Chemical Engineering Research and Design 183 (2022) 595–607

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Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Neural network-based model predictive control for

thin-film chemical deposition of quantum dots
]]
]]]]]]
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using data from a multiscale simulation

⁎
Niranjan Sitapure a,b, Joseph Sang-Il Kwon a,b,
a
Texas A&M Energy Institute, Texas A&M University, College Station, TX 77845, USA
b
Artie McFerrin Department of Chemical Engineering, Texas A&M University, College Station, TX 77845, USA

a r t i c l e i n f o a b s t r a c t

Article history: Recently, thin-film deposition of quantum dot (QDs) to manufacture solar cells and dis­
Received 3 May 2022 plays have received significant attention due to the lucrative optoelectronic properties of
Received in revised form 23 May these devices. Unfortunately, (a) the existing macroscopic thin-film deposition models in
2022 the literature do not consider the surface-level interactions; (b) the detailed surface-level
Accepted 26 May 2022 models do not consider the entire thin-film deposition ensemble; and (c) multiscale
Available online 1 June 2022 modeling studies considering both the scales are not tailored for QD systems. Thus, to
address this knowledge gap, in this work, a multiscale thin-film deposition model is de­
Keywords: veloped. First, the droplet distribution and evaporation dynamics during the thin-film
Thin-film deposition deposition of QDs are described using heat and mass balance equations. Second, a mi­
Model-predictive controller croscopic discrete-element method (DEM)-based particle aggregation model that describes
Neural networks the surface-level particle interactions is developed and combined with the macroscopic
Spray coating dynamics. Furthermore, a model predictive controller (MPC) is designed to regulate the
Quantum dots film thickness and minimize the film roughness by manipulating key process variables. To
design a feasible MPC, a computationally efficient artificial neural network (ANN) model of
the thin-film deposition model is constructed, and it is incorporated within the MPC. The
closed-loop simulation results showcase the capability of the MPC to achieve the required
film thickness and minimize the roughness.
© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.

plethora of research in the discovery, optimization, and

1. Introduction
commercial production of QD-based optoelectronics like
solar cells and LED displays (Zhang et al., 2021; Park and Zhu,
Perovskite quantum dots (QDs) have recently garnered a lot
2020). In pursuit of this goal, thin-film deposition techniques
of attention as a promising semiconducting material for ap­
like spray coating of QDs have come into the limelight for the
plications in next-generation solar cells, and light-emitting
manufacturing of QD-based thin-films for solar cells and QD-
diode (LED)-based displays (Zhang et al., 2016b; Petrus et al.,
based LED displays (Yuan et al., 2019; Gao et al., 2020).
2017; Sitapure et al., 2022, 2020b; Yang et al., 2020). This is
In these processes, micron-sized droplets of a colloidal QD
because, these QD systems have relatively high photo­
solution are sprayed over an appropriate substrate. Then,
luminescence quantum yield, provide tunable absorption/
since the substrate is at an elevated temperature, the solvent
emission spectra, and follow a low-cost room-temperature
evaporates leaving behind deposited QD particles, which
synthesis route (Protesescu et al., 2015; Yu et al., 2019;
forms a thin-film. Various process parameters, like thin-film
Sitapure et al., 2020a, 2021). These advantages have fueled a

⁎
Corresponding author at: Texas A&M Energy Institute, Texas A&M University, College Station, TX 77845, USA.
E-mail address: kwonx075@tamu.edu (J.S.-I. Kwon).
https://doi.org/10.1016/j.cherd.2022.05.041
0263-8762/© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
596 Chemical Engineering Research and Design 183 (2022) 595–607
deposition rate, droplet size, substrate temperature affect the
film characteristics (i.e., film thickness and roughness). Since
these film characteristics are paramount to the performance
of these devices (i.e., light-trapping efficiency, and electron-
hole transport), optimal choice of these operating conditions
is necessary (Makhdoumi-Kakhaki et al., 2016; Azri et al.,
2019). However, predicting the film characteristics for dif­
ferent operating conditions requires an adequate thin-film
deposition model.
The literature is rife with macroscopic thin-film deposi­
tion models that consider droplet distribution, droplet
transport and evaporation dynamics (Hilton et al., 2013;
Fogliati et al., 2006). For example, Miller and his co-workers
developed a mathematical thin-film deposition model for a
silicon-based chemical vapor deposition (CVD) application,
which includes the mass and energy balance associated with
thin-film deposition along with detailed dynamic chemical
reactions for silane and other chemical species (Coltrin et al.,
1984). Although such a model can describe the effect of de­
position rate, temperature, and other factors on film thick­
ness, it does not provide insights into film roughness or film
morphology. In another study, Marathe and his coworkers
developed a detailed finite element-based thin-film deposi­
tion model that considers the trajectory and distribution of
atomized particles via a detailed transport model (Andulkar
et al., 2015). Although the developed model is able to predict
film thickness for a variety of different geometries and
varying operating conditions, it does not consider surface-
level particle interactions and aggregation phenomenon,
which is critical in predicting film roughness.
