N-type Doping Effect Research Articles

Investigation of electronic, optical and thermoelectric properties in orthorhombic perovskite SmFeO3

In this work, we have investigated the electronic, optical, and thermoelectric properties of orthorhombic perovskite SmFeO3 using density functional and Boltzmann transport theories, for renewable energy applications. The modeling of the exact electron exchange-correlation has been carried out using both Generalized Gradient Approximation (GGA) and a functional modified with Hubbard interactions. The spin-polarized calculations show that SmFeO3 adopts a G-type antiferromagnetic configuration. The studied compound's electronic band structure and density of states analysis reveal its p-type semiconductor behavior. Furthermore, the optical properties such as real ε1(ω) and imaginary ε2(ω) components of the dielectric function as well as other conventional optical parameters, were investigated. The results show that SmFeO3 is a promising material for optoelectronic applications. The calculated transport properties including the Seebeck coefficient (S), the electrical conductivity (σ/τ), the electronic thermal conductivity (k0/τ) and the electronic figure of merit (ZTe) show significant results. The studied perovskite is also a potential candidate for thermoelectric applications, due to its high Seebeck coefficient, reaching 2388 μV/K, and the large electronic figure of merit which is close to 1 at room temperature. To improve the thermoelectric performance of SmFeO3 material, we have studied the effect of both p-type and n-type doping on its thermoelectric behavior at different temperature values.

Enhanced thermoelectric performance of n-type Mg3.2Sb1.5Bi0.5 by rare-earth elements (Er, Tb, Tm) doping into Mg site

The n-type Mg3.2Sb1.5Bi0.5 has emerged as a promising candidate for thermoelectric materials and has attracted significant research interest. However, effective n-type dopants have been predominantly limited to chalcogens. In our work, we found that rare-earth elements (Er, Tb, Tm) are highly effective dopants for n-type Mg3.2Sb1.5Bi0.5. Through a combination of theoretical predictions and experimental validations, we demonstrate that these dopants significantly enhance the carrier concentration, leading to improved thermoelectric performance. Specifically, we employed direct ball milling and spark plasma sintering to introduce rare-earth elements at the Mg sites. Experimental results show that doping rare-earth elements in n-type Mg3.2Sb1.5Bi0.5 has a higher carrier concentration ( ≈ 8.4 × 1019 cm−3), which is higher than that of chalcogen-doped samples ( ≈ 2 × 1019 cm−3). High power factor (S2σ) ≈ 16 μW cm−1K−2 was obtained in rare-earth elements (Er, Tb, Tm) doped samples. Combined with the lowered lattice thermal conductivity due to the introduction of effective phonon scattering centers in Mg3.2−xAxSb1.5Bi0.5 (A= Er, Tb, Tm) sample. Finally, the ZT values of all doped samples reached ≈ 1.44 at 750 K. The highest peak ZT is ≈ 1.65 at 750 K for Mg3.195Er0.005Sb1.5Bi0.5. The rare-earth elements (Er, Tb, Tm) doped n-type Mg3Sb1.5Bi0.5 has comparable thermoelectric performance with the chalcogen-doped n-type Mg3Sb1.5Bi0.5, exhibiting promising potential for practical applications. This present work offers a comprehensive understanding of the effect of cation site doping improves the thermoelectric properties of n-type Mg3Sb2.

N-Type Doping Effect of Anthracene-Based Cationic Dyes in Organic Electronics.

n-Type doping for improving the electrical characteristics and air stability of n-type organic semiconductors (OSCs) is important for realizing advanced future electronics. Herein, we report a selection method for an effective n-type dopant with an optimized structure and thickness based on anthracene cationic dyes with high miscibility induced by a molecular structure similar to that of OSCs. Among the doped OSCs evaluated, rhodamine B (RhoB)-doped OSC exhibits the highest density, a smallest roughness of 2.69 nm, a phase deviation of 0.85° according to atomic force microscopy measurements, and the highest electron mobility (μ), showing its high miscibility. Surface doping of RhoB affords the lowest contact resistance of 2.01 × 105 Ω cm compared to bulk and contact doping, resulting in an effective doping structure. The RhoB-doped OSC retains 81.63% of the original μ value of 6.13 × 10-2 cm2 V-1 s-1 after 15 days, whereas pristine OSC shows a lower μ of 2.33 × 10-2 cm2 V-1 s-1 and maintains only 4.41% of the original value after 15 days. Our findings demonstrate that this methodology is effective for the selection of a high-performance n-type dopant for OSCs toward the development of high-performance and air-stable n-type organic electronics.

