Broad Band Gap Research Articles

Topology Optimization Enabled High Performance and Easy‐to‐Fabricate Hybrid Photonic Crystals

AbstractPhotonic crystals (PtCs) can confine and guide electromagnetic waves within specific frequency ranges, forming the foundation for promising optical applications. To numerically design PtCs with broad bandgaps, materials with high dielectric constants are favored. However, fabricating these high dielectric constant materials into microstructures is extremely challenging and it suffers from limitation of low fabricating resolution. To address this problem, this paper proposes hybrid microstructures composed of an easy‐to‐fabricate core and a high dielectric constant coating layer, which leverages the strength of both materials. This paper establishes a topology optimization algorithm to generate these PtCs with maximized bandgaps. Numerical examples demonstrate the effectiveness of the proposed method in generating optimized unit cells for both transverse magnetic (TM) and transverse electric (TE) modes. The hybrid PtCs offer unprecedented opportunities for the fabrication of optical devices, encouraging further research on multimaterial optical systems and advanced optimization methods to explore photonic bandgap materials beyond those offered by the current photonic technology.

Floating periodic pontoons for broad bandgaps of water waves

Floating periodic pontoons for broad bandgaps of water waves

Gradient Hole Injection Inducing Efficient Exciton Recombination in Blue (475 nm) Perovskite QLEDs.

Perovskite quantum dots (QDs) are emerging as excellent light sources for light-emitting diodes (LEDs). However, the performance of blue perovskite QD-based LEDs (QLEDs) still lags behind that of red and green counterparts, which is hindered by blue perovskite QDs with broad bandgaps that tend to increase nonradiative recombination. Here, we designed a gradient energy for hole injection utilizing multiple hole injection layers (HTLs) combined with carbazole-based small-molecule modification to reduce the hole injection barrier between HTLs and QD layers and improve the hole injection efficiency, realizing efficient exciton recombination in blue perovskite QLEDs. Moreover, the QD film on the designed HTLs demonstrates a lower surface roughness and improved photoluminescence properties. The optimized blue CsPbCl3-xBrx QLEDs exhibit an impressive external quantum efficiency of 20.7% with an electroluminescence peak at 475 nm and a turn-on voltage of 2.6 V, representing the state-of-the-art for blue perovskite LEDs emitting in the range of 460-480 nm.

Precisely Tuning Band Gaps of Hexabenzocoronene-Based MOFs Toward Enhanced Photocatalysis.

Precise adjusting the band gaps in metal-organic frameworks (MOFs) is crucial for improving their visible-light absorption capacity during photocatalysis, presenting both a formidable challenge and a charming opportunity. This present study employed a symmetry-reduction strategy to pre-design six novel 4-connected ligands with systematic substituents (-NO2, -H, -tBu, -OCH3, -OH and -NH2) and synthesized the corresponding pillared-layer Zr-MOFs (NKM-668) retaining the hexaphenylbenzene fragment. Subsequently, the NKM-668 MOFs were transformed into large-π-conjugated hexabenzocoronene-based MOFs (pNKM-668) via the Scholl reaction. These twelve MOFs exhibited broad and tunable band gaps over 1.41 eV (ranging from 3.25 eV to 1.84 eV), and the photocatalytic CO2 conversion rate raised by 33.2-fold. This study not only enriches the type of hexaphenylbenzene-based MOFs, but also paves the way for nanographene-containing MOFs in the further application of photocatalysis.

Zinc telluride material properties for solar cell application: Absorber layer

Over recent years, Zinc Telluride (ZnTe) has garnered significant interest from researches. This p-type semiconductors boasts a broad band gap, rendering it valuable in various optoelectronic uses like solar cells, LEDs, and laser displays. Given the growing interest in environmentally friendly energy alternatives, exploring the potential of nano-scale semiconducting materials for solar cells is particularly intriguing. ZnTe stands out due to its direct, wide, and adjustable optical band gap, along with its simple doping process, positioning it as a promising candidate for applications in photochemistry. This study aims to consolidate the research conducted by multiple investigators concerning the optical characteristics and electrical attributes of ZnTe thin films. The primary focus is on understanding how deposition methods and doping impacts these properties. The investigation reveals that the diverse doping techniques employed by different researchers have been extensively examined, demonstrating a positive influence of doping on these properties as well. Following the creation of solar cells based on ZnTe, they have emerged as viable and competitive substitutes for silicon solar cells, thanks to their economical nature and stable performance. As a result, there has been notable focus on advancing ZnTe thin film solar cell technology due to their promising capacity to serve as sustainable energy generators.

