Jan. 1, 1963 W.

HANLEIN 3,071,495
METHOD OF MANUFACTURING A PELTIER THERMOPILE
Filed Jan. 14, 1959
 United States Patent Office 3,071,495
Patented Jan. 1, 1963
2
3,971,495 FIG. 1 is a top view of the pile,
METHOD OF MANUFACTURENG A PELER FIG. 2 is a partial and partly sectional view upon a
THERMOPELE longitudinal side of the pile; and
Walter Hänlein, Erangen, Germany, assig Ror to Sienaeis FIG. 3 a front view of the pile.
Schuckertwerke Aktiengeseischaft, Berlin-Siemensstadt, 5 The illustrated thermopile has a series of thermoelec
Germany, a corporation of Germany trically dissimilar components A and B deposited on an
Fied Fan. 14, 1959, Ser. No. 786,790 insulating carrier strip i) which also carries a number of
Claims priority, application Germary Jan. 7, 1958 heat-conducting fins C extending away from the series on
7 Cains. (C. 117-212) alternately different sides thereof. Each two adjacent
My invention relates to piles or arrays of thermo 0 components A and B are slightly spaced from each other
couples, and in a preferred aspect, to thermopiles of the and are electrically interconnected by a strip-shaped coat
Peltier type for use as heat pumps or cooling devices. ing E integral with one of the respective fins C.
In the conventional thermopiles the thermoelectrically The thermopile, according to the invention, is prefer
dissimilar components of the thermocouples are joined ably produced by vaporizing the thermoelectric compo
together by soldering. The electric transition resistance 5 nents in high vacuum upon the carrier C with the aid of
at the solder bonds has a considerable effect upon the masks or stencils so used, that during a first vaporization
efficiency of the individual couples and hence upon that step only the components A are deposited upon the carrier
of the thermopile as a whole. Various methods have whereas the areas of the components B are shielded from
become known for producing thermocouples and piles vapor deposition by the mask. In the next step the areas
with the aim of reducing the transition resistance. These 20 of components A are covered by a mask, and the compo
methods are rather complicated and expensive with respect nents B are deposited by vaporization.
to manufacturing requirements. This is particularly so Suitable as insulating carrier B are glass or ceramic
if heat conducting fins are to be solder-bonded between materials. Other thermically and electrically poor con
the thermoelectric components. Other known proposals, ducting substances are also applicable, provided they are
such as joining the thermoelectric components by elec 25 resistant to the vaporization temperatures to be used.
trolytic methods or by contacting pressure have been After depositing the components A and B upon the
found unsatisfactory. carrier strip in the manner described, the junction strips
It is therefore an object of my invention to provide a E are deposited upon the marginal areas, again with the
thermopile equipped with heat conducting fins, that does 30 aid of a mask, by vaporization of good conducting metal,
away with the soldering process and is considerably preferably copper or aluminum. The openings of the
simpler and less costly to manufacture than the thermo mask then being used are such that the fins C are simul
piles heretofore known. taneously deposited from the metal vapor upon the car
Another object of my invention, subsidiary to the one c.
mentioned, is to devise a method and a thermopile, partic 35 The method is particularly favorable if the two thermo
ularly suitable for use as Peltier pile, which affords a electric components A and B consist fundamentally of
greatly minimized transition resistance at the couple junc the same semiconductor substance and differ from each
tions conjointly with the above-mentioned simplified other only by the conductance-promoting doping applied
manufacture. thereto. Among the substances suitable as fundamental
According to a feature of my invention, the thermopile Substance for the two components is bismuth teiluride.
comprises an electrically and thermally insulating carrier 40 When using this semiconductor compound, a bismuth
which has a portion of its surface covered by a series of telluride coating may first be deposited upon the entire
coatings which alternately form the respective thermo length of the insulating carrier by vaporizing bismuth
electrically dissimilar components of the pile and are all and tellurium from two separate boats within the vacuum
area-bonded to the carrier, the mutually adjacent marginal 45 container in which the method is being performed. In
zones of each two consecutive areas of the series being a Second vaporization step, the areas of components A
coated with a junction strip of good conducting metal are Subjected to vaporized tin. Subsequently the areas
which is integral with fin areas of the same metal that of components B are subjected to the vapor of silver
are also area-bonded to the carrier on alternately differ iodide. If desired, the assembly thus far produced, may
ent sides of the series. According to a more specific and 50 be subjected to tempering. Due to the doping described,
preferred feature, the coatings that form the couple com the areas A become p-conducting and the areas B be
ponents as well as those forming the junction strips and come n-conducting. During the individual vaporizing
fins, consist all of vapor-deposited substance. Steps, the particular areas, such as A in one case, and B
According to one of the method features of my inven in the other case, are masked-off as mentioned above.
