PtSe2 Films Research Articles

Improvement of Contact Resistance and 3D Integration of 2D Material Field‐Effect Transistors Using Semi‐Metallic PtSe2 Contacts

AbstractIn this work, the potential of 2D semi‐metallic PtSe2 as source/drain (S/D) contacts for 2D material field‐effect‐transistors (FETs) through theoretical and experimental investigations, is explored. From the density functional theory (DFT) calculations, semi‐metallic PtSe2 can inject electrons and holes into MoS2 and WSe2, respectively, indicating the feasibility of PtSe2 contacts for both n‐ and p‐metal‐oxide‐semiconductor FETs (n‐/p‐MOSFETs). Indeed, experimentally fabricated flake‐level MoS2 n‐MOSFETs and WSe2 p‐MOSFETs exhibit a significant reduction in contact resistance with semi‐metallic PtSe2 contacts compared to conventional Ti/Au contacts. To demonstrate the applicability for large‐area electronics, MoS2 n‐MOSFETs are fabricated with semi‐metallic PtSe2 contacts using chemical vapor deposition‐grown MoS2 and PtSe2 films. These devices exhibit outstanding performance metrics, including high on‐state current (≈10−7 A/µm) and large on/off ratio (>107). Furthermore, by employing these high‐performance MoS2 n‐MOSFETs, vertically stacked n‐MOS inverters are successfully demonstrated, suggesting that 3D integration of 2D material FETs is possible using semi‐metallic PtSe2 contacts.

Giant optical absorption of a PtSe2-on-silicon waveguide in mid-infrared wavelengths.

Low-dimensional platinum diselenide (PtSe2) is a promising candidate for high-performance optoelectronics in the short-wavelength mid-infrared band due to its high carrier mobility, excellent stability, and tunable bandgap. However, light usually interacts moderately with low-dimensional PtSe2, limiting the optoelectronic responses of PtSe2-based devices. Here we demonstrated a giant optical absorption of a PtSe2-on-silicon waveguide by integrating a ten-layer PtSe2 film on an ultra-thin silicon waveguide. The weak mode confinement in the ultra-thin waveguide dramatically increases the waveguide mode overlap with the PtSe2 film. Our experimental results show that the absorption coefficient of the PtSe2-on-silicon waveguide is in the range of 0.0648 dB μm-1 to 0.0704 dB μm-1 in a spectral region of 2200 nm to 2300 nm wavelengths. Furthermore, we also studied the optical absorption in an ultra-thin silicon microring resonator. Our study provides a promising approach to developing PtSe2-on-silicon hybrid optoelectronic integrated circuits.

In situ construction of PtSe2/Ge Schottky junction array with interface passivation for broadband infrared photodetection and imaging

AbstractInfrared (IR) detection is vital for various military and civilian applications. Recent research has highlighted the potential of two‐dimensional (2D) topological semimetals in IR detection due to their distinctive advantages, including van der Waals (vdW) stacking, gapless electronic structure, and Van Hove singularities in the electronic density of states. However, challenges such as large‐scale patterning, poor photoresponsivity, and high dark current of photodetectors based on 2D topological semimetals significantly impede their wider applications in low‐energy photon sensing. Here, we demonstrate the in situ fabrication of PtSe2/Ge Schottky junction by directly depositing 2D PtSe2 films with a vertical layer structure on a Ge substrate with an ultrathin AlOx layer. Due to high quality junction, the photodetector features a broadband response of up to 4.6 μm, along with a high specific detectivity of ~1012 Jones, and operates with remarkable stability in ambient conditions as well. Moreover, the highly integrated device arrays based on PtSe2/AlOx/Ge Schottky junction showcases excellent Mid‐IR (MIR) imaging capability at room temperature. These findings highlight the promising prospects of 2D topological semimetals for uncooled IR photodetection and imaging applications.image

Probing Carrier Dynamics in Large-Scale MBE-Grown PtSe2 Films by Terahertz Spectroscopy.

