WO2009140730A1 - Thermoelectric element - Google Patents
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- WO2009140730A1 WO2009140730A1 PCT/AU2009/000631 AU2009000631W WO2009140730A1 WO 2009140730 A1 WO2009140730 A1 WO 2009140730A1 AU 2009000631 W AU2009000631 W AU 2009000631W WO 2009140730 A1 WO2009140730 A1 WO 2009140730A1
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- thermoelectric element
- thermoelectric
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/857—Thermoelectric active materials comprising compositions changing continuously or discontinuously inside the material
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/8556—Thermoelectric active materials comprising inorganic compositions comprising compounds containing germanium or silicon
Definitions
- the present invention relates to a thermoelectric element containing nanometre-sized features.
- the present invention relates to a method for forming a thermoelectric element containing nanometre-sized features.
- thermoelectric effect is the conversion of temperature differences to electric voltage, or the conversion of electric voltage to temperature differences.
- a thermoelectric device creates an electric voltage when there is a different temperature on each side of the device.
- a thermoelectric device creates a temperature difference when a voltage is applied to it.
- the thermoelectric effect can be used to generate electricity, to measure temperature, to cool objects, or to heat objects.
- thermoelectric devices for cooling and heating and for the generation of electricity have been known for many years.
- thermoelectric devices have not been cost competitive (except for limited or specialised applications) because of the lack of thermoelectric materials having appropriate thermoelectric properties.
- This patent also describes thermoelectric elements having a very large number of alternating layers of semiconductor material, the alternating layers having the same crystalline structure.
- This patent described one thermoelectric material as comprising a superlattice of Si, as a barrier material, and SiGe as a conducting material, both of which have the same cubic structure.
- thermoelectric material described in this patent comprises a superlattice of B-C alloys, the layers of which would be different stoichiometric forms of B-C but in all cases the crystalline structure would be alpha rhombohedral.
- Other United States patents that have been assigned to Hi-Z Technology Inc include US 6096964, 6096965, 6828579, 7038234 and 7342170. The entire contents of each of those patents are incorporated herein by cross-reference.
- thermoelectric material layers of the thermoelectric material are deposited on to a substrate.
- Deposition of the layers of the thermoelectric material occurs via molecular beam epitaxy or sputtering.
- the substrates that are used present flat surfaces for receiving the deposited layers of thermoelectric material.
- the substrates used include silicon wafers and flexible films of silicon or polyimides.
- Hi-Z is an example of thermoelectric materials that have nanometre-sized features. It uses a large number of alternating layers of materials, -lOnrn thick, where the layers are essentially flat and parallel, deposited on a flat substrate. In the Hi-Z patents, the layers are oriented so that the electron flow in the thermoelectric element is parallel to the layers.
- thermoelectric elements having a large number of alternating layers which are of nanometre-sized thickness.
- the layers are also essentially flat and parallel, deposited onto a flat substrate.
- the layers are oriented in the thermoelectric element so that the direction of electron movement is perpendicular to the layers.
- Specific materials include alternating layers OfBi 2 Te 3 and Sb 2 Te 3 .
- thermoelectric materials with nano-scale features e.g. Harman et al (US patent 6,605,772).
- the most common effect of nanoscale features appear to be suppression of thermal conductivity, which may be achieved without a drop in electrical conductivity of similar proportion.
- Various mechanisms of phonon blocking have been proposed.
- Another effect that has been predicted theoretically and observed experimentally is an increased Seebeck coefficient that arises due to quantum confinement. This effect is predicted to increase as the dimension of the quantum confinement approaches, or drops below, the exciton Bohr radius.
- the surface that is being deposited on is essentially smooth.
- thermoelectric materials with nanometre-sized features are expensive and/or difficult to scale up. There is therefore a need for new methods and materials that are more commercially viable for production of high performance thermoelectric elements with nanometre-sized features.
- thermoelectric devices require thermoelectric films that are sufficiently thick to enable management of heat flow. Production of sufficiently thick thermoelectric films with nano-scale features is a challenge.
- the thermoelectric material may be about 1-2 mm thick. Making the devices thinner is desirable for lightness and reduced material use, however the thinner the material, the higher the heat flow across the device for a given temperature difference. This can create problems with thermal management since heat flow is typically limited at either the cold side (removal of heat) or the hot side (addition of heat).
- minimum thicknesses have been proposed for devices used in conventional applications, e.g. about 50 micrometres thick or about 100 micrometres thick have been proposed as minimum thicknesses.
