Al-doped ZnO and N-doped CuxO thermoelectric thin films for self-powering integrated devices

With the use of a thermoelectric material, terrestrial heat can be harvested then converted to electrical power. The advent of these devices has led to the idea of self-powering wherein devices are driven by heat from their working environment. The focus of this study is to fabricate low cost thermoelectric materials, such as aluminum-doped ZnO (ZnO:Al) and nitrogen-doped Cu_xO (Cu_xO:N) that can effectively harvest heat for power generation.ZnO:Al (n-type) and Cu_xO:N (p-type) thin films with nanocrystallites were deposited in (1.27×0.64) cm² glass substrates via spray pyrolysis technique. These materials exhibit significantly high thermoelectric properties, which is comparable to previous works on thermoelectric materials. ZnO:Al showed to have a maximum Seebeck coefficient (S) of 448 μV/K ranging from 300 to 330 K. Cu_xO:N exhibited a significantly much larger |S| of 1002 μV/K at the same temperature range. A prototype of a thermoelectric device was constructed based from these grown thin films and showed to generate a maximum of 32.8 mV at 28 K temperature difference.     

p型方钴矿化合物BayFeCo3Sb12的热电性能研究

用两步固相反应法合成了单相的p型BayFeCo3Sb12化合物,并系统地研究了Ba不同填充分数对方钴矿化合物热电性能的影响:化合物载流子浓度强烈地依赖于填充原子的填充分数,随Ba填充分数y的增加,载流子浓度及电导率降低;塞贝克系数随温度T的上升而增加,比CoSb3的塞贝克系数有一定程度的提高,尤其是在中温部分有大幅度提高,得到的最大塞贝克系数由CoSb3的107μVK-1提高到Ba1.0FeCo3Sb12的235μVK-1晶格热导率随Ba的填充分数y的增加而进一步下降,Ba08FeCo3Sb12甚至降到2.2 Wm1K1;Ba08FeCo3Sb12化合物显示最大热电性能指数,在850K左右其最大无量纲热电性能指数ZT值达0.75.     

Non-stoichiometry in SnTe thin films and temperature instabilities of thermoelectric properties

The temperature dependences of the Seebeck coefficient and the electrical conductivity for (0 0 1)KCl/SnTe monocrystalline thin films with thicknesses d=20–600 nm were obtained in the range of 80–300 K. In contrast with SnTe bulk crystals, these dependences exhibited anomalies (plateaus, steps, bends). It is suggested that as temperature increases, the system passes through a number of intermediate states of quantum origin and/or corresponding to different distributions of non-stoichiometric defects (cation vacancies) over the crystal lattice. The observed effect is attributed to a high concentration of non-stoichiometric defects, which leads to the defect interaction stimulating their ordering, to loosening of the crystal lattice and to an increase in the diffusion rate. It is suggested that the observed temperature instabilities of properties are typical for other phases with high concentrations of non-stoichiometric defects.     

Ca_3Co_4O_9热电材料前驱体制备及性能表征

分别采用固相反应法和空间俘获法制备了Ca3Co4O9前驱体,并经冷等静压后常压烧结工艺制备了块体陶瓷样品。利用TG-DSC、XRD、SEM等方法对前驱体进行了表征,同时测试了陶瓷样品的热电性能。结果表明:空间俘获法可获得纯相、晶粒较小的前驱粉体,同时降低了合成温度,而且合成样品的Seebeck系数和功率因子明显高于固相反应法。在976 K获得最大Seebeck系数和功率因子分别为179μV/K、7.5×10–7 W/(cm·K2),较固相反应优化60%、16倍;电阻率略有升高。     

I-型硅基笼合物Ba8Ga16ZnxSi30-x的合成及电传输特性

用固相反应法结合熔融法合成Zn掺杂单相n型Ba8Ga16ZnxSi30-x化合物，探索Zn在Si位的取代对其结构及电传输特性的影响规律. 研究结果表明：x=1时化合物的平均键角畸变Δθ最大为4.4. ；当取代分数x＝0, 2, 4时，对应样品的电导率明显高于x＝1, 3时对应样品的电导率，在室温附近，Ba8Ga16Zn2Si28化合物表现出较高的电导率，约为3.0e5S/m，当x=1时，对应化合物的电导率在测试温度范围内最低；当取代分数x＝0, 2, 4时对应样品的Seebeck系数明显高于x＝1, 3时对应样品的Seebeck系数，且随着填充分数的增加，Seebeck系数分别逐渐降低；Ba8Ga16Zn2Si28化合物在测试温度范围内表现出较好的电性能，在1000K处具有最大的功率因子1.03e-3W/ (m·K2) .     