Atomically thin platinum diselenide (PtSe2) films are promising for applications in the fields of electronics, spintronics, and photodetectors owing to their tunable electronic structure and high carrier mobility. Using terahertz (THz) spectroscopy techniques, we investigated the layer-dependent semiconducting-to-metallic phase transition and associated intrinsic carrier dynamics in large-scale PtSe2 films grown by molecular beam epitaxy. The uniformity of large-scale PtSe2 films was characterized by spatially and frequency-resolved THz-based sheet conductivity mapping. Furthermore, we use an optical-pump-THz-probe technique to study the transport dynamics of photoexcited carriers and explore light-induced intergrain carrier transport in PtSe2 films. We demonstrate large-scale THz-based mapping of the electrical properties of transition metal dichalcogenide films and show that the two noncontact THz-based approaches provide insight in the spatial and temporal properties of PtSe2 films.

Revealing the influence of edge states on the electronic properties of PtSe2

The properties and performance of 2D nanostructures are known to be critically affected by localized edge states. Here, platinum diselenide (PtSe2) films, synthesized by thermally assisted conversion, are characterized by a variety of spectroscopic and microscopic methods, including scanning tunneling microscopy and spectroscopy, and scanning transmission electron microscopy. We report the presence of distinct edge states, and use surface Green's function methodology in atomistic modeling of different edge atomic structures, together with other theoretical tools, to investigate their origin. Our results indicate that the edges, inherent and abundant in polycrystalline films, can be semiconducting or semimetallic in nature depending on the edge configuration. Experimental results in conjunction with first-principles calculations demonstrate a mapped band profile of the atomically-sharp step edges of PtSe2, which form lateral heterojunctions possessing large asymmetric band offsets in the conduction and valence bands. We further explore the viability of a single step monomaterial heterojunction based field-effect transistor, through atomistic quantum transport simulations. This reveals the critical role of the edge states in creating a wider energy band for carrier transport in the ON-state and hence enabling a remarkably large ION/IOFF ratio > 1010 and near-ideal subthreshold slope, fulfilling the requirements for low-power applications.

Carrier transport across PtSe2/n-type GaN heterojunction

We fabricated PtSe2/n-type GaN heterojunction diode by transferring a large-scale grown two-dimensional (2D) PtSe2 layered film onto a 3D GaN substrate. The PtSe2 film transferred onto GaN was ∼5.84-nm thick and had 11 layers with interlayer spacing of 0.52 nm. An exploration of the temperature-dependence of the current–voltage (I–V) characteristics of the PtSe2/n-type GaN heterojunction in the range 125–400 K revealed a strong dependency of the ideality factor and barrier height on measurement temperature. This indicates a presence of low- and high-barrier-height patches resembling barrier inhomogeneities along the interface. A barrier inhomogeneity analysis with a consideration for the Gaussian barrier heights distribution demonstrated the existence of a double Gaussian barrier distribution having a mean barrier height of 0.97 and 1.41 eV in low- and high-temperature regimes, respectively. An examination of the temperature-dependency of reverse leakage current indicated the dominance of variable-range hopping conduction in lower temperature region (<225 K) and Poole–Frenkel emission mechanism in higher temperature region (>250 K). The interface state density Nss of the PtSe2/n-type GaN heterojunction determined from the capacitance method was lesser than that attained from the forward I–V characteristics that can be accredited to the inhomogeneous spreading of the Nss.

