Chemical Engineering Science 94 (2013) 316–329

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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 II:
Experimental validation and mechanistic analysis
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 Methodology for estimating kinetic parameters involved in the ALD gas–surface reactions.
c Assessment of the statistical reliability of the parameter estimates and the model response.
c Continuous flow ALD reactor model was validated experimentally and showed high predictability.
c Mechanistic dependence of process operating parameters on ALD film growth profiles were assessed.
c Application of a heuristic optimization algorithm implemented in a cluster environment.

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

Article history: This paper demonstrates the experimental validation and mechanistic analysis of the continuous cross-
Received 20 February 2012 flow atomic layer deposition (ALD) reactor model developed in the first article of this series (Holmqvist
Accepted 28 June 2012 et al., in press). A general nonlinear parameter estimation problem was formulated to identify the
Available online 11 July 2012
kinetic parameters involved in the developed ALD gas–surface reaction mechanism, governing ZnO film
Keywords: growth, from ex situ film thickness measurements. The presented methodology for comprehensive
Atomic layer deposition model assessment considers the statistical uncertainty of least-squares estimates and its ultimate
Experimental model validation impact on the model predicted response. Joint inference regions were determined to assess the
Parameter identification significance of parameter estimates and results indicate that all estimates involved in the precursor
Optimisation
half-reactions were adequately determined. The reparameterization of the Arrhenius equation
Dynamic simulation
effectively decreased the characteristically high correlations between Arrhenius parameters, leading
Kinetics
to improvement in precision of individual parameter estimates. Model predictions of the spatially
dependent film thickness profile with narrow confidence band were in good agreement with both
calibration and validation experimental data, respectively, under a wide range of operating conditions.
The subsequent extensive theoretical analysis exhibits that the experimentally validated model
successfully reproduces the detailed process dynamics revealed by in situ quartz crystal microbalance
and quadrupole mass spectroscopy diagnostics, and thereby provides a supplementary analysis tool.
Finally, the univariate sensitivity analysis revealed the mechanistic dependence of all the measured
process operating parameters on the spatially dependent film thickness profile, resolved at the level of
a single pulse sequence. Hence, the presented model-based framework serves as a means to guide
future research efforts in the field of ALD process optimization.
& 2012 Elsevier Ltd. All rights reserved.

1. Introduction requirement for the understanding and modeling of atomic layer

Knowledge of the microscopic physicochemical growth process
and the underlying macroscopic mass transport is a fundamental
n
Corresponding author. Tel.: þ46 46 222 8301; fax: þ46 46 222 4526.
E-mail address: anders.holmqvist@chemeng.lth.se (A. Holmqvist).
deposition (ALD), see part I of this article series (Holmqvist et al., in
press or Elliott, 2007). According to the International Technology
Roadmap for Semiconductors (ITRS) (Semiconductor Industry
Association, 2011), process models have the potential to yield
insight that will enable improved efficiency and throughput in
manufacturing and in the design and evaluation of reactors. Due to
the lack of reliable fundamental physical and chemical data for new

0009-2509/$ - see front matter & 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2012.06.063
 A. Holmqvist et al. / Chemical Engineering Science 94 (2013) 316–329 317

precursors, and the introduction of new process configurations and
regimes, calibration and experimental validation of process models
have been identified as an important step in the field.
There are two main ways of providing additional physical
insight into the nature of the reaction mechanisms concerned
and determining reliable estimates of the kinetic parameters.
(i) Ab initio quantum-chemical and quantum-kinetic calculations
(Deminsky et al., 2004; Xu and Ye, 2010), and (ii) model calibra-
tion and experimental validation (Lim et al., 2000; Park et al.,
2000). However, the main objective of the published work was to
determine the principal features of the kinetic mechanism, and
detailed fluid dynamics was neglected at that stage. It was
emphasized by Puurunen and Vandervorst (2004) that model
calibration utilizing experimental saturation curves determined
from flow-type reactors, which are dominated by mass transport
(Aarik and Siimon, 1994; Siimon and Aarik, 1995; Ylilammi, 1995),
are generally not suitable for extracting kinetic parameters gov-
erning ALD growth without a reactor scale model. For this reason,
the novel mathematical model of the continuous cross-flow
reactor system F-120 by ASM Microchemistry Ltd. (Suntola,
1992) presented in the first article of this series (Holmqvist
et al., in press) was derived to mechanistically describe the
complex interactions between the gas-phase fluid dynamics, the
mass transport of individual species, and the ALD heterogeneous
surface reaction mechanism (Ritala and Leskelä, 2002). Thereby,
the model incorporates all relevant physicochemical phenomena
governing ALD growth required to assist in parameter estimation.
Furthermore, in contrast to the mathematical models proposed in
the aforementioned cited studies this model, comprises a system
of nonlinear partial differential equations (PDEs), provides spatial
resolution of the substrate film thickness profile (Siimon and
Aarik, 1995, 1997). Given the novel application, the detailed
experimental investigation on growth of ZnO films from Zn(C2H5)2
and H2O reported in Holmqvist et al. (in press) was performed in
order to assess the validity of the derived mathematical model on
a discrete set of sampling positions on the substrate, see e.g.
Cleveland et al. (2012) and Henn-Lecordier et al. (2011).
The overall objective of this study was to experimentally
validate and demonstrate the generally applicable mechanistic
model for the analysis and design of ALD processes developed in
the first article of this series (Holmqvist et al., in press). This paper
focuses around three main points. (i) To formulate and solve a
nonlinear parameter estimation problem using ex situ experimen-
tal data and the modeling environment presented in Holmqvist
et al. (in press), and (ii) to assess the statistical reliability of the
reactions and can thus be used to estimate the kinetic parameters
(Holmqvist et al., in press):
b ¼ ½L,kT ref,i ,i ,Ei y 8i A f1; 2, . . . ,4g ð1Þ
Nb
where b A R is the Nb -dimensional parameter space. However,
identifying the restricted set of kinetic parameters, b, in an ALD
process model represents a non-trivial task. The two main reasons
are:
(i) There is a complex interdependence between the sequential
and parallel elementary surface reactions (Pinto et al., 2011)
involved in ALD, such that the reactivity in one half-cycle is
influenced by that in the half-cycle preceding it (Kuse et al.,
2003; Ritala and Leskelä, 2002). Consequently, the kinetics of
each reaction step must be balanced with respect to the other.
(ii) The intrinsic mathematical structure of the nonlinear Arrhe-
nius equation introduces high correlation between the fre-
quency factor, Ai, and the activation energy, Ei (Buzzi-Ferraris
and Manenti, 2009; Héberger et al., 1987; Nagy and Turányi,
2011; Schwaab and Pinto, 2007, 2008; Schwaab et al., 2008b;
Varga et al., 2011).
For this purpose, a carefully chosen experimental design have
been recognized as an important element in comprehending the
coupled nature of the ALD growth kinetics and to obtain ade-
quately determined parameters (Park et al., 2000). The aim of the
experimental design is to yield the most possible information, in a
statistical sense, for use in parameter estimation and model
validation (Franceschini and Macchietto, 2008). Further, given a
set of discriminating experiments (Alberton et al., 2010, 2011), it
is important to utilize the experimental information in an optimal
preserving manner. As emphasized by Schwaab et al. (2008a), the
error structure of the kinetic constants in nonlinear models may
be non-convex, open and constitute of discontinuous regions. For
this reason, it was recommended that the entire calibration
parameter vector, b, should be calibrated simultaneously using
the entire experimental calibration data set, y, ^ presented in
Holmqvist et al. (in press).
2.1. Formulation of the nonlinear parameter estimation problem
The nonlinear parameter estimation problem is formulated as
a general nonlinear optimization problem:
min FðbÞ
bAR
Nb

