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AZORBAYCAN KIMYA JURNALI № 3 2018
ISSN 2522-1841 (Online) ISSN 0005-2531 (Print)
with the stoichiometric composition of FeGa2Se4 melts at 1285 K and forms eutectics with a- and P-phases based on the initial binary compounds.
I IDC 546 (72.681.682.23)
REFINEMENT OF THE PHASE DIAGRAMS OF THE FeSe-Ga2Se3 AND
Ga2Se3-In2Se3 SYSTEMS
F.M.Mainmadov
M.Nagiev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan
faikmamadov@mail. ru Received 22.02.2018
The quasi-binary systems FeSe-Ga2Se3 and Ga2Se3-In2Se3 were reinvestigated by using DTA as well as
RFA methods and their refined T-x phase diagrams were constructed. A comparative analysis of the
results obtained with literature data is carried out.
Keywords: FeSe-Ga2Se3 and GajSes-In^Ses systems, phase diagram, iron, gallium and indium
selenides.
Introduction
Multi component chalcogenides and phases based on them are advanced functional materials possess thermoelectric, photoelectric, optical, magnetic and other functional properties [1-6].
AB2X4 compounds (A - Mn, Fe, Co, Hi; B - p -p elements; X - chalcogen) are characterized by phenomena of electronically or optically governed magnetism; so they are promising materials for the production of wide-gap converters of optical radiations, light modulators, photodetectors, sensors, and data storage devices as well as spintronic and other magnetic-field-controllable functional devices [7-14].
In order to search and develop the phy-sicochemical basis for the production of new magnetic semiconductors, we undertook a phase equilibria study in the MX-Ga2X3-In2X3 (M - Mn, Fe; X - S, Se, Te) systems. The preliminary results obtained [15, 16] showed the formation of wide regions of solid solutions along the MGa:X4-M 1112X4 sections of these systems. The analysis of the literature data showed that the phase diagrams of some boundary quasibinary systems of these quasiternary systems need to be refined.
In this paper, new refined T-x diagrams of the quasibinary FeSe-Ga2Se3 and Ga2Se3-In2Se3 systems are presented and compared with literature data.
Results and its discussion
FeSe-Ga2Se3 system (Figure 1) belongs to the distectic type. The intermediate y-phase
1278
FeSe
Ga,Se,
40 60 mol % Ga^Se,
Fig.l. Phase diagram of the FeSe-Ga2Se3 system.
The eutectics ei and e2 have compositions of 27 and 67 mol% Ga2Se3 and crystallize at 1220 and 1175 K, respectively. At the eutectic temperatures, the homogeneity regions of the a-, y- and p-phases cover the composition intervals of 0-4; 43-59 mol% (1220 K) and 75-100 mol % Ga2Se3. At 725 K a eutectoid reaction ao (FeSe)i+y takes place, where (FeSe)i is a low-temperature modification of iron monoselenide.
The homogeneity regions of the P- and y-phases decrease slightly with a decrease in temperature and at room temperature are 49-57 and 80-100 mol % of Ga2Se3, respectively.
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Comparison with the data of [17-19] shows that the T-x diagram of this system constructed by us qualitatively coincides with the results of [17]. However, the temperature of the distectic and eutectoid equilibria, determined by us, significantly differs from those given in [17] (1318 and 1223 K, respectively). We also did not confirm the immiscibility region specified by authors of [17]. Moreover, the data of [19], according to which the FeGavSej compound melts by peritectic decomposition are not confirmed by us. Authors of [18] showed congruent melting ofFeGa2Se4 at 1283 K. This practically coincides with our data.
Ga2Se3-In2Se3 (Figure 2). A characteristic feature of this system is the presence of wide regions of solid solutions based on Ga2Se3 (a-phase), an intermediate modification of In2Se3 (yi-phase), and an intermediate y2-phase. The latter decomposes on a solid-phase reaction at 1120 K. The Yi-phase is formed by peritectic reaction at 1145 K. The peritectic point (P) has a composition of 65 mol % In2Se3. At 1100 K the homogeneity regions of the a- and yi-phases cover the ranges of 0-25 and 55-88 mol % In2Se3, respectively.
Ga3Sej 20 40 60 SO In,Se3 mol% ln,Se3
Fig.2. Phase diagram of the Ga2Se3-In2Se3 system.
The formation of the yi-phase is accompanied by temperature increasing of the phase transition at 1005 K to 1125 K and a decreasing of the temperature of the phase transition at 920 to 470 K. The latter corresponds to the eutectoid equilibrium (3'o-P+yi. Solubility based on low-temperature modifications of In2Se3 does not exceed 2-3 mol %.
Until our investigation, two variants of the phase diagram of the Ga?Se.! In^Se.! system were known [20, 21]. According to [20], wide areas (45 mol %) of solid solutions (a-phase) and intermediate phase (y) with a homogeneity region of 50-88 mol % based on Ga2Se3 are formed in the system. However, a detailed X-ray study [21] showed that the region of homogeneity of the a- phase does not exceed 20 mol %, while y-phase is a solid solution based on the intermediate modification of In2Se3. In addition, authors of [21] discovered a new intermediate phase with a relatively narrow region of homogeneity (35-42 mol % In2Se3). The low-temperature region of the phase diagram in [21] has not been studied.
The phase diagram of Ga2Se3-In2Se3 system constructed by us, combines the elements of both variants of the phase diagram. In this case, the character of solid-phase equilibria almost completely coincides with the data [21]. However, the distectic maximum of melting of the yi-phase indicated in [21] is not confirmed by us.
Conclusion
FeSe-Ga2Se3 and Gap^-feaSea systems were re-studied by means of DTA and RFA methods taking into account the inconsistency of the available literature data on phase equilibria. New refined variants of the phase diagrams of these systems were constructed based on the experimental results obtained, and taking into account earlier data. Comparative analysis with literature data was carried out.
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FeSe-Ga2Se3 (In2Se3) va Ga2Se3-In2Se3 КЛ/.Л DiAQRAMLARININ D0QiQL0§DiRiLM9Si
F.M.Mammadov
FeSe-Ga2Se3 (In2Se3) \o Ga2Se3-In2Se3 kvazibinar sistcmlori DTA \o RFA metodlan ilo ycnidon lodqiq cdilmis \o onlann doqiqlosdirilmis T-x faza diaqramlan qurulmusdur. O!do cdilmis noticolorin odobiwat lmlumatlan ilo muqayisali tohlili apanlmisdir.
Agar si'n.br: FeSe-Ga2Se3 уэ Ga2Se3- In2Se3 sistembri, faza diaqrarm, damir, qallium Щ mdhmnm selenidbri.
АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 3 2018
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УТОЧНЕНИЕ ФАЗОВЫХ ДИАГРАММ СИСТЕМ FcSe-Ga2Sc3 И Ga2Se3-In2Se3
Ф.М.Мамедов
Методами ДТА и РФА повторно изучены квазибинарные системы FeSc-Ga2Se3 (In2Se3) и Ga2Se3-In2Se3 и построены их уточненные Г-х-фазовые диаграммы. Проведен сравнительный анализ полученных результатов с литературными данными.
Ключевые слова: системы FeSe-Ga2Se3 и GajSej-In^Ses, фазовая диаграмма, селениды железа, галлия, индия.
This work was supported by the Science Development Foundation under the President of the Republic of Azerbaijan - Grant EIF/MQM/Elm- Tehsil-1-2016-1(26)- 71/01/4-M-33
