Structural Phase Stability Research Articles

EFFECT OF ANNEALING TEMPERATURE ON THE STRUCTURAL AND THERMOELECTRIC PROPERTIES OF CuFeS2 NANOPARTICLES PREPARED BY THE HYDROTHERMAL METHOD

The current study described precise and simple hydrothermal method used to synthesize CuFeS2 nanoparticles. The thermoelectric properties of CuFeS2 nanoparticles were studied under different conditions of annealing treatment. The phase structure, functional groups, and thermal stability of the CuFeS2 nanoparticles samples were analyzed via X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA). The X-ray diffraction (XRD) results of the synthesized nanoparticles closely matched the CuFeS2 chalcopyrite patterns. FT-IR measurements confirmed the presence of the characteristic S-O, Fe-S, and O-H groups in the structure of the prepared nanoparticles. The TGA results indicate that the CuFeS2 nanoparticles are thermally stable below 650°C. The scan electron microscope (SEM) measurements revealed that the particle size of all the samples was less than 100 nm after the annealing treatment. The optical measurements showed that the absorbance edges of the CuFeS2 samples shifted to longer wavelengths after the annealing treatment. The thermoelectric measurements indicated that the annealing treatment modulated the electrical conductivity, Seebeck coefficient, power factor, and thermal conductivity of the CuFeS2 samples.

Acoustic shock wave-induced structural phase stability of tetrahedral amorphous carbon, graphite and graphene by Raman and X-ray photoelectron spectroscopic approaches

Acoustic shock wave-induced structural phase stability of tetrahedral amorphous carbon, graphite and graphene by Raman and X-ray photoelectron spectroscopic approaches

Morphology of Secondary Phase Particles and Stability of Subgrain Structure in Martensitic Steel 10Cr9Co3W2MoVNbB (ASTM A335 P92) Under Creep Conditions

Morphology of Secondary Phase Particles and Stability of Subgrain Structure in Martensitic Steel 10Cr9Co3W2MoVNbB (ASTM A335 P92) Under Creep Conditions

Computational investigation of the phase stability, electronic, optical, phonon spectrum, and elastic behavior of layered perovskites Ca2XO4 (X = Zr, Hf) for optoelectronic applications.

A significant class of solid-state materials, Ruddlesden-Popper (RP) perovskites are well-known for their rich chemical compositions that make them excellent electrocatalysts. Therefore, in this work, we conduct thorough analysis of RP perovskites, specifically Ca2XO4 (X = Zr, Hf). We delve into the structural, electronic, optical, and mechanical properties presenting their insights for the first time. Our investigations reveal that Ca2XO4 (X = Zr, Hf) exhibits stable tetragonal phase structures, with energies (E0) of - 10,522.93eV and - 33,520.14eV, respectively. The calculated in terms of the ground state determines to possess distinct values such as - 4.79 eV/atom for LiScTe2 and - 3.95 eV/atom for Ca2ZrO4 and Ca2HfO4. Notably, the semiconductor characteristics of Ca2ZrO4 and Ca2HfO4 are underscored by their respective wide direct band gap of 5.02eV and 5.30eV. Then, we discuss the optical parameters encompassing the dielectric function, absorption coefficient, optical conductivity, refractive index, and energy loss function. is described as ductile, whereas is defined as brittle. Our outcomes underscore remarkable ability of these materials to absorb ultraviolet radiation from the electromagnetic spectrum, positioning them as promising candidates for optoelectronic applications. We made these calculations by employing first-principles approach rooted in density functional theory (DFT) and utilizing the Perdew-Burke-Ernzerhof-Generalized Gradient Approximation (PBE-GGA) and Tran and Blaha-modified Becke-Johnson (TB-mBJ) functional within the WEIN2K framework. In this framework, Kramers-Kronig relations are used to obtain crucial optical parameters. Mechanical behavior is assessed by employing Voigt-Reuss-Hill approximation (VRH) fulfilling the Born's criteria which emphasizes that these materials are equally appropriate for a broad range of mechanical applications.

