Influence of the local structure in phase-change materials on their dielectric permittivity
© Shportko and Venger; licensee Springer. 2015
Received: 19 October 2014
Accepted: 6 January 2015
Published: 5 February 2015
Ge-Sb-Te alloys, which belong to the phase-change materials, are promising materials for data storage and display and data visualization applications due to their unique properties. This includes a remarkable difference of their electrical and optical properties in the amorphous and crystalline state. Pronounced change of optical properties for Ge-Sb-Te alloys is linked to the different bonding types and different atomic arrangements in amorphous and crystalline states. The dielectric function of phase-change materials has been investigated in the far infrared (FIR) range. Phonons have been detected by FTIR spectroscopy. Difference of the dispersion of the dielectric permittivity of amorphous and crystalline samples is caused by different structures in different states which contribute to the dielectric permittivity.
Ge-Sb-Te alloys are characterized by a profound change of optical and electrical properties between the amorphous and crystalline state, which makes them attractive for data storage [1,2] and display and data visualization  applications. The electrical resistivity of the amorphous and crystalline phases commonly differs by about 3 to 4 orders of magnitude, which is very favorable for phase-change memory operation .
These properties might be used in memories based on PC materials (PCRAM), which operation relies on the fact that chalcogenide-based materials, such as phase-change alloys that contain Ge, Sb, and Te, can be reversibly switched from an amorphous phase (‘0’ state) to a crystalline phase (‘1’ state) or vice versa by an external electric current. PCRAM are a candidate to replace flash memory for non-volatile data storage applications due to their lower power consumption and higher operation speed [5-7].
Phase-change materials have already been employed in optical data storages (CDs, DVDs, Blu-Ray disks) due to the profound change in the optical properties between the amorphous and the crystalline state. In , it was demonstrated that by combining the optical and electronic properties of phase-change materials, display and data visualization applications that go beyond data storage applications can be created. This motivates researchers to investigate and to understand the optical properties of the phase-change materials in a wide spectral range.
Samples investigated in this study were prepared in a following way: firstly, a 150-nm Al layer was deposited onto a glass substrate. After that, the Ge-Sb-Te film (1,000 nm) was d.c. sputter deposited onto it. In this work, we have investigated two phase-change alloys: Ge2Sb2Te5 and Ge3Sb2Te6. To obtain polycrystalline samples, the as-deposited amorphous films were annealed in Ar atmosphere for 30 min at temperatures about 20°C above their corresponding crystallization temperatures. The structure of the phase-change samples was checked by X-ray diffraction . The phase-change layer thickness was determined on reference samples prepared in the same sputter session using an Alpha-Step 200 profilometer (Tencor Instruments, Milpitas, CA, USA).
IR reflectance spectra were measured at room temperature in the range from 50 to 650 cm−1, using a Bruker IFS 66v/s spectrometer with a Hg lamp (Bruker Optics, Ettlingen, Germany) as the radiation source employing a resolution of 1 cm−1. Two hundred fifty-six scans were collected in each experiment. A gold mirror (300 nm thick layer of gold, deposited on glass) with a reflectance of 0.99 in the IR served as a reference for the measurements. To normalize the data, the IR reflectance spectra of the reference and the sample were measured subsequently. After dividing the sample’s spectrum by the reference, the final spectrum was obtained. The relative measurement error for the reflectance is 0.2% in the measured wavelength range.
Experimental reflectance spectra were analyzed using the SCOUT software. The model of the dielectric function ε(ν) used is composed of the following parts: a constant, which is responsible for the polarizability in the higher energy range, a Drude contribution for free charge carriers (in the case of the crystalline samples), and a sum of Kim oscillators to describe the contribution of the IR-active phonons [9,10].
Results and discussion
The amorphous state of phase-change materials is bonded covalently, while the crystalline phase utilizes resonant bonding. Due to this fact, the dielectric permittivity of the crystalline phase above the reststrahlen and below the optical band gap is several times bigger than that of the amorphous phase . Vibrational properties of phase-change materials have been studied using Raman spectroscopy in [14-16]. In this study, we have focused on the dispersion of dielectric function of phase-change materials in the reststrahlen. The dielectric function of two Ge-Sb-Te alloys: Ge2Sb2Te5 and Ge3Sb2Te6, has been investigated.
Positions of the phonons’ absorption peaks (in cm −1 ) in the ε 2 ( ν ) of studied Ge-Sb-Te alloys
Ge 2 Sb 2 Te 5
Ge 3 Sb 2 Te 6
In Ge-Sb-Te alloys, the Ge and Te atoms build the octahedral and tetrahedral structures. A. Kolobov et al.  claim that the Ge atoms occupy the octahedral and tetrahedral symmetry positions in the crystalline and amorphous states in Ge-Sb-Te alloys, respectively. Authors  have reported the phonon energies in Ge-Sb-Te alloys and assigned them to the vibrations of the structures built from the Ge and Te atoms.