Low-Temperature Transport Properties of Sn<Subscript>24</Subscript>P<Subscript>19.3</Subscript>Br<Subscript>8</Subscript> and Sn<Subscript>17</Subscript>Zn<Subscript>7</Subscript>P<Subscript>22</Subscript>Br<Subscript>8</Subscript>

We report on temperature-dependent thermal conductivity, resistivity, and Seebeck coefficient of two polycrystalline Br-containing Sn-clathrate compounds with the type I crystal structure. Interstitial Br atoms reside inside the polyhedral cavities formed by the framework, resulting in hole conduction. The framework bonding directly influences the transport properties of these two compositions. The transport properties of these two clathrates are compared with those of other Sn-clathrates. We also discuss our results in terms of the potential for thermoelectric applications.     

Thermoelectric Properties of Co<Subscript>4</Subscript>Sb<Subscript>12</Subscript> Skutterudite Materials with Partial In Filling and Excess In Additions

The properties of Co₄Sb₁₂ with various In additions were studied. X-ray diffraction revealed the presence of the pure δ-phase of In_0.16Co₄Sb₁₂, whereas impurity phases (γ-CoSb₂ and InSb) appeared for x = 0.25, 0.40, 0.80, and 1.20. The homogeneity and morphology of the samples were observed by Seebeck microprobe and scanning electron microscopy, respectively. All the quenched ingots from which the studied samples were cut were inhomogeneous in the axial direction. The temperature dependence of the Seebeck coefficient (S), electrical conductivity (σ), and thermal conductivity (κ) was measured from room temperature up to 673 K. The Seebeck coefficient of all In-added Co₄Sb₁₂ materials was negative. When the filler concentration increases, the Seebeck coefficient decreases. The samples with In additions above the filling limit (x = 0.22) show an even lower Seebeck coefficient due to the formation of secondary phases: InSb and CoSb₂. The temperature variation of the electrical conductivity is semiconductor-like. The thermal conductivity of all the samples decreases with temperature. The central region of the In_0.4Co₄Sb₁₂ ingot shows the lowest thermal conductivity, probably due to the combined effect of (a) rattling due to maximum filling and (b) the presence of a small amount of fine-dispersed secondary phases at the grain boundaries. Thus, regardless of the non-single-phase morphology, a promising ZT (S ² σT/κ) value of 0.96 at 673 K has been obtained with an In addition above the filling limit.     

Thermoelectric Properties of TlCu3Te2 and TlCu2Te2

We performed thermoelectric characterizations on TlCu₃Te₂: (Tl¹⁺)(Cu¹⁺)₃ (Te²⁻)₂ and TlCu₂Te₂: (Tl¹⁺)(Tl³⁺)(Cu¹⁺)₄(Te²⁻)₄, in order to understand the relationship between the thermoelectric properties (especially the lattice thermal conductivity κ _lat) and the valence states of Tl. The thermal conductivity of TlCu₂Te₂ is high (about 8 W m⁻¹ K⁻¹), while that of TlCu₃Te₂ is extremely low (around 0.5 W m⁻¹ K⁻¹) like other thallium tellurides. This high κ of TlCu₂Te₂ was caused not only by its large electronic contribution but also by its intrinsically high κ _lat. The present study implies that the valence states of Tl would play some important roles in determining the magnitude of κ _lat.     

