Motif based high-throughput structure prediction of superconducting monolayer titanium boride.

Two-dimensional boron structures, due to their diverse properties, have attracted great attention because of their potential applications in nanoelectronic devices. A series of TiBn (2 ≤ n ≤ 13) monolayers are efficiently constructed through our motif based method and theoretically investigated through high-throughput first-principles calculations. The configurations are generated based on the motifs of boron dimeric/triangular/quadrilateral fragments and multi-coordinate titanium-centered boron molecular wheels. Besides previously reported TiB4 and TiB9 which were discovered by the global search method, we predict that high symmetry monolayer TiB7 (Cmmm), which is octa-coordinate titanium boride, is dynamically stable. The TiB7 monolayer is a BCS superconductor with a transition temperature Tc of up to 8.3 K. The motif based approach is proved to be efficient in searching stable structures with prior knowledge so that the potentially stable transition metal monolayers can be quickly constructed by using basic cluster motifs. As an efficient way of discovering materials, the method is easily extended to predict other types of materials which have common characteristic patterns in the structure.

Atom Classification Model for Total Energy Evaluation of Two-Dimensional Multicomponent Materials.

The tunable properties of materials originate from variety of structures; however, it is still a challenge to give an accurate and fast evaluation of stabilities for screening numerous candidates. Herein, we propose an atom classification model to describe the multicomponent materials based on the structural recognition, in which the atoms are classified to estimate the total energies. Taking two-dimensional planar C1-xBx and C1-2x(BN)x as examples, we have found that the test error of total energies is about 3 meV per atom. Notably, the distributions of classified atoms demonstrate the evolution of configurations as a function of temperature, providing a clearer picture of phase transition. In addition, our method is universal, which can be flexibly extended to the bulk structures with more components.

Opening the Band Gap of Graphene via Fluorination for High-Performance Dual-Mode Photodetector Application.

Fluorination is an effective process to open the band gap of graphene (Gr), which is beneficial to the development of optoelectronic devices working in wide wavelength. Herein, we report a dual-mode broadband photodetector (PD) by integrating fluorinated graphene (F-Gr) with silicon (Si). It is found that when working in photoconductive mode, the F-Gr/Si heterojunction exhibited a remarkable photoresponse over a wide spectral region from ultraviolet (UV), visible to near infrared (NIR) light with a high responsivity ( R) of 1.9 × 107 A W-1 and specific detectivity ( D*) of 4.4 × 1012 Jones at 650 nm. Nonetheless, both parameters will be considerably reduced when the F-Gr/Si heterojunction works in the photodiode mode. In this mode, the Ilight/ Idark ratio is as high as 2.0 × 105 and the response speed is accelerated by more than 3 orders of magnitude from about 5 ms to 6.3 µs. Notably, the responsivity of the device in the UV and NIR regions was remarkably enhanced in comparison with that of pristine Gr/Si-heterojunction-based devices. Considering the F-coverage-dependent band gap of the F-Gr revealed by the first-principle calculations, we believe that the enhancement was ascribed to the opening of the band gap in the partially fluorinated Gr, which is stabilized due to the configuration entropy as the temperature increases. The dual-mode PD enabled the simultaneous weak light detection and fast photodetection, which overcome the limitation of the traditional monomode PD.

Coexistence of Strong Second Harmonic Generation Response and Wide Band Gap in AZn4 Ga5 S12 (A=K, Rb, Cs) with 3D Diamond-like Frameworks.

Mid-infrared (MIR, 2-20 µm) second-order nonlinear optical (NLO) materials with outstanding performances are of great importance in laser science and technology. However, the enormous challenge to design and synthesize an excellent MIR NLO material lies in achieving simultaneously a strong second harmonic generation (SHG) response [dij >0.6 × AgGaS2 (AGS)] and wide band gap (Eg >3.5 eV). Herein three new MIR NLO materials, AZn4 Ga5 S12 (A=K, Rb, Cs) are reported, which crystallize in the KCd4 Ga5 S12 -type structure and adopt a 3D diamond-like framework (DLF) consisting of MS4 (M=Zn/Ga) tetrahedra; achieving the desired balance with strong powder SHG response (1.2-1.4 × AGS) and wide band gap (Eg ≈3.65 eV). Moreover, they also show large laser induced damage thresholds (LIDTs, 36 × AGS), a wide range of optical transparency (0.4-25 µm) and ultrahigh thermal stability (up to 1400 K). Upon analyzing the structure-property relationship of AXII4 XIII5 Q12 family, these 3D DLF structures can be used as a highly versatile and tunable platform for designing excellent MIR NLO materials.

