WO2011145159A1 - 半導体装置及びその製造方法 - Google Patents

半導体装置及びその製造方法 Download PDF

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Publication number
WO2011145159A1
WO2011145159A1 PCT/JP2010/007010 JP2010007010W WO2011145159A1 WO 2011145159 A1 WO2011145159 A1 WO 2011145159A1 JP 2010007010 W JP2010007010 W JP 2010007010W WO 2011145159 A1 WO2011145159 A1 WO 2011145159A1
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Prior art keywords
electrode
semiconductor substrate
semiconductor device
film
end portion
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PCT/JP2010/007010
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English (en)
French (fr)
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青井信雄
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パナソニック株式会社
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    • H01L27/04—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body
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Definitions

  • the present invention relates to a semiconductor device and a manufacturing method thereof, and more particularly to a chip-chip stacking, a chip-wafer stacking or a wafer-wafer stacking semiconductor device and a manufacturing method thereof.
  • FIGS. 6A to 6D A conventional method for laminating semiconductor substrates is shown in FIGS. 6A to 6D (see, for example, Non-Patent Document 1).
  • a first silicon substrate 11 is prepared in which the bottom of the through silicon via 12 is exposed on the back surface (opposite surface of the circuit formation surface) 11b side.
  • a transistor 16 and a wiring layer 17 having a multi-layer wiring electrically connected to the through silicon via 12 and the transistor 16 are formed. Yes.
  • the sidewall surface of the through silicon via 12 is covered with an insulating film 18 with a barrier film (not shown) interposed therebetween, and the back surface 11 b of the first silicon substrate 11 is covered with a protective insulating film 19.
  • an insulating adhesive 13 is formed on the protective insulating film 19 and the exposed bottom of the through silicon via 12 by a spin coating method, and then pre-baked.
  • a second silicon substrate 14 having a front surface (circuit forming surface) 14a and a back surface (opposite surface of the circuit forming surface) 14b is prepared.
  • a transistor 20 and a wiring layer 21 having a multilayer wiring electrically connected to the transistor 20 are formed on the surface (circuit formation surface) 14 a of the second silicon substrate 14.
  • a metal electrode portion 15 is formed on the outermost surface portion of the wiring layer 21.
  • the metal electrode portion 15 of the second silicon substrate 14 joined to the through silicon via 12 of the first silicon substrate 11 is opposed to the through silicon via 12.
  • the first silicon substrate 11 and the second silicon substrate 14 are arranged to face each other with the insulating adhesive 13 interposed therebetween.
  • the first silicon substrate 11 and the second silicon substrate 14 are pressure-bonded in order to bond the first silicon substrate 11 and the second silicon substrate 14 together.
  • the insulating adhesive 13 is cured.
  • the insulating adhesive 13 is interposed between the through silicon via 12 and the metal electrode portion 15, but the silicon shown in FIG.
  • the insulating adhesive 13 interposed between the through via 12 and the metal electrode portion 15 is pushed out to the periphery, and the through silicon via 12 and the metal electrode portion 15 are directly connected.
  • the thermal conductivity of the adhesive connecting the semiconductor substrates is low and the heat dissipation efficiency is poor.
  • the heat generated by the operation of the transistors integrated in the logic LSI chip is accumulated in the vicinity of the heat generating portion of the logic LSI chip, causing a temperature rise, resulting in an operation failure or a reliability failure. there were.
  • an object of the present invention is to provide a semiconductor device having a three-dimensional stacked structure capable of efficiently dissipating heat generated from the semiconductor device, and a method for manufacturing the same.
  • the present inventor has proposed a resin containing carbon nanotubes as a filler (filler), which has been proposed as a high heat conductive material for heat dissipation in a packaged semiconductor device or the like (for example, Patent Documents). 1)).
  • the carbon nanotube is a general term for a material in which a sheet of a six-membered ring network formed by carbon atoms is formed into a single-layer or multi-layer coaxial tube. These are called multi-walled carbon nanotubes, but all have the feature of extremely high thermal conductivity.
  • carbon nanotubes have electrical conductivity. Specifically, as the single-walled carbon nanotube, those showing metallic properties and those showing semiconductor properties are mixed in the manufacturing process, and it is difficult to separate them. Multi-walled carbon nanotubes exhibit metallic properties.
  • the inventor of the present application for example, using an adhesive containing conductive carbon nanotubes as a filler, or a heat dissipation member containing conductive carbon nanotubes, The inventors have invented a semiconductor device having a three-dimensional stacked structure that can efficiently dissipate heat generated from the semiconductor device while preventing leakage current between the electrodes, and a manufacturing method thereof.
  • a first semiconductor device includes a first semiconductor substrate and a second semiconductor substrate that are bonded to each other by an adhesive, and a surface of the first semiconductor substrate that faces the second semiconductor substrate. And a second electrode provided such that at least the end portion is exposed on a surface of the second semiconductor substrate facing the first semiconductor substrate.
  • An electrode, the end of the first electrode and the end of the second electrode are connected to each other, the adhesive contains carbon nanotubes, and the first electrode It is formed in a region excluding the connection portion between the end portion and the end portion of the second electrode and the vicinity thereof.
  • the first semiconductor substrate and the second semiconductor substrate are bonded together using an adhesive containing carbon nanotubes, and the adhesive is attached to each semiconductor substrate. It is formed away from the electrode. Therefore, it is possible to obtain a semiconductor device having a three-dimensional laminated structure that can efficiently dissipate heat generated from the semiconductor device while preventing leakage current between electrodes, that is, a highly reliable three-dimensional laminated chip having no malfunction. Can do.
  • the adhesive is provided at least 2 ⁇ m or more away from the connection portion between the end portion of the first electrode and the end portion of the second electrode. Also good. In this way, it is possible to separate the adhesive containing carbon nanotubes from the electrodes of each semiconductor substrate while ensuring a sufficient margin in consideration of the substrate alignment accuracy, lithography accuracy, and the like.
  • the length of the carbon nanotube is determined by the connection between the end of the first electrode and the end of the second electrode, and the adhesive. It may be less than half of the separation distance. In this way, when the adhesive containing the carbon nanotubes is selectively removed from the connection part between the electrodes of each semiconductor substrate and the vicinity thereof, even if the carbon nanotubes remain in the connection part and the vicinity thereof, Generation of leakage current between the electrodes can be reliably prevented.
  • a carbon nanotube is not included between the connection portion between the end portion of the first electrode and the end portion of the second electrode and the adhesive.
  • An insulating adhesive may be further filled. In this way, it is possible to reliably prevent leakage current between the electrodes due to the carbon nanotubes.
  • the insulating adhesive may also be formed between the second semiconductor substrate and the adhesive.
  • the adhesive may have photosensitivity. If it does in this way, the adhesive agent containing a carbon nanotube can be selectively removed from the connection part of the electrodes of each semiconductor substrate, and its vicinity using lithography and image development processing.
  • the carbon nanotube may be a single-walled carbon nanotube, a multi-walled carbon nanotube, or a mixture thereof.
  • the first electrode may be a through electrode penetrating the first semiconductor substrate.
  • the first method for manufacturing a semiconductor device includes a step (a) of preparing a first semiconductor substrate in which at least an end portion of the first electrode is exposed on the surface; A step (b) of forming an adhesive film containing carbon nanotubes on the surface of the first semiconductor substrate excluding the end portion and the vicinity thereof; and after the step (b), the second electrode A second semiconductor substrate having at least an end portion exposed on the surface is prepared, and the end portion of the first electrode and the end portion of the second electrode are connected to each other. A step (c) of bonding the substrate and the second semiconductor substrate together with the adhesive film.
  • the first semiconductor substrate and the second semiconductor substrate are bonded together using an adhesive containing carbon nanotubes, and the adhesive is applied to each of the adhesives. It is formed away from the electrodes of the semiconductor substrate. Therefore, it is possible to obtain a semiconductor device having a three-dimensional laminated structure that can efficiently dissipate heat generated from the semiconductor device while preventing leakage current between electrodes, that is, a highly reliable three-dimensional laminated chip having no malfunction. Can do.
  • a step (d) of forming a conductive adhesive film may be further provided. In this way, it is possible to reliably prevent leakage current between the electrodes due to the carbon nanotubes. Further, in this case, a portion other than the portion formed in the vicinity of the end portion of the first electrode in the insulating adhesive film between the step (d) and the step (c).
  • the method may further include a step (e) of removing.
  • the adhesive may have photosensitivity. If it does in this way, the adhesive agent containing a carbon nanotube can be selectively removed from the connection part of the electrodes of each semiconductor substrate, and its vicinity using lithography and the image development process.
  • the carbon nanotube may be a single-walled carbon nanotube, a multi-walled carbon nanotube, or a mixture thereof.
  • the first electrode may be a through electrode penetrating the first semiconductor substrate.
  • a second semiconductor device includes at least a first semiconductor substrate and a second semiconductor substrate bonded to each other with an adhesive, and a surface of the first semiconductor substrate that faces the second semiconductor substrate.
  • a first electrode provided such that an end portion is exposed; and a second electrode provided such that at least the end portion is exposed on a surface of the second semiconductor substrate facing the first semiconductor substrate; And the end portion of the first electrode and the end portion of the second electrode are connected to each other, and between the first semiconductor substrate or the second semiconductor substrate and the adhesive
  • a carbon nanotube-containing film is formed in a region excluding the connection portion between the end portion of the first electrode and the end portion of the second electrode and the vicinity thereof.
  • the carbon nanotube-containing film is separated from the electrode of each semiconductor substrate between the first semiconductor substrate or the second semiconductor substrate and the adhesive that bonds the two substrates together. Forming. Therefore, it is possible to obtain a semiconductor device having a three-dimensional laminated structure that can efficiently dissipate heat generated from the semiconductor device while preventing leakage current between electrodes, that is, a highly reliable three-dimensional laminated chip having no malfunction. Can do.
  • the carbon nanotube-containing film is provided at least 2 ⁇ m away from the connection portion between the end portion of the first electrode and the end portion of the second electrode. It may be. In this way, the carbon nanotube-containing film can be separated from the electrodes of each semiconductor substrate while ensuring a sufficient margin in consideration of substrate alignment accuracy, lithography accuracy, and the like.
  • the length of the carbon nanotubes included in the carbon nanotube-containing film is the connecting portion between the end portion of the first electrode and the end portion of the second electrode. And a half or less of the separation distance from the carbon nanotube-containing film. In this way, when the carbon nanotube-containing film is selectively removed from the connection portion between the electrodes of each semiconductor substrate and the vicinity thereof, even if carbon nanotubes remain in the connection portion and the vicinity thereof, Leakage current generation can be reliably prevented.
  • the carbon nanotubes contained in the carbon nanotube-containing film may be single-walled carbon nanotubes, multi-walled carbon nanotubes, or a mixture thereof.
  • the first electrode may be a through electrode penetrating the first semiconductor substrate.
  • the method for manufacturing a second semiconductor device includes a step (a) of preparing a first semiconductor substrate having at least an end portion of the first electrode exposed on the surface, and the end portion of the first electrode.
  • the insulating adhesive film connects the first semiconductor substrate and the second semiconductor substrate so that the end portion of the first electrode and the end portion of the second electrode are connected to each other.