Optical conductivity and linear dichroism in monolayer C[formula omitted]N

We theoretically study the optical properties of monolayer C3N within the framework of linear response theory by using a two band effective k⋅p Hamiltonian. We find that both the effective masses and optical conductivities are anisotropic arising from the anisotropic band structure at the M point. Although the inter-band coupling only exists in the armchair (x-)direction, the effective mass along the armchair direction is larger than that along the zigzag (y-)direction. Interestingly, the absorption part of the optical conductivity Re σxx excited by linearly polarized light along the armchair direction is an order of magnitude larger than Re σyy excited by linearly polarized light along the zigzag direction, resulting in a strong linear dichroism, because the inter-band optical conductivity is dominated by inter-band coupling which only exists in the armchair direction. Finite doping can adjust the optical conductivities i.e., Re σxx and Re σyy and modulate the linear dichroism, but the effects of n-type doping and p -type doping are different because of the electron–hole asymmetry. Our results provide further understanding of the electronic state of monolayer C3N and maybe useful to design polarized optical devices based on it.

Performance enhancement of solar-blind UV photodetector by doping silicon in β-Ga2O3 thin films prepared using radio frequency magnetron sputtering

Si-doped β-Ga2O3 thin films were prepared on c-plane (001) sapphire substrates by radio frequency magnetron sputtering, and then annealed at 800 °C under Ar atmosphere for 1 h. Finally, Metal-Semiconductor-Metal type solar-blind UV photodetectors were prepared using the annealed β-Ga2O3 films. The structure, composition, optical properties and photoelectric detection performance of the films were studied using XRD, EDS, UV–Vis, PL spectroscopy and Keithley-4200 system. Results show that after silicon doping, the preferred orientation of the β-Ga2O3 film varies from (−201) to (200) and (201) crystal planes. EDX and XPS results show that 2.34 at% silicon was doped into Ga2O3 films by substituting Ga atoms. Both XPS and PL results show a decline of defect concentration within the Si-doped films, including oxygen vacancy. Si-doped β-Ga2O3 films exhibit enhanced solar-blind detection performance, with lower dark current (32.2 × 10−12 A) under 15 V bias, higher light-to-dark current ratio (3.2 × 104), higher light power density of 2.4 μW/cm2, and shorter response time. The resultant responsivity, detectivity, and external quantum efficiency are 1.146A/W, 7.14 × 1011Jones, and 5.605 %, respectively, more than one order of magnitude higher than the undoped device. This work indicates that Si is an effective n-type dopant for improving the detection performance of β-Ga2O3 film based solar-blind UV photodetectors.

In-situ constructing Co/Mo co-doped Na3V2(PO4)3 with coral cluster porous structure boosting high performance for sodium ion batteries

Na3V2(PO4)3 (NVP) is suffered from poor conductivities and terrible structure stability. Herein, Co/Mo co-doped NVP with unique cluster porous structure is prepared. Notably, Co2+ replacing V3+ provides useful p-type effects, manufacturing more acceptor levels and generating equal hole carriers, which facilitates the ionic conductivity. Moreover, the larger ionic radius of Co2+ significantly enlarges the interplanar spacing to broaden ionic migration channel. The doped Co2+ can function as pillar ions to reinforce the crystal structure, further improving structure stability. Meanwhile, Moderate Mo6+ is introduced to keep charge balance, resulting in beneficial n-type doping effects, which can bring more electrons and increase the electronic concentration to speed up electronic conduction. Notably, a unique coral cluster porous structure is formed after controlling the added Co/Mo contents. This distinctive morphology allows active materials expose more contact areas with electrolyte to enhance infiltration effects, increasing the active sites to release more reversible capacity. Moreover, the porous construction withstands the stress resulting from the volume contraction during Na+ de-insertion. Comprehensively, NVCMP0.15 exhibits a value of 90.7 mAh g−1 at 50C and retains 68.5 mAh g−1 after 2000 cycles with retention ratio of 75.52 %. Ex-situ XRD/XPS/SEM after cycling indicate great improvements in crystal stability of NVCMP0.15.

