Solid State Ionics 345 (2020) 115178

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Solid State Ionics

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Dielectric properties and electrical conductivity of LiNbO3:Zn crystals in the T

temperature range 310–900 К
M.N. Palatnikova, A.V. Yatsenkob, V.A. Sandlera, N.V. Sidorova, O.V. Makarovaa,
⁎
D.V. Manukovskayaa,
a
Tananaev Institute of Chemistry, Subdivision of the Federal Research Centre «Kola Science Centre of the Russian Academy of Sciences», 184209, Murmansk region,
Apatity city, Russian Federation
b
V.I. Vernadsky Crimean Federal University, Prospekt Vernadskogo 4, Simferopol, Republic of Crimea 295007, Russian Federation

A R T I C LE I N FO A B S T R A C T

Keywords: Electrical conductivity and dielectric constant have been researched in a series of crystals LiNbO3:Zn
Single crystal (~4.0–9.0 mol% ZnО in a melt) by application of constant voltage with a couple of electrodes (~ < 500 K) and
Lithium niobate impedance spectroscopy (~ > 500 К). In order to compare results we have also researched electrical con-
Doping ductivity σdc of congruent LiNbO3congr and magnesium doped LiNbO3:Mg crystals. We have established that
Impedance spectroscopy
electron contribution to electrical conductivity of doped crystals LiNbO3:Zn and LiNbO3:Mg is greatly smaller
Electron conductivity
than that of a congruent crystal LiNbO3congr. A decrease in conductivity is apparently connected with a re-
Ion conductivity
structure of LiNbO3 crystals at high concentrations of magnesium and zinc. Doping of crystals with Zn leads to
drastic changes not only in the electron conductivity area (T < 500 K), but also in a lithium ion conductivity
area (Т > 500 K). At this, parameters of temperature dependence of lithium ion conductivity depend on both
zinc concentration and crystallographic orientation of samples.

1. Introduction An interest towards strongly doped LiNbO3:Zn crystals in the dopant

A lithium niobate crystal (LiNbO3) is now intensively researched by
specialists of integrated and nonlinear optics, acoustoelectronics,
quantum electronics, solid state physics [1–3]. Study of mechanisms of
electron and ion transfer in ferroelectric crystals like LiNbO3 is an im-
portant task for analysis of many physical characteristics of these ma-
terials and predicting of their changes under high temperatures action.
This task has an especially high relevance for crystals with a great
concentration of bulk intrinsic defects, such as crystals grown from a
congruent melt (LiNbO3congr). The main type of defects in nominally
pure crystals LiNbO3congr (ratio [Li]/[Nb] ~ 0.946) are lithium va-
cancies VLi′ and anti-structure niobium ions in lithium sites NbLi4+ [4].
Due to some authors [5,6] these defects form clusters (4 VLi′ + NbLi),
and besides all four VLi′ are located quite close to NbLi4+. As-grown
LiNbO3congr crystals always contain some OH-groups [4,7] and prob-
ably, some oxygen vacancies VO [8]. Besides, lithium niobate crystals of
different composition are known to contain “stubborn” domains that
fail to vanish during turning of a crystal to a single domain state which
substantially decreases the degree of unipolarity. The “stubborn” do-
mains are wedge-shaped non-through domains with charged oblique
walls [9].
concentration area ~ 4.0 ÷ 9.0 mol% in the melt is caused by a high
optical damage resistance, low coercive fields and a possibility to use
them in technology of optical converters on periodically polarized
structures [4,10]. An influence of cation doping on the crystal proper-
ties is jump-like and is called “concentration threshold” [4,11,12]. The
strongest changes of LiNbO3:Zn crystals are observed in the area of the
main concentration threshold ~ 6.8 mol% ZnO in the melt [12]. At this
structure and physic-chemical properties of the melt changes and the
mechanism of the doping cation integration to the LiNbO3:Zn crystal
lattice also becomes different [4,11,12].
Although mechanisms of electron and ion transfer are a highly in-
teresting topic, it has not been studied in detail for real doped lithium
niobate crystals. This is the reason why we have researched electrical
conductivity and dielectric constant in a series of crystals LiNbO3:Zn in
a wide range of temperatures (~ 310-900К). The study was carried out
by application of constant voltage with a couple of electrodes
(~ < 500 K) and impedance spectroscopy (~ < 500 K). The research
was carried out in a range of dopant concentration (~4.0–9.0 mol%
ZnО in a melt). In order to compare results we have also researched
electrical conductivity σdc of LiNbO3congr and LiNbO3:Mg crystals by
application of constant voltage with a couple of electrodes (~ < 500 K).