- Nano-layer thermoelectric materials are being commercialised by
- Hi-Z corporation have made thicker nanostructured devices by first depositing layered materials on a flat substrate, then cutting up the resultant materials and orientating them perpendicularly to the original flat plane. The cut up pieces must be stuck together. In this way they can make thicker devices with an 'in-plane' orientation of nanolayers.
- this has obvious problems for larger scale manufacture, and the original planar substrate is generally incorporated into the device, leading to heat losses.
- thermoelectric material A range of patents and patent applications seek to protect methods for production of nanostructured thermoelectric whereby a porous scaffold is first produced, which is then filled with thermoelectric material.
- the size, amount and morphology of the thermoelectric material is set by the size, amount and morphology of the pores.
- These methods have difficulties in producing precisely controlled nanostructures since, for example, it may be difficult to get all of the pores exactly the same size.
- the size of the pores sets the size of the thermoelectric material, the pores must be very small if the thermoelectric material is to be nano-scale.
- One proposed benefit of nano-scale features is quantum confinement leading to increased Seebeck coefficients.
- the exciton Bohr radius can be very small for many materials, e.g. ⁇ 2.4 nm for ZnO. Pores of such small size create problems with transport of thermoelectric material or precursors of thermoelectric material. In these methods the porous scaffold may be removed. Porous materials with controlled porosity on the nano-scale, for example so-called MCM-41 silica materials and the like, can have significant amounts of solid material. If this solid is not removed, it obviously remains in the thermoelectric device, where it can conduct heat. This reduces the efficiency of the device. Therefore with many porous materials the original porous material must be removed in order to obtain an efficient device.
- thermoelectric elements comprising nanotubes of thermoelectric material.
- the nanotubes are created by first depositing a metal coating inside the pores of a template/substrate then the thermoelectric material may be deposited on top of the metal via electrodeposition.
- the nanotubes will comprise either an n- doped or a p-doped semiconductor composition.
- the nanotubes can be deposited by electrochemical deposition or by electrochemical atomic layer epitaxy, where a monolayer or sub-monolayer of each element is deposited sequentially from separate baths.
- thermoelectric material is set by the wall thickness of the nanotube. In this application there are no examples where materials have actually been fabricated or a thermoelectric effect measured.
- thermoelectric devices above the minimum useful thicknesses specified above, thermal management can still be an issue.
- a current device may be 2mm thick and operate at a temperature difference of 200 K. It's thermal system is designed to manage 20W/cm2. Reducing the thickness to 200 ⁇ m, i.e. by a factor of 10, would normally increase the heat flow by a factor of 10. However since the thermal system cannot cope with this, the temperature difference will decrease to limit the heat flow and the efficiency of the device will drop.
- One method that has been used to overcome this problem is to reduce the amount of thermoelectric material.
- the equation for heat flow via conduction is; IcA &T
- thermoelectric material i.e. only 10% of the device is actually thermoelectric material. This, however, can lead to losses via heat shunting across the gaps from the hot side to the cold side.
- One way of addressing this problem is to separate the sides via spacers (see Figure 1). Insulating material may also be added in between the thermoelectric material. However it would be advantageous to have a better solution to this problem.
- thermoelectric element or at least to provide a commercially useful alternative. It is also an object of the present invention to provide an improved method for forming thermoelectric elements with nanometre-sized features, or at least to provide a commercially useful alternative.
- the present invention provides a thermoelectric element for use in a thermoelectric device, the thermoelectric element comprising a porous substrate coated with one or more materials, at least one of which is a thermoelectric material.
- the coating may completely coat the surface of the porous substrate. Alternatively, the coating may only partially coat the surface of the porous substrate.
- the porous substrate comprises a non-ordered porous substrate.
- non-ordered porous substrate it is meant that the porous substrate has a pore structure with pores of varying sizes and pores that extend in many different directions. The pores are non-straight. The pores may twist or turn and represent a tortuous path.
- the thermoelectric element may include porosity after the porous substrate has been coated with the thermoelectric material.
- coating of the porous substrate material does not completely fill the pore structure of the porous substrate material, thereby resulting in the thermoelectric element retaining porosity. It will be understood that, as the original pore structure of the substrate has been coated with the thermoelectric material, the porosity of the thermoelectric element will be somewhat lower than the porosity of the original, uncoated substrate.
- the porous substrate may have a high surface area with pore sizes in the nanometer to micrometre range. If an essentially solid film is desired, pore size distributions and types are designed to achieve high volume fractions of solid throughout the film. Pore size distributions and types may also be designed to improve ingress and penetration of gaseous vapours used in the coating process. In the case of porous final materials, the pore size distributions and types may also be designed to minimise thermal conductivity through the structure.