Enhanced photocatalytic and supercapacitor performance of CeO2 nano foam integrated MWCNT and rGO nanocomposites

In this study, Cerium oxide nanoparticles (CeO2 NPs) with foam like morphology were prepared using the Moringa Oleifera seed extract-assisted green synthesis method. The prepared CeO2 NPs were integrated respectively with reduced graphene oxide (CeO2/rGO) and multi-walled carbon nanotubes (CeO2/MWCNT) via a simple one-pot reflex method. The structural and morphological features and elemental characteristics, including the physico-chemical and thermal characteristics of the samples, were assessed. The photocatalytic degradation ability of the catalyst was tested against Alizarin Red (AR) and Safranin (SF) dyes. Under sunlight, degradation efficiencies of 92.62%, 95.46%, and 99.62% were achieved against Safranin dye by CeO2, CeO2/MWCNT, and CeO2/rGO, respectively. The XRD analysis shows the structural phase stability of the nanocatalyst even after five cycles. The supercapacitor characteristics of all anode electrode samples were assessed. Moreover, the specific capacitance values of 370, 413, and 554 Fg-1 were measured using cyclic voltammetry at a scan rate of 5 mV/s for CeO2, CeO2/MWCNT, and CeO2/rGO, respectively. After undergoing 3000 charge-discharge cycles, the hybrid CeO2/rGO nanocomposite revealed admirable cycling stability with an 8.6% decrease in its specific capacitance. According to the results, the green-mediated CeO2/rGO heterojunction nano semiconducting materials are promising candidates for twin applications in photocatalysis and supercapacitors.

High-performance multiphase Sm-Co-B alloys with coercivities up to 6.71 MA·m−1

SmCo4B-based alloys with high magnetocrystalline anisotropy are expected to be used as raw materials or constituent phases for new permanent magnets. In this work, we develop Sm(Co, Fe, Ni)4B alloys with excellent hard magnetic properties by tuning the contents of Fe, Co, and Ni. The addition of Fe enhances the amorphous formation ability of the as-spun ribbons, whereas Ni addition improves the structural stability of the crystalline phases. During annealing, the amorphous phase crystallizes into different Sm-Co-B phases in stages. A high coercivity of 5.68–6.71 MA·m−1 is obtained in the annealed SmCo4–x–yFexNiyB (x = 1.0–2.0, y = 0.8–1.0) ribbons composed of platelet-shaped and equiaxed grains in comparison with the coercivity of 2.89–5.18 MA·m−1 in the x = 1.0–1.2 and y = 0–0.8 ribbons with equiaxed grains. Here, we show the strong correlations between the microstructure and magnetic properties and provide insights for the future development of high-performance SmCo4B-based magnets.

Characterization of the Tensile Properties and Nanoscale Phase Structures of Modified Asphalts and Their Aging Behavior.

This study focuses on exploring tensile properties and nanoscale phase structures of different modified asphalts, and their aging behavior. For this, one virgin asphalt and three modified asphalts, namely, 4% SBS-modified asphalt, 2% SBS and 20% crumb rubber (CR) composite asphalt, and 4% SBS and 2%TiO2 composite asphalt, were prepared and investigated using the force-ductility test and atomic force microscopy (AFM). Also, detailed experiments of short-term (STA) and long-term (LTA) aging were conducted to obtain aged asphalt specimens. The results showed that a ductile fracture was found for the three modified asphalts. However, for the activation energy, SBS asphalt and SBS&TiO2 asphalt were 2.87 times and 3.31 times that of SBS&CR asphalt, respectively. This demonstrates that the activation of the SBS polymer phase requires more energy during the stretching process when the rubber powder is not present. SBS&CR asphalt and SBS&TiO2 asphalt showed better tensile properties and aging resistance in terms of the quantitative results of tensile property indicators, indicated by a larger value of fracture ductility, tensile compliance, and the toughness ratio under the same aging condition. According to the AFM results, SBS modifier had little effect on the phase structure of virgin asphalt, while TiO2 modifier increased the number of bee phases and made their distribution more uniform, indicating the formation of a more stable phase structure system. This may contribute to its better tensile properties and aging resistance. Moreover, TiO2 molecules inhibited the aggregation behavior of polar molecules during the aging process, which led to a reduction in surface roughness. By comparison, the effect of aging on the phase structure of SBS&CR asphalt was more significant among the three modified asphalts. This result can be attributed to the interaction between rubber powder particles and asphalt.