Effects of annealing on the thermoelectric and microstructural properties of deformed n-type Bi2Te3-based compounds

We studied the effects of deformation and annealing of n-type 90Bi₂Te₃-5Sb₂Te₃-5Sb₂Se₃ thermoelectric compound. Hot-extrusion was conducted to prepare the deformed compound and then this compound was annealed at 400°C for 1–24 hr. When the undoped cast-ingot was extruded, the compound was changed from p-type to n-type due to the electrons generated during the extrusion process. For the compound extruded with SbI₃-doped powders, the thermoelectric properties were also varied for the extrusion process. After annealing at 400°C more than 9 hr, the powder-extruded compound was recrystallized. This caused a decrease in carrier concentration and crystallographic anisotropy. In case of the compound extruded at the ratio of 10:1, the Seebeck coefficient α and the electrical resistivity ρ increased due to recrystallization. However, thermal conductivity κ of the compound decreased. This resulted in an increase in the figure-of-merit from 1.23 × 10⁻³ to 1.63 × 10⁻³ K⁻¹.     

Hydrothermal synthesis and photocatalytic properties of anatase TiO2 nanocrystals obtained from peroxytitanium complex precursor

This article describes a study of the influence of parameters of the hydrothermal synthesis on the structural characteristics and photocatalytic activity of the materials synthesized from peroxytitanium complex precursor. The materials were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning and transmission electron microscopy (SEM and TEM). The active oxidative species produced on the photocatalyst surface were investigated by measuring the fluorescence derived from their reaction with terephthalic acid (TPA). Also, the photocatalytic efficiency of the synthesized materials was assessed by monitoring the degradation of the methylene blue (MB) dye. The morphological characteristics and photocatalytic efficiency of the synthesized materials exhibited greater dependence on temperature than time of synthesis. The photocatalytic results show that the main factor for the effectiveness of the synthesized materials was crystallinity. Furthermore, it was observed that the photodegradation process occurred by the attack of active radicals on the MB molecules and not by the direct oxidation of adsorbed MB molecules on the photocatalyst surface.     

p型透明导电氧化物CuCrl-xMgxO2的制备及光电性能研究

采用溶胶-凝胶法制备了CuCr1-xMgO2粉末,压制烧结形成了CuCr1-xMgxO2陶瓷样品,研究了Mg2+掺杂量和压制压强对CuCrO2粉末和陶瓷的相组成、显微结构及光电性能的影响.结果表明:随着Mg2+掺杂量从0.01增加到0.07,所制CuCr1-xMgxO2粉末对紫外-可见光的吸收度增加,光学带隙宽度由3.25eV逐渐减小到2.86eV.随着Mg2+掺杂量或压制压强的增加,其相应陶瓷样品的电导率均先增大后减小.当Mg掺杂量x为0.03,压制压强为550 MPa时,制备的CuCr0.97Mg0.03O2陶瓷样品的电导率达到最大值,为19.8S/cm.     

High-pressure preparation and thermoelectric properties of Bi0.85Sb0.15

Nanocrystalline Bi_0.85Sb_0.15 powders were prepared by a novel mechanical alloying method. The bulk samples were formed by applying a pressure of 6 GPa at different pressing temperatures and times. Electrical conductivity, Seebeck coefficients, and thermal conductivity were measured in the temperature range 80–300 K. The Seebeck coefficient reaches a maximum value of −173 μV/K at 150 K. The largest figure of merit, 3.46 × 10⁻³ K⁻¹, achieved in this experiment is 50% higher than that of its single-crystal counterpart at 200 K.     

键合界面对面发射激光器的光、热性质影响

分析了采用双面键合长波长面发射激光器时,键合界面光吸收系数和电、热导率的变化对器件的光、热性质的影响。对于1λ光学腔的面发射激光器,键合界面吸收系数对器件光学性能影响较大,而对于1.5λ光学腔的面发射激光器,其光学性能基本不受键合界面吸收系数的影响。由有限元方法对面发射激光器的温度分布计算结果可知,当键合界面电、热导率小于GaAs电、热导率的1%时,激光器有源层的温度会有较大的上升。     

Thermal-lens and photo-acoustic methods for the determination of SiC thermal properties

