Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 41
Filtrar
Mais filtros

Base de dados
Tipo de documento
Intervalo de ano de publicação
1.
Nano Lett ; 24(20): 6002-6009, 2024 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-38739273

RESUMO

Two-dimensional van der Waals heterostructures (2D-vdWHs) based on transition metal dichalcogenides (TMDs) provide unparalleled control over electronic properties. However, the interlayer coupling is challenged by the interfacial misalignment and defects, which hinders a comprehensive understanding of the intertwined electronic orders, especially superconductivity and charge density wave (CDW). Here, by using pressure to regulate the interlayer coupling of non-centrosymmetric 6R-TaS2 vdWHs, we observe an unprecedented phase diagram in TMDs. This phase diagram encompasses successive suppression of the original CDW states from alternating H-layer and T-layer configurations, the emergence and disappearance of a new CDW-like state, and a double superconducting dome induced by different interlayer coupling effects. These results not only illuminate the crucial role of interlayer coupling in shaping the complex phase diagram of TMD systems but also pave a new avenue for the creation of a novel family of bulk heterostructures with customized 2D properties.

2.
Nano Lett ; 23(6): 2121-2128, 2023 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-36877932

RESUMO

Two-dimensional (2D) van der Waals heterostructures (VDWHs) containing a charge-density wave (CDW) and superconductivity (SC) have revealed rich tunability in their properties, which provide a new route for optimizing their novel exotic states. The interaction between SC and CDW is critical to its properties; however, understanding this interaction within VDWHs is very limited. A comprehensive in situ study and theoretical calculation on bulk 4Hb-TaSe2 VDWHs consisting of alternately stacking 1T-TaSe2 and 1H-TaSe2 monolayers are investigated under high pressure. Surprisingly, the superconductivity competes with the intralayer and adjacent-layer CDW order in 4Hb-TaSe2, which results in substantially and continually boosted superconductivity under compression. Upon total suppression of the CDW, the superconductivity in the individual layers responds differently to the charge transfer. Our results provide an excellent method to efficiently tune the interplay between SC and CDW in VDWHs and a new avenue for designing materials with tailored properties.

3.
J Am Chem Soc ; 145(30): 16828-16834, 2023 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-37467160

RESUMO

Two-dimensional (2D) van der Waals (vdW) materials, featuring relaxed phase-matching conditions and highly tunable optical nonlinearity, endow them with potential applications in nanoscale nonlinear optical (NLO) devices. Despite significant progress, fundamental questions in 2D NLO materials remain, such as how structural distortion affects second-order NLO properties, which call for advanced regulation and in situ diagnostic tools. Here, by applying pressure to continuously tune the displacement of Nb atoms in 2D vdW NbOI2, we effectively modulate the polarization and achieve a 3-fold boost of the second-harmonic generation (SHG) at 2.5 GPa. By introducing a Peierls distortion parameter, λ, we establish a quantitative relationship between λ and SHG intensity. Importantly, we further demonstrate that the SHG enhancement can be achieved under ambient conditions by anionic substitution to tune the distortion in NbO(I1-xBrx)2 (x = 0-1) compounds, where the chemical tailoring simulates the pressure effects on the structural optimization. Consequently, NbO(I0.60Br0.40)2 with λ = 0.17 exhibits a giant SHG of over 2 orders of magnitude higher than that in monolayer WSe2, reaching the record-high value among reported 2D vdW NLO materials. This work unambiguously demonstrates the correlation between Peierls distortion and SHG property and, more broadly, opens new paths for the development of advanced NLO materials by manipulating the structure distortions.