- the porous substrate may be specifically chosen in order to achieve a target volume fraction of thermoelectric material using a target coating thickness. Substrates with higher surface areas per unit volume will require thinner coatings compared to substrates with lower surface areas per unit volume, to achieve the same volume fraction of coating material.
- an aerogel may have a surface area greater than 30 m 2 /cc. This material may only require a coating thickness of a few nanometers to achieve significant volume fraction of coating. In this case, quantum confinement effects and significant phonon blocking effects may be achieved by using only a single layer of material since the layer is of nanometer thickness.
- Some cellulosic-based papers may have a surface area of a few m 2 /cc. These require thicker coatings to achieve a significant volume fraction of coating. The thicker coatings enable more complex nanostructures to be set up, for example multiple nano-layer structures. Therefore the substrate may be designed to suit a designed or required final nanostructure.
- the porous substrate has a significant number of pores in the mesoporous range.
- the porous substrate may have a significant number of pores in the range from 7nm to 250nm.
- the porous substrate may have a significant number of pores ranging from 20nm to several ⁇ m.
- the porous film or substrate may comprise a substrate that is formed with suitable porosity.
- the porous film may be free-standing.
- the porous film or substrate may be provided by forming a porous film or a porous layer onto a solid substrate.
- the porous layer or substrate may be of high surface area.
- the surface area of the porous layer or substrate may be greater than Im 2 /g, or > 10m 2 /g, or >100m 2 /g, or at least several hundred m 2 /g.
- the porous substrate may comprise a porous substrate having a thickness of between ⁇ 10 ⁇ m and ⁇ 2mm, more preferably between ⁇ 50 ⁇ m and ⁇ lmm.
- porous frameworks with low volume fractions of solid.
- Using a porous framework having a lower volume fraction of solid results in the formation of a thermoelectric element that has a lower volume or amount of the original substrate or layer material therein.
- the final material will contain higher amounts of the material that is used in the film or coating.
- the porous framework may have less than 20% solid, or less than 10% solid, or less than 5% solid.
- Part of the porous framework may be a reinforcement component, for example, fibres, whiskers, particles fibrous mat or tissue, and the like. It is preferable that this reinforcement be orientated in-plane, so that cross-plane heat transport across the device, through the reinforcement phase, is reduced. It is also preferable that the diameter of the reinforcement is less than the thickness of the thermoelectric material, so as to avoid a direct heat path between the hot side and the cold side, along the reinforcement.
- the porous substrate may comprise an aerogel.
- the aerogel may comprise a silica aerogel.
- aerogels are highly porous solids derived from highly crossed linked wet gels. Aerogels are formed by nanometre sized particles randomly interconnected into an open cell network typically with a large degree of mesoporosity (> 80%, approximately) and high surface area (> 50m 2 /g, approximately).
- xerogel Another porous structure that can be used is a xerogel.
- Xerogels are similar to aerogels. According to one definition, xerogels are distinguished from aerogels by their processing method. Aerogels commonly require supercritical drying whereas xerogels are not produced using supercritical drying. Xerogels are normally denser than aerogels, i.e. their solid fraction is higher.
- the porous substrate may comprise an L 3 phase material.
- One suitable material may be a silicate L 3 material.
- the porous substrate may comprise a high internal phase emulsion polymer.
- the porous substrate may comprise three dimensional pore structures.
- three dimensional pore structures we mean pore structures that have pores oriented in three dimensions. Possible advantages of such structures are increased accessibility, and multiple orientations of structures put down on the porous film. Such structures may include layers of nanometer-thickness, or other nanometer-sized features that have orientation, e.g. rods, plates or wires.
- Yet another embodiment of the invention involves using a porous substrate or coating with controlled ranges of pore sizes, sometimes called 'hierarchical' structures.
- An example of such a pore structure might be micrometer-sized channels that lead into channels of around lOOnm, which further lead to pores of around IOnm, which might have roughness of the order of 2nm. Such structures can combine high surface areas with good fluid access.
- Yet another embodiment of the invention involves using a porous substrate or coating that is comprised of a skeleton or framework, where the coating is applied externally to the skeleton or framework.
- the surface of the coating increases with coating thickness. Examples of such skeletons or frameworks are shown in Figure 2.
- Yet another embodiment of the invention involves using a porous substrate or coating that is comprised of a solid with holes through it, where the coating is applied internally to the holes.
