Thermoelectric micro pillar array devices, methods and uses thereof

Abstract

The present invention relates to a thermoelectric device for heat harvesting and a method for obtaining the device, wherein the thermoelectric device comprises: a substrate; a bottom conductive layer deposited on the substrate; a top conductive layer; a plurality of pillars of thermoelectric semiconductor material; an electrically insulating and thermally insulating layer enclosing the plurality of pillars; wherein the electrically insulating and thermally insulating layer and the thermoelectric material are disposed between the bottom conductive layer and the top conductive layer.

Description

Technical Field

[0001] This invention relates to a device for converting thermal energy into electrical energy. Specifically, it relates to a heterogeneous thermoelectric device for use in windows, touch displays, photovoltaic panels, and solar thermal panels, for collecting thermal energy and converting it into electrical energy. Background Technology

[0002] Approximately 60% of the world's energy production is wasted due to transmission losses, particularly as heat. Thermoelectric materials can reduce this energy loss by converting heat into electricity. For example, it is well known that most window glass in buildings is not effective at suppressing heat loss in indoor cooling or heating environments. The thermal conductivity of most glass at room temperature ranges from 0.5 W·m. -1 ·K -1 (High-lead glass) to approximately 1.4 W·m -1 ·K -1 (Pure quartz glass) The thermal conductivity of commonly used silicate glasses ranges from 0.9 to 1.2 W·m. -1 ·K -1 Therefore, although these values ​​are smaller compared to most metallic structures, energy loss still exists.

[0003] The thermoelectric (TE) effect has historically been recognized as the phenomenon where a temperature difference across a material is directly converted into voltage. Thermoelectric materials have been studied for many years. The earliest example is the thermocouple, which consists of two different electrical conductors forming an electrical junction. This discovery was made by Alessandro Volta in 1794, and subsequently rediscovered independently by Thomas Johann Seebeck in 1821. Since then, the thermoelectric effect has generally been referred to as the Seebeck effect. Newer thermoelectric materials are based on metals and semiconductors, such as zinc, lead, antimony, bismuth, copper, and alloys of varying compositions, as well as many more complex systems developed over the years, such as ceramics, polymers, and composites. Most of these materials have a high Seebeck coefficient (S), defined as the electromotive force (∆V) generated by the material divided by the temperature difference (∆T) across the material. Optimal thermoelectric materials must possess high electrical conductivity (σ) and low thermal conductivity (κ) to achieve a high thermoelectric figure of merit (ZT=S) at a specific temperature (T). 2 σ / κ⋅Τ), and thus obtain a high power factor (PF=S 2 (σ). However, if optical transparency is required, the above materials cannot be applied to glass. To solve this problem, researchers began to work on transparent thermoelectric materials, especially transparent metal oxide coatings. But so far, these metal oxide coatings have been designed to collect heat on their surfaces and are not suitable for applications such as touch displays or window glass.

[0004] There are many types of thermoelectric generator devices in the existing technology, and a variety of different solutions and applications have been proposed.

[0005] First, regarding non-transparent devices, Boukai et al. [1] reported the high-efficiency thermoelectric performance of single-component silicon (Si) nanowire systems with cross-sectional areas of 10 nm × 20 nm and 20 nm × 20 nm. By changing the size and impurity doping level of the nanowires, a ZT value about 100 times higher than that of bulk silicon was obtained over a wide temperature range, including ZT < 1 at 200 K. Hochbaum et al. [2] reported the electrochemical synthesis of large-area, wafer-level, rough silicon nanowire arrays with diameters of 20–300 nm, which have a thermoelectric figure of merit of ZT = 0.6 at room temperature. Since the thermoelectric (TE) modules are composed of complementary p-type and n-type materials in series, the universality and scalability of this synthesis method are promising for the fabrication of silicon-based devices. Zhou et al. [3] also reported the use of nanowires to continuously convert human body heat into electrical energy, which can be applied to portable / wearable electronic devices. However, despite the good thermoelectric properties of the aforementioned silicon nanowires, these nanowires are not optically transparent unless applied to the substrate surface in a mesh form, which inevitably reduces the transparency of windows or touch displays. Kim et al. [4] proposed another flexible thermoelectric generator (TEG) for harvesting heat energy from human skin. The TEG is composed of n-type (Bi2Te3) and p-type (Sb2Te3) materials with a weight areal density of 0.13 g / cm³. 2 Tan et al. [5] reported on the growth mechanism of hierarchical columnar arrays and ordinary Sb2Te3 films. The hierarchical structure of p-type antimony telluride columnar arrays can be self-assembled on a large scale by a simple vacuum thermal evaporation technique. The hierarchical film is composed of well-oriented columnar arrays perpendicular to the substrate. Another work [6] reported on n-Bi2Te3 films with layered silver (Ag) electrodes prepared by magnetron sputtering and mask-assisted deposition techniques. 2.7 Se 0.3 Columnar array leg microdevices. These last two schemes are closest to the present invention, the main difference being the vertical columns involved. These schemes focus on the growth method of the thin film, while the scheme proposed in this invention concerns the geometry of the thin film. However, these STEGs are not optically transparent, which hinders their application in structures requiring transparency. Furthermore, the microfabrication steps for preparing the transparent thermoelectric microarray in this invention are also different.

[0006] Further, regarding semi-transparent devices, Wang et al. [7] reported a flexible TEG module based on the polymer composite material PEDOT:PSS, consisting of 16 legs, capable of outputting a stable TE voltage of 4.6 mV in response to human body heat. The results show that thermoelectric polymers have great potential for large-scale production in industrial applications, despite their shortcomings in optical transparency and high absorption in the visible spectrum. Klochko [8] reported a novel design of a semi-transparent solar thermoelectric nanogenerator (n-TEG) ​​based on an array of zinc oxide (ZnO) nanorods pulsedly electrodeposited on a transparent conductive fluorine-doped tin oxide (FTO) substrate. This solar n-TEG design combines the low thermal emissivity of FTO and ZnO coatings with the advantages of TE technology, utilizing the window itself to collect the photothermal energy of outdoor sunlight and generate electricity, while having high transparency in the infrared region. Despite its promising prospects, this TE application still has shortcomings in terms of optical transparency in the visible electromagnetic spectrum, with its highest transmittance typically below 20-30% and below 5% in the blue-green region.

