Bi Doping Research Articles

Exploring Intrinsic and Extrinsic p-Type Dopability of Atomically Thin β-TeO2 from First Principles.

Two-dimensional (2D) β-TeO2 has gained attention as a promising material for optoelectronic and power device applications, thanks to its transparency and high hole mobility. However, the mechanisms driving its p-type conductivity and dopability remain elusive. In this study, we investigate the intrinsic and extrinsic point defects in monolayer and bilayer β-TeO2, the latter of which has been experimentally synthesized, using the Heyd-Scuseria-Ernzerhof (HSE) + D3 hybrid functional. Our results reveal that most intrinsic defects are unlikely to contribute to p-type doping in 2D β-TeO2. Moreover, Si and H contamination could further impair p-type conductivity. Since the point defects do not contribute to p-type conductivity, we suggest two possible mechanisms for hole conduction: hopping conduction via localized impurity states, and substrate effects. We also explored substitutional p-type doping in 2D β-TeO2 with 10 trivalent elements. Among these, the Bi dopant is found to exhibit a relatively shallow acceptor transition level. However, all the dopants introduce deep localized states, where hole polarons are trapped by the lone pairs of Te atoms. Interestingly, monolayer β-TeO2 shows potential advantages over bilayers due to reduced self-compensation effects for p-type dopants. These findings provide valuable insights into defect engineering strategies for future electronic applications involving 2D β-TeO2.

Manipulating Magnetic Damping of Fe/GeTe Heterostructures by Band Engineering.

Understanding and manipulating magnetic damping, particularly in magnetic heterostructures, is crucial for fundamental research, versatile engineering, and optimization. Although magnetic damping can be enhanced by the band hybridization between ferromagnetic and nonmagnetic materials at the interface, the contribution of individual subbands on the hybridized bands to magnetic damping is fully unexplored. Here, it is found that magnetic damping αeff is modified by the Fermi level in Fe/GeTe heterostructures via Bi doping. By combining angle-resolved photoemission spectroscopy and density functional theory calculations, the enhancement of damping originated from the strongly hybridized band structures between Fe and the surface Rashba bands of GeTe are unveiled. More interestingly, the Fermi level modulates the density of states (DOS) ratio between the subbands of GeTe and the total DOS of hybridized states, which is directly proportional to the magnetic damping. This work gives an insightful physical understanding of the magnetic damping influenced by the hybridized band structures and opens a novel avenue to manipulate magnetic damping by band engineering.

Investigation on degraded thermoelectric performance of SnSe2 polycrystalline alloys by Bi doping

Investigation on degraded thermoelectric performance of SnSe2 polycrystalline alloys by Bi doping

Biophotoelectrocatalytic detoxification of Bisphenol A using Bismuth-doped TiO2 Nanotubes photoanode coupled with Laccase-immobilized cathode

Photoelectrocatalytic (PEC) technology has been demonstrated to be an effective method for environmental remediation, but its efficiency in detoxifying persistent pollutants such as bisphenol A (BPA) requires further enhancement. Herein, an enzyme-coupled PEC system for detoxification of BPA was proposed by integrating a Bismuth-doped TiO2 Nanotubes (Bi-TiO2 NTs) photoanode and laccase-immobilized cathode. The results reveal that the doping of Bi into TiO2 enhances the visible light absorption and reduces the recombination of photogenerated electron-hole pairs when exposed to simulated solar irradiation. When the laccase-immobilized cathode was incorporated into the PEC device, the resulting biophotoelectrocatalytic system exhibited excellent degradation performance for BPA, owing to the synergistic effect between enzymatic catalysis and photoelectrocatalysis. A potential degradation pathway for BPA was established through the analysis of intermediate products, and subsequent phytotoxicity assessments revealed a significant reduction in the toxicity of the laccase-coupled PEC-degraded BPA solution. This study highlights that coupling a laccase-immobilized cathode with Bi-doped TiO2 NTs photoanodes serves as an effective method for the detoxification of persistent pollutants.

