First-Principles Study of the Electronic Structure and Thermoelectric Properties of Al-Doped ZnO

ZnO materials doped with elements such as Al, Ga, etc. are of great interest for high-temperature thermoelectric applications. In this work, the effects of Al doping on the electronic structure and thermoelectric properties of the ZnO system are presented. The energy band structure and density of states of Al-doped ZnO were investigated using the projector-augmented plane wave pseudopotential method within the local density approximation. The calculated energy band structure was then used in combination with the Boltzmann transport equation to calculate the thermoelectric parameters of Al-doped ZnO. The electronic structure calculation showed that the position of the Fermi level of the doped sample was shifted to a higher energy level compared with the undoped material. The conduction band near the Fermi energy was a combination of hybridized Zn sp-orbitals and Al s-orbital. The calculated thermoelectric properties were compared with the experimental results, showing some agreement. For the Al-doped ZnO system, the Seebeck coefficient was shown to be negative and its absolute value increased with temperature. The electrical conductivity and electronic thermal conductivity followed the trend of the experimental results.     

Solid-State Synthesis and Thermoelectric Properties of Al-Doped Mg2Si

The electronic transport and thermoelectric properties of Al-doped Mg₂Si (Mg₂Si:Al _m , m?=?0, 0.005, 0.01, 0.02, 0.03) compounds prepared by solid-state synthesis were examined. Mg₂Si was synthesized by solid-state reaction (SSR) at 773?K for 6?h, and Al-doped Mg₂Si powders were obtained by mechanical alloying (MA) for 24?h. Mg₂Si:Al _m were fully consolidated by hot pressing (HP) at 1073?K for 1?h, and all samples showed n-type conduction, indicating that the electrical conduction is due mainly to electrons. The electrical conductivity increased significantly with increasing Al doping content, and the absolute value of the Seebeck coefficient decreased due to the significant increase in electron concentration from 10¹⁶ cm^?3 to 10¹⁹ cm^?3 by Al doping. The thermal conductivity was increased slightly by Al doping, but was not changed significantly by the Al doping content due to the much larger contribution of lattice thermal conductivity over electronic thermal conductivity. Mg₂Si:Al_0.02 showed a maximum thermoelectric figure of merit of 0.47 at 823?K.     

Theoretical and experimental investigations of the thermoelectric properties of Al-, Bi- and Sn-doped ZnO

In this paper, the thermoelectric properties of ZnO doped with Al, Bi and Sn were investigated by combining experimental and theoretical methods. The average Seebeck coefficient of Bi doped ZnO over the measured temperature range is improved from −90 to −497 μV/K. However, segregation of Bi₂O₃ in ZnO:Bi sample, confirmed by FESEM, lead to enormous grain growth and low electrical conductivity, which makes Bi is not a good dopant to improve ZT value of ZnO. As a 4+ valence cation, Sn doping actually show an increase in carrier concentration to 10²⁰ cm⁻³, further enhancing the electrical conductivity. Unfortunately, the Seebeck coefficient of ZnO:Sn samples is even lower than pure ZnO sample, which lead to a low ZT value. As for ZnO:Al sample, with nearly no change in lattice thermal conductivity, electrical conductivity and Seebeck coefficient were both enhanced. Threefold enhancement in ZT value has been achieved in ZnO:Al sample at 760 °C compared with pure ZnO.     

Thermoelectric Properties and Electronic Structure of Bi- and Ag-Doped Mg<Subscript>2</Subscript>Si<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Compounds

Mg₂Si_1−x Ge _x compounds were prepared from pure elements by melting in tantalum crucibles. The reaction was conducted under an inert gas in a special laboratory setup. Samples for thermoelectric measurements were formed by hot pressing. Structure and phase composition of the obtained materials were investigated by x-ray diffraction (XRD). Morphology and chemical composition were examined by scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy (EDS), respectively. Thermoelectric properties, i.e., the Seebeck coefficient, the electrical conductivity, and the thermal conductivity, were measured in the temperature range of 500 K to 900 K. The effect of Bi and Ag doping on the thermoelectric performance of Mg-Si-Ge ternary compounds was investigated. The electronic structures of binary compounds were calculated using the Korringa–Kohn–Rostoker (KKR) method. The effects of disorder, including Ge substitution and Bi or Ag doping, were accounted for in the KKR method with coherent potential approximation calculations. The thermoelectric properties of doped Mg₂Si_1−x Ge _x are discussed with reference to computed density of states as well as the complex energy band structure.     