 
parameter estimates and the predicted model response, and (iii) to dx
perform an extensive analysis of the experimentally validated ALD s:t: 0¼F ,x,u, b,w,t , xðt 0 Þ ¼ x0
dt
process model dynamics, and to mechanistically determine the y ¼ gðx,u, b,wÞ
sensitivity of the equipment-scale process operating parameters bmin r b r bmax
on film growth. Although assessed in several experimental studies,
with b ¼ ½L,kT ref,i ,i ,Ei y 8i A f1; 2, . . . ,4g
see e.g. Aarik et al. (2006), Jur and Parsons (2011), and Lei et al.
y
(2006), the mechanistic details of the process operating para- xE ¼ ½p,v, oa , yk ,ms  8a, k
 
meters have not yet been thoroughly studied theoretically. yE ¼ ½hs ðzÞ9f^ ,UF y  y ^f ¼ 1 , 3 , 5  9G 9
sub
The reminder of this paper is organized as follows. The non- 6 6 6
linear parameter estimation problem is formulated in Section 2, uE ¼ ½Dt ZnðC2 H5 Þ2 , Dt H2 O ,Ty
while the subsequent section describes the statistical model wE ¼ ½Dt N , Q_ , Q_ , Q_ y
2 N2 ZnðC2 H5 Þ2 H2 O ,/pS9Gout  ð2Þ
validation methodology. Section 4 outlines the optimization envir-
onment. Section 5 presents the results from the validation meth- where b is subject to lower and upper bounds acting as inequa-
odology followed by an extensive mechanistic analysis of the ALD lity constraints and estimated by minimizing an objective func-
process model. Finally, concluding remarks are drawn in Section 6. tion FðbÞ, based on the deviations between the observed, y, ^ and
predicted system response, y. By using the method of lines (Davis,
1984; Schiesser, 1991) and finite element method (Zienkiewicz
s
2. Nonlinear parameter estimation and Taylor, 2000a,b) framework in COMSOL Multiphysics
(COMSOL AB, 2008), the associated system of nonlinear differ-
The inverse method used in this study utilizes the fact that the ential algebraic equations (DAEs), in which x, u and w represent
height of the film contains information on the elementary surface dependent states, free design variables, and algebraic variables, is
318 A. Holmqvist et al. / Chemical Engineering Science 94 (2013) 316–329
denoted by F in Eq. (2). It is noteworthy that response function g,
which transforms and selects those state variables that are
experimentally measured, is a nonlinear function of b for all
states x. The weighted sum of squared residuals is used to
quantify the estimation, and is defined as
X gation of parametric uncertainty is to produce model predictions
FðbÞ ¼ ½y^ E yE ðxE ,uE , b,wE Þy W1 ^
E ½y E yE ðxE ,uE , b,wE Þ ð3Þ
E¼1
where W is the square weight matrix corresponding to the
different weights used to normalize the contribution of each
particular observation E within the N E -dimensional sample space.
The details underlying the statistical assumptions and their
implications, which lead to the use of the least-squares estimates
encompass several different aspects of the regression model, are
presented elsewhere (Bates and Watts, 1988).
3. Statistical model validation via nonlinear parameter
estimation
In accordance with the methodology employed by Pinto et al.
(2011), the statistical model validation methodology developed
for this study is subdivided into two main parts: (i) parameter
identifiability and the uncertainty of the estimates and (ii) good-
ness-of-fit of the model response and the underlying assumptions
regarding the disturbances.
3.1. Assessment of the accuracy and reliability of the parameter
estimates
Parameter precision is equivalent in mathematical terms to
the size of the inference regions of the parameter estimates
(Hamilton et al., 1982). Based on the assumptions underlying
least squares estimation, see e.g. Bates and Watts (1988), second-
order statistics (Witkowski and Allen, 1993) were explored for the
construction of the confidence regions and assessing the uncer-
tainty of b^ in the parameter space b A RNb . The approximate
100ð1aÞ% joint confidence region, obtained from a second-order
Taylor expansion of the objective function, Fðb^ Þ, around the
minimum point estimate (Schwaab et al., 2008a), is defined by
fb : ½bb^ y Rðb^ Þ1 ½bb^  r Nb F ðNb , j;aÞ g
where F ðNb , j;aÞ is the upper a quantile for Fisher’s F-distribution
with j ¼ NE Nb degrees of freedom and Rðb^ Þ is the ðNb  N b Þ
parameter variance–covariance matrix (Asprey and Macchietto,
2000). This approach also suggests the 100ð1aÞ% marginal
confidence interval for bı (Bard, 1974; Draper and Guttman,
1995), ıA f1; 2, . . . ,Nb g:
fb : 9bı b^ ı 9r Sıı ðb^ Þ1=2 t ðj;1a=2Þ g
where t ðj;1a=2Þ is the upper a=2 quantile for Student’s t-distribu-
tion and Sıı ðb^ Þ is the ðı,ıÞ th element of Rðb^ Þ. Nevertheless, as
emphasized by Bates and Watts (1988), Watts (1994) and
Witkowski and Allen (1993), this linearization approach is only
approximately applicable to nonlinear models, and in the case of
high nonlinearity it can be quite inaccurate. For this purpose, the
likelihood 100ð1aÞ% joint confidence region (Beale, 1960) is
defined for all values of b such that
fb : FðbÞFðb^ Þ rs2 Nb F ðNb , j;aÞ g
where s2 ¼ Fðb^ Þj1 is the variance estimate of s2 . In contrast to
Eq. (4), the confidence regions obtained with this method can be
disjointed and unbounded, depending on the complexity of the
parameter nonlinearity.
3.2. Assessment of the accuracy and reliability of the predicted
model response
The net effect of the statistical assumptions that are inherently
made when applying the least-squares estimates and the propa-
with an uncertainty bound (Draper, 1995). The approximate
100ð1aÞ% confidence bands for the response function (Bates
and Watts, 1988) are given by the collection of all curves
yðx,u, b,wÞ belonging to the set:
n
yðx,u, b,wÞ : 9fyðx,u, b,wÞgfyðx,u, b^ ,wÞg9
o
r ½Jðb^ Þy Rðb^ ÞJðb^ Þ1=2 ðNb F ðNb , j;aÞ Þ1=2 ð7Þ
where Jðb^ Þ ¼ @yðx,u, b,wÞð@bÞ1 9b ¼ b^ denotes the parameter Jaco-
bian matrix (Chappell and Gunn, 1998).
4. Optimization environment
The minimization of the objective function, FðbÞ, in nonlinear
parameter estimation problems is associated with complex numer-
ical problems (Buzzi-Ferraris and Manenti, 2009; Moles et al., 2003).
Therefore, the following measures must be taken into consideration
in the formulation of the method: (i) the size of the parameter space,
(ii) the multimodal nature of the objective function, (iii) the
continuity of the objective function, and (iv) the sensitivity of the
objective function to each of the model parameters (Hibbert, 1993).
One way to overcome the non-convexity of the optimization
problem is to consider a method of heuristic optimization, such as
evolution strategies and genetic algorithms (Price et al., 2005). These
algorithms overcome the starting-point problem resulting from the
multi-modal nature of the objective function, by sampling the
objective function at multiple, randomly chosen initial points where
the present parameter bounds define the domain, and rely on a large
number of objective function evaluations and a random search
character to assure a high probability of finding the global optimum.
These characteristics lead to prohibitively long computation
times for the solution of this kind of problem, making non-
sequential solution approaches necessary. According to the ITRS
ð4Þ
initiative, time-critical simulation steps or algorithms should
support parallelization on high-performance computation clus-
s
ters. Hence, the forward model simulator, COMSOL Multiphysics
(COMSOL AB, 2008) integrated with MATLABs (The MathWorks
Inc, 2010a) was extended for implementation in a cluster envir-
onment, following the master-slave paradigm (Coello et al., 2007).
The model-based methodology supports the working procedure as
follows: First, the parameter space, RNb , is sampled with Latin
ð5Þ hypercube sampling (LHS) (McKay et al., 1979), using lhsdesign in
TM
the Statistics Toolbox for MATLABs (The MathWorks Inc, 2010c) to
determine a feasible input for the heuristic optimization method.
Subsequently, the evolution strategy differential evolution (DE) DE/
rand-to-best/2/bin (Storn and Price, 1997; Price, 1999; Price et al.,
2005) was used to find the optimal least-squares estimates. Applying
the concept of distributed computation resulted in a scalable and
affordable cluster solution for the use of both the LHS and DE
algorithms.
Nonetheless, gradient methods outperform direct search
ð6Þ methods both in reliability and speed of convergence (Bard,
1974). Additionally, DE possesses no strict convergence criteria.
Therefore, in order to ensure reliability and to further enhance
convergence of the output optimal calibration parameter vector
bn A P from DE with respect to the feasible region; in which the
parameters are linearly independent (Asprey and Macchietto,
 A. Holmqvist et al. / Chemical Engineering Science 94 (2013) 316–329 319

