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CHEMICAL PROBLEMS 2024 no. 3 (22) ISSN 2221-8688
243
UDC544.31:546.56'22/24
THERMODYNAMIC PROPERTIES OF COMPLEX COPPER CHALCOGENIDES
REVIEW
1,2,3M.B. Babanly*, 1L.F. Mashadiyeva, 1S.Z. Imamaliyeva, 1D.B. Tagiev, 1,4D.M. Babanly,
5Yu.A. Yusibov
'Institute of Catalysis and Inorganic Chemistry named after. M. Nagieva MSE AR
2Baku State University 3Azerbaijan State University of Economics 4French - Azerbaijani University (UFAZ), Azerbaijan, Baku 5Ganja State University *e-mail: babanlymb@gmail.com
Received 21.03.2024 Accepted 13.05.2024
Abstract: Complex copper-based chalcogenides are a significant environmental-friendly functional material that has great application potential due to their interesting thermoelectric, photoelectric, optical, and other properties, as well as their ionic conductivity. Analysis of numerous studies shows that improving the application characteristics of these compounds is associated with manipulating their structure and composition. An effective solution for optimizing such processes requires their in-depth thermodynamic analysis, which requires reliable data on the fundamental thermodynamic characteristics of the corresponding compounds. This review summarizes the results of researches, including ours works, on the thermodynamic properties of copper chalcogenides with some p'-p3 elements. The majority of these works were carried out using various modifications of the electromotive force (EMF) method. Planning of experiments carried out by this equilibrium method of chemical thermodynamics and processing of their data is impossible without the presence of reliable data on phase equilibria. Taking this into account, in addition to thermodynamic data, the work also presents the solid-phase equilibria diagrams for a number of systems studied by the EMF method.
The analysis showed that for the Cu-Tl-X, Cu-Ge(Sn)-X (X-S, Se, Te) and Cu-As(Sb, Bi)-S(Se) ternary systems there are mutually consistent data on the phase equilibria and thermodynamic functions of the ternary compounds. For the Cu-Tl-X and Cu-Sn-Se systems, the thermodynamic functions of ternary compounds are obtained by two modifications of the EMF method by determining the partial molar functions of two different components - copper and thallium (tin). The thermodynamic properties of copper chalcogenides with gallium, indium, and silicon have not been extensively researched, and the data that is available is inconsistent.
Keywords: complex copper chalcogenides, ternary copper-containing systems, phase diagrams, thermodynamic properties, EMF method. DOI: 10.32737/2221-8688-2024-3-243-280
1. Introduction
Binary and complex metal chalcogenides have been widely studied since the middle of the last century as semiconductor, thermoelectric, photoelectric, optical, magnetic, and other functional materials. Many of them have found applications or are considered promising for use in various fields of modern engineering and technology [1-7]. The
development of nanomaterials science and the discovery of new unique quantum states of matter as a topological insulator [8], and then an antiferromagnetic topological insulator [9], gave new impetus to the research of chalcogenides. Studies have shown that many-layered chalcogenides have the properties of a topological insulator [10-14], and some of them
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CHEMICAL PROBLEMS 2024 no. 3 (22)
combine the properties of a topological insulator and a magnet [15-17] and are extremely promising for a wide variety of applications in modern high technologies [18-20].
Copper-based chalcogenides occupy an important place among advanced functional materials. In addition to unique electronic properties [3-5, 21-29], they also have high ionic conductivity [30-33] and are considered very promising for use in thermoelectric and photoelectric energy converters and optoelectronic devices, as well as solid-state electrodes and electrolytes, selective membranes, sensors, sensors, etc. Moreover, according to a number of studies in recent years, some copper-based chalcogenides are promising for use in medicine [34, 35]. On the other hand, many copper chalcogenides exist in nature in the form of minerals and are of great interest to the geochemistry of the earth [36, 37].
Analysis of numerous studies on complex copper-containing chalcogenide materials (see Sections 3-5) shows the possibility of significantly improving their functional properties by manipulating the structure and composition. For a better understanding of the relationship between composition, structure and properties, as well as for the search and design of new materials, it is especially important to have reliable, mutually consistent data on the phase equilibria and thermodynamic properties of the corresponding systems [20, 38-40]. The importance of using phase diagrams is that they make it possible not only to identify new compounds or phases of variable composition but also to establish their thermal stability, the nature of formation, areas of primary crystallization and homogeneity, the presence of phase transformations, etc. An effective solution to the optimization of processes requires a deeper thermodynamic analysis, which is only possible if reliable data are available on the fundamental thermodynamic characteristics of the relevant compounds [38].
The purpose of this review is to systematize existing literature data, including the authors' work on the study of the thermodynamic properties of copper chalcogenides with heavy p1-p3 elements.
Section 2 of the manuscript briefly describes some methodological issues related to
thermodynamic research, especially the electromotive force (EMF) method, which was employed to obtain most thermodynamic data for copper-based chalcogenides. In the following sections, available data on the fundamental thermodynamic characteristics of these ternary compounds and some phases based on them are presented and discussed. Considering the importance of phase diagrams in EMF studies, this manuscript also presents data on solid-phase equilibria of a number of studied systems in addition to thermodynamic dat. At the beginning of these sections, a brief overview of works on the most characteristic functional properties of ternary phases of this type is given. The EMF method is employed to obtain thermodynamic data for copper-based chalcogenides.
2. Some methodological issues in the thermodynamic study of metal chalcogenides
An analysis of numerous literature data shows that the EMF method occupies a leading position in the thermodynamic study of metallic and semiconductor, in particular chalcogenide, systems. Various modifications of this method, such as the classical version of concentration cells with a liquid electrolyte, the EMF method with a solid cation- and anion-conducting electrolyte, accelerated modifications of the method, etc. are successfully used in thermodynamic research [41-45].
An important advantage of the EMF method is that it is an equilibrium method of chemical thermodynamics and allows combining thermodynamic research with phase equilibria studies [42, 43]. At the same time, phase equilibria data is important for both experiment planning using the EMF method and processing results.
In practice, thermodynamic studies most often use concentration cells relative to electrodes of the following type [41-43]
(-) A (solid or liquid) | ionic conductor containing ions Az+1A in alloys (+ ) (1)
where A is the least noble component of the studied system.
EMF measurement data in a certain temperature range are presented in the form of
E = a + bT ± t
recommended in [42]. Here n - is the number of pairs of values E and T; SE and Sb are the dispersions of individual EMF measurements and coefficient b, respectively; T - the average absolute temperature; t - is Student's criterion.
linear equations, for example, in the form
S2 "
Se + Sb2(T - T)2
n
1/2
(2)
The Student's criterion is t<2 with a confidence level of 95% and the number of experimental points being n>20.
From equations (2) according to the following thermodynamic relations
AG a = —zFE
f ÔE }
ASa = zF
vôt y
AHa = —zF
E — T
vôt y
(3)
(4)
(5)
p
the partial molar functions of the mobile component A may be calculated.
Thus, by measuring the equilibrium values of the EMF of concentration cells of type (1) in a wide temperature range for various compositions of the right-hand electrodes, it is possible to calculate the relative partial molar free energy, enthalpy and entropy of component A in a multicomponent solution or heterogeneous mixture.
The issues of organizing and conducting experiments using various variants of the EMF method and methods of mathematical processing of results are discussed in detail in a number of monographs and original works [4249].
Due to the high accuracy of electrochemical measurements, the determination of thermodynamic functions by the EMF method gives reliable results. The root mean square error of EMF measurements under favorable conditions can be reduced to 0.5 mV, which corresponds to a single determination
error of the order of 100 J-mol-1. This value
1/2
decreases by another factor of n (n is the number of experimental points) for the average value. Such accuracy is incomprehensible in other methods of thermodynamic study of condensed systems. Relative partial molar entropy and enthalpy, calculated from the temperature coefficient of EMF, are determined with less accuracy. However, experience shows that by ensuring the reversibility of the
operation of electrochemical circuits in a wide temperature range, the accuracy of determination of and can reach 0.5^1 J-K-1-mol-1 and 0.3^0.5 kJ-mol-1, which is comparable with the accuracy of calorimetric measurements [42].