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.     

Structural and optical properties of (Al,K)-co-doped ZnO thin films deposited by a sol–gel technique

Thin films of Al-doped ZnO (AZO) and (Al, K)-co-doped ZnO (AKZO) were synthesized by sol–gel spin coating and their structural and optical properties were investigated. All the films had a preferential orientation in which the c-axis was perpendicular to the substrate. The optical bandgap increased after Al doping, but decreased after K doping at a given Al doping concentration. UV emission and a broad visible emission band were observed in photoluminescence (PL) spectra. The intensity of both emission bands decreased after Al and K co-doping. PL excitation (PLE) spectra of the blue emission band indicate that the initial state is possibly the same for all the samples and a similar case occurs for the orange–red emission band. The green emission can be attributed to electronic transitions involving oxygen vacancies. A possible process for the orange–red emission of the thin films is radiative recombination of an electron trapped in a zinc interstitial defect with a hole deeply trapped in interstitial oxygen.     

Solid-State Synthesis of Te-Doped Mg<Subscript>2</Subscript>Si

Te-doped Mg₂Si (Mg₂Si:Te _m , m = 0, 0.01, 0.02, 0.03, 0.05) alloys were synthesized by a solid-state reaction and mechanical alloying. The electronic transport properties (Hall coefficient, carrier concentration, and mobility) and thermoelectric properties (Seebeck coefficient, electrical conductivity, thermal conductivity, and figure of merit) were examined. Mg₂Si was synthesized successfully by a solid-state reaction at 673 K for 6 h, and Te-doped Mg₂Si powders were obtained by mechanical alloying for 24 h. The alloys were fully consolidated by hot-pressing at 1073 K for 1 h. All the Mg₂Si:Te _m samples showed n-type conduction, indicating that the electrical conduction is due mainly to electrons. The electrical conductivity increased and the absolute value of the Seebeck coefficient decreased with increasing Te content, because Te doping increased the electron concentration considerably from 10¹⁶ cm⁻³ to 10¹⁸ cm⁻³. The thermal conductivity did not change significantly on Te doping, due to the much larger contribution of lattice thermal conductivity over the electronic thermal conductivity. Thermal conduction in Te-doped Mg₂Si was due primarily to lattice vibrations (phonons). The thermoelectric figure of merit of intrinsic Mg₂Si was improved by Te doping.     

Thermoelectric Properties of Ca-Filled CoSb<Subscript>3</Subscript>-Based Skutterudites Synthesized by Mechanical Alloying

Ca _z Co_4−x (Fe/Mn) _x Sb₁₂ skutterudites were prepared by mechanical alloying and hot pressing. The phases of mechanically alloyed powders were identified as γ-CoSb₂ and Sb, but they were transformed to δ-CoSb₃ by annealing at 873 K for 100 h. All specimens had a positive Hall coefficient and Seebeck coefficient, indicating p-type conduction by holes as majority carriers. For the binary CoSb₃, the electrical conductivity behaved like a nondegenerate semiconductor, but Ca-filled and Fe/Mn-doped CoSb₃ showed a temperature dependence of a degenerate semiconductor. While the Seebeck coefficient of intrinsic CoSb₃ increased with temperature and reached a maximum at 623 K, the Seebeck coefficient increased with increasing temperature for the Ca-filled and Fe/Mn-doped specimens. Relatively low thermal conductivity was obtained because fine particles prepared by mechanical alloying lead to phonon scattering. The thermal conductivity was reduced by Ca filling and Fe/Mn doping. The electronic thermal conductivity was increased by Fe/Mn doping, but the lattice thermal conductivity was decreased by Ca filling. Reasonable thermoelectric figure-of-merit values were obtained for Ca-filled Co-rich p-type skutterudites.     

Synthesis and Thermoelectric Properties of InzCo4?xFexSb12 Skutterudites

The thermoelectric properties of In-filled and Fe-doped CoSb₃ (In _z Co_4−x - Fe _x Sb₁₂) skutterudites prepared by encapsulated induction melting were examined. A single δ-phase was obtained successfully by subsequent annealing at 823 K for 120 h. The Hall and Seebeck coefficients of the In _z Co_4−x Fe _x Sb₁₂ samples had positive signs, indicating p-type conduction. The electrical conductivity was increased by Fe doping, and the thermal conductivity was decreased by In filling due to phonon scattering. The thermoelectric properties were improved by In filling and Fe doping, and were closely related to the optimum carrier concentration and phonon scattering.     

