Chemical Engineering Science 96 (2013) 71–86

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Chemical Engineering Science

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

A model-based methodology for the analysis and design

of atomic layer deposition processes—Part III: Constrained
multi-objective optimization
A. Holmqvist a,n, T. Törndahl b, S. Stenström a
a
Department of Chemical Engineering, Lund University, P.O. Box 124, SE-221 00 Lund, Sweden
b
Ångtröm Solar Center, Solid State Electronics, Uppsala University, P.O. Box 534, SE-751 21 Uppsala, Sweden

H I G H L I G H T S

Novel methodology for the constrained multi-objective optimization of ALD reactor models.

Analysis of the manufacture of ZnO thin films with constraints on the film thickness uniformity.

Case study of incommensurable quasi-steady-state reactor throughput and conversion objectives.

The purge time is an essential parameter in the optimization of throughput in temporal ALD.

The inherent process robustness is significantly reduced with precursor conversion.

art ic l e i nf o a b s t r a c t

Article history: This paper presents a structured methodology for the constrained multi-objective optimization (MO) of a
Received 20 November 2012 continuous cross-flow atomic layer deposition (ALD) reactor model with temporal precursor pulsing. The
Received in revised form process model has been elaborated and experimentally validated in the first two papers of this series
11 March 2013
(Holmqvist et al., 2012, 2013). A general constrained MO problem (MOP) was formulated to simulta-
Accepted 25 March 2013
neously optimize quasi-steady-state reactor throughput and overall precursor conversion for the
Available online 10 April 2013
controlled deposition of ZnO films from ZnðC2 H5 Þ2 and H2 O, subject to a set of operational constraints.
Keywords: These constraints included lower bounds for the cross-substrate film thickness uniformity and post-
Atomic layer deposition precursor purge duration. The non-dominated Pareto optimal solutions obtained successfully revealed
Optimization
the relation between the incommensurable process objectives and reduced the design space of the ALD
Uncertainty and sensitivity analysis
process into a feasible set of design alternatives. The results presented here show that post-precursor
Numerical analysis
Mathematical modeling purge duration is essential when optimizing throughput in temporally separated ALD processes, and that
Transport processes this is a major drawback when considering operation at atmospheric pressure. Finally, the robustness of
the process along the Pareto optimal front, i.e. the ability of the process to accommodate variations in the
associated set of optimal decision variables (DVs), was assessed by Monte Carlo simulations, in which the
values of the parametric uncertainties were randomly generated from a multivariate normal distribution.
The uncertainty and sensitivity analysis showed that the inherent robustness of the process is
progressively lost with the precursor conversion, and revealed the mechanistic dependence of all DVs
on the proposed optimization specifications.
& 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Atomic layer deposition (ALD) is a gas phase deposition technique
that can produce conformal thin films with controlled, uniform
thickness in the nanometer range (George, 2010). There are two
n
Corresponding author. Tel.: +46 46 222 8301; fax: +46 46 222 4526.
E-mail addresses: anders.holmqvist@chemeng.lth.se (A. Holmqvist),
tobias.torndahl@angstrom.uu.se (T. Törndahl),
stig.stenstrom@chemeng.lth.se (S. Stenström).
generic ALD process technologies which both rely on decoupling self-
terminating (Puurunen, 2005) gas–surface reactions:
(i) Conventional thermal ALD, in which the substrates are sta-
tionary and precursors are injected non-overlapping in a time
sequence, separated by intermediate purge steps (Granneman
et al., 2007).
(ii) Spatial ALD (S-ALD) (Poodt et al., 2012) with rigid (Fitzpatrick
et al., 2012; Levy et al., 2009; Nelson et al., 2012) or flexible
substrates (roll-to-roll ALD) (Maydannik et al., 2012), in which

0009-2509/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2013.03.061
72 A. Holmqvist et al. / Chemical Engineering Science 96 (2013) 71–86
continuous precursor flows are separated spatially in different
zones and the substrate moves relative to the precursor
sources.
Industrial semiconductor processing has been a major stimulant
for the development of the ALD process (Ritala and Niinisto, 2009;
Sneh et al., 2002). Novel applications of ALD are expanding beyond
semiconductor processing in several emerging areas, such as
surface passivation layers in c-Si solar cells, buffer layers in
CuIn1−x Gax Se2 (CIGS) (Bakke et al., 2011), and diffusion barrier
layers in OLEDs and thin film photovoltaics (Carcia et al., 2009).
This trend brings with a growing necessity for high-throughput
and low cost production techniques (Poodt et al., 2012).
In this study, design parameters for cross-flow, low-volume ALD
reactor designs with temporal precursor pulsing were evaluated. The
aforementioned reactor designs are of substantial interest for the
equipment used to manufacture (Henn-Lecordier et al., 2011) large-
surface-area substrates (Sundaram et al., 2010). Such substrates are
subject to stringent uniformity, defined by Cleveland et al. (2012) as
the ratio between the standard deviation and the mean value of the
spatially dependent film thickness profile, constraints, while
demands on enhanced throughput (Mousa et al., 2012) and overall
precursor conversion (Lankhorst et al., 2007) require optimal reactor
designs and process operating conditions (Elers et al., 2006). Opti-
mized reactor design parameters can enable very high throughput,
specifically in the growing number of applications where only very
thin films are needed (Jur and Parsons, 2011). Moreover, optimized
design parameters also allow a significant reduction in precursor
consumption and consequently in the cost-of-ownership, especially
since it is recognized that many ALD processes under development
for new industrial applications compensate for non-ideal reactor
designs by significantly over-exposing the substrate to precursors
(Adomaitis, 2011).
Wolden et al. (2011) pointed out that the development of
competitive manufacturing techniques requires sophisticated
modeling to understand how to maintain uniformity with respect
to both space and time. Furthermore, Henn-Lecordier et al. (2011)
and Cleveland et al. (2012) emphasized that the identification of
an ALD process design space (Aelion et al., 1991) defined as the
multidimensional process design parameter space within which
thickness uniformity across the substrate is guaranteed, is non-
trivial due to the complex interdependency between the process
design parameters, and requires knowledge of several factors.
These include the characteristic time-scales, see e.g. (Adomaitis,
2010; Granneman et al., 2007), of reactor-scale mass transport
(Aarik et al., 2006; Jur and Parsons, 2011; Mousa et al., 2012),
and the gas–surface reaction mechanism (Deminsky et al., 2004).
However, Londergan et al. (2002) observed that optimal process
parameters typically fall outside of the normal operating range
or control space of an ALD process, in which the impact of
process-induced variations on film thickness uniformity is more
pronounced.
The overall objective of this study was to develop a novel,
generally applicable method for optimizing a continuous cross-
flow ALD reactor model able to handle multiple objectives and
constraints. This methodology developed was subsequently
applied to an experimentally validated mechanistic model of the
continuous cross-flow ALD reactor system F-120 manufactured by
ASM Microchemistry Ltd. Suntola (1992) and its development is
described in the first two parts of this paper series (Holmqvist
et al., 2012, 2013). These papers present also a case study of the
deposition of thin ZnO films from ZnðC2 H5 Þ2 and H2 O. The present
paper focuses on two main points:
(i) To formulate a constrained multi-objective optimization pro-
blem (MOP) with the objectives of simultaneously maximizing
reactor throughput and precursor utilization under the con-
straints of ensuring spatial control of the cross-substrate film
thickness uniformity and of assigning sufficient post-precursor
purge time.
(ii) To evaluate the robustness of the set of optimal operating
points that was determined, i.e. to assess the ability of the
process to accommodate variations in the set of optimal
decision variables (DVs) and to rank the variables according
to their importance.
The reminder of this paper is organized as follows. Section 2
presents the continuous cross-flow ALD reactor system and the
mathematical process model. Section 3 describes the formulation
of the constrained MOP, including its objective functions, algebraic
constraints, and DVs. Section 4 is dedicated to the basic compo-
nents of an uncertainty and sensitivity analysis (UA/SA), while
Section 5 outlines the modeling and optimization environment.
Section 6 presents the results from the multi-objective optimiza-
tion (MO) analysis and the UA/SA of the ALD process model.
Finally, Section 7 contains concluding remarks.
2. The continuous cross-flow ALD reactor system
2.1. Process overview
The continuous cross-flow ALD reactor system F-120 manufac-
tured by ASM Microchemistry Ltd. (Suntola, 1992) was used for the
controlled deposition of thin ZnO films on soda lime glass
substrates from ZnðC2 H5 Þ2 and H2 O precursors, shown schemati-
cally in Fig. 1. The reactor setup incorporates an actuator sub-
system that provides flow control (FC) for the carrier gas and each
precursor inflow, Q_ α and α∈fN2 ; ZnðC2 H5 Þ2 ; H2 Og, and enables
alternate injection with variable dose time, Δt α , of the αth
precursor. Mathematically, the normalized boxcar function,
Π α ðt; Δt α Þ∈½0; 1, was used to model non-overlapping precursor
injections in a cyclic time sequence, and is represented as
8
< 1 ϖ α ∑ Δt β ≤t ≤ϖ α ∑ Δt β þ Δt α
Π α ðt; Δt α Þ ¼ β≠α β≠α ð1Þ
:
0 otherwise
in which t ¼ ðnΔt −⌊nΔt ⌋ÞΔt is the normalized cycle time,
nΔt ¼ ðtΔtÞ−1 is the cycle number, Δt ¼ Δt ZnðC2 H5 Þ2 þ Δt N2 þ Δt H2 O þ
Δt N2 denotes a complete ALD cycle, and ½ϖ ZnðC2 H5 Þ2 ; ϖ H2 O  ¼ ½0; 1.
Furthermore, the continuous inert gas flow, Q_ N2 , transports
traveling waves of adsorptive precursors laterally across the active
surface of the substrates, which are mounted on opposite sides of
the reactor chamber. Temperature control (TC) is achieved through
an external induction heating setup and ensures that the operating
temperature, T, is homogenous, while the pressure, p, at the
reactor chamber outlet is controlled by a rotary vane vacuum
pump (PC). Further details of the reactor system setup are given in,
e.g. Holmqvist et al. (2012), Yousfi et al. (2000), and Baunemann
(2006).
Fig. 1. Simplified schematic diagram of the continuous flow ALD reactor system
F-120 manufactured by ASM Microchemistry Ltd. (Suntola, 1992). The vector of
manipulated variables is: u ¼ ½T; p; Q_ N2 ; Δt N2 ; Q_ ZnðC2 H5 Þ2 ; Δt ZnðC2 H5 Þ2 ; Q_ H2 O ; Δt H2 O † .
 A. Holmqvist et al. / Chemical Engineering Science 96 (2013) 71–86
Fig. 2. Sketch of the computational domain, Ω, with a partitioned boundary
Γ ¼ Γ in ∪Γ wall ∪Γ sub ∪Γ sym ∪Γ out as outlined in (Holmqvist et al., 2012). The dimen-
sions are as follows: jΓ sub j ¼ 5:0  10−2 (m), jΓ in j ¼ jΓ out j ¼ 2:0  10−3 (m), and
jΓ wall j ¼ 2:5  10−3 (m).
2.2. The mathematical process model
Modeling of an ALD continuous flow reactor system may be
performed at different levels of detail and assumptions, see e.g. Aarik
and Siimon (1994), Knoops et al. (2011), Siimon and Aarik (1995,
1997), Yanguas-Gil and Elam (2012), and Ylilammi (1995). The level
that is chosen depends on the predetermined goal of the modeling,
as defined by Hangos and Cameron(2001), and the application of the
model. However, in this study, the experimentally validated mechan-
istic model based on computational fluid dynamics, in which the
narrow flow channel inside the reactor chamber in the ALD con-
tinuous flow reactor system (Fig. 1) constitutes the computational
domain Ω (Fig. 2), developed in the first two parts of this paper series
(Holmqvist et al., 2012, 2013) was considered. The process model was
elaborated and validated experimentally such that it can adequately
predict the substrate, Γ sub , spatially dependent film thickness and
provide statistically reliable least-square estimates, β, of the para-
meters involved in the heterogeneous gas–surface reaction mechan-
ism that governs the growth of the ZnO film. Thus, no finer modeling
level of the spatial evolution of the substrate film thickness profile,
hs ðζÞ and ζ∈½0; jΓ sub j, than mass and momentum conservation
equations, while incorporating reaction rate equations, was consid-
ered, which is appropriate for the analysis, design and optimization
of ALD reactors (Elliott, 2007).
The model partial differential equations (PDEs) were approxi-
mated using the method of lines (Davis, 1984; Schiesser, 1991) and
the finite element method (Zienkiewicz and Taylor, 2000a,b). For
notational simplicity, the associated system of index-1 differential
algebraic equations (DAEs), FðÞ, in which x, u, and w represent
dependent states, free design variables, and algebraic variables,
respectively, can be written in the general form
 
