Abstract:
In an anti-reflective film comprising alternating layers of high refractive-index layers and low refractive-index layers, by designing such that a designed central wavelength λ 0  is within a wavelength range of 141 nm to 189 nm, and that when the first to eighth layers as counted from a substrate have optical film thicknesses d1 to d8 respectively, the equations of: 
 
0.45λ 0 ≦d 1 ≦0.65λ 0 ; 
 
0.05λ 0 ≦d 2 ≦0.20λ 0 ; 
 
0.29λ 0 ≦d 3 ≦0.49λ 0 ; 
 
0.01λ 0 ≦d 4 ≦0.15λ 0 ; 
 
0.05λ 0 ≦d 5 ≦0.20λ 0 ; 
 
0.23λ 0 ≦d 6 ≦0.28λ 0 ; 
 
0.23λ 0 ≦d 7 ≦0.28λ 0 ; and 
 
0.23λ 0 ≦d 8 ≦0.28λ 0  
are satisfied, the anti-reflective film can be formed so as to have a low reflectance for a light incident at such a large angle as 30 degrees or more, without increasing the whole thickness of the film.

Description:
BACKGROUND OF THE INVENTION  
       [0001]     1. Field of the Invention  
         [0002]     The present invention relates to an anti-reflective film coated on a surface of an optical element and an optical element having an anti-reflective film, and particularly to an anti-reflective film effective for ultraviolet light with a wavelength of 140 to 210 nm.  
         [0003]     2. Description of the Related Art  
         [0004]     Generally, as an anti-reflective film in an optical element such as an optical lens, a multilayer film is used which has high-refraction films and low-refraction films stacked in layers. The larger the number of the layers, the better the anti-reflective function of the film. However, when the number of layers of an anti-reflective film is increased in order to improve the anti-reflective function, the whole thickness of the anti-reflective film increases. When the thickness of the anti-reflective film becomes large, the transmittance of the anti-reflective film will lower to degrade the function as an optical element. Particularly, when using an anti-reflective film with a low refractive index, because it is necessary to increase the number of anti-reflective layers to make larger the geometrical film thickness in order to attain a desired optical function, the transmittance will lower to degrade a function as an optical element to vacuum-ultraviolet light.  
         [0005]     It has hitherto been known to use a fluoride film for an anti-reflective film to vacuum-ultraviolet light. U.S. Pat. No. 6,472,087 discloses an optical element using a fluoride film for an anti-reflective film, more specifically an anti-reflective film effective for an ultraviolet light of a wavelength of 190 to 250 nm obtained by employing Al 2 O 3  as a high refractive-index layer and AlF 3  or MgF 2  as a low refractive-index layer and stacking them alternately. Further, WO 00/058761 discloses an anti-reflective film consisting of 5 to 10 layers using a fluoride film.  
         [0006]     However, the wavelength of a light source used has become shorter and shorter in recent years, and even an F 2  laser of a wavelength of 157 nm has begun to be used. For this reason, an anti-reflective film effective in shorter wavelengths has been required. U.S. Pat. No. 6,472,087 mentioned above discloses an anti-reflective film effective for a wavelength within a range of 190 to 250 nm. However, the reflectance thereof is as high as 0.3% or more at a wavelength of 169 nm or less and is as high as 1% or more at a wavelength of 163 nm or less. In addition, an anti-reflective film having six layers disclosed in U.S. Pat. No. 6,472,087 above has a problem that the reflectance cannot be made low for a light. incident at such a large angle as 30 degrees or.more.  
         [0007]     In addition, of anti-reflective films having 5 to 10 layers disclosed in WO 00/058761 above, an anti-reflective film having 6 layers also has a problem that the reflectance cannot be made low for a light incident at such a large angle as 30 degrees or more as is the case with U.S. Pat. No. 6,472,087. Moreover, for an anti-reflective film having 10 layers, the whole thickness is as very large as 3.320 λ 0 . Therefore, it is believed that the transmittance to ultraviolet light is considerably low.  
       SUMMARY OF THE INVENTION  
       [0008]     The present invention has been accomplished in view of the above described problems.  
         [0009]     It is, therefore, an object of the present invention to provide an anti-reflective film of a 6-layer or 8-layer structure using fluoride thin films that is effective for a light of a wavelength of about 140 to 210 nm.  
         [0010]     It is another object of the present invention to realize an anti-reflective film that has a low reflectance for a light incident at such a large angle as 30 degrees or more, without increasing the whole thickness of the film.  
         [0011]     According to a first aspect of the present invention, there is provided an anti-reflective film of an eight-layer structure formed on a substrate, comprising a plurality of pairs of alternating layers comprising high refractive-index layers and low refractive-index layers having a refractive index lower than a refractive index of the high refractive-index layers, wherein the first, third, fifth, and seventh layers as counted from the substrate are the high refractive-index layers and the second, fourth, sixth, and eighth layers as counted from the substrate are the low refractive-index layers, wherein a designed central wavelength λ 0  is within a wavelength range of 141 nm to 189 nm, and wherein when the first to eighth layers have optical film thicknesses d 1 , d 2 , d 3 , d 4 , d 5 , d 6 , d 7 , and d 8  respectively, the equations of: 
 
