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CHEMICAL PROBLEMS 2018 № 2 (16) ISSN 2221-8688
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UDC [541.123.3+536]:546.289'24
PHYSICOCHEMICAL ASPECTS OF TERNARY AND COMPLEX PHASES DEVELOPMENT BASED ON THALLIUM CHALCOHALIDES
D.M. Babanly, D.B.Tagiyev
Acad. M. Nagiyev Institute of Catalysis and Inorganic Chemistry National Academy of Sciences ofAzerbaijan 113, H.JavidAve., Baku, AZ1143; e-mail: dunyababanly2012@,gmail.com
Recieved 10.05.2018
The results ofphysical and chemical investigation of some ternary and more complex systems which are of interest in terms of obtaining thallic chalcohalides and new multicomponent phases on their basis have been systematized and analyzed in the review paper. This class of inorganic substances is of scientific and practical interest as promising functional materials with thermoelectric, optical, magnetic, sensor and detector properties. The literature data on crystal structure, thermodynamic and some physico-chemical properties of thallium chalcohalides and intermediate phases on their basis have been investigated. Keywords: thallium chalcohalides, functional materials, phase diagram, solid solutions, thermodynamic properties, crystal structure.
1. Introduction
Chalcogenides and chalcohalides of heavy metals, including 5p and 6p elements, are in the cenre of attention of world scientists since the middle of the last century due to their interesting chemical bonding characteristics and fascinating physical properties [1-5]. Many of them are applied or considered perspective for application in various fields of electronics and high technologies.
The discovery of research achievements in nanomaterials over the past two-three decades [6,7] and the discovery of graphene [8] and topological insulators (TI) [9-11] have given a powerful impetus to the development of electronics and other high technologies. The discovery of graphene stimulated the search for other graphene-like two-dimensional materials, among which 2D transition metal chalcogenides, due to their unique physical properties, proved extremely promising for use in new generation optoelectronic devices [1216].
The most important applications of TI materials are new spin-off devices and permanent transistors for quantum computers, based on the quantum spin Hall effect [9-11, 17] and the anomalous quantum Hall effect [18]. These materials are also prospective for application in superior magnetoelectronics, optoelectronics, security systems, and so on
[19-21]. Currently the most widely studied substances like TI are Bi2Se3, Bi2Te3, Sb2Te3 compounds and phases based on them [9-11, 22, 23]. However, recent studies have shown that a number of tetradimide-based compounds formed in AIV-BV-Te systems also posess interesting TI properties [11, 24-27].
Heavy metal chalcogenides play an important role among the new photoelectric, thermoelectric materials and other energy-transducers generated for the use of alternative and renewable energy sources [28-31]. These materials are also used to create highly sensitive sensors and detectors for the implementation of various complex technological processes, as well as, for monitoring environmental safety on Earth in in the atmosphere [7, 32].
Chalcohalogenides of heavy metals, including 5p- and 6p-elements occupy a special place among the above mentioned promising materials for application in many other areas [3, 33-43]. For example, ferroelectric semiconductors of type BVXHal (BV-Sb, Bi, X-S, Se, Te, Hal, Cl, Br, I) possess precious photoelectric, magnetic, electrooptic, pyroelectric, pyro-optic and other properties and consiredered to be promising for application as nuclear, y- and infrared beam
detectors, light modulators, gas sensors, photon crystals, memory elements, etc.[33-35].
It is expected that the Rashba effect, which provides spin manipulation through the electric fields of these materials, will be used in devices proposed as a spin field and spin Hall transistors [36-40]. The most recent materials proposed in this direction are, for example, spin-orbit coupling, ferroelectric semiconductors controlled by electric polarization [41-43].
Over the last decade, the phase equilibrium, thermodynamic properties of BV-X-I systems have been studied extensively, primary crystallization areas and fundamental thermodynamic functions of intermediate phases, including BVXI compounds, have been determined [44-48].
Numerous studies have shown that ternary chalcogenides and chalcohalogenides of 6p (Tl, Pb, Bi) and 5p (Sn, Sb) elements have an anomalous low thermal conductivity and high thermoelectric efficiency [29-31].
According to recent studies, thallium chalcogenides and ternary chalcohalide hybrids (Tl6SeI4,Tl6SI4) have potential applications, such as radiation detectors, and form a new class of inorganic semiconductor detector materials [49-57]. These compounds and phases on their basis are far more promising than CZT (Cd0.9Zn0.1Te) of industrial importance - the most sensitive detector material for functional indications, and are one of the most promising materials for new generation electronic devices. Even though the talium compounds are toxic, compounds and intermediate phases containing thallium have an important place among such materials that have unusual electronic properties. It has been established that three-dimensional seleno- and thioiodides of thallium have three-dimensional structure (3D) and therefore possess better internal electronic and mechanical properties, demonstrating both
high hole and electron conductivity compared to linear (1D) and layered (2D) compounds [49-52].
Tl6S(Se)I4 monocrystals were studied, their electron structure, dielectric, optical properties and structure defects examined [5354]. It has been established that these ternary compounds have higher mechanical strength and optimal band gap value for radiation detectors compared to TlI and ThS(Se) binary compounds that form them.
Note that the establishment of scientific basis for the directional search and synthesis of new multicomponent inorganic materials with a combination of physical and physico-chemical properties requires a complex analysis of the corresponding systems, their phase diagrams, and the determination of the fundamental thermodynamic functions of the intermediate phases [58, 59]. From this point of view, it is of particular interest to have a complex physical-chemical study of complex systems known to be formed of solid analogues or solid solutions based on known binary and triple compounds with valuable application properties. Therefore, a physicochemical investigation of complex systems composed of structure analogs of known binary and ternary compounds with valuable application properties or solid solutions based on them is of particular interest.