dx
0¼F ; x; u; β; w; t ; xðt 0 Þ ¼ x0
dt
y ¼ gðx; u; β; wÞ
x ¼ ½p; v; ωα ; θκ ; ms † ; ∀α; κ
u ¼ ½T; 〈p〉j ; Q_ ; Δt α † ; ∀α
Γ out α ð2Þ
where gðÞ is the response function and y denotes the model
output.
3. The multi-objective optimization problem
3.1. Formulation of the constrained multi-objective optimization
problem
A MOP involves the simultaneous optimization of i∈f1; …; ni g
incommensurable objective functions f ðuÞ ¼ ½f 1 ðuÞ; …; f ni ðuÞ† ∈Rni
(Deb, 2001; Yee et al., 2003). A general MOP global minimum
problem is formally defined as
minn −f ðuÞ
u∈R j
subject to Eq: ð2Þ
0≥Cieq ðx; u; wÞ
0 ¼ Ceq ðx; u; wÞ
umin ≤u ≤umax ð3Þ
73
where Cieq ðÞ∈Rnk and Ceq ðÞ∈Rnl represent inequality and equality
algebraic constraints, respectively, and the vector of decision
variables, u∈Rnj , is subject to lower and upper bounds that act
as inequality constraints. Incompatibility between the objective
functions and their incommensurability makes it impossible to
find a single ideal solution that is optimal with respect to all
objectives simultaneously. Instead, there is an entire set of solu-
tions that are equally optimal, known as Pareto optimal solutions
(i.e. non-dominated solutions), and this set provides flexibility for
the decision maker (Miettinen, 1998).
3.1.1. Pareto terminology and the dominance relation
The most common notation of optimality adopted in MO is the
Pareto optimality. The formal definition of the Pareto optimality is:
a decision vector un ∈U is denoted Pareto optimal with respect to
the feasible region
U ¼ fun : Cieq ðx; un ; wÞ ≤0∧Ceq ðx; un ; wÞ ¼ 0g ð4Þ
if there is no another decision vector u∈U for which f ðuÞ ¼
½f 1 ðuÞ; …; f ni ðuÞ† dominates f ðun Þ ¼ ½f 1 ðun Þ; …; f ni ðun Þ† (Miettinen,
1998). In this case, a vector f ðuÞ is said to dominate the vector f ðun Þ
(denoted f ðuÞ≼f ðun Þ) if the following two conditions are satisfied:
∀i∈f1; …; ni g : f i ðuÞ ≤f i ðun Þ ∧
∃ι∈f1; …; ni g : f ι ðuÞ o f ι ðun Þ ð5Þ
n
The concept of dominance, for a given MOP f i ðu Þ, allows to define
the non-dominated, Pareto optimal solution set, P n ∈U (Laumanns
et al., 2002)
P n ¼ fun ∈U : ⇁∃u∈U; f ðuÞ≼f ðun Þg ð6Þ
and the decision vector un is termed Pareto optimal if un is non-
dominated regarding the entire feasible parameter space U
(Eq. (4)). Furthermore, the set of objective vectors f ðun Þ corre-
sponding to a set of Pareto optimal parameter vectors un ∈P n is
denoted Pareto optimal front (Veldhuizen and Lamont, 2000), and
defined as
PF n ¼ ff ðun Þ : un ∈P n g ð7Þ
3.2. Formulation of objective functions
In the present study, the industrial goal of increasing through-
put without compromising the conversion of precursors described
in Section 1 motivated the formulation of the objective functions.
In addition, the developed heterogeneous gas–surface reaction
mechanism in the quasi-steady-state growth region (Holmqvist
et al., 2012, 2013) implies that the model response is repre-
sented by limit-cycle solutions and associated with constant
growth per cycle (GPC) (Puurunen, 2003, 2004; Yim et al., 2008).
For this reason, the objective functions and algebraic constraints
are resolved at the level of a single pulse sequence, Δt. Hence, the
ALD reactor productivity, PjΔt , is defined as the accumulated mass
deposited per unit area of the substrate and cycle time
Z Z
1 ∂ms
PjΔt ¼ ∂Γ ∂t ð8Þ
ΔtjΓ sub j Δt Γ sub ∂t
where ms is governed by the sum over the sequential hetero-
geneous gas–surface reaction rates multiplied by the associated
difference in molecular weight of the outermost surface species, θκ
(Holmqvist et al., 2012). Moreover, the αth adsorptive precursor
yield is defined as the relative amount of the inlet precursor dose,
Q_ α Π α ðt; Δt α Þ (cf. Fig. 1), chemisorbed onto the active substrate
surface
Z Z Z −1 !
jΓ j
Y α jΔt ¼ 1− in N_ α jΓ ∂Γ N_ α jΓ ∂Γ ∂t ð9Þ
Δt jΓ out j Γ out Γ in
74 A. Holmqvist et al. / Chemical Engineering Science 96 (2013) 71–86

