Abstract:
A line slit nozzle for spraying steam is disposed along a diameter of a resist film. Steam containing a mist is sprayed onto a surface of the resist film. The film is thereby peeled off and removed. By using a change in physical properties (swelling, etc.) of the resist film by water, the film is easily and surely peeled off. Breakaway from much resources/energy consumption type techniques is realized. In other words, realized are environment-symbiosis type techniques by which resist films can be removed independently of the quantity of energy and kinds of chemical solvents.

Description:
BACKGROUND OF THE INVENTION  
         [0001]    1. Field of the Invention  
           [0002]    The present invention relates to apparatus and methods for removing resist (photoresist) films, indispensable to photolithographic processes for making minute structures of semiconductor integrated circuits or the like.  
           [0003]    2. Description of the Related Art  
           [0004]    As techniques for removing resist films, presently known are ashing methods in which a resist film to be removed is ashed with oxygen plasma, and heating and dissolving methods in which a resist film to be removed is dissolved using an organic solvent, such as a phenol- or halogen-base organic solvent, with being heated at 90 to 130° C., or using concentrated sulfuric acid and hydrogen peroxide. Any of these techniques requires a certain time, much energy and a specific chemical material for decomposing or dissolving the resist film. This was a strain on the photolithographic process. In spite of a great demand for new resist removing techniques to replace the above techniques by ashing or dissolving, developments of peeling techniques are yet few. As a representative of such peeling techniques, a new technique has been developed in which a peeling liquid newly developed and the peeling action of high-frequency supersonic waves are used. As such a peeling liquid, the peeling action of “an IPA-H 2 O 2 -base ingredient+salt such as fluoride” has bee appreciated.  
         SUMMARY OF THE INVENTION  
         [0005]    It is an object of the present invention to provide resist film removing apparatus and methods in which resist films can be peeled off by using a change in physical properties and a change in structure of the resist films due to application of steam and ultraviolet rays, and thereby to realize breakaway from much resources/energy consumption type techniques, that is, to realize environment-symbiosis type techniques by which resist films can be removed independently of the quantity of energy and kinds of chemical solvents.  
           [0006]    More specifically, the present invention is directed to removal of resist films by using a change in physical properties, such as softening, expansion, hydration, swelling, or solidification, or a change in structure, such as cross-linking, oxidation, or decomposition, of the resist films due to application of steam and ultraviolet rays. Additive ingredients for promoting such a change in quality may be selectively used.  
           [0007]    In other words, the present invention is directed to removal of resist films by a timely cross-combination, a spatially proper cross-combination, a proper cross-combination on temperature, or a chemically proper cross-combination of all or some of means for (or process of) spraying steam, compressed water, or compressed carbonic acid gas onto a resist film, means for (or process of) adding a chemical ingredient to the steam or compressed water, means for (or process of) heating or cooling the substrate holding thereon the resist film, and means for (or process of) irradiating the resist film with ultraviolet rays.  
           [0008]    The present inventors have taken up the following elemental techniques as subjects, and studied and developed them:  
           [0009]    Change in quality of resist films by steam;  
           [0010]    Chemical promotion of quality change of resist films; and  
           [0011]    Promotion of quality change of resist films by irradiation with ultraviolet rays.  
           [0012]    According to an aspect of the present invention, an apparatus for removing a resist film used in a lithographic process, comprises: means for bringing steam into contact with the resist film; and means for spraying steam onto the resist film, wherein the resist film is peeled off by an action of steam.  
           [0013]    According to an aspect of the present invention, the resist film is peeled off with saturated or superheated steam at a temperature within the range of 70° C. to 200° C.  
           [0014]    According to an aspect of the present invention, an apparatus for removing a resist film used in a lithographic process, comprises: means for spraying saturated steam onto the resist film, wherein the resist film is peeled off by an action of the saturated steam.  
           [0015]    According to an aspect of the present invention, the temperature of the saturated steam at the target surface is within the range of 70° C. to 100° C.  
           [0016]    According to an aspect of the present invention, steam containing an ingredient for promoting a change in quality of the resist film is brought into contact with and/or sprayed onto a surface of the resist film to peel the resist film.  
           [0017]    According to an aspect of the present invention, the apparatus comprises a steam supply system including a subsystem for generating steam, a subsystem for heating steam, a subsystem for controlling the water quantity to be supplied and the heat amount for heating, and a subsystem for controlling the pressure of steam. The steam supply system is connected to an ultrapure water supply line for selectively supplying saturated or superheated steam at a temperature within the range of 70° C. to 200° C.  
           [0018]    According to an aspect of the present invention, the steam supply system further includes a subsystem for switching lines between the ultrapure water supply line and a line for a solution containing an ingredient for promoting a change in quality of the resist film, and an injecting pump for the ingredient, so that steam containing the ingredient and steam not containing the ingredient can be switched over.  
           [0019]    According to an aspect of the present invention, the apparatus further comprises an ultraviolet reactor including an ultraviolet lamp of a wavelength corresponding to a transmissive distance of not less than 10 mm to steam. The ultraviolet lamp is disposed in parallel with a substrate surface on which the resist film is formed. The substrate surface can be irradiated while and after the resist film is peeled off the substrate surface by the action of steam.  
           [0020]    According to an aspect of the present invention, the apparatus further comprises a chamber provided with a system for taking in a substrate on which the resist film is formed and taking out the substrate off which the resist film has been peeled, a system for purging an atmosphere in the chamber, a system for discharging gas or liquid from the chamber, a system for introducing steam into the chamber, and a system for driving a steam spraying nozzle to move relatively to the substrate surface on which the resist film is formed, so as to sweep the substrate surface. The steam spraying nozzle sprays steam onto the substrate surface to peel the resist film off the substrate surface.  
           [0021]    According to an aspect of the present invention, the chamber is further provided with a system for supplying carbonic acid gas from a gas bomb into the chamber, and a gas spraying nozzle for spraying carbonic acid gas onto the substrate surface rapidly to cool the resist film to be peeled off.  
           [0022]    According to an aspect of the present invention, the apparatus further comprises a supply line for a liquid chemical for cleaning a substrate, connected to the steam supply system, wherein the substrate off which the resist film has been peeled is cleaned by irradiation with ultraviolet rays and spraying steam, and then dried by spraying superheated steam.  
           [0023]    According to an aspect of the present invention, the apparatus further comprises a filter for filtering off pieces of the resist film having been peeled off a substrate and contained in a liquid being discharged, or a centrifugal separator for separating the pieces from the liquid, wherein the liquid from which the pieces have been removed is reused.  
           [0024]    According to an aspect of the present invention, a method for removing a resist film used in a lithographic process, comprises steps of: bringing saturated or superheated steam into contact with the resist film; and spraying saturated or superheated steam onto the resist film, wherein the resist film is peeled off by an action of steam.  
           [0025]    According to an aspect of the present invention, steam containing an ingredient for promoting a change in quality of the resist film is brought into contact with a surface of the resist film to peel the resist film.  
           [0026]    According to an aspect of the present invention, in a method for removing a resist film used in a lithographic process, saturated steam is sprayed onto the resist film, and the resist film is peeled off by an action of the saturated steam.  
           [0027]    According to an aspect of the present invention, the temperature of the saturated steam at the target surface is within the range of 70° C. to 100° C.  
           [0028]    According to an aspect of the present invention, a substrate surface on which the resist film is formed, is irradiated with excimer ultraviolet rays of a wavelength corresponding to a transmissive distance of not less than 10 mm to steam, while and after the resist film is peeled off the substrate surface by the action of steam.  
           [0029]    According to an aspect of the present invention, organic, metallic, and granular contaminants are removed from a substrate surface off which the resist film has been peeled, by spraying steam with irradiating the substrate surface with ultraviolet rays, and then the substrate surface is cleaned and dried by spraying steam.  
           [0030]    According to an aspect of the present invention, steam containing an ingredient for promoting a change in quality of the resist film is brought into contact with and/or sprayed onto a surface of the resist film to peel the resist film.  
           [0031]    According to an aspect of the present invention, an apparatus for removing a resist film used in a lithographic process, comprises: means for making steam act on the resist film, wherein the resist film is peeled off by the action of the steam.  
           [0032]    According to an aspect of the present invention, the steam is saturated steam, and the temperature of the saturated steam at the target surface is within the range of 70° C. to 100° C.  
           [0033]    According to an aspect of the present invention, steam containing an ingredient for promoting a change in quality of the resist film is made to act on a surface of the resist film to be peeled off.  
           [0034]    According to an aspect of the present invention, the apparatus further comprises at least one of: means for making water act on the resist film; means for making vapor of isopropyl alcohol act on the resist film; means for making compressed carbonic acid gas act on the resist film; means for adding a chemical ingredient into the steam and/or the water; means for irradiating the resist film with ultraviolet rays; means for applying high-frequency supersonic waves to the resist film; and means for cooling a substrate on which the resist film is formed, wherein the resist film is peeled off by properly cross-combining at least one of time and/or spatial conditions, conditions on temperature, and physical and/or chemical conditions for operating each of the means.  