On the other hand, there are detailed microscopic models
that describe the microscopic surface-level particle interac­
tions during evaporation of spray coated droplets (Maki and
Kumar, 2011; Pham and Kumar, 2017; Li and Christofides,
2005; Hu and Larson, 2006). For example, Kumar and his co-
workers performed a mathematical analysis of the formation
of coffee-ring in evaporation droplets, which leads to uneven
thin-film deposition (Maki and Kumar, 2011). Duan and his
coworkers present a rule-based kinetic Monte Carlo (kMC)
simulation for describing particle aggregation in evaporating
droplets, and consider the effect of circulatory flow and
sticking-coefficient of particles during aggregation (Crivoi
and Duan, 2014). Although the above models can provide a
microscopic probe into the surface-level particle interactions
and aggregation, these models are not integrated with mac­
roscopic thin-film deposition dynamics (i.e., deposition rate,
droplet-size distribution). To resolve this issue, there have
been other studies demonstrating various multiscale thin-
film deposition models that consider the macroscopic
transport dynamics and surface-level particle aggregation
(Crose et al., 2015, 2017; Li and Christofides, 2005). For ex­
ample, Christofides and his coworkers integrated a detailed
porosity inclusive kMC model with a gas transport model to
describe the silicon thin-film growth in a CVD chamber
(Zhang et al., 2010). Although these models consider both the
surface-level thin-film morphology and macroscopic phe­
nomena (as well as their interactions), it is specific to the
silicon CVD process, and is not tailored for QD systems.
Overall, despite the existence of many different modeling
approaches, QD-specific interactions (i.e., van der Waals
force, dipole forces, circulatory force, and Brownian motion)
present at the surface-level are missing from the above-
mentioned models.
To address this knowledge gap, in this work, we devel­
oped a multiscale thin-film deposition model for QD systems,
which describes the important aspects of macroscopic spray
coating dynamics along with surface-level particle interac­
tions. First, a spray nozzle is considered, and the droplet
distribution during atomization is considered as a function of
air and liquid velocities. Second, the evaporation dynamics
of the droplets impinging on the substrate is modeled using
mass and heat transfer equations. Third, a microscopic dis­
crete-element method (DEM)-based particle aggregation
model that describes the coffee ring formation at the surface
level leading to uneven deposition of thin-films is developed.
Specifically, the DEM-based model considers dipole interac­
tions, van der Waals interaction, and Brownian motion of QD
particles in the evaporating droplets to describe the spatio­
temporal evolution of QD particles. Overall, the above three
aspects of the film-deposition process are combined to con­
struct a multiscale thin-film deposition model.
Also, since the objective of the thin-film deposition pro­
cess is to have desired film characteristics (i.e., film thickness
and minimum film roughness), a model predictive controller
(MPC) is formulated to manipulate three inputs (i.e., air ve­
locity, liquid velocity, and spray nozzle height) to achieve a
desired film thickness and roughness. It is important to note
that deploying an MPC requires a computationally efficient
surrogate model to perform the optimization within the MPC
formulation. In the literature, this issue has been addressed
by constructing an artificial neural network (ANN) to mimic
the high-fidelity model (Zheng et al., 2022; Zhao et al., 2022;
Wu et al., 2019; Wong et al., 2018; Choi et al., 2021; Kiš and
Klaučo, 2019; Lee et al., 2020). For example, Christofides and
his coworkers developed an ANN-based surrogate model for
describing the batch crystallization of a pharmaceutical
product, and integrated it within an MPC formulation to
control the crystal size distribution (Zheng et al., 2022). Thus,
the simulation data from the developed thin-film deposition
model was utilized to construct an artificial neural network
(ANN), which was used as an efficient surrogate model
within the MPC formulation. The closed-loop simulation re­
sults showcase that the desired film thickness can be
achieved while maintaining a smooth deposition profile.
Furthermore, the film thickness and roughness values that
were achieved are in good agreement with the experimental
results.
To give an exhaustive account of the above-mentioned
concepts, the rest of the manuscript is organized in the fol­
lowing way. First, the thin-film deposition process is de­
scribed using appropriate continuum equations. Then, the
DEM-based surface-level simulation is described in detail.
Further, the MPC design along with the required ANN-based
surrogate model is presented. Finally, the closed loop simu­
lation results for the developed MPC are presented, which is
followed by concluding remarks.
2. Mathematical modeling of thin-film
deposition
2.1. Process description
In this work, a spray applicator atomizes and sprays colloidal
QD solution onto a heated substrate to achieve thin-film
deposition as shown in Fig. 1. Consequently, atomized dro­
plets impinge onto the substrate and form tiny droplets fol­
lowed by solvent evaporation. Furthermore, during the
 Chemical Engineering Research and Design 183 (2022) 595–607
Fig. 1 – A schematic illustration of the proposed multiscale
spray coating process along with a heated substrate for
auto-curing of the thin-film. The red dots in the magnified
area are QD particles that are undergoing particle
aggregation.
Fig. 2 – A schematic illustration of the spray nozzle
considered in this work. The liquid velocity (vl), and gas
velocity (vg) can be manipulated along with spray nozzle
height (Hn).
solvent evaporation, the QD particles, which have a size
range of ~ 10 nm, undergo particle aggregation due to the
presence of various molecular interactions, and result in film
formation (Wang et al., 2020). Also, Fig. 2 shows that liquid
velocity (vl) and gas velocity (vg), which dictate the deposition
rate of atomized droplets, can be adjusted to change the thin-
film deposition dynamics. Furthermore, spray nozzle height
(Hn) can be adjusted to change the spread of deposited dro­
plets, which follows a Gaussian distribution, X ~ N(μ, σ). That
is to say that the density of impinging droplets decreases in a
radial manner as one moves away from the center of spray
applicator. For example, Fig. 2 shows the spread of droplets
for two different heights (i.e., HA and HB), and the spread of
droplets is higher in the case of HB than HA as HB > HA. Also,
the concentration of the colloidal QD solution is ~ 0.02 mol/
597
m3, and is computed based on previous studies (Sitapure
et al., 2020a; Epps et al., 2017, 2018).