Barrier-free semimetallic PtSe2 contact formation in two-dimensional PtSe2/PtSe2 homostructure for high-performance field-effect transistors

The search for low-resistance metal contacts on two-dimensional (2D) layered transition metal dichalcogenide (TMDC) materials for high-performance electronic devices remains challenging owing to the lack of interfacial bonding on the surface and a strong Fermi-level pinning effect. In this study, we demonstrate a high-performance 2D large-area homostructured PtSe2/PtSe2 field-effect transistor (FET) by introducing a Schottky-barrier-free and semimetallic PtSe2 film (top layer) as an ohmic contact to semiconducting 2D PtSe2 films (bottom layer) via the wet-transfer method. We successfully improved the current on/off ratio of homostructured 2D/2D PtSe2/PtSe2 FET by more than approximately twofold increase compared to the PtSe2 FET with Pt contacts owing to the barrier-free homojunction PtSe2 layer. Our finding represents a significant achievement in obtaining high-performance electronic devices with barrier-free contacts on homostructured PtSe2 FETs and paves the way toward a promising strategy for wafer-scale 2D TMDC electronic devices.

PtSe2 outperforms Pt as a counter electrode in dye sensitized solar cells

In the present study, we show that PtSe2 films, prepared by soft selenization of pre-deposited Pt, is a very efficient counter electrode (CE) in dye sensitized solar cells (DSSCs). Devices based on PtSe2 achieve better photoconversion efficiency (9.5 ± 1.2%) than those employing bare Pt CE (9.18 ± 0.21%), even if the latter use three times more Pt loading than that used to prepare the PtSe2 CE. Films with of various Pt loadings have been prepared by electrodeposition and their catalytic properties have been investigated and compared with films of corresponding Pt loading which have been transformed to PtSe2 by low-temperature selenization. The improved performance of the PtSe2 CEs has been assigned to the higher availability of catalytic active sites and the more effective mechanism of interfacial electron transfer. This is a first attempt to explore the role of PtSe2 as the CE in DSSCs. The strong advantages of PtSe2 in relation to catalytic activity, stability, efficiency, combined with cost reduction, due to the lower mass loading required for a given performance, renders this noble-transition metal dichalcogenide a promising candidate to boost the performance of third generation photovoltaics, opening-up possibilities, at the same time, for other applications where Pt is used as the catalyst.

Electronic and electrocatalytic applications based on solution‐processed two‐dimensional platinum diselenide with thickness‐dependent electronic properties

AbstractPlatinum diselenide (PtSe2) has shown great potential as a candidate two‐dimensional (2D) material for broadband photodetectors and electrocatalysts because of its unique properties compared to conventional 2D transition metal dichalcogenides. Synthesis of 2D PtSe2 with controlled layer number is critical for engineering the electronic behavior to be semiconducting or semimetallic for targeted applications. Electrochemical exfoliation has been investigated as a promising approach for mass‐producing in a cost‐effective manner, but obtaining high‐quality films with control over electronic properties remains difficult. Here, we demonstrate wafer‐scale 2D PtSe2 films with pre‐determined electronic types based on a facile solution‐based strategy. Semiconducting or semimetallic PtSe2 nanosheets with large lateral sizes are produced via electrochemically driven molecular intercalation, followed by centrifugation‐based thickness sorting. Finally, gate‐tunable broadband visible and near‐infrared photodetector arrays are realized based on semiconducting PtSe2 nanosheet films, while semimetallic films are used to create catalytic electrodes for overall water splitting with long‐term stability.image

Large-Area Black Phosphorus/PtSe2 Schottky Junction for High Operating Temperature Broadband Photodetectors.

High operating temperature (HOT) broadband photodetectors are urgently necessary for extreme condition applications in infrared-guided missiles, infrared night vision, fire safety imaging, and space exploration sensing. However, conventional photodetectors show dramatic carrier mobility decreases and carrier losses with low photoresponsivity at HOT due to the increased carrier scattering in channels at high temperatures. Herein, the HOT broadband photodetectors from room temperature to 470 K are developed for the first time by large-area black phosphorus (BP)/PtSe2 films device arrays via a depletion-enhanced photocarrier dynamics strategy. Attributed to the 2D Schottky junction at BP/PtSe2 interface and resulting in full depleted working channels, the BP/PtSe2 photodetector arrays exhibit high tolerance to carrier mobility decrease during the increasing operating temperature in a wide wavelength range from 532 to 2200nm. Thus, the photodetector shows a state-of-the-art operating temperature at 470 K with the photo-responsivity (R) and specific detectivity (D*) of 25 A W-1 and 6.4 × 1011 Jones under 1850nm illumination, respectively. Moreover, BP/PtSe2 photodetector arrays show high-uniformity photo-response in a large area. This work provides new strategies for high-performance broadband photodetector arrays with HOT by Schottky junction of large-area BP/PtSe2 films.

