• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Thermoelectric generator, comprising a semiconductor membrane (2) with a phononic structure containing at least one PN junction (3, 4) suspended between a first support (5) intended to be coupled to a cold thermal source and a second support (6) intended to be coupled to a hot thermal source and an architecture for redistributing the heat flow in the plane of said membrane.
    公开号:FR3029355A1
    申请号:FR1461760
    申请日:2014-12-02
    公开日:2016-06-03
    发明作者:Emmanuel Dubois；Jean-Francois Robillard；Stephane Monfray；Thomas Skotnicki
    申请人:STMicroelectronics Crolles 2 SAS；
    IPC主号:
    专利说明:

    [0001] Thermoelectric Generator Embodiments of the invention relate to thermoelectric generators, and more specifically integrated thermoelectric generators comprising a semiconductor material. Possible applications of the invention include the supply of low and medium power electrical devices through the recovery of thermal energy such as: - communication sensors distributed in a fixed environment (buildings, floors) or mobile (automobile aircraft); - autonomous measuring devices for medical purposes powered by the heat of the body. The present invention could also be applied for example in the context of the recovery / dissipation of thermal energy within microelectronic circuits. Integrated thermoelectric generator devices generally include a miniaturized vertical thermopile architecture coupled in series and using conventional thermoelectric materials such as bismuth telluride (Bi2Te3). However, the vertical structure of these generators and the usual thermoelectronic materials are hardly compatible with conventional CMOS manufacturing processes. According to one embodiment, there is provided a thermoelectric generator of structure compatible with embodiments in an integrated manner and with CMOS manufacturing processes. According to one embodiment, there is provided a thermoelectric generator whose active element is of substantially planar structure, and whose architecture redistributes the heat flow in the plane of the active element. According to another embodiment, there is provided a thermoelectric generator whose active element is structured by phononic engineering and whose thermal conductivity very reduced in certain directions and greater in other directions, gives it thermoelectric properties greater than those current generators. According to one aspect, there is provided a thermoelectric generator comprising a semiconductor membrane containing at least one PN junction, this membrane being suspended between a first support intended to be coupled to a cold thermal source and a second support intended to be coupled to a hot thermal source. The semiconductor membrane, which forms the active element of the thermoelectric generator, is by nature a substantially planar and generally thin element, and its embodiment easily integrates into the manufacturing process of CMOS integrated circuits. The membrane may extend parallel to the supports, for example equidistant from them. Such a configuration of the thermoelectric generator, which is distinctly different from the conventional structures of the prior art, can then be described as "planar" by abuse of language as opposed to the vertical structures of the prior art. The supports may be rigid, for example metal or semiconductors.
    [0002] Alternatively the supports can be flexible which allows the generator to marry a curved surface for example. According to one embodiment, the semiconductor membrane contains several alternating bands of N and P conductivity type forming a plurality of PN junctions coupled in series, each PN junction extending between a first face of the membrane located opposite the first support and a second face of the membrane facing the second support, said membrane being suspended by suspension means comprising thermally conductive pillars distributed alternately on both sides of the membrane, each pillar connecting a PN junction to the corresponding support. The presence of several bands N and P makes it possible to increase the power of the thermoelectric generator and the alternating distribution of the pillars makes it possible to redistribute the thermal flux in the plane of the membrane. According to yet another embodiment, the thermally conductive abutments on one of the faces comprise at least two so-called electrically conductive contact pillars coupled to at least two locations of the corresponding support so as to generate an electrical signal and isolated. the corresponding support by a thermally conductive electrical insulator; - So-called connecting pillars, electrically conductive and electrically isolated from the corresponding support by a thermally conductive electrical insulator. The pillars on the other side comprise only electrically conductive connecting pillars and electrically insulated from the corresponding support by a thermally conductive electrical insulator. It is particularly advantageous for the suspended membrane to be of phononic structure, that is to say comprising an inclusion network of constitution different from the semiconductor material of the membrane. As is well known to those skilled in the art, phonons are the modes of vibration of atoms in the crystal lattice of the silicon material. The phononic structure is notably achieved by introducing holes (artificial phononic crystal) in the membrane, for example silicon, to lead to a significant reduction in thermal conductivity. As a result, thermoelectric properties superior to current thermoelectric materials can be obtained. It is advantageously proposed a periodic inclusion network with at least one repetition step lower than the mean free path of the thermal phonons and greater than the wavelength of the thermal phonons. Indeed, the effectiveness of the phonon crystal to filter the phonons is in particular determined by the repetition step.
