Thermoelectric properties of indium-filled skutterudites prepared by combining solvothermal synthesis and melting

Indium-filled skutterudites with nominal compositions of In _x Co₄Sb₁₂ (x=0,0.1,0.2,0.3) were prepared by combining solvothermal synthesis and melting. The bulk samples were characterized by X-ray diffraction and scanning electron microscopy, respectively. The Seebeck coefficient, electrical conductivity, and thermal conductivity were measured from room temperature up to ∼773 K. Hall effect measurements were performed at room temperature. The thermoelectric properties of the samples were significantly influenced by filling In into CoSb₃. The dimensionless thermoelectric figure of merit, ZT, increased with increasing temperature and reached a maximum value of ∼0.79 for In_0.1Co₄Sb₁₂ at 573 K.     

High‐temperature stability of Au/p‐type diamond Schottky diode

Rectification properties of Au Schottky diodes were investigated in high‐temperature operation. These diodes were fabricated on a p‐type diamond single crystal using the vacuum‐ultraviolet light/ozone treatment. The ideality factor n of the Schottky diodes decreased monotonically with increasing measurement temperature whereas the Schottky barrier height ?_b increased, and ?_b reached 2.6 eV at 550 K with n of 1.1. Through high temperature heating at 870 K, the mean value of ?_b at 300 K changed permanently from 2.2 eV to 1.1 eV. Decrease of ?_b might originate from a dissolution of oxygen termination at the Au/diamond interface. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermoelectric properties of unoxidized graphene/Bi2Te2.7Se0.3 composites synthesized by exfoliation/re‐assembly method

Nanocomposites of n‐type thermoelectric Bi₂Te_2.7Se_0.3 (BTS) and unoxidized graphene (UG) were prepared from the exfoliated BTS and UG nanoplatelets. Polycrystalline BTS ingots were exfoliated into nanoscoll‐type crystals by chemical exfoliation, and were re‐assembled with UG nanoplatelets. The composites were chemically reduced by hydrazine hydrate and sintered by a spark‐plasma‐sintering method. The thermoelectric properties of the sintered composites were evaluated and exhibited decreased carrier concentration and increased thermal conductivity due to the embedded graphene. The peak ZT values for the UG/BTS‐US and UG/BTS‐EX composites were ～0.8 at the UG concentration of 0.05 wt%. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermoelectric properties of p‐type Mg2Si0.6Ge0.4 fabricated by bulk mechanical alloying and hot pressing

Bulk mechanical alloying (BMA) followed by hot pressing (HP) was used to prepare Mg₂Si_0.6Ge_0.4 thermoelectric material with high densification. Starting from the elemental power mixture, the Mg₂Si_0.6Ge_0.4 solid solution was solid‐state synthesized via BMA. In fact, the peaks for the cubic‐structured Mg₂Si_0.6Ge_0.4 solid solution phase were detected after 300 cycles in BMA. The single phase of Mg₂Si_0.6Ge_0.4 was synthesized at 600 cycles in BMA. Mg₂Si_0.6Ge_0.4 showed p‐type semiconduction without doping. Effects of hot pressing conditions on thermoelectric properties were investigated. With increasing hot pressing temperature from 673 to 773 K and pressure from 500 MPa to 1 GPa, the electrical conductivity increased and the Seebeck coefficient decreased. The maximum figure of merit was obtained with the processing parameter of 600 cycles BMA and hot pressing at 773 K, 1 GPa for 1 h. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and mechanical properties of spark plasma sintered n‐ and p‐type bismuth telluride alloys

Spark Plasma Sintering (SPS) is used for the fabrication of wafers of n‐ and p‐type thermoelectric V₂VI₃ materials. The SPS process did not change the overall chemical composition. X‐ray diffraction analysis and the electron backscattered selected area diffraction prove the preferential orientation after the SPS procedure expecting anisotropic thermoelectric prop‐ erties. The mechanical properties of the SPS material are enormously enhanced, so that the fabrication of thin wafers with only 100 µm thickness suitable for the development of Peltier devices with high cooling power density will be possible. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Improved thermoelectric figure of merit of self‐doped Ag8–xGeTe6 compounds with glass‐like thermal conductivity

Nonstoichiometric Ag_8–xGeTe₆ (x = 0, 0.01, 0.02, 0.04) compounds with complex crystal structure are demonstrated to exhibit very low thermal conductivities of <0.28 W/m K, comparable with the calculated theoretical minimum thermal conductivity κ_min. Ag deficiency leads to the improved electrical properties and a maximum thermoelectric figure of merit ZT of 0.85 has been obtained at 623 K for Ag_7.99GeTe₆, about 30% increase compared to that of stoichiometric Ag₈GeTe₆. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nanostructured thermoelectric oxides with low thermal conductivity

