Valence Band Structure Research Articles

High thermolectric properties of disordered Ge0.8-ySn0.2MnyTe semiconductor

For layered GeTe-based materials, the typical strategy to reduce the thermal conductivity of the crystal lattice is to introduce atomic disorder, increase the lattice non-harmonicity, and maximize the fluctuations of the quality/stress field in the sample. Since Sn/Mn can easily form solid solutions in the GeTe matrix, the degree of disorder in the sample is much higher than the level reported in IV-VI alloys in the past, which leads to a strong phonon scattering and a sharp decrease in the lattice thermal conductivity over the entire temperature range. In addition, Mn plays a significant role in changing the valence band structure of GeTe, i.e., Mn doping enhances the convergence of the light valence band and the heavy valence band and the change of the bandgap, significantly increasing the Seebeck coefficient of the GeTe matrix, resulting in a significant improvement in the thermoelectric performance of the Sn/Mn co-doped synthesized GeTe-based materials. Finally, we found that treating the sample with layered disorder is an effective method to improve the thermoelectric performance, and this study has certain reference value for the development of novel toxic-free, high-performance thermoelectric materials.

Ensemble Monte Carlo transport studies of zinc-blende cuprous halides

We present a comprehensive theoretical analysis of intrinsic high-field transport in cuprous halides: CuCl, CuBr, and CuI. Ensemble Monte Carlo transport simulations were performed based on analytical approximations of the multi-valley and three-band electronic structure model. The deformation potentials, extracted from carrier–phonon interaction matrix elements calculated via the Wannier function approach, were employed to determine scattering rates. Our detailed analysis uncovers intriguing transport characteristics based on the complex valence band structures, resulting from spin–orbit coupling and band inversion. Remarkably, the hole mobility in CuI was exceptionally high, reaching up to 193 cm2/V s, while CuCl exhibited unusual temperature dependencies in hole transport. Additionally, the electron mobility in CuI was found to be 254 cm2/V s, indicating a minimal disparity between carrier mobilities, which is advantageous for optoelectronic applications.

Realizing Ultrahigh Conversion Efficiency of ≈9.0% in YbCd2Sb2/Mg3Sb2 Zintl Module for Thermoelectric Power Generation.

Recently, YbCd2Sb2-based Zintl compounds have been widely investigated owing to their extraordinary thermoelectric (TE) performance. However, its p orbitals of anions that determined the valence band structure are split due to crystal field splitting that provides a good platform for band manipulation by doping/alloying and, more importantly, the YbCd2Sb2-based device has yet to be reported. In this work, single-phase YbCd1.5Zn0.5Sb2 is successfully obtained through precise chemical composition control. Then, YbMg2Sb2-alloying increases the cationic vacancy defect formation energy and further optimizes carrier concentration. Moreover, the band structure of YbCd1.5Zn0.5Sb2 is subtly manipulated, and the underlying mechanism is experimentally explored. Combined with the reduced lattice thermal conductivity, a high peak ZT value of ∼1.43 at 700K is obtained for YbCd1.425Zn0.475Mg0.1Sb2. Subsequently, choosing Fe90Sb10 as the diffusion barrier layer and adopting the transient liquid phase bonding technique, for the first time, it is demonstrated that YbCd2Sb2/Mg3(Sb, Bi)2 TE module with an ultrahigh conversion efficiency of ≈9.0% at a heat difference of 430K. More importantly, this module displays good thermal stability. This work paves the way for YbCd2Sb2 materials and devices in mid-temperature heat recovery.

Rydberg excitons in cuprous oxide: A two-particle system with classical chaos.

When an electron in a semiconductor gets excited to the conduction band, the missing electron can be viewed as a positively charged particle, the hole. Due to the Coulomb interaction, electrons and holes can form a hydrogen-like bound state called the exciton. For cuprous oxide, a Rydberg series up to high principle quantum numbers has been observed by Kazimierczuk et al. [Nature 514, 343 (2014)] with the extension of excitons up to the μm-range. In this region, the correspondence principle should hold and quantum mechanics turn into classical dynamics. Due to the complex valence band structure of Cu2O, classical dynamics deviates from a purely hydrogen-like behavior. The uppermost valence band in cuprous oxide splits into various bands resulting in yellow and green exciton series. Since the system exhibits no spherical symmetry, the angular momentum is not conserved. Thus, the classical dynamics becomes non-integrable, resulting in the possibility of chaotic motion. Here, we investigate the classical dynamics of the yellow and green exciton series in cuprous oxide for two-dimensional orbits in the symmetry planes as well as fully three-dimensional orbits. Our analysis reveals substantial differences between the dynamics of the yellow and green exciton series. While it is mostly regular for the yellow series, large regions in phase space with classical chaos do exist for the green exciton series.