4.
J Am Chem Soc ; 145(16): 8908-8916, 2023 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-37057869

RESUMO

Chiral perovskites have attracted considerable attention owing to their potential applications in spintronic- and polarization-based optoelectronic devices. However, the structural chirality/asymmetry transfer mechanism between chiral organic ammoniums and achiral inorganic frameworks is still equivocal, especially under extreme conditions, as the systematic structural differences between chiral and achiral perovskites have been rarely explored. Herein, we successfully synthesized a pair of new enantiomeric chiral perovskite (S/R-3PYEA)PbI4 (3PYEA2+ = C5NH5C2H4NH32+) and an achiral perovskite (rac-3PYEA)PbI4. Hydrostatic pressure was used, for the first time, to systematically investigate the differences in the structural evolution and optical behavior between (S/R-3PYEA)PbI4 and (rac-3PYEA)PbI4. At approximately 7.0 GPa, (S/R-3PYEA)PbI4 exhibits a chirality-dependent structural transformation with a bandgap "red jump" and dramatic piezochromism from translucent red to opaque black. Upon further compression, a previously unreported chirality-induced negative linear compressibility (NLC) is achieved in (S/R-3PYEA)PbI4. High-pressure structural characterizations and first-principles calculations demonstrate that pressure-driven homodirectional tilting of homochiral ammonium cations strengthens the interactions between S/R-3PYEA2+ and Pb-I frameworks, inducing the formation of new asymmetric hydrogen bonds N-H···I-Pb in (S/R-3PYEA)PbI4. The enhanced asymmetric H-bonding interactions further break the symmetry of (S/R-3PYEA)PbI4 and trigger a greater degree of in-plane and out-of-plane distortion of [PbI6]4- octahedra, which are responsible for chirality-dependent structural phase transition and NLC, respectively. Nevertheless, the balanced H-bonds incurred by equal proportions of S-3PYEA2+ and R-3PYEA2+ counteract the tilting force, leading to the absence of chirality-dependent structural transition, spectral "red jump", and NLC in (rac-3PYEA)PbI4.

5.
J Am Chem Soc ; 145(43): 23842-23848, 2023 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-37859342

RESUMO

Organic-inorganic halide perovskites possess unique electronic configurations and high structural tunability, rendering them promising for photovoltaic and optoelectronic applications. Despite significant progress in optimizing the structural characteristics of the organic cations and inorganic framework, the role of organic-inorganic interactions in determining the structural and optical properties has long been underappreciated and remains unclear. Here, by employing pressure tuning, we realize continuous regulation of organic-inorganic interactions in a lead halide perovskite, MHyPbBr3 (MHy+ = methylhydrazinium, CH3NH2NH2+). Compression enhances the organic-inorganic interactions by strengthening the Pb-N coordinate bonding and N-H···Br hydrogen bonding, which results in a higher structural distortion in the inorganic framework. Consequently, the second-harmonic-generation (SHG) intensity experiences an 18-fold increase at 1.5 GPa, and the order-disorder phase transition temperature of MHyPbBr3 increases from 408 K under ambient pressure to 454 K at the industrially achievable level of 0.5 GPa. Further compression triggers a sudden non-centrosymmetric to centrosymmetric phase transition, accompanied by an anomalous bandgap increase by 0.44 eV, which stands as the largest boost in all known halide perovskites. Our findings shed light on the intricate correlations among organic-inorganic interactions, octahedral distortion, and SHG properties and, more broadly, provide valuable insights into structural design and property optimization through cation engineering of halide perovskites.

6.
Inorg Chem ; 62(48): 19527-19541, 2023 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-38044824

RESUMO

The pressure-induced properties of hybrid organic-inorganic ferroelectrics (HOIFs) with tunable structures and selectable organic and inorganic components are important for device fabrication. However, given the structural complexity of polycrystalline HOIFs and the limited resolution of pressure data, resolving the structure-property puzzle has so far been the exception rather than the rule. With this in mind, we present a collection of in situ high-pressure data measured for triethylmethylammonium tetrabromoferrate(III), ([N(C2H5)3CH3][FeBr4]) (EMAFB) by unraveling its flexible physical and photophysical behavior up to 80 GPa. Pressure-driven X-ray diffraction and Raman spectroscopy disclose its soft and reversible structural distortion, creating room for delicate band gap modulation. During compression, orange turns dark red at ∼2 GPa, and further compression results in piezochromism, leading to opaque black, while decompressed EMAFB appears in an orange hue. Assuming that the mechanical softness of EMAFB is the basis for reversible piezochromic control, we present alternations in the electronic landscape leading to a 1.22 eV band narrowing at 20.3 GPa while maintaining the semiconducting character at 72 GPa. EMAFB exhibits an emission enhancement, manifested by an increase of photoluminescence up to 17.3 GPa, correlating with the onsets of structural distortion and amorphization. The stimuli-responsive behavior of EMAFB, exhibiting stress-activated modification of the electronic structure, can enrich the physical library of HOIFs suitable for pressure-sensing technologies.