Complex metal oxides, such as e.g. perovskite‐type phases are developed as potential functional materials to improve the efficiency of thermoelectric converters. Among those, cobaltates with p‐type conductivity and n‐type manganates are considered for the realisation of a ceramic thermoelectric converter. Sintered pellets with the composition AMO_3–δ (A = Ln, RE; M = Co, Mn, Ni, Ti) and “Ca₃Co₄O₉ derivates” were synthesized and characterised concerning their thermoelectric properties in a broad temperature range. It was found that the Seebeck coefficient and the electrical conductivity do not depend on the dimensions of the crystallites, while the heat conductivity can be substantially lowered by decreasing the size of the crystalline domains in these systems. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Reinvestigation of the thermoelectric properties of Ag8GeTe6

High‐density polycrystalline samples (above 98% of the theoretical density) of Ag₈GeTe₆ were prepared by solid‐state reactions of Ag₂Te, GeTe, and Te, followed by hot‐pressing. The thermoelectric properties were measured at temperatures ranging from room temperature to around 700 K. The thermal conductivity values were extremely low (0.25 Wm^–1 K^–1 at room temperature), and consequently Ag₈GeTe₆ exhibited a relatively high thermoelectric figure of merit, ZT = 0.48 at 703 K. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermoelectric properties of CoSb3 with maize‐like structure

Maize‐like CoSb₃ powders were obtained via the chemical alloying method. After the consolidation of the nanopowder using hot press, the CoSb₃ compact shows a higher Seebeck coefficient and lower thermal conductivity. For the investigated CoSb₃, a ZT of 0.15 at 673 K is shown. Though the achieved ZT does not reach the optimal value (0.17 to 0.18) for pure CoSb₃, due to its lower electrical conductivity, the novel structure fabrication provides an interesting and promising approach to enhancing the thermoelectric performance. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Surface passivation of phosphorus‐diffused n+‐type emitters by plasma‐assisted atomic‐layer deposited Al2O3

In recent years Al₂O₃ has received tremendous interest in the photovoltaic community for the application as surface passivation layer for crystalline silicon. Especially p‐type c‐Si surfaces are very effectively passivated by Al₂O₃, including p‐type emitters, due to the high fixed negative charge in the Al₂O₃ film. In this Letter we show that Al₂O₃ prepared by plasma‐assisted atomic layer deposition (ALD) can actually provide a good level of surface passivation for highly doped n‐type emitters in the range of 10–100 Ω/sq with implied‐V_oc values up to 680 mV. For n‐type emitters in the range of 100–200 Ω/sq the implied‐V_oc drops to a value of 600 mV for a 200 Ω/sq emitter, indicating a decreased level of surface passivation. For even lighter doped n‐type surfaces the passivation quality increases again to implied‐V_oc values well above 700 mV. Hence, the results presented here indicate that within a certain doping range, highly doped n‐ and p‐type surfaces can be passivated simultaneously by Al₂O₃. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermoelectric properties of n-type Sr x M y Co4Sb12 (M=Yb, Ba) double-filled skutterudites

Alkaline-earth (AE) and rare-earth (RE) atoms are usually used as void fillers in the caged compound CoSb₃ to improve the thermoelectric performance of the filled system. Polycrystalline single-filled Sr_0.21Co₄Sb₁₂, double-filled Sr _x Yb _y Co₄Sb₁₂, and Sr _x Ba _y Co₄Sb₁₂ skutterudites have been synthesized. Rietveld structure refinement confirms that both Sr and Yb occupy the Sb-icosaedron voids in skutterudite frame work. In this paper, we report the high-temperature thermoelectric properties including electrical conductivity, Seebeck coefficient, and thermal conductivity. Double filling of the Sr–Yb combinations shows a stronger suppression on lattice thermal conductivity than that of Sr–Ba combination. Furthermore, the double-filled Sr _x Yb _y Co₄Sb₁₂ skutterudites exhibit a much higher power factor than the Sr-filled system. The maximum power factor for Sr_0.22Yb_0.03Co₄Sb_12.12 reaches 41 μW cm⁻¹ K⁻² at room temperature and 57.5 μW cm⁻¹ K⁻² at 850 K, respectively. The enhanced thermoelectric figures of merit are 1.32 for Sr _x Yb _y Co₄Sb₁₂ and 1.22 for Sr _x Ba _y Co₄Sb₁₂ at 850 K, respectively.     

