阅读说明：本技术 制作集成热电转换器的方法和由此获得的集成热电转换器 (Method of making an integrated thermoelectric converter and integrated thermoelectric converter obtained thereby ) 是由 P·菲拉里 F·F·维拉 L·祖里诺 A·诺梅尔里尼 L·塞吉齐 L·扎诺蒂 B·穆拉里 于 2021-05-18 设计创作，主要内容包括：本公开的实施例涉及制作集成热电转换器的方法和由此获得的集成热电转换器。一种方法包括：提供硅基材料层,具有第一表面以及与第一表面相对并且通过硅基材料层厚度与第一表面隔开的第二表面；形成具有第一塞贝克系数的第一热电半导体材料的多个第一热电有源元件,以及形成具有第二塞贝克系数的第二热电半导体材料的多个第二热电有源元件,第一和第二热电有源元件被形成为从第一表面延伸穿过硅基材料层厚度到第二表面；形成与硅基材料层的第一和第二表面相对应的导电互连件,并且形成电连接至导电互连件的输入电端子和输出电端子,第一和第二热电半导体材料包括在多孔硅或多晶SiGe或多晶硅中选择的硅基材料。(Embodiments of the present disclosure relate to methods of fabricating integrated thermoelectric converters and integrated thermoelectric converters obtained thereby. One method comprises the following steps: providing a silicon-based material layer having a first surface and a second surface opposite the first surface and spaced from the first surface by a silicon-based material layer thickness; forming a plurality of first thermoelectric active elements of a first thermoelectric semiconductor material having a first seebeck coefficient, and forming a plurality of second thermoelectric active elements of a second thermoelectric semiconductor material having a second seebeck coefficient, the first and second thermoelectric active elements being formed to extend from the first surface through the thickness of the silicon-based material layer to the second surface; forming electrically conductive interconnects corresponding to the first and second surfaces of the layer of silicon-based material, and forming input and output electrical terminals electrically connected to the electrically conductive interconnects, the first and second thermoelectric semiconductor materials comprising a silicon-based material selected among porous silicon or poly-SiGe or poly-silicon.)

1. A method of making a thermoelectric converter, comprising:

forming a plurality of first thermoelectric active elements of a first thermoelectric semiconductor material having a first seebeck coefficient and a plurality of second thermoelectric active elements of a second thermoelectric semiconductor material having a second seebeck coefficient in a silicon-based material layer having a first surface, a second surface opposite the first surface, and a first thickness between the first surface and the second surface, the first thermoelectric active elements and the second thermoelectric active elements each being formed to extend through the first thickness from the first surface to the second surface; and

forming conductive interconnects over at least one of the first surface or the second surface of the silicon-based material layer, the conductive interconnects each electrically interconnecting a first thermoelectric active element of the plurality of first thermoelectric active elements with a corresponding second thermoelectric active element of the plurality of second thermoelectric active elements; and forming input and output electrical terminals electrically coupled to the conductive interconnect,

wherein the first thermoelectric semiconductor material and the second thermoelectric semiconductor material each comprise a silicon-based material selected from the group consisting of porous silicon, polycrystalline silicon germanium SiGe and polycrystalline silicon.

2. The method of claim 1, wherein the silicon-based material layer is in Si_0.7Ge_0.3The material of (3) is selected from poly SiGe or epitaxial polysilicon.

3. The method of claim 1, wherein the plurality of first thermoelectric active elements of the first thermoelectric semiconductor material having a first seebeck coefficient are doped with acceptor dopants and the plurality of second thermoelectric active elements of the second thermoelectric semiconductor material having a second seebeck coefficient are doped with donor dopants.

4. The method of claim 1, wherein the silicon based material layer is polysilicon, and the method comprises: and epitaxially growing the polycrystalline silicon layer on the oxidized surface of the substrate.

5. The method of claim 4, wherein forming the plurality of first thermoelectric active elements of the first thermoelectric semiconductor material having the first Seebeck coefficient comprises:

forming a first trench in the silicon-based material layer, an

Filling the first trench with polysilicon or poly SiGe doped with an acceptor dopant; and

wherein forming the plurality of second thermoelectric active elements of the second thermoelectric semiconductor material having the second seebeck coefficient comprises:

forming a second trench in the silicon-based material layer, an

Filling the second trench with polysilicon or poly SiGe doped with a donor dopant.

6. The method of claim 5, wherein each of the first and second trenches is filled with polysilicon, and further comprising:

converting the doped polysilicon filling the first and second trenches into doped porous silicon.

7. The method of claim 1, comprising:

forming the silicon-based material layer includes:

iterating the following steps at least twice:

forming a poly SiGe layer on an oxidized surface of a substrate, wherein the poly SiGe layer has a thickness that is a portion compared to the first thickness of the silicon-based material layer;

selectively doping a first region of the poly SiGe layer with an acceptor dopant; and

selectively doping a second region of the poly SiGe layer with a donor dopant,

wherein after the iteration, each stack of poly SiGe layers has an overall thickness corresponding to the first thickness of the silicon-based material layer; and

forming a trench in the stack of each of the poly SiGe layers, thereby obtaining separate portions of a doped first region and a doped second region.

8. The method of claim 1, further comprising:

and bonding the silicon-based material layer to an amorphous silicon solar photovoltaic cell wafer.

9. The method of claim 8, wherein bonding the silicon-based material layer comprises: forming a conductive bonding layer in electrical contact with the solar photovoltaic cell wafer, and forming a first electrical contact of the solar photovoltaic cell wafer.

10. The method of claim 9, wherein the solar photovoltaic cell wafer comprises a first region of a first conductivity type, the method comprising: implanting a dopant species to form a second region of a second conductivity type opposite the first conductivity type, and forming a second electrical contact electrically coupled to the second region.

11. A method of making a thermoelectric converter, comprising:

forming conductive interconnects on the first and second wafers;

printing semiconductor regions of a first conductivity type and a second conductivity type on the conductive interconnects of at least one of the first or second silicon wafers by maskless mesoscale material deposition according to a pattern;

forming bonding regions of conductive material on the other silicon wafer of the at least one of the first or second silicon wafers, the bonding regions being arranged to correspond to the pattern; and

contacting the semiconductor region with the bonding region; and

bonding the semiconductor region to the bonding region by applying pressure to the first and second silicon wafers.

12. The method of claim 11, wherein the semiconductor region is a bismuth telluride region.

13. The method of claim 11, wherein the junction region is formed using maskless mesoscale material deposition.

14. The method of claim 11, comprising: and forming an anode region on the surface of the first silicon wafer far away from the second silicon wafer.

15. The method of claim 14, comprising: a cathode region is formed in the first silicon wafer.

16. An integrated thermoelectric converter comprising:

a first pillar structure comprising one of porous silicon, polycrystalline silicon germanium, or polycrystalline silicon, and doped with a first conductivity type;

a second pillar structure comprising one of porous silicon, polycrystalline silicon germanium, or polycrystalline silicon, and doped with a second conductivity type; and

a first conductive interconnect structure in electrical contact with a first end of the first pillar structure and a first end of the second pillar structure.

17. The integrated thermoelectric converter of claim 16, comprising: a first insulating structure surrounding the first pillar structure, and a second insulating structure surrounding the second pillar structure.

18. The integrated thermionic electric converter of claim 16 wherein the first pillar structure comprises polycrystalline silicon germanium and the first pillar structure comprises a plurality of polycrystalline silicon germanium layers stacked on top of one another.

19. The integrated thermoelectric converter of claim 16, comprising a substrate, wherein the first pillar structure comprises a first portion of porous silicon and a second portion of polycrystalline silicon, the second portion being between the first portion and the substrate.

20. The integrated thermoelectric converter of claim 19, wherein the second portion of the first pillar structure is in contact with the substrate.

Technical Field

The present disclosure relates generally to the field of solid state technology, particularly semiconductor technology and devices, and more particularly to a solid state integrated thermoelectric converter and method of making the same, such as a thermoelectric generator (also referred to as a "TEG").

Background

Direct conversion of thermal energy into electrical energy (and vice versa) by the seebeck effect is a promising method of harvesting energy from heat sources, especially when reduced temperature gradients are involved and not utilized (such as residual heat of industrial plants, residual heat of automobile engines, low temperature heat sources).

Thermoelectric generators are low enthalpy waste heat utilization devices, such as used for batteryless radiator valve actuators or flashlights (in this latter case, utilizing the temperature difference between human body temperature and ambient temperature).

Thermoelectric generators utilize thermoelectric materials that are capable of generating electricity directly from heat by converting a temperature differential into a voltage.

A good thermoelectric material should have both high electrical conductivity (σ) and low thermal conductivity (κ). Having a low thermal conductivity ensures that as one side of the material heats up, the other material side remains cold, which helps generate a significant voltage even at very low temperature gradients.

Tellurium-based thermoelectric generators utilize tellurium-based materials as thermoelectric materials.

Tellurium compounds (such as bismuth telluride (Bi)₂Te₃) Exhibits good seebeck coefficient (the seebeck coefficient of a material (also known as thermal power, thermoelectric sensitivity, being a measure of the magnitude of the induced thermoelectric voltage in response to a temperature difference across the material caused by the seebeck effect), high electrical conductivity and low thermal conductivity (the thermal conductivity of bismuth telluride is 2W/mK, by way of example only). These properties make bismuth telluride suitable for use in forming "thermoelectric active elements" of thermoelectric generators (by "thermoelectric active element" or "active element" is meant a thermoelectric element in a thermoelectric material capable of converting the temperature drop or temperature gradient across them to an electrical potential by the seebeck effect).

