Phase relations in the CuI-SbSI-SbI3 composition range of the Cu–Sb–S–I quaternary system Текст научной статьи по специальности «Химические науки»

ISSN 1606-867Х (Print) ISSN 2687-0711 (Online)

Condensed Matter and Interphases

Kondensirovannye Sredy i Mezhfaznye Granitsy https://journals.vsu.ru/kcmf/

Original articles

Research article

https://doi.org/10.17308/kcmf.2021.23/3435

Phase relations in the CuI-SbSI-SbI3 composition range of the Cu-Sb-S-I quaternary system

P. R. MammadK12®, V. A. Gasymov2, G. B. Dashdiyeva3, D. M. Babanly12

1 Azerbaijan State Oil and Industry University, French - Azerbaijani University, 183 Nizami str., Baku AZ-1010, Azerbaijan

2Institute of Catalysis and Inorganic Chemistry of the Azerbaijan National Academy of Sciences, 113 H. Javid ave., Baku AZ-1143, Azerbaijan

3Baku Engineering University,

120 Hasan Aliyev str., Baku AZ-0102, Azerbaijan

Abstract

The phase equilibria in the Cu-Sb-S-I quaternary system were studied by differential thermal analysis and X-ray phase analysis methods in the CuI-SbSI-SbI3 concentration intervals. The boundary quasi-binary section Cul-SbSI, 2 internal polythermal sections of the phase diagram, as well as, the projection of the liquidus surface were constructed. Primary crystallisation areas of phases, types, and coordinates of non- and monovariant equilibria were determined. Limited areas of solid solutions based on the SbSI (р-phase) and high-temperature modifications of the Cul (a1- and a2- phases) were revealed in the system. The formation of the a1 and a2 phases is accompanied by a decrease in the temperatures of the polymorphic transitions of Cul and the establishment of metatectic (3750C) and eutectoid (2800C) reactions. It was also shown, that the system is characterised by the presence of a wide immiscibility region that covers a significant part of the liquidus surface of the Cul and SbSI based phases.

Keywords: Copper (I) iodide, Antimony iodide, Antimony sulfoiodide, Cu-Sb-S-I system, Phase diagram, Solid solutions

Acknowledgements: the work has been partially supported by the Science Development Foundation under the President of the Republic of Azerbaijan, a grant № EIF-BGM-4-RFTF-1/2017-21/11/4-M-12.

For citation: Mammadli P. R., Gasymov V. A., Dashdiyeva G. B., Babanly D. M. Phase relations in the CuI-SbSI-SbI3 composition range of the Cu-Sb-S-I quaternary system. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2021;23(2): 236-244. https://doi.org/10.17308/kcmf.2021.23/3435

Для цитирования: Маммадли П. Р., Гасымов В. А., Дашдиева Д. Б., Бабанлы Д. М. Фазовые равновесия в области составов CuI-SbSI-SbI3 системы Cu-Sb-S-I. Конденсированные среды и межфазные границы. 2021;23(2): 236-244. https://doi.org/10.17308Acmf.2021.23/3435

И Parvin Rovshan Mammadli, e-mail: parvin.mammadli@ufaz.az

© Mammadli P. R., Gasymov V. A., Dashdiyeva G. B., Babanly D. M., 2021

[^S^^^J The content is available under Creative Commons Attribution 4.0 License.

P. R. MammadLi et al. Original article

1. Introduction

Copper-antimony chalcogenides and phases based on them are considered to be potential candidates for the preparation of environmentally friendly, low-cost functional materials possessing novel desired characteristics [1-3]. The majority of ternary Cu-Sb-sulphides are naturally occurring minerals that have been widely explored as valuable electronic materials displaying high photoelectric, photovoltaic, radiation detector, thermoelectric, etc. properties. Earth abundance and environmental compatibility of these substances highlight the recent advances of investigations on these materials [4-7].

