S K and P K absorption spectra and electronic structures of layered thiophosphates MPS3

Ohno, Youichi; Hirama, Kimiaki

doi:10.1016/0022-4596(86)90176-3

Cited by 26 publications

(17 citation statements)

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“…This value is considerably less than the optical bandgap of 1.6 eV. This gap corresponds to the transitions from the valence band to the localized d-electronic states, according to the energy band scheme (19)(20)(21)(22)(23). Actually, the main valence and conduction bands are predicted to be separated by an energy gap of about 2.6 eV (23).…”

Section: Resultsmentioning

confidence: 92%

Photoelectrochemical Investigation of n‐ and p‐Doped Nickel Phosphorous Trisulfide ( NiPS3 )

Aruchamy

Berger

Lévy

1989

J. Electrochem. Soc.

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n-and p-type doped NIPS3 crystals grown by chemical vapor transport have been investigated for their electrical and photoelectrochemical properties. The photocurrent-voltage characteristics, differential capacitance, and spectral response were measured in 0.5M H2SO4. The current-voltage curves of both types of electrodes indicate significant recombination, p-type NIPS3 is stable during the photocathodic hydrogen evolution while n-type electrodes undergo photoanodic decomposition. The measured quantum efficiencies are very low due to the localized d-electronic states involved in the photoelectronic processes. Indirect bandgap analysis of the quantum efficiency data reveals transitions at 1.64 and 1.9 eV. The transition at 1.64 eV is in good agreement with the reported optical absorption edge. These results are related with the electronic-energy band scheme of NIPS3.Nickel phosphorous trisulfide (NIPS3) belongs to the group of MPX3(M = Metal, X = S, Se) compounds which are structurally related to the layered transition metal dichalcogenides (1, 2). They are wide bandgap semiconductors and show interesting intercalation reactions with several inorganic and organic species (3-16). Lithium intercalation of MPS~ compounds has been studied in greater detail due to their possible application in secondary batteries. Lithium intercalated NIPS3 is of particular interest because its energy density and cell voltage are higher than those of the LixTiS2 making it a promising cathode material (4, 7).NIPS3 crystallizes in a distorted CdC12 structure with a monoclinic unit cell (1, 2). An absorption edge at 1.6 eV photon energy characterizes its optical spectrum (8). The magnetic measurements indicate that it is antiferromagnetic and that the d-electrons are strongly localized (8, 17)i Undoped NIPS3 is considered to be nearly stoichiometric (18). Lithium intercalation studies indicate that the ionic diffusion coefficient is quite low (16). Qualitative energy band schemes have been proposed for NIPS3, based on visible and infrared optical spectra, x-ray absorptio n , and photoemission studies (19-23). Recently n-and p-doped samples of NIPS3 have been investigated by electrical conductivity, current-voltage, and Hall effect measurements in order to understand the conduction mechanism and the electron transfer processes in the intercalation reactions (16,24). While these various studies have provided considerable details on the electronic processes in NIPS3, a complete picture of the electronic structure, however, is not yet available. Therefore, more data on the electronic parameters including those on the d-electrons are needed. NIPS3 being the prototype of the transition metal MPX3 compounds it is of considerable importance to investigate its various properties in relation to its electronic structure.In this report, we present the photoelectrochemical (PEC) characterization of the n-and p-doped crystals of NIPS3. PEC studies often provide valuable information pertaining to the bulk electronic parameters of the semiconductor such a...

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Section: Resultsmentioning

confidence: 92%

Photoelectrochemical Investigation of n‐ and p‐Doped Nickel Phosphorous Trisulfide ( NiPS3 )

Aruchamy

Berger

Lévy

1989

J. Electrochem. Soc.

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“…per primitive cell and thus neglected the glide plane symmetry of the crystal. Although there are some photoemission measurements confirming the existence of Sn 2ϩ ions, 29 as well as some x-ray fluorescence and absorption spectra have been reported, 30,31 we present here a more complete systematic study of superior quality. Specifically, the experimental side is x-ray photoelectron spectroscopy ͑XPS͒ and soft x-ray fluorescence ͑SXF͒ spectroscopy.…”

Section: Introductionmentioning

confidence: 88%

Electronic structure ofSn2P2S6<

et al. 2003

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The electronic properties of the ferroelectric compound Sn 2 P 2 S 6 are investigated by x-ray photoelectron spectroscopy and soft x-ray fluorescence spectroscopy. Excellent agreement between theoretical calculations and experimental data for the electronic structure of the investigated compound is achieved. With help of the Sn core level spectra it is confirmed that the compound contains Sn 2ϩ ions. The valence band mainly consists of five resolvable bands between 3.3 eV and 14.5 eV. Consistent with the results of band-structure calculation and the soft x-ray fluorescence spectra, Sn 2 P 2 S 6 can be viewed as an ionic crystal, built of Sn 2ϩ and the (P 2 S 6 ) 4Ϫ fragments. Within the latter, P-P and P-S bonds are largely covalent and characterized by sp hybridization.

