Two-Dimensional Phosphorus Porous Polymorphs with Tunable Band Gaps

Exploring stable two-dimensional (2D) crystalline structures of phosphorus with tunable properties is of considerable importance partly due to the novel anisotropic behavior in phosphorene and potential applications in high-performance devices. Here, 21 new 2D phosphorus allotropes with porous structure are reported based on topological modeling method and first-principles calculations. We establish that stable 2D phosphorus crystals can be obtained by topologically assembling selected phosphorus monomer, dimer, trimer, tetramer, and hexamer. Nine of reported structures are predicted to be more stable than white phosphorus. Their dynamic and thermal stabilities are confirmed by the calculated vibration spectra and Born–Oppenheimer molecular dynamic simulation at temperatures up to 1500 K. These phosphorus porous polymorphs have isotropic mechanic properties that are significantly softer than phosphorene. The electronic band structures calculated with the HSE06 method indicate that new structures are semiconductors with band gaps ranging widely from 0.15 to 3.42 eV, which are tuned by the basic units assembled in the network. Of particular importance is that the position of both conduction and valence band edges of some allotropes matches well with the chemical reaction potential of H₂/H⁺ and O₂/H₂O, which can be used as element photocatalysts for visible-light-driven water splitting

Three-Dimensional Covalently Linked Allotropic Structures of Phosphorus

The discovery of new phosphorus allotropes has attracted continuous attention over recent decades, partly due to the importance of phosphorus in life and their fantastic structural diversity. Generally, phosphorus allotropes consist of covalently linked substructures, stacked together with van der Waals interactions, and a few phosphorus allotropes possess three-dimensional covalently linked structures only at high pressure. On the basis of first-principles calculations, five new phosphorus allotropes with three-dimensional covalently linked structures are predicted by assembling phosphorus units at ambient pressure, which are energetically more favorable than white phosphorus. Particularly, three of them share the same structures as those of previously reported three-dimensional nitrogen allotropes. These new allotropes are semiconductors with band gaps ranging from 0.52 to 2.39 eV, and the Young’s modulus varies from 39 to 72 GPa. The structural stability of the new phosphorus allotropes are confirmed with a phonon spectrum and Born–Oppenheimer molecular dynamic simulation at temperatures up to 700 K. Our findings enrich the phosphorus allotrope family with three-dimensional covalently linked structures at ambient pressure and versatile electronic properties

Room-Temperature Half-Metallicity in La(Mn,Zn)AsO Alloy via Element Substitutions

Exploring half-metallic materials with high Curie temperature, wide half-metallic gap, and large magnetic anisotropy energy is one of the effective solutions to develop high-performance spintronic devices. Using first-principles calculations, we design a practicable half-metal based on a layered La­(Mn_0.5Zn_0.5)­AsO alloy via element substitutions. At its ground state, the pristine La­(Mn_0.5Zn_0.5)­AsO alloy is an antiferromagnetic semiconductor. Either hole doping via (Ca²⁺/Sr²⁺,La³⁺) substitutions or electron doping via (H^–/F^–,O^2–) substitutions in the [LaO]⁺ layer induce half-metallicity in the La­(Mn_0.5Zn_0.5)­AsO alloy. The half-metallic gap is as large as 0.74 eV. Monte Carlo simulations based on the Ising model predict a Curie temperature of 475 K for 25% Ca doping and 600 K for 50% H doping, respectively. Moreover, the quasi two-dimensional structure endows the doped La­(Mn,Zn)­AsO alloy a sizable magnetic anisotropy energy with the magnitude of at least one order larger than those of Fe, Co, and Ni bulks

Fluorination and Conjugation Engineering Synergistically Enhance the Optoelectronic Properties of Two-Dimensional Hybrid Organic–Inorganic Perovskites

