Ti2Ni and the related
η-carbide structure are
known to exhibit various intriguing physical properties. The Ti2Ni structure with the cubic space group Fd3̅m is surprisingly complex, consisting of
a unit cell with 96 metal atoms. The related η-carbide compounds
correspond to a filled version of the Ti2Ni structure.
Here, we report on the structure and superconductivity in the η-carbide-type
suboxides Ti4M2O with M = Co, Rh, and Ir. We
have successfully synthesized all three compounds in the single-phase
form. We found all three compounds to be type-II bulk superconductors
with transition temperatures of T
c = 2.7,
2.8, and 5.4 K and with normalized specific heat jumps of ΔC/γT
c = 1.65, 1.28, and
1.80 for Ti4Co2O, Ti4Rh2O, and Ti4Ir2O, respectively. We found that
all three superconductors exhibit high upper critical fields. Particularly
noteworthy in this regard is Ti4Ir2O with an
upper critical field of μ0
H
c2(0) = 16.06 T, which exceeds by far the weak-coupling Pauli
limitwidely considered as the maximal upper critical fieldof
μ0
H
Pauli = 9.86 T. The
role of the void-filling light atom X has so far been uncertain for
the overall physical properties of these materials. Herein, we have
successfully grown single crystals of Ti2Co. In contrast
to the metallic η-carbide-type suboxides Ti4M2O, we found that Ti2Co displays a semimetallic
behavior down to 0.75 K. Below 0.75 K, we observe a broad decrease
in the resistivity, which can most likely be attributed to an onset
of a superconducting transition at lower temperatures. Hence, the
octahedral void-filling oxygen plays a crucial role in the overall
physical properties, even though its effect on the crystal structure
is small. Our results indicate that the design of new superconductors
by incorporation of electron–acceptor atoms may in the Ti2Ni-type structures and other materials with crystallographic
void position be a promising future approach. The remarkably high
upper critical fields, in this family of compounds, may furthermore
spark significant future interest.