Patent Publication Number: US-7903264-B2

Title: Structure inspection method, pattern formation method, process condition determination method and resist pattern evaluation apparatus

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a division of U.S. application Ser. No. 11/051,617, filed Jan. 27, 2005 now U.S. Pat. No. 7,483,155, which is based upon and claims the benefit of priority from prior Japanese Patent Application No. 2004-021647, filed Jan. 29, 2004. The entire contents of these applications are incorporated herein by reference in their entirety. 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a structure inspection method of inspecting the structure of an evaluation object from an intensity of reflection light of the evaluation object. Further, the present invention relates to pattern formation method, process condition determination method and resist pattern evaluation apparatus. 
     2. Description of the Related Art 
     Many reports with respect to the following method have been made. According to the method, a light incident on a pattern having a regular structure on a substrate, and the light is diffracted to obtain a diffraction light. Then, the dimension and shape of the pattern are evaluated from the measured result of the obtained diffraction light. For example, U.S. Pat. No. 5,963,329 discloses the method given below. According to the method, cos Δ and tan ψ of a pattern having a regular structure are measured using an ellipsometer. Then, the measured values are compared with cos Δ and tan ψ obtained from a theoretical electromagnetic wave calculation to determine the dimension. In the method, the theoretical calculation is made using the structure of a film forming a substrate and optical constant. In this case, the method is applicable to evaluation for resist pattern after development and pattern after etching. However, if the method is used for evaluating the dimension of resist pattern such that a developer film is formed on the substrate, it is impossible to accurately evaluate the pattern. This is because a mixed phase of resist reaction product and the developer exists in the vicinity of the resist pattern. According to the method disclosed in JPN. PAT. APPLN. KOKAI Publication No. 2002-25883, it is difficult to accurately evaluate the pattern. This is because a mixed phase of resist near the resist pattern and the developer is not considered like the U.S. Pat. No. 5,963,329 mentioned above. 
     The U.S. Pat. No. 5,963,329 further has the following disclosure. That is, theoretical wavelength dispersion of the diffraction light intensity is previously obtained by electromagnetic wave calculation using the structure of a film on the substrate and optical constant. Then, a comparison between the measured result of wavelength dispersion of the diffraction light in an actual substrate and the preceding theoretical wavelength dispersion is made to calculate the dimension and shape. This U.S. patent has disclosure of considering a composition distribution in the depth direction of the film caused by doping, and does not disclose the distribution features. 
     Therefore, it is impossible to accurately evaluate the pattern using the conventional method of diffracting light incident on a pattern having regular structure on a substrate, and evaluating the dimension and shape from the measured result of the obtained diffraction light. 
     BRIEF SUMMARY OF THE INVENTION 
     According to a first aspect of the present invention, there is provided a structure inspection method comprising: measuring wavelength dispersion of intensity of light reflected from an evaluation object located under an environment; preparing a complex refractive index of a substance forming the evaluation object and a complex refractive index of a substance forming the environment; setting virtual component ratios comprising a mixture ratio of the substance forming the evaluation object and the substance forming the environment in a predetermined space; making a multiple interference calculation using the complex refractive index of the substance forming the evaluation object and the complex refractive index of the substance forming the environment, thereby calculating reflectance wavelength dispersions to the virtual component ratios; extracting similar reflectance wavelength dispersions having a small difference with the measured wavelength dispersion from the reflectance wavelength dispersions; making weighted average to the virtual component ratios used for calculating the similar reflectance wavelength dispersions so that weighting is larger when the difference is smaller, thereby calculating a component ratio of the substance forming the evaluation object and the substance forming the environment; and determining a structure of the evaluation object from the calculated component ratio. 
     According to a second aspect of the present invention, there is provided a structure inspection method comprising: preparing a substrate having layers whose structure is characterized by an optical constant, film thickness, ratio and pitch, the substrate having one or more structure-determined layer and one or more structure-undetermined layer; preparing predicted structures of each of the layers; preparing a substrate structure library storing substrate structures comprising combinations of the structures in each of the layers; making light enter each of the substrate structures at a specified angle and calculating a light intensity of the light which is diffracted or reflected from the structure, thereby preparing a first light intensity library storing the substrate structures and the light intensity calculated to each of the substrate structures; newly preparing structures including a structure of a structure-determined layer; extracting a substrate structure including one of the newly prepared structures from the substrate structures in the first light intensity library, and preparing a second light intensity library storing the extracted substrate structure and a light intensity calculated with respect to the extracted substrate structure; making light enter the substrate at the specified angle and detecting a light intensity of light which is diffracted or reflected from the substrate; and comparing the detected light intensity with the light intensity stored in the second light intensity library to determine a structure of the substrate. 
     According to a third aspect of the present invention, there is provided a structure inspection method comprising: preparing a substrate having layers whose structure is characterized by an optical constant, film thickness, ratio and pitch, the substrate having one or more structure-determined layer and one or more structure-undetermined layer; preparing predicted structures of each of the layers; preparing a substrate structure library storing substrate structures comprising combinations of the structures in each of the layers; newly preparing structures of the structure-determined layers based on a structure of the structure-determined layer; extracting a substrate structure including the newly prepared structures from the first substrate structure library, preparing a second substrate structure library; predicting a light intensity of light which is diffracted or reflected from the substrate structure by calculation when making light enter each of the substrate structures in the second substrate structure library at a specified angle; making light enter the substrate at the specified angle and detecting a light intensity of light which is diffracted or reflected from the substrate; and comparing the detected light intensity with the predicted light intensity, thereby determining a structure of the substrate. 
     According to a fourth aspect of the present invention, there is provided a structure inspection method comprising: preparing a substrate having layers whose structure is characterized by an optical constant, film thickness, ratio and pitch, the substrate having one or more structure-determined layer and one or more structure-undetermined layer; preparing predicted structures of each of the structure-undetermined layers; preparing determined structure including a structure of the structure-determined layer; preparing a substrate structure library storing substrate structures comprising combinations of the predicted structures and the determined structure; making light enter at a specified angle the substrate structures stored in the substrate structure library and predicting a light intensity of light which is diffracted or reflected from the substrate structure by calculation; making light enter the substrate at the specified angle and detecting a light intensity of light which is diffracted or reflected from the substrate; and comparing the detected light intensity with the predicted light intensity, thereby determining a structure of the substrate. 
     According to a fifth aspect of the present invention, there is provided a structure inspection method of inspecting a resist pattern which is formed by development of an exposed resist film formed on a substrate, comprising: predicting an opening shape of a opening where a resist film is dissolved by developer, and predicting a distribution of a mixture ratio of a reaction product of the resist film and the developer in a liquid phase comprising the developer and the reaction product; preparing an optical constant of the resist film, the reaction product and the developer; setting structures comprising the substrate and the liquid phase based on the predicted opening shape and mixture ratio; calculating a light intensity of light which is diffracted from a substrate which has a developer film on a main surface of the substrate when making light enter the substrate at a specified angle; making light enter at the specified angle a measurement pattern on the substrate which has a developer film on a main surface of the substrate and detecting a light intensity of diffraction light from the substrate; comparing the detected intensity of the light with the calculated intensity of the light; and calculating at least one of a pattern dimension and a pattern shape of the resist film and the distribution of the ratio in the liquid phase from a best matching result in the comparison. 
     According to a sixth aspect of the present invention, there is provided a pattern forming method for evaluating a resist pattern which is formed by development of an exposed resist film formed on a substrate, and completing the development based on the evaluation result, comprising: predicting an opening shape of a opening where a resist film is dissolved by developer, and predicting a distribution of a mixture ratio of a reaction product of the resist film and the developer in a liquid phase comprising the developer and a reaction product of the resist film; giving a structure of a construction comprising the substrate and the liquid phase and optical constant based on a result of the prediction; predicting a light intensity of diffraction light from the construction when making light enter the construction at a specified angle; making light enter at the specified angle a measurement pattern on the substrate which has a developer film on a main surface of the substrate and detecting an intensity of diffraction light from the substrate; comparing the detected intensity of the diffraction light with the predicted intensity of the diffraction light; calculating a pattern dimension of the resist film from a best matching result in the comparison; and completing the development based on the pattern dimension. 
     According to a seventh aspect of the present invention, there is provided a method of determining a process condition, comprising: planning an experiment, in which experiment conditions are changed among two or more levels, the experiment conditions including a condition of controlling resist solution, a condition of forming a resist film, an exposure condition of forming a latent image on the resist film, a condition of baking a resist film formed with the latent image, and a condition of developing the resist film to form a resist pattern; changing exposure amount or defocus amount to form a latent image on the resist film, thereby forming the resist pattern based on the experiment; carrying out a measurement which includes making light enter at a specified angle a substrate which has a resist pattern thereon, detecting a light intensity of light which is diffracted or reflected from the substrate, and measuring a shape of the resist pattern using the detected light intensity and an optical constant of a material forming the substrate; calculating a process margin of exposure amount or defocus amount obtained under a level of experiment conditions based on the measured shape of the resist pattern; and predicting a combination of levels of the experiment conditions that realizes a higher process margin than a predetermined value from a relationship between levels of the experiment conditions and the process margin of the exposure amount or defocus amount. 
     According to a eighth aspect of the present invention, there is provided a resist pattern evaluation apparatus comprising: latent image forming section forming a latent image on a resist film on a substrate while changing exposure amount or defocus amount; bake section baking the resist film formed with the latent image; a process unit having development section developing the resist film to form a resist pattern; resist pattern measurement section measuring a shape of the resist pattern; and margin calculation section calculating a margin of exposure amount or defocus amount from a shape measurement value of the resist pattern corresponding to the exposure amount or defocus amount. 
    
    
     
       BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING 
         FIG. 1  is a flowchart to explain a method of determining the structure of an evaluation object according to a first embodiment of the present invention; 
         FIG. 2  is a cross-sectional view showing the development progress of a resist film; 
         FIG. 3  is a cross-sectional view showing the layer structure along the film thickness direction prepared based on a development progress model; 
         FIG. 4  is a schematic view showing the configuration of a reflectance measuring means; 
         FIG. 5  is a graph to explain a comparison between a calculated reflectance and a measured value; 
         FIG. 6  is a chart showing the dimensional variable result of a developing KrF resist using a sectional shape; 
         FIG. 7  is a graph to explain the relationship between development time and a bottom dimension; 
         FIG. 8  is a graph to explain the relationship between development time and a bottom dimension obtained from a conventional method; 
         FIG. 9  is a graph to explain the relationship between etching time and etching depth according to a second embodiment of the present invention; 
         FIG. 10  is a flowchart to explain the process of manufacturing a semiconductor device according to a third embodiment of the present invention; 
         FIGS. 11A ,  11 B and  11 C are each cross-sectional views successively showing the process of manufacturing a semiconductor device according to the third embodiment; 
         FIG. 12  is a schematic view showing a substrate A and a light intensity measurement optical system; 
         FIG. 13  is a schematic view showing a substrate B and a light intensity measurement optical system; 
         FIG. 14  is a flowchart to explain the structure inspection procedure according to the third embodiment; 
         FIG. 15  is a flowchart to explain the structure inspection procedure according to the third embodiment; 
         FIG. 16  is a flowchart to explain the structure inspection procedure according to the third embodiment; 
         FIG. 17  is a flowchart to explain the process of manufacturing a semiconductor device according to the third embodiment of the present invention; 
         FIG. 18  is a flowchart to explain the conventional structure inspection procedure; 
         FIG. 19  is a flowchart to explain the process of manufacturing a conventional semiconductor device; 
         FIG. 20  is a schematic view showing the pattern evaluation during development; 
         FIG. 21  is a flowchart to explain the procedure of a pattern evaluation method according to the third embodiment; 
         FIG. 22A  and  FIG. 22B  are each schematic views showing the development progress of a resist film; 
         FIG. 23  is a view to explain the diffusion direction of developing reaction products 
         FIG. 24  is a cross-sectional view showing the layer structure along the film thickness direction prepared based on a model shown in  FIG. 23 ; 
         FIG. 25  is a chart showing the distribution of a mixture ratio of developer and reaction product; 
         FIG. 26  is a chart showing the distribution of an refractive index based on a model of the third embodiment; 
         FIG. 27  is a chart showing the distribution of an extinction coefficient based on a model of the third embodiment; 
         FIG. 28  is a view showing a conventional development model; 
         FIG. 29  is a chart showing the distribution of an refractive index based on a conventional model; 
         FIG. 30  is a chart showing the distribution of an extinction coefficient based on a conventional model; 
         FIG. 31  is a flowchart to explain the procedure of a pattern evaluation method according to a fourth embodiment of the present invention; 
         FIG. 32  is a view showing the configuration of a photosensitive resin pattern forming system according to a fifth embodiment of the present invention; and 
         FIG. 33  is a flowchart to explain the procedure of a process condition determination method according to a fifth embodiment of the present invention. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Embodiments of the present invention will be described below with reference to the accompanying drawings. In the following description, the same reference numerals are used to designate components having the identical function and configuration, and the overlapping explanation is given if necessary. 
     (1) First Embodiment 
     The first embodiment shows an application example to a process given below. According to the process, an anti-reflection film is formed on a Si substrate, and thereafter, ArF chemically amplified resist is further formed thereon to have a film thickness of 300 nm. A pattern for processing (etching) a front-end film is exposed onto the resist film using an ArF stepper, and thereafter, baked. Development is carried out, and thereby, the following resist pattern is formed. The resist pattern has a pitch of 260 nm and a resist remaining dimension of 115 nm (ratio of the resist pattern to pitch=0.442:0.558 in developer ratio). 
       FIG. 1  is a flowchart to explain a method of determining the structure of an evaluation object according to a first embodiment of the present invention. 
     A model used for calculating the profile of a resist film under development is prepared (step S 101 ). The model corresponds to a typical state of developer and resist during development. A reaction product of the developer and the resist is generated from the developing resist pattern. In the following description, a developer containing a resist reaction product is called a mixed phase, and a ratio of the resist in the mixed phase is defined as a mixture ratio. In general, the diffusion velocity of the reaction product is not so fast. For this reason, if the diffusion of the reaction product, that is, a distribution of the mixture ratio in liquid phase is not taken into account in a model, the accuracy of developing pattern evaluation is worsened. In order to solve the foregoing problem, a development model considering the distribution is determined in a library preparation process in the first embodiment. 
     The method of forming the model will be described below.  FIG. 2  is a schematic view showing the development progress. In the initial development, the development to an exposed resist film  104  advances to the film thickness direction as seen from  FIG. 2 . As a result, reaction products diffuse to the direction shown by an arrow. Therefore, the mixture ratio has a film thickness distribution and decreases as the position gradually gets away from the substrate. When the development in the film thickness direction ends, development advances laterally. Thus, a developer model such that a ratio of developer occupying a space increases toward the arrow direction is presumed. In  FIG. 2 , a reference numeral  101  denotes a silicon substrate,  102  denotes anti-reflection film,  103  denotes a non-exposed resist film, and  105  denotes a developer. 
     The following is a description of the step of giving substrate structure and optical constant.  FIG. 3  is a cross-sectional view showing the layer structure in the film thickness direction prepared based on the above-mentioned model. Layers D 1  and D 2  comprises the developer and the mixed phase of reaction product of resist. Layers R 1  to R 4  comprises the developer, the mixed phase of reaction product of resist and resist pattern. The layers D 1  and D 2  differ from each other in a mixture ratio of the reaction product. Likewise, the layers R 1  to R 4  differ from each other in a mixture ratio of the reaction product. The reaction product is generated in the interface between the resist and the developer, and gradually diffuses to the developer layer. Therefore, the ratio of the reaction product is high at the bottom portion of the pattern. 
     Several virtual component ratios presuming the ratio of each substance forming evaluation object and measurement environment are set. In each layer, several ratios of each substance occupied in a space are set. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 Film 
                 Classification of 
                   
                 Step of 
               
               
                 structure 
                 film structure 
                 Range of ratio 
                 ratio (%) 
               
               
                   
               
             
            
               
                 Developer 
                 Layer D 2   
                 Developer/space = 
                 0.05 
               
               
                 layer 
                   
                 ratio of layer D 1 -1.00 
                   
               
               
                   
                 Layer D 1   
                 Developer/space = 
                 0.05 
               
               
                   
                   
                 0.80-1.00 
                   
               
               
                 Resist 
                 Layer R 4   
                 Developer/space = 
                 0.10 
               
               
                 layer 
                   
                 ratio of layer R 3 -1.00 
                   
               
               
                   
                 Layer R 3   
                 Developer/space = 
                 0.10 
               
               
                   
                   
                 ratio of layer R 2 -0.70 
                   
               
               
                   
                 Layer R 2   
                 Developer/space = 
                 0.10 
               
               
                   
                   
                 ratio of layer R 1 -0.70 
                   
               
               
                   
                 Layer R 1   
                 Developer/space = 
                 0.10 
               
               
                   
                   
                 0-0.70 
                   
               
               
                 Anti- 
                 Anti-reflection 
                 Anti-reflection material/ 
                 — 
               
               
                 reflection 
                 film layer 
                 space = 1.00 (fixed) 
                   
               
               
                 film layer 
                   
                   
                   
               
               
                 Si 
                 Si substrate 
                 Si/space = 1.00 (fixed) 
                 — 
               
               
                 substrate 
               
               
                   
               
            
           
         
       
     
     Database comprising reflectance wavelength dispersion calculation value in the ratio of each layer is prepared using conditions shown in the Table 1 (step S 102 ). The database is prepared in the following manner. First, several ratios of each substance occupying a space are prepared under the conditions shown in the Table 1, and average optical constant is determined in accordance with these ratios. Using the optical constant, a multiple interference calculation is carried out to determine a reflectance. The wavelength dispersion of the reflectance is calculated in a range from 300 to 800 nm. In general, RCWA (Rigorous coupled-wave analysis) by Morham et al. (J. Opt. Soc. Am., Vol. 12, No. 5, May 1995 1077-1086) is used as the calculation method to obtain electric filed, magnetic field and intensity of refraction light from regular pattern using Maxwell equations. Incidentally, the optical constant of the reaction product generated from the reaction resist with developer is set to the same as that of the resist. Complex refractive index comprising a refractive index n and an extinction coefficient k may be used as the optical constant. 
     Average (mean) complex refractive index is determined in the following manner when developer/space=0.95 in the layer D 2  of the developer layer. The average complex refractive index is obtained from the following equations (1) and (2) using complex refractive index of the developer (refractive index n, extinction coefficient k)=(1.33, 0) and complex refractive index of the resist (1.67, 0.06).
 
Average refractive index  n= 1.33×0.95+1.67×0.05=1.347  (1)
 
Average extinction coefficient  k= 0×0.95+0.06×0.05=0.003  (2)
 
     The substrate whose resist film has been subjected to pattern exposure to resist film and post exposure bake (PEB) is cooled, and thereafter, transferred to a development apparatus. A developer is supplied onto the main surface of the substrate to form a developer film, and then, development of a resist film is started (step S 103 ). The resist film has a device pattern region on which a device pattern is exposed and a monitor pattern region on which a monitor pattern is exposed. 
     A reflectance measuring means is arranged above the exposed monitor pattern for dimension measurement. Thereafter, a change of the developing pattern is watched via observation of a change of reflectance (step S 104 ). 
       FIG. 4  is a schematic view showing the configuration of the reflectance measuring means. The reflectance measuring means reflects light from a light source  211  by a mirror included in an observation optical system  212  to irradiate the light to a monitor pattern region  203  of a resist pattern  201 . The monitor pattern region  203  reflects the light, and thereby, a zero-order diffraction light is generated via diffraction. The zero-order diffraction light collected to the observation optical system  212 . Thereafter, the light is transmitted to a spectrometer  213  via silica optical fiber, and then, the spectrometer  213  measures wavelength dispersion of the light. A wavelength dispersion measurement value detected by the spectrometer  213  is successively sent to a computer  214 . Incidentally, the monitor pattern region  203  is formed outside the device pattern region  202 . A database  215  stores the reflectance wavelength dispersion calculation value calculated in step S 102 . 
     The computer  214  compares the reflectance wavelength dispersion measurement value sent from the spectrometer  213  with the wavelength dispersion calculation value stored in the database  215 . Then, the computer  214  extracts some similar reflectance wavelength dispersion calculation values having the same wavelength dispersion measurement value (step S 105 ). In this extraction, the sum of squares Si of a reflectance measurement value r λ  at a wavelength λ and a reflectance calculation value r λc  at the wavelength λ is calculated. 
     
       
         
           
             
               Sum 
               ⁢ 
               
                   
               
               ⁢ 
               of 
               ⁢ 
               
                   
               
               ⁢ 
               squares 
             
             = 
             
               
                 ∑ 
                 
                   j 
                   = 
                   1 
                 
                 n 
               
               ⁢ 
               
                 
                   
                     ( 
                     
                       
                         r 
                         
                           λ 
                           ⁢ 
                           
                               
                           
                           ⁢ 
                           j 
                         
                       
                       - 
                       
                         r 
                         
                           λ 
                           ⁢ 
                           
                               
                           
                           ⁢ 
                           jc 
                         
                       
                     
                     ) 
                   
                   2 
                 
                 
                   ( 
                   
                     
                       λ 
                       n 
                     
                     - 
                     
                       λ 
                       1 
                     
                   
                   ) 
                 
               
             
           
         
       
     
     Then, the reflectance measurement value having the minimum sum of squares is retrieved in order. In the first embodiment, the reflectance calculation value less than 110% of the reflectance measurement value which makes the minimum sum of squares is retrieved. 
     Weighted average is taken in accordance with the sum of squares of a space ratio (component ratio), which is a base of the reflectance measurement value. By doing so, a space ratio predictive value rp i  is calculated (step S 106 ). The space ratio predictive value rp i  is obtained from the following equation (4) using a space ratio r i , which is a base of the reflectance measurement value, and the sum of squares Si.
 
 rp   i =(Σ r   i   /s   i )/(Σ(1 /s   i ))  (4)
 
     Using the equation (4), each space ratio predictive value rp i  of layers R 1  to D 2  is calculated. The calculated space ratio predictive value rp i  is regarded as a ratio representing how much the pattern dimension occupies the pitch. 
     It is determined whether or not the space ratio predictive value rp i  obtained based on the weighted average is equal to a predetermined value (step S 107 ). According to the first embodiment, the predetermined value is 56%. In this embodiment, the resist pattern is formed having a pitch of 260 nm and a resist remaining dimension of 115 nm (ratio of the resist pattern to pitch=0.442:0.558 in developer ratio). Therefore, it is determined whether the space ratio predictive value rp i  of the layer R 4  is equal to 56%. 
     If the space ratio predictive value rp i  of the layer R 4  is equal to 56%, cleaning water is supplied to the substrate surface, and then, development is stopped (step S 108 ). 
     If the space ratio predictive value rp i  of the layer R 4  is not equal to 56%, development is continued, and the procedures from step S 103  to S 107  are repeated. When the space ratio predictive value rp i  of the layer R 4  is equal to 56%, cleaning water is supplied to the substrate surface, and then, development is stopped. 
     The procedures from step S 103  to S 107  will be described below. 
     In the following Table 2, there are shown space ratios r i  of each layer in order from the minimum sum of squares to the reflectance measurement value when 20 seconds elapse after development starts. 
     