Effect of n-type Cl doping on electrical conductivity of few layer WS2

Effect of n-type Cl doping on electrical conductivity of few layer WS2

Critical role of dopant bond strength in enhancing the conductivity of n-type doped κ-Ga2O3

We report a density functional theory study on the effects of n-type doping on the electrical conductivity of κ-Ga2O3. Both group-IV (X = Si, Ge, Sn) and group-VII dopants (Y = F, Cl, Br, I) are considered. All dopants introduce resonant donor states above the conduction band minimum, which induce a semiconductor-to-metal transformation. The resonant donor states interact with the extended conduction band-edge via a charge transfer mechanism, altering the band-edge effective mass me* and electron mobility μe. me* exhibits a linear dependence on the strength of X-O (Ga-Y) bonds, making the latter a good descriptor for quantifying the effect of dopants. Using this descriptor, we predict that dopant C may provide a higher conductivity under O-rich condition.

Heterostructure of Ta5+-substituted Na3V2(PO4)3–TaN promoting the activation of V4+/V5+ redox couple for high performance sodium-ion batteries

Currently, low capacity with poor kinetics seriously hinders the development of Na3V2(PO4)3 (NVP). Herein, a simultaneous optimized scheme of Ta5+ substitution and carbon nanotubes (CNTs) enwrapping is proposed. The substitution of hypervalent Ta5+ at V3+ site introduces a favorable n-type doping effect to generate extra electrons, increasing electron concentration to accelerate electronic conductivity. Ta5+ behaves as a pillar ion to expand Na + migration channel and stabilize the skeleton. Moreover, a new phase of TaN is produced, which embeds into the Na3V2(PO4)3 phase to generate grain boundary. Benefiting from this heterojunction, Na+ diffusion rate could be effectively promoted. The addition of CNTs further restricts agglomeration growth of particles, making the grains smaller and more uniform. Benefiting from the synergetic improved kinetics, a higher voltage platform at 3.9 V is activated. Due to the investigations of ex-situ X-ray photoelectron spectroscopy, the extra plateau is derived from the V4+/V5+ redox couple. Moreover, Density Functional Theoretical calculation suggests the favorable Ta5+ substitution optimizes the electronic structure of NVP to reduce the band gap. Accordingly, the modified NVPT/C@CNTs0.15 submits 125.5 mA h g−1 at 0.1C, and delivers a high value of 77.5 mA h g−1 at 100 C with retention rate of 81.03% after 12000 cycles.

Constructing heterostructure by co-doping of Ta5+ and F− with carbon nanotubes to improve kinetic properties of Na3V2(PO4)3

The advancement of Na3V2(PO4)3 has been impeded by its subpar kinetic characteristics, resulting in suboptimal electrochemical performance. In this case, a dual modification strategy involving Ta and F co-doping is employed, along with the incorporation of carbon nanotubes (CNTs), is introduced. Notably, the substitution of high-valence Ta5+ for V3+ ions induces an n-type doping effect, thereby increasing the density of free electrons and enhancing electrochemical performance. Moreover, Ta5+ possesses a comparatively larger ionic radius than V3+, which enhances the ease of Na+ transport, leading to an increased rate of ionic diffusion. Furthermore, Ta5+ ions play a crucial role in reinforcing the crystal structure, thereby strengthening the stability of the NVP system. Importantly, during the high-temperature calcination process, the reduction of carbon results in the conversion of Ta5+ to Ta3+, forming a novel conductive TaN phase through its reaction with N2. This TaN phase, known for its high conductivity, intercalates into the NVP bulk as interlayers, forming beneficial grain boundaries. Thanks to this unique TaN//NVP heterojunction, the migration of Na+ ions is notably accelerated along the grain boundaries rather than within the NVP bulk. The introduction of F contributes to reducing the grain size of active particles, consequently shortening the pathways for Na+ migration and improving kinetic properties. Moreover, the presence of carbon layers and the encapsulation of CNTs collaboratively construct a highly conductive cross-linking network, elevating both electronic conductivity and mitigating NVP particle aggregation during high-temperature sintering. Consequently, the modified NVTPF0.07/@CNTs sample exhibits outstanding performance in both half and full cells, underscoring its substantial potential for application in the field of sodium-ion batteries.

