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ZGP

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ZGP

磷锗锌晶体(ZnGeP2,简称ZGP)属于正单轴晶体。是用于光参量振荡器(OPO)技术的最常用的非线性晶体之一,ZGP晶体具有有效非线性系数大(deff=75pm/V,是其他常用非线性晶体的数倍或数十倍),损伤阈值高(>30GW/cm2),宽的透光波段(0.74~12.4μm),吸收系数小(2~3μm的吸收系数小于0.04cm-1),热导率高(360mW/cm·K),性能稳定,制作工艺成熟。能生长出大尺寸的晶体等许多优点.是3~5m波段中红外OPO的理想晶体。

特点

  • 非线性系数大
  • 透射区域为74 μm至12μm
  • 相对损坏阈值高
  • 高导热率
  • 透明区域广泛
  • 宽光谱范围内的相位匹配

参数

物理和化学特性

属性数值
化学式ZnGeP2
晶体结构四方晶系,42m
晶格参数a=b=5.467Å, c=12.736Å
质量密度4.16 g/cm3
莫氏硬度5.5
熔点大约1040°C
导热系数180 W/m/K
热膨胀系数β‖,5×10-6/K; β⊥,7.8×10-6/K
双折射正单轴

非线性光学性质

属性数值
SHG相位匹配范围3177 ∼10357nm (Type I)
NLO系数d36=75 ± 8 pm/V
Type Ⅰ deeo=d36 sin2θcos2φ
Type Ⅱ doeo =deoo=d36 sinθsin2φ
损坏阈值
在2.79 um30 GW/cm2 (150 ps)
在10.6 um 1 GW/cm2  (2 ns)

线性光学性质

属性数值
透明范围0.74 – 12 um
吸收系数α<0.05cm-1 @2050-2100 nm
折光指数 
@ 2.05微米no= 3.1478, ne= 3.1891
@ 2.79微米no= 3.1333, ne= 3.1744
@ 5.30微米no= 3.1136, ne= 3.1547
@ 10.6微米no= 3.0729, ne= 3.1143
Sellmeier方程(λ in μm)no2(λ) = 4.64467+5.10087/(λ2-0.13656)+4.27777λ2/(λ2-1653.89)
ne2(λ) = 4.71539+5.26358/(λ2-0.14386)+2.37310λ2/(λ2-1000.82)

光谱

ZGP传输光谱ZGP的SHG调谐曲线(eeo型)
ZGP的OPO调谐曲线在2800nm的泵浦灯下。ZGP的OPO调谐曲线在2090nm的泵浦灯下。

参考文献

[1]  Huang C ,  Wu H ,  Xiao R , et al. High-pressure-assisted synthesis of high-volume ZnGeP 2 polycrystalline[J]. Journal of Crystal Growth, 2018:S0022024818300411.
[2]  Liu M ,  Zhao B ,  Chen B , et al. Research of thermodynamic properties of mid-infrared single crystal ZnGeP 2[J]. Materials Science in Semiconductor Processing, 2018:S1369800117325908.
[3]  Vasilyeva I G ,  Nikolaev R E ,  Verozubova G A . Nonstoichiometry of ZnGeP2 crystals probed by static tensimetric method[J]. Journal of Solid State Chemistry, 2010, 183(9):2242-2247.
[4]  Yue X ,  Xu M ,  Du W , et al. Surface finishing of ZnGeP2 single crystal by diamond tool turning method[J]. Optical Materials, 2017:S0925346716307704.
[5] D Yang,  Zhao B ,  Chen B , et al. Impurity phases analysis of ZnGeP2 single crystal grown by Bridgman method[J]. Journal of Alloys & Compounds, 2017, 709:125-128.
[6]  Verozubova G A ,  Gribenyukov A I ,  Korotkova V V , et al. ZnGeP2 synthesis and growth from melt[J]. Materials Science and Engineering B, 1997, 48(3):191-197.
[7]  Mengyan P W ,  Baker B B ,  Lichti R L , et al. Hyperfine spectroscopy and characterization of muonium in ZnGeP 2[J]. Physica B Condensed Matter, 2009, 404(23-24):5121-5124.
[8]  Zhang S R ,  Zhu S F ,  Xie L H , et al. Theoretical study of the structural, elastic and thermodynamic properties of chalcopyrite ZnGeP2[J]. Materials Science in Semiconductor Processing, 2015, 38:41-49.
[9]  Lei Z ,  Okunev A O ,  Zhu C , et al. Photoelasticy method for study of structural imperfection of ZnGeP2 crystals[J]. Journal of Crystal Growth, 2016, 450(Complete):34-38.
[10]  Tripathy S K ,  Kumar V . Electronic, elastic and optical properties of ZnGeP2 semiconductor under hydrostatic pressures[J]. Materials Science & Engineering B, 2014, 182(1):52-58.
[11]  Yang D H ,  Zhao B J ,  Chen B J , et al. Growth of ZnGeP 2 single crystals by modified vertical Bridgman method for nonlinear optical devices[J]. Materials Science in Semiconductor Processing, 2017, 67:147-151.
[12]  Vasilyeva I G ,  Demidova M G . Chemical analysis of ZnGeP2 as a new line of research of heterogeneity in bulk crystals[J]. Talanta, 2012, 101(none):187-191.
[13] Chaudhary, K A,  K. S , et al. Generation of terahertz from ZnGeP2 crystal and its application to record the time-resolved photoacoustic spectra of nitromethane.
[14]  Yang C H ,  Wang M ,  Xia S X , et al. Synthesis and Growth of ZnGeP_2 Crystals. Journal of Synthetic Crystals.
[15]  Wang Z ,  Mao M ,  Wu H , et al. Study on annealing of infrared nonlinear optical crystal ZnGeP2[J]. Journal of Crystal Growth, 2012, 359(none):11–14.
[16]  Verozubova G A ,  Okunev A O ,  Gribenyukov A I , et al. Growth and defect structure of ZnGeP2 crystals[J]. Journal of Crystal Growth, 2010, 312(8):1122-1126.
[17]  Verozubova G A ,  Gribenyukov A I ,  Korotkova V V , et al. Synthesis and growth of ZnGeP 2 crystals for nonlinear optical applications[J]. Journal of Crystal Growth, 2000, 213(s 3–4):334-339.
[18]  Fan Q ,  Zhu S ,  Zhao B , et al. Influence of annealing on optical and electrical properties of ZnGeP2 single crystals – ScienceDirect[J]. Journal of Crystal Growth, 2011, 318(1):725-728.
[19]  Hofmann D M ,  Romanov N G ,  Gehlhoff W , et al. Optically detected magnetic resonance experiments on native defects in ZnGeP 2[J]. Physica B Condensed Matter, 2003, 340-342(none):978-981.
[20]  Verozubova G A ,  Okunev A O ,  Gribenyukov A I . Bulk growth of ZnGeP2 crystals and their study by X-ray topography[J]. Journal of Crystal Growth, 2014, 401(sep.1):782-786.
[21]  Wu X X ,  Zheng W C . Research on the EPR parameters and local structure of Cr4+ ion at the tetragonal Ge4+ site in ZnGeP2 crystal[J]. Physica B Physics of Condensed Matter, 2015, 473:72-74.

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