       
         
           
               
               
               
               
               
               
               
               
             
               
                 TABLE 2 
               
               
                   
               
               
                   
                 Layer R 1   
                 Layer R 2   
                 Layer R 3   
                 Layer R 4   
                 Layer D 1   
                 Layer D 2   
                 Sum of 
               
               
                 Rank 
                 25 nm 
                 135 nm 
                 135 nm 
                 5 nm 
                 10 nm 
                 10 nm 
                 squares 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 1 
                 0.60 
                 0.60 
                 0.60 
                 0.60 
                 1.00 
                 1.00 
                 0.115 
               
               
                 2 
                 0.60 
                 0.60 
                 0.60 
                 0.60 
                 0.95 
                 1.00 
                 0.119 
               
               
                 3 
                 0.50 
                 0.50 
                 0.50 
                 0.60 
                 1.00 
                 1.00 
                 0.120 
               
               
                 4 
                 0.50 
                 0.50 
                 0.50 
                 0.60 
                 0.95 
                 1.00 
                 0.123 
               
               
                 5 
                 0.60 
                 0.60 
                 0.60 
                 0.60 
                 0.90 
                 1.00 
                 0.126 
               
               
                 6 
                 0.50 
                 0.50 
                 0.50 
                 0.60 
                 0.90 
                 1.00 
                 0.129 
               
               
                 7 
                 0.50 
                 0.50 
                 0.60 
                 0.60 
                 1.00 
                 1.00 
                 0.130 
               
               
                 8 
                 0.60 
                 0.60 
                 0.60 
                 0.60 
                 0.95 
                 0.95 
                 0.130 
               
               
                 9 
                 0.50 
                 0.50 
                 0.50 
                 0.60 
                 0.95 
                 0.95 
                 0.133 
               
               
                 10 
                 0.50 
                 0.60 
                 0.70 
                 0.70 
                 1.00 
                 1.00 
                 0.134 
               
               
                   
               
            
           
         
       
     
     If the best matching space ratio is extracted as is in the conventional method, layers R 1  to R 4  each have the developer space ratio of 0.6, and layers D 1  and D 2  each have the developer space ratio of 1.00. In this case, the difference is slightly 4% between the sum of squares in ranks 1 and 2. The difference is within an error range considering the margin of the ratio (allowable range value: 10%). Therefore, the sum of squares ranging within 10% of the sum of squares in the rank  1  is given as a candidate. The space ratio predictive value rp i  is calculated from the ratio of developer occupying space based on weighted average. In the Table 2, ranks 1 to 5 are given as the candidate. The result of an experiment is shown in the following Table 3. 
     
       
         
           
               
               
               
               
               
               
               
             
               
                 TABLE 3 
               
               
                   
               
               
                   
                 Layer  
                 Layer  
                 Layer  
                 Layer  
                 Layer  
                 Layer  
               
               
                   
                 R 1   
                 R 2   
                 R 3   
                 R 4   
                 D 1   
                 D 2   
               
               
                   
                 25 nm 
                 135 nm 
                 135 nm 
                 5 nm 
                 10 nm 
                 10 nm 
               
               
                   
               
             
            
               
                 Ratio  
                 0.560 
                 0.560 
                 0.560 
                 0.600 
                 0.961 
                 1.000 
               
               
                 of 
                   
                   
                   
                   
                   
                   
               
               
                 resist 
               
               
                   
               
            
           
         
       
     
     According to the result, the bottom dimension of the resist in this stage was determined as 114.4 nm (=260×(1−0.56). A desired pattern dimension is 115 nm±8%; therefore, development was stopped in the stage, and rinsing was carried out. To make sure, a comparison by the database prepared under the same condition as the Table 1 in atmosphere was made; as a result, the resist remaining pattern dimension was 114.0 nm. In this case, developer/space is replaced with atmosphere/space, and modeling is carried out using optical constant of atmosphere. Further, a length measuring machine using an electron beam measured the line width of the resist pattern. As a result, the resist pattern was 114.1 nm, that is, the same value as the developing measurement value was obtained. 
     In  FIG. 5 , there is shown a comparison between a reflectance calculated using the space ratio predictive value calculated based on the foregoing weighted average and a measured value.  FIG. 5  shows the comparison in a range from 500 nm to 700 nm. In  FIG. 5 , there is shown the solid line curve fitting the measured value using a 15-order function. It can be seen that the calculated reflectance wavelength dispersion using the distribution shown in the Table 3 is very weighted in the 15-order function. Therefore, the actual measured value is sufficiently reproduced. 
     In  FIG. 5 , reflectance wavelength dispersion calculated from the minimum sum of squares model is shown by the broken line. The curves shown by the solid and broken lines locally coincide with each other. However, it is difficult to say that these curves coincide with each other in the entire wavelength range shown in  FIG. 5 . In addition, the measured resist pattern line width is 104 nm, which is 10 nm thinner than the actual value. With the measured value, the resist pattern is determined as failure; as a result, the substrate is reclaimed. The foregoing 114 nm is a true value, and thus, the result of making an incorrect determination as to whether a product is defective or not is given as a matter of course. 
     According to the first embodiment, it is possible to predict the dimension more accurately than the conventional method. In addition, it is possible to make a suitable determination as to whether a produce is defective or not. The following Table 4 shows model conditions in the case where analysis having the same accuracy as the present experiment is made using the conventional method. 
     
       
         
           
               
               
               
               
             
               
                 TABLE 4 
               
               
                   
               
               
                 Film 
                 Classification of 
                   
                 Step of 
               
               
                 structure 
                 film structure 
                 Range of ratio 
                 ratio (%) 
               
               
                   
               
             
            
               
                 Developer 
                 Layer D 2   
                 Developer/space = 
                 0.01 
               
               
                 layer 
                   
                 ratio of layer D 1  - 1.00 
                   
               
               
                   
                 Layer D 1   
                 Developer/space = 
                 0.01 
               
               
                   
                   
                 0.80-1.00 
                   
               
               
                 Resist 
                 Layer R 4   
                 Developer/space = 
                 0.01 
               
               
                 layer 
                   
                 ratio of layer R 3  - 1.00 
                   
               
               
                   
                 Layer R 3   
                 Developer/space = 
                 0.01 
               
               
                   
                   
                 ratio of layer R 2  - 0.70 
                   
               
               
                   
                 Layer R 2   
                 Developer/space = 
                 0.01 
               
               
                   
                   
                 ratio of layer R 1  - 0.70 
                   
               
               
                   
                 Layer R 1   
                 Developer/space = 
                 0.01 
               
               
                   
                   
                 0-0.70 
                   
               
               
                 Anti- 
                 Anti-reflection 
                 Anti-reflection material/ 
                 — 
               
               
                 reflection 
                 film layer 
                 space = 1.00 (fixed) 
                   
               
               
                 film layer 
                   
                   
                   
               
               
                 Si 
                 Si substrate 
                 Si/space = 1.00 (fixed) 
                 — 
               
               
                 substrate 
               
               
                   
               
            
           
         
       
     
     The number of calculated values prepared in the Table 1 is 1/2.5×10 5  of that of the Table 4; therefore, the number of data is largely reduced. The detection time is 0.2 seconds, and measurement in developing is readily made. According to the conventional method, about 14 hours are taken to make the measurement. As a result, it is considerably difficult to apply the conventional method to the measurement in developing. In addition, it is difficult to apply the conventional method to evaluation in normal atmosphere. As seen from the foregoing description, retrieval time is largely shortened, and the resist pattern dimension is readily predicted in accordance with the advance of the process. 
     The resist pattern dimension is predicted in the first embodiment. The present invention, however, is not limited to the preceding embodiment.  FIG. 6  is a graph showing dimension variations of developing KrF resist in sectional shapes using the reflectance wavelength dispersion calculation value database calculated based on the model of the Table 1. The sectional shapes are obtained by calculating a ratio of resist to space for each layer, and connecting the calculated ratios in the film thickness direction. In  FIG. 6 , a dotted line shows a sectional shape of the resist pattern after 4 seconds from the development start. A chain double-dashed line shows a sectional shape of the resist pattern after 6 seconds from the development start. A chain dashed line shows a sectional shape of the resist pattern after 10 seconds from the development start. A rough dashed line shows a sectional shape of the resist pattern after 20 seconds from the development start. A solid line shows a sectional shape of the resist pattern after 30 seconds from the development start. It can be seen that the bottom dimension of the resist pattern is wide after 4 seconds from the development start. With the advance of development, the resist pattern becomes gradually thin in its top and bottom, and then, is formed into a rectangular shape. 
       FIG. 7  is a graph showing the bottom dimension of the resist film with development time as the horizontal axis.  FIG. 7  exhibits that the time when the resist pattern becomes a 0.44 size to pitch is 20 seconds (dashed line denotes a dimension ratio calculated without stopping development). As shown in  FIG. 7 , the dimension with respect to time is calculated one after another to predict development time to obtain a desired dimension. The development is stopped, and thereby, high-accurate development control is possible.  FIG. 6  is obtained from calculation based on weighted average using several reflectance wavelength dispersion calculation values. Therefore, the relationship shown in  FIG. 7  has high accuracy. 
     On the contrary, according to the conventional method, the dimension ratio relationship with respect to development time is reversed as seen from  FIG. 8 ; for this reason, accurate development control is not obtained. Consequently, the method of this embodiment is employed, and thereby, it is possible to greatly improve the development control. 
     The first embodiment relates to dimension measurement in development and after development; however, the present invention is not limited to this embodiment. For example, the present invention is applicable to dimension measurement for etching pattern of oxide film and interconnection pattern. In this case, database and measured values are analyzed in the same method as the resist pattern dimension measurement. The database comprises materials such as oxide film and interconnection and reflectance wavelength dispersion calculation values calculated by changing the space ratio. By doing so, it is possible to effectively obtain the pattern dimension and profile with high accuracy for short time. 
     The first embodiment relates to structure prediction using reflectance calculation; however, the present invention is not limited to this embodiment. For example, cos δ and tan ψ are calculated by RCWA from film structure models which have several space ratios to prepare database. Then, similar waveforms as cos δ and tan ψ measured by ellipsometry technique are found from the database using the similar method described above. The space ratio is predicted based on weighted average where larger weight is given as the error is smaller. By doing so, it is possible to specify the structure of the measured substance. 
     In the first embodiment, the space ratio predictive value r is calculated based on the weighted average using reciprocals of the sum of squares as shown in the equation (4). However, the present invention is not limited to the calculation. The space ratio predictive value r may be calculated using any other equations so long as the space ratio is large when R, which is an absolute value R of an error of a measured value, is small. For example, the space ratio predictive value r is expressed using the following equation (5). The f(R) in the equation (5) should decreases as R increases in a range R can take, that is f(R) should be simple decreasing function in a range R can take.
 
