AEROSOL JET PRINTING AND SINTERING OF THERMOELECTRIC DEVICES

Abstract

Methods, ink compositions, and 3D conformal printed flexible films. The method may include aerosol jet printing a thermoelectric ink composition, followed by photonic or other sintering of the ink to remove surfactant included therein, and to convert the thermoelectric nanoparticles of the ink composition into a dense structure capable of charge carrier transport. The ink compositions may be solution-processed semimetal-chalcogenides (e.g., Te containing materials) in a suitable carrier (e.g., polyol(s), alcohol(s), etc.). A surfactant (e.g., PVP) may be present in the ink. Within seconds of photonic sintering, the electrical conductivity of the printed film is dramatically increased from non-conductive to a value on the order of at least 1×10.sup.4 S/m. The films may demonstrate a room-temperature power factor of at least 500 μWm.sup.−1K.sup.−2. The realized values of 730-2200 μWm.sup.−1K.sup.−2 achieved are among the highest values reported for flexible thermoelectric films. The film is durable (e.g., 500 bending cycles with no significant performance drop).

Claims

1. A conformal thermoelectric film comprising: a matrix of thermoelectric nanoparticles configured as a flexible conformal thermoelectric film; wherein the thermoelectric film has an electrical conductivity of at least 1×10.sup.4 S/m, and/or a power factor of at least 500 μWm.sup.−1K.sup.−2.

2. A thermoelectric film as recited in claim 1, wherein the thermoelectric film has an electrical conductivity of at least 1×10.sup.4 S/m, and/or a power factor of at least 700 μWm.sup.−1K.sup.−2.

3. A thermoelectric film as recited in claim 1, wherein the matrix is a photonically sintered matrix.

4. A thermoelectric film as recited in claim 1, wherein the film is an n-type thermoelectric material.

5. A thermoelectric film as recited in claim 1, wherein the film is a p-type thermoelectric material.

6. A thermoelectric film as recited in claim 1, wherein the thermoelectric nanoparticles comprise a chalcogenide.

7. A thermoelectric film as recited in claim 6, wherein the chalcogenide comprises Te.

8. A thermoelectric film as recited in claim 1, wherein the thermoelectric nanoparticles comprise a thermoelectric material comprising Bi, Te, and Se, or a thermoelectric material comprising Sb and Te.

9. A thermoelectric film as recited in claim 1, wherein the thermoelectric nanoparticles comprise at least one of Bi.sub.2Te.sub.2.7Se.sub.0.3 or Sb.sub.2Te.sub.3.

10. A thermoelectric film as recited in claim 1, wherein the thermoelectric nanoparticles comprise an Sb.sub.2Te.sub.3—Te composite including Sb.sub.2Te.sub.3 nanoplates and Te nanorods.

11. A thermoelectric film as recited in claim 1, wherein the film is 3D printed.

12. A thermoelectric film as recited in claim 1, wherein the film has a thickness or printed feature size of from 10 μm to 1000 μm.

13. A thermoelectric film as recited in claim 1, wherein the flexible, conformal film is provided on a substrate.

14. A thermoelectric film as recited in claim 13, wherein the substrate is a 2D flexible substrate, a 3D curved substrate, or a substrate which is dynamic in shape.

15. A thermoelectric film as recited in claim 13, wherein the substrate is a heat-sensitive substrate.

16. A thermoelectric film as recited in claim 15, wherein the heat-sensitive substrate comprises at least one of paper, elastic, a synthetic fabric or a natural fabric.

17. A thermoelectric film as recited in claim 16, wherein the synthetic fabric or natural fabric comprises one or more of polyester, nylon, cotton, wool, or silk.

18. A thermoelectric film as recited in claim 1, wherein the flexible, conformal film exhibits no significant delamination or cracking, and negligible change in electrical resistance and/or power factor at a minimum bending radius of from 1 mm to 10 mm.

19. A thermoelectric film as recited in claim 18, wherein the flexible, conformal film exhibits no significant delamination or cracking, and negligible change in electrical resistance and/or power factor after 500 bending cycles at a bending radius of from 1 mm to 10 mm.

20. An aerosol jet printable ink composition comprising: a carrier including at least one polyol and a lower alcohol having 1-4 carbon atoms; thermoelectric nanoparticles dispersed in the carrier; and a surfactant for preventing or minimizing agglomeration of the nanoparticles.

21. An ink composition as recited in claim 20, wherein the thermoelectric nanoparticles comprise a chalcogenide.

22. An ink composition as recited in claim 21, wherein the chalcogenide comprises Te.

23. An ink composition as recited in claim 20, wherein the thermoelectric nanoparticles comprise a thermoelectric material comprising Bi, Te, and Se, or a thermoelectric material comprising Sb and Te.

24. An ink composition as recited in claim 20, wherein the thermoelectric nanoparticles comprise at least one of Bi.sub.2Te.sub.2.7Se.sub.0.3 or Sb.sub.2Te.sub.3.

25. An ink composition as recited in claim 20, wherein the thermoelectric nanoparticles comprise an Sb.sub.2Te.sub.3—Te composite including Sb.sub.2Te.sub.3 nanoplates and Te nanorods.

26. An ink composition as recited in claim 20, wherein the carrier comprises two different polyols, the first polyol and second polyol being present at a weight ratio of from 2:1 to 10:1.

27. An ink composition as recited in claim 20, wherein the carrier comprises ethylene glycol, glycerol, and ethanol.

28. An ink composition as recited in claim 20, wherein the at least one polyol comprises from 20-60% by weight of the carrier, and the alcohol comprises from 40-80% by weight of the carrier.

29. An ink composition as recited in claim 20, wherein the thermoelectric nanoparticles comprise nanoplates.

30. An ink composition as recited in claim 20, wherein the carrier comprises at least 60%, at least 65%, at least 70%, at least 80%, or from 80-90% by weight of the ink composition.

31. An ink composition as recited in claim 20, wherein the nanoparticles comprise up to 40%, up to 35%, up to 30%, up to 25%, up to 20%, or from 10-20% by weight of the ink composition.

32. An ink composition as recited in claim 20, wherein the surfactant comprises polyvinylpyrrolidone.

33. An ink composition as recited in claim 20, wherein the ink composition is shelf-stable for at least 3 months, or at least 6 months.

34. A method for producing a thermoelectric device, the method comprising: providing an aerosol jet printable ink composition including thermoelectric nanoparticles and a surfactant in a carrier; printing the aerosol jet printable ink composition onto a substrate to provide a desired pattern thereon; and sintering the printed aerosol jet printable ink composition to remove the surfactant and convert the thermoelectric nanoparticles into a dense structure capable of charge carrier transport.

35. A method as recited in claim 34, wherein sintering of the printed aerosol jet printable ink composition comprises photonic sintering.

36. A method as recited in claim 34, wherein sintering of the printed aerosol jet printable ink composition comprises thermal sintering.

37. A method as recited in claim 34, wherein the thermoelectric nanoparticles comprise a chalcogenide.

38. A method as recited in claim 37, wherein the chalcogenide comprises Te.

39. A method as recited in claim 34, wherein the thermoelectric nanoparticles comprise a thermoelectric material comprising Bi, Te, and Se, or a thermoelectric material comprising Sb and Te.

40. A method as recited in claim 34, wherein the thermoelectric nanoparticles comprise at least one of Bi.sub.2Te.sub.2.7Se.sub.0.3 or Sb.sub.2Te.sub.3.

41. A method as recited in claim 34, wherein the thermoelectric nanoparticles comprise an Sb.sub.2Te.sub.3—Te composite including Sb.sub.2Te.sub.3 nanoplates and Te nanorods.

42. A method as recited in claim 34, wherein the carrier comprises one or more polyols and a lower alcohol having 1-4 carbon atoms.

43. A method as recited in claim 34, wherein the carrier comprises ethylene glycol, glycerol, and ethanol.

44. A method as recited in claim 42, wherein the one or more polyols comprise from 20-60% by weight of the carrier, and the lower alcohol comprises from 40-80% by weight of the carrier.

45. A method as recited in claim 34, wherein the sintering is photonic sintering, and is performed using intense pulsed light (IPL).

46. A method as recited in claim 34, wherein the sintering is photonic sintering and is completed within less than 30 minutes, less than 20 minutes, less than 10 minutes, less than 5 minutes, less than 1 minute, less than 30 seconds, less than 10 seconds, or less than 5 seconds.

47. A method as recited in claim 34, wherein the sintering is photonic sintering and is performed using intense pulsed light (IPL) with a pulse duration from 1 ms to 10 ms, from 1.5 ms to 5 ms, or from 1.5 ms to 3 ms.

48. A method as recited in claim 34, wherein the sintering is photonic sintering and is performed using intense pulsed light (IPL) with a power density from 1 kW/cm.sup.2 to 10 kW/cm.sup.2, from 2 kW/cm.sup.2 to 8 kW/cm.sup.2 or from 3 kW/cm.sup.2 to 6 kW/cm.sup.2.

49. A method as recited in claim 34, wherein the sintering is photonic sintering and is performed using intense pulsed light (IPL) with a pulse delay from 100 to 3000 ms, from 200 to 2000 ms, or from 300 to 1000 ms between adjacent photonic pulses.

