Non-centrosymmetric Crystal Structure Research Articles

Crystallographic and Optical Spectroscopic Study of Metal–Organic 2D Polymeric Crystals of Silver(I)– and Zinc(II)–Squarates

Metal–organic framework materials, as innovative functional materials for nonlinear optical technologies, feature linear and nonlinear optical responses, such as a laser damage threshold, outstanding mechanical properties, thermal stability, and optical transparency. Their non-centrosymmetric crystal structure induces a higher-order nonlinear optical response, which guarantees technological applications. ZnII– and AgI–squarate complexes are attractive templates for these purposes due to their good crystal growth, optical transparency, high thermal stability, etc. However, the space group type of the catena-((μ2-squarato)-tetra-aqua-zinc(II)) complex ([Zn(C4O4)(H2O)4]) is debatable, (1) showing centro- and non-centrosymmetric monoclinic C2/c and Cc phases. The same is valid for the catena-((μ3-squarato)-(μ2-aqua)-silver(I)) complex (Ag2C4O4), (2) exhibiting, so far, only a C2/c phase. This study is the first to report new crystallographic data on (1) and (2) re-determined at different temperatures (293(2) and 300(2)K) and the non-centrosymmetric Cc phase of (2), having different numbers of molecules per unit cell compared with the C2/c phase. There are high-resolution crystallographic measurements of single crystals, experimental electronic absorption, and vibrational spectroscopic data, together with ultra-high-resolution mass spectrometric ones. The experimental results are supported for theoretical optical and nonlinear optical properties obtained via high-accuracy static computational methods and molecular dynamics, using density functional theory as well as chemometrics.

Unveiling the recently synthesis noncentrosymmetric layered ASb3X2O12 (A = K, Rb, Cs, Tl; X = Se, Te) via first principles calculations

This study explores the structural, optical, and thermoelectric properties of non-centrosymmetric layered selenite and tellurite compounds KSb3Se2O12, RbSb3Se2O12, CsSb3Se2O12, TlSb3Se2O12, KSb3Te2O12, RbSb3Te2O12, CsSb3Te2O12, TlSb3Te2O12 to assess their potential for sustainable and renewable energy technologies. The selenite and tellurite compounds feature distinct non-centrosymmetric layered crystal structures, which are key to their unique optical and electronic properties. The materials display a layered structure without a center of symmetry, characterized by distinct atomic arrangements, and their band gaps vary depending on the constituent elements. For selenites, band gaps range from 2.97 eV to 3.19 eV, while for tellurites, they range from 2.75 eV to 3.02 eV, indicate their suitability for indirect semiconducting applications. The investigated materials exhibit high absorbance in the ultraviolet region, suggesting they are promising for solar cell applications. The energy loss function peaks at 14 eV, indicating minimal optical loss in the infrared and visible spectra. The static dielectric constants ε1(0) were calculated, showing variations based on the elemental composition. The response of ε2(ω) demonstrates strong interactions in the ultraviolet region, corresponding to electronic transitions from the valence to the conduction bands. Thermoelectric properties, evaluated with the BoltzTrap code using transport theory. The Seebeck coefficient of p-type semiconductors typically increases with temperature, but TlSb3Se2O12 shows an even greater increase, suggesting enhanced thermoelectric properties. Both selenites and tellurites have rising electrical conductivities, with ASb3Se2O12 peaking at 800 K. The Power Factor improves with temperature, reaching a peak for TlSb3Se2O12. These compounds exhibit favorable electrical conductivity and power factor, suggesting potential applications in thermoelectric systems. The figure of merit (ZT) values spanning from 0.90 to 1.51, with a maximum ZT value of 1.41 at 800 K, TlSb3Se2O12 shows great potential for high-temperature thermoelectric applications. These findings advance the understanding of non-centrosymmetric oxide materials and provide valuable insights for developing advanced materials for energy technologies.