Two excellent phase-matchable infrared nonlinear optical materials based on 3D diamond-like frameworks: RbGaSn2Se6 and RbInSn2Se6.

Mid- and far-infrared (MFIR) nonlinear optical (NLO) crystals with excellent performances are critical to laser frequency-conversion technology. However, the current commercial MFIR NLO crystals, including AgGaS2 (AGS), AgGaSe2 and ZnGeP2, suffer from certain intrinsic drawbacks and cannot achieve a good balance between large second-harmonic generation (SHG) efficiency and high laser-induced damage thresholds (LIDTs). Herein, we report two new phase-matchable MFIR NLO chalcogenides, specifically RbXSn2Se6 (X = Ga, In), which were successfully synthesized by high-temperature solid-state reactions. The remarkable structural feature of these materials was their 3D diamond-like framework (DLF) stacked by M3Se9 (M = X/Sn) asymmetric building units of vertex-sharing MSe4 tetrahedra along the c axis. Significantly, both of the materials showed the excellent NLO performances with the desired balance between their large SHG efficiencies (4.2 and 4.8 × benchmark AGS) and large LIDTs (8.9 and 8.1 × benchmark AGS), demonstrating that the title compounds meet the crucial conditions as promising MFIR NLO candidates. Furthermore, the crystal structures, synthesis, and theoretical analysis, as well as optical properties are presented herein.

Ba5Cu8In2S12: a quaternary semiconductor with a unique 3D copper-rich framework and ultralow thermal conductivity.

A novel quaternary sulfide, Ba5Cu8In2S12 (1), has been successfully synthesized via a high-temperature solid-state reaction. It contains Cu8S10S4/2 clusters as basic building blocks, which are connected to one another by discrete In3+ ions to generate a 3D copper-rich framework, where the Ba2+ cations reside. Interestingly, such large clusters that are fused by five crystallographically independent Cu sites with three different chemical environments result in the increase of phonon scattering, which is the crucial factor to the exceptionally low lattice thermal conductivity (ca. 0.28 W m-1 K-1 at 773 K) in 1.

Tailored synthesis of nonlinear optical quaternary chalcohalides: Ba4Ge3S9Cl2, Ba4Si3Se9Cl2 and Ba4Ge3Se9Cl2.

Three novel zero-dimensional quaternary chalcohalides, Ba4Ge3S9Cl2, Ba4Si3Se9Cl2 and Ba4Ge3Se9Cl2, which crystallize in the polar noncentrosymmetric space group P63 (no. 173), have been rationally synthesized by a tailored approach on the basis of unique [M3Q9]6- (M = Ge, Q = S; M = Ge/Si, Q = Se) units with Ba2+ cations and Cl- anions occupying the interspaces. The [M3Q9]6- units which consist of three Q-corner-sharing [MQ4]4- tetrahedra, are arranged along the 63 screw axis. Remarkably, Ba4Ge3S9Cl2 exhibits a strong powder second harmonic generation (SHG) response that is 2.4 times that of benchmark AgGaS2 at a laser radiation of 2.05 µm in the same particle size range of 46-74 µm. Furthermore, theoretical studies based on the density functional theory helped to gain insight into the origin of the SHG.

Non-centrosymmetric Selenides AZn4 In5 Se12 (A=Rb, Cs): Synthesis, Characterization and Nonlinear Optical Properties.

Two new non-centrosymmetric polar quaternary selenides, namely, RbZn4 In5 Se12 and CsZn4 In5 Se12 , have been synthesized and structurally characterized. They exhibit a 3D diamond-like framework (DLF) consisting of corner-shared MSe4 (M=Zn/In) tetrahedra, in which the A+ ions are located. Both compounds are thermally stable up to 1300 K and exhibit large transmittance in the infrared region (0.65-25 µm) with measured optical band gaps of 2.06 eV for RbZn4 In5 Se12 and 2.11 eV for CsZn4 In5 Se12 . Inspiringly, they exhibit a good balance between strong second harmonic generation (SHG) efficiency (3.9 and 3.5×AgGaS2 ) and high laser-induced damage thresholds (13.0×AgGaS2 ). Theoretical calculations based on density functional theory (DFT) methods confirm that such strong SHG responses originate from the 3D DLF structure.