           [0035]    According to an aspect of the present invention, the apparatus further comprises a one-by-one process chamber in which substrates to be processed are disposed one by one. The chamber is provided with a system for taking in and out the substrates, a system for purging the atmosphere in the chamber, and a system for discharging gas or liquid from the chamber, in addition to the above means. The chamber is further provided with a driving system for at least one of the means for making steam act on the resist film, the means for making water act on the resist film, and the means for making compressed carbonic acid gas act on the resist film, to move relatively to the front or back surface of each substrate.  
           [0036]    According to an aspect of the present invention, as the above time and/or spatial conditions for operating the above means and/or the above systems, the order of the operations and the intervals of the operations are properly cross-combined in relation to the portions subjected to the operations, i.e., the surface of the resist film, both or one of the front and rear surfaces of the substrate, or part of the front or rear surface of the substrate.  
           [0037]    According to an aspect of the present invention, as the above conditions on temperature for operating the above means and/or the above systems, process temperatures and the raising and lowering speeds thereof are properly cross-combined in relation to the portions subjected to the operations, i.e., the surface of the resist film, both or one of the front and rear surfaces of the substrate, or part of the front or rear surface of the substrate.  
           [0038]    According to an aspect of the present invention, as the above physical and/or chemical conditions for operating at least one of the means for adding a chemical ingredient into the steam and/or the water, the means for irradiating the resist film with ultraviolet rays, and the means for applying high-frequency supersonic waves to the resist film, the compositions of chemical ingredients for the steam and/or the water, the frequencies of supersonic waves, and the wavelengths of ultraviolet rays are properly cross-combined.  
           [0039]    According to an aspect of the present invention, the above time and/or spatial conditions, the above conditions on temperature, and the above physical and/or chemical conditions are properly cross-combined with one another.  
           [0040]    According to an aspect of the present invention, the means for making steam act on the resist film has the function of bringing the steam into contact with the resist film and the function of spraying the steam onto the resist film. The contact process and the spraying process are properly cross-combined.  
           [0041]    According to an aspect of the present invention, the means for making steam act on the resist film has the function of making saturated steam act on the resist film and the function of making superheated steam act on the resist film. The saturated steam process and the superheated steam process are properly cross-combined.  
           [0042]    According to an aspect of the present invention, the steam process by the means for making steam act on the resist film, and a chemical ingredient composition determined by the means for adding a chemical ingredient into the steam are properly cross-combined.  
           [0043]    According to an aspect of the present invention, the steam process by the means for making steam act on the resist film, and the water spraying process by the means for making water act on the resist film are properly cross-combined.  
           [0044]    According to an aspect of the present invention, the steam process by the means for making steam act on the resist film, and the ultraviolet irradiation process by the means for irradiating the resist film with ultraviolet rays are properly cross-combined.  
           [0045]    According to an aspect of the present invention, the steam process by the means for making steam act on the resist film, and the high-frequency supersonic application process by the means for applying high-frequency supersonic waves to the resist film are properly cross-combined.  
           [0046]    According to an aspect of the present invention, the steam process by the means for making steam act on the resist film, and the compressed carbonic acid gas spraying process by the means for making compressed carbonic acid gas act on the resist film are properly cross-combined.  
           [0047]    According to an aspect of the present invention, the steam process by the means for making steam act on the resist film, and the cooling process by the means for cooling a substrate on which the resist film is formed, are properly cross-combined.  
           [0048]    According to an aspect of the present invention, the steam process by the means for making steam act on the resist film, and the vapor process by the means for making vapor of isopropyl alcohol act on the resist film are properly cross-combined.  
           [0049]    According to an aspect of the present invention, the compressed carbonic acid gas spraying process by the means for making compressed carbonic acid gas act on the resist film, and the ultraviolet irradiation process by the means for irradiating the resist film with ultraviolet rays are properly cross-combined.  
           [0050]    According to an aspect of the present invention, by properly cross-combining the above time and/or spatial conditions, the above conditions on temperature, and the above physical and/or chemical conditions for operating the above means and/or the above systems, the substrate surface off which the resist film has been peeled is processed to remove residues of the resist film and alien substances. The substrate surface is thereby purified.  
           [0051]    According to an aspect of the present invention, a method for removing a resist film used in a lithographic process, comprises a step of making steam act on the resist film, wherein the resist film is peeled off by the action of the steam.  
           [0052]    According to an aspect of the present invention, the method further comprises at least one of: a step of making water act on the resist film; a step of making vapor of isopropyl alcohol act on the resist film; a step of making compressed carbonic acid gas act on the resist film; a step of adding a chemical ingredient into the steam and/or the water; a step of irradiating the resist film with ultraviolet rays; a step of applying high-frequency supersonic waves to the resist film; and a step of cooling a substrate on which the resist film is formed, wherein the resist film is peeled off by properly cross-combining at least one of time and/or spatial conditions, conditions on temperature, and physical and/or chemical conditions for performing each of the steps.  
           [0053]    According to an aspect of the present invention, as the above time and/or spatial conditions for performing the above steps, the order of the steps and the intervals of the steps are properly cross-combined in relation to the portions subjected to the steps, i.e., the surface of the resist film, both or one of the front and rear surfaces of the substrate, or part of the front or rear surface of the substrate.  
           [0054]    According to an aspect of the present invention, as the above conditions on temperature for performing the above steps, process temperatures and the raising and lowering speeds thereof are properly cross-combined in relation to the portions subjected to the steps, i.e., the surface of the resist film, both or one of the front and rear surfaces of the substrate, or part of the front or rear surface of the substrate.  
           [0055]    According to an aspect of the present invention, as the above physical and/or chemical conditions for performing at least one of the step of adding a chemical ingredient into the steam and/or the water, the step of irradiating the resist film with ultraviolet rays, and the step of applying high-frequency supersonic waves to the resist film, the compositions of chemical ingredients for the steam and/or the water, the frequencies of supersonic waves, and the wavelengths of ultraviolet rays are properly cross-combined.  
           [0056]    According to an aspect of the present invention, the above time and/or spatial-conditions, the above conditions on temperature, and the above physical and/or chemical conditions are properly cross-combined with one another.  
           [0057]    According to an aspect of the present invention, the step of making steam act on the resist film includes a sub-step of bringing the steam into contact with the resist film and a sub-step of spraying the steam onto the resist film. The contact process and the spraying process are properly cross-combined.  
           [0058]    According to an aspect of the present invention, the step of making steam act on the resist film includes a sub-step of making saturated steam act on the resist film and a sub-step of making superheated steam act on the resist film. The saturated steam process and the superheated steam process are properly cross-combined.  
           [0059]    According to an aspect of the present invention, the steam process by the step of making steam act on the resist film, and a chemical ingredient composition determined in the step of adding a chemical ingredient into the steam are properly cross-combined.  
           [0060]    According to an aspect of the present invention, the steam process by the step of making steam act on the resist film, and the water spraying process by the step of making water act on the resist film are properly cross-combined.  
           [0061]    According to an aspect of the present invention, the steam process by the step of making steam act on the resist film, and the ultraviolet irradiation process by the step of irradiating the resist film with ultraviolet rays are properly cross-combined.  
           [0062]    According to an aspect of the present invention, the steam process by the step of making steam act on the resist film, and the high-frequency supersonic application process by the step of applying high-frequency supersonic waves to the resist film are properly cross-combined.  
           [0063]    According to an aspect of the present invention, the steam process by the step of making steam act on the resist film, and the compressed carbonic acid gas spraying process by the step of making compressed carbonic acid gas act on the resist film are properly cross-combined.  
           [0064]    According to an aspect of the present invention, the steam process by the step of making steam act on the resist film, and the cooling process by the-step of cooling a substrate on which the resist film is formed, are properly cross-combined.  
           [0065]    According to an aspect of the present invention, the steam process by the step of making steam act on the resist film, and the vapor process by the step of making vapor of isopropyl alcohol act on the resist film are properly cross-combined.  
           [0066]    According to an aspect of the present invention, the compressed carbonic acid gas spraying process by the step of making compressed carbonic acid gas act on the resist film, and the ultraviolet irradiation process by the step of irradiating the resist film with ultraviolet rays are properly cross-combined.  
           [0067]    According to an aspect of the present invention, by properly cross-combining the above time and/or spatial conditions, the above conditions on temperature, and the above physical and/or chemical conditions for performing the above steps, the substrate surface off which the resist film has been peeled is processed to remove residues of the resist film and alien substances. The substrate surface is thereby purified.  
           [0068]    According to the present invention, by using a change in physical properties (such as swelling) of a resist film by steam and a light decomposition effect by ultraviolet rays, it becomes possible to peel off the resist film easily and surely. As a result, breakaway from much resources/energy consumption type techniques can be realized, that is, an environment-symbiosis type technique independent of the quantity of energy and kinds of chemical solvents can be realized. 
       