Unconventional pairing in Ising superconductors: application to monolayer NbSe2

Abstract The presence of a non-centrosymmetric crystal structure and in-plane mirror symmetry allows an Ising spin–orbit coupling to form in some two-dimensional materials. Examples include transition metal dichalcogenide superconductors like monolayer NbSe2, MoS2, TaS2, and PbTe2, where a nontrivial nature of the superconducting state is currently being explored. In this study, we develop a microscopic formalism for Ising superconductors that captures the superconducting instability arising from a momentum-dependent spin- and charge-fluctuation-mediated pairing interaction. We apply our pairing model to the electronic structure of monolayer NbSe2, where first-principles calculations reveal the presence of strong paramagnetic fluctuations. Our calculations provide a quantitative measure of the mixing between the even- and odd-parity superconducting states and its variation with Coulomb interaction. Further, numerical analysis in the presence of an external Zeeman field reveals the role of Ising spin–orbit coupling and mixing of odd-parity superconducting state in influencing the low-temperature enhancement of the critical magnetic field.

Effect of thermal annealing on the average and local structure of superconducting polycrystalline NbRe films

Abstract NbxRe1−x is a non-centrosymmetric superconductor recently realized in thin film form. The access to the basic physics that governs this material is hindered by the polycrystalline structure of the films which consist of grains of small dimensions. In these conditions, films are not decisive in revealing the nature of the superconducting order parameter, and, in particular, the possible presence of a spin-triplet component. In this work, post-deposition annealing procedures were performed to improve the crystalline quality of the as-grown films. As determined by X-ray diffraction measurements, by tuning the annealing process, it was possible to increase the crystalline size from 1-2 nm up to several nanometers, beyond the values of the superconducting coherence length. Pair distribution function analyses revealed the non-centrosymmetric crystal structure of the treated NbRe films. Finally, electrical transport measurements, performed to study the relationship between structural and transport properties of the samples, showed an improved metallicity and a reduction of the superconducting critical temperature after the thermal treatment. This last result can be reasonably ascribed, for instance, to oxygen contamination, modification of the electronic density of states at the Fermi level, or change in the electron-phonon coupling. The results of this work are useful to realize films for future experiments meant to access nature of the superconducting order parameter.

Two-Dimensional Atomically Thin Piezoelectric Nanosheets for Efficient Pyroptosis-Dominated Sonopiezoelectric Cancer Therapy.

Sonopiezocatalytic therapy is an emerging therapeutic strategy that utilizes ultrasound irradiation to activate piezoelectric materials, inducing polarization and energy band bending to facilitate the generation of reactive oxygen species (ROS). However, the efficient generation of ROS is hindered by the long distance of charge migration from the bulk to the material surface. Herein, atomically thin Bi2O2(OH)(NO3) (AT-BON) nanosheets are rationally engineered through disrupting the weaker hydrogen bonds within the [OH] and [NO3] layer in the bulk material. The ultrathin structure of AT-BON piezocatalytic nanosheets shortens the migration distance of carriers, expands the specific surface area, and accelerates the charge transfer efficiency, showcasing a natural advantage in ROS generation. Importantly, the non-centrosymmetric polar crystal structure grants the nanosheets the ability to separate electron-hole pairs. Under ultrasonic mechanical stress, Bi2O2(OH)(NO3) nanosheets with the remarkable piezoelectric feature exhibit the desirable in vivo antineoplastic outcomes in both breast cancer model and liver cancer model. Especially, the AT-BON-induced ROS bursts lead to the activation of the Caspase-1-driven pyroptosis pathway. This study highlights the beneficial impact of bulk material thinning on enhancing ROS generation efficiency and anti-cancer effects.

Bulk photovoltaic effect and high mobility in the polar 2D semiconductor SnP2Se6.

The growth of layered 2D compounds is a key ingredient in finding new phenomena in quantum materials, optoelectronics, and energy conversion. Here, we report SnP2Se6, a van der Waals chiral (R3 space group) semiconductor with an indirect bandgap of 1.36 to 1.41 electron volts. Exfoliated SnP2Se6 flakes are integrated into high-performance field-effect transistors with electron mobilities >100 cm2/Vs and on/off ratios >106 at room temperature. Upon excitation at a wavelength of 515.6 nanometer, SnP2Se6 phototransistors show high gain (>4 × 104) at low intensity (≈10-6 W/cm2) and fast photoresponse (< 5 microsecond) with concurrent gain of ≈52.9 at high intensity (≈56.6 mW/cm2) at a gate voltage of 60 V across 300-nm-thick SiO2 dielectric layer. The combination of high carrier mobility and the non-centrosymmetric crystal structure results in a strong intrinsic bulk photovoltaic effect; under local excitation at normal incidence at 532 nm, short circuit currents exceed 8 mA/cm2 at 20.6 W/cm2.

