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A new copper indium selenide, Ba3.5Cu7.55In1.15Se9, was synthesized by the KBr flux reaction at 800 °C. The compound crystallizes with orthorhombic Pnma, a = 46.1700(12) Å, b = 4.26710(10) Å, c = 19.8125(5) Å, and Z = 8. The structural framework mainly consists of four sites of cubane-type defective M4Se3 (M = Cu, Cu/In) units with disordered Cu+/In3+ ions present at the part corner of each unit. The single crystal emits intense photoluminescence at 657 nm with a relative quantum yield (RQY) 0.2 times that of rhodamine 6G powder. The compound belongs to a direct band gap at 1.91 eV, analyzed by Tauc's plot, and the energy is close to the PL position. The Hall effect measurement on a pressed pellet reveals an n-type conductivity with a carrier concentration of 3.358 × 1017 cm-3 and a mobility of 24.331 cm2 V-1 s-1. Furthermore, the compound produces a strong nonlinear third-harmonic generation (THG), with an χS(3) value of 1.3 × 105 pm2/V2 comparable to 1.6 × 105 pm2/V2 for AgGaSe2 measured at 800 nm.
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Cu2TSiS4 (T = Mn and Fe) polycrystalline and single-crystal materials were prepared with high-temperature solid-state and chemical vapor transport methods, respectively. The polar crystal structure (space group Pmn21) consists of chains of corner-sharing and distorted CuS4, Mn/FeS4, and SiS4 tetrahedra, which is confirmed by Rietveld refinement using neutron powder diffraction data, X-ray single-crystal refinement, electron diffraction, energy-dispersive X-ray spectroscopy, and second harmonic generation (SHG) techniques. Magnetic measurements indicate that both compounds order antiferromagnetically at 8 and 14 K, respectively, which is supported by the temperature-dependent (100-2 K) neutron powder diffraction data. Additional magnetic reflections observed at 2 K can be modeled by magnetic propagation vectors k = (1/2,0,1/2) and k = (1/2,1/2,1/2) for Cu2MnSiS4 and Cu2FeSiS4, respectively. The refined antiferromagnetic structure reveals that the Mn/Fe spins are canted away from the ac plane by about 14°, with the total magnetic moments of Mn and Fe being 4.1(1) and 2.9(1) µB, respectively. Both compounds exhibit an SHG response with relatively modest second-order nonlinear susceptibilities. Density functional theory calculations are used to describe the electronic band structures.
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The isostructural heteroanionic compounds ß-LiAsS2-xSex (x = 0, 0.25, 1, 1.75, 2) show a positive correlation between selenium content and second-harmonic response and greatly outperform the industry standard AgGaSe2. These materials crystallize in the noncentrosymmetric space group Cc as one-dimensional 1/∞ [AsQ2]- (Q = S, Se, S/Se) chains consisting of corner-sharing AsQ3 trigonal pyramids with charge-balancing Li+ atoms interspersed between the chains. LiAsS2-xSex melts congruently for 0 ≤ x ≤ 1.75, but when the Se content exceeds x = 1.75, crystallization is complicated by a phase transition. This behavior is attributed to the ß- to α-phase transition present in LiAsSe2, which is observed in the Se-rich compositions. The band gap decreases with increasing Se content, starting at 1.63 eV (LiAsS2) and reaching 1.06 eV (ß-LiAsSe2). Second-harmonic generation measurements as a function of wavelength on powder samples of ß-LiAsS2-xSex show that these materials exhibit significantly higher nonlinearity than AgGaSe2 (d36 = 33 pm/V), reaching a maximum of 61.2 pm/V for LiAsS2. In comparison, single-crystal measurements for LiAsSSe yielded a deff = 410 pm/V. LiAsSSe, LiAsS0.25Se1.75, and ß-LiAsSe2 show phase-matching behavior for incident wavelengths exceeding 3 µm. The laser-induced damage thresholds from two-photon absorption processes are on the same order of magnitude as AgGaSe2, with S-rich materials slightly outperforming AgGaSe2 and Se-rich materials slightly underperforming AgGaSe2.