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
       [0069]    [0069]FIG. 1 is a schematic sectional view showing a portion near a spraying nozzle of a resist removing apparatus according to the present invention;  
         [0070]    [0070]FIG. 2 is a graph showing the relation of the speed of removing a resist film by steam containing KOH, to the concentration of KOH;  
         [0071]    [0071]FIG. 3 is a schematic view showing a principal construction of a steam supply apparatus according to an embodiment of the present invention;  
         [0072]    [0072]FIG. 4 is a schematic view showing a principal construction of a resist removal apparatus according to an embodiment of the present invention;  
         [0073]    [0073]FIGS. 5A to  5 E are schematic sectional views showing the constructions of samples from each of which a resist film is to be peeled off; and  
         [0074]    [0074]FIG. 6 is a schematic sectional view of a one-by-one resist film removing apparatus including a spinning mechanism. 
     
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS  
       [0075]    Hereinafter, preferred embodiments of the present invention will be described.  
         [0076]    1. Peeling Resist Film by Steam  
         [0077]    Porousness and Hydrogen Bondability of Chemical Structure of Resist Film:  
         [0078]    In a photolithographic process for making a minute structure of, e.g., a semiconductor integrated circuit, a resist film is formed on a surface to be processed. Electromagnetic energy is then applied to the resist film through fine pattern gaps provided on an exposure mask. The thus formed pattern is developed in the resist film by using the difference in solubleness to a solvent between irradiated and non-irradiated portions of the resist film. The surface to be processed is then etched using the resist film pattern as an etching mask.  
         [0079]    In such photolithographic processes, the wavelength of ultraviolet rays used has gradually become shorter with progress of the generations of degrees of integration. That is, g line, i line, and ArF to F 2  excimer lasers were used in this order. As a matter of course, the chemical structures of resist films have been reformed with shortening the used wavelength, and will be more reformed for future X-ray and electron ray photolithography ages. In reforming the chemical structures of resist films, it is important to grasp the physical properties of the basic structures unchanging fundamentally.  
         [0080]    The present inventors have perceived the porousness and the hydrogen bondability of the basic structures of the base polymers of resist films.  
         [0081]    Table 1 shows the basic structures of the base polymers of various photoresists from an initial resist KPR to currently mainstream resists, besides, resists for ARF excimer laser.  
                             TABLE 1                       Base Polymer Basic Structure of Resist                                first generation resist   vinyl cinnamate                                             resist for g to i line   cyclo-polyisoprene                                             do.   novolac resin                                             resist for KrF   polymethyl methacrylate                                             do.   polymethyl isopropenyl ketone                                             do.   chloromethyl polystyrene                                             do.   polystyrene sulfone                                             do.   polyvinyl phenol                                             resist for ArF   alicyclic polymethacrylate                                             do.   polybutene sulfone -positive type-                                                
 
         [0082]    The chemical structures of the principal and side chains of these photoresists differ variously. But, in these various basic structures, there are two fundamental points of sameness.  
         [0083]    They are the porousness of the basic structures and the hydrogen bondability of the constituent groups. Because of the cyclic structures or the structures having side chains of, e.g., alicyclic groups or phenol groups, the polymer basic structures have considerable spaces therein.  
         [0084]    Besides, constituent groups having intensive hydrogen bondability, such as phenol groups, carbonyl groups, or ester groups, have been introduced. Introduction of these groups is necessary for the resists sensitively to react to light energy. Besides, resists must have solubility to developers, and the porousness and hydrogen bondability are physical properties necessary for the solubility.  
         [0085]    Besides, the water permeabilities of resists are higher than those of other organic polymers. For example, while the water permeability (Pa·cm 3 ·s −1 ·m −2 ) of Teflon, or polyethylene is about 3×10 −11 , those of resists are 10 −8  to 10 −7 , showing their structures more permeable to water by three to four figures.  
         [0086]    It is because the polymer structures of resists are porous in contrast to compactness of organic polymers having structural regularity, and further the polymer structures of resists have hydrogen bondability.  
         [0087]    In future, resists will be required to be chemically amplificative, and addition of chemical amplification ingredients will be done.  
         [0088]    But, “resist-peeling” is directed by base polymer basic structures. It is a characteristic feature of the present invention to utilize the porousness and hydrogen bondability which are fundamental properties of resists.  
         [0089]    Change in Quality of Resist Film by Steam:  
         [0090]    The present inventors has perceived the fact that the states of resist films change rapidly and remarkably by steam. Physical changes such as softening/expansion due to hot steam occur naturally; besides, changes in physical properties such as swelling/separation/solidification occur. There have been found changes in chemical structure of the resist films though their aspects vary in accordance with the kinds of resists and conditions of steam. The details of such changes are supposed as follows.  
         [0091]    Because the basic structures of the resist base polymers have porousness as described above, the resist transmissivity of steam is very high. A resist film is put in a pyrogenetic chemical reaction system the moment it comes into contact with steam. It is well known that the chemical action of water at a high temperature is intensive, and there are known many instances of hydrolysis of organic compounds by hot water. In a resist chemical structure, side chains having high hydrogen-bondability and photosensitive groups are present. Not only hydrolysis/oxidation of these groups but also cross-linking in the resist basic structure progresses.  
         [0092]    Action of Saturated or Superheated Steam:  
         [0093]    The temperature of steam necessary for processing a resist film varies in accordance with the kind of resist and conditions of the resist process. The steam temperature is selected to a suitable value of 70° C. to 200° C. The temperature may be more than 200° C. if circumstances of the substrate allow. In ultraviolet irradiation, superheated steam hardly brings about absorption and scattering of ultraviolet rays due to a mist, and it shows high efficiency of ultraviolet transmissivity. Besides, superheated steam is not affected by the mist when drying the surface from which a resist film has been peeled off.  
         [0094]    Peeling Swelled Resist Film off Substrate by Spraying Steam:  
         [0095]    The power of sprayed steam acts effectively for peeling a swelled resist film off a substrate. The resist film which has been hydrated/swelled and softened by hot steam, a mist, and further a swelling-promotion ingredient, is easily peeled off the substrate surface if the linear velocity of sprayed steam is several m/sec to scores m/sec. The peeling speeds depend on the kinds of resists. In particular, ion-implanted resist films have a tendency to be hard to peel off. Shape of pattern also exerts influence. In particular, high aspect ratio is a cause of the tendency to be hard to peel off. Considering such resist physical properties/substrate structures, the linear velocity and spraying time are controlled. In resist-peeling, it is important to control the spraying linear velocity in order not to damage the minute structure of the exposed surface.  
         [0096]    Contact and Spraying of Steam:  
         [0097]    Required is an apparatus capable of realizing a combination of a step of bringing a resist film into contact with steam to change the quality of the film, and a step of spraying steam onto the resist film which has changed in quality, to peel off.  
         [0098]    The surface structure exposed as a result of resist-peeling must be protected without any damage. While the power of sprayed steam at a linear velocity of one m/sec to scores m/sec is strong and effective for resist-peeling, it may damage the device surface. A two-step process is effective in which change in quality of a resist film is made to progress in a contact step, and then the film is peeled off in a spraying step of a short time. This is suitable in particular for removing an ion-implanted resist film in which the speed of change in quality is low, or a resist film on a surface where a structural aspect ratio is high.  
         [0099]    Resist-Peeling Only by Spraying Saturated Steam:  
         [0100]    The present inventors have thought out a process of peeling a resist film only by spraying steam containing droplets, i.e., saturated steam, without using the above-described two-step process of the contact and spraying steps of steam.  
         [0101]    More specifically, as shown in FIG. 1 for example, to remove a resist film 44 after patterning a SiO 2  film  43  on a substrate  42 , a steam spraying nozzle  41  is disposed to be opposed to the resist film  44 , and steam is sprayed to peel the resist film  44 . In spraying conditions of this case, the temperature of saturated steam at the portion which steam reaches, i.e., the surface portion of the resist film  44 , is controlled within the range of 70° C. to 100° C., more preferably, within the range of 75° C. to 85° C. This is because sprayed steam makes saturated steam containing droplets, suitable for peeling the resist film  44 , at the surface portion of the resist film  44  when the temperature is controlled within the above range. FIG. 1 shows an example for realizing the above temperature range, in which the distance from the spraying nozzle  41  to the surface of the resist film  44  is 10 mm. Besides, the spraying pressure of steam at the mouth of the spraying nozzle  41  is controlled to be less than 10 kg/cm 2 , more preferably, within the range of 1 to 2 kg/cm 2 . If the pressure exceeds 10 kg/cm 2 , the spraying nozzle  41  and device elements formed on the substrate  42  may be adversely affected.  
         [0102]    A process in which a contact step uses steam containing an ingredient for promoting change in quality of a resist film as described in the next section, and a spraying step uses pure water steam, is effective for preventing a metal wiring surface from being damaged.  
         [0103]    Ingredient for Promoting Change in Quality of Resist:  
         [0104]    It has been found that a change in physical properties/structure by hot steam can be accelerated by making the steam contain an ingredient for promoting the change in quality. In particular, a resist film hardened by an ion-implantation process is very hard to peel off. In spite of this fact, however, it can rapidly be peeled off by using steam which contains a promotion ingredient. Since the kind of effective promotion ingredient varies in accordance with the kind of resist, it need be selected individually. Protection of a structural substrate after resist-peeling, e.g., chemical action on a metal surface of a metal wiring substrate need be considered.  
         [0105]    Oxidative substances are effective as promotion ingredients for cross-linking or oxidation. For example, hydrogen peroxide can make even an ion-implantation-processed resist film change in quality/be peeled off in a short time. We suppose that it is by oxidation of chemical bonding in the resist because of intensive radical reaction. Ozone water is also effective as a promotion ingredient for oxidation.  
         [0106]    Also usable are other oxidative substances, such as Cl 2 —H 2 O, Br 2 —H 2 O, I 2 —KI, NaClO, NaClO 4 , KMnO 4 , K 2 CrO 7 , and Ce(SO 4 ) 2 .  
         [0107]    Alkali is a highly effective promotion ingredient. For example, usable is an aqueous solution of caustic alkali at a pH value of 8 to 14, more preferably, 10 to 12. It gives the resist surface wettability/permeability, and makes the peeling-off action rapid. As alkali, usable are KOH, NaOH, NaCO 3 , Ca(OH) 2 , Ba(OH) 2 , NH 4 OH, TMAH, etc.  
         [0108]    More specifically, examined were the removing speeds of resist films which were used as a mask for ion implantation of impurities (As), when the resist films were removed using the technique shown in FIG. 1 and using KOH of alkali as a resist quality change promotion ingredient. FIG. 2 shows the result of measurement. In FIG. 2, the axis of abscissas represents the concentration (wt. %) of KOH, and the axis of ordinates represents the removing speed (sec). As shown in FIG. 2, the higher the KOH concentration is, the higher the removing speed is. This shows that the higher KOH concentration brings about the more efficient resist-peeling. However, too high KOH concentration may cause an adverse affection on a device material, so it is seemed that about 0.1 (wt. %) or less is proper.  
         [0109]    Also acids and oxidative acids are promotion ingredients for change in quality. For example, H 2 SO 4  makes a resist cross-link strongly. Usable are H 2 SO 4 , HNO 3 , HClO, HClO 4 , HCl, HF, etc.  
         [0110]    Surface active agents have interfacial osmotic actions and surface functions for preventing peeled resist thin pieces from again adhering to the surface which they have been peeled off. As such surface active agents, usable are anionic, cationic, and nonionic surface active agents whose contact angles to resist surfaces are not more than 30 degrees, more preferably, not more than 20 degrees.  
         [0111]    2. Peeling Resist Film by Ultraviolet Rays  
         [0112]    (1) Decomposition of Resist Film by Ultraviolet Rays:  
         [0113]    Table 2 shows experimental data of decomposition tests of photoresists by ultraviolet rays. Light-decomposition of photoresists is possible by using a Xe excimer lamp (wavelength: 172 nm) as an ultraviolet lamp. But, the decomposition speed is too low to apply to removal of resist films. Although there is an attempt of acceleration by existence of ozone at a high concentration, putting it to practical use faces many hurdles.  
                                                                   TABLE 2                           Decomposition of Photoresist by Ultraviolet Rays                ultra-   decrease   speed                   violet   in   of   theoretical               irradia-   film   decom-   speed of               tion   thick-   posi-   decomposi-   quantum           time   ness   tion   tion   efficiency       photoresist   (sec)   (μm)   (nm/sec)   (nm/sec)   (%)                    positive   2700   700   0.26   0.12   47       type resist       1400 μm       thick                                  
 
