Anionic depolymerization transition in IrTe2

Yoon Seok Oh1 , J. J. Yang2 , Y. Horibe1 , and S.-W. Cheong1,2,∗

1
Rutgers Center for Emergent Materials and Department of Physics & Astronomy, Piscataway, NJ 08854, USA
2
Laboratory for Pohang Emergent Materials and Department of Physics,
Pohang University of Science and Technology, Pohang 790-784, Korea
(Dated: March 21, 2013)
Selenium (Se) substitution drastically increases the transition temperature of iridium ditelluride
(IrTe2 ) to a diamagnetic superstructure from 278 K to 560 K. Transmission electron microscopy
experiments revealed that this enhancement is accompanied by the evolution of non-sinusoidal
arXiv:1303.4772v1 [[Link]-el] 19 Mar 2013

structure modulations from q = 1/5(101̄)- to q = 1/6(101̄)-types. These comprehensive results

are consistent with the concept of the destabilization of polymeric Te-Te bonds at the transition,
the temperature of which is increased by chemical and hydrostatic pressure and by the substitution
of Te with the more electronegative Se. This temperature-induced depolymerization transition in
IrTe2 is unique in crystalline inorganic solids.

A polymer is a large molecule made up of repeating

chemical units connected by covalent bonds [1]. Many
polymers are thermally unstable and decompose at high
temperatures (T ). Other polymers undergo phase tran-
sitions upon changes in temperature. Rubbery or flexi-
ble thermoplastics can transform to glassy or crystalline
states below specific temperatures without losing their
polymeric nature. Depolymerization-polymerization
transitions have also been observed in a number of poly-
meric materials. For example, rhombic sulfur with cyclic
molecule rings (depolymerized S8 ) becomes polymerized
to form long polymerized sulfur chains above 140 ◦ C
[2, 3], and this depolymerization-polymerization transi-
tion is thermally reversible. Fullerene (C60 ) molecules
forming an fcc structure with a quasi-free molecular
rotation [4] can be polymerized to orthorhombic one- FIG. 1. (color online) (a) Schematic perspective view of the
polymeric network of Te-Te bonds. (b) Crystal structure of
dimensional chains [5] or rhombohedral two-dimensional
IrTe2 showing Te-Te bond lengths and the relative sizes of the
lattices [6] under external pressure. In addition, visible Ir4+ and Te2− ions (the radii of the Ir4+ and Te2− ions with
or ultraviolet light illumination can induce the polymer- 6 coordination sites are 0.62 Å and 2.2 Å, respectively). (c)
ization of C60 molecules [7]. Temperature dependence of the resistivity of an IrTe2 single
crystal along the c-axis (ρc ) and in the ab-plane (ρab ).
Layered chalcogenides, composed of stacking polyhe-
dron layers with van der Waals (VDW) gaps, exhibit rich
quasi-low-dimensional physical properties such as super-
conductivity (in FeSe [8, 9]), topological insulating be- Pd-intercalated and doped IrTe2 was also understood in
havior (in Bi2 Se3 [10–12]), and a high mobility in field- terms of the competition between CDW and supercon-
effect-transistor structures (in MoS2 : 200 cm2 V−1 s−1 ductivity [17]. However, a recent optical spectroscopy
[13]; in WSe2 : 500 cm2 V−1 s−1 [14]). Transition metal study suggested that the electronic/structural transition
dichalcogenides (such as 1T-TaS2 , 1T-TaSe2 , and 1T- in IrTe2 is driven by a reduction in the kinetic energy
TiSe2 , forming layered CdI2 structures (space group: of electrons due to Te 5p band splitting below the struc-
P 3̄m1)) show Charge-Density-Wave (CDW) states ac- tural transition temperature [17]. Studies using x-ray
companied by structural modulations below their tran- photoemission spectroscopy [18] and angle-resolved pho-
sition temperatures (TC s). For 1T-TaS2 and 1T-TiSe2 , toemission spectroscopy (ARPES) [19] have indicated the
applied pressure and chemical doping suppress the CDW importance of the orbital degeneracy of Ir 5d and/or
state and induce superconductivity [15, 16], attributed Te 5p for the transition. Thus, the origin of the elec-
to competition between CDW and superconductivity. tronic/structural transition below ∼260 K remains un-
IrTe2 also crystallizes in the CdI2 structure. A sud- clear.
den increase in resistivity below ∼260 K accompany- This letter provides evidence that the elec-
ing structural modulation and diamagnetism was inter- tronic/structural transition in IrTe2 is a phase transition
preted in terms of CDW instability. Similarly to the be- involving the depolymerization-polymerization of anionic
havior of 1T-TaS2 and 1T-TiSe2 , superconductivity in Te bonds. Short Te-Te bonds between adjacent Te layers
 2

