Raman spectroscopy study of pressure-induced phase transitions in single crystal CuInP2S6.

Two-dimensional ferroic materials exhibit a variety of functional properties that can be tuned by temperature and pressure. CuInP2S6 is a layered material that is ferrielectric at room temperature and whose properties are a result of the unique structural arrangement of ordered Cu+ and In3+ cations within a (P2S6)4- anion backbone. Here, we investigate the effect of hydrostatic pressure on the structure of CuInP2S6 single crystals through a detailed Raman spectroscopy study. Analysis of the peak frequencies, intensities, and widths reveals four high pressure regimes. At 5 GPa, the material undergoes a monoclinic-trigonal phase transition. At higher pressures (5-12 GPa), we see Raman peak sharpening, indicative of a change in the electronic structure, followed by an incommensurate phase between 12 and 17 GPa. Above 17 GPa, we see evidence for bandgap reduction in material. The original state of the material is fully recovered upon decompression, showing that hydrostatic pressure could be used to tune the electronic and ferrielectric properties of CuInP2S6.

AgScP2S6 van der Waals Layered Crystal: A Material with a Unique Combination of Extreme Nonlinear Optical Properties.

Research in two-dimensional layered materials (2DLMs) has exploded over the past several years for a variety of applications in photonics and optoelectronics. The 2D nature of these materials allows for a very local electronic probe of material as well as flexible integration with other functional components. Herein, using the femtosecond Z-scan technique, we report a giant two photon absorption (TPA) process and its saturation in the van der Waals gapped silver scandium thiophosphate (AgScP2S6) crystal. We have found a TPA coefficient of the order of 104 cm/GW which is orders of magnitude larger compared to many existing semiconductors and nonlinear crystals. Furthermore, we found a TPA cross-section of 103 GM and characterized the optical limiting (OL) response (0.2 mJ/cm2) and the multipulse laser damage threshold (1.09 ± 0.19 J/cm2). The combination of giant TPA, extremely low OL, and very high damage threshold suggests that this material could be extremely useful in applications like optical limiters or switches.

Dynamic Stabilization of Metastable States in Triple-Well Ferroelectric Sn2 P2 S6.

Polarization dynamics in ferroelectric materials is governed by the effective potential energy landscape of the order parameter. The unique aspect of ferroelectrics compared to many other transitions is the possibility of more than two potential wells, leading to complicated energy landscapes with new fundamental and functional properties. Here, direct dynamic evidence is revealed of a triple-well potential in the metal thiophosphate Sn2 P2 S6 compound using multivariate scanning probe microscopy combined with theoretical simulations. The key finding is that the metastable zero polarization state can be accessed through a gradual switching process and is stabilized over a broad range of electric fields. Simulations confirm that the observed zero polarization state originates from a kinetic stabilization of the nonpolar state of the triple-well, as opposed to domain walls. Dynamically, the triple-well of Sn2 P2 S6 becomes equivalent to antiferroelectric hysteresis loops. Therefore, this material combines the robust and well-defined domain structure of a proper ferroelectric with dynamic hysteresis loops present in antiferroelectrics. Moreover, the triple-well enhances mem-capacitive effects in Sn2 P2 S6 , which are forbidden for ideal double-well ferroelectrics. These findings provide a path to tunable electronic elements for beyond binary high-density computing devices and neuromorphic circuits based on dynamic properties of the triple-well.

Precision Modification of Monolayer Transition Metal Dichalcogenides via Environmental E-Beam Patterning.

