Abstract:
An apparatus and method for drying one or more workpieces. The apparatus and method include the use of a chemically reactive additive to remove contaminants from the wafer surface during processing. In particular, during processing, a wafer is rinsed in a liquid bath and subsequently exposed to a chemically reactive additive. The chemically reactive additive creates a surface tension gradient that physically and chemically alters the properties of the film of the rinse liquid so that the liquid and any contaminants contained therein are removed from the wafer surface.

Description:
BACKGROUND OF THE INVENTION  
         [0001]    1. Technical Field  
           [0002]    The present invention generally relates to a method and apparatus for removing contaminants from a workpiece, such as a semiconductor. In particular, the present invention relates to an apparatus and method for removing contaminants from a workpiece using chemically reactive additive to promote the effectiveness of surface tension gradient drying.  
           [0003]    2. Description of Relevant Art  
           [0004]    A variety of methods have been attempted to achieve drying of wafers. One common method utilizes a centrifugal dryer, which unfortunately places mechanical stresses that may result in breakage of the wafer. Also, since it is difficult to avoid evaporation of water on the wafer surface during spinning by the centrifugal dryer, dissolved silicates or suspended solids may precipitate onto the surface of the workpiece, leading to device failure.  
           [0005]    Chemical vapor drying or chemical solvent drying have the disadvantages that the chemical often forces dissolved or suspended solids such as silicates or colloidal silica to precipitate onto the surface of the workpiece, leading to device failure. A second disadvantage is that chemical vapors and solvents do not completely remove moisture and chemical/particulate impurities or contaminants. A third disadvantage is that chemical vapors and solvents have not been chosen to control acidity and basicity to dissolve minerals such as silicate to avoid precipitation on the workpiece during drying. A fourth disadvantage is that chemical vapors and solvents do not create a buffer to maintain a constant pH to effect particle removal by taking advantage of the relationship between particle zeta potential and pH. Thus a need exists to more adequately remove contaminants from a workpiece and improve drying methods for various workpieces.  
           [0006]    Matthews, 1999, in U.S. Pat. No. 5,911,837, Mohindra et al., 1996, in U.S. Pat. No. 5,571,337, McConnell et al., 1991, in U.S. Pat. No. 4,984, 597, Leenaars et al., 1993, U.S. Pat. No. 5,271,774 and Leenaars, 1990, European Patent No. 0 385 536 A1 disclose examples of drying apparatuses.  
         SUMMARY OF THE INVENTION  
         [0007]    According to one aspect of the present invention, a method for removing contaminants from a workpiece is provided. The method includes the following steps: (1) providing a workpiece; (2) contacting the workpiece with a liquid; and (3) removing the liquid from said workpiece using a chemically reactive additive.  
           [0008]    According to a second aspect of the present invention, a method for removing contaminants from a workpiece is provided. The method includes the following steps: (1) providing a workpiece; (2) contacting the workpiece with a liquid; (3) withdrawing said workpiece from said liquid, such that a portion is submerged in the liquid, and a remaining portion is exposed to a chemically reactive additive; (4) developing a concentration gradient of said chemically reactive additive in said liquid film; and (5) removing the liquid film from said workpiece using said concentration gradient of said chemically reactive additive in said liquid film.  
           [0009]    According to a third aspect of the present invention, a method for removing contaminants from a worfkpiece is provided. The method includes the following steps: (1) providing a liquid bath; (2) providing a workpiece submerged in said liquid bath; (3) providing a chemically reactive additive diffusion limiting barrier over said liquid bath and a chemically reactive additive over said chemically reactive additive diffusion limiting barrier; (4) extending a portion of the workpiece over said surface of the chemically reactive additive diffusion limiting barrier, wherein said portion is covered with a liquid film and wherein said portion of said liquid film includes some of said chemically reactive additive; (5) developing a concentration gradient of said chemically reactive additive in said liquid film; and (6) removing the liquid film from said workpiece using said concentration gradient of said chemically reactive additive in said liquid film.  
           [0010]    According to a fourth aspect of the present invention, an apparatus for drying a workpiece is provided. The apparatus includes: (1) a liquid bath; (2) a workpiece, wherein a part of the workpiece is submerged in the liquid bath, and wherein a remaining part extends above the liquid bath and is surrounded by a chemically reactive additive; and (3) a liquid film on the part of the workpiece extending above the liquid bath, wherein the liquid film has a concentration gradient of the chemically reactive additive.  