50. A method as recited in claim 34, wherein the sintering is photonic sintering and is performed using intense pulsed light (IPL) within no more than 10 s, no more than 8 s, no more than 5 s, no more than 3 s, or no more than 2 s.

51. A method as recited in claim 34, wherein the process is carried out at ambient temperature so that any heating of the substrate is minimal.

52. A method as recited in claim 34, wherein the substrate has a melting temperature of less than 400° C.

53. A method as recited in claim 34, wherein the substrate includes a curved surface to which the ink composition is applied.

54. A method as recited in claim 34, wherein the substrate is at least one of cellulose-based, polymer-based, glass, or other ceramic.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0029] To further clarify the above and other advantages and features of the present invention, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the drawings located in the specification. It is appreciated that these drawings depict only typical embodiments of the invention and are therefore not to be considered limiting of its scope. The invention will be described and explained with additional specificity and detail through the use of the accompanying drawings.

[0030] FIG. 1A shows a TEM image of Bi.sub.2Te.sub.2.7Se.sub.0.3 nanoplates.

[0031] FIG. 1B shows an HRTEM image of the Bi.sub.2Te.sub.2.7Se.sub.0.3 nanoplates of FIG. 1A.

[0032] FIG. 1C shows a schematic illustration of an exemplary aerosol jet 3D printer conformal deposition head.

[0033] FIG. 1D shows an SEM image of the printed film before sintering, with the scale bar being 500 nm.

[0034] FIG. 1E shows an SEM image of the printed film of FIG. 1D, after sintering, with the scale bar being 500 nm.

[0035] FIG. 1F shows an exemplary 3D conformally printed thermoelectric structure, including thermoelectric material printed on a substrate (e.g., polymer, such as polyimide), with adjacent thermoelectric stripes connected to one another by Ag ink printed legs.

[0036] FIG. 2A shows an XRD characterization of as-fabricated Bi.sub.2Te.sub.2.7Se.sub.0.3 nanoparticles based on a reflux-synthesis method.

[0037] FIG. 2B shows SEM images of the as-fabricated Bi.sub.2Te.sub.2.7Se.sub.0.3 nanoparticles from FIG. 2A.

[0038] FIG. 3 shows SEM and energy dispersive X-ray (EDX) mapping images of the printed Bi.sub.2Te.sub.2.7Se.sub.0.3 film after photonic sintering, showing substantially uniform distribution of Bi, Te and Se with reserved elemental ratio during the sintering process.

[0039] FIGS. 4A-4D show SEM images of the photonic sintered Bi.sub.2Te.sub.2.7Se.sub.0.3 films after one pass (FIGS. 4A-4B) and two passes (FIGS. 4C and 4D).

[0040] FIGS. 5A-5C show electrical conductivity (σ) of the sintered samples (on Kapton polyimide) by single pulse under power densities of 3.46, 4.23 and 5.1 kW/cm.sup.2, respectively, for pulse duration times from 0.5 to 3 ms.

[0041] FIGS. 6A-6B show electrical conductivity σ (FIG. 6A), Seebeck coefficient S (FIG. 6A), and power factor PF (FIG. 6B) as a function of number of pulses under a power density of 5.1 kW/cm.sup.2, at a pulse duration of 1.5 ms and at two different pulse delay times (between pulses) of 1000 ms and 362 ms.

[0042] FIGS. 7A-7F show SEM images of an unsintered sample (FIG. 7A), as well as after sintering with from 1 to 10 pulses (FIGS. 7B-7F), at a power density of 5.1 kW/cm.sup.2, with a 1.5 ms pulse duration, and 362 ms delay between pulses. The scale bar is 1 μm.

[0043] FIG. 7G schematically illustrates evolution of the microstructure upon pulse sintering.

[0044] FIGS. 8A-8F show electrical conductivity σ, Seebeck coefficient S, and power factor PF vs. number of pulses of the samples sintered for three sets of power densities and pulse durations (FIGS. 8A-8B: 3.46 kW/cm.sup.2 and 3 ms); (FIGS. 8C-8D: 4.23 kW/cm.sup.2 and 2.5 ms); and (FIGS. 8E-8F: 5.1 kW/cm.sup.2 and 1.5 ms). The delay time between two adjacent pulses was 1000 ms.

[0045] FIG. 9 shows EDS mapping of unsintered film (top row) and photonic sintered films sintered at 5.1 kW/cm.sup.2 power density with 1.5 ms pulse duration and 362 ms delay between pulses, with 2 pulses (2nd row), 5 pulses (3rd row), and 8 pulses (4th row).

[0046] FIG. 10 shows XRD patterns of the same unsintered and sintered Bi.sub.2Te.sub.2.7Se.sub.0.3 samples as FIG. 9, which also correspond to FIGS. 7A-7F. No impurities were found to be introduced during the sintering process under the resolution of XRD. The main peaks become sharper, evidencing the growth of nanoparticles.

[0047] FIGS. 11A-11B show changes to electrical resistance of the photonic sintered Bi.sub.2Te.sub.2.7Se.sub.0.3 thin films on polyimide as a function of number of bending cycles (FIG. 11A), and as a function of bending radius (FIG. 11B).

[0048] FIGS. 12A-12D show performance of a flexible TE device fabricated using aerosol jet printed Bi.sub.2Te.sub.2.7Se.sub.0.3 films, with FIG. 12A showing open circuit voltage vs. temperature difference (ΔT); FIG. 12B showing device operating voltage vs. current, shown for various ΔT values; FIG. 12C showing power output vs. electrical current, shown for various ΔT values; and FIG. 12D showing electrical power density versus ΔT.

[0049] FIG. 13A shows a SEM image of Sb.sub.2Te.sub.3 nanoplates.

[0050] FIG. 13B shows an HRTEM image of the Sb.sub.2Te.sub.3 nanoplates of FIG. 13A.

[0051] FIG. 13C shows an SEM image of a Sb.sub.2Te.sub.3 film on a polyimide substrate, after sintering at 400° C. for 1 hour.

[0052] FIG. 13D shows an example of the complex, intricate printed traces that can be prepared, using the present processes, with microscale resolution.

[0053] FIG. 14 shows Powder X-ray diffraction (XRD) characterization of pure Sb.sub.2Te.sub.3 product before sintering, as well as standard XRD patterns for Sb.sub.2Te.sub.3 and Te, for comparison. The peaks corresponding to the rhombohedral Sb.sub.2Te.sub.3 phase as labeled by the Miller indexes. No noticeable appearance of Te phase was observed.

[0054] FIG. 15 shows atomic force microscopy (AFM) characterization of a pure 2D Sb.sub.2Te.sub.3 nanoplate. The average thickness of the plate is determined to be about 10 nm.

[0055] FIGS. 16A-16B show temperature dependent in-plane TE properties (FIG. 16A shows electrical conductivity and Seebeck coefficient, and FIG. 16B shows power factor) of flexible Sb.sub.2Te.sub.3 films printed on polyimide after sintering at 400° C. A high-power factor over a wide temperature range (350-550 K) was achieved. The inset in FIG. 16B shows the excellent flexibility of the film under repeated bending tests, with R.sub.0 being the original resistance of the film and r being the bending radius.

[0056] FIGS. 17A-17D show SEM images and Energy-dispersive X-ray spectroscopy (EDS) characterization of Sb.sub.2Te.sub.3 films (FIGS. 17A-17B) and Sb.sub.2Te.sub.3—Te composite films (FIGS. 17C-17D). The Te-rich composite film has about 8 wt % Te more than the standard stoichiometric ratio of pure Sb.sub.2Te.sub.3.

[0057] FIG. 18 shows Powder X-ray diffraction (XRD) characterization of Sb.sub.2Te.sub.3—Te product before sintering, showing the appearance of trigonal Te phase. The standard XRD patterns for Sb.sub.2Te.sub.3 and Te are also given for comparison.

[0058] FIGS. 19A-19B show temperature dependent in-plane TE properties, including electrical conductivity and Seebeck coefficient (FIG. 19A) and power factor (FIG. 19B) of the flexible Sb.sub.2Te.sub.3—Te composite film printed on polyimide after sintering at 400° C.

[0059] FIGS. 19C-19D show a TEM image (FIG. 19C) and a HRTEM image (FIG. 19D) of the interface between Te and Sb.sub.2Te.sub.3 from a cross-plane viewpoint of the printed film. The marked dashed circles mark the existence of additional Te nanorods. Local EDS and element line-scan analysis is given in FIGS. 21B-21C and Table 7.

[0060] FIGS. 20A-20C show a comparison of TE performance between Sb.sub.2Te.sub.3 and 8 wt % Te-rich Sb.sub.2Te.sub.3—Te films, showing particularly electrical conductivity (FIG. 20A), Seebeck coefficient (FIG. 20B) and power factor (FIG. 20C).

[0061] FIGS. 21A-21C show an SEM image (FIG. 21A) and local EDS analysis (FIGS. 21B-21C and Table 7) on Sb.sub.2Te.sub.3—Te films at different positions corresponding to those marked in FIG. 21A.