Construction of S/g-C3N4@β-Bi2O3 heterojunction and its photocatalytic degradation of toluene in the gas phase.

In this paper, a modification of g-C3N4 was carried out by combining non-metal doping with the construction of heterojunctions, and a type II heterojunction composite, S/g-C3N4@β-Bi2O3, was prepared. The phase structure, morphology, elemental composition, valence band structure, and light absorption performance of the photocatalyst were analyzed using characterization techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). The performance of the composite photocatalyst in the photocatalytic degradation of gaseous toluene, one of the typical volatile organic compounds (VOCs), under simulated solar light was studied. The effects of preparation conditions, toluene concentration, and recycling on the photocatalytic performance of the composite photocatalyst were investigated. The results show that under the optimal preparation conditions, S/g-C3N4@β-Bi2O3 achieved a degradation efficiency of 74.0% for 5ppm toluene after 5h of light irradiation. Although the degradation efficiency decreased to 61.2% after five cycles, it maintained 83% of its initial activity, indicating good stability of the composite photocatalyst. Free radical quenching experiments demonstrated that h+ was the main active species in the photocatalytic degradation of toluene, followed by ·O2-. Based on all experimental results, the migration law of photo-generated charges was analyzed, and a possible photocatalytic mechanism was proposed. In this study, a new material was obtained for the photocatalytic removal of VOCs by improving the photocatalytic properties of g-C3N4.

Versatile Method for Preparing Two-Dimensional Metal Dihalides.

Ever since the ground-breaking isolation of graphene, numerous two-dimensional (2D) materials have emerged with 2D metal dihalides gaining significant attention due to their intriguing electrical and magnetic properties. In this study, we introduce an innovative approach via anhydrous solvent-induced recrystallization of bulk powders to obtain crystals of metal dihalides (MX2, with M = Cu, Ni, Co and X = Br, Cl, I), which can be exfoliated to 2D flakes. We demonstrate the effectiveness of our method using CuBr2 as an example, which forms large layered crystals. We investigate the structural properties of both the bulk and 2D CuBr2 using X-ray diffraction, along with Raman scattering and optical spectroscopy, revealing its quasi-1D chain structure, which translates to distinct emission and scattering characteristics. Furthermore, microultraviolet photoemission spectroscopy and electronic transport reveal the electronic properties of CuBr2 flakes, including their valence band structure. We extend our methodology to other metal halides and assess the stability of the metal halide flakes in controlled environments. We show that optical contrast can be used to characterize the flake thicknesses for these materials. Our findings demonstrate the versatility and potential applications of the proposed methodology for preparing and studying 2D metal halide flakes.

Enhancing the dipole ring of hexagonal boron nitride nanomesh by surface alloying

Surface templating by electrostatic surface potentials is the least invasive way to design large-scale artificial nanostructures. However, generating sufficiently large potential gradients remains challenging. Here, we lay the groundwork for significantly enhancing local electrostatic fields by chemical modification of the surface. We consider the hexagonal boron nitride (h-BN) nanomesh on Rh(111), which already exhibits small surface potential gradients between its pore and wire regions. Using photoemission spectroscopy, we show that adding Au atoms to the Rh(111) surface layer leads to a local migration of Au atoms below the wire regions of the nanomesh. This significantly increases the local work function difference between the pore and wire regions that can be quantified experimentally by the changes in the h-BN valence band structure. Using density functional theory, we identify an electron transfer from Rh to Au as the microscopic origin for the local enhancement of potential gradients within the h-BN nanomesh.

