Chemical Engineering Science 81 (2012) 260–272

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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 I: Mechanistic modelling
of continuous flow reactors
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

c Development of an experimentally validated continuous flow ALD reactor model.

c ALD reaction mechanism is based on consecutive and parallel elementary Eley–Rideal reaction steps.
c The model provides extensive real-time quantitative information regarding reactor conditions.
c Experimental investigation with focus of the impact of process operating parameters.
c Case study on deposition of ZnO films from Zn(C2H5)2 and H2O in a continuous flow reactor.

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

Article history: This paper presents the development of an experimentally validated model that mechanistically compre-
Received 20 February 2012 hends the complex interaction between the gas-phase fluid dynamics, the mass transport of individual
Received in revised form species, and the heterogeneous gas–surface reaction mechanism in a continuous cross-flow atomic layer
3 July 2012
deposition (ALD) reactor. The developed ALD gas–surface reaction mechanism, purely based on consecutive
Accepted 13 July 2012
Available online 22 July 2012
and parallel elementary Eley–Rideal reaction steps, was incorporated into the computational fluid dynamic
representation of the equipment-scale. Thereby, the model mechanistically relates local gas-phase condi-
Keywords: tions in the vicinity of the substrate surface to the transient production and consumption of the fractional
Atomic layer deposition surface coverage of chemisorbed species, ultimately underlying epitaxial film growth. The model is oriented
Ex situ film characterization
towards optimization and control and enables identification of substrate film thickness uniformity
Mathematical modelling
sensitivities to process operating parameters, reactor system design and gas flow distribution. For the
Computational fluid dynamics
Transport processes experimental validation of the derived mathematical model, a detailed experimental investigation with the
Reaction engineering focus on the impact of process operating parameters on the spatial evolution of ZnO film thickness profile
was performed. The controlled deposition of ZnO from Zn(C2H5)2 and H2O was carried out in the continuous
cross-flow ALD reactor system F-120 by ASM Microchemistry Ltd. and ex situ film thickness measurements
at a discrete set of sampling positions on the substrate were performed using X-ray reflectivity and X-ray
fluorescence analysis. The experimental results reported here, underscore the importance of substrate-scale
uniformity measurements in developing mechanistic ALD process models with high predictability of the
dynamic evolution of the spatially dependent film thickness profile. The experimental validation and
extensive mechanistic analysis of the ALD reactor model are presented in the second article of this series
(Holmqvist et al., in press).
& 2012 Elsevier Ltd. All rights reserved.

1. Introduction conformal films on topographically complex structures, a unique

Atomic layer deposition (ALD) is being increasingly utilized for
the manufacture of thin inorganic films with thickness on
the nanometer scale (George, 2010). ALD can be used to deposit
n
Corresponding author. Tel.: þ46 46 222 8301; fax: þ46 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).
feature among thin-film deposition techniques (Sneh et al., 2002).
Conventional ALD is a special modification of the chemical vapor
deposition (CVD) technique based on sequential self-terminating
gas–surface reactions (Masel, 1996), where the non-overlapping
alternate injection of the precursors1 separated by intermediate
1
Precursors are the gas phase chemical species that react to form the
deposited film (see Puurunen, 2005 for an overview relevant to ALD).

