Elucidating the phase change memory properties of (GeTe)1-x(GeSe2)x (0 ≤ x ≤ 0.

21) films

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Abdul Whab, Shahin Parveen, Nidhi Bhatt and Pumlianmunga*

Department of physics, Jamia Millia Islamia (A central university), New Delhi 110025, India

*Corresponding author: pumlianmunga@[Link]

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Abstract: GeSe2-doped GeTe phase change memory alloys are considered for high-temperature
applications. Films of compositions (GeTe)1-x(GeSe2)x(x= 0, 0.07, 0.14, 0.21) showed an increase
in the crystallization temperature (Tc) from 170 oC to 258 oC after doping with GeSe2, which is

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caused by an increase in the activation energy. Incorporation of GeSe2 increases the amorphous
as well as crystalline resistances, resulting in the decrease in threshold current (Ith) from 0.9 mA

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to 0.4 mA. The 10 years of data retention temperature have been increased from 96oC to 128oC
with a corresponding increase in the activation energy from 2.43 eV to 2.73 eV. The amorphous
phase crystallized to a rhombohedral structure with no phase separation, and the crystallite size
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decreases with the increase in the GeSe2 concentration. X-ray photoelectron spectroscopy (XPS)
confirmed the presence of stronger Ge-Se bonds, which increase the localization of charge
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carriers, resulting in the increase in optical band gap. Increased thermal stability (high Tc), high
electrical resistance contrast between the amorphous and crystalline states, high crystalline
resistance, and single-phase GeTe are characteristics of phase change memory (PCM) material
for high-temperature applications.
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Keywords: GeTe, Phase change memory, thermal stability, Chalcogenides, and activation
energy.
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Introduction: - The upcoming big data age will require data to be continuously stored and
retrieved for extended periods of time, which will provide an enormous challenge to existing
data centres. The separation between memory and processing components can be integrated into
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a single unit of data storage and in-memory computation using a non-volatile phase change
memory technology [1]. Phase change memory (PCM) has emerged as a leading candidate for
next-generation non-volatile memory technology, offering fast read and write speeds, good
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endurance, less power consumption, and high scalability. PCM devices utilize materials that
undergo a reversible phase transition between amorphous and crystalline states, enabling the
storage of binary data [2]. In a PCM, the amorphous phase (RESET/high resistance state) and
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the crystalline phase(SET/low resistance state) have large resistance differences between them
[3] which can go up to six orders for applications in electronics and in neuromorphic

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 memories[4][5][6]. This resistivity contrast is used to store information in the form of a binary
bit, either ‘0’(RESET) and ‘1’(SET) states[7]. This unique properties of chalcogenide materials

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are attractive for memory applications[8]. Random access memory (RAM) based on PCM has
recently been studied for advancing topics such as brain-inspired computing [9][10].The most
commonly used and explored PCM material lie on the line that connects GeTe to Sb2Te3. In this

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pseudo-binary tie line, the phase change materials’ properties (i.e., thermal stability of
amorphous phase, crystallization temperature, melting point, and activation energy) decrease on
moving from one binary composition, GeTe, to the second binary composition, Sb2Te3 [7]. So,
the thermal stability of GeTe is superior to that of GST, taking into account the higher activation

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energy (Ea), crystallization temperature (Tc), and ten years of data retention [11]. The thermal

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stability is the major challenge in phase change random access memory (PCRAM) materials. For
high-temperature memory applications in automotive and industrial technologies, the demand is
that the amorphous phase stability of the film be ~ 260 oC at least for 2 min at the time of
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soldering and remain at that temperature for an extended time post soldering. For such
demanding applications, the pseudo-binary tie line Germanium-Telluride (GeTe) alloy has
shown better PCM properties for high-temperature memory applications, whose crystallization
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temperature can be raised either by doping or synthesising new materials[7][12].