Table 1 Stokes equations (Holmqvist et al., 2012) in the spatial domain, Ω,

The decision variables, uj and j∈f1; …; 5g, involved in the MOP (Eq. (3)) and their and the second integral of Eq. (10) was derived to assist in the
lower and upper boundaries. The maximum injected αth precursor dose,
physical interpretation of the optimization results. In addition, the
maxðQ_ Π α ðt; Δt α ÞÞj , corresponds to 1:94  102  ΛjΓ j2 (mol), determined with
α Γ in sub
temperature is the most readily accessible attribute to activation
Λ ¼ 1:53  10−5 ðmol m−2 Þ (Holmqvist et al., 2013).
energies of the elementary gas–surface reactions (Lei et al., 2006).
j Decision variables u Units Lower limit umin Upper limit umax There are two main ways of varying the half-cycle average
substrate exposure dose for the αth adsorptive precursor
1 T (K) 3:0  10 2
6:0  102 Z Z
1
2 Q_ (sccm)a 1:0  10 0
2:0  103 〈δα 〉 ¼ p j ∂Γ ∂t ð11Þ
N2
jΓ sub j Δtα Γsub α Γ
3 〈p〉jΓ out (Pa) 5:0  101 1:0  105
4 Q_ ðC2 H5 Þ
Zn 2
(sccm) 0:0  100 2:0  101 either by changing the mass flow of the precursors, Q_ α , thereby
5 Δt ZnðC2 H5 Þ2 (s) 1:0  10−1 1:0  100 changing the partial pressure, or by changing the duration of the
a
pulse, Δt α . Moreover, given a specific set of u ¼ ½T; 〈p〉jΓout ; Q_ N2 , the
Standard cubic centimeters per minute at STP (T ¼273.15 (K) and p ¼1.0
required minimum substrate saturation exposure dose of the αth
(atm)).
adsorptive precursor is governed by
Z Z
1
where N_ α jΓ ¼ −n  ðρωα v−ρDαβ ∇ωα Þ is the total mass flux Λ¼ ∑ ξ r ℓ ∂Γ ∂t
jΓ sub j Δt sat;α Γsub ℓ ¼ 1 α;ℓ
ð12Þ
(calculated using Fick's law of binary diffusion (Bird et al., 1960))
of the αth species normal to the boundary Γ (cf. Fig. 2). Thus, the where the ℓth forward gas–surface reaction rate is proportional to
formulated objective functions can be collectively written as the αth precursor partial pressure in the vicinity of the substrate
f ¼ ½PjΔt ; Y α jΔt † and α∈fZnðC2 H5 Þ2 ; H2 Og. However, in this study, surface, i.e. r ℓ ∝pα jΓ sub (Holmqvist et al., 2012; Masel, 1996).
only the yield of the most expensive ZnðC2 H5 Þ2 precursor was However, productivity enhancement dictates that the overall ALD
considered, reducing the objective space to f ∈R2 . cycle time, Δt, must be substantially reduced, and this leads to

