AbstractQuartz crystal microbalance (QCM) is a type of

very high sensitivity mass sensing device, its sensitivity can be

characterized by either frequency shift or phase shift. The main
effect inducing this characteristic is the mass effect. That is to
say, when the sensing surface of the device is perturbed by
adding a thin film of or a mass layer, the resonant frequency
will change, and so do the corresponding phase. A classical
quantitative equation relating resonant frequency to added
mass of the film was first derived by Sauerbrey, it reveals that
frequency decrease proportional to the mass that was added to
the surface of the QCM. In this paper, a new method called
phase response analysis method(PRAM) is proposed to study
the relation between phase shift and mass change of a rigid thin
film coated on QCM from the point of physical view. It is a new
way to describe the mass change that coated on the surface of
the QCM quantitatively. It is a simple mathematic model and
might be useful in some phase controlled sensor array systems.
Numerically calculated results of this model show that there
has a linear relationship between the phase shift and mass
change. Meanwhile, the high fundamental frequency and small
surface area can improve sensitivity. The principle of phase
shift measurement and corresponding measurement system is
also discussed.
I. INTRODUCTION
UARTZ crystal microbalance (QCM) is thought of one
of the ultra-sensitive mass sensors. It is often served as
a device to measure the mass density deposited onto the
crystal surface. The quartz crystal microbalance earns its
name from its ability to measure the mass of thin films that
have adhered to its surfaces. It is more sensitive than other
conventional analytical microbalances. The mechanics of a
microbalance is that mass adding or removing on the
electrode surface can cause frequency shift. A quantitative
equation relating resonant frequency shift to added mass of a
rigid thin film was first explored by Sauerbrey in 1959[1],
and governed by:
0
2
0
f
m
m
A N
m f
f
q

A
=
A
= A

(1)
This expression showed that the decreasement of the
resonant frequency of a thickness shear vibrating quartz
crystal resonator is proportional to the added mass of the
deposited rigid thin film. Where
0
f is the fundamental
frequency of the quartz crystal resonator, N is the frequency
constant of the special crystal cut,
q
is the quartz density, A
is the surface area of the deposited film, m is the mass of
the crystal, m A is the mass change.
The equation is based on three assumptions:
(1) The added mass is evenly distributed over the
electrode(s);
(2) The added mass is much smaller than the weight of
the quartz disk;
(3) The mass is rigidly attached to the electrodes, with
no slip or deformation due to the oscillatory motion.
Sauerbreys equation is modified by Behrndt[7]. Later,
perturbation analysis, energy transfer model, transmission
line mode, the composite acoustic model and equivalent
circuit model were introduced [8-12] to analyze the
frequency shift caused by the deposited mass.
Up to now, there is still a lack of a simple mathematical
model that describes the relation of m A and A in gas
phase. There is an absence of literatures discussing this topic.
In this paper, an expression which quantifies the phase shift
versus mass change of a rigid thin film coated on QCM is
derived from the point of physical view.
Like the classical frequency-mass relation that deduced by
Sauerbrey, the characterization based on phase-shift concept
is also useful. This PRAM is a new way to quantify the mass
change coating on the surface of the QCM sensor and it
might have a potential advantage to easily implement a
QCM sensor array system with a high level of integration
capability[6].
II. THEORY MODEL EVOLUTION
A. Prior Works
As we can know from prior investigations, people paid
more attentions on the frequency shift but less concerned on
the phase shift deduced by the deposited mass on the surface
of quartz crystal resonator in the past several decades. It is
up to 1990s, Glenn C. Komplin derived the phase-frequency
relationships from the Sauerbrey equation for solution-phase
microgravimetry in 1995[2].
df
d
A
f
dm
d
q q

=
2
0
2
(2)
Where
q
is the stiffened shear modulus, d , df is the
phase shift and frequency shift respectively. Obviously, the
expression above is just a simple mathematical expansion of
the Sauerbrey equation.
For liquid-phase analyzing, an alternative approach
based on a semi-empirical method was also used to model
and calculate phase change as a function of coating mass in
2003 by Saha[3]. And in 2009, Antonio[4] derived a new
equation which quantifies the phase shift versus a change in
the coating mass of the solution phase from motional
Phase and Mass Relationship of the QCM sensor Coated with
Rigid Thin Film
Feng Tan, Xianhe Huang, Shuyong Zhou, Chun Qing
School of Automation Engineering,University of Electronic Science and Technology of China,610054
E-mail: tanfeng@uestc.edu.cn
Q
376 978-1-4799-3051-7/13/$31.00 2013 IEEE
impedance view.
e q t