A tellurium-based thermoelectric generator includes a plurality of interconnected n-doped bismuth telluride active elements and p-doped bismuth telluride active elements (these active elements are also referred to as "legs") interconnecting the plurality of n-doped and p-doped bismuth telluride active elements between a pair of opposing ceramic substrates and wires provided with metal (Cu or Au) contact regions. The n-doped bismuth telluride active element is typically formed as a discrete element by means of the following process: involves forming an ingot starting from powdered material, then cutting the ingot to form pellets, and then forming seebeck feet between two ceramic substrates where the pellets are placed (in a manual or semi-automatic assembly stage).

Thus, existing tellurium-based thermoelectric generators are discrete components. Bismuth telluride is not suitable for use as a material in standard Integrated Circuit (IC) fabrication processes, which are silicon-based.

Moreover, tellurium-based thermoelectric generators typically exhibit relatively good efficiency only over a limited temperature range (typically, about 100K at room temperature), as well as thermoelectric properties that degrade rapidly with increasing temperature. This reduces the application area of the tellurium-based thermoelectric generator.

Additionally, tellurium is a relatively rare element, which inherently limits its widespread use.

Furthermore, the use of large amounts of tellurium compounds (such as bismuth telluride) may present environmental concerns, particularly in the disposal of scrapped equipment.

In silicon-based thermoelectric generators, silicon-based materials (n-doped and p-doped to exhibit different seebeck coefficients) are used as thermoelectric materials to form active elements.

Silicon-based thermoelectric generators fabricated using compatible silicon technologies can be classified into two families: in the first series of devices, the heat flow is parallel to the substrate, while in the other series, the heat flow is orthogonal to the substrate ("out-of-plane" heat flux). The architecture of these integrated thermoelectric generators typically includes a plurality of base units having n-p doped legs, arranged in such a way that the base units are thermally parallel and electrically series connected. Generally, an integrated thermoelectric generator with heat flow parallel to the substrate can deposit electrically conductive legs of thermoelectrically active material on a very high thermal resistance material or film (suspended a few hundred microns above the substrate), or the active material legs themselves are free-standing (no film).

The out-of-plane heat flux thermoelectric generator minimizes heat loss, simplifies system-level thermal coupling, enhances overall performance, and is suitable for miniaturization and integration of other applications, such as microelectronics and optoelectronic devices.

Tomita et al criticize a Planar silicon-based Thermoelectric generator using silicon nanowires about 10 to 100 μm long as active elements suspended on a cavity to cut off a thermal current bypass to ensure a temperature difference across the silicon nanowires, in 2018, 6, 18 to 22 days, 6/cm, 2-Class High Power Density Planar Si-nano wire Thermoelectric generator, 50 th IEEE VLSI Technology seminar of VLSI Technology 2018 in santalasan us, usa. The authors of the paper propose a design concept for a planar short silicon nanowire thermoelectric generator without a cavity structure that uses a steep temperature gradient formed near the main thermal current.

WO 2018/078515 discloses an integrated thermoelectric generator in an out-of-plane heat flux configuration. The generator further comprises a top capping layer deposited on a free surface of said planar non-conductive cover layer oriented in an opposite direction with respect to said void space so as to cover the through-holes of the non-conductive cover layer.

Disclosure of Invention

The applicant has perceived that the silicon-based thermoelectric generators proposed in the art exhibit drawbacks.

Silicon has a large electrical conductivity and a good seebeck coefficient, but as a thermoelectric material, it has a disadvantage of having a higher thermal conductivity (148W/mK) than bismuth telluride (thermal conductivity of 2W/mK). Furthermore, silicon-based thermoelectric generators with cavities have a low mechanical stability due to the presence of the cavities. Other drawbacks of known silicon-based thermoelectric generators are: the industrialization is difficult; low power (-100 muW/cm)²) (ii) a And high semiconductor area consumption.

The applicant has tackled the problem of devising a novel thermoelectric converter which overcomes the drawbacks affecting the known thermoelectric generators.

The applicant has found that the active elements of a thermoelectric converter can be realized in alternative materials (except bismuth telluride and silicon as known in the art) which are good thermoelectric materials and which are suitable for standard IC manufacturing techniques, thereby making it possible to fabricate integrated thermoelectric converters.

The applicant has found that a good thermoelectric material suitable for realizing an alternative to the active elements of the integrated thermoelectric converter is porous silicon, for example n-doped or p-doped.

The n-doped and p-doped porous silicon thermoelectrically active element can be obtained by converting n⁺And p⁺Doped polysilicon. Porous silicon advantageously has very low thermal conductivity (0.15 to 1.5W/mK at a porosity of about 75%).

The applicant has also found that another suitable alternative good thermoelectric material for realizing the active elements of an integrated thermoelectric converter is for example n-doped or p-doped polycrystalline silicon germanium (poly SiGe). Poly SiGe has a thermal conductivity of 3 to 5W/mK and applicant uses it as a material for realizing an active element of a thermoelectric converter.

Another thermoelectric material for realizing the active element of the integrated thermoelectric converter is polysilicon, for example n-doped and p-doped.

According to one aspect of the present disclosure, a method of fabricating an out-of-plane (e.g., having a heat flux orthogonal to a substrate) thermoelectric converter includes:

providing a silicon-based material layer having a first surface and a second surface opposite the first surface and spaced from the first surface by a silicon-based material layer thickness;

forming a plurality of first thermoelectric active elements of a first thermoelectric semiconductor material having a first seebeck coefficient and forming a plurality of second thermoelectric active elements of a second thermoelectric semiconductor material having a second seebeck coefficient, wherein the first thermoelectric active elements and the second thermoelectric active elements are formed to extend from the first surface through the thickness of the silicon-based material layer to the second surface;

forming electrically conductive interconnects corresponding to the first and second surfaces of the silicon-based material layer to electrically interconnect the plurality of first thermoelectric active elements and the plurality of second thermoelectric active elements, an

Input and output electrical terminals are formed electrically connected to the conductive interconnects.

The first thermoelectric semiconductor material and the second thermoelectric semiconductor material comprise a silicon-based material selected between porous silicon or poly-SiGe or poly-silicon.

In an embodiment, the silicon-based material layer is in poly-SiGe (in particular poly-Si)_0.7Ge_0.3) Or epitaxial polysilicon.

In an embodiment, the plurality of first thermoelectric active elements of the first thermoelectric semiconductor material having the first seebeck coefficient comprises doped porous silicon or poly-SiGe or poly-si doped with acceptor or donor dopants, and the plurality of second thermoelectric active elements of said second thermoelectric semiconductor material having the second seebeck coefficient comprises doped porous silicon or poly-SiGe or poly-si each doped with donor or acceptor dopants.

In an embodiment, the providing the layer of silicon-based material comprises epitaxially growing a layer of polysilicon on an oxidized surface of the substrate.

In an embodiment, the forming a plurality of first thermoelectric active elements of a first thermoelectric semiconductor material having a first seebeck coefficient comprises:

forming a first groove in the silicon-based material layer; and

the first trench is filled with polysilicon or poly SiGe doped with acceptor or donor dopants.

In an embodiment, the forming the plurality of second thermoelectric active elements of the second thermoelectric semiconductor material having the second seebeck coefficient includes:

forming a second groove in the silicon-based material layer; and

the second trench is filled with polysilicon or poly SiGe doped with donor or acceptor dopants.

In an embodiment, the method may further include converting the doped polysilicon filling the first trench and the second trench into doped porous silicon.

In an embodiment, the providing a silicon based material layer comprises:

iterating at least twice the following steps:

forming a poly SiGe layer on an oxidized surface of a substrate, wherein the poly SiGe layer has a thickness that is a fraction of a thickness of the silicon-based material layer;

selectively doping a first region of the poly SiGe layer with an acceptor or donor dopant; and

selectively doping a second region of the poly SiGe layer with a donor or acceptor dopant,

such that after said iteration, each stack of poly SiGe layers has an overall thickness corresponding to the thickness of said silicon-based material layer; and

a trench is formed in each of the stacks of poly SiGe layers to obtain separate portions of the doped first region and the doped second region.

According to another aspect of the present disclosure, an out-of-plane integrated thermoelectric converter is presented. The apparatus comprises:

a silicon-based material layer having a first surface and a second surface opposite the first surface and spaced from the first surface by a silicon-based material layer thickness;

a plurality of first thermoelectric active elements of a first thermoelectric semiconductor material having a first seebeck coefficient and a plurality of second thermoelectric active elements of a second thermoelectric semiconductor material having a second seebeck coefficient, wherein the first thermoelectric active elements and the second thermoelectric active elements extend from the first surface through the thickness of the silicon-based material layer to the second surface;

electrically conductive interconnects corresponding to the first and second surfaces of the silicon-based material layer to electrically interconnect the first and second pluralities of thermoelectric active elements, an

An input electrical terminal and an output electrical terminal electrically connected to the conductive interconnect.

The first thermoelectric semiconductor material and the second thermoelectric semiconductor material comprise a silicon-based material selected among porous silicon or polycrystalline SiGe.

In an embodiment, the silicon-based material layer is in poly-SiGe (in particular poly-Si)_0.7Ge_0.3) Or epitaxial polysilicon.

