An Update Review on N-Type Layered Oxyselenide Thermoelectric Materials

Compared with traditional thermoelectric materials, layered oxyselenide thermoelectric materials consist of nontoxic and lower-cost elements and have better chemical and thermal stability. Recently, several studies on n-type layered oxyselenide thermoelectric materials, including BiCuSeO, Bi₂O₂Se and Bi₆Cu₂Se₄O₆, were reported, which stimulates us to comprehensively summarize these researches. In this short review, we begin with various attempts to realize an n-type BiCuSeO system. Then, we summarize several methods to optimize the thermoelectric performance of Bi₂O₂Se, including carrier engineering, band engineering, microstructure design, et al. Next, we introduce a new type of layered oxyselenide Bi₆Cu₂Se₄O₆, and n-type transport properties can be obtained through halogen doping. At last, we propose some possible research directions for n-type layered oxyselenide thermoelectric materials.     

Influence of Doping on the Topological Surface States of Crystalline Bi2Se3 Topological Insulators

We present STM/STS, ARPES and magnetotransport studies of the surface topography and electronic structure of pristine Bi₂Se₃ in comparison to Bi_1.96Mg_0.04Se₃ and Bi_1.98Fe_0.02Se₃. The topography images reveal a large number of complex, triangle-shaped defects at the surface. The local electronic structure of both the defected and non-defected regions is examined by STS. The defect-related states shift together with the Dirac point observed in the undefected area, suggesting that the local electronic structure at the defects is influenced by doping in the same way as the electronic structure of the undefected surface. Additional information about the electronic structure of the samples is provided by ARPES, which reveals the dependence of the bulk and surface electronic bands on doping, including such parameters as the Fermi wave vector. The subtle changes of the surface electronic structure by doping are verified with magneto-transport measurements at low temperatures (200 mK) allowing the detection of Shubnikov-de Haas (SdH) quantum oscillations.     

Thermoelectric Properties of Cu2Te Nanoparticle Incorporated N-Type Bi2Te2.7Se0.3

To develop highly efficient thermoelectric materials, the generation of homogeneous heterostructures in a matrix is considered to mitigate the interdependency of the thermoelectric compartments. In this study, Cu₂Te nanoparticles were introduced onto Bi₂Te_2.7Se_0.3 n-type materials and their thermoelectric properties were investigated in terms of the amount of Cu₂Te nanoparticles. A homogeneous dispersion of Cu₂Te nanoparticles was obtained up to 0.4 wt.% Cu₂Te, whereas the Cu₂Te nanoparticles tended to agglomerate with each other at greater than 0.6 wt.% Cu₂Te. The highest power factor was obtained under the optimal dispersion conditions (0.4 wt.% Cu₂Te incorporation), which was considered to originate from the potential barrier on the interface between Cu₂Te and Bi₂Te_2.7Se_0.3. The Cu₂Te incorporation also reduced the lattice thermal conductivity, and the dimensionless figure of merit ZT was increased to 0.75 at 374 K for 0.4 wt.% Cu₂Te incorporation compared with that of 0.65 at 425 K for pristine Bi₂Te_2.7Se_0.3. This approach could also be an effective means of controlling the temperature dependence of ZT, which could be modulated against target applications.     

The Effect of Niobium Doping on the Electrical Properties of 0.4(Bi0.5K0.5)TiO3-0.6BiFeO3 Lead-Free Piezoelectric Ceramics