 r =(Σ r   i   ×f ( F ))/(Σ f ( R ))  (5)
 
     where, f(R)=1/R, 1/R x : x is positive real number, e −R , etc. 
     (2) Second Embodiment 
     An etching depth is calculated in the same manner as the first embodiment. More specifically, etching pattern materials and a space ratio of etching atmosphere (supply gas and reaction gas) are changed, and a reflectance wavelength dispersion calculation value database is prepared. Measured values are compared with the database to extract several wavelength dispersion calculation values similar to these measured values. The etching depth is calculated from weighted average based on the sum of squares of the original space ratio. 
       FIG. 9  is a graph showing etching depth calculated from reflectance measured for each etching time of oxide film. The depth (dashed line) calculated by the conventional method has a large drift of etching rate as time passes; as a result, the calculated depth is unstable. On the contrary, the etching depth (solid line) to etching time calculated based on weighted average according to the present embodiment is very favorable. A constant value is obtained in the etching rate after 20 seconds (i.e., a change of the etching depth to unit etching time is constant). Thus, in the second embodiment, etching depth analysis is carried out without receiving an influence by analysis error. 
     Etching stop control is possible using  FIG. 9 . However, the conventional method has the following problem. The drift is large, and etching stop accuracy worsens; for this reason, the stopper film under the oxide film may be etched. On the contrary, according to the method of the second embodiment, etching stop control is possible with high accuracy. Therefore, fine processing is realized without giving damages to the stopper material under the oxide film; as a result, the process of forming the stopper film is largely reduced. 
     (3) Third Embodiment 
     The third embodiment relates to a structure inspection method of films in a process of manufacturing a semiconductor device. 
     [3-1] Flow of the Process of Manufacturing a Semiconductor Device 
     The process of manufacturing a semiconductor device will be described below with reference to  FIG. 10  to  FIG. 12 .  FIG. 10  is a flowchart to explain the process of manufacturing a semiconductor device according to the third embodiment of the present invention.  FIGS. 11A to 11C  are each cross-sectional views successively showing the process of manufacturing a semiconductor device according to the third embodiment. 
     As shown in  FIG. 11A , a first silicon oxide film  502  having a film thickness of 100 nm is formed on a non-processed silicon substrate  501  (step S 201 ). Thereafter, the film thickness of the silicon oxide film  502  is measured (step S 202 ). 
     As illustrated in  FIG. 11B , a second silicon oxide film  503  having a film thickness of 500 nm is formed on the first silicon oxide film  502  (step S 203 ). The first and second silicon oxide films  502  and  503  have optical constant slightly different from each other. The substrate formed with the second silicon oxide film  503  is called a substrate A. 
     In order to measure the film thickness of the second silicon oxide film  503 , the light intensity of the substrate A (step S 204 ) is measured.  FIG. 12  is a schematic view showing a light intensity optical system. Light travels into the substrate A. A reflected light from the substrate A is measured, and thereby, wavelength dispersion of intensity change (tan ψ) and phase change (cos Δ) of the reflected light are measured. TM, TE polarized lights and polarized light beam such as other polarized lights may be used as the reflected light measured here, or reflected light may be directly used without using a deflection plate. Incident angle may be vertical to the substrate A. Light of single wavelength may be used, and then, incident angle and detection angle are changed to measure the intensity. In brief, any method can be taken as long as reflected incident light is measured. 
     The film thickness of the second silicon oxide film  503  is determined from the measured light intensity of the substrate A (step S 205 ). 
     As depicted in  FIG. 11C , an anti-reflection film  504  having a film thickness of 50 nm and a resist film  505  of 250 nm are coated and formed on the second silicon oxide film  503  (step S 206 ). The resist film  505  is exposed using ArF excimer laser via reticle. Baking and development are carried out; as a result, a resist pattern having 100 nm line/space (1:1) is formed. The resist pattern has lines and spaces which have a width of 100 nm and are arranged alternatively. The substrate of the foregoing state is called a substrate B. 
     In order to measure the film thickness of the anti-reflection film  504 , the pattern dimension and film thickness of the resist film  505 , light intensity of the substrate B is measured (step S 207 ).  FIG. 13  is a schematic view showing an optical system used for the process of inspecting the substrate B. Light is radiated to the substrate B. Zero-order light of diffraction lights from the substrate B is measured, and thereby, the wavelength dispersion of intensity change (tan ψ) and phase change (cos Δ) of the diffraction light are measured. TM, TE polarized lights and polarized light beam such as other polarized lights may be used as the measurement target, or diffraction light may be directly used without using a deflection plate, like the film thickness measurement. In addition, first-order or more light may be used instead of the zero-order light. Vertical or oblique incident angle may be used as the incident angle of light. Light is made incident on the substrate B at single wavelength, and then, incident angle and detection angle are changed to measure the intensity. In brief, any method can be taken as long as reflected incident light is measured. 
     The resist pattern dimension (line width) is measured from the light intensity of the substrate B as the inspection for anti-reflection film  504  and resist pattern (step S 208 ). In semiconductor wafer process, processes and the inspection of structure (film thickness, pitch, ratio, dimension, optical constant) changed or added by the process are repeatedly carried out. 
     [3-2] Inspection Procedure 
     The inspection procedure will be explained in detail below.  FIG. 14  is a flowchart to explain the structure inspection procedure according to the third embodiment. Prior to inspection, a light intensity library storing substrate structure and light intensity corresponding thereto is prepared. 
     A structure group including structures predicted in at least each layer is prepared with respect to all layers on the substrate (step S 301 ). Layer structure is optical constant of layer, film thickness, pitch, ratio, dimension, etc. Predicted layer structure is included in a range of structure variations occurring in process. A substrate structure is prepared by combining structures of each layer. 
     A substrate structure library A comprising various substrate structures prepared in step S 301  is prepared (step S 302 ). Light is irradiated to each substrate structure stored in the substrate structure library A under the same condition as the actual inspection. Thus, light intensity obtained by reflection or diffraction is calculated, and further, wavelength dispersion of the light intensity in each substrate structure is calculated (step S 303 ). In general, RCWA (Rigorous coupled-wave analysis) by Morham et al. (J. Opt. Soc. Am., Vol. 12, No. 5, May 1995 1077-1086) is used as the calculation method. According to the foregoing RCWA, electric filed, magnetic field and intensity of refraction light from regular pattern are obtained using Maxwell equations. 
     A light intensity library B is prepared (step S 304 ). The light intensity library B stores substrate structures stored in the substrate structure library A and wavelength dispersion of light intensity corresponding thereto. 
     Prior to structure inspection, the inspection result of structure actually prepared in the manufacture process is used, and thereby, light intensity library is extracted (narrowed down). In the extraction, substrate structures including structures diverging from already-existing structures obtained by inspection are removed from the inspection comparison target. By doing so, it is possible to reduce the number of comparison target substrate structures stored in library in the comparison process between substrate structures in inspection target and library. Namely, layers having the layer structure determined by actual inspection (e.g., structure-inspected layers under inspection target layer) are extracted (step S 401 ). Then, a layer structure group is prepared with respect to the extracted layer based on the layer structure inspection result (step S 402 ). In this case, the layer structure group is prepared considering inspection accuracy. 
     The structure group of the extracted layer is compared with the substrate structure library A prepared in step S 302 . By doing so, substrate structures including the structure group of the extracted layer are extracted. As a result, a substrate structure library B is prepared (step S 403 ). 
     Light intensity corresponding to substrate structures in the substrate structure library B is fetched from the light intensity library B. By doing so, a light intensity library C is prepared (step S 404 ). 
     Substrates having actual several layers on it are carried into the inspection apparatus having the optical system shown in  FIG. 2  and  FIG. 3 . Thereafter, wavelength dispersion of the light intensity in the inspection area is measured (step S 501 ). Wavelength dispersion of the measured light intensity is compared with wavelength dispersion stored in the light intensity library C (Step S 502 ). The wavelength dispersion which matches best with the wavelength dispersion of the measured light intensity is detected from the light intensity library C. The substrate structure corresponding to the detected wavelength dispersion is determined as an inspection target substrate structure (step S 503 ). 
     For comparison, the conventional inspection procedure will be described below with reference to  FIG. 18 . As seen from  FIG. 18 , the light intensity library B based on the inspection result of already-obtained layers is not prepared in the conventional inspection procedure unlike the second embodiment. In other words, the light intensity library A is compared with the light intensity measured result (step S 512 ). 
     [3-3] Another Embodiment of Inspection Procedure 
     Various methods may be given as the procedure of preparing the light intensity library C. The procedure shown in  FIG. 15  is given as one of these methods. According to the inspection procedure shown in  FIG. 15 , no wavelength dispersion calculation of light intensity of substrate structures stored in the substrate structure library A is made. Instead of that, wavelength dispersion of light intensity of each substrate structure is calculated after the substrate structure library B (step S 414 ). By doing so, a light intensity library C is prepared (step S 415 ). 
     The procedure taken according to a flowchart shown in  FIG. 16  is given as another embodiment of the present invention. According to the inspection procedure shown in  FIG. 16 , a layer having no determined structure (e.g., layer which has undergone no structure inspection because the structure is not determined) is extracted in detecting a substrate structure of a certain state (step S 421 ). Thereafter, a structure group relevant to the layer extracted in step S 421  is prepared (step S 422 ). 
     In addition, a structure-determined layer (e.g., actually formed layer already having undergone structure inspection) is extracted (step S 423 ). Thereafter, a structure group of the structure-determined layer is prepared (step S 424 ). A substrate structure library B is prepared based on the structure groups prepared in steps S 422  and S 424  (step S 403 ). In other words, various structures are formed by putting the predicted structures on structure-inspected layers. The structures obtained like this makes the substrate structure library B. 
     [3-4] Process of Manufacturing a Semiconductor Device Including Inspection Process 
     An example of embodiment in which the inspection procedure described with reference to  FIG. 11A  to  FIG. 11C  is applied to the process of manufacturing the semiconductor device will be described.  FIG. 17  is a flowchart to explain the process of manufacturing a semiconductor device according to the third embodiment of the present invention. When the light intensity is measured (step S 204 ), silicon oxide films A and B (first and second silicon oxide films) are formed on the Si substrate. Therefore, a substrate structure library IIA includes each predicted structure group of the foregoing Si substrate, silicon oxide films A and B (step S 301 ). The substrate structure library IIA was prepared using each structure group prepared in step S 301  (step S 302 ). The number of structure groups of the Si substrate, silicon oxide films A and B prepared in step S 301  were 1, 21 and 101, respectively. Thus, the number of structure groups stored in the substrate structure library IIA was 2121. 
     A structure group of the silicon oxide film A is newly prepared using the film thickness of the silicon oxide film measured in step S 202  (step S 402 ). In other words, a structure group including the actually formed silicon oxide film A is prepared. The film thickness d A  of the silicon oxide film was determined as 102 nm, and the measurement accuracy was set as ±1 nm in an experiment. Thus, a structure group of the silicon oxide film A shown in the following Table 5 was prepared. The allowable range value of the film thickness was set to 1 nm in order to improve the measurement accuracy 
     
       
         
           
               
               
               
               
               
               
             
               
                 TABLE 5 
               
               
                   
               
               
                   
                   
                   
                 Allowable 
                   
                   
               
               
                   
                   
                   
                 range of 
                   
                   
               
               
                   
                 Refractive 
                 Extinction 
                 film 
                   
                 Number of 
               
               
                 Layer 
                 index 
                 coefficient 
                 thickness 
                 Step 
                 structures 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Si substrate 
                 n 0   
                 k 0   
                 — 
                 — 
                 1 
               
               
                 Silicon oxide 
                 n 1   
                 k 1   
                 d A  ± 1% 
                 1 nm 
                 3 
               
               
                 film A 
                   
                   
                   
                   
                   
               
               
                 Silicon oxide 
                 n 2   
                 k 2   
                 d B  ± 1% 
                 1 nm 
                 101 
               
               
                 film B 
               
               
                   
               
            
           
         
       
     
     Therefore, in the substrate structure library IIA, necessary substrate structure is combinations of structure groups shown in the Table 5. As a result, the number of structures of Si substrate, silicon oxide films A and B prepared in step S 403  are 1, 3 and 101, respectively. Thus, a substrate structure library IIB was composed of substrate structures comprising these combinations. Wavelength dispersion of the light intensity corresponding to each substrate structure stored in the substrate structure library IIB is extracted from the light intensity library IIA. By doing so, a light intensity library IIB is prepared. Therefore, the number of wavelength dispersions of the light intensity stored in the light intensity library IIB prepared in step S 404  was 303. 
     When the wavelength dispersion of light intensity in step S 207  is measured, silicon oxide films A, B, anti-reflection film (ALF) and resist film are formed. Each structure group is prepared from predicted structures of the foregoing silicon oxide films A, B, anti-reflection film (ALF) and resist film. In this case, each structure of the silicon oxide films A and B was detected in steps S 202  and S 205 . Thus, based on the detection result, each structure group of the silicon oxide films A and B was prepared (step S 422 ). In addition, each structure group of Si substrate, anti-reflection film and resist film having undergone no structure detection is prepared based on predicted several structures (step S 424 ). 
     The film thickness d A  of the silicon oxide film A was determined as 102 nm, and the film thickness d B  of the silicon oxide film A was determined as 510 nm, and further, the measurement accuracy was set as ±1 nm. Therefore, each structure group of the silicon oxide films A and B shown in the following Table 6 is prepared. These structure groups are combined, and thereby, various substrate structures are obtained; therefore, a substrate structure library IIIB was prepared based on these substrate structures. In the Table 6, each structure group of Si substrate, anti-reflection film and resist film is shown. 
     