7.
Angew Chem Int Ed Engl ; 62(9): e202217238, 2023 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-36461902

RESUMO

The unique intermolecular van der Waals force in emerging two-dimensional inorganic molecular crystals (2DIMCs) endows them with highly tunable structures and properties upon applying external stimuli. Using high pressure to modulate the intermolecular bonding, here we reveal the highly tunable charge transport behavior in 2DIMCs for the first time, from an insulator to a semiconductor. As pressure increases, 2D α-Sb2 O3 molecular crystal undergoes three isostructural transitions, and the intermolecular bonding enhances gradually, which results in a considerably decreased band gap by 25 % and a greatly enhanced charge transport. Impressively, the in situ resistivity measurement of the α-Sb2 O3 flake shows a sharp drop by 5 orders of magnitude in 0-3.2 GPa. This work sheds new light on the manipulation of charge transport in 2DIMCs and is of great significance for promoting the fundamental understanding and potential applications of 2DIMCs in advanced modern technologies.

8.
Angew Chem Int Ed Engl ; 62(37): e202304494, 2023 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-37464980

RESUMO

Low-dimensional (low-D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both organic and inorganic components. However, for most of low-D OMHHs, especially the zero-D (0D) compounds, the inferior electronic coupling between organic ligands and inorganic metal halides prevents efficient charge transfer at the hybrid interfaces and thus limits their further tunability of optical and electronic properties. Here, using pressure to regulate the interfacial interactions, efficient charge transfer from organic ligands to metal halides is achieved, which leads to a near-unity photoluminescence quantum yield (PLQY) at around 6.0 GPa in a 0D OMHH, [(C6 H5 )4 P]2 SbCl5 . In situ experimental characterizations and theoretical simulations reveal that the pressure-induced electronic coupling between the lone-pair electrons of Sb3+ and the π electrons of benzene ring (lp-π interaction) serves as an unexpected "bridge" for the charge transfer. Our work opens a versatile strategy for the new materials design by manipulating the lp-π interactions in organic-inorganic hybrid systems.

9.
Angew Chem Int Ed Engl ; 61(33): e202206816, 2022 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-35715388

RESUMO

Highly-polarizable materials are favorable for photoelectric conversion due to their efficient charge separation, while precise design of them is still a big challenge. Herein a novel polar oxyselenide, Sr6 Cd2 Sb6 O7 Se10 , is rationally designed. It contains lateral sublattices of polarizable [Sb2 OSe4 ]4- chains and highly-orientated [CdSe3 ]4- chains. The intense polarization was evaluated by significant second-harmonic generation (SHG) signal (maximum: 12.6×AgGaS2 ) in broad spectrum range. The polarization was found to mainly improve the carrier separation with a much longer recombination lifetime (76.5 µs) than that of the nonpolar compound Sr2 Sb2 O2 Se3 (18.0 µs), resulting in better photoelectric performance. The single-crystal photoelectric device exhibited excellent response covering broad spectrum in 500-1000 nm with stable reproducibility. This work provides some new insights into the structure design of highly-polarizable heteroanionic materials for photoelectric conversion.

10.
J Am Chem Soc ; 143(6): 2545-2551, 2021 Feb 17.
Artigo em Inglês | MEDLINE | ID: mdl-33465309

RESUMO

Pressure processing is efficient to regulate the structural and physical properties of two-dimensional (2D) halide perovskites which have been emerging for advanced photovoltaic and light-emitting applications. Increasing numbers of studies have reported pressure-induced and/or enhanced emission properties in the 2D halide perovskites. However, no research has focused on their photoresponse properties under pressure tuning. It is also unclear how structural change affects their excitonic features, which govern the optoelectronic properties of the halide perovskites. Herein, we report significantly enhanced photocurrents in the all-inorganic 2D perovskite Cs2PbI2Cl2, achieving over 3 orders of magnitude increase at the industrially achievable level of 2 GPa in comparison with its initial photocurrent. Lattice compression effectively regulates the excitonic features of Cs2PbI2Cl2, reducing the exciton binding energy considerably from 133 meV at ambient conditions to 78 meV at 2.1 GPa. Impressively, such a reduced exciton binding energy of 2D Cs2PbI2Cl2 is comparable to the values of typical 3D perovskites (MAPbBr3 and MAPbI3), facilitating the dissociating of excitons into free carriers and enhancing the photocurrent. Further pressurization leads to a layer-sliding-induced phase transition and an anomalous negative linear compression, which has not been observed so far in other halide perovskites. Our findings reveal the dramatically enhanced photocurrents in the 2D halide perovskite by regulating its excitonic features and, more broadly, provide new insights into materials design toward extraordinary properties.

