Patent Publication Number: US-2011068402-A1

Title: Thin film transistor and method for producing thin film transistor

Description:
This application is a continuation of International Application No. PCT/JP2009/057176 filed on Apr. 8, 2009, which claims priority to Japanese Patent Document No. 2008-106119, filed on Apr. 15, 2008. The entire disclosure of the prior applications are herein incorporated by references in their entireties. 
    
    
     BACKGROUND OF THE INVENTION 
     The present invention relates to a transistor having electrode films composed of a copper alloy and a method for producing such a transistor. 
     BACKGROUND ART 
     Conventionally, metallic wiring films are connected to a source area and a drain area of a TFT (thin film transistor) inside an electronic circuit of, such as, the TFT or the like. 
     Recently, since the TFTs and the wiring films have been made finer and finer, wiring films which have copper as a main ingredient, are used to obtain wiring films having low resistances. 
     However, experiments revealed that although the wiring films made mainly of copper have high adhesion to silicon, exfoliation may occur when TFTs are produced by using the copper wiring films, which is the problem to avoid. 
     See, Japan Patent documents JP-A 2001-73131 and JP-A 11-54458. 
     SUMMARY OF THE INVENTION 
     The inventors of the present invention have determined the cause for deterioration of the adhesion between the copper wiring film and the silicon layer lies in a treatment of improving the characteristics of the TFT in which the silicon layer is exposed to a hydrogen plasma during a production step of the TFT so as to restore the damage of the silicon layer. 
     Since pure copper has poor adhesion to silicon, a metallic wiring film to form a source electrode film and a drain electrode film is designed in a two-layer structure of an adhesion layer made of a copper alloy to which magnesium and oxygen are added in order to render high adhesion to silicon, and a low-resistance metallic layer made of pure copper having a resistance lower than that of the adhesion layer. 
     It is considered that when such a metallic wiring film is exposed to the hydrogen plasma, a copper compound in the adhesion layer is reduced, so that pure Cu precipitates at an interface between the silicon and the adhesion layer, which causes the deterioration of the adhesion. 
     As a result of investigation and study of additives for preventing pure copper from precipitation at the interface between the copper wiring film and silicon, the inventors of the present invention have thus discovered the use of oxides of Ti, Zr and Cr in the production of the present invention. 
     In other words, an embodiment of the present invention is directed to a method for producing a thin film transistor of an inverted staggered type, comprising the steps of: forming a gate electrode on an object to be processed; forming a gate insulation layer on the gate electrode; forming a semiconductor layer on the gate insulation layer; forming an ohmic contact layer on the semiconductor layer; forming a metallic wiring layer on the ohmic contact layer; and forming a first and a second ohmic contact layers, a source electrode, and a drain electrode by patterning the ohmic contact layer and the metallic wiring film. The step of forming the metallic wiring film includes a step of sputtering a target of a copper alloy having an additive metal including at least one of Ti, Zr or Cr and copper in a vacuum atmosphere with a gas including a sputtering gas and oxidizing gas for forming an adhesion layer having copper, the additive metal and oxygen on the ohmic contact layer. 
     The present embodiment may be directed to a method for producing the thin film transistor, wherein the additive metal is included in the copper alloy target at a rate of between at least 5 atom % and at most 30 atom %. 
     The present embodiment is further directed to a method for producing the thin film transistor, which includes the step of, after forming the adhesion layer, forming a metallic low-resistance layer on the adhesion layer, the metallic low-resistance layer having a higher copper content rate than that of the adhesion layer and a resistance lower than that of the adhesion layer. 
     The present embodiment is further directed to a method for producing the thin film transistor, wherein a CO 2  gas is used as the oxidizing gas, and the CO 2  gas is included in a range of between at least 3 parts by volume and at most 30 parts by volume relative to 100 parts by volume of the sputtering gas. 
     The present embodiment is further directed to a method for producing the thin film transistor, wherein an O 2  gas is used as the oxidizing gas, and the O 2  gas is included in a range of between at least 3 parts by volume and at most 15 parts by volume relative to 100 parts by volume of the sputtering gas. 