tion, the thermoelectric components of a thermopile are 55 Ultimately, the junction strips and appertaining fins of
deposited by vaporization upon an electrically insulating copper are vaporized onto the particular boundary zones
and thermally poor conducting carrier so as to coat a of the n-type and b-type bismuth telluride areas.
series of respective areas, and the mutually adjacent More in detail, the method just described is preferably
marginal zones of each two consecutive areas are then performed in accordance with the one disclosed and
coated by vaporization with a thermally good conducting 60 claimed in the copending application of Karl-Georg Gin
metal so as to form a bonded junction between the com ther, Serial No. 739,577, filed June 3, 1958, and assigned
ponents of each couple, but each latter coating is given to the assignee of the present invention. The thermopile
an extended area alongside of the said series so as to form carrier to be used for the purpose of the present inven
a heat conducting fin integral with the bonded junction, tion consists preferably of a strip of mica. At first a
the coated fin areas being located alternately on opposite 65 uniform layer of BigTea is vaporized in a vacuum vessel
sides of the series of thermocouple components. onto the masked-off carrier surface. This is done by
The foregoing and other features of my invention, set simultaneously evaporating, from separate boats, the bis
forth with particularity in the claims annexed hereto, will muth component at a temperature of 700 to 800° C. and
be further explained with reference to the embodiment of the Te component at a temperature between 300 and
a Peltier pile according to the invention schematically il 70 400° C. Due to the difference in temperature, the vapor
lustrated by way of example on the accompanying draw pressure of Te and hence the excess of the component
ing in which: Te in the vaporous phase is about 10 to 40 times that of
 3,071,495
3. 4.
the Bi component, the mica strip being kept at a tem I claim:
perature between 400 and 500° C. in this manner, a 1. The method of producing a thermopile, which com
BizTe3 coating of n-type conductance is produced, a layer prises coating a continuous surface portion of an elec
thickness of about 10 microns being sufficient in general. trically and thermally insulating carrier on serially al
For forming the p-type areas, alternate n-type areas ternating and mutually adjacent areas with separate coat
are masked, and the exposed areas of the coating are then ings of two thermoelectrically different thermocouple ma
Subjected to vaporized acceptor substance, such as Sn, terials, depositing upon the respective adjacent marginal
Pb or Si, for instance. The quantity of the vapor-de Zones of each two consecutive ones of said coatings a
posited doping Substance, i.e. the duration of the doping layer of thermally good conducting metal and simul
treatment, is chosen in accordance with the desired de 0. taneously depositing said metal upon a contiguously
gree of doping and is generally between 1 and 10-2 dop adjacent area on another portion of said carrier surface
ing Substance per mill by weight of semiconductor sub so as to simultaneously form a joining strip interconnect
Stail ce. ing said two coatings and an integral fin extending lat
Thereafter, the junction strips and fins are vapor de erally away from said series of coatings, the fin areas
posited in the above-described manner and are given a 5 being larger than the strip areas and extending alternate
thickness approximately equal to that of the thermopile ly in different directions away from the series of coatings.
components, namely about 10 microns. Preferably used 2. The method of producing a thermopile, which com
for this purpose is copper at a vaporization temperature prises the steps of vaporizing in vacuum a number of
of about 1200° C., the insulating carrier then being kept first thermoelectric coatings upon a series of mutually
at approximate room temperature, i.e. at about 20 C. 20 Spaced and masked-off area on a continuous surface of
Well Suitable as thermopile carrier, aside from mica, a single electrically and thermally insulating carrier,
are certain kinds of glasses, available in industry, whose Vaporizing in Vacuum a number of second thermoelectric
thermal coefficient of expansion is nearly coincident with coatings upon masked-off areas each located between
that of Bisies and whose heat conductance is as much two of those previously covered by said first coatings,
below that of BizTea as feasible. These requirements are 25 and vaporizing in vacuum upon another number of
met by foam glass with an air content of about 80% by masked-off areas of the carrier a number of layers of
Volume. thermally good conducting material, each of the latter
The BigTea coating produced in the above-described areas having a portion overlapping the adjacent marginal
manner exhibit thermoelectric data substantially identical Zones of each two consecutive ones of said coatings and
with those of BigTea produced by the conventional melt 30 having an integral fin portion extending laterally away
ing-together of the components. Thus, the effectiveness from the series of coatings in a direction different from
was found to be 2.10-3 degree l; and the thermoforce that of the next following fin portion.
