Barium-based pnictide compounds, nonlinear optical crystals thereof, and methods of making and using the same

Abstract

The application discloses a pnictogen compound, a nonlinear optical crystal thereof, and a preparation method and application thereof. The nonlinear optical crystal of the application has large nonlinear optical effect and large laser damage threshold (7.5-9.4*AGS). The nonlinear optical crystal of barium phosphosilicate gallium, barium phosphosilicate zinc has good infrared transmission performance in a 2.510-micron wave band. The nonlinear optical crystal of barium arsenosilicate gallium, barium arsenosilicate indium has good infrared transmission performance in a 2.512-micron wave band. The nonlinear optical crystal has the advantages of large nonlinear optical effect, good mechanical property and easy processing, and can be widely applied in various nonlinear optical fields and a middle infrared wave band.

Description

Technical Field

[0001] This invention belongs to the field of functional crystal materials, and relates to a phosphorus compound, its nonlinear optical crystal, its preparation method and use, specifically involving a phosphorus silicon gallium barium compound, an arsenic silicon gallium barium compound, an arsenic silicon indium barium compound, a phosphorus silicon zinc barium compound, a phosphorus silicon gallium barium nonlinear optical crystal, an arsenic silicon gallium barium nonlinear optical crystal, an arsenic silicon indium barium nonlinear optical crystal, a phosphorus silicon zinc barium nonlinear optical crystal, and their preparation methods and uses. Background Technology

[0002] Mid-infrared lasers (2.5–25 μm), especially long-wavelength infrared tunable lasers in the 8–14 μm range, have important applications in both military and civilian fields, such as laser guidance, optoelectronic countermeasures, infrared remote sensing, medical diagnosis, and environmental monitoring. Currently, the practical nonlinear optical crystal materials used to obtain long-wavelength infrared lasers using nonlinear optical methods are mainly AgGaS2, AgGaSe2, ZnGeP2, and CdSe. However, with the rapid development of solid-state laser technology and the increasing national demand for ultrashort pulse, high repetition rate, and high-power mid-infrared laser output, there is an urgent need to develop novel long-wavelength infrared nonlinear optical crystals with superior overall performance, particularly high laser damage thresholds. Phosphorus compounds possess large nonlinear optical coefficients, high thermal conductivity, and a wide transmission range, making them ideal candidate material systems. Summary of the Invention

[0003] To improve the above-mentioned technical problems, the present invention provides a chemical formula BaM x Zn y Si 7+z Pn 10+n The compound wherein: M is selected from Al, Ga or In; Pn is selected from P or As; x is an integer between 0 and 3, for example, x = 0, 1, 2 or 3; y is between 0 and 3, for example, y = 0, 1, 2, 2.5 or 3; and x and y are not both 0 at the same time; z is between 0 and 3, for example, z = 0, 1, 2, 2.5 or 3; n is an integer from 1 to 5, for example, n = 1, 2, 3, 4 or 5.

[0004] According to an embodiment of the present invention, the BaM x Zn y Si 7+z Pn 10+n The compound is BaM x Si7Pn 10+n Where: M is selected from Al, Ga or In; Pn is selected from P or As; x is an integer from 1 to 3, for example x=1 or 2; n is an integer from 1 to 3, for example, n=1 or 2.

[0005] According to an embodiment of the present invention, the BaM x Zn y Si 7+z Pn 10+n The compound is BaZn y Si 7+z Pn 10+n Where: Pn is selected from P or As; z is 1 to 3, for example, z = 1, 2, 2.5 or 3; n is an integer from 2 to 5, for example, n = 2, 3, 4 or 5.

[0006] According to an embodiment of the present invention, the chemical formula is BaM x Zn y Si 7+z Pn 10+n The compound is barium gallium phosphide (BaGaSi7P). 11 BaGa2Si7P 12 Or arsenic-silicon-gallium-barium compound BaGa2Si7As 12 Or arsenic, silicon, indium, barium compounds BaIn2Si7As 12 Or a compound of phosphorus, silicon, zinc, and barium (BaZnSi8P) 12 , BaZn 2.5 Si 9.5 P 15 .

[0007] According to an embodiment of the present invention, the BaM x Zn y Si 7+z Pn 10+n The preparation method of the compound includes: mixing Ba source material, M source material, Zn source material, Si source material and Pn source material, grinding, and calcining at high temperature to obtain the BaM. x Zn y Si 7+z Pn 10+n Compounds.

[0008] In some embodiments, the method for preparing the barium gallium phosphosilicate compound includes mixing Ba source material, Ga source material, Si source material and P source material, grinding them, and calcining them at high temperature to obtain the barium gallium phosphosilicate compound.

[0009] In some embodiments, the preparation method of the arsenic silicon gallium barium compound includes: mixing Ba source material, Ga source material, Si source material and As source material, grinding, and calcining at high temperature to obtain the arsenic silicon gallium barium compound.

[0010] In some embodiments, the preparation method of the arsenic silicon indium barium compound includes: mixing Ba source material, In source material, Si source material and As source material, grinding, and calcining at high temperature to obtain the arsenic silicon indium barium compound.

[0011] In some embodiments, the preparation method of the barium phosphosilicate zinc compound includes: mixing Ba source material, Zn source material, Si source material and P source material, grinding, and calcining at high temperature to obtain the barium phosphosilicate zinc compound.

[0012] The present invention also provides the above-mentioned BaM x Zn y Si 7+z Pn 10+n A method for preparing the compound, the method comprising: mixing Ba source material, M material, Zn source material, Si source material and Pn source material, grinding, and calcining at high temperature to obtain the BaM. x Zn y Si 7+z Pn 10+n Compounds.

[0013] According to an embodiment of the present invention, the M source material is provided by Ga source material and In source material.

[0014] According to an embodiment of the present invention, the Pn source material is provided by a P source material or an As source material.

[0015] According to an embodiment of the present invention, the molar ratio of elements Ba, M, Zn, Si, and Pn in the Ba source material, M source material, Zn source material, Si source material, and Pn source material is 1:0-3:0-3:7-10:11-15, for example, 1:1:0:7:11, 1:2:0:7:11, 1:3:0:7:11, 1:1:0:7:12, or 1:2:0:7:12. 1:3:0:7:12, 1:0:1:8:12, 1:0:2:8:12, 1:0:2.5:8:12, 1:0:3:8:12, 1:0:2:9:12, 1:0:2.5:9.5:12, 1:0:2.5:9.5:13, 1:0:2.5:9.5:14, 1:0:2.5:9.5:15 or 1:0:3:10:15.

[0016] According to an embodiment of the present invention, the Ba source material is selected from elemental Ba.

[0017] According to an embodiment of the present invention, the Ga source material is selected from elemental Ga, GaAs, or GaP.

[0018] According to an embodiment of the present invention, the Si source material is selected from elemental Si.