In this paper we report the use of photothermal techniques such as Thermal lens (TL) spectrometry, Photoacoustic and heat capacity, ρc_p, to determine the thermo-optical parameters, such as thermal conductivity (K), thermal diffusivity (D), specific heat (c_p) and the optical path dependence with temperature (ds/dT), of an undoped polycrystalline 3C-SiC. To our knowledge, this is the first time that Thermal lens technique is used for wide band-gap systems. Results obtained for the polycrystalline sample with TL technique indicates that ds/dT is negative at room temperature. Moreover, the obtained values of thermal diffusivity and thermal conductivity are in good agreement with that found in the literature, indicating that the phototermal techniques can be used to obtain the referred parameters in circumstances where other techniques cannot be used, for example, in harsh environments.     

Correlation between microstructure and drastically reduced lattice thermal conductivity in bismuth telluride/bismuth nanocomposites for high thermoelectric figure of merit

The concept of nanocomposite/nanostructuring in thermoelectric materials has been proven to be an effective paradigm for optimizing the high thermoelectric performance primarily by reducing the thermal conductivity. In this work, we have studied the microstructure details of nanocomposites derived by incorporating a semi-metallic Bi nanoparticle phase in Bi₂Te₃ matrix and its correlation mainly with the reduction in the lattice thermal conductivity. Incorporating Bi inclusion in Bi₂Te₃ bulk thermoelectric material results in a substantial increase in the power factor and simultaneous reduction in the thermal conductivity. The main focus of this work is the correlation of the microstructure of the composite with the reduction in thermal conductivity. Thermal conductivity of the matrix and nanocomposites was derived from the thermal diffusivity measurements performed from room temperature to 150 °C. Interestingly, significant reduction in total thermal conductivity of the nanocomposite was achieved as compared to that of the matrix. A detailed analysis of high-resolution transmission electron microscope images reveals that this reduction in the thermal conductivity can be ascribed to the enhanced phonon scattering by distinct microstructure features such as interfaces, grain boundaries, edge dislocations with dipoles, and strain field domains.     

Progress on the controllable synthesis of all-inorganic halide perovskite nanocrystals and their optoelectronic applications

In the past five years,all-inorganic metal halide perovskite(CsPbX3,X=Cl,Br,I)nanocrystals have been intensely studied due to their outstanding optical properties and facile synthesis,which endow them with potential optoelectronic applications.In order to optimize their physical and chemical properties,different strategies have been developed to realize the controllable synthesis of CsPbX3 nanocrystals.In this short review,we firstly present a comprehensive and detailed summary of existed synthesis strategies of CsPbX3 nanocrystals and their analogues.Then,we introduce the regulations of several reaction parameters and their effects on the morphologies of CsPbX3 nanocrystals.At the same time,we provide stability improvement methods and representative applications.Finally,we propose the current challenges and future perspectives of the promising materials.     

The UV and blue light emission properties of Mn doped ZnO nanocrystals

We present a study of the light emission properties over wavelengths from UV to blue of Mn doped ZnO nanocrystals fabricated by means of a thermal evaporation vapor phase deposition process. The samples were grown with a Mn mole ratio in the Zn/Mn mixed source of 0% (pure ZnO sample, used as a reference), 5%, 10%, or 15% in a constant O₂/Ar gas mixture flowing at 500 °C. The pure ZnO nanocrystals exhibited a strong and predominantly UV emission peaking at 377 nm. In the photoluminescence spectra of mixed ZnO:Mn nanocrystals the major UV emission shifts from 377 to 408 nm, and a strong blue emission appears at 435 nm. The former is mainly induced by the impurity levels of Mn introduced in the band gap of the ZnO nanocrystals, while the latter is closely related to defect and Mn²⁺ ions. With increasing Mn concentration the blue emission is enhanced due to the strong exchange interaction in the short range spin system and the excess impurities on the surface. The results show that the optical properties of ZnO can be tuned by the doping concentration of Mn. Mn doped ZnO nanocrystals with strong blue emission can be used in the fabrication of blue light devices.     

