CN1141513A - Thermoelectric cooling device, method for mfg. semiconductor thereof, and thermoelectric refrigerator - Google Patents
Thermoelectric cooling device, method for mfg. semiconductor thereof, and thermoelectric refrigerator Download PDFInfo
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- CN1141513A CN1141513A CN95119063.6A CN95119063A CN1141513A CN 1141513 A CN1141513 A CN 1141513A CN 95119063 A CN95119063 A CN 95119063A CN 1141513 A CN1141513 A CN 1141513A
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Abstract
Disclosed is a thermoelectric cooling element group 5 which is composed of an endothermic side electrode8, P type semiconductor layers10 formed on the electrode8, n type semiconductor layers11 and a heat-dissipating side electrode12 to connect the P type semiconductor layers10 and the n type semiconductor layers11, which are arranged at certain intervals. The P type semiconductor layers10 and the n type semiconductor layers11 are arranged in parallel and are electrically connected in series(shown in picture6). Silicone grease layers 17,17 are respectively formed between the thermoelectric cooling element group 5 and a heat absorber4, and between thermoelectric cooling element group 5 and a radiator6.
Description
The application is dividing an application of application for a patent for invention CN94105222.2.
The present invention relates to a kind of thermoelectricity (temperature difference) formula cooling device, particularly relate to a kind of thermoelectric cooling device that is used for thermoelectric refrigerator.The invention still further relates to a kind of thermoelectric refrigerator that is applicable to the semi-conductive preparation method of this thermoelectric cooling device and has used this thermoelectric cooling device.
In thermoelectric cooling device, the sort ofly the cooling device of required object refrigeration can be called peltier device or thermoelectric cooling device behind the electric energy, and be used to as in small-sized cooler bin and so on device in input.As the cooling device that need not use as any coolant of " fluorine Lyons (Freon) " or chlorofluorocarbons such as " fluorine human relations (Flon) ", said apparatus causes that day by day people pay close attention to.
The structure of common thermoelectric cooling device as shown in figure 35.That is, on the heat absorbing side dielectric substrate made from aluminium oxide and so on material 100, form a heat absorbing side electrode 102 by a heat absorbing side soldering-tin layer 101.On this heat absorbing side electrode 102, form a p type semiconductor layer 103 and a n type semiconductor layer 104 simultaneously.
Heat radiation side electrode 105 makes this p type semiconductor layer 103 and this n type semiconductor layer 104 be connected to each other.On this heat radiation side electrode 105, formed a heat radiation side dielectric substrate 107 of making by aluminium oxide and so on material by heat radiation side soldering-tin layer 106.
Many this p type semiconductor layers 103 and n type semiconductor layer 104 place between alternately between the dielectric substrate 107 of the dielectric substrate 100 of above-mentioned heat absorbing side and heat radiation side, and are electrically connected in series.
This thermoelectric cooling device is passed to a scheduled current, just can make heat absorbing side dielectric substrate 100 1 sides that hot absorption takes place, thereby, around this heat absorbing side dielectric substrate 100, cool off.On the other hand, around heat radiation side dielectric substrate 107, dispel the heat.Just cause heat transmission by fin and so on device to outside distribute heat again.
The pump heat energy of above-mentioned thermoelectric cooling device is represented with following formula (i):
Q
Ab=nSTcI-(1/2) I
2In R-K Δ T (i) formula,
Q: pump heat energy power (W)
N: semiconductor element number of packages (sheet)
S: Seebeck coefficient V (V/K)
Tc: semi-conductive cold-side temperature (K)
I: the current value (A) that feeds thermoelectric cooling device
R: the interior resistance (Ω) of thermoelectric cooling device
K: through the coefficient of heat conduction (W/K) of this thermoelectric (al) cooling device
But, following formula is made from consideration qualitatively, and its notion is based on such hypothesis; That is, the Temperature Distribution in this device is linear.And this is one to calculate at the heat of thermoelectric (al) cooling device fully, thereby, can't assess the character of the whole system (for example, thermoelectric refrigerator) that comprises this thermoelectric cooling device.
In addition, the relation between quality factor of this thermoelectric cooling device (Z) and the coefficient of efficiency maximum max is (ii) defined by following formula:
Max=1/T
C(T
C/ 2-Δ T/Z/T
C) (ii) wherein
max: the coefficient of efficiency maximum,
Tc: this semiconductor cold-side temperature (K)
Z: these semi-conductive quality factor
Z=S
2σ/K
S: Seebeck coefficient
σ: conductivity
K: thermal conductivity
Δ T: the thermoelectricity between this semi-conductive cold side and the hot side poor (K)
According to formula (ii), the difference (referring to Technical Report (II) of Electricsoci-ety of Japan, No.43) that in Figure 36, has compared thermoelectric cooling system and other cooling system by coefficient of efficiency (Cop).In the figure, under the identical situation of the temperature at the hot junction of condensing temperature and the evaporating temperature of other system of supposition and thermoelectric cooling device and cold junction place, the coefficient of efficiency that has compared compression refrigeration, absorption refrigeration system and directly driven heat pump (DDHP) formula refrigerating system.
But this figure only shown when thermoelectric cooling device can be regarded independent device as, that is when being prerequisite with unlimited heat exchange, the upper limit of coefficient of efficiency theoretical value.This figure can't assess the performance of the whole system that comprises this thermo-electric cooling device.
In common thermoelectric cooling device, dielectric substrate 100 and 107 itself promptly has big thermal resistance, because as mentioned above, it is to be made by aluminium oxide and so on.
In addition, also have a lot of thermal resistances, comprise, in the heat carrier of heat absorbing side such as the contact heat resistance on the contact-making surface between fin (not shown) and the heat absorbing side dielectric substrate 100, and between heat absorbing side dielectric substrate 100 and heat absorbing side soldering-tin layer 101, between heat absorbing side soldering-tin layer 101 and heat absorbing side electrode 102, in heat absorbing side electrode 102 and P type and n type semiconductor layer 103, between 104, in P type and n type semiconductor layer 103,104 and heat radiation side electrode 105 between, between heat radiation side electrode 105 and heat radiation side soldering-tin layer 106, between heat radiation side soldering-tin layer 106 and heat radiation side dielectric substrate 107, contact heat resistance on each contact-making surface between heat radiation side dielectric substrate 107 and heat radiation side heat carrier such as the fin (not shown), and the thermal resistance of the heat carrier of heat absorbing side and heat radiation side self.Thereby make the internal difference in temperature of semiconductor device bigger, so that cooling characteristics and all significantly attenuatings of coefficient of efficiency than what need.Therefore actual cooling coefficient of efficiency be about limit value in theory shown in Figure 36 50% or lower.
An object of the present invention is, a kind of thermoelectricity (temperature difference) formula cooling device that is used for thermoelectric refrigerator is provided, this device can overcome this field shortcoming before, and obviously improves cooling performance and coefficient of efficiency; Another purpose of the present invention is, provides a kind of high yield to make method for semiconductor and a kind of thermoelectric refrigerator without features such as fluorine Lyons or fluorine human relations and tool small size, in light weight and low noises.
In view of this, present inventors have successfully derived a thermoelectric differential equation, and this equation can more properly reflect the heat conducting truth through thermoelectric cooling device.According to this thermoelectricity differential equation, present inventors have set up a kind of thermally equilibrated method of analyzing whole thermoelectric (al) type refrigeration system, this system comprises the heat carrier and the first outer heat carrier in first, this two heat carrier all is arranged at the outside of the heat absorbing side electrode of this thermoelectric cooling device, and the second interior heat carrier and the second outer heat carrier all place the outside of the heat radiation side electrode of this thermoelectric cooling device.Present inventors have also set up a simulation program, and this program can be used a better simply electronic computer-as the personal electric computer, and uses said method effectively.
In the process of described simulation program of checking and experimental data, the present invention has noted the correlation between following parameters:
(1) average quality factor of P type and n N-type semiconductor N, Z,
(2) these two kinds semi-conductive average thickness t,
(3) at the every cm of semiconductor
2Thermal conductance on the sectional area, the heat absorbing side first interior heat carrier,
KCP,
(4) at the every cm of semiconductor
2The thermal conductance of the heat absorbing side first outer heat carrier on the cross-sectional area,
K
C,
(5) at the every cm of semiconductor
2The heat of heat carrier in the heat radiation side second on the cross-sectional area
Lead K
HP, and
(6) at the every cm of semiconductor
2The heat of the heat radiation side second outer heat carrier on the cross-sectional area
Lead K
H
Above-mentioned purpose reaches by the number range of determining each parameter as described below.
