Patent Publication Number: US-2013233489-A1

Title: Apparatus for wet etching while forming interconnect trench in insulating film

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a divisional of application Ser. No. 12/035,832, filed Feb. 22, 2008. This application is also based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2007-42303, filed on Feb. 22, 2007, the entire contents of which are incorporated herein by reference. 
    
    
     TECHNICAL FIELD 
     The present invention relates to a novel wet etching technology. More specifically, the present invention relates to technology capable of reduction of etching damage which occurs during formation of an interconnect trench during the formation process of, for example, a semiconductor device. 
     BACKGROUND OF THE INVENTION 
     Although semiconductor integrated circuits or semiconductor devices, such as a multilayer interconnect device and the like, are known to have increased power consumption due to leakage current within the interconnect layer insulating film, the overall effect of leakage current on the device (semiconductor device) was small during device generations for which spacing of interconnects forming the semiconductor device exceeded 1 μm. However, as the spacing of interconnects becomes less than or equal to 1 μm, the effect on power consumption has increased due to size reduction of interconnect spacing and an increase of dimensions of interconnects. In particular, when circuits in the future are formed using an interconnect spacing less than or equal to 0.1 μm, leakage current of such interconnects becomes large enough to greatly affect device characteristics and working life. 
     Presently the damascene method is generally used for interconnect formation of such semiconductor devices. According to the damascene method, a trench shaped like the interconnect is first formed in the insulating film by etching. Thereafter, this method forms a copper interconnect in this trench by plating and the like. However, during interconnect trench formation by etching according to this damascene method, the sidewall of this interconnect trench is readily damaged by etching. Thus leakage current increases due to damage arising in the interior of the insulating film. Also TDDB (Time Dependent Dielectric Breakdown) characteristics worsen due to the occurrence of bowing of the interconnect trench and the like. These phenomena become large factors resulting in lowering of reliability and yield during semiconductor device production. 
     Here the term “bowing” of the interconnect trench is taken to mean an expansion phenomenon of the trench profile in the lateral direction. This phenomenon can be observed, for example, by slicing the etching trench in the depth direction and then viewing the resultant cross section, as shown in  FIG. 1A . In this manner, the cross-sectional profile (i.e., interior of the etching trench) expands in the direction (i.e., lateral direction) indicated by the X arrow. The occurrence of this phenomenon is thought to depend on etching isotropism (i.e., a lack of anisotropy). When such bowing occurs, TDDB characteristics worsen due to narrowing of the effective spacing between interconnects. Furthermore, in  FIG. 1A , item  181  is a resist, item  182  is an insulating film, and item  183  is an underlayer of the insulating film. Although for illustrative purposes  FIG. 1A  shows a profile having the greatest expansion (i.e., removal of the interior wall face of the trench) in the vicinity of the center, since actual etching is isotropic, the trench of insulating film  182  has a shape for which bowing near the resist  181  side is larger than the bowing of the lower layer  183  side. 
     Due to such circumstances, attention is being paid to technologies for the suppression of damage to the insulating film caused by the etching solution during the interconnect formation process. 
     As a method for suppression of damage to the insulating film by the etching solution when etching is performed by wet etching, the interconnect trench part of the insulating film has been irradiated with light. The light used for irradiation, for example, is ultraviolet light (UV light). For example, refer to the Japanese Patent Application Laid-Open No. 2001-1724161 and No. 2004-335847. According to these citations, by the use of this method, damage by the etching solution to the interconnect trench sidewall can be suppressed, and an increase of dielectric constant due to moisture can be suppressed. 
     The above mentioned UV light irradiation is thought to perhaps promote hydrophilicity of the irradiated face, a phenomenon which causes faster etching. That is to say, damage to the interconnect trench sidewall due to etching is not suppressed. 
     However, performance of etching by wet etching using this type of conventional technology is deficient in that the occurrence of damage to the trench part formed in the insulating film by the etching solution can not be suppressed. 
     SUMMARY OF THE INVENTION 
     According to one aspect of the present invention, a wet etching method includes forming an insulating film on a substrate, and irradiating laser light to the insulating film during wet etching of the insulating film using an etching solution. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIGS. 1A and 1B  are cross-sectional drawings of bowing of a conventional interconnect trench. 
         FIGS. 2A and 2B  are diagrams showing the wet etching apparatus according to the present embodiment. 
         FIGS. 3A to 3K  are cross-sectional drawings showing the production method of a multilayer interconnect substrate according to the present embodiment (in the case of separate formation of the via layer and the interconnect layer). 
         FIGS. 4A to 4F  are cross-sectional drawings showing the production method of a multilayer interconnect substrate according to the present embodiment (in the case of simultaneous formation of the via layer and the interconnect layer). 
     