3D printing flexible Ga-doped ZnO films for wearable energy harvesting: thermoelectric and piezoelectric nanogenerators

The 3D printing of energy harvesters using earth-abundant and non-toxic elements promotes energy sustainability and market competitiveness. The semiconducting behavior and non-centrosymmetric wurtzite crystal structure of gallium-doped zinc oxide (GZO) films make them attractive for thermoelectric and piezoelectric nanogenerators. This study investigates the thermal, structural, mechanical, thermoelectric, and piezoelectric properties of 3D-printed GZO nanocomposite films. Thermal analysis demonstrates the stability of the nanocomposite film up to 230 °C, making it suitable for wearable energy harvesters. The crystalline structure of the nanocomposite film aligns with the hexagonal wurtzite structure of ZnO and displays a bulk-like microstructure with a uniform distribution of elements. The presence of Ga 2p, Zn 2p, O 1 s, and C 1 s core levels confirms the development of the nanocomposite film, characterized by a fine granular structure and a conductive domain compared to the neat resin film. The inclusion of GZO nanofillers tailors the stress–strain behavior of the nanocomposite film, enhancing flexibility. The 3D-printed GZO nanocomposite films demonstrate a promising thermoelectric power factor and piezoelectric power densities, along with mechanical flexibility and thermal stability. These advancements hold significant potential for wearable and hybrid energy generation technologies.

Structure and optical properties of LixAg1–xAlSe2

The complete solid solution LixAg1–xAlSe2 was prepared at 850 °C in the form of phase-pure powder samples as well as single crystals. They adopt noncentrosymmetric crystal structures belonging to the tetragonal CuFeS2-type (space group I4‾2d) for x = 0–0.5 and orthorhombic β-NaFeO2-type (space group Pna21) for x = 0.6–1, both being built up from corner-sharing metal-centred tetrahedra and exhibiting complete disorder of Li and Ag atoms. Solid-state 7Li NMR spectra support the presence of unique Li sites. The substitution of Li for Ag atoms allows control of optical band gaps, which increase linearly from 2.7 eV to 3.6 eV. Second harmonic generation responses were measured to evaluate the potential of these compounds as infrared nonlinear optical materials.

Toward rationally designing high-performance perovskite sensing material: Role of dielectric constant and crystal symmetry

P-type oxide semiconductor gas sensors have gained increasing attention for their distinctive catalytic activity, high oxygen adsorption, and high humidity resistance. However, the low gas response of p-type sensors restricts their utilization, prompting numerous attempts to overcome this limitation. In this study, we have successfully engineered a promising p-type gas sensor by increasing the dielectric constant and optimizing crystal symmetry, departing from conventional approaches such as reducing particle size, constructing complex heterojunctions, and decorating with noble metals. The as-prepared multiferroic Bi0.92Dy0.8FeO3 gas sensor exhibits a well-defined gas response to acetone, demonstrating ultralow detection limits, distinctive selectivity, high humidity resistance, and long-term stability. Through comparisons of crystal symmetry, morphology, specific surface area, atomic chemical environment, dielectric properties, and sensing properties among a series of Dy3+ doped BiFeO3 solid solutions, we attribute this extraordinary sensing performance of Bi0.92Dy0.8FeO3 to its higher dielectric constant and unique domain-wall structure arising from its non-centrosymmetric crystal structure. This work provides additional perspective for preparing high-performance gas sensors.

Beyond Conventional Catalysts: Monoelemental Tellurium as a Game Changer for Piezo-Driven Hydrogen Evolution.

The increasing demand for clean hydrogen production over fossil fuels necessitates the development of sustainable piezoelectrochemical methods that can overcome the limitations of conventional electrocatalytic and photocatalytic approaches. In this regard, existing piezocatalysts face challenges related to their low piezoelectricity or active site coverage for hydrogen evolution reaction (HER). Driven by global environmental concerns, there is a compelling push to engineer practical materials for highly efficient HER. Herein, monoelemental 2D tellurium (Te) is presented as a class of layered chalcogenide with a non-centrosymmetric crystal structure (P3121 space group). The refined Te nanosheets demonstrate an unprecedented highly efficient H2 production rate ≈9000µmolg-1h-1 under ultrasonic mechanical vibration due to built-in piezo-potential in the system. The remarkable piezocatalytic performance of Te nanosheets arises from a synergistic interplay between their semi-metallic nature, favorable free energy landscape, enhanced electrical conductivity and outstanding piezoelectricity. As a proof of concept, the theoretical approach based on Density Functional Theory (DFT) validates the findings due to the gradual exposure of active sites on the Te nanosheets leading to a self-optimized catalytic performance for hydrogen generation. Therefore, mechanically driven Te emerges as a promising piezocatalyst with the potential to revolutionize highly efficient and sustainable technology for futuristic applications.

