Effect of temperature variation on shift and broadening of exciton band in Cs₃Bi₂I₉ layered crystals

The exciton reflection spectra of Cs₃Bi₂I₉ layered crystals is investigated in the temperature region 4.2–300 K with light polarization E ⊥ c. It is estimated that the energy gap Eg equals 2.857 eV (T = 4.2 K) and the exciton binding energy Ry is 279 meV. A nontraditional temperature shift of...

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Автори: Machulin, V.F., Motsnyi, F.V., Peresh, E.Yu., Smolanka, O.M., Svechnikov, G.S.
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Опубліковано: Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України 2004
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Цитувати:Effect of temperature variation on shift and broadening of exciton band in Cs₃Bi₂I₉ layered crystals / V.F. Machulin, F.V. Motsnyi, E.Yu. Peresh, O.M. Smolanka, G.S. Svechnikov // Физика низких температур. — 2004. — Т. 30, № 12. — С. 1283–1286. — Бібліогр.: 30 назв. — англ.

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Digital Library of Periodicals of National Academy of Sciences of Ukraine
id nasplib_isofts_kiev_ua-123456789-120368
record_format dspace
spelling Machulin, V.F.
Motsnyi, F.V.
Peresh, E.Yu.
Smolanka, O.M.
Svechnikov, G.S.
2017-06-12T06:29:41Z
2017-06-12T06:29:41Z
2004
Effect of temperature variation on shift and broadening of exciton band in Cs₃Bi₂I₉ layered crystals / V.F. Machulin, F.V. Motsnyi, E.Yu. Peresh, O.M. Smolanka, G.S. Svechnikov // Физика низких температур. — 2004. — Т. 30, № 12. — С. 1283–1286. — Бібліогр.: 30 назв. — англ.
0132-6414
PACS: 64.70.Kb, 71.35.Cc, 78.40.Fy
https://nasplib.isofts.kiev.ua/handle/123456789/120368
The exciton reflection spectra of Cs₃Bi₂I₉ layered crystals is investigated in the temperature region 4.2–300 K with light polarization E ⊥ c. It is estimated that the energy gap Eg equals 2.857 eV (T = 4.2 K) and the exciton binding energy Ry is 279 meV. A nontraditional temperature shift of Eg(T) for the layered substances is found for the first time. It is learned that this shift is described very well by the Varshni formula. A transition region in the temperature broadening of the half-width H(T) of the exciton band with the increase of temperature is registered in the interval between 150 and 220 K. It is shown that this region may be identified as the heterophase structure region where ferroelastic and paraelastic phases coexist. A surge of H(T) at the point of the ferroelastic phase transition (Tc = 220 K) is also observed.
en
Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України
Физика низких температур
Квантовые эффекты в полупpоводниках и диэлектриках
Effect of temperature variation on shift and broadening of exciton band in Cs₃Bi₂I₉ layered crystals
Article
published earlier
institution Digital Library of Periodicals of National Academy of Sciences of Ukraine
collection DSpace DC
title Effect of temperature variation on shift and broadening of exciton band in Cs₃Bi₂I₉ layered crystals
spellingShingle Effect of temperature variation on shift and broadening of exciton band in Cs₃Bi₂I₉ layered crystals
Machulin, V.F.
Motsnyi, F.V.
Peresh, E.Yu.
Smolanka, O.M.
Svechnikov, G.S.
Квантовые эффекты в полупpоводниках и диэлектриках
title_short Effect of temperature variation on shift and broadening of exciton band in Cs₃Bi₂I₉ layered crystals
title_full Effect of temperature variation on shift and broadening of exciton band in Cs₃Bi₂I₉ layered crystals
title_fullStr Effect of temperature variation on shift and broadening of exciton band in Cs₃Bi₂I₉ layered crystals
title_full_unstemmed Effect of temperature variation on shift and broadening of exciton band in Cs₃Bi₂I₉ layered crystals
title_sort effect of temperature variation on shift and broadening of exciton band in cs₃bi₂i₉ layered crystals
author Machulin, V.F.
Motsnyi, F.V.
Peresh, E.Yu.
Smolanka, O.M.
Svechnikov, G.S.
author_facet Machulin, V.F.
Motsnyi, F.V.
Peresh, E.Yu.
Smolanka, O.M.