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“…On the one hand, the number of electrons in the outmost shell or d orbital of the metal elements constituted in MPX 3 contributes to their unique properties. On the other hand, the [P 2 X 6 ] 4− provides a weak ligand field, resulting in a high spin state of the metal atoms . Accordingly, a plethora of results about the magnetism of these materials are published from the perspective of experiments and calculations.…”

Section: Introductionmentioning

confidence: 99%

New Frontiers on van der Waals Layered Metal Phosphorous Trichalcogenides

Wang

Shifa

et al. 2018

Adv Funct Materials

284

290

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The exponentially growing works on 2D materials have resulted in both high scientific interest and huge potential applications in nanocatalysis, optoelectronics, and spintronics. Of especial note is that the newly emerged and promising family of metal phosphorus trichalcogenides (MPX 3 ) contains semiconductors, metals, and insulators with intriguing layered structures and architectures. The bandgaps of the members in this family range from 1.3 to 3.5 eV, significantly enriching the application of 2D materials in the broad wavelength spectrum. In this review, emphasizing their remarkable structural, physicochemical, and magnetic properties, as well as the numerous applications in various fields, the innovative progress on layered MPX 3 crystals is summarized. Different from other layered materials, these crystals will advance a fascinating frontier in magnetism and spintronic devices with their especially featured atomic layered nanosheets. Thus, their crystal and electronic structures, along with some related researches in magnetism, are discussed in detail. The assortments of growth methods are then summarized. Considering their potential applications, the prominent utilization of these 2D MPX 3 nanoscrystals in catalysis, batteries, and optoelectronics is also discussed. Finally, the outlook of these kinds of layered nanomaterials is provided. Metal Phosphorus Trichalcogenidesions. Friedel [17] and Ferrand [18,19] discovered them in the late 1800s. Based on the interesting structure of these materials, significant research works were reported in the early 2000s. As expected, 2D MPX 3 phases share most of the abovementioned specific properties of 2D TMDs. According to the theoretical and experimental results, MPX 3 compounds are the most sought functional materials for their intermediate bandgaps ranging from 1.3 to 3.5 eV, [20,21] indicating their enhanced light absorption efficiency as compared to the TMD materials. In addition, their unusual intercalation-substitution or intercalation-reduction behavior as well as the incipient ionic conductivity promote their usage in Li-ion batteries, [22,23] gas storage, [24] and photo-electrochemical reactions. [25] Unlike TMDs, several MPX 3 materials show intrinsic anti-ferromagnetism below the Neel temperatures of 78 K for MnPS 3 , 116 K for FePS 3 , and 155 K for NiPS 3 . [26,27] Recently, Li et al. [28] predicted that transformation from the anti-ferromagnetism to ferromagnetism for exfoliated MnPSe 3 nanosheet will be reduced by carrier doping. And the Monte Carlo simulation reveals the Curie temperature of the doped MnPSe 3 nanosheets can reach 206 K, rendering it with potential for utilizations in spintronic devices at high temperature. Therefore, the members in the MPX 3 family have the abovementioned properties along with structural flexibility stemming from their van der Waals nature; thus, it is reasonable to assume that they will contribute to the next major frontier in 2D vdW layered materials.Herein, we emphasize on reviewing the impressive recent progress...

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S K and P K absorption spectra and electronic structures of layered thiophosphates MPS3

Cited by 26 publications

References 26 publications

Photoelectrochemical Investigation of n‐ and p‐Doped Nickel Phosphorous Trisulfide ( NiPS3 )

Photoelectrochemical Investigation of n‐ and p‐Doped Nickel Phosphorous Trisulfide ( NiPS3 )

Electronic structure ofSn2P2S6<

New Frontiers on van der Waals Layered Metal Phosphorous Trichalcogenides

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