    
    
     DETAILED DESCRIPTION OF THE EMBODIMENTS 
     Embodiments of the present invention will be explained below using figures, tables, working examples, and the like. Furthermore, these figures, tables, working examples, and the like and their explanation are illustrative of the present invention and do not limit the scope of the present invention. Of course, other embodiments according to the gist of the present invention come within the meaning of the present invention. Identical elements within the figures are referred to by the same reference numerals throughout the application. 
     Wet etching will be explained next. That is to say, during etching of a workpiece using the etching solution, when the workpiece is irradiated by a laser light  180 , damage by the etching solution can be suppressed, for example, as shown in  FIG. 1B , and a clean etching shape can be obtained. For example, when the workpiece is the insulating film of a semiconductor device, this means that it is possible to suppress the increase of leakage current caused by damage due to the etching solution, possible to suppress worsening of TDDB (time dependent dielectric breakdown) characteristics due to bowing of the interconnect trench, and the like. It thus becomes possible to cause an improvement of reliability during semiconductor device production. This improvement is tied to a simultaneous improvement of yield and furthermore makes possible production of a semiconductor device which has low power consumption and high reliability. For example, according to the present embodiment, an LSI interconnect layer can be obtained which has a low effective value of the relative dielectric constant, and by this means, it becomes possible to produce a faster semiconductor device. Furthermore, the term “clean” in referring to the present embodiment means that the desired shape could be obtained correctly. That is to say, one example of the term “clean” is the angle formed by two orthogonal faces not assuming a rounded shape as observed visually under a microscope. Another example of the term “clean” is the ability to suppress bowing. 
     The above mentioned effect is thought to occur for the reasons described below. 
     (1) Firstly, under irradiation by laser light, this phenomenon is thought to occur as the trench material of the workpiece irradiated by the laser beam becomes excited, bringing about polarization of the electrons in the chemical bonds of the trench material. Then due to this polarization of electrons, this phenomenon occurs due to the workpiece having increased affinity for the etching solution (i.e., the workpiece can become hydrophilic). 
     (2) Secondly, this phenomenon is thought to be due to the characteristic of laser light, in contrast to simple UV radiation, of largely rectilinear propagation. Irradiation by this laser light of just the target part becomes possible since laser light has this type of characteristic. That is to say, for example, during formation of an interconnect trench, the laser light is concentrated only at the bottom face, and the laser light does not reach the sidewall. For this reason, etching of the hydrophilized bottom face proceeds preferentially in the downward direction, and the sidewall becomes less hydrophilized. Due to selective hydrophilization in this manner, the sidewall is thought to become less susceptible to damage by the etching solution. 
     (3) Thirdly, when using irradiation by laser light, etching is thought to proceed more smoothly than conventionally since hydrophilization of the irradiated part is faster in comparison to the use of other light. 
     Furthermore, in addition to physical damage, damage by the etching solution due to hydrophilization of the sidewall is also caused by a phenomenon of bonding of polar groups, such as the hydroxyl group and the like, to the material of the sidewall due to contact between the etching solution and the hydrophilized sidewall. Such bonding with polar groups causes, for example, and increased absorption of moisture to the bonded part, results in an increase of the dielectric constant, and a rise in the leakage current. 
     Although irradiation by laser light may be performed during wet etching, such laser light irradiation may also be performed prior to wet etching. Furthermore, the laser light irradiation may be intermittent. 
     When the laser irradiation is performed through a lens during irradiation of the insulating film (i.e., workpiece) by laser light, resolution can be increased, and scattering of light can be decreased. Cleaner etching becomes possible for this reason, and damage by the etching solution can be suppressed. By the use of a lens in this manner, the direction of the central axis of irradiation of the spreading laser light can be aligned. Furthermore, the utilized lens can be selected appropriately from among known lenses. One example of a lens which can be used is a so-called projection lens. Placement of the lens such that the lens contacts the etching solution is preferred due to the ability to prevent the etching solution surface from causing diffuse reflection of light output from the laser. Such contact is sufficient if the liquid face side of the lens is submerged in the etching solution (i.e., the solution surface side of the lens is in a state of contact with the etching solution). A significant part of the lens may also be immersed in the etching solution. 