20 800
in the normal state of IrTe2 have already been suggested
(a) IrTe2-x Sex (b)

$ DC (10-6 emu/mole)
to result in three-dimensional polymeric networks with x = 1.10
0
multiple covalent Te-Te bonds (Figure 1(a)) [20, 21]. 600 1.00
0.70
Formation of the polymeric Te-bond networks in the -20

# (!" cm)
0.50
polymerized state is associated with a fractional ionic 0.45 crystal
-40 x = 0.05 400
character of Te (Te1.5− ) and with the destabilization 0.1 0.40
of the highly oxidized state of Ir, resulting in effective -60 0.3 0.30
Ir3+ valence states [22]. Consistently, the Te-Te distance 0.7 200
0.20
-80 0.10
(3.567 Å) between neighboring Te-Te layers is ∼10 % 0.05
shorter than that in each Te layer [21] (Figure 1(b)). 100
(c) IrTe2 crystal 0.00
0 kbar 0
As a result, IrTe2 has a c/a ratio of 1.37, significantly 2.8 0 100 200 300 400 500 600
80 T (K)

(!" cm)
smaller than the c/a ratio of 1.6-1.8 for the typical 3.5 70
4.9
hexagonal close-packed CdI2 structure with VDW gaps 60
(d)

(!" cm)
60
[23]. For example, in HfTe2 (1T-TiSe2 ), where Hf (Ti) 40 50 IrTe2
ions are in a stable, highly oxidized state of 4+, VDW crystal
20 40
gaps are allowed between the Te-Te (Se-Se) layers, and 30
thus HfTe2 (1T-TiSe2 ) exhibits a large c/a ratio of 0
0 100 200 300 400 0 1 2 3 4 5 6
1.68 (1.70) [22, 23]. Combined with the results of an T (K) P (kbar)
earlier x-ray spectroscopy study [18], our comprehensive
experimental results on IrTe2 with Se substitution and
hydrostatic pressure strongly suggest that below ∼260 FIG. 2. (color online) Temperature dependence of (a)
the magnetic susceptibility of polycrystalline IrTe2−x Sex in
K, the covalent Te-Te bonds weaken and the polymeric
µ0 H=1 T upon warming, and (b) the resistivity of polycrys-
Te-bond network becomes depolymerized. This depoly- talline IrTe2−x Sex and a single crystal. ρ(T ) curves for x
merization of Te-Te bonds is associated with an increase values other than x=0 are shifted by arbitrary constants for
in the ionic character of Te1.5−δ/2− and a mixed valence clarity. (c) The temperature dependence of the resistivity of
state of Ir3+δ+ in the diamagnetic superstructure, where an IrTe2 single crystal upon warming under various hydro-
δ indicates the change in the Ir valence state. static pressures. (d) Pressure dependence of the resistivity of
IrTe2−x Sex specimens were prepared in polycrys- an IrTe2 single crystal at 300 K.
talline and single crystalline forms. For polycrystalline
IrTe2−x Sex , Ir, Te, and Se elements were mixed sto-
ichiometrically, ground, pelletized, and synthesized in Fig. 2(b), which shows the T dependence of electric re-
vacuum-sealed quartz ampules. X-ray diffraction (XRD) sistivity (ρ(T )) of polycrystalline specimens up to x=1.1.
experiments were performed using a Rigaku D/Max-RB A maximum TC of ∼560 K was observed for IrTe0.9 Se1.1 ,
x-ray diffractometer with Cu Kα radiation. Single crys- corresponding to the chemical solubility limit of Se. A
talline samples were grown from the Te metal flux. The single crystal of IrTe2 undergoes its transition at 283 K
Se compositions of IrTe2−x Sex single crystals were esti- (279 K) upon warming (cooling), as shown in Fig. 1(c).
mated by comparing their TC s with those of polycrys- As shown in Fig. 2(c), applying hydrostatic pressure (P )
talline IrTe2−x Sex . Magnetization and electrical resistiv- to an IrTe2 single crystal also increases TC . The sharp
ity were measured up to 400 K using the Quantum De- transition in ambient pressure increases monotonically
sign MPMS-XL7 and PPMS-9. High-T transport prop- with increasing hydrostatic pressure. At 300 K, hydro-
erties were measured in a tube furnace using the DS340 static pressure consistently induces the transition at 3.5
function generator and an SR510 lock-in amplifier, and kbar (2.7 kbar) upon increasing (decreasing) pressure.
hydrostatic pressure experiments were performed using Note that the magnitude of diamagnetic susceptibil-
Easylab Pcell30. Samples for transmission electron mi- ity suddenly increases from approximately −60 × 10−6
croscopy (TEM) studies were prepared by cleaving and emu/mole (x=0.0 [24], 0.05 and 0.1) to −70 × 10−6
Ar ion milling. TEM experiments were carried out with emu/mole (x=0.3 and 0.7). The estimated core diamag-
JEOL-2010F and JEOL-2000FX transmission electron netism is approximately −170 × 10−6 emu/mole, and
microscopes equipped with a low-T sample stage and a the difference between the core diamagnetism and the
room-T double-tilt sample stage. observed diamagnetic signals corresponds to the contri-
Figure 2(a) exhibits the Se substitution effect on bution of Pauli paramagnetism from itinerant electrons.
χDC (T ) of polycrystalline IrTe2−x Sex , measured upon This sudden change in Pauli paramagnetism reflects an
warming. As Se concentration increases, the transition to abrupt change in the electronic structure of IrTe2−x Sex
the low-T diamagnetic state increases significantly from with respect to Se doping. Indeed, TEM below TC re-
278 K (x=0.05) to 288 K (x=0.1) and 370 K (x=0.3). At veals the existence of two distinct modulated structures,
x=0.7, the material only shows diamagnetic susceptibil- characterized by the presence of two distinct superlat-
ity up to 400 K. This TC enhancement is more evident in tice peaks. Figures 3(a)-3(f) show electron diffraction
 3