[0019] According to an embodiment of the present invention, the P source material is selected from elemental P or GaP, Zn3P2.

[0020] According to an embodiment of the present invention, the As source material is selected from elemental As, InAs, or GaAs.

[0021] According to an embodiment of the present invention, the In source material is selected from elemental In or InAs.

[0022] According to an embodiment of the present invention, the Zn source material is selected from elemental Zn or Zn3P2.

[0023] According to an embodiment of the present invention, the high-temperature calcination temperature is 900℃-1100℃, for example, 900℃, 950℃, 980℃, 1000℃, 1050℃, 1080℃, or 1100℃. Preferably, the heating rate of the high-temperature calcination is 20℃ / h-80℃ / h, for example, 30-40℃ / h, exemplarily 20℃ / h, 50℃ / h, or 80℃ / h. Preferably, the high-temperature calcination time is 24 hours-120 hours, for example, 24 hours, 36 hours, 48 ​​hours, 60 hours, 72 hours, 80 hours, 96 hours, or 120 hours.

[0024] According to an embodiment of the present invention, the preparation method further includes cooling after high-temperature calcination. Preferably, the cooling refers to reducing the temperature at a rate of 1℃ / h-5℃ / h (e.g., 1℃ / h, 3℃ / h, or 5℃ / h) to 700℃-300℃ (e.g., 300℃, 400℃, 500℃, 600℃, or 700℃), and then reducing it to room temperature.

[0025] According to an embodiment of the present invention, the preparation method includes: mixing Ba source material, M material, Si source material and Pn source material, grinding, and calcining at high temperature to obtain the BaM. x Si7Pn 10+n Compounds.

[0026] According to an exemplary embodiment of the present invention, the molar ratio of elements Ba, M, Si, and Pn in the Ba source material, M source material, Si source material, and Pn source material is 1:1-3:7-10:11-13, for example, 1:1:7:11, 1:2:7:11, 1:3:7:11, 1:1:7:12, 1:2:7:12, 1:3:7:12, or 1:3:8:12.

[0027] In some embodiments, the barium gallium phosphide compound BaGaSi7P 11 BaGa2Si7P 12The preparation method includes mixing Ba source material, Ga source material, Si source material and P source material, grinding, and calcining at high temperature to obtain the barium gallium phosphosilicate compound.

[0028] According to an exemplary embodiment of the present invention, the molar ratio of elements Ba, Ga, Si, and P in the Ba source material, Ga source material, Si source material, and P source material is 1:1-3:7-10:11-13, for example, 1:1:7:11, 1:2:7:11, 1:3:7:11, 1:1:7:12, 1:2:7:12, 1:3:7:12, or 1:3:8:12.

[0029] In some embodiments, the arsenic-silicon-gallium-barium compound BaGa2Si7As 12 The preparation method includes: mixing Ba source material, Ga source material, Si source material and As source material, grinding, and calcining at high temperature to obtain the arsenic silicon gallium barium compound.

[0030] According to an exemplary embodiment of the present invention, the molar ratio of elements Ba, Ga, Si, and As in the Ba source material, Ga source material, Si source material, and As source material is 1:1-3:7-10:11-13, for example, 1:1:7:11, 1:2:7:11, 1:3:7:11, 1:1:7:12, 1:2:7:12, 1:3:7:12, or 1:3:8:12.

[0031] In some embodiments, the arsenic silicon indium barium compound BaIn2Si7As 12 The preparation method includes: mixing Ba source material, In source material, Si source material and As source material, grinding, and calcining at high temperature to obtain the arsenic silicon indium barium compound.

[0032] According to an exemplary embodiment of the present invention, the molar ratio of elements Ba, In, Si, and As in the Ba source material, In source material, Si source material, and As source material is 1:1-3:7-10:11-13, for example, 1:1:7:11, 1:2:7:11, 1:3:7:11, 1:1:7:12, 1:2:7:12, 1:3:7:12, or 1:3:8:12.

[0033] According to an embodiment of the present invention, the preparation method includes: mixing Ba source material, Zn material, Si source material and Pn source material, grinding, and calcining at high temperature to obtain the BaZn. y Si 7+z Pn 10+n Compounds.

[0034] According to an exemplary embodiment of the present invention, the molar ratio of elements Ba, Zn, Si, and Pn in the Ba source material, Zn source material, Si source material, and Pn source material is 1:1-3:8-10:12-15, for example, 1:1:8:12, 1:2:8:12, 1:2.5:8:12, 1:3:8:12, 1:2:9:12, 1:2.5:9.5:12, 1:2.5:9.5:13, 1:2.5:9.5:14, 1:2.5:9.5:15, or 1:3:10:15.

[0035] In some embodiments, the phosphorus-silicon-zinc-barium compound BaZnSi8P 12 BaZn 2.5 Si 9.5 P 15 The preparation method includes: mixing Ba source material, Zn source material, Si source material and P source material, grinding, and calcining at high temperature to obtain the phosphorus silicon zinc barium compound.

[0036] According to an exemplary embodiment of the present invention, the molar ratio of elements Ba, Zn, Si, and P in the Ba source material, Zn source material, Si source material, and P source material is 1:1-3:8-10:12-15, for example, 1:1:8:12, 1:2:8:12, 1:2.5:8:12, 1:3:8:12, 1:2:9:12, 1:2.5:9.5:12, 1:2.5:9.5:13, 1:2.5:9.5:14, 1:2.5:9.5:15, or 1:3:10:15.

[0037] The present invention also provides a nonlinear optical crystal with the chemical formula BaM x Zn y Si 7+z Pn 10+n ;in: M is selected from Al, Ga, or In; Pn is selected from P or As; x is an integer between 0 and 3, for example, x = 0, 1, 2 or 3; y is between 0 and 3, for example, y = 0, 1, 2, 2.5 or 3; and x and y are not both 0 at the same time; z is between 0 and 3, for example, z = 0, 1, 2, 2.5 or 3; n is an integer from 1 to 5, for example, n = 1, 2, 3, 4 or 5.

[0038] According to an embodiment of the present invention, the chemical formula of the nonlinear optical crystal is BaM x Si7Pn 10+nWhere: M is selected from Al, Ga or In; Pn is selected from P or As; x is an integer from 1 to 3, for example x=1 or 2; n is an integer from 1 to 3, for example, n=1 or 2.

[0039] According to an embodiment of the present invention, the chemical formula of the nonlinear optical crystal is BaZn. y Si 7+z Pn 10+n Where: Pn is selected from P or As; z is 1 to 3, for example, z = 1, 2, 2.5 or 3; n is an integer from 2 to 5, for example, n = 2, 3, 4 or 5.