         [0114]    The present inventors have perceived a change in quality of resists by ultraviolet rays. It aims not at resist decomposition but at resist-peeling. Since ultraviolet photons have strongly promoting actions for cross-linking or oxidation, the action of changing the quality of resists is intensive. An incorporated effect with a quality-change effect by steam is used. Besides, since ultraviolet rays have high resist transmissivity, they can fully reach the boundary layer of resist/substrate. It is an intensive permeating action. A change in quality of the boundary layer is directly related to the peeling effect.  
         [0115]    3. Steam supply Apparatus  
         [0116]    [0116]FIG. 3 shows the fundamental construction of a steam supply apparatus. An evaporator  1  and a heating block  2  for generating saturated steam, and a superheater  3  and a heating block  4  for generating superheated steam, are disposed between a fixed flow rate pump  5  and a pressure control needle valve  6 . The internal pressure of this steam generation system is measured with a pressure gauge  7 . The temperatures of saturated and superheated steams are measured with thermometers  8  and  9 , respectively. The heating area in the evaporator  1  is so designed as to satisfy the burnout point condition of a boiling characteristic curve.  
         [0117]    Switching Between Steam of Pure Water and Steam Containing Promotion Ingredient:  
         [0118]    When steam of ultrapure water is generated, a valve  10  for an ultrapure water line is opened. When steam containing a promotion ingredient is generated, a valve  11  for an aqueous solution line is opened.  
         [0119]    Switching Between Saturated and Superheated Steams:  
         [0120]    When saturated steam is supplied, the heating block  4  for superheating is not supplied with heats. At this time, the superheater  3  merely functions as a passage for steam. When superheated steam is supplied, the heating block  4  is supplied with heats to perform superheating by the superheater  3 .  
         [0121]    Switching Between Steam-Contact and Steam-Spraying:  
         [0122]    When steam is introduced into a process chamber  15 , an introduction valve  12  is opened. When steam is sprayed onto a surface to be processed, a steam-spraying valve  13  is opened and steam is sprayed onto the surface  16  to be processed, through a steam-spraying nozzle  14 .  
         [0123]    Table 3 exemplifies control conditions for steam supply. Table 4 exemplifies conditions of the steam spraying nozzle. The nozzle shape/steam quantity/spraying velocity can freely be designed so as to meet the purpose.  
                                                                                                                                             TABLE 3                           Control Condition for Steam Supply                saturated steam generation   superheated steam generation            water supply   conditions   conditions            quantity and heat   internal   tempera-   steam   internal   tempera-   steam       quantity   pressure   ture   quantity   pressure   ture   quantity            ml/sec   KWH   Kg/cm 2     ° C.   L/sec   Kg/cm 2     ° C.   L/sec                    1.5   3.9   1.0   100   2.55   —   —   —       1.5   3.9   2.0   120   2.69   1.00   120   2.69       1.5   4.0   3.6   140   2.83   1.00   140   2.83       1.5   4.0   6.0   160   2.96   1.00   160   2.96                                          
 
         [0124]    [0124]                                                                         TABLE 4                           Condition Example of Steam-spraying Nozzle                point nozzle   line slit nozzle                    steam-       steam-               spraying       spraying       steam       linear       linear       quantity       velocity       velocity       L/sec   nozzle shape   m/sec   nozzle shape   m/sec                    2.55   inside   120   200 mm × 0.5 mm   52           diameter of           5 mm       2.55   inside   32   200 mm × 1.0 mm   13           diameter of           10 mm                    
         [0125]    4. Ultraviolet Reactor  
         [0126]    Selections of the ultraviolet wavelength and time characteristics of a lamp used in an ultraviolet reactor are important technical factors.  
         [0127]    Selection of Ultraviolet Wavelength:  
         [0128]    The shorter the ultraviolet wavelength is, the greater the energy is and the lower the transmissivity to the irradiation atmosphere is. The ultraviolet wavelength must be so selected as to satisfy the objective transmissivity.  
         [0129]    A relation between the light absorption sectional area of molecules present in the atmosphere and the light transmissivity, is given by expression (1). Logarithms of the transmissivity are proportional to distances. The present inventors use 50% transmissive distance as an index. This 50% transmissive distance is given by expression (2). Table 5 shows relations between ultraviolet wavelengths and 50% transmissive distances to air, water, and steam obtained by expression (2) or actual measurements. For example, the 50% transmissive distance of ultraviolet rays of the wavelength of 172 nm to air is obtained as 3.1 mm from the light absorption sectional area of oxygen (0.259×10 −19  molecules/cm 2 ) while the actual measurement of 2.2 mm was obtained. Both are practically almost equal.  
         δCL=ln(I°/I)  (1)  
         [0130]    δ: light absorption sectional area (molecules/cm 2 ), O 2  . . . 0.259×10 −19    
         [0131]    C: molecule concentration (partial pressure of molecule)  
         [0132]    L: transmissive distance (cm)  
         I°/I: light transmissivity=incident light intensity/transmitted light intensity  (2)  
         [0133]    δCL 50 =ln (100/50)  
         [0134]    L 50 : 50% transmissive distance  
                                                                                                   TABLE 5                           Ultraviolet Wavelength and 50% Transmissive distances       to Air/Water/Steam                50% transmissive distance            excimer   wavelength   energy   air   water   steam       ultraviolet lamp   nm   eV   mm   mm   mm                    Xe excimer lamp   172   7.21   3   —            ArCl excimer lamp   175   7.08   6   &lt;10   &lt;10           185   6.70   40   10   &gt;1 × 10 4         KrI excimer lamp   191   6.49   100   28           ArF excimer lamp   193   6.42   &gt;100   42           KrBr excimer lamp   207   5.99       &gt;100           KrCl excimer lamp   222   5.58           low pressure   185 • 254           mercury lamp           i-line lamp   365   3.41                      
 
