ABSTRACT
Midinfrared nonlinear optical (NLO) rare earth chalcogenides have attracted extensive research interest in recent several decades. Employing charge-transfer engineering strategy in the early stage, rigid tetrahedral [GeS4] was introduced into rare-earth sulfides to synthesize KYGeS4, which had an enlarged band gap while maintaining a strong second harmonic generation (SHG) effect. Based on KYGeS4, La was equivalently substituted to successfully synthesize KLaGeS4 with a stronger SHG effect (dij = 1.2 × AgGaS2) and lower cost. Meanwhile, a larger band gap (Eg = 3.34 eV) was retained and realized phase matching (Δn = 0.098 @ 1064 nm). KLaGeS4 enabled an effective balance among band gap, SHG effect, and birefringence, making it a promising candidate for infrared NLO optical materials among various rare-earth sulfides.
ABSTRACT
Improving the laser damage threshold (LDT) of mid-infrared nonlinear-optical (MIR NLO) crystal materials is crucial for their applications in areas such as environmental monitoring and pharmaceutical detection. This paper presents the successful synthesis of SrZnSiSe4, a new MIR NLO crystal material that balances the LDT and second-harmonic-generation (SHG) effects and achieves phase matching. By replacement of Sn with Si in the existing SrZnSnSe4 material, the band gap of the material was increased, resulting in an LDT that is twice that of SrZnSnSe4, while maintaining the 2 × AgGaS2 effect. The SHG and band gap of SrZnSiSe4 derived from the experiments are 2 × AgGaS2 and 1.95 eV. The band gap of SrZnSiSe4 is better than that of SrZnSnSe4 (1.82 eV), and the LDT of SrZnSiSe4 is about twice that of SrZnSnSe4. Moreover, first-nature principal calculations confirm that SrZnSiSe4 can achieve phase matching after 1520 nm with a birefringence of 0.10, making it an excellent candidate for MIR NLO crystals.
ABSTRACT
Birefringence, an important optical performance parameter for optoelectronic functional materials, is mainly influenced by the types of anion groups and their spatial arrangement. Inspired by the relationship between the structure and properties of chalcogenides, combined with the dimensional transformation, we successfully synthesized a sulfide compound (Cs2ZnSn3S8) with a two-dimensional layered structure and a large birefringence. The experimental results showed that, compared with Rb10Zn4Sn4S17, Cs2ZnSn3S8 achieved the structural transition from a zero-dimensional arrangement to a two-dimensional lamellar arrangement and achieved a breakthrough of birefringence from 0 to 0.12, which was determined by both experiments and first-principles calculations. These findings demonstrated that Cs2ZnSn3S8 was a potential birefringent material and provided instructions for the study of the synthesis of birefringent materials.
ABSTRACT
In the military and civilian fields, with the development of new technologies, high-powered nonlinear optical (NLO) crystals demonstrate broad application prospects. In this work, for purposes of designing a better NLO material, a new chalcogenide Rb10Zn4Sn4S17 was successfully designed with a high temperature solid-state method on the basis of previously reported compound Sr3MnSn2S8. The experimental results indicate that Rb10Zn4Sn4S17 possesses a prominent band gap of 3.59 eV, compared with the laser damage threshold (LDT) of Sr3MnSn2S8 (3 times that of AgGaS2); Rb10Zn4Sn4S17 shows an outstanding LDT about 5 times that of AgGaS2. Meanwhile, it has an ideal second harmonic generation (SHG) response approximately 0.7 times that of AgGaS2.
ABSTRACT
In this work, we design and synthesize a new chalcogenide LiGaGe2S6 on the basis of known infrared (IR) material LiGaS2 by partially substituting Ga with Ge. This compound possesses very strong nonlinear (NLO) response (2.5 × LiGaS2) and large band gap (3.52 eV), manifesting a better balance between band gap and NLO response compared with that for LiGaS2. Moreover, LiGaGe2S6 exhibits a much lower melting point (663 °C) than that of LiGaS2 (1050 °C). This would result in the much smaller vapor pressure of sulfur in the fused quartz vessels used for the crystal growth, and thus, it should be greatly beneficial to obtain the large stoichiometric LiGaGe2S6 single crystal. Our studies demonstrate that LiGaGe2S6 is a good candidate material for IR NLO applications.