           [0011]    According to a fifth aspect of the present invention, an apparatus for drying a workpiece is provided. The apparatus includes: (1) a liquid source; (2) a rotating workpiece; and (3) a liquid film on the surface of the rotating workpiece, wherein the liquid film is exposed to a chemically reactive additive and wherein the liquid film has a concentration gradient of the chemically reactive additive.  
           [0012]    Workpieces, such as silicon wafers, often undergo a series of wet chemical steps during processing. If removal of the residues from these chemicals is incomplete or if soluble silicates or insoluble silica that are byproducts from reaction of the chemicals with the wafer remain on the surface of the wafer, device failure may result. It is therefore an advantage of the present invention to provide an apparatus and method to remove these contaminants from a workpiece, such as a silicon wafer, without leaving contaminants on the surface of the workpiece that may result in device failure. A second advantage of the present invention is to provide an apparatus and method to remove typical contaminants such as soluble and insoluble metal oxides and hydroxides, mineral particulates, colloidal silica and silicates from a workpiece, such as a semiconductor wafer, by chemically dissolving them by exposing the workpiece to the chemically reactive additive. A third advantage of the present invention is to provide an apparatus and method to control the equilibrium between contaminants such as soluble silicates (SiO 3    −2 ) and insoluble silica (SiO 2 ). A fourth advantage of the present invention is an apparatus and method to remove contaminants by exposing the workpiece to the chemically reactive additive without pitting the workpiece by controlling the temperature and pH of the liquid film, the concentration of the chemically reactive additive over the liquid bath and the rate at which the wafer is exposed to the chemically reactive additive. A fifth advantage is an apparatus and method to use a mixture of acidic and basic chemically reactive additives (e.g. NH 3  and HCl) to create a buffer to maintain a constant pH to effect removal of contaminants by taking advantage of the relationship between contaminant particle zeta potential and pH.  
       
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
       [0013]    These and other features and advantages of this invention will be more readily understood from the following detailed description of the various aspects of the invention taken in conjunction with the accompanying drawings in which:  
         [0014]    [0014]FIG. 1 depicts an apparatus for wet processing of workpieces, such as silicon wafers, that often utilizes wet chemical steps, according to a preferred embodiment of the present invention;  
         [0015]    [0015]FIG. 2 depicts an apparatus for rinsing the workpiece with liquid and introducing a chemically reactive additive over the liquid, according to a preferred embodiment of the present invention;  
         [0016]    [0016]FIG. 3 depicts an apparatus for forming a surface tension gradient in the liquid film on the surface of the workpiece, according to a preferred embodiment of the present invention;  
         [0017]    [0017]FIG. 4 depicts an apparatus for removal of contaminants from the surface of the workpiece, according to a preferred embodiment of the present invention.  
         [0018]    [0018]FIG. 5 depicts an apparatus for rinsing the workpiece with liquid and introducing a chemically reactive additive diffusion limiting barrier over a liquid, to protect the liquid from exposure to a chemically reactive additive, according to a preferred embodiment of the present invention;  
         [0019]    [0019]FIG. 6 depicts an apparatus in which a liquid bath is protected from exposure to a chemically reactive additive during formation of a surface tension gradient in the liquid film on the surface of the workpiece, according to a preferred embodiment of the present invention;  
         [0020]    [0020]FIG. 7 depicts an apparatus for removal of contaminants from the surface of a workpiece, wherein a liquid bath is protected from exposure to a chemically reactive additive, according to a preferred embodiment of the present invention; and  
         [0021]    [0021]FIG. 8 depicts an apparatus for removal of contaminants from the surface of a workpiece, wherein a liquid film is removed from the surface of the workpiece by rotating the workpiece and exposing the liquid film to a chemically reactive additive, according to a preferred embodiment of the present invention.  
         [0022]    It is noted that the drawings of the preferred embodiments of the invention are not to scale. The drawings are merely schematic representations, not intended to portray specific parameters of the invention. The drawings are intended to depict only a typical embodiment of the invention, and therefore should not be considered as limiting the scope of the invention. In the drawings, like numbering represents like elements between the drawings. 