(inset of Fig. 3(a)) reveals that all four 1/5(101̄)-type

superlattice peaks exhibit similar intensities. A simi-
lar trend can be observed for the superlattice peaks of
other compositions. The presence of high harmonics with
strong intensities indicates that the superstructure mod-
ulations are highly non-sinusoidal and rather rectangu-
lar. This highly non-sinusoidal modulation is different
from the typical sinusoidal modulation in CDW states,
for example, in 1T-TaSe2 and 1T-TaS2 [25]. In addition,
most CDW transitions in M X2 are associated with three
q modulations, but the modulation in IrTe2 occurs to-
gether with a “single q and three domains”. Indeed, the
three domains (or twins), corresponding to three q values
with a relative 120◦ in-plane angle, are visible in polar-
ized optical microscope images (lower left inset in Fig.
3(h)) as well as in TEM images (see Fig. S1).
Figure 4(a) presents the T versus x phase diagram
FIG. 3. (color online) (a)-(f) Electron diffraction patterns be- of IrTe2−x Sex , where the phase boundaries are deter-
tween the 1̄20 and 021̄ fundamental spots for IrTe2−x Sex . The mined from the results of TEM and ρ(T ) experiments
intensity profile between the 1̄20 and 021̄ fundamental peaks with warming and cooling. The thermal hysteresis (∆T )
of x=0.0 is shown in the inset. Dark-field images in (g) x=0.0 of TC , estimated from warming and cooling ρ(T ) curves
at ∼85 K, and (h) x=0.45 at room temperature. The upper
as a function of x (see Fig. 4(b)), exhibits a sudden
right insets of (g) and (h) are high-resolution TEM images
for x=0.0 at ∼85 K and x=0.45 at room temperature, re- jump at x=0.2-0.3, coinciding with the abrupt change of
spectively. The (g) and (h) insets show the superlattice mod- superstructure from the 1/5(101̄) to the 1/6(101̄) type.
ulations with periodicities of 1.4 nm and 1.7 nm associated Thus, although TC appears to increase monotonically as
with the 1/5(101̄) and 1/6(101̄) superlattice peaks, respec- a function of x across the phase boundary of the 1/5(101̄)
tively, as well as antiphase boundaries (APB) due to phase and 1/6(101̄) superstructures, ∆T accurately reflects the
shifts of the superlattice modulations. The lower left inset presence of the phase boundary.
of (h) displays a polarized optical microscope image of twin
domains of x=0.45. XRD experiments at room T are highly informative re-
garding the physical nature of the transition. As shown in
Fig. 4(c), the a- and c-axis lattice constants for x ≤ 0.1
decrease linearly with increasing x (i.e., following Ve-
patterns around the 1̄20 and 021̄ fundamental spots for gard’s law), consistent with the fact that Se ions are
x=0.0, 0.15, 0.2, 0.3, 0.5, and 1.0, respectively. Figure smaller than Te ions. However, a sudden increase in “c”
3(a) presents data for pure IrTe2 obtained at ∼85 K, (along with a smaller increase in “a”) occurs at x=0.1-
while Figs. 3(b)-3(f) present data recorded at room T . 0.15, corresponding to the phase boundary (purple ver-
The 1/5(101̄)-type superlattice spots observed at x=0.0 tical line) between the high-T polymerized state and the
