QCM

QUARTZ CRYSTAL MICROBALANCE - THEORY AND MODELLING

Marco Mauro
M.Ph. Scientific Coordinator
Novaetech S.r.l.
Via J.F. Kennedy, n.5 80125 Napoli (Italy)
email mauro@novaetech.it
web www.novaetech.com
twitter @novaetech
July 24, 2014
Revision 1.0
This work is licensed under a Creative Commons
Attribution-ShareAlike 4.0 International License.
Hypotesis
- film thickness less than that of the quartz
- inertial load uniform, rigid and fixed to the quartz surface
- no dissipation crystal oscillation takes place in air or in vacuum
SAUERBREY EQUATION
Sauerbrey equation changes in resonant frequency of the quartz shear
vibration is proportional to the mass deposited on its active surface
Additional mass causes the decrease of the resonant frequency.
Sauerbray equation: linear relationship between resonance frequency variations and deposited thiny-stiff mass
NOT working
- liquid is not integral to the quartz, resistance to the
free motion
- viscosity loss of mechanical energy
|
.
|

\
| A
|
.
|

\
|
= A
A
m
q q
f
f
2 / 1
2
0
2

q

_shear modulus
q

_density
_resonant frequency
0
f
A
_electrode area
Sauerbrey G. Zeitschrift Fr Physik, vol. 155, no. 2, pp. 206-222, (1959)
Sauerbrey equation is directly derived from the solution of the one-dimensional shear wave equation (Helmholtz equation).
The proportionality factor depends on the physical-geometrical characteristics of quartz crystal.
Resonance Frequency and Vibration Amplitude as
function of the distance from the centre of the quartz
(Mecea 2005).
s
v
q
f
q q
f
A
m
f
S

2
0
2
2 / 1
2
0
2 =
|
.
|

\
|
=
|
.
|

\
| A
A
=
q

= 2.947 x 10
11
g
-1
cm
2
s
-1


q

= 2.648 g cm
-3
q q
v
s
=
= 3.340 x 10
5
cm s
-1
Mecea, V. M. From Quartz Crystal Microbalance to Fundamental Principles of Mass Measurements, Anal. Lett., vol. 38, no.
5, pp. 753-767, (2005)
QCM Sensitivity is not uniform over the surface of the
quartz, it is maximum in the centre and decreases near the
edges of the electrode.
Gaussian distribution of the QCM mass sensitivity
Distribution of the vibration amplitude.
QCM sensitivity with frequency resolution of 1 Hz
MHz 25
0
= f
2
cm 1 . 0 = A ng 07 . 0 ~ Am
QCM measures deposited mass in the range of
nanogram 10
-9
g
exe
SAUERBREY EQUATION
QCM Sensitivity
Relationship between the variation of the resonance
frequency and that of the density mass deposited:

QCM IN LIQUID KANAZAWA - GORDON
Kanazawa - Gordon model Hypotesis
No Dissipation quartz is a perfectly elastic solid
Newtonian Liquid purely viscous liquid, linear relationship
between stress - strain rate
QCM in Liquid Relationship between the variation of the
resonance frequency of a quartz crystal immersed in a fluid
The vibration consists of both a stationary shear wave in the
quartz and an acoustic damped wave in the liquid. (Kanazawa
Gordon 1985)
Kanazawa, K. and Gordon G.J. Frequency of a Quartz Microbalance in Contact with Liquid Anal. Chem., vol. 57, no. 9, pp. 1770-1771, (1985).
Kanazawa, K. and Gordon G.J. The oscillation frequency of a quartz resonator in contact with liquid Anal. Chim. Acta, 175, pp. 99-105, (1985)
Characteristic Length of the damped vibration
L
L
e
q

0
2
=
L
q
_liquid viscosity
_liquid density
L

exe
QCM into water at T = 20C
nm 250 =
Liquid Effective Mass
0
2
e
q

L L
L L
m = = A
MHz 5
0
= f
Resonance Frequency Variation
q q
L L
f f
t
q
2 / 3
= A
exe
QCM in water at T = 20C and
Hz 6100 = Af

