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Development and characterization of a microcalorimeter based on a Si-N

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Journal of the Korean Physical Society, Vol. 49, No. 4, October 2006, pp. 1370∼1378

Development and Characterization of a Microcalorimeter Based on

a Si-N Membrane for Measuring a Small Specific Heat
with Submicro-Joule Precision

Ki Sung Suh, Hyung Joon Kim, Yun Daniel Park∗ and Kee Hoon Kim†
Center for Strongly Correlated Materials Research and School of Physics, Seoul National University, Seoul 151-742

Sang-Wook Cheong
Department of Physics and Astronomy, Rutgers University, Piscataway, New Jersey 08854, U.S.A.

(Received 6 March 2006)

We report on development of a silicon-nitride-based microcalorimeter for measuring the heat

capacity of a small single crystal or films over a wide temperature range and under high magnetic
fields. The fabricated calorimeter is adapted to a commercial cryostat equipped with a 9 T magnet
(Quantum Design, PPMSTM ) and is operated by using a custom-made program based on a thermal
relaxation method considering two relaxation times. The measured heat capacity data for Cu are
consistent with the literature values within ∼20 % in a temperature range between 20 and 300 K.
Measurements of a flux-grown LuMnO3 single crystal of ∼300 µg exhibit large residual entropy
below its Néel temperature, which seems to be a common feature in the hexagonal RMnO3 (R =
rare earth) system.

PACS numbers: 07.10.Cm, 07.20.Fw, 65.40.+g

Keywords: Heat capacity, Silicon nitride, MEMS, Microcalorimeter

I. INTRODUCTION single crystalline or a thin-film form, whose heat capac-

The heat capacity provides key basic information on
the physical properties of a material. Fundamental prop-
erties, such as the electron and the phonon densities
of states [1–3], magnetic interactions [4–11], and struc-
tural and electronic phase transitions [12–19], can all be
studied with great detail through heat capacity measure-
ments. Accurate heat capacity measurements, however,
are often complicated and limited by the heat capacity
of the addenda, i.e., an isothermal calorimeter platform
with a sensor and a heater. As a common practice, the
heat capacity of a sample is obtained by subtracting the
addenda heat capacity from the measured total heat ca-
pacity. Therefore, if the addenda contribution is much
larger than that of a sample, the sample heat capacity is
often subject to large errors. Furthermore, above 100 K
a common calorimeter platform made of a thin sapphire
crystal shows a significant phonon specific heat contribu-
tion as high as ∼10−3 – 10−2 J/K so that heat-capacity
measurements on a small-volume sample become increas-
ingly challenging at high temperatures.
To increase the sample quantity has been a tradi-
tional way of circumventing the above problem. How-
ever, the material of interest often exists in a very small
∗ E-mail:
parkyd@phya.snu.ac.kr;
† E-mail: khkim@phya.snu.ac.kr
-1370-
ity only reaches a small fraction of the addenda heat ca-
pacity. Therefore, accurate measurements of its small
heat capacity become quite difficult based on a com-
mon conventional calorimeter. As an alternative ap-
proach, reducing the addenda heat capacity would be
of great help. In fact, numerous efforts have been made
to fabricate novel calorimeters with greatly reduced ad-
denda heat capacities. In particular, a micro-electro-
mechanical-system (MEMS)-based microcalorimeter has
been recently constructed by using a modern semicon-
ductor micro-fabrication technique to produce an ex-
tremely small addenda heat capacity [20–23], thus en-
abling the aforementioned limitations to be overcome.
In this approach, MEMS fabrication techniques, such as
lithography and dry/wet etching, can be used to build
the heater/sensor structure of a calorimeter with mi-
crometer or nanometer length scale. Also in a recent
development, even the specific heats of nano-liters of or-
ganic liquids and bio-materials can be successfully mea-
sured by using a platform with a special structure [24–
26].
In this paper, we report the development and the
characterization of a microcalorimeter based on a sil-
icon nitride (Si-N) membrane structure fabricated by
using a MEMS technique. Section II gives the de-
tailed procedures to fabricate the Si-N microcalorime-
ter. Section III has a description of the characterization
Development and Characterization of a Microcalorimeter Based on· · · – Ki Sung Suh et al. -1371-

of the microcalorimeter. In particular, we will explain

custom-made software based on the so-called curve fit-
ting method (CFM) [27] in detail to show its advantages
over conventional thermal relaxation methods. Both a
small piece of Cu and a ∼300-µg LuMnO3 crystal are
measured to show the performance of the microcalorime-
ter. Finally, Section IV concludes the paper.