Layered Transition Metal Dichalcogenides (TMDs) are an important class of materials that exhibit a wide variety of optoelectronic properties. The ability to spatially tailor their expansive property-space (e.g., conduction behavior, optical emission, surface interactions) is of special interest for applications including, but not limited to, sensing, bioelectronics, and spintronics/valleytronics. Current methods of property modulation focus on the modification of the basal surfaces and edge sites of the TMDs by the introduction of defects, functionalization with organic or inorganic moieties, alloying, heterostructure formation, and phase engineering. A majority of these methods lack the resolution for the development of next-generation nanoscale devices or are limited in the types of functionalities useful for efficient TMD property modification. In this study, we utilize electron-beam patterning on monolayer TMDs (MoSe2, WSe2 and MoS2) in the presence of a pressure-controlled atmosphere of water vapor within an environmental scanning electron microscope (ESEM). A series of parametric studies show local optical and electronic property modification depending on acceleration voltage, beam current, pressure, and electron dose. The ultimate pattern resolution achieved is 67 ± 9 nm. Raman and photoluminescence spectroscopies coupled with Kelvin Probe Force Microscopy reveal electron dose-dependent p-doping in the patterned regions, which we attribute to functionalization from the products of water vapor radiolysis (oxygen and hydroxyl groups). The modulation of the work function through patterning matches well with Density Functional Theory modeling. Finally, post-functionalization of the patterned areas with an organic fluorophore demonstrates a robust method to achieve nanoscale functionalization with high fidelity.

Exfoliation procedure-dependent optical properties of solution deposited MoS2 films.

The development of high-precision large-area optical coatings and devices comprising low-dimensional materials hinges on scalable solution-based manufacturability with control over exfoliation procedure-dependent effects. As such, it is critical to understand the influence of technique-induced transition metal dichalcogenide (TMDC) optical properties that impact the design, performance, and integration of advanced optical coatings and devices. Here, we examine the optical properties of semiconducting MoS2 films from the exfoliation formulations of four prominent approaches: solvent-mediated exfoliation, chemical exfoliation with phase reconversion, redox exfoliation, and native redox exfoliation. The resulting MoS2 films exhibit distinct refractive indices (n), extinction coefficients (k), dielectric functions (ε1 and ε2), and absorption coefficients (α). For example, a large index contrast of Δn ≈ 2.3 is observed. These exfoliation procedures and related chemistries produce different exfoliated flake dimensions, chemical impurities, carrier doping, and lattice strain that influence the resulting optical properties. First-principles calculations further confirm the impact of lattice defects and doping characteristics on MoS2 optical properties. Overall, incomplete phase reconfiguration (from 1T to mixed crystalline 2H and amorphous phases), lattice vacancies, intraflake strain, and Mo oxidation largely contribute to the observed differences in the reported MoS2 optical properties. These findings highlight the need for controlled technique-induced effects as well as the opportunity for continued development of, and improvement to, liquid phase exfoliation methodologies. Such chemical and processing-induced effects present compelling routes to engineer exfoliated TMDC optical properties toward the development of next-generation high-performance mirrors, narrow bandpass filters, and wavelength-tailored absorbers.

Ultrafast Nonlinear Absorption and Second Harmonic Generation in Cu0.33In1.30P2S6 van der Waals Layered Crystals.

The advancement of ultrafast photonics and optoelectronic devices necessitates the exploration of new materials with optical and chemical stability to implement practical applications. Layered quaternary metal-thio/selenophosphate has attracted much interest over the past few years. Ferroelectric CuInP2S6 (CIPS) is an emerging material that belongs to this family. When synthesized with Cu deficiencies, CIPS forms self-assembled in-plane heterostructures, which in turn exhibit properties that are both compositionally and thermally dependent. These characteristics can be explored for applications in nonlinear optoelectronic and photonic devices. Herein, we study the second and third order nonlinear optical behavior of Cu0.33In1.30P2S6 bulk heterostructure. We observed large two photon induced nonlinear absorptions and self-defocusing at 1032 nm pulsed laser excitation using the Z-scan technique. Furthermore, we identified a polarization-dependent second harmonic signal and determined the laser-induced optical damage threshold. Our observations allow for the designing of optoelectronic and ultrafast photonic devices based on these materials.

Revealing Fast Cu-Ion Transport and Enhanced Conductivity at the CuInP2S6-In4/3P2S6 Heterointerface.