3.3. Definition of decision variables (i) A compromise between Δt α and Δt sat;α .

The set of DVs, u∈Rnj , involved in the optimization procedure
(shown in Fig. 1) may be classified into operating condition
parameters, u ¼ ½T; 〈p〉jΓ out , Q_ N2 , and ALD pulse sequence para-
meters, u ¼ ½Q_ ZnðC2 H5 Þ2 , Δt ZnðC2 H5 Þ2 . The decision vector is subject to
the lower, umin , and upper, umax , constraints listed in Table 1, and
this further bounds the feasible decision space u∈U in addition to
the algebraic constraints, Cieq and Ceq . Furthermore, the exclusion
of Y H2 O jΔt from the objective vector, f , means that the non-
dominated solutions for u ¼ ½Q_ H2 O ; Δt H2 O  will target max PjΔt ,
whereas Y ZnðC2 H5 Þ2 jΔt is insensitive to perturbations in the DVs.
For this reason, the constant values, ½Q_ H2 O ; Δt H2 O  ¼ ½max Q_ ZnðC2 H5 Þ2 ;
min Δt ZnðC2 H5 Þ2 , were assigned to the DVs in the optimization
procedure that governs max PjΔt . The implications and validity of
this postulate will be assessed in Section 6.
Optimizing productivity and precursor yield (Eqs. (8) and (9))
require that an optimal dose of precursors is introduced in
minimal time into the reactor chamber that is held at optimal
operating conditions. Aarik et al. (2006), Jur and Parsons (2011),
and Mousa et al. (2012) have all independently shown that the DVs
of the operating conditions comprise the flow rate and pressure of
the carrier gas, and the process temperature. These parameters
together govern the hydrodynamic flow field, and consequently,
determine the characteristic time constant for the external mass
transport of precursors to the substrate surface and the reactor
residence time. The interdependence between the DVs, deter-
mined from the inherent formalism of the equation of state
ðρ ¼ pMðRTÞ−1 ; M ¼ ð∑∀α ωα M −1 −1
α Þ Þ, governs the integral mean
value of the velocity field in Ω (cf. Fig. 2)
Z Z
1 1 1 1− Γsub jhs ðζÞ−h s ðζÞj∂ζ Γsub hs ðζÞ∂ζ
〈v〉jΩ ¼ v ∂Ω ¼ ∑ρ Q_ Π α ðt; Δt α Þ ∂Ω ð10Þ
jΩj Ω jΩj Ω ρAΩ ∀α STP;α α
For clarification purposes, the reactor system in Fig. 1 utilizes a
continuous viscous flow of nitrogen carrier gas, Q_ N2 , supplied via a
mass flow controller, see Holmqvist et al. (2012). Consequently,
during the carrier gas purge, Π ZnðC2 H5 Þ2 ¼ Π H2 O ¼ 0 (see Eq. (1)) and
the second integral of Eq. (10) is exclusively governed by the
carrier gas mass flux ðρv≡ρSTP;N2 Q_ N2 ðAΩ Þ−1 Þ. Furthermore, it is
evident that 〈v〉jΩ in Eq. (10) is the average mass velocity of all
the components in the mixture. It is, however, noteworthy that the
velocity field, v, in Eq. (2) is governed by the compressible Navier–
(ii) The need to minimize post-precursor purge times, Δt N2 .
Adsorptive precursors are normally alternately injected into the
continuous inert carrier gas flow using gas switching valves,
where the minimum duration of the pulse is determined by the
time required for reliable valve actuation, and is of the order of
tenths of a second (Londergan et al., 2002). Moreover, the post-
precursor purge times are adjusted to prevent the co-existence of
precursors in the reactor chamber, thereby avoiding non-ALD
reactions and growth mechanisms (Dasgupta et al., 2012).
3.4. Formulation of algebraic constraints
Two algebraic constraints are now introduced to ensure spatial
control of the cross-substrate film thickness uniformity, UFjΔt , and
to ensure that a sufficient post-precursor purge time, Δt N2 , is
allowed. These constraints limit the MOP (Eq. (3)) and define the
feasible decision space, u∈U, (Eq. (4)).
3.4.1. Cross-substrate film thickness uniformity
The design of the continuous cross-flow ALD reactor (Section 2)
leads to the trailing edge of the substrate being exposed to more
depleted precursor flow than the leading edge, and the cross-
substrate film deposition rate is consequently inhomogeneous
(Granneman et al., 2007; Cleveland et al., 2012; Henn-Lecordier
et al., 2011). A cross-substrate uniformity metric, UFjΔt , (Cheng and
Hsiao, 2008) which relates the absolute deviation from the mean
film height, has been defined
8 R −1
< R
∃hs ðζÞ 4 0
UFjΔt ¼ ð13Þ
:
1 otherwise
where hs ðζÞ is the normalized film height, h s ðζÞ is the mean film
height, and ζ∈½0; jΓ sub j is the substrate boundary, Γ sub , local
coordinate variable as outlined previously (Holmqvist et al.,
2012). This allows the inequality algebraic constraint to be
expressed as
C ieq ¼ UFjΔt;min −UFjΔt ð14Þ
where UFjΔt;min denotes the minimum acceptable degree of film
thickness uniformity. Moreover, it is noteworthy that C ieq ≤0 in
 A. Holmqvist et al. / Chemical Engineering Science 96 (2013) 71–86
order for a candidate solution to fulfil the formal feasibility
requirement, see Eqs. (3) and (4).
3.4.2. Post-precursor purge duration
Precursor physisorption occurs to some extent on internal
surfaces throughout the entire reactor system (cf. Fig. 1), main-
tained at or near the substrate temperature during the exposure.
Desorption will subsequently occur during the sequential precur-
sor exposure period if the reactor has not been subjected to
sufficient purging by an inert carrier gas. In order to achieve
sufficient removal of precursors, the characteristic time constant
for the temperature-dependent desorption process (Groner et al.,
2004), the reactor system mean residence time (Elers et al., 2006),
and the carrier gas entrainment (Aarik et al., 2006), must be
assessed to quantify the background precursor level. Jur and
Parsons (2011) and Mousa et al. (2012) suggested that the lower
bound of the purge time, Δt N2 , needed in the ALD sequence to
ensure negligible precursor interaction is determined from the
maximum values of:
(i) The average gas residence time
jΓ sub j þ 2jΓ wall j
τ¼ ð15Þ
〈v〉jΩ
for removing species from the reactor by the bulk purge flow,
and ultimately determined from the interdependence of Q_ N2 , p
and T through Eq. (10).
(ii) The mixing time
Δ2
τDαβ ¼ ð16aÞ
Dαβ
!1=2
ηz1
Δ ¼ 4:64 ð16bÞ
ρvz1 jΓsym
which is required for physisorbed precursors and vapor
product species that are generated to traverse the laminar
boundary layer thickness, Δ, over a flat surface into the bulk
flow through diffusion (Bird et al., 1960).
Hence, the lower boundary of the N2 purge period, Δt N2 , is
imposed by the equality constraint.
C eq ¼ Δt N2 −maxðNΩ τ; τDαβ Þ ð17Þ
in which N Ω denotes the number of reactor chamber volumes to
be purged. However, given the narrow dimensions of the flow
channel (Fig. 2) and the DV boundaries that are listed in Table 1,
τDαβ ⪡τ and, consequently, the purge period, Δt N2 , is exclusively
determined by τ. It is noteworthy that the continuum gas flow
calculations (Eqs. (15) and (16)) do not consider specific time
constants for the species desorption kinetics. This would ulti-
mately require a reaction mechanism for the desorption of
physisorbed precursors, which is not considered in the ALD
process model (Holmqvist et al., 2012, 2013).
4. Uncertainty and sensitivity analysis
The stability and repeatability of the optimized ALD process
will depend on the impact of variations of the key operating
condition parameters on the resulting film quality and process
performance. The industrial goal of increasing throughput and the
conversion of precursors dictate the use of very short ALD cycle
times, Δt. This regime is typically outside of a conventional ALD
process design space, in which the surface reactions approach
saturation as the substrate becomes over-exposed to precursors
75
(Lecordier, 2009; Londergan et al., 2002). To evaluate the robust-
ness of the optimized continuous cross-flow ALD reactor (Section
2), i.e. to examine how it accommodated variations in optimal DVs,
model-based uncertainty and sensitivity analysis (UA/SA) (Helton
et al., 2006) was carried out. The main aim was to assess the
impact of variations in key parameters in the Pareto optimal
solution set, P n (Eq. (6)), on product quality, measured by the film
thickness uniformity (Eq. (13)), and on process performance,
measured by productivity and precursor yields (Eqs. (8) and (9)),
along the Pareto optimal front, PF n (Eq. (7)). Several approaches
to UA/SA have been developed, however, an approach based on
Monte Carlo methods was used in this study.
4.1. Sampling-based methods
The initial component that underlies the implementation of
sampling-based methods involves assigning distributions that
characterize the uncertainty in each of the elements of u. When
no information on the variability of an input parameter is avail-
able, a normal distribution, uj ∼N ðμuj ; s2uj Þ, is generally a good
approximation (according to the central limit theorem
Vardeman, 1994). The subsequent component comprises the gen-
eration of a sample. Latin hypercube sampling (LHS) is suitable for
use with computationally demanding models because its stratifi-
cation properties ensure that the whole variable range is uni-
formly sampled, even with a relatively small sample size (Helton
and Davis, 2003). The final component explores and illustrates the
mapping (Helton and Davis, 2002), during which an approxima-
tion of an empirical probability density function (pdf) of the model
output provides the most complete representation of the uncer-
tainty in the elements of y that is derived from individual
distributions in u. The pdf, ϕðXÞ, of the jdimensional multivariate
normal distribution of the vector X, collecting elements of u and y,
is given by
 j=2  
1 1 1 † −1
ϕðXÞ ¼ exp − ½X−μX  ΣðXÞ ½X−μ X  ð18Þ
2π ðdet ΣðXÞÞ1=2 2
which is parametrized with a mean vector, μX , and a ðj  jÞ
covariance matrix
0 1
s21 ϱ12 s1 s2 … ϱ1j s1 sj
B C
B ϱ12 s1 s2 s22 … ϱ2j s2 sj C
B C
ΣðXÞ ¼ B C ð19Þ
B ⋮ ⋮ ⋱ ⋮ C
@ A
ϱ1j s1 sj ϱ2j s2 sj … sj 2
Determining the expectation values and correlation coefficients
associated with Eqs. (18) and (19) lays the foundation for ranking
the contributions from individual elements of u with respect to
the uncertainty in the elements of y.
5. Modeling and optimization environment
s
COMSOL Multiphysics (COMSOL AB, 2008), a finite element
analysis, solver and simulation software package for encoding of
complex and coupled physical systems aimed at simulation, is
used for reactor modeling (see Section 2.2). It also offers an
extensive interface to MATLABs (The MathWorks, Inc., 2010a),
and hence, is a suitable platform for optimization, to be used in
s
conjunction with COMSOL Multiphysics .
5.1. Multi-objective evolutionary algorithms
From the class of multi-objective evolutionary algorithms
(MOEAs), two state-of-the-art algorithms: NSGA-II (Deb et al.,
2002) and SPEA2 (Zitzler et al., 2001), are widely used, since they
76 A. Holmqvist et al. / Chemical Engineering Science 96 (2013) 71–86

are based on principles of dominance and Pareto optimality

(defined in Section 3.1.1) and they possess the desired convergence
and diversity-preservation properties (Laumanns et al., 2002). The
model-based methodology proposed in this study is based on the
following procedure: the parallelized evolutionary algorithm dif-
ferential evolution (DE) (Price, 1999; Price et al., 2005; Storn and
Price, 1997), following the master–slave parallel and distributed
programming paradigm (Coello et al., 2007) as outlined previously
(Holmqvist et al., 2013), was extended for handling MOPs by
adopting the external elitist archive from the SPEA2 algorithm and
the constraint-handling approach from the NSGA-II algorithm. The
algorithm thus implemented is similar to the existing multi-
objective self-adaptive differential evolution (MOSADE) algorithm
proposed by Wang et al. (2010) in that it adopts the elitist
reservation strategy and the preservation of diversity based on
crowding degree (in the objective space Rni ). However, the self-
adaptation strategy for the DE control parameter derived by Qin
and Suganthan (2005) and Qin et al. (2009) was used.

5.1.1. Assessment of Pareto optimal solution sets

Furthermore, the deterministic weighted-sum-method (Kim
and de Weck, 2005) was used in order to assess the reliability of
the output from the implemented algorithm and the convergence
to the true Pareto optimal front, PF n . This method aggregates all
objectives, f ðuÞ∈Rni , into one multi-attribute utility function
(MAUF), Uðu; λÞ, by a linear combination via the normalized weight
vector, λ, as follows:
Uðu; λÞ ¼ ∑ λi f i ðuÞ
i¼1
Fig. 3. Projection of the feasible objective space f ¼ ½PjΔt ; Y ZnðC2 H5 Þ2 jΔt † ∈R2 for the
constrained MOP (Eq. (3)) subject to the set of DVs and associated boundaries listed
in Table 1. The Pareto optimal fronts, PF n , are shown for: ð−○−Þ UFjΔt;min ¼ 0:90;
ð−▿−Þ UFjΔt;min ¼ 0:95; ð−◊−Þ UFjΔt;min ¼ 0:99. Pareto optimal solutions generated by
the resolution of Uðun ; λÞ and associated weight vector λ1 ¼ ½0:0; 0:1; …; 1:0† are
shown for: ð
Þ UFjΔt;min ¼ 0:90; ð▾Þ UFjΔt;min ¼ 0:95; ð♦Þ UFjΔt;min ¼ 0:99. ðÞ Domi-
nated solutions for UF min jΔt ¼ 0:90; ð◀Þ Ex situ XRR film thickness measurement
ð20Þ data presented previously (Holmqvist et al., 2012).

