WO2009101664A1 - 半導体装置の製造方法 - Google Patents

半導体装置の製造方法 Download PDF

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Publication number
WO2009101664A1
WO2009101664A1 PCT/JP2008/003544 JP2008003544W WO2009101664A1 WO 2009101664 A1 WO2009101664 A1 WO 2009101664A1 JP 2008003544 W JP2008003544 W JP 2008003544W WO 2009101664 A1 WO2009101664 A1 WO 2009101664A1
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Prior art keywords
conductive
electrode
substrate
mask
semiconductor substrate
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PCT/JP2008/003544
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English (en)
French (fr)
Inventor
Masataka Mizukoshi
Taisuke Iwai
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Fujitsu Limited
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Application filed by Fujitsu Limited filed Critical Fujitsu Limited
Priority to JP2009553292A priority Critical patent/JP5051243B2/ja
Publication of WO2009101664A1 publication Critical patent/WO2009101664A1/ja
Priority to US12/823,750 priority patent/US8735274B2/en

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    • H05K2203/05—Patterning and lithography; Masks; Details of resist
    • H05K2203/0548—Masks
    • H05K2203/0557—Non-printed masks

Definitions

  • the present invention relates to a method for manufacturing a semiconductor device in which conductive nanotubes are grown on an electrode formed on the surface of a semiconductor substrate.
  • the conductive pads on the mounting board and the conductive pads on the semiconductor chip are mechanically and electrically connected by metal bumps made of metal such as solder.
  • the metal atoms constituting the metal bump are easily moved by electromigration.
  • the movement of metal atoms causes the disconnection of the bump.
  • Sn which is a bump material, easily moves.
  • disconnection is likely to occur at the portion where the density is reduced.
  • the temperature of the semiconductor chip and the mounting substrate becomes high during solder fusion bonding.
  • stress is generated due to the difference in thermal expansion coefficient between them.
  • the thermal expansion coefficient of the mounting substrate is 10 times or more that of the semiconductor chip.
  • the mounting substrate is further contracted. Thereby, a compressive stress in the in-plane direction is applied to the semiconductor chip.
  • stress is generated, fracture occurs in the mechanically weakest part. For example, metal bumps, low dielectric constant insulating materials of semiconductor chips, etc. are destroyed.
  • a similar stress is also generated by a temperature change during operation after mounting.
  • Patent Document 1 A technique for connecting a conductive pad of a mounting substrate and a conductive pad of a semiconductor chip using carbon nanotubes is known (for example, Patent Document 1). Hereinafter, this connection method will be described.
  • Carbon nanotubes are grown from the conductive pads of the semiconductor chip by plasma enhanced chemical vapor deposition (PECVD).
  • PECVD plasma enhanced chemical vapor deposition
  • the base of the carbon nanotube is embedded in the conductive pad of the semiconductor chip, and the tip is embedded in the conductive pad of the mounting substrate. That is, both ends of the carbon nanotube are soldered to the semiconductor chip and the conductive pads of the mounting substrate. Thereby, the semiconductor chip is mechanically and electrically connected to the mounting substrate via the carbon nanotube.
  • the mounted semiconductor chip can slightly move in the in-plane direction with respect to the mounting substrate. For this reason, the destruction by the mechanical stress resulting from the difference in a thermal expansion coefficient can be prevented.
  • a catalytic metal such as Ni or Co is dispersed on the conductive pad, and carbon nanotubes are grown using acetylene as a source gas.
  • the substrate temperature must be heated to about 600 ° C.
  • the characteristics of the semiconductor element formed on the semiconductor substrate deteriorate.
  • Patent Documents 2 and 3 a technique for transferring carbon nanotubes grown on an alumina substrate or the like onto a conductive pad of a semiconductor substrate is disclosed (for example, Patent Documents 2 and 3). In this method, it is not necessary to grow carbon nanotubes directly on the semiconductor substrate. For this reason, high quality carbon nanotubes can be fixed to the conductive pads without heating the semiconductor substrate to a high temperature.
  • a conductive binder such as a conductive paste or a low-melting-point metal is disposed on a region of the substrate surface where the carbon nanotubes are to be planted.
  • Carbon nanotubes grown on the surface of an alumina substrate or the like are fixed to the conductive binder.
  • the conductive paste or the molten low melting point metal may spread laterally on the surface of the substrate. For this reason, it is difficult to transfer the carbon nanotube only to a desired region.
  • a manufacturing method of a first semiconductor device for solving the above-described problem is as follows. Exposing the electrodes formed in a partial region of the surface of the semiconductor substrate and the tips of a plurality of conductive nanotubes grown on the surface of the growth substrate to rare gas plasma; Contacting the tip of the conductive nanotube exposed to the rare gas plasma with the electrode of the substrate, and fixing the conductive nanotube to the electrode; Separating the growth substrate from the semiconductor substrate together with the conductive nanotubes not in contact with the electrodes, and leaving the conductive nanotubes fixed to the electrodes on the semiconductor substrate side.
  • a second method for manufacturing a semiconductor device for solving the above-described problem is as follows. Disposing a mask in which an opening corresponding to the electrode is formed on the surface of the semiconductor substrate on which the electrode is formed in a partial region of the surface; Depositing a conductive material on the electrode exposed at the bottom of the opening of the mask; The growth substrate having a plurality of conductive nanotubes on its surface is opposed to the semiconductor substrate, and the conductive nanotubes in the region where the openings of the mask are disposed are deposited in the openings.
  • the conductive material Since the conductive material is loaded in the opening of the mask, the conductive material can be prevented from spreading in the lateral direction of the substrate when the conductive nanotubes are brought into contact with each other.
  • a third method for manufacturing a semiconductor device for solving the above-described problem is as follows.
  • the base film is formed of a metal having a property of improving the adhesion between the conductive nanotube and the surface layer film, and the surface layer film is formed of a metal softer than the base film.
  • the contact area between the electrode and the tip metal member can be increased by deformation of the surface layer film.
  • 1A to 1C are sectional views (part 1) of the device in the middle of the method of manufacturing a semiconductor device according to the first embodiment.
  • 1D and 1E are sectional views (part 2) of the device in the middle of the method for manufacturing a semiconductor device according to the first embodiment.
  • 2A to 2C are sectional views (part 1) of the device in the middle of the semiconductor device manufacturing method according to the second embodiment.
  • 2D to 2F are sectional views (part 2) of the device in the middle of the semiconductor device manufacturing method according to the second embodiment.
  • 3A to 3C are sectional views (part 1) of the device in the middle of the semiconductor device manufacturing method according to the third embodiment.
  • 3D to 3F are sectional views (part 2) of the device in the middle of the semiconductor device manufacturing method according to the third embodiment.
  • FIGS. 4A is a cross-sectional view of the device in the middle of the semiconductor device manufacturing method according to the fourth embodiment
  • FIGS. 4B and 4C are cross-sectional views of the tips of the carbon nanotubes.
  • 4D to 4F are sectional views of the device in the middle of the method for manufacturing a semiconductor device according to the fourth embodiment.
  • 4G and 4H are cross-sectional views of the device in the middle of the semiconductor device manufacturing method according to the fourth embodiment.
  • FIGS. 4I and J are cross-sectional views of the tip of the carbon nanotube in the middle of the semiconductor device manufacturing method according to the fourth embodiment
  • FIG. 4K is a cross-sectional view of the device.
  • 4L and 4M are sectional views of the device in the middle of the semiconductor device manufacturing method according to the fourth embodiment.
  • FIG. 4N and 4O are cross-sectional views of the device in the middle of the semiconductor device manufacturing method according to the fourth embodiment.
  • 4P and 4Q are a cross-sectional view of the device in the middle of the method for manufacturing a semiconductor device according to the fourth embodiment and a cross-sectional view of the completed semiconductor device.
  • FIG. 5 is a cross-sectional view of a semiconductor device manufactured by a method according to a modification of the fourth embodiment.
  • FIGS. 1A to 1E a method of manufacturing a semiconductor device according to the first embodiment will be described.
  • FIG. 1A shows a cross-sectional view of a growth substrate 10 in which a large number of carbon nanotubes 15 are forested.
  • a method for growing carbon nanotubes will be described.
  • a Ti film 11 is formed on the surface of the growth substrate 10 made of quartz glass, silicon or the like, and a Ni film 12 is formed thereon.
  • a number of carbon nanotubes 15 are grown on the surface of the Ni film 12 by chemical vapor deposition (CVD) using a source gas such as acetylene.