         [0135]    Selection of Time Response:  
         [0136]    An ultraviolet lamp is selected in accordance with the type of ultraviolet process, i.e., which of a moment type and a constant type is performed.  
         [0137]    An ultraviolet excimer lamp can be used in a moment-type process. It reaches its stationary state in several seconds after being lit.  
         [0138]    It is suitable for a sequential process in seconds in a one-by-one ultraviolet process. A low pressure mercury lamp, an i-line lamp, or the like, can be used in a constant-type process. Although they require scores minutes for reaching their stationary states after being lit, they are stable after then.  
         [0139]    5. One-by-One Resist-Peeling Apparatus  
         [0140]    (1) Construction of Apparatus:  
         [0141]    A one-by-one resist-peeling apparatus comprises a steam process chamber and an ultraviolet lamp chamber.  
         [0142]    The steam process chamber has a substrate taking-in/out system, an atmosphere purge system, and a liquid discharge system. In the chamber, a driving system is provided for moving a steam-spraying nozzle relatively to a substrate surface to be processed, so as to sweep the substrate surface. A point nozzle or a line slit nozzle is disposed in the chamber.  
         [0143]    [0143]FIG. 4 shows a one-by-one resist-peeling apparatus including a spinning mechanism. This apparatus comprises a steam process chamber  23  provided with a spinning mechanism  22  for rotating a substrate  21 , and a lamp chamber  26  including an ultraviolet lamp  24  and having a quartz window board  25 . A gas inlet  27  to the chamber and a discharge duct  28  are accompanied.  
         [0144]    When steam is introduced into the process chamber from the steam supply apparatus (see FIG. 3), the steam introduction valve  12  is opened. When steam is sprayed onto a surface to be processed, the steam-spraying valve  13  is opened and steam is sprayed onto the surface of the substrate  21  through the steam-spraying nozzle  14 .  
         [0145]    Shown is an example of the steam-spraying nozzle  14  in which a line slit nozzle is disposed in a radial direction.  
         [0146]    Alternatively, usable is a system including a spot nozzle driven radially, or several nozzles movable in a proper distance or fixed. The spraying angle and spraying distance of the nozzle and the linear velocity of sprayed steam are optimized in various respects, such as the object of the process, the surface structure of the substrate, and protection for damage.  
         [0147]    The steam process chamber  23  is kept in temperature. Steam is condensed little by little on the inner wall of the chamber. It serves for cleaning the inner wall. In this manner, the interior of the chamber is always kept clean.  
         [0148]    The gas inlet  27  to the chamber is used for changing the atmosphere when a substrate is taken in/out. It is used also for adding an ingredient effective for the process, to the atmosphere. The discharge duct  28  preferably has a cooling structure.  
         [0149]    (2) Physical Peeling Promotion:  
         [0150]    Quenching (Rapidly Cooling) Resist Film:  
         [0151]    Although not shown in FIG. 4, a carbonic acid gas-spraying nozzle can be disposed to be opposite to a substrate surface. It is for spraying carbonic acid gas and the resultant dry ice particles onto the substrate surface to quench (cool rapidly) the resist film. The resist film which was heated and swelled, shrinks/solidifies and is peeled off the substrate. It has been confirmed that such a quenching process promotes the peeling-off operation of some kinds of resists.  
         [0152]    High-Speed Spinning:  
         [0153]    When the number of revolution of the substrate is set at 2000 rpm or more using the spinning mechanism, the peeling-off operation is promoted. In particular, the peeling-off operation is promoted when the steam-spraying effect is weak on the peripheral portion.  
         [0154]    6. Making Resist-Peeling Process and Surface-Cleaning Process after Peeling Off, Sequential  
         [0155]    A resist-peeling process and a surface-cleaning process after resist-peeling can be a sequential process.  
         [0156]    Switching from the resist-peeling apparatus to a surface-cleaning apparatus after resist-peeling is simple.  
         [0157]    By altering the aqueous solution line 11 of the steam supply apparatus of FIG. 3 into a switching system between a peeling-promotion solution line  11 A and a surface-cleaning solution line  11 B, the resist-peeling apparatus and a surface-cleaning apparatus after resist-peeling can be switched freely.  
         [0158]    Since the combination of the steam and ultraviolet processes effectively shortens both the peeling time and the cleaning time, the unity of the processes can be realized with no decrease in throughput.  
       EXAMPLES  
       [0159]    Hereinafter, specific examples of the present invention will be described. Although the description is omitted in each example, the resist-peeling state is obtained by observing the peeled surface at each spraying time with an optical microscope.  
       Example 1  
       [0160]    Shown are examples of peeling resist films by steam of pure water.  
         [0161]    Sample: FIG. 5A; a resist film formed on a dry-etched thermal oxidation film;  
         [0162]    [0162]FIG. 5B; a resist film formed on a dry-etched gate electrode (polysilicon film)  
         [0163]    Steam: steam of pure water  
         [0164]    Result of Peeling:  
         [0165]    As shown in the below Table 6, peeling could be performed by spraying for thirty seconds to one minute.  
                                                   TABLE 6                           Steam Effect and Peeling Result                pure-water   spraying time                steam   15 sec   30 sec   1 min               oxide film dry-   100° C.   partially   fully peeled           etched surface   saturated   remained           steam       gate electrode   100° C.   —   partially   fully peeled       etched surface   saturated       remained           steam                                          
 
       Example 2  
       [0166]    Shown are examples of peeling resist films by steam containing promotion ingredients.  
         [0167]    The resist films have been ion-implanted and are known to be very hard to peel off.  
         [0168]    Sample: FIG. 5C; silicon thermal oxidation film dry-etched; its underlayer of a silicon substrate ion-implanted;  
         [0169]    Ion-implantation conditions: acceleration energy of 80 keV; dose amount of phosphorus of 6×10 15 /cm 2 ;  
         [0170]    Promotion ingredient-containing steam: promotion ingredient; alkali (KOH) and a surface active agent.  
         [0171]    Result of Peeling:  
         [0172]    As shown in Table 7, peeling could be performed by spraying steam for two minutes. In case of the promotion ingredient of alkali, some peeled-off pieces adhering to the surface after peeling were observed. But, in case of the promotion ingredient of alkali+surface active agent, no peeled-off piece is found.  
                                                                 TABLE 7                           Effect of Quality-change Promotion Ingredient and       Peeling Result                quality-               change           promotion   spraying time                ingredient   1 min   2 min                        oxide film   alkali   partially   fully peeled       etched/ion-implanted       remained   (peeled-off pieces       surface           adhered)       oxide film   alkali +   partially   fully peeled       etched/ion-implanted   surface   remained   (no peeled-off piece       surface   active agent       adhered)                  
 
       Example 3  
       [0173]    Shown are further examples of peeling resist films by steam containing promotion ingredients.  
         [0174]    Sample: FIG. 5D; silicon thermal oxidation film wet-etched; a negative-type resist film;  
         [0175]    [0175]FIG. 5E; after etching metal wiring; a positive-type resist film;  
         [0176]    Promotion ingredient-containing steam: promotion ingredient; hydrogen peroxide and a surface active agent.  
         [0177]    Result of Peeling:  
         [0178]    The resist film was fully peeled off the surface of the thermal oxidation film by spraying steam containing the promotion ingredient for one minute. The resist film was fully peeled even off the etched metal wiring/ion-implanted surface inferior in ability of peeling, in two minutes.  
                                                   TABLE 8                           Effect of Quality-change Promotion Ingredient and       Peeling Result                quality-               change           promotion   spraying time                 ingredient   30 sec   1 min   2 min               oxide film wet-   hydrogen   partially       fully peeled       etched surface   peroxide   remained       metal wiring   hydrogen       partially   fully peeled       etched/ion-implanted   peroxide       remained       surface                  
 