Bismuth sensitized iron oxide on exfoliated graphene oxide (Bi–Fe2O3@GO) for oxygen evaluation reaction

Electrochemical water splitting is a promising approach towards a sustainable and renewable energy source. However, the demand for high anodic potential and sluggish kinetics of oxygen evolution reaction (OER) restrict the efficiency and feasibility of the water-splitting process. In this quest, transition metal oxides and alloys are considered potential candidates owing to their natural occurrence and high redox potential for OER. However, many associated challenges in their use are still there to be addressed. Here, we designed a new class of bismuth-doped iron oxide on exfoliated graphene oxide by optimizing the metal loading on the conductive support to facilitate the flow of charge during catalysis. The catalytic ability of the synthesized Bi-doped nanocomposites was evaluated in activating the OER under extreme alkaline conditions (1 MKOH). On screening different combinations, 20Bi–Fe2O3@GO was identified as the most efficient and sustainable electrocatalyst even under harsh operating conditions, with an onset potential of 1.48 V and a Tafel slope of 65 mV/dec. The current study offers a new class of Bi-doped electrocatalysts, where the precise doping of Bi and the optimized loading of metal was found the key to achieving low onset potential and high current density to initiate OER.Graphical abstract

P and Bi Doped Pt-Zn Alloy as an Effective Electrocatalyst for Hydrogen Evolution Reaction: A First-Principles Study

Platinum (Pt) is a highly effective catalyst for the hydrogen evolution reaction (HER), but its high cost and scarcity have spurred efforts to reduce Pt usage without compromising catalytic performance. Various strategies, such as alloying Pt with earth-abundant elements and doping with other elements to modify the electronic structure and improve activity, have been explored to achieve this objective.In this study, we propose a phosphorus (P) and bismuth (Bi) doped Pt-Zn catalyst with a reduced platinum content and enhanced HER activity. Using First-Principles calculations, we identified the stable structure of the PtZn alloy and the optimal doping configurations of P and Bi. In addition, we calculated the adsorption energies of a key intermediate to construct the reaction free energy diagram, validating the enhanced catalytic activity of the P and Bi doped Pt-Zn catalyst. To gain atomistic-level insights, we performed detailed calculations to analyze the electronic structure of the doped configurations, revealing the role of these dopants in optimizing the electronic structure at the active sites. Our analysis demonstrates that the introduction of P and Bi not only stabilizes the catalyst structure but also effectively modifies the electronic properties to improve HER activity. This approach offers a promising pathway to develop cost-effective and high-performance Pt-based catalysts for electrochemical applications.

Effect of Bi Doping on the Kinetics of Nickel Oxides-Based Electrocatalyst in Alkaline Oxygen Evolution Reaction