  • the carbon nanotube-containing film is formed from the electrode of each semiconductor substrate between the first semiconductor substrate or the second semiconductor substrate and the adhesive that bonds the two substrates. They are separated from each other. Therefore, it is possible to obtain a semiconductor device having a three-dimensional laminated structure that can efficiently dissipate heat generated from the semiconductor device while preventing leakage current between electrodes, that is, a highly reliable three-dimensional laminated chip having no malfunction. Can do.
  • the carbon nanotubes contained in the carbon nanotube-containing film may be single-walled carbon nanotubes, multi-walled carbon nanotubes, or a mixture thereof.
  • the first electrode may be a through electrode penetrating the first semiconductor substrate.
  • the heat generated from the semiconductor device can be efficiently radiated while preventing leakage current between the electrodes.
  • a semiconductor device having a stacked structure and a method for manufacturing the same can be realized, whereby a highly reliable three-dimensional stacked chip without malfunction can be obtained.
  • FIGS. 1A to 1D are cross-sectional views showing respective steps of the semiconductor device manufacturing method according to the first embodiment.
  • FIG. 2A is a diagram showing a cross-sectional configuration of a three-dimensional multilayer chip in which an adhesive containing carbon nanotubes is formed also in the connection portion between electrodes of each semiconductor substrate and in the vicinity thereof as a comparative example.
  • FIG. 2B is a diagram showing a cross-sectional configuration of the three-dimensional multilayer chip formed by the method for manufacturing the semiconductor device according to the first embodiment.
  • 3A to 3F are cross-sectional views showing respective steps of a method for manufacturing a semiconductor device according to a modification of the first embodiment.
  • FIG. 1A to 1D are cross-sectional views showing respective steps of the semiconductor device manufacturing method according to the first embodiment.
  • FIGS. 5A to 5E are cross-sectional views showing respective steps of the semiconductor device manufacturing method according to the second embodiment.
  • 6A to 6D are cross-sectional views showing respective steps of a conventional method for manufacturing a semiconductor device.
  • FIGS. 1A to 1D are cross-sectional views showing respective steps of a semiconductor device manufacturing method according to the first embodiment.
  • a first semiconductor substrate (for example, a silicon substrate) 101 in which the bottom of the through via 104 is exposed on the back surface (opposite surface of the circuit formation surface) 101b side is prepared.
  • a transistor 102 and a wiring layer 103 having a multilayer via that is electrically connected to the through via 104 and the transistor 102 are formed on the surface (circuit formation surface) 101 a of the first semiconductor substrate 101.
  • the through via 104 penetrates the first semiconductor substrate 101 and reaches the wiring layer 103, and the side wall surface of the through via 104 is covered with an insulating film 105 with a barrier film (not shown) interposed therebetween.
  • the back surface 101 b of the first semiconductor substrate 101 is covered with a protective insulating film 106.
  • the first semiconductor substrate 101 is provided with a plurality of through vias 104.
  • a negative photosensitive divinylsiloxane-bis-benzocyclo in which single-walled carbon nanotubes are dispersed on the protective insulating film 106 and the exposed bottom of the through via 104, for example, a negative photosensitive divinylsiloxane-bis-benzocyclo in which single-walled carbon nanotubes are dispersed.
  • a 1,3,5-trimethylbenzene solution of butene (BCB) monomer (for example, the concentration of BCB monomer is 20 to 40% by mass and the concentration of single-walled carbon nanotubes is 1 to 40% by mass) is applied, for example, by spin coating. After coating at a thickness of about 5 ⁇ m, pre-baking is performed at 90 ° C. for 90 seconds, for example, to form the BCB monomer film 107.
  • BCB butene
  • a region near the through via 104 (that is, formed on the second semiconductor substrate 111 prepared in a later step and bonded to the through via 104 by a lithography process).
  • a polymerization reaction is caused to form a BCB film 107A insoluble in the developer.
  • the BCB monomer film 107 located in the vicinity region 108 of the through via 104 that is, the BCB monomer film 107 formed on and near the exposed bottom of the through via 104 is dissolved and removed by the developer.
  • a second semiconductor substrate (for example, a silicon substrate) 111 having a front surface (circuit forming surface) 111a and a back surface (opposite surface of the circuit forming surface) 111b is prepared.
  • the transistor 112 and a wiring layer 113 having a multilayer wiring electrically connected to the transistor 112 are formed.
  • an electrode portion 114 made of, for example, metal is formed on the outermost surface portion of the wiring layer 113.
  • a BCB film is used to bond the first semiconductor substrate 101 and the second semiconductor substrate 111 so that the through via 104 and the electrode portion 114 are connected.
  • the BCB film 107A is cured for about 1 hour at a temperature of about 350 ° C., for example. To do.
  • the semiconductor device of this embodiment is completed.
  • the BCB monomer film 107 formed on and near the exposed bottom of the through via 104 is dissolved and removed by the developer, the carbon nanotubes contained in the BCB monomer film 107 are also exposed to the through via 104. It has been removed from and near the bottom. For this reason, it is possible to prevent the through vias 104 from being electrically connected to each other through the carbon nanotubes and thus the insulating property is deteriorated.
  • the first semiconductor substrate 101 and the second semiconductor substrate 111 are bonded to each other using the BCB film 107A that is an adhesive containing carbon nanotubes, and the adhesive is applied to each of the adhesives. It is formed away from the electrodes of the semiconductor substrate. Therefore, it is possible to obtain a semiconductor device having a three-dimensional laminated structure that can efficiently dissipate heat generated from the semiconductor device while preventing leakage current between electrodes, that is, a highly reliable three-dimensional laminated chip having no malfunction. Can do.
  • FIG. 2A shows, as a comparative example, an adhesive (BCB film 107A) containing carbon nanotubes at the connection portion between the electrodes (through via 104 and electrode portion 114) of each of the semiconductor substrates 101 and 111 and in the vicinity thereof.
  • FIG. 2B shows the cross-sectional configuration of the three-dimensional multilayer chip formed by the manufacturing method of the present embodiment described above.
  • the carbon nanotube 115 contained in the adhesive has a risk of bridging between adjacent electrodes. There is a concern that leakage current may occur.
  • the adhesive (BCB film 107A) around the electrodes (through vias 104 and electrode portions 114) of the semiconductor substrates 101 and 111 is removed by patterning. Therefore, it is possible to prevent leakage current between the electrodes due to the carbon nanotube 115 contained in the adhesive.
  • the through via 104 is used as the electrode formed on the back surface (opposite surface of the circuit formation surface) 101b of the first semiconductor substrate 101.
  • it is formed by another method.
  • an electrode such as a bump made of metal may be used.
  • a through via may be formed instead of the electrode portion 114.
  • a photosensitive BCB film is used as an adhesive between the first semiconductor substrate 101 and the second semiconductor substrate 111.
  • the type of adhesive is particularly limited as long as it has insulating properties. It is not limited.
  • single-walled carbon nanotubes are used as carbon nanotubes contained as a filler in the adhesive between the first semiconductor substrate 101 and the second semiconductor substrate 111.
  • multi-walled carbon nanotubes or single-walled carbon nanotubes are used. A mixture of carbon nanotubes and multi-walled carbon nanotubes may be used.
  • the BCB film 107A which is an adhesive between the first semiconductor substrate 101 and the second semiconductor substrate 111, is separated from the connection portion between the through via 104 and the electrode portion 114 by at least 2 ⁇ m or more. It is preferable to be provided. In this way, it is possible to separate the adhesive (BCB film 107A) containing carbon nanotubes from the electrodes of each semiconductor substrate while ensuring a sufficient margin in consideration of the substrate alignment accuracy, lithography accuracy, and the like. Needless to say, when the electrode portion 114 is larger than the through via 104 as in the present embodiment, it is preferable that the BCB film 107 ⁇ / b> A is provided so as not to contact the electrode portion 114.
  • the length of the carbon nanotube included in the BCB film 107A is sufficiently smaller than the size of the vicinity region 108 of the through via 104 where the BCB monomer film 107 is developed and removed.
  • the length of the carbon nanotubes included in the BCB film 107A is preferably less than or equal to half the distance between the connection portion between the through via 104 and the electrode portion 114 and the BCB film 107A.
  • the length of the carbon nanotube contained in the BCB film 107A is the width of the removal region of the BCB monomer film 107.
  • the carbon nanotubes remain on the first semiconductor substrate 101 in the removal region when the BCB monomer film 107 is removed, leakage current between electrodes, that is, insulation failure occurs. Can be sufficiently suppressed.
  • the BCB monomer film 107 is removed by performing plasma ashing for a short time after removing the BCB monomer film 107 on and near the connection portion between the through via 104 and the electrode portion 114 using lithography and development processing. The carbon nanotubes remaining in the region can be removed almost completely.
  • the spin coating method is used for forming the BCB monomer film 107, but it is also possible to use an ink jet printing method or the like instead. In this case, the BCB film does not require photosensitivity.
  • the semiconductor device and the manufacturing method thereof include chip-chip stacking (stacking of chip-state semiconductor devices obtained by wafer dicing), chip-wafer stacking (chip-state semiconductor device and pre-dicing semiconductor device).
  • the semiconductor device can be applied to any of the semiconductor devices in which the wafer state semiconductor device is stacked) or the wafer-wafer stack (lamination of the semiconductor devices in the wafer state) and the manufacturing method thereof.
  • FIGS. 3A to 3F are cross-sectional views showing respective steps of a method for manufacturing a semiconductor device according to a modification of the first embodiment.
  • a first semiconductor substrate (for example, a silicon substrate) 101 is prepared.
  • a transistor 102 and a wiring layer 103 having a multilayer via that is electrically connected to the through via 104 and the transistor 102 are formed.
  • the through via 104 penetrates the first semiconductor substrate 101 and reaches the wiring layer 103, and the side wall surface of the through via 104 is covered with an insulating film 105 with a barrier film (not shown) interposed therebetween.
  • the back surface 101 b of the first semiconductor substrate 101 is covered with a protective insulating film 106.
  • a single layer is formed on the protective insulating film 106 and the exposed bottom of the through via 104 as shown in FIG. 1,3,5-trimethylbenzene solution of negative photosensitive divinylsiloxane-bis-benzocyclobutene (BCB) monomer in which carbon nanotubes are dispersed (for example, the concentration of BCB monomer is 20 to 40% by mass, single layer carbon A nanotube concentration of 1 to 40 mass% is applied by a spin coating method to a thickness of about 5 ⁇ m, for example, and then pre-baked at 90 ° C. for 90 seconds to form the BCB monomer film 107.
  • BCB negative photosensitive divinylsiloxane-bis-benzocyclobutene
  • a region near the through via 104 (that is, a first step prepared in a later step) is formed by a lithography step.
  • a BCB film 107A (hereinafter referred to as a first BCB film 107A) insoluble in the developer is formed.
  • the BCB monomer film 107 located in the vicinity region 108 of the through via 104 that is, the BCB monomer film 107 formed on and near the exposed bottom of the through via 104 is dissolved and removed by the developer.
  • the second BCB film 121 containing no carbon nanotube is formed by coating and pre-baking.
  • the second BCB film 121 that does not contain carbon nanotubes, on the first BCB film 107A in which single-walled carbon nanotubes are dispersed and on the exposed bottom portion of the through via 104
  • the part formed in is removed.
  • the second BCB film 121 is left only in the vicinity of the through via 104.
  • the second BCB film 121 other than the region near the through via 104 can be removed.
