Bi Thin Films Research Articles

Optimizing the thermoelectric performance of Bi-Sb-Te thin films through compositional engineering

The objective of the present investigation was to systematically investigate the structural and thermoelectric (TE) properties of BixSb2-xTe3 thin films with varying content of Bi. We investigated the impact of different atomic percentages of Bi (4, 6, 8 at. %) on the properties of carrier transport and TE performance. In general, the Seebeck coefficient remained consistent across the thin films. For the 8 at. % Bi thin film, the Seebeck coefficient and electrical conductivity were measured at 230 μV/K and 730 S/cm, respectively, at room temperature. These values were more than 20 times greater than the electrical conductivity observed in the thin films with compositions of 6 and 4 at. % Bi. As a result, the Bi-Sb-Te compound exhibited a TE power factor (PF) of 38x10−4 W/mK2 at 40 °C, surpassing the PFs observed in previous compositions. The analysis of surface microstructure, combined with atomic force microscopy and Kelvin probe microscopy images, revealed that the transport of carriers in films with high Bi content was impeded by the size of particles and scattering sites. On the other hand, an augmentation in Bi content promoted the transfer of charge through crystalline regions, hence improving the mobility of carriers and the total electrical conductivity. The aforementioned results emphasize the significant influence of Bi content on the electrical properties of semiconductors and demonstrate the effectiveness of compositional engineering based on Bi content in the development of TE materials with superior performance. The present study investigates the influence of Bi content on the electrical properties of Bi-Sb-Te thin films, demonstrating that compositional adjustments based on Bi content can impact the performance of TE materials. These findings contribute to the understanding of material optimization in the field of TE.

Hot probe technique for thin films Seebeck coefficient measurement

A new experimental method using a 50 μm diameter hand fabricated hot probe of Pt90/10Rh alloy is proposed as a tool to measure the Seebeck coefficient of thin films deposited onto electrically insulated substrates. A thermal model for heat transfer inside the probe and to the sample was developed to simulate the corresponding temperature distributions. Simulations showed that the ratio of the temperature rise in the contact point to the average temperature of the probe evolves basically independent on electrical current and film-substrate properties. Moreover, the values of contact radius and thermal contact resistance should not be necessary known, but only the pairs which are best fitting the probe thermal resistance in contact with the film-substrate. This brings a great simplification in respect with certain AFM based hot probe methods for which is necessary to determine these two parameters by calibration of the two substrates with known thermal conductivity. The values can be further used to evaluate the Seebeck coefficient of the sample with a macroscopic probe, within 1 % precision. By variance to the classical measuring methods, which resort to a heater-heat sink ensemble instrumented with thermocouples, heated metallic rods with built-in thermocouples or microfabricated structures, the proposed method is fast, reliable and of higher spatial resolution. The method was validated by measuring the Seebeck coefficient on CdS, Bi and Cr thin films reference samples, respectively.

Precise synthesis of In–Bi alloy nanodroplets through controlled surface reactions on a Si(111) surface at ambient temperature

The synthesis of alloy nanocatalysts with controllable sizes and shapes is a critical prerequisite for vapor–liquid–solid (VLS) growth of one-dimensional nanostructures. In this work, we comprehensively examined surface reactions between evaporated In atoms and a Bi thin film on a Si(111) surface at ambient temperature. InBi2 liquid nanodroplets nucleate and grow during initial vapor–solid (VS) reaction between the In vapor and surface Bi atoms, and the reaction proceeds until a saturation point is reached, following which InBi2 begins to catalyze subsequent VLS growth of various nanocrystals under persistent In-beam flux. The scaled size distribution of individual InBi2 nanodroplets could be explained adequately using the classical capillary nucleation theory, which suggests that the simultaneous homogeneous nucleation of InBi2 nanodroplets occurs during the vapor–solid (VS) reaction of In and Bi.