II. FABRICATION

1. General Consideration

Reducing the addenda heat capacity can be achieved

by reducing the volume of the calorimeter. However,
a reduction of the lateral size becomes challenging, as
one should make a platform, a heater and a sensor in a
limited area while allowing for enough space to mount
a sample. A thin-film-based calorimeter can be quite
effective in meeting these requirements. Furthermore,
techniques to make a suspended thin film are now well
established in semiconductor fabrication processing. In
choosing suitable materials for a suspended thin film, the
etch chemistry between the thin film and the supporting
frame and the durability of the thin film are important
factors to be considered. In these regards, the etch rate
between Si and Si-N is known to be quite different. Fur-
thermore, a thin film made of Si-N is strong enough to
endure the weights of certain small bulk samples up to
∼1000 µg, making Si-N very attractive for developing a
microcalorimeter. Thus, in this study, we choose Si-N as
a membrane material to develop a microcalorimeter by
use of a semiconductor micro-fabrication technique.
Several research groups so far have been developing
various kinds of microcalorimeters made of Si-N mem-
branes [21, 22]. However, in most previous studies, a
quantitative comparison of the measured data with the
data for a standard sample such as Cu is still lacking so
that actual accuracy of the heat capacity measured by
the microcalorimeter made of a Si-N membrane is not
clearly known. The lack of an accuracy check in the liter-
ature seems to be partly caused by the fact that the ther-
mal conductivity of Si-N is a lot lower than that of metals
such as Au and Cu. As a result, there can be a weak ther-
mal link between a sample and a Si-N membrane, as well
as poor thermal equilibrium of a sample, making accu-
rate heat capacity measurements challenging. Therefore,
in designing a microcalorimeter, we have tried to over-
come those problems by deposition of a metallic isother-
mal layer, as previously reported. However, those efforts
turn out still not to be enough. Furthermore, we have
developed a custom-made program that can correct the
bad thermal link problem between a sample and a mem-
brane. By measuring a piece of standard Cu by use of
the custom-made software, we checked the accuracy of
our microcalorimeter made of a Si-N membrane. We
find that the accuracy of the measurements critically de-
pends on the thermal conductance of the heater/sensor
Fig. 1. Fabrication procedures for the Si-N membrane-
based microcalorimeter: (a) low-stress Si-N deposition using
LPCVD, (b) photolithography to form a heater and a sen-
sor, (c) metallization, (d) lift-off, e) etch mask patterning ,
(f) reactive ion etching of the Si-N layer, (g) removal of the
residual photoresist, (h) Si bulk etching in a hot KOH so-
lution, (i) isothermal layer deposition using a shadow mask,
and (j) fabricated microcalorimeters with different isothermal
layers and heater designs. (see Fig. 2)
wires through the lateral line width and on the thermal
conductance of the deposited materials.
2. Fabrication Procedure
To make a suspended Si-N thin membrane, we used
anisotropic Si bulk etching in a hot KOH solution. De-
tailed fabrication procedures are summarized below and
in Fig. 1.
(a) A double-side polished Si (001) wafer was prepared,
and pattern both sides of the wafer were patterned.
When a single-side-polished wafer is used, the un-
polished side can be attacked in a forthcoming bulk
etch processing due to its rough surface. Low-stress
amorphous silicon nitride was deposited on both
sides of the Si wafer by using a low-pressure chem-
ical vapor deposition (LPCVD) technique. The
thickness of a Si-N membrane was varied from 170
nm to 1 µm. The top-side Si-N was used as an etch
mask of Si during the KOH bulk etching. The Si-N
layer deposited on the bottom side electrically iso-
lated the heater/sensor from the sample and acted
as a platform to hold the sample.
-1372- Journal of the Korean Physical Society, Vol. 49, No. 4, October 2006
(b) Photolithography was used to form heater/sensor
patterns on the bottom surface of the wafer with a
mask-aligner (Karl Süss MJB-3).
(c) A Ti/Au or A Ti/Pt (3 nm / 50 nm) film was de-
posited on the bottom side through e-beam evap-
oration or sputtering.
(d) After a lift-off process, only heater/sensor regions
remained on the wafer.
(e) To form a rectangular etch mask of the Si-N layer
on the top side (∼5 mm × 5 mm area), we pat-
terned it by using the same photolithography tech-
nique. During this photolithography step, the
wafer was well aligned with the mask to within
1◦ because a highly directional etch will be used in
a later step. To cut a calorimeter easily from the
wafer, we separated the each rectangles by a 300-
µm line, which was etched as a V-shaped groove
during a subsequent etching process. To prevent
etching at the corners of rectangles, we left behind
the boundary lines of each calorimeter at every in-
tersection.
(f) To etch the Si-N, we used a reactive ion etcher
(South Bay Technology RIE-2000) with CF4 : O2
= 9 : 1 gas at 100 mTorr and forward power of 60
Watt. In this etch step, the photoresist acted as
an etch mask of Si-N. The total etching time was
5 to 30 min, depending on the thickness of Si-N.
(g) The residual photoresist was removed with ace-
tone.
(h) After Si-N etching with RIE, the exposed Si was
etched anisotropically in a KOH solution (20 wt.%
of water) for about 4 hours. The temperature
was kept at 90 – 95 ◦ C within a hot bath. The
etch rate was found to be ∼2 µm/min. The etch
rate increased with the temperature of the solution
and showed maximum at a 20 wt.% concentration.
With a 33 wt.% and at a temperature about 80
◦
C, the total etch took over 6 hours. As the KOH
etch is directional, ratio between the etch rates for
the [100] and the [111] directions was ∼400 : 1.
Thus, as the etch process went on, an etched sur-
face with a slope of ∼54.7◦ along the (111) surface
was formed. The etch rate of the Si-N layer in
the KOH solution was negligible compared to that
of the silicon region. To avoid breaking the Si-N
membrane during the etching process, we used a
special carrier made of TeflonTM . The heaters and
the sensors showed no significant damage during
the KOH etching. As a result of the bulk etching,
a large (∼5 mm × 5 mm) free-standing membrane
structure was fabricated. The wafer with this thin
nitride membrane was carefully cleaned in deion-
