QCM & EQCM

- Principle & Application in Ion Transport

State Key Laboratory of Electroanalytical Chemistry

Changchun Institute of Applied Chemistry
Chinese Academy of Sciences
 Resonance & Standing Wave

External Stumili

Resonance - The increase in amplitude of oscillation of an

electric or mechanical system exposed to a
periodic force whose frequency is equal or
very close to the natural undamped frequency
of the system.

Standing Wave - A wave characterized by lack of vibration

at certain points, between which areas of
maximum vibration occur periodically.
 Adsorbed
Quartz
Layer

External Stumili fm Area=A

dq  da
q a
f0
q

fm – final or total frequency that we measured

f0 – intrinsic frequency of quartz crystal
dq – thickness of quartz crystal
q – velocity in crystal of wave transfer
q – density of quartz crystal
a – density of adsorbed layer
 da – thickness of adsorbed layer
 Adsorbed
Quartz
Layer

External Stumili fm Area=A

dq  da
q a
f0
q


1
d q  q mq
2 q  2
A q
d q A q  mq

 f df  df m  
f
d  
f0
dm  
f0 mm
)
f0
f  df   d d (2 dmm
 2  2
q 2
q 2
q A q d q A q

d ~ d q  d Constant f0 Minute Change in Mass

df  dm
 Sauerbrey,s equation,
f = -2mf02/A()1/2
where  m is the mass change of quartz crystal
surface,  f is the frequency change caused by  m, f0
is the fundamental resonant frequency of quartz crystal
in the absence of the deposited mass, A is the
geometric area of electrode,  is the shear modulus of
quartz and  is the density of quartz.
 f = C m
C is called as calibration constant of QCM

Ref : Sauerbrey, G. Z. Phys. 1959, 155, 206.

 Liquid
y Surface Mass
,  Layer f, f
Quartz Crystal hf

Metal Electrode
Displacement

Front Lead Wire

Back Lead Wire AT-Quartz

Illustration of quartz crystal oscillator The shearing stationary wave in quartz crystal
and its propagation
 Illustration of EQCM instrument

f
Regulator Counter f

Working
Oscillator
W

R C Potentiostat I, V, t

Cell

Ref.: S. Bruckenstein, M. Shay, Electrochim. Acta, 30(1985)1295.

S. Bruckenstein, S. Swathnaian, Electrochim. Acta, 30(1985)851.
 Illustration of Time-resolved EQCM

Reference fH
Oscillator Counter

Mixer & f Frequency- f/n Multi-

Regulator divider trigger Data High Frequency
Memory Time-base

Working
Oscillator
W

C Potentiostat A/D-D/A Computer

R interface
Cell
 Previous Methods for Determining the Calibration Constant C

Calculation based upon the Sauerbrey formular

(   2.947  1011 gcm1s1 ,   2.648gcm3 )
Ref : Ostrom, G.S.& Buttry, D.A. J. Electroanal. Chem. 256(1988)411.

Measurement based upon electrochemical deposition of Ag

Ref : Bruckenstein, S. & Swathirajan, S. Electrochim. Acta, 30(1985)851.
Keita, B.; Nadjo, L. ; Belanger, D. et al. J. Electroanal. Chem. 384(1995)155.
 Typical EQCM Response at Bare Au

10 0.10

0 0.05
0.00
-10

I /mA
-0.05
f /Hz

-20
-0.10
-30 -0.15

-40 -0.20
-0.25
-50
-0.5 0.0 0.5 1.0 1.5
E / V vs. Ag|AgCl

Scan Rate : 100mV/s, in 1M H2SO4

 Typical EQCM Response of Bare Pt

10 0,2

0 0,1

-10 0,0
f /Hz

I /mA
-20 -0,1

-30 -0,2

-0,5 0,0 0,5 1,0 1,5

E /V vs. Ag|AgCl

Scan Rate : 100mV/s, in 1M H2SO4