In an embodiment, said first thermoelectric semiconductor material having a first seebeck coefficient is porous silicon or polysilicon or poly-SiGe doped with acceptor or donor dopants, and said second thermoelectric semiconductor material having a second seebeck coefficient is porous silicon or polysilicon or poly-SiGe each doped with donor or acceptor dopants.

In the examples:

each of the plurality of first and second thermoelectric active elements and each of the second thermoelectric active elements has a first end at the first surface of the silicon based material layer and a second end at the second surface, the electrically conductive interconnects electrically connected:

a first end of a common first thermoelectric active element to a first end of a second thermoelectric active element; and

a second end of the common first thermoelectric active element to a second end of another second thermoelectric active element such that the plurality of first thermoelectric active elements and the plurality of second thermoelectric active elements are connected in series and alternate with each other.

According to yet another aspect of the present disclosure, an electronic system comprising a thermoelectric converter according to the previous aspect is presented.

The advantages resulting from using such alternative materials to form the active element of a thermoelectric converter are:

ease of industrialization;

the power level is about 1mA (whereas the characteristic power level of conventional thermoelectric generator structures is about 100 μ W/cm for a typical Δ T-10K²)；

Ability to operate at low or high Δ T;

no mechanical stability problems; and

low area consumption.

Drawings

These and other features and advantages of the present disclosure will become apparent from the following description of exemplary embodiments, which is provided by way of non-limiting example only.

For better readability, the following description should be read with reference to the accompanying drawings, in which:

fig. 1A to 1G illustrate some steps of a method of fabricating a thermoelectric converter according to an example embodiment of the present disclosure;

fig. 2A-2L illustrate some steps of a method of fabricating a thermoelectric converter according to an example embodiment of the present disclosure;

3A-3I illustrate some steps of a method of fabricating a thermoelectric converter in accordance with yet another example embodiment of the present disclosure;

fig. 4A-4E illustrate some steps of a fabrication method subsequent to the steps of fig. 2A-2L or fig. 3A-3I in an example embodiment of the disclosure (the same or similar process steps may also be subsequent to the steps of fig. 1A-1G);

FIG. 4F shows example steps for forming contact pads;

FIG. 5 illustrates in a top plan view a layout of a thermoelectric converter obtained by a method according to an example embodiment of the present disclosure, the method of an example embodiment including the steps illustrated in FIGS. 1A-1G and steps similar to FIGS. 4A-4E;

fig. 6 shows in a top plan view a layout of a thermoelectric converter obtained by a method according to an embodiment of the present disclosure, the method of an example embodiment comprising the steps shown in fig. 2A to 2L or fig. 3A to 3I and fig. 4A to 4E;

FIG. 7 shows a simplified block diagram of an electronic system including a thermoelectric converter, according to an embodiment of the present disclosure;

FIG. 8 shows a cross-section of a solar energy recovery device using the thermoelectric converter of FIG. 4F taken along section line VIII-VIII of FIGS. 9A and 9B after bonding of the thermoelectric and solar cell wafers;

FIG. 9A is a top plan view of the thermoelectric chip of FIG. 8 prior to bonding;

FIG. 9B is a bottom plan view of the solar cell wafer of FIG. 8 prior to bonding;

FIG. 10 is a cross-section of the solar energy recovery device of FIG. 8 in a further manufacturing step;

FIG. 11 is a cross-section of the solar energy recovery apparatus of FIG. 10 taken along section line XI-XI of FIGS. 12A and 12B in a further manufacturing step;

FIG. 12A is a top plan view of the thermoelectric wafer of FIG. 11;

FIG. 12B is a bottom plan view of the solar cell wafer of FIG. 11;

FIG. 13 is a scheme depicting possible connections of the solar recovery apparatus of FIG. 11;

figures 14 and 15 show cross-sections of another solar energy recovery device in different manufacturing steps;

FIG. 16 is a cross-section of a different solar energy recovery apparatus;

FIG. 17 is a schematic representation of a system disclosed herein; and

fig. 18 is a cross section of an example of a solar cell wafer that can be used in a solar energy recovery device according to the present disclosure.

It is noted that the drawings in the figures are not necessarily to scale.

Detailed Description

In the following, reference will be made to the accompanying drawings, which illustrate some steps of a method of fabricating a thermoelectric converter according to an example embodiment of the present disclosure. In the drawings, like and/or corresponding elements are referred to by like reference numerals.

Reference is first made to fig. 1A to 1G, which illustrate some steps of a fabrication method according to an example embodiment of the present disclosure.

Starting from a silicon substrate (first silicon wafer) 105, the surface of the silicon substrate 105 is oxidized (for example by means of thermal oxidation) to form an oxide layer 110, for example silicon dioxide (SiO)₂). A poly SiGe layer 115 is then formed over the oxide layer 110. The resulting structure is schematically depicted in fig. 1A.

The poly SiGe layer 115 is, for example, poly Si_0.7Ge_0.3And (3) a layer. The poly SiGe layer 115 may be formed, for example, by means of deposition, such as, but not limited to, chemical deposition, e.g., Chemical Vapor Deposition (CVD); among the various CVD techniques, low pressure CVD (lpcvd) may be utilized, for example. The deposition is from Silane (SiH)₄) And germane (GeH)₄) The method is carried out. Alternatively, the SiGe polysilicon layer 115 may be formed by means of epitaxial growth in an epitaxial reactor. Both techniques result in a conformal poly SiGe layer 115.

The poly SiGe layer 115 may for example have a thickness of some microns, for example about 1 μm.

Then, as depicted in fig. 1B and 1C, alternating n + doped regions 120a and p + doped regions 120B of n + doped and p + doped poly SiGe are each formed in the poly SiGe layer 115. Dopants (donor dopants for the n + doped region 120a and donor dopants for the p + doped region 120b) may be selectively introduced into the poly SiGe layer 115 by ion implantation. For example, a suitable donor dopant may be phosphorus or arsenic and a suitable acceptor dopant may be boron. The n + doped regions 120a and the p + doped regions 120B may, for example, have the shape of substantially parallel strips formed in the poly SiGe layer 115 (where "parallel" is intended to be along a direction orthogonal to the plane of the drawing of fig. 1B and 1C), the n + doped regions 120a and the p + doped regions 120B alternating and, for example (but not limited to), being continuous with one another (in a direction from left to right of the drawing).

The steps of forming the poly SiGe layer and forming the n + doped region and the p + doped region in the poly SiGe layer are repeated two or more times. As depicted in fig. 1D, each new layer of poly SiGe is formed (e.g., by the same technique as the first poly SiGe layer 115) on a previous layer of poly SiGe, and is formed (e.g., by ion implantation) in each newly formed poly SiGe layer in a manner aligned (e.g., vertically in the direction from the bottom to the top of the drawing sheet of fig. 1D) with the previously formed n + doped region 120a and p + doped region 120b formed in the previous poly SiGe layer(s). In this way, a stack 125a of n + doped regions and a stack 125b of p + doped regions are obtained, whereby a thermoelectric element of the thermoelectric converter will be formed. In this way, the stacks 125a and 125b of n + and p + doped regions take the form of substantially parallel strips formed in a stack of poly SiGe layers (where again "parallel" is intended along a direction orthogonal to the plane of the drawing of fig. 1D), the stacks 125a and 125b of n + and p + doped regions alternating and for example (but not limited to) continuous with each other (along a direction from left to right of the drawing), as visible for example in fig. 1E.

The number of repetitions of the steps of forming the poly SiGe layers and forming the n + and p + doped regions in the poly SiGe layers depends on the thickness of each of the poly SiGe layers (the stacked poly SiGe layers may have all the same thickness or different thicknesses from each other), and on the desired overall thickness of the stack of poly SiGe layers. The overall thickness of the stack of poly SiGe layers should be such that a sufficient thermal difference is ensured between the bottom and top of the stack of n + doped regions 125a and the stack of p + doped regions 125b, even for relatively low temperature gradients. For example, the overall thickness of the stack of poly SiGe layers may be several tens of microns, in particular about 10 μm to about 30 μm (thus, for an exemplary thickness of a common poly SiGe layer of about 1 μm, the steps of forming the poly SiGe layer and forming the n + doped region and the p + doped region in the poly SiGe layer are repeated several tens of times).

The trench 130 is then formed in the stack of n + doped regions 125a and the stack of p + doped regions 125 b. The groove 130 is formed, for example, as a cylindrical shell. The trench 130 extends down to the oxide layer 110. A plurality of grooves 130 are formed along each of the stacks 125a and 125b, which are in the shape of strips, as shown in fig. 1E. Each trench 130 defines a respective (e.g. cylindrical) portion 133a of the respective stack 125a of n + doped regions or a respective (e.g. cylindrical) portion 133b of the respective stack 125b of p + doped regions, these portions 133a and 133b remaining separate from the rest of the respective stack 125a of n + doped regions and the stack 125b of p + doped regions. The (e.g. cylindrical) portions 133a and 133b of the stack 125a of n + doped regions and the stack 125b of p + doped regions will form the thermoelectrically active elements (e.g. the "legs") of the thermoelectric converter.