ABSTRACT
Microencapsulated phase change materials (MCPCM) as a green energy storage material not only prevent leakage of phase change materials but also increase the heat transfer area of phase change materials. Extensive previous work has shown that the performance of MCPCM depends on the shell material and MCPCM with polymers, as the shell material suffers from low mechanical strength and low thermal conductivity. In this study, a novel MCPCM with hybrid shells of melamine-urea-formaldehyde (MUF) and sulfonated graphene (SG) was prepared by in situ polymerization using SG-stabilized Pickering emulsion as a template. The effects of SG content and core/shell ratio on the morphology, thermal properties, leak-proof properties, and mechanical strength of the MCPCM were investigated. The results showed that the incorporation of SG into the shell of MUF effectively improved the contact angles, leak-proof performance, and mechanical strength of the MCPCM. Specifically, the contact angles of MCPCM-3SG were reduced by 26°, the leakage rate was reduced by 80.7%, and the breakage rate after high-speed centrifugation was reduced by 63.6% compared to MCPCM without SG. These findings suggest that the MCPCM with MUF/SG hybrid shells prepared in this study has great potential for application in thermal energy storage and management systems.
ABSTRACT
The incorporation of different functional fillers has been widely used to improve the properties of polymeric materials. The polyhydroxy structure of PVA with excellent film-forming ability can be easily combined with organic/inorganic multifunctional compounds, and such an interesting combining phenomenon can create a variety of functional materials in the field of materials science. The composite membrane material obtained by combining MOF material with high porosity, specific surface area, and adjustable structure with PVA, a non-toxic and low-cost polymer material with good solubility and biodegradability, can combine the processability of PVA with the excellent performance of porous filler MOFs, solving the problem that the poor machinability of MOFs and the difficulty of recycling limit the practical application of powdered MOFs and improving the physicochemical properties of PVA, maximizing the advantages of the material to develop a wider range of applications. Firstly, we systematically summarize the preparation of MOF/PVA composite membrane materials using solution casting, electrostatic spinning, and other different methods for such excellent properties, in addition to discussing in detail the various applications of MOF/PVA composite membranes in water treatment, sensing, air purification, separation, antibacterials, and so on. Finally, we conclude with a discussion of the difficulties that need to be overcome during the film formation process to affect the performance of the composite film and offer encouraging solutions.
ABSTRACT
In the field of cooling materials, ZnTiO3 (ZT) is still a new member that needs to be further studied. In this paper, pure cubic ZT was synthesized by the sol-gel method, and the effect of calcination temperature on ZT synthesis was investigated. The hydrophobic modification was carried out on ZT to prepare near-infrared reflective thermal insulation functional composite coatings based on silicone resin (SI). Compared with unmodified ZT (U-ZT), the modified ZT (M-ZT) exhibits better dispersion in the SI matrix, contributing to improved solar reflectance and anti-graffiti performance. The EnergyPlus software was used to simulate energy consumption in the air conditioning system. The excellent chemical stability and high NIR reflectance made the synthesized pigments potential candidates for energy-saving coatings. The simulation showed that homeowners could save $10.29 a month by applying an energy-efficient coating consisting of ZT to the walls and roofs of their buildings. Besides, these coatings show potential anti-graffiti application due to the exceptional repellency of coated surfaces against water-based ink, oily red marker, and paint.
ABSTRACT
The new compound LiGaGe(2)Se(6) has been synthesized. It crystallizes in the orthorhombic space group Fdd2 with a = 12.501(3) Å, b = 23.683(5) Å, c = 7.1196(14) Å, and Z = 8. The structure is a three-dimensional framework composed of corner-sharing LiSe(4), GaSe(4), and GeSe(4) tetrahedra. The compound exhibits a powder second harmonic generation signal at 2 µm that is about half that of the benchmark material AgGaSe(2) and possesses a wide band gap of about 2.64(2) eV. LiGaGe(2)Se(6) melts congruently at a rather low temperature of 710 °C, which indicates that bulk crystals can be obtained by the Bridgman-Stockbarger technique. According to a first-principles calculation, there is strong hybridization of the 4s and 4p orbitals of Ga, Ge, and Se around the Fermi level. The calculated birefractive index is Δn = 0.04 for λ ≥ 1 µm, and the calculated major SHG tensor elements are d(15) = 18.6 pm/V and d(33) = 12.8 pm/V. This new material is promising for application in IR nonlinear optics.