[0062] FIGS. 22A-22D show transport properties from Boltzmann transport calculations and carrier pocket visualization for bulk Sb.sub.2Te.sub.3. FIG. 22A shows Seebeck coefficient as a function of carrier concentration at 300, 400 and 500 K. FIG. 22B shows Seebeck coefficient as a function of temperature for two fixed doping levels. FIG. 22C shows electronic fitness function (EFF). FIG. 22D shows a carrier pocket visualization, showing isosurfaces 0.1 eV below the valence band maximum. In FIG. 22D, transport data shown are direction averages.

[0063] FIGS. 23A-23D show performance of a flexible TE device fabricated by 3D conformal aerosol jet printing using Sb.sub.2Te.sub.3 strips connected with Ag legs. FIG. 23A shows experimental open circuit voltage (Voc) vs. temperature differences (ΔT). FIG. 23B shows operating device voltage vs. current at various ΔT values. FIG. 23C shows power output vs. electrical current at various ΔT values. FIG. 23D shows experimental power density at various ΔT values.

[0064] FIG. 24 shows band structure of Sb.sub.2Te.sub.3 showing a single parabolic band (SPB) model.

[0065] FIG. 25 schematically shows the experimental setup used for measuring Seebeck coefficient and electrical conductivity of the fabricated thin films.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

I. Definitions

[0066] Before describing the present invention in detail, it is to be understood that this invention is not limited to particularly exemplified systems or process parameters that may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments of the invention only and is not intended to limit the scope of the invention in any manner.

[0067] All publications, patents and patent applications cited herein, whether supra or infra, are hereby incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference.

[0068] The term “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, unrecited elements or method steps.

[0069] The term “consisting essentially of” limits the scope of a claim to the specified materials or steps “and those that do not materially affect the basic and novel characteristic(s)” of the claimed invention.

[0070] The term “consisting of” as used herein, excludes any element, step, or ingredient not specified in the claim.

[0071] It must be noted that, as used in this specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the content clearly dictates otherwise.

[0072] Numbers, percentages, ratios, or other values stated herein may include that value, and also other values that are about or approximately the stated value, as would be appreciated by one of ordinary skill in the art. As such, all values herein are understood to be modified by the term “about”. A stated value should therefore be interpreted broadly enough to encompass values that are at least close enough to the stated value to perform a desired function or achieve a desired result, and/or values that round to the stated value. The stated values include at least the variation to be expected in a typical manufacturing process, and may include values that are within 10%, within 5%, within 1%, etc. of a stated value. Furthermore, where used, the terms “substantially”, “similarly”, “about” or “approximately” represent an amount or state close to the stated amount or state that still performs a desired function or achieves a desired result. For example, the term “substantially” “about” or “approximately” may refer to an amount that s within 10% of, within 5% of, or within 1% of, a stated amount or value.

[0073] Some ranges may be disclosed herein. Additional ranges may be defined between any values disclosed herein as being exemplary of a particular parameter. All such ranges are contemplated and within the scope of the present disclosure.

[0074] Unless otherwise stated, all percentages described herein are by weight.

[0075] In some embodiments, the films and compositions described herein may be free or substantially free from any specific components not mentioned within this specification. By ‘substantially free of’ it is meant that the composition or article preferably comprises 0% of the stated component, although it will be appreciated that very small concentrations may possibly be present, e.g., through incidental formation, contamination, or even by intentional addition. Such components may be present, if at all, in amounts of less than 1%, less than 0.5%, less than 0.25%, less than 0.1%, less than 0.05%, less than 0.01%, less than 0.005%, less than 0.001%, or less than 0.0001%.

[0076] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although a number of methods and materials similar or equivalent to those described herein can be used in the practice of the present invention, the preferred materials and methods are described herein.

II. Introduction

[0077] The present invention is directed to 3D conformal printed flexible films, as well as methods and ink compositions useful for preparing such. The method may include aerosol jet printing a thermoelectric ink composition, followed by photonic or other sintering of the ink composition to drive off carrier or solvent included therein, and to remove any included surfactant. Such sintering converts the thermoelectric nanoparticles of the ink composition into a dense structure capable of charge carrier transport. The ink compositions may be solution-processed chalcogenides (e.g., Te containing materials, such as Bi.sub.xTe.sub.ySe.sub.z (Bi.sub.2Te.sub.2.7Se.sub.0.3), Sb.sub.2Te.sub.3, or a Sb.sub.2Te.sub.3—Te composite) suspended or otherwise provided in a suitable carrier or solvent (e.g., polyol(s), alcohol(s), etc.). As already noted, the term “carrier” is used for simplicity, and it will be appreciated that for some systems, the carrier could actually be a solvent, such that “carrier” is to be construed broadly. A surfactant (e.g., a polymer surfactant such as PVP) may also be present in the ink. Non-limiting examples of other possible surfactants include cetrimonium bromide (CTAB) and ethylenediaminetetraacetic acid (EDTA) salts, e.g., ETDA disodium salt, as well as combinations of more than one surfactant. The chalcogenide(s) present may be in the form of nanoparticles (e.g., nanoplates, nanorods, or the like), e.g., which may be dispersed, suspended, or otherwise provided within the ink composition. The present ink compositions are stable, allowing storage of the composition, which can be used anytime within a period of months (e.g., up to 3 months, or up to 6 months) after formulation, for printing using such methods as described herein.

[0078] Once sintered, (which occurs within a matter of seconds in the case of photonic sintering), the electrical conductivity of the printed film is dramatically increased from non-conductive (for the ink composition) to a value on the order of at least 1×10.sup.4 S/m (e.g., in the range of 1×10.sup.4 S/m to 1×10.sup.6 S/m, or 1×10.sup.4 S/m to 1×10.sup.5 S/m, characteristic of semiconductors). Films printed and sintered as described herein exhibit room-temperature power factors of at least 100, 200, 300, 400, or at least 500 μWm.sup.−1K.sup.−2. The realized values of 730 to 2200 μWm.sup.−1K.sup.−2 achieved in the Examples herein are among the highest values reported for flexible thermoelectric films. The films show negligible performance changes (e.g., less than 3%, less than 2%, less than 1%, or less than 0.5% increase in electrical resistance) after 500 bending cycles (e.g., at a bending radius of 10 mm, 7 mm, or the like). Even upon such repeated bending about a tight 1.5 mm radius, electrical resistance only increased ˜10%. The highly scalable and low-cost fabrication process paves the way for large-scale manufacturing of flexible devices using a variety of high-performing semiconductor nanoparticle inks.

III. Exemplary Methods, Compositions, and Devices

[0079] Solution-printable and shape-conformable thermoelectric (TE) devices have attracted considerable attentions due to their broad applications in cooling and energy harvesting for powering flexible electronics and sensors. Compared with early strategies like vacuum filtration and spin/spray coating that have been used in attempts to fabricate flexible TE films, ink based printing methods have not been widely explored, and have the potential to directly transform TE particles into a completed device pattern without the need for other complex fabrication processes. However, it has been a major challenge to achieve outstanding TE properties and mechanical flexibility in printed films due to the typically reduced density of printed films and the restricted sintering temperature when printing on flexible substrates with low melting points. Sintering is an important step in colloidal nanoparticle-based printing in order to remove any surfactant that may be present and to transform the nanoparticles into a dense structure capable of charge carrier transport. However, most of the better performing TE materials reported within the field require high sintering temperatures above 400° C. for several hours, severely limiting substrate choices.

[0080] According to at least some embodiments of the present invention, sintering is accomplished using photonic sintering, which does not significantly raise the temperature of the substrate, greatly expanding the choice of materials that can be used for the substrate. Another alternative sintering method disclosed herein uses thermal sintering. In at least some thermal sintering embodiments, the sintering temperature may still be no more than 400° C., which shows excellent results as detailed in the Examples below, with various substrate materials (e.g., a polyimide polymer).

[0081] In contrast to thermal sintering methods, rapid and versatile photonic sintering using intense pulsed light (IPL) offers great advantages as it can sinter the printed films at elevated temperatures without overheating or damaging the underlying substrate by confining energy delivery to the printed films (e.g., minimizing heating in the substrate). IPL may refer to use of light for sintering, where the light provides a power density of at least 500 kW/cm.sup.2, or at least 1 kW/cm.sup.2. In an embodiment, IPL may exclude collimated laser light. According to an embodiment, the present disclosure provides flexible TE films fabricated using an innovative and versatile 3D conformal aerosol jet printing method, which can directly print TE devices with microscale spatial resolution with sub-micron thickness control on both 2D planar and 3D curved or other shaped substrates using colloidal nanoparticle ink compositions with a wide range of viscosities. Such membranes can be directly 3D printed onto any of a wide variety of surfaces. Furthermore, since they can be 3D printed (e.g., additive printing, in additive layers, if desired), they can be printed as any desired pattern, the options of which are unlimited. The ability to fabricate films on flexible and low temperature substrates is a key advantage. In addition, the ability to directly print the devices onto virtually any 3D conformal surface and integrate the TE device with the end use system or product is advantageous, providing greatly increased manufacturing flexibility as compared to existing methods. Thus, while at least some of the examples described herein may be directed to printing onto a given film for purposes of illustrating the capability, the present printing methods can directly convert the nanoparticles into complete thermoelectric devices with any desired sophisticated design pattern, which advantages are not provided by existing alternatives. A greater range of viscosity in the ink composition is tolerated when aerosol jet printing (e.g., 1 to 1000 cps), as compared to ink jet printing, where viscosity characteristics must be carefully controlled (e.g., 5 to 15 cps).