[0007] Regarding transparent TEG, Faustino et al. [9] reported on copper iodide (CuI) p-type thermoelectric films prepared by three different methods, thereby maximizing optical transparency (visible range >70%) and electrical conductivity (σ=1.1×10⁻⁶). -4 ⁻ S·m -1) and thermoelectric properties (ZT=0.22 at 300K). However, these planar transparent pn-type TE modules are designed to collect in-plane temperature differences. Chen and his collaborators

[10] proposed an innovative transparent micro-thermoelectric generator (μ-TEG) ​​designed, simulated and fabricated using microelectromechanical systems (MEMS) surface microfabrication technology, which also uses planar pn-type TE modules for solar energy conversion applications. This resulted in a μ-TEG with a suspended bridge-type polycrystalline silicon Peltier element and transparent conductive indium tin oxide (ITO) films as hot and cold side electrodes, which are fabricated on glass or quartz wafers to collect in-plane temperature differences. In some cases, according to Fan et al.

[11] , these transparent thermoelectric devices can be fabricated as stretchable transparent ion gels. Ferreira and his colleagues

[12] reported on the TE performance of tin oxide (SnO2) prepared by RF sputtering technology, with or without post-deposition annealing in air at atmospheric pressure, and compared its performance with that of other potential environmentally friendly metal oxide materials. Studies have shown that when a thin planar film (250 nm) is annealed to 500 °C, the absolute Seebeck coefficient increases monotonically from 150 μV / K to 250 μV / K at room temperature. In 2019, Coroa et al.

[13] reported the first highly transparent and flexible pn-type thermoelectric generator containing 17 pn modules connected in series / parallel for both electrical and thermal purposes. The device has been successfully constructed and tested for in-plane temperature differences up to 30 °C. The reported ZT values ​​for copper iodide (CuI) and gallium-doped zinc oxide (GZO) are 0.29 and 0.07, respectively, and the Seebeck coefficients for CuI (p-type) and GZO (n-type) are 206 μV / K and -60 μV / K, respectively. However, the electrical properties of CuI films are observed to be unstable at temperatures above 80 °C. Ishibe et al.

[14] reported a single-legged (n-type) thin-film TEG composed of domain-engineered SnO2 films, which produced approximately 54 μW·m when an in-plane temperature difference of 20 K was applied. -2 The maximum power density is sufficient to power some IoT sensors. The sample exhibits approximately 0.04 μW·m at room temperature. -1 ·K -2 The maximum power factor and high optical transmittance of >80% in the visible light region. Another promising n-type thermoelectric material is niobium-doped titanium dioxide (TiO2:Nb). According to the research of Ribeiro et al.

[15] , a nanoscale junctionless thermoelectric element was constructed. The element consists of a TiO2:Nb thin film layer with a thickness of 120-300 nm deposited on a borosilicate glass substrate. The maximum average optical transmittance in the visible light range is 73%, the n-type resistivity is 0.05 Ω·cm, and the thermal conductivity is 1.7 W·m. -1 ·K -1The absolute Seebeck coefficient is greater than 220 μV / K. The resulting maximum thermoelectric power factor is 60 μW∙m⁻¹. -1 ∙K -2 The maximum thermoelectric figure of merit is 0.014. Patent document PT110639

[16] filed for the latter type of n-type thermoelectric coating, which is used to collect heat in the in-plane direction.

[0008] Table 1 summarizes the aforementioned TEG devices: their applications, types of materials used, and construction methods.

[0009] Table 1

[0010] Therefore, applying thermoelectric coatings to window glass, touch screens, photovoltaic panels, and other types of structures and devices to convert thermal energy into electrical energy, and to make the devices more energy sustainable under certain conditions, has an attractive prospect.

[0011] These facts are disclosed to illustrate the technical problem that this invention aims to solve. Summary of the Invention

[0012] This invention relates to a heterostructure thermoelectric device capable of efficiently converting thermal energy into electrical energy. The device comprises a series of heterostructure layers that improve thermoelectric performance by optimizing the Seebeck coefficient and electrical conductivity while reducing thermal conductivity. This device can be integrated into various applications such as windows, touch displays, photovoltaic panels, and solar thermal panels, enabling it to collect thermal energy and convert it into electrical energy.

[0013] The heterogeneous thermoelectric device of this invention has a layered structure, combining the structure, materials, and thickness of layers, significantly improving the thermoelectric energy conversion efficiency compared to traditional thermoelectric devices. This invention integrates a thermoelectric material layer, an interface layer that enhances material bonding and device stability, and a conductive layer (electrode) that provides a highly efficient conductive path. This synergistic combination endows the device with excellent thermoelectric performance, enabling its effective integration into various applications, such as windows, touch displays, photovoltaic panels, and solar thermal panels. This integration capability allows for flexible heat energy harvesting from different sources, filling a significant gap in the field of energy conversion technology. Furthermore, depending on the selected substrate, the heterogeneous structure device can be fabricated as a rigid structure (when glass is used as the substrate) or a flexible structure (when polymer is used as the substrate).

[0014] This invention relates to a heterogeneous structural material, specifically a microarray matrix of pillars or columns with thermoelectric properties, capable of collecting heat energy conducted perpendicular to the outer and inner surfaces (out-of-plane direction), possessing optical transparency in the visible light range, and incorporating the integrated functions proposed in this invention. This invention is applicable to structures where a temperature difference exists between two surfaces (typically between the inner and outer surfaces) to collect heat from the hotter surface and, if a temperature difference exists, convert it into electrical energy.

[0015] This effect is called the Seebeck effect, which can be expressed as: the absolute voltage or potential difference generated between the hot and cold electrodes of a thermoelectric material divided by the temperature difference passing through the material.

[0016] Currently, many transparent thermoelectric coatings are designed to collect temperature differences on the material surface (in-plane direction), rather than temperature differences passing through the material (out-of-plane direction), which are the temperature differences passing through the cross-section of window glass. In the prior art, there are no disclosures regarding microarrays of matrix-arranged pillars or columns with thermoelectric properties. Such microarrays can collect heat energy conducted perpendicular to the outer and inner surfaces (out-of-plane direction), possess optical transparency in the visible light range, and integrate the various functions proposed in this invention.