Svechnikov, G.S.
topic Квантовые эффекты в полупpоводниках и диэлектриках
topic_facet Квантовые эффекты в полупpоводниках и диэлектриках
publishDate 2004
language English
container_title Физика низких температур
publisher Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України
format Article
description The exciton reflection spectra of Cs₃Bi₂I₉ layered crystals is investigated in the temperature region 4.2–300 K with light polarization E ⊥ c. It is estimated that the energy gap Eg equals 2.857 eV (T = 4.2 K) and the exciton binding energy Ry is 279 meV. A nontraditional temperature shift of Eg(T) for the layered substances is found for the first time. It is learned that this shift is described very well by the Varshni formula. A transition region in the temperature broadening of the half-width H(T) of the exciton band with the increase of temperature is registered in the interval between 150 and 220 K. It is shown that this region may be identified as the heterophase structure region where ferroelastic and paraelastic phases coexist. A surge of H(T) at the point of the ferroelastic phase transition (Tc = 220 K) is also observed.
issn 0132-6414
url https://nasplib.isofts.kiev.ua/handle/123456789/120368
citation_txt Effect of temperature variation on shift and broadening of exciton band in Cs₃Bi₂I₉ layered crystals / V.F. Machulin, F.V. Motsnyi, E.Yu. Peresh, O.M. Smolanka, G.S. Svechnikov // Физика низких температур. — 2004. — Т. 30, № 12. — С. 1283–1286. — Бібліогр.: 30 назв. — англ.
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fulltext Fizika Nizkikh Temperatur, 2004, v. 30, No. 12, p. 1283–1286 Effect of temperature variation on shift and broadening of exciton band in Cs3Bi2I9 layered crystals V.F. Machulin1, F.V. Motsnyi1, E.Yu. Peresh2, O.M. Smolanka1, and G.S. Svechnikov1 1 V. Lashkaryov Institute of Semiconductor Physics of the National Academy of Sciences of Ukraine 41 Nauky Ave., Kyiv 03028, Ukraine E-mail: motsnyi@sun.semicond.kiev.ua 2 Uzhgorod National University, Chemical Faculty, 46 Pidgirna Str., Uzhgorod 88000, Ukraine Received February 26, 2004, revised April 29, 2004 The exciton reflection spectra of Cs3Bi2I9 layered crystals is investigated in the temperature re- gion 4.2–300 K with light polarization E � c. It is estimated that the energy gap Eg equals 2.857 eV (T = 4.2 K) and the exciton binding energy Ry is 279 meV. A nontraditional temperature shift of Eg(T) for the layered substances is found for the first time. It is learned that this shift is described very well by the Varshni formula. A transition region in the temperature broadening of the half-width H(T) of the exciton band with the increase of temperature is registered in the inter- val between 150 and 220 K. It is shown that this region may be identified as the heterophase struc- ture region where ferroelastic and paraelastic phases coexist. A surge of H(T) at the point of the ferroelastic phase transition (Tc = 220 K) is also observed. PACS: 64.70.Kb, 71.35.Cc, 78.40.Fy 1. Introduction Cs3Bi2I9 crystals belong to an extensive family of little-studied three-component A3B2X9 layered com- pounds (A are alkaline atoms, B = As, Sb, Bi, Fe, Cr, Mo, or W, and X = Br, Cl or I) [1,2], which are kin- dred to the well-known perovskites. Interest in these crystals is caused by the manifestation of a ferroelastic second-order phase transition at the temperature Tc = = 220 K [2–4] accompanied by a reversible change of crystal symmetry class from hexagonal 6/mmm to centrosymmetric monoclinic 2/m, the prediction of an incommensurate phase at T < 220 K [1,5], and the possibilities of practical use in recorder systems, pres- sure and �-emission sensors, and acousto- and opto- electronics. The optical data on Cs3Bi2I9 crystals concern to the birefrigence [2], exciton states [6,7], phonon spectra [8], and low-temperature optical characteristics [9]. On the other hand, one of the important physical properties of layered crystals is the anomalous tempe- rature dependence of energy gap Eg(T), which in- creases at T < Òm and decreases at T > Òm. For differ- ent layered crystals Tm varies within a temperature range of 30–45 K [10–14]. The phenomenon originates from high anisotropy of the chemical bonding due to the strong ionic—covalent bonding in separate sand- wich layers and the weak van der Waals binding between neighboring sandwiches. This is confirmed by the presence of low-frequency optical vibrations in the Raman spectra of layered crystals [8,13,15–18] which determine the exciton—phonon interaction [14,19,20], spin—lattice relaxation [21], temperature dependence of electron paramagnetic resonance (EPR) spectra [21,22], and also a large difference in linear broaden- ing coefficients in directions perpendicular to