Abstract:
A semiconductor device comprises: a semiconductor chip; a first frame; a solder layer which bonds the solder bonding metal layer of the semiconductor chip and the first frame; and a second frame bonded to the rear face of the semiconductor chip. The semiconductor chip includes: a semiconductor substrate; a first metal layer provided on a major surface of the semiconductor substrate and forming a Schottky junction with the semiconductor substrate; a second metal layer provided on the first metal layer and primarily composed of aluminum; a third metal layer provided on the second metal layer and primarily composed of molybdenum or titanium; and a solder bonding metal layer provided on the third metal layer and including at least a forth metal layer which is primarily composed of nickel, ion or cobalt.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2004-202989, filed on Jul. 9, 2004; the entire contents of which are incorporated herein by reference. 
       BACKGROUND OF THE INVENTION 
       [0002]    This invention relates to a semiconductor device in which a semiconductor chip (hereinafter referred to as “chip”) is electrically solder bonded to a frame serving as an external terminal, and to its surface laminated electrode structure and a method of manufacturing the semiconductor device. 
         [0003]    Schottky barrier diodes (SBD) and Zener diodes often have a junction near the metal surface. For such semiconductor device products, there is an existing technology in which an aluminum (Al) layer is sandwiched in a laminated electrode on the surface (Japanese Laid-Open Patent Applications 2000-114302 and 63-289956 (1988)). Such existing semiconductor devices have the following problems: 
         [0004]    1. A Schottky barrier diode having the conventional metal structure (low V F -SBD and low IR-SBD) will be described. 
         [0005]    With respect to this diode, when Schottky metal (in general, high melting point metal such as V and Ti is used) is formed on a silicon semiconductor substrate surface, its protecting film (typically high melting point metal such as Mo, like the Schottky metal) is consecutively formed at the same time. This is carried out in order to prevent the Schottky surface from being damaged during a heat treatment step (performed for the purpose of controlling the Schottky metal to have a prescribed work function, φB) when the process is advanced from the metal film patterning step to the heat treatment step. 
         [0006]    Next, oxide film on the protecting film formed during the heat treatment is removed and a solder bonding metal layer (composed of: two-layer bonding material made of a Ni layer and a V or Ti layer; bonding material made of a Ni layer to be contacted with assembly solder; and antioxidant film for Ni made of a Au or Ag (silver) layer) is formed. After its patterning, a chip having finally three to five layers of surface metal is completed. The top and rear of the chip are then bonded to upper and lower frames (conductive metal on the substrate or strip) with assembly solder to complete a diode. 
         [0007]    In this structure, typically, if there is any thin portion of assembly solder, the chip surface is directly susceptible to rapid heating during assembly of upper and lower frames, rapid heating during installation on a customer site, and/or frame stress due to temperature difference in the commercial use environment. This causes stress on the surface junction, and junction breakdown may occur due to the stress. 
         [0008]    2. Next, the case of pn junction chip products including shallow junction chip products (Xj being 3 μm or less, e.g., constant voltage diode having low withstand voltage) will be described. 
         [0009]    In manufacturing this product, a solder bonding metal layer (composed of: bonding material made of a V or Ti layer to be contacted with silicon; bonding material made of a Ni layer to be contacted with assembly solder; and antioxidant film for Ni made of a Au or Ag layer) is formed on a surface junction of the silicon semiconductor substrate. After its patterning, a chip having finally three layers of surface metal is completed. Subsequently, during assembly, the top and rear of the chip are bonded to upper and lower frames (conductive metal on the substrate or strip) with assembly solder to complete a diode. 
         [0010]    In this structure again, typically, if there is any thin portion of assembly solder, the chip surface is directly susceptible to rapid heating during assembly of upper and lower frames, rapid heating during installation on a customer site, and/or frame stress due to temperature difference in the commercial use environment. This causes stress on the surface junction, and junction breakdown may occur due to the stress. 
       SUMMARY OF THE INVENTION 
       [0011]    According to an aspect of the invention, there is provided 
         [0012]    a semiconductor device comprising:
       a semiconductor chip including:   a semiconductor substrate;   a first metal layer provided on a major surface of the semiconductor substrate and forming a Schottky junction with the semiconductor substrate;   a second metal layer provided on the first metal layer and primarily composed of aluminum;   a third metal layer provided on the second metal layer and primarily composed of molybdenum or titanium; and   a solder bonding metal layer provided on the third metal layer and including at least a forth metal layer which is primarily composed of nickel, ion or cobalt;       
 
         [0019]    a first frame; 
         [0020]    a solder layer which bonds the solder bonding metal layer of the semiconductor chip and the first frame; and 
         [0021]    a second frame bonded to the rear face of the semiconductor chip. 