The germanium-based chalcogenides, attracted increased attention in electrical storage, and

GeTe is most commonly studied [13]. There has been an attempt to improve the PCM of GeTe
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by doping; however, results are not quite satisfactory. For example, in Cu-doped GeTe, the
crystallization temperature (Tc) increases from 185 oC to 258 oC, but the resistivity contrast
between the amorphous and crystalline states decreases [14], which will affect the signal to noise
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ratio in PCRAM applications. Similarly, in Ni-doped GeTe system, the Tc increases from 192 oC
to 250 oC after doping, but the resistivity contrast is decreased [15]
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In Cr-doped GeTe, there is no improvement in the Tc after doping, but at high doping
concentrations, a trend reversal is seen in the resistance between the amorphous and crystalline
states[16]. In Si-doped GeTe at 12.6 at. %, there is a phase separation[17]. In Se-doped GeTe,
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phase separation is observed in the system [5]. All the above systems being nonstoichiometric
compositions, it affects the lattice structure and the PCM properties. Phase separation reduces
the endurance by causing elemental segregation within the material, leading to uneven switching
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behaviour and ultimately device failure when repeatedly switched between amorphous and
crystalline states due to the formation of voids with different electrical properties. Due to the

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 atomic migration, two types of switching failure, stuck set (in crystalline state) and stuck reset
(in amorphous state) are reported in PCM devices[18].

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In the present study, GeTe has been doped in such a way that issues such as a decrease in
resistivity contrast and phase separation, which are observed in the system, may be avoided.

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Doping of GeSe2 in Sb2Te3 improved the phase change properties for PCM [19]. Thus, the
addition of GeSe2 in GeTe may give useful insight for future PCM devices and discover useful
ternary phase change material.

GeTe has two crystalline structures: rhombohedral and cubic NaCl structures. Fig. 1 shows the

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rhombohedral and cubic structures, which are drawn using VESTA[20]. GeTe exists in a

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rhombohedral structure at temperatures between 273K - 700K with a space group of R3m, and
above 700K, it transforms into a rock salt structure with a space group of Fm-3m. The
rhombohedral shape with space group (R3m) has lattice parameters a = b = 4.164 Å and c =
10.690 Å), which arises due to structural distortion along direction (111) of the cubic structure
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at temperatures below 700K. This distortion occurs because the central atom doesn’t stay at the
centre and depends on various factors like bond length difference or electronic structure [21]. In
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cubic structure, the Ge atom sits at the centre with six Te atoms in the octahedron and makes
GeTe bonds, while in rhombohedral structure, the Ge atom sits off-centre in the octahedron; it
makes three longer bonds and three shorter bonds. Due to Ge atom distortion, it occupies the
cation lattice, and the Te atoms occupy the anion positions. The presence of two different atoms
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with different electronegativities in GeTe causes it to exhibit ferroelectricity. It becomes the heart
of many experimental and theoretical studies due to its attractive properties, such as ferroelectric
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and phase change behaviour [27][23].

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Fig. 1(a) Crystal structure of GeTe at room temperature rhombohedral (R3m) which transforms 1(b) to cubic
structure (Fm-3m) at 675K.

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 Experimental details: - Bulk samples were prepared from high-purity elements Ge, Te, and Se
(99.99% Sigma Aldrich) using the melt quenching technique. The desired proportions (GeTe)1-

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x(GeSe2)x (x= 0, 0.07, 0.14, 0.21) were transferred to clean quartz ampoules. These ampoules
were evacuated and sealed in low pressure of 1 × 10―5 mbar. The sealed samples were put into
an electric furnace and heated up to 850oC. They were kept at that temperature for 40 hours[19].

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To ensure the homogeneity of the molten materials, the ampoules were rotated and quenched in
ice-cold water. Microscopic glass slides washed with Vim+ isopropyl alcohol solution (IPA) and
deionized water (DI water) were used for depositing the films. Amorphous films of thickness
measuring 200 nm were deposited at room temperature on a glass and aluminum-coated glass

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(for I-V) under a vacuum chamber pressure of 8 × 10―6mbar by a thermal evaporation unit

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(HPVT-305B)[24] from their respective alloys (GeTe)1-x(GeSe2)x (x = 0, 0.07, 0.14, 0.21). To
check the variation of resistance (R) with temperature (T) and data retention, the Keithley
electrometer 6514 was used. Different temperatures were used to anneal the films under a
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vacuum pressure of 1 × 10―3mbar. The structure of the annealed films was confirmed using an
X-ray diffractometer (Bruker D8 Advance Cu Kα ). Raman spectroscopy (LAB RAM HR Horiba
France 532 nm Nd-YAG laser 100mW) measurements were carried out using the 512nm Argon
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Laser. Current (I)-voltage (V) characteristics of the films deposited on aluminium-coated glass
by using Keithley source meter (model 2540). X-ray photoelectron spectroscopy (XPS) was
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Fig. 2. (a) R-T measurement of (GeTe)1-x(Ge-Se2)x (x=0, 0.07, 0.14, 0.21) (b) Crystallization Temperature vs
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composition (c) composition vs set resistance & reset resistance calculated at 50oC & 350oC,
respectively.

