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AZERBAIJAN CHEMICAL JOURNAL № 2 2019
UDC 546.19:546.682.22.23
PHASEFORMATION IN THE SYSTEM InAs2S3Se-InAs2Se3S AND PROPERTIES OF OBTAINED PHASES
I.LAliyev, O.M.Aliyev, R.S.Mahammadrahimova
M.Nagiyev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan
[email protected] Received 05.10.2018
Compound InAs2S2Se2 was found during studying the system InAs2S3Se-InAs2Se3S. It was established that the compound InAs2S2Se2 melts congruently at 615 K. crystallizes in tetragonal syngony with lattice parameters: a=9.22±0.01, c=5.81±0.002 Â; Z=3. Coordinates of eutectic points: 40 mol % InAs2Se3S, T=548 K and 60 mol % InAs2Se3S, T=580 K. Narrow solid solution ranges are formed on the basis of primary components. Solid solutions based on InAs2S3Se at room temperature reach up to 5 mol %, but on the basis of InAs2Se3S - up to10 mol %.
Keywords: system, quasi-binary, solid solution, syngony, microhardness.
https://doi.org/10.32737/0005-2531-2019-2-44-47
Indium selenide InSe and arsenic chalco-genides (As2S3, As2Se3) are ones of prospective semiconductor compounds, possessing photosensitive and acousto-optical properties [1-8]. Therefore, study of the interaction in the system InAs2S3Se - InAs2Se3S is of scientific and practical interest.
Earlier we have studied some internal sections of quasi-binary system As2S3-InSe-As2Se3 [9-11]. Compound InAs2S3Se has a monoclinic structure, unit cell parameters: a=12.32, b= 11.43, c=6.62 A; P=107° [12].
Aim of the present work is to construct phase diagram of the system InAs2S3Se-InAs2Se3S in all ranges of concentrations and to study physical and chemical properties of the new phase.
Experimental part
High-purity chemical agents: arseni-um-B3, indium In-000, sulphur e.p. - 19-3, selenium e.p. - 16-4 were used for synthesis. Quaternary alloys were synthesized from a ligature InAs2S3Se and InAs2Se3S previously synthesized from the elements evacuated and exhausted in quartz ampoules at 650-1000 K depending on the alloy composition. After synthesis cast specimens were annealed at 500 K for two weeks.
Annealed alloys were studied using the methods of DTA (NTR-73 with an accuracy of
3 -5 K, chromel-alumel thermocouple, calcined Al2O3 was used as a standard. Heating rate - 90 C/min). X-ray phase (D2 PHASER Bruker. CuXa-radiation, Ni-filter), MSA (MIM-8). Mi-crohardness of phases was measured on the de-vite PMT-3 with an accuracy of 5%, density of examples was determined by pycnometer method.
Results and discussion
T-x phase diagram of system InAs2S3Se-InAs2Se3S constructed on the basis of data physical and chemical analysis is given in Figure 1. As shown in Figure, congruently melting compound InAs2S2Se2 which divides the system into two secondary systems InAs2S3Se-InAs2S2Se2 and InAs2S2Se2-InAs2Se3S.
Both secondary systems belong to eutectic type with limited solubility based on primary ternary compounds. Coordinates of eutectic points: 40 mol % InAs2Se3S, T=548 K and 60 mol % InAs2Se3S, 7=580 K. According to X-ray phase (Figure 2) and microstructural analysis, sample of the composition 50 mol % InAs2S3Se + 50 mol % InAs2Se3S is one-phase.
It was established that compound InAs2S2Se2 crystallizes in tetragonal syngony with unit cell parameters of a=9.22, c=5.81 A; Z=3, V=493.9 A3. Calculation of X-ray pattern of the compound InAs2S2Se2 is presented in Table 1.
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I.I ALIYEV et al.