Strategies for regulating crystallinity and surface quality based on solvent multistage volatilization

In this paper, Bi2212 superconducting thin films were prepared with metal acetate as salt source and a mixture of acetic acid and N,N-dimethylformamide (DMF) as solvent. The volatilization process of the solvent was regulated by changing the ratio of the mixed solvent, which in turn achieved the regulation of the surface morphology and crystallinity of the Bi2212 superconducting films. The mechanism of the mixed solvents on the crystallinity and surface quality of Bi2212 superconducting films was systematically investigated. The results showed that the Bi2212 superconducting films were all (00l) epitaxial growth. The grain size of Bi2212 increased continuously with the increase of the proportion of acetic acid in the solvents. The grain size of the largest grain size was 43.8 nm when the proportion of acetic acid was 80 %. However, the high proportion of acetic acid in the mixed solvents reduced the surface quality of Bi2212 thin films. The minimum surface roughness was 15.0 nm at 40 % acetic acid. All the samples exhibited good superconducting properties. This work provides a research basis for the systematic preparation of multicomponent oxide thin films.

Synthesis of α-Bi/SrTiO3 heterostructure through the Eu-induced reduction of Bi2O2Se/SrTiO3

Thin Bi films, especially noncentrosymmetric α-phase Bi films (α-Bi), have attracted considerable attention in recent years due to their intriguing physical properties such as ferroelectricity, nonlinear optical response, and coherent spin transport. However, the current experimental preparation of α-Bi films still presents substantial challenges, resulting in only isolated α-Bi islands being achieved. In this study, α-Bi/SrTiO3 (α-Bi/STO) was synthesized from a Bi2O2Se/STO (BOS/STO) heterostructure by depositing a Eu layer and reducing a BOS film. The so-formed α-Bi/STO interface features metallic conductivity with electron mobility of 7.7 × 104 cm2/V s and ultralow resistivity of 1 nΩ cm at 2 K, as well as high residual resistance ratios R300 K/R2 K up to 2353. Furthermore, we observed a complex weak antilocalization–weak localization–weak antilocalization crossover with increasing magnetic field at temperatures below 10 K. Our work presents the synthesis of α-Bi films, which could potentially serve as a valuable platform for experimental validation of diverse theoretical predictions associated with α-Bi heterostructures. Furthermore, this special synthesis method provides valuable insights into the preparation of other metastable films.

A novel method to enhance the superconducting properties of Bi2Sr2CaCu2O8+δ superconducting thin films by self-assembly NiO nanorods

The utilization of Bi-based superconductors in magnetic field environments is limited due to their anisotropic structure and lack of efficient magnetic flux pinning sites. Therefore, to enhance the performance of Bi-based superconductors in a magnetic field, this study presents the preparation of Bi2212 high-temperature superconducting thin films with varying NiO doping levels on SrTiO3 (STO) single crystal substrates with different concentrations of NiO seed layers via the self-assembly method. Additionally, phase purity, crystal structure, surface morphology, and transport properties were thoroughly analyzed. According to the results, the NiO seed layers prepared on the STO substrates presented epitaxial growth characteristics, with the NiO second phase in the Bi2212 matrix growing epitaxially along the seed layers. As NiO doping slightly broadens the phase formation temperature range of Bi2212 superconducting thin films, the self-assembly method can be utilized to prepare NiO nanorods with epitaxial growth in Bi2212 thin films. Notably, the self-assembled NiO-doped Bi2212 thin film demonstrated higher critical current carrying capacity, with its Jc reaching 6.28 × 104 A/cm2 at 10 K in self-field. This provides a technical reference for improving the performance of high-temperature superconducting thin films under a high magnetic field.