         [0022]    According to other aspect of the invention, there is provided a semiconductor device comprising: 
         [0023]    a semiconductor chip including:
       a semiconductor substrate having a diffusion region that is formed in a surface region of a major surface thereof and constitutes a p-n junction;   a first metal layer provided on the major surface of the semiconductor substrate and primarily composed of aluminum;   a second metal layer provided on the first metal layer and primarily composed of molybdenum or titanium; and       
 
         [0027]    a solder bonding metal layer provided on the second metal layer and including at least a third metal layer which is primarily composed of nickel, ion or cobalt; 
         [0028]    a first frame; 
         [0029]    a solder layer which bonds the solder bonding metal layer of the semiconductor chip and the first frame; and 
         [0030]    a second frame bonded to the rear face of the semiconductor chip. 
         [0031]    According to other aspect of the invention, there is provided a method of manufacturing a semiconductor device comprising: 
         [0032]    forming a laminated structure on a major surface of a semiconductor substrate, the laminated structure including at least a first metal layer that forms a Schottky junction with the semiconductor substrate, a second metal layer primarily composed of aluminum, and a third metal layer primarily composed of molybdenum or titanium; 
         [0033]    patterning the laminated structure into a predetermined configuration; 
         [0034]    forming a solder bonding metal layer including at least nickel, ion or cobalt on the major surface of the semiconductor substrate having the patterned laminated structure formed thereon; 
         [0035]    patterning the solder bonding metal layer into a pattern configuration identical to that of the laminated structure; 
         [0036]    cutting the semiconductor substrate on which the laminated structure and the solder bonding metal layer are patterned to form a plurality of semiconductor chips; and 
         [0037]    bonding the semiconductor chip to a first frame using at least one solder layer formed on the solder bonding metal layer on the major surface of the semiconductor substrate, and 
         [0038]    bonding the rear face of the semiconductor chip to a second frame. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0039]      FIGS. 1A to 1C  are cross-sectional and plan views of a low V F  Schottky barrier diode, and  FIG. 1C  is a cross-sectional view of a chip  1  thereof, according to a first embodiment of the invention; 
           [0040]      FIGS. 2A to 2D  are cross-sectional views of a process up to the step of cutting out a chip from the silicon semiconductor substrate according to the first embodiment of the invention; 
           [0041]      FIGS. 3A to 3D  are process cross-sectional views illustrating a method of forming a surface laminated electrode structure used in soldering to the chip an upper frame serving as an external terminal; 
           [0042]      FIG. 3E  is a sectional view illustrating the finished chip; 
           [0043]      FIGS. 4A to 4D  are process cross-sectional views illustrating a method of forming a surface laminated electrode structure used in soldering to the chip an upper frame serving as an external terminal; 
           [0044]      FIG. 4E  is a sectional view illustrating the finished chip; 
           [0045]      FIGS. 5A and 5B  are cross-sectional and plan views of p-n junction products containing bipolar transistor, MOS transistor, and the like without shallow junction chip; 
           [0046]      FIG. 5C  is a cross-sectional view of a chip  1 ; and 
           [0047]      FIGS. 6A to 6D  are process cross-sectional views illustrating a method of forming a surface laminated electrode structure used in soldering an upper frame serving as an external terminal to the chip. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0048]    Embodiments of the invention will now be described with reference to examples. 
       First Example 
       [0049]    The first example of the invention is now described with reference to  FIGS. 1A to 1C  and  2 A to  2 D. 
         [0050]      FIGS. 1A and 1B  are cross-sectional and plan views of a low V F  Schottky barrier diode, and  FIG. 1C  is a cross-sectional view of a chip  1 . 
         [0051]      FIGS. 2A to 2D  are process cross-sectional views illustrating a method of forming a surface laminated electrode structure used in soldering to the chip an upper frame serving as an external terminal. That is,  FIGS. 2A to 2D  are cross-sectional views of a process up to the step of cutting out a chip from the silicon semiconductor substrate. 
         [0052]    As shown in  FIGS. 1A to 1C , the chip  1  is sandwiched between an upper frame  3  and a lower frame  5  serving as external terminals, and is bonded thereto with solder layers  2  and  4 . The upper and lower frames  3 ,  5  and the chip  1  are resin sealed with resin sealant  6  such as epoxy ( FIGS. 1A to 1C ). A laminated electrode structure  7  including a Schottky metal layer is formed on the surface of the chip  1  sandwiched between the upper and lower frames  3 ,  5  so that the chip  1  may be solder bonded to the upper frame  3  ( FIGS. 2A to 2D ). 