     
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT  
       [0023]    Referring to the drawings, FIGS. 1 through 4 show a preferred embodiment of an apparatus  25  and a method for removing contaminants from a workpiece  50 , such as a silicon wafer. In the preferred embodiment, depicted in FIGS. 1 through 4, the apparatus is equipped with ports  70  and  75 , through which the chemically reactive additive flows into and out of the apparatus. If the chemically reactive additive includes, but is not limited to ammonia, hydrogen chloride, carbon dioxide, hydrogen fluoride and combinations thereof, and is naturally a gas at a temperature and pressure chosen for operation of the apparatus, it is provided to the apparatus through one of ports  70  and  75 , and it exits from the apparatus through the other of ports  70  and  75 , according to the preferred embodiment of the present invention. Alternatively, if the chemically reactive additive will condense to form a liquid or solid at a temperature and pressure chosen for operation of the apparatus, it may be provided to the apparatus through one of ports  70  and  75  using a liquid spray, liquid puddle or other equivalent technique and it exits from the apparatus through the other of ports  70  and  75 , according to the present invention. Alternatively, the apparatus may be a container that has only one port equipped with a valve, through which the apparatus can be pressurized with said chemically reactive additive, wherein said chemically reactive additive is naturally a gas at a temperature and pressure chosen for operation of the apparatus. The wafer is preferably silicon, although many equivalents exist.  
         [0024]    Workpieces, such as silicon wafers, often undergo a series of wet chemical steps during processing. If removal of these chemicals and impurities in these chemicals or their chemical byproducts is incomplete or if soluble silicates or insoluble silica that are byproducts from reaction of the chemicals with the wafer remain on the surface of the wafer, device failure may result. FIG. 1 depicts a wet chemical step of submerging a wafer  50  below a surface  62  of a liquid bath  60 . Hereinafter, a liquid bath  60  wherein the liquid bath is a chemical bath, includes acidic or basic liquids, organic solvents, oxidizing agents or combinations thereof, used to clean a surface of a workpiece.  
         [0025]    As depicted in FIG. 2, a rinsing step, wherein the wafer  50  is submerged in the liquid bath  40 , follows the wet chemical step depicted in FIG. 1. The liquid bath  40  is preferably deionized water, or alternatively distilled water or its equivalent. Hereinafter, fluids from rinsing, wherein the fluids contain residues from wet chemical processing, soluble silicates or soluble minerals, insoluble silica or inorganic precipitates and organic solvents, remaining on the surface of the wafer after processing will be referred to as contaminants.  
         [0026]    Referring to FIG. 3, removal of the contaminants from the wafer includes withdrawing the wafer, or alternatively lowering of the liquid bath  40 , away from the wafer, resulting in extending a portion of the workpiece  55  through a surface  45  of the liquid bath  40 , wherein the portion  55  is covered with a liquid film  35  and wherein the liquid film is exposed to a chemically reactive additive  65 . Hereinafter, a liquid film is a layer of liquid on a surface of a workpiece, wherein the layer of liquid is formed on the surface of the workpiece by withdrawing it from a liquid bath. Introducing a chemically reactive additive either as a static atmosphere or as a flow over the surface  45  of the liquid bath  40  in FIG. 2 provides a chemically reactive additive  65  in apparatus  25 . In the preferred embodiment, ammonia is the chemically reactive additive  65  and deionized water is the liquid bath  40 . However, the chemically reactive additive may be one of, but not limited to hydrogen chloride, hydrogen fluoride, carbon dioxide, ammonia, and combinations thereof. Alternatively, the chemically reactive additive may be strongly acidic carboxylic acids such as mono-, di-, or trifluoroacetic acid, mono-, di-, or trichloroacetic acid and sulfonic acids. Alternatively, the liquid bath may be distilled water wherein distilled water is preferred over deionized water because distillation removes organic and ionic impurities in the water. In contrast, purification by deionization only removes ionic impurities. Distilled organic solvents are another alternative liquid bath for removing organic contaminants on the surface of the wafer.  
         [0027]    Precipitated mineral particulates, colloidal silica, silicates, other base-soluble contaminants and organic solvents are the most common contaminant on the surface  15  of the wafer  50  after completion of rinsing. Removal of this contaminant is necessary in order to manufacture a defect free wafer. Referring to FIG. 3, the chemically reactive additive  65  begins dissolving into liquid film  35 , immediately upon extending the portion  55  of the workpiece into the chemically reactive additive  65 , wherein the concentration of the chemically reactive additive  65  in the liquid film  35  decreases in the direction of the liquid bath. Thus the concentration of the chemically reactive additive  65  in the liquid film  35  exhibits a concentration gradient in the liquid film  35 . Also, since dissolving the chemically reactive additive  65  in the liquid film  35  results in a surface tension lowering, compared to the surface tension of the liquid film  35  at the interface  45  between the liquid film  35  and the liquid bath  40 , a surface tension gradient also develops, decreasing in the direction away from the liquid bath  40 . Developing the surface tension gradient drives the liquid film in the direction of the liquid bath  40 , resulting in removal of contaminants from the portion  55  of the wafer extending away from the liquid bath  40 , as depicted in FIG. 4. The finished wafer is then completely removed from the liquid bath  40 .  