    [0003] To benefit from a cumulative effect of the filtering of the thermal phonons at different frequencies, it is proposed to use a succession of different incremental pitch steps, that is, a repetition step gradient.
    [0004] It is also proposed to use, for example, a succession of inclusions of increasing size in order to reinforce the cumulative effect of the filtering of the thermal phonons at different frequencies. Advantageously, the phononic structure semiconductor membrane can provide for combining the two preceding characteristics (no repetition and increasing size inclusions) to further increase the filtering of the thermal phonons at different frequencies and thus further improve the performance of the thermoelectric generator. When the semiconductor material is silicon, the inclusion repetition step is advantageously greater than 2 nm and less than 200 nm and the thickness of the membrane is advantageously between 10 nm and 2 μm. The network of inclusions is advantageously symmetrical. The symmetry of the inclusion network provides an interesting effect for inducing properties dependent on the direction of propagation. The different densities of inclusions in the directions of orientations within a symmetrical inclusion network influence the thermal conductivities of the corresponding directions of orientation. The higher the density of inclusions, the lower the corresponding thermal conductivity. It is therefore preferable to have a higher density of inclusions (that is to say a lower thermal conductivity) between two zones of the phononic structure semiconductor membrane coupled to the two adjacent pillars respectively connected to the supports. different to obtain a minimal influence of the difference of temperature between these two zones. Similarly, a lower inclusion density (i.e. higher thermal conductivity) can be left in the junction orientation direction to obtain a more homogeneous temperature along these junctions .
    [0005] Thus according to one embodiment, the symmetrical inclusion network comprises first orientation directions comprising a first inclusion density and a second orientation direction comprising a second inclusion density lower than the first density, the PN junction strips are parallel to the second orientation density, and the trace on one of the faces of a pillar located on the other side is aligned in the first orientation directions with any one of the pillars adjacent on one of the faces.
    [0006] According to another embodiment, the pillars are distributed alternately staggered alternately on both sides of the membrane, the pillars on each of the two faces of the membrane forming groups of squares, the trace on one of the faces a pillar located on the other side located in the center of a square of pillars located on said one of the faces. The generator is advantageously made in an integrated manner, and in another aspect, there is provided an integrated circuit incorporating a thermoelectric generator as defined above. Other advantages and features of the invention will become apparent upon studying the detailed description of embodiments and embodiments, given by way of nonlimiting examples and illustrated by the appended drawings in which: FIGS. to 3 relate to different embodiments of a thermoelectric generator according to the invention - Figures 4 to 20 schematically illustrate different steps of an exemplary method for producing a thermoelectric generator according to the invention. Referring now to Figures 1 to 3 to illustrate an embodiment of a thermoelectric generator according to the invention incorporated within an integrated circuit CI. In Figure 1, there is shown a top view by sky of an embodiment of a thermoelectric generator 1 according to the invention. FIG. 2 is a section along the line II-II of FIG. 1. FIG. 3 illustrates an enlargement of the network of inclusions of the suspended membrane with phonon structure in FIG. 1. Referring to FIGS. 1 and 2, FIG. see that the thermoelectric generator 1 here comprises a semiconductor thin membrane of plane geometry 2. The membrane 2 is said to be suspended: the membrane is held by pillars 7-23 between a first support 5 and a second support 6. The two supports 5 and 6 are intended to be coupled respectively with a cold thermal source and a hot thermal source.
    [0007] The hot source may for example be a hot part of an integrated circuit and cold source may be a cooler part of the integrated circuit. Alternatively the hot source may be for example a pipe carrying a hot fluid and the cold source ambient air.