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Two-dimensional (2D) semiconductors have emerged as an excellent platform for studying various excitonic matter under strong quantum and dielectric confinements. However, such effects can be seriously overestimated for Coulomb binding of two excitons to form a biexciton by a naive interpretation of the corresponding photoluminescence (PL) spectrum. By using 2D halide perovskite single crystals of [CH3(CH2)3NH3]2Pb1-xMnxBr4 (x = 0-0.09) as a model system, we investigated both population and relaxation kinetics of biexcitons as a function of excitation density, temperature, polarization, and Mn doping. We show that the biexciton is formed by binding of two dark excitons, which are partially bright, but they radiatively recombine to yield a bright exciton in the final state. This renders the spectral distance between the exciton peak and the biexciton peak as very different from the actual biexciton binding energy (Ï) because of large bright-dark splitting. We show that Mn doping introduces paramagnetism to our 2D system and improves the biexciton stability as evidenced by increase in Ï from 18.8 ± 0.7 to 20.0 ± 0.7 meV and the increase of the exciton-exciton capture coefficient C from 2.4 × 10-11 to 4.3 × 10-11cm2/ns within our doping range. The precisely determined Ï values are significantly smaller than the previously reported ones, but they are consistent with the instability of the biexciton against thermal dissociation at room temperature. Our results demonstrate that electron-hole exchange interaction must be considered for precisely locating the biexciton level; therefore, the Ï values should be reassessed for other 2D halide perovskites that even do not exhibit any dark exciton PL.
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APbBr3 (A = Cs, CH3NH3) are prototype halide perovskites having bandgaps of 2.30-2.35 eV at room temperature, rendering their apparent color nearly identical (bright orange but opaque). Upon optical excitation, they emit bright photoluminescence (PL) arising from carrier recombination whose spectral features are also similar. At 10 K, however, the apparent color of CsPbBr3 becomes transparent yellow, whereas that of CH3NH3PbBr3 does not change significantly due to the presence of an indirect Rashba gap. With increasing the excitation level, evolution of the PL spectra, which are excitonic at 10 K, reveals the emergence of P-band emission arising from inelastic exciton-exciton scattering. Based on the spectral location of the P-band, exciton binding energies are determined to be 21.6 ± 2.0 and 38.3 ± 3.0 meV for CsPbBr3 and CH3NH3PbBr3, respectively. Intriguingly, upon further increase in the exciton density, electron-hole plasma appears in CsPbBr3 as evidenced by both red-shift and broadening of the PL. This phase, however, does not occur in CH3NH3PbBr3 presumably due to polaronic effects. Although the A-site cation is believed not to directly impact optical properties of APbBr3, our results underscore its critical role, which destines different high-density phases and apparent color at low temperatures.
RESUMEN
The mixed cation compounds Na1-xKxAsSe2 (x = 0.8, 0.65, 0.5) and Na0.1K0.9AsS2 crystallize in the polar noncentrosymmetric space group Cc. The AAsQ2 (A = alkali metals, Q = S, Se) family features one-dimensional (1D) 1/∞[AQ2-] chains comprising corner-sharing pyramidal AQ3 units in which the packing of these chains is dependent on the alkali metals. The parallel 1/∞[AQ2-] chains interact via short As···Se contacts, which increase in length when the fraction of K atoms is increased. The increase in the As···Se interchain distance increases the band gap from 1.75 eV in γ-NaAsSe2 to 2.01 eV in Na0.35K0.65AsSe2, 2.07 eV in Na0.2K0.8AsSe2, and 2.18 eV in Na0.1K0.9AsS2. The Na1-xKxAsSe2 (x = 0.8, 0.65) compounds melt congruently at approximately 316 °C. Wavelength-dependent second harmonic generation (SHG) measurements on powder samples of Na1-xKxAsSe2 (x = 0.8, 0.65, 0.5) and Na0.1K0.9AsS2 suggest that Na0.2K0.8AsSe2 and Na0.1K0.9AsS2 have the highest SHG response and exhibit significantly higher laser-induced damage thresholds (LIDTs). Theoretical SHG calculations on Na0.5K0.5AsSe2 confirm its SHG response with the highest value of d33 = 22.5 pm/V (χ333(2) = 45.0 pm/V). The effective nonlinearity for a randomly oriented powder is calculated to be deff = 18.9 pm/V (χeff(2) = 37.8 pm/V), which is consistent with the experimentally obtained value of deff = 16.5 pm/V (χeff(2) = 33.0 pm/V). Three-photon absorption is the dominant mechanism for the optical breakdown of the compounds under intense excitation at 1580 nm, with Na0.2K0.8AsSe2 exhibiting the highest stability.