By means of an oxidation process, the trench 130 is filled with oxide and the top surface of the structure (e.g. the surface opposite the silicon substrate 105) is covered by an oxide layer 135. The oxide may be, for example, SiO₂. In particular, the oxidation process may involve a thermal oxidation process to coat the sidewalls of the trenches 130 with oxide, followed by depositing a thick oxide layer using TEOS (tetraethylorthosilicate) to fill the trenches and cover the structure surface with an oxide layer 135. The resulting structure is shown in FIG. 1F. In this way, the (e.g. cylindrical) portions of the stack of n + doped regions 125a and the stack of p + doped regions 125b defined by the trench 130 remain insulated from the remaining portions of the respective stack of n + doped regions 125a and the stack of p + doped regions 125 b. As mentioned, the (e.g. cylindrical) portions of the stack 125a of n + doped regions and the stack 125b of p + doped regions defined by the trenches 130 will form thermoelectric elements (e.g. legs) 133a (n-doped, e.g. with a first seebeck coefficient, in particular with a first sign, e.g. positive) and 133b (p-doped, e.g. with a second, different seebeck coefficient, in particular with an opposite sign, e.g. negative) of the thermoelectric converter.

As can be seen in fig. 1G, contact openings are formed in the oxide layer 135, corresponding to the n + doped thermoelectric elements 133a and the p + doped thermoelectric elements 133b defined by the trenches 130, and exampleA conductive layer 140, such as a metal, is formed on the oxide layer 135 and then patterned to define conductive lines 143 interconnecting the n + doped thermoelectric elements 133a and the p + doped thermoelectric elements 133 b. The surface of the structure is then oxidized (e.g., SiO)₂) Layer 145 covers.

Reference is now made to fig. 2A-2L, which illustrate some steps of a method according to another example embodiment of the present disclosure.

Starting from a silicon substrate (first silicon wafer) 205, the surface of the silicon substrate 205 is oxidized to form an oxide layer 210, for example silicon dioxide (SiO)₂)。

A (relatively thick) layer 215 of polysilicon ("epitaxial poly") is then formed over the oxide layer 210. For example, polysilicon layer 215 is formed by means of epitaxial growth in an epitaxial reactor.

The resulting structure is depicted in fig. 2A.

The thickness d of the polysilicon layer 215 should ensure, for example, that there is a sufficient thermal differential (as described below) between the bottom and top of the thermoelectric elements to be formed therein, even for relatively low ambient temperature gradients. For example, the thickness of layer 215 may be several tens of microns, particularly from about 10 μm to about 30 μm.

The surface of the polysilicon layer 215 is then oxidized to form an oxide layer 220, such as silicon dioxide (SiO)₂) And (3) a layer. The resulting structure is shown in FIG. 2B.

As shown in fig. 2C, a trench 225 is then formed in polysilicon layer 215. The trench 225 extends down to the oxide layer 210 covering the surface of the silicon substrate 205. The groove 225 may be cylindrical, for example. The trench 225 may, for example, have a width w of about 3 μm.

Then, as depicted in fig. 2D, the walls of the trench 225 are oxidized by a layer 230 (e.g., silicon dioxide (SiO), for example, by thermal oxidation₂) Layer) is covered. In this manner, a cylindrical shell of oxide 230 is created within trench 225.

An n + doped poly SiGe layer 235 is formed over a surface of the structure (e.g., the surface opposite the silicon substrate 205). The n + doped poly SiGe layer 235 is, for example, n + doped poly Si_0.7Ge_0.3A polysilicon layer. The n + doped poly SiGe layer 235 may be formed, for example, by means of deposition, in particular chemical deposition, even more particularly Chemical Vapor Deposition (CVD); among the various CVD techniques, low pressure CVD (lpcvd) may be utilized. The deposition is from Silane (SiH)₄) And germane (GeH)₄) The method is carried out. The n + doped poly SiGe is conformal. During the deposition process, the n + doped poly SiGe fills the trench 225 (its walls are covered by oxide 230). The resulting structure is shown in FIG. 2E.

By means of a chemical mechanical polishing ("CMP") step, the n + doped poly SiGe layer 235 is removed from over the surface of the oxide layer 220, leaving only a (e.g. cylindrical) portion 237 of n + doped poly SiGe within the trench 225, the walls of which are covered by the oxide 230, as depicted in fig. 2F.

Then, other trenches 240 are formed in layer 215. Similar to trench 225, the other trenches 240 extend down to the oxide layer 210 covering the surface of the silicon substrate 205. The other grooves 240 may be cylindrical, for example. Similar to trench 225, trench 240 may, for example, have a width of about 3 μm. Other trenches 240 are formed to obtain the structure shown in fig. 2G, where other trenches 240 alternate with trenches 225.

Then, as depicted in fig. 2H, the walls of the other trenches 240 are oxidized by a layer 245 (e.g., silicon dioxide (SiO) such as by a thermal oxidation process₂) Layer) is covered. In this way, a cylindrical shell of oxide 245 is created within the trench 240.

A p + doped poly SiGe layer 247 is formed over the surface of the structure. The p + doped poly SiGe layer 247 is, for example, p + doped poly Si_0.7Ge_0.3And (3) a layer. The p + doped poly SiGe layer 247 may be formed, for example, by means of deposition, in particular chemical deposition, even more particularly Chemical Vapor Deposition (CVD); among the various CVD techniques, low pressure CVD (lpcvd) may be utilized. The deposition is from Silane (SiH)₄) And germane (GeH)₄) The method is carried out. The p + doped poly SiGe is conformal. During the deposition process, the p + doped poly SiGe fills the further trenches 240 (whose walls are covered by oxide 245). The resulting structure is shown in FIG. 2I.

By means of a chemical mechanical polishing ("CMP") step, the p + doped poly SiGe layer 247 is removed from over the surface of the oxide layer 220, leaving only a (e.g. cylindrical) portion 249 of p + doped poly SiGe (whose walls are covered by oxide 245) within the further trench 240, as depicted in fig. 2J.

In this way, the (e.g. cylindrical) portions 237 of n + doped poly SiGe and the (e.g. cylindrical) portions 249 of p + doped poly SiGe, defined by the trenches 225 and 245 whose walls are covered by the oxides 230 and 245, remain insulated from the surrounding polysilicon layer 215. These n + -doped poly SiGe (e.g., cylindrical) portions 237 and p + -doped poly SiGe portions 249 will form the thermoelectric elements (e.g., the "legs") of the thermoelectric converter.

It is noted that each of the n + -doped poly SiGe portions 237 and each of the p + -doped poly SiGe portions 249 visible in fig. 2J may identify a respective array of n + -doped poly SiGe portions 237 (each formed within a respective trench 225, whose walls are covered by the oxide 230) and a respective array of n + -doped poly SiGe portions 249 (each formed within a respective further trench 240, whose walls are covered by the oxide 245) extending in a direction orthogonal to the drawing plane of fig. 2J (as may be clearly understood at fig. 5 described later).

The surface of the structure (opposite the silicon substrate 205) is then oxidized to form an oxide layer 250, such as silicon dioxide (SiO), covering the entire surface of the structure₂) Layer as shown in fig. 2K.

As can be seen in fig. 2L, corresponding to each of the n + doped poly SiGe portions 237 and each of the p + doped poly SiGe portions 249, contact openings are formed on the oxide layer 250, and a conductive layer 255, e.g., a metal, is formed on the oxide layer 250 and then patterned to define first leads 257 interconnecting the thermoelectric elements 235 and 245. The surface of the structure is then covered by a further oxide layer 260, for example SiO₂. Together, oxide layers 250 and 260 form a surface oxide layer 270 embedded in first conductive line 257.

In an alternative embodiment, instead of being doped with n + doped poly SiGe and p +, respectivelyPoly SiGe, thermoelectric elements 235 and 245 may be made of n-doped porous silicon and p-doped porous silicon, respectively. As mentioned in the foregoing, porous silicon advantageously has very low thermal conductivity (0.15 to 1.5W/mK at a porosity of about 75%). n-doped porous silicon and p-doped porous silicon thermoelements 235 and 245 may be formed by separately converting n⁺And p⁺Doped polysilicon.

Fig. 3A-3I depict some steps of a process of forming thermoelectric elements 235 and 245 made of porous silicon.

Starting with the structure shown in fig. 2B, a mask layer 305 (e.g., a silicon nitride layer or a thick oxide layer) is formed over the oxide layer 220, as depicted in fig. 3A.

As shown in fig. 3B, a trench 310 is then formed by selective etching, the trench 310 extending from the surface of the mask layer 305 (which protects the structure from etching when the trench is not formed) down to the oxide layer 210 covering the silicon substrate 205. The trench 310 may be similar to the trench 225 of the previously described embodiments (e.g., a cylindrical trench having a width of about 3 μm).

As depicted in fig. 3C, the walls of the trench 310 are then coated with an oxide layer 315, for example by means of a thermal oxidation process.

A mask layer 320, such as silicon nitride, is then deposited over the entire structure, as shown in fig. 3D. The material of mask layer 320 penetrates into trench 310 and coats the walls and bottom of trench 310.

Moving to FIG. 3E, the structure is etched, during which a portion of the mask layer 320 is etched away; when the material of the mask layer 320 and the portion of the oxide layer 210 at the bottom of the trench 310 are removed, the etching stops, thereby exposing the silicon substrate 205 at the bottom of the trench 310.

Process steps similar to fig. 2E-2J are then performed to fill the trenches 310 with n + doped polysilicon and p + doped polysilicon.

After the chemical mechanical polishing step, the structure depicted in fig. 3F is obtained (in this and the following figures, the silicon nitride layer remaining on the top surface and sidewalls of trench 310 after the etching of step 3E is not shown for better readability). Trenches 310 are filled with n + doped polysilicon pillars 325a and p + doped polysilicon (e.g., cylindrical) pillars 325b, respectively.