  • a second semiconductor substrate (for example, a silicon substrate) 111 having a front surface (circuit forming surface) 111a and a back surface (opposite surface of the circuit forming surface) 111b is prepared.
  • the transistor 112 and a wiring layer 113 having a multilayer wiring electrically connected to the transistor 112 are formed.
  • an electrode portion 114 made of, for example, metal is formed on the outermost surface portion of the wiring layer 113.
  • a first The first semiconductor substrate 101 and the second semiconductor substrate 111 are pressure-bonded with the BCB film 107A (that is, an adhesive containing carbon nanotubes) and the second BCB film 121 (that is, an adhesive not containing carbon nanotubes) interposed therebetween.
  • the BCB films 107A and 121 are cured for about 1 hour at a temperature of about 350 ° C., for example.
  • the semiconductor device of this modification is completed.
  • the BCB monomer film 107 formed on and near the exposed bottom of the through via 104 is dissolved and removed by the developer, the carbon nanotubes contained in the BCB monomer film 107 are also exposed to the through via 104. It has been removed from and near the bottom. For this reason, it is possible to prevent the through vias 104 from being electrically connected to each other through the carbon nanotubes and thus the insulating property is deteriorated.
  • the first semiconductor substrate 101 and the second semiconductor substrate 111 are bonded to each other using the BCB film 107A that is an adhesive containing carbon nanotubes, and the adhesive is applied to each of the adhesives. It is formed away from the electrodes of the semiconductor substrate. Therefore, it is possible to obtain a semiconductor device having a three-dimensional laminated structure that can efficiently dissipate heat generated from the semiconductor device while preventing leakage current between electrodes, that is, a highly reliable three-dimensional laminated chip having no malfunction. Can do.
  • the removal region of the adhesive containing carbon nanotubes (first BCB film 107A), that is, the connection between the through via 104 and the electrode part 114, and the first BCB film 107A is provided.
  • an insulating adhesive (second BCB film 111) that does not contain carbon nanotubes is filled, leakage current between the electrodes due to the carbon nanotubes, that is, insulation deterioration can be more reliably prevented. it can.
  • the portion formed on the first BCB film 107A is removed from the second BCB film 121 in the step shown in FIG. 3E.
  • FIG. 4 the first semiconductor substrate 101 and the second semiconductor substrate 111 are bonded together while leaving the portion of the second BCB film 121 formed on the first BCB film 107A. May be.
  • the through via 104 is used as the electrode formed on the back surface (opposite surface of the circuit formation surface) 101b of the first semiconductor substrate 101.
  • it is formed by another method.
  • an electrode such as a bump made of metal may be used.
  • a through via may be formed instead of the electrode portion 114.
  • a BCB film is used as an adhesive between the first semiconductor substrate 101 and the second semiconductor substrate 111.
  • the type of adhesive is not particularly limited as long as it has insulating properties.
  • single-walled carbon nanotubes were used as the carbon nanotubes contained as the filler in the first BCB film 107A serving as an adhesive, but instead of this, multi-walled carbon nanotubes, or single-walled carbon nanotubes and multi-walled carbon nanotubes, A mixture of these may also be used.
  • the first BCB film 107A which is an adhesive between the first semiconductor substrate 101 and the second semiconductor substrate 111, is separated from the connection portion between the through via 104 and the electrode portion 114 by at least 2 ⁇ m or more.
  • the adhesive containing carbon nanotubes can be separated from the electrodes of each semiconductor substrate while ensuring a sufficient margin in consideration of the substrate alignment accuracy, lithography accuracy, and the like. it can.
  • the first BCB film 107A is preferably provided so as not to contact the electrode portion 114. Yes.
  • the length of the carbon nanotubes included in the first BCB film 107A is desirably sufficiently smaller than the size of the vicinity region 108 of the through via 104 where the BCB monomer film 107 is developed and removed.
  • the length of the carbon nanotubes included in the first BCB film 107A is not more than half of the separation distance between the connection portion between the through via 104 and the electrode portion 114 and the first BCB film 107A. Is preferred.
  • the length of the carbon nanotubes contained in the first BCB film 107A is the removal of the BCB monomer film 107.
  • the width of the region is 1 ⁇ 2 or less, that is, 1 ⁇ m or less, even if carbon nanotubes remain on the first semiconductor substrate 101 in the removal region when the BCB monomer film 107 is removed, generation of leakage current between electrodes, that is, insulation The occurrence of defects can be sufficiently suppressed.
  • the BCB monomer film 107 is removed by performing plasma ashing for a short time after removing the BCB monomer film 107 on and near the connection portion between the through via 104 and the electrode portion 114 using lithography and development processing. The carbon nanotubes remaining in the region can be removed almost completely.
  • the spin coating method is used to form the BCB monomer film 107, but it is also possible to use an ink jet printing method or the like instead. In this case, the BCB film does not require photosensitivity.
  • a BCB monomer film may be formed as the second BCB film 121 by a spin coating method or the like.
  • an ink jet printing method or the like can be used instead of the spin coating method.
  • the BCB monomer film does not require photosensitivity.
  • the BCB monomer film is formed only in the vicinity of the through via 104 by the printing method, it is not necessary to remove unnecessary portions by etch-back as in the case of using the coating method.
  • the semiconductor device and the manufacturing method thereof according to this modification include chip-chip stacking (stacking of chip-state semiconductor devices obtained by wafer dicing), chip-wafer stacking (chip-state semiconductor device and pre-dicing semiconductor device).
  • the semiconductor device can be applied to any of the semiconductor devices in which the wafer state semiconductor device is stacked) or the wafer-wafer stack (lamination of the semiconductor devices in the wafer state) and the manufacturing method thereof.
  • FIGS. 5A to 5E are cross-sectional views showing respective steps of the semiconductor device manufacturing method according to the second embodiment.
  • the bottom of the through via 104 is exposed on the back surface (opposite surface of the circuit forming surface) 101b side.
  • a first semiconductor substrate (for example, a silicon substrate) 101 is prepared.
  • a transistor 102 and a wiring layer 103 having a multilayer via that is electrically connected to the through via 104 and the transistor 102 are formed.
  • the through via 104 penetrates the first semiconductor substrate 101 and reaches the wiring layer 103, and the side wall surface of the through via 104 is covered with an insulating film 105 with a barrier film (not shown) interposed therebetween.
  • the back surface 101 b of the first semiconductor substrate 101 is covered with a protective insulating film 106.
  • the first semiconductor substrate 101 is provided with a plurality of through vias 104.
  • a carbon nanotube film 131 made of, for example, single-walled carbon nanotubes is formed on the protective insulating film 106 and on the exposed bottoms of the through vias 104 by using, for example, a spin coating method. .
  • a region near the through via 104 (that is, formed on the second semiconductor substrate 111 prepared in a later step and joined to the through via 104 by a lithography process).
  • a resist pattern (not shown) is formed to cover the carbon nanotube film 131 located in a region excluding the electrode portion 114 near the electrode portion 114 and the resist pattern is used as a mask. The carbon nanotube film 131 located at is removed.
  • the carbon nanotubes are formed on the remaining carbon nanotube film 131, the exposed bottom of the through via 104, and the protective insulating film 106 near the through via 104 by, for example, coating and pre-baking.
  • a BCB film 132 containing no hydrogen is formed.
  • a portion of the BCB film 132 formed on the exposed bottom portion of the through via 104 may be removed.
  • a second semiconductor substrate (for example, a silicon substrate) 111 having a front surface (circuit formation surface) 111a and a back surface (opposite surface of the circuit formation surface) 111b is prepared.
  • the transistor 112 and a wiring layer 113 having a multilayer wiring electrically connected to the transistor 112 are formed.
  • an electrode portion 114 made of, for example, metal is formed on the outermost surface portion of the wiring layer 113.
  • a BCB film is used to bond the first semiconductor substrate 101 and the second semiconductor substrate 111 so that the through via 104 and the electrode portion 114 are connected.
  • the BCB film 132 is cured for about 1 hour at a temperature of about 350 ° C., for example. To do.
  • the portion of the BCB film 132 formed on the exposed bottom of the through via 104 is not removed, in the step shown in FIG.
  • the BCB film 132 interposed between the through via 104 and the electrode portion 114 is pushed out to the periphery, and the through via 104 and the electrode portion are 114 is directly connected.
  • the semiconductor device of this embodiment is completed.
  • the carbon nanotube film 131 formed on the exposed bottom portion of the through via 104 and in the vicinity thereof is removed, the through vias 104 are electrically connected to each other through the carbon nanotube and the insulating property is deteriorated. Can be prevented.
  • the carbon nanotube film 131 is formed between the adhesive (the BCB film 132) for bonding the first semiconductor substrate 101 and the second semiconductor substrate 111 and the first semiconductor substrate 101. It is formed away from the electrodes of the semiconductor substrate. Therefore, it is possible to obtain a semiconductor device having a three-dimensional laminated structure that can efficiently dissipate heat generated from the semiconductor device while preventing leakage current between electrodes, that is, a highly reliable three-dimensional laminated chip having no malfunction. Can do.
  • an insulating adhesive that does not contain carbon nanotubes is formed between the carbon nanotube film 131 and the removal region of the carbon nanotube film 131, that is, between the connection portion between the through via 104 and the electrode portion 114 and the carbon nanotube film 131. Since the BCB film 132) is filled, it is possible to more reliably prevent the occurrence of leakage current between the electrodes due to the carbon nanotubes, that is, the deterioration of the insulating property.
  • the through via 104 is used as the electrode formed on the back surface (opposite surface of the circuit formation surface) 101b of the first semiconductor substrate 101.
  • it is formed by another method.
  • an electrode such as a bump made of metal may be used.
  • a through via may be formed instead of the electrode portion 114.
  • the BCB film is used as the adhesive between the first semiconductor substrate 101 and the second semiconductor substrate 111, but the type of the adhesive is not particularly limited as long as it has insulating properties.
  • single-walled carbon nanotubes are used as the material of the carbon nanotube film 131.
  • multi-walled carbon nanotubes or a mixture of single-walled carbon nanotubes and multi-walled carbon nanotubes may be used.
  • a thin film containing carbon nanotubes may be formed.
  • the carbon nanotube film 131 is formed between the first semiconductor substrate 101 and the adhesive (BCB film 132) for bonding the first semiconductor substrate 101 and the second semiconductor substrate 111.
  • a carbon nanotube film or a carbon nanotube-containing film may be formed between the adhesive (BCB film 132) and the second semiconductor substrate 111.
  • the carbon nanotube film 131 that is a heat dissipation member formed between the first semiconductor substrate 101 and the second semiconductor substrate 111 is at least from the connection portion between the through via 104 and the electrode portion 114. It is preferable that they are provided 2 ⁇ m or more apart. In this way, the carbon nanotube film 131 can be separated from the electrodes of each semiconductor substrate while ensuring a sufficient margin in consideration of the substrate alignment accuracy, lithography accuracy, and the like. Needless to say, when the electrode portion 114 is larger than the through via 104 as in the present embodiment, the carbon nanotube film 131 is preferably provided so as not to contact the electrode portion 114.
  • the length of the carbon nanotubes included in the carbon nanotube film 131 is desirably sufficiently smaller than the size of the vicinity region 108 of the through via 104 from which the carbon nanotube film 131 is removed.
  • the length of the carbon nanotubes included in the carbon nanotube film 131 is preferably less than or equal to half of the distance between the connection portion between the through via 104 and the electrode portion 114 and the carbon nanotube film 131.