Molybdenum oxide thin films in CdTe‐based electronic and optoelectronic devices

This paper reports on the both possible applications of molybdenum oxide (MoO_x) thin films in combination with hole or electron conducting CdTe. The high quality ohmic contancts and strongly rectifying photodiodes were prepared by the DC magnetron sputtering of MoO_x thin films onto freshly cleaved p‐ and n‐type CdTe single crystal substrates. The analysis of DC and AC electrical properties of the MoO_x/ p‐CdTe ohmic contact was carried out. The dominating current transport mechanisms through the MoO_x/p‐CdTe heterojunction at forward and reverse bias were determined. The unoptimized heterojunction photodiode showed promising rectifying and photoelectrical characteristics for practical application in the photoconductive mode. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Lattice dynamics and low‐temperature Raman spectroscopy studies of PMN–PT relaxors

In this work we present a Raman scattering study of a specific region of the morphotropic phase boundary (MPB) of the [Pb(Mg_1/3Nb_2/3)O₃]_1−x (PbTiO₃)_x relaxor system. We performed low‐temperature measurement for the x = 0.4 composition in the 20–300 K temperature range, and a detailed analysis of Raman spectra of x = 0.4 and x = 0.37 compositions at 180 K. The analysis of Raman spectra indicates a structural phase transition at around 170 K for x = 0.4. The comparison of Raman data from x = 0.4 and x = 0.37 compositions suggests different phases for these samples at 180 K. These results are in accordance with the tetragonal to monoclinic structural phase transition observed in the PMN–PT MPB and contribute to improve the knowledge of the MPB of this solid solution. Additionally, we have performed the lattice dynamics phonon calculation of the (1 − x) PMN–xPT relaxor in order to best understand its complex Raman spectral properties. The normal mode analyses (at q ∼ 0) were performed by considering tetragonal symmetry for the (1 − x) PMN–xPT system and using the rigid ion model and mean field approximation. Our calculated wavenumber values are in good agreement with experimental and calculated results reported for PbTiO₃ thus providing a reliable assignment of the various Raman modes. The low wavenumber modes are interpreted as arising from a lifting of the degeneracy of the vibrational modes related to Mg, Nb and Ti sites. Copyright © 2009 John Wiley & Sons, Ltd.     

Thermoelectric figure-of-merit in <Emphasis Type="Italic">p</Emphasis>-type bismuth- and antimony-chalcogenide-based solid solutions above room temperature

The specific features of the variation in the thermoelectric figure-of merit Z for p-type bismuth- and antimony-chalcogenide-based solid solutions p-(Bi,Sb)₂(Te,Se)₃ have been analyzed with allowance made for the data amassed in the investigation of thermoelectric and galvanomagnetic properties. It has been shown that, in the samples with optimum carrier concentrations, the increase in Z in the multicomponent p-Bi_{2 − x} Sb _x Te_{3 − y} Se _y composition (x = 1.3, y = 0.06) in the temperature range 300–370 K is mediated by the high carrier mobility and the low lattice thermal conductivity. The higher effective mass of the density of states and the larger slope of the temperature dependence of the mobility as compared to the other compositions bring about an increase in Z in the p-Bi_{2 − x} Sb _x Te₃ solid solution for x = 1.6 in the temperature range 370–550 K. The increase in the figure-of merit reached in the compositions under study stems also from the increasing contraction of constant-energy ellipsoids along the binary and bisector directions and from the change in the angle θ between the principal axes of the ellipsoids and the crystallographic axes.     

Surface passivation schemes for high‐efficiency n‐type Si solar cells

An effective passivation on the front side boron emitter is essential to utilize the full potential of solar cells fabricated on n‐type silicon. However, recent investigations have shown that it is more difficult to achieve a low surface recombination velocity on highly doped p‐type silicon than on n‐type silicon. Thus, the approach presented in this paper is to overcompensate the surface of the deep boron emitter locally by a shallow phosphorus diffusion. This inversion from p‐type to n‐type surface allows the use of standard technologies which are used for passivation of highly doped n‐type surfaces. Emitter saturation current densities (J_0e) of 49 fA/cm² have been reached with this approach on SiO₂ passivated lifetime samples. On solar cells a certified conversion efficiency of 21.7% with an open‐circuit voltage (V_oc) of 676 mV was achieved. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Rotational disorder in 2‐piperidyl‐5‐nitro‐6 ‐methylpyridine: structural phase transition and its vibrational characteristics

