We report here new solid-solution KTiOPO4 (KTP) isomorphs, namely K1-x
NbxTi1-xOPO4 and K1-xTaxTi1-xOPO4, suitable for the second-harmonic ge
neration (SHG) of blue light. Aliovalent substitution of the Ti4+-K+ p
air in KTP with Nb5+ or Ta5+ increases substantially the optical biref
ringence (n(2)-n(y,x)) of KTP, and blueshifts the SHG cutoff wavelengt
hs for propagation along the x and y axes. A birefringence increase of
similar to 70%, and a SHG cutoff wavelength as short as 892 nm have b
een experimentally observed in crystals of K1-xNbxTi1-xOPO4. Detailed
single-crystal x-ray structure determination reveals that the Nb subst
itution is ordered, with Nh strongly favoring the cis-Ti(l) sites. We
discuss possible correlation between this preferential substitution an
d the observed compositional dependence of nonlinear susceptibilities
d(24), and d(15). Optimal solid-solution compositions for the noncriti
cally phase-matched frequency doubling of the 1.064 and 0.946 mu m lin
es of Nd:YAG lasers are presented, and potential applications for thes
e new materials are outlined.