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 performed using Kα (Thermo Fisher Scientific Pvt. Ltd. UK). The chemical bond states were
investigated by X-ray photoelectron spectroscopy (XPS). The microstructure was analyzed

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through High Resolution Transmission Electron Microscopy (HRTEM) and Selected Area
Electron Diffraction (SAED) performed by Tecnai at 200 kV acceleration voltage.

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Results and Discussion: -

R-T measurement: - The thermal stability was investigated by conducting a resistance (R) vs.
temperature (T) measurement. The two-probe method was employed for measuring the variation
of resistance as a function of temperature (R-T) of (GeTe)1-x(Ge-Se2)x (x=0, 0.07, 0.14, 0.21)

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amorphous films, heated at 10 oC/min inside a vacuum chamber of pressure 10-3 mbar. From Fig.

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2, it can be seen that the amorphous films (Fig. 3) showed a monotonic decrease in electrical
resistance with the increase in temperature and suddenly dropped upon reaching the
crystallization temperature (Tc). A further increase in the temperature beyond the Tc did not cause
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a significant reduction in the electrical resistance. The R-T curve shows a single transition from
amorphous to crystalline (rhombohedron). With the increase in GeSe2 concentration, the
crystallization temperature (Tc) increases monotonously, as shown in Fig. (2a). This observation
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can be explained based on the chemical bond approaches[25]. The increases in GeSe2
concentration increase the amorphous and the crystalline resistances. This is due to the presence
of stronger Ge-Se bonds in the structure, which increases the localization of charge carriers with
doping[26]. The Tc of GeTe (x=0) is observed at 170 oC which is consistent with literature[27],
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[28]. Films with x=0.07, 0.14, and 0.21 crystallized at 170 oC, 222 oC, 241oC, and 258 oC
respectively. The first-order derivative of resistance with temperature d(logR)/dT is shown in
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Fig. (2a), confirming a single thermal transition event during the R-T process. The sharpness of
the derivative peak indicates the rate of amorphous-to-crystalline transition. A wider derivative
peak (d(logR)/dT) indicates slow crystallization rate, whereas a sharp peak indicates faster
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crystallization. It can be seen that the derivative peaks remain more or less the same with the
GeSe2, suggesting that the amorphous to crystallization rate will remain comparable with the
addition of GeSe2. An increase in GeSe2 concentration also increases gradually the difference in
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the values of resistances between the amorphous and crystalline phases, which is approximately
six orders of magnitude in x = 0.21. This larger resistance contrast makes it possible for
multilevel memory device applications [25], [27].
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Fig. 3 XRD results of (GeTe)1-x(Ge-Se2)x (x=0, 0.07, 0.14, 0.21) films (a) as deposited (b) at 240oC (c) at 280oC
(d) 320oC

X-ray diffraction studies: - Fig. 3(a, b, c, & d) depicts the XRD patterns of all compositions
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(GeTe)1-x(Ge-Se2)x (0 ≤ x ≤ 0.21) in the as-deposited and annealed films at different annealing

temperatures, 240, 280 and 320 oC. All the as-deposited films are amorphous at room
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temperature, as illustrated by Fig. 3(a). Fig. 3(b, c, and d) display the films annealed at different
temperatures for an hour, showing the evolution of the amorphous to crystalline phase with
doping concentration.
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When the films are annealed at 240 oC, the amorphous phase of both the GeTe and x = 0.07 (7
at. % of GeSe2) films changes to GeTe rhombohedral structure. The dominant diffraction peak
featuring at ~30 o angle (2θ) of x=0.07 is small, indicative of small crystalline size in the sample,
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whereas films with x = 0.14 and x = 0.21 remained in an amorphous phase. This pattern is
consistent with the R-T result (Fig. 2a). All the diffraction peaks can be compared with the
standard rhombohedral GeTe phase (ICDD PDF 00-047-1079) with a space group of -R3m[29]
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[23][30]. The diffraction peaks do not shift it position with doping, suggesting the GeSe2 does
not replace the lattice sites or occupy the interstitial positions. When the films were annealed at

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 280 oC, they all crystallized into rhombohedral structure. The peak intensity of both GeTe and x
= 0.07 films increased. At 280 oC, both the x= 0.14 and x = 0.21 films undergo crystallization,

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which is consistent with the R-T result. When the temperature is increased to 320 oC, there is no
change in the diffraction pattern; however, the intensity of the diffraction peaks is increased,
signifying a growth in the size of the crystalline structure with the increase in annealing

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temperature. On careful observation, it can be seen that the intensity of the peak decreases with
the increase in GeSe2 concentration for films annealed at the same temperatures. This shows that
the addition of GeSe2 retards the phase transition process of GeTe, indicating an increase in the
thermal stability of the films is enhanced.