0.45λ 0 ≦d 1 ≦0.65λ 0 ; 
 
0.05λ 0 ≦d 2 ≦0.20λ 0 ; 
 
0.29λ 0 ≦d 3 ≦0.49λ 0 ; 
 
0.01λ 0 ≦d 4 ≦0.15λ 0 ; 
 
0.05λ 0 ≦d 5 ≦0.20λ 0 ; 
 
0.23λ 0 ≦d 6 ≦0.28λ 0 ; 
 
0.23λ 0 ≦d 7 ≦0.28λ 0 ; and 
 
0.23λ 0 ≦d 8 ≦0.28λ 0  
 
 are satisfied. 
 
         [0012]     According to a second aspect of the present invention, there is provided an anti-reflective film of a six-layer structure formed on a substrate, comprising a plurality of pairs of alternating layers comprising high refractive-index layers and low refractive-index layers having a refractive index lower than a refractive index of the high refractive-index layers, wherein the first, third, and fifth layers as counted from the substrate are the high refractive-index layers and the second, fourth, and sixth layers as counted from the substrate are the low refractive-index layers, wherein a designed central wavelength λ 0  is within a wavelength range of 143 nm to 181 nm, and wherein when the first to sixth layers have optical film thicknesses d 1 , d 2 , d 3 , d 4 , d 5 , and d 6  respectively, the equations of: 
 
0.05λ 0 ≦d 1 ≦0.27λ 0 ; 
 
0.01λ 0 ≦d 2 ≦0.15λ 0 ; 
 
0.10λ 0 ≦d 3 ≦0.32λ 0 ; 
 
0.23λ 0 ≦d 4 ≦0.29λ 0 ; 
 
0.23λ 0 ≦d 5 ≦0.29λ 0 ; and 
 
0.23λ 0 ≦d 6 ≦0.28λ 0  
 
 are satisfied. 
 
         [0013]     According to a third aspect of the present invention, there is provided an anti-reflective film of a six-layer structure formed on a substrate, comprising a plurality of pairs of alternating layers comprising high refractive-index layers and low refractive-index layers having a refractive index lower than a refractive index of the high refractive-index layers, wherein the first, third, and fifth layers as counted from the substrate are the high refractive-index layers and the second, fourth, and sixth layers as counted from the substrate are the low refractive-index layers, wherein a designed central wavelength λ 0  is within a wavelength range of 140 nm to 210 nm, and wherein when the first to sixth layers have optical film thicknesses d 1 , d 2 , d 3 , d 4 , d 5 , and d 6  respectively, the equations of: 
 
0.05λ 0 ≦d 1 ≦0.27λ 0 ; 
 
0.01λ 0 ≦d 2 ≦0.15λ 0 ; 
 
0.10λ 0 ≦d 3 ≦0.32λ 0 ; 
 
0.47λ 0 ≦d 4 ≦0.67λ 0 ; 
 
0.23λ 0 ≦d 5 ≦0.29λ 0 ; and 
 
0.23λ 0 ≦d 6 ≦0.28λ 0  
 
 are satisfied. 
 