- the surface of the coating decreases with coating thickness. Examples of such skeletons or frameworks are shown in Figure 3.
- Yet another embodiment of the invention involves using a porous substrate or coating that is comprised of a solid structure which enables both internal and external coating, such as a network of tubes. Examples of such structures are shown in Figure 4.
- Yet another embodiment of the invention involves using a porous substrate or coating that is comprised of a solid structure which is essentially comprised of continuous surfaces or membranes (Figure 5).
- these substrates include L 3 phase and high internal phase emulsion polymers.
- Yet another embodiment of the present invention involves using a porous substrate that may be subsequently removed following coating, so that the final material contains much less of the original porous substrate material.
- a porous substrate that may be subsequently removed following coating
- An example of this is a carbon aerogel which may be removed by subsequent combustion.
- porous substrates that could be removed by combustion include polymeric products such as papers, filter papers, membranes or the like. Cellulose-based forms of these are specific examples. Other substrates could be used which could alternatively be removed by combustion, dissolution, evaporation etc.
- Yet another embodiment of the present invention involves using a porous substrate that has significant roughness at a nanometer scale.
- the substrate being coated is essentially smooth.
- Porous substrates such as aerogels and xerogels may be thought of as being comprised of 'strings' of nanoparticles. Their surfaces are therefore much rougher, on a nanometer scale, than flat substrates or smooth porous structures such as PAA.
- Yet another embodiment of the present invention involves using a porous substrate that is essentially free of pores that provide a direct 'line of sight' from one electrode to the other, and particularly essentially free of pores that provide a direct 'line of sight' from one electrode to the other whilst being orientated close to perpendicularly to the electrodes.
- 'Line of sight' pores can provide a path for heat transfer via infra-red radiation and also heat transfer via convection.
- Tortuous pores can reduce infra-red heat transfer by providing infra-red absorbing solid between electrodes and can minimize convection.
- Yet another embodiment of the present invention involves nano-layer structures that can utilize both cross-plane and in-plane effects.
- Cross-plane effects that are being targeted in the field include reduction of thermal conductivity, energy filtering effects and thermionic effects.
- Energy filtering and thermionic effects arise from using layers that provide potential barriers to carrier movement.
- the barriers are characterized by a height and a width.
- Figures 6(a) and (b) show a highly magnified view of the surface of a nanolayered material of the present invention. At the top of the filament of porous substrate, the nanolayers wrap around. To make a device, a contact is placed on top.
- carriers electrosprays
- carriers electrosprays
- the surface has been removed by, for example, plasma etching. This enables direct contact to the layers, and therefore allows a device with much reduced or no cross-plane effects.
- the material that is coated onto the porous substrate may contain nano-sized features that lead to quantum confinement effects such as increased Seebeck coefficients. Such effects are known to become significant when the size of the confinement approaches, or is less than, the Bohr exciton radius of the material.
- the nano-sized features may lead to decreased thermal conductivity, which may be due to increased phonon scattering at interfaces, or energy filtering, or other phonon blocking mechanisms associated with nano-scale features.
- the material that is coated onto the porous substrate may be of nanometer thickness, i.e. the coating thickness may be measured in nanometers.
- the coating may have a thickness of from lnm to lOOnm, more suitably 1 nm to 50nm, even more suitably from lnm to 20nm, even more suitably from lnm to IOnm.
- the most suitable ranges of thickness of the coated material may be modified according to the exciton Bohr radius of the material, eg. the coating may have a thickness that is three times the exciton Bohr radius, or two times the exciton Bohr radius, or equal to the exciton Bohr radius, or less than the exciton Bohr radius.
- the optimal thickness to provide the optimal combination of Seebeck coefficient, thermal resistivity and electrical resistivity is expected to be dependent upon the material used in the coating.
- quantum confinement may be achieved within the single layer, i.e. the dimension of the quantum confinement is the thickness of the layer.
- phonon-blocking effects may be achieved through the nano-metre scale thickness of the layer. These effects may be enhanced by providing a tortuous path.
- the material that is coated onto the porous substrate may also comprise a plurality of layers of material.
- the plurality of layers may comprise a plurality of layers having a thickness in the nanometre range.
- the plurality of layers may comprise a plurality of layers of different materials.
- the plurality of layers may comprise alternating layers of different material.
- One or more of the materials should be a thermoelectric material.
- the thermoelectric material may comprise a semiconductor material.
- quantum confinement may be achieved within a layer, i.e. the dimension of the quantum confinement may be the layer thickness. This may be in addition to any quantum effects from the total coating thickness.