In [42-44], methods for calculating integral thermodynamic functions of ternary and more complex phases based on partial thermodynamic functions of potential-forming components and a phase diagram are described in detail.
Let's consider the main types of concentration cells used in thermodynamic studies of complex chalcogenides.
1) In several researches, including studies our group [43, 44, 50-55], concentration cells of the following type
(-) A (solid) | glycerol+Az+ | (A in alloy) (solid) (+) (6)
were used in the thermodynamic study of chalcogenide systems.
Using of glycerol solutions of alkali or alkaline earth metals' chlorides makes it possible to conduct experiments in the 300-430 K temperature range, i.e. under conditions close to standard. It should be noted that electrochemical cells with glycerol electrolyte, first applied in 1963 by authors of [56] to amalgam systems, and later successfully used to study various binary and complex systems
2) The discovery of superionic conductors with pure Cu+ and Ag+ conductivity at room temperature, primarily the Ag4RbI5 [57] and Cu4RbI3Cl2 compounds [58], gave new impetus to thermodynamic studies of copper- and silver-containing systems. In a number of works [5963], concentration cells relative to a copper (silver) electrode with the indicated electrolytes were used to study ternary chalcogenides of copper and silver
(-) A1 (solid) |solid electolyte +А+ | (A1 in alloys) (solid) (+) (7)
(here A1 is Cu+ or Ag+).
The authors of [64-67] successfully used concentration cells with glassy Ag+ conducting electrolyte for thermodynamic studies of silver-containing systems.
It should be noted that to determine the thermodynamic functions of the formation of complex chalcogenide phases, including copper and silver, calorimetric methods are used relatively less frequently. This is apparently due to the complexity of calorimetric experiments, as well as the fact that during the synthesis or combustion of substances in a calorimetric bomb, the processes often do not proceed to completion and it is very difficult to quantify the degree of conversion [38, 43]
At the same time, the differential scanning calorimetry (DSC) is successfully used to determine the thermodynamic functions of reversible phase transitions of the first order -polymorphic transformations or melting [6870].
3. Copper chalcogenides with elements of the gallium subgroup
Copper chalcogenides with gallium and indium, as well as solid solutions and doped phases based on them, are excellent materials for use in photovoltaic devices [71-84], optoelectronics [75, 85-87], and also as luminescent materials [88- 91].
The use of these phases as solar energy absorbers is due to their band gap, which correlates well with the maximum photon power density in the spectrum of sunlight and at the same time demonstrates long-term stability and
resistance to radiation [82-84]. In the past few years, substantial research has been conducted to enhance their effectiveness. For this purpose, several studies have proposed changing the bulk or surface composition through sulfidization (selenidization) [77, 79, 80], adjusting the ratios of Cu, Ga, and In atoms [73, 84], adding alloying components [71, 78] and other strategies [78]. Note, that by sulfidization of the Cu(Ga, In)Se2 layers, a solar cell with a record efficiency of 23.35% was obtained [81]. Thin-film solar cells based on Cu(Ga, In)Se2 are considered as a promising for electricity generation in space stations [82, 84].
Authors of the review [76] using a fundamental thermodynamic approach discussed the main reasons for the relatively low efficiency of photovoltaic systems based on copper-gallium (indium) chalcogenides and ways to optimize methods for obtaining their crystals with specified characteristics. The latest advancements in the production of nanocrystals of these phases with controlled compositions and band gaps are presented in another review [78].
Copper chalcogenide compounds, which have a wide bandgap energy range, are very attractive for applications in optoelectronic and light-emitting devices [86]. Due to their unique optical properties, they can also be used in nonlinear optical devices [87]. The authors of [88] report the development of quantum dot LEDs that exhibit red color with a narrow emission peak by controlling the copper content of Cu-Ga-In-S alloys.
Copper selenides and tellurides with elements of the gallium subgroup, especially thallium, are of interest as thermoelectric materials with low thermal conductivity [9295].
3.1. The Cu-Ga-Х и Cu-In-X (X-S, Se, Te) systems
Copper with gallium and indium forms ternary phases with a wide homogeneity region, which have a disordered cubic structure. With decreasing temperature, these phases transform into low-temperature compounds with ordered structures. The most typical compounds are the CuBmX2, CuBnI3X5 and CuBnI5X8. These compounds form on Cu2X-BIII2X3 quasi-binary sections and form stable connodes with the
corresponding elemental chalcogen [96-99]. chalcogenides. The thermodynamic properties
We have not found any literature data on of copper-indium sulfides and selenides have the thermodynamic properties of copper-gallium been studied in a number of works (Table 1).
Table 1. Standard integral thermodynamic functions of ternary compounds of the Cu-Ga(In)-X
systems
Compound -A G0(298K) -A H0(298K) S0 (298K) J-mol-1-K-1 Ref.
KJ-mol"1
CuIn5S8 1238±113 [99]
CuInS2 315±54 - [99]
221.8±13 [100]
327.6 136±0.8 [30] [101]
CuIn5Se8 1060 [102]
CuIn3Se5 380.0±1,4 398.2±28,6 373±28 [59]
*467.1±28.0 *486.3±27.0 [59]
658 [102]
CuInSe2 153.2±0,6 158.0±9.6 163±11 [59]
*196.8±9.8 *201.6±9.2
220.0 218.5 [102]
Note: * - values calcu lated from data [59] using other thermodynamic data for I n2Te3.
Table 1 shows that the available data are insufficient and contradictory. Complete complexes of standard integral thermodynamic functions were determined only for compounds CuIn3Se5 and CuInSe2 by the EMF method with a Cu+ conducting electrolyte (cell of type 7) [59]. For processing the experimental results, the authors of [54] used the following data for the In2Se3 compound: -A,G0(298K) = 224.3 ±
0.8 kJ/mol; -ah0(298k) =239.3 ± 18.4
kJ/mol; S098 =201.3 ± 16.7 J/(mol-K).
Considering that modern reference books, for example [112], recommend significantly different from the above data ( AfH0(298K) = -
326.4±16.7 kJ/mol ; S098 = 201.3±16.7
J/(mol-K)), the latter was used in our calculations for CuIn3Se5 and CuInSe2 (marked with an asterisk in Table 1). The data obtained for CuInSe2 are in better agreement with the results of [102].
3.2. The Cu-Tl-X systems
The results of multiple studies on phase equilibria and thermodynamic properties of these systems, carried out before the early 90s of the last century, are summarized in [21].
Below the results of thermodynamic
studies, including more recent studies, as well as brief information of solid-phase equilibria in the appropriate system are given.
The Cu-Tl-S system. The Cu2S-Tl2S quasi-binary section of this system was studied almost simultaneously by two teams of authors [103, 104]. According to [103], this system is characterized by the formation of the Cu9TlS5, Cu3TlS2 and CuTlS ternary compounds. The first two compounds melt with decomposition by peritectic reactions at 706 and 693 K, respectively, and the last one melts congruently at 689 K. According to [104], there are two congruently melting ternary compounds CuTlS and Cu8Tl2S5 in the system. The phase diagram presented in [103] was confirmed by the authors of [105].
The results of a comprehensive study of the phase equilibria of the Cu-Tl-S system are presented in [106-108]. The projection of the liquidus surface, solid-phase equilibria diagram at 300 K and a number of polythermal sections of the phase diagram are constructed. In [108], the results of a thermodynamic study of copper-thallium sulfides by EMF measurements of concentration cells of type (6) are also presented. Later, in [109], a thermodynamic study of the Cu-Tl-S system was carried out by
EMF measurements of concentration cells of type (7) relative to a copper electrode. It should be noted that the thermodynamic data obtained in [108, 109] are independent: they use the results of EMF measurements of different concentration cells, based on which the partial thermodynamic functions of various components of the system - thallium and copper are calculated, which characterize various potential-forming reactions.