Enhanced mechanical hardness of mixed-phase BiFeO3 films through quenching

Due to epitaxial strain, BiFeO3 (BFO) thin films exhibit a morphotropic phase boundary with coexisting rhombohedral-like (R-like) and tetragonal-like (T-like) phases. The T-like phase, distinguished by its large c/a ratio and giant polarization, has garnered extensive interest. In this work, by quenching an epitaxial mixed-phase BFO thin film grown on a LaAlO3 substrate, a pronounced transition from the R-like to the T-like phase is observed. This transition is concomitant with improved phase structure stability under the force field induced by an atomic force microscope tip. PeakForce Quantitative NanoMechanics mapping reveals that the T-like phase exhibits a higher Young's modulus than the R-like phase, signifying an overall enhancement in the mechanical hardness of the BFO film. This work introduces a simple but powerful approach to manipulating the fraction of the T-like phase in the mixed-phase BFO films, presenting prospects for enhancing their performance and expanding their application range in advanced techniques.

Temperature and Pressure Effects on Phase Transitions and Structural Stability in CsPb2Br5 and CsPb2Br4I Perovskite-Derived Halides.

All-inorganic perovskites exhibit outstanding light absorption properties in the visible range suitable for solar energy applications. We focus on the synthesis of CsPb2(Br,I)5 using mechanochemical procedures. Synchrotron X-ray diffraction (SXRD) data are essential for determining the crystallographic evolution in the 295-753 K temperature range. From room temperature to 573 K, the crystal structure is refined in a two-dimensional (2D) tetragonal framework (space group: I4/mcm) consisting of layers of face sharing [Pb(Br,I)8] polyhedra. Above a transition temperature of Tt = 630 and 621 K, identified from differential scanning calorimetry (DSC) curves for CsPb2Br5 and CsPb2Br4I, respectively, a cubic three-dimensional (3D) corner-sharing perovskite structure is identified, showing substantial Cs and (Br,I) deficiency. A more ionic character for Cs-halide versus Pb-halide is derived from the evolution of the anisotropic atomic displacements. An ultralow thermal conductivity of 0.35-0.18 W m-1 K-1 is related to the low Debye temperatures. From high-pressure SXRD studies, the change in B0 can be attributed to a basic expansion of the unit-cell volume caused by the chemical pressure from iodine within the CsPb2Br5 framework. UV-vis-NIR spectroscopy revealed optical gaps of approximately 2.93 and 2.50 eV, respectively, which agrees with ab initio calculations.

Superior energy storage performance in (Bi0.5Na0.5)TiO3-based ceramics via entropy engineering strategy

In order to meet the application requirements in the field of advanced pulse power capacitors, the energy storage performance of dielectric materials urgently needs to be enhanced. Due to the novel high-entropy effects being beneficial for improving energy storage performance, entropy engineering has received widespread attention in dielectric energy storage materials. Herein, CaHfO3 modified (Bi0.5Na0.5)TiO3-based ceramics, (0.95-x)[(0.6BNT-0.4SBT)]-0.05La-xCaHfO3 (BNT-SBT-La-xCH) (0.01 <x< 0.10) ceramics, were designed by entropy engineering strategy and synthesized via a hydrothermal-assisted method. It is found the introduction of CaHfO3 enhances the configuration entropy and promotes the generation of high-entropy ceramics. The enhancement of configuration entropy leads to stable single phase structure, reduction of grain size, formation of polar nanoregions, enhancement of dielectric relaxation behavior, expansion of band gap, and increase in resistivity, resulting in large Eb and η. Accordingly, BNT-SBT-La-0.07CH high-entropy ceramic displays superior energy storage performance (Wrec = 6.30 J/cm3, η = 86.5 %) under a great Eb of 554 kV/cm along with good thermal, frequency, and cycle stability. These results confirm that entropy regulation provides a feasible way to produce high-performance energy storage ceramics.