Electro-Mechanical Model
General model predicts quantitatively the effects of a
generic load on the quartz surface . This model is the
base for using QMC as biosensor (Johansmann).
Electrical System Mechanical System
Resistance R Friction
Inductance L Mass m
Capacitor C Elasticity k
Current i(t) Velocity v(t)
Voltage V(t) Force F(t)
jL
q
R
q
1/jC
q
1/jC
0
mechanical
branch
electrical
branch
Schematic of the electro-mechanical equivalence
Johansmann, D. Modeling of QCM data , unpublished manuscript, available on-line
Butterworth - Van Dick Circuit
Equivalent circuit of the quartz crystal
Small loads
Variation close the resonance

Mechanical Branch
Inductance Quartz crystal initial mass
Capacitor Mechanical Elasticity
Resistance Friction/Dissipation

Electrical Branch
Capacitor Capacitance between the electrodes

Load Impedance Z
m
Ratio between surface stress and velocity field.
ELECTRO MECHANICAL MODEL
SMALL-LOAD APPROXIMATION
Mechanical Electrical System Equivalence
Resonance Frequency and Load Impedance
Load Impedance is the crucial physical quantity in QCM sensing applications under the most general conditions.
Conductance curve (i.e. resistance inverse) as a
function of the quartz vibration frequency
Complex Resonance Frequency
Load Impedance Z
L
in BVD circuit is the electrical equivalent
of a generic load on the quartz surface.
Small load approximation
At the resonance the complex part of total impedance is null
o
u
Shear stress
Quartz surface velocity
q
Z = 8.8 x 10
9
gm
-2
s
-1
Acoustic impedance of AT-cut quartz
ELECTRO MECHANICAL MODEL
SMALL-LOAD APPROXIMATION
Resonance frequency
Half Band Half Width (HBHW)
r
e
I
Layered Systems Applications of Interest
We use the small-load approximation model to calculate the variation of the resonance frequency for layered systems, that
is planar loads uniformly distributed on the quartz crystal surface

Viscoelastic Medium (semi-infinite)
Inertial Load (Sauerbrey equation)
Viscoelastic Film
Viscoelastic Film in Liquid