Structural insight into nanoscale inhomogeneity of electrical properties in highly conductive polycrystalline ZnO thin films doped using methane

Recently, methane has been demonstrated as an effective n-type dopant for ZnO thin films deposited using the RF-magnetron sputtering method. It was shown that the major electrical doping effect of methane is caused by hydrogen released during methane decomposition. This work investigates the origin of the observed increase in conductivity of methane-doped ZnO films with the increase in thickness. The study is aimed at describing the nature of this thickness-dependent effect through a detailed analysis of the thickness-dependent morphology and crystalline structure. A combination of structural, electrical, and optical characterization revealed a transition from fine-grained films with a random orientation at early stages to partially (002)-textured films with columnar grains at later stages of growth. It is demonstrated that grain/sub-grain boundaries increase the electrical conductivity and that the contribution of such buried inner boundaries increases with increasing thickness. It is proposed that hydrogen diffuses along the grain and sub-grain boundaries during growth, leading to continuous doping of the buried interfaces. This hydrogen diffusion mechanism results in an apparent ‘additional doping’ of thicker films. The results provide new insights into the thickness-dependent conductivity of doped polycrystalline ZnO films mediated by hydrogen diffusion along internal interfaces.

Charge transfer in superbase n-type doping of PCBM induced by deprotonation.

N-type electronic doping of organic semiconductors (OSCs) by using superbase compounds shows high doping efficiency (H. Wei, Z. Cheng, T. Wu, Y. Liu, J. Guo, P.-A. Chen, J. Xia, H. Xie, X. Qiu, T. Liu, B. Zhang, J. Hui, Z. Zeng, Y. Bai and Y. Hu, Adv. Mater. 2023, 35, 2300084). While a deprotonation reaction is believed to trigger the doping process, the detailed mechanism therein is not yet fully understood. In the present work we theoretically study the electronic structure of the deprotonated Phenyl-C61-butyric acid methyl ester (PCBM) molecule, as well as the charge transfer (CT) between PCBM and its deprotonated species. We find that deprotonated PCBM without formation of a new bond between the deprotonated side chain and fullerene induces electronic structure with broken spin symmetry, where an in-gap state is singly occupied by an unpaired electron. A second scenario that we find to be possible is the formation of a new bond between the deprotonated side chain and a fullerene. This leads to a spin symmetric electronic structure with partially localized in-gap state, which is expected to contribute less to the effective doping. These results show that the deprotonated PCBM species without new bond formation predominantly accounts for the effective n-type doping of PCBM, an insight that will be useful for optimization of this recently discovered doping method.

On-water surface synthesis of electronically coupled 2D polyimide-MoS2 van der Waals heterostructure

The water surface provides a highly effective platform for the synthesis of two-dimensional polymers (2DP). In this study, we present an efficient on-water surface synthesis of crystalline monolayer 2D polyimide (2DPI) through the imidization reaction between tetra (4-aminophenyl) porphyrin (M1) and perylenetracarboxylic dianhydride (M2), resulting in excellent stability and coverage over a large area (tens of cm2). We further fabricate innovative organic-inorganic hybrid van der Waals heterostructures (vdWHs) by combining with exfoliated few-layer molybdenum sulfide (MoS2). High-resolution transmission electron microscopy (HRTEM) reveals face-to-face stacking between MoS2 and 2DPI within the vdWH. This stacking configuration facilitates remarkable charge transfer and noticeable n-type doping effects from monolayer 2DPI to MoS2, as corroborated by Raman spectroscopy, photoluminescence measurements, and field-effect transistor (FET) characterizations. Notably, the 2DPI-MoS2 vdWH exhibits an impressive electron mobility of 50 cm2/V·s, signifying a substantial improvement over pristine MoS2 (8 cm2/V·s). This study unveils the immense potential of integrating 2D polymers to enhance semiconductor device functionality through tailored vdWHs, thereby opening up exciting new avenues for exploring unique interfacial physical phenomena.