2000; Vajda et al., 1989): the hybrid numerical procedure described in Section 4. The
Nb Nb experimental calibration data sets, y^ E , 8E 2
= f2; 11,23g used for
P ¼ fb A R n
: rank Jðb Þ ¼ Nb 4:(b A R , UðbÞ r Uðb Þg
n n
ð8Þ
evaluation of FðbÞ are reported in Holmqvist et al. (in press)
the gradient-based algorithm lsqcurvefit in the Optimization and the operating conditions associated with the E th index are
TM
Toolbox for MATLABs (The MathWorks Inc, 2010b) was uti- listed in Table 1. The remaining data sets are used for experi-
lized to yield the final least-squares estimates, b^ . mental model validation (see Section 5.1.3).

5.1.1. Assessment of the accuracy and reliability of the parameter

5. Results and discussion
estimates
The statistical significance and reliability of b^ is assessed by
5.1. Parameter estimation and statistical model validation
evaluating the confidence statements presented in Section 3.1.
A large confidence interval (Eq. (5)) or region (Eqs. (4) and (6))
Parameter estimation of the kinetic parameters (Eq. (1))
suggests either that a parameter estimate cannot be discriminated
involved in the ALD gas–surface reactions was performed with
from another with the experimental design considered or that there
Table 1 is a high uncertainty in the precision associated to this parameter,
Outline of the experimental design. The ALD pulse sequence considered for the growth i.e. the model is inadequate in distinguishing a phenomenon in the
of ZnO was the following ðDt ZnðC2 H5 Þ2 , Dt N2 , Dt H2 O , Dt N2 Þ including a nitrogen purge system (Bard, 1974; Bates and Watts, 1988).
DtN2 ¼ 4:0  101 s between the non-overlapping alternate injections of the precur- The approximate marginal confidence intervals (Eq. (5)) and the
sors for all cases E. All experiments were performed with the process operating corresponding margin of error, eb^ ¼ Sıı ðb^ Þ1=2 t ðj;1a=2Þ , with a sig-
parameters: /pS9Gout ¼ 2:0  102 Pa, ½Q_ ZnðC2 H5 Þ2 , Q_ H2 O , Q_ N2  ¼ ½0:11,0:16,5:0  102 ı
nificance level of a ¼ 5:0  102 and 8ıA N b are reported in Table 2.
sccm [standard cubic centimeters per minute at STP] (cf. Holmqvist et al., in press
The narrow confidence intervals for parameters b^ ı and
for physical interpretation). The uniformity factors for the experimentally observed
response, UF y^ , and the model generated response, UFy, and the relative model error, dy,
8ıA f1; 2, . . . ,5g indicate that these estimates are adequately deter-
for all calibration sets are also presented. mined. Consistently larger relative errors, though still remaining
moderate, were obtained for parameters b^ ı and 8ıA f6; 7, . . . ,9g, i.e.
E DtZnðC2 H5 Þ2  101 DtH2 O  101 T  10  2 UF y^ UFy dy the kinetic parameters governing the rehydroxylation reaction (see
(s) (s) (1C) (%) (%) (%)
e.g. Holmqvist et al., in press; Deminsky et al., 2004; Matero et al.,
2000; Rahtu et al., 2001), and these are thus the most difficult
1 2.0 4.0 1.0 97.1 94.4 5.9
2a 4.0 4.0 1.0 94.7 95.6 4.1 parameters to statistically discriminate against others satisfactorily
3 6.0 4.0 1.0 93.8 95.9 6.7 with the experimental design considered.
4 12.0 4.0 1.0 90.1 96.4 5.7 In addition, the maximum molar concentration of surface sites
5 18.0 4.0 1.0 94.7 95.9 2.7 L can be deduced from the physical properties determined from
6 6.0 1.0 1.0 92.3 96.2 9.9
the analysis of film growth experiments (Coltrin et al., 2008). The
7 6.0 2.0 1.0 93.7 95.8 9.3
8 6.0 4.0 1.0 93.8 95.6 6.1 experimental surface site density, determined from the density of
deposited ZnO films, rs ¼ 5:4  103 kg m3 at T ¼423.2 K in
9 1.0 4.0 1.5 96.8 96.9 2.2 ~ 2=3 N~ ¼
10 2.0 4.0 1.5 95.7 97.8 5.3 Törndahl et al. (2007), was found to be L ¼ ðrs M 1 s NÞ
5 2
11a 4.0 4.0 1.5 98.4 99.1 1.9 1:94  10 mol m . This value shows reasonable agreement
12 6.0 4.0 1.5 98.3 99.4 2.2 with the final estimate b^ 1 presented in Table 2, further verifying
13 12.0 4.0 1.5 99.0 99.9 0.76 that this estimate was adequately determined.
14 6.0 1.0 1.5 97.8 95.8 3.0
Another aspect affecting the reliability of b^ is parameter
15 6.0 2.0 1.5 95.7 99.5 7.3
16 6.0 4.0 1.5 98.4 99.4 2.2 correlation, which may originate from an inappropriate model
representation and/or experimental design (Schwaab and Pinto,
17 1.0 4.0 2.0 97.7 97.9 2.8
18 2.0 4.0 2.0 97.5 98.4 2.9 2007). Despite the implication of the intrinsic mathematical
19 4.0 4.0 2.0 96.8 99.1 5.9 structure of the Arrhenius equation (Nagy and Turányi, 2011;
20 6.0 4.0 2.0 98.9 99.0 3.8 Varga et al., 2011), the majority of the elements of the parameter
21 12.0 4.0 2.0 99.1 99.6 5.1 correlation matrix, C ı‘ ðb^ Þ and 8ıa ‘ A Nb , are moderately low (see
22 6.0 1.0 2.0 99.0 99.0 1.0 P
23a 6.0 2.0 2.0 99.1 99.6 1.3
Table 2) and yielding an overall correlation level C ¼ ð ı a ‘
24 6.0 4.0 2.0 99.0 99.1 3.8 C ı‘ ðb^ Þ2 ðN2b N b Þ1 Þ1=2 (Pritchard and Bacon, 1978) of 0.43. This
implies that the characteristically high parameter correlations,
a
Experimental validation set. almost equal to one (Héberger et al., 1987), were successfully

Table 2
Regression analysis of the parameter least-squares estimates, b^ . The correlation matrix Cðb^ Þ and normalized margin of error e b^ were determined at a significance level of
a ¼ 5  102 . The specific reaction rate kT ref,i ,i and 8i A f1; 2, . . . ,4g are defined at the reference temperature T ref,i ¼ 4:19  102 K. According to Elam and George (2003), the
variable numbers of surface hydroxyl groups that react with the ZnðC2 H5 Þ2 adsorptive precursor molecule in the elementary surface reactions (cf. Holmqvist et al., in press)
was defined as n ¼ 1:37. Parameter units: kT ref,1 ,1 ððmol m2 Þ1n Pa1 s1 Þ; kT ref,2 ,2 ððmol m2 Þn1 Pa1 s1 Þ; kT ref,3 ,3 ððmol m2 Þ1 s1 Þ; kT ref,4 ,4 ðPa1 s1 Þ.