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Fig. 4 (a) Arrhenius plot of (GeTe)1-x(Ge-Se2)x (x=0, 0.07, 0.14, 0.21) films as deposited (b) activation energy vs
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GeSe2 % content.

Data retention studies: A data retention study estimates the ability of PCM material to reliably
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store data for extended periods in the absence of power without degradation over time. The
failure time and activation energy are calculated by using the Arrhenius relation 𝑡 = 𝜏𝑒𝑥𝑝
(𝐸𝑎 ∕ 𝑘𝐵𝑇) [31], where t, 𝜏, Ea, kB, and T are failure time, proportional time constant,
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crystallization activation energy, Boltzmann constant, and absolute temperature, respectively.

The failure time is calculated by measuring the time taken to reach half the value of its initial
resistance at a particular temperature. Fig. 4(a) displays the increase in the failure temperatures
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with the increase in GeSe2 estimated for 10 years. The activation energies for crystallization
corresponding to ten years of failure temperatures for samples x=0 (GeTe), 0.07, 0.14, and 0.21
are 2.43 eV (96oC) [34-35], 2.53 eV (104 oC), 2.65 eV (118 oC) and 2.73 eV (128 oC),
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respectively, revealing that the failure temperature of data retention is increased significantly
with the increase in GeSe2 percentage. The increase in activation energy with GeSe2

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 concentration is shown in Fig. 4(b). The addition of GeSe2 has been found to improve data
retention and thermal stability, making valuable enhancements for PCM applications [34].

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Fig.5-Raman spectra of (a) as deposited and, (b) annealed films at 320 oC.
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Raman studies: - Raman spectroscopy has been carried out to investigate the structural units
present in the films and the evolution of the unit with GeSe2 concentration. The Raman spectra
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of the as-deposited films and films annealed at 320 oC for all compositions (GeTe)1-x(Ge-
Se2)x(x=0, 0.07, 0.14, and 0.21) are shown in Fig. 5(a, b). In the amorphous film GeTe (x=0),
there are five peaks arising at 68 cm-1, 86 cm-1, 131 cm-1, 148 cm-1 and 168 cm-1 positions. The
peaks at 68 cm-1 and 86 cm-1 are due to symmetric bending modes, v2 (E), and v4 (F2) of
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tetrahedral unit GeTe4-nGen (n=0, 1, 2, 3) respectively, which are lower energy in than the
symmetric stretching unit of v1 (A1) mode at 168 cm-1[35]. The band at position 131 cm-1 is
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attributed to edge-sharing of tetrahedron GeTe4 [36], [37]. The band at 148 cm-1 is the symmetric
stretching vibration of Te-Te bond[38]. After the addition of GeSe2, it leads to a continual
increase in the disorder of the amorphous network. This is indicated by the decrease in the peak
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intensity caused by variations in the bond angle and bond length [19]. In x = 0.21 except for the
symmetric stretching mode at 86 cm-1, all the other vibrational bands disappeared [24]. In Fig.
5(b), the Raman bands at 118 cm-1 to 135 cm-1 are assigned to the symmetric stretching modes
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of 𝜈1(A1) of GeTe4-nGen(n=2,3) corner-sharing tetrahedral and Te vibrations [25] [39],

respectively, which shifts (118 cm-1) to a higher wavenumber with the increase in GeSe2
concentration[40]. The blue shifts in the peak position of this are characteristic of Raman
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vibration when a lighter Se atom replaces the heavier Te atom in the GeTe4-nGen (n = 2, 3)
structural units; consequently, the vibrational energy is shifted to a higher wavenumber[39]. The
crystalline films x = 0.07, 0.14 and 0.21 have a new peak appearing at 165 cm-1, which is

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 assigned to the edge-sharing of GeTe4-nGen(n=0,1,2,3) [39] vibration. This intensity of the band
increases with GeSe2.