         [0014]     In the present invention, it is preferred that the low refractive-index layer comprises at least one material selected from the group consisting of MgF 2 , AlF 3 , NaF, LiF, CaF 2 , BaF 2 , SrF 2 , and Na 3 AlF 6 , and the high refractive-index layer comprises at least one material selected from the group consisting of LaF 3 , NdF 3 , GdF 3 , DyF 3 , YF 3 , and PbF 2 .  
         [0015]     Further, in the present invention, it is also preferred that the substrate comprises quartz or calcium fluoride.  
         [0016]     According to a fourth aspect of the present invention, there is provided an optical element having the above-mentioned anti-reflective film formed on a surface thereof.  
         [0017]     According to a fifth aspect of the present invention, there is provided an optical system comprising at least one optical element mentioned above.  
         [0018]     According to a sixth aspect of the present invention, there is provided an exposure system comprising an illumination optical system for illuminating a mask and a projection optical system for projecting a pattern formed on the mask onto a substrate, wherein the illumination optical system or the projection optical system comprises the above-mentioned optical system.  
         [0019]     The above and other objects of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings. 
     
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
       [0020]      FIG. 1  is a schematic view showing an anti-reflective film comprising eight layers in accordance with Example 1;  
         [0021]      FIG. 2  is a graphical representation showing the reflectance characteristics of the anti-reflective film in accordance with Example 1;  
         [0022]      FIG. 3  is a graphical representation showing the reflectance characteristics of an anti-reflective film consisting of two layers in accordance with a comparative example;  
         [0023]      FIG. 4  is a graphical representation showing the characteristic dependency on a light incidence angle of a reflectance to a light of a wavelength of 157 nm of the anti-reflective film of Example 1;  
         [0024]      FIG. 5  is a graphical representation showing the reflectance characteristics of an anti-reflective film comprising six layers in accordance with Example 2;  
         [0025]      FIG. 6  is a graphical representation showing the reflectance characteristics of an anti-reflective film comprising six layers in accordance with Example 3;  
         [0026]      FIG. 7  is a schematic view showing an exposure system comprising an optical element having an anti-reflective film in accordance with the present invention;  
         [0027]      FIG. 8  is an operation flow showing a production process of a semiconductor device; and  
         [0028]      FIG. 9  is an operation flow showing details of wafer processing in production steps of a semiconductor device. 
     