the lay- ers and in the planes of the layers [23]. Anomalous temperature behavior of Eg(T) can be explained on the basis of the essential influence of anharmonic opti- cal vibrations of the layered lattice starting at low temperature and of low-frequency optical phonons starting at higher temperatures [14,24]. However, this temperature dependence has not been studied for A3B2X9 compounds in general and for Cs3Bi2I9 crys- tals in particular. The aim of this paper is to study the temperature behavior of the exciton band of Cs3Bi2I9 layered crys- tals. © V.F. Machulin, F.V. Motsnyi, E.Yu. Peresh, O.M. Smolanka, and G.S. Svechnikov, 2004 2. Experimental Cs3Bi2I9 layered crystals were grown by the Bridgman method. The peculiarities of this technology are given in [25,26]. Samples with dimensions approxi- mately 7�5�0.02 mm were cut off from a bulk crystal in air with a blade. Special care was taken to avoid de- formations. The samples had the mirror-smooth sur- face with optical c axis perpendicular to cleavage sur- face. The reflection spectra were measured in the heating regime. They were recorded with an auto- mated experimental setup based on a MDR-23 mono- chromator in the energy interval of 2.0–3.5 eV in the temperature range of 4.2–300 K and with light polar- ization E � c. The energy resolution was better than 0.5 meV. The relative error of measurement of the re- flection spectra did not exceed 3%. The temperature was stabilized with accuracy better than 0.1 K. The resonance energies of the exciton absorption bands were determined from the inflection point of the exciton oscillation with quantum number n = 1 by set- ting the second derivative of the reflection coefficient with respect to energy equal to zero (d2R/dE2 = 0). The inflection point found in such a way coincides up to T � 200 K with the one determined in the ordinary way as the half energy interval or the half distance on the reflectance scale between the extrema of the exciton oscillation. The half-width H(T) of the exci- ton absorption band was found as the energy diffe- rence between the maximum and the minimum of the fundamental exciton oscillation. The insertion errors in the measured values of the temperature variations of the energy position of the exciton band Eex(T) and its half-width are insignificant [11] and do not influ- ence their qualitative course. 3. Results and discussion A typical reflection spectrum at 4.2 K and E � c and the dependence of [�2(�)��]2 as a function of en- ergy �� for Cs3Bi2I9 crystals are shown in Fig. 1. The intense oscillation with inflection point at energy 2.578 eV and the two shorter-wave length maxima at energies of 2.961 and 3.073 eV (Fig. 1,a) are caused by excitons in the ground state (n = 1) and interband electron transitions, respectively [6,7]. On the basis of this spectrum, the extrapolation by the Yahoda method*, and the Kramers—Kronig relations, we have previously [9] found the real �1(�) and imagi- nary �2(�) parts of the complex dielectric function �(�). Knowing �2(�), we estimated the direct band gap Eg of Cs3Bi2I9 crystals at 4.2 K and E � c. The dependence of [�2(�)��]2 as a function of energy �� was constructed in accordance with [27] (Fig. 1,b). One can see three intense bands with maxima at ener- gies of 2.548, 2.986, and 3.079 eV. The calculated spectrum satisfactorily correlates with the experimen- tal reflection spectrum. The value of Eg in such a case is estimated as the energy of the cut off. It equals 2.857 eV. The binding energy Ry of the exciton is found as the difference between Eg and the maximum of the exciton band, that is Ry = 279 meV. It should be noted that Ry in the Cs3Bi2I9 crystals is high, and higher than in basic BiI3 (Ry = 144 meV) [19]. This may be explained by that fact that Cs3Bi2I9 crystals are alkali halide compounds. In such substances the polar type of chemical bonding takes place, and there- fore Ry may be high. 1284 Fizika Nizkikh Temperatur, 2004, v. 30, No. 12 V.F. Machulin, F.V. Motsnyi, E.Yu. Peresh, O.M. Smolanka, and G.S. Svechnikov * The optical functions of a system of two noninteracting classical oscillators were simulated taking into account the traditional extrapolations by the Philipp—Taft and Yahoda methods. It was found that the functions are in good agreement with the model functions only in the second case. 0 2.2 2.4 2.6 2.8 3.0 3.2 Ry b 5 10 15 20 25 30 35 40 R ,% a E, eV 200 400 600 800 E = 2.857 eVg [ ( ) , e V � � � � 2 � 2 2 Fig. 1. Reflection spectrum (T = 4.2 K, E � c (a) and [�2(�)��]2 (b)) of Cs3Bi2I9 layered crystals. The temperature shift of the energy gap Eg(T) and the temperature dependence of the half-width H(T) of the exciton absorption band of Cs3Bi2I9 crystals are shown in Fig. 2. In Fig. 2,a the points are