2.2. Macroscopic thin-film deposition model
In this work, a heated silicon substrate was considered with a
spray applicator positioned at the substrate center, and op­
erating at a deposition rate, F. It is important to note that F is
a function of gas and liquid velocity at the spray nozzle
(Fig. 2). Also, as mentioned above, the spray cone from the
spray applicator follows a normal distribution, X ~ N(μ, σ),
which indicates that the density of atomized droplets de­
creases with the radial distance from the nozzle center (Payri
et al., 2008 as shown in Fig. 1). Following the abovementioned
methodology, the evolution of QD thin-film thickness is
given as follows:
dhx, y
t t 1 x2 + y2
Asub = F (t ) exp (1)
0 dt 0 2 Hn2
where hx,y indicates the film height at location (x, y) ∈ L, Asub
is the substrate area, and L represents the substrate lattice.
Thus, the evolution of film thickness varies with F, and Hn
across the substrate lattice. Specifically, an arbitrary location
(x1, y1), which is at a certain distance from the substrate
center (x = 0, y = 0), will have less deposition than at the
substrate center. Furthermore, the quality of thin-film was
calculated using the root-mean-square error-based rough­
ness (ψRMSE) of thin-film, which is defined as follows:
L
1
RMSE = (hx, y h¯ )2 (2)
L
where h̄ is the average film height, and L represents all the
lattice points on the substrate. The film roughness is an
important feature that affects the performance of thin-film-
based optoelectronic devices, and thus, tracking the evolu­
tion of film roughness and thickness is imperative to the
manufacturing of high-performance QD thin-films.
2.2.1. Deposition rate and droplet size
The deposition rate (F) in the above equations is determined
by liquid velocity, and is given as F = vlAnoz, where Anoz is the
cross-sectional area of nozzle. Furthermore, along with the
deposition rate, droplet size and the distribution of droplet
size are important considerations. Specifically, the ratio of air
velocity (vg) and liquid velocity (vl) controls the droplet size
distribution in a spray nozzle. For example, at a high vg∕vl
ratio, the droplets are atomized to a fine size (< 100μm) while
at a low vg∕vl ratio they can be in the range of ~ 500 μm. Thus,
to include the size variation of atomized droplets, the fol­
lowing correlation for two-phase gas/liquid nozzles is uti­
lized (Kim and Marshall, 1971):
0.45
585 l µl 1000vg
ds = + 597 (3)
vg vl l l l vl
where ds is the Sauter-mean diameter (SMD) of atomized
droplets, σl is the surface tension of solvent, ρl is the solvent
density, and μl is the solvent viscosity. Furthermore, for a
given vg∕vl ratio, the size of atomized droplets will have a
slight deviation from SMD, and it results in a droplet size
distribution around SMD. Thus, to include this droplet-to-
droplet size variation, atomized droplets are assumed to
have a Gaussian distribution as shown below:
di = Nd (SMD, d) (4)
598 Chemical Engineering Research and Design 183 (2022) 595–607
Fig. 3 – A schematic illustration of the evaporating droplet
considered in this work. The blue dots in the magnified
area are QD particles within each atomized droplets.
where di indicates the diameter of an arbitrary droplet, and σd
is the standard deviation of the droplet size around SMD.
2.3. Surface-level droplet evaporation
Now that we know the deposition rate and the size dis­
tribution of impinging droplets, it is important to consider
their evaporation dynamics. Basically, atomized droplets
land on the heated substrate as shown in Fig. 3, and the
solvent (toluene) starts to evaporate leaving behind the QD
particles that are deposited to form the QD thin-film. Speci­
fically, consider droplets of radius Rd that are now stationary
on the substrate surface as shown in Fig. 3. Here, it can be
assumed that there is no external flow of gas or liquid, and
thus, a diffusion-controlled droplet evaporation dynamics is
considered as shown below (Eslamian, 2013):
dm
= 4 Rd Dg ( g, Rd g, )
dt
g, Rd = Psat R gas T
where m is the total mass of evaporating droplet, Rd is the
radius of droplet, Dg is the gas-vapor mutual diffusion coef­
ficient, and g, Rd and ρg,∞ are the solvent vapor concentration
(kg∕m3) at the surface and ambient condition, respectively.
Also, Psat is the saturation pressure of toluene at temperature
T, and can be computed using a combination of the Clausius-
Clapeyron equation and the latent heat of solvent (ΔHL) as
follows:
Psat HL 1 1
= exp
Po Rgas To T this work.
where (P0, To) is a known pressure-temperature pair within
the vapor-liquid equilibrium space of toluene, and Rgas is the
universal gas constant.
