Intrinsic point defects (vacancies and antisites) in CdGeP2 crystals

Cadmium germanium diphosphide (CdGeP2) crystals, with versatile terahertz-generating properties, belong to the chalcopyrite family of nonlinear optical materials. Other widely investigated members of this family are ZnGeP2 and CdSiP2. The room-temperature absorption edge of CdGeP2 is near 1.72 eV (720 nm). Cadmium vacancies, phosphorous vacancies, and germanium-on-cadmium antisites are present in as-grown CdGeP2 crystals. These unintentional intrinsic point defects are best studied below room temperature with electron paramagnetic resonance (EPR) and optical absorption. Prior to exposure to light, the defects are in charge states that have no unpaired spins. Illuminating a CdGeP2 crystal with 700 or 850 nm light while being held below 120 K produces singly ionized acceptors (VCd−) and singly ionized donors (GeCd+), as electrons move from VCd2− vacancies to GeCd2+ antisites. These defects become thermally unstable and return to their doubly ionized charge states in the 150–190 K range. In contrast, neutral phosphorous vacancies (VP0) are only produced with near-band-edge light when the crystal is held near or below 18 K. The VP0 donors are unstable at these lower temperatures and return to the singly ionized VP+ charge state when the light is removed. Spin-Hamiltonian parameters for the VCd− acceptors and VP0 donors are extracted from the angular dependence of their EPR spectra. Exposure at low-temperature to near-band-edge light also introduces broad optical absorption bands peaking near 756 and 1050 nm. A consistent picture of intrinsic defects in II-IV-P2 chalcopyrites emerges when the present CdGeP2 results are combined with earlier results from ZnGeP2, ZnSiP2, and CdSiP2.

[1]  B. N. Carnio,et al.  The Coming Age of Pnictide and Chalcogenide Ternary Crystals in the Terahertz Frequency Regime , 2022, IEEE Transactions on Terahertz Science and Technology.

[2]  G. Medvedkin.  Optical dichroism in ZnGeP2 crystals at deep levels , 2022, Journal of the Optical Society of America B.

[3]  Shiyou Chen,et al.  Defect Physics of Ternary Semiconductor ZnGeP2 with a High Density of Anion-Cation Antisites: A First-Principles Study , 2021 .

[4]  O. E. Porodinkov,et al.  The Influence of Defects on the Absorption of Terahertz Radiation in a CdSiP2 Single Crystal , 2020, Optics and Spectroscopy.

[5]  G. Kelly.  Chap. IV , 2020, Varieties of Female Gothic.

[6]  Matthew B. Johnson,et al.  Terahertz generation by optical rectification in chalcopyrite crystals ZnGeP2, CdGeP2 and CdSiP2. , 2019, Optics express.

[7]  Ming-Hsien Lee,et al.  Size effect and identified superior functional units enhancing second harmonic generation responses on the II-IV-V2 type nonlinear optical crystals , 2019, Chemical Physics.

[8]  P. Schunemann,et al.  Electron paramagnetic resonance and optical absorption study of acceptors in CdSiP2 crystals , 2018, AIP Advances.

[9]  X. Tao,et al.  Intrinsic defects and their effects on the optical properties in the nonlinear optical crystal CdSiP2: a first-principles study. , 2017, Physical chemistry chemical physics : PCCP.

[10]  P. Schunemann,et al.  Defect-related Optical Absorption Bands in CdSiP 2 Crystals , 2017 .

[11]  Peter G. Schunemann,et al.  Advances in nonlinear optical crystals for mid-infrared coherent sources , 2016 .

[12]  P. Schunemann,et al.  Identification of native defects (vacancies and antisites) in CdSiP2 crystals , 2015 .

[13]  Valentin Petrov,et al.  Frequency down-conversion of solid-state laser sources to the mid-infrared spectral range using non-oxide nonlinear crystals , 2015 .

[14]  E. Toberer,et al.  Solar energy conversion properties and defect physics of ZnSiP2 , 2015, 1506.05371.

[15]  David E. Zelmon,et al.  Growth and characterization of large CdSiP2 single crystals , 2010 .

[16]  P. Schunemann,et al.  Optical and EPR study of point defects in CdSiP2 crystals , 2010 .

