Journal of ElectronicMaterials,Vo91 26, No.

8, 1997

Regular Issue Paper

Cryogenic Thermoelectric Cooler with a Passive Branch

C. CIPAGAUTA MINO, t J.W. COCHRANE, '~E.H. VOLCKMANN,* and G.J. RUSSELL ~ *Advanced Electronic Materials Group, School of Physics, The University of New South Wales, Sydney, NSW 2052 Australia *Marlow Industries, Inc., 10451 Vista Park Road, Dallas, TX 75238-1645 Cryogenic thermoelectric coolers have been fabricated from an active element (polycrystalline Bi0.ssSbo.12) and three different passive elements, a high-T c superconductor (polycrystalline YBa2Cu3OT.~), and lengths of high purity copper and aluminum wires. The results for a single couple show that for low, hot junction (sink) temperatures the superconducting element gives rise to maxim u m temperature drops of 6.6 degrees K at 70K and 7.3 degrees K at 75K in applied magnetic fields of 0.0 and 0.07 T, respectively. Temperature drops of ~9 and 11K, respectively, are expected for such a couple when form factors are taken into account. The copper couple with an applied magnetic field resulted in large cooling AT values at Thot = 150 and 293K, indicating the importance of metallic passive elements for intermediate sink temperatures. Performance curves for the superconductor based cryogenic thermoelectric cooler show promise with further improvement possible by the use of single crystalline Bi0 ssSb0.15.

Key words: Bi0.ssSi0.12, coolers, cryogenic thermoelectric, high-T c superconductors

INTRODUCTION A thermoelectric cooler or Peltier refrigerator operating at a hot junction (sink) temperature of liquid nitrogen, would be very useful for the cooling of electronic and optoelectric devices below 77K to improve their efficiency and sensitivity. The advantages of the thermoelectric cooler over other available cooling systems, which are more efficient, are its low cost, small size and weight, no moving components, low electrical noise, maintenance-free operation, long life, minimal environmental impact, and ease of providing precise temperature control. The performance of a single stage cooler, which is shown schematically in Fig. 1, is characterized by its figure of merit 1,2

subscripts p and n refer to the positive and negative branch materials. The m a x i m u m temperature difference across this cooler can be realized if the following equation involving the form factor (UA), where g is the length and A the cross-sectional area of a branch, is satisfied, 1,2
(Pn /~n)(~n / A 2__ n)(pp

/tp)(~p/Ap)2

(2)

Thus, the m a x i m u m temperature difference, for a cold junction temperature TcolVis given by 2 ( A T ) ~ = ZTi2ola/ 2 (3)

z-- (s,-so)2/Lt opp)

[-/

\1/2

\1/272

(1)

where S is the Seebeck coefficient, X is the thermal conductivity, p is the electrical resistivity, and the (Received March 3, 1997; accepted March 28, 1997)

According to the analysis of Goldsmid et al.,a the best material for the negative branch of the thermoelement at liquid nitrogen temperatures are the alloys of bismuth with antimony, especially in the presence of a magnetic field. ~ The choice of material for the positive branch would normally be a bismuth-telluride alloy but, as indicated by Goldsmid et al., the figure of merit of the thermoelement would be significantly improved at liquid nitrogen temperatures by the use of a normal 915