⁎
Corresponding author.
E-mail address: manukovskaya@chemy.kolasc.net.ru (D.V. Manukovskaya).

https://doi.org/10.1016/j.ssi.2019.115178
Received 1 November 2019; Accepted 2 December 2019
0167-2738/ © 2019 Published by Elsevier B.V.
M.N. Palatnikov, et al. Solid State Ionics 345 (2020) 115178

2. Method Table 1
Impurity composition of initial charge and studied lithium niobate crystals of
Lithium niobate granular charge with a high bulk density (~3.4 g/ different composition.
sm3) for growth of LiNbO3congr, LiNbO3:Zn and LiNbO3:Mg was ob- Impurity type Concentration in the initial Concentration in the crystal, wt%
tained by a thorough mixing of Nb2O5 and Li2CO3 or Nb2O5, ZnO(MgO) charge, wt%
and Li2CO3. After that the mixture was synthered at high temperature Top of the Bottom of the
boule boule
by granulating synthesis [13]. The ratio Li2O/Nb2O5 in the initial
mixture corresponded to a congruent melting composition (~ 0.946). Mn, V, Sn, Cu < 1·10−4 < 5·10−4 < 5·10−4
Crystals LiNbO3congr, LiNbO3:Zn and LiNbO3:Mg ~ 35–40 mm long with Pb, Ni, Cr < 1·10−4 < 1·10−3 < 1·10−3
a diameter 40 mm were grown in the direction (001) by Czochralski Co, Mo < 4·10−4 < 1·10−3 < 1·10−3
Si, Fe < 10·10−4 < 1·10−3 < 1·10−3
from Pt crucibles 75 mm in diameter in air atmosphere. Growth was
Ti < 5·10−4 < 1·10−3 < 1·10−3
carried out on plants of induction type, equipped with a system of aт Al < 10·10−4 < 5·10−4 < 5·10−4
automatical crystal diameter control. The boule growing rate was Zr < 2·10−3 < 5·10−3 < 4·10−3
1.1 mm/h for LiNbO3:Zn(Mg) crystals and 2.2 mm/h for LiNbO3congr. Ca < 10·10−4 < 5·10−3 < 5·10−3
The axis temperature gradient was ~2.5 K/mm for LiNbO3congr and Te, Sb < 10·10−4 – –
Bi < 4·10−4 – –
~1 K/mm for LiNbO3:Zn(Mg) crystals. The turning rate was approxi-
mately ~14–16 rpm for all studied crystals. In order to lift thermo-
elastic stresses all studied crystals were thermally treated after growth conductivity were carried out by a two-electrode method: constant
at Т = 1473 K during 24 h. All studied crystals were turned to a single- voltage was applied to samples on a universal installation described in
domain state by a high-temperature electrodiffusion annealing [15]. Maximal field strength was 2.1 kV/sm. The method of electro-
(HTEDA): a constant electrical field was applied at cooling with the physical measurements at a sample temperature measurement was
speed 20°С/h from ~ 1240 to 890°С for crystals LiNbO3:Zn(Mg) and described in detail in [16]. Used installation allows precision mea-
from ~ 1200 to 850°С for crystals LiNbO3congr [14]. The degree of surements at a constant current. A real sensibility of measurements is ~
unipolarity was controlled by detecting of the value of static piezo- 30 fA and it is limited by currents of pyroelectric nature (due to in-
electric constant (d333st) of a crystal sample. The measurement of static stability of the sample temperature) and instability of the high voltage
piezoelectric constant of a z-oriented LiNbO3:Zn crystal was carried out source. At research of temperature dependence of electrical con-
at a room temperature. The essence of the experiment is the following: ductivity along a non-polar direction electric fields of pyroelectric
measured value of piezoelectric constant (in the d333 geometry) de- nature were supposed to be minimized and breakdowns – to be elimi-
pends on the sample unipolarity linearly in static conditions. The de- nated. In order to achieve these goals polar surfaces of samples were
gree of the sample unipolarity can be determined as covered by aquadag and these additional electrodes were inter-
V+ − V− V+ − V− connected and grounded. A thermostat and a temperature control
ξ= = ,
V+ + V− V0 (1) system provided long-term instability of a system in the range 0.3 K/h
+ −
and a short-term instability ± 0.006 K/min. The sample temperature
where V and V - sum volumes of all conditionally positive and ne- was measured by a calibrated differential thermocouple copper-con-