         [0028]    Formation of a concentration gradient and resulting surface tension gradient in said liquid film  35  depends on one or more of several features. The features include: 1) a solubility of the chemically reactive additive  65  in the liquid film  35 , 2) a partial pressure of the chemically reactive additive  65 , 3) a temperature gradient in the liquid film  35 , increasing in the direction of the liquid bath  40  that results when chemically reactive additive  65  dissolves in liquid film  35 , and 4) a rate that the portion  55  of the wafer extends away from the liquid bath  40 . Control of these features enables formation of the concentration gradient and resulting surface tension gradient. The greatest possible surface tension gradient is desirable.  
         [0029]    In the case of chemically reactive additives such as ammonia, hydrogen chloride, carbon dioxide, hydrogen fluoride, the concentration range of the chemically reactive additive  65  for forming a concentration gradient in liquid film  35  is from about 0.001 mole % to about 10 mole % in an inert gas, wherein the inert carrier gas includes but is not limited to helium, nitrogen, argon or combinations thereof. Alternatively, the inert carrier gas includes any gas that is chemically unreactive when it mixes with the chemically reactive additive. Combinations of chemically reactive additives (e.g. NH3 and HCl) that form pH buffered solutions may be used. Also, chemically reactive additives such as hydrogen fluoride that volatilizes silica by forming silicon tetrafluoride may be used. Alternatively, vaporizing a chemically reactive additive that is naturally a liquid or a solid at a temperature and pressure chosen for operation of the apparatus, using heat, such as mono-, di-, or trichloroacetic acid, citric acid, sulfonic acids, mono-, di-, trifluoroacetic acid and combinations thereof, provides sufficient concentrations in the atmosphere surrounding the liquid film for concentration gradient formation. Instead of vaporizing the chemically reactive additive, spraying an aqueous solution of the chemically reactive additive wherein a liquid spray contacts a liquid film is an alternative technique to form a concentration gradient of a chemically reactive additive in a liquid film.  
         [0030]    When the portion  35  of the liquid film becomes basic, as when the chemically reactive additive includes but is not limited to ammonia, contaminants such as mineral particulates, colloidal silica, silicates and other base solubles from the surface  15  of the wafer  50  are dissolved in the portion  35  of the liquid film. Instead of introducing ammonia gas into the portion  35  of the liquid film, an alternative is contacting the liquid film  35  using a liquid spray, wherein the liquid spray is an aqueous solution of ammonia and wherein the aqueous solution has a concentration of ammonia in water from about 0.001 mole % to about 10 mole %. Alternatively, contacting the liquid film  35  with a liquid spray, wherein the chemically reactive additive in the liquid spray includes but is not limited to one of the group of amino-functionalized surfactants, alkylbenzene sulfonates, olefinsulfonates, water soluble basic polymers, anionic surfactants and combinations thereof, provides sufficient concentration of chemically reactive additive in the atmosphere surrounding the liquid film for a concentration gradient to form. Specifically, a reaction that occurs between the portion  35  of the liquid film that is made basic by introducing the chemically reactive additive  65  and the group including residual mineral particulates, colloidal silica, silicates and other base soluble contaminants on the surface  15  of the wafer  50  is shown in the following example:  
         SiO 2 +2OH −1 →SiO 3   −2 +H 2 O  
         [0031]    In addition, dissolving other metal oxides such as calcium oxide and transition metal oxides such as chromium oxide and iron oxide on the surface  15  of the wafer  50 , are analogous alternatives to dissolving silica in the above example.  