The convex MAUF was optimized by the indirect single-objective

optimization routine fmincon, in the Optimization Toolbox™ for
MATLABs (The MathWorks, Inc., 2010b). It is worth noting that
Uðu; λÞ is the convex function of normalized objectives, f i
 ϑi
max f i ðuÞ−f i ðuÞ
f i ðuÞ ¼ ð21Þ
max f i ðuÞ−min f i ðuÞ
in which ϑi are the relative tolerances (Benyahia et al., 2011) and
the weights λi are chosen such that λi ≥0 and ∑i ¼ 1 λi ¼ 1. For
further details and geometric interpretation in the objective
function space of the weighted-sum-method see e.g. Logist et al.
(2009).
6. Results and discussion
Previous work on optimization and design strategies for ALD
processes has mainly focused on throughput enhancement. This is
true of both theoretical work (Lim et al., 2000, 2001; Park et al.,
2000) and experimental studies (Aarik et al., 2006; Jur and
Parsons, 2011; Kuse et al., 2003; Lei et al., 2006; Mousa et al.,
2012). The strategies developed in this way are primarily based on
optimizing the average precursor substrate exposure dose, 〈δα 〉
(Eq. (11)). Furthermore, the comprehensive univariate sensitivity
analysis of u on mass gain per cycle (MGPC) (Burton et al., 2009),
〈ms 〉, and UFjΔt , presented in Holmqvist et al. (2012) extends the
framework for throughput enhancement to include the impact
of inhomogeneous precursor flux profiles across the substrate
during the exposure period (Gobbert et al., 2002). This exten-
sion complements experimental studies (Cleveland et al., 2012;
Henn-Lecordier et al., 2011) that assessed the uniformity of film
thickness in cross-flow ALD reactor designs.
However, the univariate method makes a fundamental assump-
tion about the structure of the covariance matrix, ΣðXÞ (Eq. (19)),
with ϱjj ≡0 and ∀j. This assumption is not adequate in a situation in
which DVs and relations between the DVs and the objectives and
algebraic constraints are interdependent. Hence, it is not possible
to avoid sub-optimal solutions when using the sequential one-
variable-at-a-time (OVAT) approach. In contrast, the extended
multivariate MO method presented in Section 3 makes no
assumptions about the structure of ΣðXÞ, and this method is
therefore more appropriate for determining the optimal decision
space, un ∈P n .
6.1. Multi-objective optimization analysis
The proposed model-based methodology for the multivariate
and constrained MOP gives adequate importance to the incom-
mensurable objective functions (Eqs. (8) and (9)) under the
constraints of film thickness uniformity (Eq. (14)), purge duration
(Eq. (17)), and set of DV boundaries (Table 1). Fig. 3 presents the
approximation of the Pareto optimal front, PF n , for UFjΔt;min ∈
½0:90; 1:0½ and N Ω ¼ 2:0 obtained with the implemented MOEA,
subject to Eq. (3). The figure presents also the solutions generated
by the fmincon algorithm (The MathWorks, Inc., 2010b) subject to
Eq. (20) and the associated weight vector λ1 ∈½0:0; 1:0 and relative
tolerance vector ϑ ¼ ½5:0; 5:0  10−2 . It is noteworthy that the
solutions Uðun ; λÞ are superjacent to the solutions f ðun Þ, validating
that the optimization has converged to the true PF n . Furthermore,
the objective function values, f ¼ ½PjΔt ; Y ZnðC2 H5 Þ2 jΔt , associated
with the experimental X-ray reflectivity (XRR) ZnO film thickness
measurement data presented previously (Holmqvist et al., 2012)
clearly show the prospects of optimizing temporally separated
ALD processes. It is, however, noteworthy that the experimental
operating conditions governed the number of reactor chamber
volumes purged in the range N Ω;XRR ∈3:0; 4:0½102 , and thus,
explains the large difference between the experimental deter-
mined and the model generated PjΔt .
In addition, Fig. 3 shows that the discrepancy between the Pareto
optimal fronts for UFjΔt;min ∈½0:90; 1:0½ is lower for Y ZnðC2 H5 Þ2 jΔt o
0:40. As emphasized in Section 3.4.1, the non-uniform film height,
 A. Holmqvist et al. / Chemical Engineering Science 96 (2013) 71–86 77

Fig. 4. Film thickness profile, hs ðζÞ, as a function of the substrate boundary, Γ sub , local coordinate variable, ζ∈½0; jΓ sub j, for unλ associated with λ1 ¼ ½0:1; 0:2; 0:4; 0:6† and
−1
UFjΔt;min ∈½0:90; 1:0½. hs ðζÞ (Å cycle ) associated with: (–) UFjΔt;min ¼ 0:90; ð−  −Þ UFjΔt;min ¼ 0:95; (– –) UFjΔt;min ¼ 0:99.

hs ðζÞ, in the range ζ∈½0; jΓ sub j originates from the decrease in gas–
surface reaction driving force, hence r ℓ ∝pα jΓsub (Holmqvist et al.,
2012), which in turn results from depletion of the precursor pulse
along the direction of the flow. This phenomenon is evident when
analyzing the spatial resolution of hs ðζÞ for the set of optimal
operating points
unλ ¼ fun : ⇁∃u∈Rnj ; Uðu; λÞ≥Uðun ; λÞ∧f ðun Þ∈PF n g
and associated weight vector, λ1 ¼ ½0:1; 0:2; 0:4; 0:6, depicted in
Fig. 4, where higher values of Y ZnðC2 H5 Þ2 jΔt lead to lower film thickness
uniformity (Eq. (13)). Consequently, in order to fulfill more stringent
constraints on the uniformity of film thickness (corresponding to
UFjΔt;min -1:0), sufficient driving forces in the forward reaction rates,
r ℓ , must be preserved as ζ-jΓ sub j, which in turn requires higher
half-cycle average substrate exposure doses, 〈δZnðC2 H5 Þ2 〉 (Eq. (11)),
at the expense of lower Y ZnðC2 H5 Þ2 jΔt . This is apparent when analyzing
Fig. 3, where the optimal Pareto front, PF n , in the range
Y ZnðC2 H5 Þ2 jΔt ∈0:0; 0:4½ is forced towards the origin as UFjΔt;min -1:0.
Fig. 5 shows the dynamic model response resolved at the
level of a single ALD pulse sequence for the set of optimal
operating points, unλ , in order to demonstrate the implication
of a single-objective optimization of the incommensurable objec-
tives, f ¼ ½PjΔt ; Y ZnðC2 H5 Þ2 jΔt . The normalized integral mean mass
increment trajectory, 〈ms 〉 ¼ 〈ms 〉ðΛM s Þ−1 , for unλ and λ1 ¼ 0:9
(Fig. 5a) exceeds 90% of the theoretical maximum deposited ZnO
film mass at t ¼ Δt, whereas the associated mean gas–phase molar
compositions, 〈ψ α 〉, at Γ in and Γ out correspond to low ZnðC2 H5 Þ2
yield, Y ZnðC2 H5 Þ2 jΔt ¼ 14:8%. In contrast, the model response asso-
ciated with unλ and λ1 ¼ 0:1 (Fig. 5d) corresponds to a high
ZnðC2 H5 Þ2 yield, Y ZnðC2 H5 Þ2 jΔt ¼ 96:2%, whereas 〈ms 〉 o 0:70 at
ð22Þ t ¼ Δt. Hence, λ1 ¼ ½0:0; 1:0 comprises the anchor points of the
solutions of the single-objective optimization problems for each
criterion.
6.1.1. Assessment of the optimal operating condition parameters
The projection of the feasible objective function space and
the feasible inequality algebraic constraint space depicted in Fig. 6
provide rigorous information about the Pareto optimal solution
set, P n ∈U, which comprises the ALD process design space. More-
over, the distinctive scatter of feasible dominated solutions in
Fig. 6 reveals the corresponding dependence in the objective
function space f ∈R2 for UFjΔt;min ¼ 0:90 depicted in Fig. 3. For
clarification purposes, the feasible dominated solutions, u∈U, in
Fig. 6 are distributed between the DV lower and upper boundaries
that are listed in Table 1, and reveal the relations between the DVs
and the objective functions, PjΔt and Y ZnðC2 H5 Þ2 jΔt , and the algebraic
78 A. Holmqvist et al. / Chemical Engineering Science 96 (2013) 71–86
Fig. 5. Dynamic process analysis resolved at the level of one ALD pulse sequence, Δt, for UFjΔt;min ¼ 0:90 and unλ associated with λ1 ¼ ½0:1; 0:4; 0:6; 0:9† . (–) 〈ms 〉 ¼ 〈ms 〉ðΛM s Þ−1
(a.u.) at Γ sub . Integral mean gas–phase molar composition 〈ψ α 〉jΓ (a.u.) of the αth precursor ðα∈fZnðC2 H5 Þ2 ; H2 OgÞ at Γ in and Γ out : ð−  −Þ 〈ψ ZnðC2 H5 Þ2 〉jΓ in ; ð○−Þ 〈ψ ZnðC2 H5 Þ2 〉jΓ out ;
(- -) 〈ψ H2 O 〉jΓ in ; ð−▿−Þ 〈ψ H2 O 〉jΓ out .
constraint, UFjΔt . Furthermore, the superposed non-dominated
solution set, P n ∈U, shows the subset of feasible solutions that
governs the Pareto optimal front, PF n , depicted in Fig. 3. Thus, the
presented multivariate MO method enables simultaneous investi-
gation of the interdependence of the DVs, and the dependence
of the optimal DVs on the proposed objectives and algebraic
constraints.
The dependence of the feasible dominated solutions for the
temperature, T, (Fig. 6) exhibits convex behavior with respect to
both PjΔt and Y ZnðC2 H5 Þ2 jΔt . The model response in the range
T∈½3:0; 4:5½102 (K) is attributed to the activation energy in the
Arrhenius equation (Schwaab and Pinto, 2007, 2008; Schwaab
et al., 2008) of the elementary gas–surface reaction mechanism as
defined in Holmqvist et al. (2012). The model response in the
range T∈4:5; 6:0  102 (K), however, originates from extensive
dehydroxylation, which overrides the effect of the increase in
hydroxyl groups during the H2 O exposure sequence (Deminsky
et al., 2004; Matero et al., 2000). Additionally, Eqs. (10) and (15)–
(17) make it clear that Δt N2 ∝pðT Q_ N2 Þ−1 , which implies that the
optimal T (which corresponds to max PjΔt ) is a compromise
between a high gas–surface reaction rate and a low Δt N2 . On the
other hand, Y ZnðC2 H5 Þ2 jΔt is time-invariant (Eq. (9)), and is not
affected by the parametric dependence of Δt N2 .
The projection of the non-dominated solutions for Q_ N2 shown in
Fig. 6 exhibits weak convex behavior with respect to PjΔt . Accordingly,
−1
a reduction in Q_ N2 increases the inlet mass fraction ðωα jΓin ∝Q_ N2 Þ of
the αth precursor, and promotes the driving force in the forward
elementary gas–surface reactions (r ℓ ∝pα (Holmqvist et al., 2012)) at
−1
the expense of an increase in the duration, Δt N ∝Q_ , of the post- 2 N2
precursor purge. However, since Y ZnðC2 H5 Þ2 jΔt (Eq. (9)) is time-invar-
iant, maxY ZnðC H Þ j is achieved at the lower boundary of Q_ , as
2 5 2 Δt N2
expected. Likewise, the dependence of the non-dominated solutions
for 〈p〉jΓout on Y ZnðC2 H5 Þ2 jΔt is dictated to a high degree by the
aforementioned parametric dependence, and corresponds to an
optimal gas–surface reaction rate ðr ℓ ∝pα Þ, in which the molar fraction,
ψ , of the αth precursor is ultimately governed by Q_ .
α N2
The feasible dominated solutions of 〈p〉jΓout also depend on PjΔt
in a convex manner (Fig. 6). The model response in P Δt for 〈p〉jΓout is
ultimately determined by the incommensurability between the
forward elementary gas–surface reaction rates, r ℓ ∝p, and the post-
precursor pulse duration, Δt N2 ∝p. This is evident from analyzing
the associated post-precursor purge period, which arises from
the parametric interdependence of u ¼ ½T; 〈p〉jΓout ; Q_ N2  through
Eqs. (10) and (15)–(17) for the set of non-dominated solutions.
Hence, as 〈p〉jΓout approaches atmospheric pressure, the overall
 A. Holmqvist et al. / Chemical Engineering Science 96 (2013) 71–86 79