Optically Controlling Broadband Terahertz Modulator Based on Layer-Dependent PtSe2 Nanofilms

In this paper, we propose an optically controlling broadband terahertz modulator of a layer-dependent PtSe2 nanofilm based on a high-resistance silicon substrate. Through optical pump and terahertz probe system, the results show that compared with 6-, 10-, and 20-layer films, a 3-layer PtSe2 nanofilm has better surface photoconductivity in the terahertz band and has a higher plasma frequency ωp of 0.23 THz and a lower scattering time τs of 70 fs by Drude-Smith fitting. By the terahertz time-domain spectroscopy system, the broadband amplitude modulation of a 3-layer PtSe2 film in the range of 0.1-1.6 THz was obtained, and the modulation depth reached 50.9% at a pump density of 2.5 W/cm2. This work proves that PtSe2 nanofilm devices are suitable for terahertz modulators.

Predicting defect stability and annealing kinetics in two-dimensional PtSe2 using steepest entropy ascent quantum thermodynamics

The steepest-entropy-ascent quantum thermodynamic (SEAQT) framework was used to calculate the stability of a collection of point defects in 2D PtSe2 and predict the kinetics with which defects rearrange during thermal annealing. The framework provides a non-equilibrium, ensemble-based framework with a self-consistent link between mechanics (both quantum and classical) and thermodynamics. It employs an equation of motion derived from the principle of steepest entropy ascent (maximum entropy production) to predict the time evolution of a set of occupation probabilities that define the states of a system undergoing a non-equilibrium process. The system is described by a degenerate energy landscape of eigenvalues, and the entropy is found from the occupation probabilities and the eigenlevel degeneracies. Scanning tunneling microscopy was used to identify the structure and distribution of point defects observed experimentally in a 2D PtSe2 film. A catalog of observed defects includes six unique point defects (vacancies and anti-site defects on Pt and Se sublattices) and twenty combinations of multiple point defects in close proximity. The defect energies were estimated with density functional theory, while the degeneracies, or density of states, for the 2D film with all possible combinations or arrangements of cataloged defects was constructed using a non-Markovian Monte-Carlo approach (i.e. the Replica–Exchange–Wang–Landau algorithm (Vogel et al 2013 Phys. Rev. Lett. 110 210603)) with a q-state Potts model. The energy landscape and associated degeneracies were determined for a 2D PtSe2 film two molecules thick and unit cells in area (total of 5400 atoms). The SEAQT equation of motion was applied to the energy landscape to determine how an arbitrary density and arrangement of the six defect types evolve during annealing. Two annealing processes were modeled: heating from 77 K (−196 C) to 523 K (250 ∘C) and isothermal annealing at 523 K. The SEAQT framework predicted defect configurations, which were consistent with experimental STM images.

Enhanced Transverse Seebeck Coefficients in 2D/2D PtSe2/MoS2 Heterostructures Using Wet-Transfer Stacking.