A Theoretical Search for Efficient Dopants in Mg<Subscript>2</Subscript>X (X = Si,Ge, Sn) Thermoelectric Materials

Intentional alloying and doping are well-established ways of improving the thermoelectric properties of Mg₂X (X = Si, Ge, Sn). In this study the results of electronic structure calculations for alloying and impurity dilution are presented. We have adapted the fully self-consistent Korringa–Kohn–Rostoker method with the coherent potential approximation (KKR-CPA) to treat various types of chemical disorders and to calculate an electronic band structure with complex energy. In Mg₂Si_1−x Sn _x , as the Sn content increases, the conduction and valence bands near the Fermi energy tend to overlap but do not cross each other. In contrast, in Mg₂Si_1−x Ge _x , an energy gap was detected for 0 ≤ x ≤ 1. Moreover, the site preference of selected impurities (Al, P, Zn, Ga, Ag, Cd, In, Sb) in Mg₂Si is discussed in view of total energy calculations. It was found that In, Cd, Ag, and Zn preferentially occupy the Mg site, whereas in other cases site selectivity markedly depends on impurity amount as well as chemical potentials. The sign of the thermopower in the doped systems is analyzed from the position of the Fermi level with respect to valence/conduction band edges. The Seebeck coefficient was estimated from the simplified Mott formula at standard dopant concentrations, diluted at both crystallographic sites in Mg₂Si.     

Low-Temperature Thermoelectric Properties of Fe2VAl with Partial Cobalt Doping

Ternary metallic alloy Fe₂VAl with a pseudogap in its energy band structure has received intensive scrutiny for potential thermoelectric applications. Due to the sharp change in the density of states profile near the Fermi level, interesting transport properties can be triggered to render possible enhancement in the overall thermoelectric performance. Previously, this full-Heusler-type alloy was partially doped with cobalt at the iron sites to produce a series of compounds with n-type conductivity. Their thermoelectric properties in the temperature range of 300?K to 850?K were reported. In this research, efforts were made to extend the investigation on (Fe_1?x Co _x )₂VAl to the low-temperature range. Alloy samples were prepared by arc-melting and annealing. Seebeck coefficient, electrical resistivity, and thermal conductivity measurements were performed from 80?K to room temperature. The effects of cobalt doping on the material??s electronic and thermal properties are discussed.     

Enhanced Thermoelectric Performance in GeTe by Synergy of Midgap state and Band Convergence

The good co-existence of midgap state and valence band degeneracy is realized in Bi-alloyed GeTe through the In-Cd codoping to play different but complementary roles in the valence band structure modification. In doping induces midgap state and results in a considerably improved Seebeck coefficient near room temperature, while Cd doping significantly increases the Seebeck coefficient in the mid-high temperature region by promoting the valence band convergence. The synergistic effects obviously increase the density of state effective mass from 1.39 to 2.65 m₀, and the corresponding carrier mobility still reaches 34.3 cm² V⁻¹ s⁻¹ at room temperature. Moreover, the Bi-In-Cd co-alloying introduces various phonon scattering centers including nanoprecipitates and strain field fluctuations and suppresses the lattice thermal conductivity to a rather low value of 0.56 W m⁻¹ K⁻¹ at 600 K. As a result, the Ge_0.89Bi_0.06In_0.01Cd_0.04Te sample obtains excellent thermoelectric properties of zT_max ≈2.12 at 650 K and zT_avg ≈1.43 between 300 and 773 K. This study illustrates that the thermoelectric performance of GeTe can be optimized in a wide temperature range through the synergy of midgap state and valence band convergence.     