[0017] This invention relates to a thermoelectric device comprising: a substrate; a bottom conductive layer deposited on the substrate; a top conductive layer; a plurality of pillars of thermoelectric semiconductor material located between the top conductive layer and the bottom conductive layer; an electrically insulating and thermally insulating layer [located between the top conductive layer and the bottom conductive layer] and surrounding each of the plurality of pillars; wherein the electrically insulating and thermally insulating layer is transparent to visible light; wherein each of the plurality of pillars is cylindrical and has a diameter of 50 nm to 500 μm; wherein the plurality of pillars of thermoelectric semiconductor material generate a potential difference when the bottom conductive layer and the top conductive layer are subjected to a temperature difference.

[0018] In an embodiment, the heterostructure material includes a transparent thermoelectric micropillar or pillar array etched along its thickness into a glass substrate or structure. The array includes transparent bottom and top conductive layers (electrodes), a patterned transparent electrically insulating glass matrix with holes, and thermoelectric semiconductor material deposited in these holes.

[0019] In an embodiment, the heterostructure material includes a transparent thermoelectric micropillar or pillar array etched along the thickness direction into a polymer substrate. The array includes transparent bottom and top conductive layers (electrodes), a patterned transparent electrically insulating polymer matrix with pores, and thermoelectric semiconductor material deposited in these pores, thereby forming a flexible and transparent device.

[0020] In one embodiment, a transparent matrix comprising cylindrical thermoelectric pillars or columns generates a potential difference when the top and bottom electrodes are subjected to a temperature difference. The current generated from these pillars or columns is collected to provide an output DC power, which can, for example, charge a battery or be converted to AC power.

[0021] Therefore, the heterostructure material allows for the recovery of thermal energy from its surface, which is typically wasted thereon, and its conversion into electrical energy. Preferably, all layers, substrate pillars or columns, and electrodes are optically transparent in the visible electromagnetic spectrum. Furthermore, the top and bottom electrodes, made of transparent conductive oxide (TCO) materials such as fluorine-doped tin oxide (FTO), or indium tin oxide (ITO), or indium-doped, aluminum-doped, and / or gallium-doped zinc oxide (IZO, AZO, GZO), are not only transparent but also have a density greater than 1 × 10⁻⁶. 4 The electrode exhibits a conductivity of S / cm and good adhesion to the glass substrate. The electrode thickness ranges from 50 to 300 nm. The electrically insulating matrix can be made of a transparent, electrically and thermally insulating oxide material such as silicon oxide or aluminum oxide, for example, with a thickness between 200 and 2000 nm. The thermoelectric pillar or column should be made of a transparent semiconductor material, n-type or p-type, or a combination of both, with high conductivity, preferably greater than 1 × 10⁻⁶. 4 S / cm, low thermal conductivity, preferably less than 2 W·m -1 ·K -1 The material is preferably derived from doped metal oxides, such as zinc oxide, copper oxide, or titanium dioxide. To avoid transmission loss through the heterostructure material on the glass, its total thickness should preferably be less than 3 μm; however, in the range of 3 to 30 μm, its average transmittance in the visible light region should also be about 80%.

[0022] In this embodiment, the invention is applied to the glass and civil engineering industry, specifically to window glass. These glass structures can be functionalized with the aforementioned heterogeneous structural material to collect heat from either side of the glass, depending on atmospheric conditions. For example, in summer, the outer surface of the window glass should be much warmer than the inner surface, while in winter / cold weather, the opposite is expected.

[0023] In one embodiment, a glass structure having TCO electrode layers on both surfaces can be etched with a matrix of hole arrays throughout its thickness, into which thermoelectric material can be deposited to collect heat from either side of the glass surface.

[0024] In one embodiment, a polymer substrate having TCO electrode layers on both surfaces can be etched with a matrix of pore arrays throughout its thickness, into which thermoelectric material can be deposited to collect heat from either side of the polymer surface.

[0025] Because the heterogeneous structural material includes thermoelectric pillars or pillar arrays, the temperature difference between the outer and inner surfaces of the window glass will generate a potential difference. The same concept can be applied to other devices, such as touch displays, photovoltaic panels, solar thermal panels, or similar structures / surfaces. Therefore, this invention can also be applied to the electronic components industry, etc.

[0026] This invention discloses a thermoelectric device for collecting thermal energy and converting it into electrical energy, comprising: Base; A bottom conductive layer deposited on the substrate; Top conductive layer; Multiple pillars of thermoelectric semiconductor material; An electrically and thermally insulating layer surrounds the plurality of pillars; The electrically insulating and thermally insulating layer and the thermoelectric material are located between the bottom conductive layer and the top conductive layer.

[0027] In an embodiment, each column is separated from its adjacent column by the electrically and thermally insulating layer.

[0028] In one embodiment, each column is separated from its adjacent column by the glass structure in which the column is etched.

[0029] In one embodiment, each pillar is separated from its adjacent pillar by the polymer substrate, and the pillar is etched into the polymer substrate.

[0030] In one embodiment, the electrically and thermally insulating layer is transparent to visible light.

[0031] In an embodiment, the material of the transparent electrically and thermally insulating layer is selected from: glass, polymer, or a combination thereof.

[0032] In the embodiments, each column is cylindrical or cuboid, preferably cylindrical.

[0033] In an embodiment, each of the plurality of pillars has a diameter of 50 nm to 500 μm, preferably 50 μm to 200 μm.

[0034] In an embodiment, each of the plurality of pillars has a spacing of 50 nm to 500 μm, preferably 50 μm to 200 μm.

[0035] In an embodiment, each of the plurality of pillars has a height of 50 nm to 500 μm, preferably 0.5 μm to 1 μm.

[0036] In this embodiment, the bottom conductive layer and the top conductive layer are transparent to light, preferably transparent to visible light.

[0037] In this embodiment, the top and bottom conductive layers are made of transparent conductive metal oxide layers with a conductivity greater than 1000 S / cm. Ionic conductivity can be measured using a standard method, namely electrochemical impedance spectroscopy (EIS) at 300 K.

[0038] In an embodiment, the top and bottom conductive layers are made of materials selected from: fluorine-doped tin oxide, indium tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, or mixtures thereof.

[0039] In the embodiments, each of the top and bottom conductive layers has a thickness of 50 nm to 500 nm, preferably 100 nm to 300 nm.

[0040] In one embodiment, the electrically and thermally insulating matrix layer is made of a metal oxide.