Analysis and simulation of opto-electronics characterization of two-dimensional Janus monolayers for energy applications

First-principles simulations are conducted to investigate the absorption and optoelectronic efficacy of molybdenum–sulfur–selenium, referred to here as MoSSe, and molybdenum–sulfur–oxygen, referred to here as MoSO, Janus monolayers. The materials MoSSe and MoSO demonstrate characteristics of semiconductors, as they possess bandgaps of 2.00 eV (direct) and 1.61 eV (indirect), respectively. This property renders them highly suitable for efficient light absorption. The efficiency of absorption of the device was calculated for the MoSSe and MoSO families, leading to the observation that these material families demonstrate a broad absorption range spanning from the infrared to the ultraviolet regions of the electromagnetic spectrum. This finding represents a novel discovery. Furthermore, the design as a topmost cell is particularly attractive due to its exceptional device absorption efficiency and broader bandgap. This particular family ensures that its band edges remain in alignment with the water-redox potentials. Molybdenum sulfide and molybdenum selenide exhibit promising potential as photocatalysts and in optoelectronic device applications. This is attributed to their appealing photocatalytic properties and notable efficiency in absorbing light for the purpose of water splitting.

Polymerization-induced highly brilliant and color-recordable mechanochromic photonic gels for ink-free patterning

Mechanochromic photonic crystals (MPCs) are extremely attractive since they can adjust their structural color by forces. However, the poor color saturation and color-recordability of conventional MPCs significantly limit their practical applications. Herein, a highly brilliant and color-recordable MPC gel (MPCG) has been fabricated by photopolymerizing the liquid photonic crystals with silica particles non-closely packed in acrylate, dichlorobenzene, and oleylamine. Photopolymerization induces elastic gradient non-close-packing structures and thus broad photonic bandgaps (>100 nm), resulting in 1) high color saturation despite possessing a small refractive index contrast (0.06), 2) remarkable mechanochromic properties, including a large wavelength tuning range (228 nm), fast responsiveness (8.8–10.3 nm/ms), and high sensitivity (4.4 nm/kPa), and 3) unconventional color-recordable properties. MPCGs were experimentally proved to be ideal rewritable papers for constructing multicolor and high-resolution patterns in an ink-free way, difficult for traditional MPC-based units. The unique working mechanism of polymerization-induced phase separation and thus continuous swelling and gelation, and precise design of materials and structures are the keys to MPCGs’ characteristics. This study paves a new way for constructing advanced stimulus-responsive photonic structures and will promote their applications in printing, display, anti-counterfeiting, etc.

Synthesis of Starfish-Shaped ZnS Nanostructures by Hydrothermal Method and Their Electrochemical Sensing of Dopamine.

Introduction Dopamine serves an essential function as a neurotransmitter, influencing the regulation of movement, cognitive processes, and emotional states. The identification of abnormal dopamine levels is critical for clinical diagnoses and scientific research, given its links to various disorders, including depression, schizophrenia, and Parkinson's disease. The distinctive electrochemical characteristics, stability, and broad bandgap of zinc sulfide (ZnS) nanostructures render them particularly fascinating. The hydrothermal method is recognized as an effective and economical approach for the fabrication of ZnS nanostructures, exhibiting a range of morphologies. Utilizing this method to create ZnS nanostructures leads to the formation of structures characterized by extensive surface areas, hierarchical designs, and improved electrochemical properties. Aim The objective is to examine the electrochemical characteristics of ZnS starfish-shaped nanostructures produced through the hydrothermal technique and to assess their viability as a sensing platform for dopamine detection. Materials and methods To synthesize ZnS nanoflowers, stoichiometric amounts of transition metal salts were prepared: 10 mM of Zn(NO3)2•3H2O and 30 mM of sodium thiosulfate (Na2S2O3•5H2O) were dissolved in 30 mL of deionized water and stirred for 20 minutes. The solutions were then combined and transferred into a 100 mL Teflon autoclave reactor, which was heated at 200 °C for 12 hours in a furnace. This process utilized the hydrothermal technique to produce the desired ZnS nanoflowers. Result The crystalline arrangement of ZnS was validated by X-ray diffraction (XRD) analysis, aligning with the Joint Committee on Powder Diffraction Standards (JCPDS). Moreover, field emission scanning electron microscopy (FE-SEM) illustrated the particle morphology of ZnS, showing a range between 200 and 500 nm size. Additionally, the cyclic voltammetry results indicated that the modified electrode produced a greater current response than the bare electrode, highlighting its improved sensitivity to dopamine molecules. Conclusion ZnSnanoparticles were synthesized via a hydrothermal method and characterized using XRDand FE-SEM. These nanoparticles were used for electrochemical dopamine detection, showing potential for advanced sensing platforms. Integrating ZnS into microfluidic devices enables real-time dopamine monitoring, opening new possibilities for healthcare and neurochemical research. Exploring surface engineering techniques could further enhance the electrochemical performance of ZnS-based sensors.