         [0053]    Each chip including the semiconductor substrate  10  of this example has a laminated electrode structure formed thereon. The laminated electrode structure is composed of a Schottky metal layer (first layer)  11  of V or Ti film having a film thickness of 0.1 to 0.3 μm, a Mo or Ti layer (second layer)  12  having a film thickness of 0.1 to 0.4 μm serving as protecting film for Schottky metal, an Al layer (third layer)  13  having a film thickness of 0.5 to 1.0 μm serving as protecting film used for buffer film, a Mo layer (fourth layer)  14  having a film thickness of 0.1 to 0.4 μm serving as protecting film for aluminum, a V or Ti layer (fifth layer)  15  having a film thickness of 0.02 to 0.05 μm serving as a first solder bonding layer, a Ni layer (sixth layer)  16  having a film thickness of 0.1 to 0.4 μm serving as a second solder bonding layer of bonding material to be contacted with solder, and a Au, Ag, or Pt or their alloyed layer (seventh layer)  17  having a film thickness of 0.03 to 0.2 μm serving as a third solder bonding layer of antioxidation film for Ni. One of these layers is Schottky metal  11 , and the three upper layers  15 ,  16 , and  17  constitute a bonding metal layer  8  to be contacted with solder. 
         [0054]    Next, a method of manufacturing the semiconductor device shown in  FIG. 2  will be described. 
         [0055]    First, on a semiconductor substrate  10  of silicon or the like to be eventually cut into chips, existing methods are used to laminate four metal layers composed of Schottky metal  11  of V or Ti, a Mo or Ti layer  12  serving as protecting film for the Schottky metal, an Al layer  13  serving as protecting film used for buffer film, and a Mo layer  14  serving as protecting film for aluminum ( FIG. 2A ). 
         [0056]    Next, these laminated metal layers  11  to  14  are patterned by wet etching or the like to leave these metal layers on each chip formation region of the semiconductor substrate  10 . Subsequently, the semiconductor substrate  10  is heat treated to sinter the Schottky metal ( FIG. 2B ). 
         [0057]    Next, after oxide film formed on the surface of the Mo layer  14  due to the heat treatment is removed, a solder bonding metal layer  8  is formed on the semiconductor substrate  10  including the Mo layer  14 . The solder bonding metal layer  8  is composed of three layers: a V or Ti layer  15 , a Ni layer  16  serving as bonding material to be contacted with solder, and a Au or Ag layer  17  serving as antioxidation film for Ni. 
         [0058]    Next, these laminated metal layers  15  to  17  are patterned by wet etching or the like to leave these metal layers on each chip formation region of the semiconductor substrate  10 . Since etching is performed for each metal layer, three iterations of etching are performed in total ( FIG. 2C ). 
         [0059]    Next, a rear face metal layer  9  is formed on the rear face of the semiconductor substrate  10 . 
         [0060]    The semiconductor substrate  10  is then diced along the boundary of the chip formation region shown by dashed lines to form a plurality of chips having the laminated electrode structure ( FIG. 2D ). 
         [0061]    Next, upper and lower frames  3 ,  5  are attached to the chip  1  with solder to form a semiconductor device (see  FIG. 1 ). 
         [0062]    In the background technology described above, only a Mo layer is provided on the Schottky metal for its protection. On the contrary, in this example, protecting film composed of an Al layer and a Mo layer thereon is added to form a seven-layer laminated electrode structure  7 . 
         [0063]    In this example, the aluminum layer  13  achieves an effect of buffering stress. More specifically, aluminum can serve as soft buffering material for reducing stress on the Schottky metal such as solder stress during assembly of the semiconductor device, rapid heating stress during installation of the semiconductor device on a customer site, and stress due to temperature difference in a commercial actual use environment. 
         [0064]    In addition, Mo is less prone to formation of intermetallic compound with V or Ti. That is, the Mo layer  14  laminated on the Al layer  13  can prevent the formation of intermetallic compound with the V or Ti layer  15  thereon. This results in a semiconductor device that is free from deterioration of electric characteristics (V F  loss) due to the formation of intermetallic compound, and from junction breakdown due to the stress on the Schottky metal. 
         [0065]    Furthermore, the thick aluminum layer  13  added to the entire surface of the chip serves to spread current across the chip, which has an effect of reducing V F  loss and improving surge current capacity (overcurrent breakdown capacity). As a result, it is possible to manufacture and market semiconductor devices with improved product yield and high reliability and functionality, and without concern about failure on a customer site and in the market. 