Ceramics in the system (Bi_0.5K_0.5)TiO₃-BiFeO₃ have good electromechanical properties and temperature stability. However, the high conductivity inherent in BiFeO₃-based ceramics complicates measurement of the ferroelectric properties. In the present work, doping with niobium (Nb) is carried out to reduce the conductivity of (Bi_0.5K_0.5)TiO₃-BiFeO₃. Powders of composition 0.4(K_0.5Bi_0.5)Ti_1−xNb_xO₃-0.6BiFe_1−xNb_xO₃ (x = 0, 0.01 and 0.03) are prepared by the mixed oxide method and sintered at 1050 °C for 1 h. The effect of Nb doping on the structure is examined by X-ray diffraction. The microstructure is examined by scanning electron microscopy. The variation in relative permittivity with temperature is measured using an impedance analyzer. Ferroelectric properties are measured at room temperature using a Sawyer Tower circuit. Piezoelectric properties are measured using a d₃₃ meter and a contact type displacement sensor. All the samples have high density, a rhombohedral unit cell and equiaxed, micron-sized grains. All the samples show relaxor-like behavior. Nb doping causes a reduction in conductivity by one to two orders of magnitude at 200 °C. The samples have narrow P-E loops reminiscent of a linear dielectric. The samples all possess bipolar butterfly S-E loops characteristic of a classic ferroelectric material. Nb doping causes a decrease in d₃₃ and S_max/E_max.     

Fe-Doping Effect on Thermoelectric Properties of p-Type Bi0.48Sb1.52Te3

The substitutional doping approach has been shown to be an effective strategy to improve ZT of Bi₂Te₃-based thermoelectric raw materials. We herein report the Fe-doping effects on electronic and thermal transport properties of polycrystalline bulks of p-type Bi_0.48Sb_1.52Te₃. After a small amount of Fe-doping on Bi/Sb-sites, the power factor could be enhanced due to the optimization of carrier concentration. Additionally, lattice thermal conductivity was reduced by the intensified point-defect phonon scattering originating from the mass difference between the host atoms (Bi/Sb) and dopants (Fe). An enhanced ZT of 1.09 at 300 K was obtained in 1.0 at% Fe-doped Bi_0.48Sb_1.52Te₃ by these synergetic effects.     

Synthesis,Characterization, and Photocatalytic Activity of Ba-Doped BiFeO3 Thin Films

In the present paper, Bi_1−xBa_xFeO₃ (BBFO) thin films (where x = 0, 0.02 and 0.05) were prepared by a combined sol-gel and spin-coating method. The influence of Ba substitutions on the structural, microstructural, optical properties, and photocatalytic activity of BiFeO₃ thin films has been studied. X-ray diffraction pattern correlated with FTIR analysis results confirms that all the films have a perovskite structure of rhombohedral symmetry with an R3m space group. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to investigate the surface morphology and reveals microstructural modifications with the increase in Ba concentration. The optical properties show that the band gap is narrowed after doping with Ba ions and decreases gradually with the increase of doping content. The photocatalytic investigations of deposited films revealed that Ba doping of BFO material leads to the enhancement of photocatalytic response. The present data demonstrates that Bi_1−xBa_xFeO₃ (BBFO) thin films can be used in photocatalytic applications.     

Syntheses and Characterizations of CuIn1-xZnxSe2 Chalcopyrite Nanoparticles

CuIn_1-xZn_xSe₂ powders with various atomic percentages (x = 0, 0.05, 0.11, 0.16 and 0.21) were synthesized with the solvothermal method using metal chlorides and ethylendiamine as sources of precursors and a solvent, respectively. The experiment aims to investigate the effect of atomic percentages of Zn_x compounds on the structural and optical properties of CuIn_1-xZn_xSe₂ in order to improve future technological applications based on this material. The powders’ chalcopyrite phases were identified by X-ray diffraction. Energy dispersive X-ray spectroscopy analysis revealed the presence of Cu, In, Zn and Se with the expected atomic ratio of Zn/(In + Zn). Scanning electron microscopy and transmission electron microscopy analysis showed that the powders have large-scale desert rose-like structures. The nanopowders’ optical study by UV-visible spectrophotometry showed that the CuIn_1-xZn_xSe₂ energy gap values increase with the molar fraction of Zn_x. A change from 1.15 to 1.4 eV was observed.     