     In this case, however, attention must be paid to assure that the lens does not become contaminated and that air bubbles do not become caught beneath the lens. If contamination occurs, the contamination will cause diffuse reflection. Moreover, if air bubbles are present, diffuse reflection of light due to air bubbles will occur at the interface between the air bubbles and the etching solution, and a possibility exists of the occurrence of damage by the etching solution. A useful means to solve such problems uses a known mechanism for causing constant flow of the etching solution or includes a surfactant in the etching solution. No particular limitation is placed on this surfactant, and the surfactant can be selected appropriately from among known surfactants used for wet etching. 
     Wavelength range of the utilized laser light is preferably 150 nm to 400 nm, in the so-called UV spectrum. A wavelength in the range of 180 to 300 nm is further preferred. Particular improvement in the effect of the present embodiment is not observed when the wavelength is less than 150 nm. Conversely in this case, there are instances of the occurrence of a phenomenon of increased damage by the etching solution. Moreover, the effect of the present embodiment becomes difficult to obtain when the wavelength exceeds 400 nm. 
     Although no particular limitation is placed on the type of laser light which can be used for the present embodiment, examples of the laser light which can be cited are: ArF laser light, KrF laser light, KrCl laser light, Nd:YAG 4th harmonic laser light, Nd:YAG 5th harmonic laser light, and the like. The wavelength of each of these laser lights is within the wavelength range of 180 to 300 nm, and these laser lights are preferred from the standpoint of having sufficient light intensity. Specifically, ArF laser light has a wavelength of about 193 nm, KrF laser light has a wavelength of about 248 nm, KrCl laser light has a wavelength of about 222 nm, Nd:YAG 4th harmonic laser light has a wavelength of about 266 nm, and Nd:YAG 5th harmonic laser light has a wavelength of about 213 nm. 
     Furthermore, the step-and-repeat method or the step-and-scan method for light irradiation is preferably used with such laser light. According to the step-and-repeat method, exposure of the workpiece (e.g. semiconductor chip) is repeated in workpiece units. For example, after exposure is completed for 1-2 semiconductor chips, the exposure location is moved (stepped) according to the size of the semiconductor chip. Then the step-and-repeat method exposes the next semiconductor chip. According to the step-and-scan method, the workpiece is moved-scanned relative to a zonal irradiation light beam (or conversely the zonal irradiation light beam is moved-scanned relative to the workpiece), and exposure is continued in a zonal single exposure field. According to this method, after exposure of one exposure field, step movement by just one exposure field takes place, and the next one exposure field is exposed. Both the step-and-repeat method and the step-and-scan method have the advantage of making exposure of a large field possible while using a small projection optical system. 
     No particular limitation is placed on the wet etching method of the present embodiment, and the wet etching method can be selected appropriately from among known wet etching methods. Specific examples which can be cited of the wet etching method are the immersion method which immerses the workpiece in the etching solution and the spray method which sprays the etching solution against the workpiece. Amore preferred effect is obtainable by use also of ultrasound irradiation during performance of immersion or spraying. During spraying of the etching solution of the spray method, a spray nozzle is normally attached to the tip of a spray discharge aperture, and the etching solution is sprayed out by pressure. 
     The utilized etching solution of the present invention can be selected appropriately from among known etching solutions as an etching solution suitable for the workpiece. Example etching solutions which can be used include: hydrazine type solutions; aliphatic amine type solutions such as solutions of ethylenediamine, ethanolamine, diethanolamine, hexamethylene diamine, and the like; aromatic amine type solutions such as solutions of benzylamine, p-phenyldiamine, m-phenyldiamine, 3-xylylenediamine, 4-xylylenediamine, and the like; solutions containing alkali metal compounds such as potassium hydroxide, sodium hydroxide, and the like; and basic solutions combined with such. 