Vacancy Manipulation Induced Optimal Carrier Concentration,Band Convergence and Low Lattice Thermal Conductivity in Nano-Crystalline SnTe Yielding Superior Thermoelectric Performance

Synergetic optimization of electrical and thermal transport properties is achieved for SnTe-based nano-crystalline materials. Gd doping is able to suppress the Sn vacancy, which is confirmed by positron annihilation measurements and corresponding theoretical calculations. Hence, the optimal hole carrier concentration is obtained, leading to the improvement of electrical transport performance and simultaneous decrease of electronic thermal conductivity. In addition, the incremental density of states effective mass m* in SnTe is realized by the promotion of the band convergence via Gd doping, which is further confirmed by the band structure calculation. Hence, the enhancement of the Seebeck coefficient is also achieved, leading to a high power factor of 2922 µW m⁻¹ K⁻² for Sn_0.96Gd_0.04Te at 900 K. Meanwhile, substantial suppression of the lattice thermal conductivity is observed in Gd-doped SnTe, which is originated from enhanced phonon scattering by multiple processes including mass and strain fluctuations due to the Gd doping, scattering of grain boundaries, nano-pores, and secondary phases induced by Gd doping. With the decreased phonon mean free path and reduced average phonon group velocity, a rather low lattice thermal conductivity is achieved. As a result, the synergetic optimization of the electric and thermal transport properties contributes to a rather high ZT value of ≈1.5 at 900 K, leading to the superior thermoelectric performance of SnTe-based nanoscale polycrystalline materials.     

Thermoelectric Oxides: Effect of Doping in Delafossites and Zinc Oxide

The electrical resistivity (ρ) and Seebeck coefficient (S) of the three delafossites CuFe_0.9Cr_0.1O₂, CuCr_0.98Mg_0.02O₂, and CuRh_0.9Mg_0.1O₂ have been measured and their power factor (PF) calculated. These p-type oxides show PF values at 800 K from 1.4 × 10⁻⁴ W K⁻² m⁻¹ to 6.9 × 10⁻⁴ W K⁻² m⁻¹. In contrast to delafossites containing Fe or Cr, for which ρ exhibits a regime, the Rh-based delafossite shows a metallic regime from 5 K to 1000 K. This points toward the role of the transition-metal electronic configuration in the transport properties. Otherwise, similar PF values are obtained in the case of the n-type Al-doped ZnO. For these oxides, the ρ and PF values are minimum and maximum, respectively, for x = 0.01. However, the presence of spinel impurities even for x = 0.01 in Zn_1−x Al _x O or for x = 0.02 in CuCr_1−x Mg _x O₂ calls into question the role of the doping element in the physical properties. This should motivate a deeper insight into the physics of thermoelectric oxides.     

Preparation and Thermoelectric Properties of p-Type Yb-Filled Skutterudites

p-Type Yb _z Fe_4?x Co _x Sb₁₂ skutterudites were prepared by encapsulated melting and hot pressing, and the filling and doping (charge compensation) effects on the transport and thermoelectric properties were examined. The electrical conductivity of all specimens decreased slightly with increasing temperature, indicating that they were in a degenerate state due to high carrier concentrations of 10²⁰ cm^?3 to 10²¹ cm^?3. The Hall and Seebeck coefficients exhibited positive signs, indicating that the majority carriers are holes (p-type). The Seebeck coefficient increased with increasing temperature to maximum values of 100 μV/K to 150 μV/K at 823 K. The electrical and thermal conductivities were reduced by substitution of Co for Fe, which was responsible for the decreased carrier concentration. Overall, the Yb-filled Fe-rich skutterudites showed better thermoelectric performance than the Yb-filled Co-rich skutterudites.     

Improved Thermoelectric Properties of Al-Doped Higher Manganese Silicide Prepared by a Rapid Solidification Method

Polycrystalline higher manganese silicides (HMS) Mn(Al _x Si_1−x )_1.80 (x = 0 to 0.009) were prepared by a rapid melt-spinning process combined with a spark plasma sintering method (MS-SPS). The phase composition, microstructure, and thermoelectric properties of the bulk samples were investigated. X-ray diffraction (XRD) patterns showed that all samples possessed the HMS structure, but minor amounts of the MnSi phase could be observed from the backscattered electron images. When the Al content did not exceed the solid solubility limit, the electrical conductivity of Al-doped HMS increased dramatically, and the thermal conductivity decreased, as a result of the enhancement of phonon scattering due to an increased number of defects. In addition, the maximum ZT value of 0.65 was obtained at 850 K for the sample with x = 0.0015, whereas further increase in the Al content (x > 0.0015) significantly deteriorated the thermoelectric properties, mainly because the Al content exceeded its solid solubility limit in HMS.     