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Recently, halide perovskites have gained significant attention from the perspective of efficient spintronics owing to the Rashba effect. This effect occurs as a consequence of strong spin-orbit coupling under a noncentrosymmetric environment, which can be dynamic and/or static. However, there exist intense debates on the origin of broken inversion symmetry since the halide perovskites typically crystallize into a centrosymmetric structure. In order to clarify the issue, we examine both dynamic and static effects in the all-inorganic CsPbBr3 and organic-inorganic CH3NH3PbBr3 (MAPbBr3) perovskite single crystals by employing temperature- and polarization-dependent photoluminescence excitation spectroscopy. The perovskite single crystals manifest the dynamic effect by photon recycling in the indirect Rashba gap, causing dual peaks in the photoluminescence. However, the effect vanishes in CsPbBr3 at low temperatures (<50 K) accompanied by a striking color change of the crystal, arising presumably from lower degrees of freedom for inversion symmetry breaking associated with the thermal motion of the spherical Cs cation compared with the polar MA cation in MAPbBr3. We also show that the static Rashba effect occurs only in MAPbBr3 below 90 K, presumably due to surface reconstruction via MA-cation ordering, which likely extends across a few layers from the crystal surface to the interior. We further demonstrate that this static Rashba effect can be completely suppressed upon surface treatment with polymethyl methacrylate (PMMA) coating. We believe that our results provide a rationale for the Rashba effects in halide perovskites.
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The pressure-induced structural evolution of formamidinium-based perovskite FAPbI3 was investigated using in situ synchrotron X-ray diffraction and laser-excited photoluminescence methods. Cubic α-FAPbI3 ( Pm3Ì m) partially and irreversibly transformed to hexagonal δ-FAPbI3 ( P63 mc) at a pressure less than 0.1 GPa. Structural transitions of α-FAPbI3 followed the sequence of Pm3Ì m â P4/ mbm â Im3Ì â partial amorphous during compression to 6.59 GPa, whereas the δ-phase converted to an orthorhombic Cmc21 structure between 1.26 and 1.73 GPa. During decompression, FAPbI3 recovered the P63 mc structure of the δ-phase as a minor component (â¼18 wt %) from 2.41-1.40 GPa and the Pm3Ì m structure of the α-phase becomes dominant (â¼82 wt %) at 0.10 GPa but with an increased fraction of δ-FAPbI3. The photoluminescence behaviors from both the α- and δ-forms were likely controlled by radiative recombination at the defect levels rather than band-edge emission during pressure cycling. FAPbI3 polymorphism is exquisitely sensitive to pressure. While modest pressures can engineer FAPbI3-based photovoltaic devices, irreversible δ-phase crystallization may be a limiting factor and should be taken into account.
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Cationic rearrangement is a compelling strategy for producing desirable physical properties by atomic-scale manipulation. However, activating ionic diffusion typically requires high temperature, and in some cases also high pressure in bulk oxide materials. Herein, we present the cationic rearrangement in bulk Mn2 FeMoO6 at unparalleled low temperatures of 150-300â (o) C. The irreversible ionic motion at ambient pressure, as evidenced by real-time powder synchrotron X-ray and neutron diffraction, and second harmonic generation, leads to a transition from a Ni3 TeO6 -type to an ordered-ilmenite structure, and dramatic changes of the electrical and magnetic properties. This work demonstrates a remarkable cationic rearrangement, with corresponding large changes in the physical properties in a bulk oxide at unprecedented low temperatures.