(Fig. 3(a)) remain intact for x=0.15 and 0.2 (Fig. 3(b) 1/5(101̄) superstructure. Thus, the dominant structural
and 3(c)) but change suddenly to the 1/6(101̄)-type at effect at the transition to the diamagnetic superstructure
x ≥ 0.3 (Figure 3(d)-3(f)). The 1/5(101̄) and 1/6(101̄) is the sudden increase in “c”, which reflects the sudden
superlattice peaks correspond to 1.4 nm and 1.7 nm spac- weakening of interlayer coupling. This increase in “a”
ings in real space, respectively. In both cases, we have and “c” gradually lessens for values of x beyond the phase
frequently observed fine antiphase boundaries within a boundary (green vertical line) between the 1/5(101̄) and
large strain-relieving twin domain in dark-field images 1/6(101̄) superstructures. The structural evolution over
obtained using a 021̄ fundamental spot. Dark-field im- x seems better reflected in a plot of the c/a ratio vs. x.
ages of x=0.0 at ∼85 K and x=0.45 at room T are The c/a ratio increases drastically at the phase bound-
shown in Fig. 3(g) and 3(h), respectively. Fine antiphase ary between the high-T polymerized state and the dia-
boundaries perpendicular to the superlattice modulation magnetic 1/5(101̄) superstructure, suggesting a weaken-
wave vectors are clearly visible in both Fig. 3(g) and ing of the polymerized Te bonds through the first-order
3(h). The typical spacing between antiphase boundaries phase transition. As the c/a ratio (1.39-1.4) is still sig-
is approximately 10 nm in both cases. High-resolution nificantly smaller than that (1.6-1.8) of the true VDW
TEM images in the upper right insets of Fig. 3(g) and systems, the depolymerization in the diamagnetic super-
3(h) clearly indicate that these antiphase boundaries are structure is likely still partial. In fact, the modulated
associated with phase shifts of the superlattice modula- superstructure may result from an ordered arrangement
tion waves across the boundaries. The intensity profile of polymerized and depolymerized Te bonds. We empha-
between the 1̄20 and 021̄ fundamental peaks of x=0.0 size that the most drastic observation in our experimental
 4

600
polymerized 1/5(101) 1/6(101) The increase in TC with increasing hydrostatic pres-
(a) IrTe2-xSex 4.00 5.50 sure is summarized in Fig. 4(e). Thus, hydrostatic
500 (c) pressure also destabilizes the polymerized state, which
Polymerized 3.95 5.45
RT seems to be counter-intuitive. However, the application

c (A)
a (A)
State 3.90 5.40
c
400 TC, of hydrostatic pressure to PtTe2 [27] with anionic poly-
T (K)

3.85 a 5.35
TC, meric Te-Te bonds increases the ratio of interlayer to in-
crystals 3.80 5.30
300
(d) tralayer Te-Te distance. Thus, this increase in the in-
1.40 c/a terlayer/intralayer ratio with hydrostatic pressure likely
1.00

V/V0
c/a
200 1/5 1/6 (101) 1.39
V/V0 stabilizes the low T depolymerized state, leading to the
(101) 0.96
1.38 increase in TC . The magnitude of the chemical pres-
100 1.37 0.92 sure resulting from Se doping has been estimated using
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
40
(b) poly IrTe2-xSex the initial slope of a(x) and c(x) for 0 ≤ x ≤ 0.1 and
400
30 crystals
(e) the bulk modulus [28, 29]. Fig. 4(e) compares the ef-
T (K)