[0082] Combined with photonic sintering or thermal sintering, the present disclosure achieves flexible films and devices fabricated from solution-processed chalcogenides (e.g., Te-chalcogenide based nanoparticles) on a variety of substrates. The sintering dramatically improves the electrical conductivity of the printed films from non-conductive (of the ink as printed) to values from 1×10.sup.4 S/m to 1×10.sup.6 S/m (e.g., 2.7×10.sup.4 S/m in an example) within seconds, which lead to a very high power factor, e.g., of at least 500 μWm.sup.−1K.sup.−2, such as 500 to 3000 μWm.sup.−1K.sup.−2 (e.g., 730 μWm.sup.−1K.sup.−2, 1500 μWm.sup.−1K.sup.−2, or 2200 μWm.sup.−1K.sup.−2 in various examples) at room temperature. The 3D conformal aerosol jet printing and photonic sintering or thermal sintering opens the opportunity to directly integrate high-efficiency nanoparticles into a broad range of complex systems where TE devices could be useful for cooling and energy harvesting applications.

[0083] To demonstrate the aerosol jet printing and photonic sintering, n-type Bi.sub.2Te.sub.2.7Se.sub.0.3 nanoplates were synthesized using a bottom-up wet-chemical method and converted into printable ink. X-ray diffraction (XRD) measurement was conducted, as can be seen in FIGS. 2A-2B, with all XRD spectra indexed with rhombohedral symmetry with space group R3m. Here, no detectable peaks of any impurities were observed. The as-fabricated Bi.sub.2Te.sub.2.7Se.sub.0.3 nanocrystals were also investigated by high-resolution transmission electron microscopy (HRTEM), as shown in FIGS. 1A-1B, indicating high crystalline quality.

[0084] Scanning electron microscopy (SEM) shown in FIG. 2A demonstrates the uniform size distribution of the nanoplates. The as-fabricated Bi.sub.2Te.sub.2.7Se.sub.0.3 nanoplates were dispersed in a mixed carrier (or solvent) of ethylene glycol, glycerol and ethanol with ratios specifically selected to produce a printable ink with desired viscosity (e.g., 1 to 1000, such as 5 to 500, or 5 to 15 cps). Additional details are provided in the examples section. Using the colloidal nanocrystal ink, TE films with virtually any desired pattern can be fabricated by the present aerosol jet printing methods onto any of various suitable substrates, such as a 2D flexible substrate (e.g., paper, polymer such as polyimide, or other) or a 3D curved or other shaped substrate (e.g., a glass tube), whether flexible or rigid. FIG. 1C schematically illustrates an exemplary aerosol jet printing method, which is more versatile than an ink jet method, allowing use of a wider range of viscosity ink compositions, as well as other benefits.

[0085] The thickness of the printed film can be precisely controlled by regulating the ink mass flowrate and number of printing passes. For example, in an embodiment, any desired thickness in a range from 10 to 1000 μm can easily be achieved. Finally, either photonic sintering or thermal sintering can be employed to achieve the densification and grain growth of the aerosol-printed nanoparticles. Photonic sintering in particular provides an ultrafast pathway to improve the carrier mobility and thermoelectric performance.

[0086] To systematically investigate the processing-structure-property correlations of intense pulsed light (IPL) sintering, different values for the pulsed light power density, pulse duration and number of pulses were tested, and the resulting microstructures and TE properties were evaluated. For photonic sintering with a single pulse, the IPL power density was adjusted in order to achieve suitable electrical conductivity σ. In the present examples, all samples were printed with one pass on Kapton (a polyimide). Initially, unsintered Bi.sub.2Te.sub.2.7Se.sub.0.3 printed films have high (e.g., infinite) resistivity as a result of the non-conductive surfactant (e.g., polyvinylpyrrolidone (“PVP”)) included in the ink composition. The print process parameters were as shown below, in Table 1. Of course, various other values may also be suitable for use (e.g., ±50% from those shown).

TABLE-US-00001 TABLE 1 Parameter Value Nozzle Diameter (μm) 150 PA Atomizer Flow (sccm) 550 Exhaust Flow (sccm) 500 Sheath Gas Flow (sccm)  12 Platen Temperature (° C.) 70-75  Process Speed (mm/s)  5-5.5

[0087] Upon photonic sintering (5 pulses, as shown in FIG. 7D), the insulating PVP is at least partially removed (e.g., typically substantially fully removed), as verified by CHN analysis, shown below in Table 2. The result after sintering is a 3D network composed of Bi.sub.2Te.sub.2.7 Se.sub.0.3 nanoplates.

TABLE-US-00002 TABLE 2 Carbon Nitrogen Sample (wt %) (wt %) Unsintered Bi.sub.2Te.sub.2.7Se.sub.0.3 2.7  0.07 Sintered Bi.sub.2Te.sub.2.7Se.sub.0.3 0.38 0.03

[0088] After sintering, the electrical conductivity of all samples is increased by orders of magnitude. As can be seen in FIGS. 5A-5C, the electrical conductivity σ increases with increasing pulse duration until it reaches a maximum value and then decreases with further exposure. The maximum σ was achieved in the tested samples with pulse durations of 3, 2.5 and 1.5 milliseconds (ms) under power densities of 3.46, 4.23 and 5.1 kW/cm.sup.2 respectively. For a power density of 3.46 kW/cm.sup.2, the further increased σ may be achieved with longer pulse duration, as this was the maximum selectable value for the photonic sintering machine used in the particularly performed testing.

[0089] In order to further improve the TE properties, the number of pulses can be adjusted. For example, three sets of varied pulse duration values and power density values as identified above for single pulse sintering were tested. The electrical conductivity σ, Seebeck coefficient S, and power factor PF, where PF=σ.Math.S.sup.2, with different number of pulses were measured, as shown in FIGS. 8A-8F. Here, 1000 ms delay time was imposed between adjacent pulses. In general, a significant increase in σ is observed with multiple pulses, as compared to single pulse sintering. The σ peaks at an ideal number of pulses before it drops drastically. The Seebeck coefficient S is relatively insensitive to pulse number, indicating the composition and charge carrier concentration of the films remain relatively unchanged during the sintering process. Therefore, the power factor (PF) follows a similar trend as the σ, showing a maximum value at an optimum number of pulses that yields the maximum σ. It is notable that the electrical conductivity and power factor reach 2×10.sup.4 S/m and 630 μWm.sup.−1K.sup.−2 within a few seconds of photonic sintering, as shown in FIGS. 2A-2B.

[0090] The performance of the present n-type Bi.sub.2Te.sub.2.7Se.sub.0.3 films can be further improved by further adjusting the pulse delay time during the multiple pulse sintering process. The pulse delay time was reduced from 1000 ms to 362 ms, which was the shortest pulse delay time allowed by the particular sintering machine employed in the tests. As shown in FIG. 2A, the maximum electrical conductivity of 2.7×10.sup.4 S/m was achieved with this reduced pulse delay time, representing a 35% enhancement over the electrical conductivity of films sintered with a 1000 ms pulse delay time. Despite a slight decrease in Seebeck coefficient, the final PF shows a 16% enhancement with the total sintering time reduced from 4 seconds to less than 1.5 seconds. In short, the maximum PF of aerosol jet printed n-type Bi.sub.2Te.sub.2.7Se.sub.0.3 films under photonic sintering conditions as described reaches 730 μWm.sup.−1K.sup.−2 at room temperature, which is among the highest demonstrated values for flexible n-type TE materials. Table 3 summarizes the comparison of TE performance of various flexible n-type TE materials, demonstrating the promise of aerosol jet printing followed by sintering, for providing high performance, low cost flexible TE devices, e.g., whether such printing is combined with photonic sintering, or thermal sintering. Examples using thermal sintering are described in greater detail hereafter.

TABLE-US-00003 TABLE 3 PF Sintering Material (μWm.sup.−1K.sup.−2) Time (s) Method The Present Bi.sub.2Te.sub.2.7Se.sub.0.3 730 <1.5 Aerosol Jet Printing Bi.sub.2Te.sub.2.8Se.sub.0.2 560 2700 Screen Printing Bi.sub.2Te.sub.3 + Epoxy 280 43200 Dispenser Printing Cu.sub.0.01Bi.sub.2Se.sub.2.8 + PDVF 103 18000 Drop Coating Bi.sub.2Te.sub.3 163 7200 Ink Jet Printing C.sub.60/TiS.sub.2 400 3600 Vacuum Filtering TiS.sub.2/(hexyl- 450 >3600 Electrochemical ammonium).sub.x(H.sub.2O)y(DMSO).sub.z Intercalation WS.sub.2 5-7 3600 Vacuum Filtration Carbon Nanotube 150 N.A. Drop Casting

[0091] The physical mechanism of intense pulsed light sintering was further studied from viewpoints of microstructure and charge carrier properties. As can be seen in FIG. 7A, the printed Bi.sub.2Te.sub.2.7Se.sub.0.3 films prior to sintering show a network of nanoplates isolated by the insulating PVP surfactant at the particle interfaces, which explains the observed infinite resistivity of the unsintered films. A single pulse is sufficient to remove most of the surfactant, but results in a porous microstructure, which limits the carrier mobility, as shown in FIG. 7B. With continued energy input (FIG. 7C-7D) the grain size grows and porosity decreases as the particles coalesce, forming a well-connected interface, resulting in increased electrical conductivity and PF, as shown in FIG. 7D (showing an example sintered with five pulses). With more than five pulses, the film becomes increasingly porous, e.g., believed to be due to excess energy overheating the film and causing sublimation of the nanoparticle constituents, which is detrimental to charge carrier transport (see FIGS. 7E-7F). FIG. 7G schematically illustrates this evolution of the microstructure of the nanoplate films during photonic pulse sintering.