Face-centered cubic carbon as a fourth basic carbon allotrope with properties of intrinsic semiconductors and ultra-wide bandgap

Carbon is considered to exist in three basic forms: diamond, graphite/graphene/fullerenes, and carbyne, which differ in a type of atomic orbitals hybridization. Since several decades the existence of the fourth basic carbon allotropic form with the face-centered cubic (fcc) crystal lattice has been a matter of discussion despite clear evidence for its laboratory synthesis and presence in nature. Here, we obtain this carbon allotrope in form of epitaxial films on diamond in a quantity sufficient to perform their comprehensive studies. The carbon material has an fcc crystal structure, shows a negative electron affinity, and is characterized by a peculiar hybridization of the valence atomic orbitals. Its bandgap (~6 eV) is typical for insulators, whereas the noticeable electrical conductivity (~0.1 S m−1) increases with temperature, which is typical for semiconductors. Ab initio calculations explain this apparent contradiction by noncovalent sharing p-electrons present in the uncommon valence band structure comprising an intraband gap. This carbon allotrope can create a new pathway to ‘carbon electronics’ as the first intrinsic semiconductor with an ultra-wide bandgap.

Unraveling the Presence and Positions of Nitrogen Defects in Defective g‐C3N4 for Improved Organic Photocatalytic Degradation: Insights from Experiments and Theoretical Calculations

AbstractIn this work, nitrogen‐defective g‐C3N4 with different nitrogen defect densities is synthesized for ciprofloxacin photocatalytic degradation. Compared with pristine g‐C3N4, g‐C3N4 etched with NaBH4 for 1 h exhibits an approximately ten‐fold increase in the rate constant of ciprofloxacin (CIP) degradation. The combined experimental analysis and theoretical calculations reveal that nitrogen defects can be incorporated into g‐C3N4 in all nitrogen sites and that C─N═C is the most susceptible site. By incorporating nitrogen defects to induce defect states between the conduction band (CB) and valence band (VB), the electronic and band structures are tuned. The induced defect states can be downshifted to approach the valance band, reaching increased nitrogen defect density within optimum ranges to accommodate excited electrons to narrow the bandgap, extend the light absorption capability, and enhance the charge carrier separation and transfer efficiency. The g‐C3N4 etched by NaBH4 for 2 h with over‐introduced nitrogen defects exhibits a declined performance due to a deteriorated structure, and the over‐downshifted defect states turn out to be a new recombination center for charge carriers.

Observations on Valence‐Band Electronic Structure and Surface States of Bulk Insulators Based on Fast Stabilization Process of Sample Charging in UPS

AbstractThe valence‐band electronic structure is one of the most basic properties of materials and ultraviolet photoelectron spectroscopy (UPS) is the most commonly used technique for its measurement. To obtain credible UPS spectra on insulator surfaces, eliminating the charging effects at the surfaces is essential but is very difficult. Here, a reliable measurement for the valence‐band structure of bulk insulators is shown. It has been observed that, during UPS measurements without any charge compensation, the charging on irradiated insulator surfaces reaches its steady state very quickly and the fluctuation of the charging‐induced surface potential is very small. Therefore, the whole UPS spectrum undergoes just a parallel shift and can be calibrated by comparison with the corresponding X‐ray photoelectron spectroscopy (XPS) spectrum even though XPS often has a poorer resolution than UPS. From the calibrated valence‐band spectra, it is found that noticeable electronic energy levels (i.e., the “surface states”) exist in the bandgap, and based on the density of states (DOS) calculations, the surface states are attributed to the truncation of the bulk periodic structure at the surfaces. This work is anticipated to provide a way to obtain the valence band structure and the surface states of bulk insulators which play crucial roles in many physical processes.

Gaussian-process-regression-based method for the localization of exceptional points in complex resonance spectra

Resonances in open quantum systems depending on at least two controllable parameters can show the phenomenon of exceptional points (EPs), where not only the eigenvalues but also the eigenvectors of two or more resonances coalesce. Their exact localization in the parameter space is challenging, in particular in systems, where the computation of the quantum spectra and resonances is numerically very expensive. We introduce an efficient machine learning algorithm to find EPs based on Gaussian process regression (GPR). The GPR-model is trained with an initial set of eigenvalue pairs belonging to an EP and used for a first estimation of the EP position via a numerically cheap root search. The estimate is then improved iteratively by adding selected exact eigenvalue pairs as training points to the GPR-model. The GPR-based method is developed and tested on a simple low-dimensional matrix model and then applied to a challenging real physical system, viz., the localization of EPs in the resonance spectra of excitons in cuprous oxide in external electric and magnetic fields. The precise computation of EPs, by taking into account the complete valence band structure and central-cell corrections of the crystal, can be the basis for the experimental observation of EPs in this system.