     Any workpiece without particular limitation can be used as the workpiece according to the present embodiment as long as the workpiece can be used as a target for wet etching. However, the effect of the present embodiment is particularly anticipated when the workpiece is “part of a semiconductor device” since damage to a workpiece subjected to wet etching is seen as a problem particularly in the field of semiconductor devices. Furthermore, here the expression “part of a semiconductor device” does not indicate part of a semiconductor device as a completed product but rather is taken to mean part of a semiconductor device occurring at an intermediate step during production of this semiconductor device. The part of the semiconductor device may comprise multiple parts as in the case of the “low dielectric constant film  17  having a vinyl group and TEOS-SiO 2    18  as a protective film” of the below mentioned working example 5. 
     Although an insulating film provided with an interconnect or via hole can be cited as this part of the semiconductor device, the part of the semiconductor device is not limited to this case. 
     Although this insulating film is frequently called an interlayer insulating film, whatever the name used for the insulating film, the insulating film can be the workpiece of the present embodiment. Since the effect is particularly great if the workpiece is an LSI interlayer insulating film, the workpiece is preferably the LSI interlayer insulating film. During production of the interconnect of the LSI, the present procedure is particularly effective for lowering of damage undergone by the interlayer insulating film due to the etching solution used for the interlayer insulating film of the LSI. 
     No particular limitation is placed on the material which can be used for the insulating film. Semiconductor devices having a narrow interconnect spacing, for which the present embodiment can be used with advantage, frequently utilize a low dielectric constant insulating film material. The present embodiment can be used with advantage for such insulating film. 
     Examples which can be cited as the insulating film material used by the present embodiment are: known insulating film-forming materials having silicon and oxygen as major components; known insulating film-forming materials having silicon, oxygen, and carbon as major components; known insulating film-forming materials having silicon, oxygen, and nitrogen as major components; and organic type known insulating film-forming materials. SiO 2  type insulating films, for example, can be cited as specific examples of the insulating film having silicon and oxygen as major components. Additional examples are materials having atomic compositions close to SiO 2 . Specific known examples of materials having such compositions are: SiOC-containing insulating compositions (e.g., carbon-topped SiO 2  produced by CVD with a relative dielectric constant of about 3.3-3.5), SiOCH-containing insulating compositions, SiOCHN-containing insulating compositions, and the like. 
     The insulating film-forming material containing silicon, oxygen, and carbon as main ingredients, for example, is frequently produced by using as raw materials polycarbosilanes containing silicone and carbon in the backbone or polycarboxysilanes containing oxygen in the backbone. However, the insulating film-forming material containing silicon and carbon as main ingredients may also be produced from other arbitrary materials. 
     Examples of organic-type known insulating film-forming materials are: methyl group-containing SiO 2  (methyl silsesquioxane=MSQ), hydrosilsesquioxane (HSQ), polyimide type materials, SiLK® (The Dow Chemical Company), FLARE® (Honeywell Electric Materials Inc.), HSG (Hitachi Chemical Co., Ltd.), nanoclustering silica (NCS, specific dielectric constant=2.25), amorphous carbon (F doped), and the like. 
     The insulating film formed from these insulating film-forming materials preferably has a relative dielectric constant less than or equal to 2.7. When the relative dielectric constant is greater than 2.7, density of the insulating film-forming material tends to be high, and thus there is thought to be a high probability that an insulating film having such a relative dielectric constant can withstand dry etching which presently is the major interconnect trench formation method for insulating film. However, when the relative dielectric constant becomes less than or equal to 2.7, there is a tendency for damage to occur due to dry etching as an increase of leakage current or as a lowering of the relative dielectric constant. Thus when the relative dielectric constant is less than or equal to 2.7 in this manner, an effect is readily realized which is the obtaining of a clean pattern shape or lessening of damage due to the etching solution. 
     From the standpoint of increasing the effect of the laser light, it was judged preferable that the material constituting the workpiece have an unsaturated bond. Specifically, the insulating film-forming material preferably has an unsaturated bond. Furthermore, the insulating film-forming material may be both a silicon containing material and an organic type material. 
     The reason for this preference is thought to be that electrons in unsaturated bonds are readily polarized due to excitation by laser light. Alternatively as may be the case, the unsaturated bond is thought to be opened and broken by laser light, and this results in reaction with moisture and the like in the atmospheric gas which generates hydrophilic groups. It does not matter whether the material constituting the workpiece has the unsaturated bond in the backbone of the material or in a substituting group. 