- phonon-blocking effects may be achieved through the nano-metre features of the layers, either solely or in addition to the nano-scale thickness of the layer. These effects may be enhanced by providing a tortuous path.
- the plurality of layers may comprise alternating layers of Si and SiGe, alternating layers of B-C of different compositions, such as B 4 C and BgC or even BnC, or alternating layers of Si and SiC.
- Other thermoelectric materials such as lead telluride or bismuth telluride thermoelectric materials coated onto a porous substrate, at least one of which is a thermoelectric material.
- the layers may also be comprised of more than two different materials. They may also be comprised of layers with different crystal structures. Other examples include layers of silicon carbide and boron carbide, where the boron carbide may have a range of compositions.
- the layers may be thermally stable.
- the plurality of layers may comprise alternating layers of doped zinc oxide material and other materials.
- alternating layers of Al-doped zinc oxide and Al 2 O 3 or alternating layers of Al-doped zinc oxide and Zn x Mg y O z , where the Zn x Mg y O z may be doped or undoped.
- Both single layer and multi-layer coatings may incorporate quantum dots.
- quantum confinement may occur in the dimension of the quantum dot. It may also occur in the dimensions of the coating thickness, and/or the nanolayer thickness.
- the material that is coated onto the porous substrate may be comprised of other nanometer-sized features such as quantum dots, rods, plates, wires, or combinations of these. Combinations of these with the alternating nanometer-thickness layers is also possible.
- the material that is coated onto the porous substrate may have a surface 'capping' layer that provides a specific function.
- a capping layer that quenches surface defects may provide increased electrical conductivity.
- Al 2 O 3 capping layers have been shown to decrease the effects of surface defects in zinc oxide-based semiconductors.
- the porous substrate may first be coated with a material that allows better nucleation of subsequent coated layers. It may also be coated with a 'diffusion barrier' material, prior to subsequent coating, to minimise diffusion of elements into and/or out of the porous substrate. Such diffusion may deteriorate the structure and hence performance.
- the porous substrate may also be first coated with a material or materials, including nanolayered materials, that act as thermal barriers. This coating may also perform any combination of nucleation, thermal barrier and diffusion barrier.
- the material may be coated onto the porous substrate using any technique known to be suitable to the person skilled in the art.
- the porous substrate may be coated with the thermoelectric material using atomic layer deposition (ALD).
- ALD atomic layer deposition
- precursors are added to a chamber at low pressure and form a monolayer on the surface. This monolayer acts as a barrier to further precursor deposition.
- the precursors are purged, then a reactant gas is added that reacts with the precursor monolayer to form a product that is able to accept another monolayer of precursor.
- areas that are more exposed to precursor gases receive exactly the same monolayer coating as areas that take longer to be exposed to precursors.
- films deposited by ALD may be 'pinhole-free' at much thinner thicknesses compared to other methods.
- ALD thereby offers control of layer deposition at an unparalleled fine scale.
- the coatings produced by ALD are commonly 'conformal', i.e. they conform to the shape of the substrate.
- Plasma- enhanced ALD is a variation of ALD that may also be used.
- Other coating techniques may be suitable, such as chemical vapour deposition, physical vapour deposition, electron evaporation, sputtering and variations of these.
- the present invention provides a method for making a thermoelectric element comprising providing a porous substrate and applying a coating of a thermoelectric material to the porous substrate.
- the coating of thermoelectric material is supplied such that the porous structure of the substrate is not completely filled by the thermoelectric material. Therefore, the thermoelectric element formed by this embodiment of the method retains a degree of porosity in its final structure.
- the method comprises forming a plurality of layers of thermoelectric material on the porous substrate.
- the layers of thermoelectric material may comprise layers of different material.
- the layers of different material may comprise alternating layers of different material.
- thermoelectric material may be deposited on the substrate using any technique known to be suitable to a person skilled in the art.
- a suitable technique comprises atomic layer deposition.
- Another embodiment of the present invention involves a coated porous substrate, in which significant porosity remains after coating, and which exhibits low thermal transport despite there being a relatively low amount of thermoelectric material being present.
- the volume fraction of porous substrate is low, so that the ratio of active thermoelectric material to porous substrate is increased. This is particularly important as the amount of thermoelectric material decreases.
- This embodiment is particularly relevant to commercial production of high performance thermoelectric materials at low cost. It has been found that higher performance thermoelectric materials such as some nanostructured thermoelectric materials are capable of carrying very high power densities, e.g. higher than lOOW/cm 2 . This is a much higher power density than can be practically delivered to the device with heat transfer restrictions.