Let us consider the results of these works
in more detail. In Fig.1 a solid-phase equilibria diagram of the Cu-Tl-S system is presented. This diagram is characterized by the presence of four ternary compounds, which form a series of three-phase regions between themselves, as well as with binary compounds and the initial components of the system. Tables 2 and 3 list the equations of type (2) for the temperature dependences of the EMF of cells of types (6) and (7).
Table 2.Temperature dependences of the EMF of concentration cells of type (6) in some phase
areas of the Cu-Tl-S system (T=300^380K) [108]
Phase area in Fig.1 E,mV = a + bT ± 2SE(T)
Cu9TlS5+Cu2 S+CuS 580.0-0.044r ± 2 2 4 — + 0.0001(r - 346.7)2 _ 40 _ 1/2
CusTlS2+Cu9TlS5+CuS 585.5+ 0.315T ± 2 1 52 + 0.0035(r 349.6)2 _ 40 _ 1/2
CuTlS+ CusTlS2+ CuTlS2 598.6+ 0.351T ± 2 135 — + 0.0017(r - 351.5)2 88 1/2
CuTlS2+ CuS+S 435.1+ 0.140r ± 2 " 40 — + 0.0006(r - 350.6)2 1/2
Table 3. Temperature dependences of the EMF of concentration cells of type (7) in some phase
areas of the Cu-Tl-S system (T=300^380K) [109]
Phase area in Fig.1 E,mV = a + bT ± 2SE(T)
CuTlS2+TlS2+S 452.2-0.056T ± 2 2.5 — + 7.2 -10-5(r - 343.7)2 _ 24 _ 1/2
CuTlS+CuTlS2+Tl4S3 389.4+ 0.086T ± 2 2 7 — + 9.7 -10-5(r - 346.1)2 _ 22 _ 1/2
CusTlS2+CuTlS2+ CuS 340.2+ 0.067T ± 2 18 18 + 5 . 8 -10-5(r - 344.1)2 _ 22 _ 1/2
Cu9TlS5+Cu3TlS2+ CuS 292.1+ 0.134T ± 2 — + 5.2 -10-5(r - 342.6)2 _ 22 _ 1/2
From these equations, using relations (3)-(5), thallium (Table 4) and copper (Table 5) were the relative partial thermodynamic functions of calculated.
Table 4. Relative partial thermoc ynamic functions of thallium in Cu-T -S alloys at 298 K
Phase area in Fig.1 -AGT1 -AHT1 ASi J-mol-1 K-1
Kj-mol-1
Cu9TlS5+Cu2S+CuS 53.28±0.69 44.23±3.99 30.36±11.38
Cu3TlS2+Cu9TlS5+CuS 48.56±0.49 38.46±2.79 33.90±8.07
CuTlS+ Cu3TlS2+ CuTlS2 46.01±0.30 41.98±1.67 13.53±4.73
CuTlS2+ CuS+S 54.69±0.01 55.96±0.68 -4.25±1.93
Table 5. Relative partial thermodynamic functions of copper in Cu-Tl-S alloys at 298 K
Phase area in Fig.1 - AGCu -AHcu AScu J-mol-1-K-1
KJ-mol-1
CuTlS2+TlS2+S 42.02+0.10 43.64+0.56 -5.40+1.64
CuTlS+CuTlS2+Tl4S3 40.04+0.11 37.57+0.66 8.30+1.90
Cu3TlS2+CuTlS2+ CuS 34.75+0.09 32.82+0.52 6.46+1.47
CujTlS5+Cu3TlS2+ CuS 33.20+0.08 28.18+0.50 12.93+1.38
The EMF isotherms of cells (6) and (7) along the Cu2S-Tl2S section are presented in Fig.2. As can you see, the EMF values of both types of cells is constant within a certain phase region and changes abruptly when moving from one phase region to another. In this case, the numerical values of the EMF increase with a decrease in the thallium concentration in the alloys. For cells (6) this is expected, but for cells (7) such a picture, at first view, contradicts the well-known requirement [43] that it is
impossible to reduce the EMF value with a decrease in the concentration of the potential-forming component in the alloy. However, a comparison of Fig. 2 with the phase diagram (Fig. 1) shows that both dependences are in accordance with the above requirement, namely, the EMF values increase with decreasing concentration of the potential-forming component along the corresponding ray straight lines (red and blue lines in Fig. 1).
Fig.1. The solid-phase equilibria diagram of the Cu-Tl-S system at 300 K.
Fig.2. EMF isotherms of concentration cells (6) and (7) along the Cu2S-Tl2S section
The partial molar functions of thallium values of thallium in the indicated phase regions
and copper (Tables 4 and 5) characterize various (Table 4) are the thermodynamic characteristics
virtual potential formation reactions. According of the following potential formation reactions
to the phase diagram (Fig. 1), the partial molar (all substances are in crystalline form):
Tl+CuS+S=CuTlS2 (8)
Tl+CuS+Cu2S=CujTlS5 (9)
1 4
Tl+CuS+ - Cu9TlS5= - CU3TIS2 3 3
Tl+0. 5CU3TIS2 +0.5 CuTlS2=2CuTlS
(10) (11)
Similarly, the partial molar functions of copper (Table 5) are the thermodynamic characteristics
of the below potential formation reactions:
Cu+TlS2=CuTlS2
Cu+0.25Tl4S3+0.25CuTlS2=1.25CuTlS
Cu+0.5CuTlS2 =0.5Cu3T1S2
Cu+0.333Cu3TlS2+CuS=0 .333cu9t1s5
(12)
(13)
(14)
(15)
Using the above equations for potential formation reactions, the standard thermodynamic functions of formation and standard entropies of copper-thallium sulfides
AZ!
'CuTlS,
CuS
SCuTl% — ASTl + STl + SCuS
were calculated. For example, in accordance with reaction (8) for the CuTlS2 compound, calculations were carried out using the relations
(16) (17)
(here AZ°=AG° or AH0 of the corresponding compound, AZ = AGqj or AHu ) and taking
into account reaction (12) according to the relations:
az0
CuTlS,
— azcu +az:
TlS
s:
CuTlS-
— as^, + s° + s:
TlS
(18) (19)
In addition to the partial molar values of thallium or copper (Tables 4 and 5), thermodynamic data for the compounds TlS2, TI4S3 [110], Cu2S and CuS [111] (Table 6), as well as standard entropies of copper (S0
=33.1±0.5
Jmol-1K-1)
and thallium (S
298
=64.18±0.21 Jmol-1K-1) [112] were used for calculations equations (8)-(15).
The obtained two series of values of standard integral thermodynamic functions of copper-thallium sulfides are listed in Table 6.
0
0
0
Table 6. Standard integral thermodynamic functions of ternary compounds of the Cu-Tl-S system
and some binary compounds used in ca culations
Compounds -A G0(298K) -A H0 (298K) S0(298K) Ref.
KJ-mol-1 Jmol-1K-1
CuS 36.8+0.4 42.7+3.4 46.4+2.9 [111]
Cu2S 66.1+0.8 63.2+5.9 108.8+5.4 [111]
TIS2 52.3+0.5 50.0+0.8 145.0+0.9 [110]
TI4S3 196.8+1.5 197.4+6.5 348.5+20.5 [110]
CuTlS2 91.5+0.5 98.6+4.0 [108]
94.3+0.7 93.6+1.4 172.7+2.8 [109]
CuTlS 84.1+1.5 82.1+4.9 [108]
90.3+0.7 88.3+2.1 132.4+6.2 [109]
Cu3TlS2 152.7+1.8 145.8+12.3 [108]
163.8+2.6 159.2+9.8 251.8+5.8 [109]
Cu9TlS5 354.6+4.5 373.8+3.9 339.7+30.8 371.8+21.4 529.0+19.0 [108]
[109]
Table 6 shows that the values of the standard thermodynamic functions for the formation of ternary compounds obtained by two modifications of the EMF method are in satisfactory agreement with each other. This confirms the reversibility of the concentration cells of (6) and (7) types, and the reliability of thermodynamic data for copper and thallium sulfides [110,111], used by the authors [108, 109] in the calculations.