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS  
     EXAMPLE 1  
       [0029]      FIG. 1  is a schematic view showing an anti-reflective film consisting of eight layers for F 2  laser (157 nm) in accordance with Example 1 of the present invention. The anti-reflective film of the present example was prepared using an LaF 3  film with a refractive index of 1.765 at a wavelength of 157 nm for a high refractive-index layer, and an MgF 2  film with a refractive index of 1.466 at a wavelength of 157 nm for a low refractive-index layer. Table 1 shows the optical film thickness of each layer of the anti-reflective film for ultraviolet light with a designed central wavelength of λ 0 =157 nm. The refractive-index layers were sequentially formed by use of a vacuum evaporation method so as to have the thicknesses shown in Table 1, respectively. In the present example, calcium fluoride was used as a substrate.  
                                             TABLE 1                                       Optical Film           Material   Thickness                                        Medium on light   air               incidence side           Eighth layer   MgF 2     0.2588λ 0             Seventh layer   LaF 3     0.2639λ 0             Sixth layer   MgF 2     0.2614λ 0             Fifth layer   LaF 3     0.1138λ 0             Fourth layer   MgF 2     0.0569λ 0             Third layer   LaF 3     0.3907λ 0             Second layer   MgF 2     0.1094λ 0             First layer   LaF 3     0.5681λ 0             Medium on light   calcium fluoride           exit side   substrate                        
         [0030]     The reflection characteristics of the anti-reflective film shown in Table 1 were measured. In addition, for the purpose of comparison, an anti-reflective film of two layers consisting of an LaF 3  layer and an MgF 2  layer each having a thickness of 0.25λ 0  was also prepared following the same procedure, and the reflection characteristics were measured.  
         [0031]      FIG. 2  shows the results of the reflectance measurement of the anti-reflective film of the present example. In addition,  FIG. 3  shows the results of the reflectance measurement of the anti-reflective film consisting of two layers as the comparative example. It can be seen from  FIG. 2  that the anti-reflective film of the present example has good characteristics with a reflectance of 1.0% or lower within a wide wavelength range of 143 nm to 189 nm, and particularly that in a wide wavelength range of 146 nm to 184 nm, the anti-reflective film has good characteristics with a reflectance of 0.3% or lower.  
         [0032]     In contrast to this, it can be seen from  FIG. 3  that the comparative example shows good characteristics with a reflectance of 0.3% or lower within a wavelength range of 151 nm to 164 nm. However, at wavelengths of less than 151 nm or more than 164, the reflectance characteristics are degraded.  
         [0033]     In addition,  FIG. 4  shows the results of measurement for reflectance to an F 2  laser of a wavelength of 157 nm at various incidence angles of the anti-reflective film of the present example. It can be seen from  FIG. 4  that the anti-reflective film shows a reflectance of about 1% at an incidence angle of 50°, and therefore that the film shows good anti-reflection characteristics to a light with a large incidence angle.  
         [0034]     Similarly, it has also been found that when a designed central wavelength λ 0  is within a wavelength range of 141 nm to 189 nm, and when the first to eighth layers as counted from the substrate have optical film thicknesses d 1  to d 8  respectively and satisfy the equations of: 
 
0.45λ 0 ≦d 1 ≦0.65λ 0 ; 
 
0.05λ 0 ≦d 2 ≦0.20λ 0 ; 
 
0.29λ 0 ≦d 3 ≦0.49λ 0 ; 
 
0.01λ 0 ≦d 4 ≦0.15λ 0 ; 
 
0.05λ 0 ≦d 5 ≦0.20λ 0 ; 
 
0.23λ 0 ≦d 6 ≦0.28λ 0 ; 
 
0.23λ 0 ≦d 7 ≦0.28λ 0 ; and 
 
0.23λ 0 ≦d 8 ≦0.28λ 0  
 
 the same effect can be exhibited. 
 
       EXAMPLE 2  
       [0035]     An anti-reflective film in accordance with the present example has a six-layer structure having high refractive-index layers and low refractive-index layers alternately stacked. The anti-reflective film was prepared using an LaF 3  film with a refractive index of 1.765 at a wavelength of 157 nm for a high refractive-index layer, and an MgF 2  film with a refractive index of 1.466 at a wavelength of 157 nm for a low refractive-index layer. Table 2 shows the optical film thickness of each layer of the anti-reflective film for ultraviolet light with a designed central wavelength of λ 0 =157 nm. The refractive-index layers were sequentially formed by use of a vacuum evaporation method so as to have the thicknesses shown in Table 2, respectively. In the present example, calcium fluoride was used as a substrate.  
                                             TABLE 2                                       Optical               Film           Material   Thickness                                        Medium on light   air               incidence side           Sixth layer   MgF 2     0.2534λ 0             Fifth layer   LaF 3     0.2645λ 0             Fourth layer   MgF 2     0.2667λ 0             Third layer   LaF 3     0.1207λ 0             Second layer   MgF 2     0.0768λ 0             First layer   LaF 3     0.2505λ 0             Medium on light   calcium fluoride           exit side   substrate                      
 