The review article summarized and comparatively analyzed the literature data and experimental results obtained by the authors on the ternary Tl-X-Hal systems, ThTe-TlHal-TlHal/ and Tl5Te3-Tl9BiTe6-Tl5Te2Hal concentration ranges of the Tl-X-X-Hal va Tl-X-Hal-Hal/ (X,X/ -S,Se,Te; Hal,Hal/ -Cl,Br,I) quaternary systems, and on the phase equilibria, thermodynamic, crystallographic and some physicochemical properties of the complex thallium chalcohalogenide systems.
2. Phase equilibria in the Tl-X-Hal (X-S, Se, Te, Hal -Cl, Br, I) systems and some physico-chemical properties of intermediate phases
Initial researches on Tl-X-Hal (X-S, Se, with the stydy of ThX-TlHal and TlX-TlHal Te, Hal -Cl, Br, I) systems began in the 1980-s quasibinary sections.
2.1. Phase equilibria in the T1 - S - CI (Br,I ) systems
Tl-S-Cl system. TICI-TI2S quasi-binary section of this system is of peritectic type [60, 61] and forms a congruently melted TI6SCI4 ternary compound at 683 K (Fig. 1, a). In [62], the system was re-visited, formation of the TI6SCI4 peritectic ternary compound was confirmed and coordinates of the peritectic and eutectic equilibriums were found to be essentially different from the results of the [60.61] (Fig.1, b). In contrast to [60,61], existence of the immiscibility area (~13-50 mol% TI2S) of two liquid phases has been
established [62].
The system was studied at the Tl-TlCl-S concentration range by means of DTA, X-ray and SEM analysis, as well as through the measurement of microhardness and EMF. A series of polythermal and isothermal sections, liquidus sufrace projection of its phase diagram was constructed [62-64].
It found that TlCl-S system is also a quasibinary, forming a phase diagram with a monotectic and degenerated eutectic equilibrium near the sulfur [63].
mol % TI,S
a) b)
Fig 1. Phase diagram of the system TlCl-ThS: a) - [61], b) - [63]
Tl-S-Br system. TlBr-ThS and TlBr-S sections of this ternary system are quasi-binary [65,66]. According to [60], TlBr-Tl2S system is characterised by formation of incongruently melting ternary Tl6SBr4 compound at 716K (Fig.2,a). The phase equilibrium in the system was re-examined; the formation of the above mentioned ternary compound proved, and coordinates of nonvariant equilibria specified (Fig. 2,b) [66].
TlBr-S system is of monotectic and degenerated eutectic type. Tl - S - Br ternary system was investigated at the Tl-TlBr-S concentration range, some isopleth sections and the projection of the liquidus surface of its phase diagram were constructed, types and coordinates of non- and monovariant equilibria determined [65,66].
T.K.
740
720 700 680 ^660 640
■ 716 _
690 \/
(67%)
CQ
H
T.K
700
(>25
733 a^P, L J
L— t£> cn H
® t- C, U.SBrjTLS 1 1 1
TIBi 20
TIBr 20
40 60 mol%TUS
SO
T1,S
40 № mol%Tl,S
72 H
NO
TL.S
a)
b)
Fig.2. Phase diagram of the system TlBr-ThS: a) - [61], b) - [67]
Tl - S - I system. TlI-ThS quasi-binary section is characterized by formation of ternary Tl6Sl4 compound melting congruently at 713K, and a phase of the TI3SI composition that is stable at 640-670K temperature intervale [61]. According to the results of [60], Tl6Sl4 melts congruently at 710K and has a ~4 mol % (according to [67,68] ~2 mol %) homogeneity area [69] report that, Tl6Sl4 melts congruently at 710K, TbSI -incongruently at 673K by peritectic reaction.
The latter decomposes at 653K according to solidphase reaction into TI2S and T16SI4 compounds.
The full description of phase equilibria of the Tl-S-I ternary system is given in the Fig.3 [65,69,70]. Three polythermic sections (TlI-ThS, TlI-S va Tl6SI4-Tl) of this system are quasi-binary. TlI-S and T16SI4-T1 systems are characterized by monotectic and eutectic equilibriums.
i
alïv S
Fig. 3. The projection of the liquidus surface of the system Tl-TlI-S. Primary crystallization areas: 1-Tl2S, 2.-TI4S3, 3-TlS, 4-TIbSI, 5-Tl6SI4 (Y), 6-(T1I)ii, 7-TI2I3, 8-TlI3, 9- I2, 10-T1, 11-S and 12-TI2S5
There are 2 immiscibility areas in the system Tl-S-I. Monovariant eutectic and peritectic equilibrium curves are transformed into nonvariant monotectic equilibria while
intersecting this immiscibility regions (Fig.3 -MiMi7, M2M, MaMa7, M4M/, M5M57 conjugate pairs).
2.2. Phase equilibria in the Tl - Se - Cl (Br,I ) systems
Tl - Se - Cl system. A ternary compound Tl5Se2Cl melting by sintectic reaction at 725K is formed in the first version of the ThSe-TlCl phase diagram [71] (Fig.4a). This compound is in eutectic equilibrium with T1C1, and in peritectic equilibrim with ThSe. The homogeneity area of ThSe at the peritectic reaction temperature is ~20 mol%. The T-x diagram of this system constructed by [72]
(Fig. 4,b) is consistent at 0-66.7 mol% ThSe composition intervale with results of [71]. However, results obtained by [72,73] at the ThSe2Cl-ThSe composition range differs qualitatively from those given in [71] and is characterized by formation of continious solid solutions. Note that this agrees with the fact that the primary constituents of the sub-system TbSe2Cl-ThSe are iso-structural (see section 3).
T, K
700
650
/ L1+L2 \ 1 \ 1 1 1 1
/ 1 / i 1 \
11 \
... \
T, K
720
TlCl
20
40 60 mol % Tl2Se
80
Tl2Se
20 40 60
mol % Tl2Se
Tl2Se
a) b)
Fig. 4. Phase diagram of the system ThSe-TlCl: a) -[72], b) - [73]
TlSe-TlCl section is also quasi-binary and forms a phase diagram having monotectic and eutectic equilibria [60]. The Tl-S-Cl ternary system was studied in detail at the Tl-TlCl-Se concentartion interval, and some izopleth sections, izothermal section at 400K , as well as the projection of the liquidus surface of its were constructed [72-76].