     An embodiment of the present invention is directed to a thin film transistor of an inverted staggered type, including: a gate electrode formed on an object to be processed; a gate insulation layer formed on the gate electrode; a semiconductor layer formed on the gate insulation layer; a first and a second ohmic contact layers, which are separated from each other, formed on the semiconductor layer; and a source electrode and a drain electrode formed on the first and the second ohmic contact layers, respectively. The source electrode and the drain electrode have adhesion layers on surfaces, which contact the first and the second ohmic contact layers, the adhesion layers having a copper alloy including an additive metal made of at least one of Ti, Zr or Cr, and oxygen. 
     The present embodiment is further directed to a thin film transistor, wherein the first and second ohmic contact layers are n-type semiconductor layers. 
     The present embodiment is further directed to a thin film transistor, wherein a low-resistance metallic layer, which has a content rate of copper higher than that of the adhesion layer and a resistance lower than that of the adhesion layer, is arranged on the adhesion layer. 
     The present embodiment is further directed to a thin film transistor, wherein the additive metal is included at a rate of between at least 5 atom % and at most 30 atom % relative to atoms of the metals including the additive metal in the adhesion layer. 
     In the present invention, a semiconductor which has silicon (such as, polysilicon, amorphous silicon or the like) as a main ingredient is called silicon layer. 
     Since the electrode film does not exfoliate even when exposed to the hydrogen plasma, the yield increases. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1(   a ) is a cross-sectional view for illustrating a method for producing the transistor used in an embodiment of the present invention. 
         FIG. 1(   b ) is a cross-sectional view for illustrating the method for producing the transistor used in an embodiment of the present invention. 
         FIG. 1(   c ) is a cross-sectional view for illustrating the method for producing the transistor used in an embodiment of the present invention. 
         FIG. 1(   d ) is a cross-sectional view for illustrating the method for producing the transistor used in an embodiment of the present invention. 
         FIG. 1(   e ) is a cross-sectional view for illustrating the method for producing the transistor used in an embodiment of the present invention. 
         FIG. 1(   f ) is a cross-sectional view for illustrating the method for producing the transistor used in an embodiment of the present invention. 
         FIG. 1(   g ) is a cross-sectional view for illustrating the method for producing the transistor used in an embodiment of the present invention. 
         FIG. 1(   h ) is a cross-sectional view for illustrating the method for producing the transistor used in an embodiment of the present invention. 
         FIG. 2  is a cross-sectional view for illustrating a metallic wiring film. 
         FIG. 3  is a schematic block diagram for illustrating a film forming apparatus to be used for producing the transistor in an embodiment of the present invention. 
         FIG. 4  is a graph for showing a comparison between the specific resistances of an adhesion layer using a CO 2  gas and an adhesion layer using an O 2  gas. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     In  FIG. 1(   a ), a reference numeral  10  denotes an object to be processed, for which the transistor producing method according to an embodiment of the present invention is to be used. 
     The object  10  to be processed has a transparent substrate  11  made of glass or the like; and a gate electrode  12  and a pixel electrode  13  are arranged spaced-apart on the transparent substrate  11 . 
     A gate insulation film  14 , a silicon layer  16  and an n-type silicon layer  18  are placed on the transparent substrate  11  in this order from a side of the transparent substrate  11 , covering the gate electrode  12  and the pixel electrode  13 . The n-type silicon layer  18  is a silicon layer in which a resistance value is made smaller than that of the silicon layer  16  by adding an impure substance. In this embodiment, the n-type silicon layer  18  and the silicon layer  16  are constituted by amorphous silicon, but they may be a single crystal or polycrystal. The gate insulation layer  14  is an insulation film (such as, a thin film of silicon nitride or the like), but may be a film of silicon oxynitride film or another insulation film. 
     In  FIG. 3 , a reference numeral  100  denotes a film forming apparatus for forming a metallic wiring film on a surface of the object  10  to be processed. 