         [0066]    On the other hand, various companies are currently taking measures to complete Pb-free (lead-free) devices. In this respect, Sn-based solder is about to be substituted for Pb-based solder. However, use of Sn-based solder causes increase of stress. Reducing this stress is also an effect achieved by the Al—Mo structure of the present example. In particular, a great effect can be expected in a semiconductor device intended for in-vehicle or other applications used in a severe temperature environment. 
         [0067]    In the laminated electrode structure described above, the second metal layer (Mo or Ti layer)  12  formed for protecting the Schottky metal is formed as needed, and is not an indispensable constituent material in the invention. The fifth V or Ti layer formed on the fourth Mo layer serving as protecting film is formed as needed, and is not an indispensable constituent material in the invention. 
         [0068]    The fifth Ni layer to be contacted with solder is not limited to this material. In this example, instead of the Ni layer, a Co or Fe layer can also be used. Furthermore, in this example, the film thickness of the third Al layer can be greater than the film thickness of the first layer (Schottky metal), the second layer (protecting film for the Schottky metal), and the fourth layer (protecting film for aluminum). In addition, the Al layer can be twice or more as thick as the film thickness of its upper or lower metal layer. 
         [0069]    In this example, the four-layer laminated metal layer is patterned before heat treating the semiconductor substrate  10  to sinter the Schottky metal  11  (see  FIG. 2B ). This is carried out in order to control φB (work function of the Schottky portion). In addition, in this example, the first to seventh layers (lamination of the fifth layer may be omitted) can be formed on the semiconductor substrate to form a laminated electrode structure before the sixth and seventh layers are patterned. Furthermore, in this example, the first to seventh layers (lamination of the fifth layer may be omitted) can be consecutively formed on the semiconductor substrate to form a laminated electrode structure before this structure is patterned and then heat treated. 
       Second Example 
       [0070]    The second example of the invention is now described with reference to  FIGS. 3A to 3E . 
         [0071]      FIGS. 3A to 3D  are process cross-sectional views illustrating a method of forming a surface laminated electrode structure used in soldering to the chip an upper frame serving as an external terminal. That is,  FIGS. 3A to 3D  are cross-sectional views of a process up to the step of cutting out a chip from the silicon semiconductor substrate. 
         [0072]      FIG. 3E  is a sectional view illustrating the finished chip. 
         [0073]    A semiconductor device used in this example is a Schottky barrier diode of low-IR type. A complete structure thereof having upper and lower frames is basically the same as the one shown in  FIGS. 1A and 1B , therefore, a detailed explanation thereof will be appropriately omitted. 
         [0074]    Each chip including the semiconductor substrate  10  of this example has a laminated electrode structure  27  formed thereon. The laminated electrode structure  27  includes a Schottky metal layer (first layer)  21  of V or Ti film having a film thickness of 0.1 to 0.5 μm, an Al layer (second layer)  22  having a film thickness of 0.5 to 1.0 μm serving as protecting film used for buffer film, a Mo layer (third layer)  23  having a film thickness of 0.1 to 0.5 μm serving as protecting film for aluminum, a V or Ti layer (forth layer)  24  having a film thickness of 0.02 to 0.05 μm serving as a first solder bonding layer, a Ni layer (fifth layer)  25  having a film thickness of 0.1 to 0.4 μm serving as a second solder bonding layer of bonding material to be contacted with solder, and a Au, Ag, or Pt or their alloyed layer (sixth layer)  26  having a film thickness of 0.03 to 0.2 μm serving as a third solder bonding layer of antioxidation film for Ni. One of these layers is Schottky metal  21 , and the three upper layers  24 ,  25 , and  26  constitute a bonding metal layer  28  to be contacted with solder. 
         [0075]    Next, a method of manufacturing the semiconductor device shown in  FIGS. 3A through 3D  will be described. 
         [0076]    First, on a semiconductor substrate  10  of silicon or the like to be eventually cut into chips, existing methods are used to laminate three metal layers composed of Schottky metal  21  of V or Ti, an Al layer  22  serving as protecting film used for buffer film, and a Mo layer  23  serving as protecting film for aluminum ( FIG. 3A ). 
         [0077]    Next, these laminated metal layers  21  to  23  are patterned by wet etching or the like to leave these metal layers on each chip formation region of the semiconductor substrate  10 . Subsequently, the semiconductor substrate  10  is treated with heat to sinter the Schottky metal ( FIG. 3B ). 