[0092] Hall effect measurements were carried out to provide insight into the charge carrier transport behavior of the films sintered by IPL. As shown in Table 4, the carrier mobility μ increases dramatically from 8.2 to 25 cm.sup.2 V.sup.−1 s.sup.−1 (at 5 pulses) and then drops by almost 50%, at 8 pulses. Here, the increasing mobility can be ascribed to the increased film density and larger grains with decreased grain boundary and pore boundary scattering, as demonstrated in FIGS. 7A-7F. The carrier concentration n is relatively insensitive to the number of pulses, indicating that the films preserve substantially the same composition as the starting nanocrystals, which is confirmed in the corresponding EDS mapping images shown in FIG. 9. The corresponding XRD patterns in FIG. 10 show no noticeable changes of the crystalline structure of the Bi.sub.2Te.sub.2.7Se.sub.0.3 films during the sintering process. Although illustrated particularly with Bi.sub.2Te.sub.2.7Se.sub.0.3, it will be appreciated that various other suitable nanoparticle TE materials could alternatively be employed (e.g., other chalcogenide containing materials that can provide the desired electrical conductivity once sintered).

[0093] Table 4 below shows Room-temperature thermoelectric and carrier transport properties of photonic sintered films prepared under a power density of 5.1 kW/cm.sup.2, 1.5 ms pulse duration and 362 ms pulse delay time with different pulse numbers. Reported characteristics include the Seebeck coefficient (S), electrical conductivity (σ), carrier mobility (μ), carrier concentration (n), and power factor (PF). The energy J is the total amount of energy incident upon the printed film surface during the sintering process.

TABLE-US-00004 TABLE 4 Pulses Energy (J) S (μV/K) σ (10.sup.3 S/m) μ (cm.sup.2V.sup.−1s.sup.−1) n (10.sup.19cm.sup.−3) PF (μWm.sup.−1K.sup.−2) 1 2.3 −144.8 1.15 8.2 3 24.1 2 4.6 −166.0 8.87 12.7 3.4 244.5 5 11.5 −163.4 27.2 24.9 3.1 730.2 8 18.4 −165.8 16.9 12.6 2.7 465.1

[0094] Bending tests were performed to evaluate the mechanical flexibility and robustness of the printed TE films in thermal energy harvesting applications on curved surfaces, particularly flexible surfaces that may undergo repeated bending (e.g., clothing, fabrics, flexible sensors, etc.). As shown in FIG. 11A, the printed films show a slight increase in electrical resistance of about 4% after 500 bending cycles. Bending tests based on different radii were also performed, with an increase of about 10% in electrical resistance at a tight bending radius of 1.5 mm (FIG. 11B).

[0095] Finally, a flexible TE generator with aerosol jet printed Bi.sub.2Te.sub.2.7Se.sub.0.3 films was tested to demonstrate the potential of the present systems for energy harvesting. FIG. 12A shows that the measured device open circuit voltage increases linearly with temperature difference (ΔT) by virtue of the Seebeck effect, achieving a maximum output voltage of 25 mV at ΔT of 50 K. FIGS. 12B-12C show the device operating voltage and power output as a function of electrical current tested at different ΔT values, respectively. A maximum power output of 141 nW was obtained with a ΔT of 50 K when the external load resistance matches the internal resistance of the device. The device power density increases with ΔT and reaches 2.7 mW/cm.sup.2 at a ΔT of 50K, as shown in FIG. 12D. The power density was evaluated based on the total cross-sectional area of the four TE elements perpendicular to the heat flow direction. It should be noted that only 4 printed TE film elements were used in the fabricated inplane device, and the device power output can be increased by increasing the number of TE elements (e.g., any desired number of elements could be provided, whether in series or parallel).

[0096] The present disclosure presents the first demonstration of aerosol jet printing of nanoparticle thermoelectric inks coupled with ultrafast photonic sintering to create flexible, high-performance and low-cost thermoelectric films. Using intense pulsed light sintering, the electrical conductivity of non-conductive n-type Bi.sub.2Te.sub.2.7Se.sub.0.3 film is improved to 2.7×10.sup.4 S/m within a few seconds. Achieving a power factor of 730 μWm.sup.−1 K.sup.−2 at room temperature within 1.5 seconds of initiating sintering is unprecedented, allowing highly scalable roll-to-roll printing of TE devices on a wide variety of low-temperature substrates, as well as directly printing TE devices onto 3D curved surfaces, whether flexible or not. The 3D conformal aerosol jet printing combined with ultrafast photonic sintering opens up exciting opportunities to transform semiconducting nanocrystals into functional and flexible devices for broad industrial and personal applications.

[0097] In addition to the various embodiments described above, the present invention is also directed to other solution-processable semiconducting TE materials. For example, 2D nanoplates and 1D nanorods are attractive building blocks for diverse technologies, including thermoelectrics, optoelectronics, and electronics. However, as noted above, transforming solution-processable colloidal nanoparticles into high-performance and flexible devices remains a challenge. As already noted, flexible films prepared by solution processed semiconducting nanocrystals are typically plagued by poor thermoelectric and electrical transport properties. The present disclosure also provides a highly scalable 3D conformal additive printing approach to directly convert solution-processed 2D nanoplates and 1D nanorods into high-performing flexible devices. The flexible films printed using Sb.sub.2Te.sub.3 nanoplates as described herein demonstrated an exceptional thermoelectric power factor of 1.5 mW/m.Math.K.sup.2 over a wide temperature range (e.g., 350-550 K). By synergistically combining Sb.sub.2Te.sub.3 2D nanoplates with Te 1D nanorods, the power factor of the flexible film reached an unprecedented maximum value of 2.2 mW/m.Math.K.sup.2 at 500 K, which is significantly higher than the best reported values for p-type flexible thermoelectric films. A fully printed flexible generator device exhibited a competitive electrical power density of 7.65 mW/cm.sup.2 with a reasonably small temperature differential of 60 K. The versatile printing method for directly transforming nanoscale building blocks into functional devices paves the way for developing not only flexible energy harvesters but also a broad range of flexible/wearable electronics and sensors.

[0098] Flexible thermoelectric generators (f-TEGs) based on materials such as Sb.sub.2Te.sub.3 and Bi.sub.2Te.sub.3, carbon nanotube, graphene, conductive polymer and hybrids, have the ability to interconvert thermal to electrical energy without moving parts. These f-TEGs can be integrated with portable/wearable electronics and sensors and enable self-powered devices. In this context, V.sub.2—VI.sub.3 metal chalcogenides (e.g., Bi.sub.2Te.sub.3, Sb.sub.2Te.sub.3 and related alloys and compounds) have attracted particular attention because of their high figure of merit (ZT) near room temperature. For example, p-type Bi.sub.2Te.sub.3—Sb.sub.2Te.sub.3 alloys show high performance near room temperature and benefit considerably from nano-structuring.

[0099] Similar to Bi.sub.2Te.sub.3, Sb.sub.2Te.sub.3 is also a topological insulator, which leads to a complex, nonparabolic band structure, often highly favorable for thermoelectric performance. It has an extremely high dielectric constant of ε.sub.0˜100, favorable for high mobility even with a large concentration of defects. Thus, Sb.sub.2Te.sub.3 is potentially an important TE material, the key challenge being to find methods to control its carrier concentration and to effectively nanostructure the material while maintaining this control. Up to now, most of the reported Sb.sub.2Te.sub.3 related materials are p-type semiconductors, which is determined by its intrinsic defects including Sb vacancies and anti-site defects of Sb atoms on the Te sites (Sb.sub.Te). Typically, Sb.sub.2Te.sub.3 bulk single crystals stand out for their unique advantages including a high electrical conductivity (σ) of about 3×10.sup.5 S/m to 5×10.sup.5 S/m, and a reasonable thermal conductivity (κ) around 1˜6 W/m.Math.K. However, Sb.sub.2Te.sub.3 also has a less competitive Seebeck coefficient (S), of about 83-105 μV/K arising from its high degenerate hole concentration (n>10.sup.20 cm.sup.−3) created by the acceptor state mentioned above, especially Sb.sub.Te.

[0100] Nanostructuring has been employed to enhance S, and to reduce κ as a result of the increased phonon scattering effect. For example, Sb.sub.2Te.sub.3 with 2D nanoplate morphology presents a 30% increase in S (S=125 μV/K) near room temperature. S and ZT enhancement in nanostructured Sb.sub.2Te.sub.3 by anti-site defect suppression through sulfur doping was also achieved in nanobulk thermoelectrics. Bi—Te and Sb—Te solid solutions (e.g. Bi.sub.0.5Sb.sub.1.5Te.sub.3) also increase S (S>170 μV/K at 450 K) and suppress κ. Unfortunately, the reduced band gap limits the ability of the Bi—Sb—Te system to retain high ZT above 450 K. Despite the high ZT (e.g., >1) observed in the Bi—Sb—Te system, the ZT normally peaks at narrow temperature range near or below 100° C. It has been a challenge to develop materials with consistently high ZT across a broad temperature plateau. Meanwhile, there is also an absence of high ZT materials in the middle temperature range (200-300° C., i.e., 473-573 K) where the majority of available waste heat resides.