2D Multiferroics in As‐Substituted Bilayer α‐In2Se3 with Enhanced Magnetic Moments for Next‐Generation Nonvolatile Memory Device

AbstractSearching for multiferroic materials with ferromagnetic (FM) and ferroelectric (FE) properties holds promise for ultra‐high‐density and low‐energy‐consumption memory device applications, but 2D materials with both properties are rare. Herein, a general strategy to achieve nonvolatile electric field control of magnetism in the bilayer (BL) α‐In2Se3 by hole doping is proposed. By first‐principles calculations, it is demonstrated that hole doping can induce robust ferromagnetism in the bilayer α‐In2Se3 due to its unique flat Mexican‐hat‐shape valence band structure. Such band edges cause van Hove singularities (VHS), and proper hole doping can lead to time‐reversal symmetry breaking. The bilayer α‐In2Se3 exhibits ferromagnetism and ferroelectricity within a wide range of doping concentrations, resulting in an unexpected multiferroic phase. Furthermore, when the electrical polarization of α‐In2Se3 flips from downward to upward, it becomes non‐magnetic (NM) from ferromagnetic states in the As‐substituted bilayer α‐In2Se3, which can work as a nonvolatile magnetic storage unit. Remarkably, the As‐substituted bilayer α‐In2Se3 exhibits an enhanced magnetic moment of 1.2 μB per AsSe due to substantial charge transfer across the interface. Notably, the mechanism of electrically controlled magnetism is elucidated as the coupling among the Mexican‐hat‐like dispersion, ferromagnetism, and ferroelectricity. The findings offer a promising strategy for electrical writing and the magnetic reading memory device.

Promoted Na Solubility and Modified Band Structure for Achieving Exceptional Average ZT by Extra Mn Doping in PbTe.

Na doping strategy provides an effective avenue to upgrade the thermoelectric performance of PbTe-based materials by optimizing electrical properties. However, the limited solubility of Na inherently restricts the efficiency of doping, resulting in a relatively low average ZT, which poses challenges for the development and application of subsequent devices. Herein, to address this issue, the introduced spontaneous Pb vacancies and additional Mn doping synergistically promote Na solubility with a further modified valence band structure. Furthermore, the induced massive point defects and multiscale microstructure greatly strengthen the scattering of phonons over a wide frequency range, leading to a remarkable ultralow lattice thermal conductivity of ∼0.42 W m-1 K-1. As a result, benefiting from the significantly enhanced Seebeck coefficient and superior thermal transports, a high peak ZT of ∼2.1 at 773 K and an excellent average ZT of ∼1.4 between 303 and 823 K are simultaneously achieved in Pb0.93Na0.04Mn0.02Te. This work proposes a simple and constructive method to obtain high-performance PbTe-based materials and is promising for the development of thermoelectric power generation devices.

Hierarchical nano-/micro-architecture phonon scattering of p-type Bismuth telluride bulk composites with Ag-TiO2 nano particles synthesized by fluidized bed spray coating method

We optimize the thermoelectric (TE) properties by minimizing thermal conductivity utilizing by hierarchical phonon scattering from long to mid wavelength of phonon in p-type Bi0.4Sb1.6Te3.4 (BST) composite with nano Ag-coated TiO2 (Ag/TiO2). We employed an Ag nano particle (20 nm) modulation into TiO2 (500 nm) particles by spray coating method and dispersed in a p-type Bi0.4Sb1.6Te3.4 (BST), giving rise to a hierarchical architecture from nano to micro scale. The nano particle modulation of Ag/TiO2 particles decreases grain sizes of p-type BST matrix. The hierarchical structure of modulating nano particles and small grain sizes of the matrix significantly decreases lattice thermal conductivity due to wide range of wavelength phonon scattering, resulting in the enhancement of thermoelectric performance over a large temperature range. The maximum thermoelectric figure-of-merit zT value reaches to 1.28 for 0.9 wt% Ag/TiO2 modulation doping, which is superior to the other reported ones. The optimized modulating Ag/TiO2 nano-particle dispersion effectively maintains the valence band structure while concurrently mitigating the scattering of charge carriers. Therefore, the nano particle modulation by spray coating method is an effective way to manifest hierarchical architecture from nano to micro-scale phonon scattering, which can be applied in thermoelectric materials design and process.