gative domains, their sum is the sample of the whole sample V0. stantan. Due to the fact that LiNbO3 crystals possess relatively strong
Perfectly single-domain crystal (with ξ = 1) has the maximal pos- pyroelectrical properties [1], local switching of polarization had to be
sible value of piezoelectric constant d333MAX. Completely polydomain minimized under the action of a pyroelectrical field. In order to do so,
crystal (ξ = 0) has the constant value d333MIN = 0. In our case, the change of the temperature and heating and cooling of samples was
piezoelectric constant d333 is proportional to ξ, thus, carried out at a rate not faster than ~2 K/min. Measuring electrodes
ξ = d333/d333max , (2) were applied on the corresponding pair of faces by rubbing in an in-
dium‑gallium eutectic followed by cauterization at Т ≅ 450 К. The
where d333 is a measured value of piezoelectric constant of a real par- crystal faces were pre-polished by corundum powder. In order to ex-
tially unipolar (single domain) state. clude influence of surface conductivity that might appear due to Н2О
The measurement can be considered as a sensitive indicator for vapor absorption [17] electrode-free faces of samples were degreased
changes in unipolarity since measurements are carried out during de- and dehydrated, heated and soaked at 430К for 3 h before the experi-
termination of direct piezoelectric effect at low conductivity of LiNbO3 ment. Dehydrated silica gel was added to a thermostat after cooling.
at a room temperature. In our case experimental values of piezoelectric Samples LiNbO3:Zn, LiNbO3:Mg and LiNbO3congr for two-electrode
constant d333 were obtained at direct measurement of polarization measurements were x-cut parallelepipeds with sizes 6 × 8 × 5 (x, y, z)
charge that was induced by static mechanical load of a sample in a mm.
given geometry. Polarization charge was measured using electrometric In the temperature range ~ < 500 K dielectric properties and con-
measurer Keithley 6514 (by Keithley Instruments, Inc., USA). The load ductivity of LiNbO3:Zn crystals were researched in the frequencies
on the sample was stepwise with addition of 8 identical loads ~8.5 N range 20 Hz – 1 МHz using measurer of an impedance Solartron 1260
each. Action of the load was directed along the z axis of the sample. (by Solartron Analytical Ltd., Great Britain); measurements on fixed
The growing process of the LiNbO3:Zn crystal series is described in frequencies were carried out by and immitance measurer Е7-20 (by
detail in a paper [14]. The concentration of a dopant (zinc or magne- MNIPI, Belarus). The sample holder was a symmetrical coaxial line with
sium) in crystals was detected by atomic emission spectrometry (Shi- a flat and needle Pt contacts with isolators made of leucosapphire (by
madzu model ICPS-9000). Monocrystal, Russian Federation). The holder shape provided negli-
The concentration of uncontrollable cation impurities (Al, Si, Ca, Ti, gibly small values of mounting reactive parameters and intrinsic par-
V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Sn, Pb) was determined by allel conductivity. Temperature control system provided temperature
spectral analysis in the initial charge and grown lithium niobate crys- instability ± 0.1 K in the range ~350–900 K. Measurements of samples
tals. The results are demonstrated in Table 1. The table contains max- temperature were carried out by differential thermocouple chromel/
imal values among all measured samples in a series of grown crystals. alumel. Thermocouple support junction was stabilized by melting ice.
A series of totally 17 LiNbO3:Zn crystals was grown in identical Thermocouple emf was measured by a standard voltmeter В7-78/1
growth conditions in the dopant concentration range ~4.0–9.0 mol% (AKIP, PriST ltd, Russia) with an error ± 0.5 μV. Sample for im-
ZnO in a melt. pedance spectroscopy were plane-parallel plates ~ 6 × 8 × 1 mm z-
In the temperature area ~ < 500 K precision measurements of