ized water for 30 min.
Fig. 2. Enlarged geometry of the two microcalorimeters,
Type I and Type II. The heater/sensor of Type I is made of
Au film and has a uniform lead width while that of Type II is
made of Pt film and has a lead width that gradually decreases
toward a center region.
(i) After N2 drying, a Au layer of ∼200 nm was evap-
orated on the bottom side of the nitride mem-
brane to enhance thermal conduction between the
calorimeter and the sample and to achieve isother-
mal properties. First, a Ti layer was deposited to
enhance adhesion. To define the Au isothermal
layer, we employed a silicon shadow mask made by
using a similar KOH etching process. The shadow
mask and the Si-N membrane maintain a 100-µm
gap during evaporation.
(j) After the isothermal layer had formed, the wafer
carefully was cut into pieces. To avoid breaking
the membrane, we took care not to touch it. The
V-shaped groove made during the KOH etching
enabled us to cleave calorimeters easily without
breaking the membrane.
We particularly note that in all previously known fab-
rication sequences [21,22], the procedures of (b)-(d), i.e.,
definition and deposition of the heater/sensor, were per-
formed after those of (c)-(h), i.e., the Si bulk etching pro-
cess. It turned out that the specific sequence in the liter-
ature [21,22] has often caused damage to the membrane
during heater/sensor lithography processing, resulting
in a low yield. We find that the above new sequence
makes fabrication procedures much simpler so that the
risk of breaking membranes during processing is greatly
reduced, resulting in a higher yield. Therefore, with a
4-inch Si wafer, we could get 37 devices (1 cm × 1 cm in
size) at the same time. On the other hand, the original
sequence in the literature has been intermittently used
in cases where a single calorimeter is fabricated to test a
lithography condition and a new design.
In this study, two kinds of the microcalorimeters were
fabricated as shown in Fig. 2. The heater/sensor of
Development and Characterization of a Microcalorimeter Based on· · · – Ki Sung Suh et al.
Fig. 3. Schematic diagram of the instrumentation and cir-
cuit connections for the heat-capacity measurements by use
of a microcalorimeter.
Type I is made of Au and has a uniform lead width
in the joint region while that of Type II is made of Pt
and has a lead width that gradually decreases from the
edge region toward the central region. In the latter case,
we tried to confine the heating area to prevent heat-
ing except in the isothermal layer. On the other hand,
both microcalorimeters were fabricated to have the same
heater/sensor line width (thickness), 100 µm (50 nm),
inside the isothermal layer region.
III. MEASUREMENT SCHEME
1. Heat-capacity Measurement Scheme
To measure the heat capacity at low temperatures,
we replaced the sapphire platform in a commercial
calorimeter (for PPMSTM , Quantum Design) with our
microcalorimeter. The temperature of the PPMS was
controlled to regulate the reservoir temperature of the
calorimeter. Before measuring the heat capacity, we cal-
ibrated the sensor by measuring its resistance in a four-
probe configuration. Fig. 3 shows the detailed circuit
wirings used for the heat-capacity measurement. The
ac voltage output of a lock-in amplifier (SR830), VC , is
sent as an input to a current calibrator (Valhalla 2500)
to generate an ac current IS , with a frequency ∼1 kHz
to be applied to the sample. IS is proportional to VC
and is controlled automatically by software to vary from
10 µA to 100 µA. Then, the lock-in amplifier continu-
ously records VS , i.e., the voltage generated across the
temperature sensor. Another thin film made of either by
-1373-
Au or Pt is used as a heater. At each stabilized block
temperature, a source meter (KE236) is turned on for
a specified time to apply a constant dc current IH and
to measure the dc voltage VH generated across the film
heater; then, it is turned off. This heating sequence is
repeated at least two times to record the exponential
temperature variation of the isothermal layer.
We developed a custom-made program based on
LabVIEWTM to control all of above instruments simul-
taneously, to set the block temperature of the calorime-
ter, to measure the exponential temperature variation
of a sensor with the heater current on or off, and to
calculate heat capacity based on the CFM, as explained
below. During the heat capacity measurements, the sam-
ple chamber of the PPMS was evacuated with a turbo-
molecular pump, and a charcoal absorber was attached
at the bottom of the radiation shield.
To test the performance of the microcalorimeter, we
mounted a piece of high-purity Cu (∼500 µg) to a Si-N
membrane covered with a thermal grease (Apiezone N).
The weight of the sample was carefully measured by use
of a microbalance. The heat capacity of the addenda (the
membrane plus the thermal grease) was measured before
mounting the Cu sample. Then, the heat capacity of
the Cu sample was obtained by subtracting the addenda
contribution from the total heat capacity. A small piece
of a flux-grown LuMnO3 crystal with a mass of ∼300
µg was also measured in a similar way at temperatures
between 30 and 140 K.
2. Curve Fitting Method (CFM)
A clever measurement scheme can be another impor-
tant factor in obtaining accurate heat capacity data. For
example, various measurement techniques have been de-
veloped to detect a small variation of the temperature
and to determine the thermal relaxation time accurately
[28–33]; to name a few, a DC thermal relaxation method,
a general heat pulse technique, and an AC calorimet-
ric technique [34–36]. Among them, we have adopted
the CFM in our measurement scheme due to its having
several advantages over the other methods, as explained
below (Section 3.3) [27].
The usual DC thermal relaxation method assumes that
the sample and the platform have perfect thermal con-
duction. Then, the platform is weakly connected to the
thermal reservoir through a finite thermal conductance
λl between the platform (membrane) and the reservoir.
Then, the heat transfer process can be described as
dT
P (t) = c + λl (T − T0 ), (1)
dt
where P , c, and T are the applied power, the heat capac-
ity, and the temperature of a sample, respectively. T0 is
the temperature of the thermal reservoir (Si block). This
predicts an exponential temperature variation with one
-1374- Journal of the Korean Physical Society, Vol. 49, No. 4, October 2006