As a generation process of hydrogen fuel, an alkaline water electrolysis is considered as one of the most promising pathway. The water electrolysis is able to divide into two half-cell reaction: hydrogen evolution reaction (HER) in cathode and oxygen evolution reaction (OER) in anode. However, high activation energy of OER is regarded as a major bottleneck for utilization of water electrolysis, therefore it is necessary to use an electrocatalyst to improve the reaction rate. Currently, commercially used electrocatalysts of OER is precious metal such as platinum (Pt), ruthenium (Ru), and iridium (Ir) based compound which have critical drawback for high cost and low stability in alkaline electrolyte.As a substitute of platinum group materials for electrocatalyst of oxygen evolution reaction (OER), the development of cost-effective and high-active nickel oxide catalyst has attracted intense research interest. Alkaline OER is composed by five states: M, M-OH, M-O, M-OOH, and M + O2, and the gibbs free energy of final state is 4.92 eV higher than the first state. Thus, the free energy difference between each states equally becomes 1.23 eV to minimize the activation energy of rate determining step (RDS). In this point, nickel oxide shows a remarkable catalytic activity because a rapid and reversible electrochemical oxidation on the surface of nickel oxide triggers reconstructions to form hydroxide which is suitable structures for intermediate of OER. However, the nickel oxide still has high activation energy of reaction step from nickel(II) oxide to nickel(III) oxyhydroxide (3rd step of OER, Ni-O à Ni-OOH), which becomes RDS of OER. Because the catalytic activity seriously reduces without the balanced rate between each step of reaction, it is necessary to control the electric structure of nickel oxide to optimize adsorption energy of intermediates.In this context, bismuth doped nickel oxide is synthesized for electrocatalyst of OER. Because bismuth has higher electronegativity than nickel, the adsorption energy of positively charged nickel with proton decreases and the adsorption energy of positively charged nickel oxide with hydroxide ion increases. Therefore, the activation energy of RDS of OER is expected to reduce than the pristine nickel oxide.In practice, the bismuth doped nickel oxide is synthesized by hydrothermal process and the composition of bismuth is controlled by the concentration of precursors. The crystal structure of nickel oxide is maintained after the addition of bismuth, but the inter-planar spacing of overall plane of nickel oxide structure decreases according to selected area electron diffraction (SAED) pattern of transmission electron microscopy (TEM). In this context, the bismuth additive does not form the bi-metal oxide with nickel, but it substitutes the nickel site of nickel oxide structure. According to the nickel 2p3/2 spectra of x-ray photoelectron spectroscopy (XPS), a binding energy of nickel oxide peak positively shifts when the composition of bismuth additive increased due to the shifted electron from nickel to bismuth atom. As electrochemical measurement for evaluation of catalytic activity, the bismuth doped nickel oxide shows 59 mV lower overpotential at 20 mA cm-2 in alkaline OER, respectively, than the nickel oxide. In particular, the addition of bismuth is especially influenced to intrinsic activity, the bismuth doped nickel oxide catalyst shows higher turnover frequency than the pristine nickel oxide although it has similar active surface area. Figure 1

Conjugated Polymer-Supported Doped Bi2WO6 S-Scheme Heterojunction for Proficient Water Splitting via Dual Regulation of Band Gap Engineering and Improved Charge Separation

Conjugated Polymer-Supported Doped Bi₂WO₆ S-Scheme Heterojunction for Proficient Water Splitting via Dual Regulation of Band Gap Engineering and Improved Charge Separation

Enhanced Photocatalytic Activity of Nickel(II)‐Doped Bi2O2CO3 Nanosheets for Efficient Nitric Oxide Removal

AbstractBi2O2CO3 is a typical bismuth‐based semiconductor photocatalyst that has attracted much attention because of layered structure and polarization characteristics. However, the wide bandgap of Bi2O2CO3 limits its practical applications in photocatalysis. In this study, the nickel (II)‐doped Bi2O2CO3 (Ni2+‐Bi2O2CO3) with oxygen vacancies was prepared by adding a controllable amount of nickel ions. The photocatalytic efficiency of the optimized sample for ppb‐grade NO under visible light irradiation is 59.4 %, which is 2.8 times than that of its counterpart, Bi2O2CO3 (21.2 %). Based on experiments and characterizations, Introduction of nickel ions and oxygen vacancies improves the photocatalytic performance of Ni2+‐Bi2O2CO3, which not only lowered the bandgap from 3.25 eV to 2.92 eV, but also reduced the recombination of photogenerated carriers by formation of the impurity level. Furthermore, the adsorption and photocatalytic conversion pathway of NO was explored by in situ DRIFTS, the principal byproducts of photocatalytic oxidation of NO are NO3− and NO2−. This work offers a new perspective to improve the photocatalytic activity by doping mothed for air purification.

Enhancing Thermoelectric Performance of Mg3Sb2 Through Substitutional Doping: Sustainable Energy Solutions via First-Principles Calculations

