A review of structures and physical properties of rare earth chalcophosphates

Revisiting two thiophosphate compounds constituting d0transition metal HfP2S6and d10transition metal α-Ag4P2S6as multifunctional materials for combining second harmonic generation response and photocurrent response

“…After many years of intensive study, few materials, including AgGaS 2 , ZnGeP 2 , and AgGaSe 2 , have been commercialized due to their balanced properties which play an important role in scientific research and industrial applications. 1–29 These commercial materials, AgGaS 2 , ZnGeP 2 , and AgGaSe 2 , are impeded from high energy use due to their intrinsic limitations including low laser damage threshold, double-photon absorption, and non-phase-matching behavior, respectively. 13,30–32 In addition to energy loss, these commercial materials cannot be employed to cover the full range of the infrared spectrum.…”

“…Thiophosphates, which combine both phosphorus and sulfur, are demonstrated to be good candidates for infrared nonlinear optical materials, where the promising properties originate from structure and chemical flexibility. The flexible [P x S y ] motifs interact with various cations generating many promising nonlinear optical materials including Rb 2 Ga 2 P 2 S 9 , 33 [K 3 Cl][Ga 3 PS 8 ], 34 [Rb 3 Cl][Ga 3 PS 8 ], 34 [K 3 Br][Ga 3 PS 8 ], 34 [Rb 3 Br] [Ga 3 PS 8 ], 34 LiZnPS 4 , 35 CuZnPS 4 , 36 CuHgPS 4 , 37 AgZnPS 4 , 35 Ag 3 -PS 4 , 38 LiGa 2 PS 6 , 39 AgGa 2 PS 6 , 40 LiCd 3 PS 6 , 39 CuCd 3 PS 6 , 41 AgCd 3 -PS 6 , 42 Zn 3 P 2 S 8 , 43 Hg 3 P 2 S 8 , 44 Sn 2 P 2 S 6 , [45][46][47] KBiP 2 S 6 , 48 K 2 BaP 2 S 6 , 49 KSbP 2 S 6 , 49 Pb 2 P 2 S 6 , 50 α-Ba 2 P 2 S 6 , 50 Pb 3 P 2 S 8 , 51 RbBiP 2 S 6 , 52 Eu 2 P 2 -S 6 , 53 Hg 2 P 2 S 6 , 54 ASrPS 4 (A = Li, Na, K, Rb, Cs), 55 AAg 2 PS 4 (A = K, Na/K), 56 etc. From the perspective of the constituting cations, the most explored cations for thiophosphate nonlinear optical materials are alkali metals and d 10 transition metals.…”

γ-P4S3I2: a new metal-free infrared second-order nonlinear optical crystal designed by polymorphism strategy

“…Exploring non-centrosymmetric (NCS) inorganic compounds is of great significance in the development of piezoelectric, pyroelectric, ferroelectric, and especially nonlinear optical (NLO) materials. [1][2][3][4][5][6] NLO materials are indispensable for applications in medical treatment, atmospheric detection and optical communication relying on frequency conversion. 7,8 To date, many well-known NLO crystals, such as β-BaB 2 O 4 , LiB 3 O 5 and CsLiB 6 O 10 as well as KTiOPO 4 and LiNbO 3 , have basically met the needs in the UV and visible (vis) regions.…”

“…Thiophosphates are a very promising system for mid-IR NLO applications because the existence of strong covalent P-S bonds not only improves the NLO response but can also drive the blue shift of the short-wave absorption edge; 29 for example, Hg 3 P 2 S 8 (2.72 eV, 4.2 × AgGaS 2 ), Eu 2 P 2 S 6 (2.54 eV, 0.9 × AgGaS 2 ), RbBiP 2 S 6 (2.10 eV, 11.9 × AgGaS 2 ) and CuHgPS 4 (2.03 eV, 6.5 × AgGaS 2 ) exhibit good IR-NLO performances. [30][31][32][33] In addition, positive valence P atoms have a flexible coordination environment (2)(3)(4), which is favorable in forming polymorphs. For example, the polymorphism of P 2 S 7 (α: P2 1 /c, β: P1 ˉ)34 exhibits two different crystal structures.…”

MB3P2S10 (M = Rb, Cs): two new alkali metal thioboratephosphates with [B6P4S20] T3-supertetrahedra

“…Chalcogenides have received considerable attention recently because of their rich chemical and structural diversity, 1–3 and have shown wide applications in the fields of nonlinear optics, 4–11 batteries, 12 solar cells, 13,14 catalysis, 15,16 neutron detection, 17 and so on. 18,19 In general, chalcogenides can be divided into metal chalcogenides (in which the nonmetallic element is limited to S/Se/Te), chalcoborates, 20–22 chalcophosphates, 23–26 chalcohalides, 27–29 and others. 30–34 Among them, chalcoborates inherit the inborn advantages in coupling the merits of borates and chalcogenides.…”