4466 IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 64, NO.

11, NOVEMBER 2017

Modeling of Phase-Change Memory: Nucleation,

Growth, and Amorphization Dynamics During
Set and Reset: Part I—Effective
Media Approximation
Zachary Woods and Ali Gokirmak, Senior Member, IEEE

Abstract — We have constructed a framework that

enables finite-element modeling of nucleation, growth, and
amorphization processes in phase-change memory devices
using a single rate equation that tracks evolution of local
crystal density at each mesh point. The rate equation,
current continuity equation, and Fourier heat transfer equa-
tion are solved simultaneously to perform electro-thermal
simulations that capture the device dynamics during set
and reset operations. The functionality of this framework is
demonstrated through simulation of various set and reset
operations and consecutive set/reset cycles of a mushroom
cell using temperature and crystallinity dependent parame-
ters for Ge2 Sb2 Te5 .
Index Terms — Amorphization, finite-element simulations, Fig. 1. (a) Simulated 2-D rotational geometry with thermal profile during
nucleation and growth, phase-change memory (PCM), set the melting stage of a reset pulse. Voltage is applied to the top TiN
and reset. contact and the bottom TiN contact (diameter = 10 nm) is grounded
through a 10-kΩ load resistor. Illustration of (b) domain-based crystal
I. I NTRODUCTION model with high mesh density at the boundaries, (c) mesh-based model
with a binary switch between crystalline (yellow) and amorphous (blue),

T HE drive to scale conventional CMOS devices down

to <10 nm has led to a technology which enables
fabrication of new devices that complement CMOS, such as
and (d) CD model with a range of CD values. (Multimedia available at
http://ieeexplore.ieee.org.)

phase-change memory (PCM) [1]–[3]. PCM is a high density,
high speed, and nonvolatile memory that utilizes a class of
materials–chalcogenides, with Ge2 Sb2 Te5 (GST) being the
most common—that can be rapidly and reversibly switched
between a highly resistive amorphous (reset) state and a con-
ductive crystalline (set) state [4]–[6]. Phase-change material
is crystallized (set) by heating above the glass transition
temperature and amorphized by melting followed by rapid
solidification (reset) [7], [8] [Fig. 1(a)]. Unlike conventional
electronic devices, the material in the active region changes
dynamically between amorphous, crystalline, and liquid [9]
phases as the local temperature cycles from ∼300 to ∼1000 K
in nanoseconds during device operation. Thermal gradients
can exceed 50 K/nm [10] and thermoelectric contributions
Manuscript received June 29, 2017; revised August 21, 2017; accepted
August 22, 2017. Date of publication September 8, 2017; date of current
version October 20, 2017. This research was supported by National
Science Foundation under Grant ECCS CAREER 1150960. The review
of this paper was arranged by Editor C. M. Compagnoni. (Corresponding
author: Zachary Woods.)
The authors are with the Department of Electrical and Computer
Engineering, University of Connecticut, Storrs, CT 06269 USA (e-mail:
Zachary.woods@uconn.edu; ali.gokirmak@uconn.edu).
Color versions of one or more of the figures in this paper are available
online at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/TED.2017.2745506
are very significant [10], [11]. PCM design tools have to
simultaneously capture rapidly changing material behaviors
and local metastable electrical [12], thermal [13], [14], and
electro-thermal properties [15].
Thus far compact models [13], [16]–[19] and finite-element
approaches [8], [20]–[26] have been proposed to simulate
the operation of PCM devices. Compact models can be con-
structed for given pulse and load conditions [27], [28] for
a certain device architecture based on parameters extracted
from experiments. These models can be integrated with circuit
design tools for memory array and module design.
Finite-element models are necessary for detailed analysis of
individual PCM cells to evaluate the contributions of the mate-
rials, geometry, load and pulse conditions, short- and long-term
impact of thermal cycling, and process conditions.
Typically, simplified crystallization models, such as Johnson–
Mehl–Avrami–Kolmogorov (JMAK) models [16], [17],
[19], [26], [29]–[32], are used for electro-thermal device
operation, or more sophisticated growth models [29] are
used for process simulation that are not integrated with
electro-thermal models.
JMAK models over simplify the crystallization kinetics and
do not model the stochastic nucleation process or the effects
of multiple crystal grains. The JMAK models rely on the