As it is known, one of the ways to increase the efficiency of thermoelectric materials is to complicate their composition and crystal structure [8]. In this regard, Cu-Sb chalcohalides could be considered promising research objects in terms of the search and design of new eco-friendly functional materials. However, we could not find literary information about the phase equilibria of the Cu-Sb-S-I quaternary system. There is a literary report about the formation, crystal structure, and conductivity of the Cu5SbS3I2 compound [9]. Cu5SbS3I2 crystallises in the orthorhombic system, space group Pnnm with the following lattice parameters a = 10.488(2), b = 12.619(2), c =7.316(1) A, and Z = 4 [9]. Electric conductivity and dielectric parameters of the Cu-Sb-S-I glasses have been investigated in order to evaluate their practical importance in memory switching, electrical threshold, optical switching devices, and so forth [10].

The search and design of new complex functional materials require investigation of the respective phase diagrams. The information accumulated in phase diagrams of the corresponding systems is always helpful in materials science for the development of advanced materials [11-13].

Considering above mentioned facts, in terms of the search for new multicomponent phases, the concentration plane Cu2S-CuI-SbI3-Sb2S3 of the Cu-Sb-S-I quaternary system is of great interest. The present contribution is dedicated to the study of physicochemical interaction in the CuI-SbSI-SbI3 (A) concentration area of the above-mentioned concentration plane.

Primary compounds of the system (A) possessing interesting functional properties

have been studied in detail. Copper (I) iodide CuI is a non-poisonous, wide-gap semiconductor possessing stable p-type electrical conductivity at room temperature, fast-ionic conductivity at high temperatures, an unusually large temperature dependency, negative spin-orbit splitting, etc [14-16]. It has wide application in light-emitting diodes, solid-state dye-sensitised solar cells, high-performance thermoelectric elements, etc [17, 18]. Antimony triiodide SbI3 has been intensively studied as a dopant in thermoelectric materials, as a potential material for radiation detectors, as cathodes in solid-state batteries, in high-resolution image microrecording, information storage, etc. [1921]. SbSI exhibits important ferroelectricity, piezoelectricity, photoconduction, dielectric polarisation properties and is widely used in the fabrication of nanogenerators and nanosensors [22-25].

CuI melts at 606 °C without decomposition and has 3 modifications [26, 27]. The low-temperature g-modification transforms to the b-phase at 369 °C. The b-CuI phase exists in a small temperature range (~ 10 K) and transforms into a-phase at 407 °C. SbI3 melts at 172 °C [28] and crystallises to rhombohedral lattice [29]. SbSI melts congruently at 300 °C [22,30]. Three phases of SbSI have been reported: ferroelectric (T < 20 °C), antiferroelectric (20 °C < T <140 °C) and paraelectric (T < 140 °C) [31]. Both in the paraelectric and ferroelectric phases, SbSI crystallises in the orthorhombic structure [32, 33].

Crystallographic parameters of the constituent compounds of the system A are represented in Table 1.

CuI-SbI3 and SbSI-SbI3 boundary quasi-binary sections of the quasi-ternary CuI-SbSI-SbI3 system have been investigated by [35-37], respectively. CuI-SbI3 system forms a monotectic phase diagram. At the monotectic equilibrium temperature (~ 220 °C) the immiscibility region ranges within ~15-93 mol% SbI3 concentration interval [35]. SbSI-SbI3 quasi-binary section is characterised by a eutectic equilibrium at 160 °C [12, 30].

2. Experimental part

A CuI binary compound, as well as, antimony and iodine elementary components of the Alfa

P. R. MammadLi et al.

Original article

Table 1. Crystal lattice types and parameters of the CuI, SbI3 and SbSI compound

Compound, modification Crystal lattice type and parameter, A

LT-CuI Cubic lattice; SpGr. F; a = 6.05844(3) A [27]

HT1-CuI Trigonal: SpGr. P3; a = 4.279±0.002; c = 7.168±0.007 (673 K) [34] Triqonal: SpGr. R-3; a = 4.29863(11); c = 21.4712(6) (603 K) [26] Triqonal: SpGr. R-3 a = 4.30571 (12); c = 21.4465(7) (608 K) [26]

HT2-CuI Cubic: SpGr. F a = 6.16866(6) [27]

SbI3 Rhombohedral: SpGr. ; a = 7.48; c = 20,90; Z = 6 [29]

SbSI Orthorhombic: SpGr. Pnam; a = 8.556(3); b = 10.186(4); c = 4.111(2); z = 4 [32] Orthorhombic: SpGr. Pna2,; a = 8.53; b = 10.14; c = 4.10 [33]

The symbols HT2, HT1, and LT indicate high, intermediate, and low-temperature modifications of CuI, respectively.

out at room temperature on the Bruker D2

Aesar German brand (99.999 % purity) were used in the course of experimental studies.