The Cu-Tl-Se system. The quasi-binary Cu2Se-Tl2Se section of this system is characterized by the formation of the ternary CuTlSe, CuyTlsSe5, Cu3TlSe2, Cu8TfcSe5 and Cu9TlSe5 compounds [113]. According to [21], the CuTlSe-TlSe, CuTlSe-Tl and CuTlSe-Se sections are also quasi-binary. The first section forms a phase diagram of a simple eutectic type,
the second section is related to a monotectic type, and the third one is characterized by the formation of an incongruently melting ternary CuTlSe2 compound.
There is literature data about the synthesis and crystal structure of ten copper selenides with thallium [21, 114]. However, up to now, a complete picture of phase equilibria in the Cu-Tl-Se system has not been obtained. In [115], a fragment of the solid-phase equilibria diagram of this system was constructed, which reflected three ternary compounds (Fig. 3) and their thermodynamic properties were studied by the EMF method with a solid electrolyte. For the compounds CuTlSe2 and CuTlSe, the corresponding thermodynamic data were previously obtained [43] by EMF measurements of (6) type cells (Table 7).
Table 7. Standard thermodynamic functions of formation and standard entropies of TlSe and some
ternary phases of the Cu-Tl-Se and Cu-Tl-Te systems
Compounds -A G0 (298K) -A H0(298K) S0 (298K), Ref
Kj-mol-1 J-mol-1-K-1
CuTlSe2 96.29+0.16 97.91+0.95 176.1+5.1 [115]
96.5+0.6 97.2+1.3 [43]
CuTlSe 84.49+0.16 81.37+0.85 149.9+2.8 [115]
84.2+1.3 80.5+3.9 [43]
Cu2TlSe2 119.06+0.27 118.61+1.54 216.2+6.8 [115]
CuTlTe2 75.1+0.4 72.6+1.3 208+4 [118]
Cu2TlTe2 99.2+0.5 94.3+2.1 249+6 [118]
94.8+0.9 92+7 237+3 [119]
Cu3TlTe2 122.0+0.6 115.2+2.7 288+8 [118]
117.1+1.2 117+5 263+4 [119]
CujTlTe5 264.3+2.6 253.8+9.8 637+15 [118]
244.0+2.4 2431+14 621+7 [119]
5(Cu0,2Tl4,8Te3) 210.2+1.7 213.0+2.2 454+7 [118]
5(Cu0,4Tl4,6Te3) 207.8+1.6 210.5+2.3 449+7 [118]
ô(Cu0,6Tl4,4Te3) 205.3+1.6 207.6+2.4 444+8 [118]
ô(Cu0,8Tl4,2Te3) 203.8+1.5 206.0+2.5 438+8 [118]
CuTl4Te3 201.4+1.4 203.8+2.6 433+9 [118]
Fig. 3. Fragments of solid-phase equilibria diagrams of the Cu-Tl-Se [115] and Cu-Tl-Te [118]
systems at 300 K.
The Cu-Tl-Te system. According to available data [21, 118], the Cu2Te-Tl2Te section is non-quasi-binary and is characterized by the formation of ternary Cu9TlTe5 and Cu3TlTe2 compounds with incongruent melting. Ternary compounds with the compositions CuTlTe2, Cu2TlTe2 and CuTl4Te3 are also reported [21, 114, 116, 117].
The fragments of the Cu-Tl-Te solidphase equilibria diagram and the results of a thermodynamic study of some copper-thallium tellurides by EMF measurements of concentration cells (6) and (7) are presented by authors of [118, 119]. Figure 3 shows the phase diagram at 300 K according to the data of [119], which reflects the above ternary compounds. The integral thermodynamic functions of three of them were determined by two modifications of the EMF method and are in satisfactory agreement (the discrepancies do not exceed 10%). Table 7 also shows thermodynamic data for CuTl4Te3-Tl5Te3 solid solutions [118].
4. Copper chalcogenides with p elements
The most characteristic and studied copper chalcogenides with p2- elements are compounds of the Cu2BIVX3 and Cu8BIVX6 types. Below is a brief overview of studies on the functional properties of these compounds.
Compounds of the Cu2BIVX3 type, especially Cu2SnSe3, Cu2GeSe3, and alloys based on them have been widely studied as environmentally friendly and affordable thermoelectric materials [120-130]. It has been
shown that Cu2SnSe3 doped with various elements (In, Zn, Ag, Sb, Pb, S, Te) [123, 124, 126, 129], as well as its composites with graphene and other phases [125, 128, 130], demonstrate good thermoelectric indicators. The thermoelectric characteristics of Cu2GeSe3 doped with various elements [121, 129], as well as solid solutions based on it [122] also improve.
Studies have shown that Cu2BIVX3 compounds are also promising for use as photovoltaic and optoelectronic materials [131144]. The photoelectric and optical properties of the Cu2SnS3 compound and alloys based on it have been studied in most detail [136-144]. Authors of [134] presents a review of works on the synthesis, structural transformation, morphological engineering and restructuring of the energy gap of nanoparticles of Cu-Sn-S(Se) systems and discusses the prospects for the development of solar cells based on them. In addition, other photovoltaic applications such as photoelectrocatalytic hydrogen production and dye degradation of Cu-Sn-S(Se) nanoparticles are also noted.
Another review [144] shows that the Cu2SnS3 ternary compound, consisting of non-toxic and readily available elements, is the preferred photovoltaic material for solar cell applications due to its optimal structural and optical properties. This paper also discusses the issues of efficiency loss in solar cells based on this compound and possible ways to eliminate them.
Copper-containing compounds of the
argyrodite family with the general formula Cu8BIVX6 are also of great interest as effective ionic conductors, thermoelectric, photoelectric and nonlinear optical materials [145].
Cu argyrodites, being typical superionic semiconductors with two independent structural units (a rigid anionic framework and weakly bound Cu+ cations), can serve as very good base compounds for the development of highperformance thermoelectric materials by separately tuning the electrical and thermal properties [145, 146]. It should be noted that only a small part of the research of the thermoelectric properties of argyrodites is devoted to the study of compounds of stoichiometric composition [146-148]. Most of the existing works on argyrodite thermoelectrics are focused on the production of nano- and single crystals, thin films, high-density polycrystals, complex phases, and composite materials based on them [145, 146, 149-151]. To increase thermoelectric efficiency, researchers often vary the composition of argyrodite compounds in the following ways [145]: 1. Complicating the composition through various types of substitution with analogue atoms; 2. Adding dopants; 3. Creation of a deficiency of individual elements in the stoichiometric composition.
The optical properties of some AI8BIVX6 compounds were studied in [152, 153]. It was shown [152] that replacing Ag with Cu in isostructural AI8BIVX6 compounds causes a clear increase in secondary harmonic generation. This result opens up the possibility of synthesizing high-quality infrared nonlinear optical materials based on them. Authors of [153] report the preparation of Cu8SiS6 and Cu8SiSe6 thin-film layers for optoelectronic applications.
4.1. The Cu-Si-X systems
Phase equilibria in the Cu-Si-S-Se ternary systems were studied along quasi-binary Cu2S-SiS2 [154] and Cu2Se-SiSe2 sections [155]. According to these works, copper and silicon form ternary compounds of the Cu8SiX6 and Cu2SiX3 compositions. The thermodynamic properties of these compounds have been practically not studied. There are works [68-70] in which the functions of phase transitions of some compounds were determined by the DSC method. These data are given in subsection 4.2.
(Table 10).
4.2. The Cu-Ge-X systems
The Cu-Ge-S system. According to [156, 157], the Cu2S-GeS2 quasi-binary section is characterized by the formation of Cu8GeS6 and Cu2GeS3 compounds with incongruent melting at 1253 and 1213 K. Cu8GeS6 undergoes a polymorphic transformation at 328 K. An isothermal section of the phase diagram of the Cu-Ge-S system at 300 K (Fig. 4), at which the above ternary compounds were reflected is presented in [21].