  • CVD chemical vapor deposition
  • the diameter of each carbon nanotube 15 is 5 nm to 10 nm, and the distribution density is 5 ⁇ 10 10 to 1 ⁇ 10 11 pieces / cm 2 .
  • the interval between adjacent carbon nanotubes 15 is 30 nm to 100 nm.
  • FIG. 1B shows a cross-sectional view of a semiconductor substrate to which carbon nanotubes are to be transferred.
  • a pad 21 made of Al or the like is formed on the outermost surface of the semiconductor substrate 20 on which a semiconductor element such as a MOSFET and a multilayer wiring layer are formed.
  • a protective film 22 made of an insulating material is formed on the pad 21 and the semiconductor substrate 20.
  • a plurality of openings are formed in the protective film 22, and the pad 21 is exposed on the bottom surface of each opening.
  • An electrode 23 made of Al or the like is formed on the pad 21 exposed in the opening. The electrode 23 extends to the upper surface of the protective film 22 slightly outside the outer peripheral line of the opening.
  • the semiconductor substrate 20 and the growth substrate 10 are arranged in a vacuum chamber, and the electrode 23 is opposed to the carbon nanotube 15 with an interval of, for example, about 15 cm.
  • An argon plasma generator 30 is loaded in the vacuum chamber.
  • Argon plasma 31 is irradiated from the argon plasma generator 30 toward the tips of the carbon nanotubes 15 standing on the surface of the growth substrate 10 and the surface of the electrode 23 formed on the semiconductor substrate 20. Thereby, the tip of the carbon nanotube 15 is activated.
  • each of the carbon nanotubes 15 is normally cylindrical with a closed end, but becomes a cylindrical shape with an open end when irradiated with argon plasma.
  • the natural oxide film on the surface of the electrode 23 is removed, and a clean surface is exposed.
  • plasma of rare gas other than argon may be used.
  • the growth substrate 10 is brought close to the semiconductor substrate 20 without taking out the semiconductor substrate 20 and the growth substrate 10 into the atmosphere, and the tip of the carbon nanotube 15 is placed on the electrode 23. Touch the surface. Since the tip of the carbon nanotube 15 is activated by argon plasma and the surface of the electrode 23 is cleaned, the carbon constituting the carbon nanotube 15 and the aluminum constituting the electrode 23 are in contact with each other. And alloyed. Thereby, the carbon nanotube 15 is fixed to the electrode 23.
  • the growth substrate 10 is separated from the semiconductor substrate 20.
  • the carbon nanotubes 15 that have not been in contact with the electrode 23 leave the semiconductor substrate 20 while being fixed to the growth substrate 10.
  • the carbon nanotubes 15 fixed to the electrode 23 are peeled off from the growth substrate 15 and the state of being fixed to the electrode 23 is maintained.
  • Example 1 since the paste-like conductive adhesive is not used, even if the carbon nanotube 15 is brought into contact with the electrode 23, the adhesive does not spread within the substrate surface. Further, since the solder is not melted, the melted solder does not spread in the substrate surface. For this reason, it is possible to prevent the carbon nanotube 15 from adhering to a region other than the electrode 23 of the semiconductor substrate 20.
  • Example 1 aluminum was used for the electrode 23, but other metals alloyed with the carbon nanotubes 15 may be used.
  • metals include titanium (Ti), molybdenum (Mo), tungsten (W), chromium (Cr), nickel (Ni), iron (Fe), cobalt (Co), magnesium (Mg), and the like. It is also possible to use an alloy mainly composed of these metals.
  • the semiconductor substrate 20, pad 21, protective film 22, and electrode 23 shown in FIG. 2A are the same as those used in Example 1 shown in FIG. 1B.
  • the semiconductor substrate 20 is disposed in the vacuum chamber, and the mask 40 is disposed on the semiconductor substrate 20.
  • an opening 40A that matches the electrode 23 is formed in the mask 40.
  • the electrode 23 is exposed on the bottom surface of the opening 40A.
  • a region where the electrode 23 is not formed is covered with a mask 40.
  • aluminum films 41a and 41b are formed by vapor-depositing aluminum on the surface of the electrode 23 and the surface of the mask 40.
  • the aluminum films 41a and 41b may be formed by sputtering.
  • the thickness of the aluminum films 41a and 41b is, for example, 1 ⁇ m.
  • the electrode 23 and the aluminum film 41a deposited on the surface thereof constitute an electrode 23A.
  • the growth substrate 10 in which the carbon nanotubes 15 are forested is disposed above the semiconductor substrate 20 so that the carbon nanotubes 15 face the semiconductor substrate 20.
  • Argon plasma 31 is irradiated to the tip of the carbon nanotube 15, the electrode 23A, and the aluminum film 41b.
  • the growth substrate 10 is brought close to the semiconductor substrate 20 and the tips of the carbon nanotubes 15 are brought into contact with the aluminum film 41 b on the mask 40. Further, the growth substrate 10 is pressed against the semiconductor substrate 20, and the tip of the carbon nanotube 15 in the region where the opening 40A is disposed is brought into contact with the surface of the electrode 23A.
  • the carbon nanotubes 15 in contact with the aluminum film 41b on the mask 40 are elastically deformed and bent. For example, by applying a force of 3 to 5 N to an area of 1 mm 2 , it is possible to deflect about 30% of the carbon nanotubes standing at a distribution density of 5 ⁇ 10 10 to 1 ⁇ 10 11 / cm 2 .
  • “x% bending” means that the linear distance from the base portion to the tip of the carbon nanotube is bent so as to be shorter by x% than the length of the carbon nanotube itself.
  • An alloy of carbon and aluminum is formed at the contact portion between the carbon nanotube 15 and the electrode 23A and at the contact portion between the carbon nanotube 15 and the aluminum film 41b. Thereby, the carbon nanotube 15 in contact with the electrode 23A is fixed to the electrode 23A. Further, the carbon nanotubes 15 in contact with the aluminum film 41 b on the mask 40 are fixed to the mask 40.
  • the force pressing the growth substrate 10 against the semiconductor substrate 10 is released.
  • the growth substrate 10 is lifted from the semiconductor substrate 20 by the restoring force of the bent carbon nanotubes 15.
  • the carbon nanotubes 15 fixed to the electrode 23A are separated from the growth substrate 10 and remain (transferred) on the semiconductor substrate 20 side.
  • the growth substrate 10 is separated from the semiconductor substrate 20. Since the mask 40 is connected to the growth substrate 10 via the carbon nanotubes 15, the mask 40 is also separated from the semiconductor substrate 20 together with the growth substrate 10.
  • Example 2 similarly to Example 1, it is possible to prevent the carbon nanotubes 15 from adhering to unnecessary regions other than the electrodes 23A of the semiconductor substrate 20.
  • the growth substrate 10 can be separated from the semiconductor substrate 20 only by releasing the force pressing the growth substrate 10 against the semiconductor substrate 20 from the state shown in FIG. 2D. For this reason, it is not necessary to externally apply a force for peeling the carbon nanotubes 15 fixed to the electrode 23A from the growth substrate 10.
  • the thickness of the mask 40 is preferably set within a range of 10 to 30% of the length of the carbon nanotube 15.
  • the semiconductor substrate 20, pad 21, protective film 22, and electrode 23 shown in FIG. 3A are the same as those used in Example 1 shown in FIG. 1B.
  • a mask 40 is disposed on the semiconductor substrate 20. In the mask 40, an opening 40A that matches the electrode 23 is formed. The electrode 23 is exposed on the bottom surface of the opening 40A. A region where the electrode 23 is not formed is covered with a mask 40.
  • a paste-like conductive material 51 is deposited on the electrode 23 in the opening 40A.
  • a conductive resin such as a silver paste, a solder paste, or the like can be used.
  • the conductive material 51 can be deposited by a screen printing method using a squeegee.
  • the growth substrate 10 with the carbon nanotubes 15 standing on the surface is opposed to the semiconductor substrate 20.
  • the growth substrate 10 is pressed against the semiconductor substrate 20.
  • the carbon nanotubes 15 in contact with the mask 40 are bent, and the tips of the carbon nanotubes 15 in the region where the openings 40A are formed enter the paste-like conductive material 51.
  • the deposition amount of the conductive material 51 is adjusted so that the conductive material 51 does not overflow from the opening 40A.
  • the conductive material 51 is cured by heating the semiconductor substrate 20.
  • the heating temperature depends on the binder resin of the conductive material 51. For example, when an epoxy resin is used, the heating temperature is 150 to 200 ° C., and when a polyimide resin is used, the heating temperature is 200 to 250 ° C.