0009-2509/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2012.07.015
 A. Holmqvist et al. / Chemical Engineering Science 81 (2012) 260–272
purge step prevents reaction in the gas phase, allowing the use of
highly reactive precursors and providing sufficient time for each
reaction step to reach completion (Leskelä and Ritala, 2003). Conse-
quently, the deposition process is highly dependent on the adsorption
and surface reaction kinetics (Ritala and Leskelä, 2002), and the under-
lying mass transport (Yanguas-Gil and Elam, 2012; Ylilammi, 1995).
ALD has already emerged as the prime candidate for depositing of
ultra-thin layers with high conformality in semiconductor manufac-
turing (Lei et al., 2006). Recently, the interest in ALD as a photovoltaic
manufacturing technique has increased and the functions of ALD
have expanded (Poodt et al., 2012). Applications include deposition of
surface passivation layers in crystalline silicon (c-Si) solar cells and
buffer layers in CuIn1 xGaxSe2 (CIGS) based thin film solar cells
(Bakke et al., 2011). In this context, experimental and mathematical
modelling studies on deposition of ZnO films were performed in the
present work. ZnO-based compounds by ALD are of great interest as
buffer layers in CIGS based thin film solar cells (Naghavi et al., 2010,
2011) as a replacement of standard CdS buffer layers prepared by
chemical bath deposition (CBD) for environmental reason, and due to
the ability to change the electrical and optical properties of ZnO
by addition of other elements. CIGS based devices with ZnO1 xSx
(Platzer-Björkman et al., 2006), Zn1 xMgxO (Törndahl et al., 2007,
2009) and Zn1 xSnxOy (Hultqvist et al., 2011, in press) films
deposited by ALD have already shown comparable device efficiency
to CdS devices. A cross-section transmission electron microscopy
(TEM) micrograph of a CuInSe2 (CIS) thin film solar cell device with
an ALD-ZnO buffer layer is depicted in Fig. 1, where the experi-
mental parameters for growing this device are described in Platzer-
Björkman et al. (2003).
1.1. Review of mathematical models for ALD processes
Despite the numerous successful applications of material growth
by ALD (Kim, 2003; Kim et al., 2009), significant developmental
issues remain in many applications. Further, recognition that many
physicochemical processes controlling ALD growth are not suffi-
ciently understood has motivated recent modelling studies. A num-
ber of models have been presented to date, featuring a multitude of
approaches and levels of modelling detail (Elliott, 2007). The diversity
of published work in the field is a consequence of the broad range of
modelling objectives and applications. The models proposed so far
can be divided into four different categories.
(i) Atomic-scale models, applying first-principle density func-
tional theory (Elliott and Greer, 2004) and quantum-chemical
cluster calculations, have been developed to investigate
Fig. 1. Cross-section TEM micrograph of CIS solar cell with an ALD-ZnO buffer
layer. The general device structure of a CIGS solar cell is: soda lime glass (SLG)/Mo/
CuIn1  xGaxSe2/buffer layer/i-ZnO/ZnO:Al, where the buffer layer is either CBD-CdS
or a high performing alternative buffer layer as described in Naghavi et al. (2010).
The entire stack of thin film materials in a CIGS based solar cell is commonly
around 2–4 mm in thickness.
261
reaction pathways of the chemical reactions taking place at
the different stages of ALD growth, the surface intermediates
formed and their corresponding energies. These results
provide additional physical insight into the nature of these
reaction mechanisms and demonstrate the relative ener-
getics of adsorption and ligand elimination (Heyman and
Musgrave, 2004). The kinetic parameters determined with
these models can be used in high-level simulations such as
transport models (Yanguas-Gil and Elam, 2012; Ylilammi,
1995) and kinetic Monte Carlo schemes (Adomaitis, 2010;
Mazaleyrat et al., 2005).
(ii) Empirical models of ALD growth kinetics for the prediction of
initial growth reactions on the substrate have been developed
to investigate the potential use of ALD for depositing thin films
on silicon-based surfaces in the semiconductor industry.
Generally, simple phenomenological models, based on nuclea-
tion and growth (Alam and Green, 2003; Yim et al., 2008) and
island formation (Puurunen and Vandervorst, 2004; Puurunen
et al., 2004), have been used to investigate the origin of
different growth modes. Furthermore, models based on gen-
eral gas–surface reaction kinetics (Lim et al., 2000a,b, 2001;
Park et al., 2000) have been developed to predict incomplete
surface saturation growth.
(iii) Ballistic transport and surface reaction models have been
developed for simulating ALD processes in high-aspect-ratio
nanopores, such as those found in integrated circuit fabrication
(Gordon et al., 2003). Because of thevery large Knudsen number
corresponding to these processes, transport models for transi-
ent deposition processes and direct solution to Boltzmann’s
equations describing molecular level precursor transport
dynamics were developed in Gobbert et al. (2002a,b). Addi-
tionally, Adomaitis (2011) derived expressions for transmission
probability functions describing fluxes between the pore sur-
face features based on the work of Cale (1991) and Cale and
Raupp (1990). These models can be exploited to determine
optimal precursor exposure levels for intricate deposition sur-
face topographies.
(iv) Mechanistic models of continuous cross-flow ALD reactors,
incorporating gas–surface reaction mechanisms of the film
growth on the atomic scale into a continuum description of
precursor gas transport at the macroscopic level, have been
developed to investigate the substrate spatially dependent
film thickness profile (Aarik and Siimon, 1994; Siimon
and Aarik, 1995, 1997). In the cited studies, the 1D model
comprises continuity equations for the precursor mass transport
and equations for the spatial evolution of the surface adsorbent
coverage. A potential model reduction, quantified by the magni-
tude of the Peclet number, was presented in Ylilammi (1995).
The transient plug-flow model was later on generalized by
Yanguas-Gil and Elam (2012) to account for the influence of
axial diffusion. Additionally, Deminsky et al. (2004) and Knoops
et al. (2011) carried out simulations based on the plug-flow
limit, however both studies have excluded the mathematical
description. Essentially, the mechanistic models can be categor-
ized into two separate types, based on how the gas–surface
interaction is incorporated into the transport model. One
approach is to define an effective sticking coefficient (Aarik
and Siimon, 1994; Siimon and Aarik, 1995; Yanguas-Gil and
Elam, 2012; Ylilammi, 1995), lumping many significant factors
of the surface reaction process into a single parameter. The other
approach is to use a kinetic mechanism to describe the relevant
elementary gas–surface reactions based on the Arrhenius
equation (Deminsky et al., 2004).
Atomic-scale models often provide a basic understanding of
the adsorption process, while valuable insight into the complicated
262 A. Holmqvist et al. / Chemical Engineering Science 81 (2012) 260–272
details of the process can be obtained by integration with a relevant
equipment-scale model. Reactor geometry and gas flow conditions
have been recognized as vital elements in film deposition using ALD
(Elliott, 2007). The relative importance of process operating para-
meters on the character and mechanism of surface reactions has been