heater power is on or off:

T 0 = A exp[−t/τ1 ] + B exp[−t/τ2 ] + C. (4)
τ1 is, roughly speaking, the thermal relaxation time for
a relaxation between the addenda platform and the heat
sink, and τ2 is that for a relaxation between the sam-
ple and the platform. In most practical cases, τ2 is not
negligible, so it must be considered if the temperature
variation is to be fitted accurately.
To get a solution of Eq. (3) with the two time con-
stants, we used the CFM [27]. This technique relies on
Eq. (3) to model the time-dependent temperature vari-
ation of a microcalorimeter and a sample to the applied
time-dependent heat sequence. From Eq. (3), one can
get the following equation:
c
λs
Γ(t) = H(t)
c0 + c + c λλsl
1 −λl
+ λl
Q(t) + S(t) (5)
c0 + c + c λs c + c + c λλsl
0

 
0
where Γ(t) ≡ T 0 (t) − T 0 (0), H(t) ≡ P (t) − c0 dT
dt0 
 −
  t0 =t
dT 0 
 Rt Rt
Fig. 4. (a) Schematic diagram explaining the thermal re-
laxation model used in the curved fitting method (CFM).
With this model, the temperature of the microcalorimeter
(T 0 ) can be described as an exponentially varying function
with the relaxation times τ1 and τ2 . See texts for details.
(b) Variation of the membrane temperature when a constant
heater current is turned on and subsequently turned off. The
start and the end times of the heater current are indicated by
two arrows. The blown-up inset shows a fast increase (drop)
of temperature just after the heater current start (end) due
to the presence of the τ2 effects. The red line refers to fits
to the experimental data (solid circles) by using the CFM,
resulting in τ1 = 4.77 s and τ2 =0.11 s.
time constant, τ , when a constant heater power is turned
on or off:
T = A exp[−t/τ ] + B. (2)
The τ is given as τ = c/λl . However, when a finite ther-
mal conduction exists between a sample and a membrane
platform, the temperature difference between them must
also be considered (see Fig. 4(a)). Thus, Eq. (1) should
be extended as
0