- thermoelectric material when using thinner devices, most applications require reduction of heat flow, which may be achieved by decreasing the area fraction of the thermoelectric material.
- thermoelectric material required to produce a given output by using a much lower volume fraction of thermoelectric material in the thermoelement.
- the heat flux in may be relatively low, but the 'active heat flux' through the thermoelectric materials is much higher due to its low volume fraction. For example, if 10W/cm 2 heat is delivered to a thermoelement, and the thermoelement comprises only 10% thermoelectric material, the active heat flux may be ⁇ 100W/cm 2 .
- thermoelectric material Coated nanoporous substrates provide a solution to this problem as structures such as aerogels, while very low in solid fraction, are amongst the most thermally insulating materials known to man.
- a porous structure may be coated with an amount of thermoelectric material that leads to only a low total volume fraction of thermoelectric material, and still be very thermally insulating. In this case it is even more advantageous to have a low volume fraction of initial porous substrate, since the amount of thermoelectric material is smaller and thus the ratio of thermoelectric material to inert substrate is potentially higher.
- Coated porous materials may be designed to inhibit thermal transfer via convection and infra-red radiation.
- Convection may be inhibited by utilising porous structures that have relatively small pores and tortuous paths.
- Infra-red radiation may be reduced by ensuring that there is no clear path from one side of the device to the other, in other words the infra-red radiation must pass through significant coating material before it gets to the other side.
- Use of thermoelectric materials that are good absorbers of infra-red radiation, such as doped ZnO, is useful in this respect.
- Use of contact metals that are low infra-red emitters, for example silver and aluminium, may also help.
- thermoelectric materials have never previously been used to form thermoelectric materials. It is known that the properties of materials can vary significantly with deposition method. Indeed, atomic layer deposition can form materials that are quite different from materials with similar compositions deposited by other methods. Atomic layer deposition can form materials having larger amounts of amorphous material than other deposition techniques. Atomic layer deposition also can result in the formation of crystalline materials of differing structures or composition. Atomic layer deposition can deposit thin coatings with very small nanocrystals (i.e. nano-sized grains). Small grain sizes can be deleterious to thermoelectric properties.
- thermoelectric materials have only been used for very thin layers, typically less than tens of nanometers, which is much thinner than the thicknesses of typical thermoelectric materials in current devices (of the order of mm). Therefore, heretofore, atomic layer deposition has not been considered to be a suitable candidate for forming thermoelectric materials.
- Atomic layer deposition into porous structures can also be problematical due to problems with penetration of gaseous precursors. This can lead to impractically long cycle times, or non-uniform coatings.
- a preferred method for coating via ALD is flow-through mode, where gaseous species are forced through the porous material. This can greatly reduce coating times and waste of precursor gas.
- the present invention provides a method for making a thermoelectric element by depositing one or more materials onto a substrate wherein at least one of the materials is a thermoelectric material, characterised in that the one more materials are deposited by atomic layer deposition.
- atomic layer deposition may be used to deposit alternating layers of material, with at least one of the layers comprising a thermoelectric material.
- atomic layer deposition is used to deposit a first layer of thermoelectric material, and then deposit a second layer of thermoelectric material. A plurality of alternating layers of first thermoelectric material and second thermoelectric material may be deposited. Quantum dots may also be formed using atomic layer deposition. These dots could be contained within alternating nanolayers.
- the substrate which is to be subjected to coating using atomic layer deposition comprises a porous material having small pores or tortuous pore paths through the substrate.
- ALD has encountered difficulties in coating such pore structures that can be considered as 'high aspect ratio' pore structures. Such structures can lead to excessively long processing times and/or non-uniform coatings, due to the large barrier to the diffusion of gaseous reactants or reactant species in and out of the substrate.
- the present inventors have surprisingly found that thermoelectric materials can be made using the combination of ALD with the specified substrates, and particularly when the substrates have practical thicknesses (> ⁇ 50 ⁇ m).
- nanostructures deposited by ALD such as nanolaminates
- ALD atomic layer deposition
- thermoelectric materials It is an object of this invention to provide a useful method for producing thermoelectric materials. It is another object to provide a useful method for producing thermoelectric materials with nano-scale dimensions and/or nano-scale features. It is another object to provide a useful method for producing thermoelectric materials with nano-scale dimensions and/or nano-scale features, whereby the thermoelectric material is of a practically useful thickness. It is another object to provide a useful method for producing thermoelectric materials with nano-scale dimensions and/or nano-scale features, whereby the nano-scale features and/or dimensions are very tightly controlled.