T1 - Se - Br system. TlBr-ThSe system forms a congruently melting ternary compound TbSe2Br [71] (Fig.5a). It is stoichiometric to be in eutectic equilibrium with TlBr (~10 mol%ThSe, 705k), and in peritectic equilibrium with ThSe (~90 mol %Tl2Se, 720K). There is a wide solid solution
area (75-100 mol% ThSe, 720K) based on ThSe [71]. New phase diagram [73,77] of the system TlBr-Tl2Se coincides with the results of [71] at the TlBr-TbSe2Br composition interval, whereas it differs considerably from it at the Tl5Se2Br-Tl2Se interval (Fig.5b). According to [71], Tl5Se2Br forms a large (66.7-75 mole% ThSe) solid solution area.The results of Ref. [71] agree with the results of Ref. [78-80] that ThSe2Br is of variable composition.
Experimental results in the Tl-TlBr-Se concentration range were summarized, some polythermal and isotermal sections, liquidus surface projection constructed in Ref. [77].
T, k
TlBr
40 60 mol.% Tl2Se
Tl2Se
T, k L D --*---- (745)
740 / r
733 ■ 720 y L+S(Tl5Se2Br) 705 vl+s\ \717\p f 1 \ \
700 1 e3 L+TlBr I 1 \L+a \ II N. V 11 \ \
680 8 1 1 \ \ 1 1 X
660 TlBr+S(Tl5Se2Br) 1 i a+8 V \< ^ a .11. .
TlBr
20
40 60
mol % Tl2Se
80 Tl2Se
a) b)
Fig.5. Phase diagram of the system ThSe-TlBr: a) - [72], b) - [78]
Tl - Se -I system. The phase equilibria in the Tl-Se-I ternary system was investigated in a whole concentartion range [60, 65, 71, 81-86]. Both ternary compounds -Tl5Se2l and Tl6Sel4 detected in the Tl-Se-I system are formed on the TlI-Tl2Se section [60, 71, 83-84]. Tl5Se2I melts congruently at 720K, Tl6SeI4 melts by peritectic decomposition at 705K [71]. TbSe2l has a wide hogeneity region and is in peritectic equilibrium with ThSe. However, according to the results of [60], both compounds are non-stoichiometric phases which melt congruently.
A re-study of the TlI-ThSe system [83,84] confirmed the existence of congruently melting ternary compounds TbSe2l (720K) and Tl6SeI4 (705K).
TlSe-TlI [60], TlSe-Tl5Se2I and TlSe-Tl6SeI4 [84,85] polythermal sections of the system Tl-Se-I are quasi-binary and
form eutectic phase diagram. TlI-Se [86], Tl5Se2I-Tl [84] va Tl6SeI4-Tl [84] polythermal sections are also quasi-binary and characterized by monontectic and degenerated eutectic equilibriums.
The projection of the liquidus surface of the system Tl-Se-I is given by the Ref. [65,84].
It consists of 10 primary crystallization areas (Fig.6). Liquidus surfaces of the elemenetal Tl and Se are degenerated on the relevant vertices of a concentration triangle. The largest area of crystallization belongs to the high temperature modification of thallium monoiodide - (TlI)II. This compound involves most non- and monovariant equilibriums in the Tl-Se-I system.
Tl-Se-I system is divided into 8 subsystems by 7 quasi-binary sections (Fig.6, dashed lines). 3 of those sub-systems (Tl-TlI-Tl6SeI4, Tl-Tl6SeI4-Tl5Se2I, TlI-TlSe-Se) are characterized by nonvariant monotectic and eutectic equilibria, two of them (TlI-Tl6Sel4-TlSe, Tl6SeI4-Tl5Se2I-TlSe) are of eutectic type, one - Tl2Se-Tl5Se2I-TlSe is of transition type, and one - Tl-Tl2Se-Tl5Se2I is of monotectic and transition types. The latter system - TlI-Se-I covers half of the concentration triangle and reflects a series of non- and monovariant equilibria. The hogeneity areas and dissociation in the liquid state of the Tl5Se2Hal and Tl6S(Se)I4 compounds are comprehensively studied [61,67,68,78-80].
Fig.6. The projection of the liquidus surface of the system Tl-Se-I. Primary crystallization areas: 1-I2, 2.-TII3, 3-ThI3, 4-(T1I)ii, 5-TlSe, 6 -TkSeI4, 7-Tl5Se2I (5-phase), 8-T^Se (a-phase), 9-Tl, 10-Se.
2.3. Phase equilibria in the Tl - Te - Cl (Br,I ) systems
Tl - Te - Cl system. Phase equilibria in Tl(TlTe,ThTe3,TbTe3) polythermal sections this system were studied by [73,76,87-89]. The further study of phase
TlCl-Te(TlTe,Tl2Te3), TbTe2Cl- equilibria in the Tl-TlCl-Te composition area
was carried out by [90-92], a number of polythermal sections, the projection of a liquidus surface of the system constructed, types and coordinates of non- and monovariant equilibriums determined.
TlCl-Tl2Te quasi-binary section is characterized by formation of ternary TbTe2Cl that melts incongruently by syntectic reaction at 708 K [90,92]. The aliquation area at this temperature ranges between ~7-85 mol% ThTe concentration region. TlsTe2Cl is r. K
L./ t \ L =
70S
703, /" * ' *
700 ij \L:-S\
i ®2 j
690 * * ' * !
5 \
T1C1+T1; Te^Cl ! 01
630
in eutectic equilibrium with TlCl, whereas it is a solid solution area with ThTe (Fig. 7,a).