ABSTRACT
Increasing the energy band gap under the premise to maintain a large nonlinear optical (NLO) response is a challenging issue for the exploration and molecular design of mid-infrared nonlinear optical crystals. Utilizing a charge-transfer engineering method, we designed and synthesized a rare earth chalcogenide, KYGeS4. With an NLO effect as large as that in AgGaS2, KYGeS4 breaks through the limitation of energy band gap, i.e., the "3.0 eV wall", in NLO rare earth chalcogenides, and thus exhibits an excellent comprehensive NLO performance. First-principles electronic structure analysis demonstrates that the large band gap in KYGeS4 is ascribed to the decreased covalency of Y-S bonds by transferring charge from [YS7] to [GeS4] polyhedra. The charge-transfer engineering strategy would have significant implications for the exploration of good-performance NLO crystals.
ABSTRACT
The new compound BaGa(4)Se(7) has been synthesized for the first time. It crystallizes in the monoclinic space group Pc with a = 7.6252 (15) Å, b = 6.5114 (13) Å, c = 14.702 (4) Å, ß = 121.24 (2)°, and Z = 2. In the structure, GaSe(4) tetrahedra share corners to form a three-dimensional framework with cavities occupied by Ba(2+) cations. The material is a wide-band gap semiconductor with the visible and IR optical absorption edges being 0.47 and 18.0 µm, respectively. BaGa(4)Se(7) melts congruently at 968 °C and exhibits a second harmonic generation response at 1 µm that is approximately 2-3 times that of the benchmark material AgGaS(2). A first-principles calculation of the electronic structure, linear and nonlinear optical properties of BaGa(4)Se(7) was performed. The calculated birefractive indexΔn = 0.08 at 1 µm and the major SHG tensor elements are: d(11) = 18.2 pm/V and d(13) = -20.6 pm/V. This new material is a very promising NLO crystal for practical application in the IR region.
ABSTRACT
Zero thermal expansion (ZTE) materials, keeping size constant as temperature varies, are valuable for resisting the deterioration of the performance from environmental temperature fluctuation, but they are rarely discovered due to the counterintuitive temperature-size effect. Herein, we demonstrate that a family of borates with sodalite cage structure, Zn4B6O12X (X = O, S, Se), exhibits intrinsic isotropic near-ZTE behaviors from 5 to 300 K. The very low thermal expansion is mainly owing to the coupling rotation of [BO4] rigid groups constrained by the bonds between Zn and cage-edged O atoms, while the central atoms in the cage have a negligible contribution. Our study has significant implications on the understanding of the ZTE mechanism and exploration of new ZTE materials.
ABSTRACT
A new germanium-based sulfide, Ba6Cu2FeGe4S16, achieves a band-gap broadening of more than 1 eV relative to CuFeS2. Remarkably, Ba6Cu2FeGe4S16 exhibits excellent comprehensive NLO performance (SHG, 1.5 × AgGaSe2; LDT, 2 × AgGaSe2), satisfying the essential requirements of mid-IR NLO candidates.