assessed in several experimental studies. The influence of the carrier
gas flow rate and pressure on the film growth rate was investigated
by Aarik et al. (2006) and Jur and Parsons (2011), whereas the effect
of non-uniform gas distribution and non-uniform distribution of the
precursor in the carrier gas was emphasized by Elers et al. (2006).
Further, the temperature, which is the most readily attribute to
activation energies of the elementary reactions, as well as the process
time parameters, i.e. precursor exposure and purge times, depen-
dence have been undertaken seriously by Lei et al. (2006).
However, the mechanistic details of equipment-scale process
operating parameters have not yet been thoroughly studied theore-
tically. Because the main objective of the models described above
was to determine the main features of the chemical mechanism and
atomic nature of film growth, detailed fluid dynamics have been
neglected. The Semiconductor Industry Association (2011) recently
published the International Technology Roadmap for Semiconductors
(ITRS) guidelines in which the importance of understanding the
mechanistic process was emphasized within the scope of developing
predictive models and in situ diagnostics for ALD processes. Hence,
validated, predictive ALD models are critical for the successful
prediction of the influence of equipment on the properties of the
film, as such models can be used in the design and evaluation of
reactors, and to improve the efficiency of film growth in existing
reactors. As reliability becomes more and more important, modelling
will become increasingly necessary to provide design tools, not only
to optimize throughput in manufacturing, but also to achieve more
robust reliability margins. In the ITRS initiative, the need for model-
ling is emphasized to investigate the impact of equipment and
process-induced variations, and to minimize the impact of process
variations that have critical effects in manufacturing and the robust-
ness of designs.
In order to be able to validate models, the ITRS guidelines promote
the use of modern process analytical and monitoring technologies,
including the in situ quartz crystal microbalance (QCM) (Aarik et al.,
1994a,b; Elam et al., 2002a; Fan and Toyoda, 1992; Yousfi et al.,
2000) and quadrupole mass spectroscopy (QMS) (Juppo et al., 2000;
Lei et al., 2006; Rahtu and Ritala, 2002), which provide extensive real-
time quantitative information regarding process chemistry and
reactor conditions. In order to utilize the detailed process dynamics
revealed by in situ monitoring technologies in the development
of validated, predictive ALD process models, computational fluid
dynamics (CFD) including the surface reaction mechanism is becom-
ing increasingly necessary.
1.2. The multi-scale nature of the problem and its implication for
modelling
Ideally, a model for ALD processes describes all relevant physico-
chemical processes in the reactor, and relates these phenomena to
the properties of the deposited film. All ALD processes are controlled
through equipment-scale process operating parameters, such as
pressure, temperature and flow rates, and the macroscopic scale
gas flow dynamics determine the external mass transport of gas-
phase precursors to the active surface of the substrate. Thereby, a
complete model for a deposition system cannot avoid the largest
scale framework. However, the heterogeneous ALD gas–surface
reactions underlying the epitaxial film growth are determined by
phenomena at the atomic scale.
In addition to the two length scales, the full ALD process is also
characterized by two time scales (Adomaitis, 2010): the slower time-
scale of film growth and faster time corresponding to heterogeneous
surface reactions and the precursor exposure period duration. This
splits the model problem neatly into a combination of spatial and
temporal scales, and the phenomenological aspects of coupling the
atomic-scale model of the heterogeneous surface reactions and film
growth to the continuum description of gas flow dynamics and
precursor mass transport within the reactor are illustrated in Fig. 2a.
The coupling between the spatial scales is bidirectional (Kleijn et al.,
2007), where the net impingement mass flux onto the flat active
substrate surface is balanced with the sum of the heterogeneous ALD
surface reactions that takes place over each exposure period (Gordon
et al., 2003). It is noteworthy that the precursor pulses become
depleted in the direction of the flow, and consequently, the impinge-
ment mass flux of precursors and thereby the surface reaction rates
are not spatially constant throughout the substrate.
The gaseous precursors are admitted separately in an alternate
fashion (see Fig. 2a), which enables individual chemisorption onto
the substrate surface. The ALD binary reaction sequence chem-
istry (Park et al., 2000) for growing compound AB from Axx and
Byy is schematically illustrated in Fig. 2b. Generally, during the
first adsorptive precursor exposure sequence (i) the intermediate
chemisorption complex on the surface By reacts with the incom-
ing volatile precursor Axx which thereby becomes anchored to
the surface. The subsequent reaction sequence (iii) proceeds in an
analogous manner during the Byy precursor exposure, where the
outermost intermediate chemisorption complex Ax undergo reac-
tion (Matero et al., 2000).
1.3. Objectives of this series of articles
The overall objective of this series of articles is to present a
model-based methodology for simulating an ALD process that can
be widely used to assist in process analysis, design and optimiza-
tion, bearing in mind the recent ITRS guidelines. The proposed
methodology applies the systematic modelling procedure pro-
posed by Hangos and Cameron (2001) and is founded on an
experimentally validated ALD process model using the COMSOL
s
Multiphysics (COMSOL AB, 2008b) modelling environment. The
case study on the growth of ZnO films deposited from Zn(C2H5)2
and H2O was used to demonstrate the applicability of the
framework.
The development of the experimentally validated ALD reactor
model for deposition of ZnO films in this study involved two
sequential steps.
(i) To derive a novel mathematical model that mechanistically
describes the complex interactions between the gas-phase
fluid dynamics, the mass transport of individual species, and
the heterogeneous surface reaction mechanism in a contin-
uous cross-flow ALD reactor (Suntola, 1992). The model is
oriented towards optimization and control and should be able
to accurately predict the dynamic response of the substrate
spatially dependent film thickness profile (Siimon and Aarik,
1995, 1997) to the variations of all the measured equipment-
scale process operating parameters (see Section 2). This
modelling approach is motivated by the substantial interest
of cross-flow, low-volume ALD reactor designs for manufac-
turing equipment of production-size substrates where strin-
gent uniformity; defined by Cleveland et al. (2012) as the
ratio of the standard deviation over the mean value of the
spatially dependent film thickness profile; constraints (Henn-
Lecordier et al., 2011) and demands for enhanced throughput
and precursor conversion (Lankhorst et al., 2007) require
optimal reactor designs and process operating conditions
(Elers et al., 2006).
(ii) To perform a detailed experimental investigation in order to
assess the validity of the model generated spatially dependent
 A. Holmqvist et al. / Chemical Engineering Science 81 (2012) 260–272 263

