Highly Passivated n‐Type Colloidal Quantum Dots for Solution‐Processed Thermoelectric Generators with Large Output Voltage

Colloidal quantum dots (CQDs) are attractive materials for thermoelectric applications due to their simple and low‐cost processing; advantageously, they also offer low thermal conductivity and high Seebeck coefficient. To date, the majority of CQD thermoelectric films reported upon have been p‐type, while only a few reports are available on n‐type films. High‐performing n‐ and p‐type films are essential for thermoelectric generators (TEGs) with large output voltage and power. Here, high‐thermoelectric‐performance n‐type CQD films are reported and showcased in high‐performance all‐CQD TEGs. By engineering the electronic coupling in the films, a thorough removal of insulating ligands is achieved and this is combined with excellent surface trap passivation. This enables a high thermoelectric power factor of 24 µW m^?1 K^?2, superior to previously reported n‐type lead chalcogenide CQD films operating near room temperature (<1 µW m^?1 K^?2). As a result, an all‐CQD film TEG with a large output voltage of 0.25 V and a power density of 0.63 W m^?2 at ?T = 50 K is demonstrated, which represents an over fourfold enhancement to previously reported p‐type only CQD TEGs.     

Flexible Thermoelectric Generators Composed of n‐and p‐Type Silicon Nanowires Fabricated by Top‐Down Method

This study demonstrates the fabrication and characterization of a flexible thermoelectric (TE) power generator composed of silicon nanowires (SiNWs) fabricated by top‐down method and discusses its strain‐dependence analysis. The Seebeck coefficients of the p‐ and n‐type SiNWs used to form a pn‐module are 156.4 and ?146.1 µV K^?1, respectively. The maximum power factors of the p‐ and n‐type SiNWs are obtained as 8.79 and 8.87 mW (m K²)^?1, respectively, under a convex bending of 1.11%, respectively; these are the largest values among the power factors hitherto reported for SiNWs. The dimensionless figure of merit (ZT ) values of the SiNWs at room temperature are 6.8 × 10^?2 and 6.7 × 10^?2 for the convex bent p‐ and n‐type SiNWs, respectively, with a strain of 1.11%. The thermoelectric properties of the pn‐module and its component SiNWs are characterized under strain conditions ranging from ?1.11% to 1.11%. The maximum Seebeck coefficient and power factor of the pn‐module are obtained as 448 µV K^?1 and 14.2 mW (m K²)^?1, respectively, under convex bending of 1.11%. Moreover, the mechanical stability of the TE characteristics of the pn‐module is demonstrated through a continuous bending test of 3000 cycles under convex bending of 0.66%.     

High Thermoelectric zT in n‐Type Silver Selenide films at Room Temperature

In this work, a zT value as high as 1.2 at room temperature for n‐type Ag₂Se films is reported grown by pulsed hybrid reactive magnetron sputtering (PHRMS). PHRMS is a novel technique developed in the lab that allows to grow film of selenides with different compositions in a few minutes with great quality. The improved zT value reported for room temperature results from the combination of the high power factors, similar to the best values reported for bulk Ag₂Se (2440 ± 192 µW m^?1 K^?2), along with a reduced thermoelectric conductivity as low as 0.64 ± 0.1 W m^?1 K^?1. The maximum power factor for these films is of 4655 ± 407 µW m^?1 K^?2 at 103 °C. This material shows promise to work for room temperature applications. Obtaining high zT or, in other words, high power factor and low thermal conductivity values close to room temperature for thin films is of high importance to develop a new generation of wearable devices based on thermoelectric heat recovery.     