  • the carbon nanotube film 131 having a width of 2 ⁇ m is removed around the connection portion between the through via 104 and the electrode portion 114
  • the length of the carbon nanotube included in the carbon nanotube film 131 is the width of the removal region of the carbon nanotube film 131. If the carbon nanotube film 131 is removed, even if the carbon nanotubes remain on the first semiconductor substrate 101 when the carbon nanotube film 131 is removed, leakage current between electrodes, that is, insulation failure occurs. Can be sufficiently suppressed.
  • a BCB monomer film may be formed by a spin coating method or the like.
  • an ink jet printing method or the like can be used instead of the spin coating method.
  • the BCB monomer film does not require photosensitivity.
  • the BCB monomer film is formed only around the through via 104 by the printing method, the BCB monomer film formed on the exposed bottom of the through via 104 is removed as in the case of using the coating method. There is no need.
  • the semiconductor device and the manufacturing method thereof include chip-chip stacking (stacking of chip-state semiconductor devices obtained by wafer dicing), chip-wafer stacking (chip-state semiconductor device and pre-dicing semiconductor device).
  • the semiconductor device can be applied to any of the semiconductor devices in which the wafer state semiconductor device is stacked) or the wafer-wafer stack (lamination of the semiconductor devices in the wafer state) and the manufacturing method thereof.
  • the semiconductor device of the present invention and the method for manufacturing the same can be used for the electrical connection between the electrodes that electrically connect the stacked semiconductor devices even when using an adhesive or a heat dissipation member containing carbon nanotubes.
  • the heat generated from the semiconductor device can be efficiently dissipated while preventing the insulative deterioration, and in particular, the chip-chip stack, the chip-wafer stack or the wafer-wafer stack semiconductor device and the manufacturing method thereof Etc. are useful.

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Abstract

　第１の半導体基板（１０１）と第２の半導体基板（１１１）とが接着剤（１０７Ａ）によって貼り合わされている。第１の半導体基板（１０１）には、少なくとも端部が露出する第１の電極（１０４）が設けられていると共に、第２の半導体基板（１１１）には、少なくとも端部が露出する第２の電極（１１４）が設けられている。接着剤（１０７Ａ）は、カーボンナノチューブを含有すると共に、第１の電極（１０４）と第２の電極（１１４）との接続部及びその近傍を除く領域に形成されている。

Description

半導体装置及びその製造方法
　本発明は、半導体装置及びその製造方法に関し、特に、チップ－チップ積層、チップ－ウェーハ積層又はウェーハ－ウェーハ積層された半導体装置及びその製造方法に関する。
　近年、半導体集積回路装置の高集積化、高機能化及び高速化に伴って、半導体基板のチップ－チップ積層、チップ－ウェーハ積層又はウェーハ－ウェーハ積層による３次元集積化技術が提案されている。
　従来技術による半導体基板の積層方法を図６（ａ）～（ｄ）に示す（例えば非特許文献１参照）。
　まず、図６（ａ）に示すように、裏面（回路形成面の反対面）１１ｂ側にシリコン貫通ビア１２の底部が露出した第１のシリコン基板１１を用意する。ここで、第１のシリコン基板１１の表面（回路形成面）１１ａ上には、トランジスタ１６と、シリコン貫通ビア１２及びトランジスタ１６と電気的に接続する多層配線を有する配線層１７とが形成されている。また、シリコン貫通ビア１２の側壁面はバリア膜（図示省略）を挟んで絶縁膜１８によって覆われていると共に、第１のシリコン基板１１の裏面１１ｂは保護絶縁膜１９によって覆われている。
　次に、図６（ｂ）に示すように、保護絶縁膜１９上及びシリコン貫通ビア１２の露出底部上に、絶縁性接着剤１３を回転塗布法により形成した後、プリベークを施す。
　次に、図６（ｃ）に示すように、表面（回路形成面）１４ａ及び裏面（回路形成面の反対面）１４ｂを有する第２のシリコン基板１４を用意する。ここで、第２のシリコン基板１４の表面（回路形成面）１４ａ上には、トランジスタ２０と、トランジスタ２０と電気的に接続する多層配線を有する配線層２１とが形成されている。また、配線層２１の最表面部には金属電極部１５が形成されている。
　次に、図６（ｃ）に示すように、第１のシリコン基板１１のシリコン貫通ビア１２と接合される第２のシリコン基板１４の金属電極部１５がシリコン貫通ビア１２と対向するように、絶縁性接着剤１３を挟んで第１のシリコン基板１１と第２のシリコン基板１４とを対向配置する。
　次に、図６（ｄ）に示すように、第１のシリコン基板１１と第２のシリコン基板１４とを貼り合わせるために、第１のシリコン基板１１と第２のシリコン基板１４とを圧着した状態で絶縁性接着剤１３に対してキュアを行う。
　ここで、図６（ｃ）に示す状態では、シリコン貫通ビア１２と金属電極部１５との間には絶縁性接着剤１３が介在しているが、図６（ｄ）に示す圧着により、シリコン貫通ビア１２と金属電極部１５との間に介在していた絶縁性接着剤１３は周囲に押し出されて、シリコン貫通ビア１２と金属電極部１５とが直接接続される。
特開２００４－０２７１３４号公報
Naoya Watanabe他、Compliant Bump Technology for 3D Chip-Stacking、Technical Digest of the International 3D System Integration Conference 2008 、p.321（Fig.2）
　前述のような３次元集積化技術が注目される中において、例えば、ロジックＬＳＩチップと他のチップとを積層した場合、半導体基板間を接続する接着剤の熱伝導性が低く放熱効率が悪いことに起因して、ロジックＬＳＩチップに集積されたトランジスタの動作によって発生した熱がロジックＬＳＩチップの発熱箇所近傍に蓄積されて温度上昇が引き起こされ、動作不良や信頼性不良等が発生するという問題があった。
　前記に鑑み、本発明は、半導体装置から発生する熱を効率的に放熱できる３次元積層構造の半導体装置及びその製造方法を提供することを目的とする。
　前記の目的を達成するために、本願発明者は、パッケージされた半導体装置等における放熱用の高熱伝導性材料として提案されている、カーボンナノチューブを充填材（フィラー）として含有する樹脂（例えば特許文献１参照）に着目した。ここで、カーボンナノチューブとは、炭素原子によって作られる六員環ネットワークのシートが単層又は多層の同軸管状になった物質の総称であり、単層のものを単層カーボンナノチューブ、多層のものを多層カーボンナノチューブと呼ぶが、いずれも熱伝導性が極めて高いという特徴を有している。
　しかしながら、カーボンナノチューブは電気伝導性を有している。具体的には、単層カーボンナノチューブとしては、製造過程において金属的な性質を示すものと半導体的な性質を示すものとが混在しており、両者の分離は困難である。また、多層カーボンナノチューブは金属的な性質を示す。
　従って、貫通電極等によって複数の半導体基板を積層した場合において、従来の絶縁性接着剤に置き換えて、例えば、カーボンナノチューブを充填材として含有する接着剤を半導体基板間の接着剤として使用すると、１つの半導体基板に設けられている貫通電極の露出部分同士の間で電気的絶縁性の劣化が生じてしまう。
　そこで、本願発明者は、種々の検討を重ねた結果、例えば、導電性を有するカーボンナノチューブを充填剤として含有する接着剤、又は導電性を有するカーボンナノチューブを含有する放熱部材等を用いても、電極間のリーク電流発生を防止しつつ半導体装置から発生する熱を効率的に放熱できる３次元積層構造の半導体装置及びその製造方法を発明するに至った。
　すなわち、本発明に係る第１の半導体装置は、接着剤によって互いに貼り合わされた第１の半導体基板及び第２の半導体基板と、前記第１の半導体基板における前記第２の半導体基板と対向する表面に少なくとも端部が露出するように設けられた第１の電極と、前記第２の半導体基板における前記第１の半導体基板と対向する表面に少なくとも端部が露出するように設けられた第２の電極とを備え、前記第１の電極の前記端部と前記第２の電極の前記端部とは互いに接続されており、前記接着剤は、カーボンナノチューブを含有すると共に、前記第１の電極の前記端部と前記第２の電極の前記端部との接続部及びその近傍を除く領域に形成されている。
