We present the studies of electrical transport and magnetic interactions in Zn1−xMnxGeAs2 crystals with low Mn content 0≤x≤0.042. We show that the ionic-acceptor defects are mainly responsible for the strong p-type conductivity of our samples. We found that the negative magnetoresistance with maximum values of about −50% is related to the weak localization phenomena. The magnetic properties of Zn1−xMnxGeAs2 samples show that the random Mn-distribution in the cation sites of the host lattice occurs only for the sample with the lowest Mn-content, x = 0.003. The samples with higher Mn-content show a high level of magnetic frustration. Nonzero Curie-Weiss temperature observed in all our samples indicates that weak ferromagnetic (for x = 0.003) or antiferromagnetic (for x>0.005) interactions with the Curie-Weiss temperature, |Θ|<3 K, are present in this system. The Ruderman-Kittel-Kasuya-Yosida model, used to estimate the Mn-hole exchange integral Jpd for the diluted Zn0.997Mn0.003GeAs2 sample, makes possible to estimate the value of Jpd=(0.75 ± 0.09) eV.

We present systematic studies of magnetic and transport properties of Zn1−xMnxGeAs2 semimagnetic semiconductor with the chemical composition varying between 0.053≤x≤0.182. The transport characterization showed that all investigated samples had p-type conductivity strongly depending on the chemical composition of the alloy. The Hall effect measurements revealed carrier concentrations p≥1019 cm−3 and relatively low mobilities, μ≤15 cm2/(V s), also chemical composition dependent. The magnetic investigations showed the presence of paramagnet-ferromagnet phase transitions with transition temperatures greater than 300 K for the samples with x≥0.078. We prove by means of x-ray diffraction, nuclear magnetic resonance, and scanning electron microscopy techniques that the observed room temperature ferromagnetism is due to the presence of MnAs inclusions. The high field magnetoresistance showed the presence of giant magnetoresistance effect with maximum amplitudes around 50% due to the presence of nanosize ferromagnetic grains.

We have studied vacancy defects in chalcopyrite semimagnetic semiconducting mixed Zn 1−x ͑Mn, Co͒ x GeAs 2 bulk crystals with alloy composition x varying between 0.052 to 0.182 using positron annihilation spectroscopy. We identified As vacancies, potentially complexed with the transition metal alloying elements, in all the studied samples, while no cation vacancy related defects were detected. The positron lifetimes for the bulk ZnGeAs 2 lattice and neutral As vacancy were determined to be B = 220-230 ps and As = 300Ϯ 10 ps, respectively. Our results also show that the p-type conductivity in the samples is not due to cation vacancy related acceptor centers. The As vacancies were found to be present at such low concentrations that they cannot be responsible for the compensation of the p-type conductivity or the reduction of mobility in the Zn 1−x ͑Mn, Co͒ x GeAs 2 samples.

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