Liquid Crystallinity as a Self‐Assembly Motif for High‐Efficiency,Solution‐Processed,Solid‐State Singlet Fission Materials

Solution and solution‐deposited thin films of the discotic liquid crystalline electron acceptor–donor–acceptor (A‐D‐A) p‐type organic semiconductor FHBC(TDPP)₂, synthesized by coupling thienyl substituted diketopyrrolopyrrole (TDPP) onto a fluorenyl substituted hexa‐peri‐hexabenzocoronene (FHBC) core, are examined by ultrafast and nanosecond transient absorption spectroscopy, and time‐resolved photoluminescence studies to examine their ability to support singlet fission (SF). Grazing incidence wide‐angle X‐ray (GIWAX) studies indicate that as‐cast thin films of FHBC(TDPP)₂ are “amorphous,” while hexagonal packed discotic liquid crystalline films evolve during thermal annealing. SF in as‐cast thin films is observed with an ≈150% triplet generation yield. Thermally annealing the thin films improves SF yields up to 170%. The as‐cast thin films show no long‐range order, indicating a new class of SF material where the requirement for local order and strong near neighbor coupling has been removed. Generation of long‐lived triplets (µs) suggests that these materials may also be suitable for inclusion in organic solar cells to enhance performance.     

Low‐Temperature‐Processed Colloidal Quantum Dots as Building Blocks for Thermoelectrics

Colloidal quantum dots (CQDs) are demonstrated to be promising materials to realize high‐performance thermoelectrics owing to their low thermal conductivity. The most studied CQD films, however, are using long ligands that require high processing and operation temperature (>400 °C) to achieve optimum thermoelectric performance. Here the thermoelectric properties of CQD films cross‐linked using short ligands that allow strong inter‐QD coupling are reported. Using the ligands, p‐type thermoelectric solids are demonstrated with a high Seebeck coefficient and power factor of 400 μV K^?1 and 30 µW m^?1 K^?2, respectively, leading to maximum ZT of 0.02 at a lower measurement temperature (<400 K) and lower processing temperature (<300 °C). These ligands further reduce the annealing temperature to 175 °C, significantly increasing the Seebeck coefficient of the CQD films to 580 μV K^?1. This high Seebeck coefficient with a superior ZT near room temperature compared to previously reported high temperature‐annealed CQD films is ascribed to the smaller grain size, which enables the retainment of quantum confinement and significantly increases the hole effective mass in the films. This study provides a pathway to approach quantum confinement for achieving a high Seebeck coefficient yet strong inter‐QD coupling, which offers a step toward low‐temperature‐processed high‐performance thermoelectric generators.     

Optimum Carrier Concentration in n‐Type PbTe Thermoelectrics

Taking La‐ and I‐doped PbTe as an example, the current work shows the effects of optimizing the thermoelectric figure of merit, zT, by controlling the doping level. The high doping effectiveness allows the carrier concentration to be precisely designed and prepared to control the Fermi level. In addition to the Fermi energy tuning, La‐doping modifies the conduction band, leading to an increase in the density of states effective mass that is confirmed by transport, infrared reflectance and hard X‐ray photoelectron spectroscopy measurements. Taking such a band structure modification effect into account, the electrical transport properties can then be well‐described by a self‐consistent single non‐parabolic Kane band model that yields an approximate (m*T)^1.5 dependence of the optimal carrier concentration for a peak power factor in both doping cases. Such a simple temperature dependence also provides an effective approximation of carrier concentration for a peak zT and helps to explain, the effects of other strategies such as lowering the lattice thermal conductivity by nanostructuring or alloying in n‐PbTe, which demonstrates a practical guide for fully optimizing thermoelectric materials in the entire temperature range. The principles used here should be equally applicable to other thermoelectric materials.     

Studies on Thermoelectric Properties of n‐type Polycrystalline SnSe1‐xSx by Iodine Doping

Iodine‐doped n‐type SnSe polycrystalline by melting and hot pressing is prepared. The prepared material is anisotropic with a peak ZT of ≈0.8 at about 773 K measured along the hot pressing direction. This is the first report on thermoelectric properties of n‐type Sn chalcogenide alloys. With increasing content of iodine, the carrier concentration changed from 2.3 × 10¹⁷ cm^?3 (p‐type) to 5.0 × 10¹⁵ cm^?3 (n‐type) then to 2.0 × 10¹⁷ cm^?3 (n‐type). The decent ZT is mainly attributed to the intrinsically low thermal conductivity due to the high anharmonicity of the chemical bonds like those in p‐type SnSe. By alloying with 10 at% SnS, even lower thermal conductivity and an enhanced Seebeck coefficient were achieved, leading to an increased ZT of ≈1.0 at about 773 K measured also along the hot pressing direction.     