Additionally, since the substrate is at an elevated tem­
perature and the droplet is at 30 ∘C, the temperature evolu­
tion of droplet needs to be monitored. To this end, we can
write an energy balance equation across droplet as follows:
dT dm
s Cp = Rd2 (Ts T ) + HL
dt dt
where T is the droplet temperature, λ is the heat transfer
coefficient, and Cp is the heat capacity of solvent. Here, it is
assumed that heat transfer from the substrate surface to
droplet takes place in the laminar regime (Aissa et al., 2015),
and thus, the Nusselt Number (Nu) has a value of ~ 2.
2.4. Surface-level QD particle interactions
As mentioned above, atomized spray droplets impinge onto
the heated substrate and undergo evaporation.
Simultaneously, the QD particles within the droplets, which
are under the influence of various molecular interactions,
undergo particle aggregation as shown in Fig. 3. Specifically,
the complex interplay between these interactions can result
in interesting spatiotemporal variation of deposited QD par­
ticles, which contributes to film roughness. Thus, a detailed
investigation of surface-level particle interaction is im­
portant.
To accurately describe the microscopic dynamics of this
phenomenon, a DEM model is developed. In the model, the
resultant force on each QD particle in the system is com­
puted in accordance with Newton’s law of motion. The re­
sulting force is then utilized to update the position of that QD
particle, and this process is repeated for every QD particle for
all simulation times. Here, the displacement for each QD
particle in the simulation space can be described in the fol­
lowing manner:
dvp
mp = F = fd + fvdW + fb + fc (8)
dt
where mp is the mass of a single QD particle, vp is the in­
stantaneous particle velocity, fd is the dipole force, fvdW is the
van der Waal’s force, fb describes Brownian motion, and fc
represents the circulatory flow in an evaporating droplet.
After computing the resultant force on each QD particle, the
instantaneous velocity and displacement of the QD particle
is calculated in the x and y directions, and given as follows:
Xti + ts = Xti + ts vxi , t ; vxi , t = (Fxi mp ) ts
(9)
(5) Y ti + ts = Y ti + ts vyi , t ; vyi , t = (Fyi mp ) ts
where Xi and Yi represent the position of the ith QD particle in
the Cartesian space, and Δts is the microscopic simulation
time-step. Also, vxi and vyi are the instantaneous velocity of
the ith QD particle in the x, and y directions, respectively.
Finally, a schematic illustration of the computation of the
resultant force on a particular QD particle is shown in Fig. 4.
As mentioned above, the QD particles are under the in­
fluence of various molecular interactions, and the effect of
these interactions can be modeled via a DEM approach as
seen in Eq. (8) and Eq. (9). Thus, the following sub-sections
describe the various molecular interactions considered in
(6)
2.4.1. Brownian motion
The QD particles are in the size range of 5–20 nm, and at this
length scale, Brownian motion becomes a dominant trans­
port mechanism. Thus, all QD particles within the boundary
of droplets will exhibit Brownian motion. The stochasticity of
Brownian motion is effectively captured by Gaussian white
noise, which is given as follows (Peng et al., 2010):
12 Rµl kB T
(7) fB =
ts
(10)
where R is the radius of QD particles, kB is the Boltzmann
constant, and ξ ∈ (0, 1] is a random number.
2.4.2. van der Waal’s interactions
At the nanoscale, it is important to consider the effect of van
der Waal’s force between QD particles. The van der Waal’s
 Chemical Engineering Research and Design 183 (2022) 595–607
Fig. 4 – A schematic illustration of resultant force
calculation in the developed microscopic DEM model. Here,
dcut is the cut-off distance, after which the strength of
molecular interactions is negligible, and d is the distance
between two QD particles.
force is inversely proportional to the distance between QD
particles. Thus, in the literature, a Hamaker approximation
of the van der Waal’s interaction has been developed for the
system of QD particles, which is given as follows (Wang
et al., 2019):
2 As mentioned earlier, an accurate description of the entire
2A131 2 1 1
R [d + 2R ] if d > 0.1(R + h0 )
3 d2 + 4Rx [d + 2R]2
fvdw =
R A232 2A123 A131
+ if d < 0.1(R + h0 )
12 d2 [d + h0]2 [d + 2h0]2
where d is the distance between two QD particles, R is the
radius of the QD particle, and h0 is the equilibrium length
of ligand. A131, A123, and A232 are the Hamaker constants for
CH3NH3PbX3 QDs, n-octylamine (ligand), and toluene (sol­
vent), respectively (Wang et al., 2019). Specifically, A131
= 4.69 × 10−20 J, A232 = 4.29 × 10−22 J, and A123 = 1.05 × 10−21J. It
is important to note that these QD-specific molecular para­
meters can be altered if another QD system is considered.
2.4.3. Dipole interactions
Due to the asymmetric distribution of electron cloud within
QD particles, a significant dipole moment is found for the
family of QD particles (i.e., CdTe, CdSe, CsPbX3, MAPbX3) (Cho
et al., 2005; Zhang et al., 2016a). As a result, neighboring QD
particles are attracted towards each other, and therefore, this
effect needs to be considered during the aggregation of QDs.
The literature suggests that the dipole force between two QD
particles can be defined as follows (Wang et al., 2019):
2 2
µ12 C1
d 6 6 3 2 3
fd = e 4
+ 3 + 2 +
4 0 eff d d d d
where μ12 = 1.18 × 10−26 Cm is the dipole moment of the two
interacting QD particles, ϵ0 is the dielectric constant for va­
cuum (8.854 × 10−12 Fm−1), ϵeff is the relative permittivity of
solvent, 1∕κ is Debye screening length, and C1 is a pro­
portionality constant.