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M.N. Palatnikov, et al. Solid State Ionics 345 (2020) 115178

Table 2 3. Results and discussion

Sizes of studied crystal samples in LiNbO3:Zn(LiNbO3:Mg) and LiNbO3congr,
concentration of a dopant in the melt and in the crystal. Since in the main threshold area (~6.8 mol% ZnO in the melt) the
Sample type and № ZnO ZnO Sample Sample cut distribution coefficient sharply decreases (by approximately 20%) [12],
concentration concentration size, mm3 crystals grown from melts with different dopant concentrations can
in the melt, in the crystal, have the same dopant concentration. Note that defective structure and
mol% mol%
properties of such crystals can be drastically different. Due to this,
1. LiNbO3:Zn 6.76 5.2 6 × 8 × 1 Z description of a series of doped LiNbO3:Zn crystals grown from a melt
2. LiNbO3:Zn 6.76 5.2 6 × 8 × 1 X with a wide range of concentrations should be with indication of a
3. LiNbO3:Zn 7.8 5.2 6 × 8 × 1 Z dopant concentration in both the crystal and the melt during the crystal
4. LiNbO3:Zn 4.03 3.43 6 × 8 × 1 Z
growth. This will provide exact indication of the crystal. Crystal sam-
5. LiNbO3:Zn 6.76 5.2 6 × 8 × 5 X
6. LiNbO3:Mg 5.4 5.0 6 × 8 × 5 X
ples sizes and concentration of a dopant in the melt and in the crystal
7. LiNbO3congr – – 6 × 8 × 5 -X are demonstrated in the Table 2.
Electrical conductivity of crystals LiNbO3:Zn was researched mostly
in the area of lithium ion conductivity [18,19]. At the same time,
conductivity measured at near-room and above-room temperature,
where the main contribution is an electron (polaron or jump me-
chanism) [20] reports are scarce.
Conductivity anisotropy in lithium niobate crystals in the low-
temperature region of electronic conductivity is practically absent [20].
Thus, minimizing the pyroelectric contribution (which strongly de-
creases measurement accuracy) can be achieved at temperatures
~ < 500 K by choosing X-cut samples.
Fig. 1 demonstrates temperature dependences of specific electron
conductivity σdc(Т) of a crystal LiNbO3:Zn along a nonpolar axis X in
the temperature range ~ < 500 K obtained at measurements at direct
current. It is obvious that σ(Т) dependence is described by the Ar-
rhenius law with two types of carriers. Eq. (1) for the process of mixed
ion-electron conductivity can be written in the following form:

A E E
σdc (T ) = σi + σe = ⎡ ⋅exp ⎛ a1 ⎞ + B⋅exp ⎛ a2 ⎞ ⎤,
⎜ ⎟ ⎜ ⎟
⎢T ⎝ k T ⎠ ⎝ k ⎥
o T ⎠⎦ (3)
⎣ o