High Thermoelectric Performance in p‐type Polycrystalline Cd‐doped SnSe Achieved by a Combination of Cation Vacancies and Localized Lattice Engineering

Herein, a high figure of merit (ZT) of ≈1.7 at 823 K is reported in p‐type polycrystalline Cd‐doped SnSe by combining cation vacancies and localized‐lattice engineering. It is observed that the introduction of Cd atoms in SnSe lattice induce Sn vacancies, which act as p‐type dopants. A combination of facile solvothermal synthesis and fast spark plasma sintering technique boosts the Sn vacancy to a high level of ≈2.9%, which results in an optimum hole concentration of ≈2.6 × 10¹⁹ cm^?3 and an improved power factor of ≈6.9 µW cm^?1 K^?2. Simultaneously, a low thermal conductivity of ≈0.33 W m^?1 K^?1 is achieved by effective phonon scattering at localized crystal imperfections, as observed by detailed structural characterizations. Density functional theory calculations reveal that the role of Cd atoms in the SnSe lattice is to reduce the formation energy of Sn vacancies, which in turn lower the Fermi level down into the valence bands, generating holes. This work explores the fundamental Cd‐doping mechanisms at the nanoscale in a SnSe matrix and demonstrates vacancy and localized‐lattice engineering as an effective approach to boosting thermoelectric performance. The work provides an avenue in achieving high‐performance thermoelectric properties of materials.     

Rear Surface Passivation for Ink-Based,Submicron CuIn(S,Se)2 Solar Cells

A N, N-dimethylformamide and thiourea-based route is developed to fabricate submicron (0.55 and 0.75 µm) thick CuIn(S,Se)₂ (CISSe) thin films for photovoltaic applications, addressing challenges of material usage, throughput, and manufacturing costs. However, reducing the absorber film thickness below 1 µm in a regular CISSe solar cell decreases the device efficiency due to losses at the highly-recombinative, and mediocre-reflective Mo/CISSe rear interface. For the first time, to mitigate the rear recombination losses, a novel rear contacting structure involving a surface passivation layer and point contact openings is developed for solution processed CISSe films and demonstrated in tangible devices. An atomic layer deposited Al₂O₃ film is employed to passivate the Mo/CISSe rear surface while precipitates formed via chemical bath deposition of CdS are used to generate nanosized point openings. Consequently, Al₂O₃ passivated CISSe solar cells show an increase in the open-circuit voltage (V_OC) and short-circuit current density when compared to reference cells with equivalent absorber thicknesses. Notably, a V_OC increase of 59 mV contributes to active area efficiencies of 14.2% for rear passivated devices with 0.75 µm thick absorber layers, the highest reported value for submicron-based solution processed, low bandgap CISSe solar cells.     

Freely Shapable and 3D Porous Carbon Nanotube Foam Using Rapid Solvent Evaporation Method for Flexible Thermoelectric Power Generators

A rapid solvent evaporation method based on the triple point of a processing solvent is presented to prepare carbon nanotube (CNT) foam with a porous structure for thermoelectric (TE) power generators. The rapid solvent evaporation process allows the preparation of CNT foam with various sizes and shapes. The obtained highly porous CNT foam with porosity exceeding 90% exhibits a low thermal conductivity of 0.17 W m^?1 K^?1 with increased phonon scattering, which is 100 times lower than that of a CNT film with a densely packed network. The aforementioned structural and thermal properties of the CNT foam are advantageous to develop a sufficient temperature gradient between the hot and cold parts to enhance TE output characteristics. To improve the electrical conductivity and Seebeck coefficient further, p‐ and n‐molecular dopants are easily introduced into the CNT foam, and the optimized condition is investigated based on the TE properties. Finally, optimized p‐ and n‐doped CNT foams are used to fabricate a vertical and flexible TE power generator with a combination of series and parallel mixed circuits. The maximum output power and output power per weight of the TE generator reach 1.5 µW and 82 µW g^?1, respectively, at a temperature difference of 13.9 K.     