The n + doped polysilicon pillars 325a and p + doped polysilicon pillars 325b are then converted into n + doped porous silicon pillars and p + doped porous silicon pillars. For this purpose, the structure is immersed in a tank or anodising cell, for example made of polytetrafluoroethylene, filled with a solution of Hydrogen Fluoride (HF) acid and provided with an anode and a cathode. The structure to be treated is connected to an anode (the cathode may be, for example, a mesh electrode made of platinum). The HF acid affects the n + doped polysilicon pillars 325a and the p + doped polysilicon pillars 325b, thereby converting them into n + doped porous silicon pillars and p + doped porous silicon pillars. Preferably, the process is stopped before the bottoms (bases) of the n + doped polysilicon pillars 325a and the p + doped polysilicon pillars 325b are converted to porous silicon. This ensures that the integrity of the porous silicon is preserved during subsequent stages of the fabrication process. The resulting structure is depicted in fig. 3G, where reference numerals 330a and 330b denote pillars of n + doped porous silicon and pillars of p + doped porous silicon, respectively, and reference numeral 335 denotes the bottom of pillars 330a and 330b that have not undergone conversion to porous silicon.

It is noted that in an embodiment, the step of converting the n + doped polysilicon pillars 325a and the p + doped polysilicon pillars 325b into n + doped porous silicon pillars and p + doped porous silicon pillars may be avoided: the applicants have found that even though the performance is inferior to n + doped porous silicon and p + doped porous silicon, n + doped polysilicon and p + doped polysilicon are viable options as thermoelectric materials.

In an embodiment, the process may contemplate forming (e.g., by deposition) a polysilicon layer 340 over the surface of the structure. Donor dopant ions and acceptor dopant ions are then selectively implanted into the polysilicon 340 to form n + doped polysilicon regions 345a and p + doped polysilicon regions 345b, respectively, over the pillars of n + doped porous silicon 330a and p + doped porous silicon 330 b. The resulting structure is depicted in fig. 3H. The remaining portions of polysilicon layer 340 (except for n + doped polysilicon region 345a and p + doped polysilicon region 345 b) are then etched away to obtain the structure depicted in fig. 3I. In this way, the n + doped polysilicon regions 345a and p + doped polysilicon regions 345b over the pillars of n + doped porous silicon 330a and p + doped porous silicon 330b provide an enlarged contact area to the pillars of n + doped porous silicon 330a and p + doped porous silicon 330b, which may facilitate forming electrical contacts to the pillars. Similar considerations apply to the first two embodiments described in the foregoing.

Fig. 4A-4E illustrate some steps of a method for continuing to fabricate a thermoelectric converter of any of the previously described embodiments, according to example embodiments of the present disclosure. Although the steps of the manufacturing method to be described hereinafter are also applicable to any of the embodiments described so far, they will be described and illustrated with reference to the second embodiment described in fig. 2A to 2L for the sake of simplicity only.

As shown in fig. 4A, starting with the structure of fig. 2L, a second silicon wafer 405 is bonded to the surface of the structure opposite the silicon substrate (first silicon wafer) 205.

Then as shown in fig. 4B (in this figure and the following figures, fig. 4C and 4D, the structure is depicted upside down compared to fig. 4A), the silicon substrate (first silicon wafer) 205 is removed. After the silicon substrate (first silicon wafer) 205 is removed, the oxide layer 210 remains uncovered.

Corresponding to the thermoelectric elements 237 and 249, contact openings are formed in the oxide layer 210, and an electrically conductive layer 410, e.g., a metal, is formed on the oxide layer 210 and then patterned to define a second wire 413 interconnecting the thermoelectric elements 237 and 249. The resulting structure is shown in FIG. 4C.

The surface of the structure is then coated with a further oxide (e.g. SiO)₂) Layer 415 is overlaid to obtain the structure of fig. 4D.

The second silicon wafer 405 is then selectively etched to form trenches, leaving the material of the second silicon wafer only over the thermoelectric elements 237, 249, and with the second silicon wafer 405 removed, the oxide layer 260 covering the first wire 257 is etched and removed to expose portions 257', 257 ″ of the first wire 257; exposed portions 257', 257 ″ of first wire 257 will form contact pads of the thermoelectric converter for bonding wires 265 (similar portions of wire 143 in the configuration of fig. 1G will form contact pads). The resulting structure is shown in fig. 4E (oriented similarly to fig. 2A-2L).

In use, the side of the structure where (a portion of) the second silicon wafer 405 (left side and not removed) is present will for example be the "hot" side of the thermoelectric converter (e.g. the side where the temperature of the environment in which the thermoelectric converter is inserted is higher), while the opposite side of the structure will for example be the "cold" side of the thermoelectric converter (e.g. the side where the temperature of the environment in which the thermoelectric converter is inserted is lower) in use. Naturally, in use, the roles of the "hot" and "cold" sides of the thermoelectric converter may be reversed: typically, both sides of the thermoelectric converter will experience a temperature gradient in use. The portion(s) of the second silicon wafer 405 that are left and not removed may form a structural support of the device.

Fig. 4F shows an alternative to the steps of fig. 4D and 4E for forming the contact pads of bond wires 265. In this case, the contact pad may be a portion of the second wire 413 interconnecting the thermoelectric elements 237 and 249. To open the contact areas of the contact pads, the oxide layer 415 is selectively etched. Without having to selectively etch the second silicon wafer 405, the second silicon wafer 405 can be left to act as a mechanical support for the structure.

Fig. 5 shows the layout of the structure obtained by the fabrication process of fig. 1A to 1G and the subsequent steps shown in fig. 4A to 4E. The device comprises a plurality of first thermoelectric elements 133a (n-doped, for example with a first seebeck coefficient, in particular with a first sign, for example positive) and a plurality of second thermoelectric elements 133b (p-doped, for example with a second, different seebeck coefficient, in particular with an opposite sign, for example negative). Each first thermoelectric element and each second thermoelectric element has a first end on a "hot" side of the device and a second end on a "cold" side of the device. The first and second thermoelectric elements 133a and 133b are arranged in an alternating array extending parallel to each other and are contacted in a "zigzag" manner by means of wires 143 (here forming first wires 257) and second wires 413 (at opposite ends of the thermoelectric elements, the "hot" side and the "cold" side). The first wire 257 has an input contact pad 257' and an output contact pad 257 ".

The first thermoelectric element 133a and the second thermoelectric element 133b are thermally connected in parallel and electrically connected in series.

Fig. 6 shows the layout of the structure obtained by the fabrication process of fig. 2A to 2L (or fig. 3A to 3I) and fig. 4A to 4D and 4F.

Thus, the device of fig. 6 comprises a plurality of first thermoelectric elements 237 (n-doped, for example having a first seebeck coefficient, in particular having a first sign, for example positive) and a plurality of second thermoelectric elements 249 (p-doped, for example having a second, different seebeck coefficient, in particular having an opposite sign, for example negative). Each first thermoelectric element 237 and each second thermoelectric element 249 has a first end on the "hot" side of the device and a second end on the "cold" side of the device. The first 237 and second 249 thermoelectric elements are arranged in alternating rows or arrays extending parallel to each other and are contacted in a "zig-zag" manner by first 257 and second 413 leads (on opposite ends of the thermoelectric elements, the "hot" side and the "cold" side). The second conductive line 413 has an input contact pad 413' and an output contact pad 413 ".

The first and second thermoelectric elements 237, 249 are thermally connected in parallel and electrically connected in series.

Fig. 7 schematically illustrates, in a simplified block diagram, an electronic system 700 including a thermoelectric converter in accordance with an embodiment of the present disclosure.

The system 700 comprises a thermoelectric converter 705, such as a thermoelectric generator, the thermoelectric converter 705 being adapted to convert heat, indicated by arrow 710, in an environment in which the system 700 is located into electrical energy, which is used to charge a battery 715 of the system 700. The battery 715 supplies electrical energy to an application 720, for example, an electronic subsystem, such as a smart watch, wearable device, flashlight, or the like.

The proposed solution presents a number of advantages. It is easy to industrialize, provides power level of mA magnitude, has low semiconductor area consumption, and works with low temperature difference or high temperature difference. Moreover, the proposed solution allows to reduce the size of standard thermoelectric devices from the macro scale to the micro scale and makes use of the technical steps typical of semiconductor (silicon) manufacturing techniques.

Thermoelectric converters according to the present disclosure may be utilized in several practical applications, such as: wearable and fitness equipment, pedometers and cardiometers, smart watches and wristbands, wireless sensor nodes for smart homes and cities, and other energy harvesting systems, as discussed below with reference to fig. 17.

Furthermore, as disclosed herein, thermoelectric converters according to the present disclosure may be used in solar energy recovery devices.

Fig. 8-13 illustrate some steps of a method for manufacturing a solar energy recovery device using a thermoelectric converter of any of the previously described embodiments, according to an example embodiment of the present disclosure. For the sake of simplicity, the steps of the manufacturing method which will be described hereinafter will be described and illustrated with reference to the continuation of the process steps described with reference to fig. 4A to 4D and 4F, although they are also applicable to any embodiment described so far. In the cross-sections of fig. 8, 10 (taken along the section plane VIII-VIII of fig. 9A, 9B) and in the cross-section of fig. 11 (taken along the section plane XI-XI of fig. 12A, 12B), only the first wire 257 is fully visible; the second conductor 413 is only partially visible.