P (t) = c0 dT 0 0
dt + λs (T − T ) + λl (T − T0 ),
dT 0 (3)
0 = c dt + λs (T − T ),
in which c0 and T 0 are the heat capacity and the tem-
perature of the platform and λs is a finite thermal con-
ductance between the sample and the platform. These
equations predict an exponential temperature variation
with two time constants, τ1 and τ2 , when the constant
dt0  , Q(t) ≡ 0 P (t0 )dt0 , and S(t) ≡ 0 T 0 (t0 )dt0 .
t0 =0
Γ(t), H(t), Q(t), and S(t) are determined experimentally
as functions of time. By employing a least-squares fitting
method, the constant coefficients in front of the H(t), the
Q(t), and the S(t) terms can be determined to match
with the experimental Γ(t) [27].
3. Advantages of CFM
The CFM has several advantages over the single-time
thermal relaxation method described in Eq. (1). In par-
ticular, the advantages can be significant in measuring
the heat capacity of the a microcalorimeter in which the
τ2 effect can often cause a serious problem due to the bad
thermal conduction between the sample and the isother-
mal layer. The τ2 effect is partly caused by the fact that
one cannot press the sample on the membrane due to
the membrane’s fragility. Furthermore, the usual ther-
mal relaxation method with a single relaxation time at
least requires a total measurement time of ∼10τ to de-
termine the thermal conductance λl between the sample
and the thermal sink. However, in the CFM, a total mea-
surement time of 1 – 2 τ is enough to reliably determine
the three unknown coefficients in Eq. (5), with which one
can calculate c0 , λs , and λl . [c is determined indepen-
dently from the addenda measurement.] In addition, the
heat capacity based on the CFM can be determined even
when the temperature of the heat sink changes linearly
in time [27].
Fig. 4 (b) illustrates the fitting results based on the
CFM of a microcalorimeter. Just after applying a con-
stant IH for ∼1.5 times the total relaxation time, we
Development and Characterization of a Microcalorimeter Based on· · · – Ki Sung Suh et al.
Fig. 5. Comparison between the temperature dependent
heat capacity of a commercial sapphire platform (Quantum
Design, PPMSTM ) and that of a Si-N membrane platform in
the microcalorimeter fabricated in this study (Type I). The
heat capacity of the membrane platform is smaller by 3 to 4
orders of magnitudes than that of the commercial sapphire
platform.
turned off the heater. In this procedure, the tempera-
ture of the membrane is continuously measured with a
lock-in amplifier to record the exponential increase (or
decrease) of the temperature when the heater is turned
on (off). The value of the applied IH is adjusted to pro-
duce a temperature variation of less than ∼3 % of the
main block temperature. In addition to the main expo-
nential variation, however, the measured temperatures
(solid circles in Fig. 4 (b)) show a very fast exponential
variation with a time constant τ2 . The fast exponential
variation comes from a finite λs in Eq. (3). The fits
(solid line) based on the CFM result in τ1 = 4.77s and
τ2 = 0.11s. Note that the rise and the fall times for the
heater current were less than 5 ms so that they hardly
affected τ2 = 0.11s.
IV. RESULTS AND DISCUSSION
1. Measurements of Cu
To compare the performance of our microcalorimeters
to that of a commercial calorimeter, we show the ad-
denda heat capacity of the Type I microcalorimeter in
Fig. 5 at temperatures between 20 and 360 K. The heat
capacity of the addenda is 3 to 4 orders of magnitude
smaller than that of the commercial sapphire platform,
enabling us to obtain the sensitivity of sample heat ca-
pacity down to ∼1 µJ/K. Due to the sensitivity, a sharp
peak is observed around 30 K and is thought to be come
from an α − β phase transition of solid oxygen trapped
in the membrane surface [37].
-1375-
Fig. 6. Comparison of the specific heat data of standard
oxygen-free-high-purity Cu as measured with the two differ-
ent types of microcalorimeters. The inset shows the calcu-
lated relative errors of the measured Cp values as compared
with the standard data. Above 60 K, the errors for Type II
become smaller than those of Type I (see the text for details)
while below 60 K, they are larger.
To check the performance of the two types of the mi-
crocalorimeter, we measured the specific heat of a 550-
µg piece of Cu with, based on the CFM measurement
scheme. Fig. 6 compares the determined Cu data with
the standard data [38]. The inset shows the relative er-
rors calculated from these data. We find that the errors
for Type I are only ∼10 % below 60 K and increase to
as large as 30 % above 60 K while those for Type II are
less than 20 % above ∼60 K and increase significantly
below ∼60 K. These intriguing temperature-dependent
errors in rather similar microcalorimeters suggest that