Photothermal Killing of A549 Cells and Autophagy Induction by Bismuth Selenide Particles

With a highly efficient optical absorption capability, bismuth selenide (Bi₂Se₃) can be used as an outstanding photothermal agent for anti-tumor treatment and shows promise in the field of nanotechnology-based biomedicine. However, little research has been completed on the relevant mechanism underlying the photothermal killing effect of Bi₂Se₃. Herein, the photothermal effects of Bi₂Se₃ particles on A549 cells were explored with emphasis put on autophagy. First, we characterized the structure and physicochemical property of the synthesized Bi₂Se₃ and confirmed their excellent photothermal conversion efficiency (35.72%), photostability, biocompatibility and ability of photothermal killing on A549 cells. Enhanced autophagy was detected in Bi₂Se₃-exposed cells under an 808 nm laser. Consistently, an elevated expression ratio of microtubule-associated protein 1 light chain 3-II (LC3-II) to LC3-I, a marker of autophagy occurrence, was induced in Bi₂Se₃-exposed cells upon near infrared (NIR) irradiation. Meanwhile, the expression of cleaved-PARP was increased in the irradiated cells dependently on the exposure concentrations of Bi₂Se₃ particles. Pharmacological inhibition of autophagy by 3-methyladenine (3-MA) further strengthened the photothermal killing effect of Bi₂Se₃. Meanwhile, stress-related signaling pathways, including p38 and stress activated protein kinase/c-Jun N-terminal kinase (SAPK/JNK), were activated, coupled with the attenuated PI3K/Akt signaling. Our study finds that autophagy and the activation of stress-related signaling pathways are involved in the photothermal killing of cancerous cells by Bi₂Se₃, which provides a more understanding of photothermal materials.     

Raman Spectroscopy of Two-Dimensional Bi2TexSe3 ? x Platelets Produced by Solvothermal Method

In this paper, we report a facile solvothermal method to produce both binary and ternary compounds of bismuth chalcogenides in the form of Bi₂Te_xSe_{3 − x}. The crystal morphology in terms of geometry and thickness as well as the stoichiometric ratio can be well controlled, which offers the opportunities to systematically investigate the relationship between microstructure and phonon scattering by Raman spectroscopy. Raman spectra of four compounds, i.e., Bi₂Se₃, Bi₂Se₂Te, Bi₂SeTe₂ and Bi₂Te₃, were collected at four different excitation photon energies (2.54, 2.41, 1.96, and 1.58 eV). It is found that the vibrational modes are shifted to higher frequency with more Se incorporation towards the replacement of Te. The dependence of Raman vibrational modes on excitation photon energy was investigated. As the excitation photon energy increases, three Raman vibrational modes (A_1g¹, E_g² and A_1g²) of the as-produced compounds move to low frequency. Three Infrared-active (IR-active) modes were observed in thin topological insulators (TIs) crystals.     

Understanding the Effect of Introducing Micro- and Nanoparticle Bismuth Oxide (Bi2O3) on the Gamma Ray Shielding Performance of Novel Concrete

The aim of this study is to investigate the radiation shielding properties of novel concrete samples with bulk Bi₂O₃ and Bi₂O₃ nanoparticles (Bi₂O₃ NP) incorporated into its composition. The mass attenuation coefficient of the concrete samples without Bi₂O₃ and with 5 and 7 wt% bulk Bi₂O₃ were experimentally determined and were compared against values obtained using the XCOM and Geant4 simulations. Both methods greatly agree with the experimental values. The linear attenuation coefficients (LAC) of blank concrete (C-0), concrete with 5% bulk Bi₂O₃ (C-B5), and concrete with 5% nanoparticle Bi₂O₃ (C-N5) were determined and compared at a wide energy range. We found that the LAC follows the trend of C-0 < C-B5 < C-N5 at all the tested energies. Since both C-B5 and C-N5 have a greater LAC than C-0, these results indicate that the addition of Bi₂O₃ improves the shielding ability of the concretes. In addition, we investigated the influence of nanoparticle Bi₂O₃ on the LAC of the concretes. The half-value layer (HVL) for the concretes with bulk Bi₂O₃ and Bi₂O₃ nanoparticles is also investigated. At all energies, the C-0 has the greatest HVL, while C-N15 has the least. Thus, C-N15 concrete is the most space efficient, while C-0 is the least space efficient. The radiation protection efficiency (RPE) of the prepared concretes was found to decrease with increasing energy for all five samples. For C-0, the RPE decreased from 63.3% at 0.060 MeV to 13.48% at 1.408 MeV, while for C-N15, the RPE decreased from 87.9 to 15.09% for the same respective energies. Additionally, C-N5 had a greater RPE than C-B5, this result demonstrates that Bi₂O₃ NP are more efficient at shielding radiation than bulk Bi₂O₃.     