11.
Angew Chem Int Ed Engl ; 59(40): 17533-17539, 2020 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-32627251

RESUMO

A remarkable PL enhancement by 12 fold is achieved using pressure to modulate the structure of a recently developed 2D perovskite (HA)2 (GA)Pb2 I7 (HA=n-hexylammonium, GA=guanidinium). This structure features a previously unattainable, extremely large cage. In situ structural, spectroscopic, and theoretical analyses reveal that lattice compression under a mild pressure within 1.6 GPa considerably suppresses the carrier trapping, leading to significantly enhanced emission. Further pressurization induces a non-luminescent amorphous yellow phase, which is retained and exhibits a continuously increasing band gap during decompression. When the pressure is released to 1.5 GPa, emission can be triggered by above-band gap laser irradiation, accompanied by a color change from yellow to orange. The obtained orange phase could be retained at ambient conditions and exhibits two-fold higher PL emission compared with the pristine (HA)2 (GA)Pb2 I7 .

12.
J Am Chem Soc ; 141(42): 16903-16914, 2019 Oct 23.
Artigo em Inglês | MEDLINE | ID: mdl-31566959

RESUMO

Layered sulfides with high selectivity for binding heavy metal ions and radionuclide ions are promising materials in effluent treatment and water purification. Here we present a rationally designed layered sulfide Kx[Bi4-xMnxS6] (x = 1.28) deriving from the Bi2Se3-structure type by targeted substitution to generate quintuple [Bi4-xMnxS6]x- layers and K+ cations between them. The material has dual functionality: it is an attractive semiconductor with a bandgap of 1.40 eV and also an environmental remediation ion-exchange material. The compound is paramagnetic, and optical adsorption spectroscopy and DFT electronic structure calculations reveal that it possesses a direct band gap and a work function of 5.26 eV. The K+ ions exchange readily with alkali or alkaline-earth ions (Rb+, Cs+, and Sr2+) or soft ions (Pb2+, Cd2+, Cr3+, and Zn2+). Furthermore, when the K+ ions are depleted the Mn2+ ions in the Bi2Se3-type slabs can also be replaced by soft ions, achieving large adsorption capacities. The ion exchange reactions of Kx[Bi4-xMnxS6] can be used to create new materials of the type Mx[Bi4-xMnxS6] in a low temperature kinetically controlled manner with significantly different electronic structures. The Kx[Bi4-xMnxS6] (x = 1.28) exhibits efficient capture of Cd2+ and Pb2+ ions with high distribution coefficient, Kd (107 mL/g), and exchange capacities of 221.2 and 342.4 mg/g, respectively. The material exhibits excellent capacities even in high concentration of competitive ions and over a broad pH range (2.5-11.0). The results highlight the promise of the Kx[Bi4-xMnxS6] (x = 1.28) phase to serve not only as a highly selective adsorbent for industrial and nuclear wastewater but also as a magnetic 2D semiconductor for optoelectronic applications.

13.
J Am Chem Soc ; 141(2): 790-793, 2019 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-30601005

RESUMO

Noncentrosymmetric MoS2 semiconductors (1H, 3R) possess not only novel electronic structures of spin-orbit coupling (SOC) and valley polarization but also remarkable nonlinear optical effects. A more interesting noncentrosymmetric structure, the so-called 1T‴-MoS2 layers, was predicted to be built up from [MoS6] octahedral motifs by theoreticians, but the bulk 1T‴ MoS2 or its single crystal structure has not been reported yet. Here, we have successfully harvested 1T‴ MoS2 single crystals by a topochemical method. The new layered structure is determined from single-crystal X-ray diffraction. The crystal crystallizes in space group P31m with a cell of a = b = 5.580(2) Å and c = 5.957(2) Å, which is a √3 a × âˆš3 a superstructure of 1T MoS2 with corner-sharing Mo3 triangular trimers observed by the STEM. 1T‴ MoS2 is verified to be semiconducting and possesses a band gap of 0.65 eV, different from metallic nature of 1T or 1T' MoS2. More surprisingly, the 1T‴ MoS2 does show strong optical second-harmonic generation signals. This work provides the first layered noncentrosymmetric semiconductor of edge-sharing MoS6 octahedra for the research of nonlinear optics.