[0101] Although TE nanostructures with enhanced ZT have been extensively studied, a big gap exists in translating these nanostructures into high-performance and flexible TE devices. The majority of reported TE devices were fabricated by exploiting the above-mentioned inorganic nanostructures into bulk configurations. However, rigid bulk devices not only consume large amounts of TE materials but also present challenges in applications on curved, and particularly flexible surfaces such as the human body, other flexible surfaces, or even exhaust pipes. According to the present disclosure, a highly scalable 3D conformal aerosol jet printing method is provided to fabricate flexible TE generators using metal-chalcogenide nanostructures as building blocks. The spatial resolution of the aerosol jet printing may be about 20 μm in the lateral dimension and several hundred nanometers in film thickness. Printed flexible Sb.sub.2Te.sub.3 films demonstrated herein can have exceptional average power factor (PF), for example, of 1.5 mW/m.Math.K.sup.2 across a wide temperature plateau (e.g., from 350-550 K). The PF can be further increased to 2.2 mW/m.Math.K.sup.2 at 500 K by including excess Te (e.g., Te nanorods) with the Sb.sub.2Te.sub.3 nanoplates, e.g., as a composite material of the two. A fully printed flexible TE generator exhibited a power density of 7.65 mW/cm.sup.2 under a temperature gradient of 60 K, demonstrating great potential to power wearable electronics and sensors.

[0102] Sb.sub.2Te.sub.3 nanoplates were fabricated using a simple energy-saving hydrothermal method (See details in the examples section). FIG. 13A-13B show the SEM and HRTEM images of the 2D Sb.sub.2Te.sub.3 nanoplates with high crystallization. The lattice spacing of 0.209 nm corresponds to the lattice planes (110) in Sb.sub.2Te.sub.3. FIG. 14 presents the powder X-ray diffraction (XRD) pattern of the as-fabricated Sb.sub.2Te.sub.3 plates, together with the major diffraction peaks which correspond to rhombohedral Sb.sub.2Te.sub.3 phase (R3m, JCPDS No. 15-0874). No noticeable appearance of a separate Te phase was observed. The average thickness of the plate was determined as 10 nm by atomic force microscopy (AFM) analysis, with lateral size of the plates being from about 1 to 1.5 μm (FIG. 15). This highly anisotropic growth is believed to be due to the inherent crystal structure of the material. The as-fabricated Sb.sub.2Te.sub.3 nanoplates were cleaned with hydrazine hydrate and redispersed in a mixture of ethylene glycol (EG), glycerol and ethanol having a ratio of 35:5:60 by weight. The remaining PVP surfactant helps prevent the nanoplates from prematurely aggregating, and the surfactant can be removed in the sintering process which follows application of the ink composition to the substrate.

[0103] The same conformal aerosol jet printing process described in conjunction with FIG. 1C can be used to apply ink compositions including Sb.sub.2Te.sub.3 nanoplates. Similar to Table 1, Table 5 below shows exemplary parameters that can be used to print such an ink (e.g., Sb.sub.2Te.sub.3, Sb.sub.2Te.sub.3—Te, or other semiconductor chalcogenide nanoparticle ink compositions). Of course, various other values may also be suitable for use (e.g., ±50% from those shown).

TABLE-US-00005 TABLE 5 Parameter Value Sb.sub.2Te.sub.3 or other TE nanoparticles (wt %)  20 Nozzle Diameter (μm) 150 Line Spacing (μm)  15 PA Atomizer flow (sccm) 550 Exhaust Flow (sccm) 500 Sheath Gas Flow (sccm)  12 Platen Temperature (° C.)  70 Process Speed (mm/s)  5

[0104] The synthesized ink composition with 20% inorganic TE particles exhibits high stability, e.g., printable for at least 3 months after synthesis. Using the nanocrystal or nanoparticle ink, TE films with virtually any desired pattern can be produced using the present methods, whether applied onto flat or curved surfaces, and whether such surfaces are rigid or flexible. The film thickness can be adjusted by adjusting the ink composition, the mass flow rate, and number of printing passes. For example, a dense and continuous Sb.sub.2Te.sub.3 thin film (thickness of about 1.5 μm) can be printed on polyimide or other desired substrate material, with competitive internal resistance while maintaining excellent flexibility. FIG. 13C shows the corresponding SEM image after sintering of such an embodiment, revealing well connected Sb.sub.2Te.sub.3 networks that facilitate efficient charge carrier transport across neighboring nanoplates. Films with variously designed patterns were printed on various substrates, including intricately printed tracery patterns, application of thin-film patterns printed on a cylindrical tube, and others, demonstrating the high resolution and 3D conformal printing ability of the present approach.

[0105] Sintering (whether photonic, thermal, or otherwise) plays an important role in removing the surfactant and consolidating the relatively loose nanoparticle assembly into a densified continuous network. While photonic sintering is described above, in this example, thermal sintering, at a temperature of 400° C. was used in order to decompose and remove the PVP surfactant, as well as drive off any carrier or solvent present in the ink. Of course, temperatures varying from the 400° C. can also be used. It is advantageous that such sintering temperature be no more than 400° C., although it will be appreciated that higher temperatures can also be used, (e.g., up to 600° C., or up to 500° C.). That said, it is advantageous for sintering to be achieved at temperatures of 400° C. or less, as many substrate materials cannot be exposed to such elevated temperatures without damage.

[0106] In an embodiment, it may be advantageous for the sintering to occur at a temperature not more than 250° C., no more than 200° C., no more than 150° C., no more than 100° C., or not more than 50° C. higher than the environmental temperature in which the waste heat is to be harvested.

[0107] FIG. 16A shows the temperature dependent electrical conductivity σ and Seebeck coefficient S measured along the in-plane direction of the sintered film. The film shows degenerate semiconducting behavior of decreasing σ with temperature, which is typical for Sb.sub.2Te.sub.3 nanostructures after sintering. The σ is lower than that of the single-crystal bulk counterpart due to the electron scattering at the nano-grain boundaries. Nevertheless, the room-temperature σ reaches 7.8×10.sup.4 S/m, which is among the highest reported values for printed TE films. The carrier concentration (p) and mobility (μ) were determined by Hall measurement to be 1.06×10.sup.20 cm.sup.−3 and 48.5 cm.sup.2V.sup.−1 s.sup.−1, respectively. The high carrier concentration is in agreement with the Te-deficient defects as verified by energy-dispersive X-ray spectroscopy (EDS) analysis (FIG. 17A-17B and Table 6, below).

TABLE-US-00006 TABLE 6 Sample Element Weight % Atomic % Sb.sub.2Te.sub.3—Te Sb 34.9 36.0 Te 65.1 64.0 Sb.sub.2Te.sub.3 Sb 40.7 41.8 Te 59.3 58.2

[0108] The Seebeck coefficient S also shows degenerate semiconductor behavior, i.e., S increases with increasing temperature. The room-temperature S of 130 μV/K, is over 30% higher than that of the single-crystal bulk counterpart. The temperature dependent power factor (PF) is shown in FIG. 16B, demonstrating a competitive value around 1.37 mW/m.Math.K.sup.2 at room temperature. It is noteworthy that the PF shows an average value of 1.5 mW/m.Math.K.sup.2 over a wide temperature plateau (350-550 K), which is promising for harvesting waste heat which is abundant in this low-to-middle temperature range. The flexibility of the film was also studied using various bending tests under different radius curvatures. A slight increase of 0.6% in electrical resistance was observed after 1000 bending cycles at bend radius of 7 mm, demonstrating excellent flexibility for films printed using embodiments as disclosed herein.

[0109] A nanocomposite of mixed 2D Sb.sub.2Te.sub.3 plates and 1D Te nanorods was also prepared, having even further improved TE properties. When the atomic percent of Te precursor was over 60 at %, the excess Te was segregated from stoichiometric Sb.sub.2Te.sub.3 phase as a crystalline Te phase. XRD characterization of the nanocomposite is provided in FIG. 18. The formation mechanism of nanostructure Sb.sub.2Te.sub.3 is

TeO.sub.2+N.sub.2H.sub.4=Te+N.sub.2↑+2H.sub.2O  (1)

2Te+N.sub.2H.sub.4+4OH.sup.−=2Te.sup.2−+N.sub.2↑+4H.sub.2O  (2)

2Sb.sup.3++3Te.sup.2−═Sb.sub.2Te.sub.3  (3)

[0110] In other words, TeO.sub.2 is first reduced to Te.sup.2− ions with metal ions (Sb.sup.3+) remaining unchanged, after which Te.sup.2− and Sb.sup.3+ react to generate the telluride product. This means that 1D-Te nanostructures, which are an intermediary product, may act as a template during the early stage of fabrication. Sb.sub.2Te.sub.3 with 2D plate-like morphology are developed if 1D rod-like Te templates were destroyed in step (2) under alkaline conditions at proper temperature (e.g., about 155° C.). Otherwise, Te with 1D rod-like morphology is preserved where there is excess Te precursor. By appropriately controlling the amount of reducing agent (N.sub.2H.sub.4.H.sub.2O) and the precursors TeO.sub.2, pure 2D Sb.sub.2Te.sub.3 and Te-rich 2D/1D Sb.sub.2Te.sub.3—Te composites can be obtained.