In one aspect of the invention, provide a kind of thermoelectric cooling device that is used for thermoelectric refrigerator, described device is by forming with the lower part:
Arrange a plurality of P-type semiconductor layer and the n-type semiconductor layer of putting side by side;
Have the first interior heat carrier of heat absorbing side electrode, electrode places the outside of heat absorbing side one end of this P type and n type semiconductor layer;
Place the first outer heat carrier in the heat carrier outside in first;
Have the second interior heat carrier of heat radiation side electrode, described electrode places the outside of heat radiation side one end of this P-type and n-type semiconductor layer; And
Place the second outer heat carrier in the heat carrier outside in second,
Described p type semiconductor layer and described n type semiconductor layer are connected on electricity by described heat absorbing side electrode and heat radiation side electrode;
Wherein, described P type semiconductor and n N-type semiconductor N have the average thickness t of 0.08cm at least, and the average quality factor (Z) of described p type semiconductor layer and n type semiconductor layer is controlled at and is at least 2.7 * 10
-3(/K); Thermal conductance (the K of heat carrier in described first
CP) be controlled at P type and the every cm of n type semiconductor layer
2Cross-sectional area be 8-20W/ ℃ of cm
2Scope; The thermal conductance of the described first outer heat carrier (Kc) is controlled at P type and the every cm of n type semiconductor layer
2Cross-sectional area be 3-10W/ ℃ of cm
2Scope; Thermal conductance (the K of heat carrier in described second
HPBe controlled at P type and the every cm of n type semiconductor layer
2Cross-sectional area be 8-20W/ ℃ of cm
2Thermal conductance (the K of the described second outer heat carrier
H) be controlled at P type and the every cm of n type semiconductor layer
2Cross-sectional area be 3-10W/ ℃ of cm
2Thus to absorb heat J
QRatio (J with input electric energy P
Q/ P) coefficient of efficiency (COP) of definition is at least 0.6.
In a second aspect of the present invention, provide a kind of similar in the thermoelectric cooling device of the thermo-electric cooling device of gained according to a first aspect of the invention.
Wherein, the average thickness t of described p type semiconductor layer and n type semiconductor layer is less than 0.08cm, and the average quality factor (Z) of described p type semiconductor layer and n type semiconductor layer is controlled at least 3.0 * 10
-3(/K); The thermal conductance (Kcp) of heat carrier is controlled at every cm in described first
2The P type and the cross-sectional area of n type semiconductor layer be 8-20W/ ℃ of cm
2Scope; Thermal conductance (the K of the described first outer heat carrier
C) be controlled at every cm
2The P type and the cross-sectional area of n type semiconductor layer be 7-10W/ ℃ of cm
2Scope; Thermal conductance (the K of heat carrier in described second
HP) be controlled at every cm
2The P type and the cross-sectional area of n type semiconductor layer be 8-20W/ ℃ of cm
2Scope; Thermal conductance (the K of the described second outer heat carrier layer
H) be controlled at every cm
2The P type and the cross-sectional area of n type semiconductor layer be 7-10W/ ℃ of cm
2Thus, with caloric receptivity (J
Q) and the ratio (J of input power P
Q/ P) coefficient of efficiency (COP) of definition is at least 0.6.
In a third aspect of the present invention, provide a kind of and be applicable to according to of the present invention first or the method for making semiconductor of the thermoelectric cooling device of second aspect gained, said method comprising the steps of:
Sintering is used to make semi-conductive granular ceramic mixture, simultaneously on this granular ceramic mixture, pass to predetermined voltage, between the particle of this granular ceramic mixture, producing plasma discharge, thereby activate microparticle surfaces, and remove the oxide of deposit and the gas of absorption from microparticle surfaces.
In a fourth aspect of the present invention, a kind of thermoelectric refrigerator is provided, this refrigerator has comprised according to of the present invention first or the thermoelectric cooling device of second aspect gained, wherein, the heat carrier and the described first outer heat carrier are arranged in the refrigerating chamber of this refrigerator in described first, and the described second interior heat carrier and the described second outer heat carrier are arranged at the refrigerating chamber outside of this refrigerator, in addition, at least provide a fan to the described second outer heat carrier, so that this second outer heat carrier is done air cooling.
According to first and second aspect of the present invention, the thermal conductance (K of the average quality factor of semiconductor layer (Z) and each heat carrier
Cp, K
c, K
HP, K
H) respectively corresponding to the specific thicknesses scope of semiconductor layer and be limited in the particular range.Guaranteed that therefrom coefficient of efficiency COP is at least 0.6.
As mentioned above, make COP remain on 0.6 at least, a kind of thermoelectric cooling device that is used for thermoelectric refrigerator just can be provided, this refrigerator can replace the refrigerator of compression.
According to a third aspect of the invention we, can make semiconductor in high production rate ground with high average quality factor (Z).
According to a forth aspect of the invention, make COP remain at least 0.6, can obtain thermoelectric refrigerator as compression type refrigerator substituent.Thus, can bring following advantage again: the size, weight and the noise that reduce refrigeration machine.
Above-mentioned and other purpose, feature and advantage of the present invention can be in conjunction with appended accompanying drawing, from following narration and appended claims is clear sees.
Fig. 1 is a diagrammatic sectional view of having used the thermoelectric refrigerator of the thermoelectric cooling device in the first embodiment of the present invention.
Fig. 2 is the local amplification view of one of described thermoelectric cooling device.
Fig. 3 is the right view of described thermoelectric cooling device.
Fig. 4 (a) and Fig. 4 (b) are the schematic diagram that is used for the radiator of thermoelectric cooling device.
Fig. 5 is the amplification view that is used for one group of thermoelectric cooling element of thermoelectric cooling device.
Fig. 6 is the enlarged perspective of described thermoelectric cooling element group.
Fig. 7 is the plane graph that is used for the heat dump of thermoelectric cooling device.
Fig. 8 is the cutaway view that is used for the heat dump of thermoelectric cooling device.
Fig. 9 is the cutaway view of the amplification of explanation pellumina surface appearance.
Figure 10 carries out the amplification view that pin hole is filled (pinhole filling) processing pellumina surface appearance afterwards for being presented at.
Figure 11 is the partial sectional view of explanation thermoelectric cooling element assembling distribution structure.
Figure 12 is the amplification view of a cone shaped spring packing ring.
Figure 13 is the fragmentary, perspective view of a support.
Figure 14 is the block schematic of a plasma sintering equipment.
Figure 15 is the block schematic of an isobaric sintering equipment.
Figure 16 is according to a second embodiment of the present invention the diagrammatic cross-sectional view of thermoelectric cooling device.
Figure 17 one is used for the perspective view of the aciculiform fin in the thermoelectric cooling device of above-mentioned second embodiment.
Figure 18 one is used for the perspective view of heat pipe radiating fin of the thermoelectric cooling device of a third embodiment in accordance with the invention.
Figure 19 one is used for the fin perspective view of the thermoelectric cooling device of a fourth embodiment in accordance with the invention.
Figure 20 is for describing the performance plot of heat transfer coefficient (air side pyroconductivity) as face (preceding wind) function of speed of the fin shown in Figure 19.
Figure 21 is the performance plot of the relation of face (preceding wind) speed of the fin shown in expression thermal resistance and Figure 19.
Figure 22 is the cutaway view of thermoelectric cooling device according to a fifth embodiment of the invention.
Figure 23 is the left view of the thermoelectric cooling device of above-mentioned the 5th embodiment.
Figure 24 is the graphic extension of the naive model of thermoelectric cooling device of the present invention.
The performance plot that Figure 25 distributes and compares with the actual temperature distribution for analog temperature.
Figure 26 is the graphic extension of the naive model of another thermoelectric cooling device of the present invention.
Figure 27 is the performance diagram of Kc-COP.
Figure 28 is K
HThe performance diagram of-COP.
Figure 29 is K
CpThe performance diagram of-COP.
Figure 30 is K
HPThe performance diagram of-COP.
Figure 31 is another K
cThe performance diagram of-COP.
Figure 32 is another K
HThe performance diagram of-COP.
Figure 33 is another K
CpThe performance diagram of-COP.
Figure 34 is another K
HPThe performance diagram of-COP.
