Cu₄MnGe₂S₇ and Cu₂MnGeS₄: two polar thiogermanates exhibiting second harmonic generation in the infrared and structures derived from hexagonal diamond

The new, quaternary diamond-like semiconductor (DLS) Cu₄MnGe₂S₇ was prepared at high-temperature from a stoichiometric reaction of the elements under vacuum. Single crystal X-ray diffraction data were used to solve and refine the structure in the polar space group Cc. Cu₄MnGe₂S₇ features [Ge₂S₇]^6- units and adopts the Cu₅Si₂S₇ structure type that can be considered a derivative of the hexagonal diamond structure. The DLS Cu₂MnGeS₄ with the wurtz-stannite structure was similarly prepared at a lower temperature. The achievement of relatively phase-pure samples, confirmed by X-ray powder diffraction data, was nontrival as differential thermal analysis shows an incongruent melting behaviour for both compounds at relatively high temperature. The dark red Cu₂MnGeS₄ and Cu₄MnGe₂S₇ compounds exhibit direct optical bandgaps of 2.21 and 1.98 eV, respectively. The infrared (IR) spectra indicate potentially wide windows of optical transparency up to 25 μm for both materials. Using the Kurtz-Perry powder method, the second-order nonlinear optical susceptibility, χ⁽²⁾, values for Cu₂MnGeS₄ and Cu₄MnGe₂S₇ were estimated to be 16.9 ± 2.0 pm V^-1 and 2.33 ± 0.86 pm V^-1, respectively, by comparing with an optical-quality standard reference material, AgGaSe₂ (AGSe). Cu₂MnGeS₄ was found to be phase matchable at λ = 3100 nm, whereas Cu₄MnGe₂S₇ was determined to be non-phase matchable at λ = 1600 nm. The weak SHG response of Cu₄MnGe₂S₇ precluded phase-matching studies at longer wavelengths. The laser-induced damage threshold (LIDT) for Cu₂MnGeS₄ was estimated to be ∼0.1 GW cm^-2 at λ = 1064 nm (pulse width: τ = 30 ps), while the LIDT for Cu₄MnGe₂S₇ could not be ascertained due to its weak response. The significant variance in NLO properties can be reasoned using the results from electronic structure calculations.