The transformation of type-I La2O3/α-Bi2O3 into multi-heterojunctions during photocatalysis with enhanced photoreactivity

A small quantity of broad bandgap rare earth lanthanum oxide (La2O3) was incorporated into monoclinic bismuth oxide (α-Bi2O3) through a one-step facile calcining route to construct an efficient type-I La2O3/α-Bi2O3 heterojunction photocatalyst for pollutant degradation under UV-light irradiation. The effect of adding La2O3 on the morphology, textural, optical, photoelectrochemical, and photocatalytic properties of α-Bi2O3 was investigated. Interestingly, feeding as low as five molar percent (5 %) La2O3 could significantly increase the BET surface area and generate more h+ and •O2− for photocatalytic reaction. Moreover, the calcining-induced carbon in La2O3/α-Bi2O3 revealed a vital role in suppressing the charge carrier recombination by quickly transferring charges to the photocatalyst's surface. In particular, during the recycling process, the in-situ formed Bi2O2CO3 changes the charge carrier transferring pathway and reveals a transformation of type-I La2O3/α-Bi2O3 into multi-heterojunction of type-I and type-II. Furthermore, the formation of Bi2O2CO3 results in more active sites for the photocatalytic reaction with improved reaction kinetics. This work provides a new direction for understanding a photocatalytic system's recycling phenomena and intrinsic kinetics.

Cyclic Atomic Layer Etching of PdSe2

AbstractThe unique characteristic of 2D transition‐metal dichalcogenide (TMD) semiconductor materials such as PdSe2 is the ability of the bandgap to vary on the basis of the number of layers present. This variation results in a broad bandgap range spanning from semi‐metallic to semiconducting materials, underscoring the significance of precisely controlling the material thickness. In this study, the thicknesses of chemical vapor deposited PdSe2 films are precisely controlled layer‐by‐layer via cyclic atomic layer etching (ALE), which comprised a radical adsorption step generated by oxygen and chlorine plasmas, followed by a desorption step with an organic solvent vapor such as formic acid. Cyclic etching with one monolayer of PdSe2/cycle is achieved using both types of adsorption gases while maintaining the ratio of Se/Pd underlying PdSe2 at ≈2. This cyclic ALE method is also applicable for smoothing TMD material surfaces by isotropically removing individual rough surface layers. Because this etching method only utilizes chemical reactions with radicals generated by plasmas and organic vapors, it is not only unaffected by the physical damage caused by the irradiation of energetic particles such as ions in plasmas, but also is applicable to 3D structure processing.

Phase Transition of a Chiral Lead‐Free Hybrid Antimony(III) Halide Crystal

AbstractChiral organic–inorganic hybrid lead halides have recently attracted great attention due to their unique chirality and diverse functional properties. However, they suffer from highly toxic lead, while lead‐free chiral hybrid metal halides especially those with phase transitions remain sparse. Here, we report a new lead‐free chiral metal halide crystal [R‐3‐fluoropiperidinium]2SbCl5 ([R‐3‐FPP]2SbCl5), which crystalizes in chiral P212121 space group at 293 K and consists of chiral [3‐FPP]+ cations and one‐dimensional [SbCl5]n2− zigzag chains of corner‐sharing SbCl6 octahedrons. Notably, [R‐3‐FPP]2SbCl5 undergoes an above room temperature phase transition at 313 K, which can be attributed to the order‐disorder transition of both the organic [R‐3‐FPP]+ cation and inorganic [SbCl5]2− anions. In addition, [R‐3‐FPP]2SbCl5 also shows a broad band gap of 3.21 eV. This work promotes the exploration of chiral lead‐free hybrid lead halides with phase transitions.