[0111] In the case of the Sb.sub.2Te.sub.3—Te composite, several Te peaks were observed beyond the XRD pattern of Sb.sub.2Te.sub.3, as shown in FIG. 18. About 8 wt % excess tellurium was found in the form of tellurium nanorods based on EDS analysis and SEM characterization (FIG. 17C-17D and Table 6). Related temperature-dependent TE properties are presented in FIGS. 19A-19B. Similar to the pure Sb.sub.2Te.sub.3 films, σ also decreases with the increasing temperature after a slight increase below 350 K. The room-temperature S shows a 13.5% increase from 130 to 147 μV/K, and the room-temperature PF maintains almost the same value as the pure Sb.sub.2Te.sub.3 film despite a small decrease in σ with Te addition. The S of Sb.sub.2Te.sub.3—Te nanocomposite film keeps increasing to about 200 μV/K at 525 K (FIG. 19B), which is about 16.3% higher than that of the Sb.sub.2Te.sub.3 film (about 172 μV/K). Meanwhile, the σ of the Sb.sub.2Te.sub.3—Te film also surpasses that of the pure Sb.sub.2Te.sub.3 film when temperature exceeds 450 K. Comparison of the TE properties between Sb.sub.2Te.sub.3 and Sb.sub.2Te.sub.3—Te films is given in FIGS. 20A-20C. As a result, the PF of the Sb.sub.2Te.sub.3—Te film continues to increase substantially linearly and reaches a peak value of 2.2 mW/mK.sup.2 at around 500 K, 46.7% higher than that of the Sb.sub.2Te.sub.3 film. This composite-based film not only can serve as a power source for flexible electronics around room temperature (as can the pure Sb.sub.2Te.sub.3 film), but also fills a gap in the absence of high-performance and cost effective TE materials in the low-medium temperature range around 400-500 K.

[0112] TEM and high-resolution TEM images of printed Sb.sub.2Te.sub.3—Te films are provided in FIG. 19C-19D. The Te precipitates are easily identified from the Sb.sub.2Te.sub.3 matrix as a result of the lattice mismatch. The printed 1D/2D composite is composed of Sb.sub.2Te.sub.3 nanoplates and Te nanorods. The Te second phase appears as substantially circular dots on the cross-section of the focused ion beam (FIB) milled film. The local EDS analysis and element line-scan (Table 7 and FIGS. 21A-21C) confirms the Te-rich phase of >85 at % Te. Here, the larger nanorods are believed to be formed during the sintering process. The room temperature carrier concentration and mobility of the Sb.sub.2Te.sub.3—Te films were determined to be 4.95×10.sup.19 cm.sup.−3 and 79.3 cm.sup.2V.sup.−1 s.sup.−1, respectively.

TABLE-US-00007 TABLE 7 Position Element Weight % Atomic % I Sb 40.4 41.5 Te 59.6 58.5 II Sb 14.7 15.3 Te 85.3 84.7

[0113] FIG. 22A shows Seebeck coefficient S as obtained from Boltzmann transport calculations as a function of carrier concentration p. The value of p can be estimated by comparing experimental values with the obtained curves. FIG. 22B shows the calculated S(T) for two carrier concentrations, specifically 4.3×10.sup.19 cm.sup.−3 and 6.1×10.sup.19 cm.sup.−3. These values were chosen to be consistent with the ambient temperature experimental S. As can be seen, the curve for 4.3×10.sup.19 cm.sup.−3 is close to the experimental data of FIG. 19A for the Sb.sub.2Te.sub.3—Te system, while the higher doping level curve compares well with the Sb.sub.2Te.sub.3 data in FIG. 16A. Note that the p in these theoretical curves is the chemical carrier concentration, which may not necessarily be the same as the Hall values due to the nonparabolic band structure. The similar temperature dependence of the calculated curves and the experimental data supports the inference that reduced doping level in the nanostructured Sb.sub.2Te.sub.3—Te leads to enhancement in S. The calculated electronic fitness function (EFF), shown in FIG. 22C measures the decoupling of S and σ through band structure effects, and is closely related to the PF. The EFF shows both high values and an increase with reduction in carrier concentration in the range where S is consistent with the experimental values. The EFF indicates that the nanostructured Sb.sub.2Te.sub.3—Te is close to optimum doping at 500 K. It is also noteworthy that the calculated values of the EFF are quite high, reaching 1.3×10.sup.−19 W.sup.5/3 ms.sup.−1/3 K.sup.−2 at 500 K. A value of 1.2×10.sup.−19 W.sup.5/3 ms.sup.−1/3 K.sup.−2 is obtained at 300 K, albeit at lower carrier concentration. These values are comparable to some of the best reported TE materials. Table 8 below shows performance characteristics of various other p-type films, near room temperature. The high EFF may be attributable at least in part to the topological insulator behavior of Sb.sub.2Te.sub.3, which leads to a highly nonparabolic band structure. This can be seen in the carrier pocket visualization of FIG. 22D. Here, there are multiple, highly anisotropic carrier pockets, favorable for high TE performance, and very different from the single spherical section characteristic of the isotropic parabolic band model.

TABLE-US-00008 TABLE 8 Material σ (10.sup.4 S/m) S (μV/K) S.sup.2σ (mW/mK.sup.2) The Present Sb.sub.2Te.sub.3—Te 6.3 147 ~1.36 PEDOT/Bi.sub.2Te.sub.3 4.8 168 ~1.35 Ag—Sb.sub.2Te.sub.3 3.5 103 ~0.37 Bi.sub.0.5Sb.sub.1.5Te.sub.3 0.2 278 ~0.18 PANI/Te 1.2 93 ~0.10 CuI/PET 1.3 172 ~0.38 Doped CNT ~17 ~20 ~0.7 Ca.sub.3Co.sub.4O.sub.9 ~1.5 ~125 ~0.23

[0114] A flexible/wearable TE generator with aerosol jet printed Sb.sub.2Te.sub.3 films and Ag electrodes was fabricated to demonstrate the printed f-TEG for energy harvesting. The output voltage (FIG. 23B) and power (FIG. 23C) show great promise for the development of small-scale flexible/wearable TE generators, where the high PF of the printed TE films plays a significant role. FIG. 23A shows that the measured device open circuit voltage (Voc) increases linearly with temperature differential (ΔT) of 60 K with only 4 TE elements. FIGS. 23B-23C show the device operating voltage and power output as a function of electrical current tested at different ΔT values, respectively. A maximum power output of 1.15μW was obtained with a ΔT of 60 K, as shown in FIG. 23D. Here the power density was evaluated based on the total cross-sectional area of the four TE elements perpendicular to the heat flow direction. The high power density (e.g., at least 1 mW/cm.sup.2, at least 1.1 mW/cm.sup.2, or at least 1.2 mW/cm.sup.2, such as 1.1 mW/cm.sup.2 to 10 mW/cm.sup.2) indicates that a compactly sized printed f-TEG would be sufficient to power a range of typical devices and sensors, fueled by a waste heat temperature differential of for example, at least 10 K, such as from 20 K to 60 K.

[0115] Creating functional TE materials with acceptable mechanical compliance while retaining competitive TE properties is a long-standing challenge. In the present disclosure, high-performance and flexible thermoelectric films were produced by aerosol jet printing Sb.sub.2Te.sub.3 nanoplates on flexible substrates. The power factor of printed Sb.sub.2Te.sub.3 films reaches 1.37 mW/mK.sup.2 at around 300 K, with a competitive average power factor larger than 1.5 mW/mK.sup.2 from 350 to 500 K. In addition, the present disclosure demonstrates a 1D/2D nanocomposite film (e.g., 1D Te nanorods and 2D Sb.sub.2Te.sub.3 nanoplates) that exhibits an ultrahigh peak power factor of 2.2 mW/mK.sup.2 at 500 K, which is especially attractive for waste heat recovery applications at medium-temperature ranges. A flexible all-printed thermoelectric generator was demonstrated, achieving a competitive device power density of 7.65 mW/cm.sup.2 with a temperature differential of 60 K. The aerosol jet printing technique not only provides enormous opportunities in scalable manufacturing of flexible TE devices for energy harvesting and cooling applications, but also can be readily applied to explore other device architectures for broad applications beyond thermoelectric devices.

IV. Examples

Example 1

[0116] Bi.sub.2Te.sub.2.7Se.sub.0.3 nanoplates fabrication: In order to fabricate Bi.sub.2Te.sub.2.7Se.sub.0.3 nanoplates, 2 mmol Bi(NO.sub.3).sub.3, 2.7 mmol Na.sub.2TeO.sub.3 and 0.3 mmol SeO.sub.2 were dissolved in 70 mL ethylene glycol (EG), 1.5 g NaOH was added with vigorous stirring, and followed by 0.5 g polyvinylpyrrolidone (PVP, Ms=40,000 g/mol) and refluxing the mixture solution at 185° C. with nitrogen protection. After the mixture cool down to room temperature, acetone was used to precipitate the fabricated Bi.sub.2Te.sub.3 nanoplates and then re-dissolve with ethanol. This process was repeated three times to remove any unreacted chemicals and ethylene glycol from the surface.