Fig. 2. Schematic representation of the multi-scale nature of the dynamic ALD process. (a) Illustrating the hydrodynamic flow field and the external mass transport of
precursors to the substrate surface at the reactor-scale. (b) Illustrating the two precursor (Axx, Byy) exposures and two purge steps constituting one complete ALD cycle
ðDt ¼ Dt A þ 2DtP þ Dt B Þ at the atomic-scale. yk denotes the fractional surface coverage of chemisorbed species k A fAx,Byg.

Fig. 3. Simplified P&ID of the continuous flow ALD reactor system F120 by ASM Microchemistry Ltd. (Suntola, 1992). The vector of set points for the measured equipment-
scale process operating parameters is: Yr ¼ ½Q_ N2 ,p,T, Q_ ZnðC2 H5 Þ2 , Q_ H2 O , Dt ZnðC2 H5 Þ2 , Dt H2 O , Dt N2 y .

film thickness profile on a discrete set of sampling positions
on the substrate. The focus was on understanding the impact
of process operating parameters on the spatial evolution of
the substrate film thickness profile.
On the basis of the derived mathematical model and the experi-
mental measurement data, a nonlinear parameter estimation
problem was formulated in the second article of this series
(Holmqvist et al., in press) to determine reliable estimates of
the kinetic parameters involved in the ALD gas–surface reaction
mechanism governing ZnO film growth.
The reminder of this paper is organized as follows. Section 2
presents the continuous cross-flow ALD reactor system and the
measured process operation parameters. Section 3 concerns the
derivation of the mathematical ALD reactor model. In Section 4
the experimental investigation is described, while the subsequent
section outlines the modelling environment. Finally, concluding
remarks are drawn in Section 6.
2. Overview of the continuous flow ALD reactor system
Most ALD studies have been carried out in low-pressure, flow-
type reactors where a continuous flow of inert carrier gas is
introduced over the substrate (Elers et al., 2006). There are
various types of ALD reactor systems (Granneman et al., 2007),
however, in this study, the continuous cross-flow reactor system
F-120 by ASM Microchemistry Ltd. (Suntola, 1992) was consid-
ered. The simplified process and instrumentation diagram (P&ID)
is depicted in Fig. 3. The whole reactor chamber (RC) and
precursor transport system is placed in a 1.2 m long quartz glass
tube with a diameter of 1:2  101 m. This tube is divided into
264 A. Holmqvist et al. / Chemical Engineering Science 81 (2012) 260–272
separate heating zones that are externally heated by an induction
heating setup; where a solid state RF power supply sends an AC
current through a copper coil; controlled by a PID controller to
generate a homogeneous operating temperature, T. To further
prevent temperature induced fluctuations in the reaction cham-
ber, all gases pass through a preheating zone before entering the
reaction chamber. The reactor system utilizes a continuous
viscous flow of ultra-high-purity nitrogen carrier gas, Q_ N2 , sup-
plied via a mass flow controller (MFC). After the nitrogen flow
passed through the reaction chamber, the flow was pumped by a
rotary vane vacuum pump and the operating pressure, p, in the
reactor system was monitored by a pressure transducer mounted
upstream the exhaust pump. Furthermore, the reaction chamber
was equipped with two 5:0  102  5:0  102 m substrates
positioned inside a 2:0  103  5:0  102 m flow channel. As a
consequence of the relatively small characteristic length scale of
the narrow flow channel, the linear flow rate over the substrate
surface is high, and the precursor pulse dispersion is thus very
small, and residence time very short (George, 2010).
The highly volatile precursors (H2O and Zn(C2H5)2) are stored
in reservoirs (maintained at room temperature) outside the
quartz glass tube. Regulating valves on the precursor gas lines
were used to control the mass flow of the doses, Q_ H2 O and
Q_ ZnðC2 H5 Þ2 , into the reactor chamber. Prior to the reaction chamber,
a three way gas switching mechanism (GSM), represented as two
on–off diaphragm valves and one mixing valve, controlled the
precursor pulse exposure times, Dt H2 O and Dt ZnðC2 H5 Þ2 , and the
subsequent nitrogen purge time, Dt N2 . It is noteworthy that
the GSM is an inherent physical structure of the reactor chamber
inlet and not a valve arrangement as depicted in Fig. 3 for
clarification, see e.g. Baunemann (2006) for a comprehensive
description of the reaction chamber design. The reactive precur-
sors are admitted separately in an alternate fashion and the
continuous inert gas flow transports travelling waves of precur-
sors laterally across the active surface of the substrates in the
reactor chamber.
3. Mechanistic modelling of the continuous flow ALD reactor
system
Modelling of an ALD continuous flow reactor system may be
performed in different levels of detail and assumptions, see e.g.
Aarik and Siimon (1994), Yanguas-Gil and Elam (2012) and
Ylilammi (1995), and the chosen level depends on the predeter-
mined modelling goal, as defined by Hangos and Cameron (2001),
and model application. Reactor-scale effects propagate to the
atomic scale and, to accommodate this relation, a two-dimen-
sional model; where the narrow flow channel inside the reactor
chamber in the ALD continuous flow reactor system (see Fig. 3)
constitutes the computational domain O (see Fig. 4), based on
computational fluid dynamics, incorporating the ALD heteroge-
neous surface reaction mechanism, was considered. This implies
that no finer modelling level representing the spatial evolution of
the substrate film thickness profile than mass and momentum
conservation equations incorporating reaction rate equations are
Fig. 4. Sketch of the computational domain, O, with partitioned boundary G ¼ Gin [ Gwall [ Gsub [ Gsym [ Gout . z A ½0,9Gsub 9 represents the substrate boundary Gsub local
coordinate variable. The quantities pentr and Lentr were used in Eq. (7) considering the boundary condition at the inlet, prescribing a laminar velocity profile. The dimensions
are as follows: 9Gsub 9 ¼ 5:0  102 m, 9Gin 9 ¼ 9Gout 9 ¼ 2:0  103 m, 9Gwall 9 ¼ 2:5  103 m and Lentr ¼ 1:0  103 m.
considered, which is appropriate for analysis, design and optimi-
zation of ALD rectors as noted in Elliott (2007).
3.1. Formulation of underlying model assumptions
In order to simplify the overall modelling framework and reduce
the computational requirements, several assumptions have been
made without sacrificing the accuracy and applicability of the
model. Some of these are derived from the operation of the ALD
reactor system (see Section 2) and others are theory related. The
assumptions derived from the operation of the reactor system are:
(i) In the conventional pressure-driven flow system in the con-
tinuous flow ALD reactor (cf. Fig. 3), a mass flow controller
(located upstream of the reactor) supplies the carrier gas at a
constant mass flow rate, and a vacuum pump (located down-
stream of the reactor) maintains the flow through the system
and establishes the operating pressure. Hence, the pressure
field inside the reactor chamber is inhomogeneous and the gas
density can no longer be considered constant. The chemical
reactions and precursor pulsing sequence also contribute to
density variations. Therefore, it is beneficial to consider com-
pressible fluid dynamics in order to achieve continuity,
although the Mach number (Ma) is below unity.
(ii) It should be noted that the hot-wall flow-type reactor
provides a reasonably isothermal environment, in which
the fixed-bed quartz chamber and the gas delivery lines are
inductively heated. Hence, it was assumed that the tempera-
ture field within the reactor was homogeneous.
(iii) Under the operating conditions normally encountered in the
ALD reactor, the continuum hypothesis is assumed to be
valid, thereby utilizing computational fluid dynamics of the
compressible viscous fluid in the laminar region, since the
range of Reynolds (Re) numbers is significant below the value
at the onset of turbulence.
The theory related assumptions are:
(iv) The system is assumed to be thermodynamically ideal,
behaving in accordance with the ideal gas law, thereby
having the necessary pressure dependence on the fluid
density.
(v) The computational domain considered is the narrow flow
channel in the reactor chamber (cf. Fig. 4), and was simplified
using a spatial symmetry plane, thereby reducing the number
of degrees of freedom, and consequently the computational
time and memory requirement.
(vi) Only immobile surface species were considered, i.e. surface
diffusion is neglected.
(vii) The same maximum surface site density is available for the
deposition of all surface species, and the corresponding
maximum amount of adsorbed species is assumed to be a
monolayer (as in chemisorption).
(viii) All adsorption sites on the surface are assumed to be
identical, and neighboring adsorbed species are assumed
not to interact with each other.
 A. Holmqvist et al. / Chemical Engineering Science 81 (2012) 260–272 265