The main feature of the system Tl-TlCl-Te is the existence of a wide immisciblity areas on the basis of 3 different liquid phases. These aliquaition fields cover more than 90% of the Tl-TlCl-Te concetration triangle. There is a wide triple immiscibility region which is surrounded by corresponding double immiscbility areas [92].
T.K
750
ft 93
690
L: ' , ^ \ \ L: I
/ " *
f Ll+5
\ Lftfl \
HBr-T№:Br<5) VTOO] O 1 uc 1 1 Ö 1 1 . 1
P.
6%
TlCl
20 40 60 30 Tl-Te
mal % II-Te
TlBr
20 -0 SO SO mol % TUT e
TVTe
a)
b)
Fig. 7. Phase diagram of the systems TlCl-Tl2Te (a) [94] and TlBr-ThTe (b) [97]
T1 - Te - Br system. This system was studied in the Tl-TlBr-Te composition area [87, 89, 91, 93-95]. It revealed that the only quasi-binary section of this system - TlBr-ThTe forms a phase diagram with syntectic, eutectic and peritectic equilibriums. Tl5Te2Br melts by syntectic reaction at 750K. Its homogeneity area occupies 66.7-87 mol% ThTe concentration interval [91,95] (Fig. 7,b).
TlBr-Te system is quasi-binary, whereas TlBr-TlTe(ThTe3), ThTe2Br-TlTe, ThTe2Br-ThTe3 isopleth sections are stable in subsolidus. The latter forms a continuous series of solid solutions.
The projection of the liquidus surface consists of 5 fields which agrees with the primary crystallization of the TlBr, S-phase, TlTe, ThTe3 and elemental Te [95]. Formation of the triple immiscibility area in the system is due to the presence of extensive double immiscibility areas on all sides of the Tl-TlBr-ThTe subsystem. The triple immiscibility area is chracterized by the nonvariant syntectic L1+L2+L3 ^ S reaction.
In Ref. [96-102] ternary compounds ThTeBr(I)6 were detected, their homogeneity areas defined and some properties of their moncrystals examined.
T1 - Te - I system was investigated in a whole concentration interval.
TlI-Tl2Te quasi-binary section forms a ternary ThTe2I compound meltig at 775K by syntectic reaction [60]. ThTe2I is a phase of variable composition and has a ~10 mol % homogeneity region along the TlI-Tl2Te system (Fig.8).
Tl2TeI6 compound melting congruently at 700K was detected on the TlI-TeI4 quasi-binary section, its crystal structure and some physical properties were studied [97-102]. New option of the TlI-TeI4 phase diagram [108] differs from the one described in Ref. [100] by melting temperature of ThTek -654K.
T-x-y digram of the Tl-Te-I system is given in [105-110]. It found that TlI-Te, TlI-Tl2Te, TlI-TeI4, Tl2TeI6-Te and Tl2TeI6-I polythermal sections are quasi-binary. The
phase diagram of the TlI-ThTe system has been specified by [98]. The results obtained are close to [60].
The solid-phase diagram of the Tl-Te-I system at 300K reflects 2 ternary compounds
T.K. 800
Til 20 40 60 80 TKTe mol.% T12Te
Projection of the liquidus surface consists of 11 primary crystallization areas (Fig.9) [108]. Liquidus surfaces of the elemental Tl and a-phase based on ThTe are degenerated.
To sum up, let's look at characteristic features of phase equilibria in the Tl-X-Hal systems.
6 ternary compounds of the type TbX2Hal (in all Se and Te containing), 4 compounds of the type Tl6XHal4 (in all S containing systems) and ThTeHal6 compounds have been detected in the Tl-X-Hal systems. It revealed that all compounds, except for the
(TbTe2l; Tl2Tel6) and their equilibria with other phases. There is a wide homogeneity area based on TbTe2l, however ThTeL has almost a stoichiometric composition.
Fig. 8. Phase diagram of the system TlI-ThTe
698
latter ones, are formed on the TlHal-Tl2X quasi-binary sections. TbX2Hal compounds decompose incongruently by syntectic reaction except for the TbSe2l and TbSe2Br that melt congruently. Tl6XHal4 compounds melt congruently (Tl6Sl4 and Tl6Sel4) or by peritectic decomposition.
TbX2Hal compounds are phases of variable composition possessing a wide homogeneity area, whereas Tl6XHal4 and Tl2TeHal6 compounds are practically stoichiometric. Crystal structures of all three types of compounds are discussed in the next section.
m, |5.c,r».40 p, M' p.
■«it ® '
Fig.9. Liquidus surface projection of the system Tl-Te-I. Primary crystallization fields: 1- 5 phase, 2- (TlI)n, 3-T№, 4-Tll3, 5-TlsTe2l, 6-Tel4, 7-TeI, 8-Te, 9-Tl2Te3, 10- TlTe, 11- I2
The characteristic feature of the Tl-X-Hal systems is the existence of wide immiscibility areas in a liquid state. There are
triple immiscibility areas together with double ones in the 6 systems out of the 9 Tl-X-Hal systems. The comparative analysis of the
liquidus surfaces shows that the character phase of equilibria changes regularly in three directions of S^Se^Te and Cl^Br^I, which is due to changes in the nature of chemical bonding in these systems.
Criteria of aliquation was revealed in the T1-X-Hal ternary systems as a result of the comparative analysis of T-x diagrams of more than 50 quasi-binary and quasi-stable sections [109, 110]. It showed that there is an immiscibility area in the systems when the
degree of ionisation (DOI) is more that 17, and the systems with DOI <16-17 don't demostrate aliquation.
To summarize, there is a rare case of practice in the TbX2Hal-ThX and TbTe2Hal-Tl5Te3 sections of the Tl-X-Hal systems. Despite the presence of extensive immiscibility areas in liquid state, these systems are characterized by formation a wide or continuous solid solution areas in subsolidus.