Simultaneous modification of dual-substitution with CeO2 coating boosting high performance sodium ion batteries

Na3V2(PO4)3 (NVP) is highly valued based on the stable construction among the polyanionic compounds. Nevertheless, the drawback of low intrinsic conductivity has been impeded its further application. In this paper, the internal channels of the crystal structure are extended by the introduction of larger radius Ce3+, which increases the transport rate of Na+. The introduction of Mo6+ replacing the V site leads to a beneficial n-type doping effect and facilitates the transportation of electrons. Besides, CeO2 cladding is introduced to further enhance the electronic conductivity of NVP system. Initially, CeO2 serves as an n-type semiconductor and functions as a conductive additive to significantly enhance the electronic conductivity of the electrode, thereby improving the electrochemical characteristics. Moreover, CeO2 functions as an oxygen buffer, aiding in the maintenance of active metal dispersion during operation and enabling efficient electron transfer between CeO2 and [VO6] octahedra in NVP, thus fostering outstanding electrical connectivity between the oxides. CeO2 cladding can be effectively integrated with the carbon layer to stabilize the NVP system. Comprehensively, the modified Na3V1.79Ce0.07Mo0.07(PO4)3/C@8wt.%CeO2 (CeMo0.07@8wt.%CeO2) composite exhibits excellent rate and cycling properties. It delivers a capacity of 113.4 mAh/g at 1C with a capacity retention rate of 80.3 % after 150 cycles. Even at 10C and 40C, it also submits high capacities of 84.7 mAh/g and 76 mAh/g, respectively. Furthermore, the CHC//CeMo0.07@8wt.%CeO2 asymmetric full cell possesses excellent sodium storage property, indicating its prospective application potentials.

N-type doping of diamond surface by potassium

For diamond with exceptional physical and chemical properties, it is a challenging task to develop an effective n-type dopant with satisfactory electronic properties. In this work, using the first-principles calculation, we report the n-type doping of diamond surface (areal electron density of 2.508 × 1013–4.090 × 1013 cm−2 and carrier mobility of 189–1186 cm2 V−1 s−1 at 298 K) by surface transfer doping using potassium (K). Electrons are transferred from the K atoms to the diamond surface, then electrons accumulation appears on the diamond surface. In addition, the areal electron density and electron affinity values increase with increasing K concentration. This work provides a new strategy for producing n-type diamond-based devices.

Suppressing Excess Lead Iodide Aggregation and Reducing N-Type Doping at Perovskite/HTL Interface for Efficient Perovskite Solar Cells.

Excess lead iodide (PbI2 ) aggregation at the charge carrier transport interface leads to energy loss and acts as unstable origins in perovskite solar cells (PSCs). Here, a strategy is reported to modulate the interfacial excess PbI2 by introducing π-conjugated small-molecule semiconductors 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline] (TAPC) into perovskite films through an antisolvent addition method. The coordination of TAPC to PbI units through the electron-donating triphenylamine groups and π-Pb2+ interactions allows for a compact perovskite film with reduced excess PbI2 aggregates. Besides, preferred energy level alignment is achieved due to the suppressed n-type doping effect at the hole transport layer (HTL) interfaces. As a result, the TAPC-modified PSC based on Cs0.05 (FA0.85 MA0.15 )0.95 Pb(I0.85 Br0.15 )3 triple-cation perovskite achieved an improved PCE from 18.37% to 20.68% and retained ≈90% of the initial efficiency after 30 days of aging under ambient conditions. Moreover, the TAPC-modified device based on FA0.95 MA0.05 PbI2.85 Br0.15 perovskite produced an improved efficiency of 23.15% compared to the control (21.19%). These results provide an effective strategy for improving the performance of PbI2 -rich PSCs.

Direct Observation of Contact Reaction Induced Ion Migration and its Effect on Non-Ideal Charge Transport in Lead Triiodide Perovskite Field-Effect Transistors.

The migration of ionic defects and electrochemical reactions with metal electrodes remains one of the most important research challenges for organometal halide perovskite optoelectronic devices. There is still a lack of understanding of how the formation of mobile ionic defects impact charge carrier transport and operational device stability, particularly in perovskite field-effect transistors (FETs), which tend to exhibit anomalous device characteristics. Here, the evolution of the n-type FET characteristics of one of the most widely studied materials, Cs0.05 FA0.17 MA0.78 PbI3, is investigated during repeated measurement cycles as a function of different metal source-drain contacts and precursor stoichiometry. The channel current increases for high work function metals and decreases for low work function metals when multiple cycles of transfer characteristics are measured. The cycling behavior is also sensitive to the precursor stoichiometry. These metal/stoichiometry-dependent device non-idealities are correlated with the quenching of photoluminescence near the positively biased electrode. Based on elemental analysis using electron microscopy the observations can be understood by an n-type doping effect of metallic ions that are created by an electrochemical interaction at the metal-semiconductor interface and migrate into the channel. The findings improve the understanding of ion migration, contact reactions, and the origin of non-idealities in lead triiodide perovskite FETs.