916

Mino, Cochrane, Volckmann, and Russell active element and support a current density, J = 240 A cm -2 at 77K in a magnetic field of -0.2T. In 1988, bulk high temperature superconducting (HTSC) material with these characteristic properties was not available and the predictions of Goldsmid et al. could not be verified. In 1992, Dashevskii et alY fabricated a singleelement Bil_xSbx-(YBa2Cu3OT~ + Ag) thermocouple with the superconducting passive element having a T c = 92K and J > 103 A cm -2 at 77K. The effect of an external magnetic field on Jc was not reported and consequently the increased cooling of the thermocouple due to a magnetic field was not given. The results reported indicated a maximum temperature difference, with the sink temperature at 77K, in the range 5.8 to 9 degrees K depending on the crystallinity of the active branch, t h a t is, whether an extruded polycrystal or single crystal, respectively. This work confirms the ideas ofGoldsmid et al. 3 and shows t h a t the m a n y problems related to the fabrication of such a thermocouple, for example, very low resistance connections between the branches and different thermal expansion coefficients of the materials, can be overcome. A second single-element thermoelectric cooler based on a passive superconducting branch was fabricated by N a k a n o and H a s h i m o t o ~ using a BiosgSb011(Bi,Pb)2Sr2Ca2Cu3Oy thermocouple. The (Bi-2223) material had a T c= l l 0 K , a J = 580 A cm-~ at 78K, but again no magnetic field data were reported. The m a x i m u m temperature difference obtained was 7.1K with the temperature of the sink temperature being 78K. Using the thermocouple Bio85Sbl~-(Bi-2223), it was also reported t h a t cooling could be obtained at temperatures above the superconductivity transition temperature. Other work on a thermoelectric cooler using a superconducting passive branch has also been reported by Fee. 9 Using an active bismuth-antimonide alloy branch and a passive YBa2Cu3OT~ branch, the maxim u m cooling obtained was 5.35 degrees K below a sink temperature of 79K. It was further indicated t h a t improvements could produce temperature differences up to 16 degrees K. Further, Trodahl and Fee 1~ have reported t h a t a Cu vs Bi-Sb cooler achieved a temperature difference o f - 5 degrees K in a magnetic field at liquid nitrogen temperature. An optimized single stage element should produce a AT >_14K. In this study, we report on the characteristics of a Bi0 ssSbo.t2-YBa2CthOT_~thermoelectric cooler as a function of sink temperatures, above and below T c of the superconductor, with and without an external applied magnetic field. Comparison is also made with the results from a similar couple using either pure copper or a l u m i n u m wire as the passive element.
EXPERIMENTAL

Low temperature ~ d e r
Ccld ~'~r copper C.31romet-ol~l difler entiol

'~ Y123

ther mocc+Jp~e !

Current leod
O~ode

Copper s

IL

Copper or atuminium w i r e

Jl

do,,

copper

Fig. 1. Schematic diagram of the thermoelectric cooler with (a) a superconductor as passive element, and (b) a metal wire as passive element.

metal as a passive branch. However, ira superconductor is used to replace the p-type branch in Eq. (1), Z reduces to: Z = z = S: /~nPn (4)

as S and p are both zero for a superconductor below the transition temperature, T c. With the appropriate form factor, a superconductor would provide a perfect passive branch for the thermoelectric cooler. This improvement arises from the fact t h a t the superconductor branch does not contribute to the Joule heating which limits the m a x i m u m temperature difference for a junction fabricated with a normal metal branch. H i g h - T superconducting materials having T c>90K are now available for liquid nitrogen temperature operation. According to Goldsmid et al., the crosssectional area of the superconducting passive element should have a thermal conductance < 10% of the

A single stage thermoelectric cooler was fabricated from a polycrystalline Bio.ssSbo.~2 material {negative (active) branch} and either a polycrystalline high-T c YBa2Cu3OT~ material, a pure copper wire or a pure