Fig. 1. Temperature dependence of specific conductivity at DC σdc of a crystal
LiNbO3:Zn (ZnО concentration ~ 5.2 mol% in a crystal, ~ 6.76 mol% ZnО in a
melt, sample 5). X-orientation.
Fig. 2. Temperature dependence of specific conductivity at DC σdc of crystals: 1
– LiNbO3:Zn (ZnО concentration ~ 5.2 mol% in a crystal, ~ 6.76 mol% ZnО in
a melt), X-orientation; 2 – LiNbO3:Mg (Mg concentration ~ 5.0 mol% in a
crystal); 3 - LiNbO3congr.
and х-cut. Pt electrodes were applied by a magnetron sputtering of a Pt
target at ВС in the Ar atmosphere (pAr ≈ 1 × 10−5 Pa) on the prepared
sample surfaces. The surfaces were cleared by an ion method.
where the first term describes the ionic and the second describes the
electronic contribution. At this, A = μiNi|e| = Ni|e|2 Di0/ko where μi is
ion mobility, Ni - their colume concentration, Di0 - diffusion coefficient;
B = μeNeff|e|, where μе – electron mobility, Neff – effective volume
concentration of electron traps. At this, Еa1 and Еa2 correspond to ac-
tivation energies for high- and low-temperature dependence areas, re-
spectively (3).
Treatment of experimental data on current flowing along nonpolar
direction revealed the following values of activation energy:
Eа1 = 1.21 ± 0.02 and Eа2 = 0.31 ± 0.05 eV. Due to literature data,
in LiNbO3 crystals Eа2 value is characteristic of jump-like electron
conductivity on impurity centers, Eа1 value – ion conductivity through
lithium, or, with a lesser possibility, proton conductivity [4,21]. Com-
paratively narrow range of temperature measurements (~310К < T <
500 K) by a two-electrode method at direct current is caused by the fact
that the minimal recorded current was less than ≤~14 fА at the lowest
temperature (~ 310К). The upper temperature (500 K) is limited to this
value due to high possibility of sample breakdown with increasing
temperature and, accordingly, conductivity.
Besides LiNbO3:Zn we have also researched electrical conductivity
in crystals LiNbO3congr and LiNbO3:Mg in the temperature interval
~ < 500 K. For LiNbO3:Mg activation energies were
Eа1 = 1.13 ± 0.02 and Eа2 = 0.29 ± 0.05 eV, for LiNbO3congr -
Eа1 = 1.07 ± 0.02 and Eа2 = 0.30 ± 0.05 eV.
Fig. 2 clearly shows that electron contribution to electrical con-
ductivity of crystals doped by non-photorefractive impurities LiN-
bO3:Zn (LiNbO3:Mg) sharply decreases in comparison with nominally
dopant-free crystal LiNbO3congr. At this conductivity of LiNbO3:Zn
crystals decreases in > 20 time in comparison with LiNbO3congr.
A decrease in conductivity around Troom is apparently connected
with drastic restructure of LiNbO3 crystals lattice at high concentration
of dopants.
Real sites of Fe, Zn and Mg in LN crystals depend on dopant type,

3
M.N. Palatnikov, et al. Solid State Ionics 345 (2020) 115178

Fig. 3. Typical temperature dependences of specific conductivity (a, c) and dielectric constant (b, d) at fixed frequencies of LiNbO3:Zn (~5.4 < СZnO ≤ 6.8 mol%
ZnО in the melt) crystals turned to a single domain state. Z orientation (a, b); X orientation (c, d). 1–100 Hz, 2–1 KHz, 3–10 KHz, 4–100 KHz. Dependences
correspond to crystal samples 1 (a, b) and 2 (c, d).