ı Parameter b Parameter estimates b^ Margin of error e b^ (%) Approximate correlation matrix Cðb^ Þ

1 L 1.53  10  5 0.183 1.00 0.63 0.74 0.46 0.52  0.80 0.61 0.39  0.35
2 kref,1 8.16  10  6 1.24 1.00  0.53 0.12  0.22 0.19 0.11 0.10  0.06
3 E1 3.57  104 0.172 1.00 0.21  0.15  0.72 0.19 0.21  0.23
4 kref,2 1.33  10  6 1.16 1.00 0.52  0.28 0.13  0.97  0.30
5 E2 4.04  104 0.155 1.00  0.11 0.09 0.20  0.17
6 kref,3 3.45  10  6 3.29 1.00  0.56  0.31 0.36
7 E3 2.67  104 2.56 1.00 0.38 0.29
8 kref,4 4.68  10  7 5.21 1.00  0.59
9 E4 3.79  104 4.95 1.00
320 A. Holmqvist et al. / Chemical Engineering Science 94 (2013) 316–329

decreased through reparameterization of the Arrhenius equation

and definition of a reference temperature, see Holmqvist et al. (in
press), Schwaab et al. (2008b), and Schwaab and Pinto (2007,
2008), leading to significant improvement in the precision of
individual parameter estimates. In this study, T ref,i , 8i, were
assigned the inverse average temperature over the experimental
range analyzed (cf. Table 1).
In order to understand the behavior of the relative errors and
the parameter correlations, a more rigorous statistical evaluation
of the parameter estimates is obtained by considering confidence
regions (Eqs. (4) and (6)), described by function evaluations
performed by the heuristic optimization method along the search,
as discussed in Schwaab et al. (2008a). The likelihood 100ð1aÞ%
joint confidence regions, with a significance level of a ¼ 5  102 ,
for pairs of parameters bı and 8ıA f1; 2,3; 6g are depicted in Fig. 1.
From the figure it is evident that the significant reduction in
parameter correlation, through the reparameterization method
applied in Holmqvist et al. (in press), also provides an improve-
ment in the elliptical representation of the confidence regions
(Bates and Watts, 1988) associated with the pair of parameters
b2 b3 (of the gas–surface reaction i¼1 Holmqvist et al., in press).
Furthermore, it is noteworthy that the pairwise plots of the
likelihood joint confidence regions clearly do not extend into
negative parameter regions, which is required for interpreting
physically meaningful parameters (Beale, 1960).
Fig. 2. Nominal 95% likelihood confidence region for the normalized and centered
However, when considering the 95% likelihood joint confi- parameters b4 and b8 . (– –) Approximate marginal 95% confidence interval
dence region (Eq. (6)) associated with ıA f4; 8g depicted in Fig. 2, ð7 e b^ Þ; (–) approximate joint 95% confidence region; (þ ) Normalized and
ı
it is evident that the approximate 95% joint confidence region centered least-squares estimates, b^ ı .