Binary SbI3 and ternary SbSI compounds were synthesised from the elemental components in evacuated (~10-2 Pa) silica ampoules followed by a specially designed method taking into account the high volatility of iodine and sulphur. The synthesis was performed in an inclined two-zone furnace, with the hot zone kept at a temperature 20-30 °C higher than the corresponding melting point of the synthesised compound, whereas the temperature of the cold zone was kept at about 130 °C. After the main portion of iodine and sulphur had reacted, the ampoules were relocated such that the products could melt at 230 °C (SbI3) and 450 °C (SbSI). After stirring the homogeneous liquid at this temperature, the furnace gradually cooled. The purity and individuality of the obtained products were monitored using DTA and PXRD methods.

Two sets of samples (0.5 g by mass each) were prepared by co-melting of different proportions of the preliminarily synthesised compounds and CuI of the Alfa Aesar company. After melting, most of the alloys were annealed at about ~20-30 °C below the solidus temperature for ~1000 hours in order to achieve complete homogenisation.

The DTA and PXRD methods were used to monitor the purity and individuality of the synthesised compounds and to conduct experimental studies. DTA of the samples was carried out in evacuated quartz ampoules on a differential scanning calorimeter of the 404 F1 Pegasus System (NETZSCH). Results of measurements were processed using the NETZSCH Proteus Software. The accuracy of the temperature measurements was within ±2 °C. X-ray analysis of the annealed alloys was carried

PHASER diffractometer with CuK^ radiation. The diffraction patterns were indexed using the Topas 4.2 Software (Bruker).

3. Results and discussion

A co-analysis of experimental results together with the literature data regarding boundary binary systems helped us to obtain the full description of phase equilibria in the CuI-SbSI-SbI3 concentration triangle.

3.1. CuI-SbSI boundary quasi-binary system

The powder X-ray diffraction patterns of the thermally treated CuI-SbSI alloys are given in Fig. 1. As can be seen, diffraction patterns of samples in the full composition range consist of the diffraction peaks of the SbSI and low-temperature modification of CuI.

The T-x phase diagram of the system (Fig. 2) was constructed using DTA results (Table 2). Note that, a1 and a2 are solid solutions based on the HT1 - CuI and HT2 - CuI respectively, and p - is a solid solution based on SbSI.

The system is quasi-binary and forms a eutectic phase diagram. Eutectics has a ~ 45 mol% SbSI composition and crystallises at 327 °C by the reaction: L ^ a2 + p.

The formation of a1 and a2 solid solution areas based on the high-temperature modifications of CuI is accompanied by a decrease in temperature of its' both phase transformations and these phase transitions occur by metatectic and eutectoid reactions.

Isotherms corresponding to the 375 and 280 °C temperatures on the phase diagram, reflect metatectic

P. R. Mammadli et al.

Original article

Fig. 1. X-ray images of different alloys of the CuI-SbSI system: 1 - CuI, 2 - 10 mol% CuI, 3 - 20 mol% CuI, 4 - 40 mol% CuI, 5- 60 mol% CuI; 6 - 80 mol% CuI; 7 - 90 mol% CuI; 8 - SbSI

Cul 20 40 60

mol%

Fig. 2. T-x phase diagram of the CuI-SbSI system

P. R. Mammadli et al.

Table 2. DTA results of the CuI-SbSI system

Original article

Composition, Thermal effects, °C

mol% SbSI Isothermal Polythermal

0 (pure CuI) 369; 407;606 -

5 280;385 470-573

10 280; 325;375 375-534

20 282;327;373 373-455

30 280; 328;376 -

40 278;327 -

50 280;327 327-343

60 280;328 328-360

70 279;327 327-375

80 327 327-382

90 - 352-394

95 - 380-398

100 (pure SbI3) 402 -

^ L + a2

and eutectoid LT-CuI + ß.

a2 ~

equilibriums, respectively.