Van der Waals layered ferroelectrics, such as CuInP2S6 (CIPS), offer a versatile platform for miniaturization of ferroelectric device technologies. Control of the targeted composition and kinetics of CIPS synthesis enables the formation of stable self-assembled heterostructures of ferroelectric CIPS and nonferroelectric In4/3P2S6 (IPS). Here, we use quantitative scanning probe microscopy methods combined with density functional theory (DFT) to explore in detail the nanoscale variability in dynamic functional properties of the CIPS-IPS heterostructure. We report evidence of fast ionic transport which mediates an appreciable out-of-plane electromechanical response of the CIPS surface in the paraelectric phase. Further, we map the nanoscale dielectric and ionic conductivity properties as we thermally stimulate the ferroelectric-paraelectric phase transition, recovering the local dielectric behavior during this phase transition. Finally, aided by DFT, we reveal a substantial and tunable conductivity enhancement at the CIPS/IPS interface, indicating the possibility of engineering its interfacial properties for next generation device applications.

Nanoscale Control of Polar Surface Phases in Layered van der Waals CuInP2S6.

Antiferroelectric (AFE) materials, in which alternating dipole moments cancel out to a zero net macroscopic polarization, can be used for high-density energy storage and memory applications. The AFE phase can exist in bulk CuInP2Se6, CuBiP2S6, and a few other transition-metal thiophosphates below 200 K. The required low temperature poses challenges for practical applications. In this work, we report the coexistence of ferrielectric (FE) states and a stable surface phase that does not show piezoelectric response ("zero-response phase") in bulk CuInP2S6 at room temperature. Using piezoresponse force microscopy (PFM) tomographic imaging together with density functional theory, we find that direct and alternating voltages can locally and stably convert FE to zero-response phases and vice versa. While PFM loops show pinched hystereses reminiscent of antiferroelectricity, PFM tomography reveals that the zero-response areas form only on top of the FE phase in which the polarization vector is pointing up. Theoretical calculations suggest that the zero-response phase may correspond to AFE ordering where stacked CuInP2S6 layers have alternating polarization orientations thereby leading to a net-zero polarization. Consistent with experimental findings, theory predicts that the FE polarization pointing down is robust up to the top surface, whereas FE polarization pointing up energetically favors the formation of an AFE surface layer, whose thickness is likely to be sensitive to local strains. AFE order is likely to be more robust against detrimental size effects than polar order, therefore providing additional opportunities to create multifunctional heterostructures with 2D electronic materials.

Lowering of Tc in Van Der Waals Layered Materials Under In-Plane Strain.

The dependence of electromechanical behavior on strain in ferroelectric materials can be leveraged as parameter to tune ferroelectric properties such as the Curie temperature. For van der Waals materials, a unique opportunity arises because of wrinkling, bubbling, and Moiré phenomena accessible due to structural properties inherent to the van der Waals gap. Here, we use piezoresponse force microscopy and unsupervised machine learning methods to gain insight into the ferroelectric properties of layered CuInP2S6 where local areas are strained in-plane due to a partial delamination, resulting in a topographic bubble feature. We observe significant differences between strained and unstrained areas in piezoresponse images as well as voltage spectroscopy, during which strained areas show a sigmoid-shaped response usually associated with the response measured around the Curie temperature, indicating a lowering of the Curie temperature under tensile strain. These results suggest that strain engineering might be used to further increase the functionality of CuInP2S6 through locally modifying ferroelectric properties on the micro- and nanoscale.

Oxidation of Gallium-based Liquid Metal Alloys by Water.

Gallium alloys with other low melting point metals, such as indium or tin, to form room-temperature liquid eutectic systems. The gallium in the alloys rapidly forms a thin surface oxide when exposed to ambient oxygen. This surface oxide has been previously exploited for self-stabilization of liquid metal nanoparticles, retention of metastable shapes, and imparting stimuli-responsive behavior to the alloy surface. In this work, we study the effect of water as an oxidant and its role in defining the alloy surface chemistry. We identify several pathways that can lead to the formation of gallium oxide hydroxide (GaOOH) crystallites, which may be undesirable in many applications. Furthermore, we find that some crystallite formation pathways can be reinforced by typical top-down particle synthesis techniques like sonication. This improved understanding of interfacial interactions provides critical insight for process design and implementation of advanced devices that utilize the unique coupling of flexibility and conductivity offered by these gallium-based liquid metal alloys.