       Example 4  
       [0179]    Shown are examples by two-step steam processes for metal-wiring surfaces.  
         [0180]    Object of two-step process: it aims at avoiding chemical damage to metal wiring. A promotion ingredient is used when the metal-wiring surface is covered with a resist film. No promotion ingredient is used after the resist film is peeled off the metal-wiring surface to be exposed.  
         [0181]    Details of two-step process:  
         [0182]    first step (steam-contacting process); using steam containing alkali;  
         [0183]    second step (steam-spraying process); using steam of pure water.  
         [0184]    Result of Peeling:  
         [0185]    Table 9 shows the results. The resist film was removed by the steam process of the second step for thirty seconds, and the metal wiring was not damaged.  
         [0186]    For comparison, an example of process only with steam containing alkali is shown. This case required two minutes of spraying time, and some damages to the metal wiring on the surface after removing the resist film were observed.  
                                     TABLE 9                           Effect of Two-step Steam Processing for Device                    first step   second step   resist removal               steam-   steam-   state           processing   contacting   spraying   [state of metal           step   process   process   wiring]               condition   kind of steam   saturated   saturated   removed in           removal   steam   steam no   process time           promotion   containing   promotion   of 1 min and           ingredient   alkali   ingredient   30 sec           temperature   100° C.   100° C.   [no damage to           of steam           metal wiring]           processing   1 min   30 sec           time       comparison   kind of steam   no first   saturated   removed in           removal   step   steam   spraying time           promotion       contain-   of 2 min           ingredient       ing alkali           temperature       100° C.   [damages to           of steam           metal wiring]           processing       2 min           time                  
 
       Example 5  
       [0187]    Shown are examples by hot steam processes for ion-implanted resist films, which are hard to peel off.  
         [0188]    Sample: FIG. 5C; silicon thermal oxidation film etched; its underlayer of a silicon substrate ion-implanted;  
         [0189]    Ion-implantation conditions: acceleration energy of 80 keV; dose amount of phosphorus of 6×10 13 /cm 2    
         [0190]    Result of Peeling:  
         [0191]    Table 10 shows the results.  
         [0192]    In the 100° C. saturated steam process of the condition 1, the resist film could not be removed even by spraying for ten minutes.  
         [0193]    In the 120° C. saturated steam process of the condition 2, the resist film could be removed by contacting process for two minutes and spraying process for one minute.  
         [0194]    In the 140° C. superheated steam process after the 130° C. saturated steam process for thirty seconds of the condition 3, the resist film could be removed by spraying process for thirty seconds.  
         [0195]    A quality-change effect by hot saturated steam and a peeling effect by superheated steam at a high temperature were confirmed.  
                                     TABLE 10                           Effect of High-temperature Superheated Steam for Ion-       implanted Resist Removal                    first step   second step                   steam-   steam-           processing   contacting   spraying   resist removal           step   process   process   result               condition 1   kind of   no first step   saturated   could not be           steam       steam   removed by           temperature       100° C.   spraying for           of steam           10 min           processing       10 min           time       condition 2   kind of   saturated   saturated   removed in           steam   steam   steam   processing           temperature   120° C.   120° C.   time of 3 min           of steam           processing   2 min   1 min           time       condition 3   kind of   saturated   superheated   removed in           steam   steam   steam   processing           temperature   130° C.   140° C.   time of 1 min           of steam           processing   30 sec   30 sec           time                  
 
       Example 6  
       [0196]    Shown are examples by combinations of steam and ultraviolet processes for ion-implanted resist films, which are hard to peel off.  
         [0197]    Ultraviolet lamp: KrI excimer lamp, wavelength; 191 nm;  
         [0198]    Ultraviolet irradiation quantity: 10 mW/cm 2  (surface to be processed).  
         [0199]    Result of Peeling:  
         [0200]    Table 11 shows the results.  
         [0201]    After the 100° C. saturated steam process and the ultraviolet irradiation process for two minutes of the condition 1, the resist film could be removed by spraying process for one minute.  
         [0202]    After the 120° C. saturated steam process and the ultraviolet irradiation process for thirty seconds of the condition 2, the resist film could be removed by spraying process for thirty seconds.  
                                     TABLE 11                           Effect of Ultraviolet Irradiation Superimposition for       Ion-implanted Resist Removal                    first step                       steam-               contacting               process               ultraviolet   second step               irradiation   steam-           processing   super-   spraying   resist removal           step   imposition   process   state               condition 1   kind of   saturated   saturated   removed in           steam   steam   steam   processing           temperature   100° C.   100° C.   time of 3 min           of steam           processing   2 min   1 min           time       condition 2   kind of   saturated   superheated   removed in           steam   steam   steam   processing           temperature   120° C.   130° C.   time of 1 min           of steam           processing   30 sec   30 sec           time                  
 
       Example 7  
       [0203]    Shown are examples by a sequential process of resist-peeling and surface-cleaning after peeling.  
         [0204]    Ultraviolet lamp: KrI excimer lamp, wavelength; 191 nm;  
         [0205]    Ultraviolet irradiation quantity: 10 mW/cm 2  (surface to be processed).  
         [0206]    Resist-Peeling Step:  
         [0207]    Saturated steam at temperatures to meet various resist processes was used. Resist-peeling is performed by the first step of steam-contacting and the second step of steam-spraying with combining ultraviolet irradiation.  
         [0208]    Cleaning Step:  
         [0209]    Steams containing chemicals are generated by supplying the chemicals one after another through a cleaning liquid supply line. First, saturated steam containing fluoric acid and hydrogen peroxide is sprayed onto a substrate surface to remove metal and organic matters. At this time, particles are removed by the spraying power of a steam mist. Next, saturated steam containing diluted fluoric acid is sprayed onto the substrate surface. For example, the silicon surface of a contact hole in the substrate becomes bare silicon. Finally, steam of pure water is sprayed to wash. Such a chemical prescription is selected in accordance with the object of the process.  
         [0210]    Drying Step:  
         [0211]    Because superheated steam contains no mist, rapidly drying can be performed. Ultraviolet irradiation combined performs completion of surface-cleaning as well as a promotion of drying.  
         [0212]    Result of Peeling:  
         [0213]    Both the resist removal and the surface-cleaning were completely performed.  
                                                                                 TABLE 12                           Making Resist-peeling Process and Surface-cleaning       Process after Peeling Sequential                first/second step   cleaning step       drying step           steam   steam       steam           processing   processing       processing           ultraviolet   ultraviolet       ultraviolet           irradiation   irradiation       irradiation           super-   super-       super-       processing step   imposition   imposition       imposition               kind of   saturated                   steam   steam       temperature   100 to 140° C.       of steam       processing   according to       time   each resist       kind of       saturated       steam       steam       temperature       100 to 140° C.       of steam            kind of       fluoric acid/   dil.   pure       cleaning       hydrogen   fluoric   water       liquid       peroxide   acid       cleaning       15 sec   15 sec   10 sec       time            kind of               superheated       steam               steam       temperature               120 to 140° C.       of steam       drying time               10 sec       nitrogen               10 sec       introduction       time                  
 