Green synthesis of magnesium oxide nanoparticles using Hyphaene thebaica extract and their photocatalytic activities

Magnesium oxide nanoparticles (MgO NPs) represent an interesting inorganic material widely utilized across various fields including sensing, antimicrobial applications, optical coatings, water purification, fuel additives, absorbents, and catalysis, owing to their exceptional broad energy band gap, surface affinity, and strong chemical and thermal durability. In this investigation, MgO NPs were successfully synthesized through a green approach employing fruit extract from the gingerbread tree (Hyphaene thebaica). Analysis via scanning electron microscopy (SEM) and transmission electron microscopy (TEM) confirmed their agglomerated quasi-spherical shape with a size range of 20–60 nm. The X-ray diffraction (XRD) pattern exhibited prominent peaks at planes (200) and (220), indicating the high crystallinity of MgO NPs with a crystallite size of 32.6 ± 5 nm while Energy-dispersive X-ray spectroscopy (EDS) analysis highlighted the composition comprises 40.47% Magnesium and 48.64% Oxygen by weight. Fourier transform infrared spectroscopy (FT-IR) revealed characteristic Mg-O bonds through peaks at 560 cm−1 and 866 cm−1, while Raman spectroscopy affirmed the cubic structure of MgO. Subsequently, the photocatalytic performance of MgO NPs under visible light irradiation was evaluated. Remarkably, the addition of 1 g/L of MgO nano-catalyst resulted in a degradation efficiency of 98% after 110 min on methylene blue dye, showcasing the high catalytic activity of MgO NPs. This remarkable photocatalytic efficiency emphasizes the potential of MgO NPs in environmental remediation.

Improvement of SAW Resonator Performance by Petal-like Topological Insulator.

This article introduces a novel petal-like SAW topology insulator, which can transmit sound waves with low loss and high flexibility in an ultra-wide frequency band by simultaneously adjusting multiple structural parameters of phononic crystals. Using finite element analysis, it was found that adjusting these parameters can generate a broadband gap of 55.8-65.7 MHz. This structure can also achieve defect immunity and sharp bending in waveguide transmission. When this topology insulator is applied to resonators, compared to traditional designs, the insertion loss is reduced by 22 dB, the on-load quality factor is increased by 227%, the off-load quality factor is increased by 1024.5%, and the quality sensitivity is improved by 3.7 times compared to bare devices.

The Influence of Defects on the Structural, Optical, and Antibacterial Properties of Cr/Cu Co-Doped ZnO Nanoparticles

In this research, Cu/Cr codoped ZnO nanoparticles (Zn₀.₉₉₋ₓCu₀.₀₁CrxO) were prepared using the sol-gel technique. The dopant ratio was systematically varied, ranging from x = 0.01 to 0.05 in increments of 0.01. This variation allowed for an exploration of the impact of defects on the structural, microstructural, optical, and antibacterial properties of Cu/Cr-codoped ZnO nanoparticles. Structural analysis of the Zn₀.₉₉₋ₓCu₀.₀₁CrxO nanoparticles was conducted using X-ray diffraction. The findings confirmed the presence of a hexagonal wurtzite structure in the ZnCuCrO nanoparticles, as determined by the c/a ratios in the range of 1.6013 and 1.6039. The surface morphology, crystallite size, and nanoparticle shapes were determined through scanning electron microscopy. The nanoparticle elemental compositions were analyzed through electron dispersive spectroscopy. The optical characteristics of the samples were assessed using a UV spectrophotometer. The energy band gaps for the nanoparticles were computed, and we discussed how dopant elements and defects affected their optical properties. We determined the refractive index using five distinct models. Notably, the highest band gap was observed for Zn₀.₉4Cu₀.₀₁Cr₀.₀5O (Eg=3.27 eV).Positron annihilation lifetime spectroscopy was employed to investigate the defect type, defect density, and crystal quality of Cu/Cr-codoped ZnO nanoparticles. The shortest lifetime τ1 obtained the highest value (0.181 ns) for Zn0.97 Cu0.01Cr0.02O nanoparticles. Zn₀.₉₉₋ₓCu₀.₀₁CrxO NPs were assessed for their antibacterial effects on E. coli (gram-negative) and S. aureus (gram-positive). Cu/Cr codoped ZnO nanoparticles show potential as materials for optoelectronic and sensor applications due to their broad band gap (Eg > 3) and high refractive index (n > 2).