Fast Scanning Probe Microscopy via Machine Learning: Non-Rectangular Scans with Compressed Sensing and Gaussian Process Optimization.

Fast scanning probe microscopy enabled via machine learning allows for a broad range of nanoscale, temporally resolved physics to be uncovered. However, such examples for functional imaging are few in number. Here, using piezoresponse force microscopy (PFM) as a model application, a factor of 5.8 reduction in data collection using a combination of sparse spiral scanning with compressive sensing and Gaussian process regression reconstruction is demonstrated. It is found that even extremely sparse spiral scans offer strong reconstructions with less than 6% error for Gaussian process regression reconstructions. Further, the error associated with each reconstructive technique per reconstruction iteration is analyzed, finding the error is similar past ≈15 iterations, while at initial iterations Gaussian process regression outperforms compressive sensing. This study highlights the capabilities of reconstruction techniques when applied to sparse data, particularly sparse spiral PFM scans, with broad applications in scanning probe and electron microscopies.

Local Strain and Polarization Mapping in Ferrielectric Materials.

CuInP2S6 (CIPS) is a van der Waals material that has attracted attention because of its unusual properties. Recently, a combination of density functional theory (DFT) calculations and piezoresponse force microscopy (PFM) showed that CIPS is a uniaxial quadruple-well ferrielectric featuring two polar phases and a total of four polarization states that can be controlled by external strain. Here, we combine DFT and PFM to investigate the stress-dependent piezoelectric properties of CIPS, which have so far remained unexplored. The two different polarization phases are predicted to differ in their mechanical properties and the stress sensitivity of their piezoelectric constants. This knowledge is applied to the interpretation of ferroelectric domain images, which enables investigation of local strain and stress distributions. The interplay of theory and experiment produces polarization maps and layer spacings which we compare to macroscopic X-ray measurements. We found that the sample contains only the low-polarization phase and that domains of one polarization orientation are strained, whereas domains of the opposite polarization direction are fully relaxed. The described nanoscale imaging methodology is applicable to any material for which the relationship between electromechanical and mechanical characteristics is known, providing insight on structural, mechanical, and electromechanical properties down to ∼10 nm length scales.

Piezoelectric domain walls in van der Waals antiferroelectric CuInP2Se6.

Polar van der Waals chalcogenophosphates exhibit unique properties, such as negative electrostriction and multi-well ferrielectricity, and enable combining dielectric and 2D electronic materials. Using low temperature piezoresponse force microscopy, we revealed coexistence of piezoelectric and non-piezoelectric phases in CuInP2Se6, forming unusual domain walls with enhanced piezoelectric response. From systematic imaging experiments we have inferred the formation of a partially polarized antiferroelectric state, with inclusions of structurally distinct ferrielectric domains enclosed by the corresponding phase boundaries. The assignment is strongly supported by optical spectroscopies and density-functional-theory calculations. Enhanced piezoresponse at the ferrielectric/antiferroelectric phase boundary and the ability to manipulate this entity with electric field on the nanoscale expand the existing phenomenology of functional domain walls. At the same time, phase-coexistence in chalcogenophosphates may lead to rational strategies for incorporation of ferroic functionality into van der Waals heterostructures, with stronger resilience toward detrimental size-effects.

Tunable quadruple-well ferroelectric van der Waals crystals.

The family of layered thio- and seleno-phosphates has gained attention as potential control dielectrics for the rapidly growing family of two-dimensional and quasi-two-dimensional electronic materials. Here we report a combination of density functional theory calculations, quantum molecular dynamics simulations and variable-temperature, -pressure and -bias piezoresponse force microscopy data to predict and verify the existence of an unusual ferroelectric property-a uniaxial quadruple potential well for Cu displacements-enabled by the van der Waals gap in copper indium thiophosphate (CuInP2S6). The calculated potential energy landscape for Cu displacements is strongly influenced by strain, accounting for the origin of the negative piezoelectric coefficient and rendering CuInP2S6 a rare example of a uniaxial multi-well ferroelectric. Experimental data verify the coexistence of four polarization states and explore the temperature-, pressure- and bias-dependent piezoelectric and ferroelectric properties, which are supported by bias-dependent molecular dynamics simulations. These phenomena offer new opportunities for both fundamental studies and applications in data storage and electronics.