[0117] Bi.sub.2Te.sub.2.7Se.sub.0.3 inks preparation and 3D aerosol jet printing: The Bi.sub.2Te.sub.2.7Se.sub.0.3 nanoplates were dispersed in solution to form a stable ink to allow aerosol jet printing. The ink composition was optimized to achieve optimal film deposition and all-printed TE devices. The solvent or carrier for the Bi.sub.2Te.sub.2.7Se.sub.0.3 ink was a mixture of ethylene glycol (EG), glycerol and ethanol with ratio of EG:Glycerol:Ethanol of 35:5:60 by weight.

[0118] After that, Bi.sub.2Te.sub.2.7Se.sub.0.3 particles (15% by weight) were added, followed by a strong probe sonication (20 minutes) and bath sonication (30 minutes) at room temperature. High resolution (minimum 10 μm feature size) aerosol jet printing was used to print precise patterns with a printing speed of from 1 to 6 mm/s. The printer was digitally programmed with computer-aided design software (AutoCAD) for pattern formation, enhancing the flexibility for the design and manufacturing of all-printed TE devices.

[0119] Photonic sintering of Bi.sub.2Te.sub.2.7Se.sub.0.3 films: Photonic sintering was performed using a Sinteron 2100 (Xenon Corp., USA) with a 107 mm Xenon spiral lamp. The S-2100 can be configured for maximum pulse durations of 3 ms with the sintering carried out in an ambient environment. The S-2100 can produce pulse energy ranging from 30 to 2850 Joules as well as a maximum pulse energy of 950 J/ms.

[0120] Characterizations: The synthesized Bi.sub.2Te.sub.2.7Se.sub.0.3 nanoplates were analyzed by X-ray diffraction (XRD) using Cu Kα radiation (λ=1.5418 Å, Bruker D2 Phaser). Transmission Electron Microscope (TEM) and High Resolution TEM techniques including the selected 12 area electron diffraction (SAED) images were performed using a JEM-2100 electron microscope. The morphology of all films was measured by the Scanning Electron Microscope Magellan 400 (FEI Company), with working voltage 15 KV and working of distance 4.5 mm.

[0121] Device fabrication and testing: In order to fabricate a thermoelectric device, four printed films were electrically connected in series using silver electrodes. The thermoelectric device was measured using a custom-built testing system with controlled hot-side and cold-side temperatures, and a variable resistor to match the TE device resistances in order to obtain the maximum power output.

[0122] Various performance characteristics relative to Example 1 are shown in the Figures and Tables and described in the detailed description section herein.

Example 2

[0123] Nanoparticle fabrication (Sb.sub.2Te.sub.3 and Sb.sub.2Te.sub.3—Te): To synthesize pure Sb.sub.2Te.sub.3, 70 ml ethylene glycol (EG) solution containing mixed antimony trichloride (SbCl.sub.3, 6 mmol), tellurium dioxide (TeO.sub.2, 9 mmol), sodium hydroxide (NaOH, 1.5 g), and polyvinylpyrrolidone (PVP, Ms of about 40000 g/mol, 0.8 g) were heated to 120° C. 10 ml hydrazine hydrate (N.sub.2H.sub.4) was swiftly injected. The mixture was maintained at 130° C. for 30 minutes, then heated to 155° C. under reflux for another 10 hours. The precipitates were collected by centrifugation at 5000 rpm, washed using ethanol, three times. To fabricate the Te-rich nanocomposite (Sb.sub.2Te.sub.3—Te), a nominal 10 at % excess of TeO.sub.2 was added with the other conditions remaining the same.

[0124] Ink preparation and aerosol jet printing: The as-fabricated nanoplates were dispersed in solution to form a stable ink to allow aerosol jet printing (OPTOMEC AJP 300) using a pneumatic atomizer (PA). Normal inkjet printing has a strict requirement that viscosity be maintained in a range of 5-15 cps. Aerosol jet printing, on the other hand, can print ink with viscosities across a wider range, e.g., from 1-1000 cps, with different nanostructures, providing a versatile approach with high spatial resolution. In the present disclosure, the ink composition was formulated to provide excellent film deposition and all printed TE devices. The solvent or carrier for the Sb.sub.2Te.sub.3 ink was a mixture of ethylene glycol (EG), glycerol and ethanol with an EG:Glycerol:Ethanol ratio of 35:5:60 percent by weight. Sb.sub.2Te.sub.3 particles were added at a weight ratio of 20%, followed by a strong probe sonication (20 minutes) and bath sonication (30 minutes).

[0125] Silver conductive ink (PRELECT TPS 50G2) was purchased from CLARIANT, and mixed with deionized water at a volume ratio of 1:3 to prepare the Ag ink. Aerosol jet printing with ultrasonic atomizer (UA) was used to print the Ag electrodes. The printing parameters were as summarized in Table 5.

[0126] Sintering of as-printed film: After cold pressing at 15 MPa for 15 minutes, thermal sintering was performed. The films were pre-heated at 110° C. for 90 minutes to remove remaining solvent under an N.sub.2 atmosphere, and then sintered at 400° C. for 1 hour with an increasing rate of 1.5° C./min, then decreased to 250° C. and held for another 2 hours. Finally, the samples were cooled down to room temperature (e.g., 20-25° C.).

[0127] Characterizations: The synthesized Sb.sub.2Te.sub.3 nanoplates were analyzed by X-ray diffraction (XRD) using Cu Kα radiation (λ=1.5418 Å, Bruker D2 Phaser). TEM and High Resolution TEM techniques including the selected area electron diffraction (SAED) images were performed using a JEM-2100 electron microscope. TEM specimens were prepared using focused ion beam (FIB) milling process, a FEI Helios FIB-SEM (FEI Company, Hillsboro, Oreg., USA) was used for serial sectioning and data collection. The morphology of all films (cross section and top-view) was measured by the Scanning Electron Microscope Magellan 400 (FEI Company), with a working voltage of 15 KV and a working distance of 4.5 mm.

[0128] Thermoelectric properties measurement: Seebeck coefficients were measured with a transient method wherein the temperature difference is increased from 1 to 5 K at approximately 0.5 K/min. Electrical conductivity was measured before Seebeck coefficient when temperatures are held at steady state with less than 0.05 K/min change in absolute temperature and in temperature difference. A schematic of the measurement setup is shown in FIG. 25. Seebeck coefficient and electrical conductivity are measured at the same time and temperature using the configuration shown in FIG. 25.

[0129] The film being tested is held to a dielectric support substrate with two electrodes through which current I is supplied for electrical conductivity measurement. Two thermocouples are brought into contact with the film and the measurement apparatus placed in a helium environment to improve thermal contact between the thermocouple tips and the film. On the other side of the electrodes are gradient heaters allowing precise control over the temperatures T.sub.h and T.sub.c and thus the temperature gradient ΔT=T.sub.h−T.sub.c. Before measurement begins, the temperature gradient across the film is prescribed to be ΔT=1K. When all temperatures are at steady state (less than 0.05 K/min change in absolute temperature and in temperature gradient ΔT) the current switch is closed and current is sent through the sample. The voltage is measured across the negative leads of the thermocouples. This was done for five equally spaced current values. The sample resistance R is the slope of the best fit line through the V/I data and the conductivity is then calculated as σ=L/RA, where L is the distance between the thermocouple tips and A is the cross-sectional area of the sample.

[0130] Seebeck coefficient measurement begins by opening the current switch and slowly ramping the temperature gradient ΔT from 1K to about 5 K while recording ΔT and voltage difference ΔV across the negative leads of the thermocouples with alternating measurements equally spaced in time. The negative of the slope of the best fit line through the ΔV/ΔT data gives the Seebeck coefficient relative to the material comprising the negative lead of the thermocouple. The absolute Seebeck coefficient of the sample is obtained by adding the absolute Seebeck coefficient of the negative thermocouple wire material to the measured sample relative Seebeck coefficient. The measurement error of the set-up was less than 2% for electrical conductivity and less than 3% for the Seebeck coefficient, respectively. The instrument was calibrated using a standard constantan sample of known properties.

[0131] Transport and electronic structure calculations: Density functional calculations were performed for bulk Sb.sub.2Te.sub.3 with the Perdew-Burke-Ernzerhof Generalized Gradient

[0132] Approximation (PBE-GGA). The calculations were done using the general potential linearized augmented planewave method as implemented in the WIEN2k code. Experimental lattice parameters were used, and the non-symmetry constrained atomic positions were determined by total energy minimization. Transport calculations were done using the BoltzTraP code with the constant scattering time approximation. The electronic fitness function was then obtained from the transport data using the transM code.

[0133] Various performance characteristics relative to Example 2 are shown in the Figures and Tables and described in the detailed description section herein.

[0134] Features from any of the disclosed embodiments or claims may be used in combination with one another, without limitation. It will also be appreciated that the present claimed invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative, not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.