Zintl Phases as Thermoelectric Materials: Tuned Transport Properties of the Compounds CaxYb1–xZn2Sb2

Zintl phases are ideal candidates for efficient thermoelectric materials, because they are typically small‐bandgap semiconductors with complex structures. Furthermore, such phases allow fine adjustment of dopant concentration without disrupting electronic mobility, which is essential for optimizing thermoelectric material efficiency. The tunability of Zintl phases is demonstrated with the series Ca_xYb_1–xZn₂Sb₂ (0 ≤ x ≤ 1). Measurements of the electrical conductivity, Hall mobility, Seebeck coefficient, and thermal conductivity (in the 300–800 K temperature range) show the compounds to behave as heavily doped semiconductors, with transport properties that can be systematically regulated by varying x. Within this series, x = 0 is the most metallic (lowest electrical resistivity, lowest Seebeck coefficient, and highest carrier concentration), and x = 1 is the most semiconducting (highest electrical resistivity, highest Seebeck coefficient, and lowest carrier concentration), while the mobility is largely independent of x. In addition, the structural disorder generated by the incorporation of multiple cations lowers the overall thermal conductivity significantly at intermediate compositions, increasing the thermoelectric figure of merit, zT. Thus, both zT and the thermoelectric compatibility factor (like zT, a composite function of the transport properties) can be finely tuned to allow optimization of efficiency in a thermoelectric device.     

Influence of Thermal Aging Phenomena on Thermoelectric Properties of Al-Substituted ZnO

The thermoelectric properties and stability of Al-substituted ZnO as a potential high-temperature n-type material were studied in heating?Ccooling cycles. Zn_1?x Al _x O (x?=?0.02, 0.06) was prepared by soft chemistry and solid-state reaction synthesis methods. Cycling during the thermoelectric measurement leads to an increase of the electrical resistivity and Seebeck coefficient values. The reason for this aging phenomenon can be assigned to a change in composition due to oxygen uptake along with modification in the defect concentrations. The aging is enhanced if the cycling is performed in oxygen. ZT value of 0.21 is reached at 1275?K for samples with 2% Al substitution made by soft chemistry synthesis.     

Thin-Film Thermoelectric Module for Power Generator Applications Using a Screen-Printing Method

A new process for fabricating a low-cost thermoelectric module using a screen-printing method has been developed. Thermoelectric properties of screen-printed ZnSb films were investigated in an effort to develop a thermoelectric module with low cost per watt. The screen-printed Zn _x Sb_1−x films showed a low carrier concentration and high Seebeck coefficient when x was in the range of 0.5 to 0.57 and the annealing temperature was kept below 550°C. When the annealing temperature was higher than 550°C, the carrier concentration of the Zn _x Sb_1−x films reached that of a metal, leading to a decrease of the Seebeck coefficient. In the present experiment, the optimized carrier concentration of screen-printed ZnSb was 7 × 10¹⁸/cm³. The output voltage and power density of the ZnSb film were 10 mV and 0.17 mW/cm², respectively, at ΔT = 50 K. A thermoelectric module was produced using the proposed screen-printing approach with ZnSb and CoSb₃ as p-type and n-type thermoelectric materials, respectively, and copper as the pad metal.     

On Intensifying Carrier Impurity Scattering to Enhance Thermoelectric Performance in Cr‐Doped CeyCo4Sb12

The beneficial effect of impurity scattering on thermoelectric properties has long been disregarded even though possible improvements in power factor have been suggested by Ioffe more than a half century ago. Here it is theoretically and experimentally demonstrated that proper intensification of ionized impurity scattering to charge carriers can benefit the thermoelectric figure of merit (ZT) by increasing the Seebeck coefficient and decreasing the electronic thermal conductivity. The optimal strength of ionized impurity scattering for maximum ZT depends on the Fermi level and the density of states effective mass. Cr‐doping in Ce_yCo₄Sb₁₂ progressively increases the strength of ionized impurity scattering, and significantly improves the Seebeck coefficient, resulting in high power factors of 45 μW cm^?1 K^?2 with relatively low electrical conductivity. This effect, combined with the increased Ce‐filling fraction and thus decreased lattice thermal conductivity by charge compensation of Cr‐dopant, gives rise to a maximum ZT of 1.3 at 800 K and a large average ZT of 1.1 between 500 and 850 K, ≈30% and ≈20% enhancements as compared with those of Cr‐free sample, respectively. Furthermore, this study also reveals that carrier scattering parameter can be another fundamental degree of freedom to optimize electrical properties and improve thermal‐to‐electricity conversion efficiencies of thermoelectric materials.