Locally Controlled Cu-Ion Transport in Layered Ferroelectric CuInP2S6.

Metal thiophosphates are attracting growing attention in the context of quasi-two-dimensional van der Waals functional materials. Alkali thiophosphates are investigated as ion conductors for solid electrolytes, and transition-metal thiophosphates are explored as a new class of ferroelectric materials. For the latter, a representative copper indium thiophosphate is ferrielectric at room temperature and, despite low polarization, exhibits giant negative electrostrictive coefficients. Here, we reveal that ionic conductivity in this material enables localized extraction of Cu ions from the lattice with a biased scanning probe microscopy tip, which is surprisingly reversible. The ionic conduction is tracked through local volume changes with a scanning probe microscopy tip providing a current-free probing technique, which can be explored for other thiophosphates of interest. Nearly 90 nm-tall crystallites can be formed and erased reversibly on the surface of this material as a result of ionic motion, the size of which can be sensitively controlled by both magnitude and frequency of the electric field, as well as the ambient temperature. These experimental results and density functional theory calculations point to a remarkable resilience of CuInP2S6 to large-scale ionic displacement and Cu vacancies, in part enabled by the metastability of Cu-deficient phases. Furthermore, we have found that the piezoelectric response of CuInP2S6 is enhanced by about 45% when a slight ionic modification is carried out with applied field. This new mode of modifying the lattice of CuInP2S6, and more generally ionically conducting thiophosphates, posits new prospects for their applications in van der Waals heterostructures, possibly in the context of catalytic or electronic functionalities.

Chemical Changes in Layered Ferroelectric Semiconductors Induced by Helium Ion Beam.

Multi-material systems interfaced with 2D materials, or entirely new 3D heterostructures can lead to the next generation multi-functional device architectures. Physical and chemical control at the nanoscale is also necessary tailor these materials as functional structures approach physical limit. 2D transition metal thiophosphates (TPS), with a general formulae Cu1-xIn1+x/3P2S6, have shown ferroelectric polarization behavior with a T c above the room temperature, making them attractive candidates for designing both: chemical and physical properties. Our previous studies have demonstrated that ferroic order persists on the surface, and that spinoidal decomposition of ferroelectric and paraelectric phases occurs in non-stoichiometric Cu/In ratio formulations. Here, we discuss the chemical changes induced by helium ion irradiation. We explore the TPS compound library with varying Cu/In ratio, using Helium Ion Microscopy, Atomic Force Microscopy (AFM), and Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS). We correlate physical nano- and micro- structures to the helium ion dose, as well as chemical signatures of copper, oxygen and sulfur. Our ToF-SIMS results show that He ion irradiation leads to oxygen penetration into the irradiated areas, and diffuses along the Cu-rich domains to the extent of the stopping distance of the helium ions.

Metal Thio- and Selenophosphates as Multifunctional van der Waals Layered Materials.

Since the discovery of Dirac physics in graphene, research in 2D materials has exploded with the aim of finding new materials and harnessing their unique and tunable electronic and optical properties. The follow-on work on 2D dielectrics and semiconductors has led to the emergence and development of hexagonal boron nitride, black phosphorus, and transition metal disulfides. However, the spectrum of good insulating materials is still very narrow. Likewise, 2D materials exhibiting correlated phenomena such as superconductivity, magnetism, and ferroelectricity have yet to be developed or discovered. These properties will significantly enrich the spectrum of functional 2D materials, particularly in the case of high phase-transition temperatures. They will also advance a fascinating fundamental frontier of size and proximity effects on correlated ground states. Here, a broad family of layered metal thio(seleno)phosphate materials that are moderate- to wide-bandgap semiconductors with incipient ionic conductivity and a host of ferroic properties are reviewed. It is argued that this material class has the potential to merge the sought-after properties of complex oxides with electronic functions of 2D and quasi-2D electronic materials, as well as to create new avenues for both applied and fundamental materials research in structural and magnetic correlations.