It is very challenging to estimate thermoelectric (TE) properties when applying millimeter-scale two-dimensional (2D) transition metal dichalcogenide (TMDC) materials to TE device applications, particularly their Seebeck coefficient due to their high intrinsic electrical resistance. This paper proposes an innovative approach to measure large transverse (i.e., in-plane) Seebeck coefficients for 2D TMDC materials by placing a low resistance (LR) semimetallic PtSe2 film on high-resistance (HR) semiconducting MoS2 (>10 MΩ), whose internal resistance is too high to measure the Seebeck coefficient, forming a heterojunction structure using wet-transfer stacking. The vertically stacked LR-PtSe2 (3 nm)/HR-MoS2 (12 nm) heterostructure film exhibits a high Seebeck coefficient > 190 μV/K up to 5 K temperature difference. This unusual behavior can be explained by an additional Seebeck effect induced at the interface between the LR-2D/HR-2D heterostructure. The proposed stacked LR-PtSe2/HR-MoS2 heterostructure film offers promising phenomena 2D/2D materials that enable innovative TE device applications.

Thickness-dependent optical response and ultrafast carrier dynamics of PtSe2 films

As a novel transition metal dichalcogenide material with high carrier mobility, adjustable band gap and excellent stability, the photocarrier ultrafast dynamics of PtSe2 films with the different thickness is researched by ultrafast transient absorption spectrum and optical pump and terahertz probe spectrum. The experimental results show that the few-layer PtSe2 films present semiconductor phase which exhibits a triple exponential decay process, while multi-layer of PtSe2 films present semi-metallic phase which exhibits a double exponential decay process. And the principle of light response and carrier dynamics of PtSe2 films after excitation is analyzed, one found that the defect state carrier recombination exists in all samples. The carrier relaxation is dominated by Auger exciton–exciton annihilation in few-layer PtSe2 film, and the defect state of multiple-layer PtSe2 film plays a dominant role in the photo carrier relaxation, which is promising to a further application in modulators and detectors for characterizing the transition from semiconductor to semi-metal by controlling its film thickness.

Effect of crystallinity and thickness on thermal transport in layered PtSe2

We present a comparative investigation of the influence of crystallinity and film thickness on the acoustic and thermal properties of layered PtSe2 films of varying thickness (1–40 layers) using frequency-domain thermo-reflectance, low-frequency Raman, and pump-probe coherent phonon spectroscopy. We find ballistic cross-plane heat transport up to ~30 layers PtSe2 and a 35% reduction in the cross-plane thermal conductivity of polycrystalline films with thickness larger than 20 layers compared to the crystalline films of the same thickness. First-principles calculations further reveal a high degree of thermal conductivity anisotropy and a remarkable large contribution of the optical phonons to the thermal conductivity in bulk (~20%) and thin PtSe2 films (~30%). Moreover, we show strong interlayer interactions in PtSe2, short acoustic phonon lifetimes in the range of picoseconds, an out-of-plane elastic constant of 31.8 GPa, and a layer-dependent group velocity ranging from 1340 ms−1 in bilayer to 1873 ms−1 in eight layers of PtSe2. The potential of tuning the lattice thermal conductivity of layered materials with the level of crystallinity and the real-time observation of coherent phonon dynamics open a new playground for research in 2D thermoelectric devices and provides guidelines for thermal management in 2D electronics.

Defect-gradient-induced Rashba effect in van der Waals PtSe2 layers

Defect engineering is one of the key technologies in materials science, enriching the modern semiconductor industry and providing good test-beds for solid-state physics. While homogenous doping prevails in conventional defect engineering, various artificial defect distributions have been predicted to induce desired physical properties in host materials, especially associated with symmetry breakings. Here, we show layer-by-layer defect-gradients in two-dimensional PtSe2 films developed by selective plasma treatments, which break spatial inversion symmetry and give rise to the Rashba effect. Scanning transmission electron microscopy analyses reveal that Se vacancies extend down to 7 nm from the surface and Se/Pt ratio exhibits linear variation along the layers. The Rashba effect induced by broken inversion symmetry is demonstrated through the observations of nonreciprocal transport behaviors and first-principles density functional theory calculations. Our methodology paves the way for functional defect engineering that entangles spin and momentum of itinerant electrons for emerging electronic applications.