  • the conductive material 51 is cured, the carbon nanotubes 15 are fixed to the electrode 23.
  • the mask 40 is made of a material having heat resistance enough to withstand this heating temperature.
  • the force pressing the growth substrate 10 against the semiconductor substrate 20 is released.
  • the growth substrate 10 is lifted from the semiconductor substrate 20 by the restoring force of the bent carbon nanotubes 15.
  • the carbon nanotubes 15 fixed to the electrode 23 are peeled off from the growth substrate 10 and remain (transferred) on the semiconductor substrate 20 side.
  • the growth substrate 10 is separated from the semiconductor substrate 20. Since the carbon nanotubes 15 fixed to the electrode 23 have already been peeled off from the growth substrate 10, the growth substrate 10 can be easily separated from the semiconductor substrate 20. As shown in FIG. 3F, the mask 40 is separated from the semiconductor substrate 20.
  • Example 3 as shown in FIG. 3C, the paste-like conductive material 51 is loaded in the opening 40 ⁇ / b> A formed in the mask 40. For this reason, it can prevent that the conductive material 51 spreads to the area
  • the carbon nanotubes 15 are fixed to the mask 40 in the process illustrated in FIG. 3C.
  • the growth substrate 10 can be easily separated from the mask 40 in the step shown in FIG. 3E.
  • the thickness of the mask 40 is preferably in the range of 10 to 30% of the length of the carbon nanotube 15 as in the case of the second embodiment.
  • Example 4 A method for manufacturing a semiconductor device according to Example 4 will be described with reference to FIGS. 4A to 4Q.
  • the growth substrate 10, Ti film 11, Ni film 12, and carbon nanotube 15 shown in FIG. 4A have the same configuration as that of FIG. 1A used in Example 1.
  • a base metal and a surface metal are sequentially attached to the tip of the carbon nanotube 15 by sputtering, for example.
  • FIG. 4B shows an enlarged cross-sectional view of the tip of the carbon nanotube 15.
  • a tip metal member 57 is attached to the tip of the carbon nanotube 15.
  • the tip metal member 57 is composed of two layers, a base film 55 that covers the tip surface of the carbon nanotube 15 and a surface layer film 56 that covers the surface.
  • the base film 55 may be distributed discretely without continuously covering the surface of the tip of the carbon nanotube 15.
  • the surface layer film 56 adheres to each surface of the base film 55 distributed discretely.
  • the base film 55 is made of a metal that forms an alloy with carbon, such as Ti, W, or Cr.
  • a metal softer than the metal of the base film 55 such as Al or Au, is used.
  • the thickness of the carbon nanotube 15 is 5 to 10 nm, and the thickness of each of the base film 55 and the surface layer film 56 is about half of the diameter of the carbon nanotube 15.
  • the tip metal members 57 adhering to the tips of the carbon nanotubes 15 adjacent to each other do not continuously form one film.
  • the growth substrate 10 may be tilted with respect to the sputtering target.
  • the growth substrate 10 is tilted, it becomes difficult for metal atoms to be attached to reach the root of the carbon nanotube 15. Thereby, a metal can be effectively attached to the tip of the carbon nanotube 15.
  • the growth substrate 10 may be rotated along its surface during sputtering. By rotating the growth substrate 10, it is possible to prevent the tip metal member 57 from being biased in one direction.
  • FIG. 4D shows a cross-sectional view of the first substrate 66 provided with electrodes for adhering carbon nanotubes.
  • Electronic circuit elements such as MOSFETs are formed on the surface of the semiconductor substrate 60.
  • a multilayer wiring layer 61 is formed on the surface on which the electronic circuit element is formed.
  • a plurality of electrodes 62 are formed on the multilayer wiring layer 61.
  • a through via hole 63 is formed from the back surface of the semiconductor substrate 60 to reach the bottom surface of the front electrode 62 through the semiconductor substrate 60 and the multilayer wiring layer 61.
  • An insulating film 64 is formed on the side surface of the through via hole 63 and the surface on the back side of the semiconductor substrate 60.
  • a vertical connecting member 65 is filled in the through via hole 63.
  • the vertical connection member 65 is connected to the front electrode 62.
  • a method for manufacturing a substrate including the vertical connection member 65 extending from the back surface of the semiconductor substrate 60 to the front electrode 62 is disclosed in, for example, International Publication WO2004 / 064159.
  • a first metal mask 68 is disposed on the surface on the back side of the first substrate 66.
  • the first metal mask 68 is provided with an opening corresponding to the vertical connection member 65.
  • a metal film 70 such as aluminum is formed on the surface of the vertical connection member 65 exposed in the opening of the first metal mask 68 by sputtering, vapor deposition, or the like.
  • the thickness of the metal film 70 is, for example, 1 to 2 ⁇ m.
  • the metal film 70 also adheres to the surface of the first metal mask 68.
  • the first metal mask 68 is removed from the first substrate 66.
  • the metal film 70 remains on the surface of the vertical connection member 65.
  • a second metal mask 73 is disposed on the surface on the back side of the first substrate 66. Similar to the first metal mask 68 shown in FIG. 4E, the second metal mask 73 is provided with an opening corresponding to the vertical connection member 65.
  • the first substrate 66 and the growth substrate 10 are mutually connected so that the surface on which the carbon nanotubes 15 of the growth substrate 10 shown in FIG. 4A stand and the surface on the back side of the first substrate 66 face each other. Place them at intervals.
  • the Ar plasma 31 is irradiated on the surfaces facing each other. Thereby, the metal oxide and contaminants on the surface of the metal film 70 and the surface of the tip metal member 57 are removed, and the metal surface is activated.
  • the growth substrate 10 is brought close to the first substrate 66, and the tip metal member 57 at the tip of the carbon nanotube 15 is brought into contact with the metal mask 73. Further, pressure is applied until the carbon nanotubes 15 are bent, and the tip metal member 57 is brought into contact with the metal film 70. In this state, the first substrate 66 is heated to about 300 ° C. Thereby, the surface layer film 56 of the tip metal member 57 is bonded to the metal film 70.
  • the tip metal members 57 attached to the tips of the carbon nanotubes 15 adjacent to each other are continuously formed into a film shape, the carbon nanotubes 15 are less likely to enter the opening of the second metal mask 73.
  • the tip metal member 57 is preferably thin enough that the tip metal members 57 attached to the carbon nanotubes 15 adjacent to each other are not continuous.
  • the surface layer film 56 at the tip of the carbon nanotube 15 is deformed to follow the surface of the metal film 70 by pressure and heat, and the contact area between the surface layer film 56 and the metal film 70 increases.
  • FIG. 4J even when the tip metal member 57 is discretely attached, the contact area between the metal film 70 and the surface layer film 56 is deformed by the deformation of the surface layer film 56 in contact with the metal film 70. Will increase.
  • the carbon nanotube 15 is easily deformed such as a curve macroscopically, but is hardly deformed microscopically. For this reason, when the carbon nanotube 15 is in direct contact with the metal film 70, the contact between them is almost a point contact. In Example 4, the carbon nanotube 15 is more firmly fixed to the metal film 70 by increasing the contact area between the surface layer film 56 and the metal film 70.
  • the growth substrate 10 is separated from the first substrate 66.
  • the carbon nanotube 15 in which the tip metal member 57 is in contact with the metal film 70 is detached from the growth substrate 10 and fixed (transferred) to the semiconductor substrate 70 side.
  • the tip of the transferred carbon nanotube 15 (the end attached to the growth substrate 10) is in a state where carbon is exposed.
  • the carbon nanotube 15 in which the tip metal member 57 is in contact with the metal mask 73 remains on the growth substrate 10.
  • a tip metal member 85 is attached to the tip of the carbon nanotube 15 transferred to the first substrate 66.
  • the tip metal member 85 has a two-layer structure of a base film and a surface layer film, similarly to the tip metal member 57 shown in FIG. 4I or 4J.
  • the material of the base film and the surface layer film is the same as that of the tip metal member 57.
  • a second substrate 66a to be connected to the first substrate 66 is prepared. Similar to the first substrate 66 shown in FIG. 4D, the second substrate 66a includes a semiconductor substrate 60a, a multilayer wiring layer 61a, an electrode 62a, a through via hole 63a, an insulating film 64a, and a vertical connection member 65a.
  • the electrode 62a is made of, for example, aluminum.
  • the back surface of the first substrate 66 and the front surface of the second substrate 66a are arranged so as to be opposed to each other.
  • Ar plasma 31 is irradiated to the mutually opposing surfaces of the first substrate 66 and the second substrate 66a. Thereby, the surface of the tip metal member 85 and the surface of the electrode 62a are activated.