       
         
           
               
               
               
               
               
               
               
               
             
               
                 TABLE 6 
               
               
                   
               
               
                   
                   
                   
                 Allowable 
                   
                   
                   
                   
               
               
                   
                   
                   
                 range of 
                   
                 Allowable 
                   
                   
               
               
                   
                 Refractive 
                 Extinction 
                 film 
                   
                 range of 
                   
                 Number of 
               
               
                 Layer 
                 index 
                 coefficient 
                 thickness 
                 Step 
                 dimension 
                 Step 
                 structures 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Si substrate 
                 n 0   
                 k 0   
                 — 
                 — 
                 — 
                 — 
                 1 
               
               
                 Silicon oxide 
                 n 1   
                 k 1   
                 d A  ± 1% 
                 1 nm 
                 — 
                 — 
                 3 
               
               
                 film A 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Silicon oxide 
                 n 2   
                 k 2   
                 d B  ± 1% 
                 1 nm 
                 — 
                 — 
                 11 
               
               
                 film B 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Anti-reflection 
                 n 3   
                 k 3   
                 d 3  ± 2% 
                 1 nm 
                 — 
                 — 
                 3 
               
               
                 film 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Resist film 
                 n 4   
                 k 4   
                 d 4  ± 2% 
                 1 nm 
                 w 4  ± 10% 
                 1 nm 
                 231 
               
               
                   
               
            
           
         
       
     
     As depicted in the Table 6, the substrate structure library IIIB stores substrate structures obtained from the combination of structure groups shown in the Table 6. The number of each structure group of silicon oxide films A, B, Si substrate, anti-reflection film and resist film were 1, 3, 11, 3, 231, respectively. Therefore, the number of substrate structures stored in the substrate structure library IIIB was 22869. A light intensity library IIIC is prepared from wavelength dispersion of the light intensity corresponding to substrate structures stored in the substrate structure library IIIB. 
     In preparation for the structure group of silicon oxide films A and B, the structure group was prepared based on a measurement accuracy range (±1%) as seen from the Table 6. The structure group may be prepared based on a measurement accuracy range (±2%) of two times as much as the foregoing definition in view of a margin. In preparation for the structure group of anti-reflection film and resist film, the structure group may be prepared based on a measurement accuracy range (±4%) of two times as much as the foregoing range in view of a margin against drift. 
     For comparison, the case where the conventional structure inspection method shown in  FIG. 18  is applied to the flow shown in  FIG. 10  will be described below with reference to  FIG. 19 . As seen from  FIG. 19 , according to the conventional method, the light intensity library IIB based on the inspection result of obtained layers is not prepared unlike the third embodiment. For this reason, a comparison is required between the light intensity library IIB and the light intensity measurement result (step S 503 ). 
     In step S 204  of making light intensity measurement for inspecting the structure of the silicon oxide film B, silicon oxide films A and B are formed on the Si substrate. Therefore, each predicted structure group of Si substrate, silicon oxide films A and B was prepared (step S 301   a ). 
     
       
         
           
               
               
               
               
               
               
             
               
                 TABLE 7 
               
               
                   
               
               
                   
                   
                   
                 Allowable 
                   
                   
               
               
                   
                   
                   
                 range of 
                   
                   
               
               
                   
                 Refractive 
                 Extinction 
                 film 
                   
                 Number of 
               
               
                 Layer 
                 index 
                 coefficient 
                 thickness 
                 Step 
                 structures 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Si substrate 
                 n 0   
                 k 0   
                 — 
                 — 
                 1 
               
               
                 Silicon oxide 
                 n 1   
                 k 1   
                 d A  ± 10% 
                 1 nm 
                 21 
               
               
                 film A 
                   
                   
                   
                   
                   
               
               
                 Silicon oxide 
                 n 2   
                 k 2   
                 d B  ± 10% 
                 1 nm 
                 101 
               
               
                 film B 
               
               
                   
               
            
           
         
       
     
     The refractive index and the extinction coefficient have no drift in the process flow of inspecting silicon oxide films A and B. The silicon oxide films A and B each had a film thickness of ±10% with respect to the main value; therefore, a structure group shown in the Table 7 was defined. 
     As shown in the Table 7, the number of structure groups of Si substrate, silicon oxide films A and B were 1, 21 and 101, respectively. Therefore, the number of substrate structures stored in the light intensity library IIA was 2121 (step S 302   a ). The light intensity library IIA was prepared based on the substrate structure library IIA (step S 303   a ). For this reason, it stores the same number of wavelength dispersion samples as the substrate structure library IIA. 
     In step S 207  of making light intensity measurement for inspecting anti-reflection film and resist film, silicon oxide films A, B, anti-reflection film and resist film are formed on the Si substrate. Therefore, each predicted structure group of the foregoing Si substrate, silicon oxide films A, B, anti-reflection film and resist film were prepared (step S 301   b ). 
     Each structure group of components described above is shown in the following Table 8. 
     
       
         
           
               
               
               
               
               
               
               
               
             
               
                 TABLE 8 
               
               
                   
               
               
                   
                   
                   
                 Allowable 
                   
                   
                   
                   
               
               
                   
                   
                   
                 range of 
                   
                 Allowable 
                   
                   
               
               
                   
                 Refractive 
                 Extinction 
                 film 
                   
                 range of 
                   
                 Number of 
               
               
                 Layer 
                 index 
                 coefficient 
                 thickness 
                 Step 
                 dimension 
                 Step 
                 structures 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Si substrate 
                 n 0   
                 k 0   
                 — 
                 — 
                 — 
                 — 
                 1 
               
               
                 Silicon oxide 
                 n 1   
                 k 1   
                 d A  ± 10% 
                 1 nm 
                 — 
                 — 
                 21 
               
               
                 film A 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Silicon oxide 
                 n 2   
                 k 2   
                 d B  ± 10% 
                 1 nm 
                 — 
                 — 
                 101 
               
               
                 film B 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Anti-reflection 
                 n 3   
                 k 3   
                 d 3  ± 2%  
                 1 nm 
                 — 
                 — 
                 3 
               
               
                 film 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Resist film 
                 n 4   
                 k 4   
                 d 4  ± 2%  
                 1 nm 
                 w 4  ± 10% 
                 1 nm 
                 231 
               
               
                   
               
            
           
         
       
     
     The refractive index and the extinction coefficient have no drift in the process flow, and the film thickness of silicon oxide film, anti-reflection film and resist film was ±10%, ±2% and ±2% with respect to the center value, respectively. Therefore, a structure group shown in the Table 8 was defined. The number of each structure group of Si substrate, silicon oxide films A, B, anti-reflection film and resist film were 1, 21, 101, 3, 231, respectively. As a result, the number of substrate structures stored in a substrate structure library IIIA defined in step S 302   b  was 453789. A light intensity library IIIA was prepared based on the substrate structure library IIIA (step S 303   b ). Thus, the light intensity library IIIA stores the same number of wavelength dispersion samples as the substrate structure library IIIA. 
     [3-4] Advantages 
     [3-4-1] Improvement in Measurement Accuracy 
     The conventional method has the following problems when determining the film thickness of the silicon oxide film B in the structure inspection procedure (step S 205 ). Wavelength dispersions are sometimes almost same in the case where individual film thickness of silicon oxide films A and B are d 11  nm, d 21  nm and in the case where individual film thickness of silicon oxide films A and B are d 12  nm, d 22  nm. In such a case, individual film thickness of silicon oxide films A and B may be miscalculated as d 12  nm, d 22  nm. According to the third embodiment, the value d 12  is not calculated as the film thickness as long as the value d 12  is not included in a rage of d 1 +1% (see  FIG. 9 ). Therefore, an erroneous measurement is unlikely, that realizes an improved measurement accuracy. 
     [3-4-2] Large Reduction of the Number of Samples Stored in Library 
     According to the conventional method, the substrate structure library comprising samples including all structural combinations predicted in each layer is prepared and the light intensity library comprising the same number of samples stored in the substrate structure library is prepared. For this reason, the light intensity library stores huge number of samples. On the contrary, according to the third embodiment, the inspection result prior to the inspection in a certain structure inspection process is considered to prepare the light intensity library. Therefore, the number of samples stored in the light intensity library largely decreases. As a result, it is possible to shorten time to retrieve similar wavelength dispersions of light intensity as the measured result of the wavelength dispersions of light intensity. 
     The following Table 9 shows the number of samples stored in each light intensity library. 
     
       
         
           
               
               
               
             
               
                   
               
             
            
               
                   
                 Light intensity 
                 Light intensity 
               
               
                   
                 library IIA 
                 library IIB 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Number of samples 
                 2121 
                 303 
               
               
                   
               
            
           
           
               
               
               
            
               
                   
                 Light intensity 
                 Light intensity 
               
               
                   
                 library IIIA 
                 library IIIB 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Number of samples 
                 453789 
                 22869 
               
               
                   
               
            
           
         
       
     