     The film forming apparatus  100  has a carrying in/out chamber  102 , a first film forming chamber  103   a , and a second film forming chamber  103   b . The carrying in/out chamber  102  and the first film forming chamber  103   a , and the first film forming chamber  103   a  and the second film forming chamber  103   b  are connected via gate valves  109   a  and  109   b , respectively. 
     Vacuum evacuating systems  113 ,  114   a ,  114   b  are connected to the carrying in/out chamber  102  and the first and second film forming chambers  103   a ,  103   b , respectively. Consequently, while the gate valves  109   a ,  109   b  are closed, the interiors of the first and second film forming chambers  103   a ,  103   b  are preliminarily evacuated to vacuum. 
     Next, a door between the carrying in/out chamber  102  and the air is opened, an object  10  to be processed is carried into the carrying in/out chamber  102 , and the door is closed; then, after the interior of the carrying in/out chamber  102  is evacuated to vacuum, the gate valve  109   a  is opened, and the object  10  to be processed is moved into the first film forming chamber  103   a  to be held on a substrate holder  108 . 
     A copper alloy target  111  and a pure copper target  112  are placed on sides of bottom walls inside the first and second film forming chambers  103   a ,  103   b , respectively; and the object  10  to be processed is held on the substrate holder  108  such that the n-type silicon layer  18  may face each of the targets  111 ,  112 . 
     Gas introduction systems  105   a ,  105   b  are connected to the first and second film forming chambers  103   a ,  103   b , respectively; and accordingly, when the copper alloy target  111  is sputtered while introducing a sputtering gas and an oxidizing gas from the gas introduction system  105   a  in a state such that the interior of the first film forming chamber  103   a  is being evacuated to vacuum, sputtered particles made of a constitutent material of the copper alloy target  111  reach a surface of the n-type silicon layer  18 , and an adhesion layer which contacts the n-type silicon layer  18  is formed. 
     The copper alloy target  111  includes copper and at least one of the additive metals of Ti (titanium), Zr (zirconium) and Cr (chromium); and when the number of atoms of the copper and the additive metal is taken as 100 atom %, the additive metal is contained at a rate of between at least 5 atom % and at most 30 atom %. 
     The oxidizing gas is a gas which oxidizes the additive metal and produces an oxide of the additive metal. Consequently, when the copper alloy target  111  is sputtered, an adhesion layer having copper as a main ingredient and the oxide of the additive metal is formed on a surface of the object  10  to be processed. 
     Thereafter, when the substrate holder  108  on which the object  10  to be processed is held is moved to the second film forming chamber  103   b , and the sputtering gas is introduced from the gas introduction system  105   b  to sputter the pure copper target  112 , sputtered particles made of copper atoms as the constituent material of the pure copper target  112  reach the surface of the object  10  to be processed; and a low-resistance metallic layer made of pure copper is formed on the surface of the adhesion layer. The oxidizing gas is not introduced into the second film forming chamber  103   b.    
     In  FIG. 1(   b ), a reference numeral  20   a  denotes a metallic wiring film composed of the adhesion layer and the low-resistance layer; and reference numerals  51 ,  52  in  FIG. 2  denote the adhesion layer and the low-resistance metallic layer, respectively. 
     A resist layer is placed on a surface of the portion of the metallic wiring film  20   a , which is located above the gate electrode  12 ; and by etching a laminated film composed of the metallic wiring film  20   a , the n-type silicon layer  18  and the silicon layer  16 , the portion of the laminated film which is not covered with the resist film is removed. 
       FIG. 1(   c ) shows a state in which the resist film is removed after etching the laminated film, and a reference numeral  20   b  shows the metallic wiring film that remains with the resist film thereon. 
     Next, as shown in  FIG. 1  ( d ), a patterned resist film  22  is placed on the metallic wiring film  20   b , and then, by immersion into an etching liquid of a mixed liquid of phosphoric acid, nitric acid, and acetic acid; a mixed liquid of sulfuric acid, nitric acid, and acetic acid; or a solution of ferric chloride or the like, in such a state that a surface of the metallic wiring film  20   b  is exposed at a bottom face of an opening  24  of the resist film  22 , the exposed portion of the metallic wiring film  20   b  is etched. Thus, the metallic wiring film  20   b  is patterned. 