The homogeneity region of the b-phase based on SbSI is maximum (~15 mol%) at the eutectic temperature (Fig. 2). Moreover, reflection angles belonging to LT-Cul and SbSI phases on powder diffractograms are fully compatible with appropriate pure compounds. It shows that the mutual solubility of these compounds is negligible at room temperature. Therefore, in Fig. 2, the decomposition curve of the b-phase is extrapolated to the SbSI compound.

3.2. Projection of the liquidus surface (Fig. 3)

Fig. 3 represents a projection of the T-x-y diagram of the CuI-SbSI-SbI3 system, where liquidus isotherms are given in blue. The liquidus surface consists of three fields describing the primary crystallisation of the a1 (a2), b-phases, and SbI3. The latter occupies a small region near the appropriate corner of the concentration triangle.

Primary crystallisation surfaces of phases are limited by a number of monovariant equilibrium curves and non-variant equilibrium points (Table 3).

The L1+L2 immiscibility region in the CuI-SbI3 boundary system sharply penetrates into the concentration triangle and covers part of

Fig. 3. Projection of the liquidus surface of the system CuI-SbSI-SbI3. Primary crystallisation fields: 1 - a1 (a2); 2 - b phase; 3 -polythermal sections

SbI3. Dotted lines are studied

the liquidus area of the b phase by crossing the eutectic curve from the point e1. Consequently, the L ^ a2 + b monovariant eutectic equilibrium shifts to the L1 ^ L2+a2 + b nonvariant monotectic equilibrium (Fig. 3, Table 1 - MM' conjugate pair). K is the critical point of stratification and has a temperature of ~350 °C.

Crystallisation across the whole system ends at 165 °C by nonvariant eutectic (E) reaction.

3.3. Polythermal sections

The CuI-[B] (Fig. 4) and [A]-SbSI (Fig. 5) polythermal sections of the phase diagram of the CuI-SbSI-SbI3 ternary system are given below and analysed in context with the projection of the liquidus surface of the system. Here, [A] and [B] are 1:1 mix ratios of the constituent compounds of the CuI-SbI3 and SbSI-SbI3 side binary systems, consequently.

The system CuI-[B] (Fig. 4). This section passes through the initial crystallisation areas of the a1 (a2) and b-phases and the immiscibility area in the ~ 30-70 mol% CuI concentration range. Crystallisation in the compositions rich in CuI initially continues by the monovariant monotectic L1 ^ L2 + a1 reaction and leads to the formation of the L1 + L2 + a1 three-phase area. At 377 °C this phase field is replaced by the L1 + L2 + a1 three-phase area as a result of the a1 ^ a2 phase transition. Crystallisation in the 20-40 mol% CuI

P. R. Mammadli et al

Original article

Point in Fig. 3 Equilibrium Composition, mol% Temperature, °C

SbSI SbI3

ei L — a2 + p 45 - 327

e2 L — LT-CuI + SbI3 - 97 168

e3 L — SbSI + SbI3 7 93 167

m (mO L1 — L2 + «1 - 15 (93) 493

M (MO L1 — L2 + «2 + P 34 (6) 20 (87) 318

E L — LT-CuI + P +SbI3 - - 165

Curve in Fig. 3 Equilibrium Temperature interval, °C

mM (m'MO L1 — L2 + «1 493-318

KM (KMO Li - L2 + p 340-318

e1M L — a2 + p 327-318

M'E L — a2 (LT-CuI) + P 318-165

e2E L — LT-CuI + SbI3 168-165

езЕ L — p + SbI3 167-165

Composition, mol%

SbSI

SbI,

Temperature, °C

45

m (m') M (M') E

L ^ SbSI + SbI3

L1 ~ L2 + «1

L1 ~ L2 + «2 + ß L ^ LT-CuI + ß +SbI3

34 (6)

97 93 15 (93) 20 (87)

327 168 167 493 318 165

Curve in Fig. 3

Equilibrium

Temperature interval, °C

mM (m'M') KM (KM') e1M M'E

e2E

e3E

L1 ~ L2 + «1

493-318 340-318 327-318 318-165 168-165 167-165

- — 1 Zi •

monotectic scheme and forms the L1 + L2 + p phase area. Horizontal line at 318 °C belongs to the L1 ^ L2 + a2 + p nonvariant monotectic reaction (Table 2). After this reaction, the L2 + a2 + p three-phase area forms in the system. At 280 °C, the a2 ^ LT-CuI phase transitions occur and the latter phase area passes to the L2 + p + LT-CuI.