Hypothesis
Quartz crystal and the layers are laterally homogeneous and infinite
The vibration is a tranverse shear wave, whose direction is perpendicular to the surface (thickness shear mode).
The stress tensor is proportional to the deformation, which means that linear viscoelasticity is verified
the contribution due to the piezoelectric stiffness is neglected
ELECTRO MECHANICAL MODEL
SMALL-LOAD APPROXIMATION
Johansmann, D. Modeling of QCM data , unpublished manuscript, available on-line
Quartz Crystal Microbalance, Wikipedia, http://en.wikipedia.org/wiki/Quartz_crystal_microbalance
Viscoelastic Medium (Semi-Infinite)
Shear wave inside the crystal and a propagation wave inside the medium, that
travels away from the crystal surface.
Quartz Crystal in contact with a semi-
infinite viscoelastic medium
Inertial Load - Sauerbrey Equation
Quartz Crystal in contact with a purely
inertial load.
Newtonian liquid = cost. e = 0 not a function of frequency.
The variaition of the resonance frequency is equal and opposite to that of the
bandwidth of the resonance curve Kanazawa Gordon equation
Inertial Load there is only the shear wave propagating inside both the quartz
crystal and the layer. The surface stress is caused only by the inertia of the
deposited film.
The variation of the complex resonance frequency is given by:
ELECTRO MECHANICAL MODEL
SMALL-LOAD APPROXIMATION
Viscoelastic Film
More general formulation respect to Sauerbrey hypothesis, it is considered
viscoelastic film of arbitrary thickness . The vibration consists of a shear wave
inside the quartz crystal and a wave transmitted reflected inside the
viscoelastic film.
Quartz Crystal in contact with a
viscoelastic film of arbitrary
thickness
The relation can be written in function of the physical quantity related to the
viscoelastic film
If the film thickness is very small, we can derive an approximated relation that explicitely contains the film viscoelastic
constants (by expanding the tangent function in Taylors series to the second order):
Sauerbrey equation
film thickness is negligible
ELECTRO MECHANICAL MODEL
SMALL-LOAD APPROXIMATION
The variation of the complex resonance frequency is given by:
Viscoelastic Correction
film thicknes is not negligible
Viscoelastic Film in Liquid
On the quartz crystal surface is deposited a viscoelastic film of arbitrary
thickness and they are immersed in a liquid. Vibrations consists of a shear-wave
inside the quartz, a transmitted wave propagating through the film and
reflected at the boundary quartz-film and film-liquid, and a propagation wave in
the liquid, that travels away from the film surface.
Quartz Crystal in contact with a
viscoelastic film and immersed in a
fluid
The variation of the complex resonance frequency is given by:
If we consider small thickness film, by expanding in Taylors series d
f
0
Kanazawa-Gordon Missing Mass
Johannsmann, D. Viscoelastic analysis of organic thin films on quartz resonators, Macromol. Chem. Phys. 200, 501 (1999)
Voinova, M.V. , Jonson, M.B. and Kasemo, B., Biosens. Bioelectr. 17, 835 (2002)
Missing mass effect viscoelastic correction reduces the mass measured for soft-film (deviation from Sauerbrey equation)
ELECTRO MECHANICAL MODEL
SMALL-LOAD APPROXIMATION
Resonance frequency variation is measured respect to reference state, the quartz is immersed in the fluid (KG + Sauerbrey)
Sauerbrey
QCM-D QUARTZ CRYSTAL MICROBALANCE
WITH DISSIPATION MONITORING
Dixon, M. C. Quartz crystal microbalance with dissipation monitoring: enabling real-time characterization of biological
materials and their interactions., Journal of biomolecular techniques, vol. 19, no. 3, pp. 151-8, (2008).
Resonance frequency variation f Mass deposited on the quartz surface
Measurement of energy losses due to dissipation D Viscoelastic properties of liquid in contact with quartz
Life sciences applications DNA, proteins, lipids and cells and so on...
Principle of Measurement
Measurement of the
characteristics of quartz
damped oscillations, caused
by a rapid excitation of the
quartz.
- Protein = rigid layer,
frequency variation (mass)
- Biomacromolecules =
frequency and dissipation
variation (viscolastic mass)
stored
dissipated
E
E
Q f
D
t t t 2
1 1
= = =
Adsorption of the protein serum albumin step a) and his
antibody step c). Step b) and d) rinse with buffer solution.
a) Frequency variation - no change in dissipation serum
albumin is a rigid protein
c) Frequency and dissipation variation antibody causes an
increase in mass and viscoelasticity (water)
d) Dissipation variation change in antibodies conformation
QCM SPOTLIGHTING RESEARCH
SURFACE-SPECIFIC VESCICLE INTERACTIONS
Kanazawa K. and Cho C., Quartz Crystal Microbalance to characterize Macromolecular Assembly dynamics, Journ. Sens. (2009)
Adsorption Kinetics of vesicles on solid
layers
a) Lipids double-layer on SiO
2
b) Intact vescicles on Au layer
c) Two-steps di fusione kinetics of
vescicles unilamellar bilayer
d) Adsorption Kinetics of intact vescicles
frequency and dissipation variation
a)
b)
d) c)
Review Papers from 2001 to 2011: detailed informations on the most recent research on QCM sensing in the fields of
Biosensors Materials Science

Cooper, M. A. and Singleton, V. T. A survey of the 2001 to 2005 quartz crystal microbalance biosensor literature:
applications of acoustic physics to the analysis of biomolecular interactions, Journal of Molecular Recognition, pp. 154-184,
(2007).
Vashist S.K. and Vashist P. Recent advances in Quartz Crystal Microbalance-Based Sensors, Journal of Sensors, 2011,
Article ID 571405, (2011).

Detailed bibliography on QCM: Theoretical model, Instruments, Applications for specific load, Biosensor, Chemical sensor,
last review 2005 by Stanford Research System

Stanford Research System Quartz Crystal Microbalance References, available on-line at
http://www.thinksrs.com/downloads/PDFs/ApplicationNotes/qcmref.pdf (last revision 2005)

Marco Mauro
M.Ph. Scientific Coordinator
Novaetech S.r.l.
Via J.F. Kennedy, n.5 80125 Napoli (Italy)
email mauro@novaetech.it
web www.novaetech.com
twitter @novaetech
July 24, 2014
Revision 1.0
This work is licensed under a Creative Commons
Attribution-ShareAlike 4.0 International License.
ADDITIONAL REFERENCES