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I-V Characteristics: - I-V characteristics elucidate the behaviour of the films under the effect
of an electric field. An electric current causes the PCM material to switch between the amorphous

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and crystalline states. For the study of the switching properties, the PCM materials (GeTe)1-
x(GeSe2)x (x=0, 0.07, 0.14 & 0.21) were deposited on aluminium-coated glass in a sandwich
geometry (Al/GeTeGeSe2/Al). When an electric current is applied to the amorphous film (high
resistance), the voltage follows a linear path at low voltages, and at higher voltages near threshold

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voltage (Vth), it follows a non-linear path. The current corresponding to the Vth is called the
threshold current (Ith)[19]. A Vth is the point at which a snapback in the voltage occurs. On

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increasing the current beyond Ith, the voltage snaps back due to the formation of a conducting
path. On reducing the current from its peak value (5 mA), the curve follows the I-V pattern of a
crystalline semiconductor, confirming the formation of a crystalline phase during the rises in the
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current from 0 mA to 5 mA. All the films showed an amorphous-to-crystalline transition. With
the increase in GeSe2, the Vth increases, whereas the Ith decreases. Amorphous chalcogenide
material has a large number of localized states (traps) in the gap between the conducting and the
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valence bands as a result of the interaction of lone-pair (LP) electrons with the surrounding
atoms, which controls its transport properties. Doping alters the optical bandgap and electrical
conductivity of the material. Low electronegative dopants increase the energy of LP electrons
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and outspread the valence band, which reduces the optical energy bandgap[41]. On the other
hand, a higher electronegative dopant would localize the LP electrons and increase the optical
bandgap. The presence of a large density of weak bonds resulting from low electronegative
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dopants would lead to Mott’s delocalization of charge carriers and decrease the bandgap. In
chalcogenide materials, the threshold voltage (Vth) is linearly related to the optical energy
bandgap[42]. When an electric field is applied, the charge carriers start to fill the trap states,
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which is seen in the linear portion of the I-V curves (Fig. 6a). When the voltage is increased
further, the trap filling is enhanced and the charge carrier travels the sample with improved
mobility. This portion is displayed in the non-Ohmic region in the amorphous state[43]. At higher
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voltage, the trap states are neutralized by the charge carriers, and the large density of charge
carriers forms a conducting path, resulting in the collapse of the Vth. During the charge transport
in the disordered network, energetic electrons collide with the atoms and generate Joule heating.
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A permanent current channel is formed [44](P = I2R). According to chemical bond approaches,
higher energy bonds are preferred initially in covalent networks. The possible bonds and their

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 energies are Ge-Se, Te-Se, Ge-Te, and Te-Te bonds, which are 205.4 kJ/mol, 184.9 kJ/mol, 157.3
kJ/mol, and 138.3 kJ/mol, respectively [45]. The presence of different bond strengths would

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result in varying energy separation between the valence and conduction bands[46]. A large
density of weak bonds would move the conduction-band edge to a lower energy, which will
delocalize the charge carrier (Mott delocalization) because of Coulomb repulsion and

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correlation[46]. Due to the increase in strong bonds Ge-Se (205.4 kJ/mol), Mott’s localization
will decrease the charge carrier density. Consequently, a decrease in the Ith with a corresponding
increase in the Vth is observed, as shown in Fig. 6b. The average bond energy in the system will
rise as the GeSe2 network grows, leading to a higher crystallisation temperature and greater

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thermal stability of the amorphous network.

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Fig. 6. (a)I-V characteristics of (GeTe)1-x(Ge-Se2)x (x=0, 0.07, 0.14, 0.21) (b) For composition (x), Vth vs Ith
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X-ray photoelectron spectroscopy (XPS - The high-resolution XPS was performed on GeTe
and (GeTe)0.79(GeSe2)0.21 films to confirm the chemical bonding state with doping in the
crystalline (320oC). The XPS spectra of Ge 3d, Te 3d, and Se 3d are illustrated in Fig. 7 (a, b, c
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& d). The film surface confirms the presence of Ge, Te, and Se atoms. The spectra of Te 3d are
shown in Fig. 7 (a & b). In pristine GeTe, two main peaks at positions 573.86 and 584.36 eV
correspond to oxidized Te as TeO2. Two peaks of metallic Te 3d5/2 and 3d3/2 occur at 570.30 eV
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and 580.75 eV, respectively. The spin-orbit splitting is approximately at 10.5 eV, which is
consistent with reported results [47][48]. For GeSe2 doping (x = 0.21), there are two oxidized
peaks of Te as TeO2 at 574.20 eV and 584.70 eV. Two peaks of metallic Te 3d5/2 and Te 3d3/2
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are at 570.80 eV and 581.40 eV, respectively. After GeSe2 doping, the binding energy (B.E.) is
shifted to higher B.E. due to Se having higher electronegativity with respect to Ge and Te [49],

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 [50]. The electronegativity of Se, Ge and Te is 2.55, 2.01 and 2.1, respectively. The Ge 3d peaks
occur at 29.9 eV and 30.4 eV, as shown in Fig. 7(c), confirming the presence of a GeTe bond.