Optoelectronic Properties of α-MoO3 Tuned by H Dopant in Different Concentration

The optoelectronic properties of layered α-MoO₃ are greatly limited due to its wide band gap and low carrier concentration. The insertion of hydrogen (H) can effectively tune the band structure and carrier concentration of MoO₃. Herein, first-principles calculations were performed to unravel the physical mechanism of a H-doped α-MoO₃ system. We found that the modulation of the electronic structure of H-doped MoO₃ depends on the doping concentration and position of the H atoms. It was found that the band gap decreases at 8% doping concentration due to the strong coupling between Mo-4d and O-2p orbits when H atoms are inserted into the interlayer. More interestingly, the band gap decreases to an extreme due to the Mo-4d orbit when all the H atoms are inserted into the intralayer only, which has a remarkable effect on light absorption. Our research provides a comprehensive theoretical discussion on the mechanism of H-doped α-MoO₃ from the doping positions and doping concentrations, and offers useful strategies on doping modulation of the photoelectric properties of layered transition metal oxides.     

Effects of the Interface between Inorganic and Organic Components in a Bi2Te3–Polypyrrole Bulk Composite on Its Thermoelectric Performance

We provided a method to hybridize Bi₂Te₃ with polypyrrole, thus forming an inorganic/organic bulk composite (Bi₂Te₃–polypyrrole), in which the effects of energy band junction and phonon scattering were expected to occur at the interface of the two components. Bi₂Te₃–polypyrrole exhibited a considerably high Seebeck coefficient compared to pristine Bi₂Te₃, and thus it recorded a somewhat increased power factor despite the loss in electrical conductivity caused by the organic component, polypyrrole. Bi₂Te₃–polypyrrole also exhibited much lower thermal conductivity than pristine Bi₂Te₃ because of the phonon scattering effect at the interface. We successfully brought about the decoupling phenomenon of electrical and thermal properties by devising an inorganic/organic composite and adjusting its fabrication condition, thereby optimizing its thermoelectric performance, which is considered the predominant property for n-type binary Bi₂Te₃ reported so far.     

The Effect of Reactive Electric Field-Assisted Sintering of MoS2/Bi2Te3 Heterostructure on the Phase Integrity of Bi2Te3 Matrix and the Thermoelectric Properties

In this work, a series of Bi₂Te₃/X mol% MoS₂ (X = 0, 25, 50, 75) bulk nanocomposites were prepared by hydrothermal reaction followed by reactive spark plasma sintering (SPS). X-ray diffraction analysis (XRD) indicates that the native nanopowders, comprising of Bi₂Te₃/MoS₂ heterostructure, are highly reactive during the electric field-assisted sintering by SPS. The nano-sized MoS₂ particles react with the Bi₂Te₃ plates matrix forming a mixed-anion compound, Bi₂Te₂S, at the interface between the nanoplates. The transport properties characterizations revealed a significant influence of the nanocomposite structure formation on the native electrical conductivity, Seebeck coefficient, and thermal conductivity of the initial Bi₂Te₃ matrix. As a result, enhanced ZT values have been obtained in Bi₂Te₃/25 mol% MoS₂ over the temperature range of 300–475 K induced mainly by a significant increase in the electrical conductivity.     