the details of the geometry and the different materials of
the microcalorimeters can sensitively affect the quality
of the measured heat capacity.
To further understand the origin of the errors, we com-
pared the thermal conductance λl between the platform
and the thermal reservoir of each microcalorimeter in
Fig. 7. Interestingly, we find that the temperature de-
pendence of λl for each microcalorimeter has a shape
very similar to that of the errors shown in the inset of
Fig. 6. This finding suggests that the magnitude of λl
can be an important parameter for producing reliable
heat-capacity data from the microcalorimeter. Further-
more, the apparently increased heat capacity, as com-
pared with the standard value, is most likely caused by
an unrecognized loss of heater power due to an inaccu-
rate determination of average temperature of the mem-
brane platform. In fact, the average temperature of the
sensor element can critically depend on the isothermal
condition of the membrane platform. The correlation
between Cp errors and λl indicate that as λl increases,
the temperature gradient near the edge of the platform
also increases, resulting in an inaccurate determination
-1376- Journal of the Korean Physical Society, Vol. 49, No. 4, October 2006
Fig. 7. Comparison between experimentally determined λl
(symbols) and the theoretical estimates (lines) for (a) Type I
and (b) Type II. In both (a) and (b), the dashed lines repre-
sent the contributions of the metal leads to the theoretically
estimated λl while the dotted lines represent those of the Si-
N membrane. To calculate the metal-lead contribution, the
number of leads, their thickness, and their width are multi-
plied by the thermal conductivity of each metal given in the
literature (see the text for details). The contribution of Si-N
is also estimated from the literature values [40] multiplied by
the thickness and a constant α.
of the average temperature. Through this mechanism,
we expect the amount of power loss and resultant Cp
errors to be directly related to the magnitude of λl , as
observed.
2. Estimation of thermal conductance
To further confirm the critical role of λl in the mea-
surement of Cp , we tried to estimate actual λl in both
Type I and Type II microcalorimeters. We can as-
sume that the thermal conductance λl can be divided
into two main contributions: one from the metallic leads
and the other from the Si-N membrane layer. In other
words, we can write λl (T ) ≡ λAu (T ) + λSi−N (T ) =
ntAu wAu kAu (T )/lAu + atSi−N kSi−N (T ) for Type I and
λl (T ) ≡ λPt (T ) + λSi−N (T ) = ntPt wPt kPt (T )/lPt +
atSi−N kSi−N (T ) for Type II, where n, t, w, and k are the
number of links, the thickness, the width, and the ther-
mal conductivity of the specific material, respectively.
While the thermal conductivities of Au and Pt, kAu (T )
and kPt (T ), can be taken from the literature [39], the
parameters related to the dimensions of electrodes can
be directly determined from Fig. 2, which gives as n
= 4 and tAu = tpt = 50 nm. Furthermore, for Type I,
the ratio between the width and the length of electrode
was wAu /lAu = 0.1, as determined from the electrode
geometry. For Type II, wPt /lpt = 1.1 was obtained af-
ter taking an integrated average of wPt that varied from
100 mm to 600 mm. By use of the ellipsometry tech-
nique, we measured thicknesses of silicon nitride tSi−N
for Type I and II as 950 nm and 750 nm, respectively.
The thermal conductivity of amorphous silicon nitride,
kSi−N (T ), was taken from the literature [40] with a ap-
proach similar to one used in Ref. 41. After combining
all of these experimental results, considering the design
of our microcalorimeter, we adjusted the 2D geometrical
number α as the only free-fitting parameter. In this way,
we could estimate separately the values for λAu and λPt
(dashed lines) and λSi−N (dotted lines) for both types
of calorimeters, resulting in the total estimated λl (solid
lines). The best α value to match the estimated λl with
the experimental one (symbols) in Fig. 7 is found to be
∼20 for both calorimeters. From Ref. 39, the bulk ther-
mal conductivities of Au and Pt show peaks at ∼10 K.
This results in a sudden increase of thermal conductance
below 60 K for Type II. For Type I, on the other hand,
this increase was compensated for by the thermal con-
ductance decrease of the Si-N membrane, resulting in a
quasi-linear decrease. The difference between the mea-
sured and the estimated thermal conductances above 100
K is thought to come from thermal radiation.
The close match between the estimated and measured
λl (T ) of the thermal link and the measured one strongly
supports that λl (T ) is a key parameter that causes the
errors in the Cp measured by using the microcalorime-