Fig. 6. Projection of the feasible objective function space and the feasible inequality constraint space for UFjΔt;min ¼ 0:90 and the set of DVs u ¼ ½T; 〈p〉jΓ out ; Q_ N2 , and the
associated post-precursor purge time, Δt N2 (Eqs. (10) and (15)–(17)). ð○Þ Feasible Pareto optimal solution set, P n ∈U; ðÞ Feasible dominated solutions, u∈U; ð◀Þ Ex situ XRR film
thickness measurement data presented previously (Holmqvist et al., 2012).

productivity (Eq. (8)) is favored more by a reduction in Δt N2 than it
is by promoting the forward gas–surface reaction rates. The impact
of 〈p〉jΓ out on PjΔt for N Ω ∈½2:0; 1:0  102  (Eq. (17)) will be discussed
in detail in Section 6.1.2.
In conclusion, the projection of the non-dominated solutions
depicted in Fig. 6 demonstrates that it is impossible to optimize
the set of DVs u ¼ ½T; 〈p〉jΓ out ; Q_ N2  using an OVAT approach without
obtaining solutions that are essentially of a local optimization
nature. This is a consequence of the severe parametric interde-
pendence, ultimately determined from the inherent mathematical
structure of Eq. (10).
solutions accumulate near the lower boundary (Table 1). This
shows that a reduction in Δt N2 favors the overall productivity
(Eq. (8)) more than it promotes the forward gas–surface reaction
rates. It is, however, noteworthy that the severe dependence of
Δt N2 on P Δt falls as N Ω -1:0. This implies that the duration of the
post-precursor purge is of key importance when optimizing the
throughput of cross-flow, low-volume ALD reactor designs with
temporal precursor pulsing, and that it presents a major obstacle
when considering the optimal operation of atmospheric pressure
ALD designs.