Mg3Sb2-based materials, part of the Zintl compound family, are known for their low thermal conductivity but face challenges in thermoelectric applications due to their low energy conversion efficiency. This study addressed these limitations through first-principles calculations using the CASTEP module in Materials Studio 8.0, aiming to enhance the thermoelectric performance of Mg3Sb2 via strategic doping. Density functional theory (DFT) calculations were performed to analyze electronic properties, including band structure and density of states (D.O.S.), providing insights into the influence of various dopants. The semiclassical Boltzmann transport theory, implemented in BoltzTrap (version 1.2.5), was used to evaluate key thermoelectric properties such as the Seebeck coefficient, electrical conductivity, electronic thermal conductivity, and electronic figure of merit (eZT). The results indicate that doping significantly improved the thermoelectric properties of Mg3Sb2, facilitating a transition from p-type to n-type behavior. Bi doping reduced the band gap from 0.401 eV to 0.144 eV, increasing carrier concentration and mobility, resulting in an electrical conductivity of 1.66 × 106 S/m and an eZT of 0.757. Ge doping increased the Seebeck coefficient to −392.1 μV/K at 300 K and reduced the band gap to 0.09 eV, achieving an electronic ZT of 0.859 with low thermal conductivity (11 W/mK). Si doping enhanced stability and achieved an electrical conductivity of 1.627 × 106 S/m with an electronic thermal conductivity of 11.3 W/mK, improving thermoelectric performance. These findings established the potential of doped Mg3Sb2 as a highly efficient thermoelectric material, paving the way for future research and applications in sustainable energy solutions.

Structural Modifications due to Bi-Doping in MAPbBr3 Single Crystals and Their Impact on Electronic Transport and Stability.

Doping strategy in lead halide perovskites is essential to enhance its optoelectrical properties and expand the potential applications. In this work, the mechanisms, for how dopants affect the overall structural, optical, electrical, and chemical properties and stability of lead halide perovskite materials, are investigated. This is done by specifically considering various bismuth (Bi)doping concentrations in MAPbBr3 single crystals grown using the inverse temperature crystallization method. The resultant doped single crystals exhibit a saturation point when Bi concentration exceeds 0.063% which is considered an optimum doping point. The highest thermal stability is also achieved at this doping concentration among the doped single crystals. This study clearly identifies how Bi doping affects the properties of MAPbBr3 and extends to consider stability, which has not been fully considered for MA-based perovskites previously. This will provide a clear understanding of evaluating doped perovskite materials for enhanced material properties, device performance, and stability.

Bi doping induces the quantum dots to improve the supercapacitor performance of cobalt carbonate hydroxide hydrate

Cobalt carbonate hydroxide has been widely used in supercapacitor electrodes because of its excellent theoretical electrochemical properties and easy synthesis. However, in actual synthesis, its excellent electrochemical properties are often weakened due to its oxide-like properties, which restricts its further development. Herein, the Bi heteroatoms are introduced into the Co(CO3)0.5(OH)·0.11H2O, which not only modifies the microstructure, but also induces the formation of quantum dots, thus improving the performance of supercapacitors. By regulating the doping amount of Bi, the optimized Co/Bi-3:1 exhibits a specific capacitance of 680 F g−1 at 1 A g−1, which is 5.74 times than the pristine Co(CO3)0.5(OH)·0.11H2O. Furthermore, the assembled Co/Bi-3:1//activated carbon soft-pack asymmetric supercapacitor has a relatively superior power density (10547.58 W kg−1, relative to 14.06 Wh kg−1 energy density) and energy density (17.83 Wh kg−1, relative to 2146.76 W kg−1 power density). The present study demonstrates that Bi doping not only facilitates the formation of quantum dots and enhances electron conduction ability, but also regulates the microscopic morphology, thereby enhancing the electrochemical energy storage capacity of cobalt carbonate hydroxide hydrate electrode materials.

Evidence and engineering of x-ray luminescence in lead free perovskite Cs2AgInCl6 with Bi substitutions

Cs2AgInCl6 belongs to the family of lead-free halide double perovskites. Lead-free halide double perovskite appears as a viable contender for scintillator applications due to its inexpensive production costs, low intrinsic trap density, and nanosecond quick reaction. Perovskite crystals have a substantially lower trap density than lead halide and traditional oxide scintillator materials, according to thermo-luminescence measurements. Cs2AgInCl6 structure and dimensionality were engineered by Bi doping. Bi substitution reduces the bandgap, making it suited for scintillation applications. Bi substitution allows for easy tuning of Cs2AgIn(1−x)BixCl6 (0 ≤ x ≤ 50) due to its wide versatility in scintillation properties. For Cs2AgIn(1−x)BixCl6 (0 ≤ x ≤ 50), x-ray power dependent luminescence increases with increasing power. Because of their nontoxicity, sensitivity, reaction time, and stability, Cs2AgIn(1−x)BixCl6 (0 ≤ x ≤ 50) double perovskite crystals are promising for x-ray scintillation.