According to the data of the microstructural analysis the samples containing 0-5, 50 and 90 -100 mol % InAs2Se3S are one-phase. At the concentration range of 0-50 mol % InAs2Se3S a-phase (solid solutions on the basis of InAs2S3Se) and compound InAs2S2Se2 crystallize jointly but at the concentration range of 50-90 mol % InAs2Se3S two-phase alloys crystallize jointly (P+InAs2S2Se2). P-solid solutions belong to the type of substitution and crystallize in tetragonal syngony. Crystal lattice parameters vary in the ranges of a=9.36-9.42 A, c=6.15-6.29 A. Some physical and chemical properties of alloys of the system InAs2S3Se-InAs2Se3S are given in the Table 2.
Three sets of values are distinguished on microhardness measurements of cast alloys of InAs2S3Se-InAs2Se3S system (Table 2). The first of those is relevant to microhardness of a-phase (solid solutions basis of on the InAs2S3Se) (1230-1240) MPa, value of micro-hardness 1300 MPa corresponds to the new phase InAs2S2Se2, for P-phase it corresponds to (1170-1180) MPa.
Thus, T-x diagram of InAs2S3Se-InAs2Se3S system was studied and constructed and formation of InAs2S2Se2 compound con-gruently melting at 615 K and crystallizing in a tetragonal syngony was established.
Table 1. Calculation of X-ray pattern of compound InAs2S2Se2
I, % dex.? A dcal. ? A hkl
26 9.2214 9.2214 100
4 5.8075 5.8075 001
100 4.6139 4.6139 200
7 3.3602 3.3634 121
4 3.2513 3.2599 220
10 2.8234 2.8241 221
8 2.7229 2.7257 301
9 1.9311 1.9367 003
4 1.9015 1.8956 103
6 1.8470 1.8440 500
4 1.7836 1.7857 203
3 1.5401 1.5366 600
Table 2. Results of DTA, InAs2S3Se-InAs2Se3S
microhardness measuring and density determination of alloys of the system
Composition, mol. % Thermal effects, K Density, 103kg/m3 Microhardness of phases, MPa
InAs2S3Se InAs2Se3S a InAs2Se2S2 ß
P=0.15 N
100 0.0 643 4.66 1240 - -
97 3.0 635 4.66 1240 - -
95 5.0 600.643 4.66 1240 - -
90 10 550.640 4.70 1235 - -
80 20 548.625 4.70 1230 - -
70 30 548.600 4.70 1230 - -
60 40 548 4.70 Eutec. Eutec. -
55 45 548. 605 4.70 - 1300 -
50 50 615 4.70 - 1300 -
45 55 580.590 4.72 - 1300 -
40 60 580 4.72 - Eutec. Eutec.
35 65 580.670 4.74 - - -
30 70 580.770 4.75 - 1290 -
20 80 580.900 4.77 - 1290 1180
10 90 700.1025 4.78 - 1290 1180
5.0 95 890.1085 4.80 - - 1180
3.0 97 985.1100 4.82 - - 1175
0.0 100 1118 4.82 - - 1170
AZERBAIJAN CHEMICAL JOURNAL № 2 2019
PHASEFORMATION INTHE SYSTEM InAs2S3Se-InAs2Se3S
47
References
1. Seema Kandpal Kushwaha R. P. S. Photoacoustic spectroscopy of thin films of As2S3, As2Se3 and GeSe2. Indian Academy Sci. PRAM ANA J. Phys. 2007. V. 69. No 3. P. 481-484.
2. Koziuhin S.A., Fairushin A.R., Voronkov E.N. Svoistva amorfnykh plenok halkogenidov my-shiaka, modifitcirovannykh kompleksnymi soedi-neniiami redkozemelnykh elementov. Fizika i tekhnika poluprovodnikov. 2005. T. 39. № 8. S. 2012-2016.
3. Svechnikov S.V., Himinetc V.V., Dovgoshei N.I. Slozhnye nekristallicheskie halkogenidy i halko-galogenidy i ikh primenenie v optoelektronike. Kiev: Nauk. Dumka. 1992. 375 s.
4. Abdinov A.Sh., Eivazova T.Kh., Babaeva R.F. Vliianie legirovaniia redkozemelnymi atomami na ishodnuiu i sensibilizirovannuiu IK-chuvstvitelnost sloistykh kristallov selenida indiia. Fizika. 2006. № 1. S. 62-65.