     By this patterning, the opening  24 , where the n-type silicon layer  18  is exposed on the bottom face, is formed in the portion of the metallic wiring film  20   b  which is above the gate electrode  12 , so that the metallic wiring film  20   b  is divided by the opening  24  in order to form a source electrode film  27  and a drain electrode film  28  as shown in  FIG. 1  ( e ). Thus, the transistor  5  used in an embodiment of the present invention is attained. 
     Next, the object is carried into an etching device, then by etching the n-type silicon layer  18 , which is exposed to the bottom face of the opening  24  by being exposed to a plasma of an etching gas, a silicon layer  16  is exposed at a bottom face of an opening  24  formed in the n-type silicon layer  18 . 
     The opening  24  formed in the n-type silicon layer  18  is in a position above the gate electrode  12 ; and the n-type silicon layer  18  is divided into a source area  31  and a drain area  32  by the opening  24 . 
     A surface of the silicon layer  16  is exposed to a surface of the opening  24 ; and when the silicon layer  16  is exposed to the plasma of the etching gas when etching the n-type silicon layer  18 , hydrogen atoms are lost from the surface of the silicon layer  16 , which may result in the formation of dangling bonds. 
     Such dangling bonds cause inferiority in characteristics of the TFT (such as, leak current). In order to modify the dangling bonds with hydrogen again, hydrogen is introduced to generate a hydrogen plasma; and then the silicon layer  16 , which is exposed at the bottom of an opening  25  is exposed to the plasma of the hydrogen gas in such a state that the source electrode film  27  and the drain electrode film  28  are exposed as shown in  FIG. 1  ( f ), silicon atoms on the surface of the silicon layer  16  bind to hydrogen, thereby reducing the dangling bonds. 
     In the metallic wiring film  20   a  ( 20   b ) in this embodiment of the present invention, the source electrode film  27  and the drain electrode film  28  includes the adhesion layer  51  having copper as a main ingredient and the additive metal at the rate of between at least 5 atom % and at most 30 atom %; and the adhesion layer  51  adheres tightly to silicon and to silicon dioxide of the transistor, so that even when the source electrode film  27  and the drain electrode film  28  are exposed to the hydrogen plasma, copper does not precipitate at the interface between the n-type silicon layer  18  (and the source area  31  and the drain area  32 ), which prevents the electrode film constituted by the metallic wiring film  20   a  ( 20   b ) (such as, the source electrode film  27 , the drain electrode film  28  or the like) from exfoliation. 
     Following the treatment with the hydrogen plasma, after a passivation film  34  is formed as shown in  FIG. 1  ( g ), and contact holes  37  are formed in the passivation film  34 , a liquid crystal display panel is obtained by forming a transparent electrode film  36  in order to connect the source electrode film  27  or the drain electrode film  28  with the pixel electrode  13  as shown in  FIG. 1  ( h ). 
     Gases which are able to be used for etching the silicon layer (including a polysilicon layer and an amorphous silicon layer) are Cl 2 , HBr, Cl 2 , HCl, CBrF 3 , SiCl 4 , BCl 3 , CHF 3 , PCl 3 , HI, I 2  or the like. One kind of these halogen gases may be used alone as the etching gas, or a mixture of two or more kinds thereof may be used as the etching gas. Further, an additive gas, (such as, O 2 , N 2 , SF 6 , N 2 , Ar, NH 3  or the like), other than one of the halogen gases can be added to the etching gas. 
     The halogen gases listed above are able to be used to etch other objects to be etched, (such as, silicon nitride (SiN), silicon oxide (SiO 2 ), GaAs, SnO 2 , Cr, Ti, TiN, W, Al or the like). 
     For etching gases for the polysilicon (for example, Cl 2 , Cl 2 +HBr, Cl 2 +O 2 , CF 4 +O 2 , SF 6 , Cl 2 +N 2 , Cl 2 +HCl, HBr+Cl 2 +SF 6  or the like) can be used. 
     For etching gases for Si (for example, SF 6 , C 4 F 8 , CBrF 3 , CF 4 +O 2 , Cl 2 , SiCl 4 +Cl 2 , SF 6 +N 2 +Ar, BCl 2 +Cl 2 +Ar, CF 4 , NF 3 , SiF 4 , BF 3 , XeF 2 , ClF 3 , SiCl 4 , PCl 3 , BCl 3 , HCl, HBr, Br 2 , HI, I 2  or the like) can be used. 
     For etching gases for the amorphous silicon (for example, CF 4 +O 2 , Cl 2 +SF 6  or the like) can be used. 