The Cu-Ge-Se system. According to [158], the nature of phase equilibria along the Cu2Se-GeSe2 section is similar to the sulfide system: ternary compounds Cu8GeSe6 and Cu2GeSe3 melt with decomposition by peritectic reactions at 1080 K and 1037 K. The presented in [159] T-x diagram confirms Cu2GeSe3 compound with congruent melting at 1033 K, but instead of Cu8GeSe6 a compound of similar composition Cu6GeSe5 is presented. Later, this system was re-studied in the composition range of 15-60 mol% GeSe2 [160] and it was shown that the congruent melting temperature of Cu2GeSe3 is 1053 K, and Cu8GeSe6 melts with decomposition at 1083 K and has a polymorphic transformation at 328 K.
The Cu-Ge-Te system studied in a number of works, the results of which are summarized in [21]. There is one ternary compound Cu2GeTe3 in the system.
Fig. 4 shows the phase diagrams of the Cu-Ge-S, Cu-Ge-Se and Cu-Ge-Te systems at room temperature [21]. The thermodynamic properties of copper-germanium chalcogenides were studied in [45, 161-163, 167] by EMF measurements of concentration cells of type (7).
When planning experiments on the Cu-Ge-S and Cu-Ge-Se systems, the authors of [161] proceeded from the fact that the Cu8GeS6 and Cu8GeSe6 compounds have polymorphic transitions in the temperature range of EMF measurements. Experiments have shown that the temperature dependences of the EMF for electrode alloys containing the Cu8GeS6 and Cu8GeSe6 compounds have the form of two straight lines with a break point at the temperature of their polymorphic transformation (Fig. 5). From the EMF measurements data, the partial molar functions of copper were
calculated for two modifications of the indicated formation (Table 9) and polymorphic transitions compounds (Table 8), which were used to (Table 10). calculate the thermodynamic functions of
Fig.4. Solid-phase equilibria diagrams of Cu-Ge-X and Cu-Sn-X systems at 300 K [21].
Fig.5. EMF dependences of concentration cells (7) for Cu8GeS6 and Cu8GeSe6 compounds [161]
Table 8. Partial molar thermodynamic functions of copper in some phase regions of the Cu-Ge-S
and Cu-Ge-Se systems [161]
Phase area T, K -AGcu - AHcu AScu J-mol-1-K-1
Kj-mol-1
a-Cu8GeS6+Cu2GeS3+S 298 37.925+0.013 35.37+0.32 8.56+1.04
p-Cu8GeS6+Cu2GeS3+S 400 -39.000+0.098 34.52+0.55 11.19+1.52
a-Cu8GeSe6+Cu2GeSe3+Se 298 26.735+0.009 24.59+0.19 7.20+0.59
p-Cu8GeSe6+Cu2GeSe3+Se 400 27.856+0.059 22.61+0.27 13.12+0.70
Table 9. Standard integral thermodynamic functions of the argyrodite family compounds
Phase - A G0 - A H0 S0 JK-1mol-1 Ref.
Kj-mol-1
Cu2GeS3 211.3+2.4 213.7+2,3 190.3+5.5 [167]
RT-Cu8GeS6 438.9+2.5 425.9+4.2 536.3+13.1 [161]
HT-Cu8GeS6 *445.3+3.1 420.8+5.6 552.1+15.8 [161]
Cu2GeSe3 178.4+18.8 174.5+19.7 223.4+6.6 [45]
176.8±3.1 173.9±3.1 233.3±5.1 [162]
RT- Cu8GeSe6 341.1+3.3 327.4+4,5 596.7+11.6 [161]
105.1+1.9 114.5+9.2 143+2 [162]
HT- Cu8GeSe6 *348.1+3.7 315.6+5.0 632.3+12.5 [161]
Cu2Sn4S9 659.9+4.3 650.9+29.7 560.3+74.7 [45]
165.4+1.5 141.6+6.3 639.8+18.3 [165]
Cu2SnS3 239.6+1.5 242.6+12.0 196.3+21.9 [45]
169.3+1.3 150.0+5.5 278.6+15.7 [165]
Cu4SnS4 316.4+2.4 327.7+18.8 266.5+28.2 [45]
261.3+2.4 220.8+9.4 414.4+20 [165]
Cu2SnSe3 189.5±2.6 187.5±4.8 251.6±5.0 [45,166]
198.4±0.6 198.5±2.9 237±5 [43]
Cu2SnTe3 117.7±1.4 116.2±2.4 264±6 [45]
*Note: data at 400 K is marked with an asterisk.
In [161], the thermodynamic functions of the polymorphic transformations of the Cu8GeS6 and Cu8GeSe6 compounds were calculated from EMF measurements data. Let us consider the
method of these calculations using Cu8GeS6 as an example. Since in the temperature range of EMF measurements the heat of formation of this compound is almost constant, then
AHp, =AfHu((3)-AfH» . where AHpt. - is the heat of polymorphic transformation; A H°(P) and A H0(a) - are the
(20)
heats of formation of two modifications of this compound. On the other hand, from following relation
6Cu+Cu2GeS3+3S=Cu8GeS,
>6
it follows that the contribution of Cu2GeS3 to the AH°(P) and AH°(a) functions is the same.
(21)
Therefore, the calculation of AHp.t was carried out according to the relation
AH t. = 6[AHcu(P) -AHcu(a)].
(22)
which does not include the value and error of the heat of formation of Cu2GeS3.
The entropy of the polymorphic transformation is calculated using the relation
ASp. t.=AHp,/Tp. t
Table 10 shows the thermodynamic functions of phase transitions of these compounds and their silicon analogues, obtained by the DSC method [69, 70, 164]. Table 10 demonstrates that the data obtained by both methods (exception for the Cu8GeS6) are in
(23)
good agreement. Calorimetric data is more accurate. Relatively high errors in the data obtained by the EMF method are due to the fact that in this method partial enthalpy and entropy are calculated indirectly from the temperature dependence coefficient of the EMF [42, 43].
Table 10. Temperatures and thermodynamic functions of phase transitions of some CusBIVX6
compounds
Compound Tp.t. AHp,., kJ-mol"1 ASp.t.., J-mol"1-K"1 Method, Ref.
Cu8GeS6 328 5.1±2.4 15.5±7.5 EMF, [161]
330 15.54±0.62 47.09±1.88 DSC, [70]
Cu8GeSe6 335 11.9±2.8 35.5±8.4 EMF, [161]
330 11.23±0.45 34.03±1.36 DSC, [164]
Cu8SiS6 336 14.85±0.59 44.20±1.77 DSC, [70]
Cu8SiSe6 325 14.73+0.59 45.32+1.81 DSC,[69]
4.3. The Cu-Sn-X systems The Cu-Sn-S system. Some polythermal sections of this system were studied in the 70s of the last century and summarized in [21]. It is shown that the Cu2S-SnS and Cu2S-SnS2 sections are quasi-binary. The first belongs to the eutectic type, and in the second 4 intermediate phases are formed: Cu2SnS3, Cu4SnS4, Cu4Sn3S6, and Cu2Sn4S9. The isothermal section of the phase diagram at 300 K (Fig. 4), presented in [21], reflects the above copper-tin sulfides.
The Cu-Sn-Se system. The only ternary compound of this system, Cu2SnSe3, is formed
on the quasi-binary Cu2Se-SnSe2 section and melts congruently at 963 K [21]. The T-x-y diagram and isothermal section of the phase diagram at 300 K (Fig. 4) based on data from a number of works were constructed in [21].
The Cu-Sn-Te system. In [21], a complete T-x-y diagram of this system is presented, characterized by the presence of one ternary compound Cu2SnTe3. This compound has a cubic structure and melts incongruently at 680 K.