[0040] According to an embodiment of the present invention, the nonlinear optical crystal is a barium gallium phosphide (BaGaSi7P) nonlinear optical crystal. 11 Barium gallium phosphide nonlinear optical crystal BaGa2Si7P 12 Barium arsenide-silicon-gallium-barium nonlinear optical crystal BaGa2Si7As 12 Barium indium arsenide nonlinear optical crystal BaIn2Si7As 12 nonlinear optical crystal BaZnSi8P phosphorus silicon zinc barium 12 Or, a nonlinear optical crystal made of phosphorus, silicon, zinc, and barium (BaZn). 2.5 Si 9.5 P 15 .

[0041] According to an embodiment of the present invention, the barium gallium phosphate nonlinear optical crystal BaGaSi7P 11 It belongs to the triclinic crystal system, and its structural diagram is shown below. Figure 1 As shown; the space group is P 1. The unit cell parameters are: a = 8.11-8.12 Å, b = 8.84-8.85 Å, c = 12.58-12.59 Å, α = 90°. o β = 105 o γ = 111 o z=2. V= 804-805 Å 3 .

[0042] Preferably, the barium gallium phosphide gallium phosphate nonlinear optical crystal is BaGaSi7P. 11 The unit cell parameters are: a = 8.1189 Å, b = 8.8472 Å, c = 12.5802 Å, α = 90.455 o β = 105.317 o γ = 111.561 o z=2. V = 804.97 Å 3 .

[0043] According to an embodiment of the present invention, the barium gallium phosphate nonlinear optical crystal BaGa2Si7P 12 It belongs to the trigonal crystal system, and its structural diagram is shown below. Figure 2 As shown; the space group is R 3. The unit cell parameters are: a = 13.10-13.11 Å, b = 13.10-13.11 Å, c = 8.89-8.90 Å, α = β = 90 o , γ =120, z=3. V= 1323-1324 Å 3 .

[0044] Preferably, the barium gallium phosphide nonlinear optical crystal is BaGa2Si7P. 12 The unit cell parameters are: a = 13.1030 Å, b = 13.1030 Å, c = 8.8996 Å, α = β = 90°. o , γ =120, z=3. V = 1323.3 Å 3 .

[0045] According to an embodiment of the present invention, the barium arsenide-silicon-gallium-barium nonlinear optical crystal BaGa2Si7As 12 It belongs to the trigonal crystal system, and its structural diagram is shown below. Figure 2 As shown; the space group is R 3. The unit cell parameters are: a = 13.63-13.64 Å, b = 13.63-13.64 Å, c = 9.26-9.27 Å, α = β = 90° o , γ =120, z=3, V= 1491-1492 Å 3 .

[0046] Preferably, the barium arsenide-silicon-gallium-barium nonlinear optical crystal BaGa2Si7As 12 The unit cell parameters are: a = 13.6362 Å, b = 13.6362 Å, c = 9.2608 Å, α = β = 90°. o , γ =120, z=3, V = 1491.3 Å 3 .

[0047] According to an embodiment of the present invention, the arsenic silicon indium barium nonlinear optical crystal BaIn2Si7As 12 It belongs to the trigonal crystal system, and its structural diagram is shown below. Figure 2 As shown; the space group is R 3. The unit cell parameters are: a = 13.78-13.79 Å, b = 13.78-13.79 Å, c = 9.35-9.36 Å, α = β = 90°o , γ =120, z=3, V= 1540-1541 Å 3 .

[0048] Preferably, the arsenic silicon indium barium nonlinear optical crystal BaIn2Si7As 12 The unit cell parameters are: a = 13.7845 Å, b = 13.7845 Å, c = 9.3599 Å, α = β = 90°. o , γ =120, z=3, V = 1540.22 Å 3 .

[0049] According to an embodiment of the present invention, the nonlinear optical crystal BaZnSi8P... 12 It belongs to the trigonal crystal system, and its structural diagram is shown below. Figure 3 As shown; the space group is R 3. The unit cell parameters are: a = 13.05-13.06 Å, b = 13.05-13.06 Å, c = 8.86-8.87 Å, α = β = 90° o , γ =120, z=3, V= 1308-1309 Å 3 .

[0050] Preferably, the nonlinear optical crystal BaZnSi8P is a phosphorus-silicon-zinc-barium alloy. 12 The unit cell parameters are: a = 13.0528 Å, b = 13.0528 Å, c = 8.8655 Å, α = β = 90°. o , γ =120, z=3, V = 1308.10 Å 3 .

[0051] According to an embodiment of the present invention, the barium phosphorus silicon zinc nonlinear optical crystal BaZn 2.5 Si 9.5 P 15 It belongs to the cubic crystal system, and its structural diagram is shown below. Figure 4 As shown; the space group is I 3 m The unit cell parameters are: a = 10.39–10.40 Å, b = 10.39–10.40 Å, c = 10.39–10.40 Å, α = β = γ = 90°. o z=2, V= 1123-1124 Å 3 .

[0052] Preferably, the nonlinear optical crystal BaZn is a phosphorus-silicon-zinc-barium crystal. 2.5 Si 9.5 P 15The unit cell parameters are: a = 10.3966 Å, b = 10.3966 Å, c = 10.3966 Å, α = β = γ = 90°. o z=2. V = 1123.76 Å 3 .

[0053] The present invention also provides a method for preparing the above-mentioned nonlinear optical crystal, which adopts a co-solvent method. The preparation method includes: mixing Ba source material, M source material, Zn source material, Si source material and Pn source material, adding co-solvent, grinding, calcining at high temperature, cooling and washing away the co-solvent to obtain the nonlinear optical crystal.

[0054] According to an embodiment of the present invention, the M source material is provided by Ga source material and In source material.

[0055] According to an embodiment of the present invention, the Pn source material is provided by a P source material or an As source material.

[0056] According to an embodiment of the present invention, the molar ratio of elements Ba, M, Zn, Si, and Pn in the Ba source material, M source material, Zn source material, Si source material, and Pn source material is 1:0-3:0-3:7-10:11-15, for example, 1:1:0:7:11, 1:2:0:7:11, 1:3:0:7:11, 1:1:0:7:12, or 1:2:0:7:12. 1:3:0:7:12, 1:0:1:8:12, 1:0:2:8:12, 1:0:2.5:8:12, 1:0:3:8:12, 1:0:2:9:12, 1:0:2.5:9.5:12, 1:0:2.5:9.5:13, 1:0:2.5:9.5:14, 1:0:2.5:9.5:15 or 1:0:3:10:15.

[0057] According to an embodiment of the present invention, the Ba source material is selected from elemental Ba.

[0058] According to an embodiment of the present invention, the Ga source material is selected from elemental Ga, GaAs, or GaP.

[0059] According to an embodiment of the present invention, the Si source material is selected from elemental Si.

[0060] According to an embodiment of the present invention, the P source material is selected from elemental P or GaP, Zn3P2.

[0061] According to an embodiment of the present invention, the As source material is selected from elemental As, InAs, or GaAs.