Two-dimensional (2D) hybrid organic–inorganic perovskites (HOIPs) are expected to be a viable alternative to three-dimensional (3D) analogs in solar cells (SCs) and optoelectronic devices due to their high stability, diverse composition, and physical properties. However, unsuitable band alignment and large bandgaps limit the power conversion efficiency (PCE) improvement of SCs based on 2D HOIPs. Here, we report a molecular design strategy that combines fluorination and conjugation engineering to tune the electronic structure and optimize the PCE of 2D HOIPs. Our results show that type IIa band alignment and tunable bandgaps can be achieved in 2D Dion–Jacobson (DJ) HOIPs by H/F substitution of organic cations with different degrees of conjugation. In general, the bandgap of 2D DJ-HOIPs decreases monotonously with the increase of the number of F atoms, which is due to the gradual decrease of the lowest unoccupied molecular orbitals (LUMO) of organic cations. In addition, the enhanced interlayer charge transfer and higher dielectric constant suggest that the fluorination-induced dielectric limitations are weakened. The estimated PCE of 2D DJ-HOIPs is exponentially increased and positively correlated with the degree of conjugation and fluorination of organic cations, with a PCE approaching 29% under their synergistic effect. Our results not only provide promising candidates for photovoltaic device applications but also provide an effective method for PCE optimization

Turning Nonmagnetic Two-Dimensional Molybdenum Disulfides into Room-Temperature Ferromagnets by the Synergistic Effect of Lattice Stretching and Charge Injection

Exploring two-dimensional (2D) room-temperature magnetic materials in the field of 2D spintronics remains a formidable challenge. The vast array of nonmagnetic 2D materials provides abundant resources for exploration, but the strategy to convert them into intrinsic room-temperature magnets remains elusive. To address this challenge, we present a general strategy based on surface halogenation for the transition from nonmagnetism to intrinsic room-temperature ferromagnetism in 2D MoS2 based on first-principles calculations. The derived 2D halogenated MoS2 are half-semimetals with a high Curie temperature (TC) of 430–589 K and excellent stability. In-depth mechanistic studies revealed that this marvelous nonmagnetism-to-ferromagnetism transition originates from the modulation of the splitting as well as the occupation of the Mo d orbitals by the synergy of lattice stretching and charge injection induced by the surface halogenation. This work establishes a promising route for exploring 2D room-temperature magnetic materials from the abundant pool of 2D nonmagnetic counterparts

Fluorination and Conjugation Engineering Synergistically Enhance the Optoelectronic Properties of Two-Dimensional Hybrid Organic–Inorganic Perovskites

Two-dimensional (2D) hybrid organic–inorganic perovskites (HOIPs) are expected to be a viable alternative to three-dimensional (3D) analogs in solar cells (SCs) and optoelectronic devices due to their high stability, diverse composition, and physical properties. However, unsuitable band alignment and large bandgaps limit the power conversion efficiency (PCE) improvement of SCs based on 2D HOIPs. Here, we report a molecular design strategy that combines fluorination and conjugation engineering to tune the electronic structure and optimize the PCE of 2D HOIPs. Our results show that type IIa band alignment and tunable bandgaps can be achieved in 2D Dion–Jacobson (DJ) HOIPs by H/F substitution of organic cations with different degrees of conjugation. In general, the bandgap of 2D DJ-HOIPs decreases monotonously with the increase of the number of F atoms, which is due to the gradual decrease of the lowest unoccupied molecular orbitals (LUMO) of organic cations. In addition, the enhanced interlayer charge transfer and higher dielectric constant suggest that the fluorination-induced dielectric limitations are weakened. The estimated PCE of 2D DJ-HOIPs is exponentially increased and positively correlated with the degree of conjugation and fluorination of organic cations, with a PCE approaching 29% under their synergistic effect. Our results not only provide promising candidates for photovoltaic device applications but also provide an effective method for PCE optimization

Room-Temperature Ferromagnetism in Two-Dimensional Fe₂Si Nanosheet with Enhanced Spin-Polarization Ratio

Searching experimental feasible two-dimensional (2D) ferromagnetic crystals with large spin-polarization ratio, high Curie temperature and large magnetic anisotropic energy is one key to develop next-generation spintronic nanodevices. Here, 2D Fe₂Si nanosheet, one counterpart of Hapkeite mineral discovered in meteorite with novel magnetism is proposed on the basis of first-principles calculations. The 2D Fe₂Si crystal has a slightly buckled triangular lattice with planar hexacoordinated Si and Fe atoms. The spin-polarized calculations with hybrid HSE06 function method indicate that 2D Fe₂Si is a ferromagnetic half metal at its ground state with 100% spin-polarization ratio at Fermi energy level. The phonon spectrum calculation and ab initio molecular dynamic simulation shows that 2D Fe₂Si crystal has a high thermodynamic stability and its 2D lattice can be retained at the temperature up to 1200 K. Monte Carlo simulations based on the Ising model predict a Curie temperature over 780 K in 2D Fe₂Si crystal, which can be further tuned by applying a biaxial strain. Moreover, 2D structure and strong in-plane Fe–Fe interaction endow Fe₂Si nanosheet sizable magnetocrystalline anisotropy energy with the magnitude of at least two orders larger than those of Fe, Co and Ni bulks. These novel magnetic properties render the 2D Fe₂Si crystal a very promising material for developing practical spintronic nanodevice