- thermoelectric materials comprised of a coated framework, whereby the coating is of nano-scale thickness. It is a further object that the nano-scale thickness is tightly controlled.
- thermoelectric materials comprised of a coated framework, whereby the coating contains nano-scale features. It is a further object that the dimensions of the nano-scale features are tightly controlled.
- thermoelectric materials comprised of a coated framework, whereby the coating contains nano-scale features or is of nano-scale thickness, where the dimensions of the nano-scale features and/or nano-scale thickness may or may not be tightly controlled, where the total thickness of the thermoelectric material structure is of practical thickness.
- thermoelectric materials comprised of a coated framework, whereby the coating is an external coating on the framework.
- thermoelectric materials are deposited as a coating onto a scaffold material, where the scaffold material has a low volume fraction and may be left in the device.
- thermoelectric material that may have a reduced volume fraction of thermoelectric material, whilst still providing good thermal insulation between the hot side and the cold side of the device.
- Figure 3 Example of porous solids that may be coated internally.
- Figure 4. Examples of structures that may be coated both internally and externally Figure
- Figure 6 Schematic diagram showing contacts to nanolayered materials.
- the contact is put directly over the nanolayered materials and carriers must go across planes before they can travel along the planes.
- a layer of material has been removed by, e.g., plasma etching. The contact is now directly onto the planes, and cross-plane effects are reduced.
- Figure 7 Scanning electron micrograph of cross-section (fracture surface) of the material from example 1.
- Figure 8 Scanning electron micrograph of cross-section (fracture surface) of the material from example 2.
- Figure 9 Transmission electron micrograph showing the coating from example 2. The nanolayers can be seen in this micrograph.
- Figure 10 Dark-field transmission electron micrograph of the coating from example 2.
- the bright dots are nano-sized grains.
- the coating appears thicker than in Figure 9 because in this micrograph the coating is inclined at an angle to the beam.
- Figure 1 Scanning electron micrograph of cross-section (fracture surface) of the material from example 6.
- Figure 12. EDS data showing Al (k) and Zn (k) integrated peak intensities across the full cross section of the film from example. 6.
- Figure 13. Scanning electron micrograph of cross-section (fracture surface) of the material from example 7.
- Figure 15 Scanning electron micrograph of cross-section (fracture surface) of the material from example 9. Examples
- Cellulose acetate filter membrane material thickness ⁇ 130 ⁇ m
- a nucleating coating of Al 2 O 3 was first put down on the material.
- the target coating thickness was ⁇ 12 nm. From subsequent weight measurements, the volume fraction of coating was estimated to be ⁇ 6%.
- Figure 7 shows a scanning electron micrograph of a cross-section (fracture surface) of the coated material. From transmission electron microscopy the thickness of the coating was estimated to be very close to the target thickness.
- the cellulose acetate material from example 1 was coated with alternating nano-layers of
- FIG. 8 shows a scanning electron micrograph of a cross-section (fracture surface) of the coated material.
- Figure 9 shows a transmission electron micrograph of the coating, indicating a coating thickness of ⁇ 12nm. The nanolayers can also be seen.
- the thickness of the Al-doped ZnO layers is estimated to be ⁇ 3nm and the thickness of the Al 2 O 3 layer is less than lnm.
- Figure 10 shows a dark field transmission electron micrograph of the coating showing nano-sized grains (bright). The apparent thickness of the coating in this micrograph is thicker than 12nm because the coating is inclined to the beam.
- Cellulose acetate material from example 1 was coated with 2% Al-doped ZnO using flow-through ALD, with a target coating thickness of ⁇ 40nm.
- a nucleating coating of Al 2 O 3 was first put down on the material. From subsequent weight measurements, the volume fraction of coating was estimated to be 17.1%. Contacts were put on the specimen, one side was heated, and the voltage difference between hot and cold side measured to observe thermoelectric behavior. The results are listed in Table 1.
- Example 4 The cellulose acetate material from example 1 was coated with alternating nano-layers of 2% Al-doped ZnO, and Al 2 O 3 using flow-through ALD.
- the target coating thickness was ⁇ 40nm.
- the final surface layer was Al 2 O 3 .
- the volume fraction of coating was estimated to be 17.9%. Contacts were put on the specimen, one side was heated, and the voltage difference between hot and cold side measured to observe thermoelectric behavior. The results are listed in Table 2. Comparing the results in Table 2 with Table 1, the nanolayer material clearly has a much higher Seebeck coefficient (WK) than the material with a homogenous coating.