         [0036]     The reflection characteristics of the anti-reflective film shown in Table 2 were measured.  FIG. 5  shows the results of the reflectance measurement of the anti-reflective film. It can be seen from  FIG. 5  that the anti-reflective film of the present example has good characteristics with a reflectance of 1.0% or lower within a wide wavelength range of 143 nm to 181 nm, and particularly that in a wide wavelength range of 146 nm to 173 nm, the anti-reflective film has good characteristics with a reflectance of 0.2% or lower.  
         [0037]     Similarly, it has also been found that when a designed central wavelength λ 0  is within a wavelength range of 143 nm to 181 nm, and when the first to sixth layers as counted from the substrate have optical film thicknesses d 1  to d 6  respectively and satisfy the equations of: 
 
0.05λ 0 ≦d 1 ≦0.27λ 0 ; 
 
0.01λ 0 ≦d 2 ≦0.15λ 0 ; 
 
0.10λ 0 ≦d 3 ≦0.32λ 0 ; 
 
0.23λ 0 ≦d 4 ≦0.29λ 0 ; 
 
0.23λ 0 ≦d 5 ≦0.29λ 0 ; and 
 
0.23λ 0 ≦d 6 ≦0.28λ 0  
 
 the same effect can be exhibited. 
 
       EXAMPLE 3  
       [0038]     An anti-reflective film in accordance with the present example has a six-layer structure having high refractive-index layers and low refractive-index layers alternately stacked. The anti-reflective film was prepared using an LaF 3  film with a refractive index of 1.765 at a wavelength of 157 nm for a high refractive-index layer, and an MgF 2  film with a refractive index of 1.466 at a wavelength of 157 nm for a low refractive-index layer. Table 3 shows the optical film thickness of each layer of the anti-reflective film for ultraviolet light with a designed central wavelength of λ 0 =157 nm. The refractive-index layers were sequentially formed by use of a vacuum evaporation method so as to have the thicknesses shown in Table 3, respectively. In the present example, calcium fluoride was used as a substrate.  
                                             TABLE 3                                       Optical               Film           Material   Thickness                                        Medium on   air               light           incidence           side               Sixth layer   MgF 2     0.269λ 0             Fifth layer   LaF 3     0.274λ 0             Fourth layer   MgF 2     0.57λ 0             Third layer   LaF 3     0.205λ 0             Second layer   MgF 2     0.079λ 0             First layer   LaF 3     0.136λ 0             Medium on   calcium           light exit   fluoride           side   substrate                      
 
         [0039]     The reflection characteristics of the anti-reflective film shown in Table 3 were measured.  FIG. 6  shows the results of the reflectance measurement of the anti-reflective film. It can be seen from  FIG. 6  that the anti-reflective film of the present example has good characteristics with a reflectance of 1.0% or lower within a wide wavelength range of 142 nm to 210 nm, and particularly that in a wide wavelength range of 144 nm to 207 nm, the anti-reflective film has good characteristics with a reflectance of 0.7% or lower.  
         [0040]     Similarly, it has also been found that when a designed central wavelength λ 0  is within a wavelength range of 140 nm to 210 nm, and when the first to sixth layers as counted from the substrate have optical film thicknesses d 1  to d 6  respectively and satisfy the equations of: 
 
0.05λ 0 ≦d 1 ≦0.27λ 0 ; 
 
0.01λ 0 ≦d 2 ≦0.15λ 0 ; 
 
0.10λ 0 ≦d 3 ≦0.32λ 0 ; 
 
0.47λ 0 ≦d 4 ≦0.67λ 0 ; 
 
0.23λ 0 ≦d 5 ≦0.29λ 0 ; and 
 
0.23λ 0 ≦d 6 ≦0.28λ 0  
 
 the same effect can be exhibited. 
 