Molecular beam epitaxy of PtSe2 using a co-deposition approach

The structural properties of co-deposited ultrathin PtSe2 films grown at low temperatures by molecular beam epitaxy on c-plane Al2O3 are studied. By simultaneously supplying a Se flux from a Knudsen cell and Pt atoms from an electron-beam evaporator, crystalline (001)-oriented PtSe2 films were formed between 200 °C and 300 °C. The long separation between substrate and electron beam evaporator of about 60 cm ensured minimal thermal load. At optimum deposition temperatures, a ten times or even higher supply rate of Se compared to Pt ensured that the pronounced volatility of the Se was compensated and the PtSe2 phase was formed and stabilized at the growth front. Postgrowth anneals under a Se flux was found to dramatically improve the crystalline quality of the films. Even before the postgrowth anneal in Se, the crystallinity of PtSe2 films grown with the co-deposition method was superior to films realized by thermal assisted conversion. Postgrowth annealed films showed Raman modes with narrower peaks and more than twice the intensity. Transmission electron microscopy investigations revealed that the deposited material transitioned to a two-dimensional layered structure only after the postgrowth anneal. PtSe2 growth was found to start as single layer islands that preferentially nucleated at atomic steps of the substrate and progressed in a layer-by-layer like fashion. A close to ideal wetting behavior resulted in coalesced PtSe2 films after depositing about 1.5 PtSe2 layers. Detailed Raman investigation of the observed PtSe2 layer breathing modes of films grown under optimized co-deposition conditions revealed an interlayer coupling force constant of 5.0–5.6 × 1019 N m−3.

Interface-Induced Seebeck Effect in PtSe2/PtSe2 van der Waals Homostructures.

The Seebeck effect refers to the production of an electric voltage when different temperatures are applied on a conductor, and the corresponding voltage-production efficiency is represented by the Seebeck coefficient. We report a Seebeck effect: thermal generation of driving voltage from the heat flowing in a thin PtSe2/PtSe2 van der Waals homostructure at the interface. We refer to the effect as the interface-induced Seebeck effect. By exploiting this effect by directly attaching multilayered PtSe2 over high-resistance PtSe2 thin films as a hybridized single structure, we obtained the highly challenging in-plane Seebeck coefficient of the PtSe2 films that exhibit extremely high resistances. This direct attachment further enhanced the in-plane thermal Seebeck coefficients of the PtSe2/PtSe2 van der Waals homostructure on sapphire substrates. Consequently, we successfully enhanced the in-plane Seebeck coefficients for the PtSe2 (10 nm)/PtSe2 (2 nm) homostructure approximately 42% compared to that of a pure PtSe2 (10 nm) layer at 300 K. These findings represent a significant achievement in understanding the interface-induced Seebeck effect and provide an effective strategy for promising large-area thermoelectric energy harvesting devices using two-dimensional transition metal dichalcogenide materials, which are ideal thermoelectric platforms with high figures of merit.

Morphology-controlled growth of large-area PtSe2 films for enhanced hydrogen evolution reaction

Morphology-controlled growth of large-area PtSe2 films for enhanced hydrogen evolution reaction

Broadband Optical Properties of Atomically Thin PtS2 and PtSe2.

Noble transition metal dichalcogenides (TMDCs) such as PtS2 and PtSe2 show significant potential in a wide range of optoelectronic and photonic applications. Noble TMDCs, unlike standard TMDCs such as MoS2 and WS2, operate in the ultrawide spectral range from ultraviolet to mid-infrared wavelengths; however, their properties remain largely unexplored. Here, we measured the broadband (245–3300 nm) optical constants of ultrathin PtS2 and PtSe2 films to eliminate this gap and provide a foundation for optoelectronic device simulation. We discovered their broadband absorption and high refractive index both theoretically and experimentally. Based on first-principle calculations, we also predicted their giant out-of-plane optical anisotropy for monocrystals. As a practical illustration of the obtained optical properties, we demonstrated surface plasmon resonance biosensors with PtS2 or PtSe2 functional layers, which dramatically improves sensor sensitivity by 60 and 30%, respectively.