[0062] According to an embodiment of the present invention, the In source material is selected from elemental In or InAs.

[0063] According to an embodiment of the present invention, the Zn source material is selected from elemental Zn or Zn3P2.

[0064] According to an embodiment of the present invention, the co-solvent is selected from BaBr2 or BaCl2.

[0065] According to an embodiment of the present invention, the high-temperature calcination temperature of the co-solvent method is 900℃-1100℃, for example, 900℃, 950℃, 980℃, 1000℃, 1050℃, 1080℃, or 1100℃. Preferably, the heating rate of the high-temperature calcination is 20℃ / h-80℃ / h, for example, 30-40℃ / h, exemplarily 20℃ / h, 50℃ / h, or 80℃ / h. Preferably, the calcination time is 24 hours-120 hours, for example, 24 hours, 36 hours, 48 ​​hours, 60 hours, 72 hours, 80 hours, 96 hours, or 120 hours.

[0066] According to an embodiment of the present invention, the preparation method further includes cooling after high-temperature calcination using a co-solvent method. Preferably, the cooling refers to reducing the temperature at a rate of 1℃ / h-5℃ / h (e.g., 1℃ / h, 3℃ / h, or 5℃ / h) to 700℃-300℃ (e.g., 300℃, 400℃, 500℃, 600℃, or 700℃), and then reducing it to room temperature.

[0067] According to an embodiment of the present invention, the preparation method of the nonlinear optical crystal includes: mixing Ba source material, M material, Si source material and Pn source material, adding a fluxing agent, grinding, calcining at high temperature, cooling and washing away the fluxing agent to obtain the BaM x Si7Pn 10+n Nonlinear optical crystals.

[0068] According to an exemplary embodiment of the present invention, the molar ratio of elements Ba, M, Si, and Pn in the Ba source material, M source material, Si source material, and Pn source material is 1:1-3:7-10:11-13, for example, 1:1:7:11, 1:2:7:11, 1:3:7:11, 1:1:7:12, 1:2:7:12, 1:3:7:12, or 1:3:8:12.

[0069] According to an exemplary embodiment of the present invention, the method for preparing the nonlinear optical crystal includes: mixing and grinding Ba source material, M source material, Si source material, Pn source material and a co-solvent, heating to 900℃-1100℃ at a rate of 20℃ / h-80℃ / h, and calcining at a constant temperature for 24 hours-120 hours; then cooling to 700℃-300℃ at a rate of 1℃ / h-5℃ / h, and washing away the co-solvent with deionized water after cooling to obtain the nonlinear optical crystal.

[0070] According to an exemplary embodiment of the present invention, the barium gallium gallium phosphate nonlinear optical crystal BaGaSi7P 11 BaGa2Si7P 12 The preparation method includes: mixing and grinding Ba source material, Ga source material, Si source material, P source material and co-solvent, calcining at high temperature, cooling and washing away the co-solvent with deionized water to obtain the barium gallium phosphosilicate nonlinear optical crystal.

[0071] According to an exemplary embodiment of the present invention, the barium arsenide-silicon-gallium-barium nonlinear optical crystal BaGa2Si7As 12 The preparation method includes: mixing and grinding Ba source material, Ga source material, Si source material, As source material and co-solvent, calcining at high temperature, cooling and washing away the co-solvent with deionized water to obtain the arsenic silicon gallium barium nonlinear optical crystal.

[0072] According to an exemplary embodiment of the present invention, the arsenic silicon indium barium nonlinear optical crystal BaIn2Si7As 12 The preparation method includes: mixing and grinding Ba source material, In source material, Si source material, As source material and co-solvent, calcining at high temperature, cooling and washing away the co-solvent with deionized water to obtain the arsenic silicon indium barium nonlinear optical crystal.

[0073] According to an embodiment of the present invention, the method for preparing the nonlinear optical crystal includes: mixing Ba source material, Zn material, Si source material and Pn source material, adding a fluxing agent, grinding, calcining at high temperature, cooling and washing away the fluxing agent to obtain the BaZn. y Si 7+z Pn 10+n Compounds.

[0074] According to an exemplary embodiment of the present invention, the molar ratio of elements Ba, Zn, Si, and Pn in the Ba source material, Zn source material, Si source material, and Pn source material is 1:1-3:8-10:12-15, for example, 1:1:8:12, 1:2:8:12, 1:2.5:8:12, 1:3:8:12, 1:2:9:12, 1:2.5:9.5:12, 1:2.5:9.5:13, 1:2.5:9.5:14, 1:2.5:9.5:15, or 1:3:10:15.

[0075] According to an exemplary embodiment of the present invention, the nonlinear optical crystal BaZnSi8P... 12 BaZn 2.5 Si 9.5 P 15The preparation method includes: mixing and grinding Ba source material, Zn source material, Si source material, P source material and co-solvent, calcining at high temperature, cooling and washing away the co-solvent with deionized water to obtain the phosphorus-silicon-zinc-barium nonlinear optical crystal.

[0076] According to an exemplary embodiment of the present invention, the molar ratio of element Ba to flux in the Ba source material is 1:4-10, for example, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

[0077] The present invention also provides the use of the above-mentioned nonlinear optical crystal, preferably in the field of nonlinear optics or in the mid-infrared band, for example in nonlinear optical devices.

[0078] The present invention also provides a nonlinear optical device, the nonlinear optical device comprising the above-mentioned chemical formula BaM x Zn y Si 7+z Pn 10+n Compounds and / or nonlinear optical crystals.

[0079] According to an embodiment of the present invention, in the nonlinear optical device, at least one beam of incident electromagnetic radiation is passed through at least one nonlinear optical crystal to generate at least one beam of output radiation with a frequency different from the incident electromagnetic radiation.

[0080] According to embodiments of the present invention, the nonlinear optical device includes, but is not limited to, at least one of an infrared laser frequency converter, an infrared electro-optic device, an infrared communication device, an infrared laser guidance device, and an infrared optoelectronic countermeasures system.