Signal oscillations in helium scattering by bismuth atoms in the low energy range

Low Energy Ion Scattering (LEIS) analysis of bismuth selenide (Bi2Se3), a strong 3D topological insulator, revealed oscillations of the detected signal in dependence on primary ion beam energy. Bismuth is a part of the group of elements where oscillatory behaviour was already noticed, such as gallium, indium, or lead. Generally, it is ascribed to quasi-resonant charge exchange processes between primary ion and target atom. Moreover, clear differences exist between data for target atoms in elemental form and for atoms in compound form. A study of Bi signal yields in different material forms was performed for primary He+ projectiles within the energy range from 0.50 to 6.00 keV. A foil of pure Bi, Bi2Se3, Bi2O3 and thin Bi films deposited on several substrates (SiO2, CuOx) by Molecular Beam Epitaxy were analysed. The energy shift in the position of oscillations was observed when the oxygen atoms were present at the surface and bonded to Bi atoms. A description of the Bi ion yield variation is provided to facilitate the quantification process in LEIS.

Floquet engineering of axion and high-Chern number phases in a topological insulator under illumination

Quantum anomalous Hall, high-Chern number, and axion phases in topological insulators are characterized by its Chern invariant C (respectively, C=1, integer C>1, and C=0 with half-quantized Hall conductance of opposite signs on top and bottom surfaces). They are of recent interest because of novel fundamental physics and prospective applications, but identifying and controlling these phases has been challenging in practice. Here we show that these states can be created and switched between in thin films of Bi_22Se_33 by Floquet engineering, using irradiation by circularly polarized light. We present the calculated phase diagrams of encountered topological phases in Bi_22Se_33, as a function of wavelength and amplitude of light, as well as sample thickness, after properly taking into account the penetration depth of light and the variation of the gap in the surface states. These findings open pathways towards energy-efficient optoelectronics, advanced sensing, quantum information processing and metrology.

Ultrasensitive detection of L-phenylalanine on DC magnetron sputtered bismuth thin films using label-free SERS method

Quantitative imbalances in monomers such as amino acids, nucleotides etc. act as biomarkers for various health conditions like cancer, Alzheimer’s, genetic disorders etc. Different atmospheric annealed bismuth (Bi) thin films deposited by DC magnetron sputtering were compared to select a better Surface Enhanced Raman Spectroscopy (SERS) platform. The tailored morphology favoured confining of localized surface plasmon resonance (LSPR) between close-packed Bi nanoparticles. The Multiple SPRs (Mult. SPRs) from interband plasmonic transitions are majorly present in the ultraviolet (UV)-near-visible region making the film a promising UV- SERS platform. The varied annealing’s have tuned the SPR and are supported by the colour changes of Bi films. The Raman modes confirmed the chemical stability the films. XPS etching revealed the metallic state of the optimized Bi-D-PDV2 film. The preliminary SERS applications on Rhodamine 6 G (RH6G) selected a Bi-D-PDV2 film with an enhancement factor (EF) of ∼4 ×105. This optimized film used for L-phenylalanine (Phe) detection, resulted in enhanced sensitivity of ∼2 ×106 EF with a sub-micromolar (0.1 μM) limit of detection (LOD). The ultra-sensitive responses in the sub-μM level from the optimized Bi thin film for standard as well as biomolecule is reported for the first time to the best extent of knowledge. The potential responses from the optimized film gives promising response for its use in ultra-sensitive bio detections even down to single molecular level in future.

Fabrication of Bi-doped In2S3 thin films for highly sensitive UV photodetector applications