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As reported, the Ge-Se bonds are stronger than the Ge-Te and Te-Se bonds. After GeSe2 doping
(x = 0.21), the Ge peak shifted to higher binding energy due to the creation of Ge-Se bond caused
by the higher electronegativity of Se that shifts toward higher binding energy and confirming the

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presence of strong Ge-Se bonds. [25], [51][26], [52]. The XPS of Se 3d is shown in Fig. 7(d). A
peak detected at 54.7eV has been reported, which corresponds to Se bonding to the as Ge-Se.
This further confirms the formation of Ge-Se bonds in the doped films [52][53][54].

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Fig. 7. XPS measurements of (a)Te 3d, (b) Te 3d for x=0.21 (c) Ge 3d for x=0, 0.21 (d) Se 3d for x= 0.21
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High Resolution Transmission Electron Microscopy (HRTEM) and Selective Area

Electron Diffraction (SAED) studies: - The microcrystalline structures of the GeTe (x=0) and
(GeTe)0.79(GeSe2)0.21 films are analysed using the HRTEM and SAED studies. Fig. 8 (a,b,c & d)
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display the HRTEM and SAED patterns of GeTe and (GeTe)0.79(GeSe2)0.21 samples annealed at
320 oC. The HRTEM image of GeTe (x=0) shows good crystallinity with a single diffraction
plane (d-spacing or adjacent planes) measured to be 0.34 nm, and the corresponding plane (hkl)
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is (021). Fig. 8(b) displays the polycrystalline nature of the (GeTe)0.79(GeSe2)0.21 sample with d-
spacings of 0.69, 0.29, and 0.34 nm, and their corresponding lattice planes are (002), (202), and

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 (021) [5][55]. This proves that the growth of crystallization is impeded by GeSe2 doping, and the
crystallization behaviour of GeTe (x=0) changes from being growth-dominated to nucleation-

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dominated[56].

The SAED pattern of both films (x=0 and x=0.21) is shown in Fig. 8 (c & d). On careful

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observation, the sample x = 0 has comparatively brighter-scattering spots arising from
rhombohedral structure (GeTe), distributed in the concentric rings. The structure is consistent
with the XRD result (Fig. 3). The sample x=0.21, which has a low-intensity scattering spot in
the diffused concentric rings, indicates the reduction of the grain size after doping. Smaller grains

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increase lattice scattering of charge carriers during charge transports, which increases the
electrical resistivity and reduces the heat dissipation[19]. High crystalline resistance will reduce

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the heat required for the reverse processes (crystal to amorphous transitions)[57].

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Fig. 8. HR-TEM and SAED pattern of GeTe (a & c) , and (GeTe)0.79(GeSe2)0.21 (b & d)

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 VIS-NIR studies: -

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The transmission spectra and Tauc plots of the as-deposited films are shown in Fig. 9(a &b). The
films were scanned in the range of 500 - 2400 nm. The absorption coefficient of the sample is
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calculated using the relation, 𝛼 = 𝑑𝑙𝑛(𝑇1), where d represents the thickness of the films and T is

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the transmittance. The higher values of 𝛼 > 104 cm-1 have been used following the relation (𝛼ℎ𝜐)
1/2 1/2E [25], Where B1/2 is the Tauc parameter, h is Plank`s constant, 𝑣 is the frequency, and
=B g

Eg is the optical band gap of the samples. The optical band gaps (Eg) have been calculated by
extending the linear region to the x-axis region when the y-axis is zero from linear plots (𝛼ℎ𝜐)1/2

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vs. ℎ𝑣 [24]. The calculated optical band gap of as-deposited films is shown in Fig. 9(b). The