  • the first substrate 66 and the second substrate 66a are brought close to each other, and the tip metal member 85 of the carbon nanotube 15 is brought into contact with the electrode 62a.
  • the tip metal member 85 is joined to the electrode 62a by applying pressure and heat.
  • the distance between the first substrate 66 and the second substrate 66a is, for example, about 10 ⁇ m to 50 ⁇ m.
  • the third substrate 66b is connected to the surface on the back side of the second substrate 66a.
  • An electrode 62b is formed on the front surface of the third substrate 66b, and a metal film 70a is formed on the back surface of the second substrate 66a. Both are mechanically and electrically connected by the carbon nanotube 15a.
  • the same method as the method of connecting the second substrate 66a to the first substrate 66 is applied to the connection of the third substrate 66b.
  • resins 80a and 80b are filled between the first substrate 66 and the second substrate 66a and between the second substrate 66a and the third substrate 66b, respectively.
  • the filled resins 80a and 80b for example, epoxy, cyanate ester, benzocyclobutene, or the like is used.
  • the filling of these resins is performed, for example, by immersing a substrate mounted three-dimensionally in a resin solution under reduced pressure and then returning to normal pressure.
  • the vertical connection members 65 and 65a penetrate the multilayer wiring layers 61 and 61a from the back surface of the semiconductor substrates 60 and 60a.
  • the electrodes 62 and 62a on the front side are reached.
  • a substrate having another structure may be used as a structure for electrically connecting the front-side electrode and the back-side electrode of the substrate.
  • FIG. 5 shows an example of three-dimensional mounting of a substrate in which the front and back electrodes of the substrate are electrically connected with another structure.
  • the vertical connection members 95 and 95a penetrate the semiconductor substrates 60 and 60a, but do not penetrate the multilayer wiring layers 61 and 61a.
  • the vertical connection members 95 and 95a are connected to the front-side electrodes 62 and 62a through wirings, plugs, and the like in the multilayer wiring layers 61 and 61a.
  • Metal films 70 and 70a are formed on the back surface of the vertical connection members 95 and 95a.
  • Such vertical connecting members 95 and 95a are formed by, for example, performing chemical mechanical polishing from the back side surface until the conductive member is exposed after filling a conductive member into a low and low recess having an opening on the front side surface.
  • Such vertical connecting members 95 and 95a are formed by, for example, performing chemical mechanical polishing from the back side surface until the conductive member is exposed after filling a conductive member into a low and low recess having an opening on the front side surface.
  • Example 4 as shown in FIGS. 4I and 4J, the tip metal member 57 is deformed, so that the mechanical bonding strength between the carbon nanotube 15 and the metal film 70 is increased, and the electrical contact resistance is increased. Decreases.
  • the base film 55 is preferably made of a metal that can improve the adhesion between the surface layer film 56 and the carbon nanotube 15.
  • metals include metals that form an alloy with carbon, such as Ti, W, and Cr.
  • the surface layer film 56 is preferably made of a metal softer than the metal used for the base film 55 in order to increase the contact surface with the electrodes to be joined. It is more preferable to use a metal that is the same as or softer than Cu. Examples of such metals include Al and Au. Further, Au is more preferable in that it is difficult to be oxidized.
  • Example 4 As shown in FIG. 4G, after forming the metal film 70 and attaching the tip metal member 57, both surfaces were activated by Ar plasma. After the metal film 70 is formed and after the tip metal member 57 is attached, the treatment with Ar plasma may not be performed when both are bonded while maintaining the vacuum atmosphere.

