CaB 2 C 2 : Reinvestigation of a Semiconducting Boride Carbide with a Layered Structure and an Interesting Boron/Carbon Ordering Scheme

Calcium diboride dicarbide, CaB(2)C(2), was synthesized as a crystalline powder and investigated by electron energy loss spectroscopy, X-ray powder diffractometry, conductivity measurements, and LMTO band structure calculations. A new structure model was derived, and the crystal structure was refined by Rietveld methods in the tetragonal space group I4/mcm (No. 140, a = 537.33(1) pm and c = 741.55(2) pm, Z = 4). The boron and carbon atoms are well ordered within layers consisting of four- and eight-membered rings. A convincing coloring scheme is proven by the detection of a superstructure reflection. An earlier assignment of the compound into the LaB(2)C(2) structure family (space group P2c or P4(2)/mmc, respectively) has been shown to be incorrect. LMTO band structure calculations suggest semiconducting behavior for CaB(2)C(2), which has been confirmed by conductivity measurements.