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A Thin Film Module For Thermoelectric Conversion
A Thin Film Module For Thermoelectric Conversion
Abstraet--A thermoelectric converter based on thin film technology, in which thermocouples are de-
posited by vacuum evaporation of Bi-Te-Sb-Se doped alloys onto a thin polyimide film, is presented
for application in a plutonium battery as power supply in a biomedical device.
High figure of merit and good reproducibility of characteristics of the films are attained by means
of an appropriate technique of evaporation and subsequent annealing, the fundamentals of which
are described in detail.
NN
decreases rapidly with input voltages below 0.6 V.
ab c d
In most plutonium batteries available up to nob
[1-4] thermoelectric conversion is obtained by an
array of bar thermoelements with extremity connec-
f
tions.
Materials in use are doped semiconductor alloys
of Bi, Te, Se, Sb compounds and the thermoelements
are obtained by slicing sintered blocks. Since
mechanical properties of these materials are poor,
high miniaturization is difficult to achieve, and the B
number of thermocouples fitting in the space avail-
able makes it impossible to obtain output voltages Fig. 1. Scheme of a thin film thermoelectric converter, (al,
in excess of 1 V with this kind of converter. (b) thermoelectric legs, (c) connecting bridges, (d) flexible
insulating substrate, (e) assembled module, (f) heat source.
In order to overcome these limitations, a thermoe- A--Single series _ connection; B--Series-parallel
lectric module based on thin film technology has been connection.
55
56 CHINAGL1A, VALLANA AND BOSIO: FILM MODULE
and then rolled so that a compact device with a high of-merit thin films by vacuum evaporation followed
number of thermocouples can be obtained. by annealing. The Pu-238 capsule is thermally insu-
The thin film technology offers, in principle, many lated by a vacuum system which acts as mechanical
advantages in the design of a direct conversion device. support, so that the radial dimension is kept at a
The cross section of each thermoelement can be minimum.
reduced to very small figures in comparison with
those attainable with the same material in bulk form.
As a consequence it is possible to get a high number
2. THEORETICAL BACKGROUND
of thermocouples resulting in a high output voltage
without affecting power output and conversion effi- Let us recall the basic equations of thermoelectric
ciency. energy conversion, in order to deduce interesting con-
Another advantage is represented by the connec- siderations for the case of an array of thin film ther-
tions between thermocouple legs, which can be made moelements deposited onto a substrate.
of thin films of suitable metals with non-diffusion It is well known [8, 9], that if:
properties, thus avoiding problems of impurity
W is the electrical power output from the battery,
migration into the semiconductor materials.
Qt is the thermal power flowing through thermoele-
Direct conversion devices based on this concept
meats,
can attain limited figures of heat capacity and thermal
$1,2 is the Secbeck coefficient of the couple of mater-
conductance and are therefore suitable for various
ials 1 and 2,
kind of thermometric applications, such as micro-
k~ (i = 1,2) is the thermal conductivity of material i,
calorimeters of good sensitivity and response time,
ai (i = 1,2) is the electrical conductivity of material
devices for measuring spot temperature in a small
i,
volume or surface temperature by applying the hot
junctions zone to the body surface. Z = $1,2
Another kind of application concerns the measure- x/kiP1 + x/'k2P2
ment of radiation energy, which can be attained, for
is the figure of merit of the couple l, 2
instance, by an array of series connected thermoele-
T1, TOare the absolute temperatures respectively of hot
ments on a plane surface, with hot junctions covered
and cold junctions of thermocouples,
by a n absorber with respect to the wavelengths of
R~. is the external load connected to the battery,
interest, and cold junctions shielded against radiation
R~ is the internal resistance of the battery,
and thermally connected with the heat sink.