Optimizations of Pulsed Plated p and n‐type Bi2Te3‐Based Ternary Compounds by Annealing in Different Ambient Atmospheres

This work presents a comprehensive study of the fabrication and optimization of electrodeposited p‐ and n‐type thermoelectric films. The films are deposited on Au and stainless steel substrates over a wide range of deposition potentials. The influence of the preparative parameters such as the composition of the electrolyte bath and the deposition potential are investigated. Furthermore, the p‐doped (Bi_xSb_1‐x)₂Te₃ and the n‐doped Bi₂(Te_xSe_1‐x)₃ films are annealed for a period of about 1 h under helium and under tellurium atmosphere at 250 °C for 60h. Annealing in He already leads to significant improvements in the thermoelectric performance. Furthermore, due to the equilibrium conditions during the process, annealing in Te atmosphere leads to a strongly improved film composition, charge carrier density and mobility. The Seebeck coefficients increase to values up to +182 μV K^?1 for p‐doped and–130 μV K^?1 for n‐doped materials at room temperature. The power factors also exhibit improvements with 1320 μW m^?1 K^?2 and 820 μW m^?1 K^?2 for p‐doped and n‐doped films, respectively. Additionally, in‐situ XRD measurements performed during annealing of the films up to 600K under He atmosphere show stepwise improvements of the crystal structure leading to the improvements in thermoelectric parameters. The thermal conductivity is between 1.2 W m^?1 K^?1 and 1.0 W m^?1 K^?1.     

Cerium Oxide Decorated Polymer Nanofibers as Effective Membrane Reinforcement for Durable,High‐Performance Fuel Cells

High‐power, durable composite fuel cell membranes are fabricated here by direct membrane deposition (DMD). Poly(vinylidene fluoride‐co ‐hexafluoropropylene) (PVDF‐HFP) nanofibers, decorated with CeO₂ nanoparticles are directly electrospun onto gas diffusion electrodes. The nanofiber mesh is impregnated by inkjet‐printed Nafion ionomer dispersion. This results in 12 µm thin multicomponent composite membranes. The nanofibers provide membrane reinforcement, whereas the attached CeO₂ nanoparticles promote improved chemical membrane durability due to their radical scavenging properties. In a 100 h accelerated stress test under hot and dry conditions, the reinforced DMD fuel cell shows a more than three times lower voltage decay rate (0.39 mV h^?1) compared to a comparably thin Gore membrane (1.36 mV h^?1). The maximum power density of the DMD fuel cell drops by 9%, compared to 54% measured for the reference. Impedance spectroscopy reveals that ionic and mass transport resistance of the DMD fuel cell are unaffected by the accelerated stress test. This is in contrast to the reference, where a 90% increase of the mass transport resistance is measured. Energy dispersive X‐ray spectroscopy reveals that no significant migration of cerium into the catalyst layers occurs during degradation. This proves that the PVDF‐HFP backbone provides strong anchoring of CeO₂ in the membrane.     

Synergistically Optimizing Electrical and Thermal Transport Properties of BiCuSeO via a Dual‐Doping Approach

The layered oxyselenide BiCuSeO system is known as one of the high‐performance thermoelectric materials with intrinsically low thermal conductivity. By employing atomic, nano‐ to mesoscale structural optimizations, low thermal conductivity coupled with enhanced electrical transport properties can be readily achieved. Upon partial substitution of Bi³⁺ by Ca²⁺ and Pb²⁺, the thermal conductivity can be reduced to as low as 0.5 W m^?1 K^?1 at 873 K through dual‐atomic point‐defect scattering, while a high power factor of ≈1 × 10^?3 W cm^?1 K^?2 is realized over a broad temperature range from 300 to 873 K. The synergistically optimized power factor and intrinsically low thermal conductivity result in a high ZT value of ≈1.5 at 873 K for Bi_0.88Ca_0.06Pb_0.06CuSeO, a promising candidate for high‐temperature thermoelectric applications. It is envisioned that the all‐scale structural optimization is critical for optimizing the thermoelectricity of quaternary compounds.     