[0041] In the embodiments, the electrically and thermally insulating matrix layer is made of glass and / or polymer; preferably a thin film.

[0042] In an embodiment, the electrically and thermally insulating layer is made of a material selected from the group consisting of silicon oxide, bismuth oxide, titanium oxide, vanadium oxide, chromium oxide, tantalum oxide, zinc oxide, hafnium oxide, aluminum oxide, copper oxide, zirconium oxide, aluminum oxide, or mixtures thereof.

[0043] In an embodiment, the electrically and thermally insulating layer is made of a polymer selected from the following: polyethylene terephthalate, polyethylene, polyvinyl chloride, polypropylene, polystyrene, poly(methyl acrylate), SU-8, cellulose acetate, and polyamide.

[0044] In the embodiments, the electrically and thermally insulating layer in thin film form has a thickness of 50 nm to 500 μm, preferably 0.5 μm to 1 μm.

[0045] In the embodiments, the electrically and thermally insulating layer in polymer form has a thickness of 10 μm to 10 mm, preferably 20 μm to 1 mm.

[0046] In the embodiments, the glass-type electrically and thermally insulating layer has a thickness of 1 mm to 10 mm, preferably 2 mm to 4 mm.

[0047] In this embodiment, the thermoelectric semiconductor material is transparent to light, preferably transparent to visible light.

[0048] In this embodiment, the thermoelectric semiconductor material is a metal oxide doped with cations or anions.

[0049] In the embodiments, the thermoelectric semiconductor material is a doped or undoped carbon material selected from the list of carbon materials, such as carbon nanowires, carbon nanofibers, or carbon nanotubes.

[0050] In the embodiments, the thermoelectric semiconductor material is undoped titanium oxide or titanium oxide doped with elements selected from the following: niobium, aluminum, gallium, molybdenum, iron, antimony, bismuth, vanadium, tantalum, nitrogen, phosphorus, arsenic, indium, sulfur, carbon, or mixtures thereof.

[0051] In an embodiment, the thermoelectric semiconductor material is undoped zinc oxide or zinc oxide doped with elements selected from the following: niobium, aluminum, gallium, molybdenum, iron, antimony, bismuth, vanadium, tantalum, nitrogen, phosphorus, arsenic, indium, sulfur, carbon, or mixtures thereof.

[0052] In an embodiment, the thermoelectric semiconductor material is undoped copper oxide or copper oxide doped with elements selected from the following: niobium, aluminum, gallium, molybdenum, iron, antimony, bismuth, vanadium, tantalum, nitrogen, phosphorus, arsenic, indium, sulfur, carbon, or mixtures thereof.

[0053] In the embodiments, the substrate is glass or polymer.

[0054] In this embodiment, the plurality of pillars are a microarray.

[0055] In this embodiment, the bottom conductive layer is an anode or a cathode, and the top conductive layer is a cathode or an anode.

[0056] The present invention also discloses a method for obtaining the thermoelectric device, comprising the following steps performed in sequence: Deposit a bottom conductive layer on the substrate; An electrically insulating and thermally insulating layer is deposited on the surface of the bottom conductive layer. The electrically and thermally insulating layer is coated with a photoresist layer; A hole matrix is ​​patterned on the photoresist layer by optical lithography or laser direct writing until the electrically and thermally insulating layer is reached. The electrically and thermally insulating layer not covered by the photoresist layer (i.e. uncoated) is etched using reactive ion etching until the bottom conductive layer is reached; Deposited thermoelectric materials; Remove excess thermoelectric material, that is, remove the thermoelectric material above the surface of the photoresist layer, and retain the thermoelectric semiconductor material inside the hole to form multiple pillars of thermoelectric semiconductor material; Remove the photoresist layer; Deposit the top conductive layer.

[0057] In the embodiments, the bottom conductive layer and the top conductive layer are deposited by physical vapor deposition, chemical vapor deposition, atomic layer deposition, wet chemical deposition, including sol-gel method, electrodeposition, molecular beam epitaxy, pulsed laser sintering, pulsed laser deposition or arc plating.

[0058] In an embodiment, the electrically and thermally insulating matrix layer is deposited by physical or chemical vapor deposition, spin coating, or wet chemical methods.

[0059] In the embodiments, the electrically insulating and thermally insulating matrix layer is deposited by physical vapor deposition, chemical vapor deposition, atomic layer deposition, wet chemical deposition, including sol-gel method, electrodeposition, spin coating, molecular beam epitaxy, pulsed laser sintering, pulsed laser deposition, or arc plating.

[0060] In the embodiments, the deposition of the thermoelectric material is carried out by physical vapor deposition, chemical vapor deposition, atomic layer deposition, electrodeposition, wet chemical processes such as sol-gel method, molecular beam epitaxy, pulsed laser sintering, pulsed laser deposition or arc plating.

[0061] In an embodiment, for an n-type or p-type semiconductor thermoelectric material, the bottom conductive electrode is an anode or a cathode, and the top conductive electrode is a cathode or an anode.

[0062] The present invention also discloses the use of the device for collecting heat energy from a window. Attached Figure Description

[0063] The following figures provide preferred embodiments for illustrating the present disclosure and should not be construed as limiting the scope of the invention.

[0064] Figure 1 : A schematic diagram of an embodiment of a microfabrication step cross-section for obtaining a thermoelectric transparent microarray, showing the following steps: a) starting from a glass substrate; b) depositing a bottom electrode; c) depositing a SiO2 insulating matrix layer; d) coating with a photoresist layer; e) defining a micropillar array or micropillar array; f) etching the insulating matrix layer; g) depositing thermoelectric pillars or pillars; h) removing unwanted material; and finally i) depositing a top electrode.