    [0008] If the generator is placed in a watch for example, the hot source may be the human skin and the cold source the ambient air. The membrane 2 is here equidistant from the supports 5 and 6. This symmetry of the structure makes it possible in particular to facilitate the production of the membrane. The membrane comprises an alternation of N and P-doped bands 3, 4 forming a plurality of P-N 3, 4 junctions connected in series. Each P-N junction extends between a first face Fi of the membrane located opposite the first support 5 and a second face F2 of the membrane located opposite the second support 6. The materials of two supports may be metal or silicon. For example, the support 6 may be a part of a silicon substrate made in conventional CMOS manufacturing processes. It is also possible to use metal films, for example stainless steel or aluminum, for the supports 5 and 6. The supports can be rigid or have a certain flexibility in the same way as the silicon membrane 2. The pillars 7 at 23 are thermally and electrically conductive. Each pillar connects a P-N junction on one side and is insulated from the corresponding support by an electrically insulating (eg: 24 for the pillar 8) thermally conductive. The pillars located on the first face Fi behavior said two pillars of contacts 25 and 26 electrically conductive coupled to two locations El, E2 of the support 5 so as to generate an electrical signal. They are isolated from the support 5 by a thermally conductive electrical insulator (Ex: 27 for the contact pillar 26). When the supports 5 and 6 are respectively coupled to the cold source and the hot source, the thermoelectric membrane 2 is subjected to a thermal gradient which generates a potential difference between the two locations E1 and E2. The other pillars are actually so-called liaison pillars. The space between the face F2 and the support 6 comprises only connecting pillars 11, 12, 13.
    [0009] These so-called connecting pillars 8, 9, 19, 11, 12, 13 contribute to redistribute the thermal flux in the plane of the membrane at the level of the P-N junctions. As illustrated in FIGS. 1 and 2, the pillars 7 to 23 are distributed alternately staggered alternately on the two faces Fi and F2 of the membrane 2 (Ex: the pillars 7, 8, 17, 18 on the face Fi and the pillar 14 on F2). It can be seen that the pillars located on each of the two faces of the membrane form groups of squares, for example the pillars 7, 8, 17 and 18.
    [0010] The trace on the face Fi of the pillar 14 located on the face F2 is located in the center of the square of pillars 7, 8, 17 and 18 located on the face Fi. Reference will now be made more particularly to FIG. 3 to show examples of characteristic elements of an inclusion network of the silicon membrane.
    [0011] To preserve the electrical properties of the crystal lattice while reducing the propagation of phonons, it is preferable to work in the ballistic regime, that is to say to introduce a structure of inclusions of sizes smaller than the average free path of phonons. (-200 nm to 300 K for silicon).
    [0012] FIG. 3 shows a thin silicon phonon structure membrane comprising a periodic set of patterns (inclusions) having a mechanical contrast with the material of the thin membrane. Thus, the inclusions may comprise a semiconductor material different from that of the membrane, for example Ge or SiGe, or simply be filled with air. Moreover, it is advantageous for the phononic structure to have the following characteristics, taken separately or preferably in combination, at least for some of them: a repetition step p less than the average free path of the thermal phonons (-200 nm to 300K in silicon) and greater than the wavelength of thermal phonons (-2 nm to 300K in silicon); a symmetry of the network (hexagonal, square, etc.), a size t of periodic inclusions (phononic crystal) less than the mean free path of the thermal phonons and greater than the wavelength of the thermal phonons; - a symmetrical shape of inclusions (square, cylindrical, triangular). Moreover, the thickness e of the membrane also has an influence. Thus this thickness is normally between 10 nm and 2 iam for silicon in order to have thermoelectric properties significantly better than in the state of the art. On the other hand, another interesting effect offered by the symmetry of the phononic structure within the semiconductor membrane illustrated in FIG. 3 is to induce properties dependent on the direction of propagation.
