Transmittance and radiation induced absorbance in VUV-UV-visible spectral region were measured in several binary
and complex fluoride single crystals at room temperature. Influence of the intentional doping and material stochiometry
is demonstrated. X-ray induced coloration and degradation of transmittance characteristics are observed and discussed in
terms of creation of various electron (F-like) and hole (VK- and H-like) centers and in terms of near band-edge transitions
arising due to imperfect periodicity of the lattice in a general sense. It is shown that VUV characteristics cannot be
derived or predicted from those observed in UV-visible spectral region.
We developed an analysis system for simulating birefringence of an annealed ingot of CaF<sub>2</sub> single crystal caused by the
residual stress after annealing process. The analysis system comprises the heat conduction analysis that provides the
temperature distribution during the ingot annealing, the stress analysis to calculate the residual stress after ingot
annealing, and the birefringence analysis of an annealed ingot induced by the residual stress. In the residual stress
calculation, we can select either the elastic thermal stress analysis using the assumption of a stress-free temperature or
more exact stress analysis considering the time-dependent nonlinear behavior of a material called creep. When we use
the residual stress calculated from the creep deformation analysis of a CaF<sub>2</sub> ingot, we can obtain reasonable results both
for the optical path difference values and for its distributions in comparison with the experimental results.
BaLiF<sub>3</sub> single crystal has been studied as the candidate for the last lens material of the next generation high index
immersion lithography system. Although the refractive index of BaLiF<sub>3</sub> is 1.64 at 193nm which is not sufficient for the
requirement, other optical properties such as 193nm transparency and laser durability fulfill the requirement.
It is estimated that the cause of both high SBR part and inhomogeneity of refractive index of BaLiF<sub>3</sub> seems to present
along the faces of slip planes which are observed by crossed Nicol observation. As a result of comparative study of
various direction perpendiculars to the growth axis, good crystallinity with less slip planes has been obtained by shifting
the growth axis from <100> which is adequate for the last lens production.
MgF<sub>2</sub> single crystal studied as the polarizer material for high power ArF laser oscillator, and crystal with excellent
laser durability and large diameter (>100mm) has been developed by CZ technique. In addition crystals oriented along
both c-axis and a-axis were successfully grown.
BaLiF<sub>3</sub> single crystal has been studied as the lens material for the candidate of the next generation high index immersion lithography system. Although the refractive index of BaLiF<sub>3</sub> is 1.64 at 193nm which is not sufficient for the requirement, other optical properties such as 193nm transparency and laser durability might fulfill the requirement, and intrinsic birefringence is relatively lower than other candidate materials.
It is estimated that the cause of scattering in the BaLiF<sub>3</sub> crystal is aggregation of excess LiF component. The special annealing process to eliminate excess LiF component was applied to improve the transparency. The internal transparency was improved to more than 97%/cm by optimizing growth conditions and annealing conditions.
CaF<sub>2</sub> single crystals are required for the most suitable lens materials for the ArF laser lithography stepper because of its excellent transparency and laser durability in the DUV region. We have succeeded in growing the large size and high quality CaF<sub>2</sub> single crystals with both <111> and <100> orientation, and the diameter of 300mm by means of the Czochralski (CZ) method. The refractive index homogeneity is one of the most important optical properties required for the lithography lens material. Particularly, the residual homogeneity which is a high-order refractive index distribution after subtraction of Zernike 36 coefficient is very important. The vein-like striations were observed in the residual homogeneity pattern of the CaF<sub>2</sub> single crystals. The structure of CaF<sub>2</sub> single crystal correlating with the residual homogeneity is characterized by using the reflection X-ray topography. It is observed that the structure of CaF<sub>2</sub> single crystal composed with sub-grains parted by the small-angle tilt boundaries. The sub-grains are grown along the growth direction. It is understood that the large angle tilt type sub-boundaries among the domains composed of small sub-grains correspond to the vein-like striations. In the growth of CaF<sub>2</sub> single crystal, the sub-grain structure of seed is introduced into grown crystal. While the bending of crystal lattice plane from the neck toward the shoulder lead to the large angle tilt type sub-boundaries. Use of high crystalline seed and control of crystal lattice plane in the shoulder are effective in the growth of high crystalline CaF<sub>2</sub> single crystal getting good residual homogeneity.
CaF2(Calcium fluoride) lens materials are required for the most important component of the ArF laser lithography stepper for the reason of its excellent transparency in DUV region and excellent laser durability as compared with quartz. Last year we reported to succeed in growing both <111> and <100> crystals, which had 210m diameter and 150mm length by the Czochralski (CZ) method with high productivity<sup>1</sup>). The obtained CaF2 crystal had low stress birefringence by way of the optimized annealing process. Although, for the higher NA system, larger CaF2 single crystals are required for the lens materials having the high quality and high productivity.
To meet the above mentioned demands, we made efforts to produce and succeeded the first in the world ultra-large (φ300mm over) and high quality CaF2 single crystal by the CZ method with high productivity. The crystal had very low stress birefringence, good transparency in DUV region and good homogeneity. It was also easy to control the orientation of the crystal by the selection of seed crystal.