Preparation of BiOCl/Bi2WO6 Photocatalyst for Efficient Fixation on Cotton Fabric: Applications in UV Shielding and Self-Cleaning Performances

In this work, a visible-light-driven BiOCl/Bi₂WO₆ photocatalyst was obtained via a facile hydrothermal method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), ultraviolet/visible light diffuse reflection spectroscopy (UV/Vis), and photocurrent (PC). BiOCl/Bi₂WO₆ was modified with (3-chloro-2-hydroxypropyl) trimethyl ammonium chloride to obtain the cationized BiOCl/Bi₂WO₆. Cotton fabric was pretreated with sodium hydroxide (NaOH) and sodium chloroacetate solution to obtain carboxymethylated cotton fabric, which was further reacted with cationized BiOCl/Bi₂WO₆ to achieve finished cotton fabric. The cotton fabrics were characterized by Fourier-transform infrared spectroscopy (FT-IR), XRD, SEM, and EDS. The photocatalytic activity of the BiOCl/Bi₂WO₆ photocatalyst and cotton fabrics was assessed by photocatalytic degradation of MB (methylene blue) solution under simulated visible light. The self-cleaning property of cotton fabrics was evaluated by removing MB solution and red-wine stains. Results revealed that the coated cotton fabrics exhibited appreciable photocatalytic and self-cleaning performance. In addition, anti-UV studies showed that the finished cotton fabrics had remarkable UV blocking properties in the UVA and UVB regions. Therefore, the finished cotton fabric with BiOCl/Bi₂WO₆ can provide a framework for the development of multifunctional textiles.     

Enhanced N-Type Bismuth-Telluride-Based Thermoelectric Fibers via Thermal Drawing and Bridgman Annealing

N-type bismuth telluride (Bi₂Te₃) based thermoelectric (TE) fibers were fabricated by thermal drawing and Bridgman annealing, and the influence of Bridgman annealing on the TE properties of n-type Bi₂Te₃-based TE fibers was studied. The Bridgman annealing enhanced the electrical conductivity and Seebeck coefficient because of increasing crystalline orientation and decreasing detrimental elemental enrichment. The TE performance of n-type Bi₂Te₃-based TE fibers was improved significantly by enhancing the power factor. Hence the power factor increased from 0.14 to 0.93 mW/mK², and the figure-of-merit value is from 0.11 to 0.43 at ~300 K, respectively.     

Al2O3-Cu-Ni Composites Manufactured via Uniaxial Pressing: Microstructure,Magnetic, and Mechanical Properties

This study’s main goal was to obtain and characterize Al₂O₃-Cu-Ni composites with different metallic phase content. The study analyzed the three series of samples differing in the metallic phase 5, 10, 15 vol.% volume contents. An identical volume share of the metallic components in the metallic phase was used. Ceramic–metal composites were formed using uniaxial pressing and sintered at a temperature of 1400 °C. The microstructural investigation of the Al₂O₃-Cu-Ni composite and its properties involved scanning electron microscopes observations and X-ray diffraction. The size of the metallic phase in the ceramic matrix was performed using a stereological analysis. Microhardness analysis with fracture toughness measures was applied to estimate the mechanical properties of the prepared materials. Additionally, magnetic measurements were carried out, and the saturation magnetization was determined on the obtained magnetic hysteresis loops. The prepared samples, regardless of the content of the metallic phase in each series, were characterized by a density exceeding 95% of the theoretical density. The magnetic measurements exhibited that the fabricated composites had ferromagnetic properties due to nickel and nickel-rich phases. The hardness of the samples containing 5, 10, 15 vol.% metallic phases decreased with an increase in the metallic phase content, equal to 17.60 ± 0.96 GPa, 15.40 ± 0.81 GPa, 12.6 ± 0.36 GPa, respectively.     

Doping Effect on Cu2Se Thermoelectric Performance: A Review

Cu₂Se, owing to its intrinsic excellent thermoelectric (TE) performance emerging from the peculiar nature of “liquid-like” Cu⁺ ions, has been regarded as one of the most promising thermoelectric materials recently. However, the commercial use is still something far from reach unless effective approaches can be applied to further increase the figure of merit (ZT) of Cu₂Se, and doping has shown wide development prospect. Until now, the highest ZT value of 2.62 has been achieved in Al doped samples, which is twice as much as the original pure Cu₂Se. Herein, various doping elements from all main groups and some transitional groups that have been used as dopants in enhancing the TE performance of Cu₂Se are summarized, and the mechanisms of TE performance enhancement are analyzed. In addition, points of great concern for further enhancing the TE performance of doped Cu₂Se are proposed.     