         [0214]    —Various Embodiments According to Other Aspects of the Present Invention— 
         [0215]    As described above, the present inventors have realized techniques of peeling resist films with steam, besides, they have established techniques for combining them with promotion effects by chemical ingredients and effects by ultraviolet irradiation.  
         [0216]    Additionally, the present inventors now propose techniques to make the peeling-off operation more sure and rapid by closely cross-combining applications of peeling actions, i.e., operations of peeling mechanisms, in relation to timely and spatial conditions, temperature conditions, and physicochemical conditions. That is, the present inventors grasp the peeling techniques from a new viewpoint that the properly cross-combining manners of the above conditions are considered, and make it possible to realize the techniques for this purpose and grasp them practically.  
         [0217]    1. Cross-Combination of Process conditions  
         [0218]    In general, process conditions are mostly set in a stationary state. However, peeling a film is a phenomenon of a break of a stationary state, i.e., an adhering state. Therefore, peeling is a non-stationary phenomenon essentially. For example, a resist film is hydrated and swelled by an effect of steam, but it is never peeled off only by keeping the physicochemical state. A physical action, i.e., spraying, is required for peeling the film. Thus the peeling process requires a non-stationary cross-combination of various conditions.  
         [0219]    Proper cross-combination is not a mere combination of different conditions. Proper cross-combination is an arrangement of conditions on the premise of an estimate and grasp of means and results. In detail, it includes interception condition design, inversion condition design, variation condition design, etc. A proper cross-combination of such process conditions produces an effect.  
         [0220]    In particular, the following is the most principal reason why peeling techniques for resist films require such a proper cross-combination of process conditions. There is an untouchable ground that protection of the minute structure of the exposed surface after peeling must be ensured. In a peeling process, the surface of the resist film and the surface of the minute structure coexist temporarily. Conditions effective for peeling may cause damages on the minute structure surface. For reconciling peeling and protection of the minute structure surface, a proper cross-combination of process conditions is necessary.  
         [0221]    2. Specific Modes of Proper Cross-Combinations of Process conditions  
         [0222]    (1) Modes of Timely and Spatially Proper Cross-Combinations  
         [0223]    In modes of timely cross-combinations, for example, the order of operations of two conditions or mechanisms A and B is set at A→B, A←B, or A and B at once, and an operation time is set to either of A and B.  
         [0224]    Modes of spatially proper cross-combinations include, e.g., cases of processing the whole surfaces, one surface, and a partial surface.  
         [0225]    (2) Modes of Proper Cross-Combinations on Temperature  
         [0226]    The portions to be heated and/or cooled are selected to the whole surfaces, one surface, or a partial surface to be processed. For example, a combination of one surface heating and one surface cooling is made. Preheating or rapid heating, or pre-cooling or rapid cooling is selected. Also possible are modes in which cross-combinations on temperature are further cross-combined timely or spatially.  
         [0227]    (3) Modes of physicochemically Proper Cross-Combinations  
         [0228]    These modes include combinations on composition and combinations on concentration of chemical ingredients, and timely and spatially proper cross-combinations of applications of chemical ingredients. Irradiation with high frequency supersonic waves or ultraviolet rays may be combined.  
         [0229]    The above modes (1), (2), and (3) can be properly cross-combined with one another.  
         [0230]    3. Specific Examples of Proper Cross-Combinations of Process conditions  
         [0231]    Specific examples of proper cross-combinations will be described below, though the present invention is not limited to those examples.  
         [0232]    (1) Cross-Combination of Steam-Contact and Steam-Spraying (Timely Cross-Combination)  
         [0233]    A certain time is required for a resist film to be swelled and hydrated by a chemical action. For this process, suitable is a process of stationary contact with steam. After the resist film has changed in its quality due to the steam, spraying power of steam is required. That is, a steam-contact process and a steam-spraying process should be combined at a time interval.  
         [0234]    A specific example of this mode is the above example 4, which is a proper cross-combination of a steam-contact process, a steam-spraying process, and alkali.  
         [0235]    (2) Cross-Combination of Saturated Steam Process and Superheated Steam Process (Timely and Physicochemically Proper Cross-Combination and Proper Cross-Combination on Temperature)  
         [0236]    Saturated steam gives wetting conditions, and superheated steam gives hot drying conditions. For example, a 100° C. saturated steam process and a 100° C. saturated-150° C. superheated steam process are properly cross-combined. In the 100° C. saturated steam process, swelling and hydration of a resist film progress. In the 100° C. saturated-150° C. superheated steam process, the adhesion boundary of the resist film is dried, and this causes peeling at the boundary. Thus effective is a combination of the 100° C. saturated steam process and the 100° C. saturated-150° C. superheated steam process at a proper time interval.  
         [0237]    Besides, a superheated steam process can be effectively used for drying after peeling and washing.  
         [0238]    A specific example of this mode is the above example 5, which is a proper cross-combination of saturated and superheated steams.  
         [0239]    (3) Cross-Combination of Steam Process and Chemical Ingredient-Containing Steam Process (Physicochemically and Timely Proper Cross-Combination)  
         [0240]    It has been confirmed that a change in quality of a resist film is accelerated by steam containing a chemical ingredient. For example, steam containing an alkali ingredient can rapidly peel a resist film. However, if the underlayer is a minute structure of, e.g., a metal wiring surface, the wiring material such as aluminum or copper (in particular, aluminum) is etched and damaged by alkali. In this case, by using steam containing a certain kind of surface active agent, chemical damage on aluminum can be reduced to the extent that is usually negligible.  
         [0241]    Specific examples of this mode are the above examples 2 and 3, which are proper cross-combinations of alkali and hydrogen peroxide.  
         [0242]    (4) Cross-Combination of Steam Process and Isopropyl Alcohol (IPA) Vapor Process  
         [0243]    A resist-peeling effect of an IPA-water-salt base peeling liquid is known. Gas-liquid interface action of IPA is well-known as Marangoni effect. The present inventors have found that IPA vapor shows an resist-peeling promotion effect in an atmosphere of steam. Since IPA is an organic chemical ingredient which never acts on a surface material, it can be used without any damage on a metal wiring surface.  
         [0244]    Cross-Combination Mode 1: (Timely and Physicochemically Proper Cross-Combination)  
         [0245]    A steam process and an IPA vapor process are timely cross-combined.  
         [0246]    Cross-Combination Mode 2: (Physicochemically Proper Cross-Combination)  
         [0247]    An IPA vapor process, i.e., a composition of chemical ingredient is cross-combined.  
       Example 8  
       [0248]    Effects of cross-combinations of IPA vapor processes in steam processes were examined in relation to various kinds of resist films.  
         [0249]    By cross-combined process conditions shown in the below table 13, resist-peeling could be performed in one to two minutes.  
                                 TABLE 13                           Cross-Combination with IPA Vapor Process                    time   resist           combined processes   distribution   removal time               cross-   first step: steam process    0.4   1-2 min       combination   second step: IPA vapor   0.2           mode 1   process           third step: steam process   0.4       cross-   IPA-containing steam process   —   1-2 min       combination       mode 2                                          
 
         [0250]    (5) Cross-Combination of Steam Process and Water-spraying Process and Application of High-frequency Supersonic Waves  
         [0251]    There are resist films which can fully be peeled off by the spraying power of steam after a steam process, and resist films which require certain times for being peeled off only by the spraying power of steam. In the latter case, a cross-combination of a water-spraying process is effective. When the sprayed quantities are the same, the collision power of water is greater than that of steam in proportion to the difference in mass by about three figures. Besides, the resist which has been softened at the temperature of steam, is cooled by sprayed water to be hardened. This serves as an additional peeling action.  
         [0252]    Highly compressed water, i.e., a jet water stream is used for cutting a silicon wafer or as a surgical knife. Spraying compressed water can peel any stable film, but protection of the surface to be minutely processed, from being damaged, must be fully ensured. Therefore, important is design of the linear velocity of sprayed water, for relieving pressure and sprayed quantity, i.e., for protection of minute structure.  
         [0253]    Cross-Combination Mode 1: (Timely and Physicochemically Proper Cross-Combination)  
         [0254]    A water-spraying process at a relieved pressure is performed after a steam-contact process. Obtained is a united effect of a pyrogenetic chemical reaction of steam and a cooling action of compressed water.  
         [0255]    Cross-Combination Mode 2: (Spatially Proper Cross-Combination and Proper Cross-Combination on Temperature)  
         [0256]    In spinning a surface, a steam-spraying process is performed on one side, and a water-spraying process is performed on the other side. Vibration of temperature is thereby applied to the surface in a cycle of heating and cooling in accordance with the spinning speed. Also in this cross-combination mode, the same peeling effect as the above can be obtained.  
         [0257]    Cross-Combination Mode 3: (Physicochemically Proper Cross-Combination)  
         [0258]    In one of the above cross-combination modes 1 and 2, the water-spraying process is performed using a high-frequency supersonic nozzle. Because the spraying energy and the supersonic energy are summed to increase the peeling power, the process is performed under conditions by which each energy is relieved in order to ensure the protection of the target minute circuit structure.  
       Example 9  
       [0259]    Effects of cross-combinations of steam processes and water-spraying processes and applications of high-frequency supersonic waves were examined in relation to various kinds of resist films. By cross-combined process conditions shown in the below table 14, resist-peeling could be performed in one to two minutes.  
                                 TABLE 14                           Cross-Combination with Water spraying Process and High-       frequency Supersonic Process                    time   resist           combined process   distribution   removal time               cross-   first step: steam contact   0.5   1-2 min       combination   second step: water spraying   0.5       mode 1       cross-   one surface steam spraying   simultaneous   1-2 min       combination   one surface water spraying   simultaneous       mode 2       cross-   one surface steam spraying   simultaneous   1-2 min       combination   one surface water spraying   simultaneous       mode 3   with applying high-frequency           supersonic                          
 