[0065] Figure 2 Schematic diagram of a heterogeneous thermoelectric material and an experimental apparatus for determining the Seebeck coefficient and output current. Figure 2 Heterogeneous structural materials are presented from multiple perspectives; Figure 2 a shows a cross-section of a heterostructured material; Figure 2 b presents the heterostructured material from two perspectives, indicating the locations of the bottom and top electrodes; in Figure 2 In c, the device is vertically separated into its constituent layers; Figure 2Figure d shows the apparatus for conducting thermoelectric experiments, including two Peltier elements, a sample and a heat sink, and electrical connections; Figure 2 e and Figure 2 f shows Peltier elements without heterostructured materials used for cooling and heating, respectively; Figure 2 g presents another view of the experimental setup, with leads for current and voltage measurements. Detailed Implementation

[0066] This invention relates to an optically transparent thermoelectric heterostructure semiconductor material capable of collecting heat energy, for example, through a glass window, provided there is a temperature difference between the outer and inner surfaces of the window, regardless of which side is hotter. This effect, the Seebeck effect, is not new; however, the heterostructure material and its architecture that generate this thermoelectric effect are novel. The novelty lies in the architecture of the heterostructure layer, which can be effectively applied to glass windows, touchscreens, photovoltaic devices, building structures, etc. Currently, several transparent thermoelectric coatings exist for use on glass surfaces, for example, generating a thermoelectric voltage if there is a surface (in-plane) temperature difference rather than a temperature difference passing through it (out-plane), because the entire coating is heated through either side (inner or outer) of the glass. This invention provides a transparent matrix comprising cylindrical thermoelectric pillars or columns with low thermal conductivity, generating a potential difference when the top and bottom electrodes of the matrix are subjected to a temperature difference. The current generated from these pillars or columns is collected to provide an output DC power, which can, for example, charge a battery or be converted to AC power. Similarly, for other devices such as touch displays, photovoltaic panels, and solar thermal panels, the same heterostructure thermoelectric device can be applied to collect heat energy and convert it into electrical energy, thereby making the device more sustainable.

[0067] The disclosed heterostructure thermoelectric materials are intended for use in structures with a temperature difference between two surfaces (typically an inner and an outer surface), where heat is conducted perpendicularly to these surfaces and converted into electrical energy. Embodiments include transparent thermoelectric micropillars or arrays of pillars comprising transparent bottom and top conductive layers (electrodes), a patterned transparent insulating matrix (with pores), and an n-type or p-type thermoelectric semiconductor material deposited in these pores.

[0068] In the embodiments, the transparent bottom and top conductive layers (electrodes) are made of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), or any combination, mixture, or alloy of these materials, as well as other transparent conductive metal oxides with a conductivity greater than 1000 S / cm.

[0069] In the embodiments, the transparent bottom and top conductive layers have a thickness of 50 to 300 nm.

[0070] In embodiments, the patterned transparent matrix having pores (the pores being spaces for accommodating the base pillars or pillars) is made of silicon dioxide (SiO2), aluminum oxide (Al2O3), titanium oxide (TiO, TiO2, Ti2O3), copper oxide (CuO, CuO2, Cu2O), zirconium oxide (ZrO2), bismuth oxide (BiO, Bi2O3, Bi2O5), hafnium oxide (HfO2), vanadium oxide (VO, VO2), tantalum oxide (Ta2O3), iron oxide (Fe2O3, Fe3O4), chromium oxide (Cr2O3), zinc oxide (ZnO), or any combination, mixture, or alloy of these metal oxides, or is made of transparent electrically insulating metal oxides.

[0071] In the embodiments, the patterned transparent substrate with pores is an electrically and thermally insulating material, which may be in the form of glass and / or polymer films.

[0072] In the embodiments, the thickness of the patterned transparent matrix ranges from 50 nm to 500 μm, but larger thicknesses can also be considered. These thickness ranges correspond to the depth of the pores.

[0073] In the embodiments, the patterned transparent substrate has cylindrical or rectangular holes with a diameter or size ranging from 50 nm to 500 μm. Preferably, the substrate or pillar of the thermoelectric semiconductor material can be cylindrical or rectangular.

[0074] In one embodiment, the patterned transparent substrate has pores with a spacing ranging from 50 nm to 500 μm.

[0075] In the embodiments, the thermoelectric semiconductor material deposited in the holes to form the pillars or columns is a semiconductor metal oxide, preferably titanium dioxide (TiO2), zinc oxide (ZnO), or any combination, mixture or alloy of these oxides, or any other transparent n-type or p-type metal oxide with good thermoelectric properties, such as copper oxide-based metal oxides, or transparent doped or undoped carbon materials, such as carbon nanowires, carbon nanofibers or carbon nanotubes.

[0076] In the embodiments, the thermoelectric semiconductor material deposited in the holes is n-type or p-type and doped with an element (cation or anion) selected from the following: niobium, aluminum, gallium, molybdenum, iron, antimony, bismuth, vanadium, tantalum, nitrogen, phosphorus, arsenic, indium, or any combination or mixture of the above elements.

[0077] In the embodiments, the thermoelectric material is deposited using physical vapor deposition, chemical vapor deposition, atomic layer deposition, wet chemical deposition (including sol-gel method and electrodeposition), molecular beam epitaxy, pulsed laser sintering, pulsed laser deposition, arc plating, and other common deposition techniques.

[0078] In the embodiments, the microfabrication process required to obtain the thermoelectric transparent microarray includes a series of steps: starting from a glass substrate ( Figure 1 a); Deposited bottom electrode ( Figure 1 b); Deposited insulating matrix layer ( Figure 1 c); Coated with a photoresist layer ( Figure 1 d); Defined micropillar array ( Figure 1 e); Etching the insulating substrate layer ( Figure 1 f); Deposited thermoelectric material substrate ( Figure 1 g); Remove unwanted materials ( Figure 1 h); and finally deposit the top electrode (h); and finally deposit the top electrode ( Figure 1 i).

[0079] In an embodiment, Figure 1 The diagram shows: 1 substrate, 2 bottom conductive layer, 3 electrically and thermally insulating layer, 4 photoresist material, 5 thermoelectric semiconductor material, and 6 top conductive layer.

[0080] Figure 2 This illustrates a heterogeneous material structure and the experimental setup used to measure the Seebeck coefficient and output current.

[0081] Figure 2 Heterogeneous structural materials are presented from multiple perspectives. Figure 2 a) shows a cross-section of the heterostructure material. Multiple layers constituting the heterostructure material are deposited on a glass substrate covered with a transparent conductive layer. Throughout the fabrication process, the edges of the sample were protected to allow contact with the bottom electrode, ultimately resulting in a material similar to... Figure 2 The design shown in b) is in... Figure 2 In b), the heterostructure material can be seen from two perspectives, showing the locations of the bottom and top electrodes. Figure 2 In c), the device is separated into its constituent layers.

