinciples calculations for ZnO Frequency, cm–1 Symmetry of lines Assignment
crystals [27] and the temperature dependence of its in ZnO:Mn2+ in ZnO [25]
intensity [6]. ZnO:Mn2+ ZnO [25]
One essential distinction between the spectra of 98 99 1
E2
ZnO:Mn2+ and ZnO is that the former contains a
1
broad band in the range 500–600 cm–1. In some of the 201 203 A1 2TA; 2 E 2
scattering geometries, this band is stronger than the 2 1
fundamentals (Fig. 1). Earlier, it was detected in the 250 284 A1 B1 − B1
Raman spectra of ZnO:Mn2+ nanoparticles [5–8], 2 1
334 333 A1 E2 − E2
films [13–15], and crystals [16]. This band is referred
to as anomalous because it is missing in spectra of 377 378 A1(TO)
ZnO. In this spectral region, ZnO has weak features 409 410 E1(TO)
near 536 and 574 cm–1 (Table 2), assignable to an over 2
tone of the Ramanforbidden mode В1 (536 cm–1) and 437 438 E2
to the longitudinal mode A1(LO), respectively. Let us 480 483 A1 2LA
discuss the behavior of the anomalous band. 1
522 536 A1 2 B1
The intensity of the anomalous band was reported
to depend on the manganese concentration in ZnO: 572 574 A1 A1(LO)
Mn2+ [5–8, 13, 15]. According to the present results 660 657 A1 TA + LO
(Fig. 1), the symmetry of the anomalous band is А1. Of 1000 980 A1 + E1 + E2 2TO
key importance is the dependence of its intensity on
excitation wavelength. The point is that the incorpora 1060 1044 A1 + E1 + E2 TO + LO
tion of manganese atoms into the ZnO lattice induces 1100 1105 A1 + E1 + E2 2LO
an optical absorption in the range 400–600 nm [9, 14], 1150 1158 A1 + E1 + E2 2LO
where undoped ZnO crystals are transparent. This
absorption was assigned to electronic transitions of the
Mn2+ ion [9, 14]. Various results have been reported as band can be thought of as the Fermi resonance of an
to the intensity of the anomalous band under visible overtone of the Ramanforbidden mode В1 with the
excitation. According to Gleize et al. [15], it depends longitudinal mode A1(LO). In addition, ab initio calcu
on the excitation wavelength. Yadav et al. [13] hold lations by Schumm et al. [28] suggest that, in contrast
that the intensities of both the anomalous band and to the other fundamentals, B1 is only due to cations.
other Raman bands are independent of excitation When the excitation wavelength lies in the induced
wavelength. The discordance arises from the weak absorption region due to electronic transitions of the
spectral dependence of the induced absorption in the Mn2+ ion, resonance Raman scattering by the 2В1
wavelength range in question. In the visible and near overtone is possible.
IR excitation Raman spectra (Fig. 2), if the excitation
wavelength falls in the induced absorption band
(514.5nm excitation) of the transparency region
(1064 nm), the anomalous band in the range 500–
600 cm–1 is very weak or missing under excitation in
the transparency region. This finding leads us to con
clude that the anomalous band arises predominantly
from vibrations of the manganese atoms.
In several recent reports [14, 15, 28], the anoma
Intensity

lous band was tentatively attributed to local (LVM) or 514.5 nm

defect modes of manganese atoms in ZnO. The LVM
frequency can be estimated in a simple mass defect
model [29]:
ωLVM  ωZnO μ ZnO μ MnO, 1064 nm
where µ is a reduced mass. In this approximation, the
LVM frequencies differ from the fundamental fre 0 200 400 600 800 1000 1200
quencies of ZnO by less than 2%, which is well below Frequency, cm–1
the frequency of the anomalous mode. Since no LVMs
are expected near the anomalous band and its symme Fig. 2. Visible and nearIR excitation Raman spectra of
try is A1, it is reasonable to assume that the anomalous ZnO:Mn2+ single crystals.

INORGANIC MATERIALS Vol. 47 No. 6 2011

652 DEM’YANETS et al.

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