         [0260]    (6) Cross-Combination of Steam Process and Compressed Carbonic Acid Gas-spraying Process  
         [0261]    This cross-combination produces a special effect in addition to the effect of cooling and hardening in the cross-combination of the above water-spraying process.  
         [0262]    The temperature of fine dry ice particles generated by spraying compressed carbonic acid gas, is −55° C. Moisture which has permeated into the adhesion boundary in the steam process, momentarily crystallizes and expands by spraying carbonic acid gas. This freezing of the moisture brings about an effect of ice columns, and serves as a strong additional peeling power.  
         [0263]    Cross-Combination Mode 1: (Timely and Physicochemically Proper Cross-Combination and Proper Cross-Combination on Temperature)  
         [0264]    By alternately repeating a steam process and a compressed carbonic acid gas-spraying process, obtained is a peeling effect by temperature vibration of heating and cooling. This is because the coefficient of expansion varies in accordance with the kind of material. For example, the linear expansion coefficient of silicon is 0.076×10 −4 /K, while those of many organic materials are 2.2 to 5.0×10 −4 /K. There is a difference by about one to two figures. The difference in linear expansion coefficient between a silicon substrate and a resist film brings about a peeling power at the boundary by the temperature amplitude of about 150° C.  
         [0265]    Cross-Combination Mode 2: (Spatially and Physicochemically Proper Cross-Combination and Proper Cross-Combination on Temperature)  
         [0266]    In spinning a surface, a steam-spraying process is performed on one side, and a compressed carbonic acid gas-spraying process is performed on the other side. Vibration of temperature is thereby applied to the surface in a cycle of heating and cooling in accordance with the spinning speed. Also in this cross-combination mode, the same peeling effect as the above can be obtained.  
         [0267]    Cross-Combination Mode 3: (Spatially and Physicochemically Proper Cross-Combination and Proper Cross-Combination on Temperature)  
         [0268]    A steam-spraying process is performed onto the resist-side surface of a substrate, and a compressed carbonic acid gas-spraying process is performed onto the opposite surface of the substrate. A difference in temperature is thereby made between the resist film and the substrate at their boundary. Also in this cross-combination mode, the same peeling effect as the above can be obtained.  
       Example 10  
       [0269]    Effects of cross-combinations of steam processes and compressed carbonic acid gas-spraying processes were examined in relation to various kinds of resist films. By cross-combined process conditions shown in the below table 15, resist-peeling could be performed in one to two minutes.  
                                                   TABLE 15                           Cross-Combination with Compressed Carbonic Acid Gas       spraying Process                    time   resist           combined process   distribution   removal time                        cross-   steam spraying 5 sec/process   alternate   1-2 min       combination   CO 2  gas spraying 5 sec/   alternate           mode 1   process           cross-   one surface steam spraying   simultaneous   1-2 min       combination   one surface CO 2  gas spraying   simultaneous           mode 2           cross-   front surface steam spraying   simultaneous   1-2 min       combination   back surface CO 2  gas spraying   simultaneous           mode 3                              
 
         [0270]    (7) Cross-Combination of Steam Process and Substrate Cooling Process (Proper Cross-Combination on Temperature)  
         [0271]    The resist-side surface of a substrate is processed by steam with supporting the substrate on a cooling plate. The cooling plate may perform cooling by any of an electronic cooling method using a Peltier element, a fluoric oil coolant circulation method, and a ventilation cooling method by spraying compressed carbonic acid gas.  
         [0272]    Obtained are the same united effect and peeling action as those by cooling by the above water- or compressed carbonic acid gas-spraying process.  
       Example 11  
       [0273]    Effects of cooling substrates in steam processes were examined in relation to various kinds of resist films. The cross-combination order of a steam-spraying process and a substrate cooling process and the process time of each of them vary in accordance with the kind of resist, so conditions to obtain greater effects are selected. The below table 16 shows examples of such conditions. By the conditions shown, resist-peeling could be performed in one-to two minutes.  
                                                   TABLE 16                           Cross-Combination with Substrate Cooling Process                    time   resist           combined process   distribution   removal time            cross-   substrate cooling step   0.5   1-2 min       combination   steam spraying step   0.5       mode 1           cross-   front surface steam spraying   0.5   1-2 min       combination   (120° C. saturated)           mode 2   back surface cooling   0.5                                      
 
         [0274]    (8) Cross-Combination of Steam Process and Ultraviolet Irradiation Process (Physicochemically Proper Cross-Combination)  
         [0275]    In case of combination with a steam process, used are ultraviolet rays whose 50% transmissive distance to steam is 2 mm or more. A combination with a superheated steam process is effective. Since superheated steam contains no mist, scattering loss of ultraviolet rays is little. A light quantity and an irradiation time of ultraviolet rays suffice if they bring about a change in quality of the adhering surface of a resist film by a photochemical action.  
         [0276]    A specific example of this mode is the above example 6, which is a proper cross-combination of steam and ultraviolet rays.  
         [0277]    (9) Cross-Combination of High-pressure Carbonic Acid Gas Process and Ultraviolet Irradiation Process (Physicochemically Proper Cross-Combination)  
         [0278]    In an atmosphere of carbonic acid gas, even short-wavelength ultraviolet rays whose 50% transmissive distance to steam is less than 2 mm, can be used with a high transmissivity. The transmissive distance of ultraviolet rays of the wavelength of 172 nm is about 30 cm. That is, a Xe excimer lamp (wavelength: 172 nm) can be used. This is effective to decompose and remove fine resist pieces which have remained within fine gaps of the structure after peeling a resist film.  
       Example 12  
       [0279]    In case of processes of peeling resist films off device surfaces having minute structural patterns, after which processes fine resist pieces remain at the corners of the patterns and within gaps of wiring patterns, decomposing and removing processes for the remaining resist pieces were performed by ultraviolet irradiation processes.  
         [0280]    Surfaces to be processed were irradiated by a Xe excimer lamp with spraying carbonic acid gas onto the surfaces. The below table 17 shows the results.  
                             TABLE 17                           Ultraviolet Irradiation Process for Remaining Resist       Pieces            resist remaining   ultraviolet   surface SEM inspection after process       state   irradiation time   remaining resist               remaining a little   10-20 sec   could not detect       in minute pattern           gaps.           resist residues   about 1 min   could not detect       scattered                              
 
         [0281]    (10) Cross-Combination with Cleaning Process  
         [0282]    The purification level of the surface which a resist film has been peeled off, or the purification level of the surface required in the subsequent process varies in accordance with the process in question. Therefore required is a system in which proper cross-combinations of steam conditions and a cross-combination of ultraviolet irradiation can easily be set.  
         [0283]    A specific example of this mode is the above example 6, which is a cross-combination with a cleaning process.  
         [0284]    4. Resist Film Removing Apparatus  
         [0285]    A specific example of resist film removing apparatus wherein cross-combination modes of various processes (means) are taken into consideration, will be described.  
         [0286]    [0286]FIG. 6 is a schematic sectional view of a one-by-one resist film removing apparatus including a spinning mechanism.  
         [0287]    This resist film removing apparatus is provided with a chamber having a substrate taking-in/out system, an atmosphere purge system, and a discharge system. In the chamber, in addition to a system for introducing steam, provided is at least one of systems for respectively introducing IPA vapor, water, and compressed carbonic acid gas; a system for adding a chemical ingredient to the above steam or water; systems for respectively performing irradiation with ultraviolet rays and high-frequency supersonic waves; and a system for heating and cooling substrates. A driving system is provided for moving each spraying nozzle relatively to the front or back surface of a substrate-so as to sweep the surface.  
         [0288]    A spinning mechanism is provided in the steam process chamber  101 . The spinning mechanism comprises a rotor  104  provided with support pins  103  for fixing a substrate  102 , and a hollow cylindrical motor  105 .  
         [0289]    As a substrate cooling system, a cooling plate  106  is supported by a supporting mechanism fixed in the motor  105 .  
         [0290]    As an ultraviolet irradiation system, a lamp chamber  110  including an ultraviolet lamp  108  and having a quartz window board  109  is disposed on the upper part of the steam process chamber  101 . FIG. 6 shows a cross section of the ultraviolet lamp  108 .  
         [0291]    As systems for respectively introducing steam, water, IPA vapor, and compressed carbonic acid gas, the steam process chamber  101  is provided with a steam inlet  111  and a steam spraying nozzle  112 , a water spraying nozzle  113 , an IPA vapor spraying nozzle  114 , and a compressed carbonic acid gas spraying nozzle  115 . A rear side nozzle  116  for compressed carbonic acid gas is used for cooling the substrate  102  in place of the cooling plate  106 .  
         [0292]    As a high-frequency supersonic irradiation system, the water spraying nozzle  113  is provided with a high-frequency supersonic oscillator  117 . The shape of each spraying nozzle is schematically shown in FIG. 6.  
         [0293]    The steam process chamber  101  is further provided with an atmosphere purge gas inlet  118  and a discharge system  119 .  
         [0294]    As a system for adding a chemical ingredient to steam or water, a chemical injecting device  122  comprising a fixed flow rate pump is connected to an ultrapure water supply line  121  for a steam generator  120  and the and the water spraying nozzle  113 .