[0082] Considering the arrangement of micropillars or arrays of micropillars, a temperature difference must be applied to all layers. Figure 2 d) illustrates the setup constructed for thermoelectric measurements, where a heterogeneous material structure is "sandwiched" between two Peltier modules to create a temperature difference. For each Peltier module, one side is heated 8a, and the other side is cooled 8b. A radiator is connected to the unused side of the Peltier module to emphasize the side actually used to generate the temperature difference. 7 indicates the radiator. Figure 2 e) and Figure 2 f) shows a decomposition apparatus without heterostructured materials and two Peltier stages for heating 8a and cooling 8b, with thermocouples for temperature measurement. Figure 2 g) presents another view of the experimental setup, with leads for current and voltage measurements.

[0083] The resulting output potential difference and current are measured using, for example, an Agilent 34401A high-precision multimeter. Thermocouples are used to accurately measure the temperature on the top and bottom electrodes. The Peltier modules are power-controlled; special care must be taken not to exceed the maximum voltage and current values ​​of these modules. This device allows measurement of the potential between the top and bottom electrodes and the output current (the sum of all currents flowing from each base / pillar) when a temperature difference is applied between them.

[0084] like Figure 2 As shown, the Peltier module generates a temperature difference on a heterogeneous material structure, which is monitored by a thermocouple. This temperature difference is responsible for creating a potential difference between the top and bottom electrodes, which in turn generates a current through the thermoelectric base / pillar. Both quantities are measured by electrodes implemented in the device.

[0085] In this embodiment, the heterogeneous structural material can be applied to window glass. Depending on atmospheric conditions, these structures can be functionalized with the heterogeneous structural material to collect heat from either side of the glass structure. For example, in summer, the outer surface of the window glass should be much warmer than the inner surface, while in winter / cold weather, the opposite is expected.

[0086] In this embodiment, the manufacturing process required to obtain the thermoelectrically transparent microarray includes a series of steps, in this example, starting with a soda-lime glass (SLG) substrate or other types of commercial glass used for window glass, for transparency ( Figure 1 a). Then, a fluorine-doped tin oxide (FTO) film is deposited on the glass substrate as the bottom electrode (or anode for n-type semiconductor thermoelectric materials), due to its transparency and good thermal and electrical conductivity ( Figure 1 b). Alternatively, other transparent conductive metal oxide (TCO) materials, such as aluminum-doped zinc oxide (ZnO:Al or AZO), gallium-doped zinc oxide (ZnO:Ga or GZO), and indium tin oxide (ITO) films, can be used to coat the glass. These TCO films can be deposited by physical vapor deposition, including thermal evaporation, sputtering, preferably, or by chemical vapor deposition, including atomic layer deposition, or by wet chemistry, such as sol-gel methods, and other deposition techniques. FTO-coated glass can also be used as a substrate material.

[0087] The next step is to deposit an electrically and thermally insulating matrix layer. Figure 1 c), preferably made of silicon oxide (SiO2) or aluminum oxide (Al2O3). This electrically and thermally insulating film can be deposited by chemical vapor deposition (CVD), preferably, or by atomic layer deposition (ALD), wet chemical deposition (e.g., sol-gel method), or physical vapor deposition (PVD, sputtering, thermal evaporation), and other deposition techniques. This insulating layer forms the thermoelectric substrate pillar or column created in subsequent steps.

[0088] Then, using photolithography or other stencil methods, an electrically and thermally insulating matrix layer is coated with photoresist or another type of mask material. Figure 1 d). Photolithography: laser direct writing, defining micropillars or arrays of micropillars to obtain the desired pattern ( Figure 1 e).

[0089] In an embodiment, the desired pattern includes pillars spaced apart to form an array of holes with a diameter ranging from 50 nm to 500 μm, a spacing of 50 nm to 500 μm, and a depth of 50 nm to 500 μm.

[0090] After the pattern is imprinted onto the photoresist layer, reactive ion etching is used to etch the insulating substrate layer that is not covered by the photoresist. Figure 1 f). This will produce an insulating matrix with cylindrical pores in which thermoelectric material will be deposited.

[0091] In the next step, thermoelectric materials, such as TiO2:Nb as an example of an n-type semiconductor, are deposited by sputtering, preferably by PVD (sputtering, evaporation), CVD or ALD, or by wet chemistry, such as sol-gel method, or by electrodeposition and other deposition techniques. Figure 1 g). Once the TiO2:Nb substrate is fabricated, excess material on top of the photoresist is removed. Excess TiO2:Nb is removed using a photoresist stripping technique, and the remaining photoresist is subsequently removed. Figure 1 h).

[0092] Finally, the entire device is covered with a top contact layer, preferably a top conductive layer, which serves as the top electrode (or cathode for n-type thermoelectric materials). Figure 1 i). This layer is made of FTO or other transparent conductive metal oxide (TCO) materials, such as aluminum-doped zinc oxide (ZnO:Al or AZO), gallium-doped zinc oxide (ZnO:Ga or GZO), and indium tin oxide (ITO) films, which can also be used to coat glass.

[0093] Throughout the manufacturing process, the edges of the sample are protected to allow contact with the bottom electrode, ultimately achieving a result similar to... Figure 2 Design shown in b.

[0094] In this embodiment, the device is a thermoelectric transparent microarray heterostructure deposited on a transparent substrate. Preferably, the transparent substrate is glass or a polymer.

[0095] In this embodiment, the top and bottom electrodes are made of a transparent conductive metal oxide layer. Preferably, fluorine-doped tin oxide is used. In this embodiment, the transparent conductive layer is composed of doped tin oxide, doped titanium oxide, or doped zinc oxide.

[0096] In an embodiment, the transparent conductive layer is composed of fluorine-doped tin oxide or indium tin oxide.

[0097] In an embodiment, the transparent conductive layer is composed of aluminum oxide doped with gallium and / or bismuth and / or indium and / or aluminum.

[0098] In this embodiment, the thickness of the transparent conductive layer ranges from 50 nm to 500 μm.

[0099] In an embodiment, the transparent conductive layer is deposited by physical or chemical vapor deposition.

[0100] In one embodiment, a transparent, electrically insulating, and thermally insulating layer is deposited on the bottom electrode.

[0101] In an embodiment, the thickness of the transparent electrically and thermally insulating layer ranges from 50 nm to 500 μm.