Fig. 4. A typical impedance diagram of turned to a single domain state samples

of LiNbO3:Zn (~5.4 < СZnO ≤ 6.8 mol% ZnО in the melt) crystals at Т < Т⁎
and Т > Т⁎. Z-orientation. Frequencies are in Hz. The dependence is given on
an example of the sample 1.
Fig. 5. Typical temperature dependences of bulk static conductivity and re-
laxation time of turned to single-domain state LiNbO3:Zn
concentration and valence. The connection between the named factors (~5.4 < СZnO ≤ 6.8 mol% ZnО in the melt) crystals. Dependences are mea-
and ion sites are discussed in numerous works, including our own pa- sured in sample 1.
pers [4,12,22-25].
Due to data in the literature, when zinc concentration in melt is traps [4]. For example, iron ions re-charge Fe3+ + e− = Fe2+ or po-
lower than < ~4.0 mol% ZnO which is much lower that the threshold larons appear at capture of electrons by anti-site defects NbLi. Thus
concentration (~6.8 mol% ZnO in melt [12]) the main acceptor centers these defects participate in jump-like electron or polaron conductivity
(transition metals (Fe, Co, etc.), anti-site defects NbLi) act as electron of LiNbO3:Zn crystals. In “under-threshold” ((~4.0 < СZnO < 6.8 mol