     When an adhesion layer  51  is formed with 100% of an additive metal (a metallic Ti film, a metallic Zr film or the like) and a metallic wiring film is obtained by laminating a low-resistance metallic layer  52  of pure copper on a surface thereof, the low-resistance metallic layer  52  made of pure copper and the low-resistance metallic layer  52  having copper as a main ingredient can be etched by using the mixed liquid of phosphoric acid, nitric acid, acetic acid; the mixed liquid of sulfuric acid, nitric acid, acetic acid; or the solution of ferric chloride as the etchant. However, because the adhesion layer  51  made of 100% of the additive metal or the adhesion layer  51  including a large amount of the additive metal largely differs from the low-resistance metallic layer  52  made of pure copper in etching speeds, the low-resistance metallic layer  52  and the adhesion layer  51  may significantly differ in width. (A pure Ti thin film and a pure Zr thin film are insoluble in the etchant for the low-resistance metallic layer  52  made of pure copper, but can be soluble in a strongly-acid etching liquid of a hydrofluoric acid type; however, since such an etching liquid dissolves glass or Si, it cannot be used for TFTs.) 
     Consequently, when the adhesion layer  51  of 100% of the additive metal is used as a barrier layer for the silicon layer and a copper thin film is formed thereon, exposing a surface of the barrier film, first of all, by patterning the copper thin film with the use of the etching liquid (such as, the mixed liquid of phosphoric acid, nitric acid, acetic acid or the like), is necessary. Thereafter, a dry etching process is performed by means of an etching gas. This may make the number of necessary steps to increase, and the cost to rise. 
     In this embodiment of the present invention, since the adhesion layer  51  includes more copper than the additive metal, the adhesion layer  51  and the low-resistance metallic layer  52  can be wet etched by means of the same etching liquid. In addition, since the adhesion layer  51  and the low-resistance metallic layer  52  can be etched with the same resist film without rearranging a resist film, cost becomes low. 
     EXAMPLES 
     A copper alloy target  111  was sputtered with an argon gas used as a sputtering gas and an oxygen gas used as an oxidizing gas, an adhesion layer  51  was formed to 50 nm thick on a glass substrate, and thereafter a low-resistance metallic layer  52  was formed to 300 nm thick on the adhesion layer  51  by sputtering a pure copper target  112  by means of the argon gas, thereby obtaining a metal wiring film of a two-layer structure. The temperature of the substrate was 100° C., the sputtering gas was Ar gas, and the sputtering pressure was 0.4 Pa. 
     Following exposure of a surface of the formed metallic wiring film to be exposed to a hydrogen plasma, a film of silicon nitride was formed on the surface thereof. 
     The treatment with a hydrogen gas plasma was such that the flow rate of the hydrogen gas was 500 sccm, the pressure was 200 Pa, the temperature of the substrate was 250° C., the power was 300 W and the time was 60 seconds. 
     The silicon nitride film was formed such that respective gases were introduced into a CVD apparatus, in which the substrate was arranged, at the rates of SiH 4 : 20 sccm, NH 3  gas: 300 sccm and N 2  gas: 500 sccm, the pressure was 120 Pa, the temperature of the substrate was 250° C., and the power was 300 W. 
     Adhesion as deposited (i.e., adhesion of a film, which when immediately after formation still remains to be treated in ways that include annealing) of the metallic wiring film before the exposure to the hydrogen plasma and adhesion (adhesion after the H 2  plasma treatment) after the formation of a film of silicon nitride on a surface thereof, following the exposure to the hydrogen plasma, were measured by a tape test in which an adhesive tape was adhered and was then peeled. Evaluations were carried out by taking examples having surfaces of the glass substrates marked with crosses “X”, and different ones marked with circles “◯”. 
     Experiments were carried out, while content rates of additive metals and the introduction rate of an oxidizing gas were changed. Evaluation results are shown as “adhesion” in the following Tables 1 to 3. 
     Also, after the same metallic wiring film as explained above was formed on a surface of a silicon wafer, it was annealed in a vacuum atmosphere; and following removal of the metallic wiring film by etching, the surface is observed in order to determine if there is a diffusion of copper into the silicon with an SEM. 
     In each of the experiments, the sputtering gas was argon gas, the oxidizing gas was oxygen gas, and the partial pressure of the sputtering gas in the sputtering atmosphere was 0.4 Pa. 
     Further, a target including an additive metal was sputtered by means of CO 2  gas as oxidizing gas in place of oxygen gas. With Ar gas used as a sputtering gas and Ti used as an additive metal, the adhesion and barrier properties were evaluated. The partial pressure of the sputtering gas was the same as explained above. 
     Observation results were shown as “barrier property” in the following Tables 1 to 3 (with oxygen gas used as an oxidizing gas) and Table 4 (with CO 2  used as an oxidizing gas). Examples in which diffusion was observed were marked with crosses “X”, while those in which diffusion was not observed were marked with circles “◯”. 
     