Ai (i = 1,2) is the overall cross section of material
Since all the above applications require direct con-
i,
version of thermal into electrical energy, a general
Kt is the overall thermal conductance of the thermo-
requirement for thin film materal is a high value of
elements,
figure of merit Z. In particular for thermometric ap-
Ko is the joint thermal conductance of the insulating
plications, it is also required that the Seebeck coeffi-
system and of the thermoelements supporting system,
cient S be high.
the efficiency of conversion is a function of the ratios
For several years researchers have been working
R ~ R i and AlIA 2 and reaches the maximum value
towards the realization of a thin film conversion
device [5-7]. The results however were not, until now,
AT M - 1
encouraging, owing to the difficulty of obtaining thin
,//max T 1 M -.1- To/T 1 (1)
films of good thermoelectric properties and high sta-
bility with time, in the desired configuration. when
Furthermore, the requirements which must be met
by the supporting substrate (low electrical and ther- R L _ X/1 + Z T = M , (2)
mal conductivity, good mechanical properties, dimen- Ri
sional and chemical stability at the temperatures A1 / ~10"1 (3)
reached during the film deposition) limit the choice A2 ~/k2 a2'
to the field of polyimide resins. With these materials,
however, a substrate thermal conductance lower than where:
the thermoelement conductance cannot in practice be AT = T1 - To
attained, and, as a consequence, high efficiency of the
conversion device is obtained only on the condition T TI+To
that an insulating system with very low thermal con- 2
ductance is available.
This paper describes a thin film thermoelectric From the above expression for efficiency it is poss-
module to be used with a Plutonium-238 heat source ible to derive an approximate relation which is linear
for the power supply of cardiac pacemakers. with respect to the temperature.
High conversion efficiency has been achieved by Since in the field of interest T < 330°K always, it
setting up a proper technique leading to high-figure- happens that, even for the highest attainable value
CHINAGLIA, VALLANA AND BOSIO: FILM MODULE 57
of Z(~ 3"10-3°K-1), Z T < 1 and one can consider and the electrical power is given by:
Optimum conditions are therefore fulfilled when the is less than a critical value of damage for thermoelec-
heat flow from the source is equally distributed tric material;
between thermoelements and insulating-supporting (b) to set up a deposition apparatus which allows
materials. In this case the electrical power output is to get a thickness ti of thin films such that:
directly proportional to the figure of merit of the
ks
couple of materials 1 and 2. ti >~ ts ~ . (14)
In a thin film conversion device further remarks
can be made. As a matter of fact, in this case the
3. MODULE
presence of a substrate onto which the film must be
deposited determines a dependence between Ko and For the realization of the thermoelectric module
Kt due to the fixed ratio 2 between the thermal con- a particular evaporation technique (10) has been set
ductances of the substrate and the films: up, the fundamentals of which will be discussed in
a following section.
2 = ks ts (10) As a substrate we chose a film of Kapton® poly-
?(kit1 + k2t2i" mide resin, 12.5 #m thick. This kind of resin is avail-
able in foils of excellent mechanical properties and
where:
tolerates exposure up to 250°C occurring in the eva-
ks is the thermal conductivity of the substrate; poration and annealing process without dimensional
t s is the thickness of the substrate; alterations. The thermal conductivity is limited to
t i (i = 1,2) is the thickness of thin film of material 5.5 × 10 -3 W/cm °C which is the lowest available
i; for this kind of material.
3' is the ratio between the deposition area of the A thermoelectric module consists of 3 strips, 35 mm
thermoelements and the substrate surface. wide and 1050 mm long, connected in series by means
of electrical and mechanical bonds.
The following relation must hold for the thermal con-
Each strip holds 518 thermocouple legs series con-
ductance Ki,s of the insulating system:
nected by gold bridges which are also deposited by
vacuum evaporation.
k~ts ]
(11) The materials of thermocouples are alloys of Bi--
Kin~ <~ K, 1 3)(kit I + kzt2 ) ,
Te-Se-Sb compounds with doping agents, which
exhibit semiconductor behaviour. Their character-
® Du Pont: De Nemour trade name. istics in thin film form are listed in Table 1.
58 CHINAGLIA, VALLANA AND BOSIO: FILM MODULE
Table 1. Thermoelectric characteristics of thin film thermo- Table 2. Physical characteristics of thin film thermoelectric
couples in the direct conversion module module
4. EXPERIMENTAL METHODS
I I I III
1000 Bi 2-1.355 Sbl.355 Te3÷o.7 HEATING • • II
500
t,211 pm
0 t I I I I I I
2.0 2.2 2A 2.6 2.8 3,0 3.2
L [10-' OK"]
T
Fig. 4. Variation of electrical conductivity with repeated annealing cycles in a thin film of p-1 type
alloy.