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absorbance edge for x = 0 is at ~ 800 nm. After increasing GeSe2, it shifts to shorter wavelengths
gradually till x = 0. 21. The increase in GeSe2 concentration causes the band gap to increase,
indicating that the optical absorption decreases with increasing GeSe2 concentration. For x = 0,
the calculated band gap is 0.65 eV[5]. The band gaps for the doped films, x = 0.07, 0.14, and
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0.21 are calculated to be 0.68 eV, 0.70 eV, and 0.75 eV, respectively. The increase in the band
gap as a function of composition (x) can be explained by the change in the localized states with
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doping. Ovshinsky et al. proposed that exchanges of lone pair electrons of atoms with other local
environments result in localized states in chalcogenide semiconductors[43]. The
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Fig. 9. (a) Transmission spectra and (b) (𝛼ℎ𝜐)1/2 vs photon energy of as deposited films (c) composition vs band
gap
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This preprint research paper has not been peer reviewed. Electronic copy available at: [Link]
 valence band, which is formed by the lone pair electrons, experiences enhanced band tailing with
the increase in the number of elements in the alloy[41]. Therefore, the lone pair electrons will be

ed
pushed to a higher energy state, and the band tailing will grow by the addition of lower
electronegative atoms. On the other hand, if higher electronegative elements are introduced, band
tailing will be decreasing. A similar band tailing behaviour is expected in the conduction band,

iew
which may not be symmetrical. In the present GeSe2-doped GeTe system, depending upon the
bond strength of doping, the lone pair electrons of the valence will be shrunken or broadened.
The electronegativity values of the elements Se, Ge, and Te are 2.55, 2.01, and 2.10 (in the
Pauling scale), respectively. The introduction of GeSe2 into GeTe will induce reorganization of

v
bonds in the system. The bond energies decrease in the order of Ge-Se, Te-Se, Ge-Te, Te-Te

re
(205.4, 184.9, 157.3,138.3 in kJ/mol.)[25]. With the increase in GeSe2 concentration, the density
of Ge-Se bonds would increase. This will enhance the localization of charge carriers, resulting
in a decrease of the energy of lone pair states by shrinking the band tailing. Additionally, the
er
cohesive energy of the system will increase, and the band gap will increase. A correlation
between cohesive energy and optical band gap is demonstrated in Bi-doped Se-Te system [58].
Thus, the increase in GeSe2 increases the threshold voltage and band gap, with a reduction in the
pe
threshold current (Ith). In Ge10Se90-xTex, with the decrease in optical band gap, the cohesive
energy and electronegativity have decreased[59]. Hence, the optical band gap increased as GeSe2
increased. Widening the band gap reduced the threshold current, which is useful in PCM.
ot

Conclusions: - This work reports the doping of GeSe2 in GeTe in an attempt to design high-
temperature PCM material with enhanced thermal stability as compared with the standard GeTe.
After doping, it has been found that the transition temperature has increased from 170 oC to 258
tn

oC. The increased crystallization temperature (Tc) and improved crystalline resistance are good
for data retention and low power consumption. With the increase in the content of GeSe2, the
activation energy is enhanced compared to pristine GeTe. The XRD and TEM images show that
rin

grain sizes decreased remarkably by the presence of GeSe2 in the amorphous network. The
threshold current (Ith) significantly decreases from 0.9 mA to 0.4 mA, which facilitates the low
power consumption, and the 10 years of data retention temperature has improved from 96 to 128
ep

oC. XPS confirms the formation of Ge-Se bonds, which localized the lone-pair electrons, leading
to Mott’s localization and an increase in the optical band gap. The absence of phase separation
and improved thermal stability in the presence of GeSe2 is effective for high-temperature PCM
Pr

applications.

This preprint research paper has not been peer reviewed. Electronic copy available at: [Link]
 Acknowledgement

ed
This work is supported by the Science and Engineering Research Board (SERB), Govt of India,
for the financial support (EEQ/2018/001158). The authors thank Central Sophisticated
Instrumentation Facility (CSIF), BITS Pilani, K K Birla Goa Campus for XRD characterisation

iew
and Raman spectroscopy. We thank the Sophisticated Analytical and Technical Help Institute
(SATHI), Banaras Hindu University, Varanasi, for providing the XPS facility. Dr Motiur
Rahman Khan, Department of Physics, Jamia Millia Islamia, New Delhi, is acknowledged for
helping in I-V measurements. We thank the Centre for Nanoscience and Nanotechnology, JMI

v
New Delhi, for providing the HR-TEM facility.

re
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