Cryogenic Thermoelectric Cooler with a Passive Branch aluminum wire {positive (passive) branch}, see Fig. 1. The polycrystalline Bio.ssSbo.~2material was supplied by Marlow Industries and its temperature dependent figure of merit is similar to those reported by Yim and Amith for single crystalline materials, 6 see Fig. 2. Obviously, single crystalline material would be the ideal negative branch element, but due to its handling difficulties and tendency to cleave when stressed, which m a y occur during repeated temperature cycling of prototype devices, it was not used in this study. Further, we have included the calculated (using approximation given in Ref. 2) temperature dependent figure of merit for a couple using the polycrystalline Bio~ssSbo.12as the negative branch and the best available p-type semiconducting material-excess Te-doped (Sb2 Te3)72 (Bi 2 T%)25 (Sb2S%)31~-as the positive branch. It is clear that the figure of merit of the n-p semiconductor couple decreases as the temperature decreases in the vicinity of 100K and the result is typical for all such couples. If a magnetic field of 0.75 T is used with the couple at these low temperatures, then the best available p-type material is Bio.ssSbo.12doped with 300 ppm Sn. 6 However, the resultant Z for this couple at sink temperature - 8 0 K is still significantly below that for a superconducting passive branch and a very small applied magnetic field, as we show below. The polycrystalline Bio.ssSbo.~2active element used in this work had an area of 4.25 4.25 mm 2 and a length of 4.50 mm. The polycrystalline s u p e r c o n d u c t i n g m a t e r i a l YBa2Cu3OT_~was prepared from a stoichiometric mixture of Y203, CuO, and BaCO3, calcined at 850~ in nitrogen for 24 h, ground and sintered at 930~ in air for 24 h, followed by two more sintering cycles. The material was finally oxygenated at 500~ in I atmosphere of pure oxygen for 150 h, followed by a very slow cool to room temperature. The YBCO had a T = 91.5K, a Jc > 1500 A c m -2 in zero field and a J~ = 340 A cm -2 in a field of 0.5T at 77K. The YBCO element used had an area of 2.68 x 2.68 mm 2 and a length of 4.50 mm. This is not an optimum sized component as its cross-sectional area is - 4 times that required at 80K; b u t due to the prototype fabrication processes, it allowed for ease of handling, including the preparation of ultra-flat, parallel sided (top and bottom) surfaces of the materials used in each branch. Further work is continuing in this area. The high-purity copper and aluminum wires used as passive metal elements had areas of 2.38 and 0.79 mm 2, respectively. Using published resistivity and thermal conductivity data as a function of temperature for these elements, ~ lengths of 67,205, and 410 mm for copper and 45, 90, 200, and 400 mm for aluminum were chosen. The first length should correspond to a suitable form factor at room temperature while the 410 mm Cu and 200 mm A1 to form factors at ~80K. Wire length >400 mm could not be fitted into the cryocooler chamber without significant strain being produced in the wire. In fact, to determine an accurate theoretical form factor for the wires over a

917 particular temperature range, precise values of the thermal conductivity and electrical resistivity must be known over the temperature range under consideration. In fabricating the cooler, a copper bridge was used as the cold junction; but as for all such devices not only must the contact resistance between the different materials be as small as possible but the contacts must be sufficiently flexible to accommodate the different thermal expansion coefficients of the couple materials. These two competing goals create the primary obstacle in the fabrication process. After experimenting with a large number of materials and techniques to provide the requisite contacts, we finally used the following process. The two opposite ends of the BiossSb0.n element were nickel plated and soldered to the copper heat sink and bridge using a low temperature (melting point 58~ solder of composition 23% In: 47% Bi: 18% Pb: 12% Sn. The contacts for the YBCO element were fabricated by evaporating a 7 pm layer of silver onto the ends and then annealing in oxygen for two days at 500~ Both the YBCO and copper elements were soldered into position using the low temperature solder. The fabricated cooler was attached to a cold finger of a cryocooler by nylon screws with a mica spacer for electrical isolation and thermal paste for good thermal contact (Fig. la). In the case of the aluminum wire, a pure zinc solder and a temperature of 400~ was used to form a very low resistance contact between the aluminum wire and each of the copper heat sink and bridge. These copper elements were then soldered into position using the low temperature solder (Fig. lb). In all cases, the final thermoelement had a total resistance <0.1 ohm. The temperature of the hot junction was measured with both a diode and a copper-constantan thermo7.0

~....~Bi85Sb15single crystal along the trigonol axis (6)

"~Si88Sb12 via powder metaLLurgyfrom Mar'towIndustries %50[_

\'f~-~88S'b121Ml)/lSb2 Te3)72|Bi2Te3)zS(Sb2Se3)3 {ref'[1Z]}

~.3.0 1
0 75

.
100 125

0
150 175

~
200 T/K 225 250 2 5 3

Fig. 2. Temperature variation of the figures of merit for three individual active elements: single crystalline Bio.ssSbo.ls, single crystalline Bio.~Sbo.12,polycrystalline Bio.=Sbo12from Marlow Industries and three thermoelectric coolers, potycrystalline Bio.~Sbo.JCu with an applied magnetic field and polycrystalline Bio.~Sbo.~(123 with no magnetic field, as obtained in this work and a calculated2 Z for polycrystalline Bio.~Sbo.,21(Sb2Te3)z2(Bi2 Te3)2s (Sb2Se3)3.'2

918

Mino, Cochrane, Volckmann, and Russell

Bis8 Sb12/ Y123

8{

RESULTS AND DISCUSSION Passive Superconducting Branch

70 K 75 K I 8 0 K

6.C
o

"o 4"0
L.