- WK Seebeck coefficient
- Cellulose acetate material from example 1 was coated with 2% Al-doped ZnO using flow-through ALD, with a target coating thickness of ⁇ 20nm.
- a nucleating coating of Al 2 O 3 was first put down on the material. From subsequent weight measurements, the volume fraction of coating was estimated to be 9.4%. Contacts were put on the specimen, one side was heated, and the voltage difference between hot and cold side measured to observe thermoelectric behavior. The results are listed in Table 4.
- FIG. 11 shows a scanning electron micrograph of a cross-section (fracture surface) of the coated material.
- Energy dispersive spectroscopy (EDS) measurements indicated that the Zn and Al concentrations were similar through the thickness of the film ( Figure 12), indicating successful deposition.
- EDS Energy dispersive spectroscopy
- Example 7 The cellulose nitrate material from example 5 was coated with alternating nano-layers of 1% Al-doped ZnO, and Al 2 O 3 using flow-through ALD. The total thickness of the coating was targeted to be 12nm. The final surface layer was Al 2 O 3 . From subsequent weight measurements, the volume fraction of coating was estimated to be ⁇ 6%.
- Figure 13 shows a scanning electron micrograph of a cross-section (fracture surface) of the coated material. Energy dispersive spectroscopy (EDS) measurements indicated that the Zn:Al ratio was similar through the thickness of the film ( Figure 14), indicating successful deposition. In Figure 14 it is thought the composition fluctuations mainly result from morphology changes on the fracture surface. Poor penetration of precursors during ALD coating would lead to a constant decrease of the related element and this is not observed.
- EDS Energy dispersive spectroscopy
- Cellulose nitrate filter membrane material from example 5 was coated with 2% Al-doped ZnO using flow-through ALD.
- the target coating thickness was 40nm. From subsequent weight measurements, the volume fraction of coating was estimated to be 19.1 %.
- Example 9
- the cellulose nitrate material from example 5 was coated with alternating nano-layers of 2% Al-doped ZnO, and Al 2 O 3 using flow-through ALD.
- the target coating thickness was 40nm.
- the final surface layer was Al 2 O 3 . From subsequent weight measurements, the volume fraction of coating was estimated to be 20%. Contacts were put on the specimen, one side was heated, and the voltage difference between hot and cold side measured to observe thermoelectric behavior. The results are listed in Table 5. Similarly to the results in Example 4, this nanolayer sample shows high Seebeck coefficients.
- Cellulose filter membrane material thickness ⁇ 85 ⁇ m, was coated with 1% Al-doped ZnO using flow-through ALD. From subsequent weight measurements, the volume fraction of coating was estimated to be ⁇ 6%. The thickness of the coating was targeted to be ⁇ 12nm.
- Figure 15 shows a scanning electron micrograph of a cross-section (fracture surface) of the coated material.
- the cellulose material from example 10 was coated with alternating nano-layers of 1% Al-doped ZnO, and Al 2 O 3 .
- the final surface layer was Al 2 O 3 . From subsequent weight measurements, the volume fraction of coating was estimated to be ⁇ 6%. The total thickness of the coating was targeted to be ⁇ 12nm.
- Example 12 A free standing silica aerogel film was created, wherein the volume fraction of solid in the aerogel was ⁇ 2%. The thickness of the film was ⁇ 250 ⁇ m. The aerogel was reinforced with fiberglass, where the volume fraction of fiberglass reinforcement was ⁇ 4%. The fibre diameter was ⁇ 13 ⁇ m.
- This film was coated with 2% Al-doped ZnO. Subsequent mass measurements indicated the volume fraction of coating was ⁇ 5%.
- the silica aerogel film of example 12 was coated with alternating nano-layers of 2% Al- doped ZnO, and Al 2 O 3 .
- the final surface layer was Al 2 O 3 .
- the surface of the material was plasma-etched to a depth of - l ⁇ m. From subsequent weight measurements, the volume fraction of coating was estimated to be ⁇ 6%. Contacts were put on the specimen, one side was heated, and the voltage difference between hot and cold side measured to observe thermoelectric behavior. The results are listed in Table 6.
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US12/993,567 US20110139207A1 (en) | 2008-05-21 | 2009-05-21 | Thermoelectric Element |
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EP2297795A4 (en) | 2013-07-31 |
US20110139207A1 (en) | 2011-06-16 |
EP2297795A1 (en) | 2011-03-23 |
AU2009250336A1 (en) | 2009-11-26 |
JP2011521459A (en) | 2011-07-21 |
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