         [0078]    Next, after oxide film formed on the surface of the Mo layer  23  due to the heat treatment is removed, a solder bonding metal layer  28  is formed on the semiconductor substrate  10  including the Mo layer  23 . The solder bonding metal layer  28  is composed of three layers: a V or Ti layer  24 , a Ni layer  25  serving as bonding material to be contacted with solder, and a Au or Ag layer  26  serving as antioxidation film for Ni. 
         [0079]    Next, these laminated metal layers  24  to  26  are patterned by wet etching or the like to leave these metal layers on each chip formation region of the semiconductor substrate  10 . Since etching is performed for each metal layer, three iterations of etching are performed in total ( FIG. 3C ). 
         [0080]    Next, a rear face metal layer  9  is formed on the rear face of the semiconductor substrate  10 . 
         [0081]    The semiconductor substrate  10  is then diced along the boundary of the chip formation region shown by dashed lines to form a plurality of chips having the laminated electrode structure ( FIG. 3D ). 
         [0082]    Next, upper and lower frames  3 ,  5  are attached to the chip  1  with solder to form a semiconductor device (see  FIGS. 1A and 1B ). 
         [0083]    In this example, protecting film composed of an Al layer formed on the Schottky metal and a Mo layer formed on Al layer is added to form a six-layer laminated electrode structure. 
         [0084]    In this example, aluminum can serve as soft buffering material for reducing stress on the Schottky metal such as solder stress during assembly of the semiconductor device, rapid heating stress during installation of the semiconductor device on a customer site, and stress due to temperature difference in a commercial actual use environment. 
         [0085]    In addition, Mo is less prone to formation of intermetallic compound with V or Ti. That is, the Mo layer  14  laminated on the Al layer  13  can prevent the formation of intermetallic compound with the V or Ti layer  15  thereon. This results in a semiconductor device that is free from deterioration of electric characteristics (V F  loss) due to the formation of intermetallic compound, and from junction breakdown due to the stress on the Schottky metal. 
         [0086]    Furthermore, the thick aluminum layer  22  added to the entire surface of the chip serves to spread current across the chip, which has an effect of reducing V F  loss and improving surge current capacity (overcurrent breakdown capacity). As a result, it is possible to manufacture and market semiconductor devices with improved product yield and high reliability and functionality, and without concern about failure on a customer site and in the market. 
         [0087]    On the other hand, various companies are currently taking measures to complete Pb-free (lead-free) devices. In this respect, Sn-based solder is about to be substituted for Pb-based solder. However, use of Sn-based solder causes increase of stress. Reducing this stress is also an effect achieved by the Al—Mo structure of the present example. In particular, a great effect can be expected in a semiconductor device intended for in-vehicle or other applications used in a severe temperature environment. 
         [0088]    The forth V or Ti layer  24  formed on the third Mo layer  23  serving as protecting film is formed as needed, and is not an indispensable constituent material in the invention. 
         [0089]    The fifth Ni layer  25  to be contacted with solder is not limited to this material. In this example, instead of the Ni layer, a Co or Fe layer can also be used. Furthermore, in this example, the film thickness of the second Al layer  22  can be greater than the film thickness of the first layer (Schottky metal)  21 , and the fourth layer (protecting film for aluminum)  24 . In addition, the Al layer  22  can be twice or more as thick as the film thicknesses of its upper or lower metal layers. 
         [0090]    In this example, the thee-layer laminated metal layer is patterned before heat treating the semiconductor substrate  10  to sinter the Schottky metal  11  (see  FIG. 3B ). This is carried out in order to control φB (work function of the Schottky portion). Alternatively, the forth layer  24  through sixth layer  26  can be formed and patterned at the same time. 
         [0091]    In addition, in formation of laminated metal layer  27  of this example, V or Ti layer  24  may be omitted. That is, five-layer laminated metal layer including a Schottky metal layer (first layer), Al layer (second layer), Mo or Ti layer (third layer), Ni layer (forth layer) and a Au, Ag, or Pt or their alloyed layer are continuously formed without V or Ti layer on Mo layer (forth layer) may be formed and patterned before the laminated metal layer is treated with heat. 
         [0092]    Alternatively, in this example, the first to sixth layers can be consecutively formed on the semiconductor substrate to form a laminated electrode structure before this structure is patterned and then heat treated. 
       Third Example 
       [0093]    The third example of the invention is now described with reference to  FIGS. 4A to 4E . 