　本発明に係る第１の半導体装置によると、カーボンナノチューブを含有する接着剤を用いて、第１の半導体基板と第２の半導体基板とを貼り合わせていると共に、当該接着剤を各半導体基板の電極から離間させて形成している。このため、電極間のリーク電流発生を防止しつつ半導体装置から発生する熱を効率的に放熱できる３次元積層構造の半導体装置、つまり、動作不良のない信頼性の高い３次元積層チップを得ることができる。
　本発明に係る第１の半導体装置において、前記接着剤は、前記第１の電極の前記端部と前記第２の電極の前記端部との前記接続部から少なくとも２μｍ以上離して設けられていてもよい。このようにすると、基板位置合わせ精度やリソグラフィ精度等を考慮した十分なマージンを確保しつつ、カーボンナノチューブを含有する接着剤を各半導体基板の電極から離間させることができる。
　本発明に係る第１の半導体装置において、前記カーボンナノチューブの長さは、前記第１の電極の前記端部と前記第２の電極の前記端部との前記接続部と、前記接着剤との離間距離の半分以下であってもよい。このようにすると、各半導体基板の電極同士の接続部及びその近傍から、カーボンナノチューブを含有する接着剤を選択的に除去した際に、当該接続部及びその近傍にカーボンナノチューブが残存したとしても、電極間のリーク電流発生を確実に防止することができる。
　本発明に係る第１の半導体装置において、前記第１の電極の前記端部と前記第２の電極の前記端部との前記接続部と、前記接着剤との間に、カーボンナノチューブを含有しない絶縁性接着剤がさらに充填されていてもよい。このようにすると、カーボンナノチューブに起因する電極間のリーク電流発生を確実に防止することができる。また、この場合、前記絶縁性接着剤は、前記第２の半導体基板と前記接着剤との間にも形成されていてもよい。
　本発明に係る第１の半導体装置において、前記接着剤は感光性を有していてもよい。このようにすると、リソグラフィ及び現像処理を用いて、各半導体基板の電極同士の接続部及びその近傍から、カーボンナノチューブを含有する接着剤を選択的に除去することができる。
　本発明に係る第１の半導体装置において、前記カーボンナノチューブは、単層カーボンナノチューブ、多層カーボンナノチューブ又はそれらの混合物であってもよい。
　本発明に係る第１の半導体装置において、前記第１の電極は、前記第１の半導体基板を貫通する貫通電極であってもよい。
　また、本発明に係る第１の半導体装置の製造方法は、第１の電極の少なくとも端部が表面に露出した第１の半導体基板を準備する工程（ａ）と、前記第１の電極の前記端部上及びその近傍を除く前記第１の半導体基板の前記表面上に、カーボンナノチューブを含有する接着剤膜を形成する工程（ｂ）と、前記工程（ｂ）の後、第２の電極の少なくとも端部が表面に露出した第２の半導体基板を準備して、前記第１の電極の前記端部と前記第２の電極の前記端部とが互いに接続するように、前記第１の半導体基板と前記第２の半導体基板とを前記接着剤膜によって貼り合わせる工程（ｃ）とを備えている。
　本発明に係る第１の半導体装置の製造方法によると、カーボンナノチューブを含有する接着剤を用いて、第１の半導体基板と第２の半導体基板とを貼り合わせていると共に、当該接着剤を各半導体基板の電極から離間させて形成している。このため、電極間のリーク電流発生を防止しつつ半導体装置から発生する熱を効率的に放熱できる３次元積層構造の半導体装置、つまり、動作不良のない信頼性の高い３次元積層チップを得ることができる。
　本発明に係る第１の半導体装置の製造方法において、前記工程（ｂ）と前記工程（ｃ）との間に、前記第１の半導体基板の前記表面上に、カーボンナノチューブを含有していない絶縁性接着剤膜を形成する工程（ｄ）をさらに備えていてもよい。このようにすると、カーボンナノチューブに起因する電極間のリーク電流発生を確実に防止することができる。また、この場合、前記工程（ｄ）と前記工程（ｃ）との間に、前記絶縁性接着剤膜における前記第１の電極の前記端部の近傍に形成されている部分以外の他の部分を除去する工程（ｅ）をさらに備えていてもよい。
　本発明に係る第１の半導体装置の製造方法において、前記接着剤は感光性を有していてもよい。このようにすると、リソグラフィ及び現像処理を用いて、各半導体基板の電極同士の接続部及びその近傍から、カーボンナノチューブを含有する接着剤を選択的に除去できる。
　本発明に係る第１の半導体装置の製造方法において、前記カーボンナノチューブは、単層カーボンナノチューブ、多層カーボンナノチューブ又はそれらの混合物であってもよい。
　本発明に係る第１の半導体装置の製造方法において、前記第１の電極は、前記第１の半導体基板を貫通する貫通電極であってもよい。
　本発明に係る第２の半導体装置は、接着剤によって互いに貼り合わされた第１の半導体基板及び第２の半導体基板と、前記第１の半導体基板における前記第２の半導体基板と対向する表面に少なくとも端部が露出するように設けられた第１の電極と、前記第２の半導体基板における前記第１の半導体基板と対向する表面に少なくとも端部が露出するように設けられた第２の電極とを備え、前記第１の電極の前記端部と前記第２の電極の前記端部とは互いに接続されており、前記第１の半導体基板又は前記第２の半導体基板と前記接着剤との間における前記第１の電極の前記端部と前記第２の電極の前記端部との接続部及びその近傍を除く領域に、カーボンナノチューブ含有膜が形成されている。
　本発明に係る第２の半導体装置によると、第１の半導体基板又は第２の半導体基板と、両基板を貼り合わせる接着剤との間にカーボンナノチューブ含有膜を各半導体基板の電極から離間させて形成している。このため、電極間のリーク電流発生を防止しつつ半導体装置から発生する熱を効率的に放熱できる３次元積層構造の半導体装置、つまり、動作不良のない信頼性の高い３次元積層チップを得ることができる。
　本発明に係る第２の半導体装置において、前記カーボンナノチューブ含有膜は、前記第１の電極の前記端部と前記第２の電極の前記端部との前記接続部から少なくとも２μｍ以上離して設けられていてもよい。このようにすると、基板位置合わせ精度やリソグラフィ精度等を考慮した十分なマージンを確保しつつ、カーボンナノチューブ含有膜を各半導体基板の電極から離間させることができる。
　本発明に係る第２の半導体装置において、前記カーボンナノチューブ含有膜に含まれるカーボンナノチューブの長さは、前記第１の電極の前記端部と前記第２の電極の前記端部との前記接続部と、前記カーボンナノチューブ含有膜との離間距離の半分以下であってもよい。このようにすると、各半導体基板の電極同士の接続部及びその近傍から、カーボンナノチューブ含有膜を選択的に除去した際に、当該接続部及びその近傍にカーボンナノチューブが残存したとしても、電極間のリーク電流発生を確実に防止することができる。
　本発明に係る第２の半導体装置において、前記カーボンナノチューブ含有膜に含まれるカーボンナノチューブは、単層カーボンナノチューブ、多層カーボンナノチューブ又はそれらの混合物であってもよい。
　本発明に係る第２の半導体装置において、前記第１の電極は、前記第１の半導体基板を貫通する貫通電極であってもよい。
　本発明に係る第２の半導体装置の製造方法は、第１の電極の少なくとも端部が表面に露出した第１の半導体基板を準備する工程（ａ）と、前記第１の電極の前記端部上及びその近傍を除く前記第１の半導体基板の前記表面上にカーボンナノチューブ含有膜を形成する工程（ｂ）と、前記工程（ｂ）の後、前記第１の半導体基板の前記表面上に、カーボンナノチューブを含有していない絶縁性接着剤膜を形成する工程（ｃ）と、前記工程（ｃ）の後、第２の電極の少なくとも端部が表面に露出した第２の半導体基板を準備して、前記第１の電極の前記端部と前記第２の電極の前記端部とが互いに接続するように、前記第１の半導体基板と前記第２の半導体基板とを前記絶縁性接着剤膜によって貼り合わせる工程（ｄ）とを備えている。
　本発明に係る第２の半導体装置の製造方法によると、第１の半導体基板又は第２の半導体基板と、両基板を貼り合わせる接着剤との間にカーボンナノチューブ含有膜を各半導体基板の電極から離間させて形成している。このため、電極間のリーク電流発生を防止しつつ半導体装置から発生する熱を効率的に放熱できる３次元積層構造の半導体装置、つまり、動作不良のない信頼性の高い３次元積層チップを得ることができる。
　本発明に係る第２の半導体装置の製造方法において、前記カーボンナノチューブ含有膜に含まれるカーボンナノチューブは、単層カーボンナノチューブ、多層カーボンナノチューブ又はそれらの混合物であってもよい。
　本発明に係る第２の半導体装置の製造方法において、前記第１の電極は、前記第１の半導体基板を貫通する貫通電極であってもよい。
　本発明によれば、カーボンナノチューブを含有する接着剤又はカーボンナノチューブを含有する放熱部材を用いても、電極間のリーク電流発生を防止しつつ半導体装置から発生する熱を効率的に放熱できる３次元積層構造の半導体装置及びその製造方法を実現でき、それにより、動作不良のない信頼性の高い３次元積層チップを得ることができる。
図１（ａ）～（ｄ）は、第１の実施形態に係る半導体装置の製造方法の各工程を示す断面図である。 図２（ａ）は、比較例として、各半導体基板の電極同士の接続部及びその近傍にも、カーボンナノチューブを含有する接着剤が形成されている３次元積層チップの断面構成を示す図であり、図２（ｂ）は、第１の実施形態に係る半導体装置の製造方法により形成された３次元積層チップの断面構成を示す図である。 図３（ａ）～（ｆ）は、第１の実施形態の変形例に係る半導体装置の製造方法の各工程を示す断面図である。 図４は、第１の実施形態の変形例に係る半導体装置の断面構成の一例を示す図である。 図５（ａ）～（ｅ）は、第２の実施形態に係る半導体装置の製造方法の各工程を示す断面図である。 図６（ａ）～（ｄ）は、従来の半導体装置の製造方法の各工程を示す断面図である。
　（第１の実施形態）
　以下、本発明の第１の実施形態に係る半導体装置及びその製造方法について、図面を参照しながら説明する。
　図１（ａ）～（ｄ）は、第１の実施形態に係る半導体装置の製造方法の各工程を示す断面図である。
　まず、図１（ａ）に示すように、裏面（回路形成面の反対面）１０１ｂ側に貫通ビア１０４の底部が露出した第１の半導体基板（例えばシリコン基板）１０１を用意する。ここで、第１の半導体基板１０１の表面（回路形成面）１０１ａ上には、トランジスタ１０２と、貫通ビア１０４及びトランジスタ１０２と電気的に接続する多層配線を有する配線層１０３とが形成されている。また、貫通ビア１０４は、第１の半導体基板１０１を貫通して配線層１０３中にまで達していると共に、貫通ビア１０４の側壁面はバリア膜（図示省略）を挟んで絶縁膜１０５によって覆われている。また、第１の半導体基板１０１の裏面１０１ｂは保護絶縁膜１０６によって覆われている。尚、図１（ａ）では貫通ビア１０４の１つを示しているが、第１の半導体基板１０１には複数の貫通ビア１０４が設けられている。
　次に、図１（ｂ）に示すように、保護絶縁膜１０６上及び貫通ビア１０４の露出底部上に、例えば、単層カーボンナノチューブを分散させたネガ型の感光性ジビニルシロキサン－ビス－ベンゾシクロブテン（ＢＣＢ）モノマーの１，３，５－トリメチルベンゼン溶液（例えば、ＢＣＢモノマーの濃度が２０～４０質量％、単層カーボンナノチューブの濃度が１～４０質量％）を、回転塗布法により例えば厚さ５μｍ程度で塗布した後、例えば９０℃で９０秒間のプリベークを施してＢＣＢモノマー膜１０７を形成する。