5. Sanchez-Royo I.F., Segura A., Lang O. Optical and photovoltaic properties of InSe thin films prepared by van-der Waals epitaxy. J. Appl. Phys. 2006. V. 90. P. 2818-2823.
6. Madelung O. Semiconductors. Data handbook.
Springer. 2004. 691 p.
7. Littler I. C. M., Fu L., B. Magi E. C. Pudo D. Eggleton B. J. Widely tunable, acousto-optic resonances in Chalcogenide As2Se3 fiber. Optics Express. 2006. V. 14. Issue 18. P. 8088-8095.
8. Lovu M., Shutov, Rebeja S., Colomeyco E., Popescu M. Optical adsorption and photoconductivity of As2Se3-Sn. J. Optoelectronics and Adv. Mater. 2000. V. 2. Issue 1. P. 53-58.
9. Rustamov P.G., Safarov M.G., Aliev I.I. Sistema As2S3-InSe. Zhurn. neorgan. himii. 1980. T. 25. № 4. S. 1073-1077.
10. Aliev I.I., Magammedragimova R.S. Harakter vzaimodeistviia i stecloobrazovaniia v sisteme As2Se3-InAs2S3Se. Himicheskie problemy. 2006. № 3. S. 500-503.
11. Aliev I.I., Magammedragimova R.S., Farzaliev A.A., Veliev Dzh.A. Fazovaia diagramma soedi-neniia sistemy In3As2Se6-In3As2S3Se3. Zhurn. neorgan. himii. 2009. T. 54. № 4. S. 638-640.
12. Aliev I.I. Fiziko-himicheskie osnovy polucheniia novykh materialov v sistemakh halkogenidov myshiaka s halkogenidami kadmiia, indiia i talliia. Diss. ... dokt. him. nauk. Baku. INFKH. 1992. 380 s.
InAs2S2Se-InAs2Se3S SISTEMINDO FAZAOMOLOGOLMO VO ALINMI§ FAZALARIN XASSOLORI
LLOliyev, O.M.Oliyev, R.S.Mahammadrahimova
InAs2S3Se-InAs2Se3S sisteminin öyranilmasi naticasinda InAs2S2Se2 birla§masinin alindigi a§kar edilmi§dir. Müayyan edilmi§dir ki, InAs2S2Se2 birla§masi 615 K temperaturda konqruyent ariyir va tetraqonal sinqoniyada kristallaíjir, elementar qafas parametrlari: а=9.22±0.01, c=5.81±0.002 Á; Z=3. Sistemda amala galan iki evtektikanin tarkibi 45 mol % InAs2Se3S, Т=580 К va 60 mol % InAs2Se3S. Т=548 К-dir. ilkin komponentlar asasinda bark mahlullarin ensiz sahalari amala galmi§dir. Otaq temperaturunda InAs2S3Se asasinda 5 mol %, InAs2Se3S asasinda isa 10 mol % bark mahlul amala galir.
Agar sözlzr: sistem, kvazibinar, Ьэгк шэк1ы1, sinqoniya, mikrobarklik.
ФАЗАОБРАЗОВАНИЕ В СИСТЕМЕ InAs2S3Se-InAs2Se3S И СВОЙСТВА ПОЛУЧЕННЫХ ФАЗ
И.И.Алиев, О.М.Алиев, Р.С.Магомедрагимова
Соединение InAs2S2Se2 было обнаружено при изучении системы InAs2S3Se-InAs2Se3S. Установлено, что соединение InAs2S2Se2 плавится конгруэнтно при температуре 615 К. кристаллизуется в тетрагональной сингонии с параметрами. элементарной ячейки: а=9.22±0.01, с=5.81±0.002 Á; Z=3. Координаты эвтектических точек: 45 мол. % InAs2Se3S, 7=580 К и 60 мол. %. InAs2Se3S. 7=548 К. На основе исходных компонентов образуются узкие области твердых растворов. Твердые растворы на основе InAs2S3Se при комнатной температуре доходят до 5 мол. %, а на основе InAs2Se3S - до 10 мол. %.
Ключевые слова: система, квазибинарный. твердый раствор, сингония, микротвердость.
АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 2 2019