14.
Inorg Chem ; 58(1): 69-72, 2019 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-30585480

RESUMO

A new two-dimensional (2D) layered oxysulfide, namely, SrOCuSbS2, was successfully synthesized at 160 °C by using a hydrazine-hydrothermal method. The compound crystallizes in the space group C2 h2- P21/ m (No. 11) of the monoclinic system. The crystal structure is composed of distorted chalcostibite-like ∞2[CuSbS2O]2- layers along the ab plane, in which the adjacent layers are separated by Sr2+ ions. Each layer contains infinite ∞1[Cu2S6]10- chains linked by [SbS4O]7- units. The optical band gap of the compound is 1.9 eV, presenting the dark red color. Due to the electronic insulating layer (EIL) of the SrO, SrOCuSbS2 shows a high photoelectric property with a photocurrent density of 3.5 mA/cm2 at 1 V. The results of density of states (DOS) reveal that the valence band maximum (VBM) mainly consists of Cu-3d and S-3p states, while Sb-5p, S-3p, and S-3s contribute to the conductive band minimum (CBM).

15.
Inorg Chem ; 58(14): 9482-9489, 2019 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-31241920

RESUMO

The layered oxyselenides with the formula LnCrSe2O (Ln = Ce-Nd) were synthesized via molten salt methods. The isostructural compounds crystallize in the monoclinic space group of C2/m. The crystal structures feature ∞2[CrSe2O]3- motifs stacked along the a axis, which are separated by Ln3+ ions. The ∞2[CrSe2O]3- layers are composed of [Cr1Se6]9- and [Cr2Se4O2]9- octahedra via corner and edge sharing. Powder X-ray diffraction results confirm the phase purities of the as-synthesized compounds. LnCrSe2O (Ln = Ce-Nd) show typical antiferromagnetic ordering with TN = 125, 120, and 118 K, respectively. Heat capacity measurement for NdCrSe2O indicates that the Debye temperature is 278.4 K. Similar metal-to-semiconductor phase transitions were observed for LnCrSe2O (Ln = Ce-Nd) plates with transition temperatures of 115, 109, and 95 K, respectively. NdCrSe2O also possesses a magnetoresistance effect at low temperature (<25 K) with a significant positive magnetoresistance ∼ 16% at 2 K and 1 T.

16.
Angew Chem Int Ed Engl ; 58(24): 8078-8081, 2019 Jun 11.
Artigo em Inglês | MEDLINE | ID: mdl-30985053

RESUMO

A new nonlinear optical (NLO) oxysulfide, Sr6 Cd2 Sb6 O7 S10 , which contains the functional groups [SbOx S5-x ]7- (x=0, 1) with a 5s2 electron configuration, is synthesized by a solid-state reaction. This compound displays a phase-matchable second harmonic generation (SHG) response four times stronger than AgGaS2 (AGS) under laser irradiation at 2.09 µm. Single-crystal-based optical measurements reveal a SHG intensity that can be tuned by temperature and novel photoluminescence properties. Theoretical analyses demonstrate that tetragonal [SbOS4 ]7- and [SbS5 ]7- pyramids make the predominant contribution to the enhanced SHG effect. Among those, the [SbOS4 ]7- units with mixed anions make a larger contribution. This work proposes that oxysulfide groups with an ns2 electron configuration can serve as new functional building units in NLO materials and opens a new avenue for the design of other optoelectronic materials.