Behavioural responses of larvae of Colorado potato beetle,Leptinotarsa decemlineata (Coleoptera: Chrysomelidae), to host plant volatile blends attractive to adults

Abstract

• 1 Orientation of second‐ and fourth‐instar Colorado potato beetle (CPB) Leptinotarsa decemlineata (Say) (Coleoptera: Chrysomelidae), to volatiles emitted from a solanaceous host, potato, and seven synthetic blends or three individual chemicals emitted by potato plants were investigated in laboratory bioassays.
• 2 Both second‐ and fourth‐instar CPB were attracted to intact and mechanically damaged (MD) potato foliage. When offered a choice between intact and MD foliage, no preference was observed.
• 3 Among seven synthetic blends tested (of which six are attractive to adult CPB), second‐ and fourth‐instar CPB were attracted only to a single three‐component blend comprising (±)‐linalool, methyl salicylate, and (Z)‐3‐hexenyl acetate. Individual compounds and two‐component blends were inactive. No significant difference was noted between larval responses to the attractive synthetic blend vs. MD potato foliage.
• 4 Second‐and fourth‐instar larvae had similar thresholds for behaviour for the three‐component blend (50 µg source load). Female CPB were attracted to source loads 10× below the larval threshold (5 µg). Male CPB were the most sensitive life form tested with a behavioural threshold at 0.5 µg source load which was 10× and 100× below female and larval thresholds, respectively
• 5 This is the first report of a synthetic chemical attractant for CPB larvae. As both larval and adult CPB are attracted to a single chemical blend, the usefulness of the attractant as a component of an attracticide or ‘push‐pull’ strategies for management of pestiferous populations is enhanced.

     

Realizing High Thermoelectric Performance in n‐Type Highly Distorted Sb‐Doped SnSe Microplates via Tuning High Electron Concentration and Inducing Intensive Crystal Defects

In this study, a record high figure of merit (ZT) of ≈1.1 at 773 K is reported in n‐type highly distorted Sb‐doped SnSe microplates via a facile solvothermal method. The pellets sintered from the Sb‐doped SnSe microplates show a high power factor of ≈2.4 µW cm^?1 K^?2 and an ultralow thermal conductivity of ≈0.17 W m^?1 K^?1 at 773 K, leading a record high ZT. Such a high power factor is attributed to a high electron concentration of 3.94 × 10¹⁹ cm^?3 via Sb‐enabled electron doping, and the ultralow thermal conductivity derives from the enhanced phonon scattering at intensive crystal defects, including severe lattice distortions, dislocations, and lattice bent, observed by detailed structural characterizations. This study fills in the gaps of fundamental doping mechanisms of Sb in SnSe system, and provides a new perspective to achieve high thermoelectric performance in n‐type polycrystalline SnSe.     

Microfluidic device‐assisted etching of p‐HEMA for cell or protein patterning

The construction of biomaterials with which to limit the growth of cells or to limit the adsorption of proteins is essential for understanding biological phenomena. Here, we describe a novel method to simply and easily create thin layers of poly (2‐hydroxyethyl methacrylate) (p‐HEMA) for protein and cellular patterning via etching with ethanol and microfluidic devices. First, a cell culture surface or glass coverslip is coated with p‐HEMA. Next, a polydimethylsiloxane (PDMS) microfluidic is placed onto the p‐HEMA surface, and ethanol is aspirated through the device. The PDMS device is removed, and the p‐HEMA surface is ready for protein adsorption or cell plating. This method allows for the fabrication of 0.3 µm thin layers of p‐HEMA, which can be etched to 10 µm wide channels. Furthermore, it creates regions of differential protein adhesion, as shown by Coomassie staining and fluorescent labeling, and cell adhesion, as demonstrated by C2C12 myoblast growth. This method is simple, versatile, and allows biologists and bioengineers to manipulate regions for cell culture adhesion and growth. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 34:243–248, 2018     

Tunable mid‐infrared luminescence from Er3+‐doped germanate glass

Er³⁺‐doped germanate glasses with superior thermal stability were prepared. Judd–Ofelt intensity parameters and important spectroscopic properties were discussed in detail. Upon 800 nm and 980 nm LD pumping, 2.7 µm fluorescence characteristics were investigated and it was found that the effective 2.7 µm emission bandwidth can reach to 101.79 nm in prepared glasses. The tunability of the 2.7 µm emission band can be realized by adjusting the Er³⁺ content. Moreover, a high‐emission cross‐section (11.09 ×10^‐21 cm²), large gain bandwidth (772.30 ×10^‐28 cm³) and gain coefficient (6.72 cm^‐1) were obtained in the prepared sample. Hence, Er³⁺‐doped germanate glass might be a promising mid‐infrared material for tunable amplifiers or lasers. Copyright © 2014 John Wiley & Sons, Ltd.     