Cation-Eutectic Transition via Sublattice Melting in CuInP2S6/In4/3P2S6 van der Waals Layered Crystals.

Single crystals of the van der Waals layered ferrielectric material CuInP2S6 spontaneously phase separate when synthesized with Cu deficiency. Here we identify a route to form and tune intralayer heterostructures between the corresponding ferrielectric (CuInP2S6) and paraelectric (In4/3P2S6) phases through control of chemical phase separation. We conclusively demonstrate that Cu-deficient Cu1-xIn1+x/3P2S6 forms a single phase at high temperature. We also identify the mechanism by which the phase separation proceeds upon cooling. Above 500 K both Cu+ and In3+ become mobile, while P2S64- anions maintain their structure. We therefore propose that this transition can be understood as eutectic melting on the cation sublattice. Such a model suggests that the transition temperature for the melting process is relatively low because it requires only a partial reorganization of the crystal lattice. As a result, varying the cooling rate through the phase transition controls the lateral extent of chemical domains over several decades in size. At the fastest cooling rate, the dimensional confinement of the ferrielectric CuInP2S6 phase to nanoscale dimensions suppresses ferrielectric ordering due to the intrinsic ferroelectric size effect. Intralayer heterostructures can be formed, destroyed, and re-formed by thermal cycling, thus enabling the possibility of finely tuned ferroic structures that can potentially be optimized for specific device architectures.

Polarization Control via He-Ion Beam Induced Nanofabrication in Layered Ferroelectric Semiconductors.

Rapid advances in nanoscience rely on continuous improvements of material manipulation at near-atomic scales. Currently, the workhorse of nanofabrication is resist-based lithography and its various derivatives. However, the use of local electron, ion, and physical probe methods is expanding, driven largely by the need for fabrication without the multistep preparation processes that can result in contamination from resists and solvents. Furthermore, probe-based methods extend beyond nanofabrication to nanomanipulation and to imaging which are all vital for a rapid transition to the prototyping and testing of devices. In this work we study helium ion interactions with the surface of bulk copper indium thiophosphate CuM(III)P2X6 (M = Cr, In; X= S, Se), a novel layered 2D material, with a Helium Ion Microscope (HIM). Using this technique, we are able to control ferrielectric domains and grow conical nanostructures with enhanced conductivity whose material volumes scale with the beam dosage. Compared to the copper indium thiophosphate (CITP) from which they grow, the nanostructures are oxygen rich, sulfur poor, and with virtually unchanged copper concentration as confirmed by energy-dispersive X-ray spectroscopy (EDX). Scanning electron microscopy (SEM) imaging contrast as well as scanning microwave microscopy (SMM) measurements suggest enhanced conductivity in the formed particles, whereas atomic force microscopy (AFM) measurements indicate that the produced structures have lower dissipation and are softer as compared to the CITP.

Quantitative Analysis of the Local Phase Transitions Induced by Laser Heating.

Functional imaging enabled by scanning probe microscopy (SPM) allows investigations of nanoscale material properties under a wide range of external conditions, including temperature. However, a number of shortcomings preclude the use of the most common material heating techniques, thereby limiting precise temperature measurements. Here we discuss an approach to local laser heating on the micron scale and its applicability for SPM. We applied local heating coupled with piezoresponse force microscopy and confocal Raman spectroscopy for nanoscale investigations of a ferroelectric-paraelectric phase transition in the copper indium thiophosphate layered ferroelectric. Bayesian linear unmixing applied to experimental results allowed extraction of the Raman spectra of different material phases and enabled temperature calibration in the heated region. The obtained results enable a systematic approach for studying temperature-dependent material functionalities in heretofore unavailable temperature regimes.