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Abstract

　半導体基板の表面の一部の領域に形成されている電極と、成長用基板の表面に林立した複数の導電性ナノチューブの先端とを、希ガスプラズマに晒す。希ガスプラズマに晒された導電性ナノチューブの先端を該電極に接触させ、該導電性ナノチューブを該電極に固定する。成長用基板を、電極に接触していない導電性ナノチューブとともに半導体基板から離し、電極に固定された導電性ナノチューブは半導体基板側に残す。

Description

半導体装置の製造方法
　本発明は、半導体基板の表面に形成されている電極に導電性ナノチューブを林立させた半導体装置の製造方法に関する。
　従来、半導体チップを実装基板に実装する場合、半田等の金属からなる金属バンプにより、実装基板上の導電パッドと半導体チップ上の導電パッドとを、機械的及び電気的に接続していた。
　半導体チップの集積度が向上し、導電パッドの微細化が進むと、金属バンプを流れる電流密度が増大する。このため、エレクトロマイグレーションにより、金属バンプを構成している金属原子が移動し易くなる。金属原子の移動は、バンプの断線を引き起こす。例えば、半田バンプを用いる場合、バンプ材料であるＳｎが移動し易い。Ｓｎが移動することによってＳｎ密度の低下した部分が生じると、密度の低下した部分で断線が生じ易くなる。
　さらに、半田溶融接合の際に、半導体チップと実装基板が高温になる。実装後、半導体チップ及び実装基板が室温まで低下すると、両者の熱膨張係数の相違によって応力が発生する。通常、実装基板の熱膨張係数は、半導体チップの熱膨張係数の１０倍以上である。このとき、半導体チップ及び実装基板が室温まで低下すると、実装基板がより大きく収縮する。これにより、半導体チップに、面内方向の圧縮応力が印加される。応力が発生すると、機械的に最も弱い部分に破壊が生ずる。例えば、金属バンプ、半導体チップの低誘電率絶縁材料等が破壊されてしまう。なお、実装後の動作時における温度変化によっても、同様の応力が発生する。
　カーボンナノチューブを用いて、実装基板の導電パッドと半導体チップの導電パッドとを接続する技術が知られている（例えば、特許文献１）。以下、この接続方法について説明する。
　半導体チップの導電パッドから、プラズマ化学気相成長（ＰＥＣＶＤ）によりカーボンナノチューブを成長させる。カーボンナノチューブの根元を、半導体チップの導電パッドに埋め込むとともに、先端を、実装基板の導電パッドに埋め込む。すなわち、カーボンナノチューブの両端が、半導体チップ及び実装基板の導電パッドに半田付けされた状態になる。これにより、カーボンナノチューブを介して、半導体チップが実装基板に機械的及び電気的に接続される。
　カーボンナノチューブ１本に流すことができる電流密度は、従来の金属に比べて２～３桁高いことが知られている。このため、エレクトロマイグレーションによる断線の発生が生じにくくなる。
　また、カーボンナノチューブは柔軟性を持つため、実装された半導体チップは、実装基板に対して面内方向に僅かに移動することができる。このため、熱膨張係数の相違に起因する機械的応力による破壊を防止することができる。
　一般的に、半導体基板の導電パッド上にカーボンナノチューブを形成する場合、ＮｉやＣｏ等の触媒金属を導電パッド上に散布し、原料ガスとしてアセチレンを用いてカーボンナノチューブを成長させる。このとき、基板温度を６００℃程度まで加熱しなければならない。ところが、６００℃程度の高温に加熱すると、半導体基板に形成されている半導体素子の特性が劣化してしまう。
　半導体素子の性能が劣化しない程度の温度、例えば３５０℃程度の低温でカーボンナノチューブの成長を行うと、形成されたカーボンナノチューブの品質が悪くなり、かつ数週間という長い成長時間が必要になる。
　その他、アルミナ基板等に成長させたカーボンナノチューブを、半導体基板の導電パッド上に転写する技術が開示されている（例えば、特許文献２、３）。この方法では、半導体基板に直接カーボンナノチューブを成長させる必要がない。このため、半導体基板を高温に加熱することなく、導電パッドに高品質のカーボンナノチューブを固定することができる。
特表２００４－５２８７２７号公報 特開２００７－１８８６６２号公報 特開２００４－２８１３８８号公報
　上述の方法では、基板表面のうち、カーボンナノチューブを林立させるべき領域に、導電ペーストまたは低融点金属等の導電性バインダを配置する。アルミナ基板等の表面に成長したカーボンナノチューブが、導電性バインダに固着される。カーボンナノチューブの先端を導電性バインダに押し当てたときに、導電ペーストや、溶融した低融点金属が、基板の表面上で横方向に広がってしまう場合がある。このため、所望の領域のみにカーボンナノチューブを転写することが困難である。
　基板上の所望の領域にのみ、カーボンナノチューブ等の導電性ナノチューブを転写することが可能な方法の実現が望まれる。
　上述の課題を解決するための第１の半導体装置の製造方法は、
　半導体基板の表面の一部の領域に形成されている電極、及び成長用基板の表面に林立した複数の導電性ナノチューブの先端を、希ガスプラズマに晒す工程と、
　前記希ガスプラズマに晒された前記導電性ナノチューブの先端を、前記基板の電極に接触させ、該導電性ナノチューブを該電極に固定する工程と、
　前記成長用基板を、前記電極に接触していない前記導電性ナノチューブとともに前記半導体基板から離し、前記電極に固定された導電性ナノチューブは前記半導体基板側に残す工程と
を有する。
　ペースト状の導電性材料を用いないため、電極上にのみ導電性ナノチューブを固定することが可能になる。
　上述の課題を解決するための第２の半導体装置の製造方法は、
　表面の一部の領域に電極が形成されている半導体基板の該表面上に、該電極に対応する開口が形成されたマスクを配置する工程と、
　前記マスクの開口の底面に露出した前記電極の上に、導電性材料を堆積させる工程と、
　表面に複数の導電性ナノチューブが林立した成長用基板を、前記半導体基板に対向させ、前記マスクの開口が配置されている領域の前記導電性ナノチューブを、該開口内に堆積している前記導電性材料に接触させると共に、該開口が配置されていない領域の前記導電性ナノチューブを前記マスクに押し付けて撓ませる工程と、
　前記導電性材料に接触している前記導電性ナノチューブを、該導電性材料に固定する工程と、
　前記成長用基板を、前記導電性材料に固定されていない前記導電性ナノチューブとともに前記半導体基板から離し、前記導電性材料に固定された導電性ナノチューブは前記半導体基板側に残す工程と、
　前記マスクを前記半導体基板から離す工程と
を有する。
　導電性材料がマスクの開口内に装填されているため、導電性ナノチューブを接触させたときに、導電性材料が基板の横方向に広がることを抑制できる。
　上述の課題を解決するための第３の半導体装置の製造方法は、
　成長用基板の表面に林立した複数の導電性ナノチューブの先端に、下地膜及び表層膜がこの順番に積層された先端金属部材を形成する工程と、
　半導体基板の表面の一部の領域に形成されている電極に、前記先端金属部材を接触させ、前記導電性ナノチューブを前記電極に固定する工程と、
　前記成長用基板を、前記半導体基板から離し、前記電極に固定された導電性ナノチューブを前記半導体基板側に残す工程と
を有し、
　前記下地膜は、前記導電性ナノチューブと前記表層膜との密着性を高める性質を有する金属で形成され、前記表層膜は、前記下地膜よりも柔らかい金属で形成されている。
　表層膜の変形によって、電極と先端金属部材との接触面積を増大させることができる。
図１Ａ～図１Ｃは、第１の実施例による半導体装置の製造方法の途中段階における装置の断面図（その１）である。 図１Ｄ及び図１Ｅは、第１の実施例による半導体装置の製造方法の途中段階における装置の断面図（その２）である。 図２Ａ～図２Ｃは、第２の実施例による半導体装置の製造方法の途中段階における装置の断面図（その１）である。 図２Ｄ～図２Ｆは、第２の実施例による半導体装置の製造方法の途中段階における装置の断面図（その２）である。 図３Ａ～図３Ｃは、第３の実施例による半導体装置の製造方法の途中段階における装置の断面図（その１）である。 図３Ｄ～図３Ｆは、第３の実施例による半導体装置の製造方法の途中段階における装置の断面図（その２）である。 図４Ａは、第４の実施例による半導体装置の製造方法の途中段階における装置の断面図であり、図４Ｂ及び図４Ｃは、カーボンナノチューブの先端の断面図である。 図４Ｄ～図４Ｆは、第４の実施例による半導体装置の製造方法の途中段階における装置の断面図である。 図４Ｇ及び図４Ｈは、第４の実施例による半導体装置の製造方法の途中段階における装置の断面図である。 図４Ｉ及び図Ｊは、第４の実施例による半導体装置の製造方法の途中段階におけるカーボンナノチューブの先端の断面図であり、図４Ｋは、装置の断面図である。 図４Ｌ及び図４Ｍは、第４の実施例による半導体装置の製造方法の途中段階における装置の断面図である。 図４Ｎ及び図４Ｏは、第４の実施例による半導体装置の製造方法の途中段階における装置の断面図である。 図４Ｐ及び図４Ｑは、第４の実施例による半導体装置の製造方法の途中段階における装置の断面図、及び完成した半導体装置の断面図である。 図５は、第４の実施例の変形例による方法で製造した半導体装置の断面図である。