6.1.3. Assessment of the optimal pulse sequence parameters

6.1.2. Assessment of the constraint on post-precursor purge duration
Fig. 8 shows how the feasible non-dominated solutions,
Fig. 7a shows Pareto optimal fronts, PF n , for N Ω ∈½2:0; 1:0
2 P n ¼ ½Q_ ZnðC2 H5 Þ2 , Δt ZnðC2 H5 Þ2 ∈U, depend on f ¼ ½PjΔt ; Y ZnðC2 H5 Þ2 jΔt . It
10 , and demonstrates the impact of the predefined number of
is noteworthy that the ultimate model response is governed by the
reactor chamber volumes purged, NΩ in Eq. (17), during the post-
product of these two DVs, which represent the precursor dose
precursor purge period, Δt N2 , on the feasible objective space,
injected, ðQ_ α Π α ðt; Δt α ÞÞjΓin . Consequently, the MOEA is incapable of
f ¼ ½PjΔt ; Y ZnðC2 H5 Þ2 jΔt . It is apparent that max Y ZnðC2 H5 Þ2 jΔt ¼ 1:0 is
distinguishing between values of Δt ZnðC2 H5 Þ2 ≠0 when Q_ ZnðC2 H5 Þ2 -0,
achieved for the entire range of N Ω , since this optimization
due to the way in which the parameters depend on each other.
criterion is time-invariant, whereas the response in PjΔt is non-
The projection of the dominated solutions for Δt ZnðC2 H5 Þ2 shown
linear and max PjΔt is reduced by a factor of 5.5.
in Fig. 8, behave in a non-convex manner with respect to both
In addition, the behavior of 〈p〉jΓout with respect to PjΔt (Fig. 7b)
objectives, and the non-dominated solutions accumulate at the
is non-convex for N Ω ¼ 1:0  102 , and the non-dominated lower boundary, min Δt ZnðC2 H5 Þ2 . Furthermore, the non-dominated
80 A. Holmqvist et al. / Chemical Engineering Science 96 (2013) 71–86
Fig. 7. Feasible objective space f ¼ ½PjΔt ; Y ZnðC2 H5 Þ2 jΔt † ∈R2 for the constrained MOP
(Eq. (3)) subject to u and the boundaries listed in Table 1. (a) Pareto optimal front,
PF n , for N Ω ∈½2:0; 1:0  102 . (b) Normalized productivity, P jΔt , as a function of the
non-dominated solutions for log10 〈p〉jΓ out . ð○Þ N Ω ¼ 2:0  100 ; ð▿Þ N Ω ¼ 1:0  101 ;
ð◊Þ N Ω ¼ 2:5  101 ; ð△Þ N Ω ¼ 1:0  102 ; ð◀Þ Ex situ XRR film thickness measurement
data presented previously (Holmqvist et al., 2012).
solutions associated with Q_ ZnðC2 H5 Þ2 are distributed in the range
½min Q_ ZnðC2 H5 Þ2 ; max Q_ ZnðC2 H5 Þ2 . Accordingly, the optimal injected
precursor dose with respect to PjΔt is governed by max Q_ α min Δt α ,
whereas min Q_ α min Δt α is optimal with respect to Y α jΔt and
α ¼ ZnðC2 H5 Þ2 . This implies that minΔt ZnðC2 H5 Þ2 ≡Δt sat;ZnðC2 H5 Þ2 as
maxQ_ ZnðC2 H5 Þ2 gives the saturation half-cycle average substrate
exposure dose, 〈δZnðC2 H5 Þ2 〉 (Eq. (11)), which satisfies Eq. (12). Once
it has been guaranteed that Eq. (12) is satisfied, Δt α and ∀α can be
safely excluded from the set of DVs listed in Table 1 and they can
be assigned their minimum acceptable values, since the optimiza-
tions of Eqs. (8) and (9) both strive to minimize Δt α . Furthermore,
it was postulate in Section 3.3 that ½Q_ H2 O , Δt H2 O  ¼ ½max Q_ ZnðC2 H5 Þ2 ,
min Δt ZnðC2 H5 Þ2  governs max PjΔt , and Fig. 8 shows that this is valid
for the ZnðC2 H5 Þ2 precursor.
6.2. Uncertainty and sensitivity analysis
The non-dominated solutions, P n ∈U, shown in Figs. 6 and 8
provide flexibility for the decision maker, but information from the
UA/SA analysis about the robustness along the Pareto optimal
front, PF n , (Fig. 3) is also needed in order to determine the
optimal control space in which the process accommodates input
variability in the optimal set of DVs without volatility in the
assigned constraints (Eq. (4)). It was shown in Section 6.1 that the
inequality constraint of the uniformity of cross-substrate film
thickness (Eq. (14)) dictates to a high degree the extension of
the Pareto optimal front, and this is the reason that the post-
optimization analysis is needed. Consequently, several of the
solutions along the Pareto optimal front possess the minimum
acceptable degree of film thickness uniformity ðUFjΔt ≡UFjΔt;min Þ,
and the existence of these solutions implies that the process is on
the verge of failure.
6.2.1. Uncertainty analysis
In order to evaluate the robustness of the set of non-dominated
solutions, the associated optimal decision space, unλ (Eq. (22)), was
subject to the assigned normal distribution, u^ λ ∼N ðunλ ; s2un Þ, with
λ
lower and upper control limits with a percentage deviation of
sunλ ¼ ½1:0; 5:0; 10:0ð%Þ, in all the DVs listed in Table 1 and with a
limit of 95% of the values drawn from the distribution within two
standard deviations, sunλ , away from the mean, unλ . For each case
λ1 ¼ ½0:1; 0:2; 0:4; 0:5; 0:6; 0:8; 1:0, ju^ λ j ¼ 2:0  103 process scenar-
ios were selected using lhsnorm in the Statistics Toolbox™ for
MATLABs (The MathWorks, Inc., 2010c), and assigned a duration
n
of post-precursor purge, Δt N2 , of u^ λ as specified by Eq. (17). Fig. 9
shows the resulting model response in f ¼ ½PjΔt , Y ZnðC2 H5 Þ2 jΔt  for
½UFjΔt;min ; N Ω  ¼ ½0:95; 2, while Table 2 lists the fraction of the
sample, ju^ λ ∉Ujðju^ λ jÞ−1 that violates the algebraic inequality con-
straint (Eq. (14)) for each case and degree of DV perturbation. In
addition, Fig. 9 shows the projection along the principal axes of
the concentric hyperellipsoid contour with equal probability ð1−αÞ
centered at μ^ X
^
fX : ½X−μ^ X † ΣðXÞ −1
½X−μ^ X  ¼ χ 2ðφ;αÞ g ð23Þ
with the estimated covariance matrix, ΣðXÞ ^ (Eq. (19)), using
gmdistribution in the Statistics Toolbox™ for MATLABs . By this
means, it was possible to quantify the magnitude and direction
of displacements associated with the model response, X ¼ f ðu^ λ Þ.
It is apparent from Fig. 9 that the eigenvector of the estimated
covariance matrix, Σðf ^ ðu^ λ ÞÞ, approximately intersects the origin
for each case λ1 . This means that the process uncertainties,
u^ λ ∼N ðunλ ; s2un Þ, display a loss in f in the direction towards the
λ
origin. Accordingly, the difference between the estimated μ^ f ðu^ λ Þ
n
of Eq. (18) and f ðu^ λ Þ has a significant trend along the PF n , where
PjΔt is most uncertain as λ1 -1:0 and Y ZnðC2 H5 Þ2 jΔt as λ1 -0:0
(cf. Table 2).
Fig. 10 shows in a similar manner the simulated model
response distribution in UFjΔt for each case λ1 and sunλ ¼ 10:0ð%Þ.
It is evident that the robustness of the process increases as the
parameter set moves towards the operating points as λ1 -1:0. This
observation is consistent with the findings presented in Section
6.1, where the discrepancy between the Pareto optimal fronts for
UFjΔt;min ∈½0:90; 1:0½ was lower for Y ZnðC2 H5 Þ2 jΔt o 0:40. In conclu-
sion, it is impossible to attain max Y ZnðC2 H5 Þ2 jΔt while preserving
the process robustness, inherent to higher half-cycle average
 A. Holmqvist et al. / Chemical Engineering Science 96 (2013) 71–86 81

Fig. 8. Projections of the feasible objective function space and the feasible inequality constraint space for UFjΔt;min ¼ 0:90 and for the set of DVs u ¼ ½Q_ ZnðC2 H5 Þ2 ; Δt ZnðC2 H5 Þ2 , and
the associated half-cycle average substrate exposure dose, 〈δZnðC2 H5 Þ2 〉 (Eq. (11)). ð○Þ Feasible Pareto optimal solution set, P n ∈U; ðÞ Feasible dominated solutions, u∈U; ð◀Þ Ex
situ XRR film thickness measurement data presented previously (Holmqvist et al., 2012).

Table 2
Analysis of the impact of the sample u^ λ ∼N ðunλ ; s2un Þ, with a percentage deviation of
λ

sunλ ¼ ½1:0; 5:0; 10:0ð%Þ in the set unλ (Eq. (22)) on f ¼ ½P jΔt ; Y ZnðC2 H5 Þ2 jΔt † and on
UFjΔt along the Pareto optimal front for ½UFjΔt;min ; N Ω  ¼ ½0:95; 2.

λ1 n
jμ^ f 1 ðu^ λ Þ −f 1 ðu^ λ Þj (%)
n
jμ^ f 2 ðu^ λ Þ −f 2 ðu^ λ Þj (%) ju^ λ ∉Uja
(%)
ju^ λ j

0.1 0.08,0.63,2.23 0.30,2.18,7.98 10.6,26.4,36.1

0.2 0.10,0.74,2.82 0.26,1.74,6.53 8.06,17.1,30.3
0.4 0.14,1.21,4.36 0.25,1.56,5.59 11.2,29.0,38.6
0.5 0.20,1.26,4.83 0.16,0.98,3.59 0.00,1.40,12.2
0.6 0.21,1.51,5.84 0.13,0.81,3.09 0.00,0.00,0.05
0.8 0.27,1.71,6.78 0.05,0.41,1.70 0.00,0.00,0.00
1.0 0.79,3.56,10.7 0.04,0.17,0.52 0.00,0.00,0.00

a
j  j denotes the cardinality of a set.

6.2.2. Sensitivity analysis

Fig. 9. Analysis of the impact of the sample u^ λ ∼N ðunλ ; s2un Þ, with a percentage
λ uncertainty in f ¼ ½P jΔt ; Y ZnðC2 H5 Þ2 jΔt  and UFjΔt , and it shows the
deviation of sunλ ¼ 10:0ð%Þ in the set unλ (Eq. (22)) and the associated weight vector
λ1 ¼ ½0:1; 0:2; 0:4; 0:5; 0:6; 0:8; 1:0† , on f ¼ ½P jΔt ; Y ZnðC2 H5 Þ2 jΔt † along the Pareto opti-
mal front, PF n , for ½UFjΔt;min ; N Ω  ¼ ½0:95; 2 with the set of DVs listed in Table 1.
(−▿−) PF n for sunλ ¼ 0:0ð%Þ (cf. Fig. 3); ðÞ Projection of the model response, f ðu^ λ Þ;
ð
Þ Estimated μ^ f ðu^ λ Þ of Eq. (18); (–) Projection of the hyperellipsoid with a
significance level α ¼ 5:0ð%Þ (Eq. (23)); (- -) The principal axes are given by the
eigenvectors of Σðf^ ðu^ λ ÞÞ (Eq. (19)).
substrate exposure doses, 〈δα 〉, and hence, the process disturbances
must be more strictly controlled to ensure high performance when
targeting this optimization criterion.
Section 4 describes how the sensitivity analysis involves esti-
mating the parameters μ^ X and ΣðXÞ, ^ which are associated with the
approximated pdf, ϕðXÞ with X ¼ ½u; PjΔt ; Y ZnðC2 H5 Þ2 jΔt ; UFjΔt 
(Eqs. (18) and (19)), from the sample, u^ λ ∼N ðunλ ; s2un Þ. Fig. 11 shows
λ
the impact of individual elements of the DV vector, u, on the
projection of the concentric hyperellipsoid contour (Eq. (23)).
The pattern of scatter plots shows if the correlation is high, as
do also the forms of the estimated equal probability contours,
which are elongated along the principal axes of ΣðXÞ, ^ not parallel
to the figure axes. Table 3 lists the associated correlation coeffi-
^
cients, ϱ^ X in ΣðXÞ, for each DV and case, λ1 ¼ ½0:1; 0:2; 0:4; …; 1:0.
The absolute magnitudes of the elements of ϱ^ X , show that the
temperature, T, and mass flow of the carrier gas, Q_ N2 , are less
sensitive than other variables for all optimization specifications
82 A. Holmqvist et al. / Chemical Engineering Science 96 (2013) 71–86