A controllable conduction-type photovoltaic effect in MoTe2

In this study, we unveiled that a conduction type can be controlled from the 2H-MoTe2 ambipolar semiconducting phase to the selective opposite n-type or p-type FETs. The polarity inversion has been achieved through the trapped interface states that exist between h-BN and SiO2 upon illumination with an external gate voltage. For the n-type doping effect, we found that it has a positive coefficient with the thickness of h-BN but the p-type doping was not achieved with a thickness of 50 nm or beyond. For the n-type MoTe2 FET, the carrier concentration n(n−MoTe2) and mobility μ(n−MoTe2) were calculated to be ∼2.07 × 1012 cm−2 and ∼20.17 cm2/V/s, respectively, while for the p-type FET n(p−MoTe2) and μ(p−MoTe2) are ∼2.16 × 1012 cm−2 and ∼24.04 cm2/V/s, respectively. Moreover, we also develop a lateral PIN diode with an intrinsic region that was in-between n- and p-type FETs. An electrical performance was also monitored, and an ideal rectifying behavior was reached with a rectification ratio (IfIr) of almost >106. The PIN diode also exhibits a self-biased photovoltaic behavior with an open-circuit voltage (Voc = 440.9 mV). This research work may pave the way for fabricating photodiodes with low power consumption using transition metal dichalcogenides materials.

Influence of AlGaN n-type doping and AlN thickness on the two-dimensional electron gas density (ns) and resistance (R2DEG)

In this paper, electrical characterizations by C(VG) and ID(VG) and comparison with 1D Schrödinger-Poisson simulations are carried out to investigate the effects of AlN layer thickness and n-type AlGaN barrier doping on the two-dimensional electron gas resistance (R2DEG). Specifically, these effects are related to either the electron sheet density (ns) or the mobility (µ). We show that varying the AlN thickness from 0.7 nm (ns = 7.8 × 1012 cm−2) to 1.5 nm (ns = 9.0 × 1012 cm−2) leads to a linear increase of ns. However, simultaneous degradation of the transport properties probably due to intensifying roughness mechanism at high ns tends to limit the improvement of the device properties. Furthermore, we show that the heavily doped AlGaN barrier slightly increases ns and reduces the 2DEG mobility to ∼ 1770 cm2.V−1.s−1 leading to a degraded 2DEG resistance. However, the overall resistance is improved (R = 323 Ω/□) compared to the undoped case (R = 380 Ω/□) due to the simultaneous contribution of two conducting channels at VG = 0 V. To go further, the polarization charges at the AlGaN/AlN and AlN/GaN interfaces are computed in the 1D Schrödinger-Poisson simulations to account for the presence of the AlN layer. A reduced polarization for very thin AlN layers is considered to account for the experimental results. Finally, a very simple empirical model is proposed that predicts the enhancement of polarization charges (σ) as a function of AlN thickness.

N-Type doping of BiVO4 with different F-doped concentrations for improving the electronic character of BiVO4 as a photoanode nanomaterial for solar water splitting: a first-principles study.

Atom doping has been realized as an effective way to improve the photocatalytic performance of the most promising photoanode material, BiVO4, but the effects of doping mass concentration still need to be explored. In this work, the effects of F-doping with different doping mass concentrations (1%, 2%, 5%, 10%, 15%, and 20%) on the electronic character of BiVO4 were examined theoretically using density functional theory (DFT) calculations. The thermal stability of BiVO4 with different F-doped mass concentrations was confirmed using formation energy (Ef) calculations though F-doped BiVO4 becomes harder as the mass concentration of induced dopants increases. n-Type doping effects on the electronic character of BiVO4 were observed upon F-doping, leading to the energy level of CBM shifting far away from the Fermi level and giving F-doped BiVO4 metallic character. Moreover, a linear relationship between the frontier energy level shifts and the total charge transfer amounts from doped F atoms to other atoms involved in F-doped BiVO4 was observed, which means the oxidizing capacity of the VBM is increased and the reducing capacity of the CBM is decreased upon increased F-doped mass concentration. Moreover, the recombination of photogenerated electron-hole pairs is suppressed by F-doping strategies, which will not change a lot with the increased F-doped mass concentration. This means atom doping is an effective strategy to improve the photocatalytic efficiency of the BiVO4, but the number of atoms introduced into BiVO4 should be appropriate.