符号の説明
１０　成長用基板
１１　Ｔｉ膜
１２　Ｎｉ膜
１５、１５ａ　カーボンナノチューブ
２０　半導体基板
２１　パッド
２２　保護膜
２３、２３Ａ　電極
３０　アルゴンプラズマ発生装置
３１　アルゴンプラズマ
４０　マスク
４０Ａ　開口
４１ａ、４１ｂ　アルミニウム膜
５１　導電性材料
５５　下地膜
５６　表層膜
５７　先端金属部材
６０、６０ａ、６０ｂ　半導体基板
６１、６１ａ、６１ｂ　多層配線層
６２、６２ａ、６２ｂ　電極
６３、６３ａ　貫通ビアホール
６４、６４ａ　絶縁膜
６５、６５ａ　垂直接続部材
６６　第１の基板
６６ａ　第２の基板
６６ｂ　第３の基板
６８　メタルマスク
７０、７０ａ　金属膜
７３　メタルマスク
８０ａ　樹脂
８５　先端金属部材
９５、９５ａ　垂直接続部材
　以下、図面を参照しながら、実施例について説明する。
　図１Ａ～図１Ｅを参照して、実施例１による半導体装置の製造方法について説明する。
　図１Ａは、多数のカーボンナノチューブ１５が林立した成長用基板１０の断面図を示す。以下、カーボンナノチューブの成長方法について説明する。
　石英ガラス、シリコン等からなる成長用基板１０の表面に、Ｔｉ膜１１を形成し、その上にＮｉ膜１２を形成する。アセチレン等の原料ガスを用いた化学気相成長（ＣＶＤ）により、Ｎｉ膜１２の表面に、多数のカーボンナノチューブ１５を成長させる。一例として、カーボンナノチューブ１５の各々の直径は、５ｎｍ～１０ｎｍであり、分布密度は、５×１０１０～１×１０１１本／ｃｍ２である。相互に隣り合うカーボンナノチューブ１５の間隔は、３０ｎｍ～１００ｎｍである。
　図１Ｂに、カーボンナノチューブを転写すべき半導体基板の断面図を示す。ＭＯＳＦＥＴ等の半導体素子、及び多層配線層が形成された半導体基板２０の最表面に、Ａｌ等のパッド２１が形成されている。パッド２１及び半導体基板２０の上に、絶縁材料からなる保護膜２２が形成されている。保護膜２２に複数の開口が形成されており、各開口の底面にパッド２１が露出する。開口内に露出したパッド２１の上に、Ａｌ等の電極２３が形成されている。電極２３は、開口の外周線よりもやや外側の保護膜２２の上面まで広がっている。
　図１Ｃに示すように、半導体基板２０と成長用基板１０とを真空チャンバ内に配置し、電極２３を、カーボンナノチューブ１５に、例えば約１５ｃｍの間隔を隔てて対向させる。真空チャンバ内に、アルゴンプラズマ発生装置３０が装填されている。アルゴンプラズマ発生装置３０から、成長用基板１０の表面に林立しているカーボンナノチューブ１５の先端、及び半導体基板２０に形成されている電極２３の表面に向けて、アルゴンプラズマ３１を照射する。これにより、カーボンナノチューブ１５の先端が活性化される。例えば、カーボンナノチューブ１５の各々は、通常は端部が閉じた円筒状であるが、アルゴンプラズマを照射することによって、端部が開いた円筒状になる。また、電極２３の表面の自然酸化皮膜が除去されて、清浄な表面が露出する。なお、アルゴンプラズマに代えて、アルゴン以外の希ガスのプラズマを用いてもよい。
　図１Ｄに示すように、アルゴンプラズマの照射後、半導体基板２０及び成長用基板１０を大気中に取り出すことなく、成長用基板１０を半導体基板２０に近づけて、カーボンナノチューブ１５の先端を、電極２３の表面に接触させる。カーボンナノチューブ１５の先端が、アルゴンプラズマによって活性化されており、かつ電極２３の表面が清浄化されているため、両者の接触箇所において、カーボンナノチューブ１５を構成する炭素と、電極２３を構成するアルミニウムとが合金化する。これにより、カーボンナノチューブ１５が電極２３に固定される。
　図１Ｅに示すように、成長用基板１０を半導体基板２０から離す。電極２３に接触していなかったカーボンナノチューブ１５は、成長用基板１０に固定されたまま半導体基板２０から離れる。電極２３に固定されたカーボンナノチューブ１５は、成長用基板１５から剥離され、電極２３に固定された状態が維持される。
　実施例１では、ペースト状の導電性接着剤を用いないため、カーボンナノチューブ１５を電極２３に接触させても、接着剤が基板面内に広がることはない。また、半田を溶融させないため、溶融した半田が基板面内に広がることもない。このため、半導体基板２０の電極２３以外の領域に、カーボンナノチューブ１５が接着されてしまうことを防止することができる。
　実施例１では、電極２３にアルミニウムを用いたが、カーボンナノチューブ１５と合金化するその他の金属を用いてもよい。このような金属として、チタン（Ｔｉ）、モリブデン（Ｍｏ）、タングステン（Ｗ）、クロム（Ｃｒ）、ニッケル（Ｎｉ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、マグネシウム（Ｍｇ）等が挙げられる。また、こられの金属を主成分とする合金を用いることも可能である。
　図１Ｄに示した合金化工程においては、カーボンナノチューブ１５と電極２３とが合金化するのに十分な圧力を加える必要がある。カーボンナノチューブ１５と電極２３との接続強度が、成長用基板１０側のＮｉ膜１２とカーボンナノチューブ１５との接続強度よりも強くなるように、カーボンナノチューブ１５と電極２３との接触部を合金化する必要がある。
　次に、図２Ａ～図２Ｆを参照して、実施例２による半導体装置の製造方法について説明する。
　図２Ａに示した半導体基板２０、パッド２１、保護膜２２、及び電極２３は、図１Ｂに示した実施例１で用いたものと同一である。半導体基板２０を真空チャンバ内に配置し、半導体基板２０の上に、マスク４０を配置する。マスク４０には、電極２３に整合する開口４０Ａが形成されている。開口４０Ａの底面に、電極２３が露出する。電極２３が形成されていない領域は、マスク４０で覆われる。
　図２Ｂに示すように、電極２３の表面、及びマスク４０の表面に、アルミニウムを蒸着することにより、アルミニウム膜４１ａ及び４１ｂを形成する。なお、アルミニウム膜４１ａ及び４１ｂは、スパッタリングにより形成してもよい。アルミニウム膜４１ａ及び４１ｂの厚さは、例えば１μｍとする。電極２３と、その表面に堆積したアルミニウム膜４１ａとが、電極２３Ａを構成する。
　図２Ｃに示すように、半導体基板２０の上方に、カーボンナノチューブ１５が林立した成長用基板１０を、カーボンナノチューブ１５が半導体基板２０に対向するように配置する。カーボンナノチューブ１５の先端、電極２３Ａ、及びアルミニウム膜４１ｂに、アルゴンプラズマ３１を照射する。
　図２Ｄに示すように、成長用基板１０を半導体基板２０に近づけ、カーボンナノチューブ１５の先端を、マスク４０上のアルミニウム膜４１ｂに接触させる。さらに、成長用基板１０を半導体基板２０に押し付け、開口４０Ａが配置されている領域のカーボンナノチューブ１５の先端を、電極２３Ａの表面に接触させる。マスク４０上のアルミニウム膜４１ｂに接触しているカーボンナノチューブ１５は、弾性変形して撓む。例えば、１ｍｍ２の領域に、３～５Ｎの力を加えることにより、分布密度５×１０１０～１×１０１１本／ｃｍ２で林立しているカーボンナノチューブを約３０％撓ませることができる。ここで、「ｘ％撓む」とは、カーボンナノチューブの基部から先端までの直線距離が、カーボンナノチューブ自体の長さよりもｘ％短くなるように撓むことを意味する。
　カーボンナノチューブ１５と電極２３Ａとの接触部、及びカーボンナノチューブ１５とアルミニウム膜４１ｂとの接触部に、炭素とアルミニウムの合金が形成される。これにより、電極２３Ａに接触しているカーボンナノチューブ１５が、電極２３Ａに固定される。また、マスク４０上のアルミニウム膜４１ｂに接触しているカーボンナノチューブ１５は、マスク４０に固定される。
　図２Ｅに示すように、成長用基板１０を半導体基板１０に押し付けている力を解放する。撓んでいるカーボンナノチューブ１５の復元力により、成長用基板１０が半導体基板２０から浮き上がる。このとき、電極２３Ａに固定されているカーボンナノチューブ１５が、成長用基板１０から引き離され、半導体基板２０側に残る（転写される）。
　図２Ｆに示すように、成長用基板１０を半導体基板２０から離す。マスク４０がカーボンナノチューブ１５を介して成長用基板１０に接続されているため、マスク４０も、成長用基板１０と共に半導体基板２０から離される。
　実施例２においても、実施例１と同様に、半導体基板２０の電極２３Ａ以外の不要な領域に、カーボンナノチューブ１５が接着されてしまうことを防止することができる。また、実施例２では、図２Ｄに示した状態から、成長用基板１０を半導体基板２０に押し付けていた力を解放するのみで、成長用基板１０を半導体基板２０から引き離すことができる。このため、電極２３Ａに固定されたカーボンナノチューブ１５を成長用基板１０から引き剥がすための力を外部から付与する必要がない。
　図２Ｄに示した状態で、カーボンナノチューブ１５の撓み量が少なすぎると、その復元力によって成長用基板１０を半導体基板２０から引き離すことができなくなる。逆に、カーボンナノチューブ１５の撓み量が大きすぎると、成長用基板１０に過大な押し付け力を加えなければならなくなる。また、カーボンナノチューブ１５の撓みが弾性変形の限界を超えると、復元力を利用することができなくなる。これらを考慮して、カーボンナノチューブ１５が１０～３０％撓むように、カーボンナノチューブ１５の長さとマスク４０の厚さとを設定することが好ましい。すなわち、マスク４０の厚さを、カーボンナノチューブ１５の長さの１０～３０％の範囲内とすることが好ましい。