     Any type of element may participate in the unsaturated bond, and this bond may be a double bond, triple bond, conjugated unsaturated bond, or a pi bond. Although the unsaturated bond, for example, can be a C═N bond, preferred bonds in practice are a carbon-to-carbon double bond or a carbon-to-carbon triple bond. 
     Examples which can be cited of unsaturated bonds within the backbone are the acetylene group, diazo group, and the like. Examples which can be cited of unsaturated double bonds in the substituting group are the vinyl group, phenyl group, and the like. Moreover, examples which can be cited of the insulating film-forming material having an unsaturated bond are vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tripropoxysilane, vinyl trichlorosilane, and the like. 
     The wet etching method according to the present embodiment is preferably implemented using the wet etching apparatus shown in  FIGS. 2A and 2B  for etching the workpiece using the etching solution. Specifically, the wet etching method according to the present embodiment can preferably be implemented using a wet etching apparatus  300  comprising an emersion tank  208  for emersion of the workpiece in an etching solution  200  or a spray device  220  for spraying the etching solution  200  against the workpiece, and a laser irradiation device  210  for irradiation of the workpiece by a laser light  180  during etching. The wet etching apparatus further comprises a stage  203  carrying a workpiece  207  on which an interconnect layer  206  is formed on a silicon wafer  205 , and the wet etching apparatus further comprises a support platform  201  for carrying the stage  203 . 
     This wet etching apparatus  300  preferably further comprises a lens  211  (lens for incident laser light) such that the irradiation by laser light  180  is possible through the lens  211 . Moreover, the lens  211  is preferably disposed such that the lens can contact the etching solution  200 . 
     The above mentioned wet etching method was explained for the above mentioned workpiece  207  and the laser light  180 , which are above mentioned constituent elements, and for the other constituent elements. This preferred aspect, configuration, attribute, and the like can also be used for aspects of the present embodiment. 
     If the present apparatus is used in this manner, damage to the wet etching workpiece is suppressed, and a clean etching shape can be obtained. 
     The method and apparatus of the present embodiment can be incorporated in the production process for a semiconductor device. Then if trench formation of an interconnect and the like is performed by using wet etching in such a form, the leakage current can be reduced, and an interconnect layer can be obtained which has high TDDB resistance ability. By this means, power consumption can be reduced, and a semiconductor device having high reliability can be produced. 
     WORKING EXAMPLES 
     Working examples and comparative examples of the present embodiment are explained next in detail. Furthermore, measurement of etching rate, etching maximum width, and relative dielectric constant were performed by the below described methods. 
     (Etching Rate) 
     A spectral ellipsometer was used to measure film thickness by the spectral ellipsometry method. Then etching rate was calculated by comparison with the layer thickness before and after etching. The increase of etching rate due to laser light irradiation is taken to mean the selective increase of etching rate which occurs in the direction of incident laser light. That is to say, this means the rate of highest anisotropy. By this means, damage of the workpiece during wet etching becomes suppressed, and a clean etching shape can be obtained. 
     (Etching Maximum Width) 
     This is measured using an SEM (scanning electron microscope) to observe the cross-sectional profile after etching. Specifically, the etched part is cleaved, and the length of the X dimension of  FIGS. 1A and 1B  is measured. The ability to suppress the etching maximum width means that etching anisotropy is increased. By this means, the damage to the workpiece during wet etching is suppressed, and it becomes possible to obtain a clean etching shape. 
     (Relative Dielectric Constant) 
     The dielectric constant was calculated from capacitance measured using a mercury prober (CVmap92A; Four Dimensions, Inc.). Furthermore, a precision LCR meter (4284A; Agilent Technologies, Inc.) was used for measurement of effective relative dielectric constant, which is that of the device and entire element. 
     Working Example 1 
     Relative dielectric constant 2.4 coating-type low dielectric constant insulating material formed from a compound containing silicon containing a vinyl group and produced from a monomer which has the below listed structure was spin coated on an ion doped Si low resistivity substrate to produce a 250 nm thick film. Then after prebaking was performed for 3 minutes at 250° C., curing was performed in a N 2  atmosphere electric furnace under 30 minutes, 400° C. conditions. 
       H 2 C=(CH)—Si(OC 2 H 5 ) 3  
 