Photoemission spectroscopy and microscopy for Ta@Si16 superatoms and their assembled layers.

Superatoms (SAs) with specific compositions have the potential to significantly advance the field of nanomaterials science, leading to next-generation nanoscale functionalities. In this study, we fabricated assembled layers with tantalum metal-atom encapsulating silicon cage (Ta@Si16) SAs on an organic C60 substrate through deposition, and we characterized their electronic and optical properties by photoelectron spectroscopy and microscopy. The alkaline nature of Ta@Si16 SAs reveals their electronic behaviors, such as charge transfer and electromagnetic near-field sensing, through two-photon photoemission (2PPE) spectroscopy and microscopy with a femtosecond laser. The evolution of the work function for Ta@Si16 SAs on C60, observed by 2PPE spectroscopy, demonstrates charge transfer complexation between the topmost C60 layer and the first Ta@Si16 layer, consistent with the electron-donating alkaline characteristics of Ta@Si16 SAs. Specifically, a small amount of Ta@Si16 SA deposition leads to a dramatic increase in 2PPE intensity, attributable to electromagnetic near-field enhancements, suggesting applications as sensitizers for nonlinear imaging in photoemission microscopy. For the assembled Ta@Si16 SA layers, a plasmonic response of hνp = 17.9 eV is spectroscopically identified, including their valence and conduction band structures, and the plasmonic energetics are discussed in the context of metal doping in bulk silicon.

Interfacial electronic state between hexagonal ZnO and cubic NiO.

The interface of two dissimilar materials gives rise to a myriad of interesting structural, magnetic, and electronic properties that may be utilized to produce novel materials with unique characteristics and functions. In particular, growing a cubic oxide film on top of a hexagonal oxide substrate results in such unique properties due to the conflict of their respective stabilization mechanisms within the interface layer. This study aims to elucidate the electronic properties of the interface between hexagonal ZnO and cubic NiO by analyzing the interface electronic states within epitaxial NiO films grown on ZnO substrates, expressed in the form of ultraviolet photoemission spectroscopy (UPS) for valence band structure and X-ray absorption spectroscopy (XAS) spectra for conduction band structure. This is accomplished through a modeling approach in which the film, substrate, and interface signals are assumed to be related to each other by a set of mathematical equations, and then rearranging and modulating the equations to obtain unique UPS and XAS spectra that depict the interface electronic states.

First synthesis of RuSn solid-solution alloy nanoparticles and their enhanced hydrogen evolution reaction activity.

Solid-solution alloys based on platinum group metals and p-block metals have attracted much attention due to their promising potential as materials with a continuously fine-tunable electronic structure. Here, we report on the first synthesis of novel solid-solution RuSn alloy nanoparticles (NPs) by electrochemical cyclic voltammetry sweeping of RuSn@SnOx NPs. High-angle annular dark-field scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy maps confirmed the random and homogeneous distribution of Ru and Sn elements in the alloy NPs. Compared with monometallic Ru NPs, the RuSn alloy NPs showed improved hydrogen evolution reaction (HER) performance. The overpotentials of Ru0.94Sn0.06 NPs/C and Ru0.87Sn0.13 NPs/C to achieve a current density of 10 mA cm-2 were 43.41 and 33.19 mV, respectively, which are lower than those of monometallic Ru NPs/C (53.53 mV) and commercial Pt NPs/C (55.77 mV). The valence-band structures of the NPs investigated by hard X-ray photoelectron spectroscopy demonstrated that the d-band centre of RuSn NPs shifted downward compared with that of Ru NPs. X-ray photoelectron spectroscopy and X-ray absorption near-edge structure analyses indicated that in the RuSn alloy NPs, charge transfer occurs from Sn to Ru, which was considered to result in a downward shift of the d-band centre in RuSn NPs and to regulate the adsorption energy of intermediate Hads effectively, and thus enable the RuSn solid-solution alloy NPs to exhibit excellent HER catalytic properties.