17.
J Am Chem Soc ; 140(17): 5719-5727, 2018 05 02.
Artigo em Inglês | MEDLINE | ID: mdl-29644854

RESUMO

TiO2 mesoporous crystal has been prepared by one-step corroding process via an oriented attachment (OA) mechanism with SrTiO3 as precursor. High resolution transmission electron microscopy (HRTEM) and nitrogen adsorption-desorption isotherms confirm its mesoporous crystal structure. Well-dispersed ruthenium (Ru) in the mesoporous nanocrystal TiO2 can be attained by the same process using Ru-doped precursor SrTi1- xRu xO3. Ru is doped into lattice of TiO2, which is identified by HRTEM and super energy dispersive spectrometer (super-EDS) elemental mapping. X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance spectroscopy (EPR) suggest the pentavalent Ru but not tetravalent, while partial Ti in TiO2 accept an electron from Ru and become Ti3+, which is observed for the first time. This Ru-doped TiO2 performs high activity for electrocatalytic hydrogen evolution reaction (HER) in alkaline solution. First-principles calculations simulate the HER process and prove TiO2:Ru with Ru5+ and Ti3+ holds high HER activity with appropriate hydrogen-adsorption Gibbs free energies (Δ GH).

18.
Chemistry ; 24(60): 15942-15954, 2018 Oct 26.
Artigo em Inglês | MEDLINE | ID: mdl-29693734

RESUMO

The 2H molybdenum disulfide (MoS2 ), as a stable hexagonal phase, has been one of the most studied transition metal dichalcogenides over the past decades. In the last five years, the metastable phases of MoS2 (1T, 1T', 1T'', and 1T''') have seen a revival of interests. Different from the edge-sharing [MoS6 ] trigonal prisms in the 2H MoS2 phase, these metastable phases are composed of the edge-sharing [MoS6 ] octahedra, in which the neighboring Mo-Mo distances differ. Due to the various crystal structures and different electronic configurations of the building [MoS6 ] motifs, these metastable polytypes are endowed with intriguing physical properties and potential applications in diverse fields. In this Review, the recent research progress on metastable MoS2 is summarized, especially with an emphasis on the diverse synthetic approaches and the newly uncovered physical properties. The phase structures and electronic band structures are also outlined. In the end, a perspective of the future investigation on metastable MoS2 is discussed.

19.
Inorg Chem ; 57(3): 1449-1454, 2018 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-29309131

RESUMO

Six isostructural antiperovskite-derived chalcohalides, Ba2MQ3X (M = As, Sb; Q = S, Se; X = Cl, Br, I), crystallizing in the space group Pnma, have been synthesized by solid-state reactions. The crystal structure features a 3D framework with the [XBa5]9+ disordered square pyramids as building blocks and [MQ3]3- units filling the interspace. [XBa5]9+ disordered square pyramids are edge-sharing along [010], derived from the fusing of the two pyramids in octahedral [XBa6]11+. Surprisingly, Ba2AsS3X (X = Cl, Br, I) show almost the same optical band gap of 2.80 eV, and Ba2AsSe3X (X = Br, I) also have a similar band gap of 2.28 eV. The optical band gap of Ba2SbS3I is 2.64 eV. First-principles calculations reveal that the optical absorption is attributed to the transitions between Q np at the valence band maximum (VBM) and M np-Q np at the conduction band minimum (CBM). These compounds also possess interesting photoluminescence properties with splitting emission peaks on excitation at 200 nm.

20.
Inorg Chem ; 57(7): 3956-3962, 2018 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-29561142

RESUMO

Intermediate band (IB) materials are of great significance due to their superior solar absorption properties. Here, two IBs peaking at 0.88 and 1.33 eV are reported to be present in the forbidden gap of semiconducting SnS2 ( Eg = 2.21 eV) by doping titanium up to 6 atom % into the Sn site via a solid-state reaction at 923 K. The solid solution of Sn1- xTi xS2 is able to be formed, which is attributed to the isostructural structure of SnS2 and TiS2. These two IBs were detected in the UV-vis-NIR absorption spectra with the appearance of two additional absorption responses at the respective regions, which in good agreement with the conclusion of first-principles calculations. The valence band maximum (VBM) consists mostly of the S 3p state, and the conduction band minimum (CBM) is the hybrid state composing of Ti 3d (eg), S 3p, and Sn 5s, and the IBs are mainly the nondegenerate t2g states of Ti 3d orbitals. The electronic states of Ti 3d reveal a good ability to transfer electrons between metal and S atoms. These wide-spectrum absorption IBs bring about more solar energy utilization to enhance solar thermal collection and photocatalytic degradation of methyl orange.

SELEÇÃO DE REFERÊNCIAS
Detalhe da pesquisa