Fig. 1. Nominal 95% likelihood confidence region for pairs of normalized and centered parameters bı and 8ıA f1; 2,3; 6g; (– –) approximate marginal 95% confidence interval
ð 7 e b^ Þ; (þ ) normalized and centered least-squares estimates, b^ ı .
ı
 A. Holmqvist et al. / Chemical Engineering Science 94 (2013) 316–329
(Eq. (4)) provides a poor representation, and thus, lead to erro-
neous conclusions about the confidence on model parameters. In
Fig. 2, the point estimate of model parameters is placed at the
center of the hyper-ellipsoid and the likelihood confidence region
is non-convex and unbounded, since the parameter b8 does not
have an upper limit. Hence, the model is unable to discriminate
between high values of b8 , as high values of this parameter lead to
a constant model response, y. The occurrence of the elongated
likelihood joint confidence region reflects the parameter correla-
tion (Emig and Hosten, 1974). In order to further reduce the
parameter correlation and simultaneously improve the precision
of the parameter estimates, two essential points are: (i) use an
experimental design with extended information that enables
discrimination (Franceschini and Macchietto, 2008) of the afore-
mentioned parameters and (ii) perform the numerical optimiza-
tion procedure proposed in Schwaab et al. (2008b) and Schwaab
and Pinto (2007, 2008) to provide the optimum reference tem-
peratures, T ref,i , for every ith Arrhenius reaction rate equation,
respectively. An optimal experimental design and a set of optimal
reference values holds the potential to yield precise estimates of
uncorrelated parameters, and the likelihood joint confidence
region would tend towards being elliptical.
Moreover, on the subject of improving information content, in
a statistical sense, obtained from the measured response, y, ^ to
maximize the calibration parameter discrimination capacity, the
ITRS guidelines promote the use of in situ diagnostics, including
quartz crystal microbalance (QCM) (Aarik et al., 2006; Elam and
George, 2003) and quadrupole mass spectroscopy (QMS) (Lei
et al., 2006; Rahtu and Ritala, 2002). These monitoring techniques
provide extensive dynamic information during the ALD pulse
sequence, thereby improving the information content and enhan-
cing the reliability of the parameter estimates. However, the main
objective of the derived ALD process model in this article series
was to accurately predict the response of the substrate spatially
dependent film thickness profile to the variations of all the
measured equipment-scale process operating parameters. For this
reason, the ex situ instrumentation used for film characterization
in Holmqvist et al. (in press) are superior to the aforementioned
in situ diagnostics, since the latter measurement response pro-
vides no information regarding the nature of the spatial depen-
dence of the deposition rate. Consequently, to further enhance the
reliability of the parameter estimates, b^ , while still maintaining
the precision of the spatial model response, the utilization of both
in situ and ex situ diagnostic methods may become necessary.
5.1.2. Assessment of the accuracy and reliability of the predicted
model response
In order to verify the precision of the model response, the
statistical uncertainties and their effects on the model response
were addressed by considering the model 100ð1aÞ% approximate
confidence band (Eq. (7)). The model generated spatially dependent
film thickness profile, hs ðzÞ, for the least-squares estimates (see
Table 2) and the associated 95% approximate confidence band are
depicted in Fig. 3 along with the experimentally observed film
thickness, y9 ^ f^ , sampled at three spatially equidistant positions,
f^ ¼ ½16 , 36 , 56  9Gsub 9 (m), on the substrate, Gsub .
Essentially, to statistically assess the reliability of the spatially
dependent film thickness profile hs ðzÞ, it is necessary that the
confidence bandwidth is moderately narrow and that it replicates
the spatial dependency of the model response. According to Fig. 3
it is possible to statistically assure that the model output predicts
a non-uniform film thickness profile for E ¼ 17, in contrast to the
case of E ¼ 10. Hence, the accuracy and predictability of the model
can thus be determined by analyzing the bandwidth and shape of
the approximate inference band. In addition, the effect of the
321
uncertainty on the precision of the parameter estimates given by
the model can be evaluated.
The graphic representation of some of the experimental
calibration data sets E A f1; 3,8; 9,10; 14,17; 20,24g in Fig. 3a–c
indicates that the model output and the experimental data show
good agreement. The comparison between the uniformity factors
for the experimentally observed, UF y^ , and model generated
response, UF y , in Table 1 also shows satisfactory agreement for
the majority of the calibration data sets. The worst fit is found for
the calibration data sets employing a temperature of 1:0  102 1C
and short pulse duration of the adsorptive precursors, which give
film profiles with the lowest uniformity factors. This is evident
when visualizing the model accuracy, the associated bandwidth
of the inference bands and when analyzing the relative error dyE
and 8EA NE for each calibration index (see Table 1). On the other
hand, the calibration sets with longer adsorptive precursor pulse
duration, especially for the H2O precursor, have significantly
lower relative errors, demonstrating that the model describes
this part of the calibration region better.
When growing oxide films by ALD in a viscous flow reactor
with alternating injection of adsorptive precursors, Groner et al.
(2004) reported that complete purging of reactants, especially
H2O, takes significant longer time at low temperatures ð r1:0 
102 1CÞ because of slower desorption from the reactor walls.
Hence, purge times must be increased with decreasing tempera-
ture in order to prevent simultaneous presence of both precursors
in the gas phase which results in regular CVD growth, comprising
a higher growth rate than in true ALD (Elers et al., 2006; Jur and
Parsons, 2011). In this study, the N2 purge time was held constant
at Dt N2 ¼ 4:0  101 s (see Table 1) in the entire temperature
region and local CVD growth may occur on the leading edge of the
substrate in the cross-flow reactor, causing the sharp change in
growth rate over the substrate, and thus degrading the overall
uniformity. Consequently, this phenomena could explain the
discrepancy between the model predicted response and the
experimental measurement data at T ¼ 1:0  102 1C.
A more comprehensive presentation of the reliability and the
adequacy of the model response can be achieved by examining
the distribution of the residual errors for the calibrated model.
This can be graphically visualized by plotting the relative error dyE
and 8EA N E for all calibration sets against the cumulative distribu-
tion, determined using the empirical cumulative distribution
TM
function ecdf in the Statistics Toolbox for MATLABs (The
MathWorks Inc, 2010c). On the basis of the cumulative distribu-
tion of residual errors in Fig. 4, it is evident that 90% of the
residual errors is below 7.3% and the only errors above this arise
from experimental indices E A f6; 7g. However, the relative errors
are below 10% for all experimental indices, confirming rather high
predictability even for the worst cases studied.
The fitted normal cumulative distribution function, using
TM
normcdf in the Statistics Toolbox for MATLABs (The
MathWorks Inc, 2010c), depicted in Fig. 4, demonstrates reason-
able agreement with the cumulative frequency of the relative
model error, implying that the residual errors follow a normal
distribution with an expected value and a variance (Hines et al.,
2003), in accordance with the chi-square goodness-of-fit test as
defined in Schwaab et al. (2006), Pinto et al. (2011), and Alberton
et al. (2011). Thus, the underlying statistical assumptions on
which the use of the least squares was based are not violated.
5.1.3. Experimental model validation
The ultimate test of the adequacy of the model is to compare it
to the validation set, and if the experimentally observed and
model predicted response show good agreement, the model can
be considered valid. The region of validity can subsequently be
322 A. Holmqvist et al. / Chemical Engineering Science 94 (2013) 316–329

1.14 1.49 1.48

1.03 1.34 1.34

0.93 1.2 1.2

0.82 1.06 1.07

0.71 0.92 0.93

1.98 2.27 2.22

1.86 2.1 2.06

1.74 1.93 1.9

1.62 1.76 1.74

1.49 1.59 1.58

2.09 2.21 2.21

1.96 2.07 2.07

1.84 1.92 1.92

1.72 1.78 1.78

1.59 1.63 1.64

1.26 2.27 2.01

1.16 2.17 1.93

1.06 2.07 1.86

0.95 1.97 1.79

0.85 1.87 1.72

Fig. 3. Spatially dependent film thickness profile hs ðzÞ as a function of the substrate boundary Gsub local coordinate variable z A ½0,9Gsub 9 (m). The operating conditions
associated with the E th index are specified in Table 1. Model response hs ðzÞ (Å cycle  1) for: (a) calibration data sets performed at T ¼ 1:0  102 1C; (b) calibration data sets
performed at T ¼ 1:5  102 1C; (c) calibration data sets performed at T ¼ 2:0  102 1C; (d) validation data sets. (þ ) Experimental response hs ðf^ Þ (Å cycle  1) at f^ ¼ ½16 , 36 , 56 
9Gsub 9 (m); (–) spatial film thickness profile; (– –) 95% approximate confidence band (Eq. (7)); (––) uncertainty band for the expected response determined by uniformity
distribution with the parameter bounds specified according to the marginal confidence intervals given in Table 2.