As shown in fig. 8, a third silicon wafer 501 is bonded to a surface 500A of the structure of fig. 4F, here denoted by 500 and also referred to as a thermoelectric generator structure 500; the surface 500A is opposite the second silicon wafer 405. The third silicon wafer 501 may be a silicon wafer, in particular monocrystalline silicon, which is doped with acceptor dopants and is therefore P-type, and has a first surface 501A and a second surface 501B. The third silicon wafer 501 is bonded at its first surface 501A to the thermoelectric generator structure 500.

For this purpose, the bonding multilayer 502 is used; for example, the bonding multilayer 502 may include a first bonding layer 504 extending over the surface 500A of the thermoelectric generator structure 500; a second bonding layer 505 extending on the first surface 501A of the third silicon wafer 501; and an intermediate bonding layer 506. The material of the first bonding layer 504 and the second bonding layer 505 may be copper (Cu); and the material of the intermediate bonding layer 506 may be tin (Sn).

The first bonding layer 504, the second bonding layer 505, and the intermediate bonding layer 506 may be applied on the surface 500A of the thermoelectric generator structure 500 or on the first surface 501A of the third silicon wafer 501. In an alternative, a first bonding layer 504 may be applied to the surface 500A of the thermoelectric generator structure 500, a second bonding layer 505 may be applied to the first surface 501A of the third silicon wafer 501, and an intermediate bonding layer 506 may be applied to one of the first bonding layer 504 or the second bonding layer 505.

In some embodiments, joining the multiple layers 502 is defined as forming an annular portion 502A that surrounds the area housing the thermoelectric elements 237, 249 in the thermoelectric generator structure 500 (see also fig. 9A and 9B). The bonding multilayer 502 also forms an intermediate finger portion 502B, which may be arranged in various ways so as to allow good bonding and to allow connection on the surface 500A of the thermoelectric generator structure 500 or to extend on the first surface 501A of the third silicon wafer 501.

For example, the thermoelectric elements 237, 249 of fig. 8 form a plurality of thermoelectric modules 510 (see fig. 9A) coupled in parallel with one another. In the embodiments of fig. 8, 10, and 11, each thermoelectric module 510 may include a row of thermoelectric elements 237 and a row of thermoelectric elements 249 (see, e.g., fig. 6) coupled as also shown in fig. 6; in the alternative, each thermoelectric module 510 may comprise the entire structure shown in fig. 6, for example.

In some embodiments, thermoelectric modules 510 are coupled by connections 511, which connections 511 may be formed partially in oxide layer 270 and partially on oxide layer 415 (fig. 8). To engage the annular portion 502A discontinuity of the multilayer 502, the connector 511 is coupled to an input pad 512 and an output pad 513 disposed at the periphery of the thermoelectric generator structure 500. The input pad 512 and the output pad 513 may be coupled to the input contact pad 413' and the output contact pad 413 ″ by vias in a manner known per se. In addition, the annular portion 502A forms an anode pad 514, as explained below.

In FIG. 10, N⁺Implantation of a type dopant species is performed in the third wafer 501 through its second surface 501B. For example, N is appropriate⁺The type dopant species may be phosphorus or arsenic.

The implant is then annealed and activated by an intense laser beam pulse. The pulse length may be about one hundred nanoseconds (< 200 ns). Thereby, the cathode region 520 is formed. The heat generated by the pulse is sufficient to perform a local anneal, thereby eliminating the local implant damage and activating the dopants. In particular, with very short pulses, no temperature variations are produced in the metal region; therefore, the bonding multilayer 502, the first wire 257 and the second wire 413, and the connection 511 are not affected.

The cathode region 520 forms together with the basic portion of the third wafer 501 (also referred to below as P-substrate 521) a diode which is capable of converting solar energy into electrical current in a manner known per se. Thereby, the third wafer 501 forms the solar photovoltaic cell wafer 201.

In fig. 11, the third wafer 501 is etched to remove a portion thereof covering the pads 512-514 (see also fig. 12A, 12B, which show that the thermoelectric generator structure 500 and the third wafer 501 have not yet been bonded together). Etching may be performed by laser or blade cutting. Thus, a recess 525 is formed, which exposes the pads 512 to 514.

Electrical wires 530 are bonded to the input pads 512 and the output pads 513, and external connections 531A, 531B are each bonded to the anode pads 514 and the cathode regions 520. The external connections 531A, 531B may be wires or cables.

Thereby, the solar photovoltaic thermoelectric module 550 is obtained.

Fig. 13 shows three solar photovoltaic thermoelectric modules 550 to form an example connection of a hybrid solar energy recovery device 570. In general, a plurality of solar photovoltaic thermoelectric modules 550 may be coupled to each other in series or in parallel, wherein the input pads 512 of all the solar photovoltaic thermoelectric modules 550 are coupled together and the output pads 513 of all the solar photovoltaic thermoelectric modules 550 are coupled together by respective external connections 531A, 531B. The hybrid solar photovoltaic thermoelectric device 570 can effectively recover electric energy.

Conventional solar cells are only capable of absorbing the photon energy of solar radiation at frequencies close to the band gap of the solar cell, and the remaining energy is converted to thermal energy and wasted. Furthermore, the conversion efficiency decreases with temperature.

In contrast, with the solar photovoltaic thermoelectric modules of fig. 8 to 12, the waste heat generated at the solar photovoltaic cell wafer 501 can be recovered by the thermoelectric generator structure 500, and the total power is the sum of the power supplied by the thermoelectric generator 500 and the power supplied by the solar photovoltaic cell wafer 501, thereby providing synergy.

Fabrication can be performed using techniques commonly used in the semiconductor industry. For example, the solar photovoltaic cell wafer 501 is bonded before the front end. In this way, possible fractures (of the metal areas, for example) that may occur during bonding due to the pressure exerted by the piston on the two wafers are avoided.

Fig. 14 and 15 show another embodiment of a thermoelectric generator obtained by aerosol jet printing of a semiconductor material. In particular, maskless mesoscale material deposition (M3D) may be used to deposit semiconductor material. According to one aspect of the disclosure, bismuth telluride (Bi) of a relative conductivity type₂Te₃) The areas are printed.

For example, fig. 14 shows a first wafer 600 and a second wafer 601. The first wafer 600 and the second wafer 601 may be silicon wafers, such as single crystal silicon wafers. One of the wafers 600, 601 (here the second wafer 601) is P-type.

The first wafer 600 has a surface 600A on which surface 600A alternatively the bismuth P-telluride region 604 and the first adhesion region 605 have been deposited using M3D.

The second wafer 601 has a surface 601A on which surface 601A alternatively the bismuth N-telluride region 606 and the second adhesion region 607 have been deposited using M3D.

A region of bismuth P-telluride 604 and a first adhesion region 605 are deposited on a first metal region 610 extending over the surface 600A of the first wafer 600. A bismuth N-telluride region 606 and a second adhesion region 607 are deposited on the second metal region 611. The first and second metal regions 610 and 611 may be, for example, gold (Au).

For example, a bismuth telluride region 604 or 606 and an adhesion region 605 or 607 are formed on each metal region 610, and the distance between the P-type bismuth telluride region 604 and the adjacent first adhesion region 605 is the same as the distance between the N-type bismuth telluride region 606 and the adjacent second adhesion region 607.

In addition, although fully visible in fig. 14-15, the metal regions 610, 611 typically have the pattern shown in fig. 5 or 6 for the conductive lines 143 or 257 and 413 for connecting the bismuth telluride regions 604, 606 in series. Adhesion regions 605 and 607 may be a tin-silver (Sn-Ag) alloy and have a lower thickness than bismuth telluride regions 604, 606. Here, the bismuth telluride regions 604, 606 have the same thickness, for example in the range 20 to 30 μm; the adhesive areas 605, 607 have the same thickness, for example in the range 1 to 2 μm.

The first wafer 600 and the second wafer 601 are bonded to each other by turning one wafer (here, the second wafer 601) upside down and bonding the P-type bismuth telluride region 604 to the second adhesion region 607, and bonding the N-type bismuth telluride region 606 to the first adhesion region 605 (fig. 15).

Bonding may be accomplished by applying pressure (e.g., 1 to 20MPa) at low temperatures (e.g., about 400 ℃).

After bonding, the bismuth telluride regions 604, 606 form the thermoelectric elements.

Then, N⁺An implant of a type dopant species is performed in one of the wafers 600, 601 (here the second wafer 601) through its exposed surface. For example, phosphorus or arsenic ions are implanted.

The implant is then annealed and activated by an intense laser beam pulse to form the cathode region 620. The remaining portion of the second wafer 601 forms an anode region 621.

The structure of fig. 15 may be subjected to the fabrication steps discussed above with reference to fig. 11, 12A, and 12B.

Thereby, the solar photovoltaic thermoelectric module 650 is obtained.

As shown in fig. 13, a plurality of solar photovoltaic thermoelectric modules 650 may be coupled to form a hybrid solar energy recovery device.

Fig. 16 shows a solar photovoltaic thermoelectric module 650 similar to that of fig. 15, but for an arrangement of regions 604, 606 of bismuth telluride formed here on the same wafer (here the first wafer 600) and an adhesion region, here indicated by reference numeral 705, formed on another wafer (here the second wafer 601). Other elements have been denoted by the same reference numerals as in fig. 14 to 15.

In some implementations, in the embodiment of fig. 16, the P-type bismuth telluride region 604 and the N-type bismuth telluride region 606 are printed on the first wafer 600 (after the first metal region 610 is formed) and the adhesion region 705 is printed entirely on the second wafer 601 (after the second metal region 611 is formed) by an M3D printing technique.