Ba4RuMn2O10: A Noncentrosymmetric Polar Crystal Structure with Disordered Trimers.

Phase-pure polycrystalline Ba4RuMn2O10 was prepared and determined to adopt the noncentrosymmetric polar crystal structure (space group Cmc21) based on results of second harmonic generation, convergent beam electron diffraction, and Rietveld refinements using powder neutron diffraction data. The crystal structure features zigzag chains of corner-shared trimers, which contain three distorted face-sharing octahedra. The three metal sites in the trimers are occupied by disordered Ru/Mn with three different ratios: Ru1:Mn1 = 0.202(8):0.798(8), Ru2:Mn2 = 0.27(1):0.73(1), and Ru3:Mn3 = 0.40(1):0.60(1), successfully lowering the symmetry and inducing the polar crystal structure from the centrosymmetric parent compounds Ba4T3O10 (T = Mn, Ru; space group Cmca). The valence state of Ru/Mn is confirmed to be +4 according to X-ray absorption near-edge spectroscopy. Ba4RuMn2O10 is a narrow bandgap (∼0.6 eV) semiconductor exhibiting spin-glass behavior with strong magnetic frustration and antiferromagnetic interactions.

Out-of-Plane Ferroelectricity in Two-Dimensional 1T‴-MoS2 Above Room Temperature.

Two-dimensional (2D) molybdenum disulfide (MoS2), one of the most extensively studied van der Waals (vdW) materials, is a significant candidate for electronic materials in the post-Moore era. MoS2 exhibits various phases, among which the 1T‴ phase possesses noncentrosymmetry. 1T‴-MoS2 was theoretically predicted to be ferroelectric a decade ago, but this has not been experimentally confirmed until now. Here, we have prepared high-purity 2D 1T‴-MoS2 crystals and experimentally confirmed the room-temperature out-of-plane ferroelectricity. The noncentrosymmetric crystal structure in 2D 1T‴-MoS2 was convinced by atomically resolved transmission electron microscopic imaging and second harmonic generation (SHG) measurements. Further, the ferroelectric polarization states in 2D 1T‴-MoS2 can be switched using piezoresponse force microscopy (PFM) and electrical gating in field-effect transistors (FETs). The ferroelectric-to-paraelectric transition temperature is measured to be about 350 K. Theoretical calculations have revealed that the ferroelectricity of 2D 1T‴-MoS2 originates from the intralayer charge transfer of S atoms within the layer. The discovery of intrinsic ferroelectricity in the 1T‴ phase of MoS2 further enriches the properties of this important vdW material, providing more possibilities for its application in the field of next-generation electronic devices.

Observation of Anisotropic Second Harmonic Generation in Two-Dimensional Niobium Diselenide.

The intrinsic anisotropy of NbSe2 provides a favorable prerequisite of second harmonic generation (SHG) and rich possibilities for tailoring its nonlinear optical (NLO) properties. Here we report the highly efficient SHG of mechanically exfoliated NbSe2 flakes. The nonlinear optical response changes with excitation wavelengths, layer thicknesses, and polarizations of the excitation laser. The anisotropic SHG response further exhibits the intrinsic non-centrosymmetric crystal structure and could effectively assign the crystalline orientation of NbSe2 flakes. Interestingly, although NbSe2 flakes with tens of nanometers thickness experience attenuations in SHG performance, more efficient SHG anisotropy ratios were obtained, which are around 4 times higher than that of the 5-layer counterpart. The determined second-order nonlinearities of NbSe2 flakes (monolayer: ∼1.0 × 103 pm/V; 3-layer: ∼73 pm/V) are comparable to those of the commonly reported two-dimensional materials (e.g., MoS2, WSe2, graphene) with the same number of layers and much higher than those of commercial nonlinear optical crystals.