The thermodynamic properties of copper-tin chalcogenides were studied by the EMF method with a solid electrolyte [45, 165, 166],
and the Cu2SnSe3 compound was also studied by the classical version of the EMF method with a liquid electrolyte. From the measurement data of the EMF of cells of type (7) using relations (3)-(5), the partial molar functions of copper in the alloys were calculated. The authors employed solid-phase equilibrium diagrams of the corresponding systems (Fig. 4) to calculate the integral thermodynamic functions. Table 9 show that the thermodynamic functions of Cu2SnSe3 obtained by two modifications of the EMF method are in good agreement with each other. It is also clear from Table 9 that the numerical values of the thermodynamic functions of copper-tin sulfides according to [165] are significantly lower than the data from [45]. For the compounds Cu2Sn4S9 and Cu4SnS4, the data [165] are even lower than the
sum of the corresponding values for Cu2S and SnS2, which is thermodynamically impossible. It was noted in [21] that this is the result of incorrect definition of potential-forming reactions by the authors of [165].
4.4. Quaternary systems including chalcogenides of copper and p -elements
In the last decade, in order to search for solid solutions with various types of substitutions based on copper chalcogenides with p2 elements, some quasi-ternary (Cu2S-Ag2S-GeS2 [168], Cu2Se-Ag2Se-GeSe2 [168], Cu2Se-GeSe2-SnSe2 [169], C^S-CugSiS6-CusGeS6 [70], Cu2Se-CusSiSe6-CugGeSe6 [170]) and reciprocal (2Cu2S+GeSe2o2Cu2Se+GeS2 [171, 172], 2Cu2S+SnSe2^2Cu2Se+SnS2 [168]) systems.
Cu:Se 20 40 c 60 80 u, Ag,Se SnS. 20 40 60 80 SnSe7 mol% mol%
Fig.6. Solid-phase equilibria diagrams of quasi-ternary Cu2S-Ag2S-GeS2 Cu2Se-Ag2Se-GeSe2 and
reciprocal 2Cu2S+GeSe2-o2Cu2Se+GeS2 u 2Cu2S+SnSe2-o2Cu2Se+SnS2 systems
Isothermal sections of phase diagrams at room temperature (Fig. 6) clearly demonstrate the formation of unlimited or broad solid solutions based on ternary compounds. A number of works [70, 167-169, 172-175] present the results of a comprehensive study of phase equilibria and thermodynamic properties of the above and some similar systems.
As an example, let's consider Cu2S-Ag2S-GeS2 system [167]. The results of EMF measurements of concentration chains of type (7) were in accordance with the solid-phase equilibrium diagram (Fig. 6) and confirmed the formation of wide areas of solid solutions based
on Cu2GeS3 and Ag2GeS3 compounds. The concentration dependence curves of EMF (Fig. 7) and partial molar functions of copper at 298 K (Fig. 8) have a form which is characteristic for systems with the formation of limited solid solutions based on the starting compounds. Within the homogeneity region of a- and P-solid solutions based on Cu2GeS3 and Ag2GeS3, respectively, the partial molar functions of copper are monotonic functions of composition, and in the heterogeneous a+P region have constant values, since the compositions of the coexisting phases are almost constant.
Fig.7. Isotherms of EMF of cells of type (7) and partial molar functions of copper in the Cu2GeS3-
Ag2GeS3 system
Based on the analysis of the Cu-Ag-Ge-S concentration tetrahedron (Fig. 8), the authors of [167] determined potential-forming reactions for individual compositions of Cu2-xAgxGeS3 solid solutions. As can be seen, the ray lines from the top of Cu, passing through the Cu2GeS3-Ag2GeS3 section, reach the concentration plane of the side ternary system
Ag-Ge-S in the three-phase region Ag2GeS3+GeS2+S. Therefore, in the overall potential-forming reaction for Cu2-xAgxGeS3 solid solutions, the phases of the indicated three-phase region and elemental copper must interact. For example, for a solid solution with Cu02Ag18GeS3 composition the potential-forming reaction has following form:
Cu+4.5Ag2GeS3+0.5GeS2+0.5S= 5Cu0.2AgL8GeS3,
and the relations for calculating its integral below: thermodynamic functions ( AZ = AG or AH ) as
AfZ0=0.2AZCu+0.9AfZ0(Ag2GeS3)+0.1AfZ0(GeS2) S0=0.2AS Cu+0.2S0(Cu)+0.9S0(Ag2GeS3)+0.1S°(GeS2)+0.1S0(S)
In a similar way, the standard integral thermodynamic functions of Cu2-xAgxGeS3 solid solutions were calculated for x = 0.4; 0.6; 1.6;
1.8 compositions. The results are presented in Table 11.
Fig.8. For calculation of integral thermodynamic functions of phases in the Cu2GeS3- Ag2GeS3
system
Table 11. Standard integral thermodynamic formation functions and standard entropies of the Cu2GeS3 and Ag2GeS3 compounds and (Cu2GeS3)x(Ag2GeS3)1-x solid solutions [167]
Composition -AfG°(298K) -AfH°(298K) S°(298K) J-K-1-mol-1
kJ-mol-1
Cu2GeS3 211.3+2.4 213.7+2.3 190.3+5.5
(Cu2GeS3)0.9(Ag2GeS3)0.1 212.2+2.1 210.7+2.2 199.9+5.2
(Cu2GeS3)0.8(Ag2GeS3)0.2 213.3+2.1 209.6+2.2 209.4+5.7
(Cu2GeS3)0.7(Ag2GeS3)0.3 214.0+2.1 208.2+2.2 219.1+5.8
(Cu2GeS3)0.2(Ag2GeS3)0.8 208.9+2.1 200.7+2.2 235.8+8.0
(Cu2GeS3)0.1(Ag2GeS3)0.9 207.4+2.1 199.6+2.2 238.3+8.3
Ag2GeS3 206.0+2.1 198.0+2.2 239.1+8.8
5. Copper chalcogenides with arsenic subgroup elements
Cu-As(Sb)-chalcogen systems attract close attention of researchers for two reasons. Firstly, the compounds of these systems and phases based on them are valuable environmentally friendly functional materials with photoelectric, optical [176-192] and thermoelectric [193-202] properties. Secondly, many known ternary compounds of these systems occur in nature in the form of minerals: enargite and lucionite Cu3AsS4; tennantite
Cu12As4S31, tetrahedrite Cu12Sb4S31; chalcostibite CuSbS2; synnergite Cu6As4S9; lautite CuAsS, etc. These mineral compounds are of great interest for mineralogy and geochemistry and provide valuable information about the physical conditions on Earth at the time of their occurrence [36, 37].
Copper-arsenic (antimony) sulfides [176192] are considered promising candidates for use as ^-type absorbers in solar cells due to the wide availability and environmental friendliness of the raw material, suitable band gap and high absorption coefficient. The suitable band gap of
these phases indicates the prospect of their application also as wide-bandgap semiconductors in third-generation photovoltaic devices. The largest number [184-191] of works is devoted to chalcostibite CuSbS2, which is considered as a substitute material for CuInS2 due to its similar optical properties and the additional advantage of a higher content of antimony in the Earth and its lower cost compared to indium.
Synthetic analogues of multiple copper minerals [193-198], as well as solutions and composites based on them [198-202] have low thermal conductivity and an anistropic crystal structure and exhibit promising thermoelectric properties. Thus, in review [198], it was noted that by 2015, zT values of the order of ~1.0 at ~723 K were achieved for a number of natural and doped tetrahedrite materials, which is comparable to conventional ^-type thermoelectric materials. The authors of [202] proposed a new concept for increasing the stability and efficiency of copper thermoelectrics, which consists in producing composites of the "copper chalcogenide-copper tetrahedrite" type. According to these authors, the proposed solution can successfully block excessive migration of copper and stabilize the composition and properties of the material during subsequent thermal cycles.
It should also be noted that, according to a number of studies, copper-bismuth chalcogenides, in particular CuBiS2,
demonstrate good photothermal properties and an anticancer effect [34]. Due to their high X-ray attenuation coefficient, these compounds have the ability to visualize computed tomography [35].