Figure 35 is the local amplification view of a common thermo-electric cooling device.
Figure 36 is for being described as the COP under each cooling device temperature on the characteristic curve circle of the function of temperature difference.And
Figure 37 shows the cooling characteristics of the cooling characteristics compared thermoelectric refrigerator of the present invention and common compressed steam refrigeration device with chart.
When using thermoelectric cooling element, practice up to now is to suppose used semi-conductive cold junction temperature T in thermoelectric cooling elementoWith hot junction temperature TLEqual respectively one Fixed temperature and carry out heat and calculate. In fact, ToAnd TLCold according to being arranged at respectively this The work of the condition of work of the heat carrier in the outside of contact and hot junction and thermoelectric (al) type cooling element Condition and fixed. Therefore, as mentioned above, it is inappropriate that common heat is calculated at this.
That derive according to people such as Ogawa and be reported in August, 1992 (" NEC The information communication monthly magazine ", C-11, J75-C-11 (8), 416-424, August, 1992) Thermal conduction differential equation has been done research to one-dimensional model as shown in figure 24, leads in this model Hot body is connected to the two relative ends of thermoelectric (al) type cooling element, utilizes Peltier effect, heat Absorb from the left side, drive the input of the electric energy of thermoelectric (al) type cooling element, the loosing of institute's absorbing heat Send out, all occur in right side shown in the drawings. The cross-sectional area of described thermoelectric (al) type cooling element As the cross-sectional area (1cm of unit2), each heat carrier has that (heat absorbing side is K with respect to the thermal conductance of semiconductor per unit cross-sectional areac, heat radiation side is KH)。
Suppose in this accompanying drawing, to be respectively along X-axle temperature everywhere:
T
cχ=-LcThe place;
T
oAt χ=O place;
T
LAt χ=L place; And
T
HAt χ=LMThe place.
The equation of heat conduction under stable state provides as follows:
κ(d
2T/dχ
2)=J·〔d(αT)/dχ〕-J
2/σ-dκ/dχ·dT/dχ(1)
And hot-fluid JQ(χ) then be given:
J
Q(χ)=α JT-κ (dT/d χ) (2) wherein,
κ: thermal conductivity (W/cmdeg)
D: Seebeck coefficient (V/deg) (is negative value in the N-shaped occasion, and in P type occasion is
On the occasion of)
σ: electrical conductivity (S/cm)
J: current density (A/cm2) (occasion at N-shaped is negative value)
Further suppose, in formula (1),
αT=-(βT+|E
F/q|) (3)
(β=2K
B/|q|,E
F: Fermi can) and κ and σ be constant, formula (1) can be exchanged into following linear differential equation:
κ(d
2T/dχ
2)=βJ
odT/dχ-J
o 2/σ,J
oThe general solution of=-J (4) equation (4) can be expressed from the next: T=κ/β2σ+J
oχ/βσ-C
1κ/βJ
o
+C
2exp(βJ
oχ/κ) (5) wherein, C1,C
2: integral constant.
On the other hand, formula (2) can be rewritten as following form:
J
Q(χ)=-αJ
oT-κJ
o/βσ-C
2βJ
oexp(βJ
oχ/κ) (6)
For a passive heat carrier part, can set up following formula:
κ(d
2T/dχ
2)=0 (7)
J
Q(χ)=-κ(dT/dχ) (8)
Obtain following general solution:
T=C
3χ+C
4 (9)
J
Q(χ)=-κC
3 (10)
Introduce then boundary condition.
Suppose to work as-LC≤ χ≤0 o'clock κ=κC
T=(T
O-T
C)X/L
C+T
O (11)
J
Q(O)=κ
C(T
C-T
O)/L
C(12) suppose as L≤χ≤L
HThe time κ=κ
H
T=((T
H-T
L)χ-T
HL+T
LL
H) (13)
J
Q(L)=K
H(T
L-T
H)/(L
H-L) (14) as 0≤X≤L,
T
O=κ/β
2σ-C
1κ/βJ
O+C
2 (15)
T
L=κ/β
2σ+J
OL/βσ-C
1κ/βJ
O
+C
2exp(βJ
OL/κ) (16)
J
Q(O)=-(α T
O+ κ/β σ+C
2β) XJ
OPump heat energy power (17)
J
Q(L)=-J
O{αT
O+κ/βσ
+ C
2β exp (β J
OL/ κ) } (18) from formula (15) and (16),
C
2=B(T
L-T
O-J
OL/βσ)
C
1=βJ
O/κ(κ/β
2σ+C
2-T
O) (19)
B=1/ (exp (β J
OL/ κ)-1} now again the hypothesis
F
O=(-α+Bβ)J
O+κ
C/L
C
G
O=κ
CT
C/L
C+J
O(κ/βσ-βJ
OL/σ)
F
L={-α-β(1+B)}J
O-κ
H/L
H-L
G
L=-κ
HT
H/(L
H-L)
+ J
O(κ/β σ-J
OL (1+B)/σ) (20) the then temperature of relative two ends of thermoelectric (al) type cooling element can be expressed as:
D=F
OF
L+(βJ
O)
2B(1+B)
T
O=(F
LG
O+BβJ
OG
L)/D
T
L=(F
OG
L-(1+B) β J
OG
O)/D (21) input power density P is expressed from the next:
P=J
O 2L/ σ+| α | J
O(T
L-T
O) (22) COP can be expressed as follows:
COP=J
Q(O)/P (23) can obtain the numerical value of various necessity thus.
Then, confirm whether the temperature of being made according to formula (5) conforms to actual numerical value.Sectional area is 3 * 3mm
2, high be mounted to π shape, Control current density at 44.4A/cm for the semiconductor chip of 10mm
2Then, with this semi-conductive side wall temperatures of the contactless thermometer measure of an infrared acquisition type.
Below be the condition of used Semiconductor Physics performance etc.:
Seebeck coefficient: 205 μ V/K thermal conductivities: 0.0115W/cmK conductivity: 600S/cmK
C: 0.1W/ ℃ of cm
2K
H: 1W/ ℃ of cm
2T
C: 4.18 ℃ of T
H: 35 ℃
Above-mentioned comparison the results are shown in Figure 25, wherein, solid-line curve shows continuously, the Temperature Distribution in the thermoelectric cooling element that simulation is made according to formula (5), each point is then represented the numerical value that records according to actual conditions.Can see that this theoretical distribution conforms to the actual data of surveying very much.
The above results is to draw according to the one dimension hot-fluid model of simplifying.In fact, more commonly be, heat carrier is divided into, for example, as the outer heat carrier of fin etc. and as the interior heat carrier of scolding tin, electrode, heat-conduction medium etc.A kind of like this model structure is shown in Figure 26, wherein, and K
C, K
H, K
CPAnd K
HPBe defined as follows:
K
C, K
H: the thermal conductance that is respectively the outer heat carrier that places heat absorbing side and heat radiation side.These thermal conductances are the per unit semiconductor sectional area for thermoelectric cooling element.For example, when the thermal conductance of the whole fin that is positioned at heat absorbing side is 5W/ ℃, and the total sectional area of semiconductor layer is 2cm
2, K then
CBe the W/ ℃ of cm in 2.5 (=5/2)
2
K
CP, K
HP: comprise the thermal conductance that is inserted in the whole interior heat carriers between thermoelectric (al) type cooling element and each the outer heat carrier.They comprise, for example, (A) connect brazing metal (B) copper electrode of described semiconductor layer, (C) ceramic substrate (substrate) and (D) heat-conducting medium of silicone grease with high heat conductance as described below and so on.Consider their thermal conductivity and thickness, when doing actual calculating, only need consider (C) and (D) just much of that because of (A) and (B) to have than (C) and (D) much bigger thermal conductance.
Be the thermal conductivity and the typical thickness of heat carrier in these below:
The thermal conductivity typical thickness
(W/cm
2℃) (cm) (A) brazing metal 0.51 0.0005-0.002 (B) copper electrode 4.0 0.03-0.05 (C) pottery (aluminium oxide) 0.21 0.05-0.1 (D) heat-conducting medium 0.008 0.0005-0.001
(silicone grease)
Because the heat-conduction medium as silicone grease places between each electrode and the corresponding outer heat carrier thereof between being, and in various embodiments of the present invention, does not use any ceramic substrate, K
CpAnd K
HPAll up to 8-20W/ ℃ of cm
2
The efficient of a cooling system is represented with coefficient of efficiency (COP).This COP is by the pump heat energy power J of cooling segment
QTo the ratio of input power P, the formula of as above having stated (23) (COP=J
Q/ P) defines.