     Thereafter, the film sample produced in this manner was immersed in etching solution, and a projection lens was placed in contact with the alkali etching solution using water as a solvent. Thereafter, light was irradiated through the projection lens, and the etching rate was measured. Sample 2 was produced using an Ar gas laser, sample 3 was produced using a KrF laser, sample 4 was produced using an ArF laser, and sample 5 was produced using a Kr2 laser. A sample 1 was produced in the same manner without laser light irradiation. Moreover, for comparison, a relative dielectric constant 2.6 coating-type low dielectric constant insulating material was spin coated in the above described manner to produce a 250 nm thick film just as the low resistivity substrate above. Then prebaking was performed for 3 minutes at 250° C. This relative dielectric constant 2.6 coating-type low dielectric constant insulating material was a material which resembled the above mentioned silicon containing vinyl containing compound except for a lack of the vinyl group. Moreover, this relative dielectric constant 2.6 coating-type low dielectric constant insulating material was produced from a monomer which had the below listed structure, and this material was made from a silicon containing compound which did not include the vinyl group. Thereafter, curing was performed in a N 2  atmosphere electric furnace for 30 minutes under 400° C. conditions, and then sample 6 was produced by performance of treatment in the same manner as sample 3. 
       H 3 C—Si(OC 2 H 5 ) 3  
 