[0081] Beneficial effects The present invention relates to the nonlinear optical crystal BaGaSi7P of silicon gallium barium. 11 Barium gallium phosphide nonlinear optical crystal BaGa2Si7P 12 Barium arsenide, silicon, gallium, barium nonlinear optical crystal BaGa2Si7As 12 Barium indium arsenide, silicon, and arsenic nonlinear optical crystal BaIn2Si7As 12 Nonlinear optical crystals BaZnSi8P (phosphorus silicon zinc barium) 12 nonlinear optical crystals BaZn (phosphorus silicon zinc barium) 2.5 Si 9.5 P 15 It has large nonlinear optical effects (BaGaSi7P) 11 BaGa2Si7P 12 BaGa2Si7As 12 ,BaIn2Si7As 12The harmonic output intensities of BaZnSi8P are approximately 3.1, 5.5, 6.1, and 6.3 times that of AgGaS2 under the same conditions, respectively. 12 BaZn 2.5 Si 9.5 P 15 The frequency harmonic output intensity is approximately 2.6 times and 3.7 times that of ZnGeP2 under the same conditions, respectively, and the laser damage threshold is large (7.5-9.4×AGS). Barium gallium phosphide and barium zinc phosphide nonlinear optical crystals have good infrared transmission performance in the 2.510 micrometer band, while barium gallium arsenide and barium indium arsenide have good infrared transmission performance in the 2.512 micrometer band. They have advantages such as easy growth, high hardness, good mechanical properties, resistance to breakage and deliquescence, and ease of processing and storage. They can be applied in various nonlinear optical fields or in the mid-infrared band (for example, they can be used to prepare infrared laser frequency conversion devices, infrared electro-optic devices, infrared communication devices, or infrared laser guidance devices). Attached Figure Description

[0082] Figure 1 BaGaSi7P is a nonlinear optical crystal made of barium gallium phosphide. 11 A schematic diagram of the crystal structure.

[0083] Figure 2 Barium gallium phosphide, barium gallium arsenide, and barium indium arsenide are nonlinear optical crystals, such as BaGa2Si7P. 12 BaGa2Si7As 12 ,BaIn2Si7As 12 A schematic diagram of the crystal structure.

[0084] Figure 3 BaZnSi8P is a nonlinear optical crystal made of phosphorus, silicon, zinc, and barium. 12 A schematic diagram of the crystal structure.

[0085] Figure 4 BaZn is a nonlinear optical crystal made of phosphorus, silicon, zinc and barium. 2.5 Si 9.5 P 15 A schematic diagram of the crystal structure.

[0086] Figure 5 The nonlinear optical crystal BaGaSi7P obtained in Example 1 is a biphosphorus gallium gallium barium phosphate crystal. 11 Optical bandgap diagram.

[0087] Figure 6 The nonlinear optical crystal BaGa2Si7P obtained in Example 2 is a phosphosilicon gallium barium nonlinear optical crystal. 12 Optical bandgap diagram.

[0088] Figure 7The nonlinear optical crystal BaGa2Si7As obtained in Example 3 is an example of this. 12 Optical bandgap diagram.

[0089] Figure 8 The nonlinear optical crystal BaIn2Si7As obtained in Example 4 is an example of this. 12 Optical bandgap diagram.

[0090] Figure 9 The nonlinear optical crystal BaZnSi8P obtained in Example 5 is a phosphorus-silicon-zinc-barium crystal. 12 Optical bandgap diagram.

[0091] Figure 10 The nonlinear optical crystal BaZn phosphorus silicon zinc barium obtained in Example 6 2.5 Si 9.5 P 15 Optical bandgap diagram.

[0092] Figure 11 The nonlinear optical crystal BaGaSi7P obtained in Example 1 is a biphosphorus gallium gallium barium phosphate crystal. 11 Comparison of X-ray powder diffraction and simulated X-ray diffraction.

[0093] Figure 12 The nonlinear optical crystal BaGa2Si7P obtained in Example 2 is a phosphosilicon gallium barium nonlinear optical crystal. 12 Comparison of X-ray powder diffraction and simulated X-ray diffraction.

[0094] Figure 13 The nonlinear optical crystal BaGa2Si7As obtained in Example 3 is an example of this. 12 Comparison of X-ray powder diffraction and simulated X-ray diffraction.

[0095] Figure 14 The nonlinear optical crystal BaIn2Si7As obtained in Example 4 is an example of this. 12 Comparison of X-ray powder diffraction and simulated X-ray diffraction.

[0096] Figure 15 The nonlinear optical crystal BaZnSi8P obtained in Example 5 is a phosphorus-silicon-zinc-barium crystal. 12 Comparison of X-ray powder diffraction and simulated X-ray diffraction.

[0097] Figure 16 The nonlinear optical crystal BaZn phosphorus silicon zinc barium obtained in Example 6 2.5 Si 9.5 P 15 Comparison of X-ray powder diffraction and simulated X-ray diffraction.

[0098] Figure 17The nonlinear optical crystal BaGaSi7P obtained in Example 1 is a phosphosilicon gallium barium nonlinear optical crystal. 11 The infrared transmission spectrum was measured after the material was ground into powder.

[0099] Figure 18 The nonlinear optical crystal BaGa2Si7P obtained in Example 2 is a phosphosilicon gallium barium nonlinear optical crystal. 12 The infrared transmission spectrum was measured after the material was ground into powder.

[0100] Figure 19 The nonlinear optical crystal BaGa2Si7As obtained in Example 3 is an example of this. 12 The infrared transmission spectrum was measured after the material was ground into powder.

[0101] Figure 20 The nonlinear optical crystal BaIn2Si7As obtained in Example 4 is an example of this. 12 The infrared transmission spectrum was measured after the material was ground into powder.

[0102] Figure 21 The nonlinear optical crystal BaZnSi8P obtained in Example 5 is a phosphorus-silicon-zinc-barium crystal. 12 The infrared transmission spectrum was measured after the material was ground into powder.

[0103] Figure 22 The nonlinear optical crystal BaZn phosphorus silicon zinc barium obtained in Example 6 2.5 Si 9.5 P 15 The infrared transmission spectrum was measured after the material was ground into powder.

[0104] Figure 23 The nonlinear optical crystals BaGaSi7P obtained in Examples 1, 2, 5, and 6 are shown. 11 Barium gallium phosphide nonlinear optical crystal BaGa2Si7P 12 Nonlinear optical crystals BaZnSi8P (phosphorus silicon zinc barium) 12 nonlinear optical crystals BaZn (phosphorus silicon zinc barium) 2.5 Si 9.5 P 15 The frequency doubling intensity versus sample particle size curve of commercially available AgGaS2 crystal.

[0105] Figure 24 The nonlinear optical crystals BaGa2Si7As obtained in Examples 3 and 4 are examples of this type. 12 Barium indium arsenide, silicon, and arsenic nonlinear optical crystal BaIn2Si7As 12 The frequency doubling intensity versus sample particle size curve of commercially available ZnGeP2 crystals. Detailed Implementation

[0106] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0107] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0108] Example 1 BaGaSi7P synthesized by flux method 11 The specific operating steps for the barium gallium phosphosilicate nonlinear optical crystal are as follows: The raw materials Ba elemental, GaP compound, Si elemental, P elemental, and BaBr2 co-solvent were uniformly mixed and ground in a molar ratio of 1:2:4:11:4, then placed into a quartz tube and evacuated to 10°C. -3 Pa was sealed and placed in a muffle furnace; the temperature was increased to 1080℃ at a rate of 50℃ / h and held at that temperature for 72 hours, then decreased to 500℃ at a rate of 3℃ / h. The muffle furnace was then closed, and after cooling to room temperature, the quartz tube was removed, cut open, and the flux BaBr2 was washed away with deionized water. The tube was then dried in an oven to obtain BaGaSi7P. 11 Barium gallium phosphide silicon nonlinear optical crystal. Its crystal structure is as follows: Figure 1 As shown, its X-ray powder diffraction is as follows: Figure 11 As shown.