　次に、図３Ａ～図３Ｆを参照して、実施例３による半導体装置の製造方法について説明する。
　図３Ａに示した半導体基板２０、パッド２１、保護膜２２、及び電極２３は、図１Ｂに示した実施例１で用いたものと同一である。半導体基板２０の上に、マスク４０を配置する。マスク４０には、電極２３に整合する開口４０Ａが形成されている。開口４０Ａの底面に、電極２３が露出する。電極２３が形成されていない領域は、マスク４０で覆われる。
　図３Ｂに示すように、開口４０Ａ内の電極２３上にペースト状の導電性材料５１を堆積させる。導電性材料５１には、銀ペースト等の導電性樹脂や、半田ペースト等を用いることができる。導電性材料５１は、スキージを用いたスクリーン印刷法により堆積させることができる。
　図３Ｃに示すように、表面上にカーボンナノチューブ１５が林立した成長用基板１０を半導体基板２０に対向させる。カーボンナノチューブ１５の先端がマスク４０に接触した後、成長用基板１０を半導体基板２０に押し付ける。マスク４０に接触しているカーボンナノチューブ１５が撓み、開口４０Ａが形成されている領域のカーボンナノチューブ１５の先端が、ペースト状の導電性材料５１内に侵入する。このとき、導電性材料５１が開口４０Ａから溢れないように、導電性材料５１の堆積量が調整されている。
　この状態で半導体基板２０を加熱することにより、導電性材料５１を硬化させる。加熱温度は、導電性材料５１のバインダ樹脂に依存する。例えば、エポキシ系樹脂を用いている場合には、加熱温度を１５０～２００℃とし、ポリイミド系樹脂を用いている場合には、加熱温度を２００～２５０℃とする。導電性材料５１が硬化することにより、カーボンナノチューブ１５が電極２３に固定される。マスク４０には、この加熱温度に耐えることができる程度の耐熱性を持つ材料が用いられる。
　図３Ｄに示すように、成長用基板１０を半導体基板２０に押し付けている力を解放する。撓んでいたカーボンナノチューブ１５の復元力により、成長用基板１０が半導体基板２０から浮き上がる。このとき、電極２３に固定されているカーボンナノチューブ１５が、成長用基板１０から剥離され、半導体基板２０側に残る（転写される）。
　図３Ｅに示すように、成長用基板１０を半導体基板２０から離す。電極２３に固定されているカーボンナノチューブ１５は、既に成長用基板１０から引き剥がされているため、成長用基板１０を半導体基板２０から容易に離すことができる。図３Ｆに示すように、マスク４０を半導体基板２０から離す。
　実施例３では、図３Ｃに示したように、ペースト状の導電性材料５１がマスク４０に形成された開口４０Ａ内に装填されている。このため、導電性材料５１が基板面内の電極２３が形成されていない領域まで広がることを防止することができる。
　マスク４０に、炭素と化合物を生成する材料を用いると、図３Ｃに示した工程において、カーボンナノチューブ１５がマスク４０に固定されることが懸念される。マスク４０に、炭素と化合物を生成しない材料を用いることにより、図３Ｅに示した工程において、成長用基板１０をマスク４０から容易に引き離すことができる。また、マスク４０の厚さは、実施例２の場合と同様に、カーボンナノチューブ１５の長さの１０～３０％の範囲内とすることが好ましい。
　図４Ａ～図４Ｑを参照して、実施例４による半導体装置の製造方法について説明する。
　図４Ａに示す成長用基板１０、Ｔｉ膜１１、Ｎｉ膜１２、及びカーボンナノチューブ１５は、実施例１で用いた図１Ａのものと同一の構成である。カーボンナノチューブ１５の先端に、例えばスパッタリングにより下地金属及び表層金属を順番に付着させる。
　図４Ｂに、カーボンナノチューブ１５の先端の拡大断面図を示す。カーボンナノチューブ１５の先端に、先端金属部材５７が付着している。先端金属部材５７は、カーボンナノチューブ１５の先端の表面を覆う下地膜５５と、その表面を覆う表層膜５６の２層で構成される。なお、図４Ｃに示すように、下地膜５５は、カーボンナノチューブ１５の先端の表面を連続的に被覆することなく、離散的に分布する場合もある。このとき、表層膜５６は、離散的に分布している下地膜５５の各々の表面に付着する。
　下地膜５５には、カーボンと合金を形成する金属、例えばＴｉ、Ｗ、Ｃｒ等が用いられる。表層膜５６には、下地膜５５の金属よりも柔らかい金属、例えばＡｌ、Ａｕ等が用いられる。一例として、カーボンナノチューブ１５の太さは５～１０ｎｍであり、下地膜５５及び表層膜５６の各々の厚さは、カーボンナノチューブ１５の直径の約半分である。
　カーボンナノチューブ１５の間隔が３０ｎｍ～１００ｎｍ程度であるため、相互に隣り合うカーボンナノチューブ１５の先端に付着している先端金属部材５７同士が連続して１枚の膜を構成することはない。
　下地膜５５及び表層膜５６の成膜時に、スパッタリングのターゲットに対して、成長用基板１０を傾けてもよい。成長用基板１０を傾けると、付着すべき金属原子がカーボンナノチューブ１５の根元まで到達しにくくなる。これにより、カーボンナノチューブ１５の先端に、効果的に金属を付着させることができる。また、スパッタリング時に、成長用基板１０を、その表面に沿って自転させてもよい。成長用基板１０を自転させることにより、先端金属部材５７が一方向に偏って付着することを防止できる。
　図４Ｄに、カーボンナノチューブを接着させる電極が設けられた第１の基板６６の断面図を示す。半導体基板６０の表面に、ＭＯＳＦＥＴ等の電子回路素子が形成されている。電子回路素子が形成された表面の上に、多層配線層６１が形成されている。多層配線層６１の上に、複数の電極６２が形成されている。半導体基板６０の裏側の表面から、半導体基板６０及び多層配線層６１を貫通して表側の電極６２の底面に達する貫通ビアホール６３が形成されている。
　貫通ビアホール６３の側面、及び半導体基板６０の裏側の表面に、絶縁膜６４が形成されている。貫通ビアホール６３内に、垂直接続部材６５が充填されている。垂直接続部材６５は、表側の電極６２に接続される。このように、半導体基板６０の裏側の表面から、表側の電極６２まで達する垂直接続部材６５を含む基板の作製方法は、例えば国際公開公報ＷＯ２００４／０６４１５９に開示されている。
　図４Ｅに示すように、第１の基板６６の裏側の表面に、第１のメタルマスク６８を配置する。第１のメタルマスク６８には、垂直接続部材６５に対応する開口が設けられている。第１のメタルマスク６８の開口内に露出している垂直接続部材６５の表面に、アルミニウム等の金属膜７０を、スパッタリング、蒸着等により形成する。金属膜７０の厚さは、例えば１～２μｍである。第１のメタルマスク６８の表面にも、金属膜７０が付着する。
　図４Ｆに示すように、第１のメタルマスク６８を第１の基板６６から取り外す。垂直接続部材６５の表面には、金属膜７０が残る。
　図４Ｇに示すように、第１の基板６６の裏側の表面に、第２のメタルマスク７３を配置する。第２のメタルマスク７３には、図４Ｅに示した第１のメタルマスク６８と同様に、垂直接続部材６５に対応する開口が設けられている。図４Ａに示した成長用基板１０のカーボンナノチューブ１５が林立する面と、第１の基板６６の裏側の表面とが対向するように、第１の基板６６と成長用基板１０とを、相互に間隔を隔てて配置する。両者の対向する表面にＡｒプラズマ３１を照射する。これにより、金属膜７０の表面、及び先端金属部材５７の表面の金属酸化物や汚染物が除去され、金属表面が活性化する。
　図４Ｈに示すように、成長用基板１０を第１の基板６６に近づけ、カーボンナノチューブ１５の先端の先端金属部材５７をメタルマスク７３に接触させる。さらに、カーボンナノチューブ１５が撓むまで加圧し、先端金属部材５７を金属膜７０に接触させる。この状態で、第１の基板６６を３００℃程度まで加熱する。これにより、先端金属部材５７の表層膜５６が、金属膜７０に接合される。
　相互に隣り合うカーボンナノチューブ１５の先端に付着した先端金属部材５７同士が、相互に連続して膜状になると、カーボンナノチューブ１５が第２のメタルマスク７３の開口内に侵入し難くなる。先端金属部材５７を金属膜７０に接触させるために、先端金属部材５７を、相互に隣り合うカーボンナノチューブ１５に付着した先端金属部材５７同士が連続しない程度の薄さにすることが好ましい。
　図４Ｉに示すように、カーボンナノチューブ１５の先端の表層膜５６が、圧力及び熱により、金属膜７０の表面に倣うように変形し、表層膜５６と金属膜７０との接触面積が増大する。図４Ｊに示すように、先端金属部材５７が離散的に付着している場合でも、金属膜７０に接触した部分の表層膜５６が変形することにより、金属膜７０と表層膜５６との接触面積が増大する。
　カーボンナノチューブ１５は、巨視的には湾曲等の変形が生じやすいが、微視的には変形しにくい。このため、カーボンナノチューブ１５が金属膜７０に直接接触する場合には、両者の接触は、ほぼ点接触となる。実施例４において、表層膜５６と金属膜７０との接触面積が増大することにより、カーボンナノチューブ１５が金属膜７０に、より強固に固定される。
　図４Ｋに示すように、成長用基板１０を第１の基板６６から引き離す。先端金属部材５７が金属膜７０に接触していたカーボンナノチューブ１５は、成長用基板１０から脱離し、半導体基板７０側に固定（転写）される。転写されたカーボンナノチューブ１５の先端（成長用基板１０に付着していた端部）は、カーボンが露出した状態になる。先端金属部材５７がメタルマスク７３に接触していたカーボンナノチューブ１５は、成長用基板１０に残ったままである。