The structural, elastic, optoelectronic properties and hydrogen storage capability of lead-free hydrides XZrH3 (X: Mg/Ca/Sr/Ba) for hydrogen storage application: A DFT study

Perovskite hydrides are promising materials for hydrogen capacity application to achieve the US DOE on-board criteria. We have investigated novel perovskite hydrides XZrH3 (X: Mg/Ca/Sr/Ba) for H2 storage and transportation applications. In this study we investigates the physical properties of XZrH3 light materials for solid-state hydrogen storage application by incorporating the DFT framework with the CASTEP code. We have theoretically examined the structural, mechanical, electronic, optical, and hydrogen storage properties of these materials. The selected compounds were fully relaxed and optimized in the cubic phase space group Pm-3 m. Structural phase stability was confirmed through thermodynamic, and mechanical analyses. Mechanical properties, evaluated based on Poisson’s ratio, the Puagh’s ratio, and Cauchy pressure, indicate the ductile behavior with a preference for ionic bonding. The electronic structure analysis reveals the metallic behavior of these materials. Optical calculations were also performed to provide additional insights into the physical properties of H2 compounds. The gravimetric hydrogen storage capacities were calculated as 2.55, 2.25, 1.66, and 1.31 wt% for MgZrH3, CaZrH3, SrZrH3, And BaZrH3 hydrides respectively. The identified properties of XZrH3 suggest that these materials could significantly enhance hydrogen storage systems, with potential integration into existing energy technologies, offering a pathway toward more efficient and sustainable hydrogen-based solutions.

Entropy Engineering of 2D Materials.

Entropy, a measure of disorder or uncertainty in the thermodynamics system, has been widely used to confer desirable functions to alloys and ceramics. The incorporation of three or more principal elements into a single sublattice increases the entropy to medium and high levels, imparting these materials a mélange of advanced mechanical and catalytic properties. In particular, when scaling down the dimensionality of crystals from bulk to the 2D space, the interplay between entropy stabilization and quantum confinement offers enticing opportunities for exploring new fundamental science and applications, since the structural ordering, phase stability, and local electronic states of these distorted 2D materials get significantly reshaped. During the last few years, the large family of high-entropy 2D materials is rapidly expanding to host MXenes, hydrotalcites, chalcogenides, metal-organic frameworks (MOFs), and many other uncharted members. Here, the recent advances in this dynamic field are reviewed, elucidating the influence of entropy on the fundamental properties and underlying elementary mechanisms of 2D materials. In particular, their structure-property relationships resulting from theoretical predictions and experimental findings are discussed. Furthermore, an outlook on the key challenges and opportunities of such an emerging field of 2D materials is also provided.

Ingenious regulation and activation of sites in the 2H-MoS2 basal planes by oxygen incorporation for enhanced photocatalytic hydrogen evolution of CdS

The 2H phase of MoS2 has the advantages of stable phase structure and tunable preparation approach, while the unfavorable H adsorption ability at the basal plane sites hinders the H2 evolution performance. Here, we developed an effective strategy for the regulation of the basal plane properties of MoS2 via oxygen doping. It is demonstrated that the Gibbs free energy of hydrogen adsorption (ΔGH*) at the sites in the basal plane can be effectively optimized. Using oxygen-doped MoS2 (OMoS) as a cocatalyst, the constructed OMoS/CdS heterojunction photocatalyst shows a stronger built-in electric field and improved photocatalytic H2 production activity. The optimized OMoS/CdS sample with only 0.3 wt% OMoS loading amount achieved an H2 evolution rate of 58.47 mmol g-1h−1 under AM 1.5 light irradiation, which is significantly superior to that of conventional MoS2 modified CdS and even higher than the 1 wt% Pt modified CdS. Our results not only highlighted the significant potential of OMoS as a photocatalyst for hydrogen production, but also proposed a superior to and effective conception for optimizing the H2 evolution activity at the basal plane sites of 2H-MoS2.

Mechanism of Defect Passivation in Sb2Se3 Solar Cells via Buried Selenium Seed Layer

AbstractQuasi‐1D antimony selenide (Sb2Se3) is known for its stable phase structure and excellent light absorption coefficient, making it a promising material for high‐efficiency light harvesting. However, the (Sb4Se6)n ribbons align horizontally, increasing defect interference and limiting vertical carrier transport. Herein, a novel strategy of burying selenium (Se) seed layers to reduce lattice mismatch at the heterojunction interface, promote crystal orientation, mitigate deep donor defects, increase P‐type carrier concentration, and purify the PN junction, is proposed. Admittance spectroscopy reveals that Sb2Se3 solar cells with Se seed layers have higher activation energies for defect states and significantly lower defect densities (1.2 × 1014, 2.7 × 1014, and 1.3 × 1015 cm−3 for D1, D2, and D3) compared to an order of magnitude higher densities in Sb2Se3 solar cells without a Se seed layer. First‐principles calculations support these findings, showing that Se seed layers create a Se‐rich environment, reducing selenium vacancies (VSe), antimony on selenium sites (SbSe), and interface defects. This dual passivation mechanism suppresses defect formation and activation, increasing carrier concentration and open‐circuit voltage (VOC). Ultimately, employing this novel method, a VOC of 498.3 mV and an efficiency of 8.42%, the highest performance reported for Sb2Se3 solar cells prepared via vapor transport deposition (VTD), are achieved.