Common, wherein use " Flon " gas as coolant, and in the homemade compression-type refrigerator of the basis of 90 liters of capacity of tool, under summer hot climate condition, when this refrigerator ambient temperature was 30 ℃, Mean Input Power and pump heat energy power were respectively 70.5W and 42.3W.This moment, its coefficient of efficiency COP was 42.3/70.5=0.6.In the winter time, ambient temperature is 15 ℃ around the refrigerator, and its pump heat energy power is 19.9W, that is, less than summer pump heat energy power half.Thereby required input power is less this refrigerator this moment, therefore, as target, is to select COP=0.6 or bigger.COP=0.6 is in summer, used numerical value when environmental condition is harsh all around.
If in thermoelectric cooling device, coefficient of efficiency COP is 0.6 or bigger, then should thermoelectricity or cooling device can be used as the cooling system of the compressed steam refrigeration device that replaces those uses " Flon " gas.This replacement cooling system institute tool advantage is that the use of " Flon " will no longer be essential.And the refrigerator that has reduced size, weight, noise or the like can be provided.
In order to make coefficient of efficiency COP be increased to 0.6 or bigger, present inventors have studied many methods.As a result, find that coefficient of efficiency is subjected to obviously the influencing of parameter of the following stated:
(1) average quality factor of P type and n N-type semiconductor N, Z,
(2) semi-conductive average thickness t,
(3) to the every cm of semiconductor
2Sectional area, heat absorbing side first in the thermal conductance of heat carrier
K
CP,
(4) to the every cm of semiconductor
2Sectional area, heat absorbing side first outside the thermal conductance of heat carrier
K
C,
(5) to the every cm of semiconductor
2Sectional area, heat absorbing side second in the thermal conductance of heat carrier
K
HP, and
(6) to the every cm of semiconductor
2Cut long-pending, heat absorbing side second outside the thermal conductance of heat carrier
K
H。
In these parameters, average quality factor Z will be described at first.Current a large amount of semi-conductive average quality factor Z that makes is 2.5 * 10
-3(/K) or littler.Make a kind of method for semiconductor as being applicable to average quality factor Z higher than at present general semi-conductive quality factor, have plasma sintering, etc. static pressure compacting and zone melting etc.Utilize one of above-mentioned manufacture method, can provide a kind of have be at least 2.7 * 10
-3(/K), for example, from 2.7 * 10
-3To 3.5 * 10
-3The semiconductor of the average quality factor Z of (/K).The semiconductor that is made by these methods can be used for the present invention.To introduce some these semi-conductive particular method of manufacture below in detail.
As for average thickness t, semiconductor can as following will narrate according to Z, K
Cp, K
C, K
HPAnd K
HAnd be divided into two groups: one group is film, semiconductor, has 0.08cm or bigger thickness t, and for example, its thickness is 0.08-0.15cm; And another group is as thin as a wafer semiconductor have the thickness t less than 0.08cm, and for example, its thickness is at 0.03cm at least but less than 0.08cm.In last group, this upper thickness limit, promptly 0.15cm is not absolute the requirement, but will causes higher manufacturing cost greater than the thickness of 0.15cm, thereby is unfavorable.On the other hand, in one group in the back, the lower limit of this thickness t, promptly 0.03cm neither definitely require, and still, easily cracks when making or handle the semiconductor of making or cracked less than the thickness of this lower limit.Therefore, so excessive little thickness also is undesirable.
These K
CPAnd K
HP, for example, can be controlled by regulating one or more material thickness that places the element (as above-mentioned soldering-tin layer, electrode, ceramic substrate, silicone grease etc.) between semiconductor element and the corresponding outer heat carrier or the like separately.
On the other hand, K
CAnd K
H, for example, can be separately material, shape and heat transfer area by regulating corresponding outer heat carrier (that is, heat absorption or radiating fin) accordingly and/or the air capacity that blows into by respective fans and/or use heat pipe and controlled.
Figure 27 has shown when Z=2.7 * 10
-3(/K), K
H=3 (W/ ℃ of cm
2), K
CP=8 (W/ ℃ of cm
2) and K
HP=8 (W/ ℃ of cm
2) time K
CAnd the relation between the COP.In the figure, continuous solid line is corresponding to t=0.08cm, and dotted line is corresponding to t=0.10cm, and chain-dotted line is corresponding to t=0.15cm.
In this experiment, the internal temperature T of refrigerator
CWith external temperature T
NBe located at 0 ℃ and 30 ℃ respectively.Therefore this refrigerator is to experimentize under the inside and outside temperature difference is 30 ℃ severe condition.Used temperature conditions is used for following test too.
By can be obvious among the figure, for obtaining 0.6 or bigger COP, K
CMust be 3W/ ℃ of cm
2Or it is bigger.Even K
CIncrease to 10W/ ℃ of cm
2Or bigger, can not produce tangible attendant advantages yet, but excessive big K
CCause higher manufacturing cost, therefore, K
CGet 3-10W/ ℃ of cm
2Scope is better at 5-10W/ ℃ of cm
2Scope.
Figure 28 has shown when Z=2.7 * 10
-3(/K), K
C=3 (W/ ℃ of cm
2), K
CP=8 (W/ ℃ of cm
2), and K
HP=8 (W/ ℃ of cm
2) time, K
HAnd the relation between the COP.In the figure, solid line is corresponding to t=0.08cm continuously, and dotted line is corresponding to t=0.10cm, and chain-dotted line is corresponding to t=0.15cm.
Can be obvious by this figure, for obtaining 0.6 or bigger COP, K
HMust be 3W/ ℃ of cm
2Or it is bigger.Even K
HIncrease to 10W/ ℃ of cm
2Or bigger, do not produce tangible attendant advantages, but excessive big K
HTo cause higher manufacturing cost.Therefore, K
HGet 3-10W/ ℃ of cm
2Scope, better, get 5-10W/ ℃ of cm
2Scope.
Figure 29 has shown when Z=2.7 * 10
-3(/K), K
C=3 (W/ ℃ of cm
2), K
H=9 (W/ ℃ of cm
2) and 3 (W/ ℃ of cm
2), and K
HP=8 (W/ ℃ of cm
2) time, K
CPAnd the relation between the COP.In the figure, solid line is corresponding to t=0.08cm continuously, and dotted line is corresponding to t=0.10cm, and chain-dotted line is corresponding to t=0.15cm.
Can be obvious by this figure, for obtaining 0.6 or bigger COP, K
CPMust be 8W/ ℃ of cm
2Or it is bigger.Even K
CPIncrease to 20W/ ℃ of cm
2Or bigger, do not produce tangible attendant advantages, but excessive big K
CPTo cause higher manufacturing cost.Therefore, K
CPGet 8-20W/ ℃ of cm
2Scope, better, get 10-20W/ ℃ of cm
2Scope.
Figure 30 has shown when Z=2.7 * 10
-3(/K), K
C=3 (W/ ℃ of cm
2), K
H=9 (W/ ℃ of cm
2), and K
CP=8 (W/ ℃ of cm
2) time, K
HPAnd the relation between the COP.In the figure, continuous solid line is corresponding to t=0.08cm, and dotted line is corresponding to t=0.10cm, and chain-dotted line is corresponding to t=0.15cm.
Can be obvious by this figure, for obtaining 0.6 or bigger COP, K
HPMust be 8W/ ℃ of cm
2Or it is bigger.Even K
HPIncrease to 20W/ ℃ of cm
2Or bigger, can not produce tangible attendant advantages yet, but excessive big K
HPTo cause higher manufacturing cost.Therefore, K
HPGet 8-20W/ ℃ of cm
2Scope, better, get 10-20W/ ℃ of cm
2Scope.
Figure 31 has shown when Z=3.0 * 10
-3(/K), K
H=7 (W/ ℃ of cm
2), K
CP=8 (W/ ℃ of cm
2), and K
HP=8 (W/ ℃ of cm
2) time, K
CAnd the relation between the COP.In the figure, solid line is corresponding to t=0.03cm continuously, and dotted line is corresponding to t=0.05cm, and chain-dotted line is corresponding to t=0.07cm.