5.1. The Cu-As-X systems
The Cu-As-S system. Numerous works on phase equilibria and properties of ternary phases in the Cu-As-S system covering the period until the early 90s of the last century are summarized in [21, 203]. It is shown that the available data on the Cu2S-As2S3 phase diagram section are contradictory and differ from each other both in the number and composition of ternary compounds, and in the temperatures and nature of their melting. In particular, it was shown in [204] that this system is quasi-binary and is characterized by the formation of ternary compounds Cu5AsS4, Cu3AsS3, Cui2As4Si3, Cu4As2S5 and Cu6As4S9. The authors of [203], taking into a number of studies, presented a slightly different version of the phase diagram from [204], according to which there are 3 ternary compounds in the system: Cu12As4S13, Cu4As2S5 and Cu6As4S9. It should be noted that the composition of the Cu12As4S13 phase is outside the plane of this section, which casts doubt on the data [203] on its quasi-binarity. [205] presented a new review of the literature on the Cu-As-S system and carried out a critical assessment and thermodynamic modeling of the phase diagram.
Fig. 9. Diagrams of solid-phase equilibria for the Cu-As-S and Cu-As-Se systems
The studies [206-209] published by our study of phase equilibria and thermodynamic research team the results of a comprehensive properties of the Cu-As-S system were
presented. The solid-phase equilibrium diagram Cu6As4S9 and CuAsS compounds. (Fig. 9) shows ternary Cu3AsS4, Cu12As4S13,
Table 12. Standard thermodynamic functions of formation and standard entropies of the ternary _phases of the Cu-As-S(Se) systems_
Compound -Af G0 (298K) -A H0(298K) S0 (298K), JK-1mol-1 Ref.
KJmol-1
Cu?AsS4 (enargite) 179.2±0.6 172.2±2.6 278±8 [208, 209]
211.6 215.7 276.6 [216]
230.4 224.0 285.0 [205]
179.0 256.4 [37]
277.2 [217]
Cu6As4S9 (synnerite) 445.3±1.6 434.6±7.5 668±22 [208, 209]
517.8 505.1 673.0 [205]
Cu12As4S13 (tennantite) 701.8±2.5 673.7±10.7 1050±13 [208, 209]
CuAsS (lautite) 69.5±0.3 64.1±1.7 109±5 [208, 209]
76.2 76.5 100.0 [205]
Cu3AsSe4 147.3+0.5 146.3+1.5 307+13 [213]
Cu7As6Se9 441.8+2.3 446.1+11.7 970+27 [59]
CuAsSe2 61.1+0.4 62.1+1.9 149.5+4.5 [215]
66.6+0.4 67.33+2.0 150.9+6.2 [215]
Cu3AsSe3 141.8+0.5 140.0+2.0 258.5+5.6 [59]
CuAsSe 55.1+0.3 55.6+2.0 109.5+4.7 [59]
The Cu-As-Se system. Phase equilibria in this system have been studied in detail along the quasi-binary Cu2Se-As2Se3 section [21, 210, 211]. According to [210], the Cu3AsSe3 and CuAsSe2 compounds are formed in the system. Authors of [211] show the formation of the Cu3AsSe3, Cu4As2Se5 and CuAsSe2 ternary compounds.
The studies [45, 212-215] present the results of studying the phase equilibria and thermodynamic properties of the Cu-As-Se system. It has been established that it is characterized by the presence of ternary compounds Cu3AsSe3, Cu7As6Se9, CuAsSe2, Cu3AsSe4 and CuAsSe (Fig. 9).
The Cu-As-Te system. According to available data [21], no ternary compounds are formed in this system.
Table 12 shows the standard integral thermodynamic functions of copper-arsenic chalcogenides. The data sets obtained by the EDS method [208, 209] for Cu?AsS4, CusAs4S9, and CuAsS are significantly (up to 20%) lower than those given in [205] and are closer to the data in [37, 216]. The standard entropy values
presented in various papers are consistent with each other. Unfortunately, the data [37, 205, 216, 217] are presented without errors, which makes it difficult to assess their reliability. We believe that the data from [205] are greatly overestimated.
5.2. The Cu-Sb-X systems
The Cu-Sb-S system. Research of phase equilibria in the Cu-Sb-S system began at the beginning of the last century. The results of numerous studies in different years were summarized in the monograph [21] and papers [218, 219]. Phase equilibria of the Cu-S-Sb system are calculated in the recently published work [220] utilizing the CALPHAD (CALculation of PHAse Diagrams) technique and a new version of the T-diagram of the Cu2S-Sb2S3 section was presented. This diagram significantly different from previous reports.
The complete T-x-y diagram and various sections of the phase diagram, including the isothermal section at 300 K (Fig. 10), are presented by us in [221, 222]. According to their data, the system contains ternary compounds Cu3SbS4, Cu12Sb4S13, Cu14Sb4S13,
Cu3SbS3 and CuSbS2, in addition, the Cu2S- non-quasi-binary. Sb2S3 cut, in contrast to the literature data, is
Table 13. Standard thermodynamic functions of formation and standard entropy of some ternary _copper -antimony (bismut) chalcogenides_
Compound -Af G0(298K) -A H0(298K) S0 (298K), JK-1mol-1 Ref.
Kj-mol-1
Cu3SbS4 254.7 ± 2.3 247.8 ± 2.3 295.6 ± 7.0 [221]
CuSbS2 128.5 ± 2.2 126.9 ± 2.4 147.5 ± 3.8 [221]
*132.7±4.2 130.8±4.4 - [223]
130.6±6.0 131.7±5.2 - [224]
Cu12Sb4S13 958.7 ± 9.6 929.7 ± 11.2 1092.0 ± 29.0 [221]
Cu3SbS3 226.4 ± 2.3 219.0 ± 2.6 265.5 ± 7.2 [221]
*221.6±6.0 215.0±6.2 - [223]
Cu14Sb4S13 971.7 ± 9.8 984.8 ± 11.9 1018.0 ± 33.0 [221]
Cu3SbSe4 191.6±2.5 178.6±5.4 358.18 [59]
CuSbSe2 101.4±1.8 98.5±2.2 173±8 [59]
77.3±1.3 104.8±1.7 - [224]
Cu3SbSe3 175.6±2.5 164.0±5.3 311±15 [59]
CuBiS2 138.6±4.0 138.2±2.9 156±12 [45]
Cu3BiS3 213.0±4.4 209.9±5.2 264±21 [45]
CuBi3S5 248.7±1.9 248.6±5.8 421.9±7.8 [45]
CuBiSe2 107.6±0.8 105.9±2.51 189.8±2.4 [225]
Cu3BiSe3 162.5±1.2 155.9±5.7 315.0±8.5 [225]
Cu9BiSe6 324.8±3.5 313.1±18.6 659±28 [225]
Note: * - our calculation from calorimetric data [223].
Fig. 10. Diagrams of solid-phase equilibria of the Cu-Sb-S and Cu-Sb-Se systems
The Cu-Sb-Se system is characterized by the formation of ternary compounds Cu3SbSe4, CuSbSe2 and Cu3SbSe3 [21] (Fig. 10). The first two compounds melt congruently, and the third one melts incongruently via a peritectic
reaction.
The Cu-Sb-Te system. According to available data [21], no ternary compounds are formed in this system. The compound CuSbTe2 indicated in some early studies was not
subsequently confirmed. the available data is given in [21, 219].
5.3. The Cu-Bi-X systems According to the solid-phase equilibrium
The Cu-Bi-S system. Phase equilibria in diagram, the following copper-bismuth sulfides
this system have been studied in numerous exist at room temperature: CuBi3S5, CuBiS2 and
studies over more than 100 years. A review of Cu3BiS3 (Fig. 11).