ter. In other words, a large value of λl can generate a
large thermal gradient in the heater/sensor leads that
will cause an unexpected heat loss in the isothermal re-
gion. Therefore, in future, this problem should be cir-
cumvented by careful adjustment of λl (T ), composed of
contributions from the metallic leads and the Si-N mem-
brane, by narrowing electrical leads or by using different
electrode materials with low thermal conductivities.
3. Measurements on the LuMnO3 Crystal
We further tested the performance of Type I by mea-
suring the specific heat of a 300-µg single-crystal of
LuMnO3 . To correct the above mentioned measurement
errors, we measured Cu just before the measurement of
LuMnO3 ; then, we corrected the LuMnO3 specific heat
data by using the same factor that were used to adjust
the measured Cu data to the literature value. The cor-
rection factor was about 10 % below 60 K and less than
30 % above it, as illustrated in the inset of Fig. 6. The
inset of Fig. 8 shows the corrected C vs. T data (solid
circles) for the LuMnO3 crystal. To extract magnetic
specific-heat contribution from the Mn3+ spin interac-
tion, we estimated the phonon contribution was esti-
mated by use of the Debye model. We used two Debye
temperatures, 420 K for heavy ions (Lu and Mn) and 800
K for light ions (O) [11]. As the inset of Fig. 8 shows, the
specific-heat data (solid circles) of LuMnO3 around 150
K show good agreement with the phonon specific-heat
(the solid line) predicted by using the Debye model with
Development and Characterization of a Microcalorimeter Based on· · · – Ki Sung Suh et al.
Fig. 8. Magnetic specific heat over temperature Cm /T
(left scale) of LuMnO3 (300 µg) obtained after subtracting
the phonon contribution estimated as a solid line in the inset
(see texts for details). The solid line represents the mag-
netic entropy (right scale) obtained by integration of Cm /T .
For the low temperature integration, Cm /T is assumed to be
proportional to T 2 below 25 K. The entropy at T = 150 K is
estimated to be 15.034 Jmol−1 K−1 , which is close to the ex-
pected ∆Sm = R ln(2S + 1) = 13.38 Jmol−1 K−1 for a Mn3+
ion (S = 2).
the two Debye temperatures. The magnetic specific-heat
Cm over temperature, Cm /T , was obtained by subtract-
ing the phonon contribution from the total specific-heat,
as shown in the left panel of Fig. 8.
The sharp peak around ∼90 K corresponds to an anti-
ferromagnetic ordering of Mn3+ spins, as similarly ob-
served in a polycrystalline LuMnO3 sample [11]. By
integrating Cm /T from 0 to 150 K, we found the en-
tropy of this system is found to be 15.034 Jmol−1 K−1 .
This value is closed to the expected magnetic entropy
change ∆Sm with the long range antiferromagnetic or-
dering of Mn3+ spins with S = 2; ∆Sm = R ln(2S + 1)
= 13.38 Jmol−1 K−1 . We also note that ∆Sm is close
to the value obtained from a polycrystalline sample of
a relatively large quantity, ∼10 mg, or size, ∼1 mm3
[11]. Furthermore, the shape of Cm /T at low tempera-
tures below 90 K is characterized by an additional hump
around 60 K, which seems to be a common feature in
the present RMnO3 (R = rare earth) system. While the
origin of this low-temperature hump should be further
clarified, all of these results consistently prove that the
specific heat of a small crystal can be reliably measured
by using the microcalorimeters fabricated in this study.
V. SUMMARY
We developed a microcalorimeter made of a silicon ni-
tride membrane by using MEMS techniques. To test the
performance of the microcalorimeter, we utilized ac in-
strumentation and custom-made LabVIEWTM software
-1377-
based on a curve-fitting method. The microcalorime-
ter was successfully adapted to a commercial cryostat,
PPMSTM , with minor modifications. The measured
standard Cu data showed errors within the ∼20 % range.
We also measured the specific heat of LuMnO3 by using
the standard Cu data to correct errors. The corrected
specific heat and the calculated entropy show good agree-
ments with the data in the literature.
As we find in this study, the performance of the mi-
crocalorimeter critically depends on the thermal conduc-
tance between the heat sink and the membrane and on
the thermal gradients in the isothermal layer. There-
fore, if accuracy is to be improved, it is quite desirable
to incorporate a new design concept with a smaller line
width and a more confined heater/sensor region or to
use a new electrode material with a low thermal conduc-
tivity. We are working toward this direction to improve
the accuracy. The microcalorimeter fabricated in this
work can become an indispensable laboratory asset to
investigate the thermodynamics of various samples on
a mesoscopic length scale, such as a microgram single
crystal and a thousand-angstrom-thick thin film, and a