3.2. Governing equations of the ALD reactor sub-model Sa , in the convection–diffusion equations (Eq. (4)) since no
reaction is expected in the gas phase.
The mathematical model of the continuous cross-flow ALD
reactor chamber is based on fully coupled equations for the 3.2.1. Boundary conditions
conservation of mass, momentum, individual gas phases and In the following, the essential and natural boundary conditions
surface species, together with constitutive relations for momen- for the partitioned boundary G ¼ Gin [ Gwall [ Gsub [ Gsym [ Gout
tum and mass fluxes, defined on the two-dimensional spatial of the domain O (see Fig. 4) are derived. Gh is the subset of the
domain O (cf. Fig. 4) with spatial coordinates z ¼ ½z1 ,z2 . To total boundary, G ¼ Gg [ Gh , where Neumann-type boundary
capture the detailed process dynamics at the level of the ALD conditions are prescribed and Gg is the part of the boundary on
pulse sequence (cf. Section 1.2), transient conditions prevail for all which Dirichlet boundary conditions are applied.
governing equations in the temporal domain t A ½t 0 ,t end . The In order to prescribe an inlet velocity profile, the Navier–
characteristic time-scales for ALD precursor chemisorption on Stokes equation is projected onto the boundary (COMSOL AB,
flat substrates and precursor mass balances corresponding to 2008b). In mathematical terms this becomes:
the macroscopic-scale transport, respectively, are presented in
Lentr rt  ðpdm½rt v þðrt vÞy 23ðrt  vÞdÞ ¼ npentr
Granneman et al. (2007).
Based on the modelling assumptions in Section 3.1, the rt  v ¼ 0 at Gin  Gg ð7Þ
Navier–Stokes equations governing viscous compressible fluid where rt is the gradient in the direction tangential to the
flow are boundary and n is the outward unit vector normal to the
@rv boundary. The applied condition corresponds to the situation
¼ ðr  rvvÞðr  pÞ þf in O for t A ½t 0 ,t end  ð1Þ presented in Fig. 4, where a fictitious entrance region of length
@t
Lentr is assumed to be attached to the inlet of the computational
and assuming Newtonian fluid, the molecular momentum flux
domain O. The pressure at the end of the entrance region, pentr , is
tensor, p, is defined by
determined such that the desired inlet velocity or mass flow is
p ¼ pdm½rv þ ðrvÞy 23ðr  vÞd ð2Þ obtained. The associated integral mean value of the velocity
profile at Gin is given by
where r,v,f, p, d and m are the density, velocity, body force, Z Z
pressure, unity tensor and dynamic viscosity, respectively. The 1 1 1 X
/vS9Gin ¼ v@G ¼ r Q_ a @G ð8Þ
compressibility imposed on the conservation of mass yields the 9Gin 9 Gin 9Gin 9 Gin rAGin a ¼ 1 STP, a
continuity equation:
where Q_ a is the volumetric flow rate at STP of the individual
@r gaseous species a. Furthermore, the total inlet mass flux of the
¼ ðr  rvÞ in O for t A ½t 0 ,t end  ð3Þ
@t non-overlapping alternate injection of the ath species can be
Hence, the transport of the ath species, a A f1,2, . . . ,Na 1g and Na expressed as
is the total number of gaseous species, is governed by the 1
conservative formulation of the convection–diffusion equation: n  ðroa v þja Þ ¼ r Q_ Pa ðt, Dt a Þ at Gin  Gh ð9Þ
AGin STP, a a
@roa
¼ ðr  roa vÞðr  ja Þ þ Sa in O for t A ½t 0 ,t end  ð4Þ which was implemented by taking each of the inlet mass fractions
@t
oa 9Gin fixed and prohibiting species diffusion through the inlet
where oa is the mass fraction, Sa is the source and ja is the total boundary Gin :
diffusive mass flux, relative to the mass-averaged velocity field v
of the gas mixture, of the ath species. The constitutive relation for rSTP, a Q_ a Pa ðt, Dta Þ
oa 9Gin ¼ P _
at Gin  Gg
the mass flux can be obtained from either Fick’s law of binary a ¼ 1 rSTP, a Q a Pa ðt, Dt a Þ
diffusion (Eq. (5a)) or the generalization of Fick’s law to include n  ja ¼ 0 at Gin  Gh ð10Þ
multicomponent diffusion (Eq. (5b)):
Here, the shift in arguments Pa ðt, Dt a Þ A ½0,1 was implemented
8
< rDab roa ðaÞ through the superposition of time-dependent smoothed Heavi-
P
ja ¼ roa D ab ðrcb þðcb ob Þr ln pÞ ðbÞ ð5Þ side functions with a continuous second derivative without
: b¼1 overshoot (COMSOL AB, 2008a), and where Dt a is the pulse
duration of the ath gaseous species.
where cb is the molar fraction of the species b. The symmetric,
The no-slip boundary condition on Gwall eliminates all compo-
multicomponent Fick diffusivities (Dab ¼ Dba ), as outlined by
nents of the velocity vector and the total mass flux is prescribed
Curtiss and Bird (1999), are related to the Maxwell–Stefan
to zero:
diffusivities Dab (Wesselingh and Krishna, 2000) through the
relation: v¼0 at Gwall  Gg ð11Þ
P
ca cb g a a Dag ðadj Ba Þgb n  ðroa v þ ja Þ ¼ 0 at Gwall  Gh ð12Þ
Dab ¼  P ð6Þ
oa ob g a a ðadj Ba Þgb
Furthermore, Gout is a free boundary where the normal stress is
in which a, b A f1,2, . . . ,N a g, ðBa Þbg ¼ Dbg Dag and adj Ba is the prescribed to zero together with a Dirichlet condition on the
matrix adjoint to Ba . Furthermore, for multicomponent diffusion pressure, and the diffusive mass is prescribed to zero:
in gases at low density, to a very good approximation, the Dab
ðm½rv þ ðrvÞy 23ðr  vÞdÞn ¼ 0 at Gout  Gh ð13Þ
may be replaced by the binary diffusivities Dab (Bird et al., 1960).
The transport coefficients, Dab and ma , were determined from the p ¼ /pS9Gout at Gout  Gg
Chapman–Enskog kinetic theory of dilute gases (Hirschfelder
n  ja ¼ 0 at Gout  Gh ð14Þ
et al., 1964; Reid et al., 1988) and the viscosity for the multi-
component mixture of gases, m, was determined from the semi- The integral mean value of the pressure at the inlet, /pS9G , was
in
empirical mixing formula in Wilke (1950). Furthermore, the body determined in an iterative manner for a specific mass flow of the
force term, f, in the full Navier–Stokes equations (Eq. (1)) is carrier gas and process temperature, using fsolve in the Optimiza-
omitted as the force of gravity is negligible, as is the source term, tion Toolbox TM for MATLABs (The MathWorks, Inc, 2010b), until
266 A. Holmqvist et al. / Chemical Engineering Science 81 (2012) 260–272
the governed pressure at the outlet, /pS9Gout , was consistent with
the applied reference value. This procedure was performed prior
to the simulation of the gaseous precursor mass balances (Eq. (4))
and determines the initial conditions for the velocity and pressure
fields in O. Finally, the boundary condition on Gsym , according to
Eq. (11) is valid, and no penetration or vanishing shear stress
conditions are prescribed:
t  ðpdm½rv þ ðrvÞy 23ðr  vÞdÞn ¼ 0 at Gsym  Gh
nv¼0 at Gsym  Gg
where t is the unit vector tangential to the boundary.
3.2.2. Coupling reactor gas transport to heterogeneous surface
reactions
Owing to the heterogeneous surface reactions, see Section 3.3,
there will be a net mass consumption or production of gaseous
species at the substrate surface. As a consequence of the net mass
flux between the gas bulk and the surface, a velocity, the so-called
Stefan velocity (Kuijlaars et al., 1995), is induced in the normal
direction and, assuming that the no-slip condition holds, the
tangential component is zero:
1X X R T T ref,i
nv¼ Ma xa,i ri
ra¼1 i¼1
tv¼0 at Gsub  Gg
where ri is the net molar reaction rate of the ith elementary
surface reaction, and xa,i the stoichiometric coefficient corre-
sponding to the ath species. The resulting boundary condition
for the species-continuity equations at the gas–surface interface,
Gsub , yields
X species must be unity at all times, i.e. k ¼ 1 yk ¼ 1. No inhibition is
n  ðroa v þja Þ ¼ M a xa,i ri at Gsub  Gh ð17Þ
i¼1
which states that the total gas-phase mass flux of the ath species
normal to the surface is balanced by the net consumption or
production of mass per unit area.
3.3. Governing equations of the heterogeneous surface reaction sub-
model
The characteristic of the surface reaction, i.e. the probability
that the reaction proceeds through the formation of adsorbed
species, is dependent on the properties of the exposed adsorbent
surface. During the initial stage of ALD, the pre-deposited sub-
strate surface is gradually converted into a film as the deposition
process proceeds. Therefore, there is a transient region, which
leads to the nonlinear dependence of film thickness increment on
the number of deposition cycles (Alam and Green, 2003; Lim
et al., 2000a; Puurunen and Vandervorst, 2004). Subsequently,
when the substrate is fully covered by the ALD-grown film,
the effect of the substrate is lost and the thickness increment
becomes linearly dependent on the number of deposition cycles.
According to Masel (1996) there are three generic types of
surface reactions: those that follow the Langmuir–Hinshelwood
mechanism (Park et al., 2000), those that follow the Eley–Rideal
mechanisms (Lim et al., 2001, 2000b) and the precursor mechan-
isms. In the present study, the binary reaction (in the case of
conventional CVD) was separated into two half-reactions, and
assumed to follow the Eley–Rideal mechanism, where the surface
reactions are considered to proceed without the formation of an
intermediate adsorption complex. Additional assumptions under-
lying the derivation of the general surface reaction model are
presented in Section 3.1. Based on these assumptions, the general
surface reaction model, describing the spatial and temporal frac-
tional surface coverage, referred to as chemisorption coverage, is
governed by
X
@Lyk
¼ xk,i r i at Gsub for t A ½t 0 ,t end  ð18Þ
@t i¼1
and subject to insulating boundary conditions, cf. Eq. (14) with
canceled convection and diffusion terms. Here, yk is the fractional
surface coverage of the kth surface species, k A f1,2, . . . ,Nk g and N k
is the total number of surface species, and L is the maximum molar
concentration of surface sites per unit area available for deposition.
ð15Þ
The kinetic mechanism used gives the general reversible formalism
of the ith surface reaction rate:
!nads,i
X
r i ¼ kads,i pa 9G L Ly‘ kdes,i ðLyk Þndes,i ð19Þ
sub
‘¼1
where nads,i is the adsorption order related to the interaction
between adsorbents, and ndes,i is the corresponding desorption
order. The temperature dependency of adsorption, kads,i , and deso-
rption, kdes,i , rate constants is governed by reparameterization of the
Arrhenius equation (Schwaab et al., 2008; Schwaab and Pinto, 2007,
2008) by introducing a reference temperature, T ref,i , in the form
  