Can be obvious by this figure, for obtaining 0.6 or bigger COP, K
CMust be 5W/ ℃ of cm
2Or it is bigger.Even K
CIncrease to 10W/ ℃ of cm
2Or bigger, do not produce tangible attendant advantages yet, but excessive big K
CTo cause higher manufacturing cost.Therefore, K
CGet 5-10W/ ℃ of cm
2Scope, better, get 7-10W/ ℃ of cm
2Scope.
Figure 32 has shown when Z=2.7 * 10
-3(/K), K
C=7 (W/ ℃ of cm
2), K
CP=8 (W/ ℃ of cm
2) and K
HP=8 (W/ ℃ of cm
2) time K
HAnd the relation between the COP.In the figure, continuous solid line is corresponding to t=0.03cm, and dotted line is corresponding to t=0.05cm, and chain-dotted line is corresponding to t=0.07cm.
Can be obvious by figure, for obtaining 0.6 or bigger COP, K
HMust be 5W/ ℃ of cm
2Or it is bigger.Even K
HIncrease to 10W/ ℃ of cm
2Or bigger, can't produce tangible attendant advantages, but excessive big K
HTo cause higher manufacturing cost.Therefore, K
HGet 5-10W/ ℃ of cm
2Scope, better at 7-10W/ ℃ of cm
2Scope.
Figure 33 has shown when Z=2.7 * 10
-3(/K), K
C=7 (W/ ℃ of cm
2), K
H=7 (W/ ℃ of cm
2) and K
HP=8 (W/ ℃ of cm
2) time K
CPAnd the relation between the COP.In the figure, continuous solid line is corresponding to t=0.03cm, and dotted line is corresponding to t=0.05cm, and chain-dotted line is corresponding to t=0.07cm.
Can be obvious by figure, for obtaining 0.6 or bigger COP, K
CPMust be 8W/ ℃ of cm
2Or it is bigger.Even K
CPIncrease to 20W/ ℃ of cm
2Or bigger, can not produce tangible attendant advantages yet, but excessive big K
CPTo cause higher manufacturing cost.Therefore, K
CPGet 8-20W/ ℃ of cm
2Scope, better at 10-20W/ ℃ of cm
2Scope.
Figure 34 has shown when Z=3.0 * 10
-3(/K), K
C=7 (W/ ℃ of cm
2), K
H=7 (W/ ℃ of cm
2) and K
CP=8 (W/ ℃ of cm
2) time, K
HPAnd the relation between the COP.In the figure, solid line is corresponding to t=0.03cm continuously, and dotted line is corresponding to t=0.05cm, and chain-dotted line is corresponding to t=0.07cm.
Can be obvious by this figure, for obtaining 0.6 or bigger COP, K
HPMust be 8W/ ℃ of cm
2Or it is bigger.Even K
HPIncrease to 20W/ ℃ of cm
2Or bigger, do not produce tangible attendant advantages, but excessive big K
HPTo cause higher manufacturing cost.Therefore, K
HPGet 8-20W/ ℃ of cm
2Scope, better at 10-20W/ ℃ of cm
2Scope.
Comprehensively consider Figure 27-Figure 34, we can be divided into said circumstances two kinds of situations; In one case, used have 0.08cm or bigger thickness t than the thin semiconductor element; And in another case, used the element of N-type semiconductor N as thin as a wafer that has less than the thickness t of 0.08cm (referring to Figure 31-Figure 34).
When having used the semiconductor element of t 〉=0.08cm, can be by control Z at least 2.7 * 10
-3(/K), K
CAnd K
HAt 3-10W/ ℃ of cm
2, K
CPAnd K
HPAt 8-20W/ ℃ of cm
2Scope in, making COP with lower manufacturing cost is 0.6 or bigger thermo-electric cooling device.
On the other hand, when having used the semiconductor element of t<0.08cm, can be by control Z at least 3.0 * 10
-3(/K), K
CAnd K
HAt 7-10W/ ℃ of cm
2, K
CPAnd K
HPAt 8-20W/ ℃ of cm
2Scope, making COP with lower manufacturing cost is 0.6 or bigger thermo-electric cooling device.Also find by other test, when using as thin as a wafer the N-type semiconductor N element, consider productivity ratio and manufacturing cost, even K
C, K
H, K
CPAnd K
HPIncrease, the Z less than 3.0 also make reach 0.6 or bigger COP become difficulty.
Present inventors increase K with regard to how finding out one
CPAnd K
HPValue to 8-20W/ ℃ cm
2Method, done various researchs.As a result, find, use the grease of a high thermal conductivity, and alumina substrate (K that need not be common
CP, K
HP: about 3.3W/ ℃ cm
2, at common 0.635mm thickness) and by this oil layer each electrode is thermally coupled to its corresponding outside heat carrier, can obtain sufficiently high K as described below
CPAnd K
HPValue.
Present inventors also increase K with regard to how finding out one
CAnd K
HValue to 3-10W/ ℃ cm
2Method and done various researchs.The result, find,, constitute outer heat carrier as copper or aluminium with the material of high heat conductance, it is poor with the heat with high heat transference efficiency fin with enough heat transfer area to be produced compulsory cross-ventilation and/or be used in combination fan with fan, just can obtain so high K fully
CAnd K
HValue.
Below, with reference to corresponding accompanying drawing some embodiments of the invention are described.
At first, with reference to Fig. 1-Fig. 8, the thermoelectric refrigerator of the thermo-electric cooling device that has utilized first embodiment of the invention is described.
As shown in Figure 1, this thermoelectric refrigerator is equipped with: casing 1, and this casing is made with the heat insulator of foamed polyurethane resin and so on; Gate 2 is made with identical heat insulator, and can be arranged on the sidewall of this casing 1 with opening.Part at the back upper wall of casing 1 thermoelectric cooling device in the first embodiment of the present invention is housed, and label is 3.
As shown in Figure 2, each thermoelectric cooling device 3 is basically by a heat absorber 4, and radiator 6 places the thermoelectric (al) type cooling element group 5 between this heat absorber 4 and the radiator 6, and support 20 and a fan 19 constitute.
As shown in Figure 7 and Figure 8, in a side of each flange portion 21, (this side is the opposite side in the face of this refrigerator inside) is carved with many narrow grooves 23 with V-arrangement cross section and preserved groove 24 at the adhesive in the U-shaped cross section in these narrow groove 23 outsides along the length direction of this flange portion 21.
At trapezoidal position 22, along the length direction of this trapezoidal portions 22 at certain intervals, be formed with three countersunks 25 and three element installing holes 26 in couples.
As shown in Figure 2, relative two sides of above-mentioned fin 6 also are provided with flange portion 27.Each flange portion 27 also is carved with the narrow groove in many V-arrangement cross sections and the adhesive in U-shaped cross section is preserved groove (not shown).Be positioned at a side of fan 19 at each flange portion 27, vertically be provided with many blades 29.
The sheet metal that punching out is become reservation shape is layer folding repeatedly, forms the blade 29 shown in Fig. 4 (b).For guaranteeing between each blade and adjacent blades thereof, to leave the space, as shown in Fig. 4 (a), formed incorporate compartment 29A.
As shown in Figure 5 and Figure 6, thermoelectric (al) type cooling element group 5 is by the heat absorbing side electrode 8 that is provided with at certain intervals, be formed on p type semiconductor layer 10 and n type semiconductor layer 11 on these electrodes with for example piece or film (thick film or film) shape, and the heat radiation side electrode 12 that p type semiconductor layer 10 and n type semiconductive layer body 11 link together is formed.A plurality of p type semiconductor layers 10 and n type semiconductor layer 11 be arranged in parallel, and connect on electricity as illustrated in fig. 6.
As mentioned above, in first embodiment, do not have to use as the made dielectric substrate of aluminium oxide ceramics, heat absorbing side electrode 8 is exposed to a side, and heat radiation side electrode 12 is exposed to opposite side.
The silicone grease of described silicone grease layer 17 can suitably be formed by base oil and the particulate filler that is not more than 50% (weight).This particulate filler is by a kind of inorganic compound.(for example, silicon dioxide, aluminium oxide or zinc oxide), or one and metal, the fine particle of (for example, silver, copper or aluminium) (average grain diameter: 10 μ m or littler) form.The thermal conductivity of each silicone grease layer 17 that is wherein keeping above-mentioned high levels of filler dispersedly is up to 6.0 * 10
-3Cal/cmsec ℃ or higher.With 3 * 10 of common silicone grease
-4Cal/cmsec ℃ by comparison, and this thermal conductivity exceeds one more than the order of magnitude.One in-55 ℃ to 200 ℃ wide temperature range, this silicone grease layer 17 has kept good elasticity and viscosity.