/
J
..,~_~..~ ......

o 2-0

,~\\
\
\ss
-

ie
~ 0

" ~ ~ - , ~ - ,
f
. . . . .

200 K
286 K / "
J I , I , l

90K
100 K
l I J l

-2"0 0

2-0 Z..O 6-0 8.0 Applied current (A)

IO'O

Fig. 3. Variation of the temperature drop in degrees K with applied current for the polycwstalline Bio.~Sbo.1~5'123 couple operating at different sink temperatures.

z.-Ol

9
/~ 175 K

Bi88Sb12tY123

3'0 t

\~jS0 K

Otg
, , ,
L I

H:: ',", \\

2.0 Z..0 6-0 Temperoture drop AT (K)

8.0

Fig. 4. Maximum coefficient of performance as a function of the temperature drop for the Bi~.~Sbo.jY123 couple operating at different sink temperatures.

couple to an accuracy of 0.1 degree K while the t e m p e r a t u r e difference was measured with a very fine gauge chromel-alumel thermocouple to an accuracy of +0.1 degree K. The thermoelectric cooler current was limited to 10 ampere, the applied magnetic field to 1.0 T, and the sink temperatures studied were mainly in the range 70-293K with a focus on temperatures about 77K, as liquid nitrogen would be the ideal coolant for commercial operation.

Figure 3 shows the temperature drop, AT (K), across the cooler, as a function ofthermocouple current for a series of sink temperatures, and no applied magnetic field. At a sink temperature of 85K, the Y123 superconducting element starts to become normal at a current >6A. For the lower sink temperatures shown, the superconductor does not go normal at 10 A, the maximum current allowed by the system wiring. It should be noted that these smooth curves are "best fits" to averaged experimental data that showed a time variation of 0.2K, while actual peak values are taken from the original data. To show the actual experimental data in such figures would completely obscure the results. It is clear that a temperature drop does occur for all sink temperatures from room temperature to 70K, whether the superconducting element is in the normal or superconducting state. From this set of curves, the maximum temperature drop attained under the experimental conditions for the temperature range 70-100K was 6.6K with a thermocouple current of 9.5 A and a sink temperature of 70K. For sink temperatures below 70K, (AT)m~ was found to decrease very significantly and the couple currents were <10 A. Also, cooling of the cold junction decreases significantly as the sink temperature approaches and exceeds T c of the superconducting element. Under ideal conditions the maximum temperature drop should be -9 degrees K at 80K which indicates that a further 30% increase in (AT)~ x can be obtained with improved design. In fact, the cross-sectional area of the superconducting passive element was a factor of four larger than that required for optimum performance, 3 and the results presented here can be immediately improved b u t requires expertise in the fabrication of rather small devices. Using Eq. (3) for derivation of the figure of merit, Z, of the Bi0.ssSb01~123 couple, Fig. 2 shows the variation of Z with the sink temperature for our Peltier refrigerator. As expected, the measured maximum figure of merit is 2.0 x 10 -3 K -1 at 80K which is -60% of the value given for the negative branch element of 3.5 x 10 -3 K -1 at 80K. This latter value appears to be relative constant around 75K while for our refrigerator operating at 70K the measured figure of merit increases to 3.3 x 10-3 K. This further increase of Z for sink temperatures in the range 70 to 80K is rather unexpected as z is almost constant for the active element over the temperature range 70-100K, while the thermal conductivity of the superconducting element increases significantly immediately below the transition temperature.t3 Thus, Z for the couple should decrease continuously for sink temperature <80K. F u r t h e r work is being undertaken to elucidate this point. The most important parameter that determines the effectiveness of the Peltier refrigerator is the coeffi-

Cryogenic Thermoelectric Cooler with a Passive Branch cient of performance which shows the relationship between the rate of cooling and the energy expended for this cooling. From Goldsmid, 2 the m a x i m u m coefficient of performance m a y be written as