UI% Hi
Fig. 11. Solid-phase equilibrium diagrams of Cu-Bi-S(Se) systems
The Cu-Bi-Se system. The paper [225] summarizes the results of all available studies on phase equilibria and presents a complete picture of phase equilibria, including the liquidus surface, a series of polythermal sections and an isothermal section at room temperature of the phase diagram (Fig. 11). In this system, as in the sulfur-containing system, three ternary compounds CuBi3Se5, CuBiSe2 and Cu3BiSe3 were identified. These compounds melt incongruently.
The Cu-Bi-Te system. According to available data [21], no ternary compounds are formed in this system.
Table 13 shows data on the standard integral thermodynamic functions of copper-antimony and medibismuth chalcogenides. For almost all of these compounds, complete sets of thermodynamic quantities were obtained using the EMF method with a Cu+ conducting electrolyte. The thermodynamic functions of CuBi3Se5, CuBiSe2 and Cu3BiSe3, determined by the EDS method [59, 221] (exception for the
G0 (298K) of the last compound) are in
good agreement with calorimetric data [223, 224].
Conclusion
This work summarizes the results of studies, including ours, on the thermodynamic properties of copper chalcogenides with heavy p1-p3 elements. It is shown that, there are mutually consistent sets of data on solid-phase equilibria and fundamental thermodynamic functions for copper chalcogenides with thallium and with elements of the germanium and arsenic subgroups. It is also noted that most of the existing works were carried out using various modifications of the equilibrium method of chemical thermodynamics - the EMF method.
Considering the exceptional importance of phase diagrams in studies by this method, in addition to thermodynamic data, this work also presents data on solid-phase equilibria of the corresponding systems.
Our analysis also showed that the thermodynamic properties of copper chalcogenides with gallium, indium and silicon have been practically not studied, and the available data are contradictory.
In conclusion, we note that the capabilities of the thermodynamic approach are not fully
used in the development of complex functional materials, in particular copper-based chalcogenides; the empirical approach often prevails. We consider it important to develop
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Acknowledgment
This work is supported by the Azerbaijan Science Foundation 1(42)-12/10/4-M-10.
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MiSiN MÜR9KK9B XALKOGENiDLORiNiN TERMODiNAMiK XASSOLORÎ
1,2,3M.B. Babanli*, 1L.F. Maçadiyeva, 1S.Z. imamaliyeva, 1D.B. Tagiyev, 1,4D.M. Babanli,
5Yu.A. Yusibov
1AR ETN akad. M. Nagiyev adina Kataliz vd Qeyri-üzvi Kimya institutu
2Baki Dövlst Universiteti
3Azdrbaycan Dövht iqtisad Universiteti
4Fransiz - Azarbaycan Universiteti (UFAZ), Azsrbaycan, Baki 5Ganc3 Dövlst Universiteti *e-mail: babanlymb@gmail.com
Misin mürakkab xalkogenidlari maraqli termoelektrik, fotoelektrik, optik, ion ke9iriciliyi va digar xassalara malik olan an mühüm ekoloji tahlükasiz funksional materiallar hesab edilirlar. £oxsayli tadqiqatlarin tahlili göstarir ki, bu birla§malarin tatbiq xüsusiyyatlarinin yax§ila§dirilmasi struktur va tarkibin manipulyasiyasi ila alagalidir. Bela proseslarin optimalla§dirilmasinin effektiv halli onlarin darin termodinamik analizini talab edir ki, bu da öz növbasinda müvafiq maddalarin fundamental termodinamik xassalari haqqinda etibarli malumatlarin olmasini labüd edir. icmalda misin bazi p^p3 elementlari ila xalkogenidlarinin termodinamik xassalari üzra tadqiqatlarin, o cümladan müalliflarin öz i§larinin naticalari ümumila§dirilmi§dir. Odabiyyat analizi göstardi ki, bu i§larin böyük aksariyyati elektrik harakat qüvvasi (EHQ) metodunun müxtalif modifikasiyalarindan istifada etmakla hayata ke?irilib. Kimyavi termodinamikanin bu tarazliq üsulu ila aparilan tacrübalarin planla§dirilmasi va onlarin malumatlarinin emali etibarli faza tarazligi manzarasi olmadan mümkün deyil. Bunu nazara alaraq, i§da termodinamik malumatlarla yana§i, EHQ üsulu ila tadqiq olunan bir sira sistemlarin bark faza tarazliqlarinin diaqramlari da taqdim edilmi§dir.
Odabiyyat tahlili göstardi ki, Cu-Tl-X, Cu-Ge(Sn)-X (X-S, Se, Te) va Cu-As(Sb, Bi)-S(Se) sistemlarinda faza tarazliqlari va ü9lü birla§malarin termodinamik xassalari haqqinda qar§iliqli tanzimlanmi§ malumatlar mövcuddur. Cu-Tl-X va Cu-Sn-Se sistemlarin ü9lü birla§malarinin termodinamik funksiyalari EHQ metodunun iki modifikasiyasi, yani iki müxtalif komponentin misin va ya talliumun (qalayin) parsial molyar funksiyalarinin tayin etmakla müayyan edilmi§diir. Misin qallium, indium va silisium ila xalkogenidlarinin termodinamik xassalari praktiki olaraq öyranilmami§dir, mövcud olan malumatlar isa ziddiyyatlidir.
A?ar sözlar: misin mürakkab xalkogenidlari, ekoloji tahlükasiz materiallar, mis asasinda ü9lü sistemlar, faza diaqramlari, termodinamik xassalar, EHQ üsulu.
ТЕРМОДИНАМИЧЕСКИЕ СВОЙСТВА СЛОЖНЫХ ХАЛЬКОГЕНИДОВ МЕДИ
1,2'3М.Б. Бабанлы*, ХЛ.Ф. Машадиева, 1С.З. Имамалиева, ХД.Б. Тагиев, 1,4Д.М. Бабанлы,
5Ю.А. Юсибов
1Институт катализа и неорганической химии им. акад. М. Нагиева МНО АР 2Бакинский государственный университет 3Азербайджанский Государственный Экономический Университет 4Французский - Азербайджанский университет (УФАЗ), Азербайджан, Баку 5Гянджинский государственный университет e-mail: *babanlymb@gmail.com
Сложные халькогениды на основе меди относятся к важнейшим экологически безопасным функциональным материалам, имеющим большой потенциал применения, благодаря интересным термоэлектрическим, фотоэлектрическим, оптическим и др. свойствам, а также ионной проводимостью. Анализ данных многочисленных исследований показывает, что улучшение прикладных характеристик этих соединений связано с манипуляцией структуры и состава. Эффективное решение вопросов оптимизации таких процессов требует их глубокого термодинамического анализа, для которого необходимы надежные данные по фундаментальным термодинамическим характеристикам соответствующих веществ. В данном обзоре обобщены результаты работ, в том числе авторов, по термодинамическим свойствам халькогенидов меди с некоторыми р1-р3 элементами. Анализ показал, что подавляющее большинство этих работ выполнено
различными модификациями метода электродвижущих сил (ЭДС). Планирование экспериментов проводимых этим равновесным методом химической термодинамики и обработка их данных невозможна без наличия надежных по фазовым равновесиям. Учитывая это в работе помимо термодинамических данных приведены также диаграммы твердофазных равновесий ряда систем, изученных методом ЭДС.
Анализ показал, что для тройных систем Си-Т1-Х, Си-Ое(Бп)-Х (Х-Б, Бе, Те) и Си-аб(8ь, Ы)-8(8е) имеются взаимосогласованные данные по фазовым равновесиям и термодинамическим функциям тройных соединений, причем для систем Си-Т1-Х и Си-Бп-Бе термодинамические функции тройных соединений определены двумя модификациями метода ЭДС путем определения парциальных молярных функций двух различных компонентов - меди и таллия(олова). В тоже время термодинамические свойства халькогенидов меди с галлием, индием и кремнием практически не изучены, а имеющиеся данные противоречивы.
Ключевые слова: сложные халькогениды меди, экологически безопасные материалы, тройные медьсодержащие системы, фазовые диаграммы, термодинамические свойства, метод ЭДС.