Dielectric Relaxation, Electrical Conductivity, Dielectric Permittivity, and Correlated Barrier Hopping Conduction Mechanism Analysis in Ag Doped Bi2S3 at Low Temperatures

AbstractPure and 6% Ag doped bismuth sulfide (Bi2S3) were synthesized via solid‐state reaction method at 500 °C. The X‐ray diffraction method confirmed the orthorhombic phase with average crystallite size ∼25 nm and average lattice strain ∼0.5% and ∼0.6% for pure and 6% Ag doped Bi2S3. The scanning electron microscope (SEM) images confirmed nanobelt morphology. A direct bandgap of ∼3.3 and ∼3.4 eV for pure and doped Bi2S3 was estimated using UV–vis spectroscopy, respectively. AC measurements were performed from 200 Hz to 2 MHz at temperature 223–298 K. Investigation of Nyquist plots of 6% Ag doped Bi2S3 nanobelts suggested space‐charge‐dependent behavior and indicated an negative temperature coefficient of resistance (NTCR). AC conductivity adhered to Jonscher's power law in which the decreasing trend of s‐parameter with increasing temperature indicates correlated barrier hopping conduction mechanism. From this model, hopping distance (∼10−9–10−11 m) and density of states (∼1022–1023 eV−1 cm−3) were estimated. The dielectric permittivity exhibited dispersion at low frequencies due to the combined effect of electronic, ionic, and interfacial polarizations. Presence of two semicircular arcs in the complex modulus analysis suggested the presence of both grain and grain‐boundary effects.

Bandgap Engineering via Doping Strategies for Narrowing the Bandgap below 1.2 eV in Sn/Pb Binary Perovskites: Unveiling the Role of Bi3+ Incorporation on Different A-Site Compositions.

The integration of perovskite materials in solar cells has garnered significant attention due to their exceptional photovoltaic properties. However, achieving a bandgap energy below 1.2 eV remains challenging, particularly for applications requiring infrared absorption, such as sub-cells in tandem solar cells and single-junction perovskite solar cells. In this study, we employed a doping strategy to engineer the bandgap and observed that the doping effects varied depending on the A-site cation. Specifically, we investigated the impact of bismuth (Bi3+) incorporation into perovskites with different A-site cations, such as cesium (Cs) and methylammonium (MA). Remarkably, Bi3+ doping in MA-based tin-lead perovskites enabled the fabrication of ultra-narrow bandgap films (~1 eV). Comprehensive characterization, including structural, optical, and electronic analyses, was conducted to elucidate the effects of Bi doping. Notably, 8% Bi-doped Sn-Pb perovskites demonstrated infrared absorption extending up to 1360 nm, an unprecedented range for ABX3-type single halide perovskites. This work provides valuable insights into further narrowing the bandgap of halide perovskite materials, which is essential for their effective use in multi-junction tandem solar cell architectures.

Bismuth-doping Induced Enhanced Humidity Sensing Properties of Spinel NiFe2O4 Nanoparticles

Bi-doped NiFe2O4 nanoparticles were tested for humidity detection at various RH levels at room temperature. The findings indicated that sensors with higher Bi concentrations, particularly the ones with 20 % Bi doping, showed significantly enhanced sensing response—up to 97 %, a sixfold increase compared to undoped sensors. This significant improvement suggests that Bi contributes to synergistic effects that boost sensor performance. Density Functional Theory (DFT) calculations support this by showing that Bi introduces acceptor electronic states, heightening electrical responsiveness to moisture. These Bi-doped sensors exhibit quick response times, high accuracy, negligible hysteresis, and impressive stability, making them promising candidates for reliable humidity detection.

Modulating the Bader Charge Transfer in Single p-Block Atoms Doped Pd Metallene for Enhanced Oxygen Reduction Electrocatalysis.