After the first wafer 600 and the second wafer 601 are bonded, the solar photovoltaic thermoelectric module 750 is obtained.

As shown in fig. 17, the energy recovered by the solar photovoltaic thermoelectric module 650 of fig. 15 or the solar photovoltaic thermoelectric module 750 of fig. 16 may be increased by using a passive cooling system.

Fig. 17 shows a solar energy recovery system 800 comprising a solar collector panel 801 and a loop 802 for recirculating a cooling fluid. In the embodiment considered, the cooling fluid is water, and the following description is made in view of water; however, other cooling fluids may be used.

A trough 803 having a cold water input tap 804 and a warm water output tap 805 is disposed along the water recirculation loop 802.

The solar collector panel 801 houses a plurality of solar photovoltaic thermoelectric modules 550, 650 or 750 coupled together as shown in fig. 13. The solar photovoltaic thermoelectric module 550, 650, or 750 may be attached to a support wall 810 defining a water chamber 811 arranged along the loop 802. The water chamber 811 has an input (cold) side 811A and an output (warm) side 811B; the groove 803 is disposed near the output (warm) side 811B of the water chamber 811.

Due to the temperature gradient between the input (cold) side 811A and the output (warm) side 811B, and due to the principle of communicating vessels, the water in the loop 802 does not need a pump to circulate.

For example, in an embodiment, loop 802 may include a subterranean zone 820 that extends below ground level (indicated by 830 in fig. 17). In particular, by arranging the subterranean zone 820 at a depth of 8 to 10m below ground level 830, a particularly efficient heat extraction from the cooling water is obtained and a refrigerator or pump is not required.

By recirculating the cooling water, the loop 802 provides cooling of the solar collector panel 801 and thus reduces the temperature of the solar photovoltaic cell wafers 501, 601 and increases the photovoltaic effect.

Fig. 18 shows a possible embodiment of a solar photovoltaic cell wafer 900.

The solar photovoltaic cell wafer 900 is based on the use of amorphous silicon and comprises a stack formed by a first doped layer 901 having N-type conductivity, in the case of being passivated by hydrogen (a-Si: H); an intermediate intrinsic layer 902 covering the first doped layer 901; and a second doped layer 903 having P-type conductivity, which covers the middle intrinsic layer 902.

For example, the structure of fig. 18 may be obtained by depositing an aluminum layer 905, a first doped layer 901, an intermediate intrinsic layer 902, a second doped layer 903, a Transparent Conductive Oxide (TCO) layer 906, and a glass layer 907 over the third wafer 501, starting from the structure of fig. 8.

In an embodiment, the first doped layer 901 may have a thickness of about 10 nm; the intermediate intrinsic layer 902 may have a thickness of about 400 nm; and the second doped layer 901 may have a thickness of about 10 nm.

The TCO layer 906 can be, for example, indium tin oxide.

Due to the fact that electron-hole recombination is particularly high in doped silicon, the intermediate intrinsic layer 902 provides an efficient absorption of light radiation, while the first and second doped layers 901, 903 provide an efficient generation of electron current. Thus, the solar photovoltaic cell wafer 900 is very efficient and may be advantageously combined with the thermoelectric generator structures described herein, such as the thermoelectric generator structure 500.

A method of fabricating an integrated thermoelectric converter can be summarized as including: providing a layer of silicon-based material (115; 215) having a first surface and a second surface opposite the first surface and spaced from the first surface by a thickness of the silicon-based material layer; forming a plurality of first thermoelectric active elements (133 a; 237; 330a) of a first thermoelectric semiconductor material having a first seebeck coefficient, and forming a plurality of second thermoelectric active elements (133 b; 249; 330b) of a second thermoelectric semiconductor material having a second seebeck coefficient, wherein the first thermoelectric active elements and the second thermoelectric active elements are formed to extend from the first surface through a thickness of the silicon based material layer (115; 215) to the second surface; forming electrically conductive interconnects (143, 413; 257, 413) corresponding to the first and second surfaces of the layer of silicon based material (115; 215) to electrically interconnect the plurality of first thermoelectric active elements and the plurality of second thermoelectric active elements, and forming input electrical terminals (257 ') and output electrical terminals (257') electrically connected to the electrically conductive interconnects, wherein the first thermoelectric semiconductor material and the second thermoelectric semiconductor material comprise a silicon based material selected between porous silicon or poly SiGe or poly silicon.

The silicon-based material layer (115; 215) may be in poly SiGe (in particular poly Si)_0.7Ge_0.3) Or epitaxial polysilicon.

The plurality of first thermoelectric active elements (133 a; 237; 330a) of the first thermoelectric semiconductor material having the first Seebeck coefficient may comprise doped porous silicon or polycrystalline SiGe or polycrystalline silicon doped with acceptor dopants or donor dopants, and the plurality of second thermoelectric active elements (133 b; 249; 330b) of the second thermoelectric semiconductor material having the second Seebeck coefficient may comprise doped porous silicon or polycrystalline SiGe or polycrystalline silicon each doped with donor dopants or acceptor dopants.

The providing of the layer of silicon based material (115; 215) may comprise epitaxially growing a layer of polysilicon (115; 215) on an oxidized surface of the substrate.

Said forming a plurality of first thermoelectric active elements (237) of a first thermoelectric semiconductor material having a first seebeck coefficient may comprise forming a first trench (225, 230) in the silicon based material layer (215), the first trench being filled with polysilicon or poly-SiGe doped with an acceptor or donor dopant, and wherein said forming a plurality of second thermoelectric active elements (249) of a second thermoelectric semiconductor material having a second seebeck coefficient may comprise forming a second trench (240, 245) in the silicon based material layer (215), the second trench being filled with polysilicon or poly-SiGe doped with a donor or acceptor dopant.

The method may further include converting the doped polysilicon filling the first and second trenches to doped porous silicon.

The providing of the silicon based material layer may comprise iterating at least twice the following steps: forming a poly SiGe layer (115) on an oxidized surface of a substrate (205), wherein the poly SiGe layer (115) has a thickness that is a fraction of a thickness of the silicon-based material layer; -selectively doping a first region (120a) of the poly-SiGe layer with an acceptor or donor dopant, and-selectively doping a second region (120b) of the poly-SiGe layer with a donor or acceptor dopant, such that after said iteration the stack of respective poly-SiGe layers (115) has an overall thickness corresponding to the thickness of said silicon-based material layer, -forming a trench (130) in the stack of respective poly-SiGe layers to obtain separate portions (133a, 133b) of the doped first region and the doped second region.

An integrated thermoelectric converter can be summarized as including: a silicon-based material layer (115; 215) having a first surface and a second surface opposite the first surface and spaced from the first surface by a silicon-based material layer thickness; a plurality of first thermoelectric active elements (133 a; 237; 330a) of a first thermoelectric semiconductor material having a first Seebeck coefficient and a plurality of second thermoelectric active elements (133 b; 249; 330b) of a second thermoelectric semiconductor material having a second Seebeck coefficient, wherein the first and second thermoelectric active elements extend from the first surface through the thickness of the silicon-based material layer to the second surface; electrically conductive interconnects (143, 413; 257, 413) corresponding to the first and second surfaces of the layer of silicon-based material to electrically interconnect the plurality of first thermoelectric active elements and the plurality of second thermoelectric active elements; and input electrical terminals (257 ') and output electrical terminals (257') electrically connected to the electrically conductive interconnects, wherein the first thermoelectric semiconductor material and the second thermoelectric semiconductor material comprise a silicon-based material selected between porous silicon or polysilicon or poly SiGe.

The silicon-based material layer may be in poly-SiGe (in particular poly-Si)_0.7Ge_0.3) Or epitaxial polysilicon.

The first thermoelectric semiconductor material having a first seebeck coefficient may be porous silicon or polysilicon or poly-SiGe doped with acceptor dopants or donor dopants, and the second thermoelectric semiconductor material having a second seebeck coefficient may be porous silicon or polysilicon or poly-SiGe each doped with donor dopants or acceptor dopants.

Each of the plurality of first and second thermoelectric active elements and each of the second thermoelectric active elements may have a first end at the first surface and a second end at the second surface of the silicon based material layer, and the conductive interconnect may electrically connect the first end of the common first thermoelectric active element to the first end of the second thermoelectric active element and the second end of the common first thermoelectric active element to the second end of another second thermoelectric active element, such that the plurality of first thermoelectric active elements and the plurality of second thermoelectric active elements are connected in series and alternate with each other.

The electronic system (600) may be summarized as including a thermoelectric converter.

The present disclosure may also be understood based on the following example implementations.

Example implementation 1: a method of making a thermoelectric converter, comprising: forming a thermoelectric active element of a first thermoelectric semiconductor material having a first seebeck coefficient and a plurality of second thermoelectric active elements of a second thermoelectric semiconductor material having a second seebeck coefficient in a silicon-based material layer having a first surface, a second surface opposite the first surface, and a first thickness between the first surface and the second surface, the first thermoelectric active element and the second thermoelectric active element each being formed to extend from the first surface through the first thickness to the second surface; and forming conductive interconnects over at least one of the first surface or the second surface of the silicon-based material layer, the conductive interconnects each electrically interconnecting a first thermoelectric active element of the plurality of first thermoelectric active elements with a corresponding second thermoelectric active element of the plurality of second thermoelectric active elements; and forming input and output electrical terminals electrically coupled to the electrically conductive interconnects, wherein the first and second thermoelectric semiconductor materials each comprise a silicon-based material selected from the group consisting of porous silicon, polycrystalline silicon germanium (SiGe), and polysilicon.