Pellumina electric insulation layer 18 as thin as a wafer is formed at least one side of each side of heat dump 4 and radiator 6, and a described side is to thermoelectric (al) type cooling element group 5.
Pellumina is formed by anodized or similar approach usually.As shown in Figure 9, being formed with a plurality of pin holes 30 stretches into to its inside from electric insulation layer (aluminium oxide rete) surface.Although behind a large amount of formation pin holes 30, the insulation property of this electric insulation layer 18 obviously do not reduce, there is the pin hole 30 as actual situation, in fact be equivalent between this heat absorber 4 (or radiating fin 6) and thermoelectric (al) type cooling element group 5, form an air layer, like this, thermal resistance promptly becomes greatly, and thermal conductivity is extremely low.
In order to overcome this problem, used a kind of sealant in this embodiment, inject pin hole 30 as nickel acetate, to improve its thermal conductivity.Better, pin hole 30 should fill up the sealing agent fully, even 31 of sealants are injected in the pin hole 30 to a certain extent, also can significantly reduce air layer, thereby observes the improvement of pyroconductivity.
Further, as shown in figure 10, sealant film 31 has guaranteed to contact with the tight of silicone grease layer 17 in the formation on electric insulation layer 18 (pellumina) surface, thereby can further improve pyroconductivity.
As the thickness of electric insulation layer (aluminium oxide rete) 18, the thickness about 3-20 μ m is enough from the electric insulation angle.
When making heat absorber 4 and radiator 6 and each thermoelectric (al) type cooling element group 5 with copper, need only between heat absorber 4 and radiator 6, form an electric insulation layer 18, this electric insulation layer comprises the inorganic compound particulate as silicon dioxide, aluminium oxide or chromium oxide etc., and has the thickness that is as thin as about 10-50 μ m.
As shown in Figure 3, this embodiment comprises two thermoelectric (al) type cooling element groups 5 that are provided with by predetermined space along the length direction of thermoelectric (al) cooling device.As shown in figure 11, each thermoelectric (al) type cooling element group 5 places between heat absorber 4 and the radiator 6, and is fixing by a holding screw 32 and a conical spring washer 33, and all holes from the lithium head of heat absorber 4 and 25 insert.In first embodiment, a kind of screw that contains the polyamide system of 50% (weight) glass fibre is used as holding screw 32, and the stainless steel conical spring washer is as conical spring washer 33.Utilize this conical spring washer 33 and respectively between place between heat absorber 4 and the thermoelectric (al) type cooling element group 5 and place silicone grease layer 17 between radiator 6 and the thermoelectric (al) type cooling element group 5, be installed between heat absorber 4 and the radiator 6 to these thermoelectric (al) type cooling element group 5 toughness.
In first embodiment, after each holding screw 32 is screwed, be full of the space of corresponding countersink with the silicone grease 34 that is analogous to tool high thermoconductivity used in this silicone grease layer 17.
As shown in Figure 2, be fixed in the thermoelectric (al) type cooling element group 5 between heat absorber 4a and the radiator 6, by a sealant layer 35 sealings, prevent that gas and liquid from feeding around it.As sealant layer can with encapsulant have: epoxy resin. vinyl, amide resin, fluorocarbon resin, silicone resin and rubber.What be used for first embodiment is a kind ofly to contain the epoxy resin microballon content that 20-65% (weight) is dispersed in hollow glass micropearl wherein and be preferably 30-60%).These small bead particle diameters are 20-13 μ m, and about 0.5-2 μ m mean specific gravities of wall thickness are 0.1-0.4.The epoxy resin that contains this hollow glass micropearl has 1 * 10
-4Cal/cmsec ℃ very low thermal conductivity.As shown in Figure 2, support 20 is plugged between the flange portion 27 of the flange portion 21 of heat absorber 4 and radiator 6, and its perisporium length extends between them.This support 20 has alveolate texture as shown in figure 13, and makes with in fact inelastic material, in other words, promptly makes with the material of high rigidity, low-thermal conductivity.For example, through the paper of water-proofing treatment; Synthetic resin; Pottery; The metal of tool low thermal conductivity; Hard rubber as high-strength polyurethane etc.; Or it is wooden.Particularly through waterproofing agent, as paraffin, the paper that wax or fluorocarbon oil are handled because of it is stiff, has enough rigidity and light weight and low production cost and enjoys recommendation.
Above-mentioned flange portion 21 and support 20 usefulness one adhesive layer 36 bond together, and flange portion 27 and support 20 also bond together with another adhesive layer 36.The exemplary binder that can be used for this adhesive layer 36 has; Epoxy resin, vinyl, amide resin, mylar and rubber.Used epoxy resin in this embodiment.
As mentioned above, the formation of many narrow grooves makes binding agent be convenient to disperse on the flange portion 21,27, and like this, binding agent can enough amounts stay in the need bonded part.Thereby, can guarantee the fastening connection between support 20 and the flange portion 21,27.
Because alveolate texture, support 20 inside have just formed many independently areolas.And for example the above, support 20 places between flange portion 27 and 21, many independently air layers 39 promptly are formed in each hollow space 38 as illustrated in fig. 2.
Here, what need point out is, here used " alveolate texture ", to have on the plane be the structure of hexagon cavity 38 except as shown in Figure 13, also referring to those and having on the plane is the structure of polygonal cavity, for example, has triangle, the structure of rectangle or pentagon cavity; Or has a structure as the cavity of required forms such as garden shape, ellipse.Described cavity is divided into each independent cavity by the perisporium that links into an integrated entity.This alveolate texture can be in this special recommendation, because it can provide high rigidity and many independently cavitys 38 (air layer 39) simultaneously.
This support 20 as shown in Figure 3, is arranged at relative two sides of thermoelectric (al) type cooling element group 5, and is installed on the outer surface of sealant layer 35, and like this, this thermoelectric (al) type cooling element group 5 can obtain the protection of machinery.
A kind of method for making semiconductor of the present invention that can be used for will be described below.One of its method example activates sintering for plasma.According to this method, directly on the graininess ceramic mixture that will be shaped, apply a voltage.Just produce plasma discharge between the particulate of particulate ceramic mixture, microparticle surfaces is activated.As a result, can remove the oxide of deposit and the gas of absorption from this microparticle surfaces.Then, under low pressure carry out the sintering of short time again.
Referring to Figure 14, plasma sintering equipment once is described again.In chamber 40, the granular ceramic mixture 42 of desiring sintering is placed in the sintering mould 41.Granular ceramic mixture 42 is contained between punch 43 and the lower punch 44, imposes a predetermined pressure at right angle by a press 45 again.
Be connected to the epirelief membrane electrode 46 of punch 43 and lower punch electrode 47 inputs one pulse current that is connected to lower punch 44 from sintering power supply 42 through one.Carry out sintering when between the particle of granular ceramic mixture 42, producing plasma discharge.
Explanation by way of parenthesis can be through the sintered powder mixture 42 and the metal electrode of precompressed, and for example foil or stacked powdery metal layer on it are put in the sintering mould together.This can make in sintered semiconductor, forms holistic metal electrode.
With (BiSb)
2(TeSe)
3Under the sintering condition as sintering powder mixture 42 examples, should select the argon atmospher of a decompression for use, 250Kg/cm
2Sintering pressure and 250-400 ℃ sintering temperature.
In the available in the present invention method for making semiconductor, the static pressure compacting such as also can enumerate as another kind of manufacture method.As shown in figure 15, will be used for making the flexible mould 81 that semi-conductive granular ceramic mixture 80 is packed into class material systems such as a usefulness rubber.This mould 81 that has loaded granular ceramic mixture 80 immerses in the pressure medium 82 of a hold-down container.This hold-down container is by a cylinder pressure 83, and lower cover 84 and loam cake 85 are formed.This hold-down container has been full of as, the pressure medium of being made up of the mixture of polypropylene glycol and water.This pressure medium 82 of nationality, granular ceramic mixture 80 is by isobaric, press forming equably.This method of having used pressure medium 82 is a wet processing method.Also can use method for processing dried, at this moment, granular ceramic mixture be filled in the flexible mould.Then, the model that this has been loaded granular ceramic mixture directly places a pressurizing vessel to carry out equipressure and evenly compacting.