Effects of mechanical alloying methods on structural phase stability, chemical state, optical, electrical and ferroelectric properties in Sc-doped α-Fe2O3 system

The development of metal doped α-Fe2O3 (hematite) based wide band gap semiconductors with high electrical conductivity, high electrical polarization and wide optical band gap is a challenging problem and also useful for application point of view. In this work, a substantial enhancement of electrical conductivity, optical band gap and ferroelectric polarization have been recorded at room temperature for Sc doped α-Fe2O3 system. Two different methods of the mechanical alloying and subsequent heat treatment have been used to synthesize the samples of α-Fe2-xScxO3 oxide (x = 0.2–1.0). The X-ray diffraction patterns have confirmed formation of single-phased Rhombohedral structure for low Sc doping content (x = 0.2), whereas a mixture of Rhombohedral-structured α-Fe2O3 type phase and cubic-structured Sc2O3 type phase has been formed for the higher Sc contents (x = 0.5 and 1.0). The phase fractions varied depending on the amount of Sc content, chemical reaction during mechanical alloying of the elementary oxides and solid-state reaction during the heat treatment. Response of the Sc2O3 type phase in Raman spectra is sensitive depending on the methods of inter-mixing the α-Fe2O3 and Sc2O3 by mechanical alloying. X-ray photoelectron spectroscopy (XPS) confirmed the metal (Fe, Sc) ions in +3 charge state, although the samples for low Sc content x = 0.2 showed a signature of Fe+2 and Sc+4 states. A detailed analysis of the Fe 3s XPS band confirmed a strong 3s-3d spins exchange coupling of strengths 1.18 eV–1.34 eV.

Controlled Vapor-Liquid-Solid Growth of Long and Remarkably Thin Pb1-xSnxTe Nanowires with Strain-Tunable Ferroelectric Phase Transition.

The Pb1-xSnxTe family of compounds possess a wide range of intriguing and useful physical properties, including topologically protected surface states, robust ferroelectricity, remarkable thermoelectric properties, and potential topological superconductivity. Compared to bulk crystals, one-dimensional (1D) nanowires (NWs) offer a unique platform to enhance the functional properties and enable new capabilities, e.g., to realize 1D Majorana zero modes for quantum computations. However, it has been challenging to achieve controlled synthesis of ultrathin Pb1-xSnxTe (0 ≤ x ≤ 1) nanowires in the truly 1D region. In this work, we report on a Au-catalyzed vapor-liquid-solid (VLS) growth of remarkably thin (20-30 nm) and sufficiently long (several to tens of micrometers) Pb1-xSnxTe nanowires of high single-crystalline quality in a controlled fashion. This controlled growth was achieved by enhancing the incorporation of Te into the Au catalyst particle to facilitate the precipitation of the Sn/Pb species and suppress the enlargement of the particle, which we identified as a major challenge for the growth of ultrathin nanowires. Our growth strategy can be easily extended to other compound and alloy nanowires, where the constituent elements have different incorporation rates into the catalyst particle. Furthermore, the growth of thin Pb1-xSnxTe nanowires enabled strain-dependent electrical transport measurements, which shows an enhancement of electrical resistance and ferroelectric transition temperature induced by uniaxial tensile strain along the nanowire axial direction, consistent with density functional theory calculations of the structural phase stability.