2.4.4. Circulatory flow
Another important microscopic force that needs to be con­
sidered, particularly during the evaporation of micron-sized
droplets, is circulatory flow. Experimental observations sug­
gest that the degree of solvent evaporation near the contact
line (i.e., edge of the evaporating droplet) is higher than that
at the center (Maki and Kumar, 2011; Crivoi and Duan, 2014;
599
Xu et al., 2017). Further, Deegan and co-workers advocated
that this phenomenon results in a diffusive gradient from the
center to the periphery of droplet (Deegan et al., 1997). This
preferential flow also carries the solute (i.e., QD particles in
our case) to the periphery of droplet leading to preferential
deposition of solute at the droplet edge. To provide a math­
ematical expression of this phenomenon, Hu and Larson
defined an analytical expression to compute circulatory flow
velocity as shown below (Hu and Larson, 2006):
3 1 z¯ 2
v¯ r = [(1 r¯ 2 ) 0]
2
8r¯ 1 t¯ h¯
(13)
2z¯ ¯ 2 h¯
rh z¯ 3z¯ 2
+ 02 [¯J 0 (1 r¯ 2 ) 0 1 + 1]
h¯ R0 h¯ 2h¯
2
where v¯ r = vr t f Rd is the dimensionless circulatory flow ve­
locity, t¯ = t t f is the dimensionless evaporation time, z¯ h¯ is
the dimensionless droplet height, tf is the total time for
complete evaporation of droplet, J̄ is the dimensionless
evaporation rate, and r̄ is the dimensionless droplet radius.
Also, 0 = ( 21 ) is the modified contact angle, and θ is 3∘ in
this work (Xue et al., 2010).
2.5. Multiscale thin-film deposition model
thin-film deposition process requires modeling of the various
(11) aspects of the film-deposition process. Specifically, (a) thin-
film deposition equations; (b) droplet size distribution data;
(c) evaporation dynamics; and (d) information from the sur­
face-level particle interactions are integrated to construct a
multiscale thin-film deposition model as shown in Fig. 5.
First, at the macroscopic-level, the three inputs (i.e., gas
and liquid velocities, and spray nozzle height) are selected,
and used to find the deposition rate, the droplet size, and the
spread of droplets. Second, for each impinging droplet, the
surface-level particle aggregation is described by a detailed
DEM-based model. Here, it is important to note that surface-
level modeling of a single droplet is representative of the
entire ensemble of droplets in the film-deposition model. For
example, it is assumed that the particle aggregation dy­
namics for a single evaporation droplet is assumed to be very
similar to the particle aggregation dynamics of the entire
ensemble of impinging droplets. Without this assumption,
the high-fidelity surface-level simulation of millions of im­
pinging droplets would not have been implemented in
practice. Finally, the information about deposition rate and
the spread of droplets at the macroscopic level is combined
with the surface-level particle aggregation at the microscopic
(12) model to formulated a multiscale thin-film deposition model
as shown in Fig. 5.
Remark 1. It is important to note that modeling approaches,
similar to the one presented in this work, have been utilized
to describe various chemical and biological process systems
(Salciccioli et al., 2011; Chaffart and Ricardez-Sandoval, 2018).
For example, crystallizers for manufacturing of quantum dot
and other products (Sitapure et al., 2021; Kwon et al., 2013);
pulp digesters in the paper and pulp industry (Choi and
Kwon, 2020); sputtering systems (Lou and Christofides, 2005;
Zhang et al., 2020); and electrochemical systems (Lee et al.,
2021 have been described using various multiscale modeling
approaches. In majority of these cases, a microscopic model
describing the surface level (i.e., crystal growth, thin-film
deposition, polymerization) phenomenon is coupled with a
600 Chemical Engineering Research and Design 183 (2022) 595–607
Fig. 5 – Schematic illustration of the multiscale thin-film deposition framework developed in this work.
macroscopic model (i.e., heat and mass balance, and
transport equations) to provide a high-fidelity description
of the concerned process.
3. Simulation results
In this section, the simulation results for the film-deposition
model are presented. Specifically, results regarding the
macroscopic film formation and the surface-level particle
aggregation are showcased.
3.1. Droplet size distribution
As mentioned earlier, during the operation of a spray nozzle
for thin-film deposition, gas velocity (vg) and liquid velocity
(vl) are manipulated to adjust the deposition rate and the size
of atomized droplets. In this work, vg ∈ [10,20] m/s and vl
∈ [1,2] m/s, and Fig. 6 shows the variation of mean droplet
size across the entire range of operation. Specifically, Fig. 6a
shows that a smaller droplet size is achieved as gas velocity
is increased for a constant liquid velocity (i.e., large vg∕vl
ratio). Also, the overall mean droplet size ranges from 50 μm
to 130 μm.
Fig. 6 – The variation of SMD of atomized droplets is shown for varying liquid and gas velocities.
3.2. Droplet evaporation dynamics
Evaporation dynamics for droplets impinging on the heated
substrate have a dependency on droplet size and substrate
temperature. In this case, the substrate is maintained at an
elevated temperature (Ts), and the impinging micron-sized
droplets get heated up and initiate solvent evaporation.