     According to the conventional method, the substrate structure is determined using light intensity libraries IIA and IIIA. On the contrary, according to the third embodiment, the substrate structure is determined using light intensity libraries IIB and IIIB. 
     The number of samples stored in the light intensity library is largely reduced, and thereby, the inspection procedure can be taken without preparing additional light intensity library as seen from  FIG. 15  and  FIG. 16 . For example, it is needed to prepare the substrate structure library IIIA and the light intensity library IIIA covering all possible predicted structural combination before the inspection process as preparation for the structure determining process (step S 208 ). 
     On the contrary, according to the third embodiment, it is not required to prepare the light intensity library IIIA. After the substrate structure is determined (step S 205 ), the light intensity library IIIB reflecting the substrate structure result is prepared. The substrate structure library IIA having all possible samples is not prepared; therefore, the capacity of the library is largely reduced. 
     When a conventional coater/developer has a structure inspection function, the structure inspection may be made until the process for a series of lots is completed. Thus, it suffices that the light intensity library IIIB is prepared until a series of processes is completed, and the measured light intensity is compared with the light intensity library IIIB to obtain the inspection result. As a result, the capacity of the library is largely reduced while inspection is made with high accuracy. 
     (4) Fourth Embodiment 
     The fourth embodiment relates to a pattern evaluation method in development. 
     [4-1] The Entire Flow of Development 
       FIG. 20  is a schematic view to explain the pattern evaluation during development, and  FIG. 21  is a flowchart to explain the procedure of a pattern evaluation method. The procedure of the pattern evaluation method of the fourth embodiment will be described below with reference to  FIG. 20  and  FIG. 21 . 
     As shown in  FIG. 20 , a resist film  304  is coated on a specified front-end substrate (comprising Si substrate  301 , lower-layer film  302  and anti-reflection film  303  in order from the bottom). The resist film  304  is baked and exposed, and thereafter, baked again. After a developer is supplied onto the front-end substrate, light is irradiated to the monitor region on the front-end substrate, and then, a diffraction light is detected. Therefore, in addition to the developer  305 , a reaction product of the resist film  304  and a mixed phase of the developer exist over the resist film  304  and each pattern thereof. Broad light having several wavelengths (e.g., halogen lamp light) is used as the incident light. TM deflection intensity of zero-order diffraction light is measured within a wavelength range from 400 to 800 nm. The TM deflection is obtained by arranging a deflection plate in the optical path of the zero-order diffraction light. Wavelength dispersion of the intensity of the diffraction light detected here is uniquely determined depending on the structure of measurement region and optical constant. According to the fourth embodiment, the diffraction light from pattern is measured during development, and dimension is evaluated from the measured result. 
     The evaluation procedure will be explained below with reference to  FIG. 21 . In the fourth embodiment, the diffraction light intensity is predicted before the development process, and a library is prepared. The evaluation procedure comprises a process of preparing a library before development and a process of evaluating a pattern dimension in the development process. 
     In the process of preparing a library, the following parameters are given to determine a development model (step S 601 ). One of the parameters is an opening shape of the development region when the resist film is dissolved in the developer. Another one is a distribution of a mixture ratio of reaction product and developer in a liquid phase consisting of the reaction product of resist and the developer. 
     Then, the following parameters, that is, substrate structure comprising liquid phase and the substrate with films thereon, and optical constant of a developer, the substrate and the reaction product are given (step S 602 ). Calculation when light is introduced at a specified angle is made based on the given structure and optical constant to obtain a wavelength dispersion of diffraction light intensity (step S 603 ). RCWA (Rigorous coupled-wave analysis) by Morham et al. (J. Opt. Soc. Am., Vol. 12, No. 5, May 1995 1077-1086) is used as the calculation method to acquire electric filed, magnetic field and intensity of refraction light from regular pattern using Maxwell equations. Calculation is made with respect to all conditions of the given structure and optical constant to prepare a wavelength dispersion library of the diffraction light intensity (step S 604 ). The preparation for the library will be described later. 
     The process of evaluating a pattern dimension will be described below. The substrate (wafer) is carried to a development unit (step S 605 ). A developer is supplied onto the substrate, and then, development is started (step S 606 ). Thereafter, the reflection light of the monitor region is measured (step S 607 ). The position of the substrate and a monitor unit must be controlled so that light advances onto the monitor region and a detector detects the diffraction light. The control may be carried out before the developer is supplied if the substrate is not moved. If not so, the control is carried out after the developer is supplied. A comparison is made between wavelength dispersion of the measured diffraction light intensity and wavelength dispersion of diffraction light stored in the library (step S 608 ). The best wavelength dispersion matching with the wavelength dispersion of diffraction light stored in the library is determined, and thus, pattern dimension is calculated (step S 609 ). 
     [4-2] Method of Preparing Library 
     The process of preparing the library will be described below. As described in  FIG. 20 , the reaction product of resist is generated from the developing resist pattern. In the following description, a developer containing the reaction product of resist call is called a mixed phase, and a ratio of resist in the mixed phase is defined as a mixture ratio. In general, the diffusion velocity of the reaction product is not so fast. For this reason, if the diffusion of the reaction product, that is, a distribution of the mixture ratio in liquid phase is not considered in a model, the accuracy of developing pattern evaluation worsens. In order to solve the problem, a development model considering the distribution is determined in a library preparation process in the fourth embodiment (step S 601 ). 
       FIG. 22A  is a schematic view showing the development progress at the initial development. In the initial development, development advances to the film thickness direction in the development region. As a result, the reaction product diffuses to the direction shown by an arrow (downwardly toward the Si substrate  301 ). Thus, the mixture ratio has a distribution in a film thickness direction, and the ratio decreases as the position gets away from the Si substrate  301 . 
     When the development in the film thickness direction completes, development advances laterally as illustrated in  FIG. 22B . Thus, the reaction product diffuses to direction shown by arrows in  FIG. 23  (toward remaining resist film  304  from the opening position of the resist film  304 ). As a result, the mixture ratio decreases as the position gets away from pattern sidewall in the lateral direction. In fact, the changes of the mixture ratios are overlapped, and thereby, the combined changes make a distribution. According to the distribution, the mixture ratio decreases toward the arrow direction shown in  FIG. 23  (i.e., direction separating from the Si substrate  301  and direction toward the opening position from the remaining resist film  304 ). 
     The following is a description of the step of giving substrate structure and optical constant.  FIG. 24  shows a layer structure in the film thickness direction prepared based on the model of  FIG. 23 . In  FIG. 24 , p denotes a pattern pitch, and w 1  denotes a resist pattern dimension. A layer L 0  comprises a developer, and a layer L 01  comprises the developer and the mixed phase of the reaction product of resist. Layers L 11  to L 13  each comprise the developer, the mixed phase of the reaction product of resist and resist pattern. A layer L 2  comprises an anti-reflection film. A layer L 3  comprises a lower-layer film, and a layer L 4  comprises a Si substrate. Layers L 11  to L 13  differ from each other in the mixture ratio of the reaction product. The reaction product is generated in the interface between resist and developer, and diffuses to the developer layer; for this reason, the ratio is higher in the lower layer (L 13 ) of the pattern. 
       FIG. 25  shows a distribution of the mixture ratio of Layers L 0  to L 13 . The layer L 0  comprises only the developer; therefore, the mixture ratio is 0. The layer L 01  comprises the developer and the mixed phase of the reaction product, and the mixture ratio is set as a fixed value r 01 . Layers L 11  to L 13  each comprise the developer, the mixed phase of the reaction product of resist and resist pattern; therefore, the mixture ratio r is given as a positional function, and distributes as shown in  FIG. 25 . As depicted in  FIG. 25 , the mixture ratio is 0 in the resist pattern region (0&lt;x&lt;w 1 /2, p−w 1 /2&lt;x&lt;p). The mixture ratio takes a value between 0 and 1 in a mixed phase region of the developer and the reaction product of resist (w 1 /2, &lt;x&lt;p−w 1 /2). Layers L 11 , L 12  and L 13  each take a function corresponding to the position, that is, r 11 (x), r 12 (x) and r 13 (x). The functions r 11 (x) to r 13 (x) have a relation such that the mixture ratio decreases as the position gets away from the interface between liquid phase and substrate. 
     Based on the distribution of the mixture ratio shown in  FIG. 25 , parameters required for obtaining structure and optical constant are given. The parameters include each refractive index, extinction coefficient, film thickness and dimension of layers L 0  to L 4 . Table 10 shows given refractive index, extinction coefficient, film thickness and dimension of the layers L 0  to L 4 .  FIG. 26  shows a refractive index of each layer.  FIG. 27  shows an extinction coefficient of each layer. The refractive index and the extinction coefficient of layers L 01 , L 11  to L 13  are expressed as a function of the position (x). 
     
       
         
           
               
               
               
               
               
               
             
               
                 TABLE 10 
               
               
                   
               
               
                   
                   
                 Refractive 
                 Extinction 
                 Film 
                   
               
               
                   
                 Layer 
                 index 
                 coefficient 
                 thickness 
                 Dimension 
               
               
                   
               
             
            
               
                   
                 L 0   
                 n 0   
                 k 0   
                 — 
                 — 
               
               
                   
                 L 01   
                 n 01   
                 k 01   
                 d 01   
                 — 
               
               
                   
                 L 11   
                 n 11 (x) 
                 k 11 (x) 
                 d 11   
                 w 1   
               
               
                   
                 L 12   
                 n 12 (x) 
                 k 12 (x) 
                 d 12   
                   
               
               
                   
                 L 13   
                 n 13 (x) 
                 k 13 (x) 
                 d 13   
                   
               
               
                   
                 L 2   
                 n 2   
                 k 2   
                 d 2   
                 — 
               
               
                   
                 L 3   
                 n 3   
                 k 3   
                 d 3   
                 — 
               
               
                   
                 L 4   
                 n 4   
                 k 4   
                 — 
                 — 
               
               
                   
               
            
           
         
       
     
     The layer L 0  comprises the developer only; therefore, the refractive index no and the extinction coefficient k 0  both take the value of the developer. The layer L 01  comprises the developer and the mixed phase of the reaction product of resist; therefore, the refractive index n 01  and the extinction coefficient k 01  both take a value between that of the developer (n 0 , k 0 ) and the resist (n 1 , k 1 ). The film thickness is d 01 . 
     Layers L 11  to L 13  each comprise the developer and the mixed phase of the reaction product of resist and resist pattern. Therefore, the refractive index and the extinction coefficient are expressed as a function of the position, and given as shown in  FIG. 26  and  FIG. 27 , respectively. In the resist pattern region (0&lt;x&lt;w 1 /2, p−w 1 /2&lt;x&lt;p), the refractive index and the extinction coefficient both take the resist value (n 1 , k 1 ), In the mixed phase region of the developer and the reaction product of resist (w 1 /2&lt;x&lt;p−w 1 /2), the refractive index and the extinction coefficient both take a value between that of the developer and the reaction product. These film thicknesses are respectively d 11 , d 12  and d 13 . 
     The layer L 2  comprises an anti-reflection film; therefore, the refractive index n 2  and the extinction coefficient k 2  both take a value of the anti-reflection film. The film thickness is d 2 . The layer L 3  comprises a lower-layer film; therefore, the refractive index n 3  and the extinction coefficient k 3  both take a value of the lower-layer film. The film thickness is d 3 . The layer L 4  comprises a Si substrate; therefore, the refractive index n 4  and the extinction coefficient k 4  both take a value of the Si substrate. 
     It is assumed that parameters variable in the process are film thickness d 1 , refractive index n 01 , and extinction coefficient k 01  of layer L 01 , film thickness d 11 , refractive index n 11  (x), and extinction coefficient k 11  (x) of layer L 11 , film thickness d 12 , refractive index n 12 , and extinction coefficient k 12  (x) of layer L 12  film thickness d 13 , refractive index n 13  (x), and extinction coefficient k 13  of layer L 13 , dimension w 1  of layer L 1 , film thickness d 2  of layer L 2 , and film thickness d 3  of layer L 3 . Then, if each parameter has five levels, the combination of structures and optical constants are given as 5 9 , that is, 1953125 (step S 601 , S 602 ). The refractive index and the extinction coefficient change depending on the diffusion of the reaction product. Calculation is made with respect to each structure and optical constant (step S 603 ), and 1953125 wavelength dispersions of diffraction light intensity are prepared (step S 604 ). 
     In a comparison of measured waveform in pattern evaluation (step S 608 ), wavelength dispersion of measured reflection light intensity is compared with wavelength dispersion of measured reflection light intensity stored in the library to calculate a dimension. 
     [4-3] Advantages 
     For comparison, a conventional developer model is shown in  FIG. 28 . As seen from  FIG. 28 , no consideration is taken with respect to the distribution of the mixture ratio of the developer and the reaction product in the film thickness direction. In addition, no consideration is taken with respect to the distribution of the mixture ratio of the developer and the reaction product between resist patterns. The following Table 11 shows values of refractive index, extinction coefficient, film thickness and dimension. The refractive index and extinction coefficient of the conventional developer model are shown in  FIG. 29  and  FIG. 30 , respectively. 
     