RESUMEN
The synthesis and properties of the hybrid organic/inorganic germanium perovskite compounds, AGeI3, are reported (A = Cs, organic cation). The systematic study of this reaction system led to the isolation of 6 new hybrid semiconductors. Using CsGeI3 (1) as the prototype compound, we have prepared methylammonium, CH3NH3GeI3 (2), formamidinium, HC(NH2)2GeI3 (3), acetamidinium, CH3C(NH2)2GeI3 (4), guanidinium, C(NH2)3GeI3 (5), trimethylammonium, (CH3)3NHGeI3 (6), and isopropylammonium, (CH3)2C(H)NH3GeI3 (7) analogues. The crystal structures of the compounds are classified based on their dimensionality with 14 forming 3D perovskite frameworks and 57 1D infinite chains. Compounds 17, with the exception of compounds 5 (centrosymmetric) and 7 (nonpolar acentric), crystallize in polar space groups. The 3D compounds have direct band gaps of 1.6 eV (1), 1.9 eV (2), 2.2 eV (3), and 2.5 eV (4), while the 1D compounds have indirect band gaps of 2.7 eV (5), 2.5 eV (6), and 2.8 eV (7). Herein, we report on the second harmonic generation (SHG) properties of the compounds, which display remarkably strong, type I phase-matchable SHG response with high laser-induced damage thresholds (up to â¼3 GW/cm(2)). The second-order nonlinear susceptibility, χS(2), was determined to be 125.3 ± 10.5 pm/V (1), (161.0 ± 14.5) pm/V (2), 143.0 ± 13.5 pm/V (3), and 57.2 ± 5.5 pm/V (4). First-principles density functional theory electronic structure calculations indicate that the large SHG response is attributed to the high density of states in the valence band due to sp-hybridization of the Ge and I orbitals, a consequence of the lone pair activation.
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The new Li2MnGeS4 and Li2CoSnS4 compounds result from employing a rational and simple design strategy that guides the discovery of diamond-like semiconductors (DLSs) with wide regions of optical transparency, high laser damage threshold, and efficient second-order optical nonlinearity. Single-crystal X-ray diffraction was used to solve and refine the crystal structures of Li2MnGeS4 and Li2CoSnS4, which crystallize in the noncentrosymmetric space groups Pna21 and Pn, respectively. Synchrotron X-ray powder diffraction (SXRPD) was used to assess the phase purity, and diffuse reflectance UV-vis-NIR spectroscopy was used to estimate the bandgaps of Li2MnGeS4 (Eg = 3.069(3) eV) and Li2CoSnS4 (Eg = 2.421(3) eV). In comparison with Li2FeGeS4, Li2FeSnS4, and Li2CoSnS4 DLSs, Li2MnGeS4 exhibits the widest region of optical transparency (0.60-25 µm) and phase matchability (≥1.6 µm). All four of the DLSs exhibit second-harmonic generation and are compared with the benchmark NLO material, AgGaSe2. Most remarkably, Li2MnGeS4 does not undergo two- or three-photon absorption upon exposure to a fundamental Nd:YAG beam (λ = 1.064 µm) and exhibits a laser damage threshold > 16 GW/cm(2).
Asunto(s)
Complejos de Coordinación/química , Germanio/química , Rayos Láser , Compuestos de Litio/química , Dinámicas no Lineales , Fenómenos Ópticos , Semiconductores , Cristalografía por Rayos X , Modelos Moleculares , Conformación MolecularRESUMEN
Cu2CdSnS4 and α/ß-Cu2ZnSiS4 meet several criteria for promising nonlinear optical materials for use in the infrared (IR) region. Both are air-stable, crystallize in noncentrosymmetric space groups, and possess high thermal stabilities. Cu2CdSnS4 and α/ß-Cu2ZnSiS4 display wide ranges of optical transparency, 1.4-25 and 0.7-25 µm, respectively, and have relatively large second-order nonlinearity as well as phase matchability for wide regions in the IR. The laser-damage threshold (LDT) for Cu2CdSnS4 is 0.2 GW/cm(2), whereas α/ß-Cu2ZnSiS4 has a LDT of 2.0 GW/cm(2) for picosecond near-IR excitation. Both compounds also exhibit efficient third-order nonlinearity. Electronic structure calculations provide insight into the variation in properties.