was found to be 200 microvolt per degree. The specific 3. The method of producing a thermopile, which com
conductivity was 600 (ohm cm.) -1 for an amount of prises the steps of vaporizing in vacuum a number of
doping corresponding to 2.1019 lattice defect atoms per 35 first thermoelectric coatings upon a series of mutually
cm.3. Spaced and masked-off areas on a continuous surface of
The invention is analogously applicable for all other an electrically and thermally insulating carrier, vaporiz
thermoelectric Substances capable of being vaporized. ing in vacuum a number of second thermoelectric coat
Suitable, for example, are cadmium antimonide (CdSb), ings upon masked-off areas each located between two of
40 those previously covered by said first coatings, separately
as well as indium arsenide (InAs) and other intermetallic Vaporizing onto each of said numbers of first and sec
Seniconductor compounds of the type AIB v, formed by ond coatings a substance forming mixed crystals with
respective elements of the third and fifth groups of the the substance of said respective first and second coatings,
periodic system and having higher carrier mobility than and vaporizing upon another number of masked-off areas
germanium, Such semiconductors being particularly favor
able for thermoelectric purposes. 45 of the carrier a number of layers of thermally good con
The method of producing a thermopile according to ducting material, each of the latter areas having a por
the invention also permits, in a simple manner, to form tion overlapping the adjacent marginal zones of each
mixed crystals to serve as thermoelectric components. two consecutive ones of said coatings and having an
For this purpose, in the above-described example of bis 50 Seriesintegral fin portion extending laterally away from the
muth telluride, the areas of components B are subjected of coatings in a direction opposed to that of the
to vaporized selenium and the areas of components. A next following fin portion.
are vapor coated with antimony in two sequential steps 4. The method of producing a thermopile, which com
With the aid of masks as described above, this being done prises the steps of vaporizing in vacuum a number of
prior to doping the two areas A and B in the above first thermoelectric coatings of semiconductor compound
upon a series of masked-off areas on the surface of an
described manner. As a result, mixed crystals are pro 55 electrically
duced, composed of bismuth telluride (BioTes) and bis and thermally insulating carrier, vaporizing
muth selenide (BioSea) in the areas B, and composed of in vacuum a doping substance upon each second one of
bismuth teiluride and antimony telluride in areas A. The said areas and another doping substance upon each inter
composition of each mixture can be selected in accord 60 donor mediate area, one of said doping substances being a
ance with the desired difference of the respective thermo and the other an acceptor whereby alternating
forces. areas of said series are made thermoelectrically dissimi
Among the various mix-crystal components thus pro lar, and vaporizing upon another number of masked-off
duceable for thermopiles according to the invention are areas of the carrier a number of layers of thermally
those of indium arsenide (IAS) and indium phosphide ing good conducting material, each of the latter areas hav
(inP), or gallium arsenide (GaAs) and gallium phos a portion overlapping the adjacent marginal zones
phide known from U.S. Patent No. 2,858,275 of O. G. of each two consecutive ones of said coatings and having
an integral fin portion extending laterally away from
Folberth. the series of coatings in a direction opposed to that of
Aside from the above-mentioned advantages of thermo the next following fin portion.
piles and their manufacturing method according to the 70 5. In the method of making thermopiles according to
invention, the components of the pile according to the claim 4, said semiconductor compound being bismuth
invention, being of foil thickness, possess relatively small telluride and said doping substances being tin and silver
cross sections and thus afford the use of correspondingly iodide respectively.
high operating voltages when using such a pile as a Peltier 6. The method of producing a thermopile, which com
cooling device. 75 prises the steps of vaporizing in vacuum a number of
 3,071,495
5 6
first thermoelectric coatings of semiconductor compound of coatings in a direction opposed to that of the next
upon a series of masked-off areas on the surface of an following fin portion.
electrically and thermally insulating carrier, vaporizing 7. In a method of making thermopiles according to
in vacuum two different mix crystals forming substances claim 6, said semiconductor compound being bismuth
upon alternating ones of said areas whereby each two 5 telluride, and said mix-crystal forming substances being
adjacent areas are converted into dissimilar thermocou selenium and antimony respectively.
ple components, vaporizing in vacuum a doping substance
upon each second one of said areas and another doping References Cited in the file of this patent
substance upon each intermediate area, one of said dop UNITED STATES PATENTS
ing substances being a donor and the other an acceptor, 10
2,844,638 Lindenblad ------------- July 22, 1955
and vaporizing upon another number of masked-off areas 2,849,331 Turbolente ------------- Aug. 26, 1958
of the carrier a number of layers of thermally good con 2,865,783. Henderson et al.--------- Dec. 23, 1958
ducting material, each of the latter areas having a por 2,877.283 Justi ------ ------------ Mar. 10, 1959
tion overlapping the adjacent marginal Zones of each
two consecutive ones of said coatings and having an inte 5 FOREIGN PATENTS
gral fin portion extending laterally away from the series 307.775 Switzerland ------------ Aug. 16, 1955