    [0013] In other words, phononic modes of the same frequency acquire different speeds in the direction of propagation. In the case of said phononic structure membrane, this means that the higher the inclusions are dense in an orientation direction, the lower the thermal conductivity in this direction. In FIG. 3, the diagonal orientation directions D1 have a maximum density of inclusions. Therefore, the lowest thermal conductivities in these orientation directions D1 (called minimum thermal conductivity orientation direction) are found. D2 directions with a lower inclusion density have higher thermal conductivities. Thus, the heat flux will be guided towards these directions D2 for a faster and more homogeneous redistribution of the heat flow along the P-N junctions. Referring back to FIG. 1, the enlarged zone illustrates the structure of the inclusions network RZ of the silicon membrane with phononic structure 2. The inclusion network is periodic and symmetrical. More precisely, this inclusion network is in the form of squares having a higher density of inclusions in the first directions D1 and a lower density in the second directions of orientation D2. As can be seen in FIG. 1, the trace 14 on one of the faces (F1 for example) of a pillar 14 situated on the other face (F2) and any one of the adjacent pillars (7, 8, 17, 18) located on said one of the faces (F1) are aligned in the first orientation directions D1. As a result, the thermal conductivity of the phonon-structured silicon membrane between these pillars is minimized and the more efficient thermoelectric properties and a larger temperature difference are then obtained. Thus, the voltage generated by the thermoelectric generator will also be higher. In addition, the directions of orientation D2 inducing the higher thermal conductivities are parallel to the junctions of the P-N junctions. As a result, a more homogeneous temperature can be obtained in the junctions. These characteristics of thermal conductivity in combination with a redistribution of the thermal flux in the plane of the membrane through the alternating distribution of the pillars make it possible to obtain a thermoelectric generator having improved performances. Examples of technological steps for producing an example of a thermoelectric generator according to the invention are presented in FIGS. 4 to 20. This embodiment is shown for illustrative purposes and is not limiting. Several variants can be envisaged. As illustrated in FIG. 4, a silicon-on-insulator substrate commonly designated by the person skilled in the art under the acronym "SOI" ("Silicon On Insulator") is used here. The silicon-on-insulator substrate comprises a semiconductor film 28, for example made of silicon, situated beneath a buried insulating layer 29, commonly known by the acronym "BOX" ("Buried-OXide"). itself located above a carrier substrate 30, for example a semiconductor box. The thickness of the silicon film 28 determines the final thickness of the thermoelectric membrane 2. According to the characteristics defined above, it is preferable to have a thickness between 10 nm and 2 i.tm. Figures 5 to 9 relate to the steps of the implantation of the film 28. In Figure 5, it begins with the deposition of a layer of photoresist 31 to prepare a photolithography 32 in the next step. For example, a negative inorganic resin layer called HSQ may be used.
    [0014] An exposure gradient photolithography 32 is then applied (FIG. 6). By applying direct laser writing, the different exposure depths are then obtained on the resin layer 31. The photoresist layer 31 now has a profile of variable thickness after development (FIG. 7) and serves as a mask. for the ion implantation dilution in the next step. As illustrated in FIG. 8, it is possible to use a second organic resin 33 (for example the resin known as SAL 601) having a selectivity with respect to the resin 31 serving as a mask. Following a second-level lithography and the development of the second resin 33, an implantation of N-type dopants 34 is carried out. The vertical profile of the inorganic resin mask 31 makes it possible to modulate the dopant concentration laterally so as to improve thermoelectric efficiency. By analogy, a third level of lithography on a new layer of organic resin 35 (for example the so-called SAL 601 resin) and implantation of P-type dopants 36 are applied as illustrated in FIG. 9. Annealing of the film 28 is carried out in the end for activating dopants. In this way, P-N 3 ', 4' junctions coupled in series in the silicon film 28 were formed. They are distinguished from the P-N junctions 3, 4 described above by the fact that they do not yet have a phononic structure.
    [0015] It may be noted that the implantation of doping elements with a concentration modulation in the plane of the active membrane (film 28) is optional here. It can be performed by exposure gradient photolithography method or by any other method to achieve a dilution mask.