4
M.N. Palatnikov, et al.
Fig. 6. Typical temperature dependences of specific conductivity at fixed fre-
quencies of LiNbO3:Zn crystals (~4.0 ≤ СZnO < 5.4 mol% and
СZnO > 6.8 mol% in the melt). 1–100 Hz, 2–1 KHz, 3–100 KHz. The de-
pendences were measured for crystal samples 3 and 4.
Fig. 7. Temperature dependence of specific conductivity at DC σdc (1) and
static bulk specific conductivity σsv (2) of a crystal LiNbO3:Zn (~5.2 mol% ZnO
in a crystal, ~6.76 mol% ZnО in a melt) with X orientation. The dependences
were measured for crystal samples 5 (1) and 2 (2).
% in melt) and “after-threshold” ((~6.8 mol% ZnO in melt [12]) con-
centrations in LiNbO3:Zn (LiNbO3:Mg) crystals Fe3+ ion occupy Nb
sites [23]. The center [Fe3+
Nb ]
2−
obviously cannot be an electron trap
and participate in electron conductivity.
At the same time, numerous works, including our works, claim that
such electron traps as antistructure defects NbLi are almost absent from
“under-threshold” and “after-threshold” LiNbO3:Zn crystals
[4,12,24,25]. Thus, an electron component of conductivity in crystals
LiNbO3:Zn(LiNbO3:Mg) drastically decreases at relatively low tem-
peratures in comparison with a crystal LiNbO3congr, Fig. 2.
The difference between the influence of Zn and Mg on the LN
structure is revealed in papers [4,25]. Based on the data of these stu-
dies, it can be assumed that a slightly less drastic decrease in the
electronic conductivity of LiNbO3: Mg crystals compared to LiNbO3:Zn
crystals is due to the fact that the complete rearrangement of the
structure in LiNbO3:Mg crystals according to the type described above
5
Solid State Ionics 345 (2020) 115178
occurs at a slightly higher magnesium concentration [4] than in our
sample.
Electron low- and high-temperature lithium ion components of
conductivity were researched in the LiNbO3:Zn crystals samples cut
from one boule by several different methods in the temperature range
~310–900 K. The research demonstrated that electrical properties of
LiNbO3 crystals doped by Zn drastically change not only in the electron
conductivity area (T ~ < 500 K), but also in the lithium ion con-
ductivity area (Т > 500 K). At this, the character of temperature de-
pendence of ion conductivity (contrary to low-temperature electron
component of conductivity) of LiNbO3:Zn crystals depends not only on
Zn concentration in the melt, but also on crystallographic orientation of
samples.
Fig. 3 demonstrates a typical temperature dependence of a specific
conductivity σ(Т) in Arrhenius coordinates and real part of dielectric
constant ε′(Т) measured at fixed frequencies (heating) for single-do-
main samples of LiNbO3:Zn with X- and Z-orientation. Numerous ex-
perimental data obtained at study of tens of samples LiNbO3:Zn [18,19]
demonstrated that all studied samples with Z orientation grown form a
melt with ~5.4 < СZnO ≤ 6.8 mol% have a drastic jump-like increase
in conductivity and dielectric constant at Т⁎ ≈ 800 ± 10 K [18,19],
Fig. 3a, b. In a wide range of temperatures both under and above Т⁎
σ(Т) dependence follows Arrhenius law with the same conductivity
activation energy value Еа ≈ 1.23 eV, characteristic of Li + con-
ductivity in LiNbO3 structure [21]. At Т ≥ Т⁎ we have observed a
pronounced low-frequency dielectric dispersity; note that typical shape
of ε′(Т) dependences shows that the ion conductivity makes prevailing
contribution to measured ε′ values, Fig. 3b. A jump-like increase in
conductivity at Т⁎ is accompanied by an increase in unipolarity and
thus, in piezoelectric constant d333 of a single-domain crystal LiN-
bO3:Zn [18]. The latter is apparently connected with disappearance of
the so-called “stubborn” domains [9]. This phenomenon is caused by a
jump-like increase in conductivity in crystals LiNbO3:Zn (~
5.4 < СZnO ≤ 6.8 mol% ZnО in the melt) at Т* ≈ 800К, which in its
turn is caused by thermal decomposition of polar clusters. Such clusters
usually stabilize boundaries of “stubborn” domains and are formed by a
complex of intrinsic and impurity defects. Thus, thermal decomposition
of polar clusters in LiNbO3:Zn crystals leads to a jump-like injection of
charge carriers, which causes a sharp increase in a conductivity and
instability with following decomposition of “stubborn” domain struc-
ture [26]. AT the same time, we failed to observe a jump-like increase
in conductivity and dielectric constant at Т* in LiNbO3:Zn
(~5.4 < СZnO ≤ 6.8 mol% ZnО in the melt) crystals with X orientation
[18], Fig. 3c, d.
We have researched dispersity of a complex impedance of crystals
LiNbO3:Zn (~5.4 < СZnO ≤ 6.8 mol% ZnО in the melt). It is widely
known that analysis of impedance and admittance diagrams allows us
to separate a contribution of bulk conductivity into the measurements
correctly [27–29]. Such analysis also provides temperature de-
pendences of static specific conductivity σSV(Т) and relaxation time of
bulk conductivity of samples τV(Т). A typical impedance diagram of
turned to a single domain state samples of LiNbO3:Zn
(~5.4 < СZnO ≤ 6.8 mol% ZnО in the melt) crystals at different
temperatures is featured on Fig. 4.