Below, with reference to Figure 16 and 17, the thermoelectric (al) cooling device according to second embodiment of the invention is described.
As shown in figure 16, the heat absorbing side fin 62 that is made of substrate 60 and a plurality of needle-like fin 61 provided thereon is connected to a side (upside) of each thermoelectric (al) type cooling element group 5.At the opposite side (downside) of this thermoelectric (al) type cooling element group 5, be connected with the heat radiation side fin of forming by substrate 60 and a plurality of needle-like fin 63 provided thereon 63.Each thermoelectric cooling device group 5 is identical with the structure that is used for first embodiment.Roughly the same above-mentioned silicone grease (not shown) is inserted between each thermoelectric (al) type cooling element group 5 and the relative substrate 60.
Heat absorbing side fin 62 is loaded among the heat absorbing side pipeline 64A, like this, air can axially blast along heat absorbing side fin 62, on the other hand, heat radiation side fin 63 is loaded among the heat radiation side pipeline 64B, but so that extracts out at heat radiation side fin 63 ambient air mat heat radiation side fan 65B.
The example of available needle-like fin 61 comprises: pin directly is 0.3-0.5mm, and needle gage is 0.9-2.5mm, and the pin height is the fin of 5-20mm.Above-mentioned parameter is selected in combination for use, can obtain the area of heat transfer that needs.
Figure 18 has illustrated suction (loosing) backing that the thermoelectric (al) cooling device of the 3rd embodiment of the present invention is used.In this embodiment, the minor diameter heat pipe 66 of annular is installed on the substrate 60, evaporation and the condensation and fast transmit of heat by being loaded on working media in the heat pipe 66 volatile liquid of (for example, as ethanol and so on).When using these heat pipes 66, and cooling wind speed and input power be when being respectively 2m/s and 50W, and thermal resistance is 0.8 ℃/W or lower.
Figure 19 has shown fin (fin) used in the thermoelectric (al) cooling device of the 4th embodiment of the present invention.In this embodiment, arc thin slice fin 67 is arranged on the substrate 60 to give fixed spacing with becoming some row.
In Figure 18 and 19, arrow X represents the air approach axis.In the embodiment of Figure 19, each sheet type fin 67 is arranged in rows on air approach axis X.But, each sheet type fin 67 also can be done the indentation arrangement on air approach axis X.
Figure 20 is with the chart attirbutes of air side thermal conductivity as the function of the fin face velocity described in Figure 19 (preceding wind front wind speed), and Figure 21 is with the chart attirbutes of thermal resistance as face (preceding wind) function of speed of this same fin.Think among the figure that fin has excellent heat transfer performance.
Below, with reference to Figure 22 and Figure 23, the thermoelectric (al) cooling device according to the 5th embodiment of the present invention is described.As shown in figure 22, a thermoelectric (al) cooling device 3 is installed on the plane heated portion 70 of heat pipe by the silicone grease (not shown).The vaporizer side pipeline 71a of heat pipe and condenser side pipeline 71b are connected to heated portion 70.The other end of pipeline 71a, 71b is connected to a heat radiation position 72 that ventilates of heat pipe.This heat radiation partly 72 is obliquely installed.This heat pipe comprises that it is formed at inner die, and has been full of the volatility working media as ethanol and so on.By the evaporation repeatedly and the condensation of this working media, this heat pipe can distribute after thermoelectric (al) cooling device 3 absorbs heat.
Above-mentioned heated portion 70, radiator portion 72 and this type of component packages are in pipeline 73.One cooling blower 74 places the bottom of this pipeline 73, so that air can be blown into along direction shown in the arrow X.In addition, label 75 expressions one built-in fans, this fan blows to air the heat absorbing side of thermoelectric (al) cooling device 3.
Use the heat pipe of deflection can reduce the shock and vibration that put on this thermoelectric (al) cooling device.
Below with reference to Figure 37, the result of the cooling performance test that thermoelectric refrigerator according to the present invention and common compressed steam refrigeration device are done is described.
In this cooling test, it is 60 liters refrigerator (refrigerator) that 10 bottles of capacity beer that is 500ml is placed capacity respectively, under 30 ℃ of the temperature, records the cooling degree of beer in the above-mentioned bottle around.
In Figure 37, curve X and Y represent the cooling performance according to thermoelectric refrigerator of the present invention respectively, and curve Z represents the cooling performance of common compressed steam refrigeration device.Here, be equipped with 512 block semiconductors corresponding to the thermoelectric refrigerator of curve X, rated watt consumption is 106W, and is equipped with the semiconductor piece of same quantity corresponding to the refrigerator of curve Y, and rated watt consumption is 48W.On the other hand, the rated watt consumption of common compressed steam refrigeration device is 61W.
Can be obvious from above-mentioned chart.Thermoelectric refrigerator according to the present invention is better than the common compressed steam refrigeration device with this thermoelectric refrigerator tool same nominal power consumption on cooling performance.
Claims (3)
1. be applicable to the semi-conductive preparation method of thermoelectric refrigerator with thermoelectric cooling device, described thermoelectric refrigerator comprises with lower member with thermoelectric cooling device:
A plurality of p type semiconductor layers that are set up in parallel (10) and n type semiconductor layer (11);
The first interior heat carrier (K with heat absorbing side electrode (8)
CP17), described electrode places the outside of heat absorbing side one end of this P type and n type semiconductor layer (10,11);
Place heat carrier (K in first
CP17) Wai Ce the first outer heat carrier (K
C4);
The second interior heat carrier (K with heat radiation side electrode (12)
HP17), described electrode places the outside of heat radiation side one end of this P type and n type semiconductor layer (10,11); And
Place heat carrier (K in second
HP17) Wai Ce the second outer heat carrier (K
H6),
Described p type semiconductor layer (10) and described n type semiconductor layer (11) are connected on electricity by described heat absorbing side electrode (8) and heat radiation side electrode (12);
Wherein, described p type semiconductor layer (10) and n type semiconductor layer (11) have the average thickness t of 0.08cm at least, and the average quality factor (Z) of described p type semiconductor layer (10) and n type semiconductor layer (11) is controlled at least 2.7 * 10
-3(/K); Heat carrier (K in described first
CP17) thermal conductance (K
CP) be controlled at every cm
2The P type and the cross-sectional area of n type semiconductor layer be 8-20W/ ℃ of cm
2Scope; The described first outer heat carrier (K
C4) thermal conductance (K
C) be controlled at every cm
2P type and n type semiconductor layer cross-sectional area be 3-10W/ ℃ of cm
2Scope; Heat carrier (K in described second
HP17) thermal conductance (K
HP) be controlled at every cm
2P type and n type semiconductor layer cross-sectional area be 8-20W/ ℃ of cm
2The described second outer heat carrier (K
H6) thermal conductance (K
H) be controlled at every cm
2P type and n type semiconductor layer cross-sectional area be 3-10W/ ℃ of cm
2, and to absorb heat J
QRatio (J with input electric energy P
Q/ P) coefficient of efficiency (COP) of definition is at least 0.6,
The preparation method is characterised in that:
Sintering is made semi-conductive granular ceramic mixture, simultaneously on this granular ceramic mixture, pass to predetermined voltage, between the particle of this granular ceramic mixture, producing plasma discharge, thereby activate microparticle surfaces, and remove the oxide of deposit and the gas of absorption from microparticle surfaces.