919 significant cooling power of the single element when the positive branch becomes superconducting. Maxim u m cooling occurs for hot junction temperatures between 75-80K with the Peltier absorption decreasing with decreasing hot junction temperatures as also found by Nakano and Hashimoto2 This decrease explains the diminution of (AT)m= at low temperatures.

where T M is the m e a n temperature (Ti.k + T o~d)/2. Figure 4 shows Om~plotted as a function of(T~ k - T o~a) = AT for different sink temperatures. It is clear r increases with decreasing T ~ k reaching a m a x i m u m value at 70K. In fact, this single element device first becomes efficient, that is, r >1 with a cooling of 2.3 degrees K at 70K, and would be commercially viable in the form of a multi-element device operating with a sink temperature at 77K. To further characterize our single element couple, we have calculated the cooling power of the couple, that is, the Peltier absorption power at the cold junction minus half of the Joule h e a t generated in the couple at applied currents of 3, 6, and 9A. Here, we have assumed that the only heat conduction in the couple is due to Peltier adsorption and Joule heating, half of which is transmitted to the cold junction, with the other half to the hot junction. Figure 5 shows the results for the range of hot junction temperatures 70150K. In producing these curves, experimental values were used for the Seebeck coefficient of the two branches and the total electrical resistance of the couple. Note the sudden decrease of Joule heating at the superconducting transition temperature and the Bisa Sb~2/Yt23 2"0 f -

80

Bi88 Sblz/Y123

~o
o-.croI=3A

0
I=6A

-Z.0

-80

-100

60

80 100 120 1Z.O Hot junction temperature (K}

Fig9 5. Peltier absorption power - ~- (Joule heating) as a function of sink temperatures for couple currents of 3, 6, and 9A.

200 K

8"0

BissSbiz 1Y 123

!
1-6

8o K /

/
-

z
..~0 K

6.0

/-"~

~1.2z..O, /

75K

', ~ 8 5 K
~' ~ ,r/ ~ ' .t- I~ ~ 1 5

2.

0.8

i/.l Y

J-J

286

~.
I~I

~200
0

K
K

::0-< [/)qi
o
0 I / I/"~ (-"l'I" ~

Ill

;X-- . . ..

~ ./ . ... .~ _ 2"0 . r . ~ .~ . . ..~ . ~ E-"~-----,=---~i

.....

286K

'-.9o K

~J00 K

i 0"4

I ""1 0-6 field

I 0-8 (T )

~"

I 1-0

0-2 Applied

0 0

magnetic

......... 90 K 1 I { I J I I I I 0"2 0"4 0"6 0"8 1"0 Applied mognetic field (T)

Fig. 6. (a) Variation of the differential temperature drop obtained with an applied magnetic field for different sink temperatures and a Bi0.~SboJY123 couple current set to the value to obtain (/vr)m~ at T,i.k with no applied magnetic field9 (b) Total temperature drop as a function of applied magnetic field for the conditions of part (a).

920
7 I_ Bi~Sb,~/Cu
~6
t=67 ram, ~ =1"74 m m

Mino, Cochrane, Volckmann, and Russell

7
Bi~ Sb,2/Cu = 200 ram, r

7, L mm

~ 6 " (=L10mm. o~5

Bisa Sb~z/Cu r

r mm
/

293 K ~ - - . ~

"o L
ea

g LL

293 K \

I00 K ~ ~3 "6
75 K ~

~
-......~

100K,
75

\ ~--.-

2
\ ~

K(I=BA)
75 K (I:IOA)
8iasSb~2/Cu [=410 ram, ~:1-74mm

,~293
E2~1 / ~ .
i

K
80 K
9
I
I

~-'~100 K ( I = 1 0 h )

"6

~z
0

~2
E
0 , i , i , i , i 10

~ ~ ,'~./'~
, q ,

E
, 0 2 &
I , 10

~ ' - - ~ 75 K J , 1 , 6 8 Apptied current(A}

\
L I

AppUed

6 8 c u r r e n t (A)

6 B Apptied current (A)

t.