Fig. 10. Analysis of the impact of the sample u^ λ ∼N ðunλ ; s2un Þ, with a percentage deviation of sunλ ¼ 10:0ð%Þ in the set unλ (Eq. (22)) and associated weight vector
λ
λ1 ¼ ½0:1; 0:2; 0:4; 0:5; 0:6; 0:8† , on UFjΔt . (Histogram) Colored bars represent unfeasible solutions, u^ λ ∉U, that violate the algebraic inequality constraint (Eq. (14)); (–)
Cumulative frequency of the distribution.

and cases λ1 ∈0:0; 1:0 considered. In contrast, the pressure at the
outlet, 〈p〉jΓout , was the most critical variable, having remarkably
high correlation coefficients for λ1 o 0:6. Moreover, the sensitivity
of pulse sequence parameters, Δt ZnðC2 H5 Þ2 and Q_ ZnðC2 H5 Þ2 , to UFjΔt
increased with λ1 as expected (cf. Section 6.1). In addition,
Δt ZnðC2 H5 Þ2 was the most critical variable with respect to f as
λ1 -1:0, and this places stringent demands on the actuation
of valves for consistent precursor delivery, in agreement with
previous studies (Londergan et al., 2002).
In conclusion, Figs. 9–11 and Tables 2 and 3 make it clear that
both the uncertainty in the optimization specifications and the
sensitivity of the associated optimal DVs differ significantly along
the Pareto optimal front. It has, however, been possible to identify
the critical variables that require strict process control, and to
evaluate the robustness of the process, given the assigned pertur-
bation in the optimal DVs, sunλ .
7. Concluding remarks
This paper presents quasi-steady-state, constrained MO of the
mechanistic model of the continuous cross-flow reactor system
F-120 manufactured by ASM Microchemistry Ltd. (Suntola, 1992)
with temporal precursor pulsing. The process model has been
elaborated and experimentally validated in the first two parts of
this paper series (Holmqvist et al., 2012, 2013). The MOP involves
simultaneous optimization of the incommensurable objectives of
reactor throughput and overall precursor conversion, subject to a
set of operational constraints. The constraints include lower
bounds for the uniformity of cross-substrate film thickness and
duration of the post-precursor purge. For this reason, a novel
model-based methodology for rendering large scale constrained
MOPs for ALD processes was proposed. The non-dominated Pareto
optimal solution set was obtained by a MOEA developed and
tested for this purpose, and reduced the ALD process design space
into a feasible set of design alternatives.
The comprehensive assessment of the Pareto optimal solution
set reported here shows how increasingly stringent constraints on
the uniformity of cross-substrate film thickness and the duration
of the post-precursor purge affect the process objectives. More
stringent constraints on film thickness uniformity lead to higher
half-cycle average substrate exposure doses, provide a driving
force for the ALD gas–surface reactions towards the trailing edge
of the substrate, at the expense of lowered overall precursor yield.
Moreover, increasing the number of reactor chamber volumes
purged during the post-precursor purge period shows that the
productivity criterion is favored more by a reduction in the purge
period than by promoting the ALD gas–surface reaction rates.
 A. Holmqvist et al. / Chemical Engineering Science 96 (2013) 71–86 83

Fig. 11. Analysis of the impact of the individual elements of the sample u^ λ ∼N ðunλ ; s2un Þ, with a percentage deviation of sunλ ¼ 10:0ð%Þ in the set unλ (Eq. (22)) and associated
λ
weight λ1 ¼ 0:1, on f ¼ ½P jΔt ; Y ZnðC2 H5 Þ2 jΔt † and UFjΔt for the set of DVs listed in Table 1. ðÞ Projection of the model response; (–) Projection of the hyperellipsoid with a
percentage significance level α ¼ 5:0ð%Þ (Eq. (23)); (- -) The principal axes are given by the eigenvectors of ΣðXÞ ^ (Eq. (19)).

The subsequent UA/SA based on LHS to the non-dominated
solutions along the Pareto optimal front was carried out to assess
the impact of variability in the associated set of optimal DVs on the
optimization specifications and to identify the most critical vari-
ables. The UA/SA shows that the inherent process robustness is
progressively lost as the precursor yield increases. The process
objectives and constraints, however, may not necessarily be
affected by the same DVs along the Pareto optimal front, but the
model-based stochastic methodology presented here allows to
identify the key DVs.
Finally, the contribution of this paper is the novel model-
based methodology that considers MO in conjunction with UA/SA,
for optimizing manufacturing performance metrics of throughput
and precursor utilization in continuous cross-flow ALD reactor
designs without compromising the film quality and process
control. The fundamental process understanding gained here is of
practical interest when scaling ALD processes to large-surface-
area substrates in high-throughput productions where even small
variations in the growth rate can be detrimental to the end-use
properties.
84 A. Holmqvist et al. / Chemical Engineering Science 96 (2013) 71–86

Table 3 λ normalized weights (–)

Sensitivity of the DVs listed in Table 1 with respect to the uncertainty in the μ mean value of the normal distribution (–)
^ in
elements of ½PjΔt ; Y ZnðC2 H5 Þ2 jΔt ; UFjΔt  based on the correlation coefficients, ϱ,
Πα characteristic function of t and Δt α (–)
Eq. (19). The variability of the input originates from a normal distribution with a
percentage deviation of sunλ ¼ 10:0 ð%Þ in the set unλ (Eq. (22)) and the associated
Σ ðj  jÞ covariance matrix (–)
ξℓ surface reaction stoichiometric coefficient (–)
weight vector λ1 ¼ ½0:1; 0:2; 0:4; …; 1:0† .
ρ density (kg m−3)
u jϱ^ u^ ;PjΔt j  102 jϱ^ u^ ;Y ZnðC j j  102 jϱ^ u^ ;UFjΔt j  102 s standard deviation of the normal distribution (–)
2 H5 Þ2 Δt
ϱ correlation coefficient (–)
T 5.73,2.42,5.87 6.78,3.33,4.80 1.62,3.14,8.08 τ residence time (s)
13.2,10.5,9.34 12.2,10.4,8.40 13.7,20.3,14.9, ϕ empirical probability density function (–)
Q_ N2 2.34,1.51,4.28 7.38,2.38,5.71 5.31,3.27,7.83
ψα molar fraction of gaseous species (–)
8.08,8.27,7.95 11.3,9.65,9.88 12.9,11.8,16.1
Ω spatial domain (–)
〈p〉jΓ out 72.2,61.9,54.9 71.2,58.7,49.6 63.8,56.4,55.2 ωα mass fraction of gaseous species (–)
5.54,12.6,13.0 1.74,12.7,14.1 48.5,46.8,40.0
Q_ Zn ðC2 H5 Þ2 11.7,13.2,11.8 12.9,19.9,24.9 33.9,35.5,36.7 Subscripts and superscripts
7.95,7.60,2.57 31.0,30.9,31.1 36.2,23.0,22.1
Δt ZnðC2 H5 Þ2 13.6,6.20,4.30 12.3,29.2,24.4 41.3,40.2,37.7 0 initial value
7.05,12.9,13.8 31.5,33.8,32.0 40.9,26.4,21.1 α; β gaseous species indices
κ surface species index
i objective function index
Nomenclature j decision variable index
k; l algebraic constraint indices
Roman letters ℓ surface reaction index
AΩ cross section area of the reactor chamber (m2) STP state variable at STP
C algebraic constraint (–) sat substrate surface saturation
Dαβ s solid
binary diffusivity ðm2 s−1 Þ
F system of differential algebraic equations (–)
f objective function vector (–)
g response function (–)
hs film height ðÅÞ Acknowledgment
M molecular weight (kg mol−1)
ms film mass per unit area (kg m−2)
This work has been supported by the Swedish Research Council
Q_ α
volumetric flow rate at STP (sccm)
under Grant no. 2006-3738.
−2 −1
N_ α jΓ total mass flux normal to the boundary Γ (kg m s )
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