Band-Gap Engineering <i>via</i> Tailored Line Defects in Boron-Nitride Nanoribbons, Sheets, and Nanotubes

We perform a comprehensive study of the effects of line defects on electronic and magnetic properties of monolayer boron-nitride (BN) sheets, nanoribbons, and single-walled BN nanotubes using first-principles calculations and Born–Oppenheimer quantum molecular dynamic simulation. Although line defects divide the BN sheet (or nanotube) into domains, we show that certain line defects can lead to tailor-made edges on BN sheets (or imperfect nanotube) that can significantly reduce the band gap of the BN sheet or nanotube. In particular, we find that the line-defect-embedded zigzag BN nanoribbons (LD-zBNNRs) with chemically homogeneous edges such as B- or N-terminated edges can be realized by introducing a B₂, N₂, or C₂ pentagon–octagon–pentagon (5–8–5) line defect or through the creation of the antisite line defect. The LD-zBNNRs with only B-terminated edges are predicted to be antiferromagnetic semiconductors at the ground state, whereas the LD-zBNNRs with only N-terminated edges are metallic with degenerated antiferromagnetic and ferromagnetic states. In addition, we find that the hydrogen-passivated LD-zBNNRs as well as line-defect-embedded BN sheets (and nanotubes) are nonmagnetic semiconductors with markedly reduced band gap. The band gap reduction is attributed to the line-defect-induced impurity states. Potential applications of line-defect-embedded BN nanomaterials include nanoelectronic and spintronic devices

Band-Gap Engineering <i>via</i> Tailored Line Defects in Boron-Nitride Nanoribbons, Sheets, and Nanotubes

We perform a comprehensive study of the effects of line defects on electronic and magnetic properties of monolayer boron-nitride (BN) sheets, nanoribbons, and single-walled BN nanotubes using first-principles calculations and Born–Oppenheimer quantum molecular dynamic simulation. Although line defects divide the BN sheet (or nanotube) into domains, we show that certain line defects can lead to tailor-made edges on BN sheets (or imperfect nanotube) that can significantly reduce the band gap of the BN sheet or nanotube. In particular, we find that the line-defect-embedded zigzag BN nanoribbons (LD-zBNNRs) with chemically homogeneous edges such as B- or N-terminated edges can be realized by introducing a B₂, N₂, or C₂ pentagon–octagon–pentagon (5–8–5) line defect or through the creation of the antisite line defect. The LD-zBNNRs with only B-terminated edges are predicted to be antiferromagnetic semiconductors at the ground state, whereas the LD-zBNNRs with only N-terminated edges are metallic with degenerated antiferromagnetic and ferromagnetic states. In addition, we find that the hydrogen-passivated LD-zBNNRs as well as line-defect-embedded BN sheets (and nanotubes) are nonmagnetic semiconductors with markedly reduced band gap. The band gap reduction is attributed to the line-defect-induced impurity states. Potential applications of line-defect-embedded BN nanomaterials include nanoelectronic and spintronic devices

Unusual Metallic Microporous Boron Nitride Networks

Two metallic zeolite-like microporous BN crystals with all-sp² bonding networks are predicted from an unbiased structure search based on the particle-swarm optimization (PSO) algorithm in combination with first-principles density functional theory (DFT) calculations. The stabilities of both microporous structures are confirmed via the phonon spectrum analysis and Born–Oppenheimer molecular dynamics simulations with temperature control at 1000 K. The unusual metallicity for the microporous BN allotropes stems from the delocalized p electrons along the axial direction of the micropores. Both microporous BN structures entail large surface areas, ranging from 3200 to 3400 m²/g. Moreover, the microporous BN structures show a preference toward organic molecule adsorption (e.g., the computed adsorption energy for CH₃CH₂OH is much more negative than that of H₂O). This preferential adsorption can be exploited for water cleaning, as demonstrated recently using porous boron BN nanosheets (Nat. Commun. 2013, 4, 1777)