Fabrication of highly sensitive, high-speed photodetectors, especially using cost-effective and less toxic materials, has attracted continuous attention due to their outstanding advantages. In this report, we present different properties of Bi-doped (0,1, 3, and 5 wt%) In2S3 thin films for UV photodetectors. Bi-doped (0, 1, 3, and 5 wt%) In2S3 thin films were coated on glass substrates at a temperature of 350 °C using a low-cost nebulizer spray pyrolysis method. X-ray diffraction XRD analysis confirmed the cubic phase β-In2S3 for all the deposited films and high crystallinity is obtained for 1 wt% Bi-doped film. The presence of densely packed grains in 1 wt% Bi-doped In2S3 thin film and also small grains observed for undoped In2S3 sample is evident form morphology studies. Bi doping has caused an enhancement of optical absorption and incorporation of 1 wt% of Bi3+ into In2S3 has shifted the optical band gap from 2.87 to 2.78 eV. Current − Voltage characteristics and Current–Time characterization are used to know the key parameters of the photodetectors. Among all fabricated photodetectors, the In2S3 thin film doped with 1 wt% Bi showed superior photodetector performance with calculated Responsivity (R), Detectivity (D*), and External quantum efficiency (EQE) values of 0.65 AW−1, 15 × 1010 Jones, 125 % respectively. Transient photo-response analysis showed low rise and fall time of 3.21 and 3.78 s respectively for the 1 wt% Bi-doped sample. Optimally doped In2S3: Bi (1 wt%) thin film is most suited to fabricate photo sensing-based optoelectronic devices in UV region of the spectrum.

Ultra-sensitive SERS detection of L-tyrosine on the microstructurally tuned DC sputtered plasmonic Bi thin films

Ultra-sensitive SERS detection of L-tyrosine on the microstructurally tuned DC sputtered plasmonic Bi thin films

Structure, ferroelectric, and enhanced fatigue properties of sol–gel-processed new Bi-based perovskite thin films of Bi(Cu1/2Ti1/2)O3–PbTiO3

Bi-based perovskite ferroelectric thin films have wide applications in electronic devices due to their excellent ferroelectric properties. New Bi-based perovskite thin films Bi(Cu1/2Ti1/2)O3–PbTiO3 (BCT–PT) are deposited on Pt(111)/Ti/SiO2/Si substrates in the present study by the traditional sol–gel method. Their structures and related ferroelectric and fatigue characteristics are studied in-depth. The BCT–PT thin films exhibit good crystallization within the phase-pure perovskite structure, besides, they have a predominant (100) orientation together with a dense and homogeneous microstructure. The remnant polarization (2P r) values at 30 μC/cm2 and 16 μC/cm2 are observed in 0.1BCT–0.9PT and 0.2BCT–0.8PT thin films, respectively. More intriguingly, although the polarization values are not so high, 0.2BCT–0.8PT thin films show outstanding polarization fatigue properties, with a high switchable polarization of 93.6% of the starting values after 108 cycles, indicating promising applications in ferroelectric memories.

Hidden Direct Bandgap of Bi2O2Se by Se Vacancy and Enhanced Direct Bandgap of Bismuth Oxide Overlayer.

The Bi2O2Se surfaces are well-known to possess 50% Se vacancies, yet they have shown no in-gap states within the indirect bandgap (∼0.8 eV). We have found that the hidden in-gap states arising from the Se vacancies in a 2 × 1 pattern induce a reduced direct bandgap (∼0.5 eV). Such a reduced direct bandgap is responsible for the high electron mobility of Bi2O2Se. Moreover, the Bi oxide overlayers of the Bi thin films, formed through air exposure and annealing, unexpectedly exhibit a large direct bandgap (∼2.1 eV). The simplified fabrication of Bi oxide overlayers provides promise for improving Bi2O2Se electronic devices and enhancing photocatalytic activity.

Co-deposition of bismuth-nitrogen films on MgO (001) by molecular beam epitaxy

We attempted to grow a thin film of BiN by co-deposition of bismuth and nitrogen on rock-salt structure MgO (001) substrates. Furthermore, we studied the effect of variation of the growth temperature and the nitrogen to bismuth flux ratios on sample growth. For the samples grown and conditions used, we do not find strong evidence for the formation of a bulk Bi-N alloy. Even for very high nitrogen to bismuth flux ratio, we observed only bismuth and no nitrogen using bulk Rutherford back-scattering spectroscopy measurements, and only 1%–2% nitrogen was seen through surface Auger electron spectroscopy measurements. The in-plane lattice measurements show that the resulting Bi (110) samples are strained, which is presumably caused by lattice mismatch between the sample and the substrate when grown without any buffer layer. The use of a high-temperature buffer layer helps to release strain in the sample but only along one axis. Measurements of the atomic layer spacing using x-ray diffraction and also scanning tunneling microscopy confirm the Bi (110) thin film sample structure.