[0102] In one embodiment, the transparent electrically and thermally insulating layer is made of a metal oxide.

[0103] In an embodiment, the transparent, electrically insulating, and thermally insulating material is glass, a polymer, or a combination thereof.

[0104] In an embodiment, the transparent electrically and thermally insulating thin film is selected from silicon oxide, bismuth oxide, titanium oxide, vanadium oxide, chromium oxide, tantalum oxide, or zinc oxide, hafnium oxide, aluminum oxide, copper oxide, zirconium oxide, or any combination, mixture or alloy of these metal oxides, or transparent metal oxides.

[0105] In an embodiment, the transparent electrically and thermally insulating layer is deposited by physical or chemical vapor deposition or by wet chemical synthesis.

[0106] In one embodiment, the transparent electrically and thermally insulating layer is etched with cylindrical holes along its thickness, with a diameter ranging from 50 nm to 500 μm. In another embodiment, the transparent electrically and thermally insulating layer is etched with cylindrical holes along its thickness, with a spacing ranging from 50 nm to 500 μm. In yet another embodiment, the transparent electrically and thermally insulating layer is etched with cylindrical holes along its thickness, with a depth ranging from 50 nm to 500 μm.

[0107] In an embodiment, the transparent electrically and thermally insulating layer is a polymer and has cylindrical holes etched along its thickness, with diameters ranging from 50 nm to 500 μm.

[0108] In one embodiment, the transparent electrically and thermally insulating layer is etched with cylindrical holes along the polymer thickness, with a spacing ranging from 50 nm to 500 μm.

[0109] In one embodiment, the transparent electrically and thermally insulating layer is etched with cylindrical holes along its thickness, with a depth ranging from 100 nm to 10 mm.

[0110] In an embodiment, the transparent electrically and thermally insulating layer is a polymer and has cylindrical holes etched along its thickness, with diameters ranging from 50 nm to 500 μm.

[0111] In one embodiment, the transparent electrically and thermally insulating layer is etched with cylindrical holes along the glass thickness, with a spacing ranging from 50 nm to 500 μm.

[0112] In one embodiment, the transparent electrically and thermally insulating layer is etched with cylindrical holes along its thickness, with a depth ranging from 2 mm to 4 mm.

[0113] In one embodiment, a transparent thermoelectric material is deposited into cylindrical pores in the transparent electrically and thermally insulating matrix.

[0114] In an embodiment, the transparent thermoelectric material filling the cylindrical pores of the matrix is ​​a semiconductor n-type metal oxide.

[0115] In an embodiment, the transparent thermoelectric material filling the cylindrical pores of the matrix is ​​a semiconductor p-type metal oxide.

[0116] In one embodiment, the transparent thermoelectric material filling the cylindrical pores of the matrix is ​​a combination of n-type and p-type metal oxide semiconductors.

[0117] In this embodiment, the transparent thermoelectric material is a metal oxide doped with cations.

[0118] In this embodiment, the transparent thermoelectric material is a metal oxide doped with anions.

[0119] In the embodiments, the transparent thermoelectric material is a doped or undoped carbon material, such as carbon nanowires, carbon nanofibers, or carbon nanotubes.

[0120] In the embodiments, the transparent thermoelectric material is undoped titanium oxide or titanium oxide doped with elements selected from the following: niobium, aluminum, gallium, molybdenum, iron, antimony, bismuth, vanadium, tantalum, nitrogen, phosphorus, arsenic, indium, or any combination and mixture of the above elements.

[0121] In the embodiments, the transparent thermoelectric material is undoped zinc oxide or zinc oxide doped with elements selected from the following: niobium, aluminum, gallium, molybdenum, iron, antimony, bismuth, vanadium, tantalum, nitrogen, phosphorus, arsenic, indium, or any combination and mixture of the above elements.

[0122] In the embodiments, the transparent thermoelectric material is undoped copper oxide or copper oxide doped with elements selected from the following: niobium, aluminum, gallium, molybdenum, iron, antimony, bismuth, vanadium, tantalum, nitrogen, phosphorus, arsenic, indium, or any combination or mixture of the above elements.

[0123] In the embodiments, the transparent electrically and thermally insulating layer is deposited using techniques selected from: physical vapor deposition, chemical vapor deposition, atomic layer deposition, wet chemical deposition (including sol-gel method, electrodeposition), molecular beam epitaxy, pulsed laser sintering, pulsed laser deposition, arc plating, and other common deposition techniques.

[0124] In one embodiment, the top conductive layer, which serves as the electrode, is deposited onto the aforementioned matrix composed of thermoelectric pillars / pillar arrays.

[0125] When used in this document, the term "comprising" is intended to indicate the presence of the said feature, integer, step, or component, but does not exclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

[0126] This disclosure should not be construed as limiting in any way to the described embodiments, and those skilled in the art will foresee many possible modifications. The above embodiments are composable.

[0127] The following claims further illustrate specific embodiments of the present disclosure.

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[16] THERMOELECTRIC TRANSPARENT THIN FILM AND METHOD THEREOF, CarlosJosé Tavares, Joana Ribeiro,Filipe Correia Costa – Portuguese Patent PT110639.

Claims

1. A thermoelectric device, comprising: Base; A bottom conductive layer deposited on the substrate; Top conductive layer; Multiple pillars of thermoelectric semiconductor material; An electrically and thermally insulating layer surrounds each of the plurality of pillars; The electrically and thermally insulating layer is transparent to visible light. Each of the plurality of cylindrical pillars has a diameter of 50 nm to 500 μm; When the bottom conductive layer and the top conductive layer are subjected to a temperature difference, the multiple pillars of the thermoelectric semiconductor material generate a potential difference.

2. The device of the preceding claim, wherein, The transparent, electrically and thermally insulating material is glass, a polymer, or a combination thereof; preferably a thin film.

3. The device of any of the preceding claims, wherein, The electrically and thermally insulating layer has a thickness of less than 30 μm.

4. The device of any of the preceding claims, wherein, The electrically and thermally insulating polymer layer has a thickness of less than 10 mm; preferably less than 5 mm; more preferably less than 1 mm.

5. The device of any of the preceding claims, wherein, The electrically and thermally insulating glass layer has a thickness of less than 10 mm; preferably less than 5 mm; more preferably less than 4 mm.