350 TC(P) 0.2 fect of mechanical hydrostatic pressure with the effect
T (K)

20

10 300
0.15 of Se chemical pressure on TC . This qualitative agree-
0.1 TC(x)
x = 0.05 ment indicates that the effect of Se substitution also fits
0 250
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 0 2 4 6 8 10 12 14 16 18 the role of an archetypal chemical pressure effect. How-
IrTe2-xSex P (kbar)
ever, the positive slope with respect to chemical pressure,
∂TC /∂P = +6.8 K/kbar, is larger than that in response
FIG. 4. (color online) (a) Temperature (T ) versus Se concen-
to hydrostatic pressure, ∂TC /∂P = +5.4 K/kbar. Thus,
tration (x) phase diagram of IrTe2−x Sex constructed with TC the depolymerization of the polymeric Te bond appears
values obtained from T -dependent resistivity measurements to be further enhanced by the electronegative character
under warming (triangle) and cooling (inverted triangle). The of Se ions. Note that the increase in TC in IrTe2 with in-
diamond symbols indicate the TC values of IrTe2−x Sex sin- creasing chemical/hydrostatic pressure is in contrast with
gle crystals (x=0 and 0.45). (b) Width of the thermal hys- the effect of chemical/hydrostatic pressure on transition
teresis (∆T ) as a function of x in IrTe2−x Sex . The green metal dichalcogenides (such as 1T-TaS2 [15], 1T-TiSe2
guide line depicts the phase boundary between the 1/5(101̄)
and 1/6(101̄) superstructures. Se-doping dependence of (c)
[16], and 1T-TiSe2−x Sx [30]), in which the CDW state is
the a- and c-axis lattice constants, (d) the c/a ratio and the suppressed by pressure.
normalized volume determined from x-ray diffraction results. A number of our findings from the chemi-
The purple and green lines indicate the phase boundaries of cal/hydrostatic pressure, TEM, and XRD experiments
the paramagnetic to 1/5(101̄) transition and the 1/5(101̄) to are distinct from the typical behavior of CDW systems.
1/6(101̄) transitions, respectively. (e) Hydrostatic pressure
A peak near 1/5(101̄) in the charge susceptibility of IrTe2
and calculated chemical pressure dependence of TC of IrTe2 .
was interpreted as an indication for the presence of a
nesting vector of Fermi surface and CDW instability [24],
but the charge susceptibility exhibited other features.
results is the large increase in TC resulting from the sub- Our results, first, reveal that the superlattice modula-
stitution of Se ions, which not only have a smaller ionic tions are associated with a single q and three domains
radius but are also more electronegative than Te ions. and are highly non-sinusoidal, uncommon characteristics
These electronegative Se ions should destabilize covalent of typical CDW systems. Second, the drastic increase
anionic bonding, thus leading to the drastic increase in in TC up to 560 K with the application of chemical and
TC . hydrostatic pressure to IrTe2 has never been observed
Furthermore, the increase in the number of depoly- in any other CDW systems, which tend to have modest
merized Te bonds with increasing Se substitution is also TC values due to the small energy scale associated with
consistent with the decrease in the magnitude of the mod- Fermi surface instability. In addition, the sudden in-
ulating wave vector from a 1/5 to 1/6 type. We also note crease in the c/a ratio below TC is also unique compared
that this scenario is consistent with the weakening of an- with the behavior of CDW systems. These empirical
ionic polymeric Te-Te bonds with Se doping observed in observations, combined with the earlier proposal of
Pt(Te,Se)2 [26]. Depolymerization reorganizes the ionic charge modulations based on x-ray photoemission
characteristics of Te anions, and reorganized Te1.5−δ/2− spectroscopy experiments [18], are consistent with our
ions lead to a mixed valence state of Ir cations such as proposed scenario of a depolymerization-polymerization
Ir3+δ+ . In fact, evidence of mixed valence Ir ions in the transition at TC associated with the charge ordering of
low-T diamagnetic superstructure was observed in a pre- Ir3+ /Ir4+ ions. We emphasize that the earlier study of
vious study using x-ray spectroscopy [18]. Note that the Fermiology [24] did not take into account the lattice con-
non-sinusoidal structural modulations in the TEM ex- tributions such as phonon contribution, and we cannot
periments here appear to be consistent with the charge rule out that the Fermi surface instability contributes
ordering of the mixed valence states of Ir ions. to the depolymerization-polymerization transition in a
 5

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