The growth mechanism and properties of Bi2212 thin films on miscut substrates by sol-gel method

A sol-gel methodology is employed to prepare Bi2212 thin films on single crystal LaAlO3 miscut substrates with nominal tilt angles of 0°, 5°, 10°, and 15°. The study focuses on examining the phase purity, crystal structure, surface morphology, microstructure, and properties of these thin films. Experimental results indicate that the growth of Bi2212 thin films on miscut substrates proceeds through the step-flow mode using the sol-gel method. Higher tilt angles lead to an increase in the conventional resistivity of Bi2212 thin films. Tilted Bi2212 thin films exhibit a typical transverse Seebeck effect when comparing the resistivity in different directions. Notably, the Seebeck coefficient difference reaches 12 V/K when the substrate tilt angle is set at 15°. Meanwhile, tilted Bi2212 thin films consistently exhibit outstanding superconducting transition temperature (Tc) while demonstrating lower critical current density (Jc) values. These findings offer valuable insights for the development of Bi2212 high temperature superconducting thin films (HTSFs) in thermoelectric and superconductive devices, serving as a reference point for achieving optimal film characteristics.

Grain size effect on the transport properties of polycrystalline Bi(000l) films grown in MgO(001) and glass

The crystal growth and transport properties of the polycrystalline Bi(0001) films grown on MgO(001) and glass substrates were compared. The morphology and electron transport properties with different thickness have been analyzed. The stress-induced bandgap leads to the shift of transition temperature from semimetal to semiconductor transition. Compared with MgO(001) substrates, Bi(0001) thin films on glass substrates have the higher semimetal-semiconductor transition temperature. Furthermore, the electron transport performance is improved, which is attributed to the strain-free van-der-Waals epitaxial preferred orientation grown on the glass substrate. The strain effect on the transport performance is greater than that on in-plane grain boundaries.

Strain and atomic stacking of bismuth thin film in its quasi-van der Waals epitaxy on (111) Si substrate.

We report on the structural properties of Bi thin films grown on (111) Si substrates with a thickness of 22-30 BL. HRXRD and EBSD measurements show that these Bi films are mainly composed of twinning grains in the (0003) direction. The grain size can be as large as tens of microns. From a double-peak (01[Formula: see text]4) φ-scan, we found two pairs of twinning phases coexisting with a rotation angle of ~ 3.6°. We proposed a coincidence site lattice model based on preferential close-packed sites for Bi atoms on Si (111) surface to explain the coexistence of the rotation phases in the quasi-van der Waals epitaxy. From the measured lattice constants c and a of our samples, along with the data from the literature, we derived a c-a relation: (c-c0) = - 2.038(a-a0), where c0 and a0 are the values of bulk Bi. The normalized position of the second basis atom in the unit cell x, in these strained Bi films is found very close to that of bulk Bi, indicating that the strain does not disturb the Peierls distortion of the lattice. The fixed ratio of bilayer thickness to lattice constant c, reveals that the elastic properties of covalent-bonded bilayer dominate those of Bi crystal.