Synthesis and optical properties of cubic Co3O4 nanoparticles via thermal treatment of a trinuclear cobalt complex

Cubic cobalt oxide nanoparticles with the formula of Co₃O₄ were synthesized via thermal treatment in air, using [Co^II{(µ-L)(µ-OAc)Co^III(NCS)}₂]; [H₂L=salen=1,6-bis(2-hydroxyphenyl)-2,5-diazahexa-1,5-diene]; as precursor. Effect of calcination temperature and citric acid, as emulsifier, was investigated on the phase formation and particle size distribution of the products. Calcination of the precursor at 600 °C in the presence of citric acid results in the formation of Co₃O₄ nanoparticles with the average crystallite size of ∼13 nm. The presence of citric acid provides conditions for the formation of more pure Co₃O₄ crystalline phase with smaller particles. The as-prepared nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), particle size analyzer (PSA), transmission electron microscopy (TEM), UV–vis and Photoluminescence (PL) spectroscopies. The optical property studies indicate that the absorption peaks of Co₃O₄ nanoparticles, prepared in the presence of citric acid, shift towards short wavelengths. This blueshift is related to the quantum size effect.     

Green synthesis of multifunctional zinc oxide (ZnO) nanoparticles using Cassia fistula plant extract and their photodegradative,antioxidant and antibacterial activities

The present study involves green synthesis of ZnO nanoparticles (Nps) using aqueous Cassia fistula plant extract as fuel by solution combustion synthesis. The ZnO Nps were characterized by Powder X- ray diffraction (PXRD), UV–visible studies and Transmission electron microscopy (TEM). The Nps were evaluated for photodegradative, antimicrobial and antioxidant activities. The extract was found to contain reducing components such as polyphenols (11%) and flavonoids (12.5%). The Nps were found to have a hexagonal wurtzite structure. UV–visible absorption of ZnO Nps showed absorption band at 370 nm which can be assigned to the intrinsic band-gap absorption of ZnO due to the electron transitions from the valence band to the conduction band. TEM image confirms the formation of nanoparticles and the average crystallite sizes were found to be ~5–15 nm. Methylene blue (MB) dye was effectively degraded under UV and Sun light illumination in the presence of ZnO Nps. Significant antioxidant activity was exhibited by Nps through scavenging of 1, 1-Diphenyl-2-picrylhydrazyl (DPPH) free radicals. Excellent bactericidal activity was shown by the Nps on Klebsiella aerogenes, Escherichia coli, Plasmodium desmolyticum and Staphylococcus aureus. Synthesis of multifunctional ZnO Nps using naturally occurring plant products has been advocated as a possible environment friendly alternative to chemical methods.     

Facile and rapid production of conductive flexible films by deposition of polythiophene nanoparticles on transparent poly(ethyleneterephthalate): Electrical and morphological properties

In this work, polythiophene (PTh) nanoparticles were successfully deposited on poly(ethyleneterephthalate) (PET) substrate as thin film by a facile and rapid chemical oxidative deposition method using a binary organic solvent system in the presence of N-cetyl-N,N,N-trimethylammonium bromide (CTAB) as cationic surfactant. The electrical conductivity of PTh nanoparticles deposited on PET was optimized by adjusting the surfactant/oxidant/monomer molar ratio, monomer concentration and time of polymerization. Resulted film was conductive, transparent and flexible which can be used in electronic devices such as OLEDs. Electrical conductivity for the un-doped deposited PTh nanoparticles at oxidant/monomer molar ratio of 5:1 at 0 °C polymerized for 12 min was measured to be 1.18×10⁻² S/cm. The effect of oxidant and monomer concentration on polymerization yield was also investigated. The structural confirmation and transparency of the PTh nanoparticle coated PET films were characterized by FTIR and UV–vis spectroscopy, respectively. Field emission scanning electron microscopy (FESEM), laser particle size analysis and transmission electron microscopy (TEM) were employed for surface morphology and size distribution measurements of PTh nanoparticles. The results showed that the PTh nanoparticles are deposited as globular aggregates with average size of about 50 nm on PET.