nano-liter solution of DNA molecules. Furthermore, heat
capacity measurements above 300 K with the present mi-
crocalorimeter are quite promising due to its small ad-
denda heat capacity value even above room temperature.
ACKNOWLEDGMENTS
This work is supported by the Korea Research Founda-
tion (KRF) of the Korean Government (Ministry of Ed-
ucation & Human Resources Development: MOEHRD)
(R08-2004-000-10228-0) and the Korea Science and En-
gineering Foundation (KOSEF) and Samsung Electron-
ics Endowment through Center for Strongly Correlated
Materials Research (CSCMR). KHK is also partially sup-
ported by Samsung Semiconductors. This work is also
partly supported by the Seoul Research Business Devel-
opment (R&BD) Program.
REFERENCES
[1] J. E. Lorenzo, R. Currat, A. J. Dianoux, P. Monceau
and E. Levy, Phys. Rev. B 53, 8316 (1996).
[2] S. E. Regan and G. J. Morgan, J. Phys.: Condens. Mat-
ter 4, L195 (1992).
[3] J. W. Loram, J. Phys. C: Solid State Phys. 19, 6113
(1986).
[4] Y. Jo, J. G. Park, H. C. Kim, H. C. Ri, S. Xu, Y. Morit-
omo, A. D. Hillier and S. H. Kilcoyne, J. Korean Phys.
Soc. 47, 123 (2005).
[5] K. N. Lee, R. Bachmann, T. H. Geballe and J. P. Maita,
Phys. Rev. B 2, 4580 (1970).
[6] P. H. Keesom, Phys. Rev. B 33, 6512 (1986).
-1378- Journal of the Korean Physical Society, Vol. 49, No. 4, October 2006
[7] F. Bouquet, Y. Wang, I. Sheikin, T. Plackowski, A.
Junod, S. Lee and S. Tajima, Phys. Rev. Lett. 89, 257001
(2002).
[8] J. Konig, H. H. Lin and A. H. MacDonald, Phys. Rev.
Lett. 84, 5628 (2000).
[9] P. A. Sharma, J. S. Ahn, N. Hur, S. Park, S. B. Kim, S.
Lee, J. G. Park, S. Guha and S. W. Cheong, Phys. Rev.
Lett. 93, 177202 (2004).
[10] H. W. Xu, J. Iwasaki, T. Shimizu, H. Satoh and N.
Kamegashira, J. Alloys Compd. 221, 274 (1995).
[11] D. G. Tomuta, S. Ramakrishnan, G. J. Nieuwenhuys
and J. A. Mydosh, J. Phys.: Condens. Matter 13, 4543
(2001).
[12] Y. W. Song and B. A. Strukov, J. Korean Phys. Soc. 35,
362 (1999).
[13] H. Shigematsu, Y. Akishige. H. Mashiyama, T. Tojo, H.
Kawaji, T. Atake and T. Matsui, J. Korean Phys. Soc.
46, 235 (2005).
[14] H. Y. Yoon, S. H. Park, Y. H. Jeong and W. K. Choo,
J. Korean Phys. Soc. 35, S1499 (1999).
[15] M. Barmatz, L. R. Testardi, F. J. Di Salvo and J. M. E.
Harper, Phys. Rev. B 13, 4637 (1976).
[16] I. Hatta and W. Rehwald, J. Phys. C: Solid State Phys.
10, 2075 (1977).
[17] K. R. Juraitis, J. B. Domiciano and W. Sano, Phys. Rev.
B 42, 2586 (1990).
[18] L. R. Testardi, Phys. Rev. B 12, 3849 (1975).
[19] V. N. Smolyaninova, K. Ghosh and R. L. Greene, Phys.
Rev. B 58, R14725 (1998).
[20] S. G. Doettinger-Zech, M. Uhl, D. L. Sisson and A. Ka-
pitulnik, Rev. Sci. Instrum. 72, 2398 (2001).
[21] D. W. Denlinger, E. N. Abarra, K. Allen, P. W. Rooney,
M. T. Messer, S. K. Watson and F. Hellman, Rev. Sci.
Instrum. 65, 946 (1994).
[22] S. L. Lai, G. Ramanath, L. H. Allen, P. Infante and Z.
Ma, Appl. Phys. Lett. 67, 1229 (1995).
[23] Y. Y. Zhang and S. Tadigadapa, Appl. Phys. Lett. 86,
(2005).
[24] E. A. Olson, M. Y. Efremov, A. T. Kwan, S. Lai, V.
Petrova, F. Schiettekatte, J. T. Warren, M. Zhang and
View publication stats
L. H. Allen, Appl. Phys. Lett. 77, 2671 (2000).
[25] M. Y. Efremov, E. A. Olson, M. Zhang, Z. Zhang and L.
H. Allen, Phys. Rev. Lett. 91, (2003).
[26] Z. S. Zhang, O. M. Wilson, M. Y. Efremov, E. A. Olson,
P. V. Braun, W. Senaratne, C. K. Ober, M. Zhang and
L. H. Allen, Appl. Phys. Lett. 84, 5198 (2004).
[27] J. S. Hwang, K. J. Lin and C. Tien, Rev. Sci. Instrum.
68, 94 (1997).
[28] C. N. King, Ph. D. Dissertation, Stanford University,
1972.
[29] R. E. Schwall, Ph. D. Dissertation, Stanford University,
1972.
[30] R. Bachmann, F. J. DiSalvo Jr., T. H. Geballe, R. L.
Greene, R. E. Howard, C. N. King, H. C. Kirsch, K. N.
Lee, R. E. Schwall, H.-U. Thomas and R. B. Zubeck,
Rev. Sci. Instrum. 43, 205 (1972).
[31] R. E. Schwall, R. E. Howard and G. R. Stewart, Rev.
Sci. Instrum. 46, 1054 (1975).
[32] H. Wilhelm, T. Luhmann, T. Rus and F. Steglich, Rev.
Sci. Instrum. 75, 2700 (2004).
[33] R. W. Newsome and E. Y. Andrei, Rev. Sci. Instrum.
75, 104 (2004).
[34] J. M. E. Harper, Ph. D. Dissertation, Stanford Univer-
sity, 1975.
[35] F. Pesty and P. Garoche, Rev. Sci. Instrum. 74, 2575
(2003).
[36] J. F. Cochran, C. A. Shiffman and J. E. Neighbor, Rev.
Sci. Instrum. 37, 499 (1966).
[37] B. Kuchta, T. Luty and R. J. Meier, J. Phys. C: Solid
State Phys. 20, 585 (1987).
[38] Guenter Ahlers, Rev. Sci. Instrum. 37, 477 (1966).
[39] David R. Lide, CRC Handbook of Chemistry and
Physics: a Ready-Reference Book of Chemical and Phys-
ical Data (CRC Press, Boca Raton, 1994), p. 161.
[40] B. L. Zink and F. Hellman, Solid State Commun. 129,
199 (2004).
[41] B. Revaz, B. L. Zink, D. O’Neil, L. Hull and F. Hellman,
Rev. Sci. Instrum. 74, 4389 (2003).