defined as the union between of the calibration region and the
region covered by the validation experiments (Brereton, 2003).
Fig. 3d visualizes the model response for the experimental
validation data set with EA f2; 11,23g (see Table 1). The uncertain-
ties enclosed bands were constructed from the extreme model
response generated from Latin hypercube sampling (LHS) (McKay
TM
et al., 1979), using lhsdesign in the Statistics Toolbox for
s
MATLAB (The MathWorks Inc, 2010c), with the parameter
boundaries specified in accordance with the marginal confidence
intervals (see Eq. (5) and Table 2). The graphical presentation of
the model response in Fig. 3d demonstrates that the performance
of the model and the resulting predictability are satisfactory, with
low relative residual errors, dy, and conformal uniformity factors
for the model generated, UF y , and the experimentally observed,
UF y^ , response, which confirms that the model is valid within the
calibration region.
5.2. Mechanistic analysis of the ALD process model
This section demonstrates the universal applicability of the
mechanistic model of the continuous cross-flow ALD reactor
(Suntola, 1992), derived in the first article of this series
(Holmqvist et al., in press), with statistical reliable least-squares
estimates (see Eq. (1) and Table 2) for the kinetic parameters
involved in the elementary ALD gas–surface reactions. Based on
the experimentally validated mathematical model, with adequate
predictability of the spatial resolution of the film thickness profile
(see Section 5.1), an extensive theoretical investigation was
performed with the focus on mechanistic understanding of ALD
process dynamics and the influence of equipment-scale process
operating parameters on ALD film growth. The mechanistic
model-based analysis complements available experimental
results deduced from the literature, see e.g. Aarik et al. (2006),
 A. Holmqvist et al. / Chemical Engineering Science 94 (2013) 316–329
100
80
60
40
20
0
0 2 4 6 8 10 12
Fig. 4. The cumulative distribution of the relative residual errors, dyE , and 8E A N E .
(–) The cumulative frequency for the calibration data set; (– –) fitted normal
TM
cumulative distribution function normcdf in the Statistics Toolbox for MATLABs
(The MathWorks Inc, 2010c).
Elam and George (2003), Jur and Parsons (2011), Kuse et al.
(2003), Lei et al. (2006), and Rahtu et al. (2001).
5.2.1. General characteristics of the ALD film growth process
In the context of deposition of ZnO films in continuous cross-
flow ALD reactors, 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, dependence have been undertaken seriously in Elam
et al. (2002), Elam and George (2003), Törndahl et al. (2007), and
Yousfi et al. (2000). According to Deminsky et al. (2004) and
Matero et al. (2000), either the dehydroxylation reaction or the
rehydroxylation reaction (surface reaction index i A f3; 4g,
Holmqvist et al., in press) determines the overall growth rate in
the high-temperature region. This is evident when considering
the temperature dependence of the degree of hydroxylation, /gS,
after the H2O sequence t A ½0, Dt ZnðC2 H5 Þ2 þ Dt N2 þ Dt H2 O , graphically
presented in Fig. 5, and expressed as
Z Z
1 yOH
/gS ¼ @G@t ð9Þ
9Gsub 9 t Gsub yOH þ yO
At the highest temperatures, dehydroxylation is so extensive that
it overrides the increase in hydroxyl groups during the water
sequence. In contrast, the overall growth rate decreases in the
low-temperature region, which is attributed to the activation
energy of the elementary surface reactions i A f1; 2g.
A graphic representation of the transient production and
consumption of fractional surface species, yk and k A fOH,
ZnðC2 H5 Þ2n ,Og, during one complete ALD pulse sequence
ðDt ¼ Dt ZnðC2 H5 Þ2 þ 2Dt N2 þ Dt H2 O Þ sampled at three different tem-
peratures is presented in Fig. 6. It is evident from this figure that
the fractional surface coverage of elementary oxygen, yO , is the
source of the decrease in yOH at elevated temperatures. Because of
the sequential nature of the surface reactions, the effect of the net
yO production is twofold: the fractional surface coverage of yOH is
reduced, which limits the number of adsorption sites for the
adsorptive ZnðC2 H5 Þ2 precursor, thereby preventing the produc-
tion of yZnðC2 H5 Þ2n , which successively reduces the number of
323
2 1
1.8 0.9
1.6 0.8
1.4 0.7
1.2 0.6
1 0.5
0.8 0.4
0.6 0.3
0.4 0.2
0.2 0.1
0 0
0 50 100 150 200 250 300
14
Fig. 5. Dependence of the film mass increment on the process temperature during
one ALD sequence. (–) The integral mean value of the mass increment /ms S over
Gsub per ALD sequence and unit area; ð,Þ analogous to (–) but using the
generalization of Fick’s law (cf. Holmqvist et al., in press); (– –) the degree of
hydroxylation /gS (a.u.) after the H2 O exposure in the pulse sequence. Process
operating parameters: /pS9Gout ¼ 3:0  102 Pa, /pS9Gin ¼ 4:3  102 Pa, ½Q_ ZnðC2 H5 Þ2 ,
Q_ H2 O , Q_ N2  ¼ ½0:10,0:15,5:0  102 sccm (standard cubic centimeters per minute at
STP), pulse sequence, ½Dt ZnðC2 H5 Þ2 , Dt N2 , Dt H2 O , Dt N2  ¼ ½2:0,4:0,2:0,4:0  101 s.
adsorption sites for the adsorptive H2O precursor in the subse-
quent pulse sequence. The pseudo-steady-state process corre-
sponding to one pulse sequence can be seen in the figure, where
the initial surface fraction composition is also governed at the end
of the same pulse sequence. This is a consequence of the initial
normally hydroxylated surface, resulting in a constant mass gain
per cycle (MGPC) (Burton et al., 2009), and consistent with the
ex situ XRR analysis in Holmqvist et al. (in press).
However, all states governing the system’s behavior do not
remain constant throughout the duration of the pulse sequence;
therefore, the system is evidently not time-invariant. The
response of the transient system is apparent when analyzing
the mean mass deposited per unit area resolved at the level of
each cycle, see Fig. 7. The theoretical trajectory resembles
previous experimental QCM measurements for ZnO: i.e. a mass
increment due to irreversible adsorption of the adsorptive
Zn(C2H5)2 precursor, a flat portion of the trajectory during the
purge exposure, and a decrease in mass during the adsorptive
H2O precursor sequence (Elam and George, 2003; Yousfi et al.,
2000).
The general formalism of the sequential elementary surface
reactions i A f1; 2g (Holmqvist et al., in press) incorporating a
variable number of reacting hydroxyl groups, n, enables the
surface chemistry to be analyzed during one pulse sequence,
and the discrepancy between different reaction mechanisms to be
investigated on the basis of mass increment during the respective
half-reactions. The theoretical mass increment trajectories shown
in Fig. 7 demonstrate the characteristic dependence of n A 0, nL ½,
where nL represents the total number of ligands of the adsorptive
organometallic precursor, and corresponding DM 2 DM 1 1 ratios
(Elam and George, 2003). Thus, the inherent structure of the
model supports the utilization of the entire information content
of observed mass increment trajectories when extracting detailed
surface chemistry data, i.e. when determining n and the calibra-
tion parameter vector, b (Eq. (1)).
An additional method of assessing n considers temporal and
spatial integration over an arbitrary boundary G, of the reaction
324 A. Holmqvist et al. / Chemical Engineering Science 94 (2013) 316–329

100
1

0.8
80
0.6

0.4
60
0.2

0
40

1
20
0.8

0.6
0
0.4
15
0.2
12
0
9
6
1
3
0.8 0
0.6

0.4 0 0.2 0.4 0.8 1 1.2

0.2

0 Fig. 7. (a) Transient analysis of the integral mean mass increment /ms Sðng cm2 Þ
0 0.2 0.6 0.8
Fig. 6. Integral mean value of the fractional surface coverage /yk S (a.u.) at Gsub
during one ALD sequence at: (a) T ¼ 1:5  102 1C; (b) T ¼ 2:0  102 1C;
(c) T ¼ 2:5  102 1C. (-) /yOH S; ð,Þ analogous to (-) but using the generalization
of Fick’s law (cf. Holmqvist et al., in press); (- -) /yZnðC2 H5 Þ2n S; ð  Þ /yO S. The
dotted lines perpendicular to the t-axis represent the individual adsorptive
precursors and purge exposures of one pulse sequence. The process operating
parameters are analogous to those defined in Fig. 5.
byproduct released during the surface reaction i¼1 (Holmqvist
et al., in press) and the entire pulse sequence. Consequently, this
quantity is governed by
Y Z Z ð1ÞW þ 1
n ¼ nL pC2 H6 @G@t
W¼1 tW G formulation may be omitted, to a very good approximation, and
where W ¼ f1; 2g and t 1 A ½0, Dt ZnðC2 H5 Þ2 þ Dt N2  for the nominator
respective t 2 A ½0, Dt ZnðC2 H5 Þ2 þ 2Dt N2 þ Dt H2 O  denominator tem-
poral integrals. The trajectories of the integral mean value of the
gas-phase composition at the outlet boundary, Gout , during one
pulse sequence are presented graphically in Fig. 8. It is clear that
the /pC2 H6 S9Gout trajectory is explicitly governed by xa,i /r i S9G
sub
and Eq. (10) provides the specified nominal value of n.
The aforementioned method, which considers spatial integra-
tion, provides quantitative, chemically specific information and
can be used as a supplementary theoretical analysis quantity in
in situ QMS diagnostics (Lei et al., 2006; Rahtu et al., 2001). It is
noteworthy that the spatial boundary integration or point evalua-
tion can be utilized anywhere downstream of the substrate to
adequately reproduce the output of QMS sampling systems.
at Gsub during one ALD sequence. (–) /ms S with the number of reacting hydroxyl
groups n ¼ 1:37; (– –) /ms S with the number of reacting hydroxyl groups n ¼ 1:0.
1.2 (b) Transient analysis of the integral mean gas-phase composition, /pa S (Pa), of
the adsorptive precursor at Gin . (–) /pZnðC2 H5 Þ2 S; ð,Þ analogous to (–) but using the
generalization of Fick’s law (cf. Holmqvist et al., in press); (– –) /pH2 O S. The
dotted lines perpendicular to the t-axis represent the individual adsorptive
precursors and purge exposures of one pulse sequence. The process operating
parameters are analogous to those defined in Fig. 5 and T ¼ 1:5  102 1C.
Together, Figs. 7 and 8 reveal rigorous process dynamics of the
ZnO ALD process that are essential process analysis, design and
optimization.
The comparison of the model response in Figs. 5–8, using the
binary and multicomponent formulations (cf. Holmqvist et al., in
press), respectively, for the mass flux show only minor deviations.
This is due to the low molar composition of C2 H6 relative the
remaining species, and hence, the rigorous, multicomponent
ð10Þ
one-way solute–solvent interactions suffice. Therefore, the dis-
cussion regarding the sensitivity of the process operating para-
meters in Section 5.2.2 will be addressed solely on the basis of the
binary formulation for the mass flux.
5.2.2. Sensitivity of process operating parameters on ALD film
growth
In their experimental investigation of deposition efficiency in a
continuous flow ALD reactor, Aarik et al. (2006) and Jur and
Parsons (2011) observed the influence of carrier gas flow para-
meters on ALD growth rate. To verify whether the predicted model
response resemble the experimental observations, a comprehen-
sive univariate sensitivity analysis of the measured process oper-
ating parameters u ¼ ½/pS9Gout ,T, Q_ a , Dt a y , a A fN2 ,ZnðC2 H5 Þ2 ,H2 Og,
 A. Holmqvist et al. / Chemical Engineering Science 94 (2013) 316–329 325