       
         
           
               
               
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                   
                 Ti Addition 
                 O 2  Addition 
                   
                 Barrior 
                   
               
               
                   
                 Amount 
                 Amount 
                   
                 Property 
                 Adhesion After 
               
               
                 Copper alloy 
                 (at %) 
                 (%) 
                 Adhesion 
                 300° C. 
                 H 2  Plasma Treatment 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Cu/Cu—Ti—O 
                 3 
                 — 
                 X 
                 X 
                 X 
               
               
                   
                   
                 1 
                 X 
                 X 
                 X 
               
               
                   
                   
                 3 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 5 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 7 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 10  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 15  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                 5 
                 — 
                 ◯ 
                 X 
                 ◯ 
               
               
                   
                   
                 1 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 3 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 5 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 7 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 10  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 15  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                 10 
                 — 
                 ◯ 
                 X 
                 ◯ 
               
               
                   
                   
                 1 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 3 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 5 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 7 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 10  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 15  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                 30 
                 — 
                 ◯ 
                 X 
                 ◯ 
               
               
                   
                   
                 1 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 3 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 5 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 7 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 10  
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 15  
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
               
               
                 O 2  addition amount is the O 2  introduction amount where introduction amount of sputtering gas is 100. 
               
               
                 Ti addition amount is the number of the Ti atoms where the number of the atoms of the entire metals is inclusive of Ti. 
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
             
               
                 TABLE 2 
               
               
                   
               
               
                   
                 Zr Addition 
                 O 2  Addition 
                   
                 Barrior 
                   
               
               
                   
                 Amount 
                 Amount 
                   
                 Property 
                 Adhesion After 
               
               
                 Copper alloy 
                 (at %) 
                 (%) 
                 Adhesion 
                 300° C. 
                 H 2  Plasma Treatment 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Cu/Cu—Zr—O 
                 3 
                 — 
                 X 
                 X 
                 X 
               
               
                   
                   
                 1 
                 X 
                 X 
                 X 
               
               
                   
                   
                 3 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 5 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 7 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 10  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 15  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                 5 
                 — 
                 ◯ 
                 X 
                 ◯ 
               
               
                   
                   
                 1 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 3 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 5 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 7 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 10  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 15  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                 10 
                 — 
                 ◯ 
                 X 
                 ◯ 
               
               
                   
                   
                 1 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 3 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 5 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 7 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 10  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 15  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                 30 
                 — 
                 ◯ 
                 X 
                 ◯ 
               
               
                   
                   
                 1 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 3 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 5 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 7 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 10  
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 15  
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
               
               
                 O 2  addition amount is the O 2  introduction amount where introduction amount of sputtering gas is 100. 
               
               
                 Zr addition amount is the number of the Zr atoms where the number of the atoms of the entire metals is inclusive of Zr. 
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
             
               
                 TABLE 3 
               
               
                   
               
               
                   
                 Cr Addition 
                 O 2  Addition 
                   
                 Barrior 
                   
               
               
                   
                 Amount 
                 Amount 
                   
                 Property 
                 Adhesion After 
               
               
                 Copper alloy 
                 (at %) 
                 (%) 
                 Adhesion 
                 300° C. 
                 H 2  Plasma Treatment 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Cu/Cu—Cr—O 
                 3 
                 — 
                 X 
                 X 
                 X 
               
               
                   
                   
                 1 
                 X 
                 X 
                 X 
               
               
                   
                   
                 3 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 5 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 7 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 10  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 15  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                 5 
                 — 
                 ◯ 
                 X 
                 ◯ 
               
               
                   
                   
                 1 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 3 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 5 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 7 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 10  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 15  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                 10 
                 — 
                 ◯ 
                 X 
                 ◯ 
               
               
                   
                   
                 1 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 3 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 5 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 7 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 10  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                   
                 15  
                 ◯ 
                 ◯ 
                 X 
               
               
                   
                 30 
                 — 
                 ◯ 
                 X 
                 ◯ 
               
               
                   
                   
                 1 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 3 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 5 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 7 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 10  
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                   
                 15  
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
               
               
                 O 2  addition amount is the O 2  introduction amount where introduction amount of sputtering gas is 100. 
               