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WOODS AND GOKIRMAK: MODELING OF PCM: PART I—EFFECTIVE MEDIA APPROXIMATION
assumptions that nucleation is random, uniform, and time
independent [19]. During the operation of PCM devices, large
local temperature gradients result in spatially variable nucle-
ation probabilities. Ignoring these local effects can greatly
alter device operation due to local current density and heating
conditions.
Dedicated crystallization models, relying on classical nucle-
ation and growth theory, only examine uniformly heated
rectangular geometries [21], [26]. These models generally are
computationally intensive and are not integrated with heat
transfer and current continuity physics for device simulations.
Unified models to date [20] do not combine field-dependent
electrical conductivity, which is necessary to simulate set [8],
thermoelectric effects [10], [11], which are significant due to
high temperatures and thermal gradients, with crystallization–
amorphization dynamics [20].
Here, we describe a computationally efficient empirical
finite-element model based on classical nucleation and growth
dynamics using an effective media approach (Part I) and using
discrete nucleation and grain growth tracking grain orienta-
tions and grain boundaries (Part II) integrated with electro-
thermal models using temperature and electric field-dependent
materials properties [8], [10], [27]. Our models can simulate
crystallization of GST in any structure in 2-D or 3-D under
arbitrary heating conditions where a thermal gradient and/or a
transient may be present. Simulations performed in COMSOL
multiphysics model crystallization–amorphization dynamics
alongside Joule heating, heat transport, and thermoelectric
effects to comprehensively model the device behavior. This
approach allows for the modeling of dynamic crystallization
during a set or reset operation, allowing for updates of the
electrical, thermal, and mechanical properties of the material
as it changes phase.
The changes in the temperature and its impact on the
material properties can be captured in electro-thermal sim-
ulations that solve the current continuity (1) and heat
transfer (2) expressions self-consistently using temperature
dependent material properties [8], [10], [22], [27]
J = −∇ · σ (T )∇V − ∇ · (σ (T )S∇T ) = 0 (1)
dT J2
dG C P (T ) − ∇ · (κ(T )∇T ) = − JT · ∇ S (2)
dt σ (T )
where J is the current density, σ is the electrical conductivity,
V is the electric potential, S is the Seebeck coefficient, dG is
the mass density, C p is the heat capacity, T is the temper-
ature, t is the time, and κ is the thermal conductivity. The
thermoelectric effects are handled through the Seebeck current
term in (1) and the Thomson heat term in (2) [10]. A field-
dependent electrical conductivity component for the phase-
change material is used to capture the dielectric breakdown
for set operation [8] and SPICE models are used to capture
the impact of the access devices [28].
II. DYNAMIC M ODELING
Finite-element modeling of the mixed phase materials using
isolated domains [Fig. 1(b)] [23] is computationally intensive
as the interfaces need to be heavily meshed and the domains
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4467
TABLE I
A SSOCIATED C ONSTANTS W ITH U NITS
have to be dynamically altered to capture growth. A mesh-
based approach using a crystallinity variable is more efficient.
This can be implemented using a uniform mesh spacing of
∼1 nm and a binary variable to indicate crystalline state to cap-
ture the stochastic nature of nucleation [Fig. 1(c)] [22] or an
effective media approximation can be used within each mesh
element to allow variations in mesh size [Fig. 1(d)]. The
latter approach, which we have chosen for this paper, also
allows for 2-D rotationally symmetric simulations. To fully
capture the nucleation, growth, and amorphization processes
during electro-thermal simulation (1) and (2) and allow
nonuniform meshing, we have constructed a single rate equa-
tion (3) tracking local crystal density (CD) [Fig. 1(d)], where
CD = 0 and 1 limits correspond to fully amorphous and fully
crystalline volumes
dCD
= Nuc(T, CD) + Grow(T, CD) + Amorph(T, CD)
dt
(3)
where Nuc(T, CD), Grow(T, CD), and Amorph(T, CD) model
crystallization contributions from nucleation, growth, and
amorphization, respectively.
Nucleation is modeled by
1
Nuc(T, CD) = N(T )(1 − CD)e CD+0.3 rnd(r, z, t) (4)
−(T −α1 )2
N(T ) = e α2 (5)
where r and z in (4) are spatial variables of the cylindrical
coordinates of a rotationally symmetric geometry [Fig. 1(a)],
and αn are the constants listed in Table I. The Nuc(T, CD)
term (4) is used to initiate a change in local CD, modeling
nucleation. N(T ) (ns−1 ) in (5) is a calibration term and has
constant α1 and α2 selected to match the published nucleation
rate of GST [17] assuming nuclei of 1 nm3 . Nucleation
is scaled with (1-CD), remaining amorphous fraction, and
by an exponential term to model reduced nucleation rate in
close proximity to other nuclei (for CD > 0.3). The random
function, rnd(r, z, t), is distributed continuously and uniformly
between 0 and 1. This function is updated at every timestep
and is used to capture the stochastic nature of nucleation.
Growth is modeled by
Grow(T, CD) = G InMesh (T, CD) + G InterMesh (T, CD)
(6)
G InMesh (T, CD) = α3 v G (T )F1 (CD) (7)
 