       
         
           
               
               
               
               
               
               
             
               
                 TABLE 11 
               
               
                   
               
               
                   
                   
                 Refractive 
                 Extinction 
                 Film 
                   
               
               
                   
                 Layer 
                 index 
                 coefficient 
                 thickness 
                 Dimension 
               
               
                   
               
             
            
               
                   
                 L 0   
                 n 0   
                 k 1   
                 — 
                 — 
               
               
                   
                 L 1   
                 n 1 (x) 
                 k 1 (x) 
                 d 1   
                 w 1   
               
               
                   
                 L 2   
                 n 2   
                 k 2   
                 d 2   
                   
               
               
                   
                 L 3   
                 n 3   
                 k 3   
                 d 3   
                   
               
               
                   
                 L 4   
                 n 4   
                 k 4   
                 — 
               
               
                   
               
            
           
         
       
     
     It is assumed that parameters variable in the process are film thickness d 1  and dimension w 1  of layer L 01 , film thickness d 2  of layer L 2  and film thickness d 3  of layer L 3 . Then, if each parameter has five levels, structure and optical constant are given as 54 that is, 625. Calculation is made with respect to each structure and optical constant, and 625 wavelength dispersions of diffraction light intensities are prepared. Wavelength dispersion of measured reflection light intensity is compared with 626 wavelength dispersions to calculate a dimension. 
     The method of the fourth embodiment has the following effect as compared with the conventional method. According to the method of this embodiment, consideration is given to the mixture ratio of the reaction product of resist and the developer. Thus, a great number of samples of wavelength dispersion are stored in the library; therefore, high accuracy is obtained. 
     The wavelength dispersion is measured in the fourth embodiment. A single wavelength, however, may be measured if sufficient accuracy is obtained using the single wavelength. The library may be prepared during the development process instead of preparing it before the development process. The pattern dimension is evaluated in the fourth embodiment. A pattern shape and the mixture ratio of developer and reaction product, however, may be evaluated. 
     TM deflection light is evaluated using a deflection plate in the fourth embodiment, however, it may be detected without using the deflection plate if sufficient accuracy is obtained. Evaluation may be carried out with respect to TE deflection light, other deflection lights, intensity change (Tan ψ) and phase change (cos Δ). First-order or more diffraction lights may be detected. The angle of incident light is not necessarily vertical. 
     1953125 wavelength dispersion samples are subjected to the comparison because the mixture ratio model is complicated in the fourth embodiment. However, if the time zone for carrying out evaluation is the second-half of the development, the reaction product has already considerably diffused at the point. Therefore, a comparison with a library including a model having no diffusion advance of the reaction product is not made, and thereby, the process time is shortened. Therefore, it is effective to determine comparative data in accordance with time zone. 
     (5) Fifth Embodiment 
     The fifth embodiment relates a pattern forming method. 
     The drawing schematically showing pattern during development is  FIG. 11A  to  FIG. 11C  like the third embodiment. The drawing shown as the flowchart to explain the procedure is  FIG. 31 . The procedure of the present invention will be described below with reference to  FIG. 11A  to  FIG. 11C  and  FIG. 31 . 
     As shown in  FIG. 11A  to  FIG. 11C , a resist film  505  is coated on a specified front-end substrate (comprising Si substrate  501 , lower-layer film  502 ,  503  and anti-reflection film  504  in order from the bottom). The resist film  505  is baked and exposed, and thereafter, baked again. After a developer is supplied onto the front-end substrate, light is irradiated to the monitor region on the front-end substrate, and then, a diffraction light is detected. Broad light having several wavelengths (e.g., halogen lamp light) is used as the incident light. Thus, the intensity of zero-order diffraction light is measured within a wavelength range from 400 to 800 nm without using a deflection plate. Wavelength dispersion of the intensity of the diffraction light detected is uniquely determined depending on the structure of measurement region and optical constant. According to the fifth embodiment, the diffraction light from pattern is measured during development, and dimension is evaluated from the measured result. Further, development ends in accordance with the measured result. 
     The procedure will be explained below with reference to  FIG. 31 . In the fifth embodiment, the diffraction light intensity is predicted before the development process, and a library is prepared. The evaluation procedure comprises a process of preparing a library before development and a development process. In the process of preparing a library, the following parameters are given to determine a development model (step S 701 ). One of the parameters is an opening shape of the development region when the resist film is dissolved in the developer. Another one is a distribution of a mixture ratio of reaction product and developer in a liquid phase consisting of the reaction product of resist and the developer. 
     Then, the following parameters, that is, substrate structure comprising liquid phase and the substrate with films thereon, and optical constant are given (step S 702 ). 
     Calculation when light is introduced at a specified angle is made based on the given structure and optical constant to calculate a wavelength dispersion of diffraction light intensity (step S 703 ). 
     Calculation is carried out with respect to all conditions of the given structure and optical constant to prepare a wavelength dispersion library of diffraction light intensity (step S 704 ). RCWA (Rigorous coupled-wave analysis) by Morham et al. (J. Opt. Soc. Am., Vol. 12, No. 5, May 1995 1077-1086) is used as the calculation method to acquire electric filed, magnetic field and intensity of refraction light from regular pattern using Maxwell equations. Calculation is made with respect to all conditions of the given structure and optical constant. 
     The development process will be described below. The substrate (wafer) is carried to a development unit (step S 711 ). Developer is supplied onto the substrate, and then, development is started (step S 712 ). Thereafter, the reflection light of the monitor region is measured (step S 713 ). The position of the substrate and the monitor unit must be controlled so that light advances onto the monitor region and a detector detects diffraction light. The control may be carried out before the developer is supplied if the substrate is not moved. If not so, the control is carried out after the developer is supplied. A comparison is made between wavelength dispersion of the measured diffraction light intensity and wavelength dispersion of diffraction light stored in the library. The best wavelength dispersion matching with the wavelength dispersion of diffraction light stored in the library is determined (step S 714 ), and thus, pattern dimension is calculated (step S 715 ). 
     The calculated dimension is compared with a desired dimension to determine if the development should end or not. If the calculated dimension matches the desired value, the development is finished (step S 717 ). If not, the reflection light is again measured (step S 713 ), and then, a comparison with the wavelength dispersion library is made (step S 714 ). The foregoing procedure is continuously taken until the calculated pattern dimension reaches the desired value. 
     The fifth embodiment differs from the third embodiment in way of giving structure and optical constant (step S 702 ). The difference will now be explained. The development model and the schematic view of film structure are the same as the third embodiment and are shown in  FIG. 23  and  FIG. 24 , respectively. The distribution of optical constants of the layer L 1  is the same as the first embodiment and is shown in  FIG. 26  and  FIG. 27 . According to the fifth embodiment, structure and optical constant are given (the same as the third embodiment so far), and thereafter, average of the optical constant is made in each layer. The optical constant of each layer is given as a fixed value. Therefore, a refractive index n 1i  of a layer L 1i  is obtained from the following equation. 
     
       
         
           
             
               n 
               
                 1 
                 ⁢ 
                 
                     
                 
                 ⁢ 
                 i 
               
             
             = 
             
               
                 1 
                 p 
               
               ⁢ 
               
                 
                   ∫ 
                   0 
                   p 
                 
                 ⁢ 
                 
                   
                     
                       n 
                       
                         1 
                         ⁢ 
                         i 
                       
                     
                     ⁡ 
                     
                       ( 
                       x 
                       ) 
                     
                   
                   ⁢ 
                   
                     ⅆ 
                     x 
                   
                 
               
             
           
         
       
     
     An extinction coefficient k 1i  of the layer L 1i  is obtained from the following equation. 
     
       
         
           
             
               k 
               
                 1 
                 ⁢ 
                 i 
               
             
             = 
             
               
                 1 
                 p 
               
               ⁢ 
               
                 
                   ∫ 
                   0 
                   p 
                 
                 ⁢ 
                 
                   
                     
                       k 
                       
                         1 
                         ⁢ 
                         i 
                       
                     
                     ⁡ 
                     
                       ( 
                       x 
                       ) 
                     
                   
                   ⁢ 
                   
                     ⅆ 
                     x 
                   
                 
               
             
           
         
       
     
     Consequently, finally obtained structure and optical constant are as shown in the following Table. 
     
       
         
           
               
               
               
               
               
               
             
               
                 TABLE 12 
               
               
                   
               
               
                   
                   
                 Refractive 
                 Extinction 
                 Film 
                   
               
               
                   
                 Layer 
                 index 
                 coefficient 
                 thickness 
                 Dimension 
               
               
                   
               
             
            
               
                   
                 L 0   
                 n 0   
                 k 0   
                 — 
                 — 
               
               
                   
                 L 01   
                 n 01   
                 k 01   
                 d 01   
                 — 
               
               
                   
                 L 11   
                 n 11 (x) 
                 k 11 (x) 
                 d 11   
                 w 1   
               
               
                   
                 L 12   
                 n 12 (x) 
                 k 12 (x) 
                 d 12   
                   
               
               
                   
                 L 13   
                 n 13 (x) 
                 k 13 (x) 
                 d 13   
                   
               
               
                   
                 L 2   
                 n 2   
                 k 2   
                 d 2   
                 — 
               
               
                   
                 L 3   
                 n 3   
                 k 3   
                 d 3   
                 — 
               
               
                   
                 L 4   
                 n 4   
                 k 4   
                 — 
                 — 
               
               
                   
               
            
           
         
       
     
     It is assumed that parameters variable in the process are film thickness d 01  of layer L 01 , the way of diffusion of reaction product (n 01 , k 01 ) in the layer L 01 , film thickness (d 11 ) of layer L 11 , the way of diffusion of reaction product (n 11 , k 11 ) in the layer L 11 , film thickness (d 12 ) of layer L 12 , the way of diffusion of reaction product (n 12 , k 12 ) in the layer L 12 , film thickness (d 13 ) of layer L 13 , the way of diffusion of reaction product (n 13 , k 13 ) in the layer L 13 , dimension w 1  of layer L 1 , film thickness (d 2 ) of layer L 2 , and film thickness (d 3 ) of layer L 3 . If each parameter has five levels, the combination of structures and optical constants are given as 5 9 , that is, 1953125 (step S 701 , S 702 ). Calculation is carried out with respect to each combination (step S 703 ), and thus, 1953125 wavelength dispersions of diffraction light intensity are prepared (step S 704 ). 
     In a comparison of measured wavelength in pattern evaluation (step S 714 ), the wavelength dispersion of the measured reflection light intensity is compared with those stored in the library to calculate a dimension, and thereafter, development ends. High accuracy is obtained by using the library considering the mixture ratio of the reaction product of resist and the developer rather than using the library giving no consideration described above. 
     The wavelength dispersion is measured in the fifth embodiment, however a single wavelength may be measured if sufficient accuracy is obtained using the single wavelength. The library is prepared before the development process in the fifth embodiment, however it may be prepared during the development process. 
     In the fifth embodiment, evaluation is made without using the deflection plate, however evaluation may be carried out with respect to TE deflection light, other deflection lights, intensity change (Tan ψ) and phase change (cos Δ). First-order or more diffraction lights may be detected. The angle of incident light is not necessarily vertical. 
     In the fifth embodiment, the library stores 1953125 wavelength dispersion samples because the mixture ratio model is complicated. However, the reaction product has already considerably diffused in the second-half of the development and the comparison with samples including small advance of diffusion may be omitted, thereby shortening the comparison time. On the other hand, the reaction product has not diffused so much in the first-half of the development. Therefore, the comparison with samples including big advance of diffusion may be omitted to shorten the comparison time. Consequently, it is effective to determine data to be compared in accordance with time zone. 
     According to the fifth embodiment, the development model of the liquid phase comprising the reaction product of resist and the developer is clarified. In other words, it is assumed that the resist ratio in the mixed phase simply changes to 0 as the position in the mixed phase gets away from the interface between the mixed phase and the resist. This assumption is used, and thereby, it is possible to accurately predict the diffraction light intensity of developing pattern. As a result, the evaluation accuracy of patterns is greatly improved. 
     (6) Sixth Embodiment 
     The sixth embodiment relates to a resist pattern process condition determination system. 
       FIG. 32  is a view showing the configuration of a resist pattern process condition determination system according to a fifth embodiment of the present invention. 
     The system is composed of coater/developer equipment, transport equipment  408  and exposure equipment  406 . The coater/developer equipment comprises comparison operation feedback section  401 , coating unit  402  using spin coating, post-coating baking unit  403 , post-exposure baking (PEB) unit  404  and development unit  405 . The development unit  405  includes a shape measuring instrument  405   a . The transport equipment  408  can carry a wafer between the exposure equipment  406  and a carrier station  407  and between the foregoing units at 1 wafer unit. The coating unit  402  may be equipped with a chemical solution control section  402   a . The chemical solution control section  402   a  mixes first resist solution (not shown) and second resist solution (solvent or photosensitive solution, solution partially extracted from the first resist solution). The control section supplies the mixed chemical solution to a nozzle for dropping chemical solution on a substrate. 
     The comparison operation feedback section  401  has experiment plane registration section  401   a , margin registration section  401   b  and control value predicting section  401   c.    
     The following is a description of the method of determining the optimum process condition of a resist newly developed using the foregoing system. The method will be explained below using part of experiment results. The carrier station  407  of the system was loaded with 24 substrates (wafers). The loaded substrates are processed at a unit of several substrates. 
     The procedure of automatically determining the process condition will be described below with reference to  FIG. 33 .  FIG. 33  is a flowchart to explain the procedure of a process condition determination method according to a fifth embodiment of the present invention. 
     The initial condition recorded in the coater/developer equipment and the exposure equipment  406  is read (step S 801 ). In the coating unit  402 , a coating film is formed with respect to three substrates according to a rotational speed of the initial condition shown in the following Table 13 (step S 802 ). 
     