A new seismic metamaterial design with ultra-wide low-frequency wave suppression band utilizing negative Poisson's ratio material

In this paper, we present a new seismic metamaterial (SM) for the suppression of Lamb waves and surface waves utilizing the negative Poisson's ratio (NPR) foam. The periodic cell of the metamaterial is composed of a square cylinder made of steel in the center and NPR foam connecters at the corners. Utilizing the unique resonance properties of the NPR material, an ultra-low-frequency broadband wave suppression is achieved. First, the characteristics of bandgaps (BGs) of the proposed structure with different materials were analyzed using the finite element (FE) method. It shows that the application of the NPR foam can significantly broaden the BGs compared with the case using traditional rubber. The vibration modes were analyzed to investigate the mechanism of BG generation, and the results show that the broad BG is achieved via the unique local resonance mechanism of the NPR foam. Subsequently, the frequency-domain analysis was carried out to verify the shielding effect of the designed SM on Lamb waves, using a periodic structure consisting of 10 × 6 unit cells. It shows that the designed SM can effectively attenuate Lamb waves in the range of 3–44 Hz with attenuation up to −590 dB at 32 Hz. A parametric analysis shows that the NPR foam with small thickness, high modulus, low mass density, and low Poisson's ratio can broaden the first complete BG. In addition, the acoustic cone method was combined with the frequency-domain analysis to calculate the BGs of the proposed structure against the surface wave, using a periodic structure consisting of 20 unit cells. It shows that the surface wave can be significantly attenuated within the BG. Finally, real seismic excitations were applied for time-domain analyses, and the simulation results show that the proposed structure can effectively shield the low-frequency seismic surface waves in the range of 0.1–20 Hz. The design scheme proposed in this paper is simple in structure and easy to implement, and is believed to possess bright application potentials in seismic protection.

Two-Dimensional Janus XY (X/Y=P, As, Sb, Bi, X≠Y) material with excellent piezoelectricity and carrier mobility for Visible-Light water splitting

Janus materials, with unique physical and chemical properties, show promise in turning solar energy into clean hydrogen through photocatalytic water splitting. Herein, utilizing first-principles calculations, we have confirmed the stabilities of newly discovered two-dimensional XY materials (X/Y=P, As, Sb, Bi, X≠Y), unveiling their promising capabilities in photocatalytic water splitting. These Janus structures exhibit broad bandgaps, paired with remarkable electron carrier mobilities. Their out-of-plane piezoelectric coefficients (d31) varying from 0.10 pm/V to 0.31 pm/V, surpass those of many typical two-dimensional materials, highlighting their considerable potential in energy conversion applications. These materials stand out in water splitting due to their favorable band edges and electrostatic potential gradients, achieving solar-to-hydrogen (STH) efficiencies above 20 % and visible light absorption efficiencies over 10 %. Remarkably, Janus PBi showcases STH and visible light absorption efficiencies up to 29.01 % and 19.33 %, respectively. By using biaxial strain, Janus PAs and PSb can reach a peak STH efficiency of over 30 % and a top visible light absorption efficiency above 20 %. Janus AsSb (PBi) exhibits exceptionally high photocatalytic activity for the oxygen (hydrogen) evolution reaction. These attributes suggest that these Janus XY materials are promising contenders as photocatalytic catalysts for water-splitting applications.

Strategically designed metal-free deep-ultraviolet birefringent crystals with superior optical properties.

Finding new birefringent materials with deep-ultraviolet (DUV, λ < 200 nm) transparency is urgent, as current commercial materials cannot meet the rapidly growing demands in related application fields. Herein, three guanidinium-based compounds, C(NH2)3CH3SO3, β-C(NH2)3Cl, and γ-C(NH2)3Cl, all featuring [C(NH2)3·X]∞ (X = CH3SO3 and Cl) pseudo layers, were designed through structural motif tailoring. Theoretical calculations indicate that these metal-free compounds all possess broad bandgaps (6.49-6.71 eV, HSE06) and remarkable birefringence (cal. 0.166-0.211 @ 1064 nm). Centimeter-sized C(NH2)3CH3SO3 crystals have been grown using a feasible aqua-solution method. Subsequently, to further optimize the properties, β/γ-C(NH2)3Cl was remolded by further tailoring the [C(NH2)3]+ cationic unit and the acceptor Cl- anion, and then the fourth compound NH2COF was theoretically constructed. Interestingly, NH2COF exhibits the desired coexistence of a wider bandgap (7.87 eV, HSE06) and giant birefringence (cal. 0.241 @ 1064 nm) attributed to its higher density of well-aligned birefringence-active groups (BAGs). Furthermore, among these four designed compounds, C(NH2)3CH3SO3 has been experimentally synthesized and exhibits a short UV cutoff edge. Centimeter-sized crystals have been grown using a feasible aqueous solution method. This study provides an effective strategy to optimize the density of BAGs for large birefringence and offers valuable insights into the strategic design of metal-free DUV birefringent crystals.