　次に、図１（ｃ）に示すように、リソグラフィ工程により、貫通ビア１０４の近傍領域（つまり、後工程で用意する第２の半導体基板１１１上に形成されており且つ貫通ビア１０４と接合される電極部１１４の近傍領域）１０８を除く領域に位置するＢＣＢモノマー膜１０７を露光することによって、重合反応を起こさせて、現像液に不溶なＢＣＢ膜１０７Ａを形成する。その後、現像液により、貫通ビア１０４の近傍領域１０８に位置するＢＣＢモノマー膜１０７、つまり、貫通ビア１０４の露出底部上及びその近傍に形成されたＢＣＢモノマー膜１０７を溶解して除去する。
　次に、図１（ｄ）に示すように、表面（回路形成面）１１１ａ及び裏面（回路形成面の反対面）１１１ｂを有する第２の半導体基板（例えばシリコン基板）１１１を用意する。ここで、第２の半導体基板１１１の表面（回路形成面）１１１ａ上には、トランジスタ１１２と、トランジスタ１１２と電気的に接続する多層配線を有する配線層１１３とが形成されている。また、配線層１１３の最表面部には、例えば金属からなる電極部１１４が形成されている。
　次に、図１（ｄ）に示すように、貫通ビア１０４と電極部１１４とが接続するように第１の半導体基板１０１と第２の半導体基板１１１とを貼り合わせるために、例えば、ＢＣＢ膜１０７Ａ（つまりカーボンナノチューブを含有する接着剤）を挟んで第１の半導体基板１０１と第２の半導体基板１１１とを圧着した状態で、例えば３５０℃程度の温度で１時間程度のキュアをＢＣＢ膜１０７Ａに対して行う。
　以上のようにして、本実施形態の半導体装置が完成する。ここで、現像液により、貫通ビア１０４の露出底部上及びその近傍に形成されたＢＣＢモノマー膜１０７を溶解して除去しているので、ＢＣＢモノマー膜１０７に含まれるカーボンナノチューブも貫通ビア１０４の露出底部上及びその近傍から除去されている。このため、貫通ビア１０４同士がカーボンナノチューブを介して電気的に接続して絶縁性が劣化することを防止できる。
　すなわち、本実施形態によると、カーボンナノチューブを含有する接着剤であるＢＣＢ膜１０７Ａを用いて、第１の半導体基板１０１と第２の半導体基板１１１とを貼り合わせていると共に、当該接着剤を各半導体基板の電極から離間させて形成している。このため、電極間のリーク電流発生を防止しつつ半導体装置から発生する熱を効率的に放熱できる３次元積層構造の半導体装置、つまり、動作不良のない信頼性の高い３次元積層チップを得ることができる。
　図２（ａ）は、比較例として、各半導体基板１０１及び１１１の電極（貫通ビア１０４及び電極部１１４）同士の接続部及びその近傍にも、カーボンナノチューブを含有する接着剤（ＢＣＢ膜１０７Ａ）が形成されている３次元積層チップの断面構成を示しており、図２（ｂ）は、前述の本実施形態の製造方法により形成された３次元積層チップの断面構成を示している。
　比較例においては、図２（ａ）に示すように、接着剤（ＢＣＢ膜１０７Ａ）中に含まれるカーボンナノチューブ１１５が、隣接する電極間を架橋する危険性があるため、リークパス１１６が発生してリーク電流が生じることが懸念される。
　一方、本実施形態によれば、図２（ｂ）に示すように、各半導体基板１０１及び１１１の電極（貫通ビア１０４及び電極部１１４）周辺の接着剤（ＢＣＢ膜１０７Ａ）がパターニングにより除去されているので、当該接着剤に含まれるカーボンナノチューブ１１５に起因する電極間のリーク電流発生を防止することが可能となる。
　尚、本実施形態では、第１の半導体基板１０１の裏面（回路形成面の反対面）１０１ｂに形成されている電極として、貫通ビア１０４を用いたが、これに代えて、他の方法によって形成された電極、例えば金属からなるバンプ等を用いてもよい。また、第２の半導体基板１１１において、電極部１１４に代えて、貫通ビアが形成されていてもよい。
　また、本実施形態では、第１の半導体基板１０１と第２の半導体基板１１１との接着剤として、感光性のＢＣＢ膜を用いたが、絶縁性を有していれば接着剤の種類は特に限定されない。また、第１の半導体基板１０１と第２の半導体基板１１１との接着剤に充填剤として含まれるカーボンナノチューブとして、単層カーボンナノチューブを用いたが、これに代えて、多層カーボンナノチューブ、又は単層カーボンナノチューブと多層カーボンナノチューブとの混合物を用いてもよい。
　また、第１の実施形態において、第１の半導体基板１０１と第２の半導体基板１１１との接着剤であるＢＣＢ膜１０７Ａは、貫通ビア１０４と電極部１１４との接続部から少なくとも２μｍ以上離して設けられていることが好ましい。このようにすると、基板位置合わせ精度やリソグラフィ精度等を考慮した十分なマージンを確保しつつ、カーボンナノチューブを含有する接着剤（ＢＣＢ膜１０７Ａ）を各半導体基板の電極から離間させることができる。尚、本実施形態のように、貫通ビア１０４と比較して電極部１１４の方が大きい場合、ＢＣＢ膜１０７Ａが電極部１１４と接しないように設けられていることが好ましいことは言うまでもない。
　また、本実施形態において、ＢＣＢ膜１０７Ａに含まれるカーボンナノチューブの長さは、ＢＣＢモノマー膜１０７が現像除去される貫通ビア１０４の近傍領域１０８の寸法よりも十分に小さいことが望ましい。具体的には、ＢＣＢ膜１０７Ａに含まれるカーボンナノチューブの長さは、貫通ビア１０４と電極部１１４との接続部と、ＢＣＢ膜１０７Ａとの離間距離の半分以下であることが好ましい。例えば、貫通ビア１０４と電極部１１４との接続部周辺において幅２μｍのＢＣＢモノマー膜１０７を現像除去する場合、ＢＣＢ膜１０７Ａに含まれるカーボンナノチューブの長さが、ＢＣＢモノマー膜１０７の除去領域の幅の１／２以下つまり１μｍ以下であれば、ＢＣＢモノマー膜１０７の除去時に当該除去領域にカーボンナノチューブが第１の半導体基板１０１上に残存したとしても、電極間のリーク電流発生つまり絶縁不良の発生を十分に抑制することができる。尚、リソグラフィ及び現像処理を用いて、貫通ビア１０４と電極部１１４との接続部上及びその近傍からＢＣＢモノマー膜１０７を除去した後、プラズマアッシングを短時間行うことによって、ＢＣＢモノマー膜１０７の除去領域に残存するカーボンナノチューブをほぼ完全に除去することができる。
　また、本実施形態において、ＢＣＢモノマー膜１０７の形成に回転塗布法を用いたが、これに代えて、インクジェットによる印刷法などを用いることも可能である。この場合には、ＢＣＢ膜には感光性は必要とされない。
　また、本実施形態に係る半導体装置及びその製造方法は、チップ－チップ積層（ウェハダイシングにより得られたチップ状態の半導体装置同士の積層）、チップ－ウェーハ積層（チップ状態の半導体装置と、ダイシング前のウェーハ状態の半導体装置との積層）、又はウェーハ－ウェーハ積層（ウェーハ状態の半導体装置同士の積層）された半導体装置及びその製造方法のいずれにも適用可能である。
　（第１の実施形態の変形例）
　以下、本発明の第１の実施形態の変形例に係る半導体装置及びその製造方法について、図面を参照しながら説明する。
　図３（ａ）～（ｆ）は、第１の実施形態の変形例に係る半導体装置の製造方法の各工程を示す断面図である。
　まず、第１の実施形態の図１（ａ）に示す工程と同様に、図３（ａ）に示すように、裏面（回路形成面の反対面）１０１ｂ側に貫通ビア１０４の底部が露出した第１の半導体基板（例えばシリコン基板）１０１を用意する。ここで、第１の半導体基板１０１の表面（回路形成面）１０１ａ上には、トランジスタ１０２と、貫通ビア１０４及びトランジスタ１０２と電気的に接続する多層配線を有する配線層１０３とが形成されている。また、貫通ビア１０４は、第１の半導体基板１０１を貫通して配線層１０３中にまで達していると共に、貫通ビア１０４の側壁面はバリア膜（図示省略）を挟んで絶縁膜１０５によって覆われている。また、第１の半導体基板１０１の裏面１０１ｂは保護絶縁膜１０６によって覆われている。尚、図３（ａ）では貫通ビア１０４の１つを示しているが、第１の半導体基板１０１には複数の貫通ビア１０４が設けられている。
　次に、第１の実施形態の図１（ｂ）に示す工程と同様に、図３（ｂ）に示すように、保護絶縁膜１０６上及び貫通ビア１０４の露出底部上に、例えば、単層カーボンナノチューブを分散させたネガ型の感光性ジビニルシロキサン－ビス－ベンゾシクロブテン（ＢＣＢ）モノマーの１，３，５－トリメチルベンゼン溶液（例えば、ＢＣＢモノマーの濃度が２０～４０質量％、単層カーボンナノチューブの濃度が１～４０質量％）を、回転塗布法により例えば厚さ５μｍ程度で塗布した後、例えば９０℃で９０秒間のプリベークを施してＢＣＢモノマー膜１０７を形成する。
　次に、第１の実施形態の図１（ｃ）に示す工程と同様に、図３（ｃ）に示すように、リソグラフィ工程により、貫通ビア１０４の近傍領域（つまり、後工程で用意する第２の半導体基板１１１上に形成されており且つ貫通ビア１０４と接合される電極部１１４の近傍領域）１０８を除く領域に位置するＢＣＢモノマー膜１０７を露光することによって、重合反応を起こさせて、現像液に不溶なＢＣＢ膜１０７Ａ（以下、第１のＢＣＢ膜１０７Ａという）を形成する。その後、現像液により、貫通ビア１０４の近傍領域１０８に位置するＢＣＢモノマー膜１０７、つまり、貫通ビア１０４の露出底部上及びその近傍に形成されたＢＣＢモノマー膜１０７を溶解して除去する。
　次に、図３（ｄ）に示すように、単層カーボンナノチューブを分散させた第１のＢＣＢ膜７Ａ上、貫通ビア１０４の露出底部上、及び貫通ビア１０４近傍の保護絶縁膜１０６上に、例えば塗布及びプリベークによって、カーボンナノチューブを含有しない第２のＢＣＢ膜１２１を形成する。
　次に、図３（ｅ）に示すように、カーボンナノチューブを含有しない第２のＢＣＢ膜１２１のうち、単層カーボンナノチューブを分散させた第１のＢＣＢ膜１０７Ａ上及び貫通ビア１０４の露出底部上に形成されている部分を除去する。言い換えると、貫通ビア１０４の近傍領域のみに第２のＢＣＢ膜１２１を残存させる。ここで、例えば、第２のＢＣＢ膜１２１の全面に対してエッチバックを行うことにより、貫通ビア１０４の近傍領域以外の第２のＢＣＢ膜１２１を除去することができる。
　次に、図３（ｆ）に示すように、表面（回路形成面）１１１ａ及び裏面（回路形成面の反対面）１１１ｂを有する第２の半導体基板（例えばシリコン基板）１１１を用意する。ここで、第２の半導体基板１１１の表面（回路形成面）１１１ａ上には、トランジスタ１１２と、トランジスタ１１２と電気的に接続する多層配線を有する配線層１１３とが形成されている。また、配線層１１３の最表面部には、例えば金属からなる電極部１１４が形成されている。
　次に、図３（ｆ）に示すように、貫通ビア１０４と電極部１１４とが接続するように第１の半導体基板１０１と第２の半導体基板１１１とを貼り合わせるために、例えば、第１のＢＣＢ膜１０７Ａ（つまりカーボンナノチューブを含有する接着剤）及び第２のＢＣＢ膜１２１（つまりカーボンナノチューブを含有しない接着剤）を挟んで第１の半導体基板１０１と第２の半導体基板１１１とを圧着した状態で、例えば３５０℃程度の温度で１時間程度のキュアをＢＣＢ膜１０７Ａ及び１２１に対して行う。
　以上のようにして、本変形例の半導体装置が完成する。ここで、現像液により、貫通ビア１０４の露出底部上及びその近傍に形成されたＢＣＢモノマー膜１０７を溶解して除去しているので、ＢＣＢモノマー膜１０７に含まれるカーボンナノチューブも貫通ビア１０４の露出底部上及びその近傍から除去されている。このため、貫通ビア１０４同士がカーボンナノチューブを介して電気的に接続して絶縁性が劣化することを防止できる。
　すなわち、本変形例によると、カーボンナノチューブを含有する接着剤であるＢＣＢ膜１０７Ａを用いて、第１の半導体基板１０１と第２の半導体基板１１１とを貼り合わせていると共に、当該接着剤を各半導体基板の電極から離間させて形成している。このため、電極間のリーク電流発生を防止しつつ半導体装置から発生する熱を効率的に放熱できる３次元積層構造の半導体装置、つまり、動作不良のない信頼性の高い３次元積層チップを得ることができる。