−2
F1 (CD) = + 1 FStability (8)
1 + eCD+0.1
 
FStability = α4 e−(CD−0.5) + α5
2
(9)
 
CD−0.5 −1
G InterMesh (T, CD) = α6 v G (T ) 1 + e 0.1 ∇ 2 CD. (10)
4468 IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 64, NO. 11, NOVEMBER 2017

Fig. 2. Nucleation, growth, and amorphization rates for CD = 0.5.

The Grow(T, CD) term (6) is composed of an in-mesh growth

component (7) and (8) responsible for increasing CD within
individual mesh points (volume) and an intermesh compo-
nent (9) to model the expansion of grains. The published
growth rate [17] v G (T ) is calibrated via α3 in (7) such that Fig. 3. Empirical (a) ρ(T, CD) and (b) S(T, CD) (solid lines) for GST
complete crystallization of a large volume is possible in 100 ns based on our experimental results (points) and the expected values
at Tmelt . ρ(300K, CD) is displayed in the inset.
and appropriate growth velocities are observed in simulation.
v G (T ) data is also modified such that no growth occurs
above Tmelt . F1 term of G InMesh (8) is included to enable
growth only after nucleation, while an exponential with α4 and
α5 provide stability at CD = 0, 1 (9). Intermesh growth (10)
is setup to allow growth at the amorphous side of the crystal–
amorphous boundaries with a maximum growth velocity
of 1 nm/ns [17] by selecting α6 . The exponential term in (10)
is present to prevent a nonphysical negative value of G Intermesh
in locations of high CD where a negative value of ∇ 2 CD
is present. Amorphization is turned on at Tmelt (873 K) by
the exponential term in (11) which acts as a step function,
stabilizing at CD = 0 within 4 ns (Fig. 2).
Amorphization is modeled by

1
Amorph(T, CD) = CD T −873
−1 (11)
1 + e 0.5
Fig. 4. Simulated I–V curves of a slow voltage sweep of a mushroom cell
and has units of ns−1 . starting in the reset state (8 MΩ), with arrows indicating time evolution.