Transport studies in piezo-semiconductive ZnO nanotetrapod based electronic devices

ZnO nanotetrapods (ZnO NTs) with a non-centrosymmetric crystal structure consisting of four 1-D arms interconnected together through a central crystalline core, introduce interesting piezoelectric semiconducting responses in nanorods in the bent state. Considering the widespread applications of nanotetrapods in semiconductor devices, it becomes very crucial to establish a coupled model based on piezoelectric and piezotronic effects to investigate the carrier transport mechanism, which is being reported here in detail for the first time. In this work, we established a multiphysics coupled model of stress-regulated charge carrier transport by the finite element method (FEM), which considers the full account of the wurtzite (WZ) and zinc blende (ZB) regions as well as the spontaneous polarization dependence and the dependence of the material properties on the arm orientation. It is discovered that the forward gain of ZnO NT in the lateral force working mode is almost 50 % higher than that in the nanorod or in the normal force working mode while the reverse current is reduced to negligible. Through the simulation calculations and corresponding analysis, it is confirmed that the developed piezoelectric polarization charges are able to regulate the transport and distribution of carriers in ZnO crystal, which lays a theoretical foundation for the application of piezo-semiconductive ZnO NT devices in advanced technologies.

Research on the Stability of Different Polar Surfaces in Aluminum Nitride Single Crystals

Wurtzite aluminum nitride (AlN) crystal has a non-centrosymmetric crystal structure with only a single axis of symmetry. In an AlN crystal, the electronegativity difference between the Al atom and N atom leads to a distortion of electron cloud distribution outside the nucleus and a spontaneous polarization (SP) along the c-axis direction. The N-polar surface along the directions of [000-1] has higher surface energy than the Al-polar surface along the directions of [0001]. Due to the different atomic arrangement, Al atoms on the Al-polar surface bond with O and OH− in the environment to generate Al2O3·xH2O, which prevents the reaction from occurring inside the crystal. After the Al2O3·xH2O dissolve in an alkaline environment, N atoms have three dangling bonds exposed on the surface, which can also protect OH− from destroying the internal Al-N bonds, so the Al-polar surface is more stable than the N-polar surface.

Van der Waals quaternary oxides for tunable low-loss anisotropic polaritonics.

The discovery of ultraconfined polaritons with extreme anisotropy in a number of van der Waals (vdW) materials has unlocked new prospects for nanophotonic and optoelectronic applications. However, the range of suitable materials for specific applications remains limited. Here we introduce tellurite molybdenum quaternary oxides-which possess non-centrosymmetric crystal structures and extraordinary nonlinear optical properties-as a highly promising vdW family of materials for tunable low-loss anisotropic polaritonics. By employing chemical flux growth and exfoliation techniques, we successfully fabricate high-quality vdW layers of various compounds, including MgTeMoO6, ZnTeMoO6, MnTeMoO6 and CdTeMoO6. We show that these quaternary vdW oxides possess two distinct types of in-plane anisotropic polaritons: slab-confined and edge-confined modes. By leveraging metal cation substitutions, we establish a systematic strategy to finely tune the in-plane polariton propagation, resulting in the selective emergence of circular, elliptical or hyperbolic polariton dispersion, accompanied by ultraslow group velocities (0.0003c) and long lifetimes (5 ps). Moreover, Reststrahlen bands of these quaternary oxides naturally overlap that of α-MoO3, providing opportunities for integration. As an example, we demonstrate that combining α-MoO3 (an in-plane hyperbolic material) with CdTeMoO6 (an in-plane isotropic material) in a heterostructure facilitates collimated, diffractionless polariton propagation. Quaternary oxides expand the family of anisotropic vdW polaritons considerably, and with it, the range of nanophotonics applications that can be envisioned.

Fonony, magnony i eksitony v netsentrosimmetrichnommagnitoelektrike - antiferromagnetike CuB2O4

In the last two decades copper metaborate CuB2O4 with a unique noncentrosymmetric crystal structure has become the subject of active research due to its unusual magnetic and optical properties. We consider the propagation and absorption of light in CuB2O4 based on the solution of Maxwell’s equations. We present an overview of the main results on the investigation of the phonon spectrum using infrared and Raman spectroscopy. Studies in the region of electronic transitions in Cu2+ ions in the crystal field have allowed the separation of contributions to the optical absorption from copper ions in inequivalent positions. A splitting of zero-phonon absorption lines in a magnetic field has been detected, and these results have received a theoretical explanation in terms of the exciton model. A rich structure of exciton–magnon states has been observed in the photoluminescence spectra. We have carried out a spectroscopic study of the optical second harmonic generation in the region of excitonic transitions, which has allowed the contribution of the toroidal moment and the Fano resonance to the observed signals to be revealed.