         [0041]     In Examples 1 to 3 described above, an LaF 3  film was used for a high refractive-index layer, and an MgF 2  film was used for a low refractive-index layer. However, the present invention is not limited thereto, and an NdF 3  film, a GdF 3  film, a DyF 3  film, a YF 3  film, and a PbF 2  film, other than an LaF 3  film, can also be used for a high refractive-index layer. In addition, an AlF 3  film, an NaF film, an LiF film, a CaF 2  film, a BaF 2  film, an SrF 2  film, and an Na 3 AlF 6  film, other than an MgF 2  film, can also be used for a low refractive-index layer.  
         [0042]     In addition, in the above described examples 1 to 3, calcium fluoride was used as a substrate, but quartz is also available.  
         [0000]     &lt;Example of Exposure System&gt; 
         [0043]      FIG. 7  is a schematic view showing a main part of an exposure system (aligner) for producing a semiconductor device using an optical system. The optical system has an optical element having the anti-reflective film in accordance with Example 1, 2 or 3 described above. In the figure, reference numeral  1  denotes a light source for emitting ultraviolet light of a wavelength of 157 nm. Reference numeral  2  denotes an illumination system for illuminating a reticle  4  with a light beam from the light source  1 . Reference numeral  3  denotes a mirror. Reference numeral  5  denotes a projection optical system for projecting a pattern on the reticle  4  to a wafer  6 . Each of optical elements such as a lens used in the mirror  3 , the illumination system  2  and the projection optical system  5  has an anti-reflective film in accordance with the present invention applied on a surface thereof. Thereby, reflection of the light beam at each surface is prevented to suppress the occurrence of a flare or ghost, thus providing an excellent projected pattern image.  
         [0000]     &lt;Example of Production Method of Device&gt; 
         [0044]     In the next place, a method of producing a semiconductor device using the exposure system shown in  FIG. 7  will be described.  FIG. 8  shows a production flow of a semiconductor device (a semiconductor chip such as IC or LSI, a liquid crystal panel or CCD). In Step  1  (circuit design), a circuit of a semiconductor device is designed. In Step  2  (mask production), a mask (a reticle  4 ) having the designed circuit pattern formed thereon is prepared. On the other hand, in Step  3  (wafer manufacture), a wafer (wafer  6 ) is manufactured using a material such as silicon or the like. In Step  4  (wafer processing) which is called a pre-process, an actual circuit is formed on the wafer using the above prepared mask and the wafer by means of lithography. Next, Step  5  (assembly), which is called a post-process, is a step of making a chip by the use of the wafer prepared in Step  4  and includes an assembling step (dicing and bonding), a packaging step (chip encapsulation) and the like. In Step  6  (inspection), the semiconductor device produced in Step  5  is subjected to tests such as an operation check test and a durability test. A semiconductor device is thus completed through the above steps and is shipped (Step  7 ).  
         [0045]      FIG. 9  shows a detailed flow of the above described wafer process. In Step  11  (oxidation), the surface of the wafer (wafer W) is oxidized. In Step  12  (CVD), an insulation film is formed on the surface of the wafer. In Step  13  (electrode formation), an electrode is formed on the wafer through vapor deposition. In Step  14  (ion implantation), ions are implanted into the wafer. In Step  15  (resist treatment), a resist (sensitized material) is applied to the wafer. In Step  16  (exposure), the wafer is exposed through an image of a circuit pattern of the mask (reticle  4 ) with the exposure system. In Step  17  (development), the exposed wafer is developed. In Step  18  (etching), a portion except a developed resist portion is removed. In Step  19  (resist stripping), the resist is removed which has become unnecessary after completion of the etching step. A circuit pattern is formed on the wafer by repeating these steps.  
         [0046]     As described above, according to the present invention, there can be provided an anti-reflective film of a 6-layer or 8-layer structure using fluoride thin films that is effective for a light of a wavelength of about 140 to 210 nm. Further, it is possible to realize an anti-reflective film that has a low reflectance for a light incident at such a large angle as 30 degrees or more, without increasing the whole thickness of the film.  
         [0047]     This application claims priority from Japanese Patent Application No. 2004-178534 filed on Jun. 16, 2004, which is hereby incorporated by reference herein.