A closer look at how symmetry constraints and the spin–orbit coupling shape the electronic structure of Bi(111)

Fully relativistic density-functional-theory calculations of Bi(111) thin films are analyzed to revisit their two metallic surface-states branches. We first contrast these metallic branches with surface states arising at gaps in the valence band opened by the spin–orbit coupling (SOC). We find that the two metallic branches along do not overlap with the bulk band at the zone boundary, M. We show that the spin texture observed in such states cannot be traced to the lifting of Kramers’ degeneracy. Instead, we track them to the – SOC splitting, the potential anisotropy for in-plane and out-of-plane states, and the coupling between the opposite surfaces of a slab occurring near M, which is driven by a spatial redistribution of the four metallic states composing the two metallic branches. Each of these branches appears to be non-degenerate at the tested surface, yet each is degenerate with another state of opposite spin at the other surface. Nevertheless, the four metallic states bear some contribution on both surfaces of the film because of their spatial redistribution near M. The overlapping among these states near M, afforded by their spatial redistribution on both surfaces, causes a hybridization that perpetuates the splitting between the two branches, makes the film’s electronic structure thickness dependent near M, extinguishes the magnetic moment of the metallic states avoiding the magnetic-moment discontinuity at M, and denies the need or expectancy of the metallic branches becoming degenerate at M. We propose that the opposite spin polarization observed for the two metallic branches occurs because the surface atoms retain their covalent bonds and thus cannot afford magnetic polarization. We show that the Rashba-splitting of the metallic states for inversion-asymmetric films does not have a fixed magnitude but can be tuned by changing the perturbation breaking inversion symmetry.

Phase-Selective Epitaxy of Trigonal and Orthorhombic Bismuth Thin Films on Si (111).

Over the past three decades, the growth of Bi thin films has been extensively explored due to their potential applications in various fields such as thermoelectrics, ferroelectrics, and recently for topological and neuromorphic applications, too. Despite significant research efforts in these areas, achieving reliable and controllable growth of high-quality Bi thin-film allotropes has remained a challenge. Previous studies have reported the growth of trigonal and orthorhombic phases on various substrates yielding low-quality epilayers characterized by surface morphology. In this study, we present a systematic growth investigation, enabling the high-quality growth of Bi epilayers on Bi-terminated Si (111) 1 × 1 surfaces using molecular beam epitaxy. Our work yields a phase map that demonstrates the realization of trigonal, orthorhombic, and pseudocubic thin-film allotropes of Bi. In-depth characterization through X-ray diffraction (XRD) techniques and scanning transmission electron microscopy (STEM) analysis provides a comprehensive understanding of phase segregation, phase stability, phase transformation, and phase-dependent thickness limitations in various Bi thin-film allotropes. Our study provides recipes for the realization of high-quality Bi thin films with desired phases, offering opportunities for the scalable refinement of Bi into quantum and neuromorphic devices and for revisiting technological proposals for this versatile material platform from the past 30 years.

A novel method to improve the morphology of Bi2212 film by PVA-assisted Pechini sol-gel method

Bi2212 high-temperature superconducting thin films (HTSFs) have emerged as the most promising material for terahertz (THz) devices due to their intrinsic Josephson effect. Enhancing the surface smoothness of these films is crucial for their practical application. In this study, metal nitrates were utilized as the raw material to prepare Bi2212 HTSFs on SrTiO3 (100) substrates using the Pechini sol-gel method. The chelating agent ethylenediamine tetraacetic acid (EDTA) and the surfactant polyvinyl alcohol (PVA) were employed to improve the dissolution characteristics of Bi2212 solution. The influence of various parameters such as sintering temperatures, surfactant concentrations, and metal ion ratios was systematically investigated to assess the phase purity, crystallinity, surface morphology, and electrical properties of the Bi2212 superconducting thin films. The results demonstrated that a higher concentration of PVA led to reduced solubility of the Bi2212 solution. Notably, when the PVA concentration was set at 1 %, the fabricated Bi2212 thin film exhibited exceptional epitaxial properties, enhanced Bi2212 phase purity, reduced surface roughness, and higher Tc. These outcomes provide valuable insights for the development of Bi2212 HTSFs in superconducting devices, as they serve as a reference point for achieving optimal film characteristics.