10 However, it is reasonable to exclude the decrease in reactor

1
chamber residence time t ¼ ð9Gsub 9 þ29Gwall 9Þ/vS9O (s) at ele-
vated linear flow rates as the underlying cause of the observed
significant decrease in /ms S, since t 5 Dt a , a A fZnðC2 H5 Þ2 ,H2 Og,
8 for the entire range of /vS9O studied. In contrast, the decrease in
/ms S can be mechanistically correlated to the hydrodynamic
interdependence governed by Eq. (11), which originates from the
6 ideal gas law. At constant applied /pS9Gout and T, Eq. (11) states
that the linear flow rate is directly proportional to the mass flow
of the carrier gas, /vS9O pQ_ N2 . Consequently, the increase
4 in Q_ N2 with /vS9O imposes a decrease in local mass fraction of
the a th adsorptive precursors, oa , and ultimately resulting in
reduced driving force in the gas–surface reaction rates, hence
r i pðpca Þ9G and 8i a 3 (Holmqvist et al., in press).
2 sub
According to Eq. (11), a decrease in carrier gas pressure at Gout ,
at constant applied /vS9O and T, imposes a decrease in Q_ N2 and
an increase in the overall local oa , respectively. Additionally,
0 overall lower local p also implies that the binary gas diffusion
coefficient is increased, since Dab pp1 (Bird et al., 1960), which
10 increases the rates of impingement mass flux to the substrate
surface, ja ¼ rDab roa (Holmqvist et al., in press). In summary,
8
these mechanistic characteristics will promote a higher molar
6 composition of the a th adsorptive precursors, ca , in the vicinity
4 of the substrate, enhancing the rate of elementary surface reac-
tions. In contrast, a decrease in the local carrier gas pressure will
2
limit this driving force. However, the net increase in mass
0 deposited, /ms S, can be mechanistically correlated to the inverse
pressure dependence of the impingement mass flux, ja , which
compensates for the reduction in reaction driving force,
r i pðpca Þ9G for 8i a 3.
sub
0 0.2 0.4 0.8 1 1.2 The temperature dependence on /ms S is thoroughly dis-
cussed in Section 5.2.1. The interdependence of the process
temperature on the applied pressure and linear flow rate of the
Fig. 8. (a) Transient analysis of the integral mean gas-phase composition, /pa S
carrier gas is graphically presented in Fig. 9b and c. It is evident
(Pa), at Gout during one ALD sequence. (–) /pZnðC2 H5 Þ2 S; ð,Þ analogous to (–) but
using the generalization of Fick’s law (cf. Holmqvist et al., in press); (––) that the sensitivity to /vS9O is higher than to /pS9Gout , and the
/pC2 H6 S  5; (–) /pH2 O S. (b) Transient analysis of the integral mean value of absolute effect on /ms S is more pronounced at temperatures
elementary surface reactions /r i S ðmol m2 s1 Þ at Gsub . (–) /r 1 S; (– –) /r2 S. The corresponding to high growth rates.
dotted lines perpendicular to the t-axis represent the individual adsorptive Provided that /pS9Gout , /vS9O , and T are held constant, there
precursors and purge exposures of one pulse sequence. The process operating
are two main ways of varying the half-cycle average exposure
parameters are analogous to those defined in Fig. 5 and T ¼ 1:5  102 1C.
dose for the a th adsorptive precursor (Adomaitis, 2010; Gordon
et al., 2003; Jur and Parsons, 2011):
Z Z
1
on the increment of film mass per unit area, resolved at the level /da S ¼ p @G@t ð12Þ
9Gsub 9 Dta Gsub a
of a single pulse sequence, /ms S was performed. Furthermore, the
model-based analysis is extended to comprehend the mechanistic either by changing the mass flow of the precursors, Q_ a , thereby
parameter impact on the spatially dependent film thickness changing the partial pressure, or by changing the duration of the
profile, conveniently represented by the uniformity factor, UF. pulse, Dt a . Hence, under prevailing operating conditions, the
In Aarik et al. (2006), the influence of carrier gas mass flow, required minimum substrate saturation exposure dose of the
Q_ N2 , was evaluated on the basis of the linear flow rate, and in this a th adsorptive precursor is governed by
study, expressed mathematically as the integral mean value of the Z Z
1 n  ðroa v þ ja Þ
velocity field, /vS9O , in the computational domain O (cf. L¼ @G@t ð13Þ
9Gsub 9 Dtsat, a Gsub Ma
Holmqvist et al., in press):
Z Z As emphasized by Kuse et al. (2003), a net effect of Q_ a and Dt a on
1 1 X 1 /ms S can only be observed provided that the saturation exposure
/vS9O ¼ v@O ¼ r Q_ a @O ð11Þ
9O9 O 9O9 O rAO a ¼ 1 STP, a dose according to Eq. (13) is not achieved. The interdependence of
mass flow and the pulse duration of ZnðC2 H5 Þ2 adsorptive pre-
where AO is the cross section area of O and r ¼ pMðRTÞ1 the local cursor on /ms S is graphically presented in Fig. 9d. It is evident
density. The predicted model response depicted in Fig. 9a shows that /ms S reached a plateau as saturation of the surface sites is
that /ms S decreases, at an applied carrier gas pressure, /pS9Gout , achieved, which demonstrates the characteristic self-limiting
at Gout , when increasing the linear flow rate of the carrier gas. nature of the ALD processes (Lim et al., 2003; Puurunen, 2005).
Analogous dependencies were observed when increasing the As emphasized by Cleveland et al. (2012), the across substrate
carrier gas pressure while maintaining a constant linear flow uniformity is a useful process metric to evaluate the self-limiting
rate, although in this case, the sensitivity of the carrier gas behavior of the ALD process. In agreement with experimental
pressure on /ms S was weaker. This conclusion is consistent with observations in Henn-Lecordier et al. (2011), enhanced uniformity
the experimentally observed parametric behavior in Aarik et al. at higher precursor exposure doses, /dZnðC2 H5 Þ2 S, were obtained in
(2006). Fig. 10d. However, it is noteworthy that the film thickness
326 A. Holmqvist et al. / Chemical Engineering Science 94 (2013) 316–329