2 2
L L q q
c c
L q
c
v
h
m m
m
+
=
+
A
= A (3)
Where
c
m A is the coating mass,
q
m is the crystal mass,
L
m is the equivalent surface mass density of the contacting
liquid,
q
q is the loss viscosity of the unperturbed sensor and
q
v is the wave propagation speed in quartz,
L
and
L
o are,
respectively, the liquid density and the wave penetration
depth of the wave in the liquid.
In 2011, Y. J. Montagut and J. V. Garca adopted a similar
mathematical method described in[4] and developed the next
generalized approximated equation for the phase-shift of a
signal, of constant frequency very close to the motional
series resonant frequency of the resonator sensor, to small
changes both in the coating mass and liquid properties, is
found[5][6]:
L q
L c
m m
m m
+
A + A
= A (4)
B. Theory Model Derivation of Phase Shift
The following derivation is based on AT-cut quartz crystal.
Here defines the coordinate system associated with the
quartz disc in Fig 1 firstly.
Fig.1 The coordinate system associated with the quartz disc
As it is known, the QCM generally comprises a thin
AT-cut quartz wafer with a diameter of 0.25-1.0 inches,
sandwiched between two metal electrodes which are used to
establish an alternating electric field across the crystal.
When an AC voltage is applied over the electrodes the quart
crystal starts to oscillate at its resonance frequency due to the
piezoelectric effect. Using Newtons second law, one can
obtain:
z
T
y
T
x
T
t
U
zx
xy
xx x
q
c
c
+
c
c
+
c
c
=
c
c
2
2
(5)
Where
q
is the quartz density, T is the stress, andt is time.
If a potential | , is applied along the y direction, assuming
the wave propagating in the y direction only, and taking into
account the constitutive equations of AT-cut crystal, writing
the time and special dependences, one obtains:
2
2
2
2
26
2
2
66
t
U
y
e
y
U
C
x
q
x
c
c
=
c
c
+
c
c

|
(6)
And
0
2
2
22
2
2
26
=
c
c

c
c
y y
U
e
x
|
c (7)
Combining equation (6) with (7), resulting in:
2
2
2
t
U
y
U
x
q
x
q
c
c
=
c
c
(8)
Where
q
is the stiffened quartz elastic constant. And can
be expressed as:
22
2
26
66
c

e
C
q
+ = .
The general solution of the differential equation (8)
represents the superposition of two shear waves traveling
in y + and y directions and given as follows:
) ( ) ( t ky j t ky j
x
e U e U U
e e +

+
+
+ = (9)
Of course,
0
U U U = =
+
, if boundary conditions are
considered : 0 ) , 0 ( = t T
xy
and 0 ) , ( = t l T
q xy
. It is should
be noted that the upper and lower surface of this crystal can
be considered to be stress free surfaces when the quartz
crystal is excited in air. Hence, equation (9) could be turned:

t j
x
e ky U U
e
) cos( 2
0
= (10)
Obviously, the displacement of the quartz crystal is
constrained by the phase termky . Defining the phase term
as:
ky = ,
q
q
k

e = (11)
Where k is the wave number which describing shear wave
propagation in AT-cut quartz crystal. It would be a constant
if the thickness l A of the deposited rigid thin film on quartz
crystal surface is very tiny. Therefore, the ratio of the phase
shift induced by coating film with thickness l A to unloaded
quartz crystal with thickness
q
l is given as follows:
q q
l
l
kl
l k A
=
A
=
A
0

(12)
Adopting a similar method described in [14] [22], the
phase shift can be expressed:
m
S
f
m
m
q q
A

