In the semiconductor lithography technology, the polarized illumination system is applied to make the resolution more
microscopic, therefore the polarizer material with excellent durability against the high power ArF laser has been
required. Magnesium fluoride (MgF<sub>2</sub>) is one of a suitable material because of its laser durability and high transparency
in VUV region. Previously we reported MgF<sub>2</sub> single crystal with diameter of 100mm by using the Czochralski (CZ)
method. By optimizing the crystal growth conditions, MgF<sub>2</sub> single crystals with over 150mm in diameter have been
stably grown. Also these crystals show good optical properties and crystallinity.
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.
We tried to investigate various kinds of metal fluoride materials which have higher gravity than CaF<sub>2</sub> and cubic crystal system, and we found out barium lithium fluoride (BaLiF<sub>3</sub>) and potassium yttrium fluoride (KY<sub>3</sub>F<sub>10</sub>) as candidates for the last lens material. We have developed unique Czochralski (CZ) machines and techniques for the growth of large calcium fluoride single crystals. And we applied these technologies to the growth of fluoride high index materials. We have succeeded to grow the large BaLiF<sub>3</sub> single crystal with 120mm in diameter and a KY<sub>3</sub>F<sub>10</sub> single crystal, and measured their basic properties such as refractive index, VUV transmittance, birefringence, and so on. As a result of our basic research, we found out that BaLiF<sub>3</sub> single crystal is transparent at VUV region, and the refractive index at 193nm is 1.64, and KY<sub>3</sub>F<sub>10</sub> single crystal has the index of 1.59 at the wavelength of 193nm which is slightly higher than fused silica. We expect that these fluoride high index materials are useful for the last lens material of the next generation immersion lithography.
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.
CaF<sub>2</sub> (Calcium fluoride) lens materials are required for the composition of F<sub>2</sub> laser lithography stepper. Recently, it is reported that both <111> crystal and <100> crystal are necessary for the lens blanks, which can resolve the intrinsic birefringence of CaF<sub>2</sub>. Although CaF<sub>2</sub> single crystal has been produced by Bridgman method, some problems are pointed out on the optical properties and production yield especially on <100> crystal with large diameter. So it is worried that the amount of the supply of CaF<sub>2</sub> will be short when F<sub>2</sub> stepper will start on a large scale. To resolve the above mentioned problems, we tried to grow a large CaF<sub>2</sub> single crystal by Czochralski (CZ) technique, because we expected that CZ technique could provide higher productivity and higher quality which mean lower residual stress than conventional method. CZ technique can also easily control the growing crystal axis by the selection of seed crystal. Consequently we succeeded in growth both <111> and <100> direction single crystal which has 210mm diameter and 150mm length. The obtained crystal is a single crystal over a whole boule and it shows high transparency in vacuum ultraviolet region. Moreover it shows very low birefringence value and good homogeneity after annealing process. We hope our challenge should prompt the development of F<sub>2</sub> lithography.
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.