Metallene is considered as an emerging family of electrocatalysts due to its atomically layered structure and unique surface stress. Here we propose a strategy to modulate the Bader charge transfer (BCT) between Pd surface and oxygenated intermediates via p-d electronic interaction by introducing single-atom p-block metal (M=In, Sn, Pb, Bi) into Pd metallene nanosheets towards efficient oxygen reduction reaction (ORR). X-ray absorption and photoelectron spectroscopy suggests that doping p-block metals could facilitate electron transfer to Pd sites and thus downshift the d-band center of Pd and weaken the adsorption energy of O intermediates. Among them, the developed Bi-Pd metallene shows extraordinarily high ORR mass activity of 11.34 A mgPd -1 and 0.86 A mgPd -1 at 0.9 V and 0.95 V in alkaline solution, respectively, representing the best Pd-based ORR electrocatalysts ever reported. In the cathode of a Zinc-air battery, Bi-Pd metallene could achieve an open-circuit voltage of 1.546 V and keep stable for 760 h at 10 mA cm-2. Theoretical calculations suggest that the BCT between Pd surface and *OO intermediates greatly affects the bond length between them (dPd-*OO) and Bi doping could appropriately reduce the amount of BCT and stretch the dPd-*OO, thus enhancing the ORR activity.

Modulating the Bader Charge Transfer in Single p‐Block Atoms Doped Pd Metallene for Enhanced Oxygen Reduction Electrocatalysis

AbstractMetallene is considered as an emerging family of electrocatalysts due to its atomically layered structure and unique surface stress. Here we propose a strategy to modulate the Bader charge transfer (BCT) between Pd surface and oxygenated intermediates via p‐d electronic interaction by introducing single‐atom p‐block metal (M=In, Sn, Pb, Bi) into Pd metallene nanosheets towards efficient oxygen reduction reaction (ORR). X‐ray absorption and photoelectron spectroscopy suggests that doping p‐block metals could facilitate electron transfer to Pd sites and thus downshift the d‐band center of Pd and weaken the adsorption energy of O intermediates. Among them, the developed Bi−Pd metallene shows extraordinarily high ORR mass activity of 11.34 A mgPd−1 and 0.86 A mgPd−1 at 0.9 V and 0.95 V in alkaline solution, respectively, representing the best Pd‐based ORR electrocatalysts ever reported. In the cathode of a Zinc‐air battery, Bi−Pd metallene could achieve an open‐circuit voltage of 1.546 V and keep stable for 760 h at 10 mA cm−2. Theoretical calculations suggest that the BCT between Pd surface and *OO intermediates greatly affects the bond length between them (dPd‐*OO) and Bi doping could appropriately reduce the amount of BCT and stretch the dPd‐*OO, thus enhancing the ORR activity.

Effects of Bi Doping on Zn-Rich Phase Evolution and Physical and Chemical Properties of Sn-6.5Zn Lead-Free Solder Alloy

Effects of Bi Doping on Zn-Rich Phase Evolution and Physical and Chemical Properties of Sn-6.5Zn Lead-Free Solder Alloy

Ultrahigh Stability and Operation Performance in Bi-doped GeTe/Sb2Te3 Superlattices Achieved by Tailoring Bonding and Structural Properties.

Changes in bond types and the reversible switching process between metavalent and covalent bonds are related to the operating mechanism of the phase-change (PC) behavior. Thus, controlling the bonding characteristics is the key to improving the PC memory performance. In this study, we have controlled the bonding characteristics of GeTe/Sb2Te3 superlattices (SLs) via bismuth (Bi) doping. The incorporation of Bi into the GeTe sublayers tailors the metavalent bond. We observed significant improvement in device reliability, set speed, and power consumption induced upon increasing Bi incorporation. The introduction of Bi was found to suppress the change in density between the SET and RESET states, resulting in a significant increase in device reliability. The reduction in Peierls distortion, leading to a more octahedral-like atomic arrangement, intensifies electron-phonon coupling with increased bond polarizability, which are responsible for the fast set speed and low power consumption. This study demonstrates how the structural and thermodynamic changes in phase change materials alter phase change characteristics due to systematic changes of bonding and provides an important methodology for the development of PC devices.