Fig. 7a shows the temperature evolution of a droplet during
this process for different values of Ts. Specifically, Ts is
maintained at a constant temperature ∈ [50,100]∘C, and the
droplet on the substrate surface is initially at 30 ∘C. It can be
seen that droplet temperature steadily increases from 30∘C
until it reaches the steady value of Ts. Similar behavior is
observed for all the three cases of varying substrate tem­
peratures.
Second, simultaneous to the temperature evolution, the
droplet also absorbs the latent heat of evaporation, which
leads to solvent evaporation. Consequently, the droplet size
shrinks with time until it entirely dries up (i.e., size becomes
zero). To understand this effect, Fig. 7b shows the depen­
dence of solvent evaporation rate on droplet radius for dif­
ferent values of Ts. Specifically, the initial droplet size is 100
μm, and by the virtue of solvent evaporation, the droplet size
steadily decreases with time.
 Chemical Engineering Research and Design 183 (2022) 595–607
Fig. 7 – (a) Temporal evolution of temperature, and (b) dependence of evaporation rate on droplet radius.
3.3. Surface-level particle aggregation
Although Fig. 7 provides an overview of the macroscopic
evaporation dynamics, it is equally important to elucidate
the surface-level deposition pattern of QD particles. The
DEM-based model of an evaporating QD solution droplet was
simulated for a representative impinging droplet with a size
of 100 μm as shown in Fig. 8. It can be seen that at t = 0, the
QD particles are randomly distributed across the droplet
space. Then, the droplet starts to evaporate, which is de­
marcated by the receding black circular curve, and even­
tually, the entire droplet is evaporated at tf of ~ 37 ms. Along
with evaporation, the QD particles can aggregate and move
around in the QD suspension, and these are called mobile
particles ( ?). However, once these particles go outside the
droplet boundary, then they are no longer suspended in the
QD solution, and are considered to be deposited at that fixed
location. Such particles are termed as static particles ( ?), as
they can no longer move around under the effect of Brow­
nian motion or other abovementioned molecular interac­
tions.
Furthermore, there are two competing phenomena during
droplet evaporation and particle aggregation. First, the at­
tractive molecular forces keep the QD particles within the
central bulk of the evaporating droplet. Second, considera­
tion of the circulatory flow, which adds an additional velocity
component in the outward radial direction, helps the QD
particles overcome the weak attractive molecular interac­
tions, and pushes the QD particles towards the periphery.
More precisely, this phenomenon results in the characteristic
coffee-ring effect (CRE) of QD particles (Maki and Kumar,
2011; Jiang et al., 2016; Li et al., 2019). The existence of a CRE
showcases the uneven deposition of QD particles, which will
contribute to the roughness of the as-deposited thin-film,
and thus, it is an important aspect that needs investigation.
Previous experimental studies focusing on QD thin-film de­
position have observed a similar coffee-ring effect, and are
qualitatively in agreement with our simulation results (Jiang
et al., 2016; Li et al., 2019). In simpler terms, along with the
macroscopic droplet size distribution, the evaporation dy­
namics and surface-level CRE contribute to the uneven de­
position of QD thin-films.
Remark 2. It is important to note that in practice, two or more
droplets can coalesce before fully evaporating, and this can
601
lead to a distorted droplet periphery and QD interactions
across the droplets. To incorporate these additional effects,
an even more detailed model is required, and a dedicated
study will be undertaken in the future to address these
aspects. Thus, in the developed model it is assumed that
droplet evaporation and the surface-level particle
interactions occur within a stand-alone evaporating droplet.
3.4. Thin-film deposition
As mentioned in the previous sections, millions of QD solu­
tion droplets will be deposited using spray coating, and their
combined effect will result in thin-film deposition on the
substrate. Specifically, Fig. 9 shows the simulated film topo­
graphy when the three inputs (i.e., gas and liquid velocities
and spray nozzle height) follow an arbitrary input profile. It
can be seen in Fig. 9 that thin-film deposition on the sub­
strate is pretty uneven, and this can be quantified by a nu­
merical roughness parameter (ψRMSE), which is ~ 10 nm in this
case. Furthermore, the film thickness itself varies largely
from 100 to 250 nm, which is not suitable for direct utilization
in QD-based thin-film applications as it is detrimental to the
optoelectronic performance (Makhdoumi-Kakhaki et al.,
2016; Mahdy et al., 2021; Azri et al., 2019; Marinova et al.,
2015). Thus, it is evident from Fig. 9 that there is a need to
regulate the thin-film deposition process to ensure mini­
mized roughness, and achieve the desired set-point
thickness.
4. Controller design
In order to control thin-film thickness (h) and film roughness
(ψRMSE), a controller can be designed to manipulate the var­
ious inputs to regulate the film characteristics. MPCs have
been utilized in a variety of chemical, mechanical, and
electrical engineering applications for set-point tracking, and
disturbance rejection in nonlinear systems (Kwon et al., 2013;
Hwang et al., 2022). Thus, an MPC framework is utilized to
control the uniformity and film thickness of thin-film de­
position of QDs as it can handle the model complexity and
provide optimal inputs tailored to the developed thin-film
deposition model (Li and Christofides, 2005; Kimaev and
Ricardez-Sandoval, 2019).
602 Chemical Engineering Research and Design 183 (2022) 595–607
Fig. 8 – Simulation snapshots of surface-level spatio-
temporal evolution of deposition of QD particles. The blue
colored ( ?) QD particles are termed as mobile particles, and
are within the bulk of the evaporating drop. The red colored
QD particles ( ?) are static particles. The black boundary
indicates the receding radius of the evaporating drop. Here,
Ts is 100∘C, and the droplet size is 100 μm.