THE EFFECT OF THE ELECTROLYTE COMPOSITION ON THE MICROSTRUCTURE AND MECHANICAL PROPERTIES OF STEEL 45 AFTER CATHODIC ELECTROLYTE-PLASMA NITRIDING

This research offers an in-depth exploration of the impact of cathodic nitriding on the structural and mechanical characteristics of 45 steel treated in different aqueous electrolytes. Through a combination of Xray diffraction and electron microscopy analyses, it was determined that the nitriding process facilitates the development of a multilayered surface structure, which includes oxide, nitride, and martensitic layers. The composition of the electrolyte plays a crucial role in determining the phase composition and thickness of the modified layers, directly influencing the steel's mechanical properties, as reflected by variations in hardness and wear resistance post-treatment. Notably, an electrolyte containing sodium carbonate (Na₂CO₃) and urea (CH₄N₂O) achieved a maximum microhardness of 986 HV due to the formation of a dense nitride layer. On the other hand, introducing ammonium nitrate to the electrolyte, while slightly decreasing the microhardness to 882 HV, resulted in the formation of a more intricate and stable phase structure, including additional nitrides and oxides, which contributed to enhanced corrosion resistance. These findings underscore the critical importance of optimizing electrolyte composition to improve the performance characteristics of steel, such as hardness, wear resistance, and corrosion resistance. This study underscores the effectiveness of cathodic nitriding as a method for significantly enhancing the mechanical and surface properties of 45 steel, thereby expanding its potential for use in high-load and aggressive environments.

High Piezoelectric Performance of KNN-Based Ceramics over a Broad Temperature Range through Crystal Orientation and Multilayer Engineering.

Uninterrupted breakthroughs in the room temperature piezoelectric properties of KNN-based piezoceramics have been witnessed over the past two decades; however, poor temperature stability presents a major challenge for KNN-based piezoelectric ceramics in their effort to replace their lead-based counterparts. Herein, to enhance temperature stability in KNN-based ceramics while preserving the high piezoelectric response, multilayer composite ceramics were fabricated using textured thick films with distinct polymorphic phase transition temperatures. The results demonstrated that the composite ceramics exhibited both outstanding piezoelectric performance (d33~467 ± 16 pC/N; S~0.17% at 40 kV/cm) and excellent temperature stability with d33 and strain variations of 9.1% and 2.9%, respectively, over a broad temperature range of 25-180 °C. This superior piezoelectric temperature stability is attributed to the inter-inhibitive piezoelectric fluctuations between the component layers, the diffused phase transition, and the stable phase structure with a rising temperature, as well as the permanent contribution of crystal orientation to piezoelectric performance over the studied temperature range. This novel strategy, which addresses the piezoelectric and strain temperature sensitivity while maintaining high performance, is well-positioned to advance the commercial application of KNN-based lead-free piezoelectric ceramics.

Grain boundary diffusion in additively manufactured CoCrFeMnNi high-entropy alloys: Impact of non-equilibrium state, temperature and relaxation

Grain boundary diffusion of Ni in the equiatomic CoCrFeMnNi high-entropy alloy, produced by additive manufacturing, is measured using a radiotracer technique in an extended temperature interval of 350 to 703 K. A strongly non-monotonic temperature dependence of the Ni grain boundary diffusion coefficients (with a spectacular intermittent retardation of the diffusion rates with increasing temperature) is seen and explained by relaxation of a non-equilibrium state induced by rapid solidification during fabrication. The grain boundary excess energy of the non-equilibrium state of these grain boundaries, as estimated from the diffusion data, is found to be larger than 0.3 J/m2. This corresponds to an increase of about 30% of the interface energy compared to relaxed general high-angle grain boundaries. The temperature-induced evolution of the grain boundary state is analyzed in terms of the concomitant structure evolution, segregation, phase stability and precipitation in the multi-component alloy.

High-fidelity transfer of helical phase via hyper-Raman scattering in a monolayer graphene

Graphene is a fascinating two-dimensional optical material with a unique electronic band structure and a giant optical nonlinearity under the action of a strong magnetic field. Here we propose a scheme to transfer helical phase of the orbital angular momentum (OAM) light via hyper-Raman scattering in a monolayer graphene assisted by a magnetic field. Due to the unique electronic properties and selection rules near the Dirac point, it is found that high-fidelity transfer of phase structure and, in particular, of OAM from a pump field to the Raman field generated in a hyper-Raman scattering process occurs under the resonance condition. Interestingly, the obtained results allow us to control the intensity of Raman field with stable phase structure by varying the intensities of two pump fields. Hereby, the mechanism of efficient generation and manipulation of OAM Raman field may have exciting potential applications in the generation of short-wavelength coherent radiation, conversion of frequency as well as nonlinear spectroscopy in graphene materials.