Crystal growth, structure, and physical properties of Ln(Cu,Al)12 (Ln = Y, Ce, Pr, Sm, and Yb) and Ln(Cu, Ga)12 (Ln = Y, Gd-Er, and Yb).

Single crystals of Ln(Cu,Al)12 and Ln(Cu,Ga)12 compounds (Ln = Y, Ce-Nd, Sm, Gd-Ho, and Yb for Al and Ln = Y, Gd-Er, Yb for Ga) have been grown by flux-growth methods and characterized by means of single-crystal x-ray diffraction, complemented with microprobe analysis, magnetic susceptibility, resistivity and heat capacity measurements. Ln(Cu,Ga)12 and Ln(Cu,Al)12 of the ThMn12 structure type crystallize in the tetragonal I4/mmm space group with lattice parameters a approximately 8.59 Å and c approximately 5.15 Å and a approximately 8.75 Å and c approximately 5.13 Å for Ga and Al containing compounds, respectively. For aluminium containing compounds, magnetic susceptibility data show Curie-Weiss paramagnetism in the Ce and Pr analogues down to 50 K with no magnetic ordering down to 3 K, whereas the Yb analogue shows a temperature-independent Pauli paramagnetism. Sm(Cu,Al)12 orders antiferromagnetically at T(N)approximately 5 K and interestingly exhibits Curie-Weiss behaviour down to 10 K with no Van Vleck contribution to the susceptibility. Specific heat data show that Ce(Cu,Al)12 is a heavy fermion antiferromagnet with T(N) approximately 2 K and with an electronic specific heat coefficient γ0 as large as 390 mJ K2 mol(-1). In addition, this is the first report of Pr(Cu,Al)12 and Sm(Cu,Al)12 showing an enhanced mass (approximately 80 and 120 mJ K(2) mol(-1)). For Ga containing analogues, magnetic susceptibility data also show the expected Curie-Weiss behaviour from Gd to Er, with the Yb analogue being once again a Pauli paramagnet. The antiferromagnetic transition temperatures range over 12.5, 13.5, 6.7, and 3.4 K for Gd, Tb, Dy, and Er. Metallic behaviour is observed down to 3 K for all Ga and Al analogues. A large positive magnetoresistance up to 150% at 9 T is also observed for Dy(Cu,Ga)12. The structure, magnetic, and transport properties of these compounds will be discussed.