1 1

0.8 0.8

0.6 0.6

0.4 0.4

0.2 0.2

0 0
50 50
180 180
310 310
440 26 15 440 90 50
570 48 37 570 170 130
700 70 59 700 250 210

1 1

0.8 0.8

0.6 0.6

0.4 0.4

0.2 0.2

0 0
15 1.5
26 1.2
37 0.9
48 90 50 0.6 16 20
59 170 130 0.3 8 12
70 250 210 0 0 4

Fig. 9. Normalized integral mean mass increment /ms S (a.u.) as a function of (a) integral mean value of the velocity field /vS9O ðm s1 Þ on O and pressure at the outlet
/pS9Gout (Pa); (b) process temperature T (1C) and outlet pressure /pS9Gout (Pa); (c) process temperature T (1C) and integral mean value of the velocity field /vS9O ðm s1 Þ on
O; (d) inlet mass flow Q_ ZnðC2 H5 Þ2 (sccm) and pulse duration DtZnðC2 H5 Þ2 (s). The values of the parameters not varied in each case were assigned according to the reference
conditions: temperature T ¼ 1:5  102 1C, pressure at the outlet /pS9Gout ¼ 3:0  102 Pa, integral mean value of the velocity field /vS9O ¼ 3:0  101 m s1 on O, inlet
adsorptive precursor mass flow ½Q_ ZnðC2 H5 Þ2 , Q_ H2 O  ¼ ½5:0,5:0 sccm, pulse sequence ½Dt ZnðC2 H5 Þ2 , Dt N2 , Dt H2 O , Dt N2  ¼ ½2:0,4:0,2:0,4:0  101 s).

uniformity factor, UF, is not strictly increasing with the precursor
exposure dose.
Furthermore, the interdependence of /pS9Gout and /vS9O
depicted in Fig. 10a reveals that UF approaches unity at the lower
parameter boundaries. By analysing the spatially dependent film
thickness profiles depicted in Fig. 3, it is evident that thickness
uniformity enhancement imposes higher reaction driving forces,
r i pðpca Þ9G and 8i a 3, as z-9Gsub 9 (m). As aforementioned, the
sub
decrease in /pS9Gout and /vS9O promoted enhanced mass flux, ja ,
to the substrate surface and mass fraction, oa , of the a th
precursor, respectively, and thus, explains the parametric depen-
dence on UF. In addition, the UF temperature dependence resem-
bles that of /ms S (cf. Figs. 9 and 10), however the impact is not
that pronounced in the lower temperature region, in which the
overall growth rate is attributed to the activation energy of r i and
i A f1; 2g (cf. Section 5.2.1).
6. Concluding remarks
This paper demonstrates the universal applicability of the
mechanistic model of the continuous cross-flow reactor system
F-120 by ASM Microchemistry Ltd. Suntola (1992) derived in the
first article of this series (Holmqvist et al., in press). According to
the ITRS initiative, models of ALD processes must have a high
level of accuracy if they are to be used to assist in process
analyses, design or optimization. For this reason, a systematic
methodology to support the development and statistical valida-
tion of ALD process models was proposed. Within this framework,
the statistical uncertainty of least-squares estimates of kinetic
parameters involved in the ALD gas–surface reaction mechanism
governing ZnO film growth, and its ultimate impact on the model
response have been assessed.
The comprehensive model assessment reported here showed
that the expected high parameter correlation, originating from
the complex interdependence between elementary surface reac-
tions involved in ALD and the intrinsic mathematical structure of
the Arrhenius equation, was successfully diminished through
reparameterization of the Arrhenius equation, and hence, leading
to the improvement in precision of the parameter estimates. It is
also shown that the model predictions of the spatially dependent
film thickness profile are in good agreement with both calibration
and validation experimental data, respectively, under a wide
range of operating conditions.
The novel model-based methodology presented in this paper
constitutes a general platform for mechanistic investigations of the
detailed process dynamics of a continuous cross-flow ALD reactor.
The extensive theoretical analysis exhibits that the experimentally
validated model, successfully reproduces the detailed process
dynamics revealed by modern in situ monitoring technologies, as
advocated by the ITRS initiative, and thereby provides a supplemen-
tary analysis tool. Furthermore, the univariate sensitivity analysis
 A. Holmqvist et al. / Chemical Engineering Science 94 (2013) 316–329 327

a b
1 1

0.96 0.96

0.92 0.92

0.88 0.88

0.84 0.84

0.8 0.8
50 50
180 180
310 310 250
440 59 70 440 210
570 48 570 130 170
26 37 90
700 15 700 50

c d
1 1

0.96 0.96

0.92 0.92

0.88 0.88

0.84 0.84

0.8 0.8
15 1.5
26 1.2
37 0.9
48 210 250 0.6 4 0
59 130 170 0.3 12 8
70 50 90 0 20 16

Fig. 10. Across substrate film thickness uniformity, UF, as a function of (a) integral mean value of the velocity field /vS9O ðm s1 Þ on O and pressure at the outlet /pS9Gout
(Pa); (b) process temperature T (1C) and outlet pressure /pS9Gout (Pa); (c) process temperature T (1C) and integral mean value of the velocity field /vS9O ðm s1 Þ on O;
(d) inlet mass flow Q_ ZnðC2 H5 Þ2 (sccm) and pulse duration Dt ZnðC2 H5 Þ2 (s). The values of the parameters not varied in each case were assigned according to the reference
condition in Fig. 9.

revealed the mechanistic dependence of the measured process g response function –

operating parameters on ALD film growth performance metrics. hs film height m
Hence, the presented model-based framework also serves as a means J parameter Jacobian matrix –
to guide future research efforts in the field of ALD process optimiza- ja diffusive mass flux vector kg m2 s1
tion. On the basis of the characteristic timescales of the mass ki reaction rate constant ðmol m2 Þ1nads,i Pa1 s1 ,
transport and the surface reaction mechanism considered, it is
ðmol m2 Þ1ndes,i s1
possible to determine the optimal process operating parameters to
Ma molar mass kg mol
1
achieve optimal film growth rate and adsorptive precursor utiliza-
tion, while simultaneously controlling film thickness uniformity ms film mass increment kg m2
across the substrate. N~ Avogadro’s number mol
1

ni surface reaction adsorption –

and desorption order
p pressure Pa
Nomenclature
Q_ a volumetric flow rate at STP Nm3 s1
R universal gas constant 1
J mol K1
Roman letters
s2 the variance estimate of s2 –
Ai frequency factor in the ðmol m2 Þ1nads,i Pa1 s1 , T temperature K
Arrhenius equation ðmol m2 Þ1ndes,i s1 t time s
C Nb  N b parameter – t ðj;a=2Þ Student’s t-distribution –
correlation matrix UF spatial film profile –
Dab binary diffusivity m2 s1 uniformity factor
Ei activation energy J mol
1 u design variables –
F system of differential – v velocity vector m s1
algebraic equations W weight matrix –
F ðNb , j;aÞ Fisher’s F-distribution – w algebraic variables –
328 A. Holmqvist et al. / Chemical Engineering Science 94 (2013) 316–329

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