E 1 1
ki ¼ kT ref,i ,i exp  i  ð20Þ
where kT ref,i ,i ¼ Ai expðEi ½RT ref,i 1 Þ is the specific reaction rate at
ð16Þ T ref,i , Ai is the frequency factor, and Ei is the activation energy of the
ith elementary reaction. The subscript ‘ in Eq. (19) represents all kth
surface species with which the ath gaseous species cannot undergo
P
a reaction, hence ð1 ‘ ¼ 1 y‘ Þ defines the fractional surface cover-
age available for reaction. Eq. (19) imposes the restriction that the
finite sum of the fractional surface coverage of the kth surface
P
explicitly imposed on the surface reaction rate to account for steric
hindrance (Puurunen, 2003; Ylilammi, 1996), however, these effects
are still considered through the reversible formalism. Hence, when
the kth fractional surface coverage approaches unity, the desorption
effects become more significant, and thus limit the net reaction rate
(Wei et al., 1994). Consequently, growth behavior when the max-
imum surface site density is not covered, even at saturated pre-
cursor dosage conditions, is taken into account.
The continuity equation for the fractional surface coverage of
surface species (Eq. (18)) includes the partial pressure of gas-phase
species, pa 9G , at the position, z A Gsub , on the substrate surface.
sub
Hence, the continuity equation for the gas phase and the substrate
surface species, respectively, are coupled through the surface reac-
tions via the boundary condition (Eq. (17)), at the substrate surface.
In general, it is impossible to find a closed-form solution, yk , to the
partial differential equation (PDE), see Eq. (18), because the impin-
gement flux of precursors, equalized by the source term in the same
equation, is not spatially constant throughout the substrate, as
emphasized by Gobbert et al. (2002a).
3.4. Governing equations of the film growth sub-model
The mass increment per unit area and the time from the
chemisorption of the precursor at position z A Gsub on the sub-
strate surface is governed by
@ms X
¼ xk,i ri DMi at Gsub for t A ½t0 ,tend  ð21Þ
@t i¼1
Eq. (21) is subject to insulating boundary conditions, cf. Eq. (14)
with canceled convection and diffusion terms and where DM i is
the difference in molecular weight of the outermost surface
species governed by the ith elementary reaction. The correspon-
dence between mass increment per unit surface area and the
equivalent thickness of the layer is ms ¼ rs hs , where rs is the bulk
 A. Holmqvist et al. / Chemical Engineering Science 81 (2012) 260–272
density of the film. Additionally, the mean mass deposited per
unit area at a certain time /ms S is governed by
Z coverage of hydroxyl groups, forming oxygen bridges or unsatu-
@/ms S 1 @ms
¼ @Gsub at Gsub for t A ½t 0 ,t end  ð22Þ
@t 9Gsub 9 Gsub @t
which is an essential scalar quantity for reproduction of in situ
QCM diagnostics.
3.5. Elementary surface reaction mechanism
The model-based methodology presented in Sections 3.2–3.4
was applied to a case study on sequential surface chemical
reactions for the controlled deposition of ZnO films (Özgur
et al., 2005; Triboulet and Perriére, 2003) from Zn(C2H5)2 and
H2O (Elam et al., 2002b; Ferguson et al., 2005; Ott and Chang,
1999; Yousfi et al., 2000). In the case of conventional CVD of ZnO
films using these precursors, the binary reaction is
ZnðC2 H5 Þ2 þ H2 O!ZnO þ 2C2 H6 ð23Þ
During ALD of thin oxide films it is generally accepted that surface
hydroxyl groups remain as intermediate species after exposure to
water, and that these react with the incoming metal precursors
during the subsequent metal precursor sequence (Matero et al.,
2000). A reduced chemistry model that includes only the primary
sequential elementary surface reaction mechanism was devel-
oped to obtain reliable values of the required kinetic parameters,
and to provide a predictive model of the ALD process. The two
sequential elementary surface reactions for a normally hydro-
xylated surface were thus defined as
ð1Þ nðOHÞ/sSþ ZnðC2 H5 Þ2 /gS
!ðOÞn ZnðC2 H5 Þ2n /sSþ nC2 H6 /gS ð24aÞ
ð2Þ ðOÞn ZnðC2 H5 Þ2n /sSþ ð2nÞH2 O/gS
!ðOÞn ZnðOHÞ2n /sSþ ð2nÞC2 H6 /gS ð24bÞ
in which /sS and /gS denote surface and gaseous species,
respectively, and n is the average number of hydroxyl groups
reacting with each Zn(C2H5)2 molecule. Eqs. (24a) and (24b)
represent irreversible forward surface reactions, where deso-
rption (or the reverse reaction) has been neglected in order to
reduce the number of unknown kinetic reaction parameters.
Therefore, the contribution corresponding to desorption in Eq.
(19) was omitted when deriving the mathematical formulation of
the surface reaction rate. However, Rahtu and Ritala (2002) have
shown that this assumption is not generally valid for all adsorp-
tive precursors.
The sequential elementary surface reactions were defined to
allow a variable number of reacting hydroxyl groups (Rahtu et al.,
2001). In the simplest case, for n ¼ 1, QCM studies have shown
that the mass increment during the alternate injection of the
precursors was not consistent with the proposed sequential
elementary surface reactions (Yousfi et al., 2000). The quotient
of the difference in molecular weight of the outermost surface
species is governed by Eqs. (24a) and (24b), i.e. DM2 DM 11 , and
gives the ratio of mass change occurring during the half-reactions.
This quantity was extracted from QCM pulse shapes given by
Elam and George (2003) and determined to be n ¼ 1:37.
However, the reaction mechanism defined in Eqs. (24a) and
(24b) cannot explain the sharp decrease in mass increment per
cycle at elevated temperatures, which was observed experimen-
tally at constant adsorption energy, Eads . This phenomenon was
assumed to be a consequence of the gradual decrease in the
density of the surface hydroxyl groups, in accordance with
Deminsky et al. (2004), Matero et al. (2000), and Rahtu et al.
(2001), through the recombination reaction:
ð3Þ 2ðOHÞ/sS!ðOÞ/sSþ H2 O/gS ð24cÞ
267
In this process, adjacent surface hydroxyl groups react, which is a
second-order reaction with respect to the fractional surface
rated bonds on the surface. This becomes a limiting factor with
respect to the rate of film growth under conditions of extensive
dehydroxylation. The hydroxyl groups may be reformed on the
oxide surface during exposure to water by rehydroxylation
through the reversed reaction of Eq. (24c):
ð4Þ ðOÞ/sSþ H2 O/gS!2ðOHÞ/sS ð24dÞ
which is of first order with respect to the fractional surface
coverage of oxygen groups. In mathematical terms, Eq. (24c)
was interpreted as a desorption reaction, and consequently, only
the contribution corresponding to desorption in Eq. (19) was
considered. In contrast, only the adsorption contribution in
Eq. (19) was used when considering Eq. (24d).
3.5.1. Kinetic parameters for the elementary surface reactions
In this study, ex situ film thickness measurements were
performed (see Section 4), and thus no reliable information
regarding the transient mass increment occurring during the
half-reactions could be obtained. Therefore, the average number
of reacting hydroxyl groups was set to the value presented
by Elam and George (2003). The stoichiometric coefficients xi ,
adsorption nads,i and desorption ndes,i order associated with the ith
elementary surface reaction are defined according to Eqs. (18),
(19) and (24). Consequently, the remaining kinetic parameters,
including the maximum molar concentration of surface sites, the
specific reaction rate at T ref,i and the associated activation energy
for the ith elementary surface reaction, constitute calibration
parameter vector:
b ¼ ½L,kT ref,i ,i ,Ei y ð25Þ
where i A f1,2, . . . ,4g, and 8i a3 takes adsorption into account, cf.
Eq. (19), and where b A RNb is the N b -dimensional parameter
space.
4. Experimental investigation
4.1. Experimental setup
The controlled deposition of ZnO films on soda lime glass
(SLG), from Zn(C2H5)2 and H2O, was carried out in the continuous
cross-flow reactor system described in Section 2. This system
setup enables measurement of all necessary input signals, control
the appropriate variables and adjust several system parameters
(see Fig. 3). In the current study the operation of the ALD reactor
has been tested under a wide range of conditions, and the focus
was on understanding the impact of process operating para-
meters on the spatial evolution of the substrate film thickness
profile, see e.g. Cleveland et al. (2012) and Henn-Lecordier et al.
(2011).
4.2. Experimental design
The operating conditions used in this investigation are listed in
Table 1. The experimental design was intended to address the
interdependence of the pulse duration of the adsorptive precur-
sors, Dt ZnðC2 H5 Þ2 A ½1:0,18:0  101 s and Dt H2 O A ½1:0,4:0  101 s,
and the temperature, T A ½1:0,2:0  102 1C, on the spatial depen-
dence of the film deposition rate. Using this approach, parameter
estimation can be carried out over a wide region defining the
model’s region of validity, including the ALD processing window
(Yousfi et al., 2000) and considers both saturated and non-
saturated (Park et al., 2000) deposition.
268 A. Holmqvist et al. / Chemical Engineering Science 81 (2012) 260–272