2. be applicable to the semi-conductive preparation method of thermoelectric refrigerator with thermoelectric cooling device, described thermoelectric refrigerator comprises with lower member with thermoelectric cooling device:
A plurality of p type semiconductor layers that are set up in parallel (10) and n type semiconductor layer (11);
The first interior heat carrier (K with heat absorbing side electrode (8)
CP17), described electrode places the outside of heat absorbing side one end of this P type and n type semiconductor layer (10,11);
Place heat carrier (K in first
CP17) Wai Ce the first outer heat carrier (K
C4);
The second interior heat carrier (K with heat radiation side electrode (12)
HP17), described electrode places the outside of heat radiation side one end of this P type and n type semiconductor layer (10,11); And
Place heat carrier (K in second
HP17) Wai Ce the second outer heat carrier (K
H6),
Described p type semiconductor layer (10) and described n type semiconductor layer (11) are connected on electricity by described heat absorbing side electrode (8) and heat radiation side electrode (12);
Wherein, described p type semiconductor layer (10) and n type semiconductor layer (11) have the average thickness t of 0.08~0.15cm, and the average quality factor (Z) of described p type semiconductor layer (10) and n type semiconductor layer (11) is controlled at 2.7 * 10
-3-3.5 * 10
-3The scope of (/K); Heat carrier (K in described first
CP17) thermal conductance (K
CP) be controlled at every cm
2The P type and the cross-sectional area of n type semiconductor layer be 8-20W/ ℃ of cm
2Scope; The described first outer heat carrier (K
C4) thermal conductance (K
C) be controlled at every cm
2P type and n type semiconductor layer cross-sectional area be 3-10W/ ℃ of cm
2Scope; Heat carrier (K in described second
HP17) thermal conductance (K
HP) be controlled at every cm
2P type and n type semiconductor layer cross-sectional area be 8-20W/ ℃ of cm
2The described second outer heat carrier (K
H6) thermal conductance (K
H) be controlled at every cm
2P type and n type semiconductor layer cross-sectional area be 3-10W/ ℃ of cm
2, and to absorb heat J
QRatio (J with input electric energy P
Q/ P) coefficient of efficiency (COP) of definition is at least 0.6,
The preparation method is characterised in that:
Sintering is made semi-conductive granular ceramic mixture, simultaneously on this granular ceramic mixture, pass to predetermined voltage, between the particle of this granular ceramic mixture, producing plasma discharge, thereby activate microparticle surfaces, and remove the oxide of deposit and the gas of absorption from microparticle surfaces.
3. be applicable to the semi-conductive preparation method of thermoelectric refrigerator with thermoelectric cooling device, described thermoelectric refrigerator comprises with lower member with thermoelectric cooling device:
Arrange a plurality of p type semiconductor layers (10) and the n type semiconductor layer (11) of putting side by side;
The first interior heat carrier (K with heat absorbing side electrode (8)
CP17), described electrode places the outside of heat absorbing side one end of this P type and n type semiconductor layer (10,11);
Place heat carrier (K in first
CP17) Wai Ce the first outer heat carrier (K
C4)
The second interior heat carrier (K with heat radiation side electrode (12)
HP17), described electrode places the outside of heat radiation side one end of this P type and n type semiconductor layer (10,11); And
Place heat carrier (K in second
HP17) Wai Ce the second outer heat carrier (K
H6);
Described p type semiconductor layer (10) and described n type semiconductor layer (11) are connected on electricity by described heat absorbing side electrode (8) and heat radiation side electrode (12);
Wherein, the average thickness t of described p type semiconductor layer (10) and n type semiconductor layer (11) is less than 0.08cm, and the average quality factor (Z) of described p type semiconductor layer (10) and n type semiconductor layer (11) is controlled at least 3.0 * 10
-3(/K); Heat carrier (K in described first
CP17) thermal conductance (K
CP) be controlled at every cm
2The P type and the cross-sectional area of n type semiconductor layer be 8-20W/ ℃ of cm
2Scope; The described first outer heat carrier (K
C4) thermal conductance (K
C) be controlled at every cm
2The P type and the cross-sectional area of n type semiconductor layer be 7-10W/ ℃ of cm
2Scope; Heat carrier (K in described second
HP17) thermal conductance (K
HP) be controlled at every cm
2The P type and the cross-sectional area of n type semiconductor layer be 8-20W/ ℃ of cm
2The described second outer heat carrier (K
H6) thermal conductance (K
H) be controlled at every cm
2The P type and the cross-sectional area of n type semiconductor layer be 7-10W/ ℃ of cm
2And with caloric receptivity (J
Q) and the ratio (J of input power P
Q/ P) coefficient of efficiency (COP) of definition is at least 0.6,
The preparation method is characterised in that:
Sintering is made semi-conductive granular ceramic mixture, simultaneously on this granular ceramic mixture, pass to predetermined voltage, between the particle of this granular ceramic mixture, producing plasma discharge, thereby activate microparticle surfaces, and remove the oxide of deposit and the gas of absorption from microparticle surfaces.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP105526/1993 | 1993-05-06 | ||
JP10552693A JP3451107B2 (en) | 1992-10-05 | 1993-05-06 | Electronic cooling device |
JP105526/93 | 1993-05-06 | ||
JP244786/1993 | 1993-09-30 | ||
JP244786/93 | 1993-09-30 | ||
JP24478693A JP3495393B2 (en) | 1993-09-30 | 1993-09-30 | Electronic refrigerator for electronic refrigerator, method of manufacturing semiconductor used for electronic refrigerator, and electronic refrigerator using the electronic refrigerator |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN94105222.2A Division CN1034252C (en) | 1993-05-06 | 1994-05-06 | Thermoelectric cooling device for thermoelectric refrigerator, process for the fabrication of semiconductor suitable for use in the thermoelectric cooling device, and thermoelectric refrigerator..... |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1141513A true CN1141513A (en) | 1997-01-29 |
CN1074585C CN1074585C (en) | 2001-11-07 |
Family
ID=26445797
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Application Number | Title | Priority Date | Filing Date |
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CN94105222.2A Expired - Fee Related CN1034252C (en) | 1993-05-06 | 1994-05-06 | Thermoelectric cooling device for thermoelectric refrigerator, process for the fabrication of semiconductor suitable for use in the thermoelectric cooling device, and thermoelectric refrigerator..... |
CN95119063A Expired - Fee Related CN1074585C (en) | 1993-05-06 | 1995-12-05 | Thermoelectric cooling device, method for mfg. semiconductor thereof, and thermoelectric refrigerator |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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CN94105222.2A Expired - Fee Related CN1034252C (en) | 1993-05-06 | 1994-05-06 | Thermoelectric cooling device for thermoelectric refrigerator, process for the fabrication of semiconductor suitable for use in the thermoelectric cooling device, and thermoelectric refrigerator..... |
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CN (2) | CN1034252C (en) |
Families Citing this family (11)
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CN100353534C (en) * | 2004-06-16 | 2007-12-05 | 华孚科技股份有限公司 | Method for making electric-heating radiator and electric-heating radiator thereby |
JP5468554B2 (en) * | 2008-02-07 | 2014-04-09 | ビーエーエスエフ ソシエタス・ヨーロピア | Semiconductor materials containing doped tin telluride for thermoelectric applications |
CN102147166A (en) * | 2010-02-10 | 2011-08-10 | 郑云兵 | Semiconductor refrigerator |
CN103124132A (en) * | 2011-11-18 | 2013-05-29 | 永济新时速电机电器有限责任公司 | Locomotive traction converter |
CN103745960A (en) * | 2013-12-31 | 2014-04-23 | 吴江亿泰真空设备科技有限公司 | Miniature semiconductor heat radiation device |
DE102015006561A1 (en) * | 2014-06-16 | 2015-12-17 | Liebherr-Hausgeräte Lienz Gmbh | Vakuumdämmkörper with a thermoelectric element |
CN104266344A (en) * | 2014-09-28 | 2015-01-07 | 南宁市磁汇科技有限公司 | Uniform heating method for use in pipeline |
CN104266517A (en) * | 2014-09-28 | 2015-01-07 | 南宁市磁汇科技有限公司 | Pipeline capable of internally and uniformly transferring heat |
CA3088588A1 (en) * | 2018-01-26 | 2019-08-01 | Basf Se | Solids-packed apparatus for performance of endothermic reactions with direct electrical heating |
CN112802954A (en) * | 2019-11-13 | 2021-05-14 | 银河制版印刷有限公司 | Thermoelectric power generation device and manufacturing method thereof |
CN112090244A (en) * | 2020-09-29 | 2020-12-18 | 天津金盛吉达新能源科技有限公司 | Active adsorption dehumidification system |
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EP0335213A3 (en) * | 1988-03-30 | 1990-01-24 | Idemitsu Petrochemical Co. Ltd. | Method for producing thermoelectric elements |
JPH02198179A (en) * | 1989-01-27 | 1990-08-06 | Matsushita Electric Ind Co Ltd | Thermoelectric element and manufacture thereof |
-
1994
- 1994-05-06 CN CN94105222.2A patent/CN1034252C/en not_active Expired - Fee Related
-
1995
- 1995-12-05 CN CN95119063A patent/CN1074585C/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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CN1100236A (en) | 1995-03-15 |
CN1034252C (en) | 1997-03-12 |
CN1074585C (en) | 2001-11-07 |
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