[0109] Tests show that BaGaSi7P 11 The space group of the crystal is P 1. The unit cell parameters are: a = 8.1189 Å, b = 8.8472 Å, c = 12.5802 Å, α = 90.455 o β = 105.317 o γ = 111.561 o z=2. V = 804.97 Å 3 .

[0110] Example 2 BaGa2Si7P synthesized by flux method 12 The specific operating steps for the barium gallium phosphosilicate nonlinear optical crystal are as follows: The raw materials Ba elemental, GaP compound, Si elemental, P elemental, and BaBr2 co-solvent were uniformly mixed and ground in a molar ratio of 1:3:8:12:6, then placed into a quartz tube and evacuated to 10°C. -3Pa was sealed and placed in a muffle furnace; the temperature was increased to 1080℃ at a rate of 50℃ / h and held at that temperature for 72 hours, then decreased to 500℃ at a rate of 3℃ / h. The muffle furnace was then closed, and after cooling to room temperature, the quartz tube was removed, cut open, and the flux BaBr2 was washed away with deionized water. The tube was then dried in an oven to obtain BaGa2Si7P. 12 Barium gallium phosphide silicon nonlinear optical crystal. Its crystal structure is as follows: Figure 2 As shown, its X-ray powder diffraction is as follows: Figure 12 As shown.

[0111] Tests show that BaGa2Si7P 12 The space group of the crystal is R 3. The unit cell parameters are: a = 13.1030 Å, b = 13.1030 Å, c = 8.8996 Å, α = β = 90°. o , γ =120, z=3. V = 1323.3 Å 3 .

[0112] Example 3 Synthesis of BaGa2Si7As using a fluxing method 12 The specific operating steps for the arsenic-silicon-gallium-barium nonlinear optical crystal are as follows: The raw materials Ba elemental, GaAs compound, Si elemental, As elemental, and BaCl2 co-solvent were uniformly mixed and ground in a molar ratio of 1:2:8:12:8, then placed into a quartz tube and evacuated to 10°C. -3 Pa was sealed and placed in a muffle furnace; the temperature was increased to 900℃ at a rate of 50℃ / h and held at that temperature for 72 hours, then decreased to 300℃ at a rate of 3℃ / h. The muffle furnace was then closed, and after cooling to room temperature, the quartz tube was removed, cut open, and the flux BaCl2 was washed away with deionized water. The tube was then dried in an oven to obtain BaGa2Si7As. 12 Arsenic, silicon, gallium, barium nonlinear optical crystal. Its crystal structure is as follows: Figure 2 As shown, its X-ray powder diffraction is as follows: Figure 13 As shown.

[0113] Tests show that BaGa2Si7As 12 The space group of the crystal is R 3. The unit cell parameters are: a = 13.6362 Å, b = 13.6362 Å, c = 9.2608 Å, α = β = 90°. o , γ =120, z=3. V = 1491.3 Å 3 .

[0114] Example 4 Synthesis of BaIn2Si7As by flux method 12The specific operating steps for using barium indium arsenide silicon nonlinear optical crystals are as follows: The raw materials Ba elemental, InAs compound, Si elemental, As elemental, and BaCl2 co-solvent were uniformly mixed and ground in a molar ratio of 1:2:8:12:8, then placed into a quartz tube and evacuated to 10°C. -3 Pa was sealed and placed in a muffle furnace; the temperature was increased to 900℃ at a rate of 50℃ / h and held at that temperature for 72 hours, then decreased to 300℃ at a rate of 3℃ / h. The muffle furnace was then closed, and after cooling to room temperature, the quartz tube was removed, cut open, and the flux BaCl2 was washed away with deionized water. The tube was then dried in an oven to obtain BaIn2Si7As. 12 Arsenic-silicon-indium-barium nonlinear optical crystal. Its crystal structure is as follows: Figure 2 As shown, its X-ray powder diffraction is as follows: Figure 14 As shown.

[0115] Tests show that BaIn2Si7As 12 The space group of the crystal is R 3. The unit cell parameters are: a = 13.7845 Å, b = 13.7845 Å, c = 9.3599 Å, α = β = 90°. o , γ =120, z=3. V = 1540.22 Å 3 .

[0116] Example 5 Synthesis of BaZnSi8P using a fluxing method 12 The specific operating steps for the nonlinear optical crystal made of phosphorus silicon zinc barium are as follows: The raw materials Ba elemental, Zn3P2 compound, Si elemental, P elemental, and BaCl2 co-solvent were uniformly mixed and ground in a molar ratio of 1:1:8:12:5, then placed into a quartz tube and evacuated to 10°C. -3 Pa was sealed and placed in a muffle furnace; the temperature was increased to 1050℃ at a rate of 50℃ / h and held at that temperature for 120 hours, then decreased to 500℃ at a rate of 3℃ / h. The muffle furnace was then closed, and after cooling to room temperature, the quartz tube was removed, cut open, and the flux BaCl2 was washed away with deionized water. The tube was then dried in an oven to obtain BaZnSi8P. 12 Phosphorus-silicon-zinc-barium nonlinear optical crystal. Its crystal structure is as follows: Figure 3 As shown, its X-ray powder diffraction is as follows: Figure 15 As shown.

[0117] Tests show that BaZnSi8P 12 The space group of the crystal is R 3. The unit cell parameters are: a = 13.0528 Å, b = 13.0528 Å, c = 8.8655 Å, α = β = 90°. o, γ =120, z=3. V = 1308.10 Å 3 .

[0118] Example 6 Synthesis of BaZn using flux method 2.5 Si 9.5 P 15 The specific operating steps for the nonlinear optical crystal made of phosphorus silicon zinc barium are as follows: The raw materials Ba, Zn, Si, P, and BaCl2 flux were uniformly mixed and ground in a molar ratio of 1:2.5:9.5:15:6, then placed into a quartz tube and evacuated to 10°C. -3 Pa was sealed and placed in a muffle furnace; the temperature was increased to 1050℃ at a rate of 50℃ / h and held at that temperature for 120 hours, then decreased to 500℃ at a rate of 3℃ / h. The muffle furnace was then closed, and after cooling to room temperature, the quartz tube was removed, cut open, and the flux BaCl2 was washed away with deionized water. The tube was then dried in an oven to obtain BaZn. 2.5 Si 9.5 P 15 Phosphorus-silicon-zinc-barium nonlinear optical crystal. Its crystal structure is as follows: Figure 4 As shown, its X-ray powder diffraction is as follows: Figure 16 As shown.