         [0032]    It should be appreciated, however, that a chemically reactive additive  65  that mixes with the liquid film  35  on the extended portion  55  of the wafer, depicted in FIG. 3, to yield an acidic solution can be employed depending on the purpose. For example, introduction of the chemically reactive additive  65  that includes, but is not limited to hydrogen chloride, carbon dioxide, hydrogen fluoride, mono-, di-, or trichloroacetic acid, citric acid, sulfonic acids, mono-, di-, or trifluoroacetic acid and combinations thereof to the portion  35  of the liquid film dissolves metal salt residues from wet chemical treatment of the wafer including but not limited to oxides of alkaline earth and transition metals such as calcium, chromium, zinc, iron, aluminum, cobalt, titanium and copper. Alternatively, use of a chemically reactive additive  65  wherein a portion of the chemically reactive additive is an acid in water and a remaining portion is a base in water offers the opportunity to buffer the pH of the liquid film  35  in FIG. 3 to control the equilibrium between soluble silicates (SiO 3    −2 ) and insoluble silica (SiO 2 ). In addition, use of a chemically reactive additive  65  wherein a portion of the chemically reactive additive is an acid in water and a remaining portion is a base in water offers the opportunity to buffer the pH of the liquid film  35  in FIG. 3 to remove contaminants by exposing the workpiece to the chemically reactive additive without pitting the workpiece. In addition, use of a chemically reactive additive  65  wherein a portion of the chemically reactive additive is an acid in water and a remaining portion is a base in water or wherein a first portion of the chemically reactive additive is an acid in water, a second portion is a base in water and a third portion is an inert gas, offers the opportunity to buffer the pH of the portion  35  of the liquid film in FIG. 3 to maintain a constant pH to effect contaminant removal by taking advantage of the relationship between the particle zeta potential and pH. Alternatively, dissolving a carboxylic acid chemically reactive additive such as mono-, di-, or trichloroacetic acid, citric acid, sulfonic acids, mono-, di-, or trifluoroacetic acid and combinations thereof, and mono-, di-, and tri-sodium phosphate in a thin film, also offers the opportunity to buffer the pH of the portion  35  of the liquid film in FIG. 3 to maintain a constant pH less than about 3 +/−0.2 pH units.  
         [0033]    [0033]FIG. 3 depicts, according to the present invention, a preferred embodiment for removing silica from the surface  15  of the wafer  50 , wherein a fraction of the chemically reactive additive is ammonia and a remaining fraction is an inert gas, that is preferred because a basic solution is formed in portion  35  of the liquid film on the extended portion  55  of the wafer. When the liquid bath  40  is deionized water and the chemically reactive additive  65  is ammonia, the preferred concentration of ammonia is about 1 mole % or its equivalent in inert gas. If the concentration of the chemically reactive additive  65  is lower than said amount, a smaller concentration gradient and smaller surface tension gradient results, leading to a longer time to drive the liquid film  35 , including contaminants into the liquid bath  40 . Likewise, if the concentration is higher than about 1 mole % or its equivalent in inert gas, a smaller concentration gradient or surface tension gradient results as the liquid film  35  approaches saturation by the chemically reactive additive  65  throughout its cross-section.  
         [0034]    Formation of the surface tension gradient of the chemically reactive additive  65  in liquid film  35  is also a function of a temperature differential between the liquid bath  40  and the liquid film  35 , as depicted in FIG. 3. Dissolving the chemically reactive additive in the liquid film  35  raises its temperature due to an exothermic reaction between the chemically reactive additive  65  and the liquid film  35 , creating a temperature differential or gradient in the liquid film that increases in the direction away from the liquid bath. In the preferred embodiment using hydrogen chloride gas as the chemically reactive additive, if the temperature of the liquid bath is about 0.1° C. to about 50° C., a temperature differential will enhance a surface tension gradient in the liquid film  35 , as depicted in FIG. 3 that decreases in the direction away from the liquid bath  40 , thus favoring removal of contaminants and the liquid film  35  into the liquid bath  40 . In other embodiments, the largest surface tension gradient may be created using a liquid bath  40  temperature from about a freezing point of the liquid bath  40  to from about 18° C. to about 22° C., wherein the freezing point depends on a pressure chosen for operation of the apparatus and the freezing point depression of pure water due to colligative properties of the soluble materials in the liquid bath  40 .  
         [0035]    Referring to FIG. 3, rate of formation of the surface tension gradient is also determined by a rate at which the wafer is withdrawn from the liquid bath  40  or the rate at which liquid bath  40  is lowered away from the wafer, to extend a portion of the wafer  55  away from the liquid bath  40 , also depicted in FIG. 3. If the rate exceeds 15 cm/sec, the chemically reactive additive  65  will have less time to dissolve in the liquid film  35  furthest from the liquid bath, so a smaller concentration gradient or surface tension gradient will result.  