=
A
= A

0 0
0
2
(13)
377
Where S is the surface area of the quartz,
q
is the quartz
density,
q
is the stiffened quartz elastic constant,
0
f is the
fundamental frequency,
0
is the phase corresponding to the
frequency
0
f and m A is the mass of the coating thin film.
Introducing the equation as described in [13] with
frequency constant
AT
N :
0
f
N
l
AT
q
= (14)
By substituting (14) in (11), one can get:
0
0
f
N
k
AT
= (15)
Therefore, equation (13) could be expressed as follows:
m
S
N k
m
S
f
q q
AT
q q
A

= A

= A

2 2
0 0
(16)
Obviouslyparameter A could be measured, and rest
parameters are known when the crystal resonator is designed.
The mass of the deposited rigid thin film on the surface of
crystal could be calculated by:

= A
AT
q q
N k
S
m
2
(17)
At first glance, equation (17) looks like have nothing to do
with the resonant frequency
0
f . In fact, the wave number
k is a function of the fundamental frequency
0
f .
Substituting equation (11) into (17), phase shift versus mass
change relationship also could be represented:

A


= A
AT
q
N f
S
m
0
0
360 2
(18)
III. PRINCIPLE OF PHASE SHIFT MEASUREMENT AND
SYSTEM
When a rigid thin film deposited on the surface of the
QCM sensor, the frequency will shift, and the corresponding
phase will be also changed. Qualitative description of the
phase-shift characterization of QCM sensor is shown in
Figure 2.
As it is can be noted in fig 2, the phase characterization of
QCM sensor without deposited film could be described as
curve A in Fig 2, and the curve B is a description of the
phase characterization with loaded film. Phase shift A is a
qualitative description of the QCM sensor deposited a thin
film before and after.
Fig.2. The description of phase-shift ( A )of QCM sensor, measured with
E5062A (Agilent company)
As it is described in [4], traditional measurement methods
mentioned can be classified into two types: (1) those which
passively interrogate the sensor which is maintained external
to the measuring system and (2) those in which the sensor
forms part of the characterization system, such as oscillators.
In the first type, impedance or network analyzers and decay
methods are included. The advantages of impedance
analyzers are acknowledged and are mainly related to the
fact that the resonator sensor is almost characterized in
isolation and no external circuitry influences the electrical
behaviour of the sensor; additionally, electrical external
influences can be excluded by calibration.
To get the phase different, a phase comparison circuit
must be applied. A phase-shift monitoring at a constant
frequency in the sensor resonance bandwidth has been
recently proposed as an alternative characterization method
for high resolution QCM applications [15]. Based on this
idea, a very simple principal circuit [16] can be used for the
phase-mass characterization approach as depicted in Fig. 3,
where a mixer based phase detector is used. The advantage
of this approach is that the sensor is interrogated with an
external source which can be designed to be very stable and
with extremely low phase and frequency noises, even at very
high frequencies. This method has been already applied
under different conditions by some authors [17][18].
ATTENUATION
NETWORK
P
O
W
E
R
S
P
L
I
T
T
E
R
LPF
U
0
QCM
SENSOR
R
U
1
U
2
Fig.3. Simple system for measuring the phase shift
To accomplish this purpose easily, an integrated chip
named AD8302 must be introduced, as shown in Fig.4.
378
LOG AMP
DETECTOR
PHASE
10mV/
o
LOG AMP
DETECTOR
CHANNEL B
CHANNEL A
Fig.4. The AD8302 comprises a pair of accurately matched log amps
and a high-frequency phase detector.
The AD8302 can measure the phase difference between
two signals, from low frequencies up to 2.5 GHz. Each of
the individual log amps generates a hard-limited output at
its final stage. These signals are applied to the two inputs of
a novel multiplier-style phase detector having exact
symmetry with regard to its two inputs and a range of 180
o
.
The phase output,
PHS
V is given by[19][20]:
GP PHS
V V V + A = ) 90 (
0