         [0094]      FIGS. 4A to 4D  are process cross-sectional views illustrating a method of forming a surface laminated electrode structure used in soldering to the chip an upper frame serving as an external terminal. That is,  FIGS. 4A to 4D  are cross-sectional views of a process up to the step of cutting out a chip from the silicon semiconductor substrate. 
         [0095]      FIG. 4E  is a sectional view illustrating the finished chip. 
         [0096]    A semiconductor device used in this example is a low breakdown constant voltage diode of shallow-junction type such as a Zener diode. A complete structure thereof having upper and lower frames is basically the same as the one shown in  FIGS. 1A and 1B , therefore, a detailed explanation thereof will be appropriately omitted. 
         [0097]    Each chip region including the semiconductor substrate  10  of this example has a laminated electrode structure  37  formed thereon. 
         [0098]    The laminated electrode structure  37  is composed of a Mo or Ti layer (first layer)  31  film having a film thickness of 0.1 to 0.5 μm serving as protecting film for spike prevention, an Al layer (second layer)  32  having a film thickness of 0.5 to 1.0 μm serving as protecting film used for buffer film, a Mo or Ti layer (third layer)  33  having a film thickness of 0.1 to 0.5 μm serving as protecting film for aluminum, a V or Ti layer (forth layer)  34  having a film thickness of 0.02 to 0.05 μm serving as a first solder bonding layer, a Ni layer (fifth layer)  35  having a film thickness of 0.1 to 0.4 μm serving as a second solder bonding layer of bonding material to be contacted with solder, and a Au, Ag, or Pt or their alloyed layer (sixth layer)  36  having a film thickness of 0.03 to 0.2 μm serving as a third solder bonding layer of antioxidation film for Ni. Three upper layers  34 ,  35 , and  36  in the laminated electrode structure  37  constitute a bonding metal layer  38  to be contacted with solder. In a surface shallow region of the substrate  10 , a diffused layer  10   a  which forms a shallow junction is formed. 
         [0099]    Next, a method of manufacturing the semiconductor device shown in  FIG. 4  will be described. 
         [0100]    First, on a semiconductor substrate  10  of silicon or the like to be eventually cut into chips, existing methods are used to laminate three metal layers composed of a Mo or Ti layer  31  film serving as protecting film for spike prevention, an Al layer  32  serving as protecting film used for buffer film, a Mo or Ti layer  33  serving as protecting film for aluminum ( FIG. 4A ). 
         [0101]    Next, these laminated metal layers  31  to  33  are patterned by wet etching or the like to leave these metal layers on each chip formation region of the semiconductor substrate  10 . Subsequently, the semiconductor substrate  10  is heat treated to sinter the Schottky metal ( FIG. 4B ). 
         [0102]    Next, after oxide film formed on the surface of the Mo layer  33  due to the heat treatment is removed, a solder bonding metal layer  38  is formed on the semiconductor substrate  10  including the Mo layer  33 . The solder bonding metal layer  38  is composed of three layers: a V or Ti layer  34 , a Ni layer  35  serving as bonding material to be contacted with solder, and a Au, Ag, Pt or their alloyed layer  36  serving as antioxidation film for Ni. 
         [0103]    Next, these laminated metal layers  34  to  36  are patterned by wet etching or the like to leave these metal layers on each chip formation region of the semiconductor substrate  10 . Since etching is performed for each metal layer, three iterations of etching are performed in total ( FIG. 4C ). 
         [0104]    Next, a rear face metal layer  9  is formed on the rear face of the semiconductor substrate  10 . 
         [0105]    The semiconductor substrate  10  is then diced along the boundary of the chip formation region shown by dashed lines to form a plurality of chips having the laminated electrode structure  37  ( FIG. 4D ). 
         [0106]    Next, upper and lower frames  3 ,  5  are attached to the chip  1  with solder to form a semiconductor device (see  FIGS. 1A and 1B ). 
         [0107]    In the background technology described above, only a Mo layer is provided on the Schottky metal for its protection. In contrast to this, in this example, protecting film composed of an Al layer and a Mo layer thereon is added to form a six-layer laminated electrode structure. 
         [0108]    In this example, the aluminum layer  32  achieves an effect of buffering stress. More specifically, aluminum can serve as soft buffering material for reducing stress on the Schottky metal such as solder stress during assembly of the semiconductor device, rapid heating stress during installation of the semiconductor device on a customer site, and stress due to temperature difference in a commercial actual use environment. 
         [0109]    In addition, Mo is less prone to formation of intermetallic compound with V or Ti. That is, the Mo layer  33  laminated on the Al layer  32  can prevent the formation of intermetallic compound with the V or Ti layer  34  thereon. This results in a semiconductor device that is free from deterioration of electric characteristics (V F  loss) due to the formation of intermetallic compound, and from junction breakdown due to the stress on the Schottky metal. 