3. Crystal structure and some physico-chemical properties of thallium chalcohalides
The literature data on the crystal structure and some physico-chemical properties of tallium chalco-halides are discussed in this section. As mentioned above (section 2), there are 3 types of ternary compounds in Tl-X-Hal systems: TbX2Hal, TbXHaU and ThTeHab. Crystal lattice types and parameters of those compounds are listed in the Table 1.
TbX2Hal compounds are crystallized in a tetragonal lattice of the TbTe3 type. The crystal structure of Tl5Te3 has been analyzed in a number of studies [111-114] following which this compound is crystallized in a tetragonal structure of the Cr5B3 type (Sp.gr. \4/mcm). In the unit cell there are 4 formula units (z = 4).
The main structural elements of the TbTe3 crystal lattice (Fig. 10) are tellurium octahedra in which tellurium atoms have two different positions: part (Te1) is located at two opposite vertices of octahedra along the c axis, and the other part (Te2) occupies the remaining positions.
Thallium atoms are also subdivided into 2 types according to their positions in the crystal lattice: one part of the cations - Tl (1) is located in equivalent positions with a multiplicity of 16, and another part - Tl (2) - in positions with a multiplicity of 4. Chemical composition of the unit cell is Th6TUTe8Te4. Considering the electroneutrality condition, it can be assumed that in positions with a multiplicity of 4, the Tl+ and Tl3+ cations alternate and the unit cell can be represented as
Tl1J(Tl0+5B3°+5)Te3]4 . Linking to the vertices, the octahedra form a skeleton of the com-
position TUTei2 or (TlTe3)4 (Fig. 10, a). Thallium prisms are formed around the octahedra, and antiprisms of thallium are formed around the anions at the vertices of the octahedra, which bind the octahedra along the c axis. Prisms and anti-prisms are alternated along the c axis. These structural elements create a structure of the TbTe3 type with the chemical composition of the cell Tl16(TlTe3)4 (Fig. 10, b).
Due to the above mentioned features of the crystal lattice, TbTe3 forms a series of cation- and anion-substituted derivatives. Typical representatives of cation-substituted ternary analogues of TbTe3 are compounds of the types Tl9BTe6 (B-Sb, Bi, In, Au, rare earth elements) [115-119] and Tl4ATe3 (A-Sn, Pb, Cu, Mo, Nd) [115,118, 120-122].
TUATe3 and Tl16[A2+Te3]4 compounds are formed when all the thallium atoms in the centers of the octahedra (Tl2) are replaced by the A2+ cations. Replacement of half of the Tl atoms located in the vacancies of octahedra (Tl2), with B3 + cations leads to the formation of Tl9BTe6 compounds [117].
The crystal structures of Tl5X2Hal compounds - anion-substituted derivatives of Tl5Te3 were studied in detail. According to the available data (Table 1), all these compounds, with an exception of TbSe2Cl (Sp.gr P4 / ncc), belong to the spatial group I4 / mcm. Se or Te atoms located at two opposite vertices of the octahedra are replaced by halogen atoms in the crystal lattices of these compounds.
The interesting aspect of the anion replacement is that it enables formation of solid solutions at the composition interval Tl5Te3-xHalx (0<x<1). Meantime, Tl gradually
changes its oxidation state by switching to Tl+ their structural analogues are phases of
and provides electroneutrality. The analysis of variable composition with a wide one-sided
the TbTe3 type structures show that both homogeneity areas. TbTe3 and TbSe3-x compounds, as well as
Fig.10. Crystal structure of TbTe3. The main structural element (a), the projection along
the surfaces b, c (b)
Table 1. Crystal lattice parameters of TbTe3 and tallium chalcohalides
Compound Syngony, Space Group Lattice parameters, A Reference
Tl5Te3 Tetragonal, I4/mcm a=8.930; c=12.598; z=4 [114]
Tl6Sl4 Tetragonal, P4/mnc a=9,176; c=9,608; z=2 [61,82]
Tl6SBr4 cc cc a=8,721; c=9,328; z=2 [61,82]
Tl6SCl4 "-" a=8,830; c=9,170; z=2 [61,82]
Tl6Sel4 a=9,178; c=9,675; z=2 [81,82]
Tl5Se2l Tetragonal, I4/mcm a=8,663; c=13,463; z=4 [71]
Tl5Se2Br a=8,594; c=12,788; z=4 [123]
Tl5Se2Cl Tetragonal, P4/ncc a=8,565; c=12,741; z=4 [123]
Tl2Tel6 Monoclinic, P2i/c a=7,765; b=8,174; c=13,756; 0=124,2°; z=2 [102]
Tl2TeBr6 Tetragonal, P4/mnc a=7,468; c=1°,682; z=2 [102]
Tl2TeCl6 Cubic, Fm-3m a=1°,1°7; z=4 [124]
Tl5Te2l Tetragonal, I4/mcm a=9.°°1; c= 13.291; z=4 [108]
Tl5Te2Br Tetragonal, I4/mcm a =8.974; c= 12.812; z = 4 [125]
Tl5Te2Cl Tetragonal, I4/mcm a =8.921; c= 12.692; z = 4 [90,92]
Crystal structure of TbSe2Hal tallized with the In5Bi3 structure which is a
compounds was studied, their lattice subfamily of the &5B3 type: TbSe2l(Br) is parameters, and positions of atoms in the unit crystallized in the space group 14/mcm ,
cell determined [71,123]. All of them are crys TbSe2Cl as a lower symmetric distorted vari-
ant in P4/ncc. Around one central thallium atom there are slightly distorted octahedra of two halogen and four selenium atoms occur. These octahedra are covered by cubes of thallium atoms. The octahedra are interconnected via common vertices and the cubes via common edges to give the three-dimensional structure [123].
The crystal structure study of TbTe2Cl(Br) compounds was carried out by the Rietveld method based on powder X-rays analysis. The unit cell parameters and isotropic atomic positions of the atoms were refined by TOPAS-4.2 program [90,125].