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Above-room-temperature polar magnets are of interest due to their practical applications in spintronics. Here we present a strategy to design high-temperature polar magnetic oxides in the corundum-derived A2BB'O6 family, exemplified by the non-centrosymmetric (R3) Ni3TeO6-type Mn(2+)2Fe(3+)Mo(5+)O6, which shows strong ferrimagnetic ordering with TC = 337â K and demonstrates structural polarization without any ions with (n-1)d(10)ns(0), d(0), or stereoactive lone-pair electrons. Density functional theory calculations confirm the experimental results and suggest that the energy of the magnetically ordered structure, based on the Ni3TeO6 prototype, is significantly lower than that of any related structure, and accounts for the spontaneous polarization (68â µC cm(-2)) and non-centrosymmetry confirmed directly by second harmonic generation. These results motivate new directions in the search for practical magnetoelectric/multiferroic materials.
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In2 Se3 , 2D ferroelectric-semiconductor, is a promising candidate for next-generation memory device because of its outstanding electrical properties. However, the large-area manufacturing of In2 Se3 is still a big challenge. In this work, spray pyrolysis technique is introduced for the growth of large-area In2 Se3 thin film. A polycrystalline γ-In2 Se3 layer can be grown on 15 cm × 15 cm glasss at the substrate temperature of 275 °C. The In2 Se3 ferroelectric-semiconductor field effect transistor (FeS-FET) on glass substrate demonstrates a large hysteresis window of 40.3 V at the ±40 V of gate voltage sweep and excellent uniformity. The FeS-FET exhibits an electron field effect mobility of 0.97 cm2 V-1 s-1 and an on/off current ratio of >107 in the transfer curves. The memory behavior of the large-area, In2 Se3 FeS-FETs for next-generation memory is demonstrated.
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Structural imperfections can cause both beneficial and detrimental consequences on the excitonic characteristics of transition metal dichalcogenides (TMDs). Regarding valley selection, structural defects typically promote valley depolarization in monolayer TMDs, but defect healing via an additional growth process can restore valley polarization in vertical heterobilayers (VHs). In this study, we analyzed the valley polarization of center-nucleated and edge-nucleated VHs (WS2/MoS2) grown using a controlled growth process and discovered that defect-related photoluminescence (PL) is strongly suppressed in the center-nucleated VHs due to defect healing. Additionally, we demonstrated that the valley polarization of lower-lying intralayer excitons is more sensitive to the defect density of the sample than to higher-lying intralayer excitons. Despite defect healing in the center-nucleated VHs, the temperature-dependent PL study indicated that valley depolarization of the lower-lying intralayer excitons becomes significant below 100 K because of stronger hybridization of defect states. Also, we conducted a comprehensive study on the excitation intensity dependence to investigate the electron-doping-induced Auger recombination mechanism, which also contributes to valley depolarization of intralayer excitons via regeneration of intervalley trions. Our findings provide valuable insight into the development of VH-based valleytronic devices.
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The efficiency of light emission is a critical performance factor for monolayer transition metal dichalcogenides (1L-TMDs) for photonic applications. While various methods have been studied to compensate for lattice defects to improve the quantum yield (QY) of 1L-TMDs, exciton-exciton annihilation (EEA) is still a major nonradiative decay channel for excitons at high exciton densities. Here, we demonstrate that the combined use of a proximal Au plate and a negative electric gate bias (NEGB) for 1L-WS2 provides a dramatic enhancement of the exciton lifetime at high exciton densities with the corresponding QY enhanced by 30 times and the EEA rate constant decreased by 80 times. The suppression of EEA by NEGB is attributed to the reduction of the defect-assisted EEA process, which we also explain with our theoretical model. Our results provide a synergetic solution to cope with EEA to realize high-intensity 2D light emitters using TMDs.
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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 (â¼0.6 eV) semiconductor exhibiting spin-glass behavior with strong magnetic frustration and antiferromagnetic interactions.