experimen- tal data for Eg(T) and the continuous curve represents Eg(T) as obtained from the computation by the Varshni formula [28] E T E T Tg g( ) ( )� 0 2 � , (1) where Eg(0) = 2.857 eV, = –7·10–4 eV/K and � = = 258.654 K. We would like to stress a few points: 1) the experimental results are described very well by this formula; 2) the energy position of the energy gap does not change at T < 45 K and shifts to the long- wavelength side with increase of temperature up to 300 K without any anomalies at Tc = 220 K. Such behavior of Eg(T) is not peculiar to layered semi- conductors but is typical for the majority of the well-studied ones, for example Ge, Si, SiC, A2B6, and A3B5. It can therefore be explained in the following manner. First, at low temperatures the mechanisms caused by the interaction of electrons and holes with acoustic and optical phonons are included and then at higher temperature the other mechanisms connected with the thermal expansion of the crystal lattice take place. It is very important that all mechanisms contribute with the minus sign. The absence of an anomaly in the temperature shift of Eg(T) allow us to suppose that the anisotropy of the optical properties in the monoclinic structure is not high. This conclusion correlates very well with the low intensities of the low-frequency doublets (33.4, 38.3), (44.3, 48.2) cm–1 in the Raman spectra at 4.2 K. Therefore Cs3Bi2I9 crystals are not typical lay- ered compounds. These crystals can be considered as layered semiconductors in the hexagonal phase and normal ones in the monoclinic phase. Thus Cs3Bi2I9 crystals demonstrate nontraditional temperature behavior of Eg(T) for layered substances. The experimental temperature dependence of the half-width H(T) (points) of the exciton band of Cs3Bi2I9 crystals is depicted in Fig. 2,b. With increas- ing temperature from 4.2 to 150 K the half-width in- creases nonlinearly from 48.9 to 99.7 meV. Then H(T) begins to rise less sharply, forming a plateau (the transition region) up to T < 220 K with a surge at T = 220 K. After that H(T) returns almost to the starting point at T = 225 K and increases linearly (H(T) = k(T – 225 K) + H0, where k = 0.758 meV/K and H0 = 116.3 meV) in the temperature range 225 K � T � 300 K. We made an effort to model the temperature de- pendence of the half-width of the exciton band. It was found that the half-width can be described at T � 150 K by the following equation: H T H kT ( ) ( )� � � � � �0 2 coth ph�� , (2) obtained by Toyozawa [29] for weak exciton—phonon interaction. Here H(0) is the half-width at absolute zero temperature and ��ph is the energy of the inter- acting phonon. The results of the modeling are given in Fig. 2,b for H(0) = 48.92 meV and two real optical phonons which were registered in Raman spectra [8] at 4.2 K. The calculated curves are localized above (�ph = 99.8 cm–1) and under (�ph = 114.8 cm–1) the experimental dependence. The best correlation be- tween experiment and theory exists for an effective phonon with frequency 105.8 cm–1 (thick curve). Es- tablished dependence is essentially differed from H(T) dependence of exciton band of BiI3 classical layered semiconductor in which the phase transitions are absent and high exciton—phonon interaction takes place [14,24]. The deviation of experimental dependence H(T) from the theoretical (2) and appearance of the transi- tion region indicates the reconstruction of the monoclinic crystal lattice between 150 and 220 K. As Effect of temperature variation on shift and broadening of exciton band in Cs3Bi2I9 layered crystals Fizika Nizkikh Temperatur, 2004, v. 30, No. 12 1285 40 60 80 100 120 140 160 5 50 100 150 200 250 300 H , m eV b 2.80 2.81 2.82 2.83 2.84 2.85 2.86 a T , K T = 220 Kc E , e V g Fig. 2. Temperature shift of the energy gap Eg(T) (a) and broadening of half-width H(T) (b) of the exciton band of Cs3Bi2I9 layered crystals. was shown in Ref. 30, the region 183–221 K corres- ponds to a heterophase structure where ferroelastic and paraelastic phases coexist. Therefore the whole transition region may be identified with the hetero- phase structure. The appearance of a surge at T = 220 K is probably due to the ferroelastic phase transition (as T = Tc [2–4]). Thus the half-width of the exciton band may be used as a highly sensitive nondestructive probe for re- vealing a phase transition. 4. Conclusions We have presented analyses of the effect of tempe- rature variation on the exciton reflection spectra of Cs3Bi2I9 layered crystals. It was found that these crys- tals are not typical layered ones. These crystals are layered semiconductors in the hexagonal phase and be- have like conventional semiconductors in the mono- clinic phase. 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