Based on the phase diagram of the Tl-Te-I system, it was proposed and implemented
an original method of growing single crystals of Tl5Te2I which melts incongruently by syntectic reaction [65,126]. The method has been used in order to control the crystallization process from two immiscible liquid phases L1 + L2. In this method the liquid phase L1 was in dynamic equilibrium with another liquid phase and the compositions of the coexisting liquid phases always constant at the given temperature. During very slow crystallization from the L1, the phase L2 gradually dissolves in L1, and provides constancy of its composition to form consequently the Tl5Te2I by the syntectic reaction at 775 K according to phase diagram.
a)
b)
Fig.11. Crystal structure of TbTe2I : a) view along the [010] direction; b) Projection along the c-axis. Tl1 atoms in lighter color.
Fig. 12. Perspective view of TlsTe2I showing a layer of Tl5Te2I corner-sharing octahedral. Color codes like in Fig. 11 and Tl1 atoms in lighter color
Single crystal X-ray diffraction data was collected at room temperature on a STOE Sta-diVari diffractometer. The structure was refined using as starting model that of TbTe3; refinement performed with the program system JANA2006. All atoms were refined with occupancies according to the stoichiometric formula, anisotropic thermal displacement parameters and without any constrain. Images of chemical structure were visualized using VESTA software. Full crystal structure details, data collection and structure refinement details are given in [108]. The structure can be described as layers of corner sharing TlTe4l2 octahedral (Tl2 central atom) with additional interstitial Tl1 atoms with trigonal prism coordination. Octahedra consecutive along the c-axis are rotated 45 relative to each other. A projec-
The synthesys, identification of the homogeneity areas, growth of monocrystals and study of some properties of the ThTeHal6 (Hal - I,Br) compounds are reported in [96102,128-130]. The crystal structure of ThTeBr6(l6) compounds was studied in Ref. [98,102] (Fig. 14). Both compounds are crys-
tion along the [010] and [001] directions, and perspective view of the structure are shown in the Fig. 11 and 12 [127] reported formation mechanism of the anion- and cation substituted anologs of Tl5Te3 takes into consideration structural properties of this compound and the electronic structure of thallium. The rational content of these analogues TI4BX3, TI9BX6 and TbX2Hal was justified, and the reasons for their one-sided stoichiometry determined.
Tl6SHal4 and Tl6Sel4 (Hal- I,Br,Cl) ternary compounds are crystallized in a tetragonal lattice of the type Tl4HgBr6 [61,81,82] (Fig. 13). There are two distinct crystallographic sites for Tl cations. Each Tl+ ion is coordinated with four Hal- ions and one (S2-)Se2- ion.
Fig. 13. The crystal structure of Tl6Sel4. Two distinct sites for Tl ions are shown as Tl1 and Tl2, respectively [50].
Fig.14. The unit cell of ThTeBr(I)6 compounds. Tl cations are shown by a large gray circles, Te atoms - by dark blue circles and the halogen atoms -by small circles.
tallized in a crystal lattice of the K2PtCl6 type. Tl2TeCl6 ternary compound crystallize in a cubic unit cell [124] (Table 1).
The methods for the synthesis and monocrystal growth, and some physico-chemical properties of the Tl6XHal4 and
TbSe2Hal chalcohalides were analyzed in Ref. [66,67,78,131,132].
The 3D homogeneity areas were defined and some electrophysical properties of Tl6Sl4
and Tl6Sel4 monocrystals examined in [131,132].
4. Thermodynamic propertis of thallium chalcohalides and related phases
The fundamental thermodynamic characteristics of substances are important to ensure the effectiveness of thermodynamic calculations for optimization of various processes, in particular, conditions for the synthesis and growth of crystals [133, 134].
Thermodynamic propertis of intermediate phases in the Tl-X-Hal systems were excamined through the EMF measurements of the concentration chains
(-) Tl (solid) | gluserol + KlCl + TlCl | (Tl-X-Hal) (solid) (+) (1)
In the chains of type (1), metallic thallium was used as the left electrode, while equilibrium alloys of the Tl-X-Hal systems were used as the right electrodes. A saturated glycerin solution of KCl with the addition of 0.1 mass% TlCl was used as an electrolyte. EMF was measured by the compensation method in the temperature range of 300-430 K and in the 300-380K temperature intervals for sulphur containing systems.
Table 2. Thermodynamic properties of thallium chalcohalides
Compound -A fG 0(298K ) -A f H 0(298K ) S0(298K ), (J- mol-1- K-1) Reference
(kJmol-1)
TI6SI4 601.7±2.5 595.1±4.0 672±10 [69]
Tl6SBr4 767.0±2.9 790.3±5.2 644±9 [65]
Tl6SCl4 833.5±3.7 928.1±14.0 599±9 [64,65]
Tl6Sel4 613.1±1.5 609.7±2.6 671 ±5 [84]
Tl5Se2l 341.7±0.8 345.3±2.5 449±8 [84]
Tl5Se2Br 374.3±1.0 384.3±2.7 447.6±6.4 [77]
Tl5Se2Cl 392.8±1.1 421.6±5.1 433.9±7.2 [72]
Tl5Te2l 300.4±1.3 301.1±2.3 475.8±6.6 [104]
Tl5Te2Br 340.6±1.6 344.5±2.7 483.4±6.2 [95]
Tl5Te2Cl 355.9±1.1 377.1±5.0 474.1±6.8 [92]
The homogeneity areas of phases were refined, the relative partial molar functions of thallium in alloys and the integral thermody-namic functions of thallium chalcohalides and solid solutions based on them calculated on the basis of the results of EMF measurements of the chains type (1). The standard thermody-namic functions of formation and the standard entropies of ternary thallic chalco-halides are summarized in the Table 2.