6. The device of any of the preceding claims, wherein, The electrically and thermally insulating layer has a thickness of less than 1 mm, more preferably less than 15 μm.

7. The device of any of the preceding claims, wherein, The electrically and thermally insulating layer has a thickness of less than 5 μm, preferably less than 3 μm.

8. The apparatus according to any one of the preceding claims, wherein, Each column is cylindrical or cuboid in shape, preferably cylindrical.

9. The apparatus according to any one of the preceding claims, wherein, Each of the plurality of cylindrical columns has a diameter of 50 nm to 500 μm, preferably 50 μm to 200 μm.

10. The apparatus according to any one of the preceding claims, wherein, Each of the plurality of pillars has a spacing of 50 nm to 500 μm, preferably 50 μm to 200 μm.

11. The apparatus according to any one of the preceding claims, wherein, Each of the plurality of pillars has a height of 50 nm to 500 μm, preferably 0.5 μm to 1 μm.

12. The apparatus according to any one of the preceding claims, wherein, The bottom conductive layer and the top conductive layer are transparent to light, preferably to visible light.

13. The apparatus according to any one of the preceding claims, wherein, The top conductive layer and the bottom conductive layer are made of a transparent conductive metal oxide layer, the conductivity of which is greater than 1000 S / cm.

14. The apparatus according to any one of the preceding claims, wherein, The top conductive layer and the bottom conductive layer are made of materials selected from the group consisting of fluorine-doped tin oxide, indium tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, or mixtures thereof.

15. The apparatus according to any one of the preceding claims, wherein, Each of the top conductive layer and the bottom conductive layer has a thickness of 50 nm to 500 nm, preferably 100 nm to 300 nm.

16. The apparatus according to any one of the preceding claims, wherein, The electrically and thermally insulating matrix layer is made of metal oxide.

17. The apparatus according to any one of the preceding claims, wherein, The electrically and thermally insulating layer is made of a material selected from the group consisting of silicon oxide, bismuth oxide, titanium oxide, vanadium oxide, chromium oxide, tantalum oxide, zinc oxide, hafnium oxide, aluminum oxide, copper oxide, zirconium oxide, aluminum oxide, or mixtures thereof.

18. The apparatus according to any one of the preceding claims, wherein, The electrically and thermally insulating layer has a thickness of 50 nm to 500 μm, preferably 0.5 μm to 1 μm.

19. The apparatus according to any one of the preceding claims, wherein, The thermoelectric semiconductor material is transparent to light, preferably transparent to visible light.

20. The apparatus according to any one of the preceding claims, wherein, The thermoelectric semiconductor material is a metal oxide doped with cations or anions.

21. The apparatus according to any one of the preceding claims, wherein, The thermoelectric semiconductor material is selected from the following doped or undoped carbon materials: carbon nanowires, carbon nanofibers, or carbon nanotubes.

22. The apparatus according to any one of the preceding claims, wherein, The thermoelectric semiconductor material is undoped titanium oxide or titanium oxide doped with elements selected from the following: niobium, aluminum, gallium, molybdenum, iron, antimony, bismuth, vanadium, tantalum, nitrogen, phosphorus, arsenic, indium, sulfur, carbon, or mixtures thereof.

23. The apparatus according to any one of the preceding claims, wherein, The thermoelectric semiconductor material is undoped zinc oxide or zinc oxide doped with elements selected from the following: niobium, aluminum, gallium, molybdenum, iron, antimony, bismuth, vanadium, tantalum, nitrogen, phosphorus, arsenic, indium, sulfur, carbon, or mixtures thereof.

24. The apparatus according to any one of the preceding claims, wherein, The thermoelectric semiconductor material is undoped copper oxide or copper oxide doped with elements selected from the following: niobium, aluminum, gallium, molybdenum, iron, antimony, bismuth, vanadium, tantalum, nitrogen, phosphorus, arsenic, indium, sulfur, carbon, or mixtures thereof.

25. The apparatus according to any one of the preceding claims, wherein, The substrate is glass or polymer.

26. The apparatus according to any one of the preceding claims, wherein, The multiple pillars are a microarray.

27. The apparatus according to any one of the preceding claims, wherein, The bottom conductive layer is an anode or a cathode, and the top conductive layer is a cathode or an anode.

28. A method for obtaining a thermoelectric device according to any one of the preceding claims, comprising the following steps: Deposit a bottom conductive layer on the substrate; An electrically insulating and thermally insulating layer is deposited on the surface of the bottom conductive layer. The electrically and thermally insulating matrix layer is coated with a photoresist layer; A hole matrix is ​​patterned on the photoresist layer by optical lithography or laser direct writing until the electrically and thermally insulating layer is reached. The electrically and thermally insulating layer not covered by the photoresist layer is etched using reactive ion etching until the bottom conductive layer is reached; Deposited thermoelectric semiconductor materials; Remove excess thermoelectric semiconductor material, and retain the thermoelectric semiconductor material that fills the hole and forms multiple pillars; Remove the photoresist layer; Deposit the top conductive layer.

29. The method according to claim 27, wherein, The bottom conductive layer and the top conductive layer are deposited by physical vapor deposition; chemical vapor deposition; atomic layer deposition; wet chemical methods, including sol-gel method, electrodeposition; molecular beam epitaxy; pulsed laser sintering; pulsed laser deposition or arc plating.

30. The method according to any one of claims 27 to 28, wherein, The electrically and thermally insulating matrix layer is deposited by physical or chemical vapor deposition, spin coating, or wet chemical methods.

31. The method according to any one of claims 27 to 29, wherein, The electrically and thermally insulating matrix layer is deposited by physical vapor deposition; chemical vapor deposition; atomic layer deposition; spin coating; wet chemical processes, including sol-gel method, electrodeposition; molecular beam epitaxy; pulsed laser sintering; pulsed laser deposition; or arc plating.

32. The method according to any one of claims 27 to 30, wherein, The deposition of the thermoelectric material is carried out through physical vapor deposition; chemical vapor deposition; atomic layer deposition; electrodeposition; wet chemistry, including sol-gel method; molecular beam epitaxy; pulsed laser sintering; pulsed laser deposition; or arc plating.

33. The apparatus according to any one of claims 1 to 27 is used for collecting thermal energy from a window and converting it into electrical energy.

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