　また、本変形例では、カーボンナノチューブを含有する接着剤（第１のＢＣＢ膜１０７Ａ）の除去領域、つまり、貫通ビア１０４と電極部１１４との接続部と、第１のＢＣＢ膜１０７Ａとの間に、カーボンナノチューブを含有しない絶縁性の接着剤（第２のＢＣＢ膜１１１）を充填しているため、カーボンナノチューブに起因する電極間のリーク電流発生つまり絶縁性劣化をより確実に防止することができる。
　尚、本変形例において、図３（ｅ）に示す工程で、第２のＢＣＢ膜１２１のうち第１のＢＣＢ膜１０７Ａ上に形成されている部分を除去したが、これに代えて、例えば図４に示すように、第２のＢＣＢ膜１２１のうち第１のＢＣＢ膜１０７Ａ上に形成されている部分を残存させたまま、第１の半導体基板１０１と第２の半導体基板１１１とを貼り合わせてもよい。
　また、本変形例では、第１の半導体基板１０１の裏面（回路形成面の反対面）１０１ｂに形成されている電極として、貫通ビア１０４を用いたが、これに代えて、他の方法によって形成された電極、例えば金属からなるバンプ等を用いてもよい。また、第２の半導体基板１１１において、電極部１１４に代えて、貫通ビアが形成されていてもよい。
　また、本変形例では、第１の半導体基板１０１と第２の半導体基板１１１との接着剤として、ＢＣＢ膜を用いたが、絶縁性を有していれば接着剤の種類は特に限定されない。また、接着剤となる第１のＢＣＢ膜１０７Ａに充填剤として含まれるカーボンナノチューブとして、単層カーボンナノチューブを用いたが、これに代えて、多層カーボンナノチューブ、又は単層カーボンナノチューブと多層カーボンナノチューブとの混合物を用いてもよい。
　また、本変形例において、第１の半導体基板１０１と第２の半導体基板１１１との接着剤である第１のＢＣＢ膜１０７Ａは、貫通ビア１０４と電極部１１４との接続部から少なくとも２μｍ以上離して設けられていることが好ましい。このようにすると、基板位置合わせ精度やリソグラフィ精度等を考慮した十分なマージンを確保しつつ、カーボンナノチューブを含有する接着剤（第１のＢＣＢ膜１０７Ａ）を各半導体基板の電極から離間させることができる。尚、本変形例のように、貫通ビア１０４と比較して電極部１１４の方が大きい場合、第１のＢＣＢ膜１０７Ａが電極部１１４と接しないように設けられていることが好ましいことは言うまでもない。
　また、本変形例において、第１のＢＣＢ膜１０７Ａに含まれるカーボンナノチューブの長さは、ＢＣＢモノマー膜１０７が現像除去される貫通ビア１０４の近傍領域１０８の寸法よりも十分に小さいことが望ましい。具体的には、第１のＢＣＢ膜１０７Ａに含まれるカーボンナノチューブの長さは、貫通ビア１０４と電極部１１４との接続部と、第１のＢＣＢ膜１０７Ａとの離間距離の半分以下であることが好ましい。例えば、貫通ビア１０４と電極部１１４との接続部周辺において幅２μｍのＢＣＢモノマー膜１０７を現像除去する場合、第１のＢＣＢ膜１０７Ａに含まれるカーボンナノチューブの長さが、ＢＣＢモノマー膜１０７の除去領域の幅の１／２以下つまり１μｍ以下であれば、ＢＣＢモノマー膜１０７の除去時に当該除去領域にカーボンナノチューブが第１の半導体基板１０１上に残存したとしても、電極間のリーク電流発生つまり絶縁不良の発生を十分に抑制することができる。尚、リソグラフィ及び現像処理を用いて、貫通ビア１０４と電極部１１４との接続部上及びその近傍からＢＣＢモノマー膜１０７を除去した後、プラズマアッシングを短時間行うことによって、ＢＣＢモノマー膜１０７の除去領域に残存するカーボンナノチューブをほぼ完全に除去することができる。
　また、本変形例において、ＢＣＢモノマー膜１０７の形成に回転塗布法を用いたが、これに代えて、インクジェットによる印刷法などを用いることも可能である。この場合には、ＢＣＢ膜には感光性は必要とされない。
　また、本変形例において、第２のＢＣＢ膜１２１として、例えばＢＣＢモノマー膜を回転塗布法等により形成してもよい。或いは、回転塗布法に代えて、インクジェットによる印刷法などを用いることも可能である。この場合には、ＢＣＢモノマー膜には感光性は必要とされない。また、印刷法により貫通ビア１０４の近傍のみにＢＣＢモノマー膜を形成した場合には、塗布法を用いた場合のように全面エッチバックによる不要部分の除去を行わなくてもよい。
　また、本変形例に係る半導体装置及びその製造方法は、チップ－チップ積層（ウェハダイシングにより得られたチップ状態の半導体装置同士の積層）、チップ－ウェーハ積層（チップ状態の半導体装置と、ダイシング前のウェーハ状態の半導体装置との積層）、又はウェーハ－ウェーハ積層（ウェーハ状態の半導体装置同士の積層）された半導体装置及びその製造方法のいずれにも適用可能である。
　（第２の実施形態）
　以下、本発明の第２の実施形態に係る半導体装置及びその製造方法について、図面を参照しながら説明する。
　図５（ａ）～（ｅ）は、第２の実施形態に係る半導体装置の製造方法の各工程を示す断面図である。
　まず、第１の実施形態の図１（ａ）に示す工程と同様に、図５（ａ）に示すように、裏面（回路形成面の反対面）１０１ｂ側に貫通ビア１０４の底部が露出した第１の半導体基板（例えばシリコン基板）１０１を用意する。ここで、第１の半導体基板１０１の表面（回路形成面）１０１ａ上には、トランジスタ１０２と、貫通ビア１０４及びトランジスタ１０２と電気的に接続する多層配線を有する配線層１０３とが形成されている。また、貫通ビア１０４は、第１の半導体基板１０１を貫通して配線層１０３中にまで達していると共に、貫通ビア１０４の側壁面はバリア膜（図示省略）を挟んで絶縁膜１０５によって覆われている。また、第１の半導体基板１０１の裏面１０１ｂは保護絶縁膜１０６によって覆われている。尚、図５（ａ）では貫通ビア１０４の１つを示しているが、第１の半導体基板１０１には複数の貫通ビア１０４が設けられている。
　次に、図５（ｂ）に示すように、保護絶縁膜１０６上及び貫通ビア１０４の露出底部上に、例えばスピンコート法を用いて、例えば単層カーボンナノチューブからなるカーボンナノチューブ膜１３１を形成する。
　次に、図５（ｃ）に示すように、リソグラフィ工程により、貫通ビア１０４の近傍領域（つまり、後工程で用意する第２の半導体基板１１１上に形成されており且つ貫通ビア１０４と接合される電極部１１４の近傍領域）１０８を除く領域に位置するカーボンナノチューブ膜１３１を覆うレジストパターン（図示省略）を形成し、当該レジストパターンをマスクとして、例えばプラズマエッチングにより、貫通ビア１０４の近傍領域１０８に位置するカーボンナノチューブ膜１３１を除去する。
　次に、図５（ｄ）に示すように、残存するカーボンナノチューブ膜１３１上、貫通ビア１０４の露出底部上、及び貫通ビア１０４近傍の保護絶縁膜１０６上に、例えば塗布及びプリベークによって、カーボンナノチューブを含有しないＢＣＢ膜１３２を形成する。ここで、ＢＣＢ膜１３２のうち貫通ビア１０４の露出底部上に形成されている部分を除去してもよい。
　次に、図５（ｅ）に示すように、表面（回路形成面）１１１ａ及び裏面（回路形成面の反対面）１１１ｂを有する第２の半導体基板（例えばシリコン基板）１１１を用意する。ここで、第２の半導体基板１１１の表面（回路形成面）１１１ａ上には、トランジスタ１１２と、トランジスタ１１２と電気的に接続する多層配線を有する配線層１１３とが形成されている。また、配線層１１３の最表面部には、例えば金属からなる電極部１１４が形成されている。
　次に、図５（ｅ）に示すように、貫通ビア１０４と電極部１１４とが接続するように第１の半導体基板１０１と第２の半導体基板１１１とを貼り合わせるために、例えば、ＢＣＢ膜１３２（つまりカーボンナノチューブを含有しない接着剤）を挟んで第１の半導体基板１０１と第２の半導体基板１１１とを圧着した状態で、例えば３５０℃程度の温度で１時間程度のキュアをＢＣＢ膜１３２に対して行う。
　ここで、図５（ｄ）に示す工程において、ＢＣＢ膜１３２のうち貫通ビア１０４の露出底部上に形成されている部分が除去されていない場合には、図５（ｅ）に示す工程において、第１の半導体基板１０１と第２の半導体基板１１１とを圧着した際に、貫通ビア１０４と電極部１１４との間に介在していたＢＣＢ膜１３２が周囲に押し出され、貫通ビア１０４と電極部１１４とが直接接続される。
　以上のようにして、本実施形態の半導体装置が完成する。ここで、貫通ビア１０４の露出底部上及びその近傍に形成されたカーボンナノチューブ膜１３１を除去しているため、貫通ビア１０４同士がカーボンナノチューブを介して電気的に接続して絶縁性が劣化することを防止できる。
　すなわち、本実施形態によると、第１の半導体基板１０１と第２の半導体基板１１１とを貼り合わせる接着剤（ＢＣＢ膜１３２）と、第１の半導体基板１０１との間にカーボンナノチューブ膜１３１を各半導体基板の電極から離間させて形成している。このため、電極間のリーク電流発生を防止しつつ半導体装置から発生する熱を効率的に放熱できる３次元積層構造の半導体装置、つまり、動作不良のない信頼性の高い３次元積層チップを得ることができる。
　また、本実施形態では、カーボンナノチューブ膜１３１の除去領域、つまり、貫通ビア１０４と電極部１１４との接続部と、カーボンナノチューブ膜１３１との間に、カーボンナノチューブを含有しない絶縁性の接着剤（ＢＣＢ膜１３２）を充填しているため、カーボンナノチューブに起因する電極間のリーク電流発生つまり絶縁性劣化をより確実に防止することができる。
　尚、本実施形態では、第１の半導体基板１０１の裏面（回路形成面の反対面）１０１ｂに形成されている電極として、貫通ビア１０４を用いたが、これに代えて、他の方法によって形成された電極、例えば金属からなるバンプ等を用いてもよい。また、第２の半導体基板１１１において、電極部１１４に代えて、貫通ビアが形成されていてもよい。
　また、本実施形態では、第１の半導体基板１０１と第２の半導体基板１１１との接着剤として、ＢＣＢ膜を用いたが、絶縁性を有していれば接着剤の種類は特に限定されない。
　また、本実施形態では、カーボンナノチューブ膜１３１の材料として、単層カーボンナノチューブを用いたが、これに代えて、多層カーボンナノチューブ、又は単層カーボンナノチューブと多層カーボンナノチューブとの混合物を用いてもよい。また、カーボンナノチューブ膜１３１に代えて、カーボンナノチューブを含有する薄膜を形成してもよい。
　また、本実施形態では、第１の半導体基板１０１と第２の半導体基板１１１とを貼り合わせる接着剤（ＢＣＢ膜１３２）と、第１の半導体基板１０１との間にカーボンナノチューブ膜１３１を形成した。しかし、これに代えて、又は、これに加えて、接着剤（ＢＣＢ膜１３２）と第２の半導体基板１１１との間にカーボンナノチューブ膜又はカーボンナノチューブ含有膜を形成してもよい。
　また、本実施形態において、第１の半導体基板１０１と第２の半導体基板１１１との間に形成される放熱部材であるカーボンナノチューブ膜１３１は、貫通ビア１０４と電極部１１４との接続部から少なくとも２μｍ以上離して設けられていることが好ましい。このようにすると、基板位置合わせ精度やリソグラフィ精度等を考慮した十分なマージンを確保しつつ、カーボンナノチューブ膜１３１を各半導体基板の電極から離間させることができる。尚、本実施形態のように、貫通ビア１０４と比較して電極部１１４の方が大きい場合、カーボンナノチューブ膜１３１が電極部１１４と接しないように設けられていることが好ましいことは言うまでもない。