RESUMEN
Monolayer transition metal dichalcogenides (TMDs) have been extensively studied for their optoelectronic properties and applications. However, even at moderate exciton densities, their light-emitting capability is severely limited by Auger-type exciton-exciton annihilation (EEA). Previous work on EEA used oversimplified models in the presence of excitonic complexes, resulting in seriously underestimated values for the Auger coefficient. In this work, we transferred monolayer WS2 on a gold substrate with hBN encapsulation, where excitons persist as the main species at 3-300 K via metal proximity. We numerically solved the rate equation for excitons to accurately determine the Auger coefficient as a function of temperature by considering laser pulse width and spatially inhomogeneous exciton distribution. We found that the Auger coefficient consists of temperature-dependent and independent terms, consistent with a theoretical model for direct and exchange processes, respectively. We believe that our results provide a guide for enhancing the luminescence quantum yield of TMDs.
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Vertical type II van der Waals heterobilayers of transition metal dichalcogenides (TMDs) have attracted wide attention due to their distinctive features mostly arising from the emergence of intriguing electronic structures that include moiré-related phenomena. Owing to strong spin-orbit coupling under a noncentrosymmetric environment, TMD heterobilayers host nonequivalent +K and -K valleys of contrasting Berry curvatures, which can be optically controlled by the helicity of optical excitation. The corresponding valley selection rules are well established by not only intralayer excitons but also interlayer excitons. Quite intriguingly, here, we experimentally demonstrate that unusual valley switching can be achieved using the lowest-lying intralayer excitons in H-type heterobilayer WS2/MoS2 prepared by one-step growth. This TMD combination provides an ideal case for interlayer coupling with an almost perfect lattice match, thereby also in the momentum space between +K and -K valleys in the H-type heterostructure. The underlying valley-switching mechanism can be understood by bright-to-dark conversion of initially created electrons in the valley of WS2, followed by interlayer charge transfer to the opposite valley in MoS2. Our suggested model is also confirmed by the absence of valley switching when the lowest-lying excitons in MoS2 are directly generated in the heterobilayer. In contrast to the H-type case, we show that no valley switching is observed from R-type heterobilayers prepared by the same method, where interlayer charge transfer does not occur between the opposite valleys. We compare the case with the series of valley polarization data from other heterobilayer combinations obtained under different excitation energies and temperatures. Our valley switching mechanism can be utilized for valley manipulation by controlling the excitation photon energy together with the photon helicity in valleytronic devices derived from H-type TMD heterobilayers.
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A new series of germanium chalcophosphates with the formula A(4)GeP(4)Q(12) (A = K, Rb, Cs; Q = S, Se) have been synthesized. The selenium compounds are isostructural and crystallize in the polar orthorhombic space group Pca2(1). The sulfur analogues are isostructural to one another but crystallize in the centrosymmetric monoclinic space group C2/c. All structures contain the new molecular anion [GeP(4)Q(12)](4-); however, the difference between the sulfides and selenides arises from the change in crystal packing. Each discrete molecule is comprised of two ethane-like P(2)Q(6) units that chelate to a central tetrahedral Ge(4+) ion in a bidentate fashion. The selenides were synthesized pure by stoichiometric reaction of the starting materials, whereas the sulfides contained second phases. The band gaps of the molecular salts are independent of the alkali metal counterions and have a value of 2.0 eV for the selenides and 3.0-3.1 eV for the sulfides. All A(4)GeP(4)Se(12) compounds melt congruently, and the potassium analogue can be quenched to give a glassy phase that retains its short-range order as shown by Raman spectroscopy and powder X-ray diffraction. Interestingly, K(4)GeP(4)Se(12) is a phase-change material that reversibly converts between glassy and crystalline states and passes through a metastable crystalline state upon heating just before crystallizing into its slow-cooled form. Initial second harmonic generation (SHG) experiments showed crystalline K(4)GeP(4)Se(12) outperforms the other alkali metal analogues and exhibits the strongest second harmonic generation response among reported quaternary chalcophosphates, ~30 times that of AgGaSe(2) at 730 nm. A more thorough investigation of the nonlinear optical (NLO) properties was performed across a range of wavelengths that is almost triple that of previous reports (λ = 1200-2700 nm) and highlights the importance of broadband measurements. Glassy K(4)GeP(4)Se(12) also exhibits a measurable SHG response with no poling.