An atomically tailored chiral magnet with small skyrmions at room temperature

Creating materials that do not exist in nature can lead to breakthroughs in science and technology. Magnetic skyrmions are topological excitations that have attracted great attention recently for their potential applications in low power, ultrahigh density memory. A major challenge has been to find materials that meet the dual requirement of small skyrmions stable at room temperature. Here we meet both these goals by developing epitaxial FeGe films with excess Fe using atomic layer molecular beam epitaxy (MBE) far from thermal equilibrium. Our atomic layer design permits the incorporation of 20% excess Fe while maintaining a non-centrosymmetric crystal structure supported by theoretical calculations and necessary for stabilizing skyrmions. We show that the Curie temperature is well above room temperature, and that the skyrmions have sizes down to 15 nm as imaged by Lorentz transmission electron microscopy (LTEM) and magnetic force microscopy (MFM). The presence of skyrmions coincides with a topological Hall effect-like resistivity. These atomically tailored materials hold promise for future ultrahigh density magnetic memory applications.

Enhancing nonlinear optical responses via Methoxy Positional Isomerism in Chalcone-Based Materials

The functional moieties present in chalcone derivatives play a pivotal role in finely adjusting the thermal, optical, structural, and nonlinear optical (NLO) characteristics of the chalcone material. This paper details the synthesis of chalcone derivatives where three distinct trimethoxy substituents are integrated into the benzoyl moiety through carboxyl bonding with 2-acetyl pyridine. The synthesis employs the Schmidt condensation method, and the resultant samples are subject to scrutiny through FTIR and FT-Raman techniques to ascertain phase purity. The outcomes reveal substantial alterations in the structural, thermal, optical, and NLO attributes of the samples. The electron-donating property of the trimethoxy groups augments electron density within the chalcone molecule, thereby effecting multiple shifts in the material's characteristics. Interestingly, a methoxy group located at positions 2, 4, and 5 forms crystals with centrosymmetric properties. Conversely, relocating the methoxy groups to positions 3, 4, 5, and 2, 4, 6 induces a transformation from centrosymmetric to non-centrosymmetric crystal structures, resulting in a remarkable enhancement of NLO properties, encompassing second and third harmonic generation. Notably, the compound featuring trimethoxy substitution at positions 3, 4, and 5 demonstrates a 27-fold increase in second harmonic generation compared to the urea crystal. The detailed discussion encompasses the intricate relationship between the molecular structure and nonlinear properties, encompassing third harmonic generation.

A perspective on piezotronics and piezo-phototronics based on the third and fourth generation semiconductors

The rapid development of semiconductor materials and devices has brought tremendous development opportunities to optoelectronics, intelligent manufacturing, Internet of Things, power electronics, and even innovative energy technologies. Among them, the third and fourth generation semiconductors represented by ZnO, GaN, SiC, and Ga2O3 are two kinds of emerging strategic material systems. Due to their large energy bandgaps, they exhibit excellent performance in application scenarios of high voltage, high frequency, and high temperature resistance, making them great candidates in high-power, radio frequency, and optoelectronic devices. The third and fourth generation semiconductors usually possess non-centrosymmetric crystal structures, which makes the piezoelectric polarization effect a fundamental characteristic for the third and fourth generation semiconductors in contrast to the first and second generation semiconductors as represented by Si, Ge, and GaAs. Research studies on the coupling of piezoelectricity, semiconductor, and light excitation properties were coined as piezotronics and piezo-phototronics in 2007 and 2010, respectively, by Zhong Lin Wang. The piezotronic and piezo-phototronic effects open another avenue for further improvement of the performance of electronic and optoelectronic devices. This Perspective will first introduce the basic concepts and principles of piezotronics and piezo-phototronics and the basic characteristics of the third and fourth generation semiconductors. Then, progress, challenges, and opportunities of ideal materials, comprehensive physical models, and outstanding applications based on piezotronics and piezo-phototronics are presented with emphasis. Finally, conclusions and outlooks are drawn for the piezotronics and piezo-phototronics based on the third and fourth generation semiconductors.