(19)
Where

V is the scaling voltage for the phase output
and A is the phase difference between the two inputs. The
choice of sign depends on which two quadrants constitute
the 180
o
phase interval. With the inclusion of this feature,
the AD8302 becomes a network analyzer on a
chip[19][20].
Therefore, the phase shift measurement system could be
implemented by using the following circuit, It is introduced
in elsewhere[4][16]. Fig.5 shows the schematic interface for
the phase-shift characterization.
AD8302
INA
INB
PHFB
VPHS
A
POWER
SPLITTER
A
B
10mV/
O
P
R
E
C
I
S
I
O
N
A
M
P
L
I
F
I
E
R
OUT
REAITIMEPHASE
MEASUREMENTCIRCUIT
WITHQCMSENSOR
PHASEFOLLOWING
CIRCUIT
EXTERNAL
STABLE
SIGNAL
RESOURSE
Fig.5.Schematic Block Diagram of phase-shift Measurement
The circuit above is formed by two parallel branches
forming a differential circuit. Detail information about this
circuit may see reference [16]. The external stable signal is
divided into two signals, and then, pass through the branches
A and B. Assuming components in this circuit are thought to
be constants except for QCM sensor. The phase difference
can be got by measuring the output voltage of the AD8302.
Because the voltage related to phase shift of AD8302 is
relatively small, a precision operating amplifier must be used.
When there is no coating mass on the QCM sensor, one can
get a phase difference
0
A ; If a mass is added on the QCM
sensor, one can get another phase difference
1
A ; The phase
shift of the QCM sensor deposited by the thin film before
and after can be calculated by:
1 0
A A = A (20)
Using equation (18)-(20), the mass of coating film could
be calculated.
IV. NUMERICAL VALIDATION OF THE PHASEMASS
EQUATION
To verify the validity of equation (17) and (19), numerical
calculations were made.
For typical commercial 10MHz sensors, a value of 14mm
for the diameter of the quartz blank was selected. Firstly, we
calculate the sensitivity by using the parameters of 10MHz
AT cut quartz crystal as shown in table2. Substituting these
parameters into equation (19), one can get the mass
sensitivity of 2.469
2
mm ng , when the phase shift is
equal to0.001
o
.
Table 2. Parameters of 10MHz AT cut quartz crystal
Quartz parameter Value Description
f
0
10 Fundamental frequency
e
26
(A s m
2
) 9.65710
-2
Piezoelectric constant

22
(A
2
s
4
kg
1

m
3
)
3.98210
-11
Permittivity
C
66
(N m
-2
) 2.94710
10
Elastic constant
N
AT
(Hz m) 1.66110
3
Frequency constant
q
(N m
-2
) 2.9710
10
stiffened shear modulus
d(m) 1410
-3
Resonator Diameter
S(m
-2
) 1.53910
-4
Resonator surface area
Obviously, there is a simple linear relationship between
the phase shift and the mass change as we can see from
expressions (16) and (18). The phase shift is proportional to
the mass change. High fundamental frequency is helpful to
improve the resolution. The phase shift versus mass change
curve is shown in figure 6.
Fig.6. Phase shift versus mass density curve. Here three phase responses
with frequency of 5MHz, 10MHz and 20MHz were simulated. The
parameters are shown in table 2. The sign of minus in equation (17) and (19)
is ignored.
Applying equations (16) and (18), one can also find that
the phase shift is a function of the surface area of the crystal.
It is inverse proportional to the size. Assuming the same
amount of mass is deposited on surface of the different three
frequencies of 5MHz, 10MHz and 20MHz, the phase
379
sensitivity is obviously sensitive if the area is small. The
smaller the surface area is, the higher the sensitivity is. The
phase sensitivity versus surface area curve is shown in figure
7.
Fig.7. Phase shift versus surface area curve. Here three phase responses
with frequency of 5MHz, 10MHz and 20MHz were simulated. By assuming
the deposited mass is equal to 100ng. the rest parameters is shown in table
2.
V. CONCLUSION
Quartz crystal microbalance is a mass sensitive device,
and it is widely used in many fields. There are many
researches focused on its frequency response in the past
decades, but few studied about the phase response,
especially the rigid thin film that deposited on the surface of
crystal. A simple expression related to phase shift versus
mass change is derived from the point of physical view in
this paper.
Theoretically, the phase response analysis method, PRAM,
proposed in this paper has the same resolution as that of the
frequency response analysis method. We can only get the
phase shift indirectly by measuring the voltage of the phase
detector. that is to say, one must measure the voltage of the
phase detector firstly, and then calculate the phase. This
PRAM is a new way to quantify the mass change coating on
the surface of the QCM sensor and it might have a potential
advantage to easily implement a QCM sensor array system
with a high level of integration capability.
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