However, for the MPC to find the optimal series of inputs
at every time-step, it needs to solve the optimization pro­
blem, and it includes performing multiple iterations over the
thin-film deposition model. Since the MPC is deployed in
Fig. 9 – Surface evolution of the thin-film deposition when
various inputs (i.e., the gas and liquid velocities, and the
spray nozzle height) have arbitrary values within the
operating range of the spray nozzle.
real-time, the solution to the optimization problem needs to
be obtained very quickly, which is not possible if we use the
above developed multiscale thin-film deposition model as it
takes 5–10 min to compute the film morphology for a given
set of inputs. Thus, an ANN is developed to significantly in­
crease the computational efficiency of the high-fidelity
model of QD thin-film deposition and used within the MPC.
4.1. ANN training and testing
In the last two decades, ANNs have been widely used for
various chemical engineering applications such as process
control, fault diagnosis, system identification, and process
design (Himmelblau, 2000). This success can be attributed to
their ability to learn and approximate any underlying com­
plex nonlinearities among input and output variables using a
simple architecture. Thus, given the complex dynamics
within the thin-film deposition model, a well-designed ANN
would be able to capture the input-to-output dynamics,
which will be then used in Eq. (14).
For this particular ANN, we are interested in predicting
film thickness (i.e., now represented by y1) and roughness
(i.e., now represented by y2). Here, y1 and y2 are dependent on
various inputs (i.e., u1, u2, and u3), and thus, the ANN shown
in Fig. 10 is sufficient to mimic the thin-film deposition
process. A similar approach has been utilized across various
chemical systems in the literature (Sitapure et al., 2020a;
Jagtap and Karniadakis, 2020; Zhao et al., 2001).
Remark 3. In a thin-film deposition apparatus, there are
various process parameters (i.e., gas and liquid velocities,
substrate temperature, spray nozzle height, and spray nozzle
angle) that can be manipulated (Andulkar et al., 2015;
Stoltenhoff et al., 2002; Li and Christofides, 2005; Crose
et al., 2017; Chen et al., 2002). However, among these
different inputs, gas and liquid velocities, and spray nozzle
height have a significant and immediate impact on the thin-
film deposition as compared to substrate temperature and
spray nozzle angle, thereby being especially considered in
this work (Yang et al., 2018; Yuan et al., 2019).
Thus, simulation data for 4000 sets of arbitrary input
combinations was collected and stored in the form of the
above mentioned augmented inputs and outputs, and gave a
total of 20 K data points for the ANN training. Generally
 Chemical Engineering Research and Design 183 (2022) 595–607 603

Fig. 10 – Schematic of the developed ANN showcasing the augmented input vector and the desired thin-film outputs.

speaking, during ANN training, 70% of the data points are 4.2. MPC formulation
used for training, and 15% are used for validation, and 15% of
the data is used for testing (i.e., data points that the ANN has Utilizing the ANN-based computationally efficient surrogate
not seen in its training phase). Such a split allows the ANN to model in the previous section, an MPC can be formulated as
avoid being prone to overfitting, and enables the ANN to in­ follows:
terpolate well across the entire range of data. Furthermore,
various ANN architectures (i.e., varying hidden layers and Minimize ¯
1 (h hsp )2 + 2 ( RMSE sp )
2
u1, u2, u3
neurons) were trained and tested, and the ANN with 5 inputs, s.t 10 u1 20 (m s)
three hidden layers with 20 neurons in each layer, and 2
1 u2 2 (m s ) (14)
outputs (i.e., [5, 20, 20, 20, 2]) gave the best training, valida­
0.1 u3 0.5 (cm)
tion and testing performance as shown in Fig. 11. Specifically,
Fig. 11a shows that the predicted film thickness from the [h¯ , RMSE] = fANN (u1, u2, u3)
ANN and the thin-film deposition model are in excellent
agreement with an R2 value of 0.99. Also, it is important to where α1 and α2 are the weights for the objective function,
note that in Figure 11a, the straight line (i.e., Y=T) acts as a fANN is the ANN from Fig. 10, and the manipulated inputs u1,
reference to compare between the film thickness values from u2, and u3 represent the gas velocity, liquid velocity, and
the high-fidelity model (HF) and the ANN, thereby generating spray nozzle height, respectively. Here, it is important to
a partiy plot. Similarly, Fig. 11b shows the error profile for the note that the input constraints are chosen considering the
training, validation, and testing error. It can be observed that practical limitations of a thin-film deposition apparatus, and
the error for all the three datasets converge over the entire the ANN has been trained using arbitrary input profiles that
training horizon, and is an indicator of a well-trained ANN. satisfy these constraints.

Fig. 11 – Summary of the ANN training and testing. (a) Parity plot for the film thickness from the ANN and the high-fidelity
thin-film deposition model, and (b) error profile for training, validation and testing of the ANN.