　また、本実施形態において、カーボンナノチューブ膜１３１に含まれるカーボンナノチューブの長さは、カーボンナノチューブ膜１３１が除去される貫通ビア１０４の近傍領域１０８の寸法よりも十分に小さいことが望ましい。具体的には、カーボンナノチューブ膜１３１に含まれるカーボンナノチューブの長さは、貫通ビア１０４と電極部１１４との接続部と、カーボンナノチューブ膜１３１との離間距離の半分以下であることが好ましい。例えば、貫通ビア１０４と電極部１１４との接続部周辺において幅２μｍのカーボンナノチューブ膜１３１を除去する場合、カーボンナノチューブ膜１３１に含まれるカーボンナノチューブの長さが、カーボンナノチューブ膜１３１の除去領域の幅の１／２以下つまり１μｍ以下であれば、カーボンナノチューブ膜１３１の除去時に当該除去領域にカーボンナノチューブが第１の半導体基板１０１上に残存したとしても、電極間のリーク電流発生つまり絶縁不良の発生を十分に抑制することができる。
　また、本実施形態において、ＢＣＢ膜１３２として、例えばＢＣＢモノマー膜を回転塗布法等により形成してもよい。或いは、回転塗布法に代えて、インクジェットによる印刷法などを用いることも可能である。この場合には、ＢＣＢモノマー膜には感光性は必要とされない。また、印刷法により貫通ビア１０４の周辺のみにＢＣＢモノマー膜を形成した場合には、塗布法を用いた場合のように、貫通ビア１０４の露出底部上に形成されているＢＣＢモノマー膜を除去する必要はない。
　また、本実施形態に係る半導体装置及びその製造方法は、チップ－チップ積層（ウェハダイシングにより得られたチップ状態の半導体装置同士の積層）、チップ－ウェーハ積層（チップ状態の半導体装置と、ダイシング前のウェーハ状態の半導体装置との積層）、又はウェーハ－ウェーハ積層（ウェーハ状態の半導体装置同士の積層）された半導体装置及びその製造方法のいずれにも適用可能である。
　以上に説明したように、本発明の半導体装置及びその製造方法は、カーボンナノチューブを含有する接着剤又は放熱部材等を用いても、積層された半導体装置同士を電気的に接続する電極間における電気的な絶縁性劣化を防止しつつ、半導体装置から発生する熱を効率的に放熱できるものであり、特に、チップ－チップ積層、チップ－ウェーハ積層又はウェーハ－ウェーハ積層された半導体装置及びその製造方法等に有用である。
　１０１　　第１の半導体基板
　１０１ａ　　第１の半導体基板の表面
　１０１ｂ　　第１の半導体基板の裏面
　１０２　　トランジスタ
　１０３　　配線層
　１０４　　貫通ビア
　１０５　　絶縁膜
　１０６　　保護絶縁膜
　１０７　　ＢＣＢモノマー膜
　１０７Ａ　　ＢＣＢ膜（第１のＢＣＢ膜）
　１０８　　貫通ビアの近傍領域
　１１１　　第２の半導体基板
　１１１ａ　　第２の半導体基板の表面
　１１１ｂ　　第２の半導体基板の裏面
　１１２　　トランジスタ
　１１３　　配線層
　１１４　　電極部
　１１５　　カーボンナノチューブ
　１１６　　リークパス
　１２１　　第２のＢＣＢ膜
　１３１　　カーボンナノチューブ膜
　１３２　　ＢＣＢ膜

Claims (22)

  1. 　接着剤によって互いに貼り合わされた第１の半導体基板及び第２の半導体基板と、
    　前記第１の半導体基板における前記第２の半導体基板と対向する表面に少なくとも端部が露出するように設けられた第１の電極と、
    　前記第２の半導体基板における前記第１の半導体基板と対向する表面に少なくとも端部が露出するように設けられた第２の電極とを備え、
    　前記第１の電極の前記端部と前記第２の電極の前記端部とは互いに接続されており、
    　前記接着剤は、カーボンナノチューブを含有すると共に、前記第１の電極の前記端部と前記第２の電極の前記端部との接続部及びその近傍を除く領域に形成されていることを特徴とする半導体装置。
  2. 　請求項１に記載の半導体装置において、
    　前記接着剤は、前記第１の電極の前記端部と前記第２の電極の前記端部との前記接続部から少なくとも２μｍ以上離して設けられていることを特徴とする半導体装置。
  3. 　請求項１又は２に記載の半導体装置において、
    　前記カーボンナノチューブの長さは、前記第１の電極の前記端部と前記第２の電極の前記端部との前記接続部と、前記接着剤との離間距離の半分以下であることを特徴とする半導体装置。
  4. 　請求項１～３のいずれか１項に記載の半導体装置において、
    　前記第１の電極の前記端部と前記第２の電極の前記端部との前記接続部と、前記接着剤との間に、カーボンナノチューブを含有しない絶縁性接着剤がさらに充填されていることを特徴とする半導体装置。
  5. 　請求項４に記載の半導体装置において、
    　前記絶縁性接着剤は、前記第２の半導体基板と前記接着剤との間にも形成されていることを特徴とする半導体装置。
  6. 　請求項１～５のいずれか１項に記載の半導体装置において、
    　前記接着剤は感光性を有することを特徴とする半導体装置。
  7. 　請求項１～６のいずれか１項に記載の半導体装置において、
    　前記カーボンナノチューブは、単層カーボンナノチューブ、多層カーボンナノチューブ又はそれらの混合物であることを特徴とする半導体装置。
  8. 　請求項１～７のいずれか１項に記載の半導体装置において、
    　前記第１の電極は、前記第１の半導体基板を貫通する貫通電極であることを特徴とする半導体装置。
  9. 　第１の電極の少なくとも端部が表面に露出した第１の半導体基板を準備する工程（ａ）と、
    　前記第１の電極の前記端部上及びその近傍を除く前記第１の半導体基板の前記表面上に、カーボンナノチューブを含有する接着剤膜を形成する工程（ｂ）と、
    　前記工程（ｂ）の後、第２の電極の少なくとも端部が表面に露出した第２の半導体基板を準備して、前記第１の電極の前記端部と前記第２の電極の前記端部とが互いに接続するように、前記第１の半導体基板と前記第２の半導体基板とを前記接着剤膜によって貼り合わせる工程（ｃ）とを備えていることを特徴とする半導体装置の製造方法。
  10. 　請求項９に記載の半導体装置の製造方法において、
    　前記工程（ｂ）と前記工程（ｃ）との間に、
    　前記第１の半導体基板の前記表面上に、カーボンナノチューブを含有していない絶縁性接着剤膜を形成する工程（ｄ）をさらに備えていることを特徴とする半導体装置の製造方法。
  11. 　請求項１０に記載の半導体装置の製造方法において、
    　前記工程（ｄ）と前記工程（ｃ）との間に、
    　前記絶縁性接着剤膜における前記第１の電極の前記端部の近傍に形成されている部分以外の他の部分を除去する工程（ｅ）をさらに備えていることを特徴とする半導体装置の製造方法。
  12. 　請求項９～１１のいずれか１項に記載の半導体装置の製造方法において、
    　前記接着剤は感光性を有することを特徴とする半導体装置の製造方法。
  13. 　請求項９～１２のいずれか１項に記載の半導体装置の製造方法において、
    　前記カーボンナノチューブは、単層カーボンナノチューブ、多層カーボンナノチューブ又はそれらの混合物であることを特徴とする半導体装置の製造方法。
  14. 　請求項９～１３のいずれか１項に記載の半導体装置の製造方法において、
    　前記第１の電極は、前記第１の半導体基板を貫通する貫通電極であることを特徴とする半導体装置の製造方法。
  15. 　接着剤によって互いに貼り合わされた第１の半導体基板及び第２の半導体基板と、
    　前記第１の半導体基板における前記第２の半導体基板と対向する表面に少なくとも端部が露出するように設けられた第１の電極と、
    　前記第２の半導体基板における前記第１の半導体基板と対向する表面に少なくとも端部が露出するように設けられた第２の電極とを備え、
    　前記第１の電極の前記端部と前記第２の電極の前記端部とは互いに接続されており、
    　前記第１の半導体基板又は前記第２の半導体基板と前記接着剤との間における前記第１の電極の前記端部と前記第２の電極の前記端部との接続部及びその近傍を除く領域に、カーボンナノチューブ含有膜が形成されていることを特徴とする半導体装置。
  16. 　請求項１５に記載の半導体装置において、
    　前記カーボンナノチューブ含有膜は、前記第１の電極の前記端部と前記第２の電極の前記端部との前記接続部から少なくとも２μｍ以上離して設けられていることを特徴とする半導体装置。
  17. 　請求項１５又は１６に記載の半導体装置において、
    　前記カーボンナノチューブ含有膜に含まれるカーボンナノチューブの長さは、前記第１の電極の前記端部と前記第２の電極の前記端部との前記接続部と、前記カーボンナノチューブ含有膜との離間距離の半分以下であることを特徴とする半導体装置。
  18. 　請求項１５～１７のいずれか１項に記載の半導体装置において、
    　前記カーボンナノチューブ含有膜に含まれるカーボンナノチューブは、単層カーボンナノチューブ、多層カーボンナノチューブ又はそれらの混合物であることを特徴とする半導体装置。
  19. 　請求項１５～１８のいずれか１項に記載の半導体装置において、
    　前記第１の電極は、前記第１の半導体基板を貫通する貫通電極であることを特徴とする半導体装置。
  20. 　第１の電極の少なくとも端部が表面に露出した第１の半導体基板を準備する工程（ａ）と、
    　前記第１の電極の前記端部上及びその近傍を除く前記第１の半導体基板の前記表面上にカーボンナノチューブ含有膜を形成する工程（ｂ）と、
    　前記工程（ｂ）の後、前記第１の半導体基板の前記表面上に、カーボンナノチューブを含有していない絶縁性接着剤膜を形成する工程（ｃ）と、
    　前記工程（ｃ）の後、第２の電極の少なくとも端部が表面に露出した第２の半導体基板を準備して、前記第１の電極の前記端部と前記第２の電極の前記端部とが互いに接続するように、前記第１の半導体基板と前記第２の半導体基板とを前記絶縁性接着剤膜によって貼り合わせる工程（ｄ）とを備えていることを特徴とする半導体装置の製造方法。
  21. 　請求項２０に記載の半導体装置の製造方法において、
    　前記カーボンナノチューブ含有膜に含まれるカーボンナノチューブは、単層カーボンナノチューブ、多層カーボンナノチューブ又はそれらの混合物であることを特徴とする半導体装置の製造方法。
  22. 　請求項２０又は２１に記載の半導体装置の製造方法において、
    　前記第１の電極は、前記第１の半導体基板を貫通する貫通電極であることを特徴とする半導体装置の製造方法。
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JP2009164152A (ja) * 2007-12-28 2009-07-23 Nikon Corp 積層型半導体装置
JP2009246258A (ja) * 2008-03-31 2009-10-22 Nikon Corp 半導体装置および製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009164152A (ja) * 2007-12-28 2009-07-23 Nikon Corp 積層型半導体装置
JP2009246258A (ja) * 2008-03-31 2009-10-22 Nikon Corp 半導体装置および製造方法

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