~O

0-2

0-1,

Applied magnetic

0.6 08 field {T)

1.0

a b c d Fig. 7. (a), (b), and (c) are: variation of the temperature drop with applied couple current for different lengths of copper wire in the passive branch and different sink temperatures. (d) Total temperature drop as a function of applied magnetic field for a fixed length of copper wire, a couple current set to the value to obtain (AT)m~ at the different T,~,k temperatures with no applied magnetic field.

P a s s i v e S u p e r c o n d u c t i n g B r a n c h a n d an Applied Magnetic Field At each sink temperature studied, the thermocouple current corresponding to (AT)maxwas applied to the refrigerator and maintained constant, while the effect of an applied magnetic field (range 0-1 T) was then recorded. The incremental change in temperature with field is shown in Fig. 6a while Fig. 6b shows the total temperature drop (AT) with applied field for a thermocouple current O f I a x. It should be noted that at 70K no increase in (AT)m~ was found with applied field, while the figure of merit for the couple reached its maximum value at 75K, which is below the superconducting transition temperature of the superconducting material. The maximum temperature drop of 7.3 degrees K was obtained at a sink temperature of 75K in an applied magnetic field of 0.07 T. This result is consistent with the work of Yim and Amith 8 who show that for single crystals of the alloy Bi0.88Sbo.12 the thermoelectric figure of merit (along the trigonal axis) is a maximum at a temperature of 80K for a magnetic field -0.03 T applied along the bisectrix axis; while for the higher z alloy Bio.ssSb0.1~ , the equivalent field is - 0.13 T. Further, the maximum figure of merit obtained was 3.3 x 10 -3 K -1 at 75K which is close to that expected for the polycrystalline Bio.ssSbo.12 , element (4.2 x 10 4 K -1 at 75K) as single crystalline Bio.88Sbo.12only increases from 6 x 10 -3 to 7 10 -s K -1 (Yim and Amith) 6 with an optimum magnetic field at a temperature of 80K. Thus, a 17% increase in z is expected for the polycrystalline active element in an optimum field, with the experimental increase of 0.7 x 10 -3 K -~ representing a 27% increase. This more than expected increase, as well as the well defined peak in (AT)m~ at 75K, m a y be associated with a decrease in the thermal conductivity ~ of the polycrystalline YBCO when placed in a magnetic field. Such a decrease in ~ has been found for single crystals of YBCO '4 and again further work is required in this area using bulk and melt-processed superconducting materials. From the curves of Fig. 6, it is seen that the passive branch was completely superconducting at temperatures below 85K. However, even when the supercon-

ductor is in the normal state, that is, it is a metal, it still maintains a significant temperature drop for sink temperatures in the range 90-293K. Further, the advantage of using a higher T c superconducting material with the relevant current and magnetic properties would lead to less criticality when operating at a liquid nitrogen sink temperature. The use of single crystalline Bio.85Sbo.15alloy with applied magnetic field should show a significant increase in the final figure of merit for this superconducting passive branch refrigerator2 Superconducting material with the relevant characteristics (melt processed material) is now readily available and with further work on single element coolers it should not be a big step to the development of a practical cooling unit operating at a sink temperature of 77K. P a s s i v e Metal B r a n c h With the active element being identical to that used for the previous couple, Fig. 7 shows the temperature drop, AT, as a function of applied current for different lengths of Cu wire. An external magnetic field was only applied for the results shown in Fig. 7c. It is clear from the results that a length of copper wire >410 mm or an applied current >10 A is required if we are to determine experimentally the optimum length of wire at both low temperatures and room temperature. However, the copper results show that at temperatures -80K, the maximum temperature drop at 10 A is - S K which is only - 1 K less than that for the superconducting element. Optimization of both types of passive elements would indicate a maximum temperature drop - 7 K which would be consistent with the figure of merit of the active element (-9 degrees K). In the case of the aluminum passive element, the 45 and 90 mm lengths gave rise to the largest temperature drop for all sink temperatures, while the longer lengths showed the expected temperature sequence for (AT)=~. However, for sink temperatures -80K, the maximum temperature drop obtained was - 4 degrees K, which suggests further work is required for this passive element. According to Trodahl and Fee, 1~the aluminum passive element should give a larger temperature drop than that of copper. This has not been the case and it may arise from the difficulty of obtain-