Crystallisation of all samples along the system ends at 165 oC by the nonvariant eutectic reaction

(E) and the p + LT-CuI + SbI3 three-phase mixture forms.

The system [A]-SbSI (Fig. 5). This polyther-mal section is situated in the L1 + L2 immiscibility area at the 0-40 mol% SbSI composition range and crystallisation processes occur by monotectic reactions (Fig. 3, mMK and m^K/ conjugate curves). In the course of those processes the L1 + L2 + a1, L1 + L2 + a2, L1 + L2 + LT-CuI and L1 + L2 + p three-phase areas are formed. In the alloys rich in SbSI, crystallisation of this compound initially occurs from the liquid solution, then continues by the L1 ^ L2 + SbSI monotectic scheme. All alloys are exposed to the nonvariant monotectic

60 40 mol%

Fig. 4. T-x phase diagram of the system CuI-[B]

40 60 mol%

Fig. 5. T-x phase diagram of the system [A]-SbSI

3

7

e

3

3

4—»

P. R. Mammadli et al. Original article

reaction (m) at 318 0C and fully crystallise by the nonvariant eutectic reaction at 165 °C.

Fig. 6 shows the DTA heating curves of selected annealed samples along the boundary quasi-binary system Cul-SbSI and the above-mentioned internal sections. Comparison of these curves with the corresponding T-x diagrams (Fig. 2, 4, 5), the projection of the liquidus surface (Fig. 3) and the table shows that they accurately reflect the character and temperatures of the processes occurring in the system.

4. Conclusion

The phase equilibria in the CuI-SbSI-SbI3 composition range of the Cu-Sb-S-I quaternary system have been studied for the first time. Several polythermal sections of the phase diagram including the CuI-SbSI boundary system and T-x-y projection of the liquidus surface of the system was obtained by co-analysis of experimental results along with the literature data on boundary binary systems. It was determined that there are limited solid solutions based on SbSI (b-phases) and HT-CuI (ax- and a2-phases) and the system is characterised by the formation of a large immiscibility area. The types and coordinates of non- and monovariant equilibria, as well as, primary crystallisation areas of phases were determined.

Contribution of the authors

P. R. Mammadli - experimental investigations, writing original draft, making conclusions. V. A. Gasymov - powder X-ray analysis. G. B. Dashdiyeva - research concept, methodology development. D. M. Babanly - scientific management, review and editing.

Conflict of interests

The author declares that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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P. R. MammadLi et al. Original article

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Information about the authors

Parvin R. Mammadli, PhD student in Chemistry, a Chemistry Teacher at French-Azerbaijani University, Azerbaijan State Oil and Industry University, Baku, Azerbaijan; e-mail: parvin.mammadli@ufaz.az. ORCID iD: https://orcid.org/0000-0002-8062-1485.

Vagif A. Gasymov, PhD in Chemistry, Assistance Professor, Institute of Catalysis and Inorganic Chemistry, Azerbaijan National Academy of Sciences, Baku, Azerbaijan; e-mail: v-gasymov@rambler.ru. ORCID iD: https://orcid.org/0000-0001-6233-5840.

Ganira B. Dashdiyeva, PhD in Chemistry, Chemistry Teacher, Baku Engineering University, Baku, Azerbaijan; e-mail: ganira.dasdiyeva@mail.ru.

Dunya M. Babanly, DSc in Chemistry, Coordinator of the Chemistry Department, Lecturer at French-Azerbaijani University, Senior Researcher of the Institute of Catalysis and Inorganic Chemistry, Azerbaijan National Academy of Sciences, Baku, Azerbaijan; e-mail: dunya.babanly@ufaz.az. ORCID iD: https://orcid.org/0000-0002-8330-7854 .

Received 16 February2021; Approved after reviewing 9 April 2021; Accepted 15 May 2021; Published online 25 June 2021.

Edited and proofread by Simon Cox