         [0110]    Furthermore, the thick aluminum layer  32  added to the entire surface of the chip serves to spread current across the chip, which has an effect of reducing V F  loss and improving surge current capacity (overcurrent breakdown capacity). As a result, it is possible to manufacture and market semiconductor devices with improved product yield and high reliability and functionality, and without concern about failure on a customer site and in the market. 
         [0111]    On the other hand, various companies are currently taking measures to complete Pb-free (lead-free) devices. In this respect, Sn-based solder is about to be substituted for Pb-based solder. However, use of Sn-based solder causes increase of stress. Reducing this stress is also an effect achieved by the Al—Mo structure of the present example. In particular, a great effect can be expected in a semiconductor device intended for in-vehicle or other applications used in a severe temperature environment. 
         [0112]    In a semiconductor device using this example, the Al layer  32  serving as stress buffer and current diffuser can be formed sufficiently thicker than two layers adjoining both sides of the Al layer  32 . The Al layer  32  may be formed twice or more as thick as two adjacent layers thereof. 
         [0113]    In addition, in formation of laminated metal layer  37  of this example, V or Ti layer  34  may be omitted. That is, a Ni layer (forth layer) serving as bonding material to be contacted with solder and a Au, Ag, Pt or their alloyed layer (fifth layer) serving as antioxidation film for Ni can be formed and patterned to form the solder bonding metal layer  38   
       Forth Example 
       [0114]    The forth example of the invention is now described with reference to  FIGS. 5A through 6D . 
         [0115]      FIGS. 5A and 5B  are cross-sectional and plan views of p-n junction products containing bipolar transistor, MOS transistor, and the like without shallow junction chip, and  FIG. 5C  is a cross-sectional view of a chip  1 . 
         [0116]      FIGS. 6A to 6D  are process cross-sectional views illustrating a method of forming a surface laminated electrode structure used in soldering an upper frame serving as an external terminal to the chip. That is,  FIGS. 6A to 6D  are cross-sectional views of a process up to the step of cutting out a chip from the silicon semiconductor substrate. 
         [0117]    As shown in  FIGS. 5A and 5B , the chip  1  is sandwiched between an upper frame  3  and a lower frame  5  serving as external terminals, and is bonded thereto with solder layers  2  and  4 . The upper and lower frames  3 ,  5  and the chip  1  are resin sealed with resin sealant  6  such as epoxy. A laminated electrode structure including a Schottky metal layer is formed on the surface of the chip  1  sandwiched between the upper and lower frames  3 ,  5  so that the chip  1  may be solder bonded to the upper frame  3  ( FIG. 5C ). 
         [0118]    Each chip including the semiconductor substrate  10  of this example has a laminated electrode structure  47  formed thereon. The laminated electrode structure  47  includes an Al layer (first layer)  41  having a film thickness of 0.5 to 1.0 μm serving as protecting film used for buffer film, a Mo or Ti layer (second layer)  42  having a film thickness of 0.1 to 0.4 μm serving as protecting film for aluminum, a V or Ti layer (third layer)  43  having a film thickness of 0.02 to 0.05 μm serving as a first solder bonding layer, a Ni layer (forth layer)  44  having a film thickness of 0.1 to 0.4 μm serving as a second solder bonding layer of bonding material to be contacted with solder, and a Au, Ag, or Pt or their alloyed layer (fifth layer)  45  having a film thickness of 0.03 to 0.2 μm serving as a third solder bonding layer of antioxidation film for Ni. Three upper layers  43 ,  44 , and  45  constitute a bonding metal layer  48  to be contacted with solder. In the surface region on the semiconductor substrate  10 , a diffused layer  10   b  which forms a p-n junction is provided. 
         [0119]    Next, a method of manufacturing the semiconductor device shown in  FIGS. 6A through 6D  will be described. 
         [0120]    First, on a semiconductor substrate  10  of silicon or the like to be eventually cut into chips, existing methods are used to laminate four metal layers composed of an Al layer  41  serving as protecting film used for buffer film, and a Mo layer  42  serving as protecting film for aluminum ( FIG. 6A ). 
         [0121]    Next, these laminated metal layers  41  and  42  are patterned by wet etching or the like to leave these metal layers on each chip formation region of the semiconductor substrate  10 . Subsequently, the semiconductor substrate  10  is heat treated ( FIG. 6B ). 