Table 1
Outline of the experimental design. The observed system response, y^ (Å cycle  1), contains ex situ film thickness measurements by XRF at the sampling positions
f^ ¼ ½16 , 36 , 56  9Gsub 9 (m) on the substrate. The ALD pulse sequence considered for growth of ZnO was the following ðDtZnðC2 H5 Þ2 , DtN2 , DtH2 O , DtN2 Þ including a nitrogen purge
DtN2 ¼ 4:0  101 s between the non-overlapping alternate injections of the precursors for all cases E. All experiments were performed with the process operating
parameters: /pS9Gout ¼ 2:0  102 Pa, ½Q_ ZnðC2 H5 Þ2 , Q_ H2 O, Q_ N  ¼ ½0:11,0:16,5:0  102 sccm [standard cubic centimeters per minute at STP].
2

E DtZnðC2 H5 Þ2  101 ðsÞ DtH2 O101 ðsÞ T  102 ^ z^ ¼ ð1=6Þ9G

y9 ^ z^ ¼ ð3=6Þ9G
y9 ^ z^ ¼ ð5=6Þ9G
y9 UF y^
sub 9 sub 9 sub 9
(1C) (%)
(Å cycle  1) (Å cycle  1) (Å cycle  1)

1 2.0 4.0 1.0 0.931 0.923 0.860 97.1

2a 4.0 4.0 1.0 1.12 1.06 0.941 94.7
3 6.0 4.0 1.0 1.30 1.14 1.08 93.8
4 12.0 4.0 1.0 1.67b 1.37 1.18 90.1
5 18.0 4.0 1.0 2.23b 1.54 1.39 94.7
6 6.0 1.0 1.0 1.05 0.893 0.843 92.3
7 6.0 2.0 1.0 1.17 1.05 0.916 93.7
8 6.0 4.0 1.0 1.30 1.14 1.08 93.8

9 1.0 4.0 1.5 1.84 1.72 1.64 96.8

10 2.0 4.0 1.5 2.04 1.84 1.83 95.7
11a 4.0 4.0 1.5 2.13 2.05 2.05 98.4
12 6.0 4.0 1.5 2.60b 2.15 2.07 98.3
13 12.0 4.0 1.5 2.62b 2.22 2.25 99.0
14 6.0 1.0 1.5 2.06 1.97 1.90 97.8
15 6.0 2.0 1.5 2.28 2.05 2.09 95.7
16 6.0 4.0 1.5 2.60b 2.15 2.07 98.4

17 1.0 4.0 2.0 1.83 1.73 1.74 97.7

18 2.0 4.0 2.0 1.88 1.76 1.80 97.5
19 4.0 4.0 2.0 1.95 1.82 1.76 96.8
20 6.0 4.0 2.0 1.95 1.94 1.89 98.9
21 12.0 4.0 2.0 1.97 1.93 1.91 99.1
22 6.0 1.0 2.0 1.86 1.83 1.80 99.0
23a 6.0 2.0 2.0 1.88 1.84 1.84 99.1
24 6.0 4.0 2.0 1.95 1.94 1.89 99.0

a
Experimental validation set.
b
Detected experimental outlier.

A general characteristic feature of cross-flow reactors is that

the trailing edge of the substrate is exposed to more depleted
reacting precursor flow than the leading edge, and the film
deposition rate is consequently not uniform across the substrate
(Granneman et al., 2007). For this reason, every Eth calibration and
validation data set, y^ E 9f^ (Å cycle  1), listed in Table 1 contains film
thickness measurements at three spatially equidistant sampling
positions, f^ ¼ ½16 , 36 , 56  9Gsub 9 (m), on the substrate as depicted in
Fig. 5. Thus, it is convenient to classify the experiments on the
basis of the film uniformity across the substrate. A uniformity
factor (Cheng and Hsiao, 2008), UF, that relates the absolute
deviation from the mean film height, is defined as
Z Z 1
UF ¼ 1 9hs ðzÞh s ðzÞ9@z hs ðzÞ@z ð26Þ
Gsub Gsub

where hs ðzÞ is the normalized film height, h s ðzÞ is the correspond-

ing mean value, and z A ½0,9Gsub 9 is the substrate boundary Gsub
local coordinate variable (see Fig. 4). The uniformity factor for
every Eth experimental data set determined from Eq. (26) is listed
in Table 1 and fall within the range UF y^ A ½90:1,99:1%.
Fig. 5. Spatial film thickness profile as a function of the substrate local coordinate
variable z A ½0,9Gsub 9. (  ) Representative model generated film thickness hs ðzÞ
4.3. Instrumentation and data preprocessing
(Å cycle  1); (– –) Model generated mean film thickness h s ðzÞ (Å cycle  1); ðJÞ
Model generated film thickness hs ðzÞ9f^ (Å cycle  1) at the sampling positions
The instrumentation used for film characterization and the
data preprocessing methodology are identical to that of Törndahl f^ ¼ ½16 , 36 , 56  9Gsub 9 (m) where the experimental measurements were conducted.
The colored area represents the absolute deviation from the mean film hight
et al. (2007); the reader is referred to that paper for further R
details. The ex situ thickness measurements of the ZnO films Gsub 9hs ðzÞh s ðzÞ9@G (cf. Eq. (26)).