[0119] Tests have shown that BaZn 2.5 Si 9.5 P 15 The space group of the crystal is I 3 m The unit cell parameters are: a = 10.3966 Å, b = 10.3966 Å, c = 10.3966 Å, α = β = γ = 90°. o z=2. V = 1123.76 Å 3 .

[0120] Example 7 The BaGaSi7P obtained in Examples 1-6 11 Barium gallium phosphide, BaGa2Si7P 12 Barium gallium phosphide, BaGa2Si7As 12 Arsenic, silicon, gallium, barium, BaIn2Si7As 12 Arsenic, silicon, indium, barium, BaZnSi8P 12 Phosphorus, silicon, zinc, barium, BaZn 2.5 Si 9.5 P 15 Phosphorus-silicon-zinc-barium nonlinear optical crystals were ground into powders with a particle size of approximately 1.8 micrometers. The infrared transmission spectra of each crystal were measured as follows: Figure 17-22 As shown, the results indicate that BaGaSi7P 11Barium gallium phosphide, BaGa2Si7P 12 Barium gallium phosphide, BaZnSi8P 12 Phosphorus, silicon, zinc, barium, BaZn 2.5 Si 9.5 P 15 Barium zinc phosphate (BSP) nonlinear optical crystals exhibit good infrared transmittance in the 2.5-10 micrometer wavelength range; BaGa2Si7As 12 Arsenic, silicon, gallium, barium, BaIn2Si7As 12 The barium indium arsenide nonlinear optical crystal has good infrared transmission performance in the 2.512 micrometer band.

[0121] Example 8 The nonlinear optical crystal BaGaSi7P obtained in Example 1 11 The nonlinear optical crystal BaGa2Si7P obtained in Example 2 12 The nonlinear optical crystal BaZnSi8P obtained in Example 5 12 The nonlinear optical crystal BaZn obtained in Example 6 2.5 Si 9.5 P 15 Commercially available AgGaS2 crystals (denoted as AGS) were sieved through a sieve to obtain six particle size ranges (25-40μm, 40-60μm, 60μm-75μm, 75-110μm, 110-150μm, and 150-220μm). These were then placed in six sample boxes for frequency doubling effect testing. The frequency doubling intensity versus sample particle size curve under 2.05 μm laser testing is shown in [Figure number missing]. Figure 23 .from Figure 23 As can be seen from this, BaGaSi7P 11 BaGa2Si7P 12 、BaZnSi8P 12 BaZn 2.5 Si 9.5 P 15 The harmonic intensities were 3.1 times, 5.5 times, 6.1 times, and 6.3 times that of AgGaS2, respectively.

[0122] Example 9 The nonlinear optical crystal BaGa2Si7As obtained in Examples 3 and 4 12 ,BaIn2Si7As 12Commercially available ZnGeP2 crystals (denoted as ZGP) were sieved through a sieve to obtain six particle size ranges (25-40μm, 40-60μm, 60μm-75μm, 75-110μm, 110-150μm, and 150-220μm). These were then placed in six sample boxes for frequency doubling effect testing. The frequency doubling intensity versus sample particle size curve under 2.05 μm laser testing is shown in [Figure number missing]. Figure 24 .from Figure 24 As can be seen from BaGa2Si7As 12 ,BaIn2Si7As 12 The harmonic intensities were 2.6 times and 3.7 times that of ZnGeP2, respectively.

[0123] The exemplary embodiments of the present invention have been described above. However, the scope of protection of this application is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A chemical formula BaM x Zn y Si 7+z Pn 10+n The compound, characterized in that, in: M is selected from Al, Ga, or In; Pn is selected from P or As; x is an integer between 0 and 3; y is between 0 and 3; and x and y are not both 0 at the same time; z is 0~3; n is an integer from 1 to 5.

2. The compound according to claim 1, characterized in that, The BaM x Zn y Si 7+z Pn 10+n The compound is BaM x Si7Pn 10+n wherein: M is selected from Al, Ga or In; Pn is selected from P or As; x is an integer from 1 to 3; n is an integer from 1 to 3; and / or, the BaM x Zn y Si 7+z Pn 10+n compound is BaZn y Si 7+z Pn 10+n wherein: Pn is selected from P or As; z is 1~3; n is an integer from 2 to 5; And / or, the BaM x Zn y Si 7+z Pn 10+n The compound is barium gallium phosphide, specifically BaGaSi7P. 11 BaGa2Si7P 12 Or arsenic-silicon-gallium-barium compound BaGa2Si7As 12 Or arsenic, silicon, indium, barium compounds BaIn2Si7As 12 Or a compound of phosphorus, silicon, zinc, and barium (BaZnSi8P) 12 ,BaZn 2.5 Si 9.5 P 15 .

3. The BaM as described in claim 1 x Zn y Si 7+z Pn 10+n A method for preparing a compound, characterized in that, The preparation method includes: mixing Ba source material, M material, Zn source material, Si source material and Pn source material, grinding, and calcining at high temperature to obtain the BaM. x Zn y Si 7+z Pn 10+n Compounds.

4. The preparation method according to claim 3, characterized in that, The M source material is provided by Ga source material and In source material; And / or, the Pn source material is provided by a P source material or an As source material; And / or, in the Ba source material, M source material, Zn source material, Si source material, and Pn source material, the molar ratio of elements Ba, M, Zn, Si, and Pn is 1:0-3:0-3:7-10:11-15; And / or, the Ba source material is selected from elemental Ba; And / or, the Ga source material is selected from elemental Ga, GaAs, or GaP; And / or, the Si source material is selected from elemental Si; And / or, the P source material is selected from elemental P or GaP, Zn3P2; And / or, the As source material is selected from elemental As, InAs, or GaAs; And / or, the In source material is selected from elemental In or InAs; And / or, the Zn source material is selected from elemental Zn or Zn3P2; And / or, the high-temperature calcination temperature is 900℃-1100℃; And / or, the heating rate of the high-temperature calcination is 20℃ / h-80℃ / h; And / or, the high-temperature calcination time is 24-120 hours.

5. A nonlinear optical crystal, characterized in that, Its chemical formula is BaM x Zn y Si 7+z Pn 10+n ; in: M is selected from Al, Ga, or In; Pn is selected from P or As; x is an integer between 0 and 3; y is between 0 and 3; and x and y are not both 0 at the same time; z is 0~3; n is an integer from 1 to 5.