     The etching solution was continuously stirred, and laser light irradiation was continuous. 
     Etching of each sample was performed until film thickness reached 200 nm. The obtained etching rates are listed below. 
     
       
         
           
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 Sample no. 
                 Laser wavelength (nm) 
                 Etching rate (nm/sec.) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 1 
                 no irradiation 
                 0.02 
               
               
                 2 
                 488 (Ar gas) 
                 0.02 
               
               
                 3 
                 248 (KrF) 
                 4.3 
               
               
                 4 
                 193 (ArF) 
                 5.9 
               
               
                 5 
                 146 (Kr 2  excimer) 
                 15.3 
               
               
                 6 (no vinyl group) 
                 248 (KrF) 
                 0.05 
               
               
                   
               
            
           
         
       
     
     Working Example 2 
     Relative dielectric constant 2.4 coating-type low dielectric constant insulating material formed from a compound containing silicon containing a vinyl group in the same manner as working example 1 was spin coated to form a 250 nm thick film on the same substrate as working example 1, and the film was pre-baked for 3 minutes at 250° C. Thereafter the substrate coated with the coating-type low dielectric constant insulating material was cured in a N 2  atmosphere electric furnace for 30 minutes under 400° C. conditions. Thereafter resist was formed on the sample, and this resist was patterned using a 70 nm pattern width. Thereafter, this film sample was immersed in etching solution, and a projection lens was placed in contact with the alkali etching solution using water as a solvent. Thereafter, laser light was irradiated through the projection lens, and the etching rate was measured. Sample 2′ was produced using an Ar gas laser, sample 3′ was produced using a KrF laser, sample 4′ was produced using an ArF laser, and sample 5′ was produced using a Kr2 laser. Also a sample 6′ was produced using a mercury lamp rather than laser light, and a similar experiment was performed without laser light irradiation to produce a sample 1′. The experimental method compared the maximum width of the resist pattern when the insulating film had been subjected to 100 nm of etching. Results are shown in Table 2. Furthermore, the etching solution was continuously stirred, and laser light irradiation was continuous. 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                   
                 Laser wavelength 
                 Etching maximum width 
               
               
                   
                 Sample no. 
                 (nm) 
                 (nm) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                   
                 1′ 
                 no irradiation 
                 261.0 
               
               
                   
                 2′ 
                 488 (Ar gas) 
                 255.9 
               
               
                   
                 3′ 
                 248 (KrF) 
                 75.4 
               
               
                   
                 4′ 
                 193 (ArF) 
                 78.3 
               
               
                   
                 5′ 
                 146 (Kr 2  excimer) 
                 107.2 
               
               
                   
                 6′ 
                 254 (mercury lamp) 
                 184.1 
               
               
                   
                   
               
            
           
         
       
     
     Working Example 3 
     The relative dielectric constants were measured for samples 3, 4, and 5 used in working example 1. The measured results are shown in Table 3. Within Table 3, the term “beta film” refers to a sample prior to etching treatment. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 3 
               
               
                   
                   
               
               
                   
                   
                 Presence or 
                   
                 Relative 
               
               
                   
                 Sample 
                 absence of the 
                 UV laser 
                 dielectric 
               
               
                   
                 no. 
                 vinyl group 
                 wavelength (nm) 
                 constant 
               
               
                   
                   
               
             
            
               
                   
                 3 
                 present 
                 248 (KrF) 
                 2.5 
               
               
                   
                 4 
                 present 
                 193 (ArF) 
                 2.5 
               
               
                   
                 5 
                 present 
                 146 (Kr 2  excimer) 
                 4.7 
               
               
                   
                 beta film 
                 present 
                 — 
                 2.4 
               
               
                   
                   
               
            
           
         
       