    [0016] The embodiment of the phononic structure is illustrated in FIGS. 10 to 13. FIG. 10 is an enlargement of the P-type dopant zone 4 'of the thin film 28. A layer of photosensitive or electro-sensitive positive resin 37 (for example PMMA or ZEP520 resin) is deposited on the thin film. By performing an electronic lithography 38 in the step illustrated in FIG. 11, the patterns of the phonon crystal can be obtained by electronic writing. The areas exposed in the step illustrated in FIG. 11 are then eliminated in the step shown in FIG. 12, and the silicon is etched to form the inclusions 39. Alternatively, the realization of the phononic structure can be carried out by means of FIG. other structuring methods such as nano-printing followed by dry or wet etching.
    [0017] Finally, the positive electrosensitive resin layer is removed in the step shown in FIG. 13. As a result, the thermoelectric thin film 28 containing the phonon-structured P-N junctions (3, 4) is produced.
    [0018] The further development of the thermoelectric generator is illustrated in FIGS. 14 to 20. First, a deposit of a metal layer 40 is deposited on the phononically structured film, for example by a so-called "PECVD" deposit, which determines the height of pillars.
    [0019] After depositing a first layer of photoresist, a structuring mask is used to determine the geometry of the pillars by optical lithography. A cathode sputtering is then performed to form an electrical insulator layer 41 located above the metal layer 40 and the structuring resin layer. The latter is removed by a so-called "Lift-Off" process and the final micro-structuring of the pillars is carried out by laser-thermal ablation on the uncovered metal areas of the thermally conductive electrical insulating layer, as illustrated in FIG. Figure 14.
    [0020] In Figure 15, a temporary adhesive resin layer 42 is deposited on the face F2 of the membrane comprising the metal pillars. The temporary adhesive resin layer 42 is then adhered to a temporary support 43 made of a material resistant to subsequent etching steps.
    [0021] Mechanical and chemical etching is then carried out in order to remove the silicon substrate 30 and the oxide layer 29 from the SOI substrate. As a result, the thin film 28 is ready for the realization of the pillars on the face Fi as shown in FIG. 16. Metal pillars of the face Fi are formed in a manner analogous to that illustrated in FIG. that the metal pillars are implemented staggered alternately on both sides of the film. Each pillar is coupled with a P-N junction and the two-sided pillars are not aligned on the same vertical plane as shown in Figure 17.
    [0022] It can also be noted that the thicknesses of pillars and thermally conductive electrical insulators above the pillars are identical on both sides of the membrane. As illustrated in FIG. 18, the first support 5, for example a sheet of flexible metal (such as stainless steel, aluminum, etc. with good thermal conductivity) intended to be coupled to a thermal source cold is deposited on the insulating layers located above the metal pillars 7 to 10 of the face Fi by a conventional step of transfer and bonding.
    [0023] Subsequently, contact vias are conventionally made for the electrical connection at locations E1, E2 (FIG. 19). Finally, the temporary adhesive resin 42 can be dissolved on the face F2 of the film in order to release it and obtain the membrane 2 of the thermoelectric generator 1. The second support 6 intended to be coupled to a hot thermal source is produced in a manner analogous to that of the first support 5 (Figure 20). The integrated thermoelectric generator 1 is thus obtained comprising a semiconductor membrane 2 with a suspended phonon structure.
    权利要求:
    Claims (18)
    [0001]
    REVENDICATIONS1. Thermoelectric generator, comprising a semiconductor membrane (2) containing at least one PN junction (3, 4) suspended between a first support (5) intended to be coupled to a cold thermal source and a second support (6) intended to be coupled to a hot thermal source.
    [0002]
    2. thermoelectric generator according to claim 1, wherein the semiconductor membrane (2) contains several alternating bands of N (3) and P (4) conductivity type constituting a plurality of PN junctions coupled in series, each PN junction extending. between a first face of the membrane facing the first support (5) and a second face of the membrane facing the second support (6), said membrane (2) being suspended by suspension means comprising thermally conductive pillars (7-23) distributed alternately on both sides (F1, F2) of the membrane, each pillar connecting a PN junction to the corresponding support.