III. M ATERIAL P ROPERTIES M ODEL

The local material properties all depend on CD and T ,
and are based on measured values. It is assumed that fully
crystallized face centered cubic GST (fcc-GST, CD = 1) has
a constant resistivity value of ρ = 2.07 · 10−3  · cm for
T < Tmelt . Resistivity for 0 < CD < 0.3 remains very close to
the amorphous value until percolation paths form (Fig. 3) [23].
ρ (T, CD) and S(T, CD) functions were constructed with
simultaneously measured [15] ρ–T and S–T curves from a
series of anneals, and ρliquid = 2.1 · 10−4  · cm [9], Sliquid =
2 · 10−5 V/K at Tmelt [10], [33]. The field dependence of
electrical conductivity is modeled as in [8] to enable modeling
of the set operation: σ (T, CD, E) = σT (T, CD) + α7 eα8 |E| .
Thermal conductivity is modeled as the sum of electronic
and phonon (κph ) components. κph is a weighted average of
amorphous (κph-a ) and crystalline (κph-fcc ) values
κ(T, CD) = Lσ T + κph (T, CD)
κph (T, CD) = κph-a · (1 − CD) + κph-fcc · CD
where L is the Lorenz number (2.44 · 10−8 W · K−2 ) [10],
κph−a is 0.27 W·m−1 ·K−1 and κph-fcc is 0.4 W·m−1 · K−1 [34].
C p is modeled as a constant (202 J/kg · K) [10], [35] with a
peak at the melting (Tmelt ) [10] to account for the latent heat
of fusion (126 k J/kg)[11] and the mass density, dG , of GST
is 6.2 g ·cm3 [36]. Peltier heat at the GST-metal interfaces and
the thermal boundary resistances are modeled as in [10].
IV. R ESULTS
To simulate the commonly known “snapback” scenario, seen
in slow experiments [37], the mushroom cell geometry from
Fig. 1(a) is reset using a 50 ns 2.5 V pulse followed by a
2-μs voltage sweep from 0 to 2.8 V and back to 0 V (a trian-
gular pulse). The I –V characteristics (Fig. 4) first follow the
high-resistance amorphous behavior until a threshold voltage,
when the “snapback” takes place, the cell resistance drops due
(12) to electric breakdown resulting in a voltage drop across the
(13) cell. Further increase in the applied voltage heats the device