Simulation and analysis of solar cells based on InN/p-Si: influence on thickness, doping concentration, and temperature dependence

ABSTRACT The current research project intends to enhance solar cells' power and conversion efficiency based on InN/p-Si utilizing the PC1D simulator. A broad direct bandgap of Indium nitride (0.65 eV) makes it suitable for various applications. The InN-based solar cells show an excellent candidate for generating a higher efficiency device, incorporating well-established silicon substrate technology. The open-source PC1D is well-known software for simulating future solar devices without the need to fabricate real devices. The simulated area was adjusted to 10 cm2. The Si substrate and InN layer thicknesses were designed to be 350 μm and 1×10-3 μm, respectively. The n- and p-regions have doping concentrations of 1×1021 cm-3 and 1×1017 cm-3, respectively. This work analyses the influence of geometrical and technological aspects such as both n-p regions thickness, doping concentrations, and temperature dependency to enhance the conversion efficiency of these structures under the AM1.5G solar spectrum with intensity 0.1 W/cm2. It has been demonstrated that the growth of high-quality InN layers and p-type doping persists to be problematic. It appears challenging to find the most suitable material substrate for InN solar. To produce compatible solar cells with simple structures and cost-effective, however, extremely thin layers of n-layer material are required due to the high absorption coefficient of type III-nitrides. The results illustrate that by adjusting the optimized parameter at room temperature to the lowest temperature (200 K), the solar efficiency may increase up from 19.18% to 27.67%.

Optimization of InGaN-based solar cells by numerical simulation: Enhanced efficiency and performance analysis

The development of efficient solar cells is limited by the inability of the materials to absorb light from the entire solar spectrum. InGaN solar cells have become promising, due to the broad bandgap coverage of the solar spectrum from 0.7 eV to 3.42 eV. The performance of InGaN devices is simulated using SCAPS-1D software. The impacts of layer thickness and defect density on the performance of p-n and p-p-n junction InGaN solar cells were investigated, including holistic optimization of power conversion efficiency and quantum efficiency. A notable observation was the improvement in conversion efficiency with rising indium content, peaking at 23.8 % for In0.6Ga0.4N. For p-p-n junction cells, a thicker p-layer plus an additional thin top p-layer with a larger bandgap proved advantageous. The n-layer defect density in p-n junction cells showed minimal effects on open-circuit voltage and fill factor but reduced short-circuit current and efficiency as it increased. Conversely, the p-layer defect density influenced performance only at high densities beyond 1016 cm−3, while for p-p-n junctions, the top p-layer’s defect density had minimal impact. The optimized designs for both p-n and p-p-n junction cells, incorporating graded bandgaps, achieved optimal conversion efficiencies of 33.89 % and 34.07 %, respectively. The p-p-n design showed an enlarged high-efficiency area for suitable indium concentrations, offering broader indium concentration tuning possibilities and better lattice constant tuning. Quantum efficiency evaluations show the differences of defect densities and thicknesses across specific wavelength intervals, reaffirming the potential for strategic cell design choices.

Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials

AbstractOriented synthesis of functional materials is a focus of attention in material science. As one of the most important function materials, infrared nonlinear optical materials with large second harmonic generation effects and broad optical band gap are in urgent need. In this work, directed by the theoretical structure prediction, the first series of non‐centrosymmetric (NCS) alkali‐alkaline earth metal [PS4]‐based thiophosphates LiCaPS4 (Ama2), NaCaPS4 (P21), KCaPS4 (Pna21), RbCaPS4 (Pna21), CsCaPS4 (Pna21) were successfully synthesized. Comprehensive characterizations reveal that ACaPS4 could be regarded as promising IR NLO materials, exhibiting wide band gap (3.77–3.86 eV), moderate birefringence (0.027–0.064 at 1064 nm), high laser‐induced damage threshold (LIDT, ~10×AGS), and suitable phase‐matching second harmonic generation responses (0.4–0.6×AGS). Structure‐properties analyses illustrate that the Ca−S bonds show non‐ignorable covalent feature, and [PS4] together with [CaSn] units play dominant roles to determine the band gap and SHG response. This work indicates that Li‐, Na‐ and K‐ analogs may be promising infrared nonlinear optical material candidates, and this is the first successful case of “prediction to synthesis” involving infrared (IR) nonlinear optical (NLO) crystals in the thiophosphate system and may provide a new avenue to the design and oriented synthesis of high‐performance function materials in the future.