　図４Ｌに示すように、第１の基板６６に転写されたカーボンナノチューブ１５の先端に、先端金属部材８５を付着させる。先端金属部材８５は、図４Ｉまたは図４Ｊに示した先端金属部材５７と同様に、下地膜と表層膜との２層構造を有する。下地膜と表層膜の材料は、先端金属部材５７のものと同じである。
　図４Ｍに示すように、第１の基板６６に接続すべき第２の基板６６ａを準備する。第２の基板６６ａは、図４Ｄに示した第１の基板６６と同様に、半導体基板６０ａ、多層配線層６１ａ、電極６２ａ、貫通ビアホール６３ａ、絶縁膜６４ａ、及び垂直接続部材６５ａを含む。電極６２ａは、例えばアルミニウムで形成される。
　図４Ｎに示すように、第１の基板６６の裏側の表面と、第２の基板６６ａの表側の表面とが対向するように、両者を間隔を隔てて配置する。第１の基板６６と第２の基板６６ａとの相互に対向する面に、Ａｒプラズマ３１を照射する。これにより、先端金属部材８５の表面、及び電極６２ａの表面の活性化が行われる。
　図４Ｏに示すように、第１の基板６６と第２の基板６６ａとを近づけて、カーボンナノチューブ１５の先端金属部材８５を電極６２ａに接触させる。圧力及び熱を加えることにより、先端金属部材８５を電極６２ａに接合させる。第１の基板６６と第２の基板６６ａとの間隔は、例えば１０μｍ～５０μｍ程度である。
　図４Ｐに示すように、第２の基板６６ａの裏側の表面に、第３の基板６６ｂを接続する。第３の基板６６ｂの表側の面には、電極６２ｂが形成され、第２の基板６６ａの裏側の表面には、金属膜７０ａが形成されている。両者が、カーボンナノチューブ１５ａにより、機械的及び電気的に接続される。第３の基板６６ｂの接続には、第１の基板６６に第２の基板６６ａを接続する方法と同じ方法が適用される。
　図４Ｑに示すように、第１の基板６６と第２の基板６６ａとの間、及び第２の基板６６ａと第３の基板６６ｂとの間に、それぞれ樹脂８０ａ及び８０ｂを充填する。充填される樹脂８０ａ及び８０ｂには、例えばエポキシ、シアネートエステル、ベンゾシクロブテン等が用いられる。これらの樹脂の充填は、例えば、３次元実装された基板を、減圧下で樹脂溶液中に浸漬させ、その後常圧に戻すことにより行われる。
　上記実施例４で示した第１の基板６６及び第２の基板６６ａにおいては、垂直接続部材６５、６５ａが、半導体基板６０、６０ａの裏側の表面から、多層配線層６１、６１ａを貫通して、表側の電極６２、６２ａまで達している。基板の表側の電極と裏側の電極とを電気的に接続する構造として、他の構造を有する基板を用いることも可能である。
　図５に、基板の表側の電極と裏側の電極とを他の構造で電気的に接続した基板を３次元実装した例を示す。垂直接続部材９５、９５ａは、半導体基板６０、６０ａを貫通するが、多層配線層６１、６１ａは貫通しない。垂直接続部材９５、９５ａは、多層配線層６１、６１ａ内の配線、プラグ等を介して、表側の電極６２、６２ａに接続される。垂直接続部材９５、９５ａの裏側の表面には、金属膜７０、７０ａが形成されている。このような垂直接続部材９５、９５ａは、例えば表側の表面に開口を持つ有低の凹部内に導電部材を充填した後、裏側の表面から、導電部材が露出するまで化学機械研磨を行うことにより形成される（例えば、国際公開公報ＷＯ２００５／１１９７７６、特開平１１－２６１００１号公報等）。
　実施例４においては、図４Ｉ及び図４Ｊに示したように、先端金属部材５７が変形することによって、カーボンナノチューブ１５と金属膜７０との機械的な接合強度が高まるとともに、電気的な接触抵抗が低下する。
　次に、先端金属部材５７の下地膜５５及び表層膜５６に用いられる好ましい材料について説明する。下地膜５５には、表層膜５６とカーボンナノチューブ１５との密着性を高めることができる金属を用いることが好ましい。このような金属として、カーボンと合金を形成する金属、例えばＴｉ、Ｗ、Ｃｒ等が挙げられる。表層膜５６には、接合すべき電極との接触面を増大するために、下地膜５５に用いられている金属よりも柔らかい金属を用いることが好ましい。また、Ｃｕと同一か、またはＣｕよりも柔らかい金属を用いることが、より好ましい。このような金属として、Ａｌ、Ａｕ等が挙げられる。また、酸化され難いという点で、Ａｕがより好ましい。
　実施例４では、図４Ｇに示したように、金属膜７０を形成し、先端金属部材５７を付着させた後、Ａｒプラズマによって、両者の表面を活性化した。金属膜７０の成膜後、及び先端金属部材５７を付着させた後、真空雰囲気を維持したまま両者を接合させる場合には、Ａｒプラズマによる処理を行わなくてもよい。
　以上実施例に沿って本発明を説明したが、本発明はこれらに制限されるものではない。例えば、種々の変更、改良、組み合わせ等が可能なことは当業者に自明であろう。

Claims (10)

  1. 　半導体基板の表面の一部の領域に形成されている電極と、成長用基板の表面に林立した複数の導電性ナノチューブの先端とを、希ガスプラズマに晒す工程と、
    　前記希ガスプラズマに晒された前記導電性ナノチューブの先端を、前記電極に接触させ、該導電性ナノチューブを該電極に固定する工程と、
    　前記成長用基板を、前記半導体基板から離し、前記電極に固定された導電性ナノチューブを前記半導体基板側に残す工程と
    を有する半導体装置の製造方法。
  2. 　前記電極を前記希ガスプラズマに晒す前に、前記電極が形成されている表面上に、該電極に対応する開口が形成されたマスクを配置し、
    　前記希ガスプラズマに晒す工程において、該マスクの表面と、該マスクの開口内に露出している該電極の表面とを前記希ガスプラズマに晒し、
    　前記導電性ナノチューブを固定する工程において、前記マスクの開口が配置されている領域の前記導電性ナノチューブを、該開口を通して前記電極に接触させると共に、前記開口が配置されていない領域の前記導電性ナノチューブを、前記マスクに押し付けることによって撓ませ、
    　前記成長用基板を前記半導体基板から離す工程が、前記マスクを前記半導体基板から離す工程を含む請求項１に記載の半導体装置の製造方法。
  3. 　前記マスクの厚さが、前記導電性ナノチューブの長さの１０～３０％の範囲内である請求項２に記載の半導体装置の製造方法。
  4. 　前記導電性ナノチューブと前記電極との接触部分において、前記導電性ナノチューブの材料と前記電極の材料とを合金化することにより、該導電性ナノチューブを該電極に固定する請求項１乃至３のいずれか１項に記載の半導体装置の製造方法。
  5. 　前記導電性ナノチューブの先端を希ガスプラズマに晒す前に、該導電性ナノチューブの先端に、下地膜及び表層膜がこの順番に積層された先端金属部材を形成する工程を有し、
    　前記下地膜は、前記導電性ナノチューブと前記表層膜との密着性を高める性質を有する金属で形成され、前記表層膜は、前記下地膜よりも柔らかい金属で形成されており、
    　前記希ガスプラズマに晒す工程において、前記先端金属部材が前記希ガスプラズマに晒される請求項１乃至４のいずれか１項に記載の半導体装置の製造方法。
  6. 　前記下地膜及び前記表層膜は、ターゲットに対して前記成長用基板を傾けた状態でスパッタリングにより形成する請求項５に記載の半導体装置の製造方法。
  7. 　前記成長用基板を自転させながら、スパッタリングにより前記下地膜及び前記表層膜を形成する請求項５または６に記載の半導体装置の製造方法。
  8. 　表面の一部の領域に電極が形成されている半導体基板の該表面上に、該電極に対応する開口が形成されたマスクを配置する工程と、
    　前記マスクの開口の底面に露出した前記電極の上に、導電性材料を堆積させる工程と、
    　表面に複数の導電性ナノチューブが林立した成長用基板を、前記半導体基板に対向させ、前記マスクの開口が配置されている領域の前記導電性ナノチューブを、該開口内に堆積している前記導電性材料に接触させると共に、該開口が配置されていない領域の前記導電性ナノチューブを前記マスクに押し付けて撓ませる工程と、
    　前記導電性材料に接触している前記導電性ナノチューブを、該導電性材料に固定する工程と、
    　前記成長用基板を前記半導体基板から離し、前記導電性材料に固定された導電性ナノチューブを前記半導体基板側に残す工程と、
    　前記マスクを前記半導体基板から離す工程と
    を有する半導体装置の製造方法。
  9. 　前記導電性材料が導電性ペーストまたは半田ペーストである請求項８に記載の半導体装置の製造方法。
  10. 　成長用基板の表面に林立した複数の導電性ナノチューブの先端に、下地膜及び表層膜がこの順番に積層された先端金属部材を形成する工程と、
    　半導体基板の表面の一部の領域に形成されている電極に、前記先端金属部材を接触させ、前記導電性ナノチューブを前記電極に固定する工程と、
    　前記成長用基板を前記半導体基板から離し、前記電極に固定された導電性ナノチューブを前記半導体基板側に残す工程と
    を有し、
    　前記下地膜は、前記導電性ナノチューブと前記表層膜との密着性を高める性質を有する金属で形成され、前記表層膜は、前記下地膜よりも柔らかい金属で形成されている半導体装置の製造方法。
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