Example implementation 2: the method of example implementation 1, wherein the silicon-based material layer is in Si_0.7Ge_0.3A material selected from the group consisting of poly SiGe and epitaxial polysilicon.

Example implementation 3: the method of example implementation 1, wherein the plurality of first thermoelectric active elements of the first thermoelectric semiconductor material having a first seebeck coefficient are doped with acceptor dopants and the plurality of second thermoelectric active elements of the second thermoelectric semiconductor material having a second seebeck coefficient are doped with donor dopants.

Example implementation 4: the method of example implementation 1, wherein the layer of silicon-based material is polysilicon, and the method includes epitaxially growing the polysilicon layer on an oxidized surface of a substrate.

Example implementation 5: the method of example implementation 4, wherein forming the plurality of first thermoelectric active elements having the first thermoelectric semiconductor material with the first seebeck coefficient includes: forming a first trench in the silicon-based material layer, and filling the first trench with polysilicon or poly-SiGe doped with an acceptor dopant; and wherein forming the plurality of second thermoelectric active elements of the second thermoelectric semiconductor material having the second seebeck coefficient comprises: forming a second trench in the silicon-based material layer, and filling the second trench with polysilicon or poly SiGe doped with a donor dopant.

Example implementation 6: the method of example implementation 5, wherein each of the first and second trenches is filled with polysilicon, and the method further comprises: converting the doped polysilicon filling the first and second trenches into doped porous silicon.

Example implementation 7: the method of example implementation 1, comprising: forming the silicon-based material layer includes: iterating the following steps at least twice: forming a poly SiGe layer on an oxidized surface of a substrate, wherein the poly SiGe layer has a thickness that is a portion compared to the first thickness of the silicon-based material layer; selectively doping a first region of the poly SiGe layer with an acceptor dopant; and selectively doping a second region of the poly SiGe layers with a donor dopant, wherein after the iteration, each stack of poly SiGe layers has an overall thickness corresponding to the first thickness of the silicon-based material layer; and forming a trench in the stack of the respective poly SiGe layers, thereby obtaining separate portions of a doped first region and a doped second region.

Example implementation 8: the method of example implementation 1, further comprising: and bonding the silicon-based material layer to an amorphous silicon solar photovoltaic cell wafer.

Example implementation 9: the method of example implementation 8, wherein bonding the silicon-based material layer includes forming a conductive bonding layer in electrical contact with the solar photovoltaic cell wafer, and forming a first electrical contact for the solar photovoltaic cell wafer.

Example implementation 10: the method of example implementation 9, wherein the solar photovoltaic cell wafer includes a first region of a first conductivity type, the method including implanting a dopant species to form a second region of a second conductivity type opposite the first conductivity type, and forming a second electrical contact electrically coupled to the second region.

Example implementation 11: a method of making a thermoelectric converter, comprising: forming conductive interconnects on the first and second wafers; printing semiconductor regions of a first conductivity type and a second conductivity type on the conductive interconnects of at least one of the first or second silicon wafers by maskless mesoscale material deposition according to a pattern; forming bonding regions of conductive material on the other silicon wafer of the at least one of the first or second silicon wafers, the bonding regions being arranged to correspond to the pattern; and contacting the semiconductor region with the bonding region; and bonding the semiconductor region to the bonding region by applying pressure to the first and second silicon wafers.

Example implementation 12: the method of example implementation 11, wherein the semiconductor region is a bismuth telluride region.

Example implementation 13: the method of example implementation 11, wherein the junction region is formed using maskless mesoscale material deposition.

Example implementation 14: the method of example implementation 11, comprising: and forming an anode region on the surface of the first silicon wafer far away from the second silicon wafer.

Example implementation 15: the method of example implementation 14, comprising: a cathode region is formed in the first silicon wafer.

Example implementation 16: an integrated thermoelectric converter comprising: a first pillar structure comprising one of porous silicon, polycrystalline silicon germanium, or polycrystalline silicon, and doped with a first conductivity type; a second pillar structure comprising one of porous silicon, polycrystalline silicon germanium, or polycrystalline silicon, and doped with a second conductivity type; and a first conductive interconnect structure in electrical contact with a first end of the first pillar structure and a first end of the second pillar structure.

Example implementation 17: the integrated thermoelectric converter of example implementation 16, comprising: a first insulating structure surrounding the first pillar structure, and a second insulating structure surrounding the second pillar structure.

Example implementation 18: the integrated thermoelectric converter of example implementation 16, wherein the first pillar structure comprises polycrystalline silicon germanium and the first pillar structure comprises a plurality of polycrystalline silicon germanium layers stacked on top of one another.

Example implementation 19: the integrated thermoelectric converter of example implementation 16, comprising: a substrate, wherein the first pillar structure comprises a first portion of porous silicon and a second portion of polysilicon, the second portion being between the first portion and the substrate.

Example implementation 20: the integrated thermoelectric converter of example implementation 19, wherein the second portion of the first pillar structure is in contact with the substrate.

Example implementation 21: the integrated thermoelectric converter of example implementation 16, wherein each thermoelectric active element of the first plurality of thermoelectric active elements and each thermoelectric active element of the second plurality of thermoelectric active elements is cylindrical.

Example implementation 22: the integrated thermoelectric converter of example implementation 16, comprising: a third pillar structure comprising one of porous silicon, polycrystalline silicon germanium, or polycrystalline silicon, and doped with the second conductivity type; and a second conductive interconnect structure in electrical contact with a second end of the first pillar structure and a second end of the third pillar structure.

Example implementation 23: the integrated thermoelectric converter of example implementation 16, comprising: a fourth pillar structure comprising one of porous silicon, polycrystalline silicon germanium, or polycrystalline silicon, and doped with the first conductivity type; and a third conductive interconnect structure in electrical contact with a second end of the second pillar structure and a second end of the fourth pillar structure.

Example implementation 24: the integrated thermoelectric converter of example implementation 16, comprising: an insulating layer covering the first conductive interconnect structure; and a silicon wafer on the insulating layer.

Example implementation 25: an integrated solar photovoltaic thermoelectric module comprising: a substrate wafer; a first conductive interconnect on the substrate wafer; a thermoelectric converter structure on the substrate layer, the thermoelectric converter structure comprising a plurality of first thermoelectric active elements of a first thermoelectric semiconductor material having a first seebeck coefficient and a plurality of second thermoelectric active elements of a second thermoelectric semiconductor material having a second seebeck coefficient, the first and second thermoelectric active elements being pillar-shaped and each having a first end and a second end, the first end of each first thermoelectric active element being electrically coupled to the first end of a second thermoelectric active element by a respective first electrically conductive interconnect; a second electrically conductive interconnect coupled to the second ends of the first and second thermoelectric active elements; a solar cell wafer of amorphous silicon bonded to the thermoelectric converter structure, the solar cell wafer comprising an anode region and a cathode region; a first input electrical terminal and a first output electrical terminal electrically coupled to the conductive interconnect; and a second input electrical terminal and a second output electrical terminal each electrically coupled to the anode region and the cathode region.

Example implementation 26: an integrated thermoelectric converter comprising: a silicon-based material layer having a first surface and a second surface opposite the first surface, the second surface separated from the first surface by a first thickness of the silicon-based material; a plurality of first thermoelectric active elements of a first thermoelectric semiconductor material having a first seebeck coefficient; and a plurality of second thermoelectric active elements of a second thermoelectric semiconductor material having a second seebeck coefficient; the first thermoelectric active element and the second thermoelectric active element each extend from the first surface through the silicon-based material layer; electrically conductive interconnects on at least one of the first surface or the second surface of the silicon-based material layer and each electrically contacting a first thermoelectric active element of the plurality of first thermoelectric active elements and a corresponding one of the plurality of second thermoelectric active elements; and input and output electrical terminals electrically coupled to the electrically conductive interconnects, wherein the first and second thermoelectric semiconductor materials each comprise a silicon-based material selected from the group consisting of porous silicon, polycrystalline silicon germanium (SiGe), and polysilicon.

Example implementation 27: the thermoelectric converter of example implementation 26, wherein the silicon-based material layer is in Si_0.7Ge_0.3Is selected from poly SiGe or epitaxial poly silicon.

Example implementation 28: the thermoelectric converter of example implementation 26, wherein the first thermoelectric semiconductor material having a first seebeck coefficient is doped with an acceptor dopant and the second thermoelectric semiconductor material having a second seebeck coefficient is doped with a donor dopant.

Example implementation 29: the thermoelectric converter of example implementation 26, wherein: each of the plurality of first thermoelectric active elements and the plurality of second thermoelectric active elements has a first end at the first surface of the silicon-based material layer and a second end at the second surface of the silicon-based material layer; and the conductive interconnects electrically connect: a first end of the first thermoelectric active element to a second end of the second thermoelectric active element; and a second end of the first thermoelectric active element to a second end of another second thermoelectric active element such that the plurality of first thermoelectric active elements and the plurality of second thermoelectric active elements are coupled in series and alternate with each other.

The various embodiments described above can be combined to provide further embodiments. Various aspects of the embodiments may be modified to provide other embodiments.

These and other changes can be made to the embodiments in light of the above detailed description. In general, in the following claims, the terms used should not be construed to limit the claims to the specific embodiments disclosed in the specification and the claims, but should be construed to include all possible embodiments along with the full scope of equivalents to which such claims are entitled. Accordingly, the claims are not limited by the disclosure.