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WOODS AND GOKIRMAK: MODELING OF PCM: PART I—EFFECTIVE MEDIA APPROXIMATION
Fig. 5. (a) Applied voltage and (b) current versus time for a full reset–
read–set cycle for two different set cases and the calculated energy
of each operation. (c) Simulated I–V characteristics for reset and set
operations and (d) tapered set pulse with a long fall time (300 ns),
resulting in melting and crystallization. Arrows indicate the time evolution.
Time evolution of crystallization (100 ns/frame) during (e)–(g) set by
a low-amplitude long-duration pulse, Rinitial /Rfinal = 1 MΩ/6 kΩ and
(h)–(j) set by growth-from-melt, Rinitial /Rfinal = 8 MΩ/8.7 kΩ. White
contours indicate solid–liquid interface and arrows indicate direction
of crystal growth. Heater diameter =10 nm. (Multimedia available at
http://ieeexplore.ieee.org.)
further, crystallizing the amorphous region as in Fig. 5(e)–(g),
and eventually melting the active area at peak voltage. Slowly
ramping the voltage down again allows for recrystallization
as in Fig. 5(h)–(j), and the current follows the low-resistance
crystalline behavior.
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4469
Fig. 6. Simulated consecutive set (open symbols)/reset (solid symbols)
results for a mushroom cell Vreset = 2 V (green), Vreset = 2.25 V (blue)
and Vreset = 2.5 V (red). All set pulses are 1.2 V with 300 ns duration.
Both simulations start in the set state with Rinitial = 4 kΩ (black). The
read operations are performed after cell returns to ambient temperature.
It has been experimentally demonstrated that the reset
is achieved by melting or bringing the cell close to Tmelt
and set operation can be achieved by either annealing at
a lower temperature or by melting and recrystallizing with
a tapered pulse [38]. Our simulation setup can reproduce
these reset/read/set cycles for both options for the set oper-
ation as demonstrated through the V –t, I –t characteristics
[Fig. 5(a) and (b)] and the pulsed I –V constructed using
these results [Fig. 5(c) and (d)]. The two set operations
use a distinctly different mechanism that are advantageous
for different geometries, length scales, and materials: the
nucleation and growth approach, using a long duration low-
amplitude pulse, can set the cell with much less energy with a
crystalline volume growing up from the heater/GST interface
[Fig. 5(a) and (e)–(g). However, the amorphous volume has
to be relatively large to initiate nucleation in the hearth
of the amorphous plug in a reasonable time scale and it
is more suitable for nucleation-dominated materials such as
GST. The growth-from-melt approach using melting pulses
with tapered ramp-down requires significantly more energy
and peak current but is more consistent for small amorphous
plug volumes as the crystal front grows from the top of the
amorphous dome to the bottom and does not rely on nucleation
[Fig. 5(a) and (h)–(j)]. Hence, the cell geometry and scaling,
and the set approach to be used has to be included in the design
considerations depending on the target applications [39].
As this framework handles the changes in the phase-change
materials in real time, the set and the reset simulations do not
have to be divided into two separate studies to change the
material states. Hence, it is possible to simulate consecutive
set/reset operations (cycling) of any device geometry by apply-
ing repeated set and reset pulses and construct the simulated
resistance window (Rreset /Rset ) for various amplitudes (Fig. 6)
and waveforms similar to the experiments [40], [41].
4470
Fig. 7. Rreset of tapered reset as a function of τdown . The dashed line
shows fully set resistance. Applied voltage waveforms are shown in the
inset.
We are able to see the evolution of the resistance of each
state in time, get more insight into the mechanisms of device
failure, and determine the peak reset voltage needed to achieve
the desired memory window.
PCM offers the possibility of storing multiple bits per cell.
This is typically achieved by setting a cell to one or more
intermediate resistance levels in addition to the lowest resis-
tance state. If melting and growth-from-melt is used for the
set operation, multiple resistance states can be achieved by
controlling the ramp-down time (τdown ) (Fig. 7) [38]. It is
important to note that once the cell is molten, the voltage
required to keep the cell in molten state is much less than
Vreset . Hence, significant portion of the active region remains
in molten state for much of the τdown , while the rest stays at
an elevated temperature, allowing templated growth from the
crystalline dome [Fig. 5(i)].
V. S UMMARY
The simulation of PCM cells with arbitrary geometries and
multiple set/reset cycles is now possible using the framework
described in this paper. The rate expression used to model
nucleation, growth, and amorphization functions is integrated
with the electro-thermal models we have developed earlier.
The model includes stability terms to keep the CD within the
0 < CD < 1 window and allow continuous simulation of
multiple operations. The results shown here are from rotation-
ally symmetric simulations that do not capture the variability
in various angles. Hence, the active region amorphizes and
recrystallizes as a symmetric mushroom. The same approach
can be applied for 3-D simulations to capture this variability.
The CD approach using an effective media approximation
allows for variable mesh and high-speed computation. Adjust-
ments have to be made to the nucleation function and a higher
density mesh needs to be used to capture discrete nucleation
as discussed in manuscript Part II.
ACKNOWLEDGMENT
The authors would like to thank A. Faraclas for his work on
the electro-thermal model, L. Adnane for the characterization
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IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 64, NO. 11, NOVEMBER 2017
of Seebeck coefficient and resistivity of GST, and F. Dirisaglik
for his characterization of metastable amorphous GST.
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Zachary Woods received the B.S. degree in
biomedical engineering from the University of
Connecticut, Storrs, CT, USA, in 2015, and the
M.Eng. degree in biomedical engineering from
Cornell University, Ithaca, NY, USA, in 2016.
He was an Undergraduate Research Assis-
tant with the Nanoelectronics Laboratory, Univer-
sity of Connecticut, with Dr. Ali Gokirmak and
Dr. Helena Silva.
Ali Gokirmak (SM’12) received the B.S. degree
in electrical engineering and physics from the
University of Maryland, College Park, MD, USA,
in 1998, and the Ph.D. degree in electrical and
computer engineering from Cornell University,
Ithaca, NY, USA, in 2005.
He is currently an Associate Professor of elec-
trical and computer engineering with the Univer-
sity of Connecticut, Storrs, CT, USA.