[17]  A. Hoffmann,et al.  EPR identification of intrinsic and transition metal-related defects in ZnGeP2 and other II-IV-V2 compounds , 2009 .

[18]  W. Lambrecht,et al.  The importance of the self-interaction correction for Jahn–Teller distortion of the zinc vacancy in ZnGeP2 , 2009 .

[19]  M. Miao,et al.  Theoretical study of the phosphorus vacancy in Zn Ge P 2 , 2006 .

[20]  V. Storchak,et al.  Room temperature ferromagnetism in III–V and II–IV–V2 dilute magnetic semiconductors , 2006 .

[21]  C. Castleton,et al.  Relative concentration and structure of native defects in GaP , 2005 .

[22]  M. Miao,et al.  Theoretical study of cation-related point defects in ZnGeP2 , 2005 .

[23]  N. Stone.  Table of Nuclear Magnetic Dipole and Electric Quadrupole Moments , 2005 .

[24]  B. Meyer,et al.  Optically detected magnetic resonance experiments on native defects in ZnGeP2 , 2003 .

[25]  A. Krost,et al.  EPR and electrical studies of native point defects in ZnSiP2 semiconductors , 2003 .

[26]  W. Gehlhoff,et al.  EPR studies of native and impurity-related defects in II–IV–V2 semiconductors , 2003 .

[27]  D. Sarma,et al.  Novel Mn-doped chalcopyrites , 2003 .

[28]  N. Dietz,et al.  Structure and energy level of native defects in as-grown and electron-irradiated zinc germanium diphosphide studied by EPR and photo-EPR , 2003 .

[29]  S. Setzler,et al.  Infrared absorption bands associated with native defects in ZnGeP2 , 2003 .

[30]  N. Dietz,et al.  Energy levels of native defects in zinc germanium diphosphide , 2001 .

[31]  A. Zunger,et al.  Room-temperature ferromagnetism in Mn-doped semiconducting CdGeP2. , 2001, Physical review letters.

[32]  Takayuki Ishibashi,et al.  Ferromagnetic phenomenon revealed in the chalcopyrite semiconductor CdGeP2:Mn , 2001 .

[33]  S. Setzler,et al.  Characterization of defect-related optical absorption in ZnGeP2 , 1999 .

[34]  S. Setzler,et al.  Electron paramagnetic resonance of a cation antisite defect in ZnGeP2 , 1999 .

[35]  M. Ohmer,et al.  Atomistic Calculations of Defects in ZnGeP2. , 1996 .

[36]  Peter G. Schunemann,et al.  Electron‐nuclear double resonance of the zinc vacancy in ZnGeP2 , 1995 .

[37]  P. Schunemann,et al.  Photoinduced electron paramagnetic resonance of the phosphorus vacancy in ZnGeP2 , 1995 .

[38]  Peter G. Schunemann,et al.  Electron paramagnetic resonance study of a native acceptor in as‐grown ZnGeP2 , 1994 .

[39]  A. Räuber,et al.  ESR detection of antisite lattice defects in GaP, CdSiP2, and ZnGeP2 , 1976 .

[40]  G. Boyd,et al.  Linear and nonlinear optical properties of ternary A II B IV C 2 V chalcopyrite semiconductors , 1972 .

[41]  E. Buehler,et al.  Electroreflectance, Absorption Coefficient, and Energy-Band Structure of CdGeP 2 near the Direct Energy Gap , 1971 .

[42]  S. Abrahams,et al.  Luminescent Piezoelectric CdSiP2: Normal Probability Plot Analysis, Crystal Structure, and Generalized Structure of the AIIBIVC2V Family , 1971 .

[43]  J. C. Phillips,et al.  New Set of Tetrahedral Covalent Radii , 1970 .

[44]  R. Grigorovici,et al.  The structure of crystalline and amorphous CdGeP2 , 1968 .

[45]  K. Masumoto,et al.  The preparation and properties of ZnSiAs2, ZnGeP2 and CdGeP2 semiconducting compounds , 1966 .

[46]  Arthur Schweiger,et al.  EasySpin, a comprehensive software package for spectral simulation and analysis in EPR. , 2006, Journal of magnetic resonance.

[47]  R. Grant,et al.  Structural dependence of birefringence in the chalcopyrite structure. Refinement of the structural parameters of ZnGeP2 and ZnSiAs2 , 1973 .