ABSTRACT
The first two members in alkaline-earth/group XI/group XIII/chalcogen system, namely Ba(2)AgInS(4) and Ba(4)AgGa(5)Se(12), were synthesized along with a Li analogue Ba(4)LiGa(5)Se(12). Ba(2)AgInS(4) crystallizes in space group P2(1)/c. It contains [AgInS(4)](4-) layers built from AgS(3) triangles and InS(4) tetrahedra with Ba(2+) cations inserted between the layers. Ba(4)AgGa(5)Se(12) and Ba(4)LiGa(5)Se(12) adopt two closely-related structure types in space group P4[combining macron]2(1)c with structural difference originating from the different positions of Ag and Li in them. The three-dimensional framework in Ba(4)AgGa(5)Se(12) is composed of GaSe(4) tetrahedra with the Ba and Ag atoms occupying the large and small channels respectively, whereas that in Ba(4)LiGa(5)Se(12) is built from LiSe(4) and GaSe(4) tetrahedra with channels to accommodate the Ba atoms. As deduced from the diffuse reflectance spectra measurement, the optical band gaps were 2.32 (2) eV, 2.52 (2) eV, and 2.65 (2) eV for Ba(2)AgInS(4), Ba(4)AgGa(5)Se(12), and Ba(4)LiGa(5)Se(12), respectively.
ABSTRACT
The four compounds BaGa(2)MQ(6) (M = Si, Ge; Q = S, Se) have been identified as a new series of IR nonlinear optical (NLO) materials and are promising for practical applications. They are isostructural and crystallize in the noncentrosymmetric polar space group R3 of the trigonal system. Their three-dimensional framework is composed of corner-sharing (Ga/M)Q(4) (M = Si, Ge; Q = S, Se) tetrahedra with Ba(2+) cations in the cavities. The polar alignment of one (Ga/M)-Q2 bond for each (Ga/M)Q(4) tetrahedra along the c direction is conducive to generating a large NLO response, which was confirmed by powder second-harmonic generation (SHG) using a 2090 nm laser as fundamental wavelength. The SHG signal intensities of the two sulfides were close to that of AgGaS(2) and those for the two selenides were similar as that of AgGaSe(2). The large band gaps of 3.75(2) eV, 3.23(2) eV, 2.88(2) eV, and 2.22 (2) eV for BaGa(2)SiS(6), BaGa(2)GeS(6), BaGa(2)SiSe(6), and BaGa(2)GeSe(6), respectively, will be very helpful to increase the laser damage threshold. Moreover, all the four BaGa(2)MQ(6) (M = Si, Ge; Q = S, Se) compounds exhibit congruent-melting behavior, which indicates that bulk crystals needed for practical applications can be obtained by the Bridgman-Stockbarger method. The calculated birefringence indicates that these materials may be phase-matchable in the IR region and the calculated SHG coefficients agree with the experimental observations. According to our preliminary study, the BaGa(2)MQ(6) compounds represent a new series of promising IR nonlinear optical (NLO) materials which do not belong to the traditional chalcopyrite-type materials such as AgGaQ2 (Q = S, Se) and ZnGeP(2).
ABSTRACT
The new compound Ba(5)Ga(4)Se(10) has been synthesized for the first time. It crystallizes in the tetragonal space group I4/mcm with a = 8.752(2) Å, c = 13.971(9) Å, and Z = 2. The structure contains discrete [Ga(4)Se(10)](10-) anions and charge-compensating Ba(2+) cations. The novel highly anionic [Ga(4)Se(10)](10-) cluster is composed of two Ga(Se)(4) tetrahedra and two Ga(Ga)(Se)(3) tetrahedra with Ga in the 2+/3+ valence states. It also exhibits an unusually long Ga-Se distance of 2.705(2) Å, which has only been observed under high pressure conditions before. A band gap of 2.20(2) eV was deduced from the UV/vis diffuse reflectance spectrum.
ABSTRACT
The new compound BaAl(4)Se(7) has been synthesized by solid-state reaction. It crystallizes in the non-centrosymmetric space group Pc and adopts a three-dimensional framework built from AlSe(4) tetrahedra and with Ba(2+) cations in the cavities. The material has a large band gap of 3.40(2) eV. It melts congruently at 901 °C and exhibits a second harmonic generation (SHG) response at 1 µm that is about half that of AgGaS(2). From a band structure calculation, BaAl(4)Se(7) is a direct-gap semiconductor with strong hybridization of the Al 3s, Al 3p, and Se 4p orbitals near the Fermi level. The calculated birefractive index is about 0.05 for wavelength longer than 1 µm and major SHG tensor elements are: d(15) = 5.2 pm V(-1) and d(13) = 4.2 pm V(-1).