Lead‐Free Thermoelectrics: High Figure of Merit in p‐type AgSnmSbTem+2

Thermoelectric materials based on Pb‐free compositions are of considerable current interest in environmentally friendly power‐generation applications derived from waste‐heat sources. Here, a new study of the thermoelectric properties of the tin‐based compositions with the general formula AgSn_mSbTe_m+2 (m = 2, 4, 5, 7, 10, 14, 18) is presented, where the m value is used as the tuning parameter of the thermoelectric properties. The electrical conductivity, Seebeck coefficient, and thermal conductivity are measured from 300 K to 723 K and the resulting thermoelectric figure of merit is determined as a function of the SnTe/AgSbTe₂ ratio. A thermoelectric figure of merit ZT ≈1 is obtained at 710 K for m = 4, indicating that the system AgSn_mSbTe_m+2 holds great promise as an alternative p‐type, lead‐free, thermoelectric material.     

Grain Boundary Scattering of Charge Transport in n‐Type (Hf,Zr)CoSb Half‐Heusler Thermoelectric Materials

High thermoelectric figure of merit zT of ≈1.0 has been reported in both n‐ and p‐type (Hf,Zr)CoSb‐based half‐Heusler compounds, and further improvement of thermoelectric performance relies on the insightful understanding of electron and phonon transport mechanisms. In this work, the thermoelectric transport features are analyzed for (Hf_0.3Zr_0.7)_1?xNb_xCoSb (x = 0.02–0.3) with a wide range of carrier concentration. It is found that, although both temperature and energy dependencies of charge transport resemble ionized impurity scattering, the grain boundary scattering is the dominant scattering mechanism near room temperature. With increasing carrier concentration and grain size, the influence of the grain boundary scattering on electron transport weakens. The dominant scattering mechanism changes from grain boundary scattering to acoustic phonon scattering as temperature rises. The lattice thermal conductivity decreases with increasing Nb doping content due to the increased strain field fluctuations. These results provide an in‐depth understanding of the transport mechanisms and guidance for further optimizing thermoelectric properties of half‐Heusler alloys and other thermoelectric systems.     

Individual differences in temperature perception: Evidence of common processing of sensation intensity of warmth and cold

The longstanding question of whether temperature is sensed via separate sensory systems for warmth and cold was investigated by measuring individual differences in perception of nonpainful heating and cooling. Sixty-two subjects gave separate ratings of the intensity of thermal sensations (warmth, cold) and nociceptive sensations (burning/stinging/pricking) produced by cooling (29°C) or heating (37°C) local regions of the forearm. Stimuli were delivered via a 4?×?4 array of 8 mm?×?8?mm Peltier thermoelectric modules that enabled test temperatures to be presented sequentially to individual modules or simultaneously to the full array. Stimulation of the full array showed that perception of warmth and cold were highly correlated (Pearson r?=?0.83, p?<?0.05). Ratings of nonpainful nociceptive sensations produced by the two temperatures were also correlated, but to a lesser degree (r?=?0.44), and the associations between nociceptive and thermal sensations (r?=?0.35 and 0.22 for 37 and 29°C, respectively) were not significant after correction for multiple statistical tests. Intensity ratings for individual modules indicated that the number of responsive sites out of 16 was a poor predictor of temperature sensations but a significant predictor of nociceptive sensations. The very high correlation between ratings of thermal sensations conflicts with the classical view that warmth and cold are mediated by separate thermal modalities and implies that warm-sensitive and cold-sensitive spinothalamic pathways converge and undergo joint modulation in the central nervous system. Integration of thermal stimulation from the skin and body core within the thermoregulatory system is suggested as the possible source of this convergence.