               
                 Cr addition amount is the number of the Cr atoms where the number of the atoms of the entire metals is inclusive of Cr. 
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
             
               
                 TABLE 4 
               
               
                   
               
               
                   
                   
                   
                 Barrier 
                   
               
               
                   
                 CO 2   
                 Adhesion 
                 Property 
                 Adhesion After 
               
               
                 Metal 
                 (%) 
                 300° C. 
                 300° C. 
                 H 2  Plasma Treatment 
               
               
                   
               
             
            
               
                 Cu/Cu—Ti—CO 2   
                 — 
                 ◯ 
                 X 
                 ◯ 
               
               
                   
                 3 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                 5 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                 7 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                 10 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                 15 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                 20 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                 25 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                   
                 30 
                 ◯ 
                 ◯ 
                 X 
               
               
                   
               
            
           
         
       
     
     The above-listed results indicate that, when the additive metal included at least 5 atom %, adhesion (adhesion before and after the H 2  plasma treatment) and the barrier properties were desirable. 
     It is also indicated that the oxidizing gas should be introduced in a range of between at least 3 parts by volume and at most 15 parts by volume relative to an introduction amount of 100 parts by volume of the argon gas. 
       FIG. 4  is a graph showing specific resistances of adhesion layers (corresponding to the adhesion layers in the test results in Table 1) obtained when the copper alloy targets  111  including 10 atom % of Ti as the additive metal were sputtered with Ar gas and O 2  gas and specific resistances of the adhesion layers (corresponding to the adhesion layers in the test results in Table 4) obtained when the sputtering was carried out with Ar gas and CO 2  gas. The specific resistance of CO 2  gas is small in a range wider than that of O 2  gas, which is considered to be due to the oxidizing power of CO 2  gas which is lower than that of O 2  gas. 
     A minimal value of the specific resistance of oxygen appears in a range of the partial pressure of 3 to 5%. To the contrary, the specific resistance of carbon dioxide is low in a wider range of the partial pressure of 3 to 25%. Consequently, it is easier to adjust the concentration of carbon dioxide. Even if it is difficult to make constant the concentration of the oxidizing gas in a case of a large-scale substrate, a low resistance is obtained by utilizing carbon dioxide such that the partial pressure may be set in the above-discussed wider range; thus, carbon dioxide is more preferable. 
     Moreover, the minimum value of the specific resistance is lower in the case of carbon dioxide. 
     A low resistance may not be required when a thin barrier film is formed. However, when a barrier film is formed to be thicker, or when an entire electrode is formed by an alloy layer, with oxidizing gas being introduced, an electrode having a low resistance is required, which makes the use of carbon dioxide more preferable. 
     Next, the obtained metal wiring film was immersed into an etching liquid, then it is observed whether it is possible to etch both the low-resistance metallic layer  52  and the adhesion layer  51  with the same etching liquid. Phosphoric/nitric/acetic acids (H 3 PO 4 :HNO 3 :CH 3 COOH:H 2 O)=16:1:2:1 were used in the etching liquid, of which temperature was set at 40° C. 
     Observation results in the etching are given in the following Table 5. In Table 5, examples in which an etching residue is not observed are shown by a circle “◯”, while those in which an etching residue is observed are shown by a cross “X”. 
     
       
         
           
               
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                 Adhesion Amount 
                 Whether wet etching was possible or not 
               
            
           
           
               
               
               
               
            
               
                 X(at %) 
                 Cu—X at % Ti 
                 Cu—X at % Zr 
                 Cu—X at % Cr 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 0 
                 ◯ 
                 ◯ 
                 O 
               
               
                 3 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                 5 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                 7 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                 10 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                 15 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                 30 
                 ◯ 
                 ◯ 
                 ◯ 
               
               
                 50 
                 X 
                 X 
                 ◯ 
               
               
                 75 
                 X 
                 X 
                 ◯ 
               
               
                 100 
                 X 
                 X 
                 ◯ 
               
               
                   
               
            
           
         
       
     
     As to Ti and Zr, it is indicated that at most 30 atom % is desirable. There is no residue of Cr observed, even if it is over 50 atom %; however, since widths of the adhesion layer  51  and the low-resistance metallic layer  52  may significantly differ, at most 30 atom % is preferable in the case of Cr, too. 
     Moreover, since adhesion of the adhesion layer  51  to silicon or silicon oxide, as well as to the low-resistance metallic layer  52  are desirably higher, the adhesion layer  51  in the present invention includes at least 50% of copper as a component of the low-resistance metallic layer  52 .