The Mechanism Behind the High zT of SnSe<sub>2</sub> Added SnSe at High Temperatures

SnSe is a promising thermoelectric material due to its low toxicity, low thermal conductivity, and multiple valence band structures, which are ideal for high electronic transport properties. The multiple valence band structure has attracted many attempts to engineer the carrier concentration of the SnSe via doping, to place its fermi level at a position where the maximum number of valence bands can participate in the electronic transport. Up until now, ~5 × 10<sup>19</sup> cm<sup>-3</sup> was the highest carrier concentration achieved in SnSe via doping. Recently, introducing SnSe<sub>2</sub> into SnSe was found to effectively increase the carrier concentration as high as ~6.5 × 10<sup>19</sup> cm<sup>-3</sup> (at 300 K) due to the generated Sn vacancies. This high carrier concentration at 300 K, combined with the reduction in lattice thermal conductivity due to SnSe<sub>2</sub> micro-domains formed within the SnSe lattice, improved the thermoelectric performance (<i>zT</i>) of SnSe – <i>x</i>SnSe<sub>2</sub> as high as ~2.2 at 773 K. Here, we analyzed the changes in the electronic band parameters of SnSe as a function of temperature with varying SnSe<sub>2</sub> content using the Single Parabolic Band (SPB) model. According to the SPB model, the calculated density-of-states effective mass and the fermi level are changed with temperature in such a way that the Hall carrier concentration (<i>nH</i>) of the SnSe – xSnSe2 samples at 773 K coincides with the optimum <i>nH</i> where the theoretically maximum <i>zT</i> is predicted. To optimize the <i>nH</i> at high temperatures for the highest <i>zT</i>, it is essential to tune the 300 K <i>nH</i> and the rate of <i>nH</i> change with increasing temperature via doping.

Differences in N species induced by pyrolysis temperature: D-band center adjustment over the biomass carbon-supported CoP for boosting hydrogen evolution reaction

Nitrogen (N) species in biomass-based carbon can be adjusted through pyrolysis at different temperatures, optimizing the valence band structure of supported metal nanoparticles through electronic metal-support interactions (EMSIs). Herein, ginkgo leaves-based carbon supported cobalt phosphide (CoP@NSPC-T, T = 850, 900 and 950 °C) was obtained via carbothermal reduction method at different pyrolysis temperature. Pyridinic N and pyrrolic N in carbon lattice were dramatically decreased with pyrolysis temperature raised, whereas the graphitic N showed the opposite trend. The change in N species (pyridinic N, pyrrolic N and graphitic N) reconfigured the valence band structure of CoP@NSPC-T, inducing the enhancement of work function and the upshift of d-band center. A relationship between the ratio of (pyridinic N + pyrrolic N)/graphitic N, work function, d-band center, and HER activity (η10) of catalysts was established. CoP@NSPC-900 with a moderate work function value and d-band center tend to achieve a balance for Volmer process and Heyrovsky process, exhibiting the lowest η10 value activity among the resulted catalysts as the ratio of (pyridinic N + pyrrolic N)/graphitic N is 1.33.

Quasi van der Waals Epitaxy of Rhombohedral-Stacked Bilayer WSe2 on GaP(111) Heterostructure.

The growth of bilayers of two-dimensional (2D) materials on conventional 3D semiconductors results in 2D/3D hybrid heterostructures, which can provide additional advantages over more established 3D semiconductors while retaining some specificities of 2D materials. Understanding and exploiting these phenomena hinge on knowing the electronic properties and the hybridization of these structures. Here, we demonstrate that a rhombohedral-stacked bilayer (AB stacking) can be obtained by molecular beam epitaxy growth of tungsten diselenide (WSe2) on a gallium phosphide (GaP) substrate. We confirm the presence of 3R-stacking of the WSe2 bilayer structure using scanning transmission electron microscopy (STEM) and micro-Raman spectroscopy. Also, we report high-resolution angle-resolved photoemission spectroscopy (ARPES) on our rhombohedral-stacked WSe2 bilayer grown on a GaP(111)B substrate. Our ARPES measurements confirm the expected valence band structure of WSe2 with the band maximum located at the Γ point of the Brillouin zone. The epitaxial growth of WSe2/GaP(111)B helps to understand the fundamental properties of these 2D/3D heterostructures, toward their implementation in future devices.