       
         
           
               
               
               
               
             
               
                 TABLE 13 
               
               
                   
               
               
                   
                 1 
                 2 
                 3 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Coating 
                 Number of revolutions (rpm) 
                 2000 
                 2500 
                 3000 
               
               
                   
                 Supply Amount of solution (cc) 
                 2 
                 ← 
                 ← 
               
               
                   
               
            
           
         
       
     
     The shape measuring instrument  405   a  measures the film thickness of a photosensitive resin film immediately after coating (step S 803 ). The comparison operation feedback section  401  compares the measured film thickness with a predetermined range (step S 804 ). 
     If the film thickness is within the predetermined range, the rotational speed of the initial condition is set as the process condition (step S 805 ). If the film thickness is not within the predetermined range, the comparison operation feedback section  401  determines the optimum rotational speed required for obtaining a desired film thickness based on the relationship between rotational speed and film thickness (step S 806 ). In the sixth embodiment, a resist film having the predetermined range was not obtained under the condition shown in the Table 13. Then, the rotational speed was corrected as 2400 rpm; as a result, a resist film having a predetermined range was obtained. Thus, the 2400 rpm was set as the process condition. 
     Then, the following plan was made. More specifically, exposure and focus position are each changed on the surface of the substrate. Three parameters, that is, the temperature and time of post-exposure bake (PEB) for each substrate and development time are given, and each of these parameters has two levels. The experiment plan is stored in the experiment plan registration section  401   a . Based on the experiment plan, coating, exposure, post-exposure bake (PEB), development and shape measurement are successively carried out to the total of eight substrates (step S 807 ). The following Table 14 shows setting values of each parameter. 
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 14 
               
               
                   
               
               
                   
                 4 
                 5 
                 6 
                 7 
                 8 
                 9 
                 10 
                 11 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 Coating 
                 Number of 
                 2400 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
               
               
                   
                 revolutions 
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                   
                 (rpm) 
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                   
                 Supply amount 
                 2 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
               
               
                   
                 (cc) 
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 PEB 
                 Temperature 
                 130 
                 140 
                 130 
                 130 
                 140 
                 140 
                 130 
                 140 
               
               
                   
                 (° C.) 
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                   
                 Time (second) 
                 60 
                 60 
                 60 
                 90 
                 90 
                 60 
                 90 
                 90 
               
               
                 Development 
                 Concentration 
                 0.27 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
               
               
                   
                 N 
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                   
                 Temperature 
                 25 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
               
               
                   
                 (° C.) 
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                   
                 Time (second) 
                 30 
                 60 
                 60 
                 30 
                 60 
                 30 
                 60 
                 30 
               
               
                   
               
            
           
         
       
     
     The shape measuring instrument  405   a  measures the dimension and shape of an opening portion (region without photosensitive resin) of photosensitive resin pattern (step S 808 ). The dimension and shape are measured using RCWA by Morham et al. (J. Opt. Soc. Am., Vol. 12, No. 5, May 1995 1077-1086) is used as the calculation method to obtain electric filed, magnetic field and intensity of refraction light from regular pattern using Maxwell equations. 
     It is determined whether or not the measured value is within an allowable range (step S 809 ). The allowable range of the pattern dimension is 100 nm±5%. The allowable range of the pattern shape is a range from 88° to 90° at a sidewall angle. 
     If the measured value is within the allowable range, another exposure-focus range (ED-margin) to obtain a shape within the range to determine wider ED-margin as much as possible. The ED-margin is registered in the margin registration section  401   b.    
     ED-margin data about eight substrates was compared with the level of coating, PEB and development. This comparison shows that longer bake time realizes the wider ED-margin. Therefore, the comparison operation feedback section  401  allocates longer time of the two levels to the post-exposure baking unit  404 . The control value predicting section  401   c  of the comparison operation feedback section  401  takes the setting procedure given below. More specifically, the control value predicting section  401   c  determines that interaction exists between bake temperature and development time. The section  401   c  sets the bake temperature to an optimum temperature and ±2° C. (smaller than the temperature range used for the first-time experiment level) thereof (three levels). Likewise, section  401   c  sets the development time to an optimum time and ±10% (smaller than the time range used for the first-time experiment level) thereof (three levels). As a result, the comparison operation feedback section  401  gave instructions to coating unit  402 , post-exposure bake (PEB) unit  404 , development unit  405  and exposure equipment  406  to carry out coating, exposure, PEB, development and shape measurement on the total of nine substrates. 
     
       
         
           
               
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 15 
               
               
                   
               
               
                   
                 12 
                 13 
                 14 
                 15 
                 16 
                 17 
                 18 
                 19 
                 20 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Coating 
                 Number of 
                 2400 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
               
               
                   
                 revolutions 
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                   
                 (rpm) 
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                   
                 Supply amount 
                 2 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
               
               
                   
                 (cc) 
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 PEB 
                 Temperature 
                 135 
                 133 
                 137 
                 137 
                 135 
                 135 
                 133 
                 133 
                 137 
               
               
                   
                 (° C.) 
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                   
                 Time (second) 
                 60 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
               
               
                 Development 
                 Concentration 
                 0.27 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
               
               
                   
                 N 
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                   
                 Temperature 
                 25 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
                 ← 
               
               
                   
                 (° C.) 
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                   
                 Time (second) 
                 40 
                 36 
                 36 
                 44 
                 44 
                 36 
                 44 
                 40 
                 40 
               
               
                   
               
            
           
         
       
     
     The comparison operation feedback section  401  finds a condition that can realize the maximum ED-margin, and determines the optimum condition corresponding to the condition was +0.4° C. to the standard for bake temperature and −5% of the standard for development time. Then, the comparison operation feedback section  401  sets the optimum condition to baking unit and development unit. In addition, the section  401  sets focus offset and optimum exposure to the exposure equipment. 
     As described above, the photosensitive resin pattern forming system automatically measures the dimension and shape of the photosensitive resin pattern in the process of treating the total of 20 substrates and feeds the result back to associated means to determine coating, bake, exposure and development conditions. 
     A semiconductor device with largely improved dimension accuracy was realized when the semiconductor device is obtained through carrying out etching with a photosensitive resin pattern as a mask which is formed in accordance with the conditions determined in the manner. This semiconductor device has a greatly high reliability. 
     It took two minutes to determine the film thickness and to make feedback, and 23 minutes to make evaluation of 3 parameters having two levels, and 25 minutes to determine detailed conditions (2 parameters having 3 levels) in the operation. Thus, patterning using a new photosensitive resin material is optimized in about 50 minutes. On the other hand, the conventional destructive inspection needed eight days. Therefore, the present embodiment can greatly reduce condition determination time. 
     The number of substrates required for determining selected parameters, level, correction target and conditions is not limited to the foregoing embodiment. In this case, various procedures may be taken in accordance with target photosensitive resin material, required items and values to photosensitive resin pattern and its range. 
     Incidentally, fine control for the level is preferably carried out in the following manner. 
     1) Correction on resist pattern dimension of positive resist 
     a) If dimension is thicker than desired one, any of corrections given below is made. 
     The corrections include: 
     increasing the exposure of exposure means; 
     increasing the bake temperature of bake means used for post-exposure bake; 
     lengthening the development time of development means; 
     increasing the developer concentration of development means; and 
     increasing the developer temperature of development means 
     b) If dimension is thinner than desired one, any of corrections given below is made. 
     The corrections include: 
     decreasing the exposure of exposure means; 
     decreasing the bake temperature of bake means used for post-exposure bake; 
     shortening the development time of development means; 
     decreasing the developer concentration of development means; and 
     decreasing the developer temperature of development means 
     2) Correction on opening dimension of positive resist 
     a) If dimension is thicker than desired one, any of corrections given below is made. 
     The corrections include: 
     decreasing the exposure of exposure means; 
     decreasing the bake temperature of bake means used for post-exposure bake; 
     shortening the development time of development means; 
     decreasing the developer concentration of development means; and 
     decreasing the developer temperature of development means 
     b) If dimension is thinner than desired dimension, any of corrections given below is made. 
     The corrections include: 
     increasing the exposure of exposure means; 
     increasing the bake temperature of bake means used for post-exposure bake; 
     lengthening the development time of development means; 
     increasing the developer concentration of development means; and 
     increasing the developer temperature of development means 
     3) Correction on resist pattern dimension of negative resist 
     a) If dimension is thicker than desired dimension, any of corrections given below is made. 
     The corrections include: 
     decreasing the exposure of exposure means; 
     decreasing the bake temperature of bake means used for post-exposure bake; 
     shortening the development time of development means; 
     decreasing the developer concentration of development means; and 
     decreasing the developer temperature of development means 
     b) If dimension is thinner than desired dimension, any of corrections given below is made. 
     The corrections include: 
     increasing the exposure of exposure means; 
     increasing the bake temperature of bake means used for post-exposure bake; 
     lengthening the development time of development means; 
     increasing the developer concentration of development means; and 
     increasing the developer temperature of development means 
     4) Correction on opening dimension of negative resist 
     a) If dimension is thicker than desired dimension, any of corrections given below is made. 
     The corrections include: 
     increasing the exposure of exposure means; 
     increasing the bake temperature of bake means used for post-exposure bake; 
     lengthening the development time of development means; 
     increasing the developer concentration of development means; and 
     increasing the developer temperature of development means 
     b) If dimension is thinner than desired dimension, any of corrections given below is made. 
     The corrections include: 
     decreasing the exposure of exposure means; 
     decreasing the bake temperature of bake means used for post-exposure bake; 
     shortening the development time of development means; 
     decreasing the developer concentration of development means; and 
     decreasing the developer temperature of development means 
     RCWA is employed for shape measurement in the sixth embodiment, however any other methods are applicable to shape measurement means so long as they predict pattern dimension and shape. 
     The sixth embodiment relates to condition determination for forming resist pattern in the lithography process, however it is not limited to the process. The present embodiment is applicable to condition determination in the etching process. If a process condition determination apparatus includes resist control means, resist solution may be simultaneously optimized. According to the sixth embodiment, chemical solution is prepared for each kind of resin, photosensitive agent, anti-soluble material and solvent in the resist control means. The chemical solution having a blend ratio changed using a mixer is coated on the substrate. By doing so, conditions such as coating, bake and development are optimized while materials are optimized. Therefore, material maker carries out the foregoing embodiments of the present invention, and thereby, it is possible to readily sell materials attached with optimum process condition. 
     In each of embodiments of the present invention, samples with respect to all combinations of setting level are prepared as the experiment plan; however, the present invention is not limited to above. Taguchi method using orthogonal table such as L 18  may be employed, and thereby, the possibility of finding optimum condition using reduced samples is high. 
     Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.