AXXTe12 (A = Rb, Cs; XII = Mn, Zn, Cd; XIII = Ga, In): quaternary semiconducting tellurides with very low thermal conductivities.

The discovery of novel materials with very low thermal conductivity is paramount to improving the efficiency of thermoelectric devices. Here we present a series of quaternary semiconducting tellurides AXXTe12 (A = Rb, Cs; XII = Mn, Zn, Cd; XIII = Ga, In) with three-dimensional (3D) diamond-like frameworks (DLFs) and they exhibit a very low thermal conductivity (ca. 0.26-0.42 W m-1 K-1) around 800 K.

Pb5Ga6ZnS15: a noncentrosymmetric framework with chains of T2-supertetrahedra.

A novel noncentrosysmmetric sulfide, Pb5Ga6ZnS15 (1), was synthesized for the first time. Its crystal structure revealed the presence of [GaS2](-)∞ (chain 1, chains of [GaS4](5-) tetrahedra) and [Ga4S9](6-)∞ (chain 2, chains of T2-supertetrahedra) connected by isolated [ZnS4](6-) tetrahedra. Structure correlation with the network constructed solely using chain 1 (Pb4Ga4GeQ12-type) is discussed. Pb5Ga6ZnS15 was calculated to have a suitable static briefringence (Δn) of 0.1137, and a large nonlinear optical susceptibility d31 of 58.32 pm V(-1) at a wavelength of 2.05 µm (0.6 eV), much higher than that of the benchmark AgGaS2 (18.14 pm V(-1)).

CsBi4Te6: a new facile synthetic method and mid-temperature thermoelectric performance.

CsBi4Te6 is one of the best performing low-temperature thermoelectric (TE) materials. However, it has not received worldwide intensive investigation due to the limitation of synthetic methods. Here we report a new facile approach by not using the reactive Cs metal and the mid-temperature TE properties have been studied for the first time.

Syntheses, structures, physical and electronic properties of quaternary semiconductors: Cs[RE9Cd4Se18] (RE = Tb-Tm).

Five new quaternary rare-earth selenides, Cs[RE9Cd4Se18] (RE = Tb-Tm), which are the first examples with closed cavities in the quaternary A/RE/Cd/Q (A = alkali metal; RE = rare earth metal; Q = chalcogenide) system, have been synthesized by high-temperature solid state reactions with a modified reactive CsCl flux. Single crystal X-ray diffraction analyses show that these isostructural materials adopted a known BaV13O18-structure type in the trigonal space group R3[combining macron] (no. 148) with cell parameters of a = 17.773(2)-17.489(6) Å, c = 9.918(2)-9.765(5) Å and Z = 3. The structure is composed of MSe6 (centered by disordered RE and Cd) and RESe6 octahedra that share edges to form a 3D framework, inside which the cuboctahedral Se12 closed cavities accommodate Cs cations. It is interesting to note that these compounds exhibit atomic distributions different from the recently reported Mn-compounds Cs[RE9Mn4Se18]. In Cd-compounds, Cd and RE atoms are statistically mixed only at one of the 18f sites; the rest of the RE atoms are fully occupied at the two framework sites: 18f and 3a. Moreover, the theoretical studies have greatly aided the understanding of the site-preference about a Cd atom in the 3D framework. The synthesis, structural characterization, electronic band structure as well as physical properties of the title compounds are also discussed.

(Cs6Cl)6Cs3[Ga53Se96]: A Unique Long Period-Stacking Structure of Layers Made from Ga2Se6 Dimers via Cis or Trans Intralayer Linking.

The new compound (Cs6Cl)6Cs3[Ga53Se96] with its own structure type has been discovered by high-temperature solid-state reactions. The compound features a unique long period-stacking structure of layers that are built by the commonly observed dimeric Ga2Se6 unit extending in cis or trans intralayer linking. Single-crystal X-ray diffraction analyses show the trigonal space group R3̅m (No. 166) and a = 11.990(5) Å, c = 50.012(4) Å, and V = 6226.5(6) Å(3). The UV-vis-near-IR spectrum reveals a wide band gap of 2.74 eV that agrees well with the electronic structure calculation.