D. Bravo et al., EPR OF TUNGSTEN IMPURITIES IN KTIOPO4 SINGLE-CRYSTALS GROWN FROM MOLTEN TUNGSTATE SOLUTIONS, Physical review. B, Condensed matter, 52(5), 1995, pp. 3159-3169
The presence of tungsten impurities in KTiOPO4 (KTP) crystals grown fr
om molten tungstate solutions has been observed by means of electron p
aramagnetic resonance (EPR) at 90 K. The angular dependence of the EPR
signals and their behavior under thermal treatments allow us to disti
nguish two tungsten centers. The analysis of the measured g and hyperf
ine matrices for both centers indicates that the signals are due to W5
+ located at the two titanium sites of the KTP structure. Moreover, it
is shown that pentavalent tungsten is incorporated as the tungstenyl
WO3+ ion, whose formation is favored by the existence of one short ''t
itanyl'' Ti-O bond for each site. The results for the tungstenyl ion a
re compared to those for other oxycations previously studied in KTP. O
n the other hand, the intensity changes induced on the EPR signals by
the thermal treatments indicate that most tungsten impurities enter th
e Til site in the hexavalent state for the as-grown crystals. Besides,
the presence of some tetravalent tungsten at the Ti2 site created by
the reducing treatment is inferred.