Influence of Quenching and Subsequent Annealing on the Conductivity and Electromechanical Properties of Na1/2Bi1/2TiO3-BaTiO3

Na_1/2Bi_1/2TiO₃-based materials have gained considerable attention for their potential to exhibit giant strain, very-high ionic conductivity comparable to yttria stabilized zirconia or high mechanical quality factor for use in high power ultrasonics. In recent times, quenching Na_1/2Bi_1/2TiO₃-based compositions have been demonstrated to enhance the thermal depolarization temperature, thus increasing the operational temperature limit of these materials in application. This work investigates the role of quenching-induced changes in the defect chemistry on the dielectric, ferroelectric and piezoelectric properties of quenched Na_1/2Bi_1/2TiO₃-BaTiO₃. The quenched samples indeed demonstrate an increase in the bulk conductivity. Nevertheless, while subsequent annealing of the quenched samples in air/oxygen atmosphere reverts back the depolarization behaviour to that of a furnace cooled specimen, the bulk conductivity remains majorly unaltered. This implies a weak correlation between the defect chemistry and enhanced thermal stability of the piezoelectric properties and hints towards other mechanisms at play. The minor role of oxygen vacancies is further reinforced by the negligible (10–15%) changes in the mechanical quality factor and hysteresis loss.     

Enhanced Structural Stability and Electrochemical Performance of LiNi0.6Co0.2Mn0.2O2 Cathode Materials by Ga Doping

Structural instability during cycling is an important factor affecting the electrochemical performance of nickel-rich ternary cathode materials for Li-ion batteries. In this work, enhanced structural stability and electrochemical performance of LiNi_0.6Co_0.2Mn_0.2O₂ cathode materials are achieved by Ga doping. Compared with the pristine electrode, Li[Ni_0.6Co_0.2Mn_0.2]_0.98Ga_0.02O₂ electrode exhibits remarkably improved electrochemical performance and thermal safety. At 0.5C rate, the discharge capacity increases from 169.3 mAh g⁻¹ to 177 mAh g⁻¹, and the capacity retention also rises from 82.8% to 89.8% after 50 cycles. In the charged state of 4.3 V, its exothermic temperature increases from 245.13 °C to more than 271.24 °C, and the total exothermic heat decreases from 561.7 to 225.6 J·g⁻¹. Both AC impedance spectroscopy and in situ XRD analysis confirmed that Ga doping can improve the stability of the electrode/electrolyte interface structure and bulk structure during cycling, which helps to improve the electrochemical performance of LiNi_0.6Co_0.2Mn_0.2O₂ cathode material.     

Study of the Structure,Magnetic, Thermal and Electrical Characterisation of ZnCr2Se4: Ta Single Crystals Obtained by Chemical Vapour Transport

The new series of single-crystalline chromium selenides, Ta-doped ZnCr₂Se₄, was synthesised by a chemical vapour transport method to determine the impact of a dopant on the structural and thermodynamic properties of the parent compound. We present comprehensive investigations of structural, electrical transport, magnetic, and specific heat properties. It was expected that a partial replacement of Cr ions by a more significant Ta one would lead to a change in direct magnetic interactions between Cr magnetic moments and result in a change in the magnetic ground state and electric transport properties of the ZnCr_2−xTa_xSe₄ (x = 0.05, 0.06, 0.07, 0.08, 0.1, 0.12) system. We found that all the elements of the cubic system had a cubic spinel structure; however, the doping gain linearly increased the ZnCr_2−xTa_xSe₄ unit cell volume. Doping with tantalum did not significantly change the semiconductor and magnetic properties of ZnCr₂Se₄. For all studied samples (0 ≤ x ≤ 0.12), an antiferromagnetic order (AFM) below T_N~22 K was observed. However, a small amount of Ta significantly reduced the second critical field (H_c2) from 65 kOe for x = 0.0 (ZnCr₂Se₄ matrix) up to 42.2 kOe for x = 0.12, above which the spin helical system changed to ferromagnetic (FM). The H_c2 reduction can lead to strong competition among AFM and FM interactions and spin frustration, as the specific heat under magnetic fields H < H_c2 shows a strong field decrease in T_N.