The results of EMF measurements devoted to the determination of homogeneity areas of the TbX2Hal compounds and calculation of thermodynamic functions of solid solutions are presented and discussed in [84,104,135-138]. As an example, Fig. 15 presents the data of [138] on the refinement of the homogeneity region of the TbSe2Br compound.
TIBr
Fig.15. Application of the EMF method for the determination of homogeneity area of TbSe2Br compound [138]. a) the concentration dependence of the EMF of chains type (1) for alloys along the ray lines from the vertex TlSe b) a fragment of the phase diagram of the Tl-Se-Br system at 300 K.
The relative parsial thermodynamic functions of tallium in the TbTe2BrxIi-x solid solutions at 298K were calculated and their dependence graph upon concentration constructed. It has been established that formation of solid solutions in the TbTe2Br-TbTe2l system is not accompanied by significant energy and structural changes, and the formed 5-phase is a solid solution of substraction type [139].
The standard thermodynamic functions of formation and atomization, as well as standard entropies of tallium chalcocahalides and variable phases on their base were
calculated on the basis of partial thermodynamic functions of thallium using phase diagrams [140].
By using EMF measurements a regulated complex of thermodynamic properties for the Tl6SBr4 compound was obtained. The data regarding the thermodynamic properties of all thallium chalco-halides were systematized and comparatively analyzed. Some correlations between thermodynamic functions of thallium chalco-halides and their binary constituents, as well as the ionization degree of chemical bonding were revealed [141,142].
5. Phase equilibria and physico-chemical properties of intermediate phases in some multi-component systems containing thallium, chalcogen and halogen
Some concentration areas of the Tl- X-X-Hal and Tl-X-Hal-Hal7 (X,X7- chalcogen; Hal,Hal- halogen) four-component systems are of a significant interest in terms of search and development of scientific basis for designing new multicomponent phases based on thallium chalcohalides. Another way for varying the properties of ternary compounds is
to investigate the phase equilibrium in systems composed of them and their structural analogues. In this regard, TbTe2Hal-Tl9BVX6 and Tl5Te3-TbTe2Hal-Tl9BvX6 systems are very interesting, since all initial constituents of these systems are isostructural thermoelectrics possessing a low thermal conductivity [29].
5.1. Tl-X-X'-Hal (X, X'-chalcogen, Hal-halogen) systems.
The phase equilibria in the systems Tl2S-ThSe-Tll(Br) were studied, some polythermal sections and the liquidus surface projections of these systems constructed [143,144]. It was shown that, the Tl6Sl4-Tl6Sel4 [145,146] and ThS-TbSe2I [147] quasi-binary sections divide the ThS-ThSe-Tll system into 3 sub-systems. The ThS-ThSe-Tl5Se2l subsystem is of monotectic eutectic type [143] due to the formation of continuous solid solutions along the Tl6Sl4-Tl6Sel4 section [145].
3 monocrystals of the Tl6Sl4-Tl6Sel4 solid solutions were grown by direct crystallization and their some physico-chemical properties studied [148].
The physicochemical interaction of components in the TlI-Tl6SI4-Tl6SeI4 system was studied by means of DTA and X-ray analysis, the projection of the liquidus surface and the TlI-Tl6S0,5Se0,5l4 polythermal section of the system were constructed [149]. The monovariant eutectic L^a+p/ equilibrium curve of the TlI-Tl6S0,5Se0,5I4 system is calculated based on mathematical modeling.
Three vertical cross sections (Tl2S-Tl2Se,Tl2S-Tl5Se2Br, Tl6SBr4-Tl5Se2Br) and the liquidus surface projection of the ThS-Tl5Se2Br-TlBr system were constructed, the boundaries of phase areas, as well as the coordinates of nonvariant equilibriums determined [150].
5.2. Tl-X-Hal-Hal' systems
The research results of the systems composed of selenides and halides of tallum are reported in [151-153]. It revealed that the TlSe-TlCl-TlI system belongs to the nonvari-ant eutectic type [151], whereas TlSe-TlBr-TlI [152] and TlSe-TlCl-TlBr [153] are of the monovariant eutectic type.
Tl5Se2Br-Tl5Se2I and TbTe2Br-TbTe2I systems are characterized by formation of continuous solid solutions [154,155].
The interaction between A2TeC6 (A-K,Rb,Cs,Tl; C-Br,I) compounds was studied and their T-x diagrams constructed [99,154]. These systems are quasi binary and form a phase diagram of eutectic type containing a large solid solution areas on the base of primary constituents.
The effect of the crystallochemical factor on the interaction of the components in these systems was determined by the ratio of the type of A2TeC6 compounds and the extent of the interaction of these cations and their anions in determining the nature of the interaction in these systems.
By the influence of the crystallochemical factor on the interaction of components in these systems it was determined that the main parameter defining the structur type of A2TeC6 compounds and the character of chemical
interaction in these systems is the size ratio of cations and anions.
The phase equilibria in the T2Te-TlBr-TlI, Tl2Te-TlCl-TlI, Tl2Te-TlCl-TlBr systems were studied by means of DTA and X-ray analysis, as well as by measurement of microhardness and EMF of the concentration chains relative to the thallium electrode [141,157,158]. Some polythermal sections, an isothermal section at 300K, as well as the projection of the liquidus surface of all three systems were constructed. The primary crystallization areas, types and coordinates of non- and monovariant equilibriums determined.
Tl5Te2Hal-Tl5Te2Hal/ systems are nonquasi-binary due to the incongruent melting character of ternary compounds and consists of aliquation fields. However, isostructural Tl5Te2Hal (Hal - Cl, Br, I) compounds form continuous solid solutions in solid state. Thus, a very interesting and rare phenomenon is observed in these systems -despite the fact that, there is a complete aliquation in liquid state, the initial constituents of these systems are completely dissolved in each other in solid state. Realization of a such an unusual phenomenon in the Tl5Te2Hal-Tl5Te2Hal/ systems is related to the fact that the aliquation in these systems
does not reflect the character of interaction between the ternary compounds, but rather the melting character of these compounds and solid solutions based on them [159]. Also the composition of the layered liquid phases is outside of the T-x plane of these systems.