To explain the contrast in the dispersion of the dielectric function between amorphous and crystalline Ge-Sb-Te samples, we compared our experimental results with data from . According to , we assigned oscillators used to model the dielectric function of Ge2Sb2Te5 and Ge3Sb2Te6 (Table 1) to the vibrations of Ge-Te octahedra and tetrahedra. In amorphous Ge-Sb-Te, peaks A and B are close to the energies of the vibrations of Ge-Te octahedra; the peak C corresponds to the vibrations of Ge-Te tetrahedra. In case of crystalline Ge-Sb-Te alloys, peaks D, E, and F correspond to the vibrations of Ge-Te octahedra.
The contrast of the dielectric function of amorphous and crystalline phase-change materials has been observed in the FIR. In this range, the dielectric function is mainly governed by the phonons, and it was modeled by the sum of oscillators, which were attributed to the vibrations of Ge-Te octahedra and tetrahedra. Observed contrast of optical properties of phase-change materials in the FIR is caused by different contributions of the local structures into the dielectric permittivity of Ge-Sb-Te alloys.
One of the authors (K. Shportko) gratefully acknowledges the support from the DAAD (German Academic Exchange Service) and the SFB 917 ‘Resistively Switching Chalcogenides for Future Electronics - Structure, Kinetics and Device Scalability’.
- Ovshinsky SR. Reversible electrical switching phenomena in disordered structures. Phys Rev Lett. 1968;21:1450–6.View ArticleGoogle Scholar
- Wuttig M, Yamada N. Phase-change materials for rewriteable data storage. Nat Mater. 2007;6:824–32.View ArticleGoogle Scholar
- Hosseini P, Wright CD, Bhaskaran H. An optoelectronic framework enabled by low-dimensional phase-change films. Nature. 2014;511:206–12.View ArticleGoogle Scholar
- Friedrich I, Weidenhof V, Njoroge W, Franz P, Wuttig M. Structural transformations of Ge2Sb2Te5 films studied by electrical resistance measurements. J Appl Physics. 2000;87:4130–4.View ArticleGoogle Scholar
- Kang D, Ahn D, Kim K, Webb JF, Yi K. One-dimensional heat conduction model for an electrical phase change random access memory device with an 8F2 memory cell F = 0.15 mkm. J App Phys. 2003;94:3536–42.View ArticleGoogle Scholar
- Hosaka S, Miyauchi K, Tamura T, Yin Y, Sone H. Prototype of phase-change channel transistor for both nonvolatile memory and current control. IEEE Trans Electron Dev. 2007;54:517–24.View ArticleGoogle Scholar
- Karpov VG, Kryukov YA, Savransky SD, Karpov IV. Nucleation switching in phase change memory. Appl Phys Lett. 2007;90(1–3):123504.View ArticleGoogle Scholar
- Shpotyuk O, Calvez L, Petracovschi E, Klym H, Ingram A, Demchenko P. Thermally-induced crystallization behaviour of 80GeSe2–20Ga2Se3 glass as probed by combined X-ray diffraction and PAL spectroscopy. J Alloy Comp. 2014;582:323–7.View ArticleGoogle Scholar
- Fox M. Optical properties of solids. New York: Oxford University Press; 2001.Google Scholar
- Uhanov YI. Optical properties of semiconductors. Moscow: Nauka; 1977.Google Scholar
- Shportko KV, Pasechnik Yu A, Wuttig M, Rueckamp R, Trukhan VM, Haliakevich TV. Plasmon–phonon contribution in the permittivity of ZnP2 single crystals in FIR at low temperatures. J Vibr Spectr. 2009;50:209–13.View ArticleGoogle Scholar
- Shportko KV, Izotov AD, Trukhan VM, Shelkovaya TV, Venger EF. Effect of temperature on the region of residual rays of CdP2 and ZnP2 single crystals. Russ J Inorg Chem. 2014;59:986–91.View ArticleGoogle Scholar
- Shportko K, Kremers S, Woda M, Lencer D, Robertson J, Wuttig M. Resonant bonding in crystalline phase-change materials. Nat Mater. 2008;7:653–8.View ArticleGoogle Scholar
- Mazarello R, Caravati S, Angioletti-Uberti S, Bernasconi M, Parrinello M. Signature of tetrahedral Ge in the Raman spectrum of amorphous phase-change materials. Phys Rev Lett. 2010;104(1–4):085503.View ArticleGoogle Scholar
- Sosso GC, Caravati S, Gatti C, Assoni S, Bernasconi M. Vibrational properties of hexagonal Ge2Sb2Te5 from first principles. J Phys Condens Matter. 2009;21(1–8):245401.View ArticleGoogle Scholar
- Sosso GC, Caravati S, Mazzarello R, Bernasconi M. Raman spectra of cubic and amorphous Ge2Sb2Te5 from first principles. Phys Rev B. 2011;83(1–8):134201.View ArticleGoogle Scholar
- Kolobov AV, Fons P, Frenkel AI, Ankudinov AL, Tominaga J, Uruga T. Understanding the phase-change mechanism of rewritable optical media. Nat Mater. 2004;3:703–8.View ArticleGoogle Scholar
- Matsunaga T, Yamada N, Kojima R, Shamoto S, Sato M, Tanida H, et al. Phase-change materials: vibrational softening upon crystallization and its impact on thermal properties. Adv Funct Mater. 2011;20:1–8.View ArticleGoogle Scholar
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly credited.