6. The nonlinear optical crystal as described in claim 5, characterized in that, The chemical formula of the nonlinear optical crystal is BaM x Si7Pn 10+n Where: M is selected from Al, Ga, or In; Pn is selected from P or As; x is an integer from 1 to 3; n is an integer from 1 to 3; And / or, the chemical formula of the nonlinear optical crystal is BaZn. y Si 7+z Pn 10+n Where: Pn is selected from P or As; z is 1~3; n is an integer from 2 to 5; And / or, the nonlinear optical crystal is a barium gallium phosphide gallium phosphide (BaGaSi7P) nonlinear optical crystal. 11 Barium gallium phosphide nonlinear optical crystal BaGa2Si7P 12 Barium arsenide-silicon-gallium-barium nonlinear optical crystal BaGa2Si7As 12 Barium indium arsenide nonlinear optical crystal BaIn2Si7As 12 nonlinear optical crystal BaZnSi8P phosphorus silicon zinc barium 12 Or, a nonlinear optical crystal made of phosphorus, silicon, zinc, and barium (BaZn). 2.5 Si 9.5 P 15 ; And / or, the barium gallium phosphide gallium phosphate nonlinear optical crystal BaGaSi7P 11 It belongs to the triclinic crystal system, and its structural diagram is shown in Figure 1; the space group is P 1. The unit cell parameters are: a = 8.11-8.12 Å, b = 8.84-8.85 Å, c = 12.58-12.59 Å, α = 90°. o β = 105 o γ = 111 o z=2. V= 804-805 Å 3 ; And / or, the barium gallium phosphide gallium phosphate nonlinear optical crystal BaGaSi7P 11 The unit cell parameters are: a = 8.1189 Å, b = 8.8472 Å, c = 12.5802 Å, α = 90.455 o β = 105.317 o γ = 111.561 o z=2. V = 804.97 Å 3 ; And / or, the barium gallium phosphide nonlinear optical crystal BaGa2Si7P 12 It belongs to the trigonal crystal system, and its structural diagram is shown in Figure 2; the space group is R 3. The unit cell parameters are: a = 13.10-13.11 Å, b = 13.10-13.11 Å, c = 8.89-8.90 Å, α = β = 90°. o , γ =120, z=3. V= 1323-1324 Å 3 ; And / or, the barium gallium phosphide nonlinear optical crystal BaGa2Si7P 12 The unit cell parameters are: a = 13.1030 Å, b = 13.1030 Å, c = 8.8996 Å, α = β = 90°. o , γ =120, z=3. V = 1323.3 Å 3 ; And / or, the barium arsenide-silicon-gallium-barium nonlinear optical crystal BaGa2Si7As 12 It belongs to the trigonal crystal system, and its structural diagram is shown in Figure 2; the space group is R 3. The unit cell parameters are: a = 13.63-13.64 Å, b = 13.63-13.64 Å, c = 9.26-9.27 Å, α = β = 90 o , γ =120, z=3, V= 1491-1492 Å 3 ; And / or, the barium arsenide-silicon-gallium-barium nonlinear optical crystal BaGa2Si7As 12 The unit cell parameters are: a = 13.6362 Å, b = 13.6362 Å, c = 9.2608 Å, α = β = 90°. o , γ =120, z=3, V = 1491.3 Å 3 ; And / or, the arsenic silicon indium barium nonlinear optical crystal BaIn2Si7As 12 It belongs to the trigonal crystal system, and its structural diagram is shown in Figure 2; the space group is R 3. The unit cell parameters are: a = 13.78-13.79 Å, b = 13.78-13.79 Å, c = 9.35-9.36 Å, α = β = 90 o , γ =120, z=3, V= 1540-1541 Å 3 ; And / or, the arsenic silicon indium barium nonlinear optical crystal BaIn2Si7As 12 The unit cell parameters are: a = 13.7845 Å, b = 13.7845 Å, c = 9.3599 Å, α = β = 90°. o , γ =120, z=3, V = 1540.22 Å 3 ; And / or, the barium zinc phosphorus nonlinear optical crystal BaZnSi8P 12 It belongs to the trigonal crystal system, and its structural diagram is shown in Figure 3; the space group is R 3. The unit cell parameters are: a = 13.05-13.06 Å, b = 13.05-13.06 Å, c = 8.86-8.87 Å, α = β = 90°. o , γ =120, z=3, V= 1308-1309 Å 3 ; And / or, the barium zinc phosphorus nonlinear optical crystal BaZnSi8P 12 The unit cell parameters are: a = 13.0528 Å, b = 13.0528 Å, c = 8.8655 Å, α = β = 90°. o , γ =120, z=3, V = 1308.10 Å 3 ; And / or, the barium zinc phosphorus nonlinear optical crystal BaZn 2.5 Si 9.5 P 15 It belongs to the cubic crystal system, and its structural diagram is shown in Figure 4; the space group is I 3 m The unit cell parameters are: a = 10.39–10.40 Å, b = 10.39–10.40 Å, c = 10.39–10.40 Å, α = β = γ = 90°. o z=2, V= 1123-1124 Å 3 ; And / or, the barium zinc phosphorus nonlinear optical crystal BaZn 2.5 Si 9.5 P 15 The unit cell parameters are: a = 10.3966 Å, b = 10.3966 Å, c = 10.3966 Å, α = β = γ = 90°. o z=2. V = 1123.76 Å 3 .

7. The method for preparing the nonlinear optical crystal according to claim 5 or 6, characterized in that, The preparation method includes: mixing Ba source material, M source material, Zn source material, Si source material and Pn source material, adding a co-solvent, grinding, calcining at high temperature, cooling and washing away the co-solvent with deionized water to obtain the nonlinear optical crystal.

8. The preparation method according to claim 7, characterized in that, The M source material is provided by Ga source material and In source material; And / or, the Pn source material is provided by a P source material or an As source material; And / or, in the Ba source material, M source material, Zn source material, Si source material, and Pn source material, the molar ratio of elements Ba, M, Zn, Si, and Pn is 1:0-3:0-3:7-10:11-15; And / or, the Ba source material is selected from elemental Ba; And / or, the Ga source material is selected from elemental Ga, GaAs, or GaP; And / or, the Si source material is selected from elemental Si; And / or, the P source material is selected from elemental P, GaP, or Zn3P2; And / or, the As source material is selected from elemental As, InAs, or GaAs; And / or, the In source material is selected from elemental In or InAs; And / or, the Zn source material is selected from elemental Zn or Zn3P2; And / or, the co-solvent is selected from BaBr2 or BaCl2; And / or, the high-temperature calcination temperature of the co-solvent method is 900℃-1100℃; And / or, the heating rate of the high-temperature calcination is 20℃ / h-80℃ / h; And / or, the calcination time is 24 hours to 120 hours; And / or, the molar ratio of element Ba to flux in the Ba source material is 1:4-10.

9. Use of the nonlinear optical crystal according to claim 5 or 6, preferably in the field of nonlinear optics or in the mid-infrared band, for example in nonlinear optical devices.

10. A nonlinear optical device, characterized in that, The nonlinear optical device includes the nonlinear optical crystal as described in claim 5 or 6.

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