Due to a typical shape, impedance diagrams are similar in the stu-
dies frequencies range both under and above Т⁎. Electrodes polarization
effect described in detail in [30] for a wide number of ion-conducting
materials, is almost absent. This is caused by two facts: existence of only
one Debye type relaxation process in middle frequencies (which cor-
responds to ion conductivity); absence of co-existing low-frequency
process on the diagram (such process governs electrodes polarization),
Fig. 4.
Fig. 5 demonstrates σSV(Т) and τV(Т) dependences for bulk ion
conductivity obtained as a result of analysis of impedance diagrams of
crystals LiNbO3:Zn (~5.4 < СZnO ≤ 6.8 mol% ZnО in the melt) ob-
tained at different temperatures.
M.N. Palatnikov, et al.
At the same time, for LiNbO3:Zn crystals turned to a single-domain
state with both X and Z orientation, grown from a melt with a dopant
concentration much lower (~4.0 ≤ СZnO < 5.4 mol%) and higher
(СZnO > 6.8 mol%) than the main concentration threshold we failed to
observe jump-like increase in temperature at Т⁎, Fig. 6. Thus, their
conductivity at temperatures below Т⁎ is almost one order of magnitude
lower, and activation energy is slightly higher (~1.29 eV) than that of
crystals grown from a melt with a near-threshold
(~5.4 < СZnO ≤ 6.8 mol% ZnО in the melt) dopant concentrations,
Figs. 3 and 6. Note that temperature dependences of LiNbO3:Zn crystals
grown from both Li-rich and Li-poor melts almost completely coincide,
Fig. 6.
Results of research of electrical conductivity of crystals LiNbO3:Zn
(~4.0–9.0 mol% ZnО in the melt) by a two-electrode method with a
constant DC application (T ~ < 500 K) and by an impedance spec-
troscopy (T ~ < 500 K) correlate pretty well. Fig. 7 reveals tem-
perature dependences of a specific conductivity at constant ВС σdc and
static bulk specific conductivity σsv. These values were researched by
impedance spectroscopy in a crystal LiNbO3:Zn (~5.2 mol% ZnO in a
crystal, ~6.76 mol% ZnО in a melt) with X orientation. It is clear that
extrapolation of a low-temperature part of the dependence to the high-
temperature area leads to almost complete coincidence of dependences
σdc(Т) and σsv(Т), obtained by different methods, Figs. 1, 5, 7. At this,
energy of activation of ion conductivity, calculated from constant DC
measurements (Edc = 1.21 ± 0.02 eV) and from impedance spectro-
scopy (Est = 1.21 ± 0.02 eV) coincide within error, Fig. 7.
4. Conclusion
This paper considers study of electrical conductivity and dielectric
constant in a series of 17 crystals LiNbO3:Zn(~4.0–9.0 mol% ZnО in the
melt) by two-electrode application of direct current (T ~ < 500 K) and
impedance spectroscopy (T ~ < 500 K). In order to compare results,
electrical conductivity was also studied in crystals of a congruent
composition nominally pure LiNbO3congr and doped by magnesium
LiNbO3:Mg by two-electrode application of constant DC
(T ~ < 500 K). We have proved that electron contribution to electrical
conductivity of crystals doped by non-photorefractive dopants
LiNbO3:Zn (LiNbO3:Mg) is sharply lower than that of undoped sample
LiNbO3congr.
A decrease in conductivity at temperatures above Troom was found
to be connected with strong restructure of LiNbO3 crystals lattice at
high concentration of zinc and magnesium. As a result, Fe3+ cations,
for example, localize in Nb sites and such electron traps as antisite
defects NbLi are almost absent in under-threshold and above-threshold
crystals LiNbO3:Zn.
A research in the wide range of temperatures (~310-900К) revealed
that electrical properties of LiNbO3:Zn crystals strongly change not only
in the area of electron conductivity (T ~ < 500 K), but also in the area
of lithium ion conductivity (Т > 500 K) compared to congruent LN
crystals. At this, type and parameters of temperature dependence of
lithium ion conductivity of LiNbO3:Zn crystals change with an increase
in zinc concentration in the melt and in the crystal and depend on the
samples crystallographic orientation.
A jump-like increase in conductivity accompanied by an increase in
unipolarity degree is observed in a crystal LiNbO3:Zn
(~5.4 < СZnO ≤ 6.8 mol% ZnО in the melt) with Z orientation at
Т⁎ = 800 ± 10К. The crystal was turned to a single domain state.
Apparently, an increase in unipolarity degree is caused by a jump-like
injection of charge carriers (most probably Li+ cations because Еа
under and above Т⁎ = 800 ± 10К is the same) that causes a sharp
increase in conductivity and leads to a thermal decomposition of
“stubborn” domain structure in the crystal at temperatures higher than
Т* ≈ 800К.
6
Solid State Ionics 345 (2020) 115178
Funding source
This work was supported by the Ministry of Science and Higher
Education of the Russian Federation scientific topic No 0226-IC-2018-
0004 (registration # АААА-А18-118022190125-2).
Data availability statement
The raw data required to reproduce these findings are available to
download from [31].
Declaration of competing interest
The authors declare no conflict of interest.
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