deposited on SLG substrates were performed using X-ray reflec-

tivity (XRR) (Siemens D5000 X-ray powder diffractometer,
equipped with a slit system) at the centre sampling position
(z^ ¼ 36 9Gsub 9 (m)) on the substrate. In accordance with Burton
et al. (2009), the thickness was calibrated independently from the
experimental XRR data in the range of N Dt A ½1:25,5:0  102
complete ALD cycles ðDt ¼ Dt ZnðC2 H5 Þ2 þ2Dt N2 þ Dt H2 O Þ using the
WinGixa software package (Leenaers and de Boer, 1998). The
film thickness, y~ E 9z^ ¼ ð3=6Þ9G 9 (Å), obtained from the fits to XRR
sub
 A. Holmqvist et al. / Chemical Engineering Science 81 (2012) 260–272
Fig. 6. Preprocessing of experimental XRR data for various numbers of ZnO
ALD cycles N Dt ¼ ½1:25,2:5,3:75,5:0  102 cycle at T ¼ ½1:0,1:5,2:0  102 1C on
SLG substrates. XRR film thickness data, y~ E 9z^ ¼ ð3=6Þ9G 9 Å, at the sampling position
sub
z^ ¼ 36 9Gsub 9 (m) and at: ðJÞ T ¼ 1:0  102 1C; (&) T ¼ 1:5  102 1C; ð,Þ
T ¼ 2:0  102 1C; (–) linear fit, dy~ E 9z^ ¼ ð3=6Þ9G ðdNDt Þ1 (Å cycle  1), to XRR film
sub 9
thickness data. The process operating parameters are analogous to those defined
in Table 1 and ½Dt ZnðC2 H5 Þ2 , Dt N2 , Dt H2 O , Dt N2  ¼ ½6:0,4:0,4:0,4:0  101 s.
data as a function NDt is depicted in Fig. 6. The dependence of
y~ E 9z^ ¼ 36 9Gsub 9 on NDt is consistent with constant growth per cycle
(GPC) of dy~ E 9z^ ¼ ð3=6Þ9G ðdN Dt Þ1 ¼ ½1:2,2:1,1:9 (Å cycle  1) at
sub 9
T ¼ ½1:0,1:5,2:0  102 1C, respectively. It is noteworthy that only
this quasi-steady state growth regime is considered in this
experimental investigation and, consequently, elementary surface
reactions of the initial regime (Puurunen, 2004), in which
2 2
d y~ E 9z^ ¼ ð3=6Þ9G 9 ðdN Dt Þ1 a0, were not developed in Section 3.5.
sub
The relative thickness or amount of deposited material per
unit area at the sampling positions f^ ¼ ½16 , 36 , 56  9Gsub 9 (m) on the
substrate was measured by energy dispersive X-ray fluorescence
spectrometry (XRF) (Spectro X-Lab 2000, using Mo-target for Zn
excitation). The absolute thickness determination using XRF was
obtained by integration of the net peak intensity for the selected
element of the spectrum, and the extracted GPC at z^ ¼ 36 9Gsub 9
(m) of the XRR analysis served as the required calibration data.
The sampled spatially dependent film thickness profiles, for the
operating conditions specified in Section 4.2, are listed in Table 1
and constitutes the observed system response, y, ^ in the model
calibration and validation procedure (see Holmqvist et al., in press).
The experimental measurement data, y^ E 9z^ ¼ ð1=6Þ9G 9 and
sub
E A f4,5,12,13,16g, identified as outliers are denoted by super-
scripts in Table 1. It is noteworthy that the detected outliers were
all belonging to the sampling position closest to the leading
edge of the substrate (cf. Fig. 5), and associated with analogous
deposition conditions; including T r 150 1C and long precursor
pulse lengths. Under such conditions, the precursor coverage by
adsorption on internal surfaces of the reactor chamber (main-
tained at the substrate temperature) may be enhanced by higher
precursor exposures. At the same time, the rate of precursor
desorption from the same surfaces decreased with decreasing
deposition temperature (Groner et al., 2004). Thus, the coherent
phenomena will ultimately put restrictions on significantly longer
purge periods. However, in this study, the N2 purge times were
269
maintained constant at Dt N2 ¼ 4:0  101 s for consistency. It is
therefore plausible that the outliers on the leading edge of the
substrates were caused by insufficient N2 purge (Jur and Parsons,
2011), resulting in simultaneous presence of both precursors in
the gas phase, which enables regular CVD growth with a higher
growth rate than in true ALD (Elers et al., 2006).
5. Modelling environment
s
COMSOL Multiphysics (COMSOL AB, 2008b), a finite element
analysis, solver and simulation software package for encoding of
complex and coupled physical systems aimed at simulation and
offers an extensive interface to MATLAB s (The MathWorks, Inc,
2010a) and its toolboxes is used for reactor modelling. The
programming language also allows for entering coupled systems
of PDEs in either strong form or weak form. To solve transient
s
PDEs, COMSOL Multiphysics employs the method of lines
(Davis, 1984; Schiesser, 1991) which proceeds by first discretizing
the spatial domain O into finite elements (Zienkiewicz and Taylor,
2000a,b). The associated system of DAEs is solved by the IDA
solver in the SUNDIALS package (Hindmarsh et al., 2005). The DAE
solver applies a variable-order variable-step-size backward dif-
ferentiation formulas and solves the system of nonlinear equa-
tions at each time step, using a Newton LU solver, which in turn,
utilizes the UMFPACK library.
The derived mathematical model of complete two-way coupling
of the governing equations will be solved numerous times in the
calibration procedure, see Holmqvist et al., (in press), and it is
therefore important to improve the computational efficiency. In this
context, the underlying flow problem (Eqs. (1) and (3)) was
stabilized by the Galerkin least-squares scheme (Hauke, 2001;
Hauke and Hughes, 1994), which circumvents the Ladyzhenskaya–
Babuška–Brezzi condition, such that equal order velocity and
pressure elements can be used to reduce the computational cost.
In order to overcome the numerical instabilities arising from do-
minant convection times in the convection–diffusion equations
(Eq. (4)), and to avoid using an extremely fine mesh, the Streamline
Upwind Petrov–Galerkin method (Codina, 1998) was added to the
basic Galerkin formulation. A mesh independence test was carried
out to determine the appropriate mesh size. Approximately 1:5 
103 elements were needed to obtain grid-independent solutions
with second-order Lagrange elements for all fields except the pres-
sure and the velocity field, for which first-order elements sufficed.
6. Concluding remarks
In this paper, a novel mathematical model that mechanistically
describes the complex interactions between the gas-phase fluid
dynamics, the mass transport of individual species, and the hetero-
geneous surface reaction mechanism in a continuous cross-flow ALD
reactor was derived. The overall objective of the model, oriented
towards optimization and control, was to accurately predict the
dynamic response of the substrate spatially dependent film thick-
ness profile to the variations of all the measured equipment-scale
process operating parameters. The general formalism of the math-
ematical model is valid for all spatial dimensions applied to arbitrary
geometries, for an arbitrary number of gaseous and surface coverage
species, and for any process chemistry, thereby providing a frame-
work for model-based process design and scalability.
A contribution of this paper is the detailed discussion pre-
sented on the multi-scale nature of the ALD process and the
associated mathematical coupling of reactor gas transport to
heterogeneous surface reactions. The incorporation of the devel-
oped ALD gas–surface reaction mechanism; purely based on
270 A. Holmqvist et al. / Chemical Engineering Science 81 (2012) 260–272

consecutive and parallel elementary Eley–Rideal reaction steps; yk fractional surface coverage of surface species,
into the CFD representation of the equipment-scale, successfully dimensionless
related local gas-phase conditions in the vicinity of the substrate L maximum molar concentration of surface sites, mol m  2
surface to the transient production and consumption of the m dynamic viscosity of the gas mixture, Pa s
fractional surface coverage of chemisorbed species; ultimately xi surface reaction stoichiometric coefficient, dimensionless
underlying epitaxial film growth. r density of the gas mixture, kg m  3
A comprehensive experimental investigation on deposition of p molecular momentum flux tensor, Pa
ZnO films from Zn(C2H5)2 and H2O in the continuous cross-flow n number of surface OH groups reacting with each
reactor system F-120 by ASM Microchemistry Ltd. (Suntola, 1992) Zn(C2H5)2, dimensionless
has been carried out. The experimental results reported here, Pa characteristic function of t and Dt a , dimensionless
underscore the importance of substrate-scale uniformity mea-
ca molar fraction of gaseous species, dimensionless
surements in developing ALD process models. The conducted
O spatial domain, dimensionless
ex situ X-ray reflectivity and X-ray fluorescence film thickness
oa mass fraction of gaseous species, dimensionless
measurements at a discrete set of sampling positions on the
substrate are to be used for parameter estimation of the Arrhenius Subscripts and superscripts
kinetic parameters involved in the derived heterogeneous ALD
gas–surface reaction mechanism governing ZnO film growth. The 0 initial value
formulation and solution to a nonlinear parameter estimation a, b gaseous species indices
problem and an extensive simulation study on the ALD process entrentrance
are presented in the second article of this series (Holmqvist et al., g Dirichlet boundary condition
in press). h Neumann boundary condition
i surface reaction index
E calibration and validation set index
Nomenclature k surface species index
STP state at the standard temperature and pressure
Roman letters s solid
ref state at the reference temperature
Ai frequency factor in the Arrhenius equation,
ðmol m2 Þ1nads,i Pa1 s1 ,ðmol m2 Þ1ndes,i s1
Da b Maxwell–Stefan multicomponent diffusivity, m2 s1
Acknowledgment
Dab Fick multicomponent diffusivity, m2 s1
Dab binary diffusivity, m2 s1 This work has been supported by the Swedish Research
Ei activation energy, J mol
1
Council under Grant no. 2006-3738. The authors would like to
f body force vector, N m3 thank Dr. Jun Lu for the TEM micrograph of the CIS solar cell
hs film height, m device.
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