         [0122]    Next, after oxide film formed on the surface of the Mo layer  42  due to the heat treatment is removed, a solder bonding metal layer  48  is formed on the semiconductor substrate  10  including the Mo layer  42 . The solder bonding metal layer  48  is composed of three layers: a V or Ti layer  43 , a Ni layer  44  serving as bonding material to be contacted with solder, and a Au, Ag or Pt layer  45  serving as antioxidation film for Ni. 
         [0123]    Next, these laminated metal layers  43  to  45  are patterned by wet etching or the like to leave these metal layers on each chip formation region of the semiconductor substrate  10 . Since etching is performed for each metal layer, three iterations of etching are performed in total ( FIG. 6C ). 
         [0124]    Next, a rear face metal layer  9  is formed on the rear face of the semiconductor substrate  10 . 
         [0125]    The semiconductor substrate  10  is then diced along the boundary of the chip formation region shown by dashed lines to form a plurality of chips having the laminated electrode structure  47  ( FIG. 6D ). 
         [0126]    Next, upper and lower frames  3 ,  5  are attached to the chip  1  with solder to form a semiconductor device (see  FIGS. 5A and 5B ). 
         [0127]    In the background technology described above, only a Mo layer is provided on the Schottky metal for its protection. On the contrary, in this example, protecting film composed of an Al layer and a Mo layer thereon is added to form a five-layer laminated electrode structure. 
         [0128]    In this example, the aluminum layer  41  and the Mo layer  42  achieve an effect of buffering stress. More specifically, aluminum can serve as soft buffering material for reducing stress on the Schottky metal such as solder stress during assembly of the semiconductor device, rapid heating stress during installation of the semiconductor device on a customer site, and stress due to temperature difference in a commercial actual use environment. 
         [0129]    In addition, Mo is less prone to formation of intermetallic compound with V or Ti. That is, the Mo layer  42  laminated on the Al layer  41  can prevent the formation of intermetallic compound with the V or Ti layer  43  thereon. This results in a semiconductor device that is free from deterioration of electric characteristics (V F  loss) due to the formation of intermetallic compound, and from junction breakdown due to the stress on the Schottky metal. 
         [0130]    Furthermore, the thick aluminum layer  41  added to the entire surface of the chip serves to spread current across the chip, which has an effect of reducing V F  loss and improving surge current capacity (overcurrent breakdown capacity). As a result, it is possible to manufacture and market semiconductor devices with improved product yield and high reliability and functionality, and without concern about failure on a customer site and in the market. 
         [0131]    On the other hand, various companies are currently taking measures to complete Pb-free (lead-free) devices. In this respect, Sn-based solder is about to be substituted for Pb-based solder. However, use of Sn-based solder causes increase of stress. Reducing this stress is also an effect achieved by the Al—Mo structure of the present example. In particular, a great effect can be expected in a semiconductor device intended for in-vehicle or other applications used in a severe temperature environment. 
         [0132]    As an additional effect expected according to the example, the above-described structure having thick metal layers formed above and below the chip can be used to reduce assembly stress on the surface of a chip of a bipolar or MOSFET transistor because the outermost surface on both sides of the chip to be solder bonded has thick metal layers (with step size being 0.5 μm or more) which protect the underlying p-n junction. 
         [0133]    In a semiconductor device of this example, the Al layer  41  for stress reduction and current diffusion may be laminated sufficiently thicker than the Mo or Ti layer  42  thereon. This Al layer  41  may be twice or more as thick as the layer  42 . 
         [0134]    In the method of manufacturing a semiconductor device of this example, a total of four layers composed of the Al layer (first layer), Mo or Ti layer (second layer), Ni layer (third layer), and Au, Ag, or Pt or their alloyed film (fourth layer) can be consecutively formed, and thereafter this laminated metal film can be patterned and then heat treated. That is, the V or Ti layer  43  on the Mo layer  42  may be omitted. Alternatively, in the method of manufacturing a semiconductor device of this example, a total of five layers composed of the Al layer (first layer), Mo or Ti layer (second layer), the V or Ti layer (third layer) on the Mo layer, Ni layer (fourth layer), and Au, Ag, or Pt or their alloyed film (fifth layer) can be consecutively formed, and thereafter this laminated metal film can be patterned and then heat treated. 
         [0135]    While the present invention has been disclosed in terms of the embodiment in order to facilitate better understanding thereof, it should be appreciated that the invention can be embodied in various ways without departing from the principle of the invention. Therefore, the invention should be understood to include all possible embodiments and modification to the shown embodiments which can be embodied without departing from the principle of the invention as set forth in the appended claims.