         [0036]    Referring to FIG. 4, formation of the surface tension gradient drives liquid film  35  and contaminants from the surface  15  of the extended portion  55  of the wafer into liquid bath  40 , leaving only an edge  59  of the extended portion  55  of the wafer in contact with liquid bath  40  at an interface  45 . The chemically reactive additive can then be purged from the apparatus  25  and the wafer removed from the apparatus.  
         [0037]    In another embodiment of the present invention, FIG. 5 depicts introducing a chemically reactive additive diffusion limiting barrier over the liquid bath  40  and a chemically reactive additive  65  over the chemically reactive additive diffusion limiting barrier prior to withdrawing the wafer from the liquid bath  40 . The purpose of the chemically reactive additive diffusion limiting barrier is prevention of chemically reactive additive  65  from dissolving into liquid bath  40 .  
         [0038]    Referring to FIG. 6, removal of the contaminants from the wafer includes withdrawing the wafer, or alternatively lowering of the liquid bath  40 , and chemically reactive additive diffusion limiting barrier  30  away from the wafer, resulting in extending a portion of the workpiece  55  through the surface  32  of the chemically reactive additive diffusion limiting barrier  30 , wherein said portion  55  is covered with a liquid film  35  and wherein said liquid film is exposed to chemically reactive additive  65 . Introducing the chemically reactive additive either as a static atmosphere or as a flow over the surface  32  of the chemically reactive additive diffusion limiting barrier  30  in FIG. 2 provides the chemically reactive additive  65  in apparatus  25 . If ammonia is the chemically reactive additive  65 , the preferred chemically reactive additive diffusion limiting barrier  30  is one of an organic solvent, a hydrocarbon oil or a fluorocarbon oil, although many alternatives exist. The chemically reactive additive diffusion limiting barrier includes liquids such as non-polar organic compounds that do not react with the wafer, are insoluble in water and in which ammonia is also insoluble, having a density less than the liquid bath  40  and a boiling point greater than about 60° C. at a pressure chosen for operation of the apparatus. Alternatively, the chemically reactive additive diffusion limiting barrier can also be an elastomer such as a fluorinated rubber that is not soluble in the liquid bath  40 , resistant to corrosion by reactive gases such as ammonia, hydrogen chloride, carbon dioxide, hydrogen fluoride, carboxylic acids and combinations thereof, and will allow extending a portion  55  of the wafer through the chemically reactive additive diffusion limiting barrier  30 , wherein said portion  55  is covered with a liquid film  35  wherein said liquid film  35  is exposed to chemically reactive additive  65 .  
         [0039]    Referring to FIG. 7, formation of the surface tension gradient drives liquid film  35  and contaminants from the surface  15  of the extended portion  55  of the wafer, into the chemically reactive additive diffusion limiting barrier  30 , and then into liquid bath  40 , leaving only an edge  59  of the extended portion  55  of the wafer in contact with liquid bath  40  at an interface  45 . The chemically reactive additive can then be purged from the apparatus  25  and the wafer removed from the apparatus.  
         [0040]    Referring to FIG. 8, a liquid film  35  is applied as a spray or liquid puddle to the surface of a flat workpiece,  50 , such as a silicon wafer. The wafer,  50 , is rotated around a rotation axis that is through the center,  77 , and normal to the surface of the workpiece or alternatively it may be rotated around a rotation axis that is off center,  79 , and normal to the surface of the workpiece. The centripetal force that results from rotation of the wafer,  50 , around the rotation axis removes a portion of liquid film  35  from the surface  81 , of wafer  50 . Chemically reactive gas  65  is introduced around the perimeter,  83 , of a remaining portion of liquid film  35 , such that a concentration gradient of the chemically reactive gas forms wherein the concentration gradient decreases in the direction away from the center,  77 , of the wafer,  50 . Formation of the surface tension gradient drives liquid film  35  and contaminants from the surface of the wafer. The chemically reactive additive can then be purged from the apparatus  25  and the wafer removed from the apparatus.  
         [0041]    The foregoing description of the preferred embodiments of this invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and obviously, many modifications and variations are possible. Such modifications and variations that may be apparent to a person skilled in the art are intended to be included within the scope of this invention as defined by the accompanying claims.