X‐ray diffraction (XRD) studies have shown that 2‐piperidyl‐5‐nitro‐6‐methylpyridine, C₁₁H₁₅N₃O₂, undergoes a structural phase transition at T = 240 K. The room temperature structure is tetragonal, space group I4₁/a, with the unit‐cell dimensions a = 13.993(2) and c = 23.585(5) Å. The pyridine ring takes trans conformation with respect to the piperidine unit. While pyridine is well ordered, the piperidine moiety shows apparent disorder resulting from a libration about the linking N C bond. The low‐temperature phase is monoclinic, space group I2/a. Contraction of the unit‐cell volume by 2.3% at 170 K enables the C H···O linkage between the molecules of the neighbouring stacks. As result, the asymmetric unit becomes bi‐molecular. The thermal librations of the piperidine and methyl groups become considerably reduced at 170 K and nearly fully reduced at about 100 K. The IR spectra and polarised Raman spectra agree with the X‐ray structure and confirm the disorder effect on the piperidine ring. The assignment of the bands observed was made on the basis of DFT chemical quantum calculations. Copyright © 2008 John Wiley & Sons, Ltd.     

P‐type tin‐oxide thin film transistors for blue‐light detection application

We reported the characteristics of p‐type tin‐oxide (SnO) thin film transistors (TFTs) upon illumination with visible light. Our p‐type TFT device using the SnO film as the active channel layer exhibits high sensitivity toward the blue‐light with a high light/dark read current ratio (I_light/I_dark) of 8.2 × 10³ at a very low driven voltage of <3 V. Since sensing of blue‐light radiation is very critical to our eyes, the proposed p‐type SnO TFTs with high sensitivity toward the blue‐light show great potential for future blue‐light detection applications.

     

High‐temperature thermoelectric properties of Cu2In4Te7

Cu₂Ga₄Te₇ has recently been reported to have a relatively high thermoelectric (TE) figure of merit (ZT). However, the TE properties of Cu₂In₄Te₇, which has the same defect zinc‐blende structure as Cu₂Ga₄Te₇, have been hardly investigated. Here, we demonstrate that Cu₂In₄Te₇ has relatively high ZT values that are similar to those of Cu₂Ga₄Te₇. High‐density polycrystalline bulk samples of Cu₂In₄Te₇ were prepared and their electrical resistivity (?), Seebeck coefficient (S), and thermal conductivity (κ) were measured. Cu₂In₄Te₇ has a maximum ZT of 0.3 at 700 K, with ?, S, and κ values of 62.1 × 10^–5 Ω m, 394 μV K^–1, and 0.61 W m^–1 K^–1, respectively. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Bond cutting in K‐doped tris(8‐hydroxyquinoline) aluminium

A series of Al 2p, K 2p, O 1s and N 1s core‐level spectra have been used to characterize the interaction between potassium (K) and tris(8‐hydroxyquinoline) aluminium (Alq₃) molecules in the K‐doped Alq₃ layer. All core‐level spectra were tuned to be very surface sensitive in selecting various photon energies provided by the wide‐range beamline at the National Synchrotron Radiation Research Center, Taiwan. A critical K concentration (x = 2.4) exists in the K‐doped Alq₃ layer, below which the K‐doped atoms generate a strained environment near the O and N atoms within 8‐quinolinoline ligands. This creates new O 1s and N 1s components on the lower binding‐energy side. Above the critical K coverage, the K‐doped atoms attach the O atoms in the Al—O—C bonds next to the phenoxide ring and replace Al—O—C bonds by forming K—O—C bonds. An Alq₃ molecule is disassembled into Alq₂ and Kq by bond cutting and bond formation. The Alq₂ molecule can be further dissociated into Alq, or even Al, through subsequent formations of Kq.     

Ga填充n型方钴矿化合物的结构及热电性能

用熔融退火结合放电等离子烧结(SPS)技术制备了具有不同Ga填充含量的Ga_xCo₄Sb₁₂方钴矿化合物,研究了不同Ga含量对其热电传输特性的影响规律. Rietveld结构解析表明,Ga占据晶体学2a空洞位置,Ga填充上限约为0.22,当Ga的名义组成x≤0.25时,样品的电导率、室温载流子浓度N_p随Ga含量的增加而增加,Seebeck系数随Ga含量的增加而减小. 室温下霍尔测试表明,每一个Ga授予框架0.9个电子,比Ga的氧化价态Ga³⁺小得多. 由于Ga离子半径相对较小,致使Ga填充方钴矿化合物的热导率κ及晶格热导率κ_L较其他元素填充的方钴矿化合物低. 当x＝0.22时对应的样品在300K时的热导率和晶格热导率分别为3.05Wm^-1·K^-1和 2.86Wm^-1·K^-1.在600K下Ga_0.22Co_4.0Sb_12.0样品晶格热导率达到最小,为1.83Wm^-1·K^-1,最大热电优值Z,在560K处达1.31×10^-3K^-1. 关键词： skutterudite化合物 Ga原子填充 结构 热电性能