604 Chemical Engineering Research and Design 183 (2022) 595–607
Herein, the objective function consists of the deviation
from desired film thickness (hsp), and minimum roughness
(ψsp). This implies that the MPC formulation demands that
the set-point film thickness is reached and the roughness be
minimized. Also, it is important to note that in the case of
thin-film deposition, the deposition process is very quick
(i.e., ~ few seconds), and thus, a process time of five seconds
is considered (Yuan et al., 2019; Yang et al., 2018). Further, it
is assumed that the spray apparatus can manipulate its input
condition every second, and thus, a control horizon of five
time-steps with a sampling time of one second is considered
for the MPC (Khan et al., 2012; Ko et al., 2005). Finally, the
MPC implements the optimal inputs to the thin-film de­
position model which acts as a virtual experiment.
Remark 4. The DEM-based surface-level particle aggregation
model was developed in-house using C#, and the raw-data
generated from this simulation was analyzed in MATLAB,
and then incorporated into a MATLAB-based film deposition
model. Also, MATLAB’s neural network toolbox was used to
construct an ANN model, which was incorporated into a
fmincon module to develop an MPC framework. Lastly, all the
above simulations were performed on a computer with Intel
Core i7–6700 CPU with 3.40 GHz and 16.0 GB RAM, running
Windows 10, 64-bit operating system, and MATLAB 2022b.
Fig. 12 – Compilation of the optimal inputs, viz., (a) gas velocity, (b) liquid velocity, (c) spray nozzle height, and the output, (d)
thin-film achieved by applying the optimal inputs.
4.3. Closed-loop MPC results
The above section describes an ANN that mimics the thin-
film deposition model and acts as a computationally efficient
surrogate model that can be used in Eq. (14) for deploying an
online MPC for thin-film deposition process. For QD-based
thin-film optoelectronic applications, the film thickness in
the range of 50–100 nm is often seen in the literature (Yuan
et al., 2019; Yang et al., 2018). Thus, the set-point film
thickness (h̄sp ) of 50 nm was considered along with the ob­
jective of minimizing the roughness, and then the perfor­
mance of the MPC was analyzed. Fig. 12 shows the
compilation of the optimal input values and the resultant
thin-film with the desired film thickness and a minimum
value of roughness. First, the variation in the gas velocity
results in different droplet sizes due to atomization, and it
affects the evaporation dynamics and the surface-level par­
ticle aggregation. Second, the variation in liquid velocity
largely affects the deposition rate as more liquid is sprayed
onto the substrate. Thus, throughout the thin-film deposition
process, a fairly steady liquid velocity is maintained. How­
ever, towards the end of the process, the thin-film thickness
is very close to the set-point value of 50 nm, and thus, the
liquid velocity is decreased to avoid an excess thin-film
 Chemical Engineering Research and Design 183 (2022) 595–607
deposition. Third, spray nozzle height controls the spread of
droplets as shown in Fig. 2. Throughout the deposition pro­
cess, the spray nozzle height is fairly consistent. However,
towards the end of the process, to further minimize the
roughness of the thin-film, the spray nozzle is increased
significantly as it will allow a high spray cone area leading to
uniform thin-film deposition while maintaining a low
roughness value.
Furthermore, the film roughness of ~ 5 nm is in excellent
agreement with experimental observations for spray coating
of QDs from the literature (Yuan et al., 2019). Specifically,
Tian and his coworkers synthesized a 50 nm thin-film using a
spray nozzle, and used atomic-force microscopy (AFM) to
measure film roughness of ~ 6 nm, which is very close to
simulation results from Fig. 12d.
5. Conclusions
The recent interest in QD-based thin-film optoelectronic
devices has probed research in modeling and control of thin-
film deposition for manufacturing of these devices. To this
end, a multiscale thin-film deposition model was developed
to consider the macroscopic thin-film deposition factors
along with a surface-level description of the thin-films (i.e.,
uneven deposition and roughness). First, the effect of gas and
liquid velocity on droplet size, solvent evaporation, and thin-
film deposition rate were considered. Second, at the surface-
level, a DEM-based model was developed to investigate par­
ticle aggregation and determine the deposition pattern of QD
particles. Probing into these surface-level deposition pat­
terns is important as they contribute to the roughness of the
as-deposited thin-films. These different factors and their
individual models were integrated to construct a multiscale
thin-film deposition model (Fig. 5). Third, to regulate the film
characteristics by manipulating the various inputs (i.e., li­
quid and gas velocities, and the spray nozzle height), an MPC
was designed. In particular, for deploying an MPC in real-
time, a highly computationally efficient surrogate thin-film
deposition model is required. Thus, an ANN which accu­
rately mimics the thin-film formation was trained, tested,
and was incorporated within the MPC formulation. Finally, to
showcase the applicability of the developed MPC, set-point
tracking for achieving the desired film thickness, and mini­
mizing the film roughness was analyzed. The closed-loop
simulation results suggest that the MPC drives the thin-film
deposition process to the set-point film thickness, and the
value of film roughness is very similar to the values obtained
from the literature. Overall, the current work presents a
multiscale thin-film deposition framework to regulate im­
portant thin-film properties by developing an adequate thin-
film deposition model that focuses on the macroscopic and
surface-level phenomena, and integrating its surrogate
model within an MPC to enable process control of thin-film
deposition in QD systems. Future models can build on the
developed framework to add further macroscopic and sur­
face-level details specific to their QD system of interest.
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have
appeared to influence the work reported in this paper.
605
Acknowledgments
The authors gratefully acknowledge financial support from
the Artie McFerrin Department of Chemical Engineering and
the Texas A&M Energy Institute.
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