Cryogenic Thermoelectric Cooler with a Passive Branch ing a very low contact resistance between the aluminum wire and copper sinks. Since the results for the long copper length appears close to the expected optimum results, a magnetic field was applied to the couple when a current flowed through the junction corresponding to (AT)m~.Figure 7d shows the temperature drop as a function of applied magnetic field. The low temperature results are very similar to those obtained with the superconducting passive element, the significant differences being (AT)m~ - 1.5K smaller for sink temperatures -80K, while (AT)m~ - 6 degrees K larger for sink temperatures of 150 and 293K. Also, the curves corresponding to these latter temperatures are significantly different to those of Fig. 6b for the superconducting passive element. CONCLUSION The results clearly confirm the original work of Goldsmid et al2 concerning the effectiveness of a passive element for a Peltier refrigerator operating at low temperatures. Even without optimization of the form factors for the passive elements, it is clear that at low, hot junction (sink), temperatures, the superconductor/active couple provides cooling performance, with and without an applied magnetic field, that is not totally consistent with that expected theoretically for the active element ofpolycrystalline Bi0 ssSb0.12.As an alternative passive element, lengths of pure Cu and A1 wire have been used. Optimization of the lengths was not achieved for either wire type, but in the case of Cu the results were only 1.5 degrees Kless for the temperature drop at Ts~ -80K than that obtained for the case of a superconducting passive element. At Ts~ = 150 and 293K, (AT), with an applied magnetic field, was very large and significantly different to the equivalent result for the metallic superconducting materials branch. Finally, these results show clearly that using a superconducting passive element, a magnetic field and a single crystalline Bi0.s~Sb0.1~ active element,

921 thermoelectric coolers should be able to be fabricated that are commercially efficient when operated at a sink temperature of 77K, have a substantial performance when fabricated in cascade form and should produce an ideal single element temperature drop as large as 16 degrees K in zero field or 27K in a 0.12 T field.3,6,9 In fact, by optimizing the form factors for a parallel combination of a metal and superconductor as the passive branch, it should be possible to take advantage of both materials, above and below the superconducting transition temperature.

ACKNOWLEDGMENT
The authors would like t h a n k Professor H.J. Goldsmid for stimulating discussions and suggestions during this work. REFERENCES
1. A.F. Ioffe, Semiconductor Thermoelements and Thermoelectric Cooling, (London: Infosearch, 1957). 2. H.J. Goldsmid, Thermoelectric Refrigeration, (New York: Plenum Press, 1964). 3. H.J. Goldsmid, K.K. Gopinathan, D.N. Matthews, K.N.R. Taylor and C.A. Baird, J. Phys. D:Appl. Phys. 21,344 (1988). 4. G.E. Smith and R. Wolfe, J. Appl. Phys. 33, 841 (1962). 5. R. Wolfe and G.E. Smith, Appl. Phys. Lett. 1, 5 (1962). 6. W.M. Yim and A. Amith, Solid-State Electron. 15, 1141 (1972). 7. Z.M. Dashevskii, N.A. Sidorenko, N.A. Tsvetkova, C. Ya Skipidarov and A.B. Mosolov, Supercond. Sci. Technol. 5,690 (1992). 8. T. Nakano and J. Hashimoto, Jpn. J. Appl. Phys. 33, L1728 (1994). 9. M.G. Fee, Appl. Phys. Lett. 62, 1161 (1993). 10. H.J. Trodahl and M.G. Fee, Advances in Superconductivity IV: Proc. 6th Intl. Symp. on Superconductivity (ISS'93), October, 1993, Hiroshima (Springer-Verlag, 1994), p. 1215. 11. G.K. White, Experimental Techniques in Low-Temperature Physics, (Oxford: Clarendon Press, 1959). 12. W.M. Yim and F.D. Rosi, Solid-State Electron. 15, 1121 (1972). 13. B.M. Suleiman, I. U1-Haq, E. Karawacki, A. Maqsood and S.E. Gustafsson, Phys. Rev. B 48, 4095 (1993). 14. R.A.Richardson, S.D. Peacor, F. Nori and C. Uher, Phys. Rev. Lett. 67, 3856 (1991).