     
     The increase of relative dielectric constant of sample 5 is thought to have been due to etching damage by the etching solution at the bottom part of the etching. 
     Working Example 4 
     A sample was produced using a KrF laser in the same manner as working examples 1 and 2 except for positioning of the projection lens so that the projection lens did not contact the water. The obtained etching rate was 3.7 nm/second, and the etching maximum width was 178.5 nm. 
     Working Example 5 
     The method for production of the multilayer interconnect substrate according to the present embodiment is shown in  FIG. 3A . First, a Si wafer  1  was partitioned by an inter-element partitioning film  2 . Then a transistor layer ( FIG. 3A ) was formed by forming a source diffusion layer  5   a  and a drain diffusion layer  5   b  and by forming a gate electrode  4  having a sidewall insulating film  3 . Thereafter, on this Si wafer  1  containing this formed transistor layer were formed in turn an interlayer insulating film  6  and a stopper film  7  ( FIG. 3B ). Thereafter a contact hole for electrode extraction was formed ( FIG. 3C ). 
     A TiN  8  film of 30 nm thickness was formed on this contact hole by the sputtering method ( FIG. 3D ). Thereafter, the contact hole was buried with a conductor plug  9  by reduction of a mixture of WF 6  and hydrogen ( FIG. 3E ), and the part outside the via was removed by the chemical mechanical polishing (CMP) method ( FIG. 3F ). 
     Thereafter, an insulating film  10  (interconnect partition insulating film, relative dielectric constant=2.4) made from a low dielectric constant insulating material having vinyl groups in the same manner as working example 1 was formed under conditions to produce a 150 nm film on the Si wafer. Thereafter, a TEOS-SiO 2    11  of 30 nm thickness was deposited on this Si wafer as a protective film ( FIG. 3G ). 
     Thereafter, a resist layer having a first layer interconnect pattern was used as a mask while these films (insulating film  10  and protective film  11 ) were subjected to wet etching while undergoing irradiation by laser light  180  using the conditions of sample 4′ of working example 2 ( FIG. 3H ). 
     Furthermore, in the interconnect trench formed by processing was formed a TiN  12  film acting as a barrier to prevent diffusion of Cu into the insulating film and a seed layer Cu film acting as an electrode during electrolytic plating. These films were each formed by the sputtering method at a respective layer thickness of 30 nm ( FIG. 3I ). Then electrolytic plating was used to further deposit a 600 nm thick layer of Cu  13  ( FIG. 3J ). Thereafter, CMP was used to remove metal outside the interconnect pattern part to form the interconnect layer ( FIG. 3K ). 
     Next, explanation will be provided for the dual damascene method which is used when simultaneously forming the via layer and the interconnect layer. 
     Firstly, a cap SiN  14  is deposited 30 nm thick on the first layer interconnect layer with the object of preventing diffusion of Cu. Next, a SiOC film  15  is deposited 150 nm thick by plasma CVD. 
     At the interconnect layer part, firstly plasma CVD using silane and ammonia gas was used to deposit 30 nm thickness of a SiN film  16  as a stopper film. Thereafter, a low dielectric constant insulating film  17  (interconnect partition insulating film, relative dielectric constant=2.4, made from a low dielectric constant film having a vinyl group) in the same manner as described above was deposited under conditions to give a thickness of 250 nm on the Si slab. Thereafter, a 30 nm thick film of TEOS-SiO 2    18  was deposited as a protective film ( FIG. 4A ). 
     Using a resist layer having a via pattern as a mask for this insulating film, these films were subjected to wet etching. Specifically, these films in order (TEOS-SiO 2    18 , low dielectric constant insulating film  17 , SiN  16 , SiOC  15 , and SiN  14 ) were subjected to wet etching processing while irradiating with laser light  180  using the conditions of sample 4′ of working example 2 ( FIG. 4B ). 
     Thereafter, a resist layer applied as a mask for the second layer interconnect pattern was used to form an interconnect trench by treating the low dielectric constant insulating film  17  and the protective film  18  under the same conditions as described previously (treatment of  FIG. 4B ), ( FIG. 4C ). Furthermore, a TiN  19  film acting as a barrier to diffusion of Cu into the insulating film and a seed layer Cu film acting as an electrode during electrolytic plating were formed in the via hole and interconnect trench. These films were each formed by the sputtering method at a respective layer thickness of 30 nm ( FIG. 4D ). Then electrolytic plating was used to further deposit a 1400 nm thick layer of Cu  20  ( FIG. 4E ). Thereafter, CMP was used to remove metal outside the interconnect pattern part to form the interconnect layer ( FIG. 4F ). These steps were then repeated to form 3 layers of interconnects. When capacitance between interconnects was measured using a test multilayer interconnect comb-tooth pattern, the effective relative dielectric constant was 3.0. 
     Comparative Example 1 
     3 layers of interconnects were formed in exactly the same manner except for non-use of wet etching during the etching processing of working example 5 (etching by F plasma using CF 4 /CHF 3  gas as raw material). When capacitance between interconnects was measured using a test multilayer interconnect comb-tooth pattern, the effective relative dielectric constant was 3.7. 
     According to the present embodiment in this manner, technology is provided which suppresses damage by the etching solution to the workpiece during wet etching and which obtains a clean etching shape. According to the present embodiment, an interconnect layer of high TDDB resistance ability can be obtained with low leakage current. By this means, a semiconductor device can be produced which has low power consumption and high reliability.