In all ThTe-TlHal-TlHal7 systems, the homogeneity areas of the solid solutions based
on the Tl5Te2Hal compounds fall outside the Tl5Te2Hal-Tl5Te2Hal/ sections and occupy a wide area in the ThTe-Tl5Te2Hal-TbTe2Hal/ subsystems. This is due to the existence of a large one-sided homogeneity area on the basis of Tl5Te2Hal compounds in the ThTe-TlHal systems.
6. Phase equilibria in some systems consisting of compounds of the TlsTe3 type crystal structure
Tl5Te3-Tl9BiTe6-Tl5Te2Hal systems are of great interest in terms of preparation of thermoelectric materials with very low heat conductivity. The point is that one of the components - T№iTe6 compound has a record high thermoelectric efficiency [29]. By incorporating halogen atoms in the crystal lattice of this compound, it is possible to further complicate them and reduce the thermal conductivity.
Phase equilibriums in the TbTe3-Tl9BiTe6-Tl5Te2Hal systems were investigated by physico-chemical analysis methods, the isothermal sections at 760 and 800K and the projections of the liquidus surfaces of these systems were consrtucted [160-163].
Tl5Te3-Tl9BiTe6 and TbTe3-TbTe2Hal boundary systems of the TbTe3-T№iTe6-Tl5Te2Hal concentration trangles were studied in [83,89,164]. It showed that these systems are characterized by unlimited dissolution of components one into another. Tl9BiTe6-Tl5Te2Hal systems form a continuous solid solutions (S-phase) and are quasi-binary due to the incongruent melting of tellurohalides
[163]. The composition of liquid phases go beyond the T-x diagram of these systems. Powder diffractograms of all aloys have a Tl5Te3 type tetragonal structure while the dependence of lattice parameters on the composition is almost linear.
The liquidus surfaces of the TbTe3-Tl9BiTe6-Tl5Te2Hal systems are composed of two parts matching to the primary crystallization of S-phase from the homogeneous alloy and L+L1 immiscibility area. The ab curve connecting these two regions is characterized by the L+L1 ^6 monovariant syntectic equilibrium. The solidus of the system consists of a surface to comply with the end of crystallization (dashed line) [160-162]. The liquidus projection of all three systems is qualitatively similar and differs only by the size of the L+L1 immiscibility area. The results on the phase equilibrium can be used to select the composition of the sample and temperature regimes when growing S-solid solution crystals of given composition [159].
Conclusion
In the review paper, the literature data and results of the work of the authors on physico-chemical research into some ternary and more complex systems which are considered important in terms of creation of physico-chemical bases for directional synthesis of tallium chalcohalides and related multicomponent non-stoichiometric phases. It revealed that as a result of the studies in these systems, a wide range of ternary compounds and multicomponent solid solutions of great
interest as promising functional materials with thermoelectric, optical, magnetic, sensor and detector properties were identified. These data open up great opportunities for optimizing the functional properties of phases by directional variation of their composition. Besides, the fundamental thermodynamic properties of thallium chalcohalides and many phases of variable composition which are valuable as scientific data and important for optimizing conditions of their design were determined.
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D.M. Babanli, D.B. Tagiyev
AMEA akad.M.Nagiyev adina Kataliz v3 Qeyri-Üzvi Kimya institutu AZ1143, Baki §зк., H.Cavidpr., 113; e-mail: dunyababanly2012@gmail.com
icmal maqalada talliumun xalkohalogenidhrinin уз onlar asasinda yeni goxkomponentli fazalarin alinmasi baximindan maraq kasb edan bazi üglü уз daha mürskksb sistembrin fiziki-kimyavi tadqiqinin naticabri sistemb§dirilmi§ v3 bhlil edilmi§dir. Qeyri-üzvi maddabrin bu sinfi termoelektrik, optik, maqnit, sensor уз detektor xassahrina malik olan perspektivli funksional materiallar kimi elmi уз praktiki maraq kasb edir. Burada hamginin, tallium xalkohalogenidhrinin уз onlar 3sasinda dayi§3n brkibli araliq fazalarin kristal qurulu§ xüsusiyy3tl3ri, termodinamik уз bazi fiziki-kimyavi xassahrina aid adabiyyat malumatlari ara§dirilmi§dir.
Agar sözlar: tallium xalkohalogenidbri, funksional materiallar, faza diaqrami, bark mahlullar, termodinamik xassabr, kristal qurulu§.
ФИЗИКО-ХИМИЧЕСКИЕ АСПЕКТЫ РАЗРАБОТКИ ТРОЙНЫХ И СЛОЖНЫХ ФАЗ НА ОСНОВЕ ХАЛЬКОГАЛОГЕНИДОВ ТАЛЛИЯ
Д.Б.Бабанлы, Д.Б. Тагиев
Институт Катализа и Неорганической химии им. акад. M.Ha¿:ueea Национальной АН Азербайджана Пр. Г. Джавида, 113, Баку, AZ1143; e-mail: dunyababanly2012@gmail.com
В обзоре систематизированы и проанализированы результаты физико-химических исследований тройных и более сложных систем, представляющих интерес с точки зрения получения халъкогалогенидов таллия и новых многокомпонентных фаз на их основе. Этот класс неорганических веществ представляет научный и практический интерес как перспективные функциональные материалы с термоэлектрическими, оптическими, магнитными, сенсорными и детекторными свойствами. Также проанализированы литературные данные о кристаллической структуре, термодинамических и некоторых физико-химических свойствах халькогалогенидов таллия и фаз на их основе.
Ключевые слова: халькогалогениды таллия, функциональные материалы, фазовая диаграмма, твердые растворы, термодинамические свойства, кристаллическая структура.