~_~ zoo
c/)
100
I II
HEATING • &
Bi 2-1.35, Sbl.3s5 Te 3+o.~ COOLING O A
Tc,,1090°C Ts,,170°C t,2.11 lum
I I I I
200 300 400 500
T K]
Fig. 5. Variation of Seebeck coefficient with repeated annealing cycles in a thin film of p-1 type
alloy.
E.C. 16 1/2 E
60 CHINAGLIA, VALLANA AND BOSIO: FILM MODULE
Bi 2 Te3_o, 5 S e o . 5 I 14
HEATING • •
Tc.1300°C Ts.125 °C
COOLING O Z~
t . 0 . 3 5 ~Jm
-200
:> - lO0
I t I
200 300 400 500
Fig. 7. Variation of Seebeck coefficient with repeated annealing cycles in a thin film of n 1 type
alloy.
CHINAGLIA, VALLANA ANt) BOSIO: FILM MODULE 61
Bi 2 Te 3,13
Tc,1000 °C Ts,55°C
%
(n
- 200
-100
t - 0,45 pm
J HEATING •
I
•
II
COOLING 0 ZI
o i J i , I i i i
200 300 ,oo ,oo
r [OK]
Fig. 9. Variation of Seebeck coefficient with repeated annealing cycles in a thin film of n-2 type
alloy.
62 CHINAGLIA, VALLANA AND BOSIO: FILM MODULE
Bi2-1,~sSb~55Tes+o~
1,0.t0
TYPE
AFTER ANNEALING
0.1.5
0,2.13
I I ' ' i , [ r i ~ i I
lO 20 .30 40
9o
BEFORE ANNEALING
L.
._ 1~).I0
0.1.5 I
' I
10
'
A i i , I
20
' i l
--
' I
30
,~ , I , I
40
'
e*
Fig. 11. X-ray diffraction spectra for a thin film of p-1 type alloy taken before and after annealing
cycles.
CHINAGLIA, VALLANA AND BOSIO: FILM MODULE 63
Bi 2 Te 3,13
TYPE n
AFTER ANNEALING
1.0.10
5 1.0,16
0.t`5 tl 1115
0123 1~2511E6
BEFORE ANNEALING
0.0.6
Bi2Te S,4
0.1,5
TYPE n
AFTER ANNEALING
1.O.lO
I I . . . . I , 4, , I
10 20 30 40
eo
0.1,5
BEFORE ANNEALING
1.1.0
1~1o
1.1.15
lO 2o SO 40
eo
Fig. 13. X-ray diffraction spectra for a thin film of n-3 type alloy taken before and after annealing
cycles.
64 CHINAGLIA, VALLANA AND BOSIO: FILM MODULE
, , F:o w]
\r ~ 0~11~'
~ Bi"1"355 S b " s s 5 Te 3 ÷ °,7
200 tJ -\~,\
4 ?x\x
100 - \ x
\
%
10
i J ~ ~llllll-
L
100
i i ~llllll
1000
I I IIIIIII
10"000
I I I illil
0~* [l~l.-lcm-1J
Fig. 14. Plot of Seebeck coefficient and electrical conductivity for thin films of p-1 type alloy after
annealing.
Thermal power at beginning of life is 122 mW, cor- system with thermal shields with an overall thermal
responding to an c~ activity of 3.75 Ci. conductance of 1.38 mW/°C. Since thermal conduc-
The capsule is designed to meet the ENEA require- tance of module-substrate system is 1.74 mW/°C, the
ments for specific biomedical applications. resulting temperature difference between hot and cold
The thermal insulation consists of an in-vacuum junctions is 38.5°C.
s' [,o-'w I
, ~ ' , \ / t ..... ..i
-200 ',,¢,,,,,%,'
, \
I- ", \ll',~\',
I \ ". " ~ ' "
I-==.I
" ~ -100
i ', %. ,,,~,%. "~,,"
%%
[,,'," cm-']
Fig. 15. Plot of Seebeck coefficient and electrical conductivity for thin films of n-2 type alloy after
annealing.
CHINAGLIA, VALLANA ANt) BOSIO: FILM MODULE 65