    [0003]
    3. thermoelectric generator according to claim 2, wherein the pillars on one of the faces comprise at least two so-called electrically conductive contact pillars (25, 26) coupled to at least two locations of the support (E1, E2) corresponding to in order to generate an electrical signal and isolated from the corresponding support by a thermally conductive electrical insulator (27), and so-called electrically conductive connecting pillars electrically insulated from the corresponding support by a thermally conductive electrical insulator (24), and the pillars located on the other face comprise only so-called connecting pillars electrically conductive and electrically isolated from the corresponding support by a thermally conductive electrical insulator.
    [0004]
    4. thermoelectric generator according to one of the preceding claims, wherein said suspended membrane (2) is phononic structure (27) comprising an array of inclusions (39) of different constitution of the semiconductor material of the membrane.
    [0005]
    The thermoelectric generator according to claim 4 and one of claims 2 and 3, wherein the inclusion network (RZ) is symmetrical and comprises first orientation directions (D1) having a first inclusion density and a second orientation direction (D2) having a second inclusion density lower than the first density, the PN junction strips (3 and 4) are parallel to the second orientation density (D2), and the trace on the second orientation density one of the faces of a pillar (15) on the other side is aligned in the first orientation directions with any one of the adjacent pillars (8, 9, 18, 19) on one of the faces.
    [0006]
    6. thermoelectric generator according to claim 5, wherein the pillars (7-23) are distributed alternately staggered alternately on both sides of the membrane, the pillars on each of the two faces of the membrane forming groups of squares. , the trace on one of the faces of a pillar (15) located on the other face located in the center of a square of pillars (8, 9, 18, 19) located on said one of the faces.
    [0007]
    7. thermoelectric generator according to one of claims 4 to 6, wherein the inclusion network (RZ) is periodic with at least one step (p) of repetition lower than the mean free path of the thermal phonons and greater than the length of wave of thermal phonons.
    [0008]
    8. thermoelectric generator according to claim 7, wherein the network of inclusions (RZ) comprises a succession of different steps (p) of repetition of increasing sizes.
    [0009]
    9. thermoelectric generator according to one of claims 7 and 8, wherein the inclusion network (RZ) comprises a succession of inclusions of increasing size.
    [0010]
    10. thermoelectric generator according to one of claims 7 to 9, wherein the semiconductor material (2) comprises silicon and at least one step (p) of repetition is greater than 2 nm and less than 200 nm.
    [0011]
    11. thermoelectric generator according to one of the preceding claims, wherein the semiconductor material (2) comprises silicon and the thickness (e) of the membrane is between 10 nm and 2 pm.
    [0012]
    12. thermoelectric generator according to one of the preceding claims, wherein the membrane (2) extends parallel to the supports (5, 6).
    [0013]
    13. thermoelectric generator according to one of the preceding claims, wherein the membrane (2) is equidistant from the supports (5, 6).
    [0014]
    14. Thermoelectric generator according to one of the preceding claims, wherein the supports (5, 6) are rigid.
    [0015]
    15. Generator according to claim 14, wherein the materials of the supports (5, 6) are metallic or semiconductors.
    [0016]
    16. Thermoelectric generator according to one of claims 1 to 13, wherein the supports (5, 6) are flexible.
    [0017]
    17. Thermoelectric generator according to one of the preceding claims, made in an integrated manner.
    [0018]
    Integrated circuit incorporating a thermoelectric generator according to one of claims 1 to 17.
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1461760|2014-12-02|
    FR1461760A|FR3029355B1|2014-12-02|2014-12-02|THERMOELECTRIC GENERATOR|FR1461760A| FR3029355B1|2014-12-02|2014-12-02|THERMOELECTRIC GENERATOR|
    US14/851,536| US10103310B2|2014-12-02|2015-09-11|Thermo-electric generator|
    CN201510614149.3A| CN105655473B|2014-12-02|2015-09-23|thermoelectric generator|
    CN201520742953.5U| CN205028926U|2014-12-02|2015-09-23|Thermoelectric generator and integrated circuit|
    US16/047,505| US10741740B2|2014-12-02|2018-07-27|Thermo-electric generator|
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